(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property Organization

International Bureau
(10) International Publication Number
(43) International Publication Date , ,
21 July 2011 (21.07.2011) WO 201 1/085520 Al

(51) International Patent Classification:
C09D 167/08 (2006.01)
(21) International Application Number:
PCT/CN20 10/000068
(22) International Filing Date:
15 January 2010 (15.01 .2010)
(25) Filing Language:
(26) Publication Language:
(71) Applicant (for all designated States except US): DOW
GLOBAL TECHNOLOGIES LLC [US/US]; 2040
Dow Center, Midland, MI 48674 (US).
Tech Plaza, No.l, Wangzhuang Road, Haidian District,
Beijing 100083 (CN).
(81) Designated States (unless otherwise indicated, for every
kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ,
CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO,
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
English HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP,
KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD,
English ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI,
NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD,
SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR,
TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.

(72) Inventors; and
(75) Inventors/ Applicants (for US only): LEE, Yupeng [CN/
CN]; Room 202, No. 580 YaoHua Road, Shanghai
200120 (CN). CHEN, Ling [CN/CN]; No. 30, Xueyuan
Road, Beijing 100083 (CN). FANG, Haibo [CN/CN];
Room 401, No. 321 Jin Feng Xin Cun, Shanghai 200120
(CN). HU, Jiangqiang [CN/CN]; Room 204, Building
30, Shanghai 200120 (CN). ZHANG, Ping [US/US];
Room 702, No. 26 Shanghai 200433 (CN).
(74) Agent: CHINA SCIENCE PATENT & TRADEMARK
AGENT LTD; 25/F., Building B, Tsinghua Tongfang H i
(84) Designated States (unless otherwise indicated, for every
kind of regional protection available): ARIPO (BW, GH,
GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ,
TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE,
ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, SM,
TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
ML, MR, NE, SN, TD, TG).
Published:
— with international search report (Art. 21(3))

o
© (54) Title: ALKYD COATING FORMULATIONS
(57) Abstract: A coating formulation including (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant; (c)
water; (d) at least one solvent; (e) at least one solvent borne air drying alkyd resin coating; and (f) optionally, at least one amino-
methyl propanol co-dispersant. The coating formulation is useful for making topcoats and primer coats.
 ALKYD COATING FORMULATIONS

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to coating formulations. More specifically, the

present invention relates to solvent-borne (SB) alkyd coating formulations, in particular to
low cost SB air-drying alkyd coating formulations having low volatile organic compounds
(VOC) and a low viscosity. The coating formulations of the present invention may be useful
for example as protective topcoats or primer coats.

Description of Background and Related Art

Alkyd coating formulations containing solvents are widely used for wall
paints; and for wood and metal coatings for protective and aesthetic reasons. The coating
industry is continually seeking the development of lower VOC coating formulations, i.e.,
formulations containing no solvents or at least a solvent concentration of less than about
10 weight percent. Also, currently solvent prices have increased in line with oil prices, and
therefore, the challenge for paint formulators and alkyd coat formulators is to develop alkyd
coatings with lower solvent levels (i.e., lower VOC), that have unchanged paint and dry film
properties, and which are cost effective.

In some cases, water can be formulated in solvent based alkyd coats as a

partial replacement for the solvent present in the coating formulation via the use of
surfactants as emulsion stabilizers in the alkyd coats. In an attempt to reduce the use of
solvents in a solvent-based coating, certain surfactants have been tried in the coating
formulation. Introducing certain surfactants into a solvent-based alkyd coat may allow
water to replace the solvent in the coat. However, it has been difficult to properly formulate
an alkyd coat when introducing surfactant and water; and typically the formulation cannot
maintain the desired physical properties performance and viscosity requirements for many
end uses. Performances such as viscosity, dry time, gloss, impact resistance and hardness,
adhesion, flexibility, and the like are difficult to maintain in previously known coating
formulations.
 It would be desirable to provide a coating formulation with a low VOC, a low
cost and a good emulsion performance which would meet certain requirements of industry
performance standards.

SUMMARY OF THE INVENTION

The present invention uses a combination of two or more surfactants as an

emulsifier that allows water to replace solvent present in SB, self-drying alkyd coating
formulations. The formulations of the present invention achieve excellent performance.
The paint performance and dry film performance of the coating formulations can meet
requirements of standards in the industry. For example, an alkyd topcoat or a primer coat of
the present invention is useful for providing several performance attributes or properties to
the final cured coating. In addition, the alkyd coating formulation of the present invention
has a lower viscosity than known coating formulations; and therefore, the coating
formulation of the present invention can be easily applied to a substrate.

One embodiment of the present invention is directed to a coating composition

or formulation including (a) at least one hydrophilic surfactant; (b) at least one hydrophobic
surfactant; (c) water; (d) at least one solvent; and (e) at least one solvent borne air drying
alkyd coating resin.

Another optional embodiment of the present invention includes adding at

least one amino-methyl propanol co-dispersant such as AMP or AMP95 into the above
coating formulation.

Yet another embodiment of the present invention is directed to an alkyd

protective top coat or an alkyd primer coat utilizing the above coating formulations; wherein
the coating formulation has a low VOC and a low viscosity. The VOC level of the coating
formulation of the present invention can be for example a VOC level of less than about
10% VOC based on the total formulation of the SB alkyd coating. The coating formulation
of the present invention can have a viscosity of, for example, less than about 600 mPa-s.

Other embodiments of the present invention include a process for making the
above coating formulations.
DETAILED DESCRIPTION OF THE INVENTION

In the following detailed description, specific embodiments of the present

invention are described. However, the present invention is not limited to such embodiments.

One broad scope of the present invention is directed to a coating formulation

including (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant;
(c) water; (d) at least one solvent; and (e) at least one solvent borne air drying alkyd coating
resin. In another embodiment, the coating formulation, optionally, may include (f at least
one amino-methyl propanol co-dispersant.

"HLB" with reference to a surfactant herein stands for the hydrophilic-

lipophilic balance of a surfactant (which is a measure of the degree to which a surfactant is
hydrophilic or lipophilic, as determined by calculating values for different regions of a
molecule, as described in Griffin W.C., "Classification of Surface-Active Agents by 'HLB,'"
Journal of the Society of Cosmetic Chemists 1 (1949), page 3 1 1; and Griffin W.C.,
"Calculation of HLB Values of Non-Ionic Surfactants," Journal of the Society of Cosmetic
Chemists 5 (1954), page 259. Another method which may be useful for determining HLB
may be found in Davies J.T., "A Quantitative Kinetic Theory of Emulsion Type, I. Physical
Chemistry of the Emulsifying Agent," Gas/Liquid and Liquid/Liquid Interface, Proceedings
of the International Congress of Surface Activity (1957), pages 426-438.

A "hydrophilic surfactant" herein means a surfactant with a HLB of equal to

or greater than about 10.

A "hydrophobic surfactant" herein means a surfactant with a HLB of less

than about 10.

The at least one hydrophilic surfactant used in the present invention may be
selected from (i) nonionic hydrophilic surfactants, (ii) anionic hydrophilic surfactants, and
(iii) mixtures thereof.

The nonionic hydrophilic surfactant used in the present invention may

include for example ethylene oxide/propylene oxide (EO/PO) copolymers, ethoxylates; and
mixtures thereof.

