JP2003227077A - Low foaming type dyeing auxiliary - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low foaming type dyeing auxiliary that assists dispersion and level-dyeing properties in the dyeing process by means of a jet dyeing machine. <P>SOLUTION: The dyeing auxiliary comprises a mixture of an anionic surfactant including alkylene oxide adducts of which the oxide addition form and degree are restricted and one kind or two or more kinds of ester type nonionic surfactants in a certain proportion. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a dyeing aid used for high temperature dyeing of polyester fiber, polyamide fiber, polyvinyl chloride fiber and acetate fiber or a mixed spun woven product of these fibers and other fibers with a disperse dye. Regarding agents. More specifically, the present invention relates to a low-foaming dyeing aid capable of exhibiting excellent dispersion leveling property in jet dyeing and a dyeing method using the low-foaming dyeing aid.

[0002]

2. Description of the Related Art Conventionally, various ester type surfactants have been mainly used as a dyeing aid for synthetic fibers. However, these surfactants have a poor dye dispersibility and cause a terling phenomenon on an object to be dyed. There was a defect such as occurrence of. recent years,
In order to make up for the drawbacks of the ester type surfactant, attempts have been made to use anionic type surfactants such as polyoxyethylene alkyl ether sulfate and polyoxyethylene aryl ether sulfate together. However, when these anionic surfactants are used, the dyeing bath foams during dyeing, which causes dyeing failure. Further, in order to solve this, a method of simultaneously adding an antifoaming agent has been carried out, but there is a drawback that scum and stains occur due to the added antifoaming agent.

As a method for solving these drawbacks, JP-A-55-76176, JP-A-59-1784 and the like disclose certain limited ester type nonionic surfactants and polyoxyethylene aryl ether sulfate type. A method of using an anionic surfactant in combination has been proposed. However, these methods are still insufficient in terms of dispersion leveling property and low foaming property.

[0004]

DISCLOSURE OF THE INVENTION The present invention uses a low-foaming type dyeing aid capable of exhibiting excellent disperse leveling property in high temperature dyeing of synthetic fibers using the above disperse dye, and this dyeing aid. It is an object to provide a dyeing method.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have reached the completion of a low foaming type dyeing auxiliary agent capable of exhibiting excellent disperse dyeing property. . That is, the present invention provides an anionic surfactant (A) represented by the following general formula (I).

[Chemical 6] (In the formula, X is a naphthyl group, or

[Chemical 7] (However, R ₁ , R ₂ , and R ₃ are each a hydrogen atom, a phenyl group, a benzyl group, a styryl group, or a carbon number of 1 to 1.
2 alkyl group or (mono-di) benzylphenyl group or (mono-di) styrylphenyl group or cumyl group or (mono-di) benzylcumyl group or (mono-
Di) represents a styryl cumyl group. ) And y is 2-1
0 and z are integers of 7 to 20, and y ≦ z. M is K, N
a, NH ₄ or N-alkylammonium having 6 or less carbon atoms or N-alkanolammonium is shown. )
And an ester type nonionic surfactant (B) represented by the following general formula (II), (III) or (IV)

[Chemical 8]

[Chemical 9]

[Chemical 10] (However, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ ,
R ₁₀ , R ₁₁ and R ₁₂ are higher fatty acid residues having 6 to 18 carbon atoms, a, b, c, d, e, f, g and h are integers of 0 to 4, respectively, i, j, k and l. , M, n, o and p each represent an integer of 4 to 8. 1) or two or more kinds thereof) are blended in a weight ratio of A: B = (0.5 to 1): 2.

In the present invention, the X group of the anionic surfactant (A) represented by the general formula (I) is exemplified as follows.
Phenyl group, monobenzylated phenyl group, dibenzylated phenyl group, tert-butylphenyl group, octylphenyl group, nonylphenyl group, dinonylphenyl group, cumylphenyl group, bisphenyl group, monobenzylated nonylphenyl group, monostyrylated nonyl group Examples thereof include a phenyl group and a naphthyl group. Of these, a (mono to tri) benzylated phenyl group or a (mono to tri) styrylized phenyl group is preferable in terms of effects.

In the present invention, the general formulas (II) and (II
Examples of R _{4 to} R ₁₂ of the ester type nonionic surfactant (B) represented by I) or (IV) include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid. Fatty acid residues such as oleic acid and isostearic acid can be mentioned, and stearic acid and oleic acid residues are preferable.

