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WO2024120897A1 - Couches minces de polyuréthane et leur procédé de production - Google Patents

Couches minces de polyuréthane et leur procédé de production Download PDF

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Publication number
WO2024120897A1
WO2024120897A1 PCT/EP2023/083385 EP2023083385W WO2024120897A1 WO 2024120897 A1 WO2024120897 A1 WO 2024120897A1 EP 2023083385 W EP2023083385 W EP 2023083385W WO 2024120897 A1 WO2024120897 A1 WO 2024120897A1
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WIPO (PCT)
Prior art keywords
polyurethane
layer
system components
less
polyurethane system
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Ceased
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PCT/EP2023/083385
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German (de)
English (en)
Inventor
Andre Kamm
Ann-kristin KLEEMANN
Amir Doroodian
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BASF SE
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BASF SE
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Publication of WO2024120897A1 publication Critical patent/WO2024120897A1/fr
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    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
    • 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
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers

Definitions

  • the present invention relates to processes for producing a compact polyurethane layer with a thickness of less than 250 pm, in which (i) a separating layer is provided, (ii) polyurethane system components containing an isocyanate component (A) and a polyol component (B) are applied to the separating layer in the desired thickness to form the polyurethane layer, (iii) optionally a substrate layer is applied to the polyurethane system components, (iv) the polyurethane system components are cured to form a polyurethane layer and (v) the separating layer is separated from the polyurethane layer, wherein the polyurethane system components comprise a silicone-polyalkylene oxide copolymer which has a hydroxyl number of less than 50 mg KOH/g and the polyurethane system components contain less than 1% by weight, based on the total weight of components (a) to (e), of solvent.
  • the present invention further relates to a polyurethane layer with a thickness of less than 250 pm
  • polyurethane layers for example on textiles as a carrier layer
  • the best known example is the production of artificial leather.
  • Artificial leather can be produced using a so-called "wet" process.
  • Thermoplastic polyurethanes are dissolved in solvents, applied to a release paper and then precipitated in a coagulation process in a precipitation bath based on water and solvent.
  • the resulting layer of polyurethane has a thickness of between 0.4 and 5 mm.
  • Dimethylformamide for example, is used as a solvent in such a process. This solvent-based technology is still widely used in industry and is also part of academic research (Sur et al., International Journal of Polymer Science 2018: 1-9).
  • WO 2013/041397 describes a process in which the artificial leather layer can be produced using a solvent-free spray process. However, the process described in WO 2013/041397 is not completely free of solvents, as a thin top layer is applied in a first step. According to WO 2013/041397, a top layer based on a DMF solution or a polyurethane dispersion in water can be used for this purpose.
  • WO202218680 also describes a process in which, in a first step, a solvent-based topcoat is applied to a release paper, onto which, after drying, a solvent-free polyurethane reaction mixture is applied.
  • Thin polyurethane layers based on aqueous polyurethane dispersions are environmentally friendly but have the disadvantage that they have very poor mechanical stability, so layers made of polyurethane dispersions are only used in thicker layers or in combination with other layers, such as in the manufacture of artificial leather. This is also disclosed in the teaching of WO 2008/077785.
  • Thermoplastic polyurethanes are dissolved in a solvent such as DMF, a thin layer of this solution is applied to a release paper and the solvent is then evaporated in an oven.
  • the resulting film shows excellent mechanical properties that cannot be achieved using a polyurethane dispersion.
  • the solvents used such as dimethylformamide or N,N'-dimethylacetamide, are toxicologically questionable
  • WO 2017/040109 discloses a process that uses a trialkyl phosphate as a solvent. The disadvantages of this process are immediately apparent to those skilled in the art.
  • the object of the present invention was therefore to develop a solvent-free process for the production of thin films from polyurethane reactive systems, which has a low release force of the films from the release paper.
