CA2081414A1 - Aqueous polyurethane dispersion - Google Patents
Aqueous polyurethane dispersionInfo
- Publication number
- CA2081414A1 CA2081414A1 CA002081414A CA2081414A CA2081414A1 CA 2081414 A1 CA2081414 A1 CA 2081414A1 CA 002081414 A CA002081414 A CA 002081414A CA 2081414 A CA2081414 A CA 2081414A CA 2081414 A1 CA2081414 A1 CA 2081414A1
- Authority
- CA
- Canada
- Prior art keywords
- polyurethane
- groups
- acetone
- conversion
- anionic
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof
Abstract
BASFAKTIENGESELLSCHAFT O.Z. 0050/42811 Aqueous Polyurethane Dispersion Abstract of the disclosure:
An aqueous dispersion containing a polyurethane and from 5 to 60wt%, based on the polyurethane, of a polymeric adhesion enhancer, the polyurethane being essentially built up of (a) an organic polyisocyanate, (b) a dihydroxyl compound having a molecular weight exceeding 500 and ranging up to 5000g/mol and not containing any anionic groups or groups capable of conversion to anionic groups, (c) a di- or mono-hydroxyl compound containing carboxylic acid groups or carboxylate groups, (d) optionally a further compound different from (c) and containing one or two isocyanate-reactive functional groups and at least one anionic group or a group capable of conversion to an anionic group, (e) optionally a compound different from (c) and (d) and having two isocyanate-reactive functional groups and a molecular weight of from 60 to 500 g/mol, and the polyurethane or its prepolymer is prepared in a water-miscible solvent boiling below 100°C and, following the addition of the polymeric adhesionenhancer, is dispersed in water and, in the case of the prepolymer, the conversion of the latter to the polyurethane is carried out.
An aqueous dispersion containing a polyurethane and from 5 to 60wt%, based on the polyurethane, of a polymeric adhesion enhancer, the polyurethane being essentially built up of (a) an organic polyisocyanate, (b) a dihydroxyl compound having a molecular weight exceeding 500 and ranging up to 5000g/mol and not containing any anionic groups or groups capable of conversion to anionic groups, (c) a di- or mono-hydroxyl compound containing carboxylic acid groups or carboxylate groups, (d) optionally a further compound different from (c) and containing one or two isocyanate-reactive functional groups and at least one anionic group or a group capable of conversion to an anionic group, (e) optionally a compound different from (c) and (d) and having two isocyanate-reactive functional groups and a molecular weight of from 60 to 500 g/mol, and the polyurethane or its prepolymer is prepared in a water-miscible solvent boiling below 100°C and, following the addition of the polymeric adhesionenhancer, is dispersed in water and, in the case of the prepolymer, the conversion of the latter to the polyurethane is carried out.
Description
BASF~K ~ IE~GESELLSCt1~F~ 0 ~ ~oso/4i~8 1 1 ~8 Aqueous Polyurethane Dispersion .. . . _ . ... _ _ . .
The invention relates to an aqueous dispersion containing a polyurethane and from 5 to 60wt~/~, based on the polyurethane, of a polymeric adhesion enhancer, the polyurethane being essentially built up of s (a) an organic polyisocyanate, (b1 a dihydroxyl compound having a molecular weight exceeding 500 and ranging up to 5000g/mol and not containing any anionic groups or groups capable of conversion to anionic groups, (c) a di- or mono-hydroxyl compound containing at least one anionic group or a group capable of conversion to an anionic group, (d) optionally a further compound different from (c) and containing one or two isocyanate-reactive functional groups and at least one anionic group or a group capable of conversion to an anionic group, (e) optionally a compound having at least two isocyanate-reactive functional groups and a molecular weight of from 60 to 500g/m~l and not containing 20 any anionic groups or groups capable of conversion to anionic groups, and the polyurethane or its prepolymer is prepared in a water-miscible solvent boiling below 1 00C and, following the addition of the polymeric adhesion enhancer, is dispersed in water and, in the case of the prepolymer, the conversion 25 of the latter ~o the polyurethane is carried out.
German Patent Application 4,024,567 and DE-A 3,903,538 disclose emulsifier-free dispersions for usa as adhesives, which contain a polyurethane and other polymers, for example a phenol-formald0hyde resin, which enhance the adhesive 30 characteristics. In the process described in DE-A 3,903,538, the polyurethane is prepared in a low-boiling water-miscible solvent, after which the polymeric adhesion enhancer is added and the resulting rnixture is then dispersed in water.
This procedure produces stable aqueous dispersions in wnich the added polymeric 35 adhesion enhancer is presumably located inside the dispersed particles, where it is surrounded by a stabilizing layer of poiyurethane. A particularly marked positive I~ASF~YT EllGtSE' ~SC~lAF' O Z ooso/4;2~ 1 i feature of such dispersions, when used as adhesives, is their good init~ v~l¦
strength.
A negative feature of these dispersions, however, is that they are stil! too viscous.
s Such adhesives must in general be applied in the form of highly concentrated dispersions, preferably of low viscosity. At the same time, the particles contained therein must be fine to ensure that the dispersion has a high shear strength.
It is thus an object of the invention to provide dispersions having good adhesion properties and minimum viscosity.
Accordingly, we have found the dispersions defined above and their use as adhesives.
Preferred embodiments of the invention are disclosed in the sub-claims.
The emulsion-free dispersions of the invention contain a polyurethane and from 5to 60 wt~, based on the polyurethane, of a polymeric adhesion enhancer.
The invention relates to an aqueous dispersion containing a polyurethane and from 5 to 60wt~/~, based on the polyurethane, of a polymeric adhesion enhancer, the polyurethane being essentially built up of s (a) an organic polyisocyanate, (b1 a dihydroxyl compound having a molecular weight exceeding 500 and ranging up to 5000g/mol and not containing any anionic groups or groups capable of conversion to anionic groups, (c) a di- or mono-hydroxyl compound containing at least one anionic group or a group capable of conversion to an anionic group, (d) optionally a further compound different from (c) and containing one or two isocyanate-reactive functional groups and at least one anionic group or a group capable of conversion to an anionic group, (e) optionally a compound having at least two isocyanate-reactive functional groups and a molecular weight of from 60 to 500g/m~l and not containing 20 any anionic groups or groups capable of conversion to anionic groups, and the polyurethane or its prepolymer is prepared in a water-miscible solvent boiling below 1 00C and, following the addition of the polymeric adhesion enhancer, is dispersed in water and, in the case of the prepolymer, the conversion 25 of the latter ~o the polyurethane is carried out.
German Patent Application 4,024,567 and DE-A 3,903,538 disclose emulsifier-free dispersions for usa as adhesives, which contain a polyurethane and other polymers, for example a phenol-formald0hyde resin, which enhance the adhesive 30 characteristics. In the process described in DE-A 3,903,538, the polyurethane is prepared in a low-boiling water-miscible solvent, after which the polymeric adhesion enhancer is added and the resulting rnixture is then dispersed in water.
This procedure produces stable aqueous dispersions in wnich the added polymeric 35 adhesion enhancer is presumably located inside the dispersed particles, where it is surrounded by a stabilizing layer of poiyurethane. A particularly marked positive I~ASF~YT EllGtSE' ~SC~lAF' O Z ooso/4;2~ 1 i feature of such dispersions, when used as adhesives, is their good init~ v~l¦
strength.
A negative feature of these dispersions, however, is that they are stil! too viscous.
s Such adhesives must in general be applied in the form of highly concentrated dispersions, preferably of low viscosity. At the same time, the particles contained therein must be fine to ensure that the dispersion has a high shear strength.
It is thus an object of the invention to provide dispersions having good adhesion properties and minimum viscosity.
Accordingly, we have found the dispersions defined above and their use as adhesives.
Preferred embodiments of the invention are disclosed in the sub-claims.
The emulsion-free dispersions of the invention contain a polyurethane and from 5to 60 wt~, based on the polyurethane, of a polymeric adhesion enhancer.
2~) The polyurethane is substantially, and preferably exclusively, composed of the constituents (a) to (e). The isocyanate-reactive Func~ional groups are hydroxyl groups or primary or secondary amino groups.
Particularly suitable poiyisocyanates (a) are aliphatic, cycloaliphatic, and aromatic 25 diisocyanates. The polyisocyanates preferably used have the general formula X(NCO)2, where x stands for an aliphatic hydrocarbon radical having from 4 to 12carbon atomsl a cycloaliphatic hydrocarbon radical haviny from 6 to 15 carbon atoms, or an aromatic hydrocarbon radical having from 6 to 15 carbon atoms.
Examples of suitable aliphatic, cycloaliphatic, and aromatic diisocyanates are 1,4-butane diisocyanate, 1 ,6-hexane diisocyanate, Z,2,4- and 2,4,4-tl imethylhexa-methylene diisocyanates, cyclohexane diisocyanate, methylcyclohexane diisocya-nate, isophorone diisocyanate, 4,4'-diisocyanatodiphenylm0thane, 4,4'-diisocya-natodicyclohexylmethane, and 2,4- and 2,6-toluene diisocyanates.
Mixtures of these diisocyanates may be used, if desired. Particularly suitable mixtures are those of aliphatic or cycloaliphatic diisocyanates with aromatic diisocyanates in a molar ratio of from 1:4 to 5:1.
40 The diisocyanates may be supplemented by minor quantities of monoisocyanates, BA SFi~rl~`.G~ FI _ 2 ~ ~o~/~Z~
if desired. to regulate the molecular weight.
