WO2015052214A1 - Polymère, composition et utilisation - Google Patents

Polymère, composition et utilisation Download PDF

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Publication number
WO2015052214A1
WO2015052214A1 PCT/EP2014/071504 EP2014071504W WO2015052214A1 WO 2015052214 A1 WO2015052214 A1 WO 2015052214A1 EP 2014071504 W EP2014071504 W EP 2014071504W WO 2015052214 A1 WO2015052214 A1 WO 2015052214A1
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Prior art keywords
weight
component
crosslinking
anionic
polyurethane
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PCT/EP2014/071504
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English (en)
Inventor
Ronald Tennebroek
Roel Johannes Marinus Swaans
DE Paul KOK
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Dsm Ip Assets B.V.
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Publication of WO2015052214A1 publication Critical patent/WO2015052214A1/fr

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Classifications

    • 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
    • C08G18/10—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
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C08G18/3231—Hydrazine or derivatives thereof
    • 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
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to the field of polyurethanes especially urethane-acrylic based dispersions.
  • Urethane-acrylic (U-A) dispersions have good resistance to water, chemicals, solvents and abrasion and so are commonly used in coating compositions such as decorative and protective coatings.
  • both the acrylic part and the polyurethane (PU) part must be dispersed in water.
  • suitable groups such as ionic or non-ionic hydrophilic groups in the polyurethane polymer either pendant to the polymer chain or in-chain.
  • groups include anions such as carboxylic, sulfonic, sulphate or phosphate groups that are typically incorporated into the PU by reacting compounds containing reactive hydrogen and at least one suitable acid group (typically a carboxylic acid) with polyisocyanate to form the polyurethane component of the urethane-acrylic dispersion. It is undesirable that large amounts of acidic materials remain in the resultant dispersion thus a substantial part (if not all) of the acid present must be neutralised in the final product.
  • volatile amines also have various disadvantages. For example they readily evaporate volatile organic compounds (VOC) during the film formation causing unacceptable environmental pollution and/or poor indoor air quality when used indoors. The use of such materials may be more strictly regulated in the future. Therefore it is desirable to find an alternative method of providing stable aqueous urethane-acrylic dispersions and/or neutralising acidic materials used during their preparation.
  • VOC volatile organic compounds
  • US 2968575 describes a PU latex dispersed in water using an emulsifier.
  • US 4,501 ,852 describes stable aqueous dispersions of polyurethane- ureas containing (i) 10-120 meq per 100 g of anionic groups chemically incorporated therein and (ii) up to about 10% by weight of hydrophilic chains containing ethylene oxide (EO) units.
  • the formulation contains a mixture of volatile and non volatile cations in a equivalent ratio from about 1 :4 to 4:1.
  • component (ii) a nonionic polyether monoalcohol of n-butanol, ethylene oxide and propylene oxide (in a molar ratio 83:17) having an OH-number of 26. This component aids dispersion but increases water sensitivity.
  • the examples also use the undesirable NMP as a solvent.
  • US 4,701 ,480 describes aqueous polyurethane-urea dispersions with improved hydrolytic stability formed from an aqueous polyurethane-urea-dispersion containing carboxylic acid groups neutralized with volatile organic bases which are then converted to non volatile cations by adding alkali metal salts of organic or inorganic acids in an amount sufficient to displace at least a portion of the volatile organic bases.
  • the volatile organic bases may be optionally removed by distillation under reduced pressure. All the examples contain NMP and distillation is undesirable because it uses large amounts of energy and may cause excessive foaming (as described in Example XVI of US 2010/0099967).
  • US 2010-0098867 (Costa) describes a method of making aqueous dispersions of carboxylated anionic polyurethanes that are free of volatile amines and do not contain any polyoxyethylene or polyoxypropylene side chains.
  • a prepolymer (containing 2-10% by weight of isocyanate groups and 10-100 meq of carboxylic groups) is prepared by reacting: a polyol with a carboxylic acid group; a non ionic polyol, and a (cyclo)aliphatic polyisocyanate.
  • the prepolymer is dispersed in an aqueous solution of an alkaline metal hydroxide and then the prepolymer is chain extended with a polyamine.
  • EP1 153051 describes aqueous dispersions of anionic polyurethanes with pendant carboxylic acid groups that are neutralised with a reactive volatile amine compound (tertiary aminofunctional acrylic monomer (DMAEMA)) that is subsequently incorporated in the polymer backbone by radical polymerization. Unreacted free monomer remains in the final product which thus still contains volatile amines.