In the anionic surfactant (A) of the general formula (I), y is 2-10, preferably 3-6, z.
Is an integer of 7 to 20, preferably 10 to 15, y ≦ z
Is. When y is larger than 10, the dye dispersibility decreases.
When z is less than 7, the water solubility is low and the dye dispersibility decreases. Further, if z is larger than 20 or y is smaller than 2, dyeing trouble due to foaming occurs.

The anionic surfactant (A) represented by the general formula (I) can be prepared by a known method, that is, by using an already exemplified arylphenol or alkylarylphenol with an alkali catalyst such as caustic soda or caustic potash.
It can be obtained by adding a predetermined amount of propylene oxide and ethylene oxide at 120 to 170 ° C. under pressure and then sulfating with chlorosulfonic acid, sulfuric anhydride, sulfamic acid or the like.

Further, the addition method of propylene oxide and ethylene oxide for obtaining the anionic surfactant (A) represented by the general formula (I) according to the present invention may be either block addition or random addition. However, the block addition in which ethylene oxide is added after the addition of propylene oxide gives preferable results particularly in terms of low foaming property.

General formula (II), (III) or (I
Ester-type nonionic surfactant (B) represented by V)
Can be easily obtained by a known method. That is, the compound (I
I) may be obtained by adding propylene oxide to polyethylene glycol and then esterifying it with a fatty acid and an acid or an alkali catalyst in the presence of compound (III).
Alternatively, with respect to (IV), propylene oxide and ethylene oxide may be added to glycerin and diglycerin, respectively, and then esterified in the same manner. The number of moles of propylene oxide added is 0 per hydroxyl group
It is up to 4 mol, and if it is more than 4 mol, the hydrophobicity is increased and the leveling effect of the dye is reduced. Further, the number of moles of ethylene oxide added is 4 to 8 moles per hydroxyl group, and if it is less than this, the hydrophobicity increases, the dispersibility of the dye is significantly destroyed, and if it is more than this, the foam suppressing property becomes poor. The dye transfer effect is also reduced and the dispersibility of the dye is not necessarily improved.

Further, the general formula (II) according to the present invention,
The addition method of propylene oxide and ethylene oxide for obtaining the ester type nonionic surfactant (B) represented by (III) or (IV) may be either block addition or random addition.

The compounding ratio of the anionic surfactant (A) and the ester nonionic surfactant (B) of the present invention is (A) :( B) = (0.5-1): The range of 2 is essential, and when the former (A) anionic surfactant is increased or decreased from this range relative to the latter (B) nonionic surfactant 2 parts, or when each is used alone. Causes deterioration of dispersibility, deterioration of dye transfer property or increase of foamability, and also gives unfavorable results as a dyeing aid which is the object of the present invention.

The gist of the present invention is to provide a dyeing auxiliary agent and a dyeing method using the same for obtaining an excellent article to be dyed, which is free from scum in dyeing synthetic fibers at a high temperature and is free from stains. The present invention provides a specific anionic surfactant (A) represented by the general formula (I) to which propylene oxide and ethylene oxide are added.
And the ester type nonionic surfactant (B) represented by the general formula (II), (III) or (IV) in a specific ratio, which is the basis of the present invention. Is.

No dyeing aid capable of exhibiting excellent dyeing performance has hitherto been proposed in such high-temperature dyeing, and it can be said that the invention is a very useful invention. Although the reason why the dyeing aid used in the present invention is excellent in dyeability has not been completely clarified, the balance of the alkylene glycol chains of the general formulas (A) and (B) according to the present invention and the specific hydrophobic group It is speculated that they work together and are effective.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The dyeing assistant of the present invention is a synthetic fiber,
It can be applied to natural fibers, and mixed woven mixed fibers thereof. Examples of synthetic fibers include polyester, nylon, acrylic, and triacetate fibers. Examples of the natural fiber include cotton, hemp, and wool. Examples of the mixed spun woven fiber include these mixed spun woven fibers.

When dyeing with the dyeing assistant of the present invention, the conventional dyeing machine can be used as it is, and the dye used in the dyeing bath, the acid for pH adjustment, the chelating agent and the like can be used as usual. it can.

