JPH11189919A - Antimicrobial polypropylene terephthalate fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene terephthalate fiber having durable antimicrobial activity and excellent stretchability, and excellent in elastic recovery. SOLUTION: An antimicrobial polypropylene terephthalate fiber carrying at least one kind of metal ion selected from silver, copper, zinc and platinum in an amount of 0.1-20 wt.%, containing phosphoric salt particles having an average particle diameter of <=10 μm in an amount of 0.01-20 wt.% in the fiber, having a Young's modulus of the fiber of <=30 g/d and a stretch recovery of >=90% at 10% stretch. This antimicrobial polypropylene terephthalate fiber is suitable for the application to an inner which especially requires stretchability and cleanness.

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 fiber containing phosphate particles having an antibacterial action, and having a Young's modulus of 30 g / d or less and an elongation recovery at 10% elongation. And 90% or more, and relates to an antibacterial polypropylene terephthalate fiber suitable for inner use requiring cleanliness and stretchability.

[0002]

2. Description of the Related Art Synthetic fibers such as polyester, nylon, and acrylic have excellent properties such as heat resistance and chemical resistance, and are therefore widely used in applications such as clothing, industrial materials, and bedding.

[0003] In recent years, in these fiber applications, there has been an increasing demand for fibers provided with antibacterial properties as one of the comfort functions. Among them, the inner use is an application that requires particularly antibacterial properties because it comes into direct contact with the skin. However, at present, there is no fiber that has stretchability and weather resistance as well as antibacterial properties.

[0004] Generally, as a method for imparting antibacterial properties to fibers, a method of adhering an aromatic halogen compound, an organic silicon-based quaternary ammonium salt, an organic nitrogen compound, or the like to the fibers has been adopted. There is a problem in durability because it easily falls off due to washing or the like. Therefore, SiO ₂ / which carries silver, copper and zinc ions as antibacterial agents
Al ₂ O ₃ molar ratio is 14 or less, specific surface area is 150 m ² /
g of a resin containing zeolite particles of
No. 9-133235) has been proposed. This resin has excellent antibacterial effect durability. However, since these particles easily absorb moisture, foaming occurs when the particles are blended with the resin, and even after blending with the resin, the particles are easily adsorbed by moisture, so that the moldability is reduced. There was a problem of coloring. Therefore, a method of improving the moldability of the resin by coating the zeolite particles with a liquid paraffin, a silicone-based coating agent or a fluororesin and subjecting the zeolite particles to a hydrophobizing treatment (Japanese Patent Laid-Open No.
JP-A-7-746, JP-A-62-7747, JP-A-62-7748) and a method of blending a zeolite particle holding metal ions and ammonium ions with a discoloration inhibitor (JP-A-63-265958). Gazette) has been proposed. However, these improvement effects were hardly sufficient, and the polymer used in these applications was mainly polyethylene terephthalate, and the stretchability was poor.

[0005]

SUMMARY OF THE INVENTION The present inventors have no disadvantages of the above-mentioned conventional method, have a durable antibacterial action,
As a result of studying for the purpose of providing a fiber having excellent elastic recovery properties with excellent stretchability, a metal ion having an antibacterial property to phosphate particles having an average particle size in a specific range in polypropylene terephthalate fiber And a specific amount of the phosphate particles are blended, and the Young's modulus of the fiber is 30 g / d or less, and the elongation recovery at 10% elongation is 90% or more.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is that at least one metal ion selected from silver, copper, zinc, gold and platinum is supported in an amount of 0.1 to 20% by weight, and the average particle Phosphate particles having a diameter of 10 μm or less,
It can be achieved by an antibacterial polypropylene terephthalate fiber containing 0.01 to 20% by weight of the fiber, having a Young's modulus of the fiber of 30 g / d or less and an elongation recovery at 90% or more at 10% elongation. it can.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The phosphate particles used in the present invention must have an average particle diameter of 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less.
When the average particle diameter exceeds 10 μm, the dispersibility of the phosphate particles in the resin is insufficient, so that the moldability of the obtained resin is reduced or the strength of the resin is reduced due to defects in fibers. In some cases, thread breakage is likely to occur.

