CN1590429A - Polyurethane resin,water polyurethane resin,hydrophilic modifier,moisture resin and process for producing polyurethaneresin - Google Patents
Polyurethane resin,water polyurethane resin,hydrophilic modifier,moisture resin and process for producing polyurethaneresin Download PDFInfo
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- CN1590429A CN1590429A CN 200410070267 CN200410070267A CN1590429A CN 1590429 A CN1590429 A CN 1590429A CN 200410070267 CN200410070267 CN 200410070267 CN 200410070267 A CN200410070267 A CN 200410070267A CN 1590429 A CN1590429 A CN 1590429A
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Abstract
The present invention provides a polyurethane resin, aqueous polyurethane resin, aqueous modifier, moisture permeating resin and a method for making the polyure thane resin. To provide an aqueous polyurethane resin which can endow excellent hydrophilicity to the aqueous resin because of excellent compatibility and water swellability in the formed film, or the aqueous polyurethane resin composed of polyurethane resin and the hydrophilic modifier comprising the aqueous polyurethane resin, a moisture permeating resin comprising the polyurethane resin, and a method for preparing the polyurethane resin, in the invention at least the polyurethane prepolymer comprising anionic group is reacted with the polyamine containing polyoxyethylene group to obtain polyurethane resin. The polyurethane resin is dispersed and/or dissolved into the water and the aqueous polyurethane resin is obtained, and the moisture permeating resin can be obtained by assorting the aqueous modifier composed of the aqueous polyurethane resin in the aqueous resin.
Description
Technical field
The invention relates to urethane resin, waterborne polyurethane resin, hydrophilic modifier, the manufacture method of water vapour permeability resin and this urethane resin, in more detail, be about being fit to be engaged in the various water-base resins, be used for water-permeable, water vapour permeability, water-retentivity, water-swellable, the wetting ability of static resistance etc. is carried out the urethane resin of modification, the perhaps waterborne polyurethane resin that constitutes by this urethane resin, and comprise the hydrophilic modifier of this waterborne polyurethane resin, and the water vapour permeability resin that comprises these urethane resins, the manufacture method of this urethane resin in addition.
Background technology
Up to now, water swellable polymer also is called water-absorbing polymer, utilize wetting ability that polymkeric substance self has and cross-linked network and keep high water-retentivity, use separately or and other resin and usefulness, in requiring water-permeable or water vapour permeability and water-retentivity, water-swellable, static resistance etc., hydrophilic various fields or purposes, use.
In addition, in recent years, consider the toxicity of organic solvent and to atmospheric contaminative, wish to lower the use of organic solvent, people are studying in various resin purposes, are that resin changes to the water-base resin that makes water as dispersion solvent from the organic solvent as solvent with an organic solvent how.
Therefore, just require in water-base resin, can easily cooperate and can give the water-swellable polymer of high-hydrophilic.
In general, import wetting ability base, particularly polyoxyethylene groups therein in order to show high-hydrophilic be known to water-swellable polymer.In water-swellable polymer,, just can improve wetting ability if improve polyoxyethylene groups content, but then, if polyoxyethylene groups content is too high and the affinity of water is just strong excessively, gelation then takes place, or makes the water-base resin that finally obtains become unstable.
In addition, in order to keep water-soluble physical strength when bloated, it is crosslinked preferentially to select it wherein to comprise, but in case comprise crosslinkedly, hinders water-swellable on the contrary, consequently generation intermiscibility bad when cooperating with water-base resin.
For example, open the aqueous dispersions that has proposed to comprise the cross-linked polyurethane particle that contains polyoxyethylated polyamines and water-dispersible polyisocyanates in the flat 11-228808 communique the spy.
In addition, though the fiber of moisture-permeability waterproof in the past processing is to obtain by solution, drying that coating urethane resin on fabrics such as nylon is dissolved in the mixture of water and organic solvent, a large amount of polar organic solvent that uses for the dissolve polyurethane resin need be removed in aftertreatment.
For example, in the public clear 60-47954 communique of spy,, dimethyl formamide, methyl-sulphoxide, tetrahydrofuran (THF) etc. have been enumerated as polar organic solvent.
, open the aqueous dispersions of putting down in writing in the flat 11-228808 communique the spy, stability is bad, in addition, even be engaged in the water-base resin, it is bad also to produce intermiscibility, even film forming also can not get the uniform overlay film of wetting ability, consequently can not give wetting ability in fact.
In addition, the moisture-permeability waterproof processing method of putting down in writing in the special public clear 60-47954 communique is used a large amount of polar organic solvents, from toxicity, topsoil, energy efficiency consideration, is worthless.
Summary of the invention
The object of the present invention is to provide, have water miscible, can give water-base resin good hydrophilic urethane resin with the good water-swellable after its good intermiscibility and the film forming, the perhaps waterborne polyurethane resin that constitutes by this urethane resin, and comprise the hydrophilic modifier of this waterborne polyurethane resin, and the water vapour permeability resin that comprises these urethane resins, the manufacture method of this urethane resin in addition.
Urethane resin of the present invention is a feature to make the polyurethane prepolymer with anionic property base react and obtain with the polyamines that contains polyoxyethylene groups at least.
In addition, urethane resin of the present invention is in polyurethane prepolymer, and it is suitable that every 100g polyurethane prepolymer contains 5～200 millinormal above-mentioned anionic property bases.
In addition, in urethane resin of the present invention, above-mentioned polyurethane prepolymer contains polymeric polyisocyanate and polyoxyalkylene polyol is suitable as raw material.
In addition, in urethane resin of the present invention, the polyoxyethylene groups content in the above-mentioned polyurethane prepolymer is for being suitable more than or equal to 40 weight %.
In addition, in urethane resin of the present invention, the polyoxyethylene groups content in the above-mentioned urethane resin is for being suitable more than or equal to 40 weight %.
In addition, urethane resin of the present invention further with contain primary amine or have primary amine groups and the polyglycidyl compounds of secondary amine better.
In addition, to disperse and/or be dissolved in the water with above-mentioned urethane resin be feature to waterborne polyurethane resin of the present invention.
Hydrophilic modifier of the present invention is a feature to contain above-mentioned urethane resin.
In addition, water vapour permeability resin of the present invention is a feature to contain above-mentioned hydrophilic modifier and water-base resin.
In addition, in the water vapour permeability resin of the present invention, above-mentioned water-base resin is a polyaminoester emulsion, above-mentioned polyaminoester emulsion, contain macromole (マ Network ロ) polyvalent alcohol as raw material, macromolecular polyol is that the carbonatoms from polyester polyol, polycarbonate polyol and alkyl is select the group formed of 3～10 polyoxyalkylene polyol at least a, the total amount of the urethane raw of polyaminoester emulsion relatively, and it is suitable containing more than or equal to 50 weight % macromolecular polyols.
The manufacture method of urethane resin of the present invention is a feature so that the polyurethane prepolymer with anionic property base is reacted with the polyamines that contains polyoxyethylene groups.
Urethane resin of the present invention, waterborne polyurethane resin and hydrophilic modifier have the good water-swellable after good intermiscibility and the film forming, and it can also give good wetting ability to water-base resin.Therefore, contain the water vapour permeability resin of the present invention of hydrophilic modifier of the present invention and water-base resin, be coated on the base fabric, on base fabric, form film, can realize moisture-permeability waterproof processing with moisture-permeability waterproof by curtain coating.Therefore can be effectively used to dress material purposes etc.
Embodiment
Urethane resin of the present invention can obtain by the polyurethane prepolymer with anionic property base is reacted with the polyamines that contains polyoxyethylene groups.
In the present invention, polyurethane prepolymer with anionic property base, for example be the polyurethane prepolymer that on molecular side chain, has the anionic property base, has the free isocyanate group in molecular end, by polymeric polyisocyanate and polyvalent alcohol and the compound that contains active hydrogen base with anionic property base react and just can access.
