GB2173210A - Basic disazo pyridone dyes - Google Patents
Basic disazo pyridone dyes Download PDFInfo
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- GB2173210A GB2173210A GB08607702A GB8607702A GB2173210A GB 2173210 A GB2173210 A GB 2173210A GB 08607702 A GB08607702 A GB 08607702A GB 8607702 A GB8607702 A GB 8607702A GB 2173210 A GB2173210 A GB 2173210A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B44/00—Azo dyes containing onium groups
- C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
- C09B44/08—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group from coupling components containing heterocyclic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/021—Disazo dyes characterised by two coupling components of the same type
- C09B35/03—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a heterocyclic compound
- C09B35/031—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a heterocyclic compound containing a six membered ring with one nitrogen atom as the only ring hetero atom
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
New metal-free or metallised compounds of formula I, free from sulphonic acid groups, are useful for dyeing paper, textiles and leather <IMAGE> wherein the two pyridone couplers are identical; each n is 0, 1 or 2; R1, R2 and T are each H or specified substituents; X0 is a direct bond or a bridging group; and B is -A, -NR7R8 or <IMAGE> where A1 is C2-8-alkylene and R7-R9 are specified substituents or form a ring with the adjacent nitrogen atom.
Description
SPECIFICATION
Improvements in or relating to organic compounds
The invention relates to sulphonic acid free basic compounds useful for dyeing substrates such as paper, textile and leather.
According to the invention there is provided a compound in free base or acid addition salt form, in metal-free, 1:1 or 1:2 metal complex form, of formula I
in which the R1's are identical and are hydrogen, C1-4alkyl, C5-6cycloalkyl, phenyl, benzyl or phenyl-ethyl;
each n, independently, is 0, 1 or 2;
each R2, independently, is hydrogen, halogen, hydroxy, nitro, -COOH, C1,4alkyl or C1-4alkoxy;
the T's are identical and are hydrogen; -CN;
-COOR4;-CON(R5)2;-SO2N(R5)2;
the Xa's are identical and are -0--S-, or~N-R5; each R3, independently, is hydrogen, C14alkyl, -N(R5)2 or -CON(R5)2;
the R4's are identical and are C1-6alkyl or phenyl-C1-3alkyl;
each R5, independently, is hydrogen or C1.4alkyl; or when two R5'S are present attached to a nitrogen atom, both R5,s together with the N-atom to which they are attached may form a saturated ring which contains one to three heteroatoms and is unsubstituted or substituted by one to three C1-4alkyl;
the R6's are identical and are C1-4alkyl; # the B's are identical and are -A1-NR7R8; or -A1-NR7R8R9A#;; the A1's are identical and are C2 8alkylene; the R7,s are identical and are C1 6alkyl, C2-6alkyl monosubstituted by halogen, -OH or -CN,phenyl(C13) alkyl, the phenyl ring of which is unsubstituted or substituted by 1 to 3 groups selected from halogen, C14alkyl and C1-4alkoxy; or C5 6cycloalkyl, unsubstituted or substituted by 1 to 3 C14alkyl groups;
the R8's are identical and have one of the significances of R7, independently,
or R7 and R8 together with the N-atom to which they are attached form a saturated ring which contains one to three heteroatoms and is unsubstituted or substituted by one to three C1-4alkyl;
the Rg 's are identical and are C1.4alkyl unsubstituted or substituted by phenyl, -CH2COCH3, -CH2CONH2 or -CH2-CHOH-CH2Cl,
or R7, R8, R9 and the N-atom to which they are attached form a pyridinium group (attached by its N-atom) unsubstituted or substituted by one to three C1-4alkyl groups, or a saturated ring which contains one to three heteroatoms and is unsubstituted or substituted by one to three C1-4 alkyl;;
X, when all four groups R2 are hydrogen, is selected from X1 to X65 and from X100 to X109; in which X1 is a direct bond, X2 is a linear or branched C1 4alkylene group;
X100 -CO-NH-R43-CO-NH-R43-NH-CO-,
X101 -CO-NH-R43-NH-CO-CH2-CH2-CO-NH-R43-NH-CO-,
X102 -CO-NH-R43-NH-CO-CH=CH-CO-NH-R43-NH-CO-,
each R42 independently, is halogen, C1 4alkyl or C1-4alkoxy, each R43 independently, is a linear or branched C1-4alkylene group, each R44 independently, is hydrogen or C1-4alkyl group,
g is 1,2,3or4, each R45 independently, is halogen, -NH-CH2-CH2-OH,
-N(CH2-CH2-OH)2, -NH2, -OH, -NH-(CH2)2-3N(C2H5)2,
or X0, when at least one R2 is other than hydrogen, is selected from X1,X2,X11,X12,X14,X15,X17 to X21,X25,
X27,X32,X34,X57,X64 and X103; and
As is an anion.
For the avoidance of doubt in X0 where the bridging group is asymmetric, it can be attached to phenyl group D at either end. For the avoidance of doubt a compound of formula I can be present in a mixture which may include one or more other compounds of formula I or not of formula I.
When the compounds of formula I are in 1:1 metal complex form, preferably the metal atom is selected from copper, zinc, chromium, cobalt, nickel, iron or manganese and when the compounds of formula I are in 1:2 metal complex form, preferably the metal atom is selected from chromium, nickel, cobalt or iron.
The alkylene group as A1 may be linear or branched.
In the specification halogen means fluorine, chlorine, bromine, or iodine, preferably chlorine or bromine, particularly chlorine.
According to the invention, the molecule of a compound of formula I contains two identical pyridone coupling component residues. Depending on the significances of T and B, each pyridone residue of the molecule bears either one protonatable basic group optionally together with a quaternary ammonium group or one or two quaternary ammonium groups.
The term "protonatable basic group" includes protonatable primary, secondary and tertiary amino groups.
R1 is preferably R'1 where R'1 is methyl, ethyl, phenyl, benzyl, or cyclohexyl. More preferably R1 is R" where R"1 is methyl or phenyl, especially methyl.
R2 is preferably 9'2 where 9'2 is hydrogen, methyl, ethyl, hydroxy, methoxy, ethoxy, chlorine or bromine.
R2 is more preferably 9"2 where 9"2 is hydrogen, hydroxy, methyl, methoxy or chlorine, especially hydrogen.
T is preferably T' where T' is hydrogen, -CN, -CON(R'5)2 where R'5 is as defined below, or
where R'3 is as defined below. More preferably T is T" where rH is hydrogen, cyano, -CONH2 or
where R"3 is defined below.
Most preferably T is T"' where T"' is hydrogen
Preferably R3 is R'3 where R'3 is hydrogen, methyl, ethyl, -NH2 or -N(CH3)2. More preferably R3 is R"3 where R"3 is hydrogen or methyl.
Preferably R5 is R'5 where R'5 is hydrogen, methyl or ethyl, or when two R5 groups are present attached to a nitrogen atom, both R'5 groups together with the N-atom may form an unsubstituted pyrrolidinyl, piperidino, morpholino, piperazinyl or N-methylpiperazinyl radical. More preferably R5 is hydrogen.
