U.S. patent application number 15/410203 was filed with the patent office on 2017-05-11 for ici thickener composition and uses.
The applicant listed for this patent is Elementis Specialties, Inc.. Invention is credited to Stanley Leon FREEMAN, Eduardus Maria MANGNUS, Alart MULDER, Onno RIENSTRA, Kenneth F. SMITH.
Application Number | 20170130073 15/410203 |
Document ID | / |
Family ID | 52584102 |
Filed Date | 2017-05-11 |
United States Patent
Application |
20170130073 |
Kind Code |
A1 |
MANGNUS; Eduardus Maria ; et
al. |
May 11, 2017 |
ICI THICKENER COMPOSITION AND USES
Abstract
A composition comprising linked segments of: (a) a polyhydroxy
segment derived from a compound independently selected an acyclic
polyhydric alcohol having 4 to 6 carbon atoms and 4 to 6 reactive
hydroxyl groups; a cyclic polyhydric alcohol having 4 to 6 carbon
atoms and 4 to 6 reactive hydroxyl groups, a poly(hydroxyethyl)
polyethyleneamine having 4 to 6 reactive hydroxyl groups and
combinations thereof; (b) polyoxyalkylene segments wherein each
hydroxyl group of the polyhydroxyl segment is linked to a
polyoxyalkylene segment; (d) and aliphatic end segments or aromatic
end segments, each end segment having 6 to 32 carbon atoms and a
hydroxyl reactive group, wherein the mole ratio of the
polyoxyalkylene segment to the polyhydroxy segment is at least 4:1
and the mole ratio of the aliphatic or aromatic end segment to the
polyhydroxy segment is at least 0.25:1.
Inventors: |
MANGNUS; Eduardus Maria;
(Deventer, NL) ; RIENSTRA; Onno; (Deventer,
NL) ; FREEMAN; Stanley Leon; (Plainsboro, NJ)
; MULDER; Alart; (Delden, NL) ; SMITH; Kenneth
F.; (Doylestown, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Elementis Specialties, Inc. |
East Windsor |
NJ |
US |
|
|
Family ID: |
52584102 |
Appl. No.: |
15/410203 |
Filed: |
January 19, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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14465206 |
Aug 21, 2014 |
9550859 |
|
|
15410203 |
|
|
|
|
61873766 |
Sep 4, 2013 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 2650/32 20130101;
C08G 18/4837 20130101; C08G 18/003 20130101; C08G 65/33348
20130101; C08G 2650/08 20130101; C08G 65/332 20130101; C08G 65/2603
20130101; C08G 18/3206 20130101; C08G 18/71 20130101; C08G 65/331
20130101; C08G 2650/58 20130101; C09D 7/43 20180101; C08G 65/2609
20130101; C08G 65/333 20130101 |
International
Class: |
C09D 7/00 20060101
C09D007/00; C08G 18/00 20060101 C08G018/00; C08G 18/32 20060101
C08G018/32; C08G 65/331 20060101 C08G065/331; C08G 18/71 20060101
C08G018/71 |
Claims
1-11. (canceled)
12. A composition comprising linked segments of: (a) a polyhydroxy
segment derived from a compound independently selected from the
group of an acyclic polyhydric alcohol having 4 to 6 carbon atoms
and 4 to 6 reactive hydroxyl groups; a cyclic polyhydric alcohol
having 4 to 6 carbon atoms and 4 to 6 reactive hydroxyl groups, an
alkoxylated acyclic polyhydric alcohol, an alkoxylated cyclic
polyhydric alcohol, a poly(hydroxyethyl) polyethyleneamine having 4
to 6 reactive hydroxyl groups and combinations thereof; (b)
aliphatic linking segments or aromatic linking segments, each
linking segment having at least two linking groups independently
selected from the group consisting of: urethane linking group
(O--C(.dbd.O)--NH), urea linking group (N(R)--C(.dbd.O)--NH) ether
linking group (--O--), ester linking group (--C(.dbd.O)O--), amine
linking group (--NH--), an aminoplast segment, a linking group
which is the residue from reaction of an epihalohydrin and a
hydroxyl group, and mixtures thereof, wherein each hydroxyl group
of the polyhydroxy segment is linked to an aliphatic linking
segment or aromatic linking segment; (c) polyoxyalkylene segments;
and (d) aliphatic end segments or aromatic end segments, each
aliphatic or aromatic group, of said end segments, having 6 to 32
carbon atoms and a hydroxyl reactive linking group, wherein the
mole ratio of the polyoxyalkylene segment to the polyhydroxy
segment is at least 4:1 and the mole ratio of the aliphatic or
aromatic end segment to the polyhydroxy segment is at least
0.25:1.
13. The composition as in claim 12, wherein the poly(hydroxyethyl)
polyethyleneamine is independently selected from
tetra(hydroxyethyl) ethylene diamine, penta(hydroxyethyl)
diethylene triamine, hexa(hydroxyethyl) triethylene tetraamine and
mixtures thereof.
14. The composition as in claim 12, wherein the acyclic polyhydric
alcohol is independently selected from the group consisting of:
pentaerythritol, erythritol, xylitol, sorbitol, mannitol and
mixtures thereof.
15. The composition as in claim 12, wherein the alkoxylated acyclic
polyhydric alcohol is independently selected from the group
consisting of: alkoxylated pentaerythritol, alkoxylated erythritol,
alkoxylated xylitol, alkoxylated sorbitol, alkoxylated mannitol and
mixtures thereof.