Polymeric polyisocyanate is optional to be used in normally used polymeric polyisocyanate in the manufacturing of urethane resin, and have no particular limits, for example can enumerate the derivative of aromatic diisocyanate, aromatic-aliphatic vulcabond, aliphatic diisocyanate, alicyclic diisocyanate and these vulcabond or modifier etc.
As aromatic diisocyanate, for example can enumerate m-benzene diisocyanate, PPDI, 4,4 '-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4-or 2,6-tolylene diisocyanate, 4,4 '-Tolylamine vulcabond, 4,4 '-the phenyl ether vulcabond etc.
As the aromatic-aliphatic vulcabond, for example can enumerate 1,3-or 1,4-Xylene Diisocyanate or its mixture etc.
As aliphatic diisocyanate, for example can enumerate trimethylene vulcabond, tetramethylene vulcabond, HDI, penta-methylene vulcabond, 1,2-trimethylene diisocyanate, 1,2-butylidene vulcabond, 2,3-butylidene vulcabond, 1,3-butylidene vulcabond, 2,4,4-or 2,2,4-trimethyl-hexamethylene diisocyanate, 2,6-vulcabond caproic acid methyl etc.
As alicyclic diisocyanate, for example can enumerate 1,3-cyclopentenes vulcabond, 1, the 4-cyclohexyl diisocyanate, 1, the 3-cyclohexyl diisocyanate, 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (different phorone vulcabond), 4,4 '-methylene-bis (two NSC 87419), methyl-2, the 4-cyclohexyl diisocyanate, methyl-2, the 6-cyclohexyl diisocyanate, 1, two (isocyanato-methyl) hexanaphthenes of 4-, 1, two (isocyanato-methyl) hexanaphthenes of 3-, 2,5 (2,6)-two (isocyanato-methyl) dicyclos [2.2.1] heptane etc.
In addition, as the derivative of polymeric polyisocyanate, for example can enumerate dipolymer, trimer, biuret, allophanate, carbodiimide, urea diketone (ウ レ ッ ト ジ オ Application), oxadiazine triketone, polymethylene polyphenyl base polymeric polyisocyanate (Network Le-De MDI, Port リ メ リ ッ Network MDI) and the Network Le-De TDI etc. of above-mentioned polymeric polyisocyanate.
Have again, modifier as polymeric polyisocyanate, for example make the derivative and the polyvalent alcohol (aftermentioned) of above-mentioned polymeric polyisocyanate or polymeric polyisocyanate, under the condition of the equivalence ratio hydroxyl groups surplus of the isocyanate group of polymeric polyisocyanate, react and the polyalcohol modified thing that obtains.
These polymeric polyisocyanates can use separately or will also use more than 2 kinds or 2 kinds.In addition, among these polymeric polyisocyanates, from with the viewpoint of the weathering resistance of the side reaction of water or resin, aliphatic diisocyanates such as preferential use HDI, 1, two (isocyanato-methyl) hexanaphthenes, 4,4 of 3-'-methylene-bis alicyclic diisocyanates such as (NSC 87419).
Polyvalent alcohol just has no particular limits if normally used in the manufacturing of urethane resin, but preferentially uses polyoxyalkylene polyol.
As polyoxyalkylene polyol, can enumerate the segmented copolymer or the random copolymers that obtain as the addition reaction of the oxyethane of initiator by with low molecular weight polyols.
As low molecular weight polyols, for example can enumerate ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, 1, the 2-butyleneglycol, 1, the 6-hexylene glycol, neopentyl glycol, alkane (carbonatoms 7～22) glycol, glycol ether, triglycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-glycol (carbonatoms 17～20), Hydrogenated Bisphenol A, 1,4-dihydroxyl-2-butylene, 2,6-dimethyl-1-octene-3,8-glycol, the dihydroxyl phenetole, dimethylbenzene ethylene glycol (xyleneglycol), low molecular weight diols such as the two hydroxyl glycol esters of terephthalic acid, glycerine for example, 2-methyl-2-methylol-1, ammediol, 2,4-dihydroxyl-3-methylol pentane, 1,2, the 6-hexanetriol, 1,1,1-three (methylol) propane, 2, lower molecular weight triols such as two (the methylol)-3-butanols of 2-etc.
As epoxide, for example can enumerate oxyethane, propylene oxide etc.
These polyoxyalkylene polyols can use separately, also can will also use more than 2 kinds or 2 kinds.The preferential high polyoxyalkylene polyol of polyoxyethylene groups content that uses specifically, for example preferentially uses the polyoxyethylene glycol of number-average molecular weight 500～3000.
In addition, in the scope that does not hinder chain lengthening reaction described later, also can use masked polyoxyalkylene one alcohol of a part that makes hydroxyl by monohydroxy-alcohols such as methyl alcohol or butanols.
Have again,, can use polyoxyalkylene polyol high molecular weight polyols or low molecular weight polyols in addition as polyvalent alcohol.Such polyvalent alcohol as high molecular weight polyols, for example can be enumerated the macromolecular polyol of polyester polyol, polycaprolactone polyol, polycarbonate polyol etc., the polyvalent alcohol of the preferential number-average molecular weight of selecting enumerated 500～4000.In addition, as low molecular weight polyols, for example can enumerate ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,2-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, alkane (carbonatoms 7～22) glycol, glycol ether, triglycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-glycol (carbonatoms 17～20), Hydrogenated Bisphenol A, 1,4-dihydroxyl-2-butylene, 2,6-dimethyl-1-octene-3,8-glycol, dihydroxyl phenetole, dimethylbenzene ethylene glycol (xyleneglycol), the two hydroxyl glycol esters of terephthalic acid etc.
In addition; what have the anionic property base contains the active hydrogen based compound; for example be to have an anionic property base that betaine structures such as carboxyl, alkylsulfonyl, phosphate, sultaine contain base etc., and and the isocyanic ester radical reaction obtain, for example contain the compound of hydroxyl, amino isoreactivity hydrogen base.
Contain the active hydrogen based compound as what have such anionic property base, have no particular limits, for example can enumerate and have 1 anionic property base and have compound more than or equal to 2 active hydrogen bases.More specifically, contain the active hydrogen based compound as what have a carboxyl, for example can enumerate 2,2-dihydroxymethyl acetate, 2,2-dihydroxymethyl lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolpropionic acid, 2, diamino monocarboxylic acids such as dihydroxy carboxylic acids, for example Methionin, arginine such as 2-dihydroxymethyl valeric acid etc.
Contain the active hydrogen based compound as what have an alkylsulfonyl, for example can enumerate N, two (2-the hydroxyethyl)-2-aminoethane sulfonic acids, 1 of N-; 3-phenylenediamine-4; 6-disulfonic acid, diamino butyl sulfonic acid, 3,6-diamino-2-toluenesulphonic acids, 2,4-diamino-5-toluenesulphonic acids etc.
Contain the active hydrogen based compound as what have a phosphate, for example can enumerate 2,3-dihydroxyl propyl phenyl phosphoric acid ester etc.
Contain the active hydrogen based compound as what have that betaine structure contains base, for example can enumerate tertiary amines and 1 such as N methyldiethanol amine, the reaction of 3-third sultone and obtain contain sultaine based compound etc.
Have again, also can enumerate and have the containing in the active hydrogen based compound of these anionic property bases, make oxiranes such as oxyethane or propylene oxide carry out addition reaction and the oxirane modifier that obtains.
What these had an anionic property base contains the active hydrogen based compound, can use separately, and also can more than 2 kinds or 2 kinds and use.In addition, these have containing among the active hydrogen based compound of anionic property base, preferential select contain the active hydrogen based compound as what have a carboxyl.
