JPS5933718B2 - Dyeing method for cellulose fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing cellulose fibers, and is a method for dyeing cellulose fibers having the general formula (1) or (1') [where A represents a benzene residue having at least one sulfonic acid group]. and B is naphthol or 1-
It represents an aryl-5-pyrazolone residue, and R,,R2 represents a hydrogen atom or a methyl group.

X represents an aliphatic, aromatic, compound residue, morpholino group or amino group bonded via an oxygen atom, nitrogen atom, and B represents a 1-aryl-5-pyrazolone residue. Y
may have an aliphatic group having at least 2 carbon atoms, a methyl group, a methoxy group, a sulfozoic acid group, a carboxylic acid group, a phenylene group or a diphenylene group which may have a chloro atom, or a sulfozoic acid group. Naphthylene group or -Z→
◆◆← represents a group (here Z is -0-, -S-, -SO
2-, -CH2-, -NH-, CH2CH2-, -CO
-, -NHCO-, -CH; C or -NHCH2CH
2NH-.

) or -N-Y-N- represents 1,4-piperazinylene ▲VIlvl.

This invention relates to a method for dyeing cellulose fibers, which is characterized by using a novel disazo dye represented by the following formula in the presence of an acid binder.

Various dyes having monohalogenotriazine groups have been known so far, and they react well with cellulose fibers in the presence of an acid binder such as sodium carbonate and fix thereon.

For example, in the case of dyeing, in the presence of salts and acid binders, 60
The method of heating and absorbing at ~100'C gives fast and practical dyeings. When used for textile printing or patain ink dyeing, it is well fixed to cellulose fibers by short-term steaming or dry heat treatment in the presence of an acid binder. However, dyes with monohalogen triazine groups generally cannot fix all of the dye obtained on cellulose fibers, and a considerable amount of unfixed dye is always contained in cellulose fibers. Wet fastness, especially washing fastness test (JISLO84
4) and water test (JISLO846), it is extremely poor.

Therefore, in order to obtain high wet fastness, washing with hot soaping containing a suitable surfactant is an essential step as a means of removing those unfixed dyes after dyeing.

However, in practice, the washing process including hot soaping requires as much time and effort as the dyeing process, or even more, and it has been pointed out that the major disadvantage of the washing process is that it is extremely difficult to perform the dyeing process. The emergence of this type of dye, which does not require any process and has excellent wet fastness, has been eagerly awaited. As a result of intensive research, the present inventor has found that the novel disazo dye represented by the general formula (1) or (1) of the present invention has an extremely high reaction fixation rate of the dye obtained on cellulose fibers, and surprisingly, it has been found that When dyeing at a high concentration, there is no need to carry out the washing process of hot soaping containing a surfactant as mentioned above, and the product has excellent fastness to harsh washing by simply washing lightly with water after dyeing and then treating it with a commonly available fixing agent. It has been found that a yellow to bluish-red color can be obtained in response to the test (JISLO844, A-4:7 ``C''), which is characterized by an extremely excellent wet fastness of grade 4 or above for cotton staining.

The dye used in the method of the present invention is a new compound, and its production method is shown below, for example.

1) The dye represented by the general formula (1) or (1') is expressed by the following formula (2) or (2 molar ratio of the target monoazo compound and the following formula (
3) diamine 1 molar ratio [in the formula A. B. X. Rl.
R2 and Y are as described above.

]D Manufactured by reaction.

Ii) The dye represented by the general formula (1) is obtained by tetrazotizing 1 molar ratio of the diamino compound of the following formula (4) and producing the dye represented by the following formula (5).
2 molar ratio of the coupling components and [in the formulas (4) and (5), R1, R2, Y, A and B are as described above, and X' represents the above-mentioned X or a chlorine atom.

] By coupling, or when X' in formula (5) is a chlorine atom, it is produced by further reacting with 2 molar ratios of the compound of formula (6) below.

[X is as described above. [111) The dye represented by the general formula (C) is obtained by tetrazotizing 1 molar ratio of the diamino compound of the formula (4) and coupling it with 2 molar ratios of aminonaphthol or 1-(aminoaryl)-5-pyrazoburane compound. , furthermore, the 2 molar ratio of cyanuric chloride and the formula (6
) and 2 molar ratios of the compound in any order.

