JPS6147885A - Dyeing of cellulosic fiber material - 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 The present invention relates to a method for obtaining uniform dyeing with a high dye fixation rate when dyeing cellulose-based m-fiber materials by an exhaust dyeing method.

Conventional exhaust dyeing of cellulose fibers using reactive dyes 6
In 7ζ, dye fixation rate is relatively low and dye usage efficiency tends to be low, so dyeing costs are high. The problem is that the dyeing wastewater treatment cost is relatively high. Furthermore, because reactive dyes are attached to cellulose fibers through chemical bonds between the fibers and dyes, dyes cannot be transferred once dyed.
Another problem remains that it is more difficult to obtain uniform dyeing than with other dyes for cellulose fibers. In order to solve these problems, reactive groups with many different levels of reactivity have been developed, and
However, no fundamental solution has been reached.

As a result of intensive studies to solve these problems, the present inventors have found that a reactive dye for cellulose contains one or more nucleophilic substitution reactive groups and one or more nucleophilic addition reactive groups in the same molecule,
Using a reactive dye in which the leaving group of the nucleophilic substitution reactive group is a quaternary nitrogen substituent, first dyeing treatment is carried out at a temperature range of 30° C. or more and 100° C. or less while the pH of the dye bath is in the range of 4 or more and less than 8. After that, by adjusting the pH of the dye bath to a range of 8 to 14 and dyeing at a temperature of 25 to 90 degrees Celsius, dyed products with high dye fixation rate and good level dyeing properties can be produced for industrial use. We have found that this can be obtained with good reproducibility.

In the dyeing method of the present invention, first dyeing is carried out at a temperature range of 30°C or more and 100°C or less while the pH of the dye bath is in the range of 4 or more and less than 8. The nuclear substitution reactive group reacts with the fiber, but under these conditions 1It
The reaction rate with iiJk is relatively slow, and dangerous dyeing does not occur, so uniform dyeing can be obtained. However, sufficient dye fixation rate cannot be obtained by dyeing with a nucleophilic substitution reactive group containing a quaternary nitrogen substituent as a leaving group.
Subsequently, adjust the pH of the dye bath to a range of 8 or more and 14 or less.
By treating at a temperature of 5°C or higher and 90°C or lower, the nucleophilic addition reactive groups of the undyed dye remaining in the dye bath react with the fibers and dye them, resulting in a high dye fixation rate. will be obtained.

In the case of conventional reactive dyes, it is not possible to obtain a high dye fixation rate as in the method of the present invention, but dyeing is performed by determining the amount of inorganic salt and alkaline agent to be used so as to obtain the highest possible fixation rate. Therefore, if a predetermined amount of an inorganic salt and an alkaline agent are added from the initial stage of dyeing, the initial dyeing speed is extremely high and uneven dyeing tends to occur. In order to solve these problems, in industrial dyeing, measures have been taken to adjust the dyeing speed by adding inorganic salts and alkaline agents separately to the dye bath. Since it is difficult to quantitatively control the dyeing speed and the operation is very complicated, there has been a desire to develop dyes and dyeing methods that are easier to dye.

The present invention takes advantage of the characteristics of two types of reactive groups that have different reactivity with cellulose fibers, and can be used without complicated operations.
It is of high industrial value in that it allows dyed products with high dye fixation rate and good level dyeing properties to be obtained with good reproducibility.

The reactive dye for cellulose used in the first aspect of the present invention has a nucleophilic substitution reactive group and a nucleophilic addition reactive group in the same molecule, and the leaving group of the nucleophilic substitution reactive group is 4th I&
Refers to dyes that are nitrogen substituents, and nucleophilic substitution reactive groups include pyridine, pyridazine, pyridazone, pyrimidine, s-triazine, 1,2.4-) riazine, thiazole, Examples include reactive groups such as benzoxazole, benzothiazole, quinoline, isoquinoline, quinoxaline, quinazoline, and phthalazine. Further, as the tertiary nitrogen compound used as a leaving group, tertiary amine type and correspondingly dorazine type compounds are used.