The amount of the dyeing aid of the present invention used in the case of synthetic fiber is usually 0.2 to 1.0 g / L, and it is used after being diluted with a solvent or the like in order to lower the viscosity and improve the solubility. You may. The bath ratio of the treatment bath is usually 1: 5 to 1:30.
And exhibits an excellent effect in the low bath ratio region.

[0019]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 (1) A four-necked flask equipped with a thermometer, a dropping device, and a stirring device was charged with 94 g of phenol and 0.6 g of anhydrous aluminum chloride, heated to 95 ° C., and 250 g of benzyl chloride took about 4 hours. It was dripped slowly. After stirring at the same temperature for about 5 hours, the mixture was transferred to a pressure reactor, 2 g of potassium hydroxide was added, and 1
At 20 to 130 ° C., 232 g of propylene oxide was added for about 5 hours, and then at 160 to 170 ° C., 352 g of ethylene oxide was added for about 4 hours to obtain a reddish brown oily substance. This product was subjected to catalyst neutralization-dehydration-filtration, and 430 g was placed in another four-necked flask, and 59 g of chlorosulfonic acid was gradually added dropwise at 40 ° C or lower for about 3 hours, and then nitrogen gas was introduced for about 4 hours. Dehydrochlorination was performed, and the obtained sulfated product was neutralized with a caustic potash solution. (2) Add 240 g of polyethylene glycol having an average molecular weight of 240 and 0.6 g of caustic potash to the pressure reactor, and add 120
At ~ 130 ° C, 58 g of propylene oxide is added in about 1 hour. After that, this adduct was transferred to a four-necked flask equipped with a thermometer, a water receiver and a stirrer, charged with 1.4 g of caustic potash and 400 g of lauric acid, heated to 220 ° C., and esterified at the same temperature for about 8 hours. The chemical reaction was carried out. The obtained esterified product was neutralized with an acetic acid solution. 20 g of the compound obtained in (1) and 80 g of the compound obtained in (2) were placed in a beaker and stirred for about 30 minutes to obtain the mixture of Example 1.

Example 2 (1) To a pressure reactor, 144 g of α-naphthol and 1.1 g of caustic potash were added, and 116 g of propylene oxide was added at 120 to 130 ° C. for about 3 hours, followed by 1
About 3 g of 308 g of ethylene oxide at 60-170 ℃
Addition took place over time to give a reddish brown oil. This was subjected to catalyst neutralization-dehydration-filtration, and 284 was placed in another four-necked flask.
After taking g, 59 g of chlorosulfonic acid was gradually added dropwise at 40 ° C. or lower for about 3 hours, nitrogen gas was introduced and dehydrochlorination was performed for about 4 hours, and the obtained sulfated product was neutralized with a caustic potash solution. (2) Glycerin 92 g, caustic potash in a pressure reactor 2.
4 g was added and 174 g of propylene oxide was added at 120 to 130 ° C. in about 4 hours, followed by 160 to 1
After aging 924 g of ethylene oxide at 70 ° C. for about 4 hours, the mixture is aged. Then this product 560
g, 1.9 g of caustic potash, and 400 g of oleic acid were placed in a four-necked flask equipped with a thermometer, a moisture receiver, and a stirrer, the temperature was raised to 220 ° C., and the esterification reaction was carried out at the same temperature for about 8 hours. . The obtained esterified product was neutralized with an acetic acid solution. In a beaker, the compound 25 obtained in (1)
g, 75 g of the synthetic product obtained in (2) were taken and stirred for about 30 minutes to obtain the mixture of Example 2.

