JP2011001652A - Dyed product of blended yarns or fabric of polyamide fiber and polyurethane fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dyed product of blended yarns or fabric of polyamide fibers and polyurethane fibers, which has high color development, is free from exposure of undyed fibers and bleeding, has high color fastness, and holds a soft texture, and to provide a method for producing the dyed product of the blended yarns or fabric.SOLUTION: There are provided the dyed product of blended yarns or fabric of polyamide fibers and the polyurethane fibers, wherein the blended yarns or fabric of polyamide fibers and polyurethane fibers preliminarily containing a quaternary ammonium salt are dyed with a metal complex azo reactive dye; and the method for producing the dyed product of blended yarns or fabric of polyamide fibers and polyurethane fibers, including the following step: dyeing the blended yarns or fabric of polyamide fibers and polyurethane fibers preliminarily containing a quaternary ammonium salt with a metal complex azo reactive dye.

Description

  The present invention relates to a mixed yarn of polyamide fiber and polyurethane fiber or a dyed product of fabric, and a method for producing the same.

Polyamide fibers have excellent properties such as mechanical strength, chemical resistance, heat resistance, color development, washing durability, and soft touch.
On the other hand, polyurethane fibers have many excellent properties such as a comfortable stretch function, shape retention, fit, moldability, and wrinkle resistance.
Therefore, taking advantage of the soft feel of the polyamide fiber and the expansion and contraction function of the polyurethane fiber, skins such as inner clothing represented by foundations, sports clothing represented by swimwear, leg clothing represented by pantyhose, where both materials are mixed. Widely used for applications worn near the side.

  The mixed fabric of polyamide fiber and polyurethane fiber is generally dyed with an acid dye, and particularly in the dark color field, it is dyed with a metal-containing dye among acid dyes. When dyed with such an acid dye, the polyurethane fiber has a low dyeing property due to the acid dye, so that the same colorability with the polyamide fiber is poor, and the polyurethane fiber is not dyed. When stretched at the time of wearing or the like, there is a problem that a polyurethane fiber having a different color can be seen and a so-called “eye-sucking” phenomenon occurs. In addition, due to this unevenness, there is a problem that the glare feeling peculiar to polyurethane fibers is seen and the commercial value of the product is remarkably lowered.

For this reason, in order to improve the dyeability of the polyurethane fiber with an acid dye, a method of incorporating polyamide fine particles having a specific particle diameter is disclosed in the following Patent Document 1, and a method of incorporating a polymer having a maleimide structure is disclosed. It is disclosed in the following Patent Document 2.
However, with these methods, although the eye lashes are eliminated, when the dye is dyed with a metal-containing dye in the dark color dyeing, when the product is washed or worn with rain, the white color from the dark dyed part is removed. A so-called “color crying” phenomenon occurs in which the dye moves to the field or the light-colored portion, particularly in black, amber, and red, and there is a problem that the commercial value is remarkably lowered.

Further, methods for coloring the polyurethane fiber itself with a pigment, carbon black or the like are disclosed in Patent Documents 3 and 4 below.
However, these methods are effective for eyes with color limited to black, but lack of vividness of color, so that not only a deep and glossy hue can be obtained, but in any color. Has the problem that the same color as polyamide fiber cannot be obtained.

Furthermore, Patent Document 5 discloses a method for obtaining an excellent dyed product of polyamide fiber using a reactive dye.
However, with this method, although the color crying phenomenon is improved, there is a problem in that the eye squeak problem cannot be solved because it is not dyed onto the polyurethane fiber.
Therefore, the actual condition is that satisfactory products are not obtained as a mixed fabric dyed product of polyamide fiber and polyurethane fiber having good quality and excellent color developability and fastness to dyeing without tingling or crying.

