EP3149062A1 - Matériau composite comprenant une couche de revêtement et une couche de mousse de polyuréthane - Google Patents

Matériau composite comprenant une couche de revêtement et une couche de mousse de polyuréthane

Info

Publication number
EP3149062A1
EP3149062A1 EP15725046.5A EP15725046A EP3149062A1 EP 3149062 A1 EP3149062 A1 EP 3149062A1 EP 15725046 A EP15725046 A EP 15725046A EP 3149062 A1 EP3149062 A1 EP 3149062A1
Authority
EP
European Patent Office
Prior art keywords
polyurethane foam
catalysts
polyurethane
cover layer
groups
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Withdrawn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
EP15725046.5A
Other languages
German (de)
English (en)
Inventor
Gerd Rischko
Jörg Pöltl
Julio Albuerne
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
Publication of EP3149062A1 publication Critical patent/EP3149062A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/3225—Polyamines
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    • C08G18/324—Polyamines aromatic containing only one aromatic ring
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    • C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • 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
    • B29K2627/00—Use of polyvinylhalogenides or derivatives thereof for preformed parts, e.g. for inserts
    • B29K2627/06—PVC, i.e. polyvinylchloride
    • 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
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3005—Body finishings
    • B29L2031/3008—Instrument panels
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • 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
    • C08G2110/0016—Foam properties semi-rigid
    • 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
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • 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
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • 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

Definitions

  • the present invention relates to a composite element comprising at least one cover layer and polyurethane foam, in which a cover layer is placed in a mold and a polyurethane reaction mixture is added to the cover layer and reacted to form a polyurethane foam, the polyurethane reaction mixture being obtained by mixing (a) polyisocyanate (b) compounds having isocyanate-reactive OH groups, (c) blowing agents containing water, (d) thickening agents and optionally (e) catalysts, and (f) other auxiliaries and additives, and the polyurethane foam having a density of not more than 200 g / dm 3 has. Further subject of the present invention is a method for producing such composite elements and the use of the composite elements in the interior of transport.
  • Polyurethanes are characterized by a variety of uses. In particular, in the automotive industry, these are often used, for example in the car outer trim as spoilers, roof elements, spring elements and in the automotive interior trim as roof linings, Carpet Deutschen Finction, door panels, instrument panels, steering wheels, buttons and seat cushion.
  • These polyurethane foams are usually used in the form of composites with a topcoat. The preparation of these composites is usually done by placing the topcoat in a mold, applying the reaction mixture to make the polyurethane foam and curing. Processes for the preparation of these composites which are suitable for use in automotive interiors are described, for example, in EP 1361239 or DE 10 2005 01 1 572.
  • a trend in the automotive industry is the weight reduction of components. This is done in the field of polyurethane foams usually by reducing the density and by reducing the material thickness. Furthermore, thinner polyurethane foams leave more room, for example for cabling.
  • the use of known systems for the production of polyurethane foams show processing problems at low density and low mold part thickness, since the material introduced into the molds no longer fills them free of defects. It is also necessary that polyurethanes used in automotive interiors cause the lowest possible emissions of volatile compounds. This is particularly important for composite components, since the emitted compounds can lead to material changes in the cover layer. Furthermore, the emitted compounds are usually perceived as an odor nuisance. Emissions are often caused by the use of volatile, highly active amine catalysts.
  • these highly active catalysts are replaced in whole or in part by installable catalysts. These compounds catalyze the polyurethane reaction, but at the same time also have isocyanate-reactive groups, whereby a solid incorporation of the catalysts in the polyurethane takes place. Thereby The compulsion to use installable catalysts, the number of possible, usable catalysts is greatly reduced, which further complicates the adaptation of the reaction profile.
  • This object is achieved by a method for producing a composite element of cover layer and polyurethane foam, in which a cover layer is placed in a mold and a polyurethane reaction mixture on the cover layer and reacted to a polyurethane foam, wherein the polyurethane reaction mixture is obtained by mixing see of (a ) Polyisocyanate with (b) compounds with isocyanate-reactive OH
  • the polyurethane foam has a density of at most 200 g / dm 3 , preferably 50 to 180 g / dm 3 and more preferably 60 to 150 g / dm 3 .
