JP4412979B2 - Dyeing aid for fiber material and method for dyeing fiber material using the same - Google Patents

Description

  The present invention relates to a dyeing aid for fiber material and a method for dyeing a fiber material using the same to obtain a dyed product having no blurring in dyeing a fiber material.

  Traditionally, textile materials are dyed using dyes such as direct dyes, sulfur dyes, selenium dyes, naphthol dyes, reactive dyes, basic dyes, oxidation dyes, and disperse dyes according to the fiber material of the object to be dyed. There are various dyeing methods. For example, polyester fibers are generally dyed using disperse dyes under high temperature and pressure.

  In order to obtain uniform dyeability in dyeing such fiber materials, dyeing assistants are used in the dye bath depending on the respective fiber materials and dyes, but depending on the dyeing conditions, the dye dispersibility is excellent. Even when a dyeing agent is used, the dye may aggregate or precipitate during dyeing, resulting in uneven dyeing such as taring and dyeing spots.

  Most of the water used in the dyeing process is made by softening groundwater, but soft water is rarely used in the previous process (for example, the scouring process). Metals often adhere to the dough, causing them to be brought into the dye bath. If the dyeing bath contains a metal component, the dye undergoes reductive decomposition, causing problems such as failure to obtain the desired color after dyeing. Furthermore, the hardness of water and the content of the mineral components contained differed depending on the land and the time of use, and it was difficult to always reproduce stable colors.

  In addition, reduction washing is performed to remove unfixed and undyed dye remaining on the fiber surface accompanying dyeing and improve various dyeing fastnesses, but leveling agents, dispersants, etc. Even when dyeing is performed in combination with the above dyeing assistant, if there is a large amount of unfixed or undyed dye remaining on the fiber surface, the effect of reduction cleaning or the like is often very poor.

  In order to solve such problems, there is also a method of capturing and improving the hardness component of water by using a chelating agent such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, sodium tripolyphosphate, etc. Although there is a little effect in stabilizing the color, the effect is small, and when these chelating agents are used in combination, the chelating agent forms a complex salt with the metal as the chromophoric group in the dye. There is a fatal problem that the balance of bonding is lost and the hue at the time of dyeing is different from the hue that should be obtained from the dye used.

  Further, a method for improving by using a polyacrylate together (Patent Document 1) and a method for improving by using a salt of a copolymer of maleic acid and (meth) acrylic acid (Patent Document 2). ) Is also disclosed, but it has not yet reached a radical solution.

JP 59-21688 A JP 59-216987 A

  The present invention solves the problems of the prior art as described above, and provides a dyeing aid for fiber material and a method for dyeing fiber material, which makes it possible to obtain a dyed product having no blurring in dyeing fiber material. It is in.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a dyed product with no blurring by using a dyeing assistant combined with a specific compound when dyeing a fiber material. Based on this finding, the present invention has been completed.

  That is, the present invention provides a dyeing aid for fiber material, which contains a polycarboxylic acid polymer and a polyvalent carboxylic acid having a hydroxyl group.

  The dyeing aid for fiber material of the present invention is characterized in that the polycarboxylic acid polymer has a weight average molecular weight of 1,000 to 20,000.

  The dyeing aid for fiber material of the present invention is characterized in that a mass ratio of the polycarboxylic acid polymer to the polyvalent carboxylic acid having a hydroxyl group is 20/80 to 95/5.

  The dyeing aid for fiber material of the present invention is characterized by containing an antioxidant in addition to the polycarboxylic acid polymer and the polyvalent carboxylic acid having a hydroxyl group.

  The dyeing aid for fiber material of the present invention is characterized in that the polyvalent carboxylic acid having a hydroxyl group is citric acid.

  Moreover, this invention provides the dyeing | staining method of the fiber material characterized by dye | staining a fiber material with the dyeing bath containing the dyeing aid for fiber materials in any one of said.

