JP2012202012A - Improved deodorant fabric - Google Patents

Abstract

An object of the present invention is to provide a mixed fabric of unmodified cellulose fibers and polyurethane fibers, which has excellent deodorizing performance against aging odors, maintains a supple texture, has excellent color clarity, and is excellent in wearing feeling. And the production method thereof.
SOLUTION: A deodorant fabric in which unmodified cellulose fibers and polyurethane fibers to which a carboxyl group is imparted are mixed, and the rate of reduction of isovaleric acid in the deodorant processed fiber product certification standard after 50 washings A deodorant fabric characterized in that it is 85% or more and has a nonenal reduction rate of 75% or more.
[Selection figure] None

Description

  The present invention relates to a mixed fabric of cellulose fibers and polyurethane fibers having excellent deodorizing performance. More specifically, the present invention relates to a mixed fabric of cellulose fibers and polyurethane fibers that has excellent deodorizing properties, has a supple texture, and is excellent in color sharpness.

Cellulose fibers such as cotton are often used in clothes, but in recent years, deodorization performance is required as a function for satisfying comfort in daily life especially in summer.
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 of applying heat treatment by attaching a flavone derivative and a polycarboxylic acid as a method of imparting durable deodorant properties.
However, this method has a problem that the durability performance after 50 washings of the ammonia odor is poor and the effect of the acidic odor is weak.
Thus, at present, a dyed product having excellent deodorizing performance against aging odors, a supple texture, and excellent dyeability has not been obtained in fabrics used without modifying cellulose fibers.

JP 2002-030552 A JP 2007-126664 A Japanese Patent No. 4235244 WO2009 / 101995 Publication Japanese Patent No. 2946339

  The problem to be solved by the present invention is that, in a mixed fabric of cellulose fibers and polyurethane fibers that are not modified, it has excellent deodorizing performance against aging odors, retains a supple texture, has excellent color clarity, and is worn It is to provide a deodorant fabric excellent in feeling and a method for producing the same.

The present inventor has intensively studied to solve the above problems and repeated experiments. In a mixed product of cellulose fiber and polyurethane fiber that is not modified, the cellulose fiber is reduced by a cellulose-degrading enzyme, so that the cellulose fiber is reduced. By forming a streak-like groove of a specific size along the fiber axis direction of the surface and treating with polyacrylic acid, it was found that excellent deodorizing performance against aging odor was expressed, and the present invention It came to be completed.
That is, the present invention is as follows.

[1] A deodorant fabric using a mixture of a non-modified cellulose fiber to which a carboxyl group has been added and a polyurethane fiber, and has an isovaleric acid reduction rate of 85 according to the deodorant processed fiber product certification standard after 50 washings. % Deodorant fabric characterized in that the percentage of decrease in Nonenal is 75% or more.

[2] The deodorizing fabric according to [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], which is treated with a polycarboxylic acid.

  The present invention is a deodorant fabric composed of cellulose fibers and polyurethane fibers, and the cellulose fibers are subjected to a weight-reducing treatment with a cellulose-degrading enzyme to form a streak-like groove having a specific size on the surface of the cellulose fibers. In addition to improving the deodorizing performance, the treatment with polycarboxylic acid gives the cellulose fiber an excellent deodorizing performance against aging odors by imparting a carboxyl group, and the washing durability of the deodorizing performance is achieved. Is done.

Hereinafter, the present invention will be described in detail.
The present invention is a fabric composed of unmodified cellulose fibers and polyurethane fibers described later, and is excellent in deodorizing performance against aging odors, particularly isovaleric acid and nonenal, and has improved washing durability.

In the present invention, the cellulose fiber refers to unmodified natural cellulose fibers such as cotton and hemp, and regenerated cellulose fibers such as rayon and polynosic, and regenerated cellulose fibers can be preferably used. When is used, the effect of the present invention appears most remarkably.
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 Yarn, knitted knitted yarn, etc.

  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.

