JP3247293B2 - Antibacterial cellulose acetate fiber and antibacterial fiber product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial cellulose acetate fiber and an antibacterial fiber product containing the antibacterial cellulose acetate fiber.

[0002]

2. Description of the Related Art Cellulose acetate (hereinafter, also referred to as "acetate") fibers have excellent coloring properties and a dry feel, and are used as materials for fashion (outer garments, inner garments).
It demonstrates its excellent properties. However, even such cellulose acetate fibers do not necessarily have characteristics that sufficiently satisfy recent advanced market needs.

[0003] For example, in recent years, the demand for antibacterial fiber products has been increasing due to the improvement of living standards and the spread of hygiene philosophy. In addition, in recent years, the problem of nosocomial infections caused by methicillin-resistant Staphylococcus aureus has been noticed. Attempts have been made to impart antibacterial properties not only to the most frequently used cotton fiber but also to various synthetic fibers.

[0004] As for cotton fibers, those obtained by treating the surface of the fibers with various antibacterial agents have been proposed. For example,
There is known a method of immobilizing a quaternary ammonium salt containing silicic acid or an antibacterial deodorant such as polyoxyethylene trialkylammonium chloride on the fiber surface. However, the cotton fiber surface treated with an antibacterial agent in this way has a problem that the antibacterial agent falls off due to long-term use or washing, the effect is reduced, and stable antibacterial properties cannot be maintained over a long period of time. There is. Synthetic fibers have been improved using conjugate fibers in order to maintain this stable antibacterial property (see, for example,
No. 175117, Japanese Utility Model Application Laid-Open No. Sho 60-79433, Japanese Utility Model Application Laid-Open No. 61-67739, etc.). Further, as an antibacterial agent added to these synthetic fibers, JP-A-4-27
No. 3803 describes a metal-containing phosphoric acid compound.

However, even if this antibacterial agent is applied to cellulose acetate fiber which is a semi-synthetic fiber,
The compatibility of the antibacterial agent is insufficient, and stable antibacterial properties cannot be obtained over a long period of time.

Accordingly, an antibacterial fiber product which is particularly suitable for the fields of towels, mats, nursing clothes, etc., which are frequently washed, maintains excellent water-absorbing and moisture-absorbing properties at the cotton fiber level, and has a good feeling. The emergence of is expected.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cellulose acetate fiber having excellent properties and a semi-permanent antibacterial property, without deteriorating feeling, without deactivation by washing or the like, and without discoloration. An object of the present invention is to provide a fiber and a fiber product containing the fiber.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the object, and as a result, it has been found that cellulose acetate fibers contain a specific antibacterial agent and a fiber product in which the fibers are mixed in a specific ratio is: It has been found that the cellulose acetate fiber has a semi-permanent antibacterial property while maintaining the properties of the cellulose acetate fiber, and can be formed into a good antibacterial fiber product, and has reached the present invention.

That is, the present invention is characterized in that the cellulose acetate fiber contains an antibacterial agent comprising a metal-containing phosphate compound and zinc oxide in an amount of 0.1 to 5% by weight based on the weight of the fiber. An antibacterial fiber product characterized in that the cellulose acetate fiber and the antibacterial cellulose acetate fiber are mixed in at least 5% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Cellulose acetate which is an object of the present invention is one in which an average of 1 to 3 hydroxyl groups out of 3 hydroxyl groups present in a repeating unit of cellulose is an acetate ester. Those in which 1.9 to 2.8 are esterified (acetylation degree 47 to 60%) are preferred.

In the acetate fiber of the present invention, it is necessary that the acetate contains a specific amount of an antibacterial agent comprising a metal-containing phosphoric acid compound and zinc oxide.

[0012] The metal-containing phosphoric acid compound is a compound represented by the following formula [1].
No. 73803 describes in detail.

[0013]

(M ¹ ) _a (A) _b (M ² ) _c (PO ₄ ) _d · nH ₂ O [1] wherein M ¹ is at least selected from silver, copper, zinc, tin or lead One kind of metal ion, A is an alkali metal ion,
At least one metal ion selected from the group consisting of alkaline earth metal ions and ammonium ions, M ² is a tetravalent metal, n is an integer of 0 to 6, ad is a positive number, and pa + qb = 1 When C = 2, d = 3, pa + qb =
In the case of 2, c = 1 and d = 2. Here, p is the valence of M ¹ and q is the valence of A. Among them, compounds in which M ¹ in the above formula [1] is silver, A is an alkali metal ion or ammonium ion, and M ² is zirconium, tin or titanium (particularly zirconium) are preferred.

