U.S. patent application number 09/801306 was filed with the patent office on 2001-08-23 for 6,13-dihydroquinacridone derivatives.
Invention is credited to Babler, Fridolin.
Application Number | 20010016655 09/801306 |
Document ID | / |
Family ID | 26816340 |
Filed Date | 2001-08-23 |
United States Patent
Application |
20010016655 |
Kind Code |
A1 |
Babler, Fridolin |
August 23, 2001 |
6,13-Dihydroquinacridone derivatives
Abstract
A 6,13-dihydroquinacridone derivative of formula I:
(MO.sub.3S).sub.m--Q--[CH.sub.2--(X)--(Y).sub.n].sub.o (I) wherein:
Q represents a 6,13-dihydroquinacridone moiety of formula II; 1 A
and B each independently represent a substituent selected from H,
F, Cl, C.sub.1-C.sub.3alkyl and C.sub.1-C.sub.3alkoxy 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 or 6 atom ring or
a hetero aromatic group with at least one 5 or 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 zero to 2.5; and o is a number from zero to 4, wherein
m and o are not zero simultaneously.
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: |
26816340 |
Appl. No.: |
09/801306 |
Filed: |
March 7, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09801306 |
Mar 7, 2001 |
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09496493 |
Feb 2, 2000 |
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6225472 |
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60118419 |
Feb 2, 1999 |
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Current U.S.
Class: |
546/6 |
Current CPC
Class: |
C09B 67/0033 20130101;
C09B 67/0036 20130101; C09B 48/00 20130101 |
Class at
Publication: |
546/6 |
International
Class: |
C07F 005/06; C07D
498/04 |
Claims
What is claimed:
1. A 6,13-dihydroquinacridone derivative of formula I:
(MO.sub.3S).sub.m--Q--[CH.sub.2--(X)--(Y).sub.n].sub.o (I) wherein:
Q represents a 6,13-dihydroquinacridone moiety of formula II; 3A
and B each independently represent a substituent selected from H,
F, Cl, C.sub.1-C.sub.3alkyl and C.sub.1-C.sub.3alkoxy 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 5 or 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 a
number from zero to 2.5; and o is a number from zero to 4, and
where m and o are not simultaneously zero.
2. A 6,13-dihydroquinacridone derivative of claim 1, wherein the
substituents A and B of formula II are each H.
3. A 6,13-dihydroquinacridone derivative of claim 1, wherein the
metal cation M is sodium, potassium, calcium, magnesium or
aluminum.
4. A 6,13-dihydroquinacridone derivative of claim 1, wherein X is
an aromatic group selected from a 5 carbon or 6 carbon ring or a
polycyclic group comprising two to six fused 5 carbon and/or 6
carbon rings.
5. A 6,13-dihydroquinacridone derivative of claim 1, wherein the
aromatic group is phenylene, naphthalene, anthracene, phenanthrene,
pyrene or perylene.
6. A 6,13-dihydroquinacridone derivative of claim 5, wherein the
aromatic group is phenylene or naphthalene.
7. A 6,13-dihydroquinacridone derivative of claim 1, wherein said
cyclo-hetero aliphatic group comprises at least one 5 or 6 atom
ring.
8. A 6,13-dihydroquinacridone derivative of claim 5, wherein said
cyclo-hetero aliphatic group is barbituric acid.
9. A 6,13-dihydroquinacridone derivative of claim 1, wherein said
hetero aromatic group which is not a phthalimido group comprises a
5 or 6 atom ring or fused 5 and/or 6 atom rings and contains 1 to 4
hetero atoms selected from N, S and/or O.
10. A 6,13-dihydroquinacridone derivative of claim 9, wherein the
hetero aromatic group is a pyridine, quinoline, pyrrole, imidazole
or pyrazole group.
11. A 6,13-dihydroquinacridone derivative of claim 1, wherein said
aromatic, cyclohetero 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.18alkoxy
groups.
12. A 6,13-dihydroquinacridone derivative of claim 11, wherein said
aromatic, cyclohetero aliphatic or hetero aromatic group is
optionally substituted with one or more C.sub.1-C.sub.3alkyl or
C.sub.1-C.sub.3alkoxy groups.
