JP2011001651A - Dyed product of blended yarns or fabric of polyamide fiber, cellulose fiber, and polyurethane fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dyed product of blended yarns or fabric of polyamide fibers, cellulose 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: In the dyed product of the blended yarns or fabric of the polyamide fibers, the cellulose fibers, and the polyurethane fibers, the blended yarns or fabric of the polyamide fibers, the cellulose fibers, and the polyurethane fibers are dyed with two kinds of metal complex azo reactive dye and non-metal complex azo reactive dye.

Description

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

In recent years, with the diversification of consumption trends for textile products, product development with composite materials has been actively carried out, and in particular, innerwear satisfies wear comfort, fashionability, durability, and kindness to the skin. Products are required.
Therefore, the excellent mechanical strength, chemical resistance, heat resistance, color development, washing durability, soft touch of polyamide fiber, excellent texture, water absorption, moisture absorption and release of cellulose fiber, and comfortable polyurethane fiber. Taking advantage of features such as stretchability, form retention, fit, moldability, and wrinkle resistance, products that satisfy the above-mentioned required characteristics with these three composite materials have been developed.

  For the dyeing of the mixed fabric of polyamide fiber, cellulose fiber and polyurethane fiber, the dyeing conditions in consideration of the same color property and fastness performance of polyamide fiber and cellulose fiber are adopted. Generally, the polyamide fiber side is dyed with an acid dye. However, although the cellulose fiber side is dyed with a reactive dye, the polyurethane fiber is not the main material on the product, so that the dyeing conditions with special consideration are not taken.

  When dyed under such dyeing conditions, polyurethane fibers have a low dyeing property for both acid dyes and reactive dyes, so that the same color characteristics of polyamide fibers, cellulose fibers and polyurethane fibers are poor, and polyurethane fibers Due to the fact that the fibers are not dyed, when the fabric product is stretched at the time of wearing or the like, a polyurethane fiber having a different color is seen, and there is a problem that a so-called “eye-feeling” 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. In addition, when cellulose fibers are directly dyed with a dye, polyurethane fibers are also dyed properly, so that the unevenness of the eyes is eliminated. However, both materials of cellulose fibers and polyurethane fibers have a problem of poor fastness performance, particularly dark dyeing. In this case, there is a problem that the polyamide fiber is greatly contaminated and the fastness performance is remarkably lowered, and it is necessary to dye the polyurethane fiber with a dye that can obtain high fastness of both the polyamide fiber and the cellulose fiber.

For this reason, as a means for improving the dyeability of polyurethane fibers with an acid dye, a method of containing polyamide fine particles having a specific particle diameter is disclosed in the following Patent Document 1, and a polymer having a maleimide structure is contained. The method is disclosed in Patent Document 2 below.
However, with these methods, although the unevenness of the eyes is eliminated, when dyed with a metal-containing dye in the dark dyeing of polyamide fiber, the dyeing of the dark color is performed when the product is washed or worn with rain. There is a so-called “color crying” phenomenon in which the dye moves from the white part to the white field or the light-colored part, 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 a limited shade of black, but lack of vividness in the color, so that a deep and calm hue can not be obtained. However, there is a problem that the same color as polyamide fiber and cellulose fiber cannot be obtained.

Further, a method for obtaining an excellent dyed product of polyamide fiber using a reactive dye is disclosed in the following Patent Document 5, and an excellent dyed product is obtained using a reactive dye from polyamide fiber and cellulose fiber. The method is disclosed in Patent Document 6 below.
However, although these methods improve the color crying phenomenon, there is a problem that the eye squeak problem cannot be solved because it does not stain the polyurethane fiber.
Therefore, in reality, satisfactory products are not obtained as a mixed fabric dyed product of polyamide fiber, cellulose fiber and polyurethane fiber with good quality and excellent color development and fastness to dyeing without eye lashes and tingling. is there.

JP 2007-46170 A JP 2009-74184 A JP 2003-268603 A JP 2004-60093 A Japanese Patent No. 4229653 JP 2002-69864 A

  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 fiber, cellulose fiber and polyurethane fiber, and a production method thereof.

As a result of intensive investigations and repeated experiments to solve the above-mentioned problems, the present inventor has found that, in a mixed yarn or fabric of polyamide fibers, cellulose fibers, and polyurethane fibers, a reactive dye for polyamide fibers and a reaction for cellulose fibers. When dyeing with two kinds of dyes, it has been found that by giving a specific compound to a polyurethane fiber in advance, an excellent dyed or dyed product of the thread or fabric can be obtained. It came to make.
That is, the present invention is as follows.

