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WO2021209284A1 - Stratifié comprenant une dispersion aqueuse de polyuréthane et un polyuréthane à deux composants et son utilisation - Google Patents

Stratifié comprenant une dispersion aqueuse de polyuréthane et un polyuréthane à deux composants et son utilisation Download PDF

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Publication number
WO2021209284A1
WO2021209284A1 PCT/EP2021/058948 EP2021058948W WO2021209284A1 WO 2021209284 A1 WO2021209284 A1 WO 2021209284A1 EP 2021058948 W EP2021058948 W EP 2021058948W WO 2021209284 A1 WO2021209284 A1 WO 2021209284A1
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Prior art keywords
laminate according
aqueous polyurethane
weight
polyurethane dispersion
range
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PCT/EP2021/058948
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English (en)
Inventor
Zhong Kai ZHANG
Feng Chao HU
Dan Shen
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BASF SE
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BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to CN202180028257.6A priority Critical patent/CN115443356A/zh
Publication of WO2021209284A1 publication Critical patent/WO2021209284A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • D06N3/145—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 two or more layers of 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
    • D06N3/12—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
    • D06N3/146—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 characterised by the macromolecular diols used
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/14—Furniture, upholstery
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Definitions

  • a laminate comprising aqueous polyurethane dispersion and 2-component polyurethane and the use thereof
  • the present invention relates to a laminate comprising aqueous polyurethane dispersion and 2- component polyurethane and the use thereof.
  • Non-solvent PU synthetic leather is one of eco-friendly solutions for synthetic leather industry. It normally needs aqueous dispersions as top coat layer and 2-component polyurethane as base coat layer. However, the combination of aqueous dispersions and 2-component polyurethane have problems of poor instant peel strength and bad curing, and thus cannot satisfy in-situ pro duction requirement.
  • US 9,234,071 B2 discloses an aqueous dispersion and its use for the production of sheet-like substrate.
  • the dispersion contains silicone compound having reactive group.
  • this pa tent does not involve combination of aqueous dispersions and 2-component polyurethane.
  • EP 1 ,861 ,251 B2 discloses a method for producing polyurethane layers and use thereof as imi tation leather. The document discloses applying substrate layer on the polyurethane layers, so as to obtain imitation leather. Said imitation leather does not contain any top coat.
  • US 2005/0354133 A1 relates a polyurethane dispersion based synthetic leather.
  • the top coat comprises a wetting agent and an acrylate polymer having a glass transition temperature of -20°C or less. This document does not involve technical problems of poor instant peel strength and bad curing related to laminates.
  • US 2014/0215850 A1 discloses a method for producing an artificial leather with improved flex ing endurance properties.
  • a laminate structure composed of top coat layer, intermediate layer and optionally substrate layer.
  • a first polyurethane system component with the isocyanate index ranging from 101 to 140 must be contained in the intermediate layer.
  • the document does not involve a top coat layer containing hydrophilic groups. This document also does not involve technical problems of poor instant peel strength and bad curing related to laminates.
  • US4870129 discloses an adhesive comprising an aqueous solution or a dispersion of a poly urethane and the use of such an adhesive for the formation of bonds on any substrates.
  • the document does not involve combination of aqueous dispersions and 2-component polyure thane. Therefore, it is still required to provide new combination of aqueous dispersions and 2-compo- nent polyurethane, which may overcome one or more the above disadvantages and thus cansatisfy in-situ production requirement.
  • An object of this invention is to overcome the problems of the prior art discussed above and to provide a laminate comprising a top coat skin layer based on an aqueous polyurethane disper sion and a base coat layer underneath the top coat skin layer and based on a solvent-free 2- component polyurethane. Meanwhile, the laminate achieves improved properties in terms of in stant peel strength, curing property and/or flexing endurance.
  • the laminate may further comprise a substrate layer underneath the base coat layer.
  • the molar ratio of hydroxyl and/or amino group to the isocyanate group present in the aqueous polyurethane dispersion is 0.9 to 1.5, preferably 1.10 to 1.25.
  • the aqueous polyurethane dispersion contains no more than 0.1% of carboxylate group.
  • the isocyanate index of the polyurethane system is in the range of from 100 to 120.