  • the monomer may also contain impurities in the monomer and hydrolysis may generate the undesirable side product dimethylethanol amine.
  • W093/24551 describes an aqueous polyurethane polymer dispersion comprising the reaction product of: organic polyisocyanate; polyester polyol which incorporate polymerized units derived from dimer acid; nonionic and/or ionic dispersing groups and at least one of the following polymerized units: cyclo-aliphatic polyol of molecular weight (Mw) ⁇ 400; cyclo-aliphatic polyacid of MW ⁇ 400, aromatic polyol MW ⁇ 500, aromatic diacid Mw ⁇ 500 and an active hydrogen chain extending compound.
  • Mw molecular weight
  • WO 2001 -027179 (Stahl) describes an anionic polyurethane dispersion which is neutralised by a tertiary amine functional urethane polymer or oligomer.
  • the polymeric material is less volatile than reagents such as TEA, this method adds extra expense and complexity to preparation of the PU dispersion and is not completely successful at removing all acidic groups.
  • PCT/EP2013/057457 (claiming priority from EP12163513.0) and PCT/EP2013/057455 (claiming priority from EP12163515.5) discloses similar compositions to those described herein, but where the component three is not specified to be hydrophobic (especially as hydrophobic is defined herein).
  • the invention comprises a process for preparing an aqueous dispersion of a polyurethane A the process comprising the steps of:
  • (1 ) component one comprises 10 to 80% by weight of at least one
  • polyisocyanate optionally containing at least one anionic or potentially anionic dispersing group
  • optional component two comprises up to 15% by weight of at least one isocyanate-reactive polyol containing at least one anionic or potentially anionic dispersing group;
  • component three comprises 15 to 85% by weight of at least one
  • isocyanate reactive hydrophobic polyol and having a weight average molecular weight greater than or equal to 500 Daltons optionally containing at least one anionic or potentially anionic dispersing group;
  • optional component four comprises up to 20% by weight of at least one isocyanate reactive polyol other than component three and two if present and having a weight average molecular weight less than 500 Daltons;
  • component two is not present component one or three contains at least one anionic or potentially anionic dispersing group;
  • step (a) where the mixture used in step (a) is substantially free of volatile amines and N-alkyl pyrrolidinones;
  • step (b) adding to the reaction mixture from step (a) an alkali metal neutralising agent in an amount from 0.05 to 6 parts by weight substantially to neutralise the isocyanate terminated prepolymer obtained from step (a); where the amount (in weight parts) of the alkali metal neutralising agent is calculated based on the weight of alkali metal in the neutralising agent relative to the total amount of components one to four in step (a) being equal to 100 parts by weight; and
  • step (c) reacting the neutralised prepolymer from step (b) with an active hydrogen compound to extend the chain of the prepolymer to form an aqueous dispersion of polyurethane A;
  • the aqueous dispersion of polyurethane A is crosslinkable preferably by a crosslinking method selected from: silane-crosslinking, UV-crosslinking, auto-oxidative crosslinking, isocyanate crosslinking, carbodiimide crosslinking and/or Schiff base cross-linking between carbonyl groups and polyamine and/or polyhydrazide compounds.
  • a crosslinking method selected from: silane-crosslinking, UV-crosslinking, auto-oxidative crosslinking, isocyanate crosslinking, carbodiimide crosslinking and/or Schiff base cross-linking between carbonyl groups and polyamine and/or polyhydrazide compounds.
  • polyurethane A is mixed with a vinyl polymer B (as described later) and the vinyl polymer B is cross-linked as described above then polyurethane A may optionally not be cross-linked as long as at least one of polyurethane A and vinyl polymer B are crosslinked. Schiff base crosslinking is preferred, especially of the vinyl polymer B.
  • the process of the invention is free of tin catalysts, more preferably comprises catalysts selected from no catalyst and/or carboxylates of zinc, zirconium, copper, bismuth, titanium and/or molybdenum, most preferably is substantially free of any catalysts for any of the reaction steps.
  • hydrophobic denotes that a moiety (e.g. a molecule or part thereof) is a hydrophobe, a term which is well understood by those skilled in the art.
  • Hydrophobes are usually substantially immiscible with (preferably insoluble in) water.
  • Usefully hydrophobes may also be lipophilic, that is substantially miscible with (preferably soluble in) fats, oils, lipids, and/or non-polar materials such as hexane and/or toulene. More preferred hydrophobes are themselves substantially non polar or have a low polarity (for example may have a net difference in electronegativity between the atoms of the moiety of from 0 to 0.4 on the Pauling scale).
