JPH06346381A - Dyeing assistant for polyester-based fiber - Google Patents

Abstract

PURPOSE:To obtain a dyeing assistant for polyester-based fiber capable of providing a level dyed material with good reproducibility by use thereof not only for ordinary polyester-based fiber but also for new synthetic fiber polyester (fine denier or combined filament polyester of different shrinkages) in dyeing. CONSTITUTION:This dyeing assistant for polyester-based fiber is composed of a polyalkylene glycol ester of a fatty acid, a sulfuric ester salt of a polyalkylene oxide adduct to polycyclic phenols (4-20 number of rings), and hindered phenols.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dyeing aid for polyester fibers. More specifically, it relates to a dyeing aid used when dyeing a polyester fiber with a disperse dye.

[0002]

2. Description of the Related Art Conventionally, as a dyeing aid for polyester fibers, one containing a polyoxyalkylene-based surfactant having an HLB of 6 or more and a hindered phenol compound (Japanese Patent Publication No. 55-4877). Comprising a mixed ester of a polyhydric alcohol oxyalkylene ether with a dicarboxylic acid and an aliphatic monocarboxylic acid (Japanese Patent Publication No. 4-18070), an alkylene oxide adduct of styrenated phenols, sulfuric acid. Ester salt
No. 12036) is known. However, in the case of ordinary polyester fibers, leveling and dispersibility higher than conventional levels are required. Further, in the case of dyeing polyester fibers composed of fine denier and heterogeneous shrinkage mixed yarn, which are generally called new synthetic fibers in recent years, good levelness cannot be obtained by the above technique. In Japanese Patent Publication No. 55-4877,
It is described that a polyoxyalkylene-based surfactant having HLB of 6 or more and a hindered phenol-based compound may be used in combination with a polyoxyalkylene alkylphenyl ether sulfate ester salt, but in this system, a normal polyester is used. In the case of fibers, it is not possible to cope with higher levels, and in the case of new synthetic fibers, the leveling and dispersibility are insufficient.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to cope with the recent increase in the level when dyeing ordinary polyester fibers, and even when dyeing new synthetic fibers, the dye is used in the dyeing bath during dyeing. To obtain good dispersibility and dye transferability to obtain a level dyeing product, and to obtain a dyeing aid having good reproducibility.

[0004]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors provide ordinary polyester fibers with a high level and impart reproducible leveling properties to new synthetic fibers. The present invention has been achieved as a result of intensive studies on dyeing assistants.

That is, the present invention relates to a higher fatty acid ester of polyalkylene glycol (A), a sulfuric acid ester salt of an alkylene oxide adduct of polycyclic phenols (having 4 to 20 rings) (B) and a hindered phenol. -A dyeing aid for polyester fibers composed of the group (C).

The polyalkylene glycol forming the higher fatty acid ester (A) of polyalkylene glycol is
An oxyalkylene group is added to a polyvalent alcohol. As the polyhydric alcohol, ethylene glycol
And divalent alcohols such as propylene glycol, trivalent alcohols such as glycerin and trimethylolpropane
Tetravalent alcohols such as alcohol and pentaerythritol, and tetravalent alcohols such as sorbitan, sorbitol and sucrose
And so on. Among the polyhydric alcohols, ethylene glycol, propylene glycol and the like are preferable.
Valuable alcohol.

Examples of the oxyalkylene group include oxyethylene group, oxypropylene group, oxybutylene group, oxystyrene group and a mixture thereof. Preferred are oxyethylene groups and oxyethylene groups.
It is an oxypropylene group (random type and / or block type).

The average molecular weight of the polyalkylene glycol is usually 200 to 2,000, preferably 400 to 1,000.
Is. The average molecular weight of the polyalkylene glycol is 20
When both are less than 0 and more than 2,000, the dye transferability during dyeing is lowered, and the levelness of the dyed product is lowered.

As the higher fatty acid, a saturated or unsaturated higher fatty acid having 10 to 22 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, erucic acid, oleic acid, linoleic acid, linoleic acid, Examples thereof include ricinolenic acid, tallow fatty acid, palm oil fatty acid and soybean oil fatty acid. Preferred are myristic acid, stearic acid, oleic acid and linoleic acid. Particularly preferred are stearic acid and oleic acid.

(A) is usually a mono-to-triester,
It is preferably a diester.

