Note: Descriptions are shown in the official language in which they were submitted.
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Reactive Dye Compounds
Technical Field
The present invention relates to reactive dye compounds. In particular the
present
invention relates to reactive dye compounds having improved dye-bath
Exhaustion (E)
and improved dye-fibre covalent Fixation (F).
Background of the Invention
Reactive dye compounds are known in the art for dyeing various substrates.
Such
substrates include for example proteinaceous materials such as keratin, e.g.
found in hair,
skin and nails and various animal body parts such as horns, hooves and
feathers, and
other naturally occurring protein containing materials, e.g. silk and
saccharide-derived
materials such as those derived from cellulose or cellulose derivatives, e.g.
natural
products such as cotton, and synthetic fibres such as polyamides.
Examples of classes of such reactive dyes which are well known in the art
include dyes
containing a mono- or dichloro- or fluoro- 1,3,5-triazinyl group, trichloro or
mono- or di-
fluoro-pyrimidyl group, beta-halogen-propionyl group, beta-halogenoethyl-
sulphonyl
group, beta-halogenoethylsulphamyl group, chloroacetyl amino, beta-(chloro-
methyl)-
beta-sulphatoethylsulphamyl group, or a vinyl sulphonyl group.
In the case of the dyes containing a triazinyl group or a pyrimidyl group, in
place of the
reactive halogen atoms one can use other groups which dissociate in the
presence of
alkali. Canadian Patent 771632, for example, discloses examples of such other
groups
including sulphonic acid, thiocyanate, sulphophenoxy, sulphophenyl thio,
nitrosulphophenoxy groups, and quaternary ammonium groups.
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"The Synthesis and Properties of some Triazine-Stilbene Fluorescent
Brighteners",
LGrabtchev, discloses the synthesis of certain triazine stilbene fluorescent
brighteners
containing methacrylic groups.
The Journal of Macromoleular Chemistry 64 (1977), 205-210 (Nr. 951) discloses
the
polymerisation of acrylonitrile in dimethylformamide in the presence of some
unsaturated
triazine derivatives. The Journal of Macromolecular Chemistry 50 (1976) 1-8
(Nr.728)
discloses the polymerization of styrene in the presence of some coloured
anthraquinone
and azoderivatives of 1,3,5-triazine, containing a group able to copolymerize.
The Journal of the Chemical Society, 1963, pages 4130-4144, "The Hydrolysis of
Some
Chloro-1,3,5-Triazines" by S. Horrobin, discloses that dichloro-m-
sulphoanilinotriazine
is rapidly hydrolysed in acetate (pH 4.7) or phthalate (pH 4.0) buffers.
There are many different types of commercially-available reactive dyes for
dyeing
cellulosic and polyamide-type substrates. However, a critical problem still
facing the
textile dye industry today is the significant level of dyestuff material which
remains in the
effluent waste water after the dyeing process is finished. The industry
measure for this
problem is known as dye-bath Exhaustion (E). A high Exhaustion value for a
particular
dye compound means that a low level of spent dye remains in the effluent after
the dyeing
process is complete, while a low Exhaustion value means that a high level of
spent dye
remains in the effluent. There is clearly a need therefore for new dye
compounds which
have higher Exhaustion Values compared with commercially available dye
compounds,
and which provide benefits in terms of reducing levels of spent dyestuff in
effluent water.
As well as having a high Exhaustion Value, it is also important for a dye
compound to
have a high dye-fibre covalent Fixation Value (F). The Fixation Value (F) of a
reactive
dye compound is a measure of the extent of covalent bonding with the substrate
based on
the dye originally absorbed during the dyeing process. Thus 100% Fixation
means that
100% of the absorbed dye covalently bonds to the substrate. Thus, there is
clearly a need
to provide dye compounds having increased Fixation Values. A high Fixation
Value can
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result in a simplification of the post dyeing "soaping off process"
traditionally associated
with fibre reactive dye compounds. In particular, a high Fixation Value can
result in a
reduced time spent on the "soaping off process" together with a reduced cost.
It has now been surprisingly found that a new class of fibre reactive dye
compounds
comprising a nitrogen-containing heterocycle substituted with at least one
phosphonate
derivative, exhibit significantly increased values of Exhaustion (E) and
Fixation (F).
These dyes can be used on a wide variety of substrates. They are particularly
useful for
cellulosic substrates, such as cotton, and materials such as keratin, hair,
wool and silk,
and show significant improvements in terms of reducing spent dyestuff in
effluent,
increasing dye affinity to the substrate, increasing the efficiency of the dye-
substrate
covalent reaction, and simplifying the post dyeing "soaping off process"
traditionally
associated with reactive dyes. In addition, the compounds of the present
invention
provide significantly more intense dyeings, and can be used for both high and
low
temperature dyeing, hence reducing the cost of the dyeing process.
