CN101142250B - Aqueous polyurethane compositions - Google Patents

Aqueous polyurethane compositions Download PDF

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CN101142250B
CN101142250B CN2006800086294A CN200680008629A CN101142250B CN 101142250 B CN101142250 B CN 101142250B CN 2006800086294 A CN2006800086294 A CN 2006800086294A CN 200680008629 A CN200680008629 A CN 200680008629A CN 101142250 B CN101142250 B CN 101142250B
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isocyanate
acid
aqueous polyurethane
polyurethane composition
hydrazides
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CN101142250A (en
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巴布罗·斯帝温克尔
安德里亚斯·雅格布斯·约斯恩·谷斯
保卢斯·约翰内斯·玛丽亚·霍内
格拉尔杜斯·柯纳里斯·欧文比克
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Kostron Netherlands Co ltd
Covestro Netherlands BV
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DSM IP Assets BV
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Priority claimed from PCT/EP2006/002454 external-priority patent/WO2006097318A1/en
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Abstract

An aqueous polyurethane composition comprising a polyurethane which is the reaction product of: (A) an isocyanate-terminated prepolymer and (B) at least one active- hydrogen chain-extending compound comprising at least 0.20 stoichiometric equivalents with respect to the isocyanate content of the isocyanate-terminated prepolymer (A), of an active-hydrogen chain-extending compound selected from the group consisting of hydrazine, hydrazine derivatives and mixtures thereof; and wherein at least 0.2 stoichiometric equivalents of the anionic or potentially anionic water-dispersing groups are neutralised with ammonia.

Description

Aqueous polyurethane composition
The present invention relates to aqueous polyurethane composition, this method for compositions of preparation and the purposes of this compsn in coated substrate.
Polyurethane composition is used to make the coating with desired coating characteristic for a long time.For example, such coating comprises the undercoat of the base material that is used for plastic basis material, particularly uses in film packaging industry (comprising food product pack) and the undercoat that is used for film, label and fine arts application.This undercoat uses with heat sealable top coat usually.Top coat comprises negatively charged ion and positively charged ion polyvinylidene dichloride (PVDC), acrylic acid or the like, urethane and composition thereof.
US 5656701 has described through the mixture with chainextender and telomex polyurethane prepolymer has been carried out the polyurethane resin composition that chain extension prepares.The characteristic of these urethane is to have the group that at least one is selected from diazanyl, hydrazide group and amino urea groups in the molecule.This urethane resin can use chainextender and/or telomex with at least one diazanyl or hydrazide group to prepare.The use of telomex can cause forming low molecular weight substance, and this adhesivity to urethane is deleterious.
EP 646609 has described terminal hydrazide group functional polyurethane dispersion, and this dispersion-s is through for example comprising hydrazine or hydrazides (adipic dihydrazide for example, the crossing expansion and obtain of chainextender ADH) or its mixture.
EP 350157 has described the waterborne polyurethane resin of crossing expansion and the purposes that contains the acrylic acid polymer dispersion of carboxamido-group or ketone group.Here, urethane is described as through having-NHNH with expanding above the normal hydrazine derivative of stoichiometry 2Sense.
Using above a normal a kind of or more kinds of shortcoming that contains the hydrazine chainextender is in the product dispersion-s, usually can detect free hydrazine, and free hydrazine to be considered to have toxicity usually thereby not to expect.
Surprisingly; Aqueous polyurethane composition use ammonia of the present invention is as at least a portion neutralizing agent and use hydrazine or hydrazine derivative as chainextender; This can provide the good adhesivity to plastic basis material (when as undercoat); And obtain high initial sealing intensity and moist sealing intensity (when top coated during), and, therefore there is not free hydrazine owing to used smaller or equal to a normal chainextender of stoichiometry with hot sealing layer.
The invention provides a kind of aqueous polyurethane composition; Said compsn comprises the urethane that acid number is 4-150mgKOH/g, and said compsn comprises the reaction product of following material: (A) by the isocyanate-terminated prepolymer that comprises that following component reaction obtains:
(i) at least a organic multiple isocyanate;
(ii) at least a isocyanate-reactive compound, said isocyanate-reactive compound have anionic property or potential anionic property water-dispersion group;
The (iii) at least a isocyanate-reactive compound that is not (ii) comprised,
Wherein said isocyanate-terminated prepolymer component is with 1.1: 1-6: 1 isocyanic ester reacts with the ratio of isocyanate-reactive group; With
(B) at least a active hydrogen chain extension compound, it comprises with respect to isocyanate-terminated prepolymer
(A) the normal active hydrogen chain extension compound that is selected from hydrazine, hydrazine derivative and composition thereof of isocyanate content at least 0.2 stoichiometry,
Wherein (A) and (B) with 1: 0.5-1: the ratio reaction of 1 isocyanic ester and isocyanate-reactive group, and
Wherein normal said anionic property of at least 0.2 stoichiometry or potential anionic property water-dispersion group neutralize with ammonia.
Term used herein " urethane " comprises a kind of urethane and more than a kind of urethane.
Term used herein " isocyanate-terminated prepolymer " comprises a kind of isocyanate-terminated prepolymer and more than a kind of isocyanate-terminated prepolymer.
Being used for method for producing polyurethanes is known in the art, and for example at the Polyurethane of G.Oertel Handbook 2 NdEdition, a Carl Hanser Publication, 1994 or Szycher ' the s Handbook of Polyurethanes of Michael Szycher, CRC Press has description in 1999, by reference these methods is incorporated into this.Can with at least a organic multiple isocyanate and the reaction of at least a isocyanate-reactive compound, prepare urethane in a conventional manner through method commonly known in the art.Isocyanate-reactive group comprises-CHR 1-COOH (R wherein 1Can be H), alkyl (more preferably C 1-C 8Alkyl) ,-OH ,-SH ,-NH-and-NH 2, wherein-OH ,-NH-and-NH 2Be preferred.
Component (i) comprises any suitable organic multiple isocyanate, comprises POLYMETHYLENE POLYPHENYLISOCYANATE aliphatic series, alicyclic, araliphatic (araliphatic) and/or aromatics.Suitable POLYMETHYLENE POLYPHENYLISOCYANATE instance comprises ethylidene diisocyanate, 1; 6-hexamethylene diisocyanate (HDI) and oligopolymer thereof, isophorone diisocyanate (IPDI), hexanaphthene-1,4-vulcabond, 4,4 '-dicyclohexyl methane diisocyanate (4; 4 '-H12MDI), p-Xylol support vulcabond, to tetramethylxylene diisocyanate (p-TMXDI) (and meta-isomer m-TMXDI), 1; 4-phenylene vulcabond, hydrogenation 2,4 toluene diisocyanate, hydrogenation 2,6-tolylene diisocyanate, 4; 4 '-diphenylmethanediisocyanate (4; 4 '-MDI), polymethylene polyphenylene(poly)isocyanate, 2,4 '-diphenylmethanediisocyanate, 3 (4)-NCO methyl isophthalic acid-isocyanatomethyl (IMCI) and l,5 naphthylene diisocyanates.Can use the mixture of POLYMETHYLENE POLYPHENYLISOCYANATE, also can use the POLYMETHYLENE POLYPHENYLISOCYANATE of modification through introducing carbamate, allophanate, urea, biuret, carbodiimide, uretonimine (uretonimine), urea diketone (urethdione) or isocyanuric acid ester residue.Preferably, POLYMETHYLENE POLYPHENYLISOCYANATE is the araliphatic vulcabond.More preferably, POLYMETHYLENE POLYPHENYLISOCYANATE is selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 toluene diisocyanate and composition thereof.Most preferably, POLYMETHYLENE POLYPHENYLISOCYANATE is an isophorone diisocyanate.
Preferably, isocyanate-terminated prepolymer comprises 10-90wt%, more preferably 15-60wt%, the component of 20-40wt% (i) the weight meter of (that is, with respect to (i)+(ii)+(iii)) most preferably.
Component (ii) comprises any suitable polyvalent alcohol that contains anionic property or potential anionic property water-dispersion group, preferred diol.
Preferred anionic surfactants water-dispersion group is carboxyl, phosphoric acid or sulfonic acid group.The preferred embodiment of this compound comprises carboxylic two pure and mild triols, for example 2, and 2-dimethylol propionic acid (DMPA) or 2, the dihydroxyl alkanoic acid, particularly DMPA of 2-dimethylolpropionic acid (DMBA).Other useful compound comprises aminocarboxylic acid, for example Methionin, halfcystine and 3, and 5-diaminobenzoic acid, and sulfonic acid, for example 4,6-diaminobenzene-1,3-disulfonic acid, 5-sodium are for sulfoisophthalic acid (SSIPA) and taurine.
More high-molecular weight contains anionic water and disperses the examples for compounds of group to comprise polyethers, polyester and the polycarbonate polyol that contains hydroxy-acid group; The fumaric acid polyethers glycol ester of for example describing among the US 4460738, or the binary alkanoic acid of caprolactone modification for example.
Perhaps, can be by following introducing anionic property or potential anionic property water-dispersion group: before being attached to this part in the final urethane, during or afterwards, make OH official can polyvalent alcohol or urethane react with cyclic anhydride.
The compound that preferably contains anionic property or potential anionic property water-dispersion group is DMBA, DMPA and composition thereof.
In polyurethane dispersions, it is the form of salt that anionic water disperses group preferred all or part of.The form that is converted into salt realizes through the neutralization of urethane and alkali that alternatively this preferably carries out in the preparation process of urethane and/or in the preparation process of water-based paint compositions of the present invention.
