CN1718606A - Water-based polyurethane emulsion, its mfg. method and use - Google Patents
Water-based polyurethane emulsion, its mfg. method and use Download PDFInfo
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Abstract
The present invention provides an aqueous polyurethane emulsion, capable of obtaining a film excellent in re-dissolving property, close adhesion, coated film physical properties, and its method. This aqueous polyurethane emulsion is obtained by emulsifying in water a polyurethane resin obtained by reacting (A) an organic polyisocyanate, (B) an active hydrogen-containing compound, (C) a compound containing an anionic polar group and the active hydrogen group and (D) a neutralizing agent. The rganic polyisocyanate contains (A1) an allophanate-modified polyisocyanate obtained from (A1-1) an alkoxypoly(oxyalkylene) glycol containing >=50 mol % oxyethylene group in its recurring units and (A1-2) hexamethylene diisocyanate.
Description
Technical field
The present invention relates to can be by existing installation make and aqueous polyurethane emulsion that thin film physics is well-behaved, and relate to the Manufacturing approach and use of this emulsion.
Background technology
Because aqueous polyurethane emulsion has the good binding property to base material, wearability, shock-resistance, solvent resistance etc., thereby in paper, plastics, film, metal, fibre product etc., be widely used as coating, printing ink, tackiness agent, various coating agent, and its manufacture method is studied.And, developed in the independent or mixed solvent of for example acetone, methylethylketone, N-Methyl pyrrolidone (being designated hereinafter simply as NMP), aromatic organic solvent etc., make polyurethane resin solution after, through waterborne polyurethane resins such as the emulsion of water-dispersionization and desolventizing treating processes, soliquid, the aqueous solution.
If with allophanate-modified polyisocyanates and other urethane-modified polyisocyanates or isocyanurate-modified polyisocyanates comparison, usually has lower viscosity, and, can in the isocyanic ester skeleton, import various side-chain radicals by selecting properties-correcting agent.For example, if import the polyoxyethylene group, then can obtain hydrophilic polyisocyanates.And,, then can obtain dissolving in the polyisocyanates of poor solvent if import alkyl with more carbonatoms.
In patent documentation 1, disclose and in the isocyanate prepolymer composition of urethane resin, used the aqueous polyurethane emulsion that has imported the allophanate-modified polyisocyanates of polyoxyethylene group at side chain.
[patent documentation 1] spy opens flat 1-104612 communique
But, in patent documentation 1, in the raw material of allophanate-modified polyisocyanates, usually use 2, the 4-tolylene diisocyanate (is designated hereinafter simply as 2,4-TDI), isophorone diisocyanate (IPDI) etc. comprises the organic diisocyanate (asymmetric vulcabond) of 2 isocyanate groups with differential responses.Because general asymmetric organic diisocyanate has ring structure (a kind of ladder structure) usually, thereby the flexibility of molecular skeleton is low and viscosity also uprises easily.
In patent documentation 2, method is with an organic solvent disclosed when making the waterborne polyurethane resin dispersion not.
[patent documentation 2] spy opens flat 10-265539 communique
But, in the manufacture method of patent documentation 2, because the viscosity of isocyanate end prepolymer is very high, if do not use even mixer, homogenizer, Micro Fluid bed with strong shearing force, then usually exist and to carry out the situation of water-dispersion, thereby be necessary producing apparatus is transformed.
Summary of the invention
The object of the present invention is to provide a kind of during fabrication not with an organic solvent or can reduce the usage quantity of organic solvent, and can access and have the good aqueous polyurethane emulsion of the film of solvability, adaptation etc. again, its manufacture method, and the water-borne coatings and the water-based printing ink that use this emulsion.
For achieving the above object, of the present invention theing contents are as follows stated shown in (1)～(5).
(1) a kind of aqueous polyurethane emulsion, it is characterized in that described aqueous polyurethane emulsion is by making by organic multiple isocyanate (A), the compound (B) that contains reactive hydrogen, the compound (C) that contains anionic polar group and reactive hydrogen, and urethane resin emulsification in water that neutralizing agent (D) reaction obtains obtains, and wherein said organic multiple isocyanate (A) comprises and obtained by poly-(alkylidene oxide) glycol (A1-1) of the alkoxyl group that contains the above oxygen ethylidene of 50mol% in repeating unit and hexamethylene diisocyanate (A1-2) reaction, and be substantially free of the allophanate-modified polyisocyanates (A1) of isocyanurate group.
(2) above-mentioned (1) described aqueous polyurethane emulsion, the compound (B) that wherein contains reactive hydrogen comprises the macromolecule polyol (B1) of number-average molecular weight more than 500 and the low molecule polyamines and/or the water (B2) of number-average molecular weight less than 500 at least.
(3) a kind of manufacture method of aqueous polyurethane emulsion, it is characterized in that comprising: will be except that the compound that contains reactive hydrogen (B) low molecule polyamines and/or the water (B2) and the compound (C) and the organic multiple isocyanate (A) that contain anionic polar group and reactive hydrogen, under the condition that does not have organic solvent basically, react, use neutralizing agent (D) neutralization then, make the emulsification in water of resulting isocyanate end prepolymer then, and carrying out transfer reaction with low molecule polyamines and/or water (B2), wherein said organic multiple isocyanate (A) comprises and is obtained by poly-(alkylidene oxide) glycol (A1-1) of the alkoxyl group that contains the above oxygen ethylidene of 50mol% in repeating unit and hexamethylene diisocyanate (A1-2) reaction, and be substantially free of the allophanate-modified polyisocyanates (A1) of isocyanurate group.
(4) a kind of water-borne coatings is characterized in that comprising above-mentioned (1) or (2) described aqueous polyurethane emulsion.
(5) a kind of water-based printing ink is characterized in that comprising above-mentioned (1) or (2) described aqueous polyurethane emulsion.
Owing to use the allophanate-modified body in the isocyanate prepolymer composition of urethane resin, be substantially free of the tricarbimide ester group and can obtain by poly-(alkylidene oxide) glycol of the alkoxyl group that in repeating unit, contains the oxygen ethylidene more than the 50mol% and hexamethylene diisocyanate (hereinafter to be referred as HDI), therefore, when making aqueous polyurethane emulsion of the present invention (particularly when making the isocyanate end prepolymer), even not with an organic solvent, the viscosity of reaction solution is very not low yet.And certain resulting emulsion does not contain organic solvent yet.In addition, the film that is formed by this aqueous polyurethane emulsion has good solvability, adaptation etc. again, and when being used for water-based printing ink, the space of a whole page is detained (version is closely questioned ま リ) property and is further improved.