JP 2007-46170 A JP 2009-74184 A JP 2003-268603 A JP 2004-60093 A Japanese Patent No. 4229653

  The problem to be solved by the present invention has been made in the background of such circumstances, and even when dyed with a reactive dye, color development is high, there is no unevenness, and the color fastness is excellent and the quality is good. It is to provide a dyed article of a mixed fabric of polyamide fibers and polyurethane fibers, and a method for producing the same.

As a result of intensive investigations and repeated experiments in order to solve the above problems, the present inventor has previously obtained polyurethane fibers when dyeing with a specific reactive dye in a mixed yarn or fabric of polyamide fibers and polyurethane fibers. By adding a specific compound to the above, it was found that an excellent dyed product of the yarn or fabric having no tingling and tingling was obtained, and the present invention was made.
That is, the present invention is as follows.

  [1] A mixed yarn or fabric dyed product of polyamide fiber and polyurethane fiber, wherein the mixed yarn or fabric of polyamide fiber and polyurethane fiber preliminarily containing a quaternary ammonium salt is a metal complex type azo The dyed product characterized by being dyed with a reactive dye.

  [2] A dyed product of a mixed yarn or fabric of a polyamide fiber and a polyurethane fiber according to the above [1], which has a Daimaru method color fastness of 4-5 grade or higher.

[3] A method for producing a mixed yarn of polyamide fiber and polyurethane fiber or a dyed product of fabric, comprising the following steps:
Dyeing a mixed yarn or fabric of polyamide fiber and polyurethane fiber preliminarily containing a quaternary ammonium salt with a metal complex type azo reactive dye,
Including said method.

  [4] A mixed yarn of a polyamide fiber and a polyurethane fiber obtained by the method according to [3] or a dyed product of a fabric.

  [5] A dyed article of a mixed yarn or fabric of the polyamide fiber and the polyurethane fiber according to the above [4], which has a Daimaru method color fastness of 4-5 grade or higher.

  The mixed yarn of the polyamide fiber and the polyurethane fiber according to the present invention or the dyed product of the fabric has high color developability, no unevenness, no color crying, and excellent dyeing fastness.

Hereinafter, the present invention will be described in detail.
According to the present invention, prior to or at the time of dyeing a mixed yarn or fabric of polyamide fiber and polyurethane fiber, the mixed quaternary ammonium salt is adsorbed to the polyurethane fiber constituting the mixed yarn or fabric, thereby the mixed use. If the yarn or fabric is dyed with a metal complex salt type azo reactive dye, it is possible to obtain a dyed product of a mixed yarn or fabric that has high color developability, has no eye-feel, does not cry, and has excellent color fastness. .

In the present invention, “polyamide fiber” includes aliphatic polyamide fibers such as nylon 6, nylon 66, nylon 610, nylon 11, and nylon 12, xylylenediamine polyamide fibers, polymetaphenylene isophthalamide fibers, and polyparaphenylene terephthalamide. Synthetic polyamide fibers such as aromatic polyamide fibers such as fibers, natural polyamide fibers such as silk and wool, and the like can be appropriately selected and used depending on the application.
Further, the form of the fiber may be long fiber or short fiber, and may be uniform or thick in the length direction. Also in the cross section, round shape, triangle shape, L shape, T shape, Y shape, W It may be a polygonal shape such as a shape, an eight-leaf shape, a flat shape, or a dogbone shape, a multi-leaf shape, a hollow shape, or an irregular shape. Furthermore, the yarn forms include spun yarn such as ring spun yarn, open-end spun yarn, multifilament yarn (including extra fine yarn), sweet-twisted yarn to strongly twisted yarn, mixed yarn, false twisted yarn, air-jet processed yarn, etc. Is mentioned. In addition, pigments such as titanium oxide and carbon black, various antioxidants, anti-coloring agents, anti-lighting agents, antistatic agents and the like may be added as long as the object of the present invention is not impaired.