In addition, contain the active hydrogen based compound for what have an anionic property base, though have no particular limits, the anionic property base, preferably cooperates with 10～100 millinormal ratios preferably with 5～200 milligramequivalents with respect to every 100g polyurethane prepolymer.By making anionic property base content in every 100g polyurethane prepolymer, when the water-dispersion of polyurethane prepolymer, can improve stability more than or equal to 5 milligramequivalents.In addition, be less than or equal to 20 milligramequivalents, can realize more economical manufacturing, and water-retentivity is remained in the suitable scope by making the anionic property base content in every 100g polyurethane prepolymer.
So, adjust polymeric polyisocyanate, polyvalent alcohol and have the proportioning that contains the active hydrogen based compound of anionic property base, the isocyanate group that makes polymeric polyisocyanate with respect to polyvalent alcohol and the equivalence ratio that contains the active hydrogen based compound (NCO/ active hydrogen base) with anionic property base for surpassing 1, being preferably 1.1～20, like this, for example adopt known reaction methods such as mass polymerization or solution polymerization, just can access polyurethane prepolymer.
In addition, in this reaction,, preferentially each composition is cooperated though have no particular limits, so that in the polyurethane prepolymer that obtains, polyoxyethylene groups content for more than or equal to 40 weight % so that be 45～95 weight %, be in particular 50～90 weight %.If the polyoxyethylene groups content in the polyurethane prepolymer reaches more than or equal to 40 weight %, compare than less than 40 weight % the time, can access high water swelling ratio, that is, can give higher wetting ability.Therefore, at the higher water swelling ratio of needs, when wetting ability is given performance, the polyoxyethylene groups content in the polyurethane prepolymer is reached more than or equal to 40 weight %.
In the mass polymerization, for example under nitrogen gas stream, stir polymeric polyisocyanate, contain the active hydrogen based compound, under 75～85 ℃ of temperature of reaction, carry out the reaction about 1 to a few hours to what wherein add polyvalent alcohol and have an anionic property base.
In the solution polymerization, for example under nitrogen gas stream, stir polymeric polyisocyanate in reaction solvent, contain the active hydrogen based compound to what wherein add polyvalent alcohol and have an anionic property base, the boiling point of being less than or equal to reaction solvent in temperature of reaction carries out reacting about 1 to a few hours.As reaction solvent, what use is as inert and be imbued with low boiling point solvent hydrophilic, easy removal to isocyanate group and active hydrogen base, as such reaction solvent, for example can enumerate acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran (THF), acetonitrile etc.
Moreover, in this reaction, as required, can add catalysts, and, use as known means such as distillation or extraction, also can from reaction system, remove the monomer of unreacted polymeric polyisocyanate.
In addition, in this reaction, before prepolymer reaction, react after, perhaps after chain lengthening reaction described later, preferential selection is added for example from amines such as Trimethylamine 99, triethylamine, Tri-n-Propylamine, Tributylamine, trolamines, for example inorganic salt such as potassium hydroxide, sodium hydroxide also have the middle neutralizing agents of selecting such as ammoniacal liquor, and form the salt of anionic property base.The addition of neutralizing agent, for example per 1 equivalent anionic property base is 0.4～1.2 equivalent, and then is more preferably 0.6～1.0 equivalent.And, after prepolymer being disperseed and/or be dissolved in the water, when carrying out chain lengthening reaction described later,, be preferably in before water-dispersion and/or dissolving in order to improve the stability of the prepolymer in the water, make it to form the salt of anionic property base.
Therefore, urethane resin of the present invention can use the polyamines that contains polyoxyethylene groups as the chain lengthening agent, makes it to react with the polyurethane prepolymer with the anionic property base that obtains like this, obtains by chain lengthening.
The polyamines that contains polyoxyethylene groups for example preferentially uses polyoxyethylene ether diamine with following structural formula (1) expression, with the polyoxyalkylene ether diamine of following structural formula (2) expression, with the polyoxyethylene ether diamine of following structural formula (3) expression, with the polyamines of following structural formula (4) expression.The number-average molecular weight of these polyoxyethylene ether diamines or polyoxyalkylene ether diamine for example is the scope 100～2000, is more preferably the scope 140～10000.Can enumerate ジ ェ Off ア ミ Application ED-2003 (being equivalent to structural formula (2)), EDR-148 (being equivalent to structural formula (3)) as greasy PEG#1000 diamines of Japan (being equivalent to structural formula (1)) or Ha Application Star マ Application company, XTJ-512 (being equivalent to structural formula (4)) etc. particularly.
H
2NCH
2CH
2CH
2O(CH
2CH
2O)
nCH
2CH
2CH
2NH
2
.....(1)
(in the formula, n represents the polymerization degree.)
(in the formula, n, m, l represent the polymerization degree.)
H
2N(CH
2CH
2O)
nCH
2CH
2NH
2????.....(3)
(in the formula, n represents the polymerization degree.)
H
2N[(CH
2CH
2O)
nCH
2CH
2NH]
mH???????????.....(4)
(in the formula, m, n represent the polymerization degree.)
In addition, in such reaction, as the chain lengthening agent, for example can and with primary amine or have primary amine groups and the polyglycidyl compounds of secondary amine.Such polyglycidyl compounds, can enumerate particularly: γ-An Bingjisanyiyangjiguiwan, N-phenyl-γ-An Bingjisanjiayangjiguiwan etc. contains an amine of alkoxysilyl, and N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl) γ-aminopropyl methyl dimethoxysilane etc. contain alkoxysilyl two amines.For and the urethane resin that obtains with polyglycidyl compounds, can intramolecularly have can be crosslinked the functional group, use the resin of this urethane resin, can make the molecule quantitative change big by crosslinked.Therefore,, just can access the urethane resin of any molecular weight, can freely control water-soluble and water-swellable by the usage quantity of control polyglycidyl compounds.
Except the above-mentioned polyamines and polyglycidyl compounds that contain polyoxyethylene groups, as the chain lengthening agent, can also and with other amine.As such amine, can enumerate for example ethamine, butylamine, Isopropylamine, one amine such as dibutylamine, quadrol for example, 1, the 3-propylene diamine, 1, the 4-butanediamine, 1, the 6-hexanediamine, 1, the 4-cyclohexanediamine, 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (different phorone diamines), 4,4 '-the dicyclohexyl methyl hydride diamines, 2,5 (2,6)-two (aminomethyl) dicyclo [2.2.1] heptane, 1, two (aminomethyl) hexanaphthenes of 3-, two amines such as hydrazine, Diethylenetriamine for example, three second tetramines, polyamines classes such as tetraethylene-pentamine, for example alkamine such as N-(2-aminoethyl) thanomin etc.Moreover the amine as these chain lengthening agent and usefulness can use separately, also can be used in combination more than 2 kinds or 2 kinds.Moreover amine can use with the so masked form of ketoimine, ketazine or amine salt.
The chain lengthening agent, except the polyamines that contains polyoxyethylene groups, can also be also with above-mentioned polyglycidyl compounds or other amine, but the polyamines that contains polyoxyethylene groups is with more than or equal to 10 weight % at least in the total amount of chain lengthening agent, be more preferably with more than or equal to 40 weight %, preferably to cooperate more than or equal to 60 weight %.
And this reaction for example also can be wherein to cooperate above-mentioned chain lengthening agent after with polyurethane prepolymer and water cooperation.The relative polyurethane prepolymer amount that can be dissolved in the water, the polyurethane prepolymer of 100 parts by weight for example, the use level of water is 20～500 parts by weight.In addition, the use level of chain lengthening agent surpasses 1, preferably 1.1～20 ratio with the isocyanate group of polyurethane prepolymer with respect to the equivalence ratio (isocyanate group/amino) of the amino of chain lengthening agent and cooperates, and adopts just can access as known reaction methods such as mass polymerization or solution polymerizations.