  • the aqueous polyurethane dispersion contains an amine neutralization agent with gel reactivity which is selected from the group consisting of tri- ethylenediamine (TEDA), 1,2-dimethylimidazole, N,N-dimethylcyclohexylamine, N,N,N',N'-Tetra- methylethylenediamine and tertiaryamine.
  • an amine neutralization agent with gel reactivity which is selected from the group consisting of tri- ethylenediamine (TEDA), 1,2-dimethylimidazole, N,N-dimethylcyclohexylamine, N,N,N',N'-Tetra- methylethylenediamine and tertiaryamine.
  • the aqueous polyurethane dispersion comprises no acrylate polymer. In a preferable embodiment of the invention, the aqueous polyurethane dispersion comprises no other polymer than polyurethane.
  • the polyurethane system further comprises a cata lyst (c) with a content of no more than 2wt%, based on the total weight of the components of the polyurethane system.
  • the aqueous polyurethane dispersion is obtainable by reaction of an isocyanate component (a’) and a polyol component (b’), the polyol component (b’) comprising:
  • (b’-1) a polyol having a weight-average molecular weight in the range of from 500 g/mol to 10000 g/mol, and functionality in the range of from 2 to 4,
  • (b’-2) a polyol having a weight average molecular weight in the range of from 500 g/mol to 3000 g/mol, and functionality in the range of from 2 to 4,
  • (b’-3) a chain extender having a molecular weight of less than 400 g/mol
  • (b’-4) a hydrophilic chain extender containing carboxylate group or sulphonate group.
  • the polyol (b’-1) is different from the polyol (b’-2).
  • the hydrophilic chain extender (b’-4) is different from the chain extender (b’-3).
  • the hydrophilic chain extender (b’-4) preferably contains carboxylate group.
  • the hydrophilic chain extender (b’-4) preferably contains sulphonate group.
  • the hydrophilic chain extender (b’-4) further con tains hydroxy group or amino group.
  • the top coat skin layer further contains a cross linker with a content of no more than 20wt%, preferably 5-10wt%, based on the total solid weight of the aqueous polyurethane dispersion.
  • the crosslinker used here is selected from aro matic- or aliphatic- polycarbodiimide (PCDI) with or without hydrophilic modification.
  • the inventive laminate has improved properties in terms of instant peel strength, curing property and/or flexing endurance by using, as top coat layer, in novative aqueous dispersions containing a specified amount of carboxylate group and prefera bly, a specified molar ratio of hydroxyl and/or amino group to the isocyanate group, and option ally neutralizing the aqueous dispersion with gel catalytic amines.
  • Figure 1 shows the process for preparing 2-layer Laminates consisting of the top coat layer and the base coat.
  • Figure 2 shows the process for preparing non-solvent PU synthetic leather.
  • the articles “a” and “an” refer to one or to more than one (i.e., to at least one) of the grammatical object of the article or component.
  • total solid weight refers to the total weight of the system minus the weight of all the solvents (including water).
  • all the weight percentages (%) of the additives and/or auxiliaries refer to percentages of “the solid weight of the additives and/or auxiliaries di vided by total solid weight of the aqueous polyurethane dispersion”.
  • the temperature refers to room temperature and the pressure refers to ambient pressure.
  • the present invention provides a laminate, comprising
  • the aqueous polyurethane dispersion used in the top coat skin layer is prepared from an isocyanate component (a’) and a polyol component (b’).
  • the isocyanate component (a’) comprises the customary aliphatic, cycloaliphatic and aromatic di- and/or polyi socyanates.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocya nate
  • polymeric MDI polyphenylene polymethylene polyisocyanates
  • diphenylmethane diisocyanate monoomeric MDI
  • Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and hydrogenated diphenylmethane-4,4’-diisocyanate (H12MDI) are also preferable.
  • the isocyanates or else hereinbelow described isocyanate prepolymers may also be in a modi fied state, for example through incorporation of uretidione, carbamate, isocyanurate, car- bodiimide or allophanate groups. It is further possible to use blends of the various isocyanates.
  • the polyisocyanates may also be employed in the form of polyisocyanate prepolymers. These prepolymers are known in the prior art. They are prepared in a conventional manner by reacting above-described polyisocyanates with hereinbelow described compounds having isocyanate- reactive hydrogen atoms to form the prepolymer. The reaction may for example be carried out at temperatures of about 80°C.
