JP2008013866A - Method for dyeing and functional processing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for dyeing, which maintains functionality and quality of fibers at the same time in dyeing fiber materials by using a supercritical carbon dioxide fluid, etc. <P>SOLUTION: In the method, when dyeing in the supercritical carbon dioxide fluid, a functionalizing agent which is previously kneaded in the fiber is contained in the supercritical carbon dioxide fluid, concentration gradient of the functionalizing agent in the fiber and in the supercritical carbon dioxide fluid is balanced, and bleed out of the functionalizing agent in the fiber is suppressed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dyeing and functional processing method in a supercritical carbon dioxide fluid, and in particular, when dyeing, a supercritical fluid is obtained without impairing the functional properties and quality of the fiber itself before dyeing. It is related with the method of using and dye | staining.

  Conventionally, various methods are known as methods for dyeing and functionally processing fiber structures. As for the dyeing method, a method of dyeing with water and a large amount of heat energy in combination with a dye and various auxiliary agents is generally used, and regarding a functional processing method using an aqueous dispersion functional agent and / or an aqueous functional agent. In addition, there are known a method of processing the simultaneous dyeing exhaust function and a method of padding (Dip → Nip → Dry → Cure) using a binder, and in any case, a large amount of waste liquid is generated. While recent efforts to improve the global environment are screamed, improvement of wastewater treatment technology is desired.

  For example, as a new wastewater (wastewater) treatment process, wastewater containing a large amount of dyes, processing agents, and various functional agents in dyeing function processing due to consideration for the global environment (air pollution, wastewater pollution, effective use of resources, etc.) A method has been proposed for decomposing sucrose using a photocatalyst or a microorganism. However, since the treatment involves an increase in chemical cost, equipment cost, etc., it is quite difficult as an industrialization technology for wastewater treatment, and there is a disadvantage at present.

  In addition, as a method for reducing wastewater (waste liquid) treatment costs after other dyeing and functional processing, Patent Document 1 discloses that wastewater (waste liquid) is dyed by using a supercritical fluid for dyeing fiber structures. In addition, a method has been proposed in which dyes that have not been dyed (dye exhausted) (undyed dyes) can be completely recovered without using dyeing assistants that have been used in large quantities in the past. Yes. Although there is a possibility that the waste water for dyeing and functional processing can be greatly reduced by this method, it is performed at a higher pressure than normal dyeing, so a special device such as an autoclave type device is required for the dyeing device, and therefore fluid circulation Since the process is carried out in the absence of the above, the processing quality (uniform dyeability, processability, texture, solubility of the processing agent and availability, etc.) cannot be said to be sufficient.

  As a solution to this problem, Patent Document 2 proposes a method of attaching a dye and a functional agent while circulating a supercritical fluid. Dyeing with improved processing quality can be achieved by this method, but a functional agent such as a flame retardant kneaded into the fiber itself or a UV absorber (light resistance improver) is bleeded out by a supercritical dyeing process, There was a problem that it was difficult to achieve both the functional characteristics and quality of the fiber.

JP-A-4-245918 JP 2002-212884 A

  The object of the present invention is to solve the above-mentioned problems of the prior art and retain the dyeing and functional characteristics and quality of the fiber when dyeing all fiber materials using a supercritical fluid such as a supercritical carbon dioxide fluid. It is to provide a processing method.

  As a result of diligent investigations to achieve the above object, the present inventors have determined that a functional agent previously kneaded in the fiber is supercritical dioxide when exhausting (dying) the dye while circulating the supercritical carbon dioxide fluid. By investigating in the fluid, it was found that the bleeding out of the functional agent kneaded into the fiber can be suppressed, and the present invention has been achieved.

  That is, according to the present invention, when dyeing in a supercritical carbon dioxide fluid, a function agent kneaded in advance is included in the supercritical carbon dioxide fluid, so that the function in the fiber and in the supercritical carbon dioxide fluid is achieved. Since the concentration gradient of the agent can be balanced and bleed-out of the functional agent in the fiber can be suppressed, the functional characteristics and quality of the fiber can be maintained simultaneously with the dyeing.

  When dyeing in supercritical carbon dioxide fluid, bleeding out of the functional agent in the fiber, which was a problem, is suppressed, so that not only the characteristics and quality of the fiber are maintained, but also drainage (waste liquid) is dyed zero. Therefore, it becomes a very efficient processing method.

  A supercritical fluid is a fluid under temperature and pressure above the critical temperature and pressure and is defined as a non-condensable dense fluid. This state cannot be said to belong to either the gas phase or the liquid phase, and has a mobility comparable to that of a gas, although the density is similar to that of a liquid.

The supercritical fluid includes a gas or liquid fluid which is in a high pressure state sufficiently higher than the pressure of an apparatus used in normal fiber processing, for example, 1 MPa or more.
Examples of such supercritical fluids (including gas or liquid fluids in a high pressure state) include carbon dioxide, nitrogen, water, ethanol, methanol, etc. In consideration of safety, heat resistance / pressure resistance / corrosion resistance of equipment, etc., carbon dioxide is used in the present invention. Carbon dioxide has a critical temperature of 31.1 ° C. and a critical pressure of 7.2 Mpa.

