JP2009007724A - Method of dyeing with acid dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of dyeing with an acid dye, in which a dihalogenotriazine-based sodium salt having a hydrophilic substituent, the acid dye, and at least one kind of a water soluble metal-containing acid dye, and a milling dyestuff are co-existed, and preferably a heat-treatment in an acidic dyeing liquid bath at a normal temperature of ≤30°C up to 100°C enables the dyeing of a fibrous structural material in a short time to, improve a deep dyeing effect and contribute fastness improvement, also which achieves the dyeing time-shortening and increased efficiency by the dyeing method with the acid dye, suppresses thermal energy, and since the amount of the acid dye used is decreased and the salt forming bond of the dihalogenotriazine-based sodium salt having the hydrophilic substituent with the acid dye with the fibrous structural materials is produced in a good efficiency, waste water load (biochemical oxygen demand) formed in the dyeing step is reduced to prevent the pollution of a river caused by the un-reacted or released dye in the waste water. <P>SOLUTION: The method for dyeing the fibrous structural material with the acid dye has coexistence of the dihalogenotriazine-based sodium salt having the hydrophilic substituent, the acid dye, and at least one kind of the water soluble metal-containing acid dye, and the milling dyestuff are co-existed, and preferably has the heat-treatment step in the acidic dyeing liquid bath at a normal temperature of ≤30°C up to 100°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the present invention, a fiber structure can be dyed in a short time by improving the fastness and fastness by performing a heat treatment step in the presence of a dihalogenotriazine-based Na salt having a hydrophilic substituent and an acidic dye. This acid dye dyeing method shortens the dyeing time and improves efficiency, suppresses heat energy, reduces the amount of acid dye used, and reduces hydrophilic substitution. Since the dihalogenotriazine-based Na salt and the acidic dye have an efficient salt-forming reaction with the fiber structure, the dyeing solution becomes transparent and the neutralization process is used, so that the wastewater generated in the dyeing process (biological scientific) It relates to a method for dyeing acid dyes that reduces the load on oxygen demand and prevents river pollution due to drainage in the absence of dye adsorption and shedding.

  The acidic dye is a water-soluble dye having a property of being dyed well from an acidic dye bath such as natural animal fibers such as wool and silk, synthetic fibers such as nylon, and leather.

  Acid dyes are anionic (anionic) dyes, as are direct dyes, but generally have a lower molecular weight than direct dyes. Therefore, it is highly water-soluble and has strong water-soluble groups such as sulfonic acid groups and carboxylic acid groups, but it cannot be dyed on cellulosic fibers such as cotton, hemp and rayon.

  Wool, silk, nylon, and the like are dyed with acetic acid, formic acid, and sulfuric acid as auxiliary agents, but they have a leveling effect, but the fastness of the fiber structure in a wet state is not good.

  Since fiber structures dyed with acid dyes do not have good fastness in a wet state, unbonded sites of dyes and dyes fall off in post-processing such as washing with water, washing with hot water, and boiling. The dyeing effect is lost, and a large amount of dye is contained in the effluent, causing pollution in river drainage.

  Since acid dyes do not have good fastness in a wet state and cannot obtain a deep dyeing effect, use a dyeing method in which metal-containing acid dyes and chromium dyes coexist in the same bath, or use potassium dichromate later. It is a normal dyeing method to obtain a fiber structure having improved after-chrome dyeing method in which chromium treatment is performed with a sulfuric acid acidic solution to improve washing fastness and washing fastness.

  Acid dyes generally dye wool, silk, and nylon. Acid dyes show an anion (anion) for a positively charged basic group (alkaline, PH> 7) in an acid dye bath. It is said that the dye is dyed by electrostatic salt formation.

  Acid dyes are dyed by salt-forming bonds, but the salt-forming bonds are weaker than reactive dyes used for dyeing cellulosic fibers, so that it is impossible to dye in a short time and to obtain a deep dyeing effect Has a long dyeing time at high temperature in an acidic dye bath, and is treated with potassium dichromate to improve fastness and obtain a deep color.