  • Hydrophobes may also exhibit a high (>90°C) water contact angle (preferably > 100°C, more preferably > 120°C, most preferably > 150°C) when liquid water is applied to their surface.
  • Hydrophobicity denotes a relative property of a material. Therefore unless expressly stated herein it may not always be possible to set an absolute borderline between a hydrophobe and hydrophile.
  • the relative and/or absolute hydrophobic character of a component, composition, monomer, oligomer and/or polymer described herein can nevertheless be determined by several different well known methods available to the person skilled in the art. Surface tension is one such method, water breakthrough pressure is another.
  • a micro-porous membrane can prepared identically but from two different materials. The water flux through each membrane can be independently and separately measured by any suitable technique well-known to those skilled in the art to determine which of the test materials is relatively the more hydrophobic.
  • Surface tension is another appropriate physical property that may be generally used to distinguish a hydrophobe from a hydrophile.
  • surface tensions of materials such as polymers can be accurately determined by observing whether or not droplets of liquids such as water spontaneously spread on their surface (spreading indicates a hydrophile).
  • a material is denoted herein as hydrophobic (such as the hydrophobic polyols of component three) when it exhibits a water contact angle of more than 90° (preferably > 100°C, more preferably > 120°C, for example > 150°C).
  • the hydrophobic polyol(s) of component three are hydrophobic insofar as relative to the other components one to four, they have a more hydrophobic character than any of the other components one, two and/or four that are present.
  • hydrophobic polyol(s) of component three are hydrophobic insofar as they have an absolute hydrophobicity measured by having a water contact angle of at least 90°C.
  • hydrophobic polyol(s) of component three are hydrophobic relative to the other components one to four and also by having a water contact angle of at least 90°C.
  • optional component two is a non-hydrophobe, but if component two is hydrophobic then component three and component two are not the same.
  • hydrophile and non-hydrophobe are used synonymously.
  • step (a) comprises:
  • step (b) occurs during or substantially immediately after step (a).
  • the metal cation from the alkali metal neutralising agent forms a counterion for the anionic group thereon (and/or anionic group formed from the potential anionic groups thereon)
  • a further aspect of the invention provides a process for preparing an aqueous coating composition comprising bringing into initimate admixture components (i) and (ii):
  • composition (and both components (i) and (ii)) are substantially free of volatile amines and N-alkyl pyrrolidinones;
  • At least one of the aqueous dispersion of polyurethane A and/or the vinyl polymer B is crosslinkable preferably by a crosslinking method selected from: silane-crosslinking, UV-crosslinking, auto-oxidative crosslinking, isocyanate crosslinking, carbodiimide crosslinking and/or Schiff base cross-linking between carbonyl groups and polyamine and/or polyhydrazide compounds.
  • a crosslinking method selected from: silane-crosslinking, UV-crosslinking, auto-oxidative crosslinking, isocyanate crosslinking, carbodiimide crosslinking and/or Schiff base cross-linking between carbonyl groups and polyamine and/or polyhydrazide compounds.
  • the Tg of polymer B preferably is greater than -10°C, preferably greater than 0°C, most preferred > 15°C.
  • the glass transition temperature of a polymer is the temperature at which it changes from a glassy, brittle state to a plastic, rubbery state.
  • the glass transition temperatures may be determined experimentally using differential scanning calorimetry DSC, taking the peak of the derivative curve as Tg, or calculated from the Fox equation.
  • Tg in degrees Kelvin, of a copolymer having "n" copolymerised comonomers is given by the wt fractions W of each comonomer type and the Tg's of the homopolymers (in degrees Kelvin) derived from each comonomer according to the equation:
  • the calculated Tg in degrees Kelvin may be readily converted to °C.
  • both components (i) and (ii) form different phases which are present in the same particles.
  • the weight percentage of each of these components in the compositions of the invention may be as follows.
  • component (1 ) (the polyisocyanate) is present in an amount from 15% to 70%, more preferably from 20% to 60%, most preferably 25% to 50% by weight.
  • component (2) (the anioinic isocyanate-reactive polyol) is present in an amount from 2% to 12%, more preferably from 3% to 10%, most preferably 4% to 7% by weight.
  • component (3) (the high (>500D) mw isocyanate-reactive hydrophobic polyol) is present in an amount from 20% to 80%, more preferably from 25% to 75%, most preferably 30% to 60% by weight.