  Supercritical carbon dioxide causes a large density change with a slight change in pressure, and also has low viscosity and high diffusivity, so it can dissolve various dyes, especially those that have no polarity. The dye can penetrate into the details of the fiber structure and is considered to be a fluid suitable for dyeing. However, in the fiber material in which the functional agent is kneaded, the functional agent bleeds out in the dyeing using the supercritical carbon dioxide fluid, and it is difficult to express original fiber characteristics and basic quality. There was a problem.

  In view of the present situation, the present invention contains a functional agent of the same type as the functional agent kneaded in the fiber as a means for suppressing bleed out of the functional agent, preferably the same amount or more is contained in the supercritical carbon dioxide fluid. Thus, the present invention has been completed by finding out that the bleeding out of the functional agent can be remarkably suppressed.

  The fiber referred to in the present invention may be any shape such as fabric, yarn, cotton, and non-woven fabric, and if it is a fiber material in which a functional agent is kneaded, polyester, polypropylene, polyethylene, PBO, aramid, Nylon-based or polyvinyl chloride-based may be used, and may be mixed fiber, mixed spinning, knitted fabric made of each, or mixed fiber, mixed spinning, knitted fabric with natural fibers such as cotton, wool, hemp, etc. .

  In addition, although the dye used by this invention can use a disperse dye, a cationic dye, and an oil-soluble dye, a disperse dye is especially preferable. As the disperse dye, a dye which is hardly soluble in water and used for dyeing hydrophobic fibers from a system dispersed in water can be used, and benzeneazo type (monoazo) which is usually used for dyeing polyester fibers, acetate fibers and the like. , Disazo, etc.), heterocyclic azo series (thiazole azo, benzothiazole azo, quinoline azo, pyridine azo, imidazole azo, thiophenone azo, etc.), anthraquinone series, and condensed systems (quinophthaline, styrin, coumarin) can be arbitrarily used. Moreover, the one where the pigment | dye solid content density | concentration in dye is higher is easy to dye and is preferable.

  In addition, the functional agent referred to in the present invention is kneaded and added to a fiber in a certain amount to provide flame retardancy, antioxidant properties, ultraviolet absorption (light resistance), dyeability (improvement), antistatic properties, bactericidal properties, It is an agent that imparts functions such as deodorizing properties. For example, as a flame retardant, a known halogen-based, phosphoric ester-based flame retardant, as an antioxidant, a known hindered phenol-based antioxidant, an ultraviolet absorber, etc. Are known UV absorbers of benzophenone and benzotriazole, cationic dyeing improvers such as cation dyeing improvers such as alkylbenzenesulfonic acid onium salts, and known antistatic agents such as carbon black and polyalkylene glycol as antistatic agents. An antistatic agent etc. can be used conveniently. Further, pigments for coloring and gloss adjustment, inorganic particles, and the like can also be used. It is preferable to use one or more functional agents selected from the group of these functional agents.

  The treatment with the supercritical carbon dioxide fluid is preferably performed at 100 ° C. or higher, more preferably 130 ° C. or higher. When the treatment temperature is less than 100 ° C., stained spots become obvious and processing reproducibility may be inferior. The pressure is preferably 15 Mpa, and if it is less than 15 Mpa, the reproducibility and workability may be inferior. In addition, if the circulating flow rate of the fluid is significantly reduced, the workability and quality may be deteriorated. Therefore, the higher the processing temperature, pressure, and circulating flow rate, as much as possible in the equipment specifications, the more uniform and the deep dyeing property. improves.

Next, the present invention will be described in more detail with reference to examples. In addition, the physical property in an Example was measured with the following method.
(1) Dyeability Evaluation of stainability was performed using Macbeth COLOR-EYE model CE-3100.
The dyeing property of the entire fabric is expressed by the lightness index L *. The lightness index L * is JIS Z 8701 (color display method by 2 degree visual field XYZ system) or JIS Z 8728 (color by 10 degree visual field XYZ system). Using the tristimulus value Y defined in (Display method), the following expression is used. Here, the lightness index L * indicates that the smaller the value, the deeper the dyeing.
In the case of Y / Y _n > 0.008856 Y: Tristimulus value in XYZ Y _n : Y value by standard light of a completely diffuse reflecting surface L * = 116 (Y / Y _n ) ^1/3 -16
However, in the case of Y / Y _n ≦ 0.008856, the following formula is used.
_{L * = 903.29 (Y / Y} n)
(2) Fineness, fiber length, strength, elongation, shrinkage rate Measured according to JIS L1015.

[Example 1]
Dissolve 30 g of poly-m-phenyleneisophthalamide of IV 1.35 dl / g in 110 g of N-methyl-2-pyrrolidone, and mix and dissolve 3.6 g of tributylbenzylammonium ammonium dodecylbenzenesulfonate which is a cationic dye. Then, vacuum degassing was performed to obtain a spinning dope.

