JPH01153759A - Basic dye complex salt composition and dyeing by using said composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent dyeing property to fiber in dyeing, high dissolution rate in a dyeing bath and free from formation of scum in the dyeing bath in dyeing, by compounding a basic dye complex salt, a polystyrene sulfonic acid salt and a specific additive. CONSTITUTION:The objective composition can be produced by compounding (A) a basic dye complex salt composed of a basic dye and a polystyrene sulfonic acid salt having a sulfonation degree of the benzene nucleus of 90-99%, (B) the above polystyrene sulfonic acid salt and (C) an additive selected from esters of a fatty acid and a polyoxyalkylene glycerol ether, ethers of formula (R is nonyl or styryl; X is H, nonyl or styryl; M<+> is Na<+>, K<+> or NH4<+>; n is 1-10) or sodium polyacrylate. The compound of formula in the component C can be produced e.g. by adding ethylene oxide to nonylphenol, sulfonating with chlorosulfonic acid and neutralizing with an alkaline agent.

Description

[Detailed description of the invention] Industrial applications The present invention relates to dye compositions and their uses.

More specifically, the present invention relates to a basic dye complex salt composition and a dyeing method using the same.

BACKGROUND OF THE INVENTION Generally, basic dyes are commercially available in powder or liquid form, but they have the drawback of being highly contaminating to workers' skin, clothing, or dyeing equipment. In addition, when dyeing in the same bath with dyes containing anionic groups, such as acid dyes, direct dyes, reactive dyes, or disperse dyes containing anionic dispersants, these anions are difficult to interact with the cations of basic dyes. Since it forms a soluble complex salt, it has a major drawback in terms of dyeing operations in that it tends to cause troubles such as tarring.

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

(1) Special Publication No. 57-2747 (21B P 1428010 (3) Special Publication No. 57-4740 (4) Special Publication No. 55-57079 (5) Special Publication No. 55-107583 (6) Special Publication No. 55-94053 (7) Special Publication No. 57-74 -101154 That is, (1) and (2) are examples in which the sodium salt of the formaldehyde condensate of naphthalenesulfonic acid or methylnaphthalenesulfonic acid is used as a complex salt forming agent and a dispersing agent for the complex salt, and (3) is an example in which (1) , is an example of using sodium ligninsulfonate for the same purpose as in (2).These methods have improved contamination to the human body and equipment, and have good compatibility with other types of dyes, but they cannot be used. Because the dispersant has a strong bond with the basic dye, the transfer (dyeing) of the basic dye to the fiber during dyeing is suppressed, making it impossible to obtain sufficient density in deep dyeing for dip dyeing or printing. The drawback is that the dyeing wastewater is heavily colored.

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

(5) and (6) are examples in which a sulfonic acid type anionic activator having a polyoxyethylene group is used. in this case,
Since complex salts of basic dyes are formed by relatively weak bonds, the complex salts obtained by this method have properties similar to ordinary basic dyes that are not complexed, and therefore are less likely to cause human body contamination or equipment contamination. , it is insufficient in terms of improving compatibility with other types of dyes, and furthermore, because the dispersant used is liquid, the dye composition is limited to liquid type dyes and is not suitable for producing powder dyes. There is a drawback.

(7) is an example in which a basic dye complex salt is obtained from a polymer of a basic dye and styrene sulfonic acid, and this complex salt is further made into fine particles to obtain a basic dye complex salt composition. When this complex salt composition is used for dyeing, the dissolution rate in the dye bath is poor, and the complex salt composition has the disadvantage that it floats in the form of scum on the interface, especially during dyeing.

Problems to be Solved by the Invention A base that has sufficient dyeability to fibers during dyeing, has a sufficient dissolution rate in a dye bath, and does not form scum in the dye bath during dye bath preparation and dyeing. There is a need for a dye complex salt composition or dyeing method.

Means for Solving the Problems The present inventors conducted extensive studies to solve the above-mentioned problems, and as a result, they arrived at the present invention.

That is, the present invention provides a basic dye complex salt obtained from a basic dye and a polystyrene sulfonate having a sulfonation rate of 90 to 99 relative to the benzene nucleus, the polystyrene sulfonate, and the following three additives, namely (1) fatty acid; and polyoxyalkylene glycerin ether ■Formula (I) (In formula (I), R is a nonyl group or a styryl group,
is a nonyl group, a styryl group or a hydrogen atom, W is Na+,
A basic product characterized by containing one or more additives selected from ethers represented by K+ or NH4+, where n is an integer from 1 to 10, respectively), or (1) sodium polyacrylate. A dye complex salt composition and a method for dyeing synthetic fibers dyeable with basic dyes are provided.

