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
• • 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
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• • 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
• • 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
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
• • 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
  • C08G2290/00—Compositions for creating anti-fogging
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249987—With nonvoid component of specified composition
  • Y10T428/24999—Inorganic
• • 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]
  • Y10T442/647—Including a foamed layer or component
• • 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]
  • Y10T442/659—Including an additional nonwoven fabric

Definitions

• This invention describes composites comprising a polyurethane foam core and an outer layer of a textile material.
• Suitable polyurethane foam cores for the composite materials of the present invention comprise hydrophilic polyester-polyurethane foam materials. These composite materials can be used for the production of vehicle interior trim parts.
• polyester-polyurethane foamed materials are splitting of long blocks of block foamed material to form strip material, followed by further processing to produce composite materials suitable for use as interior trim parts in vehicles after lamination with textiles or sheeting materials.
• Composite materials for vehicle trim are understood to mean textile-laminated PUR foamed materials such as, for example, seat or seat back upholstered supports.
• the strip material which is used according to the invention is of sufficient thickness, this disadvantage can also be compensated for, at least in part, by the moisture absorption behavior of the layer of foamed material which remains in the sandwich lamination (i.e., from the top side of the textile to the underside of the sheeting).
• flame-lamination is a technique which has proved to be a particularly inexpensive. Flame lamination is, however, an efficient technique for joining strip materials made of flexible foamed materials to textiles and sheeting.
• foamed material strips are joined to textile strip material, in a continuous process at, for example, operating speeds within the range from 15 to 40 m/minute.
• This process comprises melting the surface of the foamed material by flaming (i.e., burning) it with a gas flame burner bar immediately before the textile strip is supplied.
• flaming i.e., burning
• gas flame burner bar i.e., a gas flame burner bar
• decomposition reactions also occur on the surface.
• the textile and foamed material strips are pressed together by, for example, being passed between pairs of rotating rollers of the flame-laminating installation. After pressing, the melt which is formed on the surface of the foamed material has to form a relatively continuous bond.
• ether-PUR foamed materials possess properties which, in practice, make them highly suitable for use as upholstery materials. These include, for example, a significantly higher permeability to air at a comparable bulk density, and a considerably higher level of elasticity.
• Ester-PUR foamed materials have a comparatively pronounced thermoplastic character, thus improving their capacity for flame-laminating.
• ester-PUR foamed materials with sufficiently open cell structure exhibit appreciable moisture absorption properties, and enable an improved seat climate, and thus, are expected to result in an increased level of seat comfort in one or the other upholstery situation.
• polyether-PUR flexible foamed materials are preferably produced in a single-stage (“one shot”) process. Details of the chemistry and process technology are given, for example, in the Kunststoff-Handbuch, Volume VII, Carl Hanser-Verlag Kunststoff/Vienna, 3rd Edition (1993), on pages 193-220. This process results in block foamed materials (for further processing) which exhibit unsatisfactory hydrophilic properties, even when they are mainly of an open-cell character.
• the object of the present invention was thus to provide polyurethane foamed materials which exhibit good hydrophilic properties and which are suitable for the production of composite materials which are particularly suitable for vehicle interior trim.
• polyester-PUR foamed materials which have been produced by replacing part of the polyester polyols in the formulations by polyether polyols which have a degree of ethoxylation greater than 30% by weight, achieve this object particularly well.
• the present invention relates to a composite comprising a polyurethane core and at least one outer layer wherein the polyurethane core comprises hydrophilic polyester-polyurethane foamed materials.
• Suitable polyester-polyurethane foams materials comprise the reaction product of:
• the present invention also relates to a process for the production of these composite materials, and particularly to a continuous process for the production of a flame-laminated composite of textile and foamed material.
• the degree of ethoxylation of the polyether polyols which are used is usually greater than 30% by weight, and is preferably between 50 and 95% by weight.
• Trimethylolpropane derived polyether polyols, and/or polyether polyols which are derived from glycerol, preferably highly ethoxylated polyether polyols which are derived from glycerol, are usually employed (e.g. VP PU41WB01, a trifunctional polyether polyol commercially available from Bayer AG).
• the content of highly ethoxylated polyether polyols present in the polyol mixture is usually between 2 and 50% by weight, based on the combined weight of components b), c) and d).
• Suitable polyester polyols can be produced by the condensation reaction of organic dicarboxylic acids, which contain 2 to 12 carbon atoms, and polyhydric alcohols.
• Succinic acid, glutaric acid or adipic acid, or corresponding mixtures of dicarboxylic acids are preferably used as the organic dicarboxylic acids.
• Araliphatic dicarboxylic acids such as, for example, ortho- or terephthalic acid, or unsaturated carboxylic acids such as, for example, maleic and fumaric acid, can also be used.
• polyhydric alcohols When used as condensation reactants in the preparation of polyester polyols, they generally also contain from 2 to 12 carbon atoms.