Furthermore, the
compounds of the present invention can be used together with specific
chromophores for
cellulose substrate dyeing leading to significantly reduced levels of salt
needed for
dyeing.
Summary of the Invention
According to the present invention there is provided a reactive dye compound
comprising:
(a) at least one chromophore moiety;
(b) at least one nitrogen-containing heterocycle
(c) a linking group to link each chromophore moiety to each nitrogen-
containing
heterocycle;
characterised in that at least one nitrogen-containing heterocycle is
substituted with at
least one Y group wherein Y is a phosphonate derivative or borate derivative,
preferably
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wherein the phosphonate derivative is selected from polyphosphonate groups
preferably
having a formula -O-(P=O)(OH)R' wherein R' is any suitable nucleophile but is
not OH.
The compounds of the present invention exhibit increased Exhaustion (E) and
Fixation
(F) values and provide improvements in terms of reducing spent dyestuff in
effluent,
increasing dye affinity to the substrate, increasing the efficiency of the dye-
substrate
covalent reaction, ability to carry out the long-liquor dyeing process at room
temperature
as well as at elevated temperatures, and simplifying the post dyeing "soaping
off process"
traditionally associated with fibre reactive dyes. In addition, the compounds
of the
present invention provide significantly more intense dyeings, i.e. greater
colour intensity
in the dyed substrate, without compromising levelness. Typical Exhaustion
Values for
the compounds and products herein are greater than 95%. Typical Fixation
Values for the
compounds and products herein are greater than 95%.
Detailed Description of the Invention
As used herein the term "reactive dye" means a dye containing one or more
reactive
groups, capable of forming covalent bonds with the substrate to be dyed, or a
dye which
forms such a reactive group in situ.
As used herein the term "Exhaustion" in relation to reactive dyes means the
percentage of
dye which is transferred from a solution of the dye to the substrate to be
treated at the end
of the dyeing process, before rinsing and soaping. Thus 100% Exhaustion means
that
100% of the dye is transferred from the dye solution to the substrate. Typical
Exhaustion
Values for the dye compounds herein are > 95%.
As used herein the term "Fixation" in relation to reactive dyes means the
percentage of
dye which covalently bonds with the substrate, based on the dye originally
absorbed
during the dyeing process. Thus 100% Fixation means that 100% of the dye
absorbed is
covalently bonded with the substrate. Typical Fixation Values for the dye
compounds
herein are 95%.
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The total efficiency of reactive dyes can be measured by their Efficiency
Value (T) which
can be calculated from the Exhaustion Value (E) and Fixation Value (F) using
the
following equation:
%T = (FxE)/100
The compounds of the present invention comprise a chromophoric moiety and a
nitrogen-
containing heterocycle linked via a linking group. The nitrogen-containing
heterocycle is
substituted by at least one Y group wherein Y is a phosphonate or borate
derivative.
Chromonhoric Moietv
The reactive dye compounds herein can comprise one or more chromophoric
moieties (D
or D'). In reactive dye compounds comprising two or more chromophoric moieties
these
can be the same or different. Preferably the reactive dye compounds herein
comprise
from one to three chromophoric moieties.
Any chromophoric moieties suitable for use for dyeing substrates can be used
in the
present invention. The term chromophore as used herein means any photoactive
compound and includes any coloured or non-coloured light absorbing species,
eg.
fluorescent brighteners, UV absorbers, IR absorbing dyes.
Suitable chromophoric moieties for use in the dye compounds herein include the
radicals
of monoazo, disazo or polyazo dyes or of heavy metal complex azo dye derived
therefrom or of an anthraquinone, phthalocyanine, formazan, azomethine,
dioxazine,
phenazine, stilbene, triphenylmethane, xanthene, thioxanthene, nitroaryl,
naphthoquinone, pyrenequinone or perylenetetracarbimide dye.
Suitable chromophoric moieties for use in the dye compounds herein include
those
disclosed in EP-A-0,735,107 (Ciba-Geigy), incorporated herein by reference,
including
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the radicals described therein which contain substituents customary for
organic dyes, such
as sulphonate substituents which enhance the water-soluble properties of the
dye
compound.
Most preferred chromophoric D or D' groups for use herein are potysulphonated
azo
chromophores such as those present in Procion (RTM) dyes commercially
available from
BASF, Drimalan ~(RTM) dyes commercially available from Clariant, Drimarene
(RTM)
dyes commercially available from Clariant and Levafix (RTM) dyes commercially
available from Dystar.
Nitrogen-containing heterocycle
The reactive dyes of the present invention comprise at least one nitrogen-
containing
heterocyclic moiety. In reactive dye compounds containing two or more nitrogen-
containing heterocycles these can be the same or different. Preferably the
reactive dye
compounds herein comprise from one to three nitrogen-containing heterocycles.
At least
one of the nitrogen-containing heterocycle moieties herein is substituted with
at least one
Y group defined below.
