EP0000029B1 - Verfahren zur Herstellung von wässrigen Polyurethan-Dispersionen und -Lösungen und deren Verwendung zur Beschichtung von flexiblen Substraten - Google Patents

Verfahren zur Herstellung von wässrigen Polyurethan-Dispersionen und -Lösungen und deren Verwendung zur Beschichtung von flexiblen Substraten Download PDF

Info

Publication number
EP0000029B1
EP0000029B1 EP19780100046 EP78100046A EP0000029B1 EP 0000029 B1 EP0000029 B1 EP 0000029B1 EP 19780100046 EP19780100046 EP 19780100046 EP 78100046 A EP78100046 A EP 78100046A EP 0000029 B1 EP0000029 B1 EP 0000029B1
Authority
EP
European Patent Office
Prior art keywords
groups
nco
das
water
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19780100046
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0000029A1 (de
Inventor
Josef Dr. Pedain
Klaus Dr. Nachtkamp
Klaus Dr. Noll
Jürgen Dr. Grammel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000029A1 publication Critical patent/EP0000029A1/de
Application granted granted Critical
Publication of EP0000029B1 publication Critical patent/EP0000029B1/de
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • Processes for producing stable, aqueous polyurethane-polyurea dispersions are known (e.g. DT-PS 1 184946, DT-PS 1 178 586, DT-AS 1237306, DT-Osen 1 495 745, 1 595 602, 1 770 068, 2 019 324, see also D. Dieterich et al, Angew. Chem. 82, 53 (1970)).
  • the dispersions described are based on the principle of incorporating hydrophilic centers in a macromolecular chain of a polyurethane-polyurea molecule.
  • These hydrophilic centers or so-called internal emulsifiers are ionic groups or ether functions in the known dispersions.
  • the ionic groups are either incorporated into the prepolymer in the form of special diols or used as modified amines for chain extension of the prepolymers, each of which has at least two terminal NCO functions.
  • High quality polyurethane films e.g.
  • the value level necessary for textile coating has so far been obtained from dispersions which are produced using organic solvents during polyaddition.
  • the polyaddition in solution makes it possible to build up a high molecular weight polyurethane in a homogeneous phase before it is dispersed in water. As a result, the solid of the disperse particles is also highly homogeneous.
  • This chain extension reaction can take place in the presence of water, so that an aqueous dispersion of a polyurethane is formed immediately.
  • This process is particularly suitable for the production of cationically modified polyurethanes or for the production of polyurethanes containing anionic carboxylate groups.
  • the required combination of the isocyanate polyaddition reaction with the chain extension reaction mentioned via polycondensation-capable methylol groups bonded to terminal acylamino groups represents a comparison to the known isocyanate polyaddition by the prepolymer process, in which prepolymers containing isocyanate groups with the classic chain extenders such as e.g. Water or diamines are implemented, increased effort. This effort could be justified in the process of DOS 1 770068 by the fact that it was possible for the first time to produce polyurethane dispersions without the aid of special stirrers and without the aid of emulsifiers and without the aid of solvents.
  • DT-OS 2 446 440 describes a further process which relates to the solvent-free production of polyurethanes in aqueous dispersion.
  • a sulfonate and NCO group-containing prepolymer is then reacted without the use of solvents with a compound which is difunctional in the sense of the isocyanate polyaddition reaction and has hydrogen atoms which are reactive toward isocyanate groups.
  • the NCO prepolymer is reacted with the NCO group reactive compound during the dispersing process, i.e. after the previous solution of the chain extender in the dispersion water or after the dispersion of the prepolymer in water.
  • the process mentioned enables the production of high-quality, sulfonate-containing polyurethanes in aqueous dispersion.
  • it has the disadvantage that it is limited to polyurethanes bearing sulfonate groups and only water or water-soluble polyamines are used as chain extenders; can be.
  • the object of the present invention was therefore to provide a solvent-free or low-solvent process which allows the production of polyurethanes in the aqueous phase with improved properties, the improvement being achieved in particular by the high molecular weight solids distributed in the liquid aqueous medium should be obtained by polyaddition in the most homogeneous phase possible.
  • polyurethanes can be produced in aqueous dispersion or solution by pre-dispersing NCO-containing prepolymers which contain a hydrophilic radical and / or an external emulsifier with a polyamine prior to dispersion in water. Chain extenders mixed in at least partially blocked form and then dispersed in water.
  • the present invention therefore relates to a process for the preparation of aqueous solutions or dispersions of polyurethane polyureas by reacting chemically incorporated hydrophilic groups and / or external prepolymers containing at least 2 free isocyanate groups and not containing chemically bound emulsifiers and having at least 2 primary and / or Organic compounds containing secondary amino groups in the aqueous phase, characterized in that the prepolymer containing hydrophilically modified and / or an isocyanate group containing an external emulsifier is mixed in the absence of water with compounds which contain at most one free primary or secondary amino group and at least one blocked, under which Influence of water a free primary or secondary amino group forming group and a total of at least two at least partially blocked primary and / or secondary amino groups, and then this mixture with What mixed up.
  • the present invention also relates to the use of the dispersions or solutions produced by this process for coating flexible substrates.
  • Starting materials for the process according to the invention are at least 2 terminal NCO prepolymers containing isocyanate groups.
  • Difunctional NCO prepolymers are preferably used.
  • the NCO prepolymers to be used in the process according to the invention are preferably those which have one or more hydrophilic groups (s) which are responsible for their solubility or dispersibility in water.
  • hydrophilic groups s
  • hydrophobic NCO prepolymers per se in the process according to the invention if their solubility or dispersibility in Water is taken care of by using external emulsifiers.
  • NCO prepolymers which have already been used in the preparation of aqueous polyurethane dispersions or solutions are suitable for carrying out the process according to the invention. They are produced using known methods of the prior art and are described, for example, in DT-OSen 1 495 745, 1 495 847, 2 446 440 2 340 512, US Pat. No. 3,479,310, GB Patents 1,153,088 or 1 076 688.
  • NCO prepolymers with chemically incorporated hydrophilic groups which are preferably used in the process according to the invention, is carried out in analogy to the methods as mentioned in the literature references mentioned by way of example.
  • Starting materials for the production of these NCO prepolymers are accordingly 1. any organic polyisocyanates, preferably diisocyanates of the formula wherein Q represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group having 6 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms or an araliphatic hydrocarbon group having 7 to 15 carbon atoms.
  • diisocyanates examples include hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate and mixtures consisting of these compounds.
  • polyisocyanates known per se in polyurethane chemistry or modified ones known per se, for example carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups.
