EP3430063A1 - Composition de revêtement aqueuse - Google Patents

Composition de revêtement aqueuse

Info

Publication number
EP3430063A1
EP3430063A1 EP17710304.1A EP17710304A EP3430063A1 EP 3430063 A1 EP3430063 A1 EP 3430063A1 EP 17710304 A EP17710304 A EP 17710304A EP 3430063 A1 EP3430063 A1 EP 3430063A1
Authority
EP
European Patent Office
Prior art keywords
polyurethane
vinyl polymer
coating composition
aqueous coating
polymer hybrid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17710304.1A
Other languages
German (de)
English (en)
Inventor
Saskia Carolien Van Der Slot
Gerardus Cornelis Overbeek
Ronald Tennebroek
Alexander Wilhelmus Martinus Cornelis Donders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Priority claimed from PCT/EP2017/056112 external-priority patent/WO2017158016A1/fr
Publication of EP3430063A1 publication Critical patent/EP3430063A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture 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
    • C08G18/0866—Manufacture 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents

Definitions

  • the present invention relates to an aqueous coating composition comprising a urethane-acrylic hybrid, a process for preparing such a composition and a coating obtained from such a composition.
  • polyurethane binders can be applied to a variety of substrates to provide coatings with good mechanical and chemical resistances.
  • a major application for such coatings is as clear coatings for wood flooring.
  • the coatings need to have good black marking resistance and resistance to damage as well as good (micro) scratch resistance. Black heel marks occur especially in floor coatings when the heel or sole of a shoe leaves residue on the floor after a shoe scuffs (black marking) or scrapes (damage) the coating surface.
  • Urethane binders often require solvent in the production process in order to reduce the viscosity of the prepolymer to acceptable values.
  • the legislation regarding the presence of VOC's (volatile organic components) in indoor applied binders is under pressure.
  • the use of solvents containing VOC's in the urethane prepolymer preparation is therefore less and less preferred and a lot of effort and energy is required to remove such solvent after preparation.
  • the use of vinyl monomers as diluent have shown to be a good alternative for solvent containing VOC's , leading to urethane acrylic hybrids.
  • the object of the present invention is to provide aqueous coating compositions of polyurethane-vinyl polymer hybrid particles which compositions can result in coatings with good mechanical properties, in particular the combination of (micro) scratch resistance and Black Heel Mark Resistance (BHMR) .
  • BHMR Black Heel Mark Resistance
  • the object of the present invention has been achieved by providing an aqueous coating composition comprising dispersed polyurethane-vinyl polymer hybrid particles wherein (i) the polyurethane-vinyl polymer hybrid is obtained by free-radical polymerization of at least one vinyl monomer in the presence of a polyurethane,
  • the polyurethane is obtained by the reaction of at least (I) an isocyanate- terminated polyurethane prepolymer and (II) at least one active-hydrogen containing chain extending compound, wherein the isocyanate-terminated polyurethane prepolymer is obtained by the reaction of at least one polyol with at least one polyisocyanate, wherein from 50 to 100 wt.% of the total amount of the polyisocyanates used to form the polyurethane are aromatic polyisocyanates,
  • the polyurethane-vinyl polymer hybrid is ketone functional and contains from 50 to 1000 mmol of ketone groups per 1000 g polyurethane-vinyl polymer hybrid,
  • polyurethane-vinyl polymer hybrid ranges from 90:10 to 35:65
  • the polyurethane-vinyl polymer hybrid has an acid value from 7 to 60 mg KOH/g polyurethane-vinyl polymer hybrid, preferably from 9 to 40 mg KOH/g polyurethane-vinyl polymer hybrid and most preferably from 12 to
  • the aqueous coating composition comprises a dihydrazide functional
  • the molar ratio of hydrazide groups (present in the dihydrazide functional compound (vii)) to ketone groups is from 1.5 to 0.1.
  • US2009/0137734 discloses aqueous dispersions of polyurethane/acrylic polymer hybrid made by forming a mixture of urethane prepolymer or polymer, acrylic monomer or polymer, ketone functional molecule/oligomers, and hydrazine functional molecule/oligomers.