  The polyamide fiber preferably has a single yarn decitex of 0.01 to 5 dtex, more preferably 0.1 to 3 dtex, and a total decitex of 10 to 250 dtex. When such a fiber is used, a fabric excellent in dyeability and texture can be obtained.

In the present invention, as the “polyurethane fiber”, a polyether type having a polyether diol such as polytetramethylene glycol as a diol component, an aromatic diisocyanate such as 4,4′diphenylmethane diisocyanate as a diisocyanate component, and ethylenediamine or the like as a diamine component Polyurethane fiber, polyester diol composed of polycaprolactone, polyester composed of adipic acid / 1,6-hexanediol / neopentyl glycol, aliphatic diol such as butanediol, etc. as diol components, 4,4'diphenylmethane diisocyanate, etc. Polyester-based polyurethane fibers having the aromatic diisocyanate as a diisocyanate component can be appropriately selected and used depending on the application.
In addition, as the polyurethane fiber, either a bright yarn with high sharpness or a semi-dull type with reduced gloss can be appropriately selected and used depending on the application. These types can be controlled by, for example, the amount of titanium oxide added.
The polyurethane fiber may contain a chlorine water deterioration preventing agent such as a metal oxide or a metal hydroxide as necessary. For example, magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide Aluminum hydroxide, hydrotalcite compounds, etc. may be used alone or as a mixture of two or more. The addition amount is preferably 0.1 to 6.0 wt%. In addition, other known stabilizers, ultraviolet absorbers and the like may be contained.

  In the present invention, it is preferable that the polyurethane fiber contains a polymer having a maleimide structure in an amount of 0.2 wt% to 10 wt% from the viewpoint of enhancing the dyeing property of the reactive dye and enhancing the fastness performance. If the amount is less than 0.2 wt%, sufficient dyeability cannot be obtained. On the other hand, if the amount exceeds 10 wt%, the overdyeing is excessively caused, resulting in unevenness of the eyes and deterioration of fastness.

で表されるイソブチレン単位と下記式（ＩＩ）：

｛式中、Ｒ^１は、炭素数２〜６の直鎖又は分岐アルキレン基であり、そしてＲ^２、及びＲ^３は、炭素数１〜６の直鎖又は分岐アルキル基である。｝で表されるマレイミド単位とからなるものであり、イソブチレン単位とマレイミド単位とが交互に反復してなるものが好ましい。 As the polymer having a maleimide structure used in the present invention, the following formula (I):

And an isobutylene unit represented by the following formula (II):

{Wherein, R ¹ is a linear or branched alkylene group having 2 to 6 carbon atoms, and R ² and R ³ are linear or branched alkyl groups having 1 to 6 carbon atoms. }, And those obtained by alternately repeating isobutylene units and maleimide units are preferred.

The weight average molecular weight Mw of the polymer having a maleimide structure contained in the polyurethane fiber according to the present invention is preferably 80,000 to 150,000, and Mw / Mn (Mn is the number average molecular weight) is 3.5 or less. Preferably there is.
The shear viscosity of the polymer having a maleimide structure is preferably in the range of 80 to 300 poise when a 50% dimethylacetamide solution is used.

  The mixing ratio of the polyamide fiber and the polyurethane fiber according to the present invention can be appropriately determined depending on the use, but a preferable result can be obtained when the polyurethane fiber is generally mixed at 40 wt% or less. The mixed dyed product of the present invention is composed of polyamide fiber and polyurethane fiber. In addition to these fibers, cotton, silk, hemp, cupra, viscose rayon and the like may be mixed.

  The mixed dyed product according to the present invention is roughly classified into a yarn form and a fabric form. As the form of the yarn, a yarn in which a bare yarn of polyurethane fiber, that is, a bare yarn (10 to 500 dtex) is coated with a polyamide fiber, for example, a so-called covering yarn (single or double covering), a twisted yarn, a core yarn, an entangled yarn, etc. The form of a well-known covering yarn is mentioned.