  The deodorant fabric of the present invention contains cellulose fibers and polyurethane fibers that are not modified, and the ratio of cellulose fibers and polyurethane fibers can be determined as appropriate depending on the application, but the cellulose fibers are generally used in an amount of 30% or more. A preferable result is obtained when 25% or less is mixed. From the standpoint of fabric performance and deodorant properties, it is more preferable that the cellulose fiber is 40 to 90% and the polyurethane fiber is 5 to 25%. 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.
As the thread form, a polyurethane fiber bare thread (10 to 500 dtex) coated with other fibers such as cellulose fiber, polyester, nylon, etc., for example, so-called covering yarn (single and double covering), twisted yarn, core yarn, Examples of known coated yarn forms such as crossed yarns.
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 or other fibers.
The form of mixing in the present invention is not limited at all, and it is sufficient that cellulose fibers and polyurethane fibers are mixed by known mixing means.

In the deodorant fabric according to the present invention, the above-mentioned mixed fabric is reduced by 1.5% to 10% of the fabric weight by a cellulose-degrading enzyme treatment described later before dyeing, and streaks are formed on the surface of the cellulose fiber. Can be formed.
When the weight loss ratio is in the above range, there are 10 or more streak-like grooves having a width of 0.05 to 1.50 μm and a length of 3 to 25 μm per 50 μm of fiber axis length on the surface of the cellulose fiber. 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 streak-like grooves, 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 further, the carboxyl fiber is added to the cellulose fiber by polycarboxylic acid treatment. By adding the group, the deodorizing effect in the fabric mixed with the polyurethane fiber is enhanced, and a product having a high deodorizing effect of the aging odor referred to in the present invention is obtained, and a supple texture is obtained. The sharpness also increases.
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 it is supple. A texture is obtained and the color becomes clear, which is preferable.
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. 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 used is deactivated, and preferably at 70 to 100 ° C. for 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.

  From the viewpoint of the deodorizing effect, the fabric according to the present invention is preferably subjected to a weight-reducing treatment of 1.5 to 10.0% with cellulolytic enzyme prior to dyeing the mixed fabric of cellulose fibers and polyurethane fibers. A weight reduction treatment of 2.0 to 8.5% is more preferable because it can impart washing durability, a supple texture, and color clarity 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.

In the fabric according to the present invention, the deodorizing performance is further improved by adding a carboxyl group to the cellulose fiber by the polycarboxylic acid treatment.
As the polycarboxylic acid in the present invention, an organic compound containing two or more carboxyl groups or one or more acid anhydride groups in one molecule can be preferably used. Polycarboxylic acids can be classified into dibasic acids, tribasic acids, tetrabasic acids, etc., depending on the number of carboxyl groups, but any of them may be used.
Polycarboxylic acids can be classified according to the type of residues other than carboxyl groups. For example, they can be classified into aliphatic groups, alicyclic groups, aromatic groups, etc. When the group contains an element other than hydrogen, it can be classified into oxyacids and amino acids.

  Representative examples of aliphatic dibasic acids that can be used as polycarboxylic acids are succinic acid, glutaric acid, succinic acid, maleic acid, fumaric acid, valeric acid, adipic acid, azelaic acid, sebacic acid, and their acid anhydrides. It is a thing.

  Examples of typical aliphatic tribasic acids include 1,2,3-propanetricarboxylic acid and acid anhydrides thereof, and examples of typical aliphatic tribasic acids include 1,2 3,4-butanetetracarboxylic acid and its anhydride. Among these, 1,2,3,4-butanetetracarboxylic acid can give a carboxyl group exactly to the hydroxyl groups at positions 2, 3, and 6 in the molecular structure of the regenerated cellulose fiber, and washing 50 times. Later, 15% or more of carboxyl groups per glucose unit which is a repeating unit of cellulose remains and is excellent in washing durability performance.

  Representative aliphatic polycarboxylic acids that can be used as the polycarboxylic acid include hexahydrophthalic acid, tetrahydrophthalic acid, naduccinic acid, tricarboxycyclopentylacetic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, and Diels-Alder compounds by reaction of maleic anhydride and dienoic acid represented by their acid anhydrides Or the polycarboxylic acid of the hydrogenated product.

