JP2648480B2 - Dyeing assistant for cationic dyeable fiber - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a dyeing aid for cationic dyeable fibers. More specifically, the present invention relates to a dyeing assistant comprising a novel cationic surfactant which gives an excellent slow dyeing effect when dyeing a cationic dyeable fiber with a basic dye or a cationic dye.

[Conventional technology and its problems]

Examples of the cationic dyeable fiber include an acrylic fiber and a cationic dyeable polyester fiber.

Acrylic fibers are a general term for copolymer fibers of acrylonitrile and other components, and there are a great variety of types, but most of them have an acidic group at the molecular chain terminal or in the molecular chain.

Therefore, non-ionic dyes such as cationic dyes such as basic dyes and cationic dyes or disperse dyes are used for dyeing acrylic synthetic fibers.
In order to obtain a fast dyed product, a cationic dye is frequently used.

Cationic dyeable polyester fiber (hereinafter abbreviated as CDP) is a fiber obtained by introducing an acidic group such as a sulfonic acid group into polyester fiber, and can be dyed with a cationic dye.

As shown in the following formula (1), the cationic dye ion (D ⁺ ) is converted into an anionic ion (X ⁻ ) in the acrylic fiber or CDP by ion exchange as shown in the following formula (1). It is said to form a salt-forming bond at a ratio of 1: 1.

However, in actual dyeing, acrylic fiber or CD
Since the affinity of the cationic dye for P is very strong, rapid dyeing occurs. Therefore, it is difficult to obtain a uniform dyed product by an easy dyeing method.

Therefore, when dyeing acrylic fibers or CDP with a cationic dye, a cationic dyeing agent for leveling is used as a dyeing assistant.

The cationic dye is structurally similar to the cationic dye, can be regarded as a colorless cationic dye, and is considered to have the same adsorption behavior to acrylic fibers and CDP as the cationic dye. Therefore, when acrylic fiber or CDP is dyed with a cationic dye in a system to which a cationic dyeing agent has been added, dyeing progresses while the dye and dyeing agent compete for dyeing seats in the fiber, resulting in dyeing. As a result, a uniform dyed product is obtained.

As the cationic release agent, those which are generally commercially available include those mainly containing quaternary ammonium salts such as lauryl dimethyl benzyl ammonium salt, lauryl trimethyl ammonium salt, coco dimethyl benzyl ammonium salt and coco trimethyl ammonium salt. Almost. However, these quaternary ammonium salts have a problem that a large amount of the quaternary ammonium salt needs to be added because the slow dyeing effect is not sufficient.

[Means for solving the problem]

Therefore, the present inventors have conducted intensive studies to solve the above-described problems of poor dyeing of cationic dyeable fibers such as acrylic fibers and CDP, and as a result, a specific compound is excellent as a cationic dyeing agent, The present inventors have found that a uniform dyed product can be obtained by a slow dyeing effect by using a small amount, and the present invention has been completed.

That is, the present invention provides a dyeing aid for cationic dyeable fibers comprising a compound represented by the following general formula (2).

(Wherein, R ₁ and R ₂ each independently represent an alkyl or alkenyl group having 6 to 22 carbon atoms, and at least one of R ₃ , R ₄ and R ₅ is a methyl, ethyl or benzyl group, and the others are carbon atoms. Represents a saturated or unsaturated alkyl group of 1 to 4, and may be the same or different, and Y represents a halogen ion or an alkyl sulfate ion.) A quaternary ammonium salt represented by the above general formula (2) The starting material is a branched alcohol obtained by the so-called Guerbet reaction or a branched fatty acid obtained by oxidizing the branched alcohol. The Guerbet reaction is a reaction in which a primary alcohol is heated using a catalyst to obtain a branched alcohol having a side chain at the β-position as shown in the following formula.

(In the formula, R and R ′ represent an alkyl or alkenyl group.) A tertiary amine is synthesized using such a branched alcohol or a branched fatty acid as a starting material, and this tertiary amine is converted into benzyl chloride, benzyl bromide, methyl chloride,
The quaternary ammonium salt of the present invention can be obtained by a general method of quaternizing with methyl bromide, dimethyl sulfate, diethyl sulfate, or the like.

