Note: Descriptions are shown in the official language in which they were submitted.
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Title: PIGMENT COMPOSITIONS
Backctround of the Invention
Field of the Invention
This invention relates to novel azo yellow pigments,
azo dyes, processes for their preparation and to paint,
plastic and ink compositions containing such pigments.
Description of Related Art
Azo yellow pigments known in the art are useful as
coloring agents for paints and printing inks. Use in
plastics is more limited due to the fact that these
pigments tend to bloom and discolor at high temperatures.
German Offenlegungsschrift specification No. 2616981
describes the calcium salt of diazotized 2-amino-4,5-
dichlorobenzene-1-sulfonic acid coupled into 1-(3'-
sulfophenyl)-3-methyl-5 pyrazolone (3-sulfo-PMP) (C. I.
Pigment Yellow 183). U.S. Patent 4,980,458 describes the
mixed sodium, ammonium or half-calcium salts of
diazotized 2-amino-4,5-dichlorobenzene-1-sulfonic acid
coupled into 3-sulfo-PMP. U.S. Patent 4,594,411 describes
the calcium salts of diazotized 2-amino-5-
acetylaminobenzene-1-sulfonic acid, 2-amino-5-
methoxybenzene-1-sulfonic acid, 2-amino-5-methylbenzene-
1-sulfonic acid or 2-amino-5-chlorobenzene-1-sulfonic
acid coupled into 3-sulfo-PMP. U.S. Patent 5,047,517
describes the calcium salt of diazotized 2-amino-4-
chloro-5-methylbenzene-1-sulfonic acid coupled into 3-
sulfo-PMP (C. I. Pigment Yellow 191). German
Offenlegungsschrift specification No. 4444348 describes
the strontium salt of diazotized 2-amino-4-chloro-5-
methylbenzene-1-sulfonic acid coupled into 3-sulfo-PMP.
Also, the pigment from diazotized 3,3'-dichlorobenzidine
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coupled into 1-(4'-methylphenyl)-3-methyl-5-pyra~olone
(PTMP) is known as C.I. Pigment Orange 34.
There is a need for azo yellow pigments that show
improved performance in one or more of the following
S properties: color strength, resistance to polar
solvents, lightfastness and heat stability.
Summary of the Invention
This invention relates to azo pigments suitable for
use as coloring agents, dye compositions useful in the
preparation of such pigments and processes for their
preparation.
In one embodiment, this invention relates~to a
composition comprising one or more compounds
comprising the formula:
15'
(Y)a
. O
wherein Ar is an aromatic moiety having at least one-
substituent which is an acid group or salt thereof; X is
a hydrocarbyl, carboxylic acid ester, sulfonic acid
ester,' carboxylic acid amide or sulfonic acid amide
group; each Y is independently a hydrocarbyl, halogen,
hydrocarbyloxy, carboxylic acid ester, sulfonic acid
ester, carboxylic acid amide, imidazolone, sulfonic acid
amide or vitro group; and a is 1, 2 or 3.
In another embodiment, this invention relates to a
process for preparing an azo dye which comprises coupling
(i) at least one diazonium component of oiie or more
aromatic amines containing at least one sulfonic acid
group or carboxylic acid group, or salts of such groups;
3S with (ii) at least one coupling component represented by
the formula:
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C
a
A2C
wherein X is a hydrocarbyl, carboxylic acid ester,
sulfonic acid ester, carboxylic acid amide or sulfonic
acid amide group; each Y is independently a hydrocarbyl,
halogen, hydrocarbyloxy, carboxylic acid ester, sulfonic
acid ester, carboxylic acid amide, imidazolone, sulfonic
acid amide or nitro group; and a equals 1, 2 or 3.
In still another embodiment, this invention relates
to azo dye compositions prepared by the foregoing process
and azo pigments prepared by metallization of these dyes.
In one other embodiment, this invention relates to
paint, plastic and ink compositions containing the azo
pigment compositions of this invention.
