JP2578059B2 - Dyeing aid for polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Hitherto, as a dyeing aid for polyester-based fibers, those containing a polyoxyalkylene-based surfactant having an HLB of 6 or more and a hindered phenol-based compound (Japanese Patent Publication No. 55-4877). Consisting of a mixed ester of an oxyalkylene ether of a polyhydric alcohol with a dicarboxylic acid or an aliphatic monocarboxylic acid (Japanese Patent Publication No. Hei 4-18070), and an alkylene oxide adduct of a styrenated phenol sulfuric acid Ester salt (JP 50
-12036) and the like. However, in the case of ordinary polyester fibers, leveling properties and dispersibility higher than conventional levels are required. Further, in the case of dyeing a polyester fiber composed of fine denier and hetero-shrinkage mixed fiber, which is collectively referred to as a new synthetic fiber in recent years, good levelness cannot be obtained by the above technique. In Japanese Patent Publication No. 55-4877,
There is a description that a polyoxyalkylene surfactant having an HLB of 6 or more and a polyoxyalkylene alkylphenyl ether sulfate salt may be used in combination with the hindered phenol-based compound. In the case of fiber, it cannot cope with a higher level, and in the case of new synthetic fiber, levelness and dispersibility are insufficient.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to cope with the recent increase in the level of dyeing of ordinary polyester fibers, and to dye new synthetic fibers in a dyeing bath during dyeing. To obtain a uniform dyeing by imparting excellent dispersibility and dye transferability to the dyeing aid, and to obtain a dyeing aid having good reproducibility.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have responded to the demand for higher levels of ordinary polyester fibers and imparted leveling properties with good reproducibility to new synthetic fibers. As a result of intensive studies on the dyeing aid, the present invention has been reached.

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

The polyalkylene glycol forming the higher fatty acid ester (A) of the polyalkylene glycol is
An oxyalkylene group is added to a dihydric alcohol. Examples of the dihydric alcohol include ethylene glycol and propylene glycol.

The oxyalkylene group includes an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxystyrene group and a mixture thereof. Preferred are an oxyethylene group and an oxyethylene group.
It is an oxypropylene group (random type and / or block type).

The average molecular weight of the polyalkylene glycol is usually from 200 to 2,000, preferably from 400 to 1,000.
It is. The average molecular weight of the polyalkylene glycol is 20
When it is less than 0 or more than 2,000, the transferability of the dye at the time of dyeing decreases, and the leveling property of the dyed product decreases.

The higher fatty acids include saturated and unsaturated higher fatty acids 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, Risinolenic 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 and oleic acids.

(A) is usually a mono- to triester,
Preferably it is a diester.

The polycyclic phenols (4 to 20 rings) forming the sulfate salt (B) of the alkylene oxide adduct of the polycyclic phenols (4 to 20 rings) include styrenated phenols. Monocyclic phenols such as phenol, styrenated cresol and α-methylstyrenated phenol (phenol
1 to 19 mol of styrenes (styrene, α-methylstyrene, etc.) added to styrene, alkylphenol, polyvalent phenol); styrenated phenylphenol, styrenated cumylphenol, styrenated Naphthole, α
Examples thereof include those obtained by adding 1 to 18 moles of styrenes (styrene, α-methylstyrene, etc.) to a polycyclic phenol such as -methylstyrenated phenylphenol. Preferred are styrenated (3-10 mol) phenols,
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 a mixture thereof. Preferred are ethylene oxide, propylene oxide and ethylene oxide / propylene oxide combined (block and / or random). The number of moles of alkylene oxide added is usually 3 to 100, preferably 5 to 100.
~ 50.

(B) is the above-mentioned polycyclic phenols (with 4 rings).
To 20) according to a conventional method.
It is obtained by sulfate esterification, neutralization with an alkaline compound, and reaction with ammonium sulfamate. As the alkaline compound, caustic so-
Da, caustic potash, magnesium hydroxide, calcium hydroxide, ammonia, alkylamine having 1 to 5 carbon atoms, monoethanolamine, diethanolamine, triethanol-
And preferred are caustic soda,
Caustic potash, ammonia and monoethanolamine.

As the hindered phenols (C),
6-tert-butyl-2,4-xylenol, 2-t
tert-butyl-4-ethylphenol, 2,6-di-
tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-t
tert-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-methylphenol-
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;
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-
And polycyclic (three 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-nophenol.
rt-butyl-4-methylphenol, 2,2'methylenebis- (6-tert-butyl-4-methylphenol-
), 4,4'-butylidene-bis (6-tert-butyl-3-methylphenol) and 4,4'-thiobis (6-tert-butyl-3-methylphenol).