13. A 6,13-dihydroquinacridone derivative of claim 1, wherein said
aromatic group is toluene, ortho- meta- or para-xylene,
chlorobenzene, 1- or 2-methyinaphthalene or anthraquinone.
14. A 6,13-dihydroquinacridone derivative 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.
15. A 6,13-dihydroquinacridone derivative of claim 1, wherein said
group Y is a free carboxylic acid or sulfonic acid group or a
sodium, potassium, magnesium, calcium, aluminum, quaternary
ammonium or alkyl ammonium salt thereof.
16. A 6,13-dihydroquinacridone derivative of claim 15, wherein said
group Y is a free sulfonic acid group or a sodium, potassium or
aluminum salt thereof.
17. A mixture of 6,13-dihydroquinacridone derivatives according to
claim 1, wherein m is on average from zero to 1, n is on average
from zero to 1.2, and o is on average from zero to 1.5.
18. A process for the preparation of 6,13-dihydroquinacridone
derivative of claim 1, whereby: A) the 6,13-dihydroquinacridone
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.; the mixture of step C) is heated
to 50 to 100.degree. C.; and the resulting precipitate is
isolated.
19. A process according to claim 18 wherein the mixture in step C
is heated for about 30 minutes to 6 hours and wherein the process
further comprises the step of drowning the reaction mixture from
step D in water to produce a precipitate.
20. A process for the preparation of a 6,13-dihydroquinacridone
derivative of claim 18, wherein the molar ratio of
6,13-dihydroquinacridone:intermed- iate X:formaldehyde is 1:1 to
1.2:1 to 2.
21. 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 comprising
the step of synthesizing said pigment in the presence of 0.1 to 25
weight percent of a 6,13-dihydroquinacridone derivative of claim 1,
based on the weight of pigment being synthesized.
22. 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 0.5 to 8 percent by weight of a
6,13-dihydroquinacridone derivative of claim 1, based on the weight
of pigment being synthesized.
23. A process for the preparation of a direct pigmentary
quinacridone, 2,9-dichloro-quinacridone, 4,11
-dichloroquinacridone, 2,9-dimethylquinacridone pigment or a solid
solutions thereof comprising the step of synthesizing the said
pigment or solid solution thereof in the presence of 0.5 to 8
percent by weight of a 6,13-dihydroquinacridone derivative of claim
1, based on the weight of pigment being synthesized.
24. A process for the preparation of a pigmentary grade
anthraquinone, phthalocyanine, perinone, perylene,
diketopyrrolopyrrole, thioindigo, iminoisoindoline,
iminoisoindolinone, quinacridone, flavanthrone, dioxazine,
indanthrone, anthrapyrimidine and quinophthalone pigment comprising
a kneading, solvent or aqueous milling finishing step in the
presence of 0.1 to 25 weight percent of a 6,13-dihydroquinacridone
derivative of claim 1, based on the weight of the pigment being
finished.
25. A process for the preparation of a pigmentary grade
anthraquinone, phthalocyanine, perinone, perylene,
diketopyrrolopyrrole, thioindigo, iminoisoindoline,
iminoisoindolinone, quinacridone, flavanthrone, dioxazine,
indanthrone, anthrapyrimidine and quinophthalone pigment comprising
a premilling followed by an after treatment step in an organic
solvent in the presence of 0.1 to 25 weight percent of a
6,13-dihydroquinacridone derivative of claim 1, based on the weight
of the pigment being finished.
26. A process for the preparation of a pigmentary grade
diketopyrrolopyrrole or quinacridone pigment comprising a
premilling followed by an after treatment step in an organic
solvent in the presence of 0.1 to 25 weight percent of a
6,13-dihydroquinacridone derivative of claim 1, based on the weight
of the pigment being finished.
27. A method of improving the heat stability, rheological and
flocculant properties of pigment particles 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 or finishing of an organic pigment.
BACKGROUND OF THE INVENTION
[0002] Dihydroquinacridones are intermediates for the production of
the well known quinacridone pigments like C.I. Pigment Violet 19,
C.I. Pigment Red 202 and C.I. Pigment Red 122.
