GB2337270A

GB2337270A - Yellow reactive dye composition comprising at least two [(1,3,5-triazin-2-ylaminophenyl)azo]naphthalene-(di-/tri-)sulphonic acid fibre reactive monoazo dyes

Info

Publication number: GB2337270A
Application number: GB9910939A
Authority: GB
Inventors: Katsumi Agata; Nobutaka Kunimi; Shinichi Yamate; Junichi Sekihachi
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1998-05-13
Filing date: 1999-05-11
Publication date: 1999-11-17
Anticipated expiration: 2019-05-11
Also published as: DE19921634A1; GB2337270B; GB9910939D0

Abstract

A reactive dye composition which is excellent in build-up property and which reveals a high fixing ratio in the dark color range is provided which comprises 1) a first compound of formula (I) or a salt thereof: and 2) a second compound, which is not identical to the first compound, and which is (i) a compound of formula (I) or a salt thereof; (ii) a compound of formula (II) or a salt thereof: (iii) a compound of formula (III) or a salt thereof: (57) continued overleaf (57) cont wherein R<SP>1</SP>,R 4 and R 7 independently represent ureido, alkylcarbonylamino, alkenylcarbonylamino or phenylcarbonylamino, each of which is optionally substituted; R<SP>2</SP>,R<SP>3</SP>,R<SP>5</SP>,R<SP>6</SP> and R<SP>8</SP> independently represent a hydrogen atom or an optionally substituted alkyl group; B<SP>1</SP>,B<SP>2</SP>,B<SP>3</SP>,B<SP>4</SP> and B<SP>5</SP> independently represent an optionally substituted phenylene group or an optionally substituted naphthylene group; m, m2 and m3 independently represent 1 or 2; n, n2 and n3 independently represent 0 or 1, provided that the sum of m and n for each pair is 2 or 3; and Y<SP>1</SP>,Y<SP>2</SP>,Y<SP>3</SP>,Y<SP>4</SP> and Y<SP>5</SP> independently represent -CH 2 CH 2 L (wherein L represents a group releasable by the action of alkali eg. halogen or -O-SO 3 H) or a vinyl group, and one of Y<SP>1</SP> and Y<SP>2</SP> may also be -CH 2 CH 2 OH. The composition may be used to dye or print materials containing a hydroxyl group and/or an amide group

Description

1 2337270 YELLOW REACTIVE DYE COMPOSITION

FIELD OF THE INVENTION

The present invention relate to a yellow reactive dye composition and to applications thereof.

DESCRIPTION OF THE RELATED ART

Conventionally. various reac tive dyes and mixtures thereof are known, and widely used in.the field of dying or printing of cellulose-based fiber materials. However, even if fiber materials are dyed or printed using these reactive dyes and mixtures thereof, there are problems that dyeing properties, such as exhaustion property, solubility, leveling property, fixing property, build-up property, alkali bath stability, easiness of washing and removal of an unf ixed dye from a f iber material, and the like, particularly, exhaustion property, solubility, leveling property, alkali bath stability, and the like, are not satisf actory.as compared with recent high requirements.

Under such circumstances, the present inventors have intensively studied f or developing a reactive dye composition which is excellent in dyeing-properties, particularly, in exhaustion property, solubility, leveling property and alkali bath stability, in._dyeing or printing treatment of a cellulose-based fiber a rial, and can provide a dyed product or a printed productlicellent in various fastness. As a result, the present inventors have f ound that a speci f ic reactive dye composition caiir"complish the above-described __1 - object, and completed the present invention.

SUMMARY OF THE INVENTION

The present invention provides a reactive dye composition, which comprises:

1) a first compound selected from a group consisting of i) compounds represented by the following general formula (I):

H NI N=N N- N N- (S03H)m (S0A. R1 R 2 L 1 N B111. so -Y1 N-Bz 1 3 R (I) wherein R1 represents ureido, alkylcarbonylamino which may be optionally substituted and in which the alkyl moiety has 1-4 carbon atoms, alkenylcarbonylamino which may be optionally substituted and in which the alkenyl moiety has 2-4 carbon atoms or phenyl carbonyl amino which may be optionally substituted; R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1-4 carbon atoms which may be optionally substituted; B1 and B 2 each independently represents a phenylene group which may be optionally substituted or a naphthylene group which may be optionally substituted; m represents 1 or 2; n represents 0 or 1, providing m+n is 2 or 3; 2 Y1 and y2 represent -CH2CH2L, wherein L represents a group releasable by the action of alkali, a vinyl group, or -CH2CH20H, providing at least one of Y1 and Y 2 is not - CH2CH2OH; or a salt thereof; and 2) a second compound, which-is not identical to said first compound and which is selected from a group consisting of i) a compound represented by the formula (I), as described above; or a salt thereof; ii) a compound represented by the following general formula (SCH)m2 (S03He E3-S(:-Y3 N N-0, S(:-y4 wherein R represents ureido, alcarbonylamino which may be optionally substituted in which the alkyl moiety has 1-4 carbon atoms, alken arbonylamino which may be optionally substituted in which the alkenyl moiety has 2-4 carbon atoms or -,.-.vl carbonyl amino which may be optionally substituted; R5 and R 6 each independe'- y represents a hydrogen atom or an alkyl group havin1-4 carbon atoms which may be optionally substituted; WL B 3 and B 4 each independently represents a phenylene group which may be optionally substituted or a naphthylene group which may be optionally substituted; m2 represents 1 or 2; n2 represents 0 or 1, providing m2+n2 is 2 or 3; and Y 3 and y4 each independently represents -CH2CH2L, wherein L represents a group releasable by the action of alkali, or a vinyl group; or a salt thereof; iii) a compound represented by the following general formula (III):

R 8 1 -Y 5 N-B5-S02 N=N-Q-N--\ A N N R 7 cl (S03H)m3 (S03H).3 (III) wherein R 7 represents ureido, alkylcarbonylamino which may be optionally substituted and in which the alkyl moiety has 1-4 carbon atoms, alkenylcarbonylamino which may be optionally substituted and in which the alkenyl moiety has 2-4 carbon atoms or phenyl c arbonyl amino which may be optionally substituted; R 8 represents a hydrogen atom or an alkyl group having 14 carbon atoms which may be optionally substituted; B5 represents a phenylene group which may be optionally substituted or a naphthylene group which may be optionally substituted; - 4 m3 represents.1 or 2; n3 represents 0 or 1, providing m3+n3 is 2 or 3; and Y5 represents -CH2CH2L, wherein L represents a group releasable by the action of alkali, or a vinyl group; or a salt thereof.

Examples of the reactive dye composition of the present invention include a reactive dye composition which comprises at least two compounds selected from a group consisting of compounds of formula (I) and salts thereof; and a reactive dye composition---Which comprises at least one compound selected from a group consisting of compounds of formula (1) and salts thereof, and at least one compound selected from a group consisting of compounds of formula (II) compounds of formula (III)-nd salts thereof.