  • Any organic compounds with at least two groups that are reactive toward isocyanate groups in particular a total of two amino groups, thiol groups, carboxyl groups and / or hydroxyl-containing organic compounds of the molecular weight range 62-10,000, preferably 1,000 to 6,000.
  • the corresponding dihydroxy compounds are preferably used.
  • tri-functional or higher-functional compounds in the sense of the isocyanate polyaddition reaction in small proportions to achieve a certain degree of branching is possible, as is the possible use of tri- or higher-functional polyisocyanates already mentioned for the same purpose.
  • Hydroxyl compounds to be preferably used are the hydroxypolyesters, hydroxypolyethers, hydroxypolythioethers, hydroxypolyacetals, hydroxypolycarbonates and / or hydroxypolyesteramides known per se in polyurethane chemistry.
  • the hydroxyl group-containing polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature.
  • polyhydric alcohol oils include, for example, ethylene glycol, propylene glycol, (1,2) and - (1,3), butylene glycol 1,4) and - (2,3), hexanediol- (1,6), bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), further Polyethylene glycols, polypropylene glycols, and polybutylene glycols in question.
  • the polyesters may have a proportion of terminal carboxyl groups. Polyesters of lactones, for example E- caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, can also be used.
  • the polyethers which are preferred according to the invention and preferably have two hydroxyl groups are those of the type known per se and are, for example, polymerized by themselves with epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, for example in the presence of BF 3 , or by adding these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols and amines, for example water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxy-diphenylpropane, Aniline.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin
  • reactive hydrogen atoms such as alcohols and amines
  • Polyethers modified by vinyl polymers such as those produced by polymerizing styrene or acrylonitrile in the presence of polyethers (American Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695), German Patent 1 152 536) are also suitable.
  • the proportionally higher-functionality polyethers to be used, if appropriate, are formed in an analogous manner by alkoxylation of higher-functionality starter molecules known per se, for example ammonia, ethanolamine, ethylenediamine or sucrose.
  • polythioethers the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
  • polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, and formaldehyde.
  • Suitable polycarbonates containing hydroxyl groups are those of the type known per se.
  • polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures. Polyhydroxyl compounds already containing urethane or urea groups can also be used.
  • Low molecular weight polyols can also be used, e.g. Ethanediol, 1,2-and 1,3-propanediol, 1,4-and 1,3-butanediol, pentanediols, hexanediols, trimethylolpropane, hexanetriols, glycerol and pentaerythritol.
  • the preferred hydrophilically modified structural components include, in particular, the sulfonate group-containing aliphatic diols according to DT-OS 2 446 440, the cationic or also anionic built-in internal emulsifiers according to German patent application P 26 51 506.0 and also the monofunctional built-in polyether described in this patent application.
  • the reactants are generally used in such proportions that a ratio of isocyanate groups to hydrogen atoms reactive toward NCO, preferably from hydroxyl groups, of from 1.05 to 10, preferably from 1.1 to 3 correspond.
  • the order in which the individual reactants are added is largely arbitrary. You can either mix the hydroxyl compounds and add the polyisocyanate, or you can gradually add the mixture of hydroxyl compounds or the individual hydroxyl compounds to the polyisocyanate component.
  • the NCO prepolymers are preferably produced in the melt at 30-190 ° C., preferably at 50-120 ° C.
  • the prepolymers could of course also be produced in the presence of organic solvents, although one of the main advantages of the process according to the invention can be seen in the fact that such solvents can be dispensed with.
  • Suitable solvents e.g. in an amount up to 25% by weight, based on the solid, could be used e.g. Acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide or cyclohexanone.
  • NCO prepolymers in the process of the invention, in the production of which none of the hydrophilic structural components mentioned under 3 were used, in which the content of those mentioned under b) or c) above Groups is therefore 0. If such NCO prepolymers are used, which also have the properties mentioned under a) and d) above, the use of external emulsifiers is essential when carrying out the process according to the invention.
  • Suitable emulsifiers of this type are described, for example, by R. Heusch in "Emulsions", Ullmann, Volume 10, pages 449-473, Weinheim 1975.
  • Both ionic emulsifiers such as alkali and ammonium salts of long-chain fatty acids or long-chain aryl (alkyl) sulfonic acids are suitable, as well as non-ionic emulsifiers such as ethoxylated alkylbenzenes with an average molecular weight of 500 to 10,000.
  • These external emulsifiers are thoroughly mixed with the NCO prepolymers before the process according to the invention is carried out. They are generally used in amounts of 1 to 30, preferably 5 to 20% by weight, based on the weight of the NCO prepolymer. It is entirely possible, even when using hydrophilically modified NCO prepolymers, to increase their hydrophilicity by additionally using such external emulsifiers, although this is generally not necessary.
  • At least 2 organic compounds having primary and / or secondary amino groups are used in the process according to the invention. These compounds are preferably aliphatic or cycloaliphatic diamines with only primary and / or secondary amino groups.
  • araliphatic diamines are also to be regarded as aliphatic diamines.
  • Diprimary diamines are particularly preferably used, with particular preference being given to those diprimary diamines which have at least one cycloaliphatic ring in their molecule with in particular 6 ring carbon atoms, it being irrelevant whether the amino groups are linked directly to this cycloaliphatic ring or to an alkyl Substituents, especially methyl substituents of this aliphatic ring are linked.
  • the diamines to be used in the process according to the invention generally have a molecular weight of 60-500, preferably 100-250.
  • Suitable polyamines to be used in the process according to the invention are ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, propylene diamine-1,2, the mixture of isomers of 2,2,4- and 2,4,4-trimethylhexamethylene diamine, 1,3- and 1,4-xylylenediamine , Bis (2-aminoethyl) amine and methyl bis (3-aminopropyl) amine.
  • the preferred diamines include, for example: It is particularly preferred:
  • blocked amino groups are to be understood in particular as those primary or secondary amino groups which have been converted into the corresponding ketimine, aldimine or enamine group by reaction with an aldehyde or ketone.
  • Such ketimine, aldimine or enamine groups are largely inert to isocyanate groups at room temperature in the absence of moisture (cf.
  • the amines to be used in the process according to the invention are on average at most 1 mol free amino groups, preferably at most 0.15 mol free Have amino groups per mole of polyamine.
  • a triamine having a total of 3 primary and / or secondary amino groups which is not preferred but conceivable, it is also necessary if 2 of the total of 3 amino groups are present in blocked form.
  • the diamines mentioned by way of example it is necessary according to the statements made, but in extreme cases it is already sufficient if one of the two amino groups is present in blocked form.
  • suitable aldehydes or ketones are any at least one ketone or aldehyde group and having, otherwise inert under the reaction conditions, organic compounds.