Suitable nitrogen-containing heterocycles for use herein include monocyclic,
bicyclic or
polycyclic, unsaturated heterocycles containing at least one nitrogen
heteroatom. When
monocyclic rings are used, they are preferably selected from unsaturated rings
having
from about 3 to about 7 ring atoms, especially 5 or 6 ring atoms, comprising
from about 1
to about 3 nitrogen heteroatoms, preferably 2 or 3 nitrogen heteroatoms. When
bicyclic
heterocycles are used, they preferably comprise an unsaturated nitrogen
containing
heterocycle having 3 to 7 ring atoms, preferably an unsaturated nitrogen
containing
heterocycle having 5 or 6 ring atoms comprising 1 or 2 nitrogen atoms, fused
to a 5 to 7
membered carbocycle preferably a 6-membered unsaturated carbocycle. When
bicyclic
heterocycles are used, the oxy- or thio- carbonyl substituents are preferably
attached to
the nitrogen-containing heterocyclic ring.
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Preferred for use herein are 5 or 6 membered unsaturated nitrogen-containing
monocyclic
heterocyclic rings comprising 2 or 3 nitrogen heteroatoms or bicyclic rings
containing a 5
or 6 membered unsaturated heterocyclic ring containing 2 nitrogen heteroatom
fused to a
6 membered unsaturated carbocycle.
Examples of suitable heterocycles for use herein include, but are not
necessarily limited
to triazine, pyrimidine, quinoxaline, pyrimidinone, phthalazine, pyridazone
and pyrazine.
Preferred for use in the compounds herein are triazine, pyrimidine and
quinoxaline.
Linking Moiety
The compounds herein further comprise a linking moiety to link each nitrogen-
containing
heterocycle to each chromophoric moiety. Any linking moieties suitable for use
in
dyeing substrates can be used in the present invention. Preferably the linking
moiety is
selected from NR, NRC=O, C(O)NR, NRS02 and -S02NR wherein R is H or C1-C4
alkyl which can be substituted by halogen, preferably fluorine or chlorine,
hydroxyl,
cyano, Cl-C4 alkoxy, C2-CS alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or
sulfato.
When the heterocycle is a triazine or pyrimidine a preferred linking moiety is
NR,
preferably where R is H or Cl-C4 alkyl, more preferably where R is H or CH3,
especially
H. When the heterocycle is quinoxaline or phthalazine, a preferred linking
moiety is
NRC=O, where R is H or C 1-C4 alkyl, more preferably where R is H or CH3,
especially
H.
Substituent Y
The nitrogen-containing heterocycle is substituted with at least one Y group
wherein Y is
a phosphonate or borate derivative. Preferred phosphonate derivative are
polyphosphonate derivatives having the formula -O-(P=O)(OH)R' wherein R' is
any
suitable nucleophile group which is not OH.
As used herein the term "nucleophilic group" means a negative ion or any
neutral
molecule that has an unshared electron pair. Preferred nucleophilic groups
herein can be
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selected from NH2, SH, COOH, -N=, NHR' and NR'RZ wherein R' and RZ may be the
same or different and may be selected from C~-C4 alkyl.
Suitable R' groups for use herein are alkyl or aryl residues which contain at
least one
nucleophilic group. Preferably the R' groups herein are selected from the
following
groups each substituted with or containing at least one nucleophilic group:
substituted or
unsubstituted, straight chain or branched chain C,-C8 alkyl, substituted or
unsubstituted
straight chain or branched chain CZ-C8 alkenyl having at least one olefinic
group,
substituted or unsubstituted, saturated or unsaturated or aromatic 3-9 atom
monocyclic
carbocycle or substituted or unsubstituted, saturated or unsaturated or
aromatic 7-17
polycyclic carbocycle, ubstituted or unsubstituted, saturated or unsaturated
or aromatic 3-
9 atom monocyclic heterocycle or substituted or unsubstituted, saturated or
unsaturated or
aromatic 7-17 atom polycyclic heterocycle, wherein said heterocycles each have
one or
more heteroatoms selected from O, N or S.
In the definition of R' above, where the term "substituted" is used such
substitution may
be with one or more substituents. Such substituents include, but are not
limited to, those
listed in C.Hansch and A. Leo, Substituent Constants for Correlation Analysis
in
Chemistry and Biolo~y (1979), hereby incorporated by reference herein.
Preferred
substituents include, but are not limited to, alkyl, alkenyl, alkoxy, hydroxy,
oxo, amino,
aminoalkyl (e.g. aminomethyl, etc.), cyano, halo, carboxy, alkoxyacetyl (e.g.
carboethoxy, etc.), thio, aryl, cycloalkyl, heteroaryl, heterocycloalkyl,
(e.g. piperidinyl,
morpholinyl, piperazinyl, pyrrolidinyl, etc.), imino, thioxo, hydroxyalkyl,
aryloxy,
arylalkyl, and combinations thereof.
