DE2404357A1 - COLORING PROCESS - Google Patents

Description

PATENT LAWYERS DR.-ING. H. FINCKE Ol PL.-I NG. H. BOHR DIPL.-ING. S. STAEGER

Fern call ι '26 60 60

Tiltgrammn Cloimi Munich PoiUchtckkontoi Munich 27044-602

Bank details Bayer. Vereinibank MOnchen, account 430404

Mapp.No. 23449 - Dr.K / P Please indicate in the answer

β Munich β, January 30th

MOIIerwrofie 31

Case Dd. 25832

IMPERIAL CHEMICAL INDUSTRIES LIMITED London, United Kingdom

Dyeing process
Priority: 1/30/1973 - Great Britain

The invention relates to a method of dyeing, and in particular to a method for dyeing polyamide textile materials.

According to the invention there is provided a method for dyeing polyamide textile materials proposed, which is carried out by a polyamide textile material with an aqueous Solution of an azo dye of the formula

HOOC

AT

NO-

N ^ X

JU.

(I)

409831/1082

treated, wherein A stands for the remainder of a diazo component of the benzene or naphthalene series; X stands for "N-,""C-Clor"C-CN; Y represents chlorine or bromine; Q is -O- or -S-; Q for a direct bond, -0-, -GO-, -SO ₂ -, -SO ₂ NH-, -NHSO ₂ -, -CONH-, -NHCO-, -000 -, - 0CO-, -OSo ₂ - , -S- or -NR -, where R is hydrogen or lower alkyl; R for an alkylene, cycloalkylene or arylene

₂
radical; R stands for an optionally substituted one

Alkyl, cycloalkyl, aralkyl or aryl radical is such that R and R together do not have more than 13 carbon atoms contain; R * represents hydrogen or lower alkyl; and the ring B carries one or more substituents can.

The radical represented by A can carry the usual substituents such as are suitable for diazo components. Examples for such substituents are sulfopic acid and carbon ■ acid groups, chlorine, bromine, cyano, hydroxy alkyl, alkoxy, Trifluoromethyl, -NHCOR, where R ^ is an alkyl, aryl, alkoxy, Is aryloxy, alkylamino, arylamino or amino radical,

⁶ S where R ^{6 is} an alkyl or aryl radical, and R ⁷

QO

QO

Is hydrogen or an alkyl radical, and -SO ₂ R, where R is an alkyl or aryl radical. Other substituents that can be present on A are phenylazo and naphthylazo radicals, which in turn can themselves be substituted.

The two sulfonic acid groups can both be bonded in radical A or both on ring B, or one can be attached to A and the others be bound to B. In addition to one or two sulfonic acid groups the ring B can carry one or more other substituents, such as chlorine or bromine atoms and hydroxy, Alkyl or alkoxy groups or groups of the formula -NHCOR, where R ^ has the meaning given above.

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Throughout the specification, the term "low" refers to Alkyl "refers to alkyl radicals having 1 to 4 carbon atoms.

1 2

R is preferably an arylene radical and R is preferably an alkyl radical having 4 to 7 carbon atoms. In these cases

1 2

len, Q is preferably oxygen and Q is preferably one direct bond.

The dyes of the formula I can be prepared by adding a compound of the formula

(II)

wherein X and Y have the meanings given above, in any order with equimolecular amounts of an azo compound the formula

OU

(III) ^:

H-NR ³ H

. i

409831/1082

where A, B and Ή? have the meanings given above, and a compound of the formula

ρ ρ Λ 1 ΈΓ - Q - R '-Q ¹ -H

(IV)

Λ Ο Λ 2

wherein R, R, Q and Q have the meanings given above, implements.

The dyes of the formula I can also be prepared by diazotizing an aromatic amine and these obtained diazo compound with a coupling component of 1-Phenyl-3-carboxy-5-pyrazolone series couples, with the amine and the coupling component together have 2 sulfonic acid groups and a group of the formula

(V)

in which X and Y have the meanings given above, contain, being a dye of the formula

HOOC.

NR ³

409831/1082

arises, which then in turn with a compound of the formula IV is reacted, except when R is an alkylene or cycloalkyl is radical.