  • aliphatic or cycloaliphatic aldehydes or ketones with a total of 2 to 18, or in the case of the cycloaliphatic compounds 5 to 18, preferably 3 to 6, or in the case of the cycloaliphatic compounds 5 to 6 carbon atoms are preferably used.
  • aldehydes or ketones examples include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclohexanone or cyclopentanone.
  • Aromatic aldehydes or ketones such as benzaldehyde, acetophenone or benzophenone are also suitable, but less preferred.
  • the NCO prepolymers which may contain external emulsifiers are mixed with the at least partially blocked polyamines mentioned.
  • the quantitative ratio between NCO prepolymer and at least partially blocked polyamine is generally chosen so that the equivalent ratio (NCO groups of the prepolymer): (free + blocked amino groups of the amine component) is between 4: 1 and 1: 1, 5, preferably between 2: 1 and 1: 1.25 and in particular between 1.2: 1 and 1: 1.2.
  • the two components are mixed in a temperature range from -20 to 100 ° C., preferably from 20 to 60 ° C.
  • the subsequent step of the process according to the invention consists in mixing the mixture with water to produce the aqueous dispersion with simultaneous hydrolysis of the blocked polyamine. So much water is used for this step that the dispersion has as high a solids content as possible. Dispersions with 40 to 70% solids can preferably be prepared very well. Further dilution with water is easily possible. The water is preferably added in one pour or gradually as desired.
  • the mixing of the prepolymer with capped polyamine with water can also be carried out by introducing the mixture into the aqueous phase or by first mixing the prepolymer and capped polyamine and then water using a continuous process in suitable mixing units. Water from 0 to 90 ° C., preferably from 20 to 60 ° C., is used.
  • the resulting dispersions are very fine, the particles preferably have a size of 20-200 nm, can of course also be larger.
  • the dispersions produced by the process according to the invention can of course be further modified in a known manner. You can e.g. add another water-soluble polyamine such as hydrazine after the dispersion, if the equivalent ratio of NCO to (blocked) amino groups has been selected so that free NCO groups are still present.
  • another water-soluble polyamine such as hydrazine
  • the question of whether the ver drive solutions or dispersions of the polyurethanes are obtained in water, is mainly dependent on the molecular weight and the hydrophilicity of the dissolved or dispersed particles, which in turn by suitable choice of type and ratio of the starting materials, especially in the preparation of the NCO prepolymers according to the known Principles of polyurethane chemistry can be set.
  • the use of an NCO prepolymer with a mean NCO functionality slightly below 2 leads to the polyaddition reaction being terminated before excessively high molecular weights are reached.
  • the polyurethanes produced by the process according to the invention and present in aqueous dispersion or solution are on a par with the known polyurethanes produced in organic solvents. Films made from them have excellent mechanical strength and hydrolysis resistance and can be used for a wide variety of applications.
  • a particularly preferred area of use of the dispersions or solutions according to the invention is the coating of flexible substrates.
  • the dispersions are particularly suitable for textile finishing, for glass fiber sizing or as adhesives.
  • a dispersion is formed with a solids content of 40% and a Ford cup viscosity (4 mm nozzle) of 14 seconds.
  • the dispersion shows a Tyndall effect in the translucent light.
  • the dispersion dries to clear, elastic films and is suitable for textile coating.
  • a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 250.2 g of a ketimine composed of isophoronediamine and methyl ethyl ketone (amino groups blocked to 87%) are stirred in and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
  • a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 225 g of a ketimine composed of isophoronediamine and acetone (amino groups blocked to 80%) are stirred in and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
  • a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 250.2 g of an aldimine composed of isophoronediamine and isobutyraldehyde (99% blocked amino groups) are stirred in and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall. Effect.
  • a prepolymer according to Example 1 is produced. After cooling to 60 ° C., 297 g of a ketimine composed of isophoronediamine and cyclohexanone (99% blocked amino groups) are stirred in and then dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
  • a prepolymer according to Example 1 is produced. After cooling to 50 ° C., 25.3 g of a condensation product of diethylene triamine and methyl ethyl ketone of the formula are added to, whereupon a temperature rise of 10 ° C occurs. The amount of free NH groups used corresponds to a conversion of 5% of the available NCO groups. 200.1 g of a ketimine composed of isophoronediamine (90% blocked amino groups) and methyl ethyl ketone are then stirred in and the mixture is dispersed as described in Example 1. The resulting dispersion is thin and shows a Tyndall effect.
  • a dispersion with a solids content of 30% and a Ford cup viscosity (4 mm nozzle) of 15 seconds is formed.
  • the dispersion shows a Tyndall effect in the translucent light.
  • the dispersion dries to clear, colorless, elastic films. It is suitable for coating paper and leather.
  • a dispersion is formed with a solids content of 30% and a Ford cup viscosity (4 mm nozzle) of 15 seconds.
  • the dispersion shows a Tyndall effect in the translucent light.
  • the dispersion is suitable as a binder in leather finishing. It dries to clear, colorless, elastic films.
  • a dispersion is formed with a solids content of 30% and a Ford cup viscosity (4 mm nozzle) of 13 seconds.
  • the dispersion shows a Tydall effect in the translucent light.
  • a dispersion is formed with a solids content of 30% and a Ford cup viscosity (4 mm nozzle) of 17 seconds.
  • the dispersion shows a strong Tyndall effect in the translucent light.
  • a mixture of the isophorone diisocyanate and the hexamethylene (1,6) diisocyanate is added to the mixture of the polyester, the two polyethers and the bisulfite adduct, which has been dewatered in vacuo at 120 ° C., and stirred at 100 ° C., until an NCO value of 6.2% is reached.
  • the prepolymer is cooled to 60 ° C., the bis-ketimine is added and water is then run into the well-stirred mixture. After 5 minutes, the hydrazine hydrate is added and stirring is continued for 2 hours.
  • a dispersion is formed with a solids content of 40% and a Ford cup viscosity (4 mm nozzle) of 13 seconds. The dispersion shows a Tyndall effect in the translucent light.
  • the dispersion is suitable for textile coating. It dries to a clear, colorless, elastic film, - which is characterized by hydrolysis resistance and resistance to UV radiation.
  • a dispersion is formed with a solids content of 30% and a Ford cup viscosity (4 mm nozzle) of 13 seconds.
  • the dispersion shows a Tyndall effect in the translucent light.
  • a dispersion is formed with a solids content of 30% and a Ford cup viscosity (4 mm nozzle) of 14 seconds.
  • the dispersion shows a Tyndall effect in the translucent light.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
EP19780100046 1977-06-07 1978-06-01 Verfahren zur Herstellung von wässrigen Polyurethan-Dispersionen und -Lösungen und deren Verwendung zur Beschichtung von flexiblen Substraten Expired EP0000029B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2725589 1977-06-07
DE19772725589 DE2725589A1 (de) 1977-06-07 1977-06-07 Verfahren zur herstellung von waessrigen polyurethan-dispersionen und -loesungen