Examples of the at least one nonionic hydrophilic surfactant includes alkyl

and alkylarylpolydiol ethers such as ethoxylation products of lauryl, oleyl, and stearyl
alcohols; alkylphenol glycol ethers such as ethoxylation products of octylphenol or
nonylphenol and the like; and mixtures thereof. Preferably, the at least one nonionic
hydrophilic surfactant used in the present invention may include, for example, alkyl EO/PO
copolymers such as Tergitol XH, Tergitol XD, and Tergitol L series; and nonylphenol
ethoxylates (NPE) such as Tergitol NP series surfactants commercially available from The
Dow Chemical Company.

The anionic hydrophilic surfactant used in the present invention may include
for example commercially available products such as Dowfax™ 1A1, Dowfax 3B2, Dowfax
CIOL, Dowfax 30599 , TRITON™ XQS-20 , TRITON H-55 (trademarks of The Dow Chemical
Company), and the like; and mixtures thereof. In one embodiment, the at least one anionic
hydrophilic surfactant includes for example Dowfax 1A1.

The concentration of nonionic or anionic hydrophilic surfactant present in the

coating formulation of the present invention is generally between 0.01 weight percent (wt%)
to about 1.5 wt%, preferably between about 0.1 wt% to about 1.2 wt%, and more preferably
between about 0.4 wt% to about 0.8 wt%, based on the weight of the total formulation. If
the usage is below the recommended concentration, water may be introduced into the
coating formulation; and the formulation may not be stable, that is, the water may phase
separate out of the formulation after a period of time. If the usage level is above the
recommended concentration, the resulting cured coating's water resistance will be impacted
detrimentally.

In another embodiment of the present invention, a mixture of any of the

nonionic and anionic hydrophilic surfactants described above may be used in the
formulation of the present invention. When a mixture of hydrophilic surfactants is used, the
ratio of nonionic hydrophilic surfactant to anionic hydrophilic surfactant may be generally
from about 10 to about 0.5, preferably from about 8 to about 1, and more preferably from
about 8 to about 5, based on the weight of the total formulation.

The at least one hydrophobic surfactant used in the present invention may be
selected from (i) nonionic hydrophobic surfactants, (ii) anionic hydrophobic surfactants, and
(iii) mixtures thereof.
 The nonionic hydrophobic surfactant used in the present invention may
include, for example, alkylphenol ethoxylates or EO/PO copolymers or ethoxylates, and
mixtures thereof.

Preferably, the nonionic hydrophobic surfactant used in the present invention

includes, for example, octylphenol ethoxylates such as TRITON X-15, NP-4,
NP-6, TMN-3 (trademarks of The Dow Chemical Company), other oil soluble surfactants,
and mixtures thereof.

The anionic hydrophobic surfactant used in the present invention may include
for example commercially available products such as TRITON GR-7M; and the like; and
mixtures thereof. In one embodiment, the at least one anionic hydrophobic surfactant
includes for example TRITON GR-7M.

The concentration of nonionic or anionic hydrophobic surfactant present in

the coating formulation of the present invention is generally between 0.001 wt% to about 0.8
wt%, preferably between about 0.01 wt% to about 0.6 wt%, and more preferably between
about 0. 1 wt to about 0.4 wt%, based on the weight of the total formulation. If the
concentration of the hydrophobic surfactant is above the recommended concentration, the
coating formulation's viscosity may significantly increase.

In another embodiment of the present invention, a mixture of any of the

nonionic and anionic hydrophobic surfactants described above may be used in the
formulation of the present invention. When a mixture of hydrophobic surfactants is used,
the ratio of nonionic hydrophobic surfactant to anionic hydrophobic surfactant may be
generally from about 10 to about 1, preferably from about 8 to about 1, and more preferably
from about 5 to about 1, based on the weight of the total formulation.

The water component used in the coating formulation of the present

invention may be preferably deionized water, tap water or a mixture thereof. The
concentration of the water present in the coating formulation of the present invention
is generally between 1 wt% to about 30 wt%. In another embodiment the water
concentration may be from about 3 wt% to about 20 wt%, preferably between about 5 wt%
to about 20 wt%, and more preferably between about 5 wt% to about 15 wt%, based on the
weight of the total composition. If the water is added above about 30 wt%, the paint
viscosity may become too high (e.g. greater than about 1000 mPa-s) to apply with air spray
techniques; the system may tend to be unstable; and the resulting coating's performance
may become poor such as for example low gloss for alkyd finishes. In the coating
formulation of the present invention, water may be added into the coating formulation for
example at the last stage of the paint making process.

The solvent useful for the coating formulation of the present invention may
be any conventional solvent known in the art. Examples of suitable organic solvents include,
but are not limited to, xylene, benzene, toluene, white spirits, and mixtures thereof. For
example, the solvent may include xylene, white spirit (Exxsol D40), 200# solvent and the
like; and mixtures thereof. The concentration of solvent present in the coating formulation
of the present invention is generally between 10 wt% to about 40 wt%, based on the weight
of the total formulation.

The coating formulation of the present invention also includes at least one
alkyd resin. The alkyd resin useful for the coating formulation of the present invention may
be any unsaturated alkyd resin well known in the art. For example, the alkyd resin may
include air drying natural oil modified alkyd resin. Preferably, the alky resin used in the
present invention includes air drying soybean oil alkyd resins, air drying tall oil alkyd resins
and any other unsaturated oil modified alkyd resin which is air drying.

Other examples of the alkyd resin useful in the present invention include for
example commercial alkyd resin such as Alkyd Resin 389-37; or Alkyd Resin 389-5, 389-6,
389-7, 389-8, or 389-9; or any other air drying alkyd for protective coating applications. A
preferred example of a commercially available alkyd resin may be for example, the alkyd
resin commercially available under the trade name Alkyd Resin 389-37 or Alkyd Resin
389-9 (50-60% non-volatile mass—soybean oil alkyd resin with 60% oil length,
40% xylene, p= . 3 g/ cm 3) commercially available from Shanghai Xinhua Resin
Manufacturer. Such soybean oil alkyd resin types may be used for protective coatings.

The concentration of the alkyd resin present in the coating formulation of the
present invention is generally between about 30 wt% to about 80 wt%, which is dependent
on the formulation designs of the coating. If the alkyd resin usage is above or below the
recommended concentration range, the final cured coating's performance such as the
coating's anti-corrosive properties may be detrimentally impacted.
 The alkyd resins useable in the present invention may include any of the
conventional alkyds typically used in air drying alkyd coatings formulations. Long to
medium oils length are preferred such as for example above 50% oil weight percent by
weight in the alkyd resin. Alkyd resins may be, for example, thermosetting reaction
products of a dihydric or polyhydric alcohol (e.g., ethylene glycol or glycerol) and a
mono/polybasic acid (e. g., phthalic anhydride) in the presence of a drying oil (e.g., linseed,
soybean), wherein the drying oil acts as a modifier. Alkyd resins may be produced for
example by direct fusion of glycerol, phthalic anhydride and drying oil at from about
210° C to about 232° C. Solvents may be added to reaction mixture to produce alkyd resins
and then further added to adjust the solids content of the mixture.

The coating formulation of the present invention may also include one or
more optional components including for example at least one amino-methyl propanol
co-dispersant. The amino-methyl propanol co-dispersant may include for example AMP or
AMP-95. In one embodiment of the present invention, AMP95 may be added into the SB
coating at the last stage of the paint making process. The concentration of AMP95 of the
present invention is generally between 0 wt% to about 0.5 wt%, preferably between
about 0.01 wt% to about 0.3 wt%, and more preferably between about 0.05 wt% to about
0.15 wt%, based on the weight of the total formulation.