Suitable compounds of the formula II are cyanuric chloride, cyanuric bromide, 2,4,6-trichloropyrimidine, 2,4,6-tribromopyrimidine, 2,4,5,6-tetrachloropyrimidine and 2,4,6-trichloro-5-cyanopyrimidine.

Azo compounds of the formula III are described in detail in the literature. They can be made from diazotizable ones aromatic amines and suitable coupling components in the usual manner, for example by diazotizing a aromatic amine, which can also contain an acetylamino group, and coupling under alkaline conditions with 1- (aminophenyl- or acetylaminophenyl) -3-carboxy-5-pyrazolone, and subsequent hydrolysis of the acetylamino group, if necessary.

Examples of aromatic amines which can be used in the preparation of the azo compounds of the formula III, are: 3-aminoacetanilide, 4-aminoacetanilide, aniline-2-, - »3— or -4-sulfonic acid, aniline-2,5- »-2,4- or -3,4-disulfonic acid, 2-aminophenol-4- or-6-sulfonic acid, 4- or 5-sulfo-2-aminobenzoic acid, 4- (or 6-) chloro-2-aminophenol-6- (or 4-) sulfonic acid, 2-aminophenol-4,6-disulfonic acid, 4- (acetylamino- or methyl or methoxy) aniline-2-sulfonic acid, 1-naphthylamine-3-, -4-, -5-, -6- »" "7- or -8-sulfonic acid, 2-aminonaphthalene-i-, -5- * -6-, -7- or -8-sulfonic acid, i-naphthylamine-2,7-, -3,6-, -3,8-, -4,6- or -4,7-disulfonic acid, 2-naphthylamine-1,5- »-3» 7- »-4.8-, -5.7- or -6,8-disulfonic acid, 5-acetylaminoaniline-2-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid and aniline-5-sulfonanilide-2-sulfonic acid.

'k 09831/1082

Examples of coupling components which can be used in the preparation of the azo compounds of the formula III are: i-phenyl-J-carboxy - ^ - pyrazolone, 1- (2 · -, 3 '~ or 4- ¹ -sulfophenyl) -3 -carboxy-5-pyrazolone, 1- (2 * -σΐι1οΓο-5'-sulfophenyl) -3-carboxy-5-pyrazolone, 1- (2 ^f , 4 · '- or 2 ¹ , 5'-disulfophenyl) -3 -carboxy-5-pyrazolone, 1- (3'- or 4 · -acetylaminophenyl) -J-carboxy- ^ pyrazolone, 1 - (2 ·, ~ 5 '-dichloro-4-' -sulfophenyl) -3-carboxy- 5-pyrazolone, 1- (4'-aminophenyl) -3-carboxy-5-pyrazolone, 1- (4- ^f -amino-3 '-sulfophenyl) -3-carboxy-5-pyrazolone, 1- (3' -Aminophenyl) -3-carboxy-5-pyrazolone and 1- (3'-amino-4 ^l sulfophenyl) -3-carboxy-5-pyrazolone.

Suitable compounds of the formula IV are alkylphenols, such as, for example, o-, m- and p-butylphenol, -amylphenol and -hexylphenol; Cycloalkylphenols such as o- and p -cyclohexylphenol; Aralkylphenols, such as o-, m- and p-benzylphenol; Arylphenols, such as e.g., o-, m- and p-phenylphenol; Alkoxyphenols, e.g. Hydroquinone and resorcinol monoalkyl ethers, in which the alkyl radical consist of ethyl, propyl, butyl, amyl, hexyl and heptyl can; Cycloalkoxyphenols such as p-cyclohexyloxyphenol; Aralkoxyphenols such as p-benzyloxyphenol; Aryloxyphenols, such as p-phenoxy phenol; thio-substituted phenols, such as o-, m- and p- (butylthio) phenol, o- and m- (hexylthio) phenol, o- (Heptylthio) phenol, o- and p- (Benzylthio) phenol and o-, m- and p- (phenylthio) phenol; Benzene thiols, such as p-butyl benzene thiol, p-butoxybenzenethiol, p- (butylthio) benzenethiol, p-amylbenzenethiol, p-hexylbenzenethiol, p-hexyloxybenzenethiol, p-biphenylenethiol and m- (phenylthio) benzenethiol; aliphatic Alcohols and thiols, such as nonanol, dodecanol, 3,3,5-trimethyl-cyclohexanol, p-butylcyclohexanol, 2-octyloxyethanol, p-butoxycyclohexanol, p-lthylthiocyclohexanol, 2-benzylcyclohexanol, 3-phenyl-1-methylpropanol, 2-phenoxyethanol, 2-phenylthioethanol, Nonaneethiol and 2-phenoxyethane thiol.