  As described above, acid dyes are dyeing methods that do not have good fastness to moisture on wool, silk, and nylon, but they are dyed and processed widely because they have clear dyeability compared to metal-containing acid dyes.

  Traditionally, acid dyes have been widely dyed on wool, silk and nylon, but high energy consumption in dyeing process at high temperature for a long time, pollution of drainage in unbound or after-treatment dye drainage, There is a problem that the load of wastewater (biological scientific oxygen demand) becomes high, such as environmental effects such as heavy metals and chromium.

  A processing method has been proposed in which form-stabilized processing is performed on an organic natural fiber material using a dihalogenotriazine-based Na salt having a hydrophilic anchoring group used in the present invention (Patent Document 1).

However, the prior art of Patent Document 1 is different from the acid dye dyeing method in any of the purpose, configuration, and effect.
Japanese Patent No. 3415576 (Publication) (Claims)

  In the present invention, the fiber structure can be dyed in a short time by co-existing a dihalogenotriazine-based Na salt having a hydrophilic substituent and an acid dye and performing a heat treatment step. It is characterized by contributing to the improvement of fastness, and this dyeing method of acid dyes shortens the dyeing time and improves efficiency, suppresses heat energy, reduces the amount of acid dyes used, and is hydrophilic. Since the dihalogenotriazine-based Na salt having a substituent and an acidic dye efficiently carry out the salt-forming reaction with the fiber structure, the wastewater generated in the dyeing process (biological matter) by using a neutralization process and the dyeing solution becomes transparent The present invention relates to a method for dyeing acid dyes that reduces scientific oxygen demand) and prevents contamination of rivers by drainage when unbound acid dyes fall off.

Means to solve the problem

  The acidic dye dyeing method of the present invention for solving the above problems is characterized in that a dihalogenotriazine-based Na salt having a hydrophilic substituent is allowed to coexist.

In the present invention, the dihalogenotriazine-based Na salt having a hydrophilic substituent is 2.6-dichloro-4-oxy-S-triazine Na salt 2.6-dichloro-4-thio-S-triazine Na salt. It is characterized in that at least one 6-dichloro-4- (3-sulfoanilino) -S-triazine Na salt coexists.

  The dyeing method of the acid dye according to the present invention uses a “bath exhaustion method”, a dihalogenotriazine-based Na salt having a hydrophilic substituent, an acid dye, a water-soluble metal-containing acid dye, and a milling dye. The conditions for coexisting at least one species and dyeing with the fiber structure can be processed under conditions similar to those for the monochlorotriazine reactive dye. It reduces the amount of dye used and saves energy, dyes in a short time, improves the effect of deep dyeing, improves fastness and drainage load (biological oxygen demand), reduces river pollution, and improves the economics and efficiency of dyeing. Achieved and can significantly improve environmental adaptability.

  In the “bath exhaustion method”, the present invention is charged with at least one kind of a dichlorotriazine compound having a hydrophilic substituent in a normal temperature aqueous solution and an acidic dye, a water-soluble metal-containing acidic dye and a milling dye, The dye bath operates at a temperature of 60 ° C. to 65 ° C. over 20 minutes. When the temperature reaches 60 ° C. to 65 ° C., an acidic dye bath is prepared using a dyeing assistant, acetic acid, formic acid, sulfuric acid, etc., and then heated to 100 ° C. and heat-treated at the dye bath temperature. It is what.

  In the “bath exhaustion method”, dichlorotriazine-based Na salt having a hydrophilic substituent in an aqueous solution at normal temperature and an acid dye, as well as water-soluble substances, in order to improve the deep dyeing effect and fastness of the fiber structure. A metal-containing acid dye can be charged into the bath solution and processed by the same dyeing method as the acid dye.

The invention's effect

  The method for dyeing acid dyes in a short time, wherein at least one kind of dihalogenotriazine-based Na salt having a hydrophilic substituent of the present invention, an acid dye, a water-soluble metal-containing acid dye and a milling dye coexist in the same bath. Dyeing is possible, the effect of dark dyeing is obtained, the fastness of the fiber structure is improved, the amount of dye used disappears, the thermal energy is suppressed and the wastewater generated in the dyeing process (biological oxygen demand) is reduced. It can prevent river pollution due to acid dye unbonding or dropping.