Publications (2)

Publication Number Publication Date
EP0000029A1 EP0000029A1 (de) 1978-12-20
EP0000029B1 true EP0000029B1 (de) 1980-07-23

Family

ID=6010910

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19780100046 Expired EP0000029B1 (de) 1977-06-07 1978-06-01 Verfahren zur Herstellung von wässrigen Polyurethan-Dispersionen und -Lösungen und deren Verwendung zur Beschichtung von flexiblen Substraten

Country Status (10)

Country Link
US (1) US4829122A (enrdf_load_stackoverflow)
EP (1) EP0000029B1 (enrdf_load_stackoverflow)
JP (1) JPS543196A (enrdf_load_stackoverflow)
AT (1) AT371487B (enrdf_load_stackoverflow)
AU (1) AU516678B2 (enrdf_load_stackoverflow)
BR (1) BR7803624A (enrdf_load_stackoverflow)
CA (1) CA1129128A (enrdf_load_stackoverflow)
DE (2) DE2725589A1 (enrdf_load_stackoverflow)
ES (1) ES470537A1 (enrdf_load_stackoverflow)
IT (1) IT1104711B (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0004069A1 (de) * 1978-03-15 1979-09-19 Bayer Ag Verfahren zur Herstellung von wässrigen Lösungen oder Dispersionen von Polyurethanen sowie ihre Verwendung zur Herstellung von Überzügen, Lacken oder Beschichtungen
EP0009760A1 (de) * 1978-10-06 1980-04-16 Bayer Ag Verfahren zur Herstellung von wässrigen Dispersionen oder Lösungen von Polyurethan-Polyharnstoffen sowie ihre Verwendung
EP0075775A1 (de) * 1981-09-23 1983-04-06 Bayer Ag Verfahren zur Herstellung von hitzeaktivierbare Vernetzer enthaltenden wässrigen Dispersionen oder Lösungen von Polyurethan-Polyharnstoffen, die nach dem Verfahren erhältlichen Dispersionen oder Lösungen, sowie ihre Verwendung zur Herstellung von Überzügen
EP0098752A3 (en) * 1982-07-01 1984-12-12 Resem S.P.A. Process for producing aqueous dispersions of polyurethanes
EP0237997A1 (en) * 1986-03-18 1987-09-23 Takeda Chemical Industries, Ltd. Thermosetting resins and electrodeposition coating compositions containing the same
EP0531249B2 (en) † 1991-09-04 2008-08-06 Basf Corporation Novel coating compositions which may be ambient cured

