JP2003268628A - Antibacterial polyester fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial polyester fiber usable for an alkali thinning use. <P>SOLUTION: This antibacterial polyester fiber is made of a polyethylene terephthalate containing ≥85 mol% ethylene terephthalate repeating unit, contains 0.3-5.0 wt.% phosphate-based antibacterial particles containing a metallic ion and has a residual elongation of 30-200%. <P>COPYRIGHT: (C)2003,JPO

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 capable of suppressing the loss of phosphate-based antibacterial particles containing a metal ion after alkali reduction and developing the use for alkali reduction.

[0002]

2. Description of the Related Art Since synthetic fibers such as polyester and nylon have excellent heat resistance and chemical resistance, they are widely used for clothing, industrial materials, bedding and the like. A large number of techniques have been disclosed for incorporating inorganic particles in order to increase the specific gravity, texture, and deodorization of these synthetic fibers. For example, Japanese Patent Application Laid-Open No. 64-40614 discloses a technique for polyester fiber containing condensed zirconium phosphate as a deodorant. In recent years, there has been an increasing demand for comfortable fibers having further antibacterial properties.

Generally, as a method of imparting antibacterial properties to fibers, a method of adhering aromatic halogen compounds, organic silicon quaternary ammonium salts, organic nitrogen compounds, etc. to fibers is adopted, but these compounds are washed. There is a problem in durability because it easily falls off due to such reasons. Therefore, a method of precipitating a metal salt by irradiating a base material to which a silver compound is attached as an antibacterial agent (JP-A-50-6717), a metal such as gold, silver, copper and oxide particles thereof are used as a fiber. A method of fixing to the surface (JP-A-54-82500) has been proposed. However, these particles are not only expensive, but the particles fall off, or the particles themselves are colored, resulting in undesired coloring of the product, or the particles have a large specific gravity so that the particles settle out when attempting to blend them into the resin. There was a problem such as poor moldability.

Japanese Unexamined Patent Publication (Kokai) No. 3-43457 discloses a technique of incorporating phosphate-based antibacterial particles into a resin. Further, JP-A-3-83905 and JP-A-3-83905.
JP-A-83906 discloses a phosphate-based antibacterial particle, and the above-mentioned problems such as coloring have been solved for the time being. However, the antibacterial polyester fiber that is melt-spun by blending these antibacterial particles has low crystallinity around the antibacterial particles, and when the alkali amount is reduced, it is eroded from the polyester around the antibacterial particles and the amount is reduced, There is a problem that the antibacterial particles fall off, and the performance remarkably deteriorates or the performance is lost.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, suppresses the loss of phosphate-based antibacterial particles containing metal ions after alkali reduction, and has antibacterial properties that can be applied to alkali reduction applications. It relates to polyester fibers.

[0006]

Means for Solving the Problems As a result of earnest studies for solving the above problems, in polyethylene terephthalate fiber having an ethylene terephthalate repeating unit of 85 mol% or more, the phosphate-based antibacterial particles containing a metal ion are 3 to 5.0% by weight and residual elongation of 30 to
The object of the present invention can be achieved by the antibacterial polyester fiber characterized by being 200%.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The antibacterial polyester fiber of the present invention comprises 0.3 to 5.0 phosphate-based antibacterial particles containing metal ions.
Must be contained by weight percent. If the content of the phosphate-based antibacterial particles containing metal ions is 0.3% or more, stable antibacterial performance can be obtained, while if it is 5.0% by weight or less, stable yarn production can be performed. More preferably, it is 1.0 to 3.0% by weight.

The phosphate-based antibacterial particles containing metal ions of the present invention preferably have an average secondary particle size of 0.5 μm or less in terms of process stability such as filtration layer exchange period and thread breakage. . More preferably, it is 0.3 μm or less. Examples of the metal ion in the phosphate-based antibacterial particle containing the metal ion of the present invention include silver, copper, zinc, gold and platinum. From the viewpoint of antibacterial performance and cost, silver ion is preferable. Further, the content of the metal ion is preferably 0.1% by weight or more from the viewpoint of stable bacteriostatic performance, and is preferably less than 20% by weight in order to suppress coloring of the raw yarn.

