JPH07189033A - Antimicrobial polyester fiber - Google Patents

Abstract

PURPOSE:To provide a white antimicrobial polyester fiber not requiring the limitation of an oiling agent when melt-spun, almost perfectly prevented in the coloration of the fiber with time, having a sufficiently antimicrobial property even before an alkali weight-reducing treatment, and further substantially perfectly prevented in the coloration of the fiber due to the alkali weight-reducing treatment. CONSTITUTION:The antimicrobial polyester fiber comprises a polyester in which at least 80mol.%m of the components composing the polyester comprises ethylene terephthalate units. The fiber contains both an antimicrobial agent A and an antimicrobial agent B in the total amount of 0.1-10wt.% within a wt.% ratio range satisfying an inequality: 0.02 S the wt.% of the antimicrobial agent A in the fiber/the wt.% of the antimicrobial agent B in the fiber <=2.5. The antimicrobial agent A comprises white phosphate salt particles or hydroxyapatite particles carrying 0.1-10wt.% of silver ions and having an average particle diameter of <=5mum. The antimicrobial agent B comprises white phosphate salt particles or hydroxyapatite particles having an average particle diameter of <=5mum and produced by carrying 0.1-10wt.% of silver ions and subsequently calcining at a higher temperature than the melting point of the silver.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial polyester fiber, and more particularly to a white antibacterial polyester fiber containing two specific types of white antibacterial agents in a specific ratio.

[0002]

2. Description of the Related Art Polyester fibers, especially polyethylene terephthalate, are widely used for clothing, industrial materials, bedding and the like because the fibers have excellent fiber performance such as heat resistance and chemical resistance. . In recent years, in these fiber applications, there is an increasing demand for fibers having antibacterial properties as one of the comfort functions.

Generally, as a method of imparting antibacterial properties to fibers, a method of adhering an aromatic halogen compound, an organic silicon quaternary ammonium salt, an organic nitrogen compound, etc. to the fibers is adopted. There is a problem with durability because it easily falls off when washed. Therefore, a polymer composition such as fiber containing zeolite particles carrying antibacterial metal ions such as silver ions as an antibacterial agent has been proposed (Japanese Patent Publication No. 63-54013). However, the fibers such as polyester to which these particles have been added and contained at the time of melt spinning are considerably colored, and there is a problem that the degree of coloring increases with time.

Phosphate particles or hydroxyapatite particles carrying antibacterial metal ions such as silver ions, or the like in order to prevent the above-mentioned coloring during the production of fibers and the subsequent increase in the degree of coloring over time. Polymer compositions such as fibers containing such particles have been proposed (JP-A-2-
96508, JP-A-2-180270, JP-A-3-
38504, JP-A-3-43457, and JP-A-3-8.
3905 etc.). Certainly, coloring during the production of fibers such as polyester containing white particles of these particles is almost completely prevented by devising the composition of the oil agent during melt spinning, and coloring over time is also almost complete. To be prevented.
However, in the case of polyester fiber, alkali weight reduction treatment is often carried out for the purpose of improving the texture, and although this weight reduction treatment hardly increases or decreases the antibacterial activity of the fiber, it is considerably colored, so the original color is restored. Therefore, it is necessary to perform further bleaching treatment, and in some cases, the original color may not be restored.

On the other hand, there have been proposed phosphate particles or hydroxyapatite particles which have been carried out at a temperature above the melting point (about 960 ° C.) of silver after supporting silver ions, or fibers containing such particles. (JP-A-3-2187
65, JP-A-4-13605, and JP-A-4-1633.
08, JP-A-4-170960, and JP-A-4-234.
303, JP-A-4-288006, etc.). Certainly, coloring during the production of fibers such as polyester containing white particles of these particles is almost completely prevented without limiting the composition of the oil agent during melt spinning, and coloring over time is also almost complete. In addition, the coloring by the above-mentioned weight reduction treatment which is often carried out in the case of polyester fiber is almost completely prevented. However, although this weight loss treatment significantly increases antibacterial properties, it is still inferior to that of polyester fibers containing phosphate particles or hydroxyapatite particles that have not been fired at a temperature above the melting point of silver.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to limit the composition of the oil during melt spinning, to prevent almost complete coloration over time, and to obtain sufficient antibacterial properties even before alkali reduction treatment. It is an object of the present invention to provide a white antibacterial polyester fiber which has properties and is almost completely prevented from being colored by alkali reduction treatment.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that polyester fibers containing two specific types of white antibacterial agents in specific weight percentages are melt-spun. There is no limitation on the composition of the oil agent at that time, and coloring over time is almost completely prevented, and it has sufficient antibacterial properties even before the alkali weight reduction treatment. Further, coloring due to the alkali weight reduction treatment is almost completely prevented. The inventors have found that they have excellent properties, and have completed the present invention. Note that the present inventors have considered that those having a sterilization rate of 80% or more by the shake flask method using Klebsiella pneumoniae described in Examples below have sufficient antibacterial properties.