Methods for synthesizing tertiary amines include aminolysis of higher alcohols, alkylation of dimethylamine with alkyl chloride, reductive methylation of primary amines with formaldehyde, aminolysis of fatty acids or esters, methylation of amines with methanol, dimethylamine There are catalytic reduction reactions of nitriles in the presence, and the methods for synthesizing primary amines include catalytic reduction of nitriles obtained by dehydration of fatty acid and ammonia, hydrogenation ammonolysis of fatty acids or esters, ammonolysis of higher alcohols, etc. However, any method may be used.

The optimal amount of the dyeing aid of the present invention to be added to the dyeing bath is
It should be calculated taking into account the saturation factor of the fiber to be dyed and the dye used, but
0.05 to 5% by weight is suitable, preferably 0.1 to 2% by weight.

The dye added to the dye bath is determined by the desired color density. Generally, 0.01 to 5 based on the weight of the material to be dyed
% By weight.

The dyeing bath may contain an organic or inorganic acid for pH adjustment and a buffering agent such as an alkali metal acetate for stabilizing to a predetermined pH value. In addition, the dye bath may contain an electrolyte or other surfactant.

In the present invention, examples of the cationic dyeable fibers include acrylic fibers and CDP. Acrylic fibers are commercially available acrylonitrile polymers or copolymers. In the case of acrylonitrile copolymer, the acrylonitrile component is at least 80% by weight of the copolymer.
It is desirable to be present.

Further, CDP is a polyester fiber exemplified by an acid having an acidic group such as sulfonated isophthalic acid and a copolymer such as terephthalic acid and ethylene glycol.

That is, the dyeing assistant for cationic dyeable fibers of the present invention can be applied to all kinds of acrylic fibers and CDPs, that is, all kinds of acrylic fibers and CDPs having various dyeing properties.

Fiber material to be dyed is not only acrylic synthetic fiber, but also polyamide synthetic fiber, polyester synthetic fiber,
Including, but not limited to, woven, knitted, non-woven, piled materials, etc., which are blended with other materials such as cellulosic synthetic fibers, natural fibers such as cotton and wool, and twisted is not.

(Operation)

When dyeing cationic dyeable fibers such as acrylic fibers and CDP with a basic dye or a cationic dye, the use of the quaternary ammonium salt of the present invention as a dyeing agent makes it possible to use a smaller amount of dye than conventional dyeing agents. A superior dyeing effect can be imparted by using, and a uniform dyed product can be obtained.

As described above, although the mechanism by which a quaternary ammonium salt using a Guerbet-type alcohol as a raw material exhibits an excellent dyeing effect with a small amount of use is not necessarily clear, the quaternary ammonium salt of the present invention is located at the β-position of N. It is thought that since the molecule is a bulky molecule having an alkyl group, it also affects the adsorption behavior of the dye on the blank dyeing seat, and excellent dyeing is achieved. In addition, the quaternary ammonium salt of the present invention has a higher affinity for acrylic fibers and CDP than conventional quaternary ammonium salts, and therefore, competitively adsorbs to acrylic fibers and CDP with basic dyes or cationic dyes. Is considered to be high and excellent dyeing is achieved.

In addition, the shape of the textile product which is the object of the present invention is performed in any state, such as loose state, sliver, semi-finished state such as top, thread, woven fabric, knit, mat, etc. Conditions are also appropriately selected according to each state. In addition, in actual dyeing, in addition to adding the above quaternary ammonium salt as a dyeing aid, a dyeing aid conventionally used such as a dyeing acid such as acetic acid and a neutral salt such as sodium acetate is used. Can be added.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Synthesis Examples and Examples, but the present invention is not limited to only these examples.

Comparative Synthesis Example 1 0.4 mole (1 mole) of dimethyl-type tertiary amine synthesized from a mixed gas of isostearyl alcohol (for example, Emazole 875 manufactured by Emery Corporation, USA) and dimethylamine / hydrogen
18.8 g) and water (169.4 g) were charged into a 500 ml four-necked flask, heated with stirring and maintained at 60 ° C., and 0.48 mol (60.8 g) of benzyl chloride was added dropwise over 60 minutes. After dripping 6
Aged at 0 ° C. for 4 hours. After completion of the reaction, unreacted benzyl chloride was removed by steam distillation, and then the concentration was adjusted with water.

 The reaction rate was 98.9%, and the effective component was 47.6%.