  • the polyurethane foam is preferably a polyurethane rigid foam which has a compressive stress at 10% compression and / or compressive strength according to DIN 53 421 of 15 kPa to 80 kPa.
  • cover layer materials are usually used which give the composite element a decorative appearance, such as plastic films, plastic skins, textiles and / or leather. Preference is given to using PU sprayed or cast or slush skins and / or PVC slush skins, and deep-drawn foils made from thermoplastic materials.
  • the thickness of the outer layer is generally 0.6 to 2 mm, preferably 0.8 to 1.2 mm.
  • the cover layers are produced in one embodiment of the invention in a separate operation and inserted into the mold.
  • the cover layers are produced in a first working step by applying the starting materials for producing the cover layer, for example a polyurethane reaction mixture or molten plastic, into the mold and then curing to the cover layer before the reaction mixture is added to the cover layer to produce the polyurethane foam ,
  • the starting materials for producing the cover layer for example a polyurethane reaction mixture or molten plastic
  • the polyisocyanates (a) used for producing the integral polyurethane foams according to the invention comprise the aliphatic, cycloaliphatic and polyisocyanates known from the prior art. (aliphatic and aromatic divalent or polyvalent isocyanates component (a-1), and any mixtures thereof.
  • Examples are 4,4 '-Metandiphenyldiisocyanat, 2,4' -Metandi- phenyl diisocyanate, the mixtures of monomeric Metandiphenyldiisocyanaten and higher-nuclear homologues of Metandiphenyldiisocyanats (Polymer -MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,4- or 2,6-toluene diisocyanate (TDI) or mixtures of said isocyanates.
  • Polymer -MDI tetramethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TDI 2,4- or 2,6-toluene diisocyanate
  • the preferred MDI mixtures used may contain up to about 20% by weight of allophanate- or uretonimine-modified polyisocyanates.
  • the proportion of higher-nuclear homologs of MDI is preferably 2 to 30 wt .-%, preferably 4 to 20 wt .-% and in particular 5 to 15 wt .-%, each based on the total amount of MDI used in component (a1).
  • the polyisocyanate component (a) can be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers are obtainable by reacting polyisocyanates (a-1) described above, for example at temperatures of 30 to 100 ° C., preferably at about 80 ° C., with polyols (a-2) to give the prepolymer. Polyols (a-2) are known to the person skilled in the art and described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. The polyols (a-2) used are preferably the polyols described under b).
  • polyethers for example starting from ethylene oxide and / or propylene oxide.
  • customary chain extenders or crosslinking agents are added to the said polyols in the preparation of the isocyanate prepolymers.
  • Compounds with isocyanate-reactive OH groups (b) contain polyols.
  • Polyols have a molecular weight of at least 300 g / mol and preferably contain polyesterols and / or polyetherols.
  • Polyetherols are prepared by known processes, for example by anionic polymerization with alkali metal hydroxides or alkali metal alkoxides as catalysts and with the addition of at least one starter molecule containing 2 to 3 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids such as antimony pentachloride or borofluoro etherate from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 3-propylene oxide, 1, 2 or 2,3-butylene oxide and preferably ethylene oxide and 1, 2-propylene oxide.
  • Suitable starter molecules are water or dihydric and trihydric alcohols, such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol or trimethylolpropane.
  • the polyether polyols preferably polyoxypropylene polyoxyethylene polyols, preferably have a functionality of 2 to 5, more preferably 2 to 4 and more preferably 2 to 3 and molecular weights of 500 to 10,000, preferably from 1, 000 to 8,000 and most preferably from 2,000 to 6,000 g / mol.
  • Polyester polyols can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms and polyhydric alcohols, preferably diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • Suitable dicarboxylic acids are, for example: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in admixture with each other. Instead of the free dicarboxylic acids, it is also possible to use the corresponding dicarboxylic acid derivatives, for example dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides.
  • dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, 20 to 35: 35 to 50: 20 to 32 parts by weight, and in particular adipic acid.
  • dihydric and polyhydric alcohols, in particular diols are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10 -Decandiol, glycerol and trimethylolpropane.
