U.S. patent application number 14/875097 was filed with the patent office on 2016-01-28 for oxidized carbon blacks treated with polyetheramines and coating compositions comprising same.
The applicant listed for this patent is Cabot Corporation. Invention is credited to Lang H. Nguyen, Joshua B. Preneta, Angelica Maria Sanchez Garcia, Jeffrey Scott Sawrey, Eugene N. Step.
Application Number | 20160024345 14/875097 |
Document ID | / |
Family ID | 48050268 |
Filed Date | 2016-01-28 |
United States Patent
Application |
20160024345 |
Kind Code |
A1 |
Sanchez Garcia; Angelica Maria ;
et al. |
January 28, 2016 |
Oxidized Carbon Blacks Treated with Polyetheramines and Coating
Compositions Comprising Same
Abstract
Disclosed herein are materials and compositions comprising: an
oxidized carbon black having a BET surface area ranging from 50 to
700 m.sup.2/g, a DBP oil adsorption number ranging from 50 to 200
mL/100 g, and a primary particle size ranging from 7 to 30 nm; and
a polyetheramine comprising ethylene oxide and propylene oxide
monomers, wherein the polyetheramine coats the oxidized carbon
black. Also disclosed are coatings and coating compositions
comprising these materials and methods of making the same.
Inventors: |
Sanchez Garcia; Angelica Maria;
(Birmingham, MI) ; Step; Eugene N.; (Newton,
MA) ; Sawrey; Jeffrey Scott; (Westford, MA) ;
Nguyen; Lang H.; (Lowell, MA) ; Preneta; Joshua
B.; (Billerica, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Cabot Corporation |
Boston |
MA |
US |
|
|
Family ID: |
48050268 |
Appl. No.: |
14/875097 |
Filed: |
October 5, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14387293 |
Sep 23, 2014 |
9150739 |
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PCT/US2013/031290 |
Mar 14, 2013 |
|
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14875097 |
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61616451 |
Mar 28, 2012 |
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Current U.S.
Class: |
524/496 ;
427/212 |
Current CPC
Class: |
C09C 1/56 20130101; C01P
2006/64 20130101; C01P 2006/12 20130101; C08K 2201/006 20130101;
C09D 171/02 20130101; C01P 2006/19 20130101; C08K 3/04 20130101;
C09D 7/62 20180101; C09D 7/67 20180101; Y10T 428/2998 20150115;
C01P 2006/63 20130101; C08K 9/08 20130101; C01P 2006/62 20130101;
C09D 179/02 20130101; C08K 2201/003 20130101; C09C 1/565 20130101;
B82Y 30/00 20130101; C01P 2004/64 20130101; C09D 5/00 20130101 |
International
Class: |
C09D 179/02 20060101
C09D179/02; B05D 1/02 20060101 B05D001/02; C08K 3/04 20060101
C08K003/04 |
Claims
1. A powdered material comprising: an oxidized carbon black having
a BET surface area ranging from 50 to 700 m.sup.2/g, a DBP oil
adsorption number ranging from 50 to 200 mL/100 g, and a primary
particle size ranging from 7 to 30 nm; and a polyetheramine wherein
said polyetheramine consists of ethylene oxide and propylene oxide
monomers and one or more amine groups and wherein the
polyetheramine coats the oxidized carbon black.
2. The powdered material of claim 1, wherein the polyetheramine has
a molecular weight ranging from 250 to 5,000.
3. (canceled)
4. The powdered material according to claim 1, wherein the
propylene oxide and ethylene oxide monomers are present in the
polyetheramine in a ratio ranging from 1:2 to 9:1.
5. (canceled)
6. The powdered material according to claim 1, wherein the
polyetheramine is present in the powdered material in an amount
ranging from 5 to 30% by weight.
7. (canceled)
8. The powdered material according to claim 1, wherein the oxidized
carbon black is present in the powdered material in an amount
ranging from 65 to 95%.
9. (canceled)
10. The powdered material according to claim 1, wherein the
oxidized carbon black is formed by oxidation of unmodified carbon
black.
11. The powdered material according to claim 1, wherein the
material is a bulk powdered material.
12. The powdered material of claim 1, wherein: the polyetheramine
has the formula: ##STR00003## wherein x=1-35, y=3-30, x/y is at
least 0.15, and the polyetheramine coats the oxidized carbon
black.
13. The powdered material of claim 12, wherein x/y is at least
0.3.
14. (canceled)
15. A pellet comprising: an oxidized carbon black having a BET
surface area ranging from 50 to 700 m.sup.2/g, a DBP oil adsorption
number ranging from 50 to 200 mL/100 g, and a primary particle size
ranging from 7 to 30 nm; and a polyetheramine wherein said
polyetheramine consists of ethylene oxide and propylene oxide
monomers and one or more amine groups and wherein the
polyetheramine coats the oxidized carbon black.
16. The pellet of claim 15, wherein: the polyetheramine has the
formula: ##STR00004## wherein x=1-35, y=3-30, x/y is at least 0.15,
and the polyetheramine coats the oxidized carbon black.
17. The pellet of claim 15, wherein the pellet has a D50 of at
least 100 .mu.m.
18-21. (canceled)
22. A coating composition, comprising: an oxidized carbon black
having a BET surface area ranging from 50 to 700 m.sup.2/g, a DBP
oil adsorption number ranging from 50 to 200 mL/100 g, and a
primary particle size ranging from 7 to 30 nm, a polyetheramine
wherein said polyetheramine consists of ethylene oxide and
propylene oxide monomers and one or more amine groups and wherein
the polyetheramine coats the oxidized carbon black and a resin
having a molecular weight of at least 10,000.
23. The composition of claim 22, wherein the resin is selected from
acrylics, polyesters, polyurethanes, alkyds, cellulose acetate
butyrate, nitro cellulose, melamines, epoxies, and blends and
copolymers thereof.
24-25. (canceled)
26. The composition according to claim 22, wherein the
polyetheramine has a molecular weight ranging from 500 to
5,000.
27. The composition according to claim 22, wherein the propylene
oxide and ethylene oxide monomers are present in the polyetheramine
in a ratio ranging from 1:2 to 9:1.
28. The composition according to claim 22, wherein the resin is
present in the composition in an amount of at least 60% by
weight.
