Compositions: coating or plastic – Materials or ingredients – Pigment – filler – or aggregate compositions – e.g. – stone,...
Reexamination Certificate
1999-07-23
2001-03-13
Green, Anthony (Department: 1755)
Compositions: coating or plastic
Materials or ingredients
Pigment, filler, or aggregate compositions, e.g., stone,...
C106S413000, C106S493000, C106S494000, C106S495000, C106S496000, C106S497000, C544S047000, C544S051000, C544S056000, C544S058500, C544S058600, C544S058700
Reexamination Certificate
active
06200378
ABSTRACT:
BACKGROUND OF THE INVENTION
Thiazine indigo compounds are an important series of pigments. Prior art processes for forming these pigments involve the reaction of certain o-aminomercapto- carbocycles or heterocycles with maleic acid or a derivative thereof in the presence of a solvent. The solvents useful for this purpose were recognized to be either a carboxylic acid (which also acted to catalyze the reaction) or an inert polar aprotic solvent.
Thus in DE 2 151 723 a process is described for making certain symmetrically substituted benzothiazine indigo compounds wherein certain substituted ortho-aminomercapto-carbocycles or heterocycles are reacted with a maleic acid derivative in a carboxylic acid, e.g. acetic acid. The pigments formed in this way are produced in good yield but they exhibit dull shades. By symmetrically substituted is meant that there is identical substitution on each of the thiazine rings.
In DE OS 25 36 120 a process is described for making certain other symmetrically substituted benzothiazine indigo compounds wherein certain substituted ortho-aminothiophenols are reacted with a maleic acid derivative in an inert polar aprotic solvent. The benzothiazine indigo compounds formed, allegedly display improved pigmentary properties, e.g. brighter and cleaner shade over the compounds made in a carboxylic acid solution, however, they can only be produced in poor yield.
There remains a need to provide further thiazine indigo pigments and an improved process of forming thiazine indigo pigments.
SUMMARY OF THE INVENTION
It has now been found that new thiazine indigo pigments can be formed in high yield and, which exhibit pigmentary properties which are better than heretofore achieved.
This invention relates to thiazine indigo pigments, solid solutions thereof and to a process of forming such pigments and solid solutions.
The invention provides in one of its aspects a pigment which is a compound according to the formula (I)
wherein R
1
and R
2
are independently the atoms necessary to complete the formation of a substituted or unsubstituted aromatic or aliphatic carbocyclic or heterocyclic ring system, the radicals R
3
and R
4
, independently of each other, are hydrogen or a group of the formulae (II), (III) or (IV)
whereby in the formulae (II), (III) and (IV)
m, n and p, independently of each other, are zero or 1;
X C
1-14
-alkalene or C
2-8
-alkylene;
Y a group —V—(CH
2
)
q
—;
Z a group —V—(CH
2
)
r
—;
V Cycloakylene;
q a number of 1 to 6; and
r a number of zero to 6,
R
8
and R
9
independently of each other, signify hydrogen, C
1-6
-alkyl, C
1-4
-alkoxy, halogen, CN, NO
2
, unsubstituted phenyl or phenoxy, phenyl or phenoxy substituted by C
1-4
-alkyl, C
1-4
-alkoxy or halogen;
Q hydrogen, CN, Si(R
8
)
3
, a group C(R
12
)(R
13
)(R
14
), in which R
12
, R
13
and R,
14
are halogen; a group
in which R
8
and R
9
have the above meaning; a group SO
2
—R,, or SR
15
, in which R
15
is C
1-4
-alkyl ; a group CH(R
16
)
2
, in which R
16
is unsubstituted phenyl or phenyl substituted by C
1-4
-alkyl, C
1-4
-alkoxy or halogen; or a group of the formula
R
10
and R
11
independently of each other, signify hydrogen, C
1-18
-alkyl, a group
in which X, Y, R
8
, R
9
, m and n have the above meaning, or
R
10
and R
11
, together with the nitrogen atom to which they are bound, build a pyrrolidinyl-, piperidinyl- or morpholinylrest,
provided that, if R
3
and/or R
4
are a group of the formula (III), Q is hydrogen and n is zero, m must be 1 and X a C
2-14
-alkylene- or C
2-8
-alkylene group which is branched at the carbon atom bound to oxygen, and if both R
3
and R
4
are hydrogen, R
1
and R
2
cannot be identical.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferably R
1
and R
2
are independently selected from the residues consisting of
where Hat is halogen which includes F, Cl and Br, especially Cl
R is C
1-4
alkyl especially methyl or ethyl
a is 1, 2, 3 or 4
b is 1, 2, 3 or 4
In a preferred pigment according to the invention R
1
is a residue which consists of the atoms necessary to complete a benzene ring which is optionally substituted with, for example halogen or alkyl and R
2
consists of the atoms necessary to complete a ring system which is a differently substituted benzene ring or a different substituted or unsubstituted aromatic or aliphatic carbocyclic or heterocyclic ring system, e.g. naphthalene, pyridine or 1,4-benzodiazine.
