U.S. patent application number 09/862673 was filed with the patent office on 2001-09-20 for pigment particle growth and/or crystal phase directors.
Invention is credited to Babler, Fridolin.
Application Number | 20010022150 09/862673 |
Document ID | / |
Family ID | 26816318 |
Filed Date | 2001-09-20 |
United States Patent
Application |
20010022150 |
Kind Code |
A1 |
Babler, Fridolin |
September 20, 2001 |
Pigment particle growth and/or crystal phase directors
Abstract
Pigment particle growth and/or crystal phase directors of the
following formula:
(MO.sub.3S).sub.m--Q--(CH.sub.2--(X)--(Y).sub.n).sub.o wherein: Q
represents a pigment moiety; M represents a metal cation,
quaternary N cation or H; X is an aromatic group, a cyclo-hetero
aliphatic group with at least one 5 atom or 6 atom ring or a hetero
aromatic group with at least one 6 atom ring and which is not a
phthalimido group; Y is a sulfonic or carboxylic acid or salt
thereof; m and n independently from each other represent an integer
from 0 to 2.5; and o is an integer from 0.05 to 4.
Inventors: |
Babler, Fridolin;
(Hockessin, DE) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
26816318 |
Appl. No.: |
09/862673 |
Filed: |
May 22, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09862673 |
May 22, 2001 |
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09496494 |
Feb 2, 2000 |
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6264733 |
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60118405 |
Feb 2, 1999 |
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Current U.S.
Class: |
106/410 ;
106/497; 106/498; 540/123; 540/131; 544/75; 546/49 |
Current CPC
Class: |
C09B 67/0036 20130101;
C09B 48/00 20130101; C09B 67/0033 20130101 |
Class at
Publication: |
106/410 ;
106/497; 106/498; 546/49; 540/123; 540/131; 544/75 |
International
Class: |
C09B 047/04; C09B
049/12 |
Claims
What is claimed:
1. A compound of formula I
(MO.sub.3S).sub.m--Q--[CH.sub.2--(X)--(Y).sub.n- ].sub.o (I)
wherein: Q represents a pigment moiety; M represents a metal
cation, quaternary N cation or H; X is an aromatic group, a
cyclo-hetero aliphatic group with at least one 5 atom or 6 atom
ring or a hetero aromatic group with at least one 6 atom ring and
which is not a phthalimido group; Y is a sulfonic or carboxylic
acid or salt thereof; m and n independently from each other are
numbers from 0 to 2.5; and o is a number from 0.05 to 4.
2. A compound of claim 1, wherein said pigment moiety is a pigment
selected from the group of anthraquinone, phthalocyanine, perinone,
perylene, diketopyrrolopyrrole, thioindigo, iminoisoindoline,
iminoisoindolinone, quinacridone, flavanthrone, dioxazine,
indanthrone, anthrapyrimidine and quinophthalone pigments.
3. A compound of claim 1, wherein the pigment moiety is a pigment
selected from the group of quinacridone or diketopyrrolopyrrole
pigments.
4. A compound of claim 1, wherein the pigment is a quinacridone of
the formula II: 2wherein A and D are independently substituents
selected from H, F, Cl, C.sub.1-C.sub.3alkyl and
C.sub.1-C.sub.3alkoxy.
5. A compound of claim 1, wherein the pigment is an unsubstituted
quinacridone.
6. A compound of claim 1, wherein the metal cation M is sodium,
potassium, calcium, magnesium or aluminum.
7. A compound of claim 1, wherein X is an aromatic group selected
from a 5 carbon or 6 carbon ring and a polycyclic groups comprising
two to six fused 5 carbon and/or 6 carbon rings.
8. A compound of claim 7, wherein said aromatic group is phenylene,
naphthalene, anthracene, phenanthrene, pyrene or perylene.
9. A compound of claim 8, wherein the aromatic group is a phenylene
or naphthalene.
10. A compound of claim 1, wherein X is a cyclo-hetero aliphatic
group comprising at least one 5 or 6 atom ring.
11. A compound of claim 10, wherein said cyclo-hetero aliphatic
group is barbituric acid.
12. A compound of claim 1, wherein said hetero-aromatic group which
is not a phthalimido group comprises a 6 atom ring or fused 5
and/or 6 atom rings, and wherein said hetero-aromatic group
contains 1 to 4 hetero atoms selected from N, S and/or O.
13. A compound of claim 12, wherein said hetero-aromatic group is a
pyridine, quinoline or carbazole group.
14. A compound of claim 1, wherein said aromatic, cyclo-hetero
aliphatic or hetero-aromatic group is optionally substituted with
one or more halogen, oxy, hydroxy, imino, amino,
C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18 alkoxy groups.
15. A compound of claim 14, wherein said aromatic, cyclo-hetero
aliphatic or hetero-aromatic group is optionally substituted with
one or more C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.3 alkoxy
groups.
16. A compound of claim 1, wherein said aromatic group is toluene,
ortho- meta- or para-xylene, chlorobenzene, ortho- meta- or
para-dichlorobenzene, 1- or 2-methyinaphthalene or
anthraquinone.
17. A compound of claim 1, wherein said hetero-aromatic group is
derived from melamine, 1,3,7-trimethylxanthin, hydantoin,
2-methylbenzimidazole, 2,6,8-trihydroxypurine, 1,8-naphtosultam,
o-benzoic acid sulfimide or 2,4-dihydroxyprimidine.