The coating formulation of the present invention may also include, as an

optional component, at least one drying catalyst. The drying catalyst or drying agent useful
for the coating formulation of the present invention may be any conventional drying catalyst
known in the art. Examples of suitable drying catalyst or drying agent include, but are not
limited to, various salts of cobalt, zirconium, calcium, zinc, and manganese; and mixtures
thereof. Preferably, the drying catalyst may include calcium octoate/ naphthenate, cobalt
octoate/ naphthenate, zirconium octoate/ naphthenate and other metal complex catalysts; and
mixtures thereof. Preferred drying catalyst or drying agent are the metal salts of
carboxylates having various chain lengths. These drying catalysts or drying agents are well
known to those skilled in the art, and are readily available in the marketplace.

The concentration of drying catalyst present in the coating formulation of the

present invention is generally between 0.01 wt% to about 1 wt%, based on the weight of the
total formulation. The usage may be based on a catalyst which has about 10 % metal
content. The drying catalyst or drying agent used as the drier package in the ambient cure
formulation of the present invention may include any drier known in the art, so long as the
drier package provides from about 0.15% to about 10% calcium content and at least about
0.01 wt% cobalt content, based on the binder solids content.

The coating formulation of the present invention may also include, as an

optional component, at least one anti-skinning agent. The anti-skinning agent useful for the
coating formulation of the present invention may be any conventional anti-skinning agent
known in the art. The term "anti-skinning agent" herein means the additive can prevent the
alkyd coating from skinning on the surface when the coating is stored in a storage container.
For example, the anti-skinning agent may include methyl ethyl ketoxime (MEKO), methyl
iso-butyl ketome (MIBKO); and the like; and mixtures thereof.

The concentration of anti-skinning agent present in the coating formulation of

the present invention is generally between about 0.1 wt% to about 1 wt%, preferably
between about 0.2 wt% to about 0.6 wt%, based on the weight of the total formulation. If
the usage is below the recommended concentration, the coating may more readily form dry
skin on a paint surface.

The coating formulation of the present invention may also include, as an

optional component, at least one thickener agent. The thickener agent useful for the
coating formulation of the present invention may be any conventional thickener agent
known in the art to improve a coating's rheological properties. For example, thickeners for
alkyd-compatible surfactant include bentonite clays, organoclays, synthetic silicas, castor oil
derivatives, modified acrylic copolymers, polyethylene glycol, polymerized oil derivatives,
organic esters, complex polyolefins; and mixtures thereof.

The concentration of thickener agent present in the coating formulation of the

present invention is generally between about 0.1 wt% to about 1 wt%, preferably between
about 0.2 wt% to about 0.6 wt%, based on the weight of the total formulation. If the
concentration of the thickener is below about 0.1 wt%, the resulting wet coating film may
possibly sag.

The above formulation may be advantageously used to prepare, for example,

one embodiment of a clear coating formulation which includes components (a)-(e) and/or
(f) at least one amino-methyl propanol co-dispersant, as described above; and one or more
of the following optional components: (g) at least one drying catalyst, (h) at least one anti-
skinning agent, and (i) at least one thickener.

In another embodiment, if a pigmented coating formulation for a primer

coating is desired, the pigmented coating formulation may comprise, in addition to
components (a)-(e), and/or (f) at least one amino-methyl propanol co-dispersant, as
described above; and (j) at least one pigment. In addition the pigmented coating formulation
for primer coating may include one or more of the following optional components: (g) at
least one drying catalyst, (h) at least one anti-skinning agent, (i) at least one thickener, and
(k) at least one filler.

The at least one pigment useful, as an optional component, for the coating
formulation of the present invention may be any conventional pigment known in the art.
Suitable well known pigments can comprise for example, titanium dioxide, carbon black,
graphite, ceramic black, antimony sulfide, black iron oxide, aluminum pastes, yellow iron
oxide, red iron oxide, iron blue, phthalo blue, nickel titanate, dianisidine orange,
dinitroaniline orange, imidazole orange, quinacridone red, violet and magenta, toluidine red,
molybdate orange, and the like; and mixtures thereof.

The concentration of the pigments present in the coating formulation of the

present invention may be generally between about 1 wt% to about 40 wt%, and preferably
between about 10 wt% to about 30 wt%, based on the weight of the total formulation. The
pigment usage may be dependent on the formulations' color and PVC (pigment volume
concentration) design. Too much or too less of the above concentrations may not meet the
coating's performance specifications such as color, hardness and other coating properties.

The at least one filler of the present invention, as an optional component and
especially useful in primer coating formulations, may be any conventional filler known in
the art. For example, the fillers useful in the coating formulation of present invention may
include clays, barium sulphate, silica, talc, quartz, or mica; flame retardant fillers such as
aluminum hydroxide or magnesium hydroxide; boehmite; or zinc phosphate; and the like;
and mixtures thereof.

The concentration of the filler present in the coating formulation of the

present invention may be generally between 0 wt% to about 50 wt%, and preferably
between about 0.1 wt% to about 40 wt%, based on the weight of the total formulation.
The filler usage may be dependent on the formulations' PVC design. Too much or too little
filler may result in the coating not meeting the coating's performance specification such as
color and anti-corrosive properties.

The average particle size of the inorganic filler is generally below about
100 micron, preferably below about 60 micron, and more preferably below about 50 micron.
If the filler has too big particle size, the coating film will have poor appearance and poor
protective performances to the substrate.

The coating formulation of the present invention may also include, as an

optional component, at least one dispersant. The dispersant useful in the coating
formulation of present invention may include any conventional dispersant known in the art.
For example, the dispersant may include ANTI-TERRA-U (p= 0.94 g/ cm 3) a dispersant
commercially available from BYK. Other examples of the dispersant may be including the
anionic and nonionic surfactants, soya lecithin, alkyl ammonium salts of fatty acids, amine
salts of alkyl aryl sulfonates, unsaturated organic acids, sulfonated castor oil, mixtures of
high boiling point aromatic and ester solvents, sodium salts of aryl sulfonic acid, and the
like; and mixtures thereof.

The concentration of the dispersant present in the coating formulation of the

present invention is generally between 0 wt% to about 1 wt%, preferably between about
0.1 wt% to about 0.8 wt%, and more preferably between about 0.1 wt% to about
0.5 wt%, based on the weight of the total formulation. In some embodiments, the
combination of surfactants of the present invention may be sufficient to act as a dispersant.
The commonly known dispersant agents such as ANTI-TERRA-U or soya lecithin for
solvent borne alkyd coatings may not be required; and therefore, the cost for their use may
be saved while achieving a very homogeneous dispersion of the pigments and fillers.

The coating formulation according to the present invention may further

include, as an optional component, one or more additives chosen from rheology modifiers,
other pigments, other fillers, plasticizers, antioxidants, thixatropes, extenders, other solvents,
diluents, other drying agents, other dispersants, other surfactants, fungicides, mildewcides,
preservatives, UV absorbers, anti-marring agents, flow and leveling agents, fragrances,
defoaming agents, chelating agents, flattening agents, anti-rusting agents, and mixtures
thereof. This list of additional optional components useful in the coating formulation of
present invention is intended to be exemplary and not limiting.

The concentration of the additional additives present in the formulation of the

present invention is generally between 0 wt% to about 1 wt%, preferably between about 0.1
wt% to about 0.5 wt%, more preferably between about 0.1 wt% to about 0.3 wt , based on
the weight of the total formulation and the formulation design. If the usage is less than the
above ranges, the coating's sag resistance may be poor or unacceptable. Too high of a
concentration may be uneconomical and may increase the formulation cost.

