JPH0816295B2 - Antibacterial fiber structure material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fiber material suitable for producing a fiber structure such as a shirt, a blouse, a uniform, a bedding, etc. having an antibacterial property.

(Prior art and its problems) It has long been known to perform post-processing with an antibacterial agent or a fungicide in order to impart antibacterial properties to a fiber structure (eg Japanese Patent Publication No. 43-4240). .

On the other hand, the present applicant previously invented an organic polymer containing zeolite-based solid particles carrying metal ions having an antibacterial action and filed a patent application (Japanese Patent Laid-Open No. 59-133235). As the shape of the organic polymer, a granular body, a film, a fiber, etc. are exemplified.

However, the former post-processing method has drawbacks such as poor wash durability and impairing the texture of the fiber structure when there are many post-processing agents. On the other hand, the latter fibrous structure composed of fibers containing zeolite-based solid particles retaining metal ions having antibacterial action (hereinafter referred to as antibacterial zeolite) has insufficient whiteness and low light fastness. Since it is contained in the organic polymer, it has a rough texture and cannot be used in shirts, blouses, etc.

The present invention has been made in view of the above problems, and an object of the present invention is to improve the whiteness, light fastness, and feel of a fiber structure containing an antibacterial zeolite.

(Means for Solving Problems) The above-mentioned object is to contain zeolite-based solid particles in which the outermost layer is a natural fiber or regenerated cellulose fiber, and at least one layer other than the outermost layer holds metal ions having an antibacterial action. It is achieved by an antibacterial fiber structure material, which is a multi-layered structured yarn made of synthetic fibers.

 Hereinafter, the present invention will be described in detail.

As the natural fiber or regenerated cellulose fiber forming the outermost layer, cotton fiber, wool fiber, rayon, polynosic fiber and the like are preferable, and mixed fiber thereof may be used.

Examples of the synthetic fibers forming at least one layer other than the outermost layer include commonly known polyester fibers, commonly known nylon fibers, and commonly known acrylic fibers.

The antibacterial zeolite itself in the present invention is disclosed in JP-A-59-
The one disclosed in Japanese Patent No. 133235 can be used. That is, in the present invention, the zeolite-based solid particles having an antibacterial effect have one or more kinds of metal ions having a bactericidal effect in the ion-exchangeable portion of the natural or synthetic zeolite made of aluminosilicate. . Ag, Cu, Z as suitable examples of metal ions with bactericidal effect
Examples thereof include n, Fe, Cr, Ni, Sn and Hg. Particularly, Ag, Cu and Zn ions are preferable. It is possible to use the above-mentioned metals having antibacterial properties alone or in combination.

Zeolite is a general aluminosilicate having a three dimensionally developed skeletal structure, generally represented by with respect to the _{Al 2 O 3 xM 2 / n} O · Al 2 O 3 · ySiO 2 · zH 2 O. M
Represents an ion-exchangeable metal ion, which is usually monovalent to
It is a divalent metal, and n corresponds to this valence. While x
And y are the metal oxide and silica coefficients, and z is the number of crystal waters. Many types of zeolites are known, which differ in composition ratio, pore size, specific surface area, and the like.

However, the specific surface area of the zeolite-based solid particles used in the present invention is 150 m ² / g (anhydrous zeolite standard) or more,
The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite constituents should be 14 or less, preferably 11 or less.

Since the solution of the metal water-soluble salt having an antibacterial effect used in the present invention easily undergoes ion exchange with the zeolite limited in the present invention, the above-mentioned metal ions required by utilizing such a phenomenon are used alone or It is possible to mix and retain the zeolite in the stationary phase of the zeolite, but the zeolite-based particles retaining metal ions have a specific surface area of 150 m ² / g or more and a SiO ₂ / Al ₂ O ₃ molar ratio of 14 or more. There are two conditions that must be met: If not, it has been found that the object to achieve an effective antibacterial action cannot be obtained. It is considered that this is because the absolute amount of the metal ions fixed to the zeolite in a state where the effect can be exerted is insufficient. In other words, it is considered to be attributed to physicochemical properties such as the amount of exchange groups of zeolite, exchange rate, and accessibility.

Therefore, SiO ₂ known as molecular sieve
Zeolites having a large / Al ₂ O ₃ molar ratio are completely unsuitable in the present invention.

