JPH032991B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a dyeing aid for dyeing polyester synthetic fibers or blended/cross-knitted woven products of polyester synthetic fibers and cellulose fibers (hereinafter abbreviated as T/C blend fibers). When dyeing synthetic fibers or T/C blend fibers at high temperatures using disperse dyes, dyeing aids are used to obtain efficient and uniform dyed products, especially dispersion destruction of disperse dyes in the presence of sulfate. This invention relates to a dyeing aid that aims to prevent staining of cellulose fibers caused by disperse dyes (hereinafter referred to as cotton staining) to a minimum. When dyeing polyester synthetic fibers at high temperatures, the rapid dyeing method has become mainstream in recent years due to the rationalization of the dyeing process. There is a growing demand for excellent level dyeing performance. Furthermore, in recent years, the bath ratio has been lowered in dyeing, and with this, dye spots caused by wrinkles have become more of a problem than before, so dyeing aids that have a softening effect in the bath are also used. It has come to be sought after as a performance feature. On the other hand, the single-bath dyeing method has also been adopted for dyeing T/C blend fibers, which has caused problems such as dispersion destruction of disperse dyes and increased cotton contamination due to the influence of sulfur sulfate present in the dye bath. It is becoming a major issue to solve such problems with dyeing aids. As a result of intensive studies aimed at solving such dyeing problems, the inventors of the present invention discovered that a certain type of surfactant has excellent performance as a desired dyeing aid. That is, the dyeing aid of the present invention is a compound represented by the following general formulas () and (). (However, A represents a polyhydric alcohol residue having 3 to 6 OH groups, and R represents a higher fatty acid residue having 6 to 22 carbon atoms. m and n are m>n, and m is 1 ~
10, n is an integer in the range of 0 to 5, x and y are x≦y, and x+y is the polyhydric alcohol.
Indicates that the number is equal to the OH base number. Further, M represents K, Na, NH ₄ or N-alkyl (or alkanol) ammonium having 6 or less carbon atoms. ) (However, R ₁ is a higher alcohol residue having 6 to 22 carbon atoms, and R ₂ is or OM (M is the same as in the general formula).
a and b are each integers from 0 to 5, but b=
In the case of 0, it indicates the range of a=0 to 3. )
At the same time, the compounding ratio is [compound]:
[Compound]=100:100 to 100:2. Examples of the polyhydric alcohol and higher fatty acid which are the raw materials of the general formula () include the compounds shown below. 1 Polyhydric alcohols glycerin, pentaerythritol, dicrycerin, arabite, sorbitol and dipentaerythritol. 2 Higher Fatty Acid Caproic Acid, Caprylic Acid, Lauric Acid, Myristic Acid, Palmitic Acid, Oleic Acid, Stearic Acid, Isostearic Acid, and Behenic Acid The compound of the present invention represented by the general formula () can be easily obtained by a known method. That is, polyhydric alcohol is subjected to an addition reaction with ethylene oxide (hereinafter referred to as EO) or EO and propylene oxide (hereinafter referred to as PO) using an alkali hydroxide catalyst, and then higher fatty acids are produced using an acid or alkali catalyst. A partial esterification reaction may be carried out with the OH group, followed by sulfation using a sulfating agent equivalent to the remaining OH group. In this case, care must be taken when sulfuric acid, chlorosulfonic acid, or sulfuric anhydride is used as the sulfating agent, since hydrolysis of the ester bond easily occurs, and sulfamic acid is preferably used. The number of added moles of EO or PO or per OH group of polyhydric alcohol is 1 to 10 moles and 0 to 10 moles, respectively.
