USOO678091 OB2

(12) United States Patent (10) Patent No.: US 6,780,910 B2

Bouvy et al. (45) Date of Patent: Aug. 24, 2004

(54) ALKYD RESIN EMULSION (58) Field of Search ................................. 524/366, 376,
524/77, 599
(75) Inventors: Alain Bouvy, Wezembeek Oppem (BE);
Bart Simon Alfons Dehuvyne, Dilbeek (56) References Cited
(BE)
(73) Assignee: Imperial Chemical Industries PLC, FOREIGN PATENT DOCUMENTS
London (GB) EP 649867 A1 * 4/1995
GB 1223O33 2/1971
(*) Notice: Subject to any disclaimer, the term of this GB 1535786 12/1978
patent is extended or adjusted under 35 WO WO 99/58617 11/1999
U.S.C. 154(b) by 0 days.
* cited by examiner
(21) Appl. No.: 10/304,016
(22) Filed: Nov. 26, 2002 Primary Examiner Patrick D. Niland
(74) Attorney, Agent, or Firm-Mayer, Brown Rowe &
(65) Prior Publication Data Maw LLP
US 2003/014.4397 A1 Jul. 31, 2003 (57) ABSTRACT
Related U.S. Application Data An aqueous emulsion of an alkyd resin which contains as an
emulsifier at least one branched primary alcohol alkoxylate
(63) Continuation of application No. PCT/GB01/02191, filed on of the formula (I). ICHs (CH), ICHs.(CH)). CHI(CH2).
May 17, 2001.
O.(AO)H), where n and m are each independently from 1
(30) Foreign Application Priority Data to 13; and p is 1 or 2; such that n+m+p is from 5 to 15; AO
May 31, 2000 (GB) ............................................. OO13028
is an alkylene oxide residue having from 2 to 4 carbon
atoms, and q is from 5 to 50. The alkyd emulsion is
(51) Int. Cl. ............................. C08J 3700; CO8K5/06; particularly Suitable for use as a waterborne paint or Surface
C08L 67/00; CO8L 73/00; CO8L 79/00 coating composition.
(52) U.S. Cl. ......................... 524/376; 524/77; 524/366;
524/599 13 Claims, No Drawings
 US 6,780,910 B2
1 2
ALKYD RESIN EMULSION Within the invention, we have found that particularly
good results may be obtained using combinations of non
CROSS REFERENCE TO RELATED ionic Surfactants, including compounds of the formula (I),
APPLICATION and anionic Surfactants to emulsify alkyd resins.
Accordingly, the invention further provides an aqueous
This application is a continuation of International Appli emulsion of an alkyd resin which comprises as an emulsifier
cation No. PCT/GB01/02191, filed May 17, 2001. This at least one branched primary alcohol alkoxylate of the
application, in its entirety, is incorporated herein by refer formula (I) above in combination with at least one anionic
CCC. Surfactant
This invention relates to emulsions and in particular to In compounds of the formula (I), n and m are desirably
aqueous emulsions of polyesters and more particularly to each independently at least 2 and not more than 12, p is
oil-modified polyester resins also known as alkyd resins and desirably 1 and the total number of carbon atoms in the
to their production. branched alkyl residue is desirably from 8 to 18, particularly
Polyester resins are well known materials with wide uses 10 to 15 and especially is about 12 (corresponding to n+m+p
in Surface coatings e.g. paints. Generally, they are film 15 from 5 to 15, particularly 7 to 12 and especially about 9).
forming Substances which are the products of esterification Mixtures of compounds having Such branched residues can
of polybasic acids and polyhydric alcohols. They can be be used.
either Saturated or unsaturated. Typical applications of poly The alkylene oxide groups are desirably ethylene oxide
esters include industrial wood coatings, can and coil and/or propylene oxide residues. Desirably, all the residues
coatings, industrial enamels, domestic appliances coatings are ethylene oxide residues although mixtures of ethylene
and Stoving enamels. oxide and propylene oxide residues, desirably with a molar
Alkyd resins are the largest group of Synthetic resins used ratio of ethylene oxide to propylene oxide residues from 1:5
in the coating industry, are polyester resins which include to 10:1, can be used. When mixed alkylene oxide residues
residues of polybasic, usually di-basic, acid(s) and are used, the polyoxyalkylene chain can be a random or
polyhydroxy, usually tri- or higher hydroxy alcohols and 25 block copolymeric chain. Within the range 5 to 50, q is
further including monobasic fatty acid residues. The desirably 10 to 30. The number of units in the polyoxyalky
monobasic residues may be derived (directly or indirectly) lene chain, q, is an average value and may be non-integral.