In some embodiments, the coating formulation of the present invention may

be useful, for example, for clear coats and pigmented protective coatings. For example, one
embodiment of the a clear coating formulation may include (a) at least one hydrophilic
surfactant; (b) at least one hydrophobic surfactant; (c) water; (d) at least one solvent; and
(e) at least one solvent borne air drying alkyd coating resin; and (f optionally, at least one
amino-methyl propanol co-dispersant; (g) at least one drying catalyst; and (h) at least one
anti-skinning agent.

In another embodiment, a pigmented coating formulation may include

(a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant; (c) water;
(d) at least one solvent; and (e) at least one solvent borne air drying alkyd coating resin; and
(f optionally, at least one amino-methyl propanol co-dispersant; (g) at least one drying
catalyst; (h) at least one anti-skinning agent; (i) at least one thickener additive; ( ) at least
one pigment; and/or (k) at least one filler.

A dispersant, component (1), may optionally be added to the coating

formulation of the present invention. Suitable dispersants, may also include other
surfactants other than components (a) and (b); and may comprise any of the readily
available dispersants and/or surfactants known in the coatings industry, including for
example the aforementioned anionic and nonionic surfactants, soya lecithin, alkyl
ammonium salts of fatty acids, amine salts of alkyl aryl sulfonates, unsaturated organic acids,
sulfonated castor oil, mixtures of high boiling point aromatic and ester solvents, sodium
salts of aryl sulfonic acid, and the like; and mixtures thereof.

The objectives of the present invention includes developing an air-drying

alkyd protective paint formulation with lower VOC, lower cost and unchanged or improved
performance for topcoat or primer coatings in protective coatings including for example
marine, maintenance, or wood coatings. The alkyd formulations of the present invention
comprise a multi-functional additive, which is the combination of surfactants of the present
invention, as an emulsifier enabling the use of, for example, approximately 4 % to about
16 % water (based on total formulation weight) replacing same amount of solvent by weight
in the solvent borne alkyd formulations, which significantly reduces the VOC level while
reducing cost and maintaining physical properties of the coating. The new air-drying alkyd
coat affords lower VOC and workable viscosity; and meets all the requirements of the
industry standards for a solvent borne alkyd coating.

For example, in one specific embodiment of the present invention

formulation, 10 % water is added and 10 % organic solvent (e.g. xylene or white spirit) is
replaced, and the dispersants can be saved under most conditions. Currently, the cost
reduction may be about 5 %. Also, the formulation viscosity is low enough to be applied by
conventional methods. The alkyd paint may be used as coatings that are used to protect
metal or wood and also give decorative functions in and around items associated with
industrial production and transport, especially manufacturing plants, as corrosion protective
coating for general applications such as metal coating for infrastructure components, beams,
and the like, and as marine coating on above-water sections of a watercraft.

In the present invention formulations, the unique surfactant product mixture

(i.e., the at least one hydrophilic surfactant mixed with the at least one hydrophobic
surfactant) is used in a concentration of, for example, from about 0. 1 % to about 1 % based
on the total formulation. This usage can thus replace from about 4 % to about 16 % solvent
in the traditional solvent borne alkyd coating with the same amount by water. Further more,
the surfactant mixture also acts as a dispersant to improve the dispersion of the pigments,
which in turn, decreases or eliminates the use of a conventional dispersant agent used in the
traditional SB alkyd coating or in some cases the conventional dispersant agent may be
removed entirely.

The present invention advantageously reduces the VOC level of traditional

SB alkyd coatings, achieves significant cost reduction, and at same time, maintains the
same level or improves the level of coating performance when compared with traditional
SB alkyd coatings of the prior art.
 One embodiment of the coating formulation of the present invention may
include (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant;
(c) water; (d) at least one solvent such as white spirits or xylene; and (e) at least one
solvent borne air drying alkyd resin; and (f) optionally, at least one amino-methyl propanol
co-dispersant; (g) optionally, at least one drying catalyst such as metal salts like cobalt
compound, calcium compound, zirconium compound and the like; (h) optionally, at least
one anti-skimiing agent such as methyl ethyl ketoxime; (i) optionally, at least one thickener
additive; (j) optionally, at least one pigment such as titanium dioxide (Ti02) or iron oxide
red; and/or (k) optionally, at least one filler. Optionally, at least one dispersant such as
ANTI-TERRA and optionally, AMP can be added to the above mixture.

The use of the surfactants of the present invention provides several benefits
such as (1) the surfactants may replace or at least decrease the amount of the dispersant
needed in the coating formulation; (2) the use of the surfactants may allow the use of an
amount of water such that the water may replace the amount of solvent needed in the coating
formulation, such as for example, up to about 10% solvent of the total coating formulation
weight can be replaced with the same amount of water; and (3) utilizing the surfactants can
reduce the VOC of the SB self-drying alkyd coating which, in turn, may provide a
significant cost saving.

The coating formulations of the present invention can be prepared in a similar

manner with traditional solvent borne coating. In general, for clear coating , the mixing
order of the surfactants employed in the coating formulation of the present invention can be
added and dispersed uniformly at any stage before water is introduced; the water is
preferably added after all the other coating components are added and dispersed uniformly.

For pigmented alkyd coating the mixing order of the surfactants employed in
the coating formulation of the present invention can be before the grinding stage or after the
grinding stage to make sure the pigment is dispersed uniformly in the paint formulation; the
water is preferably added last after any other raw materials are added and dispersed
uniformly. If an optional dispersant additive is not used in the formulation along with the
combination of surfactants, the surfactants may be first added to the formulation and
dispersed uniformly throughout the formulation before any pigments and fillers are added to
the formulation. When the optional dispersant is used in the formulation, the surfactant may
be added at a stage before water is added to the formulation. Preferably, water is added at a
final stage after all of the previous components are dispersed uniformly throughout the
formulation. The solvent borne alkyd coating is admixed employing mixing procedures and
conditions well known in the paint mixing art.

The equipment and conditions for preparing the coating formulation may be
the same as what is used in preparing traditional solvent borne coatings, such as for
example, the temperature control is preferably under 50 °C.

The final coating formulation or formulation displays superior properties

including for example a low VOC concentration, and a low viscosity. The VOC
concentration generally is from about 20 wt% to about 50 wt%; and preferably from about
2.0 wt% to about 40 wt%. The solids concentration of the formulation is generally from
about 40% to about 70% by weight. The viscosity of the formulation is generally from
about 200 mP-s to about 650 mP-s; and preferably from about 20 mP-s to about 50 mP-s.

The finished coating using the coating formulation of the present invention,
may keep excellent gloss (greater than 90 @60° as tested by method GB/T9754; China
Standard) and excellent gloss retention (as test method HG 2576-94; China Standard),
properties which are the same as a traditional solvent borne alkyd coating.

The coating formulation of the present invention may be applied to a variety

of substrates such as steel, aluminum, wood and the like. Once on the substrate, the coating
formulation can then be cured at ambient condition to form an attractive, hard and adherent
film. For example, the alkyd coating formulation of the present invention may be coated
onto a substrate and cured at room temperature (ambient cure) by methods known in the art
(e.g. by spray-applying 3 to 4 mils of wet coating onto a metal panel and drying at ambient
condition). The substrate may be any common substrate, such as, for example metals such
as, for example, aluminum or steel; glass; wood; concrete; primed (painted) substrates; and
the like.