The polycyclic phenols (number of rings 4 to 20) forming the sulfuric acid ester salt (B) of the alkylene oxide adduct of the polycyclic phenols (number of rings 4 to 20) include styrenated phenols. -Phenol, styrenated cresol, α-methyl styrenated phenol and the like (phenol)
1 to 19 moles of styrene (styrene, α-methylstyrene, etc.) added to styrene, alkylphenol, polyvalent phenol); styrenated phenylphenol, styrenated cumylphenol, styrenated Naphthol, α
Examples thereof include styrenes (styrene, α-methylstyrene, etc.) added to a polycyclic phenol such as methylstyrenated phenylphenol in an amount of 1 to 18 mol. Preferred are styrenated (3 to 10 mol) phenol,
Styrenated (3 to 10 mol) cumylphenol and α-methylstyrenated (3 to 10 mol) phenol.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and mixtures thereof. Preferred are ethylene oxide, propylene oxide and ethylene oxide / propylene oxide combinations (block and or random). The number of moles of alkylene oxide added is usually 3 to 100, preferably 5
~ 50.

(B) is the above polycyclic phenols (having 4 rings)
~ 20) alkylene oxide adduct according to a conventional method,
It can be obtained by converting to a sulfate ester, neutralizing with an alkaline compound, and reacting with ammonium sulfamate. Alkaline compounds include caustic soda
Da, caustic potash, magnesium hydroxide, calcium hydroxide, ammonia, alkylamines having 1 to 5 carbon atoms, monoethanolamine, dietanolamine, triethanolamine
Lumin and the like are preferable, and preferred one is caustic soda,
Caustic potash, ammonia and monoethanolamine.

As the hindered phenols (C),
6-tert-butyl-2,4-xylenol, 2-t
ert-Butyl-4-ethylphenol, 2,6-di-
tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-t
ert-butylphenol, n-octadecyl-3-
(4'-Hydroxy-3,5'-di-tert-butylphenyl) propionate, dioctadecyl-4-hydroxy-3,5-di-tert-butylbenzylphosphonate, diethyl-4-hydroxy- 3,5-di-te
Monocyclic hindered phenols such as rt-butylbenzylphosphonate; 4,4'-thiobis (6-tert.
-Butyl-3-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylpheno-)
, 4,4′-methylenebis (6-tert-butylphenol), 4,4′-bis (2,6-di-tert)
-Butylphenol), 4,4'-thiobis (6-te
rt-butyl-o-cresol), 4,4′-methylenebis (6-tert-butyl-o-cresol), 2,
2'-methylenebis (4-methyl-6-tert-butyl-p-cresol), 2,2'-thiobis (6-te
rt-Butyl-4-methylphenol), 1,6-bis (3,5-di-tert-butyl-4-hydroxy-2)
-Bicyclic hindered phenols such as -methylphenyl) butane; 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,
4,6-Tris (3,5-di-tert-butyl-4-
Hydroxybenzyl) mesitylene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, 1,3,5-tris (3,5-di-)
tert-Butyl-4-hydroxybenzyl) isocyanurate, tetrakis [(β-3,5-di-tert-
Examples thereof include polycyclic (tricyclic or more) hindered phenols such as butyl-4-hydroxyphenyl) propionyloxymethyl] methane. Of these, preferred are monocyclic hindered phenols and bicyclic hindered phenols, and particularly preferred are 2,6-di-te.
rt-Butyl-4-methylphenol, 2,2'methylenebis- (6-tert-butyl-4-methylphenol-
), 4,4′-butylidene-bis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol).

The weight ratio of (A) :( B) :( C) is 1: (0.1-2) :( 0.001-0.1), preferably 1: (0.3). ~ 1.5): (0.005 to 0.
05). When (B) is less than 0.1, the dispersibility of the dye becomes poor, which causes tarring. When it exceeds 2, the transferability of the dye to the polyester fiber becomes poor,
It is not possible to obtain level dyeing properties in dyed products. When (C) is less than 0.001, dye decomposition occurs in a high temperature dyeing bath, and a dyeing product with good reproducibility cannot be obtained. When it exceeds 0.1, the dispersibility of the dye is hindered, which causes tarring.

The dyeing aid of the present invention may optionally contain a dyeing carrier composition (emulsion such as methylnaphthalene, chlorobenzene, benzyl benzoate, o-phenylphenol), a defoaming agent, a sizing agent, etc. Can also be included.