  • the polyol/polyisocyanate ratio is generally chosen such that the NCO content of the prepolymer is in the range from 6% to 25% by weight.
  • the polyol component (b’) preferably comprises polyetherols and/or polyesterols. These are commonly known and described for example in "Kunststoffhandbuch Polyurethane” Gunter Oer- tel, Carl-Hanser-Verlag, 2 nd edition 1983, chapter 3.1.1. Alternative designations likewise cus tomary in the pertinent art are polyether polyols or polyether alcohols on the one hand and poly ester polyols or polyester alcohols on the other hand.
  • the polyol component (b’) is a polyol mixture.
  • the polyol component (b’) comprises (b’-1) a polyol having a weight-average molecular weight in the range of from 500 g/mol to 10000 g/mol, and functionality in the range of from 2 to 4, and (b’-2) a polyol having a weight average molecular weight in the range of from 500 g/mol to 3000 g/mol, and functionality in the range of from 2 to 4.
  • polyol (b’-1) may be pol yester, such as XCP-2000N and polyol (b’-2) may be polyether, preferably hydrophilic polyether based on polyethylene glycol, such as Ymer N120.
  • the polyol component (b’) also comprises (b’-3) a chain extender having a molecular weight of less than 400 g/mol, and (b’-4) a hydrophilic chain extender containing carboxylate group or sul- phonate group.
  • Chain extender (b’-3) that may be used are substances having a molar mass which is preferably smaller than 400 g/mol, particularly preferably from 60 to 400 g/mol, wherein chain extenders have at least 2 hydrogen atoms reactive toward isocyanates .These may be used individually or preferably in the form of a mixture. It is preferable to use diols and/or triols having molecular weights from 60 to 400, and in particular from 60 to 350. Examples of those that may be used are aliphatic, cycloaliphatic, and/or araliphatic diols having from 2 to 10 carbon atoms, e.g.
  • eth ylene glycol 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,10-decanediol, 1 ,2-, 1 ,3-, and 1 ,4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, tripropylene glycol, diethanola mine, or triols, e.g. 1 ,2,4- or 1 ,3,5-trihydroxycyclohexane, glycerol, and trimethylolpropane. It is also preferable to use diamine and/or triamine.
  • the amount of chain extender (b’-3), based on the total solid weight of the aqueous polyurethane dispersion, is preferably from 0.1 to 10% by weight, particularly preferably from 0.2 to 8% by weight.
  • Hydrophilic chain extenders (b’-4) that may be used are hydrophilic chain extenders with car boxyl group or sulphonate group. They provide hydrophilic groups for the aqueous polyurethane dispersion to ensure that the dispersion has an appropriate hydrophilicity.
  • AB-salt Sodium 2-[(2-aminoethyl)amino]ethanesulphonate
  • DM PA dimethylolpropionic acid
  • the amount of hydrophilic chain extenders (b’-4), based on the total solid weight of the aqueous polyurethane dispersion, is preferably from 0.1 to 50% by weight, particularly pref erably from 0.2 to 35% by weight.
  • the aqueous polyurethane dispersion contains no more than 0.5%, preferably less than 0.1 % of carboxylate group, based on the total solid weight of the aqueous polyurethane dispersion, wherein the carboxylate group derives from hydrophilic extenders with carboxyl group as well as other carboxyl-containing starting materials which are used to prepare the aqueous polyure thane dispersion. Additionally, the molar ratio of hydroxyl and/or amino group to the isocyanate group present in the aqueous polyurethane dispersion is 0.9 to 1.5, preferably 1.10 to 1.25.
  • the aqueous polyurethane dispersion optionally contains an amine neutralization agent with gel reactivity, so as to provide suitable pH range of 6-9 for the dispersion.
  • the amount of amine neutralization agent based on the total solid weight of the aqueous polyurethane dispersion, is preferably from 0.01 to 5% by weight, particularly preferably from 0.05 to 2% by weight.
  • the amine neutralization agent is selected from the group consisting of triethylenedi- amine (TEDA), 1 ,2-dimethylimidazole, N,N-dimethylcyclohexylamine, N,N,N',N'-Tetramethyleth- ylenediamine and tertiaryamine.
  • the aqueous polyurethane dispersion contains surfactants.