  • EP1814925 describes aqueous coating compositions comprising polyurethane vinyl polymer hybrid dispersions. None of these patent publications describe the aqueous coating compositions according to the present invention.
  • the aqueous coating composition according to the invention comprises dispersed polyurethane-vinyl polymer hybrid particles whereby the polyurethane-vinyl polymer hybrid is ketone functional and contains from 50 to 1000 mmol of ketone groups per 1000 g polyurethane-vinyl polymer hybrid, preferably from 75 to 500 mmol of ketone groups per 1000 g polyurethane-vinyl polymer hybrid, more preferably from 150 to 400 mmol of ketone groups per 1000 g polyurethane-vinyl polymer hybrid.
  • the ketone groups are present in the polyurethane and in the vinyl polymer of the polyurethane-vinyl polymer hybrid.
  • the amount of ketone groups in the polyurethane-vinyl polymer hybrid are determined by calculation as known in the art. For the sake of clarity, the calculations are illustrated in the experimental part of the description.
  • the summed amount of the amount of ketone group containing vinyl monomers used to prepare the vinyl polymer of the polyurethane-vinyl polymer hybrid and the amount of ketone group containing components used to prepare the polyurethane of the polyurethane-vinyl polymer hybrid is chosen such that the desired amount of ketone groups in the polyurethane-vinyl polymer hybrid is obtained.
  • the molar amount of ketone groups in the vinyl polymer to the total molar amount of ketone groups in the polyurethane-vinyl polymer hybrid is preferably from 40% to 95%, more preferably from 55% to 90% and most preferred from 70% to 85%.
  • the ketone groups are introduced in the vinyl polymer by
  • Suitable vinyl monomers comprise one or more polymerisable ethylenically unsaturated groups.
  • the vinyl monomers used to prepare the vinyl polymer of the polyurethane- vinyl polymer hybrid thus consist of vinyl monomer(s) not containing ketone groups (i.e. other vinyl monomer(s)) and ketone group containing vinyl monomer(s). It is preferred to use vinyl monomers not containing isocyanate or isocyanate-reactive groups. Free acid functional vinyl monomers such as methacrylic acid should preferably not be employed since they may destabilize the dispersion.
  • the ketone group containing vinyl monomers are preferably selected from the group consisting of acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, diacetone acrylate, acetonitrile acrylate and any mixture thereof. More preferably the ketone groups are introduced in the vinyl polymer by copolymerizing of diacetone acrylamide with at least one other vinyl monomer.
  • the dispersed polyurethane-vinyl polymer hybrid particles present in the aqueous coating composition of the present invention is obtained by free-radical polymerization of vinyl monomer in the presence of a polyurethane.
  • a part of the vinyl monomer is a ketone group containing vinyl monomer which is copolymerized with at least one other vinyl monomer.
  • At least 30 wt.%, more preferably at least 50 wt.%, more preferably at least 70 wt.% and even more preferably 100 wt.% of the total amount of the other vinyl monomer(s) used to prepare the vinyl polymer is selected from the group consisting of methyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, styrene and mixtures of two or more of said monomers.
  • the other vinyl monomer used to prepare the vinyl polymer is selected from the group consisting of methyl methacrylate, butyl acrylate, butyl methacrylate, styrene and mixtures thereof.
  • At least 30 wt.%, preferably at least 50 wt.% and more preferably at least 70 wt.% of the total amount of the other vinyl monomer(s) used to prepare the vinyl polymer is selected from styrene and/or methyl methacrylate.
  • the vinyl monomer(s) are polymerized using a conventional free radical yielding initiator system.
  • Suitable free radical yielding initiators include mixtures partitioning between the aqueous and organic phases.
  • Suitable free-radical-yielding initiators include inorganic peroxides such as ammonium persulphate hydrogen peroxide, organic peroxides, such as benzoyl peroxide, alkyl hydroperoxides such as t- butyl hydroperoxide and cumene hydroperoxide; dialkyl peroxides such as
  • di-t-butyl peroxide peroxy esters such as t-butyl perbenzoate and the like; mixtures may also be used.