[0003] 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 direct synthesis of pigmentary grade dioxazine in the
presence of a dioxazine derivative.
[0004] 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.
[0005] 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.
[0006] 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.
[0007] Copending U.S. Provisional Patent Application entitled
"PIGMENT PARTICLE GROWTH AND/OR CRYSTAL PHASE DIRECTORS", of the
present inventor filed Feb. 2, 1999, discloses pigment particle
growth and/or crystal phase directors which in many cases allow for
the direct synthesis of pigmentary pigments without requiring a
finishing step. However, these compounds themselves have coloristic
properties and when used with certain pigments can behave as
colored impurities and/or can reduce the saturation of the final
pigment.
[0008] Japanese Patent No. 061 45 546 describes phthalimidomethyl
dihydroquinacridones and the use thereof as pigment
dispersants.
SUMMARY OF THE INVENTION
[0009] The present invention is based on the discovery that new,
colorless or only slightly colored compounds derived from
6,13-dihydroquinacridone are effective pigment particle growth
controller and crystal phase directors when present during the
pigment synthesis or a pigment finishing step. They are
particularly effective for quinacridone and diketopyrrolo pyrrole
pigments.
[0010] Such 6,13-dihydroquinacridone derivatives 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 an additional pigment finishing
step.
[0011] Since other known particle growth inhibitors which are
derived from pigment derivatives are strongly colored and often can
behave as an impurity, the present 6,13-dihydroquinacridone
derivatives are only slightly colored. Their presence will not
particularly change the hue of the pigment. Furthermore, the
present 6,13-dihydroquinacridones derivatives are non planar
molecules. Based on the state of the art it is unexpected that non
planar molecules can act as particle growth inhibitors and crystal
phase directors for pigment crystals composed of planar organic
pigment molecules. Thus, the inventive compounds allow the
manufacturer to produce high performance, high chroma organic
pigments in an economical and environmentally friendly manner and
therefore, are of extreme commercial importance.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
[0012] 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)
[0013] wherein Q represents a 6,13-dihydroquinacridone moiety of
formula II: 2
[0014] wherein A and B each independently represent a substituent
selected from H, F, Cl, C.sub.1-C.sub.3alkyl and
C.sub.1-C.sub.3alkoxy. Preferably, substituents A and B each
represent hydrogen.
[0015] M of formula I represents a metal cation, quaternary N
cation or hydrogen, X represents an 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 5 or 6 atom ring and which
is not a phthalimido group; Y is a sulfonic or carboxylic acid or
salt thereof, m and n independent of one of the other each are
numbers from zero to 2.5, and o is a number from zero to 4, wherein
m and o are not zero simultaneously.
[0016] The present invention is further directed to a process for
the preparation of compounds of formula (I) and to the use
thereof.
[0017] Preferably, m in formula I represents a number from zero to
2 and most preferably zero to 1; n represents preferably a number
from zero to 2 and most preferably from zero to 1.2, and o
represents preferably a number from zero to 2 and most preferably
from zero to 1.5, wherein m and o are not zero simultaneously. 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).
[0018] The metal cation M of formula I is preferably sodium,
potassium, calcium, magnesium or aluminum, and the quaternary N
cation of formula I is an ammonium or an alkyl ammonium group.
[0019] Typically, the group X of the inventive compound of formula
I is an aromatic group with a 5 carbon or a 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 or 6 atom ring or fused 5 and/or 6 atom rings, or a hetero
aromatic group which is not a phthalimido group, containing a 5 or
6 atom ring or fused 5 and/or 6 atom rings, and in which there are
1 to 4 hetero atoms of N, S and/or O.
[0020] 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.
[0021] Cyclo-hetero aliphatic groups are, for example, pyrrolidine,
imidazolidine, piperidine, piperazine or morpholine.
[0022] Appropriate hetero aromatic groups are, for instance,
pyridine, pyrazine, pyrimidine, pyridazine, isoindole, quinoline,
isoquinoline, carbazole, phenothiazine, benzimidazolone,
benzothiazole, pyrrolo, imidazole or pyrazole.