  According to the textile material dyeing assistant and dyeing method of the present invention, it is possible to obtain a stable dyed article having good color reproducibility regardless of the quality of water.

  The dyeing aid for fiber material of the present invention is characterized by containing a polycarboxylic acid polymer and a polyvalent carboxylic acid having a hydroxyl group.

  The polycarboxylic acid-based polymer used in the present invention can be synthesized by a conventionally known radical polymerization method using, for example, acrylic acid, methacrylic acid, maleic acid or the like as a monomer, or a commercially available polymer is used. May be. Although there is no restriction | limiting in particular in the manufacturing method of a polycarboxylic acid type polymer, For example, the radical polymerization initiator is added to the aqueous solution of the said monomer and / or its salt, and it is made to heat-react at 30-150 degreeC for 2 to 5 hours. And so on. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the monomer and / or salt thereof. The radical polymerization initiator to be used is not particularly limited, but is a redox polymerization initiator or a peroxidation based on a persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate, or a combination of persulfate and sodium bisulfite. Examples thereof include hydrogen and water-soluble azo polymerization initiators, and these radical polymerization initiators may be used alone or in combination of two or more. Furthermore, in the case of radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.

  In addition to the above monomers, a copolymerizable monomer may be used for radical polymerization. The copolymerizable monomer used is not particularly limited, and examples thereof include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates. Although there is no restriction | limiting in particular also in acrylates or methacrylates to be used, What has a C1-C3 hydrocarbon group is preferable, This hydrocarbon group may have substituents, such as a hydroxyl group. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, and the like. These copolymerizable monomers may be used alone or in combination of two or more.

  Furthermore, the carboxyl group in the polycarboxylic acid polymer may be free or neutralized with an alkali metal or an amine compound. Here, examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

  The polycarboxylic acid polymer used in the present invention preferably has a weight average molecular weight of 1,000 to 20,000, particularly preferably 3,000 to 15,000. If the weight average molecular weight of the polycarboxylic acid polymer is less than 1000, the effect of the reproducibility of the dyed product may be insufficient, and if the weight average molecular weight exceeds 20000, the viscosity in the form of a dyeing aid for fiber materials May cause a problem in operability.

The polyvalent carboxylic acid having a hydroxyl group used in the present invention, citric acid, Li Ngosan, but tartaric acid and the like, among these, especially citric acid are preferred. The carboxyl group in these polyvalent carboxylic acids may be free or neutralized with an alkali metal or an amine compound. Here, examples of the alkali metal include sodium, potassium, and lithium, and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

  In the dyeing aid for fiber material of the present invention, the blending ratio (mass ratio) of the polycarboxylic acid polymer and the polyvalent carboxylic acid having a hydroxyl group is preferably 20/80 to 95/5, In particular, it is preferably 20/80 to 80/20. If this blending ratio (mass ratio) is less than 20/80 and the amount of the polyvalent carboxylic acid having a hydroxyl group is large, the metal chelate dispersibility may not be sufficient, exceeding 95/5, If the amount of the polyvalent carboxylic acid having a hydroxyl group is small, the stability of the hue after dyeing may be affected.

  Further, by adding an antioxidant to the dyeing aid for fiber material of the present invention, the color blur prevention property is further improved. As the antioxidant used here, any of a phenolic antioxidant, a phosphite antioxidant, a thioether antioxidant, a benzotriazole antioxidant, a hindered amine antioxidant, etc. may be used. A phenolic antioxidant is particularly preferable. Examples of the phenol-based antioxidant used include alkyl ester-based, sulfur-based, phosphorus-based, acid amide-based, and amine-based monophenols or diphenol compounds. Among these, amine-based diphenol compounds are particularly preferable. The addition amount of the antioxidant is preferably 0.01 to 10 parts by mass, particularly 0.02 to 5 parts by mass, based on 100 parts by mass of the total amount of the polycarboxylic acid polymer and the compound having a hydroxyl group. Part.