  • the surfactants may be nonionic, such as alcohol ethoxylates, alkyl polyglucosides, Bisphenol A ethoxylates, ethox- ylated natural fat/oil, fatty acid ethoxylates, or/and anionic surfactants, such as fatty alcohol ethersulfates, fatty alcohol sulfates, linear alkylbenzene sulphonates, oleic acid sulphonates, di- isodecyl sulfosuccinate, alkyl ether phosphate, alkyl ether carboxylates, or/and cationic surfac tants, such as amine ethoxylates, aminopolyol, quaternary ammonium surfactants.
  • the top coat skin layer based on an aqueous polyu rethane dispersion also contains crosslinker.
  • suitable crosslinker may be selected from aromatic- or aliphatic- polycarbodiimide (PCDI) with or without hydrophilic modification.
  • the crosslinker may be used in a mixed or single manner, preferable in a mixed manner.
  • Astacin Hardener CA and/or Astacin Hardener Cl may be used as the crosslinker.
  • the amount of the crosslinker, based on the total solid weight of the aqueous polyurethane dispersion is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, and in particular from 5 to 15% by weight.
  • the top coat skin layer based on an aqueous polyu rethane dispersion also contains other additives and/or auxiliaries which are commonly known by those skilled in the art.
  • the additives and/or auxiliaries that may be used comprise surfac tants, thickening agent, pigment, colorants, antioxidants, reinforcing agents, stabilizers and wet ting agent.
  • it is generally to employ one of above additives and/or auxiliaries, or the mixture thereof, so as to improve the properties of the obtained polyu rethane dispersion.
  • the amount of other additives and/or auxiliaries is preferably from 0 to 25% by weight, more preferably from 0.5 to 15% by weight, based on the total solid weight of of the aqueous polyurethane dispersion.
  • pigment it is possible to use all com pounds which are suitable for preparing polyurethane dispersion, such as Permutex PP-39-611 .
  • the amount of pigment, if present, based on the total solid weight of the aqueous polyurethane dispersion is preferably from 1 to 12% by weight, particularly preferably from 5 to 10% by weight.
  • thickening agent it is possible to use all compounds which are commonly used for preparing polyurethane dispersion, such as Permutex RM 4456.
  • the amount of thickening agent, if present, based on the total solid weight of the aqueous polyurethane dispersion is preferably from 0.1 to 8% by weight, particularly preferably from 0.5 to 5% by weight.
  • wetting agent it is possible to use all compounds which are commonly used for preparing polyurethane dispersion, such as BYK 348.
  • the amount of wetting agent, if present, based on the total solid weight of the aqueous polyurethane dispersion is preferably from 0.1 to 5% by weight, particu larly preferably from 0.3 to 3% by weight.
  • the solvent-free polyurethane system comprises an isocyanate compo nent (a), a polyol component (b), and optionally, a catalyst (c).
  • isocyanate component (a) it comprises polyisocyanates.
  • the polyisocyanates used com prise the customary aliphatic, cycloaliphatic and aromatic di- and/or polyisocyanates.
  • Prefer ence is given to using tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and mixtures of diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates (polymeric MDI), and especially diphenylmethane diisocyanate (monomeric MDI).
  • Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and hydrogenated diphenylmethane- 4,4’-diisocyanate are also preferable.
  • the isocyanates or else hereinbelow described isocyanate prepolymers may also be in a modi fied state, for example through incorporation of uretidione, carbamate, isocyanurate, car- bodiimide or allophanate groups. It is further possible to use blends of the various isocyanates.
  • the polyisocyanates may also be employed in the form of polyisocyanate prepolymers. These prepolymers are known in the prior art. They are prepared in a conventional manner by reacting above-described polyisocyanates with hereinbelow described compounds having isocyanate- reactive hydrogen atoms to form the prepolymer. The reaction may for example be carried out at temperatures of about 80°C.
  • the polyol/polyisocyanate ratio is generally chosen such that the NCO content of the prepolymer is in the range from 6% to 25% by weight.
  • the amount of the polyol component (b) is selected such that the isocyanate index is 100-140, preferably 100-120, more preferably 102-110, especially 105.
