JP2005187996A - Method for dyeing mixed fiber fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for dyeing mixed fiber fabric prepared by mixing polytrimethylene terephthalate fiber with polyamide fiber that can dye the mixed fiber fabric in a short time with an excellent level of dyeing and colorfastness. <P>SOLUTION: When a mixed fiber fabric including polytrimethylene terephthalate fiber and polyamide fiber is dyed through the single bath and the single step, by using azo disperse dye that shows a ratio of 15 to 60% in the percentage exhaustion, when polyethylene terephthalate fiber fabric is dyed at 130°C at a pH of 11 to the percentage exhaustion at a pH of 5 and a 1 : 2 premetalized dye, and further a polyamide fixing agent is used together on or after dyeing. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a method for dyeing a mixed article that can dye a mixed article made of polytrimethylene terephthalate fiber and polyamide fiber in a short time, and is suitable for improving leveling and fastness of dyeing. .

Polyamide fibers are light in specific gravity, have a unique luster and texture, and are often used for inner, sports, and outer applications. However, there are drawbacks such as poor dimensional stability and easy wrinkling.
Polytrimethylene terephthalate fibers, on the other hand, are very flexible and have excellent stretch properties (easiness of elongation and ease of recovery after stretching) while having dimensional stability comparable to polyethylene terephthalate fibers. is there. In recent years, there has been an increasing demand for mixed products that use these fibers in a mixed manner and make use of the characteristics of each other while complementing the drawbacks of polyamide products. As a matter of course, dyeing processing is also necessary for mixed goods, and it is required that the mixed goods have excellent levelness and fastness to dyeing.
Patent Document 1 discloses a dyeing method for dyeing polytrimethylene terephthalate fiber in an aqueous dyeing solution containing a disperse dye, and it is described that this method can also be applied when mixed with other fibers. ing. However, although there is a description of a dyeing method for polytrimethylene terephthalate fiber, a specific dyeing method for a mixed product with polyamide fiber is not described.

Disperse dyes have the property of dyeing even on polyamide fibers, but polyamide fibers dyed with disperse dyes have a problem of poor dyeing fastness.
For dyeing mixed products of polytrimethylene terephthalate fibers and polyamide fibers, a two-bath two-stage method is generally used in which polytrimethylene terephthalate fibers are dyed with disperse dyes and polyamide fibers are dyed with acid dyes. ing. However, in order to suppress the fastness reduction due to the disperse dyes dyed on the polyamide fiber, reduction cleaning is essential after the disperse dye dyeing, which requires a long time for dyeing, which increases the cost of dyeing, and depending on the hue after dyeing In some cases, the fastness was inferior.
In addition, attempts have been made to dye both materials in one bath in order to shorten the dyeing process, but at present, the dyeing fastness level of two baths and two stages has not been achieved.
Therefore, when dyeing a mixed product of polytrimethylene terephthalate fiber and polyamide fiber, one bath that provides high fastness with short dyeing time, low cost, no color development, and excellent uniform dyeability. Development of a one-step dyeing method has been desired.
JP 2000-192375 A

  An object of the present invention is to provide a method for dyeing a mixed article in which polytrimethylene terephthalate fiber and polyamide fiber are mixed and can be dyed in a short time and excellent in leveling and fastness to dyeing.

In order to solve the above problems, the present inventors have intensively studied the one-bath one-step dyeing method, and as a result, found that the above problems can be achieved by using a specific azo disperse dye and a specific metal-containing dye, The invention has been reached.
That is, the invention claimed in the present application is as follows.
(1) When dyeing a mixed article containing polytrimethylene terephthalate fiber and polyamide fiber in one bath and one stage, when dyeing a fabric made of polyethylene terephthalate fiber, the dyeing temperature is 130 ° C. and the pH is 5. An azo disperse dye having a dyeing rate of 15 to 60% when the pH is 11 relative to the dyeing rate and a 1: 2 gold-containing dye are used, and a polyamide-based fixing agent is dyed or after dyeing. A method for dyeing mixed goods, characterized by being used in combination.
(2) The method for dyeing a mixed article according to (1), wherein the polytrimethylene terephthalate-based fiber is a latently crimpable polyester fiber having at least one component made of polytrimethylene terephthalate.

  According to the method for dyeing a mixed article of the present invention, a mixed article of polytrimethylene terephthalate fiber and polyamide fiber can be dyed and processed in a short time, and is excellent in leveling and fastness to dyeing. Can be obtained.

The present invention will be specifically described below.
The dyeing method of the present invention is applied to a mixed article including polytrimethylene terephthalate fiber and polyamide fiber.
In the present invention, the polytrimethylene terephthalate fiber refers to a polyester fiber having a trimethylene terephthalate unit as a main repeating unit, and the trimethylene terephthalate unit is about 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol. % Or more, more preferably 90 mol% or more. Accordingly, the total amount of the other acid component and / or glycol component as the third component is in the range of about 50 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. Includes included polytrimethylene terephthalate.