  [1] A mixed yarn or fabric dyed product of polyamide fiber, cellulose fiber and polyurethane fiber, wherein the mixed yarn or fabric of polyamide fiber, cellulose fiber and polyurethane fiber is a metal complex type azo reactive dye and a nonmetal The dyed article characterized by being dyed with two kinds of reactive dyes of complex salt type azo reactive dyes.

  [2] A quaternary ammonium salt is previously contained in the polyurethane fiber, the polyamide fiber and the polyurethane fiber are dyed with a metal complex salt type azo reactive dye, and the cellulose fiber is a nonmetal complex salt type azo type. A mixed yarn or fabric dyed product of the polyamide fiber, the cellulose fiber and the polyurethane fiber according to [1], which is dyed with a reactive dye.

  [3] A dyed product of a mixed yarn or fabric of a polyamide fiber, a cellulose fiber, and a polyurethane fiber according to [1] or [2], wherein the Daimaru method color fastness is 4 to 5 or higher.

[4] A method for producing a mixed yarn of polyamide fiber, cellulose fiber and polyurethane fiber or a dyed product of fabric, comprising the following steps:
Two types of reactive dyes, a metal complex salt type azo reactive dye and a nonmetal complex type azo reactive dye, are mixed with a polyamide fiber, a cellulose fiber, and a polyurethane fiber preliminarily containing a quaternary ammonium salt. Dyed with,
Including said method.

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

  [6] A dyed article of a mixed yarn or fabric of a polyamide fiber, a cellulose fiber, and a polyurethane fiber according to [5], wherein the color resistance to Daimaru method is 4 to 5 or higher.

  The mixed yarn of the polyamide fiber, cellulose fiber and polyurethane fiber according to the present invention or a dyed fabric is highly colored, has no unevenness, does not cry, and is excellent in dyeing fastness.

Hereinafter, the present invention will be described in detail.
According to the present invention, when dyeing a mixed yarn or fabric of polyamide fiber, cellulose fiber and polyurethane fiber, prior to dyeing the polyamide fiber, by adsorbing a quaternary ammonium salt to the polyurethane fiber before or simultaneously with dyeing, Dyeing with metal complex type azo reactive dyes, and dyeing cellulose fibers with nonmetal complex type azo reactive dyes can be used as a mixed yarn with high color development, no eye lashes, no color crying, and excellent color fastness Alternatively, a dyed fabric can be obtained.

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, cotton, hemp, viscose rayon, cupra, tencel, and diacetate fiber can be preferably used as the “cellulose fiber”. Diacetate fibers having an acetylation degree of 45 to 59.5% are preferably used. Further, the fineness of the cellulose fiber is not particularly limited, but generally, it is preferably 250 dtex or less in the case of long fibers and 20 or more in the case of short fibers.

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.
Polyurethane fibers can be selected and used as appropriate depending on the application, such as bright yarn with high sharpness and semi-dull type with reduced gloss. 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 metal complex salt type azo 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, the cellulose fiber and the polyurethane fiber according to the present invention can be appropriately determined depending on the use. However, a preferable result is generally obtained when the cellulose fiber is mixed at 40 wt% or less and the polyurethane fiber is mixed at 30 wt% or less. Is obtained. The mixed dyed product of the present invention is composed of polyamide fiber, cellulose fiber, and polyurethane fiber. In addition to these fibers, acrylic, silk, protein fiber, etc. 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 polyurethane yarn (10 to 500 dtex) is coated with a polyamide fiber or a cellulose fiber, for example, a so-called covering yarn (single or double covering), a twisted yarn, a core yarn, an entanglement Examples of the form of a known coated yarn, such as a yarn.

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 And knitted fabrics that are mixed with polyamide fibers and cellulose fibers or combined with yarns.
In general, reactive dyes are not dyed on polyurethane fibers, so it is necessary to dye them more than measures against eyelashes, and it is necessary to dye them more firmly than measures against tears.

  In the present specification, the term “mixed yarn of polyamide fiber, cellulose fiber and polyurethane fiber or dyed fabric” includes, but is not limited to, the above forms.

