JP2002129485A - Dyed mixed fiber article of fiber dyeable with disperse dye and polyurethane fiber and method for dyeing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dyed mixed fiber article of fibers dyeable with a disperse dye with polyurethane fibers having excellent color developing properties and color fastness. SOLUTION: This dyed mixed fiber article of the fibers dyeable with the disperse dye with the polyurethane fibers is obtained by mixing the fibers dyeable with the disperse dye with the polyurethane fibers and then dyeing the resultant mixed fiber article. The dyed mixed fiber article has a color fastness to a perspiration-alkali of grade 3 or higher according to the JIS L-0848 and a surface color shade without exceeding 20 at the most in terms of L value determined by a spectro-colorimetry. The mixed fiber article is dyed with the disperse dye selected from the group of the disperse dyes including benzeneazo disperse dyes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mixed dyed product of a disperse dye dyeable fiber and a polyurethane fiber, and a method for fast dyeing the same mixed product with a disperse dye. The present invention relates to a mixed dyed product of a disperse dye dyeable fiber and a polyurethane fiber, and a method of fast dyeing the mixed product with a disperse dye.

[0002]

2. Description of the Related Art When dyeing a mixed fabric of a dye-dispersible fiber represented by polyethylene terephthalate fiber and polyurethane fiber with a disperse dye, the dye is dyed because the disperse dye is excessively dyed on the polyurethane fiber. There is a problem that the color fastness of the mixed fabric is significantly reduced. Therefore, it is necessary to remove the disperse dye excessively dyed on the polyurethane fiber by reducing and washing the dyed cloth.
However, it is difficult to sufficiently remove the disperse dye which is excessively dyed on the polyurethane fiber in the mixed dyed product by reduction washing, so that a mixed dyed product having a satisfactory color fastness cannot be obtained. In particular, with regard to the sweat alkali fastness, a dye-mixed fabric with a disperse dye has not been obtained having sufficient fastness.

[0003] There is also a problem with the dry cleaning fastness of the dyed product of the mixed fabric. This is because the dry cleaning liquid becomes extremely dirty and reversely contaminates white areas or other fibers. The cause of the contamination of the dry cleaning liquid is the disperse dye remaining in the polyurethane fiber, and the degree of the contamination of the dry cleaning liquid is almost proportional to the residual concentration of the disperse dye. For this reason, the reduction washing of the mixed dyeing dyed with the disperse dye is carried out under severe conditions in which the concentrations of the reducing agent and the alkali agent are higher than the normal concentrations, for example, 10 g / liter, respectively, and the processing temperature is also reduced. It is necessary to strengthen the cleaning conditions, such as increasing the temperature to 90 ° C. However, in a mixed knitted fabric having a high degree of polyurethane fiber coverage, such as covering yarn, not only can the disperse dye in the polyurethane fiber be removed to a satisfactory degree even if the reduction washing conditions are strengthened, The color developability of the disperse dye dyeable fiber is reduced, and the color variation between dyeing batches is increased.

For this reason, dyes that are easily decomposed by alkaline reduction washing, such as heterocyclic azo type, condensed type disperse dyes, and diester type disperse dyes, have been used. However, there is a problem that it is difficult to produce all colors only with such a dye and the price of the dye is high. Also, because spandex is dyed excessively,
There has been no improvement in coloration and blurring of the dyeing, and at present the darkness dyed products in the outer and inner fields have not yet obtained sufficient fastness performance.

JP-B-62-38479 discloses that a mixed fiber structure which is not a mixed product using elastic polyurethane fibers but contains elastic polyester filaments is dyed with a disperse dye and then treated with tannic acid and an aqueous tartar solution. A method for improving the color fastness, especially the wash fastness, has been proposed. However, since a large amount of disperse dye remains in the elastic polyester filament itself, there is a problem that when dry-cleaning is performed, the dry-cleaning liquid is significantly contaminated. Also, the sweat fastness is not at a sufficiently satisfactory level.

[0006] Therefore, in reality, high quality mixed fabrics having high color fastness, extremely low dry cleaning liquid contamination, and high quality have not been obtained. Further, in the mixed fabric of the disperse dye dyeable fiber and the polyurethane fiber, since the disperse dye is excessively dyed on the polyurethane fiber, the color developability of the disperse dye dyeable fiber is lowered, and only a product having an inferior appearance is obtained. .

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a mixed dyed product of a disperse dye dyeable fiber and a polyurethane fiber which is excellent in wet dyeing fastness such as sweat alkali resistance and washing resistance. Another object of the present invention is to provide a dyeing method for fast dyeing a mixed article of a disperse dye dyeable fiber and a polyurethane fiber to a predetermined concentration with a disperse dye while suppressing the dyeing of the polyurethane fiber.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a mixed dyed product obtained by mixing a disperse dye dyeable fiber and a polyurethane fiber and then dyeing the mixed dyeable product, wherein the mixed dyed product is at least tertiary JIS L. A dyeable disperse dyeable fiber and a polyurethane fiber, characterized in that they have a color fastness determined by a sweat alkali fastness test method according to -0848 and a surface color density represented by a color developing value L of 20 or less. This is a mixed dyed product. The mixed dyed product obtained by mixing the disperse dye-dyeable fiber of the present invention and the polyurethane fiber and then dyeing the mixture has a sweat alkali fastness of JIS L-0848 of at least grade 4 and a JIS L-0860 of at least grade 3 of JIS L-0860. It is preferable that the dyed product has a wet color fastness that further satisfies at least one of the dry cleaning solution contamination values.

[0009] The mixed dyeing product of the present invention has at least a class 4 J
In the case of having a sweat alkali fastness of IS L-0848, it is desirable that the dye-dispersible dyeable fiber constituting the mixed product is dyed with a heterocyclic azo type, a condensed type disperse dye, or a diester type disperse dye. . In the mixed dyeing product of the present invention, it is desirable that the degree of coloring of the polyurethane fiber contained in the mixed product is 60 or less. Thus, even if the mixed dyed product of the present invention is a mixed dyed product post-dyed with a disperse dye, the wet dyeing fastness can be maintained at 3 or more.

In the mixed dyeing product of the present invention, the ratio of the disperse dye dyeable fiber to the polyurethane fiber is about 40% by weight or less for the polyurethane fiber. The mixing ratio is selected according to the form or use of the mixed product. The remaining mixed dyeable disperse dyeable fibers are wool, cotton, silk,
Hemp, cupra, viscose rayon fiber and the like may be mixed. In the case of a composite product which is not dyed only with a disperse dye, such as a disperse dye dyeable fiber and a cellulose fiber, the method of the present invention is applied when the disperse dye dyeable fiber is dyed with a disperse dye, and then the cellulose fiber is directly dyed. A two-bath method of dyeing with a dye or a reactive dye can be used. Also,
Before dyeing mixed products, apply the present invention method in advance,
Then, by dyeing by a one-bath method or a one-bath two-step method, a mixed article having excellent dyeing fastness performance according to the present invention can be obtained.