The phosphate antibacterial particles are made of Ca ₃ (P
O ₄ ) ₂ , Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , Ca ₂ P ₂ O _{7 and} other calcium phosphate-based particles, HZr ₂ (PO ₄ ) ₃ , LiZ
r ₂ (PO ₄ ) ₃ , H _X Li _1-X Zr ₂ (PO ₄ ) ₃ (0 <X <
1), Zr (HPO ₄ ) ₂ , and zirconium phosphate-based particles such as NaZr ₂ P ₃ O ₁₂ . Of course, these particles may contain some water of crystallization. It is preferable to use zirconium phosphate-based particles as the phosphate-based antibacterial particles because the antibacterial property is highest and the effect of the present invention can be best exhibited.

The metal ion can be added to the particles by a conventionally known method, but an ion exchange method and a coprecipitation method, which are simple methods, are preferable.

It is necessary that the residual elongation of the antibacterial polyester fiber of the present invention is 30 to 200%. If the residual elongation is 200% or less, the promotion of crystallinity of the antibacterial polyester around the metal salt-containing phosphate-based antibacterial particles in the stretching or false-twisting step can be relaxed, and the antibacterial effect during alkali weight reduction treatment can be reduced. Since the erosion / weight loss state of the water-soluble polyester fiber becomes uniform, the holding power of the phosphate-based antibacterial particles containing metal ions can be improved. From the viewpoint of the holding power of the phosphate-based antibacterial particles containing metal ions, the residual elongation of the antibacterial polyester fiber needs to be 30% or more in terms of the stability of spinning. More preferably, it is 40 to 180%.

The cross-sectional shape of the antibacterial polyester fiber of the present invention is not particularly limited, and may have a modified cross-section other than the round cross-section. Atypical cross-section gives glossiness by three-leaf cross-section, water absorption and quick-drying performance by multi-leaf cross-section of four or more leaves, and functionality such as firmness, heat retention and lightweight feeling by hollow cross-section. You can

Further, the polyester component used in the antibacterial polyester fiber of the present invention may contain isophthalic acid, 2,2-bis {4-, if necessary, as long as the object of the present invention is not impaired.
A copolymerization component such as (β-hydroxyethoxy) phenyl} propane, a matting agent such as titanium oxide, an antioxidant such as a hindered phenol compound, and other inorganic particles may also be included. The polyester in the present invention needs to be polyethylene terephthalate having an ethylene terephthalate repeating unit content of 85 mol% or more. Since polyethylene terephthalate accounts for 85 mol% or more, the heat resistance becomes good and stable yarn production can be performed.

The antibacterial polyester fiber of the present invention is a polyester component (A) which is a polyethylene terephthalate containing 85 mol% or more of ethylene terephthalate repeating units.
10 to 5 phosphate-based antibacterial particles containing metal ions
It is preferable that the antibacterial polyester component (B) containing 0% by weight is melt-measured and then melt-blended. When the phosphate-based antibacterial particles containing a metal ion in the antibacterial polyester component (B) is less than 50% by weight, the phosphate-based antibacterial particles containing a metal ion and the polyester component (B) are formed by the polyester component. 2 in kneading and manufacturing process
Secondary aggregation can be suppressed. On the other hand, when the phosphate-based antibacterial particles containing metal ions in the antibacterial polyester component (B) is 10% by weight or more, the processing cost at the time of kneading becomes low, and the raw yarn can be provided at low cost. .
In addition, in the method for producing the present yarn, it is preferable that the polyester component (A) and the antibacterial polyester component (B) containing the phosphate antibacterial particles containing metal ions are melt-measured and then melt-blended. Phosphate-based antibacterial particles containing metal ions can be uniformly dispersed in the fiber, and variations in quality such as antibacterial performance and other physical properties of the raw yarn can be suppressed.

The melt-blending of the present invention can be carried out by utilizing a known technique, such as a method in which a static mixer is installed in an extruder or a pack for blending.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods in the examples are as follows.

