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WO2024126304A1 - Aqueous compositions comprising (meth)acrylate group carrying polyurethane which yield cross-linked layers of high hardness and good adhesion - Google Patents

Aqueous compositions comprising (meth)acrylate group carrying polyurethane which yield cross-linked layers of high hardness and good adhesion Download PDF

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Publication number
WO2024126304A1
WO2024126304A1 PCT/EP2023/084975 EP2023084975W WO2024126304A1 WO 2024126304 A1 WO2024126304 A1 WO 2024126304A1 EP 2023084975 W EP2023084975 W EP 2023084975W WO 2024126304 A1 WO2024126304 A1 WO 2024126304A1
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WIPO (PCT)
Prior art keywords
group
groups
carrying
meth
acrylate
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PCT/EP2023/084975
Other languages
French (fr)
Inventor
Susanne Neumann
Christine Roesch
Axel Becker
Peter Thuery
Vanessa KLEE
Silke FISCHER
Andrea SCHMALENBECK
Vivian Else HINDERLE
Guenter SCHAEFFLER
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Basf Se
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Priority to CN202380085470.XA priority Critical patent/CN120344582A/en
Publication of WO2024126304A1 publication Critical patent/WO2024126304A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/34Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348Hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0804Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0838Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • C08G18/227Catalysts containing metal compounds of antimony, bismuth or arsenic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/36Hydroxylated esters of higher fatty acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/675Low-molecular-weight compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • Aqueous Compositions comprising (Meth)acrylate Group carrying Polyurethane which yield Cross-Linked Layers of High Hardness and Good Adhesion
  • the present invention relates to aqueous compositions comprising (meth)acrylate group carrying polyurethanes, to aqueous coating compositions comprising these compositions, to crosslinked layers formed from the coating compositions, and to substrates coated with these layers.
  • Aqueous compositions comprising (meth)acrylate group carrying polyurethanes are used as binder in many applications, for example in coating compositions such as top-coat compositions, stain compositions, in ink compositions and in adhesive compositions.
  • cross-linked layers formed from these compositions on a substrate show a high hardness and a good adhesion to the substrate.
  • WO2011107398 (Bayer) describes an aqueous radiation-curable dispersion based on polyurethane acrylate, wherein the polyurethane acrylate comprises as formation compounds (A) one or more aromatic polyepoxy(meth)acrylates having an OH number of 20 to 300 mg KOH/g of substance, C) one or more oligo- or polyesters containing unsaturated fatty acids having an OH number of 15 to 300 mg KOH/g of substance and an iodine number of greater than 50 g 12/100 g of substance, E) one or more compounds having at least one group reactive towards isocyanate and additionally at least one hydrophilizing group and F) one or more organic polyisocyanates.
  • A one or more aromatic polyepoxy(meth)acrylates having an OH number of 20 to 300 mg KOH/g of substance
  • composition of claim 1 the coating composition of claim 14, and the layer of claim 15 and the coated substrate of claim 16.
  • composition of the present invention is a composition comprising
  • At least one polyurethane PU carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, which polyurethane is obtainable by the reaction of at least one polyisocyanate (A), at least one polyol (B1) carrying at least one COOH group, at least one polyol (B2) carrying at least one (meth)acrylate group, but no COOH group, and comprising at least one aromatic ring, at least one polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring, optionally at least monoalcohol (B4) carrying at least one (meth)acrylate groups
  • the equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is preferably at least 50%, more preferably at least 55%.
  • the weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is preferably in the range of from 2% to 30%, more preferably in the range of from 3 to 25%, and most preferably in the range of from 5 to 18%.
  • (meth)acrylate comprises acrylate and methacrylate.
  • Polyols have an OH functionality of at least 1.5.
  • the OH functionality of a polyol is (hydroxyl number polyol [g KOH/g] x molecular weight poly- ol)/molecular weight KOH. If the the polyol is an oligomer or polymer, the number average molecular weight of the polyol is used, which can be determined using gel permeation chromatography calibrated to a polystyrene standard.
  • the molecular weight of KOH is 56 g/mol.
  • the hydroxyl number of a polyol can be determined according to DIN53240, 2016.
  • Polyols can be aliphatic, alicylic or aromatic polyols.
  • Aromatic polyols are polyols, wherein at least one OH functionality is directly attached to an aromatic ring.
  • Alicyclic polyols comprise at least one alicyclic ring and each OH functionality is not directly attached to an aromatic ring.
  • Aliphatic polyols do not comprise an alicyclic ring and each OH functionality is not directly attached to an aromatic ring.
  • Preferred aliphatic and alicyclic polyols do not comprise aromatic rings.
  • Monoalcohols have an OH functionality of below 1.5.
  • the OH functionality of a monoalcohol is (hydroxyl number monoalcohol [g KOH/g] x molecular weight monoalcohol)/molecular weight KOH. If the monoalcohol is an oligomer or polymer, the number average molecular weight of the monoalcohol is used, which can be determined using gel permeation chromatography calibrated to a polystyrene standard. The molecular weight of KOH is 56 g/mol. The hydroxyl number of a monoalcohol can be determined according to DIN53240, 2016.
  • Monoalcohols can be an aliphatic, alicyclic or aromatic monoalcohol.
  • Aromatic monoalcohols are monoalcohols, wherein the OH functionality is directly attached to an aromatic ring.
  • Alicyclic monoalcahols comprise at least one alicyclic ring and each OH functionality is not directly attached to an aromatic ring.
  • Aliphatic monoalcohols do not comprise an alicyclic ring and the OH functionality is not directly attached to an aromatic ring.
  • Preferred aliphatic and alicyclic monoalcohols do not comprise aromatic rings.
  • An ethylenically unsaturated group can be any ethylenically unsaturated group that can polymerize by free radical mechanism upon heat, radiation treatment, usually UV radiation treatment, in the presence of a suitable initiator, or upon electron beam treatment.
  • ethylenically unsaturated groups are acryloyl, methacryloyl, vinyl and allyl groups.
  • Preferred ethylenically unsaturated groups are selected from the group of acryloyl and methacryloyl groups. More preferred ethylenically unsaturated groups are acryloyl groups.
  • Polyisocyanates comprise polyisocyanates carrying blocked NCO groups as well as polyisocyanates carrying free NCO groups.
  • Polyisocyanates carrying blocked NCO groups can be deblocked to the corresponding polyisocyanate carrying free NCO groups under specific condi- tons, for example at elevated temperatures, such as at temperatures above 110°C.
  • the polyisocyanate carrying blocked NCO groups is characterized in the following via its corresponding polyisocyanate carrying free NCO groups.
  • polyisocyanates comprise only polyisocyanates carrying free NCO groups.
  • Polyisocyanates have an NCO functionality of at least 1.5.
  • the NCO functionality of a polyisocyanate is NCO content x (molecular weight polyisocya- nate/molecular weight NCO). If the polyisocyanate is a polymeric polyisocyanate, the average weight molecular weight of the polyisocyanate is used. The average weight molecular weight of a polymeric polyisocyanate can be determined using gel permeation chromatography calibrated to a polystyrene standard. The NCO content of the polyisocyanate is weight NCO/weight polyisocyanate. The molecular weight of NCO is 42 g/mol.
  • the NCO content of a polyisocyanate can be determined as follows:
  • Polyisocyanate can be aliphatic, alicyclic or aromatic polyisocyanates.
  • Aromatic polyisocyanates are polyisocyanates, wherein at least one NCO functionality is directly attached to an aromatic ring. Alicyclic polyisocyanates comprise at least one alicyclic ring and each NCO functionality is not directly attached to an aromatic ring. Aliphatic polyisocyanates do not comprise an alicyclic ring and each NCO functionality is not directly attached to an aromatic ring. Preferred aliphatic and alicyclic polyisocyanates do not comprise aromatic rings.
  • the polyol (B1) carrying at least one COOH group can be any aliphatic, alicyclic or aromatic polyol (B1) carrying at least one COOH group.
  • the OH functionality of polyol (B1) carrying at least one COOH group is usually in the range of from 1.7 to 6.0, more preferably in the range of 1.8 to 5.4, even more preferably in the range of 1.8 to 3.4, most preferably in the range from 1.8 to 2.4, and in particular in the range of 1.9 to 2.2.
  • the polyol (B1) carrying at least one COOH group preferably has a number average molecular weight of below 750 g/mol, more preferably of below 500 g/mol, and most preferably of below 250 g/mol.
  • polyols (B1) carrying one COOH group are 2,2-bis(hydroxymethyl) C2-io-alkanoic acid such as 2,2-bis(hydroxymethyl) propionic acid (dimethylolpropionic acid), 2,2-bis(hydroxy- methyl) butanoic acid and 2,2-bis(hydroxymethyl) pentanoic acid.
  • 2,2-bis(hydroxymethyl) C2-io-alkanoic acid such as 2,2-bis(hydroxymethyl) propionic acid (dimethylolpropionic acid), 2,2-bis(hydroxy- methyl) butanoic acid and 2,2-bis(hydroxymethyl) pentanoic acid.
  • the polyol (B1) carrying at least one COOH group is preferably a polyol carrying one COOH group, more preferably an aliphatic or alicyclic polyol (B1) carrying one COOH group, even more preferably an aliphatic polyol (B1) carrying one COOH group.
  • polyol (B1) is selected from the group consisting of 2,2-bis(hydroxymethyl) propionic acid and 2,2- bis(hydroxymethyl) butanoic acid, and in particular 2, 2-bis(hydroxymethyl) propionic acid.
  • Polyol (B2) carrying at least one (meth)acrylate groups, but no COOH group, and comprising at least one aromatic ring can be any polyol carrying at least one (meth)acrylate group, but no COOH group, and comprising at least one aromatic ring.
  • the aromatic ring can be any aromatic ring.
  • aromatic rings are benzol rings and nathphaline rings.
  • the OH functionality of polyol (B2) is usually in the range of from 1 .7 to 6.0, more preferably in the range of 1.8 to 5.4, even more preferably in the range of 1.8 to 3.4, most preferably in the range from 1.8 to 2.4, and in particular in the range of 1.9 to 2.2.
  • the polyol (B2) preferably has a number average molecular weight in the range of from 250 to 750 g/mol.
  • the polyol (B2) is preferably of formula wherein L 1 is selected from the group consisting of
  • the polyol (B2) is more preferably of formula wherein L 1 is selected from the group consisting of
  • the polyol (B2) is most preferably of formula Polyol (B3) can be any polyol which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
  • the ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms can be a monoester, a diester or a triester.
  • the monoester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms also comprises mixtures of monoesters of glycerin with different carboxylic acids carrying at least 6 carbon atoms.
  • Carboxylic acids carrying at least 6 carbon atoms of a diester or triester can be the same or different.
  • the diester and triesters, respectively, of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms also comprise mixture of diesters and triesters, respectively.
  • the carboxylic acid carrying at least 6 carbon atoms can carry further subsituents such as OH groups.
  • the carboxylic acid carrying at least 6 carbon atoms can be a saturated carboxylic acid carrying at least 6 carbon atoms or an unsaturated carboxylic acid carrying at least 6 carbon atoms.
  • saturated carboxylic acids carrying at least 6 carbon atoms are hexanoic acid, hep- tanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), di hydroxy stearic acid, arachidic acid (C20), behenic acid (C22), lignoceric acid (C24) and cerotic acid (C26).
  • Examples of unsaturated carboxylic acids carrying at least 6 carbon atoms are myristoleic acid (C14), palmitoleic acid (C16), sapienic acid (C16), oleic acid (C18), elaidic acid (C18), vaccenic acid (C18), linoleic acid (C18), linoleidic crampic crampd, alpha linolenic acid (C18), ricinoleic acid (c18), arachidonic acid (C20), ecosapentaenoic acid (C20), erucic acid (C22).
  • the polyol (B3) is preferably an ester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein the polyol has a hydroxy number in the range of 50 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
  • the polyol (B3) is more preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, and wherein at least one of the carboxylic acids also carries at least one OH group, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
  • carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, and also carrying at least one OH group are ricinoleic acid, partially and fully hydrogenated ric- inoleic acid, as well as at least monohydroxylated carboxylic acids which are obtainable from mono- or polyunsaturated carboxylic acids carrying at least 10 carbon atoms and at most 21 carbon atoms.
  • the at least monohydroxylated carboxylic acids can for example be obtained from unsaturated carboxylic acids carrying at least 10 carbon atoms and at most 21 carbon atoms by full or partial epoxidation of the ethylenically unsaturated bond or bonds, followed by ring opening of the epoxide ring under formation of an OH group.
  • Epoxidation can be performed by methods known in the art such as by treatment of the unsaturated carboxylic acid with a peroxyacid or a peroxide.
  • Hydroxylation can also be performed by methods known in the art. For example, hydroxylation of the epxide ring occurs if the epoxidation is performed in aqueous medium.
  • polyol (B3) examples are castor oil as well as partially or fully hydrogenated castor oil.
  • polyol (B3) are at least monohydroxylated and optionally partially or fully hydrogenated vegetable or animal oils, which are triesters of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, and wherein at least one of the carboxylic acids also carries at least one OH group, and which at least monohydroxylated and optionally partially or fully hydrogenated vegetable or animal oils have a hydroxy number in the range of 10 to 250, do not carry COOH groups and (meth)acrylate groups and do not comprise at least one aromatic ring.
  • Examples of vegetable and animal oils suitable for the preparation of at least monohydroxylated and optionally partially or fully hydrogenated vegetable and animal oils are canola oil, cod liver oil, corn oil, cottonseed oil, safflower oil, lineseed oil, olive oil, palm oil, peanut oil, sesame oil, soybean oil, sunflower oil and walnut oil.
  • the preparation of at least monohydroxylated and optionally partially or fully hydrogenated vegetable and animal oils is known in the art and is, for example, described in US20100267925A1.
  • the polyol (B3) is even more preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein at least one of the carboxylic acids also carries at least one OH group and wherein at least 50 weight% of the carboxylic acids are carboxylic acids carrying at least 16 carbon atoms and at most 21 carbon atoms, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
  • the polyol (B3) is most preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein at least one of the carboxylic acids also carries at least one OH group and wherein at least 75 weight% of the carboxylic acids are carboxylic acids carrying at least 16 carbon atoms and at most 21 carbon atoms, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
  • the polyol (B3) is even most preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein at least one of the carboxylic acids also carries at least one OH group and wherein at least 80 weight% of the carboxylic acids is ricinoleic acid or fully or partially hydrogenated ricinolic acid, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
  • the polyol (B3) is in particular castor oil or partially or fully hydrogenated castor oil.
  • the triester of glycerin and ricinoleic acid is the major component of castor oil.
  • the triester of glycerin and hydrogenated ricinoleic acid is the major component of hydrogenated castor oil.
  • Monoalcohol (B4) carrying at least one (meth)acrylate group can be any aliphatic, alicyclic or aromatic monoalcohol carrying at least one (meth)acrylate group and no COOH group.
  • the monoalcohol (B4) has preferably an OH functionality in the range of from 0.8 to 1.4, preferably in the range of 0.9 to 1 .2.
  • Examples of monoalcohol (B4) carrying at least one (meth)acryloyl group are monoesters of diols with acrylic acid or methacrylic acid, diesters of triols with acrylic acid or methacrylic acid and triesters of tetraols with acrylic acid or methacrylic acid and pentaesters of hexaols with acrylic acid or methacrylic acid.
  • monoesters of diols with acrylic or methacrylic acid are monoesters of C1.10- aliphatic diols, preferably of Ci-6-aliphatic diols, with acrylic or methacrylic acid.
  • Examples of monoesters of Ci-6-aliphatic diols with acrylic or methacrylic acid are 2-hydroxy- ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate and 4-hydroxylbutyl acrylate.
  • monoalcohols (B4) carrying at least one (meth)acryloyl group are diesters of ethoxylated or propoxylated 1 ,1 ,1 -trimethylolpropane with acrylic or methacrylic acid, triesters of pentaerythritol with acrylic or methacrylic acid, triesters of ethoxylated or propoxylated di(1 ,1 ,1-trimethylol)propane with acrylic or methacrylic acid and pentaesters of dipentaerythritol.
  • Monoalcohol (B4) is preferably an aliphatic or alicyclic monoalcohol carrying one (meth)acryloyl.
  • monoalcohol (B4) is an aliphatic or alicyclic monoalcohol carrying one acryloyl group. Even more preferably monoalcohol (B4) is a monoester of a Ci-6-aliphatc diol with acrylic acid, and most preferably monoalcohol (B4) is 2-hydroxyethyl acrylate.
  • Compound, oligomer or polymer (B5) which carries at least one OH group and which is different from B1 , B2, B3 and B4 can be any compound, oligomer or polymer which is different from B1, B2, B3 and B4 and which carries at least one OH group.
  • Compound, oligomer or polymer (B5) can also carry at least one ethylenically unsaturated group.
  • Compound, oligomer or polymer (B5) can be an aliphatic, alicyclic or aromatic polyol which is different from B1 , B2 and B3.
  • Examples of aliphatic polyols which are different from B1, B2 and B3 are ethylene glycol, pro- pane-1, 2-diol, propane-1, 3-diol, butane-1, 2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3- diol, pentane-1 , 2-diol, pentane-1, 3-diol, pentane-1 ,4-diol, pentane-1,5-diol, pentane-2, 3-diol, pentane-2,4-diol, hexane-1, 2-diol, hexane-1, 3-diol, hexane-1 ,4-diol, hexane-1 ,5-diol, hexane- 1,6-diol, hexane-2,5-diol
  • aliphatic polyols which are different from B1 , B2 and B3 are di(ethylene glycol), tri(ethylene glycol), di(propylene glycol) and tri(propylene glycol).
  • aliphatic polyols which are different from B1 , B2 and B3 are glycerol, trimethylolmethane, 1 ,1 ,1-trimethylolethane, 1,1,1 -trimethylolpropane, 1 ,2,4-butanetriol and 1,3,5- tris(2-hydroxyethyl) isocyanurate and condensates thereof with ethylene oxide, propylene oxide and/or butylene oxide.
  • aliphatic polyols which are different from B1 , B2 and B3 are pentaerythritol, diglycerol, triglycerole, condensates of at least four glycerols, di(trimethylolpropane), di(pentaerythritol), and condensates thereof with ethylene oxide, propylene oxide and/or butylene oxide.
  • Examples of alicyclic polyols which are different from B1, B2 and B3 are 1,1-bis(hydroxymethyl)- cyclohexane, 1,2-bis(hydroxymethyl)-cyclohexane, 1 ,3-bis(hydroxymethyl)-cyclohexane, 1,4- bis(hydroxymethyl)-cyclohexane, 1 ,1-bis(hydroxyethyl)-cyclohexane, 1 ,2-bis(hydroxyethyl)- cyclohexane, 1 ,3-bis(hydroxyethyl)-cyclohexan, 1 ,4-bis(hydroxyethyl)-cyclohexane, 2, 2,4,4- tetramethyl-1,3-cyclobutandiol, cyclopentane- 1, 2-diol, cyclopentane- 1, 3-diol, 1,2- bis(hydroxymethyl) cyclopentane, 1 ,3-bis(hydroxymethyl) cyclopentane, cycl
  • Examples of alicyclic polyols which are different from B1 , B2 and B3 are inositol, sugars such as glucose, fructose and sucrose, sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), malitol and isomalt, as well as tris(hydroxymethyl)amine, tris(hydroxyethyl)amine and tris(hydroxypropyl)amine.
  • sugars such as glucose, fructose and sucrose
  • sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), malitol
  • polyols which are different from B1, B2 and B3 are also polyurethane polyols, polyester polyols, polycarbonate polyols, polyether polyols, polythioether polyols and polyacrylate polyols.
  • Polyurethane polyols are polymeric polyols comprising urethane groups as linking groups between two monomeric units, wherein the equivalent ratio urethane linking groups/all linking groups is at least 50/50, preferably at least 70/100, more preferably at least 80/100. Polyurethane polyols may comprise further linking groups such as carbonate, ether, thioether or ester groups.
  • Polyester polyols are polymeric polyols comprising ester groups as linking groups between two monomeric units, wherein the equivalent ratio ester linking groups/all linking groups is at least 50/50, preferably at least 70/100, more preferably at least 80/100. Polyester polyols may comprise further linking groups such as carbonate, ether, thioether or urethane groups.
  • Polyester polyols can be prepared by methods known in the art, for example by reacting at least one polyacid having a COOH functionality in the range of 1.8 to 2.4 with a polyol having an OH functionality in the range of 1.8 to 2.4.