Suitable dihydroxyl compounds (b) having a molecular weight exceeding 500 and ran~ing up to 5000g/mol are the wel7-known poiyesters, polyethers, polythio-ethers, polylactones, polyacetals, polycarbonates, and polyesteramides containing two hydroxyl groups. The preferred dihydroxyl compounds are those having molecular weights between 750 and 3000. Mixlures of these dihydroxyl compounds can, of course, be used if desired.
Suitable components (c) are aliphatic, cycloaliphatic, and aromatic mono- or di hydroxycarboxylic acids. Use is preferably made of dihydroxy-alkylcarboxylic acids, and more preferably of such acids havirlg from 3 to 10 carbon atoms, suchas are described in US-A 3,412,054. Particularly preferred compounds are those of ~he general formula COOH
in which R1 denotes a hydrogen atom or an alkyl radical of from 1 to 4 carbon zO atoms, and R2 and R3 stand for a C,-C4 alkylene group. An example of such a compound is 2,2-dimethylolpropionic acid.
The optional constituent (d~ may be a compound different from (c) and containingone or two isocyanate-reactive amino groups and at least one anionic group or a 25 group capable of conversion to an anionic group. The groups which are capable of conversion to anionic groups are usually carboxylic acid groups or sulfonic acidgroups. Worthy of mention are aminocarboxylic acids and aminosulfonic acids, forexample Iysine, -alanine, N-(2-aminoethyl)-2-aminoethanesulfonic acid, and the adducts of aliphatic diprimary diamines on -olefinic carboxylic acids as described 30 in DE-A 2,034,479, eg, the adduct of ethylenediamine on acrylic acid.
Both of the components (c) and (d) contain ionic groups, or groups which are capable of conversion to ionic groups, to ensure that the polyurethane is dispersible in water.
In order to convert potentially anionic groups, eg, carboxylic acid groups or sulfonic acid groups, to ionic groups, use may be made of inorganic and/or organic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonia, or primary, secondary, and, in particular. tertiary40 amines, eg, triethylamine or dimethylaminopropanol.
2 a ~
BASFAKTIEYaEsELLsc~AFT o...~oso/428 ~ 1 ___ The neutralization of the potentially anionic groups may be effected before, during, but preferably after, the isocyanate polyaddition reaction.
If desired, additional emulsifying constituents may also be used, for example monohydric polyether alcohols having a molecular weight of from 500 to 10,000g/mol and preferably from 1,000 to 5,000g/m~l. Monohydric polyether alcohols can be obtained by alkoxylation of monohydric starting molecules such as methanol, ethanol, or n-butanol, the alkoxylating agent being ethylene oxide or a mixture of ethylene oxide with some other alkylene oxide, especially propylene oxide. When such mix~ures are used, they preferably contain at least 40 mol~c, and more preferably at least 65 mol~, of ethylene oxide.
However, the addition of such nonionic emulsifiers is not generally necessary due to the presence of constituent (c) and, optionally, constituent (d).
The constituent (e) is essentially a compound having two hydroxyl groups, or twoamino groups, or one hydroxyl group and one amino group. Examples of suitable compounds are dihydroxyl compounds such as 1,3-propanediol, 1,4-butanediol, diamines such as ethylene diamine, hexamethylene diamine, piperazine, 2,5-20 dimethylpiperazine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isopho-rone diamine), 4,4'-diaminodicyclohexylmethane, 2,4-diaminocyclohexane, 1,2-diaminopropane, hydrazine, and amino alcohols such as ethanolamine, isopropanol-amine, methylethanolamine, and aminoetho~ye~hanol. If desired, compounds (e) having more than two isocyanate-reactive groups can be used.
Preferably, the weights of the components (a) to (e) are such that the total number of isocyanate-reactive functional groups, generally hydroxyl groups or amino groups, represents from 0.9 to 1.1 and more preferably from 0.95 to 1.05 gram equivalents per gram equivalent of isocyanate.
The most preferred situation is when the number of isocyanate-reactive functional groups is equal to that of the isocyanate groups.
The proportions of the individual components, based on one gram equivalent of 35 isocyanate, are preferably as follows:
component (b) from 0.15 to 0.8 and more preferably from 0.3 to 0.6 gram equivalents, component (c) from 0.03 to 0.4 and more preferably from 0.05 to 0.4 gram 2 ~
E~ASFAK~ GESE' ~SCI~AFT 0 Z o~so/42811 equivalents, component ~d) from 0 to 0.4 and more preferably from 0 to 0.3 gram equivalents, s component ~e) from 0 to 0.8 and more preferably from 0 ~o 0.6 gram equivalents.
In order to prepare the polyurethane, the constituents (a) to (e) are reacted in~0 known manner in a water-miscible low-boiling organic solvent, as described, for example, in D~-A 3,437,918.
Examples of particularly recomrnendable solvents are tetrahydrofuran, methylethyl ketone, N-methylpyrrolidone, are especially acetone.
s The reaction temperature is preferably from 50 to 1 00C.
The diisocyanate reaction can be accelerated by including conventional and well-known catalysts such as dibutyltin dilaurate, tin(ll) octoate, or 1,4-diazabicyclo-20 [2.2.2]octane.
The resulting polyurethane, which is substantially free from isocyanate groups, isdispersed in water after the addition of the polymeric adhesion enhancer, and the organic solvent is then removed, by distillation, to the desired extent, usually25 completely.
Alternatively, the polyurethane may be prepared by first producing a polyurethane prepolymer in the water-miscible low-boiling organic solvent. To this end, at least the constituents ~a) and (b) and a portion of (c) are interreacted. After the addition 30 of the polymeric adhesion enhancer, the resulting polyurethane prepolymer, which still contains isocyanate groups, is dispersed in water. The reaction of the prepolymer is then continued, in particular, with the r0maining constituents. The organic solvent can then be removed in the manner described above.
35 The polymeric adhesion enhancer can be one of a nurrIber of different polycondensates, polymers produced by free-radical polymerization, or poly-adducts.
The polymeric adhesion enhancer is preferably a phenoi-formaldehyde condensa-tion resin preferably having a molecular weight (weight average Mw) of from 500 to 2000 and a softening point ranging from 80 to 1 30C. Particularly preferred 2 ~
~ASF~ E'`IGESELLSC~AFT C' . ooso/4~
phenoi-formaldehyde cc~ndensation resins are novolaks, as may be obtained by acid-catalyzed reaction of phenois particularly phenol or phenol substituted by c1-c~O alky' groups, with formaldehyd~s. More particularly, the reaction is carried out using from 1.05 to 1.3 mol of phenols per mole of formaldehyde.
s Also particularly suitable are epoxy resins, preferably the reaction products ofepoxides such as epichlorohydrin with bisphenol A, those being particularly preferred which have a molecular weight (weight average Mw) o~ frorn 500 to 5000 and a softening point ranging frorn 80 to 1 30C.
Other suitabie polymeric adhesion enhancers are poly~vinyl acetate), poly(vinyl chloride), poly(methyl methacrylate), polyamides, polyethers, polyesters, polyether-diols, polyesterdiols, poiyurethanes, especially polyurethanes free from salt groups, and phenacrylates.
~s Preferred poly(vinyl acetate)s are homopolymers of vinyl acetate. Also useful are the copoiymers thereof containing up to 10wt% of comonomers such as vinyl laurate, vinyl stearate, or, preferably, esters of (meth)acrylic acid or fumaric acid or maleic acid with C1-C8 alkanols such as methanol, n-butanol, or 2-ethylhexanol.
Z0 The polymers usually have a K-value, as measured at 25C in cyclohexanone as specified in DIN 53,726, of from 45 to 60. By poly(vinyl chloride) we generally mean homopolymers of vinyl chloride or copolymers thereof containing up to 10wt% of comonomer such as ethylene or vinyl acetate. Their K-value (25C, cyclohexanone, DIN 53,726) should be between 45 and 55. The poly(methyl 25 methacrylate)s used by the person skilled in the art will normally be homopolymers of methyl methacrylate or copolyrners thereof containing up to 1 0wt%, based on the weight of the copolymer, of vinyl acetate, an ester of acrylic acid with a C1-C8 alkanol, or an ester of methacrylic acid with a C2-c8 alkanol. Their melt flow index MFI, determined as specified in DIN 53,735 (230C~3.8kg) iS generally between 30 0.1 and 3.û. The synthesis of such polymers is generally carried out by free-radical polymerization of the ethylenically unsaturated monomers at a ternperature between 30 and 150C in substance, in solution, or in emulsion, followed by drying. Such polymers are well known, eg, from Houben-Weyl, Methoden der Organischen Chemie, Vol. E20, 1987, pp. 1115-1125, 1041-1062, and 1141-35 1174.