Can be used for organic multiple isocyanate of the present invention (A) and comprise the allophanate-modified polyisocyanates (A1) that is substantially free of isocyanurate group.If comprise the isocyanuric acid ester group basically, then the viscosity owing to organic multiple isocyanate (A) increases, just must be by organic solvent diluting to reduce viscosity when the manufacturing of aqueous polyurethane emulsion.
Above-mentioned allophanate-modified polyisocyanates (A1) is obtained with HDI (A1-2) by poly-(alkylidene oxide) glycol (A1-1) of alkoxyl group that contains (more than the preferred 70mol%) oxygen ethylidene more than the 50mol% in repeating unit.Wherein, when the not enough 50mol% of oxyethylene group in the repeating unit of (A1), the water-dispersion ability of resulting urethane resin just becomes insufficient.In addition, when other organic diisocyanates that use except that HDI, for example when using TDI or IPDI, owing to have ring structure (a kind of ladder structure), the flexibility of molecular skeleton is lower, and, also form the higher material of viscosity easily.Therefore, because must be with an organic solvent when making this allophanate-modified polyisocyanates, so not preferred in the present invention.
The isocyanate content of this allophanate-modified polyisocyanates (A1) is preferably 5～15 quality %, and is preferably 8～13 quality % especially.And, be preferably below the 1000mPas 25 ℃ viscosity, be preferably 100～800mPas especially.Cross low or viscosity when too high when the content of isocyanic ester, the viscosity of the reaction solution in the reaction uprises, and it is big that the load that manufacturing installation bore becomes.Cross when low when the too high levels of isocyanic ester or viscosity, allophanate-modified degree (A1) is usually insufficient, and the dispersive ability of resulting urethane resin becomes insufficient easily.
The manufacture method of this allophanate-modified polyisocyanates (A1) is as described below.With respect to poly-(alkylidene oxide) glycol of alkoxyl group, add excessive HDI (poly-(alkylidene oxide) glycol/HDI=1/5 of preferred alkoxyl group～1/20 (mol ratio)), carry out the urethane reaction.Then, the catalyzer of the allophanic acid esterification of adding carboxylic metallic salt etc. carries out allophanic acid esterification reaction.Then, add reaction terminating agents such as phosphoric acid, stop allophanic acid esterification reaction, and remove unreacted HDI, obtain the allophanate-modified polyisocyanates of target product by thin film distillation etc.
And preferred allophanic acid esterification catalyzer is the carboxylate salt of zirconium, the carboxylate salt of zirconyl, the carboxylate salt of tin (divalence).These catalyzer can use separately, also its two or more mixing can be used.And the catalyzer of the allophanic acid esterification except these, the degree of side reactions such as reaction that the isocyanuric acid esterification takes place is big, and low as the content of the allophanate-modified polyisocyanates of target product.The average functional group number of the polyisocyanates that can obtain by this method is big, and is easy to generate gelation when making urethane resin.And,, enumerate ニ Star カ オ Network チ Star Network ス zirconium (Japanese chemical Industry Co., Ltd makes) etc. as the concrete commodity of allophanic acid esterification catalyzer.
When the organic diisocyanate that circulates extensively on the market of using except that HDI, when using above-mentioned zirconium-based catalyst to make allophanate-modified polyisocyanates, allophanic acid esterification reaction is insufficient, is difficult to obtain the allophanate-modified polyisocyanates as target product.
Poly-(alkylidene oxide) glycol (A1-1) of employed alkoxyl group usually can be by being initiator with the compound that has 1～10 carbon atom and have 1 carboxyl, the oxirane that contains the oxyethane more than the 50mol% is carried out opening obtaining in making allophanate-modified polyisocyanates (A1).
Wherein, as initiator, enumerate methyl alcohol, ethanol, propyl alcohol (comprising various isomer), butanols (comprising various isomer), aromatic-aliphatic alcohol such as amylalcohol phenolic compounds such as unsaturated fatty alcohols such as saturated fatty alcohol, vinyl carbinol, phenol, benzylalcohols such as (comprising various isomer) etc.These initiators can use separately, also its two or more mixing can be used.In the present invention, give hydrophilic effect, preferably have the Fatty Alcohol(C12-C14 and C12-C18) of 5 following carbonatomss, especially preferably have the saturated fatty alcohol of 2 following carbon atoms in order to improve.And if consider the water-dispersion ability of resulting urethane resin, the content of the oxyethane of preferred oxirane is more than the 70mol%.
The number-average molecular weight of poly-(alkylidene oxide) glycol (A1-1) of alkoxyl group is preferably 200～2000, is preferably 300～1000 especially.When the number-average molecular weight of poly-(alkylidene oxide) glycol (A1-1) of alkoxyl group is crossed when low, it is little that the wetting ability of allophanate-modified polyisocyanates (A1) is given effect, uses the water-dispersion scarce capacity of its urethane resin.And, when the number-average molecular weight of poly-(alkylidene oxide) glycol (A1-1) of alkoxyl group is too high, because the crystallization of polyethylene oxide chain, the viscosity of resulting allophanate-modified polyisocyanates (A1) becomes big or becomes and solidifies easily, thereby becomes and be difficult to not use solvent to make aqueous polyurethane emulsion.