29. The composition according to claim 22, wherein the oxidized
carbon black is present in the composition in an amount ranging
from 1% to 30% by weight.
30-32. (canceled)
33. A coating comprising: an oxidized carbon black having a BET
surface area ranging from 50 to 700 m.sup.2/g, a DBP oil adsorption
number ranging from 50 to 200 mL/100 g, and a primary particle size
ranging from 7 to 30 nm, a polyetheramine wherein said
polyetheramine consists of ethylene oxide and propylene oxide
monomers and one or more amine groups and wherein the
polyetheramine coats the oxidized carbon black and a resin selected
from acrylics, polyesters, polyurethanes, alkyds, cellulose acetate
butyrate, nitro cellulose, melamines, epoxies, and blends and
copolymers thereof.
34. (canceled)
35. A method of preparing a pellet or powdered material,
comprising: coating an oxidized carbon black with a polyetheramine,
wherein the oxidized carbon black is obtained by oxidizing an
unmodified carbon black having a BET surface area ranging from 50
to 700 m.sup.2/g, a DBP oil adsorption number ranging from 50 to
200 mL/100 g, and a primary particle size ranging from 7 to 30 nm,
wherein said polyetheramine consists of ethylene oxide and
propylene oxide monomers and one or more amine groups.
36. The method of claim 35, wherein the step of coating comprises
spraying the polyetheramine onto the oxidized carbon black.
37. The method of claim 35, wherein the oxidized carbon black is
obtained by oxidizing the unmodified carbon black with nitric
acid.
38.-41. (canceled)
Description
RELATED APPLICATION
[0001] This application claims priority under 35 U.S.C.
.sctn.119(e) to U.S. Prov. App. 61/616,451, filed Mar. 28, 2012,
the disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] Disclosed herein are oxidized carbon blacks treated with
polyetheramines and their use in coatings and coating
compositions.
BACKGROUND
[0003] Carbon black is the most widely used black pigment in both
water- and solvent-based formulations for surface coatings, which
typically include resins. The color of the coating depends on
several factors including carbon black loading, the quality of a
carbon black dispersion in the resin matrix, the specific carbon
black grade, and primary particle size and aggregate size.
Accordingly, there remains a need to improve coating
formulations.
SUMMARY
[0004] One embodiment provides a pellet or powdered material
comprising:
[0005] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm; and
[0006] a polyetheramine comprising ethylene oxide and propylene
oxide monomers, wherein the polyetheramine coats the oxidized
carbon black.
[0007] Another embodiment provides a pellet or powdered material
comprising:
[0008] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm, and
[0009] a polyetheramine having the formula:
##STR00001##
[0010] wherein x=1-35, y=3-30, x/y is at least 0.15, and the
polyetheramine coats the oxidized carbon black.
[0011] Another embodiment provides a coating composition,
comprising:
[0012] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm,
[0013] a polyetheramine comprising ethylene oxide and propylene
oxide monomers, and
[0014] a resin having a molecular weight of at least 10,000.
[0015] Another embodiment provides a coating composition,
comprising:
[0016] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm,
[0017] a polyetheramine comprising ethylene oxide and propylene
oxide monomers, and;
[0018] a resin selected from acrylics, polyesters, polyurethanes,
alkyds, cellulose acetate butyrate, nitro cellulose, melamines,
epoxies, and blends and copolymers thereof.
[0019] Another embodiment provides a coating comprising:
[0020] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm,
[0021] a polyetheramine comprising ethylene oxide and propylene
oxide monomers, and
[0022] a resin selected from acrylics, polyesters, polyurethanes,
alkyds, cellulose acetate butyrate, nitro cellulose, melamines,
epoxies, and blends and copolymers thereof.
[0023] Another embodiment provides a method of preparing a pellet
or powdered material, comprising:
[0024] coating an oxidized carbon black with a polyetheramine,
wherein the oxidized carbon black is obtained by oxidizing an
unmodified carbon black having a BET surface area ranging from 50
to 700 m.sup.2/g, a DBP oil adsorption number ranging from 50 to
200 mL/100 g, and a primary particle size ranging from 7 to 30
nm.
[0025] Another embodiment provides a method of preparing a coating
composition, comprising:
[0026] preparing a millbase comprising: [0027] an oxidized carbon
black coated with a polyetheramine comprising ethylene oxide and
propylene oxide monomers; [0028] a resin having a molecular weight
of at least 10,000; and [0029] a dispersion aid.
DETAILED DESCRIPTION
[0030] Disclosed herein are compositions directed to oxidized
carbon blacks having a polyetheramine coating, coating formulations
comprising such oxidized carbon blacks, and methods of making the
same.
[0031] Black surface coatings are often prepared from formulations
containing a dispersion of carbon black and resin. Typically, an
optimal dispersion of carbon black in the final dry coating
(occurring after solvent evaporation) arises from a coating
composition comprising a dispersion of the carbon black in a liquid
formulation that is applied to a surface. In solvent-based
coatings, the stability of carbon black dispersions in solvent is
based on steric stabilization of individual pigment particles. Such
stability can be provided by dispersion aids.
[0032] More specifically, surface-oxidized carbon black grades,
which are typically used in solvent-based coating formulations,
often include amine functionalized polymers as dispersion aids
because amine groups can anchor with acidic groups on the surface
of oxidized carbon black through acid/based interaction. Because
dispersion aids are polymeric, they can provide steric
stabilization through polymer interaction with the solvent. Thus,
typical dispersion aids have a molecular weight of 30,000 to
100,000. The relatively high molecular weight, however, can hinder
and/or slow the adsorption of the dispersion aid onto the carbon
black surface. This problem can be compounded for carbon blacks
having a high surface area and small primary particle size as the
number of particle to particle contacts increases, thereby
increasing the milling time and the amount of dispersion aid to wet
the material and form a good solvent dispersion. Typically, for a
high color carbon black dispersion in solvent coating formulations,
the typical load of dispersion aid is 50% to 100% by weight of
carbon black.
[0033] Currently in the solvent-based automotive market for
basecoats, the coating formulations balance color (L) and blue
undertone (b*) properties of the carbon black, which are typically
oxidized carbon blacks. The drawback of using many of these carbon
black grades is the long dispersion time to obtain a mill base for
full color and good hiding power.