18. A compound of claim 1, wherein Y is a free carboxylic acid or
sulfonic acid group or a sodium, potassium, magnesium, calcium or
aluminum salt thereof.
19. A compound of claim 18, wherein Y is a free sulfonic acid group
or a sodium, potassium or aluminum salt thereof.
20. A composition containing a mixture of compounds of claim 1,
wherein m represent is on average a number from 0-0.1, n is on
average from 0-1.2, and o is on average a number from 0.2 to
1.5.
21. A process for the preparation of a compound of claim 1,
wherein: A) dissolving a pigment of the pigment moiety Q in
concentrated sulfuric acid; B) adding and dissolving at temperature
less than 50.degree. C. the intermediate X to the solution; C)
adding para-formaldehyde at a temperature less than 50.degree. C.;
D) heating the mixture of step C) to about 50 to about 100.degree.
C.; E) isolating a precipitate from the reaction in step D.
22. A process according to claim 21 wherein the mixture is heated
in step D for about 30 minutes to about 6 hours and wherein the
process further comprises the step of drowning the reaction mixture
from step D in water to provide a precipitate.
23. A process according to claim 21, wherein the molar ratio of the
pigment moiety Q:intermediate X:formaldehyde is 1:1 to 1.2:1 to
2.
24. A process for the direct synthesis of a pigmentary grade
anthraquinone, phthalocyanine, perinone, perylene,
diketopyrrolopyrrole, thioindigo, iminoisoindoline,
iminoisoindolinone, quinacridone, flavanthrone, dioxazine,
indanthrone, anthrapyrimidine or quinophthalone pigment wherein
said pigment is synthesized in the presence of 0.1 to 25 weight
percent of a pigment particle growth and/or crystal phase director
compound of claim 1, based on the weight pigment being
synthesized.
25. A process for the preparation of a direct pigmentary
diketopyrrolopyrrole or quinacridone pigment or a solid solution
thereof comprising the step of adding to the reaction mixture from
which said pigment or solid solution is synthesized, 0.1 to 25
percent by weight of at least one compound of claim 1, based on the
pigment being synthesized.
26. A process according to claim 25, wherein said pigment or solid
solution is quinacridone, 2,9-dichloroquinacridone,
4,11-dichloroquinacridone, 2,9-dimethylquinacridone pigment or
solid solutions thereof.
27. A method of improving the heat stability, rheological and
flocculant properties of pigment particles, said method comprising
adding to said pigment particles at least one compound of claim 1
in an amount sufficient to reduce flocculation or improve the heat
stability.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to novel compounds which can
direct and control the growth and/or crystal phase of pigment
particles. Such compounds are particularly useful when present
during the synthesis of the pigment.
BACKGROUND OF THE INVENTION
[0002] A number of patents describe processes for the direct
synthesis of pigments in a pigmentary form to avoid the additional
expensive and oftentimes environmentally unfriendly pigment
finishing processes (e.g. processes for particle size reduction
and/or crystal-form modification). For example European Patent No.
643,110 and U.S. Pat. No. 5,424,429 describe a direct synthesis of
quinacridone solid solutions and 2,9-dichloroquinacridone in
pigmentary form, respectively, in the presence of quinacridone
phthalimidomethyl derivatives. European Patent No. 685,530
describes the preparation of a direct synthesis of pigmentary grade
dioxazine in the presence of a dioxazine derivative.
[0003] It is also known that sulfonic acid derivatives of certain
pigments can effectively diminish the crystal growth during the
isolation of the pigment from a reaction mixture. Such sulfonic
acid derivatives are described, for example, in U.S. Pat. No.
3,386,843. Other patents describe the use of sulfonic acid
derivatives of pigments to stabilize against recrystallization and
change of crystal modification as, for example, in G.B. Patent No.
1,544,839 which is directed to phthalocyanine pigments.
[0004] U.S. Pat. No. 5,755,873 describes a method for the
preparation of quinacridone pigments in which a quinacridone
derivative is incorporated during synthesis and copending
provisional application Ser. No. 60/087,773 describes a direct
synthesis of pigmentary diketopyrrolopyrrole pigments in the
presence of quinacridone or diketopyrrolopyrrole derivatives.
[0005] Although the addition of such known pigment derivatives can
be advantageous; pigment synthesis in the presence of such
derivatives in many cases does not provide the favored pigmentary
crystal size, shape or crystal modification. Therefore many
pigments so synthesized may still require finishing steps to obtain
pigments with the preferred color characteristics.
SUMMARY OF THE INVENTION
[0006] The present invention is based on the discovery that new
selected pigment derivatives in which a specific aromatic or hetero
aromatic group is linked by a methylene group to a pigment molecule
are particularly effective for directing and controlling the growth
and/or crystal modification of pigment particles when present
during the pigment synthesis step.
[0007] Such pigment particle growth directors can be prepared by
simple synthesis procedures and offer the pigment manufacturer a
means to prepare a pigment providing the preferred color
characteristic without requiring additional pigment finishing step.
The inventive compounds allow the manufacturer to produce high
performance organic pigments in an economical and environmentally
friendly manner of producing high performance organic pigments and
thus, are of extreme commercial importance.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
[0008] The present invention relates to novel compounds of formula
I:
(MO.sub.3S).sub.m--Q--[CH.sub.2--(X)--(Y).sub.n].sub.o (I)
[0009] wherein Q represents a pigment moiety, M represents a metal
cation, quaternary N cation or H, X is a aromatic group or a cyclo
hetero aliphatic group with at least one 5 or 6 atom ring or a
hetero aromatic group with at least one 6 atom ring and which is
not a phthalimido group, Y is a sulfonic acid or carboxylic acid or
salt thereof, m and n independent of one another are numbers from
zero to 2.5, and o is a number from 0.05 to 4. The present
invention further relates to a process for the preparation and use
of such compounds.