  • This object is surprisingly achieved by a process for producing a compact polyurethane layer with a thickness of less than 250 pm, in which (i) a separating layer is provided, (ii) polyurethane system components containing an isocyanate component (A) and a polyol component (B) are applied to the separating layer to form a first polyurethane layer in the desired thickness, (iii) optionally a substrate layer is applied to the polyurethane system components, (iv) the polyurethane system components are cured to form a polyurethane layer and (v) the separating layer is separated from the polyurethane layer, wherein the isocyanate component (A) contains polyisocyanates (a) and the polyol component (B) contains compounds with hydrogen atoms reactive towards isocyanates (b), optionally fill
  • polyurethane system components are all compounds used to produce the polyurethane layer according to the invention. At least some of the polyurethane system components are combined in the isocyanate component (A) or the polyol component (B) in the process according to the invention.
  • the isocyanate component contains isocyanates (a), the polyol component (B) comprises the compounds with hydrogen atoms that are reactive towards isocyanates (b).
  • the other polyurethane system components such as the silicone-polyalkylene oxide copolymer (f) and, if present, fillers (c), water scavengers (d) and catalyst (e) are preferably added to the polyol component (B).
  • the compounds (c) to (f) do not have any groups that are reactive towards isocyanate or do not destabilize the isocyanate component, they can also be added in whole or in part to the isocyanate component (A). Alternatively, these components can also be used as another separate component.
  • all polyurethane system components are contained either in the polyisocyanate component or in the polyol component or in the polyol and polyisocyanate component, so that the polyurethane layer according to the invention is obtained solely by reacting the polyisocyanate component (A) and the polyol component (B) without adding further polyurethane system components.
  • the process according to the invention comprises a separating layer in step i).
  • any layer that allows polyurethane system components converts them into polyurethane and the resulting polyurethane can be separated from the release layer again.
  • the separating layer usually has a thickness of 0.001 millimeters (mm) to 10 mm, preferably from 0.01 mm to 5 mm, in particular from 0.1 mm to 2 mm.
  • Suitable release layers are usually known in the art under the term "release paper".
  • suitable release layers are layers, for example films, made of metal, plastic or paper.
  • a paper layer is used as the separating layer, which is optionally coated with a plastic.
  • the paper layer is preferably coated with a polyolefin, preferably polypropylene.
  • the paper layer is preferably coated with silicone.
  • the PET layer is preferably coated with a polyolefin, preferably polypropylene.
  • the PET layer is preferably coated with silicone.
  • release liners examples include Warren (Sappi, USA), Binda (Italy), Arjo Wiggins (UK/USA) and Lintec (Japan).
  • the separating layers used can have a smooth or uneven surface.
  • the type of separating layer depends on the desired surface of the polyurethane layer resulting from the process according to the invention. If a resulting polyurethane layer with a smooth surface is desired, the separating layer also has a smooth surface. If a resulting polyurethane layer with an uneven or patterned surface is desired, the separating layer also has an uneven or patterned surface. The separating layer with a smooth surface is preferred.
  • polyurethane system components containing an isocyanate component (A) and a polyol component (B) are applied to the release layer to form a first polyurethane layer of the desired thickness.
  • the layer thickness of the polyurethane layer applied to the separating layer is less than 250 pm, preferably 1 to 200 pm, particularly preferably 10 to 150 pm and in particular 50 to 120 pm. When the thickness of a layer is mentioned in the context of the present invention, this is an average value. This is usually determined by the weight of the layer per unit area. For this purpose, a density of 1.0 g/cm 3 is assumed for polyurethane.
  • the polyurethane layer according to the invention can contain defects, such as defects caused by the inclusion of air bubbles, but the polyurethane layer according to the invention preferably contains no defects.
  • the polyurethane system components can generally be applied using any method that allows a layer of polyurethane system components to be applied that can be cured to form a polyurethane layer of suitable thickness.
  • the polyurethane system components are preferably applied by pouring or spraying.
  • Pouring is usually understood to mean the application of a liquid reaction mixture of the polyurethane system components, comprising isocyanate component (A) and polyol component (B).
  • the mixture of the polyurethane system components with reaction conversions of less than 90%, based on the isocyanate groups, is referred to as the reaction mixture.
  • the material is preferably applied using a high or low pressure process using standard mixing heads, for example Puromats from Krauss Maffei or Hennecke are used as dosing units.
  • the material is preferably applied in a laminar material flow.
  • the applied material is preferably distributed to a homogeneous layer thickness using a doctor blade process with scratches, for example spatulas.