Comparative Synthesis Example 2 Synthetic alcohol having a branching ratio of 94% and having 12 or 13 carbon atoms as a main component (for example, tertiary amine of dimethyl type synthesized from a mixed gas of dovanol 231 manufactured by Mitsubishi Yuka Co., Ltd. and dimethylamine / hydrogen) 0.4 mol (92.0 g) and water (145.2 g)
Charge into a 0 ml four-necked flask and heat with stirring.
Benzyl chloride 0.48 mol (60.8 g)
In minutes. After completion of the dropwise addition, the mixture was aged at 60 ° C for 4 hours. After completion of the reaction, unreacted benzyl chloride was removed by steam distillation, and then the concentration was adjusted with water.

 The reaction rate was 98.5%, and the effective component was 47.9%.

Comparative Synthesis Example 3 Nonanol (manufactured by Nissan Chemical Industries, Ltd.) and dimethylamine
0.4 mol (113.2 g) of monomethyl type tertiary amine synthesized from a mixed gas of hydrogen and water (122.9 g) are charged into a 500 ml four-necked flask, and heated to 60 ° C. while stirring,
0.48 mol (60.8 g) of benzyl chloride was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was aged at 60 ° C. for 4 hours. After the reaction,
Unreacted benzyl chloride was removed by steam distillation, and then the concentration was adjusted with water.

 The reaction rate was 99.3%, and the effective component was 66.3%.

Synthesis Example 1 of the Present Invention 0.4 mole (130 g) of dimethyl-type tertiary amine synthesized from a mixed gas of alcohol and dimethylamine / hydrogen obtained from the Guerbet reaction of decyl alcohol and water (135.5 g)
Was charged into a 500 ml four-necked flask, heated with stirring and maintained at 60 ° C., and 0.48 mol (60.8 g) of benzyl chloride was added.
Was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was aged at 60 ° C. for 16 hours. After completion of the reaction, unreacted benzyl chloride was removed by steam distillation, and then the concentration was adjusted with water.

 The reaction rate was 98.5%, and the effective component was 71.0%.

Synthesis Example 2 of the Present Invention 0.4 mol (174.8 g) of dimethyl-type tertiary amine synthesized from a mixed gas of alcohol and dimethylamine / hydrogen obtained from the Guerbet reaction of myristyl alcohol and water (16
9.1 g) was charged into a 500 ml four-necked flask, heated with stirring and maintained at 60 ° C., and treated with 0.48 mol (6%) of benzyl chloride.
0.8 g) was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was aged at 60 ° C. for 22 hours. After completion of the reaction, unreacted benzyl chloride was removed by steam distillation, and then the concentration was adjusted with water.

 The reaction rate was 96.0%, and the effective component was 66.3%.

Example 1 A commercially available acrylonitrile jersey having a saturation value of 2.1 was dyed with a cationic dye under the following conditions, and the slow-dyeing effect of the cationic slow-dyeing agent was examined.

<Dyeing conditions>Dye; Kayakryl Red 3BL, 1% owf (cationic dye manufactured by Nippon Kayaku Co., Ltd.) Acetic acid; 1% owf sodium acetate; 0.5% owf Slow dye; see Table 1 Bath ratio; 1:20 Dyeing prescription: Heat up to 100 ° C at 1 ° C / min and treat at 100 ° C for 20 minutes <Evaluation> Fabric after dyeing and process of dyeing (70, 80, 90, 100 ° C x 10)
The color was measured using a color computer SM3 manufactured by Suga Test Instruments Co., Ltd., and the a value was determined to obtain a measure of the dyeing concentration.

<Results> The results of the staining are shown in Table 1.

The a value when the dye was completely exhausted was 44.1. In the case where the slow dye was not used, the dyeing speed was extremely fast, and the dyeing was completed during the temperature rise. In this dyed cloth, remarkable dyeing unevenness was observed. In the case of the commercially available release agent Lebenol RC (a release agent manufactured by Kao Corporation) and the release agent of the comparative synthesis example, the same release effect was observed at the amount of 0.75% owf used. This is the level of general dyeing agents.

On the other hand, the slow dyeing agent of the synthesis example of the present invention showed a good slow dyeing effect even when a very small amount was added. In other words, the use amount of the present invention is about one third of that of the commercial product in the case of the slow dye of Synthesis Example 1, and three to one fifth of the commercial product is sufficient in the case of the slow dye of Synthesis Example 2.

Example 2 A commercially available cationic dyeable polyester fiber having a saturation value of 2.1 was dyed with a cationic dye under the following conditions, and a dyeing curve was obtained.

