JPH0611947B2 - Dyeing method for polyester / cellulose blended products - Google Patents

Description

The present invention relates to an exhaust dyeing method for a mixed fiber material of a cellulosic fiber and a polyester synthetic fiber.

Conventionally, for dyeing a mixed fiber material such as a blended polyester synthetic fiber and a cellulosic fiber, a mixed woven product, a disperse dye is used as the dye for the polyester fiber, and a reactive dye is used as the dye for the cellulose fiber. Although the optimum dyeing conditions for disperse dyes are dyeing temperatures of 100 ° C to 140 ° C and the pH of the dyeing bath is weakly acidic to neutral, the optimum dyeing conditions for reactive dyes are 40 ° C to 90 ° C. It was difficult to dye the polyester fiber and the cellulosic fiber at the same time in one bath because the pH was alkaline.

In industrial dyeing, a two-bath two-step method in which polyester fibers and cellulose fibers are dyed in separate baths under optimal dyeing conditions, or in the same bath, either polyester or cellulose is optimally dyed first One of the one-bath two-step dyeing methods, in which the dyeing is performed under the following conditions, and then the dyeing bath conditions are changed to the other optimal dyeing conditions, the two-bath two-step dyeing method is used. It has a drawback that it is long and requires a long time for dyeing, consumes a large amount of energy, and the dyeing cost is high. On the other hand, the one-bath two-step dyeing method solves the drawbacks of the two-bath two-step method to some extent in terms of the dyeing time, etc. However, there are problems such as uneven dyeing due to runout of the ink, poor reproducibility of dyeing, and a decrease in fastness caused by the fact that optimal dyeing conditions cannot be completely reproduced.

The present inventors have found the method of the present invention as a result of intensive studies on a method for dyeing a mixed material of a polyester-based synthetic fiber and a cellulosic fiber more reasonably and efficiently.

That is, when dyeing a polyester / cellulose mixed fiber material by a one-bath two-step dyeing method using a disperse dye and a reactive dye in combination, the following general formula (I) or (II), [Wherein D is a residue of an organic dye having a sulfonic acid group, R
₁ and R ₂ are each a hydrogen atom or a lower alkyl group, A is a substituent or a halogen atom which does not react with cellulose, X is a halogen atom, Z ₁ and Z ₂ 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 ₂ CH ₂ OZ
(Z represents a residue of a basic acid). ] The polyester side is dyed with a disperse dye at a temperature of 100 ° C or higher and 140 ° C or lower using the polyfunctional reactive dye represented by the following formula, and then the pH is adjusted to 8 in the temperature range of 80 to 95 ° C during the cooling process.
To 9.5, and then adjust the pH to 10 to 13 at a temperature of 50 to 70 ° C. for dyeing to obtain a fast dyed product having a high dye fixation rate with good reproducibility. It has been found.

Usually, when dyeing a cellulose fiber by a temperature-lowering method using a reactive dye for a cellulose fiber, dyeing is performed by adjusting the pH of a dyeing bath to a range of 10 to 13 in a temperature range of 50 to 80 ° C. Problems remain, such as the dye fixation rate is not very high, dyeing reproducibility is poor, and it is difficult to obtain uniform dyeing.

According to the method of the present invention, it is possible to control the dyeing speed of the reactive dye in the initial stage of dyeing relatively slowly by dyeing in the high temperature region (80 to 95 ° C.) of the temperature-falling dyeing program under weak alkaline conditions. This is possible, and dyeing with good levelness can be obtained in combination with good penetrability of the dye at high temperature. Furthermore, the treatment with a weak alkaline bath in a high temperature region is effective for removing the stagnation of the disperse dye contaminated on the cellulose fiber side, and a dyeing product having excellent fastness is obtained. Furthermore, the pH is 10 to 13 in the medium temperature range (50 to 70 ° C).
By adjusting to 2, the dyeing of unfixed dye that was not dyed in the high temperature region can be promoted, a high dye fixing ratio can be obtained, and a dyed product with good reproducibility can be obtained.

Polyester used as a material to be dyed in the present invention /
Examples of materials for blending with cellulose include polyester / cotton blended products, polyester / loyon blended products, polyester / linen blended products, and mixed woven products thereof. Either form may be used.

The pH adjusting agent used in the method of the present invention is an alkali metal hydroxide, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, phosphate, phosphoric acid-hydrogen salt, trihydrogen phosphate, nitrate. , Borate, perborate, acetate and the like, and further organic bases such as tertiary amines such as triethanolamine and diethylaminophenol.

The disperse dye used in the method of the present invention may be any disperse dye used for polyester fibers, for example,
COLOR INDEX Third Edition Volume 2 (The Society o
f Dyers and Colorists, 1971) and the like.

