Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ O 91/06586 2 0 7 2 0 9 6 ; ~ pc~r/N~90/0016~
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WATER-SOLUBLE RESIN
The invention relates to water-soluble resins that
can be used as dispersants.
Water-s~luble resins that can be used as
dispersants are described in, for instancè,' ~Paint Flow and
Pigment Dispersion' by T.C. Pattonj pp 290-296 (1979).
Dispersants known in the art ~uch as, for'instance,
polyphosphates, isobutylene maleic acid copolymer~sodium
salt and polyacrylates, cannot be sufficiently mixed with
binders such as, for ins~ance, alkyd resin dispersions,-to
obtain paints with good gloss properties. It is possible
also, for instance, to use water-dilutable alXyd resins as
dispersants for pigments. In order to obtain clear solutions
and good properties, such as for instance pigment wetting
proper~ies, the known resins used as dispersants will,
moreover, have to he combined with undesired compounds such
asj ~or :instance, amines or organic solvents.' "~
~-~ The object o'the invention is''to provide' a - ' '
properly processable, air-drying and water-soluble resin
suited as dispersant an~?resulting in'paintsJwith a good
-25 gloss. :- i ? ~
~ Thelwater-solubleiresin according'to the invention
is characterizediin~that the!resin is;substantially ~uilt3up;-
..from;units~.~f ~ J~
A. polyethylene~g}ycol~ith ~S-lOO)`~ethylenë oxidei'`unitsj'
B. a compound containing one or more allyl~ànd~dr'';'
`(meth)acrylate;groups and ~ J~ ?~ r~ tS~
C. the reaction product of one or more unsaturatèd~fàtty
acids or?o'ne or~'mor'e~po'lya'lcohol'l's)~who`lly'or~p'a'r~ly
esterified with unsaturated fatty acids with an J~)3~ `:
csmpsund,a~ j;J'',~" .{ ~ r ~r~ rJ r ~ e``~3 ;~
where the A:C molar ratio is between 0.5;1 and 4:1 and the ''
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WO91/06586 2 0 7 2 0 9 6 PCT/NL90/0016~ ~
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s:c ~olar ratio is between 0.5:1 and 4:1.
The A:s molar ratio is mostly between 4:1 and 1:4
and is preferably substantially 1:1.
~ hus a low-viscosity, easily processable,
air-drying and water-soluble resin is obtained. If used as a
paint dispersan~, this resin results in a paint with a good
gloss and a good water resistance. For organic as well as
inorganic pigments the resin has good pigment wetting
properties.
. This resin, moreover, need not be combined with
compounds such as, for instance, amines or organic solvents.
Here it consequently also concerns solvent-~ree systems.
Another advantase of the use of the resin as dispersant is
that in the preparation of the paint there is hardly any
foaming of the dispersant, so that hardly any or no
anti-foaming agents need be added.
According to a preferred embodiment of the
invention,.the A:C molar ratio is between O.B:1 and 2:1 and
the B:C molar ratio between 0.8:1 and 2:1.
The.best results are obtained if the A:B:C molar
.
ratio is substantially 1:1:1. ..
According to another preferred embodiment of.the
~nvention,.the polyethylene glycol has.(8 20) ethylene oxide
units.. ~
,~ Preferably the polyethylene glycol has-(10-14)..
ethylene oxide units.
~ .. The chosen number,-of ethylene:oxide..units is such
- . .. _ .. . . ~ . .
30.. that.the!resin.jconti~ues.to.be~water-soluble.. ~
The resin according to the invention;can very well
be.~used,~as a dispersant,if.it has the;;~ollowing~
cha ra cte r l s t i ~c~s ~ r ~ r,~
- a number-average moleculari~weight!Mn..~o~;between 1000 and
- " a,w~ei~ht-average~molecular weightj!:Mw of between..2000 and
SOOO,j lJ,~ 3 :7 ~3 t ~ r ~ u .1.-~l 3 t -~I 2-~
- a polydi~persity Mt~Mn of between 1.5 and 3.5;
., ~ I
.
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.-~vo9l/06586 2 0 7 2 ~`9 6` ` PCT/~L90/00'63
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- a viscosity of between 10 and 100 dPas, preferably
between lo and 30 dPas;
- an iodine value of between 50 and 150 g iodine/100
grammes resin.