B is preferably B' where B' is -A'1-NR'79'8 or A'1NR'7R'8R'g AO where the symbols are as defined below. More preferably B is B" where B" is -(-CH2-)-2N9"79"8, -(-CH2-)-3NR"7R"8, -(-CH2-)-2NR"7R"8R"9 A# or -(-CH2-)-3NR"7R"8R"9 A# where the symbols are as defined below. Most preferably B is B"' where B"' is -(CH2)2 K or -(CH2)3 K, the symbol K being selected from
A1 is preferably A'1 where A'1 is -(-CH2-)-2, -(-CH2-)-3, -(CH2-)-4,
Preferably 97 is R'7 where R'7 is linear or branched C1.6alkyl, unbranched hydroxyC2-3alkyl, benzyl, 2-chloroethyl or 2-cyanoethyl.
More preferably R7 is R"7 where R"7 is methyl or ethyl.
Preferably 98 is R'8 where R'8 has one of the significances of R'7, independently, and R9 is R'g where R'g is methyl, ethyl, propyl or benzyl.
More preferably R8 is R"8 where R"8 has one of the significances of R"7 and R9 is R''g where R"9 is methyl, ethyl or benzyl.
R'7 and R'8 together with the N-atom to which they are attached may also form a pyrrolidinyl, piperidino, morpholino, piperazinyl, N-methylpiperazinyl or N-amino-ethylpiperazinyl radical.
R'7, R'8 and R'g together with the N-atom to which they are attached may also form a pyridinium ring unsubstituted or substituted by one or two methyl groups or a radical .
A# where Z0 is a direct bond,-CH2-, -0-,
-S-, -SO2-, -SO-, -HN-, #N-R10, #N-(R10)2 A# or #N-C2H4-NH2, and each R1ol independently, is methyl or ethyl.
R"7 and R"8 together with the N-atom to which they are attached may also form a morpholino, piperidino, piperazinyl, N-methylpiperazinyl or N-aminoethylpiperazinyl radical,
Groups R"7, R"8 and R"9 together with the N-atom to which they are attached form a pyridinium, 2-or 3-picolinium, N-methyl-morpholinium, N-methyl-piperidinium, N-methyl-piperazinium or N,N'-dimethylpiperazinium ring, or a
A# ring.
X0 is preferably X'O where X'O when all four R2's are hydrogen, is selected from X1, X5, X6, X7, X10, X11, X12,
X16, X17, X22, X25, X26, X27, x30, X31, X49, X50, X51, X59, X54, X58, X59, X62, X63, X54, X101 (where R43 is -(-CH2-)-1 2), X103 (where R43 is -(-CH2-)-1-2 , and R45 is -NH(CH2)2-3-N(C2H5)2), X104 (where R44 = H and g = 2 or 3), X108 (where R43 = -(-CH2-)1-3), X70-80 and X110, where X70-90 and X110 are as defined below::
X73 -NH-CO-CH2-CO-NH-,
X74 -NH-CO-CH=CH-CO-NH x75 -NH-CO-( CH2)4 -CO-NH-,
X81 -CH2-, X82 -(CH2)2-, X83 -(CH2)3-,
X84 -(CH2)4-, X85 -CO-NH-(CH2)2-NH-CO-,
X86 -CO-NH-(CH2)3-NH-CO-, X87 -CO-NH-(CH2)4-NH-CO-,
or X'0, when at least one R2 is other than hydrogen, is X1,X11,X12,X17, X64, X70, X71, X74, X79, X80, X81, X82 X85, X86, X88 or X103 as defined above,
where R42a is hydrogen, Cl, CH3 or OCH3, and R45a is Cl, -NH(CH2)2OH, methoxy, hydroxy, -N H2, ethoxy, -N(CH2CH2OH)2, -NH(CH2)3N(C2H5)2,
More preferably X0 is X"0 when all four R2's are hydrogen, X"0 being X1,X11,X17,X27,X51,X52,X54,X64,X70 to X77,X79,X80,X81,X82,X85 to X90 to X90 or X110 especially X11,X17,X81,X82 or X85.
In the compounds of formula I, preferably each ring D or D1, independently, in addition to X0 and the azo group, bears either one further substituent, preferably a hydroxy group in the ortho position to the azo group, or no further substituent. More preferably at most one of rings D and D1 is further substituted by hydroxy. X0 is preferably attached in the 2,3 and/or 4-positions, particularly 3 and/or 4-positions on the rings
D and D1.
Preferred compounds of formula I are those, in free base or acid addition salt form and in metal-free, 1:1 or 1:2 metal complex form of formula II
where the symbols R; T', B', R2 and X0 are as defined above.
More preferred compounds of formula I are those, in free base or acid addition salt form and in metal-free, 1:1 or 1:2 metal complex form, of formula III
in which the symbols R"1, 2, T", B" and X'O are as defined above, X'O being attached in the 3-or 4-position (shown) on rings D' and D'1.
Further preferred compounds of formula I are those, in free base or acid addition salt form and in metal-free, 1:1 or 1:2 metal complex form, of formula IV
in which T"', B"' and X"O are as defined above.
Interesting compounds of formula I in 1:1 or 1:2 metal complex form and in free base or acid addition salt form are of formula V
in which each R2a, independently, is hydrogen, halogen or C1.4alkyl; Me is, when the compound of formula V is in 1:1 metal complex form, copper, chromium, manganese, cobalt or nickel and when the compound of formula V is in 1:2 metal complex form, Me is chromium, iron or cobalt, and the remaining symbols are as defined above.
Preferably Me is copper when the compound of formula I is in 1:1 metal complex form and when the compound of formula I is in 1:2 metal complex form, Me is cobalt or iron, particularly iron.
Preferred compounds of formula I in 1:1 metal complex form and in free base or acid addition salt form are of formula VI
in which R1, R2, R2a, T, B and X0 are as defined above, and Me1 is copper.
Most preferred compounds of formula I in 1:1 metal complex form are those of formula VI in which R1 is
R'1, particularly R"1, especially methyl; T is T', particularly r, especially T"'; R2 and R2a are hydrogen; B is B', preferably B", particularly B"'; and X0 is X'0, particularly X"c.
Preferred compounds of formula I in 1:2 metal complex form and in free base or acid addition salt form are of formula VII
in which R" R2, R2a, T, B and X0 are as defined above, and Me2 is chromium, cobalt or iron.
Most preferred compounds of formula I in 1:2 metal complex form are those of formula VII in which R1 is
R'1, particularly R"1, especially methyl; T is T', particularly T", especially T"'. R2 and 9211 are hydrogen; B is B', preferably B", particularly B"' and X0 is X'OT particularly X"O Further, according to the invention there is provided a process for preparing a compound of formula I comprising coupling to 1 mole of a tetrazotised compound of a diamine of formula VIII
in which R2, n and X0 are as defined above, 2 moles of a compound of formula IX
in which R1, B and Tare as defined above, and, if required, the resulting compounds of formula I may be converted into the corresponding 1::1 or 1:2 metal complex form, and/or into the corresponding acid addition salt form.
Compounds of formulae VIII and IX are known or may be made by known methods from known compounds.
Coupling to form compounds of formula I can be carried out according to known methods.
