JPH045793B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a dyeing method. More specifically, the present invention relates to a method for dyeing polyester fibers. Conventionally, alkylene oxides 1 to 4 of phenols having 3 to 6 aromatic rings have been used as dyeing aids for dyeing polyester fibers under high temperature and high pressure conditions.
It was known to use molar adducts (Tokuko Sho
54-27474). However, different types of dyes (disperse dyes and direct dyes, disperse dyes and reactive dyes, etc.) are used in combination to dye blends of polyester fibers with other fibers, mixed knitted fabrics (blends of polyester fibers with cotton or rayon, etc.) In this case, the dispersibility of the dye decreases due to the use of Glauber's salt, soda ash, etc., which causes speckles (insoluble matter) of the dye, causing staining spots. The present inventors have arrived at the present invention as a result of intensive research into a method for dyeing polyester fibers at high temperature and high pressure without reducing the dispersibility of the dye even in the presence of salts such as mirabilite and soda ash. That is, the present invention provides alkylene oxide to phenols having 2 to 6 aromatic rings selected from the group consisting of styrenated phenols, styrenated aryl phenols, styrenated halogenated phenols, chlorinated benzylated alkyl phenols, and chlorinated benzylated aryl phenols. {However, the number of moles of alkylenoxide added is 7 to 30
and the content of EO (ethylene oxide) is 35%.
This is a dyeing method characterized by subjecting polyester fibers to high-temperature, high-pressure dip dyeing in the presence of a dyeing aid consisting of the following: In the present invention, a compound in which alkylene oxide (also referred to as AO) is added to a phenol having 2 to 6 aromatic rings (also referred to as polycyclic phenol) (however, the number of moles of AO added is 7 to 30) ( Polycyclic phenols (also referred to as polycyclic phenol AO adducts) include those obtained by reacting phenols or phenols with styrenes and/or halogenated benzyls. The above phenols include phenol; naphthol; alkylphenol (alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, butyl, P-
Alkylphenols having one or more tert-butyl, hexyl, octyl, nonyl, dodecyl, etc.), arylphenols (arylphenols having an aryl group such as phenyl, cumyl, tolyl, xylyl, biphenyl, naphthyl),
Halogenated phenols (trichlorophenol,
monochlorophenol, monobromophenol, etc.). Preferred are styrenated phenols, styrenated arylphenols,
These are styrenated halogenated phenols, chlorinated benzylated alkylphenols, and chlorinated benzylated arylphenols. Styrenes include styrene, alkylstyrenes (α-methylstyrene, β-methylstyrene,
α-ethylstyrene, etc.), halogenated styrenes (α-chlorostyrene, β-chlorostyrene, α-chlorostyrene, etc.),
-bromstyrene, β-β-dichlorostyrene, etc.), preferred are styrene and α-methylstyrene, and particularly preferred is styrene. Examples of the benzyl halides include benzyl chloride and benzyl bromide. Styrene and/or reacted with phenols
Alternatively, the amount of the halogenated benzyl is within a range such that the resulting polycyclic phenol has 2 to 6 aromatic rings. If the number of aromatic rings is less than 2, the covering property will deteriorate, which is undesirable. If the number exceeds 6, the covering property and dispersibility will deteriorate, which is not preferred. There are known methods for reacting phenols and styrenes, such as the Friedel-Crafts reaction, specifically, Lewis reactions such as anhydrous aluminum chloride, boron trifluoride, phosphoric acid, sulfuric acid, antimony pentachloride, acid clay, activated clay, etc. In the presence of an acid catalyst, usually
One example is a method of reacting both at 110 to 140°C. In the polycyclic phenol AO adduct in the present invention, examples of AO include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), etc. PO or PO
A combination system (block or random, preferably random addition) with AO as the main component and other AO (eg EO) is preferred. The number of moles of AO added is usually 7 to 30, preferably 9 to 25. If it is less than 7 moles, the foam-inhibiting effect of the dye bath will be poor, and if it is more than 30 moles, the dispersibility will decrease, which is not preferred. Particularly preferred is one in which AO is PO or a random addition polymer of PO and EO, and the EO content is 3 to 35%. If the EO content is 35% or more, the foam-inhibiting effect of the dye bath will decrease. Above and below, EO stands for ethylene oxide, PO stands for propylene oxide, and BO stands for butylene oxide. The method for reacting polycyclic phenols with AO is a known method, for example, polycyclic phenols are reacted under pressure (5 kg/cm ² ) in the presence of an alkaline catalyst such as caustic soda, caustic potassium, metallic sodium, or methylate, usually at 120 to 190°C. One way is to add AO to . In this case, a polycyclic phenol AO adduct may be obtained by adding AO to the phenol in advance and then reacting it with styrene or the like using the method described above. The polycyclic phenol AO adduct in the present invention is usually a pale yellow liquid oily substance and is sparingly soluble in water. It is easily soluble in alcohols such as methanol, ethanol, and ethylene glycol, ketones such as acetone, and amides such as dimethylformamide. The dyeing aid in the present invention is polycyclic phenol AO.
