JPH09228144A - Polyurethane elastic fiber - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To obtain a polyurethane elastic fiber having both antibacterial and deodorant properties without deteriorating the original elastic physical properties of the fiber itself. SOLUTION: An amorphous silicate powder having an average particle size of 5 microns or less selected from an antibacterial agent-cyclodextrin clathrate and a divalent metal salt of zinc, copper or nickel in a polyurethane polymer solution. In parts by weight of 1: 1.5 to 1: 1
The mixture was mixed so as to be in the range of 0, and the mixed portion was mixed so as to be 5 to 10% by weight with respect to the polyurethane polymer, and the polyurethane polymer solution was spun to obtain a polyurethane elastic fiber.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The polyurethane elastic fiber of the present invention comprises a core spun yarn produced by using polyurethane elastic fiber and other fibers, coated elastic yarn such as filament twist yarn, polyurethane elastic fiber and other fibers. The present invention can be used in the field of textile products such as used cloths and non-woven fabrics, and the present invention provides polyurethane elastic fibers having antibacterial and deodorant properties in addition to the original elastic properties.

[0002]

2. Description of the Related Art In order to impart antibacterial and / or deodorant properties to a fiber or a textile product, there have been proposed many means for incorporating or processing a substance having these properties. For example, as an example in which a substance having these properties is mixed in a fiber, JP-A-54-14720 discloses that copper or a copper compound is mixed in an acrylonitrile-based fiber, and JP-A-2-99606 describes. It is disclosed that fine particles of zinc silicate composed of zinc oxide and silicon dioxide are mixed into polyester fibers, and that JP-A-3-59108 discloses that inorganic and / or organic germanium compounds are mixed into synthetic fibers. .

Conventionally, there has been no attempt to impart antibacterial and deodorant properties to polyurethane elastic fibers, but the present applicant has disclosed a polyurethane elastic yarn having antibacterial and deodorant properties in JP-A-5-33217. It is composed of porous silica microcapsules containing an antibacterial agent having an average particle size of 5 microns or less in a polyurethane polymer solution and an amorphous silicic acid powder selected from a divalent metal salt of zinc, copper or nickel. Mix so that the part ratio is in the range of 1: 5 to 1:10,
5 to 10% by weight of the mixture based on the polyurethane polymer
It is a polyurethane elastic fiber obtained by mixing and spinning the solution.

[0004]

DISCLOSURE OF THE INVENTION The invention disclosed above is
In order to impart antibacterial and deodorant performance to polyurethane elastic fiber, porous microcapsules in which spherical porous silica is immersed in an antibacterial agent solution and dried are included. When preparing a mixed solution containing a porous silica microcapsule encapsulating an antibacterial agent and an amorphous silicate powder, the handling of the microcapsule is often limited due to the properties of the microcapsule. DISCLOSURE OF THE INVENTION The inventors of the present invention have made a new study on an antibacterial agent that is easy to handle for the purpose of obtaining a polyurethane elastic fiber having both antibacterial and deodorant properties without deteriorating the original elastic physical properties of the fiber itself. The present invention has been accomplished by finding a combination of deodorants.

[0005]

The present invention provides an antibacterial agent-cyclodextrin inclusion compound in a polyurethane polymer liquid,
Amorphous silicate powder having an average particle size of 5 microns or less selected from a divalent metal salt of zinc, copper or nickel should be in the range of 1: 1.5 to 1:10 by weight. Mix and
5 to 10% by weight of the mixture based on the polyurethane polymer
And a polyurethane elastic fiber obtained by spinning the polyurethane polymer solution.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyurethane polymer solution used in the present invention comprises a polyether-based, polyester-based or polyether-ester-based linear polyhydroxy compound having hydroxyl groups at both ends and an excess of an organic diisocyanate compound. To give a prepolymer, which is reacted with a chain extender having substantially two active hydrogen groups in a polar solvent of dimethylformamide or dimethylacetamide, and then the polymerization reaction is terminated with a chain terminator. It is a substantially linear polyurethane polymer solution obtained by so-called soft segment and hard segment, and its raw material and manufacturing method are not particularly limited. or,
As a spinning method for forming the polyurethane elastic fiber of the present invention using the polyurethane polymer solution, a known method such as a dry method or a wet spinning method is adopted. The fineness of the obtained polyurethane elastic fiber is not particularly limited.
Further, a matting agent, such as titanium oxide, which is usually used, an ultraviolet protective agent, an antioxidant, etc., may be added to the polyurethane polymer solution.