Examples of the reactivqrAdye composition which comprises at least two compounds selected from a group consisting of compounds of formula (I) and salts thereof include a reactive dye compositida which comprises a compound of formula (I), or a salt h- eof, wherein Y1 and y2 each independently represents ve-described CH2CH2L group, and a compound of formulw--4(1), or a salt thereof, wherein at least one of Y1 and YINW&Dresents a vin 1 group or - CH2CH2OH; which comprises a compound of 2) a reactive dye compositiqw_ formula (I), or a salt teof, wherein Y1 represents abovedescribed CH2CH2L foup and y2 represent a vinyl group, and a compound of to=ula (I), or a salt thereof, ALi wherein Y1 represents a vinyl group and y2 represents a vinyl group or - CH2CH2OH; 3) a reactive dye composition which comprises a compound of formula (I), or a salt thereof, wherein Y1 represents above-described -CH2CH2L group and Y2 represent a vinyl group, and a compound of formula (I), or a salt thereof, wherein Y1 represents above-described -CH2CH2L group and Y2 represents -CH2CH2OH; 4) a reactive dye composition which comprises a compound of formula (I), or a salt thereof, wherein Y1 and y2 represent a vinyl group, and a compound of formula (I), or a salt thereof, wherein Y1 represents above- described -CH2CH2L group or a vinyl group and y2 represents -CH2CH2OH; 5) a reactive dye composition which comprises a compound of formula (I), or a salt thereof, wherein Y1 represents above-described -CH2CH2L group and Y2 represents CH2CH20H, and a compound of formula (I), or a salt thereof, wherein Y1 represents a vinyl group and Y2 represents -CH2CH2OH; 6) a reactive dye composition which comprises at least two compounds of formula (I), or a salt thereof, in which Y1 in the compounds are the same groups each other and y2 in the compounds are the same as each other, but the substitution position of -S02-Y 1 to B' or -S02-Y 2 to B2 is different; and 7) a reactive dye composition which comprises at least two compounds of formula (I), or a salt thereof, in which Y1 in the compounds are the same as each other and y2 in the compounds are the same groups as each other, but B1 or B 2 6 in the compounds are different from each other.

When R' in f ormula (I), R4 in f ormula (II) or R 7 in formula (III) represents a substituted alkylcarbonylamino or a substituted alkenylcarbonylamino group, examples of the substituent of the alkyl or alkenyl in the group include sul f o, carboxy, halogen atoms and the like. When R' in formula (I), R 4 in formula (II) or R 7 in,Aormula (III) represents a substituted phenyl carbonylno, examples of the substituent of the phenyl group include -sulf o, carboxy, methyl, halogen atoms and the like.

Preferably, R', R 4 and R? represent ureido or an amino group substituted by acetyljz!-:propionyl, maleinyl, succinyl or benzoyl, and more prefer, R', R4 and R 7 represent ureido or an acetylamino group. --- When R 2 or R 3 in f 6rmul- (1), RS or R 6 in formula (II) or R8 in formula (III) reprets an alkyl, examples of the alkyl group include methylhyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butol-, 2-hydroxyethyl, 2hydroxypropyl, 3-hydroxyproW-1, 2-hydroxybutyl, 3- hydroxybutyl, 4-hydrox-ybut.yl-#--2,3-dihydroxypropyl, 3,4dihydroxybutyl, methoxymet ethoxymethyl, 2-methox-yethyl, 2-ethoxyethyl, 3-methoxyprOW;, 3-ethoxypropyl, 2hydroxy-3-methoxypropyl, ctomethyl, bromomethyl, 2chloroethyl, 2-bromoethyl, 3u-chloropropyl, 3bromopropyl, 4-chlorobutyl, 4-bromobutylwrboxymethyl, 2-carboxyethy 3-carboxypropyl, 4- carboxyll, 1,2-dicarboxyethyl, methoxycarbonylmethyl. etho-carbonylmethyl, 2 methoxycarbonylethyl, 2-eth#Wcarbonylethyl, 3- iii 1 ' methoxycarbonylpropyl,3-ethoxycarbonylpropyl, 4methoxycarbonylbutyl, 4ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3methycarbonyloxypropyl, 3- ethylcarbonyloxypropyl, 4methyl carbonyl oxybutyl, 4 -ethyl carbonyl oxybutyl, sulfonyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl and the like.

Preferably, R 2 and R 3 in formula (I), R 5 and R 6 in formula (II) and R8 in formula (III) each independently represent a hydrogen atom, a methyl group or an ethyl group.

When B' or B 2 in formula (I), B 3 or B4 in formula (II) or B 5 in formula (III) represents represent a substituted phenylene group or a substituted naphthylene group, examples of the substituent thereof include an alkyl group having 1 to 4 carbon atoms, a sulfoalkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group having 2 to 8 carbon atoms, a sulf o group and the like. Specific examples thereof include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, methoxy, ethoxy, iso-propoxy, 2- hydroxyethyl, methoxymethyl, ethoxymethyl, 2-metho>cyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, sulfo, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl and the like.

Pref erably, B1 or B 2 in formula (I), B 3 or B4 in formula (II) and B 5 in formula (III) each independently represent unsubstituted phenylene and phenylene substituted by methyl and/or methoxy. Among them, unsubstituted phenylene is more 8 preferable.

L in a -CH2CH2L group, as Y1, Y 2, Y 3, y4 or y5 is a group releasable by the action of alkali, and examples thereof includesulfate, thiosulfate, acetoxyandchloro. Amongthem, sulfate is preferable.

A compound present in the reactive dye composition of the present invention may be in the free acid form represented by the formula (I), (I1) or (III) or a salt thereof. However, preferably the compound is an alkaline -earth metal salt thereof, and particularly a lithium salt, a sodium salt or a potassium salt thereof is preferable.

The compound represented by the general formula (I) or (III), or a salt thereof, used in the present invention can be produced by a known method, for example, as described in JP-A-63-210170, JP-A-63-225664(=USP 4,873,321), or USP 4,378,313, etc.

The compound represented by the general formula (II), or a salt thereof, can be produced as described below, for example. 2-Aminonaphthaleni&--3,6, '8-trisulfonic acid is diazotized according to a us"l method in an aqueous medium, then, the diazotized compoubl is coupled with 1,3- diaminobenzene according to a usual method, to obtain the following compound (IV).

S03H i N=N-O_ M2 H03S S03H NH2 (M -7LC The resulting compound (IV) is ureidized by a cyanate, such as sodium cyanate, or acylated by an acyl halide or acid anhydride and the like, to obtain the following compound (V) S03H 1 N--M- 4 NH2 S03H H03S (V) wherein, R 4 has the same meaning as described above.

The resulting monoazo compound of formula (V), cyanuric chloride, a compound represented by the following general formula (VI) and a compound represented by the following general formula (VII):

(R 5) NH-B 3_ S 02- y3 (V I (R ') NH-B4- S 02- y4 (V I I) 6 3 4 3 wherein, R ' R ' B ' B ' Y and y4 have the same meanings as described above, can be condensed in any order, to obtain a reactive dye represented by the formula (II). The above-described ureidization and acylation reaction can be conducted at a temperature preferably from 0 to 70cC, more preferably from 10 to 40C while controlling pH at preferably from 4 to 10, more preferably from 6 to 8_ The above-described condensation reaction with unsubstituted cyanuric chloride can be conducted in an aqueous medium at a temperature from -10 to 50'C, preferably from 0 to 30t while controlling pH at pref erably f rom 1 to 10, more pref erably f rom 2 to 7. The condensation reaction with mono- substituted cyanuric chloride can be conducted in an aqueous medium at a temperature from 0 to 70 C, preferably from 10 to SO C while controlling pH at preferably from 2 to 9, more preferably from 5 to 8. The condensation reaction with di- substituted cyanuric chloride can be conducted in an aqueous medium at a temperature f rom 2 0 to 1000C, pref erably from 50 to 10 0 OC while controlling pH at pref erably f rom 0. 5 to 5, more pref erably f rom 1 to 4.

The thus prepared co d represented by the general formula (II) or a salt thereof is itself useful as a reactive dye for dyeing or printing a hydroxyl group or carbonamide group- containing fiber mattrial.

The reactive dye compoeition of the present invention may be obtained by mixing tba components simultaneously in production thereof, may beobtained by mixing components separately produced, or may be prepared by mixing components when dyeing is conducted. The form of the composition may be solid such as a powder, gr&nule or the like, or an aqueous solution. Two or more forxWy be mixed, if so desired.

When reactive dye compo"tion of the present invention comprises at least two comp@Mds selected from a group consisting of compounds of--la (I), the amount of the comiDound which is iDresent i -e second larqest amount is preferably about from 5 to Idilarts by weight per 100 parts by weight of the compound w h is present in the largest amount.

The total amount of the-lound of formula (I) wherein Y1 or y2 represents CH2CH20K preferably 2 0 parts by weight or less per 100 parts by we of the reactive dye composition.

