U.S. patent application number 11/197579 was filed with the patent office on 2005-12-15 for metal chelate compounds and inks.
This patent application is currently assigned to Avecia Limited. Invention is credited to Johnson, Kevin, Patel, Prakash, Raggatt, Mairi Elizabeth, Wright, Gavin.
Application Number | 20050274280 11/197579 |
Document ID | / |
Family ID | 31191732 |
Filed Date | 2005-12-15 |
United States Patent
Application |
20050274280 |
Kind Code |
A1 |
Wright, Gavin ; et
al. |
December 15, 2005 |
Metal chelate compounds and inks
Abstract
A metal chelate compound of the Formula (1) and salts thereof: 1
wherein: one of A and B is OH and the other is an azotriazole
group; and M is a metal or boron; and n is 0 to 4; compositions and
inks containing a compound of Formula (1), a process for ink jet
printing using the inks and to an ink jet printer cartridge
containing the ink.
Inventors: |
Wright, Gavin; (Manchester,
GB) ; Johnson, Kevin; (Lancashire, GB) ;
Raggatt, Mairi Elizabeth; (Oxford, GB) ; Patel,
Prakash; (Manchester, GB) |
Correspondence
Address: |
MORGAN LEWIS & BOCKIUS LLP
1111 PENNSYLVANIA AVENUE NW
WASHINGTON
DC
20004
US
|
Assignee: |
Avecia Limited
|
Family ID: |
31191732 |
Appl. No.: |
11/197579 |
Filed: |
August 5, 2005 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11197579 |
Aug 5, 2005 |
|
|
|
10441286 |
May 20, 2003 |
|
|
|
60410806 |
Sep 16, 2002 |
|
|
|
Current U.S.
Class: |
106/31.5 ;
534/707; 534/726 |
Current CPC
Class: |
C09D 11/328 20130101;
C09D 11/32 20130101 |
Class at
Publication: |
106/031.5 ;
534/707; 534/726 |
International
Class: |
C09D 011/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 27, 2002 |
GB |
0217442.3 |
Claims
1. A metal chelate compound of the Formula (1) and salts thereof:
43wherein: one of A and B is OH and the other is an azotriazole
group; and M is a metal or boron; and n is 3.
2. A compound according to claim 1 wherein the azotriazole group is
of the Formula (2a), (2b), (2c), (2d) or (2e): 44wherein: Z is H,
--OH, --Br, --Cl, --F, --CN, --NO.sub.2, --PO.sub.3H.sub.2,
--SO.sub.3H, --CO.sub.2H, optionally substituted phosphoramide,
optionally substituted alkyl, optionally substituted alkenyl,
optionally substituted alkynyl, optionally substituted aryl,
optionally substituted aralkyl, --SR.sup.1, --SO.sub.2R.sup.1,
--SO.sub.2NR.sup.2R.sup.3, --SOR.sup.1, --OR.sup.1, --C(O)R.sup.1,
--C(O)OR.sup.1, --C(O)R.sup.2R.sup.3, --NR.sup.2R.sup.3,
--NHCOR.sup.1; and Y is --CF.sub.3 or any one of the groups defined
for Z; and wherein: R.sup.1, R.sup.2 and R.sup.3 are each
independently H, optionally substituted alkyl, optionally
substituted alkenyl, optionally substituted alkynyl, optionally
substituted aryl or optionally substituted aralkyl; or R.sup.2 and
R.sup.3 together with the nitrogen to which they are attached form
an optionally substituted 5- or 6- membered ring.
3. A compound according to claim 1 or 2 wherein M is nickel.
4. A compound according to claim 3 wherein Y is CO.sub.2H or H and
Z is H.
5. A compound according to claim 4 wherein M is nickel.
6. (canceled)
7. (canceled)
8. (canceled)
9. (canceled)
10. (canceled)
11. A compound according to claim 1 having any one of the following
formulae or a salt thereof, wherein M is nickel: 45 46
12. A composition comprising: (a) one or more compound according to
claim 1 or claim 11; and (b) one or more water-soluble dye other
than a compound according to claim 1.
13. An ink comprising: (a) a compound according to claim 1; and (b)
a liquid medium.
14. An ink according to claim 13, 19 or 20 wherein the liquid
medium comprises a mixture of water and an organic solvent.
15. A process for printing an image on a substrate comprising
applying thereto by means of an ink jet printer an ink according to
claim 13.
16. A substrate printed by means of the process according to claim
15.
17. An ink jet printer cartridge comprising a chamber and ink,
wherein the ink is present in the chamber and the ink is as defined
in claim 13.
18. An ink jet printer containing an ink jet printer cartridge,
wherein the ink jet printer cartridge is as defined in claim
17.
19. An ink comprising: (a) a compound according to claim 11; and
(b) a liquid medium.
20. An ink according to claim 19 wherein the compound is Compound
13.
Description
[0001] This invention relates to dyes, to inks and to their use in
ink jet printing ("IJP"). IJP is a non-impact printing technique in
which droplets of ink are ejected through a fine nozzle onto a
substrate without bringing the nozzle into contact with the
substrate.
[0002] There are many demanding performance requirements for dyes
and inks used in IJP. For example they desirably provide sharp,
non-feathered images having good water-fastness, light-fastness and
optical density. The inks are often required to dry quickly when
applied to a substrate to prevent smudging, but they should not
form a crust over the tip of an ink jet nozzle because this will
stop the printer from working. The inks should also be stable to
storage over time without decomposing or forming a precipitate
which could block the fine nozzle.
[0003] WO 01/48090 relates to metal chelate azo compounds which
comprise a naphthol component and certain heterocyclic groups. WO
01/48090 does not disclose such compounds further substituted by a
triazole ring.
[0004] According to a first aspect of the present invention there
is provided a metal chelate compound of the Formula (1) and salts
thereof: 2
[0005] wherein:
[0006] one of A and B is OH and the other is an azotriazole group;
and
[0007] M is a metal or boron; and
[0008] n is 0 to 4.