Families Citing this family (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3048085A1 (de) 1980-12-19 1982-07-22 Bayer Ag, 5090 Leverkusen Dispersionen von sulfonatgruppen aufweisenden polymeren, ein verfahren zu ihrer herstellung, sowie ihre verwendung als beschichtungsmittel
DE3313237A1 (de) * 1983-04-13 1984-10-18 Bayer Ag, 5090 Leverkusen Waessrige, vernetzerhaltige polyurethanzubereitungen und ihre verwendung zur thermoaktiv-einstrich-umkehrbeschichtung
DE3621706A1 (de) * 1986-06-28 1988-01-07 Bayer Ag Verfahren zur herstellung von isocyanatgruppen aufweisenden prepolymeren, die nach diesem verfahren erhaeltlichen prepolymeren und ihre verwendung als bindemittel in einkomponentenlacken
DE3630045A1 (de) * 1986-09-04 1988-03-17 Bayer Ag Klebstoff und die verwendung des klebstoffs zur herstellung von verklebungen
DE3828157A1 (de) * 1988-08-19 1990-02-22 Hoechst Ag Verwendung von polyurethanharzen fuer waessrige fuellerzusammensetzungen
DE4016713A1 (de) * 1990-05-24 1991-11-28 Bayer Ag Waessrige polymerdispersionen und deren verwendung als beschichtungsmittel fuer textile substrate und leder
US5095069A (en) * 1990-08-30 1992-03-10 Ppg Industries, Inc. Internally-curable water-based polyurethanes
JP3197130B2 (ja) * 1993-12-27 2001-08-13 第一工業製薬株式会社 熱架橋性ポリウレタンエマルジョン組成物
DE4418157A1 (de) 1994-05-25 1995-11-30 Basf Ag Thermokoagulierbare wässerige Polyurethan-Dispersionen
US5569706A (en) * 1995-06-02 1996-10-29 Bayer Corporation Aqueous polyurea dispersions with improved hardness and solvent resistance
DE19523103A1 (de) * 1995-06-26 1997-01-02 Bayer Ag Wäßrige Bindemittelkombination mit langer Verarbeitungszeit, ein Verfahren zu ihrer Herstellung und ihre Verwendung
EP0774475A3 (de) 1995-11-17 1997-10-01 Basf Ag Wässerige Dispersionen enthaltend ein Polyurethan mit oximblockierten Isocyanatgruppen und/oder Carbonylgruppen in Keto- oder Aldehydfunktion
DE19719925A1 (de) * 1997-05-13 1998-11-19 Basf Ag Wäßrige Dispersionen aminogruppenhaltiger Polyurethane
US6325887B1 (en) * 1998-04-30 2001-12-04 Morton International, Inc. Heat-activatable polyurethane/urea adhesive in aqueous dispersion
KR100746464B1 (ko) 1999-12-23 2007-08-03 아크조 노벨 엔.브이. 부가 중합체 및 폴리우레탄을 포함하는 수성 코팅 조성물
US7459167B1 (en) 2000-07-27 2008-12-02 3M Innovative Properties Company Biocidal polyurethane compositions and methods of use
DE10133789A1 (de) * 2001-07-16 2003-02-06 Basf Ag Wässrige Dispersionen für hydrolysefeste Beschichtungen
US20040092622A1 (en) * 2002-07-01 2004-05-13 Pearlstine Kathryn Amy Inkjet ink with reduced bronzing
WO2005030873A1 (ja) * 2003-09-26 2005-04-07 Dainippon Ink And Chemicals, Inc. ポリウレタン樹脂水性分散体、それを含有してなる水性接着剤、及び水性プライマーコート剤
US20050182154A1 (en) * 2004-01-21 2005-08-18 Berge Charles T. Inkjet inks containing crosslinked polyurethanes
WO2006089935A1 (de) 2005-02-24 2006-08-31 Basf Aktiengesellschaft Strahlungshärtbare wässrige polyurethandispersionen
WO2007068683A1 (en) 2005-12-15 2007-06-21 Akzo Nobel Coatings International B.V. Multilayer coating system
US20080039582A1 (en) * 2006-07-28 2008-02-14 Hari Babu Sunkara Polytrimethylene ether-based polyurethane ionomers
DE102006036220A1 (de) 2006-08-03 2008-02-07 Clariant International Limited Polyetheramin-Makromonomere mit zwei benachbarten Hydroxylgruppen und ihre Verwendung zur Herstellung von Polyurethanen
US20080175875A1 (en) * 2006-09-25 2008-07-24 Hari Babu Sunkara Cosmetic compositions
EP1918314A1 (de) 2006-10-31 2008-05-07 Sika Technology AG Polyurethanzusammensetzung mit guter Anfangsfestigkeit
US8017047B2 (en) 2006-12-22 2011-09-13 Basf Se Microcapsules comprising compounds containing carbodiimide groups
DE102008000270A1 (de) 2007-02-14 2008-08-28 Basf Se Verfahren zur Herstellung von Polyurethandispersionen mit geringem Gehalt an hochsiedenden Lösungsmitteln
DE102008000478A1 (de) 2007-03-05 2008-09-11 Basf Se Polyurethan-Dispersionen mit Polyethercarbonatpolyolen als Aufbaukomponente
EP1975187A1 (de) * 2007-03-28 2008-10-01 Sika Technology AG Verfahren zur Herstellung von Polyurethanzusammensetzungen mit niedrigem Isocyanat-Monomergehalt
DE102007026196A1 (de) 2007-06-04 2008-12-11 Basf Se Verfahren zur Herstellung wasseremulgierbarer Polyurethanacrylate
US20130022746A9 (en) * 2007-12-10 2013-01-24 Harry Joseph Spinelli Aqueous inkjet inks with ionically stabilized dispersions and polyurethane ink additives
US20090259012A1 (en) * 2007-12-10 2009-10-15 Roberts C Chad Urea-terminated ether polyurethanes and aqueous dispersions thereof
US9410010B2 (en) 2007-12-10 2016-08-09 E I Du Pont De Nemours And Company Urea-terminated polyurethane dispersants
DE102008004178A1 (de) 2008-01-11 2009-07-16 Basf Se Textile Flächengebilde, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102008014211A1 (de) 2008-03-14 2009-09-17 Bayer Materialscience Ag Wässrige Dispersion aus anionisch modifizierten Polyurethanharnstoffen zur Beschichtung eines textilen Flächengebildes
US20090306285A1 (en) * 2008-05-08 2009-12-10 E.I.Du Pont De Nemours And Company Inkjet inks containing crosslinked polyurethanes