On the other hand, the fabric forms include knitted fabrics, woven fabrics, non-woven fabrics, and composite fabrics thereof (for example, laminated fabrics). As a specific example, there is a so-called on-machine mixed product, and when weaving or weaving, the polyurethane fiber bare yarn (in the case of bare yarn, knitting or weaving, while stretching about 2 to 4 times) or coated yarn on the machine For example, a knitted fabric that is mixed with a polyamide fiber or combined with a yarn is used.
Normally, reactive dyes are not dyed on polyurethane fibers, so it is necessary to dye them with a measure against eye strain, and it is also necessary to dye them with high durability.

  In the present specification, the term “mixed yarn of polyamide fiber and polyurethane fiber or a dyed product of fabric” includes the above-described form, but is not limited thereto.

The present inventor conducted extensive studies and experiments on a method for easily dyeing a reactive dye on a polyurethane fiber and obtaining high fastness, and then adsorbed a quaternary ammonium salt to the polyurethane fiber. It was unexpectedly discovered that dyeing with reactive dyes is the optimal method.
By using a metal complex salt type azo reactive dye as a reactive dye, the present inventor not only dyes polyurethane fibers with high fastness, but also has good dyeability on polyamide fibers, high color development, and high fastness. The present invention has been completed based on these findings.

As the “quaternary ammonium salt” in the present invention, a quaternary ammonium chloride having a long-chain alkyl group, for example, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethyl Ammonium chloride, alkylbenzyldimethylammonium chloride and the like can be mentioned. Among them, alkylbenzyldimethylammonium chloride can be preferably used.
Since the aqueous solution of the quaternary ammonium chloride having a long chain alkyl group in the present invention is almost neutral, by immersing the polyurethane fiber in an aqueous solution adjusted to the acidic side of pH 4 to 5 with an acid such as acetic acid. The quaternary ammonium salt can be easily adsorbed to the polyurethane fiber.

Specific examples of the quaternary ammonium chloride having a long-chain alkyl group include, for example, Elional EL (manufactured by Huntsman, alkylbenzyldimethylammonium chloride), Sanizole C (manufactured by Kao, alkylbenzyldimethylammonium chloride), Cotamine D-86P. (Manufactured by Kao Corporation, distearyldimethylammonium chloride).
The amount of quaternary ammonium salt used in the present invention is 0.3 wt% to 4 wt% in terms of product concentration, preferably 0.5 wt% to 2 wt%. In this case, the eye strain is not eliminated, and if it exceeds this, the effect is not improved and the cost becomes uneconomical.

  The method of treating polyurethane fibers with a quaternary ammonium salt is preferably a method of immersing a mixture of polyamide fibers and polyurethane fibers in an aqueous solution containing a quaternary ammonium salt, and the treatment temperature is 40 ° C to 70 ° C. ° C is preferred, and 50 ° C to 60 ° C is more preferred. The treatment time is preferably 10 minutes to 30 minutes. At this time, the pH of the treatment solution is preferably adjusted to 3 to 5 with a pH adjusting agent such as acetic acid. In addition, the bath ratio at the time of treatment is preferably 1:10 to 50, and the treatment may be performed before dyeing or at an initial stage in the dyeing process. When performed before dyeing, after treatment, lightly wash with water, Dyeing may be performed.

The mixed dyed product of the present invention has a grade 4 to 5 or higher in the Daimaru method color fastness measurement, and can be used without problems in various applications.
The Daimaru color crying test in the present invention is a test method for evaluating a phenomenon in which a dye moves during drying or when it gets wet when it rains, and a certain color moves to another color. In the industry, since the quality of the textile product can be accurately determined by a simple method, it is a method widely used throughout clothing. Specific test methods will be described later.

  The method for obtaining the mixed dyed product of the present invention is characterized in that the quaternary ammonium salt is adsorbed on the polyurethane fiber as described above and then dyed with a reactive dye.

