CN1144813A - Hypoallergenic coating composition for latex rubber gloves - Google Patents
Hypoallergenic coating composition for latex rubber gloves Download PDFInfo
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- CN1144813A CN1144813A CN 95117179 CN95117179A CN1144813A CN 1144813 A CN1144813 A CN 1144813A CN 95117179 CN95117179 CN 95117179 CN 95117179 A CN95117179 A CN 95117179A CN 1144813 A CN1144813 A CN 1144813A
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Abstract
Disclosed are aqueous dispersions of polyurethane polymers from which films can be formed which have enhanced hydrophilicity. The enhanced hydrophilicity is provided by hydrophilic moieties chemically inorporated in the polymer network.
Description
The present invention relates to aqueous polymer composition, especially relate to the polyurethane aqueous dispersion body of the product (particularly film and the coating on any suitable matrix) that can produce water-fast and organic solvent-resistant effectively.In addition, the invention still further relates to method and the using method thereof of making described dispersion, and can be from the film and the coating of described dispersion production.
The present invention especially relates to the polyurethane-base water dispersion, and wherein polymeric constituent contains the substituting group that can give film and coating hydrophilic, and this film and coating are that the dispersion by described polymer product forms.Useful especially embodiment related to the present invention is that requirement film and coating present low friction slippage; An example of this category feature provides the coating of surgical glove the inside.Urethane has been found to be widely used in the coating of fiber, plastics, timber, metal etc., because their desirable properties, and for example excellent in chemical resistance, erosion resistant, toughness, elasticity and weather resistance, and can solidify rapidly.Described coating is to use with the solution in polarity or aromatic solvent naturally, or uses with aqueous dispersion.The application of water dispersion is more and more welcome, escapes into the latency environment harm that interrelates in the atmosphere in order to avoid financial loss with solvent vapo(u)r, and the latter can not easily or economically reclaim.
Usually tend to have high hydrophobicity at film that forms by solution in organic solvent or the dispersion in the hydrophily agent on the stromal surface and coating, even after polyether polyols with reduced unsaturation is shaped, give coating with certain degree flexibility or during elasticity.Certainly, this hydrophobicity usually is in demand character.Yet, in many application, wish many character that film performance urethane is given prominence to, it comprises above-mentioned chemically-resistant etch, corrosion-resistant, toughness, weather resistance and curing are rapid, but, film or coating performance wetting ability, soon water or other polarity and/or hydrophilic substance accumulate in the avidity on the solidified polyurethane-base polymer surfaces.Described wetting ability will be desirable, for example in some applications, wherein solidified polyether polyols with reduced unsaturation primary surface will (for example contact with other surface, static, roll or sliding contact), and wherein in addition the interface between polyether polyols with reduced unsaturation primary surface and other surface may have less water or other polar liquid.Therefore, two surfaces any tendency bonded to each other (described herein bonding be unwanted) may reduce or avoid fully therefrom.
Have one to be the wetting ability that wish to increase the polyether polyols with reduced unsaturation primary surface in the middle of in many examples, this example is to belong to the rubber gloves field, it be in family, factory and the medical specialty common fittings.Be designed to finger, thumb and hand fit quite closely gloves be that suitable difficulty puts, be because due to the frictional resistance between gloves internal surface and the skin.This difficulty can be increased when for example natural rubber latex or other synthetic polymer (being homopolymer or multipolymer) elastomerics are made by resilient material when gloves.When the internal surface of hand or gloves when being moist or wet, this difficulty can further increase.Traditional practice attempt reduces these difficulties by using dried particle lubricant such as talcum powder or starch, and described lubricant was used in the internal surface of gloves before carrying gloves, or on hand, or the both adopts.These reagent increase the cost of products, and the danger that causes particle to drop on adjacent area from gloves, and when putting in gloves are being had an operation by the surgeon, its consequence is catastrophic, when wearer at home or when working in the factory, also are inconvenient.In addition; described particle lubricant can not form an effective barrier between skin and gloves internal surface; and one deck barrier is arranged is utmost point needs; so that the protection person of having on exempts from the danger that (be present in many resilient materials, comprise the known of natural rubber latex Ruzhong) contact hypersensitivity reagent place produces.
The inventor has confirmed can give polyether polyols with reduced unsaturation base product and the hydrophilic advantage of its cast film by some technology (giving reagent according to this technology with wetting ability introduces in the polyether polyols with reduced unsaturation with chemical mode).
The US patent No. 5088125 open gloves of making by a kind of supersensitivity elastomerics, and provide a kind of ionic polyurethanes on the surface within it.This ion part is preferably by allowing suitable prepolymer and the chain extension agent reaction that contains ionic species be attached in the polyether polyols with reduced unsaturation, ionic polyurethanes can comprise a kind of second polymkeric substance, it may be another kind of ion urethane or may be derived and come by acrylic or methacrylic acid or its ester, so its hardness can change by the comonomer of introducing such as hydroxyethyl methylacrylate, methyl methacrylate or vinylformic acid to the acrylic acid/esters polymkeric substance.The ionic polyurethanes that uses in described application has following shortcoming: for stromal surface, for example the internal surface of rubber gloves may have poor binding property, do not have ability give enough low coefficient of friction between the film that forms and the second surface.In addition, the existence of ionised species can exist the danger that a kind of and other ionic compound carry out unwanted reaction, and the phase comes in contact the sort of ion urethane during use.
The US patent No. 4,575,476 and U.S patent 3,813,695 disclose rubber and latex glove, and its internal surface and hydrophilic hydrogel polymer materials are superimposed.The disclosed aquogel polymer that is suitable for does not comprise urethane, but is limited to a kind of in methacrylic acid-2-hydroxy methacrylate and methacrylic acid and the 2-ethylhexyl acrylate or both multipolymers.