Further, in the case of zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 14 or less, it is possible to uniformly hold metal ions having an antibacterial action, and for this reason, a sufficient antibacterial effect cannot be obtained by using such a zeolite. It turned out to be obtained. In addition, the acid resistance and alkali resistance of zeolite with a high silica ratio in which the SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite exceeds 14 increase with the increase of SiO ₂ , but on the other hand, the synthesis also takes a long time, Economically, it is not a good idea to use such a high silica ratio zeolite. The above mentioned SiO ₂ / Al ₂ O ₃
Natural or synthetic zeolite of ≦ 14 can be sufficiently used in terms of acid resistance and alkali resistance in the normally considered application fields of the present structure, and it is economically economical and advantageous. For this reason, the SiO ₂ / Al ₂ O ₃ molar ratio is 1
Must be 4 or less.

As the zeolite material having a SiO ₂ / Al ₂ O ₃ molar ratio of 14 or less used in the present invention, either natural or synthetic zeolite can be used. For example, natural zeolites include anarsine (Analcime: SiO ₂ / Al ₂ O ₃ = 3.6-5.6), chabazite (Chabazite: SiO ₂ / Al ₂ O ₃ = 3.2-6.0 and
6.4 to 7.6), Clinoptilolite: SiO
₂ / Al ₂ O ₃ = 8.5-10.5), Erio-nite: SiO
₂ / Al ₂ O ₃ = 5.8-7.4), Faujasite: Si
_{O 2 / Al 2 O 3 =} 4.2~4.6), mordenite (Mordenite: SiO
₂ / Al ₂ O ₃ = 8.34 to 10.0), Phillipsite
_{ite: SiO 2 / Al 2 O} 3 = 2.6~4.4) , and the like. These typical natural zeolites are suitable for the present invention. Meanwhile Typical Examples of synthetic zeolite A- type zeolite _{(SiO 2 / Al 2 O 3} = 1.4~2.4), X- type zeolite (SiO ₂
/ Al ₂ O ₃ = 2 to 3), Y-type zeolite (SiO ₂ / Al ₂ O ₃ = 3)
6), mordenite (SiO ₂ / Al ₂ O ₃ = 9 to 10) and the like, and these synthetic zeolites are suitable as the zeolite material of the present invention. Particularly preferred are synthetic A-type zeolites, X-type zeolites, Y-type zeolites and synthetic or natural mordenites.

The shape of zeolite is preferably powder particles, and the particle diameter is several microns to several tens when applied to thick denier fibers etc.
Micron or several hundreds of microns or more is sufficient, while in the case of fine denier fiber, the smaller particle size is preferable,
For example, it is preferably 5 microns or less, particularly 2 microns or less.

The metal ions must be retained in the zeolite solid particles by an ion exchange reaction. The antibacterial effect and persistence thereof are insufficient if they are simply adsorbed or adhered irrespective of ion exchange. There are two possible methods for holding metal ions. The first method is a method in which an antibacterial zeolite to which antibacterial metal ions have been previously added is added to and mixed with the synthetic fiber during or before spinning. The second method is a method in which zeolite is incorporated into synthetic fibers and spun, and then the fibers are subjected to an ion exchange treatment so that metal ions having an antibacterial action are retained in the zeolite in the fibers.

First, the first method will be described. Taking the case of converting various zeolites defined in the present invention into the Ag-zeolite of the present invention, a solution of an aqueous silver salt such as silver nitrate is usually used for the conversion of Ag-zeolite, and the concentration of this is Care must be taken not to be too large. For example, when converting A-type or X-type zeolite (sodium-type) into Ag-zeolite by using an ion exchange reaction, if the silver ion concentration is high (for example, when 1 to 2 MAgNO _{3 is} used) By the exchange, the silver ion is replaced with the sodium ion in the solid phase, and at the same time, the silver oxide and the like are precipitated in the solid phase of the zeolite. As a result, the porosity of the zeolite is reduced and the specific surface area is significantly reduced. Further, even if the specific surface area does not decrease so much, the bactericidal activity is reduced by the presence of silver oxide itself. In order to prevent such excess silver from precipitating in the zeolite phase, it is necessary to maintain the concentration of the silver solution in a more dilute state, for example 0.3 MAgNO ₃ .
The safest concentration of AgNO ₃ is below 0.1M. When the AgNO ₃ solution having such a concentration is used, the specific surface area of the obtained Ag-zeolite is almost the same as that of the zeolite of the conversion material, and the antibacterial effect can be exhibited under the optimum conditions.

