JPH07119372B2 - Basic dye complex salt composition and dyeing method using the same - Google Patents

Description

FIELD OF THE INVENTION This invention relates to dye compositions and their uses. More specifically, it relates to a basic dye complex salt composition and a dyeing method using the same.

2. Description of the Related Art Generally, basic dyes are commercially available in the form of powder or liquid, but they have a drawback that they greatly contaminate the skin of workers, clothes, or dyeing equipment. A dye containing an anion group,
For example, in the same bath dyeing with an acid dye, a direct dye, a reactive dye, or a disperse dye containing an anionic dispersant,
There is a major drawback in the dyeing operation that these anions form trouble-soluble complex salts with the cations of the basic dyes and are liable to cause troubles such as turling.

In order to improve such drawbacks of basic dyes, the improvements as shown in the following patents have been made.

(1) JP-B 57-2747 (2) BP 1428010 (3) JP-B 57-4740 (4) JP-B 55-57079 (5) JP-B 55-107583 (6) JP-B 55-94053 (7) JP-B Sho 57-101154 That is, (1) and (2) are examples of using sodium salt of a formaldehyde condensate of naphthalenesulfonic acid or methylnaphthalenesulfonic acid as a complex salt-forming agent and a dispersant for the complex salt, and (3) is (1). ), And (2), the same purpose is the use of sodium lignin sulfonate. In these methods, the stain resistance to the human body and equipment is improved, and the compatibility with dyes of other species is good, but since the dispersant used has a strong binding force with the basic dye, it is possible to form fibers in the dyeing process. The migration (dyeing) of the basic dye is suppressed, a sufficient density cannot be obtained by dark dyeing such as dip dyeing or printing, and coloring of the waste water is large.

(4) is an example in which a complex salt of a basic dye and an anionic substance is made into fine particles with a nonionic activator. In this case, the dyeing property is good, but the product form is limited to liquid dyes. At the same time, there is a drawback that the long-term stability of the obtained complex salt composition is not sufficient.

(5) and (6) are examples using a sulfonic acid type anion activator having a polyoxyethylene group. in this case,
Since the complex salt of the basic dye is formed by a relatively weak bond, the complex salt obtained by this method has a property close to that of a normal basic dye which is not complexed, and therefore human body pollution and equipment pollution. The dye composition is limited to liquid dyes and is not suitable for the production of powdered dyes because the dispersant used is liquid in that it is insufficient in terms of improving compatibility with dyes of other species. There is a drawback that.

(7) is an example in which a basic dye complex salt is obtained from a polymer of a basic dye and styrenesulfonic acid, and the complex salt is further micronized to obtain a basic dye complex salt composition. When this complex salt composition is used for dyeing, it has a drawback that the dissolution rate in the dye bath is inferior and the complex salt floats as a scum at the interface especially during dyeing.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention A basic dye which has a sufficient dyeing property for fibers at the time of dyeing and a sufficient dissolution rate in a dyebath, and which does not form scum during dyebath preparation and dyeing in the dyebath. Complex salt compositions and dyeing methods are required.

Means for Solving the Problems The present inventors arrived at the present invention as a result of extensive studies to solve the above-mentioned problems. That is, the present invention relates to a basic dye complex salt obtained from a basic dye and a polystyrene sulfonate having a sulfonation ratio of 90 to 99% with respect to a benzene nucleus, the polystyrene sulfonate, and the following three kinds of additives, namely fatty acids: Esters with polyoxyalkylene glycerin ether and formula (I) ((In the formula (I), R represents a nonyl group or a styryl group,
X is a nonyl group, a styryl group or a hydrogen atom, M ⁺ is Na ⁺ , K
⁺ Or NH ₄ ⁺ , and n represents an integer of 1 to 10), and a basic dye complex salt composition comprising one or more additives selected from ethers represented by A method for dyeing a basic dye-dyable synthetic fiber, which is characterized by using the same.

The complex salt composition of the present invention and the dyeing method using the same will be described in detail.