  A feature of the present invention is that acid dyes are dyed on fiber structures, generally wool, silk and nylon, and have a positive (+) charged basic group (alkaline PH> 7) in an acidic dyeing desire. It is said that an acid dye which shows an anion (anion) is dyed by electrostatic salt-forming bond with the end part of the fiber structure, but it has a basic, hydrophilic substituent that is coated on the fiber. The dihalogenotriazine-based Na salt and the acid dye are formed by salt formation.

  The features of the present invention will be described analytically.

  The dihalogenotriazine-based Na salt having a hydrophilic substituent is a raw material matrix. The substitution reaction of cyanuric chloride with chlorine is carried out at a reaction temperature of 0 to 10 ° C. for primary chlorine and a reaction temperature of 20 to 50 ° C. for secondary chlorine. Further, it is known that the substitution is carried out sequentially with an electron donating substituent at a reaction temperature of tertiary chlorine of 60 ° C. to 100 ° C.

In order to obtain a dihalogenotriazine-based Na salt having a hydrophilic substituent, an acid binder such as sodium bicarbonate (NaHCO ₃ ), sodium carbonate (Na ₂ CO ₃ ), sodium hydroxide (NaOH), or the like is used. When the hydrolysis is carried out, a dihalogenotriazine-based Na salt having a hydrophilic substituent is obtained.

  The dihalogenotriazine-based Na salt having a hydrophilic substituent of the present invention is disclosed in German Patent No. 2357252. Gazette, or US Pat. No. 5,601,971. As described in the specification and the like, it can be synthesized according to a known synthesis method, but the outline is as follows.

  For example, 1.00 mol of cyanuric chloride is charged into ice water at 5 ° C. or lower, and then, for example, 1.02 mol of m-sulfanilic acid and about 1 mol of sodium carbonate are gradually charged with good stirring. The preparation of m-sulfanilic acid and sodium carbonate takes about 3 hours at PH = 7 ± 1, and it is charged at 5 to 1 ° C. and analyzed by high performance liquid chromatography (HPLC). If cyanuric chloride is almost disappeared, The reaction is completed by stirring for 1 hour with moisturizing. During this time, the pH is maintained at 6-8, the composition is analyzed by HPLC, and the reaction is terminated when the monosulfanyl compound is 90% or more. After the reaction, a trace amount of insoluble matter is removed by filtration, and finally the pH is adjusted to 7. In this way, an aqueous 2.6-dichloro-4- (3-sulfoanilino) -S-triazine Na salt solution is obtained in high yield. This compound is stable for about one month when stored at 5 ° C. or lower in a refrigerator.

  In the dihalogenotriazine-based Na salt having a hydrophilic substituent of the present invention, the primary chlorine of cyanuric chloride of the dihalogenotriazine ring is O.D. It is characterized by having Na substituted.

  The dihalogenotriazine Na salt having a hydrophilic substituent is weakly acidic to weakly alkaline dye at a temperature rising time from room temperature to 60 ° C. by coexisting a dihalogenotriazine Na salt having a hydrophilic substituent and an acidic dye. In the liquid, the first reaction site O.D. Na coats the fiber structure for salt formation with the halogen site (+) of the fiber structure. At this point, the acid dye is unbound (undyed) with the fiber structure. At 60 ° C. to 65 ° C., acid dye, water-soluble metal-containing acid dye and milling dye are used as an acid bath using a dyeing assistant. At this point, the fiber structure is coated with a dihalogenotriazine-based Na salt having a basic group. The dihalogenotriazine-based Na salt having a hydrophilic substituent is a large amount of acid binder used in the production stage, and the second reaction site and the third reaction site are changed from CL to O.D. The acid dye is considered to be Na, and by further raising the temperature, the acid dye performs salt-forming bonding to the fiber structure. At this point, the fiber structure is an electron of a dihalogenotriazine-based Na salt having a hydrophilic substituent. O. in the sex substitution reaction. The salt formed by salt formation with Na or the remaining CL is ion-bonded to the halogen moiety (H) of the sulfonic acid group and carboxylic acid group of the acidic dye to form O.D. It is estimated that it is H. By using these salt-forming bonds and ionic bonds, the fiber structure can be dyed and dyed in a short time to obtain a deep dyeing effect. Furthermore, the dihalogenotriazine-based Na salt having a hydrophilic substituent contributes to improvement in fastness because the salt structure is formed even in the dyeing bath of weakly acidic to weakly alkaline with the fiber structure.