[0023] 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.
[0024] Examples of the large number of such substituted cyclo
hetero aliphatic or hetero aromatic groups are, for instance,
toluene, ortho-, meta- or para-xylene, chlorobenzene, 1- or
2-methyinaphthalene 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.
[0025] 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, aluminum, quaternary
ammonium or alkyl ammonium salt thereof.
[0026] A further embodiment, as described more fully below, of the
present invention is a process for the preparation of compounds of
formula I, wherein:
[0027] a) the moiety Q is dissolved in concentrated sulfuric
acid;
[0028] b) the intermediate X is added into the solution and
dissolved at a temperature below 50.degree. C.;
[0029] c) para-formaldehyde is added at a temperature below
50.degree. C.;
[0030] d) and then is heated to a temperature from to 50 to
100.degree. C.; and
[0031] e) then isolated.
[0032] The inventive 6,13-dihydroquinacridone derivatives are
prepared, for example, by reacting a 6,13-dihydroquinacridone
moiety of formula II and the intermediate X, a substantial portion
of which is the moiety of group X, with formaldehyde. Preferably
the reaction is carried out in concentrated (95-98%) sulfuric acid.
In one preferred method, the 6,13-dihydroquinacridone of the 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
6,13-dihydroquinacridone 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., more 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 resulting
slurry is stirred for about 5 minutes to 6 hours, preferably from
about 30 minutes to 3 hours, at a temperature of from about 0 to
50.degree. C., preferably from about 10 to 25.degree. C. The
inventive 6,13-dihydroquinacridone derivatives 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.
[0033] In general, a stochiometric amount of the
6,13-dihydroquinacridone moiety of formula II, intermediate X and
formaldehyde are used; however, an excess of the intermediate X or
formaldehyde may be used to achieve the desired product.
Preferably, the molar ratio of the
6,13-dihydroquinacridone:intermediate X:formaldehyde is 1:1 to
1.2:1 to 2.
[0034] 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.
[0035] 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. By the above preferred technical
preparation method, which does not include specific cleaning steps,
the purity of the isolated product is generally not 100% and the
product contains, depending on the starting materials and reaction
temperature, some remaining starting materials or other byproducts
which, when in concentrations that do not impact the effect of the
particle size and 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.
[0036] Generally, the inventive 6,13-dihydroquinacridone
derivatives 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 by weight, based on the weight of pigment to
be synthesized. The inventive 6,13-dihydroquinacridone derivatives
can be added before or during the final pigment synthesis step.
[0037] The inventive 6,13-dihydroquinacridone derivatives are
suitable as an additive 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 class. The said derivatives are particularly
suited for pigments of various pigment classes having different
shades because they themselves are only slightly colored and
therefore, the presence of the inventive compounds does not lower
the saturation or change the hue of the pigment.
[0038] The inventive 6,13-dihydroquinacridone derivatives are
especially suitable for the synthesis of direct pigmentary diketo
pyrrolopyrrole and quinacridone pigments and/or its solid
solutions. Said derivatives 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-dimethylquinacridone,
4,11-dichloroquinacridone and solid solutions thereof. The
inventive 6,13-dihydroquinacridone derivatives are particularly
effective, when they are completely or partially soluble in the
reaction media in which the pigment is being synthesized.
[0039] Accordingly, a further embodiment of 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 0.5 to 8 percent by weight of a
6,13-dihydroquinacridone of formula I, based on the pigment being
synthesized.
[0040] Without limiting this invention to any particular theory, it
is believed that the inventive 6,13-dihydroquinacridone derivatives
molecule is adhered to the synthesized pigment molecule and by this
is directing the crystal growth and crystal phase. The term
"directing the crystal growth" refers to controlling the synthesis
of pigment particles having a pigmentary size as well as directing
the growth of the crystals to generate particles of a specific
desirable shape such as platelet, needle, cubic, leaflet, rod and
other geometric forms, in a desirable crystal phase. The effect can
be influenced by the chemical structure of the organic pigment, the
selection of the reaction media, the pigment synthesis procedure,
the concentration and the chemical structure of the inventive
6,13-dihydroquinacridone derivatives.
