WO2006002864A1 - Low nmp aqueous polyurethane composition with a reactive diluent - Google Patents
Low nmp aqueous polyurethane composition with a reactive diluent Download PDFInfo
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- WO2006002864A1 WO2006002864A1 PCT/EP2005/006932 EP2005006932W WO2006002864A1 WO 2006002864 A1 WO2006002864 A1 WO 2006002864A1 EP 2005006932 W EP2005006932 W EP 2005006932W WO 2006002864 A1 WO2006002864 A1 WO 2006002864A1
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- aqueous composition
- dispersion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7607—Compounds of C08G18/7614 and of C08G18/7657
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31591—Next to cellulosic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
- Y10T428/31601—Quartz or glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31989—Of wood
Definitions
- the present invention relates to an aqueous composition comprising a polyurethane dispersion, an aqueous composition comprising a polyurethane vinyl hybrid dispersion, a process for making the aqueous compositions and the use of such aqueous compositions in coatings such as coatings for floors.
- polyurethane dispersions can be applied to a variety of substrates to provide coatings with good resistance to abrasion, good chemical resistance, good flexibility and durability as well as having good adhesion to the substrate.
- a major application for such coatings is as clear coatings for wood flooring.
- polyurethane compositions are prepared in organic solvents which evaporate on drying after application to a substrate.
- organic solvents which evaporate on drying after application to a substrate.
- water-based polyurethane dispersions and polyurethane vinyl hybrid dispersions have been developed and are well known.
- polyurethanes based predominantly on aromatic polyisocyanates have better hardness, better resistance against chemicals and better mechanical properties in for example flooring applications than polyurethanes based predominantly on aliphatic isocyanates. Furthermore the use of aromatic polyisocyanates tends to be more cost effective than the use of aliphatic polyisocyanates.
- US 4,801 ,644 and US 4,927,876 disclose the preparation of aqueous polyurethane compositions containing diphenylmethane-2,4-diisocyanate utilising 1-methyl-2- pyrrolidinone as an organic solvent.
- US 5,173,526 discloses a method for making aqueous polyurethane-vinyl polymer dispersions with 1-methyl-2-pyrrolidinone being used as a solvent.
- US 5,314,942 discloses an aqueous polymer dispersion containing a vinyl polymer prepared in-situ and a water-dispersible polyurethane having pendent polyethylene oxide chains and utilising 1-methyl-2-pyrrolidinone.
- US 6,239,209 discloses an air-curable polyurethane-acrylic hybrid interpenetrating polymer network.
- JP 06-08553 and JP 03-193446 disclose the preparation of polyurethane-polyurea dispersions.
- US 4,318,833 discloses water-reducible acrylic-urethane coating compositions where the polyurethanes are prepared in a solvent mixture.
- US 4,644,030 discloses aqueous polyurethane-polyolefin compositions.
- US 5,137,961 discloses the preparation of a surfactant free aqueous polymer dispersion containing an anionic polyurethane based substantially on aliphatic isocyanates and a vinyl polymer where vinyl monomers are used to reduce the viscosity of the reaction mixture.
- US 6,635,706 discloses a pre-crosslinked urethane-acrylic dispersion.
- US 6,635,723 discloses a process for making a solvent-free polyurethane dispersion using a relatively low aliphatic polyisocyanate content.
- US 6,720,385 discloses aqueous polyurethane latexes prepared without the use of organic solvents using relatively high levels of polyethylene oxide polyols.
- JP 09-150568, JP 09-150569, JP 09-102861 and JP 09-038674 disclose the preparation of aqueous polyurethane compositions utilising unsaturated monomers and hydroxyl groups bearing organic solvents.
- a disadvantage resulting from the preparation of polyurethanes based on aromatic isocyanates and with very low NMP levels or with no NMP at all is that the processing usually results in a high level of sediment and/or gel. Furthermore in the prior art there is a desire to keep the level of polyisocyanate used in the polyurethane preparation to a minimum in order to get acceptable processing.
- an aqueous composition with a sediment content ⁇ 5% comprising a polyurethane dispersion and containing ⁇ 5 wt% of 1 -methyl-2-pyrrolidinone by weight of the polyurethane, wherein the polyurethane has an acid value in the range of from 25 to 65 mgKOH/g and is obtained by the reaction of:
- the aqueous composition comprising a polyurethane dispersion contains ⁇ 3 wt%, more preferably ⁇ 1 wt%, most preferably ⁇ 0.5 wt% and especially 0 wt% of NMP by weight of the polyurethane.
- polyurethane For clarity by weight of polyurethane is meant the weight of polyurethane solids excluding the reactive diluent.
- an aqueous composition with a sediment content ⁇ 5% comprising a polyurethane vinyl hybrid dispersion and containing ⁇ 0.5 wt% of 1-methyl-2-pyrrolidinone by weight of the composition; wherein the polyurethane has an acid value in the range of from 25 to 65 mgKOH/g and is obtained by the reaction of :
- components (i) + (ii) + (iii) + (v) add up to > 42 wt% more preferably > 46 wt% and especially > 50 wt%.
- the composition of the invention contains 0 wt% of NMP.
- a polyurethane vinyl hybrid is meant that a vinyl polymer is prepared by the polymerisation of vinyl monomers in the presence of the polyurethane.
- the vinyl polymer may be grafted to the polyurethane or alternatively the vinyl polymer is not grafted to the polyurethane during the polymerisation.
- polyurethane, vinyl polymer, vinyl monomer and polyurethane vinyl hybrid are intended to cover the singular as well as the plural.
- the ratio of polyurethane to vinyl polymer in the polyurethane vinyl hybrid is in the range of from 95:5 to 30:70, more preferably 85:15 to 35:65 and most preferably 75:25 to 40:60.
- the acid value of the polyurethane is in the range of from 29 to 55 mgKOH/g, more preferably 30 to 55 mgKOH/g and most preferably 31 to 53 mgKOH/g of polyurethane.
- the aromatic polyisocyanate component (i) can be a mixture of aromatic polyisocyanates. This term (for the sake of clarity) being intended to mean compounds in which all of the isocyanate groups are directly bonded to an aromatic group, irrespective of whether aliphatic groups are also present.
- suitable aromatic polyisocyanates include but are not limited to p-xylylene diisocyanate, 1 ,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-methylene bis(phenyl isocyanate), polymethylene polypheny! polyisocyanates, 2,4'-methylene bis(phenyl isocyanate) and 1 ,5-naphthylene diisocyanate.
- the isocyanate-terminated prepolymer comprises 36 to 50 wt%, more preferably 37 to 46 wt% of component (i).
- component (i) comprises methylene bis(phenyl isocyanate) (all isomers) and/or toluene diisocyanate (all isomers). More preferably component (i) comprises from 10 to 70 wt% of toluene diisocyanate and from 90 to 30 wt% of methylene bis(phenyl isocyanate).
- component (i) comprises from 25 to 60 wt% of toluene diisocyanate and from 75 to 40 wt% of methylene bis(phenyl isocyanate) where preferably the methylene bis(phenyl isocyanate) is a mixture of 4,4' and 2,4'-methylene bis(phenyl isocyanate), where the mixture preferably contains from 5 to 70 wt% of 2,4'-methylene bis(phenyl isocyanate).
- the aliphatic polyisocyanate component (ii) can be a mixture of aliphatic isocyanates. This term (for the sake of clarity) being intended to mean compounds in which all of the isocyanate groups are directly bonded to aliphatic or cycloaliphatic groups, irrespective of whether aromatic groups are also present.
- Examples include but are not limited to ethylene diisocyanate, para- tetramethylxylene diisocyanate (p-TMXDI), meta-tetramethylxylene diisocyanate (m-TMXDI), 1 ,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1 ,4- diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.
