JP2540598B2 - Reactive dye and dyeing method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a reactive dye and a method for dyeing a cellulose fiber using the reactive dye.

2. Description of the Related Art In dyeing cellulosic fibers, reactive dyes are superior in sharpness and various fastnesses to other dyes and are currently used in large quantities. For example, dichlorotriazinyl,
Monochlorotriazinyl, fluorochloropyrimidinyl,
A substance that releases an acid binding agent by the action of an acid binding agent or heat using a reactive dye having a reactive group such as dichloroquinoxazinyl, methylsulfonylpyrimidinyl, vinylsulfonyl, and sulfatoethylsulfonyl (eg sodium carbonate , Potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, potassium pyrophosphate, sodium pyrophosphate, sodium bicarbonate, sodium trichloroacetate), alone or in combination of two or more. The pH value of the dye bath is 10
Adjusted as described above, reactive dyeing of cellulosic fibers is performed at a temperature of 100 ° C. or lower in the presence of a neutral electrolyte such as sodium chloride or sodium sulfate. On the other hand, mixed fiber materials containing cellulosic fibers (blends) are often used as fiber materials for clothing, and among them, blended products of polyester fibers and cotton (hereinafter abbreviated as T / C blends) are excellent in applicability and economical. It has come to be used in large quantities because it is. The T / C mixture is usually dyed by the following method using a reactive dye and a disperse dye.

(I) One-bath two-stage method First, the polyester fiber side is dyed with a disperse dye by a carrier dyeing method or a warm dyeing method, and then the cotton side is dyed with a reactive dye in the same bath.

 Alternatively, stain in the reverse order.

(II) Two-bath method First, the polyester fiber side is dyed by the method as described above, and then the cotton side is dyed in another bath. Or stain in the reverse order.

(III) One-bath one-step method A dyeing bath containing a reactive dye and a disperse dye is prepared, and polyester fiber and cellulose fiber are dyed simultaneously at a dyeing temperature of 120 to 140 ° C. in a neutral to acidic pH range.

Problems to be Solved by the Invention Dyeing of T / C mixture by the one-bath one-step method is considered as a rational dyeing method from the viewpoint of energy saving. For sufficient dyeing, the reactive dye is sufficiently stable even in the temperature range of 120 to 140 ° C, which is the condition for the disperse dye to dye the polyester fiber, and in the acidic or neutral pH range. It is necessary to be present and to have dyeability to cellulose fibers.

At present, it is not possible to find a reddish yellow reactive dye sufficient to satisfy the above-mentioned conditions on the market.

Means for Solving the Problems The inventors of the present invention have achieved the present invention as a result of intensive studies to solve the above-mentioned problems. That is, in the present invention, a {In the formula (1), R ₁ and R ₂ are independently -H, -SO ₃ H or -NO ₂ , R ₃ is -H or -SO ₃ H, and R ₄ and R ₅ are independently-.
_{H, -OCH 3, -OC 2 H} 5, -CH 3, -NHCOCH 3, -NHCONH 2 or -NH
₂ , R ₆ is —COOH or —CONH ₂ , and R ₇ and R ′ ₇ are —H, —CH ₃
Or -C ₂ H _5, Y is -CH = CH -, - NH- or -CONH-
And D is (L represents 1 or 2), (M represents 1, 2 or 3) or formula (2) (In the formula (2), R ₄ and R ₅ have the same meanings as described above, and n is 2
Or 3 respectively represents a compound represented by) and a reactive dye represented by: and a method for dyeing a cellulosic fiber using the same.

The reactive dye represented by the formula (1) only requires the presence of an agent having a buffering action for maintaining the dye bath at pH 5 to 9,
It has a very convenient property for the one-bath one-step dyeing method in that it can uniformly dye a T / C mixture at a temperature of 95 to 150 ° C in the presence of a disperse dye. Of course, when applied not only to T / C blends but also to fibrous materials consisting only of cellulosic fibers, it exhibits excellent effects in terms of color yield, level dyeability, reproducibility, and pilled-up property. Further, the reactive dye represented by the formula (1) has excellent solubility in water.

The reactive dye represented by the formula (1) of the present invention produces a remarkable effect when dyed with a cellulosic fiber such as cotton, rayon and hemp and a T / C mixture, but with other polyester fibers. Rayon; dyeing of cotton or rayon with triacetate fiber, polyacrylonitrile fiber, polyamide fiber, wool or silk, etc. is excellent when used in combination with disperse dye, acid-containing dye, cationic dye, etc. The effect is obtained.