Preferred R' groups for use herein include, but are not limited to, CF3,
(CHZ)"SH,
(CHZ)"NH2, CH(CH3)OH, C(OH)(CHZCOOH)2, CHZC(OH)(COZH)CHZ COOH,
(CHZ)"NHRl, CHZNR~R2, CHZNHNH2, CHZNHOH, CHZSMe, CH(NHZ)(CH2)~(COOH),
CH(NHZ)CHZSMe, CH(NHZ)CHZSSCHZCH(NHZ)COOH, 2-aminophenyl, 2-
hydroxynaphthyl, 2-pyrrolidyl, CHZSSCH2C03 , (CHZ)~-S03 , CH(NHZ)CHZS03H,
C6H40H, C6H4COOH, C6H4NHz, CSH4N, (CH2)"CSH4N, CH(R#)NH2, (CHZ)"-SS03
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(CHZ)"-S-S-(CHZ)" -C(OH)(H)C(OH)(H)COOH,-C(OH)(H)CHzCOOH, -
C(OH)(COOH)CHZCOOH, CHZ(H)(OH)COOH, derivatives of hydroxy carboxylic acid
polymerisation, eg. in the case of lactic acid dimerisation R' is
CH(CH3)O(CO)CH(CH3)OH, R' groups derived from peptide or polypeptide and
attached to the heterocyclic group via their terminal carboxylic group,
wherein R, and RZ
is independently selected from C,-C4 alkyl, wherein n is an integer in the
range of 1 to 4
wherein within the same molecule n is not necessarily the same integer and
where R#
corresponds to an amino acid sidechain. For examples of such amino acids, cf.
"Organic
Chemistry" by Graham Solomons, 5'h Edition, Wiley, New York, 1992, p1094 -
1095.
Particularly preferred Y groups herein are groups derived from phosphonate
compounds
such as aceto phosphonic acid. A preferred Y group herein is a group derived
from aceto
phosphonic acid, namely -O-PO(OH)C(CH3)(OH)PO(OH)2.
Preferred reactive dye compounds of the present invention may be represented
by the
following formula (I):
Y
D L Z
~X~m
wherein: D is a chromophoric group;
L is a linking moiety selected from NR, N(C=O)R, N(SO2)R;
R is H or C~-C4 alkyl which can be substituted by halogen, hydroxyl,
cyano, C~-C4 alkoxy, CZ-CS alkoxycarbonyl, carboxyl, sulfamoyl, sulfo,
sulfato;
Z is a nitrogen-containing heterocycle;
Y is a phosphonate or borate derivative.
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X is selected from Y (e.g. bis-phosphonate compounds), thio-derivatives,
halogen (preferably fluorine and chlorine), amines, alkoxy groups,
carboxylic acid groups, CN, N3 and quaternized nitrogen derivatives, Q+;
m is 1 or 2 (depending on the Z group, for example m is 1 when Z is
triazine and m is 2 when Z is pyrimidine).
Suitable thio-derivatives for use herein include, but are not necessarily
limited to groups
having the formula SR' wherein R' is selected from H or alkyl or preferably
short chain
alkyl (preferably less than about 6 carbon atoms), alkanol, alkyl carboxylate,
alkylamide,
alkylsulphonate, alkyl phosphonate, alkyl thiosulphonate, alkylamine, alkyl
thiosulphate,
aryl sulphonate, aryl carboxylate, aryl phosphate, aryl amine, cyanates,
sulphonates,
branched alkyl thio carboxylates, branched alkanol thiols, guanides, alkyl-a-
amino-a-
carboxylate, (di) thio alkyl esters of glycerol, alkyl thiol alkyl esters of
glycerol, alkyl
esters, mono thio diesters, thiol alkyl esters of ethylene glycol, alkyl thiol
alkyl ester of
ethylene glycol and alkyl thiolipoates. Preferably R' is selected from alkyl
carboxylates,
alkanols and alkylamines.
Examples of suitable thio-derivatives include SR' groups where R' is selected
from C1-C4
alkyl, (CH2)nCOOH, (CH2)nCONH2, (CH2)nS03H, (CH2)nCOOM, (CH2)nP03H,
(CH2)nOH, (CH2)nSS03 , (CH2)nNR"2, (CH2)nN+R"3, PhSS03 , PhS03H, PhP03H,
PhNR"2, PhN+R"3, -CN, S03 , (CH2)2CH(SH)R"(CH2)3COOH, -CH2CHOHCH2SH,
and
N+H2
C
\ NH2 .