  • the peroxy compounds are in some cases advantageously used in combination with suitable reducing agents (redox systems) such as iso-ascorbic acid.
  • Azo compounds such as azobisisobutyronitrile may also be used.
  • Metal compounds such as Fe.EDTA (EDTA is ethylene diamine tetracetic acid) may also be usefully employed as part of the redox initiator system.
  • the amount of initiator or initiator system to use is conventional, e.g. within the range of 0.05 to 6 wt% based on the weight of vinyl monomer used.
  • the glass transition temperature T g of the vinyl polymer of the polyurethane-vinyl polymer hybrid is from -10 °C to 1 10 °C, preferably from 20 °C to 1 10 °C, whereby the T g is measured by differential scanning calorimetry (DSC) taking the inflection point in the thermogram as the T g value.
  • the polyurethane present in the aqueous coating composition of the present invention is obtained by the reaction of at least (I) an isocyanate-terminated polyurethane prepolymer and (II) at least one active-hydrogen containing chain extending compound.
  • the isocyanate-terminated polyurethane prepolymer is obtained by the reaction of at least one polyol with at least one polyisocyanate, whereby from 50 to 100 wt.% of the total amount of the polyisocyanates used in the preparation of the polyurethane are aromatic polyisocyanates, preferably from 75 to 100 wt.% of the total amount of the polyisocyanates used to form the polyurethane are aromatic
  • polyisocyanates preferably 100 wt.% of the total amount of the polyisocyanates used to form the polyurethane are aromatic polyisocyanates.
  • the aromatic polyisocyanate can be a mixture of aromatic
  • polyisocyanates An aromatic polyisocyanate (for the sake of clarity) being intended to mean compounds in which all of the isocyanate groups are directly bonded to an aromatic group, irrespective of whether aliphatic groups are also present.
  • suitable aromatic polyisocyanates include but are not limited to p-xylylene diisocyanate, 1 ,4-phenylene diisocyanate, 2,4- toluene diisocyanate, 2,6- toluene diisocyanate, 4,4'- methylene bis(phenyl isocyanate), 2,4'-methylene bis(phenyl isocyanate).
  • the aromatic polyisocyanate is 2,4- toluene diisocyanate, 2,6- toluene diisocyanate, 4,4'-methylene bis(phenyl isocyanate), 2,4'-methylene bis(phenyl isocyanate) and any mixture thereof.
  • the polyurethane-vinyl polymer hybrid has an acid value from 7 to 60 mg KOH/g polyurethane-vinyl polymer hybrid, preferably from 9 to 40 mg KOH/g polyurethane-vinyl polymer hybrid and most preferably from 12 to 25 mg KOH/g polyurethane-vinyl polymer hybrid.
  • the acid value is determined by acid/base titration: A specific amount of sample, dissolved in a suitable solvent (or solvent mixture), is titrated with an alcoholic potassium hydroxide solution of known concentration. The equivalence point of the potentiometric titration is determined by means of a
  • the acid number is calculated based on the equivalence point.
  • the polyol used to prepare the isocyanate-terminated polyurethane prepolymer comprises a polyol containing ionic and/or potentially ionic water-dispersing groups having a molecular weight of from 100 to 500 g/mol (further referred to as component (b)).
  • component (b) The amount of polyol containing ionic or potentially ionic water- dispersing groups having a molecular weight of from 100 to 500 g/mol relative to the total amount of components used to prepare the polyurethane is preferably from 6 to 15.6 wt.%, more preferably from 6 to 12 wt.%.
  • potentially anionic dispersing group means a group which under the relevant conditions can be converted into an anionic group by salt formation (i.e.deprotonating the group by a base).
  • Preferred ionic water-dispersing groups are anionic water-dispersing groups.
  • Preferred anionic water-dispersing groups are carboxylic, phosphoric and/or sulphonic acid groups. Examples of such compounds include carboxyl containing diols, for example dihydroxy alkanoic acids such as 2,2-dimethylol propionic acid (DMPA) or 2,2- dimethylolbutanoic acid (DMBA).
  • DMPA 2,2-dimethylol propionic acid
  • DMBA 2,2- dimethylolbutanoic acid
  • sulfonate groups may be used as potentially anionic water-dispersing groups.