Even when the zeolites defined in the present invention are converted to Cu-zeolite, a phenomenon similar to that of Ag-zeolite described above occurs depending on the concentration of the copper salt used for ion exchange. For example, A-type or X-type zeolite (sodium-type)
When converted to Cu-zeolite by ion exchange reaction, when 1M CuSO _{4 is} used, Cu ²⁺ replaces Na ^{+ in the} solid phase,
At the same time, basic precipitates such as Cu ₃ (SO ₄ ) (OH) ₄ are precipitated in the zeolite solid phase, so that the porosity of the zeolite is reduced and the specific surface area is significantly reduced. In order to prevent such excess copper from precipitating in the zeolite phase, it is preferable to keep the concentration of the aqueous copper solution used in a more diluted state, for example, 0.05 M or less. It was found that the specific surface area of the Cu-zeolite obtained when the CuSO ₄ solution having such a concentration was used was almost the same as that of the zeolite used as the conversion material, and that the antibacterial effect could be exhibited in the optimum state.

When converting to Ag-zeolite and Cu-zeolite, it was stated that there is precipitation of solid matter on the zeolite solid phase depending on the concentration of salts used for ion exchange, but when converting to Zn-zeolite, the salts used In the vicinity of 2-3M, such a phenomenon is not seen. Usually, the Zn-zeolite used in the present invention can be easily obtained by using salts having the above concentration.

When the ion exchange reaction is carried out by the batch method upon conversion into the above-described Ag-zeolite, Cu-zeolite and Zn-zeolite, the salt solution having the above concentration may be used for the dipping treatment of the zeolite material. In order to increase the metal content in the zeolite material, the number of batch treatments should be increased. On the other hand, when treating a zeolite material by a column method using a salt solution having the above concentration, the adsorption tower is packed with the zeolite material, and if the salt solution is passed through this, the target metal-zeolite is easily obtained. can get.

The amount of metal in the above metal-zeolite (anhydrous zeolite basis) is 30% by weight or less for silver,
The preferred range is 0.001 to 5% by weight. On the other hand, regarding copper and zinc used in the present invention, the amount of copper or zinc in the metal-zeolite (based on anhydrous zeolite) is 35% by weight or less, and the preferable range is 0.01 to 15% by weight. It is also possible to use silver, copper and zinc ions in combination. In this case, the total amount of metal ions may be 35% by weight or less based on the metal-zeolite (anhydrous zeolite), and the preferred range is Depending on the composition ratio, it is approximately 0.001 to 15% by weight.

Further, even if metal ions other than silver, copper, zinc, such as sodium, potassium, calcium or other metal ions coexist, the bactericidal effect is not hindered,
There may be no residual or coexistence of these ions.

The antibacterial zeolite particles thus obtained are mixed with polyester or nylon chips, or mixed with the melted polyester or nylon to prepare a master chip in advance, or by mixing with a monomer, Included in polyester or nylon.

The antibacterial zeolite particles are made of acrylic polymer DM.
It is included in acrylic by mixing with the F solution and wet spinning according to a conventional method.

The antibacterial zeolite is preferably included in an amount of 0.05 to 5% by weight based on the synthetic fiber. If it is less than 0.05%, the antibacterial action is poor. On the other hand, if it exceeds 5% by weight, the effect is not particularly increased, and the physical properties of the fiber are deteriorated.

Next, in the second method, that is, in the method of carrying out the exchange reaction of the antibacterial metal ions after spinning the zeolite-based solid particles which do not retain the antibacterial metal ions in the synthetic fiber, the time of the ion exchange treatment is different. Can be performed according to the first method. The zeolite-based solid particles retained on the synthetic fiber still retain the ion exchange capacity.
The proportion of zeolite in the fiber that is ion-exchanged depends on the properties of the synthetic fiber. In the case of a polymer having a relatively high hydrophilicity, metal ions permeate into the interior as water permeates, so that the zeolite inside the polymer is also ion-exchanged. However, even in the case of a hydrophobic polymer, the zeolite near the surface is ion-exchanged in a considerable ratio.

The antibacterial zeolite-containing synthetic fiber of the present invention can be drawn or undrawn.

In the case of a two-layer structured yarn, the outer layer is a natural fiber or regenerated cellulose fiber, and the inner layer is a synthetic fiber containing antibacterial zeolite.

In the case of a multi-layered yarn having a three-layer structure or more, the outer layer is a natural fiber or a regenerated cellulose fiber, and the layers other than the outermost layer are not particularly limited as long as at least one layer is an antibacterial zeolite-containing synthetic fiber. .