When in during with anionic property or potential anionic property water-dispersion group, preferably at least 0.25, more preferably 0.25-3 in addition more preferably 0.5-2, most preferably 0.7-2 the normal anionic property of stoichiometry or potential anionic property water-dispersion group are neutralized by ammonia.
Alternatively, for example in the polyurethane preparation process and after the preparation, can be once or add several times more than 3 normal ammonia of stoichiometry, thus better dispersion stabilization (but only adding under prerequisite of excess ammonia after the dispersion) is provided.With in amine or the mineral alkali with remaining anionic property or potential anionic property water-dispersion group.In addition, can use the extra amine of 2 SA at the most.Suitable amine comprises tertiary amine, for example triethylamine dimethyl butylamine or N, N-dimethylethanolamine.But known triethylamine has disadvantageous toxicity.Suitable mineral alkali comprises alkali metal hydroxide and carbonate, for example Lithium Hydroxide MonoHydrate, sodium hydroxide or Pottasium Hydroxide.Also can use hyamine hydroxide, for example N +(CH 3) 4(OH).Usually, use that to provide possibly be the alkali of the desired gegenion of compsn.For example, preferred gegenion comprises Li +, Na +, K +, NH 4 +And through substituted ammonium salt.
Preferably, isocyanate-terminated prepolymer comprise 0.1-80wt%, more preferably 0.1-40wt%, most preferably 1-15wt%, particularly 2-10wt%, the most particularly 2-8wt% component (ii).
Preferably, component weight-average molecular weight (Mw) (ii) is 100-10000g/mol, more preferably 100-5000g/mol, most preferably 120-1000g/mol, particularly 125-155g/mol.
Component (iii) can comprise cationic water and disperse group and/or can also comprise nonionic water-dispersion group.Cationic water disperses examples of groups to comprise can to use the acid neutralization or by pyridyl, imidazolyl and/or the tertiary amine groups of permanent ionize (for example using methyl-sulfate).
Preferred nonionic water-dispersion group is the polyalkylene oxides base, more preferably the polyethylene oxide base.The a bit of of this polyethylene oxide base can be replaced by propylidene segment and/or oxybutylene segment, but this polyethylene oxide base should still comprise oxyethane as staple.When water dispersible group was polyethylene oxide, this polyethylene oxide base preferably had 175-5000g/mol, more preferably 350-2200g/mol, the molecular weight of 660-2200g/mol most preferably.
This examples of compounds that comprises nonionic water-dispersion group comprises that molecular weight for example is 550,750,1000 and the methoxy poly (ethylene glycol) (MPEG) of 2000g/mol.
The urethane of gained preferably (ii) and (iii) comprises the ion and/or the non-ionic water-dispersion group of enough concentration owing to component; Can make this urethane have from water dispersible (can be dispersed in the water and need not use additional dispersion agent); But the concentration of this group preferably is not big to making this urethane have the degree of unacceptable highly water-soluble, so that do not damage the water sensitivity of final coating.
And the intensity of ion and/or non-ionic water-dispersion group or its efficient as dispersion and/or stable group also possibly influence required optimum quantity.
Component (iii) also can comprise crosslinkable groups.Crosslinkable groups can provide self-crosslinkable urethane, and this self-crosslinkable urethane can be at room temperature crosslinked through multiple mechanism, and these mechanism include but not limited to, the crosslinked and silane condensation of Schiff alkali.
Schiff alkali is crosslinked to be meant; Reaction through carbonyl functional group and carbonyl reaction property amine and/or hydrazine (the perhaps amine of sealing and/or the hydrazine of sealing) functional group takes place crosslinked; Be meant aldehyde or ketone groups this carbonyl functional group, comprise the enol carbonyl that for example appears in the acetoacetyl.
Silane condensation is meant, alcoxyl silane perhaps-the SiOH base reacts in the presence of water, anhydrate and/or alkyl alcohol (for example methyl alcohol) provides siliconoxygen bond through in the drying process of water-based paint compositions, removing.
Other mechanism of crosslinking that is known in the art comprises those that following reaction provides: through the reaction of epoxide group with amino, carboxylic acid or sulfydryl; Sulfydryl and reaction such as the ethylenic unsaturated group of fumarate and acryl; The reaction of mask type (masked) epoxide group and amino or sulfydryl; The reaction of lsothiocyanates and amine, alcohol or hydrazine, amine (the for example end capped polyalkylene oxides of quadrol or polyfunctional amine) and the basic reaction that forms enamine of β-diketone (for example acetoacetyl oxygen or aceto-acetamide).Use the crosslinked group of sealing, for example the isocyanate groups of sealing possibly be favourable.Expect that at those most preferred crosslinking method is the crosslinked or alcoxyl crosslinked with silicane of Schiff alkali under crosslinked situation.
Molecular weight is that the polyvalent alcohol of 500-6000g/mol especially comprises two pure and mild triols and composition thereof, has the more polyvalent alcohol of high functionality but also can use, for example the accessory constituent in the mixture of conduct and glycol.Polyvalent alcohol can be the polyvalent alcohol that is used for or is proposed to be used in any chemical species of polyurethane formulations.Particularly, polyvalent alcohol can be polyester, polyesteramide, polyethers, polythioether, polycarbonate, polyacetal, polyolefine or ZGK 5.The weight-average molecular weight of polyvalent alcohol (Mw) is preferably 600-4000g/mol, more preferably 700-3000g/mol.
Operable polyester polyol comprises the hydroxy-end capped reaction product of polyvalent alcohol and polycarboxylic acid; Wherein said polyvalent alcohol for example is terepthaloyl moietie, Ucar 35, Diethylene Glycol, NSC 6366,1; 4-butyleneglycol, furyl dimethyl carbinol, cyclohexanedimethanol, USP Kosher, TriMethylolPropane(TMP) or tetramethylolmethane or its mixture; Said polycarboxylic acid is di-carboxylic acid or their one-tenth ester derivative particularly, for example phthalic acid, succsinic acid, pentanedioic acid, hexanodioic acid, propanedioic acid, toxilic acid and dimer (fatty acid) yl, acid anhydrides or its short-chain alkyl ester (for example terephthalic acid dimethyl esters).The polyester that can also use lactone (for example, caprolactone) and polyvalent alcohol polymerization to obtain.Polyesteramide can obtain through in the polyesterification mixture, introducing amino alcohol (for example thanomin) or polyamines.
Operable polyether glycol comprises the product by following acquisition: the for example polymerization of the ring-type oxide compound of oxyethane, propylene oxide or THF; Perhaps a kind of or more kinds of such oxide compound is added in the multifunctional initiator, this initiator for example is water, terepthaloyl moietie, Ucar 35, Diethylene Glycol, cyclohexanedimethanol, USP Kosher, TriMethylolPropane(TMP), tetramethylolmethane or dihydroxyphenyl propane.Useful especially polyester comprises through with oxyethane and propylene oxide simultaneously or be added to the polyoxy trimethylene glycol and the triol that obtain in the suitable initiator, the polytetramethylene ether diol that gathers (oxygen ethylidene-oxygen propylidene) two pure and mild triols and obtain through polymerizing tetrahydrofuran successively.
Operable polythioether polyvalent alcohol comprises through with independent condensation of thio-diethylene glycol or the product that obtains with other terepthaloyl moietie, dicarboxylicacid, formaldehyde, amino alcohol or aminocarboxylic acid condensation.
Operable polycarbonate polyol comprises through for example making 1, ammediol, 1,4-butyleneglycol, 1, the glycol of 6-pinakon, Diethylene Glycol or TEG and the diaryl carbonate reaction of for example dipheryl carbonate base ester or the product that obtains with phosgene reaction.
Operable polyacetal polyvalent alcohol comprises through those of glycol that makes for example Diethylene Glycol, triethylene glycol or pinakon and formolite reaction preparation.Suitable polyacetal can also prepare through the polymerizable cyclic acetal.
Suitable polyolefin polyhydric alcohol comprises hydroxy-end capped divinyl or terpenes homopolymer and multipolymer.
Polyvalent alcohol is preferably polyether glycol, more preferably THF homopolymer (be also referred to as polytetramethylene glycol, polybutylene oxide and gather THF).
Most preferably, component (iii) is selected from and gathers THF, W 166, polyester, amino-terminated polyalkylene oxides (Jeffamine that for example, can obtain from Huntsman) or derivatives thereof (those that for example describe EP 317258 B1) and composition thereof.Preferably, the component Mw (iii) that so selects is 300-3000g/mol.
For component (iii), can also use and contain at least one (preferably at least two) isocyanate-reactive group and weight-average molecular weight is lower than 500g/mol, is preferably the low molecular weight organic compound of 40-250g/mol.The example comprises: terepthaloyl moietie, Diethylene Glycol, triethylene glycol, TEG and similarly by Ucar 35 and 1,3-or 1, the polyglycol that the 4-butyleneglycol makes (molecular weight is 499g/mol at the most), NSC 6366; The 1-propyl alcohol, terephthalic acid two (hydroxyethyl) ester, furyl dimethyl carbinol, USP Kosher, 1, the reaction product (molecular weight is 499g/mol at the most) of 4-cyclohexyl dimethanol and these instances and Ucar 35 and/or terepthaloyl moietie.Component (iii) preferably comprises less than 15wt%, is more preferably less than these low molecular weight organic compounds of 10wt%.
Isocyanate-terminated prepolymer preferably comprise 5-90wt%, more preferably 10-80wt%, most preferably 20-75wt%, particularly 45-70wt%, the most particularly 50-70wt% component (iii).
The size of particles of the gained urethane in the compsn is preferably 20-5000nm, and more preferably 25-1000nm most preferably is 30-250nm.
The acid number of urethane is preferably 4-100mgKOH/g, and more preferably 8-65mgKOH/g most preferably is 10-42mgKOH/g, particularly 15-30mgKOH/g.
