JPH0437190B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for high-temperature dyeing of polyester fibers. More specifically, the present invention relates to a dyeing method for obtaining a uniformly dyed product when unrefined polyester fibers are dyed using a disperse dye. [Prior art and problems to be solved by the invention] [Reducing processing costs is a very important problem in recent dyeing processing, and various studies have been made. One way to reduce processing costs is to shorten the dyeing process, which currently takes a long time. In the dyeing process of polyester fibers, scouring, dyeing, and reduction washing are usually carried out separately in sequence, but a one-bath scouring dyeing method in which these steps are carried out simultaneously is desired. In the dyeing process of polyester fibers, residual monomers and low-molecular substances from polyester polymerization, as well as oils and glues used during spinning, weaving, and knitting, can be a major problem in dyeing and post-processing. Therefore, it is common to perform a scouring process in advance to remove them. Of the stains targeted in the scouring process, oils are easily removed using surfactants, but adhesives such as polyacrylic esters and polyvinyl alcohol must be removed in combination with alkaline agents. Before processing, a scouring process is performed using an alkaline agent. On the other hand, polyester fibers are usually dyed using disperse dyes at around 130℃, and the pH of the dye bath is
is adjusted to neutral to weakly acidic with a weak acid such as acetic acid. The reason for adjusting the PH to neutral to weakly acidic is that alkaline agents used in the scouring process, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium tripolyphosphate, potassium tripolyphosphate, and sodium pyrophosphate, are usually used in the scouring process. , potassium pyrophosphate, sodium metaphosphate, potassium metaphosphate, sodium metasilicate, potassium metasilicate, etc. are added to high-temperature dyeing in an alkaline region, and the stability of disperse dyes is poor.
This is because it becomes difficult to maintain dyeing reproducibility and color clarity. That is, scouring must be performed in alkaline conditions and dyeing must be performed in acidic conditions, which is a major drawback when performing scouring and dyeing in one bath. In an attempt to solve these problems, a one-bath scouring dyeing method for polyester fibers was developed.
A method disclosed in Publication No. 24554 has been proposed. The method disclosed in Japanese Patent Publication No. 62-24554 involves incorporating monovalent, divalent and polyvalent carboxylic acid esters, surfactants, and alkaline agents into the dye bath when dyeing unscoured polyester fibers at high temperatures. of
Up to around 100°C, the dye bath becomes alkaline due to the added alkaline agent, scouring treatment is performed, and the oil and sizing agent fall off from the fibers into the dye bath. Next, when the temperature exceeds that temperature, the carboxylic acid ester is hydrolyzed by an alkaline agent or high temperature conditions, generating free carboxylic acid, and the pH becomes acidic. In other words, this proposal suggests that the dye bath can be alkaline, neutral, or
It is disclosed that one-bath scouring dyeing is possible because it changes in order of acidity. However, in the method disclosed in Japanese Patent Publication No. 62-24554, the PH becomes acidic in the latter stage of dyeing, so the sizing agent becomes insoluble in water again, causing uneven dyeing and hardening of the texture, as well as polyester hydrolyzate. It has many drawbacks, such as terephthalic acid, etc., which re-adheres to the fibers and degrades their quality, making them unsuitable for industrial production. Furthermore, in the prior art, when polyester fibers are dyed with disperse dyes, problems occur in color fastness due to undyed disperse dyes that do not diffuse into the interior of the fibers but remain on the surface of the fibers. Therefore, in order to disperse and remove the dye remaining on the fiber surface after the dyeing process is completed,