  Typical aromatic dibasic acids that can be used as polycarboxylic acids are phthalic acid, diphenic acid, naphthalenedicarboxylic acid, and anhydrides thereof, and typical aromatic dibasic acids are trivalent. Mellitic acid and naphthalenetricarboxylic acid, and typical aromatic tetrabasic acids are pyromellitic acid and naphthalenetetracarboxylic acid.

As the oxyacid, malic acid, citric acid, tartaric acid and the like can be used. As the polycarboxylic acid containing an ether bond in the residue, polyethylene oxide dicarboxylic acid or polypropylene oxide dicarboxylic acid can be used. Moreover, glutaric acid can be used as an amino acid.
In addition, as the polycarboxylic acid, an acid composed of a polymer can be used. For example, polyacrylic acid, polyacrylic acid, poly (acrylic acid-maleic acid), poly (styrene-maleic acid), and polyfumaric acid can be used.

  In addition, when the aqueous polycarboxylic acid solution is applied to the fiber, it is preferable to use a catalyst in combination for enhancing the washing durability, and a phosphate or carbonate is suitable as the catalyst. As phosphates, primary sodium phosphate, dibasic sodium phosphate, tribasic lithium phosphate, sodium dihydrogen pyrophosphate, calcium triphosphate, sodium dihydrogen pyrophosphate, potassium triphosphate, orthophosphoric acid, hypophosphorous acid , Phosphorous acid, metaphosphoric acid, pyrophosphoric acid, pyrophosphorous acid, or a neutral salt or acidic salt thereof can be used. As carbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, etc. can be used.

  A suitable blending example of the polycarboxylic acid and the catalyst is a mixed aqueous solution of 0.1 to 10% by weight of the polycarboxylic acid and 0.1 to 10% by weight of the catalyst. It is preferable to dissolve the carboxylic acid and adjust the aqueous solution pH to 3 to 5, and to reduce the influence on the physical properties of the fiber, it is more preferable to adjust the aqueous solution pH to 4 to 5.

The treatment of the mixed aqueous solution of polycarboxylic acid and catalyst on the mixed fabric of cellulose fibers and polyurethane fibers of the present invention is preferably performed after the mixed fabric is dyed, and a method of immersing the mixed dyed product in the mixed aqueous solution, What is necessary is just to give by the pad, the method of spraying mixed aqueous solution, and the coating method, and it is made to dry at 90-120 ° C after giving by the method of immersion treatment and the pad method at the temperature of 20-100 ° C, It is preferable to perform heat treatment at 120 to 180 ° C. for 1 to 5 minutes.
The dyeing and finishing of the mixed fabric of cellulose fiber and polyurethane fiber of the present invention is carried out after the treatment with the cellulolytic enzyme, and the dyeing and finishing method is usually a condition in which the cellulose fiber is carried out. Any of them can be applied, and may be appropriately set according to the characteristics of the mixed fabric.
Moreover, as a finishing agent, it is preferable to use supramolecular amino-modified silicone from the viewpoint of maintaining the feel durability of cellulose fibers.

  The polyurethane fiber of the present invention is a polyether polyurethane 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 ethylenediamine or the like as a diamine component. Fibers, polycaprolactone, polyester diols made of polyester such as adipic acid / 1,6-hexanediol / neopentyl glycol, aliphatic diols such as butanediol, and the like as diol components, and aromatics such as 4,4′diphenylmethane diisocyanate It is a polyurethane fiber appropriately selected from polyester-based polyurethane fibers obtained using diisocyanate as a diisocyanate component.

｛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。 Preferred polyurethane fibers include organic polyisocyanates, polyalkylene ether diols, and active hydrogen-containing compounds that react with isocyanate groups, respectively (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. One or more of dibasic acids such as polyether diol, 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 diol 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 (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. Formula (2) is 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 Equation (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 contain a tertiary nitrogen compound by the method described in Japanese Patent No. 4002440.

  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 mixed dyed fabric composed of cellulose fibers and polyurethane fibers obtained in this way is stipulated in the deodorant processed fiber product certification standard (April 1, 2010 edition) established by the Japan Fiber Evaluation Technology Council. Excellent deodorant performance against aging odors. Specifically, the reduction rate of isovaleric acid according to the JTETC deodorant processed fiber product certification standard in the JTETC deodorant property “aged odor” deodorization test described later 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 supple texture, and good fastness performance in addition to the above deodorant performance. Specifically, JIS-L-0848 It is a dyed product with a high commercial value in which the fastness to sweat alkali in Method A is 3 or higher.