On the other hand, the reactive dye for cellulose used in the method of the present invention,
A multifunctional reactive dye having one or more nucleophilic substitution reaction type reactive groups and one or more nucleophilic addition reaction type reactive groups in the same molecule, and a multifunctional type having one or more nucleophilic substitution type reactive reaction groups Refers to reactive dyes, and examples of the nucleophilic substitution reaction type reactive group include pyridine type, pyridazine type, pyridazone type, pyrimidine type, S-triazine type, 1,2,4-triazine type, thiazole type, benzoxazole type and benzothiazole. Examples thereof include a reactive group such as a system, a quinoline system, an isoquinoline system, a quinoxaline system, a quinazoline system, and a phthalazine system.

On the other hand, as the nucleophilic addition reaction type reactive group, for example, saturated alkane monocarboxylic acid amide type, saturated alkane dicarboxylic acid amide type, cicle alkane carboxamide type, alkene mono carboxamide type, alkene dicarboxamide type,
Saturated aliphatic ketone series, saturated aliphatic sulfonic acid amide series,
Examples thereof include vinylsulfoamide-based, β-saturated ethylsulfone-based, and vinylsulfone-based reactive groups.

As the dye pigment base in the reactive dye of the present invention, monoazo dyes, disazo dyes, metal-containing azo dyes, anthraquinone dyes, phthalocyanine dyes, formazan dyes, oxazine dyes and the like are used, and at least one or more of these dyes are used. Examples thereof include those having a water-soluble group such as a sulfonic acid group or a carboxylic acid group.

Examples of dyes used in the method of the present invention include, for example, the general formula [Wherein D is a residue of an organic dye having a sulfonic acid group, R
₁ and R ₂ are each a hydrogen atom, or a lower alkyl group, X
Is a halogen atom, Z ₁ and Z ₂ are each a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxylic acid group, or a sulfonic acid group, and Y is a vinyl group or —CH ₂ CH ₂
Represents OZ (Z represents a residue of a basic acid). ] Or the general formula [Wherein D, R ₁ , X, and Y have the same meanings as described above, and A
Represents a substituent or a halogen atom that does not react with cellulose. ] Or the general formula [In the formula, D, R ₁ , R ₂ , X, Z ₁ and Z ₂ have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , R ₂ , X, Z ₁ and Z ₂ have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , R ₂ , X, Z ₁ and Z ₂ have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , R ₂ , X, Z ₁ and Z ₂ have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , R ₂ , X, Z ₁ and Z ₂ have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ and X have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , X, and Y have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , X, and A have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ and X have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , X, and A have the same meanings as described above. ] Or the general formula [Wherein D, R ₁ , R ₂ , X, Z ₁ , Z ₂ and Y have the same meanings as described above, and B represents a diamino residue bonded to the S-triazinyl nucleus by two amino groups. , R ₃ and R ₄ each represent a hydrogen atom or a lower alkyl group. ] Or the general formula [In the formula, D, R ₁ , R ₂ , X and Y have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , R ₂ , R ₃ , R ₄ , X, Y and B have the same meanings as described above. ] Or the general formula [In the formula, D, R ₁ , R ₂ , R ₃ , R ₄ , X, Z ₁ , Z ₂ and Y have the same meanings as described above. ] Etc. can be mentioned.

The dyes represented by formulas (I) to (XVI) are described in
37-17790, JP 38-10188, JP 45-19190
Japanese Patent Publication No. 38-23287, Japanese Patent Publication No. 39-18184, Japanese Unexamined Patent Publication No. 56
-163153, JP-A-58-49752, JP-A-58-8034,
JP-B-40-17113, JP-A-53-46328, JP-A-57-42
985, JP 57-49663, JP 42-2626, JP
50-178, JP-A-56-92961, JP-A-56-103247,
JP-A-57-128373, JP-A-57-143570, JP-A-58-
49752, JP58-80348, JP52121039, JP38-23287, JP56-155250, JP57-577.
54, JP-A-56-90857, JP-A-57-18762,
57-212259, JP-A-56-120769, JP-A-54-722262
Nos. 54-73827 and 57-78458.

The method of the present invention is generally applied to dyeing a polyester / cellulose mixed material from an aqueous medium, and is preferably carried out as follows.

That is, a predetermined amount of the above polyester fiber disperse dye and a pH adjuster for adjusting the pH of the disperse dye disperse dyeing agent and the dye bath from weakly acidic to neutral, for example, carbonic acid, if necessary.
An acid such as phosphoric acid, acetic acid, formic acid, citric acid, tartaric acid and the like, and their sodium salts, potassium salts, ammonium salts, etc., or a mixture thereof are added to adjust the dye bath. In this dye bath, electrolytes such as sodium sulfate or sodium chloride 1 to
Although 150 g, 1 and a predetermined amount of the reactive dye can be added, either or both of the electrolyte and the reactive dye may be added after dyeing the polyester fiber side.