• Dihydric (glycol) reactants from the series ranging from ethylene glycol to 1,6-hexanediol are particularly preferred as polyhydric alcohols in the present invention.
• Diethylene glycol or dipropylene glycol are more preferred.
• Polyester polyols prepared from adipic acid and diethylene glycol and 2 to 3 wt % of trimethylol propane as a branching agents e.g. VP PU60WB01 or VP PU 60WB02, commercially available from Bayer AG
• branching agents e.g. VP PU60WB01 or VP PU 60WB02, commercially available from Bayer AG
• other low-fogging formulations are preferably used.
• Highly ethoxylated polyether polyols of higher functionality can also be used instead of highly ethoxylated polyether diols (difunctional) or highly ethoxylated triols, e.g. polyether polyols based on glycerine (such as VP PU41 WB01 of Bayer AG), and analogous products.
• highly ethoxylated polyether diols diols
• highly ethoxylated triols e.g. polyether polyols based on glycerine (such as VP PU41 WB01 of Bayer AG), and analogous products.
• the stabilizers which are typically used are modern silicone stabilizers which result in a fine-celled foamed material structure which is as open-celled as possible.
• Examples of such stabilizers include compounds based on polydimethylsiloxane (e.g. VP Al 3613 or VP Al 3614 of Bayer AG, or B 8300 and B 8301 of Goldschmidt AG).
• the proportion of highly ethoxylated polyether polyols in the polyol mixture for the composites of the present invention typically ranges between about 2 and 50%, based on the combined weight of component b), c) and d).
• the functionality of the ethoxylated polyether polyols, as determined by the starter molecule, is usually between 2 and 6. Trifunctional components are particularly preferred.
• polyester polyols of a low-fogging formulation such as polyester polyols characterized by an OH number of 60 or 52, respectively, which are the reaction product of adipic acid and diethylene glycol and trimethylol propane as the branching component and have been processed by short-path distillation to remove volatile constituents such as cyclic diethylene glycol esters (e.g. VP PU 60WB01 or VP PU 60WB02 of Bayer AG).
• the substances which are used to catalyze the foaming reaction apart from the customary amine components (see the Kunststoff-Handbuch, Volume VII, Carl Hanser-Verlag, Kunststoff/Vienna, 3rd Edition (1993), pages 104-107 and page 219) can predominantly comprise those which contribute little to the odor or fogging of the resultant foamed materials.
• these include, for example, various compounds as described below.
• Dimethylpiperazine, bis-(dimethylaminoethyl) ether available as either Niax A 30 supplied by OSI, or as Dabco BL 11 supplied by Air Products; each of which are in the form of preparations
• dimethyl-ethanolamine and N,N,N-trimethyl-N-hydroxyethyl-bisaminoethyl ether available as Desmorapid KE 9645 supplied by Rhein-Chemie
• Another example is 1,2-dimethylimidazole (available as Dabco 2039 supplied by Air Products), or different types of mixtures of amines or urea/amine combinations such as these.
• adjuvant substances and additives are optionally added in order to influence other properties.
• examples thereof include flame retardants, emulsifiers, dispersing agents, adjuvant substances to improve the ease of punching out the material, or antioxidants to prevent discoloration of the core.
• the foamed materials can be produced with bulk densities within the range of from about 20 to 80 kg/m 3 , which is customary for polyester-PUR foamed materials.
• additional foaming agents such as, for example, by means of liquid carbon dioxide (e.g. by employing the NovaFlex technique (Hennecke/Bayer AG) and/or related processes, or by employing a reduced pressure technique or analogous techniques), the range of uses and the possibilities of use can be widened correspondingly.
• the density of the foamed material preferably falls within the range of the specifications of the automobile industry, namely from about 25 to about 45 kg/m 3 .
• the wetting capacity i.e., the accessible internal surface of the foamed material
• the range of bulk density of from 30 to 40 kg/m 3 is particularly preferred.
• the foamed materials which are used in accordance with the present invention exhibit hydrophilic properties. They are capable of absorbing 10 times the amount of water, with respect to the weight of foamed material, within 20 to 25 seconds.
• the dry foamed materials i.e., foamed materials comprising a proportion of polyether polyol of from about 10% by weight in the polyol mixture
• the foamed material sample sinks within seconds.
• the PUR foamed materials can be used for the production of foamed material-textile composite materials which are manufactured in the form of sandwich laminates, by adhesive or flame lamination.
• the polyester-PUR foamed materials are preferably used for the production of flame-laminated textile composite materials.
• suitable additives of this type include, but are not limited to, aliphatic diols of the general formula HO—(R—CH) n —OH, wherein n can be an integer within the range from 2 to 15 and R can be an alkyl or alkoxy group, as well as oligomeric polyoxypropylene glycols, polyoxyethylene glycols, propoxylation and ethoxylation products of polyhydric alcohols, or aliphatic and aromatic polyester glycols with molecular weights ranging from about 32 to 700, or OH-functional esters of phosphoric or phosphorous acid (such as Levagard 4090 N of Bayer AG, or Weston 430, commercially available from General Electric Spec. Chemicals).
