JPS5962668A - Monoazo compound containing one sylfonic acid group - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to monoazo compounds containing one sulfonic acid group,
Concerning their preparation and use as anionic dyes.

The present invention provides compounds and mixtures thereof which correspond to the following formula I in the free (t, 2 form) and are in the free I or salt form.

In the above formula, It, represents C1-6 alkyl, or C mono-modified by hydroxy, chlorine or cyanide.
3-6 alkyl, R2 is hydrogen or 01-4 alkyl (IT representation, ni, J: 1 or 2, R6
are each independently hydrogen or methyl, provided that N,
For N-di-1a-substituted sulfonamide groups, 1t1 and the optionally substituted phenyl group shall together contain from 9 to 15 carbon atoms), 174 is hydrogen, halodane, C alkyl or C1- 4 alkoxy represents 1-4, and R represents hydrogen or C4-4 alkyl.

The number of carbon atoms for R1 and the phenyl group substituted with each other is preferably 9 to 12, more preferably 9.
Also, Q is 10, most preferably 10.

Any unsubstituted alkyl as Ill may be single chain or branched. Preferably it contains 1 to 4 carbon atoms. More preferred are methyl, ethyl or straight-chain or branched butyl, most preferred is n-butyl.

Any substituted alkyl as R1 also has a substituent group of 01
It may be a straight chain or branched alkyl group, such that it is attached to more than one carbon atom.

Preferably, it contains 3 or 4 carbon atoms.

More preferably, the alkyl group is monosubstituted on hydroxy, for example, 2- or 3-hydroquine zolobyl, 2-13- or It is 4-hydroxybutyl. Even more preferred is linear 2-hydroxypropyl or 2-hydroxybutyl. Most preferred is linear 2-hydroxybutyl.

R1 is preferably R, i.e. 1G chain or branched C1-
4-alkyl or straight-chain or branched C3-4 alkyl substituted with mono-ji' by hydroquine, j-base or cyan (11"5° other than C1-position, with l-)
It is. Furthermore, the dimensions are l'1, Yζ1. , i.e. butyl,
Ethyl, straight or branched butyl, straight or branched 2- or 3-hydroxypropyl or 2-13- or 4-
It is hydroxybutyl. More preferred is R1°, ie methyl, ethyl, +1-butyl, 2-hydroxypropyl-(n) or 2-hydroxybutyl-(n).

Still more preferably C, R1, i.e. n-butyl or 2-
Hydroxybutyl (n). In particular, R1 is preferably n-butyl.

Any alkyl as R2 is preferably methyl or ethyl,! Samurai and Methyl.

R is preferably R2a, ie hydrogen, methyl or ethyl. Most preferred is R2, hydrogen or methyl.

If the phenyl group bonded to the nitrogen atom of the sulfonamide group is di-11-substituted, these two [f substituents are preferably in the 2,4-12,5- or 3,5-position, preferably in the 2,4-12,5- or 3,5-position. is in the 2,4- or 2,5-position. If the phenyl group is tri-substituted, these substituents are preferably in the 2,4.6-position.

Any halogen as R is preferably chlorine or bromine, especially chlorine. Any alkyl as R4 is preferably methyl or ethyl, especially methyl, any alkoxy is preferably methoxy or Q as ethoxy,
Especially methoxy.

The group R4 is preferably bonded to the carbon atom at the 6-position, more preferably at the 4- or 5-position of the phenyl residue.

R is preferably "4a, ie, hydrogen, chlorine, methyl or methoxy. More preferably, R4b is hydrogen or methyl. Most preferably, R4 is hydrogen.

Any alkyl as R5 is preferably methyl.

R5 is preferably ■ζ5a, ie hydrogen or methyl O
Most preferably, +15 is hydrogen.

Preferred compounds are those corresponding to formula la below in the free acid form.゛In the formula 2, N, N-substituent of the sulfonamide group, group R1
c and the optionally alkyl-substituted phenyl group together contain a total number of carbon atoms of 10, and N-phenyl 71i
(If they contain two 1be substituents, they are 2,4-1
2,5- or id3,5-positions ft2; if this group contains three substituents they are in the 2,4,6-positions.

More preferred compounds are those of formula 1a in which (1) R
A compound in which 4a is 1t45, (2) Rlo is R1
, (3) compounds where l12a is R2b, (4) those of (2) or (3) where R4a is hydrogen, (5) compounds where t1c is n-butyl and R2a and R3 are The compound (4), which is hydrogen, is.

When the compound of formula I is in salt form, the cation of the sulfo group is not: iT, j, 9N, but may be any of the non-chromogenic cations customary in the art of anionic dyes.

Examples of such cations are alkali metal cations and non-11'J- or lri-substituted ammonium cations, such as lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium 1. Triethylammonium, mo/-, no and h 1-
IJ-ethanol ammonium.