  This dope was heated to 85 ° C. and wet-spun into a coagulation bath from a spinneret having a diameter of 0.07 mm and a hole number of 200. The composition of the coagulation bath was 40% by weight of calcium chloride, 5% by weight of NMP, 55% by weight of the remaining water, and the temperature of the coagulation bath was 85 ° C. The yarn was moved about 10 cm into the coagulation bath and pulled out at a speed of 6.2 m / min. The yarn is washed with water, stretched 3.3 times with warm water at 95 ° C., dried with a roll at 120 ° C., and then stretched 1.0 times on a hot plate at 300 ° C. to draw a 364 dtex / 200 filament drawn yarn. Got. 100 stretched yarns were bundled into a 20,000 denier tow, which was crimped and then cut. The fineness, cut length, strength, elongation, shrinkage rate at 300 ° C., and shrinkage rate at 135 ° C. of wet heat were 1.5 dtex, 51 mm, 3.8 g / dtex, 43.6%, and 8.4%, respectively. It was 5.2%.

Using this short fiber, it is blended and twisted in the usual way to form a 30/2 spun yarn, then woven, and (30/2 × 30/2) / (55 / in × 54 / in) flat A woven fabric was obtained. Next, the fabric was refined with score roll 400 (manufactured by Kao) at 1 g / l and 80 ° C. for 20 minutes. After washing and drying, it was pre-set at 190 ° C. for 1 minute. Next, the following dye and an organic solvent (benzyl alcohol and water) were used, and dyeing treatment was performed in a supercritical carbon dioxide fluid using a 2.6 L supercritical carbon dioxide treatment apparatus at 130 ° C. × 25 MPa × 30 minutes. The dyed product obtained was washed with acetone and subjected to various evaluations.
Dye: C.I. I. Disperse Blue 56 1% owf
Dodecylbenzenesulfonate tributylbenzylammonium salt 2% owf
As a result, the dyeability L * was 55.1, the internal permeability of the dye was good, and the cationic dyeing agent retention rate in the fiber was 85%.

・・・式（１） [Example 2]
A fluid containing 6 wt% of a phosphate ester flame retardant represented by the following formula (1) in Example 1 and containing 6 wt% of the flame retardant in the supercritical carbon dioxide fluid concentration during supercritical carbon dioxide treatment In the same manner except that simultaneous dyeing was performed, the evaluation was performed. As a result, the dyeability L *: 53.8, the internal permeability of the dye was good, and the flame retardant retention rate in the fiber was 90%, so the flame retardancy was good.

... Formula (1)

・・・式（２） [Example 3]
In Example 1, a fiber containing 5 wt% of a benzotriazole-based ultraviolet absorber (light resistance improver) represented by the following formula (2) was used, and the supercritical carbon dioxide fluid concentration was used during supercritical carbon dioxide treatment. It processed and evaluated similarly except having performed simultaneous dyeing | staining with the fluid contained in 5 wt%.
As a result, the dyeability L * was 54.2, the internal permeability of the dye was good, and the ultraviolet absorbent retention rate in the fiber was 90%.

... Formula (2)

[Comparative Example 1]
In Example 1, the same treatment and evaluation were conducted except that tributylbenzylammonium dodecylbenzenesulfonate was not used in the supercritical carbon dioxide bath. As a result, the dyeability L *: 54.9 and the internal permeability of the dye were good, but since the dye was not added to the dye bath, the retention rate of the cationic dye in the fiber decreased to 45%. It was.

[Comparative Example 2]
In Example 2, it processed similarly and evaluated except not using the flame retardant in the supercritical carbon dioxide bath. As a result, the dyeability L *: 54.3 and the dye internal permeability were good, but the functional agent retention was 50%.

[Comparative Example 3]
In Example 3, it processed similarly and evaluated except not using the ultraviolet absorber in a supercritical carbon dioxide bath. As a result, the dyeability L *: 53.1 and the internal permeability of the dye were good, but the functional agent retention was 20%.

  When the supercritical fluid carbon dioxide is circulated while dye is exhausted (dyed), the functional agent previously kneaded in the fiber is contained in the supercritical dioxide fluid, so that the functional agent kneaded in the fiber Since bleed-out can be suppressed, it is possible to achieve both dyeing and fiber quality and function, and the industrial value is extremely high as a global environmental improvement type dyeing function processing method.

Claims (4)

  In dyeing a fiber with a dye in a supercritical carbon dioxide fluid, a functional agent previously kneaded in the fiber is contained in the supercritical carbon dioxide fluid. Dyeing and functional processing methods.   The dyeing in a supercritical carbon dioxide fluid according to claim 1, wherein the fiber comprises at least one of polyester fiber, polypropylene fiber, polyethylene fiber, nylon fiber, aramid fiber, polybenzoxazole (PBO) fiber, and polycarbonate (PC) fiber. Functional processing method.   The functional agent is at least one functional agent selected from the group consisting of flame retardants, antioxidants, ultraviolet absorbers, cationic dyes, antistatic agents, bactericides, deodorants, pigments, and inorganic particles. The dyeing | staining and functional processing method in the supercritical carbon dioxide fluid as described in any one of 1-2.   The dyeing and functional processing method according to any one of claims 1 to 3, wherein the dye is a disperse dye or an oil-soluble dye.