  • polyacids having a COOH functionality of 2 are aliphatic polyacids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelinic acid, suberic acid, azelaic acid, sebacic acid, 1,11 -undecanedicarboxylic acid, 1 ,12- dodecanedicarboxlylic acid, 2-methylmalonic acid, 2-ethylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 3,3-dimethylglutaric acid, 2-phenylmalonic acid 2-phenylsuccinic acid, alicyclic polyacids such as cyclopentane-1 ,2-dicarboxy
  • polyester polyol is also polycaprolactone diol.
  • Polycarbonate polyols are polymeric polyols comprising at least two carbonate groups in the main chain of the polymer. Polycarbonate polyols may comprise further linking groups in the main chain in lower number than the number of carbonate groups such as ester, ether, thioether or urethane linkages. Examples of polycarbonate polyols are polycarbonates carrying no COOH group comprising units derived from the group consisting of butan-1,4-diol, pentane-1 ,5-diol and hexane-1 ,6-diol. Preferred polycarbonate polyols are polycarbonate polyols, wherein the equivalent ratio carbonate groups/all linking groups is at least 70/100, more preferably at least 80/100.
  • Polyether polyols are polymeric polyols comprising at least two ether groups in the main chain of the polymer. Polyether polyols may comprise further linking groups in the main chain in lower number than the number of ether groups such as ester, carbonate, thioether or urethane groups.
  • Preferred polyether polyols are polyether polyols, wherein the equivalent ratio ether groups/all linking groups is at least 70/100, more preferably at least 80/100.
  • polyether polyols examples include polyethylene glycols, polypropylene glycol, polyethylenepolypropylene glycol, polytetramethylene diol and polytetrahydrofuran diol.
  • Polyethylenepolypropylene glycols can be random or block copolymers
  • Polythioether polyols are polymeric polyols carrying no ethylenically unsaturated group and no COOH group and having at least two thioether groups in the main chain of the polymer.
  • Polythioether polyols may comprise further linking groups in the main chain in lower number than the number of ether groups such as ester, carbonate, ether or urethane groups.
  • Poly(meth)acrylate polyols are polymeric polyols comprising at least two units derived from (meth)acrylic acid ester monomers carrying at least one OH group such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
  • the polyisocyanate (A) can be any aliphatic, alicylic or aromatic polyisocyanate, which polyisocyanate can be a monomeric or polymeric polyisocyanate.
  • Examples of monomeric aliphatic polyisocyanates carrying no ethylenically unsaturated groups are tetramethylene 1 ,4-diisocyanate, pentamethylene 1 ,5-diisocyanate, hexamethylene 1,6- diisocyanate, heptamethylene 1,7-diisocyanate, octamethylene 1,8-diisocyanate, decamethylene 1,10-diisocyanate, dodecamethylene 1,12-diisocyanate, tetradecamethylene 1,14- diisocyanate, methyl 2,6-diisocyanatohexanoate, ethyl 2,6-diisocyanatohexanoate, 2,2,4- trimethylhexane 1,6-diisocyanate and 2,4,4-trimethylhexane 1,6-diisocyanate.
  • monomeric aliphatic polyisocyanates carrying no ethylenically unsaturated groups are 1 ,4,8-triisocyanatononane and 2’-isocyanatoethyl 2,6-diisocyanatohexanoate.
  • Examples of monomeric alicyclic polyisocyanates carrying no ethylenically unsaturated groups are 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1 ,2-diisocyanatocyclohexane, 4,4’- di(isocyanatocyclohexyl)methane, 2,4’-di(isocyanatocyclohexyl)methane, 1-isocyanato- 3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate), 1,3- bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2,4- diisocyanato-1- methylcyclohexane, 2,6-diisocyanato-1-methylcyclohexane and 3(or 4),8(or 9)-bis
  • Examples of monomeric aromatic polyisocyanates carrying no ethylenically unsaturated groups are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 2,4’-diisocyanatodiphenylmethane, 4,4’-diisocyanatodiphenylmethane, 1,3- phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1 ,5- naphthylene diisocyanate, diphenylene 4,4’-diisocyanate, 4,4’-diisocyanato-3,3’- dimethylbiphenyl, 3-methyldiphenylmethane 4,4’-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanato
  • monomeric aromatic polyisocyanates carrying no ethylenically unsaturated groups are 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate and 2,4,4’-triisocyanato- diphenyl ether.
  • Monomeric polyisocyanates carrying no ethylenically unsaturated group can be prepared by methods known in the art, for example by treating the corresponding amines with phosgene.
  • Polymeric polyisocyanate comprises at least two units derived from monomeric polyisocyanates.
  • Polymeric polyisocyanates usually also comprise at least one structural unit selected from the group consisting of uretdione, isocyanurate, biuret, urea, carbodiimide, uretonimine, urethane, allophanate, oxadiazinetrione and iminooxadiazinedione.
  • the NCO functionality of polyisocyanate (A) is usually in the range of from 1.6 to 10.0, preferably in the range of 1.6 to 8.0, more preferably in the range of 1.7 to 5.4, even more preferably in the range of 1.8 to 3.4, and most preferably in the range of 1.8 to 2.4.
  • Polyisocyanate (A) can carry at least one ethylenically unsaturated group or no ethylenically unsaturated groups.
  • Polyisocyanate (A) carrying at least one ethylenically unsaturated group has preferably an ethylenically unsaturated group density in the range of 0.10 to 10.00 milliequivalents ethylenically unsaturated groups/g, more preferably 0.50 to 5.00 milliequivalents ethylenically unsaturated groups/g, and most preferably 1.50 to 2.50 milliequivalents ethylenically unsaturated groups/g (A1).
  • the ethylenically unsaturated group density of polyisocyanate (A1) is determined by 1 H- NMR by methods known in the art.
  • Polyisocyanate (A) preferably does not carry ethylenically unsaturated groups.
  • the compound (C) carrying at least one NH2 group and no OH group can be any aliphatic, alicyclic or aromatic compound carrying at least one NH2 group and no OH group.
  • Aromatic compounds (C) are compounds (C), wherein the at least one NH2 functionality is directly attached to an aromatic ring. Alicyclic compounds (C) comprise at least one alicyclic ring and each NH2 functionality is not directly attached to an aromatic ring. Aliphatic compounds (C) do not comprise an alicyclic ring and each NH 2 functionality is not directly attached to an aromatic ring. Preferred aliphatic and alicyclic compounds (C) do not comprise aromatic rings.
  • Compounds (C) carrying at least one NH2 group and no OH group can also carry other functional groups such as NH, or acidic groups such as SO3H, PO3H or COOH or salt groups thereof.
  • Examples of compounds (C) are ethylene diamine, isophorone diamine, N-aminoethyl-2- aminoethanesulfonic acid, sodium salt, N-aminoethyl-2-aminoethanecarboxylic acid, sodium salt and the sodium salt of lysin.
  • the compound (C) carrying at least one NH2 group and no OH group is preferably an aliphatic or alicyclic compound carrying one NH 2 group and no OH group.
  • Components (A), (B1), (B2), (B3), (B4), (B5) and (C) can be derived from fossil or from renewable resources such as plants. Whether the components are derived from renewable resources or not can be determined by the C- 14/C- 12 isotope ratio.
  • the C- 14/C- 12 isotope ratio of component (B3) preferably does not deviate by more than 10% from the C-14/C-12 isotope ratio of the atmosphere, more preferably it does not deviate by more than 5% from the C-14/C-12 isotope ratio of the atmosphere, and most preferably it does not deviate by more than 1% from the C-14/C-12 isotope ratio of the atmosphere.
  • the number average molecular weight Mn and the weight average molecular weight Mw can be determined using gel permeation chromatography calibrated to a polystyrene standard.
  • the salt group of the COOH group can be any salt group of the COOH group formed by the reaction of the COOH group with a base.
  • the base can be an inorganic base or compound carrying at least one tertiary amino group.
  • inorganic bases are alkali and alkaline earth metal hydroxide, alkali and alkaline earth metal carbonate as well as alkali and alkaline earth metal hydrogencarbonate.
  • Preferred inorganic bases are alkali metal hydroxide such as sodium or potassium hydroxide, alkali metal carbonate such as sodium carbonate and potassium carbonate as well as alkali metal hydrogencarbonate such as sodium hydrogen carbonate and potassium hydrogen carbonate.
  • Examples compounds carrying at least one tertiary amino group are triethanolamine, tripropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, N,N- diethylethanolamine, triethylamine, ethyldiisopriopylamine, tripropylamine, triisopropylamine and tri-n-butylamine.
  • the base is a compound carrying at least one tertiary amino group.
  • the equivalent ratio of salt groups of COOH groups/(COOH groups and salt groups thereof) of polyurethane (1) is preferably in the range of from 40/100 to 100/100, and more preferably in the range of from 60/100 to 100/100.
  • the COOH groups and salt groups thereof density of the polyurethane (PU) is preferably at least 0.20 milliequivalents COOH groups and salt groups thereof/g of polyurethane (PU), and more preferably at least 0.30 milliequivalents COOH groups and salt groups thereof/g of polyurethane (PU), and most preferably in the range of from 0.35 to 0.50 milliequivalents COOH groups and salt groups thereof/g solids of polyurethane (PU).
  • the COOH groups and salt groups thereof density of the polyurethane (PU) is the sum of [weight ratio (B1)/(A), (B1), (B2), (B3), (B4), (B5) and (C)] multiplied with the COOH group density of (B1) and
  • the (meth)acrylate group density of the polyurethane (PU) is preferably at least 0.50 milliequivalents (meth)acrylate group/g polyurethane (PU), more preferably in the range of from 0.80 to 6.00 milliequivalents (meth)acrylate group/g polyurethane (PU), even more preferably in the range of from 1.00 to 4.00 milliequivalents (meth)acrylate group/g polyurethane (PU), and most preferably in the range of from 1.50 to 3.50 milliequivalents (meth)acrylate group/g polyurethane (PU).
  • the (meth)acrylate group density of the polyurethane (PU) is determined by calculation.
  • the (meth)acrylate group density of the polyurethane (PU) is the sum of
  • The(meth)acrylate group densities of (A), (B1), (B2), (B4), (B5) and (C) can be determined by 1 H-NMR by methods known in the art.
  • the equivalent ratio of [(meth)acrylate group provided by polyol (B2)]/[(meth)acrylate group provided by components (A), (B1), (B2), (B3), (B4), (B5) and (C)] is preferably in the range of from 0.30/1 .00 to 1 .00/1.00, more preferably in the range of from 0.50/1 .00 to 1.00 /1.00 even more preferably in the range of from 0.70/1.00 to 1.00/1.00 and most preferably in the range from 0.80/1.00 to 1.00/1.00.
  • the at least one polyurethane (PU) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, is preferably obtainable by the reaction of
  • At least polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring, 0 to 50.0% of at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and
  • the at least one polyurethane (PU) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, is more preferably obtainable by the reaction of
  • At least polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring,
  • the at least one polyurethane (PU) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, is most preferably obtainable by the reaction of
  • At least polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring,
  • the equivalent ratio of NCO group of polyisocyanate (A)/OH groups of components (B1), (B2), (B3), (B4) and (B5) can be in the range of 0.80/1.00 to 1.50/1.00, preferably it is in the range of 0.90/1.00 to 1.30/1.00, and more preferably it is in the range of from 1.00/1.00 to 1.20/1.00.
  • the compound (1) carrying at least one ethylenically unsaturated group and no COOH group preferably also does not carry NCO groups or groups that are reactive towards NCO.
  • Examples of groups that are reactive towards NCO groups are OH, SH, NH2 and NH groups.
  • Compound (1) is usually referred to as “reactive diluent”.
  • Compound (1) has preferably a number average molecular weight of below 1000 g/mol.
  • the number average molecular weight can be determined using gel permeation chromatography calibrated to a polystyrene standard.
  • Coumpound (1) preferably has a boling point of more than 200 °C at 101325 Pa (standard pressure).
  • Compond (1) preferably has a melting point of less than 0 °C at at 101325 Pa (standard pressure).
  • the ethylenically unsaturated group functionality of compound (1) is usually in the range of 0.8 to 6.5, preferably in the range of 0.8 to 4.4 and more preferably in the range of 1.8 to 4.4.
  • the ethylenically unsaturated group functionality of compound (1) can be calculated by multiplying the ethylenically unsaturated group density of compound (1) with the number average molecular weight of compound (1).
  • the ethylenically unsaturated group density of compound (1) can be determined by 1 HNMR by methods known in the art.
  • compound (1) examples include styrene, p-tert-butylstyrene, p-methylstyrene, o-methylstyrene, 2-vinylnaphthalene, divinylstyrene, butadiene, isoprene, chloroprene, ethylene, propylene, 1- butene, 2-butene, isobutene, cylopentene, cyclohexene, cyclododecene, vinyl acetate, vinyl propionate, vinyl chloride and vinylidene chloride, N-vinyl formamide, N-vinylacetamide, N-vinyl- N-methyl formamide, N-vinyl-N-methyl-acetamide, N-vinyl pyrrolidone, N-vinyl caprolactam, ethylene glycol divinyl ether, di(ethylene glycol) divinyl ether, tri(ethylene glycol) divinyl ether, trimethylol
  • compound (1) are compounds carrying at least one (meth)acrylate group such as compounds carrying at least one (meth)acrylate groups and compounds carrying at least two (meth)acrylate groups.
  • Examples of compounds carrying one (meth)acrylate group are Ci-2o-alkyl(meth)acrylate such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, butyl(meth)acrylate, iso- butyl(methacrylate), sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, pentyl(meth)acrylate, iso- pentyl(meth)acrylate, 2-methylbutyl(meth)acrylate, amyl(meth)acrylate, hexyl(meth)acrylate, 2- ethylbutyl(meth)acrylate, heptyl(methacrylate, octyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-propylheptyl(meth)acrylate, nony(meth)acrylate), decyl(
  • Examples of compounds carrying two (meth)acrylate groups are diesters of Ci-20-diols with (meth)acrylic acid such as 1,2-ethyleneglycol di(meth)acrylate, 1 ,2-propyleneglycol di(meth)acrylate, 1,3-propyleneglycol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1 ,3- butanediol-di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 ,7-heptandiol di (methacrylate), 1 ,8-octanediol di(methacrylate), 1,9-nonanediol di(meth)acrylate, 1 ,10-decanediol di(meth
  • Examples of compounds carrying at least three (meth)acrylate groups are glycerol tri(meth)acrylate, 1 ,1 ,1 -trimethylolpropane tri(meth)acrylate, 1,1 ,1 -trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(1, 1 ,1 -trimethylolpropane) tet- ra(meth)acrylate and dipentaerythritol hexa(meth)acrylate, ethoxylated and/or propoxylated glycerol tri(meth)acrylate, ethoxylated and/or propoxylated 1 ,1,1-trimethylolpropane tri(meth)acrylate, ethoxylated and/or propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated and/or propoxylated di(1,
  • Preferred compounds (1) are compounds carrying at least one (meth)acrylate group. More preferred compounds (1) are compounds carrying at least two (meth)acrylate groups.
  • composition of the present invention can also comprise polymerization inihibitors.
  • polymerization inihibitors are 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4- hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL), 4-benzoyloxy-2,2,6,6-tetramethyl- piperidine-1-oxyl, 4-benzyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2-diphenyl-1 -picryl- hydrazyl (DPPH), tris(p-nitrophenyl)methane, p-phenylenediamines such as N,N'-diphenyl-p- phenylenediamine, phenothiazine, hydroxylamines such as N,N-diethylhydroxylamine DEHA), quinones such as hydroquinone (HQ), hydroquinone monomethyl ether, 1 ,4-benzoquinone, tert- butylhydroquinone, 2 , 5-bis( 1 , 1 ,
  • the composition of the present invention usually comprises polyurethane (PU) in the range of 10 to 70% by weight based on the composition, more preferably in the range of 20 to 60% by weight based on the weight of the composition, even more preferably in the range of 30 to 50% by weight based on the weight of the composition and most preferably in the range of 33 to 45% by weight based on the weight of the composition.
  • PU polyurethane
  • the composition of the present invention usually comprises water in the range of 30 to 90% by weight based on the weight of the composition, more preferably of in the range of 80 to 40% by weight based on the weight of the composition, even more preferably of in the range of 70 to 50% by weight based on the weight of the composition and most preferably in the range of 67 to 55% by weight based on the weight of the composition.
  • composition of the present invention usually comprises below 10% by weight organic solvents, more preferably below 5% by weight based on the weight of the composition.
  • the composition of the present invention can comprise compound (1) in the range of 0 to 50% by weight based on the weight of the composition, more preferably in the range of 0 to 30% by weight based on the weight of the composition, even more preferably in the range of 0 to 20% by weight, and most preferably in the range from 1 to 10% by weight based on the weight of the composition.
  • the weight ratio of PU/compound (1) is usually in the range of 0.60/1.00 to 20.00/1.00, preferably in the range of 1.00/1.00 to 15.00/1.00, more preferably in the range of 4.00/1.00 to 10.00/1.00.
  • composition of the present invention can comprise polymerization inhibitors in the range of 0.001 to 5.000% by weight based on the weight of polyurethane (PU), more preferably in the range of 0.005 to 2.000% by weight based on the weight of polyurethane (PU) and even more preferably in the range of 0.010 to 1.000% by weight based on the weight of polyurethane (PU).
  • composition of the present invention can be a dispersion or a solution.
  • dispersions are emulsions (liquid phase dispersed in liquid phase) and suspensions (solid phase dispersed in liquid phase).
  • the composition of the present invention is preferably a dispersion, more preferably a dispersion having an average particle size in the range of 10 to 200 nm and more preferably in the range of 30 to 150 nm, and most preferably 40 to 130 nm.
  • the average particle size is determined using dynamic light scattering (DLS) ISO 22412, 2017.
  • Also part of the present invention is a process for the preparation of the composition of the present invention, which process comprises the steps of
  • step (ii) optionally reacting the composition obtained in step (i) with at least one compound (C) carrying at least one NH 2 group and no OH group
  • step (iii) reacting at least part of the COOH groups of the polyurethane of the composition obtained in step (i) or (ii) with a base
  • step (iv) optionally reacting the composition obtained in step (iii) with at least one compound (C) carrying at least one NH 2 group and no OH group
  • step (v) adding water to the composition obtained in step (iv) and removing the at least one organic solvent to obtain the composition of the present invention, wherein the equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is at least 45% and wherein the weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is at least 1 %.
  • the organic solvent of step (i) can be an aliphatic ketone such as acetone, ethyl methylketone (2-butanone) or isobutyl methyl ketone, an aliphatic amide such as N-methylpyrrolidone or N- ethylpyrrolidone, an ether such as tetrahydrofuran, dipropylene glycol dimethyl ether or dioxane, a hydrocarbon such as n-heptane, cyclohexane, toluene, ortho-xylene, meta-xylene, paraxylene, and xylene isomer mixture, an ester such as butyl acetate, an acid such as acetic acid or a nitrile such as acetonitrile, or a mixture thereof.
  • an aliphatic ketone such as acetone, ethyl methylketone (2-butanone) or isobutyl methyl ketone
  • the at least one organic solvent is preferably an aliphatic ketone, and more preferably an aliphatic ketone selected from the group consisting of acetone and ethyl methyl ketone (2- butanone).
  • Step (i) is usually performed in the presence of polymerization inhibitors.
  • Step (i) can be performed in the presence of at least one catalyst.
  • Examples of catalysts are amine catalysts carrying at least one tertiary amino group and organ- ometal catalysts.
  • amine catalysts carrying at least one tertiary amino group are 1 ,4-diazabicyclo- [2.2.2]octane, N-methylmorpholine, N-methylimidazole, bis[2-(N,N-dimethylamino)ethyl] ether, 2,2’-dimorpholinyldiethylether and tetramethylethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylethanolamine and dimethylaminopropyl amine.
  • organometallic catalysts examples include organo titanium catalysts, organo tin catalysts, organo zinc catalysts, organo bismuth catalysts, organo zirconium catalysts, organo iron catalysts, organo aluminum catalysts, organo manganese catalysts, organium nickel catalysts, organo cobalt catalysts, organo molybdenum catalysts, organo tungsten catalysts and organo vanadium catalysts.
  • organo titanium catalysts are titanium(IV) tetra(isopropoxide) and titanium(IV) tet- ra(butoxide).
  • organo tin catalyst are tin(ll) diacetate, tin(ll) di(2-ethylhexanoate), tin(ll) dilaurate, dimethyltin(IV) diacetate, dibutyltin(IV) diacetate, dibutyltin(l V)dibutyrate, dibutyltin di(2-ethylhexanoate), dibutyltin(IV) dilaurate, dioctyltin(IV) dilaurate, dioctyltin(IV) diacetate, dibutyl tin(IV) oxide, diphenyl tin(IV) oxide, dibutyltin(IV) dichloride, and dibutyl tin(IV) maleate.