A multi-layer structure yarn having an outermost layer made of natural fibers or regenerated cellulose fibers and at least one layer other than the outermost layer made of synthetic fibers containing antibacterial zeolite can be obtained by a known method.

For example, when the outer layer is a cotton fiber and the inner layer is a two-layer structured yarn composed of polyester fiber yarn containing antibacterial zeolite, the roving yarn of the cotton fiber is passed through the spinning machine in order to the back roller, middle roller and front roller, while the antibacterial property is used. It is obtained by supplying a zeolite-containing polyester fiber yarn immediately before the front roller, and performing a composite spinning of both the natural fiber roving yarn and the antibacterial zeolite-containing polyester fiber yarn at the front roller nip point.

Also, for example, in the case of a three-layer structure yarn in which the outer layer is a cotton fiber, the middle layer is a polyester fiber containing antibacterial zeolite, and the inner layer is a polyester fiber yarn containing no antibacterial zeolite,
When producing roving from a sliver, a cotton fiber sliver that is being drafted is overlaid with polyester fiber containing antibacterial zeolite to form a shin, and then both are drafted together into a roving, which is then spun. While passing the roving yarn through a back roller, a middle roller and a front roller in sequence, a polyester fiber yarn containing no antibacterial zeolite is supplied immediately before the front roller, and both the roving yarn and the polyester fiber yarn are fed to the front roller. Obtained by composite spinning at the nip point.

In the present invention, when it is desired to further enhance the antibacterial performance, a fiber structure material obtained as described above is used to form a fiber structure, and an amphoteric active agent antibacterial agent, An antibacterial agent or the like having a primary ammonium base is added.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
The whiteness, light fastness, and antibacterial properties described in the examples are measured by the following methods.

1) Whiteness The reflectance at 450 nm was measured with a spectrophotometer.

2) Light fastness It was measured by the JIS L-0842 method.

3) Antibacterial property As the antibacterial test method, the bacterial count method determined by the Textile Products Sanitation Council was used.

The strain used in the test was Staphylococcus aureus
(Staphylococcus aureus) IFO 12732 was used.

Further, the antibacterial property was determined from the results of the antibacterial test by the following calculation method.

B: Number of viable cells after 18-hour culture of untreated cloth C: Number of viable cells after 18-hour culture of processed cloth The processed cloth was processed and washed by the 103 method 50 times for durability test I used one.

The antibacterial zeolite used in the present invention is Bactekiller A3.
The product is commercially available as 50BN (trademark, manufactured by Sinenen New Ceramic Co., Ltd.). This is A type zeolite with silver 3
% By weight and 5% by weight of copper are applied by ion exchange, and have an average particle diameter of 5 to 6 μm. The specific surface area is 500 to 600 m ² / g, and the SiO ₂ / Al ₂ O ₃ molar ratio is about 2.

Example 1 A 30-count double-layered structure yarn in which the outer layer was a cotton fiber and the inner layer was a Bactequiler-containing polyester fiber spun yarn was manufactured, and a plain woven fabric having a warp density of 120 yarns / inch and a weft density of 60 yarns / inch was woven.

The polyester containing Bactekiller is polyethylene terephthalate (hereinafter referred to as PET) chips, 2.0 wt% of Bactekiller A350BN is added to PET and mixed in advance, melt-spun and stretched to 1.5 denier according to a conventional method, and a length of 40 mm. It was cut into pieces and manufactured. Then, using the obtained Bactequila-containing polyester fiber, a Bactequila-containing polyester fiber yarn was produced by a spinning machine.

The two-layer structured yarn is produced by passing a roving yarn of a cotton fiber through a spinning machine through a back roller, a middle roller and a front roller in this order, while supplying the Bactequila-containing polyester fiber yarn immediately before the front roller. It is obtained by carrying out composite spinning of both the roving yarn and the above-mentioned Bactequila-containing polyester fiber yarn at the front roller nip point. At this time, the mixing ratio of the Bactekiller-containing polyester fiber and the cotton fiber was 30:70.

Then, the obtained plain weave is subjected to usual scouring, mercerizing,
Preparation processing by heat setting was performed.

50 g of glyoxal resin (manufactured by Dainippon Ink & Chemicals, Beckamine LKS) and 15 g of metal salt catalyst (Sumitomo Chemical Co., Ltd., Sumitex Accelerator MX) were added to water, and a resin solution adjusted to 1 was used. Given to plain woven fabric (drawing ratio
60%), followed by heat treatment at 150 ° C. for 3 minutes to fix the resin to the fiber to obtain the product of Example 1 of the present invention.

