JPS5922827B2 - Dyeing method for polyester synthetic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polyester synthetic fibers and blended or interwoven products of polyester synthetic fibers and other fibers such as cotton, wool, rayon, hemp, etc., using disperse dyes alone or in combination with other dyes. The present invention relates to a method for obtaining level dyed products using a novel dyeing aid that imparts dispersibility and level dyeing properties when dyeing in a bath.

Polyester synthetic fiber products (including blended products of polyester synthetic fibers with cellulose fibers and other fibers, and interwoven products) are usually dyed by a carrier dyeing method using a carrier or a high temperature dyeing method at 120 to 140°C. 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 and higher alcohol sulfate salt polyoxyethylene alkylphenol ether sulfate are not satisfactory in terms of dispersibility, level dyeing, and foaming properties. However, it has the disadvantage that dyeing problems are likely to occur due to tarring due to poor dispersion of the disperse dye, uneven dyeing due to insufficient level dyeing, and fabric lifting and twisting due to foaming.

Furthermore, even with polyoxyethylene styrenated phenyl ether sulfate, which is a known dyeing aid with excellent dispersibility and level dyeing properties, sufficient effects cannot be obtained in high-temperature, short-time dyeing, especially in terms of foaming properties. However, there is a great need for a dyeing aid that can solve these dyeing problems.

In view of the above, the present inventors have arrived at the present invention as a result of intensive research aimed at solving the problems of dyeing polyester synthetic fibers.

That is, the present invention provides an excellent dyeing aid that solves the problems of poor dispersion and poor leveling of the disperse dye, as well as problems caused by foaming, in the high-temperature, short-time dyeing of polyester synthetic fibers with disperse dyes. A dyeing method is provided.

The dyeing aid used in the present invention will be described below, and its effects will be discussed.

The dyeing aid used in the present invention is one or a mixture of two or more sulfate salts of urethane compounds represented by the general formula CI, 1.

This compound [I] is a urethane compound obtained by reacting a compound represented by the following general formula CII, l with an isocyanate compound (a type of surfactant represented by the general formula [IV] described below), or A urethane compound [■] obtained by reacting a compound represented by (ID and general formula Cl) with an isocyanate compound is sulfated using a sulfating agent such as chlorosulfonic acid, sulfamic acid, fuming sulfuric acid, or sulfuric acid, and then Alkali metal hydrate, N- having 5 or less carbon atoms
It is obtained by salt exchange or neutralization with a chlorinated substance such as an alkyl group.

Here, the compound AZ(C2H40)n(C3H60)mH"""...' represented by the general formula CID
[ID is a compound represented by the general formula [group] AZH-...
・・・・・・・・・・・・・・・・CI, 1 is ethylene oxide or an adduct of ethylene oxide and propylene oxide.

In formulas CI3 to [IV), A represents a benzene nucleus; a benzene nucleus substituted with one or more alkyl groups, aryl groups, cycloalkyl groups, or aralkyl groups; or a long-chain alkyl group; Z is 0; Any atom or atomic group of N or NH, n and m are each 0 or 1 to 50
(2) represents a group consisting of one to several alkylene groups and/or arylene groups, and M represents Na, NH4, or an alkylamine or alkanolamine having 5 or less carbon atoms, respectively.

Specific compounds represented by the general formula CI) include phenylphenol, cumylphenol, naphthol, nonylphenol, cyclohexylphenol, butylphenol, benzylphenol, styrenated phenol,
These include phenols such as styrenated cyclohexylphenol, and long-chain alkyl amines.

For the compound represented by the general formula CID, the number of moles of ethylene oxide or ethylene oxide and propylene oxide to be added is O per 1 mole of the compound represented by the general formula Cl) (however, both cannot be 0) 150 moles, preferably 0 to 100 moles, and more preferably 5 to 40 moles.

Further, in the case of block addition of ethylene oxide and propylene oxide, it is necessary that the average number of added moles of ethylene oxide, which is a hydrophilic group, is always greater than the average number of added moles of propylene oxide.

Next, the diisocyanate compounds used in the present invention include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, cyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate,
Examples include, but are not limited to, halogenated phenyl diisocyanate, phenyl diisocyanate, and mixtures of low polymers thereof.

The urethane compounds (general formula [■]) obtained as intermediate products during the above reactions have existing chemical substance official gazette numbers (7)-1343 and (9)-
It is a known substance as shown in No. 1810 and the like.

However, no method of sulfating these urethane compounds or a dyeing method using this sulfate compound as a dyeing aid has been found.

