United States Patent [19] [11] 3,920,597

Nicks et a1. [45] Nov. 18, 1975

[54] PAINT COMPOSITIONS AND METHOD OF 3,580,880 5/1971 Clarke et a1. ................ .. 260/29.6 R
THEIR PRODUCTION 3,691,123 9/1972 Clarke et al. .. 260/33.6 R
3,759,864 9/1973 Nicks . . . . . . . . . . . . . . . . .. 260/33.6 R

[75] Inventors: Peter Francis Nicks, Maidenhead; 3,804,787 4/1974 Nicks et a1. ..................... .. 260/22 R
William Anthony Ryan, Finchley,
both of England
Primary Examiner-Ronald W. Grif?n
[73] Assignee: Imperial Chemical Industries Attorney, Agent, or Firm—Cushman, Darby &
Limited, London, England Cushman
122] Filed: Aug. 16, 1974
[21] Appl. No.: 498,214
[57] ABSTRACT
[30] Foreign Application Priority Data
A method of producing a non-aqueous paint composi
Sept. 10, 1973 United Kingdom ............. .. 42430/73 tion comprising a pigmented solution of a water
insoluble ?lm forming resin in water-immiscible liquid
[52] US. Cl ...... .. 260/22 R; 117/161 K‘, 260/22 CB; in which the pigment is treated with a drying oil modi
260/33.6 R; 260/40 R ?ed alkyd resin containing more than 50% by weight
[51] Int. Cl.2 .......................................... .. C09D 3/64 of a hydrophilic moiety derived from a poly(ethylene
158] Field of Search .......... .. 260/22 R, 22 A, 22 CE, glycol) of molecular weight 400-1500 and ‘there is
260/33.6 EP:33.6 R, 32.6 R, 30.8 R also incorporated a compound which is soluble in the
paint and which in water has detergent properties.
[56] References Cited
UNITED STATES PATENTS 7 10 Claims, No Drawings
3,234,161 2/1966 Snelgrove et a1. ........... .. 260/29.6 R
 3,920,597
1 2
col) of molecular weight» 400-1500, the auxiliary resin
PAINT COMPOSITIONS AND METHOD OF THEIR being used in a proportion of not less than 1% by
PRODUCTION weight based on the total resin content of the paint
composition, and wherein the process also includes the
This invention relates to a method of producing further incorporation into the paint composition in an
paints based on a solution of resin in a water-immisci- ' amount of l—l0% by weight based on the total resin
ble diluent, more particularly to the production of dec content of the paint of a compound which is soluble in
orative paints which are emulsi?able in water. The in the solution of base resin in water-immiscible liquid
vention also relates to improved decorative paints. and which in water has detergent properties.
ln our US. appl. Pat no. 3,804,787 we have de Preferably the base resin is a drying oil-modi?ed
scribed and claimed a method of producing solvent alkyd resin.
borne paints which are emulsi?able in water in the The invention also provides improved paints pro
presence of a synthetic detergent of the type used for duced by the process herein described and paint addi
domestic purposes, for example sodium dodecylben tives herein referred to as auxiliary resins.
zene sulphonate. Such a paint may easily be removed The term “paint” is used herein to denote a composi
from an applicator, for example a brush, by treatment tion comprising pigment and a solution of a ?lm-form
of the latter with an aqueous solution of detergent. The ing resin in a water-immiscible diluent.
method in question is directed to the production of a By “the base resin” we mean that resin which is nor
paint composition which comprises a pigmented solu mally responsible for the main ?lm-forming character
tion of a water-insoluble ?lmforming base resin in a wa istics of the paint, and this resin may be present in any
ter-immiscible liquid, the solution of base resin being proportion up to 99% by weight of the total resin con
completely emulsi?able in an aqueous synthetic deter tent of the paint. The base resin may comprise more
gent solution when the pigment is absent but incom than one ?lm-forming material, for example it may be
pletely co-emulsi?able therein with pigment when the a mixture of two or more drying-oil-modi?ed alkyd res
pigment is present and the method is characterized by 25 ins. It is also within the scope of the present invention
the feature that one of the steps involved comprises to employ a mixture of one or more such alkyd resins
treating at least a proportion of the pigment in disper with minor proportions of resins of other types, for ex
sion in a water-immiscible liquid with an auxiliary resin ample polyurethane resins or polyamide resins for the
which (a) is co-emulsi?able in the aqueous detergent purpose of imparting thixotropic properties to the
solution with the pigment when dissolved in the water paint. Drying oil-modified alkyd resins suitable for use
immiscible liquid of the paint composition and (b) is in the process of the invention as base resins are any of
preferentially adsorbed by the pigment from a solution such resins described in the earlier application and
of both the base resin and the auxiliary resin in the wa more generally any of such resins conventionally used
ter-immiscible liquid of the paint composition. The in the coatings art.