In the present invention, can mix the organic multiple isocyanate that uses except that above-mentioned allophanate-modified polyisocyanates (A1), for example enumerate 2 specifically, 4-TDI, 2, the 6-tolylene diisocyanate, 2,2 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4,4 '-diphenylmethanediisocyanate, phenylbenzene dimethylmethane vulcabond, benzhydryl vulcabond, naphthalene diisocyanate, phenylene vulcabond, xylylene diisocyanate, aromatic diisocyanate such as tetramethylxylylene diisocyanate; Tetramethylene diisocyanate, HDI, lysinediisocyanate, 2-methylpentane-1,5-vulcabond, 3-methylpentane-1,5-vulcabond, 2,2,4-tri-methyl hexamethylene-1,6-vulcabond, 2,4,4-tri-methyl hexamethylene-1, aliphatic diisocyanates such as 6-vulcabond; Alicyclic diisocyanates such as IPDI, cyclohexyl diisocyanate, hydrogenation of benzene dimethylene diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation Three methyl Benzene dimethylene diisocyanate.These organic diisocyanates can use separately, it can be mixed and use.And, also can use their modification body such as addition modification body, carbodiimide modified body, allophanate-modified body (except that above-mentioned (A1)), biuret modified body, urea diketone modification body, the imine modified body of urea, isocyanurate-modified body.At this moment, with respect to whole organic multiple isocyanates (A), preferred allophanate-modified polyisocyanates (A1) is more than the 25 quality %.When the organic multiple isocyanate except that (A1) is too much, because the Intermolecular Forces of resulting urethane resin becomes excessive, thereby the cohesion easily that becomes.
Can be used for the compound (B) that contains reactive hydrogen of the present invention, preferably to comprise number-average molecular weight at least be the macromolecule polyol (B1) more than 500 and the low molecule polyamines and/or the water (B2) of number-average molecular weight less than 500.Can obtain resin by the aftermentioned prepolymer method, and prepolymer method can will provide the carbamate groups of cohesiveness/adaptation to import in the skeleton of abundant equilibrated urethane resin with the urea groups that embodies thermotolerance and intensity effect, and can reduce the viscosity in the reaction process.
The number-average molecular weight of macromolecule polyol (B1) is more than 500, preferred 1000～5000.And the average functional group number of this macromolecule polyol (B1) is preferably 2～4, more preferably 2～3.In limited time, film breaks easily under the number-average molecular weight deficiency of macromolecule polyol.And,, then be difficult to form film with sufficient physical properties if surpass the upper limit.And the number-average molecular weight of macromolecule polyol can be calculated by average functional group number and by the end group amount that the end-group analysis method obtains.
As macromolecule polyol (B1), specifically enumerating polyester polyol, polyesteramide polyvalent alcohol, polyether glycol, polyester ether polylol, polycarbonate polyol, polyolefin polyhydric alcohol, animals and plants is polyvalent alcohol etc.These polyvalent alcohols can use separately, perhaps with its two or more mixed uses.
When paying attention to adaptation, preferred macromolecule polyol (B1) is a polyester polyol among the present invention, and when paying attention to water tolerance, preferred macromolecule polyol (B1) is polyether glycol or polycarbonate polyol among the present invention.
As polyester polyol, can pass through known phthalic acid, m-phthalic acid, terephthalic acid, naphthalene dicarboxylic acids, succsinic acid, tartrate, oxalic acid, propanedioic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, propene dicarboxylic acid, nonane diacid, sebacic acid, 1, the 4-cyclohexyl dicarboxylic acid, α-hydrogen muconic acid, β-hydrogen muconic acid, α-butyl-α-Yi Jiwuersuan, α, β-diethyl succsinic acid, toxilic acid, dicarboxylic acid such as fumaric acid or acid anhydrides more than a kind with, ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 3,3-dihydroxymethyl heptane, dipropylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, hexanaphthene-1, the 4-glycol, hexanaphthene-1, the 4-dimethanol, the dimer acids glycol, the oxyethane of dihydroxyphenyl propane or propylene oxide adduct, two (beta-hydroxy ethyl) benzene, the phenylenedimethylidyne glycol, glycerine, TriMethylolPropane(TMP), low molecular polylols such as tetramethylolmethane etc. polycondensation obtains more than a kind.And also enumerating the lactone that can be obtained by 6-caprolactone, δ-Wu Neizhi, the monomeric ring-opening polymerization of cyclic esters such as δ-Wu Neizhi (so-called lactone) of alkyl replacement that 6-caprolactone, alkyl replace is polyester polyol etc.And, the part of low molecular polylol also can be replaced to low molecule polyamines such as quadrol, hexamethylene-diamine, isophorone diamine or, low molecule amino alcohol such as monoethanolamine.At this moment, can obtain the polyester-amides polyvalent alcohol.
As polyether glycol, can be with such as employed low molecular polylol class in above-mentioned polyester polyol synthetic, quadrol, propylene diamine, tolylene diamine, mphenylenediamine, diphenylmethane diamine, having more than 2 of low molecule polyamines such as phenylenedimethylidyne diamines class etc., the compound of preferred 2～3 reactive hydrogens is as initiator, by such as oxyethane, propylene oxide, the alkylene oxides of butylene oxide ring etc., alkyl glycidyl ether classes such as methyl glycidyl ether, arylolycidyl ethers classes such as phenyl glycidyl ether, single or its mixture of cyclic ether monomers such as tetrahydrofuran (THF) uses known method addition polymerization to obtain.
As polycarbonate polyol, can be by more than a kind of the low-molecular-weight diol in above-mentioned source as polyester polyol, low molecule triol etc., obtain with the dealcoholization or the dephenolize reaction of ethylene carbonate, diethyl carbonate, dipheryl carbonate base ester.And, also can use the ester exchange offspring of above-mentioned polycarbonate polyol and polyester polyol.
As polyester ether polylol, enumerate the polyol that above-mentioned polyether glycol and above-mentioned dicarboxylic acid etc. obtain.And enumerate can by above-mentioned polyester or polycarbonate and, the compound that obtains of the reaction of epoxide or cyclic ether.
As polyolefin polyhydric alcohol, enumerate polyhutadiene with 2 above hydroxyls, hydrogenation polyhutadiene, polyisoprene, hydrogenation polyisoprene etc.
As animals and plants is polyvalent alcohol, and enumerating Viscotrol C is polyvalent alcohol, silk fibroin etc.
And, so long as number-average molecular weight is the macromolecule polyol that comprises average 1 above reactive hydrogen more than 500 in (preferred 1000～5000) and per 1 molecule, except dimer acids is that polyvalent alcohol, hydrogenation dimer acids are the polyvalent alcohol, can also use Resins, epoxy, polyamide resin, vibrin, acrylic resin, Gum Rosin, urea resin, melamine resin, phenol resins, coumarone resin, polyvinyl alcohol etc. to contain the resin of reactive hydrogen as macromolecule polyol.
