WO2013153094A1 - Polymer, composition and use - Google Patents

Polymer, composition and use Download PDF

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Publication number
WO2013153094A1
WO2013153094A1 PCT/EP2013/057457 EP2013057457W WO2013153094A1 WO 2013153094 A1 WO2013153094 A1 WO 2013153094A1 EP 2013057457 W EP2013057457 W EP 2013057457W WO 2013153094 A1 WO2013153094 A1 WO 2013153094A1
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WO
WIPO (PCT)
Prior art keywords
weight
component
anionic
polyurethane
isocyanate
Prior art date
Application number
PCT/EP2013/057457
Other languages
French (fr)
Inventor
Ronald Tennebroek
Roel Johannes Marinus Swaans
DE Paul KOK
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Dsm Ip Assets B.V.
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Publication date
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Publication of WO2013153094A1 publication Critical patent/WO2013153094A1/en

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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
    • C08G18/65—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
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—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 hydrophilic acrylic part and the less hydrophilic 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, sulfate 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 an equivalent ratio from about 1 :4 to 4:1.
  • component (ii) a non-ionic 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 US 2010/0099967 in comparative example XVI).
  • 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 amino functional 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 dimethyl ethanol 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; non-ionic 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.
  • the invention comprises a process for preparing an aqueous dispersion of a polyurethane [A], the process comprising the steps of:
  • 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
  • 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; where if component two is not present component one 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);
  • 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;
  • 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 the polyurethane [A].
  • component (1 ) or (2) or both may comprise at least one anionic or potentially anionic dispersing group.
  • the isocyanate component (1 ) does not contain an anionic or potentially anionic dispersing group but instead at least one such group comprises the polyol component (2).
  • step (a) comprises:
  • step (b) occurs during or substantially immediately after step (a).
  • step (b) 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 intimate admixture components (i) and (ii):
  • composition (and both components (i) and (ii)) are substantially free of volatile amines and N-alkyl pyrrolidinones.
  • both components (i) and (ii) form different phases which are present in the same particles.
  • the following components may preferably be present in the following amounts by weight given as parts by weight or percentages by weight of the total amount of components (1 ) to (4) where present.
  • 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 5 to 8 by weight.
  • component (3) (the high (>500D) mw isocyanate-reactive 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.
  • Preferably optional component (5) (the alkali metal neutralising agent) is present in an amount from 0.1 to 6, more preferably from 0.2 to 5, most preferably 0.5 to 4 by weight.
  • 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 sulfonic 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 sulfonic acid groups. Conversion to the salt form is achieved by neutralisation of anionic groups with an alkali metal neutralising agent during step (a).
  • Component three comprises a isocyanate reactive polyol with a weight average molecular weight of greater than 500 daltons (high mw polyol).
  • Preferred polyols that comprise component three may have one or more of the following properties: hydrophobicity; comprise cyclic groups; comprise short chains that impart greater rigidity to the resultant polyurethane A prepared by the process of the invention; and/or have a glass transition temperature (measured by DSC) of from -50 to 60°C.
  • Preferred polyols that comprise component four may have one or more of the following properties: hydrophillicity; comprise linear groups; comprise long chains that impart greater flexibility to the resultant polyurethane A prepared by the process of the invention; and/or have a glass transition temperature (measured by DSC) of from -20 to 100°C.
  • 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.
  • compositions of the invention have low acid values (AV), more preferably the AV of the total composition is from 1 to 100 mg KOH / g.
  • 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.
  • a 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 (RS03H) group.
  • R03H sulfonic acid
  • Preferred are the Li, Na and K salts.
  • a 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 self cross-linkable comprising a carbonyl group capable of undergoing Schiff base cross-linking and the composition comprises a polyamine or polyhydrazide compound, most preferably adipic acid dihydrazide is employed.
  • dispersions and/or urethanes of and/or used in the present invention are crosslinked they are preferably crosslinked at ambient temperature under standard conditions, more preferably by a Schiff base mechanism which means that crosslinking takes place by the reaction of a carbonyl functional group(s) (as defined herein) with a carbonyl-reactive amine and/or hydrazine (or blocked amine and/or blocked hydrazine) functional group.
  • carbonyl functional group means an aldo or keto group and includes enolic carbonyl groups such as found in acetoacetyl groups.
  • Schiff base precursors denote any suitable compounds which under the reaction conditions described herein transform or react to form a Schiff base which is capable of undergoing Schiff base crosslinking as defined herein.
  • carbonyl i.e. aldo or ketone
  • the presence of carbonyl (i.e. aldo or ketone) functional groups in the examples of the present invention can be determined by any suitable known method such as by means of 13 C resonances in 13 C mnr spectrum.
  • ketones and aldehyde carbonyl groups these generally appear from 190 to 210 ppm irrespective of the side- chain substituents.
  • the 13 C NMR spectra of a 200 mg sample in 600 microlitres of a carrier medium of CDCI 3 and Chromium (III) acetylacetonate (also denoted as Cr(acac) 3 ) may be recorded.
  • the presence of carbonyl groups (i.e. aldo or ketone) in the process of the invention can be determined from relevant absorption peaks in the infrared spectrum of the reaction mixture. From these or other known methods the amount of unreacted carbonyl groups present in sample can be determined.
  • (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
  • Ingredients (1 ) and (4) are allowed to react together under conventional conditions to form a polyurethane dispersion to which is then added a 15% aqueous solution of KOH (65 weight parts of the solution) to neutralize the dispersion.
  • the ingredient (5) may be then be used to form a vinyl polymer in a conventional manner and combined with the PUD to form a urethane acrylic.