The molecular weights have been determined via GPC
(Ultra-styragel, waters, looA, loooA, lo,oOOA separating
capacity Mw 200- 300, 000 ) .
The viscosity has been determined at 23C using a
rotational viscosimeter (DIN 53019, Bohlin).
The iodine value has been determined via ASTM 3
1959-85.
As the polydispersity of the resin is betw'een 1.'5
and 3.5 hardly any preferential adsorption of high-molecular
weight product takes place, so.that no low-molecular weight
product is left behind in the aqueous phase.
As compound B may be used compounds containing
allyl groups such~as, for instance, allyl ethers with 3-2p
20 carbon atoms, allyl alcohol, allylglycidyl ethers, diallyl .
ethers of glycerol, diallyl ether of trimethylolpropane or
diallyl ethers of trime~hylolethane and triallyl ether of
pentaerythritol, as well as compounds containing acrylate
groups such as, for instance; hydroxyethyl(meth)acrylate,
hydroxylpropyl~meth)acrylate and hydroxybutyltmetX)acrylate.
The compound used as:~ is preferably a compound containins
allyl groups, such as allyl alcohol. '~
. Examples-of polyalcohols wholly or partly
esterified with unsaturated fatty ac.ids are linsee`'d 'oil',
30,;~suoybean.oil, safflower~bil~,: oiticica~oil, caraway oil,`'
rapeseed oil,.wood oil and ~ish oil. Further can'rbe ùsed
diesters and~triesters,of polyalcohols','~such'as'`'glycerol,-
trimethylolpropane or pentaerythritol, and-as unsàt'ur'atéd`
fatty acids.the;fatty..acids o~.the-above-mention`ed'~
35 unsaturated~oils~and~:tall~oil~.~atty~acid'~ s~ c
~ ~. J.Suita~le ~;unsaturated carbonyl~compounds:are'maieic .
anhydride, ~umaric acid or a functional twith',`'`i`n~addition.
to.the unsaturation,.another r~active?group`'not ~eing an ' '.
unsaturation) acrvlate.
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WO91/06~86 2 0;7 2 0 9 6 : PCT/~L90/0016~ ~
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A~cording to a preferred embodiment of the
invention, c is the reaction product of linseed oil and/or
safflower oil with maleic anhydride.
he invention also comprises a process for the
preparation of the present resin on the basis of A, B and C.
In a first reaction step an unsaturated compound, preferably
maleic anhydride, can react via radical reaction with an
unsaturated vegetable oil, such as linseed oil or safflower
oil, at a temperature above 150DC, so that C is obtained. ! '
Subsequently, after addition of an adduct of compounds A and
B, alcohol-anhydride reactions can be carried out. These
reactions usually take place in the presence of an
appropriate catalyst such as, for'instance, triethyl amine
at ~emperatures lower than 150C. The A:B molar ratio is
mostly between 4:1 and 1:4 and is preferably substantlally
1:1. . . -
. In this process the A:C molar ratio is'preferably
between 0~5:1 and 4:1 and the B:C molar ratio preferably
between 0.5:1 and 4:1. According to a further preferred
embodiment of the invention the said ratios are between
0.~'.:1 and.. 2:1. . ;. ' ' .
..j.... More in~particular the.A:B:C molar ratio is ''
25..substantially 1:1:1. ~. ~ '' :;' '''" ' ' '
.. . . ........ .
~ a ;, . The invention also.comprises a modified resin j '
obtained in that the resin.described'above, built-up from A, ''
B and C at temperatures lower~.than`150C,-is'modified with
one or more monofunctional-:epoxy:compounds, preferably'with
a termlnal~.copolymerizable.double bond,'i'such aslfor~!instance
glycidyl!meth)-acrylate or glyci'dylallyl'ether.'Thè~` ?
catalys ~ may be,~or~(instance,~triethyl~'amine`~o'r'`"''~
N,N dimethylaniline. The.:molarJratio'of the'l"react'ants is!-
pre~'erably;~substantially l~ This modification is
preferably appliedjif:ithe~resinehas freeiacid groups',~
.~ibecausejthelepoxyjcompounds can..then~reacc'with'the acid
gro~u7ps present ;;) ~ r ~
., ;,,~rr ~T~his~modified reaction.~product:1canrsubsequentiy
. -
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~^~O91/06586 2 0 7 2 jO 9 ~`. PCT/~L90/0016~
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react with acids or anhydrides such as, for instance, maleic
acid(anhydride).