The antibacterial agent-cyclodextrin clathrate used in the present invention means that cyclodextrin, which is a cyclic oligosaccharide composed of glucose as a constituent substance obtained by the action of an enzyme on starch, is present in the hydrophobic cavity. , A clathrate containing an antibacterial substance, cyclodextrin consisting of 6 cyclic glucose units is α-cyclodextrin, 7 is β-cyclodextrin, and 8 is γ.
-Known as cyclodextrin. To wrap the fat-soluble antibacterial substance in cyclodextrin, any fat-soluble substance having antibacterial properties may be used, but in the present invention, the fat-soluble substance of hinoki oil is preferable as the antibacterial agent, and hinoki oil is effective for cyclodextrin. Β-Cyclodextrin is suitable for inclusion in the above. The size of the β-cyclodextrin powder is not particularly limited in its particle size because it dissolves well with hinoki oil in the polar solvent used for the polyurethane polymer solution.

The average particle size of the amorphous silicate powder selected from the divalent metal salts of zinc, copper or nickel used in the present invention is preferably 5 microns or less, particularly in the process of fiber formation. As the amorphous silicate powder of the metal salt, for example, a powder obtained by the method disclosed in JP-A-2-265644 can be dried and used. Antibacterial agent
When preparing a mixed solution of the cyclodextrin clathrate and the above-mentioned amorphous silicate powder, the antibacterial agent-cyclodextrin clathrate is dissolved in the polar solvent used for the polyurethane polymer solution to form an amorphous form. Since the silicate powder is dispersed in the solvent, it is easy to adjust with a polar solvent, and it is easy to add and inject the adjusting solution into the polyurethane polymer solution.

As is clear from the description of the embodiments described below,
The antibacterial agent-cyclodextrin clathrate alone or the amorphous silicate powder alone has low antibacterial and deodorant effects, and the effects of the present invention can be obtained only by mixing both.
Mixing and adjusting the antibacterial agent-cyclodextrin inclusion compound and the amorphous silicate powder with respect to the polyurethane polymer (solid content) in a range of 1: 1.5 to 1:10 by weight. Is preferred. When it is less than 1: 1.5, the deodorizing effect is inferior, and when it is larger than 1:10, the antibacterial effect is obtained, but the spinning tone is adversely affected. Further, the total mixing ratio of the antibacterial agent-cyclodextrin clathrate and the amorphous silicate powder to the polyurethane polymer (solid content) is preferably in the range of 5 to 10% by weight. If it is out of this range, the balance of both antibacterial and deodorant properties is lost, which is not preferable.

To mix the antibacterial agent-cyclodextrin clathrate and the amorphous silicate powder with the polyurethane polymer solution and spin it, use the same solvent as previously used for the polyurethane polymer solution as described above. Addition of a control solution to obtain a polyurethane polymer solution immediately before spinning, in addition to a method of injecting and mixing a predetermined amount of the control solution into a polyurethane polymer solution and spinning the mixture, an antibacterial agent-cyclodextrin clathrate in advance in a part of the polyurethane polymer solution And amorphous silicate powder are prepared and mixed, and a spinning method is carried out while pouring a fixed amount of the prepared solution into the polyurethane polymer solution immediately before spinning, or an antibacterial agent in the spinning polyurethane polymer solution. Any method such as a method in which the cyclodextrin inclusion compound and the amorphous silicate powder are added and the solution is directly spun can be adopted.

[0011]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to this range. All parts in the examples are parts by weight.

The fineness, strength, and elongation of the polyurethane elastic fiber were measured by "Polyurethane filament yarn test method" issued by the Japan Chemical Fiber Association Technical Committee, Spandex Technical Subcommittee, October 1978.