  • organo zinc catalyst examples include zinc(ll) diacetate, zinc(ll) di(2-ethylhexanoate) and zinc(ll) dineodecanoate.
  • organo bismuth catalyst are bismuth(ll) diacetate, bis- muth(ll) dipivalate, bismuth(ll) di(2-ethylhexanoate) and bismuth(ll) dineodecanoate and bismuth (III) tri(neodecanoate).
  • organo zirconium catalysts are zirconium(IV) tet- ra(acetylacetonate) and zirconium(IV)tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate).
  • Step (i) is usually performed at elevated temperatures, such as at temperatures in the range of 50 to 150°C, preferably in the range of 50 to 100°C, more preferably in the range of 50 to 90°C.
  • Step (i) is usually stopped when an NCO content of below 2% by weight based on the weight of the reaction mixture is reached by addition of at least one organic solvent, which can be the same than the organic solvent of step (i) or different.
  • the equivalent ratio of NCO group of polyisocyanate (A)/OH groups of components (B1), (B2), (B3), (B4) and (B5) can be in the range of 0.80/1.00 to 1.50/1.00, preferably it is in the range of 0.90/1.00 to 1.30/1.00, and more preferably it is in the range of from 1.00/1.00 to 1.20/1.00.
  • Steps (ii) and (iv), if performed, are usually performed at temperatures below 80°C.
  • the base used in step (iii) can be any base. Examples of bases are given above.
  • the base is a compound carrying at least one tertiary amino group.
  • Step (v) is usually performed under rapid stirring of the composition. If compound (1) is present in the composition of the present invention, step (i) can be performed in the presence of compound (1). Compound (1) can also be added after step (i), for example between step (i) or step (ii) or between step (iv) and step (v). It is also possible to add part of compound (1) in step (i), and the other part of compound (1) later.
  • an aqueous coating composition comprising the composition of the present invention comprising polyurethane (PU), at least one additive, optionally at least one initiator and optionally at least one polymer (2) different from polyurethane (PU), wherein the coating composition comprises polyurethane (PU) in the range of 10 to 70% by weight based on the weight of the coating composition.
  • PU polyurethane
  • the coating composition comprises polyurethane (PU) in the range of 10 to 70% by weight based on the weight of the coating composition.
  • the additive can be any suitable additive.
  • additives examples include thickeners, ultraviolet absorbers, light stabilizers, surfactants, polymerization inhibitors, photosensitizers, curing catalyst, antifoamers, plasticizers, fillers, pigments, dyes, flow control agents, antioxidants, flame retardents, antistatic agents, thixotropic agents, leveling agents, tackifiers, chelating agents, matting agents and compatibilizers.
  • thickeners are hydroxymethyl cellulose and bentonite.
  • ultraviolet absorbers are benzotriazoles such as 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzo- triazole, 2-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl) phenol and 2-(2H-benzotriazol-2- yl)-p-cresol, triazines such as 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)5-((hexyl)oxy) phenol), cyanoacrylates and benzophenones.
  • Examples of light stabilizers are hindered amine light stabilizers (HALS) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-terf-butylpiperidine and bis(2, 2,6,6- tetramethyl-4-piperidyl) sebacate.
  • Examples of fillers are talc, siliceous earth, clay, aluminium silcates, magnesium silicate, calcium carbonate, calcium sulfate, barium sulfate, aluminium hydroxide aluminium oxide and organic fillers such as polyacrylic acid and cellulose.
  • Examples of chelating agenst are ethylenediamine tetraacetic acid and p-diketones.
  • the initiator is a compound that forms free radical upon heat treatment (thermal radical initiator) or upon radiation (photoinitiator).
  • thermal radical initiators are peroxides such as potassium persulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, acetyl cyclohexylsulfonyl peroxide, di- /so-propyl percarbonate, tert-butyl peroctoate, cumene hydroperoxide, dicumyl peroxide and tert-butyl perbenzoate, azobis-/so-butyronitrile and benzpinacol.
  • peroxides such as potassium persulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, acetyl cyclohexylsulfonyl peroxide, di- /so-propyl percarbonate, tert-butyl peroctoate, cumene hydroperoxide, dicumyl per
  • photoinitiators are acetophenone, 2,2-dimethoxy-2-phenylacetophenone (benzil dimethyl ketal), 2,2-diethoxyacetophenone, 4-dimethylaminoacetophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone 4-hydroxybenzophenone, 4-phenylbenzophenone, 2-chlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, thioxanthone, isopropyl-9H-thioxanthen-9-one, phenyl glyoxylic acid methyl ester, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propylether, benzoin isopropylether, benzoin n- butyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, cyclohexyl phenyl ketone, 1-
  • mixtures of initiators are mixtures of at least two photoinitiators, mixtures of at least one photoinititiator and at least one thermal radical initiator as well as mixtures of at least two thermal radical initiators.
  • Common mixtures of photoinitiators are the mixture of bis(2,6-dimethoxybenzoyl)-2,4,4 trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone, the mixture of 1- hydroxycyclohexyl phenyl ketone and benzophenone, the mixture of bis(2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexyl phenyl ketone, the mixture of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1- propanone, the mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone, and the mixture of 4-methylbenzophenone and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide.
  • the at least one initiator is preferably a photoinitiator, more preferably a UV photoinitiator.
  • a UV photoinitiator is an initiator that forms free radicals upon UV radiation treatment.
  • Preferred initiators are selected from the group consisting of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate, benzophenone, phenyl bis(2,4,6- trimethylbenzoyl) phosphine oxide, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- phenyl-1-propanone and 2,2-dimethoxy-2-phenylacetophenone (benzil dimethyl ketal).
  • the polymer (2) can be any polymer different from polyurethane (PU).
  • Polymer (2) can be a polymer carrying ethylenically unsaturated groups or a polymer not carrying ethylenically unsaturated groups.
  • Examples of polymer (2) are polyurethanes, acrylic polymers, hybrids of polyurethane and acrylic polymer, polyesters, polyethers, polycarbonates, epoxy resins, alkyd resins, polyolefins and polyvinylacetate, as well as acryated or methacrylated derivatives thereof.
  • polymer (2) is a polymer not carrying ethylenically unsaturated groups
  • the hydroxyl value of polymer (2) is preferably in the range of from 1 to 300 mg KOH/g and the acidic value is preferably below 50 mg KOH/g.
  • Acrylated ond methacrylated derivatives can be prepared by methods known in the art, for example by esterifying the OH-groups of polyesters, aryl ic polymers and polyethers wih acrylic acid or methacrylic acid, or by ring-opening the epoxy groups of epoxy resin with acrylic acid or methacrylic acid.
  • Polyurethanes are polymers comprising urethane linkages. Polyurethanes are usually obtained by reaction of diols with diisocyanates. The diol can be a polyester diol, acrylic polymer diol, polycarbonate diol or polyetherdiol. Polyurethanes may comprise further linking groups in the main chain in lower number than the number of urethane groups such as ester, ether, thioether or urethane linkages. Acrylated or methacrylated polyurethanes can also be obtained using acrylated or methacrylated alcohols or diols as synthesis component.
  • Acrylic polymers are usually obtained by radical polymerization from polymerizable unsaturated monomers comprising acrylic acid esters or methacrylic acid esters, and optionally other polymerizable unsaturated monomers, by methods known in the art such as emulsion polymerization.
  • polymerizable unsaturated monomers examples include polymerizable unsaturated monomers carrying OH groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate and (meth)allyl alcohol, and polymerizable unsaturated monomers carrying acidic groups such as acrylic acid, methacrylic acid, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and itaconic anhydride.
  • the polymerizable unsaturated monomers also comprise polymerizable unsaturated monomers carrying OH groups.
  • the hydroxyl value of the acrylic polymers is preferably in the range from 1 to 200 mg KOH/g, more preferably in the range of 2 to 100 mg KOH/g, and most preferably 3 to 50 mg KOH/g.
  • the weight average molecular weight of the acrylic polymer is preferably 1000 to 200000 g/mol, more preferably 2000 to 100000 g/mol, and most preferably 3000 to 50000 g/mol.
  • Hybrids of polyurethane and acrylic polymer can be obtained, for example, by preparing the acrylic polymer as described above, but in the presence of a polyurethane.
  • Polyesters are polymers comprising monomers linked via an ester linkage. Polyesters are usually obtained by an esterification reaction or transesterification reaction of a component carrying two acidic groups and a diol. Polyesters may comprise linking groups other the ester groups in lower number or equal than the number of ester groups such as carbonate, ether, thioether or urethane linking groups.
  • the hydroxyl value of the polyester is preferably about 1 to 300 mg KOH/g, more preferably about 50 to 250 mg KOH/g, and still more preferably about 80 to 180 mg KOH/g.
  • the acid value of the polyester resin is preferably about 1 to 200 mg KOH/g, more preferably about 15 to 100 mg KOH/g, and still more preferably below 50 mg KOH/g.
  • the weight average molecular weight of the polyester is preferably 500 to 500000 g/mol, more preferably 1000 to 300000 g/mol, and still more preferably 1500 to 200000 g/mol.
  • Polyethers are polymers comprising ether linkages. Polyethers are usually prepared by acid catalyzed polymerization of ethers such as ethyleneoxide, propylene oxide, butylene oxide or tetrahydrofuran using an alcohol. Examples of polyethers are polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether and polytetrahydrofuran. Polyethers may comprise further linking groups in the main chain in lower number than the number of ether groups such as ester, carbonate, thioether or urethane linkages.
  • Polycarbonates are polymers comprising carbonate linkages. Polycarbonates are usually obtained by reaction of carbonates with diols. Polycarbonates may comprise further linking groups in the main chain in lower number than the number of carbonate groups such as ester, ether, thioether or urethane linkages.
  • Epoxy resins are polymers carrying epoxy groups. Epoxy polymers can be obtained by reaction of polyols with epichlorohydrin followed by dehydrohalogenation. Examples of polyols are bisphenol A and bisphenol F as well as novolak resins, which are polymers formed by reaction of phenol with formaldehyde.
  • Alkyd resins are polyester carrying fatty acid-derived groups. Alkyd resins are usually obtained by an esterification reaction or transesterification reaction of a component carrying two acidic groups, a polyol and a glycerine fatty acid triester. Examples of components carrying two acidic groups are phthalic anhydride and maleic anhydride. Examples of polyols are trimethylolpropane, glycerine and pentaeryhritol. Examples of glycerine fatty acid triester are soybean oil, linseed oil and coconut oil.
  • Polyolefins are polymers obtainable by polymerizing at least one olefin monomer, optionally in the presence of at least a polymerizable unsaturated monomer which is not an olefin monomer, by methods known in the art such as emulsion polymerization.
  • Olefin monomers are monomers comprising solely H and C atoms.
  • olefin monomers examples include ethylene, propylene, 1- butene, 3-methyl-1 -butene, 4-methyl-1 -pentene, 3-methyl-1 -pentene, 1-heptene, 1-hexene, 1- decene and 1-dodecene; conjugated dienes and non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene and 1 ,5-hexadiene, and styrenes.
  • polymerizable unsaturated monomers which are no olefin monomers, are vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and itaconic anhydride.
  • Preferred polymers (2) are selected from the group consisting of polyurethanes, acrylic polymers, hybrids of polyurethane and acrylic polymer, as well as acrylated or methacrylated derivatives thereof.
  • the coating composition of the present invention usually comprises polyurethane (PU) in the range of 10 to 70% by weight based on the coating composition, more preferably of in the range of 15 to 50% by weight based on the weight of the coating composition, most preferably of in the range of 20 to 45% by weight based on the weight of the coating composition.
  • PU polyurethane
  • the coating composition of the present invention usually comprises additives in the range of 0.05 to 40% by weight based on the coating composition and most preferably of in the range of 0.1 to 25% by weight based on the weight of the coating composition.
  • the coating composition of the present invention preferably comprises at least one initiator in the range of 0.05 to 12.0% by weight based on the weight of polyurethane (PU), and more preferably in the rane of 0.1 to 10.0% by weight based on the weight of polyurethane (PU).
  • the coating composition of the present invention usually comprises compound (1) in the range of 0 to 20% by weight based on the coating composition, more preferably in the range of 0.5 to 15% by weight based on the coating composition, and most preferably in the range of 1 to 10%.
  • the coating composition of the present invention usually comprises polymer (2) in the range of 0 to 50% by weight based on the coating composition, more preferably in the range of 0 to 25% by weight based on the coating composition, and most preferably in the range of 0 to 10%.
  • the coating composition of the present invention usually comprises at least 20% by weight, more preferably at least 40% by weight water based in the weight of the coating composition.
  • the coating composition of the present invention can also comprise organic solvents.
  • organic solvents are butyl glycol, butyl diglycol, methoxypropanol, 2-butoxyethyl acetate, propylene carbonate, di(propylene glycol) methyl ether, propylene glycol n-butyl ether and di(propylene glycol) n-butyl ether.
  • the coating composition of the present invention usually comprises below 10% by weight organic solvents based on the weight of the coating composition.
  • the coating composition can be a dispersion or a solution.
  • the coating composition is a dispersion.
  • coating composition of the present invention is a clear coat composition, preferably a clear coat composition not comprising pigments.
  • the coating composition of the present invention as a pigmented coating composition.
  • the coating composition of the present invention can be prepared by mixing the composition of the present invention, the at least one additive, optionally the at least one initiator, optionally the least one polymer (2), and optionally additional water.
  • the at least one additive, the at least one initiator (if present) and the at least one polymer (2) (if present) can be used “as is” or as a solution or dispersion in an organic solvent and/or in water in the mixing step.
  • Polymers (2) which are selected from the group consisting of polyurethanes, acrylic polymers, hybrids of polyurethane and acrylic polymer, as well as acrylated or methacrylated derivatives thereof, are usually used as aqeuous solution or dispersion in the mixing step.
  • Also part of the present invention is a crosslinked-layer formed from the coating composition of the present invention.
  • the cross-linked layer is obtainable by a process, which comprises the steps of (i) applying the coating composition of the present invention to a substrate to form a layer, (ii) optionally drying the layer of step (i), and (iii) treating the layer of step (i) or of step (ii) with heat, radiation or electron beam to form a cross-linked layer.
  • the coating compositions of the present invention can be applied to the substrate by any method known in the art such as by draw down bar, spraying, troweling, knifecoating, brushing, rolling, rollercoating, flowcoating and laminating, doctor blades, various printing processes such as gravure, transfer, lithographica and ink jet printing and by using a bar.
  • the substrate can be pre-treated before the application of the coating composition, for example, the substrate can be cleaned or sanded.
  • the layer obtained directly after application of the coating composition on the substrate has preferably a thickness in the range of 20 to 500 micrometer, more preferably in the range of 40 to 300 micrometer, most preferably in the range of 60 to 240 micrometer, and in particular 60 to 200 micrometers.
  • the layer obtained directly after application of the coating composition on the substrate is commonly referred to as wet layer.
  • the layer of step (i) can be dried in step (ii) to remove at least most of the water (and other volatiles such as organic solvents).
  • the layer obtained after removal of at least most of the water (and other volatiles such as organic solvents) is commonly referred to as dried layer.
  • Step (ii), if present, is preferably performed at temperatures in the range of 15 to 160°C more preferably in the range of 40 °C to 160 °C.
  • drying conditions temperature and time
  • the layer of step (i) or of step (ii) is treated in step (iii) with electron beam, heat or radiation to form a cross-linked layer.
  • Heat can also be applied by near infrared (NIR) radition, for example radiation having a wavelength in the range of 760 to 2500 nm.
  • NIR near infrared
  • the layer of step (i) or (ii) is treated with ultraviolett radiation, daylight or electron beam.
  • the layer of step (i) or (ii) is treated with radiation having a wavelength in the range of 200 to 700 nm, even more preferably in the range of fro 200 to 500 nm, and most preferably in the range of 250 to 400 nm.
  • Examples of radiation sources are low-pressure mercury vapor lamps, medium-pressure mercury vapor lamps, high-pressure mercury vapor lamps, lasers, pulsed lamps (flashlight), halogen lamps and excimer lamps.
  • the radiation dose is normally chosen to be sufficient for crosslinking.
  • a radiation dose of 80 to 3000 mJ/cm 2 preferably 100 to 2000 mJ/cm 2 is usually used.
  • a combination of different radiation sources is also possible.
  • Step (iii) can be perfomed either in the presence of oxygen or, preferably, in the absence of oxygen such as under intert gas atmosphere. Suitable inert gases are nitrogen, argon and carbon dioxide.
  • the layer of step (i) or (ii) can also be covered with transparent media such as a transparent polymer film, glas or water and irradiated through the transparent media. Irradation can also be performed by passing the substrate coated with the layer of step (i) or (ii) at constant speed past a radiation source.
  • step (ii) is performed and in step (iii) the layer of step (ii) is treated with radiation to form a cross-linked layer.
  • Steps (i), optionally (ii) and (iii) can be repeated yielding a multi-layered cross-linked layer.
  • the substrate can be any suitable substrate.
  • the substrate can be wood substrates, engineered wood substrates, engineered bamboo substrates, engineered cellulosic substrates other than engineered wood or bamboo substrates, fibre-reinforced composite substrates (FRC), woodplastic composite substrates (WPC), plastic substrates such as melamine formaldehyde substrate, paper substrates, recycled paper substrates, paperboard (also called cardboard) substrate, recycled paperboard (also called recycled cardboard) substrates, metal substrates, stone substrate, glass substrates, textiles substrates, leather substrates, ceramic substrates, mineral building material substrates such as molded cement blocks and fiber-cement slabs.
  • the substrates can be precoated with a coating composition different from the coating composition of the present invention.
  • the substrate is not pre-coated with a coating composition different from the coating composition of the present invention.
  • wood substrates are oak, beech, maple, alder, ash, pine tree, fir tree, spruce, chestnut, robinia, birch, elm, teak and walnut as well as cork.
  • Wood can, for example, be in the form of lumber (also called timber), in the form of planks used for flooring, for example parquet flooring, in the form of devices used for house construction or domestic applications, or in the form of solid wood furnitures.
  • Cork can be, for example, in the form of tiles used for flooring, or in the form of devices used for domestic applications.
  • Engineered wood substrates are derivative wood substrates manufactured by binding or fixing the strands, particles, fibres, veneers or boards of wood with adhesives or other methods of fixation to form composite materials.
  • adhesives are urea-formaldehyde resin, phenol formaldehyde resin, melamine formaldehyde resin, polymeric methylene diphenyl diisocyanate, polyvinyl acetate and polyurethane.
  • engineered wood substrates are gue- laminated timber, cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), laminated veneer lumber (LVL), plywood, oriented strand board (OSB), composite panels, particle board (also called flakeboard or chipboard), fibreboard such as hardboard (also called high-density fibreboard, HDF) and medium density fibreboard (MDF).
  • CLT cross-laminated timber
  • PSL parallel strand lumber
  • LSL laminated strand lumber
  • LSL laminated veneer lumber
  • OSB oriented strand board
  • particle board also called flakeboard or chipboard
  • fibreboard such as hardboard (also called high-density fibreboard, HDF) and medium density fibreboard (MDF).
  • HDF high-density fibreboard
  • MDF medium density fibreboard
  • Engineered wood substrates can be in the form of lamella used for engineered wood flooring, for example laminate flooring, in the form of devices used for house construction or domestic applications, and in the form of furniture such as flat-pack furniture.
  • Engineered bamboo substrates are derivative bamboo substrates manufactured by binding or fixing parts of bamboo with adhesives or other methods of fixation to form composite materials.
  • An example of engineered bamboo substrate is laminated bamboo.
  • Engineered cellulosic substrates other than engineered wood substrates and bamboo substrates are products from lignin-containing materials other than wood and bamboo such as rye straw, wheat straw, rice straw, hemp stalks, kenaf stalks and sugar cane residue, manufactured by binding or fixing parts of the lignin-containing materials other than wood and bamboo with adhesives or other methods of fixation to form composite materials.
  • Fibre-reinforced composite substrates are made from rice-derived fibres and plastic.
  • Wood-plastic composites are composite materials made from fibres or flour of wood and thermoplastic polymers such as polyethylene, prolypropylene, polyvinyl chloride or polyacetic acid.
  • the substrate is selected from the group consisting of wood substrates and plastic substrates.
  • Also part of the present invention is a substrate coated with the layer of the present invention.
  • Also part of the present invention is the use of the coating composition of the present invention as clear coat composition. Also part of the present invention is the use of the coating composition of the present invention as pigmented coating composition.
  • compositions of the present invention are advantageous in that the compositions form cross-linked layers on substrates that show a good Martens hardness and a good indentation hardness and also form cross-linked layers on substrates that show a good adhesion to the substrate.
  • NCO content of the composition is determined by first treating the composition with di-n-butyl amine and then back-titrating unreacted di-n-butylamine in order to determine the amount of reacted di-n-butyl amine.