The specific surface area of the phosphate particles is 3 m ² /
g or more, more preferably 10 m ² / g or more.
When the specific surface area is less than 3 m ² / g, the amount of metal ions carried by the phosphate particles decreases, and the antibacterial effect of the obtained resin tends to decrease, which is not preferable.

The phosphate particles used in the present invention are silver, copper,
0.1 to metal ions selected from zinc, gold and platinum
20% by weight, preferably 0.3%
-15% by weight, more preferably 0.5-12% by weight. When the supported amount of metal ions is less than 0.1% by weight, the antibacterial effect of the obtained resin is not sufficient, and when it exceeds 20% by weight, the antibacterial effect of the obtained resin is saturated, which is not economical. The phosphate particles can be loaded with the above-mentioned metal ions by a conventionally known method, for example, an ion exchange method or a coprecipitation method, and an ion exchange method which is a simple method is preferable.

As a specific example of the phosphate particles, Ca ₃
(PO ₄ ) ₂ , Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , Ca ₂ P ₂
O ₇ , Ca ₁₀ (PO ₄ ) ₆ F ₂ , Ca ₁₀ (PO ₄ ) ₆ Cl ₂
, A magnesium phosphate compound such as Mg ₃ (PO ₄ ) _{2, a} strontium phosphate compound such as Sr ₃ (PO ₄ ) _{2, and a} barium phosphate compound such as Ba ₃ (PO ₄ ) ₂ , Ti (HPO ₄ ) _{2 and} other titanium phosphate compounds, Zr (HPO ₄ ) ₂ , NaZr ₂ P ₃
Zirconium phosphate compounds such as O ₁₂ , Sn (HP
Tin phosphate compounds such as O ₄ ) _2, hafnium phosphate compounds such as Hf (HPO ₄ ) ₂ , AlPO ₄ , Al (H ₂
Aluminum phosphate-based compounds such as PO ₄ ) ₂ , FePO ₄
And the like, and may be crystalline or amorphous, and may be a natural product or a synthetic product, but a synthetic product because uniform quality particles can be obtained. Is preferred.

In order to carry the metal ions on the phosphate particles by an ion exchange method or the like, Li,
The structure preferably includes an alkali metal ion such as Na or K or an H ion. The phosphate may contain water of crystallization.

In addition, calcium phosphate-based compounds, magnesium phosphate-based compounds and aluminum phosphate-based compounds are preferred from the viewpoint of good ability to carry metal ions,
Calcium phosphate compounds are more preferred, and Ca ₃ (P
O ₄ ) ₂ is more preferred.

Zirconium phosphate compounds are particularly preferred from the viewpoint of exhibiting high antibacterial properties with a small amount of metal ions carried.

The phosphate particles used in the present invention may carry other ions, such as ammonium ions, depending on the purpose, in addition to the specific metal ions described above. Further, the obtained antibacterial resin may contain two or more kinds of phosphate particles carrying different ion species and / or two or more kinds of phosphate particles having different ion holding amounts.

The antibacterial polypropylene terephthalate fiber in the present invention must contain 0.01 to 20% by weight of the above specified phosphate particles in the fiber, preferably 0.05 to 15% by weight. More preferably 0.1
-10% by weight. If the content of the phosphate particles in the fiber is less than 0.01% by weight, the antibacterial effect becomes insufficient, and if it exceeds 20% by weight, the antibacterial effect becomes saturated, which is not economical. Thread breakage may easily occur. Phosphoric acid particles can be blended with polypropylene terephthalate in any manufacturing process.

The antibacterial polypropylene terephthalate fiber of the present invention has a Young's modulus of 30 g / d or less,
It is necessary to simultaneously satisfy that the elastic recovery rate at% elongation is 90% or more. If the Young's modulus exceeds 35 g / d, the softness of the hand, which is a feature of the present invention, is lost, and it is preferably 20 to 30 g / d. further,
If the elastic recovery at 10% elongation is less than 80%, the stretchability is lacking. Preferably it is 90% or more.

The antibacterial polypropylene terephthalate fiber of the present invention may be a core / sheath composite fiber if the specified phosphate particles are contained in an amount of 0.01 to 20% by weight based on the fiber. The antibacterial fiber is gentle to the skin by preventing the particles from jumping out to the surface by incorporating the above specified phosphate particles in the core component in an amount of 0.01 to 20% by weight based on the core-sheath composite yarn. Also, in order to obtain a better antibacterial effect, the above-mentioned specified phosphate particles are used as a sheath component in an amount of 0.01 to the core-sheath composite yarn.
It is also preferred that the content be contained so as to be 20% by weight.
Even in this case, it is preferable that both the core and sheath polymer be polypropylene terephthalate in order to provide a soft feeling and a stretch property which are features of the present invention.

The polypropylene terephthalate of the present invention is a polyester obtained by using terephthalic acid as a main acid component and 1,3 propanediol as a main glycol component. However, 20 mol%, more preferably 1 mol%
It may contain a copolymer component capable of forming another ester bond in a proportion of 0 mol% or less. As copolymerizable compounds, for example, dicarboxylic acids such as isophthalic acid, succinic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, and sebacic acid; on the other hand, as glycol components, for example, ethylene glycol, diethylene glycol, butanediol, neopentyl glycol, Examples thereof include, but are not limited to, cyclohexanedimethanol, polyethylene glycol, and polypropylene glycol.

Also, matting agents, deodorants, coloring agents, ultraviolet absorbers, infrared absorbers, flame retardants, fluorescent brighteners, other ion adsorbents, other antibacterial agents, silica and alumina as lubricants Fine particles, hindered phenol derivatives as antioxidants,
A coloring pigment or the like can be added as needed.

The antibacterial polypropylene terephthalate fiber obtained in the present invention has not only antibacterial properties but also good stretchability, elastic recovery properties, deodorant properties and freshness retention properties. In addition to inner uses, it can be widely used as clothing materials such as futon and socks, and industrial materials such as hospital curtains and carpets. Further, since the fiber structure is used, the surface area is increased, and an effect of exhibiting an antibacterial property is higher than that of a resin.

The antibacterial polypropylene terephthalate fiber of the present invention may be used not only alone, but also as a mixture of fibers, or interwoven, interwoven or knitted.

[0022]

The present invention will be described in detail below with reference to examples. In addition, each characteristic value in an Example was calculated | required according to the following method.

(A) Average particle diameter of particles: Determined by an electron micrograph of the particles.

(B) Carrying amount of metal ion on particles: Quantified by atomic absorption method.

(D) Evaluation of antibacterial activity of tubular knitted fabric: A suspension buffer of a test bacterium (Escherichia coil NIHJ or Staphylococcus aereus IFO12732) was poured into the tubular knitted fabric, and 150 times in a closed container. The number of viable cells after shaking per minute for 1 hour was counted, and the reduction rate with respect to the number of cells in the poured suspension was determined (shake flask method).

Example 1 100 parts by weight of Ca ₃ (PO ₄ ) ₂ particles were added in an amount of 0.05 mol / l.
And stirred at room temperature for 2 hours. The particles separated by centrifugation are filtered on a filter paper for 50 minutes.
By slowly adding 00 parts by weight of deionized water, metal ions physically adsorbed on the particle surface were completely washed away. The obtained particles were vacuum-dried at 150 ° C. for 15 hours to obtain Ca ₃ (P) carrying 2.1% by weight of silver ions.
O ₄ ) ₂ (average particle diameter 0.7 μm) particles were obtained.

