GB2148921A - New formazan reactive dyes - Google Patents
New formazan reactive dyes Download PDFInfo
- Publication number
- GB2148921A GB2148921A GB08423157A GB8423157A GB2148921A GB 2148921 A GB2148921 A GB 2148921A GB 08423157 A GB08423157 A GB 08423157A GB 8423157 A GB8423157 A GB 8423157A GB 2148921 A GB2148921 A GB 2148921A
- Authority
- GB
- United Kingdom
- Prior art keywords
- group
- formula
- compound
- represented
- blue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/046—Specific dyes not provided for in group C09B62/06 - C09B62/10
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The title compounds, in free acid form are of formula (1): <IMAGE> wherein n is 1 or 2, and when n = 1, <IMAGE> is substituted or unsubstituted amino or a group represented, in a free acid form by formula (2> <IMAGE> and when n = 2, <IMAGE> is -NH-X-NH- where X is a specified bridging group; R is H, SO3H, OH, Cl, F, C1-4 alkyl, C1-4 alkoxy or CO2H, and M is Cu or Ni. Compounds (1) impart violet to blue hues to cellulosic fibres, with a high colour yield and without agglommeration in the dye bath.
Description
SPECIFICATION
Formazan compound and process for dyeing cellulosic fiber by using the same
2. Detailed Description of the Invention:
This invention relates to a formazan compound and to a process for dyeing a cellulosic fiber by using the same. More particularly, this invention relates to a formazan compound represented, in a free acid form, by formula (1):
wherein n represents 1 or 2, and when n = 1,
represents -Z1 (wherein Z1 represents an amino group; a morpholino group; an anilino group which may be substituted with one or two members selected from the group consisting of a sulfonic acid group, a carboxyl group, a C, 4 alkyl group, a C1 4 alkoxy group, a hydroxy group, chlorine, or fluorine; a mono- or dialkylamino group which may be substituted with one or two members selected from the group consisting of a carboxyl group, an HO3-SO-, a hydroxyl group, or a sulfonic acid group; a naphthylamino group having 1 to 3 sulfonic acid groups; a benzylamino group, a benzylamino group having one sulfonic acid group; or a group represented, in a free acid form, by formula (2):
(wherein R and M are as will be defined below), and when n = 2, Zj -J represents Z2 (wherein Z2 represents -HNC2H4NH-;
(wherein R1 and R2 represent independently of each other hydrogen, chlorine, a methyl group, a sulfonic acid group, or a carboxyl group);
(wherein p represents 0 or 1);
(wherein R4 and R5 represent independently of each other a methyl group, sulfonic acid group, or a carboxyl group); or
(wherein Q represents 0, S, SO2, CH = CH, NH, CH2, CH2CH2, or CONH); R represents hydrogen, a sulfonic acid group, a hydroxyl group, chlorine, fluorine, a C14 alkyl group, a C14 alkoxy group, or a carboxyl group; and M represents copper or nickel, and to a process for dyeing a cellulosic fiber by using the same.
In general, metallized formazan dyes provide dyed fabrics having a clear color tone and excellent fastness, especially, to light and rubbing. Among the formazan reactive dyes, those having a cyanuric chloride group as the reactive group are superior in respect of the pH stability of a dye bath and the stability of a color paste in printing to those having a vinylsulfone group as the reactive group, and are advantageous in that excellent level dyed fabrics can be easily obtained. The thus-featured metallized formazan reactive dyes having a cyanuric chloride group as the reactive group are used very frequently in dyeing cellulosic fibers.
Although metallized formazan reactive dyes with a cyanuric chloride group are described in
Japanese Patent Publication No. 5041/1963 and Japanese Patent Laid-Open No.
94730/1973, the dyes described therein are disadvantageous in that they are liable to cause agglomeration in a dye bath, which is undesirable for dyeing, and that their colour values and build-up property are poor when applied to medium or deep color dyeing.
As a result of extensive studies to search out a dye free from the above-mentioned drawbacks, the inventors of this invention have found that a formazan compound does not agglomerate in a dye bath and shows a high color value and build-up property in medium or deep color dyeing and have achieved this invention.
To obtain the formazan compound of this invention represented by formula (1), a formazanamino compound represented by formula (3):
wherein R and M are as defined above, is first synthesized by the following method.
Namely, a formazanamino compound of formula (3) is obtained by coupling diazotized 6acetylamino-2- aminophenol-4-sulfonic acid with a 5-sulfo-2-carboxyphenyl-hydrazone represented by formula (5):
obtained from a compound represented by formula (4)
wherein R is as defined above; allowing copper sulfate, nickel sulfate, copper chloride, nickel chloride, or the like to act upon the product; and then hydrolyzing the acetylamino group into an amino group.
The formazan compound of formula (1) is synthesized from the thus-prepared formazanamino compound according to, for example, the following methods:
1. 1 mole of a formazanamino compound represented by formula (3) is reacted with 1 mole of 2,4,6-trichloro-1 ,3,5-triazine to obtain a condensate represented by formula (6):
which is further condensed with 1 mole of ammonia or an amine represented by the formula:
Z1-H (wherein Z1 is as defined above).
II. 1 mole of a formazanamino compound represented by formula (3) is condensed with 1 mole of a compound represented by formula (7):
wherein Z1 is as defined above.
Ill. A formazanamino compound represented by formula (3) is condensed with 2,4,6-trichloro1,3,5-triazole, which is then reacted with 1 mole of a diamine represented by the formula:
(wherein Z2 is as defined above) to obtain an intermediate product represented by formula (8):
which is then reacted with 1 mole of a compound represented by above formula (6).