1. Spinnability was continuously spun for 168 hours, and spinnability was determined according to the following judgment method. ◯: Thread breakage rate is less than 3.0% ○: Thread breakage rate is 3.0% or more and less than 6.0% Δ: Thread breakage rate is 6.0% or more and less than 10.0% ×: Thread breakage rate is 10.0% or more-: Not evaluated 2. The antibacterial activity bactericidal activity value (-) is in accordance with the unified test method (JISL 1902-1998) defined by the New Textile Product Evaluation Council,
The number of Staphylococcus aureus inoculated by the bacterial transcription method was evaluated using the following formula (1), and the antibacterial performance and the performance variation were evaluated by the average value.

(1) Antibacterial performance was measured 10 times and evaluated as an average value. Bactericidal activity value (−) = log A / B (1) where A is the number of inhabiting bacteria (particles / cm ² ) immediately after planting on the particle-free polyester fiber, and B is the antibacterial property of this example. Number of inhabiting bacteria after 18-hour culturing on polyester fiber (cells / cm ² ) ◯: Bactericidal activity value is less than −1.0 ○: Bactericidal activity value is −1.0 or more and less than 0.0 ×: Bactericidal activity value Is 0.0 or more. (2) Evaluation of performance variation is 1 out of 9 samples in the same test as in (1) above.
If the sample also had a value of 0.0 or more, it was determined to be unacceptable. ○: Pass ×: Fail 3. The overall evaluation of the uniformity of surface quality mainly on the color tone and dyeing spots by the product texture hunter method was evaluated by five skilled persons by a four-level judgment method. ○○: Excellent ○: Good △: Acceptable ×: Not acceptable 4. The intrinsic viscosity is a value measured in 25 ° C. orthochlorophenol.
Hereinafter referred to as IV.

Example 1 Polyethylene terephthalate (IV = 0.65) consisting of 100% polyethylene terephthalate (PET) as the polyester component (A) was used as the antimicrobial polyester component (B) under the conditions of spinning temperature of 290 ° C. and silver-supported phosphoric acid. IV = 0.0 made of polyethylene terephthalate containing 30% by weight of zirconium particles “NOVALON” (manufactured by Toagosei Co., Ltd., average particle size 0.5 μm, silver content 3.5% by weight).
Polyethylene terephthalate of 65 has a composite ratio of polyester component (A) / antibacterial polyester component (B) =
Each is melted and weighed to be 90/10, and the total discharge amount is 45g
/ Min of molten polymer is melt-blended in a pack with a static mixer and then a 36-hole nozzle (φ
0.28 mm) and spun at a spinning speed of 3000 m / min, 150 dtex-36 filament, residual elongation 1
A 60% semi-drawn yarn was obtained. The obtained semi-stretched yarn was stretch-heat set at a stretching temperature of 90 ° C., a heat setting temperature of 145 ° C. and a draw ratio of 1.8 times to obtain a stretched yarn of 84 dtex-36 filament. The drawn yarn thus obtained is used as the warp and the weft, and the greige density is 5
A plain woven fabric of 4 × 57 pieces / in was obtained, and after scouring, alkali reduction treatment was carried out at 80 ° C. for 30 minutes under the condition of alkali concentration of 2 g / l, and the bath ratio was disperse dye / dyeing solution = 1 /
Dyeing was carried out under the conditions of 20 at 130 ° C. for 60 minutes. At the same time, a particle-free polyester was used as the polyester component (B) to obtain a blank polyester fiber cloth for evaluation in the same manner. The woven fabric containing silver-supported zirconium phosphate particles in an amount of 3.0% by weight in the antibacterial polyester fiber (level 1) has silver-supported zirconium phosphate particles uniformly and appropriately dispersed in the antibacterial polyester fiber. It had the desired antibacterial performance and product texture, and was extremely excellent in uniformity.

Levels 2 to 4 are experiments in which the addition amount of silver-supported zirconium phosphate particles in the antibacterial polyester component (B) was changed based on the conditions of level 1.

Levels 2 and 3 are experiments in which the addition amounts of silver-supported zirconium phosphate particles in the antibacterial polyester component (B) were changed to 10% by weight and 50% by weight, respectively. However, the quality and quality of the product were the same as those of Level 1.

Level 4 is the addition amount of silver-supported zirconium phosphate particles in the antibacterial polyester component (B) is 60% by weight.
However, the silver-carrying zirconium phosphate particles in the antibacterial polyester component (B) were secondarily aggregated, and due to the influence, the filter layer exchange period was extremely short and yarn breakage occurred frequently. Further, the silver-supported zirconium phosphate particles were partially trapped in the filtration layer due to the secondary agglomeration, the particles were poor in uniform dispersibility, and the antibacterial performance varied greatly. The evaluation results are shown in Table 1.