The number-average molecular weight of urethane (Mn) is preferably 2000-1000000g/mol, and 3000-200000g/mol more preferably, even 4000-100000g/mol more preferably most preferably are 8000-40000g/mol, particularly 10000-20000g/mol.Molecular weight can be through using suitable elutriant (for example THF or DMAC N,N) and being measured by GPC (GPC) with reference to polystyrene standards.
Isocyanate-terminated prepolymer forms through following method traditionally: under substantially anhydrous condition; Under about 30-130 ℃ temperature; Organic multiple isocyanate that stoichiometry is excessive and isocyanate-reactive compound reaction, the reaction between isocyanate groups and isocyanate-reactive group is complete basically; The component of isocyanate-terminated prepolymer is preferably used with certain proportion, and this ratio is preferably about 1.1 corresponding to the ratio of isocyanate groups and isocyanate-reactive group: 1-4: 1, more preferably 1.3: 1-3: 1, particularly 1.4: 1-2: 1.
If desired, can use catalyzer, zirconium or titanium base or the tertiary amine groups catalyzer of for example dibutyl tin laurate and stannous octoate to assist and form isocyanate-terminated prepolymer and/or urethane.
Isocyanate-terminated prepolymer form or final urethane form before, during or afterwards, can add organic solvent alternatively with control viscosity.The instance of solvent comprise can be miscible with water solvent, for example alkyl oxide or its mixture of N-Methyl pyrrolidone, N-ethyl pyrrolidone, N,N-DIMETHYLACETAMIDE, two pure and mild glycol ethers, acetone, ethyl methyl ketone and acetate diol ester such as butyldiglycol.If the use solvent, the minimum solvent of then preferred use.Use based on waterborne compositions weight of the present invention preferably less than 5wt%, be more preferably less than the organic solvent of 1wt%.Most preferably, during preparation waterborne compositions of the present invention, do not add organic solvent.
Aqueous polyurethane composition can be prepared as follows: with isocyanate-terminated prepolymer (A) (alternatively; Be present in the organic solvent medium) be dispersed in the aqueous medium, with at least a chainextender (B) that contains active hydrogen this isocyanate-terminated prepolymer is carried out chain extension at aqueous phase then.
With respect to the isocyanate content of isocyanate-terminated prepolymer (A), the chainextender (B) that contains active hydrogen preferably comprises the normal chain extension compound that contains active hydrogen that is selected from hydrazine, hydrazine derivative and composition thereof of at least 0.4, more preferably at least 0.5, particularly 0.8 stoichiometry.
The instance of suitable hydrazine derivative comprises: azine, for example acetone azine; Substituted hydrazine, dimethylhydrazine, 1 for example, 6-hexa-methylene-two hydrazines, carbon two hydrazines; The hydrazides of polycarboxylic acid and sulfonic acid; The for example list of hexanodioic acid or bishydrazide, amber acid dihydrazide, oxalic acid two hydrazides, m-phthalic acid two hydrazides, winestone acid dihydrazide, 1; 3-phenylene disulfonic acid two hydrazides, omega-amino--caproic acid two hydrazides, Hydrocerol A three hydrazides, 1; 2,4-butane tricarboxylic acid three hydrazides; React the hydrazides that obtains, for example two hydrazine acyl carbonic ethers of γ-maloyl group hydrazine, two semicarbazides and glycol through lactone and hydrazides; And the semicarbazides that obtains by POLYMETHYLENE POLYPHENYLISOCYANATE and excessive hydrazine reaction (forming corresponding semicarbazones with the reactive ketone of for example acetone alternatively then).
Preferred hydrazine derivative is selected from acetone azine, dimethylhydrazine, 1; 6-hexa-methylene-two hydrazines, carbon two hydrazines, hexanodioic acid list hydrazides, adipic dihydrazide, amber acid dihydrazide, oxalic acid two hydrazides, m-phthalic acid two hydrazides, winestone acid dihydrazide, 1; 3-phenylene disulfonic acid two hydrazides, Hydrocerol A three hydrazides, 1; 2,4-butane tricarboxylic acid three hydrazides, γ-maloyl group hydrazine and composition thereof.
Can use the chainextender (using) that contains active hydrogen that the residual isocyanate group in the isocyanate-terminated prepolymer (A) is carried out chain extension with hydrazine and/or hydrazine derivative; Wherein said chainextender comprises amino alcohol, elementary or secondary aliphatic series, alicyclic, aromatics, araliphatic or heterocycle family polyamines, particularly diamines.Water-soluble chainextender is preferred.The instance of the chainextender that available is suitable here comprises quadrol, NSC 446, Triethylenetetramine (TETA), tn, tetramethylenediamine, hexamethylene-diamine, cyclohexanediamine, piperazine, 2-N-METHYL PIPERAZINE, phenylenediamine, tolylene diamine, diformazan penylene diamines, three (2-aminoethyl) amine, 3; 3 '-dinitrobenzene p-diaminodiphenyl, 4; 4 '-methylene radical two (2-chloroaniline), 3; 3 '-two chloro-4; 4 '-diphenyl diamine, 2,6-diamino-pyridine, 4, the affixture of 4 '-diaminodiphenyl-methane, methane diamines, dimethylphenylene diamine, isophorone diamine and NSC 446 and propenoate or its hydrolysate.
At chainextender is for example when polyamines and/or hydrazine derivative, can it be added in the aqueous dispersion of isocyanate-terminated prepolymer, perhaps when isocyanate-terminated prepolymer is dispersed in the aqueous medium it Already in the aqueous medium.Isocyanate-terminated prepolymer also can be dissolved in the organic solvent (being generally acetone), and then in solution, adding entry becomes external phase up to water, is formed urethane by chain extension when removing solvent and form aqueous dispersion through distillation subsequently.
Chain extension can carry out under high temperature, low temperature and envrionment temperature.Optimal temperature is about 5-95 ℃, more preferably about 10-50 ℃.
The total amount of the active hydrogen chain extension compound that uses should make isocyanate groups and the ratio of the active hydrogen in the chainextender (B) in the isocyanate-terminated prepolymer (A) be about (but preferably being higher than just) 1: 1; This ratio is preferably 1: 0.6-1: 1; More preferably 1: 0.7-1: 1; Most preferably be 1: 0.8-1: 0.99, particularly 1: 0.8-1: 0.97.
One embodiment of the present invention provide a kind of aqueous polyurethane composition, and said compsn comprises the urethane that acid number is 10-42mgKOH/g, and said compsn comprises the reaction product of following material:
(A) isocyanate-terminated prepolymer that obtains by following component reaction:
(i) 10-90wt%, the more preferably at least a organic multiple isocyanate of 20-40wt%;
(ii) 0.1-80wt%, the more preferably at least a isocyanate-reactive compound of 2-8wt%, said isocyanate-reactive compound has anionic property or potential anionic property water-dispersion group;
(iii) 5-90wt%, the more preferably at least a isocyanate-reactive compound that is not (ii) comprised of 50-70wt%,
(i)+(ii)+(iii)=100% wherein,
Wherein said isocyanate-terminated prepolymer component is with 1.1: 1-6: 1 isocyanic ester reacts with the ratio of isocyanate-reactive group; With
(B) at least a active hydrogen chain extension compound, its isocyanate content with respect to isocyanate-terminated prepolymer (A) comprise the normal active hydrogen chain extension compound that is selected from hydrazine, hydrazine derivative and composition thereof of at least 0.4 stoichiometry,
Wherein (A) and (B) with 1: 0.8-1: the ratio reaction of 0.99 isocyanic ester and isocyanate-reactive group, and
Wherein normal said anionic property of 0.25-3 stoichiometry or potential anionic property water-dispersion group neutralize with ammonia.
Another embodiment of the invention provides a kind of aqueous polyurethane composition, and said compsn comprises the urethane that acid number is 10-42mgKOH/g, and said compsn comprises the reaction product of following material:
(A) isocyanate-terminated prepolymer that obtains by following component reaction:
(i) at least a organic multiple isocyanate of 20-40wt%, said organic multiple isocyanate is selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 toluene diisocyanate and composition thereof;
The (ii) at least a isocyanate-reactive compound of 2-8wt%; Said isocyanate-reactive compound has anionic property or potential anionic property water-dispersion group; It is selected from 2,2-dimethylol propionic acid (DMPA), 2,2-dimethylolpropionic acid (DMBA) and composition thereof;
The (iii) at least a isocyanate-reactive compound that is not (ii) comprised of 50-70wt%; The Mw of said isocyanate-reactive compound be 300-3000g/mol, more preferably 600-2000g/mol, most preferably be 800-1200g/mol; It is selected from gather THF, W 166, polyester, amino-terminated polyalkylene oxides or derivatives thereof, and composition thereof; (i)+(ii)+(iii)=100% wherein
Wherein said isocyanate-terminated prepolymer component is with 1.1: 1-6: 1 isocyanic ester reacts with the ratio of isocyanate-reactive group; With
(B) at least a active hydrogen chain extension compound, its isocyanate content with respect to isocyanate-terminated prepolymer (A) comprise the normal active hydrogen chain extension compound that is selected from hydrazine, hydrazine derivative and composition thereof of at least 0.4 stoichiometry,
Wherein (A) and (B) with 1: 0.8-1: the ratio reaction of 0.99 isocyanic ester and isocyanate-reactive group, and
Wherein normal said anionic property of 0.25-3 stoichiometry or potential anionic property water-dispersion group neutralize with ammonia.
Available technology well known in the art is dispersed in isocyanate-terminated prepolymer (or urethane) in the aqueous medium (for example water).Preferably, under agitation isocyanate-terminated prepolymer (or urethane) is added in the entry, or water is stirred in the adding isocyanate-terminated prepolymer (or urethane).