  • the polyol component (b) may in principle comprise compounds having isocyanate-reactive hy drogen atoms. These compounds bear, for example, two or more reactive groups selected from OH groups, SH groups, NH groups, NH2 groups and carbon-acid groups, for example b-diketo groups, in the molecule.
  • the term polyurethanes herein shall comprise polyisocyanate polyaddition prod ucts in general, including polyureas for example.
  • the polyol component (b) preferably comprises polyetherols and/or polyesterols. These are commonly known and described for example in "Kunststoffhandbuch Polyurethane” Gunter Oer- tel, Carl-Hanser-Verlag, 2 nd edition 1983, chapter 3.1.1. Alternative designations likewise cus tomary in the pertinent art are polyether polyols or polyether alcohols on the one hand and poly ester polyols or polyester alcohols on the other. Preferred polyester polyols or polyester alco hols are, for example, PTMEG, PPG, or PEG.
  • polyesterols When polyesterols are employed, these are typically obtained by condensation of polyfunctional alcohols having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms, with polyfunc tional carboxylic acids having from 2 to 12 carbon atoms, examples being 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 from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms
  • polyfunc tional carboxylic acids having from 2 to 12 carbon atoms
  • examples being succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric
  • polyetherols When polyetherols are employed, these are generally obtained by known methods, for example by anionic polymerization using alkali metal hydroxides as catalysts and with addition of a starter molecule comprising multiple reactive hydrogen atoms in attachment, from one or more alkylene oxides selected from propylene oxide (PO) and ethylene oxide (EO), butylene oxide and tetrahydrofuran.
  • a starter molecule comprising multiple reactive hydrogen atoms in attachment, from one or more alkylene oxides selected from propylene oxide (PO) and ethylene oxide (EO), butylene oxide and tetrahydrofuran.
  • Useful polyetherols (b) further include so-called low-unsaturation polyetherols.
  • Low-unsaturation polyols for the purposes of this invention are more particularly polyether alcohols comprising less than 0.02 meq/g and preferably less than 0.01 meq/g of unsaturated compounds.
  • Polyether alcohols of this type are obtained via addition of ethylene oxide and/or propylene oxide and mix tures thereof onto at least difunctional alcohols in the presence of so-called double metal cya nide catalysts.
  • the alkylene oxides may be used individually, alternatingly in succession or as mixtures.
  • the use of an EO-PO mixture leads to a polyether polyol having randomly distributed PO/EO units.
  • Starter molecules used are typically NH- or OH-functional compounds such as water, amines or alcohols. Preference is given to using di- to hexahydric alcohols, such as ethanediol, 1,2-pro- panediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol and/or sorbitol.
  • di- to hexahydric alcohols such as ethanediol, 1,2-pro- panediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol and/or sorbi
  • polyetherols obtained by ring-opening polymerization of tetrahydro- furan preferably have a functionality of about 2. They preferably further have a number average molecular weight in the range from 500 to 4000 g/mol, prefera bly in the range from 700 to 3000 g/mol and more preferably in the range from 900 to 2500 g/mol.
  • the polyol component (b) may also com prise a customary chain extender or the combination of two or more, which may be compounds having 2 or more isocyanate-reactive hydrogen atoms and molecular weights in the range from 42 to less than 400 g/mol.
  • the polyol component (b) comprises one or more constituents se lected from
  • (b-1) a polyol, preferably a polyether polyol, having a number-average molecular weight in the range from 500 g/mol to less than 3000 g/mol
  • (b-2) a polyol, preferably a polyether polyol, having a number-average molecular weight in the range from 3000 g/mol to 8000 g/mol (b-3) a chain extender having a molecular weight of less than 400 g/mol.
  • component (b-1) comprises a polyetherol or a polyesterol, more preferably a polyether polyol, having a number average molecular weight in the range from 500 to less than 3000 g/mol, preferably in the range from 800 to 2500 g/mol, and more preferably in the range from 1000 to 2200 g/mol.
  • the component (b-1) typically has an average functionality of 1.8 to 3, more preferably of 1.9 to 2.1 and especially of 2.0. Functionality here refers to the "theoretical OFI functionality" calcu lated from the functionality of the starter molecules used.
  • Polytetrahydrofuran is more preferably used as component (b-1). More particularly, polytetrahy- drofuran having a number average molecular weight in the range from 1000 to 2000 g/mol is used.