US20110039028A1 (en) * 2008-05-23 2011-02-17 E,I. Du Pont De Nemours And Company Inkjet ink with self dispersed pigments and polyurethane ink additives
US8759418B2 (en) 2008-05-23 2014-06-24 E I Du Pont De Nemours And Company Urea-terminated polyurethane dispersants
ES2377708T3 (es) 2008-08-26 2012-03-30 Basf Se Composición adhesiva para artículos autoadhesivos desprendibles, a base de polímeros adhesivos y nanopartículas orgánicas
EP2419466B1 (de) 2009-04-14 2017-09-13 Basf Se Klebstoff aus polymeren mit kristallinen domänen, amorphem polyurethan und silanverbindungen
EP2419465B1 (de) 2009-04-14 2014-09-03 Basf Se Verwendung von polyurethanklebstoff aus polyesterdiolen, polyetherdiolen und silanverbindungen zur herstellung folienbeschichteter möbel
DE102010043486A1 (de) 2009-11-16 2011-05-19 Basf Se Kaschierverfahren unter Verwendung von Carbodiimid- und Harnstoffgruppen enthaltenden Klebstoffen
EP2388283A1 (en) 2010-05-18 2011-11-23 Bayer MaterialScience AG Process for adjusting the viscosity of anionic polyurethane dispersions
WO2011150301A1 (en) 2010-05-27 2011-12-01 E. I. Du Pont De Nemours And Company Fixer inks for use with ink jet inks
EP2598546B1 (de) 2010-07-29 2019-04-10 Basf Se Biologisch desintegrierbare verbundfolien
US8956497B2 (en) 2010-07-29 2015-02-17 Basf Se Biodisintegratable composite foils
US9089624B2 (en) 2010-08-23 2015-07-28 Basf Se Ultrathin fluid-absorbent cores comprising adhesive and having very low dry SAP loss
CN103403049B (zh) 2010-12-20 2016-08-10 巴斯夫欧洲公司 制备聚氨酯-聚丙烯酸酯复合分散体的方法
DE102011015459A1 (de) 2011-03-29 2012-10-04 Basf Se Polyurethane, ihre Herstellung und Verwendung
EP2691465B1 (de) 2011-03-30 2015-09-09 Basf Se Latent reaktive polyurethandispersion mit aktivierbarer vernetzung
US8841369B2 (en) 2011-03-30 2014-09-23 Basf Se Latently reactive polyurethane dispersion with activatable crosslinking
JP2014519544A (ja) 2011-06-14 2014-08-14 ビーエーエスエフ ソシエタス・ヨーロピア 放射線硬化可能な水性ポリウレタン分散液
US9005762B2 (en) 2011-12-09 2015-04-14 Basf Se Use of aqueous polyurethane dispersions for composite foil lamination
EP2788447B1 (de) 2011-12-09 2015-09-16 Basf Se Verwendung von wässrigen polyurethandispersionen zur verbundfolienkaschierung
ES2640312T3 (es) 2012-07-04 2017-11-02 Basf Se Sistema de embalaje pegado para alimentos
WO2014044562A1 (en) 2012-09-18 2014-03-27 Basf Se Polymers comprising a polyurethane backbone endcapped with reactive (meth)acrylic terminating groups and their use as adhesives
CN104768994B (zh) 2012-11-02 2017-02-08 巴斯夫欧洲公司 聚氨酯水分散体用于层压模塑制品的用途
CN105074013B (zh) 2013-02-22 2018-10-02 巴斯夫欧洲公司 制备含水聚氨酯配制剂的方法
US10294392B2 (en) 2013-10-16 2019-05-21 Basf Se Process for preparing water-emulsifiable polyurethane acrylates
DE102014204582A1 (de) 2014-03-12 2015-09-17 Basf Se Neue Polymerdispersionen
EP3174944B1 (en) 2014-07-31 2020-08-26 DuPont Electronics, Inc. Aqueous ink-jet inks containing amphoteric polyurethane as binder
CN106795266B (zh) 2014-08-01 2021-03-09 巴斯夫欧洲公司 制备和使用水性聚氨酯/聚丙烯酸酯复合分散体的方法和所述水性聚氨酯/聚丙烯酸酯复合分散体在涂层剂中的用途
AU2015357109A1 (en) 2014-12-05 2017-06-29 Basf Se Aqueous adhesive dispersion containing polyurethanes and ethoxylated fatty alcohols
PL3230336T3 (pl) * 2014-12-09 2022-05-30 Basf Coatings Gmbh Wodna dyspersja poliuretanopolimocznikowa i wodny lakier bazowy zawierający dyspersję
WO2016162215A1 (de) 2015-04-07 2016-10-13 Basf Se Polymerdispersionen enthaltend n-acylpyrrolidine
DE112016005281T5 (de) 2015-11-18 2018-08-09 Cabot Corporation Tintenstrahltintenzusammensetzungen
US10385261B2 (en) 2017-08-22 2019-08-20 Covestro Llc Coated particles, methods for their manufacture and for their use as proppants
US10954402B2 (en) 2017-09-07 2021-03-23 Cabot Corporation Inkjet ink compositions
EP3694944B1 (de) 2017-10-11 2024-04-24 Basf Se Schutzfolien, hergestellt aus polyolefinträgermaterial, primer und strahlungsvernetzbarem schmelzklebstoff
US11814558B2 (en) 2018-02-21 2023-11-14 Basf Se Method for producing articles coated with adhesive
WO2019197234A1 (en) 2018-04-13 2019-10-17 Basf Se Oxygen scavenging aqueous lamination adhesive composition
WO2020144052A2 (de) 2019-01-11 2020-07-16 Basf Se Verfahren zur folienbeschichtung mit gravurwalzensystem
EP4114875A1 (en) 2020-03-02 2023-01-11 Basf Se Composite foils biodisintegratable at home compost conditions
US12269247B2 (en) 2020-06-09 2025-04-08 Basf Se Process for recycling of bonded articles
CN116897197A (zh) 2021-02-24 2023-10-17 巴斯夫欧洲公司 包含生物可降解的水性聚氨酯压敏胶黏剂的不干胶标签
EP4326804A1 (en) 2021-04-22 2024-02-28 Basf Se Process for preparing coated shaped bodies and their use
WO2023117937A1 (en) 2021-12-21 2023-06-29 Basf Se Environmental attributes for coating materials
WO2024083787A1 (en) 2022-10-18 2024-04-25 Basf Se Storage-stable coated particles and their preparation
WO2025002949A1 (en) 2023-06-28 2025-01-02 Basf Se Storage-stable coated particles and their preparation
WO2025162763A1 (en) 2024-01-29 2025-08-07 Basf Se Two-component lamination adhesive