The another kind of polyurethane-base polymeric system that is used for from water dispersion formation film and coating is disclosed in the US patent No. 4,644,030.This patent disclosure: form a kind of with the different propylhomoserin ester polyurethane prepolymer that is terminal and the polymerisable ethylenically unsaturated monomer material of a kind of inert liq with a kind of dispersion of form of mixtures in water, allow the prepolymer chain extension make its complete reaction, allow the ethylenically unsaturated monomer material carry out the vinyl addition polymerization on the spot then and form the copolymerization product that contains urethane and a kind of second polymkeric substance.Disclosed technology in this patent (very useful) does not have ad hoc proposal can how to improve the wetting ability of formed polymer product.
Therefore, to the polyurethane-base polymeric dispersions and the prior art of the film that forms thus (wherein polymeric constituent shows the wetting ability that has improved) also remain a requirement and can not satisfy.
General statement, one aspect of the present invention are that one or more nonionic wetting abilities are given in the polymer network of the copolymerization network that reagent directly introduces polyether polyols with reduced unsaturation or the urethane and second polymkeric substance.
An aspect of of the present present invention is the method that is used to form the stable water dispersion of a kind of polymer materials, be included under the condition that can effectively form the dispersible prepolymer that contains the unreacting isocyanate group of water, allow one or more contain the isocyanate compound of two or more side isocyanate groups, one or more contain the polyol compound of two or more pendant hydroxyl groups and one or more, and effectively to give described polymer materials hydrophilic and contain and can react with the reagent one of one or more hydroxyls of described isocyanate group reaction; Then at the effective described product of complete reaction with in water, form and allow the reaction product chain extension under the condition of its discrete item.In this embodiment, allowing from the part of formed film of dispersion and coating possess hydrophilic property is directly to introduce the polyurethane prepolymer with chemical mode, and prepolymer is chain extension subsequently.
Another embodiment of the invention is to make the method for stable polymer material water dispersion, this method comprises being that the polyurethane prepolymer of terminal and one or more can effectively make described polymer materials possess hydrophilic property and contain two or more can the reaction with the reagent of the group of described isocyanate groups reaction with the isocyanic ester, allow the reaction product chain extension then, if the complete reaction isocyanate groups, wherein the reaction both of chain extending reaction or chain extension step and formation prepolymer carries out in water dispersion.In this embodiment, wetting ability is given reagent and is used as chainextender, the prepolymer unit is linked together, thereby introduce in the polyether polyols with reduced unsaturation with chemical mode.
The present invention also has another embodiment, at first, (providing) being provided a kind of is the polyurethane prepolymer of terminal and the water dispersion of the mixture of the polymerisable ethylenically unsaturated monomer material of inertia liquid state with the isocyanic ester, and make performed polymer carry out chain extension, so that allow the isocyanate groups reaction fully, adding one or more then in dispersion can effectively give the hydrophilic olefinic of polymer materials unsaturated reagent, after experiencing these processes, unsaturated reagent of olefinic and ethylenically unsaturated monomer material carry out copolymerization together, thereby have formed a kind of stable polymer material water dispersion.Therefore, to give reagent be directly to introduce in the copolymer networks with chemical mode again to wetting ability.
Additional aspect of the present invention comprises: according to the water dispersion of the polyurethane-base polymeric system of above-mentioned any method preparation, and the composition that is included in any this type of dispersion in (being suitable for composition is coated on the stromal surface) vehicle.
Polyurethane-base polymeric system useful among the present invention can be by any manufacturing in the whole bag of tricks of the present invention.Described system can curtain coating become a kind of demonstration to improve hydrophilic film.In one embodiment, with the isocyanic ester is the polyurethane prepolymer of terminal, can be by traditional method, by allowing suitable isocyanato-compound and one or more suitable polyol reactions, prepolymer and a kind of also possess hydrophilic property as chainextender are given substituent compound and are reacted and provide subsequently.
In second embodiment, with suitable isocyanato-compound, suitable polyvalent alcohol and suitable be that the wetting ability of terminal is given reagent to put that reaction generates with the isocyanic ester together be the prepolymer of terminal with the hydroxyl, subsequently again with suitable chainextender reaction.
In the 3rd embodiment, providing with the isocyanic ester is the prepolymer of terminal, and it carries out chain extension in the presence of inertia ethylenically unsaturated monomer material, follows described material and the suitable unsaturated wetting ability of olefinic and gives reagent and carry out copolymerization.
Suitable isocyanato-compound useful when obtaining any indicated prepolymer is generally saturated or unsaturated by (the NCO group) that two isocyanate groups replace, straight chain, side chain, ring-type or polynuclear compound are formed.The compound that contains three or more isocyanate groups also can use.Best most isocyanato-compound contains two isocyanate groups.The example of satisfied isocyanato-compound is included in the isocyano compound that any usefulness described in the document that provides with the publication form generates urethane.Special example comprises aliphatic series and aromatic isocyanate, hexamethylene diisocyanate for example, trimethyl hexamethylene diisocyanate, ditan-4,4 '-vulcabond, isophorone diisocyanate, methylene-bis (isocyanato--hexanaphthene), 2-methyl-5-vinyl benzene-1, the 4-vulcabond, 1-(α-isocyanato--Alpha-Methyl) ethyl-3-(Alpha-Methyl) vinyl benzene, and polyisocyanates Mondur CB. (adducts of three moles of toluene diisocyanate and a mole of trimethylol propane) for example, Desmodur-N (1, the trifunctional biuret of 6-hexane diisocyanate), Isonate 143L (methylene-bis of polymerized form (phenyl isocyanate) or the like.Tolylene diisocyanate and in alkylidene chain, contain the α of 4 to 12 carbon atoms preferably, ω-alkylene diisocyanate, for example 1,6-hexane diisocyanate.
The useful isocyanato-compound of other that should be mentioned that comprises tetramethylxylene diisocyanate, Xylene Diisocyanate, to phenylene diisocyanate, right-cyclohexylidene vulcabond and naphthalene diisocyanate.
