CN1189171A - Aqueous non-gelling anionic polyurethane dispersions and process for their manufacture - Google Patents
Aqueous non-gelling anionic polyurethane dispersions and process for their manufacture Download PDFInfo
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- CN1189171A CN1189171A CN96194623A CN96194623A CN1189171A CN 1189171 A CN1189171 A CN 1189171A CN 96194623 A CN96194623 A CN 96194623A CN 96194623 A CN96194623 A CN 96194623A CN 1189171 A CN1189171 A CN 1189171A
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Abstract
Aqueous dispersion adhesives of anionic polyurethanes which have high heat resistance and low activation temperature, even when employed without addition of a cross-linker. The polyurethane is the reaction product of an isocyanate terminated polyurethane prepolymer, and water. The polyurethane prepolymer is the reaction product of a polyol component and a diisocyanate component, the polyolcomponent including: a sulfonated polyester polyol, a hydroxy carboxylic acid of the formula: (HO)xR (COOH)y wherein (R) represents a straight or branched, hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, and optionally, a low molecular weight aliphatic diol having a molecular weight of from 60 to 400, a non-sulfonated polyol, and the diisocyanate component being selected from the group consisting of aromatic diisocyanates, isopherone diisocyanate, hexamethylene diisocyanate and mixtures thereof. The dispersions are prepared by mixing prepolymer and water at a temperature of at least 60 DEG C for sufficient time to fully react the isocyanate groups in a prepolymer self-extension reaction with water, typically at least 0.5 hour. The dispersions of the invention provide higher strength adhesive bonds than identical prepolymer dispersions extended with diamine chain extender, instead of water, after dispersion. The adhesive composition may also be modified to include a dispersed polymer or copolymer of an ethylenically unsaturated monomer. Such compositions may be obtained by preparing the sulfonated polyurethane in the presence of an ethylenically unsaturated monomer and subsequently subjecting the mixture to free-radical polymerization.
Description
Background of invention
Invention field
The present invention relates to new aqueous urethane dispersion agent tacking compositions, said composition can be single-component or two component, is used for thermoforming.More specifically, the present invention relates to comprise the aqueous polyurethane dispersion agent tacking compositions of the polyurethane dispersions system of sulfonate radical and carboxylate radical mixed anion, also contain compatible linking agent, perhaps do not contain linking agent.These novel sizing compositions have satisfactory stability when low pH value, working life is long, the green strength height, and water resistance is good and have a resistance toheat of having improved.
Prior art
The aqueous dispersion of urethane system is known by people, for example, sees to be set forth in United States Patent (USP) 3,479 310, Angew.Chem.1972 the 82nd rolls up during 53 phases and Angew.Makromol.Chem1981 the 98th roll up.
The urethane of the no NCO root with interior ion salt group of a kind of chain full extension that is scattered in the water is disclosed in the United States Patent (USP) 3,479,310 of Dieterich etc.
Concerning negatively charged ion aqueous polyurethane dispersion system, the ion salt group is the salt of carboxylic acid or sulfonic acid.
Only there is the carboxylate radical end group only o'clock stable in pH＞7 as the aqueous polyurethane of anionicsite.This polyurethane dispersions system such as many functional group isocyanates, Resins, epoxy or aziridine, can form a kind of two-pack sizing composition by compatible linking agent.
People's such as Henning United States Patent (USP) 4,870,129 discloses sodium salt (AAS salt) the preparation polyurethane dispersions system with N-(2-amino-ethyl)-2-aminoethyl sulfonic acid.It is reported aqueous polyurethane dispersion tie up to have satisfactory stability under the low pH value (5-7), high green strength and medium resistance toheat.
Usually, after a kind of polyisocyanate crosslinking agent blend with sulfonated polyurethane dispersions system and the disperseed polymeric polyisocyanate described in people's such as Hombach United States Patent (USP) 4,663,377, their resistance toheat will improve.
The United States Patent (USP) 4,762,880 of Leung discloses the water base thermoforming tackiness agent that contains aromatic urethane, linking agent and other material.Because its aromatic urethane component, the sizing composition of these types will need high temperature to activate.
Be issued in people's such as Henning the United States Patent (USP) 4,870,129 and disclose a kind of tackiness agent of being made up of aqueous polyurethane, the former comprises with the carboxylate radical of chemical state blending or sulfonate group.The described tackiness agent of this document has demonstrated low activation temperature, but resistance toheat only is medium.
People such as Duan disclose the aqueous polyurethane dispersion system based on the sulfonated polyester polyol in WO 95/08583 and WO 96/07540, it has unusual high crystal forming rate, also has simultaneously satisfactory stability under the low pH value, high green strength and medium and resistance toheat highly.
In the preparation of anion polyurethane dispersion system, usually preferred preparation earlier contains the base polyurethane prepolymer for use as of the free isocyanic ester of small portion of residual, this performed polymer is scattered in the water, adds low relatively uncle of a kind of multi-functional molecular weight and/or parahelium then as the chain spreading agent.Need this chain expansion process, be because obtained after the expansion having high heat resistance can more high-molecular weight polyurethane-urea still, also there are some problems in the chain expansion.The reaction of the free isocyanic ester of ammonia and performed polymer is a kind of very quick, active reaction, has therefore increased the possibility of side reaction (producing side chain or network structure) and gel.
People have known that chain expansion also can be reacted by isocyanate functional group on the base polyurethane prepolymer for use as and water and have realized, it is believed that this will generate ammonia functional group on performed polymer, other isocyanate functional group of this functional group and performed polymer reacts rapidly, thereby obtains a kind of from expanding polymkeric substance.But this reaction produces carbonic acid gas, and the pH value of dispersion system descends simultaneously in the expansion reaction process.Concerning the carboxylate anion dispersion system, the decline of pH value can cause polymkeric substance to be separated out from dispersion system.P-sulfonic acid salt dispersion system will use a large amount of solvents to realize disperseing (account for dispersion system gross weight 1/3), and most of subsequently solvent is evaporated away, and for example American National Standard GB 1,128, disclosed content among 568 the embodiment.It is reported and obtained a kind of stable dispersion system.Yet it is very expensive to steam and reclaim the required equipment of excessive solvent, is unsuitable for preparing the urethane disperse phase product with optimum performance of doing the special industry application.
