Note: Descriptions are shown in the official language in which they were submitted.
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.
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
HO--R2--C--R3--OH
R1
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
-- 4
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 5320 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.
1 1
~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
1 2
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
1 3
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
1 4
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
16
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
2 0
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
DBTL O 1
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
1 7
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
COMPARATIVE EXAMPLE 3 40 74 91
EXAMPLE 1 40 87 27
___
EXAMPLE 2 40 93 16
. .. . .
EXAMPLE 3 40 89 16
_MPLE 4 40 96 18
EXAMPLE 5 40 77 20
EXAMPLE 6 40 91 17
EXAMPLE 7 40 90 _l 9
EXAMPLE 8 40 93 17
1 9