from oils (fatty acid triglycerides) and alkyd resins are also The alkoxylates of the formula (I) can be used alone or
referred to as oil modified polyester resins. Alkyds used in and desirably, in combination with Similar alkoxylates of
Surface coatings are generally curable usually either from linear primary alcohols, containing Similar numbers of car
residual carboxyl and hydroxyl functionality or by unsat bon atoms. The proportion of branched alkoxylate, of the
uration (often multiple unsaturation) in the monobasic fatty formula (I), is desirably at least 30% and more usually at
least 40%.
acid residues. Some alkyds are used as plasticisers e.g. for The alkoxylates used in this invention can be made by
other alkyd resins, and these materials are not usually alkoxylation of the corresponding primary alcohols under
curable. Alkyd resins may include other residues and/or 35
additives to provide specific functionality for the intended conventional alkoxylation conditions, typically under alkali
end use e.g. Sources of additional carboxyl groups may be catalysis, particularly alkoxide catalysis e.g. using NaOH or
included to improve water compatibility. Alkyds have found KOH to form alkoxide in situ. Where the alkoxylate is
widespread use in paints, particularly Solvent based paints. wholly of the formula (I), the alcohol used is substantially
In developing low VOC's formulations, much effort has 40 wholly branched primary alcohol as can be made by the
been directed to making aqueous emulsions of alkyd resins, guerbet process. Where the alkoxylate is a combination of
(including those using mixed Solvent/water vehicles). The alkoxylates of the formula (I) with similar alkoxylates of
alkyds are usually formed into an emulsion before incorpo linear primary alcohols, the alcohol used can be a mixture of
ration into the paint and emulsification typically involves the branched primary alcohols with linear primary alcohols,
formation of an alkyd in water emulsion in which the alkyd 45 containing similar numbers of carbon atoms. Such mixed
is dispersed in the water phase as uniformly and generally as alcohols can be made by the OXO proceSS using feedstockS
finely as possible. To do this emulsifiers, either as Single including internal olefins (internal olefins isomerise under
components or in combination, are commonly used. typical oXo reaction conditions).
The term non-ionic Surfactant is Sometimes herein used to
The present invention is based on our finding that com 50 refer to branched or mixtures of branched and linear alcohol
binations of certain classes of alcohol alkoxylates, particu alkoxylates used in this invention.
larly ethoxylates, based on branched primary alcohols can The alkyd resins used in this invention are typically resins
give alkyd resin emulsions in water that have a low average which are the reaction products of:
particle size and narrow particle Size distribution. one or more polybasic (di- or higher basic) organic
Accordingly, the present invention provides an aqueous 55 acid/anhydride: e.g. phthalic anhydride,
emulsion of an alkyd resin which comprises as an emulsifier one or more polyhydric (usually a tri- or higher) alcohol:
at least one branched primary alcohol alkoxylate of the e.g. glycerol, and
formula (I): one or more monobasic fatty acid, usually an unsaturated
ICHs.(CH), ICHs.(CH2)CHI(CH2).O.(AO).H. (I) fatty acid, or one or more ester, particularly triglyceride
60 of Such fatty acids: e.g. Soya oil, tall oil fatty acids.
where The molar proportions of these component monomers are
chosen to give the desired physical properties and molecular
in and m are each independently from 1 to 13, and p is 1 weight distribution of the resulting polyester. The monoba
or 2; such that n+m+p is from 5 to 15; sic fatty acid or triglyceride, often includes unsaturation e.g.
AO is an alkylene oxide residue having from 2 to 4 carbon 65 vegetable oils or fatty acids, and the presence of unsaturation
atoms, and leads to the air-curing properties of these materials. Most
q is from 5 to 50. alkyds are film-forming polymers with a relatively low glass
 US 6,780,910 B2
3 4
transition temperature, typically below 0°C., that are readily or potassium) hydroxide or carbonate or amines, particularly
pigmented and usually accept additives to form coatings alkanolamines Such as DELA and TELA.