When reactive dye composition of the present invention comprises one or more compounds represented by the formula (II), the total amount of the compounds represented by the formula (II) is preferably from 5 to 20 parts by weight based on 100 parts by weight of the total amount of the compounds represented by the formula (I).

When reactive dye composition of the present invention -comprises one or more compounds represented by the formula (111), the total amount of the compounds represented by the f ormula (III) is pref erably f rom 15 to 80 parts by weight based on 100 parts by weight of the total amount of the compounds represented by the formula (I).

The reactive dye composition of the present invention has reactivity with fiber, and can be used for dyeing and printing a f iber material containing a hydroxyl group and/ or an amide group. The f iber material may be used in the form of a fiber substrate, in the form of yarn, or in the form of a mixed yarn substrate. Examples of the fiber material containing a hydroxyl group include natural or synthetic hydroxyl groupcontaining materials, such as a cellulose fiber material, regenerated products thereof, polyvinyl alcohol and the like. Examples of the cellulose fiber material include cotton, other vegetable f iber, such as linen, hemp, jute, ramie fiber and the like. Examples of the regenerated cellulose f iber include viscose-stable, f ilament viscose and the like. Examples of the carbonamide group f iber material include synthetic and natural polyamide, polyurethane, particularly in the form of f iber, such as wool, other animal fur, silk, leather, polyamide6, 6, polyamide-6, polyamide-11 and polyamide-4.

The reactive dye composition of the present invention can be dyed or printed on the above-described f iber materials by a method according to phy:ical and chemical properties and conditions.

For example, when exImustion dyeing is conducted on cellulose fiber, dyeing canjD conducted at relatively lower 10 temperature in the presence Qf an acid bonding agent such as sodium carbonate, sodium tort-phosphate, sodium hydroxide and the like, optionally witji adding a neutral salt, such as sodium sulf ate or sodium chlwjde, and if necessary with using a dissolving assistant, a peation agent or a leveling agent 15 together. The neutral salt--'gI which promotes exhaustion of a dye may be added either betre or after intended dyeing temperature is obtained, ogg1ternatively, may be added in proportions.

when cellulose fiber iWA yed by a padding method, it can be padded at room temperatuWjl)r at a raised temperature and dried, then, fixed by stea- or drying.

A cellulose fiber c printed in single phase, for ex printed by a printing paste where the cellulose fiber is LL- pptaining sodium bicarbonate or other acid bonding agents,-- steamed at 95 to 160t, or it is printed in two phases#y example, where it is printed by a neutral or weak acidic nting paste, then, is allowed to pass through an alkaline I"h containing electrolytes, or - -i3 - AA subjected to over padding with padding liquid containing an alkaline electrolytes, followed by steaming or drying with heating.

As the printingpaste, for example, a glue or emulsifier such as sodium alginate or starch ether can be used, optionally together with a usual dispersing agent and/or printing aid such as urea.

The acid bonding agent suitable for fixing the reactive dye composition of the present invention on cellulose fiber is not restricted. Examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium formate, potassium carbonate, sodium primary, secondary or tertiary phosphate, sodium silicate, sodium trichloroacetate, and the like.

Synthetic or natural polyamide or polyurethane f iber can be dyed using the reactive dye composition of the present invention, for example, by a method in which exhaustion is conducted in an acidic to weak acidic dyeing bath under control of pH, then, pH of the dyeing bath is changed to neutral, or optionally alkaline. T he dyeing can be conducted at a temperature from 60 to 120t. Further, a leveling agent, such as a condensation product of cyanuric chloride with 3-times molar aminobenzenesulfonic acid or aminonaphthalenesulfonic acid, an addition product of strearylamine with ethylene oxide, and the like can be used in dyeing.

The reactive dye composition of the present invention can be mixed with other dyes if necessary f or obtaining desired hue in the range which does not deteriorate the feature of the present invention. The dye to be mixed is not restricted providing it is a reactive dye. Examples of the other dyes include dyes having, as a reactive group, at least one of a sulfatoethylsulfone group, vinylsulfone group, a monochlorotriazine group, a monofluorotriazine group, a mononicotinic acid triazine group, a dichlorotriazine group, a difluoromonochloropyrimidine group and a trichloropyrimidine group; dyes commercially available under trade name of Sumifix, Sumifix Supra, Remazol, Levafix, Procion, Cibacron, Basilen, Drimarene, Kayacion, Kayacelon React and the like; dyes described in JP-A-50-178, 56-9483, 56-15481, 56-118976, 56- 128380, 57-2365, 57-89679, 57-143360, 59-15451, 58-191755, 59-96174, 59- 161463, 60-6754, 60-123559, 60-229957, 60-260654, 61-126175, 61-155469, 61-225256, 63-77974, 63225664, 1-185370, 3-770, 5-117538, 5-247366 and 6-287463; dyes represented by C.I. Reactive Blue 19, C.I. Reactive Black 5; and the like.

The reactive dye compositions of the present invention have an excellent exhaustionproperty, dissolving property and leveling property and have a high fixing ratio, exhibit an excellent build-up property, and particularly have an excellent build-up property revealing a high f ixing ratio in the dark color range, in dyeing or printing treatment.

Further, the reactive dye compositions of the present invention do not tend to be influenced by temperature change in dyeing, changes in amount of a neutral salt, acid bonding agent, variation of dye bath ratio, and the like. As a result, a dyed product and a printed product obtained by using these - is - compositions have a stable quality and excellent various fastnesses.

The following Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof. In the Examples, percentages and parts are by weight unless otherwise stated.

Example 1 parts of a compound, the free acid thereof 10 represented by the structural formula (l):

HN-I S03H N--- N=N-- N-\\ /N H S02C2H40SO3H H03S NHCONH2 HN-G-S02C2HASO3H S03H (1) and 15 parts of a compound, the free acid thereof is represented by the structural formula (2):

HN S03H N--- N=N N--\ N H A H03S S03H N- S02C2H40SO3H NHCONH2 HN-G-SOP2H40SO3H is (2) were mixed sufficiently to obtain a reactive dye composition. 0. 1, 0. 3 and 0 - 6 parts of this reactive dye composition were respectively dissolved in 200 parts of water, 6 parts of sodium sulfate and 10 parts of cotton were added thereto. Each of 16 - the resulting mixtures were heated to 70 - C, and 4 parts of sodium carbonate was added thereto, and then dyeing was conducted for 1 hour. Thereafter, washing, soaping, washing and drying were conducted sequentially. In the washing and soaping, the colored extentof a dyed drain was low. All of the resulting dyed materials were level dark reddish yellow, and the dyed product obtained using 0. 6 parts of the reactive dye composition was fully dark as compared-with the dyed product obtained using 0.3 parts of the reactive dye composition, and the dyed p,uct obtained using 0.3 parts of the reactive dye composition was fully dark as compared with the dyed product obtained using 0. 1 part of the reactive dye composition. Therefore, the reactive dye composition used has excellent build-up property. In dyeing processing, the exhaustion property, soliffiility and leveling property were excellent and a high fixing ratio was exhibited. Various fastnesses of the resulting dyed products, light fastness, perspiration fastness, perspiration light fastness, chlorine fastness, acid-hydrolysis:tstness, alkali-fastness, washing fastness and peroxi -washing fastness, were excellent.

Example 2

The 1 same dyeing proced- is conducted as in Example 1 except that the amount of i-um sulfate is changed from 6 parts in Example 1 to 4 pai. Each of the resulting dyed products has the same qualitS as that of the dye product obtained in Example 1.

----17 - Wil Example 3 The same dyeing procedure is conducted as in Examples 1 and 2 except that the dyeing temperature is changed from 5 70r in Examples 1 and 2 to 601C. Each of the resulting dyed products has the same quality as that of the dye product obtained in Example 1 and 2.

Example 4

A color glue having the following formulation is produced using the reactive dye composition obtained in Example 1.