Abstract

There is described a process for preparing an aqueous dispersion of a polyurethane [A] (PUD) the process comprising the steps of: (a) reacting components one and three (and two and four where present) to form an acidic isocyanate terminated prepolymer that comprises anionic or potentially anionic functional groups thereon; where: (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; (2) 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; (3) component three comprises 15 to 85% by weight of at least one isocyanate reactive polyol other than component two if present, and having a weight average molecular weight greater than or equal to 500 Daltons; and (4) 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; where if component two is not present component one contains at least one anionic or potentially anionic dispersing group; where the mixture used in step (a) is substantially free of volatile amines and N-alkyl pyrrolidinones; (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); and (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. PUDs obtained from this method and coating compositions comprising the PUD with a vinyl polymer [B] are also described.

Description

POLYMER, COMPOSITION AND USE
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.
To prepare stable aqueous urethane-acrylic dispersions, both the hydrophilic acrylic part and the less hydrophilic polyurethane (PU) part must be dispersed in water. This can be achieved in part by surfactants and in part by incorporating suitable groups such as ionic or non-ionic hydrophilic groups in the polyurethane polymer either pendant to the polymer chain or in-chain. Such groups include anions such as carboxylic, sulfonic, sulfate 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.
It is also desirable to reduce or eliminate the use of surfactants in an aqueous coating dispersions as the use of large amount of surfactant increases the water sensitivity of the coatings that are formed.
When simple inorganic bases (such as KOH) are added to neutralise anionic polyurethane dispersions to neutralise acid groups therein, they are found unsatisfactory. In general the viscosity of the polyurethane dispersion rises undesirably when strong inorganic bases are added. To prevent the dispersion destabilising the polyurethane, it may be modified with large amounts of hydrophilic groups such as polyethoxy groups. The resultant films and coatings (whether the PU is modified or not) are also highly water sensitive (compared to PUD neutralised by other agents) unless a further agent is added to cross-link the polyurethane. So other neutralising agents are used to prepare commercially available PU dispersions, the most common of which are volatile amines such as the tertiary amine triethyl amine (TEA). These materials are readily available and easily removed from the final dispersion.
However it is known that 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.
Various alternatives have been proposed to improve the stability of aqueous urethane dispersions.
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. To counter the anionic groups the formulation contains a mixture of volatile and non-volatile cations in an equivalent ratio from about 1 :4 to 4:1. The examples use as component (ii) a non-ionic 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 US 2010/0099967 in comparative example XVI).
US 2006-0229409 describes polyurethane dispersions made from TMXDI with a special embodiment on page 9 where the use of metal hydroxides is mentioned. This is not exemplified in the examples nor is TMXDI a suitable
diisocyanate for use in coatings (it is too soft).
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. First 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 amino functional 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 dimethyl ethanol 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; non-ionic 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.
WO 2001 -027179 (Stahl) describes an anionic polyurethane dispersion which is neutralised by a tertiary amine functional urethane polymer or oligomer. Although 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.
Surprising the applicant has found a means to stabilise aqueous dispersions of acrylate and anionic polyurethanes without the proceeding
disadvantages.
In particular the applicant has found that adding an alkali metal neutralising agent at an early stage in the process reduces or avoids some or all of the preceding problems with the prior art.
Therefore broadly the invention comprises a process for preparing an aqueous dispersion of a polyurethane [A], the process comprising the steps of:
(a) reacting components one and three (and two and four where present) to form an acidic isocyanate terminated prepolymer that comprises anionic or potentially anionic functional groups thereon; where: (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;
(2) 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;
(3) component three comprises 15 to 85% by weight of at least one
isocyanate reactive polyol other than component two if present, and having a weight average molecular weight greater than or equal to 500 Daltons; and
(4) 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; where if component two is not present component one contains at least one anionic or potentially anionic dispersing group;