[0009] Preferred azotriazole groups are of the Formula (2a), (2b),
(2c), (2d) or (2e): 3
[0010] wherein:
[0011] Z is H, --OH, --Br, --Cl, --F, --CN, --NO.sub.2,
--PO.sub.3H.sub.2, --SO.sub.3H, --CO.sub.2H, optionally substituted
phosphoramide, optionally substituted alkyl, optionally substituted
alkenyl, optionally substituted alkynyl, optionally substituted
aryl, optionally substituted aralkyl, --SR.sup.1,
--SO.sub.2R.sup.1, --SO.sub.2NR.sup.2R.sup.3, --SOR.sup.1,
--OR.sup.1, --C(O)R.sup.1, --C(O)OR.sup.1, --C(O)NR.sup.2R.sup.3,
--NR.sup.2R.sup.3, --NHCOR.sup.1; and
[0012] Y is CF.sub.3 or any one of the groups defined for Z;
and
[0013] wherein:
[0014] R.sup.1, R.sup.2 and R.sup.3 are each independently H,
optionally substituted alkyl, optionally substituted alkenyl,
optionally substituted alkynyl, optionally substituted aryl or
optionally substituted aralkyl; or
[0015] R.sup.2 and R.sup.3 together with the nitrogen to which they
are attached form an optionally substituted 5- or 6- membered
ring.
[0016] When Y or Z is optionally substituted phosphoramide the
phosphoramide is preferably substituted by optionally substituted
alkyl, optionally substituted aryl or optionally substituted
aralkyl. Preferred substituents include for example methyl, ethyl,
n-propyl, iso-propyl, hydroxyethyl, optionally substituted phenyl
or optionally substituted benzyl.
[0017] When Y or Z is optionally substituted alkyl, the alkyl group
is preferably optionally substituted C.sub.1-4-alkyl, more
preferably C.sub.1-4-alkyl optionally substituted by halo, hydroxy,
carboxy, sulpho or cyano. Examples include methyl, ethyl, n-propyl,
iso-propyl, trifluoromethyl, hydroxyethyl, cyanoethyl, sulphopropyl
and carboxyethyl. However, when Y or Z is optionally substituted
alkyl it is especially preferred that the alkyl group is methyl,
ethyl or trifluoromethyl.
[0018] When Y or Z is optionally substituted alkenyl, Y or Z is
preferably optionally substituted C.sub.2-C.sub.4 alkenyl.
[0019] When Y or Z is optionally substituted alkynyl, Y or Z is
preferably optionally substituted C.sub.2-C.sub.6 alkynyl.
[0020] When Y or Z is optionally substituted aryl the aryl group is
preferably optionally substituted phenyl, optionally substituted
naphthyl or optionally substituted heteroaryl. It is especially
preferred that when Y is optionally substituted aryl it is
optionally substituted phenyl or optionally substituted
heteroaryl.
[0021] Preferred optional substituents on Y when Y is optionally
substituted aryl include sulpho, carboxy, nitro, cyano, halo
(preferably chloro), alkoxy (preferably C.sub.1-6-alkoxy), alkyl
((preferably C.sub.1-6-alkyl) optionally substituted by halogen
(preferably fluoro), hydroxy, carboxy, phosphoric acid and sulpho.
Especially preferred optional substituents on Y when Y is
optionally substituted aryl are selected from C.sub.1-4-alkyl,
carboxy, phosphoric acid and sulpho. However, it is most preferred
that when Y is optionally substituted aryl that the aryl group is
substituted by carboxy.
[0022] Preferred optional substituents on Z when Z is optionally
substituted aryl include sulpho, carboxy, nitro, cyano, halo
(preferably chloro), alkoxy (preferably C.sub.1-6-alkoxy), alkyl
(preferably C.sub.1-6-alkyl) optionally substituted by halogen
(preferably fluoro), hydroxy, carboxy, phosphoric acid and sulpho.
Especially preferred optional substituents on Z as optionally
substituted aryl are selected from carboxy or halogen (preferably
chloro).
[0023] When Y or Z is optionally substituted aralkyl the aralkyl
group is preferably optionally substituted benzyl.
[0024] However, Y in Formulae (2a), (2b), (2c), (2d) or (2e) is
most preferably H, thiol, carboxy, halo (preferably chloro), alkyl
((preferably C.sub.1-6-alkyl) optionally substituted by hydroxy,
carboxy, halo (preferably fluoro) or sulpho. It is especially
preferred that Y in Formulae (2a) to (2e) is H, C.sub.1-4-alkyl or
carboxy or sulpho. However, it is most especially preferred that Y
is H or CO.sub.2H.
[0025] Z in Formulae (2a) to (2e) is preferably H, ethylester or
alkyl (preferably C.sub.1-4-alkyl) optionally substituted by
hydroxy, carboxy, halo (preferably fluoro) or sulpho. It is
especially preferred that Z in Formulae (2a) to (2e) is H or
C.sub.1-4-alkyl. However, it is most especially preferred that Z is
H.
[0026] R.sup.1, R.sup.2 and R.sup.3 are preferably each
independently H, optionally substituted C.sub.1-4-alkyl or
optionally substituted aryl, more preferably H, C.sub.1-4-alkyl
optionally substituted by hydroxy, carboxy, sulpho or cyano or
phenyl optionally substituted by hydroxy, carboxy, sulpho, nitro,
trifluoromethyl or cyano. Examples of groups represented by
R.sup.1, R.sup.2 and R.sup.3 include methyl, ethyl, n-propyl,
iso-propyl, hydroxyethyl, cyanoethyl, sulphopropyl, carboxyethyl or
carboxyphenyl. It is especially preferred however that R.sup.1,
R.sup.2 and R.sup.3 are H, optionally substituted C.sub.1-4-alkyl
for example, trifluoromethyl, hydroxyethyl or cyanoethyl, or
optionally substituted aryl for example phenyl optionally
substituted by carboxy; or R.sup.2 and R.sup.3 together with the
nitrogen to which they are attached form a 5- or 6- membered ring
(preferably morpholine, piperidine or piperazine).
[0027] M preferably comprises boron or one or more of the following
metals: nickel, chromium, cobalt, copper, zinc, iron or manganese.
The metal M, is preferably able to co-ordinate to the portion of
the compound of Formula (1) within square brackets in the ratio
1:1, 2:1, 2:2, 2:3 respectively. However, it is particularly
preferred that M is nickel. It is also preferred that M is able to
co-ordinate to the portion of the compound of Formula (1) within
square brackets in the ratio 1:1 and 2:1.
[0028] It is preferable that n is 0, 1, 2 or 3 more preferably 1, 2
or 3, especially 1 or 2.
[0029] It is especially preferred that the compound of Formula (1)
is a metal chelate compound of the Formula (3) or (4): 4
[0030] wherein D is an azotriazole group, preferably of Formula
(2a), (2b), (2c), (2d) or (2e) as hereinbefore defined; n is 1 or
2; and M is nickel.
[0031] When the metal chelate compound is of Formula (3), it is
preferred that there is one sulphonic acid group at the 4-position
on the naphthylene and one sulphonic acid group at the 8-position
on the naphthylene ring, relative to D being at the 2-position on
the naphthylene ring.