The 300% modulus was determined by measuring the tensile strength (g / d) at the time of 300% elongation. To measure the deodorant performance, select any weight from 1g, 3g, and 6g of the sample, and add ammonia 4 in a 5 liter Tedlar bag.
3 liters of odorous gas adjusted to an initial concentration of 0 ppm and hydrogen sulfide of 15 ppm was filled, the gas concentration was measured after 2 hours and 6 hours, and the deodorization rate was measured by the following formula. Deodorization rate (%) = {(initial gas concentration-residual gas concentration) /
(Initial gas concentration)} × 100

The antibacterial performance was measured by the bacterial count method and the shake flask method in the processing effect evaluation manual for antibacterial and deodorant processed products of the Textile Products Hygiene Processing Council. The method is as follows.

[0015] Staphylococcus aureus IFO 1273
2) was used as a test cell, and this was preliminarily added to a normal broth medium for 5
The culture is adjusted to be about 30 × 10 ⁵ cells / ml and used as a test bacterial suspension. 0.2 ml of the suspension was uniformly inoculated to 0.2 g of the sample in a sterilized screw vial,
After stationary culture at 18 ° C. for 18 hours, 20 ml of sterile buffered physiological saline is added to the container, and the mixture is vigorously shaken by hand 25 to 30 times with an amplitude of about 30 cm to disperse the viable bacteria under test in the solution. Make a dilution series from this dispersed bacterial solution with sterilized buffered saline, put 1 ml of the diluted solution at each step into a sterile petri dish, and prepare about 15 ml standard agar medium pour plate (2 plates for the same dilution) To do. After culturing this at 35 to 37 ° C. for 24 to 48 hours, the number of grown colonies was counted, and the number of viable bacteria in the sample was calculated by multiplying by the dilution factor. The dilution factor was based on the bacterial dispersion in the culture vessel and was calculated by the following formula. Number of viable bacteria = number of colonies x 20 x multiple of dilution And the determination of the effect is based on the average number of bacteria of untreated standard cloth and 3 samples

[Equation 1] Under the conditions described above, the difference between the increased and decreased values was calculated by the following formula, and 1.6 or more was determined to have an antibacterial effect.

[0016]

[Equation 2]

Shake Flask Method Klebsiella pneumoniae IFO 13277 was used as a test bacterial cell, which was previously used in a broth medium for 1.5 to 3 ×.
The culture was adjusted to 10 ⁸ cells / ml, a phosphate buffer (34 g of potassium phosphate-potassium was dissolved in 500 ml of purified water, and about 175 ml of a 4% (w / v) sodium hydroxide aqueous solution was added thereto, After adjusting to pH 7.2, the total amount is 1,000
It was diluted 1,000 times with a stock solution (ml) to give an inoculum solution.

In an Erlenmeyer flask with a 200 ml screw cap, 70 ml of phosphate buffer was placed and the cap was loosely closed, and then sterilized in an autoclave at 125 ° C. for 15 minutes under moist heat.
After cooling, 5 ml of the inoculum solution was added and well stirred, and the number of bacteria in the Erlenmeyer flask was 1-2 × 10 ⁴ cells / ml. In the same manner, collect 1 ml of bacteria from any three Erlenmeyer flasks, make a 10-fold dilution series with phosphate buffer, and prepare a pour agar plate using standard agar medium. Four
After culturing for 8 hours, the number of grown colonies was counted and multiplied by the dilution factor to calculate the initial number of bacteria (A).

0.75 g of the unprocessed standard cloth and the processed sample were weighed, and three samples were used as samples. Each sample was added to the Erlenmeyer flask prepared by adding the inoculum solution, and 6 specimens were simultaneously rotated with a wrist action shaker at a rotation speed of 320 to 340 rpm,
After culturing with shaking for 60 minutes, 1 ml of the bacterial solution was collected in the same manner, a 10-fold dilution series was prepared with a phosphate buffer, and a pour agar plate was prepared using a standard agar medium.
After culturing for a period of time, the number of grown colonies was counted and multiplied by the dilution factor to calculate the viable cell count (B) of each sample.