[0010] Generally, the pigment moiety Q is a pigment selected from
the group of anthraquinone, phthalocyanine, perinone, perylene,
diketopyrrolopyrrole, thioindigo, iminoisoindoline,
iminoisoindolinone, quinacridone, flavanthrone, dioxazine,
indanthrone, anthrapyrimidine and quinophthalone pigments.
Preferably, the pigment moiety Q is a quinacridone or diketo
pyrrolo pyrrole pigment. Particularly preferably, the pigment
moiety Q is a quinacridone of the general formula II: 1
[0011] wherein A and D are independently 1 or 2 substituents
selected from H, F, Cl, C.sub.1-C.sub.3alkyl and
C.sub.1-C.sub.3alkoxy. The pigment moiety Q is not a compound that
produces colorless derivatives, such as derivatives of
6,13-dihydroquinacridones. Most preferably the pigment moiety Q is
an unsubstituted quinacridone.
[0012] Preferably, m of formula I is a number from about zero to
0.5, most preferably zero to 0.1; n is a number from about zero to
2, most preferably from about zero to 1.2; and o is a number from
about 0.1 to 2, most preferably from about 0.2 to 1.5. The values
for m, n and o are determined by analytical methods like mass
spectrometry such as LCMS, GCMS or the matrix-assisted laser
desorption ionization technique (MALDI).
[0013] The metal cation M of formula I is preferably sodium,
potassium, calcium, magnesium or aluminum. The quaternary N cation
of formula 1 is an ammonium or an alkyl ammonium group.
[0014] Typically, the group X of formula I is an aromatic group
with a 5 carbon or 6 carbon ring; or a polycyclic group containing
two to six fused 5 carbon and/or 6 carbon rings; a cyclo-hetero
aliphatic group including at least one 5 atom or 6 atom ring; or a
hetero aromatic group, which is not a phthalimido, and includes a 6
atom ring, fused 6 atom rings or fused 5 and 6 atom rings and in
which there are 1 to 4 hetero atoms of N, S and/or O.
[0015] Suitable aromatic groups include, for example, phenylene,
naphthalene, acenaphthylene, anthracene, phenanthrene, naphthacene,
chrysene, pyrene or perylene. Preferably the aromatic group is
phenylene, naphthalene, anthracene or pyrene, and most preferably
the aromatic group is phenylene or naphthalene.
[0016] Cyclo-hetero aliphatic groups are, for example, pyrrolidine,
imidazolidine, piperidine, piperazine or morpholine.
[0017] Appropriate hetero aromatic groups are, for instance,
pyridine, pyrazine, pyrimidine, pyridazine, indole, isoindole,
quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone
or benzothiazole, preferably pyridine or carbazole.
[0018] The above exemplified aromatic, cyclo hetero aliphatic or
hetero aromatic groups can optionally be substituted with one or
more halogen, oxy, hydroxy, imino, amino and/or
C.sub.1-C.sub.18alkyl groups, preferably C.sub.1-C.sub.3alkyl or
C.sub.1-C.sub.3alkoxy groups.
[0019] Examples of the large number of such substituted groups are
for instance toluene, ortho-, meta- or para-xylene, chlorobenzene,
1- or 2-methylnaphthalene or anthraquinone, barbituric acid,
melamine, 1,3,7-trimethylxanthin, hydantoin, 2-methylbenzimidazole,
2,6,8-trihydroxypurine, 1,8-naphtosultam, o-benzoic acid sulfimide
or 2,4-dihydroxyprimidine.
[0020] Preferred aromatic groups are toluene, ortho-, meta- or
para-xylene, chlorobenzene, 1- or 2-methylnaphthalene or
anthraquinone. Preferred hetero aromatic groups are melamine,
1,3,7-trimethylxanthin, hydantoin, 2-methylbenzimidazole,
2,6,8-trihydroxypurine, 1,8-naphtosultam, o-benzoic acid sulfimide
or 2,4-dihydroxyprimidine.
[0021] Commonly the group Y is a carboxylic acid or a sulfonic acid
group. Most preferably the group Y is a free sulfonic acid or a
sodium, potassium, magnesium, calcium or aluminum salt thereof.
[0022] A further embodiment of the present invention is a process
for the preparation of compounds of formula I or II, wherein: a)
the pigment of the pigment moiety Q is dissolved in concentrated
sulfuric acid; b) the intermediate X is added into the solution and
dissolved at a temperature below 50.degree. C.; c)
para-formaldehyde is added at a temperature below 50.degree. C.; d)
and then is heated to a temperature from to 50 to 100.degree. C.;
e) and then isolated.
[0023] The inventive compounds are prepared for example by a
process in which the pigment moiety Q and the intermediate X, a
substantial portion of which is the moiety of group X, are reacted
with formaldehyde. Preferably the reaction is carried out in
concentrated (95-98%) sulfuric acid. In one preferred method, the
pigment of the pigment moiety Q is dissolved in concentrated
sulfuric acid at a concentration of about 5 to 30 weight percent,
most preferably about 10 to 20 weight percent at a temperature
below about 50.degree. C., preferably at about 35 to 45.degree. C.
