JP2012241290A - Deodorant fabric excellent in washing durability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant fabric that is a mixed fabric including an unmodified cellulose fiber, a basic dye dyeable fiber and a polyurethane fiber, is excellent in deodorant performance against aging odors, maintains a crispy feeling, is excellent in color clarity, and is excellent in wearability.SOLUTION: There is provided a deodorant fabric including an unmodified cellulose fiber, a basic dye dyeable fiber and a polyurethane fiber all together. The deodorant fabric has an isovaleric acid reduction rate of 85% or more and a nonenal reduction rate of 75% or more after washing 50 times according to a qualification standard for deodorant processed fiber products.

Description

  The present invention relates to a mixed fabric of cellulose fiber, basic dye-dyeable fiber, and polyurethane fiber, which is excellent in deodorizing performance. More specifically, the present invention has a deodorizing property excellent in washing durability, a texture that has a sharp feeling, and is excellent in color clarity and dyeing fastness. The present invention relates to a mixed fabric of mold fibers and polyurethane fibers.

Cellulose fibers such as cotton are often used in clothing. In recent years, deodorizing performance and the feeling of stickiness on the skin have been used as functions to satisfy comfort in daily life, especially in summer. There is a need for a solution.
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 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.

In Patent Document 1 below, as a method for obtaining various deodorizing functions, a fabric formed by knitting fibrils to which a titanium oxide photocatalyst is attached is described. In Patent Document 2 below, a fabric product itself is used. A method for processing by immersing the substrate in a photocatalyst-containing treatment solution is disclosed.
However, although these methods are effective for specific odors, it is not possible to remove all the four odor components described above.

  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. Oxidation propagation caused by valmitoleic acid becomes valmitooleic acid hydroperoxide, which is cleaved and decomposed into nonenal. Therefore, as a method of inhibition, to prevent oxidative propagation due to lipid peroxide, curene extract and ougon extract However, there is a problem that these antioxidants themselves have no washing durability.

In Patent Documents 3 and 4 below, modified cellulose fibers obtained by graft copolymerization of methacrylic acid to cellulose fibers, polyester fibers, and polyurethanes as methods for expressing surprising deodorizing properties against aging odors. A composite fabric with fibers is disclosed.
However, graft copolymerization of cellulose fibers causes a decrease in strength and a decrease in whiteness, a decrease in bursting strength in the fabric, a decrease in wear resistance, and color clarity in the inner and sports garments cannot be obtained. When cellulose fiber and polyester fiber or polyamide fiber are mixed, there is a problem that the same color is poor.

  Patent Document 5 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.

  Thus, in the present situation, in the fabric used without modifying the cellulose fiber, it has excellent deodorizing performance against aging odor, has no stickiness on the skin surface, has a smooth texture, and has excellent dyeability. No dyed product has been obtained.

JP 2002-030552 A JP 2007-126664 A Japanese Patent No. 4235244 WO2009 / 101995 Publication JP 2010-242240 A

  The problem to be solved by the present invention is that, in a mixed fabric of unmodified cellulose fibers, basic dyeable fibers and polyurethane fibers, it is excellent in washing durability for deodorizing performance against aging odors, and to the skin surface. An object of the present invention is to provide a deodorant fabric which has no stickiness and has a smooth texture, is excellent in color sharpness and excellent in color fastness, and a method for producing the same.

The present inventor has intensively studied and repeated experiments in order to solve the above-mentioned problems. As a result, in a mixed product of unmodified cellulose fibers, basic dyeable fibers and polyurethane fibers, the cellulose fibers are converted into cellulolytic enzymes. By reducing the weight, a streak groove of a specific size is formed along the fiber axis direction on the surface of the cellulose fiber, and the basic dye-dyeable fiber is dyed with a cationic dye. It has been found that by combining and using a specific polyurethane fiber, the washing durability performance with excellent deodorizing performance against the aging odor is expressed, and the present invention has been completed.
That is, the present invention is as follows.

  [1] Deodorant fabric mixed with unmodified cellulose fiber, basic dyeable fiber, and polyurethane fiber, and the rate of reduction of isovaleric acid in the deodorant processed fiber product certification standard after 50 washings Is a deodorant fabric characterized by having a nonane reduction rate of 75% or more.

  [2] The deodorant fabric according to the above [1], which is subjected to a 1.5 to 10% reduction treatment with a cellulose degrading enzyme at a temperature of 60 ° C. or lower.

  [3] The deodorant fabric according to [1] or [2], wherein the basic dye-dyeable fiber is dyed with a cationic dye.

  [4] The deodorant surname fabric according to any one of the above [1] to [3], containing 0.1 to 0.7% by weight of an aromatic polyester polyether block copolymer.

  The present invention is a deodorant fabric composed of unmodified cellulose fibers, basic dyeable fibers, and polyurethane fibers. The surface of cellulose fibers is specified by reducing the amount of cellulose fibers with a cellulolytic enzyme. Deodorant performance is improved by forming streaked grooves of the size of, and hydrophilic performance is achieved by dyeing basic dye-dyeable fibers with cationic dyes and adding aromatic polyester polyether block copolymers Is improved, excellent deodorizing performance against aging odor is exhibited, and washing durability with deodorizing performance is exhibited.

Hereinafter, the present invention will be described in detail.
The present invention is a fabric composed of unmodified cellulose fibers, basic dye-dyeable fibers and polyurethane fibers, and is excellent in deodorizing performance against aging odors, especially isovaleric acid and nonenal, and has a washing durability. It is an improvement.
Conventionally, modified cellulose fibers obtained by graft copolymerization reaction of methacrylic acid to cellulose fibers have been devised for imparting deodorant performance, but the cellulose fibers in the present invention are not modified. It is a cellulose fiber, and specifically, it is a cellulose fiber to which the carboxyl group by post-processing is not provided substantially. Cellulose fibers refer to natural cellulosic fibers such as cotton and hemp, and regenerated cellulose fibers such as rayon and polynosic, and regenerated cellulose fibers can be preferably used. The effect is most noticeable.

The fabric according to the present invention is characterized in that a cellulose fiber is treated with a cellulolytic enzyme to form a streak-like groove having a specific size in the fiber axis direction. Thereby, the deodorizing effect of basic gas, such as ammonia, and the acidic gas of acetic acid and isovaleric acid increases. In particular, regenerated cellulose fibers (long fibers) are also preferable from the viewpoint of easy control of the width and length of the specific streak-like grooves in the fiber axis direction when treated with a cellulolytic enzyme.
The cellulose fiber of the present invention is not particularly limited, but is preferably a fiber having a total fineness of 30 to 300 dtex. Furthermore, in the case of the L-shaped cross section, the cross-sectional shape is easy to obtain a supple texture and the specific surface area is large, so the efficiency of the weight loss treatment with cellulase is increased, and a streak groove is easily formed around the recess. This is preferable because the effects of the invention are sufficiently achieved.

  The cellulose fiber of the present invention preferably contains 50% or more of regenerated cellulose fiber, and more preferably 100% of regenerated cellulose fiber. In addition, silk, wool, polyester, polyamide, and polyacryl fiber may be contained up to 45%.

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, air jet fine spun yarn, sweet twisted yarn-strong twisted yarn, false twisted yarn, air injection processed yarn, indentation processing There are yarn, knitted knitted yarn and the like.
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, two-feed (simultaneous feed and feed difference) air The mixed form by injection processing etc. is mentioned.

In the present invention, the basic dye-dyeable fiber is a fiber made of polyester in which polyethylene terephthalate, polybutylene terephthalate or polypyropylene terephthalate units are the main constituent components and a basic dye-dyed seating component is copolymerized.
Examples of the basic dye-dyed seat component include alkali metal salts of sulfoisophthalic acid, phosphonium salts of sulfoisophthalic acid, and ester-forming derivatives derived therefrom. Specific examples include alkali metal salts of sulfoisophthalic acid such as 5-sodium sulfoisophthalic acid and 5-lithium sulfoisophthalic acid, 5- (tetraalkyl) phosphonium sulfoisophthalic acid and ester-forming derivatives derived therefrom. It is done. Of these, 5-sodium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5- (tetrabutyl) phosphonium sulfoisophthalic acid, and 5- (tetraethyl) phosphonium sulfoisophthalic acid are preferable from the viewpoint of deodorizing performance.

  The copolymerization amount of the basic dye-dyed seat component is preferably 0.1 to 5 mol%, more preferably 0.5 to 3.5 mol%, based on the total acid component, from the viewpoint of deodorizing performance. It is. If the copolymerization amount is less than 0.1 mol%, the deodorizing performance of the present invention cannot be obtained. On the other hand, if it exceeds 5 mol%, a decrease in the yarn strength and light resistance becomes apparent, which is not preferable.

The basic dye-dyeable fiber of the present invention contains a surfactant such as titanium oxide and alkylbenzene sulfonate, a conventionally known antioxidant, anti-coloring agent, light-proofing agent, antistatic agent, alkali metal and the like. It may be manufactured by a conventionally known method.
The basic dye-dyeable fiber of the present invention is not particularly limited, but is preferably a fiber having a total fineness of 30 to 300 dtex. Furthermore, the cross-sectional shape may be flat, constricted flat, triangular, quadrilateral, three or more multi-leaf shape, C-type, H-type, X-type, and hollow cross-section in addition to the round shape, but it has a sharp feeling. From the viewpoint of texture and deodorizing performance, a fiber having an irregular cross section and a single yarn decitex of 1.1 decitex is preferable.

In addition, the basic dye-dyeable fiber of the present invention may contain up to 30% of silk, wool, polyester, polyamide, and polyacryl fiber.
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 in which the fiber is processed, a spun yarn such as a ring spun yarn, an open end spun yarn, 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 yarn, There are knit and knitted yarn.

｛式中、ｌは、１以上の整数であり、そしてＲ_４とＲ_５は、上記（イ）及び（ロ）に記載したものと同じである。｝、及び下記構造単位（Ｂ）：

｛式中、ｍは、１以上の整数であり、そしてＲ_４とＲ_６は、上記（イ）及び（ハ）に記載したものと同じである。｝の繰り返しにより表される構造を有する。 In the polyurethane fiber of the present invention, an active hydrogen-containing compound that reacts with an organic polyisocyanate, a polyalkylene ether diol, and an isocyanate group is respectively represented by the following (a), (b), and (c):
(B) an organic _{polyisocyanate:} R 4 - in (NCO) x {wherein, _{R 4} is an organic residue, and x is an integer of 2 or more. },
(B) Polyalkylene ether diol: HO—R ₅ —OH {wherein R ₅ is a residue of the polyalkylene ether diol. },
(C) Active hydrogen-containing compound that reacts with isocyanate group: HR ₆ -H and / or R ₇ -H {wherein R ₆ and R ₇ are residues of the active hydrogen-containing compound. }
Are basically represented by the following structural unit (A):

{In the formula, l is an integer of 1 or more, and R ₄ and R ₅ are the same as those described in (a) and (b) above. }, And the following structural unit (B):

{In the formula, m is an integer of 1 or more, and R ₄ and R ₆ are the same as those described in (a) and (c) above. } Has a structure represented by repetition.

からなるものであればよく、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）：

｛式中、Ｒ_１は、炭素原子数１〜５の直鎖又は分岐アルキレン基であり、Ｒ_２とＲ_３は、炭素原子数１〜３のアルキル基であるか、又はＲ_２とＲ_３は、一緒になって、脂環式炭化水素残基を形成する。｝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。 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 urea bond portion bonded to the R ₄ group can be increased or decreased. The terminal of the polyurethane polymer may be —R ₆ —H or —R ₇ .
In the present invention, the polyalkylene ether diol is mainly composed of the following structural unit (C):

For example, polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran can be used.
Other than this, the above-mentioned structural unit (C) and the following structural unit (D):

{Wherein R ₁ is a linear or branched alkylene group having 1 to 5 carbon atoms, and R ₂ and R ₃ are alkyl groups having 1 to 3 carbon atoms, or R ₂ and R ₃ Together form an alicyclic hydrocarbon residue. } May be a copolymerized polyalkylene ether diol.

The copolymerized polyalkylene ether diol has the following formula (1):
0.05 ≦ (M _D ) / (M _C + M _D ) ≦ 0.50 (1)
{Wherein M _C and M _D are respectively the total number of structural units (C) and (D) present in the polyalkylene ether diol, and the structural units (C) and (D) are The polyalkylene ether diol may be present in a random or block form. } Having a specific ratio of alkyl groups represented by Formula (1) is more preferably 0.10 ≦ (M _D ) / (M _C + M _D ) ≦ 0.45.

  Such a specific polyalkylene ether diol can be produced by reacting tetrahydrofuran with a low-molecular diol or a dehydrated cyclic low-molecular compound thereof alone or in combination, and using a heteropolyacid with a controlled hydration number as a catalyst. it can. Examples of the production method include, but are not limited to, the method described in JP-A-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 satisfies the formula (1), and further has the following formula (2):
_{0.06 ≦ (T D) / (} T C + T D) ≦ 0.70 ··· Equation (2)
{Wherein, T _C and T _D are the total number of structural units (C) and (D) present at the terminals of the polyalkylene ether diol, respectively. } It is preferable to have the alkyl group terminal of the specific ratio represented by these.

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) to the structural unit (D) in the polyalkylene ether diol is represented by the following formula (3):
1.20 ≦ {(T _D ) / (T _C + T _D )} / {(M _D ) / (M _C + M _D )} ≦ 6.0 Formula (3)
{Wherein M _C , M _D , T _C , and T _D are the same as those defined in Formula (1) and Formula (2). }
Is preferably satisfied.

  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.

The stoichiometric ratio of various compounds used in the present invention is the sum of the hydroxyl groups of the polyalkylene ether diol represented by (ii) and the active hydrogens of the active hydrogen-containing compound represented by (iii). However, it is preferable that it is 0.9-1.15 equivalent with respect to the isocyanate group of the organic polyisocyanate compound represented by said (i), and it is more preferable that it is 1.0-1.05 equivalent.
The polyurethane fiber having the above structure of the present invention may be obtained by the method described in Japanese Patent No. 4002440 and may contain a tertiary nitrogen compound.

  The polyurethane fiber may contain a metal oxide or a metal hydroxide as necessary. For example, magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrotalcite Similar compounds may be used alone or as a mixture of two or more. These addition amounts are preferably 0.1 to 6.0 wt%. In addition, the polyurethane fiber may contain other known stabilizers, ultraviolet absorbers, and the like.

  The deodorant fabric of the present invention contains unmodified cellulose fibers, basic dye-dyeable fibers, and polyurethane fibers, and the proportion of each fiber can be appropriately determined depending on the use. % Or more, 30% or more of the basic dye-dyeable fiber, and 20% or less of the polyurethane fiber can be used. In terms of fabric performance and deodorant properties, it is more preferable that the cellulose fiber is 20 to 60%, the basic dyeable fiber is 20 to 60%, and the polyurethane fiber is 3 to 15%. In addition to these fibers, polyester, nylon, acrylic, wool, silk, etc. may be mixed.

The form of the mixed fabric of the present invention is roughly classified into a thread form and a cloth form.
Examples of yarn forms when cellulose fibers and basic dye-dyeable fibers are mixed are blended (blended cotton, fleece blended, sliver blended, core yarn, silospan, silofil, hollow spindle, etc.), entangled blended fiber , Cross twist, 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 twisting, two feeds (simultaneous feed) Or feed difference) and mixed form by air injection processing.

  In addition, in order to obtain a smooth texture of the present invention, preferably, the basic dye-dyeable fiber is fused in a false false twist of a cellulose fiber and a basic dye-dyeable fiber, It is preferable to use a method of forming an untwisted portion or to form a twisted yarn with a twist number of 600 to 1200 T / m.

The form of the polyurethane fiber is, for example, a so-called covering yarn, in which a bare fiber (10 to 500 dtex) of polyurethane fiber is coated with cellulose fiber, basic dye-dyeable fiber, or other fiber such as polyester or nylon. Examples of known coated yarns include (single and double covering), twisted yarn, core yarn, and crossed yarn.
Examples of the fabric form include knitted fabrics, woven fabrics, non-woven fabrics, and composite fabrics thereof (for example, laminated fabrics). As a specific example, there is a so-called on-machine mixed 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, basic dye-dyeable fibers, and other fibers.

In the present invention, the form of mixing is not limited at all, and cellulose fibers, basic dye-dyeable fibers, and polyurethane fibers may be mixed by known mixing means.
In the deodorant fabric according to the present invention, before dyeing the above-mentioned mixed fabric, the weight of the fabric is reduced by 1.5% to 10% by the cellulolytic enzyme treatment described later, and the surface of the cellulose fiber is streaked. It is preferable to form a groove.
When the weight loss rate is in the above range, 10 or more streak grooves having a width of 0.05 to 1.50 μm and a length of 3 to 25 μm exist on the surface of the cellulose fiber per 50 μm of the fiber axis length. In addition, the streak groove does not necessarily need to be substantially parallel to the fiber axis direction, and may be inclined up to 45 degrees.

By having such a streak-like groove, the specific surface area of the fiber is increased, the supplemental amount of each odor component of ammonia, acetic acid, isovaleric acid, and nonenal is increased, and the basic dye-dyeable fiber and the polyurethane fiber are increased. The deodorizing effect in the mixed fabric is enhanced, and a product having a high deodorizing effect of the aging odor referred to in the present invention is obtained, and the color sharpness is also increased.
Control of the width | variety and length of the above-mentioned streak-like groove | channel is easier in a regenerated cellulose fiber among cellulose fibers.
In addition, by having this streak groove, when sweating, the power to quickly absorb moisture and the power to diffuse moisture are demonstrated, so that it does not stick to the body, does not feel sticky, and dries quickly The effect and texture are more supple, the skin feels better, and the comfort is improved. This effect persists even after repeated washing.

  If the weight loss rate is 1.5% or more, the width of the streak groove is 0.05 μm or more, the length is 3 μm or more, the number is 10 or more, and the deodorizing effect can be enhanced, and the supple wind This is preferable because a color is obtained and the color becomes clear. On the other hand, when the weight loss rate exceeds 10%, there is a problem that the strength reduction of the cellulose fiber becomes large.

Cellulose-degrading enzyme as used in the present invention refers to cellulases such as exoglucanase, endoglucanase, serbase, β-glucosidase, cellobiase, etc., each of which can be used alone or in combination.
Examples of means for controlling the streak-like grooves on the surface of the cellulose fiber include enzyme (cellulase) concentration, pH, bath ratio, treatment temperature, and time during cellulolytic enzyme treatment. Treatment conditions include a bath ratio of 1: 0. In the case of acidic active cellulase, acetic acid and citric acid, in the case of neutral active cellulase, sodium phosphate and alkaline active cellulase so that the pH is about 5 to 1:50. In some cases, a buffering agent such as ammonia or sodium carbonate may be used alone or in combination for adjustment. The concentration of cellulase used varies depending on the activity of the cellulase and the target weight loss, but is generally 0.3 to 15% by weight, the treatment temperature is 40 to 65 ° C., and the treatment time is 30 to 300. Minutes.

After the treatment, the enzyme is deactivated, but it may be treated at a temperature at which the enzyme to be used is deactivated, and it is preferably 70 to 100 ° C. and 15 to 30 minutes. In addition, it is preferable to use an alkaline agent in the treatment bath in order to promote enzyme desorption.
In the treatment with cellulolytic enzymes, rotary dyeing machines such as rotary drum dyeing machines, paddle dyeing machines, wins reel dyeing machines, jigger dyeing machines, liquid dyeing machines, airflow dyeing machines, etc. can be used. It is preferable to use an apparatus capable of processing in an expanded form, such as a roll or pad-jig dyeing machine, because it is easy to control the formation of the streak groove of the present invention.

  The fabric according to the present invention can be obtained by subjecting a mixed fabric of cellulose fiber, basic dyeable fiber, and polyurethane fiber to a weight loss treatment of 1.5 to 10.0% with cellulolytic enzyme prior to dyeing. From the viewpoint of the odor effect, it is preferable. A weight reduction treatment of 2.0 to 8.5% is more preferable because it can impart washing durability and color sharpness of the deodorizing effect of the mixed fabric. The weight reduction process may be performed before or after or simultaneously with processes such as scouring and relaxing.

  The dyeing of the mixed fabric of the cellulose fiber, basic dyeable dyeable fiber and polyurethane fiber of the present invention is carried out after the treatment with the cellulolytic enzyme, but the dyeing of the cellulose fiber is usually carried out under the condition where the cellulose fiber is carried out. Any can be applied. The dyeing of the basic dyeable fiber is performed using a cationic dye. Cationic dyes are water-soluble dyes that are soluble in water and have basic groups, and are di- and triacrylmethane-based, quinoneimine (azine, oxazine, thiazine) -based, xanthene-based, methine-based (polymethine, azamethine) ), Heterocyclic azo dyes (thiazole azo, triazole azo, benzothiazole azo), anthraquinone dyes and the like. In addition, as a dispersion type cationic dye that is made water-dispersible by blocking a basic group, Kayacryl ED (manufactured by Nippon Kayaku Co., Ltd.), KIWA CDP (manufactured by Kiwa Chemical Industry Co., Ltd.), Nichilon CDPN (Nissei Kasei ( Co., Ltd.), Aizen Cathilon DP (Hodogaya Chemical Co., Ltd.) is used for dyeing with one-bath dyeing with cellulose fibers, and it is easy to give an aromatic polyester polyether block copolymer during dyeing. To preferred.

Further, the deodorizing performance is further enhanced by adding an aromatic polyester polyether block copolymer to the mixed fabric of the present invention.
The aromatic polyester polyether block copolymer used in the present invention is a block copolymer composed of terephthalic acid and / or isophthalic acid and alkylene glycol and / or polyalkylene glycol. Commercially available products of the copolymer include SR-C1800 cationically emulsified by Takamatsu Yushi Co., Ltd., SR-2010A having alkali resistance, SR-5000 containing dicarboxylic acid containing a sulfonic acid metal base, and the like. SR-5000 can be preferably used to obtain a smooth texture. The method for applying the copolymer is not particularly limited. For example, dyeing and bathing, padding method, flat screen printing method, rotary screen printing method, roller printing method, gravure roll method, kiss roll method, method using a foam processor Is exemplified. The application amount of the copolymer is 0.1 to 0.7% by weight in solid content with respect to the weight of the mixed fabric. If the applied amount is less than 0.1% by weight, the deodorizing performance of the present invention is not preferable, and if it exceeds 0.7% by weight, the dyeing fastness and the light resistance are lowered. Therefore, it is not preferable.

  The dyeing and finishing process is carried out after the treatment with the cellulose-degrading enzyme. As the dyeing and finishing process, any of the conditions under which cellulose fibers are usually used can be applied. It may be set as appropriate according to the conditions.

  The mixed dyed fabric comprising cellulose fiber, basic dye-dyeable fiber and polyurethane fiber thus obtained is a deodorant processed fiber product certification standard (April 1, 2010) established by the Japan Fiber Evaluation Technology Council. Excellent in deodorizing performance against aging odor specified in Nikkan). Specifically, in the JTETC deodorant classification “aged odor” deodorization test, which will be described later, the reduction rate of isovaleric acid according to the deodorant processed fiber product certification standard defined by JTETC is 85% or more, preferably 90% or more, More preferably, it is 93% or more, and the decrease rate of Nonenal is 75% or more, preferably 85% or more, more preferably 90% or more.

  Furthermore, it is preferable to simultaneously achieve an ammonia reduction rate of 70% or more and an acetic acid reduction rate of 80% or more in the above test. More preferably, the ammonia reduction rate is 75% or more, the acetic acid reduction rate is 85% or more, more preferably the ammonia reduction rate is 80% or more, and the acetic acid reduction rate is 90% or more.

The deodorant fabric of the present invention is characterized by excellent aging deodorant 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 deodorant fabric of the present invention has an excellent color sharpness, a sharp texture, and good fastness performance in addition to the above deodorant performance. Specifically, JIS-L -0848 A dyed product with a high commercial value, wherein the fastness to sweat alkali in the A method is 3 or higher.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
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>
In accordance with the certification standard for deodorized textile products determined by JTETC, instrument analysis was performed on the above four components. Washing was performed according to JIS-L-0217-103 method.
Instrumental analysis test: An odor component and a sample were placed 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. Using the residual concentration of the container containing only odor components as the blank test concentration, the following formula:
Decrease rate (%) = (Blank test concentration after 2 hours−Sample test concentration after 2 hours) / (Blank test concentration after 2 hours) × 100
From the above, the reduction rate of the odor component was calculated. Ammonia and acetic acid were measured by a detector tube method, and isovaleric acid and nonenal were measured by a gas chromatography method.
Judgment passes the case where all the conditions of ammonia reduction rate 70% or more, acetic acid reduction rate 80% or more, isovaleric acid reduction rate 85% or more, and nonenal reduction rate 75% or more are satisfied. Other than that, it was determined as a failure “x” (see Table 1 below).

<Sensory test>
Out of the 6 judges, 5 or more people judged that the odor was weak according to the following criteria as a pass (refer to Table 1 below).
Odor “strong”: Stronger than the judgment odor gas Odor “weak”: Equivalent or weaker than the judgment odor gas

(2) State of streak-like groove on the surface of cellulose fiber Using a scanning electron microscope (manufactured by Hitachi, model S-3500N), the cellulose fiber surface of the sample was magnified 1800 times, and photographs were taken at five places as appropriate. Compared with the scale gauge, the width, length, and number of the streak grooves were measured, and the number (pieces) per 50 μm fiber length was calculated to obtain the average value.

(3) Washing condition 50 times according to JIS L-0217 103 method. The detergent used was Kao Attack 1 g / L.

(4) Texture evaluation The fabric after 10 washings of the dyed goods was subjected to relative evaluation according to the following evaluation criteria by the feel of the inspector (30 persons).
○: Good crispness △: Slightly inferior sensation ×: No crispness

(5) Fastness to sweat alkali The dyed product was evaluated using a sweat alkali artificial sweat according to the JIS-L-0848-A method. The degree of contamination of the test piece and the attached white cloth piece were judged by comparing with the gray scale for color change and the gray scale for contamination, respectively.

(6) Color clarity (saturation)
Using a spectrophotometer (manufactured by Gretag Macbeth, model; CE-7000A, D65 light source), the a and b values in the Lab color system are measured for the dyed fabric, and the following formula:
Saturation = √ (a ² + b ² )
The saturation was calculated. The larger the value, the higher the saturation and the clearer the color, and the smaller the value, the lower the saturation and the dull color.

(7) Same color property The difference in lightness between the cellulose fiber and the basic dyeable fiber was small, and the color difference, saturation difference, and irritation were small, and the determination was made in five stages according to the following evaluation criteria.
5th grade: Good 4th grade: Somewhat good 3rd grade: Normal 2nd grade: Somewhat inferior 1st grade: Inferior

[Example 1]
Mitsubishi Rayon Co., Ltd. basic dye-dyeable polyester fiber (trade name: AHY) 70 dtex / 48 f of POY is false twisted at 185 ° C. by a conventional method, The remaining 56dtex / 45f cupra (Asahi Kasei Fibers Co., Ltd. Bemberg) was inserted during the processing step and interlaced to obtain a composite yarn of 106dtex / 93f.

  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 to room temperature, N, N'-dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution. A solution in which ethylenediamine and diethylamine were dissolved in N, N′-dimethylacetamide was prepared and added to the prepolymer solution at room temperature to obtain a polyurethane solution having a solid content concentration of 30%. This solution was defoamed to obtain a 33 dtex polyurethane fiber by an ordinary dry spinning method.

Next, using the obtained composite yarn and polyurethane fiber, a bare tengumaru knitted fabric was produced at 28 gauge by a conventional method. The mixing ratio of the cellulose fibers in the knitted fabric was 48%, the mixing ratio of the basic dyeable fiber was 42%, and the mixing ratio of the polyurethane fibers was 10 wt%.
Next, after pre-wetting at 60 ° C. in a spread form, pre-setting at 185 ° C., using the enzyme treatment conditions shown below, using a liquid dyeing machine to reduce the weight loss rate to 2.8%, Adjusted and performed weight loss treatment.

<Enzyme treatment conditions>
Enzyme solution: Cellulase T (manufactured by Amano Enzyme, End + Exo-type Cellulase) 8% omf
pH: 4.5 (adjusted with acetic acid and sodium acetate)
Auxiliary agent: Immacol C2GL: 4 g / L
Bath ratio: 1:30
Processing temperature: 45 ° C
After the treatment, a deactivation treatment was performed at 80 ° C. for 15 minutes, followed by washing with water and dyeing under the following conditions.

<Dyeing conditions>
Dispersion type cationic dye: Kayacrill Red GRL-ED: 0.042% omf
Kayacrill Blue 2RL-ED: 0.252% omf
Reactive dye: Kayatheron React Red CN-3B: 0.12% omf
Kayatheron React Blue CN-BL: 0.72% omf
Sodium sulfate: 20 g / liter pH: 6.5
Aromatic polyester polyether block copolymer: SR-5000: 4% omf (manufactured by Takamatsu Oil and Fats, solid content: 8.5%)
Bath ratio: 1:25
Dyeing temperature: 100 ° C
Dyeing time: 45 minutes

After dyeing, hot water washing and water washing were repeated at 80 ° C., followed by dehydration and heat treatment.
The weight of the finished dyed fabric was 205 g / m ² , the coarse density was 100 / inch, and the well density was 50 / inch.
When the finished dyed fabric was observed with an electron microscope at a magnification of 1800 times, 14 streaks having a width of 0.4 μm and a length of 8.2 μm per 14 μm of the fiber length were present on the surface of the cellulose fiber. It was.
Table 1 below shows the evaluation results of the deodorizing performance, texture, clearness, sweat alkali fastness, and the deodorizing performance after 50 washings and the evaluation results of the texture of the obtained dyed fabric.
From the results shown in Table 1, the fabric obtained in Example 1 is excellent in deodorizing performance, has a sharp texture, has high color clarity, and has a high commercial value. I understand.

[Example 2]
After the bear tengu knitted fabric obtained in Example 1 was pre-set, it was dyed under the same conditions as in Example 1 without performing the enzyme treatment, and was heat-set so as to have the same sex weight.
Table 1 below shows the evaluation results of the deodorizing performance, texture, clearness, sweat alkali fastness, and the deodorizing performance after 50 washings and the evaluation results of the texture of the obtained dyed fabric.
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, a texture with a sharp feeling, and a high commercial value.

[Comparative Example 1]
As Comparative Example 1, the bare tengumaru knitted fabric obtained in Example 1 was used and dyeing was carried out in the same manner as in Example 1 without performing the enzyme treatment, but the aromatic polyester polyether block copolymer was used. It was done without using and heat set so as to have the same sex weight.
Table 1 below shows the evaluation results of the deodorizing performance, texture, and sweat alkali fastness of the obtained dyed fabric, and the evaluation results of the deodorizing performance and texture after 50 washings.
From the results shown in Table 1, it can be seen that the dyed fabrics obtained in Examples 1 and 2 of the present invention are dyed fabrics having excellent deodorizing performance and high commercial value as compared with the fabric obtained in Comparative Example 1.

  The deodorant fabric of the present invention is a deodorant fabric that is excellent in deodorizing performance against aging odors, maintains a crisp texture, has excellent color sharpness, and is excellent in wearing feeling. It can be suitably used in the sports clothing field.

Claims (4)

  Deodorant fabric made by mixing unmodified cellulose fiber, basic dyeable fiber, and polyurethane fiber, with an 85% reduction rate of isovaleric acid in the deodorant processed fiber product certification standard after 50 washings A deodorant fabric characterized in that it has the above-mentioned and has a nonenal reduction rate of 75% or more.   The deodorant fabric according to claim 1, which is subjected to a weight loss treatment of 1.5 to 10% at a temperature of 60 ° C or lower with a cellulolytic enzyme.   The deodorant fabric according to claim 1 or 2, wherein the basic dye-dyeable fiber is dyed with a cationic dye.   The deodorant last-name fabric of any one of Claims 1-3 which contains 0.1-0.7weight% of aromatic polyester polyether block copolymers.