CA2072096A1

CA2072096A1 - Water-soluble resin

Info

Publication number: CA2072096A1
Application number: CA002072096A
Authority: CA
Inventors: Adriaan Hofland; Dick A. Pons
Original assignee: Individual
Current assignee: Koninklijke DSM NV
Priority date: 1989-10-31
Filing date: 1990-10-30
Publication date: 1991-05-01
Also published as: EP0498834A1; AU6711390A; FI921927A0; HU9201429D0; WO1991006586A1; NO921698L; FI921927A; NO921698D0

Abstract

The invention relates to a water-soluble resin that can be used as a dispersant. The resin is substantially built up from units of: A) polyethylene glycol with (5-100) ethylene oxide units, B) a compound containing one or more allyl and/or (meth)acrylate groups and C) the reaction product of one or more unsaturated fatty acids or one or more polyalcohol(s) wholly or partly esterified with unsaturated fatty acids with a compound, where the A:C molar ratio is between 0.5:1 and 4:1 and the B:C molar ratio is between 0.5:1 and 4:1.

Description

~ O 91/06586 2 0 7 2 0 9 6 ; ~ pc~r/N~90/0016~

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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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;

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.-~vo9l/06586 2 0 7 2 ~`9 6` ` PCT/~L90/00'63 - 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 . -, ~^~O91/06586 2 0 7 2 jO 9 ~`. PCT/~L90/0016~
~: .

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''-' '~

'I
I

::: . . :

~V091/06~6 2 0 7 2 0 9 6 PCT/~L90/0016 -7~

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~ ,~

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~
t,",~ .
_9_ 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 . .

~O9l/06i86 2072~9~ PCT/NL90/~0168 ~

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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Claims

1. Water-soluble resin, characterized in that the resin is substantially built up from units of A. polyethylene glycol with (5-100) ethylene oxide units, B. a compound containing one or more allyl and/or (meth)acrylate groups and C. the reaction product of one or more unsaturated fatty acids or one or more polyalcohol(s) wholly or partly esterified with unsaturated fatty acids with an unsaturated carbonyl compound, where the A:C molar ratio is between 0.5:1 and 4:1 and the B:C molar ratio is between 0.5:1 and 4:1.
2. Resin according to claim 1, characterized in that the A:C molar ratio is between 0.8:1 and 2:1 and the B:C
molar ratio is between 0.8:1 and 2:1.
3. Resin according to any one of claims 1-2, characterized in that the A:B:C molar ratio is substantially 1:1:1.
4. Resin according to any one of claims 1-3, characterized in that the polyethylene glycol contains (8-20) ethylene oxide units.
5. Resin according to any one of claims 1-4, characterized in that B is a compound containing allyl groups.
6. Resin according to claim 5, characterized in that B is allyl alcohol.
7. Resin according to any one of claims 1-6, characterized in that C is the reaction product of linseed oil and/or safflower oil with maleic anhydride B. Process for preparing a resin substantially built up from units of A, B and C according to any one of claims 1-7, characterized in that, in a first reaction step, C
is obtained via a radical reaction of an unsaturated carbonyl compound with an unsaturated vegetable oil at a temperature above 150°C, upon which C reacts with an adduct of compounds A and B, in which reaction the A:C

molar ratio is between 0.5:1 and 4:1 and the B:C molar ratio is between 0.5:1 and 4:1.
9. Process according to claim 8, characterized in that the A:C molar ratio is between 0.8:1 and 2:1 and the B:C
molar ratio is between 0.8:1 and 2:1.
10. Process according to any one of claims 8-9, characterized in that the A:B:C molar ration is substantially 1:1:1.
11. Process according to any one of claims 8-10, characte-rized in that the polyethylene glycol contains (8-20) ethylene oxide units.
12. Process according to any one of claims 9-11, characte-rized in that B is a compound containing allyl groups.
13. Process according to claim 12, characterized in that B
is allyl alcohol.
14. Process according to any one of claims 8-13, characterized in that C is the reaction product of linseed oil and/or safflower oil with maleic anhyride.
15. Modified resin composition based on a resin according to any one of claims 1-7 or a resin obtained according to any one of claims 8-14 and one or more monofunctional epoxy compounds.
16. Use of a resin according to any one of claims 1-7 or 15 or use of a resin obtained according to any one of claims 8-14.
17. Use of a resin according to any one of claims 1-7 or 15 or use of a resin obtained according to any one of claims 8-14 as dispersant.
18. Water-soluble resin, process, modified resin composi-tion, use and use as dispersant as described in substance and/or further elucidated in the examples.