Comprise any organic compound that contains two or more (useful when generating required prepolymer) pendant hydroxyl groups with one or more polyvalent alcohols of isocyanato-component reaction, be also included within the ring compound that open loop under the reaction conditions provides the appropriate reaction activity hydroxy with the isocyanate groups reaction.Preferred polyhydric alcohols, per molecule contain on average about at least 2 active hydrogen atoms, and term " active hydrogen atom " refers to the test according to Zerewitinoff, and (J.Amer.Chem.Soc., 49,3181 (1927) have active hydrogen.It is about 400 to 5000 that suitable polyol reactant preferably has molecular weight, and average hydroxyl value is about 10 to about 300, is preferably about 30 to about 150 (as by ASTM test E 22257, method B measures).The example of suitable polyvalent alcohol comprises TriMethylolPropane(TMP), ethylene glycol, propylene glycol or the like.Suitable ring compound comprises polycaprolactone.Preferred glycol comprises α, and the alpha, omega-dihydroxy polyester is especially by alkane chain diol and C
2-10The ester that dicarboxylic acid (as hexanodioic acid) forms.Particularly preferred polyester glycol is by hexanodioic acid and 1,4-butyleneglycol and 1, and a kind of or two kinds of reactions obtain in the 6-hexylene glycol.Other that should be mentioned in that preferred two pure and mild polyvalent alcohols comprise cyclohexanedimethanol, nonanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 2-butyl-2-ethyl-1, ammediol, the 2-methyl isophthalic acid, ammediol, neopentyl glycol, alkoxylate dihydroxyphenyl propane, alkoxylate Resorcinol and other dihydroxy-benzene class.
Preferably, the polyol component that reacts with the isocyanato-compound comprises at least a reactant, provides water-dispersible for polyurethane prepolymer effectively.Described one or more reactants generally account for reaction mixture about 0.5 to about 10wt%, the example of described reactant comprises glycol or the polyvalent alcohol that contains side carboxylic acid or cationic salts group.Side carboxyl may be the form of salt or be preferably in prepolymer and form during or be neutralized into salt form with suitable alkaloid substance (for example tertiary amine) afterwards or during dispersion forms.Preferably containing the carboxyl reaction thing is α, alpha, alpha-dimethyl alcohol C
2-10Paraffinic acid, particularly 2,2-dimethanol propionic acid.When an above-mentioned component is introduced into the prepolymer that forms in the reaction, also have subsequent step, wherein with neutralization reagent for example triethylamine be added in the mixture that contains prepolymer.Help the example of suitable reactant of the water dispersible of polyurethane prepolymer to comprise the salt that contains active dydrogen compounds such as diamines, for example sulfonate sodium.
Known other any additive can be included in the reaction of polyvalent alcohol that formation is terminal with the isocyanic ester (when needs time) in the synthetic field of poly-hydrogen ester.
Generalized case, next reacts in the condition that can effectively promote to react between isocyanate groups and the hydroxyl for one or more isocyanato-compounds and one or more polyvalent alcohols.Should allow isocyanato-compound chemistry metering be in excess in polyol compound, so as with all hydroxyl complete reactions, remaining excessive unreacted isocyanate groups.
Wetting ability gives how much reagent (it in the process of synthesis of polyurethane polymeric system whenever all in reaction, so that give the product that is generated wetting ability) structurally changes and to allow reagent to be binding on the substituent essence of the needed reactive behavior of polymeric system with covalent manner relevant.But in general, wetting ability is given reagent and is characterised in that and contains one or more structures or substituent non-ionic compound, and there is high avidity the back to glassware for drinking water in being incorporated into polymer product.Preferred example comprises the compound, particularly hydroxy alkyl compound that hydroxyl replaces, for example hydroxyethyl methylacrylate and have one or more by hydroxyl or C
1-6The compound of the formed chain of alkyl (as being preferably methyl or ethyl) end capped repetition oxyethyl group and/or propoxy-unit.Other example can be found out in this manual.
Several preferred embodiment of the present invention is described below respectively:
Wetting ability gives reagent and introduces in the prepolymer
In this embodiment, but be suitable for generating one or more isocyanato-compounds and one or more polyol compounds of water dispersed polyurethane prepolymer, in reaction mixture together with can give reagent mix with one or more wetting abilities that isocyano compound and polyol reaction form prepolymer, prepolymer combines reagent with covalent manner.Relative amounts of reactants should be selected, so that make in the reaction mixture after existing all free hydroxyl groups reaction remaining unreacted isocyanate groups.In this embodiment, wetting ability gives reagent should contain at least a hydroxyl substituent, and it can make reagent enter in the prepolymer that is generated by reaction.Because any described hydroxyl is to be easy to and the isocyanate groups reaction that is present in the reaction mixture, therefore, the wetting ability of product need exist the hydroxyl-removal structure in addition of possess hydrophilic property to obtain.In this embodiment of the present invention, ether that agents useful for same is preferably alkyl-blocked or polyethers.Example comprises monoether, for example dimethyl hydroxyethyl ether, ethyl-hydroxyethyl ether or the like, and molecular weight is also included within an end C with about ethylene oxide adduct of 200 to 5000
1-6The polyethers of low alkyl group such as methyl blocking and polyoxyethylene glycol, polypropylene glycol or the like (should note these compounds each contain at least one hydroxyl).Described alcohol can have variation range preferably in the 2 various chain lengths to about 50-60 repeating unit, so glycol is liquid or solid, and it should dissolve in the reaction medium.
The reaction product of these three specified components is carried out chain extension with any traditional method then.Just the prepolymer according to specified such generation reacts with the compound that one or more can effectively be connected the isocyanate groups of adjacent prepolymer molecule.The most handy organic polyamine of chain extension, general aliphatic polyamines carries out.Polyamines has more high reaction activity than water when reacting with isocyanate groups, and preferred example comprises hydrazine, quadrol, diethylenetriamine, organosilicon/polyamide 6 hydrazine and composition thereof.