Advantageously, coupling is carried out in aqueous (acid, neutral or alkali) medium at a temperature from -10"C to room temperature, if necessary, in the presence of a coupling accelerator such as pyridine or urea.
Alternatively, coupling may be effected in a mixture of solvents, for example, water and an organic solvent.
Metallisation of the compounds of formula I can be achieved by known methods.
The disazo compounds offormula I in 1:1 metal complex form maybe prepared by metallising compounds of formula I in metal-free form with a metal selected from copper, cobalt, iron, nickel, manganese, chromium and zinc.
The disazo compounds of formula I in 1:2 metal complex form may be prepared by metallising compounds of formula I in metal-free form with a metal selected from chromium, nickel, cobalt and iron.
A further method for the preparation of a disazo compound of formula I in 1:2 metal complex form is by reacting a compound of formula I or other than formula I in metal-free form with a disazo compound 1:1 metal complex of formula I when the metal is chromium, nickel, cobalt or iron.
The metallisation process to form a 1:1 metal complex of the type of formula VI is advantageously carried out by treating 1 mole of a disazo compound with a metallising agent containing 1 equivalent of metal.
1:1 Metal complex formation using copper can be carried out by directly reacting a compound of formula I with metal salt or by oxidative coppering preferably at 40-70 C and at a pH of 4-7 in the presence of a Cu(ll) salt or with copper filings in the presence of H202 or any other oxidating material; or demethylating coppering can be applied in a pH range of 3-4 at a high temperature.
Metallisation is carried out advantageously in aqueous medium or in a mixture of water and a water-miscible organic solvent, for example acetone, lower alkyl alcohols, dimethylformamide, formamide, glycols or acetic acid at a pH range from 1.0 to 8.0, preferably pH 2 to 7. The metallisation process may be carried out at a temperature from room temperature to the boiling point of the reaction medium.
Alternatively, metallisation may be effected in a wholly organic medium (for example dimethylformamide). Advantageously, for instance, cobaltisation may be carried out in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in the ratio of 2 to 6 moles of nitrite per atom gram of cobalt.
Suitable cobalt-yielding compounds are, for example, cobalt(ll) or Co(lll) sulphate, acetate, formate or chloride.
Copper-yielding compounds are, for example cupric sulphate, cupricformate, cupric acetate and cupric chloride.
The nickel-yielding compounds are Ni(ll) or Ni(lll) compounds, such as nickel formate, nickel acetate and nickel sulphate.
Preferred manganese-yielding compounds are Mn(ll) compounds and iron-yielding compounds are Fe(ll) or Fe(lil) compounds. Examples of these and zinc-yielding compounds are manganese, iron and zinc formate, acetate and sulphate.
Preferred chromium-yielding compounds are Cr(ll) and Cr(lll) formate, acetate and sulphate.
In the compounds of formula I the anions As can be any non-chromophoric anions such as those conventional in basic dyestuff chemistry. Suitable anions include chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleate, acetate, propionate, lactate, succinate, tartrate, malate, methane sulphonate and benzoate as well as complex anions, for example zinc chloride double salts and anions of boric acid, citric acid, glycollic acid, diglycollic acid and adipic acid or addition products of ortho boric acids with polyalcohols with at least one cis diol group present. These anions can be exchanged for each other by iron exchange resins on reaction with acids or salts (for example via the hydroxide or bicarbonate) or according to German Offenlegungsschrift 2,001,748 or 2,001,816.
The compounds of formula I are suitable for dyeing, padding or printing fibres, threads or textile materials, particularly natural or regenerated cellulose materials for example cotton, polyester or synthetic polyamides modified by anionic groups. Such a polyamide is described in Belgian Patent 3,379,723.
The compounds of formula I are also used for dyeing, padding or printing fibres, threads or textiles produced therefrom which consist of or contain homo- or mixed polymers of acrylonitrile or of 1,1-dicyanoethylene.
The textile material is dyed, printed or pad-dyed in accordance with known methods. Acid modifiedpolyamide is dyed particularly advantageously in an aqueous, neutral or acid medium, at temperatures of 60"C to boiling point or at temperatures above 1 000C under pressure.
The textile material may also be dyed by the compounds of formula I in organic solvents, e.g. in accordance with the directions given in German Offenlegungsschrift 2,437,549.
Cellulose material is mainly dyed by the exhaust process, i.e. from a long or short bath, at room temperature to boiling temperature, optionally under pressure, whereby the ratio of the bath is from 1:1 to 1:100 and preferably from 1:20 to 1:50. If dyeing is effected from a short bath, then the liquor ratio is 1:5 to 1:15. The pH of the dye-bath varies between 3 and 10 (for short and long dyebaths).
Printing may be effected in accordance with known methods.
The dyestuffs of formula I are particularly suitable for dyeing or printing paper, e.g. for the production of bulk-dyed, sized and unsized paper. The dyestuffs may similarly be used for dyeing paper by the dipping process. The dyeing of paper is effected by known methods. The compounds of formula I are especially suitable for dyeing ligneous paper, particularly paper with mechanical wood pulp.
The azo compounds of formula I may also be applied to bast fibres such as hemp, flax, sisal, jute, coir or straw.
The dyestuffs of formula I are also suitable for dyeing or printing leather by known methods and dyeings with good fastness properties are obtained.
Dyeings prepared with dyestuffs of formula I on paper produce a substantially clear waste liquor which is important for environmental reasons. The dyestuffs of formula I have good build-up properties, do not bleed once applied to paper and are not pH sensitive. They have a high affinity for paper and do not mottle on ligneous paper. Dyeings produced with dyestuffs of formula I have good light fastness and the nuance on exposure for a long time to light fades tone in tone. The dyestuffs of formula I have good wetfastness properties not only for water but also for milk, soap, water, sodium chloride solution, fruit juice and sweetened mineral water. Further dyeings made with dyestuffs of formula I are fast for alcoholic beverages due to a good alcohol fastness. Further, the dyestuffs of formula I have good nuance stability.
The compounds of formula I are advantageously used in their acid addition salt form, e.g. a salt produced by addition of a carboxylic acid such as acetic acid, lactic acid, formic acid, methoxy or ethoxy acetic acid or glycollic acid, or quaternary ammonium salt form.
For their use the azo compounds of formula I are suitably worked up into stable solid or liquid preparations, according to known methods, advantageously by grinding or granulating or by dissolving in suitable solvents, optionally adding an assistant, e.g. a stabiliser, a solubilising or a diluting agent such as urea. Such preparations may be obtained, for example, as described in French Patent Specifications 1,572,030 and 1,581,900 or in accordance with German DOS 2,001,748 and 2,001,816.
Liquid dyeing compositions are preferably as follows: 1 part by weight of a compound of formula I (in acid addition salt form or quaternary ammonium
salt form); 0.01-1 part by weight of an inorganic salt (preferably 0.1 to 0.1 parts); 0.01-1 part by weight of an organic acid such as formic, acetic lactic, citric, propionic or methoxy acetic
acid; 1-8 part by weight of water; and 0-5 parts by weight of a solubilising agent such as a glycol (diethylene glycol, triethylene glycol or
hexylene glycol), a glycol ether such as methyl cellosolve methylcarbitol, butylpolyglycol, urea,
formamide and dimethylformamide.