 The present invention will be described in detail.

The reactive dye represented by the formula (1) of the present invention is synthesized, for example, by the following method.

1 mol of cyanuric chloride and formula (3), formula (4) or formula (5) (In the formula _{(3), R 4, R} 5, R '7 (4) and (5),
l, m and n have the same meanings as above) 1 mol of the compound represented by
At room temperature for 1 to 5 hours to obtain a compound of formula (6).

(In the formula _{(6), R '7,} D are as defined above) to Ajizo the 1 mol of the compound represented by a scheme (7) (In the formula (7), R ₁ , R ₂ and R ₃ have the same meanings as described above.) 1 mol of the compound of the formula (8) and, for example, water, pH 2 to 8, (In the formula (8), R ₄ , R ₅ , and R ₇ have the same meanings as described above.) The compound of the formula (9) is obtained by reacting at a temperature of 0 to 30 ° C. for 5 to 20 hours.

(In the formula (9), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₇ have the same meanings as described above.) Then, the compound of the formula (6) and the compound of the formula (9) are, for example, A compound of formula (10) is obtained by reacting at a water temperature of 40 to 70 ° C. and a pH of 3 to 8 for 2 to 7 hours. (In the formula (10), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ′ ₇ and D have the same meanings as described above.) Then, 1 mol of the compound of the formula (10) Or 1 to 3 mol of the compound represented by
The compound of formula (1) is obtained by reacting at the temperature of 5 to 10 hours.

The compound represented by the formula (1) is usually separated as an alkali metal salt of Na, K, Li or the like by a salting out method or the like. Equation (1)
Specific examples of the compounds represented by the formula (3), the formula (4), the formula (7), the formula (8) and the formula (5) used for producing the compound of .

A compound of formula (3); A compound of formula (4); A compound of formula (7); A compound of formula (8); A compound of formula (5); The compound represented by the formula (5) is represented by the following formula The compound represented by (In the above formula, R ₄ , R ₅ and R ′ ₇ have the same meanings as described above).

Next, the dyeing method of the cellulose fiber using the reactive dye represented by the formula (1) of the present invention will be explained.

The reactive dye of the formula (1) of the present invention and the disperse dye are used in combination.
The one-step one-step dyeing of T / C mixture is performed, for example, as follows.

The compound of the formula (1) of the present invention, a disperse dye, an inorganic salt (for example, Na ₂ SO ₄ , NaCl, etc.) if necessary, a buffering agent for maintaining a pH value of 5 to 9, a surfactant (dispersing agent). , Penetrant) Add a reduction inhibitor to make a dye bath, and soak the T / C mixture in it for 95 to 150
After dyeing for 20 to 90 minutes at ℃, soaping is performed by the usual method.

Blended products other than T / C blends, such as blended products of cellulose fibers and polyamide fibers (nylon, wool, silk, etc.), polyacrylic fibers, acid-modified polyester fibers, etc.
The reactive dye (1) of the present invention is used in combination with an acid dye, a basic dye or the like, and dyeing is performed in the same manner as described above.

When dyeing a fiber material consisting only of cellulosic fibers by the dip dyeing method, the compound of the present invention, an inorganic salt (for example,
After making a dyeing bath from sodium sulfate, sodium chloride, etc.), immersing the fiber and dyeing at 50 to 90 ° C for 10 to 60 minutes,
If necessary, add an acid binder or buffer and add 20
Stain for ~ 60 minutes. In this case, a method of dyeing by adding an acid binder to the dye bath from the beginning, first treating with a dye bath containing only the compound of the present invention, and then treating with a dye bath containing an acid binder and an inorganic salt. Then, a method of dyeing can also be adopted.

It is also possible to prepare a dye bath from the compound of the present invention, an inorganic salt or the like, and add a buffering agent if necessary, and dye at a temperature of 90 to 150 ° C for 10 to 60 minutes. In addition to the dip dyeing method, the padding dyeing method and the textile printing method can also be used for dyeing according to a usual method. The compounds of the present invention can be used alone or in admixture of two or more.

In the above, examples of the acid binder include sodium carbonate, potassium carbonate, potassium hydroxide, sodium metasilicate, sodium phosphate tribasic, potassium phosphate tribasic, potassium pyrophosphate, sodium pyrophosphate, sodium bicarbonate, sodium trichloroacetate, and the like. , As a buffer,
Acetic acid-sodium acetate, monopotassium phosphate-sodium phosphate, monosodium phosphate-sodium phosphate,
Maleic acid-borax or the like is used.