Can use tensio-active agent and/or high-shear by any order, to help the dispersion (even it be can self-dispersed) of isocyanate-terminated prepolymer (or urethane) in water.Suitable tensio-active agent comprises but is not limited to traditional negatively charged ion, positively charged ion and/or nonionogenic tenside, for example the Na of dialkyl sulfosuccinate succinate, K and NH 4Salt, the Na of sulfuric ester carburetion, K and NH 4The Na of salt, alkylsulphonic acid, K and NH 4Salt, vitriolic alkyl ester, Na, K and NH 4Salt, an alkali metal salt of sulfonic acid; The lipid acid of Fatty Alcohol(C12-C14 and C12-C18), ethoxylation and/or aliphatic amide, and such as Na, K and the NH of the lipid acid of StNa and sodium oleate 4Salt.Other AS comprises perhaps (alkane) aryl of alkyl that is linked to sulfonic acid group, sulfate hemiester group (being linked to the polyglycol ether group again), phosphonyl group, phosphoric acid analogue and phosphoric acid salt or hydroxy-acid group.Cats product comprises alkyl or (alkane) aromatic yl group that is linked to quaternary ammonium salt group.Ionic surfactant pack is drawn together polyglycol ether compound and polyethylene oxide compound.Amount of surfactant is preferably 0-15wt% based on weight polyurethane, more preferably 0-8wt%, more preferably 0-5wt%, particularly 0.1-3wt%, the most particularly 0.3-2wt%.
One embodiment of the present invention provide a kind of method for preparing waterborne compositions of the present invention, comprise the steps:
A) make component (i)-(iii) reaction, to form isocyanate-terminated prepolymer (A);
B) form the aqueous dispersion of said isocyanate-terminated prepolymer (A);
C) alternatively, the said isocyanate-terminated prepolymer (A) that neutralizes;
D) through reacting said isocyanate-terminated prepolymer (A) chain extension with active hydrogen chain extension compound (B).
Step b), c) and d) can take place by any order, for example these three steps can take place simultaneously or step d) at step b) and c) take place afterwards.Step c) can be after step a) and/or during and/or before step b) and/or during take place.Preferably, step b), c) and d) generation simultaneously.
Present method also can comprise step e) (interpolation reactive diluent) and step f) (with the said reactive diluent that adds in the step e) with post polymerization).The interpolation of reactive diluent (step e)) can be carried out in any stage, for example before beginning prepolymer reaction, or during prepolymer forms and/or any stage afterwards, or can be at dispersion steps b) before, during and/or afterwards it is added water.
Preferably, step f) is carried out after step b).Preferably, when isocyanate-terminated prepolymer (or urethane) disperses, there has been part or all of ammonia in the aqueous medium in aqueous medium.
Polyurethane dispersions of the present invention can combine with a kind of or more kinds of other polymkeric substance known in the art, for example vinyl polymer (comprising (methyl) acrylic ester polymer), alkyd, polyester, polyethers, polycarbonate and aminoresin.
In another embodiment of the invention, if use reactive diluent, particularly when reactive thinner comprises alkene formula unsaturated monomer (being also referred to as vinyl monomer), can be with its in-situ polymerization to prepare vinyl polymer.
The instance that can be used as the vinyl monomer of reactive diluent and the vinyl polymer of in-situ polymerization formation subsequently includes but not limited to 1,3-butadiene, isoprene; (methyl) vinylformic acid trifluoro ethyl ester (TFEMA); (methyl) vinylformic acid dimethylamino ethyl ester (DMAEMA); Two (methyl) vinylformic acid polyalkylene glycol ester, for example diacrylate 1,3 butylene glycol ester, ethylene glycol diacrylate; Vinylstyrene, vinylbenzene, alpha-methyl styrene, (methyl) acrylic amide and (methyl) vinyl cyanide; Vinyl halide, for example vinylchlorid; Vinylidene halide, for example vinylidene chloride; Vinyl ether; Vinyl ester, for example vinyl-acetic ester, vinyl propionate base ester, LAURIC ACID 99 MIN vinyl ester; Branched paraffin carboxylic acid's vinyl ester, for example VeoVa 9 and VeoVa 10 (VeoVa is the trade mark of Resolution); The heterocycle vinyl compound; Monoene belongs to the alkyl ester of unsaturated dicarboxylic acid, for example toxilic acid di-n-butyl ester and fumaric acid di-n-butyl ester; And formula CH particularly 2=CR 1-COOR 2Propenoate and methacrylic ester, R in the formula 1Be H or methyl, R 2Be the optional substituted alkyl or cycloalkyl of 1-20 carbon atom (more preferably 1-8 carbon atom), the example is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi (all isomer), (methyl) Octyl acrylate (all isomer), (methyl) 2-EHA, (methyl) isopropyl acrylate, (methyl) vinylformic acid n-propyl.Formula CH 2=CR 1-COOR 2Preferred monomers comprise (methyl) Bing Xisuandingzhi (all isomer), (methyl) methyl acrylate, (methyl) Octyl acrylate (all isomer) and (methyl) ethyl propenoate.Preferred especially vinyl monomer comprises (methyl) acrylate monomer and styrene-based monomers.Most preferred monomer is TEB 3K, (methyl) Bing Xisuandingzhi, 2-EHA, vinylbenzene and vinyl cyanide.
By comprising a kind of or more kinds of as above formula CH of definition of 40wt% at least 2=CR 1-COOR 2The vinyl polymer that makes of monomeric monomer system be defined as (methyl) acrylic ester polymer here.More preferably, monomer system comprises at least 50wt%, particularly such monomer of 60wt% at least.Other monomer in (methyl) acrylic ester polymer like this (if use) can comprise other vinyl monomer that a kind of or more kinds of this paper mentions, and/or can comprise different vinyl monomers.Preferably, vinyl polymer is (methyl) acrylic ester polymer.
Also preferred use does not comprise the vinyl monomer of isocyanic ester or isocyanate-reactive group.Therefore, suitable vinyl monomer comprises ester and the ether and the vinylbenzene of ethylenic unsaturated hydrocarbons, (methyl) acrylic acid ester and ether (particularly ester), vinyl alcohol.Specific examples comprises that low alkyl group (C1-C6) ester, vinylacetate and butyric ester, (methyl) propenoate, vinyl cyanide, allyl methacrylate(AMA), vinyl methyl, propyl group and butyl ether, divinyl ether, the divinyl of divinyl, isoprene, vinylbenzene, substituted phenylethylene, (methyl) vinylformic acid and toxilic acid vulcanize thing, vinylchlorid, Ethylene Dichloride, hexanediol diacrylate, three vinylformic acid trishydroxymethyl propyl ester etc.
Vinyl monomer can comprise the vinyl monomer of the functional group that has crosslinked group for example and/or water-dispersion group.This functionality can directly be introduced polymkeric substance through radical polymerization, and perhaps functional group can introduce through the monomeric reaction of reaction-ity ethylene base, this reaction-ity ethylene base monomer subsequently with have the reactive compounds of expect functional group and react.Some functional group can realize more than a kind of function, and for example (methyl) vinylformic acid is used as the water-dispersion monomer usually, but it also can be used as cross-linking monomer.These variations are well known by persons skilled in the art.
For for example autoxidation, Schiff alkali is crosslinked and cross-linking method silane condensation provides the preferred vinyl monomer of crosslinked group to comprise to have at least one free carboxy, hydroxyl, epoxy group(ing), acetoacetoxy groups, allyl group, lipid acid or amino vinylformic acid and methacrylic acid monomer, for example (methyl) vinylformic acid, glycidyl acrylate, SY-Monomer G, methylacrylic acid acetoacetyl 2-ethoxyethyl acetate, allyl methacrylate(AMA), methylacrylic acid TEG ester, Vinylstyrene, t-butylaminoethyl methacrylate and dimethylaminoethyl methacrylate.Can known by one of skill in the art method introduce amino functionality; For example comprise the for example vinyl polymer of the vinyl monomer of acrylic or methacrylic acid, for example at least a portion hydroxy-acid group is converted into amino (as the part of amino ester group) subsequently through the imidization of using alkylene imine (for example ethylenimine or propylidene imines) through preparation.
When combining with the linking agent that adds the outside and/or react each other and/or react with polyether polyols with reduced unsaturation, such crosslinking functionality can be used for making compsn to have potential crosslinkable property (thereby for example after waterborne compositions is dried subsequently, taking place crosslinked).
Vinyl monomer with ionic or potential ionic water-dispersion group includes but not limited to; (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, propenoic acid beta-carboxylic ethyl ester, maleic acid mono alkyl ester (for example monomethyl maleate and ethyl maleate), citraconic acid, styrene sulfonic acid, vinyl benzene methylsulphonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (for example acryloyl-oxy methylsulphonic acid), the 2-acrylamido-2-alkyl alkane sulfonic acid (for example; 2-acrylamido-2-methyl ethane sulfonic acid), 2-methacryloyl amido-2-alkyl alkane sulfonic acid (for example, 2-methacryloyl amido-2-methyl ethane sulfonic acid), mono phosphoric acid ester (acryloyloxyalkyl) ester (for example mono phosphoric acid ester (acrylyl oxy-ethyl) ester) and mono phosphoric acid ester (methacryloyl oxyalkyl) ester (for example mono phosphoric acid ester (methylacryoyloxyethyl) ester).
Yet, preferably,, do not use vinyl monomer with ionic or potential ionic water-dispersion group for the vinyl polymer of in-situ preparing, reason is that they can make polyurethane dispersions unstable.