[0014] Examples of suitable the metal-containing phosphoric acid _{compound, (1) Ag 0. 00 5} Li 0. 99 5 Zr 2 (PO 4) 3 (2) Ag 0. 01 (NH 4) 0. _{99 Zr 2 (PO 4) 3} (3) Ag 0. 05 Na 0. 95 Zr 2 (PO 4) 3 (4) Ag 0. 2 K 0. 8 Ti 2 (PO 4) 3 (5) Ag 0. _{00 1 Li 1. 99 9 Zr (} PO 4) 2 (6) Ag 0. 01 Na 1. 99 Zr (PO 4) 2 (7) Ag 0. 01 K 1. 99 Sn (PO 4) 2 · 1. 2H _{2
O (8) Ag 0. 1 (} MH 4) 1. 9 Ti (PO 4) 2 · 4
H ₂ O and Ag in each of the above exemplified compounds are converted to Zn, Pb, S
Compounds substituted with a metal selected from n and Cu can be given.

As a commercial product of the compound represented by the above formula [1], for example, "NOVALON" (trademark product) manufactured by Toagosei Co., Ltd. and the like can be mentioned.

Among the above-exemplified compounds, those containing Ag, especially the compounds (1), (2) and (3), are excellent in antibacterial performance and stably bound with Ag ions, so that cellulose is used. Silver ions are not eluted during addition and mixing in an acetate solution (spinning dope), dry spinning, or even after the product is formed, which is preferable because there is no risk of causing reduction in antibacterial properties and coloring.

On the other hand, zeolite supporting silver is not suitable because it is easily eluted by washing or the like.

On the other hand, zinc oxide (ZnO) is also a substance having an antibacterial effect. In the present invention, when used in combination with the metal-containing phosphoric acid compound of the above formula [1], the interaction between the two causes washing by washing. The antimicrobial agent has a unique effect of increasing rather than decreasing.

The antibacterial agent comprising the metal-containing phosphoric acid compound and zinc oxide may be both integrated into fine particles or a mixture of fine particles.

The average particle size of these antibacterial agents is 0.01 to 2
μm, particularly preferably 0.01 to 1 μm, is preferred in view of spinning condition of antibacterial acetate fiber, antibacterial performance and feeling of fiber product.

The antibacterial acetate fiber suitable in the present invention contains an antibacterial agent comprising the metal-containing phosphoric acid compound of the above formula [1] and zinc oxide (ZnO) in a total amount of 0.1 to 5%. %, Preferably 0.3 to 3% by weight, particularly preferably 0.5 to 2.5% by weight. If the amount of the antibacterial agent is too small, the antibacterial property is inferior. If the amount is too large, the spinnability and feeling of the antibacterial acetate fiber are reduced.

The ratio between the zinc oxide (ZnO) contained in the antibacterial acetate fiber and the metal-containing phosphoric acid compound represented by the above formula [1] is preferably 2/8 to 8/2 by weight.

When the antibacterial acetate fiber of the present invention is prepared, for example, by dissolving cellulose diacetate flakes having an oxidation degree of about 55% in a solvent such as acetone to prepare a dope for spinning, the dope described above is added to the dope. For example, a predetermined amount of at least one kind of the compound represented by the formula [1] and zinc oxide are added, and the dope is spun from a spinning nozzle into a dry atmosphere (dry spinning) and taken up under a predetermined draft. Can be manufactured by The shape of the spinning nozzle may be an ordinary circular shape, but when a fiber having a special cross section is used, a nozzle having an irregular cross section is used. In order to increase the degree of heterogeneity obtained at this time, polyoxyalkylene glycol is added to cellulose diacetate flakes in an amount of 5%.
It is useful to contain 含有 40 wt%.

Since the thus-spun acetate fiber is a long fiber (continuous filament), in the case of cotton blending and blending, it is crimped and then cut into an appropriate fiber length to form a short fiber (staple fiber). .

The antibacterial fiber product, which is another object of the present invention, must contain at least 5% by weight of antibacterial cellulose acetate fiber. Further, as the antibacterial cellulose acetate fiber, an acetate fiber containing the antibacterial agent comprising the metal-containing phosphate compound and zinc oxide in an amount of 0.1 to 5% by weight based on the weight of the fiber, which is described in detail above, is useful. It is. As the fibers other than the above-mentioned acetate fibers used in the antibacterial fiber product, fibers having excellent water absorption and hygroscopicity and good feeling are preferable from the viewpoint of use of the product, and typically, cotton (cotton) is mentioned. Can be

The cotton fiber may be a normal cotton fiber, for example, what is referred to as sea-island cotton, Egyptian cotton, Brazilian cotton, Peruvian cotton, rice cotton, Mexican cotton, Indian cotton, Chinese cotton, etc. In general, those having a size of about 0.5 to 3 inches are used.

This cotton fiber can be used as it is, as long as it has been sufficiently washed.

In order for the antimicrobial fiber product aimed at by the present invention to exhibit semi-permanent antimicrobial properties and to maintain good properties of each of the acetate fiber and the cotton fiber, the weight of the acetate fiber should be at least 5% by weight. , Preferably 10
It is preferred that 85% be mixed.

When the amount of the antibacterial acetate fiber is less than 5% by weight, the semi-permanent antibacterial effect is poor, and when the amount of the antibacterial acetate fiber is more than 85%, the antibacterial property of the textile product is sufficient, but the desirable properties of cotton fiber, wind Tend to be compromised.

In the fiber product of the present invention, other fibers such as polyester fiber and nylon fiber are used in addition to the above-mentioned antibacterial acetate fiber and cotton fiber as long as the intended performance is not impaired. You can also.

In the present invention, the fiber product may be in any form such as yarn (yarn), tape, ribbon, woven fabric, knitted fabric, non-woven fabric, etc., but is used in cotton like futon cotton, quilted cotton. You can also. When used in the form of a thread, it is used as a blended yarn, a plied yarn, a blended yarn, or the like. In the case of other textile products, besides using such blended yarns, ply-twisted yarns, and blended yarns, cotton yarn and antibacterial acetate fiber may be woven or knitted, and if used as cotton, After the antibacterial acetate long fibers are cut into short fibers (staple fibers), they are mixed with cotton for use. When the antibacterial acetate fiber is a long fiber (continuous filament), a so-called core-spun yarn in which the antibacterial acetate long fiber is covered with a cotton fiber may be used.

When the antibacterial acetate fiber and the cotton fiber are mixed at the yarn (yarn) production stage, they are blended in a short fiber state, or the cotton fiber yarn and the antibacterial acetate long fiber are twisted. Or core spun yarn. In the case of mixing at the weaving and knitting stages, the mixing can be carried out by weaving and knitting the yarn of antibacterial acetate fiber and the yarn of cotton fiber. Of course, two or more of the above mixing means can be used in combination. For example, a cotton / antibacterial acetate fiber blend spun yarn and a 100% cotton fiber yarn can be interwoven.

In any case, it is preferable to adjust the content of the antibacterial agent in all the fiber products to be 0.01 to 1% by weight.

The textile product of the present invention may be used in any field as long as it is required to have antibacterial properties. In particular, towels, mats, sheets, and the like, which can exert the effects of the present invention, may be mentioned. it can. This use is particularly preferable because not only the necessity of antibacterial is high, but also the frequency of washing is high, and since it comes into direct contact with the skin, a good feeling is required.

When manufacturing towels and mats, use cotton /
It is preferred to use a blend of antimicrobial acetate fibers. The whole may be composed of this blended yarn, or only the loop or pile portion may be composed of the blended yarn.

In addition, clothes for nursing or nursing care (eg, white coats for doctors and nurses, pajamas for patients, etc.), which are also strongly required for washing resistance and antibacterial properties, work clothes for beauty and barbers, Also suitable for working clothes in food processing plants. Furthermore, it can be used for clothing such as socks, underwear, pajamas and gowns, and also for filling cotton in futons and quilted clothing. Also,
It is also useful for sportswear linings, footwear underlays, hospital carpets, and the like.

The textile product of the present invention can further contain additives such as a deodorant, an ultraviolet ray inhibitor and an antistatic agent, if necessary. In this case, in addition to the original antibacterial properties, The above functions can be added.

[0038]

According to the present invention as described above, the metal (particularly silver) -containing phosphoric acid compound represented by the above formula [1] is combined with zinc oxide as an antibacterial agent to be present in the antibacterial acetate fiber. Surprisingly, the textile products used have a unique effect of increasing the antibacterial property by washing, and exhibit a special effect in the above-mentioned various applications such as towels and nursing clothes which are frequently washed.
At this time, when a cotton fiber is used in combination with the fiber other than the acetate fiber, the cotton fiber has excellent anti-bacterial properties for a long period of time without discoloring the good water absorption / moisture absorption and feeling of the cotton fiber, and has no discoloration. A semi-permanent antimicrobial fiber product is obtained.

[0039]

The present invention will be described more specifically with reference to the following examples. However, these examples are provided to facilitate understanding of the present invention, and the scope of the present invention is not limited by these descriptions. Unless otherwise specified, all “%” in Examples and Reference Examples are based on weight, and all quantitative ratios represent weight ratios.