  • the anionic water-dispersing groups are preferably fully or partially in the form of a salt.
  • Conversion to the salt form is optionally effected by neutralisation of the polyurethane prepolymer with a base, preferably during the preparation of the polyurethane prepolymer and/or during the preparation of the aqueous composition of the present invention.
  • the base used to neutralise the groups is preferably ammonia, an amine or an inorganic base.
  • Suitable amines include tertiary amines, for example triethylamine or ⁇ , ⁇ -dimethylethanolamine.
  • Suitable inorganic bases include alkali hydroxides and carbonates, for example lithium hydroxide, sodium hydroxide, or potassium hydroxide.
  • a quaternary ammonium hydroxide for example N + (CH3)4(OH), can also be used.
  • a base is used which gives counter ions that may be desired for the composition.
  • preferred counter ions include Li + , Na + , K + , NH4 + and substituted ammonium salts.
  • Cationic water dispersible groups can also be used, but are less preferred. Examples include pyridine groups, imidazole groups and/or quaternary ammonium groups which may be neutralised or permanently ionised (for example with dimethylsulphate).
  • a very suitable polyol containing ionic or potentially ionic water-dispersing groups is dimethylol propionic acid (DMPA).
  • the neutralising agent is preferably used in such an amount that the molar ratio of the ionic and potentially ionic water dispersing groups to the neutralizing groups of the neutralising agent are in the range of from 0.5 to 2.0, more preferably from 0.7 to 1.5 and even more preferably from 0.85 to 1.2.
  • the isocyanate-terminated polyurethane prepolymer is prepared using from 0 to 10 wt.%, preferably from 3 to 8 wt.% of at least one isocyanate-reactive polyol containing non-ionic water-dispersing groups (further referred to as component (c)).
  • Preferred non-ionic waterdispersing groups are polyalkylene oxide groups, more preferably polyethylene oxide groups.
  • a small segment of the polyethylene oxide group can be replaced by propylene oxide segment (s) and/or butylene oxide segment (s), however the polyethylene oxide group should still contain ethylene oxide as a major component.
  • the preferred ethylene oxide chain length is > 4 ethylene oxide units, preferably > 8 ethylene oxide units and most preferably > 15 ethylene oxide units.
  • the polyethylene oxide group has a Mw from 175 to 5000
  • Daltons more preferably from 350 to 2200 Daltons, most preferably from 660 to 2200 Daltons.
  • the isocyanate-terminated polyurethane prepolymer is prepared using from 2 to 40 wt. % of isocyanate reactive polyol containing ketone groups not comprised by (b) or (c) (further referred to as component (d)).
  • the ketone groups of the polyurethane are introduced in the polyurethane by incorporation of ketone group containing isocyanate reactive compounds selected from the group consisting of dihydroxy acetone, diacetone alcohol, or via isocyanate reactive ketone group containing polyols with a Mw from 500 to 5000 Daltons bearing ketone groups.
  • the isocyanate-terminated polyurethane prepolymer is prepared using from 0 to 64 wt.%, preferably from 5 to 50 wt.% of at least one isocyanate- reactive polyol not comprised by (b), (c) or (d).
  • Such polyol may be selected from any of the chemical classes of polyols that can be used in polyurethane synthesis.
  • the polyol may be a polyester polyol, a polyesteramide polyol, a polyether polyol, a polythioether polyol, a polycarbonate polyol, a polyacetal polyol, a polyvinyl polyol and/or a polysiloxane polyol.
  • the polyol is selected from
  • polyester(amide) polyol polyether polyol or polycarbonate polyol.
  • the molar ratio of hydrazide groups (present in the dihydrazide functional compound (vii)) to ketone groups is from 1.5 to 0.1 , preferably from 1 .2 to 0.2, more preferably from 0.9 to 0.25.