Iv) The dye represented by the general formula (l) is produced by diazotizing 2 molar ratios of the monoamino compound of the following formula (7), and the coupling component of the following formula (8) [A, B, in the formulas (7), (8), X'
, Rl, R2 and Y are as defined above.

] 1 molar ratio, and when X' in formula (7) is a chlorine atom, the above formula (
It is produced by reacting 6) with 2 molar ratios of the compound.

Examples of diaminobenzene, aminonaphthol, and l-(aminoaryl)-5-pyrazolone compounds used as components A, B, or B include the following.

1,3-phenylenediamine-4-sulfonic acid 1,4-
phenylenediamine-2-sulfonic acid 1,3-phenylenediamine-4,6-disulfonic acid 1,4-phenylenediamine-2,5-disulfonic acid 1,4-phenylenediamine-2-methoxy-5-sulfone acid 1,3-phenylenediamine-4-methyl-6-sulfonic acid 1-amino-
8-naphthol-3,6-disulfonic acid 1-amino-8
-Naphthol-4,6-disulfonic acid 2-amino-8-
Naphthol-3,6-disulfonic acid 1-(41 amino-
2,'2! -disulfostilben-4-yl)-3-methyl-5-pyrazolone 1-(47-amino-2,2'-
disulfostilben-4-yl)-3-carboxy-5-
Pyrazolone 1-(47-amino-2,Z-disulfostilben-4-yl)-3-carboethoxy-5-pyrazolone 1-(1-methyl-37-amino-5'-sulfofenino(ha)-3- Carboxy-5-pyrazolone 1-(
'2! -Methyl-3'-amino-5! -sulfophenyl)-3-methyl-5-pyrazolone 1-(67-amino-
4! , 81-disulfo-naphthyl-i-)-3-methyl-5-pyrazolone 1-('2'-sulfo-57-aminophenyl)-3-methyl-5-pyrazolone.

Examples of the diamine of formula (3) include the following.

Ethylenediamine N-Methylethylenediamine 1,2-Propylenediamine 1,3-Propylenediamine N-Methyl-1,3-Diaminopropane 1,4-Diaminobutane Piperazine 1,3-Diaminobenzene 1,4-Diaminobenzene 4-Amino- N-Methylaniline 1,3-diaminobenzene-4-sulfonic acid 1,4-diaminobenzene-2-sulfonic acid 1,4-diaminobenzene-2-carboxylic acid 2-chloro-1,4-diaminobenzene 2-methoxy -1,4-diaminobenzene 2-methyl-1,4-diaminobenzene 4-methyl-1,3-diaminobenzene 2,6-diaminotoluene-4-sulfonic acid 2,5-dimethyl-1,4-diaminobenzene 2,6-diaminonaphthalene-4,8-disulfonic acid 1,5-diaminonaphthaline 2,6-diaminonaphthaline 2,7-diaminonaphthaline benzidine 0-dianisidine 0-tolidine 0-dichlorobenzidine 4,4'-diamino- 1,1'-diphenyl-3,37
-Dicarboxylic acid 4,4'-diamino-1,V-diphenyl-2,1-disulfonic acid 4,4'-diamino-3,3
'-Dimethyl-1,V diphenyl-2,i-disulfonic acid 4,41-diaminodiphenyl ether 4,4'-diaminodiphenyl sulfone 4,41-diaminodiphenylmethane 4,4'-diaminodiphenylamine 4 ,4'-diaminodiphenylamine-2-sulfonic acid 4,4'-diaminodiphenyl sulfide 4,4'-diaminodiphenyl sulfide-2,2'-disulfonic acid 1,2-bis(4 '-Aminophenyl)ethane 4,41
-Diaminobenzophenone 4,4'-Diaminostilbene-2,'2'-disulfonic acid 4,41-diaminobenzanilide 4,47-diaminobenzanilide-2-sulfonic acid 1
, 2-bis(47-amino-Z-sulfophenylamino)ethane, and the like.