Color glue composition Reactive dye composition 5 parts Urea 5 parts Sodium alginate (5%) base glue 50 parts Hot water 25 parts Sodium bicarbonate 2 parts Balance (water) 13 parts Total 100 parts This color glue is printed on mercerized cotton broad, dried intermediately. Then, it is subjected to steaming at 100C for 5 minutes, and subjected to washing with hot water, soaping, washing with hot water, and drying. The resulting printed products exhibits a level dark reddish yellow and has_ an excellent build-up property and the general fastness and storage stability thereof are also excellent.

Example 5

18 parts of the reactive dye composition obtained in Example 1 is dissolved in hot water, and the mixture is cooled to 250C. To this dyeing solution are added 15 parts of a 32. 5 % aqueous sodium hydroxide solution and 150 parts of a water glass having 50 Baume degree. Further, water is added at 25 0 C to make the total amount of 1000 parts, and then immediately, cotton textile is padded using this solution as a padding solution. The padded cotton textile is wound up, and sealed up in a polyethylene film, and left for 20 hours at a room temperature of 251C. Then it is washed with a normal method, and dried. The resulting.dyed product exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storage stability thereof are also excellent.

Example 6 parts of the reactive dye composition obtained in Example 1 is dissolved in hot water, and the mixture is cooled to 25rJ. To this dyeing soliiltion are added 1 parts of sodium alginate, 10 parts of sodium Methanitrobenzenesulf onate and parts of sodium bicarbonate. Further, water is added at 25C to make the total amouikt,,.of 1000 parts, and then immediately, cotton textile is padded using this solution as a padding solution. The pad cotton textile is dried at 1200C for 2 minutes, then steamed for 5 minutes at 100'C, to f ix the dye. The resulting d product exhibits a level dark reddish yellow and has an exceftlent build-up property and the general fastness and storag6Stability thereof are also excellent.

Example 7 parts of a compound, the free acid thereof represented by the structural formula (3):

SO3H N- H N-q N=N N-- N H N A S02C2H40SO3H 1 -P- -- --q NHCOCH3 HN S03H S02C2H40SO3H (3) is parts of a compound, the free acid thereof is represented by the structural formula (4):

HN-1 S03H N-- N=N -N- N -p H N- NHCOCH3 HN-IC S03H S02CH=CH2 SO2C2H40SO3H (4) and 5 parts of a compound, the free acid thereof is represented by the structural formula (5):

SO3H N- H N-q N-N-Q1 N S02C2H40H k- NHCOCH3 HN-q S03H S02C2H40SO3H (5) are mixed sufficiently to obtain a reactive dye composition.

0. 1, 0. 3 and 0. 6 parts of this reactive dye composition are respectively dissolved in 200 parts of water, 6 parts of sodium sulfate and 10 parts of cotton are added thereto. Each of the resulting mixtures is heat ed to 700C, and 4 parts of sodium carbonate is added thereto, and then dyeing is conducted for 1 hour. Thereafter, washing, soaping, washing and drying are 5 conducted sequentially. In the washing and soaping, the colored extent of a dyed drain. is low. All of the resulting dyed material show a level da-rk neutral yellow, and the dyed product obtained using 0.6 parts of the reactive dye composition is fully dark aacompared with the dyed product obtained using 0. 3 parts of the reactive dye composition, and the dyed product obtained using 0. 3 parts of the reactive dye composition is fully dark as compared. with the dyed product obtained using 0.1 part of the reactive dye composition. Therefore, the reactive dye_composition used has excellent build-up property. In dyeizM processing, the exhaustion property, solubility and level-ing property are excellent and high fixing ratio is exhibitCl.. Various fastnesses of the resulting dyed products, lioht fastness, perspiration fastness, perspiration ligbi"astness, chlorine fastness, acid-hydrolysis fastness, all--li-fastness, washing fastness and peroxide washing fastn:, are excellent.

Example 8 The same dyeing procedu are conducted as in Examples W.

1-6 except that the reactive dye composition obtained in Example 7 is used in place W-the composition obtained in Example 1. Each of the resulting dyed products has the same quality as that of the dye 10duct obtained in Example 7.

- 211 - im The same dyeing and printing procedures as in Examples 1-6 are conducted except the reactive dye composition used in Example 1, which comprises compounds represented by the formulae (1) and (2), is changed to the reactive dye composition which comprises compounds shown in column 2 in tables 1 to 11, and the formulation is changed to those shown in column 3 in tables 1 to 11. Each of the resulting dyed or printed products exhibits a hue as shown in column 4 in tables 1 to 11 on cotton, and has the same quality as that 10 of the dyed products obtained in Examples 1-6.

Table 1 2 3 [parts] HN-q 100 N 1-N =N-H N-- S02C1H4OSO,H HO,52 SOH NHCONH2 HN-RO

OS H H -C 40 SO3H N_.< N=N-Q-N- N:

H N- S02CH=CH2 reddish H03s SO3H WCONH2 H- yellow S02CH=CH2 SO3H N S02CH=CH2 N- H03S S03H NHCONH2 HN-I S02C2H40H 22 Table 2

2 3 [parts] SO3H SO'c^0SO,H 100 N-N-P- H N_ HQ,S N CONH S0AH40SOH SO,H S03H N-N- S02MCH2 so reddish H03S"I:::5Y\ MCONHI2 SO2C2H40SO3H yellow SO3H SO3H SO2C2H40SO3H 5 N-N H03Sb NPHCOM, SO2C2H40H SO3H SO3H 100 Sa 502C2NOSO3H H035J6d-. TNHCONH2 SO2C2H40SO3H D3H SOH N-N 20 reddish b &H S021C2H40S03H HC),s NHC0t^ SO2CW-Cl- SO,H yellow SO3H H SO2C2H40H H03s NHCONN2 02C2H40SO3H iS7-. Pm scv SOH -L - W AW A -- Table 3

2 3 [parts] 4 HN 1 0 0 SO3H N-- ---'% N-q SO2C^0503H SO H03S WCONH2 HN-C)2CH=CH2 reddish SO3H N- H N-( yellow 1 0 N-N N S02CH=CH, -H N-- H0,s, SM WCONH2 HW-G- SO2CH=CH2 HN 1 0 0 SO3H N-- -1 N=N-N-- N SO2H40SO3H H N- HN HN S02C2H40SO3H 67 1 -0- S03H OC-0 HN SO3H N-- _q N=N N- -Q- H NSO2C2H40SO3H neutral HN HN 61 1 -C--S02CH=CH2 yel low 03H OC-0 HN SO3H N---- N-q N=N -N-- SOAH40SO3H -p H k- HN HN 02C2H40H 67 1 -G-S H OC 24 Table 4

2 3 4 [parts] 6 SO3H 1 0 0 N=N--,:-q SO2C2H,OSO3H HO,SJ6d NHCONH2 - ' 'j S03H Cj2Hs SO2C2H40SO3H 6 0 SO,H H=H 502C2H40SO3H reddish H03Sbd SO3H NHCONH yellow L2H5 S02CH--CH2 N=N- SO2C2H40SO3H H03S2 WCONN& SO3H 7, tHqs -1 S02C2H40H Table 5

2 3 4 [parts] 7 HN OCH, 1 0 0 S03H N=N N N- -)- H S02C2H40SO3H SO3H NHCOCH3 HN-C 02C2H40SO3H neutral HN-(:-OCH3 5 yellow 503H N- N N-- N H NS02C2H40SO3H NHCOCH3 HN-C SO3H S02CH=CH2 H3C0 8 H 1 0 0 N=4+ N- N-- N. SOC2H40SC)3H H N-( H03S SOH NHCONK2 HN-q 02C2H40SO3H H3C 2 0 HN SO,H N S02C2H10503H redd i sh HO's -,50,CH--CH2 yel low 0 H-CO H SO H H N S02C^OSOH HCS -5 SOSH MHCONH2 H 02C2H40H 26 Table 6