Furthermore, these existing chemical substances official gazette number (7)-134
3. The urethane compound [■] as shown in (9)-1810 etc. is an ethylene oxide adduct of an alkyl amine or alkyl alcohol represented by the general formula [II] or an ethylene oxide adduct of a carbon polycyclic phenol. Nonionic compounds such as mono-, di-, or higher -NCO, which are usually used in the production of urethane resins, etc.
Although it is synthesized by a normal urethane reaction with an incyanate compound having a group and used as a surfactant, it is unsatisfactory as a dyeing aid for polyester synthetic fibers.

In other words, these urethane compounds have low solubility when the average number of moles of ethylene oxide added is small, that is, when the HLB is low, as a result of the terminal 10H group of ethylene oxide, which is a hydrophilic group, being blocked by the incyanate group ζ. Therefore, a nonionic compound with extremely high HLB is used.

Therefore, in general, these 7-ionic compounds are used in large excess compared to the Durham equivalent number of the incyanate compound and used as a surfactant in the coexistence of the urethane compound and unreacted nonionic compound, or Currently, a method is adopted in which a hydrophilic group is added to a part of the -NCO group of a cyanate compound.

However, these nonionic urethane compounds or urethane compounds blocked with acidic sodium sulfite are not preferred as dyeing aids for polyester synthetic fibers because they have poor dispersibility and thermal stability.

Therefore, from the viewpoint of dispersibility, compounds having an aromatic nucleus are currently advantageous as dispersing and leveling agents for polyester synthetic fibers. ethylene oxide adduct of phenol,
That is, sulfated products of nonionic compounds such as polyoxyethylene styrenated phenol are generally used.

However, although these have excellent dispersibility and level dyeing properties, they have a large foaming property and are not suitable for the rabbit high-temperature and high-pressure dyeing method.

Therefore, a nonionic surfactant with low foaming properties of 30~
Although it is sometimes used in a 70% blend, it has drawbacks such as extremely low dispersibility and high cost, and cannot be called an ideal dyeing aid.

In contrast, in the present invention, a compound obtained by sulfating the urethane compound and then salt-exchanging or neutralizing it with a basic substance is used as an auxiliary agent for dispersion and level dyeing of polyester synthetic fibers.

However, the dyeing aid of the present invention is not intended to oxidize a nonionic urethane compound, which would leave an excessive amount of unreacted nonionic compound, as in the conventional products, but rather to The original purpose is to sulfate the remaining urethane product.

That is, in the dyeing aid of the present invention, the amount of the compound represented by the general formula CI) is as follows: -NCO group 1 of the incyanate compound
It is preferable that the ratio is such that the number of 10H groups in the compound is 025 to 2.

When the ratio of 10H groups to 1 -NCO group is 0.25 or less, a considerable amount of unreacted -NCO groups remain, and this remaining 1NCO group has a hydrophilic group represented by the general formula CHD. Because it reacts with compounds that have active hydrogen, solubility and
Level dyeing and dispersibility become poor.

On the other hand, when the ratio of -OH groups is 2 or more, large amounts of nonionic compounds remain, and the compounds obtained by sulfating these have excellent performance as dispersion and leveling agents, but foaming properties are required. It is unsuitable for staining methods.

As mentioned above, the compound according to the present invention first has the general formula [I
A urethane compound represented by VI that is not bathed or partially dispersed in water is sulfated using a conventional sulfonating agent or sulfating agent.

However, when a large excess of chlorsulfonic acid or fuming sulfuric acid is used as the sulfating agent, the aromatic ring of the compound having an aromatic group among the compounds represented by the general formula [■] is sulfated.

These purified products of sulfates are soluble in cold water, have excellent dispersibility and leveling properties, and have low foaming properties, but they require complicated purification equipment due to the use of excessive sulfating agents. I need.

On the other hand, sulfuric acid or sulfamino acid, which has been conventionally used in the synthesis of polyoxyethylene styrenated phenyl ether sulfate, etc., is used in the synthesis of many anionic surfactants because it selectively reacts with -OH groups.

In particular, sulfamino acids are NH3 (+ ion), 5O3 (
It is widely known that it is effective as a sulfating agent because it consists of amphoteric ions (-ions) and does not require a neutralization step.

By the way, as a reaction between sulfamino acid and an organic compound, a reaction with an aldehyde compound (ILS, P.

231.958, U, S, P, 2,355,600
), reaction with aliphatic alcohols (Get, P, 558
, 299), reaction with phenols (Ber, 45
1394), reaction with styrenes (Italy37
793).

Reaction with amines (Ber, 1896), reaction with amides (Ber, 9 1929), reaction of hydrogen of amine group of S/L/7 amino acid (F, P).