where the amounts of components one to four are expressed as a weight percentage calculated from the total amount of the above components (i.e. one and three and optional two and/or four where present) being 100%; and
where the mixture used in step (a) is substantially free of volatile amines and N-alkyl pyrrolidinones;
(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; and
(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 the polyurethane [A].
It will be seen that the sum of the amounts of ingredients given (a) and (b) together will total greater than 100 parts by weight.
In the process of the invention either component (1 ) or (2) or both may comprise at least one anionic or potentially anionic dispersing group. However it is preferred that the isocyanate component (1 ) does not contain an anionic or potentially anionic dispersing group but instead at least one such group comprises the polyol component (2).
Therefore in one preferred embodiment of the process of the invention, step (a) comprises:
(a) reacting:
(1 ) 10 to 80% by weight of at least one polyisocyanate;
(2) 1 to 15% by weight of at least one isocyanate-reactive polyol containing at least one anionic or potentially anionic dispersing group;
(3) 15 to 84% by weight of at least one isocyanate reactive polyol other than (2), and having a weight average molecular weight > 500 Daltons; and
(4) optionally up to 20% by weight of at least one isocyanate reactive polyol other than (2) and (3) and having a weight average molecular weight < 500 Dalton; to form an acidic isocyanate terminated prepolymer that comprises anionic or potentially anionic functional groups and which is substantially free of volatile amines and N-alkyl pyrrolidinones (such as TEA, NMP or NEP).
Preferably step (b) occurs during or substantially immediately after step (a).
Without being bound by any mechanism it is believed that in step (b) 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 intimate admixture components (i) and (ii):
(i) 10 to 95% by weight of a polyurethane dispersion A obtained and/or
obtainable by the process of the invention as described herein; and
(ii) 90 to 5% by weight of a vinyl polymer B with a glass transition temperature > 15°C
wherein
(i) and (ii) add up to 100% and are calculated based on weight of solids (excluding the water); and
where the composition (and both components (i) and (ii)) are substantially free of volatile amines and N-alkyl pyrrolidinones. Preferably both components (i) and (ii) form different phases which are present in the same particles.
The following components may preferably be present in the following amounts by weight given as parts by weight or percentages by weight of the total amount of components (1 ) to (4) where present.
Preferably 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.
Preferably component (2) (the anioinic isocyanate-reactive polyol) is present in an amount from 2 to 12, more preferably from 3 to 10, most preferably 5 to 8 by weight.
Preferably component (3) (the high (>500D) mw isocyanate-reactive 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.
Preferably optional component (5) (the alkali metal neutralising agent) is present in an amount from 0.1 to 6, more preferably from 0.2 to 5, most preferably 0.5 to 4 by weight.
The term "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. Without wishing to be bound by any mechanism it is believed that 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.
The polyurethane dispersions of the invention may (unless indicated otherwise herein) be prepared conventionally using conventional polyols and isocyanates.
For example the 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).
For example the 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. Examples of suitable polyisocyanates include ethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1 , 4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, p-xylylene diisocyanate, α,α'-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.
Preferably component two comprises a polyol with an anionic or potential anionic dispersing group thereon.
Preferred anionic dispersing groups are carboxylic, phosphate, phosphonate or sulfonic 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 sulfonic acid groups. Conversion to the salt form is achieved by neutralisation of anionic groups with an alkali metal neutralising agent during step (a). Component three comprises a isocyanate reactive polyol with a weight average molecular weight of greater than 500 daltons (high mw polyol).
Preferred polyols that comprise component three may have one or more of the following properties: hydrophobicity; comprise cyclic groups; comprise short chains that impart greater rigidity to the resultant polyurethane A prepared by the process of the invention; and/or have a glass transition temperature (measured by DSC) of from -50 to 60°C.
Preferred polyols that comprise component four may have one or more of the following properties: hydrophillicity; comprise linear groups; comprise long chains that impart greater flexibility to the resultant polyurethane A prepared by the process of the invention; and/or have a glass transition temperature (measured by DSC) of from -20 to 100°C.
In one embodiment of the invention it is preferred that 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.
In a still further embodiment of the invention it is preferred that 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. Although 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.
Optionally 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.