[0041] Under circumstances in which the reaction media of the
pigment to be synthesized is oxidative, the inventive
6,13-dihydroquinacridone derivative may be partially or completely
oxidized to the corresponding quinacridone derivative during the
pigment synthesis. Therefore, the inventive
6,13-dihydroquinacridone derivatives are particularly useful for
the quinacridone pigment synthesis when the quinacridone pigment is
obtained by the oxidation of the corresponding
6,13-dihydroquinacridone as described, for example, in U.S. Pat.
No. 5,840,901.
[0042] During the isolation of the pigment, for example in the
filtration step, these 6,13-dihydroquinacridone derivatives--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.
[0043] Additionally, it has been found that phthalimidomethyl
dihydroquinacridone, previously described as a pigment dispersant,
can be an effective pigment particle growth controller and pigment
crystal phase director.
[0044] In certain cases, it is advantageous to use the inventive
6,13-dihydro-quinacridone derivatives in mixture or in combination
with other additives including known pigment particle growth
inhibitors such as, for example, the compounds described in
Copending U.S. Provisional Patent Application entitled "PIGMENT
PARTICLE GROWTH AND/OR CRYSTAL PHASE DIRECTORS", or
phthalimidomethyl-, imidazolmethyl- or pyrazolmethyl-quinacridone,
pigment sulfonic acids, 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 such 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 added in a concentration of 0.1 to 25 percent,
preferably 0.2 to 15 percent and most preferably 0.5 to 8 percent
by weight, based on the weight of 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 or textiles.
[0045] Suitable polymers are, for example, polyacrylic acid,
polymethacrylic acid, polyvinylpyrrolidone, 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
soy-alkyl 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(ethylenox- y)ethanol,
cycloalkyloxypoly(ethylenoxy)laurate or oleate, polyethylene glycol
400 laurate or oleate, alkyl-, cycloalkyl- or
alkylaryl-poly(ethylenoxy)carboxylate or phosphonate.
[0046] Suitable surfactants belong to the group of anionic
surfactants like for example the alkylbenzene- or alkylnaphthalene
sulfonates, alkylsulfosuccinates or naphthalene formaldehyde
sulfonates; the group of cationic surfactants like for example
quaternary salts such as benzyl tributyl ammonium chloride; or the
group of nonionic or amphoteric surfactants like the
polyoxyethylene surfactants or alkyl- or amidopropyl betaines,
respectively.
[0047] 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.
[0048] 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.
[0049] Due to the ability to act as an antiflocculant as well as an
excellent particle growth inhibitor and phase director, the
inventive 6,13-dihydroquinacridone derivatives 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.
[0050] Pigment finishing processes in which the inventive
6,13-dihydroquinacridone derivatives can be used are for example
the known kneading, solvent or aqueous milling processes.
[0051] Particularly effective are the inventive
6,13-dihydroquinacridone derivatives when present in pigment
finishing processes in which a pigment crude is premilled and after
treated in an organic solvent, a process as described for example
in the U.S. Pat. Nos. 5,194,088 and 2,857,400.
[0052] The following examples further describe the 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
[0053] A one liter flask equipped with a stirrer, thermometer,
condenser and drying tube was charged with 200 ml concentrated
(95-98%) sulfuric acid. 23.6 grams (0.075 mol)
6,13-dihydroquinacridone were added at a temperature below
45.degree. C. and the resulting solution was heated to 100.degree.
C. and stirred for 6 hours at 100.degree. C., then poured into 2.5
liters of ice water. The precipitate was stirred for 30 minutes at
room temperature, then filtered. The presscake was then washed with
water to a pH of 5 and dried yielding a product in which
6,13-dihydroquinacridone sulfonic acid with the molecular weight of
394 was detected by MALDI.
EXAMPLE 2
[0054] A one liter flask equipped with a stirrer, thermometer,
condenser and drying tube was charged with 200 ml concentrated
(95-98%) sulfuric acid. 47.1 grams (0.15 mol)
6,13-dihydroquinacridone were added at a temperature below
45.degree. C. and the mixture was stirred for 10 minutes at 40 to
45.degree. C., dissolving the 6,13-dihydro-quinacridone
completely.
