JPS6026870B2 - Hydrophobic synthetic fiber dyeing aid - Google Patents

Description

[Detailed description of the invention] The present invention relates to a dyeing aid for hydrophobic synthetic fibers.

More specifically, the present invention provides dyed products with uniform hue and excellent quality when dyeing fiber materials made of hydrophobic synthetic fibers or mixed fibers containing hydrophobic synthetic fibers with disperse dyes or azoic dyes. This invention relates to dyeing aids that can be obtained. When dyeing hydrophobic synthetic fibers such as polyester, generally, disperse dyes or azoic dyes are used to carry out high-temperature, high-pressure dyeing at a temperature of 110 to 140 oo or carrier dyeing at a temperature of around 10,000 ℃.

On the other hand, recently, rapid dyeing, which shortens the dyeing time and reduces the amount of dye solution, has been put into practical use for the purpose of streamlining the dyeing process and saving energy. Therefore, compared to the conventional high-yield dyeing that rises at a low speed and takes sufficient time to mix, the dye becomes a highly concentrated liquid because it has a low-quality dye.
Tarring of the dye is promoted, causing specks to appear on the surface of the dyed product and problems with contamination. Furthermore, recently, cheap azo disperse dyes have been increasingly used, but their structure makes it difficult for them to diffuse internally, resulting in uneven dyeing with strike-like flickering or uneven dyeing on the fiber surface. occurs.

In order to solve these problems, the present inventors have conducted extensive research into dyeing aids that are free from these problems and have a high level of dye solubilization performance, and have thus arrived at the present invention.

According to the present invention, there is provided a beam coloring aid for hydrophobic synthetic fibers which has a novel ability to solubilize beam materials.

The dyeing aid according to the present invention contains at least one compound selected from the following general formulas 1, 2 and m as a main component. In the above formula, R each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, one of R2 and R3 represents a hydrogen atom, the other represents a methyl or ethyl group, and R4 represents a polycyclic phenol. , a residue of a formalin condensation polymer of polycyclic phenol, or a residue of a formalin condensation polymer of polycyclic phenol and phenol or alkylphenol, and a, c, e, g and i are each independently represents an integer from 1 to 100, b, d, f, h
and i each independently represent 0 or an integer from 1 to 100, and k' represents an integer from 2 to 10.

That is, according to the present invention, formaldehyde is added to a polyoxyalkylene glycol adduct of an alkylphenol, a polyoxyalkylene glycol adduct of a polycyclic phenol, or a derivative thereof, an alkylene glycol, a polyalkylene glycol, etc., and the mixture is dehydrated and condensed. A dyeing aid for hydrophobic synthetic fibers containing the produced ether crosslinked condensate as a main component is provided.

The phenols used in the production of the beam coloring aid according to the present invention include phenol and alkylphenol, and the formaldehyde is preferably paraformaldehyde.

In addition, alkylene oxides include ethylene oxide,
Propylene oxide, butylene oxide, etc. are used. The compound according to the present invention can be produced by a known method, for example, by adding alkylene oxide to phenol using a conventional method (when adding two or more types of alkylene oxide, either block addition or random addition can be used). good) Next, the above reactant or polyalkylene glycol was mixed with paraformaldehyde for 10
The compound of the present invention is produced by carrying out a condensation reaction in the presence of an acidic catalyst at a temperature of 0 to 12,000 ℃. Further, the dyeing aid of the present invention may contain a known beam coloring aid, dyeing carrier composition, and the like. When using the auxiliary agent of the present invention, it is preferable to add the beam coloring auxiliary agent in an amount of 40 to 100%, based on the weight of the dye, in a beam bath containing a disperse dye and an acid. Suitable dyes include disperse dyes and azoic dyes. Suitable hydrophobic synthetic fibers include synthetic fibers such as polyester acetate. The beam coloring auxiliary of the present invention has a uniform beam strength that is higher than that of ordinary nonionic beam coloring auxiliaries and a dispersibility that is equal to or higher than that of ordinary anionic dyeing auxiliaries. Has solubilizing performance.