The coating formulation of the present invention may be applied by any well
known means of application in the industry including for example, reverse roll coating,
spraying, brushing, rolling, or dipping and the like; more specifically coating methods used
in the application of organic solvent based coating formulations, such as spray coating,
electrostatic coating, immersion coating, curtain flow coating, roll coating, shower coating;
and the like.
 Curing schedules can vary depending upon the components present in the
alkyd resin coating formulation, the presence or absence of catalysts, and the environment
conditions. Typical curing schedules are same as traditional solvent borne alkyd coatings
include from about 10 hours to about 60 hours at from about 5 °C to about 35 °C.

The coating formulations or compositions of the present invention are very

suitable for coating processes for various applications including for example in for
protective coatings such as for general metal, tanks, bridges, and infrastructure and factory
coatings, and any other substrates on which air drying alkyd coating can be used. Preferably,
the coating of the present invention may be used as a protective coating for metal and wood
substrates for protection and for decoration.

The coating of the present invention has less VOC and lower cost, while the
coating displays same or superior properties than previously known coatings such as better
storage performance and better pigment dispersing effect. For example, when the coating of
the present invention is compared to a standard coating made from AMP95, the coating of
the present invention has lower or similar viscosity; and most importantly, also a better
storage stability. "Storage stability" with reference to a coating herein means that the
coating's phase stability is suitable to provide a useable formulation to form a coating with
functional properties. Storage stability may be measured according to the following test
method: Prepare a coating sample of about 100 g, in clear plastic bottle and then subject the
sample @25 °C and 60% R under storage conditions of 50 °C for 30 days. After that time
period, check the coating sample for (a) water phase separation by visually checking the
sample; (b) any change in wet coating's fineness (or grindness) as tested by GB 1724-88
(China Standard); and (c) the coating's film performances like appearance/gloss as tested
according to HG 2576-94 (China Standard).

The coating samples of the present invention, after the above storage test,
show no water phase separation by visual observation, and no grindness increase; and the
coating samples have the same film properties as before the storage test. On the other hand,
standard coating samples for example those made from AMP-95, after only one week, the
samples @25 °C &60%RH and 50 °C typically have water phase separation on the sample
bottom; the grindness of wet paint is poor (for example, from originally
35 µη increased to about 60 µ ι) after 50 °C for 30 days; and the coating film can have
"pig skin" defects for the poor grindness. "Grindness" herein means the largest average
particle size of dispersed pigments and filler in the coating. Generally, a smaller grindness
is desired for better coating performances.

Table A below shows a comparison of typical values for VOC of a coating of

the present invention versus a coating of the prior art.

Table A

The coatings' properties such as fineness, viscosity, storage stability, film

appearance, gloss, color, adhesion, flexibility, impact resistance and water resistance are
measured. In addition, important properties for the coating, for example, include viscosity,
storage stability, gloss, adhesion, and water resistance.

Generally, the viscosity of the coating formulation of the present invention

may be below about 1000 mP-s at 25 °C and preferably less than about 600 mP-s at 25 °C.

The resulting coating of the present invention generally exhibits the

following properties, according to HG 2576-94 alkyd enamel coating standards:

(1) after 30 days of storage at 50 °C, no water separation/no solid settlement;

(2) the gloss is less than about 90 at 60 °C;

(3) the adhesion is excellent; and

(4) the water resistance is as follows: for acceptable grade 2 hour water
immersion and a coating's gloss retention of greater that 80 %; and for excellent grade
18 hours water immersion and a coating's gloss retention of greater that 80 %.

Generally, a coating's anti-corrosive performance is directly related to the

coating's water resistance performance. The solvent borne alkyd coating of the present
invention shows good anti-corrosive performance because its water resistance is good.

The final coating of the present invention displays superior properties. That
is, the cured coating formulation of the present invention advantageously exhibits various
properties that make the coating useful for coating substrates. Generally, the coating should
meet the minimum standards in the industry such as for example: wet paint properties such
as condition in a paint can, viscosity, application performance and dry film properties. For
example, minimum standards may be those established by the Chinese government as
described in publication Chinese Chemical Industry Standards for Alkvd Finish Coatings
HG 2576-94. These minimum standards for certain properties are known and
conventionally acknowledged by those skilled in the art. These standards for the properties
are described in the following Table B .

Table B - Chinese Chemical Industry Standards for Alkvd Finish Coatings HG 2576-94
EXAMPLES

The following examples and comparative examples further illustrate the

present invention in detail but are not to be construed to limit the scope thereof.

Various terms, designations and raw materials used in the following

examples are explained herein as follows: "AMP" stands for an additive commercial
product of The Dow Chemical Company; Exxsol D 40 is a solvent commercially
available from Shell Company; ANTI-TERRA-U is a dispersant commercially available
from BYK Company; 389-37 or 389-9 are two soybean oil alkyd resins with 60 % oil length,
commercially available from Xinhua Resin Manufacturing Co. in China; a multifunctional
additive in the present examples is a surfactant mixture from The Dow Chemical Company;
and in the tables below, "VOC" stands for volatile organic compounds; "MS" stands for
mass solid content; "PVC" stands for pigment volume concentration; and "VS" stands for
volume solid content.

The following standard analytical equipments, methods and test procedures

are used in the Examples:

Phase separation is determined by visual observation of water phase

separation. No water separation is "good", while any water separation is "bad".

Viscosity is determined by ASTM D4287 method and is generally less than

about 600 mP-s.

Wet paint fineness (the specification to check the paint particles' dispersing
effect in the resin) is tested according to test method GB 6753.1-86.

Sheets of metal for testing the coatings in the examples were coated
according to method GB 1727.

The properties of the resulting coated sheets of metal were tested as follows:
the hard dry property was measured according to test method GB 9273; the flexibility
property was measured according to test method GB/T 6742-1986; the adhesion property
was measured according to test method GB 9286; the pencil hardness property was
measured according to test method GB6739; the impact resistance property was measured
according to test method GB/T 1732-1993; the gloss property was measured according to
GB/T9754; the water resistance property was measured according to GB/T 9274; and the
storage property was measured according to GB/T6753.

The dispersing machine used in the following examples for dispersing the
components of the formulation was a Dispermat CN F2 manufactured by
VMA-GETZMANN GmbH.

Example 1 - Preparation of a Clear Coat

In this Example 1, the general procedure used for making a paint formulation
in accordance with the present invention is described with reference to Table I as follows:

Table I - Formulation of a Clear Alkyd Coat

The general procedure used in this Example 1 is as follows:

A. Add components of steps 1, 2, 3, 4 and 5 of Table I in turn into a steel

tank and then disperse the resulting mixture of components uniformly under 800-1200
revolutions per minute (rpm).

B. Add component of step 6 of Table I into the tank and then disperse
the resulting mixture of components uniformly under 800-1200 rpm.

C. Add components of steps 7, 8, 9, 10 and 11 of Table I in turn into the

tank under a slow speed of about 500 rpm and then disperse the resulting mixture of
components under 1800-2000 rpm uniformly for about 15 minutes.
 D. Add component of step 1 of Table I into the tank and then disperse
the resulting mixture of components under 1800~2000 rpm uniformly for about 15 minutes
to form a paint formulation.

After the above procedure, the resulting paint formulation is placed in a

sealed can sealed under room temperature (about 25 °C) for one day. After one day, the
resulting paint formulation is divided into two parts - one part is stored at room temperature
for 30 days; and the other part is heated at 50 °C for 30 days. Then the parts are checked to
determine if any water phase separation occurs. The results of this Example 1 are described
in Table III below.