2 3 4 [parts] H -OCH3 1 0 0 S03H N- N=N SO2C2H40SO3H -H H, NHCOCH3 S03H 02C2H40SO3H ineutral OCH3 yellow S S03H N=N SO2C.2H40SO3H WCOCFHh3 S03H S02CH=CH2 1 0 0 SO2C^OSO3H HO,SJ5 SO,H NHCONb II-RO2C2H40SO3H 7. 1 0 SO3H N redd i sh H so,cH,OSO,H H HNCOMHZ yel low scH 502C&4=CH2 1 0 SO,H SO2C2H40SO3H HO's SOSH MRC0t^ SO40H - 117 4, Table 7

2 3 4 [parts] HN 1 0 0 S03H N--- N N-- N-q W-Q- H N- S02C2H40SO3H NHCOCH3 HN-C S03H 02C2H40SO3H neutral HN-( SO3H N--- 4 0 yellow N=N N-- N -)- H NS02CH=CH2 NHCOCH3 HN-I S03H S02CH=CH2 H3C0 12 1 0 0 H SO2C2NOSOH N-( H CH3 NHCOCH3 N HO,S/C77 1 S(),H qlSO2C2H4OSOH H3C0 2 0 H -50SOH N- 14 N W--H redd i sh N- CH' H03 NHCOC N ye I low S03N iR SO2CW-Cl2 H3C0 1 0 H SO2C2H40SO3H N NHCOCH, Ho' SO3H iqlSO2C2H40H 28 Table 8

2 3 4 [parts] 13 SO,H HN-q 1 0 0 N-< I 7N H SO,C2H40SO3H HO,Sbd S03H NHCONH2 Hk-R02C2H40SO3H SOjH 1 0 0 N=N-P- H SO2CH--CH2 reddish H NHCONN, ye 1 low SO2C2H40SO3H 1 0 N=N_.Q S02CH--CH2 NWO" H H03Sis SO3H N-C S02CH=CH2 14 SCKH S%CFr-CH2 1 0 0 H03SJ6:::k ONH2 tS02C2H40SO1H 5OsH S%H S02CH-CH 2 4 0 redd i sh O,S, MCONHa H _^ NHCON% SO2CH=CH2 ye 1 low SO3H SO3H SO2CH=CH2 5 H NHCON% SO2C2HOH S%H - -29 - Table 9

2 3 [parts] SO3H HN 1 0 0 =N S02C2H40SO3H -)- H N-- H03SJ6 NHCONH2 HN-IC SO3H 02C2H40SO3H 1 redd i sh HN 1 0 ye 1 low SO3H N=N-H N- N-q -Jlk S02C2H40SO3H HO SO3H NHCONH2 HN-q S02C2H40H 16 S03H HN-G-S02C2HASO3H 1 0 0 N-N -p H 67 NHCOCH3 H4- S02CH=CH2 S03H neutral HN-G-S02C2H40H 1 5 yellow S03H N - N---M-P-N-- N H N-- NHCOCH3 Hk-(:--S02CH::CH2 03H 17 H SC)2CW-CR21 0 0 H H03S SOSH NHCONH2 HN-CSCCW-CF]2 reddish H S02MCH2 5 yellow SO3H H%S,- S%H MHCO" H+ 02C2H,OH Table 10

2 3 4 [parts] 18 503H H SO2C2H40SO3H 1 0 0 N=N HO,Sbdk NHCONH2 S03H S02C2H40503H 502C2H40SO3H 1 5 SO3H H NHCON1H2 H03sb H S03H SO2CH-CH2 SO3H 502CH=Cf.

N-N redd i sh H0,s, INHCONH2 SO,H yellow SO2CH40SO3H SO3H SO2C2H40SO3H 5 N=N 2 H03S-6 NHCONHI, SO,H S0AH40H Ak S02C2H40H SQ,H N H03S-J NHCONK2 S" SO2C2H40SO3H fll- --_:i A - W Table 11

2 3 [parts] HN-G-SO2C2HASO3H 1 0 0 19 SO H N-( HO,S -6 SOAH40SCH HN---SO2C2H40SO3H 5 0 S03H N--- N-N-PN N H H03Sb. NHCONH2 HN-G-S02CH--CH2 SO3H SO3H HN-G-S02CH--CH2 5 N H N-' H03S WC0NH2 H SO2CH--CH2 SO3H SO3H H SO2C22040SO3H 5 N--- N- N bc"-p- H N- H03S 503H NHCONH2 HN-G-SO2C2H40H H SO2CFi=C 5 SO3H M==r-G N N-- H03 s HW-G-SO2C2H40H 4 reddi sh ye 1 low Example 9 parts of a compound, the free acid thereof is represented by the structural formula (6) HN SO3H N-- _q N= H N S02C2H40SO3H H03S S03H NHCONH2 n HN-q S02C2H40SO3H (6) and 80 parts of a compound, the free acid thereof i 32 represented by the structural formula (l):

HN S03H N--- _q N=N N-- N S02C2H40SO3H 1-P- H N- H03S S03H NHCON112 H",,.,-,/SO2C2H40SO3H (1) are mixed sufficiently to obtain a reactive dye composition.

0. 1, 0. 3 and 0. 6 parts of this reactive dye composition are respectively dissolved in 200 parts of water, 6 parts of sodium sulfate and 10 parts of cotton are added thereto. Each of the resulting mixture is heated to 701C, and 4 parts of sodium carbonate is added thereto, and then dyeing is conducted for 1 hour. Thereafter, washing, soaping, washing and drying are conducted sequentially. In the washing and soaping, the colored extent of a dyed drain is low. All of the resulting dyed materials show a level dark reddish yellow, and the dyed product obtained using 0.6 parts of the reactive dye composition is fully dark as compared with the dyed product obtained using 0. 3 parts of tub reactive dye composition, and W the dyed product obtained usthr 0. 3 parts of the reactive dye composition is fully dark as--Dmpared with the dyed product obtained using 0.1 part of reactive dye composition.

C Therefore, the reactive dye tosition used has excellent build-up property.

In dyeizm-"rocessincr, the exhaustion property, solubility and leveUng property are excellent and high fixing ratio is exhibitd.

Various fastnesses of the resulting dyed products, lig fastness, perspiration fastness, perspiration lightCastness, chlorine fastness, _m ii:- - - f KM-L acid-hydrolysis fastness, alkali- fastness, washing fastness and peroxide washing fastness, are excellent.

Example 10

The same dyeing procedure is conducted as in Example 9 except that the amount of sodium sulfate is changed from 6 parts in Example 9 to 4 parts. Each of the resulting dyed products has the same quality as that of the dye product obtained in Example 9.

Example 11

The same dyeing procedure is conducted as in Examples 9 and 10 except that the dyeing temperature is changed from 701C in Examples 9 and 10 to 600C Each of the resulting dyed products has the same quality as that of the dye product obtained in Example 9 and 10.

Example 12 A Color glue having the following formulation is produced 20 using the reactive dye composition obtained in Example 9.

Color glue composition Reactive dye composition 5 parts Urea 5 parts Sodium alginate (5%) base glue 50 parts Hot water 25 parts Sodium bicarbonate Balance (water) Total 34 - 2 parts 13 parts 100 parts The color glue is printed on mercerized cotton broad, dried intermediately. Then, it is subjected to steaming at 100C for 5 minutes, and subjected to washing with hot water, soaping, washing with hot water, and drying. The resulting printed product exhibits a level dark reddish yellow and has an excellent build-up propeX.ty and the general fastness and storage stability thereof ake also excellent.

Example 13

30 parts of the reactive dye composition obtained in Example 9 is dissolved in hot,^-ter, and the mixture is cooled to 250C. To this dyeing solutIon are added 15 parts of a 32.5 % aqueous sodium hydroxide solution and 150 parts of a water glass having 50 Baume degree., -. Further, water is added at 25C 15. to make the total amount of IMO parts, and then immediately, cotton textile is padded us this solution as a padding solution. The padded cotton textile is wound up, and sealed up in a polyethylene film, left for 20 hours at a room temperature of 251C. Then i washed with a normal method, and dried. The resulting dproduct exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storag stability thereof are also excellent.