This adduct is preferably used in combination with a polyoxyalkylene surfactant having an anionic group (also referred to as a nonionic/anionic surfactant). Examples of the nonionic/anionic activator include the following. In the following, salts include alkali metal (Na, K, etc.) salts, ammonium salts, amines (alkanolamines, etc.)
Contains salt. (1) Polyoxyalkylene alkyl ether sulfate sulfate AO adduct sulfate ester salt of linear and/or branched saturated and/or unsaturated alcohol having usually 6 to 20 carbon atoms (preferably 12 to 18): AO The number of moles added is usually 2 to 50, preferably 2 to 20, for example, decyl alcohol EO(1) sulfate ester ammonium salt (number 1 in parentheses)
indicates the number of moles of EO added. ), lauryl alcohol EO(4) sulfate ester sodium salt,
Cetyl alcohol EO(8) sulfate ester triethanolamine salt, Tergitol 15-S-9
(Secondary alcohol EO adduct manufactured by UCC)
Sulfate ester ammonium salts, etc. (2) Polyoxyalkylene alkylaryl ether sulfate salt EO adduct of alkylphenol or alkylnaphthol having at least one alkyl group having 8 to 12 carbon atoms (the number of moles of EO added is usually 2 to 1)
50, preferably 2-20) Sulfate ester salts such as nonylphenol EO (4) sulfate ester sodium salt, styryl (2) β-naphthol EO (10) sulfate ester potassium salt, dinonylphenol EO
(16) Sulfate ester sodium salt, etc. (3) Salts of sulfates of polyoxyalkylene polyol fatty acid partial esters Polyhydric alcohols or their intramolecular anhydrides (glycerin, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, sucrose, etc.) and fatty acids (usually 10 carbon atoms) ~20) (the number of moles of AO added is usually 2 to 50, preferably 10 to 40; for example, sorbitan monolaurate EO(10) sulfate ester sodium salt, sorbitan monooleate [EO
(20)/PO(10)] Sulfate ester potassium salt, sorbitan monostearate EO (30) Sulfate ester sodium salt, oleic acid monoglyceride
PO(10) sulfate potassium salt, soybean oil fatty acid monopentaerythritol ester sulfate triethanolamine salt {Note. Sorbitan monooleate [EO(20)/
PO(10)] is a product obtained by randomly adding 20 moles of EO and 10 moles of PO to sorbitan monooleate} (4) Polyoxyalkylene alkyl ether phosphate ester salt Saturated or unsaturated, usually having 6 to 20 carbon atoms EO adducts of alcohols phosphate ester salts such as stearyl alcohol EO(10) phosphoric diester monosodium salt, lauryl alcohol EO(5)
Phosphoric acid monoester potassium salt, oleyl alcohol EO(15) phosphoric acid diester sodium salt, etc. (5) Polyoxyalkylene alkyl phenyl ether acid ester salt EO adduct phosphate ester salt of alkylphenol or alkylnaphthol having one or more alkyl groups, usually having 8 to 12 carbon atoms, such as nonylphenol EO (5) Phosphoric acid diester monosodium salt, dinonylphenol
EO(16) phosphate monoester sodium salt, etc. Among the above-mentioned nonionic and anionic surfactants, preferred are polyoxyethylene alkyl phenyl ether sulfate salts and polyoxyalkylene polyol fatty acid partial ester sulfate salts. Particularly preferred is polyoxyethylene alkyl phenyl ether sulfate. The weight ratio of the polycyclic phenol AO adduct (dying aid in the present invention) to the nonionic/anionic activator is usually 100:0 to 30:70, preferably 30:70 to 60:40.