The reactive dye of the present invention has excellent solubility, and has a remarkable effect in terms of color yield leveling and reproducibility built-up, which is excellent with respect to cellulosic fibers among cellulosic fibers or cellulosic fiber-containing fiber materials. Show.

EXAMPLES Next, the present invention will be described according to examples. In the examples, parts are parts by weight and sulfonic acid groups in the formulas are in the free acid form.

Example 1. 50 parts of water was added to 4.0 parts and dissolved at 75-80 ° C. Ice was added to this to cool the temperature to 30 ° C., 4.1 parts of hydrochloric acid was added, and then 0.75 parts of sodium nitrite dissolved in 10 parts of water was added over 30 minutes, and the temperature was 30 ° C. after a minute diazotized, to erase the excess NO _'2 with sulfamic acid.

Apart 1.5 parts is dissolved in 50 parts of water, 3.2 parts of baking soda is added, and the diazo solution is added to the solution having a temperature of 15 ° C by adding ice over 30 minutes while maintaining a temperature of 15 to 20 ° C, A reaction solution containing the compound of formula (12) was obtained.

Next, 1.9 parts of cyanuric chloride was added to a liquid consisting of 20 parts of water, 20 parts of ice, and 0.5 parts of a 10% Liponox NA (made by Lion Oil and Fats, dispersant) aqueous solution, and stirred and dispersed for 30 minutes to obtain a dispersion liquid.
The other A solution prepared by dissolving 3.0 parts in 40 parts of water with 10% soda ash at pH 6.5 was added to the above dispersion over 30 minutes, and immediately neutralized to pH 7.3 with 10% soda ash. Subsequently, the reaction was carried out for 1 hour while maintaining the pH at 7.0 to 7.5 and the temperature at 5 to 10 ° C to obtain a reaction solution containing the following compound.

The reaction liquid containing the compound of the formula (12) was added to this reaction liquid, and the temperature was raised to 55 ° C. After the temperature was raised, the pH was neutralized to 4.5 with 10% hydrochloric acid. Further, the reaction was carried out for 5 hours while maintaining pH 4.5 ± 0.2 and temperature 55 ° C. ± 2 ° C. to obtain a reaction solution containing the following compound.

next 2.5 parts of powder was added to the above reaction solution and the temperature was raised to 95 ° C. The temperature was raised to pH 6.9 with 10% sodium hydroxide solution. Temperature 9
The mixture was kept at 5 ° C ± 2 ° C and reacted for 10 hours. Next, at the same temperature, 20% sodium chloride based on the weight of the reaction solution was added for salting out, and the precipitated crystals were separated and dried to obtain the compound of (11) above.
I got 20 copies.

(Maximum absorption wavelength: 423 nm) (in 20% pyridine aqueous solution ... the same applies hereinafter) Example 2. 30 parts of water was added to 3.0 parts, and the solution was neutralized to pH 7.0 with 10% soda ash and dissolved. Add ice to this and cool to a temperature of 10 ° C, and add hydrochloric acid 3.
0 part was gradually added dropwise to precipitate crystals.

Next, a solution prepared by dissolving 0.75 part of sodium nitrite in 5 parts of water was gradually added dropwise, and after diazotization at a temperature of 15 ° C. ± 2 ° C. for 1 hour, excess No ₂ ⁻ was eliminated with sulfamic acid. Apart 1.5 parts was dissolved in 50 parts of water, 3.0 parts of sodium bicarbonate was added, and ice was added to bring the temperature to 5 ° C. Add the diazo solution to this at 5-10 ℃
The reaction solution containing the compound of formula (14) was obtained by adding 40 minutes while maintaining the temperature of.

On the other hand, 1.9 parts of cyanuric chloride was added to a liquid consisting of 20 parts of water, 20 parts of ice, and 0.5 part of a 10% Liponox NA (made by Lion Oil and Fat, dispersant) aqueous solution, and stirred for 30 minutes to obtain a dispersion liquid. The compound of formula (14) was added to this dispersion in 20 minutes, and immediately neutralized to pH 7.3 with 10% soda ash. pH 7.0-7.5, temperature 5-10 ° C
The reaction was carried out for 2 hours while maintaining the above to obtain a reaction solution containing the following compound.

Formula (12) prepared in the same manner as in Example 1 was applied to this reaction solution.
The same procedure as in Example 1 was performed to obtain a reaction solution containing the following compound.

2.5 parts of powder was added to the above reaction solution and the same operation as in Example 1 was carried out to obtain 25 parts of the compound (13).