Polytrimethylene terephthalate is synthesized by combining terephthalic acid or a functional derivative thereof with trimethylene glycol or a functional derivative thereof in the presence of a catalyst under suitable reaction conditions. In this synthesis process, a suitable one or two or more third components may be added to form a copolyester. Polyesters other than polytrimethylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, nylon and polytrimethylene. Methylene terephthalate may be synthesized separately and then blended.
The third component to be added includes aliphatic dicarboxylic acids (oxalic acid, adipic acid, etc.), alicyclic dicarboxylic acids (cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (isophthalic acid, sodium sulfoisophthalic acid, etc.), fat Aliphatic glycols (ethylene glycol, 1,2-propylene glycol, tetramethylene glycol, etc.), alicyclic glycols (cyclohexanedimethanol, etc.), aliphatic glycols containing aromatics (1,4-bis (β-hydroxyethoxy) benzene Etc.), polyether glycol (polyethylene glycol, polypropylene glycol etc.), aliphatic oxycarboxylic acid (ω-oxycaproic acid etc.), aromatic oxycarboxylic acid (P-oxybenzoic acid etc.) and the like. In addition, compounds having one or three or more ester-forming functional groups (such as benzoic acid or glycerin) can also be used within the range where the polymer is substantially linear.

The spinning method of polytrimethylene terephthalate fiber is described in, for example, the pamphlet of International Publication No. 99/27168, and after obtaining an undrawn yarn at a winding speed of about 1500 m / min, about 2 to 3.5 times. Any of the method of twisting and spinning, the direct spinning drawing method (spin draw method) in which the spinning and drawing steps are directly connected, and the high speed spinning method (spin take-up method) with a winding speed of 5000 m / min or more may be employed.
As a preferable characteristic of the polytrimethylene terephthalate fiber, the strength is 2 to 5 cN / dtex, preferably 2.5 to 4.5 cN / dtex, and more preferably 3 to 4.5 cN / dtex. The elongation is 30 to 60%, preferably 35 to 55%, more preferably 40 to 55%. The elastic modulus is 30 cN / dtex or less, preferably 10 to 30 cN / dtex, more preferably 12 to 28 cN / dtex, and particularly preferably 15 to 25 cN / dtex. The elastic recovery rate at 10% elongation is preferably 70% or more, more preferably 80% or more, further 90% or more, and most preferably 95% or more.

In the present invention, as the polytrimethylene terephthalate fiber, it is preferable to use a latently crimpable polyester fiber having at least one component made of polytrimethylene terephthalate. A latently crimpable polyester having at least one component made of polytrimethylene terephthalate is composed of at least two polyester components, and at least one component is polytrimethylene terephthalate, and develops crimp by heat treatment. Is. There are no particular limitations on the composite ratio of the two polyester components (generally many are in the range of 70/30 to 30/70 by mass%) and the joint surface shape (there is a straight or curved shape). The total fineness is preferably 20 to 300 dtex and the single yarn fineness is preferably 0.5 to 20 dtex, but is not limited thereto.
Examples of such fibers include composite fibers in which two kinds of polyester polymers are joined in a side-by-side type or an eccentric core-sheath type. In the case of the side-by-side type, the melt viscosity ratio of the two polyester polymers is preferably 1.00 to 2.00, and in the case of the eccentric core-sheath type, the alkali weight loss rate ratio between the sheath polymer and the core polymer is 3 times or more. It is preferred that the sheath polymer is fast.

  Specific polymer combinations include polytrimethylene terephthalate (polyester having terephthalic acid as the main dicarboxylic acid and 1,3-propanediol as the main glycol component, glycols such as ethylene glycol and butanediol, and isophthalic acid. , Dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, etc. may also be copolymerized, and other polymers, matting agents, flame retardants, antistatic agents, pigments and other additives may be included.) And polyethylene terephthalate (polyester containing terephthalic acid as the main dicarboxylic acid and ethylene glycol as the main glycol component, copolymerized with glycols such as butanediol, isophthalic acid, and dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid) Also, other polymers, matte In combination with flame retardants, antistatic agents, pigments, etc.), polytrimethylene terephthalate and polybutylene terephthalate (terephthalic acid is the main dicarboxylic acid, and 1,4-butanediol is the main. It is a polyester as a glycol component, and may be copolymerized with glycols such as ethylene glycol, diphthalic acid such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, etc. Other polymers, matting agents, flame retardants, An additive such as an antistatic agent and a pigment may be contained.), But a cross-sectional shape of the fiber in which polytrimethylene terephthalate is disposed inside the crimp is preferable.

  Regarding latently crimpable polyester fibers (hereinafter, sometimes simply referred to as latently crimpable polyester fibers), at least one component of which is made of polytrimethylene terephthalate, Japanese Patent Application Laid-Open No. 2001-40537 and Japanese Patent Publication No. 43-19108. JP-A-11-189923, JP-A-2000-239927, JP-A-2000-256918, JP-A-2000-328382, JP-A-2001-81640, etc. Polytrimethylene terephthalate as the first component, and polyester such as polytrimethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate as the second component were compound-spun into side-by-side type or eccentric sheath-core type in which they were arranged in parallel or eccentrically. Things That. In particular, a combination of polytrimethylene terephthalate and copolymerized polytrimethylene terephthalate or polyethylene terephthalate, or a combination of two types of polytrimethylene terephthalate having different intrinsic viscosities is preferable.