The complex salt composition of the present invention and the dyeing method using the same will be explained 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 the anionic dispersant to form a complex salt (for example, , di- and triallylmethane dyes, vinylone dyes, rhodamine dyes, acridine dyes, safranin dyes, oxazine dyes, quinoline dyes, thiazole dyes, azo dyes, azomethine dyes, polymethine or azopolymethine dyes, anthraquinone dyes, quinophthalone dyes, phthalocyanine dyes, etc. These basic dyes are used in the form of an aqueous wet cake obtained by salting out and filtration after dye synthesis, or in the form of a dry cake obtained by further drying and pulverization. A plurality of dyes may be mixed and used depending on the purpose.

Next, the polystyrene sulfonate having a sulfonation rate of 90 to 99 with respect to the benzene nucleus used in the present invention can be obtained by, for example, converting polystyrene into a sulfonate using a sulfonating agent such as chlorosulfonic acid in a halogenated solvent such as dichloroethane or methylene chloride. or polymerize styrene sulfonic acid containing unsulfonated styrene 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 converted into polystyrene sulfonic acid, sodium hydroxide, potassium hydroxide, Inorganic or organic bases such as calcium hydroxide, magnesium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate magnesium carbonate, barium carbonate, ammonia, monoethanolamine, jetanolamine, triethanolamine, ethylenediamine, etc. Obtained by summing. The molecular weight of the polystyrene sulfonate is preferably 3000
-100,000, more preferably 5,000-50,000. In addition, the number of sulfonic acid groups is more preferably 0.95 to 0.99 (sulfonation rate 90 to 99) per benzene nucleus (phenyl group of styrene skeleton).
Those with a sulfonation rate of 90 to 99%) and a sulfone=9-acid group of less than 0.9 have poor particle formation ability for basic dye complex salts and are not preferred 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.
~24 fatty acids (e.g. stearic acid, palmitic acid,
It can be obtained by adding alkylene oxide such as ethylene oxide or propylene oxide to mono- or diglycerin ester of oleic acid, lauric acid, etc. The number of moles of alkylene oxide added is usually 1 to 3
00 is preferably 2 to 30 moles.

Furthermore, the ethers represented by the formula (I) used in the present invention include, for example, nonylphenol, dinonylphenol,
1 to 100 moles, preferably 2 to 20 moles of ethylene oxide are added to phenols such as styrylphenol and distyrylphenol, followed by sulfonation with chlorosulfonic acid, and then neutralized with an alkaline agent (e.g., caustic soda, caustic potash, ammonia, etc.). obtained by summing.

Furthermore, the sodium polyacrylate used in the present invention preferably has a relatively small molecular weight, usually 50 to 2,000.
More preferably, those having a molecular weight of 100 to 10,000 are used.

The basic dye complex salt composition of the present invention includes, for example, a basic dye (original substance) dissolved or made into a slurry in water, the polystyrene sulfonate and a polyoxyalkylene glycerin ester of a fatty acid, a polyoxyethylene °(di)alkyl or It can be obtained by further finely dispersing the complex salt formed after adding (di)phenyl ether sulfate salt polyacrytylene sulfonate.

In the above, one or more additives selected from polyoxyalkylene glycerol ester of fatty acid, polyoxyethylene (di)alkyl or allyl phenyl ether sulfate salt, or sodium polyacrylate are ``basic dye and polystyrene sulfonate.'' It can also be added after forming a complex salt.

The amount of polystyrene sulfonate to be used in the above (the total amount used for forming a complex salt and for making fine particles of the complex salt) varies depending on its molecular weight, sulfonation rate, etc., but the amount used is usually that of the basic dye. 0.01 for (technical substance)
~20 times the amount (weight ratio).

Note that the steps of forming complex salts and micronization are usually carried out at a moisture content of 50 to 90% to facilitate stirring, and heated to 40 to 80°C to promote micronization (dispersion). It is also possible to use a ball mill, sand mill, etc.

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 for dyeing as it is in liquid form, or it can be dried by a conventional method such as spray drying to obtain a dry product, which can then be used for dyeing.

The basic dye complex salt composition of the present invention may contain, in addition to common salt, sodium sulfate, dextrin, etc. as builders, dodecylbenzenesulfonic acid, alkylarylsulfonic acid, antifoaming agent, anti-mold agent, etc. as wetting agents. You may do so.

Next, a method for dyeing basic dye-dyeable synthetic fibers using the basic dye complex salt composition of the present invention will be explained.

Examples of 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 polyester fibers (CDP fibers) imparted with an acidic dyeing seat. Examples include synthetic fibers that can be dyed with synthetic dyes, and blended and interwoven products of these and other fibers (eg, cotton, -13=rayon, wool, nylon, polyester, etc.). Dyeing of these fibers can be carried out in various ways, but usually dyeing is carried out in an acidic to weakly alkaline aqueous medium containing the basic dye complex salt composition of the present invention and optionally containing dyes of other types and auxiliary agents. -13
Dyeing is carried out at a temperature of 0°C.