Comparative Example A - Preparation of a Clear Coat

In this Comparative Example A, the general procedure used for making a
paint formulation in accordance with the prior art is described with reference to Table II as
follows:
Table II - Formulation of a Clear Alkyd Coat

The general procedure used in this Comparative Example A is as follows:

A. Add components of steps 1, 2, 3, 4 and 5 of Table II in turn into

a steel tank and then disperse the resulting mixture of components uniformly under
800-1200 rpm.
 B. Add component of step 6 of Table II into the tank and then disperse
the resulting mixture of components uniformly under 800-1200 rpm.

C. Add components of steps 7, 8, 9, 10, and 11 of Table II in turn into

the tank under a slow speed of about 500 rpm and then disperse the resulting mixture of
components under 1800-2000 rpm uniformly for about 15 minutes.

D. Add component of step 1 of Table II into the tank and then disperse
the resulting mixture of components under 1800-2000 rpm uniformly for about 15 minutes
to form a paint formulation.

After the above procedure, the resulting paint formulation is placed in a

sealed can sealed under room temperature for one day. After one day, the resulting paint
formulation is divided into two parts - one part is stored at room temperature for 30 days;
and the other part is heated at 50 °C for 30 days. Then the parts are checked to determine if
any water phase separation occurs. The results of this Comparative Example A are
described in Table III below.

Table III - Stability Results

Example 2 - Preparation of a Topcoat

In this Example 2, the general procedure used for making a paint formulation
in accordance with the present invention is described with reference to Table IV as follows:
 Table IV - Formulation of a White Alkyd Topcoat

Notes for Table IV: MS = 60 %; PVC = 20 %; VOC = 353g/L

The general procedure used in this Example 2 is as follows:

A. Add components of steps 1, 2, 3, and 4 of Table IV in turn into a steel

tank and then disperse the resulting mixture of components uniformly under 800-1200 rpm.

B. Add component of step 5 of Table IV into the tank and then disperse
the resulting mixture of components uniformly under 800-1200 rpm.

C. Add component of step 6 of Table IV into the tank and then disperse
the resulting mixture of components under 2000 rpm for about 20 minutes; control the
temperature of the mixture of components at under 50°C; and when the grindness of the
resulting mixture of components is less than 40 µ η , go to the next step.

D. Add components of steps 7, 8, 9, 10, 11, 12, and 13 of Table IV in

turn into the tank under a slow speed of about 500 rpm and then disperse the resulting
mixture of components under 1800-2000 rpm uniformly for about 15 minutes.

E. Add component of step 1 of Table IV into the tank and then disperse
the resulting mixture of components under 1800-2000 rpm uniformly for about 15 minutes
to form a paint formulation.
 After the above procedure, the resulting paint formulation is placed in a
sealed can sealed under room temperature for one day. After one day, the wet paint
performances were tested and coating films were applied to a substrate. The coating films
were subjected to 25 °C/60 relative humidity (RH) conditions for 7 days and then the
resulting film properties were tested. The results of this Example 2 are described in Tables
IX-XIII below.

Comparative Example B

In this Comparative Example B, the general procedure used for making

a paint formulation in accordance with the prior art may be described with reference to
Table V as follows:
Table V - Formulation of a White Alkyd Topcoat

gL

The general procedure used in this Comparative Example B is as follows:

A. Add components of steps 1, 2, 3, and 4 of Table V in turn into a steel

tank and then disperse the resulting mixture of components uniformly under 800~1200 rpm.

B. Add component of step 5 of Table V into the tank and then disperse
the resulting mixture of components uniformly under 800-1200 rpm.
 C. Add component of step 6 of Table V into the tank and then disperse
the resulting mixture of components under 2000 rpm for about 20 minutes, control the
temperature of the mixture of components at under 50 °C, and when the grindness of the
mixture of components is less than 40 µηι , go to the next step.

D. Add components of steps 7, 8, 9, 10, 11, 12 and 13 of Table V in turn

into the tank under a slow speed of about 500 rpm and then disperse the resulting mixture of
components under 1800~2000 rpm uniformly for about 15 minutes.

E. Add component of step 14 of Table V into the tank and then disperse
the resulting mixture of components under 1800-2000 rpm uniformly for about 15 minutes
to form a paint formulation.

After the above procedure, the resulting paint formulation is placed in a

sealed can sealed under room temperature one day. After one day, the wet paint
performances are tested and coating films are applied to a substrate. The coating films were
subjected to 25 °C/60 RH conditions for 7 days and then the film properties were tested.
The results of this Comparative Example B are described in Tables IX-XIII below.

Comparative Example C

In this Comparative Example C, the general procedure used for making a

paint formulation in accordance with the prior art is described with reference to Table VI as
follows:
Table VI - Formulation of a White Alkyd Topcoat

Notes for Table VI: Traditional SB alkyd coating; MS = 60 %; PVC = 20 %; and VOC = 452g/L
 The general procedure used in this Comparative Example C is as follows:

A. Add components of steps 1, 2, 3, and 4 of Table VI in turn into a steel

tank and disperse the resulting mixture of components uniformly under 800~1200 rpm.

B. Add component of step 5 of Table VI into the tank and then disperse
the resulting mixture of components uniformly under 800-1200 rpm.

C. Add component of step 6 of Table VI into the tank and then disperse
under 2000 rpm about 20 minutes, control the temperature of the resulting mixture of
components at under 50 °C; and when the grindness of the resulting mixture of components
is less than 40 µη , go to the next step.

D. Add components of steps 7, 8, 9, 10, 1 , 12 and 13 of Table VI in turn

into the tank under a slow speed of about 500 rpm and then disperse the resulting mixture of
components under 1800~2000 rpm uniformly for about 15 minutes.

E. Add component of step 14 of Table VI into the tank and then disperse
the resulting mixture of components under 1800~2000 rpm uniformly for about 15 minutes.

After the above procedure, the resulting paint formulation is placed in a

sealed can sealed under room temperature one day. After one day, the wet paint
performances are tested and coating films are applied to a substrate. The coating films were
subjected to 25 °C/60 RH conditions for 7 days and then the film properties were tested.
The results of this Comparative Example C are described in Tables IX-XIII below.

Example 3 - Preparation of a Topcoat

In this Example 3, the general procedure used for making a paint formulation
in accordance with the present invention is described with reference to Table VII as follows:
 Table VII - Formulation of a White Alkyd Topcoat

Notes for Table VII: AMP is not used; MS = 60 %; PVC = 20%; and VOC = 353g/L.

The general procedure used in this Example 3 is as follows:

A. Add components of steps 1, 2, 3, 4, and 5 of Table VII in turn into

a steel tank and then disperse the resulting mixture of components uniformly under
800-1200 rpm.

B. Add component of step 6 of Table VII into the tank and then disperse
the resulting mixture of components uniformly under 800-1200 rpm.

C. Add component of step 7 of Table VII into the tank and then disperse
the resulting mixture of components under 2000 rpm about 20 minutes, control the
temperature of the resulting mixture of components at under 50 °C, and when the paint
grindness is less than 40 µ η , turn to next step.

D. Add components of steps 8, 9, 10, 11, and 12 of Table VII in turn into
the tank under a slow speed of about 500 rpm; and then disperse the resulting mixture of
components under 1800-2000 rpm uniformly for about 5 minutes.