  • Preferably optional component (4) (the low ( ⁇ 500D) mw isocyanate- reactive polyol) is present in an amount from 0.5% to 20%, more preferably from 1 % to 15%, most preferably 2% to 10% by weight.
  • the preceding components may also be present in the same number amounts given above where the percentages are replaced by relative parts by weight.
  • the amount of other components in the compositions of the invention expressed as parts per weight may be as follows.
  • Preferably optional component (5) (the alkali metal neutralising agent) may be present in an amount from 0.1 to 6, more preferably from 0.2 to 5, most preferably 0.5 to 4 parts by weight.
  • optional components (6) may be present in a total amount from 0.1 to 20, more preferably from 0.2 to 10, most preferably 0.5 to 5 parts by weight.
  • the preceding components may also be present in the same number amounts given above where the relative parts by weight are replaced by weight percentages based on the total amount of all the components being 100%.
  • alkali metal neutralising agent denotes an alkali metal compound, preferably an alkali metal salt, that is sufficiently basic under the conditions (under which the polyurethane dispersion is prepared) to neutralise the acidic groups on the polymer.
  • ions from the alkali metal neutralising agent act as counter ions to ionic groups formed from acidic groups on the polymer.
  • Preferred alkali metal salts comprise cations such as potassium, sodium and/or lithium with sodium being more preferred.
  • Preferred alkali metals salt comprise anions such as carbonate, bicarbonate, hydroxide and/or hydride, with hydroxide being more preferred.
  • the most preferred alkali metal neutralising agents are sodium and/or potassium hydroxide.
  • polyurethane dispersions of the invention may (unless indicated otherwise herein) be prepared conventionally using conventional polyols and isocyanates.
  • polyisocyanate used in the present invention as component one may be selected from those described in WO2007-006586 as polyisocyanate component (i) (see from page 7, line 33 to page 8, line 20 - this passage incorporated herein by reference).
  • NCO-reactive polyols used in the present invention as components two, three and four (subject to the other requirements for these components specified herein) may be selected from those described in WO2007- 006586 as components (ii), (iii) and/or (iv) (see from page 8, line 30 to page 9, line 24 - this passage also incorporated herein by reference)
  • Component one comprises a polyisocyanate.
  • Suitable polyisocyanates may comprise aliphatic, cycloaliphatic, araliphatic, aromatic and/or polyisocyanates modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine, urethdione or isocyanurate residues.
  • polyisocyanates examples include ethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1 , 4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, p-xylylene diisocyanate, ⁇ , ⁇ '-tetramethylxylene diisocyanate, 1 ,4- phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'- diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanates, 2,4'- diphenylmethane diisocyanate, 3(4)-isocyanatomethyl-1 -methyl cyclohexyl isocyanate, 1 ,5-naphthylene diisocyanate and mixtures thereof.
  • Preferred polyisocyanates are isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, toluenediisocyanate and 4,4'-diphenylmethane diisocyanate.
  • Components two, three and four comprises various polyols as defined herein.
  • Suitable polyols may comprise propylene glycols, poly(propylene
  • oxide/ethylene oxide copolymers polytetrahydrofuran, polybutadiene, hydrogenated polybutadiene, poysiloxane, polyamide polyesters, isocyanate-reactive polyoxyethylene compounds, polyester, polyether, polyether ester, polycaprolactone, polythioether, polycarbonate, polyethercarbonate, polyacetal and polyolefin polyols.
  • component two comprises a polyol with an anionic or potential anionic dispersing group thereon.
  • Preferred anionic dispersing groups are carboxylic, phosphate, phosphonate or sulphonic acid groups.
  • Preferred potentially anionic dispersing groups are precursors for the anionic dispersing groups described herein, i.e. groups which under the conditions of step (a) will transform into the anionic dispersing groups.
  • Most preferred anionic dispersing groups are carboxylic or sulphonic acid groups.
  • Conversion to the salt form is achieved by neutralisation of anionic groups with an alkali metal neutralising agent during step (b). Most preferably dimethylol propanoic acid is used.
  • Component three comprises an isocyanate reactive hydrophobic polyol with a weight average molecular weight of greater than 500 daltons (high mw polyol).
  • component three comprises polyols that (calculated based on the weight of the polyol being 100 wt%) comprise > 10 wt%, more preferably >20 wt%, even more preferably >30 wt%, most preferably > 40 wt% of diacids and/or dialcohols containing hydrophobic hydrocarbo moieties.
  • the hydrocarbo moiet(ies) may comprise 8 or more carbon atoms, usefully have from 8 to 50, more usefully from 12 to 44 and most usefully from 16 to 36 carbon atoms.