In the case of a combination of two types of polytrimethylene terephthalate, the intrinsic viscosity difference is preferably 0.05 to 0.4 (dl / g), particularly 0.1 to 0.35 (dl / g). Further, 0.15 to 0.35 (dl / g) is preferable. For example, when the intrinsic viscosity on the high viscosity side is selected from 0.7 to 1.3 (dl / g), the intrinsic viscosity on the low viscosity side is selected from 0.5 to 1.1 (dl / g). Is preferred. In addition, the intrinsic viscosity on the low viscosity side is preferably 0.8 (dl / g) or more, particularly 0.85 to 1.0 (dl / g), more preferably 0.9 to 1.0 (dl / g). .
The average intrinsic viscosity of the polytrimethylene terephthalate composite fiber is preferably 0.7 to 1.2 (dl / g), and more preferably 0.8 to 1.2 (dl / g). In particular, 0.85 to 1.15 (dl / g) is preferable, and 0.9 to 1.1 (dl / g) is more preferable.
In addition, the spinning of the latent crimp developing polyester fiber can be performed by the same method as the polytrimethylene terephthalate fiber.

The latent crimp-generating polyester fiber preferably has an initial tensile resistance of 10 to 30 cN / dtex, particularly 20 to 30 cN / dtex, and more preferably 20 to 27 cN / dtex. In addition, it is difficult to manufacture a material having a density less than 10 cN / dtex. Moreover, it is preferable that the expansion / contraction elongation rate of the actual crimp is 10 to 100%, particularly 10 to 80%, and further preferably 10 to 60%. Further, the elastic modulus of the actual crimp is preferably 80 to 100%, particularly preferably 85 to 100%, and more preferably 85 to 97%.
The heat shrinkage stress at 100 ° C. is preferably from 0.1 to 0.5 cN / dtex, particularly preferably from 0.1 to 0.4 cN / dtex, more preferably from 0.1 to 0.3 cN / dtex. The heat shrinkage stress at 100 ° C. is an important requirement for developing crimps in the fabric refining and dyeing processes. That is, in order to overcome the binding force of the fabric and cause crimping, it is preferable that the heat shrinkage stress at 10 ° C. is 0.1 cN / dtex or more.
The expansion / contraction elongation after the hot water treatment is preferably 100 to 250%, more preferably 150 to 250%, and particularly preferably 180 to 250%. Moreover, it is preferable that the expansion-contraction elastic modulus after a hot-water process is 90 to 100%, More preferably, it is 95 to 100%.
In addition, the value of the intrinsic viscosity as used in the present invention refers to the viscosity of the yarn being spun, not the polymer used. The reason for this is that polytrimethylene terephthalate has a disadvantage inherent to thermal decomposition as compared with polyethylene terephthalate and the like, and even if a polymer with a high intrinsic viscosity is used, the intrinsic viscosity is significantly reduced by thermal decomposition. This is because it is difficult to maintain a large difference in intrinsic viscosity between the two.

The polytrimethylene terephthalate fibers used in the present invention may be long fibers or short fibers, and may be uniform or thick in the length direction, and round, triangular, L-shaped, and T-shaped in cross section. , Y type, W type, Yaba type, flatness (flatness of about 1.3-4, W type, I type, Boomerang type, wave type, skewer type, eyebrows type, rectangular parallelepiped type, etc. There may be a polygonal type such as a dogbone type, a multi-leaf type, a hollow type or an indeterminate type.
Furthermore, as the form of the yarn, a spun yarn such as a ring spun yarn, an open-end spun yarn, a multifilament yarn (including ultrafine yarn) having a single yarn denier of about 0.1 to 5 denier, a sweet twisted yarn to a strongly twisted yarn, False twisted yarn (including POY drawn false twisted yarn), air-jet processed yarn, indented yarn, knitted knitted yarn, and the like may be used.

  In addition, within the range which does not impair the object of the present invention, usually within 30% by weight or less, other fibers such as natural fibers and synthetic fibers, for example, natural fibers such as cotton, wool, hemp and silk, cupra, Viscose, polynosic, purified cellulose, acetate, polyester fibers such as polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate, various artificial fibers such as polyamide and acrylic, and their copolymer types and the use of the same or different polymers Composite fibers (side-by-side type, eccentric sheath core type, etc.) are blended (core yarn, silo span, silofill, hollow spindle, etc.) or covered (single, double), for example, low shrinkage with a boiling water shrinkage of about 3-10% Yarn, for example, mixed yarn with high shrinkage of about 30-30% boiling water shrinkage, twisting, Twist (twist elongation difference tentative composite or the like in the draw texturing of the POY), or may be used together with 2 feed air blasting, etc. means.

  The polyamide fiber used in the present invention is a fiber obtained by spinning a long chain continuous synthetic polymer by an amide bond. For example, nylon 6, nylon 66, nylon distinguished by the number of carbons in the intermediate raw material before synthesis. 610, nylon 612, or the like is used, and the form of the fiber (long fiber or short fiber), cross-sectional shape, and thread form are not particularly limited.

The form of the mixed article to which the dyeing method of the present invention is applied is not particularly limited, and may be any form such as yarn, woven fabric, or knitted fabric. In the case of mixed use with yarn, examples of the composite form include cover ring, core spun yarn, interlace entangled yarn, air covering yarn, and twisted yarn, but there is no particular limitation. In the case of a woven fabric, it may be taffeta, twill, satin, and various changed structures. In the case of a knitted fabric (warp knitting, circular knitting, flat knitting), any structure knitted by a combination of knit and tuck welt. It may be a fabric or a piece.
In the present invention, the blending ratio of the polytrimethylene terephthalate fiber and the polyamide fiber in the mixed product is preferably 50% by weight or more of the entire mixed product. Therefore, various fibers other than these fibers may be mixed within a range of less than 50% by weight. The constituent weight ratio of the polytrimethylene terephthalate fiber and the polyamide fiber is preferably in the range of 20:80 to 80:20.