It is. The dyeing aid in the present invention is preferably used in combination with a nonionic or anionic surfactant, but it may also be used in combination with other nonionic or anionic surfactants (leveling agent, dispersing agent). good. Examples of surfactants that can be used in combination include monoesters of oleic acid and polyethylene glycol (molecular weight 600), formaldehyde condensates of naphthalene sulfonates, sulfate ester salts of higher alcohols, and salts of dioctyl sulfosuccinate (Na salts, etc.). ) etc. Examples of polyester fibers to which the dyeing method of the present invention can be applied include polyester fibers, blends of polyester fibers with other fibers such as cotton, linen, rayon, wool, silk, acetate, acrylic, etc. can be given. Examples of the molded article include cotton, thread, tow, top, filament, and knitted fabric. The dyes used include two or more types of dyes, such as disperse dyes or disperse dyes and direct dyes, reactive dyes, acid dyes, basic dyes, and vat dyes. When dyes other than disperse dyes are used together with disperse dyes, chemicals are usually used. For example, direct dyes such as mirabilite, reactive dyes such as mirabilite and soda ash, and vat dyes such as caustic soda and hydrosulfite are used. When dyeing textile products using these dyes, the dyeing methods include a one-bath, one-stage method and a one-bath, two-stage method. Polyester fibers are dyed by high-temperature, high-pressure dyeing. The dyeing aid in the present invention is usually 0.05 to 5% in the dye bath.
g/added. The amount of dye is usually 0.05-15% o.
wf (weight% of dye to fiber weight), bath ratio is usually 1:5 to 50 (fiber:bath weight ratio), pressure is usually 2
~5Kg/ ^cm2 and the soaking temperature is usually 120-135°C. After soaking, take it out, soap it, wash it with water, and then dry it. The method of the present invention has the following effects compared to conventional methods using known dyeing aids. That is, (1) in the dyeing method of the present invention, the emulsifying and dispersing properties of the dye bath are excellent, especially when dyeing polyester fibers with other fibers by high-temperature and high-pressure dyeing of blended, twisted, or knitted fabrics with different dyes. Even in the presence of chemicals such as glauber's salt and soda ash, the dispersibility of the dye decreases little and almost no dye specks (insoluble matter) occur. Therefore, according to the present invention, polyester fibers can be dyed without uneven dyeing. (2) The dyeing method of the present invention has an excellent foam suppressing effect, and even when polyester fibers and other fibers are blended, twisted, or knitted with different types of dyes and dyed at high temperature and high pressure, a large amount of foam is generated from different types of dyes. It exerts a foaming suppressing effect on the foaming that occurs, resulting in low foaming. Therefore, according to the present invention, polyester fibers can be dyed without the problem of foaming. (3) The method of the present invention also uses polyester fibers (100
%) with disperse dyes at high temperature and high pressure, this method can dye without staining spots and without the problem of foaming. Esterified dyeing aids or analogues thereof in the present invention, such as organic dibasic acid diesters of EO or adducts of EO and PO of arylphenols having 2 to 6 benzene nuclei (JP-A No. 50-26672) Publication), or aromatic ring 7
AO of polycyclic phenols having 1 or more phenols (however, all AO
When using a monocarboxylic acid ester (Japanese Patent Publication No. 53-31990) containing at least 5 moles of EO (50% by weight or more), it is possible to dye blends of polyester fibers and other fibers with different types of dyes. When dyeing is carried out in the presence of Glauber's salt, soda ash, etc., the dispersibility of the dye decreases and is not fully satisfactory. The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 Polyester/cotton (65/35) blended broad #40-10 using Colorpet 24 (manufactured by Nippon Senzo Kikai Co., Ltd.)