It is also possible to prepare a printing paste and a pad bath by a conventional method and carry out dyeing by a printing method or a pad method. For dyeing, for example, in addition to batch dyeing such as rotary bank, jigger, Winsovermeyer, and liquid jet dyeing, continuous dyeing using pad steam, and printing methods such as screen roll may be employed.

In addition, various auxiliary agents such as slowing dyes, leveling agents, penetrants, carriers, etc. may be present during dyeing.

In the basic dye complex salt composition of the present invention, the cation of the basic dye is complexed with the sulfonic acid group of polystyrene sulfonate and then finely divided, and it dissociates at normal temperature to form the basic dye cation. Since there is no generation of dyes, there is very little contamination of the human body or dyeing equipment, and it also has good compatibility with other anionic dyes or anionic dispersants, so it can be used in the same bath without causing problems such as tarring. It is characterized in that it can be dyed and exhibits a higher dyeing rate than the aforementioned synthetic fibers dyeable with basic dyes. In addition, it not only has a fast dissolution rate and a good dispersion state during dye bath preparation, but also has excellent dispersion stability during dyeing, with almost no scum formation.

EXAMPLES Next, the present invention will be explained in more detail by way of examples. Unless otherwise specified, the middle part or part of the example refers to parts by weight or parts by weight.Example 1 100 parts of water was added to 670 parts of a wet cake (containing 225 parts of dry matter) of basic yellow dye CI Basic Yellow 67. Add and stir well to make a slurry. This slurry was mixed with 675 parts of polystyrene sulfonate (molecular weight approximately 20,000, sulfonation rate 98%) and 20 parts of a 20 mole adduct of ethylene oxide of oleic acid monoglyceride in 2 parts of water.
When the dye is added to a solution of 800 parts with stirring, a dye complex is formed, but then gradually dispersed into fine particles of 1 μm or less. Heat to 60-65°C for 3 hours to achieve fine dispersion more quickly. After adding 86 parts of sodium sulfate (builder), spray drying to obtain 1000 parts of yellow basic dye complex salt composition.
I got the department.

Example 2 270 parts of a dry cake of basic yellow dye CI Basic Yellow 40 was stirred into a solution consisting of 1200 parts of 20% sodium polystyrene sulfonate (molecular weight approximately 20,000, sulfonation rate 95%) and 740 parts of water. Gradually charge to form a basic dye complex salt, then add 500 parts of a 10% sodium polyacrylate (molecular weight approximately 1,000) aqueous solution, followed by sodium polystyrene sulfonate (molecular weight approximately 20,000,
60 parts (sulfonation rate: 95%) were added and stirred while heating at 70 to 80°C to obtain 2770 parts of a yellow basic dye complex salt liquid composition.

Example 3 (al) Add 200 parts of water to 500 parts of basic red dye CI Basic Red 46 wet cake (containing 200 parts of dry matter) and stir well to form a slurry. 1
The mixture was gradually added to a mixed solution of 3,850 parts of 5,000 parts (97% sulfonation rate) and 30 parts of sodium sulfonate, an adduct of dinonylphenol with 19 moles of ethylene oxide, under stirring. Next, it was heated to 50 to 60°C to complete fine dispersion, and then spray-dried to obtain red basic dye complex salt composition 10.
I got 00 copies.

(bl) The same complex salt composition as above was also obtained by the following method.

20% sodium polystyrene sulfonate 385 was added to the slurry of CI Basic Red 46 obtained in the same manner as above.
0 parts were gradually added under stirring. - It was observed that the complex salt was formed and as sodium polystyrene sulfonate was further added, the complex salt became finely dispersed. After adding sodium polystyrene sulfonate, 30 parts of sodium sulfonate, an adduct of dinonylphenol with 19 moles of ethylene oxide, was added with stirring and heated to 50 to 60 DEG C. to complete fine dispersion and spray drying.

Example 4 Sodium sulfonate 30 of the 19 mole ethylene oxide adduct of dinonylphenol in Example 3(a)
The same procedure as in Example 3(a) was repeated except that the same amount of sulfonic acid ammonium salt of 15 moles of ethylene oxide adduct of nonylphenol was added instead of 1000 parts of a basic dye complex salt compound.

Examples 5 to 9 Basic dye complex salt compositions were prepared according to the compositions shown in the table below by a method similar to Examples 1 to 3.

Table Example 10 A dye bath is prepared by thoroughly mixing 2 parts of the yellow basic dye composition prepared in Example 1 in 5,000 parts of warm water containing 1 part of glacial acetic acid. 100 parts of polyacrylonitrile fiber thread was immersed in this at 60°C, and 98 to 1 oo
The temperature was raised to .degree. C., dyed at the same temperature for 60 minutes, and washed with water.