16. The composition of claim 15, wherein the alkoxylated acyclic
polyhydric alcohol is independently selected from the group
consisting of: ethoxylated pentaerythritol, ethoxylated erythritol,
ethoxylated xylitol, ethoxylated sorbitol, ethoxylated mannitol and
mixtures thereof.
17. The composition as in claim 12, where the cyclic polyhydric
alcohol is independently selected from the group consisting of
inositol, glucopyranose and mixtures thereof.
18. The composition of claim 12, where the alkoxylated cyclic
polyhydric alcohol is independently selected from the group
consisting of alkoxyated inositol, alkoxyated glucopyranose and
mixtures thereof.
19. The composition as in claim 12, wherein the hydroxyl reactive
group is independently selected from the group consisting of:
isocyanate group, an epoxide group, an acid group, an ester group
or a halide group.
20. The composition of claim 19, wherein the isocyanate group is
independently derived from the group consisting of
dodecylisocyanate, stearyl isocyanate and mixtures thereof.
21. The composition of claim 19, wherein the epoxide group is
independently derived from the group consisting of:
1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane,
1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane,
2-ethylhexylglycidylether, dodecyl glycidylether, tridecyl
glycidylether, hexadecylglycidylether, alkylphenyl glycidylether
and mixtures thereof.
22. The composition of claim 19, wherein the acid group is
independently derived from the group consisting of: 2-ethylhexanoic
acid, isononanoic acid, decanoic acid, dodecanoic acid, 2-butyl
octanoic acid and mixtures thereof.
23. The composition of claim 19, wherein the ester group is
independently derived from the group consisting of methyl
decanoate, methyl dodecanoate and ethyl dodecanoate.
24. The composition of claim 19, wherein the halide group is
independently derived from 1-chlorododecane, 1-bromododecane and
1-chloro-2-hydroxy-3-(dodecyloxy)propane.
25. The composition as in claim 12, wherein each polyoxyalkylene
segment has a weight average molecular weight ranging 3,000 g/mole
to 10,000 g/mole.
26. An aqueous thickener composition comprising: the composition of
claim 12, a viscosity suppressing additive selected from the group
consisting of: an organic co-solvent, a surfactant, a cyclodextrin
compound or combinations thereof, and water.
27. The aqueous thickener composition according to claim 26, having
5 wt. % to 50 wt. % of the composition according to claim 12, 0.1
wt. % to 25 wt. % of the viscosity suppressing additive, and the
balance being water.
28. A method to improve ICI viscosity of an aqueous composition
comprising: providing an effective amount of an ICI thickening
composition to an aqueous composition, the ICI thickening
composition comprises the composition according to claim 12,
wherein the ICI viscosity of the aqueous composition ranges from
0.5 to 5.0.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of U.S.
Provisional Application No. 61/873,766 filed Sep. 4, 2013, which is
incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to ICI thickener compositions
which are useful for modifying the rheological properties of paint
formulations.
BACKGROUND OF THE INVENTION
[0003] Rheology modifiers are used in waterborne coatings
formulations to control viscosity over a wide shear rate range.
They may be associative (they associate with the dispersed phase)
or non-associative (they thicken the water phase). Associative
thickeners may be derived from natural products such as
hydrophobically modified cellulose ethers, or prepared from
synthetic polymers such as hydrophobically modified ethylene oxide
urethane (HEUR) polymers. U.S. Pat. No. 4,155,892 (Emmons et al.)
describes the preparation of linear as well as branched HEUR
polymers in separate examples.
SUMMARY OF THE INVENTION
[0004] In an embodiment, the present disclosure provides for a
composition including linked segments of: (a) a polyhydroxy segment
derived from a compound independently selected from the group of an
acyclic polyhydric alcohol having 4 to 6 carbon atoms and 4 to 6
reactive hydroxyl groups; a cyclic polyhydric alcohol having 4 to 6
carbon atoms and 4 to 6 reactive hydroxyl groups, a
poly(hydroxyethyl) polyethyleneamine having 4 to 6 reactive
hydroxyl groups and combinations thereof; (b) polyoxyalkylene
segments wherein each hydroxyl group of the polyhydroxyl segment is
linked to a polyoxyalkylene segment; (c) and aliphatic end segments
or aromatic end segments, each aliphatic or aromatic group, of said
end segments, having 6 to 32 carbon atoms and a hydroxyl reactive
linking group, wherein the mole ratio of the polyoxyalkylene
segment to the polyhydroxy segment is at least 4:1 and the mole
ratio of the aliphatic or aromatic end segment to the polyhydroxy
segment is at least 0.25:1. In one embodiment, the aliphatic end
segment or aromatic end segment is linked to an unlinked end of the
polyoxyalkylene segment linked to the polyhydoxyl segment.