  • polyester polyols from lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid.
  • the polyesterpolyols obtained preferably have a functionality of 2 to 4, in particular of 2 to 3, and a molecular weight of 500 to 3,000, preferably 1000 to 3000 g / mol.
  • polymer-modified polyols preferably polymer-modified polyesterols or polyetherols, particularly preferably graft polyether or graft polyesterols, in particular graft polyetherols.
  • This is a so-called polymer polyol, which usually has a content of, preferably thermoplastic, polymers of 5 to 60 wt .-%, preferably 10 to 55 wt .-%, particularly preferably 30 to 55 wt .-% and in particular 40 to 50 wt .-%, having.
  • polymer polyesterols are described, for example, in WO 05/098763 and EP-A-250 351 and are usually prepared by free-radical polymerization of suitable olefinic monomers, for example styrene, acrylonitrile,
  • the side chains are generally formed by transferring the from growing polymeric chains to polyesterols or polyetherols.
  • the polymer polyol predominantly contains the homopolymers of the olefins, dispersed in unchanged polyesterol or polyetherol.
  • the monomers used are acrylonitrile, styrene, acrylonitrile and styrene, particularly preferably exclusively styrene.
  • the monomers are optionally polymerized in the presence of further monomers, a macromer, a moderator and using a radical initiator, usually azo or peroxide compounds, in a polyesterol or polyetherol as a continuous phase.
  • a radical initiator usually azo or peroxide compounds
  • the macromers are incorporated into the copolymer chain.
  • This forms block copolymers with a polyester or polyether and a poly-acrylonitrile-styrene block, which act as phase mediators in the interface of continuous phase and dispersed phase and suppress the agglomeration of the polymer polyesterol particles.
  • the proportion of macromers is usually 1 to 20 wt .-%, based on the total weight of the monomers used to prepare the polymer polyol. If polymer polyol is present in the compounds with isocyanate-reactive OH groups (b), this is preferably present together with further polyols, for example polyether olefins, polyesterols or mixtures of polyetherols and polyesterols.
  • the proportion of polymer polyol is greater than 5 wt .-%, based on the total weight of component (b).
  • the polymer polyols may be contained, for example, based on the total weight of component (b) in an amount of 7 to 90 wt .-%, or from 1 1 to 80 wt .-%.
  • the polymer polyol is particularly preferably polymer polyesterol or polymer polyetherol.
  • the compounds according to the invention containing isocyanate-reactive OH groups (b) may contain chain extenders and / or crosslinkers in addition to polyols.
  • the chain extenders are usually 2-functional alcohols having molecular weights of 60 g / mol to 299 g / mol, for example ethylene glycol, propylene glycol, butanediol-1, 4, pentanediol-1.5.
  • the crosslinking agents are usually compounds having molecular weights of from 60 g / mol to 299 g / mol and 3 or more isocyanate-active H atoms which, in addition to OH groups, may also contain, for example, primary or secondary amino groups, and more preferably exclusively Have OH groups, for example glycerol, triethanolamine, trimethylolpropane and / or pentaerythritol.
  • crosslinkers make it possible to achieve good elongation at low density and sufficient hardness.
  • the crosslinkers used are preferably glycerol and / or triethanolamine and / or trimethylolpropane. If chain extenders, crosslinking agents or mixtures thereof are used for producing the polyurethane foams, these are expediently used in an amount of from 0 to 20% by weight, preferably from 1 to 8% by weight, based on the total weight of the polyols (b) ,
  • the compounds containing isocyanate-reactive OH groups (b) polyether alcohol bi), which can be obtained by addition of alkylene oxides to aliphatic compounds having at least one tertiary amino group.
  • the polyether alcohols bi) are prepared by reacting aliphatic compounds having at least one tertiary amino group in the molecule with alkylene oxides. It is clear that said compounds must contain at least one, preferably at least two functional groups which can be reacted with alkylene oxides. These may in particular be hydroxyl groups or primary or secondary amino groups.
  • the abovementioned aliphatic compounds having at least one tertiary amino group in the molecule preferably have a maximum molecular weight of 400 g / mol.