  • the following method can be used: 10 mL of a 1 N solution of di-n-butyl amine in xylene is added to 1 g of the composition to be analyzed dissolved in 100 mL of N-methylpyrrolidone. The resulting mixture is stirred at room temperature for five minutes.
  • the resulting reaction mixture is subjected to back titration using 1 N hydrochloric acid to measure the volume of the hydrochloric acid needed for neutralizing the unreacted di-n-butyl amine. This then reveals how much mol di-n-butyl amine reacted with NCO groups.
  • the NCO content is (mol reacted di-n-butyl amine x molecular weight of NCO)/weight composition.
  • the weight of the composition is 1 g.
  • the molecular weight of NCO is 42 g/mol.
  • the precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C.
  • a mixture of 185.12 g isophorone diisocyanate (compound A) and 36.26 g Lupranat T80 A (consisting of 80% by weight tol- uene-2,4-diisocyanate and 20% by weight toluene-2,6-diisocyanate) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages.
  • the progress of the reaction was monitored by measurement of residual NCO. At the level of ⁇ 1.1 weight% of residual NCO content (based on reaction mixture), the reaction mixture was further diluted by addition of 300 g acetone.
  • the obtained mixture was neutralized by addition of 31.64 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring. After distilling off the solvent mixture and dilution with additional 200 g of deionized water, an aqueous composition PUD-1 comprising polyurethane PU-1 having a solid content of 37.8 weight%, and the properties as shown in table 1 was obtained.
  • the precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C.
  • a mixture of 186.2 g isophorone diisocyanate (compound A) and 36.48 g Lupranat T80 A consisting of 80% by weight toluene-2,4-diisocyanate and 20% by weight tolu- ene-2,6-diisocyanate) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages.
  • the progress of the reaction was monitored by measurement of residual NCO. At the level of ⁇ 1.1 weight% of residual NCO (based on reaction mixture), the reaction mixture was further diluted by addition of 300 g acetone.
  • the obtained mixture was neutralized by addition of 31.83 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring. After distilling off the solvent mixture and dilution with additional 200 g of deionized water, an aqueous composition PUD-2 comprising polyurethane PU-2 having a solid content of 38.6 weight%, and the properties as shown in table 1 was obtained.
  • the precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C. 306.28 g Desmodur W (Covestro, dicyclohexylmethanediisocyanate; NCO content > 31.8 weight%) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages. The progress of the reaction was monitored by measurement of residual NCO. At the level of ⁇ 1.1 weight% of residual NCO (based on reaction mixture), the reaction mixture was further diluted by addition of 300 g acetone. The obtained mixture was neutralized by addition of 45.27 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring.
  • an aqueous composition compPUD-3 comprising polyurethane compPU-3 having a solid content of 34.6 weight%, and the properties as shown in table 1 was obtained.
  • the precharge was dissolved in 300 g methyl ethyl ketone and heated to 60°C. 0.49 g Borchi ® 315, OMG Borchers (bismuth(lll) neodecanoate) was added and the reaction mixture was further heated until a temperature of 80°C is reached. The progress of the reaction was monitored by measurement of residual NCO. At the level of ⁇ 1.4 weight% of residual NCO (based on reaction mixture), the reaction mixture was further diluted by addition of 200 g acetone and cooled to 40°C. 6.78 g of isophorone diamine, diluted in 20 g of acetone was added over a period of 5 min.
  • the precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C.
  • a mixture of 229.33 g isophorone diisocyanate (compound A) and 44.92 g Lupranat T80 A (consisting of 80% by weight toluene-2,4-diisocyanate and 20% by weight toluene-2,6-diisocyanate) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages.
  • the progress of the reaction was monitored by measurement of residual NCO. At the level of ⁇ 1.1 wt. % of residual NCO, the reaction mixture was further diluted by addition of 300 g acetone.
  • the obtained mixture was neutralized by addition of 31.35 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring. After distilling off the solvent mixture and dilution with additional 200 g of deionized water, an aqueous composition compPUD-5 comprising polyurethane compPU-5 having a solid content of 38.3 weight%, and the properties as shown in table 1 was obtained.
  • aqueous polyurethane dispersions PUD-1 and PUD-2 of examples 1 and 2, respectively, and the comparative aqueous polyurethane dispersions compPUD-3, compPUD-4 and comp- PUD-5 of comparative examples 1, 2 and 3, respectively, were diluted with water to a solid content of 35 weight%.
  • 1 g Omnirad® 184 (photoinitiator, available from IGM Resins) was mixed with 1 g of butyl glycol (solvent).
  • Example 4 100 g of the diluted aqueous polyurethane dispersions (35 weight%) were mixed with 2.0 g of the 1/1 (weight/weight) mixture of Omnirad® 184 and butyl glycol (solvent) and with 1.0 g Rheovis® PE 1330 (thickener, available from BASF) using a speedmixer (2000 rpm, 2 minutes) to yield coating compositions.
  • Example 4 100 g of the diluted aqueous polyurethane dispersions (35 weight%) were mixed with 2.0 g of the 1/1 (weight/weight) mixture of Omnirad® 184 and butyl glycol (solvent) and with 1.0 g Rheovis® PE 1330 (thickener, available from BASF) using a speedmixer (2000 rpm, 2 minutes) to yield coating compositions.
  • Example 4 100 g of the diluted aqueous polyurethane dispersions (35 weight%) were mixed with 2.0 g of the 1/1 (weight/weight) mixture of Omnirad® 184 and but
  • the coating compositions of example 3 were applied on the surface of a clear glass plate by means of a box film applicator with 400 pm gap to form a layer. Resulting film thickness must be at least 10 times the expected maximal indentation depth. The resulting layers were dryed 2 minutes at room temperature and 15 minutes in a convection oven at 50 °C.
  • Preparation of white pigmented coating compositions comprising the aqueous polyurethane dispersions PUD-1 and PUD-2 of examples 1 and 2, respectively, and of comparative white pigmented coating compositions comprising the comparative aqueous polyurethane dispersions compPUD-3, compPUD-4 and compPUD-5 of comparative examples 1 , 2 and 3, respectively.
  • aqueous polyurethane dispersions 35 weight% were mixed with 1 ,0 g of Acematt TS 100 (matting agent available from Evonik) using a speedmixer (2750 rpm, 3 minutes). If the matting agent was not good incorporated, the mixture was mixed again using a speedmixer (2750 rpm, 1-2 minutes). An “Acematt TS100 dispersion” was obtained.
  • the white pigmented coating compositions of example 5 were applied on the surface of the melamine panel using a 200-micrometer small box film applicator to form a layer.
  • the layers were allowed to dry at room temperature for 2 minutes, and then at 50 °C in a drying cabinet for 15 minutes.
  • the layers were treated with UV radiation using Hg and Ga lamps, 50 % power (1 x 10 m/minute, total dose of about 1200 -1300 mJ/cm 2 ) to form cured layers.
  • the first layers were sanded using 400 grit sandpaper and wiped off with a cleaning tissue (soft absorbent). Then, the procedure was repeated once again, and a second layer was applied on the first layer using a smaller box film applicator and dried and cured in the same manner as described for the first layer.
  • the adhesion tests were performed on the panel with a knife/ blade with extra template to lead the cutting (distance 2 mm).
  • the cross cuts were carried out at least 5 mm away from the edge.
  • the cutting device was placed vertically onto the surface and six cuts (each about 2 cm long) were carried out parallel to each other. Then the samples were rotated 90° and the procedure was repeated once again to get a grid. Then the self-adhesive tapes (about 4 cm long, Tesa no. 4124) were placed on the grids, smoothed with the finger (firm pressure) and removed with a jerk at a 60° angle.
  • B is the sum of B1 , B2, B3, B4 and B5.
  • Table 1 shows that the coating compositions comprising the aqueous polyurethane dispersions PUD-1 and PUD-2 of the present invention having an equivalent ratio OH groups of B2/(OH groups of B1, B2, B3, B4 and B5 of around 59% and having a weight ratio B3/(A+B*+C) of around 11% yield cross-linked layers on clear glass plates that show a good Martens hardness of 115.2 and 116.4 N/mm 3 , respectively, and a good indentation hardness of 129.2 N/mm 3 and 132.7 N/mm 3 , respectively, and at the same time also yield cross-linked layers on melamine panels that show a good adhesion of classification 1 to 2.
  • Table 1 also shows that the comparative coating composition comprising the aqueous polyurethane dispersions compPUD-3 having an equivalent ratio OH groups of B2/(OH groups of of B1 , B2, B3, B4 and B5) of only 37.9% yields cross-linked layers on clear glass plates that show an acceptable Martens hardness of 109.0 N/mm 3 and an acceptable indentation hardness of 122.6 N/mm 3 , but only yield cross-linked layers on melamine panels that show a bad adhesion of classification 4.
  • Table 1 also shows that the comparative coating composition comprising the aqueous polyurethane dispersions compPUD-4 having a weight ratio B3/(A+B*+C) of 0% yields cross-linked layers on clear glass plates that show a good Martens hardness of 153.8 N/mm 3 and a good indentation hardness of 187.2 N/mm 3 but only yield cross-linked layers on melamine panels that show a bad adhesion of classification 5.
  • Table 1 also shows that the comparative coating composition comprising the aqueous polyurethane dispersion compPUD-5 having an equivalent ratio OH groups of B2/(OH groups of B1 , B2, B3, B4 and B5 of 20.8% yields a cross-linked layer on clear glass plates that show a bad Martens hardness of 72.2 N/mm 3 , respectively, and a bad indentation hardness of 70.1 N/mm 3 but yield a cross-linked layer on a melamine panel that show a good adhesion of classification 1 to 2.

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Abstract

The present invention relates to a composition comprising (i) at least one polyurethane PU carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, which polyurethane is obtainable by the reaction of at least one polyisocyanate (A), at least one polyol (B1) carrying at least one COOH group, at least one polyol (B2) carrying at least one (meth)acrylate group, but no COOH group, and comprising at least one aromatic ring, at least one polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring, optionally at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and optionally at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1, B2 and B3 and B4, and optionally at least one compound (C) carrying at least one NH2 group and no OH group, wherein the equivalent ratio OH groups of B2/OH groups of B1, B2, B3, B4 and B5 is at least 45% and wherein the weight ratio of B3/(A, B1, B2, B3, B4, B5 and C) is at least 1%, (ii) optionally at least one compound (1) carrying at least one ethylenically unsaturated group and no COOH group, and (iii) water. and to aqueous coating composition comprising this composition, to a crosslinked layer formed from the aqueous coating composition, and to substrates coated with this layer.

Description

Aqueous Compositions comprising (Meth)acrylate Group carrying Polyurethane which yield Cross-Linked Layers of High Hardness and Good Adhesion
Description
The present invention relates to aqueous compositions comprising (meth)acrylate group carrying polyurethanes, to aqueous coating compositions comprising these compositions, to crosslinked layers formed from the coating compositions, and to substrates coated with these layers.
Aqueous compositions comprising (meth)acrylate group carrying polyurethanes are used as binder in many applications, for example in coating compositions such as top-coat compositions, stain compositions, in ink compositions and in adhesive compositions.
It is desired that the cross-linked layers formed from these compositions on a substrate show a high hardness and a good adhesion to the substrate.
WO2011107398 (Bayer) describes an aqueous radiation-curable dispersion based on polyurethane acrylate, wherein the polyurethane acrylate comprises as formation compounds (A) one or more aromatic polyepoxy(meth)acrylates having an OH number of 20 to 300 mg KOH/g of substance, C) one or more oligo- or polyesters containing unsaturated fatty acids having an OH number of 15 to 300 mg KOH/g of substance and an iodine number of greater than 50 g 12/100 g of substance, E) one or more compounds having at least one group reactive towards isocyanate and additionally at least one hydrophilizing group and F) one or more organic polyisocyanates.
It was the object of the present invention to provide aqueous ethylenically unsaturated polyurethane compositions and coating compositions comprising these compositions, which coating compositions form cross-linked layers, which show a good Martens hardness and indentation hardness and a good adhesion to the substrate.
This object is solved by the composition of claim 1, the coating composition of claim 14, and the layer of claim 15 and the coated substrate of claim 16.
The composition of the present invention is a composition comprising
(i) at least one polyurethane PU carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, which polyurethane is obtainable by the reaction of at least one polyisocyanate (A), at least one polyol (B1) carrying at least one COOH group, at least one polyol (B2) carrying at least one (meth)acrylate group, but no COOH group, and comprising at least one aromatic ring, at least one polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring, optionally at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and optionally at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1 , B2 and B3 and B4, optionally at least one compound (C) carrying at least one NH2 group and no OH group, wherein the equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is at least 45% and wherein the weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is at least 1 %,
(ii) optionally at least one compound (1) carrying at least one ethylenically unsaturated group and no COOH group and
(iii) water.
The equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is preferably at least 50%, more preferably at least 55%.
The weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is preferably in the range of from 2% to 30%, more preferably in the range of from 3 to 25%, and most preferably in the range of from 5 to 18%.
The term “(meth)acrylate” comprises acrylate and methacrylate. Acrylate has formla -O-C(=O)- CH=CH2. Methacrylate has formula -O-C(=O)-C(CH3)=CH2.
Polyols have an OH functionality of at least 1.5. The OH functionality of a polyol is (hydroxyl number polyol [g KOH/g] x molecular weight poly- ol)/molecular weight KOH. If the the polyol is an oligomer or polymer, the number average molecular weight of the polyol is used, which can be determined using gel permeation chromatography calibrated to a polystyrene standard. The molecular weight of KOH is 56 g/mol. The hydroxyl number of a polyol can be determined according to DIN53240, 2016.
Polyols can be aliphatic, alicylic or aromatic polyols.
Aromatic polyols are polyols, wherein at least one OH functionality is directly attached to an aromatic ring. Alicyclic polyols comprise at least one alicyclic ring and each OH functionality is not directly attached to an aromatic ring. Aliphatic polyols do not comprise an alicyclic ring and each OH functionality is not directly attached to an aromatic ring. Preferred aliphatic and alicyclic polyols do not comprise aromatic rings.
Monoalcohols have an OH functionality of below 1.5.
The OH functionality of a monoalcohol is (hydroxyl number monoalcohol [g KOH/g] x molecular weight monoalcohol)/molecular weight KOH. If the monoalcohol is an oligomer or polymer, the number average molecular weight of the monoalcohol is used, which can be determined using gel permeation chromatography calibrated to a polystyrene standard. The molecular weight of KOH is 56 g/mol. The hydroxyl number of a monoalcohol can be determined according to DIN53240, 2016.
Monoalcohols can be an aliphatic, alicyclic or aromatic monoalcohol.
Aromatic monoalcohols are monoalcohols, wherein the OH functionality is directly attached to an aromatic ring. Alicyclic monoalcahols comprise at least one alicyclic ring and each OH functionality is not directly attached to an aromatic ring. Aliphatic monoalcohols do not comprise an alicyclic ring and the OH functionality is not directly attached to an aromatic ring. Preferred aliphatic and alicyclic monoalcohols do not comprise aromatic rings.
An ethylenically unsaturated group can be any ethylenically unsaturated group that can polymerize by free radical mechanism upon heat, radiation treatment, usually UV radiation treatment, in the presence of a suitable initiator, or upon electron beam treatment. Examples of ethylenically unsaturated groups are acryloyl, methacryloyl, vinyl and allyl groups. Preferred ethylenically unsaturated groups are selected from the group of acryloyl and methacryloyl groups. More preferred ethylenically unsaturated groups are acryloyl groups. Polyisocyanates comprise polyisocyanates carrying blocked NCO groups as well as polyisocyanates carrying free NCO groups. Polyisocyanates carrying blocked NCO groups, can be deblocked to the corresponding polyisocyanate carrying free NCO groups under specific condi- tons, for example at elevated temperatures, such as at temperatures above 110°C. The polyisocyanate carrying blocked NCO groups is characterized in the following via its corresponding polyisocyanate carrying free NCO groups. Preferably, polyisocyanates comprise only polyisocyanates carrying free NCO groups.
Polyisocyanates have an NCO functionality of at least 1.5.
The NCO functionality of a polyisocyanate is NCO content x (molecular weight polyisocya- nate/molecular weight NCO). If the polyisocyanate is a polymeric polyisocyanate, the average weight molecular weight of the polyisocyanate is used. The average weight molecular weight of a polymeric polyisocyanate can be determined using gel permeation chromatography calibrated to a polystyrene standard. The NCO content of the polyisocyanate is weight NCO/weight polyisocyanate. The molecular weight of NCO is 42 g/mol.
The NCO content of a polyisocyanate can be determined as follows:
10 mL of a 1 N solution of n-dibutyl amine in xylene is added to 1 g of a polisocyanate dissolved in 100 mL of N-methylpyrrolidone. The resulting mixture is stirred at room temperature for five minutes. Then, the resulting reaction mixture is subjected to back titration using 1 N hydrochloric acid to measure the volume of the hydrochloric acid needed for neutralizing the unreacted n- dibutyl amine. This then reveals how much mol n-dibutyl amine reacted with NCO groups. The NCO content is (“mol reacted n-dibutyl amine” x molecular weight NCO)/weight polyisocyanate. The weight of polyisocyanate is 1 g.
Polyisocyanate can be aliphatic, alicyclic or aromatic polyisocyanates.
Aromatic polyisocyanates are polyisocyanates, wherein at least one NCO functionality is directly attached to an aromatic ring. Alicyclic polyisocyanates comprise at least one alicyclic ring and each NCO functionality is not directly attached to an aromatic ring. Aliphatic polyisocyanates do not comprise an alicyclic ring and each NCO functionality is not directly attached to an aromatic ring. Preferred aliphatic and alicyclic polyisocyanates do not comprise aromatic rings.
The polyol (B1) carrying at least one COOH group can be any aliphatic, alicyclic or aromatic polyol (B1) carrying at least one COOH group.
The OH functionality of polyol (B1) carrying at least one COOH group is usually in the range of from 1.7 to 6.0, more preferably in the range of 1.8 to 5.4, even more preferably in the range of 1.8 to 3.4, most preferably in the range from 1.8 to 2.4, and in particular in the range of 1.9 to 2.2. The polyol (B1) carrying at least one COOH group preferably has a number average molecular weight of below 750 g/mol, more preferably of below 500 g/mol, and most preferably of below 250 g/mol.
Examples of polyols (B1) carrying one COOH group are 2,2-bis(hydroxymethyl) C2-io-alkanoic acid such as 2,2-bis(hydroxymethyl) propionic acid (dimethylolpropionic acid), 2,2-bis(hydroxy- methyl) butanoic acid and 2,2-bis(hydroxymethyl) pentanoic acid.
The polyol (B1) carrying at least one COOH group is preferably a polyol carrying one COOH group, more preferably an aliphatic or alicyclic polyol (B1) carrying one COOH group, even more preferably an aliphatic polyol (B1) carrying one COOH group. Most preferably polyol (B1) is selected from the group consisting of 2,2-bis(hydroxymethyl) propionic acid and 2,2- bis(hydroxymethyl) butanoic acid, and in particular 2, 2-bis(hydroxymethyl) propionic acid.
Polyol (B2) carrying at least one (meth)acrylate groups, but no COOH group, and comprising at least one aromatic ring can be any polyol carrying at least one (meth)acrylate group, but no COOH group, and comprising at least one aromatic ring.
The aromatic ring can be any aromatic ring. Examples of aromatic rings are benzol rings and nathphaline rings.
The OH functionality of polyol (B2) is usually in the range of from 1 .7 to 6.0, more preferably in the range of 1.8 to 5.4, even more preferably in the range of 1.8 to 3.4, most preferably in the range from 1.8 to 2.4, and in particular in the range of 1.9 to 2.2.
The polyol (B2) preferably has a number average molecular weight in the range of from 250 to 750 g/mol.
The polyol (B2) is preferably of formula
Figure imgf000006_0001
wherein L1 is selected from the group consisting of
Figure imgf000007_0001
Figure imgf000008_0001
The polyol (B2) is more preferably of formula
Figure imgf000008_0002
wherein L1 is selected from the group consisting of
Figure imgf000008_0003
The polyol (B2) is most preferably of formula
Figure imgf000008_0004
Polyol (B3) can be any polyol which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
The ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms can be a monoester, a diester or a triester. The monoester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms also comprises mixtures of monoesters of glycerin with different carboxylic acids carrying at least 6 carbon atoms. Carboxylic acids carrying at least 6 carbon atoms of a diester or triester can be the same or different. The diester and triesters, respectively, of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms also comprise mixture of diesters and triesters, respectively.
The carboxylic acid carrying at least 6 carbon atoms can carry further subsituents such as OH groups.