Furthermore, the feature of the present invention is that the dihalogenotriazine-based Na salt having a hydrophilic substituent is subjected to salt formation in an electronic substitution reaction so that the acid dye is bound to nearly 100%, thereby bringing the acid dye into the dye bath. Less residual, less polluted rivers in drainage, and dihalogenotriazine-based Na salts with hydrophilic substituents are converted into salt (Nacl) and water (H ₂ O) by salt-forming bonds. (Biological scientific requirement amount) The load can be reduced.

  In this way, the dyeing time is shortened compared to the conventional dyeing method using an acid dye, and the efficiency by coexisting an acid dye and a dihalogenotriazine-based Na salt having a hydrophilic substituent in the dye bath. It contributes to the reduction of carbon dioxide and nitrogen oxides without using enormous energy by achieving the conversion, reducing the river pollution in the reduction of dye, and the drainage (biological scientific requirement) load due to its salt formation Reduce. Furthermore, dihalogenotriazine-based Na salts and acid dyes that can expand production in the field of acid-dyed clothes with excellent economic efficiency without installing new equipment and have a hydrophilic substituent The co-existing dyeing method has high technical and practical value and can cope with recent health problems and global environmental problems, and can greatly contribute to dyeing and processing industries using acid dyes. .

  Hereinafter, the present invention will be described in detail together with preferred embodiments.

  The heat treatment is carried out by coexisting the dihalogenotriazine-based Na salt having a hydrophilic substituent of the present invention and an acidic dye to give dyeing to the fiber structure in a short time, the effect of deep dyeing, and improvement in fastness to save energy. The reduction of wastewater (biological scientific requirement) load is achieved.

    The dyeing method for acid dyes has a fiber structure that is immersed in a dihalogenotriazine-based Na salt having a hydrophilic substituent and an acid dye so that the treatment temperature, bath ratio, and time are regulated, and there are heat treatment reactions and bonding steps. That means.

  The dihalogenotriazine-based Na salt having a hydrophilic substituent has a function of dissolving in water together with an acidic dye and performing salt-forming bonding in a heat treatment and an acidic bath.

  The dyeing method for acid dyes is the main dyeing method as a heat treatment, in which a dihalogenotriazine Na salt having a hydrophilic substituent and an acid dye are allowed to coexist and salt formation is carried out on the fiber structure. It is.

    For some leathers, the “dry heat method” is used.

  The function of salt-forming bond to the fiber structure will be described in the presence of a dihalogenotriazine-based Na salt having a hydrophilic substituent and an acidic dye in the “exhaust in bath method”.