  • the starting amine substance for preparing the polyether alcohols bi) is selected from the group comprising dimethylaminoethylamine, N, N-dimethylaminopropylamine, diethylaminoethylamine, diethylaminopropylamine, N- (3-dimethylaminopropyl-N, N-diisopropanolamine, dimethylethanolamine, N, N, N'-trimethyl-N'-hydroxyethyl bis (aminoethyl) ether, N, N-bis (3-dimethylaminopropyl) amino-2-propanolamine, bis (N, N-dimethyl-3-aminopropyl) amine, ⁇ , ⁇ -dimethylaminoethoxyethanol, N- (3-aminopropyl) imidazole, N- (2-dimethyla
  • the process for the preparation of the polyether alcohols bi) is preferably carried out so that an average of 1 to 8, preferably 1 to 6, in particular 2 to 4 molecules of the alkylene oxide are attached to each active hydrogen atom of the amine starting substance.
  • the alkylene oxides used are usually ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide.
  • Polyols bi) are described for example in DE 10 2005 01 572.
  • component b) contains at least 4% by weight, based on the weight of component b), of polyether alcohol bi). At a lower content of polyether alcohol bi) there is no significant effect.
  • the content of polyether alcohol bi) is particularly preferably 4 to 50% by weight, in particular 4 to 20% by weight, in each case based on the total weight of component b).
  • propellant (c) for the process according to the invention water which reacts with isocyanate groups to form carbon dioxide is used.
  • so-called physically acting blowing agents can also be used in admixture with water.
  • Such preferably usable liquids are hydrocarbons, such as pentane, n- and iso-butane and propane, ethers, such as dimethyl ether and diethyl ether, ketones, such as acetone and methyl ethyl ketone, ethyl acetate and preferably halogenated hydrocarbons, such as methylene chloride, trichlorofluoromethane, Dichlorodifluoromethane, dichloromonofluoromethane, dichlorotetrafluoroethane and 1, 1, 2
  • hydrocarbons such as pentane, n- and iso-butane and propane
  • ethers such as dimethyl ether and diethyl ether
  • ketones such as acetone and methyl ethyl ketone
  • ethyl acetate preferably halogenated hydrocarbons, such as methylene chloride, trichlorofluoromethane, Dichlorodifluo
  • Trichloro-1, 2,2-trifluoroethane It is also possible to use mixtures of these low-boiling liquids with one another and / or with other substituted or unsubstituted hydrocarbons.
  • a blowing agent and carbon dioxide can be used, which is preferably dissolved as a gas in the starting components.
  • the amount of physical blowing agent required besides water can be easily determined depending on the desired foam density and is about 0 to 50 parts by weight, preferably 0 to 20 parts by weight per 100 parts by weight of the polyhydroxyl compound.
  • water is used as the sole blowing agent (c).
  • the thickener (d) used are substances which rapidly increase the viscosity of the reaction mixture after mixing components (a) to (f), but the reaction mixture still remains free-flowing. This is achieved by compounds having molecular weights of less than 500 g / mol and two isocyanate-reactive groups which are more reactive in the reaction with isocyanate than the isocyanate-reactive groups of the compounds of component (b). As a rule, primary OH groups are more reactive than secondary OH groups and amino groups are more reactive than OH groups. Thickeners (d) cause isocyanates to react preferentially with the thickeners.
  • the thickeners (d) preferably have a molecular weight of 58 to 300 g / mol, more preferably 100 to 200 g / mol.
  • the thickeners (d) preferably have, as isocyanate-reactive groups, two primary amino groups.
  • the primary amino groups are bonded to aromatic carbon atoms, preferably to an aromatic 6-membered ring, in particular in the metha or para position.
  • the thickener (d) used is diethylene toluenediamine (DETDA), especially DETDA 80.
  • Diethylene toluene is commercially available, for example from Lonza or Abemarle
  • Catalyst (s) strongly accelerate the reaction of the polyols (b) and chemical blowing agent (c) with the polyisocyanates (a).
  • the catalysts (e) preferably contain incorporable amine catalysts.
  • Bis (N, N-dimethylaminoethoxyethyl) carbamate, N, N, N-trimethyl-N are used as installable catalysts in the present invention.