As the reactive dye in the present invention, a metal complex salt type azo reactive dye is applied as a dye having good dyeing property to polyamide fiber and polyurethane fiber and easily obtaining high fastness.
Metal complex salt type azo dyes have a high molecular extinction coefficient, a clear hue, and a characteristic that a clear and deep hue can be obtained even for polyamide fibers. Generally, a reactive group is introduced into a dye base of a 1: 2 type metal complex hydrochloric acid dye. For example, as a type with improved light fastness, a dye described in JP-B-4-20951 is applied. Is done. In the present invention, for example, a dye having a CAS number of 854270-57-8 is particularly preferably applied in order to improve the color developability and fastness of the mixed dyed product.

The mixed article according to the present invention is a metal complex salt type azo reactive dye, and is dyed at a reaction temperature of 90 to 120 ° C., preferably 95 to 110 ° C. The dyeing time is preferably 30 to 60 minutes from the dyeing property of the dye and the embrittled surface of the polyurethane fiber. The heating rate during dyeing is preferably 1 to 2 ° C. The dyeing operation can be performed using an apparatus such as a wins, a jigger, a beam dyeing machine, or a liquid dyeing machine.
In this case, the pH of the aqueous dye solution is preferably adjusted to around 4 using a pH adjusting agent such as acetic acid. The leveling agent used in this case is not particularly limited as long as it is applied to reactive dyes. In general, nonionic surfactants such as anionic surfactants, amphoteric surfactants and alkylene oxide adducts of higher amines are used. An amphoteric surfactant or an anionic surfactant having a strong affinity for the reactive dye is preferable. Such amphoteric surfactants include, in particular, betaines derived from alkylene oxide adducts of aliphatic amines, and anionic surfactants are particularly derived from alkylene oxide adducts of aliphatic amines. And sulfate ester salts.

  For the purpose of enhancing the dyeing of the metal complex salt type azo reactive dye to the polyamide fiber and polyurethane fiber, the combined use of calcium chloride is particularly preferred. The concentration of calcium chloride used is preferably 2 to 10%, and after the temperature rise, 65 Calcium chloride dissolved in water should be added to -80 ° C, preferably 70-75 ° C. In the present invention, after completion of the dyeing operation, the mixed dyed product is subjected to a fix treatment in the presence of a hot alkaline agent for the purpose of removing residual acid and calcium chloride and enhancing fastness.

  The fixing agent used in the present invention is preferably an alkylamine, and more preferably hexamethylenediamine. The treatment method of the fixing agent is preferably a method of immersing the mixed product in an aqueous solution in which a concentration of 0.5 to 2 times the concentration of the metal complex salt type azo reactive dye is dissolved, and the treatment temperature is 80 to 95 ° C. Is preferable, more preferably 90 ° C., and the treatment time is preferably 10 to 30 minutes. At this time, the pH of the treatment solution is preferably adjusted to around 11 with an alkaline agent such as caustic soda. After the fix treatment, washing with water, neutralization, and water washing may be performed, but a small amount of metal complex type azo reactive dye that could not be fixed during the fix treatment can be easily removed under alkali. You may wash | clean for 10 to 20 minutes at 90 degreeC using 1g / L.

  Generally, when polyamide fibers are dyed in a dark color, they are post-treated in an acid bath using tannic acid or a synthetic fixing agent after dyeing. In this case, the texture after treatment has a strong squeaking feeling and a soft texture. There is a problem that it cannot be obtained. On the other hand, in the present invention, the post-treatment after dyeing is a treatment in an alkaline bath without using such a chemical substance, and thus has a characteristic that a soft texture can be obtained.