The tertiary amine is aliphatic or heterocyclic, for example, the general formula or the general formula [In the above two formulas, R4 and R5 are aliphatic groups, such as alkyl groups, oxyalkyl groups, or alkoxyalkyl groups. , R6 is an aliphatic group such as an alkylene group or an alkenylene group, W is a hydrogen atom, an optionally substituted OH group, or a formula or a formula (wherein n is an integer of 1 to 4). or an optionally substituted aryl group, R,, R8 and 2 are aliphatic groups such as alkylene groups, and z3 is a nitrogen atom or a 30H group. ]1
This is the corresponding compound. The amine has one or more tertiary
In addition to the 7-mino group, it may have a substituent that does not react with the reactive dye. Such substituents include, for example, a nitrogen atom, a nitro group, an alkoxy group, or a hydroxyl group.

The aliphatic amine represented by the general formula (II) is, for example, the general formula [wherein R6 has the same meaning as above, and (2)].

is a hydrogen atom or a hydroxyl group. ] are suitable. For example, dimethylallylamine,
Dimethyl-β-hydroxyethylamine, dimethyl-β
-Ethoxyethylamine and other compounds may be mentioned.

Similarly, aliphatic amines represented by the general formula (wherein R6 and n have the same meanings as above) are also effective.

Examples of this type of compound include poly(1)-alkylenepo-1-noamines such as 1-pentamethyldiethylenetriamine and hexamethylene-left-1noethylenetetraamine.

Furthermore, the general formula [where λ, . represents an alkylene group. ] Examples include 1,2-bis-dimethylaminoethane, 1,4-bis-dimethylbutane, and 1,6-pis-dimethylaminohexane.

General formula [wherein R1□ represents an alkyl group]. Examples of compounds represented by the following include dimethylethylamine, dimethylpropylamine, dimethylisopropylamine, and trimethylamine.

Examples of the heterocyclic amine represented by the general formula (IV) include the general formula (wherein z3 and n have the same meanings as above, and m and T represent integers of 1 to 4). ], pyrrolidibuin, 1-azabicyclo-(2,2,1)
-hebutane, quinuclidine, quinuclidine, 1-azabicyclo-(3,2)octane, 1-azabicyclo(3°2)-nonane, 1,4-diazabicyclo-(2°2.2)
)-octane (triethylenecyamine) and compounds represented by the structural formula.

On the other hand, compounds used as hydrazine-based compounds must have at least one tertiary nitrogen atom, and one of the two nitrogen atom circles of the hydrazine group has two carbon atoms as the tertiary nitrogen atom. It must be combined with
Other nitrogen atoms may be substituted or unsubstituted.

Examples of such hydrazine include general type roof tiles 2. is an aliphatic hydrocarbon group, -〇-51 (group, sulfonic acid group, or a group represented by the formula (wherein R,, R□3 has the above-mentioned meaning, and □6 indicates an alkylene group) , or represents a hydrogen atom.] More preferably, a compound represented by the general formula [wherein m and n have the above-mentioned meanings, and P represents an integer of 1 to 5.] The aliphatic hydrocarbons of these hydrazine compounds may be branched, but linear ones are more preferable.

Alternatively, a compound represented by the general formula [wherein q and q represent an integer of 3 to 4], such as N, dimethylhydrazine, N
, N,N'-4-limethylhydrazine, N-aminopiperidine, and compounds represented by the structural formulas.

or a compound represented by the structural formula [wherein λ and 6 represent an alkyl group], or a compound represented by the structural formula [wherein R16 has the same meaning as above]. ] Compounds represented by the following can be mentioned.

Furthermore, examples of compounds having tertiary nitrogen atoms in the ring include pyridine and its derivatives; unsubstituted or substituted alkyl or alkoxy groups, carboxylic acid groups and alkali metal salts thereof,
Represents carboxylic acid ester, carboxylic acid amide, sulfonic acid group and its alkali metal salt, sulfonic acid amide, cyano group, aldehyde group, hydroxyl group, etc. Among compounds having carboxylic acid, nicotinic acid and its alkali metal salt are excluded] Compounds represented by, for example, pyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, α-picoline, β-picoline, T-picoline, 3-ethyl-4methylpyridine, 4-ethyl-2methylpyridine, 5-ethyl-2-methylpyridine, 6-ethyl-3methylpyridine, 4-methoxypyridine, picolinic acid, quinolinic acid, cinchomeronic acid, isocincomeronic acid, cypifulic acid, dinicotinic acid, α-carboxycomeronic acid, β - Pyridine carboxylic acids such as carboxycomeronic acid and methylnicotinic acid, alkali metal salts thereof such as sodium and potassium salts, and esters of these carboxylic acids, pyridine carboxylic acid amides such as nicotinic acid amide, picolinic acid amide, and inniacito, 3 Examples include compounds such as -pyridine sulfonic acid, 3-pyridine sulfonic acid amide, sulf-1 pyridine, 3-pyridylacetic acid, methylidine, pyridine aldehyde, α-pyridone, β-pyridone, and 3-cyanated pyridine.