Example 14 parts of the reactilw dye composition obtained in 27 'W_ Example 9 is dissolved in hot tMter, and the mixture is cooled to 259C. To this dyeing solution are added 1 part of sodium alginate, 10 parts of sodium methanitrobenzenesulf onate and 20 parts of sodium bicarbonate. Further, water is added at 250C to make the total amount of 1000 parts, and then immediately, cotton textile is padded using this solution as a padding solution. The padded cotton textile is dried at 1200C for 2 minutes, then steamed for 5 minutes at 1000C, to fixthedye. The resulting dyed product exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storage stability thereof are also excellent.

The same dyeing and printing procedures as in Examples 9 and 14 are conducted except that the reactive dye composition used in Example 9, which comprises compounds represented by the formulae (6) and (1), is changed to the reactive dye composition which comprises compounds shown in column 2 in tables 12 to 14, and the formulation is changed to those shown in column 3 in tables 12 to 14. Each of the resulting dyed or printed products exhibits a hue as shown in column 4 in tables 12 to 14 on cotton, and has the same quality as that of the dyed products obtained in Examples 9 to 14.

36 Table 12

2 3 4 [parts] HW-G-S040SOH 7 0 NHCOChh HW-0-50tqom neutral yel low 3 0 NHCOCIb HW-G- -01q f 2 soH 8 0 N h%C soH NHCONfh -q - redd i sh yel low m-K 2 0 H.

H3C0 3 5 5 HCb reddish 4 5 yel I ow m A -W Tab 1 e 13 2 3 4 [parts] SOyH n.-SO2C2H40SO3H 9 0 H03SJ5k i--0-So2C2H40503H redd i sh SO,H M--0-S02c2H,OSOH A 1 0 ye 1 low C.

H03S SOH HCONH2 soc^oscH 's C4r> H SCKCH--CH, 7 0 N-N-H WCOCFh W-G-SO2C2H40SO3H SO3H neutral HN-C)-SO2CF=Chh 3 0 yel low N -N-P HW CS 1 WCOCFS HN--q 50,C^OSOH 38 - Tab 1 e 14 2 3 4 [parts] H3C0 6 H 4 5 N N H WCOCFh W-C)-S4DH H, 3 M 5 neutral H MCOCFh H yel low HM-1=,0503H N-( 2 0 N N-M-P 'HlIN- S%H NHCOCFh H4-q SaAl N-( 3 0 H-J% N H NHCCO>NMb. H 03H 0SO3H 3 5 redd i sh yel I ow 3 5 H Example 15 parts of a compouncT, the free acid thereof is represented by the structu3aY-formula S03H (1):

N=N N H 02C2H40SO3H NHCONH2 S02C2H40SO3H H03S S03H 1 2 (1) and 10 parts of a compound, the free acid thereof is represented by the structural formula (7):

S03H N=N-IP-NHCONH2 H03S HN N H S03H y l-N-1r,',,-rso2C2H40SO3H N N HN S02C2H40SO3H (7) are mixed sufficiently to obtain a reactive dye composition. 0.1, 0.3 and 0.6 parts of this reactive dye composition are respectively dissolved in 200 parts of water, 6 parts of sodium sulfate and 10 parts of cotton are added thereto. Each of the resulting mixture is heated to 70'C, and 4 parts of sodium carbonate is added thereto, and then dyeing is conducted for 1 hour. Thereafter, washing, soaping, washing and drying are conducted sequentially. In the washing and soaping, the colored extent of a dyed drain is low. All of the resulting dyed material show a level dark reddish yellow, and the dyed product obtained using 0.6 parts of the reactive dye composition is fully dark as compared with the dyed product obtained using 0. 3 parts of the reactive dye composition, and the dyed product obtained using 0. 3 parts of the reactive dye composition is fully dark as compared with the dyed product obtained using 0.1 part of the reactive dye composition. Therefore, the reactive dye composition used has an excellent build-up property. In dyeing processing, the exhaustion property, solubility and leveling property are excellent and high fixing ratio is exhibited. Various fastnesses of the resulting dyed products, light fastness, perspiration fastness, perspiration light fastness, chlorine fastness, acid-hydrolysis fastness, alkali- fastness, washing fastness and peroxide washing fastness, are excellent.

Example 16

The same dyeing procedure is conducted as in Example 15 except that the amount of sodium sulfate is changed from 6 parts in Example 15 to 4 parts. Each of the resulting dyed products has the same quality as that of the dye product obtained in Example 15.

Example 17

The same dyeing procedure is conducted as.in Examples 15 and 16 except that the dyeing temperature is changed from 70t in Examples 15 and 16 to 601C. Each of the resulting dyed products has the same quali ty as that of the dye product obtained in Example 15 and,l:.

Example 18

A color glue having the fowing formulation is produced using the reactive dye compo&-ion obtained in Example 15.

Color glue composition Reactive dye composition Urea Sodium alginate (5%) bae glue - 417---_- parts 5 parts 50 parts Hot water 25 parts Sodium bicarbonate 2 parts Balance (water) 13 parts Total 100 parts The color glue is printed on mercerized cotton broad, dried intermediately, then, is subjected to steaming at 10OCC f or 5 minutes, and subjected to washing with hot water, soaping, washing with hot water, and drying. The resulting printed products exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storage stability thereof are also excellent.

Example 19 parts of the reactive dye composition obtained in Example 15 is dissolved in hot water, and the mi xture is cooled to 25cC. To this dyeing solution are added 15 parts of a 32.5 % aqueous sodium hydroxide solution and 150 parts of a water glass having 50 Baume degree. Further, water is added at 25C to make the total amount of 1000 parts, and then immediately, cotton textile is padded using this solution as a padding solution. The padded cotton textile is wound up, and sealed up in a polyethylene film, and left for 20 hours at a room temperature of 25t. Then it is washed with a normal method, and dried. The resulting dyed product exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storage stability thereof are also excellent.

42 Example 20 parts of the reactive dye composition obtained in Example 15 is dissolved in hot water, and the mixture is cooled to 251C. To this dyeing solution are added 1 part of sodium 5 alginate, 10 parts of sodium methanitrobenzenesulf onate and 20 parts of sodium bicarbonate. Further, water is added at 25t to make the total amount of 1000 parts, and then immediately, cotton textile,s padded using this solution as a padding solution. The padded cotton textile is dried at 1200C for 2 minutes, then steamed for 5 minutes at 1000C, to fixthedye. The resulting dyed product exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storagti stability thereof are also excellent.

The same dyeing and priZting procedures as in Examples and 20 are conducted except that the reactive dye composition used in Exampl 5, which comprises compounds represented by the formulae and (7), is changed to the reactive dye composition whio comprises compounds shown.in column 2 in tables 15 to 17: the formulation is changed to those shown in column 3 _ables 15 to 17. Each of the resulting dyed or printed p,- cts exhibits a hue as shown in column 4 in tables 15 to on cotton, and has the same quality as that of the dyed products obtained in Examples 15 to 20.