A predetermined amount of a dihalogenotriazine-based Na salt having a hydrophilic substituent is charged into an aqueous solution at room temperature. Then, acid dye dissolved in hot water is added in advance, stirred in the dye bath, and then the fiber structure is put in and operated at room temperature for 5 to 10 minutes. After that, from about 20 minutes The temperature is gradually raised over 30 minutes, and the temperature is raised to 60 ° C to 65 ° C. The primary chlorine of the dihalogenotriazine ring of the dihalogenotriazine-based Na salt having a hydrophilic substituent is O.D. from room temperature to 60 ° C. to 65 ° C. for 20 minutes to 30 minutes. Since it is substituted with Na, salt formation is carried out with the NH ₂ group, OH group, SH group, COOH group of the fiber structure to have an OH group. Furthermore, the dihalogenotriazine-based Na salt having a hydrophilic substituent forms a dihalogenotriazine ring. In the synthesis process, the remaining CL groups for synthesis by carrying out alkaline hydrolysis using sodium bicarbonate, sodium carbonate, and sodium hydroxide are heated in a dye bath solution of weak acid to weak alkali. O. It is considered that the Na group is substituted with one or two triazine rings. Accordingly, the fiber structure forms a structure in which a triazine ring having a basic group positively charged (+) is coated. When the temperature reaches 60 ° C. to 65 ° C., an acid bath is formed using acetic acid, formic acid and sulfuric acid. After the addition, the temperature is maintained at 60 ° C. to 65 ° C. for about 5 minutes to 10 minutes, and then the temperature is increased to 85 ° C. to 100 ° C. over 20 minutes. The acid dye having a sulfonic acid group (a class of C ₆ H ₅ SO ₃ H) and a carboxylic acid group (—COOH) during this heating operation time has a positively (+) charged fiber structure and an O.D. The triazine ring having the Na group and the CL group also has the second property due to electron substitution. All the third site triazine rings are O.D. Na and CL become OH groups and become cyanuric acid, and further salt formation is carried out. By continuing the temperature of the dye bath at 85 ° C. to 100 ° C. for about 20 minutes to 60 minutes, the fiber structure is almost completely formed into a salt, and the acid dye is ion-bonded to form the dye bath in the original aqueous solution. Dyeing is complete. No further staining is necessary.

Therefore, unlike the existing dyeing method of acid dyes, the fiber structure and dihalogenotriazine-based Na salt having a hydrophilic substituent group are weakly acidic with NH ₂ group, OH group, SH group, COOH group and the like. An ionic reaction is carried out by salt formation in a weakly alkaline dye bath. Substitution with triazine ring having Na group, and acid dye having sulfonic acid group or carbosylic acid group is ion-bonded to fiber structure in acid bath to form salt bond with triazine ring which is formed into a film This reduces the amount of acid dyes used, reduces drainage (bioscientific oxygen demand) load, and prevents dye unreacted and river pollution due to shedding. It is thought that it is obtained.

  Slightly dark colors such as candy, black, brown, etc. are dyed, and water-soluble metal-containing acid dyes are combined with dihalogenotriazine-based Na salts with hydrophilic substituents and acid dyes to improve fastness to washing and sunlight. It can also be dyed.

  Furthermore, although the fastness to sunlight is not good, since the color becomes clear, it can be dyed in the presence of a milling acid dye and a dihalogenotriazine Na salt having a hydrophilic substituent.

What is a dihalogenotriazine-based Na salt having a hydrophilic substituent that can be used in the present invention 2.6-Dichloro-4-oxy-S-triazine Na salt 2.6-Dichloro-4-thio-S- Triazine Na salt 2.6-Dichloro-4- (3-sulfoanilino) -S-triazine Na salt

The conditions that these compounds should have are substitution to carry out a salt-forming bond in an acidic dye bath with an acidic dye having a sulfonic acid group (a class of C ₆ H ₅ SO ₃ H) and a carboxylic acid group (—COOH). A compound having a group.

  The metal-containing acidic dye that can be used in the present invention is a necessary condition that it must be dissolved in water, and the metal is coordinated with the dye in the form of a complex. A one-to-one type gold-containing dye that binds to a molecule to form a complex salt, with names such as Neolan (Ciba), Palatine (IG), Eisen-Opal (Hoshigaya), Sumilon (Sumitomo Chemical) . A pair of two-type metal-containing acid dyes in which metal atoms are combined with two dye molecules to form a complex salt, and have the titles Irgaran (Geigy) and Shibaran (Ciba).

  Milling acid dyes that can be used in the present invention are represented by carborane (ICI).

  In the present invention, it is preferable that a heat treatment step in an acidic bath from room temperature of 30 ° C. or lower to 100 ° C. is included.

  In the present invention, the fiber structure can be made at the stage of cotton and yarn, weaving or knitting, then non-woven fabric typified by leather, or semi-finished product in the process, finished product, dyed product stage. As long as the effect of the present invention is not hindered, it is possible to carry out salt-forming bonds on synthetic fibers.