638, 175, Get, P, 159,046), etc., but there are no reports on the reaction between urethane compounds and sulfamic acid.

The present inventors have discovered that the urethane compound represented by the general formula [■] can be arbitrarily sulfated with sulfamino acid, and that the urethane compound represented by the general formula [■] can be optionally sulfated with sulfamino acid. The present invention was completed by discovering that a salt-exchanged or neutralized compound has excellent performance as a dispersion and leveling agent.

The mechanism of this sulfation reaction is not clear.

If we were to speculate, it would be inferred that sulfamic acid reacts with the urethane bond or urea bond portion of the urethane compound.

This means that the hydrogen in the above-mentioned bonding part reacts with the -NCO group and allophane 4 human HOO III I ++ -N-C-N-C-0-1 or Biillet HOO I It I ++ 1 -N-C It is an active hydrogen as shown by the formation of -N-C-N-, and -NC represented by the general formula [■]
Completely 10H with a ratio of 10H group to 1 O group
The urethane compound in which the active hydrogen of the group has been reacted is treated with sulfamic acid under an appropriate basic catalyst at a rate of 0.2 to 1 to 1 of the functional group such as the urethane bond or urea bond of the urethane compound.
It is inferred from the fact that when used in a ratio of 8% and reacted under appropriate conditions, an anionic surfactant with a sulfation rate of 5 to 99% is obtained.

The sulfation of the urethane compound represented by the general formula [■] with sulfamic acid has excellent solubility and low foaming properties, and a compound with a controlled sulfation rate can be obtained at will, so it is suitable for other sulfations. It is more preferable.

Table 1 shows that urethane compound (X) obtained from 2 moles of 12 moles of ethylene oxide adduct of styrenated cyclohexylphenol, which is part of the present invention, and 1 mole of diphenylmethane diisocyanate is reacted with an appropriate amount of sulfamino acid. The sulfation rate, solubility state, C, P of the obtained compound (■) and its salt-exchanged product (■) with caustic soda
, (cloud point), surface tension, and foaming property are shown in comparison with comparative examples.

The comparative example is an ammonium sulfate ester salt of a 12 mole ethylene oxide adduct of styrenated cyclohexylphenol.

Table 1 also shows the data for urethane compound [X] as a reference.

These anionic surfactants have a sulfation rate of 60-9
In the case of 9%, the ratio of sulfamino acid to 1 functional group such as the urethane bond and urea bond of the urethane compound is 1 or more, but unreacted sulfamic acid and sulfamic acid generated during salt exchange or neutralization are used. If the system contains salts of 10% or more, it is preferable to dissolve them in an appropriate solvent, filter the insoluble matter, and recover the solvent by vacuuming the black section.

However, in Table 1, the sulfation rate was calculated by the paratoluidine method and the cation standard solution titration method.

In addition, the foaming test was conducted using a 1 ton measuring cylinder (inner diameter 6.3
crrt) and 80℃ adjustment solution (surfactant 0.2r/
4. Add 0.3 f/l of acetic acid, and use an air pump with an A2 ball filter at the tip to continuously pump 4.
This was carried out by blowing air at a rate of 507111/min and measuring the height (cm) of the bubbles formed.

Next, the present invention will be explained in more detail by synthesis examples of dyeing aids used in the present invention and examples using these dyeing aids.

Synthesis Example 1 In a flask equipped with a reflux condenser, a thermometer, and a dropping funnel, add 1 ethylene oxide of tristyrenated phenol.
1,045 parts of the 5-mol adduct were added, and 84 parts of hexamethylene diisocyanate was gradually added dropwise at a temperature of 40 to 50°C.Then, the temperature was raised to 80 to 90°C, and the reaction was carried out at the same temperature for 3 hours to form a urethane compound. I got it.

To this urethane compound, 97 parts of sulfamic acid was added at once at 110 to 120°C, the temperature was raised to 160 to 170°C, and the reaction was allowed to proceed at the same temperature for 4 to 5 hours, producing a light brown viscous reaction product that is easily soluble in water. 1.230 parts of the product were obtained.

The estimated structural formula of this reaction product is as follows.

. Synthesis Example 2 Using the same equipment and method as in Synthesis Example 1, 10 moles of ethylene oxide adduct 72 of styrenated cyclohexylphenol was prepared.
0 part was placed in a flask, and 125 parts of diphenylmethane diisocyanate was gradually added dropwise at a temperature of 70 to 80°C.

Next, the temperature was raised to 80 to 90°C, and a reaction was carried out at the same temperature for 5 hours to obtain a urethane compound.