Preferred cations are alkali metal cations and ammonium, with sodium being most preferred.

The cation of the sulfo group may be a mixture of the above-mentioned cations, for example, in the compound of formula I (ri 711s may be in salt form).

Compound 2 is a diazotized amine represented by the following formula 11, which is reacted with a compound represented by the following formula In, o3H or a salt thereof in the free acid form in an acidic to neutral reaction medium. It can be manufactured by a method including.

Diazotization and coupling reactions can be carried out by conventional methods. Preferably, the coupling (d in an acidic reaction medium, more preferably p) 13 to 4.5 is carried out using water or a mixture of water and a water-miscible organic solvent as the reaction medium. Preferred temperature ranges are 0-30°C, especially 0-10°C for water, and 0-20°C for mixed solvents such as water/ethanol.

The starting materials, compounds of formula (1) or Ill, are known or can be obtained by known methods from available starting materials.

The compound of formula (1) can be isolated according to conventional methods. Isolation of monoazo compounds is carried out by salting out, then filtering, washing,
This is advantageously carried out by vacuum drying. Depending on the reaction and separation conditions, the compounds of formula (1) can be obtained in free acid form or preferably in salt form or in mixed salt form containing, for example, one or more of the abovementioned cations. It can be converted by conventional means from the free acid form to the salt form or mixed salt form, or vice versa, from one salt form to the other.

Compounds of formula 1, especially in salt or mixed salt form, can be used with anionic dyes such as leather, natural or synthetic, lyamides, polyurethanes and lyolefins before basic modification.
Useful for dyeing and printing colorable substrates. These are made of or contain natural and synthetic polyamides such as nylon 6 or nylon (the latter in 4 yen) on wool, silk and /l'lr for dyeing and printing IJ fiber substrates. These compounds are particularly suitable for dyeing or printing nylon car coverings and nylon 6 or nylon 66 carpets.

The compounds of formula I may be prepared, for example, in liquid or solid compositions such as are customary for monoazo acid dyes for dyeing and printing anionically dyeable substrates such as nylon carpets. The preparation of such compositions in the form of stable liquid forms, e.g. This can be done by adding and dissolving conventional additives such as urea, or by grinding or granulating.

Additionally, compounds of formula I can be prepared into cold water dispersible formulations. Such a dispersion is, for example, lf:I
The dried or wet dyestuff is ground in an aqueous dispersion medium in the presence of t or more conventional anionic dispersants and optionally other conventional additives, optionally followed by spray drying. It can be prepared by The formulation so obtained is finely fractionated in cold water.

Dyeing and printing are carried out according to known methods, for example: - Rad dyeing or exhaust dyeing, especially from a substantially neutral aqueous bath, i.e. a weakly alkaline to weakly acidic aqueous bath. The latter can be used to the extent possible.

Furthermore, the compound of formula ■ is [space dyed j (space
-dyeing) process. These compounds are also used in the gum displacement technique used in carpet dyeing.
e) is also suitable for use.

The compounds of formula I in salt form are highly soluble in water. these(·
It also has high build-up, rapid exhaustion, and gives uniform dyeing to nylon, which migrates well and is particularly prone to myositis. For example, the dyeings obtained on nylon have very good light fastness properties. Furthermore, the compounds of formula I have a wet fastness, in particular wash +61, (cold)
It provides dyeings with good all-round fastness properties, such as fastness to water, milling, sweat or other fastnesses, such as fastness to dry or wet crocking or fastness to ozone. Historically, these compounds have good dye strength.

The compounds of formula I are also suitable for combination with other anionic dyes which are exhausted from neutral dyebaths, and are particularly effective for combination into trichromatic dye mixtures (11), whereby the above-mentioned Tone-in-tone dyeings are obtained which have advantageous properties.Furthermore, such dyeings are free from catalytic fading in water.

Example The following examples are intended to illustrate the entire history of the invention.

In the columns, parts and units are expressed in weight, and temperatures are expressed in degrees Celsius.

Bayu 30.4 parts (7) 2-7 minobenzenesulfonic acid -N-
N-Butyl-N-phenylamide is dissolved in 80 parts of ethanol at 45° by adding 56 parts of 30-thihydrochloric acid. The solution is then cooled to -5°C in a cold water bath. For 20 minutes, the temperature 'f/, -5 ~
A solution containing 7.0 parts of sodium nitrite is added dropwise to 25 parts of water while maintaining the temperature at 0°. After stirring for 30 minutes, the diazotization is complete.

This excess nitrous acid is reduced to 1 molecule by adding a small amount of amidosulfonic acid.

23.9 parts of 2-amino-8-hydroxynaphthalene
6-Sulfonic acid is dissolved in 150 liters of water by adding 12 parts of 30% sodium hydroxide solution. As a result, P[( of this solution is approximately 8. This solution is gradually added dropwise to the same siazonium solution as specified above within 1 hour, and PHff at this time is 50% sodium acetate solution. By doing 3.0~3.
Keep it at 5. After 25 hours of stirring, the coupling reaction is completed.