In the dyeing method of the present invention, the above-mentioned mixed product containing polytrimethylene terephthalate fiber and polyamide fiber is dyed in one step per bath. At this time, a dyeing temperature of 130 is used when dyeing a fabric made of polyethylene terephthalate fiber. An azo disperse dye having a dyeing rate ratio of 15 to 60% when the pH is 11 with respect to the dyeing rate when the pH is 5 ° C. (hereinafter referred to as an easily alkali-soluble azo disperse dye) In addition, it is necessary to use a mixed dye with a 1: 2 gold-containing dye and to use a polyamide-based fixing agent in combination with or after the dyeing.
By using these dyes and a fixing agent, it is possible to perform one-step one-step dyeing of the above-mentioned mixed products, and dyeing excellent in levelness and fastness to dyeing is possible.

  When the above mixed goods are dyed with ordinary disperse dyes, the disperse dyes dyed on the polyamide fibers cannot be removed sufficiently even after reduction washing after dyeing. , Color misregistration, decrease in fastness, particularly decrease in light fastness. This occurs regardless of one bath per stage or separate bath dyeing. In order to promote the removal of the dye in the polyamide fiber after dyeing, for example, a reducing cleaning method under conditions in which the reducing agent concentration and the alkaline agent concentration are higher than usual. For example, a method of reducing and cleaning by increasing the concentration to about 8 to 10 g / L is conceivable, but in this case, not only the cost is increased, but the reduction cleaning conditions are strengthened. This causes problems such as a decrease in color developability of polytrimethylene terephthalate fiber and polyamide fiber, discoloration, and a large variation in color for each dyeing batch, which is not practical.

On the other hand, when the mixed product is dyed with an easily dissolvable azo disperse dye as in the present invention, the disperse dye in the polyamide can be easily removed in the reduction washing after the dyeing. Therefore, problems such as color misregistration and low fastness do not occur.
Examples of the easily alkali-soluble azo disperse dye used in the present invention include C.I. I. Disperse Yellow 5, C.I. I. Disperse Yellow 64, C.I. I. Disperse Orange 29, C.I. I. Disperse Orange 30. C. I. Disperse thread 43, C.I. I. Disperse thread 135, C.I. I. Disperse violet 28, C.I. I. Disperse Blue 54, C.I. I. Disperse Blue 301, Dye Sumikaron Yellow S-RPD, Sumikaron Red S-RPD, Sumikaron Blue S-RPD, Sumikaron Abbe Blue SE-RPD, Sumikaron Black S-BGL, Japan The dye Kayaron polyester black BR-SF manufactured by Kayaku Co., Ltd. may be mentioned.

The metal-containing dye is an azo dye belonging to an acid dye in which a metal atom and a dye molecule are coordinated in the form of a complex salt. As the metal-containing dye, one dye molecule and one metal atom are included. Two types are known: a 1: 1 metal-containing dye having a coordinate bond, and a 1: 2 metal-containing dye in which two dye molecules and one metal atom are coordinate-bonded. In the method, it is necessary to use a 1: 2 gold-containing dye from the viewpoint of obtaining a mixed product having high dyeing fastness. This 1: 2 gold-containing dye is used as a dye for dyeing polyamide fibers, but is more dyed to polyamide fibers than 1: 1 gold-containing dyes and other acid dyes. Therefore, by using this 1: 2 gold-containing dye, it is possible to prevent color change and fading on the polyamide fiber side, which are likely to occur due to soaping and reduction washing processes that are usually carried out after dyeing with disperse dyes. It becomes possible.
Examples of 1: 2 gold-containing dyes include, for example, the dyes Lanyl Yellow GR e / c, Lanyl Orange 2R e / c, Lanyl Red GG, Lanyl Bordeaux R83%, Lanyl Blue 3G e / c manufactured by Sumika Dyetech. Lanyl Black BG conc. gran, Nippon Kayaku Co., Ltd. dye Kayakalan yellow GL143, Kayakalan red BL, Kayakalan Gray BL167, Hoizeya dye Aizen Opal black liq, etc. are mentioned.

In the present invention, when a dye shown below in which an easily dissolvable azo disperse dye and a 1: 2 gold-containing dye are mixed is used, the polyamide fiber and the polytrimethylene terephthalate fiber can be dyed almost in the same color. It is particularly suitable because it has a combination. In the case where the same color is not necessarily obtained depending on the form and shape of the fiber, in order to obtain the same color, a commercially available easily alkali-soluble disperse dye or 1: 2 gold-containing dye is further added within the range where the effect of the present invention can be achieved, and dyeing You may go.
Examples of dyes in which an easily alkali-decomposable dye and a 1: 2 gold-containing dye are blended include, for example, E / NRed 15A, E / NNavyBlue 17A, E / NBlack20N, E / NY YellowBrown 13A2, E / NY Yellow 12A manufactured by Daiichi Kasei. , E / NBlue16A, E / NYelloT-112, E / NRedT-116, E / NBlueT-124, and the like.