A reduction cleaning process that involves treatment for 10 to 30 minutes at a temperature of 80 to 100°C in a bath containing a reducing agent such as sodium hydrosulfite and an alkaline agent is essential, and it simplifies and streamlines the dyeing process. This has become an obstacle in promoting the project. [Means for Solving the Problems] Therefore, as a result of intensive studies to solve these technical problems, the present inventors found that when dyeing polyester fibers, the following (a) component and/or (b) The inventors have discovered that the above-mentioned problems can be solved by incorporating component ) into the dyebath, and have completed the present invention. That is, the present invention relates to a water-soluble or water-dispersible polymer or copolymer obtained by polymerizing or copolymerizing unscoured polyester fiber with (a) an unsaturated carboxylic acid or a monomer containing it as a main component; salt, and/or
or (b) general formula (In the formula, A is -CH ₂ COOM ₃ , or , M ₁ to M ₉ are H or Li, K, Na, NH ₄ ,
Any alkanolamine. a, b,
c and d are integers from 2 to 10. ) This relates to a one-bath scouring dyeing method for polyester fibers, which is characterized by dyeing at high temperature with an alkaline pH of 9.0 or higher in a dye bath containing a compound represented by It is possible to provide a one-bath scouring dyeing method for polyester fibers, which has little effect on the stability of the dye even when the pH of the dye is 9.0 or higher, and which makes it possible to omit reduction washing, which is a post-dying process. In the present invention, the monomers used to obtain the above component (a) include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, derivatives thereof, These include alkali metal salts (sodium salts, etc.), ammonium salts, organic amine salts (triethanolamine salts, etc.), or mixtures thereof.
In addition to these monomers, copolymerizable monomers such as vinyl acetate, isobutylene, diisobutylene, and styrene can also be used as copolymerization components. Conventionally known methods can be used to polymerize these monomers. Although there are no particular restrictions on the ratio of monomer components and the degree of polymerization of the polymer or copolymer, it is necessary that the salt of the polymer or copolymer is at least water-soluble or water-dispersible. Specific examples of salts of polymers or copolymers include alkaline acid polymers, methacrylic acid polymers, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and acrylic acid methyl ester, Polymers or copolymers such as copolymers of acrylic acid and vinyl acetate, copolymers of acrylic acid and maleic acid, copolymers of maleic acid and isobutylene, copolymers of maleic acid and styrene, etc. , salts with alkali metals, ammonia and organic amines. Two or more kinds of salts of these polymers or copolymers can also be used. The polymer or copolymer salt that can be preferably used as component (a) of the present invention has an average molecular weight of
1000 to 10000. The above component (b) that can be used in the present invention includes, for example, trisodium nitrilotriacetate, tripotassium nitrilotriacetate, trisodium ethylenediaminetetraacetate, tripotassium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, Tetrapotassium ethylenediaminetetraacetate, trisodium hydroxyethyl/ethylenediaminetriacetate, tripotassium hydroxyethyl/ethylenediaminetriacetate, tetrasodium diethylenetriaminepentaacetate, tetrapotassium diethylenetriaminepentaacetate, pentasodium diethylenetriaminepentaacetate,
Examples include pentapotassium diethylenetriaminepentaacetate. In the one-bath scouring dyeing method for polyester fibers of the present invention, the above-mentioned components (a) and (b) are preferably used alone or in a mixture, preferably in a mixture. Therefore, it becomes possible to perform one-bath scouring dyeing of polyester fibers, and the conventional problems are solved. The amount of component (a) and component (b) added in the present invention is not particularly limited, but the total amount of component (a) and (b) in the weight of the dye bath is preferably 0.01 to 10% by weight.