For the product of the present embodiment obtains with the water-dispersion form, preferably, the initial reaction that isocyanato-component, polyol component and wetting ability give reagent carries out under anhydrous condition, and chain extension step is subsequently carried out in the dispersion in water.Just as specified, water dispersible can provide by having side carboxyl or Ionized carboxyl (covalent manner is incorporated in the polyurethane prepolymer).(perhaps also have) on the other hand, water dispersible can be by allowing prepolymer provide with powerful stirring of any suitable dispersion agent in water.Many examples of suitable dispersion agent, it is several to propose having only of title, they are characterised in that as condensation product to have the hydrophobic components that contains about 8 to 20 carbon atoms and many repetition ethylene oxide units (that is 2 to 100 moles of ethylene oxide) are arranged in its structure.
Form dispersion howsoever, it preferably contains has an appointment 40 to about 90wt%, more preferably about water of 60 to 80wt%.
Give reagent with the prepolymer chain extension with wetting ability
In another preferred embodiment of the present invention, providing a kind of is the polyurethane prepolymer of terminal with the isocyanic ester.This prepolymer can pass through any currently known methods, generally prepares by one or more isocyanato-compounds and one or more polyvalent alcohols are reacted.Prepolymer can be by 4,644,030 described preparation of the US patent No..This patent all discloses among the application of being introduced into for referencial use.Prepolymer can prepare also that the wetting ability of significant quantity gives reagent in the prepolymer so that introduce by the application's aforementioned part.
The prepolymer that with the isocyanic ester is terminal gives reagent react with one or more nonionic wetting abilities then, in order that allow one or more reagent and the reaction of described isocyanate groups so that with the polyurethane prepolymer chain extension.
The described nonionic wetting ability of the available q.s of this reaction is given reagent and is carried out, so that allow the complete chain extension of whole unreacted isocyanate groups.But the available described reagent less than stoichiometric quantity of this reaction carries out, but must react the described reagent of q.s so that give the final product wetting ability.
Wetting ability gives part and can comprise by two amino main chains that replace, and tells one or more hydroxyl side chains from main chain.But more preferably, wetting ability is given by the segment of one or more side chains carrying groups or possess hydrophilic property.Provide the example of the described group of side group or chain to comprise hydroxyl and the hydroxyalkyl of (preferred 1 in the 20) carbon atom that contains 1 to 50 by diamines.Other example comprise for example contain 1 to 50 this type of repeat the hydroxy-end capped or C of oxyalkyl units
1-6End capped poly-(oxyethyl group) or poly-(propoxy-) chain.The main chain that connects two functionalized primary amine groups can be aliphatic, alicyclic or aromatics, and may contain heteroatoms for example oxygen, sulphur or nitrogen.The example that has the main chain of hydrophilic parts comprises C
2-6Alkylenediamine, for example quadrol and two alkylene triamine (containing 4 to 20 carbon atoms), for example diethylenetriamine.Therefore, the example that useful suitable reactive behavior wetting ability gives reagent in this embodiment of the present invention comprises hydroxyethyl-quadrol (3, the 4-diamino-just-butanols-1), and with containing the senior Alkylenediamine of the polyoxyethylene glycol replacement of 50 ethylene oxide units at the most.Other example that gives the hydrophilic useful chainextender of final product comprises amine end capped poly-(oxygen ethene) or poly-(oxypropylene) compound.
Follow isocyanate-terminated polyurethane prepolymer with allow the prepolymer chain extension and give final product hydrophilic reagent react, if desired, the reaction product of generation then further chain extension to allow any remaining unreacted isocyanate groups complete reaction in the prepolymer.This chain extension can be undertaken by any conventionally known method in the prior art, preferably carries out in the aqueous dispersion of polymkeric substance in water.Any suitable chainextender can be used, and for example above-mentioned chainextender comprises hydrazine, quadrol, diethylenetriamine etc.
This reactions steps is with containing two functional groups, each can react with isocyanato, and contain also that the compound that gives the hydrophilic part of final product (it can be a molecular backbone between two isocyanate group, or the substituting group of described chain) carries out.In general, the functional group with the isocyanic ester radical reaction is primary amine or secondary amine.
Giving the hydrophilic agent copolymerization is incorporated in the polyether polyols with reduced unsaturation product
The US patent No. 4,644,030 (among the application of being cited for referencial use) discloses the water dispersion of polymer materials, it prepares by following: a kind of isocyanate-terminated polyurethane prepolymer and the mixture of the polymerisable ethylenically unsaturated monomer material of inert liq are provided, the sort of product mixtures is dispersed in the water, in the water dispersion that so forms with the prepolymer chain extension so that allow its complete reaction, then, wherein dispersion can be carried out the vinyl addition polymerization of monomeric substance on the spot.Have now found that, give reagent by in the water dispersion that is carrying out before the vinyl addition polymerization step, adding one or more wetting abilities that contain the vinyl unsaturated link(age), make ethylenically unsaturated monomer material and reagent carry out copolymerization then, can give by in the prepared product wetting ability of method described in that piece patent.The copolymerization network of the resulting polyether polyols with reduced unsaturation and second polymkeric substance demonstrates needed wetting ability.
In this embodiment, isocyanate-terminated polyurethane prepolymer is by the preparation of any known technology, and then with currently known methods with its redispersion in water.As above specified, these methods can comprise to be introduced carboxyl in the polymkeric substance and/or the suitable dispersion agent of interpolation when stirring prepolymer in the entry.
The chain extension of prepolymer also can use known chain extension reagent to finish (its example provides) in the above by standard technique.The chain extension effect can be used and can give the hydrophilic reactant of product and finish (as described herein).