Alternatively, 1 mole of a intermediate product of formula (8) is reacted with 1 mole of 2,4,6trichloro-1,3,5-triazine to obtain an intermediate product represented by formula (9):
which is then reacted with 1 mole of a formazanamino compound represented by formula (3).
To separate the thus-obtained purpose product from the reaction solution, usual separation methods such as acidification or salting out may be applicable.
Mention will be made of examples of R and Z (Z = Z, when n = 1, Z = Z2 when n = 2) in formula (1).
R includes, for example, hydrogen, a sulfonic acid group, a hydroxyl group, chlorine, fluorine, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a carboxyl group, and with regard to Z, Z, in case of n = 1 includes, for example, an amino group, a morpholino group, -NHCH3, -NHC2Hs, -N(CH3)2, -N(C2Hs)2, -NHC2H4OH, -N(C2H4OH)2, -NHCH2COOH, -NHC2H4SO3H, NHC2OSO3H,
(ex. o, m or p-SO3H), an anilino group, 2-, 3-, or 4-methoxy anilino group, an 2-, 3-, or 4sulfoanilino group, an o-, m-, or p-toluidino, an 2-, 3-, or 4-carboxyanilino, an mono, di-, or trisulfonaphthyl amino, 2,4- or 2,5-disulfoanilino,
(ex. 2-CI, 4-SO3H; 2-SO3H, 4-CI; 3-SO3H, 4-CI; 3-Cl, 4-SO3 H),
(ex. 2-F, 4-SO3H; 2-SO3H, 4-CI; 3-SO3H, 4-CI; 3-CI, 4-SO3H),
(ex. 2,4-CI; 3,4-CI),
(ex. 2-Cl, 4-CH3; 2-CH3, 4-Cl; 3-Cl, 4-CH3),
(ex. O, m, or p-CI),
(ex.O, m or p-F),
(ex. 2-CH3, 4-S03H; 2-SO3H, 4-CH3; 3-SO3H, 4-CH3, 3-CH3; 4-SO3H),
(ex. 3-OH, 4COOH; 2COOH, 4OH; 3OH, 4COOH),
(ex. 2S03H, 40CH3; 20CH3, 4Cl; 30CH3, 4-S03H; 40CH3, 3SO3H) and a group represented by formula (2)
and similarly, Z2 in case of n = 2 includes, for example, -NHC2H4NH-,
(ex. 4, 5, or 6-SO3H),
(ex. 4, 5 or 6COOH),
(ex. 4, 5 or 6 CH3),
(4, 5 or 6-Cl),
(ex. 5, 6 or 7-SO3H),
The formazan compound of this invention is suitable for dyeing natural or regenerated cellulosic fibers or blended yarn fibers containing these fibers and other fibers, and the dyeing methods which are applicable may be those usually used in dyeing with reactive dyes, such as printing, dip dyeing, or padding.
In printing, sodium alginate, emulsion paste or the like used as a stock paste is mixed with a dye, an acid binder, urea, etc., to form a color paste, which is applied on a textile. After intermediate drying, if necessary, the dye is fixed on the textile by wet or dry heat-treatment. In this case, a color paste containing no acid binder may be applied on a textile which has been impregnated with a solution of an acid binder, or a color paste containing no acid binder is first applied on a textile and then treated with a solution containing an acid binder, and the dye is fixed by the same treatment as above.
When the compound (dye) of this invention is applied under conditions of a relatively high bath ratio, such as those in dip dyeing, the fiber is dyed at 20 to 1 30 C for 10 to 60 minutes in the presence of an inorganic salt such as sodium chloride or sodium sulfate, and, after adding an acid binder, the fiber is dyed further at 30 to 1 00 C for 20 to 60 minutes. In this case, it is also possible to use a method in which an acid binder is added at the beginning of the dyeing.
When the compound (dye) of this invention is applied under conditions of a relatively low bath ratio, such as those in pad dyeing, a textile is padded in a padding bath prepared from a dye, an acid binder, a penetrant, urea as a dissolving agent, sodium alginate, etc. and, after squeezing, subjected to wet or dry heat-treatment to fix the dye.
Examples of the acid binders used in the above dyeing methods include sodium hydrogencarbonate, sodium metaphosphate, trisodium phosphate, sodium ortho- or metasilicate, sodium carbonate, and sodium hydroxide.
The formazan compound (dye) of this invention, when used in a printing paste or a padding bath, shows a high stability, so that the dyed products have less concentration uneveness due to changes in conditions of wet or dry heat-treatment, and exhibit a fixing rate and build-up property as high as those attained by conventional dip dyeing. The obtained dyed products are excellent in fasteness to light, light/perspiration, washing, water and chlorine water, a peroxide bleaching agent and exhibit a hue of violet to blue. Further, the compound shows little staining on white ground when used in printing. When a mixture of two kinds of the compounds of this invention is used, an effect similar to that obtained from the use of one such compound can be obtained.
Among the compounds of formula (1) the following compounds and dye composition are preferred in view of their dyeing properties and manufacturing cost.
(1) A formazan compound represented, in a free acid form, by formula (1) wherein n is 1, Z, represents NH2,
NHCH3, N(CH3)2, N(C2H5)2, NHC2H4OH, N(C2H4OH)2, NHCH2COOH, NHC2H4SO3H, NHC2H4O
SO3H,
2,4 or 2,5-disulfoanilino,
mono, di or trisulfonaphthyl amino or a group represented, in a free acid form, by formula (2), R and M are the same meanings defined in formula (1).
(2) A formazan compound represented, in a free acid form, by formula (1), wherein n is 1, R represents H, SO3H, Cl, F, CH3, C2Hs, OCH3, OC2Hs and COOH, Z1, M are the same meanings defined in above (1).