  • catalysts which can be incorporated are used as catalyst (e). If catalysts (e) are used, they can be used, for example, in a concentration of 0.001 to 5% by weight, in particular 0.05 to 2% by weight, as catalyst or catalyst combination, based on the weight of component (b).
  • auxiliaries and / or additives (f) can be used.
  • all known for the production of polyurethanes auxiliaries and additives can be used. Mention may be made, for example, of surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, flame retardants, hydrolysis protectants, fungistatic and bacteriostatic substances. Such substances are known and described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.4.4 and 3.4.6 to 3.4.1 1.
  • polyurethane foams In the industrial production of polyurethane foams, it is customary to combine the compounds having at least two active hydrogen atoms and the other starting materials and auxiliaries and / or additives before the reaction to form a so-called polyol component.
  • the isocyanates (a) and the isocyanate-reactive compounds (b) and optionally (d) can be reacted in amounts such that the equivalence ratio of NCO groups of (a) to the sum of the reactive hydrogen atoms the other components preferably 0.6 to 2.0: 1, more preferably 0.8 to 1, 5: 1 and in particular 0.9 to 1, 2.
  • the isocyanate index is 100 at a ratio of 1: 1.
  • the conversion to the product can be carried out, for example, by high-pressure or low-pressure machines, usually in closed or preferably open molds. Suitable processing machines are commercially available (eg the company Elastogran, Isotherm, Hennecke, Kraus Maffei, etc.).
  • the starting components are usually mixed depending on the application at a temperature of 0 to 100 ° C, preferably from 20 to 80 ° C, and introduced into the mold, which already contains the cover layer.
  • the mixing can, as already stated, be carried out mechanically by means of a stirrer or a stirring screw, or can take place in a conventional high-pressure mixing head.
  • the reaction of the reaction mixture may, for example, in conventional, preferred heatable and sealable, mold can be performed.
  • the surface of which consists for example of steel, aluminum, enamel, Teflon, epoxy resin or other polymeric material, the surface may optionally be chrome plated, for example, hard chrome plated.
  • the molds should be temperature-controlled in order to adjust the preferred temperatures can be closed and preferably equipped to exert a pressure on the product.
  • conventional mold release agents can be used.
  • the conversion to the polyurethane foams is usually carried out at a molding temperature, preferably also a temperature of the starting components, from 20 to 220 ° C, preferably 30 to 120 ° C, particularly preferably 35 to 80 ° C, for a duration of usually 0.5 to 30 min, preferably 1 to 5 min.
  • the mixture of components (a) to (f) is referred to as reaction mixture at reaction conversions of less than 90%, based on the isocyanate groups.
  • the polyurethane foams obtained have an average thickness, averaged over the surface of the polyurethane foam-coated cover layer, non-polyurethane coated areas of the cover layer, such as protruding edge regions, not being taken into account in determining the average thickness, of at most one cm, preferably at most 0, 8 and at least 0.1 cm, more preferably at most 0.6 cm and at least 0.1 cm and in particular at most 0.5 and at least 0.2 cm.
  • the present invention furthermore relates to a composite element obtainable by the process according to the invention.
  • These composite elements essentially show no defects despite their low thickness and low polyurethane foam density, even in the production of fluid-demanding molds.
  • composite elements according to the invention are suitable for use in the interior of means of transport, such as in automobiles, for example as dashboard, door side panel, armrest, floor edge, center console, airbag cover or glove box.
  • Polyol 1 Glycerol-based polyether polyol based on ethylene oxide and propylene oxide having an average OH number of 28 mg KOH / g, a functionality of 2.7 and a propylene oxide content, based on the total weight of the polyether, of 84% by weight.
  • Polyol 2 Glycerol-based polyether polyol based on ethylene oxide and propylene oxide having an average OH number of 27 mg KOH / g, a functionality of 2.5 and a propylene oxide content, based on the total weight of the polyether, of 78 wt .-%.
  • Polyol 3 Glycerol-based polyether polyol based on ethylene oxide and propylene oxide with an average OH number of 55 mg KOH / g, a functionality of 2.7 and a propylene oxide content, based on the total weight of the polyether, of 87 wt .-%.