auxiliary resin should also be compatible with the base 35 As already stated, the auxiliary resin as hereinbefore
resin in that the two resins form only one phase when de?ned must be present in a proportion of not less than
mixed in any proportions. The full disclosure of the 1% by weight of the total resin content of the paint;
above mentioned application is incorporated herein by preferably it is present in a proportion of not less than
this reference thereto. 5% by weight, and even more preferably in a propor
One class of suitable auxiliary resins for use in‘the 40 tion of 75-15% by weight of the total resin content. In
above process comprises drying oil-modi?ed alkyd res certain cases it may be desirable to employ higher pro
ins which contain hydrophilic groups derived from portions than 15% of the auxiliary resin for example up
poly(ethylene glycol) moieties of molecular weight to 30%, and exceptionally the proportion used may
l00—5000. Particularly suitable resins of this class are even exceed 50% by weight of the total resin content of
stated to be those which contain 10-50% by weight of 45 the paint.
a poly(ethylene glycol) moiety of molecular weight As in the case of the auxiliary resins more broadly de
400-1000. It is preferred to use such auxiliary resins in ?ned in the earlier application, the auxiliary resins
conjunction with base resins which are also of the dry hereinbefore de?ned as being suitable for use in the
ing oil-modi?ed alkyd type. present process contain chemical groups which on the
We have now found that if in the above process there 50 one hand enable them to associate with the pigment
is used as the auxiliary resin a drying oil-modi?ed alkyd surface and which on the other hand promote emulsi?
resin containing more than 50% by weight of a poly cation of the pigment in water in the presence of a de
(ethylene glycol) moiety of molecular weight tergent compound. The auxiliary resins as herein de
400-1500, and there is also incorporated in the paint ?ned also possess the necessary property of being pref
composition a compound having detergent properties, 55 erentially adsorbed by the pigment from a solution in
the resulting paint is emulsi?able in plain water, as dis the water-immiscible liquid of the paint composition of
tinct from a pre-forrned detergent solution. both the base resin and the auxiliary resin. Con?rma
According to the present invention, therefore, we tion that the auxiliary resins employed in the present
provide a method of producing a non-aqueous paint process do possess these required characteristics may
composition, comprising a pigmented solution of a wa 60 be obtained by subjecting the resins to the emulsi?ca
ter-insoluble ?lm forming base resin in water-immisci tion and adsorption tests which are described in the
ble liquid, which is a modi?cation of the method de speci?cation of the earlier application.