The mixed article of the dye-dispersible dyeable fiber of the present invention and the polyurethane fiber may be in the form of a thread or a cloth. Examples of the form of the yarn include a bare yarn of a polyurethane fiber, that is, a bare yarn (10 to 5).
00dtex) with a disperse dye-dyeable fiber, such as a covered yarn such as so-called covering yarn (single and double covering), ply-twisted yarn, core yarn, and entangled yarn. On the other hand, examples of the form of the fabric include a knitted fabric, a woven fabric, a nonwoven fabric, and a composite fabric thereof (for example, a laminated fabric). As a specific example, there is a so-called on-machine mixed product. In knitting and weaving, a bare yarn of a polyurethane fiber (in the case of a bare yarn, at the time of knitting or weaving, it is stretched by about 2 to 4 times) or a coated yarn on the machine. There is a knitted fabric obtained by mixing with or mixing with disperse dye dyeable fibers.

The polyurethane fiber used in the present invention is obtained by using 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 ethylene diamine or the like as a diamine component. 4,4'-diphenylmethane diisocyanate, such as polyether-based polyurethane fibers, polyester diols such as polycaprolactone, polyesters composed of adipic acid / 1,6 hexanediol / neopentyl glycol, and aliphatic diols such as butanediol. Polyurethane fibers are appropriately selected from polyester-based polyurethane fibers obtained by using an aromatic diisocyanate as a diisocyanate component. Polyurethane fiber, if necessary, metal oxides, metal hydroxides and other chlorinated water deterioration inhibitors,
For example, magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrotalcite compounds, etc., alone or as a mixture of two or more thereof are preferably added in an amount of 0.1 to 6.0. % By weight, and may further contain other known stabilizers, ultraviolet absorbers, and the like.

The polyurethane fiber is appropriately selected from bright yarn having high clarity, semi-dull yarn having low gloss, and the like according to the application. The object of the present invention cannot be achieved with a mixed product with a polyester ether elastic fiber. As shown in the comparative examples described below, the polyester ether elastic fiber can be dyed in a dye bath containing tannic acid and a polyvalent metal compound at the time of dyeing using a polyester ether elastic fiber instead of the polyether polyurethane fiber. No effect of inhibiting the dyeing of the disperse dye on the dye is observed, and no improvement in the color fastness is observed.

[0014] In the present invention, the disperse dye-dyable fibers used in the mixture with the polyurethane fibers include polyethylene terephthalate, polyoxyethylene benzoate, polybutylene terephthalate, polytrimethylene terephthalate, polyamide, polyacryl, polyvinyl alcohol, acetate and the like. Fibers that can be dyed with disperse dyes. The disperse dye dyeable fiber is not particularly limited in its single yarn decitex, but is preferably 0.1 to 6 decitex, more preferably 0.5 to 3 decitex, and although not particularly limited, the total decitex is 10 to 340. Fibers with decitex are preferably applied. When these fibers are used, a fabric excellent in dyeability and feeling can be obtained.

The form of the disperse dye dyeable fiber may be a long fiber or a short fiber, may be uniform or thick in the length direction, and may be round, triangular, L-shaped or T-shaped in cross section.
It may be a polygonal type such as a type, a Y type, a W type, an eight type, a flat type, a dog bone type, etc., a multi type, a hollow type or an irregular type. The form of the yarn from which the fiber is processed is a spun yarn such as a ring spun yarn, an open-end spun yarn, a multifilament raw yarn (including an ultrafine yarn) having a single yarn decitex of about 0.1 to 6 decitex, and a sweet yarn. There are twisted yarn to strong twisted yarn, mixed fiber yarn, false twisted yarn (including drawn false twisted yarn of POY), and air jet processed yarn. The mixed product referred to in the present invention is a blend of natural fibers such as wool, cotton, and silk, cupra, viscose rayon fiber, and polyamide fiber, as long as the object of the present invention is not impaired. Etc.),
It can be formed by mixing means such as entangled blended fiber (different shrinkage blended yarn with high shrinkage yarn), intertwist, composite false twist (elongation difference false twist) and two-feed air jet processing.

In the case of a mixed article in which natural fibers, cellulose, polyamide fibers and the like are additionally mixed partially with the disperse dye dyeable fiber, the method of the present invention is used to dye the disperse dye dyeable fiber with the disperse dye. And then a two-bath method of dyeing with a dye commonly used for natural fibers, cellulose and polyamide fibers. Alternatively, the dyeing fastness referred to in the present invention is excellent by applying the method of the present invention in advance before dyeing the mixed product, and then performing additional mixed dyeing of cellulose fibers or the like in a one-bath method or a one-bath two-stage method. Mixed products are obtained. When the disperse dye dyeable fiber is a polyester fiber, ordinary polyethylene terephthalate fiber can be used. However, a mixture of products for inner and sports applications, particularly those requiring polyurethane fiber elongation recovery, is required. When it is necessary to prevent thermal embrittlement during dyeing of the produced polyurethane fiber, it is preferable to use an easily dyeable polyester fiber.

The easily dyeable polyester fiber is a disperse dye C.I. Disperse Blue 56 (C.I.
perse Blue 56; for example, resolin blue F
BL [manufactured by Meisei Chemical Industry Co., Ltd.] using a dye amount of 3% omf, a bath ratio of 50 times, pH 6 (adjusted with acetic acid), and a dispersant (eg, Disper TL). ) Means a polyester fiber having a dye exhaustion of 80% or more represented by the following formula (1) after dyeing at 100 ° C for 120 minutes in a dye bath having a content of 1 g / liter. Dye exhaustion rate (%) = [Amount of dye dyed on fiber (weight) /
Amount of dye added to dye bath (weight)] × 100

The easily dyeable polyester fiber is spun, for example, at a spinning speed of 4000 m / min or more, and is heated to 220 to 300
Fibers made of a homopolymer of polyethylene terephthalate subjected to heat treatment of 180 to 240 ° C. at a temperature of 180 ° C. or wet heat, and so-called high-speed spun fibers of a spin take-up type spun at a spinning speed of 6200 m / min or more. Further, in place of the polyethylene terephthalate fiber, a linear polymer having ethylene terephthalate as a repeating unit is easily copolymerized with isophthalic acid, a sodium salt of sulfonated isophthalic acid, polyethylene glycol, adipic acid and the like as a third component. High-speed spun fibers of dyeable copolymerized polyester may be used. These polyester fibers may contain a matting agent, a stabilizer, an antistatic agent and the like which are usually added to synthetic fibers.

Another example of the easily dyeable polyester fiber is a polytrimethylene terephthalate fiber. This fiber refers to a polyester fiber having a trimethylene terephthalate unit as a main repeating unit, and has a trimethylene terephthalate unit content of about 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more. A thing. Therefore, the total amount of the other acid component and / or glycol component as the third component is within a range of about 50 mol% or less, preferably 30 mol% or less, further 20 mol% or less, and more preferably 10 mol% or less. Polytrimethylene terephthalate contained.