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/NH2
H2C-C
COOH
HC COOH
CH2 COOH
C CH
COOHCOOH
CH3
C COOH
OH
C COOH
CH3
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O
H2 ~ O C (CH2)n
CH O CO (CH2)n SH
CH2 O CO (CH2)n SH
O
H2 ~ O C (CH2)n
CH O CO (CH2)n SR"
CH2 O CO (CH2)n SR"
O
H n~H2C) O C (CH2)n
O
CH2 O C (CH2)n
CH2 O CO (CH2)n SH
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O
H2 O C (CH2)n
CH2 O CO (CH2)n SR"
CH2CH2CH CH2CH2CH2COOH
SR"
-CH2CH2NH2.
n is an integer in the range of 1 to 4 wherein within the same molecule n is
not necessarily
the same integer; and M is a cation of alkaline earth metal, alkali metal,
NH4+ or NR"3+
and wherein R" is C,-C4 alkyl.
Preferred thio-derivatives for use herein have the formula SR~ wherein R~ is
(CHZ)nCOOH, (CHZ)~OH, and (COOH)CH2CH2(COOH)~ wherein n is an integer from 1
to 4.
Especially preferred for use herein are thioglycolate (R~ = CHzCOOH)
thioethanol (R~=
(CHz)ZOH) and thiosuccinate (R~= (COOH)CH2CH2(COOH)), especially
thioglycolate.
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Suitable quaternized nitrogen derivatives for use herein can be represented by
Q+
wherein Q is selected from amines, saturated or unsaturated, substituted or
unsubstituted
nitrogen containing heterocycles having from about 3 to about 8 ring members
and
comprising at least one nitrogen heteroatom. Preferred substituents are
carboxylates,
amides, C~-C4 alkyl and alkyl carboxylates.
Particularly preferred for use herein are Q groups selected from:
NR"3,
N
N
\COOH (nicotinate),
N COOH
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N COOH
N /
N CONH2
N /
N
CONH2
N
CONH2
N CONH2
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N
COO- (isonicotinate),
N
CONH2
N
N (DABCO),
N
CH3
N
O
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CH3
Cy
CH3
NHR"
N
R"
NR"2
N
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R"
N
N
R"
(CH3)2N-~2~
N(CH3)2CH2COOH (dimethylaminobetaine);
N(CH3)2(CH2)n~z
N(CH3)2(CH2)nN+R,~3~
N(CH3)2CH2CONH2;
wherein R" is C1-C4 alkyl and n is an integer of from 1 to 4.
Particularly preferred quaternized nitrogen derivatives for use herein are
nicotinate,
diazabicyclooctane (DABCO), dimethylaminobetaine and isonicotinate, especially
nicotinate.
The quaternized nitrogen derivative is attached to the nitrogen-containing
heterocycle via
its tertiary nitrogen atom.
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Preferred X groups include Y, SR", halogen (preferably F or Cl), NR"H, NR"2,
OR",
COOH, SCN, SS03, 503, NR1R2, CN, N3 and quaternized nitrogen derivatives Q+,
wherein R" is C1-C8 alkyl, or aryl and wherein Q, Rl and R2 are as defined
above.
Particularly preferred X groups for use herein are Y, halogen (fluorine and
chlorine) and
quaternized nitrogen derivatives.
A particularly preferred reactive dye compound of the present invention
wherein the Y
group in formula (I) above is derived from aceto phosphonic acid.
The present invention further relates to processes for the preparation of dyes
herein. In
general, dyes having the formula (I) can be prepared by reacting suitable
precursors of the
dye of formula (I) with one another, at least one of which contains a group D-
L-Z,
wherein D, L and Z are as defined above, and at least one of which contains a
Y group
(wherein Y is as defined above) and at least one of which contains an X group.
It will be
understood by those skilled in the art that in the case where X is halogen,
then the
halogen is part of the Z group in the starting materials e.g.
dichlorotriazine.
For example, dye compounds of the invention having a formula (I) wherein Z is
a triazine
heterocycle can be prepared by reacting one mole of dichlorotriazine dye, such
as those
commercially available from BASF under the trade name Procion MX (RTM), with
one
mole of a suitable reactant containing a Y group and then reacting the
intermediate dye
compounds obtained with one mole of a suitable reactant containing an X group.
It will
be understood by those skilled in the art that when X is halogen, then the
halogen is part
of the starting material containing the Z group, e.g. dichlorotriazine, and no
separate
reaction with a reactant containing an X group needs to be carried out. It
will also be
understood by those skilled in the art that in the case where X is equal to Y
(e.g. bis-
phosphonate compounds) then one mole of dichlorotriazine dye can be reacted
with two
moles of a suitable reactant containing a Y group.