  • component three comprises polyols that comprise > 10 wt %, more preferably > 20 wt% thread even more preferably >30 wt % and most preferably >40 wt% of a dimer fatty acid (calculated based on the weight of the polyol being 100 wt%).
  • weight average molecular weight of a polymer is determined using Size Exclusion Chromatography performed on a Waters Alliance 2695 (pump, degasser and autosampler) with a Waters 410 differential refractive index detector and Shimadzu CTO-20AC column oven.
  • the eluent was 1 ,1 ,1 ,3,3,3 hexafluoro isopropanol (HFIP) with the addition of 0.2M potassium trifluoro actetate (PTFA).
  • the injection volume was 50 ⁇ .
  • the flow was established at 0.8 ml/min.
  • Two PSS PFG Linear XL columns Polymer Standards Service
  • PG PSS guard column
  • the detection was performed with a differential refractive index detector.
  • the sample solutions were prepared with a concentration of 5 mg solids in 2 ml HFIP (+ 0.2M PTFA), and the samples were dissolved for a period of 24 hours.
  • Calibration is performed with eleven polymethyl methacrylate standards (polymer standard services), ranging from 500 to 2,000,000 g/mol.
  • the calculation was performed with Empower 3 software (Waters) with a third order calibration curve.
  • the molar mass distribution is obtained via conventional calibration and the molar masses are polymethyl methacrylate equivalent molar masses (g/mol).
  • component three comprises carbonate moieties that (calculated based on the weight of the carbonate moiety being 100 wt%) comprise > 10 wt%, more preferably >20 wt%, even more preferably >30 wt%, most preferably > 40 wt% of dialcohols that comprise hydrocarbo moieties.
  • the hydrocarbo moiet(ies) may comprise 8 or more carbon atoms, usefully have from 10 to 50, more usefully from 12 to 46, even more usefully from 16 to 44 and most usefully from 22 to 36 carbon atoms.
  • the carbon atoms in such hydrocarbon moieties may form a carbon chain
  • Preferred polyols that comprise component four may have one or more of the following properties: comprise short chains that impart greater rigidity to the resultant polyurethane A.
  • the molecular weight is below 500 Dalton, more preferably below 350 Dalton, most preferably 250 Daltons (typical examples are neopentylglycol, cyclohexane dimethanol, hexane diol, trimethylolpropane)
  • the acrylic urethane of the invention and/or prepared according to the process of the invention is substantially free of any non-ionic functional polyols as it is believed that such components may deteriorate water resistance.
  • the polyurethane dispersions (PUD) and/or the urethane acrylics of or prepared in the present invention are permanently basic (i.e. after neutralisation with the alkali metal neutralising agent), preferably exhibiting a pH of > 8.
  • PUDs and urethane acrylic coatings with a high pH were thought to be undesirable, the applicant has surprisingly found that they may solve some or all of the problems identified herein.
  • additional surfactant may be added to facilitate dispersing the urethane however this is not preferred as it has a detrimental effect on the water resistance.
  • the neutralising agent is added to the prepolymer as by pre-neutralizing the prepolymer urethanes with lower acid values can be synthesized which have improved water resistance. More preferably the neutralizing agent is added as aqueous solution to the prepolymer.
  • compositions of the invention have low acid values (AV), preferably the AV of the total composition is from 1 to 40 mg KOH / g, more preferably 2-20 mg KOH/g, most preferably 3-15 mg KOH/g.
  • AV low acid values
  • (alkali) metal ion neutralized urethane-acrylic based dispersions contain sufficient hydrophobic polyols to compensate for the deteriorated chemical stain resistances, specifically water resistance and optionally may also be made without a tin catalyst so the composition may be tin free.
  • Such urethane acrylic dispersions may be
  • a special embodiment of the present invention is a tin free aqueous dispersion of polyurethane A and optionally vinyl polymer B wherein said polyurethane A is prepared from components 1 , 2, 3 and optionally 4.
  • These dispersions can be prepared without using any catalyst or alternatively carboxylates of zinc, zirconium, copper, bismuth, titanium and molybdenum may be employed as catalysts.
  • Another special embodiment of the present invention is a tin free aqueous dispersion of polyurethane A and optionally vinyl polymer B wherein said polyurethane A is prepared from tin free components 2, 3 and optionally 4.
  • These components can be prepared without using any catalysts, via enzymatic catalysis or alternatively sulfonic acids or titanates may be employed as catalysts.