As low molecule polyamines, enumerate quadrol, tetramethylene-diamine, hexamethylene-diamine, isophorone diamine, dicyclohexyl methyl hydride diamines, ditan diamines, diethylenetriamine etc.These low molecule polyamines can use separately or its any mixing more than 2 kinds is used.As (B2) of the present invention composition, if consider the physical properties of resulting urethane resin film or weather resistance etc., preferably water, hexamethylene-diamine or isophorone diamine.
As can be used for the anionic property polar group that contains the compound (C) of anionic property polar group and reactive hydrogen of the present invention, enumerate carboxyl, sulfonic group, phosphate, phospho acid base, phosphonate group etc.Wherein, as the specific examples of anionic property polar group, comprise sulphonate-base, phosphate base, phospho acid alkali, phosphonic acids alkali etc.In the present invention, preferably the selection by aftermentioned neutralizing agent (D) makes variation from the emulsion state to the filminess become the carboxyl of irreversible change.
As the compound that contains carboxyl and reactive hydrogen, enumerate 2,2-dimethylol propionic acid (being designated hereinafter simply as DMPA), 2, the reaction product of 2-dimethylolpropionic acid (being designated hereinafter simply as DMBA), polyamines and acid anhydrides, with dimethylol propionic acid or dimethylolpropionic acid as lactone adduct of initiator etc.These compounds can use separately or its two or more mixing are used.Preferred in the present invention DMPA and DMBA.
As can be used for neutralizing agent of the present invention (D), enumerate ammonia, ethamine, Trimethylamine 99, triethylamine, tri-isopropyl amine, Tributylamine, trolamine, N methyldiethanol amine, N-phenyldiethanol-amine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-organic amines such as 1-propyl alcohol; Basic metal such as lithium, potassium, sodium; Inorganic base such as sodium hydroxide, potassium hydroxide etc.But, in order to improve dried weathering resistance, water tolerance, preferably can be by the easily dissociated high volatile volatile material of heating, concrete preferred ammonia, Trimethylamine 99, triethylamine.These neutralizing agents can use separately, also its two or more mixing can be used.
In the present invention, consider the physical properties of resulting urethane resin film etc., can use the low molecular polylol of number-average molecular weight less than 500.As this low molecular polylol, enumerate the low molecular polylol that constitutes above-mentioned polyester polyol.
In the present invention, when the synthesis of polyurethane resin, can use reaction terminating agent according to needs such as regulating molecular weight.As reaction terminating agent, can be unary alcohol, monobasic amine, and, also can use amino alcohol according to circumstances as reaction terminating agent.And, can use monoisocyanates such as phenylcarbimide, butyl isocyanate, cyclic isocyanate polyhexamethylene etc. as reaction terminating agent.
Can be used as the concrete unary alcohol of reaction terminating agent, enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, 2-Ethylhexyl Alcohol etc.As the monobasic amine, enumerate primary amine such as ethamine, propylamine, butylamine, secondary amine such as diethylamine, dibutylamine.As alkamine, enumerate monoethanolamine, diethanolamine etc.
As the manufacture method of aqueous polyurethane emulsion, main method is listed below described method:
Organic multiple isocyanate (A), the compound (C) that contains the compound (B) of reactive hydrogen and contain anionic property polar group and reactive hydrogen react the synthesis of polyurethane resin under the condition of reactive hydrogen surplus, use neutralizing agent (D) to neutralize then and make it be dispersed in the step of one in the water (one-shot) method
Organic multiple isocyanate (A) and the compound that contains reactive hydrogen (B) except that low molecule polyamines and/or water (B2) and the compound (C) that contains anionic property polar group and reactive hydrogen react the prepolymer of synthesizing isocyanate cardinal extremity base under the atmosphere of isocyanate group surplus, use neutralizing agent (D) neutralization then, it is dispersed in the water, and then uses low molecule polyamines and/or water (B2) to carry out the prepolymer method of transfer reaction.
In single stage method, the mol ratio of isocyanate group/reactive hydrogen is 0.5～less than 1, preferred 0.8～less than 1.When this mol ratio less than 0.5, because the molecular weight of polyether polyols with reduced unsaturation is too small, thereby the weather resistance of resin film is relatively poor.When this mol ratio is 1 when above, when synthetic polymer, cause gelation easily.
After urethane, after using neutralizing agent (D) neutralization according to circumstances,, obtain aqueous polyurethane emulsion as target compound by adding the water dispersible polyurethane resin.At this moment The faster the better for stirring velocity.
In prepolymer method, the mol ratio of the isocyanate group/reactive hydrogen base when prepolymer is synthetic is 1.1～5.0, is preferably 1.2～4.0.When this mol ratio less than 1.1, the molecular weight of prepolymer is excessive, is difficult to carry out follow-up reactions steps.When this mol ratio surpassed 5.0, it is not enough that the adaptation of resin film becomes.
After the pre-polymerization materialization, use neutralizing agent (D) to neutralize, then by adding the water-dispersion prepolymer, by adding low molecule polyamines and/or water (B2) and adding reaction terminating agent as required, to carry out the amine reaction of propagation, obtain the target product aqueous polyurethane emulsion.The temperature of reaction of amine reaction of propagation is preferably 30～50 ℃.After disperseing prepolymer, The faster the better for stirring velocity.
Aqueous polyurethane emulsion of the present invention is characterised in that and uses the allophanate-modified polyisocyanates (A1) with the effect that makes the urethane resin lowering viscousity.But, in single stage method, even use allophanate-modified polyisocyanates (A1) with lowering viscousity effect, the number-average molecular weight of the urethane resin before water-dispersion usually reaches 10, more than 000, its viscosity also reaches high viscosity (being 100 for example, more than the 000mPas) under 75 ℃ of temperature in the case, thereby becomes easily and be difficult to water-dispersion.Therefore, because the solvent free when the prepolymer method of prepolymer water-dispersion in the stage of number-average molecular weight lower (viscosity is lower) can be realized making, so preferably.
When urethane reaction or pre-polymerization physical reaction, can use known so-called urethane catalyzer as catalysts.Specifically, enumerate organic amines such as organometallic compound, triethylene diamines such as two lauric acid dioctyl tins or its salt etc.Temperature of reaction during urethane is 10～100 ℃, is preferably 30～80 ℃.