(Maximum absorption wavelength: 420 nm) Examples 3 to 26. Compounds shown in Table 1 were synthesized by the method according to Examples 1 and 2, and cotton knitted fabric was dyed by the same method as in Example 27. A red-yellow dyed product was obtained.

Example 27. 2 parts of the target compound obtained in Example 6, 80 parts of anhydrous sodium sulfate,
A dyebath was prepared consisting of 2 parts Na ₂ HPO ₄ · 12H ₂ O and 1 part KH ₂ PO ₄ , 0.5 part sodium metanitrobenzenesulfonate and 917 parts water. The pH value of the dyebath at this time was 7. Into this dyeing bath, 50 parts of scoured and unbleached cotton knitted knitted fabric was put, and the temperature was raised to 130 ° C. in 30 minutes while stirring, and dyeing was performed at the same temperature for 30 minutes. The pH value after dyeing was 7 as at the start of dyeing.
Then, it is washed with water and an aqueous solution containing 2 parts of anionic surfactant 10
Soap was used for 10 minutes at 100 ° C. with 00 parts, followed by washing with water and drying to obtain a reddish yellow dyed product.

 The color yield of this dyed product was excellent.

Example 28. 1 part of the target compound of the formula (11) obtained in Example 1 and the following composition Kayacelon.Yellow E-3GL 0.025 part Kayacelon Yellow E-13RL 0.1 part (all manufactured by Nippon Kayaku, disperse dye) disperse dye mixture, 80 parts of sodium sulfate, including formalin condensate 2 parts of naphthalenesulfonic _{acid, Na 2 HPO 4 · 12H 2} O and KH ₂ PO ₄
Polyester fiber / cotton (50/50) blended cloth (T / C blend) in a total of 1000 parts of dye bath adjusted to pH 7.0 with a buffer solution consisting of
Charge 50 parts and raise the temperature to 130 ℃ in 20 minutes.
Stained for minutes. After washing with water, soaping was performed for 20 minutes at 100 ° C. in 1000 parts of water containing 2 parts of anionic surfactant and 2 parts of soda ash. Then, it was washed with water and dried to obtain a dyed product having a good color yield, which was dyed uniformly in reddish yellow on both the polyester fiber side and the cotton side.

Example 29. 2 parts of the target compound obtained in Example 6, 80 parts of anhydrous sodium sulfate,
A dyebath was prepared consisting of 2 parts of Na ₂ HPO ₄ · 12H ₂ O and 0.5 part of KH ₂ PO ₄ , 1 part of sodium metanitrobenzenesulfonate and 917 parts of water. The pH value of the dyebath at this time was 7. Into this dyeing bath, 50 parts of scoured and unbleached mercerized cotton knitted fabric was added, the temperature was raised to 95 ° C. in 30 minutes while stirring, and dyeing was performed at the same temperature for 60 minutes. The pH value after dyeing was similar to that before dyeing was started.

Then, it is washed with water and an aqueous solution containing 2 parts of an anionic surfactant.
Using 1000 parts, soaping was carried out at 100 ° C. for 10 minutes, followed by washing with water and drying to obtain a reddish yellow dyed product.

 The color yield of this dyed product was excellent.

Effect of the Invention Color yield, level dyeing property, build-up, dyeing reproducibility, good solubility, and T / C mixture used in combination with a disperse dye in an ordinary dyeing method using a reactive dye of a cellulosic fiber. A reactive dye for reddish-yellow dyeing which gives excellent dyeing results even in the one-bath one-step dyeing method was obtained.

Claims (2)

(57) [Claims] 1. Formula (1) in the form of the free acid {In the formula (1), R ₁ and R ₂ are independently -H, -SO ₃ H or -NO ₂ , R ₃ is -H or -SO ₃ H, and R ₄ and R ₅ are independently-.
_{H, -OCH 3, -OC 2 H} 5, -CH 3, -NHCOCH 3, -NHCONH 2 or -NH
₂ , R ₆ is —COOH or —CONH ₂ , and R ₇ and R ′ ₇ are —H, —CH.
₃ or -C ₂ H _5, Y is -CH = CH -, - NH- or -CONH-
And D is (L represents 1 or 2), (M represents 1, 2 or 3) or formula (2) (In the formula (2), R ₄ and R ₅ have the same meanings as described above, and n represents 2 or 3, respectively) and the reactive dye represented by 2. A method for dyeing cellulosic fibers, which comprises using the reactive dye according to claim 1.