The basic dye used in the present invention may be any type of basic dye as long as it has sufficient basicity to ionically bond with an anionic dispersant to form a complex salt, for example, Derived from di- and triallylmethane dyes, vinylon dyes, rhodamine dyes, acridine dyes, safranine dyes, oxazine dyes, quinoline dyes, thiazole dyes, azo dyes, azomethine dyes, polymethine or azopolymethine dyes, anthraquinone dyes, quinophthalone dyes, phthalocyanine dyes, etc. Basic dyes are used. These basic dyes are salted out after dye synthesis →
Aqueous wet cake obtained by filtration, and further dried →
It is used in the form of a dry cake that has undergone a crushing step, and these dyes may be used as a mixture of a plurality of dyes depending on the purpose.

Next, the polystyrene sulfonate having a sulfonation ratio of 90 to 99% with respect to the benzene nucleus used in the present invention is prepared by sulfonating polystyrene with a sulfonating agent such as chlorosulfonic acid in a halogen solvent such as dichloroethane or methylene chloride. Styrene or styrene sulfonic acid containing unsulfonated styrene is polymerized in water in the presence of a water-soluble polymerization initiator such as ammonium persulfate or hydrogen peroxide to form polystyrene sulfonic acid, which is sodium hydroxide, potassium hydroxide, Calcium hydroxide, magnesium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate magnesium carbonate, barium carbonate,
It can be obtained by neutralizing with an inorganic or organic base such as ammonia, monoethanolamine, diethanolamine, triethanolamine or ethylenediamine. The molecular weight of the polystyrene sulfonate is preferably 3000 to 100000
It is more preferably 5,000 to 50,000. The sulfonic acid group is 0 for each benzene nucleus (phenyl group of styrene skeleton).
9 to 0.99 (sulfonation rate 90 to 99%), more preferably 0.9
Those having a number of 5 to 0.98 (sulfonation rate of 90 to 99%) and a sulfonic acid group of less than 0.9 are inferior in fine particle forming ability to the basic dye complex salt and are not preferable for preparing the complex salt composition of the present invention.

Next, the ester of fatty acid and polyalkylene glycol glycerin ether used in the present invention has, for example, 8 carbon atoms.
It can be obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a mono- or diglycerin ester of a fatty acid of 24 to 24 (eg stearic acid, palmitic acid, oleic acid, lauric acid, etc.). The addition mole number of alkylene oxide is usually 1 to 300.
It is preferably 2 to 30 mol.

Further, the ethers represented by the above formula (I) used in the present invention are, for example, nonylphenol, dinonylphenol,
Ethylene oxide is added to phenols such as styrylphenol and distyrylphenol in an amount of 1 to 100 mol, more preferably 2 to 20 mol, followed by sulfonation with chlorosulfonic acid, and then neutralization with an alkali agent (eg caustic soda, caustic potash, ammonia, etc.). Obtained.

The basic dye complex salt composition of the present invention comprises, for example, a basic dye dissolved in water or formed into a mud form (original), the polystyrene sulfonate and a polyoxyalkylene glycerin ester of a fatty acid, polyoxyethylene (di) alkyl or ( Di)
One or more selected from phenyl ether sulfate salts are added and mixed and stirred to form a complex salt of a basic dye. Then, if necessary, polystyrene sulfonate is further added, and then the complex salt formed is further finely dispersed to obtain the complex salt. In the above, one or more additives selected from polyoxyalkylene glycerin ester of fatty acid, polyoxyethylene (di) alkyl and allyl phenyl ether sulfate salt form a complex salt of basic dye and polystyrene sulfonate. You can also add it after making it.

The amount of the polystyrene sulfonate to be used in the above (the total amount used for complex salt formation and fine particle formation of complex salt) varies depending on its molecular weight, sulfonation ratio, etc. ) To 3 to 10 times (weight ratio). The amount of the above-mentioned additive used is usually 0.01 to 20 times (weight ratio) the basic dye (base material).