The polyester / cellulose mixed material is placed in the dyeing bath adjusted in this way, and the mixture is heated at a temperature of 100 ° C to 140 ° C for 10 to 10 ° C.
After dyeing for 120 minutes, preferably 20 to 60 minutes, the dyebath is cooled to 95 ° C. or less in 5 minutes to 60 minutes, and the amount of the above-mentioned multifunctional reactive dye and sodium sulfate or sodium chloride are used. Add 1 to 150 g / g of salt. (When part or all of the reactive dye and neutral salt is already added to the dye bath before dyeing on the polyester side,
The remaining portion may or may not be added. ) Then, in a temperature range of 80 ° C to 95 ° C, sodium hydrogen carbonate,
The pH of the dyeing bath is adjusted to 8 to 9.5 by mainly using a weakly alkaline pH adjusting agent such as sodium acetate or disodium phosphate.
And cool to 70 ° C or lower in 5 to 30 minutes. Then, the pH of the dyebath is adjusted to 10 to 13 by using an alkali agent such as sodium carbonate, trisodium phosphate, caustic soda and caustic potash alone or in a mixture in a temperature range of 50 to 70 ° C. Stain for 90 minutes. By this method, a dyed product having a high dyeing rate and excellent fastness can be uniformly and reproducibly obtained.

The polyester / cellulose mixed fiber material dyed in this manner can be obtained as a dyed product having excellent fastness by carrying out an ordinary washing step.

Next, the present invention will be described with reference to examples, but "parts" in the examples
Indicates "parts by weight".

Example-1 The following structural formula 2 parts of a disperse dye and 2 parts of sodium acetate,
Acetic acid 0.3 parts, anionic dispersion leveling agent (Sumipon T
F: Sumitomo Chemical Co., Ltd.) 2000 parts of a bath containing 2 parts were prepared. The pH at this time was 5.0.

In this bath, polyester / cotton blend knit (50/50) 10
0 part was charged, the temperature was raised to 130 ° C. in 30 minutes, the temperature was kept for 30 minutes, and then cooled to 90 ° C. in 20 minutes. The following structural formula in the form of free acid at 90 ° C 2 parts of dye, sodium sulfate (anhydrous) 100
Part, 8 parts of sodium hydrogen carbonate are added, and the mixture is added to 60 parts in 20 minutes.
Cooled to ° C. (The pH of the dyebath at this point was 8.6.) At 60 ° C., 10 parts of sodium carbonate and 40 Be 'caustic soda 2
Parts were added and dyeing was carried out for 30 minutes. (The pH of the dyebath at this point was 11.7.) Subsequently, 95 parts were added in 2000 parts of a bath containing 4 parts of anionic activator.
When soaping treatment was carried out at 10 ° C. for 10 minutes, followed by washing with water and drying, a dyed product in bright greenish yellow with excellent fastness was obtained.

Example-2 The following structural formula 2000 parts of a bath containing 1 part of the disperse dye represented by the following formula, 0.05 part of acetic acid, and 2 parts of an anionic dispersion leveling agent (Sumipon TF: Sumitomo Chemical Co., Ltd.) were prepared. At this time, the pH was 4.0.

100% polyester / cotton blend knit (50/50) in this bath
The parts were put in, heated to 130 ° C. in 30 minutes, held for 20 minutes, and then cooled to 95 ° C. in 20 minutes. The following structural formula in the free acid form at 95 ° C 1 part of the dye represented by and 100 parts of sodium sulfate (anhydrous) were added, and the mixture was cooled to 85 ° C. for 10 minutes. At 85 ° C, 8.2 parts of sodium hydrogen carbonate was added, and the mixture was cooled to 60 ° C in 25 minutes. The pH of the dyebath at this point was 8.6. 20 parts of Sumibix Salt NA (Sumitomo Chemical Co., Ltd. product), which is commercially available as an alkaline agent for reactive dyes, was added at 60 ° C., the pH of the dyeing bath was adjusted to 11.5, and dyeing was carried out at the same temperature for 30 minutes.

Then 97 in 2000 parts of a bath containing 4 parts of anionic detergent
A soaping treatment was carried out at 10 ° C. for 10 minutes, followed by washing with water and drying to obtain a dyed product having a bright red color with excellent fastness.