(3) A formazan compound represented, in a free acid form, by formula (1) wherein n is 2, Z2 represents -HNC2H4NH-,
R and.M are the same meanings defined in formula (1).
(4) A formazan compound represented in a free acid form by formula (1) wherein n is 2, R represents H, SO3 H, Cl, F, CH3, C2Hs, OCH3, OC2H5 and COOH, Z2 and M are the same meanings defined in above (3).
(5) A dye composition comprising a compound of formula (1) wherein n is 1, Z is NH2,
NHCH3, NHC2H5, N(CH3)2, N(C2Hs)2, NHC3H4OH, N(C2H40H2, NHCH2COOH, NHC2H4SO3H, NHC2H4OSO3H,
2,4 or 2,5-disulfoanilino,
mono, di- or tri-sulfonaphthylamino, M and R are the same meanings defined in above (4), and a compound of formula (1) wherein n is 1, Z is a group represented, in a free acid form, by formula (2), M and R are the same meanings defined in formula (1). The mixing ratio of the former compound: the latter compound B is preferably 7:3-4:6.
(6) A dye composition comprising a compound defined in above (2) and a compound defined above (5).
The mixing ratio of the former compound: the latter compound is preferably 3:7-6:4.
(7) A dye composition comprising a compound of formula (1) wherein n is 1, Z, is NH2, M is
Cu and R is H and a compound of formula (1) wherein n is 1, Z1 is a group represented by formula (2), M is Cu and R is H.
This invention will now be described in more detail with reference to examples, but it should be understood that this invention is not limited thereto. In these examples, parts are parts by weight, and the sulfonic acid group in each formula is represented in the form of a free acid.
Example 1
3.8 parts of cyanuric chloride was added under agitation to a solution comprising 20 parts of water, 40 parts of ice, 0.5 part of a 10% aqueous solution of Liponox NA (a dispersant manufactured by the Lion Co., Ltd.). After agitating the mixture for 30 minutes (suspension), a solution prepared by dissolving 3,46 parts of orthanilic acid in 40 parts of water was added thereto over a period of 30 minutes, during which its temperature was maintained at below 10"C. Thereafter, the mixture was reacted at about 10'C for 6 hours under agitation, while the pH value of the mixture was being maintained at 6 to 8 by the addition of a 10% aqueous soda ash solution.The reaction mixture was added to a solution prepared by dissolving 1 2.8 parts of the formazanamino compound of the following structure in 1 50 parts of water.
The obtained mixture was heated to a temperature of 45 to 55"C and reacted for two hours, while its pH value was being maintained at 6 to 8 by the addition of a 10% aqueous soda ash solution. The resulting mixture was salted out at the same temperature and crystals formed were dried at 60"C to obtain 24.0 parts of the compound of the above formula (10) (Amax 610 nm in water).
Example 2
A dye bath was prepared from 2 parts of the compound represented by the above formula (10), 80 parts of sodium chloride and 1000 parts of water. 50 parts of a cotton knitted fabric was immersed in this bath, treated therein at 80"C for 30 minutes and, after adding 20 parts of sodium carbonate, further treated at the same temperature for 60 minutes to effect dyeing. After water-washing, the fabric was soaped at 95 to 1 00 C for 10 minutes by using 1000 parts of an aqueous solution containing 2 parts of an anionic surfactant, washed with water, and dried to obtain a dyed fabric of a clear blue color. It had excellent fastness to light, wetness, and chlorine water. No agglomeration of the dye was observed during dyeing.
Examples 3 through 44.
Compound were synthesized and applied to cotton fabrics by dyeing according to the procedures as in Examples 1 and 2. Table 1 shows structural formulas of the synthesized compounds, hues obtained when they were applied to cotton fabrics, and their Ama, values in water.
Table 1
Example Structural Formula Hue (nm) (nm) Cu 01 \ N 3 Ex BN-- , blue 608 ~, 4 S 2 4 < blue 609 so so's CI Table 1
fl- I -1 t Structural Formula H I I CI Cu O
CH3 N O C=O
6 # HN HN # N N C N HN # blue 610
N N
SO3H # SO3H
Cl
: Dlueg610 0 H3O-HhT-a-HN t C; blue C=0 7 CHHNN?%IHNoN=NC=HN0' blue 610 SOH Cl SO II 3 3 Cu 8 N \cf blue 610 3S - 503R SO3H (5o Cl
i o cu os 9 2 < - t | blue 608 B00 ss 503H soda Cl L\lo 10 j blue; 60B J a SO3:Er SOA CI
11 EEi8 < 0- e blue / blur| 608 N (5o So Cl
Example Structural Formula Hue No. (nm) Ca~O ' 12 c blue 609 80az3 BOSH 90iH Cl O jR O 13 C CO blue 610 HOOC SO,H (i sota Ch O CE0sO0 14 E+ < blue 609 C1 O'c-o -If F-ELN Cl I 0C2HS sO:E N -I N yrT 16 < N + 9 blue 608 HOsS Y SQ3H w SO3E Cl SOsH 0 N CCI 17 1 o ED ~7 NF BOSH blue | 608 C1 C2H5 Cz O 18 oCE: N /1 18 3 > 9N we +G blue 610 cH: N C eC1 SO,II & So3H CI