The steps of complex salt formation and microparticulation are usually carried out at a water content of 50 to 90% to facilitate stirring, and are heated to 40 to 80 ° C to promote microparticulation (dispersion). A ball mill, a sand mill or the like can also be used.

As described above, the basic dye complex salt composition of the present invention is prepared as complex salt particles finely divided to about 1 μm or less.
This complex salt composition can be used as a liquid product as it is for dyeing, or can be dried by a method such as spray drying by a conventional method to obtain a dried product, which can then be dyed.

The basic dye complex salt composition of the present invention contains salt such as a builder, sodium sulfate, and dextrin, and also contains dodecylbenzenesulfonic acid, an alkylallylsulfonic acid as a lubricant, an antifoaming agent, an antifungal agent, or the like. May be.

Next, a method for dyeing a basic dye-dyeable synthetic fiber with the basic dye complex salt composition of the present invention will be described.

The fibers to which the complex salt composition of the present invention can be applied include polyacrylic fibers, fibers obtained from copolymers of acrylonitrile and other monomers, and bases such as polyester fibers (CDP fibers) provided with an acidic dyeing seat. Examples include synthetic dyeable dyeable fibers, and mixed fibers of these fibers and other fibers (for example, cotton, rayon, wool, nylon, polyester, etc.) and interwoven products. Dyeing of these fibers can be carried out in various manners, but usually in an acidic or weakly alkaline aqueous medium containing the basic dye complex salt composition of the present invention and optionally containing other group dyes and auxiliaries. Dip at a temperature of -130 ° C.

Further, it is also possible to prepare a printing paste and a bad bath by a conventional method and then perform dyeing by a printing method or a pad method. For dyeing, for example, continuous dyeing method using pad steam, printing method using screen / roll, and the like can be adopted in addition to batch dyeing such as rotary bag, jigger, wins over Mayer, and jet dyeing.

In addition, various auxiliaries such as emollients, leveling agents, penetrants and carriers may be present in the dyeing.

The basic dye complex salt composition of the present invention is one in which the cation of the basic dye is complexed with the sulfonic acid group of polystyrene sulfonate and then finely divided, and dissociates at normal temperature to disperse the basic dye cation. Since it does not generate phthalocyanine, it has very little human body contamination and stains on dyeing equipment, and has good compatibility with other anionic dyes and anionic dispersants, and does not cause problems such as turling. It is characterized in that it can be dyed and exhibits a high dyeing ratio to the basic dye-dyed synthetic fiber as described above. Further, it is characterized in that not only the dissolution rate is high at the time of preparation of the dyebath and the dispersion state is good, but also the dispersion stability at the time of dyeing is excellent and scum is hardly generated.

EXAMPLES Next, the present invention will be described in more detail by way of examples. In the examples, the parts or percentages are parts or percentages by weight unless otherwise specified.
Example 1 Basic yellow dye CI basic yellow 67 wet cake 670
To 100 parts (containing 225 parts of dry matter), add 100 parts of water and stir well to form a slurry. Sodium polystyrene sulfonate (molecular weight about 20,000, sulfonation rate 98%)
When 675 parts and 20 parts of an ethylene oxide 20 mol adduct of oleic acid monoglyceride are added to a solution prepared by dissolving 2800 parts of water with stirring, a dye complex salt is once formed, but it is sequentially dispersed into fine particles of 1 μ or less. Heat to 60-65 ° C for 3 hours for more rapid fine dispersion. After 86 parts of sodium sulfate (builder) was added, spray drying was performed to obtain 1000 parts of a yellow basic dye complex salt composition.

Example 2 Basic Yellow Dye CI Basic Yellow 40 Dry Cake 27
0 part of 20% sodium polystyrene sulfonate (molecular weight of about 20,000, sulfonation rate of 95%) 1200 parts of water, 740 parts of water was gradually added with stirring to form a basic dye complex salt, and then distyrenated. 30 parts of sodium sulfonate of 8 mol of ethylene oxide of phenol, followed by sodium polystyrene sulfonate (molecular weight about 20,000,
Sulfonation rate (95%) (60 parts) was added, and the mixture was stirred at 70 to 80 ° C under heating to obtain 2770 parts of a liquid composition of a yellow basic dye complex salt.