The number-average molecular weight of the urethane resin of the aqueous polyurethane emulsion that obtains in this way is preferably more than 5000, is preferably more than 10000 especially.When the number-average molecular weight less than 5000 of urethane resin, it is not enough that its weather resistance becomes.In the present invention, number-average molecular weight is to measure by the gel permeation chromatography (GPC method) that uses the polyoxyethylene glycol typical curve.
In aqueous polyurethane emulsion, the median size of urethane resin is below the 100nm, below the preferred 80nm.Prescribe a time limit above last when median size, existence produces sedimentary situation through after a while.And median size is to use accumulative to resolve the resulting value of being measured by dynamic light scattering of value.
The viscosity of aqueous polyurethane emulsion under 25 ℃, when solids component is 30 quality %, below 2000mPas, preferred 10～1000mPas.Prescribe a time limit above last when viscosity, it is difficult that coatingization afterwards easily becomes.
The content of the anionic property polar group of urethane resin of the present invention is preferably below the 0.5mmol/g, more preferably below the 0.3mmol/g.When the too high levels of anionic property polar group, the resin before water-dispersion or the viscosity of prepolymer become too high, are difficult to water-dispersion.And acid resistance, the alkali resistance of film easily reduce.
The content of the nonionic hydrophilic radical (polyoxyethylene) of urethane resin of the present invention is preferably 10～50 quality %, is preferably 15～40 quality % especially.When the too high levels of nonionic hydrophilic radical, the water tolerance of film reduces easily.When this content is crossed when low, when making aqueous polyurethane emulsion, the resin before water-dispersion or the water-dispersion of the prepolymer difficulty that becomes.
The summation of the concentration of the carbamate groups of urethane resin of the present invention and urea groups concentration is preferably 1.0～3.0mmol/g, more preferably 1.3～2.7mmol/g.And when not having urea groups in the resin, the concentration of carbamate groups is preferably 1.0～3.0mmol/g, more preferably 1.3～2.7mmol/g.When the total concn of the concentration of carbamate groups and urea groups concentration is lower than down in limited time, it is insufficient that film strength becomes easily.And, to prescribe a time limit above last when this total concn, it is insufficient that the adaptation of film becomes easily.
Can in aqueous polyurethane emulsion of the present invention, use additive and auxiliary agent commonly used in the aqueous systems as required.For example, can add stiffening agent, pigment, dyestuff, antitack agent, dispersion stabilizer, viscosity modifier, levelling agent, anti-gelating agent, photostabilizer, oxidation inhibitor, UV light absorber, inorganic and organic filler, softening agent, lubricant, antistatic agent, toughener, catalyzer etc.
In addition, polyaminoester emulsion of the present invention can also use with the form of the emulsion of mixing other resenes.Comprise for example ACRYLIC EMULSION, polyester emulsion, polyolefin emulsion, latex etc.
Embodiment
Be described in detail with regard to embodiments of the invention and comparative example below, but the present invention is not limited to these embodiment.Unless special qualification, " % " expression " quality % " among the embodiment.
Synthesizing of allophanate-modified polyisocyanates
Synthesis example 1
At the volume that has agitator, thermometer, water cooler and nitrogen conduit is to add 863g HDI, 137g MPEG-1,0.2g 2 ethyl hexanoic acid zirconium in the reactor of 1L, and reaction is 2 hours under 90 ℃ of temperature.Then, add 0.1g phosphoric acid, under 50 ℃ of temperature, carry out 1 hour termination reaction.The isocyanate content of the reaction product after the termination reaction is 40.2%.Under the condition of 130 ℃ * 0.04kPa, this reaction product is carried out thin film distillation, obtain allophanate-modified polyisocyanates isocyanic ester ALP-1.
The content of the isocyanic ester of ALP-1 is 11.4%, and the viscosity under 25 ℃ of temperature is 140mPas, and the content of free vulcabond is 0.1%.And, use FT-IR and
13C-NMR analyzes ALP-1, confirms not have carbamate groups, isocyanuric acid ester group basically, and confirms to exist allophanate group.
Synthesis example 2
At the volume that has agitator, thermometer, water cooler and nitrogen conduit is to add 782.6g HDI, 217.4g MPEG-2,0.2g 2 ethyl hexanoic acid zirconium in the reactor of 1L, and reaction is 2 hours under 90 ℃ of temperature.Then, add 0.1g phosphoric acid, under 50 ℃ of temperature, carry out 1 hour termination reaction.The isocyanate content of the reaction product after the termination reaction is 36.5%.Under the condition of 130 ℃ * 0.04kPa, this reaction product is carried out thin film distillation, obtain allophanate-modified polyisocyanates isocyanic ester ALP-2.
The content of the isocyanic ester of ALP-2 is 7.2%, and the viscosity under 25 ℃ of temperature is 100mPas, and the content of free vulcabond is 0.1%.And, use FT-IR and
13C-NMR analyzes ALP-2, confirms not have basically carbamate groups, isocyanuric acid ester group, and confirms to exist allophanate group.
Synthesis example 3
At the volume that has agitator, thermometer, water cooler and nitrogen conduit is to add 200g NMP, 265.6g 2 in the reactor of 1L, and 4-TDI, 534.5g MPEG-2 carry out 4 hours urethane reaction under 80 ℃ of temperature.At this moment isocyanate content is 9.6%.Then, add 0.5g PTSM, 0.025g zinc acetylacetonate, reaction is 5 hours under 100 ℃ of temperature, obtains allophanate-modified polyisocyanates ALP-3.
The solids component of ALP-3 is 80%, the content of isocyanic ester is 6.4%, and the viscosity under 25 ℃ of temperature is 50mPas, and the content of free vulcabond is 0.1%.And, use FT-IR and
13C-NMR analyzes ALP-3, confirms not have carbamate groups, and confirms to exist allophanate group and isocyanuric acid ester group.