scribed in US. Pat. No. 3,804,787 and wherein at least The poly(ethylene glycol) moieties may, for exam
a proportion of the pigment is treated in dispersion in a ple, be introduced into the auxiliary resin by reacting a
water-immiscible liquid with an auxiliary resin which is 65 hydroxyl-terminated poly(ethylene glycol) with a com
a drying oil-modi?ed alkyd resin containing more than plementary reactive group, eg a carboxyl group, in a
50% by weight based on the total weight of the resin of preformed conventional drying oil-modi?ed alkyd
a hydrophilic moiety derived from a poly(ethylene gly resin. Alternatively, a hydroxyl-terminated poly(ethy
 3,920,597
3 4
lene glycol) maybe employed as one of the initial com pound exhibiting detergent properties in water and
ponents in a condensation reaction, together with the which is soluble in the solution of base resin in water
other components normally employed in the prepara immiscible liquid. This compound may be a synthetic
tion of an alkyd resin. The auxiliary resin must contain detergent such as one of the types well known for do
more than 50% by weight based on the total weight of mestic use, for example a non-ionic surfactant of the
resin, and should preferably contain up to 90% by ethylene oxide condensate type e.g. ethylene oxide
weight, of a moiety of poly(ethylene glycol), optionally condensate/alkyl phenol, such as nonylphenol con
etheri?ed, the range of molecular weight of the moiety densed with 8 moles of ethylene oxide, or an anionic
being 400-1500. A preferred range of molecular surfactant such as sodium dodecylbenzene sulphonate
weight of the poly(ethylene glycol) moiety is 600—800. or sodium dioctylsulphosuccinate. It may be incorpo
In general the auxiliary resins containing moieties of rated in the paint composition at any convenient stage,
poly(ethylene glycol) are of relatively low acid value, for example at the stage of blending in the pigment
preferably less than 30mg. KOl-l/g. The acid value of which has been treated with the auxiliary resin. Alter
the base resin is also preferably less than 30mg. KOH/g.
Preferably trimellitic anhydride is employed as one of natively, the detergent compound may be provided by
the initial components in the alkyd condensation reac a further addition of auxiliary resin containing poly
tion. (ethylene glycol) moieties as hereinbefore described; if
Pigments, and also extenders and ?llers, suitable for desired, such further addition of the auxiliary resin may
use in paint compositions made according to the inven be combined with the addition of a synthetic detergent
tion are vthose which are described for use in the pro 20 as just mentioned. The total amount of the detergent
cess of the earlier application. Suitable pigments in compound used (not taking into account the auxiliary
clude, for example, titanium dioxide, the iron oxides, resin used to treat the pigment) is in the range 1-10%
whether black, yellow, red or brown; chrome oxide by weight based on the total resin content of the paint;
green; phthalocyanine blue; phthalocyanine green; red preferably the amount lies in the range 1-5% by weight
lead; cobalt blue; graphite; vegetable carbon black; 25
of the total resin content. In the case where the deter
mineral carbon black: metallic aluminium; metallic gent compound consists of or includes additional auxil
lead; metallic zinc; white lead sulphate, which lead car iary resin, that additional resin is preferably not in
bonate; zinc oxide. Suitable extending pigments and cluded with the main charge of auxiliary resin at the
?llers include barium sulphate; calcium sulphate; cal pigment treatment stage but is incorporated into the
. cium carbonate; magnesium carbonate: calcium sili 30 paint composition after the initial treatment with auxil
cate; magnesium silicate; and silica. iary resin, for example at the stage of blending in the
The term “water-immiscible liquid,” as used herein
with reference to the liquid in which the base resin is treated pigment.
dissolved, means either a single liquid chemical entity The present process may be used to produce a wide»
which forms a separate phase on admixture with water 35 range of paints, for example gloss, semi-gloss, matt, un
or a mixture of two or more such liquids. The presence dercoat and primer paints, including paints which are
‘of admixed liquids which are water-miscible, even of modified structure, for example those having non
though they may not affect the water-immiscibility of Newtonian flow characteristics. It is particularly appli
the base resin solvent medium as a whole, is excluded. cable to the production of paints which are normally
Suitable water-immiscible liquids include a wide range 40 applied by brush or roller, and it confers on such paints
of aliphatic and aromatic organic liquids such as esters, the very valuable property that surplus paint can
ketones and hydrocarbons; we are particularly con readily be removed from the brush or roller simply by
cerned with aliphatic hydrocarbons which are com washing the latter in a stream of plain, warm water, as
monly used in the formulation of decorative paints and for example from a tap. The added convenience of op
which may boil in the range l00°—300°C. A particularly 45 eration which is thereby achieved will be immediately
suitable hydrocarbon is commercially available white apparent, especially in the domestic decoration field. In
spirit of boiling range 140°—200°C which is predomi most cases the incorporation into the paint composi
nantly aliphatic hydrocarbon but which contains up to tion of the necessary proportions of auxiliary resin and
15% of aromatic hydrocarbon.