Table 15 t Awl 2 3 4 [parts] SO,H HN 1 0 0 H so,cH,OSCKH HO's SO,H NHCONH, H-Q SO,H scCH,OSO,H reddish HC3sb:::x H-M- NHCONH, 1 0 ye 1 low SOSH HN N H SO,C,H,OSO,H Y 'I'l-N N Y N -0- HN -(:-SO,C-.MOSO,H 2 1 SO3H HN-G-SO2C2H40503H 10 0 H 1 H,16:kN NHCONH, H SO2C2H40SO3H 503H SO3H reddish 6 NHCONH2 5 HO,S X SO3H HN_f N_.H yellow N Y N fq-(::\S02CH,OSOH HN.aSO2C,H40SO3H 3 SO3H HN-G-SO2CH:CH2 1 0 0 N-( 50,H NHCONH2 HW-SC2C2H40SC)3H SO3H N--N- HCONH, 1 5 redd i sh H HN N H - yel I ow SOH -f IIII-N-Q Y SO2CH-CV12 HN -IC:-SO2C2H40SO3H 44 Tab 1 e 16 2 3 [parts] SOH 1 0 0 N=N-j H 02C2H,OSO3H NHCOCH3 02CH4OSO,H neutral N=N-1 H06" 1 0 H yellow SO3H I-N S02C2H40SO3H N N -0 Y HN-IC2H,OSO3H 1 0 0 N-- H' 02C2H40SO3H HN SO,H oc 2C2H40SO3H S03H neutral N=N- HCO,0 1 5 yellow HNyN, SO3H -S02C2H40SO3H N Y N tic HN ID-S03H - 1 W AW 451: - A&Wii di Table 17

2 3 [parts] 6 1 SO HN-Q 1 0 0 ,H N- N= N-- N 0,C^OSOH H N- HO,Si6dr M- IHN-QSO,C^OSO,H MCOC2H4CO,H SO,H neutral N- NHCOC2H4CO2H H yel I ow HO,S6Y IIN _f N %r- N-[::-SO:)IC2H4OSOH N Y N HN -1:)-SOrH40SC,H HN-O-SCC,2H,,OSO3H 1 0 0 N=N-RN-Z&-N H k- i HN; SO3H WCO.CHi-CHCO2H S02C2H,OSO,H N=N- HCOCH--CHCO2H 2 0 neutral H ye 1 low SO3H HN 'v N%rN-CL N Y N S02C2H40SO3H HN ----k-S02C2H40SO3H Example 21 parts of a compound, the free acid thereof is represented by the structural formula (1) H N= N_N_M N H - SOHOSO3H N- H03 SJ SO3H NHCONI2 HW-S02C2H40SO3H (1) and 15 parts of a compound, the free acid thereof is 46 represented by the structural formula (8):

HN SO3H N------C N=N N- N 1 1 -Q- H N-( H03S S03H NHCONK2 cl S02C2H40SO3H (8) are mixed sufficiently to obtain a reactive dye composition. 0.1, 0.3 and 0.6 parts of this reactive dye composition are respectively di ss olved in 200 parts of water, 6 parts of sodium sulfate and 10 parts of cotton are added thereto. Each of the resulting mixture is heated to 700C, and 4 parts of sodium carbonate is added thereto, and then dyeing is conducted for 1 hour. Thereafter, washing #psoaping, washing and drying are conducted sequentially. In 'the washing and soaping, the colored extent of a dyed drain is low. Any of the resulting dyed material show a level dark reddish yellow, and the dyed product obtained using 0.6 parts of the reactive dye composition is fully dark as compared with the dyed product obtained using 0. 3 parts of thezeactive dye composition, and the dyed product obtained usM--,.0. 3 parts of the reactive dye composition is fully dark as-,--ared with the dyed product 2-K obtained using 0.1 part of --'--freactive dye composition.

Therefore, the reactive dye c AMP osition used has an excellent p build-up property.

In dye-inii--processing, the exhaustion property, solubility and lev a high fixing ratio is exhibi itng property are excellent and 7 Various fastnesses of the resulting dyed products, ligM fastness, perspiration fastness, perspiration light7fastness, chlorine fastness, Iacid-hydrolysis fastness, alkali- fastness, washing fastness and peroxide washing fastness, are excellent.

Example 22

The same dyeing procedure is conducted as in Example 21 except that the amount of sodium sulfate is changed from 6 parts in Example 15 to 4 parts. Each of the resulting dyed products has the same quality as that of the dye product obtained in Example 21.

Example 23

The same dyeing procedure is conducted as in Examples 21 and 22 except that the dyeing temperature is changed from 70r. in Examples 21 and 22 to 60t. Each of the resulting dyed products has the same quality as that of the dye product obtained in Example 21 and 22- Example 24

A color glue having the following formulation is produced 20 using the reactive dye composition obtained in Example 21. Color glue composition Reactive dye composition Urea Sodium alginate (5%) base glue Hot water Sodium bicarbonate Balance (water) Total 48 parts 2 parts 13 parts 100 parts The color glue is printed on mercerized cotton broad, dried intermediately. Then, it is subjected to steaming at 1000C for 5 minutes, and subjected to washing with hot water soaping, washing with hot water, and drying. The resulting 5 printed products exhibits a level dark reddish yellow and has an excellent build- up property and the general fastness and storage stability thereof are also excellent.

Example 25

30 parts of the reactive dye composition obtained in Example 21 is dissolved in hot water, and the mixture is cooled to 251C. To this dyeing solution are added 15 parts of a 32.5 % aqueous sodium hydroxide solution and 150 parts of a water glass having 50 Baume degree.- Further, water is added at 25 - C to make the total amount of 1M parts, and then immediately, cotton textile is padded using this solution as a padding solution. The padded cotton textile is wound up, and sealed up in a polyethylene film, and left for 20 hours at a room temperature of 251C. Then iC--io washed with a normal method, and dried. The resulting dproduct exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storage stability thereof are also excellent.

Example 26 parts of the reactive dye composition obtained in Example 21 is dissolved in hot water, and the mixture is cooled to 251C. To this dyeing solution are added 1 part of sodium - 49 - alginate, 10 parts of sodium methanitrobenzenesulf onate and 20 parts of sodium bicarbonate. Further, water is added at 251C to make the total amount of 1000 parts, and then immediately, cotton textile is padded using this solution as a padding solution. The padded cotton textile is dried at 1200C for 2 minutes, then steamed for 5 minutes at 1000C, to fixthedye. The resulting dyed product exhibits a level dark reddish yellow and has an excellent build-up property and the general fastness and storage stability thereof are also excellent.

The same dyeing and printing procedures as in Examples 21-26 are conducted except that the reactive dye composition used in Example 21, which comprises compounds represented by the formulae (1) and (8), is changed to the reactive dye composition which comprises compounds shown in column 2 in tables 18 to 21, and the formulation is changed to those shown in coluinn 3 in tables 18 to 21. Each of the resulting dyed or printed products exhibits a hue as shown in column 4 in tables 18 to 21 on cotton, and has the same quality as that of the dyed products obtained in Examples 21-26.

so Tab 1 e 18 2 3 4 [parts] 6 5 H 50AH40SO,H H H03Sis 7NHCONH2 S0AH,0SOH SO,H 3H N S0AH,0SO,H 2 5 N-N redd i sh HO,S 6 SO,,H NHCONil, ye 1 low III SOSH 1 0 H SO2C2H4OSO,H HOS,6 SO,H N H C.0 N HH.2 2 1 S03H 7 0 N=N N M-Zi 50AH40S%H H 4- 61 NHCOCH3 HN-O-WAH40SO,H SO3H neutral HN- OP2H40SO.,H 3 0 yellow S03H N-< NHCOCH3 cl 03H 3 1 3 8 0 2C2H40SOSH 2C-H SOIC2HIOSO1H WHCONH2 7SOIC' H-- HO,S J5 2:2 SO,H redd i sh SO,H H3 2 0 ye I low N S02C2NOSO,H WCONH2 HO,S Table 19

2 3 4 [parts] CH3 1 - I N 6 0 N-- ORCH3 SO:C2H40SO3H NHCONH2 H SO2C2H40SO3H SCH 1.3 neutral r-H3 N-q 4 0 ye 1 low N=N N-- N SO,C^OSO,H -)- H N-< NHCONH, cl 1 H -scC2H40SO3H 6 0 WCOCF6 HW-C.-socHIOSO3H SO,H neutral N 4 0 yellow -N N-q H 1- SO,C^OSO,H k- NHCOCH, cl 52 Table 20