In the present invention it is preferred that 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.
Preferred compositions of the invention have low acid values (AV), more preferably the AV of the total composition is from 1 to 100 mg KOH / g.
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.
A 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 (RS03H) group. Preferred are the Li, Na and K salts.
A 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 self cross-linkable comprising a carbonyl group capable of undergoing Schiff base cross-linking and the composition comprises a polyamine or polyhydrazide compound, most preferably adipic acid dihydrazide is employed.
Where the dispersions and/or urethanes of and/or used in the present invention are crosslinked they are preferably crosslinked at ambient temperature under standard conditions, more preferably by a Schiff base mechanism which means that crosslinking takes place by the reaction of a carbonyl functional group(s) (as defined herein) with a carbonyl-reactive amine and/or hydrazine (or blocked amine and/or blocked hydrazine) functional group. In this context "carbonyl functional group' means an aldo or keto group and includes enolic carbonyl groups such as found in acetoacetyl groups. Suitable carbonyl-reactive compounds may comprise Schiff bases (or precursors therefor) which are compounds comprising at least one functional group with a carbon-nitrogen double bond where the nitrogen atom is connected to an aryl and/or alkyl group (and not hydrogen), such as stable imines for example compounds having the general formula R'R"C=NR"' where R', R" and R'" are independently organic moieties. Useful Schiff bases comprise azomethine and secondary aldimines (azomethines where the carbon is connected to a hydrogen atom, i.e. of general formula R'CH=NR") and/or Schiff bases derived from aniline, where R" is a phenyl or a substituted phenyl such compounds also referred to as anils. Schiff base precursors denote any suitable compounds which under the reaction conditions described herein transform or react to form a Schiff base which is capable of undergoing Schiff base crosslinking as defined herein. Examples of carbonyl-reactive amine (or blocked amine) functional groups include any of the following compounds or groups: R-NH2, R- 0-NH2, R-0-N=C<, R-NH-C(=0)-0-N=C< and/or R-NH-C(=0)-0-NH2 where R is optionally substituted Ci to Ci5, preferably Ci to C10 alkylene, optionally substituted alicyclic, optionally substituted aryl, and/or R may also be part of a polymer. Examples of carbonyl-reactive hydrazine (or blocked hydrazine) compounds or groups include R- NH-NH2, R-C(=0)-NH-NH2, R-C(=0)-NH-N=C<, R-NH-C(=0)-NH-NH2 and/or R-NH- C(=0)-NH-N=C< where R is as described above.
The presence of carbonyl (i.e. aldo or ketone) functional groups in the examples of the present invention can be determined by any suitable known method such as by means of 13C resonances in 13C mnr spectrum. For ketones and aldehyde carbonyl groups these generally appear from 190 to 210 ppm irrespective of the side- chain substituents. These can be distinguished from carbon 13 resonances from other C=0 groups such as in carboxylic acid derivatives (amides, esters, carboxylic acids, acid chlorides etc.) which generally appear from 160 to 185 ppm. For example in one suitable method the 13C NMR spectra of a 200 mg sample in 600 microlitres of a carrier medium of CDCI3 and Chromium (III) acetylacetonate (also denoted as Cr(acac) 3) may be recorded. Alternatively the presence of carbonyl groups (i.e. aldo or ketone) in the process of the invention can be determined from relevant absorption peaks in the infrared spectrum of the reaction mixture. From these or other known methods the amount of unreacted carbonyl groups present in sample can be determined.
Without wishing to be bound by any mechanism it is believed that (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
advantageously used as coatings for surfaces such as floors.
Many other variations embodiments of the invention will be apparent to those skilled in the art and such variations are contemplated within the broad scope of the present invention.
Further aspects of the invention and preferred features thereof are given in the claims herein.
Example
The present invention will now be described in detail with reference to the following non limiting example which is by way of illustration only. The following example may be prepared as described. The amount of each component is given in brackets as a relative parts by weight of total of components below.
Example 1
Ingredients
(1 ) Isophorone diisocyanate (100 weight parts) and methylene bis (4- cyclohexylisocyanate) available under the trade name Desmodur W from Bayer (100 weight parts)
(2) Dimethylolpropionic acid (30 weight parts)
(3) Semicrystalline polyester polyol (2000 MW) having hydroxy and acid groups thereon (OH + Ac = 56) available under the trade name Priplast 3192 from Croda (340 weight parts)
(4) 1 ,4-Cyclohexanedimethanol (20 weight parts)
(5) Methyl methacrylate (200 weight parts)
Ingredients (1 ) and (4) are allowed to react together under conventional conditions to form a polyurethane dispersion to which is then added a 15% aqueous solution of KOH (65 weight parts of the solution) to neutralize the dispersion. The ingredient (5) may be then be used to form a vinyl polymer in a conventional manner and combined with the PUD to form a urethane acrylic.