Suitable polyamides have a K-value of from 65 to 80, determined in sulfuric acidat 25C as specified in DIN 53,727. They are usually polymers derived from lactams having from 7 to 13 ring units such as -caprolactam, E-capryllac~am, or -laurolactam, eg, polycaprolactam (PA6), or they may ~e polyamides produced by reacting dicarboxylic acids with diamines. Examples are poly( hexamethylene 2 Q ~
BASFAKT~ uEsEL~scH~T ~ Z ooso/42811 adipamide) (PA66), poly~hexamethylene sebacamide) (PA610), and poly(hexa-methylene dodecanamide) (PA612). Suitable dicarboxylic acids are, for example, alkanedioic acids containing from 4 to 12, and preferably from 6 to 10, carbsn atoms, and phthalic acid, terephthalic acid, and isophthalic acid, as well as arbitrary mixtures of said acids. Examples of suitable diamines are alkanediamines having from 4 to 12, and preferably from 4 to 8, carbon atoms, and also m-xylylenediamine, p-xylylenediamine, their hydrogenated derivatives, bis(4-amino-phenyl)methane, bis~4-aminocyciohexyl~methane, and bis(4-aminophenyl)propane-2,2, or mixtures thereof. Due to their good solubility properties, copolymers are preferred, for example a copolyamide of 30-40 wt~ adipic acid, 15-20 wt~Y(;
hexamethylenediamine, 30-35 wt~ ~-caprolactam, and 1~-20 wt~ -aminocaproic acid. The manufacture of these well-known polymers is part of the specialized knowledge of the person skilled in the art, cf, eg, Rompp, Chemielexikon, 8th Edition, pp. 2861, 3058, and 3267, or EP-A 129,195 and EP-A 129,196.
~s Polyetherdiols are known per se, for example from Kunststoff-Handbuch Vol.7 (1983) pp. 42 to 54. Examples are poly(ethylene oxide), poly(propylene oxide), and polytetrahydrofuran, or copolymers thereof containing two ~erminal hydroxyl groups. They are produced in known manner, generally by anionic polyaddition, of, 20 eg, N.G.Gaylord, High Polymers, Vol.13, New York 1963, Part 1. Of minor significance are polyetherols grafted with ethylene oxide to increase reactivity. The polyetherdiols generally have a molecular weight of from 300 to 3000 corresponding to a K-value of from 25 to 60, as deterrnined in DMF at 25C as specified in DIN 53,726. Preferred molecular weights are between 800 and 2200 zs corresponding to K-va!ues between 20 and 50.
The polyethers used are, eg, poly~ethylene oxide), poly(propylene oxide), and polytetrahydrofuran. The polyethers usually have a K-value in DMF at 25C (DIN
53,726) of from 20 to 50. They are well known, cf, eg, Encyclopedia of Polymer 30 Science and Techno/ogy, Vol.6, 1967, pp. 103 et seq, Vol.9, 1968, pp. 668 et seq, and Vol.13, 1970; pp. 670 et seq.
The preferred polyesters are monomer-free unsaturated polyester resins. These are known condensation polymers of polyvalent, preferably divalent, carboxylic 35 acids and their esterifiable deriva~ives, especially their anhydrides, which are linked by an ester-like bond to polyhydric, preferably dihydric, alcohols and optionally contain additional radicals of monovalen~ carboxylic acids or of monohydric alcohols. Examples of the starting materials are as follows: maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, maleic anhydride, phthalic anhydride, isophthalic anhydride, ethylene glycol, propyleneglycol, 1,4-butanediol, and neopentyl glycol. Of minor significance for the present _ 7 BA~iFAK~ GLSE~LSC~Fl o - ooso/4281 1 invention are those resins which are prepared by co-condensation of bisphenol A,epichlorohydrin-bisphenol A condensates, and methacrylic acid. In this context, "monomer-free" means that these unsaturated polyester resins (UP resins) are notdissolved in a monomer, such as styrene, which could induce cross-linking. The products usually have a viscosity at 150C of from 1000 to 6000mPa ~i and preferably from 2000 to 4000 mP~
Suitable polyesterdiols are condensation polymers containing two terminal hydroxyl groups and derived from dicarboxylic acids such as adipic acid or isophthalic acid condensed with diols such as 1,4-butanediol, 1,6-hexanediol, or neopentyl glycol.
The molecular weight range of the polyesterdiols used is generally from 300 to 5000. Preferred molecular weights are between 800 and 2500 corresponding to a K-value in DMF at 25C ~DIN 53,276) of from 30 to 55. These polymers and their manufacture are generally known, cf Kunststoff-Handbuoh Vol.7 (1983) pp. 54 to 62 and DE 1,268,842.
Salt group-free polyurethanes are known addition polymers based on polyether-diols, polyesterdiols, isocyanates such as hexamethylene diisocyanate, 2,4-diisocyanatodiphenylmethane, and possibly bifunctional or trifunctional chain extenders, which are prepared by conventional methods, cf Kunststoff-Handbuch Karl-Hanser-Verlag, Vol.7 (1966~. The preferred condensates are those having a low molecular weight (K-value in DMF at 25C as specified by DIN 53,726: from 25 to 60). Cross-linked polyurethanes are of minor irnportance.
Phenacrylates are preferably made by the addition of bisphenol A glycidyl ether (meth)acrylates to terephthalic acid. It is also possible to use phenacrylates based on epoxidized novolaks. The K-values of these polymers generally range from 30 to 55 (determined in cyclohexane at 25C as specified in DIN 53,726).
The polymeric adhesion enhancer is added to the polyurethane or its prepolymer present in a water miscible low-boiling organic solvent prior to dispersion thereof in water, ie, prior to the formation of the aqueous dispersion of the invention having an aqueous continuous phase. Basically, the resin can be added to the reaction 35 mixture of the starting components of the polyurethane at any desired time, but it is particularly advantageous not to add the resin until the prepolymer formation has reached an advanced stage and the NCO content of the prepolymer has reached a value of less than 1.5wt~/(i. Especially in the case of resins containing groupswhich are particularly reactive to isocyanates, such as the novolaks, the resins40 should only be compounded with polyurethane resins having an NCO content nearOwt%. The polymer may be added in substance or in the form of a solution.
2 ~
BASFA~, i NG~S~SC~1AF~ _ 0 Z o~so/42811 Suitable solvents for the polymer are water (eg, in the case of phenol-formaldehyde resins~ and, more particularly, again water-miscible low-boiling organic solvents.
s The dispersion of the invention, as finally obtained follcwing the dispersion of the mixture in water, the conversion of the polyurethane prepolymer to the polyurethane, if applicable, and the removal of the organic solvent by distillation, if necessary, preferably has a solids content of from 10 to 70 wt~ and more preferably from 20 to 50 wt~o.
The dispersions of the invention can be immediately used for making joints between widely varying substrates, for example wood, plastics, glass, and metal.To achieve special properties, it is possible to add auxiliaries to the dispersions, for example plasticizers, fiim formers, fillers, etc.
The dispersions have good adhesion properties and are particularly noteworthy for their initial adhesive strength, this being the result of their low viscosity. In general, the viscosity of a dispersion can be reduced by increasing the particle diameterwithout changing the solids content (û.Lorenz, G.Rose, Colloid Polym. Sci. 260 20 (1982) p. 1079). However, ~here is the risk of coagulation of larger dispersed particles, particularly when shearing forces are applied.
Surprisingly, the dispersions of the invention are even less viscous than dispersions containing particles of larger sizes.
zs Exam~lç~
The viscosities of the dispersions were measured at a shear rate of 100 ~ ~ using a rotational rheometer comprising concentric cylinders (diameter of bob: 38.7mm, 30 diameter of cup: 42.0 mm).
The particle size of the latex particles was determined indirectly via turbiditym0asurements, in which the turbidity of a dispersion having a solids content of 0.01 wt~ was compared with distilled water at room temperature for a layer 35 thickness of 2.5cm.
LD I ntensitydjSperSion x 100 I ntenSitywater In the following examples the symbols have the meanings given below:
ADA = adipic acid BASFAKrlENGES~LSC,`1~FT G Z ooso~
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .
B14 = 1,4-butanediol TDI ~ toluene diisocyanate HDI = hexamethylene diisocyanate PUD = Na salt of the Michael adduct of acrylic acid and ethylenediamine s DBTL = dibutyltin dilaurat0 DMPA = dimethylolpropionic acid Comparative Example 1 TDI was added to a mixture of dehydrated polyesterol, acetone I and catalyst. After a reaction time of 1 hour at 65C, HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixture had anNCO contant of 0.69 /0.
Chain-extension was carried out at 50C by the addition of PUD, this salt being in the form of a 40 ~0 solution in water. After 5 min, the resin solution prepared from acetone lll and Epikote 1001 was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting materials Molar amount Parts by weight [mmol~ [g~
Polyesterdiol ADA/B14 (OH number 45.2) 199 493 TDI 148 25.8 HDI 149 25.0 DBTL 0.1 Acetone 1 133 Acetone l l 532 0 Epikote 1001 (condensation product of bisphenol A and epichlorohydrin, Mw ca 450-500) 240 Acetone l l l 240 PUD (40 /0 solution of salt) 95 41 35 Deionized water 1200 Comparative Example 2 40 The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediolJ
~g)~
BASFA~r~E~lG~.E~ .C~ T __ _ _ __ _ O ~ ooso/4281 1 . _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ . _ . _ _ _ _ _ _ . . . _ _ _ _ . _ _ . _ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ . . . _ _ . . _ _ . _ _ _ _ _ _ . _ _ _ _ . _ _ _ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ acetone I and catalyst. After a reaction time of 1 hour at 65(~ he HDI was added and the reaction continued for another 90 mill. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.63 ~
s Chain-extension was carried out at 50C by the addition of PlJD, this salt being in the form of a 40 ~ solution in water. After 5 min, the resin solution prepared from acetone lll and a polyesterol was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting material~
Molar amount Parts by weight [mmol] [g]
Polyesterdiol ADA/B14 (OH number 45.0) 193 482 ~s 1,4-butanediol 58 5.2 TDI 169 29.4 HDI 169 28.3 Acetone 1 133 Acetone l l 533 20 Polyesterdiol ADA/B14 ~OH number = 45.0) 240 Acetone l l l 240 PU[3 (40 ~'~fi solution of salt) 86 37.5 Deionized water 1 20û
Comparative Example 3 The TDI was added to the mixture of dehydrated poly(tetramethylene oxide), 1,4-30 butanediol, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI
was added and the reaction continued for another 90 min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.70 /0.