According to one aspect of the invention, there is
provided an azo pigment composition comprising one or
more compounds of the formula:
X
~N
A r-N=N
N
O
(Y )a
wherein X is a hydrocarbyl, carboxylic acid
ester,sulfonic acid ester, carboxylic acid amide or
sulfonic acid amide group; each Y is independently a
hydrocarbyl, halogen, hydrocarbyloxy, carboxylic acid
ester, sulfonic acid ester, carboxylic acid amide,
imidazolone; sulfonic acid amide or nitro group; a equals
1, 2 or 3; and Ar is an aromatic moiety having as a
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substituent a divalent metal salt of a carboxylic acid or
sulfonic acid group, provided that when Ar is monocyclic
it is of the formula:
(Z)m
Halogen
(R)n
wherein each Z is independently a salt of a -C:OOH or -S03H
group; m is 1 or 2; each R is independently a halogen,
hydrocarbyl, hydrocarbyloxy, carboxylic acid ester,
sulfonic acid ester, carboxylic acid amide, imidazolone,
sulfonic acid amide or nitro group; and n is 0, 1 or 2.
According to another aspect of the invention, there
is provided a process for preparing an azo pigment which
comprises forming a dye by coupling (i) at least one
diazonium component of one or more aromatic amines
containing at least one sulfonic acid group or carboxylic
acid group, or salts of such groups wherein the aromatic
amines are selected from the group consisting of fused
cyclic aromatic amines or aromatic amines of the formula:
(Z)m
Halogen NHZ
(R)h
wherein each R is independently a halogen, hyd.rocarbyl,
hydrocarbyloxy, carboxylic acid ester, sulfonic acid
ester, carboxylic acid amide, imidazolone, sulfonic acid
amide or nitro group; n is equal to 0, 1 or 2; each Z is
independently a -COON or -S03H group, or salts of such
groups; and m is equal to 1 or 2; with (ii) at least one
coupling component of the formula:
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X N
\ (Y)a
N
O
wherein X is a hydrocarbyl, carboxylic acid ester,
sulfonic acid ester, carboxylic acid amide or sulfonic
acid amide group; each Y is independently a hydrocarbyl,
halogen, hydrocarbyloxy, carboxylic acid ester, sulfonic
acid ester, carboxylic acid amide, imidazolone, sulfonic
acid amide or nitro group; and a equals 1, 2 or 3; and
metallizing said dye with at least one divalent metal.
Description of the Preferred Embodiments
As previously stated, this invention provides azo
pigments, azo dyes and processes for their preparation.
The azo dyes of the present invention are prepared by
initially diazotizing one or more aromatic amines
containing at least one acid group or alkali metal or
ammonium salts thereof to form a diazonium component and
thereafter coupling the diazonium component with a
coupling component comprised of a pyrazolone coupler to
form the desired dye.
A variety of suitable aromatic amines can be
utilized for the purposes of the present invention.
Almost any primary aromatic amine can be used where the
aromatic moiety of such amine contains at least one
substituent acid group or alkali metal or ammonium salts
thereof (Ar). The aromatic amines may be monoamines or
polyamines containing up to four or more amine groups per
molecule. Thus, the diazonium components derived from
such amine may contain one diazonium group (mono-
diazonium), two diazonium groups (bis-diazonium), three
diazonium groups (tris-diazonium), etc. The aromatic
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amines may be monocyclic amines such as aniline and its
derivatives, or bicyclic amines such as naphthyl amine.
The aromatic amines may~also be biphenylamines or
polyamines such as aminobiphenyl, benzidine, and 3, 3', t
4, 4'-biphenyltetramine.