The carboxylic acid carrying at least 6 carbon atoms can be a saturated carboxylic acid carrying at least 6 carbon atoms or an unsaturated carboxylic acid carrying at least 6 carbon atoms.
Examples of saturated carboxylic acids carrying at least 6 carbon atoms are hexanoic acid, hep- tanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), di hydroxy stearic acid, arachidic acid (C20), behenic acid (C22), lignoceric acid (C24) and cerotic acid (C26).
Examples of unsaturated carboxylic acids carrying at least 6 carbon atoms are myristoleic acid (C14), palmitoleic acid (C16), sapienic acid (C16), oleic acid (C18), elaidic acid (C18), vaccenic acid (C18), linoleic acid (C18), linoleidic aicid, alpha linolenic acid (C18), ricinoleic acid (c18), arachidonic acid (C20), ecosapentaenoic acid (C20), erucic acid (C22).
The polyol (B3) is preferably an ester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein the polyol has a hydroxy number in the range of 50 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
The polyol (B3) is more preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, and wherein at least one of the carboxylic acids also carries at least one OH group, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring. Examples of carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, and also carrying at least one OH group are ricinoleic acid, partially and fully hydrogenated ric- inoleic acid, as well as at least monohydroxylated carboxylic acids which are obtainable from mono- or polyunsaturated carboxylic acids carrying at least 10 carbon atoms and at most 21 carbon atoms.
The at least monohydroxylated carboxylic acids can for example be obtained from unsaturated carboxylic acids carrying at least 10 carbon atoms and at most 21 carbon atoms by full or partial epoxidation of the ethylenically unsaturated bond or bonds, followed by ring opening of the epoxide ring under formation of an OH group. Epoxidation can be performed by methods known in the art such as by treatment of the unsaturated carboxylic acid with a peroxyacid or a peroxide. Hydroxylation can also be performed by methods known in the art. For example, hydroxylation of the epxide ring occurs if the epoxidation is performed in aqueous medium.
Examples of polyol (B3) are castor oil as well as partially or fully hydrogenated castor oil.
Further examples of polyol (B3) are at least monohydroxylated and optionally partially or fully hydrogenated vegetable or animal oils, which are triesters of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, and wherein at least one of the carboxylic acids also carries at least one OH group, and which at least monohydroxylated and optionally partially or fully hydrogenated vegetable or animal oils have a hydroxy number in the range of 10 to 250, do not carry COOH groups and (meth)acrylate groups and do not comprise at least one aromatic ring.
Examples of vegetable and animal oils suitable for the preparation of at least monohydroxylated and optionally partially or fully hydrogenated vegetable and animal oils are canola oil, cod liver oil, corn oil, cottonseed oil, safflower oil, lineseed oil, olive oil, palm oil, peanut oil, sesame oil, soybean oil, sunflower oil and walnut oil. The preparation of at least monohydroxylated and optionally partially or fully hydrogenated vegetable and animal oils is known in the art and is, for example, described in US20100267925A1.
The polyol (B3) is even more preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein at least one of the carboxylic acids also carries at least one OH group and wherein at least 50 weight% of the carboxylic acids are carboxylic acids carrying at least 16 carbon atoms and at most 21 carbon atoms, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
The polyol (B3) is most preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein at least one of the carboxylic acids also carries at least one OH group and wherein at least 75 weight% of the carboxylic acids are carboxylic acids carrying at least 16 carbon atoms and at most 21 carbon atoms, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
The polyol (B3) is even most preferably a triester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein at least one of the carboxylic acids also carries at least one OH group and wherein at least 80 weight% of the carboxylic acids is ricinoleic acid or fully or partially hydrogenated ricinolic acid, and wherein the polyol has a hydroxy number in the range of 50 to 250, does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring.
The polyol (B3) is in particular castor oil or partially or fully hydrogenated castor oil.
The triester of glycerin and ricinoleic acid is the major component of castor oil. The triester of glycerin and hydrogenated ricinoleic acid is the major component of hydrogenated castor oil.
Monoalcohol (B4) carrying at least one (meth)acrylate group can be any aliphatic, alicyclic or aromatic monoalcohol carrying at least one (meth)acrylate group and no COOH group.
The monoalcohol (B4) has preferably an OH functionality in the range of from 0.8 to 1.4, preferably in the range of 0.9 to 1 .2.
Examples of monoalcohol (B4) carrying at least one (meth)acryloyl group are monoesters of diols with acrylic acid or methacrylic acid, diesters of triols with acrylic acid or methacrylic acid and triesters of tetraols with acrylic acid or methacrylic acid and pentaesters of hexaols with acrylic acid or methacrylic acid.
Examples of monoesters of diols with acrylic or methacrylic acid are monoesters of C1.10- aliphatic diols, preferably of Ci-6-aliphatic diols, with acrylic or methacrylic acid.
Examples of monoesters of Ci-6-aliphatic diols with acrylic or methacrylic acid are 2-hydroxy- ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate and 4-hydroxylbutyl acrylate.
Further examples of monoalcohols (B4) carrying at least one (meth)acryloyl group are diesters of ethoxylated or propoxylated 1 ,1 ,1 -trimethylolpropane with acrylic or methacrylic acid, triesters of pentaerythritol with acrylic or methacrylic acid, triesters of ethoxylated or propoxylated di(1 ,1 ,1-trimethylol)propane with acrylic or methacrylic acid and pentaesters of dipentaerythritol. Monoalcohol (B4) is preferably an aliphatic or alicyclic monoalcohol carrying one (meth)acryloyl. More preferably monoalcohol (B4) is an aliphatic or alicyclic monoalcohol carrying one acryloyl group. Even more preferably monoalcohol (B4) is a monoester of a Ci-6-aliphatc diol with acrylic acid, and most preferably monoalcohol (B4) is 2-hydroxyethyl acrylate.
Compound, oligomer or polymer (B5) which carries at least one OH group and which is different from B1 , B2, B3 and B4 can be any compound, oligomer or polymer which is different from B1, B2, B3 and B4 and which carries at least one OH group. Compound, oligomer or polymer (B5) can also carry at least one ethylenically unsaturated group.
Compound, oligomer or polymer (B5) can be an aliphatic, alicyclic or aromatic polyol which is different from B1 , B2 and B3.
Examples of aliphatic polyols which are different from B1, B2 and B3 are ethylene glycol, pro- pane-1, 2-diol, propane-1, 3-diol, butane-1, 2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3- diol, pentane-1 , 2-diol, pentane-1, 3-diol, pentane-1 ,4-diol, pentane-1,5-diol, pentane-2, 3-diol, pentane-2,4-diol, hexane-1, 2-diol, hexane-1, 3-diol, hexane-1 ,4-diol, hexane-1 ,5-diol, hexane- 1,6-diol, hexane-2,5-diol, heptane-1, 2-diol, heptane-1 ,7-diol, octane-1, 8-diol, octane-1, 2-diol, nonane-1,9-diol, decane-1, 2-diol, decane-1 , 10-diol, dodecane-1, 2-diol, dodecane-1 ,12-diol, hexa-1 ,5-diene-3,4-diol, neopentyl glycol, 2-methyl-pentane-2,4-diol, 2,4-dimethyl-pentane-2,4- diol, 2-ethyl-hexane-1, 3-diol, 2,5-dimethyl-hexane-2,5-diol, 2,2,4-trimethyl-pentane-1 ,3-diol, pi- nacol and hydroxypivalinic acid neopentyl glycol ester.
Further examples of aliphatic polyols which are different from B1 , B2 and B3 are di(ethylene glycol), tri(ethylene glycol), di(propylene glycol) and tri(propylene glycol).
Further examples of aliphatic polyols which are different from B1 , B2 and B3 are glycerol, trimethylolmethane, 1 ,1 ,1-trimethylolethane, 1,1,1 -trimethylolpropane, 1 ,2,4-butanetriol and 1,3,5- tris(2-hydroxyethyl) isocyanurate and condensates thereof with ethylene oxide, propylene oxide and/or butylene oxide.
Further examples of aliphatic polyols which are different from B1 , B2 and B3 are pentaerythritol, diglycerol, triglycerole, condensates of at least four glycerols, di(trimethylolpropane), di(pentaerythritol), and condensates thereof with ethylene oxide, propylene oxide and/or butylene oxide.
Examples of alicyclic polyols which are different from B1, B2 and B3 are 1,1-bis(hydroxymethyl)- cyclohexane, 1,2-bis(hydroxymethyl)-cyclohexane, 1 ,3-bis(hydroxymethyl)-cyclohexane, 1,4- bis(hydroxymethyl)-cyclohexane, 1 ,1-bis(hydroxyethyl)-cyclohexane, 1 ,2-bis(hydroxyethyl)- cyclohexane, 1 ,3-bis(hydroxyethyl)-cyclohexan, 1 ,4-bis(hydroxyethyl)-cyclohexane, 2, 2,4,4- tetramethyl-1,3-cyclobutandiol, cyclopentane- 1, 2-diol, cyclopentane- 1, 3-diol, 1,2- bis(hydroxymethyl) cyclopentane, 1 ,3-bis(hydroxymethyl) cyclopentane, cyclohexane-1 ,2-diol, cyclohexane-1 ,3-diol, cyclohexane-1,4-diol, cycloheptane-1 ,3-diol and cycloheptane-1,4-diol and cycloheptane-1,2-diol.
Examples of alicyclic polyols which are different from B1 , B2 and B3 are inositol, sugars such as glucose, fructose and sucrose, sugar alcohols such as sorbitol, mannitol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), malitol and isomalt, as well as tris(hydroxymethyl)amine, tris(hydroxyethyl)amine and tris(hydroxypropyl)amine.
Examples of polyols which are different from B1, B2 and B3 are also polyurethane polyols, polyester polyols, polycarbonate polyols, polyether polyols, polythioether polyols and polyacrylate polyols.
Polyurethane polyols are polymeric polyols comprising urethane groups as linking groups between two monomeric units, wherein the equivalent ratio urethane linking groups/all linking groups is at least 50/50, preferably at least 70/100, more preferably at least 80/100. Polyurethane polyols may comprise further linking groups such as carbonate, ether, thioether or ester groups.
Polyester polyols are polymeric polyols comprising ester groups as linking groups between two monomeric units, wherein the equivalent ratio ester linking groups/all linking groups is at least 50/50, preferably at least 70/100, more preferably at least 80/100. Polyester polyols may comprise further linking groups such as carbonate, ether, thioether or urethane groups.
Polyester polyols can be prepared by methods known in the art, for example by reacting at least one polyacid having a COOH functionality in the range of 1.8 to 2.4 with a polyol having an OH functionality in the range of 1.8 to 2.4. Examples of polyacids having a COOH functionality of 2 are aliphatic polyacids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelinic acid, suberic acid, azelaic acid, sebacic acid, 1,11 -undecanedicarboxylic acid, 1 ,12- dodecanedicarboxlylic acid, 2-methylmalonic acid, 2-ethylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 3,3-dimethylglutaric acid, 2-phenylmalonic acid 2-phenylsuccinic acid, alicyclic polyacids such as cyclopentane-1 ,2-dicarboxylic acid, cyclopentane-1 ,3-dicarboxylic acid, cyclohexane-1 ,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane- 1,4- dicarboxylic acid, cycloheptane- 1,2-dicarboxylic acid, 1,2-bis(carboxymethyl)-cyclohexane, 1 ,3- bis(carboxymethyl)-cyclohexane and 1,4-bis(carboxymethyl)-cyclohexane, and aromatic polyacids such as 2-5-furandicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and bis(4-carboxyphenyl) methane.
An example of a polyester polyol is also polycaprolactone diol.
Polycarbonate polyols are polymeric polyols comprising at least two carbonate groups in the main chain of the polymer. Polycarbonate polyols may comprise further linking groups in the main chain in lower number than the number of carbonate groups such as ester, ether, thioether or urethane linkages. Examples of polycarbonate polyols are polycarbonates carrying no COOH group comprising units derived from the group consisting of butan-1,4-diol, pentane-1 ,5-diol and hexane-1 ,6-diol. Preferred polycarbonate polyols are polycarbonate polyols, wherein the equivalent ratio carbonate groups/all linking groups is at least 70/100, more preferably at least 80/100.
Polyether polyols are polymeric polyols comprising at least two ether groups in the main chain of the polymer. Polyether polyols may comprise further linking groups in the main chain in lower number than the number of ether groups such as ester, carbonate, thioether or urethane groups.
Preferred polyether polyols are polyether polyols, wherein the equivalent ratio ether groups/all linking groups is at least 70/100, more preferably at least 80/100.
Examples of polyether polyols are polyethylene glycols, polypropylene glycol, polyethylenepolypropylene glycol, polytetramethylene diol and polytetrahydrofuran diol. Polyethylenepolypropylene glycols can be random or block copolymers
Polythioether polyols are polymeric polyols carrying no ethylenically unsaturated group and no COOH group and having at least two thioether groups in the main chain of the polymer. Polythioether polyols may comprise further linking groups in the main chain in lower number than the number of ether groups such as ester, carbonate, ether or urethane groups.
Poly(meth)acrylate polyols are polymeric polyols comprising at least two units derived from (meth)acrylic acid ester monomers carrying at least one OH group such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
The polyisocyanate (A) can be any aliphatic, alicylic or aromatic polyisocyanate, which polyisocyanate can be a monomeric or polymeric polyisocyanate.
Examples of monomeric aliphatic polyisocyanates carrying no ethylenically unsaturated groups are tetramethylene 1 ,4-diisocyanate, pentamethylene 1 ,5-diisocyanate, hexamethylene 1,6- diisocyanate, heptamethylene 1,7-diisocyanate, octamethylene 1,8-diisocyanate, decamethylene 1,10-diisocyanate, dodecamethylene 1,12-diisocyanate, tetradecamethylene 1,14- diisocyanate, methyl 2,6-diisocyanatohexanoate, ethyl 2,6-diisocyanatohexanoate, 2,2,4- trimethylhexane 1,6-diisocyanate and 2,4,4-trimethylhexane 1,6-diisocyanate.
Further examples of monomeric aliphatic polyisocyanates carrying no ethylenically unsaturated groups are 1 ,4,8-triisocyanatononane and 2’-isocyanatoethyl 2,6-diisocyanatohexanoate. Examples of monomeric alicyclic polyisocyanates carrying no ethylenically unsaturated groups are 1,4-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1 ,2-diisocyanatocyclohexane, 4,4’- di(isocyanatocyclohexyl)methane, 2,4’-di(isocyanatocyclohexyl)methane, 1-isocyanato- 3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate), 1,3- bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 2,4- diisocyanato-1- methylcyclohexane, 2,6-diisocyanato-1-methylcyclohexane and 3(or 4),8(or 9)-bis (isocy- anatomethyl)tricyclo[5.2.1 ,0(2,6)]decane.
Examples of monomeric aromatic polyisocyanates carrying no ethylenically unsaturated groups are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 2,4’-diisocyanatodiphenylmethane, 4,4’-diisocyanatodiphenylmethane, 1,3- phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1 ,5- naphthylene diisocyanate, diphenylene 4,4’-diisocyanate, 4,4’-diisocyanato-3,3’- dimethylbiphenyl, 3-methyldiphenylmethane 4,4’-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene and diphenyl ether 4,4’-diisocyanate.
Further examples of monomeric aromatic polyisocyanates carrying no ethylenically unsaturated groups are 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate and 2,4,4’-triisocyanato- diphenyl ether.
Monomeric polyisocyanates carrying no ethylenically unsaturated group can be prepared by methods known in the art, for example by treating the corresponding amines with phosgene.
Polymeric polyisocyanate comprises at least two units derived from monomeric polyisocyanates. Polymeric polyisocyanates usually also comprise at least one structural unit selected from the group consisting of uretdione, isocyanurate, biuret, urea, carbodiimide, uretonimine, urethane, allophanate, oxadiazinetrione and iminooxadiazinedione.
The NCO functionality of polyisocyanate (A) is usually in the range of from 1.6 to 10.0, preferably in the range of 1.6 to 8.0, more preferably in the range of 1.7 to 5.4, even more preferably in the range of 1.8 to 3.4, and most preferably in the range of 1.8 to 2.4.
Polyisocyanate (A) can carry at least one ethylenically unsaturated group or no ethylenically unsaturated groups.
Polyisocyanate (A) carrying at least one ethylenically unsaturated group has preferably an ethylenically unsaturated group density in the range of 0.10 to 10.00 milliequivalents ethylenically unsaturated groups/g, more preferably 0.50 to 5.00 milliequivalents ethylenically unsaturated groups/g, and most preferably 1.50 to 2.50 milliequivalents ethylenically unsaturated groups/g (A1). The ethylenically unsaturated group density of polyisocyanate (A1) is determined by 1H- NMR by methods known in the art. Polyisocyanate (A) preferably does not carry ethylenically unsaturated groups.
The compound (C) carrying at least one NH2 group and no OH group can be any aliphatic, alicyclic or aromatic compound carrying at least one NH2 group and no OH group.
Aromatic compounds (C) are compounds (C), wherein the at least one NH2 functionality is directly attached to an aromatic ring. Alicyclic compounds (C) comprise at least one alicyclic ring and each NH2 functionality is not directly attached to an aromatic ring. Aliphatic compounds (C) do not comprise an alicyclic ring and each NH2 functionality is not directly attached to an aromatic ring. Preferred aliphatic and alicyclic compounds (C) do not comprise aromatic rings.
Compounds (C) carrying at least one NH2 group and no OH group can also carry other functional groups such as NH, or acidic groups such as SO3H, PO3H or COOH or salt groups thereof.
Examples of compounds (C) are ethylene diamine, isophorone diamine, N-aminoethyl-2- aminoethanesulfonic acid, sodium salt, N-aminoethyl-2-aminoethanecarboxylic acid, sodium salt and the sodium salt of lysin.
The compound (C) carrying at least one NH2 group and no OH group is preferably an aliphatic or alicyclic compound carrying one NH2 group and no OH group.
Components (A), (B1), (B2), (B3), (B4), (B5) and (C) can be derived from fossil or from renewable resources such as plants. Whether the components are derived from renewable resources or not can be determined by the C- 14/C- 12 isotope ratio.
The C- 14/C- 12 isotope ratio of component (B3) preferably does not deviate by more than 10% from the C-14/C-12 isotope ratio of the atmosphere, more preferably it does not deviate by more than 5% from the C-14/C-12 isotope ratio of the atmosphere, and most preferably it does not deviate by more than 1% from the C-14/C-12 isotope ratio of the atmosphere.
The polyurethane (Pll) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, preferably has a number average molecular weight Mn in the range of 750 g/mol to 500000 g/mol.
The polyurethane (Pll) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, preferably has a weight average molecular weight Mw in the range of 1500 g/mol to 1000000 g/mol. The number average molecular weight Mn and the weight average molecular weight Mw can be determined using gel permeation chromatography calibrated to a polystyrene standard.
The salt group of the COOH group can be any salt group of the COOH group formed by the reaction of the COOH group with a base.
The base can be an inorganic base or compound carrying at least one tertiary amino group.
Examples of inorganic bases are alkali and alkaline earth metal hydroxide, alkali and alkaline earth metal carbonate as well as alkali and alkaline earth metal hydrogencarbonate. Preferred inorganic bases are alkali metal hydroxide such as sodium or potassium hydroxide, alkali metal carbonate such as sodium carbonate and potassium carbonate as well as alkali metal hydrogencarbonate such as sodium hydrogen carbonate and potassium hydrogen carbonate.
Examples compounds carrying at least one tertiary amino group are triethanolamine, tripropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, N,N- diethylethanolamine, triethylamine, ethyldiisopriopylamine, tripropylamine, triisopropylamine and tri-n-butylamine.
In one preferred embodiment the base is a compound carrying at least one tertiary amino group.
The equivalent ratio of salt groups of COOH groups/(COOH groups and salt groups thereof) of polyurethane (1) is preferably in the range of from 40/100 to 100/100, and more preferably in the range of from 60/100 to 100/100.
The COOH groups and salt groups thereof density of the polyurethane (PU) is preferably at least 0.20 milliequivalents COOH groups and salt groups thereof/g of polyurethane (PU), and more preferably at least 0.30 milliequivalents COOH groups and salt groups thereof/g of polyurethane (PU), and most preferably in the range of from 0.35 to 0.50 milliequivalents COOH groups and salt groups thereof/g solids of polyurethane (PU).
The COOH groups and salt groups thereof density of the polyurethane (PU) is the sum of [weight ratio (B1)/(A), (B1), (B2), (B3), (B4), (B5) and (C)] multiplied with the COOH group density of (B1) and
[weight ratio (B5)/(A), (B1), (B2), (B3), (B4), (B5) and (C)] multiplied with the COOH group density of (B5) and
[weight ratio (C)/(A), (B1), (B2), (B3), (B4), (B5) and (C)] multiplied with the COOH group density of (C).