with a wide range of appearance, performance, and appli In particular where an ether carboxylate is used as an
cation characteristics. The alkyd resins used in this invention anionic Surfactant, the emulsion desirably comprises one or
are typically air-curing types as used in Surface coating end more neutralising agents. Generally, the neutralising agent is
use applications. Typically alkyd resins used in this inven added to and well mixed with the anionic Surfactant, usually
tion will have an oil length of from 25 to 100%, typically by mixing into a blend of the non-ionic and anionic Surfac
from 50 to 80%. Siliconized alkyds can also be used. tants and the resin to be emulsified, before adding the bulk
Suitable alkyds are widely available and are used exten of the water used in emulsification. The ether carboxylate
Sively in Surface coating applications. can be neutralised before mixing with the resin, but this is
Although effective emulsification can be achieved using leSS convenient because the resin may contribute to the
Surfactants of the formula (I) on their own, they can also be neutralisation requirement. For this reason an excess over
used in combination with anionic Surfactants particularly the nominal amount of neutralisation agent will usually be
phosphate esters, ether carboxylates, alkyl ether Sulphate, used. Amounts of neutralising agent are typically from 0.5 to
5% by weight of the emulsion, although, in practice, the
alkyl aryl Sulphonates or mixtures of these types of anionic 15 amount of neutralising agent used will normally be that
Surfactants. Sufficient to achieve a pH, within a desired range in the
Ether carboxylates which can be used in the invention are product emulsion. Desirably the product emulsion will typi
typically of the formula (II): cally have a pH of from 3 to 9, particularly 5 to 8.5. Modest
amounts of base may be added to the System to obtain Such
R"O-(EO), CHCOM (II) pHS by neutralising acidity in the alkyd resin even where
where the anionic Surfactant is used in the form of a Salt or where
no anionic Surfactant is used.
R" is a Co to Cls hydrocarbyl, particularly a C2 to C, The emulsions will typically contain from 45 to 60, more
alkyl, group; usually from 40 to 55 and particularly about 50% by weight
EO is an ethyleneoxy group; 25 of the emulsified resin.
n is from 3 to 10, particularly 4 to 8, especially about 6; The total amount of Surfactant, non-ionic and (when used)
and anionic, used as emulsifier in this invention will typically be
M is hydrogen, alkali metal, especially Na or K or from 2 to 20%, more usually from 5 to 15%, and desirably
ammonium (including amine onium). from 6 to 10%, by weight based on alkyd resin emulsified.
In formula (II) R' can represent mixed groups e.g. mixed In general lower amounts of emulsifier give emulsions with
alkyl groupS. Such as mixed C to Cls alkyl groups, as are larger average particle Size and usually higher
polydispersity, generally implying a longer tail of rela
commonly used in making surfactants and n (like q in tively coarse emulsion droplets. Based on emulsions con
formula (I)) is an average value and may be non-integral. taining 50% of alkyd resin these correspond to general
Ether carboxylates are commonly Supplied in the free acid amounts of surfactant of from 1 to 10%, more usually from
form and for use as Surfactants are usually neutralised (see 35 2.5 to 7.5% and desirably from 2.5 to 5% by weight on the
below). total emulsion. The amounts used for emulsions containing
Suitable alkyl aryl Sulphonates include alkyl benzene other alkyd resin concentrations will vary accordingly.
Sulphonates, typically Cs to Cls linear alkyl benzene Sul Typical emulsion compositions by weight are exemplified
phonates. These are well known Surfactants and are usually in the following table:
Sold as Salts with Suitable bases. If Supplied as free acids, 40
they can be neutralised (see below).
When used, the weight ratio of non-ionic Surfactant
(comprising compound(s) of the formula (I)) to anionic amount (parts by Weight
Surfactant, particularly alkyl aryl Sulphonate, ether carboxy Material typical preferred
late or a mixture, is usually from 90:10 to 10:90, desirably 45
80:20 to 20:80, and particularly 75:25 to 25:75. alkyd resin
total surfactant
40 to 60
O.S to 7
about 50
O6 to 6
The invention further includes an aqueous emulsion of an % surfactant on resin 2 to 20 5 to 10
alkyd resin which comprises as an emulsifier at least one when anionic surfactant used:
branched primary alcohol alkoxylate of the formula (I)
above in combination with an anionic Surfactant, particu 50 non-ionic
anionic
O.S to 5.5
O.S to 5.5
2 to 5
2 to 5
larly an alkyl benzene Sulphonate, an ether carboxylate wt ratio non-ionic: anionic 90:10 to 10:90 75:25 to 25:75
surfactant of the formula (II) above, or a mixture of these neutralising agent (1) pH 3 to 8
anionic Surfactants, in particular where the weight ratio of water to 100
non-ionic Surfactant, comprising compound(s) of the for
mula (I), to anionic surfactant is from 80:20 to 20:80. 55 (1) the neutralising agent (base) (if any) is used to give a pH in the stated
The anionic Surfactants contain acidic groups which will range (and may include base which neutralises acidity in the alkyd resin).