As the fixing agent for polyamide used in the present invention, a commercially available fixing agent for acidic dyes can be used. For example, natural tannin, synthetic tannin, polyhydric phenol sulfonic acid, aromatic oxysulfonic acid, oxysulfonic acid and its Derivatives and condensates can be used.
When the above-mentioned fixing agents for acid dyes are used, since general fixing agents bind to acid dyes when the pH becomes acidic at around 4, when these are used in one-bath one-step dyeing, leveling can be obtained. There may not be. For this reason, it is important to control the dye bath pH during the dyeing step, and it is preferable to use a pH slide agent that has a pH of about 5.5 to 6.5 at the end of dyeing from around neutrality (about pH 7).
Furthermore, it is preferable to use a fixing agent whose pH changes from neutral to acidic as the temperature rises during dyeing. For example, it is preferable to add ammonium sulfate or the like to the fixing agent, adjust to neutrality at the initial stage, disperse ammonium as the temperature rises during dyeing, and lower the pH at the end of dyeing. Examples of such a fixing agent include nylon sticker 102 and chamois sticker-Y-1020A manufactured by Shichifuku Chemical Co., Ltd.

As a preparatory step before dyeing mixed goods, normal scouring and presetting can be performed in accordance with conventional methods. Presetting can be performed after scouring or after presetting, omitting the presetting. Also good.
Although the temperature of the presetting is not particularly limited, the texture of polytrimethylene terephthalate fiber may become hard when it exceeds 190 ° C., and it is preferably performed at 120 to 190 ° C. for about 20 to 1180 seconds. A steam set may also be performed.
In the dyeing method of the present invention, dyeing of a mixed product can be performed in one step per bath. For example, the above-described easily alkali-soluble azo disperse dye, 1: 1 metal-containing dye and dyeing assistant are added to the dye bath, and polyamide fibers and polytrimethylene terephthalate fibers and / or latent crimps are developed. Dye polyester fibers simultaneously. Therefore, when a fiber other than polyamide fiber and polytrimethylene terephthalate fiber and / or latent crimpable polyester fiber is mixed in the mixed product, it may be dyed in a separate bath in order to dye the fiber. . The dyeing method may be dyed under the usual conditions for each fiber.

The dyeing assistant used in the present invention is not particularly limited, and each auxiliary agent usually used at the time of using a disperse dye and an acid dye can be used. For example, dispersing agents for disperse dyes, leveling agents, carrier agents, leveling agents for acid dyes, slow dyeing agents, fixing agents, and organic acids such as acetic acid to adjust the dye bath pH to acid, organic What is necessary is just to use the buffer which mixed acid + organic acid salt, the pH slide agent etc. whose pH changes with temperature rising.
As the dyeing temperature, both polyamide fiber, polytrimethylene terephthalate fiber, and latent crimpable polyester fiber have the property of dyeing even at a low temperature of about 90 ° C., preferably about 90 ° C. to 130 ° C., and the dyeing time is What is necessary is just to make it about 15 minutes-60 minutes.
The method for treating the fixing agent for polyamide of the present invention may be a method for treating at the same time as dyeing or after dyeing, but it is more preferable to use a fixing agent in combination in one-stage one-stage dyeing. If this method is adopted, the fixing process step of the polyamide fiber after dyeing can be omitted, dyeing can be performed for a short time, and it is more effective in preventing color change and fading on the polyamide side. However, when performing simultaneously with dyeing, it is important to pay attention to the pH as described above.

What is necessary is just to use what is used normally as a dyeing | staining apparatus. For example, in the case of fabric, liquid dyeing machine, wins dyeing machine, beam dyeing machine, zicker dyeing machine, etc., in the case of piece, paddle dyeing machine, rotary dyeing machine, in the case of yarn, after making cheese, casserole, muff A package dyeing machine, a rotary bag, a cassette dyeing machine, etc. may be appropriately selected and used.
In the present invention, soaping, reductive washing, and in some cases, a fix agent treatment may be performed after dyeing. In particular, when the dyeing density is high, these treatments are necessary in order to maintain the dyeing fastness.
In the case of performing reduction washing after dyeing, if the reducing power is too strong, there may be a hue change due to the dropping or discoloration of the dye attached to the polyamide fiber. Therefore, weak alkaline reduction using alkaline agent such as sodium carbonate and hydrosulfite, reducing agent such as thiourea dioxide, and acetic acid and sulfur reducing agent (for example, manufactured by Sumitomo Seika Co., Ltd.) Acid reduction using a redol C) or a zinc sulfoxylate formamide-based reducing agent (for example, Decolin manufactured by Mitsui BASF) is preferable. If the disperse dye having excellent alkali solubility of the present invention is used, even if it is reduced and washed under the normal to weak conditions as described above, the disperse dye dyed on the polyamide or excess of the polytrimethylene terephthalate fiber is superposed. This makes it possible to effectively remove disperse dyes.

In the present invention, finish processing such as resin processing, water absorption processing, anti-static processing, antibacterial processing, and water repellent processing, which are usually used for fiber processing, can be applied as a finishing set without impairing the object of the present invention. The finishing set temperature may be 130 to 180 ° C., preferably about 140 to 160 ° C., in order to suppress a decrease in fastness.
In particular, when it is desired to finish the texture softly, the finishing may be performed with a silicone-based softener made of alkylpolysiloxane, amino-modified silicone, carboxy-modified silicone, epoxy-modified silicone, or the like.