[0005] In another embodiment, the present disclosure provides for a
composition comprising linked segments of: (a) a polyhydroxy
segment derived from a compound independently selected from the
group of an acyclic polyhydric alcohol having 4 to 6 carbon atoms
and 4 to 6 reactive hydroxyl groups; a cyclic polyhydric alcohol
having 4 to 6 carbon atoms and 4 to 6 reactive hydroxyl groups, an
alkoxylated acyclic polyhydric alcohol, an alkoxylated cyclic
polyhydric alcohol, a poly(hydroxyethyl) polyethyleneamine having 4
to 6 reactive hydroxyl groups and combinations thereof; (b)
aliphatic linking segments or aromatic linking segments, each
linking segment having at least two linking groups independently
selected from the group consisting of: urethane linking group
(O--C(.dbd.O)--NH), urea linking group (N(R)--C(.dbd.O)--NH) ether
linking group (--O--), ester linking group (--C(.dbd.O)O--), amine
linking group (--NH--), an aminoplast segment, a linking group
which is the residue from reaction of an epihalohydrin and a
hydroxyl group, and mixtures thereof; (c) polyoxyalkylene segments;
(d) and aliphatic end segments or aromatic end segments, each
aliphatic or aromatic group, of said end segments, having 6 to 32
carbon atoms and a hydroxyl reactive linking group, wherein the
mole ratio of the polyoxyalkylene segment to the polyhydroxy
segment is at least 4:1 and the mole ratio of the aliphatic or
aromatic end segment to the polyhydroxy segment is at least
0.25:1.
[0006] In yet another embodiment, the present disclosure provides
for an aqueous thickener composition including the various
embodiments of composition described herein and a viscosity
suppressing additive selected from an organic co-solvent, a
surfactant, a cyclodextrin compound or combinations thereof, and
water. In some embodiments, the aqueous thickener composition
includes 5 wt. % to 50 wt. % of the composition 0.1 wt. % to 25 wt.
% of viscosity suppressant, and the balance being water.
[0007] In still yet another embodiment, the present disclosure
provides for a method to improve ICI viscosity of an aqueous
composition. An effective amount of an ICI thickening composition
is provided to an aqueous composition, the ICI thickening
composition described herein wherein the ICI viscosity of the
aqueous composition ranges from 0.5 to 5.0.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0008] In an embodiment, the composition comprises linked segments
of: (a) a polyhydroxy segment derived from a compound independently
selected from the group of an acyclic polyhydric alcohol having 4
to 6 carbon atoms and 4 to 6 reactive hydroxyl groups; a cyclic
polyhydric alcohol having 4 to 6 carbon atoms and 4 to 6 reactive
hydroxyl groups, a poly(hydroxyethyl) polyethyleneamine having 4 to
6 reactive hydroxyl groups and combinations thereof; (b)
polyoxyalkylene segments wherein each hydroxyl group of the
polyhydroxyl segment is linked to a polyoxyalkylene segment; (c)
and aliphatic end segments or aromatic end segments, each aliphatic
or aromatic group, of said end segments, having 6 to 32 carbon
atoms and a hydroxyl reactive linking group, wherein the mole ratio
of the polyoxyalkylene segment to the polyhydroxy segment is at
least 4:1 and the mole ratio of the aliphatic or aromatic end
segment to the polyhydroxy segment is at least 0.25:1. In one
embodiment, the aliphatic end segment or aromatic end segment is
linked to an unlinked end of the polyoxyalkylene segment linked to
the polyhydoxyl segment.
[0009] In another embodiment, the composition comprises linked
segments of: (a) a polyhydroxy segment derived from a compound
independently selected from the group of an acyclic polyhydric
alcohol having 4 to 6 carbon atoms and 4 to 6 reactive hydroxyl
groups; a cyclic polyhydric alcohol having 4 to 6 carbon atoms and
4 to 6 reactive hydroxyl groups, an alkoxylated acyclic polyhydric
alcohol, an alkoxylated cyclic polyhydric alcohol, a
poly(hydroxyethyl) polyethyleneamine having 4 to 6 reactive
hydroxyl groups and combinations thereof; (b) aliphatic linking
segments or aromatic linking segments, each linking segment having
at least two linking groups independently selected from the group
consisting of: urethane linking group (O--C(.dbd.O)--NH), urea
linking group (N(R)--C(.dbd.O)--NH) ether linking group (--O--),
ester linking group (--C(.dbd.O)O--), amine linking group (--NH--),
an aminoplast segment, a linking group which is the residue from
reaction of an epihalohydrin and a hydroxyl group, and mixtures
thereof; (c) polyoxyalkylene segments; (d) and aliphatic end
segments or aromatic end segments, each aliphatic or aromatic
group, of said end segments, having 6 to 32 carbon atoms and a
hydroxyl reactive linking group, wherein the mole ratio of the
polyoxyalkylene segment to the polyhydroxy segment is at least 4:1
and the mole ratio of the aliphatic or aromatic end segment to the
polyhydroxy segment is at least 0.25:1.
[0010] As used herein, "aliphatic" refers to saturated or partially
unsaturated linear-, branched-, or cycloaliphatic, or combinations
thereof.
[0011] For the various embodiments of the ICI viscosity regulating
compositions described herein, such compositions includes
segment(s) of a polyhydroxy segment derived from a compound
including an acyclic polyhydric alcohol having 4 to 6 carbon atoms
and 4 to 6 reactive hydroxyl groups; a cyclic polyhydric alcohol
having 4 to 6 carbon atoms and 4 to 6 reactive hydroxyl groups, an
alkoxylated acyclic polyhydric alcohol, an alkoxylated cyclic
polyhydric alcohol, a poly(hydroxyethyl) polyethyleneamine having 4
to 6 reactive hydroxyl groups and combinations thereof.