[0055] 23.2 grams (0.158 mol) phthalimide were added at a
temperature below 45.degree. C. and the mixture was stirred for 10
minutes at 40 to 45.degree. C. followed by the rapid addition of
4.9 grams (0.163 mol) of para formaldehyde. The reaction mixture
was stirred for one hour at 55-60.degree. C. then poured into 2.5
liters of ice water. The precipitate was stirred for 21/2 hours at
room temperature, then filtered. The presscake was washed with
water to a pH of 6 to 7 and dried yielding a product in which
phthalimide methyl 6,13-dihydroquinacridone having a molecular
weight of 473 was detected by MALDI.
EXAMPLE 3
[0056] The procedure of Example 2 was repeated using 19.2 grams
(0.15 mol) barbituric acid instead of phthalimide to yield a
product in which barbituric acid methyl 6,13-dihydroquinacridone
having a molecular weight of 454 was detected by MALDI.
EXAMPLE 4
[0057] The procedure of Example 2 was repeated using 18.9 grams
(0.15 mol) melamine instead of phthalimide to yield a product in
which melamine methyl 6,13-dihydro quinacridone having a molecular
weight of 452 was detected by MALDI.
EXAMPLE 5
[0058] The procedure of Example 2 was repeated using 27.6 grams
(0.15 mol) o-benzoic acid sulfimide sodium salt instead of
phthalimide to yield a product in which o-benzoic acid sulfimide
methyl 6,13-dihydro quinacridone having a molecular weight of 509
was detected by MALDI.
EXAMPLE 6
[0059] The procedure of Example 2 was repeated using 26.4 grams
benzene sulfonic acid (0.15 mol with a content of 90%) instead of
phthalimide to yield a product in which para benzene sulfonic acid
methyl 6,13-dihydro quinacridone having a molecular weight of 486
was detected by MALDI.
EXAMPLE 7
[0060] The procedure of Example 2 was repeated using 30.6 grams
Naxonate ST, a commercially available sodium toluene sulfonate from
Ruetgers-Naese (0.15 mol sodium toluene sulfonate with a content of
93%) instead of phthalimide to yield a product in which toluene
sulfonic acid methyl 6,13-dihydro quinacridone having a molecular
weight of 500 was detected by MALDI.
EXAMPLE 8
[0061] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 40 grams 6,13-dihydroquinacridone, 250
ml methanol, 52.8 grams 50% aqueous sodium hydroxide and 3.0 grams
50% aqueous benzyl tributyl ammonium chloride. The mixture was
stirred under a slow flow of nitrogen at 30 to 45.degree. C. for
five minutes, heated to 50 to 55.degree. C. and stirred at 50 to
55.degree. C. for one hour. 0.6 grams of pigment additive melamine
methyl dihydroquinacridone prepared according to Example 4 was
added, followed by the addition of 0.5 grams anthraquinone mono
sulfonic acid sodium salt, as catalyst, and the reaction mixture
was heated to reflux. 73 grams of an aqueous 17% hydrogen peroxide
solution were added into the reaction mixture with a peristaltic
pump at a setting of 0.3 ml/minute 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.
[0062] 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 a gamma type
quinacridone. When incorporated into plastics or paints the pigment
imparts a red color with excellent properties.
EXAMPLE 9
[0063] The procedure of Example 8 was repeated using 0.6 grams
dihydroquinacridone sulfonic acid additive prepared according to
Example 1 instead of 0.6 grams melamine methyl dihydroquinacridone
to yield 39 grams bluish red quinacridone.
[0064] The product showed a purity of above 99% quinacridone as
determined by a spectrophotometric method. The x-ray diffraction
pattern of the pigment shows the characteristics of a beta
quinacridone. When incorporated into plastics or paints the pigment
imparts a violet reddish color with excellent properties.