Chain-extansion was carried out at 50C by the addition of PUD, this salt being in 35 the form of a 40 % solution in water. After 5 min, the resin solution prepared from acetone lll and Epikote 1007 was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
~ASF ~,IE~ S~ H~rT __ _ O_ ooSo_4 Starting materials _ _ ~
Molar amount Parts by weight [ml1loll [~]
s Poly(tetramethylene oxide) ~OH-number 4~.0) 213 435 1,4-Butanediol 213 19.2 TDI 260 45.3 HDI 260 43.8 Acetone 1 132 Acetone ll 532 Epikote 10û7 (condensation polymer of bisphenol A and epichlorohydrin~
Mw ca 1550-2000 ) 240 Acetone lll 240 PUD (40 ~`Yr solution of salt) 94 41 Deionized water 1200 Example 1 The TDI was added to the mixture of dehydrated polyesterol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90tnin. FQIIOWjng the addition of acetone ll, thereaction mixture had an NCO content of 0.65 ~/O.
zs Chain-extension was carried out at 50C by the addition of PUD, this salt being in the form of a 40 ~/O solution in water. After 5 rnin, the resin solution prepared from acetone lll and Epikote 1007 was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting materials Molar amount Parts by weight [mrnol] [g]
35 PolyesterdiolADA/B14(0Hnumber = 45.2) 194 481 DMPA 56 7.4 TDI 164 28.6 HDI 167 28.1 DBTL 0.1 40 Acetone 1 133 BASFA~T!t!lG~S~L~SC~ T ~ (-J '7 o~
Acetone l l 533 PUD (40 ~, solution of salt) 84 36.8 Aceton lll 240 Epikote 1007 (condensation product o~
s bisphenol A and epichlorohydrin, Mw ca 1550-2000 ) 240 Deionized water 1200 . _ Example 2 Procedure:
The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.60%. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from Lupraphen VP 9186 and acetone lll. The mixture was then neutralized with 30 ~
20 caustic soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials .
Molar amount Parts by weight [mmol] lg]
Polyesterdiol ADA/B14 ~OH number = 45.0) 166 414 1,4-Butanediol 50 4.5 DMPA 250 3.5 TDI 273 47.6 HDI 273 45.9 DBTL 0.1 Acetone 1 1 34 Acetone ll 534 35 Polyester resin:
Lupraphen VP 9186 Polyesterdiol ADA/Bt 4 (OH number = 473 240 Ac0ton lll 240 NaOH solution (30%) 187 25.0 Deionized water 1 200 2 ~
BASF~TIE~OEsELLScHAF, o.z.ooso/42B11 _ _ _ _ _ .
_ple The TDI was added to the mixture of dehydrated polytetramethylene oxide, 1,4-butanediol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixhJre had an NCO content of 0.60YG. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from Epikote 1007 and acetone lll. The mixture was then neutralized with 30æ caustic soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials .. .. . _ . . . _ ~olar amount Parts by weight [mmol] [g]
Poly(tetramethylene oxide) (OH number = 45.0) 191 390 DMPA 239 32.1 1,4-butanediol 191 17.3 zO T~l 351 61.2 HDI 351 59.1 DBTL O.1 Acetone 1 137 Acetone ll 548 25 Epikote 1007 (condensation polymer of bisphenol A and epichlorohydrin, ii7W ca 1 55û-2000) 240 Aceton lll 240 NaOH soiution ( 30 ~O) 1 68 22 .3 30 Deionized water 1200 Exampl ~s The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.65%. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from Epikote 1007 and acetons Ill. The mi~ure was then neutralized with 30 O~G caustic 2 a ~
BASF~ ~, E N G 5 S E L LSC ~A FT O . . ooso /4 2 8 11 soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials .
s Molar amountParts by weight [mmol] [g]
Polyesterdiol ADA/B1 4 (OH number = 45.0) 168 419 DMPA 235 31.5 1,4-butanediol 50 4-5 TDI 267 46.5 HDI ~67 44.9 DBTL 0. 1 Acetone 1 134 Acetone ll 534 E,oikote 1 007 (condensation polymer of bisphenol A and epichlorohydrin, i~w ca 1 550-2000) 240 Aceton lll 240 NaOH solution (30 %) 176 2~.5 Deionized water 1200 _ ample 5 The TDI was added to the mixture of dehydrated polyesterol, DMPA, 1,~-butanediol, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI
was added and the reaction continued for another 90 min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.61 ~h.
Chain-extension was carried out at 50C by the addition of PUD, this salt being in the form of a 40 5~0 solution in water. After 5 min, the r~sin solution prepared from acetone lll and phenol-formaldehyde cond0nsate was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and35 the acetone distilled off.
Starting materials Molar amount Parts by weight lmmol] [g]
4D PolyesterdiolADA/B14 (OHnumber = 45.0) 192 477 __ ~ __ 1 5 ~ASF~r ~ s~ F~ ____ ___ __Z coso/q28 1,4-butanediol 57 5.2 DMPA 31 4.2 TDI 177 30.8 HDI 177 29.7 5 DBTL 0.1 Acetone 1 133 Acetone ll 531 PUD (40 % sait solution) 73 31.9 Phenol-formaldehyde condensate tO MW - ca 1000-1600, softening point = 85-1 05C 240 Aceton l l l 240 Deionized water 1200 . . _ . . _ Example 6 The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, DMPA, acetone I and catalyst. Af~er a reaction time of 1 hour at 65C, the HDI was 20 added and the reaction continued for another 90min. Following the addition ofacetone ll, the reaction mixture had an NCO content of 0.63C/G. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from polurethane and acetone lll . The mixture was then neutralized with 30 % causticsoda solution and dispersed in deionized water. The acetone was then distilled off.
zs Starting mat0rials Molar amountParts by weight [mmol] [g]
30 Polyesterdiol ADA~B14 (OHnumber = 45.0) 226 564 1,4-butanediol 6~ 6.1 DMPA 235 31.5 TDI 305 53.1 HDI 305 51.3 DBTL 0.1 Acetone 1 1 73 Acetone il 690 Polyurethane ~condensation polymer of crude MDI and BASF~TIENs~seLLsc~Fr _ o.. ooso/42811 _ _ _ _ polypropylenediol, i~-value in DMF
at 25C: 46~ 80 Aceton l l l 80 NaOH solution (30 o~c) 176 23.5 s Deionizedwater 1200 _ _ . .. _ .. ... _ _ _ample 7 The TDI was added ~o the mixture of dehydrated polyesterol, DMPA, 1,4-butanediol, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI
was added and the reaction continued for another 90 min. Following the addition of acetone ll, the reaction mixture had an NCo content of 0.45 %.
s Chain-extension was çarried out at 50C by the addition of PUD, this salt being in the form of a 40 % solution in water. After 5 min, the resin solution prepared from acetone lll and acrylate resin was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting materials Molar amount Parts by weight [mmol] ~g]
Polyesterdiol ADA/B1 4 (OH number = 45.0) 192 477 1,4-butanediol 57 5.2 DMPA 31 4.2 TDI 177 30.8 HDI 177 29.7 30 Acetone 1 133 Acetone l l 531 PUD (40 C~G salt solution) 73 31.9 Acrylate resin comprising:
50 wt~o of n-butyl acrylate, 29 wt% of ethylhexyl acrylate9 1 8.5wt% of methyl acrylate, and 2.5~% of acrylic acid 240 Aceton l l l 240 Deionized water 1200 2 ~
BASF~T~ENcEsELLschArT ___ ___ o z.ooso/42~11 ample 8 The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, 13MPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reac~ion continued for another 90~in. Following the addition of acetone ll, the reaction mixture had an NCX) content of 0.65~. The reaction mixture was cooled to 30~C and then mixed with the resin solution prepared from the acrylate resin and acetone lll. The mixture was then neutralized with 30 ~
caustic soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials . .
Molar amount Parts by weight ~5 [mmol] [g]
Polyesterdiol ADA/B1 4 (OH number = 45.0) 168 419 DMPA 235 31.5 1,4-Butanediol 50 4.5 ZOTDI 267 46.5 HDI 267 44.9 DBTL 0.1 Acetone 1 1 34 Acetone l l 534 2s Acrylate resin comprising:
50 wt~o of n-butyl acrylate, 29 wt% of ethylhexyl acrylate, 18.5 wt% of methyl acrylate, and 2.5wt/~o of acrylic acid 240 30 Aceton lll 240 NaOH solution (30 %) 176 23.5 Deionized water 1 Z00 .. _ 1 8 2~3~
8ASF~TlE?1GEsELLsCllAFT ~ ooso/428 Table _ SOLIDS CCNTENT LD VALUE VISCOSITY
_ .[r~o] lmPa s]
COMPAFU~TIVE EXAMPLE 1 40 87 146 COMPARATIVE E)(AMPLE 2 40 87 6D
___ . .. . .
_MPLE 4 40 96 18 EXAMPLE 7 40 90 _l 9
Particularly suitable poiyisocyanates (a) are aliphatic, cycloaliphatic, and aromatic 25 diisocyanates. The polyisocyanates preferably used have the general formula X(NCO)2, where x stands for an aliphatic hydrocarbon radical having from 4 to 12carbon atomsl a cycloaliphatic hydrocarbon radical haviny from 6 to 15 carbon atoms, or an aromatic hydrocarbon radical having from 6 to 15 carbon atoms.