The useful suitable unsaturated wetting ability of olefinic is given reagent and is comprised segment or the substituent any compound with the double-stranded and possess hydrophilic property of required carbon-to-carbon in the present embodiment.Its example comprises vinylformic acid hydroxyl C
1-6Alkyl ester and hydroxyethyl methacrylate C
1-6Alkyl ester, for example hydroxyethyl methylacrylate and contain 2 to 50 polyoxyethylene glycol-vinyl ether that repeat ethylene oxide units.Other example that the wetting ability that should be mentioned in that gives reagent comprises sodium vinyl sulfonate, uses C
1-6The glycerine alkyl oxide of oxyalkylated alkoxylated allylic alcohols of alkoxyl group and ethoxylation (it is the material that contains the ethoxyquin of 1 to 50 ethoxy unit).
Should add the q.s wetting ability and give reagent, so that final polymerized product presents required wetting ability.In general the reagent usage quantity for about 5wt% extremely about 40wt% can produce effective result.
Use is to causing and promoting any effective condition of polymeric to allow two kinds or the unsaturated component of multiple olefinic carry out copolymerization.Preferably use redox system (as comprising the Potassium Persulphate of 1 weight part at the most), the effectively long time (as being heated to 70 ℃ at 4 hours) of heating mixing is carried out polyreaction then.Be preferably in reaction mixture, to increase progressively in the polymerization whole process and add additional redox reaction agent, as the Sodium Pyrosulfite of about 1 weight part (in 40 parts of water) at the most.
Owing to be aggregated in when carrying out in the water dispersion, final copolymerization product also is the water dispersion form.
The prescription of polyurethane dispersions and application
A further aspect of the present invention relates to the purposes of polyether polyols with reduced unsaturation dispersion, it includes, but are not limited to the polyether polyols with reduced unsaturation dispersion, wherein non-ionic hydrophilic gives reagent with in the covalent manner introducing polymer network, found to improve the improvement prescription of film or coating adhesion, film and coating have chemical resistant properties, resistance to abrasion, toughness and flexibility.
In general, prepare a kind of prescription, it comprises the water dispersion of polyether polyols with reduced unsaturation material and the film that can give to be deposited out subsequently or the annexing ingredient of the required additional character of coating.
Dispersion described herein can directly be used to coated film and coating in many different substrates not having further batching and not adding under the situation of other component.Generally the 1-5 micron to up to 20 microns or even up to the dispersion thin layer of 50 micron levels, be to be coated on the above-mentioned surface with any conventional art, before cured film, allow water evaporate subsequently and leave away.
Described reagent can comprise additional surfactant arbitrarily, particularly contains the moieties of 6-20 carbon atom and the tensio-active agent of the poly-alkoxyl group part that contains 2 to 50 described oxyalkyl units (wherein each alkoxyl group is oxyethyl group or propoxy-).Also can comprise the reagent that final coating is further provided slippage, described reagent typically comprises silicone oil, for example poly-(dimethyl siloxane) or poly-(methylphenyl siloxane).
Measured above-mentioned polyurethane dispersions already the sticking power on the stromal surface (dispersion is painted on the stromal surface).
Also measure polyurethane dispersions and sticked to stromal surface, the ability on natural rubber latex or the synthetic elastomer material surface particularly, this ability can be by with the linking agent and the nonionic hydrophilic polymer of significant quantity, and is used for a kind of catalyzer of crosslinking reaction of cross-linking catalyst and polyether polyols with reduced unsaturation and substrate material and prepares dispersion and improved.
The polyether polyols with reduced unsaturation dispersion can Click here the explanation prepare.The polyether polyols with reduced unsaturation dispersion also can be any other polyether polyols with reduced unsaturation dispersion, be included in the US patent No. 5,088,125 and 4,644, described in 030 these, their disclosure is introduced in this specification sheets as a reference, and disclosed from here reactant but dispense wetting ability and give reagent and any other the effective copolymerization monomer of use (depending on the circumstances) alternate or chainextender and prepare the polyether polyols with reduced unsaturation dispersion.
Preferred non-ionic hydrophilic polymkeric substance comprises polyoxyethylene glycol, promptly repeats the polymkeric substance of ethoxy unit, and preferably having molecular weight is 50000 to 125000.Other preferred nonionic, hydrophilic polymers comprises polyvinyl alcohol, polyacrylic acid and polymethyl acrylic acid (hydroxyl C
1-6Alkyl) ester, preferably molecular weight is 50,000 to 125,000.Nonionic, hydrophilic polymers should account for about 5 about 20wt% of polyether polyols with reduced unsaturation dispersion, is preferably the about 15wt% of about 7-.
Preferred cross-linking agents comprises melamine and the functionality water dispersion greater than 1 epoxy compounds.Linking agent and polyether polyols with reduced unsaturation, nonionic, hydrophilic polymers stromal surface react form with stromal surface with the crosslinked integral body of covalent manner bonded.
The amount of linking agent be generally the polyurethane dispersions amount about 5 to about 20wt%.Satisfied catalyzer comprises those sulfonic amine salts, for example methanesulfonic and toluenesulphonic acids.The acceptable amount of catalyzer generally accounts for the about 20wt% of about 5-of linking agent weight.
When the preparaton that contains these components and also contain arbitrariness component (for example siloxanes slippage agent, nonionogenic tenside and deaerating agent) is applied on the matrix with form of film; the protective coating of adhesivity, non-layered, this coating chemical resistant properties and physical abrasion and corrosion have been solidified at the matrix upper film.
Coating proportional preparation preferably is divided into two independent compositions, puts together to form a complete formula.A kind of composition is the polyether polyols with reduced unsaturation dispersion in its own independent container.Another composition in an independent container comprises all other components: nonionic, hydrophilic polymers, linking agent, crosslinked with catalyzer and other required component.
In use, two kinds of compositions closely mix, and are coated on the required surface.Crosslinking reaction begins preferably to adopt mild heat.
The present invention further specifies with the following example, comprises the explanation goal of the invention, and this does not think and limits the scope of the invention.