In one embodiment, the aromatic amine is a primary
aromatic amine characterized by the formula
z )in
to O (I)
( n
wherein each R is independently a halogen, hydrocarbyl,
hydrocarbyloxy, carboxylic acid ester, sulfonic acid
15ester, carboxylic acid amide, imidazolone, sulfonic acid
amide or nitro group; n is 0, 1 or 2; each Z is
independently a -COON or -S03H group, or salts of such
groups; m is 1 or 2; wherein it is understood that ~he
imidazalone group is represented by the formula -rrx-c-r~H-
20 which, when taken together with the aromatic ring, the
nitrogen atoms are bonded to adjacent carbons to form a
five member ring. The term "hydrocarbyl" as used in this
specification and claims is intended to include
hydrocarbons which may contain substituent groups such as
25 ether, ester, nitro or halogen which do not materially
affect the hydrocarbon character of the group.
The aromatic amines characterized by Formula I may
contain 0, 1 or 2 R groups which are each independently a ,
halogen, hydrocarbyl, hydrocarbyloxy, carboxylic acid
30 ester, sulfonic acid ester, carboxylic acid amide,
imidazolone, sulfonic acid amide or nitro group. The
halogen group can be any of the halogens, although
chlorine and bromine are generally used, with chlorine
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being the most preferred example of a halogen
y substituent. The hydrocarbyl groups may independently be
alkyl, cycloalkyl, aryl, aralkyl or alkaryl groups. For
example, if R is an unsubstituted aryl group, the
aromatic amine a.s a biphenyl amine. When R is an alkyl
group, the alkyl group generally will contain from one to
four carbon atoms. As used herein, "lower alkyl" shall
mean those alkyl groups containing from 1 up to 4 carbon
atoms. When R is a hydrocarbyloxy group, the hydrocarbyl
moiety may be any of the hydrocarbyl groups discussed
above although the hydrocarbyloxy group generally is an
alkoxy group containing from 1 to about~4 or more carbon
atoms. Preferred R groups are methyl, ethyl and chloro
groups.
The aromatic amines characterized by Formula I also
contain one or two acid groups of -COOH and -S03H, or
salts thereof. In one preferred embodiment, the aromatic
amine of Formula I contains an -S03H group.
Examples of aromatic amines characterized by Formula
I wherein Z is a sulfonic acid group and m is 1 include
2-aminobenzene-1-sulfonic acid, 4-aminobenzene-1-sulfonic
acid, 2-amino-5-methylbenzene-1-sulfonic acid, 2-amino-5-
methoxybenzene-1-sulfonic acid, 3-amino-6-methylbenzene-
1- sulfonic acid, 2-amino-4-chloro-5-methylbenzene-1-
sulfonic acid, 2-amino-5-chloro-4-ethylbenzene-1-sulfonic
acid, 2-amino-5-chloro-4-methylbenzene-1-sulfonic acid,
etc.
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Examples of aromatic amines characterized by Formula
I wherein Z is a carboxylic acid group, and m is 1
include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-
aminobenzoic acid, 2-amino-5-methylbenzoic acid, 2-amino-
6-methylbenzoic acid, 3-amino-2-methylbenzoic acid, 2-
amino-3-methoxybenzoic acid, 4-amino-3-methoxybenzoic
acid, 4-amino-5-chloro-2-methoxybenzoic acid, 2-amino-4-
chlorobenzoic acid, 3-amino-4-chlorobenzoic acid, etc.
The benzene sulfonic acid and benzoic acid compounds can
be used per se or as their salts. Examples of preferred
salts include the alkali metal salts such as the sodium
and potassium salts.
The aromatic amines from which the diazonium
components are prepared may be fused cyclic aromatic
amine compounds such as compounds derived from various
naphthalenes including 2-aminonaphthalene-1-sulfonic
acid, 4-aminonaphthalene-1-sulfonic acid, etc. Examples
of aromatic amines which are biphenyl amines and
polyamines include 4-aminobiphenyl-3'- sulfonic acid, and
4,4'-diaminobiphenyl-2,2'-disulfonic acid.
Mixtures of two or more of any aromatic amines are
within the scope of this invention.
