JPS6411753B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an agent for improving dyeability of cellulose fibers. Generally, cellulose fibers are dyed using direct dyes,
This is done using dyes such as sulfur dyes, threne dyes, naphthol dyes, reactive dyes, basic dyes, and acid dyes. Among these, direct dyes are dyed by physicochemical adsorption and the color fastness can be easily improved by fixing treatment after dyeing, while sulfur dyes have excellent color fastness but low color clarity. Thren dyes have extremely good color fastness, and naphthol dyes have relatively clear color tones and good color fastness, but they require complicated processes such as dipping the fibers with a primer and developing the color through diazotization treatment with a color developer. Reactive dyes dye by forming a covalent bond between the dye and the fiber, resulting in a clear color tone and excellent color fastness.Basic dyes require a complicated mordant process and are difficult to dye. They each have their own characteristics, such as low fastness, complicated dyeing methods for acid dyes, and unstable hues. Therefore, among these dyes, direct dyes, threne dyes, reactive dyes, etc. are the main dyes. Although there are various types of direct dyes, metal-containing azo type dyes account for a large proportion, and many such metal-containing dyes are also used in acid dyes and reactive dyes. Metal-containing dyes are made by coordinately bonding metal atoms such as chromium, copper, cobalt, iron, and aluminum with dye molecules, but conventional dyeing with these types of dyes has the following problems that need to be resolved. was desired. That is, when the hardness of the water used during dyeing is high, the hardness component of the water inhibits the solubilization and dispersibility of the dye, resulting in a problem in that uniform dyeing cannot be obtained. To improve this, chelating agents such as ethylenediaminetetraacetyl acid, diethylenetriaminepentaacetyl acid, hydroxylethylenediamine triacetyl acid, and nitrilotriacetyl acid are sometimes used together; The agent captures some of the hardness components of water and is somewhat effective in uniform dyeing, but the effect is small, and what is worse is that the chelating agent forms a complex salt with the metal as the coloring group in the dye. This has caused a fatal problem in that the balance of the dye-metal coordination bond is disrupted and the hue of the dyed cloth deviates from the hue that should be obtained from the dye used. Furthermore, threne dyes, which play an important role in the dyeing of cellulose fibers, are water-insoluble dyes that have two or more carbonyl groups, and are reduced with alkali to convert the carbonyl groups into sodium leuco salts, which become water-soluble. Because it has a high affinity with cellulose fibers, it is dyed in this state, and then the sodium leuco salt is oxidized to a quinone form using an acid to develop color, and at the same time it becomes water-insoluble again. It has the following problems, and it has been desired to solve them. In other words, when the water used for dyeing has high hardness, the hard components of the water combine with the dye to form dye dimers, which are insoluble in water and have no affinity with cellulose fibers, making them difficult to use. The problem was that the desired color density could not be obtained from the dye concentration used. Furthermore, in order to improve this, chelating agents such as ethylenediaminetetraacetyl acid, diethylenetriaminepentaacetyl acid, hydroxylethylenediamine triacetyl acid, and nitrilotriacetyl acid are sometimes used in combination, but their effectiveness is not necessarily guaranteed. The current situation is that it is not sufficient and a fundamental solution has not yet been reached. Therefore, the present inventors completed the present invention as a result of intensive research to solve the various problems mentioned above regarding the dyeing of cellulose fibers. That is, the present invention is a copolymer containing maleic acid (MA) and acrylic acid or methacrylic acid {hereinafter abbreviated as (meth)acrylic acid} (AA) as essential constituent monomers, the constituent monomers being The present invention provides a dyeability improver for cellulose fibers comprising a copolymer salt having a molar ratio (MA/AA=γ) of 0.1 to 2.7 and an average molecular weight (MW) of 1000 to 8000. . When cellulose fibers are dyed with metal-containing dyes or thren dyes using highly hard water, by coexisting these dyes with the dyeability improver of the present invention, dyeing methods that are superior to conventional dyeing methods can be obtained. It is possible to obtain dyeability. Although the mechanism by which dyeing problems are solved by the coexistence of the dyeability improver of the present invention when dyeing cellulose fibers with metal-containing dyes is not necessarily clear, the Excellent metal ion sequestering ability and dispersion power act only on the hardness component of water and do not act on the metal as a coloring group in the dye, so the balance of the dye-metal coordination bond is maintained and uniform dyeing is achieved. This is thought to be due to the fact that the hue of the dyed cloth does not shift at the same time as it is dyed.
Furthermore, although the mechanism by which dyeing problems can be solved by coexisting the dyeability improver of the present invention during color development with thren dyes on cellulose fibers is not necessarily clear, the dyeability improver of the present invention has a significant This is thought to be due to its excellent metal ion sequestering ability and dispersion power. Even more preferably, when the water hardness is high, a deep color with a higher color density level is obtained compared to the color density when the water hardness is 0. Although the mechanism by which it also functions as a color deepening agent is not necessarily clear, the dyeability improver causes moderate aggregation of the threne dye on the fiber surface,
It is thought that as a result, the color becomes darker. In order to exhibit such an effect, in the salt of the copolymer containing maleic acid (MA) and (meth)acrylic acid (AA) as essential constituent monomers, the molar ratio of the constituent monomers must be adjusted. (MA/AA)
is γ and its average molecular weight is MW, then γ
is 0.1 to 2.7, and MW is required to be 1000 to 8000. If γ is too small or too large, the effect will be reduced, and if it is within the range of 0.1 to 2.7,