Solid dyeing preparations are as follows: 1 part by weight of a compound of formula I (in acid addition salt form or quaternary ammonium
salt form) 0.01-1 part by weight of an inorganic salt (preferably 0.01 to 0.1 parts) 0 - 8 parts by weight of a diluting agent such as urea, dextrin, glucose or d-glucose).
The solid compositions may usually contain up to 10% water.
The invention will now be illustrated by the following Examples in which all parts are by weight and all temperatures are in degrees Celsius.
Example 1
19.8 Parts (0.1 M) of 4,4'-diaminodiphenylmethane are tetrazotised according to known methods with 13.8 parts (0.2 M) of sodium nitrite at 0-5 in 200 parts of water and 60 parts of 30% hydrochloric acid. 64.4 Parts (0.2 M) of a compound of formula
dissolved in 250 parts of water are added over 30 minutes to the ice cold tetrazotised solution. By the addition of a 30% NaOH solution the pH is brought to 4.5. The resulting dyestuff is of formula 1 b
and is in solution.
By concentration under vacuum or by precipitation in acetone/alcohol the dyestuff is isolated.
The reaction mixture however can be used directly for dyeing without isolating the product.
The dyestuff of formula 1 b has a high solubility in water and gives yellow dyeings with good fastness properties.
Examples 2 to 64
Compounds of the formula
in which the symbols are defined in Table I below and the asterisked atom is attached to phenyl ring D, can be formed by an analogous method to that of Example 1 from appropriate reactants.
In Table I, T has the following significances: T1isH T2 is -CO NH2 T3is-CN
B has the following significances:
B1 is -(CH2)2N(CH3)2
B2 is -(CH2)3N(CH3)2
B3 is -(CH2)2N(CH3)3A# B4 is -(CH2)3N(CH3)3A# B5 is -(CH2)3N(C2H5)2 A# is -Cl#; 1/2 (-SO4#); CH3COO# or CH3CHOHCOO# position of X0 on ring D
Ex. T B X0
and ring D1
2 T4 B1 4CH2 (4,4') 3 T4 84 do. do.
4 T5 81 do. do.
5 T5 B2 do. do.
6 15 83 do. do.
7 15 B4 do. do.
8 16 B4 do. do.
9 T7 B4 do. do.
10 Tg B4 do. do.
11 T4 B2 04 64.4 12 T4 B2 -S- do.
13 T4 82 -NH- do.
14 T4 B2 -O- do.
15 T4 B2 -S02- do.
16 T4 B2 -NHCONH- do.
17 T4 B1 -NHCONH 18 T4 B2 -CONH- (4,49 19 T5 B2 -CONH- (4,4')
Ex. T B XO position of X0 on ring D and D1 20 T4 84 do. do. 21 15 B4 do. do. 22 T4 B2 do. (4,3') 23 T5 B4 do. do. 24 T4 84 do. (4,3') 25 15 82 do. (3,3') 26 T4 B1 -NH7/INH (4,4') Cl 27 T5 B4 do. do. 28 T4 82 do. do. 29 T4 B1 do. (3,3') 30 Tg 82 do. (4,4') NH(CH2)3N(C2H5)2 t4N 31 T3 B2 NHNNH (4,4') N N-CH2CH2NH2 (3,3') 32 13 / t 82 - -NH 33 T4 82 --CH2CH2 (4,4') 34 T4 82 -CONHCH2CH2NHCO- (4,4') 35 T4 82 -CONHCH2CHOHCH2NHCO- (4,4') 36 T4 B2 -*SO2NH- (4,3') 37 T4 B2 -NHCONH- (3,3') 38 T4 B4 -O-CH2-O- (4,4') 39 T4 B2 -NH- do. 40 T4 82 -S-S- do. 41 T1 B2 -CH2- do. 42 T3 82 do. do. 43 T1 Bg do. do. 44 13 Bg do. do.
Ex. T B X0 position of XO on ring D and Dl 45 T1 82 -CH2CH2 - do. 46 13 B1 do. do, 47 T1 B5 do. do. 48 T3 Bg do. do. 49 T1 B2 -C*ONH- do. 50 T3 Bg do. do. 51 T1 B2 -C*ONH- (4,3') 52 T1 82 -CONHCH2CH2NHCO- (4,4') 53 T3 82 -CONHCH2CH2NHCO- ( 4,4 54 T1 B5 do. do. 55 T3 Bg do. do. 56 T1 82 -S- do. 57 T3 82 do. do. 58 T4 82 do. (2,4 59 T1 82 do. do. 60 T3 82 -S- (2,4') 61 T4 Bg $)O2 (4,4') 02 62 T1 Bg -CONH- (4,3') 63 13 82 do. do. 64 T3 85 do. do.
The compounds of Examples 2 to 38, to 48 and 51 to 64 give yellow dyeings. The compound of Example 39 gives a blue shade and the compounds of Examples 49 and 50 give orange dyeings.
Examples 65 to 73
Compounds of the formula
in which the symbols T, X0 and R are defined in Table II below, can be produced in accordance with the procedure described in Example 1.
TABLE II
Ex. T R position X0 position of XO ofR + on rlng D and D, 65 T1 OH 2 -S O2NH- 3,4'
66 T3 do. do. do. do.
67 T4 do. do. do. do.
68 T5 do. do. de do.
69 T1 do. do. -S O2NH- 4,4'
70 T4 do. do. do. do.
71 Ti -NO2 3 -S- do.
72 T4 do. do. do. do.
73 T4 -COOH 3 do. do.
The compounds of Examples 71 and 72 give yellow dyeings, the compounds of Examples 65 to 70 give a brown shade and the compound of Example 73 gives orange dyeings.
* The asterisked S atom is attached to phenyl ring D.
Example 74
16.5 Parts of the compound of Example 67 are introduced in 200 parts of water with stirring and the mixture is heated to 60". After addition of 5.2 parts copper sulphate pentahydrate and 4 parts sodium acetate, the resulting mixture is heated to 80 and kept at this temperature for 7 hours. The resulting red solution is cooled to room temperature and, after addition of a solution of 45 parts sodium carbonate dissolved in 200 parts water, the precipitated reaction product is filtered and dried. The following dyestuff
is obtained in powdered form. It dyes paper in a yellow-brown shade and the resulting dyeings have good light and wet-fastness properties.
Example 75
By following the procedure of Example 74 but using the disazo compound of Example 70, the corresponding 1:1 copper complex is obtained.
Example 76
16.5 Parts of the compound of Example 70 are introduced in 200 parts water with stirring and the mixture is heated to 60 . After addition of 5 parts potassium çhromium (III) sulphate, 12H2O and 7 parts sodium acetate (cryst.), the mixture is heated to 93-95 . The chromation is complete after 4 to 5 hours reaction at this temperature. The resulting mixture is cooled ta room temperature after which 50 parts sodium carbonate dissolved in 250 parts water are added to the mixture. The precipitated reaction product is then filtered and dried. The dyestuff of formula
is obtained as a powder. When used in the form of an acid addition salt, it dyes paper in a red-brown shade and the resulting dyeings have good light and wet fastness properties.The resulting waste water of the dyeings is practically colourless.