usually be reacted (at least mainly) with counter ions to form The emulsions of the invention can be and are desirably
salts before use. This can be done in manufacture of the made by inverse emulsification, in particular by forming a
Surfactants e.g. as is usual with alkyl aryl Sulphonates, and mixture of the resin and Surfactant, including Surfactant of
typical counter ions include alkali metal ions, particularly 60 the formula (I), adding water to form a water in oil (resin)
Sodium and potassium, ammonium ions and amine onium, emulsion, continuing water addition until the emulsion
particularly derived from alkanolamines Such as inverts to form an oil (resin) in water emulsion and, if
di-ethanolamine (DELA) and tri-ethanolamine (TELA). necessary e.g. to prevent re-inversion of the emulsion and/or
Usually ether carboxylate Surfactants are Supplied in the free to adjust the Solids content of the emulsion, adding further
acid form and are typically neutralised at the point of use or 65 water to adjust the disperse phase content of the emulsion to
in Situ during emulsification. Neutralisation can be effected that desired. This technique is known in the art as the
using Suitable base Such as alkali metal (particularly Sodium Emulsion Inversion Point (EIP) method.
 US 6,780,910 B2
S
The invention-accordingly includes a method-of making Materials
an aqueous emulsion-of a resin, particularly an alkyd resin, Branched Primary Alcohols
which comprises forming a mixture of the resin and AL1 mixture of primary alcohols mainly having 12 to 15
Surfactant, comprising at least one branched primary alcohol carbon atoms and containing about 50% monobranched
alkoxylate Surfactant of the formula (I), comprising water in primary alcohol and about 50% linear primary alcohol
the mixture to form a water in oil (resin) emulsion, and made by the OXO process from internal olefin precursors
Subsequently adding water to the water-in-oil emulsion at Branched Primary Alcohol Alkoxylate Surfactants
least until the emulsion inverts to form an oil (resin) in water AE1 AL15-ethoxylate
emulsion and, optionally, adding further water to adjust the AE2 AL1 12.5-ethoxylate
disperse phase content of the emulsion to that desired. Other Surfactants
Generally, at least prior to the inversion to form an AS1 C14/15 alcohol 6-ethoxylate ethercarboxylate (acid
oil-in-water emulsion, the Viscosity of the mixture is typi form) 90% active
cally fairly high (reflecting the Viscosity of the resin con AS2 Atsurf 3300B anionic surfactant-alkyl arylsulphonate
tinuous phase) and to effect good mixing, the mixture will be 95% active ex Uniqema
Stirred vigorously. Usually, after inversion, the Stirring effort PS1 Hypermer A119 polymeric Surfactant 100% active ex
can be reduced because the Viscosity falls Substantially. 15 Uniqema
(Also the mixing is not providing energy for Substantial SB1 Atsurf 3863 proprietary anionic/nonionic surfactant
increase in net inter-phase Surface area.) blend (80% active) ex Uniqema
The temperature at which the emulsion is prepared SB2 Atsurf 3969 proprietary nonionic Surfactant blend
depends on the Viscosity of liquid resins and the Softening (100% active) ex Uniqema
and/or melting point of Solid resins and the properties of the Alkyd Resins
Softened and/or melted resin. Resins which are liquid at RA1 Long oil tall oil alkyd resin, 72% tall oil fatty acid, 19%
ambient temperature, Such as many alkyd resins, are usually isophthalic acid (100% active)
Sufficiently viscous to make it inconvenient to carry out RA2 Long oil alkyd resin, approx. 72% oil length (100%
emulsification at temperatures as low as ambient. For Such active)
resins, the temperature of emulsification will be moderately 25 RA3 Short oil soybean alkyd resin, oil length ca. 45% (100%
Superambient, typically up to about 75 C. e.g. in the range active)
30 to 75 C., particularly 40 to 60° C. and especially about RA4 Long oil tall oil alkyd resin, oil length ca. 74% (100%
50° C. can be used. active)
The emulsions of the invention can provide alkyd resins RA5 Linoleic rich fatty acid alkyd resin, oil length ca. 59%
in the form of emulsion droplets having an average diameter (100% active)
of less than 500 nm, and frequently less than 300 nm. RA6 Soybean oil based alkyd resin, oil length ca. 58%
The emulsions, particularly alkyd resin emulsions, of the (100% active)
invention can be used to make waterborne paints or coatings RA7 Soybean oil based alkyd resin, oil length ca. 63%
by mixing with at least one Separately prepared pigment (100% active)
35 Other Materials
dispersion. This very well known method by those skilled in TELA commercial triethanolamine ca 99% by weight
the art-often called “letdown” is typically carried out NaOH 10% aqueous NaOH solution
under gentle agitation. The Success of the letdown Step MeOPr 2-methoxypropanol (co-solvent)
depends on achieving an intimate intermingling of these two water demineralised water
disparate particle Systems to yield a stable and uniform 40 Methods
overall particle Suspension (the alkyd-based paint) and the Emulsion Manufacture
emulsions of this invention can be effectively used in Such Alkyd resin emulsions were made by the inversion emul
Systems. The invention accordingly further includes a water sification method in 250 ml or 500 ml vessels using an IKA
borne paint or Surface coating composition which comprises RW 20.n mixer with stirring using a paddle bladed stirrer at
an alkyd emulsion of the invention. 45 a rotational speed of 2000 rpm (ca 33 Hz) with a 4 cm
The practical performance of Such paint formulations can diameter 6-bladed paddle (unless otherwise stated). The
be improved by including other additives. Examples temperature of emulsification ranged from ambient to 90° C.