g to Dianic Navy Blue-BG-SE [disperse dye, manufactured by Mitsubishi Kasei Corporation] 4% OWF (for polyester fiber), Kayarasu Splat Black B-160 [direct dye, manufactured by Nippon Kayaku Co., Ltd.] 2% owf (for cotton fiber), anhydrous sodium sulfate 10 g/, acetic acid (80%) 0.3 cc/, styrenated (3) phenol EO (2) PO (10) and nonylphenol EO (10) sulfate ester sodium salt (60 % product) [Mixed product with a weight ratio (1/1)] The temperature was raised from 70°C to 130°C (60 minutes) in a 0.5g/dye bath (bath ratio 1:20),
It was dyed at the same temperature for 30 minutes, then cooled to 90°C, dyed at the same temperature for 30 minutes, and cooled to 30°C. Next, it was washed with hot water, water, and dried. The dyed cloth was level-dyed to dark blue. In other words, no dye specs were observed in the part corresponding to the casing, and level dyeing was possible. For comparison, a similar test was conducted using α-methylstyrenated (3) phenol EO (4), and the results were as follows.
Dye specks were generated on the casing, and level dyeing was not possible. Example 2-9, Comparative Example 1-2 (1) Polyoxyethylene (20) nonyl phenyl ether was added as a nonionic/anionic activator to each of the dyeing aids in the present invention and comparative dyeing aids shown in Table-1. A sulfuric acid ester sodium salt (80%) was mixed in a 1:1 ratio to conduct a dispersibility and low foaming test. The results are also shown in Table-1. (1) Dispersibility test The dye liquor was boiled under the following conditions, and after cooling, it was suctioned through Toyo Paper No. 5A, and the dye aggregates on the paper were visually determined. (Conditions) Dye liquid Kayarasu Spralet BL-200 [Direct dye manufactured by Nippon Kayaku Co., Ltd.] Resolin Red FB 2.5 g / [Disperse dye manufactured by Bayer AG] Dyeing aid 1.0 g / Acetic acid (80%) 0.3 cc / Anhydrous sodium sulfate 50 g / Liquid volume: 100c.c. Temperature, time: 30℃〓130℃ (2℃/min temperature increase),
130°C x 30 minutes, 135°C x 30°C (4°C/min temperature drop) Testing machine (judgment): Color Master HD-24 Those with significantly large amounts of dye aggregates were rated as 1st grade, and those with almost no dye aggregates were rated as 5th grade. . (Grade) (2) Foaming test Dye bath 5 below was placed in a testing machine and the solution was circulated. Heating and raising the temperature, each temperature (40℃→130℃)
℃→90℃), the liquid flow was stopped, and the amount of foaming was measured after 5 seconds. (Conditions) Dye liquid: Kayarasu Splat Black B-
160 2g/ [Direct dye made by Nippon Kayaku Co., Ltd.] Dianics Orange B-SE 2g/ [Disperse dye made by Mitsubishi Kasei Co., Ltd.] Dyeing aid 0.5g/ Acetic acid (80%) 0.3cc/ Anhydrous sodium sulfate 20g/ Circulation Flow rate: 2/min, spraying from a nozzle diameter of 1 mm Test machine: High-pressure injection type liquid flow foaming tester (Judgment) ◎: Average foaming amount from 40℃→130℃→90℃ is 10mm
Below 〇: Average foaming amount from 40℃→130℃→90℃ is 30mm
Below △: Average foaming amount from 40℃→130℃→90℃ is 60mm
Below ×: Average foaming amount from 40℃→130℃→90℃ is 100mm
