JPS602434B2 - Dyeing method for polyester synthetic fibers - Google Patents

Description

[Detailed description of the invention]

The present invention provides a method for dyeing polyester synthetic fibers and blended or cross-knitted fabrics of polyester synthetic fibers and other fibers such as cotton, wool, rayon, hemp, etc. with disperse dyes alone or with other dyes. The present invention relates to a method for obtaining evenly dyed products using a novel dyeing aid that imparts uniformity and level dyeing properties. Polyester-based synthetic fiber products (including blended products of polyester-based synthetic fibers and cellulose-based woven and other fibers, and mixed-knitted woven products) are usually dyed by a carrier dyeing method using a carrier or a high temperature dyeing method of 120 to 140 oo. There is. Recently, efforts have been made to streamline workability by shortening dyeing time and to add high added value to dyed products, and the role of dyeing aids has become extremely important. However,
Conventionally used dyeing aids such as formalin condensate of sodium naphthalene sulfonate, higher alcohol sulfate ester acid, and polyoxyethylene alkylphenol ether sulfate have excellent dispersibility, leveling properties, or foaming properties. In addition to being unsatisfactory in terms of properties, it also has the drawbacks of being prone to dyeing problems such as tarring due to poor dispersion of the disperse dye, uneven beams due to insufficient beam uniformity, and lifting and twisting of the fabric due to super bubbles. Furthermore, even with polyoxyethylene styrenated phenyl ether sulfate, which is a known dyeing aid with excellent dispersibility and uniformity, sufficient effects cannot be obtained in high-temperature, short-time dyeing. There is a great need for a beam coloring aid that can solve these dyeing problems. In view of the above, the inventors of the present invention have arrived at the present invention as a result of intensive research to determine the problems of dyeing PoIJ ester-based synthetic fibers. That is, the present invention provides a beam coloring auxiliary agent that solves the problems of poor dispersion and poor border dyeing of disperse dyes and also solves the problems caused by foaming in the high-temperature, short-time dyeing of polyester synthetic fibers with disperse dyes. It provides an excellent dyeing method to use. Below, the beam coloring aid used in the present invention will be described and its effects will be discussed. The dyeing aid used in the present invention has the general formula

It is a compound represented by [0] or [m]. In addition, the above general formula

[0] and [m], A is an alkyl group,
A benzene nucleus substituted or unsubstituted with an aryl group, an aralkyl group, or a cycloalkyl group; or a long-chain alkyl group, Z is ○, any atom or atomic group from COO, n and m are each 0 or an integer from 1 to 50 (n
and m cannot both be 0), or 0 or 1 to 5
Y is an atom or atomic group of COO, N, NH, B is a benzene nucleus substituted with an alkyl group, an alkenyl group, a halogen, or a sulfonic acid group; an alkylene sulfate; or an alkylene sulfonate. M represents either K or Na, respectively. These compounds [D] and [m] have the general formula [1]
, (in formula [1], A, Z, n, m, x are formulas

[0], [m
]) using an appropriate catalyst and solvent to add substances such as amines, carboxylic acids, alcohols, phenols, thioalcohols, and inorganic acids to the epoxide group. That's what you get. Substances added to the epoxide compound represented by the general formula [1] include, in addition to the substances represented by the general formulas [W] and [V] described below, aliphatic saturated/unsaturated dicarboxylic acids, partial salts thereof, Alternatively, acid anhydrides, sulfodibasic acid salts, aromatic di-, tri-, and tetracarboxylic acids, partial salts thereof, acid anhydrides thereof, inorganic acids, and inorganic salts are used. Here, the formulas [N] and [V] are BYH ...... [W
]HX-R-S03M...[V
], where B, Y, ×, and M are the formulas