The polytrimethylene terephthalate fiber is
After obtaining an undrawn yarn at a winding speed of about 1500 m / min,
A method of twisting by about 2 to 3.5 times, a direct drawing method (spin draw method) in which a spinning-drawing step is directly connected, and a winding speed of 5000
It may be manufactured by any spinning method of a high-speed spinning method (spin take-up method) of m / min or more. Polytrimethylene terephthalate fibers further include matting agents such as titanium, stabilizers such as phosphoric acid, ultraviolet absorbers such as hydroxybenzophenone derivatives, crystallization nucleating agents such as talc, lubricating agents such as Aerosil, and hindered phenol derivatives. And the like, an antioxidant, a flame retardant, an antistatic agent, a pigment, a fluorescent whitening agent, an infrared absorber, an antifoaming agent, and the like.

The 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 appropriate reaction conditions. . In this synthesis process, an appropriate one or more third components may be added to form a copolymerized polyester, or a polyester other than polytrimethylene terephthalate such as polyethylene terephthalate, or nylon and polytrimethylene terephthalate may be separated. After synthesizing, blending or composite spinning (sheath core, side-by-side, etc.)
May be. The third component that can be added includes aliphatic dicarboxylic acids (such as oxalic acid and adipic acid), alicyclic dicarboxylic acids (such as cyclohexanedicarboxylic acid), and aromatic dicarboxylic acids (such as isophthalic acid and sodium sulfoisophthalic acid). ), Aliphatic glycols (ethylene glycol,
1,2-propylene glycol, tetramethylene glycol, etc.), alicyclic glycol (cyclohexanedimethanol, etc.), aliphatic glycol containing aromatics (1,4-bis (β-hydroxyethoxy) benzene, etc.), polyether glycol (Eg, polyethylene glycol and polypropylene glycol), aliphatic oxycarboxylic acids (eg, ω-oxycaproic acid), and aromatic oxycarboxylic acids (eg, P-oxybenzoic acid). Compounds having one or more ester-forming functional groups (such as benzoic acid or glycerin) can also be used in a range where the polymer is substantially linear.

The mixed dyed product of the present invention includes all the mixed product products having a predetermined color fastness obtained by applying the above-mentioned known mixing means to the disperse dye dyeable fiber and the polyurethane fiber. In. That is, the disperse dye dyeable type of the present invention has at least a third-grade dyeing fastness according to a sweat alkali fastness test method according to JIS L-0848, and has a surface color density represented by a color developing value L of 20 or less. The mixed dyed product of the fiber and the polyurethane fiber can be prepared by a method of dyeing a mixed product of the undyed disperse dye dyeable fiber and the polyurethane fiber using a disperse dye.

Prior to mixing, the disperse dye dyeable fibers are dyed in a desired color in advance, or mixed with polyurethane fibers by mixing several pre-dyed disperse dye dyeable fibers with the desired color. Is prepared. In this method for preparing a mixed dyeing product, since the mixed product is not dyed with a disperse dye, the urethane fibers in the mixed product are not dyed with the disperse dye nor are contaminated, and are easily at least tertiary JIS.
A mixed dyed product having dye fastness according to the sweat alkali fastness test method according to L-0848 can be prepared. However, mixed fabrics are widely used in outerwear, innerwear, sports fields, and the like, and disadvantageous in terms of cost when color development is required. In addition, there is a problem of the "eye-opening" phenomenon in which the rubber elastic fibers appear white, which degrades the quality. From this viewpoint, it is necessary to apply the dyeing method of the present invention to an undyed mixed product to obtain a mixed dyed product.

In order to obtain the mixed dyed product of the present invention by applying the disperse dye dyeing to the undyed mixed product, the disperse dye is specially treated under the disperse dye dyeing method so that the polyurethane fibers in the mixed product are not dyed. It is essential to adopt a proper method. The present inventors, when applying the disperse dye dyeing method to undyed mixed products, dye after treating with a polyvalent metal compound and tannic acid, or dye the polyvalent metal compound and tannic acid when dyeing By dyeing in the bath, the disperse dye remarkably suppresses dyeing to the polyurethane fiber in the mixed product during dyeing, selectively dyes disperse dye dyeable fiber, and has excellent color development and dyeing fastness. It has been found that a mixed dyed product of a disperse dye dyeable fiber and a polyurethane fiber can be obtained.

Based on the above findings, the undyed mixed product of the disperse dye dyeable fiber and the polyurethane fiber shows remarkable dyeing of the disperse dye on the polyurethane fiber contained in the mixed product in the dyeing containing the disperse dye. The disperse dye on the polyurethane fiber is suppressed, and the disperse dye dyed on the polyurethane fiber is easily substantially decolored even in the reduction washing after the dyeing. Advantageously, this function is exhibited by disperse dyes commonly used in practical dyeing, irrespective of the coloring chemical structure of the dye. Therefore, the dyeing method of the present invention makes it possible to perform fast dyeing with a convenient benzeneazo-based disperse dye which is inexpensive, has many color variations and is easy to use for deep dyeing. The function of suppressing the disperse dye from adhering to the polyurethane fiber is similarly exerted on a type of dye that is easily dropped off during reduction washing, such as a heterocyclic azo disperse dye, a condensed disperse dye, and a diester disperse dye. .

According to the dyeing method of the present invention, in all disperse dyes irrespective of the structural type of the disperse dye, dyeing on the polyurethane fiber is significantly reduced. Easy to do,
It enables the problem of fastness related to the problem of disperse dye contamination on polyurethane fibers to be solved at once. In the dyeing method of the present invention, a mixed fabric product having a fastness of sweat alkali and a level of dry cleaning liquid of tertiary or higher can be obtained using not only a general benzene azo dye but also other disperse dyes. In addition, when a heterocyclic azo disperse dye, a condensed disperse dye, or a diester disperse dye, which is an alkali easily hydrolysable dye, is used, sweat alkali fastness and dry cleaning liquid contamination are extremely high, at least 4th grade. Gives excellent dyeing results.

According to the present invention, it is possible to realize fast dyeing of the mixed article using a dye from a wide dye spectrum including a heterocyclic azo type, a condensed type disperse dye including a azo type disperse dye, and a diester type disperse dye. it can. Here, the polyvalent metal compound is preferably an antimony compound,
Others include tin, aluminum, zinc, barium,
Bismuth compounds and the like can be used, and these polyvalent metal compounds may be used in combination. As the antimony compound, antimony tartrate is preferable, and there are antimony sodium tartrate and antimony potassium tartrate,
Particularly preferred is antimony sodium tartrate.

The amount of the polyvalent metal compound used is preferably 0.01 to 1.5% omf, more preferably 0.02% omf.
If it is less than 0.5% omf, the object of the present invention may not be sufficiently achieved, and even if it exceeds this, improvement of the effect cannot be expected. Tannic acid is tannin obtained from quintet or gallic, and the amount of tannin used is preferably 0.1 to 10% omf, more preferably 0.2 to 10% in product concentration.
If it is less than 5% omf, the object of the present invention may be insufficiently achieved, and if it exceeds this, the effect is not improved and the cost becomes uneconomical. The ratio of the amount of the polyvalent metal compound to the amount of the tannic acid used is 1: 1 to 1:40, the preferable ratio is 1: 3 to 1:20, and the more preferable ratio is 1: 3 to 10.