E. Add component of step 13 of Table VII into the tank and then
disperse the resulting mixture of components under 1800-2000 rpm for about 15 minutes to
form a paint formulation.
 After the above procedure, the resulting paint formulation is placed in a
sealed can sealed under room temperature one day. After one day, the wet paint
performances are tested and coating films were applied to a substrate. The coating films
were subjected to 25 °C/60 RH conditions for 7 days and then the film properties were tested.
The results of this Example 3 are described in Tables IX-XIII below.

Coating Performance Data

A coating is applied with a film applicator (Sheen drawdown bar) with a

200 wet film thickness. Then the film is subjected to room temperature (25 °C/60% RH) for
7 days and the dry film's performances are tested according to the standards previously
mentioned. The results of these tests are described in Tables 1X-XI.
Table IX - Pigmented Coating Properties

Table X -Pigmented Coating Properties

Table X I - Water Resistance Test Results

GLOSS GLOSS
FILM GLOSS
(after 1 hours RETENTION
THICKNESS (original)
immersion) (%)
FORMULATION
after 5
after 5
µ 60° immediate immediate hours
hours
drying
Example 2 58 91.6 86.4 87 94 95
Comparative B 62 91.8 86.1 86.5 94 94
Comparative C 53 92 88.7 89.3 96 97
Example 3 55 89 84.4 85 95 96
 Stability Test
A general test method for testing the stability of a coating formulation is as
follows: Place 200 g of a sample in sealed can and subject the can to a temperature of 50 °C
for one month. After one month, visually check if any water has phase separated out of the
formulation and if any settlement has occurred. After mixing the coating formulation
uniformly, manually apply the coating formulation with 250 µη wet film thickness on a
steel Q-panel. Then test the film performances of the resulting film coating. In addition,
test the fineness of the resulting wet paint formulation. The stability and fineness test results
are described in Tables XII and XIII.

Table XII - Stability Test Results

Table XIII - Wet Paint Fineness Change After Storage (¾50°C

Example 4 - Preparation of Primer

In this Example 4, the general procedure used for making a paint formulation
in accordance with the present invention is described with reference to Table XIV as follows
 Table XIV- Formulation of a Red Alkyd Primer

The general procedure used in this Example 4 is as follows:

A. Add components of steps 1, 2, 3, 4 and 5 of Table XIV in turn into

a steel tank and then disperse the resulting mixture of components uniformly under
800-1200 rpm.

B. Add component of step 6 of Table XIV into the tank and then
disperse the resulting mixture of components uniformly under 800-1200 rpm.

C. Add components of steps 7, 8, 9, 10, and 11 of Table XIV in turn into

the tank under a slow speed of about 500 rpm; disperse the resulting mixture of components
under 1800-2000 rpm uniformly for about 25 minutes; control the temperature at under
50°C of the resulting mixture of components; and when the grindness of the resulting
mixture of components is less than 60 m, go to the next step.

D. Add components of steps 12, 13, 14, and 15 of Table XIV in turn into
the tank under a slow speed of about 500 rpm and then disperse the resulting mixture of
components under 1800-2000 rpm uniformly for about 15 minutes.
 E. Add component of step 16 of Table XIV into the tank and then
disperse the resulting mixture of components under 1800-2000 rpm uniformly for about
15 minutes to form a paint formulation.

After the above procedure, the resulting paint formulation is placed in a

sealed can sealed under room temperature for one day. After one day, the wet paint
performances are tested and coating films are applied to a substrate. The coating films were
subjected to 25 °C/60 RH conditions for 7 days and then the film properties were tested.

The process used to make the paint formulation in this Example 4 was the
same as the process described in Example 3. The resulting viscosity data for this Example 4
is described in Table XVI below.

Comparative Example D

In this Comparative Example D, the general procedure used for making a

paint formulation in accordance with the prior art is described with reference to Table XV as
follows:

Table XV - Formulation of a Red Alkyd Primer

Notes for Table XV: MS = 61.4%; VS = 46%; and VOC = 328g/L

 The general procedure used in this Comparative Example D is as follows:

A. Add components of steps 1, 2, 3, 4 and 5 of Table XV in turn into

a steel tank and then disperse the resulting mixture of components uniformly under
800-1200 rpm.

B. Add component of step 6 of Table XV into the tank and then disperse
the resulting mixture of components uniformly under 800~1200 rpm.

C. Add components of steps 7, 8, 9, 10, and 11 of Table XV in turn into

the tank under a slow speed of about 500 rpm and then disperse the resulting mixture of
components under 1800-2000 rpm uniformly for about 25 minutes; control the temperature
of the resulting mixture of components at under 50 °C; and when the grindness of the
resulting mixture of components is less than 60 µη , go to the next step.

D. Add components of steps 12, 13, 14, and 15 of Table XV in turn into
the tank under a slow speed of about 500 rpm and then disperse the resulting mixture of
components under 1800-2000 rpm uniformly for about 15 minutes.

E. Add component of step 16 of Table XV into the tank and then

disperse the resulting mixture of components under 1800-2000 rpm uniformly for about
15 minutes to form a paint formulation.

After the above procedure, the resulting paint formulation is placed in a

sealed can sealed under room temperature for one day. After one day, the wet paint
performances are tested and coating films are applied to a substrate. The coating films were
subjected to 25 °C/60 R conditions for 7 days and then the film properties were tested.
The resulting viscosity data for this Comparative Example D is described in Table XVI.

Table XVI - Viscosity Data

The data in the above Examples and Comparative Examples shows that
Examples 1-4 all have a lower VOC than traditional solvent based alkyd coats (see
Formulations), and in addition, the coatings of Examples 1-4 performance can still meet the
Chinese Standard for alkyd topcoat and finish coatings in terms of drying time, impact
resistance, adhesion, flexibility, and water resistance.

The data also shows that when a formulation employs a combination of

surfactants (i.e., the multifunctional additive), the viscosity of the resulting coatings made
from such formulation is significantly reduced comparing with when only AMP95, alone, is
used to introduce water into a solvent based alkyd coat. In addition, when AMP95, alone, is
used, the water is probably not stable in the solvent borne alkyd coating: for the clear
coating, the water separates out after a short period time; and for the pigmented alkyd
coating, it causes the paint pigment particles to flocculate; and the film coating has a poor
appearance (pig skin) after the film is heated in storage for 1 month, which is a continuing
problem for current users of coating technology using AMP technology.

In addition, the above data shows that the present invention can solve the
viscosity and water stability problems. Also, the present invention provides formulations
that have low viscosity and can still meet the requirements of users of coating formulations.

It will be obvious to persons skilled in the art that certain changes may be
made in the methods described above without departing from the scope of the present
invention. It is therefore intended that all matter herein disclosed be interpreted as
illustrative only and not as limiting the scope of protection sought. Moreover, the present
invention is not to be limited by the specific examples set forth above including the tables to
which they refer. Rather, these examples, and the tables they refer to, are illustrative of the
present invention.
WHAT IS CLAIMED IS:

1. A coating formulation comprising (a) at least one hydrophilic

surfactant; (b) at least one hydrophobic surfactant; (c) water; (d) at least one solvent; and
(e) at least one solvent borne air drying alkyd resin coating.

2. The coating formulation of claim 1, wherein the hydrophilic

surfactant comprises a nonionic surfactant, an anionic surfactant, or mixtures thereof.

3. The coating formulation of claim 1, wherein the hydrophobic

surfactant comprises a nonionic surfactant, an anionic surfactant, or mixtures thereof.

4. The coating formulation of claim 1, including at least one amino-

methyl propanol co-dispersant.

5. The coating formulation of claim 1, wherein the weight ratio of the

hydrophobic surfactant to the hydrophilic surfactant is from about 1:10 to about 1:1.