That is, in the present invention, at least 80 mol% of the components constituting the polyester is ethylene terephthalate, and both of the following antibacterial agents A and B are within a weight% ratio satisfying the following general formula (1). Antibacterial polyester fiber containing 0.1 to 10% by weight Antibacterial agent A: White phosphate particles or hydroxyapatite particles having 0.1 to 10% by weight of silver ions and having an average particle diameter of 5 μm or less Antibacterial agent B: An average particle diameter of 5 μ, which was obtained by supporting 0.1 to 10% by weight of silver ions and then firing at a temperature equal to or higher than the melting point of silver.
White phosphate particles or hydroxyapatite particles having a particle size of m or less 0.02 ≦ weight% of antibacterial agent A in fibers / weight% of antibacterial agent B in fibers ≦ 2.5 ... Formula (1) It is about.

The polyester referred to in the present invention is so-called polyethylene terephthalate, in which terephthalic acid is the main dicarboxylic acid component, ethylene glycol is the main diol component, and at least 80 mol% of the components constituting the polyester are ethylene terephthalate. Is a polyester. Therefore, dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, cyclohexane-1,4-dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid, tetramethylene glycol, cyclohexane-1,4 A small amount of diol such as dimethanol, pentamethylene glycol and hexamethylene glycol may be copolymerized.

The antibacterial agent A used in the present invention is white phosphate particles or hydroxyapatite particles carrying 0.1 to 10% by weight of silver ions and having an average particle size of 5 μm or less. The average particle size needs to be 5 μm or less, preferably 2 μm or less. If the average particle diameter exceeds 5 μm, the dispersibility of the particles in the fiber becomes insufficient.
The antibacterial agent A must carry 0.1 to 10% by weight of silver ions, and 0.5 to 5% by weight is preferable. If the supported amount of silver ions is less than 0.1% by weight, the antibacterial property of the obtained fiber is not sufficient, and if it exceeds 10% by weight, the antibacterial property of the obtained fiber is saturated, which is not economical. Further, conventionally known methods for phosphate particles or hydroxyapatite particles,
For example, silver ions can be supported by the ion exchange method. The phosphate may be any white solid, and examples thereof include zirconium phosphate and tricalcium phosphate. Furthermore, it goes without saying that hydroxyapatite is a white solid.

The antibacterial agent B used in the present invention has a melting point of silver (approximately 96
(0 ° C.) or higher, preferably white phosphate particles or hydroxyapatite particles having an average particle size of 5 μm or less, which is calcined at a temperature of 1000 to 1200 ° C. The average particle size needs to be 5 μm or less, preferably 2 μm or less. If the average particle diameter exceeds 5 μm, the dispersibility of the particles in the fiber becomes insufficient. The antibacterial agent B is required to carry 0.1 to 10% by weight of silver, and
5 to 5% by weight is preferable. If the supported amount of silver is less than 0.1% by weight, the antibacterial property of the obtained fiber is not sufficient, and if it exceeds 10% by weight, the antibacterial property of the obtained fiber is saturated, which is not economical. Further, the phosphate particles or the hydroxyapatite particles may be loaded with silver ions by a conventionally known method, for example, an ion exchange method, and then fired at a temperature equal to or higher than the melting point of silver. By this calcination, all silver ions become metallic silver and / or silver oxide and are not eluted as silver ions. Incidentally, the phosphate may be any white solid as long as it is a white solid after supporting and firing silver ions, for example, zirconium phosphate,
Examples thereof include tricalcium phosphate. Furthermore, it goes without saying that hydroxyapatite is a white solid.