In performing the process of the invention, the pig 50 detergent compound has little or no adverse effect on
ment may be treated in dispersion in water-immiscible
the other paint properties of the compositions.
liquid with the auxiliary resin in the absence of base The invention is illustrated but not limited by the fol
resin or in admixture with a proportion of the base lowing Examples, in which parts and percentages are
resin. The pigment may also be treated with auxiliary by weight unless otherwise stated.
resin after the pigment has been treated with base resin. EXAMPLE 1
In this last case the full effect of the auxiliary resin on
the emulsi?cation of the paint is only realized when the Preparation of Auxiliary Resin
preferential adsorption of the auxiliary resin has taken A poly(ethylene glycol) modi?ed alkyd resin was
effect, i.e., after the paint has been stored, for example prepared as a 96% solids solution in xylene from poly
after a storage period of up to 1 month. It may be de 60
(ethylene glycol) or molecular weight 600, trimellitic
sired to treat only a proportion of the pigment in the anhydride, pentaerythritol, and tall oil fatty acids in the
paint composition according to the present process, the molar ratios 0.61/2.82/ l .67/ 3. The ?rst two ingredients
remainder of the pigment being added without such were pre-reacted and then condensed with the other
treatment. Alternatively, the pigment may be treated
65 ingredients to an acid value of 20mg. KOl-l/g and a vis
with auxiliary resin in a separate operation and stored
for use as required in making the paint composition. cosity of 30 secs. BT (bubble tube) at 25°C (96% solids
The process of the present invention also requires the in xylene). The alkyd resin so obtained contained 60% '
incorporation into the paint composition of a com poly( ethylene glycol) moieties and 30% fatty acids.
 3,920,597
5 . 6
ample 1 and 28g of white spirit. To this millbase was
Preparation of a Base Resin added 205g of base resin solution in which was dis
A base resin was prepared as a 75% solids solution in solved 3.8g of sodium dioctyl sulphosuccinate, 1g of
white spirit from linseed oil fatty acids, phthalic anhy cobalt naphthenate, 10g of calcium napthenate 15g of
dride, glycerol and pentaerythritol in the molar ratio lead naphthenate, and 50g of white spirit to thin the
3/2/1/1 and was condensed to an acid value of 15mg. paint to a viscosity of 2.5 poise at 25°C and 10,000
KOl-l/g and a viscosity of 10 secs BT at 25°C (75% secs. ‘1. The paint thus obtained could be readily emul
solids solution in white spirit). . si?ed both in detergent solution as in Example 1 and in
The auxiliary resin solution was found to be readily warm water. Similarly it could be cleaned from brushes
emulsi?ed in water whereas the base resin solution was l0 in both detergent solution and warm water.
completely non-emulsi?able. EXAMPLE 4
Preparation of a gloss paint Comparative Preparation of Auxiliary Resin
A full gloss paint was prepared by dispersing 175g of An'auxiliary resin was prepared by reacting penta
rutile titanium dioxide in a mixture of 10g of the auxil eryrithritol, glycerol, poly(ethylene glycol) of molecu
iary resin solution described above, 25.6g of the base _ lar weight 600, trimellitic anhydride and tall oil fatty
resin solution described above and 28g of while spirit in acids in the molar ratio 1/1/2/2/5 until an acid value of
a sand grinder. To this millbase was added with stirring 20mg. KOl-l/g was obtained. The resin was thinned to
a further 20g of the auxiliary resin solution, 192g of the 75% solids in white spirit and contained 38.3% poly
base resin solution, lg of cobalt naphthenate (6% c0 20
(ethylene glycol) moieties.
balt), 10g of calcium napthenate (4% calcium) and 15g
of lead naphthenate (24% lead). The paint was thinned Preparation of Gloss Paint
with 30g of white spirit to a viscosity of 4 poise mea A gloss paint was prepared by dispersing 175g of ru
sured at 25°C and 10,000 secs. ‘1. tile titanium dioxide in 19g of the auxiliary resin solu
The ease of emulsi?cation of this paint in detergent 25 tion described in this Example, 26g of the base resin so
solution and in plain, warm water respectively was then lution described in Example 1 and 28g of white spirit.