The resin according to the invention can be used as
dispersant or grinding agent and/or wetting agent for
pigments. A suitable pigment paste contains, for instance,
50-70% (wt) pigment, 3-7~ (wt) resin according to the
invention and 20-45% (wt) water. The dispersant can be used
in water-based air-drying paint systems. In order to reach
any desired pigment-volume concentration (PVC), alkyd `
dispersions, acrylate dispersions or mixtures of these can
be added to the medium also. The effect of using the resin
according to the invention as air-drying water-soluble
dispersant is that the solubility and compatibility with,
for instance, alkyd emulsions is substantially improvedj so
that good glossy systems are obtained.
The resin according to the invention can be used
also as water-soluble air-drying binder, or as water-soluble
wood preservative in the form of copper or zinc salts of the
resin.
. The resin according to the inve.ltion can further be
used as air-drying plasticizer in, for instance, acrylate
dispersions. .. .-: .. . .. ~ :.. ! '`
25 Traditional plasticizers for acrylate dispersions
are, for instance, (ethers of) ethylene and propylene
glycols. These compounds, however, evaporate during the '
drying of the film,.which is undesirable for, inter alia',
environmental reasons.- The resin according to the invent'ion
does;not.~have this disadvantage. .~
~:..., Another use of the resin is its use~as'drying "'
emulsifier for.the~preparation.of;alkyd emulsions;jand in
acrylate dispersions. ' ' ''
The resin.according-:.to the invention ca'n be..'m'ixed
with the customary addltives for obtainlng pa1n:t~
co~mpo,sitions.;.;Examples of~thesec.additives~l.are pigments ! ,,,
?;.c,olourants,.fillers,?:.thickeners,: flow-promo't'ihg agént's',':~
thixotropic agents,:flatting..-agents.,~stabiI`i'z'ers and/or~
siccatives. '~
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WO91/06~86 2 0 7 2 0 9 6 PCT/NL90/0016
The invention i's~elucidated by means of the
following non-restrictive examples.
Examples
Example I
Preparation of a resin
In a four-necked flask provided with a nitrogen
feed system, mechanical stirrer, thermocouple and dropping
funnel, 98 parts by weight maleic anhydride was added at
215C to 878 parts by weight linseed oil and stirred at'
215C for such a length of time that no reflux of maleic
anhydride was visible any more. The resulting product was an
oil-like low-viscosity liquid with a total acid number of
115 mg KO~/gramme sample.
Subsequently, after cooling'to 130C, 586 parts by
weight allyl alcohol ethoxylated with 12 ethylene oxide
units, as well as 0.3 part by weight triethyl amine, were
added to this product.
~Finally, the whole was stirred for two hours at
130C. '
The result was a low-viscosity oil-like product
25 with the following properties: '''`` '
* solids content~ 100% ' ' ' "
Mw '~ 4220~
*.. Mn ~ 2340T
* polydispersityj-M~ Mn: ' 1.80~
30 * iodine value: ~ ll0 g J2/100~g^prodiu'c;t
* acid number: ' L~ 35'~mg KOH/g product
*. viscojsity 23~C tBohlih): O~ 18-l?dPas ! ` ; ; ~`Z
Example II and Comparative Exeeriment~A'-' ~
Preparation of a~ai~t.~ 2 e'' . ~ .S 'i.' ' ~ i; '
~;3J"~3,l~,In a-Cowless~dissolver,'a pigment'pastê based on a
' dispersant,~:~titanium di'oxide;~rthickener;'a'nd demin~àter'was
prepared at -3000 rpm forr30 ~inutes--acco'rding to `-Ta~ie ~
below. ~''-'i''-' '~
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~V091/06~6 2 0 7 2 0 9 6 PCT/~L90/0016
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Subsequently, to 1 part by weight of this paste 2
parts by weight alkyd emulsion were added. Finally,
siccativation took place using a cobalt (II)-acetate
solution.
The total compositions of these paints and their
properties are shown in the following table. :
TABLE I
II A
Demin water 210 220
orotan 731 SD, 25%1) 0 25
15 Kronos 21902) . 625 625 - .
QR 10013) 40 40
Resin according to Example I 42 0 .