include:
driers (or curing catalysts) which are typically oil/resin The resin and a small amount of water were heated (if
Soluble metal Salts. Such as naphthenates, typically necessary) to the emulsification temperature, the Surfactant
incorporated at levels of 1 to 10% by weight of the
50 (s) were then added and blended thoroughly. If necessary,
resin; neutralising agent (for resin and/or anionic emulsifier) was
added and mixed in thoroughly. Further water was added
co-driers, also described as loSS of dryneSS inhibitors as gradually under mixing. Initially a water in oil (alkyd)
they can counter possible inhibition of driers by the emulsion (having poor Stability) is formed and the Viscosity
presence of e.g. anioninc Surfactants or emulsifiers, So 55 of this emulsion increases as more water is added up to a
that their inclusion can give faster or more complete maximum at or near the inversion point. The mixing during
hardening of the resin film in a coating thus enhancing water addition is Sufficient to form a homogeneous (water in
performance, typically used at levels of 1 to 10% by oil) emulsion. With the addition of more water the emulsion
weight of the resin; will reach a point where inversions occurs to form an oil
rheology modifiers, 60 (alkyd) in water emulsion. After inversion the Viscosity
wetting and compatibility agents, and usually falls So Stirring may be leSS Vigorous e.g. about 300
flow and levelling agents which will typically be incor rpm (5 Hz), and further water can be added relatively
porated at this stage. Typical applications of formula quickly. If necessary the emulsion is then cooled to ambient
tions include wood coatings and high gloSS architec temperature and as required further water added to reach the
tural paints. 65 desired product composition.
The following Examples illustrate the invention. All parts Particle Size analysis-emulsion particle Size was mea
and percentages are by weight unless otherwise Stated. Sured using a Malvern Zetasizer 4 (covering the size range
 US 6,780,910 B2
7 8
50 nm to 1 um) and the particle size reported as cumulative EXAMPLE 2
Z-average (Z-av) in nm, instrumentally calculated polydis
persity (Poly) and peak width of the largest peak (Width) in
. Alkyd resins RA1 and RA2 were emulsified using a
Viscosity-emulsion Viscosity was measured using a combination of alcohol ethoxylate AE1 and anionic Surfac
Brookfield LVT viscometer at about 25 C., the spindle used tant AS2. For resin RA1 the emulsification temperature used
is indicated in brackets in the table headings e.g. (Sp1). was 70° C. and for RA2 ambient temperature. The compo
Results are given in mPa..S. sition of the formulations is given in Table 2a:
pH-was measured using a WTW pH 537 meter
Ageing-Some emulsion samples were stored (aged) and
re-tested. The extent of ageing is indicated by a code in the TABLE 2a
tables. The first character of the code indicates the length of
Storage (0=no ageing), the next two characters indicate the Amounts of components
Storage time in months (m=month), and any further charac Sample parts by weight
ters indicate the (non-ambient) temperature of storage in 15 No RANo RA AE1 AS2 water Ratio Surf 2%
C.; So, for example, 1 m/5 indicates 1 month Storage at 5
C. and 3 m/-5/40 indicates 3 months storage with freeze 2.1 RA1 50 3.25 1.75 to 100 80:20 1O
thaw cycling between -5 C. and 40 C. with a cycle time 2.2
2.3
RA1
RA2
50
50
1.4
3
2.6
2
to
to
100
100
35:65
60:40
8
1O
of 12 hours.
2.4 RA2 50 2.4 1.6 to 100 60:40 8
In the Examples Ratio is the weight ratio of non-ionic to
anionic Surfactant and Surf 76 is the weight percentage of
total Surfactant based on the alkyd resin.