Furthermore, compounds having the 31st and nitrogen atoms in the heterocycle include, for example, pyridazine, pyrimidine, pyrazine, 4-H-
1-2-oxazine, 6-H-1-2-oxazine, 2
-H-1-3-oxazine, 4-H-1-3-oxazine, 2-H-indazole, benzimidazole, imidazole, triazole, thiazole, isothiazole, oxazole, isoxazole, furazane, benzoxazole, benzothiazole, butane, quinoline,
Examples include compounds such as isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, 1-P-naphthyridine, and butyridine, and these compounds may be substituted in the same manner as in the case of formula (XX).

Examples of the nucleophilic addition reactive group of the reactive dye for cellulose used in the method of the present invention include saturated alkane monocarboxylic acid amide type, saturated alkanedicarboxylic acid amide type, saturated alkane monocarboxylic acid type, cycloalkane carboxamide type, alkene Examples of reactive groups include monocarboxamide, alkenedicarboxamide, saturated aliphatic ketone, saturated aliphatic sulfonic acid amide, vinyl sulfamide, β-saturated ethyl sulfone, and vinyl sulfone. .

For coloring in the reactive dye of the present invention, azo-based, metal-containing azo-based, anthraquinone-based, phthalocyanine-based, formazan-based, oxazine-based dye matrices are used, and these have at least one or more sulfonic acid group. Alternatively, examples include those having a water-soluble group such as a carboxylic acid group.

Examples of dyes suitably used in the method of the present invention include, for example, in the general formula c, D is a residue of an organic dye having a sulfonic acid group, D and R2 are each a hydrogen atom or a lower alkyl group, and R
3 is a non-aromatic or aromatic tertiary compound having a quaternary nitrogen atom.
class nitrogen compound residues, 2e, and Z2 are each a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom,
Carboxylic acid group or sulfonic acid group, Y is vinyl group or -
CH, CH20Z (Z represents a group that is eliminated by the action of an alkali). ] or the general formula [where De Rle R2e R5e zl # z
l Et has the same meaning as above. ] Or the general formula [where De R1p R2p R3e zl # z
It has the same meaning as Gta. ] Or the general formula [where D e R1, RB t R3 # zl #
zl C has the same meaning as above. ] Or the general formula [where De R1e R2* R3e zz e z
l It has the same meaning as Gt1m. ] Or the general formula [where D , R, , R2, R3, z□l z, (*
Indicates the same meaning as above. ] Or the general formula [wherein D, R, and R8 have the same meanings as above. ] Or the general formula [wherein D, R, R3, and Y have the same meanings as above,
A represents a substituent or a halogen atom that does not react with cellulose. ] Or the general formula [wherein D , R, , R3 and Y have the same meanings as above. ] Or the general formula [wherein D, R□, R3, and A have the same meanings as above. ] Or the general formula [wherein D, R, and R3 have the same meanings as above. ] Or the general formula [wherein D , Ro, R2I and A have the same meanings as above. ] Or the general formula [where D, R1, R,, R3, Zl, Z2. Y
has the same meaning as above, n represents a diamino residue bonded to the $-triazinyl nucleus by two amino groups, and 1
□0. R2° each represents a hydrogen atom or a lower alkyl group. ] Or the general formula [wherein D, R, R□, R, and Y have the same meanings as above. ] Or the general formula [wherein D , R1, R2, R, , R□3. R3゜.

B and Y have the same meanings as above. ] Or general formula [In the formula, D, R, R2, R6, R and 9. R3゜.

2nd grade, z2. y has the same meaning as above. ] etc. can be mentioned.