  • the molar ratio of hydrazide groups (present in the dihydrazide functional compound (vii)) to ketone groups is determined by calculation as known in the art. For the sake of clarity, the calculation is illustrated in the experimental part of the description
  • the at least one active-hydrogen containing chain extending compound that is reacted with the polyurethane prepolymer to obtain the polyurethane of the polyurethane-vinyl polymer hybrid is preferably selected from the group consisting of hydrazine, ethylene-1 ,2-dihydrazine, propylene-1 ,3-dihydrazine, butylene- 1 ,4-dihydrazine, and any mixture thereof. More preferably, the active-hydrogen containing chain extending compound is hydrazine. Another preferred active-hydrogen containing chain extending compound is water.
  • the molar ratio of active hydrogens in the chain extending compound to isocyanate groups in the polyurethane prepolymer is preferably in the range from 0.75 to 0.99 stoichiometric amount and more preferably from 0.8 to 0.93 stoichiometric amount.
  • the polyurethane and the vinyl polymer in the polyurethane and the vinyl polymer hybrid are present in a weight ratio of polyurethane to vinyl polymer ranging from 90:10 to 35:65, preferably from 80:20 to 40:60, more preferably from
  • the weight ratio of polyurethane to vinyl polymer in the polyurethane-vinyl polymer hybrid is calculated as known in the art and is further illustrated in the experimental part.
  • the aqueous coating composition according to the invention may comprise co-solvent preferably in an amount of less than 10 wt.% of co-solvent by weight of solids, more preferably less than 7 wt.% of co-solvent by weight of solids, even more preferably less than 5 wt.% of co-solvent by weight of solids, even more preferably less than 2 wt.% of co-solvent by weight of solids and most preferably 0 wt.% of co-solvent by weight of solids.
  • a co-solvent is an organic solvent employed in an aqueous composition to ameliorate the drying characteristics thereof, and in particular to lower its minimum film forming temperature.
  • the co-solvent may be incorporated during preparation of the polyurethane-vinyl polymer hybrid or may have been added during formulation of the aqueous
  • Non-limiting examples of co-solvents include the mono- and di-alkyl ethers or esters of (di- or tri-)ethylene and (di- or tri-)propylene glycols like propylene glycol n-butyl ether (PnB), Dipropylene glycol n-butyl ether (DPnB), Dipropylene glycol methyl ether acetate (DPMA), Tripropylene glycol methyl ether (TPM), Propylene glycol methyl ether (PM), Propylene glycol methyl ether acetate (PMA), Dipropylene glycol methyl ether (DPM) and mixtures thereof.
  • co-solvents include the mono- and di-alkyl ethers or esters of (di- or tri-)ethylene and (di- or tri-)propylene glycols like propylene glycol n-butyl ether (PnB), Dipropylene glycol n-butyl ether (DPnB), Di
  • the amount of co-solvent 1 -methyl-2- pyrrolidinone in the aqueous coating composition is preferably less than 10 wt.% by weight of solids, preferably less than 5 wt.%, more preferably less than 0.5 wt.% and even more preferably is 0 wt.%.
  • the aqueous coating composition according to the invention comprises the dispersed polyurethane-vinyl polymer hybrid particles preferably in an amount of from 20 to 55 wt.%, more preferably in an amount of from 25 to 50 wt.% and most preferably in an amount of from 25 to 40 wt.% (relative to the aqueous coating composition).
  • the aqueous coating composition of the present invention preferably has pH of is at least 7, preferably from 7.5 to 8 since such compositions give less discoloration of wooden substrate.
  • the aqueous composition of the invention may contain conventional ingredients, examples include pigments, dyes, emulsifiers, surfactants, associative thickeners, heat stabilizers, matting agents, inhibitors, UV absorbers, antioxidants, drier salts, wetting agents, defoamers, fungicides, bacteriocides and the like introduced at any stage of the production process or subsequently.
  • the aqueous coating composition according to the invention typically has a solids content of from 20 to 50 % by weight, more usually from 25 to 48 % by weight and especially from 30 to 45 % by weight.