[0032] When the metal chelate compound is of Formula (4), it is
preferred that there is one sulphonic acid group at the 3-position
on the naphthylene ring and one sulphonic acid group at the
7-position on the naphthylene ring, relative to D being at the
1-position.
[0033] In view of the foregoing preferences the compound of Formula
(1) is preferably a metal chelate compound of the Formula (5) or
(6) or a salt thereof: 5
[0034] wherein:
[0035] D is a group of Formula (2a), (2b), (2c), (2d) or (2e) as
hereinbefore defined and preferred, M is a metal, more preferably
nickel.
[0036] When D is a group of Formula (2a), (2b), (2c), (2d) or (2e),
Y is preferably H or CO.sub.2H and Z is preferably H.
[0037] It is especially preferred that the compounds of Formula (1)
are magenta in colour.
[0038] The compounds of Formula (1) provide prints which exhibit a
high light-fastness and good optical density when incorporated into
inks for ink jet printing. The compounds of Formula (1) are also
highly soluble which improves operability and reduces crusting and
nozzle blockage when inks containing the compounds are used in an
ink jet printer.
[0039] Compounds of Formula (1) are preferably free from fibre
reactive groups. The term fibre reactive group is well known in the
art and is described for example in EP 0356014 A1. Fibre reactive
groups are capable, under suitable conditions, of reacting with the
hydroxyl groups present in cellulosic fibres or with the amino
groups present in natural fibres to form a covalent linkage between
the fibre and the dye. As examples of fibre reactive groups
excluded from the compounds of Formula (1) there may be mentioned
aliphatic sulphonyl groups which contain a sulphate ester group in
the beta-position to the sulphur atom, e.g.
beta-sulphato-ethylsulphonyl groups, alpha, beta-unsaturated acyl
radicals of aliphatic carboxylic acids, for example acrylic acid,
alpha-chloro-acrylic acid, alpha-bromoacrylic acid, propiolic acid,
maleic acid and mono- and dichloro maleic; also the acyl radicals
of acids which contain a substituent which reacts with cellulose in
the presence of an alkali, e.g. the radical of a halogenated
aliphatic acid such as chloroacetic acid, beta-chloro and
beta-bromopropionic acids and alpha, beta-dichloro- and
dibromopropionic acids or radicals of vinylsulphonyl- or
beta-chloroethylsulphonyl- or beta-sulphatoethyl-sulph- onyl-endo-
methylene cyclohexane carboxylic acids. Other examples of cellulose
reactive groups are tetrafluorocyclobutyl carbonyl,
trifluoro-cyclobutenyl carbonyl, tetrafluorocyclobutylethenyl
carbonyl, trifluoro-cyclobutenylethenyl carbonyl; activated
halogenated 1,3-dicyanobenzene radicals; and heterocyclic radicals
which contain 1, 2 or 3 nitrogen atoms in the heterocyclic ring and
at least one cellulose reactive substituent on a carbon atom of the
ring.
[0040] The compounds of Formula (1) may be in the free acid or salt
form. Preferred salts are water-soluble, for example alkali metal
salts, especially lithium, sodium, potassium, ammonium, substituted
ammonium and mixed salts thereof. Preferred alkali metal salts are
those with sodium, lithium, ammonium and substituted alkyl ammonium
salts.
[0041] Preferred ammonium and substituted alkyl ammonium salts have
cations of the formula .sup.+NV.sub.4 wherein each V independently
is H or optionally substituted alkyl, or two groups represented by
V are H or optionally substituted alkyl and the remaining two
groups represented by V, together with the N atom to which they are
attached, form a 5- or 6- membered ring (preferably a morpholinyl,
pyridinyl or piperidinyl ring).
[0042] Preferably each V independently is H or C.sub.1-4-alkyl,
more preferably H, --CH.sub.3 or CH.sub.3CH.sub.2--, especially
H.
[0043] Examples of cations include .sup.+NH.sub.4, morpholinium,
piperidinium, pyridinium, (CH.sub.3).sub.3N.sup.+H,
(CH.sub.3).sub.2N.sup.+H.sub.2,
H.sub.2N.sup.+(CH.sub.3)(CH.sub.2CH.sub.3- ),
CH.sub.3N.sup.+H.sub.3, CH.sub.3CH.sub.2N.sup.+H.sub.3,
H.sub.2N.sup.+(CH.sub.2CH.sub.3).sub.2,
CH.sub.3CH.sub.2CH.sub.2N.sup.+H.- sub.3,
(CH.sub.3).sub.2CHN.sup.+H.sub.3, N.sup.+(CH.sub.3).sub.4,
N.sup.+(CH.sub.2CH.sub.3).sub.4, N-methyl pyridinium, N,N-dimethyl
piperidinium and N,N-dimethyl morpholinium.
[0044] It is especially preferred that the compound is in the form
of a sodium, lithium, potassium, ammonium or substituted ammonium
salt.
[0045] Preferably the metal chelate compound is not a copper or
nickel chelate of any of Ligands a to e or any salt thereof: 6
[0046] Preferably the metal chelate compound is not a chrome
chelate of Ligand f or any salt thereof: 7
[0047] Preferably the metal chelate compound is not a cobalt
chelate of Ligands g or h or any salt thereof: 8
[0048] Preferably the metal chelate compound is not a chrome
chelate of Ligand i or j or any salt thereof: 9
[0049] Preferably the metal chelate compound is not a metal chelate
of Ligand k, l or m or any salt thereof: 10
[0050] Preferably the metal chelate compound is not a metal chelate
of any of the above Ligands f to m inclusive, more preferably a to
m inclusive, or any salt thereof.
[0051] Preferably the compounds of the invention have a chroma of
at least 50 when printed on plain paper.
[0052] The compounds of Formula (1) may be converted into a salt
using known techniques. For example, an alkali metal salt of a
compound may be converted into a salt with ammonia or an amine by
dissolving an alkali metal salt of the dye in water and passing the
solution through a column of a suitably modified ion exchange
resin.
[0053] The compounds of Formula (1) may be prepared using
conventional techniques for the preparation of metal chelate
compounds. For example, a suitable method comprises adding together
a metal salt and a solution of a compound of Formula (7): 11
[0054] wherein A, B and n are as hereinbefore defined in relation
to Formula (1).
[0055] The product of the above process may be converted to a salt
by conventional techniques as hereinbefore described.
Alternatively, the product may be isolated in its free acid form by
acidifying the reaction mixture, preferably using a mineral acid,
for example hydrochloric acid and when the product precipitates as
a solid it may be separated from the mixture by filtration.