[0034] It has been discovered that treating the carbon black with
polyetheramines prior to forming the dispersions and mill base
compositions is beneficial to the coating formulations and methods
of preparing the formulations. Accordingly, one embodiment provides
a powdered material comprising:
[0035] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm; and
[0036] a polyetheramine comprising ethylene oxide and propylene
oxide monomers, wherein the polyether amine coats the oxidized
carbon black.
[0037] In one embodiment, "oxidized carbon blacks" are carbon black
pigments generally having a pH<7.0 that feature surface-bound
ionic or ionizable groups such as alcohol, phenol, and/or
carboxylic acid groups. The extent of oxidation of carbon black can
determine the surface concentration of these groups. Exemplary
oxidizing agents for carbon blacks include oxygen gas, ozone,
peroxides such as hydrogen peroxide, persulfates such as sodium and
potassium persulfate, hypohalites such as sodium hypochlorite,
nitric acid, and transition metal-containing oxidants such as
permanganate salts, osmium tetroxide, chromium oxides, ceric
ammonium nitrates, and mixtures thereof (e.g., mixtures of gaseous
oxidants such as oxygen and ozone). In one embodiment, the
"oxidized carbon blacks" are those pigments having been subjected
to an oxidation treatment.
[0038] In one embodiment oxidized carbon black is obtained from the
oxidation of unmodified carbon blacks, as described above.
Unmodified carbon black particles can be selected from channel
blacks, furnace blacks, gas blacks, and lamp blacks. Exemplary
unmodified carbon blacks include those commercially available as
Regal.RTM., Black Pearls.RTM., Elftex.RTM., Monarch.RTM.,
Mogul.RTM., and Vulcan.RTM., such as Black Pearls.RTM. 1100, Black
Pearls.RTM. 900, Black Pearls.RTM. 880, Black Pearls.RTM. 800,
Black Pearls.RTM. 700, Black Pearls.RTM. 570, Elftex.RTM. 8,
Monarch.RTM. 900, Monarch.RTM. 880, Monarch.RTM. 800, Monarch.RTM.
700, Regal.RTM. 660, and Regal.RTM. 330.
[0039] In another embodiment, the oxidized carbon black is obtained
from commercial sources, such as Black Pearls.RTM. 1400, Black
Pearls.RTM. 1300, Black Pearls.RTM. 1000, Black Pearls.RTM. L,
Monarch.RTM. 1000, Mogul.RTM. L, and Regal.RTM. 400.
[0040] In one embodiment, the oxidized carbon black is unmodified.
For example, the oxidized carbon black is formed by oxidation of
unmodified carbon black. In other embodiments, the oxidized carbon
black is further treated with other surface modification methods to
introduce ionic or ionizable groups onto a pigment surface, such as
chlorination and sulfonylation. In another embodiment, the oxidized
carbon black is modified to include attached organic groups. For
example, U.S. Pat. No. 5,851,280 discloses methods for the
attachment of organic groups onto pigments including, for example,
attachment via a diazonium reaction wherein the organic group is
part of the diazonium salt. In yet another embodiment, the oxidized
carbon black is formed by oxidation of modified carbon black (e.g.,
modified by chlorination, sulfonylation, or by attachment of
organic groups).
[0041] In one embodiment, "coat" or "coating" refers to a physical
and/or chemical interaction between the polyetheramine and the
carbon black that is not covalent. In one embodiment, the
polyetheramine and oxidized carbon black interact via adsorption,
ionic bonding, van der Waals interaction, etc., and combinations of
such interactions. For example, oxidized carbon blacks provide
acidic groups (e.g., carboxylic acid or alcohol groups and anions
and salts thereof) that can interact with the amine groups (and
cations and salts thereof) of the polyetheramine.
[0042] In one embodiment, the oxidized carbon black has a BET
surface area ranging from 50 to 700 m.sup.2/g (e.g., from 90 to 650
m.sup.2/g), a DBP oil adsorption number ranging from 50 to 200
mL/100 g (e.g., from 60 to 160 mL/100 g), and a primary particle
size ranging from 7 to 30 nm (e.g., from 10 to 25 nm). BET surface
area can be determined according to ASTM-D6556. DBP can be
determined according to ASTM-D2414. Primary particle size can be
determined according to ASTM-D3849 (07-2011).
[0043] In one embodiment, the polyetheramine is a generally a lower
molecular weight compound relative to typical dispersion aids. For
example, the polyetheramine has a molecular weight ranging from 250
to 5,000, or a molecular weight ranging from 1,000 to 2,500. The
polyetheramine can be a mono-, di-, or triamine where the amine
groups have sufficient accessibility to interact with the surface
of the oxidized carbon black. In one embodiment, the polyetheramine
is terminated with one or more amine groups. In one embodiment, the
polyetheramine is a monoamine.
[0044] In one embodiment, the polyetheramine comprises propylene
and ethylene oxide monomers in a ratio ranging from 1:2 to 9:1,
such as a ratio ranging from 1:2 to 8:1, 1:2 to 7:1, or 1:2 to
6:1.
[0045] The polyetheramine can be branched or linear. In one
embodiment, the polyetheramine has the formula:
##STR00002##
wherein x=1-35, y=3-30, x/y is at least 0.15. In other embodiments,
x/y is at least 0.3. For example, x/y can be 9/1, 3/19, 29/6,
10/31, or 1/1. Exemplary polyetheramines can be obtained
commercially from Huntsman Corporation under the trademark
JEFFAMINE.RTM. polyetheramines.
[0046] The powdered material is a particulate material and
typically comprises aggregates of the primary particles. The
powdered material can be present as a dispersion, or as a bulk
powder, e.g., a powder substantially free of water or solvent, such
as less than 10%, less than 5%, less than 3%, or less than 1% water
or solvent. In one embodiment, the polyetheramine is present in the
powdered material (e.g., the bulk powdered material) in an amount
ranging from 5% to 30% by weight with respect to the total weight
of the powdered material, such as an amount ranging from 5% to 30%
by weight with respect to the total weight of the powdered
material. In another embodiment, the carbon black is present in the
powdered material in an amount ranging from 65% to 95% by weight
with respect to the total weight of the powdered material.