The present inventor has conducted intensive studies and experiments on a method for easily dyeing a polyurethane fiber with a metal complex salt type azo reactive dye and obtaining high fastness. As a result, the polyurethane fiber has a quaternary ammonium salt. It was unexpectedly discovered that adsorbing and then dyeing with reactive dyes is the optimal method.
The present inventor has shown that the metal complex salt type azo reactive dye not only dyes polyurethane fibers with high fastness, but also has good dyeing properties with respect to polyamide fibers, and provides high color development and 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, the mixed product is immersed 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 mixed yarn or fabric of polyamide fibers, cellulose fibers and polyurethane fibers in an aqueous solution containing a quaternary ammonium salt. 40 to 70 degreeC is preferable and 50 to 60 degreeC is more preferable. 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.

In the method for obtaining the mixed dyed product of the present invention, the quaternary ammonium salt is adsorbed on the polyurethane fiber as described above, and then the polyamide fiber and the polyurethane fiber are dyed with a metal complex salt type azo reactive dye, and the cellulose fiber is non-coated. It is characterized by dyeing with a metal complex salt type azo reactive dye.
Dyeing of polyamide fiber and polyurethane fiber with metal complex type azo reactive dye is performed under acidic pH, and dyeing of cellulose fiber with nonmetal complex type azo reactive dye is performed under alkaline condition. Dye each in a separate bath. The order of dyeing in this case is not particularly limited. However, due to color reproducibility and high fastness, after dyeing polyamide fiber and polyurethane fiber with metal complex type azo reactive dye, it is converted to nonmetal complex type azo reactive dye. It is preferable to dye cellulose fibers.

  After each dyeing, post-treatment of Fix and soaping is performed, so that contamination of the non-metallic complex type azo reactive dye to the polyamide fiber, contamination of the metal complex type azo reactive dye to the cellulose fiber, and unfixed Since the dye is removed, it is easy to obtain the same color characteristics of the polyamide fiber and the cellulose fiber, the color blur for each dyeing batch is small, and a dyed product with a high color depth is obtained as a mixed dyed product. And high fastness performance can be obtained.

In the present invention, for dyeing polyamide fibers and polyurethane fibers, a metal complex type azo reactive dye is applied as a dye having good dyeing property to both materials and easy to obtain high fastness.
The metal complex salt type azo reactive dye of the present invention is characterized by a high molecular extinction coefficient, a clear hue, and a clear and high color depth concentration even for polyamide fibers. In general, a reactive group is introduced into a dye base of a 1: 2 type metal complex hydrochloric acid dye. For example, a dye described in Japanese Patent Publication No. 4-20951 is applied. 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.

  In addition, it is particularly preferable to use calcium chloride together during dyeing for the purpose of enhancing the dyeing of the metal complex salt type azo reactive dye to the polyamide fiber and the polyurethane fiber. The concentration of calcium chloride used is preferably 2 to 10%, and calcium chloride dissolved in water is preferably added to 65 to 80 ° C., preferably 70 to 75 ° C. after the temperature rise. After the dyeing operation is completed, the mixed dyed product dyed in this way is fixed in the presence of a hot alkaline agent for the purpose of removing residual acid and calcium chloride, enhancing fastness and removing contaminating dyes on cellulose fibers. It is preferable to carry out the treatment.

  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 can be performed. However, a small amount of metal complex type azo reactive dye that was not sufficiently fixed during the fix treatment can be easily removed under alkali. You may wash | clean at 90 degreeC for 10 to 20 minutes using 1 g / L of soda ash after a process.

  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, the post-treatment after dyeing with the metal complex salt type azo reactive dye in the present invention has a feature that a soft texture can be obtained because it is an treatment in an alkaline bath without such post-treatment. is doing.

  The non-metal complex salt type azo reactive dye used in the present invention is a reactive dye having a structure having an azo bond in a dye matrix, and examples thereof include Color Index Reactive Black 5 (CAS No. 17095-24-8), Taking advantage of its high molecular extinction coefficient, it is widely used for dark dyeing such as amber and black.

  The method for dyeing the mixed article of the present invention with a non-metal complex type azo reactive dye is not limited, and may be any condition as long as it is usually carried out for dyeing cellulose fibers, and soaping after dyeing. Any other post-treatment may be used as long as it is a normal condition.