  Conventionally known nonionic surfactants, anionic surfactants or other additives can be blended with the dyeing aid for fiber materials of the present invention within a range not impairing the effects of the present invention.

  Next, the dyeing method using the dyeing aid for fiber material of the present invention will be described.

  The dyeing aid for fiber material of the present invention can be applied and processed to materials composed of polyester fibers, synthetic fibers such as polyamide fibers such as nylon, cellulosic fibers, or composite fibers composed of combinations of these fibers. These fiber materials may be in any form of fiber, yarn, knitted fabric, woven fabric and the like.

  The dyeing aid for fiber material of the present invention is used by adding to a dyeing bath when dyeing the fiber material. The addition amount is preferably 0.01 to 10 g / L, particularly 0.01 to 5 g in terms of the total amount of the polycarboxylic acid polymer and the polyvalent carboxylic acid having a hydroxyl group in the dyeing bath. / L is preferred. If the addition amount is less than 0.01 g / L, the effect of the reproducibility of the dyed product may be insufficient, and even if it is added in excess of 10 g / L, the effect corresponding to the addition amount may not be obtained. is there.

  When using the dyeing aid for textile materials of the present invention, a conventional dyeing machine can be used as it is, and the conventional method is specially changed in dyeing temperature, dyeing pressure, bath ratio, soaping after dyeing, etc. do not have to. In addition, dyes used for dyeing baths, acids for adjusting pH, chelating agents, surfactants as wrinkle inhibitors, and the like can be used as usual. Furthermore, even if a dispersion leveling agent conventionally used for improving the high-temperature dispersibility of the dye or improving the dye transfer property is used in combination, the effect of the dyeing aid for the fiber material of the present invention is hindered. There is nothing.

  The dyeing assistant and dyeing method for textile materials of the present invention are not only used for dyeing knitted fabrics with a liquid dyeing machine, but also for dyeing these with a beam dyeing machine, and for yarn, cotton etc. with a cheese dyeing machine. It is also very effective when dyeing with an Overmeier dyeing machine, a Wins dyeing machine, or a washer dyeing machine.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not restrict | limited at all by these Examples.

The weight average molecular weights of the polymers obtained in Synthesis Examples 1 to 5 were measured using gel permeation chromatography (HLC-8020GPC, manufactured by Tosoh Corporation) and calculated in terms of polyethylene glycol. In addition, TSKgel G5000PW and G3000PW (both manufactured by Tosoh Corporation) are used in combination for the column, and phosphate buffer (0.025 mol / L Na ₂ HPO ₄ · 12H ₂ O and 0.025 mol / L) are used. KH ₂ PO ₄ ) and eluted at a flow rate of 1.0 mL / min. The viscosity was measured at 20 ° C. using a B-type viscometer (BH type, manufactured by Tokyo Keiki Co., Ltd.).

Synthesis example 1
In a 1,000 mL four-necked flask, 100 g of water was added to 200 g of acrylic acid, diluted and heated to 80 ° C., 1 g of sodium persulfate was dissolved in 20 g of water, and this was added dropwise over 1 hour. A polymerization reaction was performed. After dropping, the mixture was reacted at 60 to 70 ° C. for 2.5 hours, and then 100 g of warm water at 60 ° C. was added and cooled to obtain a light yellowish brown transparent liquid polycarboxylic acid polymer solution. The viscosity of this polymer solution was 200 mPa · s, the concentration of the polymer was 48% by mass, and the weight average molecular weight of the polymer was 9,000.

Synthesis example 2
In a 1,000 mL four-necked flask, 100 g of water was added to 200 g of acrylic acid, diluted and heated to 80 ° C., 1 g of sodium persulfate was dissolved in 20 g of water, and this was added dropwise over 1 hour. A polymerization reaction was performed. After dripping, it was made to react at 80-90 degreeC for 2 hours, and then 100 g of warm water of 60 degreeC was added and cooled, and the pale tan transparent liquid polycarboxylic acid polymer solution was obtained. The viscosity of this polymer solution was 140 mPa · s, the concentration of the polymer was 48% by mass, and the weight average molecular weight of the polymer was 4,800.