Example 2 The same plain weave as in Example 1 was subjected to the usual preparatory treatment.

Amphoteric activator type antibacterial agent in water (Nikka Chemical Co., Nikkanon
RB) 20 g, glyoxal resin (manufactured by Dainippon Ink and Co., Beckamine LKS) 50 g, metal salt catalyst (Sumitomo Chemical Co., Ltd., Sumitex Accelerator MX) 15 g, and the resin solution adjusted to 1 was used to prepare this resin solution. Was applied to the above plain woven fabric (squeezing ratio 60%), followed by heat treatment at 150 ° C. for 3 minutes to fix the resin to the fiber to obtain a product of Example 2 of the present invention.

Comparative Example 1 The Bactekiller-containing polyester fiber and the cotton fiber of Example 1 were mixed and spun at a ratio of Bactequiler-containing polyester fiber 30:70 to produce a 30th-count mixed yarn, and this mixed yarn was used to obtain warp density of 120 / inch, A plain weave having a weft density of 60 / inch was woven.

The resulting plain weave is then subjected to normal preparatory treatment, Example 1.
The same finishing treatment as above was performed to obtain a product of Comparative Example 1.

Comparative Example 2 A plain weave similar to Comparative Example 1 was subjected to the usual preparation treatment, Example 2
The same finishing treatment as above was performed to obtain the product of Comparative Example 2.

Comparative Example 3 A normal polyester fiber containing no Bactekiller (1.5 denier, cut length 40 mm) and a cotton fiber were blended in a ratio of 30:70 normal polyester fiber containing no Bactekiller to produce a No. 30 blended yarn, Using this blended yarn, a plain woven fabric having a warp density of 120 yarns / inch and a weft density of 60 yarns / inch was woven.

The resulting plain weave is then subjected to normal preparatory treatment, Example 1.
The same finishing treatment as in (1) was performed to obtain a product of Comparative Example 3.

COMPARATIVE EXAMPLE 4 The same plain weave as in Comparative Example 3 was subjected to normal preparatory treatment, Example 2.
The same finishing treatment as above was applied to obtain a product of Comparative Example 4.

Next, Table 1 shows the results of comparison of the whiteness, light fastness, and antibacterial properties of the products obtained in Examples 1 and 2 of the present invention with Comparative Examples.

As is clear from Table 1, the products obtained by the present invention are excellent in whiteness, light fastness and antibacterial properties.

Example 3 A three-layered yarn having a count of 30 is prepared, in which the outer layer is a cotton fiber, the middle layer is a polyester fiber containing Bactekiller, and the inner layer is a normal polyester fiber filament yarn, and the warp density is 120 / inch and the warp density is 60. Book / inch plain weave was woven.

The above three-layer structured yarn was overdrafted with the Bactequila-containing polyester fiber sliver of Example 1 at the center of the cotton fiber sliver being drafted, and then both were drafted together into a roving, which was then spun on a spinning machine. While passing the roving yarn through the back roller, the middle roller and the front roller in sequence, 30d / 12f polyester fiber filaments containing no Bactekiller are supplied immediately before the front roller, and the roving yarn and the polyester fiber filaments containing no Bactekiller are supplied. It is obtained by composite spinning both the yarn and the yarn at the front roller nip point. At this time, the mixing ratio of the cotton fiber, the polyester fiber containing Bactekiller and the polyester fiber containing no Bactekiller was 60:20:20.

Then, a usual preparatory treatment and the same finishing treatment as in Example 1 were performed to obtain the product of Example 3.

Example 4 A 30-count three-layer structure yarn having an outer layer of rayon, an inner layer of normal polyester fiber containing no Bactekiller, and an inner layer of a polyester fiber filament containing Bactekiller is produced and has a warp density of 120 yarns / inch and a weft density of 60 yarns. / Inch plain weave was woven.

The Bactekiller-containing polyester fiber filament yarn was obtained by mixing PET chips with 2.0% by weight of Bactekiller A350BN in advance with respect to PET, spinning and drawing to 30d / 12f.