The (meth)acrylate group density of the polyurethane (PU) is preferably at least 0.50 milliequivalents (meth)acrylate group/g polyurethane (PU), more preferably in the range of from 0.80 to 6.00 milliequivalents (meth)acrylate group/g polyurethane (PU), even more preferably in the range of from 1.00 to 4.00 milliequivalents (meth)acrylate group/g polyurethane (PU), and most preferably in the range of from 1.50 to 3.50 milliequivalents (meth)acrylate group/g polyurethane (PU).
The (meth)acrylate group density of the polyurethane (PU) is determined by calculation. The (meth)acrylate group density of the polyurethane (PU) is the sum of
[weight ratio (A)/(A), (B1), (B2), (B4), (B5) and (C)] multiplied by the (meth)acrylate group density of (A)],
[weight ratio (B1)/(A), (B1), (B2), (B4), (B5) and (C)] multiplied by the (meth)acrylate group density of (B1)],
[weight ratio (B2)/(A), (B1), (B2), (B4), (B5) and (C)] multiplied by the (meth)acrylate group density of (B2)],
[weight ratio (B4)/(A), (B1), (B2), (B4), (B5) and (C)] multiplied by the (meth)acrylate group density of (B4)]
[weight ratio (B5)/(A), (B1), (B2), (B4), (B5) and (C)] multiplied by the(meth)acrylate group density of (B5), and
[weight ratio (C)/(A), (B1), (B2), (B4), (B5) and (C)] multiplied by the (meth)acrylate group density of (C).
The(meth)acrylate group densities of (A), (B1), (B2), (B4), (B5) and (C) can be determined by 1H-NMR by methods known in the art.
The equivalent ratio of [(meth)acrylate group provided by polyol (B2)]/[(meth)acrylate group provided by components (A), (B1), (B2), (B3), (B4), (B5) and (C)] is preferably in the range of from 0.30/1 .00 to 1 .00/1.00, more preferably in the range of from 0.50/1 .00 to 1.00 /1.00 even more preferably in the range of from 0.70/1.00 to 1.00/1.00 and most preferably in the range from 0.80/1.00 to 1.00/1.00.
The at least one polyurethane (PU) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, is preferably obtainable by the reaction of
5.0 to 80.0% by weight of at least one polyisocyanate (A),
0.5 to 30.0% by weight of at least one polyol (B1) carrying at least one COOH group,
5.0 to 80.0% of at least one polyol (B2) carrying at least one (meth)acrylate groups, but no COOH group, and comprising at least one aromatic ring,
1.0 to 30.0% at least polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring, 0 to 50.0% of at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and
0 to 50.0% of at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1 , B2 and B3 and B4,
0 to 30.0% of at least one compound (C) carrying at least one NH2 group and no OH group in each case based on the sum of weights of (A), (B1), (B2), (B3), (B4), (B5) and (C1).
The at least one polyurethane (PU) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, is more preferably obtainable by the reaction of
10.0 to 60.0% by weight of at least one polyisocyanate (A),
1.0 to 20.0% by weight of at least one polyol (B1) carrying at least one COOH group,
10.0 to 60.0% of at least one polyol (B2) carrying at least one (meth)acrylate groups, but no COOH group, and comprising at least one aromatic ring,
3.0 to 20.0% at least polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring,
0 to 30.0% of at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and
0 to 30.0% of at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1 , B2 and B3 and B4,
0 to 15.0% of at least one compound (C) carrying at least one NH2 group and no OH group in each case based on the sum of weights of (A), (B1), (B2), (B3), (B4), (B5) and (C1).
The at least one polyurethane (PU) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, is most preferably obtainable by the reaction of
20.0 to 50.0% by weight of at least one polyisocyanate (A),
1.0 to 10.0% by weight of at least one polyol (B1) carrying at least one COOH group,
10.0 to 60.0% of at least one polyol (B2) carrying at least one (meth)acrylate groups, but no COOH group, and comprising at least one aromatic ring,
5.0 to 15.0% at least polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring,
0 to 15.0% of at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and 0 to 15.0% of at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1 , B2 and B3 and B4,
0 to 10.0% of at least one compound (C) carrying at least one NH2 group and no OH group in each case based on the sum of weights of (A), (B1), (B2), (B3), (B4), (B5) and (C1).
The equivalent ratio of NCO group of polyisocyanate (A)/OH groups of components (B1), (B2), (B3), (B4) and (B5) can be in the range of 0.80/1.00 to 1.50/1.00, preferably it is in the range of 0.90/1.00 to 1.30/1.00, and more preferably it is in the range of from 1.00/1.00 to 1.20/1.00.
The compound (1) carrying at least one ethylenically unsaturated group and no COOH group preferably also does not carry NCO groups or groups that are reactive towards NCO.
Examples of groups that are reactive towards NCO groups are OH, SH, NH2 and NH groups.
Compound (1) is usually referred to as “reactive diluent”.
Compound (1) has preferably a number average molecular weight of below 1000 g/mol. The number average molecular weight can be determined using gel permeation chromatography calibrated to a polystyrene standard.
Coumpound (1) preferably has a boling point of more than 200 °C at 101325 Pa (standard pressure).
Compond (1) preferably has a melting point of less than 0 °C at at 101325 Pa (standard pressure).
The ethylenically unsaturated group functionality of compound (1) is usually in the range of 0.8 to 6.5, preferably in the range of 0.8 to 4.4 and more preferably in the range of 1.8 to 4.4.
The ethylenically unsaturated group functionality of compound (1) can be calculated by multiplying the ethylenically unsaturated group density of compound (1) with the number average molecular weight of compound (1). The ethylenically unsaturated group density of compound (1) can be determined by 1HNMR by methods known in the art.
Examples of compound (1) are styrene, p-tert-butylstyrene, p-methylstyrene, o-methylstyrene, 2-vinylnaphthalene, divinylstyrene, butadiene, isoprene, chloroprene, ethylene, propylene, 1- butene, 2-butene, isobutene, cylopentene, cyclohexene, cyclododecene, vinyl acetate, vinyl propionate, vinyl chloride and vinylidene chloride, N-vinyl formamide, N-vinylacetamide, N-vinyl- N-methyl formamide, N-vinyl-N-methyl-acetamide, N-vinyl pyrrolidone, N-vinyl caprolactam, ethylene glycol divinyl ether, di(ethylene glycol) divinyl ether, tri(ethylene glycol) divinyl ether, trimethylolpropane trivinyl ether, 1,4-cyclohexanedimethanol divinyl ether, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, tert-amyl vinyl ether, dodecyl vinyl ether, 1,4-butanediol divinyl ether, 1 ,6-hexanediol divinyl ether, cyclohexyl vinyl ether, allyl acetate, diallyl phthalate, triallylcyanurate, trimethylolpropane triallyl ether, alpha, beta unsaturated C4-io-dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and 2-methylenglutaric acid as well as salts thereof, esters of alpha, beta unsaturated C4-io-dicarboxylic acids such as dimethyl ester of maleic acid, ethyl methyl ester of maleic, diethyl ester of maleic acid, dimethyl ester of fumaric acid, the ethyl methyl ester of fumaric acid and the diethyl ester of fumaric acid, alpha, beta unsaturated nitriles such as (meth)acrylonitrile, and alpha, beta unsaturated aldehydes such as (meth)acrolein, and alpha, beta unsaturated amides such as (meth)acrylamide, alpha, beta unsaturated Cs-s-carboxylic acids such as acrylic acid, methacrylic acid and 3,3-dimethyl acrylic acid as well as salts thereof.
Further examples of compound (1) are compounds carrying at least one (meth)acrylate group such as compounds carrying at least one (meth)acrylate groups and compounds carrying at least two (meth)acrylate groups.
Examples of compounds carrying one (meth)acrylate group are Ci-2o-alkyl(meth)acrylate such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, butyl(meth)acrylate, iso- butyl(methacrylate), sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, pentyl(meth)acrylate, iso- pentyl(meth)acrylate, 2-methylbutyl(meth)acrylate, amyl(meth)acrylate, hexyl(meth)acrylate, 2- ethylbutyl(meth)acrylate, heptyl(methacrylate, octyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-propylheptyl(meth)acrylate, nony(meth)acrylate), decyl(methacrylate), isodecyl(methacrylate), undecyl (meth)acrylate and dodecyl(meth)acrylate, tridecyl (meth)acryte, tetradecyl(meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate and nonadecyl(meth)acrylate, C5-i2-cycloalkyl(meth) acrylate such as cyclopentyl(meth)acrylate, cyclohexyl (meth)acrylate and cycloheptyl (meth)acrylate, acetoacetoxy(C2-6-alkyl) (meth)acrylates such as acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate and acetoacetoxybutyl (meth)acrylate, [Ci- - alkoxy(Ci-io-alkoxy)o-5]Ci-io-alkyl(methacrylate) such as 2-methoxyethyl(meth)acrylate, 2- ethoxyethyl(meth)acrylate, 4-methoxybutyl(meth)acrylate, 2-(2’-methoxy- ethoxy)ethyl(meth)acrylate and 2-(2’-ethoxyethoxy)ethyl(meth)acrylate, 2-norbonyl (meth)acrylate, dihydrodicyclopentadienyl (meth)acrylate, 4-tetrahydropyranyl (meth)acrylate, 2- tetrahydropyranyl (meth)acrylate and tetrahydrofuryl (meth)acrylate
Examples of compounds carrying two (meth)acrylate groups are diesters of Ci-20-diols with (meth)acrylic acid such as 1,2-ethyleneglycol di(meth)acrylate, 1 ,2-propyleneglycol di(meth)acrylate, 1,3-propyleneglycol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1 ,3- butanediol-di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 ,7-heptandiol di (methacrylate), 1 ,8-octanediol di(methacrylate), 1,9-nonanediol di(meth)acrylate, 1 ,10-decanediol di(methacrylate), 1,2- bis(hydroxymethyl)-cyclohexane di(methacrylate), 1 ,4-bis(hydroxymethyl)-cyclohexane di(methacrylate and cyclohexan-1 ,4-diol di(meth)acrylate, diesters of ethoxylated and/or propoxylated Ci-20-diols with (meth)acrylic acid such ethoxylated and/or propoxylated 1,2- butanediol di(meth)acrylate , ethoxylated and/or propoxylated 1,4-butanediol di(meth)acrylate, ethoxylated and/or propoxalted neopentylglycol di(methacrylate), ethoxylated and/or propoxylated 1,4-bis(hydroxymethyl)-cyclohexane di(methacrylate), diethyleneglycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate as well as polyethylene glycols di(methacrylate), polypropylene glycols di(meth)acrylate, polyeth- ylene-polypropylene glycol di(meth)acrylate, the sequence of the ethylene oxide or propylene oxide units being blockwise or random, polytetramethyleneglycol di(meth)acrylate, polytetrahy- drofurane di(meth)acrylate, and ethoxylated or propoxylated bisphenol A di(methacrylate).
Examples of compounds carrying at least three (meth)acrylate groups are glycerol tri(meth)acrylate, 1 ,1 ,1 -trimethylolpropane tri(meth)acrylate, 1,1 ,1 -trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(1, 1 ,1 -trimethylolpropane) tet- ra(meth)acrylate and dipentaerythritol hexa(meth)acrylate, ethoxylated and/or propoxylated glycerol tri(meth)acrylate, ethoxylated and/or propoxylated 1 ,1,1-trimethylolpropane tri(meth)acrylate, ethoxylated and/or propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated and/or propoxylated di(1, 1 ,1 -trimethylolpropane) tetra(meth)acrylate and ethoxylated and/or propoxylated di pentaerythritol hexa(meth)acrylate.
Preferred compounds (1) are compounds carrying at least one (meth)acrylate group. More preferred compounds (1) are compounds carrying at least two (meth)acrylate groups.
The composition of the present invention can also comprise polymerization inihibitors.
Examples of polymerization inihibitors are 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4- hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL), 4-benzoyloxy-2,2,6,6-tetramethyl- piperidine-1-oxyl, 4-benzyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2-diphenyl-1 -picryl- hydrazyl (DPPH), tris(p-nitrophenyl)methane, p-phenylenediamines such as N,N'-diphenyl-p- phenylenediamine, phenothiazine, hydroxylamines such as N,N-diethylhydroxylamine DEHA), quinones such as hydroquinone (HQ), hydroquinone monomethyl ether, 1 ,4-benzoquinone, tert- butylhydroquinone, 2 , 5-bis( 1 , 1 ,3,3-tetramethylbutyl)hydroquinone, 2 , 5-bis( 1 , 1 -dimethylbutyl)- hydroquinone, p-terf-butylcatechol (TBC) and 4-methoxyphenol (MEHQ), alkylated phenols such as 2,6-di-terf-butylphenol, 2,4-di-terf-butylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl- 4,6-dimethylphenol and 2,6-di-terf-butyl-4-methylphenol.
The composition of the present invention usually comprises polyurethane (PU) in the range of 10 to 70% by weight based on the composition, more preferably in the range of 20 to 60% by weight based on the weight of the composition, even more preferably in the range of 30 to 50% by weight based on the weight of the composition and most preferably in the range of 33 to 45% by weight based on the weight of the composition.
The composition of the present invention usually comprises water in the range of 30 to 90% by weight based on the weight of the composition, more preferably of in the range of 80 to 40% by weight based on the weight of the composition, even more preferably of in the range of 70 to 50% by weight based on the weight of the composition and most preferably in the range of 67 to 55% by weight based on the weight of the composition.
The composition of the present invention usually comprises below 10% by weight organic solvents, more preferably below 5% by weight based on the weight of the composition.
The composition of the present invention can comprise compound (1) in the range of 0 to 50% by weight based on the weight of the composition, more preferably in the range of 0 to 30% by weight based on the weight of the composition, even more preferably in the range of 0 to 20% by weight, and most preferably in the range from 1 to 10% by weight based on the weight of the composition.
The weight ratio of PU/compound (1) is usually in the range of 0.60/1.00 to 20.00/1.00, preferably in the range of 1.00/1.00 to 15.00/1.00, more preferably in the range of 4.00/1.00 to 10.00/1.00.
The composition of the present invention can comprise polymerization inhibitors in the range of 0.001 to 5.000% by weight based on the weight of polyurethane (PU), more preferably in the range of 0.005 to 2.000% by weight based on the weight of polyurethane (PU) and even more preferably in the range of 0.010 to 1.000% by weight based on the weight of polyurethane (PU).
The composition of the present invention can be a dispersion or a solution. Examples of dispersions are emulsions (liquid phase dispersed in liquid phase) and suspensions (solid phase dispersed in liquid phase).
The composition of the present invention is preferably a dispersion, more preferably a dispersion having an average particle size in the range of 10 to 200 nm and more preferably in the range of 30 to 150 nm, and most preferably 40 to 130 nm. The average particle size is determined using dynamic light scattering (DLS) ISO 22412, 2017.
Also part of the present invention is a process for the preparation of the composition of the present invention, which process comprises the steps of
(i) reacting at least one polyisocyanate (A), at least one polyol (B1) carrying at least one COOH group, at least one polyol (B2) carrying at least one (meth)acrylate group, but no COOH group and comprising at least one aromatic ring, at least one polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring, optionally at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, with optionally at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1 , B2 and B3 and B4, in the presence of at least one organic solvent
(ii) optionally reacting the composition obtained in step (i) with at least one compound (C) carrying at least one NH2 group and no OH group
(iii) reacting at least part of the COOH groups of the polyurethane of the composition obtained in step (i) or (ii) with a base
(iv) optionally reacting the composition obtained in step (iii) with at least one compound (C) carrying at least one NH2 group and no OH group
(v) adding water to the composition obtained in step (iv) and removing the at least one organic solvent to obtain the composition of the present invention, wherein the equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is at least 45% and wherein the weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is at least 1 %.
The organic solvent of step (i) can be an aliphatic ketone such as acetone, ethyl methylketone (2-butanone) or isobutyl methyl ketone, an aliphatic amide such as N-methylpyrrolidone or N- ethylpyrrolidone, an ether such as tetrahydrofuran, dipropylene glycol dimethyl ether or dioxane, a hydrocarbon such as n-heptane, cyclohexane, toluene, ortho-xylene, meta-xylene, paraxylene, and xylene isomer mixture, an ester such as butyl acetate, an acid such as acetic acid or a nitrile such as acetonitrile, or a mixture thereof.
The at least one organic solvent is preferably an aliphatic ketone, and more preferably an aliphatic ketone selected from the group consisting of acetone and ethyl methyl ketone (2- butanone).
Step (i) is usually performed in the presence of polymerization inhibitors.
Step (i) can be performed in the presence of at least one catalyst.
Examples of catalysts are amine catalysts carrying at least one tertiary amino group and organ- ometal catalysts. Examples of amine catalysts carrying at least one tertiary amino group are 1 ,4-diazabicyclo- [2.2.2]octane, N-methylmorpholine, N-methylimidazole, bis[2-(N,N-dimethylamino)ethyl] ether, 2,2’-dimorpholinyldiethylether and tetramethylethylenediamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylethanolamine and dimethylaminopropyl amine.
Examples of organometallic catalysts are organo titanium catalysts, organo tin catalysts, organo zinc catalysts, organo bismuth catalysts, organo zirconium catalysts, organo iron catalysts, organo aluminum catalysts, organo manganese catalysts, organium nickel catalysts, organo cobalt catalysts, organo molybdenum catalysts, organo tungsten catalysts and organo vanadium catalysts.
Examples of organo titanium catalysts are titanium(IV) tetra(isopropoxide) and titanium(IV) tet- ra(butoxide). Examples of organo tin catalyst are tin(ll) diacetate, tin(ll) di(2-ethylhexanoate), tin(ll) dilaurate, dimethyltin(IV) diacetate, dibutyltin(IV) diacetate, dibutyltin(l V)dibutyrate, dibutyltin di(2-ethylhexanoate), dibutyltin(IV) dilaurate, dioctyltin(IV) dilaurate, dioctyltin(IV) diacetate, dibutyl tin(IV) oxide, diphenyl tin(IV) oxide, dibutyltin(IV) dichloride, and dibutyl tin(IV) maleate. Examples of organo zinc catalyst are zinc(ll) diacetate, zinc(ll) di(2-ethylhexanoate) and zinc(ll) dineodecanoate. Examples of organo bismuth catalyst are bismuth(ll) diacetate, bis- muth(ll) dipivalate, bismuth(ll) di(2-ethylhexanoate) and bismuth(ll) dineodecanoate and bismuth (III) tri(neodecanoate). Examples organo zirconium catalysts are zirconium(IV) tet- ra(acetylacetonate) and zirconium(IV)tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate).
Step (i) is usually performed at elevated temperatures, such as at temperatures in the range of 50 to 150°C, preferably in the range of 50 to 100°C, more preferably in the range of 50 to 90°C.
Step (i) is usually stopped when an NCO content of below 2% by weight based on the weight of the reaction mixture is reached by addition of at least one organic solvent, which can be the same than the organic solvent of step (i) or different.
The equivalent ratio of NCO group of polyisocyanate (A)/OH groups of components (B1), (B2), (B3), (B4) and (B5) can be in the range of 0.80/1.00 to 1.50/1.00, preferably it is in the range of 0.90/1.00 to 1.30/1.00, and more preferably it is in the range of from 1.00/1.00 to 1.20/1.00.
Steps (ii) and (iv), if performed, are usually performed at temperatures below 80°C.
The base used in step (iii) can be any base. Examples of bases are given above.
In a preferred embodiment, the base is a compound carrying at least one tertiary amino group.
Step (v) is usually performed under rapid stirring of the composition. If compound (1) is present in the composition of the present invention, step (i) can be performed in the presence of compound (1). Compound (1) can also be added after step (i), for example between step (i) or step (ii) or between step (iv) and step (v). It is also possible to add part of compound (1) in step (i), and the other part of compound (1) later.
Also part of the present invention is an aqueous coating composition comprising the composition of the present invention comprising polyurethane (PU), at least one additive, optionally at least one initiator and optionally at least one polymer (2) different from polyurethane (PU), wherein the coating composition comprises polyurethane (PU) in the range of 10 to 70% by weight based on the weight of the coating composition.
The additive can be any suitable additive.
Examples of additives are thickeners, ultraviolet absorbers, light stabilizers, surfactants, polymerization inhibitors, photosensitizers, curing catalyst, antifoamers, plasticizers, fillers, pigments, dyes, flow control agents, antioxidants, flame retardents, antistatic agents, thixotropic agents, leveling agents, tackifiers, chelating agents, matting agents and compatibilizers.
