JPH0533217A - Modified polyurethane elastic yarn - Google Patents

Abstract

PURPOSE:To obtain a modified polyurethane elastic yarn having antimicrobial properties and deodorizing performances without damaging fiber physical properties, maintaining these performances even by dyeing. CONSTITUTION:A solution of polyurethane polymer is blended with porous silica microcapsules including an antimicrobial agent and amorphous silicate powder selected from a bivalent heavy metal of zinc, copper or nickel and the solution is spun.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polyurethane elastic fiber having antibacterial / deodorant properties, such as a core spun yarn or filament twist yarn, a yarn, a knitted woven fabric, or a non-woven fabric using a normal polyurethane elastic fiber. It is intended to provide a modified polyurethane elastic fiber having antibacterial / deodorant properties, in addition to the original elastic properties, which can be used in the fields such as.

[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 a number of means for mixing or processing substances having these properties. For example, as an example of mixing a substance having these properties into a fiber, in JP-A-54-147220, it is possible to mix copper or a copper compound into an acrylonitrile fiber,
In JP-A 2-99606, fine particles of zinc silicate composed of zinc oxide and silicon dioxide are mixed in a polyester fiber, and in JP-A 3-59108, an inorganic and / or organic germanium compound is contained in a synthetic fiber. Is disclosed. However, no attempts have been made to impart antibacterial / deodorant properties to polyurethane elastic fibers.

[0003]

The fibers according to the prior art described above are synthetic fibers such as polyester, polyamide, polyacrylonitrile, etc., and these fibers themselves are products as yarns or knitted fabrics, and in the case of clothing. Was developed in response to the demands of direct contact with the body and from the viewpoint of health. However, the polyurethane elastic fiber is used by itself in combination with other natural and synthetic fibers without being made into a knitted fabric by itself. That is, in the core spun yarn yarn, polyurethane elastic fiber is used as the core and is covered with a cotton sliver, and in the filament twist yarn yarn, cotton yarn, polyamide filament, etc. are covered with the polyurethane fiber as the core. In the case of forming a woven fabric, these core spun yarn yarns and twist spun yarn yarns are woven alone or together with other fibers, and in knitting, knitted with other synthetic fibers, etc. It is usually very low. Therefore, only imparting antibacterial / deodorant properties to the fibers used for coating or knitting and weaving has not hitherto been considered to impart the antibacterial / deodorant effect to the polyurethane elastic fiber itself.

However, the inventors of the present invention can further increase the effect by providing the polyurethane elastic fiber itself with antibacterial and deodorant properties even under the above-mentioned usage conditions, and the coating can be further improved. It is possible to impart a sustained release effect to the product by imparting antibacterial / deodorant performance to the polyurethane elastic fiber even when the fiber used in knitting or weaving does not have antibacterial / deodorant performance. As a result of research, the present invention has been reached.

The present inventors obtain a polyurethane elastic fiber which has antibacterial and deodorant properties without impairing the original performance of the fiber itself, and exhibits the effect even when dyed and is excellent in safety. As a result of extensive studies aimed at that, as a result, porous silica microcapsules containing an antibacterial agent and an amorphous silicate powder selected from divalent heavy metals of zinc, copper or nickel were added to a polyurethane polymer solution. The present invention has been completed by mixing an appropriate amount and spinning.

[0006]

The present invention has an average particle size of 5
Porous silica microcapsules containing a micron or less antibacterial agent and amorphous silicate powder selected from divalent heavy metals of zinc, copper or nickel are mixed with a polyurethane polymer solution, and the polymer solution is mixed. It relates to a modified polyurethane elastic fiber obtained by spinning.

The polyurethane polymer solution used in the present invention is a polyether-based, polyester-based or polyether-ester-based linear polyhydroxy compound having a hydroxyl group at the terminal, an excess diisocyanate compound, and substantially 2 A substantially linear polyurethane polymer solution comprising a so-called soft segment and a hard segment, which is obtained by reacting a chain extender having a number of active hydrogen groups in a polar solvent, and is particularly a raw material or a production method. Etc. are not limited. The method for molding the modified polyurethane elastic fiber of the present invention using the polyurethane polymer solution may be a known method such as a dry or wet spinning method. And the fineness is not particularly limited. Further, in the polyurethane polymer solution, a matting agent such as titanium oxide, which is usually used, an ultraviolet protective agent, an antioxidant, etc. can be added.