The above-mentioned treatment before dyeing is preferably a method in which the mixed article is immersed in an aqueous solution containing a polyvalent metal compound and tannic acid, and the treatment temperature is preferably 40 to 130 ° C., particularly preferably 60 to 100 ° C. , Processing time is 10-40
Minutes are preferred. At this time, it is preferable to adjust the pH of the treatment solution to 3 to 5 with a pH adjuster such as acetic acid. For the mixed article which has been subjected to the pre-treatment, dyeing conditions using a disperse dye which is usually applied to polyester fibers and the like are applied. That is, as the dyeing bath, for example, using a dye solution containing a disperse dye, a leveling agent, a pH adjuster, and the like in addition to the disperse dye, the dyeing temperature of the disperse dye dyeable fiber, for example, 100 to 135 ° C., preferably 100 ° C.
Dye for 20-40 minutes at a temperature of １３０130 ° C.
The disperse dyes to be used are used alone or as a mixture of various disperse dyes in a desired concentration of chromatic or achromatic color.

The disperse dye is generally a benzeneazo-based disperse dye, for example, having a basic structure of 4-nitro-4 '.
An aminoazobenzene having a nitro group, a halogen atom, a cyano group, etc. at positions 2 and 2, 6 of the diazo component, an alkyl group, an alkoxy group at the position 2 'or 2', 5 'of the coupling component, Monoazo, disazo, naphthaleneazo disperse dyes, etc. in which a halogen atom, an acylamino group, etc. are introduced, or the 4 ′ amino group is substituted with an alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl, allyl, aralkyl group, etc. Can be applied. Heterocyclic azo disperse dyes,
For example, a compound using a heterocyclic compound as a diazo component or a coupling component, such as a thiazole azo, benzothiazole azo, quinoline azo, pyridone azo, imidazole azo, or thiophen azo disperse dye; a condensed disperse dye such as C.I. I. Disperse Yellow-54, C.I.
I. Quinoline-based disperse dyes such as Disperse Yellow-64 and C.I. I. Coumarin-based disperse dyes such as Disperse Yellow-82 and C.I. I. Aminoketone-based disperse dyes such as Disperse Yellow-58 and C.I. I. Disperse Red 356 and C.I. I. Benzodifuranone-based disperse dyes such as Disperse Red 367; diester-type disperse dyes such as C.I. I. Disperse dyes containing a diester group in the chemical structure, such as Disperse Red 278, are also mentioned by way of example.

In the combined dyeing method in which the above-mentioned polyvalent metal compound and tannic acid coexist in a disperse dye dyeing bath, the polyvalent metal compound and tannic acid are dissolved in an aqueous dye solution using dyeing conditions usually used for polyester fibers. Let it be 100-13
This is a method of dyeing at 5 ° C, preferably at 100 to 130 ° C. The dyeing time is preferably 20 to 40 minutes from the viewpoint of embrittlement of the polyurethane fiber and cost. At this time, the pH of the aqueous dye solution is preferably adjusted to 4 to 5 with a pH adjuster such as acetic acid. As the dispersing leveling agent used in this case, it is preferable to use a polyalkylene oxide adduct of an alkyl naphthalene-based or polyhydric alcohol fatty acid ester such as a β-naphthalenesulfonic acid formaldehyde condensate and a sulfated oxide thereof. In the present invention, after completion of the dyeing operation, the mixed dyed product is subjected to reduction washing in the presence of a hot alkaline agent.

The coexisting bath treatment of the tannic acid and the polyvalent metal compound used in the present invention suppresses the dyeing of the disperse dye to the polyurethane fiber and promotes the distribution of the disperse dye to the disperse dye dyeable fiber. This is a process focusing on. In the present invention,
The cooperative action of tannic acid and the polyvalent metal compound not only significantly suppresses the dyeing concentration of the disperse dye on the polyurethane fiber, but also disperses the disperse dye diffused into the polyurethane fiber to be rapidly decomposed by reduction washing after dyeing. Almost completely removed from polyurethane fibers. Thus, the coloring degree of the polyurethane fiber in the mixed dyed product is reduced to 60 or less, the wet dyeing fastness of the mixed dyed product is drastically improved, and the disperse dye dyeable type has a remarkably reduced contamination of the dry cleaning solution. It becomes possible to prepare a mixed dyed product of fiber and polyurethane fiber.

The post-dyeing method of the mixed article of the present invention increases the dyeing rate of the disperse dye on the disperse dye-dyeable fiber, reduces the waste of the dye, and has a high coloring property and a good appearance. In addition to being able to prepare a dyed product, there is also an effect that color variation between dyeing batches is suppressed and the operation rate of the dyeing machine is improved. Since the amount of the disperse dye attached to the polyurethane fiber is small, the concentration of the reducing agent and the concentration of the alkaline agent in the reduction washing are each sufficient at 1 to 2 g / liter, and the treatment temperature also needs to be increased. In addition, without the necessity of strengthening the reduction cleaning conditions, it is possible to prevent the occurrence of color variation for each reduction cleaning batch.

When the mixed article of the disperse dye dyeable fiber and the polyurethane fiber used in the present invention is a fabric, knitting,
After weaving, it is preferable to dye after relaxing and scouring. In this case, it is preferable to perform the scouring at a temperature of 60 to 98 ° C. while relaxing the fabric as much as possible from the viewpoint of enhancing the stretch recovery of the fabric. If morphological fixation before staining is required, 170-200 ° C.
After the reduction cleaning, finishing is performed in accordance with a conventional method, and the final set is set at a temperature lower than the preset temperature by 10 ° C. or more to obtain a preferable result.

The pretreatment for dyeing in a coexisting bath of tannic acid and a polyvalent metal compound used in the present invention comprises disperse dye dyeable fiber and natural fiber such as wool, cotton, silk, cupra, viscose rayon fiber or polyamide fiber. It is a very effective means in mixed products, piece dining, and product dyeing. The effect of suppressing dyeing on polyurethane fibers during disperse dye dyeing of the pretreated product is inferior to the combined dyeing method in which tannic acid and a polyvalent metal compound coexist in a disperse dye dyeing bath, but the fastness performance of the mixed fabric is sufficient. Is obtained.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples and the like, but the present invention is not limited to these examples and the like. The characteristic values and evaluation values in Examples and Comparative Examples are based on the following measurement methods and evaluation methods. [1] Sweat alkali fastness The mixed dyed product was evaluated using an alkaline artificial sweat liquid according to JIS L-0848. The degree of discoloration of the test piece and the degree of contamination of the attached white cloth piece were determined by comparing with the gray scale for discoloration and the gray scale for contamination, respectively. [2] Washing fastness The mixed dyed product was evaluated according to JIS L-0844 A-2 method. However, the detergent is Attack (Kao Corporation)
(Trade name) 1 g / liter. The degree of discoloration of the test piece and the degree of contamination of the attached white cloth piece were determined by comparing with the gray scale for discoloration and the gray scale for contamination, respectively.