At United States Patent (USP) the 5th, 173, No. 526 (Air Product﹠amp; Chemicals company), among United States Patent (USP) the 4th, 644, No. 030 (Witco company) and the EP 066275-A2, it is reported and narrated hydridization disperse phase product, the polymerization in the presence of the urethane disperse phase of therein ethylene base monomer.Described urethane disperse phase is not based on the sulfonated polyurethane dispersion system.
Summary of the invention
Even the present invention relates to not add in use still have under the situation of linking agent low activation temperature and high heat resistance can new aqueous sulfonated polyurethane dispersion system and prepare the method this aqueous polyurethane dispersion agent tacking compositions of the present invention of this dispersion system and the excellent compatibility that other aqueous-based polymers has, contain polyurethane dispersions system, vinyl-acetic ester emulsion and vinylformic acid vinyl ester emulsion such as other sulfonation or carboxylic acidifying, the excellent compatibility that it also has with thickening material and pigment.
The aqueous dispersion system that this composition of the present invention is a kind of anion polyurethane, this urethane comprises the reaction product of isocyanate-terminated base polyurethane prepolymer for use as and water.Base polyurethane prepolymer for use as is the reaction product of polyvalent alcohol component and vulcabond component, and described polyvalent alcohol component comprises:
A kind of sulfonated polyester polyol
With a kind of chemical formula be (HO)
xR (COOH)
yHydroxycarboxylic acid,
Wherein R represent carbonatoms be 1～12 straight chain or
Branched hydrocarbyl, x and y represent 1～3 numerical value, described vulcabond component is selected from vulcabond of aromatic diisocyanate, two isocyanic acid isophorone esters, hexamethylene glycol and composition thereof.In a preferred embodiment of the invention, the polyvalent alcohol component comprises that also molecular weight is 60～400 lower molecular weight aliphatic dihydroxy alcohol.Randomly, base polyurethane prepolymer for use as also can comprise a kind of non-sulfonation polyvalent alcohol.
Dispersion system of the present invention uses after can adding linking agent, also can be without linking agent.In preferred embodiments, even uncrosslinked tackiness agent has added the dispersion system of the prior art of linking agent when using, the former can provide suitable or better resistance toheat, and its resistance toheat also is better than the similar uncrosslinked polymer dispersed system with the preparation of diamino chain spreading agent.These polymkeric substance also have the low feature of heat activation temperature, and the activation temperature scope is about 50 ℃～about 95 ℃, and they can improve resistance toheat rapidly above 110 ℃ when not having outside linking agent.
The present invention also comprises water-based sulfonated urethane/acrylic acid or the like or water-based sulfonated polyurethane/vinyl polymer, especially according to the polymkeric substance that utilizes the water reaction that the chain expansion is made mentioned above, wherein disclosed urethane is synthetic in the presence of the ethylene linkage unsaturated monomer, thereby generates the water base blend of useful urethane/acrylic acid or the like or vinyl polymer.These products have reduced the application of volatile organic compounds (VOC), and can generate polymer alloy with strengthening interpenetrating polymer networks, and as tackiness agent, it can improve the physicals of dry film to greatest extent.
The invention still further relates to a kind of method for preparing described dispersion system, wherein the adding temperature of isocyanate functional group's anion polyurethane performed polymer in water is minimum is 60 ℃, and temperature of reaction is at 60 ℃ or be higher than 60 ℃ and keep enough times to carry out fully with the chain expansion reaction of water guaranteeing subsequently.Composition of the present invention can be used for various substrates as tackiness agent, comprise paper, timber, metal, glass, cloth, foams and synthetic polymer, also can be used for other occasion, comprise glass fibre bonding, mould, carpenter, automobile, film lamination, non-woven tackiness agent and be used for the footwear production.
Detailed Description Of The Invention
The isocyanate-terminated base polyurethane prepolymer for use as that is used for dispersion system of the present invention is the reaction product of polyol blends and polymeric polyisocyanate.This polyol blends comprises sulfonated polyester polyol, hydroxycarboxylic acid and low molecular weight diol and optional non-sulfonation polyvalent alcohol.
The sulfonated polyester polyol that is used to form isocyanate-terminated base polyurethane prepolymer for use as can be any polyester polyol that comes the blending sulfonate radical by sulfonation di-carboxylic acid residue and/or sulfonation residue of dihydric alcohol.This sulfonate radical functional group can be sour form or salt form.Suitable salt form is an alkali metal salt or tertiary ammonium salt.Typical described sulfonation di-carboxylic acid residue and/or sulfonation residue of dihydric alcohol are meant a spot of dibasic alcohol and/or two acid moieties of polyester, and its amount preferably accounts for 1.0%～10.0% of weight polyester.The non-sulfonation diacid and the glycol that are used to produce sulfonated polyester can be aromatic series or aliphatic.The example of non-sulfonation diacid comprises hexanodioic acid, nonane diacid, Succinic Acid, suberic acid and phthalic acid.The example of non-sulfonation dibasic alcohol comprises ethylene glycol, ethylene glycol polycondensate (being glycol ether, triglycol, tetraethylene-glycol and various polyoxyethylene glycol), butyleneglycol, butylene glycol, propylene glycol, neopentyl glycol, hexylene glycol, 1,4-cyclohexanedimethanol, 1,2-propylene glycol and 2-methyl isophthalic acid, ammediol.The example of sulfonation diacid comprises sulfoisophthalic acid, 1,3-dihydroxyl fourth sulfonic acid and sulfo-succinic acid.The example of sulfonation dibasic alcohol comprises 1,4-dihydroxyl fourth sulfonic acid and suceinic aldehyde bisulfite disodium salt.
Preferred sulfonated polyester polyol is based on 5-sulfoisophthalic acid one sodium salt, 1,6-hexylene glycol and hexanodioic acid.The example of preferred sulfonated polyester polyol commerical prod is Rucoflex XS-5483-55 and the Rucoflex XS-5536-60 that is produced by Ruco Polymer Company.These sulfonated polyester polyols are based on 5-sulfoisophthalic acid one sodium salt (it is heavy by 4% in XS-5483-55, and is heavy by 6% in XS-5536-60), 1,6-hexylene glycol and hexanodioic acid.
Desirable sulfonated polyester polyol will have about molecular weight of 500～10,000 and about 10～100 ℃ fusing point.Preferred molecular weight ranges is about 1,000～4,000, and preferred fusing point is between 30 ℃～80 ℃, more preferably then between 40 ℃～60 ℃.
The indication molecular weight is a number-average molecular weight herein.