Effects can be exhibited by adding 0.05 to 2% by weight. In the present invention, in addition to these components, a surfactant for imparting uniform dyeability to the fibers and a surfactant for imparting scouring properties to the oil agent can be used in combination. Examples of these surfactants include polyoxyethylene sorbitan trioleate and polyoxyethylene tribenzyl phenyl ether. Furthermore, for the purpose of preventing reductive decomposition of disperse dyes,
Sodium metanitrosulfonate, sodium chlorate, etc. can be used in combination. The method of the present invention can be applied to any textile product containing unscoured polyester fibers, and is applicable not only to yarns, knitted fabrics, and woven fabrics made of polyester fibers alone, but also to yarns, knitted fabrics, and woven fabrics made of polyester fibers in combination with other fibers. It may be a blended product, a mixed knitted fabric, or a mixed fabric containing the above material. When performing the one-bath scouring dyeing method of the present invention, the above (a)
Component and/or component (b) is added to the dye bath, and the PH of the dye bath is
is adjusted to an alkalinity of 9.0 or higher, preferably 9.0 to 10.0, and dyeing is carried out at a bath ratio of 1:5 to 1:20 at a temperature of 100 to 140°C. [Function] The mechanism by which uniform and high-quality dyed products can be obtained with good reproducibility by the one-bath scouring dyeing method for polyester fibers of the present invention is not necessarily clear, but it is thought to be as follows. First, the reason why the present invention does not inhibit the stability of disperse dyes even though they are alkaline is that these compounds are able to absorb into dye particles due to the adsorption ability of the component (a) and/or (b) of the present invention. This is to form an adsorption film on the surface of the dye and prevent it from being exposed to alkali.On the other hand, since the usual alkaline agents mentioned above do not have adsorption properties to the dye particles, the dye particles come into direct contact with the alkali and are decomposed. It is thought that this will progress. Furthermore, since the dye bath is alkaline, acrylic and polyvinyl alcohol-based glues are easily dissolved in water, and the above-mentioned component (a) has superior properties against water-insoluble inorganic substances and high-molecular organic substances. It is presumed that this is to prevent re-adhesion of acrylic, polyvinyl alcohol, starch-based sizing agents, polyester oligomers, and their scales to the fibers due to the dispersion ability of component (b). This is thought to be due to the metal ion sequestering ability that prevents the polyvalent metal ions contained in the fibers and dyeing water from binding and becoming insolubilized. Furthermore, when dyeing polyester fibers using disperse dyes that are poorly soluble in water, the disperse dyes become more hydrophobic under acidic conditions, resulting in poor dye dispersibility and aggregation of the dyes. Therefore, dyeing is carried out by adding a dispersant, which is a surfactant, but it is still not sufficient and uneven dyeing often occurs. Furthermore, since agglomerated dyes do not diffuse well into the fibers and remain attached to the surface, impairing color fastness, a reduction washing step must be performed. On the other hand, by making the dye bath alkaline, the hydrophilicity of the dye becomes stronger, which leads to the ideal monomolecularization of the dye in the dyeing of polyester fibers, and the adsorption of the dye becomes gentle, resulting in uniform dyeing properties. is obtained, and the amount of undyed agglomerated dye on the fiber surface is reduced, and it is presumed that a dyed product with good fastness can be obtained even if the reduction washing step after dyeing is omitted. Furthermore, it is believed that by making the dye bath alkaline, the hydrophobic polyester fibers are made hydrophilic, and the redeposition of the hydrophobic polyester oligomers can also be prevented. [Examples] The present invention will be specifically illustrated by examples below, but the method of the present invention is not limited only to these examples. Example 1 15 g of unscoured polyester processed yarn fabric was dyed using an experimental dyeing machine (Color Master HD- manufactured by Tsujii Dye Machinery Co., Ltd.).
12E type), add the compounds shown in Table 1,
Treatment was performed at a bath ratio of 1:10 and a treatment temperature of 130°C for 10 minutes, and then cooled to about 50°C, washed with water, and dried. The scouring property (descaling property) of the treated fabric was evaluated in a 0.1% aqueous solution of cationic dye (CI Basic Red 10).
Dyeing was carried out at .degree. C. for 5 minutes, and the adhesion of the cationic dye to the remaining paste was evaluated according to the following criteria. The formulation examples and results are shown in Table 1. <Judgment Criteria> ○...No cationic dye staining was observed, and the desizing property was good. ×: Dyeing with cationic dye was significant, and desizing performance was poor.