Synthesis example 3
In a 1,000 mL four-necked flask, 100 g of water was added to 200 g of acrylic acid, diluted and heated to 80 ° C., and 0.1 g of sodium persulfate was dissolved in 20 g of water and added. After the addition, the mixture was reacted at 60 to 70 ° C. for 2 hours, and then 100 g of warm water at 60 ° C. was added and cooled to obtain a light tan transparent liquid polycarboxylic acid polymer solution. The viscosity of this polymer solution was 280 mPa · s, the concentration of the polymer was 48% by mass, and the weight average molecular weight of the polymer was 19,000.

Synthesis example 4
In a 1,000 mL four-necked flask, 80 g of water was added to 200 g of maleic anhydride and stirred to react with maleic acid. Then 0.2 g of ferrous chloride was added, and the mixture was heated to 90 ° C. with stirring. Warm up. A polymerization reaction was carried out by dropping 150 g of 35% hydrogen peroxide solution over 3 hours. After dripping, it was made to react at 80-90 degreeC for 2 hours, then, 40 g of 60 degreeC warm water was added and cooled, and the yellowish brown transparent liquid polycarboxylic acid type polymer solution was obtained. The viscosity of this polymer solution was 122 mPa · s, the concentration of the polymer was 50% by mass, and the weight average molecular weight of the polymer was 7,000.

Synthesis example 5
In a 1,000 mL four-necked flask, 100 g of acrylic acid and 100 g of methacrylic acid were diluted with 100 g of water, heated to 80 ° C., and 5 g of sodium persulfate was added. After the addition, the mixture was reacted at 80 to 90 ° C. for 2.5 hours, and then 100 g of hot water at 60 ° C. was added and cooled to obtain a light tan transparent liquid polycarboxylic acid polymer solution. The viscosity of this polymer solution was 210 mPa · s, the concentration of the polymer was 48% by mass, and the weight average molecular weight of the polymer was 10,000.

Examples 1-9, Comparative Examples 1-5
The components shown in Table 1 and Table 2 below were blended and sufficiently stirred to prepare dyeing aids for fiber materials of Examples 1 to 9 and Comparative Examples 1 to 5.

  The anti-blurring effect of the obtained dyeing assistants for textile materials of Examples 1 to 9 and Comparative Examples 1 to 5 was evaluated by performing a dyeing treatment under the following conditions.

Evaluation test 1
Test cloth Polyester ponge Dyeing machine Mini color dyeing machine (Texam Giken Co., Ltd.)
Bath ratio 1:20
Dyeing bath composition Dye: CI Disperse Blue 56 0.25% owf
Leveling agent (Nikka Sun Salt RM-340E, manufactured by Nikka Chemical Co., Ltd.) 0.5 g / L
Dyeing aid for textile materials 0.5g / L
90% acetic acid 0.3g / L
Metal content α ppm
Water balance Temperature conditions 60 ° C. → Temperature rise (2 ° C./min)→130° C. × 30 minutes → Cooling (80 ° C.) → Drainage → Washing twice Evaluation test 2
Test cloth Nylon knit Dyeing machine Mini color dyeing machine (Texam Giken Co., Ltd.)
Bath ratio 1:20
Composition of dyeing bath Dye (Kayacyl Rhodamine FB, Nippon Kayaku Co., Ltd.) 0.1% owf
Leveling agent (Newbon D-100E, manufactured by Nikka Chemical Co., Ltd.) 1.0 g / L
Dyeing aid for textile materials 0.5g / L
90% acetic acid 1.5g / L
Metal content α ppm
Water balance Temperature conditions 40 ° C → Temperature rise (2 ° C / min) → 100 ° C × 30 minutes → Cooling (80 ° C.) → Drainage → Washing twice Evaluation test 3
Test cloth Polyester / Cotton twill (50/50)
Dyeing machine Mini color dyeing machine (Texam Giken Co., Ltd.)
Bath ratio 1:20
Dye bath composition Dye (Kayarus Supura, Nippon Kayaku Co., Ltd.) 0.1% owf
Leveling agent (Nikka Sun Salt RE-5, manufactured by Nikka Chemical Co., Ltd.) 1.0 g / L
Dyeing aid for textile materials 0.5g / L
90% acetic acid 0.3g / L
Soup glass 10g / L
Metal content α ppm
Water remainder Temperature conditions 60 ° C. → Temperature rise (2 ° C./min)→130° C. × 30 minutes → 90 ° C. × 20 minutes → Cooling (80 ° C.) → Drainage → Wash twice with water Evaluation 3 to Dye under the above conditions with the addition of the metal components shown in Table 5, the color of the dyed product to be dyed, the dyeing aid for fiber material and the dyed material under the above conditions without adding metal components The color of the dyed product (standard color) was compared and visually judged in the following five stages. The results are shown in Tables 3-5.