The dyeing assistant of the present invention is used for high temperature dyeing of polyester fibers with disperse dyes. Examples of the polyester synthetic fiber in the present invention include polyethylene terephthalate, polyethylene terephthalate isophthalate, polyethylene terephthalate paraoxybenzoate, polyethylene terephthalate butylene terephthalate and the like. Examples of the polyester fiber include cotton, thread, tow, top, case, knitted fabric, and non-woven fabric.
Further, there may be mentioned the mixed spinning of the above polyester fiber and other natural, regenerated, semi-synthetic or synthetic fiber, and mixed woven fabric.

The disperse dyes in the present invention are nonionic dyes such as azo dyes, anthraquinone dyes, nitrodiphenylamine dyes, naphthalimide dyes and methine dyes. Usually, disperse dyes are finely pulverized into fine particles of 1 micron or less, and a dye dispersant such as a formalin condensate of sodium naphthalene sulfonate is added.

The dyeing assistant of the present invention may be prepared by mixing (A), (B) and (C) in advance and adding them to a dyeing bath, a printing paste or the like (hereinafter represented by a dyeing bath). You may add separately to a dyebath. When (A), (B) and (C) are premixed, in order to obtain a stable dyeing aid, (A),
An emulsifier or solvent other than (B) may be added. As the emulsifier, nonionic emulsifiers such as polyoxyethylene alkyl allyl ether and polyoxyalkylene alkyl ether are preferable. As the solvent, water, methanol, ethanol, isopropyl alcohol, ethylene glycol
Water-soluble solvents such as ethylene glycol, ethyl ether, dimethylformamide, xylene, toluene, n-
Examples include non-aqueous solvents such as hexane and cyclohexane.

The amount of the dyeing auxiliary agent of the present invention used is usually 0.05 to 10 g / l, preferably 0.1 to 10 g, in terms of solid content, with respect to the dyeing bath.
It is 1 to 5 g / l. The amount of disperse dye used is usually 0.00
1-20% o. w. f. Is. Normal bath ratio (1: 3)
~ (1:50). The method for dyeing using the dyeing aid of the present invention can be carried out by an ordinary method, dip dyeing,
Any method such as printing or continuous dyeing may be used. As an example of the dyeing of polyester fiber, first, a dyeing bath comprising a disperse dye and the dyeing assistant of the present invention is prepared, pH is adjusted to 4 to 6, the fiber is put therein, and the temperature is raised to 110 to 140 ° C. Dye using a high pressure dyeing machine. The dyeing time is usually 30 minutes to 2 hours. After dyeing, the dyed product is obtained by washing with water, soaping or, if necessary, reducing reduction.

[0021]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Parts in the examples are parts by weight, and% is% by weight. The test method is as follows.

<Uniform dyeing test> (1) Dye transfer property: New synthetic fiber polyester woven fabric dyed with the following dye (130 ° C. × 60 minutes, no reduction washing) and undyed fabric of the same material as a dyeing aid. The treatment was carried out in a solution of 0.5 g / l at a bath ratio of 1:30 at 130 ° C for 60 minutes, and the degree of transfer of the dye to the undyed cloth was compared. Dye a: Dianis Bull-KB-FS (manufactured by Mitsubishi Kasei) 2% o. w. f. Dye b: Dyanic Thread F3B-FS (manufactured by Mitsubishi Kasei) 2% o. w. f. (2) Level dyeing ability: New synthetic fiber polyester (manufactured by Toray) was dyed under the following dyeing conditions, and the dyeing densities of the respective fabrics (A, B, C, D: same weight) were compared. Dye c: Sumikaron Red EF-BL (Sumitomo Chemical Co., Ltd.)
0.7% o. w. f. Resolin Bull-FB-RS (Made by Bayer) 0.7%
o. w. f. Parani-Louiero-3G (made by Badish) 0.7%
o. w. f. Dyeing aid concentration 0.5 g / l Bath ratio 1:30 (after adding all the cloths) pH 5 (adjusted with acetic acid) Temperature x time Temperature rises from room temperature to 60 ° C, and cloth A at 60 ° C
Is charged, the temperature is raised to 90 ° C. (1 ° C./min), the cloth B is charged at 90 ° C., and the temperature is further raised at 110 ° C. (1 ° C./min),
The temperature is lowered to 90 ° C., the cloth C is charged, the temperature is further raised to 130 ° C. (1 ° C./min), the temperature is lowered to 90 ° C., the cloth D is charged, and the temperature is raised to 130 ° C. again (1 ° C./min. ) And stain at 130 ° C. for 45 minutes. Dyeing machine Color Master HD-24 (manufactured by Tsujii Dyeing Machine)