The antibacterial polyester fiber in the present invention contains the antibacterial agent A and the antibacterial agent B in an amount of 0.1 to 10 in the fiber.
It is necessary to contain it by weight%, and 0.5 to 5 weight% is preferable. If the total amount of the antibacterial agent A and the antibacterial agent B in the fiber is less than 0.1% by weight, the antibacterial property of the obtained fiber is not sufficient.
If it exceeds 0% by weight, the antibacterial property of the obtained fiber will be saturated, which is not economical.

The weight ratio of the antibacterial agent A to the antibacterial agent B in the fiber must be 0.02 to 2.5,
~ 2 is preferred. If the weight% ratio of both antibacterial agents is less than 0.02, the antibacterial properties of the obtained fibers before the alkali weight reduction treatment are not sufficient, and if the ratio exceeds 2.5, the obtained fibers are subjected to even a slight alkali weight reduction treatment. Color it just by doing it. When the weight% ratio is in the range of 0.02 to 2.5 of the present invention, almost no coloring occurs if the weight loss rate (weight% of the portion removed by the alkali weight loss treatment with respect to the entire original fiber) is several percent. When the ratio of the weight% is particularly large, the weight reduction rate is very large. For example, if the weight reduction rate is about 20% by weight, slight coloring may occur. Therefore, it is desirable to appropriately adjust the weight reduction rate.

When both antibacterial agents are added in the polyester polymerization step, they are already colored in the polymer stage before melt spinning, so it is necessary to add both antibacterial agents during melt spinning. Of course, both antibacterial agents can be used simultaneously or separately.
For example, master pellets containing 5 to 30% by weight may be prepared in advance and mixed and melt-spun with pellets containing no antibacterial agent, or particles of both antibacterial agents themselves may be mixed and melt-spun with pellets containing no antibacterial agent. Good. Whatever method is used for melt spinning, it is sufficient to use, as an oil agent for spinning, for example, a water-soluble oil agent for spinning ordinary polyester fibers for clothing, but of course other oil agents may be used.

Further, since it is considered that the antibacterial property mainly depends on the antibacterial agent in the vicinity of the fiber surface, it is possible to incorporate the antibacterial agent only in the sheath portion of the sheath-core type cross-section yarn by utilizing the known composite spinning technique. It is possible, and in that case, it is not necessary to include an antibacterial agent in the core, and the amount of the antibacterial agent added to the entire fiber can be small, which is economically advantageous and at the same time, changes in fiber characteristics are reduced. .

The antibacterial polyester fiber in the present invention may be a matting agent, a deodorizing agent, if it does not color the fiber.
Additives such as an ultraviolet absorber and a fluorescent whitening agent may be included depending on the purpose. The antibacterial polyester fiber of the present invention can also be used as a mixture or a composite with different kinds of fibers. For example, it is possible to obtain a fiber structure in which the feel and the function are widely changed by blending, blending, or weaving or knitting with a fiber having no antibacterial property.

[0017]

EXAMPLES Next, the method of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The reduced viscosity ηsp / C was measured in orthochlorophenol at 35 ° C and the concentration was 1% (g / ml). Also,
All evaluations of antibacterial properties were conducted by the Japan Chemical Fiber Testing Association by the shake flask method using Klebsiella pneumoniae, and the degree of antibacterial properties was indicated by the sterilization rate (%). As described above, the inventors of the present invention judged that the sterilization rate of 80% or more has sufficient antibacterial property.

[0018]

Reference Example A master pellet containing 20% by weight of the antibacterial agent A or B used in the examples was prepared as follows. Polyethylene terephthalate with ηsp / C = 0.78 and commercially available Novalon (a white zirconium phosphate inorganic antibacterial agent with a silver content of about 3.5% by weight manufactured by Toagosei Kagaku Kogyo Co., Ltd.) belonging to antibacterial agent A were used. A master pellet containing 20% by weight of Novalon was prepared by melt kneading, and further polyethylene terephthalate having ηsp / C = 0.78 and a commercially available apacider AW (silver manufactured by Sangi Co., Ltd.) belonging to the antibacterial agent B were used. A hydroxyapatite-based white inorganic antibacterial agent having a content of about 2% by weight was used to prepare a master pellet containing 20% by weight of Apacider AW by melt-kneading.