5: Color is the same as standard color 4: Color is slightly inferior to standard color 3: Color is slightly inferior to standard color 2: Color is inferior to standard color 1: Color is clearly inferior to standard color Chelate dispersion Treatment bath composition Fe (iron (II) sulfate) 200ppm
Dyeing aid for textile materials 0.5g / L
90% acetic acid α g
Water remainder 200 mL of the treatment bath adjusted to pH 4.5 with acetic acid was heated at 90 ° C. for 30 minutes, cooled to room temperature, and then filtered. The presence or absence of a residue on the filter paper was visually judged in the following five steps. The results are shown in Table 3.

5: There is no metal residue on the filter paper. 4: There is very little metal residue on the filter paper. 3: There is a small amount of metal residue on the filter paper. 2: There is a metal residue on the filter paper. 1: A large amount of metal residue on the filter paper. Residual chelate dispersibility

  As can be seen from the results in Table 3, Table 4 and Table 5, the dyed fabrics obtained in Examples 1 to 9 have very little change in color after dyeing even when a metal component is present in the dyeing bath. Moreover, Examples 1-9 are excellent also in the chelate dispersibility of iron. In particular, Example 9 is particularly excellent in both anti-blurring and chelate dispersibility. Moreover, in Table 5, since the chelating agent forms a complex with the metal in the coloring group of the dye in Comparative Examples 1 to 5, particularly Comparative Example 5, there is a large difference in the hue after dyeing. It can be seen that there is no difference.

  Further, it can be seen from Comparative Examples 1 to 5 that when the metal content is small, the color blur is small, but when the metal content is increased or various metals are mixed, the color blur is likely to occur.

  The dyeing assistant for textile materials and the dyeing method using the same according to the present invention enables stable dyeing even when using water of various hardnesses. Can be provided.

Claims (5)

A hydroxyl group- containing polyvalent polymer selected from a polycarboxylic acid polymer having acrylic acid, methacrylic acid and / or maleic acid as a main component and having a weight average molecular weight of 1,000 to 20,000 and citric acid, malic acid and tartaric acid. A dyeing assistant for immersion dyeing of a fiber material , comprising a carboxylic acid. The weight ratio of the polycarboxylic acid polymer and the hydroxyl group-containing polycarboxylic acid is 20 / 80-95 / 5, dyeing Irosukezai of claim 1. Further comprises an antioxidant, dye Irosukezai according to claim 1 or 2. The hydroxyl group-containing polycarboxylic acid is citric acid, dye Irosukezai according to any one of claims 1-3. Process for dyeing fiber materials, which comprises immersing dyeing fiber materials with dye bath containing dye Irosuke agent according to any one of claims 1-4.