Example No. Structural (nm) Hue max (nm) 19 l SOa - blue 609 19 E038 N \HA)o blue 609 E03S 1 SO3E SO;;E Cl 20 EOEZCS1C,Li(/ jHN--)-L3,hjlC--f-HN7/ blue 608 BOSH EOH2 BOSH Cl Cu o C=O 21 H,s-ta?e 1 2 no blue 610 N' -N SOIL 0 So3R I Cl soli 22 Ca 0\H O NN103a , Boils P blue 609 N 23 blue 595 N N N SI Y BOSH Cl BOSH BOSH ------0C3C 24 < | blue 609 BOSH CCI SR Cl Co C N I 25 S3SCE N e LK,,'; ;F-plZJ-C.IN-Fi-blue blue 608 N 0 So BOSH Cl
Example Structural Formula Hue (nm) BOSH N R 9 ple 26 pur- 530 soa BOSH BOSH Cl c=a0 N I pur- I 27 H1N7 B2N--,BN pIe N N pur- 529 C BOSH Cl 28 E4CI\ EjC > Nmf 28 Cc: > c{JW/= Ca-C blue 610 1yN 1 BOSH 29 EOE GC N N l ASH /so;a o . I Aă I - BOSH 503R Cl BOSH o oa3a 0 > w 31 Cl BOSH Cl BOSH
Example Structural Formula Hue | Amax No. (nm) BOSH (; 'Cl=0 ISOrH = blue 609 BOSH BOSH Cl 34 çEFr 2e blue 610 BOW BOSH a Ni-C CI3:a 35 | < < vio- 530 NN let BOSH Oo SlOSH BOSH 0Ni-% Ni I 35 f e pur- 529 N1 I ple BOSH BOSH a 0 ^-F3- lo38- e BlOW (5c I BOSH 37 a blue 611 O owCz /12 BOSH i BOSH Cl- 0% N c-aC z blue 610 BOSH B1OSH Cl
v Example Structural Formula Rue Amax No. (nm) Co -- 4 0 0 39 EiC +N Nr + e blue 610 39 S v CC > EO,S BOSH OCOCE BC Cl Cii 'N / DO 40 CH3 C blue 607 (tie sotlr Cu--0,'OIO ~ ~ C 42 (H3C)oN < (H3 K c--;;a 4 blue 608 SOSH SOs Cl 43 | HOOCC}2NE NS < blue 608 S SOz Cu 0% 0 blue 44 N"N--C 1 blue 610 N N 0 Cl OC H Example 45
1 2.8 parts of the formazanamino compound of the following structure was dissolved, with agitation, in a solution comprising 1 50 parts of water, 50 parts of ice, and 0.5 part of a 10% aqueous Liponox NA
3.8 parts of cyanuric chloride was added thereto, and the mixture was reacted at below 10"C for one hour, while the pH value of the mixture was being maintained at 6 to 8 by the addition of a 10% aqueous soda ash solution. To this reaction solution was added a solution prepared by dissolving 1.85 parts of 2,2'-disulfo-4,4'-diaminodiphenylethane in 50 parts of water. The obtained mixture was heated to a temperature of 45 to 55"C and reacted for 4 hours while its pH value was being maintained at 6 to 8 by the addition of a 10% aqueous soda ash solution.
The mixture was salted out at the same temperature, and precipitated crystals were filtered and dried at 60"C. 23.0 parts of the compound of the above formula (11) was obtained (A,,, 600 nm in water).
Example 46
A dye bath was prepared from 2 parts of the compound represented by formula (11), 40 parts of sodium chloride and 1000 parts of water. 50 prts of a cotton knitted fabric was immersed in this bath, treated therein at 80"C for 30 minutes and, after adding 20 parts of sodium carbonate, dyed further at the same temperature for 60 minutes. The dyed fabric was soaped in the same way as in Example 2, washed with water, and dried to obtain a dyed fabric of a clear blue color. It had excellent fastness to light, wetness and chlorine water.
Examples 47 through 73
According to the procedures as in Example 40, compounds were synthesized and applied to cotton fabrics by dyeing. Table 2 shows structural formulas of the synthesized compounds, hues obtained when they were applied to cotton fabrics and their Ama, values in water.
Table 2
Example (nm) AO C / \ \ OtH RN t > N-N-C-N-HN > NH 47 H ( SOtH Ny;1)2 H blue 595 48 0Nffi7N0 N\ HN SOSIHOHI NH- b 1 ue597 50tH A HNYy ss HN g o e NH- flut);;$P12 OaS O Cu OOH 49 e-N-NN j HN - 0 NH- blue 596 \\ StH SOH Nyji12 HOOC 0-C N-NC Xj-HNr > HN W HNNH 50 )W{NosiHN$r HlCS)H)a blue 597 a Cu HOOC A C U A0 N~~~ 51 & N-N-C-N-HN -QtoHN 'i blue 598 5l t So,N 4 COoR 505R CI - Cu o . N 50tH 52 ;iN;NCNHN4r)$f2 t só,N blue t W HOtS O-Co C U\0 N SOaR 53 2 ( $ C-N N+NNY iNN@NN@NN blue | 595 SO,X SO3X Y 2 l
rw Example 1 Structural Formula Hue Amax (rim) Cu 0 50tH 54 t C / < < NN4gCNCNeNP blue 600 SOtH 50tH 55 doNNC-NHNRN-1'HNCH1 CH1NH- blue 598 SlOtH (5o 50tH 'C12 56 & 1N- 6 ( k > i blue 5 97 c NH- blue 598 57 [ N-N X NN9NN- SOaR \ & OtH 1N Cu O-C0 \ 0N Cl 58 | / < NNgNN- blue 600 50tH 0C'1 SOaR N-fmblue Yj)2 59 ( NNXCNENt? HNt t HNNH- blue 597 gO ?CRt SOaR J SOaa SOaR Ni 0 1 OaR 60 | $≈ N / -C-N-bN + NNf t NN g CN.CN. e NN- l pur- g S lN%12 RotS 0 -HNs6N ple 55 N