  • the material can also be applied using slot nozzles.
  • Spraying is understood to mean applying the liquid material via a spray head.
  • the spray head preferably atomizes the material into droplets, in particular fine droplets. This preferably creates a fan-shaped spray jet.
  • the polyurethane system components are preferably sprayed in the form of particles, with the particles preferably being in the form of droplets, with a particle diameter of 1 to 1000 pm, particularly preferably 10 to 500 pm, and most preferably 15 to 150.
  • the isocyanate component (A) contains polyisocyanates (a).
  • the polyisocyanates used include the usual aliphatic, cycloaliphatic and especially aromatic di- and/or polyisocyanates.
  • the diphenylmethane diisocyanate particularly preferably contains at least 50% by weight, more preferably at least 75% by weight and in particular at least 95% by weight of the isomer 4,4'-MDI.
  • isocyanates or isocyanate prepolymers described below can also be modified, for example by incorporating uretdione, carbamate, isocyanurate, carbodiimide or allophanate groups. Mixtures of the various isocyanates can also be used.
  • the polyisocyanates (a) are preferably used in the form of polyisocyanate prepolymers. These prepolymers are known in the art. They are prepared in a manner known per se by reacting the polyisocyanates (a) described above, preferably MDI, particularly preferably 4,4'-M DI, with compounds described below with hydrogen atoms (b) that are reactive toward isocyanates to form the prepolymer. The reaction can take place, for example, at temperatures of around 80°C.
  • the polyol-polyisocyanate ratio is generally selected so that the NCO content of the prepolymer is preferably 10 to 25% by weight, particularly preferably 12 to 22% by weight and in particular 15 to 20% by weight.
  • This mixture preferably has an NCO content of 10 to 22%, particularly preferably 12 to 20%.
  • the polyol component (B) contains compounds with hydrogen atoms (b) that are reactive toward isocyanates. These compounds are those that carry two or more reactive groups selected from OH groups, SH groups, NH groups, NH2 groups and CH-acidic groups, such as ß-diketo groups, in the molecule.
  • the term polyurethanes in the context of this invention generally includes polyisocyanate polyaddition products, for example also polyureas.
  • Compounds (b) preferably have a number-average molecular weight of greater than 400 g/mol, particularly preferably 400 to 10,000 g/mol and in particular 500 to 8,000 g/mol.
  • the polyol component (B) preferably contains polyetherol and/or polyesterol. These are generally known and are described, for example, in "Kunststoffhandbuch Polyurethane” Günter Oertel, Carl-Hanser-Verlag, 2nd edition 1983, chapter 3.1.1. Alternative terms that are also commonly used in the field are polyether polyols or polyether alcohols or polyester polyols or polyester alcohols.
  • polyesters are usually prepared by condensation of polyfunctional alcohols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as monoethylene glycol, diethylene glycol, propanediol, butanediol, pentanediol and hexanediol, with polyfunctional carboxylic acids having 2 to 12 carbon atoms, for example succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid and preferably phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • polyfunctional alcohols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as monoethylene glycol, diethylene glycol, propanediol, butanediol, pentanediol and hexanediol
  • polyetherols are used, they are generally prepared from one or more alkylene oxides selected from propylene oxide (PO) and ethylene oxide (EO), butylene oxide and tetrahydrofuran by known processes, for example by anionic polymerization with alkali hydroxides as catalysts and with the addition of a starter molecule containing several reactive hydrogen atoms bonded to it.
  • alkylene oxides selected from propylene oxide (PO) and ethylene oxide (EO), butylene oxide and tetrahydrofuran by known processes, for example by anionic polymerization with alkali hydroxides as catalysts and with the addition of a starter molecule containing several reactive hydrogen atoms bonded to it.
  • the alkylene oxides can be used individually, alternately one after the other or as mixtures.
  • the use of an EO/PO mixture leads to a polyether polyol with a statistical PO/EO unit distribution. It is possible to first use a PO/EO mixture and then use only PO or EO before stopping the polymerization. This then gives a polyether polyol with a PO or EO endcap.
  • NH- or OH-functional compounds such as water, amines or alcohols are usually used as starter molecules.