Between 0.1 and less than 1.0 and 1.0 and more and 2.7 or less, the latter is more effective, and the range of 1.15 to 2.7 is even more effective. If the MW is too small or too large, the effect will be small. Furthermore, among the salts of such copolymers, γ is 1.15 to 2.7, MW is 1000 to 8000,
Those that satisfy the condition of γ×MW of 3000 or more exhibit the greatest effect. And to obtain these salts, 1.2 to 1.2 to 1 mole of maleic acid per mole of (meth)acrylic acid is used.
It is preferable to copolymerize 3.0 mol with an aqueous solution of an alkali metal hydroxide using a polymerization initiator and then neutralize it, but other methods can also be used. The salt of the copolymer containing maleic acid and (meth)acrylic acid as essential constituent monomers of the present invention includes:
Forms such as alkali metal salts, ammonium salts, and alkanolamine salts such as diethanolamine and triethanolamine can be used, and maleic acid and (meth)acrylic acid are essential constituent monomers to the extent that they do not impair performance. There is no problem even if an unneutralized portion remains in the copolymer. Furthermore, the copolymer of the present invention contains a tertiary acid other than maleic acid and (meth)acrylic acid to the extent that the performance is not impaired.
It may also be in the form of a copolymer containing the third component.
Ingredients include acrylamide, various sulfonic acids such as methacrylsulfonic acid and vinylsulfonic acid,
2-Hydroxyethyl acrylate, various acrylic esters, various methacrylic esters, N-
Methyloacrylamide or other copolymerizable substances can be used. In addition to cellulose natural fibers such as cotton and hemp, cellulosic fibers include mixed fibers of these cellulose natural fibers and synthetic fibers such as nylon, polyester, and acrylic, as well as semi-synthetic fibers such as acetate. It can be applied to mixed fibers, mixed fibers with recycled fibers such as rayon and cupora, etc., and the form when dyeing can be fibers, yarns, skeins, cheese, woven fabrics, knitted fabrics, non-woven fabrics, as well as clothing and bedclothes. It does not matter whether it is in any form, such as a final textile product such as a packaged product. The amount of the dyeability improver of the present invention varies depending on the type and concentration of the dye used, but is generally 0.01 to 20 g (in terms of solid content) per dyeing bath, preferably 0.04 to 10 g (in terms of solid content). )/Added. Next, the present invention will be explained in more detail with reference to synthesis examples and examples, but the present invention is not necessarily limited to the following examples. Synthesis Example 1 In a four-necked flask, polymerize in the presence of ammonium persulfate using a sodium acrylate aqueous solution and a sodium maleate aqueous solution obtained by neutralizing acrylic acid and maleic anhydride in the presence of an aqueous sodium hydroxide solution, respectively. Temperature 100℃, polymerization time 5
Aqueous solution polymerization was carried out under the following conditions to obtain a dyeability improver consisting of a sodium salt of a copolymer. Synthesis Example 2 In a four-necked flask, using sodium maleate aqueous solution obtained by neutralizing maleic anhydride in the presence of sodium hydroxide aqueous solution and acrylic acid aqueous solution, the polymerization temperature was adjusted in the presence of ammonium persulfate and hydrogen peroxide. Aqueous polymerization was carried out at 100° C. for 5 hours, followed by neutralization using an aqueous sodium hydroxide solution to obtain a dyeability improver consisting of a sodium salt of the copolymer. Synthesis Example 3 In a four-necked flask, ammonium persulfate, hydrogen peroxide, and sodium hydroxide were mixed using an aqueous sodium maleate solution obtained by neutralizing maleic anhydride in the presence of an aqueous sodium hydroxide solution and an aqueous acrylic acid solution. Aqueous solution polymerization was carried out in the presence of the copolymer at a polymerization temperature of 100° C. and a polymerization time of 6 hours, and then an aqueous sodium hydroxide solution was further added to obtain a dyeability improver consisting of a sodium salt of the copolymer. Synthesis Example 4 In a four-neck flask, using a sodium maleate aqueous solution obtained by neutralizing maleic anhydride in the presence of a sodium hydroxide aqueous solution and an acrylic acid aqueous solution, in the presence of hydrogen peroxide and sodium hydroxide. Aqueous solution polymerization was carried out under the conditions of a polymerization temperature of 100° C. and a polymerization time of 6 hours, and then an aqueous sodium hydroxide solution was further added to obtain a dyeability improver consisting of a sodium salt of a copolymer. Synthesis Example 5 In a four-necked flask, using a sodium maleate aqueous solution obtained by neutralizing maleic anhydride in the presence of an aqueous sodium hydroxide solution, an aqueous acrylic acid solution, and acrylamide, in the presence of hydrogen peroxide and sodium hydroxide. Aqueous solution polymerization was carried out at a polymerization temperature of 100°C and a polymerization time of 6 hours, and then an aqueous sodium hydroxide solution was further added to obtain a dyeability improver consisting of a copolymer salt containing 3% acrylamide as a third component. . Synthesis Example 6 A dyeability improver was obtained in the same manner as in Synthesis Example 4. Synthesis Example 7 Using an isopropyl alcohol solution of maleic anhydride and acrylic acid in a four-necked flask,
Copolymerization was carried out in the presence of benzoyl peroxide at a polymerization temperature of 90°C and a polymerization time of 8 hours, and then isopropyl alcohol was distilled off and neutralized with aqueous ammonia to obtain a dyeability improver consisting of an ammonium salt of the copolymer. Ta. Synthesis Example 8 According to the method of Synthesis Example 7, neutralization was performed with an aqueous triethanolamine solution instead of aqueous ammonia to obtain a dyeability improver comprising a triethanolamine salt of a copolymer. Table 1 summarizes the maleic acid/acrylic acid molar ratio (γ), average molecular weight (MW), γ×MW, and salt type of the dyeability improvers obtained in Synthesis Examples 1 to 8. Note that MW is determined by GPC (gel permulation chromatography) measurement, and γ is the total remaining monomer amount (maleic acid and acrylic acid) by the promine-promide method, and then the remaining acrylic acid monomer amount by the promide-promate method. The amounts were determined and then calculated.