Example Structural Formula Hue No. (nm) 61 RN7/oNH- pur- 520 SlosH & -r 50tH ple 0Cu 62 0-C \ 0 C(Nl2CRtCHtNH blue 598 (%CoNHN%iHN I 63 tkN4, NbNtN t] NNqFNN blue 598 H ,so,II 64 0OCuM0 N lRCONH blue 595 -NIICONR- blue 595 64 /0.F::BNNR0 e n NNtNN HNNH- blue 602 J-NIN-C-N-BN I, 55 t 4iNNv blue 66 N-NC-N-H?Th0-HN HNNE- blue 600 -c-N-aN-;BNI 0Cu N M N t 67 ! ( ~vANNgN pE blue | 600 SotHOl 50tH OCHa lNYcl2 HotS
s No. Structural Formula Hue ! AmaX (rim) 0Ni 68 V C EiNeCbH-' pur- 520 CRi pie SOaR SOaR 2 0-C0 C.ii\ 0 -Na-Pa 69 (\ w N@;Nb blue 600 0 700-NC-N-NHNR1 H0t blue 598 SlotH z SOaR %N12 Cu ~~~ 0-C0 \ , NH 71 -NC -N-NHNH NRo CR3 blue 598 SOaR0 0 2 SOaR Cl 0C2H5 Cu ~o NH 0 N, 72-N-MIf 1 blue 598 Slosh SlotH 2 C2R Cl Cu SO3H 0-C /\0N lo-c-'r-N-C-N-N cÒOg blue 595 COOR Cl SO3H Example 74
A dye bath was prepared from 1.5 parts of a mixture of 1.0 part of the compound of formula (12) and 0.5 part of the compound of formula (13), 50 parts of sodium chloride and 1000 parts of water. 50 parts of a cotton knitted fabric was immersed in this bath, treated therein at 80"C for 30 minutes and, after adding 1 5 parts of trisodium phosphate, dyed at the same temperature for 60 minutes. The dyed fabric was soaped in the same way as in Example 1, washed with water, and dried to obtain a dyed fabric of a blue color. By the way, when the dyeing was carried out by replacing the above mixture of the compounds (12) and (13) with a mixture of compounds (12) and (13) which had been obtained at the time of synthesis, a dyed fabric similar to the above was obtained.Namely, 1 2.8 parts of the formazanamino compound of the following structure:
was dissolved, under agitation, in a solution comprising 1 50 parts of water, 50 parts of ice, and 0.5 part of a 10% aqueous Liponox NA solution.
After agitating this mixture for 30 minutes, 0.9 part of cyanuric chloride was added, and the mixture was reacted at below 10"C for one hour, while its pH value was being maintained at about 7 by the addition of a 10% aqueous soda ash solution. The mixture was heated to 50"C and reacted at a temperature of 50 to 55"C, while its pH value was being maintained at 6 to 8 by the addition of a 10% aqueous soda ash solution.To the obtained reaction mixture was added a condensate separately prepared by adding 1.8 parts of cyanuric chloride under agitation to a solution comprising 10 parts of water, 30 parts of ice, and 0.5 part of Lipal OH (a dispersant manufactured by the Lion Co., Ltd.) and, after agitating the mixture for one hour, adding 1.2 parts of 29% ammonium water, and reacting the mixture at about 20"C and a pH value of 8 to 9 for one hour. The resulting mixture was heated to 50 to 55'C and reacted at a pH value of about 7 for two hours. The mixture was salted out with sodium chloride at the same temperature. The obtained crystals were filtered and dried at 60"C.
In this way, 22.0 parts of a mixture of the compounds of formulas (12) and (13) at a ratio of about 1:1 was obtained.
Examples 75 through 78
According to the procedure as in Example 74, mixtures of compounds were prepared and applied to cotton fabrics by dyeing.Table 3 shows the structures of the components of each mixture, hues obtained when applied to cotton fabrics, and the Amax values (in water) of the mixtures.
Table 3
EExample StructuraL Formula Hue max No. (nm) g NtEN~ & 73 75 > p 9 blue 610 blue -NItN'Na. blue 610 - Co HOtS N-HNbo N}N , 4 AO H 76 WCDN O blue 608 (Mtj-f-f HOI oJr a /xP NX SOH sIosECslOtHNYj: Rots 77 C: @ SO;I SCIJZ boil blue 604 -,0' HN- 80tH t0K,O > l > B + AO;I & 0.o SOH N.bC-o HNI -N-NIN-fIN 78 C1 | @) SOJ pur- 531 ple 0tH pie HIl-C-ll- HNoSmjo BOsS ~ Example 79 - A cotton gaberdine fabric was padded in 10,000 parts of a padding bath comprising 30 parts of the compound of formula (10) described in Example 1 and 970 parts of water, squeezed at a squeezing ratio of 65%, and subjected to intermediate drying.Subsequently, the dye was fixed by using a treatment bath comprising 20 parts of trisodium phosphate, 200 parts of an hydros sodium sulfate, and 780 parts of water at 80"C for 60 minutes by using jigger dyeing tester.
The fabric was soaped in the same way as in Example 2, washed with water, and dried to obtain a dyed fabric of a blue color.
Example 80
1,000 parts of a color paste was prepared from the compound of formula (14) (the compound obtained in Example 9) according to the following recipe: compound of formula (14) X parts sodium alginate 25 parts urea 100 parts sodium bicarbonate 20 parts
Polymin Lnew 10 parts water 465 parts hot water 38-X parts (wherein X is 10, 30, or 60 and Polymin Lnew is a reduction preventing agent manufactured by
Nippon Kayaku Co., Ltd.]