[Table] As can be seen from Table 1, it can be seen that the formulation examples of the present invention are excellent in desizing properties. Example 2 1 kg of unrefined polyester filament yarn was dyed using an experimental cheese dyeing machine (1LUP-F1V manufactured by Nippon Senzo Kikai Co., Ltd.).
Using a mold), the compounds shown in Table 2 were added and dyed under the following conditions, and the state of adhesion of the polyester oligomer in the inner layer of the cheese was visually judged according to the following criteria. The results are shown in Table 2. <Dyeing conditions> Dye: Panorama Black VF-6 (P) (manufactured by Nippon Chemical Products Co., Ltd.) 6% owf Bath ratio: 1:10 Temperature x time: 130℃ x 30min <Judgment criteria> ○...inner layer is outer layer No oligomers were observed. △…The inner layer is slightly whiter than the outer layer, and some oligomers are attached. ×: The inner layer is much whiter than the outer layer, and a large amount of oligomer is attached.

[Table] As can be seen from Table 2, it can be seen that in the example formulation of the present invention, the adhesion of oligomers to the inner layer of cheese is extremely less than in the comparative example formulation, indicating that it is superior. Example 3 15 g of unrefined polyester processed yarn fabric was dyed using an experimental dyeing machine (Color Master HD- manufactured by Tsujii Dye Machinery Co., Ltd.).
12E type) in a dye solution with a pH of 9.5 containing 1 g of sodium polyacrylate (molecular weight approximately 6000) and 0.5 g of tetrasodium ethylenediaminetetraacetate at a bath ratio of 1:10 and a temperature of 130°C for 30 minutes. After dyeing, the dyed fabric was washed with water and dried, and its level dyeing properties, build-up properties, color fastness, and ability to prevent scale from re-adhering to the fiber surface were examined. The results are shown in Table 3. Example 4 15 g of unscoured polyester processed yarn fabric was dyed using an experimental dyeing machine (Color Master HD- manufactured by Tsujii Dye Machinery Co., Ltd.).
12E type), sodium salt of acrylic acid/maleic acid copolymer (molecular weight approximately 3000, copolymerization ratio
After dyeing in a dye solution with a pH of 9.5 containing 1 g/0.8:0.2) and 0.5 g/tetrasodium ethylenediaminetetraacetate at a bath ratio of 1:10 and a temperature of 130°C for 30 minutes, it was washed with water and dried. About the dyed cloth,
Level dyeing properties, build-up properties, color fastness, and prevention of scale re-deposition on the fiber surface were investigated. The results are shown in Table 3. Example 5 15 g of unrefined polyester processed yarn fabric was dyed using an experimental dyeing machine (Color Master HD- manufactured by Tsujii Dye Machinery Co., Ltd.).
12E type), sodium polyacrylate (molecular weight approximately 6000) 1g/, tetrasodium ethylenediaminetetraacetate 0.5g/, sodium metanitrosulfonate 0.5g/, polyoxyethylene (15)
Contains sorbitan trioleate 0.3g/
In a dye solution with pH 9.5, bath ratio 1:10, temperature 130℃
After dyeing for 30 minutes, the dyed fabric was washed with water and dried, and its level dyeing properties, build-up properties, color fastness, and ability to prevent scale from re-adhering to the fiber surface were examined. The results are shown in Table 3. Comparative Example 1 15 g of unscoured polyester processed yarn fabric was dyed using an experimental dyeing machine (Color Master HD- manufactured by Tsujii Dye Machinery Co., Ltd.).
12E type) in a dye solution with a pH of 9.5 containing 1 g of sodium hydroxide and 0.3 g of polyoxyethylene (15) nonylphenol ether.
After dyeing at a bath ratio of 1:10 and a temperature of 130°C for 30 minutes, the dyed fabric was washed with water and dried.