[0], [m]
It is synonymous with the case of . By the way, this epoxide compound [1] is prepared by adding 1 to 10 equivalents of epichlorohydrin to 1 equivalent of -OH group of an ether type or ester type nonionic surfactant, and adding a suitable alkali metal hydrate or alkali metal hydrate. It is obtained by ring-closing using a compound. More specifically, the /ionic surfactant which is a raw material has functional groups of the compound represented by the general formula (A and Z are synonymous with formula [1]), ie, 1OH group, 1N ratio group, and 1N ratio group. An ether type/ionic compound obtained by adding ethylene oxide or ethylene oxide and propylene oxide to the SH group, or a compound having one COO group and polyethylene glycol, or a copolymer of polyethylene glycol and polypropylene glycol is esterified. The resulting ester type nonionic surfactant. The amount of the alkylene oxide is 1 to 150 mol, preferably 1 to 100 mol, per 1 mol of the compound represented by the general formula AZH. In addition, in the case of block addition of ethylene oxide and propylene oxide or their ester compounds, the average number of moles of ethylene oxide, which is a hydrophilic group, is always greater than the average number of moles of propylene oxide. is desirable. Compounds (substances) represented by the general formulas AZH and [W] include phenylphenol, cremylphenol, teftol, nonylphenol, cyclohexylphenol, butylphenol, benzylated phenol, butylenated phenol,
Phenols such as cyclohexylphenol, or amines having aromatic groups similar to these phenols,
Examples include carboxylic acids and lowest chain alkyl amines, but are not particularly limited to these exemplified compounds. On the other hand, examples of compounds having a sulfonic group represented by the general formula [V] include sulfanilic acid, sodium taurine-ysethionate, sulfobenzoic acid, sulfosalicylic acid, and sulfated phenol. Aliphatic saturated/unsaturated dicarboxylic acids (including acid anhydrides) include Q-unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid; acids, glutaric acid, adipic acid, azelaic acid, sebacic acid, methylsuccinic acid,
These include aliphatic saturated dicarboxylic acids such as methylglutaric acid, and partial salts thereof. Examples of the sulfodibasic acid salt include sulfadipic acid salt, sulfosuberic acid salt, sulfosuccinate, Q-sulfomethylsuccinate, and sulfosebacate. Aromatic di-, tri-, and tetracarboxylic acids (including acid anhydrides)
Examples include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride,
Examples include pyromellitic acid. The compounds obtained by adding these carboxylic acids are:
Depending on the case, the remaining carpoxyl group may be further neutralized with an alkali metal/alkali metal hydrate, an N-alkylamine having up to 5 carbon atoms, or an N-alkanolamine having up to 5 carbon atoms. Examples of inorganic acids include nitric acid and hydrochloric acid, and examples of inorganic salts include sodium sulfite and acidic sodium sulfite. Note that the present invention is not particularly limited to these exemplified compounds. As mentioned above, the present invention is based on the general formula [
A novel polyester system in which one or more of the compounds obtained by adding a reactive substance to the epoxide group of the epoxide compound of the nonionic surfactant represented by [b] and [m] is used as a dyeing agent. A method for dyeing synthetic fibers is provided. Although the ionicity of the dyeing aid of the present invention obtained by adding the compound represented by the general formula [N] is nonionic, it has a uniform beam effect compared to the conventionally known alkylene oxide adduct of tristyrenated phenol. It has an excellent dispersion effect, no color fading phenomenon, and low foaming properties, so it can withstand use even under severe dyeing methods such as high-temperature, short-time dyeing, and has excellent dyeing properties. Further, the ionicity of the dyeing aid of the present invention to which a compound represented by the general formula [V] or a substance having a sulfate group, a carboxyl group, or a salt thereof is added is an anion. In general, dyeing aids of anionic type are considered to be advantageous from the viewpoint of ionic adsorption, and in addition, conventionally known polyoxyethylene styrenated phenyl ether sulfates have good dispersion and beam-leveling properties. Although it is widely used because of its excellent properties, it has the disadvantage of being extremely foamy and prone to problems caused by foaming during high-temperature, short-time dyeing. In contrast, the beam color auxiliary agent of the present invention has an epichlorohydrin chain in the middle of the molecule, so it structurally suppresses foaming and exhibits excellent dyeing properties such as dispersion and beam uniformity. It is. If the dyeing aid of the present invention is insoluble in water, it can only be used in combination with a known dispersant such as sodium naphthalene sulfonate. Next, the present invention will be explained in more detail with reference to Examples. Example 1 1267 parts (1 mol) of a 20 mol adduct of tristyrenated phenol ethylene oxide are placed in a flask equipped with a reflux condenser, a thermometer and a dropping device. Using 3 parts of dimethylbenzylamine as a catalyst, *7
185 parts (2 mol) of epichlorohydrin was carefully added dropwise at 0° C. to 110 qo and reacted for 4 hours at 100 qo to 110 oo. Next, 96 parts (1.2 mol) of 50% caustic soda was added at 40 qo to 60 qo, and the mixture was incubated at the same temperature for 2 hours to remove salt and obtain an epoxide compound. The precipitated common salt was removed by filtration, and 144 parts (1 mol) of octylic acid was added to the filtrate.
, adding 4 parts of dimethylaniline as a catalyst and heating at 90°C to 1
The reaction was carried out at 00:00 for 4 hours to obtain 1,620 parts of a viscous steel material. The structural formula of the compound thus obtained (a type of compound represented by the general formula [b]) is as follows. This sticky steel material has an acid value of 2 or less and is dispersed in water. In addition, Table 1 shows the results of foaming tests comparing this compound with conventionally used dyeing aids, as well as dyeing properties such as dispersibility and level dyeing properties, and work when using a rapid circular dyeing machine. The test results are shown in Table 2. Example 2 Using the same equipment and method as Example 1, 10 moles of ethylene oxide and 5 moles of propylene oxide of nonylphenol were prepared.
1 mole of copolymerization adduct and Epik. A compound obtained from 1 mole of ruhydrin, 1.2 moles of 50% caustic potassium, and 1 mole of