In addition, in such cooperation, preferably each composition is cooperated so that in the urethane resin that obtains (Gu shape branch), polyoxyethylene groups content for more than or equal to 40 weight % so that be 45～95 weight %, especially be 50～90 weight %.If the polyoxyethylene groups content in the urethane resin reaches more than or equal to 40 weight %, just can the situation than less than 40 weight % the time obtain high water swelling ratio, that is, can give higher wetting ability.Therefore, requiring higher water swelling ratio, when wetting ability is given performance, preferentially selecting the polyoxyethylene groups content in the urethane resin is reached more than or equal to 40 weight %.
In above-mentioned use level, this reaction, specifically, at first, the polyurethane prepolymer limit is stirred to wherein adding water at leisure in the limit, and perhaps stirring waterside in limit is added polyurethane prepolymer, the aqueous solution of polyurethane preformed polymer thus at leisure in water.Preferred use ultra-high speed mixing tank etc. is given the solution high-shear when mixing for stirring.
Then, the limit is stirred the aqueous solution limit of this polyurethane prepolymer (just when the reaction of isocyanate group and water is not carried out) is splashed into the chain lengthening agent to wherein promptly.
In this reaction, preferred use ultra-high speed mixing tank etc. is given the solution high-shear when mixing for stirring.In addition, in order to suppress the isocyanate group in the polyurethane prepolymer and the reaction of water, for example preferential selective reaction temperature is controlled at 5～30 ℃.
In addition, after dripping of chain lengthening agent finished, reaction is finished while stir again at for example normal temperature.Thus, the form that urethane resin of the present invention just can the aqueous solution is prepared, and obtains waterborne polyurethane resin.The pH of waterborne polyurethane resin normally about 7～9.
After reaction finishes, for synthesis of polyurethane prepolymer by solution polymerization, by as under reduced pressure, under suitable temperature, heat, just can remove organic solvent.
The urethane resin of the present invention that obtains like this, can be prepared into the aqueous solution, make the waterborne polyurethane resin of the present invention of the aqueous solution, demonstrate good water-swellable because of its high wetting ability, other the intermiscibility of water-base resin such as the high and water-based emulsion of stability is good.And, this waterborne polyurethane resin is as hydrophilic modifier, as cooperating with other water-base resin, just can make the wetting ability such as water-permeable, water vapour permeability, water-retentivity, water-swellable, static resistance of this water-base resin be able to significant improvement, therefore by cooperating hydrophilic modifier and the water-base resin that constitutes by this waterborne polyurethane resin, just can access water vapour permeability resin of the present invention.
As water-base resin, have no particular limits.As the water-base resin that can cooperate with ratio arbitrarily, for example except the water-based emulsion of poly (vinyl acetate) emulsions, ACRYLIC EMULSION, polyaminoester emulsion, ester emulsion etc., can enumerate natural polymer aqueous solution such as synthetic resin aqueous solution, for example starch, gelatin of the polyvinyl alcohol resin aqueous solution or polyvinylpyrrolidone resin aqueous solution, polyvinyl acetal resin aqueous solution etc. etc.Preferably can be as polyaminoester emulsion.
Polyaminoester emulsion can react by making the isocyanate-based compound that contains that has 2 isocyanate group in active hydrogen based compound and per 1 molecule at least that contains that has 2 active hydrogen bases in per 1 molecule at least, obtains by disperseing and/or being dissolved in the water.
As containing the active hydrogen based compound, preferably can enumerate the macromolecular polyols such as polyoxyalkylene polyol of the carbonatoms 3～10 of polyester polyol, polycarbonate polyol, alkylidene group.
Can enumerate as polyester polyol, ethylene glycol for example, glycol ether, triglycol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 1, the 5-pentanediol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, cyclohexanediol, low molecular weight diols such as cyclohexanedimethanol more than a kind or 2 kinds or 2 kinds with for example propanedioic acid, toxilic acid, succsinic acid, hexanodioic acid, nonane diacid, tartrate, pimelic acid, sebacic acid, oxalic acid, terephthalic acid, m-phthalic acid, maleic anhydride, fumaric acid, dimeracid, the reaction of polycarboxylic acids such as trimellitic acid or its derivative and the polyester polyol that generates, 6-caprolactones etc. carry out ring-opening polymerization and polyester polyol of generating etc.
Can enumerate as polycarbonate polyol, for example ethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, glycol ether, dipropylene glycol, 1, reacting and the polycarbonate polyol that obtains with for example carbonates such as methylcarbonate, diphenyl carbonate, ethylene carbonate, carbonyl chloride more than a kind or 2 kinds or 2 kinds of glycolss such as 4-cyclohexanediol, 1,4 cyclohexane dimethanol, dihydroxyphenyl propane.
Polyoxy polyalkylene polyol as the carbonatoms 3～10 of alkylidene group can be enumerated, for example with ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol, 1,3-butyleneglycol, 1,5-pentanediol, 1,4-butyleneglycol, 1, the low-molecular-weight glycol of 6-hexylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol etc. is as initiator, makes the ring-type ethers of trimethylene oxide, tetrahydrofuran (THF), tetrahydropyrans etc. for example carry out ring-opening polymerization and the polyoxy polyalkylene polyol of the carbonatoms 3～10 of the alkylidene group that obtains.The preferential polyoxy polyalkylene polyol of selecting the carbonatoms 3～7 of alkylidene group, override is selected the polyoxy polyalkylene polyol of carbonatoms 4～6.
The molecular weight of these macromolecular polyols (number-average molecular weight) normally about 300～10000, preferably about 500～5000.
In addition, the content of the total amount of the relative urethane raw of macromolecular polyol (that is, the resin in the polyaminoester emulsion part raw material) is preferably more than or equals 50 weight %.When macromolecular polyol content is during more than or equal to 50 weight %, can improve the physical strength of water vapour permeability resin more.
In addition, as containing the active hydrogen based compound, except that macromolecular polyol, at for example ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol, 1,3-butyleneglycol, 1,5-pentanediol, 1,4-butyleneglycol, 1, the carbonatoms that makes oxyethane or propylene oxide etc. carry out the alkylidene group of addition polymerization in low-molecular-weight glycol such as 6-hexylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, glycerine, TriMethylolPropane(TMP) or ethylene glycol, the glycerine etc. are less than or equal to 2 polyoxyalkylene polyol also may be enough.
As containing isocyanate-based compound, can use the polymeric polyisocyanate that uses in the manufacturing with urethane resin identical contain isocyanate-based compound, preferably can enumerate above-mentioned aliphatic diisocyanate or above-mentioned alicyclic diisocyanate.
React for making to contain the active hydrogen based compound and contain isocyanate-based compound, need and/or be dissolved in the water,, can use emulsifying agent though this is had no particular limits with its dispersion.As emulsifying agent, for example containing the active hydrogen based compound and containing in the reaction of isocyanate-based compound, make the internal emulsifying agent of molecular chain generation modification when these compounds are reacted or make to contain the active hydrogen based compound or contain isocyanate-based compound not react, make it the outer emulsifying agent of additionally mixed.
As internal emulsifying agent, be fit to use as containing at least 3 weight % or the repeating unit that contains active hydrogen based compound, ethylene oxide,1,2-epoxyethane more than it with anionic property base, the molecular weight that contains the active hydrogen base more than at least 1 or 1 in polymkeric substance is 300～10000 the compound that contains the nonionic base.
As outer emulsifying agent, be fit to use as tensio-active agents such as polyoxyalkylene alkyl phenyl ether, alkylsurfuric acid metal-salt, linear alkyl benzene sulphonic acid metal-salts.