If there are 5 moles and both are added, random addition,
Either block addition is fine, but at least both PO
If the number of moles added to EO exceeds the number of moles added to EO, the dispersibility of the disperse dye deteriorates and furthermore, cotton staining increases, which is undesirable.In the same sense, the addition of PO alone is also unfavorable. In addition, during the esterification reaction, it is preferable to limit the esterification to 1/2 equivalent or less of the OH groups in the polyoxyalkylene adduct of the polyhydric alcohol, and then sulfate the remaining OH groups as completely as possible. Publication No. 31082 (1982), Special Publication No. 56 (1982)
As described in Publication No. 38712, the terminal OH
Sulfated products in which 1/2 equivalent or more of the groups are esterified and sulfated products in which some OH groups remain tend to have an adverse effect on dispersibility, and in particular, significantly increase cotton contamination. It is unsuitable as a dyeing aid for this purpose. The compound of the present invention represented by the general formula () has a relatively low foaming property even when used alone, and is also excellent in dispersibility, level dyeing property, and glass resistance, but on the other hand, it lacks a softening effect in a bath. There is a problem of uneven dyeing due to wrinkles. The present inventor simultaneously contains a compound represented by the general formula () and a compound represented by the general formula (),
The mixing ratio is [compound]: [compound] = 100:
By adjusting the ratio to 100 to 100:2, it is possible to further reduce foaming and improve the softening effect in the bath. Compounds represented by the general formula () can also be easily obtained by known methods. That is, after adding EO or/and PO to a higher alcohol having 6 to 22 carbon atoms or these, it may be phosphorylated with phosphorus oxychloride or phosphoric anhydride, and then neutralized with an alkali. The number of moles of EO and PO added is 0 to 5 moles, but EO
In the case of single addition, it is preferable to limit the amount to 3 mol or less in order to obtain a low-foaming dyeing aid. Further, the higher alcohol used can include the alcohols corresponding to the higher fatty acids already exemplified, but palmityl alcohol, oleyl alcohol, stearyl alcohol, behenyl alcohol, etc. are suitable in order to exhibit the softening effect in the bath. Also, the compounding ratio of the compounds represented by general formula () and general formula () is general formula (): general formula () =
The blending ratio is in the range of 100:100 to 100:2, and outside this blending ratio (a) the slag resistance is poor, and the dispersibility and leveling properties are reduced. (b) Foaming increases and causes trouble during dyeing. (c) Uneven staining occurs due to wrinkles. This is not preferable because problems such as the following may occur. In addition, the amount of the dyeing aid of the present invention to be used is usually 0.3 to 1.0 g/total of general formula () and general formula ().
is sufficient. Examples of the present invention are shown below. Example 1 92 parts (1 mol) of glycerin was charged into a pressurized reaction vessel, 0.5 part of caustic potassium was added as a catalyst, and 110-120 parts of glycerin was charged.
After dehydration under reduced pressure at °C for 1 hour, the reaction vessel was purged with nitrogen. Then, at a pressure of 2 to 3 Kg/cm ² and a temperature of 145 to 150°C.
528 parts (12 moles) of EO and 174 parts (3 moles) of PO were simultaneously injected and reacted over about 2 hours, and the mixture was aged at the same temperature for about 1 hour. Transfer the reaction mixture to a four-necked flask, add 284 parts (1 mol) of stearic acid and 3.5 parts of caustic potassium,
The dehydration reaction was carried out at 220-230℃ for about 5 hours, and the reaction rate was 95.
% or more of the esterified product was obtained. This stuff at 130℃
194 parts (2 mol) of sulfamic acid and 120 gr (2 mol) of urea as a catalyst were added, and after sulfating at the same temperature for 2 hours, the pH was adjusted to 7.0 to 8.0 with aqueous ammonia.
Compound (1) of the general formula () of the present invention is neutralized to
I got it. The structural formula of this is shown below. (however,

The arrangement of [Formula] is random, l+m+n=12, x+y+z
=3. ) Compounds (2) and (3) of the present invention represented by the general formula () represented by the following structural formula were obtained in the same manner. (However, a+b+c+d=16) (However, p+q+s+t+u+v=12) Example 2 Oleyl alcohol was prepared in the same manner as in Example 1.