1-1 of this solution, adjust to 9 by adding 30% sodium hydroxide solution. Separate the precipitated material by filtration^1
1, and the residue is washed with a 10% sodium chloride solution containing 200 parts of gold and dried under vacuum at 100°.

The dyestuff thus obtained, in free acid form, corresponds to the following formula % and dyes natural and synthetic polyamide fibers in a bluish-red color in its salt form. These dyeings have outstanding wet fastness and light fastness properties.

Furthermore, the dyes are suitable for dyeing in combination in mixtures of two, in particular three, components.

Margin Examples 2 to 47 Below, in the following table, are further listed compounds corresponding to the following formula in free 1i7fffl acid form. These compounds can be prepared according to the method described in Example 1 using the appropriate starting materials.

The dyes of Nabarami Mli Examples 2 to 47 below dye all natural and synthetic polyamide fibers bluish red. These polyamide dyeings have exceptionally good sunlight fastness and/or! Example 2
Kamo 47's Someo' is obtained in the form of its sodium salt. Depending on the reaction and isolation conditions, these dyes can also be obtained in the free r12 form or in the form of other salts by reacting their salts according to known methods. Examples are those salt forms containing one or more of the cations indicated above.

In the following example, the suitability of the dyes of the invention +4i is illustrated.

Application example A (exhaust dyeing of polyamide fabric) 9100 parts of pre-613 synthetic polyamide (e.g. nylon 66)
) was placed in a dyebath of water having the following composition: 2 parts of the dye of Example 1, 10 parts of anhydrous 11 diluted sodium, and 4000 parts of sodium.

The liquor was further heated to boiling temperature I over 30 minutes and kept at this temperature for 1 day. The dyeing was then completed by adding 4 parts of glacial acetic acid to the liquor and heating the liquor to boiling temperature for 30 minutes. The water that evaporated during staining was continuously replenished. The resulting bluish-red nylon cloth was taken out of the dye liquor, washed with water, and dried. Woolen cloth was also dyed in a similar manner.

The dyes of Examples 2 to 47 or mixtures of two or more of the dyes of Mti Examples 1 to 47 can also be used to dye polyamide according to the method shown in Application Example A or B.

The dyeing has good light and wet fastness properties.

Application example B (exhaustion dyeing of nylon thread) 100? x (s pre-j: 15 nylon 66
The yarn was placed in a dye bath with the following composition: 1 part dye of Example 1 1-2 parts oleylamine (leveling agent 9) 1 part sodium phosphate-3000 parts water.

The two-layer dyebath was heated to boiling point 119, 1 part of glacial acetic acid was added and the bath temperature was kept at this temperature for 45 minutes.

The water evaporated during the dyeing process was continuously replenished. T obtained? The red-colored nylon 66 yarn was taken out of the dye bath, washed with warm water, and dried.

Application example C (Printing of amide fabrics) The following composition: 30 parts of the dye of Example 1 50 parts of urea 50 parts of solubilizer (e.g. thiodiethylene glycol) 290 parts of water 500 parts of thickener (e.g. A polyamide fabric was printed with a printing paste containing 20 parts of an acid donor (for example, thiourea containing 7960 parts of ammonium tartrate) based on carobbean.

The printed fabric was steamed at f120° (saturated steam) for 40 minutes, washed with cold water, washed at 60° for 5 minutes with Inari solution of a conventional detergent, and washed again with cold water.

I don't like the bluish red print. It had good sunlight and hemorrhoid i5Z resistance.

By the same method, the dyes of Examples 2 to 17 or the dyes of Examples 1 to 47
A printing paste can be produced using a mixture of two or more dyes. Printing can be performed by the above method using such a printing paste.

Part 3 Example DC = i” Continuous dyeing of Liamide carpet)
Month? Four lyamide (for example, ordinary nylon 6 or ordinary nylon 66) carbons were ethoxylated with 1 to 2 parts of r-syl alcohol, 4 moles of ethylene oxide per mole of this alcohol. or a similar surfactant and 998 to 999 parts of water, and squeezed to impregnate 1 part of this wet 4" to reduce the impregnation to 80 to 100 parts. Ta.

Dye bath of the following composition: 0.5 to 5 parts of dye of Example 1 1 to 2 parts of guar thickener (e.g. Cerca gum I) -49
-D) 1 to 2 parts of decyl alcohol ethoxylated with 4 moles of ethylene oxide per mole of this alcohol (or similar surfactant), 91 to 97.5 parts of water, and to the object to be dyed. Accordingly, for example, pl(-i5
Enough to adjust to) A1 acid tris) IJium or acetic acid, said Rja 71? The lyamide carpet is impregnated using a continuous impregnation device (for example Kesters) to reach an impregnation rate of 3 (10-600%).