  When the mixed article of the polyamide fiber, the cellulose fiber and the polyurethane fiber used in the present invention is a fabric, it is preferably dyed after scouring and relaxing after knitting and weaving. 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. If it is necessary to fix the form before dyeing, dry heat presetting is performed at a temperature of 170 to 195 ° C. After dyeing and post-treatment, softeners and antistatic agents that are usually used in accordance with conventional methods. A preferable result can be obtained by applying a final set by adding an agent, a sewing agent, etc., drying, and lowering by 10 ° C. or more from the preset temperature.

  Mixed products of polyamide fiber, cellulose fiber and polyurethane fiber dyed in this way have high color developability, good color matching, soft texture, no eye-feel, fastness to Daimaru method. However, it has excellent fastness performance of 4 to 5 grades or more, and a mixed dyed product having a 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) Same color property The lightness difference between the polyamide fiber and the cellulose fiber is small, and the hue difference, the saturation difference, and the little irritation are good, and the grade is classified into five grades from grade 5 (good) to grade 1 (inferior).

(6) 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]
Nylon 6 (manufactured by Toray Nantong) 44 decitex / 30 filament, 311 decitex polyether-based polyurethane fiber (trade name Roika SC manufactured by Asahi Kasei Fibers Co., Ltd.) and cotton yarn No. 50, a 22 gauge warp knitting machine The satin knitted fabric (course density 48 loops / 2.54 cm, well density 34 loops / 2.54 cm, width 246 cm) was adjusted under normal knitting conditions. The blending rate of polyurethane fibers in this blended knitted fabric was 22%, and the blending rate of cotton was 23%.
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: 1:20
Processing temperature: 50 ° C
Treatment time: Pretreatment was performed in 20 minutes.

After the treatment, drain the residual 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): 3.5% omf
Auxiliary agent: Albegal SET (manufactured by Huntsman): 1 g / liter Acetic acid: 1 ml / L
Bath ratio: 1:20
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, 1.5% omf of calcium chloride is added, and then again 1 ° C. / Warmed in minutes and stained at 100 ° C. for 40 minutes;
Nylon 6 fiber and polyurethane fiber were dyed.

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): 2.8% omf
Caustic soda: 0.2 g / liter Bath ratio: 1:20;
And an alkali fix treatment at 90 ° C. for 20 minutes was performed.

After this fix, the remaining liquid is discharged, washed with hot water, neutralized, washed with water at 60 ° C., and the following dyeing conditions:
(Cotton dyeing conditions)
Dye: Novacron Black R (manufactured by Huntsman) (CI Reactive Black 5): 0.98% omf
Auxiliary agent: Tasfix NBA-L: 1.5 g / liter Texport DY: 1 g / liter Bow nitrate: 90 g / liter Sodium carbonate: 20 g / liter (added in portions after 20 minutes at 60 ° C.)
Bath ratio: 1:12
Dyeing temperature: 60 ° C
Dyeing war time: Cotton was dyed in 75 minutes.

After dyeing, the dyeing residual solution is discharged from the dyeing machine, water and acetic acid 0.5 ml / liter are put into the dyeing machine, neutralized at 25 ° C. for 10 minutes, washed with water, and lipotol B-6 1.5 g / liter. A liter was added and soaping was performed at 80 ° C. for 20 minutes.
After this soaping, the temperature is lowered to 60 ° C., the residual liquid is discharged from the dyeing machine, water is added to the dyeing machine, washed with water, washed with hot water at 40 ° C. and washed with water, and after dehydration, a sewing improver and antistatic agent are added. After the application and drying, a dry heat set at 150 ° C. for 40 seconds was performed.
Table 1 below shows the evaluation results of the coloring property of the finished dyed knitted fabric, the fastness to sweat alkali, the Daimaru color crying test, the eye feel, the same color property, and the 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 subjected to pretreatment before dyeing of nylon 6 fiber, and finished in the same manner.
As Comparative Example 2, the knitted fabric of Example 1 was subjected to double bath dyeing under the following conditions without being subjected to pretreatment, and finished in the same manner as Example 1.
(Cotton dyeing conditions)
Dye: Novacron Black R (manufactured by Huntsman) (CI Reactive Black 5): 1.5% omf
Auxiliary agent: Tasfix NBA-L: 1.5 g / liter Texport DY: 1 g / liter Bow nitrate: 90 g / liter Sodium carbonate: 20 g / liter (added in portions after 20 minutes at 60 ° C.)
Bath ratio: 1:12
Dyeing temperature: 60 ° C
Dyeing time: 75 minutes