  In the present invention, a dihalogenotriazine Na salt having a hydrophilic substituent, an acid dye, a water-soluble metal-containing acid dye and a milling acid dye are allowed to coexist, and salt formation is carried out to form a fiber structure in a short time. Improves the dyeing effect, improves the fast dyeing effect, improves fastness in combination with water-soluble metal-containing acid dyes, shortens dyeing time, achieves efficiency, suppresses heat energy, reduces acid dye usage, This section outlines the dyeing process conditions to reduce dyeing process wastewater (biological oxygen demand) load and prevent contamination of rivers by combining and dropping only dyes.

The present invention mainly uses the “bath exhaust method” except for the “dry heat method” such as leather. In the “bath exhaust method”, water having a water temperature of preferably 30 ° C. or less is preferably introduced into the dyeing bath so that the bath ratio is 1:60 or less with respect to the total weight of the fiber structure. A dihalogenotriazine-based Na salt having a hydrophilic substituent is added in an amount of 0.1% to 10% (owf) in terms of 100% purity in accordance with the purpose of dyeing concentration, an acid dye, and a water-soluble content. At least one of metal acid dye and milling acid dye is added in an amount of 0.1% to 20% (owf), and the mixture is stirred for 10 minutes at room temperature water temperature. Thereafter, the temperature rise in the dyeing bath is started, but the temperature is slowly raised from 60 ° C. to 65 ° C. over about 20 minutes to 30 minutes. When the temperature is increased rapidly, the CL groups at the second and third sites of the dihalogenotriazine-based Na salt having a hydrophilic substituent are hydrolyzed to become OH groups, thereby inhibiting the salt-forming bond of the acid dye, O. There is a possibility that the Na group does not form a film on the fiber structure and the leveling property is impaired. In the vicinity of 60 ° C. to 65 ° C., 0.1% to 20% (owf) of acetic acid, formic acid and sulfuric acid are added, and the water temperature in the dyeing bath is maintained for 5 to 20 minutes. Thereafter, the temperature is raised to 80 ° C. to 100 ° C., followed by heat treatment and a dyeing step at that temperature for 10 minutes to 60 minutes. The dihalogenotriazine-based Na salt having a hydrophilic substituent in this high temperature, acidic bath is partially or two-fold O.D. in the triazine ring during the dyeing process. It has Na groups and is coated on the fiber structure. In this theory, dihalogenotriazine having a hydrophilic substituent based on cyanuric chloride as a raw material matrix is converted to ricyanuric acid by OH groups at the second and third sites in an acidic bath at a high temperature due to the reaction mechanism. It is considered to form a salt bond with an acid dye having a halogen moiety (H) of a sulfonic acid group (C ₆ H ₅ SO ₃ H) or a carboxylic acid group (—COOH). Therefore, unlike salt washing with ordinary acid dyes, salt formation is carried out nearly 100%, so that the washing solution becomes transparent and dyeing is completed. Therefore, it is not necessary to carry out any further dyeing and the dyeing is completed. After completion of this, normal temperature water is poured into the dye bath, and then cooled down to 30 ° C. to 40 ° C., drained and washed with water, and the dyeing process is completed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to these Examples.