<Dyeing conditions> Test cloth; commercially available cationic dyeable polyester fiber 0.5 g x 20 sheets Dye; Kayakryl Red 3BL, 1% owf (cationic dye manufactured by Nippon Kayaku Co., Ltd.) Acetic acid; 1% owf Sodium acetate; 0.5 % Owf dyeing agent; see Table 2 Bath ratio; 1: 100 Dyeing prescription; Heat up to 100 ° C at 1 ° C / min and treat at 100 ° C for 20 minutes Test method: (1) Adjust dyeing bath by 1 (2) Put dyeing bath and fiber in separate flask Raise the temperature from room temperature.

(3) Cloth 1 at 60, 70, 80, 90, 100 ° C x 10 minutes, 100 ° C x 20 minutes
Take out the sheet and 50 cc of dye liquor.

(4) Measure the absorbance of the extracted liquid to determine the dyeing rate.

A: Absorbance of dye solution before dyeing B: Absorbance of extracted solution <Results> Fig. 1 shows a dyeing curve obtained when a commercially available product and the slow dye of Comparative Synthesis Example were used. FIG. 2 shows a dyeing curve in the case of using the slow dye, and FIG. 3 shows a dyeing curve in the case of using the slow dye of Synthesis Example 2 of the present invention.

As is clear from FIGS. 1 to 3, in the case of the commercial release agent Novenol RC (a release agent manufactured by Kao Corporation) and the release agent of Comparative Synthesis Example 2, the equivalent release amount was 0.75% owf. A dyeing effect was observed. In addition, these dyeing residual liquids were transparent. Further, the slow dyeing agents of Comparative Synthesis Examples 1 and 3 exhibited a slower dyeing effect than commercial products, but coloring was observed in the residual dye solution.

On the other hand, even when either of Synthesis Examples 1 and 2 of the present invention was used as a slow-dyeing agent, a sufficient slow-dyeing effect was recognized with a use amount of a fraction of the commercially available product. The residual dyeing solution was colored in Comparative Synthesis Examples 1 and 3 and No. 5 in which the degree of dyeing did not reach 100%, but was transparent in other dyeing examples.

Example 3 An acrylic fiber was dyed with a cationic dye under the following conditions, and a dyeing curve was obtained.

<Dyeing conditions> Test cloth; Casimiron F (saturation value = 2.2) 0.5g x 20 sheets Dye; Kayakryl Blue GRL, 1% owf (Nippon Kayaku Co., Ltd. cationic dye) Acetic acid; 1% owf Sodium acetate ; 0.5% owf slow dye; see Table 3 Bath ratio; 1: 100 Dyeing prescription; 98 ° C. × 60 minutes Test method; (1) Adjust dye bath 1 (2) Put dye bath in separate flask, heat to 98 ° C., then put fibers.

(3) Take out one cloth and 50 cc of the liquor every 10 minutes.

(4) Measure the absorbance of the extracted liquid to determine the dyeing rate.

A: Absorbance of dye solution before staining B; Absorbance of extracted solution <Results> The staining curve is shown in FIG.

As is apparent from FIG. 4, the amount of the commercially available product is less than one-half that of the commercial product in the case of the dyeing agent of Synthesis Example 1 of the present invention and less than one-third that of the commercial product in the infectious agent of Synthesis Example 2 of the present invention. It shows the same slow dyeing effect as.

[Brief description of the drawings]

1 to 3 are dyeing curves obtained in Example 2,
FIG. 1 shows the results when using a commercially available product and the slow dyeing agent of Comparative Synthesis Example.
FIG. 2 shows a dyeing curve in the case of using the slow dye of Synthesis Example 1 of the present invention, and FIG. 3 shows a dyeing curve in the case of using the slow dye of Synthesis Example 3 of the present invention. FIG. 4 is a dyeing curve obtained in Example 3.

Claims (1)

(57) [Claims] (1) General formula (Wherein, R ₁ and R ₂ each independently represent an alkyl or alkenyl group having 6 to 22 carbon atoms, and at least one of R ₃ , R ₄ and R ₅ is a methyl, ethyl or benzyl group, and the others are carbon atoms. Y represents a halogen ion or an alkyl sulfate ion, and represents a saturated or unsaturated alkyl group of 1 to 4; and Y represents a halogen ion or an alkyl sulfate ion.