(2) A 1:1 mixture of polyoxyethylene (20) nonylphenyl ether sulfate ester sodium salt as a nonionic/anionic activator to the dyeing aids of the present invention and comparative dyeing aids shown in Table-1. was used to dye polyester fibers at high temperature and pressure. Covering properties, dye migration properties, sublimation fastness and rub fastness were measured and the results are shown in Table 1. (1) Covering property test Knitted fabrics with different dyeability made of four types of polyester processed yarns with different heat histories were dyed under the following dyeing conditions, and the covering properties were visually judged. (Conditions) Dye: Phoron Navy-S-2GL (disperse dye manufactured by Sandoz Co., Ltd.) 2% owf PH: 5 (80% acetic acid 0.3cc/) Dyeing aid: 0.5g/ Bath ratio: 1:20 Temperature, time :70℃〓130℃(2℃/min temperature increase),
130°C x 60 minutes, 130°C = 90°C (4°C/min temperature drop) Testing machine: Color Master HD-24 (Judgment) ◎: There is almost no color difference between the 4 types of samples 〇: 〃 Slight difference △: A case in which a color difference between the 4 types of samples is clearly observed ×: A case in which a significant color difference between the 4 types of samples is observed (2) Dye migration test Dye in advance with each of the following dyes a, b, and c (130℃ x 60 minutes) , no reduction cleaning) and dyed cloth (three primary colors) were created. One piece of white cloth of the same quality and quantity as each of the three primary colors
A total of four fabrics were treated with the solution of the test sample, and the degree of dye transfer to each dyed fabric was visually determined. Dye a Sumikalon Red E-FBL (disperse dye
(manufactured by Sumitomo Chemical Co., Ltd.) 1% owf b Resolin Blue FBL (disperse dye manufactured by Bayer) 1% owf c Paranyl Yellow 3G (dispersed dye manufactured by Ciba and Geigy) 1% owf (conditions) Sample fabric: polyester processed yarn fabric Bath ratio: 1:20 PH: 5 (80% acetic acid 0.3cc/) Dyeing aid: 0.5g/ Temperature, time: 130℃ x 45 minutes Testing machine: Color Master HP-24 (Judgment) Three primary color dyed fabrics and attachments Grade 5 is when the white cloths are all the same color (gray), and grade 5 is when the dyes in the dyed cloths of the three primary colors have hardly progressed and the original color remains, and the color of the attached white cloth is also 1 grade.
and ranked them into five levels. (3) Sublimation and rubbing fastness The polyester processed yarn fabric was dyed under the following dyeing conditions, and after reduction washing and drying, the sublimation fastness,
Judgment was made by conducting a friction fastness test. (Conditions) Dye: Dianic Thread G-SE (disperse dye manufactured by Mitsubishi Kasei Corporation) 4% owf Dyeing aid: 0.5g/PH: 5 (80% acetic acid 0.3cc/) Temperature, time: 130℃ x 45 Minutes Reductive cleaning: Hydrosulfite 1g / Caustic soda 1g / Nonionic activator 0.5g / 80℃ x 10 minutes (bath ratio 1:20), water washing, drying (Judgment) Sublimation fastness (Tetron contamination) JIS L0879-
Compliant with 1968 180℃, 30 seconds Rubbing fastness JIS L0849−1971 (dry)

【table】

[Table] Examples 10-12 Regarding other dyeing aids of the present invention shown in Table-2,
Dispersibility and low foaming tests were conducted in the same manner as in Examples 2 to 9, and the results are also shown in Table 2.

【table】

Claims (1)

[Claims] 1 Styrenated phenols, styrenated arylphenols, styrenated halogenated phenols,
A compound in which alkylene oxide is added to a phenol having 2 to 6 aromatic rings selected from the group consisting of benzylated chlorinated alkylphenol and benzylated arylphenol chloride {however, the number of moles of alkylenoxide added is 7 to 6. 30 and the content of EO (ethylene oxide) is 35% or less.