  • Dihydric to hexahydric alcohols are preferably used, such as ethanediol, propanediol-1,2 and -1,3, diethylene glycol, dipropylene glycol, butanediol-1,4, hexanediol-1,6, glycerin, trimethylolpropane, pentaerythritol and/or sorbitol.
  • low-unsaturated polyetherols can also be used as polyetherols (b).
  • low-unsaturated polyols are understood to mean in particular polyether alcohols with an unsaturated compound content of less than 0.02 meq/g, preferably less than 0.01 meq/g.
  • Such polyether alcohols are prepared by addition of alkylene oxide, preferably propylene oxide and mixtures thereof, to at least difunctional alcohols in the presence of so-called double metal cyanide catalysts. If desired, the resulting propylene oxides are further reacted with ethylene oxide, for example with alkaline catalysts such as potassium hydroxide.
  • polyetherols (b) which are obtained by ring-opening polymerization of tetrahydrofuran.
  • These polytetrahydrofurans preferably have a functionality of about 2. Furthermore, they preferably have a number-average molecular weight of 500 to 4000 g/mol, preferably 700 to 3000 g/mol, particularly preferably 900 to 2500 g/mol.
  • the polyol component (B) can also contain conventional chain extenders, wherein in the context of this invention, chain extenders are understood to mean compounds having at least 2 hydrogen atoms reactive toward isocyanates and molecular weights of 42 to less than 400 g/mol.
  • the polyol component (B) contains one or more components selected from
  • (b-1) a polyol, preferably a polyester polyol, with a number average molecular weight of 500 g/mol to less than 3000 g/mol
  • (b-2) a polyol, preferably a polyether polyol, with a number average molecular weight of 3000 g/mol to 8000 g/mol
  • (b-3) a chain extender having a molecular weight of less than 400 g/mol.
  • a polyetherol or a polyesterol particularly preferably a polyesterol, having a number-average molecular weight of 500 to less than 3000 g/mol, preferably from 800 to 2500 g/mol, particularly preferably from 1000 to 2200 g/mol is used as component (b1) in component (b-1).
  • the components (b-1) usually have an average functionality of 1.8 to 3, more preferably 1.9 to 2.1, in particular 2.0. Functionality here is understood to mean the “theoretical OH functionality” which results from the functionality of the starter molecules used.
  • the components (b-1) are usually present in an amount of from 30 to 100% by weight, preferably from 50 to 90% by weight, based on the total weight of the compounds having hydrogen atoms (b) reactive toward isocyanates, in the component (B).
  • a compound having hydrogen atoms reactive towards isocyanates (b) is a polyetherol or a polyesterol, particularly preferably a Polyether polyol having a number average molecular weight of 3000 to 8000 g/mol, preferably 3500 to 7000 g/mol, particularly preferably 4000 to 6000 g/mol is used as component (b2).
  • the components (b-2) usually have an average functionality of 1.9 to 6, more preferably 2.3 to 4, in particular 3.0. Functionality here is understood to mean the "theoretical OH functionality" which results from the functionality of the starter molecules used.
  • a polyether polyol is used as component (b-2), obtainable by propoxylation and/or ethoxylation of glycerol or trimethylolpropane, in particular with EO end block.
  • This polyether polyol preferably has a number-average molecular weight of 4500 to 6000 g/mol.
  • Component (b-2) is usually present in component (B) in an amount of from 5 to 80% by weight, preferably from 10 to 30% by weight, based on the total weight of the compounds containing isocyanate-reactive hydrogen atoms (b).
  • the polyol component (B) can contain chain extenders as component (b-3).
  • Suitable chain extenders are compounds having at least 2 hydrogen atoms that are reactive toward isocyanates and have a molecular weight of less than 400 g/mol, and are known in the art. Preference is given to using 2-functional alcohols with molecular weights of less than 400 g/mol, in particular in the range from 60 to 150 g/mol.
  • Examples are ethylene glycol, propylene glycol, diethylene glycol, butanediol-1,4, dipropylene glycol, tripropylene glycol. 1,4-Butanediol is preferably used.
  • the chain extender is usually used in an amount of from 2 to 25% by weight, preferably from 3 to 13% by weight, particularly preferably from 3 to 20% by weight, based on the total weight of the compounds having hydrogen atoms reactive toward isocyanates (b).