Nonionic water-dispersion group can be in the chain, side group or end group.The vinyl monomer that preferably has nonionic water-dispersion group comprises alkoxyl group W 166 (methyl) propenoate, and it preferably has the Mn of 350-3000g/mol.This monomeric instance that can buy comprises ω-methoxy poly (ethylene glycol) (methyl) propenoate.Mn comprises the Diethylene Glycol mono vinyl ether less than the instance of the vinyl monomer with nonionic water-dispersion group of 350g/mol.
Most preferably, the vinyl monomer that is used to prepare vinyl polymer is selected from TEB 3K, (methyl) Bing Xisuandingzhi, ethyl propenoate, vinylbenzene, (methyl) vinylformic acid and composition thereof.
Preferably, the acid number of vinyl polymer is 0-100mgKOH/g, more preferably 0-70mgKOH/g, particularly 0-50mgKOH/g.
Known in the art, if vinyl polymer is (original position) of preparation in the presence of urethane, then preferably, the vinyl monomer that is used to prepare vinyl polymer only comprises on a small quantity, does not preferably comprise basically (methyl) vinylformic acid.
For the vinyl polymer of in-situ preparing, preferred vinyl monomer is a liquid under the temperature condition that forms isocyanate prepolymer, but does not also get rid of the possibility of using solid vinyl monomer (using with organic solvent alternatively).
For the vinyl polymer of in-situ preparing, all vinyl monomer can exist when beginning to prepare isocyanate-terminated prepolymer, perhaps can in the preparation process, add a part or whole vinyl monomers.Preferably, vinyl monomer just polymerization after chain extension is accomplished.
Be preferably the 0-95wt% of gross weight of the vinyl polymer of urethane and in-situ preparing as the ratio of vinyl monomer of the reactive diluent of preparation isocyanate-terminated prepolymer; More preferably 0-80wt%; Most preferably 5-50wt%, particularly 10-40wt%.
The acid number of the vinyl polymer of in-situ preparing is preferably 0-20mgKOH/g, and more preferably 0-10mgKOH/g particularly is essentially 0mgKOH/g.
The urethane of compsn of the present invention can also combine with the polymkeric substance (the for example vinyl polymer of independent preparation) of independent preparation.The vinyl monomer that is applicable to the vinyl polymer that forms independent preparation comprises all vinyl monomers that are applicable to the vinyl polymer that forms in-situ preparing.
The acid number of the vinyl monomer of independent preparation is preferably 0-100mgKOH/g, more preferably 0-70mgKOH/g, more preferably 0-50mgKOH/g, particularly 0-40mgKOH/g.
The weight-average molecular weight (Mw) of vinyl polymer (original position or independent preparation) is preferably 1000-10000000g/mol, more preferably 2000-5000000g/mol, most preferably 5000-3000000g/mol.
Preferably, the Tg through calculating (through known Fox equation) of vinyl polymer (original position or independent preparation) is preferably-80-150 ℃, more preferably-and 60-120 ℃; Most preferably-40-106 ℃; Particularly-and 20-80 ℃, be more especially 0-80 ℃, the most particularly 10-80 ℃.
Vinyl polymer (original position or independent preparation) can be the sequence vinyl polymer.If vinyl polymer is the sequence vinyl polymer, then there are at least two Tg values, the difference of these two Tg values is preferably at least 40 ℃, more preferably at least 55 ℃.If vinyl polymer is the sequence vinyl polymer, then the Tg of the vinyl polymer of 40wt% is preferably-40-30 ℃ at least, more preferably-and 20-15 ℃.If vinyl polymer is the mixture of differing ethylene based polyalcohol, Tg≤25 of the vinyl polymer of then preferred 30-90wt% ℃, the Tg of the vinyl polymer of 10-70wt%>=45 ℃, more preferably>=55 ℃.
Urethane total amount and vinyl polymer (original position or independent preparation) solid weight ratio is preferably 10: 90-99: 1, more preferably 30: 70-95: 5, most preferably 40: 60-90: 10, particularly 50: 50-80: 20, the most particularly 60: 40-80: 20.
In one embodiment of the invention; The ratio that aqueous polyurethane composition of the present invention comprises urethane and vinyl solid is 60: 40-80: the vinyl polymer of 20 in-situ preparing; The Tg of therein ethylene based polyalcohol is 10-80 ℃, and by the vinyl monomer preparation that is selected from TEB 3K, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, vinylbenzene and combination thereof.
In another embodiment of the invention; The ratio that aqueous polyurethane composition of the present invention comprises urethane and vinyl solid is 60: 40-80: the vinyl polymer of 20 independent preparation; The Tg of therein ethylene based polyalcohol is 0-50 ℃, and by the vinyl monomer preparation that is selected from TEB 3K, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid and combination thereof.
The preferred prepared by radical polymerisation of vinyl polymer (original position or independent preparation), but also adopt anionoid polymerization in some cases.Radical polymerization can realize for example letex polymerization, solution polymerization, suspension polymerization or mass polymerization through technology well known in the art.Preferably, for the vinyl polymer of in-situ preparing, use emulsion polymerization process.
The mass polymerization of vinyl monomer is described in detail among EP 0156170, WO 82/02387 and the US4414370.Usually, in bulk polymerisation process, the mixture of two kinds or more kinds of vinyl monomers is added the reaction zone that contains the fusion vinyl oligomer continuously, and said fusion vinyl oligomer has the vinyl monomer ratio identical with mixture of vinyl monomer.
Radical polymerization can adopt intermittently, step by step, gradient (being also referred to as powering charge) or semi-continuous polymerzation process implement to prepare single or multistage vinyl polymer.
The radical polymerization of vinyl monomer need use radical generation initiator to cause vinyl polymerization.Suitable radical generates potassium, sodium or the ammonium salt that initiator comprises persulfuric acid; Hydrogen peroxide; Peroxocarbonate; Organo-peroxide for example comprises the acyl peroxide of Lucidol; Alkyl peroxide, for example tertbutyl peroxide and cumene hydroperoxide; Dialkyl peroxide, for example ditertiary butyl peroxide; Peroxy esters, for example t-butylperoxyl benzoate etc.; Also can use mixture.Peroxy compound advantageously is used in combination (redox system) with the suitable reductive agent of for example sodium pyrosulfate or potassium or sodium sulfite anhy 96 or potassium and saccharosonic acid in some cases.For example the metallic compound of Fe.EDTA (EDTA is a YD 30) also can serviceably be used as the part of redox initiator system; For example, the combination of tertbutyl peroxide, saccharosonic acid and Fe.EDTA can distribute between water and organic phase.Also can use the azo functional initiator.Preferred azo initiator comprises azo two (isopropyl cyanide) and 4,4 '-azo two (4-cyanopentanoic acid).The consumption of initiator or initiator system is conventional, is 0.05-6wt% based on used vinyl monomer gross weight for example.Preferred initiator comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate, azo two (isopropyl cyanide) and/or 4,4 '-azo two (4-cyanopentanoic acid).
The chain-transfer agent of available for example mercaptan and halohydrocarbon is controlled molecular weight, and said mercaptan for example is n-dodecyl mercaptan, n-octyl mercaptan, uncle's lauryl mercaptan, mercaptoethanol, the different monooctyl ester of thioglycolic acid, C 2-C 8Mercaptan carboxylic acid and ester thereof (for example 3-thiohydracrylic acid and 2 mercaptopropionic acid), halohydrocarbon for example is carbon tetrabromide and bromo-trichloromethane.Also can control molecular weight with catalytic chain transfer agent; Said catalytic chain transfer agent for example is a transition metal complex, particularly is disclosed in the cobalt chelates through selecting among US 4526945, US4680354, EP 0196783, EP 0199436, EP 0788518 and the WO 87/03605.
After the polymerization, the free vinyl monomer content in the aqueous polyurethane composition of the present invention is more preferably less than 150ppm preferably less than 500ppm, most preferably less than 70ppm.
The solids content of aqueous polyurethane composition of the present invention is 1-60wt%, more preferably 2-55wt%.
Free hydrazine content≤the 20ppm of aqueous polyurethane composition of the present invention, more preferably≤10ppm, most preferably≤4ppm, particularly≤2ppm (free hydrazine that can't detect).
Aqueous polyurethane composition of the present invention can comprise other conventional ingredient; Comprise the organic solvent that condenses, pigment, dyestuff, emulsifying agent, tensio-active agent, thickening material, thermo-stabilizer, levelling agent, the agent of nonshrink hole, filler, precipitating inhibitor, rheology modifier, UV absorption agent, inhibitor, dry salt etc., their any stages in preparation technology introduce or introduce subsequently.For example, can comprise in dispersion-s that a certain amount of weisspiessglanz is to improve flame retardant resistance.In order to improve to the for example chemical resistant properties of water, washing composition and alcohol; Waterborne compositions of the present invention can comprise for example CX-100, the outside linking agent of CX-300 (can obtain from DSM NeoResins BV) or water dispersible POLYMETHYLENE POLYPHENYLISOCYANATE; Their any stages in preparation technology introduce, but preferably introduce subsequently.
By the aqueous polyurethane composition of method of the present invention preparation be can stable storage dispersion-s, do not need extra solvent or tensio-active agent, but if desired, can comprise a spot of emulsifying agent and/or solvent yet.
Aqueous polyurethane composition of the present invention can be used as coating composition; Or (for example be used to provide coating composition; Protectiveness or decorative coating compsn) main ingredient; They can further be diluted by water and/or organic solvent for this reason, perhaps can with more spissated form they be provided through the organic constituent of vaporize water and/or liquid medium.
Aqueous polyurethane composition of the present invention can be applied to various base materials through brush, dipping, the traditional methods such as coating and spraying that flow, and comprises timber, plate, metal, stone, cement, glass, cloth, leather, paper, plastics, foam etc.Through naturally perhaps through quickening the drying of (heating), the aqueous medium that generally includes water and any solubility promoter is removed, thereby form coating.