  • Polyol 4 Propoxylated dimethylaminopropylamine having an average OH number of 250 KOH / g, a functionality of 2.0 and a propylene oxide content, based on the total weight of the polyether, of 72% by weight.
  • Polyol 5 polyester of adipic acid, 1,4-butanediol, isophthalic acid, monoethylene glycol with an average OH number of 55 mg KOH / g.
  • Catalyst 1 installable amine catalyst
  • Jeffcat® ZF10 from Huntsman
  • Catalyst 2 installable amine catalyst Polycat® 15 from Air Products
  • Catalyst 3 installable amine catalyst Polycat® 58 from Air Products
  • Iso 1 Methylendiphenyldiisocyanat having an NCO content of 33.5 wt .-% and an average functionality of 2 and a 4.4 'isomer content of 49 wt .-%
  • Iso 2 Polymethylendiphenyldiisocyanat having an NCO content of 31 .5 wt. -% and a mean functionality of 2.7
  • Iso 3 methylene diphenyl diisocyanate having an NCO content of 33.5% by weight and an average functionality of 2, and a 4,4 'isomeric content of 99% by weight
  • Iso 4 prepolymer of methylene diphenyl diisocyanate, dipropylene glycol and polyether polyol having an average OH number of 250 mg KOH / g, a functionality of 2 and a propylene oxide content, based on the total weight of the polyether, of 83 wt .-%. NCO content of 23 wt .-% and an average functionality of 2
  • Iso 5 Mixture of methylene diphenyl diisocyanate and the corresponding carbodiimide with an NCO content of 29.5% by weight and an average functionality of 2.2
  • Table 2 shows the foam quality for the comparative example or Examples 1 to 3 in each case at a foam density of 160 and 145 g / l.

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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)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un élément composite comprenant au moins une couche de revêtement et de la mousse de polyuréthane, dans lequel on insère une couche de revêtement dans un moule, on dépose un mélange réactionnel de polyuréthane sur la couche de revêtement et on laisse réagir pour obtenir une mousse de polyuréthane, le mélange réactionnel de polyuréthanne étant obtenue par mélange (a) de polyisocyanate avec (b) des composés comportant des groupes OH réactifs vis-à-vis de l'isocyanate, (c) un agent gonflant contenant de l'eau, (d) un agent épaississant et éventuellement (e) des catalyseurs, et (f) d'autres agents auxiliaires ou additifs et la mousse de polyuréthane ayant une densité de 200 (50 à 180 ; 60 à 150) g/dm3 maximum. La présente invention concerne en outre un procédé de fabrication de tels éléments composites et l'utilisation des éléments composites à l'intérieur de moyens de transport.
EP15725046.5A 2014-06-02 2015-05-29 Matériau composite comprenant une couche de revêtement et une couche de mousse de polyuréthane Withdrawn EP3149062A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14170794 2014-06-02
PCT/EP2015/061935 WO2015185448A1 (fr) 2014-06-02 2015-05-29 Matériau composite comprenant une couche de revêtement et une couche de mousse de polyuréthane

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US10640618B2 (en) 2015-05-29 2020-05-05 Basf Se Polyurethane-polyisocyanurate resins for fiber composite materials with a longer open time
EP3377492B1 (fr) 2015-11-19 2022-08-31 Basf Se Catalyseur pour la préparation de polyuréthanes
CN115348983B (zh) * 2020-04-06 2025-04-01 科思创德国股份有限公司 由热塑性塑料和聚氨酯制成的复合元件、其生产方法及其用途

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EP2736939B1 (fr) * 2011-07-29 2015-09-23 Bayer Intellectual Property GmbH Éléments composites en matières thermoplastiques et polyuréthanes, ainsi que procédé pour leur fabrication
ES2530361T3 (es) * 2012-02-15 2015-03-02 Bayer Ip Gmbh Espumas semirrígidas basadas en poliuretano, su uso y su aplicación
ITMI20121126A1 (it) * 2012-06-27 2013-12-28 Dow Global Technologies Llc Metodo per preparare articoli ricoperti a base di poliuretano espanso

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WO2015185448A1 (fr) 2015-12-10

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