Examples of suitable aliphatic, cycloaliphatic, and aromatic diisocyanates are 1,4-butane diisocyanate, 1 ,6-hexane diisocyanate, Z,2,4- and 2,4,4-tl imethylhexa-methylene diisocyanates, cyclohexane diisocyanate, methylcyclohexane diisocya-nate, isophorone diisocyanate, 4,4'-diisocyanatodiphenylm0thane, 4,4'-diisocya-natodicyclohexylmethane, and 2,4- and 2,6-toluene diisocyanates.
Mixtures of these diisocyanates may be used, if desired. Particularly suitable mixtures are those of aliphatic or cycloaliphatic diisocyanates with aromatic diisocyanates in a molar ratio of from 1:4 to 5:1.
40 The diisocyanates may be supplemented by minor quantities of monoisocyanates, BA SFi~rl~`.G~ FI _ 2 ~ ~o~/~Z~
if desired. to regulate the molecular weight.
Suitable dihydroxyl compounds (b) having a molecular weight exceeding 500 and ran~ing up to 5000g/mol are the wel7-known poiyesters, polyethers, polythio-ethers, polylactones, polyacetals, polycarbonates, and polyesteramides containing two hydroxyl groups. The preferred dihydroxyl compounds are those having molecular weights between 750 and 3000. Mixlures of these dihydroxyl compounds can, of course, be used if desired.
Suitable components (c) are aliphatic, cycloaliphatic, and aromatic mono- or di hydroxycarboxylic acids. Use is preferably made of dihydroxy-alkylcarboxylic acids, and more preferably of such acids havirlg from 3 to 10 carbon atoms, suchas are described in US-A 3,412,054. Particularly preferred compounds are those of ~he general formula COOH
in which R1 denotes a hydrogen atom or an alkyl radical of from 1 to 4 carbon zO atoms, and R2 and R3 stand for a C,-C4 alkylene group. An example of such a compound is 2,2-dimethylolpropionic acid.
The optional constituent (d~ may be a compound different from (c) and containingone or two isocyanate-reactive amino groups and at least one anionic group or a 25 group capable of conversion to an anionic group. The groups which are capable of conversion to anionic groups are usually carboxylic acid groups or sulfonic acidgroups. Worthy of mention are aminocarboxylic acids and aminosulfonic acids, forexample Iysine, -alanine, N-(2-aminoethyl)-2-aminoethanesulfonic acid, and the adducts of aliphatic diprimary diamines on -olefinic carboxylic acids as described 30 in DE-A 2,034,479, eg, the adduct of ethylenediamine on acrylic acid.
Both of the components (c) and (d) contain ionic groups, or groups which are capable of conversion to ionic groups, to ensure that the polyurethane is dispersible in water.
In order to convert potentially anionic groups, eg, carboxylic acid groups or sulfonic acid groups, to ionic groups, use may be made of inorganic and/or organic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonia, or primary, secondary, and, in particular. tertiary40 amines, eg, triethylamine or dimethylaminopropanol.
2 a ~
BASFAKTIEYaEsELLsc~AFT o...~oso/428 ~ 1 ___ The neutralization of the potentially anionic groups may be effected before, during, but preferably after, the isocyanate polyaddition reaction.
If desired, additional emulsifying constituents may also be used, for example monohydric polyether alcohols having a molecular weight of from 500 to 10,000g/mol and preferably from 1,000 to 5,000g/m~l. Monohydric polyether alcohols can be obtained by alkoxylation of monohydric starting molecules such as methanol, ethanol, or n-butanol, the alkoxylating agent being ethylene oxide or a mixture of ethylene oxide with some other alkylene oxide, especially propylene oxide. When such mix~ures are used, they preferably contain at least 40 mol~c, and more preferably at least 65 mol~, of ethylene oxide.
However, the addition of such nonionic emulsifiers is not generally necessary due to the presence of constituent (c) and, optionally, constituent (d).
The constituent (e) is essentially a compound having two hydroxyl groups, or twoamino groups, or one hydroxyl group and one amino group. Examples of suitable compounds are dihydroxyl compounds such as 1,3-propanediol, 1,4-butanediol, diamines such as ethylene diamine, hexamethylene diamine, piperazine, 2,5-20 dimethylpiperazine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isopho-rone diamine), 4,4'-diaminodicyclohexylmethane, 2,4-diaminocyclohexane, 1,2-diaminopropane, hydrazine, and amino alcohols such as ethanolamine, isopropanol-amine, methylethanolamine, and aminoetho~ye~hanol. If desired, compounds (e) having more than two isocyanate-reactive groups can be used.
Preferably, the weights of the components (a) to (e) are such that the total number of isocyanate-reactive functional groups, generally hydroxyl groups or amino groups, represents from 0.9 to 1.1 and more preferably from 0.95 to 1.05 gram equivalents per gram equivalent of isocyanate.
The most preferred situation is when the number of isocyanate-reactive functional groups is equal to that of the isocyanate groups.
The proportions of the individual components, based on one gram equivalent of 35 isocyanate, are preferably as follows:
component (b) from 0.15 to 0.8 and more preferably from 0.3 to 0.6 gram equivalents, component (c) from 0.03 to 0.4 and more preferably from 0.05 to 0.4 gram 2 ~
E~ASFAK~ GESE' ~SCI~AFT 0 Z o~so/42811 equivalents, component ~d) from 0 to 0.4 and more preferably from 0 to 0.3 gram equivalents, s component ~e) from 0 to 0.8 and more preferably from 0 ~o 0.6 gram equivalents.
In order to prepare the polyurethane, the constituents (a) to (e) are reacted in~0 known manner in a water-miscible low-boiling organic solvent, as described, for example, in D~-A 3,437,918.
Examples of particularly recomrnendable solvents are tetrahydrofuran, methylethyl ketone, N-methylpyrrolidone, are especially acetone.
s The reaction temperature is preferably from 50 to 1 00C.
The diisocyanate reaction can be accelerated by including conventional and well-known catalysts such as dibutyltin dilaurate, tin(ll) octoate, or 1,4-diazabicyclo-20 [2.2.2]octane.
The resulting polyurethane, which is substantially free from isocyanate groups, isdispersed in water after the addition of the polymeric adhesion enhancer, and the organic solvent is then removed, by distillation, to the desired extent, usually25 completely.
Alternatively, the polyurethane may be prepared by first producing a polyurethane prepolymer in the water-miscible low-boiling organic solvent. To this end, at least the constituents ~a) and (b) and a portion of (c) are interreacted. After the addition 30 of the polymeric adhesion enhancer, the resulting polyurethane prepolymer, which still contains isocyanate groups, is dispersed in water. The reaction of the prepolymer is then continued, in particular, with the r0maining constituents. The organic solvent can then be removed in the manner described above.
35 The polymeric adhesion enhancer can be one of a nurrIber of different polycondensates, polymers produced by free-radical polymerization, or poly-adducts.
The polymeric adhesion enhancer is preferably a phenoi-formaldehyde condensa-tion resin preferably having a molecular weight (weight average Mw) of from 500 to 2000 and a softening point ranging from 80 to 1 30C. Particularly preferred 2 ~
~ASF~ E'`IGESELLSC~AFT C' . ooso/4~
phenoi-formaldehyde cc~ndensation resins are novolaks, as may be obtained by acid-catalyzed reaction of phenois particularly phenol or phenol substituted by c1-c~O alky' groups, with formaldehyd~s. More particularly, the reaction is carried out using from 1.05 to 1.3 mol of phenols per mole of formaldehyde.
s Also particularly suitable are epoxy resins, preferably the reaction products ofepoxides such as epichlorohydrin with bisphenol A, those being particularly preferred which have a molecular weight (weight average Mw) o~ frorn 500 to 5000 and a softening point ranging frorn 80 to 1 30C.
Other suitabie polymeric adhesion enhancers are poly~vinyl acetate), poly(vinyl chloride), poly(methyl methacrylate), polyamides, polyethers, polyesters, polyether-diols, polyesterdiols, poiyurethanes, especially polyurethanes free from salt groups, and phenacrylates.
~s Preferred poly(vinyl acetate)s are homopolymers of vinyl acetate. Also useful are the copoiymers thereof containing up to 10wt% of comonomers such as vinyl laurate, vinyl stearate, or, preferably, esters of (meth)acrylic acid or fumaric acid or maleic acid with C1-C8 alkanols such as methanol, n-butanol, or 2-ethylhexanol.
Z0 The polymers usually have a K-value, as measured at 25C in cyclohexanone as specified in DIN 53,726, of from 45 to 60. By poly(vinyl chloride) we generally mean homopolymers of vinyl chloride or copolymers thereof containing up to 10wt% of comonomer such as ethylene or vinyl acetate. Their K-value (25C, cyclohexanone, DIN 53,726) should be between 45 and 55. The poly(methyl 25 methacrylate)s used by the person skilled in the art will normally be homopolymers of methyl methacrylate or copolyrners thereof containing up to 1 0wt%, based on the weight of the copolymer, of vinyl acetate, an ester of acrylic acid with a C1-C8 alkanol, or an ester of methacrylic acid with a C2-c8 alkanol. Their melt flow index MFI, determined as specified in DIN 53,735 (230C~3.8kg) iS generally between 30 0.1 and 3.û. The synthesis of such polymers is generally carried out by free-radical polymerization of the ethylenically unsaturated monomers at a ternperature between 30 and 150C in substance, in solution, or in emulsion, followed by drying. Such polymers are well known, eg, from Houben-Weyl, Methoden der Organischen Chemie, Vol. E20, 1987, pp. 1115-1125, 1041-1062, and 1141-35 1174.