  • the polyol component contains polyester polyol (b1) and chain extender (b3) and in particular no polyether polyol (b2).
  • the reaction of the polyurethane system components (A) and (B) takes place in the absence of a blowing agent.
  • the resulting polyurethane layer is then a compact polyurethane.
  • compact polyurethane is defined as In this context, polyurethanes are understood to be those produced without the addition of blowing agents.
  • the polyurethane layer resulting in this embodiment usually has a density of 0.8 to 1.2 kg/liter, preferably 0.9 to 1.1 kg/liter.
  • the polyol component (B) used may contain a small amount of residual water for technical reasons. This is particularly the case if no water scavenger is used as component (d).
  • the residual water content is preferably less than 0.5% by weight, particularly preferably less than 0.2% by weight, based on the total weight of the component (B) used.
  • polyurethane system components with a residual water content of less than 0.5% by weight are therefore also considered to be free of blowing agents and lead to a compact polyurethane according to the invention.
  • the polyol component (B) contains fillers (c).
  • fillers in general, the usual fillers known in the field of polyurethane chemistry are suitable. Examples of suitable fillers are glass fibers, mineral fibers, natural fibers such as flax, jute or sisal, glass flakes, silicates such as mica or mica, salts such as calcium carbonate, chalk or gypsum.
  • fillers are used which create cracks in the polyurethane layer when the resulting polyurethane is stretched. These cracks generally lead to an increase in breathability.
  • Calcium carbonate is particularly preferred as a filler.
  • the fillers (c) are usually used in an amount of from 0.5 to 60% by weight, preferably from 3 to 10% by weight, based on the total weight of components (b) to (f).
  • the polyol component (B) contains water scavengers (d).
  • water scavengers in general, the usual water scavengers known in the field of polyurethane chemistry are suitable.
  • suitable water scavengers are zeolites, in particular in the form of zeolite pastes, for example Baylith® L-Paste 3A.
  • Water scavengers (d) are usually used in an amount of from 1 to 10% by weight, preferably from 3 to 8% by weight, based on the total weight of components (B).
  • the reaction of components (A) and (B) takes place in the presence of a catalyst (e).
  • a catalyst e
  • This is particularly preferably a component of component (B).
  • the usual and known polyurethane formation catalysts are optionally used as catalysts for the production of the polyurethane foams according to the invention, in which for example organic tin compounds such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and/or strongly basic amines such as diazabicyclooctane, triethylamine, or preferably triethylenediamine or bis(N,N-dimethylaminoethyl) ether.
  • organic tin compounds such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and/or strongly basic amines such as diazabicyclooctane, triethylamine, or preferably triethylenediamine or bis(N
  • Component (e) is usually used in an amount of 0.01 to 5 wt.%, preferably 0.05 to 4 wt.%, based on the total weight of components (b) to (f).
  • thermally activated catalysts when applying polyurethane system components using the casting process.
  • Thermally activated catalysts allow a long open time for the application of the polyurethane system components and yet rapid curing at elevated temperatures.
  • Thermally activated catalysts include, for example, acid-blocked, for example carboxylic acid-blocked, in particular formic acid-blocked amine catalysts, for example tertiary amine catalysts, N-acetylated amine catalysts. These can be produced, for example, by reacting acids with bases, optionally in the presence of a solvent.
  • Such catalysts are known and described, for example, in US4582861, US4232152, US4366084, US4450246, US4617286, DE19512480, EP0989146, US6525107, US5770635.
  • carboxylic acids in particular oleic acid, formic acid, acetic acid, ethylhexyl acid, phenol, ricinoleic acid, linoleic acid and/or p-toluenesulfonic acid, are preferably used as the acid component.
  • the amine catalysts to be blocked are preferably triethylenediamine, dimethylamino-N-methylpiperazine, N,N-diphenyl-N-methylamine, bis(N,N-dimethylaminoethyl)ether, N,N-dimethylaminoethoxyethanol and/or DBU. These blocked catalysts are usually present in a solvent or dispersant.
  • Glycols such as propylene glycol, dipropylene glycol, ethylene glycol and/or diethylene glycol are preferably suitable as solvents or dispersants.