  When the mixed article of the polyamide fiber and the polyurethane fiber used in the present invention is a fabric, it is preferable to perform dyeing after knitting and weaving and then relaxing and scouring. In this case, scouring is preferably performed at a temperature of 60 to 98 ° C. with the fabric as relaxed as possible for reasons such as enhancing the stretch recovery property of the fabric. In addition, when form fixation is required before dyeing, a dry heat preset is performed at a temperature of 170 to 195 ° C., and after the fixing treatment, a softener or an antistatic agent that is usually used according to a conventional method, Desirable results can be obtained by adding a sewability improver, etc., and after drying, a final setting is performed at a temperature lower than the preset temperature by 10 ° C. or more.

  The mixed article of the polyamide fiber and the polyurethane fiber dyed in this way has high color developability, has a soft feel, has no eye feel, and has excellent Daimaru method color fastness of 4-5 grades or more. A mixed dyeing product having fastness performance and high commercial value can be obtained.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these.
First, the method for measuring the characteristic values used in the present invention is shown below.
(1) Measurement of coloring property L value of dyed product The color density of the surface of the dyed fabric was measured for the L value in the Lab color system using a spectrocolorimeter (CE-7000A manufactured by Gretag Macbeth Co.). The lower the L value, the higher the color developability. An L value of 20 or less indicates a dark-colored product.

(2) Fastness to sweat alkali The mixed dyed product was evaluated using an alkaline artificial sweat according to JIS L-0844. The degree of contamination of the test piece and the attached white cloth piece was judged by comparing with the gray scale for color change and the gray scale for contamination, respectively.

(3) Fastness to color of Daimaru method We put 0.05% non-ionic surfactant aqueous solution in a beaker, put 2.5 cm x 10 cm or more of the end of JIS cotton cloth on a 2.5 x 3 cm test piece of mixed dyed fabric. After sewing, immersing one end of the test piece vertically and letting it stand at room temperature for 2 hours, remove the beaker and dry it as it is. Judged in gray scale.
The judgment was as follows:
Gray scale for pollution Grade 5: No color crying;
Contamination grayscale grade 4-5: no crying
Contamination gray scale level 4: Slightly criminal;
Gray scale for contamination Less than 4th grade: There is crying.

(4) Eye Muki The mixed dyed product (fabric) was visually judged to determine the state of eye muff as the following first to fourth grades:
Grade 4: The color density and hue difference between polyamide fiber and polyurethane fiber cannot be recognized at all;
3rd grade: Polyurethane fiber is sufficiently dyed, but the level of lightness and hue difference with polyamide fiber can be confirmed slightly;
Second grade: Polyurethane fiber is dyed, but has a large shade difference and hue difference from polyamide fiber;
First grade: Level at which it can be recognized that polyurethane fibers are hardly dyed.

(5) Texture evaluation It evaluated by the inspector (30 persons). After Fix treatment, the texture of the woven or knitted fabric was relatively evaluated according to the following criteria:
○ (good): soft;
△ (Normal): Soft feeling is slightly inferior;
X (defect): There is a feeling of squeaking and there is no soft feeling at all.

[Examples 1 to 3]
6 courses under normal knitting conditions using nylon 6 (product name: Miracosmo manufactured by Toray Industries, Inc.) 56 decitex / 17 filament and 311 decitex polyether polyurethane fiber (trade name Roika SC manufactured by Asahi Kasei Fibers Co., Ltd.) A satin net knitted fabric (course density 175 loops / 2.54 cm, well density 44 loops / 2.54 cm) was prepared. The mixing ratio of the polyurethane fibers in this polyurethane fiber mixed knitted fabric was 22%.
This mixed knitted fabric is scoured and relaxed at 90 ° C., then pre-set at 190 ° C., and the conditions shown below:
(Pre-processing conditions)
Elional EL (alkylbenzyldimethylammonium chloride): Concentration listed in Table 1 Acetic acid: 1 ml / liter Bath ratio: 1:25
Processing temperature: 50 ° C
Treatment time: Pretreatment was performed in 20 minutes.