409831/1082

Aromatic amines which contain a group of the formula Y reactive with fibers can be prepared by that one condenses a compound of formula II with the corresponding diamine under such conditions that only one of the two amino groups reacts with the compound of formula II. Specific examples of such diamines are 1,3-phenylenediamine-A-sulfonic acid, 1, ^ - phenylenediamine - ^ - sulfonic acid, 1,3-phenylenediamine-4 ·, 67disulfonic acid, 1, ^ - phenylenediamine- ^, 5-disulfonic acid and 2,6-diaminonaphthalene-4-, 8-disulfonic acid.

The reactions which lead to the formation of dyes of the formula I can be carried out using the conditions as they are extensively described in the literature on such reactions.

Polyamide textile materials made with the dyes of the formula I using conventional dyeing, padding, or printing techniques Natural and synthetic polyamide textile materials such as wool, silk and Nylon. The polyamides can have any textile form, such as the form of threads, staple fibers, yarns or woven or knitted goods.

The dyes of the formula I are particularly suitable for dyeing wool, such as wool that is non-felting or machine washable has been made, by chemical methods such as acid chlorination, applying hypochlorite under neutral or weakly alkaline conditions, application of permonosulfuric acid, application of the sodium salt of Dichloroisocyanuric acid and deposition of polymers on the surface of the roll, for example amine / epichlorohydrin resins be used. A material that has been treated in this way can be processed by conventional Wool dyeing processes are dyed, one step at a time

409831/1082

Pad dyeing process or continuous pad / steam process can use. When the dyes are applied to such fibers, they exhibit excellent fastness to wet treatments and against light.

The invention is illustrated in more detail by the following examples, in which all parts and percentages are expressed by weight are.

example 1

A solution of 4.7 parts of 1,3-bienylenediamine-4-sulfonic acid in 100 parts of water with a pH of 7.0 is added over 20 minutes at 0 to 5 ° C. to a suspension which has been prepared by dissolving 4 , 62 parts of cyanuric chloride in 15 parts of acetone and adding the resulting solution to 30 parts of water and 30 parts of ice. The mixture is then stirred at 0 to 5 ° C. for 2 hours, the pH being kept at 4 to 5 by the occasional addition of 10% sodium carbonate solution. 7-5 parts of 36% hydrochloric acid are then added, whereupon the mixture is diazotized by adding 1.7 parts of sodium nitrite in 11.5 parts of water. The diazo suspension is then added to a solution of 7 »1 parts of 1- (4'-sulfophenyl) -3-carboxy-5-pyrazolone in 100 parts of water at 0 to 5 ° C and at pH 9.0, whereupon the mixture 2 Hours at 0 to 5 ° C is stirred. While stirring, the pH is kept at 9.0 by adding 10% sodium carbonate solution. A solution of 4.2 parts of p-tert-butylphenol in 50 parts of acetone is then added to the Dichlorotriazinylazofarbstoffsuspension is raised whereupon the temperature to 30 ⁰ C. The reaction mixture is stirred for 3 hours at 30 ⁰ C, the pH being maintained by the occasional addition of 10 #iger sodium carbonate to 9.0. The pH is then adjusted to a value between 6.5 and 7.0. 10 # aqueous sodium chloride solution is then added, whereupon

409831/1 082

_ Q -

the precipitated dyestuff is filtered off, washed with 10 #iger sodium chloride solution and is dried at 4-0 ⁰ C.

When the dye is applied from a weakly acidic dyebath onto a roll that has been made machine washable (e.g. Hercosett Wool) then results in the dye a bright greenish yellow shade with excellent fastness to wet treatments and light.