The hydroxycarboxylic acid that is used to generate isocyanate-terminated base polyurethane prepolymer for use as is that chemical formula is (HO)
xR (COOH)
yCompound, wherein R represents to contain the straight or branched alkyl of 1～12 carbon atom, x and y represent 1～3 numerical value.Preferably, this hydroxycarboxylic acid is α, α-dimethylolalkanoic acids, and chemical formula is:
R wherein
1Expression H or be up to the alkyl of about 9 carbon atoms.This examples of compounds is 2,2-dihydroxymethyl acetate, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid and 2,2-dihydroxymethyl valeric acid.Preferred dihydroxyl alkanoic acid is 2,2-dimethylol propionic acid (DMPA).
The low molecular weight diol that is used to generate isocyanate-terminated base polyurethane prepolymer for use as is aliphatic diol, particularly aklylene glycol.Their molecular weight ranges is 60～400.Preferably, this low molecular weight diols is C
2-C
8Aklylene glycol is preferably C
3-C
6Aklylene glycol.The example of described glycol is an ethylene glycol, 1, ammediol, 1, the 4-butyleneglycol (1,4-BD) with 1,6 hexylene glycol.
The polyvalent alcohol component that is used to prepare polyurethane dispersions of the present invention system randomly also comprises the polyvalent alcohol of non-sulfonated polymer, for example the mixture of polyester polyol or polyether glycol or polyester and polyether glycol except that comprising the sulfonated polyester polyol.
The vulcabond that is used to generate isocyanate-terminated base polyurethane prepolymer for use as is vulcabond (HDI) of aromatic diisocyanate, two isocyanic acid isophorone esters (IPDI), hexamethylene glycol and composition thereof.The example of suitable aromatic diisocyanate has phenyl diisocyanate, toluenediisocyanate (TDI), diphenyl diisocyanate, naphthyl vulcabond and diphenylmethanediisocyanate (MDI).
In the polyvalent alcohol component, it is 10～50/0.5～5/0.1～2/0～20 to use that described polyvalent alcohol is suitable for relative weight ratio with sulfonated polyester polyol/hydroxycarboxylic acid/low molecular weight diol/non-sulfonation polyvalent alcohol, and preferred proportion is 20～40/1～3/0.5～1.5/0～10.When generating base polyurethane prepolymer for use as, the NCO base in the vulcabond component is suitable for 1.1～1.9 to the ratio of the OH base in the polyvalent alcohol component: 1, be preferably 1.2～1.6: 1.The NCO content that suitable prepolymer reaction obtains attaches most importance to 1～5%.
Base polyurethane prepolymer for use as can not mix up or in the presence of suitable solvent, is generated by reaction under the temperature of room temperature to 100 ℃, and typical temperature of reaction is 50～80 ℃.If desired, can use catalyzer, such as quaternary ammonium salt or pink salt.Performed polymer with the solvent of water compatible in the presence of can generate well, such as 1-Methyl-2-Pyrrolidone (NMP), dipropylene glycol methyl ether acetic ester (DPMA), methyl ethyl ketone (MEK) or acetone.Yet, at the usage quantity of the solvent of anionic water expansion base polyurethane prepolymer for use as report far below prior art.Suitable solvent will be equivalent to 0～10% of dispersion system weight, be 0.5～7.5% more preferably, most preferably be 1～3%.If wish to disperse the back solvent minimum, solvent can obtain at an easy rate reducing by simple distillation so, normally distillation under reduced pressure.But if the quantity of solvent height, as the method for using prior art, then required solvent distillation needs very complicated and expensive equipment, and still can not remove all solvents.
Performed polymer is scattered in it in water after generating.If sulfonate radical also is not a salt form, and can neutralize with tertiary amine to the carboxylate radical of small part performed polymer, to finish dispersion.Tertiary amine can add with water, but preferred neutralization is to finish before water adds, and tertiary amine is suitable for directly adding in performed polymer/solvent mixture.
Add after the tertiary amine, the acid number of dispersion system should be no more than 15, is preferably lower than 5, more preferably is that tertiary amine surpasses the amount of acidic group so that do not have free acid again when disperseing and exist.
In the method for the invention, thus the use of the selection of vulcabond, dihydroxy carboxylic acids and generate and free isocyanic ester partial hydrolysis in water of performed polymer all is very important with the temperature of finishing each component when addition reaction increases molecular weight at dispersion system.Add in leakage under the situation of carboxylic acid, the use of low levels solvent among the present invention when adding the performed polymer that obtains in the entry, will generate the gel that can not reprocess performed polymer/solvent/water mixture.
Under the situation that temperature is low excessively in dispersion and chain expansion process, a part of polymkeric substance may precipitate when chain expansion reaction.The proposal reactions temperature is minimum to be 60 ℃, is preferably at least 70 ℃, and the reaction times is 0.5～10hr, is preferably 1～3hr, most preferably is about 2hr.Can produce carbonic acid gas in the chain expansion reaction process, the pH value of dispersion system descends thereupon.Concerning the dispersion system that only contains the carboxylate anion group, the decline of this pH value can cause polymer precipitation.Yet in preparaton of the present invention, as long as temperature is being kept the sufficiently long time more than 60 ℃ or 60 ℃, dispersion system will be stable.It is believed that the shortest time is to finish the water isocyanate reaction and the chain self-propagation reacts the needed time.Do not advise that elevated temperature shortens the transfer reaction time, react too fast when surpassing 90 ℃ because heat up, the carbon dioxide gas cognition of emitting causes bad foamy to generate.After transfer reaction was finished, dispersion system was stable, was cooled to room temperature and can produce precipitation, gelling or foaming.
Composition of the present invention can be applied in substrate and the drying or slightly before this, obtain crosslinked by adding linking agent to dispersion system.The available linking agent comprises isocyanic ester, melamine resin, Resins, epoxy, Costumes azoles quinoline.In some cases, these polyisocyanate crosslinking agents may be not suitable for this purposes, because this polymkeric substance is few or do not have a terminal amido., crosslinkedly still can carboxylate radical be imported in the sulfonated polyurethane polymkeric substance and finish by the hydroxycarboxylic acid component of polyvalent alcohol component.These carboxylate radicals can react with the carboxylic acid active crosslinker, and the latter at room temperature has reactive behavior, such as polyfunctional group aziridine cpd, zinc carbonate ammonium, zirconium carbonate or polyfunctional group carbodiimide compound.Typically, linking agent adds with heavy 1～10% amount.