- p-TMXDI para- tetramethylxylene diisocyanate
- m-TMXDI meta-tetramethylxylene diisocyanate
- 1 ,6-hexamethylene diisocyanate isophorone diisocyanate
- cyclohexane-1 ,4- diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.
- the isocyanate-terminated prepolymer comprises 0 to 12 wt%, more preferably 0 wt% of component (ii).
- Aromatic or aliphatic polyisocyanates which have been modified by the introduction of urethane, allophanate, urea, biuret, uretonimine, urethdione or isocyanurate residues can be used for components (i) and (ii) respectively.
- the isocyanate-reactive components (iii) to (vi) will normally consist of a polyol component bearing isocyanate-reactive groups which may also bear other reactive groups.
- a polyol component it is also meant to include compounds with one or more isocyanate-reactive groups such as -OH, -SH, -NH- and -NH 2 .
- Water-dispersing groups are preferably introduced by employing at least one isocyanate-reactive compound bearing a non-ionic and/or ionic water-dispersing groups as a component in the preparation of the isocyanate-terminated prepolymer.
- component (iii) comprises anionic or potentially anionic water-dispersing groups.
- compounds bearing anionic water-dispersing groups include phosphoric acid groups, sulphonic acid groups and/or carboxylic acid groups such as carboxyl group containing diols and triols.
- component (iii) comprises dihydroxy alkanoic acids such as 2,2-dimethylolpropionic acid (DMPA) and/or 2,2-dimethylolbutanoic acid (DMBA).
- DMPA 2,2-dimethylolpropionic acid
- DMBA 2,2-dimethylolbutanoic acid
- the anionic water-dispersing groups are preferably fully or partially in the form of a salt. Conversion of for example a potentially anionic water-dispersing group to the salt form (i.e. anionic water-dispersing group) may be effected by neutralisation with a base, preferably during the preparation of the aqueous composition of the present invention.
- the base used to neutralise the groups may be selected from ammonia, an amine, an inorganic base and combinations thereof.
- ammonia and inorganic bases are only used in combination with other neutralising agents, where generally less than 0.5 equivalent, more preferably less than 0.2 equivalent of ammonia and/or inorganic base per anionic, more preferably per carboxylic acid group is used.
- Tertiary amines are preferred.
- Tertiary amines include for example triethylamine, dimethyl amino ethyl methacrylate or oxygen containing amines.
- > 60 wt%, more preferably > 80 wt% and especially 100 wt% of the polyurethane is neutralised with an oxygen containing amine.
- oxygen containing amine is selected from the group consisting of
- Suitable inorganic bases include alkali hydroxides and carbonates, for example lithium hydroxide, sodium hydroxide or potassium hydroxide.
- a quaternary ammonium hydroxide, for example N + (CH 3 ) 4 (OH), can also be used.
- a base which gives counter ions that may be desired for the composition.
- preferred counter ions include Li + , Na + , K + , NH 4 + and substituted ammonium salts.
- inorganic bases they are preferably used in combination with at least one tertiary amine as described above.
- Neutralisation is usually based on the equivalent of ionic groups, and preferably the ionic water-dispersing groups in the isocyanate-terminated prepolymer are neutralised with a neutralising agent in the range of from 0.5:1 to 1.4:1 , more preferably 0.6:1 to 1.4:1 , most preferably 0.75:1 to 1.30:1 and especially 0.95:1 to 1.25:1.
- a neutralising agent in the range of from 0.5:1 to 1.4:1 , more preferably 0.6:1 to 1.4:1 , most preferably 0.75:1 to 1.30:1 and especially 0.95:1 to 1.25:1.
- a neutralising agent in the range of from 0.5:1 to 1.4:1 , more preferably 0.6:1 to 1.4:1 , most preferably 0.75:1 to 1.30:1 and especially 0.95:1 to 1.25:1.
- Cationic water-dispersible groups can also be used, but are less preferred. Examples include pyridine groups, imidazole groups and/or quaternary ammonium groups which may be neutralised or permanently ionised (for example with dimethylsulphate).
- the isocyanate-terminated prepolymer comprises 2 to 14 wt%, more preferably 5.0 to 13.0 wt% and especially 0.7 to 13 wt% of component (iii).
- Component (iv) bears non-ionic water-dispersing groups.
- Preferred non-ionic water-dispersing groups are polyalkylene oxide groups where ethylene oxide is the major component. A small part of the polyethylene oxide segments can be replaced by propylene oxide segments and/or butylene oxide segments, however the polyalkylene oxide group should still contain ethylene oxide as a major component.
- the non-ionic water-dispersing group comprises at least 90 wt%, more preferably at least 95 wt%, especially at least 98 wt% and most especially 100 wt% of ethylene oxide.
- the water-dispersible group is polyethylene oxide
- the polyethylene oxide group has a molecular weight from 175 to 5000 Daltons, more preferably from 350 to 2200 Daltons, most preferably from 660 to 1600 Daltons.
- Examples of preferred compounds bearing non-ionic water-dispersing groups include methoxy polyethylene glycol (MPEG) with molecular weights of for example 350, 550, 750, 1000 and 2000, as described in EP 0317258.
- MPEG methoxy polyethylene glycol
- An excess of isocyanate-reactive polyols bearing non-ionic water-dispersing groups may result in lower K ⁇ nig Hardness and lower chemical or stain resistance of a resultant coating.
- the isocyanate-terminated prepolymer comprises 0 to 7 wt%, more preferably 0 wt% of component (iv).
- component (v) examples include but are not limited to ethylene glycol, neopentyl glycol, 1 ,4-cyclohexyldimethanol and less preferably water. Also included are low molecular weight polyester polyols which include hydroxyl-terminated reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1 ,4-butanediol, 1,6-hexanediol, furan dimethanol, cyclohexane dimethanol, glycerol, trimethylolpropane or mixtures thereof, with polycarboxylic acids, especially dicarboxylic acids or their ester-forming derivatives, for examples succinic, glutaric and adipic acids or their methyl esters, phthalic anhydrides or dimethyl terephthalate. Polyesters obtained by the polymerisation of lactones, for example caprolactone in conjunction with a polyol may also be used.
- component (v) has an average of 1.8 to 2.5 isocyanate-reactive groups and more preferably component (v) has two hydroxy functional groups.
- the weight average molecular weight of component (v) is in the range of from 62 to 300 and more preferably 84 to 200 g/mol.
- the isocyanate-terminated prepolymer comprises 2 to 8 wt%, more preferably 3 to 6 wt% of component (v).
- component (vi) include but are not limited to higher molecular weight examples of the compounds listed for component (v), such as polyesters, polyether polyols, polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins and/or polysiloxanes.
- Polyesteramides may be obtained by the inclusion of amino-alcohols such as ethanolamine in polyesterification mixtures.
- Polyesters which incorporate carboxy groups may be used, for example polyesters where DMPA and/or DMBA is used, provided that the esterification is carried out under conditions which allow the retention of the carboxy functionality in the final polyester.
- a feature of such carboxy functional polyesters is that they can contribute to the dispersibility of the isocyanate-terminated prepolymer in water, thus allowing a lower level of component (iii) to be used.
- Polyether polyols which may be used include products obtained by the polymerisation of a cyclic oxide, for example a minor amount of ethylene oxide, propylene oxide or tetrahydrofuran or by the addition of one or more such oxides to polyfunctional initiators, for example water, methylene glycol, ethylene glycol, propylene glycol, diethylene glycol, cyclohexane dimethanol, glycerol, trimethylopropane, pentaerythritol or Bisphenol A.