Example 1
700 liters of room temperature water was put into a room temperature type liquid flow dyeing machine, and 2.6200 dichloro-4- (3-sulfoanilino) -S-triazine Na salt was 7200 cc (pure content 720 g ows 3). %) And 1k560 g (ows 6.5%) of an acidic dye (black) previously dissolved in hot water was added. Thereafter, a fabric of 100% wool, the structure was 2/2 twill, 2 m of 4 m to be scraped by 150 cm, and a pure weight of 24 k500 g were added. At this time, the bath ratio was 1:30, and the room temperature operation was performed at room temperature (water temperature 28 ° C.) for 10 minutes. At this time, the pH of the aqueous solution was 7.2. Thereafter, the temperature was slowly raised at 1.5 ° C./min for about 20 minutes to raise the water temperature in the dye bath to 62 ° C. Acetic acid was added at 1650 cc (1.5 cc / L) to set PH to 5.2. Run at 62 ° C to 63 ° C for 10 minutes and run at 2 ° C / min to 90 ° C for about 15 minutes. After running at 90 ° C for 15 minutes and confirming the dye solution, the dye solution is almost transparent. Since it became a state, about 800L of water was thrown in and it cooled down to 40 degreeC. At about 40 ° C., washing was performed for 10 minutes to drain water, and 1000 L of normal temperature water was added again, followed by washing with water for 10 minutes. Then, the ingredients are taken out, vacuum dehydrated, and boiled at 80 ° C. for 20 minutes for dehydration and drying. Thereafter, full deca treatment was performed at 120 ° C. for 60 minutes. Table 1 shows the results of the fastness test of the 100% wool fabric. The evaluation organization was conducted at Kyoto Textile and Mechanical Metal Promotion Center.

Comparative Example 1
The same woven fabric as that used in Example 1 was subjected to the same dyeing process and time conditions without the presence of 2.6 dichloro-4- (3-sulfoanilino) -S-triazine Na salt. Table 1 shows the results of the fastness test of the 100% wool fabric.

Example 2
Take up 2/60 corn wound yarn of 100% wool into a casserole, charge 1kg into a package type room temperature dyeing machine, and then add 20L of room temperature water (24 ° C). 1:20 confirmation, then, 2.6 cc-4-thio-S-triazine Na salt was added 400 cc (pure content 40 g ow 4%) and the acid dye (blue) previously dissolved in hot water was added. 40 g (ow 4%) was charged. At this time, the water temperature was 27 ° C. After the water temperature in this dye bath is operated at room temperature for 10 minutes, the temperature is increased to 60 ° C. over about 20 minutes at 1.5 ° C./minute, and the temperature increase is stopped at 60 ° C. for 10 minutes. Acetic acid was added in three portions to make the total amount 30 ° C. (1.5 cc / L). Thereafter, the temperature was raised to 85 ° C. at 2 ° C./min and maintained at 85 ° C. for 30 minutes, and drainage was carried out after confirming that the dyeing solution became transparent. Again, 30 L of normal temperature water was added, the temperature was raised to 60 ° C., the temperature of the aqueous solution in the bath was maintained for 15 minutes, hot water was washed and drained. This was dehydrated with a centrifugal dehydrator and dried. Table 2 shows the results of the dyeing property black color developability and improvement test of the 100% wool material.

Comparative Example 2
In Example 2, a 100% wool 2/60 casserole-like yarn was used with the same dyeing processing time in the absence of 2.6-dichloro-4-thio-S-triazine Na salt. Table 2 shows the results of the dyeing property black color developability and improvement test of the 100% wool material.

Example 3
Using the same dyeing machine as in Example 1, 700 L of room temperature water was added, and 2.6800 dichloro-4-thio-S-triazine Na salt was added therein to 4800 cc (pure content: 480 g ow f4). %) Was added to the acid dye (black) previously dissolved in hot water, and 1 k320 g (ow 5.5%) and a pair of two-type metal-containing acid dye (blue) 240 g (ow f1%) And coexisted. Thereafter, using the ingredients used in Example 1, the post-treatment was carried out with the same temperature elevation, processing time, and amount of acetic acid used. Table 3 shows the fastness test results of the materials.

Comparative Example 3
The same woven fabric as used in Example 3 was subjected to the same dyeing process, time and conditions without the presence of 2.6-dichloro-4-thio-S-triazine Na salt. Table 3 shows the fastness test results of the materials.