[0012] In one embodiment, the acyclic polyhydric alcohol
independently includes pentaerythritol, erythritol, xylitol,
sorbitol, mannitol and mixtures thereof. In another embodiment, the
cyclic polyhydric alcohol independently includes inositol,
glucopyranose and mixtures thereof. In yet another embodiment, the
acyclic polyhydric alcohol independently includes pentaerythritol,
erythritol, and mixtures thereof. In one embodiment, the
poly(hydroxyethyl) polyethyleneamine having 4 to 6 reactive
hydroxyl groups includes tetra(hydroxyethyl) ethylene diamine,
penta(hydroxyethyl) diethylene triamine, hexa(hydroxyethyl)
triethylene tetraamine and mixtures thereof.
[0013] In one embodiment, the alkoxylated acyclic polyhydric
alcohol independently includes alkoxylated pentaerythritol,
alkoxylated erythritol, alkoxylated xylitol, alkoxylated sorbitol,
alkoxylated mannitol and mixtures thereof. In such embodiments, the
alkoxylated acyclic polyhydric alcohol includes 4 to 30 oxyalkylene
repeat units. In such embodiments, the alkylene oxide repeat units
include ethylene oxide repeat units, propylene oxide repeat units,
butylene oxide repeat units and mixtures thereof. In another
embodiment, the alkoxylated acyclic polyhydric alcohol
independently includes ethoxylated pentaerythritol, ethoxylated
erythritol, ethoxylated xylitol, ethoxylated sorbitol, ethoxylated
mannitol and mixtures thereof. In such embodiments, the alkoxylated
acyclic polyhydric alcohol includes 4 to 30 ethylene oxide repeat
units.
[0014] In another embodiment, the alkoxylated cyclic polyhydric
alcohol independently includes alkoxylated inositol, alkoxylated
glucopyranose and mixtures thereof. In such embodiments, the
alkoxylated acyclic polyhydric alcohol includes 4 to 30 oxyalkylene
repeat units. In yet another embodiment, the alkoxylated cyclic
polyhydric alcohol independently includes ethoxylated inositol,
ethoxylated glucopyranose and mixtures thereof. In such
embodiments, the alkoxylated cyclic polyhydric alcohol includes 4
to 30 ethylene oxide repeat units.
[0015] The various embodiments of ICI viscosity regulating
composition described herein further includes polyoxyalkylene
segments which refers to polyethylene oxide polymer segments or a
polyethylene oxide-polypropylene oxide copolymer segments,
hereinafter designated polyoxyalkylene segments or polyoxyalkylene
segments where the term "oxyalkylene" refers to units having the
structure --(O-A)-, with O-A represents the monomeric residue of
the polymerization reaction product of C.sub.2-.sub.8 alkylene
oxides or diols. Examples of oxyalkylenes include, but are not
limited to: oxyethylene with the structure --(OCH.sub.2CH.sub.2);
oxypropylene with the structure --(OCH(CH.sub.3)CH.sub.2-- or
--(OCH.sub.2(CH--)CH.sub.3; oxytrimethylene with the structure
--(OCH.sub.2CH.sub.2CH.sub.2)--; 1,2 oxybutylene with the structure
--(OCH2CH(C2H5))- or --(OCH(C2H5)CH2)-, and 1,4-oxybutylene with
the general structure --(OC.sub.4H.sub.8)--. Segments containing
these units are referred to as "polyoxyalkylenes." The
polyoxyalkylene segments can be homopolymeric or copolymeric.
Examples of homopolymers of polyoxyalkylene segments include, but
are not limited to polyoxyethylene, which contains segments of
oxyethylene; polyoxypropylene, which contains segments of
oxypropylene; polyoxytrimethylene, which contains segments of
oxytrimethylene; and polyoxybutylene, which contains segments of
oxybutylene. Examples of polyoxybutylene include a homopolymer
containing segments of 1,2-oxybutylene,
--(OCH(C.sub.2H.sub.5)CH.sub.2)--; and polytetrahydrofuran, a
homopolymer containing segments of 1,4-oxybutylene, or
--(OCH.sub.2CH.sub.2CH.sub.2CH.sub.2)--.
[0016] In other embodiments, the polyoxyalkylene segments can be
copolymeric, containing two or more different oxyalkylene segments.
The different oxyalkylene groups, within a segment, can be arranged
randomly to form a random polyoxyalkylene segment; a tapered
polyoxyalkylene segment, or can be arranged in blocks to form a
block polyoxyalkylene segment. A tapered polyoxyalkylene segments
contains mixtures of alkylene oxides as would occur from the
transition of one alkylene oxide to another during the
polymerization of different alkylene oxides. Block polyoxyalkylene
segments have two or more neighboring polymer blocks, wherein each
of the neighboring polymer blocks contain different oxyalkylene
blocks, and each polymer block contains at least two of the same
oxyalkylene blocks. In one such embodiment, an oxyalkylene group is
oxyethylene.
[0017] In other embodiments, the polyoxyalkylene segments have a
nominal number average molecular weight ranging from 3,000-10,000
g/mole. In other embodiments, the polyoxyethylene segments have a
nominal number average molecular weight ranging from 3,000-10,000
g/mole. In another embodiment, the polyoxyalkylene segments have a
number average molecular weight of up to about 6,000-9,000 g/mole.
In another embodiment, the polyoxyethylene segments have a number
average molecular weight of up to about 6,000-9,000 g/mole. In
another embodiment, the polyoxyalkylene segments have a number
average molecular weight of up to about 7,000-9,000 g/mole. In
another embodiment, the polyoxyethylene segments have a number
average molecular weight of up to about 7,000-9,000 g/mole.