[3] Contamination of dry cleaning solution A dry cleaning test is performed on the mixed dyed product in accordance with JIS L-0860, and the dry cleaning solution and the stain liquid after the dry cleaning test are placed in a porcelain container.
8 cc was taken at 0 m / m × 40 m / m × 10 m / m), and the degree of discoloration was determined by comparing the degree of liquid contamination with the gray scale for contamination. Good grades with little discoloration are grade 5
It was sequentially determined to be the first grade (large color fading). [4] Degree of coloration of polyurethane fiber in dyed product Polyurethane fiber is extracted from fabric, and the degree of coloration is determined by J
In accordance with IS Z-8730, a spectrophotometer (Kollm
It was evaluated using Macbeth MS-2020, manufactured by Orgen. The coloring degree D indicates the difference in coloring degree between polyurethane fibers before and after dyeing, and was determined by the following formula in the Lab color system. D = (ΔL ² + Δa ² + Δb ² ) ^1/2 where ΔL is the lightness index L of the polyurethane fiber before dyeing.
Is the value obtained by subtracting the measured value of the same index L of the dyeing finish from the measured value of. Similarly, Δa and Δb indicate the difference between the measured values of the chromaticness index in both states.

[5] Measurement of color development L value of dyed material The color density on the surface of the dyed fabric was measured by a spectrophotometer (Kollmor).
The L value in the Lab color system was measured using Genbe's model Macbeth MS-2020). The lower the L value, the higher the color developability. An L value of 20 or less indicates that the product is a deep-color dyed product. [6] Measurement of K / S value Using a surface spectrophotometer (manufactured by Kollmorgen, model: Macbeth MS-2020), measure the spectral reflectance of the dyed fabric (provided that the surface reflectance is the maximum). Using light) was measured using the following equation. In the formula, R is the reflectance (0 <R ≦ 1), and K is Kubelk M
The unk absorption coefficient, S, is the scattering coefficient. The greater the K / S value, the greater the degree of color development. K / S = (1-R) ² / 2R

[7] Measurement of ηsp / c To determine ηsp / c, the polymer was dissolved at 90 ° C. in a solvent of o-chlorophenol at a concentration of 1 g / deciliter, and then the resulting solution was transferred to an Ostwald viscous tube. It measured at ° C and calculated by the following formula. ηsp / c = (T / T ₀ ) / C T: Fall time of sample solution (second) T ₀ : Fall time of solvent (second) C: Solution concentration (g / deciliter) [8] Polyurethane fiber and polyester ether elasticity Fiber decitex measurement method A polyurethane fiber or a polyester ether elastic fiber is allowed to stand in a straight line with no tension and no charge in an atmosphere of 20 ° C. and a relative humidity of 65%, and is allowed to shrink. After that, 100
Ten pieces cut at a length of 0 mm are combined and weighed,
It is converted to the weight per 10,000 m, and the value is defined as decitex.

[0040]

Embodiment 1 ηsp / c = 0.65, TiO ₂ 0.4
% Polyethylene terephthalate at a spinning temperature of 290
Spinning at 70 ° C and winding speed of 70
A yarn of 56 dtex / 24f was obtained at a speed of 00 m / min. This yarn corresponded to the above-mentioned easily dyeable polyester fiber (dye exhaustion rate = 89%). Using this yarn and a 311 dtex polyether-based polyurethane fiber (trade name: Roika SC manufactured by Asahi Kasei Kogyo Co., Ltd.) under normal knitting conditions, a 6-course satin net knitted fabric (course density: 171 loops / 2.54 cm; A well density of 41 loops / inch) was prepared. The mixing ratio of polyurethane fibers in this knitted fabric with mixed polyurethane fibers was 21%.

The mixed knitted fabric was spread and relaxed at 90.degree. C., then pre-set at 180.degree. C., and dyed under the following dyeing conditions. Dyeing conditions Dye: C.I. I. Disperse Blue 167 (benzeneazo-based disperse dye) 7% omf Dispersing and leveling agent: Nikka San Salt RM-340 (manufactured by Nika Chemical Industry Co., Ltd.) 0.5 g / l acetic acid: 0.5 cc / l sodium acetate: 1 g / Liter Bath ratio: 1:20 Dyeing temperature, time: 120 ° C, 30 minutes In addition, tannic acid of various concentrations shown in Table 1 (tannic acid extract for dyeing manufactured by Dainippon Pharmaceutical Co., Ltd .; (50% pure) and sodium antimony tartrate.

After the dyeing is completed, the residual dyeing solution is discharged from the dyeing machine, water is poured into the dyeing machine, the temperature is raised to 70 ° C., and the following chemicals are added thereto to prepare a reducing washing bath having the following concentration. Then, the dyed product was subjected to reduction washing at 70 ° C. for 10 minutes. Thiourea dioxide: 2 g / l Caustic soda: 1 g / l Sunmol RC-700 (non-ionic detergent; manufactured by Nikka Chemical Co., Ltd.): 0.5 g / l Bath ratio: 1:30 After this reduction washing, The remaining solution was drained, and the dyed product was thoroughly rinsed with hot water and water, and then finished with a dry heat set at 160 ° C. for 30 seconds. Table 1 shows the results such as the evaluation of sweat fastness, washing fastness, and dry cleaning solution stainability of the finished dyed product. Almost no coloring was observed in the polyether-based polyurethane fiber constituting the mixed dyed polyurethane material.

[0043]

Comparative Example 1 A knitted fabric containing polyurethane fibers was repeatedly dyed and finished in the same manner as in Example 1, except that the dyeing bath was dyed without adding tannic acid and / or sodium antimony tartrate. Table 1 shows the properties and color fastness of the resulting dyed knitted fabric. From the results shown in Table 1, the dyed product of Example 1 of the present invention has a high coloring property (particularly, an L value is as low as 20 or less), and has a sweat alkali fastness of 3
The grade is extremely high, ie, higher than grade, the washing fastness is extremely good, ie, higher than grade 4, and the contamination of the dry cleaning liquid is higher than grade 3, which is high in commercial value. On the other hand, the dyed product according to Comparative Example 1 had a high degree of coloring of the polyether-based polyurethane fiber of 60 or more, and showed a high degree of sweat alkali fastness, washing fastness, and dry cleaning solution contamination, all of which were the same as those of Examples. Inferior to dyed goods.

[0044]

Comparative Example 2 In Example 1, a 156 dtex polyester ether elastic fiber (trade name: Lexe, manufactured by Teijin Limited) was used in place of the polyether-based polyurethane fiber. Mix rate of 16
Weight 6 course satin net knitted fabric (course density 177
Number of loops / inch, well density 43 loops / inch)
This mixed knitted fabric was dyed and finished in the same manner as in Example 1. Table 1 shows the measurement results such as the properties and the color fastness of the dyed finished knitted fabric. The coloring degree of the polyester ether elastic fiber of the dyed knitted fabric in Comparative Example 2 was as high as 60 or more, and the evaluation values of the sweat alkali fastness, the washing fastness, and the dry cleaning solution stainability were inferior to those of the dyed product of Example 1. I have.