Example 3 (1) 220 g of nonylphenol and 1.2 g of anhydrous aluminum chloride were placed in a four-necked flask equipped with a thermometer, a dropping device, and a stirring device, and the temperature was raised to 95 ° C. to obtain benzyl chloride 2.
It took about 4 hours to gradually add 50 g. After continuing stirring at the same temperature for about 5 hours, the mixture was transferred to a pressure reactor and caustic potash 2.
3 g was added, and propylene oxide (348 g) was added at 120 to 130 ° C. in about 6 hours, followed by 160 to 1
At 70 ° C., 396 g of ethylene oxide was added for about 4 hours to give a reddish brown oily substance. This was subjected to catalyst neutralization-dehydration-filtration, and 570 g was placed in another four-necked flask.
Chlorosulfonic acid (59 g) was gradually added dropwise at 40 ° C. or lower for about 3 hours, then nitrogen gas was introduced and dehydrochlorination was performed for about 4 hours, and the obtained sulfated product was neutralized with a caustic potash solution. (2) Diglycerin (178 g) and caustic potash (4 g) were placed in a pressure reactor, and propylene oxide (464 g) was added at 120 to 130 ° C. for about 5 hours, followed by 160 to 1
After 1320 g of ethylene oxide is added at 70 ° C. for about 4 hours, the mixture is aged. Then this product 60
0 g, caustic potash (1.6 g) and caprylic acid (180 g) were placed in a four-necked flask equipped with a thermometer, a moisture receiver and a stirrer, the temperature was raised to 220 ° C., and the esterification reaction was carried out at the same temperature for about 7 hours. . The obtained esterified product was neutralized with an acetic acid solution. In a beaker, compound 30 obtained in (1)
g, 70 g of the compound obtained in (2) were taken and stirred for about 30 minutes to obtain the mixture of Example 3.

Examples 4 to 10 Reactions were carried out in the same manner as in Examples 1 to 3 to obtain the compounds of the present invention shown in Tables 2 and 3.

Comparative Example 1 (1) Phenol 94 g) 0.8 g of anhydrous aluminum chloride was placed in a four-necked flask equipped with a thermometer, a dropping device and a stirrer, and the temperature was raised to 95 ° C. and about 375 g of benzyl chloride was added to about 5 parts. It took time and was dripped gradually. After stirring at the same temperature for about 5 hours, the mixture was transferred to a pressure reactor, 2 g of potassium hydroxide was added, and 1
Approximately 4 528 g of ethylene oxide at 60-170 ° C
Addition took place over time to give a reddish brown oil. This was neutralized with catalyst-dehydrated-filtered and placed in another four-necked flask.
After taking g, 59 g of chlorosulfonic acid was gradually added dropwise at 40 ° C. or lower for about 3 hours, nitrogen gas was introduced and dehydrochlorination was performed for about 4 hours, and the obtained sulfated product was neutralized with a caustic potash solution. (2) Polyethylene glycol 2 having an average molecular weight of 240 is placed in a four-necked flask equipped with a thermometer, a water receiver and a stirrer.
40 g, 0.9 g of caustic potash, and 200 g of lauric acid were added, the temperature was raised to 220 ° C., and the esterification reaction was carried out at the same temperature for about 6 hours. The obtained esterified product was neutralized with an acetic acid solution. In a beaker, compound 30 obtained in (1)
g, 70 g of the synthetic product obtained in (2) were taken and stirred for about 30 minutes to obtain a mixture of Comparative Example 1.

Comparative Example 2 (1) Phenol 94 g, caustic potash 2.
6 g was added, and 968 g of ethylene oxide was added at 160 to 170 ° C. in about 6 hours, followed by 120 to 13
At 0 ° C., 232 g of propylene oxide was added for about 5 hours to give a reddish brown oily substance. Neutralize this
Dehydration-filter, take 647 g in another four-necked flask, 4
59 g of chlorosulfonic acid was gradually added dropwise at 0 ° C. or lower for about 3 hours, nitrogen gas was introduced, dehydrochlorination was performed for about 4 hours, and the obtained sulfated product was neutralized with a caustic potash solution. (2) Polyethylene glycol 2 having an average molecular weight of 240 is placed in a four-necked flask equipped with a thermometer, a water receiver and a stirrer.
40 g, caustic potash 1.3 g, and lauric acid 400 g were added, the temperature was raised to 220 ° C., and the esterification reaction was carried out at the same temperature for about 8 hours. The obtained esterified product was neutralized with an acetic acid solution. In a beaker, compound 20 obtained in (1)
g, 80 g of the synthetic product obtained in (2) were taken and stirred for about 30 minutes to obtain a mixture of Comparative Example 2.