[0019]

Examples 1 to 7 Using polyethylene terephthalate with ηsp / C = 0.78, master pellets containing 20% by weight of Novalon and master pellets containing 20% by weight of Apacider AW, spinning temperature 290 ° C., spinning speed 1
The fiber was spun at 500 m / min and stretched at 120 ° C. so that the elongation was 25 to 30% to obtain an antibacterial agent-containing polyester fiber shown in Table 1. At this time, the oil agent used was the following water-soluble oil agent for spinning polyester fibers for clothing.

Water-soluble oil agent: aqueous solution of 10% by weight of oil agent Component of oil agent: octyl stearate 60% by weight castor oil ethylene oxide adduct 18% by weight oleyl alcohol ethylene oxide 5 mol adduct 12% by weight lauryl sulfonate sodium salt 10% by weight A part of the obtained polyester fiber containing an antibacterial agent was evaluated for antibacterial property after refining, and a part of it was further subjected to alkali reduction treatment after refining (boiling in a 4% aqueous solution of NaOH for 10 minutes: bath ratio =
After 1/50), the antibacterial properties were evaluated, and some of them were evaluated after 10 times of dyeing and washing. The results are shown in Table 2.

Scouring: Score roll [nonionic surfactant manufactured by Kao Corporation] 2 g / l 70 ° C. × 15 minutes Dyeing: Kayalon Polyester Blue 3R-SF [dye manufactured by Nippon Kayaku Co., Ltd.]
3% owf 130 ° C. × 30 minutes Reduction treatment conditions (80 ° C. × 20
Min) Sodium carbonate 2g / l Sodium hydrosulfite 2g / l Sanmor RC-700 2g / l [Nonionic surfactant manufactured by Nichika Chemical Co., Ltd.] Washing: temperature 40 ° C, bath ratio 1/30, detergent Monogen Uni (2g / l) main wash 5 minutes, rinse 2 minutes x 2 times,
Dehydration approximately 30 seconds (repeated 10 times)

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

Examples 8 to 11 In the same manner as in Examples 1 to 7, polyester fibers containing an antibacterial agent shown in Table 3 were obtained, and antibacterial properties were evaluated. The results are shown in Table 4.

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Comparative Examples 1 to 3]
An antibacterial agent-containing polyester fiber as described above was obtained, part of which was evaluated for antibacterial property after refining, and part of it was further subjected to alkali weight reduction treatment (boiling in a 4% aqueous solution of NaOH for 10 minutes: bath ratio = 1/50 ), The antibacterial properties were evaluated, and some of them were evaluated after 10 times of dyeing and washing. The results are shown in Table 6.

In some of the comparative examples, the following special components were added to the water-soluble oil agent in an amount of 0.5% by weight. Methylbenzotriazole potassium salt [Sumitomo Chemical Co., Ltd.]
Corrosion inhibitor made by Stabinol M-BTZ (K)]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Comparative Examples 4 to 9]
The polyester fiber containing the described antibacterial agent was obtained, and the antibacterial property was evaluated. The results are shown in Table 8.

[0032]

[Table 7]

[0033]

[Table 8]

[0034]

The antibacterial polyester fiber of the present invention is
It is a white fiber that is almost completely prevented from coloring over time, has sufficient antibacterial properties before and after alkali reduction treatment, and is also almost completely prevented from coloring due to alkali reduction treatment. Extremely high.

Claims (1)

[Claims] 1. At least 80 mol% of the components constituting the polyester is ethylene terephthalate, and both of the following antibacterial agents A and B are 0.1% by weight within the range of the weight ratio satisfying the following general formula (1). Antibacterial polyester fiber containing 10 to 10% by weight. Antibacterial agent A: 0.1 to 10% by weight of silver ions supported, white phosphate particles or hydroxyapatite particles having an average particle size of 5 μm or less Antibacterial agent B: 0.1 to 10% by weight of silver ions supported The average particle size after firing was 5 μm and the temperature was higher than the melting point of silver.
White phosphate particles or hydroxyapatite particles having a particle size of m or less 0.02 ≦ weight% of antibacterial agent A in fibers / weight% of antibacterial agent B in fibers ≦ 2.5 ... Formula (1)