Example-3 The following structural formula 2000 parts of a bath containing 4 parts of the disperse dye represented by the formula (1), 0.1 part of acetic acid, and 2 parts of an anionic dispersion leveling agent (Sumipon TF: Sumitomo Chemical Co., Ltd.) were prepared. At this time, the pH was 5.0.

100 parts of polyester / linen blended fabric (65/35) was put into this bath, heated to 130 ° C. in 30 minutes, held for 40 minutes, and cooled to 95 ° C. in 20 minutes. The following structural formula in the free acid form at 95 ° C 2.5 parts of dye, sodium sulfate (anhydrous) 10
0 part was added and the mixture was cooled to 80 ° C. in 15 minutes. At 80 ° C, 7.4 parts of sodium hydrogencarbonate was added, and at 50 ° C for 20 minutes.
Cooled down. At this time, the pH of the dyebath was 8.5.

At 50 ° C., 20 parts of Espolone H (on the other hand, a fat and oil product) commercially available as an alkaline agent for reactive dyes was added to adjust the pH of the dyeing bath to 11.5, and dyeing was carried out at the same temperature for 40 minutes.

Then, 9 in 2000 parts of a bath containing 4 parts of anionic detergent
Soap for 10 minutes at 7 ° C, then wash with water,
After drying, a uniform dark blue dyeing having excellent fastness was obtained.

Example-4 The following structural formula The following structural formula in the form of 3 parts of the disperse dye represented by ([CuPc] represents copper phthalocyanine.) 2 parts of reactive dye, 0.1 part of acetic acid, 100 parts of sodium sulfate (anhydrous), anionic dispersant (Sumipon
2,000 parts of a bath containing TF: Sumitomo Chemical Co., Ltd.) was prepared.
The pH at this time was 5.0.

Polyester / cotton blending unit (50/50) in this bath
Add 100 parts, heat up to 130 ° C in 30 minutes, hold for 40 minutes, cool to 90 ° C in 30 minutes, add 4.5 parts of sodium hydrogen carbonate at 90 ° C, and add 70 parts in 15 minutes.
Cooled to ° C. The pH of the dyebath at this point was 8.5. After adding 15 parts of sodium carbonate and 5.0 parts of 40Be 'sodium hydroxide at 70 ° C to adjust the pH of the dyeing bath to 11.6, dyeing was carried out at the same temperature for 40 minutes.

Then, 9 in 2000 parts of a bath containing 4 parts of anionic detergent
Soap for 10 minutes at 7 ° C, then wash with water,
When it was dried, a deep greenish blue dyeing having a high fastness and a high density was obtained.

Example-5 As the disperse dye, the following structural formula 2 parts of the dye represented by and the reactive dye in the form of a free acid 100 parts of a polyester / cotton blend knit (50/50) was dyed under the same conditions as in Example 1 by using 2 parts of the dye represented by the following formula to obtain a red dyed product having high fastness and high density.

Example-6 As the disperse dye, the following structural formula The following structural formula in the form of a free acid is used as 1 part of the dye represented by 100 parts of a polyester / cotton blending unit (50/50) was dyed using 1 part of the dye represented by the formula (1) under the same conditions as in Example-2 to obtain a uniform bright blue dyeing having excellent fastness. .

Example-7 The following structural formula as a disperse dye 2 parts of the dye represented by A polyester / cotton blend unit (50/50) was dyed under the same conditions as in Example 4 by using 2 parts of the dye represented by the following formula to obtain a scarlet red dyeing product having excellent fastness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takashi Omura, Inventor Takashi Omura 3-98 Kasugade, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. Naka 3-chome 1-98 Sumitomo Chemical Co., Ltd.

Claims (1)

[Claims] 1. When dyeing a polyester / cellulose mixed fiber material by a one-bath two-step dyeing method in which a disperse dye and a reactive dye are used in combination, the following general formula (I) or (II), [Wherein D is a residue of an organic dye having a sulfonic acid group, R
₁ and R ₂ are each a hydrogen atom or a lower alkyl group, A is a substituent or a halogen atom which does not react with cellulose, X is a halogen atom, Z ₁ and Z ₂ are each a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom. , A carboxylic acid group, or a sulfonic acid group, Y is a vinyl group or —CH ₂ CH ₂ OZ
(Z represents a residue of a basic acid). ] In the dyeing process, a polyfunctional reactive dye represented by the following is first used at a temperature of 100 ° C to 140 ° C and a pH of 4 to 7.5.
After dyeing the polyester side with the disperse dye in the range of, the pH is 8 to 9.5 at a temperature of 80 ° C to 95 ° C in the cooling process.
Adjust the pH range to 10 ℃ at a temperature of 50 ℃ ～ 70 ℃.
A dyeing method characterized in that the cellulose side is dyed with a reactive dye by adjusting to 13.