The diazotization of the aromatic amines may be
carried out in the manners known to those skilled in the
art through the use of alkali metal nitrites or lower
alkyl nitrites together with an adequately strong acid
such as a mineral acid. Examples of useful mineral acid
include hydrochloric acid and sulfuric acid. Nitrosyl
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sulfuric acid also can be utilized. The diazotization
reaction can be conducted at a temperature in the range
of from about -20 to +30°C, preferably from 0 to 20°C.
Although not required, it may be advantageous in some of
the diazotization reactions (and in the subsequent
coupling reactions) to include a surface-active agent
such as a non-ionic, anionic or cationic surface active
agent and, optionally, appropriate organic solvents such
as, for example, glacial aceticacid, lower alkanols,
l0 dioxane, formamide, dimethyl formamide, dimethyl
sulfoxide, pyridine or N-methyl pyrrolidone.
The pyrazolone couplers useful for the purposes of
this invention are represented by the formula:
C ~ N
\\ Y ) a
. ~N V
H2C
wherein X is a hydrocarbyl, carboxylic acid ester,
sulfonic acid ester, carboxylic acid amide or sulfonic
acid amide group; each Y is independently a hydrocarbyl,
halogen, hydrocarbyloxy, carboxylic acid ester, sulfonic
acid ester, carboxylic acid amide, imidazolone, sulfonic
acid amide or nitro group; and a equals 1, 2 or 3.
Alkoxy groups generally contain from 1 up to about 4
carbon atoms. Typically, X is a lower alkyl group
containing one or two carbon atoms and is preferably a
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methyl group. A useful X group is also a carboxylic acid
ester of an alcohol containing 1 or 2 carbon atoms and is
preferably an ethyl ester group. ''
Typically, each Y is independently a lower alkyl or
halogen group. The halogen group can be any of the
halogens, although chlorine and bromine are generally
used, with chlorine being the most preferred example o.f a
halogen substituent. Usually, the lower alkyl groups
contain one or two carbon atoms and.a methyl group is a
preferred substituent. Preferably, a is 1 or 2. A
particularly useful embodiment is when a is 1 and Y is a
methyl group in the 4 position.
Examples of the pyrazolone couplers useful for the
purposes of this invention include 1-(4'-methylphenyl)-3-
methyl-5-pyrazolone, 1-(4'-chlorophenyl)-3-methyl-5
pyrazolone, 1-(4'-methylphenyl)-3-carbethoxy-5
pyrazolone, etc.
Mixtures of two or more of any of the pyrazolone
components are within the scope of this invention.
The coupling reaction useful for the purposes of the
present invention may be effected preferably by adding
the diazonium components to coupling components, but the
coupling components can be added to the diazonium
components. Coupling is generally effected at a
J
temperature of from about -20 to about 80°C, preferably
from about 20 to about 65°C. As in a diazotization
reaction, coupling may be carried out in the presence of
an appropriate surface active agent or organic solvent,
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such as all of those identified above for the
diazotization reaction.
In one embodiment, the coupling component is
dissolved in a basic solution such as an aqueous alkali
metal hydroxide solution and reprecipitated with a dilute
acid such as acetic acid.
In -another embodiment, generally, the diazonium
component is coupled with a slight stoichiometric excess
of the coupling component. That is, one equivalent of
the diazonium component is coupled with slightly more
than one equivalent of the coupling component.
In another embodiment of the present invention, the
dispersibility of the pigments of the present invention
can be improved by adding alkali-soluble resin-like
products before, during, or after the coupling is
completed or after the metallization discussed below_
Various resin-like materials can be added for this
purpose, and these include for example, rosin resins,
polymeric rosins, resin soap, chemically modified rosin
resins such as rosin-maleinate resins, alkyd resins, and
other synthetic hydrocarbon resins with a higher acid
number, or combination of these resins. The resins may
be present in a product with free carboxyl groups that
are capable of forming a salt, or may be partially or
completely in the form of salts, for example, with alkali
metal ions. It may also be advantageous to perform the
coupling reaction in the presence of a finely divided
insoluble material, for example, alkaline earth metal
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sulphates and carbonates, titanium dioxide or clay
materials or very finely divided organic plastic
materials.