Dye compounds of the invention having a formula (I) wherein Z is a pyrimidine
heterocycle can be prepared by reacting a difluoromonochloro pyrimidine dyes
such as
those commercially available from Clariant under the trade names Drimalan F
(RTM) and
Drimarene R or K (RTM), or a trichloropyrimidine dyes such as those
commercially
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available from Clariant under the trade name Drimarene X, with a suitable
reactant
containing a Y group and then reacting the intermediate dye obtained with a
suitable
reactant containing an X group. As discussed above for triazines, it will be
understood by
those skilled in the art that when X is halogen, then the halogen is part of
the starting
material containing the Z group, e.g. difluoromonochloropyrimidine or
trichloropyrimidine, and no separate reaction with a reactant containing an X
group needs
to be carned out. It will also be understood by those skilled in the art that
in the case
where X is equal to Y (e.g. bis-phosphonate compounds) then one mole of
difluoromonochloro pyrimidine dye can be reacted with two moles of a suitable
reactant
containing a Y group.
Due to the assymmetric nature of the pyrimidine heterocycle, dye compounds of
the
invention having a formula (I) wherein Z is a pyrimidine heterocycle can also
be prepared
by reacting a difluoromonochloropyrimidine dye such as those commercially
available
from Clariant under the tradenames Drimalan F (RTM) and Drimarene R or K
(RTM), or
a trichloropyrimidine dye such as those commercially available from Clariant
under the
trade name Drimarene X, with a suitable reactant containing a Y group and then
reacting
the intermediate dye obtained with a suitable reactant containing an X' group.
Dye compounds of the invention having a formula (I) wherein Z is a quinoxaline
heterocycle can be prepared by reacting a dichloroquinoxaline dye such as
those
commercially available from Dystar under the tradename Levafix E (RTM), with a
suitable reactant containing a Y group and then reacting the intermediate dye
obtained
with a suitable reactant containing an X group. It will be understood by those
skilled in
the art that when X is halogen, then the halogen is part of the starting
material containing
the Z group, e.g. dichloroquinoxaline, and
no separate reaction with a reactant containing an X group needs to be carried
out. It will
also be understood by those skilled in the art that in the case where X is
equal to Y (e.g.
bis-phosphonate compounds) then one mole of dichloroquinoxaline dye can be
reacted
with two moles of a suitable reactant containing a Y group.
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Preferred dye compositions herein comprise an acidic buffer material. Any
acidic buffer
suitable for use in reactive dye compositions can be used herein. An example
of a
suitable buffer is a mixed phosphate buffer.
When the dye composition herein is in the form of a paste a preferred
ingredient is a
thickening agent. Any suitable thickening agents suitable for use in reactive
dye
compositions can be used herein.
When the dye composition is in the form of an aqueous solution or aqueous
gel/paste, the
dye composition preferably has a pH of from about 2 to about 8.
The dyeing and printing processes which can be used with the dyes herein are
conventional processes which are well known and which have been widely
described in
the technical and patent literature. The dye compounds herein are suitable for
dyeing
cotton both by the exhaust method (long liquor) and also by various pad-dyeing
methods,
whereby the goods are impregnated with aqueous, salt-containing or salt-free
dye
solutions and the dye is fixed after an alkali treatment or in the presence of
alkali, if
appropriate with the application of heat. The dye compounds herein are also
suitable for
the cold pad-batch method, in which the dye together with the alkali is
applied at the pad-
mangle melting point and then fixed by several hours of storage at room
temperature.
After fixing, the dyeings are thoroughly rinsed with cold and hot water, if
appropriate
with the addition of an agent acting as a dispersant and promoting the
diffusion of the
non-fixed portions. The dyes of the present invention are also suitable for
use in a
number of other processes such as pad-steam and pad-bake and the like.
Thus in accordance with another aspect of the present invention there is
provided a use of
the reactive dyes of the present invention for dyeing and printing substrates
such as
cotton, wool, nylon, silk, keratin, hair, leather, paper and the like. The
compounds herein
can ~be used in methods of dyeing all of the substrates listed above by
applying an
aqueous solution of one or more of the reactive dyes of the present invention
to the
substrate to be dyed under suitable conditions of pH and temperature.
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The following examples serve to illustrate the compounds and compositions of
the
present invention.
The starting compounds and components given in the examples below can be used
in the
form of the free acid or in the form of their salts with alkali metal cations.
It is to be
understood that mixtures of compounds may be obtained in the final product. In
the
Examples below the starting materials are all commercially available. Procion
(RTM)
dyes are available from BASF UK, P.O. Box 4, Earl Road, Cheadle Hulme,
Cheshire,
SK8 6QG, UK, Drimarene (RTM) and Drimalan (RTM) dyes are available from
Clariant
(Switzerland) Ltd., R&D Dyestuffs, Post Box, Building 88/1007, CH-4002 Basel,
Cibacron (RTM) dyes are available from Ciba Specialty Chemicals Inc., R&D,
Textile
Dyes Division, K-410.312, CH-4002 Basel, and Levafix (RTM) dyes are
commercially
available from Dystar Textilfarben, GmbH & Co. Deutschland KG, BU-R/F & E,
Werk
Hochst, Building 6834, D-65926 Frankfurt am Main, Germany.