Next, 97 parts of sulfamino acids were added at once at 110 to 120°C, the temperature was raised to 160 to 170°C, and the reaction was allowed to proceed at the same temperature for 5 hours to obtain 950 parts of a brown viscous reaction product that was easily soluble in water. .

The estimated structural formula of this reaction product is as follows.

Synthesis Example 3 Using the same apparatus and method as in Synthesis Example 1, 666 parts of an 8 mol adduct of ethylene oxide of distyrenated phenol was reacted with 94 parts of xylylene diisocyanate, and then 97 parts of sulfamino acid was added at once to give 160 to 170 parts of sulfamino acid. By reacting at ℃ for 10 hours, 850 parts of a light brown viscous reaction product which is easily soluble in water was obtained.

The estimated structural formula of this reaction product is as follows.

Synthesis Example 4 Using the same apparatus and method as in Synthesis Example 1, 852.5 parts of an adduct of tristyrenated phenol with 30 moles of ethylene oxide and 327.5 parts of an adduct of 10 moles of ethylene oxide with 7-nylphenol were placed in a flask, and the mixture was heated to a temperature of 70 to 80. ℃ (trowel tolylene diisocyanate) 87° 5 parts were gradually added dropwise.

Next, the temperature was raised to 80-90°C, and the reaction was allowed to proceed at the same temperature for 5 hours. Then, 97 parts of sulfur amino acid was added at once to 170 parts.
By reacting at ~180°C for 5 hours, 1,360 parts of a light brown viscous reaction product which was easily soluble in water was obtained.

The estimated structural formula of this reaction product is as follows.

Synthesis Example 5 Using the same equipment and method as in Synthesis Example 1, 10 moles of ethylene oxide adduct of styrenated cyclohexylphenol was prepared.
080 parts and stearylamine ethylene oxide 10
By reacting 404.5 parts of the molar adduct with 175 parts of tolylene diisocyanate, and then reacting 194 parts of sulfamino acid in the same manner as in Synthesis Example 2, a light brown viscous reaction product that is easily soluble in water is produced. 1,630 parts of the product were obtained.

The estimated structural formula of this reaction product is as follows.

Synthesis Example 6 Using the same apparatus as in Synthesis Example 1, 5 moles of propylene oxide adduct of nonylphenol and 1 mol of ethylene oxide were prepared.
995 parts of the 0 mole adduct were placed in a flask, and 87.5 parts of tolylene diisocyanate was slowly added dropwise to react.
Next, add 97 parts of sulfamic acid at once to give a
The temperature was raised to 0°C, and the reaction was carried out at the same temperature for 5 hours to obtain 1,175 parts of a light brown viscous reaction product that was easily soluble in water.

The estimated structural formula of this reaction product is as follows.

Synthesis Example 7 Using the same equipment and method as in Synthesis Example 1, add 10 moles of ethylene oxide adduct 82 of tristyrenated phenol to a flask.
2 parts of xylylene diisocyanate were gradually added dropwise at a temperature of 60 to 70°C, and then the temperature was raised to 80 to 90°C and the reaction was carried out at the same temperature for 3 hours to obtain a urethane compound.

To this urethane compound, 97 parts of sulfamic acid is added at once at 110 to 120°C, the temperature is raised to 160 to 170°C, and the mixture is reacted at the same temperature for 4 to 5 hours.

Thereafter, 80 parts of 50% caustic soda was gradually added dropwise at 90 to 100 DEG C., and the mixture was reacted at the same temperature for 10 hours to obtain 1,092 parts of a pale yellow viscous reaction product that is easily soluble in water.

The estimated structural formula of this reaction product is as follows.

Synthesis Example 8 Using the same equipment and method as in Synthesis Example 1, 1,045 mols of ethylene oxide adduct of tristyrenated phenol was prepared.
and 87.5 parts of tolylene diisocyanate.

Next, 194 parts of sulfamino acid was added at once at 110-120°C and reacted at 160-170°C for 10 hours.

Further, 298 parts of triethanolamine was gradually added at 80 to 90°C, and the mixture was reacted at the same temperature for 5 hours to obtain 1,606 parts of a pale yellow viscous reaction product that is easily soluble in water.

The estimated structural formula of this reaction product is as follows.

Synthesis Example 9 110 parts of chlorosulfonic acid was placed in a flask equipped with a reflux condenser, a thermometer and a dropping funnel, and 167 parts of a 15 mole adduct of monostyrenated phenol with ethylene oxide and 17. The urethane compound obtained from 5 parts is carefully added dropwise.

The temperature was gradually raised to 100-110°C for 10 hours, and after cooling to room temperature, the mixture was poured into 10 times the amount of ice water.