Examples of the compound of formula (6) include, but are not limited to, the following.

i.e. ammonia, substituted or unsubstituted alkylamines (e.g. methylamine, ethylamine, diethylamine, dimethylamine, glycine, taurine, sarcosine, etc.), alkanolamines (e.g. monoethanolamine, diethanolamine, N-methylethanolamine, etc.), substituted or unsubstituted aniline (e.g. aniline, N-methylaniline, aniline-2,3, or 4-sulfonic acid, aniline-2,5-disulfonic acid, toluidine sulfonic acid, anisidine sulfonic acid, chloroaniline sulfonic acid, sulfonate) anthranilic acid), aminonaphthalene (1 or 2-aminonaphthalene monosulfonic acid,
1 or 2-aminonaphthalene disulfonic acid, 1 or 2-
aminonaphthalene trisulfonic acid, etc.), morpholine,
Alcohol (methanol, ethanol, probanol,
isoprobanol, etc.), phenol, C, m, p-chlorophenol, C, m, p-nitrophenol, C,
Examples include m,p-sulfophenol, C,m,p-cresol, and the like.

The method of the present invention uses a novel disazo dye having a specific structure as described above in the presence of an acid binder to dye cellulosic fibers or blended fibers thereof, such as dip dyeing, padding dyeing and printing. It is something.

Examples of the cellulosic fibers used in the method of the present invention include cellulose fibers such as cotton, hemp, viscose human silk, viscose cotton, and Bemberg, as well as blended, interwoven, and interwoven products thereof.

Examples of acid binders used in dyeing include sodium bicarbonate, sodium ortho- or metasilicate, sodium carbonate, and sodium hydroxide. When the present invention is applied to batch dyeing, the dyeing solution is usually adjusted with an inorganic salt such as sodium chloride or sodium sulfate and a dye, and after dyeing with heating for 10 to 60 minutes, an acid binder is is added, and dyeing is continued for 20 to 60 minutes while heating at 6'C to 100C.

In this case, the acid binder may be added from the beginning during the dyeing process, or
Furthermore, after dyeing with a dye bath that does not contain an acid binder, the dye can be fixed using a separate solution containing an acid binder and an inorganic salt. Furthermore, when the method of the present invention is applied to a dyeing process using a padding method such as continuous dyeing or semi-continuous dyeing, the dye bath is usually mixed with a dye, an acid binder, a penetrant and, if necessary, urea to prepare the tailored fiber. After immersing it in the dye bath for a short time, it is wrung out and left at room temperature or under heating, or it is subjected to a short steam or dry heat treatment. In some cases, the fibers may be soaked in a solution of an acid binder and then padded with a dye liquor that does not contain an acid binder, or the fibers padded with a dye liquor that does not contain an acid binder may be saturated with an inorganic salt. It may be treated using a solution of an acid binder, and then left to stand or subjected to a short-time steaming or dry heat treatment. Furthermore, when the present invention is applied to a textile printing process, a colored paste is usually printed on the fibers using sodium alginate or emulsion paste as the base paste, to which a dye, an acid binder, and if necessary, urea, etc. are added. Then, the dye is either subjected to intermediate drying and subjected to short-time steaming or drying treatment, or left as it is at room temperature or under heating without performing intermediate drying to fix the dye. In this case, it is also possible to print a color paste that does not contain an acid binder on the fibers which have been padded with an acid binder solution and dried, and then to fix them in the same manner as described above. After the fibers colored by such dyeing, padding dyeing or printing are lightly washed with water, they are treated with a bath of a commercially available fixing agent for anionic dyes, preferably a fixing agent of polyethylene polyamine type. In this case, fixing treatment can be carried out immediately after dyeing without even a light washing with water. The colored fibers dyed according to the present invention exhibit a yellow to blue-red color and are excellent in various fastness properties, particularly in wet fastness including harsh washing fastness. Next, the method of the present invention will be explained with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

In the examples, "parts" indicate "parts by weight."

Dye represented by the above formula (λMax=510 mμ; in water)
2. Dye bath and tailoring using 100 parts of crystalline sodium sulfate and 1000 parts of water, heat the dye bath to 95°C, soak 50 parts of cotton thread for 30 minutes, and then add 20 parts of sodium carbonate.
The staining is continued for 60 minutes.

Next, after a light wash with water, 4 parts of San Fixtures 555 (polyamine-based fixing agent*manufactured by Sanyo Chemical Industries, Ltd.) and 1000 parts of water were added.
After treatment at 60°C for 20 minutes in a bath prepared separately using the above-mentioned ingredients, washing with water and drying results in excellent moisture fastness, especially cotton staining grade 4 or higher in the washing fastness test (JISLO844A-4; 70°C). A vivid red dyeing with good fastness is obtained. Example 2 Using 2 parts of the dye represented by formula (9) (λMax = 370; in water), 1 part of Liponox RAN (nonionic penetrant, manufactured by Lion Oil Co., Ltd.), 30 parts of sodium chloride, and 1000 parts of water. Prepare a dyebath, heat the dyebath to 30℃, soak 50 parts of spun rayon yarn in it, treat it for 30 minutes, add 2 parts of sodium hydroxide, raise the temperature to 90℃ in 20 minutes, and maintain that temperature. Staining continues for 30 minutes.