The present invention will be described with reference to examples.
(1) Intrinsic viscosity:
The intrinsic viscosity [η] (dl / g) is a value obtained based on the definition of the following formula.
[Η] = lim (ηr−1) / C
C → 0
Ηr in the definition was obtained by dividing the viscosity of a diluted solution of polytrimethylene terephthalate yarn or polyethylene terephthalate yarn dissolved in an o-chlorophenol solvent having a purity of 98% or more at 35 ° C. by the viscosity of the solvent measured at the same temperature. Value, defined as relative viscosity. C is the polymer concentration expressed in g / 100 ml. In addition, since it is difficult to measure the intrinsic viscosity of each composite multifilament using polymers having different intrinsic viscosities, two types of polymers are used under the same spinning conditions as the composite multifilament. The intrinsic viscosity measured using the yarn obtained by spinning alone was used as the intrinsic viscosity constituting the composite multifilament.
(2) Initial tensile resistance:
JIS L 1013 Test method for chemical fiber filament yarn According to the test method for initial tensile resistance, a tensile test was performed by applying an initial load of 0.0882 cN / dtex per unit fineness of the sample, and the initial tension was determined from the obtained load-elongation curve. The resistance (cN / dtex) was calculated, and the average value of 10 times was obtained.

(3) Stretch / extension rate, stretch / elastic modulus:
JIS L 1090 Bulk test yarn test method for synthetic fiber filaments Measured according to stretch test method A method, calculated stretch elongation (%) and stretch elastic modulus (%), and determined the average of 10 times. . The stretch elongation rate and the stretch elastic modulus of the actual crimp were measured after leaving the sample unwound from the winding package in an environment of a temperature of 20 ± 2 ° C. and a humidity of 65 ± 2% for 24 hours. The stretch elongation rate and the stretch elastic modulus after the hot water treatment were obtained by immersing in hot water at 98 ° C. for 30 minutes with no load and then naturally drying and drying for 24 hours with no load.
(4) Heat shrinkage stress:
Using a thermal stress measurement device (trade name KE-2, manufactured by Kanebo Engineering Co., Ltd.), the sample is cut to a length of 20 cm, both ends are connected to form a ring, and the measurement device is loaded with an initial load of 0.044 cN / dtex. The shrinkage stress is measured at a rate of 100 ° C./min, and the heat shrinkage stress at 100 ° C. is read from the change curve of the heat shrinkage stress with respect to the obtained temperature.
(5) Elastic recovery rate at 10% elongation:
The fiber was attached to a tensile tester with a distance between chucks of 10 cm, stretched to a stretch rate of 10% at a pulling speed of 20 cm / min, and left for 1 minute. Then, it shrinks again at the same speed, and draws a stress-strain curve. The elongation when the stress becomes zero during shrinkage is defined as the residual elongation (A). The elastic recovery rate was determined according to the following formula.
Elastic recovery rate at 10% elongation = (10−A) / 10 × 100 (%)

(6) Dyeing rate (easily soluble disperse dye definition):
Using 50d / 36f polyethylene terephthalate yarn, a tubular knitting machine (34GG Crimper Machining model TC-21 manufactured by Tsutsumi Seiki Co., Ltd.) is used to create a tubular knitted fabric, which contains a nonionic surfactant 2g / l. Scouring at 70 ° C. for 20 minutes in a bath, washing and drying, and cylindrical knitted poly (ethylene terephthalate) fiber preset for 30 seconds at 180 ° C. Dye usage 4% owf, bath ratio 50 times, pH 5 (adjusted with acetic acid ), A dispersant [trade name Nikkasan Salt RM-340, manufactured by Nikka Chemical Co., Ltd.] is dyed at 130 ° C. for 60 minutes in a dye bath of 0.5 g / l. Next, except that the pH is 11 (adjusted with sodium carbonate), dyes are extracted with dimethylformamide from the dyed fabrics of pH 5 and pH 11 obtained by dyeing in the same manner, and the amount of dyeing is measured by colorimetric analysis. The dyeing rate was determined by the following formula.
Dyeing rate = (Dyeing amount at pH 11 / Dyeing amount at pH 5) × 100 (%)
(7) Washing fastness:
Evaluation was performed based on JIS-L-0844, A-2 method. Polyester and nylon were used for the standard attached cloth.
(8) Light fastness:
Based on JIS-L-0842, it evaluated on the conditions of the 3rd exposure method and the black panel temperature of 63 +/- 3 degreeC.
(8) Leveling:
Ten people who obey the dyeing technique were visually judged according to the following criteria and evaluated based on the total score.
3 points: Very uniformly dyed.
2 points: Although there is a slight lack of leveling, there is no problem as a commercial product.
One point: It is dye | stained unevenly and lacks in commercial property.

[Examples 1 to 5]
Polytrimethylene terephthalate having an intrinsic viscosity [η] of 0.92 is obtained as an undrawn yarn at a spinning temperature of 265 ° C. and a spinning speed of 1200 m / min, then a hot roll temperature of 60 ° C., a hot plate temperature of 140 ° C., a draw ratio of 3 times, The yarn was drawn at a drawing speed of 800 m / min to obtain a drawn yarn of 56 dtex / 24f. The tensile strength, elastic modulus, and elastic recovery at 10% elongation of the drawn yarn were 3.3 cN / dtex, 46%, 20 cN / dtex, and 98%, respectively.
Using the obtained 56 dtex / 24f polytrimethylene terephthalate fiber as the warp and 77 dtex / 24f nylon 66 fiber (Leona (registered trademark) manufactured by Asahi Kasei Co., Ltd.) as the weft, a plain fabric production machine (density: 98 warp / 2. 54 cm, 80 wefts / 2.54 cm).
The obtained plain woven fabric machine was scoured and spread at 95 ° C. with a continuous scourer, and preset using a pin tenter at 160 ° C.
The obtained dough was dyed in one step in one bath at 40 ° C to 2 ° C / min and at 120 ° C for 30 minutes under the conditions shown below using a liquid dyeing machine, washed with water, and then 2 g of sodium carbonate. / L, Hydrosulfite 2 g / l, Sunmall RC-700 2 g / l (manufactured by Nikka Chemical Co., Ltd.), reducing and washing at a bath ratio of 1:20 at 70 ° C. for 10 minutes, neutralizing, washing with water and drying. Then, a finishing set at 150 ° C. was performed using a pin tenter.