Example 1
0.005 moles of Procion Yellow MX-3R dye is dissolved in 1 SOmI of distilled
water in a
400m1 flask. The temperature of the reaction system is adjusted and maintained
at 0-5°C.
The pH of the starting dye solution is adjusted to 5-5.5 using solid sodium
carbonate.
0.005 moles of aceto diphosphonic acid (Briquest ADPA 60A) is dissolved in
SOmI of
distilled water. The pH of this aceto diphosphonic acid solution is adjusted
to around 4.5.
The aceto diphosphonic acid solution is slowly added into the solution of
Procion Yellow
MX-3R dye. The rate of addition is such that the addition takes around 2 hours
to
complete. During the process of addition the temperature of the reaction
system is
maintained at 0-5°C. After addition of the aceto diphosphonic acid
solution is complete,
the reaction is allowed to continue for 4-5 hours. The endpoint of the
reaction is
indicated by the pH of the reaction system remaining constant for more than S
minutes.
At this point the final dye is obtained. Using 6N HCI, the pH of the system is
then
reduced to below 2.5 to terminate the reaction. KSCN (about 25% of the total
solution) is
then added to the reaction mixture in order to precipitate the dye product.
Filtration using
Whatman filter paper is then carried out. The precipitate is then washed with
acetone for
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5-6 times (about SOmI of acetone used each time) to obtain the final dye
product in fine
powder form of deep yellow colour.
A possible synthetic mechanism for the reaction of the Procion dyes with
acetophosphonic acid is as follows:
Example 2
4 g of Levafix Goldgelb EG dye is dissolved in 1 SOmI of distilled water in a
400m1 flask.
The temperature of the reaction system is adjusted and maintained at 60-
65°C. The pH of
the starting dye solution is adjusted to 4.5-5 using solid sodium carbonate. 1
g of aceto
diphosphonic acid (Briquest ADPA 60A) is dissolved in SOmI of distilled water.
The pH
of this aceto diphosphonic acid solution is adjusted to around 3-3.5. The
aceto
diphosphonic acid solution is slowly added into the solution of Levafix
Goldgelb EG dye.
The rate of addition is such that the addition takes around 3-4 hours to
complete. During
the process of addition the temperature of the reaction system is maintained
at 60-65°C.
After addition of the aceto diphosphonic acid solution is complete, the
reaction is allowed
to continue for 1-2 hours. The endpoint of the reaction is indicated by the pH
of the
reaction system remaining constant for more than 5 minutes. At this point the
final dye is
obtained. Using 6N HCI, the pH of the system is then reduced to below 2.5 to
terminate
the reaction. KSCN (about 25% of the total solution) is then added to the
reaction
mixture in order to precipitate the dye product. Filtration using Whatman
filter paper is
then carried out. The precipitate is then washed with acetone for 5-6 times
(about SOmI
of acetone used each time) to obtain the final dye product in fine powder form
of orange-
yellow colour.
A possible synthetic mechanism for the reaction of the Levafix dyes with
acetophosphonic acid is as follows:
Example 3
0.005 moles of Drimalan Yellow FR dye is dissolved in 1 SOmI of distilled
water in a
400m1 flask. The temperature of the reaction system is adjusted and maintained
at 35-
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40°C. The pH of the starting dye solution is adjusted to 4.5-5 using
solid sodium
carbonate. 0.005 moles of aceto diphosphonic acid (or 2-hydroxyethane,l,l-
diphosphonic acid, Briquest ADPA 60A) is dissolved in SOmI of distilled water.
The pH
of this aceto diphosphonic acid solution is adjusted to around 4.5. The aceto
diphosphonic acid solution is slowly added into the solution of Drimalan
Yellow FR dye.
The rate of addition is such that the addition takes around 2 hours to
complete. During
the process of addition the temperature of the reaction system is maintained
at 35-40°C.
After addition of the aceto diphosphonic acid solution is complete, the
reaction is allowed
to continue for 4-5 hours. The endpoint of the reaction is indicated by the pH
of the
reaction system remaining constant for more than 5 minutes. At this point the
final dye is
obtained. Using 6N HCI, the pH of the system is then reduced to below 2.5 to
terminate
the reaction. KSCN (about 25% of the total solution) is then added to the
reaction
mixture in order to precipitate the dye product. Filtration using Whatman
filter paper is
then carried out. The precipitate is then washed with acetone for 5-6 times
(about SOmI
of acetone used each time) to obtain the final dye product in fine powder form
of deep
yellow colour.
The compounds prepared according to Examples 1 to 3 and at standard depths all
have
high Exhaustion Values, high Fixation Values, particularly on cellulosic
substrates such
as cotton, and show significant improvements in terms of reducing spent
dyestuff in
effluent, increasing dye affinity to the substrate, increasing the dye-
substrate covalent
bonding, increasing the ability to dye substrates at room temperature,
decreasing the
amount of dye that is removed during the post dyeing "soaping off process" and
therefore
simplifying the post dyeing "soaping off process" traditionally associated
with dyeing
cotton with fibre reactive dyes and reduction of staining of adjacent white
fabrics. In
addition, the compounds prepared above provide more intense dyeings and
require less
levels of salt for dyeing cotton substrates. These advantages can be
demonstrated by the
following Examples 4 and S.