Embodiment 1
Present embodiment narration preparation polyurethane dispersions does not give reagent wetting ability and introduces in the polymkeric substance.
In the resin kettle that agitator, thermometer, condenser and heating jacket are housed, add following ingredients by indicated percentage ratio:
| Composition | Weight percentage |
| By hexanodioic acid and about 1: 1 pact, 4-butyleneglycol and 1, the polyester polyol that the mixture reaction of 6-hexylene glycol generates | ????65.55 |
| TriMethylolPropane(TMP) | ????0.61 |
| Dimethylol propionic acid | ????4.80 |
| N-Methyl pyrrolidone | ????6.17 |
| Isophorone diisocyanate | ????22.87 |
These products stir limit heating several hrs at 80-100 ℃, up to free isocyanate content reach that its theory limits the quantity of 3.38%.At this moment, established prepolymer is dispersed in the water by the described component of following table is merged by specified amount:
| Component | Weight percentage |
| Water | ????54.66 |
| The siloxanes deaerating agent | ????0.09 |
| Triethylamine | ????1.55 |
| Prepolymer | ????42.29 |
| 35% aqueous hydrazine | ????1.24 |
Add triethylamine and deaerating agent, and mix in the entry at 55-75 °F.During 10-15 minute, prepolymer is slowly added in the entry by high shear mixing.After prepolymer adds about 5 minutes add in aqueous hydrazine and the prepolymer the free end isocyanate reaction and with the polymkeric substance chain extension, the dispersion of generation has following character:
Film by this dispersion curtain coating has following character:
| Weight percent solids | ????40 |
| pH | ????8.0 |
| Brookfield viscosity (cps is in room temperature) | ????200 |
| Tensile strength, pound/inch 2 | ????5,000 |
| The elongation of limit percentage ratio | ????550 |
Embodiment 2 (with the reagent chain extension that contains hydrophilic segment)
Polyurethane dispersions is pressed embodiment 1 described same procedure manufacturing, and the different 1wt% hydroxyethyl-quadrols that are to use replace hydrazine, and consequent polymkeric substance has the side hydroxyethyl groups.Dispersion has following character:
Film by this dispersion curtain coating has following character:
| Weight percent solids | ????30 |
| Brookfield viscosity (cps is in room temperature) | ????145 |
| pH | ????8.5 |
| Tensile strength, pound/inch 2 | ???5000 |
| The elongation of limit percentage ratio | ???550 |
Embodiment 3
(wetting ability gives reagent and introduces in the polyurethane prepolymer)
The listed reactant of following table is packed in the resin kettle, and reacts, reach the theoretical limits definite value up to the percentage ratio of free isocyanate group by the method identical with first set reaction described in the embodiment 1:
| Component | The equivalent that adds reactant |
| Polyester polyol as described in example 1 above | ?????0.39 |
| TriMethylolPropane(TMP) | ?????0.094 |
| Dimethylol propionic acid | ?????0.645 |
| Isophorone diisocyanate | ?????1.864 |
| The polyoxyethylene glycol m.w.2000 of methyl blocking | ?????0.021 |
Reactant is packed in the resin kettle, and by with embodiment 1 described identical method reaction, reach the theoretical limits definite value up to free isocyanate content.Then prepolymer is added in the water that contains enough triethylamines, in and prepolymer in the carboxylic acid group, produce final polymeric dispersions with the aqueous hydrazine chain extension subsequently.Dispersion has following character:
The cast film of dispersion has following character
| Weight percent solids | ????35 |
| pH | ????8.2 |
| Viscosity (cps is in room temperature) | ????490 |
| Particle size | Hemicolloid |
| Tensile strength, pound/inch 2 | ????4,700 |
| The elongation of limit percentage ratio | ????520 |
Embodiment 4 (wetting ability gives reagent and introduces in the polyurethane/polyacrylate multipolymer)
The reactant that following table is listed mixes by the listed consumption of table, and in identical device and in embodiment 1 used condition next react, show that up to the prepolymer that generates free isocyanate content is till theoretical limit value 3.46:
| Component | Parts by weight |
| As polyester polyol as described in the embodiment 1 | ????589.0 |
| Dimethylol propionic acid | ????44.89 |
| Isophorone two different propylhomoserin esters | ????204.9 |
| Butyl acrylate | ????130 |
It is about 3.4% up to the isocyanic ester residue that this mixture is mixed 5.5 hours 55-60 ℃ of heating.Add triethylamine then, its amount be with in and the carboxyl that exists in the polymkeric substance, and thorough mixing resulting mixture.Then this mixture is added under high-speed stirring and form water dispersion in the entry.Add hydrazine amount for corresponding to reacting about 90% of required theoretical amount with whole unreacted isocyanate groups.Under the high speed shear condition, 116 gram Hydroxyethyl acrylates are added in the dispersion then.
The dispersion that generates is carried out polymerization further by adding 0.9 part of Potassium Persulphate and being heated to 70 ℃ in 4 hours.This polyreaction preferably can be used redox system, wherein adds about 0.9 part of Potassium Persulphate, subsequently about 40 ℃ in 3 hours in reaction mixture with incremental mode add 0.9 part of Sodium Pyrosulfite in 40 parts of water solution and carry out.
Embodiment 5 (preparation is used for applying the preparaton on rubber gloves surface)
The listed component of following table is mixed together by specified amount in the table:
| Component | Parts by weight |
| Water | ????4670.2 |
| Press the polyurethane dispersions of embodiment 1 preparation | ????742.3 |
| Tensio-active agent (contain 50 ethoxy units of having an appointment to nonyl phenol ethoxylate) | ????25.0 |
| The aqueous solution of 10% polyoxyethylene glycol, having the polymerization degree is 80,000-100,000 | ????749.3 |
| Melamine | ????95.9 |
| The Dimethicone lubricant | ????79.9 |
| Deaerating agent | ????0.7 |
| The amine salt of-sulfinic acid (melamine crosslinking catalyst) | ????14.9 |
Use homogenizer under about 25 ℃ of temperature, to stir this mixture 30 minutes.The dispersion solids content that generates is about 5wt%.