During dyeing, no tar or scum was generated, and the dyed object was uniformly dyed yellow.The residual rate of dye in the dye bath was 3%.
Met.

was hardly seen.

Example 11 A dye bath was prepared by thoroughly mixing 4 parts of the red basic dye composition prepared in Example 3 in 1 part of glacial acetic acid and 5,000 parts of warm water.

100 parts of polyacrylonitrile fiber cloth was immersed at 90°C, heated to 100°C for 10 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 taring without using a slowing agent. The dyeing rate was also good, and the residual rate of dye in the dye bath was 5.

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

Meanwhile, 2 parts of Kayanor Millin Blue BW (acid dye manufactured by Nippon Kayaku) were dissolved in 20 parts of boiling water. Mix these with 6.
A dye bath was prepared by adding 1 part of glacial acetic acid to the ooo part.

100 parts of acrylonitrile wool (50:50) blended yarn is immersed at 60°C, the temperature is gradually raised at a rate of 1°C per minute, dyed at 100°C for 60 minutes, and then slowly cooled to dye a uniform blue color. I got something. The dyeability was good and the dye residual rate was 3.

Example 13 1 part of the yellow basic dye composition produced in Example 5 and 2 parts of Kayalon Polyester Yellow 52l-R-8E200 (Nippon Kayaku Disperse Dye C01, Disperse Orange 55) were dispersed in lukewarm water. ,000
It was diluted with water to make a dye bath. Furthermore, 05 parts of glacial acetic acid and 14 parts of a commercially available carrier agent (IP carrier) were added to make 100. The sample was immersed at 60°C, heated at a rate of 1°G per minute, and dyed at 100°C for 60 minutes. Dyeing was possible with the dye without causing tarring, and almost no contamination of the dyeing machine with the basic dye complex salt was observed.

Example 14 3 parts of the blue dye composition prepared in Example 9 was added to 5.0 parts of water.
00 parts, and the pH was adjusted to 4 with sodium acetate and acetic acid. 100 parts of CDP fibers were immersed in this dye bath at 60°C.
The temperature was raised to 120° C. in 0 minutes, dyed at the same temperature for 60 minutes, washed with water, and then dried. There was no tarring or equipment contamination during dyeing, and the CDP fibers were uniformly dyed blue. The dyeing rate was high and the dye residual rate was 2%.

= 22- Example 15 2 parts of the basic dye composition prepared in Example 8 were mixed with 5 parts of water. O
In addition to the O'O portion, pn was adjusted to 4.

100 parts of CDP S polyester (50:50) blended yarn was immersed in this dye bath at 60°C for 30 minutes.

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, Kayanor Milling Blue EW
2 parts were dissolved in 20 parts of hot water. Add these to 6,000 yen of water
Add 15 parts of a commercially available carrier agent and adjust the pH to 4.
Adjusted to. 100 parts of CDP:wool blend yarn was immersed at 40°C, heated to 80°C for 30 minutes, heated to 105°C for another 30 minutes, and dyed at the same temperature for 60 minutes. After cooling, washing with water, soaping, washing with water and drying, a uniform blue dyed product was obtained. The basic dye composition according to the present invention has good compatibility with acid wool dyes and carriers, has almost no tarring or equipment contamination, and can be used to dye CDP:wool blend yarns in a bath. did it.

Effects of the invention: Basic dyes impair the inherent ability to dye fibers and cause scum etc. to occur during dyeing Patent applicant: Lion Co., Ltd. Nippon Kayaku Co., Ltd.

Claims (1)

[Claims] 1. The sulfonation rate for the basic dye and benzene nucleus is 9.
A basic dye complex salt obtained from 0 to 99% polystyrene sulfonate, the polystyrene sulfonate and the following three additives, namely (1) esters of fatty acid and polyoxyalkylene glycerin ether (2) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In formula (I), R is a nonyl group or a styryl group,
X is a nonyl group, styryl group or a hydrogen atom, M^+ is N
a^+, K^+ or NH_4^+, n represents an integer from 1 to 10, respectively) or (3) one or more additives selected from sodium polyacrylate. A basic dye complex salt composition 2 characterized in that it contains a sulfonation rate of 9 for the basic dye and benzene nucleus.
A basic dye complex salt obtained from 0 to 99% polystyrene sulfonate, the polystyrene sulfonate and the following three additives, namely (1) esters of fatty acid and polyoxyalkylene glycerin ether (2) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In formula (I), R is a nonyl group or a styryl group,
X is a nonyl group, styryl group or hydrogen atom, M^+ is Na^+, K^+ or NH_4^+
, n is an integer of 1 to 10, respectively) or (3) a basic dye complex salt characterized by containing one or more additives selected from sodium polyacrylate. A method for dyeing synthetic fibers dyeable with basic dyes, characterized by using a composition