These emulsifying agents, relative urethane raw, using in 15 weight % or its following scope, internal emulsifying agent the most suitable use be have an anionic property base contain the active hydrogen based compound.In addition, contain active hydrogen based compound and the cooperation ratio that contains isocyanate-based compound, the isocyanate group that promptly contains isocyanate-based compound is 0.5～4.0 to the equivalence ratio (NCO/ active hydrogen base) of the active hydrogen base (hydroxyl, amino etc.) that contains the active hydrogen based compound, preferably 1.05～2.5.
Have again, in polyaminoester emulsion, more than or equal to 1 o'clock, after Xiang Shuizhong dispersion and/or the dissolving, use chain lengthening agent such as amine, can carry out chain lengthening in above-mentioned equivalence ratio (NCO/ active hydrogen base).As amine, can use the identical amine of amine that uses in the chain lengthening with urethane resin.Preferred example as, ethamine, butylamine, Isopropylamine, one amine of dibutylamine etc., quadrol for example, 1, the 3-propylene diamine, 1, the 4-butanediamine, 1, the 6-hexamethylene-diamine, 1, the 4-cyclohexanediamine, 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (different phorone diamines), 4,4 '-the dicyclohexyl methyl hydride diamines, 2,5 (2,6)-two (aminomethyl) dicyclo [2.2.1] heptane, 1, two (aminomethyl) hexanaphthenes of 3-, two amines such as hydrazine, for example Diethylenetriamine, three second tetramines, polyamines classes such as tetraethylene-pentamine, for example alkamine such as N-(2-aminoethyl) thanomin, γ-An Bingjisanyiyangjiguiwan, N-phenyl-γ-aminopropyl trimethoxy silane etc. contains an amine of alkoxysilyl, N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl) γ-aminopropyl methyltrimethoxy silane etc. contains two amines of alkoxysilyl.
In addition, water-base resin when it is carried out curtain coating (for example, during with wide 10mm, thick 0.1mm curtain coating) physical strength, its tensile strength is more than or equal to 6MPa, preferably more than or equal to 8MPa, be more preferably more than or equal to 10MPa, unit elongation is more than or equal to 200%, preferably, be more preferably more than or equal to 400% more than or equal to 300%.
In addition, (for example, during with wide 10mm, thick 0.1mm curtain coating) water swelling ratio better is to be less than or equal to 20% to the curtain coating water-base resin, is more preferably to be less than or equal to 10%, is preferably less than or equals 5% when it is carried out curtain coating.
So,, just can access water vapour permeability resin of the present invention by in such water-base resin, cooperating above-mentioned hydrophilic modifier.In addition, in the cooperation of hydrophilic modifier and water-base resin, also can cooperate N-Methyl pyrrolidone, N simultaneously, the phase solvation of dinethylformamide etc. with them.
The cooperation ratio of hydrophilic modifier, for example the solid shape branch (resinous principle in the water-base resin and the total of the resinous principle in the hydrophilic modifier) of relative water vapour permeability resin is 20～80 weight %, preferably 30～70 weight %.The relative solid shape branch of water vapour permeability resin, the proportioning of hydrophilic modifier for example fruit is lower than 20 weight %, and the water vapour permeability that carries out the film that curtain coating obtains is step-down often, if surpass 80 weight %, the mechanical strength of resin that carries out the film that curtain coating obtains is step-down often.
Water vapour permeability resin of the present invention by curtain coating, can access the film with moisture-permeability waterproof, especially by carry out curtain coating on base fabric, for example can access the moisture-permeability waterproof raw material of use in the dress material of moisture-permeability waterproof processing etc.
Film with moisture-permeability waterproof, though this film is the micro-porous film and the film of atresia matter, any can.
In addition, as base fabric, for example can enumerate the fabric that constitutes by fibers such as polyester, nylon, cottons, cloth, non-woven fabrics etc.
Curtain coating to the base fabric of water vapour permeability resin can make in all sorts of ways, and laminating, direct coating method etc. are wherein arranged, and can select aptly according to its purposes.For example, using under the situation of laminating, can enumerate coating water vapour permeability resin on the surface of separate-type paper etc., after heat-treating, this separate-type paper is being stacked on the cloth and silk, carrying out the method that hot melt.In addition, using under the situation of direct coating method, can enumerate use as the scraper coating common coating method, on the base fabric surface or the method that directly is coated with of separate-type paper surface.
So, by such curtain coating, utilize the overlay film that constitutes by the water vapour permeability resin to be covered on the surface of base fabric with moisture-permeability waterproof, finish moisture-permeability waterproof processing thus to the base fabric surface.
Like this through the base fabric of moisture-permeability waterproof processing, be used as the moisture-permeability waterproof raw material as mentioned above and be used for dress material.
So-called moisture-permeability waterproof is meant that rain or other water are by overlay film, and the performance that moisture (water vapor) passes through, and for example in the dress material purposes, is meant that the water vapor that the sweating by health produces emits outside clothes, and prevents that rain from entering the performance in the clothes.
In addition, water vapour permeability resin of the present invention need guarantee that it has the performance of following base fabric fully, wear resisting property, anti-destructive characteristics etc.For this reason, tensile strength as the physical strength of the casting films of water vapour permeability resin of the present invention is more than or equal to 3MPa, be more preferably more than or equal to 4MPa, preferably more than or equal to 6MPa, unit elongation is more than or equal to 200%, be more preferably more than or equal to 300%, preferably more than or equal to 400%.
Have, as the water vapour permeability of water vapour permeability resin of the present invention, when the thickness of casting films was 0.03mm, the water vapour permeability in water vapour permeability test B method (JIS L1099 standard) was more than or equal to 10000 (g/m again
2Be gratifying 24h).
Moreover, at urethane resin of the present invention, waterborne polyurethane resin, in hydrophilic modifier and the water vapour permeability resin, in the scope of the excellent results that does not hinder the invention described above, can cooperate curing catalysts or various additive, for example softening agent aptly, defoamer, flow agent, anti-mildew agent, rust-preventive agent, matting agent, fire retardant, thixotropic agent, the bonding imparting agent, thickening material, smooth agent, static inhibitor, tensio-active agent, the response delay agent, oxidation inhibitor, UV light absorber, anti hydrolysis agent, weather-proof stablizer, dyestuff, mineral dye, pigment dyestuff, body pigment, solidifying agent, release agent etc.
As solidifying agent, for example if normally used solidifying agent just has no particular limits, for example can enumerate isocyanate-based solidifying agent with isocyanate group etc., the polymeric polyisocyanate that preferably for example can enumerate water dispersible is a solidifying agent etc.
In addition,, inorganic powder can be enumerated, preferably for example SiO 2 powder etc. can be enumerated as release agent.
The cooperation ratio of these various additives is selected aptly according to its purpose and purposes.
In addition, urethane resin of the present invention, waterborne polyurethane resin, hydrophilic modifier and water vapour permeability resin are not limited to above-mentioned dress material purposes, for example also can use in various uses such as automobile, electronics, building materials, imitation leather, film processing.
Below, with reference to embodiment, Comparative Examples and synthesis example, be described more specifically the present invention, but be not to limit scope of the present invention.
Embodiment 1
The preparation of polyurethane prepolymer
8.3 parts by weight 1 of in stirring reactor, packing into, two (isocyanato-methyl) hexanaphthenes (1 of 3-, 3-bis (isocyanatomethyl) cyclohexane) (trade(brand)name: ケ ネ-ト 600, the military field of Mitsui ケ ミ カ Le corporate system), 1.2 parts by weight ethylene glycol, 0.7 parts by weight dimethylol propionic acid (trade(brand)name: ニ Star カ マ-PA, Japan changes into corporate system), 2.5 parts by weight acetonitrile, temperature of reaction is adjusted in 70～75 ℃, react to reactivity more than or equal to 99%, obtain having the anionic property base at molecular side chain, the polyurethane prepolymer that has the free isocyanate group in molecular end.The carboxylic acid of every this polyurethane prepolymer of 100g is 49 milligramequivalents.