- a cyclic oxide for example a minor amount of ethylene oxide, propylene oxide or tetrahydrofuran or by the addition of one or more such oxides to polyfunctional initiators, for example water, methylene glycol, ethylene glycol, propylene glycol, diethylene glycol, cyclohexane dimethanol, glycerol, trimethylopropane, pentaerythritol or Bisphenol A.
- polyether polyols include polyoxypropylene diols and triols, poly (oxyethylene-oxypropylene) diols and triols obtained by the simultaneous or sequential addition of ethylene and propylene oxides to appropriate initiators and polytetramethylene ether glycols obtained by the polymerisation of tetrahydrofuran.
- Particularly preferred are polyether diols.
- polyether diols For clarity the presence of any ethylene oxide in such polyols is not be enough for them to be considered as non-ionic water dispersing polyols.
- Crosslinking groups are well known in the art and include groups which may crosslink at ambient temperature (22 ⁇ 3°C) by a number of mechanisms including but not limited to autoxidation (for example by fatty acid groups containing unsaturated bonds); Schiff base crosslinking (for example the reaction of carbonyl functional groups with carbonyl reactive amine and/or hydrazine functional groups); silane crosslinking (for example the reaction of alkoxy silane groups in the presence of water) and epoxy groups crosslinking with epoxy- reactive functional groups.
- an isocyanate-terminated prepolymer When an isocyanate-terminated prepolymer is prepared, it is conventionally formed by reacting a stoichiometric excess of the organic polyisocyanate (components (i) and (H)) with the isocyanate-reactive compounds (components (iii), (iv), (v) and (vi)) under substantially anhydrous conditions at a temperature between about 3O 0 C and about 130 0 C until reaction between the isocyanate groups and the isocyanate-reactive groups is substantially complete; preferably the reactants for the prepolymer are generally used in proportions corresponding to a ratio of isocyanate groups to isocyanate-reactive groups of from about 1.4:1 to about 2.0:1 and more preferably from about 1.45:1 to 1.75:1.
- the practical NCO% of the prepolymer at the end of prepolymer preparation should be equal to or less than the theoretical NCO%. If the practical NCO% is greater than the theoretical NCO%, then the prepolymer reaction has not been completed which will affect the reproducibility of the dispersion ability since the amount of residual free polyols and/or isocyanates may vary. Additionally, if the prepolymer reaction has not been completed and dispersion is started the dispersability will be decreased as any unreacted polyols and free isocyanates reduce the water up take and will therefore result in more sediment.
- catalysts such as dibutyltin dilaurate and stannous octoate, zirconium or titanium based catalysts may be used to assist the polyurethane formation. Preferably no catalyst is used.
- Active hydrogen-containing chain extending compounds which may be reacted with the isocyanate-terminated prepolymer include amino-alcohols, primary or secondary diamines or polyamines, hydrazine and substituted hydrazines.
- chain extending compounds useful herein include alkylene diamines such as ethylene diamine and cyclic amines such as isophorone diamine.
- hydrazine azines such as acetone azine, substituted hydrazines such as, for example, dimethyl hydrazine, 1 ,6-hexamethylene-bis-hydrazine, carbodihydrazine, hydrazides of dicarboxylic acids and sulphonic acids such as adipic acid dihydrazide, oxalic acid dihydrazide, isophthalic acid dihydrazide, hydrazides made by reacting lactones with hydrazine, bis-semi-carbazide, and bis-hydrazide carbonic esters of glycols may be useful. Water itself may be effective as an indirect chain extending compound.
- Another suitable class of chain extending compounds are the so-called “Jeffamine” compounds with a functionality of 2 or 3 (available from Huntsman). These are PPO or PEO-based di or triamines, e.g. “Jeffamine” T403 and “Jeffamine” D- 400.
- the ratio of active-hydrogen chain extending compound other than water to isocyanate (NCO) groups is in the range of from 0.5:1 to 1.2:1 , more preferably 0.6:1 to 1.1 :1 , especially 0.75:1 to 1.02:1 and most preferably 0.78:1 to 0.98:1.
- the chain extender is other than water, for example a polyamine or hydrazine
- it may be added to an aqueous dispersion of the isocyanate-terminated prepolymer or preferably, it may already be present in the aqueous medium when the isocyanate-terminated prepolymer is dispersed therein.
- the isocyanate-terminated prepolymer may be dispersed in water using techniques well known in the art.
- the isocyanate-terminated prepolymer is added to the water with agitation or, alternatively, water may be stirred into the isocyanate-terminated prepolymer.
- the reactive diluent is added before and/or during and/or after the formation of the isocyanate-terminated prepolymer to control the viscosity.
- Suitable reactive diluents which may be used include mono or polyunsaturated vinyl monomers, which may be polymerised in situ to prepare a vinyl polymer.
- Other reactive diluents include multifunctional materials well known in the art such as multifunctional (meth)acrylate monomers, for example (meth)acrylic acid esters of di- and tri- hydroxy! alcohols (e.g.
- esters of (meth)acrylic acid with monohydric and polyhydric compounds such as ethyl, butyl, hexyl, octyl, and decyl (meth)acrylates; neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), pentaerythritol tri(meth)acrylate and tetra(meth)acrylate, caprolactone (meth)acrylates, alkoxylated
- Additional vinyl monomers as described herein may also be added to the aqueous phase before and/or during and/or after dispersing the isocyanate-terminated prepolymer in water.
- the function of these additional vinyl monomers is not as a diluent to control the viscosity of the isocyanate-terminated prepolymer formation but to contribute to the in-situ preparation of a vinyl polymer.
- All of the vinyl monomer (comprising the reactive diluent as well as the additional vinyl monomer) may be present before commencement of vinyl polymerisation, or the additional vinyl monomer may be added to the reaction medium during the course of the vinyl polymerisation (in one or more stages or continuously).
- the additional vinyl monomer may be added to the reaction medium during the course of the vinyl polymerisation (in one or more stages or continuously).
- some or all of the vinyl monomer may be added before and/or after and/or during the isocyanate-terminated prepolymer preparation prior to its dispersion into water (and therefore may act as a reactive diluent).
- the reactive diluent comprises between 5 and 40%, more preferably between 5 and 35%, most preferably between 10 and 32% and especially between 15 to
- the reactive diluent comprises at least 80 wt%, more preferably at least 95 wt% and most preferably 100 wt% of ⁇ , ⁇ -mono-unsaturated vinyl monomers based on the total weight of vinyl monomers used.
- the reactive diluent comprises 40 to100 wt% of vinyl monomer selected from the group consisting of methylmethacrylate and ethylmethacrylate.
- the reactive diluent added before and/or during and/or after the formation of the iscocyante- terminated prepolymer to control the viscosity comprises ⁇ 45wt%, more preferably ⁇ 40wt% of styrene and styrene based vinyl monomers (such as ⁇ -methyl styrene).
- styrene and styrene based vinyl monomers such as ⁇ -methyl styrene.
- the vinyl monomers may include vinyl monomers carrying functional groups such as crosslinker groups and/or water-dispersing groups. Such functionality may be introduced directly in the vinyl polymer by free-radical polymerisation, or alternatively the functional group may be introduced by a reaction of a reactive vinyl monomer, which is subsequently reacted with a reactive compound carrying the desired functional group.
- Vinyl monomers providing ionic or potentially ionic water-dispersing groups which may be used as additional vinyl monomers include but are not limited to (meth)acrylic acid, itaconic acid, maleic acid, citraconic acid and styrenesulphonic acid.
- the level of vinyl monomers providing ionic or potentially ionic water- dispersing groups is between 0 to 5 wt%, more preferably between 0 and 1 wt% and most preferably 0 wt% of the total level of vinyl monomers used.
- the resultant vinyl polymer has an acid value in the range of from 0 to 20, more preferably 0 to 10 and especially 0 mgKOH/g.