The porous silica microcapsules containing the antibacterial agent used in the present invention are obtained by means such as immersing the spherical porous silica in a solution of the antibacterial agent and drying it. The antibacterial agent contains silicon. Examples thereof include quaternary ammonium salt, benzalkonium chloride, polyhexamethylene biguanide hydrochloride, parachlormethaxylenol and the like. The porous silica microcapsules including the antibacterial agent preferably have a size of 5 μm or less in order to prevent nozzle clogging and yarn breakage during spinning.

The amorphous silicate powder selected from divalent heavy metals such as zinc, copper or nickel used in the present invention has an average particle size similar to the above-mentioned porous silica microcapsules.
5 microns or less is preferable. As the heavy metal amorphous silicate powder, for example, a powder obtained by the method disclosed in JP-A-2-265644 can be dried and used.

As is clear from the description of the examples below,
Porous silica microcapsules clathrate the above antibacterial agent alone, or the amorphous silicate powder alone is less effective,
The effect of the present invention can be obtained only when both are mixed. The mixing ratio of the porous silica microcapsules and the amorphous silicate powder is such that the porous silica microcapsules and the amorphous silicate powder are in a weight ratio of 1: 5 to 1:10. Preferably. The total mixing ratio of the porous silica microcapsules to the polyurethane polymer and the amorphous silicate powder is selected within the range of 5 to 10% by weight.

In order to mix the porous silica microcapsules and the amorphous silicate powder in the polyurethane polymer solution and to perform spinning, these additives are directly added to the polyurethane polymer solution for spinning, or the polyurethane polymer solution is preliminarily used. The additive is dispersed in the same solvent as the coalescing solution, and the polyurethane polymer solution is injected into the polyurethane polymer solution at a constant rate immediately before spinning and mixed, or the additive is dispersed in a part of the polyurethane polymer solution in advance. Then, any method may be used, such as spinning the dispersion liquid while pouring it into the polyurethane polymer solution in a fixed amount immediately before spinning. As described above, the modified polyurethane elastic fiber of the present invention can be used for various uses of the conventionally known polyurethane elastic fiber.

[0012]

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

The fineness, strength and elongation were measured by "Polyurethane filament yarn test method" issued by Japan Chemical Fiber Association Technical Committee, Spandex Technical Subcommittee, October 1978. For the 300% modulus, the tensile strength (g / d) at 300% elongation was measured. The deodorant performance was measured by predrying the sample at 70 ° C for 1 hour and then exposing it to a standard atmosphere, and 10 g of the sample was enclosed in a 3 liter Tedlar bag containing 100 ppm of trimethylamine, 100 ppm of hydrogen sulfide, and 100 ppm of ammonia, respectively. After processing for 1 hour in the atmosphere, the change in gas concentration after processing was measured and calculated by the following formula. Deodorization rate (%) = [(initial gas concentration-residual gas concentration) / (initial gas concentration)] x 100

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

[0015] Staphylococcus aureus IFO 12732
As test cells, and pre-use this with normal broth medium for 5-30
Cultivate the cells so that the density will be 10 ⁵ cells / ml, and use this as the test bacterial suspension. 0.2 ml of the suspension was uniformly inoculated into 0.2 g of a sample in a sterilized screw vial, and after static culture at 35 to 37 ° C. for 18 hours, 20 ml of sterile buffered saline was added to the container, Shake vigorously for 25 to 30 times with an amplitude of about 30 cm to disperse the live bacteria under test in the liquid. 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 a 15 ml pour plate of standard agar medium (create 2 plates for the same dilution). To do. This at 35 ~ 37 ℃ 24 ~
After culturing for 48 hours, the number of grown colonies was counted and multiplied by the dilution factor to calculate the number of viable bacteria in the sample. The dilution factor was based on the bacterial dispersion in the culture vessel and was calculated from the following formula. The number of viable bacteria = number of colonies x 20 x dilution multiple The effect was determined based on the average number of bacteria of the untreated standard cloth and the 3 samples, using the following formula, and the difference in increase / decrease was determined by the following formula.