[0045]

[Table 1]

[0046]

Example 2 The knitted fabric mixed with polyurethane prepared in Example 1 was subjected to a scouring relaxation treatment at 90 ° C., and then pre-set at 180 ° C., and prior to dyeing, tannic acid and sodium antimony sodium tartrate having the concentrations shown in Table 1 before dyeing. And acetic acid 0.5cc
/ Liter and treated at 80 ° C. for 20 minutes. The mixed knitted fabric that had been subjected to the tannin bath treatment was then dyed under the following conditions. After dyeing, it was subjected to reduction washing under the same conditions as in Example 1 to obtain a finished dyed product. Dyeing conditions Dye: C.I. I. Disperse Blue 167 (benzeneazo-based disperse dye) 7% omf Dispersing and leveling agent: Nikka San Salt RM-340 (manufactured by Nika Chemical Co., Ltd.) 0.5 g / l acetic acid: 0.5 cc / l sodium acetate: 1 g Bath ratio: 1:20 Dyeing temperature, time: 120 ° C., 30 minutes Table 2 shows the results of evaluation of the obtained dyed product such as sweat alkali fastness, washing fastness, and dry cleaning solution contamination. The polyether-based polyurethane fiber of the dyed product obtained was hardly colored by the dye.

[0047]

Comparative Example 3 In Example 2, prior to dyeing, the knitted fabric treated in the same manner as in Example 2 was treated in place of the pretreatment of Example 2 except that the tannic acid treatment, antimony sodium tartrate treatment and untreated knitted fabric shown in Table 2 were applied. It was dyed and finished. Table 2 shows the evaluation results of the obtained dyed products. From the results shown in Table 2, the dyed product of the dyeing method of Example 2 has a high L-value of 20 or less, high color development, a very high perspiration alkali fastness of 3 grade or more, and a high wash fastness of 4%. Grade or higher was extremely good, and a dyeing product with high commercial value with less contamination of the dry cleaning solution (grade 3 or higher) was obtained. On the other hand, the dyed product of Comparative Example 3 has a high degree of coloring of the polyether-based polyurethane fiber of 60 or more, and is higher than the dyed product of Example 2 in all of the fastness to sweat alkali, the fastness to washing, and the stain property of the dry cleaning solution. Inferior.

[0048]

[Table 2]

[0049]

Example 3 Polyethylene terephthalate 56 dtex / 30f having a W-shaped cross section (trade name: Technofine, manufactured by Asahi Kasei Kogyo Co., Ltd.) and 311 dtex polyether polyurethane fiber (trade name: Leica SC, manufactured by Asahi Kasei Kogyo Co., Ltd.) A 6-course satin net was knitted in the same manner as in Example 1, and the same knitted fabric was subjected to the same relaxation and presetting as in Example 1, and then dyed under the following conditions.

Dyeing Conditions Dye: C.I. I. Disperse Blue 167 (benzeneazo-based disperse dye) 7% omf Dispersing and leveling agent: Nikkasan Salt RM-340 0.5 g / liter Acetic acid: 0.5 cc / liter Sodium acetate: 1 g / liter Tannic acid: 3% omf antimony tartrate Sodium: 0.3% omf bath ratio: 1:20 Dyeing temperature, time: 125 ° C., 30 minutes The dyed knitted fabric is subjected to reduction washing after completion of dyeing in the same manner as in Example 1, and dried at 160 ° C. for 30 seconds. Finished with a set. Table 3 shows the results of the evaluation of the dyeing properties, sweat alkali fastness, washing fastness, and dry cleaning solution contamination of the obtained dyed product. The polyether-based polyurethane fibers in the obtained dyed product were hardly colored.

[0051]

Comparative Example 4 A knitted fabric was dyed and finished by repeating the same procedure as in Example 3 except that the dyeing was carried out without using tannic acid or sodium antimony tartrate. Table 3 shows the test and evaluation results of the mixed dyed knitted fabric obtained. In Table 3, the mixed dyed product obtained by the dyeing method of Example 3 has high color developability, extremely high sweat alkali fastness, extremely good washing fastness, and high commercial value with less contamination of the dry cleaning liquid. It is clear that has been obtained. On the other hand, the mixed dyeing product of Comparative Example 4 has a high degree of coloring of the polyether-based polyurethane fiber, and has a high degree of sweat alkali fastness, washing fastness, and dry cleaning solution stainability. Inferior to things.

[0052]

[Table 3]

[0053]

Example 4 Modified polyethylene terephthalate copolymerized with sodium salt of sulfonated isophthalic acid 56 dte
x / 36f (CVT, trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) and 311 dtex polyether-based polyurethane fiber (Roica SC, trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.), and a mixed 6-course satin similar to that of Example 1. Knitted net. Next, the mixed knitted fabric was spread and relaxed at 90 ° C., then pre-set at 175 ° C., and dyed under the following conditions.

Dyeing Conditions Dye: C.I. I. Disperse Blue 167 (benzeneazo-based disperse dye) 7% omf Leveling agent: Nikkasan Salt RM-340 0.5 g / l Acetic acid: 0.5 cc / l Sodium acetate: 1 g / l Tannic acid: 3% omf antimony sodium tartrate : 0.3% omf bath ratio: 1:20 Dyeing temperature, time: 110 ° C, 30 minutes After dyeing of the knitted fabric was completed, reduction washing was performed under the following conditions. The knitted fabric subjected to the reduction cleaning was subjected to dry heat setting and finished in the same manner as in Example 1.

Conditions for reduction washing Thiourea dioxide: 1 g / liter Caustic soda: 0.5 g / liter Sun-mol RC-700: 0.5 g / liter Bath ratio: 1:30 Treatment temperature, time: 70 ° C., 10 minutes obtained Table 4 shows the results of evaluation of the dyed product thus obtained in terms of sweat alkali fastness, washing fastness, and dry cleaning solution contamination. The polyether polyurethane fibers in this dyed product were hardly colored.

[0056]

Comparative Example 5 The same procedure as in Example 4 was carried out except that the mixed knitted fabric was dyed without using tannic acid or antimony sodium tartrate. Table 4 shows the results. As shown in Table 4, the mixed dyed product by the dyeing method of the example has high color developability, extremely high sweat alkali fastness, remarkably good washing fastness, and a commercial value with little dry cleaning liquid contamination. It is a highly dyed product. On the other hand, the dyed product of Comparative Example 5 has a high degree of coloring of the polyether-based polyurethane fiber,
All of the sweat alkali fastness, washing fastness, and stain resistance of the dry cleaning solution are inferior to the dyed product obtained in Example 4.