Examples 77 to 81
By repeating the procedure of Example 76, but using the appropriate compounds, the following metal complexes are obtained.
TABLE III
Ex. Metal complex Cordinates
77 1:2 Cr Compound of Example 67
78 1:2 Co Compound of Example 67
79 1:2 Fe Compound of Example 67
80 1:2 Co Compound of Example 70
81 1:2 Fe Compound of Example 70
The compounds of Examples 77 to 81 dye paper in a brown shade.
Application Example A
70 Parts of chemically bleached sulphite cellulose obtained from pinewood and 30 parts of chemically bleached sulphite cellulose obtained from birchwood are ground in 2000 parts of water in a Hollander. 0.2
Parts of the dyestuff of Example 1 used in acid addition salt form are added into this pulp. Paper is produced from this pulp after mixing for 20 minutes. The absorbent paper which is obtained in this manner is dyed in a yellow tone and the waste water is practically colourless.
Application Example B
0.5 Parts of the dyestuff of Example 1 used in acid addition salt form) are added to 100 parts of chemically bleached sulphite cellulose which have been ground in a Hollanderwith 2000 parts of water. Sizing takes place after a thorough mixing for 15 minutes. The paper which is produced from this material has a yellow tone and has good wet fastness properties.
Application Example C
An absorbent web of unsized paper is drawn at a temperature of 40 to 50 through a dye solution having the following composition:
0.5 parts of dyestuff of Example 1 (in acid addition salt form)
0.5 parts of starch
99.0 parts of water.
The excess dye solution is squeezed out through two rollers. The dried web of paper is dyed in a yellow tone and has good fastness properties.
Any one of the dyes of Examples 2 to 81 may be used either in their water soluble salt form or in the form of dye preparation, e.g. granulates in any one of Application Examples A to C.
Application Example D
100 Parts of freshly tanned and neutralized chrome leather are agitated for 30 minutes in a vessel with a dyebath of 250 parts of water and 1 part of the dyestuff of Example 1 (in acid addition salt form) at 55"C and are then treated in the same bath for 30 minutes with 2 parts of an anionic fatty liquor based on sulphonated train oil. The leather is then dried and prepared in the normal way, giving a leather evenly dyed in a yellow tone.
Other low affinity vegetable retanned leathers can be similarly dyed by known methods.
Application Example E
2 Parts of the dyestuff of Example 1 (in acid addition salt form) are dissolved in 4000 parts of demineralised water at 40"C. 100 Parts of a prewetted cotton textile substrate are added and the bath is raised to boiling point over 30 minutes and held at the boil for 1 hour, topping up with water where necessary. After removing the dyed fabric from the bath, washing and drying, a yellow dyeing is obtained with good light fastness and wet fastness properties. The dyestuff exhausts practically totally and the waste water is practically colourless.
Any one of the dyestuffs of Examples 2 to 81 may be used in place of that of Example 1 in any one of
Application Examples D and E.
Application Example F
15 kg waste paper, 25 kg bleached mechanical pulp and 10 kg unbleached sulphate cellulose are defibrated in a pulper into a 3% aqueous pulp slurry. This stock suspension is diluted to 2% in a dyeing chest. To this diluted suspension there are added at first 5% by weight china clay and then 1,25 kg of a 5% acetic adid solution of the dyestuff of Example 1, the % being based on the dry weight of fibres. After 20 minutes, a 1% resin size dispersion (based on the weight of absolutely dry fibres) is added to the resulting pulp in the mixing chest. The homogeneous pulp slurry is then adjusted to pH 5 by addition of alum shortly before introduction into the paper machine.
A yellow 80 g/cm2 heavy bag paper is produced on the paper machine. The resulting dyed paper exhibits very good fastness properties to bleeding according to DIN 53 991 and good light fastness properties.
The resulting paper can almost completely be decolourized by hypochlorite.
Example G
Water is added to a dry pulp in a hollander consisting of 60% by weight of mechanical wood pulp and 40% by weight of unbleached sulphite cellulose and the slurry is beaten in order to obtain a dry content slightly exceeding 2.5% and having a beating degree of 40 SR. The slurry is then exactly adjusted to a high density dry content of 2.5%.
5 Parts of a 0.25% aqueous solution of the dyestuff of Example 1 are added to 200 parts of the above resulting slurry. The mixture is stirred for about 5 minutes and, after addition of 2% by weight resin size and then 4% by weight alum (based on the dry weight) is further stirred for a few minutes until homogeneous.
The resulting pulp is diluted with about 500 parts water to a volume of 700 parts and then used for the production of sheets by succion on a sheet former. The resulting paper sheets are dyed in an intense yellow shade. The residual dyestuff concentration in the waste water from the sheet former has been measured photometrically (A max. = 448 nm) and is substantially low.
Any one of the dyestuffs of Examples 2 to 81 may be used in place of that of Example 1 in any one of
Application Examples F and G. The waste water exhibits a substantially low residual dyestuff concentration.
Claims (18)
1. A compound in free base or acid addition salt form, in metal-free, 1:1 or 1:2 metal complex form, of formula I
in which the R1's are identical and are hydrogen, C1.4alkyl, C56cycloalkyl, phenyl, benzyl or phenyl-ethyl;
each n, independently, is 0, 1 or 2;
each R2, independently, is hydrogen, halogen, hydroxy, nitro, -COOH, C1-4alkyl or C1-4alkoxy;
the T's are identical and are hydrogen; -CN; -COOR4; -CON(R5)2;-SO2N(R5)2;
the Xa's are identical and are -0-, -S- orN-R5; each R3, independently, is hydrogen, C1-4alkyl, -N(R5)2 or -CON(R5)2;
the R4's are identical and are C1-6alkyl or phenyl-C1-3alkyl;
each 9, independently, is hydrogen or C1 4alkyl; or when two R5's are present attached to a nitrogen atom, both R5's together with the N-atom to which they are attached may form a saturated ring which contains one to three heteroatoms and is unsubstituted or substituted by one to three C1 4alkyl; the R6's are identical and are Ci4alkyl; the B's are identical and are -A1-NR7R8; or -A1-NR7R8R9 A9; the A1'S are identical and are C28alkylene; the R7'S are identical and are C1 6alkyl, C2-8alkyl monosubstituted by halogen,-OH or -CN, phenyl(C1-3)- alkyl, the phenyl ring of which is unsubstituted or substituted by 1 to 3 groups selected from halogen,
C1-4alkyl and C1-4alkoxy; or C5-6cycloalkyl, unsubstituted or substituted by 1 to 3 C1-4alkyl groups;
the R8's are identical and have one of the significances of R7, independently,
or R7 and Ro together with the N-atom to which they are attached form a saturated ring which contains one ::o three heteroatoms and is unsubstituted or substituted by one to three C1-4alkyl;
the R9's are identical and are C1-4alkyl unsubstituted or substituted by phenyl, -CH2COCH3, -CH2CONH2 or -CH2-CHOH-CH2Cl, or R7, R8, R9 and the N-atom to which they are attached form a pyridinium group (attached by its N-atom) Jnsubstituted or substituted by one to three C1-4alkyl groups, or a saturated ring which contains one to three @eteroatoms and is unsubstituted or substituted by one to three C1-4alkyl;
X, when all four groups R2 are hydrogen, is selected from X1 to X65 and from X100 to X109;
in which X1 is a direct bond, X2 is a linear or branched C1.4alkylene group;;
X41 -CH2-S-CH2-, X42 -SO-,
X43 -CH2-SO-CH2-,
X44 -CH2-SO2-CH2-, X45 -CH2-NH-CO-NH-CH2-,
X46 -CH2-NH-CS-NH-CH2-,
X100 -CO-NH-R43-CO-NH-R43-NH-CO-,
X101 -CO-NH-R43-NH-CO-CH2-CH2-CO-NH-R43-NH-CO-,
X102 -CO-NH-R43-NH-CO-CH=CH-CO-NH-R43-NH-CO-,
X104 -SO2-NR44-(CH2)g-NR44-SO2-,
X105 -CO-NR44-R43-O-CO-,
X108 -CONH-R43-NH-CO-NH-R43-NH-CO-,
each R42 independently, is halogen, C1.4alkyl or C1-4alkoxy, each R43 independently, is a linear or branched C1-4alkylene group, each R44 independently, is hydrogen or C1-4alkyl group, gis1,2,3Or4, each R45 independently, is halogen, -NH-CH2-CH2-OH, -N(CH2-CH2-OH)2, -NH2, -OH, -NH-(CH2)23
N(C2H5)2,
or X0, when at least one R2 is other than hydrogen, is selected from X1, X2, X11, X12, X14, X15, X17 to X21, X25,
X27, X32. X34, X57, X64 and X103; and A# is an anion.