In addition, the above-mentioned three-layer structure yarn does not contain Bactekiller at the center of the rayon sliver being drafted.
Denier polyester fiber sliver with a cut length of 40 mm is piled up to form a shino, and then both are drafted together into a roving, and the roving is passed through a back spinning machine, a middle roller, and a front roller in sequence with a spinning machine. It can be obtained by supplying a Bactekiller-containing polyester fiber filament yarn immediately before the front roller, and performing a composite spinning of both the roving yarn and the Bactekiller-containing polyester fiber yarn at the front roller nip point. At this time, the mixing ratio of rayon fiber, polyester fiber not containing Bactekiller and polyester fiber containing Bactekiller was 60:20:20.

Then, a usual preparatory treatment and the same finishing treatment as in Example 1 were performed to obtain the product of Example 4.

The whiteness, light fastness and antibacterial properties of the products obtained in Examples 3 and 4 were sufficiently satisfactory.

Example 5 A 30-layer double-layered structure yarn having an outer layer made of cotton fiber and an inner layer made of Bactequila-containing nylon fiber spun yarn was produced.
A plain weave with 0 threads / inch and weft density of 60 threads / inch was woven.

Nylon containing Bactekiller is a 6 Nylon dry tip with relative viscosity (ηrel) 2.3 measured with 95% sulfuric acid, 2.0 wt% of Bactekiller A350BN to Nylon is mixed in advance, melt-spun and stretched to 2.5 denier according to a conventional method. It was manufactured by cutting it to a length of 35 mm. Then, using the obtained nylon fiber containing Bactekiller, a nylon fiber yarn containing Bactekiller was produced by a spinning machine.

In the double-layered structure yarn, a roving yarn of a cotton fiber is passed through a spinning machine through a back roller, a middle roller, and a front roller in order, while the nylon fiber yarn containing a Bactequiler is supplied immediately before the front roller, It is obtained by composite spinning both the roving yarn and the Bactequiler-containing nylon fiber yarn at the front roller nip point. Also at this time, the mixing ratio of the Bactekiller-containing nylon fiber and the cotton fiber was 30:70.

Then, the obtained plain weave is subjected to usual scouring, mercerizing,
Preparation processing by heat setting was performed.

Glyoxal-based resin (Dainippon Ink and Beckamine LKS) 50g, metal salt catalyst (Sumitomo Chemical Co., Sumitex Accelerator MX) 15g were added to water, and the resin liquid adjusted to 1 was used. The product was applied to the above-mentioned plain woven fabric (drawing ratio 60%) and subsequently heat-treated at 150 ° C. for 3 minutes to fix the resin to the fiber to obtain a product of Example 5 of the present invention.

Example 6 The same plain weave as in Example 5 was subjected to the usual preparatory treatment.

Amphoteric activator type antibacterial agent in water (Nikka Chemical Co., Nikkanon
RB) 20 g, glyoxal resin (manufactured by Dainippon Ink and Co., Beckamine LKS) 50 g, metal salt catalyst (Sumitomo Chemical Co., Ltd., Sumitex Accelerator MX) 15 g, and the resin solution adjusted to 1 was used The liquid was applied to the above plain woven fabric (squeezing ratio: 60%), followed by heat treatment at 150 ° C. for 3 minutes to fix the resin to the fiber, to obtain a product of Example 6 of the present invention.

Comparative Example 5 Nylon fibers containing cotton and cotton fibers of Example 5 were blended in a ratio of 30:70 nylon fibers containing Bactequiler to produce a 30-th yarn blended yarn, and the blended yarn was used to obtain warp density
Weaving plain weave with 120 stitches / inch and weft density of 60 stitches / inch.

The plain fabric obtained is then subjected to the usual preparatory treatments, Example 5.
The same finishing treatment as above was applied to obtain a product of Comparative Example 5.

Comparative Example 6 A plain weave similar to that of Comparative Example 5 was subjected to a conventional preparatory treatment, Example 6
The same finishing treatment as above was applied to obtain a product of Comparative Example 6.

Comparative Example 7 Normal nylon fiber containing no Bactekiller (2.5
Denier, cut length 35 mm) and cotton fibers were mixed and spun at a ratio of 30:70 of normal nylon fibers containing no Bactekiller and 3
Manufacture 0-count blended yarn and use this blended yarn to produce warp density of 120
A plain woven fabric with a book / inch and a weft density of 60 / inch was woven.

The plain fabric obtained is then subjected to the usual preparatory treatments, Example 5.
The same finishing treatment as above was applied to obtain a product of Comparative Example 7.

Comparative Example 8 A plain weave similar to Comparative Example 7 was subjected to the usual preparation treatment, Example 6
The same finishing treatment as above was applied to obtain a product of Comparative Example 8.