[0018] In certain embodiments, a single polyoxyalkylene segment may
have from about 60 to about 225 alkylene oxide repeat units. In
certain embodiments, a single polyoxyalkylene segment may have from
about 160 to about 210 alkylene oxide repeat units. In such
embodiments, the alkylene oxide repeat units include ethylene oxide
repeat units, propylene oxide repeat units, butylene oxide repeat
units and mixtures thereof.
[0019] In certain embodiments the polyoxyalkylene segments are
built into the various ICI viscosity regulating compositions via
state of the art alkoxylation processes. The polyhydroxyl segments
are reacted with ethylene oxide, propylene oxide or butylene oxide
or mixtures thereof in the presence of a catalyst and at
temperatures ranging from 100-180.degree. C. and pressures from
1-10 Bar. The catalyst can be an alkaline catalyst from the range
of NaOH or KOH or a Lewis acid like for example BF.sub.3.
[0020] In other embodiments, the aliphatic end segments or aromatic
end segments include a hydroxyl reactive linking group including an
isocyanate group, an epoxide group, an acid group, an ester group
or a halide. In one embodiment the isocyanate containing moiety
independently includes dodecylisocyanate and stearyl isocyanate. In
another embodiment, the epoxide containing moiety independently
includes 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane,
1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane,
2-ethylhexylglycidylether, dodecyl glycidylether, tridecyl
glycidylether, hexadecylglycidylether, alkylphenyl glycidylether
and mixtures thereof. In another embodiment, the acid containing
moiety independently includes 2-ethylhexanoic acid, isononanoic
acid, decanoic acid, dodecanoic acid, 2-butyl octanoic acid and
mixtures thereof. In another embodiment, the ester containing
moiety independently includes methyl decanoate, methyl dodecanoate
and ethyl dodecanoate. In yet another embodiment the halide
containing moiety independently includes 1-chlorododecane,
1-bromododecane and 1-chloro-2-hydroxy-3-(dodecyloxy)propane.
[0021] In some embodiments, the ICI viscosity regulating
composition has polyoxyalkylene oxide segment to polyhydric alcohol
segment mole ratio ranging from: 4:1 to 6:1. In some such
embodiments, the ICI viscosity regulating composition has
polyhydric alcohol segment to aliphatic or aromatic end segment
mole ratios ranging from: 1:0.25 to 1:24.
[0022] The present disclosure further provides for an aqueous
thickening composition containing the various embodiments of the
ICI viscosity regulating composition described herein, a viscosity
suppressant and water. In some embodiments, the aqueous thickening
composition may contain 5-50 wt. % of the ICI viscosity regulating
composition described herein, 0.1-25 wt. % of a viscosity
suppressant; and the balance being water. In some embodiments, the
aqueous thickening composition may contain 5-30 wt. % of the ICI
viscosity regulating composition described herein, 0.1-25 wt. % of
a viscosity suppressant; and the balance being water. In some
embodiments, the aqueous thickening composition may contain 15-30
wt. % of the ICI viscosity regulating composition described herein,
5-25 wt. % of a viscosity suppressant; and the balance being
water.
[0023] In some embodiments, the viscosity suppressant is an organic
solvent such as butoxyethanol, diethylene glycol monobutyl ether,
triethylene glycol monobutyl ether, propylene glycol, and other
water miscible organic solvents. In other embodiments, the
viscosity suppressant is an inorganic salt such as sodium chloride.
In still other embodiments, the viscosity suppressant is a nonionic
or anionic surfactant.
[0024] In one embodiment, each nonionic surfactant and anionic
surfactant includes one or more hydrophobic group(s) and
hydrophilic group(s), each of the hydrophobic group(s) having from:
6 carbon atoms to 10 carbon atoms; or 6 carbon atoms to 8 carbon
atoms. In one embodiment, the anionic surfactant includes
M.sup.+(2-ethylhexyl sulfate.sup.-); M.sup.+(hexylsulfate.sup.-);
M.sup.+(octylsulfate.sup.-) and M.sup.+(dioctyl
sulfosuccinate.sup.-), and mixtures thereof, where M.sup.+ includes
NH.sub.4.sup.+, Na.sup.+ and K.sup.+. In another embodiment, the
anionic surfactant includes sodium 2-ethylhexyl sulfate; sodium
hexylsulfate; sodium octylsulfate, sodium dioctyl sulfosuccinate;
ammonium 2-ethylhexyl sulfate; ammonium hexylsulfate; ammonium
octylsulfate, ammonium dioctyl sulfosuccinate and mixtures thereof.
In another embodiment, the anionic surfactant includes sodium
2-ethylhexyl sulfate; sodium octylsulfate, sodium dioctyl
sulfosuccinate and mixtures thereof. In another embodiment, the
nonionic surfactant is 2-ethylhexyl ethoxylate having 2-5 moles
ethylene oxide.
[0025] In some embodiments, the aqueous thickener blend composition
may have a viscosity of up to: 2500 cP; 5000 cP; 10,000 cP; 15,000
cP; 20,000 cP; or 25,000 cP. In one such embodiment, the
composition may have a viscosity ranging from: 10 to 2500 cP; 10 to
5000 cP; 10 to 10000 cP; 10 to 15,000 cP; 10 to 20,000 cP; or 10 to
25,000 cP. Brookfield viscosities of such compositions are measured
at 25.degree. C. and 10 RPM using a Brookfield RV or RVT. Typically
a #1 spindle is used for materials having a Brookfield viscosity of
400-600 cP (40-60 dial reading), a #2 spindle is used for materials
having a Brookfield viscosity of 1600-2400 cP and a #3 spindle is
used for materials having a Brookfield viscosity of 4000-6000 cP.