To determine the effect, the sterilization rate was calculated by the following formula based on the average number of bacteria of the untreated standard cloth and 3 samples, and the sterilization of the blank test (tested only with the phosphate buffer and the inoculum) was carried out. When the rate of sterilization was within ± 10% and the sterilization rate of the unprocessed sample was 30% or less, the difference in sterilization rate of 26% or more between the processed sample and the unprocessed sample was regarded as having the antibacterial effect. Sterilization rate (%) = {(AB) / A} × 100

Example 1 With respect to 2,644 parts of polytetramethylene ether glycol having an average molecular weight of 2,000, 4,4 ′ diphenylmethane diisocyanate 1,1 was used.
25 parts was added to the reaction vessel, after synthesizing a prepolymer by stirring for 60 minutes at an N ₂ atmosphere under 80-90 ° C., diluted with dimethylformamide 6,215 parts, to obtain a solvent dilution prepolymer. Separately prepared dimethylformamide 12,
A solution of 628 parts, 112 parts of ethylenediamine, and 14 parts of diethanolamine was added to this solvent-diluted prepolymer and reacted by stirring to obtain a viscous 25% polyurethane polymer solution.

Cypress dextrin (made by Shimizu Minato Seito Co., Ltd., trade name: DEXIPEARL β-10
(1) An average of 1 part of hinoki oil-β-cyclodextrin clathrate having an average particle size of 180 micron clathrated in 0) (manufactured by Shimizu Minato Sugar Co., Ltd., trade name: Taiwan hinoki powder, hereinafter abbreviated as additive A) 5 parts of amorphous silicate powder made of zinc oxide having a particle size of 2.2 microns (manufactured by Lhasa Kogyo Co., Ltd., trade name: Shuklenz KD-211, hereinafter abbreviated as additive B) was added to 19 parts of dimethylformamide. Add and stir. Additive A was dissolved and Additive B was dispersed. This solution was added to 100 parts of a polyurethane polymer with additives A and B
Was added to the polyurethane polymer solution immediately before spinning so that a total of 5 parts was mixed. The solution was wet spun through a spinneret having 20 holes having a diameter of 0.1 mm to obtain a 140 denier polyurethane elastic fiber (Sample 1) treated with a commercially available finishing oil.

For comparison, spinning was performed without adding the additive A and the additive B to obtain a 140 denier polyurethane elastic fiber (sample 7). Similarly to Sample 1, 1 part of Additive A and 6 parts of Additive B were added to 18 parts of dimethylformamide and stirred, and this solution was added at a ratio of 6 parts of Additives A and B to 100 parts of the polyurethane polymer. It was added immediately before spinning so as to be mixed, to obtain 140 denier polyurethane elastic fiber (Sample 2).

Further, 1 part of additive A and 7 parts of additive B were added to 17 parts of dimethylformamide and stirred, and this solution was mixed in a ratio of 7 parts of additives A and B to 100 parts of the polyurethane polymer. As just before spinning,
A 0 denier polyurethane elastic fiber (Sample 3) was obtained.

Further, 1 part of Additive A and 8 parts of Additive B were added to 16 parts of dimethylformamide and stirred, and this solution was mixed in a ratio of 8 parts of Additives A and B to 100 parts of the polyurethane polymer. As just before spinning,
A 0 denier polyurethane elastic fiber (Sample 4) was obtained.

Further, 1 part of the additive A and 9 parts of the additive B were added to 15 parts of dimethylformamide and stirred, and this solution was mixed in a ratio of 9 parts of the additives A and B to 100 parts of the polyurethane polymer. As just before spinning,
A 0 denier polyurethane elastic fiber (Sample 5) was obtained.

Further, 1 part of Additive A and 10 parts of Additive B were added to 14 parts of dimethylformamide and stirred, and this solution was mixed in a ratio of 10 parts of Additives A and B to 100 parts of the polyurethane polymer. Just before spinning,
A 140 denier polyurethane elastic fiber (Sample 6) was obtained.