To be directed in the food packaging film industry that Vestolen PP 7052 (OPP) is the master, to have developed several kinds of structures (smooth, extrude jointly, space, painted, coating, lamination) and formed suitable film.
When owing to extreme require and can't adopt traditional structure the time, can solve through using specific coating.Coating not only can be used for improving print performance, gloss and the barrier property (like oxygen, moisture and smell) of marking ink, can also improve heat sealability, metallization and the outward appearance of wrapping material.Barrier if desired, polyvinylidene dichloride (PVDC) or EVOH (EVOH) coating are only products, and the additional advantages of PVDC has heat sealable.Acrylic coating is used widely because of it has excellent printing property, heat sealability and transparency.
Find that coating is a key property to the adhesivity of base material.Especially, when the Vestolen PP 7052 that is used for food product pack (OPP) film seals,, need have fabulous adhesivity on pack-thread in order to obtain best sealing intensity.Can use coating to obtain heat sealability.Sealing usually forms down in minimum possibility temperature, minimum possibility pressure and the shortest time, and preferably sealing should keep its intensity for a long time under severe condition.One of this condition is the sealing intensity wet fastness.At this moment, sealing should keep its intensity for a long time when tropicalization (that is, high-temperature and high humidity) is preserved down.The heat-seal strength of coating is preferred >=200g/inch (78.74g/cm), more preferably >=400g/inch (157.48g/cm).Heat-seal strength is the heat-seal strength (initial sealing intensity) of initial measurement and experiences the heat-seal strength of measuring after moistening and the warm conditions (wet sealing intensity).
Usually, the OPP film that is applied can have layered structure, and this structure comprises following each layer: top coat, undercoat, OPP, undercoat, top coat.
Especially, aqueous polyurethane composition of the present invention is suitable as the undercoat of plastic basis material, more specifically as the undercoat of Vilaterm and (orientation) polypropylene base.Aqueous polyurethane composition of the present invention is particularly suitable for the undercoat as (orientation) polypropylene base, and this base material is applied with polymeric dispersions subsequently.The suitable polymers dispersion-s that is used to be coated with is that vinyl polymer (comprising (methyl) acrylic ester polymer) and main ingredient are that the vinyl polymer of vinyl monomer Ethylene Dichloride (comprises more than 50wt%.More preferably more than the Ethylene Dichloride of 88wt%).The advantage that contains Ethylene Dichloride is that the coating of gained can be resealed.
Usually, plastic basis material is preheated to improve surface polarity.The technology of raising surface polarity known in the art comprises flame treating, corona treatment and handles with chromic acid (or its salt).
Aqueous polyurethane composition of the present invention also is suitable as label coating, and wherein label is applied with aqueous polyurethane composition and makes it have adhesivity to base material.Base material can be aforesaid plastic basis material.Perhaps, aqueous polyurethane composition of the present invention is suitable as the base paint of film label.
One embodiment of the present invention provide a kind of base material with the coating that comprises aqueous polyurethane composition of the present invention; A kind of method of using aqueous polyurethane composition coated substrate of the present invention also is provided, and this method comprises to be coated said aqueous polyurethane composition substrate and removes aqueous medium.
One embodiment of the present invention provide a kind of base paint that is preferred for coated plastic substrates, and it comprises aqueous polyurethane composition of the present invention.
The present invention also provides a kind of label coating that is obtained by aqueous polyurethane composition of the present invention.
With reference now to following examples, set forth the present invention.Only if statement is arranged in addition, all parts, per-cent and ratio are all based on weight.
Embodiment
Used abbreviation
The SA=stoichiometry
DMPA=2, the 2-dimethylol propionic acid
The pTHF-1000=THF homopolymer, Mw1000
The IPDI=isophorone diisocyanate
TDI=2, the 4-tolylene diisocyanate
DES W=methylene radical-two cyclohexylene vulcabond=4,4 '-dicyclohexyl methane diisocyanate
The PPG-1000=W 166, Mw1000
The EDA=quadrol
The NMP=N-SL 1332
The MMA=TEB 3K
The BMA=NSC 20956
The BOPP=bi-oriented polypropylene
The PVDC=polyvinylidene dichloride
Diofan A-050=can be from the negatively charged ion polyvinylidene dichloride of Solvin acquisition
The TEA=triethylamine
NH 3=the ammonia that uses as 25% the aqueous solution
N 2H 4=the hydrazine that uses as 15.2% the aqueous solution
Neocryl BT-36=can be from the ACRYLIC EMULSION of DSM NeoResins BV acquisition
The Water=softening water
Dynomin UM-15=Cymel UM-15=can be from the methylated urea-formaldehyde resin of Cytec acquisition
NeoCryl XK-90=can be from the sequence ACRYLIC EMULSION of DSM NeoResins BV acquisition, and its Mw is 2000000
ML-160=Michem L ü be ML-160 can be from the negatively charged ion POLISHING WAX-103 emulsion of Michelmann acquisition
FP-348=Formapol FP-348 can be from the dispersion-s of synthetic amorphous silicon oxide water of Formulated Polymer Products acquisition
Jeffamine=can be from the amino-terminated polyalkylene oxides of Huntsman acquisition, Mw1000
Embodiment 1
Step 1: with pTHF-1000 (1520.4g; OH value=110mgKOH/g; 50 ℃ of following premelts) and DMPA (168.0g) reactor drum of packing into.With mixture homogenization is thin suspension-s, adds IPDI (1111.7g) then.Use the nitrogen purge reactor drum, and its content is heated to 50 ℃.Under 50 ℃, add the stannous octoate (0.25g) of catalytic amount.Utilize institute's liberated heat and extra indirect heating, make mixture reach 90 ℃ temperature of reaction.Through the residual titration of the excessive dibutylamine that in the sample solution of prepolymer in toluene, adds, confirm the amount of remaining isocyanate groups, thus monitoring reaction course.Keep temperature of reaction, be brought down below the theoretical value of 6.7%NCO, be cooled to 75 ℃ then up to the NCO of gained polyurethane prepolymer content.
Step 2: with water (1629.5g), ammonia (neutralizing agent, 26.1g, 25% aqueous solution; DMPA acid groups with respect to polyurethane prepolymer is 1.0SA) and hydrazine (chainextender, 129.9g, 15.2% aqueous solution; Remaining isocyanate group with respect to polyurethane prepolymer is 0.95SA) second reactor drum of packing into, and the temperature of gained water is set at 30 ℃.
Step 3: use the 1L tap funnel of heating, with the water of the polyurethane prepolymer (850.0g) for preparing in the step 1 with preparation in 1 hour the time adding step 2, the temperature with polyurethane prepolymer remains on 75 ℃ simultaneously.In this dispersion steps, make the temperature of water rise to 39 ℃.In step 3, neutralization, chain extension and the dispersion in water are carried out simultaneously.
The solids content of the translucent polyurethane dispersions that obtains is 33.0%, and pH is 7.6, and the Brookfield viscosity under the room temperature (23 ± 2 ℃) is 50mPas.The concentration of the free hydrazine that HPLC measures is about 1ppm, and this is the limit of detection of equipment used.
Following table 1 gives out the relative quantity of the component that is used for all embodiment.
Embodiment 2
Method according to embodiment 1 prepares polyurethane dispersions, and difference is: with the EDA of 0.35SA, the hydrazine with 0.60SA carries out chain extension again.
Embodiment 3
Method according to embodiment 1 prepares polyurethane dispersions, and difference is: prepolymer by PPG-1000, DMPA and DES W with 1.5 NCO/OH than preparation, the NMP with 5% is as solubility promoter, neutralizes with the ammonia of 1.3SA, with the hydrazine chain extension of 0.98SA.
Embodiment 4
Method according to embodiment 3 prepares polyurethane dispersions, and difference is: before disperseing, aqueous phase with the ammonia of 1.3SA in and prepolymer, and after disperseing in water the ammonia of adding 1.7SA with raising pH.
Embodiment 5
Method according to embodiment 1 prepares polyurethane dispersions; Difference is: prepolymer is that the polyester polyol of 110mgKOH/g is (by (99.4 parts of dimer fatty acid Pripol 1009 by the OH value; Can obtain from Uniqema), the preparation of hexanodioic acid (24.8 parts) and cyclohexanedimethanol (75.8 parts)), DMPA, IPDI and Jeffamine (1/1 mole of affixture of Jeffamine M1000 and Hydroxyethyl acrylate; Can come independent preparation in 2 hours through mixing two kinds of compositions and being heated to 70 ℃ as EP 317258 B1 are said) NCO/OH with 1.5 is than preparation, carries out simultaneously then: in water, disperse, neutralize and with the hydrazine chain extension of 0.95SA with the ammonia of 1.1SA.
Embodiment 6
Method according to embodiment 1 prepares polyurethane dispersions; Difference is: prepolymer by pTHF-1000, DMPA and TDI with 1.5 NCO/OH than preparation (in ratio to be the solid of 80% in 4: 1 BMA and the monomeric mixture of MMA), carry out simultaneously then: in water, disperse, neutralize and with the hydrazine chain extension of 0.98SA with the ammonia of 1.3SA.At last, be XPA to tertbutyl peroxide (0.7g, 70% aqueous solution), saccharosonic acid (4 * 10.2g, 1% aqueous solution) (both are 0.1% based on monomer) with conversion of monomer with Fe.EDTA (2.0g, 1% aqueous solution) and redox initiation.Tg according to the BMA/MMA polymkeric substance of Fox Equation for Calculating is 34 ℃.Urethane is 80: 20 with the ratio of vinyl polymer.