In addition, general formula (II), (XXVI), (XX
The substituent A that does not react with cellulose in
(indicates the same meaning as above).

General formula (I), (II), (XX[) ~(X
Regarding dyes represented by m'Ote, dyes in which R3 is a herogen atom are disclosed in Japanese Patent Publication No. 37-17790 and Japanese Patent Publication No. 37-17790.
No. 8-10188, Special Publication No. 1973. -19190, JP 38-23287, JP 39-18184, JP 56-163153, JP 58-49752, JP 58-8034, JP 40-17113, JP-A No. 53-48328, JP-A No. 57-42985
No., Japanese Patent Publication No. 57-49663, Special Publication No. 42-2626
No., JP-A-50-178, JP-A-56-92961, JP-A-56-103247, JP-A-57-12
No. 8373, JP-A-57-143570, JP-A-58
-49752, JP 58-80348, DG 52-121039, JP 38-23287, JP 56-155250, JP 57-57754, JP 56-90857 , Japanese Patent Publication No. 57-18762
No., JP-A-57-212259, JP-A-56-12
No. 0769, JP-A-54-722262, JP-A-54
-73827, JP-A-57-78458, etc., and is synthesized from these dyes by the following method.
I can do that.

That is, general formula (I), (n), (XX[) ~(
W) can be obtained by condensing a compound represented by general formulas (mV) to (XX) with a known dye in which R3 is a halogen atom, and this reaction is carried out in an aqueous medium at 10 to 100°C. Even more wildly, 40~90℃
It can be carried out at a pH of 2 to 10, more preferably 3 to 8.

The method of the invention is usually applied to the dyeing of cellulosic fiber materials from an aqueous medium and is preferably carried out as follows.

That is, the same molecule described above contains at least one nucleophilic substitution reactive group and one or more nucleophilic addition reactive group, and the leaving group of the nucleophilic substitution reactive group is a quaternary nitrogen substituent. A bath is prepared containing a predetermined amount of a reactive dye, an electrolyte such as sodium sulfate or sodium chloride at 1 to 150 f/l as necessary, and a dyeing aid such as a bath softener as necessary. In order to adjust the pH of the dye bath to a range of 4 to 8, substances that exhibit a pH balancing action as necessary, such as acids such as carbonic acid, phosphoric acid, acetic acid, citric acid, and tartaric acid, and their sodium and potassium salts. , or a monomer such as an ammonium salt.
Or you can add a mixture. Add the cellulose fiber material to the dye bath prepared in this way and
5 minutes to 90 minutes, preferably 10 minutes to 90 minutes at a temperature of 0°C or lower
Perform the dyeing process for 30 minutes, then adjust the dye bath at a temperature of 25°C to 90°C by adding an alkaline agent such as sodium carbonate, tribasic sodium phosphate, or caustic soda so that the pH is in the range of 8 to 14. The staining process is carried out for 5 minutes to 180 minutes, preferably 10 to 60 minutes. With this method (ζ), dyed products with a higher dye fixation rate can be obtained uniformly and with good reproducibility.

The cellulosic fiber material dyed in this manner can be obtained as a dyed product having excellent waxiness by ordinary washing treatment.

Next, the present invention will be explained in detail with reference to Examples, in which "part" is "
Parts by weight.

Example-1 2 parts of dye represented by the following structural formula (%) in free acid form, 100 parts of sodium sulfate (anhydrous)
1 ml of 2,000 parts of a bath containing 4 parts of monobasic sodium phosphate, and 1 part of dibasic sodium phosphate was prepared.

Add 100 parts of silled wire knit to this bath and heat at 80°C for 30 minutes.
After dyeing for 0 minutes, it was cooled to 60°C, 40 parts of sodium carbonate was added, and dyeing was carried out for 30 minutes.

After dyeing, soaping was carried out for 10 minutes at 95°C in 2000 parts of a bath containing 4 parts of anionic detergent, followed by washing with water and drying. obtained, and the fastness was also good.

Example-2 3 parts of dye represented by the following structural formula (%) in free acid form, 10 parts of sodium sulfate (anhydrous)
2,000 parts of a bath containing 0 parts was adjusted to ¥A.

When dyeing was carried out in the same manner as in Example 3 using 3 parts of the dye represented by the formula, a uniform deep red dyed product with a high dye fixation rate was obtained, and its waxability was also good.