The compounding ratio of (A) :( B) :( C) is 1: (0.1-2) :( 0.001-0.1), preferably 1: (0.3) by weight ratio. -1.5): (0.005-0.
05). If (B) is less than 0.1, the dye dispersibility becomes poor, which causes tarring. If it exceeds 2, the dye transfer property to the polyester fiber becomes poor,
Unevenness in dyed goods cannot be obtained. When (C) is less than 0.001, dye decomposition occurs in a high-temperature dyeing bath, and a dyestuff having good reproducibility cannot be obtained. If it exceeds 0.1, the dispersibility of the dye is hindered, which causes tarring.

The dyeing assistant of the present invention may optionally contain a dye carrier composition (emulsions such as methylnaphthalene, chlorobenzene, benzylbenzoate, o-phenylphenol), an antifoaming agent, a sizing agent and the like. Can also be contained.

The dyeing aid of the present invention is used for dyeing polyester fibers at a high temperature with a disperse dye. Examples of the polyester synthetic fibers in the present invention include polyethylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / paraoxybenzoate, polyethylene terephthalate / butylene terephthalate, and the like. Cotton, thread, tow, top, sash, knitted fabric, non-woven fabric, etc. made of polyester fiber of the above.
In addition, blends of the above polyester fibers with other natural, regenerated, semi-synthetic, and synthetic fibers, mixed woven fabrics, and the like can be given.

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

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 or a printing paste (hereinafter represented by a dyeing bath). You may add to a dyeing bath separately. When (A), (B) and (C) are preliminarily mixed, (A),
Emulsifiers and solvents other than (B) may be added. As the emulsifier, a nonionic emulsifier such as polyoxyethylene alkyl allyl ether and polyoxyalkylene alkyl ether is preferable. Solvents include water, methanol, ethanol, isopropyl alcohol, ethylene glycol
, Ethylene glycol ethyl ether, dimethylformamide and other water-soluble solvents, xylene, toluene, n-
Examples include non-aqueous solvents such as hexane and cyclohexane.

The amount of the dyeing aid of the present invention to be used is generally 0.05 to 10 g / l, preferably 0.1 to 10 g / l, based on the solids content of the dyeing bath.
1 to 5 g / l. The amount of disperse dye used is usually 0.00
1-20% o. w. f. It is. Bath ratio is normal (1: 3)
~ (1:50). The method of performing dyeing using the dyeing aid of the present invention can be performed by a usual method,
Any method such as printing and continuous dyeing may be used. If an example of the dyeing of polyester fiber is shown, first, a dye bath comprising a disperse dye and the dyeing aid of the present invention is prepared, the 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, washing with water, soaping or, if necessary, reduction washing is performed to obtain a dyed product.

[0021]

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

<Leveling test> (1) Migrating property: New synthetic polyester woven fabric dyed with the following dye (130 ° C x 60 minutes, no reduction washing) and undyed fabric of the same material as dyeing assistant The solution was treated in a 0.5 g / l solution 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: 2% o.n. of Dyanix Blue-KB-FS (manufactured by Mitsubishi Kasei) w. f. Dye b: Dianic thread F3B-FS (manufactured by Mitsubishi Kasei) 2% o. w. f. (2) Leveling properties: New synthetic fiber polyester (manufactured by Toray) was dyed under the following dyes and dyeing conditions, and the dyeing densities of the fabrics (A, B, C, D: the same weight) were compared. Dye c: Sumicaron Red EF-BL (Sumitomo Chemical)
0.7% o. w. f. Resorimble-FB-RS (manufactured by Bayer) 0.7%
o. w. f. Parani-Louiero-3G (made by Buddy) 0.7%
o. w. f. Dyeing aid concentration 0.5 g / l Bath ratio 1:30 (after putting all cloths) pH 5 (adjusted with acetic acid) Temperature x time Raise the temperature from normal temperature to 60 ° C, then cloth A at 60 ° C
, 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).
After the temperature was lowered to 90 ° C., the cloth C was put in, and then the temperature was raised to 130 ° C. (1 ° C./min). Then, the temperature was lowered to 90 ° C., the cloth D was put in, and the temperature was 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)

<Dispersibility test> Wind a new synthetic fiber woven fabric (manufactured by Toray) on a color pet holder
The dye was stained under staining conditions, and the occurrence of a casing spot was visually observed to determine the cohesiveness of the dye. Dye d: Miketone Polyester Orange B Conc (Mitsui Toatsu) 3% o. w. f. Dye e: Dyanic Star-Cosible-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) The temperature was raised from 60 ° C at 1 ° C / min, and 90
When the temperature reaches ℃, remove the holder. (2) Raise the temperature from 60 ° C at 1 ° C / min.
The temperature is lowered to 0 ° C., and the holder is taken out. Dyeing machine color pet 24 (manufactured by Nippon Dyeing Machinery)