Example 2

When the 4 ·, 7 parts of 1,3-phenylenediamine-4-sulfonic acid from Example 1 by 4x.7 parts 1,4-phenylenediamine-2-sulfonic acid are replaced, then a dye is obtained which gives a bright orange hue on wool, which exhibits excellent fastness to wet treatments and light.

The following table gives further examples of dyes which are used according to the invention and can be obtained in a manner similar to Examples 1 and 2 by using the information given in the second column Diamine with 1 mole of the acid chloride compound given in the first column condensed and diazotized and the amino compound obtained with that indicated in the third column Coupling component couples, and finally the product obtained with the phenol indicated in the fourth column or condensed thiol. The dye that is obtained, when applied to wool or nylon, gives that in the color specified in the last column.

Alternatively, the diamine indicated in the second column with the alkoxy or alkoxy indicated in the first column Condense alkylthio-dichlorotriazinyl compound and · the

409831/1082

240A357

Diazotize amino compound obtained and with the in the the coupling component indicated in the third column.

409831/1082

at
game • I. - π II η III η Il IV It V 3 Cyanuric chloride 1 ₁ 3-phenylenedi- 1- (4'-sulfophenyl) - 1- (3 ■ -Sulfophenyl) - 4-t-amylphenol greenish 2.4 j 6-trichloro- amine-4-sulfonic acid 3-carb oxy-5-pyraz o- 3-carboxy-5-pyrazo- Il yellow pynmidin It lon lon η It 2,4-, 5,6-tetra It -1- (2 »-0hloro-5'- 1- (2'-ChIOrO-S ¹ - 4-hexylphenol N 5 η chloropyrimidine It It sulfophenyl) -3- sulfophenyl) -3- 4-t-butylphe- η carboxy-5-pyrazolone carboxy-5-pyrazo- nol η 'It 1- (2 ', 5'-dichloro- lon 6th It It 4 -sulfophenyl) -3- It carboxy ~ 5-pyrazolone 4-t-amylphenol η 7th It η η 4 ~ 0yclohexyl- 1 «(41-sulfophenyl) - phenol 8th η 1,4-phenylene 3-carboxy-5-pyrazo- 4-t-butyl reddish diamine-2-sulfone lon phenol yellow acid It 9 Il η 10 It 11 It 12th ti

at
game I. II III IV V 13th 2,4,6-trichloro-
5-cyanopyrimidine 1 _? 4-phenylene
diamine-2-sul-
fonic acid 1- (2 · -. ^ 1ογο-5 «-8 ^ -
fοphenyl) -3-carboxy-
5-pyrazolone 4-hexylphenol reddish
yellow 14th Cyanuric chloride 1 ^ -phenylene
diamine, 6-di-
sulfonic acid i-phenyl-3-carboxy-
5-pyrazolone It greenish
yellow 15th η It 1- (2'-chlorophenyl-
3-carboxy-5-pyrazo-
lon 4-t-butyl
phenol η 16 It It 1- (4'-chlorophenyl) -
3-carboxy-5-pyrazo-
lon ti η 17th ti 1 _? 4-phenylene
diamine-2,5-di-
sulfonic acid 1-phenyl-3-carboxy-
5-pyrazolone 4-t-amyl
phenol reddish
yellow 18th dd It 1- (2 -chlorophenyl) -
3-carboxy-5-pyrazolor 4-t-butyl
phenol η 19th It η 1-phenyl-3-carboxy-
5-pyrazolone 4-butylbenzene
thiol It 20th It η η 4-phenyl
phenol Il 21 dd π π 4-phenoxy
phenol η 22nd
• η 2,6 diamino
naphthalene-4,8-
disulfonic acid It 4-t-butyl
phenol orange 23 η Il ti 4-cresol It 24 2-benzyloxy-4, 6-
dichloro-s-tria-
z in Λ , 3-phenylene
diamine-4-sul-
fonic acid 1 «(4ι-sulfophenyl) -
3-carboxy-5-pyrazo-
lon greenish
yellow