The physical properties of Samples 1 to 7 are shown in Table 1. From these results, no difference was observed in the physical property values of Samples 1 to 6 as compared with Sample 7. For comparison, only 5 parts of Additive A was added to 20 parts of dimethylformamide and stirred, and this solution was added to 0.5 parts and 1 part of Additive A per 100 parts of polyurethane polymer immediately before spinning. After addition, each was wet-spun and 140 denier polyurethane elastic fiber (Sample 8
And sample 9) were obtained.

Also, 10 parts of additive B alone was mixed with 15 parts of dimethylformamide and stirred, and this solution was added immediately before spinning so that the content of additive B was 2 parts and 4 parts per 100 parts of the polyurethane polymer. Above, each wet spun, 140 denier polyurethane elastic fiber (Sample 10 and Sample 11)
I got Samples 8 to 11 are shown in Table 1. These physical property values were not different from those of Samples 1 to 7.

[0030]

[Table 1]

Regarding Samples 1 to 11 JIS L0217
-1995 "Indication terms and indication methods for handling textiles" 2.2 (1) Washing based on washing method No. 103, and the result of testing the antibacterial performance after 0 washings (initial processing) and 10 washings Is shown in Table 2.

[0032]

[Table 2]

Further, 6 g of each of Samples 1 to 11 was subjected to a deodorizing performance test against ammonia and hydrogen sulfide, and the results are shown in Table 3.

[0034]

[Table 3]

From the results shown in Tables 2 and 3, those obtained by mixing and adding both the additive A and the additive B are the additives A and B.
It is clear that the antibacterial / deodorant performance is remarkably improved as compared with the sample 7 in which the saturating agent was not mixed. However, the polyurethane elastic fiber obtained by mixing the additive A alone into the polyurethane polymer solution and spinning the mixture has an antibacterial performance when the additive A is mixed in an amount of 1.0 part with respect to 100 parts of the polyurethane polymer. However, since the deodorizing performance against ammonia and hydrogen sulfide is low, the purpose of imparting the desired antibacterial and deodorizing effects cannot be achieved only by mixing the additive A alone, and only the additive B is provided. It was clear that the polyurethane elastic fiber obtained by mixing and spinning alone in the polyurethane polymer solution does not have antibacterial performance, has low deodorizing performance, and cannot achieve the desired purpose.

Example 2 With respect to 5,000 parts of polytetramethylene ether glycol having an average molecular weight of 2,000, 4.4'-diphenylmethane diisocyanate 1,1 was used.
Twenty-five parts were added to the reaction vessel, and the mixture was stirred and reacted at 80 to 90 ° C. for 60 minutes under N ₂ atmosphere to synthesize a prepolymer, which was then diluted with 6,125 parts of dimethylacetamide to obtain a solvent-diluted prepolymer. Separately prepared dimethylacetamide 12,
A mixed solution of 628 parts, 112 parts of ethylenediamine, and 14 parts of diethanolamine was added to this solvent-diluted prepolymer and reacted with stirring to obtain a viscous 30% polyurethane polymer solution.

0.5 parts of additive A and 4.5 parts of additive B used in Example 1 were mixed with 15 parts of dimethylacetamide and stirred, and the solution was added to 100 parts of the polyurethane polymer.
Additives were added immediately before spinning so that the total amount of additives A and B was mixed in a ratio of 5.0 parts, and the solution was dry-spun through a spinneret with a hole number of 1 having a diameter of 0.25 mm to give a known finishing agent treatment. And then 15
A denier polyurethane elastic fiber (Sample 12) was obtained.

Further, 1 part of the additive A and 4.5 parts of the additive B were mixed with 14.5 parts of dimethylacetamide and stirred, and the solution was added to 100 parts of the polyurethane polymer, and the additives A and B were added.
Was added immediately before spinning so that the total of 5.5 parts was mixed in a ratio of 5.5 parts, and polyurethane elastic fiber of 15 denier (Sample 1
3) was obtained.