  • the component (b-1) is typically present in component (b) in an amount from 30% to 100% by weight and preferably from 50% to 90% by weight, based on the overall weight of the polyol component (b).
  • component (b-2) comprises a polyetherol or a polyesterol and more preferably a polyether polyol having a number average molecular weight in the range from 3000 to 8000 g/mol, preferably in the range from 3500 to 7000 g/mol and more preferably in the range from 4000 to 6000 g/mol.
  • the component (b-2) typically has an average functionality of 1 .9 to 6, more preferably of 2.3 to 4 and especially of 3.0. Functionality here refers to the "theoretical OH functionality" calculated from the functionality of the starter molecules used.
  • Component (b-2) is more preferably a polyether polyol obtainable by propoxylation and/or eth- oxylation of glycerol or trimethylolpropane, especially with an EO endblock.
  • This polyether pol yol preferably has a number average molecular weight in the range from 4500 to 6000 g/mol.
  • the component (b-2) is typically present in the polyol component (b) in an amount from 5% to 80% by weight and preferably from 10% to 30% by weight, based on the overall weight of the polyol component (b).
  • the polyol component (b) may further comprise chain extenders as component (b-3).
  • Suitable chain extenders are compounds having two or more isocyanate-reactive hydrogen atoms and a molecular weight below 400 g/mol and are known in the prior art. Preference is given to using 2- functional alcohols having molecular weights below 400 g/mol and especially in the range from 60 to 150 g/mol. Examples are ethylene glycol, propylene glycol, diethylene glycol, 1 ,4-butane- diol, dipropylene glycol, tripropylene glycol, glycerol, or trimethylolpropane. 1 ,4-Butanediol, glyc erol, or trimethylolpropane is preferably used.
  • the chain extender is typically used in an amount from 2% to 25% by weight, preferably from 3% to 13% by weight and more preferably from 3% to 20% by weight, based on the overall weight of the polyol component (b).
  • the solvent-free polyurethane system also contains catalyst (c) and other additives and/or auxil iaries (d) which are commonly known by those skilled in the art.
  • the customary and known polyurethane formation catalysts are optionally used as catalysts for producing the polyurethane system of the present invention, examples being or ganic tin compounds or tin and Sn complex, such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and Zn salts or Bi salts, such as Zinc octoate and Bismuth octoate, and also strongly basic amines such as diazabicyclooctane, triethylamine or preferably triethylenediamine or bis(N,N-dimethylaminoethyl)ether.
  • the amount of catalyst is preferably from 0.5 to 5% by weight, more preferably from 1 to 4% by weight, based on the total weight of components of (b)-(d).
  • the additives and/or auxiliaries may be used comprise pigment, colorants, antioxidants, silicone oil leveling agent, stabilizers and wetting agent.
  • it is generally to employ one of above additives and/or auxiliaries, or the mixture thereof, so as to improve the properties of the obtained polyurethane system.
  • the amount of additives and/or auxil iaries is preferably from 0 to 20% by weight, more preferably from 0.5 to 15% by weight, based on the total weight of componets of (b)-(d).
  • the laminate comprises a substrate layer underneath the base coat layer.
  • the substrate layer may be any layer capable of forming an adher ing bond with the base coat layer.
  • the thickness of the substrate layer is typically in the range from 0.01 mm to 20 mm, preferably in the range from 0.1 mm to 15 mm.
  • the substrate layer is selected from, for example, non-woven fabric, textile, TPU, genuine leather, wood, plastic or split leather.
  • One preferred embodiment utilizes non-woven fabric or split leather as the sub strate layer.
  • the laminate according to the invention has improved instant peel strength, curing property and/or flexing endurance.
  • the present laminate may be used as upper material for footwear, clothing, cap, luggage and bag, furniture, cushion, etc.
  • XCP-2000N was dehydrated in a vacuum at 120 °C for 30 min with stirring and cooled to 85 °C.
  • DMPA if present
  • Ymer N120 and trimethylolpropane were stirred in.
  • IPDI was added after 5 min. Stirring was continued at 85 °C until the NCO content of the mixture remains constant (A1: 1.6% by weight, A2: 4.8% by weight, A3: 2.6% by weight, A4: 2.9% by weight, A5: 4.9% by weight).