- Vinyl monomers providing non-ionic water-dispersing groups include alkoxy polyethylene glycol (meth)acrylates, preferably having a number average molecular weight of from 350 to 3000. Examples of such monomers which are commercially available include ⁇ -methoxypolyethylene glycol (meth)acrylates.
- Suitable vinyl monomers providing crosslinking groups include acrylic and methacrylic monomers having at least one free carboxyl or hydroxyl group (if used as an additional vinyl monomer), epoxy, acetoacetoxy or carbonyl group, such as acrylic acid and methacrylic acid, glycidyl acrylate, glycidyl methacrylate, aceto acetoxy ethyl methacrylate, allyl methacrylate, tetraethylene glycol dimethacrylate, divinyl benzene and diacetone acrylamide.
- acrylic and methacrylic monomers having at least one free carboxyl or hydroxyl group if used as an additional vinyl monomer
- epoxy acetoacetoxy or carbonyl group
- acrylic acid and methacrylic acid glycidyl acrylate, glycidyl methacrylate, aceto acetoxy ethyl methacrylate, allyl methacrylate, tetraethylene glycol dimethacryl
- the weight average molecular weight (Mw) of the resultant vinyl polymer is at least 60,000 Daltons, more preferably in the range of from 100,000 to 6,000,000 Daltons and most preferably in the range of from 150,000 to 2,500,000 Daltons.
- the Tg of a polymer herein stands for the glass transition temperature and is well known to be the temperature at which a polymer changes from a glassy, brittle state to a rubbery state.
- Tg values of polymers may be determined experimentally using techniques such as Differential Scanning Calorimetry (DSC) or calculated theoretically using the well- known Fox equation where the Tg (in Kelvin) of a copolymer having "n" copolymerised comonomers is given by the weight fractions "W” and the Tg values of the respective homopolymers (in Kelvin) of each comonomer type according to the equation
- the calculated Tg in Kelvin may be readily converted to 0 C.
- the calculated Tg of the resultant vinyl polymer in the polyurethane vinyl hybrid is preferably in the range of from 20 to 12O 0 C and more preferably 30 to 11O 0 C. If the resultant vinyl polymer comprises more than one stage, then preferably the Tg is the calculated Tg of the average resultant vinyl polymer and is in the range of from -20 to 125 0 C, more preferably 5 to 120 0 C and most preferably 30 to 110°C.
- the weight average particle size, assuming a substantially spherical particle shape, of the particles in the polyurethane or polyurethane vinyl hybrid dispersion is preferably less than 500 nm, more preferably in the range of from 20 to 300 nm and most preferably in the range of from 20 to 200 nm. More preferably at least 60 wt%, more preferably at least 75 wt% and most preferably at least 85 wt% of the particles have a particle size less than 500nm.
- a disadvantage of a particle size greater than 500nm is that the sediment content may be increased resulting in unacceptable processing.
- the polymerisation of the vinyl monomers may be carried out as a batch, step ⁇ wise, gradient or as a semi-continuous polymerisation process to make a single or a multistage vinyl polymer.
- Free-radical polymerisation of vinyl monomers will require the use of a free-radical- yielding initiator to initiate the vinyl polymerisation.
- Suitable free-radical-yielding initiators include hydrogen peroxide; percarbonates; organic peroxides, such as acyl peroxides including benzoyl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide (tBHPO) and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide; peroxy esters such as t-butyl perbenzoate and the like; mixtures may also be used.
- organic peroxides such as acyl peroxides including benzoyl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide (tBHPO) and cumene hydroperoxide
- dialkyl peroxides such as di-t-butyl peroxide
- peroxy esters such as t
- the peroxy compounds are in some cases advantageously used in combination with suitable reducing agents (redox systems) such as Na or K pyrosulphite or bisulphite, and iso-ascorbic acid.
- suitable reducing agents such as Na or K pyrosulphite or bisulphite, and iso-ascorbic acid.
- Metal compounds such as Fe.
- EDTA EDTA is ethylene diamine tetracetic acid
- Azo functional initiators may also be used.
- Preferred azo initiators include azobis(isobutyronithle) and 4,4'-azobis(4- cyanovaleric acid).
- the amount of initiator or initiator system used is conventional, e.g. within the range 0.05 to 6 wt % based on the total weight of vinyl monomers used.
- Preferred initiators include azobis(isobutyronitrile) and/or 4,4'-azobis(4-cyanovaleric acid) and redox couples that are active between 30 0 C and 75 0 C. Most preferred initiators are redox couples that are active between 3O 0 C and 75°C such as tBHPO and isoascorbic acid.
- Molecular weight control may be provided by catalytic chain transfer agents or may be provided by using chain transfer agents such as mercaptans and halogenated hydrocarbons, for example mercaptans such as n-dodecylmercaptan, n-octylmercaptan, t- dodecylmercaptan, mercaptoethanol, iso-octyl thioglycolate, C 2 to C 8 mercapto carboxylic acids and esters thereof and halogenated hydrocarbons such as carbon tetrabromide and bromotrichloromethane.
- chain transfer agents such as mercaptans and halogenated hydrocarbons, for example mercaptans such as n-dodecylmercaptan, n-octylmercaptan, t- dodecylmercaptan, mercaptoethanol, iso-octyl thioglycolate, C 2 to C 8 mercap
- Surfactants can be utilised in order to assist in the dispersion of the polyurethane and/or vinyl polymer in water (even if they are self-dispersible). Suitable surfactants include but are not limited to conventional anionic, cationic and/or non-ionic surfactants and mixtures thereof. Anionic and/or non-ionic surfactants are preferred.
- the amount of surfactant used is preferably 0 to 6% by weight, more preferably 0 to 3% by weight and especially 0.1 to 2% by weight based on the weight of the solids in the aqueous composition of the invention.
- a process for making an aqueous composition with a sediment content ⁇ 5% comprising a polyurethane dispersion and containing ⁇ 5 wt% of 1-methyl-2-pyrrolidinone by weight of the polyurethane, wherein the polyurethane has an acid value in the range of from 25 to 65 mgKOH/g, and where the process is carried out in steps comprising: I: reacting in the presence of (a) ⁇ 5 wt% of 1-methyl-2-pyrrolidinone by weight of polyurethane and (b) at least one reactive diluent; (i) 36 to 60 wt% of at least one aromatic polyisocyanate; (ii) 0 to 30 wt% of at least one aliphatic polyisocyanate; (iii) 0 to 15 wt% of at least one isocyanate-reactive polyol bearing ionic and/or potentially ionic water-dispersing groups with a weight average
- IV reacting the isocyanate-terminated prepolymer with at least one active hydrogen chain-extending compound to form the polyurethane; where the active hydrogen/NCO ratio is in the range of from 0.4:1 to 1.3:1 ; Vl: polymerising the reactive diluent.
- a process for making an aqueous composition with a sediment content ⁇ 5% comprising a polyurethane vinyl hybrid dispersion and containing ⁇ 0.5 wt% of 1-methyl-2-pyrrolidinone by weight of the composition, wherein the polyurethane has an acid value in the range of from 25 to 65 mgKOH/g, and where the process is carried out in steps comprising: I: reacting in the presence of (a) ⁇ 5 wt% of 1-methyl-2-pyrrolidinone by weight of polyurethane and (b) at least one reactive diluent; (i) 36 to 60 wt% of at least one aromatic polyisocyanate; (ii) 0 to 30 wt% of at least one aliphatic polyisocyanate; (iii) 0 to 15 wt% of at least one isocyanate-reactive polyol bearing ionic and/or potentially ionic water-dispersing groups with a weight average
- III forming an aqueous dispersion of the isocyanate-terminated prepolymer in water; IV: reacting the isocyanate-terminated prepolymer with at least one active hydrogen chain-extending compound to form the polyurethane; where the active hydrogen/NCO ratio is in the range of from 0.4:1 to 1.3:1 ; V: adding additional vinyl monomer; and
- step Vl polymerising the reactive diluent and vinyl monomer added in step V.