co co

O 00 to

at
game I. II III IV - V 25th 2-nonyloxy-A-, 6-
dichloro-s-tria-
interest, 1,3-ph.enylene-
diamine-4-sulfone-
acid 1- (4'-sulfophenyl) -
3-carboxy-5-pyrazo-
lon - greenish
yellow 26th 2-N ₀ nylthio-4,6-
dichloro-s-tria-
interest η It - Il 27 2-benzyloxy-4 _? 6-
dichloro-s-tria-
interest 1,4-phenylene
diamine ~ 2-sulXon-
acid η reddish
yellow 28 It 1,1-phenylene-
diamine-2,5-di-
sulfonic acid 1-phenyl-3-carboxy-
5-pyrazolone Il 29 η Ijj-phenylene-
diamine-Λ, 6-di-
sulfonic acid Il greenish
yellow 30th Il η 1- (2'-chlorophenyl) -
3-carboxy-5-pyrazo-
lon It

N> O CO

The following table gives further examples of dyes which can be used according to the invention and which can be prepared by diazotizing the amine given in the first column and with the in the second ' Coupling component indicated in the column, the acetylamino group, if necessary, hydrolyzed and the product obtained first with cyanuric chloride and then with the in condensed phenol or thiol indicated in the third column. The hue obtained when the dye is applied to wool or nylon is given in the fourth column.

409831/1082

.το co 00 co

CD 00 to

at
game I. II III IV π yellow 31 Aniline-2,5-disulfone- 1- (4 -Αΐηίηορηβη7ΐ) -3- 4-t-butylphenol greenish acid carboxy-5-pyrazolone yellow η 32 Aniline-2,4-disulfone η 4-hexyl phenol It acid 33 Aniline-2-sulfonic acid 1- (4. «- Amino-3'-sulfo- 4-t-butylphenol π reddish phenyl) -3-carboxy-5- yellow pyrazolone 34- Aniline-3-sulfonic acid 1- (3'-amino-4-sulfo- 4-t-amylphenol It phenyl) -3-carboxy-5- pyrazolone ti 35 2,5 dichloroaniline η 4-Cresol 4-sulfonic acid It 36 4-chloroaniline-2-sulfone It 4-t-butylphenol 8 acid 37 5-chloro aniline-2-sulfone η η acid 38 4 — methylaniline-2-sulfon- 1- (4'-amino-3-sulfo- η acid phenyl) -3-carboxy-5- pyrazolone 39 2-naphthylamine-1-sulfone Il η acid 40 4-methoxyaniline-2-sul- η 4-hexylphenol fonic acid

Vn I

K)

U) CJl

CXD CO

at
game 'I. II III IV 41 2-naphthylamine-1,5-di-
sulfonic acid 1- (4'-aminophenyl) -3-
- carboxy-5-pyrasolone 4-t-butylphenol yellow 42 3-aminoacetanilide 1- (2 ', 4'-disulfophenyl) -
3-carboxy-5-pyrazolone It greenish
yellow 4-3 4-aminoacetanilide η Il reddish
yellow 44 Aniline-2,5-disulfone-
acid 1- (4-aminophenyl) -3-
carboxy-5-pyrazolone 4-butylbenzene
thiol greenish
yellow

Claims (3)

Claims 1. A method for dyeing polyamide textile materials, characterized in that a polyamide textile material with an aqueous solution of an azo dye of the formula HOOC A-N = N __ γ ς, -UV-R ² treated, wherein A is the remainder of a diazo component of the benzene or naphthalene series; X for = * Ν-, «C-Cl or »C-CN stands; Y represents chlorine or bromine; Q for -O- or ρ
-S- stands; Q for a direct bond, -0-, -CO-, -SOp-, C. -SO ₀ NH-, -NHSO ₀ -, -CONH-, -NHCO-, -000 -, - OCO-, -0SO ₀ -, -S- or -NR -, where R is hydrogen or lower alkyl; R for an alkylene, cycloalkylene or arylene O
radical; R represents an optionally substituted alkyl, cycloalkyl, aralkyl or aryl radical, the- 12 ' kind that R and R together contain no more than 13 carbon atoms; R- ^{5 represents} hydrogen or lower alkyl; and the ring B can carry one or more substituents. 2. The method according to claim 1, characterized in that 1 2 R stands for an arylene radical and R stands for an alkyl radical having M to 7 carbon atoms. 409831/1082 240A357 3. The method according to claim 2, characterized in that Ί 2 Q is oxygen and Q is a direct bond. 409831/1082