[0016]

[Equation 1]

Example 1 595 parts of 4,4'-diphenylmethane diisocyanate was added to 2,644 parts of polytetramethylene ether glycol having an average molecular weight of 2,000, and the mixture was added to a reaction vessel under an N ₂ atmosphere of 80 parts.
After reacting with stirring at ˜90 ° C. for 60 minutes to prepare a prepolymer, it was diluted with 3,239 parts of dimethylformamide. Separately prepared 6,747 parts of dimethylformamide and 8 parts of ethylenediamine,
This solvent-diluted prepolymer was added to a solution of 1 part of diethanolamine and reacted with stirring to obtain a viscous 27% polyurethane polymer solution. 4 parts of porous silica microcapsules with an average particle size of 2.2 microns (hereinafter abbreviated as additive material A) were obtained by immersing a 20% aqueous solution of polyhexamethylene biguanide hydrochloride in spherical porous silica, drying it, and encapsulating it in 49%. 36 parts of amorphous silicate powder (made by Lhasa Kogyo Co., Ltd., trade name KD-211) (hereinafter abbreviated as additive material B) consisting of zinc oxide having an average particle size of 1 micron is dispersed in 100 parts of dimethylformamide. Immediately before spinning, the dispersion solution was added such that 0.5 parts of the additive A and 4.5 parts of the additive B were mixed with 100 parts of the polyurethane polymer. Diameter of the solution
Polyurethane elastic fiber of 140 denier wet-spun from a spinneret having 20 holes with a pore size of 0.1 m / m (Sample 2)
Got This physical property has a fineness of 140 (d) and strength of 1.275 (g /
d), elongation 554 (%), 300% modulus 0.311 (g /
It was d).

For comparison, a 140 denier polyurethane elastic fiber (Sample 1) spun without addition of additive A and additive B was obtained. This physical property has a fineness of 144 (d), strength
1.361 (g / d), Elongation 575 (%), 300% modulus
It was 0.321 (g / d), and the physical properties of Sample 2 to which the additive was added were not inferior to those of Sample 1. In addition, sample 2 was used with an acid dye (Nippon Kayaku Co., Ltd., Kayanol Blue N2G) with a bath ratio of 1:50, acid dye 2% (owf), acetic acid about 3.
After adding 0% and dyeing at 90 ° C. for about 30 minutes, it was washed with hot water and water to obtain a dyed polyurethane elastic fiber (Sample 3). Similarly, Sample 1 was dyed with an acid dye to obtain a dyed polyurethane elastic fiber (Sample 4). Samples 1, 2,
Regarding 3 and 4, JIS 0217-1976 "Indicators and indications regarding the handling of textiles" 2.2 (1) Washing number 103
Washing based on 0,10 times of antibacterial performance test,
Samples 1, 2, 3 and 4 were measured for deodorizing performance against trimethylamine and hydrogen sulfide, and the results are shown in Table 1.

[0019]

[Table 1]

As is clear from the results shown in Table 1, the modified polyurethane elastic fiber obtained by adding the additive A and the additive B to the polyurethane polymer solution is the unmixed product of Samples 1 and 4 regardless of the presence or absence of dyeing. Compared with antibacterial and deodorant properties, these properties were not lost even by washing.

Example 2 7 parts of additive A and 45.5 parts of additive B were previously dispersed in 100 parts of dimethylformamide, and 100 parts of a polyurethane polymer obtained in the same manner as in Example 1 immediately before spinning. ,
Polyurethane elastic fiber of 140 denier (Sample 5) was prepared by mixing and adding 1 part of additive material A and 6.5 parts of additive material B.
Got This physical property value has a fineness of 142 (d) and a strength of 1.269 (g.
/ D), elongation 560 (%), 300% modulus 0.322 (g
/ D). Further, Sample 5 was dyed as in Example 1 to obtain Sample 6. Similarly in advance with dimethylformamide 100
9 parts of additive material A and 51 parts of additive material B are dispersed in
Additive A was added to 100 parts of polyurethane polymer immediately before spinning.
Add 1.5 parts of additive material B to 8.5 parts, and add 1
A 40 denier polyurethane elastic fiber (Sample 7) was obtained.
This physical property value has a fineness of 141 (d), strength of 1.410 (g / d),
The elongation was 580 (%) and the 300% modulus was 0.341 (g / d). Further, the sample 7 was dyed in the same manner as in Example 1 to obtain the sample 8.
Got For Samples 5 to 8, antibacterial performance as in Example 1,
The deodorizing performance was measured and the results are shown in Table 2.

[0022]

[Table 2]

From the results shown in Table 2, the modified polyurethane elastic fiber has no difference in the physical properties even when the addition amounts of the additive A and the additive B are changed, and the antibacterial properties are higher than those of the samples 1 and 4 in Table 1.・
The deodorizing performance was significantly improved.