Example 5 When dyeing was carried out in the same manner as in Example 3 using 2 parts of the dye represented by the following structural formula (%) in the form of a free acid, a uniform red dyed product with a high dye fixation rate was obtained. was obtained, and its fastness was also good.

Example-6.

When dyeing was carried out under the same conditions as in Example 1 using 2 parts of the dye represented by the following structural formula (%) in the form of a free acid, a uniform bluish-red dyed product with a high dye fixation rate was obtained. , and its fastness was also good.

Example-7 2 parts of dye represented by the following structural formula (%) in acid form of a string, 100 parts of sodium sulfate (anhydrous)
A bath containing 2000 parts of

100 parts of the silled wire knit was put into this bath, the temperature was raised from 30°C to 60°C over 20 minutes, and after holding at 60°C for 10 minutes, 10 parts of tribasic sodium phosphate was added, and dyeing was continued for an additional 40 minutes. .

After dyeing, it was washed for 10 minutes at 95°C in 2000 parts of a bath containing 4 parts of an anionic detergent, washed with water, and dried. A uniform blue dyed product with a high dye fixation rate was obtained. The adhesion properties were also good.

Example 8 When dyeing was carried out under the same conditions as in Example 2 using 2 parts of the dye represented by the following structural formula in the form of a free acid, a uniform bright blue dyed product with a high dye fixation rate was obtained. , and its fastness was also good.

Example 9 Dyeing was carried out under the same conditions as Example 2 using 3 parts of a dye represented by the following structural formula (%) in the form of a free acid, resulting in a uniform blue color with a high dye fixation rate. Example 10 A dyed product was obtained with good fastness. 3 parts of the dye represented by the following structural formula (CuPc represents copper phthalocyanine) in the form of free acid and 100 parts of sodium sulfate (anhydrous) were added. Containing bath 2
100 parts of silled cotton thread was placed in 000 parts, the temperature was raised from 30°C to 80°C for 30 minutes, and after treatment at 80°C for 10 minutes,
30 parts of sodium carbonate was added and staining was carried out for 40 minutes.

After dyeing, washing was carried out at 95°C for 10 minutes in 2000 parts of a bath containing 4 parts of non-ionic detergent, followed by water washing and drying, resulting in a uniform bright greenish-blue dyed product with a high dye fixation rate. A uniform dark blue dyed product with a high rate of dyeing can be obtained, and the fastness is also good.

Claims (4)

[Claims] (1) When dyeing cellulose fiber materials, the same molecule contains at least one nucleophilic substitution reactive group and one or more nucleophilic addition reactive group, and one or more nucleophilic substitution reactive groups. Using a reactive dye whose leaving group is a quaternary nitrogen-containing group, the dye bath pH is 4 or more and less than 8 and treated at a temperature of 30°C or more and 100°C or less. A method for dyeing cellulose fiber materials, characterized by processing at a temperature of 25°C or higher and 90°C or lower, adjusted to the following range. (2) The nucleophilic substitution reactive group is an s-triazinyl group, and the nucleophilic addition reactive group is SO_2CH=CH_2 or SO_2CH_2CH
_2Z (Z represents a group that is eliminated by the action of an alkali.)
2. A method according to claim 1, using a reactive dye. (3) The reactive dye has the following general formula ▲ Numerical formula, chemical formula, table, etc. A non-aromatic or aromatic tertiary nitrogen compound residue having a quaternary nitrogen atom, Z_1 and Z_2 are each a hydrogen atom,
Lower alkyl group, lower alkoxy group, halogen atom, carboxylic acid group, or sulfonic acid group, Y is a vinyl group or -CH_2CH_2OZ
(Z represents a group that is eliminated by the action of an alkali). ] The method according to claim 1, which is a dye represented by: (4) The reactive dye has the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, D is a residue of an organic dye having a sulfonic acid group, R_1 is a hydrogen atom or a lower alkyl group, R_
3 is a non-aromatic or aromatic tertiary compound having a quaternary nitrogen atom.
Y is a vinyl group or -CH_2CH_2OZ (Z is a group that is eliminated by the action of an alkali), and A is a substituent that does not react with cellulose or a halogen atom. ] The method according to claim 1, which is a dye represented by: