JP2015203176A - Dyed fabric excellent in deodorizing performance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorizing dyed fabric which is composed of a mixed dyed fabric of a non-modified cellulose fiber, a polyester fiber and a polyurethane fiber and is excellent in deodorizing performance for age-related body odor and water-absorbing and quick-drying performance and high in whiteness in white dyeing.SOLUTION: A deodorizing dyed fabric is composed of a mixed dyed fabric of a non-modified cellulose fiber, a polyester fiber and a polyurethane fiber and shows a reduction rate of ammonia of 70% or higher, a reduction rate of acetic acid of 80% or higher, a reduction rate of isovaleric acid of 85% or higher and a reduction rate of nonenal of 75% or higher after 50-time cleaning, by the deodorization-processed fiber product accreditation criteria.

Description

  The present invention relates to a mixed dyed fabric of cellulose fiber, polyester fiber and polyurethane fiber, which is excellent in deodorizing performance. More specifically, the present invention relates to a mixed dyed fabric of cellulose fiber, polyester fiber and polyurethane fiber, which has a deodorizing performance excellent in washing durability, a high dyeing whiteness, and an excellent water-absorbing quick-drying performance.

Cellulose fibers such as cotton are often used in clothes, but in recent years, deodorant performance and water-absorbing quick-drying performance have been demanded as functions to satisfy the comfort of clothes and the room drying environment in daily life. ing.
Among the deodorizing performance, in particular, due to the progress of an aging society, a deodorizing function for an aging odor which is a unique body odor emitted by middle-aged and elderly people is required. In particular, in summer inner products, white products with fluorescent whitening have high whiteness, a durable deodorizing function, and a water-absorbing quick-drying function.
In general, the aging odor is considered to be caused by the odor components of ammonia, acetic acid, isovaleric acid, and nonenal. The deodorization of the aging odor requires a function of removing all these four components. Has been.

Patent Document 1 listed below discloses a fabric formed by knitting fibrils to which a titanium oxide photocatalyst is attached as a method for obtaining various deodorizing functions. However, although effective against a specific odor, all the four odor components described above cannot be removed, and there is a problem inferior in water absorption and quick drying performance.
Nonenal, which is one of the aging odors, is due to lipid peroxide that was not decomposed due to the deterioration of the body defense mechanism due to aging, and palmitoleic acid that increases in secretion with age. Oxidative propagation of valmitoleic acid becomes valmitoleic acid hydroperoxide, which is cleaved and decomposed into nonenal. Therefore, as a method of inhibiting oxidative propagation by lipid peroxide, There is a method of applying an antioxidant to the fiber surface, but there is a problem that these antioxidants themselves have no washing durability.

  In Patent Documents 2 and 3 below, modified cellulose fibers obtained by graft copolymerization of methacrylic acid on cellulose fibers, polyester fibers, and polyurethane fibers are disclosed as methods for expressing a surprising deodorizing property against aging odors. And a composite fabric is disclosed. However, by modifying the cellulose fiber by graft copolymerization, the strength and whiteness are lowered, and not only products with high whiteness cannot be obtained in inner and sports clothing, but also the burst strength and resistance of the fabric are reduced. There are problems of reduced wear and reduced water absorption and quick drying performance.

Patent Document 4 listed below discloses a method for hydrophilic treatment of a specific copolymer polyester fiber as a method for obtaining a deodorant fabric excellent in dyeing fastness. However, this method has excellent deodorizing performance against ammonia odor, hydrogen sulfide odor, and acetic acid odor, but has a problem that the effect on isovaleric acid and nonenal odor is weak.
Patent Document 5 below discloses a method for fixing a substance made of a hydroxy acid derivative as a method for obtaining a polyester fiber structure having deodorizing properties with excellent washing durability. However, this method has an excellent deodorizing performance against ammonia odor, but has a problem that the effect is weak against acetic acid odor, isovaleric acid odor, and nonenal odor.
Thus, in the present situation, dyed products having excellent deodorizing performance against aging odors, excellent water-absorbing quick-drying performance, and high whiteness in white dyed products have been obtained in fabrics used without modifying cellulose fibers. Absent.

JP 2002-030552 A Japanese Patent No. 4235244 WO2009 / 101995 pamphlet JP 2010-242240 A WO2011 / 118749 pamphlet

  The problem to be solved by the present invention is a dyed fabric using a mixture of non-modified cellulose fiber, polyester fiber and polyurethane fiber, with excellent washing durability for deodorizing performance against aging odor, excellent water absorption and quick drying performance, An object of the present invention is to provide a deodorant dyed fabric having high whiteness in white dyeing and a method for producing the same.

  In order to solve the above-mentioned problems, the present inventor has intensively studied and repeated experiments. As a result, in a mixed product of non-modified cellulose fiber, polyester fiber, and polyurethane fiber, non-ionization is performed under acidic conditions using hydroxy acid. / After fluorescent whitening of polyester fibers using a mixture of anionic surfactant and polyester resin of specific molecular weight, bleaching of cellulose fibers and fluorescent whitening are performed at the same time. The present inventors have found that a dyed product having a high odor washing durability and whiteness in a white dyed product and an excellent water-absorbing quick-drying performance can be obtained, and the present invention has been completed.

That is, the present invention is as follows.
[1] A dyed fabric in which unmodified cellulose fiber, polyester fiber, and polyurethane fiber are mixed, and after 50 washings, the ammonia depletion rate is 70% or more according to the deodorant fiber product certification standard, and acetic acid is reduced. A deodorant dyed fabric having a rate of 80% or more, a reduction rate of isovaleric acid of 85% or more, and a nonenal reduction rate of 75% or more.
[2] The deodorant dyed fabric according to [1] above, containing 0.1 to 0.9% by weight of a polyester resin having a molecular weight of 8000 to 15000.
[3] In a dye bath whose pH is adjusted to 4.5 to 6.0 with hydroxy acid, using a nonionic / anionic surfactant mixture, a polyester resin and a fluorescent whitening dye at a temperature of 125 to 135 ° C. The deodorant dyed fabric according to the above [2], wherein the polyester fiber is dyed.
[4] The deodorant dyed fabric according to [3] above, wherein bleaching of the unmodified cellulose fiber and dyeing with a fluorescent dye are performed simultaneously after dyeing of the polyester fiber.

  The dyed fabric of the present invention is composed of non-modified cellulose fiber, polyester fiber and polyurethane fiber, exhibits excellent deodorizing performance against aging odor, has high whiteness in white dyed products, and excellent water absorption and quick drying performance. ing.

Hereinafter, the present invention will be described in detail.
The dyed fabric of the present invention is a fabric composed of non-modified cellulose fiber, polyester fiber and polyurethane fiber, has a high whiteness in fluorescent whitening dyed products, is excellent in deodorizing performance against aging odors, and absorbs water quickly. Excellent performance and improved washing durability.
Conventionally, modified cellulose fibers obtained by graft copolymerization reaction of methacrylic acid to cellulose fibers have been devised for imparting deodorant performance, but the unmodified cellulose fibers in the present invention are modified. Specifically, it is a cellulose fiber to which a carboxyl group by post-treatment is not substantially added. Cellulose fibers refer to natural cellulosic fibers such as cotton and hemp, and regenerated cellulose fibers such as rayon and polynosic. Regenerated cellulose fibers can be preferably used, and in particular, when cupra (Asahi Kasei Fibers Bemberg) is used, The effect is most noticeable.

Although the cellulose fiber used by this invention is not specifically limited, It is preferable that the total fineness is 15-90 dtex. Further, the cross-sectional shape is not particularly limited, but in the case of the L-shaped cross section, since the supple texture is easily obtained and the specific surface area is large, the water-absorbing quick-drying performance is enhanced and the effect of the present invention is sufficiently achieved. Therefore, it is preferable.
Further, the cellulose fiber used in the present invention preferably contains 50% or more of regenerated cellulose fiber, and more preferably 100% of regenerated cellulose fiber.
The form of the fibers may be long fibers or short fibers, and may be uniform or thick in the length direction. And as the form of the yarn to be processed, the spun yarn such as ring spun yarn, open-end spun yarn and air jet fine spun yarn, sweet twisted yarn to strong twisted yarn, false twisted yarn, air injection processed yarn, indentation processing There are yarn and knitted knitted yarn.

  Examples of yarn forms when cellulose fibers and other fibers are mixed include blends (blends, fleece blends, sliver blends, core yarns, silospans, silofils, hollow spindles, etc.), entangled blends, twists, designs Twisted yarn, covering (single, double), composite false twist (simultaneous false twist, pre-twist false false twist), elongation difference false twist, phase difference, post-mixing after false twisting and two feeds (simultaneous feed and feed difference) The mixed form by air injection processing etc. is mentioned.

In the present invention, the polyester fiber is a fiber mainly composed of a polyethylene terephthalate, polybutylene terephthalate or polypyropylene terephthalate unit. If necessary, the third component may be modified by copolymerization and / or blending, and may be produced by a conventionally known method.
The polyester fiber used in the present invention may contain surfactants such as titanium oxide and alkylbenzene sulfonate, conventionally known antioxidants, anti-coloring agents, light-proofing agents and antistatic agents, and alkali metals. Good.

The polyester fiber used in the present invention is not particularly limited, but is preferably a fiber having a total fineness of 15 to 90 dtex. Further, the cross-sectional shape may be flat, constricted flat, triangular, quadrilateral, three or more multi-leaf shape, C-type, H-type, X-type, W-type, M-type and hollow cross-section in addition to the round shape. However, a fiber having a deformed cross section with a flatness of 2.0 to 4.0 and a single yarn decitex of 1.1 decitex is preferred because the water absorption and quick drying performance is enhanced.
The form of the fibers may be long fibers or short fibers, and may be uniform or thick in the length direction. As the form of the yarn on which the fiber is processed, a spun yarn such as a ring spun yarn, an open-end spun yarn and an air jet fine spun yarn, a sweet twisted yarn to a strongly twisted yarn, a false twisted yarn, an air injection processed yarn, an indented processed yarn, In addition, there are knit and knitted yarns.

（式中、ｌは１以上の整数であり、そしてＲ₄とＲ₅は上記（ｉ）及び（ｉｉ）に記載したものと同じである。）

（式中、ｍは１以上の整数であり、そしてＲ₄とＲ₆は上記（ｉ）及び（ｉｉｉ）に記載したものと同じである。） When the polyurethane fiber used in the present invention represents an active hydrogen-containing compound that reacts with an organic polyisocyanate, a polyalkylene ether diol, and an isocyanate group by the following (i), (ii), and (iii):
(I) an organic _{polyisocyanate: R 4 - (NCO) x} ( wherein, R ₄ is an organic residue, and x is an integer of 2 or more),
(Ii) polyalkylene ether diol: HO—R ₅ —OH (wherein R ₅ is a residue of polyalkylene ether diol),
(Iii) an active hydrogen-containing compound that reacts with an isocyanate group: H—R ₆ —H and / or R ₇ —H (wherein R ₆ and R ₇ are residues of the active hydrogen-containing compound),
Basically, it has a structure represented by repetition of the following structural unit (A) and structural unit (B) derived therefrom.

(In the formula, l is an integer of 1 or more, and R ₄ and R ₅ are the same as those described in (i) and (ii) above.)

(In the formula, m is an integer of 1 or more, and R ₄ and R ₆ are the same as those described in (i) and (iii) above.)

例えば、テトラヒドロフランの開環重合によって得られるポリテトラメチレンエーテルグリコールが挙げられる。これ以外に、前記した構造単位（Ｃ）及び下記構造単位（Ｄ）からなる共重合ポリアルキレンエーテルジオールであってもよい。

（式中、Ｒ₁は炭素原子数１〜５の直鎖又は分岐アルキレン基であり、Ｒ₂とＲ₃は炭素原子数１〜３のアルキル基であるか、又はＲ₂とＲ₃は一緒になって、脂環式炭化水素残基を形成する。） Furthermore, in accordance with the number of functional groups of the organic polyisocyanate compound forming the structural units (A) and (B), the urethane bond portion or the urea bond portion bonded to the R ₄ group can be increased or decreased. The end of the polyurethane polymer can be —R ₆ —H or —R ₇ .
In the present invention, the polyalkylene ether diol only needs to be mainly composed of the following structural unit (C),

Examples thereof include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran. In addition to this, a copolymerized polyalkylene ether diol composed of the above-described structural unit (C) and the following structural unit (D) may be used.

(Wherein R ₁ is a linear or branched alkylene group having 1 to 5 carbon atoms, R ₂ and R ₃ are alkyl groups having 1 to ₃ carbon atoms, or R ₂ and R ₃ are together. To form an alicyclic hydrocarbon residue.)

The copolymer polyalkylene ether diol preferably has an alkyl group having a specific ratio represented by the following formula (1).
0.05 ≦ (M _D ) / (M _C + M _D ) ≦ 0.50 (1)
(Each wherein, M _C and M _D, the total number of structural units present in the polyalkylene ether diol (C) and (D), and the structural unit (C) and the structural unit (D) is the (It may be present in the polyalkylene ether diol in either random or block form.)
In the formula (1), more preferably, 0.10 ≦ (M _D ) / (M _C + M _D ) ≦ 0.45.

  Such a specific polyalkylene ether diol is produced by reacting tetrahydrofuran and a low molecular diol or a dehydrated cyclic low molecular compound thereof alone or in combination and using a heteropoly acid with a controlled hydration number as a catalyst. Can do. Examples of the production method include, but are not limited to, the method described in JP-A No. 61-123628.

  Examples of low molecular diols and cyclic low molecular compounds that can be used with tetrahydrofuran in the production of polyalkylene ether diols include neopentyl glycol, 3,3-dimethyloxetane, 1,1-dihydroxyethylcyclohexane, 1, Examples thereof include 1-dihydroxyethylcyclopentane, among which neopentyl glycol and 3,3-dimethyloxetane are preferable.

The molecular weight, copolymer component composition, copolymerization ratio, and terminal group ratio of the polyalkylene ether diol can be easily set to specific values by variously changing the reaction method and conditions.
The specific structural unit (B) having a branched chain of the polyalkylene ether diol and the tetramethylene unit as the structural unit (A) may be distributed in a random or block form. In the reaction using a heteropolyacid catalyst, it can be distributed in either a block shape or a random shape, and the crystallinity of the diol can be effectively changed in various ways. Can be manufactured. In the present invention, a random shape is preferable from the viewpoint of elastic characteristics.

The number average molecular weight of the polyalkylene ether diol is preferably 300 to 30,000, more preferably 500 to 5,000, and still more preferably 1,000 to 4,000.
Furthermore, the polyalkylene ether diol may be mixed or used in combination with other diols in any ratio.

  Other diols include diols having a number average molecular weight of about 250 to 20,000, such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, polyoxypropylene tetramethylene glycol, and the like. Polyether diol; one or more dibasic acids such as adipic acid, sebacic acid, maleic acid, itaconic acid, azelaic acid, malonic acid, and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 2,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10-decanediol, 1,3-cyclohexanedimethanol, Polyester diol obtained from one or more of glycols such as 1,4-cyclohexanedimethanol; polylactone diols such as poly-ε-caprolactone and polyvalerolactone; polyester amide diol, polyether-ester diol, Examples thereof include polycarbonate diol.

The polyalkylene ether diol preferably satisfies the above formula (1) and further has an alkyl group terminal having a specific ratio represented by the following formula (2).
0.06 ≦ (T _D ) / (T _C + T _D ) ≦ 0.70 Expression (2)
(In the formula, each of T _C and T _D is the total number of structural units (C) and (D) present at the terminal of the polyalkylene ether diol.)
When the amounts of the structural units (C) and (D) are within the ranges of the formulas (1) and (2), a polyurethane polymer excellent in dry heat setting properties, moist heat resistance, and elastic functions can be obtained. In the formula (2), more preferably, 0.12 ≦ (T _D ) / (T _C + T _D ) ≦ 0.54.

In the present invention, the terminal group ratio of the structural unit (C) and the structural unit (D) in the polyalkylene ether diol preferably satisfies the following formula (3).
1.20 ≦ {(T _D ) / (T _C + T _D )} / {(M _D ) / (M _C + M _D )} ≦ 6.0 Equation (3)
(In the formula, M _C , M _D , T _C and T _D are the same as those defined in Formula (1) and Formula (2).)
That is, it is preferable that the ratio of the structural unit (D) at the terminal of the polyalkylene ether diol is larger than the ratio of the structural unit (D) in the whole polyalkylene ether diol. When the terminal group ratio satisfies the above formula (3), a polyurethane having good dry heat setting property is obtained, and in the production process, the reactivity of the organic polyisocyanate compound is good, the reaction is relatively short, and the temperature is low. Therefore, no side reaction occurs and gelation due to the formation of alphanate crosslinks does not occur.

In order to control the terminal group ratio of the polyalkylene ether diol, for example, by adding a large amount of the compound derived from the structural unit (D) at the end point of the reaction, there may be many structural units (D) in the terminal group. it can.
In the present invention, a polyurethane can be produced by reacting a polyalkylene ether diol and an organic polyisocyanate compound in the presence of an active hydrogen-containing compound that reacts with an isocyanate group.

  Examples of the organic polyisocyanate compound include compounds having at least two isocyanate groups in the molecule, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate ( MDI), xylene isocyanate, isophorone diisocyanate, p-phenylene diisocyanate, bis (3-methyl-4-isocyanatophenyl) methane, bis (4-isocyanatocyclohexyl) methane, hexamethylene diisocyanate and the like.

Examples of the active hydrogen-containing compound that reacts with an isocyanate group include (a) water, (b) ethylenediamine, propylenediamine, trimethylenediamine, hexamethylenediamine, hydrazine, carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, N, Bifunctional aliphatic diamines such as N′-bis (γ-aminopropyl) -N, N-dimethylethylenediamine, (c) monofunctional amino compounds such as dimethylamine, methylethylamine, diethylamine, methyl-n-propyl Monofunctional secondary amines such as amine, methyl-isopropylamine, diisopropylamine, methyl-n-butylamine, methyl-isobutylamine, methylisoamylamine, (2) ethylene glycol, propylene glycol, butylene glycol Diols such as Lumpur, the polyalkylene ether diol for use in the (E) In the present invention, (to) a number average molecular weight 250 to 5000 of about diols known, and (g) monohydric alcohols.
The organic polyisocyanate compound and the active hydrogen-containing compound may be used alone, or may be mixed in advance as necessary.

Regarding the operation of the polyurethane reaction, the following method is preferred.
(A) A known polyurethane-forming reaction, for example, a polyalkylene ether diol and an organic polyisocyanate compound are 1: 1 to 1: 3.0 (equivalent ratio), preferably 1: 1.3 to 1: 2. After reacting under an excess of organic polyisocyanate compound at a ratio of 0.0 to synthesize a urethane prepolymer, an active hydrogen-containing compound that reacts with the isocyanate group is added to the isocyanate group in the prepolymer and reacted. Let

(B) The organic polyisocyanate compound, polyalkylene ether diol, and active hydrogen-containing compound are reacted at the same time by a one-shot polymerization method in which they are reacted in one stage.
In the urethanization reaction, a solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, benzene, or toluene may be used as necessary.
Further, the stoichiometric proportions of various compounds in the polyurethane fiber used in the present invention are the hydroxyl group of the polyalkylene ether diol represented by (ii) and the active hydrogen of the active hydrogen-containing compound represented by (iii). Is preferably 0.9 to 1.15 equivalent, more preferably 1.0 to 1.05 equivalent based on the isocyanate group of the organic polyisocyanate compound represented by (i). preferable.
The polyurethane fiber having the above structure used in the present invention may be obtained by the method described in Japanese Patent No. 4002440 and may contain a tertiary nitrogen compound.

The cellulose fiber, the polyester fiber, and the polyurethane fiber used in the present invention may each contain a composite metal oxide containing zinc, copper, silica, magnesium, or aluminum element by a blending method. As the composite metal oxide, it is preferable to contain 0.1 to 6.0 wt% of fine particles having a specific surface area of 200 to 400 m ² / g in the BET value because the deodorizing performance is further enhanced.

  The dyed fabric of the present invention contains non-modified cellulose fibers, polyester fibers, and polyurethane fibers, and the proportion of each fiber can be appropriately determined depending on the use. However, the cellulose fibers are generally used in an amount of 30% or more. A preferable result is obtained when 30% or more is used and polyurethane fiber is used in an amount of 20% or less. In terms of fabric performance and deodorant properties, it is more preferable that the cellulose fiber is 30 to 60%, the polyester fiber is 30 to 60%, and the polyurethane fiber is 3 to 15%.

The mixed form of the dyed fabric of the present invention is roughly classified into a thread-mixed form and a cloth-mixed form.
Examples of the mixed form of yarns in the case of mixing cellulose fiber and polyester fiber include blended yarn (blended cotton, fleece blended fiber, sliver blended fiber, core yarn, silo span, silofil, hollow spindle, etc.), entangled mixed fiber, twisted yarn, Design twist yarn, covering (single, double), composite false twist (simultaneous false twist, pre-twist false false twist), elongation difference false twist, phase difference, post-mixing after false twist processing, 2 feeds (simultaneous feed and feed difference) ) A mixed form by air injection processing or the like.
Polyurethane fiber yarns can be mixed in the form of polyurethane fiber bare yarn (10 to 80 dtex) covered with cellulose fiber or polyester fiber, such as so-called covering yarn (single and double covering), twisted yarn, core yarn, cross yarn. The form of a well-known covering yarn, such as a kite thread, is mentioned.

Examples of the form of mixed fabric include mixed use in knitted fabrics, woven fabrics, non-woven fabrics, and composite fabrics thereof (for example, laminated fabrics). As a specific example, there is a so-called on-machine mixed article, and polyurethane fiber bare yarn (when bare yarn is stretched about 2 to 4 times during knitting or weaving) or coated yarn on the machine Examples thereof include knitted fabrics that are mixed with cellulose fibers and polyester fibers or combined with yarns.
The form of mixing in the present invention is not limited at all, and cellulose fiber, polyester fiber, and polyurethane fiber may be mixed by known mixing means.

Dyeing of the mixed fabric of cellulose fiber, polyester fiber and polyurethane fiber of the present invention is carried out after presetting the living machine, but the scouring operation before carrying out the dyeing is described later in a nonionic / anionic surfactant mixture. It is preferable to carry out by the method currently implemented normally using 1-2g / L.
In the dyeing operation of the dyed fabric of the present invention, the polyester fiber is first dyed, and then the bleaching and dyeing of the cellulose fiber are simultaneously performed. By passing through such steps, a mixed dyed fabric having high deodorizing performance as referred to in the present invention, high whiteness in a white dyed product, and high water absorption and quick drying performance can be obtained.

In the present invention, when the polyester fiber is dyed with a fluorescent whitening dye in order to improve the deodorizing performance, the whiteness of the dyed fabric, and the water-absorbing quick-drying performance, the pH of the dyeing bath is 4.5 to It is preferable to adjust to 6.0.
The hydroxy acid as used in the present invention is an aliphatic oxyacid or aromatic oxyacid having a carboxyl group and a hydroxyl group in one molecule of an organic compound, such as lactic acid, malic acid, tartaric acid, citric acid, salicylic acid, gallic acid, etc. In view of ease of handling, aliphatic oxyacids such as lactic acid, malic acid, and tartaric acid can be preferably used, and the amount used is generally 0.2 g / L or less. When the dye bath pH is less than 4.5, the whiteness after fluorescent whitening tends to be low, and when the pH exceeds 6.0, the deodorizing performance and the water-absorbing quick-drying performance tend to be inferior. It is in.

  In addition, it is preferable to use a nonionic / anionic surfactant mixture and a polyester resin in the dye bath, but the nonionic / anionic surfactant mixture referred to in the present invention means polyoxyethylene alkyl ether, Nonionic surfactants composed of oxyalkylene derivatives, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines and the like, alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, naphthalene sulfonate formalin condensates It is a mixture with an anionic surfactant consisting of etc. The effect of the deodorizing performance of the present invention is enhanced by using an anionic surfactant in combination. The mixing ratio of the nonionic surfactant and the anionic surfactant is preferably in the range of 1: 1 to 9: 1. is there. Examples of such surfactants include Lebenol TD-838 manufactured by Kitahiro Chemical Co., Ltd. The higher the ratio of the anionic surfactant, the higher the durability of the deodorizing performance, but when the combined use ratio exceeds 50%, the foaming becomes higher when dyeing with a rotary dyeing machine such as a liquid dyeing machine, The dyeing operation becomes unstable, which is not preferable. The amount of the nonionic / anionic surfactant mixture used is preferably 1 to 3 g / L. When the amount used is less than 1 g / L, the deodorizing performance is unstable, and when it exceeds 3 g / L, the adsorptivity of the dye decreases, which is not preferable.

In the present invention, it is preferable to use a polyester resin together in the dyeing bath in order to obtain a water-absorbing quick-drying performance. By applying the polyester resin, the deodorizing performance of the present invention is further enhanced.
The polyester resin used in the present invention is a block copolymer composed of terephthalic acid and / or isophthalic acid, alkylene glycol and polyalkylene glycol, and is composed of an emulsion dispersed in water. Its molecular weight is 8000-15000. Examples of such a polyester resin include SR-1801Mconc and DCOM 35-6 manufactured by Takamatsu Yushi Co., Ltd., as an example. When the molecular weight is within this range, the synergistic effect with the hydroxy acid and nonionic / anionic surfactant mixture in the dyeing bath increases the binding force between the polyester resin and the polyester fiber, deodorizing performance, water absorption quick drying performance Increased durability. When the molecular weight is less than 8000, the durability of water absorption and quick drying performance is low, and when the molecular weight exceeds 15,000, a supple texture cannot be obtained sufficiently. The amount of the polyester resin applied is preferably 0.1 to 0.9% by weight, more preferably 0.2 to 0.6% by weight, based on the weight of the mixed fabric. If the applied amount is less than 0.1% by weight, the deodorizing performance and the water-absorbing quick-drying performance of the present invention are not preferable.

  In the present invention, the polyester fiber is dyed using a fluorescent whitening dye. The fluorescent whitening dye absorbs light in the ultraviolet part (330 to 380 nm) and emits fluorescence on the short wavelength side (400 to 450 nm) of the visible part. It is a coumarin or oxazole dye and is usually applied to polyester fibers. Any dye may be used as long as it is used, and the dye concentration may be 0.3 to 3% omf. The temperature at the time of dyeing is carried out at 125 to 135 ° C. in order to increase the whiteness of the dyed fabric, and to improve the deodorizing performance and water absorption quick drying performance, and the dyeing time is 20 to 45 minutes. When the dyeing temperature is lower than 125 ° C., the whiteness, deodorizing performance, and water absorption quick-drying performance of the dyed fabric are insufficient. On the other hand, when the dyeing temperature exceeds 135 ° C., high whiteness cannot be obtained.

By simultaneously performing bleaching treatment of cellulose fibers and fluorescent whitening after dyeing of polyester fibers, a mixed dyed fabric having a higher whiteness can be obtained. As the bleaching agent, it is preferable to use hydrogen peroxide water in order to maintain the strength of the cellulose fiber, and the amount used may be 5 to 20 ml / L. As the fluorescent whitening dye, a stilbene dye or the like used for cellulose fiber is used, the concentration used is 0.2 to 0.8% omf, and the processing temperature is 90 to 100 ° C. The processing time may be 20 to 45 minutes.
After dyeing, it is preferable to use 1 to 2 g / L of hydroxy acid and treat at 40 to 60 ° C. for 20 to 30 minutes because the deodorizing performance is stabilized.

For the dyeing operation, a rotary dyeing machine such as a rotary drum dyeing machine, paddle type dyeing machine, wins reel dyeing machine, liquid dyeing machine, airflow dyeing machine, etc. can be used for uniform processing and good deodorizing performance. Since water absorption quick-drying performance is obtained, it is preferable.
As for the finishing method after dyeing, any conditions can be applied as long as the conditions are generally used for a mixed fabric of cellulose fibers and polyester fibers, and may be set as appropriate according to the characteristics of the mixed fabric. Moreover, since the deodorizing performance can be obtained more stably when the fabric pH of the dyed finishing fabric is 3.8 to 6.5, 1 to 2 g / L of hydroxy acid is added to the finishing agent bath to adjust. It is preferable to do.

  The mixed dyed fabric comprising cellulose fiber, polyester fiber and polyurethane fiber thus obtained is stipulated in the deodorant processed fiber product certification standard (April 1, 2010 edition) established by the Japan Fiber Evaluation Technology Council. Excellent deodorizing performance against aging odors. Specifically, in the JTETC deodorant classification “aged odor” deodorization test, which will be described later, the ammonia reduction rate according to the deodorant processed fiber product certification standard established by JTETC is 70% or more, preferably 75% or more. The reduction rate is 80% or more, preferably 85% or more, the reduction rate of isovaleric acid is 85% or more, preferably 90% or more, and the reduction rate of nonenal is 75% or more, preferably 85% or more.

The dyed fabric of the present invention is characterized by excellent aging odor deodorizing performance in the above test even after repeated washing. Specifically, the deodorizing performance can be maintained even in a fabric after 50 times of washing according to JIS-L-0217-103.
The dyed fabric of the present invention is a dyed fabric product that is excellent in water absorption and quick drying performance in addition to the above deodorizing performance, and has a high whiteness and a high commercial value.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited only to these examples.
The characteristic value measurement method used in the examples and the like will be described below.
(1) JTETC deodorant classification "aging odor" deodorization test Deodorization test using ammonia, acetic acid, isovaleric acid, nonenal (2-nonenal; CAS No. 463-53-8) as odor components The deodorant performance was evaluated by the following method.

<Deodorization performance evaluation>
1. Instrument analysis test: Instrument analysis was conducted on the above four components in accordance with the certification standards for deodorized textile products determined by JTETC. That is, the odor component and the sample were put in a container, and the residual concentration of the odor component after being left for 2 hours (sample test concentration after 2 hours) was measured. The reduction rate of the odor component was calculated by the following formula using the residual concentration of the container containing only the odor component as the blank test concentration.
Decrease rate (%) = [(Blank test concentration after 2 hours−Sample test concentration after 2 hours) / (2 hours
Later blank test concentration)] × 100
Ammonia and acetic acid were measured by a detector tube method, and isovaleric acid and nonenal were measured by a gas chromatography method.
Judgment is passed “○” if the conditions of ammonia reduction rate 70% or more, acetic acid reduction rate 80% or more, isovaleric acid reduction rate 85% or more, nonenal reduction rate 75% or more are satisfied. Other than that, it was determined as a failure “x”.
Washing was performed according to JIS-L-0217-103 method.

2. Sensory test: Put odor component and sample in flask, compare sample odor and odor in flask after standing for 2 hours with judgment odor, and 5 or more of 6 judges judged that odor is weak according to the following criteria The case was accepted.
Odor "strong": When stronger than the judgment odor gas Odor "weak": When it is equivalent or weaker than the judgment odor gas Note that the judgment odor is ammonia, acetic acid, isovaleric acid, nonenal with odor intensity 2.0 Gas was used.

(2) Washing conditions According to JIS L-0217 103 method, it was performed 50 times. The detergent used was Kao Attack 1 g / L.
(3) Water absorption (water drop disappearance time)
Water drop disappearance time was evaluated according to JIS L-1097 dropping method. Measurement was performed 5 times for each sample, and the average disappearance time was determined. At this time, the average amount of one water droplet was 0.039 ml.
(4) Quick drying The dyed fabric (10 cm square) is sufficiently wetted with water and dehydrated with a dehydrator at 2000 rpm for 1 minute, and then the weight of the fabric is measured to calculate the water content. %, The time (minutes) until the water content of the fabric reached 2% (water content felt dry) was measured.

(5) Whiteness of dyed fabric The dyed fabric was measured for X, Y, Z, x, and y using a spectrophotometer (manufactured by Gretag Macbeth, type: CE-7000A, D65 light source), and JIS Z8715-1991. The whiteness was determined according to A larger numerical value indicates higher whiteness, and a smaller value indicates lower whiteness.
(6) Measurement of pH of dyed finish fabric 50 g of dyed finish fabric was immersed in 500 ml of distilled water at room temperature for 30 minutes, and the pH of the aqueous solution was measured according to JIS-Z-8802.

[Example 1]
56 dtex / 30f cupra (Asahi Kasei Fibers Bemberg) and 22 dtex / 24f polyester fiber were entangled and mixed to prepare a composite mixed yarn.
Next, 4,4′-diphenylmethane isocyanate is added to polytetraoxymethylene glycol having a number average molecular weight of 1800 at an equivalent ratio of 1: 1.6, and the mixture is allowed to react under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. Thus, a polyurethane prepolymer whose ends were capped with an isocyanate was obtained. After cooling this to room temperature, N, N′-dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution. A solution prepared by dissolving ethylenediamine and diethylamine in N, N′-dimethylacetamide was prepared, and this was added to the prepolymer solution at room temperature to obtain a polyurethane solution having a solid content concentration of 30%. This solution was degassed, and 22 dtex polyurethane fiber was obtained by a normal dry spinning method.
Next, using the obtained composite blended yarn, polyurethane fiber, and 84 dtex / 144 fDTY polyester fiber, a bare tengumaru knitted fabric was produced at 32 gauge by a conventional method. The mixing ratio of cellulose fibers in the knitted fabric was 32%, the mixing ratio of polyester fibers was 60%, and the mixing ratio of polyurethane fibers was 8%.
Subsequently, it was pre-set at 190 ° C. in an expanded form, and scouring was performed with a liquid dyeing machine using the conditions shown below.

<Scouring conditions>
Nonionic / anionic surfactant mixture: Lebenol TD-838 1 g / L
(Surfactant made by Kitahiro Chemical Co., non-ionic: anionic ratio = 9: 1)
Bath ratio: 1:30
Processing temperature: 80 ° C
Treatment time: 20 minutes After the treatment, after washing with hot water and washing with water, polyester fibers were dyed with a liquid dyeing machine under the following conditions.

<Dyeing conditions>
Fluorescent whitening dye: Nikka Bright 8720 V-01S: 1.5% omf
Nonionic / anionic surfactant mixture: Lebenol TD-838 1 g / L
Polyester resin: SR-1801M Conch 2% omf (Takamatsu Yushi, solid content 15
%, Molecular weight 12000)
pH: 4.5 (adjusted with tartaric acid 0.06 g / L)
Bath ratio: 1:25
Dyeing temperature: 130 ° C
Dyeing time: 45 minutes After dyeing, after washing with hot water at 80 ° C. and washing with water, the cellulose fibers were bleached and dyed simultaneously under the following conditions.

<Bleaching and dyeing conditions>
Bleach: Hydrogen peroxide (30%) 10ml / L
Fluorescent whitening dye: Blank fore BA 0.2% omf
Sodium carbonate: 2g / L
Bath ratio: 1:30
Processing temperature: 95 ° C
Treatment time: 45 minutes After the treatment, after washing with hot water at 80 ° C. and water washing, using a tartaric acid 2 g / L and a bath softener 2 g / L, soaking at 60 ° C. for 15 minutes and then dehydrating. It was.
Next, 1 g / L of softener and tartaric acid are added to the pad bath, and a finishing agent is applied by the pad method.
After drying, it was finished by heat treatment at 130 ° C. The pH of the finished fabric was 4.5.
The weight of the finished dyed fabric was 130 g / m ² , the coarse density was 76 / inch, and the well density was 48 / inch.

Table 1 below shows the evaluation results of the deodorizing performance, water absorption, quick drying performance and whiteness of the dyed fabric, and the evaluation results of the deodorizing performance and quick drying performance after 50 washings.
From the results in Table 1, it can be seen that the fabric obtained in Example 1 is a dyed fabric having excellent deodorizing performance, excellent water absorption and quick drying performance, high whiteness, and high commercial value.

[Example 2]
Of the conditions for dyeing the polyester fiber in Example 1 after presetting and scouring the bear tengu knitted fabric obtained in Example 1, the pH was adjusted to 5.5 (adjusted with lactic acid 0.7 ml / L). Except for changing the resin concentration to 4% omf, dyeing was performed in the same manner as in Example 1, and a finishing agent was applied so as to obtain the same property amount, followed by heat setting.
Table 1 below shows the evaluation results of the deodorizing performance, water absorption quick drying performance, and whiteness of the obtained dyed fabric, and the evaluation results of the deodorization performance after 50 washes and water absorption quick drying performance.
From the results in Table 1, it can be seen that the fabric obtained in Example 2 is a dyed fabric having excellent deodorizing performance, excellent water absorption and quick drying performance, high whiteness, and high commercial value.

[Comparative Example 1]
As Comparative Example 1, dyeing is performed in the same manner as in Example 1 using the Bear Tensyumaru knitted fabric obtained in Example 1, but the pH at the time of dyeing the polyester fiber is 4.0 (0.7 g of tartaric acid). Except for the change to (adjusted with / L), all were performed under the same conditions, and heat setting was performed so that the same amount of sex was obtained.
Table 1 below shows the evaluation results of the deodorizing performance, water absorption quick drying performance, whiteness, and the deodorization performance after 50 washings and water absorption quick drying performance of the obtained dyed fabric.
From the results shown in Table 1, the dyed fabrics obtained in Examples 1 and 2 of the present invention are dyed fabrics having a high commercial value that are superior in deodorizing performance and whiteness compared to the fabric obtained in Comparative Example 1. I understand.

[Comparative Example 2]
As Comparative Example 2, dyeing is performed in the same manner as in Example 1 using the Bear Tensyumaru knitted fabric obtained in Example 1, but the nonionic / anionic surface activity used in combination with the dyeing of the polyester fiber Except for carrying out without using the agent mixture and the polyester resin, all were carried out under the same conditions, and heat setting was performed so as to obtain the same amount of properties.
Table 1 below shows the evaluation results of the deodorizing performance, water absorption quick drying performance, whiteness, and the deodorization performance after 50 washings and water absorption quick drying performance of the obtained dyed fabric.
From the results in Table 1, the dyed fabrics obtained in Examples 1 and 2 of the present invention have a high commercial value, which is superior in deodorizing performance, water absorption quick drying performance, and whiteness compared to the fabric obtained in Comparative Example 2. It turns out that it is dyed fabric.

  The dyed fabric of the present invention is a deodorant dyed fabric that has excellent deodorizing performance against aging odor, excellent whiteness, and excellent water absorption and quick drying performance, and thus can be suitably used in the inner field and sports clothing field. .

Claims (4)

  A dyed fabric in which non-modified cellulose fiber, polyester fiber and polyurethane fiber are mixed, and after 50 washings, the ammonia reduction rate is 70% or more and the acetic acid reduction rate is 80% in the deodorant processed fiber product certification standard. % Deodorant dyed fabric, characterized in that the reduction rate of isovaleric acid is 85% or more and the nonenal reduction rate is 75% or more.   2. The deodorant dyed fabric according to claim 1, comprising 0.1 to 0.9% by weight of a polyester resin having a molecular weight of 8000 to 15000. 3.   In a dye bath adjusted to a pH of 4.5 to 6.0 with hydroxy acid, the polyester fiber is treated at a temperature of 125 to 135 ° C. using a nonionic / anionic surfactant mixture, a polyester resin and a fluorescent whitening dye. The deodorant dyed fabric according to claim 2, which is dyed.   4. The deodorant dyed fabric according to claim 3, wherein after the dyeing of the polyester fiber, the unmodified cellulose fiber is bleached and dyed with a fluorescent dye at the same time.