A mercerized cotton broad fabric was printed with the above color paste, dried at 60"C for 10 minutes, wet-heat-treated in saturated steam of 100"C, and then washed with water. The time of the wet heat-treatment was varied, and was 5, 10, or 20 minutes.
The fabric was washed with hot water at 60"C for 5 minutes, and soaped in 1 ,000 parts of a boiling bath containing 2 parts of an anionic surfactant, and then washed with water. The fabric was dried to obtain a printed fabric of a clear blue color. The concentration difference was extremely small among dyed fabrics treated in different wet treatment times.
Comparative Test
A comparative test was made for comparing the colour yield of the compounds of this invention and well-known dyes according to the following method.
50 parts of an unmercerized cotton knitted fabric was immersed in a dye bath prepared from 0.5 part of the compound or dye, 80 parts of anhydrous sodium sulfate, and 899.5 parts of water, treated therein at 80"C for 30 minutes and, after adding 20 parts of anhydrous sodium carbonate, dyed at the same temperature for 60 minutes. The dyed fabric was washed with water and then with hot water, soaped in the same way as in Example 2, washed with water, and dried.
The colour yield on the dyed fabrics were compared visually by using the colour yield on the fabric dyed with the compound of this invention as a standard and summarized in the table.
Table 4
Dye Colour or Structural Formula Yield Compound (%) O Cu O Compound of N~~~ Ex.9 of this t G-N-N t B S% invent ion NN (standard) SIOR Y Cl Dye similar to Ex.5 of Japan o-C' / \ \ nese Patent etc - N - NH-;;OB FNBi 15 Publication BOSKS 50tH ~ > N N 503H No.5041/63 S0XS Cl CI 0 Compound of O O N Ex.3 of this 0N-N-I-NH0NH FNH2 100 invention 50tH N N (standard) S03B S03B Y Cl Dye similar to0 Ex.49 of Japa- QMI-rNNHz less than nese Patent 1 No.5041/63 S 3X ≈ Yo z Ny 10 Compound of { C-0 / t N ss SOH invention t NH G C < NH- 100 Cl Dye of Ex.72 O ~ Cu O SOaH of Japanese O-C / \ \ N \ ~2 Patent Laid SNNOWNH4NHS FNBeC;haNH 3o Open No ~ , SO tSOsEI Y NyNJ SOxH / ,O Cu O Compound of o-C / \ \ N ss 100 Ex.52 of this N=.N-C-N - NS9Ns-t eNB4S@Nw - (standard) invention ~ < SOsE ≈ Cl i2 SÓ
m Dye Colour or Structural Formula Yield Compound Compound (%) t Dye of Ex. 73 of Japanese O-C / \ \ N , < SOV Patent Laid > 13 Open No - s No. 94730/73 0 5() Y Cl
It is clearly understood from this table that the colour yield of the compound of this invention is extremely high as compared with those of the known dyes having structures similar to that of the compound of this invention.
Claims (14)
1. A formazan compound represented, in a free acid form, by formula (1):
wherein n represents 1 or 2, and when n = 1,
represents -Z, (wherein Z1 represents an amino group; a morpholino group; an anilino group which may be substituted with one or two members selected from the group consisting of a sulfonic acid group, a carboxyl group, a C14 alkyl group, a C14 alkoxy group, a hydroxy group, chlorine, and fluorine; a mono- or dialkyl-amino group which may be substituted with one or two members from the group consisting of a carboxyl group, an HO3SO-, a hydroxyl group and a sulfonic acid group; a naphthyl-amino group having 1 to 3 sulfonic acid groups; benzylamino group a benzylamino group having one sulfonic acid group; or a group represented, in a free acid form by formula (2)
(wherein R and M are as will be defined below), and when n = 2,
represents
(wherein Z2 represents -HNC2H4N-;
(wherein R, and R2 represent independently of each other hydrogen, chlorine, a methyl group, a sulfonic acid group, or a carboxyl group);
(wherein p represents 0 or 1);
(wherein R4 and R5 represent independently of each other a methyl group, a sulfonic acid group, or a carboxyl group); or
(wherein Q represents 0, S, SO2, CH = CH, NH, CH2, CH2CH2, or CONH); R represents hydrogen, a sulfonic acid group, a hydroxyl group, chlorine, fluorine, a C1-4 alkyl group, a C14 alkoxy group, or a carboxyl group, and M represents copper or nickel.
2. A formazan compound, according to claim represented, in a free acid form, by formula (1),
wherein n is 1, Z, represents NH2,
NHCH3, N(CH3)2, N(C2H5)2, NHC2H40H, N(C2H40H)2, NHCH2COOH, NHC2H4SO3H, NHC2H40
SO3H,
2,4 or 2,5-disulfoanilino,
mono, di or trisulfonaphtyl amino or a group represented, in a free acid form, by formula (2).
3. A formazan compound according to claim 2 represented, in a free acid form, by formula (1), wherein n is 1, R represents H, SO3H, CI, F, CH3, C2H5, OCH3, OC2H5 and COOH.
4. A formazan compound, according to claim 1 represented, in a free acid form, by formula (1), wherein n is 2, Z2 represents -HNC2H4NH-,
and
5. A formazan compound, according to claim 4, represented in a free acid form by formula (1), wherein n is 2, R represents H, SO3H, Cl, F, CH3, C2H5, OCH3, OC2Hs and COOH.