  • Another special embodiment of the present invention is an aqueous dispersion of polyurethane A and optionally vinyl polymer B wherein said polyurethane A is prepared from components 2 and/or 3 where the anionic dispersing group is a metal salt of a sulfonic acid (RS0 3 H) group.
  • the anionic dispersing group is a metal salt of a sulfonic acid (RS0 3 H) group.
  • Preferred are the Li, Na and K salts of sulphonated isophtalic acid.
  • Another special embodiment of the present invention is an aqueous dispersion of polyurethane A and optionally vinyl polymer B wherein the polyurethane A and/or the vinyl polymer B are crosslinkable.
  • Suitable types of crosslinking are silane- crosslinking, UV-crosslinking, auto-oxidative crosslinking, isocyanate crosslinking, carbodiimide crosslinking, Schiff base cross-linking between carbonyl groups and polyamine or polyhydrazide compounds and other methods known to those skilled in the art.
  • DMPA dimethylolpropionic acid
  • MMA methyl methacrylate
  • n-BA n-butylacrylate
  • EDTA ethylenediamine tetraacetic acid Viscosity was determined with a Brookfield DV-I viscometer (spindle S61 , 60 rpm, 23°C)
  • Particle size distribution was measured on a Particle Size Distribution Analyser (PSDA) from Polymer Laboratories. Samples are diluted until a concentration of approximately 0,05%. Samples are filtered over 2 micron filtered and measured on Cartridge Type 2 (20nm to 1500nm).
  • PSDA Particle Size Distribution Analyser
  • PL-PSDA Eluent concentrate 0.04% Sodium azide solution (Polymer
  • PL-PSDA Marker 0.02 g 3-nitrobenzene sulfonic acid in 250ml Ultra pure water.
  • Latex Particle Size Standards from 2-1000 nm; KSTN0026, KSTN 0027, KSTN0028 and KSTN0033 t/m KSTN0039
  • Syringe filters regenerated cellulose, 0.45 ⁇ membrane, Spartac Millex-AP 20 pre filter 25 MM, 2.0 ⁇ membrane, Millipore.
  • the median diameter is mentioned in the examples.
  • the diameter at peak value is mentioned.
  • a reaction vessel equipped with internal thermometer, stirrer and cooler, was filled, under nitrogen atmosphere and at room temperature, with 442.6 g of polypropylene ether glycol (having molecular weight 2,000 g/mol), 30.9 g of DMPA and 50.0 g of N-methylpyrrolidone.
  • the mixture was heated to 40 °C and stirred for 30 minutes.
  • 213.2 g Desmodur W available from Bayer was added under stirring to the homogeneous mixture which was then heated to 60°C for 30 minutes.
  • the reaction temperature was brought to 100°C and maintained for 2 hours, until the titrimetric determination of the free NCO groups still present gave a calculated value of 4.12% by weight.
  • 650 g of the obtained prepolymer, cooled to 65°C, are dispersed in 10 minutes under vigorous stirring into 1057.1 g of demineralised water cooled at 18°C and containing 10.84 g of potassium hydroxide. 65.2 g of a 15.5% aqueous solution of hydrazine are added in 10 minutes and a maximum temperature of 34°C is reached during the extension step. After 30 minutes stirring, the NCO peak in the IR spectrum at 2240 cm "1 is disappeared and 1.780 g of BYK® 346 are added.
  • the resulting amine free (but N-methyl pyrrolidone containing) polyurethane dispersion had a solids content of 34.3 wt %, a pH of 8.0 and a viscosity of 66 cps.
  • the median particle size was 170 nm.
  • the isocyanate content of the prepolymer was 4.99% (theoretical 5.12%).
  • 528.23 g of the obtained prepolymer was cooled to a temperature of 40°C and 186.65 g of a 5.68% KOH solution in demineralized water was added under vigorous stirring. Subsequently 744.78 g of demineralized water was added to the flask and the mixture was stirred until a homogeneous dispersion was obtained. After that, 53.19 g of a 15.5% hydrazine solution was added together with 17.6 g of water.
  • the radical polymerization was initiated by the addition of 0.74 g of tertiary butyl hydroperoxide, 0.02 g of iron(ll)EDTA and a subsequent feed addition of 26.4 g of a 1 % solution of isoascorbic acid in demineralized water, over a period of 10 minutes.
  • the batch was filtered through a filter cloth to remove any coagulum formed during the reaction.
  • the resulting amine free polyurethane acrylic hybrid dispersion had a solids content of 34.3 wt %, a pH of 7.7 and a viscosity of 15 cps.