Hereinafter, the present invention will be specifically described with reference to examples and the like, 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. Otherwise, it was determined as a failure “x” (see Table 2 and Table 3 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 (see Tables 2 and 3 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).
○: supple feeling is good △: supple feeling is slightly inferior ×: no supple feeling

(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 cellulose fiber and nylon 6 fiber was small, and the difference in hue difference, saturation difference, and irritation was determined to be good, and was judged 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]
Using a 84 dtex / 45 f cupra (Asahi Kasei Fibers Bemberg) and 33 dtex polyether-based polyurethane fibers (Asahi Kasei Fibers Leuka CR), a bare tengu-maru knitted fabric was prepared at 36 gauge by a conventional method. The mixing ratio of the polyurethane fiber at this time was 13 wt%.
Next, after pre-wetting at 60 ° C. in a spread form, pre-setting at 185 ° C., using the enzyme treatment conditions shown below, and using a liquid dyeing machine to reduce the weight loss rate to 5.5%, 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>
Reactive dye: Remazole Turquoise Blue G: 1.0% omf
Sodium carbonate: 10 g / liter Salt glass: 30 g / liter Auxiliary agent: Imacol C2GL (softener in bath): 4 g / L
Bath ratio: 1:20
Dyeing temperature: 60 ° C
Dyeing time: 50 minutes After dyeing, hot water washing and water washing were repeated at 90 ° C., and after dehydration, polycarboxylic acid processing was performed by the pad method under the following conditions, followed by heat treatment.

<Processing conditions>
Rikacid BT-W: 2.5% (1,2,3,4-butanetetracarboxylic acid manufactured by Shin Nippon Chemical Co., Ltd.)
Dibasic sodium phosphate (anhydrous): 2.5%
PH of mixed aqueous solution: 4.1
Pickup rate: 70%
Drying temperature, time: 110 ° C., 3 minutes Heat treatment temperature, time: 160 ° C., 1 minute The finished dyed fabric had a basis weight of 215 g / m ² , a coarse density of 112 lines / inch, and a well density of 61 lines / inch.

When the finished dyed fabric is observed with an electron microscope at a magnification of 1800 times, there are 16 streak-like grooves having a width of 0.4 μm and a length of 8.8 μm per 50 μm of fiber length on the surface of the cellulose fiber. It was.
The evaluation results of the deodorizing performance, texture, sharpness and sweat alkali fastness of the obtained dyed fabric are shown in the following Table 2, and the deodorizing performance after 50 washings and the evaluation results of the feeling are shown in Table 3 below. Shown in
From the results in Table 2 and Table 3, the fabric obtained in Example 1 is a dyed fabric having excellent deodorizing performance, having a supple texture, high color clarity, and high commercial value. I understand that.
In addition, in the following Table 1, the structure of the fabric obtained in Examples 1-6 and Comparative Examples 1-4 is shown.

[Comparative Example 1]
As Comparative Example 1, the Bear Tensyumaru knitted fabric obtained in Example 1 was used for dyeing by the same method, and heat setting was performed so as to obtain the same property amount.
The evaluation results of the deodorizing performance, texture and sweat alkali fastness of the dyed fabric obtained are shown in Table 2 below, and the deodorizing performance after 50 washings and the evaluation results of texture are shown in Table 3 below. .
From the results in Tables 2 and 3, the dyed fabric obtained in Example 1 of the present invention is a dyed fabric having excellent deodorizing performance and high commercial value as compared with the fabric obtained in Comparative Example 1. I understand.