Suitable polyamides have a K-value of from 65 to 80, determined in sulfuric acidat 25C as specified in DIN 53,727. They are usually polymers derived from lactams having from 7 to 13 ring units such as -caprolactam, E-capryllac~am, or -laurolactam, eg, polycaprolactam (PA6), or they may ~e polyamides produced by reacting dicarboxylic acids with diamines. Examples are poly( hexamethylene 2 Q ~
BASFAKT~ uEsEL~scH~T ~ Z ooso/42811 adipamide) (PA66), poly~hexamethylene sebacamide) (PA610), and poly(hexa-methylene dodecanamide) (PA612). Suitable dicarboxylic acids are, for example, alkanedioic acids containing from 4 to 12, and preferably from 6 to 10, carbsn atoms, and phthalic acid, terephthalic acid, and isophthalic acid, as well as arbitrary mixtures of said acids. Examples of suitable diamines are alkanediamines having from 4 to 12, and preferably from 4 to 8, carbon atoms, and also m-xylylenediamine, p-xylylenediamine, their hydrogenated derivatives, bis(4-amino-phenyl)methane, bis~4-aminocyciohexyl~methane, and bis(4-aminophenyl)propane-2,2, or mixtures thereof. Due to their good solubility properties, copolymers are preferred, for example a copolyamide of 30-40 wt~ adipic acid, 15-20 wt~Y(;
hexamethylenediamine, 30-35 wt~ ~-caprolactam, and 1~-20 wt~ -aminocaproic acid. The manufacture of these well-known polymers is part of the specialized knowledge of the person skilled in the art, cf, eg, Rompp, Chemielexikon, 8th Edition, pp. 2861, 3058, and 3267, or EP-A 129,195 and EP-A 129,196.
~s Polyetherdiols are known per se, for example from Kunststoff-Handbuch Vol.7 (1983) pp. 42 to 54. Examples are poly(ethylene oxide), poly(propylene oxide), and polytetrahydrofuran, or copolymers thereof containing two ~erminal hydroxyl groups. They are produced in known manner, generally by anionic polyaddition, of, 20 eg, N.G.Gaylord, High Polymers, Vol.13, New York 1963, Part 1. Of minor significance are polyetherols grafted with ethylene oxide to increase reactivity. The polyetherdiols generally have a molecular weight of from 300 to 3000 corresponding to a K-value of from 25 to 60, as deterrnined in DMF at 25C as specified in DIN 53,726. Preferred molecular weights are between 800 and 2200 zs corresponding to K-va!ues between 20 and 50.
The polyethers used are, eg, poly~ethylene oxide), poly(propylene oxide), and polytetrahydrofuran. The polyethers usually have a K-value in DMF at 25C (DIN
53,726) of from 20 to 50. They are well known, cf, eg, Encyclopedia of Polymer 30 Science and Techno/ogy, Vol.6, 1967, pp. 103 et seq, Vol.9, 1968, pp. 668 et seq, and Vol.13, 1970; pp. 670 et seq.
The preferred polyesters are monomer-free unsaturated polyester resins. These are known condensation polymers of polyvalent, preferably divalent, carboxylic 35 acids and their esterifiable deriva~ives, especially their anhydrides, which are linked by an ester-like bond to polyhydric, preferably dihydric, alcohols and optionally contain additional radicals of monovalen~ carboxylic acids or of monohydric alcohols. Examples of the starting materials are as follows: maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, maleic anhydride, phthalic anhydride, isophthalic anhydride, ethylene glycol, propyleneglycol, 1,4-butanediol, and neopentyl glycol. Of minor significance for the present _ 7 BA~iFAK~ GLSE~LSC~Fl o - ooso/4281 1 invention are those resins which are prepared by co-condensation of bisphenol A,epichlorohydrin-bisphenol A condensates, and methacrylic acid. In this context, "monomer-free" means that these unsaturated polyester resins (UP resins) are notdissolved in a monomer, such as styrene, which could induce cross-linking. The products usually have a viscosity at 150C of from 1000 to 6000mPa ~i and preferably from 2000 to 4000 mP~
Suitable polyesterdiols are condensation polymers containing two terminal hydroxyl groups and derived from dicarboxylic acids such as adipic acid or isophthalic acid condensed with diols such as 1,4-butanediol, 1,6-hexanediol, or neopentyl glycol.
The molecular weight range of the polyesterdiols used is generally from 300 to 5000. Preferred molecular weights are between 800 and 2500 corresponding to a K-value in DMF at 25C ~DIN 53,276) of from 30 to 55. These polymers and their manufacture are generally known, cf Kunststoff-Handbuoh Vol.7 (1983) pp. 54 to 62 and DE 1,268,842.
Salt group-free polyurethanes are known addition polymers based on polyether-diols, polyesterdiols, isocyanates such as hexamethylene diisocyanate, 2,4-diisocyanatodiphenylmethane, and possibly bifunctional or trifunctional chain extenders, which are prepared by conventional methods, cf Kunststoff-Handbuch Karl-Hanser-Verlag, Vol.7 (1966~. The preferred condensates are those having a low molecular weight (K-value in DMF at 25C as specified by DIN 53,726: from 25 to 60). Cross-linked polyurethanes are of minor irnportance.
Phenacrylates are preferably made by the addition of bisphenol A glycidyl ether (meth)acrylates to terephthalic acid. It is also possible to use phenacrylates based on epoxidized novolaks. The K-values of these polymers generally range from 30 to 55 (determined in cyclohexane at 25C as specified in DIN 53,726).
The polymeric adhesion enhancer is added to the polyurethane or its prepolymer present in a water miscible low-boiling organic solvent prior to dispersion thereof in water, ie, prior to the formation of the aqueous dispersion of the invention having an aqueous continuous phase. Basically, the resin can be added to the reaction 35 mixture of the starting components of the polyurethane at any desired time, but it is particularly advantageous not to add the resin until the prepolymer formation has reached an advanced stage and the NCO content of the prepolymer has reached a value of less than 1.5wt~/(i. Especially in the case of resins containing groupswhich are particularly reactive to isocyanates, such as the novolaks, the resins40 should only be compounded with polyurethane resins having an NCO content nearOwt%. The polymer may be added in substance or in the form of a solution.
2 ~
BASFA~, i NG~S~SC~1AF~ _ 0 Z o~so/42811 Suitable solvents for the polymer are water (eg, in the case of phenol-formaldehyde resins~ and, more particularly, again water-miscible low-boiling organic solvents.
s The dispersion of the invention, as finally obtained follcwing the dispersion of the mixture in water, the conversion of the polyurethane prepolymer to the polyurethane, if applicable, and the removal of the organic solvent by distillation, if necessary, preferably has a solids content of from 10 to 70 wt~ and more preferably from 20 to 50 wt~o.
The dispersions of the invention can be immediately used for making joints between widely varying substrates, for example wood, plastics, glass, and metal.To achieve special properties, it is possible to add auxiliaries to the dispersions, for example plasticizers, fiim formers, fillers, etc.
The dispersions have good adhesion properties and are particularly noteworthy for their initial adhesive strength, this being the result of their low viscosity. In general, the viscosity of a dispersion can be reduced by increasing the particle diameterwithout changing the solids content (û.Lorenz, G.Rose, Colloid Polym. Sci. 260 20 (1982) p. 1079). However, ~here is the risk of coagulation of larger dispersed particles, particularly when shearing forces are applied.
Surprisingly, the dispersions of the invention are even less viscous than dispersions containing particles of larger sizes.
zs Exam~lç~
The viscosities of the dispersions were measured at a shear rate of 100 ~ ~ using a rotational rheometer comprising concentric cylinders (diameter of bob: 38.7mm, 30 diameter of cup: 42.0 mm).
The particle size of the latex particles was determined indirectly via turbiditym0asurements, in which the turbidity of a dispersion having a solids content of 0.01 wt~ was compared with distilled water at room temperature for a layer 35 thickness of 2.5cm.
LD I ntensitydjSperSion x 100 I ntenSitywater In the following examples the symbols have the meanings given below:
ADA = adipic acid BASFAKrlENGES~LSC,`1~FT G Z ooso~
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .
B14 = 1,4-butanediol TDI ~ toluene diisocyanate HDI = hexamethylene diisocyanate PUD = Na salt of the Michael adduct of acrylic acid and ethylenediamine s DBTL = dibutyltin dilaurat0 DMPA = dimethylolpropionic acid Comparative Example 1 TDI was added to a mixture of dehydrated polyesterol, acetone I and catalyst. After a reaction time of 1 hour at 65C, HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixture had anNCO contant of 0.69 /0.