Claims

CLAIMS A process for preparing an aqueous dispersion of a polyurethane A the process comprising the steps of: (a) reacting components one and three (and two and four where present) to form an acidic isocyanate terminated prepolymer that comprises anionic or potentially anionic functional groups thereon; where: (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; (2) 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; (3) component three comprises 15 to 85% by weight of at least one isocyanate reactive polyol other than component two if present, and having a weight average molecular weight greater than or equal to 500 Daltons; and (4) 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; where if component two is not present component one contains at least one anionic or potentially anionic dispersing group; where the amounts of components one to four are expressed as a weight percentage calculated from the total amount of the above components (i.e. one and three and optional two and/or four where present) being 100%; and where the mixture used in step (a) is substantially free of volatile amines and N-alkyl pyrrolidinones; (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; and (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. A process as claimed in claim 1 , in which either component one or two or both may comprise at least one anionic or potentially anionic dispersing group. A process as claimed in either preceding claim, in which step (a) comprises: (a) reacting:
(1 ) 10 to 80% by weight of at least one polyisocyanate;
(2) 1 to 15% by weight of at least one isocyanate-reactive polyol containing at least one anionic or potentially anionic dispersing group;
(3) 15 to 84% by weight of at least one isocyanate reactive polyol other than (2), and having a weight average molecular weight > 500 Daltons; and
(4) optionally up to 20% by weight of at least one isocyanate reactive polyol other than (2) and (3) and having a weight average molecular weight < 500 Dalton;
to form an acidic isocyanate terminated prepolymer that comprises anionic or potentially anionic functional groups and which is substantially free of volatile amines and N-alkyl pyrrolidinones.
A process as claimed in any preceding claim, in which step (b) occurs during or substantially immediately after step (a).
A process for preparing an aqueous coating composition comprising bringing into intimate admixture components (i) and (ii):
(i) 10 to 95% by weight of a polyurethane dispersion A obtained and/or obtainable by the process as claimed in any preceding claim and
(ii) 90 to 5% by weight of a vinyl polymer B with a glass transition
temperature > 15°C
where (i) and (ii) add up to 100% and are calculated based on weight of solids (excluding the water); and
where the composition (and both components (i) and (ii)) are substantially free of volatile amines and N-alkyl pyrrolidinones.
An aqueous dispersion of a polyurethane A, obtained and/or obtainable by a process as claimed in any of claims 1 to 4. An aqueous coating composition comprising a polyurethane A and a vinyl polymer B, obtained and/or obtainable by a process as claimed in claim 5. An article and/or substrate coated by a composition as claimed in claim 7. A method of coating an article and/or substrate comprising the steps of
(I) applying a coating composition as claimed in claim 7 to an article and/or substrate, and
(II) drying the coating thereon to obtain a coated article and/or substrate.
PCT/EP2013/057457 2012-04-10 2013-04-10 Polymer, composition and use WO2013153094A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015052213A1 (en) * 2013-10-09 2015-04-16 Dsm Ip Assets B.V. Polymer, composition and use

