CN1718605A - Water-based polyurethane emulsion, its mfg. method and water-based printing ink using same - Google Patents
Water-based polyurethane emulsion, its mfg. method and water-based printing ink using same Download PDFInfo
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- CN1718605A CN1718605A CNA2005100818783A CN200510081878A CN1718605A CN 1718605 A CN1718605 A CN 1718605A CN A2005100818783 A CNA2005100818783 A CN A2005100818783A CN 200510081878 A CN200510081878 A CN 200510081878A CN 1718605 A CN1718605 A CN 1718605A
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Abstract
The present invention provides an aqueous polyurethane emulsion, capable of obtaining a coated film excellent in re-dissolving property, close adhesion, etc., especially suitable for an aqueous printing ink. This aqueous polyurethane emulsion is obtained by emulsifying in water a polyurethane resin obtained by reacting (A) an organic polyisocyanate containing (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 and substantially not containing isocyanurate group, with (B) an active hydrogen-containing compound.
Description
Technical field
The present invention relates to obtain having the good aqueous polyurethane emulsion of the film of solvability and adaptation etc. again, the invention still further relates to water-based printing ink and the manufacture method thereof of using this emulsion.
Background technology
Because aqueous polyurethane emulsion has the good adaptation 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 (hereinafter to be referred 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.Therefore, when making the allophanate-modified polyisocyanates of patent documentation 1, use NMP usually.NMP has the effect of film coalescence aid when film forms, and has the advantage that reduces viscosity etc. when making emulsion, on the other hand, also exists to cause in time and painted or precipitation or sometimes because the different emulsions of its content have the shortcoming of point of ignition etc.And, owing to NMP mixes with water with arbitrary proportion, and higher boiling point is arranged, thereby it removes difficulty than glassware for drinking water.
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 the prepolymer of isocyanate end 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
Aqueous polyurethane emulsion, its manufacture method of the film that the object of the present invention is to provide and to obtain having well again solvability, adaptation, the space of a whole page is detained (version is closely questioned ま リ) property etc. and the water-based printing ink that uses this emulsion.
For achieving the above object, of the present invention theing contents are as follows stated shown in (1)～(4).
(1) aqueous polyurethane emulsion, it is characterized in that, described aqueous polyurethane emulsion is to obtain by making by organic multiple isocyanate (A) and urethane resin emulsification in water that compound (B) reaction that contains reactive hydrogen obtains, and described organic multiple isocyanate (A) comprises by poly-(alkylidene oxide) glycol (A1-1) of the alkoxyl group that contains the above oxygen ethylidene of 50mol% in repeating unit and obtain and the allophanate-modified polyisocyanates that be substantially free of isocyanurate group (A1) of hexamethylene diisocyanate (A1-2).
(2) above-mentioned (1) described aqueous polyurethane emulsion, the compound (B) that wherein contains reactive hydrogen comprises the low molecule polyamines and/or the water (B2) of polyvalent alcohol (B1) and 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 react under the condition that does not have organic solvent basically with organic multiple isocyanate (A) except that the low molecule polyamines and/or the compound that contains reactive hydrogen (B) the water (B2) of number-average molecular weight less than 500, make the emulsification in water of resulting isocyanate end prepolymer then, carry out transfer reaction with low molecule polyamines and/or water (B2), and described 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), and be substantially free of the allophanate-modified polyisocyanates (A1) of isocyanurate group.
(4) a kind of water-based printing ink is characterized in that comprising the aqueous polyurethane emulsion of above-mentioned (1) or (2).
Owing to use the allophanate-modified body in the isocyanate prepolymer composition of urethane resin, be substantially free of the isocyanuric acid 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 (being designated hereinafter simply 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, space of a whole page anelasticity 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) can be obtained with HDI (A1-2) by poly-(alkylidene oxide) glycol (A1-1) of the alkoxyl group that contains the above oxygen ethylidene of 50mol% in repeating unit.Wherein, when the not enough 50mol% of oxygen ethylidene 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 allophanate-modified polyisocyanates (A1) is preferably 3～15 quality %, is preferably 5～13 quality % especially.And, be preferably below the 2000mPas 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 it is insufficient that the dispersive ability of resulting urethane resin becomes 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 allophanic acid esterification catalyzer except these, the degree that side reactions such as isocyanuric acid esterification reaction take 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 easy 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, comprise 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, realize hydrophilic effect, preferably have the Fatty Alcohol(C12-C14 and C12-C18) of 5 following carbon atoms, 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 low 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 comprise 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 low molecule polyamines and/or water (B2) that the compound (B) that contains reactive hydrogen of the present invention preferably comprises polyvalent alcohol (B1) and number-average molecular weight less than 500 at least.Polyvalent alcohol (B1) is macromolecule polyol and/or low molecular polylol, and the preferred mixed pure and mild low molecular polylol of macromolecular multi-component that uses.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 with thermotolerance and intensity effect, and can reduce the viscosity in the reaction process.