Chain-extension was carried out at 50C by the addition of PUD, this salt being in the form of a 40 ~0 solution in water. After 5 min, the resin solution prepared from acetone lll and Epikote 1001 was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting materials Molar amount Parts by weight [mmol~ [g~
Polyesterdiol ADA/B14 (OH number 45.2) 199 493 TDI 148 25.8 HDI 149 25.0 DBTL 0.1 Acetone 1 133 Acetone l l 532 0 Epikote 1001 (condensation product of bisphenol A and epichlorohydrin, Mw ca 450-500) 240 Acetone l l l 240 PUD (40 /0 solution of salt) 95 41 35 Deionized water 1200 Comparative Example 2 40 The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediolJ
~g)~
BASFA~r~E~lG~.E~ .C~ T __ _ _ __ _ O ~ ooso/4281 1 . _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ . _ . _ _ _ _ _ _ . . . _ _ _ _ . _ _ . _ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ . . . _ _ . . _ _ . _ _ _ _ _ _ . _ _ _ _ . _ _ _ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ acetone I and catalyst. After a reaction time of 1 hour at 65(~ he HDI was added and the reaction continued for another 90 mill. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.63 ~
s Chain-extension was carried out at 50C by the addition of PlJD, this salt being in the form of a 40 ~ solution in water. After 5 min, the resin solution prepared from acetone lll and a polyesterol was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting material~
Molar amount Parts by weight [mmol] [g]
Polyesterdiol ADA/B14 (OH number 45.0) 193 482 ~s 1,4-butanediol 58 5.2 TDI 169 29.4 HDI 169 28.3 Acetone 1 133 Acetone l l 533 20 Polyesterdiol ADA/B14 ~OH number = 45.0) 240 Acetone l l l 240 PU[3 (40 ~'~fi solution of salt) 86 37.5 Deionized water 1 20û
Comparative Example 3 The TDI was added to the mixture of dehydrated poly(tetramethylene oxide), 1,4-30 butanediol, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI
was added and the reaction continued for another 90 min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.70 /0.
Chain-extansion was carried out at 50C by the addition of PUD, this salt being in 35 the form of a 40 % solution in water. After 5 min, the resin solution prepared from acetone lll and Epikote 1007 was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
~ASF ~,IE~ S~ H~rT __ _ O_ ooSo_4 Starting materials _ _ ~
Molar amount Parts by weight [ml1loll [~]
s Poly(tetramethylene oxide) ~OH-number 4~.0) 213 435 1,4-Butanediol 213 19.2 TDI 260 45.3 HDI 260 43.8 Acetone 1 132 Acetone ll 532 Epikote 10û7 (condensation polymer of bisphenol A and epichlorohydrin~
Mw ca 1550-2000 ) 240 Acetone lll 240 PUD (40 ~`Yr solution of salt) 94 41 Deionized water 1200 Example 1 The TDI was added to the mixture of dehydrated polyesterol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90tnin. FQIIOWjng the addition of acetone ll, thereaction mixture had an NCO content of 0.65 ~/O.
zs Chain-extension was carried out at 50C by the addition of PUD, this salt being in the form of a 40 ~/O solution in water. After 5 rnin, the resin solution prepared from acetone lll and Epikote 1007 was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting materials Molar amount Parts by weight [mrnol] [g]
35 PolyesterdiolADA/B14(0Hnumber = 45.2) 194 481 DMPA 56 7.4 TDI 164 28.6 HDI 167 28.1 DBTL 0.1 40 Acetone 1 133 BASFA~T!t!lG~S~L~SC~ T ~ (-J '7 o~
Acetone l l 533 PUD (40 ~, solution of salt) 84 36.8 Aceton lll 240 Epikote 1007 (condensation product o~
s bisphenol A and epichlorohydrin, Mw ca 1550-2000 ) 240 Deionized water 1200 . _ Example 2 Procedure:
The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.60%. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from Lupraphen VP 9186 and acetone lll. The mixture was then neutralized with 30 ~
20 caustic soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials .
Molar amount Parts by weight [mmol] lg]
Polyesterdiol ADA/B14 ~OH number = 45.0) 166 414 1,4-Butanediol 50 4.5 DMPA 250 3.5 TDI 273 47.6 HDI 273 45.9 DBTL 0.1 Acetone 1 1 34 Acetone ll 534 35 Polyester resin:
Lupraphen VP 9186 Polyesterdiol ADA/Bt 4 (OH number = 473 240 Ac0ton lll 240 NaOH solution (30%) 187 25.0 Deionized water 1 200 2 ~
BASF~TIE~OEsELLScHAF, o.z.ooso/42B11 _ _ _ _ _ .
_ple The TDI was added to the mixture of dehydrated polytetramethylene oxide, 1,4-butanediol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixhJre had an NCO content of 0.60YG. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from Epikote 1007 and acetone lll. The mixture was then neutralized with 30æ caustic soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials .. .. . _ . . . _ ~olar amount Parts by weight [mmol] [g]
Poly(tetramethylene oxide) (OH number = 45.0) 191 390 DMPA 239 32.1 1,4-butanediol 191 17.3 zO T~l 351 61.2 HDI 351 59.1 DBTL O.1 Acetone 1 137 Acetone ll 548 25 Epikote 1007 (condensation polymer of bisphenol A and epichlorohydrin, ii7W ca 1 55û-2000) 240 Aceton lll 240 NaOH soiution ( 30 ~O) 1 68 22 .3 30 Deionized water 1200 Exampl ~s The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, DMPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reaction continued for another 90min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.65%. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from Epikote 1007 and acetons Ill. The mi~ure was then neutralized with 30 O~G caustic 2 a ~
BASF~ ~, E N G 5 S E L LSC ~A FT O . . ooso /4 2 8 11 soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials .
s Molar amountParts by weight [mmol] [g]
Polyesterdiol ADA/B1 4 (OH number = 45.0) 168 419 DMPA 235 31.5 1,4-butanediol 50 4-5 TDI 267 46.5 HDI ~67 44.9 DBTL 0. 1 Acetone 1 134 Acetone ll 534 E,oikote 1 007 (condensation polymer of bisphenol A and epichlorohydrin, i~w ca 1 550-2000) 240 Aceton lll 240 NaOH solution (30 %) 176 2~.5 Deionized water 1200 _ ample 5 The TDI was added to the mixture of dehydrated polyesterol, DMPA, 1,~-butanediol, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI
was added and the reaction continued for another 90 min. Following the addition of acetone ll, the reaction mixture had an NCO content of 0.61 ~h.
Chain-extension was carried out at 50C by the addition of PUD, this salt being in the form of a 40 5~0 solution in water. After 5 min, the r~sin solution prepared from acetone lll and phenol-formaldehyde cond0nsate was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and35 the acetone distilled off.
Starting materials Molar amount Parts by weight lmmol] [g]
4D PolyesterdiolADA/B14 (OHnumber = 45.0) 192 477 __ ~ __ 1 5 ~ASF~r ~ s~ F~ ____ ___ __Z coso/q28 1,4-butanediol 57 5.2 DMPA 31 4.2 TDI 177 30.8 HDI 177 29.7 5 DBTL 0.1 Acetone 1 133 Acetone ll 531 PUD (40 % sait solution) 73 31.9 Phenol-formaldehyde condensate tO MW - ca 1000-1600, softening point = 85-1 05C 240 Aceton l l l 240 Deionized water 1200 . . _ . . _ Example 6 The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, DMPA, acetone I and catalyst. Af~er a reaction time of 1 hour at 65C, the HDI was 20 added and the reaction continued for another 90min. Following the addition ofacetone ll, the reaction mixture had an NCO content of 0.63C/G. The reaction mixture was cooled to 30C and then mixed with the resin solution prepared from polurethane and acetone lll . The mixture was then neutralized with 30 % causticsoda solution and dispersed in deionized water. The acetone was then distilled off.
zs Starting mat0rials Molar amountParts by weight [mmol] [g]
30 Polyesterdiol ADA~B14 (OHnumber = 45.0) 226 564 1,4-butanediol 6~ 6.1 DMPA 235 31.5 TDI 305 53.1 HDI 305 51.3 DBTL 0.1 Acetone 1 1 73 Acetone il 690 Polyurethane ~condensation polymer of crude MDI and BASF~TIENs~seLLsc~Fr _ o.. ooso/42811 _ _ _ _ polypropylenediol, i~-value in DMF
at 25C: 46~ 80 Aceton l l l 80 NaOH solution (30 o~c) 176 23.5 s Deionizedwater 1200 _ _ . .. _ .. ... _ _ _ample 7 The TDI was added ~o the mixture of dehydrated polyesterol, DMPA, 1,4-butanediol, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI
was added and the reaction continued for another 90 min. Following the addition of acetone ll, the reaction mixture had an NCo content of 0.45 %.
s Chain-extension was çarried out at 50C by the addition of PUD, this salt being in the form of a 40 % solution in water. After 5 min, the resin solution prepared from acetone lll and acrylate resin was added and the mixture stirred for a further 5 min at 50C. The mixture was then dispersed in water and the acetone distilled off.
Starting materials Molar amount Parts by weight [mmol] ~g]
Polyesterdiol ADA/B1 4 (OH number = 45.0) 192 477 1,4-butanediol 57 5.2 DMPA 31 4.2 TDI 177 30.8 HDI 177 29.7 30 Acetone 1 133 Acetone l l 531 PUD (40 C~G salt solution) 73 31.9 Acrylate resin comprising:
50 wt~o of n-butyl acrylate, 29 wt% of ethylhexyl acrylate9 1 8.5wt% of methyl acrylate, and 2.5~% of acrylic acid 240 Aceton l l l 240 Deionized water 1200 2 ~
BASF~T~ENcEsELLschArT ___ ___ o z.ooso/42~11 ample 8 The TDI was added to the mixture of dehydrated polyesterol, 1,4-butanediol, 13MPA, acetone I and catalyst. After a reaction time of 1 hour at 65C, the HDI was added and the reac~ion continued for another 90~in. Following the addition of acetone ll, the reaction mixture had an NCX) content of 0.65~. The reaction mixture was cooled to 30~C and then mixed with the resin solution prepared from the acrylate resin and acetone lll. The mixture was then neutralized with 30 ~
caustic soda solution and dispersed in deionized water. The acetone was then distilled off.