6. A dye composition comprising a compound of formula (1) wherein n is 1, Z is NH2,
NHCH3, NHC2H5, N(CH3)2, N(C2H5)2, NHC2H40H, N(C2H40H)2, NHCH2COOH, NHC2H4S03H, NHC2H4OSO3H,
2,4 or 2,5-disulfoanilino,
mono, di- or tri-sulfonaphtylamino, M and R are the same meanings defined in claim 3, and a compound of formula (1) wherein n is 1, Z is a group represented, in a free acid form, by formula (2), M and R are the same means defined in claim 1.
7. A dye composition comprising a compound claimed in claim 3 and a compound claimed in claim 6.
8. A dye composition according to claim 6 comprising a compound of formula (1) wherein n is 1, Z is NH2, Mis Cu and R is H and a compound of formula (1) wherein n is 1, Z is a group represented by formula (2), M is Cu and R is H.
9. A process for dyeing a cellulosic fiber by using a formazan compound represented by formula (1).
10. A process for dyeing, according to claim 9, wherein the formazan compound is a compound claimed in claim 3.
11. A process for dyeing, according to claim 9, wherein the formazan compound is a compound claimed in claim 5.
1 2. A formazan compound as claimed in claim 1 and substantially as described in any one of the specific examples herein set forth.
1 3. A dye composition as claimed in claim 6 and substantially as described in any one of the specific examples herein set forth.
14. Each and every novel embodiment herein set forth taken either separately or in combination.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58176708A JPS6067562A (en) | 1983-09-24 | 1983-09-24 | Formazan compound and dyeing of cellulosic fiber using the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8423157D0 GB8423157D0 (en) | 1984-10-17 |
| GB2148921A true GB2148921A (en) | 1985-06-05 |
| GB2148921B GB2148921B (en) | 1987-05-28 |
Family
ID=16018363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08423157A Expired GB2148921B (en) | 1983-09-24 | 1984-09-13 | New formazan reactive dyes |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS6067562A (en) |
| CH (1) | CH661278A5 (en) |
| DE (1) | DE3434818C2 (en) |
| GB (1) | GB2148921B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2172896A (en) * | 1985-03-16 | 1986-10-01 | Sandoz Ltd | Reactive formazan dye mixtures |
| US4973671A (en) * | 1987-11-05 | 1990-11-27 | Basf Aktiengesellschaft | Doubled copper formazan reactive dyes containing a monofluorotriazine or monochlorotriazine group |
| US5041540A (en) * | 1988-12-02 | 1991-08-20 | Basf Aktiengesellschaft | Copper formazan reactive dyes having halotriazine ring |
| US5371200A (en) * | 1989-11-01 | 1994-12-06 | Ciba-Geigy Corporation | Fibre-reactive formazan dyes, processes for their preparation and their use |
| US5410041A (en) * | 1992-08-19 | 1995-04-25 | Ciba Geigy Corporation | Bisreactive dyes having a disulfophenylene bridging member |
| US5451665A (en) * | 1990-09-25 | 1995-09-19 | Ciba-Geigy Corporation | Fibre-reactive dyes containing two halotriazine groups and dye mixtures and their use |
| WO2000046308A1 (en) * | 1999-02-08 | 2000-08-10 | Nippon Kayaku Kabushiki Kaisha | Formazane compounds and methods of dyeing with the same |
| US6500247B1 (en) | 1999-02-05 | 2002-12-31 | Ciba Specialty Chemicals Corporation | Black-dyeing inks and their use |
| EP1787684A2 (en) | 2005-11-22 | 2007-05-23 | Henkel Kommanditgesellschaft auf Aktien | New couplers |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5012362A (en) * | 1987-06-19 | 1991-04-30 | Olympus Optical Co., Ltd. | Apparatus for positioning a transducer for recording, reproducing or erasing information on a medium |
| DE3737536A1 (en) * | 1987-11-05 | 1989-05-18 | Basf Ag | COPPER FORMAZAN REACTIVE DYES AND THEIR USE |
| JP3809974B2 (en) * | 1997-02-28 | 2006-08-16 | 日本化薬株式会社 | Formazan compound and method for dyeing cellulosic fibers using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1459453A (en) * | 1972-12-29 | 1976-12-22 | Ciba Geigy Ag | Fibre-reactive copper complex formazane dyestuffs their manu facture and use method and device for continuous winding onto a spool and undwinding from a spool of an endless band eg a cinematograph |
| EP0021351A1 (en) * | 1979-06-20 | 1981-01-07 | Sumitomo Chemical Company, Limited | Formazan reactive blue dyes, a process for their preparation and a process for dyeing cellulose fibers therewith |
| EP0074938A2 (en) * | 1981-09-14 | 1983-03-23 | Stig Sundman | Freely floating wind power plant |
| EP0099721A1 (en) * | 1982-07-19 | 1984-02-01 | Sumitomo Chemical Company, Limited | Reactive metal formazan blue dye |
| GB2125443A (en) * | 1982-04-27 | 1984-03-07 | Nippon Kayaku Kk | Exhaust dyeing of cellulose and cellulose union fibres |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1389053A (en) * | 1972-02-22 | 1975-04-03 | Ici Ltd | Reactive dyestuffs |
| GB1398601A (en) * | 1972-08-31 | 1975-06-25 | Ici Ltd | Reactive formazan dyestuffs |
| CH612448A5 (en) * | 1974-12-20 | 1979-07-31 | Ciba Geigy Ag | |
| JPS5958059A (en) * | 1982-09-28 | 1984-04-03 | Sumitomo Chem Co Ltd | Metal formazan compound, its preparation, and dyeing of fibrous material using it |
-
1983