[0047] Another embodiment provides a method of preparing a powdered
material, comprising:
[0048] coating an oxidized carbon black with a polyetheramine,
wherein the oxidized carbon black is obtained by oxidizing a carbon
black (e.g., an unmodified carbon black) having a BET surface area
ranging from 50 to 700 m.sup.2/g, a DBP oil adsorption number
ranging from 50 to 200 mL/100 g, and a primary particle size
ranging from 7 to 30 nm.
[0049] In one embodiment, the step of coating comprises spraying
the polyetheramine onto the oxidized carbon black. In one
embodiment, the spraying is performed on oxidized carbon black
powder.
[0050] Many high-color carbon blacks are available as either a
powder or pellet, which is the compacted form of the powder. While
pellets are easier to handle, e.g., due to reduced dusting, they
are more difficult to disperse. It has been discovered that pellets
formed by compacting/densifying the powdered materials disclosed
herein disperse readily while reducing the amount of dusting during
handling. In one embodiment, the pellets have a D50 of at least 100
.mu.m, e.g., a D50 ranging from 100 .mu.m to 5000 .mu.m, from 100
.mu.m to 2000 .mu.m, or from 100 .mu.m to 500 .mu.m, or a D50 of at
least 125 .mu.m, e.g., a D50 ranging from 125 .mu.m to 5000 .mu.m,
from 125 .mu.m to 2000 .mu.m, or from 125 .mu.m to 500 .mu.m.
[0051] One embodiment provides a method of making pellets,
comprising compacting unoxidized carbon black to form a compacted
material, oxidizing the compacted material, combining the oxidized
material with the polyetheramines disclosed herein. In another
embodiment, the pellets are prepared by compacting the powdered
material disclosed herein. In yet another embodiment, the pellets
are prepared by compacting oxidized carbon black and combining the
compacted oxidized carbon black with the polyetheramines disclosed
herein.
[0052] Another embodiment provides compositions for surface
coatings, or coating compositions. Accordingly, one embodiment
provides a coating composition, comprising:
[0053] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm,
[0054] a polyetheramine comprising ethylene oxide and propylene
oxide monomers, and
[0055] a resin having a molecular weight of at least 10,000.
[0056] In one embodiment, the polyetheramine coats the oxidized
carbon black.
[0057] The amount of carbon product used in the coating
compositions is generally dependent on the desired performance of
the resulting coating. For example, the amount of carbon product
can be adjusted to optimize such properties as jetness, viscosity,
and dispersion stability. In one embodiment, the carbon black is
present in the coating composition in an amount ranging from 1% to
30%, such as an amount ranging from 1% to 20% by weight with
respect to the total weight of the coating composition.
[0058] The coating composition typically comprises a resin having a
higher molecular weight than the polyetheramine, e.g., a molecular
weight of at least 10,000. The resin can be of a type that promotes
a hydrophobic surface and/or any polymer that chemically or
physically locks the carbon black particles to each other and/or to
a substrate. In one embodiment, the resin is selected from
acrylics, polyesters, polyurethanes, alkyds, cellulose acetate
butyrate, nitro cellulose, melamines, epoxies, and blends and
copolymers thereof.
[0059] In one embodiment, where the resin is capable of
cross-linking, the coating composition can further comprise
cross-linking agents. For example, where the resin is selected from
polyols (e.g., polyester polyols, acrylic polyols, and blends and
copolymers thereof), the cross-linking agent can be selected from
amine-, imine-, and isocyanate-containing compounds, such as
Cymel.RTM. 325 and Cymel.RTM. 303, from Cytec Industries, and
Resimene.RTM. 717 from INEOS Melamines. The cross-linking agent can
be provided in either the mill base or the let down composition. In
one embodiment, the resin (optionally including a cross-linking
agent) is present in the composition in an amount of at least 40%,
at least 50%, or at least 60% by weight with respect to the total
weight of the composition.
[0060] In one embodiment, the coating composition further comprises
a liquid vehicle. In one embodiment, the liquid vehicle comprises a
solvent, such as an organic solvent, or a solvent blend. Suitable
examples of organic solvents include alcohols (e.g., methanol and
isobutanol), glycols, ethers (e.g., tetrahydrofuran or
diethylether), ketones (e.g., acetone, methylethyl ketone, or
methylbutyl ketone), esters (e.g., n-butyl propionate), acetates
(e.g., methyl-, ethyl-, propyl-, and butyl acetate, and propylene
glycol methyl ether acetate (PGMEA)), amides (e.g.,
dimethylformamide), sulfoxides (e.g., dimethylsulfoxide),
hydrocarbons, aromatics (e.g., toluene), halocarbons (e.g.,
chloroform), and miscible mixtures thereof (e.g., ethylene glycol
and methanol). Conventional co-solvents include, but are not
limited to, butyl acetate, ethylcellosolve, ethylcellosolve
acetate, butylcellosolve, butylcellosolve acetate, ethylcarbitol,
ethylcarbitol acetate, diethylene glycol, cyclohexanone, propylene
glycol monomethyl ether, propylene glycol monomethyl ether acetate,
lactate esters, and mixtures of these may also be employed. In one
embodiment, the solvent is present in the coating composition in an
amount ranging from 0.1% to 60% by weight, e.g., an amount ranging
from 5% to 50% by weight, an amount ranging from 10% to 50% by
weight, or an amount ranging from 10% to 40% by weight with respect
to the total weight of the composition.
[0061] In one embodiment, the coating composition further comprises
a dispersing aid. In one embodiment, the dispersing aid is selected
from amine-functionalized or amine-terminated compounds such as
polyamine, tertiary amine, or quaternary ammonium functionalized
compounds, e.g., tetraoctylammonium bromide, block copolymers e.g.,
those having both a hydrophobic and a hydrophilic group, and
polyalkylene oxides or acrylic polymers comprising amine functional
groups, and blends and copolymers thereof. Other dispersing aids in
addition, or in alternative, to the amine-functionalized compound
include, but are not limited to, polyalkylene oxides (such as
polyethylene oxide or polypropylene oxide), polyesters (such as
polycaprolactone, polyvalerolactone, poly(hydroxy stearic acid), or
poly(hydroxyoleic acid), polyamides such as polycaprolactam,
polyacrylates, block copolymers having both a hydrophobic and a
hydrophilic group, acid functionalized compounds (such as
carboxylic acid or phosphonic acid functionalized compounds),
polyalkylene oxides or acrylic polymers comprising acid functional
groups.