Add 44 parts (1 mol) of EO to 268 parts (1 mol),
Transfer this material to a four-necked flask, and add 153 parts (1 mole) of phosphorus oxychloride to about 2
dripped for an hour. Next, dehydrochlorination was carried out at the same temperature for about 3 hours while introducing nitrogen gas, and then neutralized with 25% caustic soda to obtain compound (4) of the general formula () of the present invention. The structural formula of this product is as follows. Compound (5) having the following structural formula was obtained in a similar manner. Example 3 Various performance tests were conducted to compare the performance of the dyeing aid of the present invention and a conventional dyeing aid. The test method and test results were as follows. (1) Dispersion test Colorpet 12 type dyeing machine (manufactured by Nippon Senzo Kikai)
Pour 300ml of the following dye solution into the pot, and use commercially available polyester jersey 10gr to heat at 130℃ for 5 minutes.
After dyeing and washing with water, visually judge the dye spots on the sample cloth. The results are shown in Table-1. <Dye liquid> Dye-1 Sumikalon Yellow Brown S-2RL
0.5%owf Phuoron Rubin S-2GFL 2.0 〃 Dianix Blue BG-FS 0.5 〃 Dye-2 Dyanix Orange B-SE 0.5 〃 Dyanix Red BN-SE 0.5 〃 Phuolon Navy S-2GL 2.0 〃 80% Acetic Acid 1c.c ./ Sodium acetate 3gr/ Sodium salt 0gr/, 40gr/, 80gr/ Comparative product 1 Formalin condensate of sodium naphthalene sulfonate (50% product) Comparative product 2 Poly(14) oxyethylene glyceryl ether monooleate Comparative product 3 Ammonium monosulfate salt of poly(12)oxyethylene glyceryl ether monooleic acid <Judgment criteria> ◎...No dye spots are observed. 〇…The dye spot is only visible on about 1/4 of the sample cloth. △... Dye spots are visible up to about 1/2 of the sample cloth. ×... Dye spots are visible on more than 3/4 of the sample cloth. (2) Level dyeing test and cotton staining test Using the same amounts of commercially available processed polyester yarn fabrics and cotton broadcloth, dyed products under the following conditions were washed and dried, and the level dyeing property of the polyester was visually judged. Grades were determined using Broad's contamination gray scale. The dyeing aids and amounts used were the same as in the dispersion test. The results are shown in Table-2. Test conditions Dye Daianniphus Orange B-SE
1%owp ^* Fuoron Rubin S-2GFL 1%owp Daianniphus Blue BG-FS
1% owp *OWP indicates the weight percent based on polyester 80% acetic acid 1c.c./Sodium acetate 3gr/Salt glass 0 or 40gr/Bath ratio 1:20 Temperature/time
130°C x 30 minutes (temperature increase rate: 4°C/min) (3) Foaming test A foaming test was conducted in the following manner. Dye Phoron Rubin S-2GFL 1gr / Auxiliary agent Same as in the dispersion test 80% acetic acid 0.3cc / <Test method> Put 300ml of the above test solution into a glass column, introduce nitrogen gas, and after 1 minute at 80℃ and determine the foam height after 5 minutes. <Test Results> The test results are shown in Table-2.

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Claims (1)

[Claims] 1. A polyester synthetic fiber or polyester/cellulose, characterized in that the compounds represented by the following general formulas () and () are mixed in a ratio of 100:100 to 100:2. Dyeing aid for mixed fiber products. (However, A represents a polyhydric alcohol residue having 3 to 6 OH groups, and R represents a higher fatty acid residue having 6 to 22 carbon atoms. m and n are m>n, and m is 1 ~
10, n is an integer in the range of 0 to 5, x and y are x≦y, and x+y is the polyhydric alcohol.
Indicates that the number is equal to the OH base number. Further, M represents K, Na, NH ₄ or N-alkyl (or alkanol) ammonium having 6 or less carbon atoms. ) (However, R ₁ is a higher alcohol residue having 6 to 22 carbon atoms, and R ₂ is or OM (M is the same as in the general formula).
a and b are each integers from 0 to 5, but b=
In the case of 0, it indicates the range of a=0 to 3. )