Further, 2 parts of additive A and 4.5 parts of additive B were mixed with 13.5 parts of dimethylacetamide and stirred, and the solution was added to 100 parts of the polyurethane polymer, and the additives A and B were added.
Was added immediately before spinning so that the total of 6.5 parts was mixed in a ratio of 6.5 parts, and polyurethane elastic fiber of 15 denier (Sample 1
4) was obtained.

Further, 3 parts of the additive A and 4.5 parts of the additive B were mixed with 50 parts of dimethylacetamide and stirred, and the solution was added to 100 parts of the polyurethane polymer so that the total amount of the additives A and B was 7.5. Polyurethane elastic fiber of 15 denier (Sample 15) added immediately before spinning so that it is mixed in a ratio of 1 part.
I got

For comparison, a polyurethane polymer liquid having a concentration of 30% was similarly dry-spun without adding the additive A and the additive B to obtain a polyurethane elastic fiber of 15 denier (sample 16). Table 4 shows the physical property values of the obtained samples 12 to 16.
The antibacterial performance and the deodorizing performance of each sample were measured in the same manner as in Example 1, and the results are shown in Tables 5 and 6.

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

[Table 6]

The results shown in Table 4 show that Samples 12 to 15 are different from Sample 16 in that the polyurethane elastic fibers to which the additive A and the additive B are added have no abnormalities as compared with the physical properties of the polyurethane elastic fibers without any additives. unacceptable. From the results shown in Tables 5 and 6, it is clear that the antibacterial and deodorant performances of the samples to which both the additive A and the additive B are added are remarkably improved as compared with the sample 16.

[Application Example] Samples 12 and 1 obtained in Example 2
Polyurethane elastic fibers 5 and 16 are used as cores, and nylon S twist 10 denier (5
A single covered yarn (hereinafter abbreviated as SCY) coated with a filament was manufactured, and samples 17, 18 and 19 were manufactured.
I got Similarly, samples 12, 15, and 16 were used to produce SCY coated with nylon Z twist 10 denier (5 filaments) which was not subjected to antibacterial and deodorant treatment with each as a core, and samples 20, 21, and 22 were obtained. It was

An S twist SCY sample 17 and a Z twist sample 20 were alternately fed to a panty hose knitting machine having 400 needles to obtain a panty hose sample 23 at a rotation speed of 500 rpm. Similarly, samples 18 and 21 and samples 19 and 22 were used to obtain pantyhose samples 24 and 25.

Samples 23, 24, and 25 were treated with a preset machine at 80 ° C. for 10 minutes, sewn, and further, with a drum type dyeing machine, an acid dye (manufactured by Nippon Kayaku Co., Ltd., Kayanol Na
vy Blue R, Kayanol Red NB) using a bath ratio of 1: 2
0, acid dye 4.2% (owf), ammonium sulfate 3% (owf)
After dyeing at 90 ° C. for 30 minutes in the above bath, pantyhose samples 26, 27 and 28 were obtained by setting the final setting machine at 110 ° C. for 10 seconds. These pantyhose were made of nylon 62.2% and polyurethane elastic fiber 37.8%.

The samples 26, 27, and 28 were JIS-compliant, respectively.
L0217-1995 "Indication term and indication method for handling textiles" 2.2 (1) Washing method number 103
Washing based on 0, 10 times after washing, 20 times after washing, 3
The antibacterial performance test was performed 0 times, 40 times and 50 times, and the results are shown in Table 7. . In addition, samples 26, 27,
The deodorizing property test was performed on 28 g of 1 g and 3 g of ammonia and hydrogen sulfide, respectively, and the results are shown in Table 8.

[0050]

[Table 7]

[0051]

[Table 8]

From these results, it is clear that the panty hose product using the polyurethane elastic fiber of the present invention has an excellent effect as compared with the product in which the antibacterial and deodorant is not added.

[0053]

As is apparent from the above-described examples, according to the present invention, the antibacterial agent-cyclodextrin inclusion compound and the divalent metal salt of zinc, copper or nickel are selected in the polyurethane polymer solution. Polyurethane elastic fibers obtained by mixing and spinning amorphous silicate powder having an average particle size of 5 microns or less are antibacterial agent-cyclodextrin inclusions and amorphous silicate powder in parts by weight ratio. 1: 1.5-1: 1.
0, mixed material is 5 to 1 in total for polyurethane polymer
Since the polyurethane elastic fiber is mixed in the polyurethane elastic fiber in an amount of 0% by weight, the fiber itself has sufficient antibacterial and deodorant properties without impairing the physical properties of the fiber itself. The same effect is exerted on textile products.