Next, the liquid was removed without washing with water, and Thioset K (polyamine-based fixing agent, manufactured by Asahi Dye Co., Ltd.) 3 sounds - 100% water was used.
A bath prepared using 0 parts was heated to 60°C for 20 minutes, washed with water, and dried to prevent cotton staining in various fastness tests (JISLO844A-4; 70°C).
The result is a medium yellow dyeing with excellent wet fastness properties above grade. In this case, the same result can be obtained even if sodium hydroxide, which is added during dyeing, is added at the start of dyeing.

Example 3 Dye represented by formula (9) (λMax=513 mμ; in water) 20
200 parts of urea and 740 parts of water, and 20 parts of 5% sodium alginate paste and 20 parts of sodium carbonate were added to the solution.The cotton cloth was padded through the solution to double the original weight of the fiber. After intermediate drying, heat treatment is performed at 160° C. for 2 minutes.

Next, after washing lightly with water, apply 4 parts of Splash Fixtures WF New (polyamine-based fixing agent, manufactured by Nippon Someka Co., Ltd.) and 100 parts of water.
A bath prepared at 0 parts was heated to 60°C and treated for 20 minutes.
By washing with water and drying, a bright red dyed product with excellent wet fastness of cotton staining color grade 4 or higher can be obtained in various fastnesses, especially washing fastness test (JISLO844A-4; 70°C).

In this case, the same result can be obtained by applying a fixing process in which the dyed cloth is padded through a solution made with 30 parts of fixing agent and 1000 parts of water, squeezed to twice the weight of the fibers, and heat treated at 100°C for 2 minutes. .

Example 4 In formula (9), 15 parts of (λMax = 510 mμ; in water), 2 parts of Liponox 0CS (non-ionic penetrant, manufactured by Lion Oil Co., Ltd.), 20 parts of sodium carbonate, and 200 parts of urea were added to 500 parts of water. To this, 500 parts of a 5% sodium alginate aqueous solution is added and stirred well to prepare colored paste.

This color paste was printed on cotton cloth, and after intermediate drying, it was heated at 102℃ for 2 hours.
Steaming for 0 minutes, followed by light washing with water, fixing, washing, and drying in the same manner as in Example 3, results in various fastness tests, especially washing fastness test (JISLO844A-4:
A bright red dyeing with excellent wet fastness of grade 4 is obtained at 70°C. If the dyes having the structures shown in the table below are used in the same manner as described in Examples 1 to 4, yellow to blue-red dyeings having good wet fastness can be obtained.

The second column shows D in equation (9), the 31st column shows L in equation (9), and the hue is shown in 41e1.

Claims (1)

[Claims] 1. When dyeing cellulose fibers, there are general formulas (1) or (1)'▲mathematical formulas, chemical formulas, tables, etc.▼(1)▲
There are mathematical formulas, chemical formulas, tables, etc.▼(1)' [In the formula, A represents a benzene residue having at least one sulfonic acid group, and B represents a naphthol or 1-aryl-5 having at least one sulfonic acid group. - represents a pyrazolone residue. B' represents a 1-aryl-5-pyrazolone residue. R
_1 and R_2 represent a hydrogen atom or a methylene group. X represents an oxygen atom, a residue of an aliphatic or aromatic compound bonded via a nitrogen atom, a morpholino group or an amino group, and Y is an aliphatic group having at least 2 carbon atoms, a methyl group, a methoxy group, Represents a sulfonic acid group, a carboxylic acid group, a phenylene group or diphenylene group which may have a chlorine atom, a naphthylene group which may have a sulfonic acid group, or a ▲ mathematical formula, chemical formula, table, etc. Z is -O-
, -S-, -SO_2-, -CH_2-, -NH-, -
CH_2CH_2-, -CO-, -NHCO-, -CH
=CH- or -NHCH_2CH_2NH-. ) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is 1
．． 4 represents a piperazinylylene group. ] A method for dyeing cellulose fibers, characterized by using a novel disazo dye represented by the following in the presence of an acid binder.