- the process steps may be carried out in a number of variations. For example step
- Step II may be carried out simultaneously with or before step III.
- Steps II, III and IV may be carried out simultaneously.
- Steps II, III, IV and V may be carried out simultaneously.
- Steps II, III, IV, V and Vl may be carried out simultaneously.
- Step V may be carried out at any phase of the process.
- step Il is not carried out after step III or step IV.
- step III is not carried out after Step IV.
- Step Vl is not carried out before Step III.
- Step Vl may be carried out during and/or after Step III.
- Step Il may be carried out simultaneously with step III and the neutralising agent is substantially present in the water.
- Step II, step III and/or step IV may be carried out by means of an in-line mixer. If an in-line mixer is used, preferably at least Step Il is carried out by means of an in-line mixer.
- the time between step III and step IV is preferably less than 40 minutes, more preferably less than 15 minutes, especially less than 5 minutes and most preferably Step
- Step III and Step IV are carried out simultaneously.
- Preferably at least 50 wt% of the active- hydrogen chain extending compound is present in the water before completion of step III.
- Step Vl may be carried out by means of a batch polymerisation process.
- the aqueous composition of the invention typically has a solids content of from about 20 to 55% by weight, more usually from 25 to 45% by weight and especially from 29 to 39% by weight.
- the aqueous composition of the invention is particularly useful for providing the principle component of coating compositions (e.g. protective or decorative coating compositions) especially for coating compositions for floors, for which purpose it may be further diluted with water and/or organic solvents, or it may be supplied in a more concentrated form by evaporation of water and/or organic components of the liquid medium.
- a coating composition it may be applied to a variety of substrates including wood (in particular porous wood), board, metals, stone, concrete, glass, cloth, leather, paper plastics, foam and the like, by any conventional method including brushing, dipping, flow coating, spraying and the like.
- the aqueous composition once applied may be allowed to dry naturally at ambient temperature or the drying process may be accelerated by the application of heat.
- the aqueous composition of the invention may contain conventional ingredients, some of which have been mentioned above; examples include pigments (for example titanium dioxide, iron oxide, chromium based compounds and/or metal pthalocyanine compounds), dyes, emulsifiers, surfactants, plasticisers, thickeners, heat stabilisers, matting agents such as silica, levelling agents, anti-cratering agents, fillers, sedimentation inhibitors, UV absorbers, antioxidants, drier salts, water-soluble and/or water-insoluble co- solvents, wetting agents, defoamers, fungicides, bacteriocides, waxes and the like introduced at any stage of the production process or subsequently.
- pigments for example titanium dioxide, iron oxide, chromium based compounds and/or metal pthalocyanine compounds
- dyes for example titanium dioxide, iron oxide, chromium based compounds and/or metal pthalocyanine compounds
- emulsifiers for example titanium dioxide, iron oxide, chro
- the isocyanate-terminated prepolymer may be dispersed in a preformed polymer dispersion including vinyl polymer, polyurethane, alkyd, polyurethane vinyl hybrid dispersions and mixtures thereof.
- the aqueous composition of the invention preferably contains less than 15 wt% and more preferably less than 10 wt % of organic co-solvents based on the weight of the composition.
- the aqueous coating composition of the invention may be substantially co- solvent-free.
- a substantially co-solvent-free aqueous composition is meant that the composition must contain less than 1.5 wt % of organic co-solvents based on total polymer solids, more preferably less than 0.5 wt %, and most preferably no organic co- solvent at all.
- substantially co-solvent-free aqueous compositions which are film forming at ambient temperature it has been found that an addition of 2 to 15 wt%, more preferably 4 to 12 wt% and most preferably 6 to 10 wt% of an organic co-solvent Q based on polymer solids can give an improved level of chemical and stain resistance.
- Organic co-solvent Q may optionally be added at any stage of the isocyanate- terminated prepolymer or polyurethane or polyurethane vinyl hybrid preparation to control the viscosity.
- Organic co-solvent Q has an evaporation rate from 0.001 to 0.1 , more preferably from 0.002 to 0.05 and most preferably from 0.002 to 0.02, relative to butyl acetate with an evaporation rate of 1.0.
- the organic co-solvent Q is selected from the group consisting of oxygen containing co-solvents.
- oxygen containing co-solvents Especially preferred are ethyldiglycol, butyl glycol, butyldiglycol, Dowanol DPnB and Dowanol DPM (Dowanol is a trade mark of Dow).
- the aqueous composition of the invention can be used in combination with other polymer compositions which are not according to the invention.
- K ⁇ nig Hardness as used herein is a standard measure of hardness, this being a determination of how the viscoelastic properties of a film formed from the dispersion slows down a swinging motion deforming the surface of the film and is measured according to DIN 53157 using an Erichsen hardness equipment.
- the aqueous composition of the invention, and more preferably the aqueous composition of the second embodiment of the invention when in the form of a film has a K ⁇ nig Hardness > 120s, more preferably > 130s, most preferably > 140s, especially > 160s and especially >165s.
- Elongation at break as used herein is a measure of the elongation at break of an unsupported film (i.e. not on a substrate) and is measured using an lnstron tensile device and is defined as the maximum elongation until break under a constant strain rate.
- the aqueous composition of the invention and more preferably the aqueous composition of the second embodiment of the invention, when in the form of a film has an elongation at break > 50% and a K ⁇ nig Hardness > 120s.
- the aqueous composition of the invention containing ⁇ 2 wt% and more preferably 0 wt% of a co-solvent by weight of the composition has a minimum film forming temperature ⁇ 50 0 C, more preferably ⁇ 28°C and especially ⁇ 23 0 C.
- the aqueous composition of the invention and more preferably the aqueous composition of the second embodiment of the invention, containing ⁇ 2 wt% of a co-solvent by weight of the composition has a minimum film forming temperature ⁇ 50 0 C and when in the form of a film has a K ⁇ nig Hardness > 120s.
- the sediment content is determined after preparation of the polyurethane composition but before any filtration is carried out.
- the aqueous composition of the invention preferably has a sediment content of ⁇ 2.5%, more preferably ⁇ 1 %, more preferably ⁇ 0.5% and especially ⁇ 0.35%.
- polyurethanes based substantially on aromatic isocyanates have a tendency to yellow over time.
- polyurethane dispersion of the invention demonstrated a significant reduction in yellowing when compared to a similar aromatic polyurethane with high levels of NMP.
- the yellowness may be determined by measuring the colour co-ordinates of a film of a composition using a Dr Lange Spectro-pen (type LMG161), and 'b' is a measure of yellowness (+b) or blueness (-b).
- the coordinates approach zero for neutral colours such as white, grey or black. The higher the values are, the more saturated a colour is.
- the change in yellowness of the resultant film was determined by measuring (w) the yellowness of the substrate before UV exposure, (x) the yellowness of the film coated in the substrate before UV exposure, (y) the yellowness of the substrate after UV exposure and (z) the yellowness of the film coated on the substrate after UV exposure.
- Yellowing ( ⁇ b) is defined as ((z) - (y)) - ((x) - (w)).
- the value of ⁇ b for the composition of the invention is ⁇ 3.0 and more preferably ⁇ 2.7.
- a fifth embodiment of the present invention is provided a method for coating a substrate with an aqueous composition as described herein.
- aqueous composition as described herein in an aqueous coating composition.
- a seventh embodiment of the present invention there is provided the use of an aqueous composition as described herein for coating floors.