In WO 96/07540, it is reported that the resistance toheat of the hydration diamines expansion polyurethane dispersions system of this purposes is significantly improved by use low molecular weight diol in generating base polyurethane prepolymer for use as.In fact, in a preferred embodiment of the invention, the resistance toheat of polyether polyols with reduced unsaturation obtains by means of low molecular weight diol so significantly improving, thus without the commercial dispersion agent stick of the single-component sizing composition use linking agent compared to prior art of linking agent can Nai Genggao temperature.Surprisingly, single-component composition of the present invention even ratio have better resistance toheat in 96/07540 li disclosed similar formulations with the diamine compound expansion of WO.
The advantage and the low activation temperature of high heat resistance obtain simultaneously.In the bonding application of film, have or the dispersion agent stick of cross-linking agent-free is applied on the netted substrate of film and dry, after being heated, put second netted substrate of film.Described Heating temperature (being meant activation temperature in the art) is chosen as the temperature that excellent adhering can be provided; thereby make bonding second reticulation of tackiness agent energy; and by increase physics or chemically crosslinked change the physicals of tackiness agent; so that the tackiness agent after the heating has higher thermotolerance before heating, also has better water-fast and solvent resistance in addition usually.Usually need higher temperature to change by hope, and be not only to guarantee that tackiness agent is wetting preferably to reach on the tackiness agent resistance toheat.Unexpectedly, preferred single-component aqueous polyurethane dispersion agent stick not only has high heat resistance, and is like this too under low heat activation temperature.Even if preparation of the present invention also demonstrates effective resistance toheat low the reaching under 125 the situation of cross-linking agent-free and activation temperature.
According to the present invention, it is little and the characteristics of satisfactory stability are arranged in wide ph range (3～11) very that aqueous polyurethane dispersion system also has a particle diameter.
High green strength under low activation temperature and high heat resistance make single-component of the present invention or two component composition particularly useful in automobile, aerospace, footwear material gummed, wood working, book-binding, glass fibre bonding and film laminating are used.For example, a kind of single-component composition described in embodiment 1,2,3 and 10 hereinafter can be used for automotive industry basically, under about 102 ℃ activation temperature polypropylene foam is adhered on the polyvinyl chloride; Under the activation temperature of room temperature to 99 ℃ with DuPont Tedlar
Fluorinated ethylene propylene is adhered on the phenolic composite, can be used for aerospace; With leather bonds (66～77 ℃ of activation temperatures) to styrene-butadiene rubber(SBR), that highly plasticized polyvinyl chloride self is bonding or it is adhered to (66～77 ℃ of activation temperatures) can be used for shoe industry on other substrate; Polyvinyl chloride is adhered to (66 ℃ of activation temperatures) can be used for wood-processing industry on the fiberboard of intermediate density; Be used for book-binding under the activation temperature of room temperature to 93 ℃, paper being glued together; With Tedlar
Be adhered on polyvinyl chloride, timber, wood composites, recirculation timber and/or the paper product and be used for siding; And be used for pet film is laminated to (activation temperature is 52～66 ℃) on polypropylene, polyethylene or aluminium foil or other sheet metal.
Preparation of the present invention and other aqueous-based polymers dispersion system have good consistency, even as the same with the dispersion system of those low pH values (the pH value is 4～7).This consistency makes preparation of the present invention useful with the dispersion system of acrylic polymers, epoxy polymer and vinyl-acetic ester or other vinyl polymer and other polyether polyols with reduced unsaturation dispersion system blend the time.Can be used for shoemaking and adhesive glass fiber with the blend of water-based acrylic base polymer.Can be used among automobile, wood working and the book-binding with the blend of vinyl-acetic ester or other vinyl polymer dispersion system.
If require even higher thermotolerance, can add outside cross-linking reagent.The resistance toheat of the gluing preparation of two components that obtains surpasses about 140 ℃, and thermotolerance is measured by the stripping test of T type.
The present invention is described further by following non-limiting example, and wherein all umbers and per-cent then all refer to weight ratio as not illustrating in addition.
The embodiment thermotolerance
Go up by the clean polyvinyl chloride film (polyvinyl chloride that provides by the Laird Plastics Company) that will have or the dispersion system of cross-linking agent-free is coated onto 10 mil thick by #28 Mylar rod that (primer of 1 * 1inch) area records the resistance toheat of embodiment 1～5 and 10～12 li described urethane dispersion agent sticks thus to obtain 2.5 * 2.5cm on the wide fillet of the 2.5cm of polyvinyl chloride film.Treat that tackiness agent does after can touch, the polyvinyl chloride film that scribbles primer is cut into 2.5 * 5cm (fillet of 1 * 2inch).The fillet that has been coated with primer is to be heat sealed under the 345kPa (50psi) on another 2.5 * 5cm polyvinyl chloride fillet that is not coated with primer with the Sentinal heat sealing machine at nip pressure, and the dwell time is 30 seconds.The seal temperature of selecting (activation temperature) is as listed in each specific embodiment.Measure heat resisting temperature after bonding 7 days.