[Comparative Example 2]
As Comparative Example 1, using the bear tengumaru knitted fabric obtained in Example 1, dyeing is performed in the same manner, and after dyeing, finishing is performed under the following conditions so that the same amount of sex is obtained. Finished by heat setting.
<Processing conditions>
Camellia 1D253: 2.5% (manufactured by Nisshin Fragrance Co., Ltd., flavone derivative)
Ricacid BT-W: 2.5%
Dibasic sodium phosphate (anhydrous): 2.0%
Pickup rate: 70%
Drying temperature, time: 110 ° C., 3 minutes Heat treatment temperature, time: 160 ° C., 1 minute Evaluation results of deodorizing performance, texture, and sweat alkali fastness of the obtained dyed fabric are shown in Table 2 below. Table 3 below shows the results of evaluation of deodorizing performance and texture after rotation.
From the results in Table 2 and Table 3, the dyed fabric obtained in Example 1 of the present invention is a dyed fabric having excellent deodorizing performance and high commercial value as compared with the fabric obtained in Comparative Example 2. I understand.

[Example 2]
4,4′-diphenylmethane isocyanate was added to polytetraoxymethylene glycol having a number average molecular weight of 1800 at an equivalent ratio of 1: 1.6, and the mixture was allowed to react under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. A polyurethane prepolymer 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 defoamed to obtain a 33 dtex polyurethane fiber by an ordinary dry spinning method.

Next, using a 84 dtex / 45f cupra (Asahi Kasei Fibers Bemberg) and the above 33 dtex polyurethane fiber, a bear tengu-maru knitted fabric was produced at 36 gauge by a conventional method. The mixing ratio of the polyurethane fiber at this time was 13 wt%.
Subsequently, after pre-wetting at 60 ° C. in an expanded form, it was pre-set at 185 ° C. and dyed under the same conditions as in Example 1.
After dyeing, hot water washing and water washing were repeated at 90 ° C., and after dehydration, polycarboxylic acid processing was performed in the same manner as in Example 1 to finish.
The basis weight of the finished dyed fabric was 215 g / m ² , a coarse density of 112 lines / inch, and a well density of 61 lines / inch.
The evaluation results of the deodorized performance, texture and sweat alkali fastness of the finished dyed fabric are shown in Table 2 below, and the deodorized performance and texture evaluation results after 50 washings are shown in Table 3 below.
In addition, in the dyed fabric after 50 washings, 19% of carboxyl groups were attached per unit of glucose in the cupra.
From the results in Table 2 and Table 3, the fabric obtained in Example 2 is a dyed fabric having excellent deodorizing performance, a supple texture, high color clarity, and high commercial value. I understand that.

[Example 3]
After the bear tengumaru knitted fabric obtained in Example 2 was preset, the enzyme treatment conditions shown in Example 1 were used before dyeing, and the treatment time was set using a liquid dyeing machine so that the weight loss rate was 5.8%. The weight loss was adjusted.
After the treatment, a deactivation treatment was carried out at 80 ° C. for 15 minutes, followed by washing with water, followed by dyeing and polycarboxylic acid processing under the same conditions as in Example 1, and finishing.
When the obtained dyed fabric was observed with an electron microscope at a magnification of 1800 times, the surface of the cellulose fiber had 16 streak-like grooves having a width of 0.4 μm and a length of 9.0 μm per 50 μm of fiber length. It was.
The evaluation results of the deodorizing performance, texture, sharpness and sweat alkali fastness of the obtained dyed fabric are shown in the following Table 2, and the deodorizing performance after 50 washings and the evaluation results of the feeling are shown in Table 3 below. Shown in
From the results in Table 2 and Table 3, the fabric obtained in Example 3 is a dyed fabric having excellent deodorizing performance, a supple texture, high color clarity, and high commercial value. I understand that.

[Comparative Example 3]
As Comparative Example 3, after pre-setting the Bear Tendon Maru knitted fabric obtained in Example 2, dyeing was performed in the same manner as in Example 2, and heat setting was performed so that the same property amount was obtained.
The evaluation results of the deodorizing performance, texture and sweat alkali fastness of the dyed fabric obtained are shown in Table 2 below, and the deodorizing performance after 50 washings and the evaluation results of texture are shown in Table 3 below. .
From the results shown in Tables 2 and 3, the dyed fabrics obtained in Examples 2 and 3 of the present invention are dyed fabrics having excellent deodorizing performance and high commercial value compared to the fabric obtained in Comparative Example 3. I understand that.