<Dispersion test> A new synthetic polyester woven fabric (manufactured by Toray) is wound around a color pet holder and each of the following dyes,
Dyeing was performed under dyeing conditions, and the agglutinability of the dye was determined by visually observing the state of occurrence of casing spots. Dye d: Miketone Polyester Orange B Conc (Mitsui Toatsu) 3% o. w. f. Dye e: Dyanic Star-Coisable-G-FS 2
% O. w. f. Dyeing aid concentration 0.5 g / l Bath ratio 1:30 pH 5 (adjusted with acetic acid) Temperature x time (1) Raise the temperature from 60 ° C to 1 ° C / min, and
Remove the holder when the temperature reaches ℃. (2) Raise the temperature from 60 ℃ at 1 ℃ / min, and if it reaches 110 ℃,
The temperature is lowered to 0 ° C., and the holder is taken out. Dyeing machine Colorpet 24 (made by Nippon Dyeing Machine)

<Decoloring test (reproducibility test)> New synthetic fiber polyester (manufactured by Toray) is dyed under the following dyes and dyeing conditions,
The hue difference was visually judged. Dye f: Sumika Lomble-SE-PRO (Sumitomo Chemical Co., Ltd.)
0.05% o. w. f. Dye g: Dianic Suelo-F-3GE (manufactured by Mitsubishi Kasei) Dianix Bull-BG-FS (manufactured by Mitsubishi Kasei) Dianix Voldox GR-SE (manufactured by Mitsubishi Kasei) 1: 1: 1 (weight ratio) ) Blended 0.05
% O. w. f. Dye h: Miketone Polyester Dischargeable-R
(Mitsui Toatsu) 0.05% o. w. f. Dyeing assistant 0.5 g / l Bath ratio 1:30 pH 5 (adjusted with acetic acid) Temperature x time 130 ° C x 60 minutes Dyeing machine Kalamaster-HD-24 (manufactured by Tsujii Dyeing Machine)

Example 1 According to the following formulation, the components were blended at 55 ° C. in a paddle type reaction tank until uniform, and 1,000 parts of a dyeing assistant of the present invention having a pH of 8 (1% aqueous solution) in the form of a pale yellow liquid [1 ] Was obtained. Formulation: Polyethylene glycol (average molecular weight 500) diolate 300 parts Styrenated (5 mol) phenol ethylene oxide 30 mol adduct sulfate sodium salt 300 parts 2,6-di-tert-butyl-4- Methylphenol 10 parts Methanol 100 parts Water 290 parts

Example 2 1,000 parts of a dyeing auxiliary agent of the present invention having a pale yellow liquid pH 8 (1% aqueous solution) was blended in the paddle type reaction tank at 60 ° C. according to the following formulation until uniform. 2] was obtained. Formulation: polyoxyethylene polyoxypropylene glycol dilaurate (average molecular weight 600, oxyethylene: oxypropylene = 1: 1 weight ratio random adduct) 300 parts styrenated (7 mol) cumylphenol ethylene oxide 20 mol addition Sulfate ammonium salt 300 parts 2,2'-methylenebis- (6-tert-butyl-4-methylphenol) 10 parts isopropyl alcohol 100 parts water 290 parts

Example 3 According to the following formulation, it was blended at 80 ° C. in a paddle type reaction tank until uniform, and 1,000 parts of a dyeing auxiliary agent of the present invention having a pH of 8 (1% aqueous solution) as a pale yellow liquid [3 ] Was obtained. Formulation: polyoxyethylene glycol (average molecular weight 400) dilaurate 300 parts styrenated (7 mol) cumylphenol ethylene oxide 15 mol propylene oxide 5 mol block adduct sulfate ester triethanolamine salt 300 parts 2, 2'-Methylenebis- (6-tert-butyl-4-methylphenol) 10 parts Ethylene glycol monoethyl ether 100 parts Water 290 parts