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1064841A (en) * 1963-02-04 1967-04-12 Ici Ltd Manufacture of polymers containing biuret and urea groups
DE1770068C3 (de) * 1968-03-27 1981-01-15 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Polyurethanen Bayer AG, 5090 Leverkusen
US4108814A (en) * 1974-09-28 1978-08-22 Bayer Aktiengesellschaft Aqueous polyurethane dispersions from solvent-free prepolymers using sulfonate diols

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0004069A1 (de) * 1978-03-15 1979-09-19 Bayer Ag Verfahren zur Herstellung von wässrigen Lösungen oder Dispersionen von Polyurethanen sowie ihre Verwendung zur Herstellung von Überzügen, Lacken oder Beschichtungen
EP0009760A1 (de) * 1978-10-06 1980-04-16 Bayer Ag Verfahren zur Herstellung von wässrigen Dispersionen oder Lösungen von Polyurethan-Polyharnstoffen sowie ihre Verwendung
EP0075775A1 (de) * 1981-09-23 1983-04-06 Bayer Ag Verfahren zur Herstellung von hitzeaktivierbare Vernetzer enthaltenden wässrigen Dispersionen oder Lösungen von Polyurethan-Polyharnstoffen, die nach dem Verfahren erhältlichen Dispersionen oder Lösungen, sowie ihre Verwendung zur Herstellung von Überzügen
EP0098752A3 (en) * 1982-07-01 1984-12-12 Resem S.P.A. Process for producing aqueous dispersions of polyurethanes
EP0237997A1 (en) * 1986-03-18 1987-09-23 Takeda Chemical Industries, Ltd. Thermosetting resins and electrodeposition coating compositions containing the same
US4748200A (en) * 1986-03-18 1988-05-31 Takeda Chemical Industries, Ltd. Thermosetting resins and electrodeposition coating compositions containing the same
EP0531249B2 (en) † 1991-09-04 2008-08-06 Basf Corporation Novel coating compositions which may be ambient cured