The number-average molecular weight of macromolecule polyol is more than 500, preferred 1000～5000.And the average functional group number of this macromolecule polyol 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 is tried to achieve.
As macromolecule polyol, 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 is a polyester polyol among the present invention, and when paying attention to water tolerance, preferred macromolecule polyol 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 of above-mentioned synthesis material 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 that to enumerate Viscotrol C be polyvalent alcohol, silk fibroin etc. to polyvalent alcohol.
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.
The number-average molecular weight less than 500 of low molecular polylol is considered the physical properties of resulting urethane resin film etc., the concrete suitable low molecular polylol of enumerating the above-mentioned polyester polyol of formation.
As (B2), enumerate the low molecule polyamines of number-average molecular weight less than 500 and water and composition thereof.
Low molecule polyamines as number-average molecular weight less than 500 comprises hydrazine, 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.In the present invention, if consider the physical properties of resulting urethane resin film or weather resistance etc., preferably water, hydrazine, quadrol, hexamethylene-diamine or isophorone diamine.
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, NSC 87419 etc. as reaction terminating agent.
The concrete unary alcohol that can be used as reaction terminating agent is enumerated methyl alcohol, ethanol, propyl alcohol, Virahol, 2-Ethylhexyl Alcohol etc.Enumerate primary amine such as ethamine, propylamine, butylamine as the monobasic amine, 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) and the compound (B) that contains reactive hydrogen react the synthesis of polyurethane resin under the condition of reactive hydrogen surplus, 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 (B2) react the prepolymer of synthesizing isocyanate cardinal extremity base under the atmosphere of isocyanate group surplus, this prepolymer is dispersed in the water, uses low molecule polyamines and/or water (B2) to carry out the prepolymer method of transfer reaction then.
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,, 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,,,, obtain the target product aqueous polyurethane emulsion to carry out the amine reaction of propagation by adding low molecule polyamines and/or water (B2) and adding reaction terminating agent as required by adding the water-dispersion prepolymer.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, 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 200nm, below preferred 50～150nm.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 50～1000mPas.Prescribe a time limit above last when viscosity, it is difficult that printing inkization afterwards easily becomes.
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 urethane 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 printing ink 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 or organic filler, softening agent, lubricant, antistatic agent, toughener, catalyzer etc.
In addition, in aqueous solution polyaminoester emulsion of the present invention, can also use with the form of the emulsion of mixing other resenes.Enumerate 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 basically carbamate groups, isocyanuric acid ester group, 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
Add 200gNMP, 265.6g 2 in the volume that has agitator, thermometer, water cooler and nitrogen conduit is the reactor of 1L, 4-TDI, 534.5gMPEG-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 basically carbamate groups, and confirms to exist allophanate group and isocyanuric acid ester group.
In synthesis example 1～3:
HDI: hexamethylene 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 128.6g polyvalent alcohol-1,8.0g NPG in the reactor of 1L, mixes under 100 ℃.Then, add 165.6g ALP-1,0.05g DOTDL, reaction is 3 hours under 80 ℃ of temperature, obtains the prepolymer of isocyanate end.The isocyanate content of this prepolymer is 2.32%, and the viscosity under 75 ℃ of temperature is 1150mPas.Then, add 702g water and make its emulsification, under 40 ℃, make water carry out transfer reaction then.Termination reaction when confirming not have isocyanate group by FT-IR obtains aqueous polyurethane emulsion PU-1.
The solid component concentration of PU-1 is 30.1%, and the viscosity under 25 ℃ of temperature is 40mPas, and the pH value is 7, and median size is 130nm.
Embodiment 2,3
In embodiment 1, except polyvalent alcohol-1 is replaced to the polyvalent alcohol-2,3, the step according to identical with embodiment 1 obtains aqueous polyurethane emulsion PU-2,3.
Embodiment 4
At the volume that has agitator, thermometer, water cooler and nitrogen-sealed pipe is to add 118.2g polyvalent alcohol-1,9.2g NPG in the reactor of 1L, mixes under 100 ℃ of temperature.Then, add 171.5g ALP-2,0.05g DOTDL, reaction is 3 hours under 80 ℃ of temperature, obtains the prepolymer of isocyanate end.The isocyanate content of this prepolymer is 0.50%, and the viscosity under 75 ℃ of temperature is 3750mPas.Then, add 600g emulsifying water prepolymer, after the emulsification, the ammoniacal liquor that is pre-mixed 100g water, 1.0g EDA, 0.1gMEA by adding carries out transfer reaction.Termination reaction when confirming not have isocyanate group by FT-IR obtains aqueous polyurethane emulsion PU-4.