<Discoloration test (reproducibility test)> A new synthetic fiber polyester (manufactured by Toray) is dyed under the following dyes and dyeing conditions.
The hue difference was visually determined. Dye f: Sumikaromble-SE-PRO (Sumitomo Chemical)
0.05% o. w. f. Dye g: DIANIC Swiero-F-3GE (manufactured by Mitsubishi Chemical) DIANIC BLUE-BG-FS (manufactured by Mitsubishi Chemical) DIANICS Boldox GR-SE (manufactured by Mitsubishi Chemical) Each dye is 1: 1: 1 (weight ratio) 0.05)
% O. w. f. Dye h: Miketone polyester dischargeable-R
(Mitsui Toatsu) 0.05% o. w. f. Dyeing aid 0.5 g / l Bath ratio 1:30 pH 5 (adjusted with acetic acid) Temperature x time 130 ° C x 60 minutes Dyeing machine Kalamastar-HD-24 (manufactured by Tsujii Dyeing Machine)

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

Example 2 According to the following formulation, the mixture was mixed at 60 ° C. in a paddle-type reaction tank until uniform, and 1,000 parts of a dyeing aid of the present invention, which was a pale yellow liquid and had a pH of 8 (1% aqueous solution) [ 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 Product 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, the mixture was mixed at 80 ° C. in a paddle type reaction tank until uniform, and 1,000 parts of a dyeing aid of the present invention having a pale yellow liquid and having a pH of 8 (1% aqueous solution) [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 Sulfuric ester triethanolamine salt 300 parts 2, 2'-methylenebis- (6-tert-butyl-4-methylphenol) 10 parts Ethylene glycol monoethyl ether 100 parts Water 290 parts

[0028]

COMPARATIVE EXAMPLE 1 According to the following formulation, the mixture was blended at 80 ° C. in a paddle-type reaction tank until it became uniform, and a pale yellow liquid having a pH of 6.5 (1% aqueous solution) was prepared.
To obtain 1,000 parts of a dyeing aid [5]. 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 According to the following formulation, the mixture was mixed at 80 ° C. in a paddle type reaction tank until uniform, and 1,000 parts of a comparative dyeing aid having a pale yellow liquid and a pH of 8 (1% aqueous solution) [6] I 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 According to the following formulation, the mixture was mixed at 80 ° C. in a paddle-type reaction tank until uniform, and 1,000 parts of a comparative dyeing aid having a pale yellow liquid and a pH of 8 (1% aqueous solution) [7] I got Formulation: Polyethylene glycol (average molecular weight 500) diolate 300 parts Styrenated (5 mol) phenol ethylene oxide 30 mol adduct sodium sulfate 300 parts Methanol 100 parts Water 300 parts

Comparative Example 4 According to the following formulation, the mixture was mixed at 80 ° C. in a paddle type reaction tank until the mixture became uniform, and 1,000 parts of a comparative dyeing aid having a pale yellow liquid and a pH of 8 (1% aqueous solution) [8] I got Formulation: Polyethylene glycol (average molecular weight: 500) diolate 300 parts Nonylphenol ethylene oxide 20 mol adduct Sulfate sodium salt 300 parts 2,2'-methylenebis- (6-tert-butyl-4-methylphenol) 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 fiber undyed woven fabric (manufactured by Toray) using the dyeing assistants [1] to [8].

[0034]

[Table 1]

From the results shown in Table 1, it can be seen that the dyeing aid of the present invention has excellent leveling properties, dispersibility, and decolorability (reproducibility) even with new synthetic fibers.

Performance Test 2 Table 2 shows the results of a performance test as a dye using ordinary polyester fibers (processed yarn woven fabric: purchased from Tanika Shoten) using the dyeing assistants [1] to [8]. Shown in

[0037]

[Table 2]

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

[0039]

EFFECT OF THE INVENTION The dyeing assistant of the present invention is prepared by
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 with good reproducibility to obtain polyester dyeings with good leveling properties. . Due to the above effects, the dyeing aid of the present invention is useful as a dyeing aid for dyeing polyester fibers.

 ────────────────────────────────────────────────── ─── Continuation of the front page Examiner Satoru Fukui (56) References JP-A-55-76176 (JP, A) JP-A-54-68479 (JP, A) JP-A-48-67567 (JP, A)

Claims (3)

(57) [Claims] 1. Higher fatty acid esters of polyalkylene glycol (A), sulfates of alkylene oxide adducts of polycyclic phenols (4 to 20 rings) (B) and hindered phenols A dyeing aid for polyester fibers comprising (C). 2. The composition according to claim 1, wherein the compounding ratio of (A) :( B) :( C) is 1: (0.1-2) :( 0.001-0.1) by weight. Dyeing aid. 3. The dyeing assistant according to claim 1, wherein the number average molecular weight of the polyalkylene glycol is from 200 to 2,000.