EXAMPLE 1. Samples of these emulsions were Subjected to Storage
Alkyd resin emulsions were made up using resin RA2 stability tests and the results are set out in Table 2b:
using combinations of alcohol ethoxylate AE1 and anionic 25
surfactant AS2. For Samples 1.1 to 1.6, the inversion emul
sion process was carried out at 50 C. and for Sample 1.7 the TABLE 2b
process temperature was ambient temperature. Just after
completion of water addition, a drop of antifoam was added Sample Visc (sp) Particle Size
to knock down any foam generated during the emulsification No Age pH 60 rpm Z-av Poly Width
process. The formulations and properties of these emulsions
are set out in Table 1a below. 2.1 O 4.4 640 72 O.12 81
1 m. 4.3 570 8O O1 40
1 m/5 4.3 560 77 O.04 3O
TABLE 1 a 1 m/40 4.3 660 71 O1 85
3 m. 4.2 6OO 74 O.09 26
Sample Amounts (parts by weight Particle size 35 3 m/5 4.2 610 71 O.O3 71
3 m/40 4.3 860 69 O.04 70
No AE1 AS2 RA2 water Ratio Surf 26 Z-av 2.2 O 4.4 610 63 O.O7 70
1.1 3.75 1.25 50 to 100 80:2O 10 250 1 m. 4.4 58O 71 O1 83
1.2 2.5 2.5 50 to 1 OO SO:SO 10 148 1 mf-5 4.3 560 75 O.12 102
1.3 3.75 1.25 50 to 100 20:80 10 772 1 m/5 4.4 560 81 O1 82
40 1 m/40 4.4 560 79 O.12 98
1.4 2 2 50 to 1 OO SO:SO 8 172
1.5 1.5 1.5 50 to 1 OO SO:SO 6 624 3 m. 4.3 570 74 O.O6 29
1.6 1. 1. 50 to 1 OO SO:SO 4 2507 3 m/5 4.3 590 74 O.13 66
1.7 2.5 2.5 50 to 1 OO SO:SO 10 230 3 m/40 4.3 700 78 O.05 34
2.3 O 4.4 860 57 O.O1 42
1 m. 4.3 340 59 O.O6 95
45 1 m/5 4.4 750 59 O.09 117
These results show the finest emulsion at a weight ratio of 1 m/40 4.3 675 60 O.05 90
the two Surfactants of about 50:50, that the finest emulsion 3 m. 4.4 330 44 O.O3 63
is obtained at a concentration of emulsifier of about 8% by 3 m/5 4.4 830 44 O.08 95
weight of the resin; and that preparation at 50 C. gave a 3
6
m/40
m
4.3
4.2
840
305
41
61
O.09
O.O6
102
91
Somewhat finer emulsion. 6 m/5 4.3 770 64 O.12 135
50
Further amounts of Sample 1.4 were made by the method 6 m/40 3.9 1OOO 65 O.08 111
described above and the emulsion Subjected to Storage 2.4 O 4.3 48O 2OO O.O1 42
Stability testing. The larger Scale of preparation is believed 1
1
m.
m/5
4.3
4.3
260
450
91
93
O.09
O.O7
139
12O
to be the reason for the Slightly larger initial particle size 1 m/40 4.3 375 99 O1 154
obtained. The results are set out in Table 1b: 3 m. 4.3 260 76 O.O1 31
55 3 m/5 4.3 455 83 O.04 86
TABLE 1 b 3 m/40 4.2 435 78 O.08 123
6 m 4.0 245 98 O.04 97
Sample Viscosity Particle Size 6 m/5 4.2 430 94 O.O1 50

No Age 6 rpm 30 rpm 60 rpm Z-av Poly *Spindle 3 was used for Samples 2.1 and 2.2 and spindle 2 for samples
60 2.3 and 2.4
1.4 O 702 390 281 210 O.O90
1 m 78O 390 289 216 O.OSO
1 m/-5 702 4O6 296 246 0.2O7
1 m/40 702 374 289 212 O.1OO
These data show that these emulsions have good Storage
Stability under a range of temperature conditions, although
65 samples 2.3 and 2.4 showed a slight reduction in pH after 6
The formulation showed Stability under Storage under a months at 40 C., but without adverse effect on emulsion
wide temperature range. quality.