  • organometallic catalysts such as nickel acetylacetonate, dioctyltin diisooctylmercaptoacetate or dibutyltin diisooctylmercaptoacetate can also be used, especially in the casting process.
  • the catalyst (e) in the casting process particularly preferably contains blocked diazabicycloundecene (DBU).
  • the catalyst is selected such that when the polyurethane system components are applied by pouring, an open time at 23 °C and a humidity of 50% relative humidity of at least one minute, particularly preferably at least 10 minutes and in particular at least 15 minutes is achieved.
  • the polyurethane system components have at least one silicone-polyalkylene oxide copolymer (f) which has a hydroxyl number of less than 50 mg KOH/g, preferably 1 to 40 mg KOH/g, particularly preferably 2 to 30 mg KOH/g and in particular 5 to 15 mg KOH/g.
  • the polyalkylene oxide copolymer (f) preferably has a molecular part with organosilicon building blocks, such as dimethylsiloxane or methylphenylsiloxane, and a molecular part with a chemical structure that is similar to the polyols (b). These are preferably polyoxyalkylene units.
  • the silicone-polyalkylene oxide copolymer is preferably a polysiloxane-polyoxyalkylene block copolymer, the weight-average molecular weight of the polyoxyalkylene blocks being greater than 1000 g/mol, particularly preferably 1500 to 5000 g/mol and in particular 2000 to 3000 g/mol.
  • the oxyethylene content is preferably less than 80% by weight, particularly preferably between 10 and 75% by weight.
  • at least 50%, particularly preferably at least 60% and in particular 70 to 95% of the polyalkylene oxide groups of the polysiloxane-polyoxyalkylene block copolymer have an alkylene group as an end group.
  • the alkylene group is preferably one with 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. Methylene or ethylene end groups, in particular methylene end groups, are particularly preferred.
  • the proportion of the silicone-polyalkylene oxide copolymer (f) is preferably 0.1 to 4
  • component (B) % by weight, particularly preferably 0.2 to 3 % by weight and in particular 0.5 to 2.5 % by weight, each based on the total weight of components (b) to (h).
  • the reaction of components (A) and (B) takes place, if appropriate, in the presence of other auxiliary substances and/or additives known in the production of polyurethanes, such as pigments, surface-active compounds and/or stabilizers against oxidative, thermal, hydrolytic or microbial degradation or aging. These are preferably also part of component (B).
  • the polyurethane system components contain essentially no solvent.
  • Essentially no solvent means that they contain no solvent apart from possible production-related impurities and that no solvent has been added to the components.
  • the solvent content is thus less than 1% by weight, preferably less than 0.1% by weight, particularly preferably less than 0.01% by weight, based on the total weight of components (a) to (f).
  • solvent is generally known in the technical field. Solvents are also often referred to in the technical field as solvents or solvents. In the context of this invention, solvents are understood in the broadest sense to mean inorganic and organic liquids that can dissolve other solid substances by physical means. The prerequisite for suitability as a solvent is that neither the dissolving nor the dissolved substance undergoes chemical changes during the dissolving process and in the solution. The dissolved component can therefore be recovered by physical separation processes such as distillation, crystallization, sublimation, evaporation and/or adsorption.
  • the polyurethane system components essentially contain no organic solvent.
  • the polyurethane system components essentially contain no ethers and glycol ethers (such as diethyl ether, dibutyl ether, anisole, dioxane, monomeric tetrahydrofuran), ketones (such as acetone, butanone, cyclohexanone), esters (such as acetic acid esters), nitrogen compounds (such as dimethylformamide, dimethylacetamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (such as carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (such as nitrobenzene), halogenated hydrocarbons (such as dichloromethane, chloroform, tetrachloromethane, tri-, tetrachloroethene, 1,2-dichloroethane, chlorofluorocarbons), hydrocarbons,
  • components (A) and (B) are generally reacted in such amounts that the equivalence ratio of NCO groups to The sum of the reactive hydrogen atoms is preferably 1:0.9 to 1:1.5.
  • a ratio of 1:1 corresponds to an NCO index of 100.