The preparation of waterborne polyurethane resin
Make the above-mentioned polyurethane prepolymer that obtains be cooled to 30 ℃, add 0.5 parts by weight triethylamine, stir fully and neutralize.After this, add 25 ℃ 100 parts by weight water at leisure, after forming the aqueous solution of polyurethane prepolymer, diamines (the trade(brand)name: PEG#1000 diamines of promptly dripping successively and containing polyoxyethylene groups, Nof Corp.'s system) aqueous solution 3.0 parts by weight of the aqueous solution 70.5 parts by weight of 20 weight %, hydrazine 10 weight % carry out the chain lengthening reaction.The reacting liquid temperature of this moment is adjusted in 25～30 ℃.After this, 25～30 ℃ continue to stir 3 hours after, 40～50 ℃, under reduced pressure, remove acetonitrile and portion water, obtain the waterborne polyurethane resin that solid shape is divided 20 weight %, viscosity 190mPas.
Embodiment 2～5
Press the prescription shown in the table 1, by with embodiment 1 identical operations, obtain waterborne polyurethane resin.
Comparative Examples 1
Press the prescription shown in the table 1, by with embodiment 1 identical operations, make waterborne polyurethane resin, but finally gelation take place.
Comparative Examples 2
Press the prescription shown in the table 1, by with embodiment 1 identical operations, make waterborne polyurethane resin.
Comparative Examples 3
Isocyanate group content 15.8%), 62 weight ion exchanged waters in stirring reactor, pack into 47.1 parts by weight ケ ネ-ト WD-725 (the military field of Mitsui ケ ミ カ Le corporate system, water-dispersible polyisocyanates:, disperse equably.After this, on one side dispersed with stirring liquid, add isocyanate group and amino equivalence ratio (isocyanate group/amino) on one side at leisure and be 1.0, amine value 101 contain polyoxyethylated diamines (trade(brand)name PEG#1000 diamines, Nof Corp.'s system) 54.3 parts by weight.After this, though follow the tracks of reaction at 25 ℃, along with the carrying out of reaction, stability reduces at leisure, and gelation finally takes place.
Abbreviation in the table 1 and goods name are as follows.In addition, the prescription in the table 1 is represented with parts by weight.
H6XDI:1, two (isocyanato-methyl) hexanaphthenes of 3-, trade(brand)name ケ ネ-ト 600, the military field of Mitsui ケ ミ カ Le corporate system
H12MDI:4,4 '-methylene-bis (NSC 87419), trade(brand)name デ ス モ ジ ュ-Le W, バ イ ェ Le corporate system
WD-725: water-dispersible polyisocyanates (isocyanate group content 15.8%), trade(brand)name ケ ネ-ト WID-725, the military field of Mitsui ケ ミ カ Le corporate system
PEG1000: polyoxyethylene glycol (OH valency 112), Nof Corp.'s system
EG: ethylene glycol
DMPA: dimethylol propionic acid, trade(brand)name ニ Star カ マ-PA, Japan changes into corporate system
MPEG glycol: methoxyl group modified poly (ethylene glycol) branching glycol (OH valency 89), the military field of Mitsui ケ ミ カ Le corporate system
TEA: triethylamine
NaOH: sodium hydroxide
PEG#1000 diamines: polyethyleneoxide diamine (amine value 101), Nof Corp.'s system
ジ ェ Off ァ ミ Application ED-2003: polyoxyalkylene diamines (amine value 53.9), Ha Application Star マ Application corporate system, EO/PO mol ratio=38.7/6.0
KBM-602:N-β (aminoethyl) γ-aminopropyl methyl dimethoxysilane (amine value 544), chemical industrial company of SHIN-ETSU HANTOTAI system
Estimate
1) water-swellable test
The waterborne polyurethane resin (Gu shape is divided 20 weight %) of each embodiment and Comparative Examples 2 is carried out curtain coating, form the dry transparent overlay film of thickness 1mm.After this, 10cm * 10cm is processed in this overlay film cut-out, as sample.
Curtain coating is to use scraper to be coated on the surface coated waterborne polyurethane resin of separate-type paper, applies thermal treatment in 5 minutes at 130 ℃, obtains transparent overlay film.
Each sample that obtains flooded 12 hours in 25 ℃ distilled water, measured the length on the limit in length and breadth just taken out, with this in length and breadth the limit length on average as the water swelling ratio.(point out in passing, so-called water swelling ratio be 100% be the expression limit length all increased by 2 times in length and breadth) it the results are shown in the table 1.
2) compatibility test
As water-base resin, prepare ケ ラ ッ Network W-6010 (the military field of Mitsui ケ ミ カ Le corporate system, the aqueous dispersions of polycarbonate-based urethane resin is Gu shape is divided 30 weight %, 30MPas) and W-6020 (the military field of Mitsui ケ ミ カ Le corporate system, polyethers is the aqueous dispersions of urethane resin, Gu shape is divided 30 weight %, 20MPas), each 100 parts by weight of these aqueous dispersions relatively, waterborne polyurethane resin 150 parts by weight of mix embodiment 1～5, Comparative Examples 2, the stability of Visual Confirmation mixed solution.It the results are shown in the table 1.In table 1, the state that " zero " expression evenly mixes, the state that " * " expression is separated.
3) water vapour permeability test A method
The waterborne polyurethane resin (Gu shape is divided 20 weight %) of each embodiment and Comparative Examples 2 is carried out curtain coating, form the dry transparent overlay film of thickness 0.05mm.After this, according to this overlay film of JIS L1099-A1 standard evaluation.It the results are shown in the table 1.
Comparative Examples 2, can not be measured so do not obtain uniform overlay film because intermiscibility is bad.