The intermediate X is added to the pigment solution at a
temperature below about 50.degree. C., preferably at about 35 to
45.degree. C. and is also dissolved. Finally the formaldehyde is
added, preferably in the form of para-formaldehyde, at a
temperature below about 50.degree. C., preferably at about 35 to
45.degree. C. The reaction mixture is heated to a temperature from
about 50 to 100.degree. C. and stirred at that temperature until
the reaction is complete, preferably for about 30 minutes to 6
hours, most preferably from about 30 to 90 minutes, and drowned
into ice water. The slurry is stirred for about 5 minutes to 6
hours, preferably from about 30 minutes to 3 hours, at a
temperature from about 0 to 50.degree. C., preferably from about 10
to 25.degree. C. The inventive compounds are then isolated by
filtration or centrifugation and are preferably washed with water.
The resulting product cake can be dried or can be used in the form
of an aqueous cake as an additive during the pigment synthesis.
[0024] In general a stochiometric amount of pigment, intermediate X
and formaldehyde is used; however an excess of the intermediate X
or formaldehyde may be used to achieve the desired product.
Preferably, the molar ratio of the pigment: intermediate X:
formaldehyde is 1:1 to 1.2:1 to 2.
[0025] If a high degree of sulfonation is desired, the reaction
mixture is stirred at higher temperature, for example, above
60.degree. C. If it is desirable to have a low degree of
sulfonation, the reaction is maintained at lower temperature, for
example, below 60.degree. C.
[0026] The isolated samples can be analyzed by known methods, for
example, by elementary analysis or mass spectrometry such as LCMS,
GCMS or the matrix-assisted laser desorption ionization technique
(MALDI) or by the HPLC method, all of which are well known to those
of ordinary skill in the art. Using the preferred technical
preparation method described above, which does not include specific
cleaning steps, the purity of the isolated product is generally not
100% and contains, depending on the starting materials and reaction
temperature, some remaining starting materials or other byproducts
which, when in a concentration that does not impact the effect of
the particle size and crystal phase director, are tolerated and can
actually provide additional advantageous effects. By technically
well known methods, such as solvent treatments, recrystallization
or precipitation from basic polar solvent solutions, for example in
basic dimethyl sulfoxide or dimethyl formamide, such products can
be further purified, if desired.
[0027] Generally, the inventive pigment particle growth and crystal
phase director compounds are added at a concentration of about 0.1
to 15 percent, preferably about 0.3 to 10 percent and most
preferably about 0.5 to 8 percent, based on the pigment to be
synthesized, before or during the final steps of pigment
synthesis.
[0028] The inventive pigment particle growth and/or crystal phase
directors are suitable as additives for the synthesis of pigments
of several pigment classes including pigments of the anthraquinone,
phthalocyanine, perinone, perylene, diketopyrrolopyrrole,
thioindigo, iminoisoindoline, iminoisoindolinone, quinacridone,
flavanthrone, dioxazine, indanthrone, anthrapyrimidine and
quinophthalone pigment classes. Preferably, but not essentially,
the pigment used in the pigment moiety Q of the inventive compounds
belongs to the same pigment class as the pigment being
synthesized.
[0029] The inventive compounds are particularly suitable for the
synthesis of direct pigmentary grade diketo pyrrolopyrrole and
quinacridones and/or its solid solutions. Said compounds are highly
suitable for the synthesis of quinacridone pigments in their
specific crystal modifications, such as the alpha, beta or gamma
quinacridone, 2,9-dichloroquinacridone, 2,9-dimethyl-quinacridone,
4,11-dichloroquinacridone and solid solutions thereof. The
inventive pigment particle growth directors are particularly
effective when said pigment particle growth directors are
completely or partially soluble in the reaction media in which the
pigment is being synthesized.
[0030] A further embodiment of the present invention concerns a
process for the direct synthesis of a pigmentary grade
anthraquinone, phthalocyanine, perinone, perylene,
diketopyrrolopyrrole, thioindigo, iminoisoindoline,
iminoisoindolinone, quinacridone, flavanthrone, dioxazine,
indanthrone, anthrapyrimidine or quinophthalone pigment wherein
said pigment is synthesized in the presence of 0.1 to 25 weight
percent of a pigment particle growth director of formula I, based
on the weight pigment being synthesized.
[0031] Preferably, for the direct synthesis of a pigmentary grade
quinacridone, quinacridone, 2,9-dichloroquinacridone,
4,11-dichloroquinacridone, 2,9-dimethylquinacridone, the pigment or
solid solution thereof is synthesized in the presence of 0.1 to 25
weight percent of a pigment particle growth director compound of
formula I, based on the weight pigment being synthesized.
[0032] In addition, the present invention concerns a process for
the preparation of a direct pigmentary diketopyrrolopyrrole or
quinacridone pigment or a solid solution thereof comprising the
step of synthesizing said pigment or solid solution in the presence
of 0.1 to 25 percent by weight of at least one compound of formula
I based on the pigment being synthesized.
[0033] Without limiting this invention to any particular theory, it
is believed that the inventive particle growth director molecule
adheres to the synthesized pigment molecule and by doing so directs
the crystal growth and crystal phase. The term "directing the
crystal growth" refers to controlling the synthesis of pigment
particles to have a suitable pigmentary size as well as directing
the growth of the crystals to generate particles of a specifically
desired shape, such as platelet, needle, cubic, leaflet, prismatic
and other geometric forms, in a desired crystal phase. The effect
can be influenced by the chemical structure of the organic pigment,
the selection of the reaction media and the concentration and
chemical structure of the inventive particle growth inhibitor.