The load of 100g is applied on each polyvinyl chloride bonding coat with T type lift-off structure, is placed on then in the Tenney baking oven.This T type lift-off structure has 1 square inch bond area.T type lift-off structure is with per hour 25 ℃ of speed intensifications, up to reaching 127 ℃ (260 °F).Temperature is broken away from up to bonding coat by the Tenney sensor record.Green strength
The green strength of being reported in the embodiment 10-12 has been stated stacked the obtaining of polyvinyl chloride thin plate that method is prepared into by adopting.Use the speed measurement stripping strength of Intelet 500 instrument with per minute 30.5cm (12inches).Measure green strength behind the thin plate heat-sealing 15min.Bond strength
The bond strength of being reported in the embodiment 10-12 records as green strength, except keeping bonding 7 days before measuring stripping strength.Shortenings
Following shortenings is used for embodiment:
One kind of Rucoflex XS-5483-55 based on 5-sulfoisophthalic acid one sodium salt, oneself
Diacid and 1, the sulfonated polyester polyol of 6-hexylene glycol,
Its OH value is 49.0
The DMPA dimethylol propionic acid
1,4-BD 1, the 4-butyleneglycol
IPDI two isocyanic acid isophorone esters
The vulcabond of HDI hexamethylene glycol
The EDA quadrol
The TEA triethylamine
Embodiment 1-5
In embodiment 1-5, activation temperature is 66 ℃ (150 °F).Prescription:
The method that is used for embodiment 1-3:
| Embodiment | ????1 | ????2 | ????3 | 4 (contrasts) | 5 (contrasts) |
| Rucoflex?XS-5483-55 | ?213.8 | 213.8 | ?213.8 | ????213.8 | ????213.8 |
| DMPA | ?10.05 | 10.05 | ?10.05 | ????10.05 | ????10.05 |
| 1，4-BD | ?11.25 | 11.25 | ?11.25 | ????11.25 | ????11.25 |
| IPDI | ?31.08 | 31.08 | ?31.08 | ????31.08 | ????31.08 |
| HDI | ?47.04 | 47.04 | ?47.04 | ????47.04 | ????47.04 |
| TEA | ?6.0 | 6.0 | ?12.0 | ????6.0 | ????6.0 |
| EDA | ?0 | ?0 | ?0 | ????6.48 | ????2.16 |
| Acetone | ?70.0 | ?28.7 | ?18.1 | ????70.0 | ????70.0 |
| Water | ?604.3 | ?554.3 | ?585.4 | ????604.3 | ????604.3 |
60～70 ℃ with Rucoflex-XS-5483-55, DMPA and 1, the 4-BD fusion also mixes.Add IPDI, HDI and acetone, subsequently temperature was kept 3 hours at about 70 ℃.Under this temperature, adding TEA also stirred 10～15 minutes.By adding entry the performed polymer that obtains is disperseed.The performed polymer dispersion system was 65 ℃ of restir 2 hours.Thereby obtain disperse phase in small, broken bits.The method that is used for embodiment 4-5 (comparison example):
60～70 ℃ with Rucoflex-XS-5483-55, DMPA and 1, the 4-BD fusion also mixes.Add IPDI, HDI and acetone, subsequently temperature was kept about 3 hours at about 70 ℃.Under this temperature, adding TEA also stirred 10～15 minutes.The water of adding 554.3 disperses performed polymer.After 60 minutes, EDA adds with 50.0g water.Thereby obtain disperse phase in small, broken bits.The character of embodiment 1-5:
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 |
| Solid % | ????32.1 | ????35.4 | ????35.0 | ????33.0 | ????34.0 |
| pH | ????7.1 | ????7.2 | ????7.3 | ????10.0 | ????7.8 |
| Viscosity (cps) | ????125 | ????45 | ????15 | ????450 | ????350 |
| Particle diameter (mm) | ????150 | ????145 | ????180 | ????170 | ????160 |
| (t-peels off resistance toheat, pvc/pvc) | Just lost efficacy up to 260 °F (127 ℃) | Just lost efficacy up to 260 °F (127 ℃) | Just lost efficacy up to 260 °F (127 ℃) | ????210°F ????(99℃) | ????235°F ????(113℃) |
Except the amount of 1 li no EDA of embodiment (diamine chain spreading agent) and embodiment 4 and 5 li EDA changed, embodiment 1 and comparison example 4 and 5 were by identical forming.Last table shows that when the amount of EDA reduced, thermotolerance rose.The aqueous polyurethane performed polymer dispersion system of no chain spreading agent has the highest resistance toheat.This is the result that prior art is never pointed out.
Embodiment 6 (comparison example) starting materials:
Ten thousand methods:
| Rucoflex?XS-5483-55 | ????213.8 |
| ?1，4-BD | ????6.75 |
| ?IPDI | ????18.13 |
| ?HDI | ????27.44 |
| Acetone | ????15.2 |
| Water | ????479.0 |
Rucoflex XS-5483-55 and 1,4-BD is 45～50 ℃ of mixing.Under this temperature, add IPDI and HDI.Temperature rises to 70 ℃ and kept 2 hours, rises to 80 ℃ more then in 0.5 hour.Under this temperature, add the water that is preheated to 80 ℃ performed polymer is disperseed, mixture is gelation immediately.This preparation does not contain the hard segment anionic group.
Embodiment 7-9 starting materials:
| Embodiment | 7 (contrasts) | 8 (contrasts) | ????9 |
| ?Rucoflex?XS-5483-55 | ????213.8 | ????213.8 | ????213.8 |
| ?DMPA | ????10.05 | ????10.05 | ????10.05 |
| ?1，4-BD | ????11.25 | ????11.25 | ????11.25 |
| ?IPDI | ????31.08 | ????31.08 | ????31.08 |
| ?HDI | ????47.04 | ????47.04 | ????47.04 |
| ?TEA | ????6.0 | ????6.0 | ????6.0 |
| Acetone | ????18.1 | ????18.01 | ????18.1 |
| Water | ????604.3 | ????604.3 | ????604.3 |
| The dispersion system temperature (℃) * | ????50 | ????65 | ????80 |
| Precipitation capacity | ????10％ | ????5％ | Do not have |
*The dispersion system temperature: performed polymer and water rise to a specified temp and kept 2 hours under this temperature before mixing.
Embodiment 7-9 has illustrated the importance that keeps sufficiently high temperature when the performed polymer of isocyanate-functional and water reaction.
Embodiment 10 starting materialss:
Ten thousand methods:
| Rucoflex?XS-5483-55 | ????213.8 |
| ?DMPA | ????10.05 |
| ?1，4-BD | ????6.75 |
| ?IPDI | ????25.9 |
| ?HDI | ????39.2 |
| ?TEA | ????8.0 |
| Acetone | ????17.4 |
| Water | ????546.7 |
60～70 ℃ with Rucoflex XS-5483, DMPA and 1, the 4-BD fusion also mixes.Add IPDI, HDI and acetone, about 70 ℃ of insulations 2 hours, in 0.5 hour, be warming up to 80 ℃ then subsequently.Under this temperature, adding TEA also stirred 10 minutes.Adding the water that is preheated to 80 ℃ disperses performed polymer.Under 60 ℃ with performed polymer dispersion system restir 2 hours.