Next, Table 2 shows the results of comparison of the whiteness, light fastness, and antibacterial properties of the products obtained in Examples 5 and 6 of the present invention with Comparative Examples.

As is clear from Table 2, the products obtained by the present invention are excellent in whiteness, light fastness and antibacterial properties.

Example 7 The outer layer is cotton fiber, the middle layer is Bactequila-containing nylon fiber,
A 30-count three-layer structure yarn, which is a normal nylon fiber filament yarn containing no Bactekiller as the inner layer, was produced and a plain weave fabric having a warp density of 120 yarns / inch and a weft density of 60 yarns / inch was woven.

The above three-layer structured yarn was overdrafted with the Bactequiler-containing nylon fiber sliver of Example 5 at the center of the cotton fiber sliver being drafted, and then both were drafted together into a roving, which was then spun on a spinning machine. While passing the roving yarn through the back roller, the middle roller, and the front roller in sequence, 35d / 12f nylon fiber filaments containing no Bactekillar are fed immediately before the front roller, and the roving yarns and Bactequila-free nylon fiber filaments are fed. It is obtained by composite spinning both the yarn and the yarn at the front roller nip point. At this time, the mixing ratio of the cotton fiber, the Bactequiler-containing nylon fiber and the Bactequiler-free nylon fiber was 60:20:20.

Then, a usual preparatory treatment and the same finishing treatment as in Example 5 were performed to obtain a product of Example 7. Whiteness of the obtained product,
The light fastness and antibacterial properties were satisfactory.

Example 8 A 30-count double-layered yarn having an outer layer made of cotton fiber and an inner layer made of Bactequila-containing acrylic fiber was produced, and a plain weave having a warp density of 120 yarns / inch and a weft density of 60 yarns / inch was woven.

Bactekiller-containing acrylic is composed of an acrylic polymer of which the first component is 89% by weight of acrylonitrile, the second component is 10% by weight of methyl acrylate, and the third component is 1% by weight of sodium acrylic sulfonate. Bactekiller A350BN was added and mixed, and wet-spun and stretched according to a conventional method to obtain 3 denier, which was cut into a length of 51 mm for production. Then, using the obtained Bactequila-containing acrylic fiber, a Bactequila-containing acrylic fiber yarn was produced by a spinning machine.

The two-layer structured yarn is produced by passing a roving yarn of cotton fiber through a spinning machine through a back roller, a middle roller and a front roller in order, while supplying the Bactequiler-containing acrylic fiber yarn immediately before the front roller. It is obtained by composite spinning of both the roving yarn and the Bactequiler-containing acrylic fiber yarn at the front roller nip point. Also at this time, the mixing ratio of the Bactekiller-containing acrylic fiber and the cotton fiber was 30:70.

Then, the obtained plain weave is subjected to usual scouring, mercerizing,
Preparation processing by heat setting was performed. 50 g of glyoxal resin (Dainippon Ink and Beckamine LKS) in water,
Add 15 g of metal salt catalyst (Sumitex Accelerator MX, manufactured by Sumitomo Chemical Co., Ltd.) and use the resin solution adjusted to 1 to apply this resin solution to the above plain woven fabric (squeeze ratio 60%) and continue at 150 ° C. The product was heat treated for 3 minutes to fix the resin to the fiber, and the product of Example 8 of the present invention was obtained.

Example 9 The same plain weave as in Example 8 was subjected to the usual preparatory treatments.

Amphoteric activator type antibacterial agent in water (Nikka Chemical Co., Nikkanon
RB) 20 g, glyoxal resin (manufactured by Dainippon Ink and Co., Beckamine LKS) 50 g, metal salt catalyst (Sumitomo Chemical Co., Ltd., Sumitex Accelerator MX) 15 g, and the resin solution adjusted to 1 was used The liquid was applied to the above plain woven fabric (squeezing ratio: 60%), followed by heat treatment at 150 ° C. for 3 minutes to fix the resin to the fiber, to obtain a product of Example 9 of the present invention.

Comparative Example 9 The acrylic fiber containing the Bactekiller and the cotton fiber of Example 8 were blended in a ratio of 30: 70 Acrylic fiber containing Bactequiler to produce a 30-th yarn blended yarn, and this blended yarn was used to obtain warp density.
Weaving plain weave with 120 stitches / inch and weft density of 60 stitches / inch.