[0034] During the isolation of the pigment, for example in the
filtration step, these compounds--when soluble in the reaction
media--can be washed out and if desirable, be recollected from the
filtrate or wash liquid. Typically, these compounds are partially
left on the pigment surface and can have additional benefits. Such
benefits are, for example, improved pigment properties such as
rheological properties, dispersibility and wetting behavior,
flocculation resistance and improved heat stability.
[0035] In certain cases, it is advantageous to use the inventive
compounds in mixture or in combination with other additives
including known pigment particle growth inhibitors such as, for
example, phthalimidomethyl-, imidazolmethyl- or
pyrazolmethyl-quinacridone, pigment sulfonic acids or specific
polymers; or other optional ingredients such as wetting agents,
surfactants, defoamers, antioxidants, UV absorbers, light
stabilizers, plastisizers, or general texture improving agents and
so forth. Any such additional additives may be used as long as said
additives are stable under the pigment synthesis conditions and
have no negative impact on the final pigment properties or the
environment. Generally such additives can be used in a
concentration from about 0.1 to 25 percent, preferably from about
0.2 to 15 percent and most preferably from about 0.5 to 8 percent,
based on the pigment to be synthesized. The resulting
pigment/additive mixture can be used in any conventional pigment
application, such as in the formation of paints, inks, color
filters, fibers, paper and textiles.
[0036] Suitable polymers are, for example, polyacrylic acid,
polymethacrylic acid, polymaleic anhydride, polyurethane,
polyvinylether, polyvinylalcohol, polyalkylene glycol, polyethylene
oxide, cellulose derivatives, polyimine, polyvinylpyridine, or
copolymers such as copolymers of acrylic acid with styrene,
acrylonitrile, vinylacetate, vinylphosphonate, vinylpropionate,
vinylchloride, itaconic acid or maleic anhydride, or a mixture
thereof, or polymeric derivatives like ethoxylated or propoxylated
fatty amines such as ethoxylated cocoalkyl, oleyl or soyaalkyl
amines; ethoxylated or propoxylated fatty quaternary salts such as
ethoxylated cocoalkyltrimethyl ammonium chloride; ethoxylated fatty
amides such as ethoxylated oleamides; alkyl-, cycloalkyl- or
alkylaryl-oxypoly (ethylen-oxy)ethanol,
cycloalkyloxypoly(ethylenoxy)laurate or oleate, polyethylene glycol
400 laurate or oleate, alkyl-, cycloalkyl- or
alkylaryl-poly(ethylenoxy)carbo- xylate or phosphonate.
[0037] Suitable surfactants include anionic surfactants such as
alkylbenzene- or alkylnaphthalene-sulphonates, alkylsulfosuccinates
or naphthalene formaldehyde sulfonates; cationic surfactants
including, for example, quaternary salts such as benzyl tributyl
ammonium chloride; or nonionic or amphoteric surfactants such as
polyoxyethylene surfactants and alkyl- or amidopropyl betaines,
respectively
[0038] Suitable texture improving agents are, for example, fatty
acids such as stearic acid or behenic acid, and fatty amines such
as laurylamine and stearylamine. In addition, fatty alcohols or
ethoxylated fatty alcohols, polyols such as aliphatic 1,2-diols or
epoxidized soy bean oil, waxes, resin acids and resin acid salts
may be used for this purpose.
[0039] Suitable UV stabilizers are, for example, the known
benzotriazol derivatives known under the trade name TINUVIN or CIBA
Fast H Liquid an aryl sulfonated benzotriazol, both being products
of CIBA Specialty Chemicals Corporation.
[0040] Due to the ability to act as an antiflocculant as well as an
excellent particle growth inhibitor and phase director, the
inventive compounds can generally be used in the pigment finishing,
pigment treatment, or pigment application such as an additive
during the pigment dispersion step in bead mills, extruder,
calendar and so forth, as well as during pigment synthesis. Also,
the inventive compounds are themselves strongly colored and can be
used as coloring agents, for example in the paints, inks, color
filters, plastics, fibers, and in the paper or textile
industry.
[0041] Additionally, many of the inventive compounds provide
physical properties that are similar to those of pigments;
specifically low solubility in organic solvents or the application
media. Therefore, said compounds are non-bleeding and, for example,
will not migrate into food when a pigment composition containing
the inventive compound is used as a coloring agent in food
packaging materials.
[0042] The following examples further describe some preferred
embodiments of the invention, but do not limit the scope of the
invention. In the examples, all parts are by weight unless
otherwise indicated.
EXAMPLE 1
[0043] A one liter flask equipped with a stirrer, thermometer,
condenser and drying tube was charged with 200 ml concentrated
(95-98%) sulfuric acid. 46.8 grams (0.15 mol) MONASTRAL Red Y
RT-759-D, an unsubstituted quinacridone pigment of CIBA Specialty
Chemicals Corporation were added at a temperature below 45.degree.
C. and the mixture was stirred for 20 minutes at 40-45.degree. C.,
to completely dissolve the pigment.
[0044] 26.4 grams (0.15 mol) benzene sulfonic acid (90%) were added
at a temperature below 45.degree. C. and the mixture was stirred
for 20 minutes at 40 to 45.degree. C., followed by the rapid
addition of 4.8 grams (0.16 mol) para formaldehyde. The reaction
mixture was stirred for one hour at 55-60.degree. C., then poured
into 2.5 liter ice water. The precipitate was stirred for 21/2
hours at room temperature, then filtered. The press cake was washed
with water to a pH of 5 and dried yielding a product in which
benzene sulfonic acid methyl quinacridone with the molecular weight
of 482 was detected by MALDI.