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[Procedure amendment]

[Submission date] April 8, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004]

DISCLOSURE OF THE INVENTION The invention disclosed above is
In order to impart antibacterial and deodorant performance to polyurethane elastic fiber, porous microcapsules in which spherical porous silica is immersed in an antibacterial agent solution and dried are included. When preparing a mixed solution containing a porous silica microcapsule encapsulating an antibacterial agent and an amorphous silicate powder, the handling of the microcapsule is often limited due to the properties of the microcapsule. The present inventors have, without impairing the inherent elastic properties of the fiber itself has <br/>, antibacterial, for the purpose of obtaining polyurethane elastic fibers having both a deodorizing performance, easy new handling extensive study The present invention has been accomplished by finding a combination of various antibacterial agents and deodorants.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

[0016]

[Equation 2]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

In a Erlenmeyer flask with a 200 ml screw cap, 70 ml of phosphate buffer was placed and the cap was loosely closed, then sterilized in an autoclave at 125 ° C for 15 minutes under heat and humidity, and after cooling, 5 ml of inoculum was added and well stirred. The number of bacteria in the Erlenmeyer flask is 1-2 × 10 ⁴ cells / ml. Bacterial solution than any three of the prepared Erlenmeyer flask in the same manner as 1
Collect ml, make a 10-fold dilution series with phosphate buffer and prepare a pour agar plate using standard agar medium at 35-37 ° C.
In After culturing 24-48 hours, and counting grown colonies was calculated initial number of bacteria (A) is multiplied by the dilution multiple of it.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

To determine the effect, the sterilization rate was calculated by the following formula based on the average number of bacteria of the untreated standard cloth and 3 samples, and the sterilization of the blank test (tested only with the phosphate buffer and the inoculum) was carried out. rate is within 10% ±, unprocessed conditions sterilization of not more than 30% of the samples, processing the samples and the sterilization rate difference more than 26% of non-processed sample was there antimicrobial effect. Sterilization rate (%) = {(AB) / A} × 100

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

[Example 1] 4,4'-diphenylmethane diisocyanate 1,1 was added to 5,000 parts of polytetramethylene ether glycol having an average molecular weight of 2,000.
Add 25 parts into a reaction vessel , and 80-90 ° C under N ₂ atmosphere.
In 60 minutes to stir the reaction after synthesizing the prepolymer was diluted with dimethylformamide 6,215 parts, to obtain a solvent dilution prepolymer. Dimethylformamide 12,628 parts separately prepared, 112 parts of ethylenediamine, diethanolamine 14 parts solution, the added solvent diluted prepolymer injected stirred reaction to a viscous 25% strength polyurethane <br/> down polymer solution Obtained.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

Cypress dextrin (made by Shimizu Minato Seito Co., Ltd., trade name: DEXIPEARL β-10
0) Inclusion of cypress oil-β-cyclodextrin inclusion particles with an average particle size of 180 microns (manufactured by Shimizu Minato Sugar Co., Ltd., trade name: Taiwan cypress powder, hereinafter abbreviated as additive A) and 1 part on average 5 parts of amorphous silicate powder made of zinc oxide having a particle size of 2.2 microns (manufactured by Lhasa Kogyo Co., Ltd., trade name: Shuklenz KD-211, hereinafter abbreviated as additive B) was added to 19 parts of dimethylformamide. Add and stir. Additive A was dissolved and Additive B was dispersed. This solution was added to 100 parts of a polyurethane polymer with additives A and B
Was added to the polyurethane polymer solution immediately before spinning so that a total of 5 parts was mixed. The solution is 0.1 mm in diameter
Wet spinning from a spinneret with 20 holes having
To obtain a 140 denier polyurethane elastic fibers treated with finish oil publicly known (Sample 1).