The composition prepared by the above-described
coupling reaction can be metallized by a divalent metal
salt which forms the sulfonate or carboxylate salt. This
is also known as laking and forms the azo pigment. The
metal salt may be a salt of alkaline earth metals,
manganese, nickel or zinc or mixtures of two or more of
these metals. Alkaline earth metal salts are preferred.
Alkaline earth metal salts such as SrCl2 and CaCl2 are
particularly useful for this purpose. Metallization may
be accomplished preferably by adding the metal salt to
the dye after coupling of all the diazonium component
present is complete or, by including the metal salt in
the diazonium component whereby metallization occurs as
the dye is formed.
In most applications, it is desirable, ~in order to
achieve the full brightness and tinctorial strength, to
heat the azo pigment. For example, the product of the
metallization may be heated to reflux temperature for
about 1 to 3 hours or at temperatures above 100°C under
pressure in the presence of the above-described resin
soaps or other soluble resins.
After completion of the metallization, the azo
pigments are recovered from the water-based reaction
slurry by filtering to form a presscake of pigment which
is washed with hot (e. g., 40-60°C) waterso as to remove
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the excess acids, bases and salts formed in the,coupling
reaction. The presscake is typically washed with from
about 10 to 20 times its volume of hot water. The ffi lter
cake is generally washed until the filtrate gives only a
slightly positive test for chloride ion. The washed
presscakes can be dried, ground and used in the form of a
coarse or finely divided powder. Alternatively, the azo
pigments of this invention can be dispersed into
oleoresinous vehicles to prepare flushed bases or
dispersed into aqueous vehicles to prepare aqueous
dispersions.
The pigment compositions of this invention provide
improved color strength, resistance to polar solvent,
light fastness and/or heat stability and are useful as
coloring agents in plastics, paints and inks.
This invention, therefore, also relates to paint,
ink and plastic compositions comprising major amounts of
a paint vehicle, ink vehicle or plastic and minor amounts
of the compositions of this invention.
The paint, ink and plastic compositions in which the
compositions of this invention are useful are well known
to those of ordinary skill in the art. Examples include
printing inks, lacquers, thermoplastic and thermosetting -
materials, natural resins and synthetic resins,
polystyrene and its mixed polymers, polyolefins, in
particular polyethylene and polypropylene, polyacrylic
compounds, polyvinyl compounds, for example_polyvinyl
chloride and polyvinyl acetate, polyesters and rubber,
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and also filaments made of viscose and cellulose ethers,
cellulose esters, polyamides, polyurethanes, polyesters,
for example polyglycol terephthalates, and
polyacrylonitrile. It is also useful for pigment
printing and for the pigmenting of paper in the mass.
Due to its excellent heat resistance, the pigment is
in particular suitable for the pigmenting of plastics in
the mass, such as, for example, of polystyrene and its
mixed polymers, polyolefins, in particular polyethylene
and polypropylene and the corresponding mixed polymers,
polyvinyl chloride and polyesters in particular
polyethylene glycol terephthalate and polybutylene
terephthalate and the corresponding mixed condensation
products based on polyesters.
See, for example, with regard to ink: R. H. Leach,
editor, The Printing Ink Manual, Fourth Edition, Van
Nostrand Reinhold (International) Co. Ltd., London
(1988), particularly pages 282-591; with regard to
paints: C. H. Hare, Protective Coatings, Technology
Publishing Co., Pittsburgh (1994), particularly pages 63-
288; and with regard to plastics: T. G. Webber, Coloring
of Plastics, John Wiley & Sons, New York (1979),
particularly pages 79-204.