  • the present invention further relates to a process for preparing an aqueous coating composition according to any of the preceding claims comprising the following steps
  • step I adding from 0 to 35wt.% of vinyl monomer in step I, where the amounts of (a), (b), (c), (d) and (e) are given relative to the total amount of components used to prepare the isocyanate-terminated polyurethane prepolymer from which the building blocks from the isocyanate-terminated polyurethane prepolymer are emanated, and where the amount of (f) is given relative to (a) to (f);
  • step I and/or step III and the amount of vinyl monomer added in the process is preferably such that the weight ratio of the polyurethane to the vinyl polymer in the polyurethane-vinyl polymer hybrid ranges from 90:10 to 35:65.
  • Some or all of the vinyl monomers may be present at the
  • commencement of the preparation of the isocyanate-terminated prepolymer or some or all of the vinyl monomers may be added during the course of the preparation, or some or all of the vinyl monomers may be added after having prepared the isocyanate- terminated prepolymer or some or all of the vinyl monomers may be added to the aqueous phase in which the urethane prepolymer is dispersed or some or all of the vinyl monomers may be added to the aqueous dispersion of the chain extended polyurethane (so after step II) in which case the vinyl monomer(s) swell into the chain extended polyurethane particles.
  • step IV is preferably effected after step I and step II and in case step III is not optional, step IV is effected before step III, together with step III and/or after step III.
  • At least a part of the vinyl monomers added in the process according to the invention contain ketone groups.
  • the amount of vinyl monomers containing ketone groups added in the process of the invention is preferably such that the molar amount of ketone groups in the vinyl polymer to the total molar amount of ketone groups in the polyurethane-vinyl polymer hybrid is from 40% to 95%, more preferably from 55% to 90% and most preferred from 70% to 85%.
  • neutralizing and chain extending the isocyanate-terminated polyurethane prepolymer is effected by blending of the isocyanate-terminated polyurethane prepolymer with an aqueous phase comprising neutralization agent and chain extending compound.
  • said blending is effected by adding the isocyanate-terminated polyurethane prepolymer to an aqueous phase comprising neutralization agent and chain extending compound.
  • the aqueous composition of the invention is particularly useful for providing the principle component of coating compositions (e.g. protective or decorative coating compositions) especially for coating compositions on substrates made from wood, metal, plastic, concrete, glass and any combination thereof and in particular for coating compositions on wood substrates, especially oak substrates.
  • coating compositions e.g. protective or decorative coating compositions
  • Preferred substrates are floor, furniture and kitchen cabinets, in particular wooden floor, wooden furniture and wooden kitchen cabinets.
  • a coating obtained by (i) applying an aqueous coating composition according the invention to a substrate and (ii) drying the aqueous coating composition by evaporation of volatiles to obtain a coating, whereby no additional chemical crosslinking reaction is needed after having applied the coating composition on the substrate like for example UV curing and/or curing with the aid of a crosslinker.
  • the aqueous coating composition according to the present invention allows to obtain a coating solely by drying the aqueous coating composition by evaporation of volatiles; a crosslinker and/or external curing trigger such as UV-radiation is not needed.
  • the present invention therefore also relates to a substrate having a coating obtained by (i) applying an aqueous coating composition according to the invention to a substrate in particular as described above and (ii) drying the aqueous coating composition by evaporation of volatiles.
  • Ketone functional polyol ketone-functional polyester polyol available from DSM, which has a hydroxyl value of 80 mg KOH/g and an acid value of ⁇ 5 mg KOH/g.
  • the ketone functionality is 1.7 milli-equivalents ketone groups per g polyol.
  • Fe(lll)(EDTA) Iron-ethylenediaminetetracetic acid complex 1 % in water Inhibitor 2,6-Di-tert-butyl-4-methylphenol available from Avecia Inc Acetone dimethyl ketone available from Aldrich
  • composition (wt.%) 33.30 32.92 32.84 33.00 Procedure for obtaining the aqueous coating compositions of Comparative
  • the weight polyurethane-vinyl polymer hybrid in this calculation is defined as the sum of all raw materials that form together the polymer composition. Hence, in this calculation isocyanates, polyols, chain extending compound, neutralizing agent and vinyl monomers are included. Water, surfactant, defoamers, preservatives and other additives used in the process for preparing the polyurethane-vinyl polymer hybrid are excluded in this calculation.