Salt is added to the water until it becomes supersaturated, the precipitated fluoronated product and salts are separated, undried kijirole is added and filtered, and after the salts are removed, the black part is removed and kijirole is recovered.

This sulfonated product is neutralized with 59 parts of triethanolamine.

In this way, a light brown viscous reaction product 2 that is easily soluble in water is produced.
Got 50 copies.

The estimated structural formula of this reaction product is as follows.

Table 2 shows the foaming test results of the thus obtained dyeing aid of the present invention and conventionally used dyeing aids (Comparative Examples 1 and 2).

This is similar to the foaming test shown in Table 1, in which a 1 ton graduated cylinder (inner diameter 6.3 cm) was filled with an 80°C adjustment solution (dying aid 0.2 g/l, acetic acid O, 3 y/l). Using an air pump with a flat 2 ball filter attached to the tip, the air is continuously pumped from the bottom of the measuring cylinder to < 450 ml/mi.
Blow n air to raise the height of bubbles from the liquid surface to cm
) is filledffl.

Table 2 shows that the anionic compound of the present invention is compatible with commonly used dyeing aids, namely polyoxyethylene alkylphenol ether sulfate salt (Comparative Example 1) and polyoxyethylene styrenated phenol sulfate salt (Comparative Example 2). It is clear that the foaming property is lower than that of

Next, examples of the present invention will be shown.

Example 1 A dispersion test was conducted using a guiometer (manufactured by Suga Test Instruments) under the following test conditions.

The results are shown in Table 3, and it can be seen from this table that the product of the present invention has excellent dispersibility.

Sample: Polyester processed yarn filament Dye: ]) Sumikaron Rubine
S-2GL5 staff o, w, f.

2) Dianix Turq Blue (E-FS
5% o, w, f.

Test compound: o, 5'? /l (purity equivalent) 1) Product of the present invention (reaction product obtained in Synthesis Example 1) 2) Comparative product 1 3) Comparative product 2 Bath ratio: 1:30 Flow rate: 200 cr: / min Temperature. Time: 60℃→135℃/25 minutes, then 135℃
Example 2 Using the compound shown in Example 1, a dye migration test was conducted under the following conditions.

Sample: Polyester processed yarn Fabric dyeing machine: Karapet 12 (manufactured by Nippon Senzo Kikai) Dye Sashi 2 1) Resol ine BlueFBL 2%
o, w, f.

2) Re5ol ine Red FB 2% o
Different f.

3) Re5ol ine Yel lowRL 2%
o, w, f.

Acetic acid: 0.3 cr:/l.

Bath ratio: 1:30 Temperature/time: 135° C., 20 minutes White cloth of the same quality and amount as the above dyed cloth was placed in a treatment bath under the following conditions, and a dye transfer test was conducted.

The results are shown in Table-4.

Test compound: 0.5'? /lC pure content), same as Example 1.

Acetic acid: 0.3cr: / Bath ratio: 1:20 Temperature/time: 135°C, 20 minutes Example 3 Polyester processed yarn fabric was dyed under the following conditions using a test rapid circular dyeing machine (manufactured by Nichiita). did.

Staining condition q: Dian ix Blue BG-FS
3% o, w, f.

Acetic acid: 0.3 c / Test compound: 0.5 g/l (purity conversion) 1) Product of the present invention (synthesis example 2) 2) Comparative product 2 in Example 1 Bath ratio: 1:15 Reduction cleaning Bisnor DK (made of one side) 1'il/1
Hydrosulfide l f/to sodium hydroxide 1g/to bath ratio: 1:1
5 Temperature and time: 80°C, 20 minutes As a result, Comparative product 2 had remarkable foaming, the cloth slipped, and dyeing spots occurred, but 1 Inventive product, when the temperature was raised,
In all cases during tacking, evenly dyed products were obtained with little foaming.

Claims (1)

[Claims] 1 Represented by a general formula. A method for dyeing polyester synthetic fibers, which comprises using one or more sulfate salts of urethane compounds as a dyeing aid. In (Formula CI), A represents a benzene nucleus; a benzene nucleus substituted by one or more alkyl groups, aryl groups, cycloalkyl groups, or aralkyl groups; or a long-chain alkyl group, and Z represents 0. An atom or atomic group of N or NH, n and m are 0 or an integer from 1 to 50, ■ is a group consisting of one to several alkylene groups and/or arylene groups, and M is a group consisting of one to several alkylene groups and/or arylene groups. It represents Na 2 , K 2 , NH 4 , or an alkylamine or alkanolamine having 5 or less carbon atoms, respectively.