<Dyeing conditions>
Bath ratio; 1:20
Leveling agent: Nikka Sun Salt RM-340 0.5 g / l (manufactured by Nikka Chemical Co., Ltd.)
pH adjuster; Meisan PC 5g / l (manufactured by Meisei Chemical Co., Ltd.)
Fixing agent; E / N dye fixing agent 5% omf (Daiichi Kasei)
Dye; Example 1 E / N Red 15A 3% omf (〃)
Example 2 E / N Navy Blue 17NA 3% omf (〃)
Example 3 E / N Yellow Brown 3% omf (〃)
Example 4 E / N Yellow 12A 3% omf (〃)
Example 5 E / N Blue 16A 3% omf (〃)
*% Omf is relative to the mass of mixed goods.
The physical property evaluation results of the obtained dyed cloth are shown in Table 1. In each of the mixed products of Examples 1 to 5, the fastness to washing is grade 5, the light fastness is grade 5 or more, and the level dyeing property is 28 points or more. It was excellent in both fastness and levelness.

Example 6
Two types of polytrimethylene terephthalate having different intrinsic viscosities were extruded into a side-by-side mold at a ratio of 1: 1 to obtain an undrawn yarn at a spinning temperature of 265 ° C. and a spinning speed of 1500 m / min, and then a hot roll temperature of 55 ° C. and a hot plate temperature of 140 C., a drawing speed of 400 m / min, and a draw ratio were set so that the fineness after drawing was 84 dtex, and then twisted to obtain an 84 dtex / 12f side-by-side composite multifilament yarn. The intrinsic viscosity of the obtained raw yarn was [η] = 0.88 on the high viscosity side and [η] = 0.70 on the low viscosity side. The physical properties of this raw yarn are shown in Table 2.
The obtained raw yarn was used using a pin false twisting machine IVF338 manufactured by Ishikawa Seisakusho, with a yarn speed of 190 m / min, false twist number of 3400 T / m, false twist directions S and Z, false twisting temperature of 170 ° C., 1st feed 0. False twisting was performed under the conditions of 0% and TU feed 4.1%, and S and Z false twisted yarns were wound with twin yarns.
The resulting 167 dtex / 24f side-by-side composite multifilament false twist yarn is used as the weft, and 78 dtex / 52f nylon 66 yarn (Leona (registered trademark) manufactured by Asahi Kasei Co., Ltd.) is used as the weft yarn. Density: warp 185 Book / 2.54 cm, weft 120 / 2.54 cm). The obtained raw machine was scoured and relaxed at 90 ° C. with a softener, and preset using a pin tenter at 140 ° C.

The obtained dough was all the same as Example 1 except that the dye was E / N Black 20N 10% omf (Daiichi Kasei) and the pH adjuster was changed to 0.5 g / l of acetic acid using a liquid dyeing machine. In the same manner, the temperature was increased from 40 ° C. at 2 ° C./min, and dyeing was performed in one step in a bath for 45 minutes at 130 ° C. After washing with water, using Redol C (Degloline-based reducing agent) 4 g / l and acetic acid 1 g / l, reducing and washing at a bath ratio of 1:20 at 70 ° C. for 10 minutes, neutralizing, washing with water, and drying, A finishing set at 150 ° C. was performed using a pin tenter.
The physical property evaluation results of the obtained dyed fabric are shown in Table 1. The fastness to washing is grade 5, the fastness to light is grade 5, the leveling property is 30 points, and both the fastness and leveling property are excellent. Met. It was excellent in fastness and levelness.

[Examples 7 to 9]
Two types of polytrimethylene terephthalate having different intrinsic viscosities were extruded into a side-by-side mold at a ratio of 1: 1 to obtain an undrawn yarn at a spinning temperature of 265 ° C. and a spinning speed of 1500 m / min, and then a hot roll temperature of 55 ° C. and a hot plate temperature of 140 C., a draw speed of 400 m / min, and a draw ratio were set so that the fineness after drawing was 56 dtex, and then twisted to obtain a 56 dtex / 12 f side-by-side composite multifilament raw yarn.
The intrinsic viscosity of the obtained raw yarn was [η] = 0.90 on the high viscosity side and [η] = 0.70 on the low viscosity side. The physical properties of this raw yarn are shown in Table 2.
The obtained 56 dtex / 12f side-by-side composite multifilament raw yarn and 56 dtex / 24f nylon 66 fiber (Leona (registered trademark) manufactured by Asahi Kasei Co., Ltd.) at a ratio of 1: 1, a single circular knitting machine SM-8 (28 Using a gauge, 33.0 cm diameter, 1152 needles), adjust the course and well of the living machine to 32 pieces / 2.54 cm and 36 pieces / 2.54 cm, respectively, and then knitted with a lantern piece I got a living machine. The yarn feeding to the knitting machine was a plating method, and the surface was nylon 66 and the back was a reversible structure that was a side-by-side composite multifilament yarn.
The obtained knitted fabric was scoured at 95 ° C. with a paddle dyeing machine, and steam-set at 110 ° C. using a steam setter.
The obtained dough was dyed in one step in a single bath at 1 ° C./min from 40 ° C. under the conditions shown below using a paddle dyeing machine, 20 minutes at 100 ° C., washed with water, and scored. A roll FC-250 (a scouring agent manufactured by Kao Co., Ltd.) was used at a bath ratio of 1:20 at 70 ° C. for 10 minutes, washed with water, and tumbler dried at 80 ° C.