  • the median particle size was 59 nm.
  • a polyester polyol was synthesized from the following components: Pripol 1009 (available from Croda, 49 wt%), adipic acid (12 wt%) and 1 ,4 cyclohexane dimethanol (39 wt%).
  • the polyester polyol had a hydroxyl value of 1 13 mg KOH/g and an acid value of 0.47 mg KOH/g.
  • the batch was filtered through a filter cloth to remove any coagulum formed during the reaction.
  • the resulting amine free polyurethane acrylic hybrid dispersion had a solids content of 34.8 wt %, a pH of 7.9 and a viscosity of 12 cps.
  • PEC-205 is a ketone-functional polyester polyol, available from DSM, which has a hydroxyl value of 80 mg KOH/g and an acid value of ⁇ 1 mg KOH/g.
  • the ketone functionality is 1.7 milliequivalents carbonyl groups per g polyol.
  • the radical polymerization was initiated by the addition of 0.48 g of tertiary butyl hydroperoxide in demineralized water, 0.01 1 g of of iron(ll)EDTA and a subsequent feed addition of 17.0 g of a 1 % solution of isoascorbic acid in
  • the batch was filtered through a filter cloth to remove any coagulum formed during the reaction.
  • the resulting amine free polyurethane acrylic hybrid dispersion had a solids content of 34.2 wt %, a pH of 7.8 and a viscosity of 19 cps.
  • Formulations were prepared by slow addition of the additives (mentioned in the Table 1 below) to the polyurethane dispersion, while stirring.
  • Table 1 Formulations
  • the formulated examples, prepared and formulated as described above were cast onto a Leneta test chart using a wire rod at a wet film thickness of 125 micron.
  • the cast films were then allowed to dry at room temperature for 1 hour, followed by ageing of the coatings at 50°C for 16 hours.
  • the coatings were allowed to cool to room temperature for 1 hour.
  • the stain resistance of the coated cards towards the following stains were then assessed: water, ethanol (48%), detergent (Andy, 50% solution), coffee, hot pan.
  • a spot (1 cm 2 ) of the respective stain was placed on the coating and covered with a piece of filter paper and a watch glass.
  • a small glass beaker filled with boiling hot water was placed on cold water on a test chart.
  • E48% ethanol, 48% solution in demineralized water

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

Abstract

L'invention porte sur un procédé pour la préparation d'une dispersion aqueuse d'un polyuréthane A (PUD), le procédé comprenant les étapes consistant à : (a) faire réagir les constituants 1 et 3 (et 2 et 4 s'ils sont présents) pour former un prépolymère à terminaison isocyanate acide sur lequel se trouvent des groupes fonctionnels anioniques ou potentiellement anioniques ; (1) le constituant 1 comprenant 10 à 80 % en poids d'au moins un polyisocyanate contenant éventuellement au moins un groupe dispersant anionique ou potentiellement anionique ; (2) le constituant 2 facultatif comprenant jusqu'à 15 % en poids d'au moins un polyol réactif avec les isocyanates contenant au moins un groupe dispersant anionique ou potentiellement anionique ; (3) le constituant 3 comprenant 15 à 85 % en poids d'au moins un polyol hydrophobe réactif avec les isocyanates autre que le constituant 2 s'il est présent et ayant une masse moléculaire moyenne en poids supérieure ou égale à 500 Daltons ; et (4) le constituant 4 facultatif comprenant jusqu'à 20 % en poids d'au moins un polyol réactif avec les isocyanates autre que le constituant 3 et le constituant 2 s'il est présent et ayant une masse moléculaire moyenne en poids inférieure à 500 Daltons ; le constituant 1, si le constituant 2 n'est pas présent, contenant au moins un groupe dispersant anionique ou potentiellement anionique ; et le mélange utilisé dans l'étape (a) étant pratiquement exempt d'amines volatiles et de N-alkylpyrrolidinones ; (b) ajouter au mélange réactionnel provenant de l'étape (a) un agent neutralisant à métal alcalin à hauteur de 0,05 à 6 parties en poids pour neutraliser en grande partie le prépolymère à terminaison isocyanate obtenu à partir de l'étape (a) ; et (c) faire réagir le prépolymère neutralisé provenant de l'étape (b) avec un composé à hydrogène actif pour allonger la chaîne du prépolymère pour former une dispersion aqueuse de polyuréthane A. En l'absence d'un polymère vinylique réticulable B la dispersion aqueuse de polyuréthane A est réticulable de préférence par un procédé de réticulation choisi parmi : la réticulation par silane, la réticulation par UV, la réticulation par auto-oxydation, la réticulation par isocyanate, la réticulation par carbodiimide et/ou la réticulation par base de Schiff entre des groupes carbonyle et des composés polyamines et/ou polyhydrazides. L'invention porte également sur les PUD obtenues à partir de ce procédé et sur des compositions de revêtement comprenant la PUD ayant un polymère vinylique B, le polymère vinylique pouvant également être réticulé en particulier quand le polyuréthane A ne l'est pas.