Table 1
| Prescription | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Polymeric polyisocyanate | ????H6XDI | ????8.3 | ????- | ????- | ????- | ????- | ????- | ????- | ????- |
| ????H12MDI | ????- | ????6.2 | ????8.0 | ????5.5 | ????6.6 | ????4.9 | ????9.8 | ????- | |
| ????WD-725 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????47.1 | |
| Polyvalent alcohol | ????PEG1000 | ????- | ????12.0 | ????12.5 | ????10.8 | ????12.9 | ????6.8 | ????15.2 | ????- |
| ????EG | ????2.5 | ????- | ????- | ????- | ????- | ????- | ????- | ????- | |
| The compound that contains the active hydrogen base of anionic property base | ????DMPA | ????0.7 | ????0.8 | ????0.8 | ????0.7 | ????0.9 | ????- | ????1.0 | ????- |
| The MPEG glycol | ????- | ????- | ????- | ????- | ????- | ????7.8 | ????- | ????- | |
| Solvent | Acetonitrile | ????2.5 | ????8.1 | ????8.4 | ????7.3 | ????8.3 | ????8.3 | ????10.3 | ????- |
| Neutralizing agent | ????TEA | ????0.5 | ????0.8 | ????0.6 | ????0.6 | ????- | ????- | ????0.8 | ????- |
| ????NaOH | ????- | ????- | ????- | ????- | ????0.2 | ????- | ????- | ????- | |
| The chain lengthening agent | PEG diamines #1000 | ????14.1 | ????5.4 | ????4.5 | ????- | ????4.2 | ????5.5 | ????- | ????16.3 |
| ????ジェファミン ????ED-2003 | ????- | ????- | ????- | ????7.3 | ????- | ????- | ????- | ????- | |
| Hydrazine | ????0.3 | ????- | ????- | ????- | ????- | ????- | ????0.3 | ????- | |
| ????KBM602 | ????- | ????- | ????0.2 | ????0.2 | ????- | ????- | ????- | ????- | |
| Distilled water | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | |
| The anionic property base equivalent (milligramequivalent) of every 100g polyurethane prepolymer | ????49 | ????32 | ????32 | ????32 | ????32 | ????0 | ????32 | ????0 | |
| Polyoxyethylene groups content (weight %) | Content in the prepolymer | ????0 | ????63.3 | ????63.3 | ????63.3 | ????63.3 | ????75.0 | ????63.3 | ????- |
| Content in the urethane resin | ????56.4 | ????69.7 | ????67.8 | ????67.5 | ????68.3 | ????80.6 | ????60.6 | ????65.2 | |
| Urethane resin aqueous solution proterties | Gu shape branch (weight %) | ????20 | ????20 | ????20 | ????20 | ????20 | ????20 | ????20 | ????20 |
| Viscosity (mPas) | ????190 | ????20000 | ????16000 | ????9000 | ????21000 | Gelation | ????100000 | Gelation | |
| Water swelling ratio (%) | ????90 | ????130 | ????120 | ????122 | ????150 | ????- | ????65 | ????- | |
| Intermiscibility | ????W-6010 | ????○ | ????○ | ????○ | ????○ | ????○ | ????- | ????× | ????- |
| ????W-6020 | ????○ | ????○ | ????○ | ????○ | ????○ | ????- | ????× | ????- | |
| Water vapour permeability test A method (g/m 2·24h) | ????W-6010 | ????5500 | ????9400 | ????8000 | ????7700 | ????9200 | ????- | ????- | ????- |
| ????W-6020 | ????6000 | ????9600 | ????9000 | ????7200 | ????10000 | ????- | ????- | ????- | |
Synthesis example 1
Synthesizing of water-base resin
11.75 parts by weight 4 of in stirring reactor, packing into, 4 '-methylene-bis (NSC 87419), 31.39 the polyoxy tetramethylene ethylene glycol (trade(brand)name: PTG2000SN of the molecular weight 2000 (number-average molecular weight) of parts by weight, protect native ケ paddy chemical company system), 2.37 parts by weight dimethylolpropionic acid (trade(brand)name: ニ ッ カ マ-BA, Japan changes into corporate system) and 20.4 parts by weight acetone, reacting liquid temperature is adjusted in 53～55 ℃, as catalysts, add the stannous octoate (trade(brand)name: ス ノ Network ト of trace, the コ of API Corp.-Port レ-シ ョ Application system), make reaction proceed to reactivity, obtain having the anionic property base at molecular side chain more than or equal to 99%, the polyurethane prepolymer that has the free isocyanate group in molecular end.
Make this polyurethane prepolymer be cooled to 30 ℃, add 1.46 parts by weight triethylamines (carboxylic acid neutralization ratio 0.9), stir fully and neutralize.After this, it is added in 25 ℃ the 100 parts by weight water at leisure, form the aqueous solution of polyurethane prepolymer after, the different phorone diamines of 1.96 parts by weight that promptly drip carries out the chain lengthening reaction.The reacting liquid temperature of this moment is adjusted in 25～30 ℃.After this, 25～30 ℃ continue to stir 3 hours after, 40～50 ℃, under reduced pressure remove acetone, obtain the polyaminoester emulsion that solid shape is divided 33 weight %, viscosity 25mPas.
Synthesis example 2 and 3
Press the prescription shown in the table 2, by with synthesis example 1 identical operations, obtain polyaminoester emulsion.
Abbreviation in the table 2 and goods name are as follows.In addition, the prescription in the table 2 is represented with parts by weight.
PTG-1: the polyoxy tetramethylene ethylene glycol of number-average molecular weight 20000, trade(brand)name PTG-2000SN protects native ケ paddy chemical company system
Ester-1: the polyester polyol of number-average molecular weight 2000, the military field of trade(brand)name ケ ラ ッ Network U-5620 Mitsui ケ ミ カ Le corporate system
DMBA: dimethylolpropionic acid, trade(brand)name ニ ッ カ マ-BA, Japan changes into corporate system
IPDA: different phorone diamines, デ グ サ-ヒ ュ Le ス corporate system
Estimate
4) mechanical robustness testing
The polyaminoester emulsion (Gu shape is divided 33 weight %) of each synthesis example is carried out curtain coating, form the dry transparent overlay film of thickness 0.1mm.After this, this overlay film is cut into the rectangle of 1cm, carry out tension test, stress, unit elongation when measuring fracture with the condition of draw speed 200mm/min.It the results are shown in table 2.
Table 2
| Prescription | Synthesis example 1 | Synthesis example 2 | Synthesis example 3 | |
| Contain isocyanate-based compound | ????H12MDI | ????11.75 | ????11.78 | ????11.83 |
| Contain the active hydrogen based compound | ????PTG-1 | ????31.97 | ????33.59 | |
| ????Ester-1 | ????33.72 | |||
| Contain anionic property base active dydrogen compounds | ????DMPA | ????2.05 | ????2.05 | |
| ????DMBA | ????2.37 | |||
| Solvent | Acetonitrile | ????20.97 | ||
| Acetone | ????20.38 | ????20.92 | ||
| Neutralizing agent | ????TEA | ????1.46 | ????1.39 | ????1.32 |
| The chain lengthening agent | ????IPDA | ????1.96 | ||
| Quadrol | ????0.69 | |||
| Hydrazine | ????0.58 | |||
| Distilled water | ????100 | ????100 | ????100 | |
| Polyoxyethylene groups content (weight %) | Content in the urethane resin | ????0 | ????0 | ????0 |
| The water-base resin proterties | Gu shape branch (weight %) | ????33 | ????33 | ????33 |
| Viscosity (mPas) | ????25 | ????22 | ????14 | |
| Water swelling ratio (%) | ????2 | ????2 | ????2 | |
| Physical strength | Tensile strength (MPa) | ????18 | ????14 | ????19 |
| Unit elongation (%) | ????480 | ????580 | ????510 | |
Embodiment 6
The water-base resin that waterborne polyurethane resin that obtains with 60: 40 mix embodiment 3 of weight ratio and synthesis example 1 obtain obtains the water vapour permeability resin.It is 25.2 weight % that the solid shape of this moment is divided.
Embodiment 7
With weight ratio fully mix waterborne polyurethane resin that embodiment 3 obtains at 60: 2, as silicon-dioxide (the trade(brand)name サ イ リ シ ア 310P of additive, release agent, the シ リ シ ア of Fuji corporate system), then, water-base resin so that this compound of 62: 38 mixed and synthesis example 1 obtain obtains the water vapour permeability resin.The solid shape branch concentration of this moment is 26.5 weight %.
Embodiment 8 and 9
Press the prescription of table 3, by with embodiment 7 identical operations, obtain the water vapour permeability resin.
Embodiment 10
The water-base resin that waterborne polyurethane resin that obtains with 55: 43 mix embodiment 3 of weight ratio and synthesis example 2 obtain obtains the water vapour permeability resin.In this water vapour permeability resin,, mix WD-725 (solidifying agent (water-dispersible polyisocyanates: isocyanate group content 15.8%, the military field of Mitsui ケ ミ カ Le corporate system)) at 98: 2 again with weight ratio as additive 2.
Estimate
5) compatibility test
The stability of the water vapour permeability resin by each embodiment of Visual Confirmation.It the results are shown in the table 3.In table 3, the state that " zero " expression evenly mixes, the state that " * " expression is separated.
6) water vapour permeability test B method
The water vapour permeability resin of each embodiment is carried out curtain coating, form the dry transparent overlay film of thickness 0.03mm.After this, according to JIS L1099-B1 standard evaluation water vapour permeability.It the results are shown in the table 3.