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2968575A (en) 1953-06-30 1961-01-17 Du Pont Stable polyurethane latex and process of making same
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
WO1993024551A1 (en) 1992-06-04 1993-12-09 Zeneca Resins Bv Aqueous polyurethane dispersions
WO2001027179A1 (en) 1999-10-15 2001-04-19 Stahl International B.V. Process for the preparation of an aqueous dispersion of an anionic polyurethane free of volatile tertiary amines
EP1153051A1 (en) 1999-10-15 2001-11-14 Stahl International B.V. Process for the preparation of anionic aqueous polymer dispersions containing no volatile tertiary amine, obtained dispersion and coating resulting from said dispersion
WO2005023947A1 (en) * 2003-09-09 2005-03-17 Dsm Ip Assets B.V. Aqueous polymer compositions
US20060229409A1 (en) 2005-04-08 2006-10-12 Ilmenev Pavel E Method for preparing polyurethane dispersions
WO2007006586A1 (en) 2005-07-14 2007-01-18 Dsm Ip Assets B.V. Solvent borne polyurethane process
WO2009074541A1 (en) * 2007-12-13 2009-06-18 Dsm Ip Assets B.V. Aqueous coating composition comprising polyurethanes and vinyl polymers
US20100098867A1 (en) 2007-01-12 2010-04-22 Gabriele Costa Volatile amines free polyurethane aqueous dispersions
US20100099967A1 (en) 1998-04-30 2010-04-22 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2968575A (en) 1953-06-30 1961-01-17 Du Pont Stable polyurethane latex and process of making same
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
WO1993024551A1 (en) 1992-06-04 1993-12-09 Zeneca Resins Bv Aqueous polyurethane dispersions
US20100099967A1 (en) 1998-04-30 2010-04-22 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
WO2001027179A1 (en) 1999-10-15 2001-04-19 Stahl International B.V. Process for the preparation of an aqueous dispersion of an anionic polyurethane free of volatile tertiary amines
EP1153051A1 (en) 1999-10-15 2001-11-14 Stahl International B.V. Process for the preparation of anionic aqueous polymer dispersions containing no volatile tertiary amine, obtained dispersion and coating resulting from said dispersion
WO2005023947A1 (en) * 2003-09-09 2005-03-17 Dsm Ip Assets B.V. Aqueous polymer compositions
US20060229409A1 (en) 2005-04-08 2006-10-12 Ilmenev Pavel E Method for preparing polyurethane dispersions
WO2007006586A1 (en) 2005-07-14 2007-01-18 Dsm Ip Assets B.V. Solvent borne polyurethane process
US20100098867A1 (en) 2007-01-12 2010-04-22 Gabriele Costa Volatile amines free polyurethane aqueous dispersions
WO2009074541A1 (en) * 2007-12-13 2009-06-18 Dsm Ip Assets B.V. Aqueous coating composition comprising polyurethanes and vinyl polymers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015052213A1 (en) * 2013-10-09 2015-04-16 Dsm Ip Assets B.V. Polymer, composition and use
WO2015052214A1 (en) * 2013-10-09 2015-04-16 Dsm Ip Assets B.V. Polymer, composition and use

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