Unwanted anions may be and preferably are removed from the product
of the above process by dialysis, osmosis, ultra filtration or a
combination thereof. Alternatively, the product solution is
subjected to the above purification directly without isolation of
the product.
[0056] The compounds of Formula (7) may be prepared by, for
example, diazotising a compound of the formula A.sup.1-NH.sub.2 to
give a diazonium salt and coupling the resultant diazonium salt
with a compound of the Formula (7a): 12
[0057] wherein A.sup.1 is a triazole group, one of B and L is OH
and the other is H and n is as hereinbefore defined in relation to
Formula (1).
[0058] The diazotisation is preferably performed at a temperature
below 6.degree. C., more preferably at a temperature in the range
-10.degree. C. to 5.degree. C. Preferably the diazotisation is
performed in water, preferably at a pH below 7. Dilute mineral
acid, e.g. HCl or H.sub.2SO.sub.4, are often used to achieve the
desired acidic conditions.
[0059] The present invention also covers mixtures comprising two or
more compounds of the Formula (1) or salts thereof. Furthermore,
the compounds of Formula (1) may be mixed with commercially
available dyes, especially those listed in the International Colour
Index, to adjust the shade or other properties as desired.
[0060] According to a second aspect of the present invention there
is provided a composition comprising:
[0061] (a) one or more compound according to the first aspect of
the present invention; and
[0062] (b) one or more water-soluble dye other than a compound
according to the first aspect of the invention.
[0063] The water-soluble dye is preferably a water-soluble magenta
dye, for example a xanthene dye, an azo or bis azo dye, more
preferably an anionic azo or bis azo dye and especially an azo or
bis azo dye which contains one or more groups selected from
sulphonate, carboxylate and thiocarboxylate groups.
[0064] Preferred water-soluble magenta dyes include C.I. Acid Red
50, 52, 87, 91, 92, 95, 249 and 289; C.I. Direct Violet 106 and
107; compounds 100 to 107, 200 and 201 described on pages 8 and 9
of WO96/24636; compounds 1 to 24 shown described on columns. 4 to
10 in U.S. Pat. No. 5,542,970; compounds 1 to 55 described on pages
7 to 17 of EP-A-682 088; compounds 1 to 14 shown in Example 1 to 6
of EP-A-194,885; compounds 1 to 24 described on pages 8 to 13 of
EP-A-717 089; the compounds described in examples 1 to 16 in
columns. 5 to 11 of U.S. Pat. No. 5,262,527; and the dyes described
in Examples 1 to 21 in WO 94/16021.
[0065] Especially preferred water-soluble magenta dyes for use in
the composition according to the second aspect of the invention
include C.I. Acid Red 52, C.I. Acid Red 289 or a dye of the Formula
(8), (9) and (10) and salts thereof: 13
[0066] The dye of Formula (8) may be prepared using the method
described in Example 1 of EP 0 559 310. The dye of the Formula (9)
may be prepared using the method described in Example 3 of PCT
publication number WO 94/16021. The dye of Formula (10) may be
prepared using the method described in Example 1 of WO
96/24636.
[0067] The composition according to the second aspect of the
present invention preferably comprises:
[0068] (a) from 1 to 99, more preferably from 3 to 70 and
especially from 5 to 50 parts in total of the compound(s) according
to the first aspect of the invention; and
[0069] (b) from 99 to 1, more preferably from 30 to 97 parts and
especially 95 to 50 parts in total of the water-soluble magenta
dye(s);
[0070] wherein the parts are by weight and the sum of the parts
(a)+(b)=100.
[0071] The composition may contain a single dye of Formula (1) or a
mixture thereof. Similarly, the composition may contain a single
water-soluble magenta dye or a mixture of two or more water-soluble
magenta dyes.
[0072] The compounds and compositions according to the first and
second aspects of the present invention may be, and preferably are,
purified to remove undesirable impurities before they are
incorporated into inks for ink jet printing. Conventional
techniques may be employed for purification, for example
ultrafiltration, reverse osmosis and/or dialysis.
[0073] According to a third aspect of the present invention there
is provided an ink comprising:
[0074] (a) a compound according to the first aspect of the present
invention, or a composition according to the second aspect of the
invention; and
[0075] (b) a liquid medium.
[0076] Preferably component (a) of the ink is or comprises one of
the preferred compounds or compositions as hereinbefore described
in relation to the first or second aspect of the invention.
[0077] The liquid medium preferably comprises:
[0078] (i) water;
[0079] (ii) a mixture of water and an organic solvent; or
[0080] (iii) an organic solvent free from water.
[0081] The number of parts by weight of component (a) of the ink is
preferably from 0.01 to 30, more preferably 0.1 to 20, especially
from 0.5 to 15, and more especially from 1 to 5 parts. The number
of parts by weight of component (b) is preferably from 99.99 to 70,
more preferably from 99.9 to 80, especially from 99.5 to 85, and
more especially from 99 to 95 parts. The number of parts (a)+(b) is
100 and all parts mentioned here are by weight.
[0082] Preferably component (a) is completely dissolved in
component (b). Preferably component (a) has a solubility in
component (b) at 20.degree. C. of at least 10%. This allows the
preparation of concentrates which may be used to prepare more
dilute inks and reduces the chance of the compound(s) of component
(a) of the ink precipitating if evaporation of the liquid medium
occurs during storage.
[0083] When the liquid medium comprises a mixture of water and an
organic solvent, the weight ratio of water to organic solvent is
preferably from 99:1 to 1:99, more preferably from 99:1 to 50:50
and especially from 95:5 to 80:20.
[0084] It is preferred that the organic solvent present in the
mixture of water and organic solvent is a water-miscible organic
solvent or a mixture of such solvents. Preferred water-miscible
organic solvents include C.sub.1-6-alkanols, preferably methanol,
ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,
tert-butanol, n-pentanol, cyclopentanol and cyclohexanol; linear
amides, preferably dimethylformamide or dimethylacetamide; ketones
and ketone-alcohols, preferably acetone, methyl ether ketone,
cyclohexanone and diacetone alcohol; water-miscible ethers,
preferably tetrahydrofuran and dioxane; diols, preferably diols
having from 2 to 12 carbon atoms, for example pentane-1,5-diol,
ethylene glycol, propylene glycol, butylene glycol, pentylene
glycol, hexylene glycol and thiodiglycol and oligo- and
poly-alkyleneglycols, preferably diethylene glycol, triethylene
glycol, polyethylene glycol and polypropylene glycol; triols,
preferably glycerol and 1,2,6-hexanetriol; mono-C.sub.1-4-alkyl
ethers of diols, preferably mono-C.sub.1-4-alkyl ethers of diols
having 2 to 12 carbon atoms, especially 2-methoxyethanol,
2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol,
2-[2-(2-methoxyethoxy)ethoxy] ethanol, 2-[2-(2-ethoxyethoxy)
-ethoxy]-ethanol and ethyleneglycol monoallylether; cyclic amides,
preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone;
cydic esters, preferably caprolactone; sulphoxides, preferably
dimethyl sulphoxide and sulpholane. Preferably the liquid medium
comprises water and 2 or more, especially from 2 to 8,
water-miscible organic solvents.