2. A compound according to Claim 1, in which X0 is X'O where X'O when ail four R2's are hydrogen, is selected from
X1, X5, X6, X7, X10,X11, X12, X16, X17, X22 X25, 26, X27, X30, X31, X49, X5Q. X51, X53, X54, X58, X59, X62, X53, X64,
X101 (where R43 is -(-CH2-)-1-2), X103 (where R43 is -(-CH2-)-1-2 and R45 is -NH(CH2)2-3-N(C2H5)2), X104 (where R44 = H and g = 2 or 3), X108 (where R43 = -(-CH2-)1-3), as defined in Claim 1, X70-90 and X110, where
X70-90 and Xiio are as defined below::
X73 -NH-CO-CH2-CO-NH-,
X74 -NH-CO-CH=CH-CO-NH- ,
X75 -NH-CO-(C2H)4 -CO-NH-,
X81 -CH2-, X82 -(CH2)2- , X83 -(CH2)3
X84 -(CH2)4-, X85 -CO-NH-(CH2)2-NH-CO-,
X86 -CO-NH-(CH2)3-NH-CO-, X87 -CO-NH-(CH2)4-NH-CO-,
or X'0, when at least one R2 is other than hydrogen, is X1,X11,X12,X17,X64,X70,X71,X74,X79,X80,X81,X82, X85, X86, X88 or X103 as defined above,
where R42a is hydrogen, Cl, CH3 or OCH3, and
R45a is Cl, -NH(CH2)2OH, methoxy, hydroxy, -NH2, ethoxy, -N(CH2CH2OH)2, -NH(CH2)3N(C2H5)2,
3.A compound according to Claim 1 or Claim 2 in which X0 is X"0 when all four 92'S are hydrogen, X"O being selected from X1
X11, X17, X27, X51, X52, X54, X64, X70, to X77, X79, X80, X81t X82t X85 to X90 or X110 especially X11, X,7, X81, X82 and Xse.
4. A compound according to Claim 1, of formula II
where the R'1's are identical and are methyl, ethyl, phenyl, benzyl orcyclohexyl; each R'2, independently, is hydrogen, methyl, ethyl, hydroxy, methoxy, ethoxy, chlorine or bromine; the T's are identical and are hydrogen, -CN, -CON(R'5)2 or
where each 9', independently, is hydrogen, methyl or ethyl, or when two R'5 are present attached to a nitrogen atom, both R'5 together with the N-atom may form an unsubstituted pyrrolidinyl, piperidino, morpholino, piperazinyl or N-methylpiperazinyl radical, and each R'3, independently, is hydrogen, methyl, ethyl, -NH2 or -N(CH3)2; ;
the B"s are identical and are -A'1-NR'7R'8 or -A'1-NR'7R'8R'9 As
where A'1 is -(CH2-)-2, -(-CH2-)-3, -(-CH2-)4-,
the 9','s are identical and are linear or branched C1-6alkyl, linear hydroxy C23alkyl, benzyl, 2-chloroethyl or 2-cyanoethyl, the 9's's have one of the significances of R', independently, and the Rg's are identical and are methyl, ethyl, propyl or benzyl, or R'7 and R'8 together with the N-atom to which they are attached may form a pyrrolidinyl, piperidino, morpholino, piperazinyl, N-methyl- or N-aminoethyl-piperazinyl, or R'7, R'8 and R'g together with the N-atom to which they are attached may also form a pyridinium ring unsubstltuted or substituted by one or two methyl groups or a radical ss
where Z0 is a direct bond,-CH2-, -O-, -S-, -SO2-, -SO-, -NH-, #N-R10, #N-(R10)2 A# or #N-C2H4-NH2, and where Z0 is a direct bond, -CH2-, -O-, -S-, -SO2-, -SO-, -NH-, N-Rio, N -(R10)2A# or N-C2H4-NH2, and each Rio, independently, is methyl or ethyl; and AO is an anion, and X0 is defined as in Claim 1.
5. A compound according to any one of Claims 1,2 and 4, of formula Ill
where the R"1's are identical and are methyl or phenyl,
each R"2, independently, is hydrogen, hydroxy, methyl, methoxy or chlorine,
the T"1's are identical and are hydrogen, -CN, -CONH2 or
where 93 is hydrogen or methyl and A# is an anion, the B"'s are identical and are -(-CH2-)-2NR"7R"8, -(-CH2-)3-NR"7R"8, -(CH2-)2-NR"7R"8R"9 A# or -(CH2-)3-N R"7R"8R"9 A# where the R"7's are identical and are methyl or ethyl, the R"8's are identical and have one of the significances of R"7 and the R"g's are identical and are methyl, ethyl or benzyl, or R"7 and 9% together with the N-atom to which they are attached may also form a morpholino, piperidino, piperazinyl, N-methylpiperazinyl or N-aminoethylpiperazinyl radical, or groups R"7, 9% and R"9 together with the N-atom to which they are attached form a pyridinium, 2- or 3-picolinium, N-methyl-morpholinium, N-methyl-piperidinium, N-methyl-piperazinium or N,N'-dimethylpiperazinium ring, or a
A# ring,
and
X'0 is ad defined in Claim 2 and attached in the 3-or 4-position on rings D' and D'1.