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Example 4
All dye compounds prepared according to Examples 1 to 3 can be used to dye
cotton
using the dyeing procedures detailed below. After the cotton dyeing procedure
has been
carried out a soaping-off process can also be carried out on the cotton fibre.
Cotton dvein~~rocedure
An aqueous dye solution is prepared containing a dye compound according to any
of
Examples 1 to 3. The dye solution contains 1% on mass of fibre of dye, 80g/L
Na2S04
and 5% on mass of fibre of sodium acetate. The cotton fabrics are soaked in
water and
then the cotton fabrics are dyed in the above dye-bath at pH 7 at 25°C
for 45 minutes.
The dyed cotton fabric is then fixed in the dye-bath at pH 11.5 with addition
of 30g/L of
trisodium phosphate and dyeing continued at SO°C (25°C for the
Drimalan dye) for 60
minutes. The dyed fabric is rinsed with water.
In the above dyeing procedure the dye bath for each dye compound is almost
totally
exhausted (i.e. only slight colour in the dye bath after dyeing), indicating
that the
compounds prepared according to Examples 1 to 3 each have a high Exhaustion
Value
(>95%). The Exhaustion Values for each product can be obtained by comparing
the
photo-absorption of the dyebath liquid before and after dyeing. The Exhaustion
Values
for Examples 1 to 3 are given in Table A below.
Soapin -g off process
A soaping off process can then be carried out by washing the dyed fabrics with
an
aqueous solution of Sandozine NIE (2g/L) (available from Clariant
(Switzerland) Ltd.,
R&D Dyestuffs, Post Box, Building 88/1007, CH-4002 Basel) at 100°C for
30 minutes.
In the above soaping-off process hardly any colour was removed from the
fabric,
resulting in an almost colourless soaping liquid, indicating that the
compounds prepared
according to Examples 1 to 3 each have a high degree of dye -fibre covalent
bonding and
a high Fixation Value (>95%). The Fixation Values of the dye products prepared
according to Examples 1 to 3 are shown in Table A below.
From the Exhaustion and Fixation Values, the Efficiency Values can be
calculated.
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Table A - Exhaustion, Fixation and Efficiency Values for Examples 1 to 3
Eg. ExhaustionFixation Efficiency
Value Value Value
(E%) (F%) (T)
1 96.23% 96.61% 92.97
2 98.08% 92.65% 90.87
3 98.78% 98.60% 97.40
The E, F and T values of the dyes according to the present invention are
typically higher
than many of the commercially available starting materials. In particular, the
F and T
values of the dyes according to the present invention are significantly higher
than those of
the commercially available starting materials.
Co3 International Standards Organisation) Wash Fastness Test
The dyed fabrics are washed with an aqueous solution containing ECE Reference
Detergent (Sg/ml) and sodium carbonate (2g/ml) at 60°C for 30
minutes.
In the above wash fastness test, no noticeable colour was removed from the
cotton fibre
and no staining of the white adjacent fibres occurred (using Multiple Fibre
adjacent strip
supplied by the Society of Dyes and Colourists, Bradford, UK).
Example 5
All dye compounds prepared according to Examples 1 to 3 can be used to dye
nylon or
wool using the dyeing procedures detailed below. After the nylon/wool dyeing
procedure
has been carried out a wash-test procedure can be carried out on the dyed
fabric to test the
wash-fastness of the dye compounds.
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Wool/Nylon Dyeing Procedure
The wool/nylon fabric is soaked in a 2% w/w Alcopol-O (40% w/w sodium-d-
isooctylsulpho- succinate commercially available from Allied Colloids)
solution. The
fabric is then dyed for 1 hour at 100°C and pH 3.5 in a dye-bath
containing the following
compositions: 1.2% on mass of fibre of dye prepared according to any of
Examples 1 to
3, 5% on mass of fibre of sodium acetate, 1% Albegal B (commercially available
from
Ciba). The dyed wool/nylon fabric was then rinsed with water.
In the above procedure intense dyeings are provided for each of the compounds
prepared
according to Examples 1 to 3.
Co2 (ISO) Wash Fastness Test Procedure for Wool/Nylon Fabrics
The dyed wool/nylon fabric is washed in an aqueous solution containing Sg/L of
ECE
Reference Detergent (commercially available from the Society of Dyers and
Colourists,
Bradford, UK) at 50°C for 45 minutes.
In the above wash fastness test, no noticeable colour was removed from the
wool fibre
and no staining of the white adjacent fibres occurred ((using Multiple Fibre
adjacent strip
supplied by SDC Bradford).