[0085] Especially preferred water-soluble organic solvents are
cyclic amides, especially 2-pyrrolidone, N-methyl-pyrrolidone and
N-ethyl-pyrrolidone; diols, especially 1,5-pentane diol,
ethyleneglycol, thiodiglycol, diethyleneglycol and
triethyleneglycol; and mono- C.sub.1-4-alkyl and C.sub.1-4-alkyl
ethers of diols, more preferably mono- C.sub.1-4-alkyl ethers of
diols having 2 to 12 carbon atoms, especially
2-methoxy-2-ethoxy-2-ethoxyethanol.
[0086] A preferred liquid medium comprises:
[0087] (a) from 75 to 95 parts water; and
[0088] (b) from 25 to 5 parts in total of one or more solvents
selected from diethylene glycol, 2-pyrrolidone, thiodiglycol,
N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam and
pentane-1,5-diol;
[0089] wherein the parts are by weight and the sum of the parts (a)
and (b)=100.
[0090] Another preferred liquid medium comprises:
[0091] (a) from 60 to 80 parts water;
[0092] (b) from 2 to 20 parts diethylene glycol; and
[0093] (c) from 0.5 to 20 parts in total of one or more solvents
selected from 2-pyrrolidone, N-methylpyrrolidone, cyclohexanol,
caprolactone, caprolactam, pentane-1,5-diol and thiodiglycol;
[0094] wherein the parts are by weight and the sum of the parts
(a), (b) and (c)=100.
[0095] Examples of further suitable ink media comprising a mixture
of water and one or more organic solvents are described in U.S.
Pat. No. 4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No.
4,626,284 and EP 4,251,50A.
[0096] When the liquid medium comprises an organic solvent free
from water, (i.e. less than 1% water by weight) the solvent
preferably has a boiling point of from 300 to 200.degree. C., more
preferably of from 400 to 150.degree. C., especially from 50 to
125.degree. C. The organic solvent may be water-immiscible,
water-miscible or a mixture of such solvents. Preferred
water-miscible organic solvents are any of the hereinbefore
described water-miscible organic solvents and mixtures thereof.
Preferred water-immiscible solvents include, for example, aliphatic
hydrocarbons; esters, preferably ethyl acetate; chlorinated
hydrocarbons, preferably CH.sub.2Cl.sub.2; and ethers, preferably
diethyl ether; and mixtures thereof.
[0097] When the liquid medium comprises a water-immiscible organic
solvent, preferably a polar solvent is included because this
enhances solubility of the dye in the liquid medium. Examples of
polar solvents include C.sub.1-4-alcohols. In view of the foregoing
preferences it is especially preferred that where the liquid medium
is an organic solvent free from water it comprises a ketone
(especially methyl ethyl ketone) and/or an alcohol (especially a
C.sub.1-4-alkanol, such as ethanol or propanol).
[0098] The organic solvent free from water may be a single organic
solvent or a mixture of two or more organic solvents. It is
preferred that when the medium is an organic solvent free from
water it is a mixture of 2 to 5 different organic solvents. This
allows a medium to be selected which gives good control over the
drying characteristics and storage stability of the ink.
[0099] Ink media comprising an organic solvent free from water are
particularly useful where fast drying times are required and
particularly when printing onto hydrophobic and non-absorbent
substrates, for example plastics, metal and glass.
[0100] An especially preferred ink comprises:
[0101] (a) from 1 to 10 parts in total of a compound or composition
according to the first or second aspect of the invention;
[0102] (b) from 2 to 60, more preferably 5 to 40 parts of
water-soluble organic solvent; and
[0103] (c) from 30 to 97, more preferably 40 to 85 parts water;
[0104] wherein all parts are by weight and the sum of the parts (a)
+(b) +(c)=100.
[0105] When the liquid medium in the ink comprises a mixture of
water and an organic solvent; or an organic solvent free from
water, component (a) of the ink may comprise a compound of the
Formula (1), or salt thereof, as hereinbefore defined in relation
to the first aspect of the invention.
[0106] Preferred low melting solid media have a melting point in
the range from 60.degree. C. to 125.degree. C. Suitable low melting
point solids include long chain fatty acids or alcohols, preferably
those with C.sub.18-24 chains, and sulphonamides. A dye of Formula
(1) may be dissolved in the low melting point solid or may be
finely dispersed in it.
[0107] The inks according to the present invention may also contain
additional components conventionally used in ink jet printing inks,
for example viscosity and surface tension modifiers, corrosion
inhibitors, biocides, kogation reducing additives, anti-cockle
agents to reduce paper curling and surfactants which may be ionic
or non-ionic.
[0108] The pH of the ink is preferably from 4 to 11, more
preferably from 7 to 10.
[0109] The viscosity of the ink at 25.degree. C. is preferably less
than 50 cP, more preferably less than 20 cP and especially less
than 5 cP.
[0110] When the inks according to the invention are used as ink jet
printing inks, the ink preferably has a concentration of less than
500 parts per million, more preferably less than 100 parts per
million of halide ions. It is especially preferred that the ink has
less than 100, more preferably less than 50 parts per million of
divalent and trivalent metals, wherein parts refer to parts by
weight relative to the total weight of the ink. We have found that
purifying the inks to reduce the concentration of these undesirable
ions reduces nozzle blockage in ink jet printing heads,
particularly in thermal ink jet printers.
[0111] A fourth aspect of the present invention provides a process
for printing an image on a substrate comprising applying thereto by
means of an ink jet printer an ink containing a compound according
to the first aspect of the invention or a composition according to
the second aspect of the invention.
[0112] The ink used in this process is preferably as defined in the
third aspect of the present invention.
[0113] The ink jet printer preferably applies the ink to the
substrate in the form of droplets which are ejected through a small
orifice onto the substrate. Preferred ink jet printers are
piezoelectric ink jet printers and thermal ink jet printers. In
thermal ink jet printers, programmed pulses of heat are applied to
the ink in a reservoir by means of a resistor adjacent to the
orifice, thereby causing the ink to be ejected in the form of small
droplets directed towards the substrate during relative movement
between the substrate and the orifice. In piezoelectric ink jet
printers the oscillation of a small crystal causes ejection of the
ink from the orifice.