[Example 4]
44 dtex / 44f nylon 6 fiber was false twisted by a conventional method, and 84 dtex / 45f cupra was inserted in the processing step, interlaced and mixed to obtain a composite yarn.
Using this composite yarn and the 33 dtex polyurethane fiber of Example 3, a bare tengumaru knitted fabric was produced by a conventional method at 28 gauge. The mixing ratio of cellulose fibers in the knitted fabric was 54%, the mixing ratio of nylon 6 fibers was 34%, and the mixing ratio of polyurethane fibers was 12 wt%.
Then, after pre-wetting at 60 ° C. in an expanded form, it was pre-set at 185 ° C. and dyed under the following conditions.

<Dyeing conditions>
Reactive dye: Kayatheron React Yellow CN-EX: 0.019% omf
Kayatheron React Red CN-603: 0.019% omf
Acid dye: Aminyl yellow FD-5GL: 0.018% omf
Aminil Red FD-3BL: 0.037% omf
Auxiliary agent: kayak buffer P-7: 1 g / L
Imacall C2GL: 4g / L
Salt glass: 10 g / liter Bath ratio: 1:25
Dyeing temperature: 100 ° C
Dyeing time: 40 minutes After dyeing, hot water washing and water washing were repeated at 80 ° C., and after dehydration, polycarboxylic acid processing was performed in the same manner as in Example 1 to finish. The weight of the finished dyed fabric was 160 g / m ² , the coarse density was 59 / inch, and the well density was 45 / inch.
The evaluation results of the deodorized performance, texture and sweat alkali fastness of the finished dyed fabric are shown in Table 2 below, and the deodorized performance and texture evaluation results after 50 washings are shown in Table 3 below.
From the results in Table 2 and Table 3, the fabric obtained in Example 4 is a dyed fabric having excellent deodorizing performance, having a supple texture, high color clarity, and high commercial value. I understand that.

[Example 5]
After the bear tengumaru knitted fabric obtained in Example 4 was pre-set and before dyeing, the enzyme treatment conditions shown in Example 1 were used, and the treatment time was set using a liquid dyeing machine so that the weight loss rate was 3.5%. The weight loss was adjusted.
After the treatment, after performing a deactivation treatment at 80 ° C. for 15 minutes, washing with water and dyeing under the same conditions as in Example 4, performing the same polycarboxylic acid processing as in Example 1 after dyeing, Finished.
When the obtained dyed fabric was observed with an electron microscope at a magnification of 1800 times, there were 13 streak grooves having a width of 0.2 μm and a length of 8.3 μm per 50 μm of fiber length on the surface of the cellulose fiber. It was.
The evaluation results of the deodorizing performance, texture, sharpness and sweat alkali fastness of the obtained dyed fabric are shown in the following Table 2, and the deodorizing performance after 50 washings and the evaluation results of the feeling are shown in Table 3 below. Shown in
From the results in Table 2 and Table 3, the fabric obtained in Example 5 is a dyed fabric having excellent deodorizing performance, a supple texture, high color clarity, and high commercial value. I understand that.

[Comparative Example 4]
As a comparative example 4, after the bear tengumaru knitted fabric obtained in the example 4 was pre-set, it was dyed by the same method as in the example 4 and finished by heat setting so as to obtain the same property amount.
The evaluation results of the deodorizing performance, texture and sweat alkali fastness of the dyed fabric obtained are shown in Table 2 below, and the deodorizing performance after 50 washings and the evaluation results of texture are shown in Table 3 below. .
From the results shown in Tables 2 and 3, the dyed fabrics obtained in Examples 4 and 5 of the present invention are dyed fabrics having excellent deodorizing performance and high commercial value as compared with the fabric obtained in Comparative Example 4. I understand that.

  The deodorant fabric of the present invention can be suitably used particularly in the inner field and sports clothing field.

Claims (3)

  A deodorant fabric made by mixing unmodified cellulose fibers and polyurethane fibers to which a carboxyl group has been imparted, and after 50 washings, the rate of reduction of isovaleric acid in the deodorant processed fiber product certification standard is 85% or more And a deodorant fabric characterized by having 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, which has been treated with a polycarboxylic acid.