Example 4 According to the following formulation, it was blended at 50 ° C. in a paddle type reaction vessel until uniform, and 1,000 parts of a dyeing aid of the present invention having a pH of 8 (1% aqueous solution) as a pale yellow liquid [4 ] Was obtained. Formulation: Glycerin ethylene oxide 20 mol Propylene oxide 10 mol Adduct (block) dioleate 300 parts α-methylstyrenated (5 mol) phenol ethylene oxide 40 mol adduct sulfate potassium salt 300 parts 4,4 ′ -Thiobis (6-tert-butyl-3-methylphenol) 10 parts Methanol 100 parts Water 290 parts

Comparative Example 1 According to the following formulation, the mixture was blended at 80 ° C. in a paddle type reaction tank until uniform, and was a pale yellow liquid at pH 6.5 (1% aqueous solution).
As a result, 1,000 parts [5] of a comparative dyeing auxiliary agent was obtained. Formulation: polyoxyethylene glycol (average molecular weight 400) dilaurate 600 parts 2,2'-methylenebis- (6-tert-butyl-4-methylphenol) 10 parts ethylene glycol monoethyl ether 100 parts water 290 copies

Comparative Example 2 1,000 parts of a comparative dyeing aid of a pale yellow liquid having a pH of 8 (1% aqueous solution) [6] was blended in the paddle type reaction tank at 80 ° C. according to the following formulation. Got Formulation: Styrenated (5 mol) phenol ethylene oxide 30 mol Adduct sulfate sodium salt 600 parts 2,6-di-tert-butyl-4-methylphenol 10 parts methanol 100 parts water 290 parts

Comparative Example 3 1,000 parts of a comparative dyeing auxiliary agent having a pH of 8 (1% aqueous solution) in the form of a pale yellow liquid [7] was blended in the paddle type reaction tank at 80 ° C. according to the following formulation. Got Formulation: Polyethylene glycol (average molecular weight 500) diolate 300 parts Styrenated (5 mol) phenol Ethylene oxide 30 mol Adduct sulfuric acid ester sodium salt 300 parts Methanol 100 parts Water 300 parts

Comparative Example 4 1,000 parts of a comparative dyeing auxiliary agent of a pale yellow liquid pH 8 (1% aqueous solution) [8], which was blended according to the following formulation at 80 ° C. in a paddle-type reaction tank until uniform. Got Formulation: Polyethylene glycol (average molecular weight 500) diolate 300 parts Nonylphenol ethylene oxide 20 mol adduct Sulfuric acid ester sodium salt 300 parts 2,2'-methylenebis- (6-tert-butyl-4-methylpheno-) 10 parts methanol 100 parts water 290 parts

Performance Test 1 Table 1 shows the results of a performance test as a dyeing agent using a new synthetic polyester undyed woven fabric (manufactured by Toray) using the dyeing aids [1] to [8].

[0034]

[Table 1] Performance test judgment: ●: Very good, ◎: Very good, ○: Good, △: Slightly bad △ to ×: Poor, ×: Very bad

From the results shown in Table 1, it can be seen that the dyeing assistant of the present invention has excellent leveling property, dispersibility and decoloring property (reproducibility) even for new synthetic fibers.

Performance Test 2 Using the dyeing aids [1] to [8] and ordinary polyester fiber (textured yarn fabric: purchased from Tanigami Shoten), a performance test as a dyeing agent was conducted. Shown in.

[0037]

[Table 2] Performance test judgment: ●: Very good, ◎: Very good, ○: Good, △: Slightly bad △ to ×: Poor, ×: Very bad

From the results shown in Table 2, it can be seen that the dyeing assistant of the present invention satisfies the level dyeing and dispersibility improved with respect to ordinary polyester fibers.

[0039]

The dyeing assistant of the present invention is a regular regular dye.
It is a useful dyeing aid that can be used for dyeing not only polyester but also fine denier polyester fiber called new synthetic fiber during dyeing with good reproducibility. . The dyeing aid of the present invention is useful as a dyeing aid when dyeing polyester fibers because it exhibits the above effects.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryuichi Ito 1-11, Hitotsubashi-honmachi, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A higher fatty acid ester (A) of polyalkylene glycol, a sulfate ester salt (B) of an alkylene oxide adduct of polycyclic phenols (having 4 to 20 rings) and hindered phenols. (C) A dye aid for polyester fibers. 2. The compounding ratio of (A) :( B) :( C) is 1: (0.1-2) :( 0.001-0.1) by weight. Dyeing aid. 3. The dyeing auxiliary agent according to claim 1, wherein the polyalkylene glycol has a number average molecular weight of 200 to 2,000.