 US 6,780,910 B2
9
EXAMPLE 3
TABLE 4b
Alkyd resins RA3, RA4, RA5 and RA6 were emulsified
using a combination of alcohol ethoxylate AE1 and anionic Sample Particle Size
Surfactants AS1 and AS2 alone or in combination as Set out
No Z-av Poly Width
in Table 3a:
4.1 195 1.O 31
TABLE 3a 4.2 211 O.65 25
4.3 284 1.O 125
Sam 4C.1 412 1.O 107
ple RA Amounts (parts by weight 4C.2 443 1.O 195
4C.3 216 O.63 32
No No RA AS1, AS2 AE1 NaOH TELA Water

3.1 RA3 51.5 1.28 - 3.87 2.56 to 100

3.2 RA4 53.57 - 1.45 1.77 - to 100 The good performance of the Samples according to the
3.3 RAS SO 1.5 1.0 2.5 - 1.5 to 100 15 invention is clear. Alcohol ethoxylate AE1 used leSS anionic
3.4 RA6 50 1.2 0.8 2.0 - 1.5 to 100
Surfactant (reducing the risk of foam formation in use) and
is significantly more effective on an overall weight basis
For Sample 3.1, NaOH was used to neutralise the ether than PS1 and is more effective on a weight basis-than SB1.
carboxylate and for samples 3.3 and 3.4, TELA was used.
The results of testing during Storage are set out in Table 3b: EXAMPLE 5

TABLE 3b Resin RA6 was emulsified with a variety of emulsification

Systems. Some based on a combination of alcohol ethoxylate
Sample Visc (sp3) Particle Size 25 AE1 and anionic Surfactant AS2 according to the invention
No Age pH 60 rpm Z-av Poly Width
and some for comparison based on surfactants PS1 and SB1.
The formulations and particle sizes obtained are given in
3.1 O 6.9 1090 158 O.18 116 Tables. 5a and 5b:
1 m 6.6 740 159 0.17 101
1 m/5 6.6 98O 165 O.12 92
1 m/40 6.4 290 168 O.O3 70 TABLE 5a
3 m 6.4 570 159 O.12 91
3 m/5 6.8 910 138 O.05 58 Sam- Amounts (parts by Weight
3 m/40 5.0 2OO 152 O.11 71
3.2 O 3.7 333 262 O31 37 ple Wa- Surf
1 m 3.7 318 222 O.96 33 No RA6 AE1 AS2 TELA PS1 SB1 ter Ratio 2%
35
1 mf-5 3.8 295 241 O.66 3O
5.1 50 18 2.2 1.25 tO 45:55 8
1 m/5 3.8 3O8 238 O.28 25
1OO
1 m/40 3.7 3O8 240 O.92 29 5.2 50 2.25 2.75 155 tO 45:55 10
1 mf-5/40 3.7 3O8 248 O.61 86 1OO
3 m 3.8 318 245 O.66 32
5C.1 50 6.25 to 1O
3 m/5 3.7 315 226 O.53 86
40 1OO
3 m/40 3.7 388 235 O.82 81 5C2 50 2.75 2.25 tO 12
3 m/-5/40 3.6 310 239 1.OO 44 1OO
3.3 O 191 O.18 197
3.4 O 2O1 O.13 179

45 TABLE 5b
EXAMPLE 4
Sample Particle Size
Emulsions were made up using resin RA4 and combina No Z-av Poly Width
tions of alcohol ethoxylate AE1 and anionic surfactant AS2 5.1 183 1.19 130
according to the invention and for comparison using com 50
5.2 151 O.21 57
binations of polymeric Surfactant PS1 and AS2 and using 5C1 3O1 O.67 37
surfactant blend SB1. The formulations and particle size 5C2 167 0.17 31
results are given in Tables 4a and 4b.
55
These results show that the samples of the invention are
TABLE 4a Superior to the emulsions made using PS1 and SB1 in using
less total Surfactant.
Sample Amounts (parts by Weight
No RA4 AE1 AS2 PS1. SB1 Water Ratio Surf 2% 60 EXAMPLE 6
4.1 50 2.75 225 - to 100 55:45 10
4.2
4.3
50
50
2.2
2.15
1.8
1.35
-
-
to
to
100
100
55:45
61:39
8
7
Resin RA6 was emulsified with a variety of emulsification
4C.1 50 2.75 2.25 - to 100 - 1O
Systems. Some based on a combination of alcohol ethoxylate
4C.2 50 2.2 1.8 - to 100 - 8 AE1 and anionic Surfactant AS1 according to the invention
4C.3 50 6.25 to 100 - 1O 65 and some for comparison based on surfactants PS1, SB1 and
SB2. The formulations and particle sizes obtained are given
in Tables 6a and 6b:
 US 6,780,910 B2
12
TABLE 6a
Sample Amounts (pbw additives other surfactant
No RA6 AE1 AS1 type amount type amount Water Ratio Surf 7%
6C.1 50 MeOPr 3.25 SB2 5.3 to 100 10.6
6C.2 50 SB1 6.25 to 100 1O
6.1 50 1.8 2.2 TELA 1.25 to 100 55:45 8
6.2 50 2.25 2.75 TELA 155 to 100 55:45
6C.3 50 2.75 - PS1 2.25 to 100 55:45

2. An emulsion as claimed in claim 1 in which in the

TABLE 6b
15
compound(s) of the formula (I), n and m are each indepen
Sample Particle Size dently at least 2 and not more than 12, p is 1 and the total
number of carbon atoms in the branched alkyl residue is
No Z-av Poly Width from 8 to 18.