The resulting plain weave is then subjected to normal preparatory treatment, Example 8.
The same finishing treatment as above was applied to obtain a product of Comparative Example 9.

COMPARATIVE EXAMPLE 10 A plain weave similar to Comparative Example 9 was subjected to a conventional preparatory treatment, Example 9.
The same finishing treatment as above was applied to obtain a product of Comparative Example 10.

Comparative Example 11 Ordinary acrylic fiber containing no Bactekiller (3 denier, cut length 51 mm) and cotton fiber were mixed and spun at a ratio of 30:70 normal cotton containing no Bactekiller and 30
We manufacture a mixed yarn of count and use this mixed yarn to produce a warp density of 120
A plain woven fabric with a book / inch and a weft density of 60 / inch was woven.

The resulting plain weave is then subjected to normal preparatory treatment, Example 8.
The same finishing treatment as above was applied to obtain a product of Comparative Example 11.

Comparative Example 12 A plain weave similar to that of Comparative Example 11 was subjected to a conventional preparatory treatment, Example 2
The same finishing treatment as above was performed to obtain a product of Comparative Example 12.

Next, Table 3 shows the results of comparison of the whiteness, light fastness, and antibacterial properties of the products obtained in Examples 8 and 9 of the present invention with Comparative Examples.

As is apparent from Table 3, the products obtained by the present invention are excellent in whiteness, light fastness and antibacterial properties.

Example 10 A 30-count three-layer structured yarn in which the outer layer is a cotton fiber, the middle layer is a Bactekiller-containing acrylic fiber, and the inner layer is a normal Bactekiller-free acrylic fiber is produced, and the warp density is 120 /
Weaved a plain weave with inch and weft density of 60 / inch.

The above three-layer structured yarn was overdrafted with the Bactequiler-containing acrylic fiber sliver of Example 8 in the center of the cotton fiber sliver being drafted, and then both were drafted together into a roving, which was then spun on a spinning machine. While passing the roving yarn through the back roller, the middle roller, and the front roller in order, the acrylic fiber yarn that does not contain the 50th Bactekiller is supplied immediately before the front roller, and It is obtained by spinning both at the front roller nip point. At this time, the mixing ratio of the cotton fiber, the Bactekiller-containing acrylic fiber and the Bactekiller-free acrylic fiber was 60:20:20.

Then, a usual preparatory treatment and the same finishing treatment as in Example 8 were performed to obtain a product of Example 10.

Example 11 A 30-layer three-layer structure yarn having an outer layer of rayon, a middle layer of normal acrylic fiber containing no Bactekiller and an inner layer of acrylic fiber yarn of Bactekiller is manufactured, and has a warp density of 120 / inch, a weft density of 60 / Inch plain weave was woven.

The above three-layer structured yarn was prepared by laminating a rayon sliver being drafted on top of an acrylic fiber sliver containing 3 denier and 51 mm in cut length, containing no Bactekiller, and then drafting both together into a roving. ,
With a spinning machine, the above rovings are back roller, middle roller,
While successively passing through the front roller, the above Bactekira-containing acrylic fiber yarn was supplied immediately before the front roller, and both the roving yarn and the Bactequiler-containing acrylic fiber yarn were composite-spun at the front roller nip point. To be

At this time, the mixing ratio of rayon fiber, Bactekiller-free acrylic fiber and Bactekiller-containing acrylic fiber was 6
It was 0:20:20.

Then, the usual preparatory treatment and the same finishing treatment as in Example 8 were performed to obtain the product of Example 11.

The whiteness, light fastness, and antibacterial properties of the products obtained in Examples 10 and 11 were sufficiently satisfactory.

(Effect of the invention) The fiber structure made of the antibacterial fiber structure material of the present invention is
It has sufficient antibacterial ability, whiteness and light fastness, and since the outermost layer is natural fiber or regenerated cellulose fiber, it has an excellent texture and is suitable for use in shirts, blouses, uniforms, bedding, etc. It is useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D02G 3/04 3/36 D03D 15/00 C (56) Reference JP-A-63-175117 (JP , A) JP-A-63-219646 (JP, A) JP-A-63-190018 (JP, A) Actually developed JP-A-63-13092 (JP, U)

Claims (1)

[Claims] 1. A multi-layered yarn having an outermost layer made of natural fibers or regenerated cellulose fibers, and at least one layer other than the outermost layer made of synthetic fiber containing zeolite-based solid particles holding metal ions having an antibacterial action. An antibacterial fiber structure material characterized by being present.