EXAMPLE 2
[0045] A one liter flask equipped with a stirrer, thermometer,
condenser and drying tube was charged with 200 ml concentrated
(95-98%) sulfuric acid. 31.2 grams (0.1 mol) MONASTRAL Red Y
RT-759-D were added at a temperature below 45.degree. C. and the
mixture was stirred for 20 minutes at 40-45.degree. C. to
completely dissolve the pigment.
[0046] 41.4 grams (0.1 mol) naphthalin-1-sulfonic acid (50%) were
added at a temperature below 45.degree. C. and the mixture was
stirred for 20 minutes at 40 to 45.degree. C. followed by the rapid
addition of 3.2 grams (0.107 mol) para formaldehyde. The reaction
mixture was stirred for one hour at 55-60.degree. C. then poured
into 2.5 liter ice water. The precipitate was stirred for 21/2
hours at room temperature, then filtered. The press cake was washed
with water to a pH of 2.8 and kept as presscake. A small sample was
further washed to a pH of 5 and dried yielding a product in which
naphthalin-1-sulfonic acid methyl quinacridone having a molecular
weight of 532 was detected by MALDI.
EXAMPLE 3
[0047] The procedure of Example 2 was repeated using 0.1 mol
naphthalin-2 sulfonic acid instead of naphthalin-1-sulfonic acid to
yield a product in which naphthalin-2-sulfonic acid methyl
quinacridone having a molecular weight of 532 was detected by
MALDI.
EXAMPLE 4
[0048] The procedure of Example 2 was repeated using 0.1 mol
anthraquinone-2 sulfonic acid instead of naphthalin-1-sulfonic
acid, yielding a product in which anthraquinone sulfonic acid
methyl quinacridone having a molecular weight of 614 was detected
by MALDI.
EXAMPLE 5
[0049] The procedure of Example 2 was repeated using 18.4 grams
(0.1 mol) o-benzoic acid sulfimide sodium salt instead of
naphthalin-1-sulfonic acid, yielding a product in which o-benzoic
acid sulfimide methyl quinacridone having a molecular weight of 507
was detected by MALDI.
EXAMPLE 6
[0050] The procedure of Example 2 was repeated using 20.4 grams
(0.1 mol) Naxonate ST, a commercially available sodium toluene
sulfonate from Ruetgers-Naese (sodium toluene sulfonate with a
content of 93%) instead of naphthalin-1-sulfonic acid, yielding a
product in which toluene sulfonic acid methyl quinacridone having a
molecular weight of 496 was detected by MALDI.
EXAMPLE 7
[0051] A one liter flask equipped with a stirrer, thermometer,
condenser and drying tube was charged with 200 ml concentrated
(95-98%) sulfuric acid. 28.8 grams IRGAZIN DPP Scarlet EK (0.1 mol
of a commercial 3,6-diphenyl-1,4-diketopyrrol-[3,4-c]-pyrrole
pigment from CIBA Specialty Chemicals Corp.) were added at a
temperature of 40-45.degree. C. and the mixture was stirred for 20
minutes at 40-45.degree. C. to completely dissolve the pigment.
[0052] 18.4 grams (0.1 mol) o-benzoic acid sulfimide sodium salt
were added at a temperature below 45.degree. C. and the mixture was
stirred for 20 minutes at 40 to 45.degree. C. followed by the rapid
addition of 3.2 grams (0.107 mol) para formaldehyde. The reaction
mixture was stirred for 50 minutes at 45-50.degree. C. then poured
into 2.5 liter ice water. The precipitate was stirred for 11/2
hours at room temperature, then filtered. The press cake was washed
with water neutral and dried yielding a red brown product in which
o-benzoic acid sulfimide methyl
3,6-diphenyl-1,4-diketopyrrol-[3,4-c]-pyrrole having a molecular
weight of 483 was detected by MALDI.
EXAMPLE 8
[0053] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 40 grams 6,13-dihydroquinacridone, 180
ml methanol and 40.9 grams 50% aqueous sodium hydroxide. The
mixture was stirred under a slow flow of nitrogen at 30-45.degree.
C. for five minutes. 2.4 grams of the pigment additive prepared
according to Example 4, followed by 0.5 grams anthraquinone mono
sulfonic acid sodium salt as catalyst, were added and the reaction
mixture was heated to reflux for one hour generating the sodium
salt of 6,13-dihydroquinacridone. 73.5 grams of an aqueous 16.9%
hydrogen peroxide solution were added into the reaction mixture
with a peristaltic pump at a rate of 0.3 ml/minute while
maintaining reflux under a slow nitrogen flow. The resulting
reddish suspension was further stirred for 10 minutes at reflux
then diluted with 100 ml cold water and filtered. The presscake was
washed with hot water then dried, yielding 38.9 grams red
quinacridone.
[0054] The product showed a purity of above 98% quinacridone as
determined by a spectrophotometric method. The x-ray diffraction
pattern of the pigment shows the characteristics of an alpha
quinacridone. A microscopic view of the pigment shows crystals
having a length of 1 to 6 .mu.m and a width of 0.2 to 0.6 .mu.m.
When incorporated into plastics or paints the pigment imparted a
bright yellowish red color with excellent properties.