In synthesis example 1～3:
HDI: methylene diisocyanate
2,4-TDI: 2,4 toluene diisocyanate
MPEG-1: methoxy poly (ethylene glycol)
Number-average molecular weight=400
MPEG-2: oxyethyl group polyoxyethylene glycol
Number-average molecular weight=700
PTSM: methyl tosylate
NMP: N-Methyl pyrrolidone
Synthesizing of aqueous polyurethane emulsion
Embodiment 1
At the volume that has agitator, thermometer, water cooler and nitrogen-sealed pipe is to add 125.8g polyvalent alcohol-1,4.7g DMBA in the reactor of 1L, mixes under 100 ℃ of temperature.Then, add 148.2g ALP-1,0.05g DOTDL, after under 80 ℃ of temperature, reacting 3 hours, add among the 3.2g TEA and carboxyl, obtain the prepolymer of isocyanate end.The isocyanate content of this prepolymer is 3.19%, and the viscosity under 75 ℃ of temperature is 1350mPas.Then, add 600g water and make its emulsification.After the emulsification, the ammoniacal liquor that is pre-mixed 100g water, 18.2g IPDA by adding carries out transfer reaction.Termination reaction when confirming not have isocyanate group by FT-IR obtains aqueous polyurethane emulsion PU-1.
The solids component of PU-1 is 29.9%, and the viscosity under 25 ℃ of temperature is 32mPas, and the pH value is 7, and median size is 35nm.
Embodiment 2
In the reaction unit identical with embodiment 1, add 65.8g polyvalent alcohol-4, add 77.5g ALP-1,0.02g DOTDL then, under 80 ℃ of temperature, after the reaction 3 hours, obtain the prepolymer of isocyanate end.The isocyanate content of this prepolymer is 2.31%, and the viscosity under 75 ℃ of temperature is 12200Pas.Then, add 750g water and make its emulsification.After the emulsification, the ammoniacal liquor that is pre-mixed 100g water, 6.7g IPDA by adding carries out transfer reaction.Termination reaction when confirming not have isocyanate group by FT-IR obtains the polyaminoester emulsion PU-2 of water-based.
The solid component concentration of PU-2 is 15.0%, and the viscosity under 25 ℃ of temperature is 10Pas, and the pH value is 9, and median size is 15nm.
Embodiment 3
In the reaction unit identical, add 135.3g polyvalent alcohol-1,5.0g DMBA also mixes under 100 ℃ of temperature with embodiment 1.Add 159.3g ALP-1,0.05g DOTDL then, after under 80 ℃ of temperature, reacting 3 hours, add among the 3.4g TEA and carboxyl, obtain the prepolymer of isocyanate end.The isocyanate content of this prepolymer is 3.19%, and the viscosity under 75 ℃ of temperature is 1350mPas.Then, add 702g water and make its emulsification, under 40 ℃ of temperature, make water carry out transfer reaction then.Termination reaction when confirming not have isocyanate group by FT-IR obtains aqueous polyurethane emulsion PU-3.
The solids component of PU-3 is 30.1%, and the viscosity under 25 ℃ of temperature is 30mPas, and the pH value is 7, and median size is 35nm.
Embodiment 4～5, comparative example 1
Use reaction unit, the step identical with embodiment 3, the raw material shown in the use table 1 or 2 obtains aqueous polyurethane emulsion PU-4～5.
And,, thereby do not carry out follow-up evaluation owing to PU-7 (comparative example 1) can not all disperse equably when making prepolymer be dispersed in the water.
Embodiment 6
Use reaction unit, the step identical with embodiment 1, the raw material shown in the use table 2 obtains aqueous polyurethane emulsion PU-6.
Table 1
| Embodiment | ||||
| 1 | 2 | 3 | 4 | |
| Macromolecule polyol (g) polyvalent alcohol-1 polyvalent alcohol-2 | 125.8 | 135.3 | 135.3 | |
| Polyvalent alcohol (g) polyvalent alcohol-4 DMBA that contains the anionic property polar group | 4.7 | 65.8 | 5.0 | 5.0 |
| Organic multiple isocyanate (g) ALP-1 | 148.2 | 77.5 | 159.3 | 159.3 |
| Urethane catalyzer (g) DOTDL | 0.05 | 0.05 | 0.05 | 0.05 |
| Neutralizing agent (g) TEA | 3.2 | 3.4 | 3.4 | |
| Viscosity (mPas) under 75 ℃ of temperature of prepolymer isocyanate content (%) | 3.19 1350 | 2.31 12200 | 3.19 1350 | 3.19 2000 |
| Dispersion medium (g) water | 600 | 750 | 702 | 702 |
| Amine aqueous solution (g) IPDA water | 18.2 100 | 6.7 100 | ||
| The emulsion title | PU-1 | PU-2 | PU-3 | PU-4 |
| Viscosity (mPas) the pH value average grain diameter (nm) that analysis result outward appearance solid constituent (%) is 25 ℃ | Milky white liquid 29.9 32 7 35 | Milky white liquid 15.0 10 9 15 | Milky white liquid 30.1 30 7 35 | Milky white liquid 29.8 35 7 40 |
Table 2
| Embodiment | Comparative example | ||
| 5 | 6 | 1 | |
| Macromolecule polyol (g) polyvalent alcohol-1 polyvalent alcohol-2 polyvalent alcohol-3 | 135.3 | 138.2 | 110.4 |
| Polyvalent alcohol (g) DMBA that contains the anionic property polar group | 5.0 | 5.1 | 4.1 |
| Organic multiple isocyanate (g) ALP-1 ALP-2 ALP-3 HDI | 159.3 | 143.2 5.8 | 231.4 |
| Organic solvent (g) NMP | 28 | ||
| Urethane catalyzer (g) DOTDL | 0.05 | 0.05 | 0.05 |
| Neutralizing agent (g) TEA | 3.4 | 3.5 | 2.8 |
| Viscosity (mPas) under 75 ℃ of temperature of prepolymer isocyanate content (%) | 3.19 1100 | 1.96 1600 | 2.09 1800 |
| Dispersion medium (g) water | 702 | 600 | 655 |
| Amine aqueous solution (g) EDA water | 4.1 100 | ||
| The emulsion title | PU-5 | PU-6 | PU-7 |
| Viscosity (mPas) the pH value median size (nm) that analytical results outward appearance solids component (%) is 25 ℃ | Milky white liquid 29.9 32 7 35 | Milky white liquid 29.9 100 9 60 | - - - - - |
In embodiment 1～6, comparative example 1 and table 1～2
Polyvalent alcohol-1: by the 3-methyl isophthalic acid, the polyester polyol that 5-pentanediol and hexanodioic acid obtain
Number-average molecular weight=2000
Polyvalent alcohol-2: by 1, the polycarbonate polyol that 6-hexylene glycol and diethyl carbonate obtain
Number-average molecular weight=2000
Polyvalent alcohol-3: poly-(oxidation tetramethylene) glycol
Number-average molecular weight=2000
Polyvalent alcohol-4:, that 6-hexylene glycol, hexanodioic acid, 5-sulfoisophthalic acid methyl esters sodium obtain, contain by 1
The polyester polyol of sodium sulfonate alkali
Number-average molecular weight=1000
Sodium sulfonate (alkali) content=0.4mmol/g
DMBA: 2, the 2-dimethylolpropionic acid
DOTDL: two lauric acid dioctyl tins
IPDA: isophorone diamine
EDA: quadrol
The median size determinator:
Otsuka Electronics Co., Ltd. makes, and electrophoretic light scattering is ELS-800
In embodiment 1～6, obtain the aqueous polyurethane emulsion of target compound; And in comparative example 1, in the water-dispersion step of prepolymer, prepolymer can not disperse fully.This can think because, because NMP mixes with arbitrary proportion with water, NMP and water blended speed are a lot of rapidly than the hydration rate of prepolymer, thus cause disperseing balance destroyed due to.