[Table] Comparative Synthesis Example 1 670 g of ion-exchanged water was placed in a 2- to 4-necked flask equipped with a stirring bar, cooling tube, thermometer, N ₂ gas introduction tube, and dropping funnel, and the temperature was raised to 100°C.
When the temperature inside the system reaches 100℃, 80% acrylic acid 560
g, 492 g of 48% caustic soda aqueous solution, 74 g of 30% ammonium persulfate, and 132.8 g of 35% hydrogen peroxide solution were each simultaneously added dropwise over 4 hours. After the addition was completed, the mixture was aged at 100°C for 1 hour to obtain an aqueous solution of sodium polyacrylate. The molecular weight was approximately 5000 when measured by GPC. Comparative Synthesis Example 2 Using the equipment used in Comparative Synthesis Example 1, put 1200 g of 20% isopropyl alcohol aqueous solution in a flask.
was charged and the temperature was raised to 80°C. When the temperature inside the system reached 80° C., 224 g of 98% acrylic acid and 71 g of a 10% ammonium persulfate aqueous solution were simultaneously added dropwise over 2 hours. After the addition was completed, the mixture was aged at 80° C. for 1 hour, and then the isopropyl alcohol was removed, and 246 g of a 48% caustic soda aqueous solution was added to neutralize the mixture to obtain an aqueous solution of sodium polyacrylate. Furthermore, the molecular weight is
When measured by GPC, it was approximately 3000. Comparative Synthesis Example 3 The polyacrylic acid obtained in Comparative Synthesis Example 2 was neutralized with 179 g of 28% ammonia water instead of caustic soda.
An aqueous solution of ammonium polyacrylate having a molecular weight of about 3000 was obtained. Example 1 A cotton twill fabric was dyed, and its hue, level dyeing property, and dye dispersibility of the dye solution were examined. The results are shown in Table 2. <Dyeing conditions> Hardness of water used: 0 and 20゜DH Dye Kayarus Spra Blue 4BL conc.1%owf
(Metal-containing type direct dye manufactured by Nippon Kayaku Co., Ltd.) Glauber's salt 10% owf Concomitant agents Table 2 Reference bath Ratio 1:30 Dyeing temperature 90℃ Dyeing time 30 minutes Notes Soaping by conventional method after dyeing <Evaluation> Dyeing The color of the fabric was measured using an SM color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd., and the Hue value (value on the Munsell color wheel) was determined to determine the hue. In addition, the level staining property was determined by measuring the unevenness of partial dark color with the naked eye. Furthermore,
Prepare 300 g of a mixture (staining solution) of water, dye (0.1%), and concomitant chemicals (0.1%), and after leaving it for 24 hours, visually judge the state of the over-filtration residue using 5A paper manufactured by Toyo Shi Co., Ltd. This was used as a measure of dye dispersibility.