Examples of thickeners are hydroxymethyl cellulose and bentonite. Examples of ultraviolet absorbers are benzotriazoles such as 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzo- triazole, 2-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl) phenol and 2-(2H-benzotriazol-2- yl)-p-cresol, triazines such as 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)5-((hexyl)oxy) phenol), cyanoacrylates and benzophenones. Examples of light stabilizers are hindered amine light stabilizers (HALS) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-terf-butylpiperidine and bis(2, 2,6,6- tetramethyl-4-piperidyl) sebacate. Examples of fillers are talc, siliceous earth, clay, aluminium silcates, magnesium silicate, calcium carbonate, calcium sulfate, barium sulfate, aluminium hydroxide aluminium oxide and organic fillers such as polyacrylic acid and cellulose. Examples of chelating agenst are ethylenediamine tetraacetic acid and p-diketones.
The initiator is a compound that forms free radical upon heat treatment (thermal radical initiator) or upon radiation (photoinitiator).
Examples of thermal radical initiators are peroxides such as potassium persulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, acetyl cyclohexylsulfonyl peroxide, di- /so-propyl percarbonate, tert-butyl peroctoate, cumene hydroperoxide, dicumyl peroxide and tert-butyl perbenzoate, azobis-/so-butyronitrile and benzpinacol.
Examples photoinitiators are acetophenone, 2,2-dimethoxy-2-phenylacetophenone (benzil dimethyl ketal), 2,2-diethoxyacetophenone, 4-dimethylaminoacetophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone 4-hydroxybenzophenone, 4-phenylbenzophenone, 2-chlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, thioxanthone, isopropyl-9H-thioxanthen-9-one, phenyl glyoxylic acid methyl ester, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propylether, benzoin isopropylether, benzoin n- butyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, cyclohexyl phenyl ketone, 1-hydroxy- cyclohexyl phenyl ketone, p-isopropyl-2-hydroxyisobutyrophenone, 2-hydroxy-2-methyl-1- phenyl-1-propanone, oligo[2-hydroxy-2-methyl-1-[ 4-(1-methylvinyl)phenyl]propanone], 2- benzyl-2-dimethylamino 1-(4-morpholinophenyl) butanone-1 , 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-1-butanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 4- (2-hydroxyethoxy)phenyl 2-hydroxy-2-propyl ketone, acylphosphine oxides such as diphe- nyl(2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4 trimethylpentylphosphine oxide, methyl-2-benzoyl benzoate and ethyl phenyl(2,4,6-trimethylbenzoyl) phosphinate.
It is also possible to use mixtures of initiators. Examples of mixtures of initiators are mixtures of at least two photoinitiators, mixtures of at least one photoinititiator and at least one thermal radical initiator as well as mixtures of at least two thermal radical initiators.
Common mixtures of photoinitiators are the mixture of bis(2,6-dimethoxybenzoyl)-2,4,4 trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone, the mixture of 1- hydroxycyclohexyl phenyl ketone and benzophenone, the mixture of bis(2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexyl phenyl ketone, the mixture of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1- propanone, the mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone, and the mixture of 4-methylbenzophenone and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide.
The at least one initiator is preferably a photoinitiator, more preferably a UV photoinitiator. A UV photoinitiator is an initiator that forms free radicals upon UV radiation treatment. Preferred initiators are selected from the group consisting of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate, benzophenone, phenyl bis(2,4,6- trimethylbenzoyl) phosphine oxide, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- phenyl-1-propanone and 2,2-dimethoxy-2-phenylacetophenone (benzil dimethyl ketal).
The polymer (2) can be any polymer different from polyurethane (PU). Polymer (2) can be a polymer carrying ethylenically unsaturated groups or a polymer not carrying ethylenically unsaturated groups. Examples of polymer (2) are polyurethanes, acrylic polymers, hybrids of polyurethane and acrylic polymer, polyesters, polyethers, polycarbonates, epoxy resins, alkyd resins, polyolefins and polyvinylacetate, as well as acryated or methacrylated derivatives thereof.
If polymer (2) is a polymer not carrying ethylenically unsaturated groups, the hydroxyl value of polymer (2) is preferably in the range of from 1 to 300 mg KOH/g and the acidic value is preferably below 50 mg KOH/g. Acrylated ond methacrylated derivatives can be prepared by methods known in the art, for example by esterifying the OH-groups of polyesters, aryl ic polymers and polyethers wih acrylic acid or methacrylic acid, or by ring-opening the epoxy groups of epoxy resin with acrylic acid or methacrylic acid.
Polyurethanes are polymers comprising urethane linkages. Polyurethanes are usually obtained by reaction of diols with diisocyanates. The diol can be a polyester diol, acrylic polymer diol, polycarbonate diol or polyetherdiol. Polyurethanes may comprise further linking groups in the main chain in lower number than the number of urethane groups such as ester, ether, thioether or urethane linkages. Acrylated or methacrylated polyurethanes can also be obtained using acrylated or methacrylated alcohols or diols as synthesis component.
Acrylic polymers are usually obtained by radical polymerization from polymerizable unsaturated monomers comprising acrylic acid esters or methacrylic acid esters, and optionally other polymerizable unsaturated monomers, by methods known in the art such as emulsion polymerization. Examples of other polymerizable unsaturated monomers are polymerizable unsaturated monomers carrying OH groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate and (meth)allyl alcohol, and polymerizable unsaturated monomers carrying acidic groups such as acrylic acid, methacrylic acid, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and itaconic anhydride. Preferably the polymerizable unsaturated monomers also comprise polymerizable unsaturated monomers carrying OH groups. The hydroxyl value of the acrylic polymers is preferably in the range from 1 to 200 mg KOH/g, more preferably in the range of 2 to 100 mg KOH/g, and most preferably 3 to 50 mg KOH/g. The weight average molecular weight of the acrylic polymer is preferably 1000 to 200000 g/mol, more preferably 2000 to 100000 g/mol, and most preferably 3000 to 50000 g/mol.
Hybrids of polyurethane and acrylic polymer can be obtained, for example, by preparing the acrylic polymer as described above, but in the presence of a polyurethane.
Polyesters are polymers comprising monomers linked via an ester linkage. Polyesters are usually obtained by an esterification reaction or transesterification reaction of a component carrying two acidic groups and a diol. Polyesters may comprise linking groups other the ester groups in lower number or equal than the number of ester groups such as carbonate, ether, thioether or urethane linking groups. The hydroxyl value of the polyester is preferably about 1 to 300 mg KOH/g, more preferably about 50 to 250 mg KOH/g, and still more preferably about 80 to 180 mg KOH/g. The acid value of the polyester resin is preferably about 1 to 200 mg KOH/g, more preferably about 15 to 100 mg KOH/g, and still more preferably below 50 mg KOH/g. The weight average molecular weight of the polyester is preferably 500 to 500000 g/mol, more preferably 1000 to 300000 g/mol, and still more preferably 1500 to 200000 g/mol. Polyethers are polymers comprising ether linkages. Polyethers are usually prepared by acid catalyzed polymerization of ethers such as ethyleneoxide, propylene oxide, butylene oxide or tetrahydrofuran using an alcohol. Examples of polyethers are polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether and polytetrahydrofuran. Polyethers may comprise further linking groups in the main chain in lower number than the number of ether groups such as ester, carbonate, thioether or urethane linkages.
Polycarbonates are polymers comprising carbonate linkages. Polycarbonates are usually obtained by reaction of carbonates with diols. Polycarbonates may comprise further linking groups in the main chain in lower number than the number of carbonate groups such as ester, ether, thioether or urethane linkages.
Epoxy resins are polymers carrying epoxy groups. Epoxy polymers can be obtained by reaction of polyols with epichlorohydrin followed by dehydrohalogenation. Examples of polyols are bisphenol A and bisphenol F as well as novolak resins, which are polymers formed by reaction of phenol with formaldehyde.
Alkyd resins are polyester carrying fatty acid-derived groups. Alkyd resins are usually obtained by an esterification reaction or transesterification reaction of a component carrying two acidic groups, a polyol and a glycerine fatty acid triester. Examples of components carrying two acidic groups are phthalic anhydride and maleic anhydride. Examples of polyols are trimethylolpropane, glycerine and pentaeryhritol. Examples of glycerine fatty acid triester are soybean oil, linseed oil and coconut oil.
Polyolefins are polymers obtainable by polymerizing at least one olefin monomer, optionally in the presence of at least a polymerizable unsaturated monomer which is not an olefin monomer, by methods known in the art such as emulsion polymerization. Olefin monomers are monomers comprising solely H and C atoms. Examples of olefin monomers are ethylene, propylene, 1- butene, 3-methyl-1 -butene, 4-methyl-1 -pentene, 3-methyl-1 -pentene, 1-heptene, 1-hexene, 1- decene and 1-dodecene; conjugated dienes and non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene and 1 ,5-hexadiene, and styrenes. Examples of polymerizable unsaturated monomers, which are no olefin monomers, are vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and itaconic anhydride.
Preferred polymers (2) are selected from the group consisting of polyurethanes, acrylic polymers, hybrids of polyurethane and acrylic polymer, as well as acrylated or methacrylated derivatives thereof.
The coating composition of the present invention usually comprises polyurethane (PU) in the range of 10 to 70% by weight based on the coating composition, more preferably of in the range of 15 to 50% by weight based on the weight of the coating composition, most preferably of in the range of 20 to 45% by weight based on the weight of the coating composition.
The coating composition of the present invention usually comprises additives in the range of 0.05 to 40% by weight based on the coating composition and most preferably of in the range of 0.1 to 25% by weight based on the weight of the coating composition.
The coating composition of the present invention preferably comprises at least one initiator in the range of 0.05 to 12.0% by weight based on the weight of polyurethane (PU), and more preferably in the rane of 0.1 to 10.0% by weight based on the weight of polyurethane (PU).
The coating composition of the present invention usually comprises compound (1) in the range of 0 to 20% by weight based on the coating composition, more preferably in the range of 0.5 to 15% by weight based on the coating composition, and most preferably in the range of 1 to 10%.
The coating composition of the present invention usually comprises polymer (2) in the range of 0 to 50% by weight based on the coating composition, more preferably in the range of 0 to 25% by weight based on the coating composition, and most preferably in the range of 0 to 10%.
The coating composition of the present invention usually comprises at least 20% by weight, more preferably at least 40% by weight water based in the weight of the coating composition.
The coating composition of the present invention can also comprise organic solvents. Examples of organic solvents are butyl glycol, butyl diglycol, methoxypropanol, 2-butoxyethyl acetate, propylene carbonate, di(propylene glycol) methyl ether, propylene glycol n-butyl ether and di(propylene glycol) n-butyl ether.
The coating composition of the present invention usually comprises below 10% by weight organic solvents based on the weight of the coating composition.
The coating composition can be a dispersion or a solution. Preferably the coating composition is a dispersion.
In one preferred embodiment, coating composition of the present invention is a clear coat composition, preferably a clear coat composition not comprising pigments.
In another preferred embodiment, the coating composition of the present invention as a pigmented coating composition.
The coating composition of the present invention can be prepared by mixing the composition of the present invention, the at least one additive, optionally the at least one initiator, optionally the least one polymer (2), and optionally additional water. The at least one additive, the at least one initiator (if present) and the at least one polymer (2) (if present) can be used “as is” or as a solution or dispersion in an organic solvent and/or in water in the mixing step. Polymers (2), which are selected from the group consisting of polyurethanes, acrylic polymers, hybrids of polyurethane and acrylic polymer, as well as acrylated or methacrylated derivatives thereof, are usually used as aqeuous solution or dispersion in the mixing step.
Also part of the present invention is a crosslinked-layer formed from the coating composition of the present invention.
The cross-linked layer is obtainable by a process, which comprises the steps of (i) applying the coating composition of the present invention to a substrate to form a layer, (ii) optionally drying the layer of step (i), and (iii) treating the layer of step (i) or of step (ii) with heat, radiation or electron beam to form a cross-linked layer.
The coating compositions of the present invention can be applied to the substrate by any method known in the art such as by draw down bar, spraying, troweling, knifecoating, brushing, rolling, rollercoating, flowcoating and laminating, doctor blades, various printing processes such as gravure, transfer, lithographica and ink jet printing and by using a bar.
The substrate can be pre-treated before the application of the coating composition, for example, the substrate can be cleaned or sanded.
The layer obtained directly after application of the coating composition on the substrate has preferably a thickness in the range of 20 to 500 micrometer, more preferably in the range of 40 to 300 micrometer, most preferably in the range of 60 to 240 micrometer, and in particular 60 to 200 micrometers.
The layer obtained directly after application of the coating composition on the substrate is commonly referred to as wet layer.
The layer of step (i) can be dried in step (ii) to remove at least most of the water (and other volatiles such as organic solvents).
The layer obtained after removal of at least most of the water (and other volatiles such as organic solvents) is commonly referred to as dried layer.
Step (ii), if present, is preferably performed at temperatures in the range of 15 to 160°C more preferably in the range of 40 °C to 160 °C. In case a thermal radical initiator is present in the coating composition, drying conditions (temperature and time) are preferably chosen that do not activate the thermal radical initiator. The layer of step (i) or of step (ii) is treated in step (iii) with electron beam, heat or radiation to form a cross-linked layer. Heat can also be applied by near infrared (NIR) radition, for example radiation having a wavelength in the range of 760 to 2500 nm. Preferably, the layer of step (i) or (ii) is treated with ultraviolett radiation, daylight or electron beam. More preferably, the layer of step (i) or (ii) is treated with radiation having a wavelength in the range of 200 to 700 nm, even more preferably in the range of fro 200 to 500 nm, and most preferably in the range of 250 to 400 nm.
Examples of radiation sources are low-pressure mercury vapor lamps, medium-pressure mercury vapor lamps, high-pressure mercury vapor lamps, lasers, pulsed lamps (flashlight), halogen lamps and excimer lamps. The radiation dose is normally chosen to be sufficient for crosslinking. In case of UV radiation, a radiation dose of 80 to 3000 mJ/cm2, preferably 100 to 2000 mJ/cm2 is usually used. A combination of different radiation sources is also possible.
Step (iii) can be perfomed either in the presence of oxygen or, preferably, in the absence of oxygen such as under intert gas atmosphere. Suitable inert gases are nitrogen, argon and carbon dioxide. The layer of step (i) or (ii) can also be covered with transparent media such as a transparent polymer film, glas or water and irradiated through the transparent media. Irradation can also be performed by passing the substrate coated with the layer of step (i) or (ii) at constant speed past a radiation source.
In a preferred embodiment step (ii) is performed and in step (iii) the layer of step (ii) is treated with radiation to form a cross-linked layer.
Steps (i), optionally (ii) and (iii) can be repeated yielding a multi-layered cross-linked layer.
The substrate can be any suitable substrate. The substrate can be wood substrates, engineered wood substrates, engineered bamboo substrates, engineered cellulosic substrates other than engineered wood or bamboo substrates, fibre-reinforced composite substrates (FRC), woodplastic composite substrates (WPC), plastic substrates such as melamine formaldehyde substrate, paper substrates, recycled paper substrates, paperboard (also called cardboard) substrate, recycled paperboard (also called recycled cardboard) substrates, metal substrates, stone substrate, glass substrates, textiles substrates, leather substrates, ceramic substrates, mineral building material substrates such as molded cement blocks and fiber-cement slabs. The substrates can be precoated with a coating composition different from the coating composition of the present invention. Preferably, the substrate is not pre-coated with a coating composition different from the coating composition of the present invention.
Examples of wood substrates are oak, beech, maple, alder, ash, pine tree, fir tree, spruce, chestnut, robinia, birch, elm, teak and walnut as well as cork. Wood can, for example, be in the form of lumber (also called timber), in the form of planks used for flooring, for example parquet flooring, in the form of devices used for house construction or domestic applications, or in the form of solid wood furnitures. Cork can be, for example, in the form of tiles used for flooring, or in the form of devices used for domestic applications.
Engineered wood substrates are derivative wood substrates manufactured by binding or fixing the strands, particles, fibres, veneers or boards of wood with adhesives or other methods of fixation to form composite materials. Examples of adhesives are urea-formaldehyde resin, phenol formaldehyde resin, melamine formaldehyde resin, polymeric methylene diphenyl diisocyanate, polyvinyl acetate and polyurethane. Examples of engineered wood substrates are gue- laminated timber, cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), laminated veneer lumber (LVL), plywood, oriented strand board (OSB), composite panels, particle board (also called flakeboard or chipboard), fibreboard such as hardboard (also called high-density fibreboard, HDF) and medium density fibreboard (MDF).
Engineered wood substrates can be in the form of lamella used for engineered wood flooring, for example laminate flooring, in the form of devices used for house construction or domestic applications, and in the form of furniture such as flat-pack furniture.
Engineered bamboo substrates are derivative bamboo substrates manufactured by binding or fixing parts of bamboo with adhesives or other methods of fixation to form composite materials. An example of engineered bamboo substrate is laminated bamboo.
Engineered cellulosic substrates other than engineered wood substrates and bamboo substrates are products from lignin-containing materials other than wood and bamboo such as rye straw, wheat straw, rice straw, hemp stalks, kenaf stalks and sugar cane residue, manufactured by binding or fixing parts of the lignin-containing materials other than wood and bamboo with adhesives or other methods of fixation to form composite materials.
Fibre-reinforced composite substrates (FRC) are made from rice-derived fibres and plastic.
Wood-plastic composites (WPCs) are composite materials made from fibres or flour of wood and thermoplastic polymers such as polyethylene, prolypropylene, polyvinyl chloride or polyacetic acid.
Preferably, the substrate is selected from the group consisting of wood substrates and plastic substrates.
Also part of the present invention is a substrate coated with the layer of the present invention.
Also part of the present invention is the use of the coating composition of the present invention as clear coat composition. Also part of the present invention is the use of the coating composition of the present invention as pigmented coating composition.
The compositions of the present invention, and in particular the coating compositions of the present invention, are advantageous in that the compositions form cross-linked layers on substrates that show a good Martens hardness and a good indentation hardness and also form cross-linked layers on substrates that show a good adhesion to the substrate.
Examples
NCO content of the composition [weight NCO/weight composition] is determined by first treating the composition with di-n-butyl amine and then back-titrating unreacted di-n-butylamine in order to determine the amount of reacted di-n-butyl amine. The following method can be used: 10 mL of a 1 N solution of di-n-butyl amine in xylene is added to 1 g of the composition to be analyzed dissolved in 100 mL of N-methylpyrrolidone. The resulting mixture is stirred at room temperature for five minutes. Then, the resulting reaction mixture is subjected to back titration using 1 N hydrochloric acid to measure the volume of the hydrochloric acid needed for neutralizing the unreacted di-n-butyl amine. This then reveals how much mol di-n-butyl amine reacted with NCO groups. The NCO content is (mol reacted di-n-butyl amine x molecular weight of NCO)/weight composition. The weight of the composition is 1 g. The molecular weight of NCO is 42 g/mol.
Example 1
Preparation of an aqueus polyurethane dispersion PUD-1 comprising polyurethane PU-1
41.89 g dimethylol propionic acid (compound B1), 390.35 g Laromer EA 9143 (consisting of 75% by weight bisphenol A diglycidylether diacrylate (compound B2) and 25% by weight of propoxylated glycerine triacrylate having a degree of propoxylation of 3.8 (reactive diluent), 75.36 g ALBODRY Castor Oil Low Moisture 1500 (OH number: 160-168 mg KOH/g, iodine value: 81-91 g/100 g) (compound B3), 41.64 g Alberdingk OP 100 (urethane modified polymer based on linseed oil, 100% solids, OH number: 7 mg KOH/g) (compound B5), 0.077 g 4- hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TEMPO), and 0.54 g Borchi ® 315, OMG Borchers (bismuth (III) neodecanoate) were weighed to a stirring vessel. The precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C. A mixture of 185.12 g isophorone diisocyanate (compound A) and 36.26 g Lupranat T80 A (consisting of 80% by weight tol- uene-2,4-diisocyanate and 20% by weight toluene-2,6-diisocyanate) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages. The progress of the reaction was monitored by measurement of residual NCO. At the level of < 1.1 weight% of residual NCO content (based on reaction mixture), the reaction mixture was further diluted by addition of 300 g acetone. The obtained mixture was neutralized by addition of 31.64 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring. After distilling off the solvent mixture and dilution with additional 200 g of deionized water, an aqueous composition PUD-1 comprising polyurethane PU-1 having a solid content of 37.8 weight%, and the properties as shown in table 1 was obtained.