Example 3 (a) Basic red dye CI basic red 46 wet cake
Add 500 parts of water (containing 200 parts of dry matter) to 200 parts of water and stir well to form a slurry. This slurry was mixed with 20% sodium polystyrene sulfonate (molecular weight about 15,000 sulfonation rate 9
7%) 3850 parts and 30 parts of sodium sulfonate of 19 mol of ethylene oxide adduct of dinonylphenol were gradually added with stirring to a mixed solution. Then, the mixture was heated to 50 to 60 ° C. to complete fine dispersion, and then spray-dried to obtain 1000 parts of a red basic dye complex salt composition.

(B) A complex salt composition similar to the above was obtained by the following method.

To the slurry of CI Basic Red 46 obtained in the same manner as above, 3850 parts of 20% sodium polystyrene sulfonate was gradually added with stirring. It was observed that once the complex salt was formed and the sodium polystyrene sulfonate was added, the complex salt was finely dispersed. After addition of sodium polystyrenesulfonate, ethylene oxide 19 mol adduct of dinonylphenol sodium sulfonate
30 parts was added with stirring and heated to 50-60 ° C. to complete fine dispersion, and spray-dried.

Example 4 Instead of 30 parts of sodium sulfonate of 19 mol adduct of dinonylphenol with ethylene oxide in Example 3 (a), the same amount of ethylene oxide with nonylphenol 15 was used.
A basic dye complex salt composition 10 was prepared in the same manner as in Example 3 (a) except that a sulfonic acid ammonium salt of a molar adduct was added.
I got 00 copies.

Examples 5 to 9 By the method according to Examples 1 to 3, basic dye complex salt compositions having the compositions shown in the following table were prepared.

Example 10 A dyebath is prepared by thoroughly mixing 2 parts of the yellow basic dye composition prepared in Example 1 above in 5,000 parts of warm water containing 1 part of glacial acetic acid. Yarn of polyacrylonitrile fiber
100 parts were immersed at 60 ° C., heated to 98 to 100 ° C. for 30 minutes, dyed at the same temperature for 60 minutes, and washed with water.

During the dyeing, tar and scum were not generated at all, and the dyed object was dyed uniformly in yellow. 3% residual dye in the dye bath
Met.

Almost no body or equipment contamination of the worker was observed during the dyeing operation.

Example 11 4 parts of the red basic dye composition prepared in Example 3 was thoroughly mixed with 1 part of glacial acetic acid and 5,000 parts of warm water to prepare a dye bath.

Immerse 100 parts of polyacrylonitrile fiber cloth at 90 ℃ 1
The temperature was raised to 100 ° C. in 0 minutes, dyed at the same temperature for 30 minutes, and washed with water. Almost no scum was generated during dyeing, and a uniform red dyed product was obtained without causing tarring without using a slow-dyeing agent. The dyeing rate was also good, and the dye remaining rate in the dyebath was 5%.

Example 12 1 part of the blue basic dye composition prepared in Example 8 was used.
Dissolved in 10 parts water.

On the other hand, 2 parts of Kayanol Milling Blue BW (Nippon Kayaku acid dye) was dissolved in 20 parts of boiling water. Water these 6,000
Then, 1 part of glacial acetic acid was added to each part to prepare a dye bath. Dip 100 parts of acrylonitrile: wool (50:50) blended yarn at 60 ° C, gradually raise the temperature at a rate of 1 ° C per minute, dye at 100 ° C for 60 minutes, and then slowly cool to obtain a uniform blue dyed product. Obtained. The dyeing method was good, and the dye residual ratio was 3%.