  • the equivalence ratio of NCO groups to the sum of the reactive hydrogen atoms is particularly preferably 1:0.98 to 1:1.40, more preferably 1:1.00 to 1:1.30 and in particular 1:1.02 to 1:1.20. This corresponds to an isocyanate index of 98 to 140, more preferably 100 to 130 and in particular 102 to 120.
  • a substrate layer is applied to the polyurethane system components.
  • the substrate layer is preferably applied as long as the polyurethane system components are not yet completely cured. That is, as long as a reaction of isocyanate groups with OH groups is still taking place.
  • any layer that can form an adhesive bond with the resulting polyurethane layer is suitable as a substrate layer.
  • the substrate layer usually has a thickness of 0.01 millimeters (mm) to 20 mm, preferably from 0.1 mm to 10 mm, in particular from 0.3 mm to 5 mm.
  • suitable substrate layers are layers, for example films, made of metal, plastic, leather and/or textiles.
  • the substrate layer can consist of one or more identical or different layers that are firmly connected to one another, e.g. of close-meshed or wide-meshed fabrics, knitted fabrics, braids, networks (mesh cloths).
  • Nonwoven substrate layer Surface structures made of random fibers (e.g. felt and nonwoven fibers) that can preferably be bonded together by a binding agent.
  • the nonwoven substrate layers are usually cellulose or textile nonwovens that have been solidified with water-insoluble impregnating agents.
  • Fiber substrate layer Products made from loose, disordered fibers that are solidified using plastics as a binding agent. They are obtained, for example, by bonding leather fibers (preferably obtained from leather waste, e.g. from vegetable-tanned leather) with 8-40% by weight of a binding agent.
  • Film substrate layer Products containing (preferably homogeneous) films made of metal or plastic, for example rubber, PVC, polyamides or copolymers. The film substrate layer preferably has no fiber inclusions.
  • a textile layer is used, the following materials are particularly suitable for producing the textile layer: cotton, linen, polyester, polyamide and/or polyurethane.
  • the substrate layer is preferably applied while the last applied polyurethane system components are still flowable or have already hardened to such an extent that they are no longer flowable but will stick to the wooden spatula when touched.
  • the substrate layer is applied to the polyurethane system components by bringing it into contact with them and pressing it on.
  • the contact pressure is preferably between 0.01 and 6 bar, more preferably between 0.05 and 5 bar.
  • the pressing time is between 0.1 seconds and 100 seconds, preferably between 0.5 seconds and 15 seconds (see).
  • the substrate layer can also be applied to the polyurethane layer using a conventional adhesive.
  • preferably solvent-free adhesives are one-component polyurethane adhesives or two-component polyurethane adhesives.
  • step (iv) of the method according to the invention the polyurethane system components are cured to form the polyurethane layer.
  • This curing can be accelerated by increasing the temperature, for example in an oven, or by irradiation, for example with microwave radiation or infrared radiation. In a preferred embodiment, curing takes place at temperatures of 80 to 160 °C.
  • the curing process lasts until the reaction of isocyanate groups with OH functional groups is essentially complete.
  • the curing process preferably lasts 0.5 to 20 minutes, more preferably 1 to 10 minutes, in particular 2 to 5 minutes. If necessary, the material can then be tempered for up to 24 hours at 60-100 °C.
  • step (v) of the process according to the invention the separating layer is separated from the polyurethane layer.
  • the separation can be carried out by the usual methods known in the art. Methods can be used.
  • the separating layer is removed from the polyurethane layer.
  • the present invention further relates to a polyurethane layer having a thickness of less than 250 pm, obtainable by such a process and the use of such a polyurethane layer as a coating for textiles.
  • the process according to the invention enables the essentially non-destructive production of polyurethane layers with a thickness of less than 250 pm by reducing the required peel forces from the release layer.