In recent years, inexpensive azo disperse dyes are often used.
Due to its structure, it tends to diffuse internally and cause streak-like flickering or uneven dyeing on the surface of the fibers, resulting in unsteady beams. There is a demand for dyeing aids that can

Taking these demands into consideration, the additive of the present invention solubilizes dyes in a low temperature range of 9,000°C or higher and 110°C or lower, which is not the case with conventional nonionic color additives, so that any dye can be used under any dyeing conditions. It also has the characteristic of being able to obtain excellent dyeing results. Furthermore, the foaming property is equivalent to or higher than that of conventional low-foaming nonioso dyeing aids, and the dyeing can body is hardly contaminated. The present invention will be further explained below with reference to Examples.

"Parts" and "%" in the examples indicate parts by weight and % by weight unless otherwise specified. Example 1 26 moles of nonylphenol pine oxide ethylene and 30 moles of propylene oxide are subjected to an addition reaction at 160 to 170 oC by adding 1.1 parts of caustic soda as an addition catalyst.

Next, 3 parts of BF3 catalyst are added, and 1 mol of butylene oxide is subjected to an addition reaction at 50 to 60 o'clock. As a result, a polyoxyalkylene glycol adduct of nonyl phenol having an average molecular weight of 3,100 is obtained. Add 35 parts of rose formaldehyde to the obtained addition product, and add 50 to 6 parts of rose formaldehyde.
The addition methylolation reaction is carried out for 2 hours.

Next, 6 parts of sulfuric acid with a purity of at least 10% is added to the methylolation reaction product of the polyoxyalkylene glycol adduct of nonylphenol, and a condensation reaction is carried out at 5°C. This reaction product is in the form of a yellow viscous liquid (referred to as the beam coloring aid A of the present invention) and is soluble in water. Example 2 144 parts of Q-naphthol and 0.0 parts of caustic soda as a catalyst.
1 part of ethylene oxide, then 2 parts of propylene oxide, and finally 1 part of ethylene oxide are subjected to a block addition reaction using a known method to obtain 1 part of the addition reaction product.

Next, this addition reaction product was neutralized with monoethanolamine, and after neutralization, 35 parts of rose formaldehyde was added, and 4
The methylolation reaction is carried out at 0 to 50 oo for 5 hours. 4 parts of sulfuric acid with a purity of at least 1% is added as a catalyst to the obtained methylolation reaction product, and a condensation reaction is carried out at 105 to 115 qo for 4 hours to obtain a methylene crosslinked polycondensation product having an average molecular weight of 4420. The obtained reaction product is in the form of a yellow viscous liquid [referred to as dyeing aid B of the present invention] and is soluble in water. Example 3 Pluronic 290 base obtained by adding about 26 moles of ethylene oxide to polyoxypropylene glycol having an average molecular weight of 1740 was added with 35 parts of formaldehyde and heated at 50 to 60°C for 1 hour. Perform the addition methylolation reaction.

6 parts of sulfuric acid with a purity of 1% or more was added to the obtained methylolation reaction product of polyoxyalkylene glycol, and the mixture was heated to 110±
The condensation reaction is carried out at 5°C. This reaction product is in the form of a colorless transparent viscous liquid [referred to as the beam coloring aid C of the present invention] and is soluble in water. Example 4 In order to compare the performance of the dyeing aid of the present invention and that of a conventional dyeing aid, various performance tests were conducted as described below.

The dyeing aid of the present invention had the ability to solubilize disperse dyes particularly at low temperatures, had excellent level dyeing properties, and had low foaming properties. The results are shown in Table 1 below. Table 1 Performance test method ■ Dispersibility test (Color PET winding method) Place the following dye solution into the pot of Color PET (manufactured by Nippon Senzo Kikai), wrap the polyester processed yarn knit around the holder, and secure both ends with a ○ band'. The dyed material is set, rapidly heated to 115q0 for dyeing, and immediately cooled.