_____________________ ____________________~________________
20 Uradil XP 515 AZ4) 1750 1820
______ _____ :
CoAcetate 6% - 23 24
Pigment-volume concentration, % 20 20 1 .
25 Solids content, % `` 60 60
Viscosity 23C,
(DIN 53019), dPas 2.6 3.2
pH 7.20 ~ 6.80
BK drying time, stage 1, min5) 40 30 .. .
30 BKjdrying~time,:stage!2,:min5): - : 80; 60
BK drying.time, stage~3, min5) : -: 250;J '220
~K drying time,~stageJ4,:minS ?. ~ ; i :300'` ~` '275
~ ~ t; ' ! ~ - '
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'' ~ , ' "' ' ''' ' ' ', ,' ' .'' , ' , , . . : ', ' ~, .
WO 91/06586 2 0 7 2 0 9 6 ` Pcr/~Lgo/00l6~ ,~
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T~3LE I ( continued)
5 Gloss 20 86 78
Gloss 60 100 91
Pendulum Hardness ~s), 1 day 22. 21
Pendulum Hardness (s)~ 1 week 21 20
Adhesion to wood6 ) 3 3
10 Adhesion to alkyd6) 5 4
Water resistance6), after 1 week 4 4
Adhesion wood5), after l week 5 5 .~.
Adhesion alkyd6), after 1 week 5 . 5
1) Orotan 731 SD: dispersant, isobutylenemaleic acid
copolymer-sodium salt
2) Kronos 2190: titanium dioxide ~ ~ .
3) QR 1001: polyurethane-based thickener
4) Uradil XP 515 Aæ: alkyd emulsion of DSM Resins.
5) The drying time was determined with a BK drying recorder
(BYK-Chemie no.2710., Mickle Laboratory Engineering Co.,
Gomshall, Surrey, England).
6 ? . Visual assessment where l .
1 ~ unacceptable .; . .. - :~
~, . . . .
. 25 2 - insufficient
3 = reaionable
4 ~ good . .
~ ; 5 = very good ~ .
30 ;, The gloss was improved considerably if,~instead'of'
.the Orotan 731 dispersant, thq:resin.according:to the ~ ¦
invention was used. Moreover~ the,other.desired properties
were retained. ¦.
Examples III and Comparative Experiments B-C
Example II was repeated, the amoun~R ~y weight
belng altered as indicated in Table II.
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,~-~O 91/06586 2 0 7 2 0 9 6; PCr/NL90/0016~
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Table II
III B
Demin water 8.0 12.25 11.1
Serad FX1010 (5~) - 2 3.4
Agitan 295 - 0.05 0,07
Serad FX508 - 0.4
serad FA607 - 0.1
orotan 731 (25%) - - 0.62
Borchigen DFN - 0.83-
Resin according to Example I 1.4
Tioxyde TR92 23.24 23.5 25.7
dispersed in pearl mill and
added to:
Uradil XP 552 AZ 59.9 58 56
Acrysol RM8 (3.5%-) 5.2 2.0 1.12
Aquacat - n . 35 0.64
Siccatol 938 1.65 - -
Serad FA179 - 0.3 0.1
Agitan 295 - 0.03
Fluorad FC129 (10% solution) 0.61 0.6 0.42
Serad FA607 - 0.42
Hardness 100~ 1 day . 28 34 25
2 days 40 40 40
7 days 48 46 43
30gloss 20~/60 1 day 87/92 73/89 82/92
7 days 83/92 65/88. 79/89
.
where:
. Serad FX1010: polyurethane-based thickener
35 Agitan 295: anti-foaming agent
Serad FX50~: pigment wetting agent
Serad FA607: pigment wetting agent
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~O9l/06i86 2072~9~ PCT/NL90/~0168 ~
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Orotan 731~ dispersant,
isobutylmaleic acid
copolymer-sodium salt
sorchigen DFN: pigment wetting agent
Tioxyde TR 92: pigment
Vradil xP 552AZ: alkyd emulsion of DSM Resins
Acrysol RM8: acrylate-containing thickener
10 Aquacat: siccative
Siccatol 938: siccative
Serad FA 179: corrosion inhibitor
Fluorad FC 129: wetting agent
A paint composition based on the resin according
to the invention resulted in a good gloss and good pigment
wetting properties.
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