- Hydrazine Hydrazine hydrate available from Bayer AG Abex2545 Nonionic surfactant available from Rhodia
- BA n-Butyl acrylate available from BASF UK Ltd
- BMA n-Butyl methacrylate available from Arkema Nederland bv
- FeEDTA Iron-ethylenediaminetetracetic acid complex, 1% in water
- Dowanol DPM Di(propylene glycol) monomethyl ether available from Dow Benelux
- Stage 2 Polyurethane dispersion: A 2000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with Rubinate 9279 (511.9 g), lonol cp (0.48 g), MMA (240.0 g) and STY (240.0 g). Then a mixture containing CHDM (65.74 g), DMPA (95.20 g), the dispersing non-ionic diol prepared in stage 1 (56.0 g) and Terathane1000 (391.1 g) was added over a period of 60 minutes. The reaction was allowed to exotherm to 5O 0 C. After the exotherm was complete the reaction was kept at 85°C for 2 hours. The NCO-content of the resultant isocyanate-terminated prepolymer was 3.98% (theoretical 4.23%).
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 500 g of the isocyanate-terminated prepolymer over 1 hour to deionised water (1064 g) containing DMEA (21.7 g), 15.2% hydrazine (46.9 g) and ABEX2545 (10.5 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 50 0 C and the dispersion temperature was controlled between 25 to 30 0 C.
- Stage 3 Polyurethane vinyl (50/50) hybrid dispersion:
- Stage 1 Polvurethane dispersion: A 2000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with Rubinate 9279 (562.4 g), lonol cp (0.4g) and MMA (369.3 g). Then a mixture containing CHDM (48.4), DMPA (125.5 g) and TerathaneiOOO (494.4 g) was added over a period of 60 minutes. The reaction was allowed to exotherm to 50 0 C. After the exotherm was complete the reaction was kept at 85 0 C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was 4.47% (theoretical 4.64%).
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 300 g of the isocyanate-terminated prepolymer at 50 0 C over 1 hour to deionised water (851.6g) containing DMEA (17.20 g), 15.2% hydrazine (29.58 g) and Disponyl AFX4060 (5.77 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 50 0 C and the dispersion temperature was controlled between 25 to 30 0 C.
- Stage 2 Polyurethane vinyl (50/50) hybrid dispersion: To the dispersion prepared in Stage 1 (1204.2g) was charged BA (43.9 g) and STY (117.7 g).
- the dispersion was allowed to stir for 1 hour at ambient temperature.
- a 10% tBHPO solution in water (6.0 g) and a 1% FeEDTA solution in water (3.0 g) followed by feeding a 1% IAA solution in water (46.2 g) over a period of 45 minutes.
- the resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Stage 1 Polvurethane dispersion: A 2000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with DMPA (125.5 g), CHDM (48.5 g), PPG 1000 (574.2 g), , MMA (369.2 g), TDI (482.5 g) and lonol cp (0.4). The reaction was allowed to exotherm to 5O 0 C. After the exotherm was complete the reaction was kept at 85 0 C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was 4.80% (theoretical 4.85%).
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 275 g of the isocyanate-terminated prepolymer at 50°C over 1 hour to deionised water (782 g) containing DMEA (15.77 g), 15.2% hydrazine (31.43 g) and of Disponyl AFX4060 (10.57 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 5O 0 C and the dispersion temperature was controlled between 25 to 30°C.
- Stage 2 Polyurethane vinyl (30/70) hybrid dispersion: To the dispersion prepared in Stage 1 (540 g) was charged deionised water (321.3 g), BA (47.3 g), MMA (42.7 g) and STY (127.0 g). After the addition of the additional vinyl monomers the dispersion was allowed to stir for 1 hour at ambient temperature. To the resultant dispersion was then added a 10% tBHPO solution in water (6.5 g) and a 1% FeEDTA solution in water (3.2 g) followed by feeding a 2.5% IAA solution in water (19.9 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Example IV Example IV:
- Stage 1 Polvurethane dispersion: A 2000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with DMPA (96.0 g), CHDM (32.0 g), PPG1000 (622.1g), MMA (320.0 g), Rubinate 9279 (529.9 g) and Ionol cp (0.3 g). The reaction was allowed to exotherm to 50 0 C. After the exotherm was complete the reaction was kept at 85 0 C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was 4.48% (theoretical 4.92%).
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 375.0 g of the isocyanate-terminated prepolymer at 5O 0 C over 1 hour to deionised water (886.6 g) containing Dowanol DPM (79.0 g), DMEA (16.4 g), 15.2% hydrazine (37.9 g) and Abex2545 (18.0 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 50 0 C and the dispersion temperature was controlled between 25 to 3O 0 C.
- Stage 2 Polvurethane vinyl (60/40) hybrid dispersion: To the dispersion prepared in Stage 1 (1414.7 g) was charged MMA (25.0) and STY (100.0 g). After the addition of the additional vinyl monomers the dispersion was allowed to stir for 1 hour at ambient temperature. To the resultant dispersion was then added a 10% tBHPO solution in water (5.2 g) and a 1 % FeEDTA solution in water (2.6 g) followed by feeding a 2.5% IAA solution in water (16.0 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Stage 1 Polvurethane dispersion: A 2000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with DMPA (122.5 g), Priplast 3192 (489.2 g), MMA (420.0 g), Rubinate 9279 (368.4 g) and Ionol cp (0.4). The reaction was allowed to exotherm to 5O 0 C. After the exotherm was complete the reaction was kept at 85 0 C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was 3.22% (theoretical 3.47%).
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 500 g of the isocyanate-terminated prepolymer at 5O 0 C over 1 hour to deionised water (956.9 g) containing DMEA 32.0 g, 15.2% hydrazine (36.3 g) and Abex2545 (21.0 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 5O 0 C and the dispersion temperature was controlled between 25 to 3O 0 C.
- Stage 2 Polvurethane vinyl (30/70) hybrid dispersion:To the dispersion prepared in Stage 1 (1549.0 g) was charged a 10% tBHPO solution in water (3.90 g) and a 1% FeEDTA solution in water (2.0 g) followed by feeding a 2.5IAA solution in water (12.0 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Stage 1 Polyurethane dispersion: A dispersion of an isocyanate-terminated prepolymer was made by feeding 350 g of the isocyanate-terminated prepolymer described in Example V, Stage 1 at 5O 0 C over 1 hour to 791.0 g of deionised water containing DMEA (22.4 g), 15.2% hydrazine (25.4 g) and Abex2545 (14.7 g). The isocyanate-terminated prepolymer temperature during dispersion was kept at 50°C and the dispersion temperature was controlled between 25 to 30 0 C.
- Stage 2 Polvurethane vinyl (50/50) hybrid dispersion: To the dispersion prepared in Stage 1 (1204.6 g) was charged 2-EHA (49.Og) and STY (91.0 g). After the addition of the additional vinyl monomers the dispersion was allowed to stir for 1 hour at ambient temperature. To the resultant dispersion was then added a 10% tBHPO solution in water (6.4 g) and a 1% FeEDTA solution in water (3.2 g) followed by feeding a 2.5% IAA solution in water (19.6 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Stage 1 Polvurethane dispersion: A dispersion of the isocyanate-terminated prepolymer was made by feeding 375.0 g of the isocyanate-terminated prepolymer prepared as described in Example IV stage 1 at 5O 0 C over 1 hour to deionised water (1087.4 g) containing Dowanol DPM (79.0 g), DMEA (16.4 g), EDA (10.8 g) and Abex2545 (18.0 g). The isocyanate-terminated prepolymer temperature during dispersion was kept at 50 0 C and the dispersion temperature was controlled between 25 to 30 0 C.