Table 1 shows the foaming test results for the compound represented by [0], and Table 1 shows the dyeability and dyeing workability, respectively.
Shown in 2. Moreover, the structural formula of this compound is as follows. Example 3 Using the same equipment and method as in Example 1, 1 mole of an adduct of styrenated cyclohexylphenol with 10 moles of ethylene oxide, 1.2 moles of epichlorohydrin, 1.2 moles of 50% caustic soda, and 1 mole of sulfanyl A compound obtained from .1 mole (a type of compound represented by the general formula [m])
Similar to Example 1, the results of the foaming test and the dyeability/dying workability test are shown in Table 1 and Table 2. Moreover, the structural formula of this compound is as follows. Example 4 Obtained by a normal esterification reaction from 1 mol of stearic acid and 1 mol of polyethylene glycol (PEG-1000) having an average molecular weight of 1000/1 mol of anionic surfactant and 5 mol of epichlorohydrin, Foaming test results of a compound (a type of compound represented by general formula [m]) obtained from 1.2 mol of 50% caustic soda and 1 mol of sodium sulfosuccinate using the same equipment and method as in Example 1. Example 1: Dyeability/dyeing workability test results
Similarly, Table 1 and Table 2 show the results. The structural formula of this compound is as follows. Example 5 Using the same equipment and method as in Example 1, 15 moles of propylene oxide adduct of tristyrenated phenol, 2 moles of epichlorohydrin, 1.1 moles of 50% caustic soda, and acidic Obtained from 1.2 mol of sodium sulfite. *Compounds that can be
Similar to Example 1, Table 1 shows the results of the foaming test and the dyeability/dyeing workability test for a type of chemical compound 3 represented by the general formula [m].
, shown in Table 2. The structural formula of this compound is as follows. Table 1: Foaming test (Kan) However, for the foaming test shown in Table 1, 80 q○ of the adjustment solution (with 0 beam color aids) was added to the measuring cylinder (inner diameter 6.3 mm)
．． 2 evenings/evenings, add 0.3 tons of acetic acid and No. 2 at the tip.
450 {/mm of air was continuously blown from the bottom of the graduated cylinder using an air pump equipped with a ball filter No. 2, and the height (c) of the bubbles from the liquid surface was measured. Further, as a comparative example, the following anionic type dyeing aids were used (Comparative Example 1): A conventionally known dyeing aid was used. As is clear from Table 1, it is clearly seen that the dyeing auxiliary of the present invention has a lower foaming property than the known coloring auxiliary that has been widely used in the past. Next, Table 2 shows the test results regarding the dyeability and dyeing workability of the beam coloring auxiliary agent according to the present invention. In Table 2, in the dispersibility/uniformity column, ◎ indicates particularly good, 0 indicates good, △ indicates somewhat good, and × indicates poor. In addition, regarding the dyeing workability column, ○: Low foaming both at elevated temperature and during tacking, good workability during dyeing, and gives a level dyed product. x: Vigorous foaming occurs during heating and tacking, slippage occurs during work, and staining spots occur. Show that. Table-2 Dyeability/Dyeing Workability Test Results In Table-2, the dispersion test was performed using Diometer (manufactured by Suga Test Instruments).