PCT/EP2014/071504 2013-10-09 2014-10-08 Polymère, composition et utilisation WO2015052214A1 (fr)

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WO2005023947A1 (fr) * 2003-09-09 2005-03-17 Dsm Ip Assets B.V. Compositions polymeres aqueuses
WO2006002865A1 (fr) * 2004-06-30 2006-01-12 Dsm Ip Assets Bv Composition aqueuse de polyurethanne a faible niveau de nmp contenant un diluant
WO2008084041A1 (fr) * 2007-01-12 2008-07-17 Lamberti Spa Dispersions aqueuses de polyuréthane exemptes d'amines volatiles
WO2009074541A1 (fr) * 2007-12-13 2009-06-18 Dsm Ip Assets B.V. Composition aqueuse de revêtement comprenant des polyuréthanes et des polymères vinyliques
WO2009105396A1 (fr) * 2008-02-19 2009-08-27 Lubrizol Advanced Materials, Inc. Compositions hybrides de polyuréthanne aqueuses
WO2013153094A1 (fr) * 2012-04-10 2013-10-17 Dsm Ip Assets B.V. Polymère, composition de polymère et utilisation correspondante
WO2013153093A1 (fr) * 2012-04-10 2013-10-17 Dsm Ip Assets B.V. Polymère, composition de polymère et utilisation correspondante

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US4501852A (en) 1983-06-20 1985-02-26 Mobay Chemical Corporation Stable, aqueous dispersions of polyurethane-ureas
US4701480A (en) 1985-09-23 1987-10-20 Mobay Corporation Stable, aqueous dispersions of polyurethane-ureas
GB9211794D0 (en) 1992-06-04 1992-07-15 Ici Resins Bv Aqueous coating compositions
US6175752B1 (en) 1998-04-30 2001-01-16 Therasense, Inc. Analyte monitoring device and methods of use
NL1013300C2 (nl) 1999-10-15 2001-04-18 Stahl Int Bv Werkwijze voor de bereiding van een dispersie van een anionische polymeer in water waarin geen vluchtige tertiaire-amines voorkomen, de verkregen dispersies en coatings welke met de genoemde dispersies verkregen worden.
NL1013301C2 (nl) 1999-10-15 2001-04-18 Stahl Int Bv Werkwijze voor de bereiding van een dispersie van een anionische polyurethaan in water waarin geen vluchtige tertiaire amines voorkomen.
US20060229409A1 (en) 2005-04-08 2006-10-12 Ilmenev Pavel E Method for preparing polyurethane dispersions
EP1743911A1 (fr) 2005-07-14 2007-01-17 DSM IP Assets B.V. Composition de polyuréthanne

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Publication number Priority date Publication date Assignee Title
WO2005023947A1 (fr) * 2003-09-09 2005-03-17 Dsm Ip Assets B.V. Compositions polymeres aqueuses
WO2006002865A1 (fr) * 2004-06-30 2006-01-12 Dsm Ip Assets Bv Composition aqueuse de polyurethanne a faible niveau de nmp contenant un diluant
WO2008084041A1 (fr) * 2007-01-12 2008-07-17 Lamberti Spa Dispersions aqueuses de polyuréthane exemptes d'amines volatiles
WO2009074541A1 (fr) * 2007-12-13 2009-06-18 Dsm Ip Assets B.V. Composition aqueuse de revêtement comprenant des polyuréthanes et des polymères vinyliques
WO2009105396A1 (fr) * 2008-02-19 2009-08-27 Lubrizol Advanced Materials, Inc. Compositions hybrides de polyuréthanne aqueuses
WO2013153094A1 (fr) * 2012-04-10 2013-10-17 Dsm Ip Assets B.V. Polymère, composition de polymère et utilisation correspondante
WO2013153093A1 (fr) * 2012-04-10 2013-10-17 Dsm Ip Assets B.V. Polymère, composition de polymère et utilisation correspondante

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