Example 2
Preparation of an aqueus polyurethane dispersion PUD-2 comprising polyurethane PU-2
42.14 g dimethylolpropionic acid (compound B1), 389.26 g Laromer EA 9143 (consisting of 75% by weight bisphenol A diglycidylether diacrylate (compound B2) and 25% by weight of propox- ylated glycerine triacrylate having a degree of propoxylation of 3.8 (reactive diluent), 74.6 g hydrogenated castor oil (OH number: 157 mg KOH/g, iodine value: 2.1 l2 g/100 g) (compound B3), 41.89 g Alberdingk OP 100 (urethane modified polymer based on linseed oil, 100% solids, OH number: 7 mg KOH/g) (compound B5), 0.077 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-Hydroxy-TEMPO), and 0.54 g Borchi ® 315, OMG Borchers (bismuth(lll) neodecanoate) were weighed to a stirring vessel. The precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C. A mixture of 186.2 g isophorone diisocyanate (compound A) and 36.48 g Lupranat T80 A consisting of 80% by weight toluene-2,4-diisocyanate and 20% by weight tolu- ene-2,6-diisocyanate) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages. The progress of the reaction was monitored by measurement of residual NCO. At the level of < 1.1 weight% of residual NCO (based on reaction mixture), the reaction mixture was further diluted by addition of 300 g acetone. The obtained mixture was neutralized by addition of 31.83 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring. After distilling off the solvent mixture and dilution with additional 200 g of deionized water, an aqueous composition PUD-2 comprising polyurethane PU-2 having a solid content of 38.6 weight%, and the properties as shown in table 1 was obtained.
Comparative example 1
Preparation of a comparative aqueous polyurethane dispersion comp PUD-3 comprising comparative polyurethane compPU-3
51.42 g dimethylolpropionic acid (compound B1), 266.3 g Laromer EA 9143 (consisting of 75% by weight bisphenol A diglycidylether diacrylate (compound B2) and 25% by weight of propox- ylated glycerine triacrylate having a degree of propoxylation of 3.8 (reactive diluent), 89.56 g Albodur 921 (Alberdingk Boley) (OH functional polymer based on castor oil, 100% solids, hydroxyl number: 218 mg KOH/g) (compound B3), 26.98 g hydroxy ethyl acrylate (compound B4), 31.6 g Alberdingk OP 100 (urethane modified polymer based on linseed oil, 100% solids, OH number: 7 mg KOH/g) (compound B5), 0.077 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-Hydroxy-TEMPO), and 0.54 g Borchi ® 315, OMG Borchers (bismuth(lll) neodecanoate) were weighed to a stirring vessel. The precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C. 306.28 g Desmodur W (Covestro, dicyclohexylmethanediisocyanate; NCO content > 31.8 weight%) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages. The progress of the reaction was monitored by measurement of residual NCO. At the level of < 1.1 weight% of residual NCO (based on reaction mixture), the reaction mixture was further diluted by addition of 300 g acetone. The obtained mixture was neutralized by addition of 45.27 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring. After distilling off the solvent mixture and dilution with additional 400 g of deionized water, an aqueous composition compPUD-3 comprising polyurethane compPU-3 having a solid content of 34.6 weight%, and the properties as shown in table 1 was obtained.
Comparative example 2
Preparation of a comparative aqueous polyurethane dispersion comp PUD-4 comparative polyurethane compPU-4
32.02 g dimethylolpropionic acid (compound B1), 234.54 g Laromer EA 9143 (consisting of 75% by weight bisphenol A diglycidylether diacrylate (compound B2) and 25% by weight of propox- ylated glycerine triacrylate having a degree of propoxylation of 3.8 (reactive diluent), 174.74 g of di pentaerythritol pentaacrylate (compound B4)/dipentaeryhritol hexaacrylate (reactive diluent) ((OHZ 46 mg KOH/g, double bond density (1H-NMR) = 9,4 mol/kg), 38.47 g Laromer EA 9101 (BASF, acrylated epoxidized soybean oil, hydroxyl number: 139 mg KOH/g, double bond density (1 H-NMR): 2.0 mol/kg) (compound B5), 0.35 g Kerobit TBK (Alpha Aeser, 2,6-di-tert-butyl-4- methylphenol), 0.14 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TEMPO), 198.32 g Desmodur W (Covestro, dicyclohexylmethanediisocyanate; NCO content s 31.8 weight%) (compound A) and 15.12 g Basonat HI 100 NG (BASF, hexamethylenediisocyanate trimer, NCO content ~ 22 weight%) (compound A) are weighed to a stirring vessel. The precharge was dissolved in 300 g methyl ethyl ketone and heated to 60°C. 0.49 g Borchi ® 315, OMG Borchers (bismuth(lll) neodecanoate) was added and the reaction mixture was further heated until a temperature of 80°C is reached. The progress of the reaction was monitored by measurement of residual NCO. At the level of < 1.4 weight% of residual NCO (based on reaction mixture), the reaction mixture was further diluted by addition of 200 g acetone and cooled to 40°C. 6.78 g of isophorone diamine, diluted in 20 g of acetone was added over a period of 5 min. After a waiting time of 5 min, the reaction mixture was neutralized by the addition of 71 .69 g of NaOH (10 wt% in H2O) and dispersed with 650 g of deionized water under vigorous stirring. After 20 min, a mixture of 6.78 g of isophorone diamine and 3.25 g of diethylentriamine, diluted in 50 g of deionized water was added over a period of 15 min. After distilling off the solvent mixture and dilution with additional 400 g of deionized water, an aqueous composition compPUD-4 comprising polyurethane compPU-4 having a solid content of 39.0 weight%, and the properties as shown in table 1 was obtained. Comparative example 3
Preparation of comparative aqueous polyurethane dispersion compPUD-5 polyurethane compPU-5
41.51 g dimethylolpropionic acid (compound B1), 168.94 g Laromer EA 9143 (consisting of 75% by weight bisphenol A diglycidylether diacrylate (compound B2) and 25% by weight of propox- ylated glycerine triacrylate having a degree of propoxylation of 3.8 (reactive diluent), 232.0 g Albodur 921 (Alberdingk Boley) (OH functional polymer based on castor oil, 100% solids, hydroxyl number: 218 mg KOH/g) (compound B3), 53.91 g hydroxyethyl acrylate (compound B4), 0.077 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-Hydroxy-TEMPO), and 0.54 g Borchi ® 315, OMG Borchers (bismuth(lll) neodecanoate) were weighed to a stirring vessel. The precharge was dissolved in 229.4 g methyl ethyl ketone and heated to 60°C. A mixture of 229.33 g isophorone diisocyanate (compound A) and 44.92 g Lupranat T80 A (consisting of 80% by weight toluene-2,4-diisocyanate and 20% by weight toluene-2,6-diisocyanate) (compound A) was added in four equal portions, dosage time 5 min, 15 min waiting time between the dosages. The progress of the reaction was monitored by measurement of residual NCO. At the level of < 1.1 wt. % of residual NCO, the reaction mixture was further diluted by addition of 300 g acetone. The obtained mixture was neutralized by addition of 31.35 g triethylamine and dispersed with 1050 g of deionized water under vigorous stirring. After distilling off the solvent mixture and dilution with additional 200 g of deionized water, an aqueous composition compPUD-5 comprising polyurethane compPU-5 having a solid content of 38.3 weight%, and the properties as shown in table 1 was obtained.
Example 3
Preparation of clear coating compositions comprising the aqueous polyurethane dispersions PUD-1 and PUD-2 of examples 1 and 2, respectively, and of comparative clear coating compositions comprising the comparative aqueous polyurethane dispersions compPUD-3, compPUD- 4 and compPUD-5 of comparative examples 1 , 2 and 3, respectively.
The aqueous polyurethane dispersions PUD-1 and PUD-2 of examples 1 and 2, respectively, and the comparative aqueous polyurethane dispersions compPUD-3, compPUD-4 and comp- PUD-5 of comparative examples 1, 2 and 3, respectively, were diluted with water to a solid content of 35 weight%. 1 g Omnirad® 184 (photoinitiator, available from IGM Resins) was mixed with 1 g of butyl glycol (solvent). 100 g of the diluted aqueous polyurethane dispersions (35 weight%) were mixed with 2.0 g of the 1/1 (weight/weight) mixture of Omnirad® 184 and butyl glycol (solvent) and with 1.0 g Rheovis® PE 1330 (thickener, available from BASF) using a speedmixer (2000 rpm, 2 minutes) to yield coating compositions. Example 4
Preparation of clear glass plates coated with the clear coating compositions of example 3 and determination of the indentation hardness and of the Martens hardness of the coated layers
The coating compositions of example 3 were applied on the surface of a clear glass plate by means of a box film applicator with 400 pm gap to form a layer. Resulting film thickness must be at least 10 times the expected maximal indentation depth. The resulting layers were dryed 2 minutes at room temperature and 15 minutes in a convection oven at 50 °C. Immediately after the drying step the layers were treated with UV radiation using one Hg lamp, 50 % power (2 x 10 m/minute, total dose of about 1200 mJ/cm2) to form cured layers which were stored in a climatic chamber (temperature (23 ± 2) °C, humidity (50 ± 5) %) for 24 hours before starting the measurement of hardness and flexibility of the layers by an indentation object (diamond Vickers pyramid), where the indentation hardness and Martens hardness were measured using a Fischerscope HM2000 S with the folwing parameters: Fmax = 500 mN, Fmin = 0,4 mN, t1 = t2 = t3 = t4 = 30 seconds.
Definitions:
Fmax = maximum test force [mN] t1 = application time of the test force [s] t2 = holding time at maximum test force [s] F max = minimum test force [mN] t3 = time to withdraw the test force t4 = holding time at minimum test force [s] HM (Fmax/t1/0) = Martens hardness [N/mm2] HIT (Fmax/t1/t2/t3) = Indentation hardness [N/mm2]
Evaluation was started after two single measurements and mean values for Martens hardness (HM) and indentation hardness (HIT) were documented.
The higher the values of the Martens hardness and indentation hardness the better is the hardness.
The results are outlined in table 1.
Example 5
Preparation of white pigmented coating compositions comprising the aqueous polyurethane dispersions PUD-1 and PUD-2 of examples 1 and 2, respectively, and of comparative white pigmented coating compositions comprising the comparative aqueous polyurethane dispersions compPUD-3, compPUD-4 and compPUD-5 of comparative examples 1 , 2 and 3, respectively. The aqueous polyurethane dispersions PUD-1 and PUD-2 of examples 1 and 2, respectively, and the comparative aqueous polyurethane dispersions compPUD-3, compPUD-4 and comp- PUD-5 of comparative examples 1 , 2 and 3, respectively, were diluted with water to a solid content of 35 weight%.
21 g Luconyl white NG 0025 (aqueous pigment preparation available from BASF), 0.5 g Hy- dropalat WE 3220 (surfactant available from BASF), 1.2 g Omnirad 819 DW (photoinitiator, available from IGM Resins), 0.5 g Tego Foamex 822 (defoamer available from Evonik), 1.0 g Ultralube D-888 (wax dispersion available from Keim Additec Surface) and a mixture of 0.8 g Omnirad 184 (photoinitiator, available from IGM Resins) in 0.8 g butyl glycol (solvent) were mixed (2 min 2750 upm with the speedmixer) to yield a “paste”.
To get good incorporation of the matting agent 30 g of the aqueous polyurethane dispersions (35 weight%) were mixed with 1 ,0 g of Acematt TS 100 (matting agent available from Evonik) using a speedmixer (2750 rpm, 3 minutes). If the matting agent was not good incorporated, the mixture was mixed again using a speedmixer (2750 rpm, 1-2 minutes). An “Acematt TS100 dispersion” was obtained.
53,1 g of the aqueous polyurethane dispersions (35 weight%), the “paste” obtained above and the “Acematt TS 100 dispersion” obtained above were mixed for 2 min at 2750 upm using the speedmixer. 0,8 g Tafigel PUR 44 (thickener, available from BASF) were added to the obtained mixture and mixed again for 1 min at 2750 upm using the speedmixer.
Example 6
Preparation of melamine (melamine formaldhyde) panels coated with the white pigmented coating compositions of example 5, and determination of the “adhesion” of the coated layer to the melamine panel
The white pigmented coating compositions of example 5 were applied on the surface of the melamine panel using a 200-micrometer small box film applicator to form a layer. The layers were allowed to dry at room temperature for 2 minutes, and then at 50 °C in a drying cabinet for 15 minutes. Immediately after the drying step the layers were treated with UV radiation using Hg and Ga lamps, 50 % power (1 x 10 m/minute, total dose of about 1200 -1300 mJ/cm2) to form cured layers. The first layers were sanded using 400 grit sandpaper and wiped off with a cleaning tissue (soft absorbent). Then, the procedure was repeated once again, and a second layer was applied on the first layer using a smaller box film applicator and dried and cured in the same manner as described for the first layer.
The adhesion tests were performed on the panel with a knife/ blade with extra template to lead the cutting (distance 2 mm). The cross cuts were carried out at least 5 mm away from the edge. The cutting device was placed vertically onto the surface and six cuts (each about 2 cm long) were carried out parallel to each other. Then the samples were rotated 90° and the procedure was repeated once again to get a grid. Then the self-adhesive tapes (about 4 cm long, Tesa no. 4124) were placed on the grids, smoothed with the finger (firm pressure) and removed with a jerk at a 60° angle.
The cut surfaces were evaluated immediately and were classified as follows:
Figure imgf000040_0001
Thus, the smaller the classification, the better is the adhesion of the coated layer to the melamine panel.
The results are outlined in table 1.
Figure imgf000041_0001
Table 1. * B is the sum of B1 , B2, B3, B4 and B5.
Table 1 shows that the coating compositions comprising the aqueous polyurethane dispersions PUD-1 and PUD-2 of the present invention having an equivalent ratio OH groups of B2/(OH groups of B1, B2, B3, B4 and B5 of around 59% and having a weight ratio B3/(A+B*+C) of around 11% yield cross-linked layers on clear glass plates that show a good Martens hardness of 115.2 and 116.4 N/mm3, respectively, and a good indentation hardness of 129.2 N/mm3 and 132.7 N/mm3, respectively, and at the same time also yield cross-linked layers on melamine panels that show a good adhesion of classification 1 to 2.
Table 1 also shows that the comparative coating composition comprising the aqueous polyurethane dispersions compPUD-3 having an equivalent ratio OH groups of B2/(OH groups of of B1 , B2, B3, B4 and B5) of only 37.9% yields cross-linked layers on clear glass plates that show an acceptable Martens hardness of 109.0 N/mm3 and an acceptable indentation hardness of 122.6 N/mm3, but only yield cross-linked layers on melamine panels that show a bad adhesion of classification 4.
Table 1 also shows that the comparative coating composition comprising the aqueous polyurethane dispersions compPUD-4 having a weight ratio B3/(A+B*+C) of 0% yields cross-linked layers on clear glass plates that show a good Martens hardness of 153.8 N/mm3 and a good indentation hardness of 187.2 N/mm3 but only yield cross-linked layers on melamine panels that show a bad adhesion of classification 5.
Table 1 also shows that the comparative coating composition comprising the aqueous polyurethane dispersion compPUD-5 having an equivalent ratio OH groups of B2/(OH groups of B1 , B2, B3, B4 and B5 of 20.8% yields a cross-linked layer on clear glass plates that show a bad Martens hardness of 72.2 N/mm3, respectively, and a bad indentation hardness of 70.1 N/mm3 but yield a cross-linked layer on a melamine panel that show a good adhesion of classification 1 to 2.

Claims

Claims
1. A composition comprising
(i) at least one polyurethane PU carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, which polyurethane is obtainable by the reaction of at least one polyisocyanate (A), at least one polyol (B1) carrying at least one COOH group, at least one polyol (B2) carrying at least one (meth)acrylate group, but no COOH group, and comprising at least one aromatic ring, at least one polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring, optionally at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and optionally at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1 , B2 and B3 and B4, optionally at least one compound (C) carrying at least one NH2 group and no OH group, wherein the equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is at least 45% and wherein the weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is at least 1 %,
(ii) optionally at least one compound (1) carrying at least one ethylenically unsaturated group and no COOH group and
(iii) water.
2. The composition of claim 1 , wherein the equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is at least 50%. 3. The composition of claim 2, wherein the equivalent ratio OH groups of B2/OH groups of B1 , B2, B3, B4 and B5 is at least 55%.
4. The composition of any of claims 1 to 3, wherein the weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is in the range of from 2% to 30%.
5. The composition of any of claims 1 to 3, wherein the weight ratio of B3/(A, B1 , B2, B3, B4, B5 and C) is in the range of from 3 to 25%.
6. The composition of any of claims 1 to 5, wherein polyol (B2) is of formula
Figure imgf000043_0003
wherein L1 is a linking group comprising at least one aromatic ring.
7. The composition of any of claims 1 to 5, wherein polyol (B2) is of formula
Figure imgf000043_0001
wherein L1 is selected from the group consisting of
Figure imgf000043_0002
Figure imgf000044_0001
15 8. The composition of any of claims 1 to 5, wherein polyol (B2) is of formula
Figure imgf000045_0001
The composition of any of claims 1 to 8, wherein polyol (B3) is an ester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 10 carbon atoms and at most 21 carbon atoms, wherein the polyol has a hydroxy number in the range of 50 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring. The composition of any of claims 1 to 9, wherein polyol (B3) is a triester of glycerin and ric- inoleic acid, a triester of glycerin and hydrogenated ricinoleic acid or is derived from a triester of glycerin and ricinoleic acid, or from a triester of glycerin and hydrogenated ricinoleic acid. The composition of any of claims 1 to 10, wherein the at least one polyurethane (PU) carrying (meth)acrylate groups and COOH groups, which COOH groups are at least partly in the form of a salt group thereof, is more preferably obtainable by the reaction of
10.0 to 60.0% by weight of at least one polyisocyanate (A),
1.0 to 20.0% by weight of at least one polyol (B1) carrying at least one COOH group, 10.0 to 60.0% of at least one polyol (B2) carrying at least one (meth)acrylate groups, but no COOH group, and comprising at least one aromatic ring,
3.0 to 20.0% at least polyol (B3) which is an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, or which is derived from an ester of glycerin and at least one carboxylic acid carrying at least 6 carbon atoms, wherein the polyol has a hydroxy number in the range of 10 to 250, and does not carry COOH groups and (meth)acrylate groups and does not comprise at least one aromatic ring,
0 to 30.0% of at least monoalcohol (B4) carrying at least one (meth)acrylate group and no COOH group, and
0 to 30.0% of at least one compound, oligomer or polymer (B5) which carries at least one OH group and is different from B1 , B2 and B3 and B4,
0 to 15.0% of at least one compound (C) carrying at least one NH2 group and no OH group in each case based on the sum of weights of (A), (B1), (B2), (B3), (B4), (B5) and (C1).
12. The composition of any of claims 1 to 11 , wherein compound (1) carries at least one (meth)acrylate group.
13. The composition of any of claims 1 to 12, wherein the composition comprises the polyurethane (PU) in an amount of 10 to 70% by weight based on the weight of the composition.
14. An aqueous coating composition comprising the composition of any of claims 1 to 13, at least one additive, optionally at least one initiator and optionally at least one polymer (2) dif- feren from polyurethane (PU), wherein the coating composition comprises polyurethane (PU) in the range of 10 to 70% by weight based on the weight of the coating composition.
15. A crosslinked layer formed from the aqueous coating compositions of claim 14.
16. A substrate coated with the cured layer of claim 15.
17. The substrate of claim 16, wherein the substrate is a plastic substrate or a wood substrate.
18. The use of the coating composition of claim 14 as clear coat composition.
19. The use of the coating composition of claim 14 as pigmented coating composition.
PCT/EP2023/084975 2022-12-15 2023-12-08 Aqueous compositions comprising (meth)acrylate group carrying polyurethane which yield cross-linked layers of high hardness and good adhesion WO2024126304A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100267925A1 (en) 2007-11-01 2010-10-21 Cargill, Incorporated Natural oil-derived polyester polyols and polyurethanes made therefrom
WO2011107398A1 (en) 2010-03-02 2011-09-09 Bayer Materialscience Ag Aqueous polyurethane dispersions
EP3350243B1 (en) * 2015-09-16 2019-08-14 Covestro Deutschland AG Coated films with particularly high hydrolysis resistance and shaped articles obtained from same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100267925A1 (en) 2007-11-01 2010-10-21 Cargill, Incorporated Natural oil-derived polyester polyols and polyurethanes made therefrom
WO2011107398A1 (en) 2010-03-02 2011-09-09 Bayer Materialscience Ag Aqueous polyurethane dispersions
EP2542600B1 (en) * 2010-03-02 2014-03-26 Bayer Intellectual Property GmbH Aqueous polyuretahne dispersions
EP3350243B1 (en) * 2015-09-16 2019-08-14 Covestro Deutschland AG Coated films with particularly high hydrolysis resistance and shaped articles obtained from same

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