was used under the following conditions. Sample: Polyester filament Dye: Kawa Smmik
aRon R ribine S primary L5%0. W. f. '2
} DianixBlueBOXFS 5%o. w. f
．． Test compound: 0.5 t/t (purity equivalent) Acetic acid: 0.3
cc/bath ratio: 1:30 Flow rate: 200cc/min Temperature/time: 60q○→13500/25 minutes, then 1
3500 for 20 minutes.Also, a beam uniformity test was conducted under the following test conditions. Dyeing conditions Sample: Polyester processed yarn Fabric dyeing machine: Karabetsu 12 (manufactured by Nippon Senzo Kikai) Dye: '3'Resoli
neBI fertilizer FBL 2% o. w. f. ReSoli ship Re
dFB2%o, W, f, ReSoli Fertilizer YellowR
L2% o, W, f, acetic acid 0.3 cc/
Add evening. {41 DianixYellow G-FSO. 4%
o. w. f. DianixRedTB-SEO. 4%o
．． w. f. DianixBlueBG-FSO. 4%o
．． w. f. Add 0.3 cc' of acetic acid to these mixtures. Yu ratio: 1:20 Temperature/time: 13500, 20 minutes A white cloth of the same quality and quantity was put into the treatment under the following conditions together with the above dyed cloth, and a dye transfer test was conducted. Test compound: 0.5 ml/ml (purity conversion) Acetic acid: 0.3 cc/〆Solubility ratio: 1:20 Temperature/time: 135 x 0, 20 minutes Furthermore, the dyeing work test in Table 2 is the test A processed polyester yarn fabric was dyed using a rapid circular dyeing machine (manufactured by Hisaka) under the following conditions. Since this test is used under severe conditions, if a highly foaming beam coloring aid is used, the fabric may slip or shift due to foaming when the temperature is raised or when the fabric is tacked, causing problems such as dyeing spots. Staining conditions Dye: DjanixBlueBG-FS3%o. w. f
．． Acetic acid: 0.3 cc/Test compound: 0.5 cc (purity equivalent) Solvent ratio: 1:12 As is clear from the test results in Table 2, the dyeing aid according to the present invention is polyester-based. It is clear that when dyeing synthetic fibers, it has excellent dispersibility, gives evenly distributed dyed products, and has low foaming properties, so it can be applied to high-temperature dyeing methods.

Claims (1)

[Claims] 1. An epichlorohydrin adduct of an alkylene oxide addition polymerization type surfactant represented by the general formula [I] ▲ Numerical formula, chemical formula, table, etc.▼ A method for dyeing polyester synthetic fibers, characterized in that one or more compounds represented by the following general formula [II] and/or general formula [III] obtained by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In formulas [I], [II], and [III], A is a benzene nucleus substituted or unsubstituted with an alkyl group, aryl group, aralkyl group, or cycloalkyl group; or Represents a long-chain alkyl group, Z represents any atom or atomic group from O or COO, and n and m each represent 0 or an integer from 1 to 50 (n and m cannot both be 0). , x is 0 or 1 to 5
Y is an atom or atomic group of OOC, N, NH, B is a benzene nucleus substituted with an alkyl group, an alkenyl group, a halogen, or a sulfonic acid group; an alkylene sulfate or an alkylene sulfonate. M represents either K or Na, respectively. ).