Obtain a kind of dispersion system in small, broken bits, its solids content is 35.0%, and viscosity is 200cps, and particle diameter is 150nm, and the pH value is 7.2.Character:
| Activation temperature (℃) | ????52 | ????66 | ????79 | ????93 |
| Green strength (T-peels off, kg/cm, PVC/PVC) | ????2.4 | ????2.8 | ????3.9 | ????5.5 |
| Bond strength (T-peels off, kg/cm, PVC/PVC) | ????SF | ????SF | ????SF | ????SF |
| Heat resisting temperature (℃) (T-peels off, 100g load, PVC/PVC | ????＞127 | ????＞127 | ????＞127 | ????＞127 |
SF: substrate lost efficacy
Embodiment 11﹠amp; 12 starting materialss:
The method of embodiment 11:
| Embodiment | ????11 | 12 (contrasts) |
| ?Rucoflex?XS-5483-55 | ????213.8 | ????213.8 |
| ?DMPA | ????10.05 | ????10.05 |
| ?IPDI | ????18.1 | ????18.1 |
| ?HDI | ????27.4 | ????27.4 |
| ?TEA | ????8.0 | ????8.0 |
| ?EDA | ????0.00 | ????3.15 |
| Acetone | ????15.9 | ????15.9 |
| Water | ????699.2 | ????699.2 |
At 60～70 ℃ Rucoflex XS-5483-55 and DMPA fusion are also mixed.Add IPDI, HDI and acetone, about 70 ℃ of insulations 2 hours, in 0.5 hour, be warming up to 80 ℃ then subsequently.Under this temperature, adding TEA also stirred 10 minutes.Adding is preheated to 80 ℃ water, and performed polymer is disperseed.At 60 ℃ with performed polymer dispersion system restir 2 hours.
Obtain a kind of dispersion system in small, broken bits, its solids content is 29.8%, and viscosity is 1500mPas, and particle diameter is 180nm, and the pH value is the method for 7.1 embodiment 12 (comparison example):
As preparation performed polymer as described in the embodiment 11, and neutralize with TEA.Adding is preheated to 80 ℃ water (not enough 50g), and performed polymer is disperseed.After 30 minutes, EDA is dissolved in adding together in the 50g water.
Obtain a kind of dispersion system in small, broken bits, its solids content is 29.8%, and viscosity is 1200mPas, and particle diameter is 190nm, and the pH value is 8.5.Embodiment 11 and 12 character:
SF: substrate lost efficacy
| Activation temperature (℃) | ????52 | ????66 | ????79 | ????93 |
| (T-peels off green strength, kg/cm, PVC/PVC) embodiment 11 embodiment 12 | ????1.7 ????2.3 | ????SF ????SF | ????SF ????SF | ????SF ????SF |
| (T-peels off bond strength, kg/cm, PVC/PVC) embodiment 11 embodiment 12 | ????4.8 ????5.2 | ????8.8 ????9.4 | ????11.6 ????11.6 | ????11.6 ????12.3 |
| Heat resisting temperature (℃) (T-peels off, the 100g load, PVC/PVC) embodiment 11 embodiment 12 | ????＞127 ????100 | ????＞127 ????100 | ????＞127 ????101 | ????＞127 ????100 |
Embodiment 13
Present embodiment has been described a kind of gluing preparation that is used for automotive industry, and it can be used for ethenoid resin is adhered on the polyolefin foam.
With 0.16g ammoniacal liquor the pH value of 32.88g Airflex 426 is adjusted to 6.6, wherein Airflex426 is by aeronautical product and chemical company (Air Product﹠amp; Chemicals) a kind of vinyl-acetic ester-ethylene copolymer that provides.Polymer blending described in this material and the 56 76g embodiment 1, with 2.2g Alcogum 296W thickening, mix with 2.5g Desmodur DA then, wherein Desmodur DA is a kind of many functional group isocyanates who is scattered in the water who is provided by Bell Co. (Bayer Corporation).With #60 Meyer rod gluing mixture is applied on the polypropylene foam that the corona treatment of 5.5 * 6.0 inches of a slices crosses, then in baking oven 100 ℃ dry about 3 minutes down.The foams of this adhesive coated support ethenoid resin (by Canadian General Tower and O ' Sullivan supply) with the nothing of 5.5 * 6.0 inches of a slices and cooperate, then with Fred Carver compressor extruding 60 seconds, wherein go up plate temperature and be about 105 ℃ of thin plates at room temperature aging 3 days, be cut into the fillet of 2.54 * 2.54cm then and test the creep thermal resistance.Under separation mode, 450g weight is added to an end of sample, it was placed 1 hour in 100 ℃ baking oven, measure creep.Under the described conditions, gluing preparation does not show the creep sign.Further, place after 66 hours, this material still can creep resistance under 140 ℃, thereby demonstrates effectiveness of the present invention.
Embodiment 14
Present embodiment is described a kind of sizing composition that uses sulfonated polyurethane/acrylate copolymer, and it can be used for shoe industry.
In reactor, add 213.8g (0.21 hydroxyl equivalent) fusion Rucoflex XS-5483-55 (a kind of sulfonated polyester polyol that provides by Ruco company), 10.05g (0.15 hydroxyl equivalent) dimethylol propionic acid, 6.75g (0.15 hydroxyl equivalent) 1,4-butyleneglycol, 37.97g methyl methacrylate and 37.97g butyl acrylate.This mixture heating up to 55 ℃ adds 25.9g (0.23 isocyanurate equivalent) isophorone diisocyanate and 39.2g (0.46 isocyanurate equivalent) 1,6-two isocyanato-hexanes then.Mixture was about 3 hours of 70 ℃ of heating.Isocyanate-terminated sulfonated polyurethane performed polymer/monomer mixture adds 8.0g (0.8 mole) triethylamine again and stirred 10 minutes.Performed polymer is scattered in the 554.5g deionized water.In 10 minutes, add the solution that contains 0.20g ammonium persulphate and 20g deionized water to dispersion system.Be heated to 80 ℃ about 3 hours, the free radical emulsion polymerization is finished.Character aqueous and the exsiccant polymkeric substance is as described below:
PH value=7.7
Viscosity=900mPas
Effective diameter=228nm
Mean diameter=494nm bond test:
Be applied on the polyvinyl chloride (PVC) sheets of untreated, pressurization and polishing with No. 40 Meyer rods sample that will wet, and at room temperature dry 24 hours.Place second polyvinyl chloride on the dried glue and cut into the fillet of 2.54cm * 15.24cm.Use Sentinel
The heat seal machine, every square centimeter loads 3.515kg, lasts 30 seconds, at various temperatures with each fillet thermal activation.At room temperature aging after 24 hours and 168 hours, use Intellect
180 ° of peel value of 500 test fillets.It is as follows that the result provides:
The SF=substrate lost efficacy
| Storage period | ????51.6℃ | ????65.5℃ | ????79.4℃ | ????93.3℃ |
| 24 hours | ????21.1Kg/cm | ????3.0Kg/cm | ????4.4Kg/cm | ????5.3Kg/cm |
| 168 hours | ????3.2Kg/cm | ????SF | ????SF | ????SF |
Adopt 180 ° of release adhesive invalid temperatures of following program test:
Wet preparation is applied on polyvinyl chloride (PVC) sheet of untreated, pressurization and polishing at room temperature dry 24 hours with No. 40 Meyer rods.Place second PVC on the dried glue and be cut to the fillet of 2.54 * 15.24cm.Use Sentinel
Heat sealing machine, every square centimeter loads 3.515kg, lasts for 30 seconds, takes differing temps to make each fillet thermal activation.After at room temperature placing 7 days, fillet is inserted Tenny
Baking oven adopts 0.1kg weight, per hour heats up 25 ℃ till adhesion failure.Adhesion failure temperature Tenny
The baking oven sensor record can be up to 126 ℃.It is as follows that the result provides:
| Heat activation temperature | ??51.6℃ | ??65.5℃ | ??79.4℃ | ??93.3℃ |
| Invalid temperature | ??58.7℃ | ??＞126℃ | ??＞126℃ | ??＞126℃ |
Claims (40)
1. the aqueous dispersion of an anion polyurethane is, this urethane comprises the reaction product of isocyanate-terminated base polyurethane prepolymer for use as and water, base polyurethane prepolymer for use as comprises the reaction product of a kind of polyol component and a kind of vulcabond component, and this polyol component comprises:
A kind of sulfonated polyester polyol,
Chemical formula is (HO)
xR (COOH)
yHydroxycarboxylic acid, wherein (R) expression contains the straight or branched alkyl of 1～12 carbon atom, x and y represent 1～3 numerical value and as optional components
Molecular weight be 60～400 lower molecular weight aliphatic diol and
Non-sulfonated polymer polyvalent alcohol,
The vulcabond component is selected from the vulcabond of aromatic diisocyanate, isophorone diisocyanate, hexamethylene glycol and their mixture.