The pigments may be substituted on the ring systems with one or more of any of the non-water-solubilising substituents common in the art of pigments. Preferably the ring system substituents are selected from the group consisting of halogen, trifluoromethyl, nitro, cyano, alkyl, alkoxy, amino, alkylamino, thioalkyl, phenoxy, phenylamino, phenylthio, acyl, acyloxy or acylamino.
The term “halogen” includes fluorine and especially chlorine and bromine. The term “alkyl” or “alkoxy” includes said functionality having from 1 to 4 carbon atoms. The terms “alkylamino” and “phenylamino” include N,N-dialkylamino and N,N-diphenylamino as well as N-monoalkylamino and N-monophenylamino.
The aforementioned alkyl, alkoxy, phenyl and phenoxy substituents may themselves contain one or more substituents selected from the substituents hereinabove described.
The invention provides in one of its further aspects a process of forming thiazine indigo pigments according to the formula (I)
wherein R
1
and R
2
are independently the atoms necessary to complete the formation of a substituted or unsubstituted aromatic or aliphatic carbocyclic or heterocyclic ring system, R
3
and R
4
are hydrogen, comprising the step of reacting in the presence of a solvent system comprising a carboxylic acid and an inert polar aprotic solvent, a compound of formula (II) and a compound of formula (III)
wherein R
5
and R′
5
independently are H or a metallic ion selected from Na
+
, K
+
or Zn
2+
with a compound of formula (IV)
wherein Hal is Cl or Br, R
6
and R′
6
independently of the other is a leaving group commonly used in substitution reactions at carbonyl carbon atoms, e.g. Cl or alkoxy or together X and X′ represent an oxygen atom. A compound of formula (IV) shown in its cis-form above may also be used in its trans-form.
Preferably the molar ratio of the reactants is 1:1:1.
The process is carried out in the presence of a carboxylic acid, e.g. acetic acid, which also acts as a catalyst, and an inert polar aprotic solvent, e.g. xylene or a xylene mixture, nitrobenzene, chlorobenzene, dimethylformamide, or dimethylacetamide, in particular dimethylformamide, dimethyl acetarnide or N-methylpyrrolidone. The reaction is preferably carried out in solvent system which consists of 5 to 95% by weight of carboxylic acid, e.g. acetic acid, more preferably 10% by weight and 95 to 5% by weight of polar aprotic solvent, more preferably 90% by weight.
The reaction temperature is preferably of the order of 60 to 200° C.
The thiazine indigo pigments produced by the above process may be symmetrically substituted, that is R
1
and R
2
as well as R
3
and R
4
are identical. Alternatively, they may be asymmetrically substituted, that is, R
1
and R
2
or R
3
and R
4
are not identical. Non-identity refers to either the ring systems R
1
and R
2
being different or, in the event that the ring systems are identical, the substituents attached to the respective ring systems are different. The asymmetrical compounds are novel compounds.
Thiazine indigo pigments according to formula (I) in which at least one of the substituents R
3
and R
4
is not hydrogen, are produced by reacting the pigments of formula (I) in which both R
3
and R
4
are hydrogen, with a dicarbonate of formula (V)
R′
3
—O—R′
3
(V)
or with a trihaloacetic acid ester of the formula (VI)
(R
7
)
3
—C—R′
3
(VI)
or with a mixture of dicarbonate of the formula (V) and a dicarbonate of the formula (VII)
R′
4
—O—R′
4
(VII)
or with a mixture of trihaloacetic acid ester of the formula (VI) and a trihaloacetic acid ester of the f
Kaul Bansi Lal
Piastra Bruno
Clariant Finance (BVI) Limited
Green Anthony
Hanf Scott E.
Jackson Susan S.
LandOfFree
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