After pretreatment, drain the remaining liquid and wash it with water.
(Dyeing conditions)
Dye: Erio First Black M (manufactured by Huntsman) (CAS number 854270-57-8, metal complex salt type azo reactive dye): 4.5% omf
Auxiliary agent: Albegal SET (manufactured by Huntsman): 1 g / liter Acetic acid: 1 ml / L
Bath ratio: 1:17
Dyeing temperature and time: The dyeing bath solution is heated up to 75 ° C. at 1 ° C./min. When the dyeing temperature reaches 75 ° C., it is kept for 15 minutes, and 2% omf of calcium chloride is added, and again to 1 ° C./min. Temperature rise and dye at 100 ° C. for 40 minutes;
Stained with

After dyeing, the temperature is lowered to 60 ° C., the dyeing residual liquid is discharged from the dyeing machine, and water is put into the dyeing machine.
Erio First Fix (Hexamethylenediamine-containing product, manufactured by Huntsman): 3.6% omf
Caustic soda: 0.2 g / liter Bath ratio: 1:25.
And an alkali fix treatment at 90 ° C. for 20 minutes was performed.

After fixing, drain the remaining liquid, wash at 60 ° C with hot water, neutralize, wash with water, dehydrate, add sewing improver and antistatic agent, dry, and set at 150 ° C for 40 seconds to dry heat Done and finished.
Table 1 below shows the evaluation results of the coloring property of the finished dyed knitted fabric, fastness to sweat alkali, Daimaru color crying test, eye feel, and texture.

[Comparative Examples 1 and 2]
As Comparative Example 1, the knitted fabric of Example 1 was dyed under the same conditions as in Example 1 without being pretreated and finished in the same manner.
As Comparative Example 2, the knitted fabric of Example 1 was subjected to dyeing and Fix treatment under the following conditions without being subjected to pretreatment, and finished in the same manner as Example 1.
(Dyeing conditions)
Dye: Isolan black 2S-LD (manufactured by Dystar, 1: 2 type gold-containing acid dye): 3.5% omf
Auxiliary agent (Albegal SW (manufactured by Huntsman)): 0.5 g / liter Meisan FT (manufactured by Meisei Chemical Co., Ltd.): 0.5 g / liter
Bath ratio: 1:20
Dyeing temperature: 100 ° C
Staining time: 40 minutes (Fix condition)
Fix agent (HiFix SWA): 5% omf
Acetic acid: 0.5 ml / liter Bath ratio: 1:20
Processing temperature: 80 ° C
Processing time: 15 minutes

  Table 1 below shows the evaluation results of color developability, fastness to sweat alkali, Daimaru color crying test, eye feel, and texture of each dyed product obtained.

  From the results shown in Table 1, the dyed knitted fabrics obtained in Examples 1, 2, and 3 of the present invention have color crying in the Daimaru method of color crying test as compared with the dyed knitted fabrics obtained in Comparative Examples 1 and 2. The dyed knitted fabric is excellent in color developability, has a soft feel, and has a high commercial value.

[Examples 4 to 6]
40 g of an isobutylene-maleic anhydride alternating copolymer having an average molecular weight of about 60,000 (Isoban 04 manufactured by Kuraray Co., Ltd.), 33.8 g of diethylaminopropylamine, and 160 g of dimethylacetamide were mixed, and at 50 ° C. for 1 hour under a nitrogen atmosphere. The mixture was stirred at 100 ° C. for 1 hour, and then heated for 4 hours while distilling off the water generated at 180 ° C. under reflux. Residual volatiles were distilled off under reduced pressure, and the resulting polymer was dissolved in dimethylacetamide to give a 50% solution. The obtained polymer had a weight average molecular weight Mw = 1.0 × 10 ⁵ , a molecular weight distribution Mw / Mn = 2.7, and a shear viscosity of 104 poise.