[Examples 1-3, Comparative Examples 1-3] Degree of acetylation 5
When preparing a spinning dope by dissolving 5% of cellulose diacetate flakes in acetone, an antibacterial agent having a particle diameter of 0.3 to 0.5 μm comprising a zirconium phosphate ceramic having the following silver ions supported on the dope. (A) ~
(C) and siliconized particle size 0.015 to 0.035
μm of zinc oxide (ZnO) was mixed with cellulose diacetate at the ratios shown in Table 1 and extruded from a spinneret having 20 circular spinning nozzles into a spinning cylinder. It was dry-dried and dry-spun by drawing off with draft 1.1.

After crimping, the obtained antibacterial acetate fiber was cut into a fiber length of 25 mm to obtain a staple fiber short fiber.

This antibacterial acetate short fiber was washed well with rice cotton (average fiber length 1.5 inches) and acetate short fiber /
It was blended with rice cotton = 20/80 (weight ratio) to obtain a 18th white blended yarn.

An antibacterial test was carried out using this blended plain fabric (containing antibacterial agent A), and the results shown in Table 1 were obtained.

[0044] Antimicrobial _{agents: (A) Ag 0. 00 5} Li 0. 99 5 Zr 2 (PO 4) 3 (B) Ag 0. 01 (NH 4) 0. 99 Zr 2 (PO 4) 3 (C) _{Ag 0. 05 Na 0. 95 Zr 2} (PO 4) 3

[0045]

[Table 1]

The sterilization rate shown in Table 1 is the reduction rate (%) of Staphylococcus aureus by the shake flask method.

From the results shown in Table 1, it is found that the compound containing the composite of the antibacterial agent (A) and zinc oxide has good washing durability and discoloration resistance, especially after washing 10 times than before washing. It has been confirmed that the antibacterial effect has an extremely unique effect of improving the antibacterial performance. The feeling, water absorption and hygroscopicity were good before and after washing, substantially unchanged from those of 100% cotton.

Subsequently, the antibacterial agent (B) and the antibacterial agent (C)
A similar test was performed using each of the above, but almost the same results were obtained.

Example 4, Comparative Examples 4 to 5 The number of target bacteria was measured for the woven fabric (plain weave) made of the blended yarn shown in Example 2 and the cotton fabric (plain weave) treated with a known antibacterial agent. . Table 2 shows the results.

[0050]

[Table 2]

Example 5 Using the 18th-count blended yarn of Example 2, a loop (Single-
A toweling having a "loop" was produced, and an 18 inch wide antimicrobial towel was produced.

The towel was washed 40 times and dried under sunlight, but no change was observed in appearance and feeling.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kenkichi Nose 1-6-7 Minamihonmachi, Chuo-ku, Osaka-shi, Osaka Teijin Limited (72) Inventor Shiro Kumakawa 2-1-1 Uchisaiwaicho, Chiyoda-ku, Tokyo (56) References JP-A-3-227403 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D01F 2/28 A01N 59/26

Claims (8)

(57) [Claims] 1. An antibacterial cellulose acetate fiber, characterized in that the cellulose acetate fiber contains an antibacterial agent comprising a metal-containing phosphate compound and zinc oxide in an amount of 0.1 to 5% by weight based on the weight of the fiber. . 2. The antibacterial cellulose acetate fiber according to claim 1, wherein the metal-containing phosphate compound is at least one compound represented by the following formula [1]. Embedded image (M ¹ ) _a (A) _b (M ² ) _c (PO ₄ ) _d · nH ₂ O [1] wherein M ¹ is at least selected from silver, copper, zinc, tin or lead One kind of metal ion, A is an alkali metal ion,
At least one metal ion selected from the group consisting of alkaline earth metal ions and ammonium ions, M ² is a tetravalent metal, n is an integer of 0 to 6, ad is a positive number, and pa + qb = 1 When C = 2, d = 3, pa + qb =
In the case of 2, c = 1 and d = 2. Here, p is the valence of M ¹ and q is the valence of A. ] 3. a M ¹ in the formula [1] is silver,
A is an alkali metal ion or ammonium ion, M
^3. The antibacterial cellulose acetate fiber according to claim 2, wherein ² is zirconium, tin or titanium. 4. The method according to claim 1, wherein the ratio of the metal-containing phosphate compound to zinc oxide is 20/80 to 80/20 (weight ratio).
The antibacterial cellulose acetate fiber according to claim 3. 5. The antibacterial cellulose acetate fiber according to claim 1, wherein the antibacterial agent has an average particle size of 0.01 to 2 μm. 6. A antimicrobial fiber product of claim 1請
6. An antibacterial fiber product, wherein the antibacterial cellulose acetate fiber according to claim 5 is mixed in at least 5% by weight. 7. The antibacterial textile according to claim 6 , wherein the textile is an antibacterial towel or an antibacterial mat. 8. The antibacterial textile according to claim 6 , wherein the textile is a nursing garment.