• n represents an integer of from 2 to 4, preferably 2 to 3, and
• Q represents an aliphatic hydrocarbon radical containing 2 to 18 carbon atoms, preferably 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical containing 4 to 15 carbon atoms, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon radical containing 6 to 15 carbon atoms, preferably 6 to 13 carbon atoms, or an araliphatic hydrocarbon radical containing 8 to 15 carbon atoms, preferably 8 to 13 carbon atoms.
• polyisocyanates examples include those which are described in, for example, DE-OS 2,832,253, pages 10 to 11.
• the polyisocyanates which are particularly preferred are those which are readily accessible industrially, e.g., 2,4- and/or 2,6-toluene diisocyanate and any mixtures of these isomers (“TDI”), polyphenylpoly-methylene polyisocyanates such as those which are produced by aniline-formaldehyde condensation and subsequent phosgenation (“MDI”), and polyisocyanates which comprise carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (modified polyisocyanates), particularly those modified polyisocyanates which are derived from 2,4- and/or 2,6-toluene diisocyanate or from 4,4′-and/or 2,4′-diphenylmethane diisocyanate.
• TDI 2,4- and/or 2,6-toluene diisocyanate and any mixtures of these isomers
• MDI aniline-formalde
• reaction components were reacted by known, customary methods, wherein motor-driven devices were usually employed.
• Polyol A a low fogging polyester polyol prepared from adipic acid, diethylene glycol and 3 wt % of trimethylol propane, having an OH number of 60 (VP PU 60WB01 of Bayer AG);
• Polyol B a trifunctional polyether polyol based on glycerine and having an OH number of 37 and a degree of ethoxylation of at least 70% by weight (VP PU 41WB01 of Bayer AG);
• Polyol C an ethoxylated bisphenol A having an OH number of about 270 to about 285 (commercially available as Dianol 240/1 from Akzo-Chemie);
• Polyol D a low fogging polyester polyol prepared from adipic acid, diethylene glycol and 2 wt % of trimethylol propane having an OH number of 52 (VP PU 60WB01 of Bayer AG);
• Polyol E a difunctional polyether polyo
• Stabilizer A a silicone stabilizer based on polydimethylsiloxane (VP AI 3613 of Bayer AG); Stabilizer B: a silicone stabilizer based on polydimethylsiloxane (B8301 of Th.
• Catalyst A an amine catalyst (Niax A 30 of OSI)
• Catalyst B an amine catalyst (RC-A-117 of Rhein Chemie)
• Isocyanate A an isomeric mixture of 2,4-toluene dilsocyanate and 2,6-toluene dilsocyanate in a weight ratio of 80:20
• Isocyanate B an isomeric mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate in a weight ratio of 65:35
• each of the foamed materials produced in Examples 1-6 as described above were tested against a standard ester foamed material of a low-fogging formulation, in a simulation test which was specific to the application.
• the formulation of this standard foamed material was as follows: Standard Foam: Polyol D: 100 parts by weight Water: 3.0 parts by weight Stabilizer A: 1.0 parts by weight Catalyst A: 0.2 parts by weight Catalyst B: 0.2 parts by weight Isocyanate A: 18.4 parts by weight Isocyanate B: 18.4 parts by weight

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Laminated Bodies (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
• Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 1999
  • 1999-03-06 DE DE19909978A patent/DE19909978A1/de not_active Withdrawn
• 2000
  • 2000-02-23 DE DE50007650T patent/DE50007650D1/de not_active Expired - Lifetime
  • 2000-02-23 PT PT00103382T patent/PT1035146E/pt unknown
  • 2000-02-23 EP EP00103382A patent/EP1035146B1/de not_active Expired - Lifetime
  • 2000-02-23 SI SI200030522T patent/SI1035146T1/xx unknown
  • 2000-02-23 ES ES00103382T patent/ES2228316T3/es not_active Expired - Lifetime
  • 2000-02-23 AT AT00103382T patent/ATE275593T1/de active
  • 2000-02-25 US US09/513,089 patent/US20020094432A1/en not_active Abandoned
  • 2000-03-02 CA CA002299905A patent/CA2299905C/en not_active Expired - Fee Related
  • 2000-03-03 JP JP2000058713A patent/JP2000289174A/ja active Pending
  • 2000-03-04 KR KR1020000010850A patent/KR100582975B1/ko not_active IP Right Cessation
  • 2000-03-06 CN CNB001038931A patent/CN1172990C/zh not_active Expired - Fee Related
  • 2000-03-08 BR BR0001368-4A patent/BR0001368A/pt active Search and Examination
• 2001
  • 2001-03-07 HK HK01101665A patent/HK1030793A1/xx not_active IP Right Cessation
  • 2001-09-14 US US09/955,227 patent/US6673849B2/en not_active Expired - Fee Related

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