A polyurethane prepolymer having isocyanate groups at both ends is reacted with 1,500 g of polytetramethylene ether glycol having an average molecular weight of 1,800 and 312 g of 4,4′-diphenylmethane diisocyanate while stirring at 60 ° C. for 90 minutes in a nitrogen gas stream. A polymer was obtained. Next, after cooling to room temperature, 2,700 g of dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution.
23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 1,570 g of dry dimethylacetamide and added to the prepolymer solution at room temperature to obtain a polyurethane polymer solution having a viscosity of 2,200 poise (30 ° C.). .

In this polyurethane polymer solution, 1.0% by weight of an isobutylene adduct of a polyaddition product of p-cresol and dicyclopentadiene with respect to a polyurethane solid content, Sumilizer
GA-80 (Sumitomo Chemical Co., Ltd.) 0.4% by weight, 2- (2H-benzotriazol-2-yl) -4,6-bis (2-phenylpropan-2-yl) phenol 0.2% by weight, Hydrotalcite 5.0% by weight and the prepared polymer having the maleimide structure 1.0% by weight were mixed to prepare a spinning dope.
The spinning solution was dry-spun at a spinning speed of 800 m / min and a hot air temperature of 325 ° C. to obtain 311 dtex polyurethane fibers.

Next, in the same manner as in Example 1, a nylon 656 dtex / 17 filament and the obtained polyurethane fiber were used to prepare a 6-course satin net knitted fabric in exactly the same manner as in Example 1, and scouring was relaxed. Later, pretreatment, dyeing and finishing were carried out.
Table 2 below shows the evaluation results of the coloring property of the finished dyed knitted fabric, fastness to sweat alkali, Daimaru color crying test, eye feel, and texture.

[Comparative Examples 3 and 4]
As Comparative Example 3, the knitted fabric of Example 2 was dyed under the same conditions as in Example 1 without performing pretreatment, and finished in the same manner.
As Comparative Example 4, the knitted fabric of Example 2 was subjected to dyeing and Fix treatment under the same conditions as Comparative Example 2 without performing pretreatment, and finished in the same manner as Example 1.
Table 2 below shows the evaluation results of the color developability, fastness to sweat alkali, Daimaru color crying test, eye feel and texture of each dyed product obtained.

  From the results of Table 2, the dyed knitted fabrics obtained in Examples 4, 5, and 6 of the present invention have color crying in the Daimaru method color crying test, compared with the dyed knitted fabric obtained in Comparative Examples 3 and 4. The dyed knitted fabric is excellent in color developability, has a soft feel, and has a high commercial value.

  The mixed yarn of the polyamide fiber and the polyurethane fiber of the present invention or the dyed product of the fabric has excellent fastness performance, and when the entire fabric is wet due to sweat, washing, etc., there is no color crying and there is no unevenness of eyes. It has a soft texture and can be suitably used for sports clothing, underwear, and the like.

Claims (5)

  A mixed yarn or fabric dyed product of a polyamide fiber and a polyurethane fiber, wherein the mixed yarn or fabric of a polyamide fiber and a polyurethane fiber preliminarily containing a quaternary ammonium salt is a metal complex type azo reactive dye The said dyed goods characterized by being dyed by.   The dyed article of the mixed yarn or fabric of the polyamide fiber and the polyurethane fiber according to claim 1, wherein the Daimaru method color fastness is 4 to 5 or higher. A method for producing a mixed yarn of polyamide fiber and polyurethane fiber or a dyed product of fabric, comprising the following steps:
Dyeing a mixed yarn or fabric of polyamide fiber and polyurethane fiber preliminarily containing a quaternary ammonium salt with a metal complex type azo reactive dye,
Including said method.   A mixed yarn of a polyamide fiber and a polyurethane fiber obtained by the method according to claim 3 or a dyed product of a fabric.   The dyed article of the mixed yarn or fabric of the polyamide fiber and the polyurethane fiber according to claim 4, wherein the Daimaru method color fastness is 4 to 5 or more.