[0057]

[Table 4]

[0058]

Example 5 Polytrimethylene terephthalate having ηsp / c = 0.8 was prepared by polymerizing at a temperature of 265 ° C. and a spinning speed of 120.
It is melt spun at 0 m / min to obtain an undrawn yarn, and then stretched at a hot roll temperature of 60 ° C., a hot plate temperature of 140 ° C., a draw ratio of 3 and a draw speed of 800 m / min to obtain 56 dt.
ex / 24f drawn yarn was obtained. The stretchability, elastic modulus and elastic recovery at 10% elongation of this drawn yarn were 3.2 c each.
N / dtex, 45%, 28.4 cN / dtex and 96%. The elastic recovery rate of the yarn at 10% elongation was measured by applying an initial load of 0.011 g / dtex to the sample and elongating it at a constant rate of 20% elongation per minute. This time, the material is contracted at the same speed to draw a stress-strain curve, and the residual elongation (L) when the stress is reduced to 0.011 g / dtex, which is the same as the initial load, during the contraction, is obtained by the following equation. It is a value obtained by calculation according to

Elastic recovery rate at 10% elongation (%) = (10
-L) / 10 × 100 This polytrimethylene terephthalate yarn and 311 dte
x polyether-based polyurethane fiber (trade name: Roika SC, manufactured by Asahi Kasei Kogyo Co., Ltd.) under a normal knitting condition using a 6-course satin net knitted fabric (course density 171
Number of loops / inch, well density 41 loops / inch)
Was prepared. The mixing ratio of the polyurethane fibers in the mixed knitted fabric was 21%. This mixed knitted fabric is spread at 90 ° C.
After pre-setting at 175 ° C., the cells were stained under the following conditions.

Dyeing Conditions Dye: C.I. I. Disperse Blue 167 (benzeneazo-based disperse dye) 7% omf Dispersing and leveling agent: Nikka San Salt RM-340 (manufactured by Nika Chemical Co., Ltd.) 0.5 g / l acetic acid: 0.5 cc / l sodium acetate: 1 g / Liter bath ratio: 1:20 Dyeing temperature, time: 110 ° C., 30 minutes In each dyeing, tannic acid of various concentrations shown in Table 6 (Dyeing manufactured by Dainippon Pharmaceutical Co., Ltd.) Tannic acid extract) and antimony sodium tartrate were added for staining.

After completion of each dyeing, the dyeing residual liquid is discharged from the dyeing machine, and then water is added to the dyeing machine again, and the temperature is reduced to 70 ° C.
After the temperature was raised to 0 ° C., the following chemicals were added thereto, and a reducing washing solution having the following concentration was adjusted. After applying reducing washing at 70 ° C. for 10 minutes to the dyed product, the remaining solution was discharged and hot water was added. And after thoroughly rinsing the dyed product with water
Finished by a dry heat set at 30 ° C. for 30 seconds.

Conditions for the reduction cleaning solution Thiourea dioxide: 2 g / liter Caustic soda: 2 g / liter Sunmol RC-700 (non-ionic detergent; manufactured by Nika Chemical Industry Co., Ltd.): 0.5 g / liter Bath ratio: 1 : 30 Table 5 shows the results of evaluation of the obtained dyed product in terms of sweat alkali fastness, washing fastness, and dry cleaning solution contamination. The polyether-based polyurethane fiber in the obtained dyed product was hardly colored.

[0063]

Comparative Example 6 Dyeing was carried out in the same manner as in Example 5, except that tannic acid and antimony sodium tartrate were used in combination without dyeing, or that the respective concentrations shown in Table 5 were used alone. Finished with processing. Table 5 shows the evaluation results of the resulting dyed products. From the results shown in Table 5, the dyed product obtained by the dyeing method of Example 5 has high color developability, extremely high sweat alkali fastness, extremely good washing fastness, and high commercial value with less contamination of the dry cleaning liquid. It is clear that something has been obtained. On the other hand, the dyed product of Comparative Example 6 had a high degree of coloring of the polyether-based polyurethane fiber, and was inferior to the dyed product of Example 5 in all of the fastness to sweat alkali, the fastness to washing, and the contamination with dry cleaning liquid. ing.

[0064]

[Table 5]

[0065]

[Embodiment 6] After relaxing and presetting the six-course satin net formed in Embodiment 1 in the same manner as in Embodiment 1,
Were dyed separately under the following conditions. Dyeing conditions: Dye: Dispersol Black T-532 (diester type disperse dye) 14% omf Dianix Blue HR-FS (heterocyclic azo disperse dye) 10% omf C.I. I. Disperse Red 356 (condensed disperse dye) 15% omf Dispersing and leveling agent: Nikka San Salt RM-340 0.5 g / l acetic acid: 0.5 cc / l sodium acetate: 1 g / l tannic acid: 3% omf antimony tartrate Sodium: 0.3% omf bath ratio: 1:20 Dyeing temperature, time: 120 ° C., 30 minutes After dyeing is completed, reduction washing is performed in the same manner as in Example 1, and 160
Finished by a dry heat set at 30 ° C. for 30 seconds. Table 6 shows the evaluation results of the obtained dyed product for the fastness to sweat alkali, the fastness to washing, and the contamination of the dry cleaning solution. The polyether-based polyurethane fiber contained in the obtained dyed product was hardly colored.

[0066]

Comparative Example 7 A dyed finished knitted fabric was obtained in the same manner as in Example 6, except that dyeing was carried out without using tannic acid or sodium antimony tartrate. From the results shown in Table 6, the dyed product obtained by the dyeing method of Example 7 has a high color developability, extremely high sweat alkali fastness, extremely good washing fastness, and a commercial value with little dry cleaning liquid contamination. However, the dyed product of Comparative Example 7 was dyed according to the present invention in all of the degree of coloring, fastness to sweat alkali, fastness to washing, and stain of dry cleaning solution of the polyether polyurethane fiber. Inferior to things.

[0067]

[Table 6]

[0068]

[Embodiment 7] After relaxing and presetting the 6-course satin net formed in Embodiment 1 in the same manner as in Embodiment 1,
Staining was performed under the following conditions. In addition, the polyvalent metal compound added to each dyeing bath is shown in Table 7. Dyeing conditions Dye: Dianix Navy Blue (200) (benzeneazo-based disperse dye) 3% omf Dispersion leveling agent: Nikkasan Salt 8000 (manufactured by Nikka Chemical Co., Ltd .; polyalkylene oxide adduct of polyhydric alcohol fatty acid) 1 g / liter Acetic acid: 0.5 cc / liter Sodium acetate: 1 g / liter Tannic acid: 1% omf Polyvalent metal compound: 0.08% omf Bath ratio: 1:20 Dyeing temperature, time: 120 ° C. After completion of the staining for 30 minutes, reduction washing was performed in the same manner as in Example 1,
Finished by a dry heat set at 30 ° C. for 30 seconds. Table 7 shows the results of evaluation of the obtained dyed product in terms of sweat alkali fastness, washing fastness, and dry cleaning solution contamination. The polyether-based polyurethane fiber in the obtained dyed product was hardly colored.