6. A compound according to any one of the preceding claims, of formula IV
where @X"0 is as defined in Claim 3; the T""s are identical and are hydrogen,
sphere AO is an anion; and
the B""s are identical and are -(-CH2-)-2K or -(CH2-)3-K where K is
7. A compound according to any one of the preceding claims of formula
8. A compound according to Claim 1, of formula V
where R1, T, B and X0 are as defined in Claim 1; each R2a, independently, is hydrogen, halogen orC14alkyl; Me is, when the compound of formula V is in 1:1 metal complex form, copper, chromium, manganese, cobalt or nickel and when the compound of formula V is in 1:2 metal complex form, Me is chromium, iron or cobalt.
9. A compound according to Claim 1, of formula VI
where R1, R2, T, B and X0@ are as defined in Claim 1, R2a is as defined in Claim 8, and
Me1 is copper.
10. A compound according to Claim 1, if formula VII
where R1, R2, T, B and X0 are as defined in Claim 1, 92a is as defined in Claim 8, and
Me2 is chromium, cobalt or iron.
11. Acompound of accordipg to Claim 10, of formula
12. A process for preparing a compound of formula I comprising coupling to 1 mole of a tetrazotised compound of a diamine of formula VIII
in which R2, n and X0 are as defined in Claim 1,2 moles of a compound of formula IX
in which R1, B and Tare as defined above, and, if required, the resulting compounds of formula I may be converted into the corresponding 1:1 or 1:2 metal complex form, and/or into the corresponding acid addition salt form.
13. A process for dyeing or printing a substrate, comprising applying to that substrate a compound of formula las defined in Claim 1.
14. A process according to Claim 13, in which the substrate is ligneous paper or mechanical wood pulp.
15. A substrate whenever dyed or printed with a compound of formula I as defined in Claim 1.
16. A compound according to Claim 1 substantially as herein described with reference to any one of
Examples 1 to 81.
17. A process according to Claim 13 or Claim 14, substantially as herein described with reference to any one of Application Examples A two G.
18. A substrate according to Claim 15 substantially as herein described with reference to any one of
Application Examples Ato G.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3511733 | 1985-03-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8607702D0 GB8607702D0 (en) | 1986-04-30 |
| GB2173210A true GB2173210A (en) | 1986-10-08 |
| GB2173210B GB2173210B (en) | 1989-08-16 |
Family
ID=6266888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8607702A Expired GB2173210B (en) | 1985-03-30 | 1986-03-27 | Basic disazo pyridone dyes |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH0662869B2 (en) |
| CH (1) | CH667464A5 (en) |
| FR (1) | FR2579606B1 (en) |
| GB (1) | GB2173210B (en) |
| IT (1) | IT1203759B (en) |
| SE (1) | SE468392B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0325973A2 (en) * | 1988-01-23 | 1989-08-02 | BASF Aktiengesellschaft | Recording liquid for ink-jet printing |
| EP0341214A2 (en) * | 1988-05-06 | 1989-11-08 | Sandoz Ag | Basic 6-hydroxypyrid-2-one compounds |
| US5001226A (en) * | 1986-05-14 | 1991-03-19 | Sandoz Ltd. | Metal-free disazo and polyazo compounds having at least one 6-hydroxypyrid-2-one coupling component radical linked to a 1-amino- or hydroxy-3-amino- or hydroxybenzene coupling component radical and metal complexes thereof |
| US5077396A (en) * | 1988-10-05 | 1991-12-31 | Sandoz Ltd. | Azo compounds containing two 6-hydroxypyrid-2-one coupling component radicals the nitrogen atoms of which are linked by a biscationic radical |
| US5424404A (en) * | 1990-10-26 | 1995-06-13 | Basf Aktiengesellschaft | Biscationic azo dyes and intermediates therefor |
| FR2715159A1 (en) * | 1994-01-14 | 1995-07-21 | Sandoz Sa | Novel tetrakisazo compounds, their preparation and their use as dyes. |
| GB2289053A (en) * | 1994-05-06 | 1995-11-08 | Sandoz Ltd | Fibre-reactive disazo dyes |
| FR2736921A1 (en) * | 1995-07-21 | 1997-01-24 | Clariant Finance Bvi Ltd | NOVEL BASIC AZO COMPOUNDS, THEIR PREPARATION AND THEIR USE AS COLORANTS |
| GB2372750A (en) * | 2001-01-18 | 2002-09-04 | Avecia Ltd | Water soluble hexa co-ordinated metal complexes of monoazo dyes for use in inks suitable for ink jet printing |
| FR2864781A1 (en) * | 2004-01-07 | 2005-07-08 | Oreal | A hair dye composition giving a range of darker shades, especially of grey and black comprises a specified azopyridiniopyridone and other synthetic colorants |
| WO2008012322A1 (en) * | 2006-07-28 | 2008-01-31 | Clariant International Ltd | Basic bisazo compounds |
| EP2078737A1 (en) | 2008-01-11 | 2009-07-15 | Clariant International Ltd. | Basic monoazo compounds |
| EP2085429A1 (en) | 2008-01-25 | 2009-08-05 | Clariant International Ltd. | Basic bisazo compounds |
| EP2085428A1 (en) | 2008-01-24 | 2009-08-05 | Clariant International Ltd. | Basic bisazo compounds |
| EP2098573A2 (en) | 2008-01-17 | 2009-09-09 | Clariant International Ltd. | Basic monoazo compounds |
| EP2103656A2 (en) | 2008-01-24 | 2009-09-23 | Clariant International Ltd. | Basic monoazo compounds |
| WO2010000779A1 (en) * | 2008-07-02 | 2010-01-07 | Clariant International Ltd | Use of acid dyes |
| WO2010130382A1 (en) * | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Bisazo compounds |
| WO2010130384A1 (en) * | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Bisazo compounds |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992001840A1 (en) * | 1990-07-24 | 1992-02-06 | Sunearth Co., Ltd. | Apparatus for injecting soil conditioning fluid |
| JP5652823B2 (en) * | 2011-01-25 | 2015-01-14 | 株式会社日本触媒 | Azo compounds |
| CN111971347B (en) * | 2018-03-27 | 2023-03-24 | 保土谷化学工业株式会社 | Complex salt compound, dye composition, coloring agent for anodized aluminum, coloring method, and method for producing complex salt compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1296857A (en) * | 1968-11-12 | 1972-11-22 | ||
| GB2104090A (en) * | 1981-06-26 | 1983-03-02 | Ciba Geigy Ag | Triazine compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2627680C2 (en) | 1975-06-30 | 1986-02-06 | Sandoz-Patent-GmbH, 7850 Lörrach | Organic compounds, their manufacture and use |