[0062] Exemplary dispersants that may be employed include, but are
not limited to, the OLOA series (modified polyisobutylene
succinimides) from Chevron Chemical Co. Also included but not
limited are: BYK108, BYK 115, BYK116, BYK161, BYK163, BYK 182 BYK
2150 and BYK2050, all available from BYK Chemie, Solsperse.TM.
series of dispersants 27000, 32000, 32500, 38500, and 39000,
Efkla.TM. dispersants such as 4050, 4310, and 4061, available from
Noveon, including and K-Sperse.TM. dispersants such as K-Sperse.TM.
504 XD from King Industries.
[0063] The amount of dispersing aid can be determined based on one
or more factors, including the coated carbon black, the solvent,
and the carbon black loading level. In general, the ratio of the
amount of dispersing aid to the amount of coated carbon black can
be at least about 0.1 or more (e.g., from about 0.2 or more, or
from about 0.3 or more, or from about 0.5 or more, or even about
from about 1 or more). Alternatively, or in addition, the ratio of
the amount of dispersing aid to the amount of coated carbon black
can be about 10 or less (e.g., about 5 or less, or about 4 or less,
or about 3 or less, or about 2.5 or less). In another embodiment,
the ratio of the amount of dispersing aid to the amount of coated
carbon black can range from 0.01 to 10, from 0.1 to 5, from 0.1 to
2.5, from 0.5 to 2.5, or from 1 to 2.5.
[0064] The dispersions can be prepared by any method known in the
art. For example, the coated carbon black and solvent may be
combined with agitation to produce a stable dispersion in the
presence of a dispersing aid. Alternatively, the dispersing aid can
be combined with the pigment, and the resulting combination can
then be combined with the solvent. The pigment, dispersing aid, and
solvent may be combined in any equipment known in the art, such as
ceramic media or ball mill, or other high shear mixing equipment,
such as a rotor-stator mixer. Various conventional milling media
can also be used. Other methods for forming the dispersion/mill
base will be known to one skilled in the art.
[0065] The coating composition can be a mill base or any coating
composition that is eventually applied to a surface (e.g., after
let down). Without wishing to be bound by any theory, the
polyetheramine treated carbon black is better wetted by solvent in
a mill base in which the polyetheramine molecules can bind to the
carbon black surface via an acid/base binding interaction. While
the invention is not limited to monoamines, such molecules can
adsorb more quickly onto carbon black surfaces and provide initial
steric stabilization of carbon black particles in solvent
dispersion by virtue of the propylene oxide/ethylene oxide chains.
During milling or the formation of dispersions, the larger
dispersion aid molecules can be adsorbed on carbon black surface
and provide long term stability of mill base and paint
formulations. Due to the improved efficiency of dispersing the
treated oxidized carbon black, the amount of dispersing aid can be
reduced by at least 10% by weight, by at least 20% by weight, or by
an amount ranging from 10% to 30% by weight, relative to the amount
of dispersing aid used to create a dispersion of untreated oxidized
carbon black.
[0066] Non-aqueous coating formulations vary widely depending on
the final use and the components present, including other
additives. Two general classes of additives are fillers and
modifiers. Examples of fillers are other coloring pigments, clays,
talcs, silicas, and carbonates. Fillers can be added in an amount
ranging from 0.1% to 60% by weight, depending on final use
requirements. Examples of modifiers are flow and leveling aids
generally added at less than 5% by weight (e.g., from 0.1% to 5% by
weight). The modified pigments disclosed herein can be incorporated
into a non-aqueous coating composition using standard techniques,
e.g., as a dispersion.
[0067] The coating composition can be prepared in any suitable
manner, for example, by combining the treated oxidized carbon black
with the liquid vehicle and resin, as well as with other components
of the coating composition (e.g., other pigment(s), dispersion
aid(s), vehicle(s), other colorant(s) (e.g., dyes), coalescing
agent(s), flow additive(s), defoamer(s), surfactant(s), rust
inhibitor(s), charge control agent(s), and the like), by any
suitable methods, many of which are well known in the art. For
example, the modified pigment particles can be added to a mixture
of the liquid vehicle and resin in a solvent then dispersed therein
using any suitable methods. Alternatively, the modified pigment
particles can be added to the liquid vehicle and then dispersed
therein, with the carrier or carrier precursor added thereafter.
Additional components such as described herein can be added at any
suitable stage in the preparation of the coating composition.
[0068] Accordingly, another embodiment provides a method of
preparing a coating composition, comprising:
[0069] preparing a millbase comprising: [0070] an oxidized carbon
black coated with a polyetheramine comprising ethylene oxide and
propylene oxide monomers; [0071] a resin having a molecular weight
of at least 10,000; and [0072] a dispersion aid.
[0073] In one embodiment, the method further comprises the step of
combining the millbase with a let down comprising a cross-linking
agent. The let down can further comprise a resin, which can be the
same or different from the resin in the millbase. In one
embodiment, the let down includes at least one resin that is the
same as in the millbase. The let down can also comprise additional
components such as the cross-linking agent, organic solvents,
dispersing aids and surfactants, etc.
[0074] Also disclosed herein are coatings, e.g., the composition
that results after applying the coating composition to a substrate
surface followed by removal of the solvent, e.g., by drying.
Accordingly, another embodiment provides a coating composition,
comprising:
[0075] an oxidized carbon black having a BET surface area ranging
from 50 to 700 m.sup.2/g, a DBP oil adsorption number ranging from
50 to 200 mL/100 g, and a primary particle size ranging from 7 to
30 nm,
[0076] a polyetheramine comprising ethylene oxide and propylene
oxide monomers, and
[0077] a resin selected from acrylics, polyesters, polyurethanes,
alkyds, cellulose acetate butyrate, nitro cellulose, melamines,
epoxies, and blends and copolymers thereof.
[0078] The resin can be of any resin as disclosed herein. In one
embodiment, the resin promotes a hydrophobic surface and/or can
chemically or physically lock the carbon black particles to each
other and/or to a substrate. In one embodiment, the substrate is
selected from glasses, plastics, metals, ceramics, papers, and
woods, and painted, coated, or waxed surfaces thereof. In another
embodiment, the substrate is selected from metals, such as
automotive metal surfaces (such as the automobile body), e.g.,
steel, aluminum, magnesium, titanium, zinc, and alloys thereof.