assessed. Two paint brushes A and B having a 2 inch To this dispersion was added 167g of the base resin so
width of bristles were ?lled with the paint, ensuring that lution, 19g of a 30% solution of sodium dioctyl sulpho
the paint was thoroughly worked into the stock of each succinate dissolved in the base resin solution, lg of co
brush. Each brush was allowed to dry for 30 minutes. balt naphthenate, 10g of calcium naphthenate and 15 g
Brush A was then cleaned by being agitated vigorously of ‘lead naphthenate. The paint was thinned to 3 poise
in a warm (40°C) solution of 3.3g sodium dodecyl ben at 25°C and 10,000 secs. “1 with 48g of white spirit.
zene sulphonate in 500 mls of water. Brush B was
The paint was tested as described in Example 1. It
cleaned by being agitated vigorously in warm water was found to be emulsified readily in detergent solution
35
(40°C). and brush A could be cleaned easily in that solution.
In both cases the paint was readily emulsi?ed and
The paint was not, however, emulsi?able in plain warm
could be completely removed from the brush. water and attempts to clean brush B with warm water
A similar paint prepared as described above but in alone led to the deposit upon the bristles of a sticky res
which the auxiliary resin was replaced by its equivalent idue. '
weight of base resin (calculated on non-volatile con 40
tent) did not show any tendency to emulsify in either EXAMPLE 5
detergent solution or warm water, nor could it be
cleaned from a brush, when tested as above.
A blue gloss paint was prepared by dispersing 38g of
rutile titanium dioxide, 12g of the Colour Index pig
EXAMPLE 2 45 ment Blue 15 and 1.25 g of carbon black in 19g of the
A gloss paint was prepared from the auxiliary resin auxiliary resin solution described in Example 1, 157g
of the base resin solution described in Example 1 and
and base resin described in Example 1 in the following 17g of white spirit. To this millbase were added 7.5 5g
manner. 175 g of rutile titanium dioxide was dispersed of sodium dioctyl sulphosuccinate dissolved in 288g of
in 15g of the auxiliary resin solution, 25g of base resin the base resin solution, 1.7g of cobalt naphthenate‘,
solution and 28g of white spirit. To this millbase was 50
added 2.5g of dodecyl benzene sulphonic acid sodium 1 1.75g of lead naphthenate and 25.6g of calcium naph
salt dissolved in 205g of base resin solution, 1g of co
thenate, together with 45g of white spirit to give a paint
having a viscosity of 2.5 poise at 25°C and 10,000 secs.
balt napthenate, 10g of calcium naphthenate and 15g
of lead naphthenate. The paint was thinned to 4 poise Erushes ?lled with this paint and tested as described
at 25°C and 10,000 secs. ‘1 with 33g of white spirit. 55
in Example 1 could be cleaned readily in both the de
The ease of clean-up of a 2 inch brush was assessed
tergent solution and warm water.
by the method described in Example 1. The paint was
easily emulsi?ed in the detergent solution described in EXAMPLE 6
Example 1 and also in warm water; brush A could be Preparation of Auxiliary Resin
readily cleaned in the detergent solution and brush B in 60
warm water. A ?lm 0.004 inch thick spread on glass A poly(ethylene glycol) modi?ed alkyd resin was
dried in 16 hours and gave a gloss value of 98 when prepared as a 94% solids solution in xylene from penta
measured with a 45° gloss meter. erythritol,polyethylene glycol 600, phthalic anhydride
and tall oil fatty acids in the molar ratios
EXAMPLE 3 65 O.6/3.0/2.3/3.0. The resin was condensed to an acid
A white gloss paint was prepared by dispersing 175g value of 18.7mg KOH/g and a viscosity of 1.8 secs BT
of rutile titanium dioxide in 17g of the auxiliary resin at 25°C when tested as a 75% solids solution in ali
solution of Example 1, 25g of base resin solution of Ex phatic hydrocarbon (boiling range l50°—200°C).