Embodiment 7
The polyurethane dispersions (527.1g) of embodiment 1 is mixed with urea formadehyde resin Dynomin UM-15 (2.6g).
Embodiment 8
The polyurethane dispersions (527.1g) of embodiment 1 is mixed with sequence acrylic acid emulsion polymer (165.7g) (NeoCryl XK-90 can obtain from DSM NeoResins BV, has two Tg values (using the Fox Equation for Calculating, 0 ℃ and 80 ℃)).
Comparative example C1
Method according to embodiment 1 prepares polyurethane dispersions, and difference is: with TEA (1.0SA) but not ammonia come prepolymer is neutralized, and polyurethane dispersions (500g) is mixed with urea formadehyde resin Dynomin UM-15 (5.1g).
Comparative example C2
Method according to embodiment 1 prepares polyurethane dispersions, and difference is: with EDA (0.95SA) but not hydrazine carries out chain extension.
Comparative example C3
Method according to embodiment 1 prepares polyurethane dispersions, and difference is: with stoichiometry excessive (1.20SA) but not the hydrazine that is lower than stoichiometry carries out chain extension.The amount of the free hydrazine that exists in this dispersion-s is greater than 200ppm, thereby on toxicology, this dispersion-s can't be as undercoat.
The size of particles of embodiment 1-8 is less than 200nm.The Mn of the urethane that in these embodiment, prepares is less than 40000g/mol.Following table 1 has provided the details of embodiment.
Table 1
Embodiment 1 ?2 ?3 ?4 ?5 ?6 ?C1 ?C2 ?C3
Polyurethane prepolymer
DMPA％ 6.0 ?6.0 ?5.5 ?5.5 ?5.2 ?9.0 ?5.2 ?6.0 ?6.0
Polyvalent alcohol 1 pTHF1000 ?pTHF?1000 ?PPG?1000 ?PPG?1000 Polyester ?pTHF?1000 ?pTHF?1000 ?pTHF?1000 ?pTHF?1000
Polyvalent alcohol 1% 54.3 ?54.3 ?56.5 ?56.5 ?52.6 ?58.2 ?56.6 ?54.3 ?54.3
Polyvalent alcohol 2 ?Jeffamine
Polyvalent alcohol 2% ?5.0
Vulcabond IPDI ?IPDI ?DES?W ?DES?W ?IPDI ?TDI ?IPDI ?IPDI ?IPDI
Vulcabond % 39.7 ?39.7 ?38.0 ?38.0 ?37.2 ?37.2 ?38.2 ?39.7 ?39.7
Solubility promoter % ?NMP?(12.0) ?NMP?(12.0) ?NMP?(10.0) ?BMA?/MMA?(20)
Stannous octoate % 0.01 ?0.01 ?0.01 ?0.01 ?0.01 ?0.01 ?0.01 ?0.01 ?0.01
Additive g ?Ionol?CP?(0.2)
NCO/OH 1.80 ?1.80 ?1.50 ?1.50 ?1.80 ?1.50 ?1.80 ?1.80 ?1.80
NCO％ 6.42 ?6.42 ?3.01 ?3.01 ?5.34 ?4.12 ?6.41 ?6.42 ?6.42
Dispersion-s
Prepolymer g 850.0 ?320.0 ?500.0 ?500.0 ?611.1 ?500.0 ?500.0 ?320.0 ?320.0
Neutralizing agent g NH 3(26.1) ?NH 3?(9.8) ?NH 3?(16.9) ?NH 3?(38.9) ?NH 3?(14.5) ?NH 3?(25.1) ?TEA?(19.8) ?NH 3?(9.8) ?NH 3?(9.8)
Neutralizing agent SA 1.0 ?1.0 ?1.3 ?3.0?(1.3/1.7) ?1.1 ?1.3 ?1.0 ?1.0 ?1.0
Chainextender N 2H 4 ?EDA/?N 2H 4 ?N 2H 4 ?N 2H 4 ?N 2H 4 ?N 2H 4 ?N 2H 4 ?EDA ?N 2H 4
Chainextender g 129.9 ?4.9/33.5 ?37.0 ?37.0 ?79.0 ?50.6 ?70.3 ?16.0 ?61.8
Chainextender SA ?0.95 ?0.30/0.65 ?0.98 ?0.98 ?0.95 ?0.98 ?0.95 ?0.98 ?1.20
Water g ?1629.5 ?614.8 ?931.6 ?931.6 ?1100.0 ?693.6 ?1190.8 ?667.5 ?606.5
Character
Solid % ?33.0 ?32.5 ?30.5 ?30.1 ?30.3 ?38.5 ?27.7 ?32.5 ?32.5
Viscosity * ?50 ?30 ?184 ?120 ?51 ?72 ?40 ?40 ?40
pH ?7.6 ?8.0 ?8.5 ?9.9 ?7.7 ?6.9 ?8.1 ?9.9 ?8.2
Acid number # ?25 ?25 ?23 ?23 ?22 ?30 ?22 ?25 ?25
N 2H 4ppm ?1 ?1 ?BDL ?BDL ?BDL ?BDL ?5 ?BDL ?205
*MPas #mgKOH/g BDL: the detectability that is lower than equipment used
The urethane of describing among the embodiment 1-8 and urethane/acrylic acid dispersion are tested as the undercoat on the BOPP of corona treatment paillon foil with PVDC heat sealability top coat (Diofan A-050), and be referred to as embodiment 1 (a)-8 (a).
In embodiment 1 (b), the polyurethane dispersions of embodiment 1 is tested as the undercoat on the BOPP of corona treatment paillon foil with vinylformic acid heat sealability top coat (NeoCryl BT-36).
In embodiment 3 (b), the polyurethane dispersions of embodiment 3 is tested as the undercoat on the BOPP of corona treatment paillon foil with vinylformic acid heat sealability top coat (NeoCryl BT-36).
In embodiment 6 (b), the polyurethane dispersions of embodiment 6 is tested as the undercoat on the BOPP of corona treatment paillon foil with vinylformic acid heat sealability top coat (NeoCryl BT-36).
The polyurethane dispersions of comparative example C1 and C2 is tested as the undercoat on the BOPP of corona treatment paillon foil with PVDC heat sealability top coat (Diofan A-050).
Linging and coating experiment about the heat sealability packaging application
On experimental film coated machine (the RK coating machine of RK Print-Coat Instruments); Through reverse notch board coating system; The water base base paint that comprises the polyurethane dispersions (using softening water to be diluted to solids content is 5%) for preparing among embodiment 1-8 and comparative example C1 and the C2 respectively is coated in through the OPP of the corona treatment base film (23DR-360 of Derprosa; This substrate film is 40-42dynes/cm through the surface tension after the corona treatment) on; Dry under 80 ℃ with warm air then, obtaining dry coating weight is 0.15g/m 2The plastic basis material through linging.
Be coated on the water base negatively charged ion PVDC dispersion-s (a) or the water-based acrylic emulsion (b) of coating according to the form below 2 preparations on the plastic basis material of linging then through reverse notch board, dry down with warm air then at 90 ℃.The dry coating weight of PVDC top coat is 1.5g/m 2, and the dry coating weight of vinylformic acid top coat is 1g/m 2
Table 2
?Diofan?A-050 ?NeoCryl?BT-36 ?ML-160 ?FP-348 Water
PVDC ?83.7 ?3.7 ?0.9 ?11.7
Vinylformic acid ?70.6 ?3.4 ?0.2 ?25.8
Will be through the film of coating in room temperature (23 ± 2 ℃) 1 week of held, so that the PVDC top coat is accomplished crystallization.
Wet sealing intensity
With as above preparation through coated thin film doubling (top coat is to top coat), go up heat-sealing at Brugger heat sealing machine (HSG-C type) then, this heat sealing machine is equipped with clamp under clamp (2cm is wide) on the flat metal of heating and the flat rubber that does not heat.Under 130 ℃, at 2.8kg/cm 2Under the pressure (40psi), sealing was carried out for 1 second.
In the Instron Tensile test initial heat-seal strength of airborne measurements (g/inch).
Sealing film is kept at 4 weeks in the humidity cabinet (38 ℃, relative air humidity is 90%).The residue sealing intensity of after 1 day, 1 week, 2 weeks, 3 weeks and 4 weeks, measuring respectively should remain on similar level.
Table 3 has provided the initial adherence property and the adhesivity (in g/inch and g/cm) after warm and wet condition (38 ℃, relative air humidity is 90%) are preserved of sealing paillon foil.