[0079] The coatings disclosed herein can be used for a variety of
different end-use applications, such as, for example, automotive
topcoats, to give coatings with improved overall performance
properties. The polyetheramine-treated carbon blacks can be readily
dispersed in the coating compositions to obtain coatings with
improved jetness and blue tone. This will be further clarified by
the following examples, which are intended to be purely exemplary
of the present invention.
EXAMPLES
Example 1
[0080] Various medium color grades carbon blacks have been tested,
including Monarch.RTM. 880, a base seed carbon black (CB) particle,
and Monarch.RTM. 1000, which is a nitric acid treated oxidized
version of Monarch.RTM. 880. Monarch.RTM. 1000 carbon black was
mixed with M-2005, M-2070 and XTJ-674 grades of JEFFAMINE.RTM.
polyetheramine and tested in OEM type solvent-based
formulations.
[0081] Table 1 below lists the combinations of Monarch.RTM. 880 and
Monarch.RTM. 1000 samples with JEFFAMINE.RTM. (JA)
polyetheramines:
TABLE-US-00001 TABLE 1 Sample # JA type CB grade JA/CB 1 M-2070
M1000 0.05 2 M-2070 M1000 0.1 3 M-2070 M1000 0.25 4 M-2070 M880 0.1
5 XTJ-674 M1000 0.05 6 XTJ-674 M1000 0.1 7 XTJ-674 M1000 0.25 8
XTJ-674 M880 0.1 9 M-2005 M1000 0.05 10 M-2005 M1000 0.1 11 M-2005
M1000 0.25 12 M-2005 M880 0.1
[0082] The polyetheramines of sufficient water solubility
(JEFFAMINE.RTM. polyetheramine M-2070 and XTJ-674) were sprayed in
various amounts onto the carbon blacks as aqueous solutions.
JEFFAMINE.RTM. polyetheramine M-2005 was sprayed as a suspension in
water. The carbon black samples were rolled for 10 hours, and then
dried overnight at 85.degree. C. The majority of the samples were
powders even before oven drying since the amount of added water was
minimal (less than DBP). Dry carbon black samples were pulverized
before formulating into mill bases.
Example 2
[0083] This Example describes the use of the coated carbon black
samples of Example 1 in preparing model automotive solvent-based
formulations at 2.45% pigment loading with a standard DisperBYK 163
dispersion aid (product of BYK Chemie/Altana).
[0084] Mill bases were prepared using the following equipment:
[0085] Eiger mill; [0086] 1.0 mm Zirconium media; [0087] Blue M
Vented Drying Oven (Model POM 206); Gar Lab 15 Hour model (VWR);
[0088] air assist spray; and [0089] coarse paint strainers (Paul N.
Gardner Co.).
[0090] The following raw materials were used: [0091] Setal.RTM.
1715VX74 (polyester polyol) [0092] Setalux.RTM. 11845551 (acrylic
polyols) [0093] DisperBYK.RTM. 163 (high MW acrylate) [0094] Cymet
325.RTM. melamine resin (amino-based cross-linking agent, Cytec)
[0095] BYK.RTM. 346, wetting agent (silicone surfactant, BYK
Chemie) [0096] butyl acetate; and [0097] PGMEA.
[0098] A mill base master batch contained the materials listed in
Table 2 below:
TABLE-US-00002 TABLE 2 Setal .RTM. 1715VX74 60.75 g 47.65 DisperBYK
.RTM. 163 20 g 15.69 Butyl Acetate 23.37 g 18.33 PGMEA 23.38 g
18.34 127.5 g 100.00%
[0099] Setal.RTM. 1715VX74 was placed in a quart can and placed in
a lab mixer. DisperBYK.RTM. 163, butyl acetate and PGMEA were
premixed and then added to the Setal.RTM. 1715VX74 under good
agitation mix for 5 minutes, followed by further mixing for 10
minutes, and then discharged.
[0100] The mill base was prepared using in the proportions listed
in Table 3, below:
TABLE-US-00003 TABLE 3 Millbase master batch 127.5 g 85.0% coated
carbon black (from Example 1) 22.5 g 15.0% 2 mm ceramic media
150.00 g 100.00%
[0101] 127.5 grams (.+-.0.01) of the millbase master batch was
placed in a vessel under high speed dispermat. 22.5 grams of the
coated carbon black from Example 1 was added to the millbase master
batch under slow agitation. The speed was increased to 4000 RPM and
mixed for 5 minutes. The mixture was then recirculated through a
horizontal mill (Eiger) for four passes and the viscosity measured.
The mixture was discharge and proceeded to the letdown.
Example 3
[0102] This Example describes the let down of the mill base
composition of Example 2 and preparation of the final coating
composition.
[0103] A let down master batch was prepared in the proportions
listed in Table 4 below:
TABLE-US-00004 TABLE 4 Setalux .RTM. 1184SS51 44 g 18.27 Setal
.RTM. 1715VX74 121 g 50.25 Cymel .RTM. 325 48.8 g 20.27 BYK .RTM.
346 2 g 0.83 butyl acetate/PGMEA (1/1) 25 g 10.38 Total 240.8 g
100%
[0104] The Setalux.RTM. 1184SS51 and Setal.RTM. 1715VX74 were
weighed into a half gallon container and placed under the lab
mixer. The BYK.RTM. 346, butyl acetate, PGMEA, and Cymel.RTM. 325
were premixed together then slowly added to the
Setalux.RTM./Setal.RTM. mixture under good agitation. This master
batch was mixed for another 15 minutes then discharged.
[0105] A finish was prepared in the proportions listed in Table 5
below
TABLE-US-00005 TABLE 5 Millbase from Example 2 9.4 g 9.4% Letdown
Master batch 90.6 g 90.6% Total 100.00 g 100.00%
[0106] 90.6 grams (.+-.0.01) of the letdown master batch was added
to 9.4 g of the mill base from Example 2 into an 8 oz epoxy coated
can under good agitation. This mixture was placed in a skandex for
15 minutes and allowed to stand overnight before application
stage.
Example 4
[0107] This Example describes the preparation and evaluation of
coatings made from the coating compositions of Example 3.
[0108] The Formulations with Monarch.RTM. 1000 were sprayed on tin
plate at 0.8 mil DFT (dry film thickness) and dried at 140.degree.