After washing with water, the dispersibility is evaluated by the number of casing spots on the cloth. Dye: Holosorpine S-20FL (C.1. Disperse Thread 167) 3% o. w. f
．． Dyeing aid: 0.5% 80% acetic acid 0.3' / Bath ratio 1:15 Evaluation: ix No casing spots ○ Few casing spots △ Possible casing spots ■ Equal beam property test Dyeing under the following conditions The processed polyester yarn fabric and the same unliang fabric were placed in an aqueous solution containing only Liang color aid and acetic acid, and treated in Colorpet with 3 P0 for 5 minutes to determine how much dye from the dyed fabric was transferred to the unliang fabric ( migration).

Dyeing dye: Diamonds Orange B-SE (C.1. Disperse Orange 13) 1.0% o. lol
．． f. Diamond thread BN-SE (C.1. Disperse thread 127) 0.7% o. lol
．． f. Diamond Sprue GR-E (C.1. Disperse Blue 81) 0.3% o. w. f. 80% acetic acid
0.3'/So dyeing machine: Small Nuis (Model 30 blood) Temperature, time: 130qo x 6th generation Bath ratio: 1:15 As migration test liquid, Dyeing aid 0.5/So 80% acetic acid An aqueous solution consisting of 0.3% water was used.

However, 1 part of dyed cloth and 1 part of white cloth were used. Yuhiro: 1:1
5. Evaluation The reflectance of the dye transfer fabric and transfer white fabric obtained in the above migration test was measured, and the dye transfer rate was calculated from the reflectance using the following formula, and the larger the number, the better the level dyeing property.

Transfer rate; (density correlation value of transferred white cloth/density correlation value of transfer dyed cloth) x 100 density correlation value = (1-R0Rc/R)2/
2 (R-Rc/R)R: Reflectance/100Rc: Coefficient, Side color machine: Color Eye KCS-1, manufactured by Kollmorgen Co., Ltd.
■ Super Foam Test Take the following sample solution into a graduated cylinder (diameter 75 side), put the Pall filter and the bottom of the cylinder in the cylinder, and heat it with an air pump at 90°C for 15 minutes.
Air is blown into the foam at a rate of 19 min, and the height of the bubbles generated is measured immediately after the blowing has stopped, after 1 rat sand, and after 3 sand (in units of 1).

As the measuring solution, we used 300 parts of a dye solution containing 1 part of Diamonds Orange B-SE (C.1. Disperse Orange 13), 1 part of Tanok dyeing aid, 0.5 parts of 80% acetic acid, and 0.3 parts of 80% acetic acid. did.

■ Dye solubilization temperature test: Place the following liquid into the pot of Diometer (manufactured by Suga Test Instruments) and heat at a rate of 5℃/min from 50 to 80 o'clock.
The temperature is raised at a rate of 3° C./min to 100° C. and at a rate of 2° C./min above 100° C., and the transparent solubilization temperature of the beam liquid flowing in the glass cylinder is evaluated.

Dye: Holonrubin S-Hon FL (C.1. Disperse Thread 167) 1 Tano〆 Dyeing agent 0.5 tsp/so 80% room acid 0.3 ml , the flow rate was 200'/min.

Claims (1)

[Claims] 1. A dyeing aid for hydrophobic synthetic fibers containing at least one compound selected from the following general formulas I, II and III as a main component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R_1 is each independently a hydrogen atom or a carbon number of 1
~30 alkyl groups, one of R_2 and R_3 represents a hydrogen atom, the other represents a methyl or ethyl group, R_4 is a residue of a polycyclic phenol, a residue of a formalin condensation product of a polycyclic phenol , or represents the residue of a formalin condensation product of polycyclic phenol and phenol or alkylphenol, a, c, e, g and i each independently represent an integer from 1 to 100, b, d, f,
h and j each independently represent 0 or an integer from 1 to 100, and k represents an integer from 2 to 10.