Comparative Example 3 (1) 220 g of nonylphenol and 2 g of caustic potash were added to a pressure reactor, and 880 g of ethylene oxide was added at 160 to 170 ° C. for about 6 hours to obtain a reddish brown oily substance. This product was subjected to catalyst neutralization-dehydration-filtration, and 550 g was placed in another four-necked flask, and 59 g of chlorosulfonic acid was gradually added dropwise at 40 ° C or lower for about 3 hours, and then nitrogen gas was introduced for about 4 hours. Dehydrochlorination was performed, and the obtained sulfated product was neutralized with a caustic soda solution. (2) Polyethylene glycol 2 having an average molecular weight of 240 is placed in a four-necked flask equipped with a thermometer, a water receiver and a stirrer.
40 g, caustic potassium 1.6 g, and oleic acid 560 g were added, the temperature was raised to 220 ° C., and the esterification reaction was carried out at the same temperature for about 8 hours. The obtained esterified product was neutralized with an acetic acid solution. In a beaker, compound 70 obtained in (1)
g, 30 g of the synthetic product obtained in (2) were taken and stirred for about 30 minutes to obtain a mixture of Comparative Example 3.

The test methods used in the examples are shown below. (A) Foaming test <Test conditions> <Test method> 300 mL of the above test solution was put into a juicer mixer, and after stirring for 30 seconds, stirring was stopped,
Immediately after the stirring was stopped (0 seconds), the foam height (mm) was measured 10, 30, and 60 seconds later.

(B) Dispersibility test <Test conditions> <Test method> A commercially available polyester jersey is dyed by using Color PET 12 (manufactured by Nippon Dyeing Machinery) under the above conditions, by raising the temperature from 60 ° C to 115 ° C, and immediately when cooling reaches 115 ° C, cooling is started. After washing with water, the casing spot on the test cloth was visually judged. <Judgment Criteria> A ... Dye spots are hardly seen on the sample cloth. O: Only about 1/4 of the dye spots are seen on the sample cloth. Δ: Dye spots are seen up to about 1/2 on the sample cloth. D: 3/4 or more dye spots are seen on the sample cloth.

(C) Dye transfer test <Test conditions> <Test Method> Commercial polyester tropical dyed with the above dye and a white cloth of the same amount and the same quantity were treated in the same bath under the above conditions, and after washing with water, the dye transferability of the test cloth was examined. <Judgment method> Original dyed cloth (1) and dyed cloth (2) after the dye transfer test
The reflectance of is measured with a Hitachi color analyzer 607 model, and the K / S value is calculated from the Kubelka Munk equation,
The transfer rate was calculated. The one with a large number is considered to have good transferability. Migration rate (%) = 100 × (K / S of (2)) / ((1)
K / S)

The dyeing aids and comparative dyeing aids of the present invention shown in Table 1, Table 2, Table 3 and Table 4 were tested for foamability, dispersibility and transferability.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

From the test results, when the compounds of the general formulas (A) and (B) of the present invention were mixed and used in a certain ratio,
It was confirmed that both low foaming property and dispersion leveling property were excellent as compared with the comparative compound.

[0038]

EFFECTS OF THE INVENTION The use of the low-foaming dyeing aid for synthetic fibers of the present invention shows a dyeing performance equivalent to or better than that of conventional dyeing aids, and it should be noted that the dyeing aid is very low. Is foamy,
It is extremely effective in dyeing with a jet machine, which tends to cause dyeing problems due to foaming.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) D06P 3/54 D06P 3/54 A 3/79 3/79 Z

Claims (2)

[Claims] 1. An anionic surfactant (A) represented by the following general formula (I): (In the formula, X is a naphthyl group, or (However, R ₁ , R ₂ , and R ₃ are each a hydrogen atom, a phenyl group, a benzyl group, a styryl group, or a carbon number of 1 to 1.
2 alkyl group or (mono-di) benzylphenyl group or (mono-di) styrylphenyl group or cumyl group or (mono-di) benzylcumyl group or (mono-
Di) represents a styryl cumyl group. ), And y is 2 to 1
0 and z are integers of 7 to 20, and y ≦ z. M is K, N
a, NH ₄ or N-alkylammonium having 6 or less carbon atoms or N-alkanolammonium is shown. )
And an ester type nonionic surfactant (B) represented by the following general formula (II), (III) or (IV): [Chemical 4] [Chemical 5] (However, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ ,
R ₁₀ , R ₁₁ and R ₁₂ are higher fatty acid residues having 6 to 18 carbon atoms, a, b, c, d, e, f, g and h are integers of 0 to 4, respectively, i, j, k and l. , M, n, o and p each represent an integer of 4 to 8. 1) or 2 or more types thereof) in a weight ratio of A: B = (0.5 to 1): 2. 2. A high-temperature dyeing method for synthetic fibers, which comprises using the dyeing auxiliary agent according to claim 1.