Also Published As

Publication number Publication date
ATA406278A (de) 1982-11-15
AU516678B2 (en) 1981-06-18
DE2725589A1 (de) 1978-12-21
BR7803624A (pt) 1979-02-20
AU3690278A (en) 1979-12-13
IT1104711B (it) 1985-10-28
CA1129128A (en) 1982-08-03
JPS6237648B2 (enrdf_load_stackoverflow) 1987-08-13
IT7849700A0 (it) 1978-06-05
DE2860037D1 (en) 1980-11-13
ES470537A1 (es) 1979-01-01
US4829122A (en) 1989-05-09
AT371487B (de) 1983-06-27
EP0000029A1 (de) 1978-12-20
JPS543196A (en) 1979-01-11

Similar Documents

Publication Publication Date Title
EP0000029B1 (de) Verfahren zur Herstellung von wässrigen Polyurethan-Dispersionen und -Lösungen und deren Verwendung zur Beschichtung von flexiblen Substraten
EP0009760B1 (de) Verfahren zur Herstellung von wässrigen Dispersionen oder Lösungen von Polyurethan-Polyharnstoffen sowie ihre Verwendung
EP0004069B1 (de) Verfahren zur Herstellung von wässrigen Lösungen oder Dispersionen von Polyurethanen sowie ihre Verwendung zur Herstellung von Überzügen, Lacken oder Beschichtungen
EP0000381B1 (de) Verfahren zur Herstellung von seitenständige Hydroxylgruppen aufweisenden Isocyanat-Polyadditionsprodukten und die nach diesem Verfahren erhaltenen Produkte.
DE2446440C3 (de) Verfahren zur Herstellung von wäßrigen Dispersionen von Sulfonatgruppen aufweisenden Polyurethanen
EP0304718B1 (de) Wässrige Lösungen und Dispersionen von Polyisocyanat-Polyadditionsprodukten, ein Verfahren zur Herstellung der wässrigen Lösungen und Dispersionen sowie ihre Verwendung als Klebstoff
EP0269972B1 (de) Verfahren zur Herstellung von in Wasser löslichen oder dispergierbaren Polyurethanen und ihre Verwendung zur Beschichtung beliebiger Substrate
DE2637115C3 (de) Verfahren zur Herstellung von Polyurethanharnstoffen
EP0044460B1 (de) Feste, in Wasser dispergierbare, Isocyanatgruppen aufweisende Kunststoffvorläufer und Verfahren zur Herstellung von wässrigen Kunststoffdispersionen unter Verwendung dieser Kunststoffvorläufer
EP0792900B1 (de) Verwendung von ionischen und nichtionischen wässrigen Polyurethandispersionen als Bindemittel für Glasfaserschlichten sowie diese Dispersionen
DE60115478T2 (de) Bei niedriger Temperatur wärmeaktivierte Klebstoffe mit hoher Wärmebeständigkeit
EP0000568B1 (de) Verfahren zur Herstllung von wässrigen Dispersionen oder Lösungen von Isocyanat-Polyadditionsprodukten; Verwendung dieser Dispersionen bzw. Lösungen zur Herstellung von Überzügen und Beschichtungen
DE3630045A1 (de) Klebstoff und die verwendung des klebstoffs zur herstellung von verklebungen
EP0003785B1 (de) Überzugsmittel und Verfahren zur Beschichtung von PVC
EP1193277A2 (de) Pulverförmige, wasserdispergierbare blockierte Polyisocyanataddukte, ein Verfahren zur Herstellung und ihre Verwendung
EP0807650A1 (de) Beschichtungsmittel für Glas
EP0097290A1 (de) Einstufenverfahren zur Herstellung von Polyaminen aus NCO-Prepolymeren, Polyamine und deren Verwendung zur Herstellung von Polyurethanen
EP0000171A1 (de) Carboxylatgruppen aufweisende Polyisocyanat-Additions-produkte und ein Verfahren zu ihrer Herstellung
EP0148392A1 (de) Verwendung von Polyisocyanat-Polyadditionsprodukten als bzw.zur Herstellung von Klebemitteln
EP0133223B1 (de) Verfahren zur Herstellung von organischen Polyisocyanaten mit zumindest teilweise blockierten Isocyanatgruppen, die nach dem Verfahren erhältlichen Verbindungen und ihre Verwendung zur Herstellung von Polyurethanen, Einbrennlacken oder wässrigen Polyisocyanatlösungen bzw. -dispersionen
EP0099519B1 (de) Verfahren zur Herstellung von Kunststoffen auf Polyisocyanat-Basis
EP0538649B1 (de) Modifizierte Polyharnstoffe
EP0006204B1 (de) Wässrige Dispersionen von oligomeren oder polymeren Kunststoffen, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung
DE1595687A1 (de) Verfahren zur Herstellung grobdisperser,sedimentierender waessriger Polyurethandispersionen
DE2528212A1 (de) Verfahren zur herstellung von in wasser loeslichen oder dispergierbaren polyhydroxylverbindungen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB NL

REF Corresponds to:

Ref document number: 2860037

Country of ref document: DE

Date of ref document: 19801113

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19950522

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960513

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960601

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960619

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960620

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960630

Year of fee payment: 19

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970630

BERE Be: lapsed

Owner name: BAYER A.G.

Effective date: 19970630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19980101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980227

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19980101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980303

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT