JPS5926714B2 - Polyester fiber dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high temperature dyeing method for polyester fibers.More specifically, the present invention relates to a method for dyeing polyester fibers at high temperatures. This invention relates to a dispersion leveling agent used when dyeing knitted articles at high temperatures using disperse dyes.

Disperse dyes are usually used to dye polyester fibers, but since polyester fibers have a dense molecular structure, the color development method is so-called carrier dyeing, which is carried out at around 100°C under a dye accelerator called a carrier, or 120°C. ~1
There are two types of so-called high-temperature and high-pressure dyeing methods, which are carried out at a high temperature of 40° C. under pressure.

Particularly in recent years, as labor-saving and energy-saving trends have become stronger, methods for dyeing in a short time using high-temperature and high-pressure dyeing methods,
That is, a staining method generally referred to as a rapid staining method has been researched and developed.

However, when dyeing with these dyeing methods, many of the commonly used commercially available disperse dyes do not have satisfactory performance in terms of dispersibility, dye migration, foaming properties, etc. during high-temperature dyeing. It's causing problems.

For this reason, unless a dyeing aid with excellent dispersibility, dispersion, and low foaming (foam suppression) properties is added to the dye bath, it is impossible to obtain a good dyed product with a uniform hue without spots or irritation. I can't.

In other words, poor dispersibility of the dispersion and leveling agent promotes dye aggregation and tarring, resulting in uneven spots and irritability, and when the transferability of the disperse dye is insufficient, dyeing such as uneven hue and color breakage occurs. Causes spots.

In addition, the foaming properties of disperse dyes directly contact dyeing spots and cause troubles in dyeing operations.

As a measure to improve uneven dyeing properties caused by these factors, it has been known to use surfactants as so-called dyeing aids.

That is, formalin condensate of naphthalene sulfonic acid,
Anionic surfactants such as alkylbenzene sulfonates and higher alcohol sulfate salts, nonionic surfactants such as polyoxyethylene alkyl ethers and holoxyethylene alkylphenyl ethers, and surface active agents such as sulfate salts of these nonionic surfactants. The dyeability of disperse dyes has been improved by adding one or more agents to the dyebath, but no matter which dyeing aid is used, satisfactory results in terms of dispersibility and dye migration have not been achieved. I couldn't get it.

The present inventors have arrived at the present invention as a result of intensive research aimed at solving the problems of dyeing polyester fibers with such disperse dyes.

That is, the present invention provides a compound (R1) represented by the following general formula CI, 1, (II, 1) m-A-0(CH2CH2),
. and (R2)n-B-0(CH2CH20)qS03M-(
III) [Size, B represents a cyclohexylphenyl group, R2 is a substituent of B and represents a benzyl group or a styryl group, n is 1 or 2, and q is a numerical value of 8 to 80. , M is an alkali metal, ammonia, or an ethanolamine such as monoethanolamine, jetanolamine, triethanolamine, etc.] This is a polyester fiber dyeing method characterized by containing in the dye bath.

The compounds of the above general formulas CI and I of the present invention include phenols,
For example, derivatives of phenol, ortho- or para-phenylphenol, cresol, octylphenol, nonylphenol, dinonylphenol, which have 1 to 5 benzyl groups or styryl groups as substituents, and further have 8 to 8 ethylene oxides as substituents. 100 moles were added.

The compound of the above general formula (n) has cyclohexylphenol with 1 or 2 benzyl groups or styryl groups as substituents, and 8 to 80 moles of ethylene oxide is added to the terminal, which is further sulfated and neutralized with ammonia etc. This is what I did.

Compounds of the general formula CI), (ID exhibit dispersion and level dyeing performance even when used alone, but CI), and (ID) can be combined to balance various performances such as dispersibility and dye migration that could not be obtained with each compound alone. It is particularly effective on the surface.

The compound in the present invention can be produced by any known method.

For example, using benzyl chloride as a phenol, or using styrene as a catalyst with AlCl3.5bC15, activated clay, etc.
NaO
H, KOH.

Using an alkaline catalyst such as NaOCHa, 160-19
A polyoxyethylene compound can be obtained by addition at 0°C, and the compound can be sulfated using sulfamic acid, chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, sulfuric anhydride, etc.
After reacting under heating or cooling, alkali metals, alkali metal hydroxides, ammonia, monoethanolamine,
This can be carried out by a known method of neutralizing with jetanolamine, triethanolamine, etc. to form a sulfate ester salt.

In the method of the present invention, the weight ratio of the nonionic activator of general formula CI) and the anionic activator of general formula (■) is 90 to 10% [■] to 10 to 90% of (I). In addition to exhibiting more complete dispersion retention and stability over the entire dyeing temperature range, it also has excellent dye migration properties, making it possible to obtain dyed products with uniformity and good hue that could not be obtained conventionally.

A more preferable combination ratio of compounds CI) and (III) is CI) 20 to 70% and (II) 80 to 70% by weight.
It is 30%.

In addition, the amount of the dispersion leveling agent of the present invention added to the dye bath is 0.2 to
2.0 g/l is sufficient, and 0.3 to 1.0 g/l is particularly preferred, and it is also possible to use it in combination with conventional dispersants, leveling agents, antifoaming agents, etc. .

Specific examples of the present invention will be shown below and explained in more detail,
It is not necessarily limited to these.

Synthesis example of dyeing aid (I-a) 4 with dropping funnel, thermometer, cooler and stirring device
94 grams of phenol in a double flask, 1.0 grams of anhydrous aluminum chloride. O'f? was heated to 120-140°C, 312 g of styrene was gradually added dropwise, and after aging sufficiently at that temperature, it was transferred to an autoclave reactor, 3.91% of potassium was added as a catalyst, and the temperature was heated to 90-100°C at 720°C. After topping under imHg conditions and repeating nitrogen substitution, the temperature was raised to 1.
880 g of ethylene oxide is added and reacted under heating and pressure of 2.5 ky/cvt at 60 to 170°C.

After cooling this to 60-70°C, phosphoric acid was added to neutralize it, and the salt was filtered off to obtain a pale yellow solid substance 1272y'.

This material was a 20 mole polyethylene oxide adduct of tristyrylated phenol.

(I-b) Styrenation of ortho-phenylphenol and ethylene oxide addition reaction are carried out using the same equipment and method as in (I-a).

That is, after carrying out a styrenation reaction using 171' ortho-phenylphenol, 21 g of anhydrous aluminum chloride, and 312 g of styrene, it was transferred to an autoclave reaction vessel, and the mechanical strength was 1.1 g.
4.7P was added, and ethylene oxide 1100P was added to obtain a light brown solid substance 1550P.

This material was a 25 mole ethylene oxide adduct of tristyrylated-orno phenylphenol.

(■-c) Styrenation of para-nonylphenol and ethylene oxide addition reaction were carried out using the same equipment and method as in (I-a). After the reaction, it was transferred to an autoclave reaction vessel and the strength of the potash was 3.91.
was added, and 880 g of ethylene oxide was added to obtain a light brown solid substance 1295P.

This material was a 20 mole ethylene oxide adduct of distyrylated para-nonylphenol.

(I-d) Benzylation of meta-cresol and addition reaction with ethylene oxide are carried out using the same apparatus and method as in (I-a).

That is, meta-cresol 108t? , anhydrous aluminum chloride 2
1. After carrying out a benzylation reaction using 379.5y' of benzyl chloride, transfer it to an autoclave reaction vessel and add 379.5y' of benzyl chloride.
．． 41 was added, and ethylene oxide 7482 was added to obtain a light brown solid substance 1112f.

This material was a 17 mole ethylene oxide adduct of tribenzylated meta-cresol.

(I-e) Benzylation of ortho-phenylphenol and addition reaction with ethylene oxide are carried out using the same equipment and method as in (I-a).

That is, after carrying out a benzylation reaction using 1701 ortho-phenylphenol, 2 grams of anhydrous aluminum chloride, and 2531 grams of benzyl chloride, the mixture was transferred to an autoclave reactor, 3.91 grams of potassium was added, and 968 tons of ethylene oxide was added. was added to obtain a light brown solid substance 1300S'.

This material was a 22 mole ethylene oxide adduct of dibenzylated ortho-phenylphenol.

(na) Benzylation of ortho-cyclohexylphenol and addition reaction with ethylene oxide are carried out using the same apparatus and method as in (I-a).

That is, a benzylation reaction was performed using 88 g of ortho-cyclohexylphenol, 1 g of anhydrous aluminum chloride, and 126.5 P of benzyl chloride, and then transferred to an autoclave reaction vessel.
Add 1.81 mol of potassium and add 3301 ethylene oxide to form a 25 mol ethylene oxide adduct of dibenzylated ortho-cyclohexylphenol (hydroxyl value 60).
．． 1, average molecular weight 933) was obtained.

Next, this compound 467f (0.5 mol) was added to a stirring device,
A reactor equipped with a thermometer was charged with 63% of sulfamino acid under a nitrogen stream. Add IP (0.65 mol) little by little,
It was made to react at 20-125 degreeC for 5 hours.

After that, it was cooled, and 10,100 O of methanol was added to dissolve it, and then 54.61 (0.68 mol) of 50% caustic soda was added to make the sodium salt.After cooling, the inorganic salt was filtered off, and methane and water were added. Distilled brown viscous substance 5161
I got it.

This material was the sulfate ester sodium salt of a 15 mole ethylene oxide adduct of dibenzylated ortho-cyclohexylphenol.

(II-b) Styrenation of ortho-cyclohexylphenol and addition reaction with ethylene oxide are carried out using the same apparatus and method as in (I-a).

That is, after carrying out a styrenation reaction using 88 g of ortho-cyclohexylphenol, 1 g of anhydrous aluminum chloride, and 104 z of styrene, the mixture was transferred to an autoclave reactor, 1.91 g of potassium was added, and 440 g of ethylene oxide was added. , 20 mol ethylene oxide adduct of distyrylated ortho-cyclohexylphenol (hydroxyl value 48.6
, average molecular weight 1155).

This compound 578S' (0.5 mol) and sulfamino acid 63.12 (0.65 mol) were reacted for 6 hours using the same apparatus and method as in (II-a).

The mixture was then cooled, and 10,100 O of methanol was added to dissolve the mixture. Excess sulfamino acid was filtered off, and methanol was distilled off to obtain 612 g of a brown solid substance.

This material was the sulfate ammonium salt of a 20 mole ethylene oxide adduct of distyrylated ortho-cyclohexylphenol.

Examples Synthesis examples (■-a) to (I-e) and (, I[-a) (I
The following test was conducted using the dyeing aid synthesized in I-b).

The blending ratio of the dyeing aid and the test results are shown in Table 3 in comparison with the case where a conventional dyeing aid was used.

1 Dispersibility test dye 2゜% O1W, f Dyeing aid 0.7 g/l Bath ratio 1:30 pH 5.0 (adjusted with acetic acid) Liquid volume 300rrLl Using the above dye bath, Nippon Senzo Kikai Co., Ltd. Polyester Tropical was dyed with Colorpet 12 manufactured by Co., Ltd.

The following four types of dyes were used: Niresoline Red FB *I B: Holon Rubin S-2GFL *2 C: Dianic Navy Blue 5R-FS *3 D: Holon Navy S-2GL *2 Polyester Tropical was 10g. Wrap the piece of cloth around the dyeing machine holder, tie both ends with rubber bands, and heat at 90℃ x 5
The sample was dyed under three conditions: 110°C x 5 minutes and 130°C x 5 minutes, and then rapidly cooled.

After dyeing, the condition of spots of dye aggregates deposited on the dyed object in contact with the holder was observed and classified into the following five stages.

Grade 5: No dye aggregates observed.

Grade 4: Slightly acceptable.

〃 Grade 3: Acceptable.

〃 Grade 2: Most recognized.

〃 Grade 1: Remarkably recognized.

〃 2 Dye migration test Dye E Dia=Tsukusuizo-2,o%o0w,f.

G-FS*3 Tire Xlet 1.0% 7 TB-8E*3 Dianic Tsubu” 0.5% 7゜BG-F
S*3 Bath ratio: 1:10 pH: 5,0 (adjusted with acetic acid) Liquid volume: Using a dye bath of 3ooTLl and a dye bath using the following dye F instead of dye E, Hl-Di manufactured by Todoroki Sangyo Co., Ltd. 30 grams of polyester tropical was dyed at 140°C for 20 minutes using a dyeing machine.

Dye F Miketon Polyester I 1.5% o, w, f.

Erotic YL*4 Resolin Brilliantre 1.5% o6w, f.

Rad BS*1 Dia=Tsuku 7P" 1.5% 7RN-E*3 5 grams of the obtained dyed fabric were placed in the following treatment bath along with 5 grams of polyester tropical white fabric and treated at 140°C for 20 minutes.

Dyeing aid 0.7g/l Dyeing ratio l:30 pH5.0 (adjusted with acetic acid) Liquid volume 300ml After the treatment, the amount of dye transfer dust to the white cloth was visually determined.

The evaluation results are divided into 5 grades and shown in Table 3, with 5th grade indicating extremely noticeable dye migration and 1st grade indicating hardly any observed dye transfer.

(Note) The manufacturers of the dyes used in the examples are as follows.

*1 Bayer Japan Co., Ltd. *2 Sandoz Co., Ltd. *3 Mitsubishi Chemical Industries, Ltd. *4 Mitsui Toatsu Chemical Co., Ltd. Based on the results in Table 1, blank tests using conventional dyeing aids and without dyeing aids It can be seen that the methods of the present invention (Examples 1 to 9) have significantly improved performance in both dispersibility and dye transfer properties as compared to Comparative Examples 1 to 4.

Claims (1)

[Claims] 1. When dyeing polyester fibers at high temperatures using disperse dyes, compounds (R1) represented by general formulas CI) and (II) m A O(CH2CH2O)pH-(I
) [However, A represents a phenyl group, an ortho- or para-diphenyl group, or an alkylphenyl group having an alkyl group having 12 or less carbon atoms, and R1 is a substituent of A and represents a benzyl group or a styryl group. , m is an integer from 1 to 5, p
represents a numerical value of 8 to 100] and (R2)nBO(CH2CH20)9803M
...(II) [However, B represents a cyclohexylphenyl group, R2 is a substituent of B and represents a benzyl group or a styryl group, n is 1 or 2, and q represents a numerical value of 8 to 80. , M is an alkali metal, ammonia, or an ethanolamine such as monoethanolamine, jetanolamine, triethanolamine, etc.] A method for dyeing polyester fibers, characterized in that the dye bath includes the following. 2. The polyester fiber dyeing method according to claim 1, wherein the weight ratio of the compounds [I] and (II) contained in the dye bath is 10-90:90-10. 3 The total amount of the above compounds CI) and [■] in the dye bath is 0.2~
2. The polyester fiber dyeing method according to claim 1 or 2, characterized in that the polyester fiber dyeing method is added at a ratio of Of/l.