The latex rubber gloves of prevulcanized immersed reach 12 seconds in the above-mentioned dispersion, then 120 ℃ of minimum temperatures dry 30 to 40 minutes down.In ability (donnability) speed trial of south, road, mark 10 is south, the road ability of best degree, mark 1 is for the poorest, the gloves of handling with this method show that south, dry road ability speed is 8, moist south, road ability speed is 7-8, and show that with comparing gloves south, road ability speed is 7-8, stand several processing according to the coating of this coating and do not stand delamination.
Embodiment 6 (preparation is used for the polyurethane dispersions of the embodiment 2 on rubber gloves surface)
The listed component of following table is mixed together by measuring described in the table:
| Component | Amount (gram) |
| Press the polyurethane dispersions of embodiment 2 preparations | ????559.5 |
| Tensio-active agent (contain about 50 ethoxy alkane unitary right-nonyl phenol ethoxylate) | ????14.2 |
| The aqueous solution of 10% polyoxyethylene glycol, its molecular weight are 80, and 000-100,000 | ????423.4 |
| Melamine | ????54.2 |
| The Dimethicone lubricant | ????45.1 |
| Deaerating agent | ????0.4 |
| The amine salt of-sulfinic acid (the crosslinked catalyzer of using of melamine) | ????8.4 |
| Water | ????4519.5 |
Use homogenizer under about 25 ℃ of temperature, mixture to be mixed about 30 minutes.The solids content that dispersion had that generates is about 5wt%.The rubber gloves of prevulcanized immersed reaches 12 seconds in the above-mentioned dispersion, then in 120 ℃ in convection oven dry 40 minutes.The product that generates has the coating of the about 0.35ml of thickness, and it shows that excellent adhesion and south, dry road ability speed are 8, and south, moist road speed is 7.
Embodiment 7
With the polyurethane dispersions of this paper technology preparation or use with above-mentioned melamine cross-linking system further the polyurethane dispersions of preparation apply the gloves of making by natural rubber latex through conventional condensation technique, 130 ℃ of sulfurations 30 to 40 minutes, test south, the road ability of gloves then by the coefficient of friction of measuring the gloves that applied subsequently.Also measure tear strength (poundage of every line style inch, or " pli ") and 500% modulus intensity (pounds per square inch (p.p.s.i), or Psi).Sum up its result below:
| Glove type | Coefficient of friction | 500% modulus (psi) | Elongation (%) | Tear strength (pli) |
| The rubber gloves of uncoated (contrast) | ????1.55 | ????586 | ?850 | ????323 |
| Rubber gloves with the polyurethane dispersions coating of pressing embodiment 2 preparations | ????1.25 | ????… | ?… | ????… |
| By the rubber gloves that applies by polyurethane dispersions embodiment 2 preparations and that further prepare burden with the melamine cross-linking system | ????0.54 | ????567 | ?843 | ????370 |
| With the rubber gloves that applies by polyurethane dispersions embodiment 1 preparation and that further prepare burden with the melamine cross-linking system | ????0.30 | ????584 | ?887 | ????380 |
Claims (22)
1. method that forms stable polymer material water dispersion, comprise allow one or more can effectively give the hydrophilic non-ion reagent of described polymer materials with
(a) one or more isocyanato-compounds with two or more side isocyanate groups contain the reaction mixture of the polyol compound of two or more pendant hydroxyl groups with one or more, wherein said reagent contain one or more can with the hydroxyl of described isocyanic ester radical reaction, just this reaction product contains unreacted isocyanate groups; Or
(b) the chain link product that generates by one or more reactions with the isocyanato-compound of two or more side isocyanate groups and one or more polyol compounds that contain two or more pendant hydroxyl groups, just this product contains unreacted isocyanate groups, wherein said reagent contain two or more can with the group of described unreacted isocyanate groups reaction; Or
(c) a kind of product, it is obtained by following mode: the water dispersion that the mixture of end capped urethane pre-polymerization of a kind of NCO and the polymerisable ethylenically unsaturated monomer material of inert liq at first is provided, in described water dispersion, allow then described prepolymer chain extension complete reaction it, wherein said reagent contain can with the ethylenic unsaturated bond of described monomer key copolymerization;
Will by described reagent and described reaction mixture (a) or with described chain link product (b), if desired,, react the product that is generated and expand key effectively allowing described product complete reaction and forming under the condition of its dispersion in water.
2. stable water dispersion that produces by the method for claim 1.
3. a film forming method on matrix comprises according to claim 1 and makes a kind of dispersion, and deposit film by described dispersion on described matrix.
4. a method that forms stable polymer material water dispersion comprises
(a) allow (i) one or more contain the isocyanato-compound of two or more side isocyanate groups, (ii) one or more contain the polyol compound of two or more pendant hydroxyl groups, (iii) one or more can award described polymer materials wetting ability and contain one or more can with the non-ion reagent of the hydroxyl of the reaction of described isocyanate groups, next reacts forming the dispersible prepolymer condition of the water that contains unreacted isocyanate groups effectively;
(b) can allow described product complete reaction and forming under its dispersion condition in water, effectively with the product chain extension of step (a).
5. according to the method for claim 4, can give effectively wherein that hydrophilic these one or more non-ion reagents are selected from dimethyl hydroxyethyl ether, ethyl-hydroxyethyl ether, have molecular weight is about polyoxyethylene glycol of 200 to 5000 and to have molecular weight be about polypropylene glycol of 200 to 5000.
6. stable water dispersion of making according to the method for claim 4.
7. a film forming method in substrate comprises by claim 4 and makes dispersion and described dispersion is deposited film in described substrate.