Example 4
20 L of normal temperature water was put into a liquid dyeing machine dedicated to trial production of a normal temperature type sample, and 200 cc of 2.6-dichloro-4-oxy-S-triazine Na salt (pure content 20 g ow 2). 50 g (ow 5%) of acid dye (black) dissolved in hot water in advance and 10 g of one-on-one type metal-containing acid dye (yellow) (ow 1%) It was made to coexist. After that, a nylon and 100% taffeta (plain weave) woven fabric was added, and the operation was carried out at room temperature for 5 minutes. At 60 ° C, the temperature rise was stopped, and formic acid was added in small portions to increase the pH in the dyeing bath to 5. 5 was prepared. After maintaining the temperature of this dye bath for 5 minutes, the temperature was raised to 100 ° C. at 2 ° C./minute, and the temperature of 100 ° C. was continuously operated for 30 minutes to take out nylon and taffeta. At that time, the dye solution in the dye bath was in a transparent state. After draining, normal temperature water was added again, the temperature rising operation was performed at 2 ° C./min, and hot water was washed at 60 ° C. for 20 minutes. After draining and washing again with water at room temperature for 10 minutes, the mixture was subjected to Fix treatment in the same bath, and then dehydrated and dried. Table 4 shows the fastness test results of the materials.

Comparative Example 4
The same woven fabric used in Example 4 was subjected to the same dyeing processing time and conditions without the presence of 2.6-dichloro-4-oxy-S-triazine Na salt. Table 4 shows the fastness test results of the materials.

Test results

評価方法
後染色加工における黒発色性向上試験は３回実施する、Ｌは濃度を表し１０以下の数値は黒の濃度を示す。Ａ、Ｂは青と赤の色相差を示し、Ｌの３回実施後の数値が０．５以内であると洗濯後黒の発色が低下しないことを示す。洗濯回数は１０回実施。Black color development improvement test by post-processing

Evaluation Method The black color development improvement test in the post-dyeing process is carried out three times, L represents the density, and a numerical value of 10 or less represents the black density. A and B indicate the hue difference between blue and red. If the numerical value of L after 3 times is within 0.5, the color development of black after washing does not decrease. Washing was performed 10 times.

Test results

  From the results of the fastness test shown in Table 1, the superiority of the present invention was confirmed, for example, in Example 1 and Comparative Example 1, in which the fastness was improved and the dye liquor was not contaminated.

  As a result of the black color development improvement test by post-processing in Table 2, in Example 2 and Comparative Example 2, the present invention can dye acid dyes in a short time, the dyeing density is improved, and the fastness to washing is also improved. Thus, the superiority of the present invention was confirmed.

  From the results of the fastness test shown in Table 3, the superiority of the present invention was confirmed, for example, in Example 3 and Comparative Example 3 in which fastness was improved and the dyeing solution was not contaminated.

  From the test results in Table 4, the superiority of the present invention was confirmed in Example 4 and Comparative Example 4.

Claims (5)

  Method of dyeing acid dyes in fiber structures in the presence of dihalogenotriazine-based Na salts having hydrophilic substituents, acid dyes, water-soluble metal-containing acid dyes and milling dyes Quick dyeing in an alkaline dye bath -Dyeing method of fiber structure to give deep dyeing.   A fiber structure in which at least one of an acid dye, a water-soluble metal-containing acid dye, and a milling dye coexists, wherein the dihalogenotriazine Na salt having a hydrophilic substituent is derived from cyanuric chloride Method for dyeing acid dyestuffs. A method for dyeing an acidic dye, characterized in that at least one dihalogenotriazine-based Na salt having a hydrophilic substituent is selected from the following compounds.
2.6-Dichloro-4-oxy-S-triazine Na salt 2.6-Dichloro-4-thio-S-triazine Na salt 2.6-Dichloro-4- (3-sulfoanilino) -S-triazine Na salt   It has a dyeing method in which a dihalogenotriazine-based Na salt having a hydrophilic substituent and an acid dye are allowed to coexist, and preferably heat-treated in an acid dye bath at a room temperature of 30 ° C. or lower to 100 ° C. A method for dyeing an acid dye of a fiber structure. The fiber structure is characterized by a dyeing method in which heat treatment is performed in an acid dye bath such as silk, wool, mohair, Angola, alpaca, cashmere, animal hair, or other animal protein fiber structure, leather, nylon or the like. The dyeing | staining method of the acid dye of the fiber structure of any one of -4.