C. for 20 minutes after flash of air drying at room temperature for
10 minutes. The color was measured on Hunter Labscan colorimeter.
Table 6 shows the L a b* and M.sub.c data for the samples made from
the components of Table 1.
TABLE-US-00006 TABLE 6 M1000 No. 1 No. 2 No. 3 No. 5 No. 6 No. 7
No. 9 No. 10 No. 11 L 1.52 1.54 1.42 1.32 1.38 1.32 1.3 1.34 1.3
1.24 a* 0.02 0.01 0.02 0 0.01 0.01 0 0.03 0.07 0.04 b* 0.31 0.09
0.11 0.12 0.12 0.16 0.12 0.18 0.21 0.2 Mc 272 275 278 280 279 280
282 279 279 282
[0109] From this data, it can be seen that samples of oxidized
carbon black treated with polyetheramines show lower L (stronger
color), better (lower) color tone b*, and higher Mc values than the
control sample of oxidized carbon black without coated
polyetheramine. The increase of the amount of polyetheramine on
carbon black results in coating with better color development.
Polyetheramines with higher content of propylene oxide, which are
more hydrophobic, XTJ-674 and M-2005 yielded better color than the
more hydrophilic M-2070.
[0110] Mill bases made with non-oxidized CB M880 (sample nos. 4, 8
and 12) were too viscous for coating preparation; data could not be
collected for these samples.
Example 5
[0111] Coating compositions were made with Black Pearls.RTM. 1300
grade of oxidized carbon black and coated with JEFFAMINE.RTM.
polyetheramines, as listed in Table 7 below.
TABLE-US-00007 TABLE 7 Sample # polyetheramine carbon black grade
polyetheramine/CB A M-2070 Black Pearls .RTM. 1300 0.1 B M-2070
Black Pearls .RTM. 1300 0.15 C M-2070 Black Pearls .RTM. 1300 0.2 D
XTJ-674 Black Pearls .RTM. 1300 0.1 E XTJ-674 Black Pearls .RTM.
1300 0.15 F XTJ-674 Black Pearls .RTM. 1300 0.2 G XTJ-674 Black
Pearls .RTM. 1300 0.2 H XTJ-674 Black Pearls .RTM. 1300 0.2 I
XTJ-674 Black Pearls .RTM. 1300 0.2 J M-2005 Black Pearls .RTM.
1300 0.1 K M-2005 Black Pearls .RTM. 1300 0.15 L M-2005 Black
Pearls .RTM. 1300 0.2
[0112] The coating compositions were prepared according to the
methods outlined in Examples 1-4. The color performance (M.sub.e)
of these samples was compared with the performance of compositions
containing an oxidized carbon black from Orion (FW200), which is
uncoated. The results are shown in Table 8.
TABLE-US-00008 TABLE 8 Sample Mc FW200 284 A 277 B 286 C 287 D 288
E 289 F 291 G 292 H 290 I 289 J 288 K 289 L 292
[0113] It was found that inventive samples give better color of the
coating, with Mc value of 5 to 7 units higher than those made with
FW200. Based on these results, it can be concluded that hydrophilic
JEFFAMINE.RTM. polyetheramine M-2070), does not provide as good
jetness as medium and highly hydrophobic materials (similar to
results of M1000). JEFFAMINE.RTM. polyetheramine XTJ-674 and M-2005
perform equally well.
[0114] To achieve good jetness and hiding power, a solvent mill
base with Monarch.RTM. 1300 (uncoated) needs to pass through a
media mill 4 to 5 times. Using the oxidized carbon blacks coated
with polyetheramines, as described herein, such as aqueous
solutions of pulverized Black Pearls.RTM. 1300 pellets mixed with
polyetheramine followed by drying, the milling time through a media
mill is reduced to 1 pass.
[0115] It was also found that mill bases disclosed herein, such as
a mill base prepared with Black Pearls.RTM. 1300 (samples 1 to 12),
required substantially lower amounts of dispersion aid to achieve
good color. This behavior brings additional benefit to customers,
by lowering total cost of the formulation.
Example 6
[0116] This Example describes the formation of
polyetheramine-treated pellets.
[0117] Oxidized carbon black pellet samples Black Pearls.RTM. 1000
and Black Pearls.RTM. 1300 were treated with JEFFAMINE.RTM.
polyetheramine M-2005 in the same manner as Example 1 to produce
polyetheramine-treated pellets Sample A and Sample B,
respectively.
[0118] A representative pellet size distribution for Samples A and
B is provided in Table 9.
TABLE-US-00009 TABLE 9 2000 .mu.m 1000 .mu.m 500 .mu.m 250 .mu.m
125 .mu.m 62.5 .mu.m 8% 13% 17% 38% 18% 6%
Example 7
[0119] This Example describes the preparation of coating
compositions from the Sample A and Sample B pellets of Example 6.
Table 10 lists the materials for preparing a millbase
masterbatch:
TABLE-US-00010 TABLE 10 Raw material Amount (%) Setal .RTM.189SS65
(polyester resin) 30.77 Efka .RTM. 4310 (dispersant) 8.00 Butyl
Acetate 25.61 PGMEA 25.62 carbon black (Sample A or Sample B)
10.00
[0120] A mixture of Efka 4310, butyl acetate, and PGMEA was
prepared followed by the addition of Setal.RTM. 189SS65 under good
agitation. Carbon black was then added slowly followed by mixing
for 5 min. at 4000 rpm. This mixture was then passed through a
horizontal media Eiger mill at 10 m/s tip speed for a number of
passes, as specified below.
[0121] The mill base was reduced with the letdown formulation of
Table 11:
TABLE-US-00011 TABLE 11 Raw material Amount (%) Setal .RTM. 189SS65
48.11 CAB551-0.01 (30% BA) (cellulose acetate 29.88 butyrate resin
in butyl acetate) Cymel .RTM. 325 2.79 BYK .RTM. 346 0.45 butyl
acetate/PGMEA 18.77
[0122] A mixture of cellulose acetate butyrate resin solution,
Cymel 325, and BYK346 were blended together in butyl acetate/PGMEA.
This mixture was added to the Setal.RTM. 189SS65 under good
agitation and mixed for 15 min and discharged. A finish formulation
was prepared in the proportions listed in Table 12 below.