The evaluation of filming
Application Example 1～6
To being that host, self-emulsifying type polyisocyanates (ア Network ァ ネ one ト (registered trademark) 200 is made in Japanese polyurethane industry) are estimated for the two-component-type water-borne coatings of stiffening agent with aqueous polyurethane emulsion PU-1～6.Blending ratio is with solid component meter host/stiffening agent=100/50 (mass ratio).
Evaluation result is as shown in table 3.
Coating, curing condition
Base material: aluminium sheet (50mm * 25mm * 0.5mm)
The absorbent cotton that use is soaked with methylethylketone carries out degreasing to coated face
Glue spread: 50g/m
2
Coating temperature: 20 ℃
Curing condition: room temperature * 10 minute+50 ℃ * 24 hours+room temperature * 24 hour
Performance test
Adaptation: according to JIS K5400, the test of reticulate pattern strips method
Rub(bing)test: use the absorbent cotton that is soaked with dimethylbenzene to the obliterating 100 times of filming, observe
The variation of appearance of film
Resistance to bend(ing): measure according to JIS K5400
The axle diameter is 2mm
Table 3
| Application Example | ||||||
| 1 | 2 | 3 | 4 | 5 | 6 | |
| The emulsion title | PU-1 | PU-2 | PU-3 | PU-4 | PU-5 | PU-6 |
| Adaptation | ○ | ○ | ○ | ○ | ○ | ○ |
| Rub(bing)test | ○ | ○ | ○ | ◎ | ○ | ○ |
| Resistance to bend(ing) | ◎ | ○ | ◎ | ◎ | ◎ | ◎ |
Judgement criteria
Adaptation
Zero: the film residual rate is more than 80%
△: the film residual rate is more than 50%, but less than 80%
*: film residual rate less than 50%
Rub(bing)test
Zero: confirm almost not have film damage etc.
△: confirm more or less to exist film damage etc.
*: confirm to exist considerable film damage etc.
Resistance to bend(ing)
Zero: confirm there is not film breaks fully or peel off etc.
△: confirm more or less there is film breaks or peel off etc.
*: confirm there is significant film breaks or peel off etc.
The printing ink test
Application Example 7～12
According to following combined preparation white ink.Use the various base materials of these ink printings, estimate the ink performance of printing sample.
Evaluation result is as shown in table 4.
Ink combination
Ink combination prescription (except that PU-2)
Aqueous polyurethane emulsion 26.7g
Titanium white 32.0g
Water 17.3g
Virahol 4.0g
In dispersion medium, use the granulated glass sphere with the mixture same amount, in the coating vibrator, grind the mixture 2 hours of above-mentioned composition.Then, filter abrasive material,, make the assess sample of water-based printing ink then to the emulsifying water thing 8g that wherein adds ア Network ア ネ one ト 200 (ア Network ァ ネ one ト 200/ water=100/100, mass ratio).
Ink combination prescription (PU-2)
PU-2 53.3g
Titanium white 32.0g
Virahol 4.7g
In dispersion medium, use the granulated glass sphere with the mixture same amount, in the coating vibrator, grind the mixture 2 hours of above-mentioned composition.Then, filter abrasive material,, make the assess sample of water-based printing ink then to the emulsifying water thing 8g that wherein adds ア Network ァ ネ one ト 200 (ア Network ァ ネ one ト 200/ water=100/100, mass ratio).
Table 4
| Application Example | ||||||
| 7 | 8 | 9 | 10 | 11 | 12 | |
| The emulsion title | PU-1 | PU-2 | PU-3 | PU-4 | PU-5 | PU-6 |
| Dispersing of pigments stability | ○ | ○ | ○ | ○ | ○ | ○ |
| Space of a whole page anelasticity | ○ | ◎ | ○ | ○ | ○ | ○ |
| Adaptation | ◎ | ◎ | ◎ | ○ | ◎ | ◎ |
Each test method in the table 4 is as follows.
(assessment item)
Dispersing of pigments stability
With leaving standstill 48 hours after the printing ink mixing, confirm to have unpigmented precipitation etc.
Estimate zero: do not have the precipitation of pigment etc.
*: the precipitation of pigment etc. is arranged
Space of a whole page anelasticity
After the printing, use clean pin that the mixed solvent of isopropanol=1/1 (mass ratio) is sprayed (falling リ か け) on the gravure roll of simple type gravure printing machine, observe printing ink and whether wash from the gravure roll upper punch.
Estimate zero: easily be rinsed
*: when only using the mixed solvent spray, can not rinse out
Adaptation
After the printing and, after printing, leave standstill after 1 evening, on printing surface, paste the mucous membrane adhesive tape, and it torn fast.