- Stage 2 Polvurethane vinyl (60/40) hybrid dispersion: To the dispersion prepared in Stage 1 (1506.6 g) was charged BA (25.0) and STY (100.0 g). After the addition of the additional vinyl monomers the dispersion was allowed to stir for 1 hour at ambient temperature. To the resultant dispersion was then added a 10% tBHPO solution in water (5.2 g) and a 1 % FeEDTA solution in water (2.6 g) followed by feeding a 2.5% IAA solution in water (16.0 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Stage 1 Polvurethane dispersion: A 1000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with DMPA (48.0 g), CHDM (14.4 g), Priplast 3192 (240.6 g), MMA (120.0 g), TDI (177.04 g) and lonol cp (0.1). The reaction was allowed to exotherm to 50 0 C. After the exotherm was complete the reaction was kept at 85°C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was 5.73% (theoretical 6.15%).
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 500.0 g of the isocyanate-terminated prepolymer at 50 0 C over 1 hour to deionised water (955.9 g) containing DMEA (29.2 g), 15.2% hydrazine (63.2) g and Disponyl AFX4060 (20.0 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 5O 0 C and the dispersion temperature was controlled between 25 to 30°C.
- Stage 2 Polyurethane vinyl (80/20) hybrid dispersion: To the dispersion prepared in Stage 1 (1571.2 g) was charged a 10% tBHPO solution in water (2.6 g) and a 1% FeEDTA solution in water (1.3 g) followed by feeding a 2.5% IAA solution in water (8.0 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Stage 1 Polyurethane dispersion: A 2000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with DMPA (91.0 g), CHDM (45.5 g), Terathane1000 (343.6 g), MMA (390.0 g), Rubinate 9279 (343.9 g), IPDI (86.0 g) and lonol cp (0.4). The reaction was allowed to exotherm to 5O 0 C. After the exotherm was complete the reaction was kept at 88°C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 580.0 g of the isocyanate-terminated prepolymer at 5O 0 C over 45 min to deionised water (1113.6 g) containing DMEA (29.7 g), 15.2% hydrazine (50.7 g) and Disponyl AFX4030 (40.6 g).
- the isocyanate -terminated prepolymer temperature during dispersion was kept at 50 0 C and the dispersion temperature was controlled between 25 to 30 0 C.
- Stage 2 Polyurethane vinyl (70/30) hybrid dispersion: To the dispersion prepared in Stage 1 (800.0 g) was charged a 10% tBHPO solution in water (2.0 g) and a 1% FeEDTA solution in water (1.0 g) followed by feeding a 2.5% IAA solution in water (6.1 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Stage 1 Polvurethane dispersion: A dispersion of the isocyanate-terminated prepolymer was made by, feeding 580.0 g of the isocyanate-terminated prepolymer described in Example IX at 50 0 C over 1 hour to deionised water (1113.6 g) containing DMEA (29.7 g), 15.2% hydrazine (50.7 g) and Disponyl AFX4030 (40.6 g). The isocyanate-terminated prepolymer temperature during dispersion was kept at 50°C and the dispersion temperature was controlled between 25 to 30°C.
- Stage 2 Polvurethane vinyl (50/50) hybrid dispersion: To the dispersion prepared in Stage 1 (1000.0 g) was charged BMA (100.0) and STY (27.2 g). After the addition of the additional vinyl monomers the dispersion was allowed to stir for 1 hour at ambient temperature. To the resultant dispersion was then added a 10% tBHPO solution in water (5.8 g) and a 1 % FeEDTA solution in water (2.9 g) followed by feeding a 2.5% IAA solution in water (17.8 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Example Xl Example Xl:
- Stage 1 Polvurethane dispersion: A dispersion of the isocyanate-terminated prepolymer was made by feeding 358.0 g of the isocyanate-terminated prepolymer described in
- Stage 2 Polvurethane vinyl (50/50) hybrid dispersion: To the dispersion prepared in
- Stage 1 (1390.2 g) was charged BMA (112.50 g) and STY (31.1 g). After the addition of the additional vinyl monomers the dispersion was allowed to stir for 1 hour at ambient temperature. To the resultant dispersion was then added a 10% tBHPO solution in water
- Stage 1 Polvurethane dispersion: A 3000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with CHDM (76.8), DMPA (192.0 g), Terathanei 000 (902.2 g), TDI (749.1 g), lonol cp (0.3) and MMA (480.0 g). The reaction was allowed to exotherm to 50 0 C. After the exotherm was complete the reaction was kept at 85°C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was 4.87% (theoretical
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 550.0 g of the isocyanate-terminated prepolymer at 50 0 C over 1 hour to deionised water (1120.8 g) containing DMEA (32.2 g), EDA (16.3 g) and Disponyl AFX4060 (22.0 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 60 0 C and the dispersion temperature was controlled between 25 to 30°C.
- Stage 2 Polvurethane vinyl (80/20) hybrid dispersion: To the dispersion prepared in
- Stage 1 (1740.0 g) was added a 10% tBHPO solution in water (2.9 g) and a 1% FeEDTA solution in water (1.4 g) followed by feeding a 2.5% IAA solution in water (8.8 g) over a period of 45 minutes.
- the resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Example XIII Stage 1 : Polvurethane dispersion: A 1000 cm 3 flask equipped with a thermometer and overhead stirrer was charged with CHDM (19.2), DMPA (48.0), PEC90 (191.4 g), Rubinate 9279 (221.4 g), lonol cp (0.1) and MMA (120.0 g). The reaction was allowed to exotherm to 50°C. After the exotherm was complete the reaction was kept at 85 0 C for 2 hours. The NCO-content of the isocyanate-terminated prepolymer was 4.45% (theoretical 4.87%).
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 500.0 g of the isocyanate-terminated prepolymer at 6O 0 C over 1 hour to deionised water (939.7 g) containing DMEA (29.2 g), 15.2% hydrazine (47.2 g) and Disponyl AFX4030 (40.0 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 60 0 C and the dispersion temperature was controlled between 25 to 30°C.
- Stage 2 Polyurethane vinyl (80/20) hybrid dispersion: To the dispersion prepared in Stage 1 (1560.0 g) was added a 10% tBHPO solution in water (3.5 g) and a 1 % FeEDTA solution in water (1.7 g) followed by feeding a 2.5% IAA solution in water (10.6 g) over a period of 45 minutes. The resultant polyurethane vinyl hybrid dispersion was filtered through 75 micron filter cloths.
- Sediment is unstabilised solid material (in the order of microns rather than nanometers) which is formed during dispersing or reaction and which will settle or precipitate upon storage and / or heating. It may be determined quantitatively by centrifuging. The sediment content was determined by taking 50cm 3 of the resultant dispersion of the examples prepared above, diluting this with water (1 :1) and centrifuging the diluted composition for 15 minutes at 1500rpm (276G) rpm in a centrifuge tube.
- Each division on the tube tip represents 0.05 cm 3 or 0.05% sediment.
- the outcome, i.e. the level of solid sediment in the tube tip was then multiplied by 2 to take into account the dilution factor.
- KH K ⁇ nig Hardness
- a dispersion of the isocyanate-terminated prepolymer was made by feeding 500.0 g of the isocyanate-terminated prepolymer at 6O 0 C over 1 hour to 1127.8 g of deionised water containing DMEA (20.1 g), 15.2% hydrazine (48.1 g) and ABEX2545 (24.0 g).
- the isocyanate-terminated prepolymer temperature during dispersion was kept at 50°C and the dispersion temperature was controlled between 25 to 30 0 C.
- the polyurethane dispersion was prepared by the addition of 400.0 g prepolymer to an aqueous phase which contained triethyl amine (26.1g), hydrazine (1.0) and water (841.2 g). The residual hydrazine (0.5g) was simultaneously fed, also in 1 hour at ambient temperature. The degree of neutralisation on equivalents was 1.44:1 and the total degree of extension was 0.24:1.