The following table may also be used to determine the appropriate
spindle to use when measuring Brookfield viscosity at 25.degree. C.
and 10 RPM:
TABLE-US-00001 Viscosity (cP) Spindle Factor Mid-dial Max 1 10 500
1000 2 40 2000 4000 3 100 5000 10000 4 200 10000 20000 5 400 20000
40000 6 1000 50000 100000 7 4000 200000 400000
[0026] In another embodiment, the present invention provides for a
method to improve ICI viscosity of an aqueous composition
comprising: providing an effective amount of an ICI thickening
composition according to the various embodiments described herein
to an aqueous composition, wherein the ICI viscosity of the aqueous
composition ranges from 0.5 to 5.0.
Paint Formulations
[0027] A variety of paint formulations may be formulated using the
ICI viscosity regulating composition described herein and/or the
aqueous thickening compositions, as described herein. In one
embodiment, a paint formulation includes: 10-50 wt. % solids of a
resin system; 0.0-2.0 wt. % actives of an associative co-thickener;
0.1-3.0 wt. % actives of the ICI viscosity regulating composition
according to the various embodiments discussed herein; and
optionally 1-12 wt. % of a colorant composition.
[0028] In one embodiment, the ICI viscosity of a paint formulation
ranges from 0.5 to 5.0. In another embodiment, the ICI viscosity of
a paint formulation ranges from 0.5 to 4.0. In yet another
embodiment, the ICI viscosity of a paint formulation ranges from
0.5 to 3.0. In still yet another embodiment, the KU viscosity of a
paint formulation is at least 60. In another such embodiment, the
KU viscosity of a paint formulation ranges from 60 to 130.
[0029] A paint formulation of some embodiments of the present
invention may include one or more resin film forming binders. A
binder, or resin, is the actual film forming component of paint. It
is an essential component of a base paint; and other components
listed herein are included optionally, depending on the desired
properties of the cured film. Binders can be categorized according
to drying, or curing mechanism. The four most common are simple
solvent evaporation, oxidative crosslinking, catalyzed
polymerization, and coalescence.
[0030] In some embodiments, the resin binder is a water dispersible
resin, such as a water dispersible alkyd or water dispersible
polyurethane. In some embodiments, the resin binder is a water
soluble resin. In certain embodiments, the resin binder is an
emulsion resin, such as is typically used to manufacture latex
paints. In certain embodiments, the resin includes a hydrophobic
resin. Representative hydrophobic emulsion resins may include
(meth)acrylic resin, a styrene acrylic resin, a styrene resin or
other ethylenically unsaturated monomers. Representative examples
of hydrophilic emulsion resins may include a vinyl acrylic resin or
a vinyl acetate ethylene resin. In certain embodiments, the resin
may have a substantially spherical shape and a large particle size
or low surface area. In one embodiment, the particle size may be
greater than about 200 nm. In a further embodiment, the particle
size ranges from about 220 nm to about 650 nm. In certain
embodiments, the resin may have a substantially spherical shape and
small particle size or high surface area. In one embodiment, the
particle size may be less than about 200 nm. In a further
embodiment, the particle size ranges from about 40 nm to about 180
nm. In certain embodiments, the resin may have a multilobe shape.
Representative resins may include Optive 130 (BASF, acrylic, 160
nm), UCAR 300 (Dow, vinyl acrylic, 260 nm), UCAR 625 (Dow, acrylic,
340 nm), Rhoplex ML-200 (Rohm & Haas, acrylic, 590 nm
multilobe), and Neocryl XK-90 (DSM Neoresins, acrylic, 90 nm). In
certain embodiments, combinations of resins are used to prepare the
base paint.
[0031] The paint formulation may also include at least one
associative co-thickener. Associative co-thickeners are water
soluble, water dispersible, or water swellable polymers that have
chemically attached hydrophobic groups. In certain embodiments, a
paint formulation includes a condensation polymer associative
co-thickener including but not limited to polyether polyurethanes,
polyether polyols, polyether polyacetals, polyether aminoplasts and
the like. In some embodiments, a paint formulation includes about
0.05 wt % to about 5 wt % as active polymer of a condensation
polymer associative co-thickener, about 0.1 wt % to about 3 wt % as
active polymer of a condensation polymer associative co-thickener,
or about 0.2 wt % to about 1 wt % as active polymer of a
condensation polymer associative co-thickener.
[0032] In some embodiments, the associative co-thickener includes
polyurethane thickener; a hydrophobically modified cellulose; a
hydrophobically modified alkali soluble thickener; an alkali
soluble thickener; a cellulose thickener; a polyacetalpolyether;
polyetherpolyol thickener; smectite clays and mixtures thereof.
[0033] In other embodiments, the associative co-thickeners include
nonionic hydrophobically modified materials including nonionic
hydrophobically-modified ethylene oxide urethane copolymers,
nonionic hydrophobically-modified ethylene oxide ether copolymers,
nonionic hydrophobically-modified ethylene oxide glycouril
copolymers, hydrophobically-modified alkali soluble emulsions,
hydrophobically-modified poly(meth)acrylic acids,
hydrophobically-modified hydroxyethyl cellulose, and
hydrophobically-modified poly(acrylamide), and mixtures thereof.