  • DAAM Molecular weight ketone functional vinyl monomer
  • Weight ketone functional components used for preparing the polyurethane 0 g
  • polyurethane-vinyl polymer hybrid 175 mmol/kg
  • polyurethane-vinyl polymer hybrid 274 mmol/kg
  • aqueous coating composition is brushed on an oak panel to obtain a wet film and the coating is allowed to dry on a flat surface for a minimum of 2 hours. Slightly sand the panel with sanding paper till all grain raising is gone. After sanding apply the second layer with a brush. Again allow the coating to dry for a minimum of 2 hours on a flat surface. After drying, age the panel at room temperature for 1 week. Performance and wood coloration is tested after ageing.
  • the black heel mark resistance is tested by striking the coated surface with a heel, hit the coating with the heel (manual force). Wipe the affected area with a tissue (very soft, just to remove the loose rubber parts) to determine how much carbon black can be removed.
  • micro scratch resistance is tested by applying a coating layer of 80 micron wet by wire rod on a Leneta test cards and dry for 24 hours on a flat surface. Age cards for 1 week at room temperature. Determine micro scratch resistance using a felt-pad on the black parts of the test panels using Satra Rub tester using 24.5N weight on top of the rub tester. Check gloss level after every (increasing) 500 revolutions. Gloss level of the coating should not change.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
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Abstract

La présente invention concerne une composition de revêtement aqueuse comprenant des particules d'hybride de polyuréthane-polymère de vinyle dispersées, i. l'hybride polyuréthane-polymère de vinyle étant obtenu par polymérisation radicalaire d'au moins un monomère de vinyle en présence d'un polyuréthane, ii. le polyuréthane étant obtenu par la réaction d'au moins (I) un prépolymère de polyuréthane à terminaison isocyanate et (II) d'au moins un composé extenseur de chaîne contenant de l'hydrogène actif, le prépolymère de polyuréthane à terminaison isocyanate étant obtenu par la réaction d'au moins un polyol avec au moins un polyisocyanate, de 50 à 100 % en poids de la quantité totale des polyisocyanates utilisés pour former le polyuréthane étant des polyisocyanates aromatiques, iii. l'hybride polyuréthane-polymère de vinyle ayant une fonctionnalité cétone et contenant de 50 à 1000 mmol de groupes cétone pour 1 000 g d'hybride polyuréthane-polymère de vinyle, de préférence de 75 à 500 mmol de groupes de cétone pour 1 000 g d'hybride polyuréthane-polymère de vinyle, de manière davantage préférée de 150 à 400 mmol de groupes de cétone pour 1 000 g d'hybride polyuréthane-polymère de vinyle, iv. les groupes cétone de l'hybride polyuréthane-polymère de vinyle étant présents dans le polyuréthane et dans le polymère de vinyle, v. le rapport en poids du polyuréthane sur le polymère de vinyle dans l'hybride polyuréthane-polymère de vinyle étant compris entre 90/10 et 35/65, vi. l'hybride polyuréthane-polymère de vinyle ayant un indice d'acide de 7 à 60 mg KOH/g d'hybride polyuréthane-polymère de vinyle, de préférence de 9 à 40 mg KOH/g d'hybride polyuréthane-polymère de vinyle et idéalement de 12 à 25 mg KOH/g d'hybride polyuréthane-polymère de vinyle, vii. la composition de revêtement aqueuse comprenant un composé à fonctionnalité dihydrazide (contenant deux groupes hydrazide (O = C-NHNH2)) ayant une masse molaire inférieure à 1 000 g/mole, viii. le rapport molaire des groupes hydrazide (présents dans le composé à fonctionnalité dihydrazide (vii)) sur les groupes cétone étant de 1,5 à 0,1 (de préférence de 1,2 à 0,2, de manière davantage préférée de 0,9 à 0,25).
EP17710304.1A 2016-03-15 2017-03-15 Composition de revêtement aqueuse Withdrawn EP3430063A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP2016160503 2016-03-15
EP2016160501 2016-03-15
PCT/EP2017/056112 WO2017158016A1 (fr) 2016-03-15 2017-03-15 Composition de revêtement aqueuse

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EP3430063A1 true EP3430063A1 (fr) 2019-01-23

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