EXAMPLE 10
[0065] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 40 grams 6,13-dihydroquinacridone, 180
ml methanol, 42.5 grams 50% aqueous sodium hydroxide and 14.6 grams
of an aqueous presscake containing 1.6 grams naphthalin-1-sulfonic
acid methyl quinacridone pigment additive prepared according to
Example 2 of Copending U.S. Provisional Patent Application entitled
"PIGMENT PARTICLE GROWTH AND/OR CRYSTAL PHASE DIRECTORS". The
mixture was stirred under a slow flow of nitrogen at 50 to
55.degree. C. for one hour. 0.5 grams anthraquinone mono sulfonic
acid sodium salt, as catalyst, were added and the reaction mixture
was heated to reflux. 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
15 minutes addition time, 1.2 grams phthalimidomethyl
dihydroquinacridone obtained according to Example 2 were added into
the reaction mixture followed by another addition of 0.8 grams
phthalimidomethyl dihydroquinacridone after 45 minutes while
continuously adding the hydrogen peroxide by 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.
[0066] The product showed a high purity and only 0.7%
6,13-dihydroquinacridone left as determined by a spectrophotometric
method. The x-ray diffraction pattern of the pigment showed the
characteristics of a beta quinacridone. The specific surface area
determined by the BET method was 50 m.sup.2/g.
[0067] When incorporated into automotive paints the product
produced a strong violet color dispersion with excellent
rheological properties and displayed a semitransparent appearance
when drawn on a contrast carton, and which could be easily sprayed
on metallic panels generating violet coatings of excellent
durability.
EXAMPLE 11
[0068] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 116.6 grams 45% aqueous potassium
hydroxide, 200 ml methanol and 0.8 grams of the phthalimidomethyl
dihydroquinacridone additive prepared according to Example 2. The
mixture was stirred for 5 minutes at 30 to 40.degree. C. 45 grams
2,9-dichloro-6,13-dihydroquinacridone were added followed by 60 ml
methanol and the resulting suspension was stirred under a slow flow
of nitrogen at reflux temperature for one hour to generate the
potassium salt of 2,9-dichloro-6,13-dihydroquinacridone. 0.6 gram
of anthraquinone-2-sulfonic acid, sodium salt, was added. 68 grams
of an aqueous 16.9% hydrogen peroxide solution were then added at a
pump setting of 0.3 ml/minute while maintaining reflux under a slow
nitrogen flow over 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 to
60.degree. C. The presscake was washed with hot water and dried
yielding 44 grams of magenta-colored 2,9-dichloroquinacridone
pigment.
[0069] The x-ray diffraction pattern of the pigment showed the
characteristics of a gamma 2,9-dichloroquinacridone. The specific
surface area as determined by the BET method was 45.2 m.sup.2g.
incorporated in automotive paints the product produced a strong
magenta color dispersion with excellent rheological properties, and
which was easily sprayed on metallic panels to generate magenta
colored coatings of excellent durability.
EXAMPLE 12
[0070] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 40 grams 6,13-dihydroquinacridone, 185
ml methanol, 42 grams 50% aqueous sodium hydroxide and 1.2 grams of
the barbituric acid methyl dihydro-quinacridone additive prepared
according to Example 3. The mixture was stirred under a slow flow
of nitrogen at 50 to 55.degree. C. for one hour. 0.5 gram
anthraquinone mono sulfonic acid sodium salt, as catalyst, was
added and the reaction mixture was heated to reflux. 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 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 reddish quinacridone.
[0071] The product showed a high purity and only 0.1%
6,13-dihydroquinacridone left as determined by a spectrophotometric
method. The x-ray diffraction pattern of the pigment showed the
characteristics of a beta quinacridone. The specific surface area
determined by the BET method was 8 m.sup.2/g.
[0072] When incorporated into automotive paints the product
produced a strong violet reddish color dispersion with excellent
rheological properties, displayed an opaque appearance when drawn
on a contrast carton, and was easily sprayed on metallic panels to
generate violet reddish coatings of excellent durability.