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The following examples illustrate the compositions
of the present invention and their methods of
preparation. Unless otherwise indicated in the following
examples and elsewhere in the specification and claims,
all parts and percentages are by weight, temperatures are
in degrees centigrade and pressures are at or near
atmospheric.
Example 1
A diazo slurry is prepared by dissolving 22.2 parts
2-amino-5-chloro-4-methylbenzene-1-sulfonic acid (C
Amine) in 390 parts water containing 4.0 parts sodium
hydroxide, reprecipitating the C Amine with 26.0 parts
20° Baume hydrochloric acid, adding ice to make a 0°
slurry, adding 7.0 parts sodium nitrite dissolved in 14
parts water and stirring the slurry at 0-5° for 60
minutes.
A coupler slurry is prepared by dissolving 20.7
parts 1-(4'-methylphenyl)-3-methyl-5-pyrazolone~(PTMP) in
205 parts water containing 4.5 parts sodium hydroxide at
about 40°, reprecipitating the PTMP with 67.5 parts 10%
acetic acid, adjusting the pH to 6.5 and heating the
slurry to 60-65°.
The diazo slurry is coupled into the coupler slurry
over a period of 20 minutes, while the pH is maintained
at 6.0-6.5 by addition of 10o sodium hydroxide and the
temperature is maintained at 60-65°. The slurry is
stirred and heated for one hour, then split to give four
equal parts of slurry 1.
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Example 1-1
f
To one part of slurry 1 at 40-45° are added 12.3
parts of 30a calcium chloride dihydrate solution. The
slurry a.s then heated, boiled for 30 minutes, iced to
lower than 50° and filtered; the filtercake is washed
with hot water, dried overnight at 70° and pulverized in
an Osterizer to give a fine powder pigment 1-1.
Example 1-2
The procedure of Example 1-1 a.s repeated, except
that 17.6 parts of 30o strontium nitrate solution are
used in place of the calcium chloride solution, to give
pigment 1-2.
Example 1-3
The procedure of Example 1-1 is repeated, except
that 42.5 parts of 10% mai~.ganous sulfate monohydrate
solution are used in place of the calcium chloride
solution, to give pigment 1-3.
Example 1-4
The procedure of Example 1-1 is repeated, except
that 24.0 parts of 30o zinc sulfate heptahydrate aqueous
solution are used in place of the calcium chloride
solution, to give pigment 1-4.
Comparative Example A
The procedure of Example 1 is repeated, except that
19.2 parts of 1-phenyl-3-methyl-5-pyrazolone (PMP) are
used in place of the PTMP, to give slurry A.
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Comparative Examples A-1 to A-4
The procedures 'of Examples 1-1 to 1-4 are repeated,
except that slurry A is used in place of slurry 1, to
give Comparative Examples A-1, A-2, A-3 and A-4.
Examt~le 2
The procedure of Example 1 is repeated, except that
22.2 parts of 2-amino-4-chloro-5-methylbenzene-1-sulfonic
acid (2B Acid) are used in place of the C Amine, to give
four equal parts of slurry 2.
Examples 2-1 to 2-4
The procedures of Examples 1-1 to 1-4 are repeated,
except that slurry 2~is used in place of slurry 1, to
give Examples 2-1, 2-2, 2-3 and 2-4.
Example 3
The procedure of Example 1 is repeated, except that
23.7 parts of 2-amino-5-chloro-4-ethylbenzene-1-sulfonic
acid (Ethyl C Amine) are used in place of the C Amine and
470 parts water are used in place of the 390 parts water,
to give four equal parts of slurry 3.
Example 3-1 to 3-4
The procedures of Examples 1-1 to 1-4 are repeated,
except that slurry 3 is used in place of slurry 1, to
give Examples 3-1, 3-2, 3-3 and 3-4.
Example 4
The procedure of Example 1-1 is repeated, except
that the coupling pH is controlled at 5.0-5.2 and the
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calcium chloride solution is added after the slurry is
boiled at pH 10 for 30 minutes, to give Example 4.
r
Example 5 ,.