[0114] The substrate is preferably paper, plastic, a textile, metal
or glass, more preferably paper, an overhead projector slide or a
textile material, especially paper.
[0115] Preferred papers are plain or treated papers which may have
an acid, alkaline or neutral character. Examples of commercially
available papers include, HP Premium Coated Paper, HP Photopaper
(all available from Hewlett Packard Inc.), Stylus Pro 720 dpi
Coated Paper, Epson Photo Quality Glossy Film, Epson Photo Quality
Glossy Paper (available from Seiko Epson Corp.), Canon HR 101 High
Resolution Paper, Canon GP 201 Glossy Paper, Canon HG 101 High
Gloss Film (all available from Canon Inc.), Wiggins Conqueror paper
(available from Wiggins Teape Ltd), Xerox Acid Paper and Xerox
Alkaline paper, Xerox Acid Paper (available from Xerox).
[0116] A fifth aspect of the present invention provides a
substrate, preferably a paper, an overhead projector slide or a
textile material, printed with an ink according to the third aspect
of the present invention or by means of the process according to
the fourth aspect of the present invention.
[0117] According to a sixth aspect of the present invention there
is provided an ink jet printer cartridge comprising a chamber and
ink, wherein the ink is present in the chamber and the ink contains
a compound or a composition according to the first or second aspect
of the present invention. Preferably the ink is as defined in the
third aspect of the present invention.
[0118] According to a seventh aspect of the present invention there
is provided an ink jet printer containing an ink jet printer
cartridge, wherein the ink jet printer cartridge is as defined in
the sixth aspect of the present invention.
[0119] The invention is further illustrated by the following
Examples in which all parts and percentages are by weight unless
otherwise stated.
EXAMPLE 1
Preparation of Compound (1) Wherein M is Nickel
[0120] 14
[0121] Stage (a): Preparation of
3-hydroxynaphthalene-2,6-disulfonic Acid 15
[0122] 7-Hydroxynaphthalene-2-sulfonic acid (250 g, 1.16 mol) was
added in portions to a mixture of concentrated H.sub.2SO.sub.4 (950
g) and water (50 g). The mixture was stirred at 110-120.degree. C.
for 3 hours, cooled to room temperature, added to a mixture of ice
and water (5000 ml) and the product precipitated by the addition of
sodium chloride. The resultant slurry was warmed to 90.degree. C.
to dissolve the product, stirred for 1 hour at this temperature and
then allowed to cool. The product was filtered off and the damp
product dissolved in water (3000 ml) at pH 10 by the addition of
concentrated sodium hydroxide solution. The solution was then
filtered to remove a small amount of insoluble material. The pH of
the filtrate was lowered to 7 with concentrated HCl and the product
precipitated by the addition sodium chloride. The product was
filtered off and dried in a vacuum oven to give 117 g of a cream
solid (68% yield).
[0123] Stage (b): 16
[0124] 3-amino-1,2,4-triazole-5-carboxylic acid hydrate (3.84 g,
0.03 mol) was suspended in water (180 ml) and dissolved by the
addition of 2M NaOH to pH 8. Sodium nitrite (2.27 g, 0.033 mol) was
added and the solution stirred until the sodium nitrite had
dissolved.
[0125] The mixture was then added dropwise to a cooled mix of
ice-water (150 g) and concentrated HCl (10 ml) at 0-5.degree. C.,
the mixture was stirred for 30 minutes at 0-5.degree. C. and then
excess nitrous acid was removed by adding sulphamic acid. The diazo
suspension was added slowly to a solution of
3-hydroxynaphthalene-2,6-disulfonic acid (13.4 g, 0.03 mol) in
water (300 ml) at pH 7-8 (2N NaOH) and cooled below 5.degree. C.
The reaction mixture was then stirred at 0-5.degree. C. for one
further hour, the product was precipitated by acidification to pH 4
with 2N HCl and collected by filtration. The product was washed
with 15% brine solution and then dried in a vacuum desiccator to
give 20 g of an orange solid (60% yield).
[0126] Stage (c): Preparation of Compound (1)
[0127] A solution of nickel acetate tetrahydrate (2.5 g, 0.01 mol)
in water (20 ml) was added dropwise to the product from stage (b)
(7.43 g, 0.01 mol) dissolved in water (100 ml) at pH 7-8 (2N NaOH).
The reaction mixture was stirred for 2 hours at 20.degree. C.,
dialysed using SpectraPor membrane tubing (molecular weight cut off
3500) to low conductivity (<100 .mu.s). Compound (1) was
obtained by evaporation under reduced pressure to afford a dark
solid (5 g). Analysis by mass spectrometry found m/z 499
(M-H).sup.-. Requires M.sup.+=500.
EXAMPLES 2 to 5
[0128] Compounds (2) to (5) of the Formula (11) were prepared using
an analogous process to that described in Example 1 except that in
stage (c) a metal salt as shown in Table 1 was used in place of
nickel acetate. 17
1TABLE 1 Example Compound Metal salt M Mass spectra analysis 2 (2)
Copper acetate Cu m/z 504 (M - H).sup.- 3 (3) Chromium acetate Cr
m/z 934 (M - H).sup.- 4 (4) Zinc acetate Zn m/z 947 (M - H).sup.- 5
(5) Cobalt acetate Co m/z 941 (M - H).sup.-
EXAMPLE 6 to 8
[0129] Compounds (6) to (8) of the Formula (12) described in Table
2 were prepared using an analogous process to that described in
Example 1 except that in stage (b) in place of
3-amino-1,2,4-triazole-5-carboxylic acid there was used the
triazole compound shown in Table 2. The name of the resultant
Compound is shown in the third column of Table 2. M is nickel.
18
2TABLE 2 Example Triazole Y Compound name 6 19 CF.sub.3 Nickel
chelate of [3-hydroxy-4-(5-trifluome- thyl-
1H-[1,2,4]triazole-3-ylazo)-naphthalene-2,7- disulfonic acid
("Compound (6)"). Analysis by mass spectrometry found m/z 989 (M -
H).sup.-. 7 20 H Nickel chelate of [3-hydroxy-4-(1H-
[1,2,4]triazole-3-ylazo)-naphthalene-2,7- disulfonic acid.
("Compound (7)"). Analysis by mass spectrometry found m/z 853 (M -
H).sup.-. 8 21 C.sub.6H.sub.5 Nickel chelate of
[3-hydroxy-4-(5-phenyl-1H-
[1,2,4]triazole-3-ylazo)-naphthalene-2,7- disulfonic acid.