【table】

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[Table] As is clear from the results in Table 2, when the water hardness is high compared to when the water hardness is low, there is no difference in the Hue value and there is no discoloration (from the dye used) if no concomitant chemicals are used. Although there is no deviation from the hue that should be obtained, there are problems with level dyeing and dye dispersibility. When the concomitant agent is ethylenediaminetetraacetic acid, there is a discrepancy in the Hue value, causing problems with discoloration, and the level dyeing and dye dispersibility are also slightly inferior. On the other hand, when the dyeability improver of the present invention is used as a concomitant agent, there is no deviation in the Hue value, there is no discoloration, and the level dyeing property and dye dispersibility are also good. Note that when water hardness is low, if ethylenediaminetetraacetic acid is used as a concomitant agent, the Hue value will shift and the color will change significantly, resulting in a hue that is significantly different from the hue that should be obtained from the dye used. Example 2 Cotton knit was dyed and its hue, level dyeing property, and dye dispersibility of the dye were investigated. The results are shown in Table 3. <Dyeing conditions> Hardness of water used: 0 and 20゜DH Dye Sumifix Red 3B, 1% owf (metal-containing type reactive dye manufactured by Sumitomo Chemical Co., Ltd.) Glauber's salt 30g/Soda ash 15g/Concomitant chemicals Table 3 reference bath Ratio: 1:30 Dyeing temperature: 60℃ Dyeing time: 30 minutes Notes: After dyeing, soaping according to the usual method <Evaluation> The color of the dyed cloth was measured using an SM color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd., and the Hue value (Munsell The hue was determined by determining the value on the hue wheel. In addition, the level staining property was determined by measuring the unevenness of partial dark color with the naked eye. Furthermore,
Prepare 300 g of a mixed solution (staining solution) of water, dye (0.1%), and concomitant chemicals (0.2%), and after leaving it for 24 hours, visually judge the state of the excess residue using 5A paper manufactured by Toyo Shi Co., Ltd. This was used as a measure of dye dispersibility.