The procedure of Example 3-1 is repeated, except
that the coupling pH is controlled at 5.0-5.2, to give
Example 5.
Example 6
The procedure of Example-1-1 is repeated, except
that 18.7 parts 2-amino-5-methylbenzene-1-sulfonic acid
(4B Acid) are substituted forthe C Amine in the diazo
and the coupling pH is controlled at 5.0-5.2, to give
Example 6.
Example 7
The procedure of Example 1 is repeated, except that
the coupler is added to a 5a acetic acid solution
containing 2.2 parts of tallowalkyl propylenediamine
(coupler is not reprecipitated) and the temperature
during coupling is maintained at 20-25° to give~Example
7.
Example 8
The procedure of Example 1-1 is repeated, except
that the diazo is prepared by dissolving 13.7 parts 2-
aminobenzoic acid in 100 parts 28° water containing 34
parts 20° Baume hydrochloric acid, then adding ice to
make the 0° slurry, in place of the C Amine slurry; the
pH during coupling is allowed to fall to 0.9, then raised
to 4.0 with 65 parts sodium acetate trihydrate, to give
Example 8.
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Example 9
The procedure of Example 1-1 is repeated, except
A that 22.3 parts 2-aminonaphthalene-1-sulfonic acid
(Tobias Acid) are used in place of the C Amine, 25 parts
sodium acetate trihydrate are added to the PTMP coupler
slurry, the coupling temperature is 20-25° and the pH is
allowed to fall from 6.8 to 4.7, to give Example 9.
Example 10
The procedure of Example 1-2 is repeated, except
that 18.7 parts 2-amino-5-methylbenzene-1-sulfonic acid
(4B Acid) are used in place of the C Amine, to give
Example 10.
Example 11
The procedure of Example 2-1 is repeated, except
that 23.0 parts 1-(3'-chlorophenyl)-3-methyl-5-pyrazolone
are used in place of the PTMP, to give Example 11.
Testing of Picrments
The standard pigment, to which the experimental
pigments are compared, is Hoechst 11-3071 PV Fast Yellow
HGR (P. Y. 191).
The pigments are tested as tints with titanium
dioxide, either as 1:10 (pigment:titanium dioxide) or 1:1
tints in air-dry alkyd enamel drawdowns or as 1:19 tints
in high density polyethylene injection molded chips, as
follows:
Test Method I
A mixture of 0.60 part pigment, 6.0 parts titanium
dioxide (DuPont Ti-Pure R-960), 23._2 parts air-dry alkyd
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enamel vehicle (containing 86o medium oil alkyd, 13%
mineral spirits and 1% driers/antiskinning agent) and 75
parts media (Zirconia Zirbeads Y1304) is stirred with a
spatula to a uniform mixture, sealed with a lid and
shaken on a paint shaker for 30 minutes. The dispersion
is separated from the media, drawn down with a 0.15 mm.
gap coating bar on coated cardboard (Leneta Form 2-C) and
allowed to dry for 1-2 days. Spectrophotometric values
are measured with a Macbeth Color-Eye (specular component
included, large area) to give the apparent strength and
hue angle difference (DH) under Illuminant D, 10°, shown -
in.the Tables. The drawdowns are exposed in a carbon arc
or xenon arc Fade-O-Meter for 300 hours, then measured in -
the Color-Eye to give the Hunter Color-Difference (DE).
Test Method II
A mixture of 2.5 parts pigment, 2.5 parts titanium
dioxide, 23.5 parts air-dry alkyd enamel vehicle
described in Test Method I and 75 parts media (Zirconia
Zirbeads 41304) is stirred with a spatula to a uniform
mixture, sealed with a lid and shaken on a paint shaker
for 30 minutes. The dispersion is separated from the
media, drawn down with a 0.15 mm. gap coating bar on an
aluminum panel and allowed to dry for 1-2 days. The
panels are exposed in a Weatherometer, then measured
after 200 hours, 500 hours and 800 hours in the Color-Eye
to give the Hunter Color-Difference (DE).