7) physical strength
The water vapour permeability resin of each embodiment is carried out curtain coating, form the dry transparent overlay film of thickness 0.03mm.After this, carry out the tension test identical operations with polyaminoester emulsion, stress, unit elongation when measuring fracture.It the results are shown in table 3.
Abbreviation in the table 3 is as follows.In addition, the prescription in the table 3 is represented with parts by weight.
Additive 1: silicon-dioxide (release agent, trade(brand)name サ イ リ シ ア 310P, the シ リ シ ア of Fuji corporate system)
Additive 2:WD-725 (water-dispersible polyisocyanates isocyanate group content 15.8%, the military field of Mitsui ケ ミ カ Le corporate system)
Table 3
| Prescription | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Waterborne polyurethane resin | Kind | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 4 | Embodiment 3 |
| Parts by weight | ????60 | ????60 | ????55 | ????55 | ????55 | |
| Water-base resin | Kind | Synthesis example 1 | Synthesis example 1 | Synthesis example 2 | Synthesis example 3 | Synthesis example 1 |
| Parts by weight | ????40 | ????38 | ????43 | ????43 | ????43 | |
| Additive | Kind | ????- | Additive 1 | Additive 1 | Additive 1 | Additive 2 |
| Parts by weight | ????- | ????2 | ????2 | ????2 | ????2 | |
| Gu shape branch (weight %) | ????25.2 | ????26.5 | ????27.2 | ????27.2 | ????27.2 | |
| Intermiscibility | ????○ | ????○ | ????○ | ????○ | ????○ | |
| Water vapour permeability test B method | Thickness (μ m) | ????33 | ????28 | ????31 | ????26 | ????34 |
| Water vapour permeability (g/m 2·24h) | ????140000 | ????105000 | ????110000 | ????120000 | ????19000 | |
| Physical strength | Tensile strength (MPa) | ????4.2 | ????6.4 | ????5.7 | ????6.2 | ????13 |
| Unit elongation (%) | ????620 | ????420 | ????550 | ????480 | ????240 | |
The water vapour permeability resin that embodiment 6～9 obtains has intermiscibility well, physical strength, extremely good water vapour permeability, the water vapour permeability resin that embodiment 10 obtains, by cooperating solidifying agent, both had tough physical strength, have water vapour permeability well again, be suitable as the use of the overlay film of moisture-permeability waterproof simultaneously.
Moreover, above-mentioned explanation, though provide as illustrative embodiment of the present invention, these only are simple illustrations, can not be as determinate explanation.Can be included in the scope of claim described later by the variation of the present invention that those skilled in the art person recognized.
Claims (11)
1. urethane resin is characterized in that, the polyamines that makes polyurethane prepolymer with anionic property base at least and contain polyoxyethylene groups reacts and obtains.
2. urethane resin according to claim 1 is characterized in that, the content of above-mentioned anionic property base in polyurethane prepolymer is that every 100g polyurethane prepolymer contains the above-mentioned anionic property base of 5～200 milligramequivalents.
3. urethane resin according to claim 1 is characterized in that above-mentioned polyurethane prepolymer comprises polymeric polyisocyanate and polyoxyalkylene polyol as raw material.
4. urethane resin according to claim 1 is characterized in that, the polyoxyethylene groups content in the above-mentioned polyurethane prepolymer is more than or equal to 40 weight %.
5. urethane resin according to claim 1 is characterized in that, the polyoxyethylene groups content in the above-mentioned urethane resin is more than or equal to 40 weight %.
6. urethane resin according to claim 1 is characterized in that, as raw material, also comprises the polyglycidyl compounds with primary amino or primary amino and secondary amino group.
7. waterborne polyurethane resin is characterized in that, the polyamines that makes polyurethane prepolymer with anionic property base at least and contain polyoxyethylene groups reacts and the urethane resin that obtains disperses and/or be dissolved in water.
8. hydrophilic modifier, it is characterized in that, comprise waterborne polyurethane resin, the polyamines that this waterborne polyurethane resin makes polyurethane prepolymer with anionic property base at least and contains polyoxyethylene groups reacts and the urethane resin that obtains disperses and/or be dissolved in water to obtain.
9. water vapour permeability resin, it is characterized in that, comprise hydrophilic modifier and water-base resin, this hydrophilic modifier contains the polyamines that makes the polyurethane prepolymer with anionic property base at least and contain polyoxyethylene groups and reacts and urethane resin dispersion that obtains and/or the waterborne polyurethane resin that is dissolved in water.
10. water vapour permeability resin according to claim 9 is characterized in that,
Above-mentioned water-base resin is an ester-polyurethane resin emulsion,
Above-mentioned ester-polyurethane resin emulsion contains macromolecular polyol as raw material,
Above-mentioned macromolecular polyol is select from the group that the polyoxy polyalkylene polyol of the carbonatoms 3～10 of polyester polyol, polycarbonate polyol and alkylidene group is formed at least a,
The total amount of the urethane raw of above-mentioned relatively polyaminoester emulsion contains above-mentioned macromolecular polyol more than or equal to 50 weight %.
11. the manufacture method of urethane resin is characterized in that, polyurethane prepolymer with anionic property base and the polyamines that contains polyoxyethylene groups are reacted.
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| JP2003203507 | 2003-07-30 | ||
| JP2003203507 | 2003-07-30 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381450B (en) * | 2008-10-14 | 2011-05-18 | 旭川化学（苏州）有限公司 | Polyurethane resin for superfine fibre soaking |
| WO2013007004A1 (en) * | 2011-07-08 | 2013-01-17 | 江苏博特新材料有限公司 | Water-dispersible amphoteric polyurethane, preparation method therefor, and use thereof in reinforcing concrete |
| CN106457509A (en) * | 2014-03-14 | 2017-02-22 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polishing pad and method for producing same |
| CN106457510A (en) * | 2014-03-14 | 2017-02-22 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polishing pad and method for producing same |
| WO2018120055A1 (en) * | 2016-12-29 | 2018-07-05 | 万华化学集团股份有限公司 | Polyurethane or polyurethane-urea aqueous dispersion, preparation method therefor, and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017073171A1 (en) * | 2015-10-30 | 2017-05-04 | Dic株式会社 | Gloves |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161049A (en) * | 1995-09-15 | 1997-10-01 | H·B·富勒许可及融资股份有限公司 | Reduced solvent process for preparation of aqueous polyurethane dispersions with improved heat and solvent resistance |
| DE19916647B4 (en) * | 1999-04-14 | 2006-06-08 | Bayer Materialscience Ag | Polyol mixture for the production of rigid polyurethane foams |
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2004
- 2004-07-30 CN CNB2004100702674A patent/CN100354329C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381450B (en) * | 2008-10-14 | 2011-05-18 | 旭川化学（苏州）有限公司 | Polyurethane resin for superfine fibre soaking |
| WO2013007004A1 (en) * | 2011-07-08 | 2013-01-17 | 江苏博特新材料有限公司 | Water-dispersible amphoteric polyurethane, preparation method therefor, and use thereof in reinforcing concrete |
| CN106457509A (en) * | 2014-03-14 | 2017-02-22 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polishing pad and method for producing same |
| CN106457510A (en) * | 2014-03-14 | 2017-02-22 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polishing pad and method for producing same |
| WO2018120055A1 (en) * | 2016-12-29 | 2018-07-05 | 万华化学集团股份有限公司 | Polyurethane or polyurethane-urea aqueous dispersion, preparation method therefor, and use thereof |
| US11118000B2 (en) | 2016-12-29 | 2021-09-14 | Wanhua Chemical Group Co., Ltd. | Polyurethane or polyurethane-urea aqueous dispersion, preparation method therefor, and use thereof |
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| CN100354329C (en) | 2007-12-12 |
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