On the other hand, dimethyl terephthalic acid 19.4k
g, 15.3 kg of 1,3-propanediol, using tetrabutyl titanate as a catalyst, 140 ° C. to 230 ° C.
After the transesterification reaction was carried out while distilling off methanol at, polymerization was further carried out for 3 hours at a constant temperature of 250 ° C. to obtain a polypropylene terephthalate having an intrinsic viscosity [η] of 0.89.

30 parts by weight of the particles and 9
When 70 parts by weight of polypropylene terephthalate was mixed with an extruder, polypropylene terephthalate pellets containing 3.0% by weight of particles could be obtained without foaming.

The pellets were spun by a usual melt spinning method at a spinning temperature of 260 ° C. using a die having a hole diameter of 0.3 mm × 24 holes at a spinning take-off speed of 1800 m / min to obtain an undrawn yarn. The obtained undrawn yarn was stretched at 1 HR 60 ° C., 2 HR 90 ° C. and a draw ratio of 3 using a normal hot roll drawing machine.
The film was drawn at a draw ratio of 1 to obtain a drawn yarn of 75 denier and 24 filaments. The physical properties of the drawn yarn are as follows: Young's modulus 28.5 g / d, 10
% Elongation recovery rate was 98.6%, which had both soft texture and stretchability.

[0030] The antibacterial properties of the stretched yarn obtained by knitting it by tubular knitting and by washing it 100 times were evaluated.

The reduction rate of the number of bacteria was 99.9% for Escherichia coli and 97.2 for Staphylococcus aureus in the sample after scouring.
%, 98.8% against Escherichia coli and 93.1% against Staphylococcus aureus in the sample after washing, indicating that all samples have excellent antibacterial effects.

Examples 2 to 7, Comparative Examples 1 and 2 Using various phosphate particles, the same operation as in Example 1 was carried out to prepare phosphate particles having different silver ion carrying amounts and average particle diameters. This was blended with the polypropylene terephthalate polymerized in Example 1. Next, a drawn yarn was prepared in the same manner as in Example 1, and the drawn yarn was knitted in a tube to evaluate antibacterial properties. Table 1 shows the evaluation results of physical properties and antibacterial properties of the fibers.

[0033]

[Table 1] Regarding Examples 2 to 7, any of the phosphate particles exhibited high antibacterial properties and was excellent in soft feeling and stretchability. In particular, when the zirconium phosphate salt is used as in Examples 5 to 7, the particles have high antibacterial properties before and after washing as well as before washing when the loading amount is about the same as that of particles of other compositions.

Comparative Example 3 Particles were blended in the same manner as in Example 1 except that polyethylene terephthalate was used as a polymer to obtain polyethylene terephthalate pellets. The pellets were obtained by a usual melt spinning method at a spinning temperature of 290 ° C. and a pore diameter of 0.3 mm ×
Using a 24-hole die, spinning was performed at a spinning take-off speed of 1800 m / min to obtain an undrawn yarn. The obtained undrawn yarn was subjected to 1 HR 85 ° C., 2 HR 1
Drawing was performed at 30 ° C. and a drawing ratio of 2.4 to obtain a drawn yarn of 75 denier and 24 filaments. It was knitted in a tube and evaluated for antibacterial properties. The rate of decrease in the number of bacteria was 97.6% for E. coli, 93.6% for Staphylococcus aureus, and
The sample after washing had 92.7% against Escherichia coli and 90.5% against Staphylococcus aureus. Each of the samples had an excellent antibacterial effect, but had a Young's modulus of 95.2 g /
d, and 10% elongation recovery is as low as 48.5%.
It lacked softness and stretch.

Example 8 60 parts by weight of the Ca ₃ (PO ₄ ) ₂ particles holding silver ions obtained in Example 1 and 940 parts by weight of polypropylene terephthalate were mixed by an extruder. Was obtained in 6.0% by weight.