6. The coating formulation of claim 1, wherein the weight ratio of the

hydrophobic surfactant to the hydrophilic surfactant is from about 1:10 to about 1:3.

7. The coating formulation of claim 1, wherein the weight ratio of the

hydrophobic surfactant to the hydrophilic surfactant is from about :6 to about 1:3.

8. The coating formulation of claim 1, wherein the hydrophilic

surfactant comprises an ethylene oxide propylene oxide copolymer surfactant; and wherein
the hydrophobic surfactant comprises an alkyl phenol ethoxylate surfactant.

9. - The coating formulation of claim 1, including at least one drying

catalyst or at least one anti-skinning agent.

10. A clear coating formulation comprising the coating formulation of

claim 9 .

1 The coating formulation of claim 1, including at least one drying

catalyst, at least one anti-skinning agent, at least one a thickener agent, at least one pigment,
or at least one filler.

12. A pigmented coating formulation comprising the coating formulation

of claim 1.
 13. The coating formulation of any one of the preceding claims, wherein
the coating formulation is storage stable as measured at 50 °C for 30 days.

1 . The coating formulation of any one of the preceding claims, wherein

the at least one alkyd resin comprises an oil modified alkyd resin; and wherein the at
least one alkyd resin is present in the coating formulation at a concentration of from about
10 weight percent to about 80 weight percent, based on the weight of the total organic
compounds in the formulation.

15. The coating formulation of any one of the preceding claims, wherein
the water is deionized or tap water; and wherein the water is present in the coating
formulation at a concentration of from about 3 weight percent to about 30 weight percent,
based on the weight of the total organic compounds in the formulation.

16. The coating formulation of any one of the preceding claims, wherein
the at least one nonionic hydrophilic surfactant comprises an ethylene oxide/propylene oxide
copolymer; wherein the at least one nonionic hydrophobic surfactant comprises an alkyl
phenol ethoxylate; and wherein the surfactant mixture is present in the coating formulation
at a concentration of from about 0.01 weight percent to about 1 weight percent, based on the
weight of the total organic compounds in the formulation.

17. A process for preparing a coating formulation comprising admixing (a)

at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant; (c) water;
(d) at least one solvent; (e) at least one selvent borne air drying alkyd resin coating; and
(f optionally, at least one amino-methyl propanol co-dispersant.

18. A coating product comprising a cured coating formulation of claim 1.

19. A coated article comprising a substrate coated with a cured coating

formulation of claim 1.

20. The coating formulation of claim 1, wherein the viscosity of the

formulation is such that the formulation is readily and easily applied to a substrate.

1 The coating formulation of claim 1, wherein the storage stability of

the resulting cured coating when the formulation is cured, is at least greater than about one
month at 50 °C.
 22. The coating formulation of claim 1, wherein the formulation exhibits
no water separation, no viscosity change of greater than 200 cps, and no fineness of particles
change of greater than 10 microns after at least greater than about one month storage at 50
°C.

23. The coating formulation of claim 1, wherein the formulation has a

reduction in volatile organic compounds (VOC) of at least 100 g/L from an initial amount of
450 g/L VOC.

24. The coating formulation of claim 1, wherein the formulation has a

reduction in volatile organic compounds of at least 10 weight percent solvent based on the
total weight percent of the formulation.

25. The coating product of claim 8, wherein the coated cured product
properties, includes gloss, water resistance, and color are maintained or improved.
 International application No.
INTERNATIONAL SEARCH REPORT
PCT/CN2010/000068

A. CLASSIFICATION OF SUBJECT MATTER

C09D167/08 (2006.01 ) i
According to International Patent Classification (IPC) or to both national classification and IP C

B. FIELDS SEARCHED

Minimum documentation searched (classification system followed by classification symbols)

IPC:C09D167

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

|CNPAT,CNKI,EPODOC,WPI,COATING, SURFACTANT, SURFACE ACTIVE AGENT, HYDROPHILIC, HYDROPHOBIC,

fYTOPHILIC, ALKYD RESIN, AIR DRYING

C . DOCUMENT S CONSIDERED TO BE RELEVANT

Category' Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

X US4600440A(FLEC TO COMPANY INC),1 5 Jul. 1986(15.07.1986) 1-25

Claim 12, example, column 2 lines 31-33 and 40-68 of the description

WO2004037928A(PERSTORP SPECIALTY CHEM AB), 06 May 2004(06.05.2004) 1-25

the whole document
CN101307137A( SHANGHAI COATINGS CO LTD),19 Nov.2008(19.1 1.2008) 1-25
the whole document

KR20030065716 A(KOCHEM CO LTD), 09 Aug. 2003(09.08.2003) 1-25

the whole document

l~~l Further documents are listed in the continuation of Box C . patent family annex.

* Special categories of cited documents:
Ά " document defining the general state of the art which is not
considered to be of particular relevance
Έ" earlier application or patent but published on or after the
international filing date
'L" document which may throw doubts on priority claim (S) or
which is cited to establish the publication date of another
citation or other special reason (as specified)
Ό" document referring to an oral disclosure, use, exhibition or
other means
"T" later document published after the international filing date
or priority date and not in conflict with the application but
cited to understand the principle or theory underlying the
invention
"X" document of particular relevance; the claimed invention
cannot be considered novel or cannot be considered to involve
an inventive step when the document is taken alone
"Y" document of particular relevance; the claimed invention
cannot be considered to involve an inventive step when the
document is combined with one or more other such
documents, such combination being obvious to a person
skilled in the art

'P" document published prior to the international filing date " & "document member of the same patent family
but later than the priority date claimed
Date of the actual completion of the international search Date of mailing of the international search report
30 Aug.2010 (30.08.2010) 28 Oct. 2010 (28.10.2010)
Name and mailing address of the ISA/CN
Authorized officer
The State Intellectual Property Office, the P.R.China
6 Xitucheng Rd., Jimen Bridge, Haidian District, Beijing, China GAO Beibei
100088
Telephone No. (86-10 )62084928
facsimile No. 86-10-62019451
Form PCT ISA /210 (second sheet) (July 2009)
 INTERNATIONAL SEARCH REPORT International application No.
Information on patent family members
PCT/CN2010/000068

Patent Documents referred Publication Date Patent Family Publication Date

in the Report

US4600440A 15.07.1986 CA1260206A 26. 09.1989

WO2004037928A 06.05.2004 SE0203156A 26.04.2004

SE524568C2 3 1 . 08.2004

AU2003269776A1 13.05.2004

EP1 554349 A l 20.07.2005

BR0315525A 23.08.2005

JP2006503955T 02.02.2006

US2006052510A1 09.03.2006

MXPA05004298A 23.11 .2005

CN1708558A 14.12.2005

KR20050072116A 08. 07.2005

ZA200503027A 26.07.2006

NZ539471A 27.10.2006

US7186771B2 06.03.2007

EP1554349B1 28.03.2007

DE60312880E 10.05.2007

AU2003269776B 29.03.2007

ES2283807T 0 1 .11 .2007

DE60312880T 06.12.2007

MX251036B 30. 10.2007

CN100480335C 22. 04.2009

JP4447462B2 07.04.2010

CA2502662A 06.05.2004

AT358164T 15.04.2007

DK1554349T 07.05.2007

HK1 080883A 14.09.2007

CN101307137A 19.11 .2008 None

KR20030065716 A 09.08.2003 None

Form PCT ISA /210 (patent family annex) (July 2009)