After dyeing, the dyeing residual liquid is discharged from the dyeing machine, water and acetic acid 0.5 ml / liter are put into the dyeing machine, neutralized at 25 ° C. for 10 minutes, washed with water, and 1 g / liter of lipotol B-6 is added. And then soaped at 80 ° C. for 20 minutes.
After this soaping, the temperature was lowered to 60 ° C., the residual liquid was discharged from the dyeing machine, water was put into the dyeing machine, and nylon 6 was dyed under the following conditions:
(Nylon 6 dyeing conditions)
Dye: Isolan Black 2S-LD (manufactured by Dystar, 1: 2 type gold-containing acid dye): 2.3% 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: 95 ° C
Staining time: 40 minutes.

After dyeing, the temperature was lowered to 60 ° C., the dyeing residual liquid was discharged from the dyeing machine, water was put into the dyeing machine, the following chemicals were added, Fix treatment, and water washing were performed:
(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 the color developability, sweat alkali fastness, Daimaru method color crying test, eye feel, same color, 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. It is understood that the dyed knitted fabric is excellent in color developability, has the same color, 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, an isobutylene adduct of a polyaddition product of p-cresol and dicyclopentadiene, 1.0% by weight, and Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) 0.4% by weight with respect to the polyurethane solid content. 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 maleimide 1.0% by weight of a polymer having a structure was mixed to obtain 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 satin knitted fabric was prepared using a nylon 644 dtex / 34 filament, cotton yarn No. 50 and the obtained polyurethane fiber using a 22 gauge warp knitting machine.
The obtained knitted fabric was scoured relaxed and pre-set in the same manner as in Example 1, pretreated before dyeing of nylon 6 fiber, and dyed and finished in the same manner.
Table 2 below shows the evaluation results of the coloring property of the finished dyed knitted fabric, the fastness to sweat alkali, the Daimaru color crying test, the eye feel, the same color property, and the 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 any pretreatment before dyeing of nylon 6 fiber, and finished in the same manner.
As Comparative Example 4, the knitted fabric of Example 2 was subjected to two-bath dyeing and Fix treatment under the same conditions as Comparative Example 2 without performing pretreatment before dyeing of nylon 6 fiber, and the same as in Example 1. Finished.
Table 2 below shows the evaluation results of color developability, fastness to sweat alkali, Daimaru color crying test, eye feel, same color, 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 and color matching, has a soft feeling, and has a high commercial value.

  The mixed yarn of polyamide fiber, cellulose fiber and polyurethane fiber of the present invention or a dyed fabric has excellent fastness performance, and does not cry when the entire fabric is wet due to sweat, washing, etc. It has a soft texture and can be suitably used for sports clothing and underwear.

Claims (6)

  Polyamide fiber, cellulose fiber, and polyurethane fiber mixed yarn or fabric dyeing product, wherein polyamide fiber, cellulose fiber, and polyurethane fiber mixed yarn shape or fabric is a metal complex type azo reactive dye and a non-metal complex type azo The dyed product characterized in that it is dyed with two reactive dyes of a system reactive dye.   The polyurethane fiber contains a quaternary ammonium salt in advance, the polyamide fiber and the polyurethane fiber are dyed with a metal complex type azo reactive dye, and the cellulose fiber is a non-metal complex type azo reactive dye. The dyed article of mixed yarn or fabric of the polyamide fiber, cellulose fiber and polyurethane fiber according to claim 1, which is dyed.   The dyed article of a mixed yarn or fabric of a polyamide fiber, a cellulose fiber and a polyurethane fiber according to claim 1 or 2, wherein the Daimaru method color fastness is 4 to 5 or more. A method for producing a mixed yarn of polyamide fiber, cellulose fiber and polyurethane fiber or a dyed fabric, comprising the following steps:
Two types of reactive dyes, a metal complex salt type azo reactive dye and a nonmetal complex type azo reactive dye, are mixed with a polyamide fiber, a cellulose fiber, and a polyurethane fiber preliminarily containing a quaternary ammonium salt. Dyed with,
Including said method.   A dyed product of mixed yarn or fabric of polyamide fiber, cellulose fiber and polyurethane fiber obtained by the method according to claim 4.   The dyed article of a mixed yarn or fabric of polyamide fiber, cellulose fiber, and polyurethane fiber according to claim 5, having a color fastness to Daimaru method of 4 to 5 or higher.