8. method that forms the stable polymer dispersion, comprise (a) allow isocyanate-terminated polyurethane prepolymer and one or more can effectively give described polymer materials wetting ability and contain two or more can with the non-ion reagent reaction of the group of described isocyanate groups reaction; (b) with the product chain extension of step (a), isocyanate groups complete reaction as described in allowing as needs; Wherein step (b) or step (a) and step (b) are carried out in water dispersion.
9. method according to Claim 8, wherein said one or more can effectively give hydrophilic non-ion reagent and be selected from and replaced by two amidos, wherein each is primary amine or secondary amine and also can be selected from hydroxyl by at least one, contains the hydroxyalkyl of 1 to 50 carbon atom and contains 1 to 50 oxyethyl group or the unitary hydroxy-end capped or C of propoxy-
1-6The aliphatic series that group replaced of end capped poly-oxyalkyl chain, alicyclic and aromatic substance.
10. method according to Claim 8, wherein one or more can effectively give two alkylene triamine that hydrophilic non-ion reagent is selected from the Alkylenediamine that contains 2 to 6 carbon atoms and contains 4 to 20 carbon atoms, and described diamines and triamine are selected from hydroxyl, contain the hydroxyalkyl of 1 to 50 carbon atom and contain 1 to 50 oxyethyl group by at least one or the unitary hydroxy-end capped or C of propoxy-
1-6End-blocking poly-alkoxyl group group replaced.
11. one kind by the stable aqueous dispersion of producing by the method for claim 8.
12. a film forming method in substrate comprises by claim 8 and makes dispersion and on described matrix described dispersion is deposited film.
13. a method that forms stable polymer material water dispersion comprises
(a) provide the water dispersion of the mixture of a kind of isocyanate-terminated polyurethane prepolymer and the polymerisable ethylenically unsaturated monomer material of inert liq, and described prepolymer chain extension is allowed described isocyanate groups complete reaction;
(b) adding can effectively give hydrophilic one or more nonionic olefinics of described polymer materials unsaturated reagent in described dispersion; With
(c) allow described monomeric substance and described one or more reagent copolymerizations.
14. according to the method for claim 13, the unsaturated reagent of wherein said one or more nonionic olefinics is selected from vinylformic acid and hydroxyethyl methacrylate C
1-6Alkyl ester, contain poly-(ethylene glycol) vinyl ether, sodium vinyl sulfonate, the C of 2 to 50 ethoxy units
1-6Oxyalkylated vinyl carbinol and have the allylin of the ethoxylation of 1 to 50 ethoxy unit.
15. stable water dispersion that produces by method by claim 13.
16. a film forming method in substrate comprises by claim 13 forming dispersion and deposit film by described dispersion in described substrate.
17. a coating proportional preparation comprises:
(a) a kind of water dispersion of polyether polyols with reduced unsaturation;
(b) a kind of nonionic, hydrophilic polymers;
(c) a kind of linking agent; With
(d) catalyzer of described linking agent.
18. coating proportional preparation according to claim 17, wherein said nonionic, hydrophilic polymers account for described dispersion about 5 to about 20wt%, about 5 to about 20wt% and the described catalyzer that described linking agent accounts for described dispersion account for described linking agent about 5 to about 20wt%
19. the coating proportional preparation according to claim 18, wherein said nonionic, hydrophilic polymers is selected from polyoxyethylene glycol, polyvinyl alcohol and poly-(vinylformic acid and hydroxyethyl methacrylate C
1-6Alkyl) ester, its molecular weight are about 50000 to about 125000.
20. the coating proportional preparation according to claim 18, wherein said linking agent are selected from melamine and have the epoxide of functionality greater than 1.
21. a product comprises:
(a) in first container, a kind of water dispersion of polyether polyols with reduced unsaturation is arranged.
(b) in second container, a kind of mixture is arranged, it comprises a kind of nonionic, hydrophilic polymers, the catalyzer of a kind of linking agent and a kind of described linking agent.
22. the product according to claim 21, wherein said nonionic, hydrophilic polymers is selected from polyoxyethylene glycol, polyvinyl alcohol and polyacrylic acid and polymethyl acrylic acid (hydroxyl C
1-6Alkyl) ester, and to have molecular weight be about 50000 to about 125000; Be selected from melamine and have the epoxide of functionality with wherein said linking agent greater than 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95117179 CN1144813A (en) | 1995-09-05 | 1995-09-05 | Hypoallergenic coating composition for latex rubber gloves |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95117179 CN1144813A (en) | 1995-09-05 | 1995-09-05 | Hypoallergenic coating composition for latex rubber gloves |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1144813A true CN1144813A (en) | 1997-03-12 |
Family
ID=5081165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95117179 Pending CN1144813A (en) | 1995-09-05 | 1995-09-05 | Hypoallergenic coating composition for latex rubber gloves |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1144813A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003070811A1 (en) * | 2002-02-21 | 2003-08-28 | Shanghai Shengda Medical Health Stock Co., Ltd. | Preparation of 'multicomponent/multiphase' green emulsoid gloves |
| CN100355375C (en) * | 2005-04-15 | 2007-12-19 | 周政明 | Medicinal gloves and its preparation method |
| CN102736418A (en) * | 2004-10-26 | 2012-10-17 | Az电子材料美国公司 | Composition for coating over a photoresist pattern |
-
1995
- 1995-09-05 CN CN 95117179 patent/CN1144813A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003070811A1 (en) * | 2002-02-21 | 2003-08-28 | Shanghai Shengda Medical Health Stock Co., Ltd. | Preparation of 'multicomponent/multiphase' green emulsoid gloves |
| CN102736418A (en) * | 2004-10-26 | 2012-10-17 | Az电子材料美国公司 | Composition for coating over a photoresist pattern |
| CN100355375C (en) * | 2005-04-15 | 2007-12-19 | 周政明 | Medicinal gloves and its preparation method |
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