TABLE-US-00012 TABLE 12 Raw material Amount (%) Masterbatch letdown
89.5 Millbase 10.5
[0123] The millbase was added to the masterbatch letdown under good
agitation, mixed for 20 min. and then discharged.
[0124] Coatings were formed by casting out the formulation on cold
roll steel and BYK chart with a 0.003 cast out bar, followed by air
drying for 10 minutes at room temperature, and curing at
150.degree. F. for 10 minutes. The resulting clear coat was cast
with a 0.005 cast out bar followed by air drying for 24 hours at
room temperature.
[0125] Tables 13-18 below show the L, b, and Mc values,
respectively for the pellets disclosed herein (Samples A and B)
compared to a pelleted, oxidized black (Black Pearls.RTM. 1000)
and; a powdered oxidized black (Monarch.RTM. 1000 or Monarch.RTM.
1300).
TABLE-US-00013 TABLE 13 L values BP1000 M1000 Sample A Pass 1 11.00
8.03 1.72 Pass 2 8.52 2.63 1.52 Pass 3 7.58 2.04 1.54 Pass 4 6.63
1.76 1.55 Pass 5 5.26 1.67 1.54 Pass 6 4.98 Pass 7 3.93
TABLE-US-00014 TABLE 14 L values Sample B M1300 Pass 1 3.50 18.49
Pass 2 1.22 7.11 Pass 3 1.12 4.15 Pass 4 1.05 2.48 Pass 5 1.04
1.89
TABLE-US-00015 TABLE 15 b values BP1000 M1000 Sample A Pass 1 0.95
3.06 -0.15 Pass 2 1.41 0.78 -0.43 Pass 3 1.19 0.33 -0.44 Pass 4
1.15 0.06 -0.46 Pass 5 1.00 -0.02 -0.43 Pass 6 0.90 Pass 7 0.82
TABLE-US-00016 TABLE 16 b values Sample B M1300 Pass 1 1.66 2.57
Pass 2 -0.12 3.55 Pass 3 -0.20 2.43 Pass 4 -0.31 1.41 Pass 5 -0.27
0.91
TABLE-US-00017 TABLE 17 M.sub.c values BP1000 M1000 Sample A Pass 1
189.00 193.00 274 Pass 2 198.00 245.00 285 Pass 3 203.50 260.00 285
Pass 4 208.50 270.00 284 Pass 5 218.00 274.00 284 Pass 6 221.00
Pass 7 230.50
TABLE-US-00018 TABLE 18 M.sub.c values Sample B M1300 Pass 1 226
165 Pass 2 289 194 Pass 3 295 214 Pass 4 300 237 Pass 5 300 252
[0126] The disclosed pellets (Samples A and B) demonstrated
superior color performance relative to the oxidized carbon black
and the untreated carbon black. Faster color L and b values
development can be attributed to greater dispersion of the pigment
particle in the system. The same also can be seen with color
jetness development. Samples A and B achieved optimum color
performance in 2 passes versus 5 passes for commercial oxidize
black. The base black cannot approach the color performance of the
disclosed pellets even after 7 passes in the mill.
[0127] Moreover, Samples A and B required a dispersant loading of
just 20%, while both the base and oxidized carbon blacks require
loadings of 40% or higher. The low dispersant requirement the
disclosed pellets can be attributed to the lower surface energy of
the polyetheramine/pellet composite in a nonpolar formulation.
Example 8
[0128] This Example describes the treatment of oxidized carbon
black with polyetherdiamines and coating compositions prepared
therefrom.
[0129] A powdered, oxidized black, Monarch.RTM. 1300, was treated
with JEFFAMINE.RTM. polyetheramine grade D-230 in the same manner
as described in Example 1 to form the polyetherdiamine-treated
carbon black (Sample C). Table 19 below lists the components of the
millbase composition.
TABLE-US-00019 TABLE 19 Raw material Amount (%) Amount (%) Setal
.RTM. 189SS65 34.3 34.3 DisperBYK .RTM. 161 20 10 butyl acetate
35.7 45.7 carbon black 10 10 M1300 Sample C
[0130] A mixture of DisperBYK.RTM. 161, butyl acetate, and PGMEA
was prepared followed by the addition of Setal.RTM. 189SS65 under
good agitation. The carbon black was slowly to this mixture and
then mixed for another 5 minutes at 4,000 RPM.
[0131] This mixture was then passed through a horizontal media
through Eiger mill at 10 m/s tip speed, discharged, then run for
millbase viscosity.
[0132] The finish formulation is provided in Table 20 below.
TABLE-US-00020 TABLE 20 Raw material Amount (%) Setal .RTM. 189SS65
21.75 CAB381-2 (15% BA) 16.65 Millbase 5
[0133] The Setal.RTM. 189SS65 and cellulose acetate butyrate resin
solution were combined under good agitation, followed by combining
with the millbase and mixing for 15 min. This formulation was
discharged and coatings were prepared in the same manner as
described in Example 7.
[0134] Table 21 lists the L, a, b, and Mc values.
TABLE-US-00021 TABLE 21 M1300 Sample C L 0.99 0.84 a 0.12 0.12 b
0.12 0.16 M.sub.c 292 299
[0135] It can be seen that the polyetherdiamine-treated carbon
black achieves improved L and M.sub.c values, compared to the
untreated sample.
[0136] The Examples demonstrate that coatings prepared with the
coated oxidized carbon blacks, according to the claimed invention,
exhibited color properties significantly exceeded those prepared
with uncoated oxidized carbon blacks.
[0137] The use of the terms "a" and "an" and "the" are to be
construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by context. The
terms "comprising," "having," "including," and "containing" are to
be construed as open-ended terms (i.e., meaning "including, but not
limited to,") unless otherwise noted. Recitation of ranges of
values herein are merely intended to serve as a shorthand method of
referring individually to each separate value falling within the
range, unless otherwise indicated herein, and each separate value
is incorporated into the specification as if it were individually
recited herein. All methods described herein can be performed in
any suitable order unless otherwise indicated herein or otherwise
clearly contradicted by context. The use of any and all examples,
or exemplary language (e.g., "such as") provided herein, is
intended merely to better illuminate the invention and does not
pose a limitation on the scope of the invention unless otherwise
claimed. No language in the specification should be construed as
indicating any non-claimed element as essential to the practice of
the invention.
* * * * *