 3,920,597
7 8
oil-modified alkyd resin in water-immiscible liquid, the
Preparation of Gloss Paint improvement wherein (l) at least a proportion of the
159 parts of rutile titanium dioxide and 2.5 parts of pigment is treated in dispersion in a water-immiscible
zinc oxide were dispersed in a solution of 48.1 parts of liquid with an auxiliary resin which is a drying oil-modi
the above auxiliary resin dissolved in 38.5 parts of ali ?ed alkyd resin containing more than 50% by weight
phatic hydrocarbon (boiling range 150°—200°C). based on the total weight of the resin of a hydrophilic
3.7 parts of sodium dioctyl sulphosuccinate were dis moiety derived from a poly(ethylene glycol) of molecu
Solved in 176 parts of the base resin described in Exam lar weight 400-1500, the auxiliary resin being used in a
ple 1 together with 14.1 parts of lead naphthenate proportion of not less than 1% by weight based on the
(24% Pb), 1.15 parts of cobalt naphthenate (6% Co) total resin content of the paint composition, and (2)
and 7.0 parts of calcium napthenate (5% Ca) and the there is also incorporated into the paint composition,
blend added with stirring to the millbase. When thor after the treatment of the pigment with said auxiliary
oughly mixed 10 parts of dipentene were added and the resin, an amount of l-l 0% by weight based on the total
paint thinned to a viscosity of 4 poise measured at 25°C resin content of the paint of a compound which is solu‘
and 10,000 secs. Y“ by the addition of 17 parts of white ble in the solution of base resin in water-immiscible liq
spirit. uid and which in water has detergent properties, said
.A similar paint was prepared in which the sodium di compound being selected from the group consisting of
octyl sulphosuccinate was replaced by an equivalent compounds having the chemical structure of the auxil
weight of disodium N-octodecyl sulphosuccinamate iary resin and synthetic non-ionic or anionic surfac
20 tants.
(added as 35% solution in water).
The paints contained 25% by weight of the total resin 2. A method according to claim 1 wherein the hydro
(non volatiles) as the auxiliary resin and 2% by weight philic moiety is derived from a poly(ethylene glycol) of
of total resin as the sulphosuccinate. molecular weight 600-800.
The ease of clean up of a 2 inch brush when ?lled 3. A method according to claim 1 wherein a hydrox
with these paints was assessed by the method described yl-terminated poly(ethylene glycol) is employed as one
in Example 1. Both paints could be cleaned very readily initial component in the preparation of the auxiliary
from brushes in either warm water or the detergent so alkyd resin.
lution described in Example 1. 4. A method according to claim 1 wherein trimellitic
anhydride is employed as one initial component in the
EXAMPLE 7 30 preparation of the auxiliary alkyd resin.
Gloss paints similar in composition to that of Exam 5. A method according to claim 1 wherein the com
ple 2 were prepared but using the following detergents pound having detergent properties in water which is
instead of sodium dodecyl benzene sulphonate: further incorporated into the paint has the chemical
Ammonium nonylphenol ethylene oxide sulphate structure of the auxiliary resin.
35 6. A method according to claim 1 wherein the com
(Perlankrol FF) pound having detergent properties in water is a syn
Alkylolamide/ethylene oxide condensate (Ethylan
CH) thetic non-ionic or anionic surfactant.
Poly(ethylene glycol 600) oleate (Ethylan A6) 7. A method according to claim 1 wherein there is
Sodium aryl alkyl sulphonate (Atlas G3300) 40
employed 1—5% by weight of the compound having de
Sodium dioctyl (and dihexyl) sulphosuccinate (Aero tergent properties-in water.
sol OT and MA) 8. A method according to claim 1 wherein the water
N-octadecyl sulphosuccinamate immiscible liquid comprises aliphatic hydrocarbon.
Sodium lauryl sulphate 9. A method according to claim 1 wherein the pig
All of these detergents allowed excellent removal of 45 ment is treated in dispersion in water-immiscible liquid
'paint from a paint brush by the test of Example 1. with auxiliary resin alone or with a blend of auxiliary
What we claim is: resin and a proportion of base resin.
1. In a method of producing a non-aqueous paint 10. A paint composition when prepared by the
composition, comprising a pigmented solution of a wa method according to claim 1.
* * * * *
ter-insoluble ?lm forming base resin which is a drying 50

55

60

65