CA 02212460 2006-05-08
- 19 -
Test Method III
A mixture of 0.125 part pigment, 2.375 part titanium
dioxide (DuPont Ti-PureT"" R-960) and 500.0 parts high
density polyethylene (SolvayT"' T50-2000-G) is shaken on a
paint shaker to uniformity, then injection molded at 232°
in a 30 ton Battenfeld machine. As a measure of heat
stability, the melt is held at 232° for an additional 15
minutes. Spectrophotometric values of the molded chips
are measured as in Test Method I.
CA 02212460 1997-08-07
WO 96/25464 PCT/US96I01240
- 20 -
TABLE I
Results from Test Method I
f
DE of ter 3 0 0 hrs .
Exposure in Carbon
Pigmen t Annarent StrengthDH Arc Fade-O-Meter ,
Standard Standard
Y. 191 (K/S=4.786) (h=79.7) 2.09
P
. +54% -4.4 2.54
1-1
Ex
. +36% -3.1 3.97
1-2
Ex
. +62% -4.9 3.50
1-3 -
Ex
. +55% -5.0 2.64
Ex. 1-4
Comp.Ex. 1-1 +35% -3.3 10.34*
*
Comp.Ex. 1-2 +78% -0.9 6.90
Comp.Ex. 1-3 -10% -3.3 5.69*
Comp.Ex. 1-4 +23% -2.9 12.77
8 +7% -3.6 3.84
Ex
. *aft er 100 hrs.
TABLE TI
Results from Test Method _
I
DE after 300 hrs.
Exposure in Xenon
Pigment Apparent Strength DH Arc Fade-O-Meter
Standard Standard
P.Y..191 (K/S=4.786) (h=79.7) 1.20
1-1 +54 -4.4 1.00
Ex
. +68 -8.6 0.85
Ex. 2-1
Ex. 2-2 +57 -6.5 0.66
2-3 +72 -10.2 0.49
Ex
. +52 -10.1 0.71
Ex. 2-4
3-1 +61 -3.0 1.42
Ex
. +42 -3.2 2.17
Ex. 3-2
3-3 +17 -0.8 2.50
Ex
. +6 -2.7 2.30
Ex. 3-4
Ex. 9 +21 +2.5 13_7
+8 -8.3 6.33
Ex
. +42 +4.2 - 8.15
Ex. 11
TABLE III
Results from Test Method II
DE after Exposure m a
Weatherometer for:
Pigment Apparent Strength DH 200 hrs.- 500 hrs. 800 hrs.
Standard Standard
P.Y. 191 (K/S=20.334) (h=74.8°) 0.81 2.16 4.33
Ex. 1-1 +36% -9.8 0.70 1.02 1.56
Ex. 2-1 +43% -17.4 0.50 1.81 2.76
Ex. 3-1 _ +45% -9.1 0.63 -1.33 1.92
TABLE IV
Results from Test Method III
Changes in Color
Values After
minutes at 232°
Pigment Annarent Strength DH DE Strength
Standard Standard
P.Y. 191 (K/S=3.534) (h=85.8°) 0.28 -4%
Ex. 2-1 +22 +0.9 1.65 -4%
Ex. 4 +42 +1.7 0.32 +1%
Ex. 5 +25 +2.7 0.95 +3%
Ex. 6 +40 +1.9 0.37 Equal
SUBSTITUTE SHEET (RULE 26)
CA 02212460 1997-08-07
WO 96125464 PCT/US96101240
- 21 -
' As can be seen from the foregoing tables, the
pigments of this invention generally show significant
' improvement in color strength, lightfastness and/or heat
stability over Pigment Yellow 191 (Hoechst Yellow HGR).