6C.1 281 O.31 383 3. An emulsion as claimed in claim 1 in which in the
6.1 183 O.19 130
compound(s) of the formula (I), q is 10 to 30; the residues
6.2 151 O.21 57 AO are of ethylene oxide, propylene oxide or a mixture of
6C.3 167 0.17 31 ethylene oxide and propylene oxide residues; and, if the
residues AO include propylene oxide residues, the molar
25
ratio of ethylene oxide to propylene oxide residues is from
1:5 to 10:1.
EXAMPLE 7
4. An emulsion as claimed in claim 1 in which the
Resin RA7 was emulsified with alcohol ethoxylate AE2, compound(s) of the formula (I) are used in admixture with
and a combination of alcohol ethoxylates AE1 and AE2. The at least one alkoxylate of a linear primary alcohol containing
formulations and particle sizes obtained are given in Tables a similar number of carbon atoms and in which the propor
7a and 7b: tion of branched alkoxylate is at least 40%.
5. An emulsion as claimed in claim 1 in which the
TABLE 7a compound(s) of the formula (I) are used in admixture with
at least one anionic emulsifier.
Sample Amounts (pbw Additives surf 6. An emulsion as claimed in claim 5 in which the at least
35
No RA7 AE2 AE1 type amount Water Ratio (% one anionic emulsifier comprises at least one of: phosphate
7a 50 3.5 - NaOH 4.1 to 100 - 7
esters, ether carboxylates, alkyl ether Sulphate, alkyl aryl
7b 50 5 NaOH ca. to 100 - 1O Sulphonates or mixtures of these types of anionic Surfac
4.0 tantS.
7c 50 3 O.S. NaOH 4.1 to 1 OO 95:15 f 40 7. An emulsion as claimed in claim 6 in which the anionic
MeOPr O.S
emulsifier is or comprises at least one ether carboxylate of
* 10% the formula (II):
R"O-(EO), CHCOM (II)
TABLE 7b 45
where
Sample Particle Size
R is a Co to Cs hydrocarbyl group;
No Z-av Poly Width
EO is an ethyleneoxy group;
7a 314 O.88 438
7b 2O2 O.OS 112
50 n is from 3 to 10; and
7c 343 O.42 31 M is hydrogen, alkali metal, or ammonium.
8. An emulsion as claimed in claim 5 in which the anionic
What is claimed is: emulsifier is or comprises at least one alkyl benzene Sul
phonate.
1. An acqueous emulsion of an alkyd resin which com 55
9. An emulsion as claimed in claim 5 in which the weight
prises as an emulsifier an emulsifying amount of an at least ratio of non-ionic Surfactant (comprising compound(s) of the
one branched primary alcohol alkoxylate of the formula(I):
formula(I)) to anionic surfactant is from 80:20 to 20:80.
10. An emulsion as claimed in claim 1 in which the total
ICHs.(CH), ICHs.(CH2)CHI(CH2).O.(AO).H. (1)
60 amount of Surfactant, non-ionic and (when used) anionic,
where
emulsifier in the emulsion is from 5 to 15% by weight of the
emulsion.
in and m are each independently from 1 to 13, and p is 1 11. A method of making an emulsion as defined in claim
or 2, 1 which comprises the Steps of forming a mixture of the
Such that n+m+p is from 5 to 15; 65 resin and Surfactant, comprising at least one branched pri
AO is an alkylene oxide residue having from 2 to 4 carbon mary alcohol alkoxylate Surfactant of the formula (I), com
atoms; and q is from 5 to 50. prising water in the mixture to form a water in oil (resin)
 US 6,780,910 B2
13 14
emulsion, and Subsequently adding water to the water-in-oil 13. A waterborne paint or Surface coating composition as
emulsion at least until the emulsion inverts to form an oil claimed in claim 12 which additionally comprises at least
(resin) in water emulsion and, optionally, adding further one of driers (or curing catalysts); co-driers; rheology
water to adjust the disperse phase content of the emulsion to modifiers, wetting and compatibility agents, and/or flow and
that desired. 5 levelling agents.
12. A waterborne paint or Surface coating composition
which comprises an alkyd emulsion as defined in claim 1. k . . . .