Starting materials . .
Molar amount Parts by weight ~5 [mmol] [g]
Polyesterdiol ADA/B1 4 (OH number = 45.0) 168 419 DMPA 235 31.5 1,4-Butanediol 50 4.5 ZOTDI 267 46.5 HDI 267 44.9 DBTL 0.1 Acetone 1 1 34 Acetone l l 534 2s Acrylate resin comprising:
50 wt~o of n-butyl acrylate, 29 wt% of ethylhexyl acrylate, 18.5 wt% of methyl acrylate, and 2.5wt/~o of acrylic acid 240 30 Aceton lll 240 NaOH solution (30 %) 176 23.5 Deionized water 1 Z00 .. _ 1 8 2~3~
8ASF~TlE?1GEsELLsCllAFT ~ ooso/428 Table _ SOLIDS CCNTENT LD VALUE VISCOSITY
_ .[r~o] lmPa s]
COMPAFU~TIVE EXAMPLE 1 40 87 146 COMPARATIVE E)(AMPLE 2 40 87 6D
___ . .. . .
_MPLE 4 40 96 18 EXAMPLE 7 40 90 _l 9
Claims (5)
1. An aqueous dispersion containing a polyurethane and from 5 to 60wt%, based on the polyurethane, of a polymeric adhesion enhancer, the polyurethane being essentially built up of (a) an organic polyisocyanate, (b) a dihydroxyl compound having a molecular weight exceeding 500 and ranging up to 5000g/mol and not containing any anionic groups or groups capable of conversion to anionic groups, (c) a di- or mono-hydroxyl compound containing at least one anionic group or a group capable of conversion to an anionic group, (d) optionally a further compound different from (c) and containing one or two isocyanate-reactive functional groups and at least one anionic group or a group capable of conversion to an anionic group, (e) optionally a compound having at least two isocyanate-reactive func-tional groups and a molecular weight of from 60 to 500g/mol and not containing any anionic groups or groups capable of conversion to anionic groups, and the polyurethane or its prepolymer is prepared in a water-miscible solvent boiling below 100°C and, following the addition of the polymeric adhesionenhancer, is dispersed in water and, in the case of the prepolymer, the conversion of the latter to the polyurethane is carried out.
2. A process for the preparation of an aqueous dispersion as claimed in claim 1,wherein the polyurethane or its prepolymer is formed in a water miscible solvent boiling below 100°C and, after the addition of the polymeric adhesion enhancer, is dispersed in water and, in the case of a prepolymer, the conversion thereof to the polyurethane is carried out.
3. An aqueous dispersion as claimed in claim 1, wherein the polymeric adhesion enhancer is a phenol-formaldehyde resin or an epoxide resin.
4. A method of using a dispersion as claimed in claim 1 as an adhesive.
BASFAKTIENGESELLSCHAFT O.Z. 0050/42811
BASFAKTIENGESELLSCHAFT O.Z. 0050/42811
5. Substrates coated with adhesive whenever obtained by the use of a dispersion as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4137661A DE4137661A1 (en) | 1991-11-15 | 1991-11-15 | AQUEOUS POLYURETHANE DISPERSION |
| DEP4137661.7 | 1991-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2081414A1 true CA2081414A1 (en) | 1993-05-16 |
Family
ID=6444920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002081414A Abandoned CA2081414A1 (en) | 1991-11-15 | 1992-10-26 | Aqueous polyurethane dispersion |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0542072B1 (en) |
| JP (1) | JPH05222288A (en) |
| AU (1) | AU654055B2 (en) |
| CA (1) | CA2081414A1 (en) |
| DE (2) | DE4137661A1 (en) |
| ES (1) | ES2096006T3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5922806A (en) * | 1996-03-26 | 1999-07-13 | Bayer Aktiengesellschaft | Aqueous polyurethane dispersions based on 1-methyl-2,4-and/or -2,6-diisocyanatocyclohexane and their use as binders for glass fiber sizings |
| US5945473A (en) * | 1995-06-07 | 1999-08-31 | National Starch And Chemical Investment Holding Corporation | Modified aqueous polyurethane dispersions and methods for making same |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4137556A1 (en) * | 1991-11-15 | 1993-05-19 | Basf Ag | AQUEOUS POLYURETHANE DISPERSIONS |
| DE4320455A1 (en) * | 1993-06-21 | 1994-12-22 | Basf Ag | Aqueous polyurethane dispersions |
| DE4418157A1 (en) | 1994-05-25 | 1995-11-30 | Basf Ag | Thermocoagulable aqueous polyurethane dispersions |
| FR2782636B1 (en) | 1998-08-27 | 2001-09-14 | Oreal | COMPOSITIONS CONTAINING A POLYCONDENSATE COMPRISING AT LEAST ONE POLYURETHANE AND / OR POLYUREA PATTERN AND A SILICONE COMPRISING AT LEAST ONE CARBOXYL FUNCTION |
| FR2782637B1 (en) | 1998-08-27 | 2000-11-24 | Oreal | HAIR COMPOSITION CONTAINING A POLYCONDENSATE COMPRISING AT LEAST ONE POLYURETHANE AND / OR POLYUREA PATTERN AND A POLYOL |
| ES2220101T3 (en) | 1998-08-27 | 2004-12-01 | L'oreal | AEROSOL DEVICE CONTAINING A POLYCONDENSATE THAT INCLUDES AT LEAST A POLYURETHANE AND / OR POLYUREA UNIT. |
| FR2788972B1 (en) | 1999-02-03 | 2001-04-13 | Oreal | HAIR COMPOSITION COMPRISING A WASHING BASE, A CATIONIC POLYMER AND AN ANIONIC POLYURETHANE AND USE THEREOF |
| WO2005030873A1 (en) * | 2003-09-26 | 2005-04-07 | Dainippon Ink And Chemicals, Inc. | Water base dispersion of polyurethane resin, and water base adhesive and water base primer coating agent containing the same |
| DE10353953A1 (en) | 2003-11-18 | 2005-06-09 | Basf Ag | Laminating adhesives containing polyurethane and epoxy resin |
| US20050288431A1 (en) * | 2004-06-25 | 2005-12-29 | Gindin Lyubov K | Polyurethane dispersion prepared from a high acid functional polyester |
| US20050288430A1 (en) * | 2004-06-25 | 2005-12-29 | Gindin Lyubov K | Polyurethane dispersions with high acid content |
| KR100905265B1 (en) * | 2005-08-09 | 2009-06-29 | 디아이씨 가부시끼가이샤 | Water base dispersion of polyurethane resin, and water base adhesive for shoes and water base primer coating agent containing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3613492A1 (en) * | 1986-04-22 | 1987-10-29 | Bayer Ag | METHOD FOR THE PRODUCTION OF AQUEOUS DISPERSIONS OF POLYURETHANE-POLYHANE SUBSTANCES, THE DISPERSIONS AVAILABLE ACCORDING TO THIS METHOD AND THEIR USE AS OR FOR THE PRODUCTION OF COATING AGENTS |
| DE3630045A1 (en) * | 1986-09-04 | 1988-03-17 | Bayer Ag | ADHESIVE AND THE USE OF THE ADHESIVE TO MAKE ADHESIVES |
| DE3643791A1 (en) * | 1986-12-20 | 1988-06-23 | Basf Ag | AQUEOUS POLYURETHANE ADHESIVE DISPERSION |
| JPH04502022A (en) * | 1988-11-26 | 1992-04-09 | ヒェミッシェ ファブリーク シュトックハウセン ゲー．エム．ベー．ハー | Method for flaking water-soluble polyurethane or polyurethane urea dispersions, elastomeric forms and high-temperature lining of fiber surface structures using the dispersions |
| DE3903538A1 (en) * | 1989-02-07 | 1990-08-16 | Basf Ag | PRODUCTION OF EMULSIFIER-FREE, AQUEOUS POLYURETHANE DISPERSIONS |
-
1991
- 1991-11-15 DE DE4137661A patent/DE4137661A1/en not_active Withdrawn
-
1992
- 1992-10-26 CA CA002081414A patent/CA2081414A1/en not_active Abandoned
- 1992-10-28 JP JP4289956A patent/JPH05222288A/en not_active Withdrawn
- 1992-10-31 EP EP92118676A patent/EP0542072B1/en not_active Expired - Lifetime
- 1992-10-31 DE DE59207891T patent/DE59207891D1/en not_active Expired - Lifetime
- 1992-10-31 ES ES92118676T patent/ES2096006T3/en not_active Expired - Lifetime
- 1992-11-13 AU AU28350/92A patent/AU654055B2/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5945473A (en) * | 1995-06-07 | 1999-08-31 | National Starch And Chemical Investment Holding Corporation | Modified aqueous polyurethane dispersions and methods for making same |
| US5922806A (en) * | 1996-03-26 | 1999-07-13 | Bayer Aktiengesellschaft | Aqueous polyurethane dispersions based on 1-methyl-2,4-and/or -2,6-diisocyanatocyclohexane and their use as binders for glass fiber sizings |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0542072B1 (en) | 1997-01-15 |
| AU654055B2 (en) | 1994-10-20 |
| DE4137661A1 (en) | 1993-05-19 |
| EP0542072A1 (en) | 1993-05-19 |
| DE59207891D1 (en) | 1997-02-27 |
| AU2835092A (en) | 1993-05-20 |
| ES2096006T3 (en) | 1997-03-01 |
| JPH05222288A (en) | 1993-08-31 |
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