This bluish-red dyed polyamide carbat is then steamed for 4 to 10 minutes in a vertical or horizontal steamer.
Washed with warm water and dried.

Application Example E (Continuous Dyeing of Polyamide Carpets by Gum Displacement) Analogously to Application Example I), a polyamide (e.g. regular nylon 6 or regular nylon 66) carpet is wet treated and wrung and coated with the following composition: : 10 parts of guar thickener (e.g. cellulose gum 1) -49-
D) A layer of 989.75 parts of glacial acetic acid and 989.75 parts of water was applied in a layer.

7+ treated with the dye liquor as mentioned in the application example above? The lyamide carpet was impregnated using a continuous impregnation device (e.g. Kesters) to reach an impregnation rate of 300-600. This bluish red dyed polyamide car! ! At vertical or horizontal steamer 4
Steamed for ~10 minutes, washed with hot water, and dried.

λmax List Below is a list of the maximum absorption wavelengths of the exemplified dyes. Measurements were carried out in an 8:2 mixture of trimethylformamide/water to which phosphoric acid or glacial acetic acid had been added. Indication of 1981 Patent Application No. 141,975-2, Name of the invention Monoazo compound containing one sulfonic acid group 3, Relationship with the person making the amendment Case Name of patent applicant Title Sandoz Akchengesellschaft 4, Agent (4 others) 5. Column 6 of “Detailed Description of the Invention” of the specification to be amended, contents of the amendment (a) Page 10 of the specification, line 6 from the bottom, “Including the total number of carbon atoms, ”, insert the following statement: "The group R4a is in the 4-15- or 6-position," Correct.

(c) Page 24 of the specification, line 1, "Thrown into dye bath."
The statement was corrected to ``It was added to the dye bath at 26 to 2 gamma.''

24th page of the specification, line 199, "120°" is corrected to "102°".

Claims (1)

[Claims] 1. Compounds and mixtures thereof that correspond to the following formula (2) in free acid form and are in free acid form or salt form. In the above formula, R1 represents 01-6 alkyl or C3-6 alkyl monosubstituted by hydroxy, chlorine or cyano f:, R2 represents hydrogen or C1-4 alkyl with λ, and n represents 1 or 2. , R5 each independently represents water; ), R4 is hydrogen, C1-4
It represents alkyl or 01-4 alkoxy, and R5 represents hydrogen or 01-4 alkyl. 2. lt'! where the total number of carbon atoms 111 for R1 and the optionally substituted phenyl group is 9 to 12;
A compound according to claim 1. 3. The compound of the second aspect 4, ν, in which the total number of carbon atoms is 10 is claimed. 4. ) or 2-hydroxybutyl-(
The compound according to any one of Claims 1 to 3, which is n). 5. The compound according to any one of claims 1 to 4, wherein R2 is hydrogen, methyl or ethyl. 6. The compound according to item 3 of the scope of patent t11, wherein R1 is n-butyl and R2 and R3 are hydrogen. 7. Claims 1 to 7 in which R4 and [R5 are hydrogen]
A compound according to any one of Item 6. 8. A compound according to claim 1, which corresponds to the following formula 1a in free acid form. R28(R3)n'' in the formula, I't4a+4 water (1,''; represents 1M element, mebul or methoxy, located at the 4-15- or 6-position, Rlc is methyl, ethyl, n-butyl, 2-hydroxyzolopyl-(n) or 2-hydroxybutyl-(
n) represents gold, R2a represents hydrogen, methyl or ethyl, R3 and n are the same as defined in claim i1; The substituted phenyl groups together contain a total of 10 carbon atoms, and when the N-phenyl group contains two substituents they are in the 2,4-12,5- or 3,5-position; If this group includes three I4 substituents, they are in the 2,4,6-position. 9. The compound according to claim 8, wherein R4 is hydrogen. 10. Compounds in which R2 is hydrogen or methyl, Claim 8 or 9 5. 11. The compound according to claim 9, wherein 11R1c is n-butyl and R28 and R3 are hydrogen. 12,4 In preparing all the compounds of the formula I described in Section I'4 of Section 1 of the Permission 1 Requirement, the noazotized compound of the following formula (■), R2
(R3) A method comprising reacting an amine represented by n with a compound represented by the following formula u1, or a salt thereof, in the free lI#rl'2 form in an acidic to neutral reaction medium, or a salt thereof. 13. A method for dyeing or printing an anionic dyeable substrate, which comprises applying a compound of the formula I described in item 1 as a dyeing or printing agent to the anionic dyeable substrate. . 14. The method according to claim 13, wherein the anionically dyeable substrate is a fibrous material comprising or consisting of a natural or synthetic polyamide.