The number average molecular weights of the associative
co-thickeners may range from about 10,000 to about 500,000 g/mole
or more, depending on the chemical type of associative thickener.
In some embodiments, the number average molecular weight of the
associate do-thickeners may range from about 10,000 to about 50,000
g/mole. In some embodiments, the number average molecular weight of
the associate co-thickeners may range from about 100,000 to about
300,000 g/mole. In some embodiments, the number average molecular
weight of the associate co-thickeners may range from about 400,000
to about 500,000 g/mole or more.
[0034] In another embodiment, the associative co-thickener may
include an KU associative thickener which is used to increase the
low to mid shear viscosity of a composition.
[0035] A colorant containing paint formulation of the present
invention may also include any suitable colorant. In some
embodiments, a predispersed colorant may be added to a paint
formulation. It is to be understood that this invention is equally
effective with single colorants or mixtures of colorants.
[0036] Within the context of this invention, a colorant or colorant
compound may include one or more colored pigment(s) which have been
dispersed in an aqueous or water-miscible medium external to the
paint in which it is intended to be used by use of mechanical
energy, i.e., grinding or shearing by means of dispersing equipment
such as, for example, a ball mill and a sand mill and then
dispersed into a base paint. For the purposes of this disclosure,
colorant does not include pigments in a dry undispersed state. The
dispersion process is typically achieved by the use of auxiliary
compounds such as, for example, surfactants, wetting agents,
water-miscible solvents, and dispersants, in addition to mechanical
energy. The aqueous or water-miscible medium may also include
glycols such as ethylene glycol and propylene glycol, and alcohols
such as isopropanol. Dispersants may include polyethylene oxide
polymers, polyethylene oxide glycols and others. The aqueous or
water-miscible medium may also include extenders such as talc and
calcium carbonate; humectants; thickeners; defoamer; and biocides.
Such colorants are frequently added to a base paint or tint base at
the point-of-sale to produce custom colors.
[0037] Pigments which are commonly used to prepare colorants
include one or more inorganic or organic pigments, or metal effect
agents, or combinations thereof. Examples of suitable pigments
include titanium dioxide white, carbon black, lamp black, black
iron oxide, red iron oxide, yellow iron oxide, brown iron oxide (a
blend of red and yellow oxide with black), phthalocyanine green,
phthalocyanine blue, organic red pigment (such as naphthol red,
quinacridone red and toluidine red), quinacridone magenta,
quinacridone violet, DNA orange, and organic yellow pigment (such
as Hansa yellow) and combinations thereof.
[0038] The colorants are usually sold in concentrated form
(typically 25% to 75% solids by weight) so that modest amounts can
be used in a waterborne coating composition to provide a desired
range of color intensities while not compromising the properties of
the waterborne coating composition unduly. Typical amounts of
colorants which are used in architectural coatings are from 2 to 4
fluid ounces of colorant per gallon of base paint for light tint
bases and pastels, from 4 to 8 fluid ounces of colorant per gallon
of base paint for medium tint bases, and from 6 to 16 fluid ounces
of colorant per gallon of base paint for deep tone tint bases. Of
course, different colorants and mixtures thereof are frequently
used to provide wide latitude in color selection. Such colorants
are frequently added to a base paint at the point-of-purchase of
the colored paint, such as a paint store, followed by admixing the
colorant and the waterborne coating composition by various means
such as shaking the can of paint.
[0039] A paint system of some embodiments of the present invention
may include additional components as suitable to achieve the desire
effect, including but not limited to wetting agents, fillers;
pigments, such as titanium dioxide, mica, calcium carbonate,
silica, zinc oxide, milled glass, aluminum trihydrate, talc,
antimony trioxide, fly ash, and clay; polymer encapsulated
pigments, such as polymer-encapsulated or partially encapsulated
pigment particles such as titanium dioxide, zinc oxide, or
lithopone particles; polymers or polymer emulsions adsorbing or
bonding to the surface of pigments such as titanium dioxide; hollow
pigments, including pigments having one or more voids; dispersants,
such as aminoalcohols and polycarboxylates; surfactants; defoamers;
preservatives, such as biocides, mildewcides, fungicides,
algaecides, and combinations thereof; flow agents; leveling agents;
and additional neutralizing agents, such as hydroxides, amines,
ammonia, and carbonates.
[0040] Paint formulations may be characterized by a variety of
properties including Stormer (KU) viscosity, ICI viscosity, sag and
leveling.
[0041] Stormer viscosity relates to the in-can appearance and is
typically measured in Krebs units (KU) using a Stormer viscometer.
Mid-shear or Statiner viscosity was measured by the test method
described in ASTM D562-01 "Standard Test Method Consistency of
Paints Measuring Krebs Unit (KU) Viscosity Using a Stormer-Type
Viscometer."
[0042] ICI viscosity represents the viscosity of the paint during
typical brush and roller application conditions. It is typically
measured at 10,000 sec.sup.-1 by the test method described in ASTM
D4287-00 "Standard Test Method for High-Shear Viscosity Using a
Cone/Plate Viscometer."