The solids component of PU-4 is 29.9%, and the viscosity under 25 ℃ of temperature is 720mPas, and the pH value is 10, and median size is 91nm.
Embodiment 5
At the volume that has agitator, thermometer, water cooler and nitrogen-sealed pipe is to add 124.9g polyvalent alcohol-1,9.7g NPG in the reactor of 1L, mixes under 100 ℃ of temperature.Then, add 161.7g ALP-2,5.2g HDI, 0.05g DOTDL, reaction is 3 hours under 80 ℃ of temperature, obtains the prepolymer of isocyanate end.The isocyanate content of this prepolymer is 0.87%, and the viscosity under 75 ℃ of temperature is 4250mPas.Then, add 701g emulsifying water prepolymer, 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-5.
The solids component of PU-5 is 30.0%, and the viscosity under 25 ℃ of temperature is 850mPas, and the pH value is 7, and median size is 181nm.
Comparative example 1
In the volume that has agitator, thermometer, water cooler and nitrogen-sealed pipe is the reactor of 1L, add 64.2g NMP, 126.0g polyvalent alcohol-1,7.9g NPG, under 100 ℃ of temperature, mix.Then, add 165.0g ALP-3,0.05g DOTDL, reaction is 3 hours under 80 ℃ of temperature, obtains the prepolymer of isocyanate end.The isocyanate content of this prepolymer is 0.53%, and the viscosity under 75 ℃ of temperature is 950mPas.Then, add 500g emulsifying water prepolymer, all homodisperse.
Table 1
| Embodiment | Comparative example | |||||
| 1 | 2 | 3 | 4 | 5 | 1 | |
| Macromolecule polyol (g) polyvalent alcohol-1 polyvalent alcohol-2 polyvalent alcohol-3 | 128.6 | 128.6 | 128.6 | 118.2 | 124.9 | 126.0 |
| Low molecular polylol (g) NPG | 8.0 | 8.0 | 8.0 | 9.2 | 9.7 | 7.9 |
| Organic multiple isocyanate (g) ALP-1 ALP-2 ALP-3 HDI | 165.6 | 165.6 | 165.6 | 171.5 | 161.7 5.2 | 165.0 |
| Organic solvent (g) NMP | 64.2 | |||||
| Urethane catalyzer (g) DOTDL | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| Viscosity (mPas) under 75 ℃ of the prepolymer isocyanate contents (%) | 3.32 1150 | 3.32 1350 | 3.32 1050 | 0.50 3750 | 0.87 4250 | 0.53 950 |
| Dispersion medium (g) water | 702 | 702 | 702 | 600 | 701 | 500 |
| Amine aqueous solution (g) EDA MEA water | 1.0 0.1 100 | |||||
| The emulsion title | PU-1 | PU-2 | PU-3 | PU-4 | PU-5 | PU-6 |
| Nian degree (mPas) the pH Zhi average grain diameter (nm) that analysis result outward appearance solid constituent (%) is 25 ℃ | Milky white liquid 30.1 40 7 130 | Milky white liquid 30.0 370 7 120 | Milky white liquid 29.8 410 7 135 | Milky white liquid 29.9 720 10 91 | Milky white liquid 30.0 850 7 181 | - - - - - |
In embodiment 1～5, comparative example 1 and table 1
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
NPG: neopentyl glycol
DOTDL: two lauric acid dioctyl tins
EDA: quadrol
MEA: monoethanolamine
The median size determinator:
Otsuka Electronics Co., Ltd. makes, and electrophoretic light scattering is ELS-800
In embodiment 1～5, 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.Can think this be 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 printing ink test
Application Example 1～5
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 2.
(ink combination)
The ink combination prescription
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 ァ ネ one ト 200 (ア Network ァ ネ one ト (registered trademark) 200/ water=100/100, mass ratio).
※ ア Network ァ ネ one ト 200: self-emulsifying type polyisocyanates (Japanese polyurethane industry is made)
Table 2
| Application Example | |||||
| 1 | 2 | 3 | 4 | 5 | |
| Aqueous polyurethane emulsion | PU-1 | PU-2 | PU-3 | PU-4 | PU-5 |
| Dispersing of pigments stability | ○ | ○ | ○ | ○ | ○ |
| Space of a whole page anelasticity | ○ | ○ | ○ | ○ | △ |
| Adaptation | ◎ | ◎ | ○ | ○ | ○ |
Each test method in the table 2 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
Whether after the printing, the pin of use washes clean sprays (falling リ か け) on the gravure roll of simple type gravure printing machine with the mixed solvent of isopropanol=1/1 (mass ratio), observe printing ink and 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 employed urethane resin has good solvability again.