  • 700 g Acetone was slowly added while the temperature was maintained at 50 °C.
  • Formulations in Table 3 were prepared by blending the ingredients by sequence, and then were applied with a thickness of 100 pm within 4 hours by knife coating on a Favini B100 release pa per, followed by drying in Oven #1 at 80°C for 2 min and at 120°C for 2 min. Next, the formula tion in Table 4 was applied with a thickness of 350 pm by knife coating on top of the dried top coat formulation, and heated in Oven #2 at 120-140°C for 5-10 min, to form a base coat layer. Then, the resulting laminate was separated from the release paper to obtain a final laminate product.
  • Preparation of PU synthetic leather comprising of the top coat skin layer, the base coat layer and the substrate layer
  • Formulations in Table 3 were prepared by blending the ingredients by sequence, and then were applied with a thickness of 100 pm by knife coating within 4 hours onto a Favini B100 release paper, followed by drying in Oven #1 at 80 °C for 2 min and at 120 ° C for 2 min. Next, the formu lation in Table 4 was applied with a thickness of 350 pm by knife coating on top of the dried top coat formulation, and heated in Oven #2 at 90-120°C for 30sec-6 min. Then, a substrate layer was applied on the dried base coat layer, and heated in Oven #3 at 140°C for 2-10 min, followed by pressing. PU synthetic leather was obtained after stripping the release paper.
  • A-Component * comprises the isocyanate component (a) and catalyst (c).
  • B-component ** comprises the polyol component (b).
  • Curing property of 2-component PU layer was judged by using nail to press the top coat of the laminate (the PU synthetic leather) and then visually evaluating according to the following gra- des:
  • Grade 1 nail print is rebound > 10 sec, or the top coat is damaged
  • Grade 2 nail print rebound (7 sec - 9 sec);
  • Grade 3 nail print rebound (4 sec - 6 sec);
  • Grade 4 nail print rebound (1 sec - 3 sec);
  • the laminates obtained in the inventive examples 2-6 by using the inventive aqueous po- lyurethane dispersion as the top coat skin layer achieve improved properties in terms of instant peel strength and curing property.
  • Example 3 Preparation of PU synthetic leather comprising of the top coat skin layer, the base coat layer and the substrate layer
  • Formulations in Table 6 were prepared by blending the ingredients by sequence, and then were applied with a thickness of 100 pm by knife coating within 4 hours onto a Favini B100 release paper, followed by drying in Oven #1 at 80 °C for 2 min and at 120 °C for 2 min.
  • the formu lation in Table 7 was applied with a thickness of 350 pm by knife coating on top of the dried top coat formulation, and heated in Oven #2 at 90-120°C for 30sec-6 min.
  • a substrate layer was applied on the dried base coat layer, and heated in Oven #3 at 140°C for 2-10 min, followed by pressing.
  • PU synthetic leather was obtained after stripping the release paper.
  • A-Component * comprises the isocyanate component (a) and catalyst (c).
  • B-component ** comprises the polyol component (b).
  • the test follows the standard ISO 5402.
  • Test pieces were prepared according to ISO 2418, including cutting at least three Vertical test pieces and at least three Horizontal test pieces, conditioning the test pieces according to ISO 2419 and performing the test in conditioned atmosphere. After 25x magnification, the test pie ces were visually evaluated in terms of the cracks/loss of adhesion/change of color shade. The expression “pass” indicates no visible cracks/loss of adhesion/visible change of color shade.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention se rapporte à un stratifié comprenant A) une couche de revêtement de couche supérieure à base d'une dispersion aqueuse de polyuréthane, et B) une couche de revêtement de base sous la couche de revêtement de couche supérieure et sur la base d'un système de polyuréthane sans solvant comprenant un composant isocyanate (a) et un composant polyol (b), l'indice d'isocyanate du système de polyuréthane étant dans la plage de 100 à 140, la dispersion aqueuse de polyuréthane ne contenant pas plus de 0,5 % de groupe carboxylate, sur la base du poids total solide de la dispersion aqueuse de polyuréthane.
PCT/EP2021/058948 2020-04-15 2021-04-06 Stratifié comprenant une dispersion aqueuse de polyuréthane et un polyuréthane à deux composants et son utilisation Ceased WO2021209284A1 (fr)

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