EXAMPLE 13
[0073] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 45 grams
2,9-dichloro-6,13-dihydroquinacridone- , 136.8 grams 45% aqueous
potassium hydroxide, 280 ml methanol, 0.3 gram of the o-benzoic
acid sulfimide methyl dihydroquinacridone additive prepared
according to Example 5 and 3.4 grams 50% aqueous benzyl tributyl
ammonium chloride solution. The mixture was stirred for 5 minutes
at 30 to 40.degree. C., then heated to reflux and stirred under a
slow flow of nitrogen at reflux temperature for one hour to
generate the potassium salt of
2,9-dichloro-6,13-dihydroquinacridone. 0.6 gram of
anthraquinone-2-sulfonic acid, sodium salt, was added. 66 grams of
an aqueous 17% hydrogen peroxide solution were then added at a pump
setting of 0.3 ml/minute while maintaining reflux under a slow
nitrogen flow over 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 to
60.degree. C. The presscake was washed with hot water and dried
yielding 44 grams of magenta-colored 2,9-dichloroquinacridone
pigment.
[0074] The x-ray diffraction pattern of the pigment showed the
characteristics of a gamma 2,9-dichloroquinacridone. The specific
surface area as determined by the BET method was 20 m.sup.2/g.
Incorporated in automotive paints the product produced a strong
magenta color dispersion with excellent rheological properties, and
which was easily sprayed on metallic panels to generate magenta
colored coatings of high opacity and excellent durability.
EXAMPLE 14
[0075] 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:
[0076] 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 15
[0077] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 0.3 grams of the o-benzoic acid
sulfimide methyl dihydroquinacridone 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 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 16A
[0078] The procedure of Example 14 was repeated using instead of a
beta quinacridone a 3,6-diphenyl -1,4-diketopyrroi-[3,4-c]-pyrrole
crude yielding a brownish highly aggregated powder with a very low
crystallinity.
EXAMPLE 16B
[0079] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 0.5 grams of the toluene sulfenic acid
methyl dihydroquinacridone additive prepared according to Example 7
and 230 ml DMSO (dimethylsulfoxide). The mixture was stirred at
50-55.degree. C. for 15 minutes whereby the additive was partially
dissolved in the solvent. 20 grams of the premilled powder prepared
according to Example 16A was added and the suspension was stirred
for 2 hours at 23-25.degree. C. The resulting red suspension was
filtered. The press cake was washed with water and dried yielding a
scarlet pigment which shows a high color strength, high opacity as
well as excellent durability and a high chroma when incorporated in
paints and plastics.
EXAMPLE 17A
[0080] The procedure of Example 14 is repeated using instead of a
beta quinacridone a perylene-3,4,9,10-tetracarbonic acid diimide
yielding a dark highly aggregated powder with a very low
crystallinity.
EXAMPLE 17B
[0081] A one liter flask equipped with a thermometer, stirrer and
condenser was charged with 0.2 grams of the benzene sulfenic acid
methyl dihydroquinacridone additive prepared according to Example 6
and 250 ml DMSO (dimethylsulfoxide). The mixture was stirred at
50-55.degree. C. for 15 minutes whereby the additive was partially
dissolved in the solvent. 20 grams of the premilled powder prepared
according to Example 17A were added and the suspension was stirred
for 3 hours at 80-90.degree. C. The resulting violet suspension was
filtered. The press cake was washed with water and dried yielding a
violet pigment which shows a high color strength, excellent
durability and a high transparency when incorporated in paints.
EXAMPLE 18
[0082] 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 benzene
sulfenic acid methyl dihydroquinacridone additive prepared
according to Example 6 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 19
[0083] 63.0 grams of polyvinylchloride, 3.0 grams epoxidized soya
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 10 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 20
[0084] Five grams of the magenta 2,9-dichloroquinacridone pigment
prepared according to Example 13, 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 21
Preparation of Automotive Paint
[0085] millbase formulation:
[0086] 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%.
[0087] masstone color:
[0088] 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.
[0089] The resulting violet 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 violet
reddish colored panel, with excellent weatherability.
EXAMPLE 22
[0090] 1000 grams of polypropylene granules (DAPLEN PT-55.RTM.,
from Chemie Linz) and 10 grams of the 2,9-dichloroquinacridone
pigment obtained in Example 11 were thoroughly mixed in a mixing
drum. The granules so obtained were melt spun at 260-28.degree. C.
to magenta colored filaments of good light fastness and textile
fibers properties.
[0091] 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.
* * * * *