[0043] The sag and leveling properties of a film, on a substrate,
formed by application of a paint formulation, containing the
mid-shear regulating composition, were also measured. Sag values
were measured following the test method described in ASTM D4400-99
(Reapproved 2007) "Standard Test Method for Sag Resistance of
Paints Using a Multinotch Applicator." The leveling values were
measured following the test method described in ASTM D4062-99
(Reapproved 2003) "Standard Test Method for Leveling of Paints by
Draw-Down Method."
[0044] By way of a non-limiting example, the compounds encompassed
herein are used to make high-shear (e.g., ICI) viscosity regulating
compositions.
[0045] For the purposes of this disclosure, the term "about" means
plus or minus 10%.
EXAMPLES
[0046] The following examples further describe and demonstrate
illustrative embodiments within the scope of the present invention.
The examples are given solely for illustration and are not to be
construed as limitations of this invention as many variations are
possible without departing from the spirit and scope thereof. For
reactions using diisocyanate reactants, a catalyst such as an
organo-tin or bismuth ester or an amine may be added to accelerate
the reaction at the desired temperature. The reactions may be
conducted under conditions to minimize branching and/or side
reactions.
Comparative Example A
[0047] A viscosity regulating composition was prepared as follows:
To a 500 ml reaction kettle equipped with a nitrogen inlet,
stirrer, Dean Stark trap and a condenser, 45.13 g of PEG 8000
(Mn=7545, 0.006 mol), 0.27 g of trimethylolpropane (MW=134.17,
0.002 mol) and 300 g of toluene were added. The reaction mixture
was stirred at 250 rpm and dewatered at 130.degree. C., with a
N.sub.2 purge, 0.5 ml/min, to remove 120 ml of the toluene/H.sub.2O
mixture. The reaction was cooled to 75.degree. C. followed by
addition of 2.01 g of hexamethylene diisocyanate (HDI) (MW=168.19:
0.012 mol) and 3 drops of K-Kat 348. The reaction is stirred at
75.degree. C. for 1.5 hour. To this mixture, 1.11 g of 1-dodecanol
(MW=186.34, 0.006 mol) was added and the reaction mixture was
stirred at 75.degree. C. for 1 hour. The mixture was cooled and
poured onto a plastic tray to evaporate toluene. The polymer was
further dried in a vacuum oven.
Example 1
[0048] A viscosity regulating composition was prepared as follows:
To a 500 ml reaction kettle equipped with a nitrogen inlet,
stirrer, and a distillation setup, 4.46 g of ethoxylated
pentaerythritol (5 EO, Mn=356.7, 0.013 mol) and 1.40 g of 50%
potassium hydroxide (catalyst, MW=56.1, 0.012 mol) were added. The
reaction mixture was stirred at 250 rpm and dewatered at
125.degree. C., with a N.sub.2 purge, 0.5 ml/min, until a water
content of <250 ppm was reached. The mixture was heated to
140.degree. C. and 195.80 g ethylene oxide (Mn=44.10; 4.440 mol)
was added in 1 hour. The reaction mixture was stirred at
140.degree. C. for 3 hours. The reaction temperature was lowered to
125.degree. C. and to the reaction mixture 18.43 g of
1,2-epoxydodecane (MW=184.32, 0.100 mol) was added. The reaction is
stirred at 125.degree. C. for 3 hours, followed by cooling down to
75.degree. C. To this mixture, 1.10 g of acetic acid (MW=60.05,
0.018 mol) was added to neutralize the catalyst and stirred at
75.degree. C. for 30 minutes.
Example 2
[0049] A viscosity regulating composition was prepared as follows:
To a 500 ml reaction kettle equipped with a nitrogen inlet,
stirrer, and a distillation setup, 4.46 g of ethoxylated
pentaerythritol (5 EO, Mn=356.7, 0.013 mol) and 1.40 g of 50%
potassium hydroxide (catalyst, MW=56.1, 0.012 mol) were added. The
reaction mixture was stirred at 250 rpm and dewatered at
125.degree. C., with a N.sub.2 purge, 0.5 ml/min, until a water
content of <250 ppm was reached. The mixture was heated to
140.degree. C. and 195.80 g ethylene oxide (Mn=44.10; 4.440 mol)
was added in 1 hour. The reaction mixture was stirred at
140.degree. C. for 3 hours. The reaction temperature was lowered to
75.degree. C. and 1.10 g of acetic acid (MW=60.05, 0.018 mol) was
added to neutralize the catalyst. The temperature was raised to
120.degree. C. and the reaction mixture was dewatered with a
N.sub.2 purge, 0.5 ml/min, until a water content of <250 ppm was
reached. To the reaction mixture 14.35 g of commercial quality
stearyl isocyanate (MW=287.0, 0.050 mol) was added. The reaction is
stifled at 120.degree. C. for 3 hours, followed by cooling.
Aqueous Composition Example 1
[0050] An exemplary viscosity regulating solution composition based
on the viscosity regulating composition prepared in Example 1, was
prepared by combining 25 wt. % of the viscosity regulating
composition; 18.5% of the viscosity suppressant Butyl Carbitol and
56.5% of water.
[0051] The present disclosure may be embodied in other specific
forms without departing from the spirit or essential attributes of
the invention. Accordingly, reference should be made to the
appended claims, rather than the foregoing specification, as
indicating the scope of the disclosure. Although the foregoing
description is directed to the preferred embodiments of the
disclosure, it is noted that other variations and modification will
be apparent to those skilled in the art, and may be made without
departing from the spirit or scope of the disclosure.
* * * * *