2. dispersion system as claimed in claim 1, wherein the lower molecular weight aliphatic dihydroxy alcohol exists and is C
2～C
8Aklylene glycol.
3. dispersion system as claimed in claim 2, wherein the lower molecular weight aliphatic dihydroxy alcohol is an ethylene glycol, 1, ammediol, 1,4-butyleneglycol or 1,6-hexylene glycol.
4. dispersion system as claimed in claim 1, wherein sulfonated polyester polyol is a kind of hydroxy-terminated polyester that is formed by the residue that at least a carboxylic diacid, at least a dibasic alcohol and at least a sulfonation diacid or sulfonation glycol obtain.
5. dispersion system as claimed in claim 4, wherein the carboxylic diacid residues of sulfonated polyester polyol comprises the diacid residues that is selected from adipic acid, nonane diacid, Succinic Acid, suberic acid and phthalic acid.
6. dispersion system as claimed in claim 4, wherein the diol residue of sulfonated polyester polyol comprises and is selected from ethylene glycol, ethylene glycol condenses, butyleneglycol, butylene glycol, propylene glycol, neopentyl glycol, hexylene glycol, 1,4-cyclohexanedimethanol, 1,2-propylene glycol and 2-methyl isophthalic acid, the residue of dihydric alcohol of ammediol.
7. dispersion system as claimed in claim 4, wherein sulfonation diacid or sulfonation diol residue comprise and are selected from sulfoisophthalic acid, sulfo-succinic acid, 1, at least a residue in 4-dihydroxyl fourth sulfonic acid and the suceinic aldehyde bisulfite disodium.
8. dispersion system as claimed in claim 1, wherein sulfonated polyester polyol is based on 5-sulfoisophthalic acid one sodium salt, 1,6-hexylene glycol and hexanodioic acid.
9. dispersion system as claimed in claim 1, wherein the number-average molecular weight of sulfonated polyester polyol is about 500～10,000, melt temperature is about 10～100 ℃.
10. dispersion system as claimed in claim 9, wherein number-average molecular weight is about 1,000～4,000, melt temperature is about 40 ℃～60 ℃.
11. dispersion system as claimed in claim 1, wherein hydroxycarboxylic acid is α, α-dimethylolalkanoic acids, and chemical formulation is as follows:
R wherein
1Expression H or be up to the alkyl of about 9 carbon atoms.
12. dispersion system as claimed in claim 11, α wherein, α-dimethylolalkanoic acids is selected from 2,2-dihydroxymethyl acetate, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxymethyl valeric acid and composition thereof.
13. dispersion system as claimed in claim 12, α wherein, α-dimethylolalkanoic acids is 2, the 2-dimethylol propionic acid.
14. dispersion system as claimed in claim 1, wherein polyol component comprises described non-sulfonated polymer polyvalent alcohol, and described non-sulfonated polymer polyvalent alcohol is selected from non-sulfonated polyester polyol, non-sulfonated polyether polyvalent alcohol and composition thereof.
15. dispersion system as claimed in claim 1, the polyalcohols material in the wherein said polyol component uses with following relative weight ratio: sulfonated polyester polyol/hydroxycarboxylic acid/low molecular weight diol/non-sulfonation polyvalent alcohol=10-50/0.5-5/0.1-2/0-20.
16. dispersion system as claimed in claim 15, the polyalcohols material in the wherein said polyol component uses with following relative weight ratio: sulfonated polyester polyol/hydroxycarboxylic acid/low molecular weight diols/non-sulfonation polyvalent alcohol=20-40/1-3/0.5-1.5/0-10.
17. dispersion system as claimed in claim 1, wherein base polyurethane prepolymer for use as be described polyol component and vulcabond component in the NCO base is the product of 1.1～1.9: 1 reaction to the ratio of OH base.
18. dispersion system as claimed in claim 17, wherein base polyurethane prepolymer for use as is that described polyol component and vulcabond component are the product of 1.2～1.6: 1 reaction in the NCO base to OH base ratio.
19. by a kind of gluing preparation that dispersion system as claimed in claim 1 and the blend of acid activity linking agent are made.
20. gluing preparation as claimed in claim 19, wherein linking agent is selected from polyfunctional group aziridine, zinc carbonate ammonium and zirconium carbonate.
21. by a kind of gluing preparation that dispersion system as claimed in claim 1 and polyisocyanate crosslinking agent blend are made.
22. the adherent assembly of a pair of substrate, described assembly is bonding with the tackiness agent of the exsiccant dispersion system that comprises claim 1.