Claims (4)
1. aqueous polyurethane emulsion, be by organic multiple isocyanate (A) and urethane resin emulsification in water that compound (B) reaction that contains reactive hydrogen obtains are obtained, it is characterized in that described organic multiple isocyanate (A) comprises 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) allophanate-modified polyisocyanates that obtain, that be substantially free of isocyanurate group (A1).
2. aqueous polyurethane emulsion as claimed in claim 1, the compound (B) that wherein contains reactive hydrogen comprises the low molecule polyamines and/or the water (B2) of polyvalent alcohol (B1) and number-average molecular weight less than 500 at least.
3. the manufacture method of an aqueous polyurethane emulsion, comprise: will react under the condition that does not have organic solvent basically with organic multiple isocyanate (A) except that the low molecule polyamines and/or the compound that contains reactive hydrogen (B) the water (B2) of number-average molecular weight less than 500, 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-based printing ink is characterized in that comprising aqueous polyurethane emulsion as claimed in claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004198884A JP2006022132A (en) | 2004-07-06 | 2004-07-06 | Aqueous polyurethane emulsion, method for producing the same and aqueous printing ink by using the same |
| JP2004198884 | 2004-07-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1718605A true CN1718605A (en) | 2006-01-11 |
| CN100580000C CN100580000C (en) | 2010-01-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200510081878A Expired - Fee Related CN100580000C (en) | 2004-07-06 | 2005-07-06 | Water-based polyurethane emulsion, its manufacturing method and water-based printing ink using same |
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| JP (1) | JP2006022132A (en) |
| CN (1) | CN100580000C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260366A (en) * | 2010-05-29 | 2011-11-30 | 比亚迪股份有限公司 | Water-soluble polyurethane and preparation method thereof, and water-soluble ink composition containing water-soluble polyurethane and preparation method thereof |
| 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 |
| CN109575219A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of waterborne epoxy modified water-based polyurethane ink link stuff and preparation method thereof |
| CN115667339A (en) * | 2020-06-10 | 2023-01-31 | 爱克发有限公司 | Aqueous polyurethane resin dispersion |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5587282B2 (en) | 2010-12-16 | 2014-09-10 | キヤノン株式会社 | Ink jet ink, ink cartridge, and ink jet recording method |
| JP2016166259A (en) * | 2015-03-09 | 2016-09-15 | 三洋化成工業株式会社 | Binder for printing ink and printing ink using the same |
| JP6733198B2 (en) | 2016-02-09 | 2020-07-29 | セイコーエプソン株式会社 | INKJET INK, INK CARTRIDGE, AND INKJET RECORDING METHOD |
| CN105925054B (en) * | 2016-05-17 | 2018-12-04 | 河南工程学院 | A kind of high-wearing feature water-based polyurethane ink binder and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2314513C3 (en) * | 1973-03-23 | 1980-08-28 | Bayer Ag, 5090 Leverkusen | Process for the preparation of aqueous polyurethane dispersions |
| JPH10265539A (en) * | 1997-03-25 | 1998-10-06 | Toyo Ink Mfg Co Ltd | Water-based urethane resin dispersion |
| DE19731864A1 (en) * | 1997-07-24 | 1999-01-28 | Bayer Ag | Aqueous PU dispersions with improved properties |
| DE19822890A1 (en) * | 1998-05-22 | 1999-11-25 | Bayer Ag | New aqueous 2-component PU coating systems |
| ES2209274T3 (en) * | 1998-05-22 | 2004-06-16 | Bayer Aktiengesellschaft | MIXED POLYISOCIANATE MODIFIED THROUGH AVAILABLE POLYETERS. |
| JP4379906B2 (en) * | 2003-03-25 | 2009-12-09 | 日本ポリウレタン工業株式会社 | Aqueous one-component coating agent and coating method using the same |
-
2004
- 2004-07-06 JP JP2004198884A patent/JP2006022132A/en active Pending
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2005
- 2005-07-06 CN CN200510081878A patent/CN100580000C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260366A (en) * | 2010-05-29 | 2011-11-30 | 比亚迪股份有限公司 | Water-soluble polyurethane and preparation method thereof, and water-soluble ink composition containing water-soluble polyurethane and preparation method thereof |
| 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 |
| CN109575219A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of waterborne epoxy modified water-based polyurethane ink link stuff and preparation method thereof |
| CN109575219B (en) * | 2017-09-28 | 2021-09-03 | 中国石油化工股份有限公司 | Waterborne epoxy modified waterborne polyurethane ink binder and preparation method thereof |
| CN115667339A (en) * | 2020-06-10 | 2023-01-31 | 爱克发有限公司 | Aqueous polyurethane resin dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100580000C (en) | 2010-01-13 |
| JP2006022132A (en) | 2006-01-26 |
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