EXAMPLE 9
[0055] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 45 grams
2,9-dichloro-6,13-dihydroquinacridone- , 3.0 grams of the pigment
additive prepared according to Example 1, 280 ml methanol and 136.8
grams 45% aqueous potassium hydroxide, which was stirred for 5
minutes at 30 to 40.degree. C. The mixture was then stirred under a
slow flow of nitrogen at reflux temperature for one hour generating
the potassium salt of 2,9-dichloro-6,13-dihydroquinacridone. 0.6
grams of the sodium salt of anthraquinone-2-sulfonic acid was
added. 67.8 grams of an aqueous 16.9% hydrogen peroxide solution
were added at a pump setting of 0.3 mV minute while maintaining
reflux under a slow nitrogen flow over a period of 3 hours 20
minutes. The resulting magenta colored suspension was further
stirred for 10 minutes at reflux temperature, diluted with 100 ml
cold water, then filtered at 50-60.degree. C. The presscake was
washed with hot water then dried yielding 44 grams of
magenta-colored 2,9-dichloroquinacridone pigment.
[0056] The x-ray diffraction pattern of the pigment showed the
characteristics of a gamma 2,9-dichloroquinacridone. When
incorporated in automotive paints the product produced a strong
transparent magenta color dispersion with excellent rheological
properties, and which can be easily sprayed on metallic panels
generating coatings of excellent durability.
EXAMPLE 10
[0057] The procedure described in Example 10 was repeated using 1.8
grams, instead of 3.0 grams, of the pigment additive prepared
according to Example 1, and 80 grams 50% sodium hydroxide instead
of potassium hydroxide, yielding a strong magenta colored
2,9-dichloroquinacridone.
[0058] Incorporated in plastics the product produced a strong
bluish magenta color with an excellent heat and light
stability.
EXAMPLE 11
[0059] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 40 grams 6,13-dihydroquinacridone, 180
ml methanol and 42 grams 50% aqueous sodium hydroxide and 14.6
grams of the aqueous presscake of the naphthalin-1-sulfonic acid
methyl quinacridone pigment additive prepared according to Example
2. The mixture was stirred under a slow flow of nitrogen at
50-55.degree. C. for one hour. 0.5 gram anthraquinone mono sulfonic
acid sodium salt as catalyst were added and the reaction mixture
was heated to reflux for one hour generating the sodium salt of
6,13-dihydro-quinacridone. 67 grams of an aqueous 19.3% hydrogen
peroxide solution were added into the reaction mixture with a
peristaltic pump at a pumping rate of 0.3 ml/minute, whereby after
1/2 hour addition time 1.2 grams phthalimidomethyl-quinacridone
were introduced into the reaction mixture followed by continuing
the hydrogen peroxide addition while maintaining reflux and a slow
nitrogen flow. The resulting violet suspension was further stirred
for 10 minutes at reflux then diluted with 100 ml cold water and
filtered. The presscake was washed with hot water then dried,
yielding 38.9 grams violet quinacridone.
[0060] The product shows a high purity and only 0.3% remaining
6,13-dihydro-quinacridone as determined by a spectrophotometric
method. The x-ray diffraction pattern of the pigment shows the
characteristics of a beta quinacridone. Incorporated in automotive
paints the product produced a strong violet color dispersion with
excellent rheological properties and a semi-transparent appearance
when drawn on a contrast carton, and which can be easily sprayed on
metallic panels generating coatings of excellent durability.
EXAMPLE 12
[0061] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 50 grams 6,13-dihydroquinacridone, 310
ml methanol and 66 grams 50% aqueous sodium hydroxide and 3.8 grams
50% aqueous benzyl tributyl ammonium chloride solution and stirred
for 5 minutes at 35-40.degree. C. 0.9 grams anthraquinone sulfonic
acid methyl quinacridone pigment additive prepared according to
Example 4 was added followed by the addition of 0.5 grams
anthraquinone mono sulfonic acid sodium salt as catalyst. The
mixture was stirred under a slow flow of nitrogen and heated to
reflux. 91.4 grams of an aqueous 17% hydrogen peroxide solution
were added into the reaction mixture with a peristaltic pump at a
pumping rate of 0.3 ml/minute. The resulting red suspension was
further stirred for 10 minutes at reflux then diluted with 100 ml
cold water and filtered. The presscake was washed with hot water
then dried, yielding 48.9 grams red quinacridone.
[0062] The x-ray diffraction pattern of the pigment shows the
characteristics of a gamma-III quinacridone which is described in
U.S. Pat. No. 5,223,624. It can be easily incorporated in paints
and plastics providing strongly red colored articles.
EXAMPLE 13
[0063] Under a flow of nitrogen a one liter flask equipped with a
thermometer, stirrer and condenser is charged with 100 ml
tert.-amyl alcohol, 34.6 grams potassium tert. butylate and 144.4
grams of benzonitrile, and the mixture is heated to about
98.degree. C. A substantially anhydrous solution of 14.6 grams of
dimethyl succinate in 10 ml tert. amyl alcohol is added at
98-99.degree. C. in 145 minutes using a metering pump and methanol
is distilled of. After the complete addition the reaction mixture
is stirred for 2 hours at 99.degree. C. and 0.5 grams o-benzoic
acid sulfimide methyl 3,6-diphenyl-1,4-diketopyrrol-[-
3,4-c]-pyrrole additive prepared according to Example 8 are added,
then cooled to 65.degree. C., diluted with 100 ml methanol followed
by the addition of 250 ml water. The mixture is filtered. The
presscake is washed neutral with water and dried, yielding 19 grams
of a scarlet direct pigmentary diketopyrrolopyrrole pigment showing
a high color strength, high saturation and good light stability
when incorporated in paints and plastics.