- the final polyurethane vinyl (50/50) hybrid polymer was prepared by radical polymerisation of the vinyl monomers in the dispersion as well as additional vinyl monomers according to the following recipe: Polyurethane dispersion (851.8g), deionised water (309.6 g), tBHPO (1.3g), IAA, 1 % solution in water (60.0 g), STY (88.6 g), MMA (15.6 g), acrylonitrile (18.0 g) and BA (11.1 g).
- U/A from the dispersions described above following the procedure described in example 12, US 5,137,961.
- the resultant specification did not correspond to the specifications given in US 5,137,961.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP05756105.2A EP1761579B1 (en) | 2004-06-30 | 2005-06-28 | Low nmp aqueous polyurethane composition with a reactive diluent |
CN200580022235XA CN1980966B (en) | 2004-06-30 | 2005-06-28 | Low NMP aqueous polyurethane composition with a reactive diluent |
US11/630,363 US7951457B2 (en) | 2004-06-30 | 2005-06-28 | Low NMP aqueous polyurethane composition with reactive diluent |
HK07113239A HK1107703A1 (en) | 2004-06-30 | 2007-12-04 | Low nmp aqueous polyurethane composition with a reactive diluent |
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GB0414594A GB0414594D0 (en) | 2004-06-30 | 2004-06-30 | Aqueous composition 1 |
GB0414594.2 | 2004-06-30 |
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WO2006002864A1 true WO2006002864A1 (en) | 2006-01-12 |
Family
ID=32843270
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2005/006932 WO2006002864A1 (en) | 2004-06-30 | 2005-06-28 | Low nmp aqueous polyurethane composition with a reactive diluent |
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Country | Link |
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US (1) | US7951457B2 (en) |
EP (1) | EP1761579B1 (en) |
CN (1) | CN1980966B (en) |
GB (1) | GB0414594D0 (en) |
HK (1) | HK1107703A1 (en) |
WO (1) | WO2006002864A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009105396A1 (en) * | 2008-02-19 | 2009-08-27 | Lubrizol Advanced Materials, Inc. | Aqueous polyurethane hybrid compositions |
EP2708564A1 (en) | 2012-09-13 | 2014-03-19 | Momentive Specialty Chemicals Research Belgium S.A. | Aqueous polyurethane dispersion derived from tertiary alkenyl glycidyl esters |
WO2014040708A2 (en) | 2012-09-13 | 2014-03-20 | Momentive Specialty Chemicals Research Belgium Sa | Aqueous polyurethane dispersion derived from tertiary alkyl glycidyl esters |
EP2765147A1 (en) | 2013-02-06 | 2014-08-13 | Momentive Specialty Chemicals Research Belgium S.A. | Aqueous polyurethane dispersion derived from tertiary alkyl glycidyl esters |
WO2017158015A1 (en) | 2016-03-15 | 2017-09-21 | Dsm Ip Assets B.V. | Aqueous coating composition |
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US7676839B2 (en) * | 2004-03-15 | 2010-03-09 | Xceedid | Systems and methods for access control |
GB0414598D0 (en) * | 2004-06-30 | 2004-08-04 | Avecia Bv | Aqueous compostion III |
GB0414595D0 (en) * | 2004-06-30 | 2004-08-04 | Avecia Bv | Aqueous composition II |
US9752022B2 (en) | 2008-07-10 | 2017-09-05 | Avery Dennison Corporation | Composition, film and related methods |
JP5544724B2 (en) * | 2009-02-18 | 2014-07-09 | 東ソー株式会社 | Aqueous polyurethane resin composition and molded film using the same |
BR112012022175A2 (en) | 2010-03-04 | 2016-10-25 | Avery Dennison Corp | non pvc film and non pvc laminate |
DE102013108828B4 (en) * | 2013-08-14 | 2016-11-17 | Synthopol Chemie Dr. Rer. Pol. Koch Gmbh & Co. Kg | Aqueous hydroxyl-containing polyurethane dispersions, a process for their preparation and their use in coating compositions |
MX2016007964A (en) | 2013-12-30 | 2016-09-09 | Avery Dennison Corp | Polyurethane protective film. |
ES2706311T5 (en) * | 2014-12-23 | 2023-02-01 | Covestro Netherlands Bv | Aqueous coating composition with a soft touch after drying |
WO2018146142A1 (en) * | 2017-02-08 | 2018-08-16 | Dsm Ip Assets B.V. | Aqueous coating composition |
KR20220016901A (en) * | 2019-06-04 | 2022-02-10 | 다우 글로벌 테크놀로지스 엘엘씨 | Heat-sensitive aqueous polyurethane dispersant and method for preparing same |
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GB0414595D0 (en) * | 2004-06-30 | 2004-08-04 | Avecia Bv | Aqueous composition II |
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2004
- 2004-06-30 GB GB0414594A patent/GB0414594D0/en not_active Ceased
-
2005
- 2005-06-28 EP EP05756105.2A patent/EP1761579B1/en active Active
- 2005-06-28 WO PCT/EP2005/006932 patent/WO2006002864A1/en active Application Filing
- 2005-06-28 US US11/630,363 patent/US7951457B2/en active Active
- 2005-06-28 CN CN200580022235XA patent/CN1980966B/en active Active
-
2007
- 2007-12-04 HK HK07113239A patent/HK1107703A1/en not_active IP Right Cessation
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JPH10237138A (en) * | 1997-02-24 | 1998-09-08 | Toyo Ink Mfg Co Ltd | Production of aqueous urethane composite resin |
JPH10292024A (en) * | 1997-04-21 | 1998-11-04 | Toyo Ink Mfg Co Ltd | Production of water-based urethane composite resin |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009105396A1 (en) * | 2008-02-19 | 2009-08-27 | Lubrizol Advanced Materials, Inc. | Aqueous polyurethane hybrid compositions |
JP2011512445A (en) * | 2008-02-19 | 2011-04-21 | ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド | Aqueous polyurethane hybrid composition |
AU2009215691B2 (en) * | 2008-02-19 | 2014-08-28 | Lubrizol Advanced Materials, Inc. | Aqueous polyurethane hybrid compositions |
EP2708564A1 (en) | 2012-09-13 | 2014-03-19 | Momentive Specialty Chemicals Research Belgium S.A. | Aqueous polyurethane dispersion derived from tertiary alkenyl glycidyl esters |
WO2014040708A2 (en) | 2012-09-13 | 2014-03-20 | Momentive Specialty Chemicals Research Belgium Sa | Aqueous polyurethane dispersion derived from tertiary alkyl glycidyl esters |
EP2765147A1 (en) | 2013-02-06 | 2014-08-13 | Momentive Specialty Chemicals Research Belgium S.A. | Aqueous polyurethane dispersion derived from tertiary alkyl glycidyl esters |
WO2017158015A1 (en) | 2016-03-15 | 2017-09-21 | Dsm Ip Assets B.V. | Aqueous coating composition |
WO2017158016A1 (en) | 2016-03-15 | 2017-09-21 | Dsm Ip Assets B.V. | Aqueous coating composition |
Also Published As
Publication number | Publication date |
---|---|
CN1980966A (en) | 2007-06-13 |
EP1761579B1 (en) | 2017-11-15 |
GB0414594D0 (en) | 2004-08-04 |
US20080038563A1 (en) | 2008-02-14 |
EP1761579A1 (en) | 2007-03-14 |
US7951457B2 (en) | 2011-05-31 |
CN1980966B (en) | 2011-08-10 |
HK1107703A1 (en) | 2008-04-11 |
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