- 1983-09-24 JP JP58176708A patent/JPS6067562A/en active Granted
-
1984
- 1984-09-13 GB GB08423157A patent/GB2148921B/en not_active Expired
- 1984-09-21 CH CH453884A patent/CH661278A5/en not_active IP Right Cessation
- 1984-09-22 DE DE19843434818 patent/DE3434818C2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1459453A (en) * | 1972-12-29 | 1976-12-22 | Ciba Geigy Ag | Fibre-reactive copper complex formazane dyestuffs their manu facture and use method and device for continuous winding onto a spool and undwinding from a spool of an endless band eg a cinematograph |
| EP0021351A1 (en) * | 1979-06-20 | 1981-01-07 | Sumitomo Chemical Company, Limited | Formazan reactive blue dyes, a process for their preparation and a process for dyeing cellulose fibers therewith |
| EP0074938A2 (en) * | 1981-09-14 | 1983-03-23 | Stig Sundman | Freely floating wind power plant |
| GB2125443A (en) * | 1982-04-27 | 1984-03-07 | Nippon Kayaku Kk | Exhaust dyeing of cellulose and cellulose union fibres |
| EP0099721A1 (en) * | 1982-07-19 | 1984-02-01 | Sumitomo Chemical Company, Limited | Reactive metal formazan blue dye |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2172896A (en) * | 1985-03-16 | 1986-10-01 | Sandoz Ltd | Reactive formazan dye mixtures |
| US4973671A (en) * | 1987-11-05 | 1990-11-27 | Basf Aktiengesellschaft | Doubled copper formazan reactive dyes containing a monofluorotriazine or monochlorotriazine group |
| US5041540A (en) * | 1988-12-02 | 1991-08-20 | Basf Aktiengesellschaft | Copper formazan reactive dyes having halotriazine ring |
| US5371200A (en) * | 1989-11-01 | 1994-12-06 | Ciba-Geigy Corporation | Fibre-reactive formazan dyes, processes for their preparation and their use |
| US5892006A (en) * | 1990-09-21 | 1999-04-06 | Ciba Specialty Chemicals Corporation | Fibre-reactive dyes and dye mixtures and their use |
| US5451665A (en) * | 1990-09-25 | 1995-09-19 | Ciba-Geigy Corporation | Fibre-reactive dyes containing two halotriazine groups and dye mixtures and their use |
| US5410041A (en) * | 1992-08-19 | 1995-04-25 | Ciba Geigy Corporation | Bisreactive dyes having a disulfophenylene bridging member |
| US6500247B1 (en) | 1999-02-05 | 2002-12-31 | Ciba Specialty Chemicals Corporation | Black-dyeing inks and their use |
| US7057024B2 (en) | 1999-02-05 | 2006-06-06 | Ciba Specialty Chemicals Corporation | Black-dyeing inks and their use |
| WO2000046308A1 (en) * | 1999-02-08 | 2000-08-10 | Nippon Kayaku Kabushiki Kaisha | Formazane compounds and methods of dyeing with the same |
| US6653454B1 (en) | 1999-02-08 | 2003-11-25 | Nippon Kayaku Kabushiki Kaisha | Formazane compounds and method of dyeing using the same |
| EP1787684A2 (en) | 2005-11-22 | 2007-05-23 | Henkel Kommanditgesellschaft auf Aktien | New couplers |
| EP1787684A3 (en) * | 2005-11-22 | 2010-03-31 | Henkel AG & Co. KGaA | New couplers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3434818A1 (en) | 1985-04-04 |
| GB2148921B (en) | 1987-05-28 |
| CH661278A5 (en) | 1987-07-15 |
| GB8423157D0 (en) | 1984-10-17 |
| JPH0521945B2 (en) | 1993-03-26 |
| DE3434818C2 (en) | 1998-08-20 |
| JPS6067562A (en) | 1985-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH02102271A (en) | Anionic triazinylaminodisazo dye | |
| GB2148921A (en) | New formazan reactive dyes | |
| JPH0651954B2 (en) | Reactive dye composition for cellulose fiber | |
| JPH0231749B2 (en) | ||
| JPH0197282A (en) | Method for dyeing or printing natural or synthetic polyamide fiber material using reactive dye | |
| CA1052777A (en) | Tetrareactive disazo dyestuffs, their manufacture and their use | |
| AU747485B2 (en) | Process for the treatment of cellulose fibres | |
| ZA200006610B (en) | Mono- and disazo reactive dyes. | |
| US5942011A (en) | Process for dyeing textiles containing polyester fibers and dyeing auxiliaries | |
| JPS63112661A (en) | Water-soluble dis-azo compound, its production and use thereof as dye | |
| KR0181491B1 (en) | Reactive dyes | |
| JPS5818474B2 (en) | Dyeing method for cellulose fibers | |
| JPH07196936A (en) | Stilbene disazo dye | |
| US6086640A (en) | Formazan compounds and method of dyeing therewith | |
| JPS5857465B2 (en) | New reactive azo dye, its production method and dyeing method using it | |
| US5371200A (en) | Fibre-reactive formazan dyes, processes for their preparation and their use | |
| JPS58191755A (en) | Reactive dye for cellulosic fiber | |
| KR100460556B1 (en) | Fiber-reactive dyes, a method for producing the same, and a dyeing or printing method using the same | |
| US3509138A (en) | Reactive phthalocyanine dyestuffs | |
| JPH0210184B2 (en) | ||
| KR0131760B1 (en) | Phthalocyanine compound, rrocess for dyeing or printing of organic substructure by using the smae | |
| JPH06157932A (en) | Dye mixtures, their production and their use | |
| MXPA02008200A (en) | Dye mixture comprising water soluble fiber reactive dyes, preparation thereof and use thereof. | |
| JPS62252462A (en) | Metallized dis-zao compound containing triazinylamino terminal group | |
| JPS60215070A (en) | Fiber-reactive monoazo compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20020913 |