Comparative Example 1 Using the polyurethane polymer solution obtained in the same manner as in Example 1, 100 parts of dimethylformamide was added in advance to the additive A.
Disperse only 5 parts of the polymer, and immediately before spinning, polyurethane polymer
Additive A was mixed in an amount of 0.3 parts and 0.5 parts with 100 parts, and the respective polyurethane polymer solutions were spun in the same manner as in Example 1 to obtain 140 denier polyurethane elastic fibers (samples 9 and 10). It was The physical properties of sample 9 are 141
(D), strength 1.413 (g / d), elongation 578 (%), 300
% Modulus 0.341 (g / d), Sample 10 has a fineness of 140
(D), strength 1.288 (g / d), elongation 575 (%), 300
The% modulus was 0.325 (g / d), and the yarn quality was not abnormal. The antibacterial and deodorant performances of the respective samples were measured and the results are shown in Table 3.

[0025]

[Table 3]

As is clear from Table 3, the polyurethane elastic fiber obtained by mixing the additive material A alone with the polyurethane polymer solution has antibacterial performance when 0.5 part of the additive material A is mixed with 100 parts of the polyurethane polymer. However, the ratio thereof is low, there is no deodorizing performance for hydrogen sulfide, and the desired purpose cannot be achieved only by mixing the additive A alone.

Comparative Example 2 Using the polyurethane polymer solution obtained in the same manner as in Example 1, 50 parts of the additive B alone was previously dispersed in 100 parts of dimethylformamide, and immediately before spinning, the polyurethane polymer 100 was added. Additive B was mixed in an amount of 5 parts and 7.5 parts with respect to 1 part to prepare respective polyurethane polymer solutions in Example 1.
Spinning was performed in the same manner as in (1) to obtain polyurethane elastic fibers having 140 denier (Samples 11 and 12). Its physical properties are 142 in Sample 11.
(D), strength 1.269 (g / d), elongation 560 (%), 300
% Modulus 0.322 (g / d), Sample 12 has a fineness of 140
(D), strength 1.36 (g / d), elongation 575%, 300% modulus 0.328 (g / d), and the yarn quality was not different. The antibacterial / deodorant performance of each sample was measured, and the results are shown in Table 4.

[0028]

[Table 4]

As is clear from Table 4, the polyurethane elastic fiber mixed with only the additive B has a deodorizing performance but is inferior in antibacterial performance, and the mixing of the additive B alone achieves the desired purpose. I can't.

Application Example Additive A was previously added to 100 parts of dimethylformamide.
Parts, and 51 parts of additive B were dispersed in a polyurethane polymer solution obtained in the same manner as in Example 1, and 1.5 parts of additive A and 100 parts of the polyurethane polymer were added to 100 parts of the polyurethane polymer immediately before spinning. Mix and add the dispersion to 8.5 parts, and add
4 by wet spinning from a spinneret with 6 holes of 0.1 mmφ
A 0 denier modified polyurethane elastic fiber was obtained. The modified polyurethane elastic fiber is used as a core and is coated with an S-twisted 14 denier nylon thread not subjected to antibacterial / deodorant treatment, and further Z
A yarn double coated with 14 denier nylon yarn was made by known methods. 1 part of the yarn and 30 denier nylon yarn:
30 pairs of panty hose were trial-knitted by a panty hose knitting machine with one yarn feeding. Each sample is JIS L 0217-197.
6 “Indicators and handling methods for handling textile products” 2.2 (1) Based on washing number 103, 0, 10, 20, 3
Washed 0, 40, 50 times, each time 10 cm from the leg
A sample of × 10 cm was taken and the antibacterial / deodorant performance was measured and shown in Table 5. The weight ratio of the modified polyurethane elastic fiber in this sample was about 15%.

[0031]

[Table 5]

As is apparent from this application example, even if the modified polyurethane elastic fiber is coated with another fiber having no antibacterial / deodorant property, the modified polyurethane elastic fiber has a sustained release of the antibacterial / deodorant property. It is clear and practical that the effects will be realized.

[0033]

As is apparent from the above-mentioned examples and application examples, according to the present invention, a porous silica microcapsule in which an antibacterial agent having an average particle size of 5 microns or less is included in a polyurethane polymer solution, The modified polyurethane elastic fiber obtained by mixing and spinning amorphous silicate powder selected from divalent heavy metals such as zinc, copper or nickel has sufficient antibacterial and deodorant performance without spoiling the physical properties. Moreover, it is possible to provide a modified polyurethane elastic fiber that does not lose these properties even when dyed, and exhibits a sustained release effect when used together with other non-antibacterial / non-deodorant fibers.

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Claims (1)

Claims: 1. A polyurethane polymer solution comprising a porous silica microcapsule in which an antibacterial agent having an average particle size of 5 microns or less is included, and a divalent heavy metal of zinc, copper or nickel. Modified polyurethane elastic fiber obtained by mixing selected amorphous silicate powder and spinning the solution.