23. bonded assemblies as claimed in claim 22, wherein substrate is to comprising a member of being made up of a kind of material that is selected from following substances: polypropylene, polyvinyl chloride, phenol matrix material, leather, styrene-butadiene rubber(SBR), fiberboard, paper, fluorinated ethylene propylene, timber, wood composites, recirculation timber, polyethylene terephthalate, polyethylene and metal
24. bonded assemblies as claimed in claim 22, wherein this tackiness agent is made up of described urethane basically.
25. bonded assemblies as claimed in claim 22, wherein this tackiness agent also comprises at least a in acrylate copolymer, epoxy polymer, vinyl polymer or another polyether polyols with reduced unsaturation
26. bonded assemblies as claimed in claim 22, wherein this tackiness agent also comprises a kind of linking agent.
27. bonded assemblies as claimed in claim 22, wherein this substrate is to being selected from polypropylene foam/polyvinyl chloride, fluorinated ethylene propylene/phenol matrix material, leather/styrene-butadiene rubber(SBR), PVC/ fiberboard, paper/paper, fluorinated ethylene propylene/polyvinyl chloride, fluorinated ethylene propylene/timber, fluorinated ethylene propylene/wood composites, fluorinated ethylene propylene/recirculation timber, fluorinated ethylene propylene/paper product, polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polyethylene terephthalate/metal and plastifying polyvinyl chloride/plastifying polyvinyl chloride.
28. by a kind of gluing preparation that at least a blend in the described dispersion system of claim 1 and acrylic polymers, epoxy polymer, vinyl polymer or another polyether polyols with reduced unsaturation is made.
29. prepare the method for anion polyurethane aqueous dispersion system, this urethane comprises the reaction product of isocyanate-terminated base polyurethane prepolymer for use as and water, described method comprises:
The base polyurethane prepolymer for use as for preparing a kind of isocyanate-functional, the free isocyanic ester weight content of this base polyurethane prepolymer for use as is 1～5%, and it comprises the reaction product of polyol component and vulcabond component, and this polyol component comprises:
A kind of sulfonated polyester polyol and
Chemical formula is (HO)
xR (COO)
yHydroxycarboxylic acid, wherein (R) expression contain 1～12
The straight or branched alkyl of individual carbon atom, x and y represent 1～3 numerical value,
This vulcabond component is selected from vulcabond of aromatic diisocyanate, isophorone diisocyanate, hexamethylene glycol and composition thereof;
With poly-aggressiveness minimum be to be scattered in the sufficiently long time in the aqueous dispersion media of no primary amine or secondary amine under 60 ℃ the temperature, to allow all basically isocyanic ester to be reacted away in reaction, performed polymer is by obtaining the chain self-propagation with the water reaction in described reaction.
30. the method for claim 29, wherein also to comprise molecular weight be 60～400 lower molecular weight aliphatic diol to polyol component,
31. the method for claim 29, wherein polyol component also comprises a kind of non-sulfonated polymer polyvalent alcohol.
32. the water-based sulfonated polyurethane adhesive of an improvement, it is included in the aqueous dispersion system that there is the sulfonated polyurethane polymkeric substance that forms down at least a ethylene linkage unsaturated monomer.
33. composition as claimed in claim 32, wherein said ethylene linkage unsaturated monomer is selected from methyl methacrylate, butyl acrylate and composition thereof.
34. composition as claimed in claim 33, wherein this ethylene linkage unsaturated monomer forms back generation radical polymerization at this sulfonated polyurethane, thereby generates a kind of water-based sulfonated urethane/propylene interpenetrating(polymer)networks.
35. composition as claimed in claim 34, wherein said composition is characterised in that dried glue heat activation temperature scope is about 50 ℃～about 95 ℃ and adherend is heat-resisting surpasses 110 ℃.
36. composition as claimed in claim 33, it also comprises at least a multi-group crosslink agent who is scattered in water.
37. composition as claimed in claim 36, wherein this linking agent is selected from isocyanic ester, aziridine, melamine resin, Resins, epoxy, Costumes azoles quinoline, carbodiimide, zinc carbonate ammonium and zirconium carbonate.
38. composition as claimed in claim 37 wherein is 100 parts with said composition and makes benchmark, the amount of this linking agent in composition attached most importance to about 1 part to about 10 parts.
39. composition as claimed in claim 33, it also comprises at least a polymkeric substance or the multipolymer that is scattered in the water, and the monomer of this polymkeric substance or multipolymer is selected from acrylic acid or the like, epoxide, vinyl-acetic ester and composition thereof.
40. a footwear product has a kind of tackiness agent, dope layer or primer layer at it above at least a portion, this layer comprises a kind of polyether polyols with reduced unsaturation, and this polyether polyols with reduced unsaturation is the product of following substances reaction:
A) at least a polymeric polyisocyanate;
B) at least a aklylene glycol;
C) at least a sulfonated polyester polyol, wherein sulfo group exists with alkali metal salt; With
D) at least a dihydroxy carboxylic acids or its salt, described salt is selected from an alkali metal salt, trimethylamine salt and composition thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194623A CN1189171A (en) | 1995-06-07 | 1996-06-07 | Aqueous non-gelling anionic polyurethane dispersions and process for their manufacture |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/480,780 | 1995-06-07 | ||
| US08/561,197 | 1995-11-21 | ||
| CN96194623A CN1189171A (en) | 1995-06-07 | 1996-06-07 | Aqueous non-gelling anionic polyurethane dispersions and process for their manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1189171A true CN1189171A (en) | 1998-07-29 |
Family
ID=5128745
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194623A Pending CN1189171A (en) | 1995-06-07 | 1996-06-07 | Aqueous non-gelling anionic polyurethane dispersions and process for their manufacture |
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| CN (1) | CN1189171A (en) |
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| CN101173031B (en) * | 2006-11-01 | 2010-11-03 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
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| CN101803806B (en) * | 2010-03-08 | 2015-08-19 | 侯怡妤 | elastic protector |
| CN102140734B (en) * | 2011-01-10 | 2012-12-19 | 武汉理工大学 | Enhanced bi-component nanofiber porous membrane and preparation method thereof |
| CN102140734A (en) * | 2011-01-10 | 2011-08-03 | 武汉理工大学 | Enhanced bi-component nanofiber porous membrane and preparation method thereof |
| CN106350622A (en) * | 2016-09-30 | 2017-01-25 | 光山县博正树脂有限公司 | Cattle hide treatment agent and preparation method thereof |
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