("Compound (8)"). Analysis by mass spectrometry found m/z 1007 (M -
H).sup.-.
EXAMPLE 9
[0130] Compound (9) of the Formula (13) described in Table 3 was
prepared using an analogous process to that described in Example 1
except that in stage (b) in place of
3-hydroxynaphthalene-2,6-disulfonic acid there was used
2-hydroxynaphthalene-3,6-disulfonic acid.
[0131] Compounds (10) and (11) of the Formula (13) described in
Table 3 were prepared using an analogous process to that described
in Example 1 except that in stage (b) in place of
3-hydroxynaphthalene-2,6-disulfonic acid there was used
2-hydroxynaphthalene-3,6-disulfonic acid and in place of
3-amino-1,2,4-triazole-5-carboxylic acid there was used the amino
triazole compound shown in Table 3. 22
3TABLE 3 Example Triazole Y Dye name 9 23 CO.sub.2H Nickel chelate
of [5-(2-hydroxy-3,6-disulfo-
naphthalen-1-ylazo)-2H-[1,2,4]triazole-3- carboxylic acid].
("Compound (9)"). Analysis by mass spectrometry found mlz 941 (M -
H).sup.-. 10 24 SH Nickel chelate of [3-hydroxy-4-(5-mercapto-1H-
[1,2,4]triazole-3-ylazo)-naphthalene-2,7-dis- ulfonic acid].
("Compound (10)"). 11 25 SCH.sub.3 Nickel chelate of
[3-hydroxy-4-(5-methylsulfanyl- 1H-[1,2,4]triazole-3-ylazo)-na-
phthalene-2,7- disulfonic acid]. ("Compound (11)"). Analysis by
mass spectrometry found m/z 501 (M - H).sup.-.
EXAMPLE 12
[0132] Compound (12) Wherein M is Copper: 26
[0133] Compound (12) was prepared using an analogous process to
that described in Example 1 except that in stage (b)
2-hydroxynaphthalene-3,6-- disulfonic acid was used in place of
3-hydroxynaphthalene-2,6-disulfonic acid and in stage (c) copper
acetate was used in place of nickel acetate.
EXAMPLE 13
[0134] Preparation of Compound (13) Wherein M is Nickel: 27
[0135] Stage (a): 28
[0136] The product of Example 1 stage (a) (5g), (0.016 mol) was
added in portions during the course of 30 minutes to 27% oleum (10
ml) with stirring at room temperature. A second portion of 27%
oleum (10 ml) was added and the reaction mixture stirred overnight
at room temperature. The reaction mixture was then stirred for 3.5
hours at 120.degree. C., cooled and the product collected by
filtration using a sintered funnel and washed with concentrated
H.sub.2SO.sub.4 (5 ml). The crude product was dissolved in water
(20 ml) and precipitated by the addition of sodium chloride. The
solid was collected by filtration and dried to give a pale pink
solid.
[0137] Stage(b): Preparation of Compound (13) Wherein M is Nickel:
29
[0138] The Compound (13) was prepared using an analogous process to
that described in Example 1 except that in stage (b)
2-hydroxy-naphthalene-1,3- ,5,7-tetrasulphonic acid was used in
place of 3-hydroxynaphthalene-2, 6-disulfonic acid. Analysis by
mass spectrometry found m/z 579 (M-H).sup.-.
EXAMPLE 14
[0139] Preparation of Compound (14) Wherein M is Nickel: 30
[0140] Compound (14) was prepared using an analogous process to
that described in Example 1 except that in stage (b)
7-hydroxynaphthalene-1,3,- 6-trisulfonic acid was used in place of
3-hydroxynaphthalene-2,6-disulfoni- c acid. Analysis by mass
spectrometry found m/z 1101 (M-H).sup.-.
EXAMPLE 15
[0141] Preparation of Compound (15) Wherein M is Nickel: 31
[0142] Stage (a): Preparation of
5-(1-hydroxy-4-sulfo-naphthalen-2-ylazo)-- 2H-[1,2,4]triazole
32
[0143] 3-amino-1,2,4-triazole-5-carboxylic acid hydrate (1.28 g,
0.01 mol) was suspended in water (50 ml) and dissolved by the
addition of 2M NaOH to pH 8. Sodium nitrite (0.76 g, 0.11 mol) was
added and the solution stirred until the sodium nitrite had
dissolved.
[0144] The mixture was then added dropwise to a cooled mix of
ice-water (30 g) and concentrated HCl (3.0 ml) at 0-5.degree. C.,
the mixture was stirred for 30 minutes at 0-5.degree. C. and then
excess nitrous acid was removed by adding sulphamic acid. The diazo
suspension was added slowly to a solution of
4-hydroxy-naphthalene-1-sulfonic acid sodium salt (2.46 g, 0.01
mol) in water (100 ml) at pH 10-10.5 (2N NaOH) and cooled below
5.degree. C. The reaction mixture was then stirred at 0-5.degree.
C. for one further hour, the product was precipitated by
acidification to pH 4 with 2N HCl and collected by filtration. The
product was washed with water and then dried in a vacuum desiccator
to give 2.9 g of an orange solid.
[0145] Stage (b): Preparation of Compound (15):
[0146] A solution of nickel acetate tetrahydrate (1.39, 0.005 mol)
in water (10 ml) was added dropwise to the product from stage (a)
(1.9 g, 0.005 mol) dissolved in water (100 ml) at pH 7-8 (2N NaOH).
The reaction mixture was stirred for 2 hours at 20.degree. C.,
dialysed using SpectraPor membrane tubing (molecular weight cut off
3500) to low conductivity (<100 .mu.s). The product was obtained
by evaporation under reduced pressure to afford a dark solid (1.7
g). Analysis by mass spectrometry found m/z 781 (M-H).sup.-.
EXAMPLES 16 & 17
[0147] Compounds (16) and (17) described in Table 4 of the Formula
(14) were prepared using an analogous process to that described in
Example 15 except that in stage (b) the metal salt (M) shown in
Table 4 was used in place of nickel acetate. 33
4TABLE 4 Mass spectra Example Compound Metal salt M analysis 16
(16) Cobalt acetate Co m/z 781 (M - H).sup.- 17 (17) Chromium
acetate Cr m/z 827 (M - H).sup.-
EXAMPLE 18
[0148] Preparation of Compound (18) Wherein M is Nickel: 34
[0149] Compound (18) was prepared using an analogous process to
that described in Example 15 except that in stage (a)
3-amino-5-methylthio-1,2- ,4-triazole was used in place of
3-amino-1,2,4-triazole-5-carboxylic acid. Analysis by mass
spectrometry found m/z 785 (M-H).sup.-.