Example 13 1 part of the yellow basic dye composition produced in Example 5 and 2 parts of Kayaron Polyester Yellow 5R-SE200 (Nippon Kayaku disperse dye CI Disperse Orange 55) were dispersed in slightly warm water to obtain 6,000 parts of water. Was diluted with to obtain a dye bath. Further glacial acetic acid
0.5 part and 14 parts of a commercial carrier agent (IP carrier) were added and 100 parts of an acrylic: polyester (50:50) blended yarn was soaked and heated from 60 ° C at a rate of 1 ° C per minute to 100 ° C. 6
Stained for 0 minutes. The dye could be dyed without causing tarring, and the staining of the basic dye complex salt on the dyeing machine was hardly recognized.

Example 14 3 parts of the blue dye composition prepared in Example 9 was mixed with 5,000 parts of water.
In addition to the parts, the pH was adjusted to 4 with sodium acetate and acetic acid. 100 parts of CDP fiber was immersed in this dye bath at 60 ° C., heated to 120 ° C. for 30 minutes, dyed at the same temperature for 60 minutes, washed with water and dried. During the dyeing, there was no tarring or equipment contamination, and the CDP fiber was dyed uniformly blue. The dyeing rate was high and the dye residual rate was 2%.

Example 15 2 parts of the basic dye composition prepared in Example 8 is added to 5,000
PH was adjusted to 4. 100 parts of CDP: polyester (50:50) blended yarn is immersed in this dye bath at 60 ℃ for 120 minutes in 30 minutes.
The temperature was raised to ℃, dyed at the same temperature for 60 minutes, washed with water and dried. The dyed material was dyed blue-green on the CDP side and was left unwhite on the polyester side.

Example 16 1 part of the blue basic dye composition prepared in Example 8 was dissolved in 10 parts of water. On the other hand, 2 parts of Kyanol Milling Blue BW was dissolved in 20 parts of boiling water. These were put in 6,000 parts of water and 15 parts of a commercially available carrier agent was added to adjust the pH to 4. 40
Dip 100 parts of CDP: wool blended yarn at ℃, heat up to 80 ℃ in 30 minutes, raise to 105 ℃ in 30 minutes, and keep at 60 ℃
Stained for minutes. Cooling → washing → washing followed by washing → drying gave a blue uniform dyed product. The basic dye composition according to the present invention has good compatibility with the acid dye for wool and the carrier, and there is almost no tarring or equipment contamination, and dyeing of CDP: wool blended yarn can be performed in one bath. did it.

Effects of the invention A basic dye has a great effect of preventing human body contamination, equipment contamination, etc. without impairing the original dyeing property to fibers, and also has a good dissolution rate and dispersibility during dyeing bath preparation, and scum during dyeing. It was confirmed that a basic dye complex salt composition which does not cause the occurrence of the above was obtained, and when this composition was used for dyeing, it gave excellent exhaustibility.

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Claims (2)

[Claims] 1. A basic dye complex salt obtained from a basic dye and a polystyrene sulfonate having a sulfonation rate of 90 to 99% with respect to a benzene nucleus, the polystyrene sulfonate and the following three additives, namely fatty acids. Of polyoxyalkylene glycerin ether with the formula (I) (In the formula (I), R represents a nonyl group or a styryl group, X
Is a nonyl group, a styryl group or a hydrogen atom, M ⁺ is Na ⁺ , K ⁺
Or NH ₄ ⁺ , and n represents an integer of 1 to 10), and a basic dye complex salt composition containing one or more additives selected from ethers represented by 2. A basic dye complex salt obtained from a basic dye and a polystyrene sulfonate having a sulfonation rate of 90 to 99% with respect to a benzene nucleus, the polystyrene sulfonate and the following three additives, namely fatty acids. With polyoxyalkylene glycerin ether of formula (I) (In the formula (I), R represents a nonyl group or a styryl group, X
Is a nonyl group, a styryl group or a hydrogen atom, M ⁺ is Na ⁺ , K ⁺
Or a basic dye complex salt composition containing one or more additives selected from ethers represented by NH ₄ ⁺ , and n is an integer of 1 to 10 respectively. A method for dyeing basic dye-dyeable synthetic fibers characterized by