The build-up properties, color fastness, and prevention of scale re-deposition on the fiber surface were investigated. The results are shown in Table 3. Comparative Example 2 15 g of unscoured polyester processed yarn fabric was dyed using an experimental dyeing machine (Color Master HD- manufactured by Tsujii Dye Machinery Co., Ltd.).
12E type), acetic acid 0.3g/, polyoxyethylene (15) sorbitan trioleate 0.3g/
In a dye solution containing PH 4.5, bath ratio 1:10,
After dyeing at a temperature of 130°C for 30 minutes, the dyed fabric was washed with water and dried, and its level dyeing properties, build-up properties, color fastness, and ability to prevent scale from re-adhering to the fiber surface were examined. The results are shown in Table 3. Comparative Example 3 15 g of unscoured polyester processed yarn fabric was dyed using an experimental dyeing machine (Color Master HD- manufactured by Tsujii Dye Machinery Co., Ltd.).
12E type), diethyl glutarate 2.0g/,
In a dye solution containing 1.0 g of tribenzyl phenyl ether with a pH of 10.5, at a bath ratio of 1:10 and a temperature of
After dyeing at 130℃ for 30 minutes, the dyed fabric was washed with water and dried.
Color fastness and ability to prevent scale from re-adhering to fiber surfaces were investigated. The results are shown in Table 3. Comparative Example 4 15 g of unscoured polyester processed yarn fabric was heated to 95% by weight in a bath containing 2 g of sodium carbonate and 1 g of polyoxyethylene (9) nonylphenol ether.
Scouring treatment at ℃ for 30 minutes and washing thoroughly with water.
Thereafter, using an experimental dyeing machine (Color Master HD-12E model manufactured by Tsujii Senko Kogyo Co., Ltd.), in a dye solution containing 0.3 g of acetic acid and a pH of 4.5, the bath ratio was 1:10.
After dyeing at a temperature of 130°C for 30 minutes, the dyed fabric was washed with water and dried, and its level dyeing properties, build-up properties, color fastness, and ability to prevent scale from re-adhering to the fiber surface were examined. The results are shown in Table 3. In addition, in any of Examples 3 to 5 and Comparative Examples 1 to 4, dyeing tests were conducted using the following dyes. 1.CI Disperse Red 288 3.0%owf 2.CI Dispersu Red 258 1.0%owf 3.CI Dispersu Blue 214 1.0%owf Also, the level dyeing properties of the dyed fabrics obtained in Examples 3 to 5 and Comparative Examples 1 to 4 , build-up properties, color fastness,
The ability to prevent scale re-deposition on the fiber surface was investigated using the following method. (A) Level dyeing property The uneven dyeing condition of the dyed fabric was observed with the naked eye, and the following 5
Judgment was made based on the grade criteria. ◎…No uneven dyeing○…Slightly uneven dyeing△…Slightly uneven dyeing×…Many uneven dyeing××…Very uneven dyeing (B) Build-up property The dyed fabric was dyed using SM Color Computer SM manufactured by Suga Test Instruments Co., Ltd. -3 type, the C ^* value was determined, and the relative dyeing rate (%) was calculated using the following calculation formula. Relative dyeing rate (%) = C ^* of each dyed fabric / C ^* of dyed fabric of Comparative Example 4 × 100 (Note) C ^* is C ^* = 21.72 × 10 ^C

Claims (1)

[Scope of Claims] 1. Unscoured polyester fibers, (a) a water-soluble or water-dispersible polymer or copolymer obtained by polymerizing or copolymerizing an unsaturated carboxylic acid or a monomer containing it as a main component; polymer salts, and/or
or (b) general formula (In the formula, A is -CH ₂ COOM ₃ , or , M ₁ to M ₉ are H or Li, K, Na, NH ₄ ,
Any alkanolamine. a, b,
c and d are integers from 2 to 10. ) A one-bath scouring dyeing method for polyester fibers, which is characterized by dyeing at high temperature with an alkaline pH of 9.0 or higher in a dye bath containing the compound represented by the formula.