| CH627201A5 (en) * | 1977-03-14 | 1981-12-31 | Sandoz Ag | |
| CH647797A5 (en) * | 1980-05-08 | 1985-02-15 | Sandoz Ag | Organic dyes and preparation and use thereof |
-
1986
- 1986-03-24 CH CH1164/86A patent/CH667464A5/en not_active IP Right Cessation
- 1986-03-26 SE SE8601401A patent/SE468392B/en not_active IP Right Cessation
- 1986-03-27 GB GB8607702A patent/GB2173210B/en not_active Expired
- 1986-03-27 FR FR8604666A patent/FR2579606B1/en not_active Expired
- 1986-03-28 JP JP61068859A patent/JPH0662869B2/en not_active Expired - Lifetime
- 1986-03-28 IT IT47835/86A patent/IT1203759B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1296857A (en) * | 1968-11-12 | 1972-11-22 | ||
| GB2104090A (en) * | 1981-06-26 | 1983-03-02 | Ciba Geigy Ag | Triazine compounds |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001226A (en) * | 1986-05-14 | 1991-03-19 | Sandoz Ltd. | Metal-free disazo and polyazo compounds having at least one 6-hydroxypyrid-2-one coupling component radical linked to a 1-amino- or hydroxy-3-amino- or hydroxybenzene coupling component radical and metal complexes thereof |
| EP0325973A2 (en) * | 1988-01-23 | 1989-08-02 | BASF Aktiengesellschaft | Recording liquid for ink-jet printing |
| EP0325973A3 (en) * | 1988-01-23 | 1991-09-11 | BASF Aktiengesellschaft | Recording liquid for ink-jet printing |
| EP0341214A2 (en) * | 1988-05-06 | 1989-11-08 | Sandoz Ag | Basic 6-hydroxypyrid-2-one compounds |
| EP0341214A3 (en) * | 1988-05-06 | 1991-10-02 | Sandoz Ag | Basic 6-hydroxypyrid-2-one compounds |
| US5059683A (en) * | 1988-05-06 | 1991-10-22 | Sandoz Ltd. | Dyes containing 6-hydroxypyrid-2-one groups the 1-positions of which contain substituted 1,3,5-triazinyl or pyrimidyl-piperazino or -piperazinium groups linked through bridging radicals and intermediates therefor |
| US5077396A (en) * | 1988-10-05 | 1991-12-31 | Sandoz Ltd. | Azo compounds containing two 6-hydroxypyrid-2-one coupling component radicals the nitrogen atoms of which are linked by a biscationic radical |
| US5424404A (en) * | 1990-10-26 | 1995-06-13 | Basf Aktiengesellschaft | Biscationic azo dyes and intermediates therefor |
| FR2715159A1 (en) * | 1994-01-14 | 1995-07-21 | Sandoz Sa | Novel tetrakisazo compounds, their preparation and their use as dyes. |
| GB2289053A (en) * | 1994-05-06 | 1995-11-08 | Sandoz Ltd | Fibre-reactive disazo dyes |
| US5698681A (en) * | 1994-05-06 | 1997-12-16 | Clariant Finance (Bvi) Limited | Reactive disazo dyestuff compounds containing halo-substituted triazinyl rings |
| GB2289053B (en) * | 1994-05-06 | 1998-03-18 | Sandoz Ltd | Fibre -reactive disazo dyes |
| FR2736921A1 (en) * | 1995-07-21 | 1997-01-24 | Clariant Finance Bvi Ltd | NOVEL BASIC AZO COMPOUNDS, THEIR PREPARATION AND THEIR USE AS COLORANTS |
| GB2303634A (en) * | 1995-07-21 | 1997-02-26 | Clariant Finance Bvi Ltd | Basic azo compounds, their production and use |
| GB2303634B (en) * | 1995-07-21 | 1997-12-10 | Clariant Finance Bvi Ltd | Basic azo compounds,their production and use |
| ES2142704A1 (en) * | 1995-07-21 | 2000-04-16 | Clariant Finance Bvi Ltd | Basic azo compounds, their production and use |
| GB2372750A (en) * | 2001-01-18 | 2002-09-04 | Avecia Ltd | Water soluble hexa co-ordinated metal complexes of monoazo dyes for use in inks suitable for ink jet printing |
| GB2372750B (en) * | 2001-01-18 | 2004-09-08 | Avecia Ltd | Hexa co-ordinated metal complexes of monoazo dyes for use in inks suitable for ink jet printing |
| FR2864781A1 (en) * | 2004-01-07 | 2005-07-08 | Oreal | A hair dye composition giving a range of darker shades, especially of grey and black comprises a specified azopyridiniopyridone and other synthetic colorants |
| US7217299B2 (en) | 2004-01-07 | 2007-05-15 | L'oreal S.A. | Dye composition comprising at least one direct dye of the azo-pyridinio-pyridone family and at least one different synthetic dye, and process |
| EP1563828A1 (en) * | 2004-01-07 | 2005-08-17 | L'oreal | Colouring composition comprising at least one direct colouring agent from the azo-pyridinio-pyridone family and at least one additional synthesized colouring agent, dyeing process of keratinuous fibers |
| CN101495578B (en) * | 2006-07-28 | 2013-06-12 | 克莱里安特财务(Bvi)有限公司 | Basic bisazo compounds |
| WO2008012322A1 (en) * | 2006-07-28 | 2008-01-31 | Clariant International Ltd | Basic bisazo compounds |
| US8921564B2 (en) | 2006-07-28 | 2014-12-30 | Clariant Finance (Bvi) Ltd. | Basic bisazo compounds |
| EP2078737A1 (en) | 2008-01-11 | 2009-07-15 | Clariant International Ltd. | Basic monoazo compounds |
| EP2098573A2 (en) | 2008-01-17 | 2009-09-09 | Clariant International Ltd. | Basic monoazo compounds |
| EP2085428A1 (en) | 2008-01-24 | 2009-08-05 | Clariant International Ltd. | Basic bisazo compounds |
| EP2103656A2 (en) | 2008-01-24 | 2009-09-23 | Clariant International Ltd. | Basic monoazo compounds |
| EP2085429A1 (en) | 2008-01-25 | 2009-08-05 | Clariant International Ltd. | Basic bisazo compounds |
| WO2010000779A1 (en) * | 2008-07-02 | 2010-01-07 | Clariant International Ltd | Use of acid dyes |
| CN102076779B (en) * | 2008-07-02 | 2013-08-21 | 科莱恩金融(Bvi)有限公司 | Use of acid dyes |
| WO2010000780A1 (en) * | 2008-07-02 | 2010-01-07 | Clariant International Ltd | Acid dyes |
| WO2010130384A1 (en) * | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Bisazo compounds |
| EP2258683A1 (en) * | 2009-05-14 | 2010-12-08 | Clariant International Ltd. | Bisazo compounds |
| EP2258685A1 (en) * | 2009-05-14 | 2010-12-08 | Clariant International Ltd | Bisazo compounds |
| WO2010130382A1 (en) * | 2009-05-14 | 2010-11-18 | Clariant International Ltd | Bisazo compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2579606A1 (en) | 1986-10-03 |
| GB2173210B (en) | 1989-08-16 |
| IT1203759B (en) | 1989-02-23 |
| IT8647835A0 (en) | 1986-03-28 |
| SE8601401L (en) | 1986-10-01 |
| GB8607702D0 (en) | 1986-04-30 |
| CH667464A5 (en) | 1988-10-14 |
| FR2579606B1 (en) | 1989-08-18 |
| SE8601401D0 (en) | 1986-03-26 |
| JPH0662869B2 (en) | 1994-08-17 |
| JPS61231056A (en) | 1986-10-15 |
| SE468392B (en) | 1993-01-11 |
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| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 20060326 |