Table 3
Embodiment 1(a) 1(b) 2(a) ?3(a) 3(b) 4(a) ?5(a)
Top coat PVDC Vinylformic acid PVDC ?PVDC Vinylformic acid PVDC ?PVDC
Adhesivity (wet sealing intensity) g/inch (g/cm)
Initially 489(193) 638(251) 725(285) 778(306) 565(222) 724(285) 298(117)
1 day 357(141) 524(206) 356(140) 487(192) 524(206) 387(152) 449(177)
1 week 476(187) 621(244) 416(164) 562(221) 621(244) 535(211) 580(228)
2 weeks 517(205) 595(234) 407(160) 601(237) 636(250) 564(220) 631(248)
3 weeks 431(170) 637(251) 353(139) 616(243) 692(272) 618(243) 672(265)
4 weeks 419(165) 634(250) 300(118) 603(237) 621(244) 584(230) 628(247)
Table 3 (continuing)
Embodiment 6(a) 6(b) 7(a) 8(a) ?C1(a) C2(a)
Top coat PVDC Vinylformic acid PVDC ?PVDC ?PVDC ?PVDC
Adhesivity (wet sealing intensity) g/inch (g/cm)
Initially 756(298) 412(162) 275(108) 417(164) 84(33) 115(45)
1 day 472(186) 287(113) 268(106) 273(107) 46(18) 60(24)
1 week 634(250) 206(81) 272(107) 258(102) 44(17) 62(24)
2 weeks 669(263) 240(94) 419(165) 309(122) 46(18) 40(16)
3 weeks 577(227) 266(105) 373(147) 214(84) 112(44) 40(16)
4 weeks 624(246) 237(93) 439(173) 302(119) 78(31) 40(16)

Claims (24)

1. aqueous polyurethane composition, said compsn comprises the urethane that acid number is 4-150mgKOH/g, and comprises the reaction product of following material:
(A) by the isocyanate-terminated prepolymer that comprises that following component reaction obtains:
(i) at least a organic multiple isocyanate;
(ii) at least a isocyanate-reactive compound, said isocyanate-reactive compound have anionic property or potential anionic property water-dispersion group;
The (iii) at least a isocyanate-reactive compound that is not (ii) comprised,
Wherein said isocyanate-terminated prepolymer component is with 1.1: 1-6: 1 isocyanic ester reacts with the ratio of isocyanate-reactive group; With
(B) at least a active hydrogen chain extension compound, it comprises with respect to the normal active hydrogen chain extension compound that is selected from hydrazine, hydrazine derivative and composition thereof of isocyanate content 0.2 stoichiometry of said isocyanate-terminated prepolymer (A) at least,
Wherein (A) and (B) with 1: 0.5-1: the ratio reaction of 1 isocyanic ester and isocyanate-reactive group, and
Wherein normal said anionic property of at least 0.2 stoichiometry or potential anionic property water-dispersion group neutralize with ammonia;
Said hydrazine derivative is selected from acetone azine, dimethylhydrazine, 1; 6-hexa-methylene-two hydrazines, carbon two hydrazines, hexanodioic acid list hydrazine, the two hydrazines of hexanodioic acid, amber acid dihydrazide, oxalic acid two hydrazides, m-phthalic acid two hydrazides, winestone acid dihydrazide, 1; 3-phenylene disulfonic acid two hydrazides, omega-amino--caproic acid two hydrazides, Hydrocerol A three hydrazides, 1; 2,4-butane tricarboxylic acid three hydrazides, γ-maloyl group hydrazine, two semicarbazides and semicarbazides.
2. aqueous polyurethane composition as claimed in claim 1, the free hydrazine content≤20ppm of said compsn.
3. aqueous polyurethane composition as claimed in claim 1, the acid number of wherein said urethane are 4-100mgKOH/g.
4. aqueous polyurethane composition as claimed in claim 1; The wherein said chainextender (B) that contains active hydrogen comprises with respect to the normal active hydrogen chain extension compound that is selected from hydrazine, hydrazine derivative and composition thereof of isocyanate content 0.4 stoichiometry of said isocyanate-terminated prepolymer (A) at least; Said hydrazine derivative is selected from acetone azine, dimethylhydrazine, 1; 6-hexa-methylene-two hydrazines, carbon two hydrazines, hexanodioic acid list hydrazine, the two hydrazines of hexanodioic acid, amber acid dihydrazide, oxalic acid two hydrazides, m-phthalic acid two hydrazides, winestone acid dihydrazide, 1; 3-phenylene disulfonic acid two hydrazides, omega-amino--caproic acid two hydrazides, Hydrocerol A three hydrazides, 1; 2,4-butane tricarboxylic acid three hydrazides, γ-maloyl group hydrazine, two semicarbazides and semicarbazides.
5. aqueous polyurethane composition as claimed in claim 1, the ratio of the active hydrogen in isocyanate groups in the wherein said isocyanate-terminated prepolymer (A) and the said chainextender (B) is 1: 0.6-1: 1.
6. aqueous polyurethane composition as claimed in claim 1, wherein normal said anionic property of at least 0.25 stoichiometry or potential anionic property water-dispersion group are neutralized by ammonia.
7. aqueous polyurethane composition as claimed in claim 1, said compsn comprise the urethane that acid number is 10-42mgKOH/g, and comprise the reaction product of following material:
(A) isocyanate-terminated prepolymer that obtains by following component reaction:
(i) at least a organic multiple isocyanate of 10-90wt%;
The (ii) at least a isocyanate-reactive compound of 0.1-80wt%, said isocyanate-reactive compound has anionic property or potential anionic property water-dispersion group;
The (iii) at least a isocyanate-reactive compound that is not (ii) comprised of 5-90wt%,
(i)+(ii)+(iii)=100% wherein,
Wherein said isocyanate-terminated prepolymer component is with 1.1: 1-6: 1 isocyanic ester reacts with the ratio of isocyanate-reactive group; With
(B) at least a active hydrogen chain extension compound, it comprises with respect to the normal active hydrogen chain extension compound that is selected from hydrazine, hydrazine derivative and composition thereof of isocyanate content 0.4 stoichiometry of said isocyanate-terminated prepolymer (A) at least,
Wherein (A) and (B) with 1: 0.8-1: the ratio reaction of 0.99 isocyanic ester and isocyanate-reactive group, and
Wherein normal said anionic property of 0.25-3 stoichiometry or potential anionic property water-dispersion group neutralize with ammonia; Said hydrazine derivative is selected from acetone azine, dimethylhydrazine, 1; 6-hexa-methylene-two hydrazines, carbon two hydrazines, hexanodioic acid list hydrazine, the two hydrazines of hexanodioic acid, amber acid dihydrazide, oxalic acid two hydrazides, m-phthalic acid two hydrazides, winestone acid dihydrazide, 1; 3-phenylene disulfonic acid two hydrazides, omega-amino--caproic acid two hydrazides, Hydrocerol A three hydrazides, 1; 2,4-butane tricarboxylic acid three hydrazides, γ-maloyl group hydrazine, two semicarbazides and semicarbazides.
8. aqueous polyurethane composition as claimed in claim 7, wherein component (i) is selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 toluene diisocyanate and composition thereof.
9. aqueous polyurethane composition as claimed in claim 7, wherein component (ii) is selected from 2,2-dimethylol propionic acid (DMPA), 2,2-dimethylolpropionic acid (DMBA) and composition thereof.
10. aqueous polyurethane composition as claimed in claim 7, wherein component (iii) is selected from and gathers THF, W 166, polyester, amino-terminated polyalkylene oxides, and composition thereof.
11. like the aqueous polyurethane composition of claim 10, wherein component Mw (iii) is 300-3000g/mol.
12. like the aqueous polyurethane composition of claim 10, wherein component (iii) comprises the organic cpds that is lower than 500g/mol less than the Mw of 15wt%.
13. aqueous polyurethane composition as claimed in claim 1, said compsn also comprises vinyl polymer, and wherein the weight ratio of urethane and vinyl polymer is 10: 90-99: 1.
14. like the aqueous polyurethane composition of claim 13, wherein said vinyl polymer is (methyl) acrylic ester polymer.
15. like the aqueous polyurethane composition of claim 13, the Tg of wherein said vinyl polymer is-80-150 ℃.
16. like the aqueous polyurethane composition of claim 13, the acid number of wherein said vinyl polymer is 0-100mgKOH/g.
17. aqueous polyurethane composition like claim 13; The ratio that said compsn comprises urethane and vinyl solid is 60: 40-80: the vinyl polymer of 20 independent preparation; The Tg of wherein said vinyl polymer is 0-50 ℃, and by the vinyl monomer preparation that is selected from TEB 3K, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, vinylbenzene, (methyl) vinylformic acid and composition thereof.
18. a method for preparing the waterborne compositions of claim 1 comprises the steps:
A) make component (i)-(iii) reaction, to form isocyanate-terminated prepolymer (A);
(i) at least a organic multiple isocyanate of 10-90wt%;
The (ii) at least a isocyanate-reactive compound of 0.1-80wt%, said isocyanate-reactive compound has anionic property or potential anionic property water-dispersion group;
The (iii) at least a isocyanate-reactive compound that is not (ii) comprised of 5-90wt%,
(i)+(ii)+(iii)=100% wherein,
Wherein said isocyanate-terminated prepolymer component is with 1.1: 1-6: 1 isocyanic ester reacts with the ratio of isocyanate-reactive group;
B) form the aqueous dispersion of said isocyanate-terminated prepolymer (A);
C) alternatively, the said isocyanate-terminated prepolymer (A) that neutralizes;
D) through reacting said isocyanate-terminated prepolymer (A) chain extension with said active hydrogen chain extension compound (B).
19., also comprise step like the method for claim 18:
E) add reactive diluent;
F) the follow-up polymerization of said reactive diluent.
20. the aqueous polyurethane composition of claim 1 is used for the purposes of coated substrate.
21. the method for a use polyurethane composition coated substrate comprises that the aqueous polyurethane composition with claim 1 is coated on base material and removes aqueous medium.
22. base paint that comprises the aqueous polyurethane composition of claim 1.
23. label coating that comprises the aqueous polyurethane composition of claim 1.
24. a coating that obtains by the aqueous polyurethane composition of claim 1, it the time has in heat-sealing >=heat-seal strength of 200g/inch.
CN2006800086294A 2005-03-17 2006-03-13 Aqueous polyurethane compositions Active CN101142250B (en)

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WO2019046279A1 (en) * 2017-08-28 2019-03-07 Dsm Ip Assets, B.V. Synthetic membrane composition comprising a fluorinated polyurethane
CN112239627A (en) * 2018-05-25 2021-01-19 广东尚联新材料科技有限公司 Nano fireproof high-transparency coating
CN109401717B (en) * 2018-10-25 2019-10-18 江门市长河化工实业集团有限公司 A kind of modified polyurethane binder and preparation method thereof

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