EXAMPLE 19
[0150] Preparation of Compound (19) Wherein M is Nickel: 35
[0151] Stage (a): 36
[0152] 1,8-Naphthosultone (25.0 g, 0.119 mol) was added in portions
to concentrated sulphuric acid (75 ml), the reaction mixture was
then stirred for 2 hours at 80.degree. C. and then added to a
mixture of ice (70 g) and water (20 ml). Anhydrous sodium sulfate
(46 g) was added in portions to the reaction mixture at 30.degree.
C., the product was collected by filtration and then dissolved in
water (120 ml) at 50.degree. C. The product was precipitated by the
addition of sodium chloride (25% w/v), stirred at 40.degree. C. for
1 hour and then collected by filtration. The solid was dried in a
vacuum oven to give 30 g of a pink solid (76%).
[0153] Stage (b) - Preparation of
4-hydroxy-1,5-disulphonaphthalene: 37
[0154] The product from stage (a) (30 g) was dissolved in water
(200 ml) at pH 11 by the addition of 2N sodium hydroxide. The
solution was stirred at room temperature for 2 hrs to complete the
hydrolysis and the solution of the product used in the next stage
without isolation.
[0155] Stage (c)
[0156] Compound (19) was prepared using an analogous process to
that described in Example 15 except that in the process of Example
15, stage (a), 4-hydroxy-1,5-disulphonaphthalene acid was used in
place of 4-hydroxy-naphthalene-1-sulfonic acid. Analysis by mass
spectrometry found m/z 941 (M-H).sup.-.
EXAMPLES 20 & 21
[0157] Compounds (20) and (21) described in Table 5 of the Formula
(15) were prepared using an analogous process to that described in
Example 15 except that in stage (a)
4-hydroxy-naphthalene-1,5-disulfonic acid was used in place of
4-hydroxy-naphthalene-1-sulfonic acid and in place of
3-amino-1,2,4-triazole-5-carboxylic acid the amino triazole
compound shown in Table 5 was used. 38
5TABLE 5 Example Y Triazole Dye name 20 --CF.sub.3 39 Nickel
chelate of [4- hydroxy-3-(5-trifluoro- methyl-1H-[1,2,4]triazole-
3-ylazo)-naphthalene-1,5- disulfonic acid]. ("Compound (20)").
Analysis by mass spectrometry found m/z 989 (M - H).sup.-. 21 --H
40 Nickel chelate of [4- hydroxy-3-(1H-[1,2,4]triazol-3-ylazo)-
naphthalene-1,5-disulfonic acid]. ("Compound (21)"). Analysis by
mass spectrometry found m/z 853 (M - H).sup.-.
EXAMPLE 22
[0158] Preparation of Compound (22) Wherein M is Nickel: 41
[0159] Compound (22) was prepared using an analogous process to
that described in Example 15 except that in stage (a)
8-hydroxy-naphthalene-1,- 3,6-trisulfonic acid was used in place of
4-hydroxy-naphthalene-1-sulfonic acid. Analysis by mass
spectrometry found m/z 1157 (M-H).sup.-.
EXAMPLE 23
[0160] Preparation of Compound (23) Wherein M is Nickel: 42
[0161] Compound (23) was prepared using an analogous process to
that described in Example 15 except that in stage (a)
8-hydroxy-naphthalene-1,- 3,6-trisulfonic acid was used in place of
4-hydroxy-naphthalene-1-sulfonic acid and 3-amino-1,2,4-triazole
was used in place of 3-amino-1,2,4-triazole-5-carboxylic acid.
Analysis by mass spectrometry found m/z 534 (M-H).sup.-.
[0162] Inks
[0163] The inks described in Tables I and II may be prepared
wherein the Compound described in the first column is the Compound
made in the above Examples of the same number. Numbers quoted in
the second column onwards refer to the number of parts of the
relevant ingredient and all parts are by weight. The inks may be
applied to paper by thermal or piezo ink jet printing.
[0164] The following abbreviations are used in Table I and II:
[0165] PG=propylene glycol
[0166] DEG=diethylene glycol
[0167] NMP=N-methyl pyrollidone
[0168] DMK=dimethylketone
[0169] IPA=isopropanol
[0170] MEOH=methanol
[0171] 2P=2-pyrollidone
[0172] MIBK=methylisobutyl ketone
[0173] P12=propane-1,2-diol
[0174] BDL=butane-2,3-diol
[0175] CET=cetyl ammonium bromide
[0176] PHO=Na.sub.2HPO.sub.4 and
[0177] TBT=tertiary butanol
[0178] TDG=thiodiglycol
6TABLE I Dye Na Compound Content Water PG DEG NMP DMK NaOH Stearate
IPA MEOH 2P MIBK 1 2.0 80 5 6 4 5 2 3.0 90 5 5 0.2 3 10.0 85 3 3 3
5 1 4 2.1 91 8 1 5 3.1 86 5 0.2 4 5 6 1.1 81 9 0.5 0.5 9 7 2.5 60 4
15 3 3 6 10 5 4 8 5 65 20 10 9 2.4 75 5 4 5 6 5 10 4.1 80 3 5 2 10
0.3 11 3.2 65 5 4 6 5 4 6 5 12 5.1 96 4 13 10.8 90 5 5 14 10.0 80 2
6 2 5 1 4 15 1.8 80 5 15 16 2.6 84 11 5 17 3.3 80 2 10 2 6 18 12.0
90 7 0.3 3 19 5.4 69 2 20 2 1 3 3 20 6.0 91 4 5
[0179]
7TABLE II Dye Compound Content Water PG DEG NMP CET TBT TDG BDL PHO
2P PI2 21 3.0 80 15 0.2 5 22 9.0 90 5 1.2 5 23 1.5 85 5 5 0.15 5.0
0.2 4 2.5 90 6 4 0.12 5 3.1 82 4 8 0.3 6 1 0.9 85 10 5 0.2 7 8.0 90
5 5 0.3 8 4.0 70 10 4 1 4 11 9 2.2 75 4 10 3 2 6 10 10.0 91 6 3 1
9.0 76 9 7 3.0 0.95 5 12 5.0 78 5 11 6 13 5.4 86 7 7 20 2.1 70 5 5
5 0.1 0.2 0.1 5 0.1 5 15 2.0 90 10 1 2 88 10 2 5 78 5 12 5 1 8 70 2
8 15 5 1 10 80 8 12 1 10 80 10
* * * * *