[0069]

Comparative Example 8 A knitted fabric was dyed and finished in the same manner as in Example 7 except that the dyeing was carried out without using a polyvalent metal as shown in Table 7. Table 7 shows the evaluation results of the finished knitted fabric. From the results in Table 7, the dyed product of the dyeing method of Example 7 has higher color development, higher sweat alkali fastness, and better washing fastness than the dyed product of Comparative Example 8; It is clear that a product having a high commercial value with little contamination of the dry cleaning liquid is obtained.

[0070]

[Table 7]

[0071]

Embodiment 8 Diacetate fiber 83dtex / 21f
(Trade name: Linda, manufactured by Mitsubishi Rayon Co., Ltd.) and polyethylene terephthalate 56 dtex / 24f in the Z direction 80
Twisting is performed while applying 0 T / M twist, and this plied yarn is used as a warp (warp density: 148 yarns / inch), and a polyether-based polyurethane fiber of polyethylene terephthalate 167 dtex / 48f and 33 dtex (manufactured by Asahi Kasei Kogyo Co., Ltd.) (Loika SC) was drafted 2.5 times and twisted at 1200 T / M in the Z direction, and this yarn was used as the weft (weft density: 77 yarns / inch) to prepare a woven fabric with a 2/1 twill structure ( The mixing ratio of polyurethane fiber is 2%).

Next, the mixed woven fabric was scoured at 80 ° C., preset at 180 ° C., and dyed under the following conditions. Dyeing conditions: Dye: C.I. I. Disperse Blue 167 6% omf Leveling agent: Nikka San Salt RM-340 0.5 g / l acetic acid: 0.5 cc / l sodium acetate: 1 g / l tannic acid: 0.3% omf sodium antimony tartrate: 0.2 % Omf bath ratio: 1:15 Dyeing temperature, time: 130 ° C. × 30 min.
Finished by dry heat setting at 30 ° C for 30 seconds.

Reduction washing Hydrosulfite: 2 g / liter Soda ash: 3 g / liter Bisnol UP-10 (manufactured by Yokosha Yushi Co., Ltd.): 1 g / liter Bath ratio: 1:60 Treatment temperature, time: 80 ° C. 20 minutes The results of evaluation of the dyed product obtained for sweat alkali fastness, washing fastness, and dry cleaning solution contamination are shown in Table 8. The polyether polyurethane fiber in the obtained dyed product was hardly colored. .

[0074]

Comparative Example 9 A dyeing process was carried out in the same manner as in Example 8 except that tannic acid and sodium antimony tartrate were not used, and finished. As shown by the evaluation results in Table 9, the dyed product of the dyeing method of Example 9 had higher coloring properties than the dyed product of Comparative Example 9,
It is clear that a product having high sweat alkali fastness and high washing fastness and low contamination with a dry cleaning liquid and high commercial value can be obtained.

[0075]

[Table 8]

[0076]

Embodiment 9 Polyethylene terephthalate 56 dtex
/ 24f and viscose rayon 56dtex / 17f were interlaced and twisted at 300 T / M in the S direction. Using this mixed fiber and 33 dtex polyether-based polyurethane fiber (Roika SC manufactured by Asahi Kasei Kogyo Co., Ltd.), a knitted knit fabric was produced at 24 GG (polyurethane fiber mixing ratio was 2.7% by weight).

Then, after prewetting at 60 ° C., 18
Presetting was performed at 0 ° C., and staining was performed under the following conditions. Dyeing conditions Dyeing material: Dianix Navy Blue (200) 3.5% omf Dispersing and leveling agent: Nikkasan Salt 8000 1g / L Acetic acid: 0.5cc / L Sodium acetate: 1g / L Tannic acid (50% product) : 1% omf sodium antimony tartrate: 0.5% omf bath ratio: 1:20 Dyeing temperature, time: 125 ° C x 30 minutes

After dyeing was completed, reduction washing was performed under the following conditions. Thiourea dioxide 3 g / liter Caustic soda 2 g / liter Bisnol UP-10 1 g / liter Bath ratio: 1:60 Treatment time, temperature: 80 ° C. × 20 minutes After the treatment, the plate was washed thoroughly with water and dyed under the following conditions. Dyeing agent: Sumifix Black B 4% omf Glauber's salt: 100 g / l Soda ash: 20 g / l Bath ratio: 1:20 Dyeing temperature, time: 60 ° C x 90 minutes After dyeing, it was washed with water and soaped at 85 ° C. . After the treatment, dry heat setting was performed at 160 ° C. for 30 seconds to finish. The dyed product was evaluated for sweat alkali fastness, washing fastness, and dry cleaning solution contamination. Table 9 shows the results. The polyether-based polyurethane fiber of the obtained dyed product was hardly colored.

[0079]

Comparative Example 10 A dyeing process was carried out in the same manner as in Example 9 except that tannic acid and antimony sodium tartrate were not used at the time of dyeing the disperse dye. Table 9 shows the results. From the results shown in Table 9, the dyed product obtained by the dyeing method of Example 11 has higher coloring properties, higher sweat alkali fastness, higher washing fastness, and less dry cleaning liquid contamination than the dyed product of Comparative Example 10. It is clear that a product with high commercial value has been obtained.

[0080]

[Table 9]

[0081]

EFFECT OF THE INVENTION The disperse dye-dyed product of the present invention, which is a mixture of a dyeable dyeable fiber and a polyurethane fiber, has high sweat alkali fastness, high washing fastness, extremely low dry cleaning liquid contamination, and high color developability (color density). The present invention makes it possible to provide a deeply colored urethane fiber mixed dyeing product having high wet dyeing fastness.

Claims (4)

[Claims] 1. A mixed dyed product obtained by mixing a disperse dye dyeable fiber and a polyurethane fiber and then dyeing the mixed dyed product, wherein the mixed dyed product has at least a third grade of sweat alkali fastness according to JIS L-0848. It has a color fastness and has a dyeing density not exceeding 20 even when the spectral colorimetric L value of its surface color is large, and is dyed with a disperse dye selected from the group of disperse dyes including benzeneazo disperse dyes. A mixed dyed product of a disperse dye dyeable fiber and a polyurethane fiber, comprising: 2. A mixed dyed product obtained by mixing a disperse dye dyeable fiber and a polyurethane fiber and then dyeing the mixed dyed product, wherein the mixed dyed product is at least a quaternary or higher JISL-0848.
With a dyeing fastness of sweat alkali fastness and a dyeing density not exceeding 20 even if the spectral colorimetric L value of the surface color is large, and a heterocyclic azo type, condensed type disperse dye, diester type dispersant A mixed dyed product of a disperse dye dyeable fiber and a polyurethane fiber, which is dyed with a disperse dye selected from the group of dyes. 3. The mixed dyed product of the dyeable disperse dyeable fiber and the polyurethane fiber according to claim 1 or 2, wherein the degree of coloring of the polyurethane fiber contained in the mixed dyed product is 60 or less. . 4. A mixed dyed product obtained by mixing a disperse dye-dyeable fiber and a polyurethane fiber and then dyeing the mixture shows at least a grade 3 dry cleaning liquid contamination evaluation value according to JIS L-0860. A mixed dyed product of the disperse dye dyeable fiber according to any one of claims 1 to 3 and a polyurethane fiber.