[0024]

[Table 1] Example 2 Based on the level 1 spinning conditions, the composite ratio was changed while the addition amount of silver-supported zirconium phosphate particles in the antibacterial polyester component (B) was kept constant to obtain levels 5 to 8.

Levels 5 and 6 are experiments in which the amounts of silver-loaded zirconium phosphate particles added to the antibacterial polyester fiber were changed to 0.3% by weight and 5.0% by weight, respectively. And had antibacterial performance satisfying the present invention.

Level 7 is an experiment in which the addition amount of silver-supported zirconium phosphate particles in the antibacterial polyester fiber was 0.2% by weight. However, since the addition amount of silver-supported zirconium phosphate particles was too low, absolutely. The bactericidal activity value was low and below the antibacterial standard value.

Level 8 is an experiment in which the addition amount of silver-supported zirconium phosphate particles in the antibacterial polyester fiber was 6.0% by weight. However, since the addition amount of silver-supported zirconium phosphate particles was too large, the spinning process was performed. On the other hand, the yarn dischargeability was poor and the yarn was frequently broken. Further, many fluffs were generated at the stage of the raw yarn, and the obtained cloth had large dyeing spots and tissue spots. The evaluation results are shown in Table 2.

[0028]

[Table 2] Example 3 Level 9 is an experiment in which the blending method was changed to a chip blending method based on the level 1 yarn making conditions. However, the polyester component (A) and the antibacterial polyester component (B) containing silver-supported zirconium phosphate particles were used. Since the chip specific gravities of (1) and (2) were significantly different, the uniformity of the composite blended state of the obtained yarn was slightly lowered, but satisfactory antibacterial performance was obtained. The evaluation results are shown in Table 3.

[0029]

[Table 3] Example 4 Levels 10 to 13 are experiments in which the spinning speed was changed and the residual elongation was changed based on the spinning conditions of level 1.

Levels 10 and 11 were experiments in which the spinning speeds were changed to 2500 m / min and 6000 m / min, respectively, and the residual elongations were set to 190% and 35%, respectively. Was excellent.

Level 12 is an experiment in which the spinning speed was changed to 2000 m / min and the residual elongation was set to 205%. As a result of the high residual elongation, a high draw ratio was carried out. The antibacterial polyester component around the silver-supported zirconium phosphate particles was largely eroded / reduced, the silver-supported zirconium phosphate particles on the surface of the antibacterial polyester fiber fell off, and the antibacterial performance was much lower than the standard value.

Level 13 is an experiment in which the spinning speed was changed to 7,000 m / min and the residual elongation was 27%. However, the spinning speed exceeded the limit of the spinnability of the discharged yarn, and the yarn was frequently broken. did. The evaluation results are shown in Table 4.

[0033]

[Table 4]

[0034]

INDUSTRIAL APPLICABILITY The present invention suppresses the removal of phosphate-based antibacterial particles containing metal ions after alkali reduction in the antibacterial polyester fiber, and enables the development of alkali weight reduction applications which have been difficult to develop in the past. did.

Continued front page    F term (reference) 4J002 CF061 DH046 FD206 GK00                 4L035 BB33 BB34 EE11 JJ05

Claims (2)

[Claims] 1. An ethylene terephthalate repeating unit is 8 units.
In 5% by mole or more of polyethylene terephthalate fiber, 0.3% of phosphate-based antibacterial particles containing metal ions was used.
~ 5.0% by weight, residual elongation is 30 to 200%, antibacterial polyester fiber. 2. An ethylene terephthalate repeating unit is 8 units.
After melt-weighing each of the polyester component (A) which is 5% by mole or more of polyethylene terephthalate and the antibacterial polyester component (B) containing 10 to 50% by weight of the phosphate-based antibacterial particles containing metal ions, the metal ion is added. In-fiber weight ratio of phosphate-based antibacterial particles containing 0.3-
Melt-blend to 5.0 wt% and spin at 250
A method for producing an antibacterial polyester fiber, which comprises spinning at 0 to 6000 m / min.