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[Table] As is clear from the results in Table 3, when the water hardness is high compared to when the water hardness is low, if no concomitant chemicals are used, there will be no deviation in Hue value and no discoloration (from the dye used). Although there is no deviation from the hue that should be obtained, there are problems with level dyeing and dye dispersibility. When the concomitant agent is diethylenetriamine pentaacetyl acid, there is a discrepancy in the Hue value, causing problems with discoloration, and the level dyeing and dye dispersibility are also slightly inferior. On the other hand, when the dyeability improver of the present invention is used as a concomitant agent, there is no deviation in the Hue value, there is no discoloration, and the level dyeing property and dye dispersibility are also good. If the water hardness is low, if diethylenetriamine pentaacetic acid is used as a concomitant agent, the Hue value will shift and the color will change significantly, resulting in a hue that is very different from the hue that should be obtained from the dye used. Example 3 A cotton twill fabric was dyed and its color density was examined. The results are shown in Table 4. <Dyeing conditions> Hardness of water used 0, 25, 50゜DH Dye Mikethren Blue RSN s/f, 1%
owf (threen dye manufactured by Mitsui Toatsu Chemical Co., Ltd.) Sodium hydrosulfite 4g / Caustic soda 5g / Concomitant agents See Table 4 Dyeing temperature 60℃ Dyeing time 20 minutes Notes After dyeing, oxidation and soaping using the usual method <Evaluation> Dyeing The color of the fabric was measured using an SM color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd., and the C ^* value was determined, which was used as a measure of color density.

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[Table] As is clear from the results in Table 4, when no concomitant drugs were used, as the water hardness increased,
C ^* value becomes small and color density is not obtained. When ethylenediaminetetraacetate acid is used as a concomitant drug, although there is some improvement, the effect is small. When the stainability improver of the present invention is used as a concomitant drug for these,
Conversely, as water hardness increases, the C ^* value increases, producing a dark color effect. When using the product obtained in the comparative synthesis example, even when the water hardness increases, it shows a C ^* value that is almost the same as the level of water with zero hardness, but it does not reach the level of producing a deep color effect. Not yet. Example 4 Cotton knit was dyed and its color density was examined. The results are shown in Table 5. <Dyeing conditions> Hardness of water used 0, 25, 50゜DH Dye Mikethren Brilliant Green FFB
pdr.1% owf (threen dye manufactured by Mitsui Toatsu Kagaku Co., Ltd.) Sodium hydrosulfite 4g/ Caustic soda 5g/ Concomitant drugs See Table 5 Dyeing temperature 60℃ Dyeing time 20 minutes Notes After dyeing, oxidize and soap in the usual manner. Evaluation> The color of the dyed cloth was measured using an SM color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd., and the C ^* value was determined, which was used as a measure of color density.

【table】

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【table】

[Table] As is clear from the results in Table 5, when no concomitant drugs were used, as the water hardness increased,
C ^* value becomes small and color density is not obtained. When diethylenetriamine pentaacetic acid is used as a concomitant drug, the effect is small, although there is some improvement. On the other hand, when the dyeability improver of the present invention is used as a concomitant agent for these, the C ^* value increases as the water hardness increases, and a deep coloring effect is exhibited. When using the product obtained in the comparative synthesis example, even if the water hardness increases, the hardness level is almost the same as that of water with zero hardness.
Although it shows a C ^* value, it has not reached the point where it can produce a deep color effect.

Claims (1)

[Scope of Claims] 1 A copolymer containing maleic acid (MA) and acrylic acid or methacrylic acid (AA) as essential constituent monomers, the molar ratio of the constituent monomers (MA/
AA=γ) is 0.1 to 2.7, and the average molecular weight (MW)
A dyeability improver for cellulose fibers consisting of a salt of a copolymer having a ratio of 1,000 to 8,000. 2. The dyeability improver according to claim 1, wherein γ is 1.15 to 2.7, MW is 1000 to 8000, and γ×MW is 3000 or more.