EXAMPLE 14A
[0064] A beta quinacridone crude with a particle size of 2 to 6
.mu.m as for example obtained by the oxidation of
6,13-dihydroquinacridone with hydrogen peroxide as the oxidant as
described in U.S. Pat. No. 5,840,901 is premilled according to the
following procedure:
[0065] A 1-SDG Attritor.TM. mill manufactured by Union Process,
Inc. Akron, Ohio, which is fitted with L-arms and contains 3.78
liters of 0.6 cm diameter ceramic grinding media with 7.5 MOH
hardness, 60-65 Rockwell 45 N hardness, 3.0 kg/cm impact strength
and 8500 kg/cm compressive strength. The mill is charged with 350
grams of the beta quinacridone crude and the pigment is milled
under a nitrogen flow at a rotation speed of 500 RPM for 50
minutes. At the conclusion of the milling cycle, the product is
recovered by opening the valve at the bottom of the mill while
rotation continues for 15 minutes yielding a brown highly
aggregated powder with a very low crystallinity.
EXAMPLE 14B
[0066] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 0.3 grams of the o-benzoic acid
sulfimide methyl quinacridone additive prepared according to
Example 5 and 250 ml DMF (dimethylformamide). The mixture was
stirred at 50-55.degree. C. for 15 minutes whereby the additive was
partially dissolved in the solvent. 30 grams of the above premilled
powder from Example 14A is added and the suspension was stirred for
3 hours at 50-55.degree. C. The resulting violet suspension was
filtered. The press cake was washed with water and dried yielding a
violet pigment which shows excellent durability and a high chroma
when incorporated in paints and plastics. The X-ray diffraction
pattern shows the characteristic of a beta quinacridone.
EXAMPLE 15
[0067] 63.0 grams of polyvinylchloride, 3.0 grams epoxidized soy
bean oil, 2.0 grams of barium/cadmium heat stabilizer, 32.0 grams
dioctyl phthalate and 1.0 gram of the beta quinacridone prepared
according to Example 11 were mixed together in a glass beaker using
a stirring rod. The mixture was formed into a soft PVC sheet with a
thickness of about 0.4 mm by rolling for 8 minutes on a two roll
laboratory mill at a temperature of 160.degree. C., a roller speed
of 25 rpm and friction of 1:1.2 by constant folding, removal and
feeding. The resulting soft PVC sheet was colored in an attractive
violet shade with excellent fastness to heat, light and
migration.
EXAMPLE 16
[0068] Five grams of the magenta 2,9-dichloroquinacridone pigment
prepared according to Example 10, 2.5 grams hindered amine light
stabilizer, 1.0 gram benzotriazole UV absorber, 1.0 gram hindered
phenol antioxidant and 1.0 gram phosphite process stabilizer were
mixed together with 1000 grams of high density polyethylene at a
speed of 175-200 rpm for 30 seconds after flux. The fluxed,
pigmented resin was chopped up while warm and malleable, and then
fed through a granulator. The resulting granules were molded in an
injection molder with a 5 minute dwell time and a 30 second cycle
time at temperatures of 260.degree. C. Homogeneously colored chips
which show a bright magenta color with excellent light stability
were obtained.
EXAMPLE 17
[0069] Preparation of Automotive Paint
[0070] Millbase Formulation:
[0071] A pint jar was charged with 66 grams acrylic resin, 14.5
grams AB dispersant and 58.1 grams solvent (SOLVESSO 100 from
American Chemical). 26.4 grams quinacridone pigment obtained
according to Example 12 and 980 grams of 4 mm diameter steel
diagonal rods were added. The mixture was milled in the jar for 64
hours on a roller mill. The resulting millbase contained 16.0%
pigment with a pigment/binder ratio of 0.5 and a total non-volatile
content of 48.0%.
[0072] Masstone Color:
[0073] 47.3 grams of the above millbase, 36.4 grams of clear solids
color solution containing a melamine resin catalyst, non-aqueous
dispersion resin and a UV absorber, and 16.3 grams of a balanced
clear solid color solution containing a polyester urethane resin
were mixed and diluted with a solvent mixture containing 76 parts
xylene, 21 parts butanol and 3 parts methanol to a spray viscosity
of 20-22 seconds, as measured by a #2 Fisher Cup.
[0074] The resulting red resin/pigment dispersion was sprayed onto
a panel twice at 1.5 minute intervals as a basecoat. After 2
minutes, clearcoat resin was sprayed twice at 11/2 minute intervals
onto the basecoat. The sprayed panel was then flashed with air in a
flash cabinet for 10 minutes and then "baked" in an oven at
265.degree. F. (129.degree. C.) for 30 minutes, yielding a high
chroma red colored panel, with excellent weatherability.
EXAMPLE 18
[0075] 1000 grams of polypropylene granules (DAPLEN PT-55.RTM.,
from Chemie Linz) and 10 grams of the 2,9-dichloroquinacridone
pigment obtained in Example 9 were thoroughly mixed in a mixing
drum. The granules so obtained were melt spun at 260-285.degree. C.
to magenta colored filaments of good light fastness and textile
fibers properties.
[0076] In addition to the embodiments described above, numerous
variations of these embodiments can be made in accordance with this
invention, the scope of which should be considered limited only by
the language of the appended claims.
* * * * *