2 3 4 [parts] 6 1 SOH 5 5 SG.J4 CON redd i sh C2M40503H SOH 4 5 yel low 7 1 so H 6 0 SOANOSOH H03s-j NHCONH2 S0AH,Oso,H 7 redd i sh :50,H schH 4 0 yel low H0.5 50,H NHCONfb H H-CH2 7 5 NHCOC[h Hi#- H SO,H neutral 2 5 ye 1 low 0503H NHCOCH, SOH 9 H2 6 0 CC#12 SOH 2 0 redd i sh bc MMICOMb ye 1 low HO.S/ 502,H 2 0 so!kc[CCH2 WC Hos S" W,

Claims

1. A reactive dye composition, which comprises 1) a first compound which is i) a compound of formula (I):

R 2 1 - 1 N B \ S02-Y 1 H N- N=N-9-N-( N N -// 2 2'SO2-Y RI N-B (SOArn (S0An 1 3 R (I) wherein R' represents ureido, alkylcarbonylamino which may be optionally substituted and in which the alkyl moiety has 1-4 carbon atoms, alkenylcarbonylamino which may be optionally substituted and in which the alkenyl moiety has 2-4 carbon atoms or phenylcarbonylamino which may be optionally substituted; R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1-4 carbon atoms which may be optionally substituted; B' and B 2 each independently represent a phenylene group which may be optionally substituted or a naphthylene group which may be optionally substituted; m represents 1 or 2; n represents 0 or 1, providing m+n is 2 or 3; and Y1 and y2 each independently represent -CH2CH2L, wherein L represents a group releasable by the action of alkali, a vinyl group, or CH2CH20H, providing at least one of Y1 54- and y2 is not -CH2CH2OH; or a salt thereof; and 2) a second compound, which is not identical to said first compound and which is i) a compound of formula (I), as hereinbefore defined; or a salt thereof; ii) a compound of formula (II):

4 _hR F N 1 HW-Cl B 3 -S(:-Y3 (SOM1n2 (S(3H112 1 N N N-B4-SC-Y4 16 R wherein R 4 represents ureido, alkylcarbonylamino which may be optionally substituted and in which the alkyl moiety has 1-4 carbon atoms, alkenylcarbonylamino which may be optionally substituted and in which the alkenyl moiety has 2-4 carbon atoms or phgnylcarbonylamino which may be optionally substituted; R' and R' each independently-,- represent a hydrogen atom or an alkyl group having 1-4 carbon atoms which may be optionally substituted; B-' and B' each independently represent a phenylene group which may be optionally su Qj>,#tituted or a naphthylene group which may be optionaff.,ly substituted; m2 represents 1 or 2; n2 represents 0 or 1, providing m2+n2 is 2 or 3; and y3 and Y' each independently represent -CH2CH2L, wherein L represents a group releasable by the action of alkali, or a vinyl group; or a salt thereof; or iii) a compound of formula (III):

H N--- N=N-Q-N--\ / N 7 N- R cl (S03H)m3 (S03H).3 R8 1 -y5 N-BS-S02 (III) wherein R7 represents ureido, alkylcarbonylamino which may be optionally substituted and in which the alkyl moiety has 1-4 carbon atoms, alkenylcarbonylamino which may be optionally substituted and in which the alkenyl moiety has 2-4 carbon atoms or phenylcarbonylamino which may be optionally substituted; R' represents a hydrogen atom or an alkyl group having 1-4 carbon atoms which may be optionally substituted; B5 represents a phenylene group which may be optionally substituted or a naphthylene group which may be optionally substituted; m3 represents 1 or 2; n3 represents 0 or 1, providing m3+n3 is 2 or 3; and Y5 represents - CH2CH2L, wherein L represents a group releasable by the action of alkali, or a vinyl group; or a salt thereof.

2. A composition according to claim 1 which comprises a compound of formula (I), or a salt thereof, wherein Y1 and y2 each independently represent -CH2CH2L, wherein L represents a group releasable by the action of alkali.

3. A composition according to claim 1, wherein the second compound is a compound of formula (I), or a salt thereof.

4. A composition according to claim 1, wherein the second compound is a compound of formula (II), or a salt thereof, or a compound of formula (III), or a salt thereof.

5. A composition according to.claim 3, wherein the first compound is a compound of formula (I), or a salt thereof, wherein Y' and y2 each independently represent -CH2CH2L, wherein L represents a group releasable-by the action of alkali; and the second compound is a compound of formula (I), or a salt thereof, wherein at least one of,Y1 and y2 represents a vinyl group or -CH2CH20H.

6. A composition according to,,claim 3, wherein the first compound is a compound of formU& (I), or a salt thereof, wherein Y1 represents -CH2CH2L, Wherein L represents a group releasable by the action of alk y2 a& i, and represents a vinyl group; and the second compound-A- a co ound of formula (I) or a salt thereof, wherein Y1 represents a vinyl group or -COH M-esents a vinyl group and y2 A composition according toSelaim 3 wherein the first compound is a compound of formu.1g or a salt thereof, wherein Y1 represents -CH2CH2L, rein L represents a group releasable by the action of al-k.AI-i,, and y2 represent a vinyl W. group; and the second compoundU" a compound of formula (I), or a salt thereof, wherein Y1 represents -CH2CH,L and y2 represents - CH2CH20H. 8. A composition according to claim 3, wherein the first compound is a compound of formula (I), or a salt thereof, wherein Y1 and y2 represent a vinyl group; and the second compound is a compound of formula (I), or a salt thereof, wherein Y1 represents -CH2CH2L, wherein L represents a group releasable by the action of alkali, or a vinyl group and Y' represents -CH2CH20H. 9. A composition according to claim 3, wherein the first compound is a compound of formula (I), or a salt thereof, wherein Y' represents -CH2CH2L, wherein L represents a group releasable by the action of alkali, and y2 represents -CH2CH2OH; and the second compound is a compound of formula (I), or a salt thereof, wherein Y' represents a vinyl group and y2 represents -CH2CH20H. 10. A composition according to claim 3, wherein the first and second compounds are compounds of formula (I), or salts thereof, and the groups Y' in the first and second compounds are the same as each other and the groups y2 in the first and second compounds are the same as each other, but the substitution position of -S02-Y1 on B' or -S02 _y2 on B 2 is different in the first and second compounds. 11. A composition according to clam 3, wherein the first and second compounds are compounds of formula (I), or salts thereof, and the groups Y' in the first and second compounds are the same as each other and the groups y2 in the first and second compounds are the same as each other, but the groups B' -58- or the groups B2 in the first and second compounds are different from each other. 12. A composition according to any one of the preceding claims, wherein R', R' or R represents ureido or acetylamino. 13. A composition according to claim 1, wherein R 2, R 3, R5, R6 or R8 represents a hydrogen atom, a methyl group or an ethyl group, and B', B 2, B 3, B 4 or B 5 represents unsubstituted phenylene. 14. A composition according to any one of the preceding claims, wherein the total amount of compounds of formula (I) or salts thereof present in the composition, wherein Y' or y2 represents -CH2CH20H, is 20 parts by weight or less per 100 parts by weight of the composition. 15. A composition according to claim 4, wherein the total amount of compounds of formula (II) or salts thereof present in the composition is from 5 to 20 parts by weight based on 100 parts by weight of the total amount of compounds of formula (I) or salts thereof piment in the composition.

7 16. A composition according toclaim 4, wherein the total amount of compounds of formula-(III) or salts thereof present in the composition is from 15 to 80 parts by weight based on parts by weight of the tota Aamount of compounds of formula (I) or salts thereof pl"oent in the composition. 17. A method for dyeing or prting a cellulose fiber material, which comprises appl:ing a reactive dye composition according to any one of claime-1 to 16 to the cellulose fiber material. 18. A cellulose fiber material dyed or printed using a AW reactive dye composition according to any one of claims 1 to 16. 19. A reactive dye composition according to claim 1 substantially as hereinbefore described in any one of the Examples. 20. A method according to claim 17 substantially as hereinbefore described in any one of the Examples. 21. A cellulose fiber material according to claim 18 substantially as hereinbefore described in any one of the Examples.