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

Regarding Samples 1 to 11 JIS L0217
-1995 "Indication symbols and indication methods for handling textile products" 2. 1. (1) Table 2 shows the results of an antibacterial performance test after washing was carried out based on washing method No. 103 and after 0 times of washing (the initial stage of processing) and 10 times of washing.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

Example 2 With respect to 5,000 parts of polytetramethylene ether glycol having an average molecular weight of 2,000, 4.4'-diphenylmethane diisocyanate 1,1 was used.
25 parts was added to the reaction vessel, after synthesizing a prepolymer by 60 minutes stirring the reaction under N ₂ atmosphere at 80-90 ° C., diluted with 6,125 parts of dimethyl acetamide to obtain a solvent dilution prepolymer. Separately prepared dimethylacetamide 1
A mixed solution of 2,628 parts, 112 parts of ethylenediamine, and 14 parts of diethanolamine was added to this solvent-diluted prepolymer and reacted with stirring to obtain a viscous polyurethane polymer solution having a concentration of 30%.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

Further, 3 parts of the additive A and 4.5 parts of the additive B were mixed with 12.5 parts of dimethylacetamide and stirred, and the solution was added to 100 parts of the polyurethane polymer, and the additives A and B were added.
Was added just before spinning so that the total of 7.5 parts was mixed in a ratio of 7.5 parts, and polyurethane elastic fiber of 15 denier (Sample 1
5) was obtained.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

[0048] After 10 minutes at 80 ℃ the samples 23, 24, 25 at each preset machine processing, sewing, and even in a drum-type dyeing machine, an acid dye (Nippon Kayaku Co., Ltd., Kayan
olNavy Blue R, Kayanol Red
NB), bath ratio 1:20, acid dye 4.2%
(O.w.f.), Ammonium sulfate 3% (o.w.f.) Dyeing treatment at 90 ° C for 30 minutes, then 1 on the final set machine.
Pantyhose sample 2 set at 10 ℃ for 10 seconds
6,27,28 were obtained. These pantyhose are made of nylon 62.2%, polyurethane elastic fiber 37.8
%Met.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction contents]

The samples 26, 27, and 28 were JIS-compliant, respectively.
L0217-1995 "Indication symbols and indication methods for handling textiles" 2. 1. (1) Washing number 10
Washing was carried out based on No. 3, and the antibacterial performance test was performed after 0 times of washing (initial stage of processing), 10 times, 20 times, 30 times, 40 times and 50 times, and the results are shown in Table 7. . . Further, deodorizing test was conducted on 1 g and 3 g of ammonia and hydrogen sulfide of Samples 26, 27 and 28, respectively, and the results are shown in Table 8.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction item name] 0053

[Correction method] Change

[Correction contents]

[0053]

As is apparent from the above-described examples, according to the present invention, the antibacterial agent-cyclodextrin inclusion compound and the divalent metal salt of zinc, copper or nickel are selected in the polyurethane polymer solution. Polyurethane elastic fibers obtained by mixing and spinning amorphous silicate powder having an average particle size of 5 microns or less are antibacterial agent-cyclodextrin inclusions and amorphous silicate powder in parts by weight ratio. in 1: 1.5 to 1: 10,
Since the mixed material is mixed in the polyurethane elastic fiber in a total amount of 5 to 10% by weight based on the polyurethane polymer, the fiber itself has sufficient antibacterial and deodorant performance without deteriorating the physical properties of the fiber itself. The same effect can be exerted on the textile product provided with the polyurethane elastic fiber of the present invention.

Claims (1)

[Claims] 1. An amorphous silicate powder having an average particle size of 5 μm or less selected from an antibacterial agent-cyclodextrin inclusion compound and a divalent metal salt of zinc, copper or nickel in a polyurethane polymer solution. Body weight ratio of 1: 1.5 to 1: 1
Polyurethane elastic fiber obtained by mixing so as to be in the range of 0, mixing so as to be 5 to 10% by weight with respect to the polyurethane polymer, and spinning the polyurethane polymer solution.