<Dyeing conditions>
Bath ratio; 1:20
Leveling agent: Nikka Sun Salt RM-340 0.5 g / l (manufactured by Nikka Chemical Co., Ltd.)
pH adjuster; Meisan PC 5g / l (manufactured by Meisei Chemical Co., Ltd.)
Fixing agent; E / N dye fixing agent 5% omf (Daiichi Kasei Co., Ltd.)
Dye; Example 7 E / N Yellow T-112 0.5% omf (〃)
Example 8 E / N Red T-116 0.5% omf (〃)
Example 9 E / N Blue T-124 0.5% omf (〃)
*% Omf is relative to the mass of mixed goods.
The physical property evaluation results of the obtained dyed cloth are shown in Table 1. In each of the mixed products of Examples 7 to 9, the fastness to washing is grade 5, the light fastness is grade 5 or more, and the level dyeing property is 26 points or more. It was excellent in both fastness and levelness.

[Comparative Examples 1-3]
In Example 1, except that the dye was changed to the following, everything was the same, the temperature was increased from 40 ° C. to 2 ° C./min, and dyed in one step for 30 minutes at 120 ° C. , Water washing, reduction washing, water washing, neutralization, and setting.
The physical property evaluation results of the obtained dyed fabric are shown in Table 1. Nylon contamination of the wash fastness is as low as 2 to 3 grade, light fastness is 3 to 4 grade, and leveling property is also 20 to 24 points. The mixed articles of Comparative Examples 1 to 5 were all inferior in fastness and levelness.
Comparative Example 1 Disperse Dye Sumikaron Rubin SE-2BL 2% omf (dyeing rate over 60%)
Acid dye Lanyl Red B 1% omf (1: 2 gold included)
Comparative Example 2 Disperse Dye Sumikaron Navy-Blue S-2GL 2% o mf (dyeing rate over 60%)
Acid Dye Lanyl Navy Blue 1% omf (1: 2 gold included)
Comparative Example 3 Disperse Dye Sumikaron Brown S-5RL 2% omf
(Over 60% dyeing rate)
Acid Dye Lanyl Brown R 1% omf (1: 2 metal included)
The dyes used are all manufactured by Sumitomo Dyetech.

[Comparative Example 4]
In Example 1, except that the dye and the dyeing temperature were changed as follows, the temperature was increased from 40 ° C. to 2 ° C./min, and one-step dyeing was performed at 100 ° C. for 1/20 bath, and then Example 1 In the same manner as above, washing with water, reduction washing, washing with water, neutralization and setting were performed.
The physical property evaluation results of the obtained dyed cloth are shown in Table 1. Although the fastness to washing is as good as 4 to 5, the light fastness is as low as 2 and the leveling property is 13 points and uneven. It was a dyed fabric and was inferior in fastness and levelness. The dyes used are all manufactured by Sumitomo Dyetech.
Disperse Dye Sumikaron Blue S-3RF 0.2% omf
(Over 60% dyeing rate)
Acid dye Suminol Fast Blue G 0.1% omf
(Milling dye)

[Comparative Example 5]
In Example 1, except that the dye and the dyeing temperature were changed as follows, the temperature was increased from 40 ° C. to 2 ° C./min, and one-step dyeing was performed for 45 minutes at 130 ° C., and then Example 1 In the same manner as above, washing with water, reduction washing, washing with water, neutralization and setting were performed.
The physical property evaluation results of the obtained dyed cloth are shown in Table 1. Although the level dyeing property is good at 27 points, the nylon fastness of washing fastness is 2nd grade, and the light fastness is 3rd grade as low as fastness. Both leveling properties were not satisfied. The dyes used are all manufactured by Sumitomo Dyetech.
Disperse Dye Sumikaron Black S-RPD 4% omf
(Over 60% dyeing rate)
Acid Dye Lanyl Black F-GL 2% omf (1: 2 gold included)

  The present invention is a dyeing method for mixing polytrimethylene terephthalate fiber and polyamide fiber, and dyeing of mixed goods used in the clothing field such as inner, underwear, outer, and sports, and material fields such as narrow tape, hook-and-loop fastener, and lining. It can be suitably used as a method.

Claims (2)

  Dyeing rate when dyeing a mixed article containing polytrimethylene terephthalate fiber and polyamide fiber in a single bath and dyeing a fabric made of polyethylene terephthalate fiber at a dyeing temperature of 130 ° C. and a pH of 5 An azo disperse dye having a dyeing rate of 15 to 60% when the pH is 11 and a 1: 2 gold-containing dye, and a polyamide-based fixing agent is used together during or after the dyeing. A method for dyeing mixed goods characterized by the above. The method for dyeing mixed goods according to claim 1, wherein the polytrimethylene terephthalate-based fiber is a latently crimpable polyester fiber having at least one component made of polytrimethylene terephthalate.