Estimate ◎: printing film have 90%～100% residual
Zero: printing film have 70%～80% residual
△: printing film have 50%～70% residual
*: printing film has only residual below 50%
Printing condition
Printing ink: the white ink of above-mentioned preparation
Printing press: the simple type gravure printing machine that has intaglio plate
Print speed: 20m/ branch
Ink thickness: ink thickness 1 μ m (doing thick)
Printing element: corona treatment oriented polyester film (20 μ m are thick)
(polyethylene terephthalate (PET) film)
Water-based printing ink of the present invention demonstrates good especially space of a whole page anelasticity.This can think because the urethane resin of employed aqueous polyurethane emulsion has good solvability again.
Claims (5)
1. aqueous polyurethane emulsion, be to make organic multiple isocyanate (A), the compound (B) that contains reactive hydrogen, the compound (C) that contains anionic property polar group and reactive hydrogen, and urethane resin emulsification in water that neutralizing agent (D) reaction obtains obtains, it is characterized in that described organic multiple isocyanate (A) comprises and obtained by poly-(alkylidene oxide) glycol (A1-1) of the alkoxyl group that contains the above oxygen ethylidene of 50mol% in repeating unit and hexamethylene diisocyanate (A1-2), be substantially free of the allophanate-modified polyisocyanates (A1) of isocyanurate group.
2. aqueous polyurethane emulsion as claimed in claim 1, wherein, it is the macromolecule polyol (B1) more than 500 and the low molecule polyamines and/or the water (B2) of number-average molecular weight less than 500 that the compound (B) that contains reactive hydrogen comprises number-average molecular weight at least.
3. the manufacture method of an aqueous polyurethane emulsion, comprise: will be except that the compound that contains reactive hydrogen (B) low molecule polyamines and/or the water (B2), the compound (C) and the organic multiple isocyanate (A) that contain anionic property polar group and reactive hydrogen, under the condition that does not have organic solvent basically, react, use neutralizing agent (D) neutralization then, make the isocyanate end prepolymer emulsification in water that obtains like this, and carrying out transfer reaction with low molecule polyamines and/or water (B2), wherein said organic multiple isocyanate (A) comprises and is obtained by poly-(alkylidene oxide) glycol (A1-1) of the alkoxyl group that contains the above oxygen ethylidene of 50mol% in repeating unit and hexamethylene diisocyanate (A1-2), be substantially free of the allophanate-modified polyisocyanates (A1) of isocyanurate group.
4. a water-borne coatings is characterized in that comprising aqueous polyurethane emulsion as claimed in claim 1 or 2.
5. a water-based printing ink is characterized in that comprising aqueous polyurethane emulsion as claimed in claim 1 or 2.
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| JP2004198891A JP2006022133A (en) | 2004-07-06 | 2004-07-06 | Aqueous polyurethane emulsion, method for producing the same and use of the same |
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| CN101348703B (en) * | 2008-06-20 | 2012-06-06 | 中山大学 | Aqueous polyurethane adhesive and preparation thereof |
| CN102732089A (en) * | 2011-03-30 | 2012-10-17 | 佳能株式会社 | Ink jet ink, ink cartridge, and ink jet recording method |
| CN103429678A (en) * | 2011-03-30 | 2013-12-04 | 佳能株式会社 | Ink jet ink, ink cartridge, and ink jet recording method |
| CN104877447A (en) * | 2015-04-27 | 2015-09-02 | 安徽宏洋包装集团有限公司 | Anti-stripping non-staining water-based ink for paper printing |
| CN108690181A (en) * | 2017-04-05 | 2018-10-23 | 高鼎精密材料股份有限公司 | Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof |
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| JP5452794B2 (en) * | 2006-12-25 | 2014-03-26 | 日本ポリウレタン工業株式会社 | Aqueous polyurethane resin emulsion coating composition and method for producing the same |
| JP2010053238A (en) * | 2008-08-28 | 2010-03-11 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate composition and two-pack coating composition using the same |
| JP5225901B2 (en) * | 2009-03-17 | 2013-07-03 | 三井化学株式会社 | Method for producing aqueous polyurethane resin, aqueous polyurethane resin and film |
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| CN105860656B (en) * | 2016-06-17 | 2019-07-16 | 信丰鸿美油墨科技有限公司 | A kind of Environmental-protection water-based ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2209274T3 (en) * | 1998-05-22 | 2004-06-16 | Bayer Aktiengesellschaft | MIXED POLYISOCIANATE MODIFIED THROUGH AVAILABLE POLYETERS. |
| DE19822890A1 (en) * | 1998-05-22 | 1999-11-25 | Bayer Ag | New aqueous 2-component PU coating systems |
| DE19836696C2 (en) * | 1998-08-13 | 2000-06-08 | Case Harvesting Sys Gmbh | Cleaning device for a rotating cooling air filter |
| DE19958170A1 (en) * | 1999-12-02 | 2001-06-07 | Bayer Ag | Highly functional water-dispersible polyisocyanate mixtures |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101348703B (en) * | 2008-06-20 | 2012-06-06 | 中山大学 | Aqueous polyurethane adhesive and preparation thereof |
| CN102732089A (en) * | 2011-03-30 | 2012-10-17 | 佳能株式会社 | Ink jet ink, ink cartridge, and ink jet recording method |
| CN103429678A (en) * | 2011-03-30 | 2013-12-04 | 佳能株式会社 | Ink jet ink, ink cartridge, and ink jet recording method |
| CN102732089B (en) * | 2011-03-30 | 2015-02-18 | 佳能株式会社 | Ink jet ink, ink cartridge, and ink jet recording method |
| US9243155B2 (en) | 2011-03-30 | 2016-01-26 | Canon Kabushiki Kaisha | Ink jet ink, ink cartridge, and ink jet recording method |
| CN104877447A (en) * | 2015-04-27 | 2015-09-02 | 安徽宏洋包装集团有限公司 | Anti-stripping non-staining water-based ink for paper printing |
| CN108690181A (en) * | 2017-04-05 | 2018-10-23 | 高鼎精密材料股份有限公司 | Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof |
| CN112088178A (en) * | 2018-05-14 | 2020-12-15 | 大日精化工业株式会社 | Polyurethane resin aqueous dispersion, method for producing same, coating material, film forming body, and structure |
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| JP2006022133A (en) | 2006-01-26 |
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