  • Polyl Polyesterol based on adipic acid, monoethylene glycol and 1,4-butanediol with an OH number of 55 mg KOH/g
  • A1 Silicone stabilizer Dabco DC 193 from Air Products; polydimethylsiloxane-co-polyalkylene oxide copolymer with an OH number of 75 mg KOH/g; ; end group of the polyalkylene oxide groups: primary -OH
  • A2 Silicone stabilizer Tegostab 8905 from Evonik; polydimethylsiloxane-co-polyalkylene oxide copolymer with an OH number of 280 mg KOH/g End group of the polyalkylene oxide groups: primary -OH
  • A3 Silicone stabilizer Dabco DC 198 from Air Products; polydimethylsiloxane-co-polyalkylene oxide copolymer with an OH number of 8.7 mg KOH/g; end group of the polyalkylene oxide groups: -O-CH3
  • A4 Silicone stabilizer Tegostab 8843 from Evonik; polydimethylsiloxane-co-polyalkylene oxide copolymer with an OH number of ⁇ 10 mg KOH/g; end group of the polyalkylene oxide groups: -O-CH 3
  • A5 Silicone stabilizer Tegostab 8960 from Evonik; polydimethylsiloxane-co-polyalkylene oxide copolymer with an OH number of ⁇ 10 mg KOH/g; end group of the polyalkylene oxide groups: -O-CH3
  • the polyurethane layers were produced as follows:
  • a polyurethane reaction mixture with an isocyanate index of 103 was prepared and applied to release paper.
  • 100 g of the starting materials were mixed with a Hauschild speed mixer for 5 seconds at 800 revolutions and a further 35 seconds at 1950 revolutions.
  • the reaction mixture was processed into thin films using a film applicator from Erichsen and a doctor blade with a defined gap width and a doctor blade speed of 50 mm/s.
  • Siliconized paper (Stripkote Bor Supermat G) served as the substrate for the films. After the film had been doctored, the paper and film were reacted in an oven at 150°C for 3 minutes.
  • the reacted polyurethane films were conditioned for 7 days under standard climate and the force required to remove the polyurethane film from the paper was determined using a roller peel test in accordance with DIN EN 1464 as a function of the thickness of the polyurethane film.
  • DIN EN 1464 as a function of the thickness of the polyurethane film.
  • the films have to be removed from the release paper after a short curing time during the production process, it is essential that the peeling force is reduced to a minimum. Since the mechanical stability of the freshly produced film is very low, excessive peeling forces would destroy the film. To illustrate this, the comparative examples V4 and V5 were carried out again and attempts were made to remove the cured film from the release paper after curing for 3 minutes at 150°C. A maximum of 60 seconds passed between removing the films from the oven and attempting to remove them.
  • silicone copolymers with an OH number of ⁇ 50 mg KOH/g leads to improved detachment of the films in the fresh state. This also correlates with the peel force required after 7 days.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de production d'une couche de polyuréthane compacte ayant une épaisseur inférieure à 250 µm. Dans ledit procédé : (i) une couche de séparation est fournie, (ii) des composants de système de polyuréthane, contenant un composant isocyanate (A) et un composant polyol (B), sont appliqués à la couche de séparation dans une épaisseur souhaitée pour former une première couche de polyuréthane, (iii) facultativement, une couche de substrat est appliquée aux composants du système de polyuréthane, (iv) les composants du système de polyuréthane sont durcis pour former une couche de polyuréthane, et (v) la couche de séparation est séparée de la couche de polyuréthane, les composants du système de polyuréthane comprenant un copolymère d'oxyde de polyalkylène-silicone, qui a un indice d'hydroxyle inférieur à 50 mg KOH/g, et les composants du système de polyuréthane contiennent moins de 1 % en poids de solvant par rapport au poids total des composants (a) à (e). La présente invention concerne également une couche de polyuréthane ayant une épaisseur inférieure à 250 µm, pouvant être obtenue selon un tel procédé, et l'utilisation d'une telle couche de polyuréthane en tant que revêtement pour des textiles.
PCT/EP2023/083385 2022-12-07 2023-11-28 Couches minces de polyuréthane et leur procédé de production Ceased WO2024120897A1 (fr)

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US4366084A (en) 1981-05-26 1982-12-28 Abbott Laboratories Catalyst for making polyurethanes
US4450246A (en) 1982-10-26 1984-05-22 W. R. Grace & Co. Novel polyurethane catalysts in polyurethane foam process
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JPH08176259A (ja) * 1994-12-22 1996-07-09 Mitsui Toatsu Chem Inc 有機無機ハイブリッド型難燃発泡体組成物とその複合建材
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