Using these pellets as the core component and polypropylene terephthalate containing no particles as the sheath component, using a composite spinning machine and feeding them from separate hoppers, the composite ratio of core to sheath at a spinning temperature of 260 ° C. A 50:50 (weight ratio) core-sheath composite yarn was spun at a spinning take-off speed of 1800 m / min. The obtained undrawn yarn was stretched at 1 HR 60 ° C., 2 HR 90 ° C. and a draw ratio of 3.1 using a usual hot roll drawing machine.
The film was drawn by a factor of 2 to obtain a drawn yarn of 75 denier and 24 filaments. The physical properties of the drawn yarn are Young's modulus 32.5 g / d, 10%
Elongation recovery rate was 95.3%, soft texture and stretchability.

The drawn yarn was knitted in a tubular knit and scoured and further washed 100 times, and the antibacterial property was evaluated.

The rate of decrease in the number of bacteria was 96.5% for E. coli and 93.2 for Staphylococcus aureus in the sample after scouring.
%, 92.6% against Escherichia coli and 90.8% against Staphylococcus aureus in the sample after washing, indicating that the sample has an excellent antibacterial effect.

Example 9 60 parts by weight of the Ca ₃ (PO ₄ ) ₂ particles holding silver ions obtained in Example 1 and 940 parts by weight of polypropylene terephthalate were mixed by an extruder. Was obtained in 6.0% by weight.

The pellets were used as a sheath component, and polypropylene terephthalate containing no particles was used as a core component. A composite spinning machine was used to supply the pellets from separate hoppers. A 50:50 (weight ratio) core-sheath composite yarn was spun at a spinning take-off speed of 1800 m / min. The obtained undrawn yarn was stretched at 1 HR 60 ° C., 2 HR 90 ° C. and a draw ratio of 3.1 using a usual hot roll drawing machine.
The film was drawn by a factor of 2 to obtain a drawn yarn of 75 denier and 24 filaments. The physical properties of the drawn yarn are Young's modulus 32.3 g / d, 10%
The elongation recovery rate was 95.5%, and it had a soft texture and stretchability.

The antibacterial properties of the stretched yarn obtained by knitting it by tubular knitting and washing it 100 times were evaluated.

The rate of decrease in the number of bacteria was 98.5% for E. coli and 95.4 for Staphylococcus aureus in the sample after scouring.
%, 94.3% against Escherichia coli, and 91.8% against Staphylococcus aureus in the sample after washing, indicating an excellent antibacterial effect.

[0043]

The antibacterial polypropylene terephthalate fiber obtained by the present invention has not only antibacterial properties but also good stretchability, elastic recovery, deodorant properties and freshness retention properties. In addition to the inner use, it can be widely used as clothing materials such as futon cotton and socks, and industrial materials such as hospital curtains and carpets. Furthermore, since the fiber structure is used, the surface area is increased, and the effect of expressing antibacterial properties is higher than when the resin is used.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI D01F 1/10 D01F 1/10 8/14 8/14 Z

Claims (3)

[Claims] 1. A phosphate particle carrying 0.1 to 20% by weight of at least one metal ion selected from silver, copper, zinc, gold and platinum and having an average particle size of 10 μm or less, An antibacterial polypropylene terephthalate fiber, which is contained in a resin in an amount of 0.01 to 20% by weight, has a Young's modulus of 30 g / d or less, and has an elongation recovery at 90% or more at 10% elongation. 2. A phosphate particle containing 0.1 to 20% by weight of at least one metal ion selected from silver, copper, zinc, gold and platinum and having an average particle diameter of 10 μm or less. 2. The antibacterial polypropylene terephthalate fiber according to claim 1, wherein said polypropylene terephthalate polymer constitutes a core component. 3. A phosphate particle carrying 0.1 to 20% by weight of at least one metal ion selected from silver, copper, zinc, gold and platinum and having an average particle diameter of 10 μm or less. The antibacterial polypropylene terephthalate fiber according to claim 1, wherein the polypropylene terephthalate polymer comprises a sheath component.