JPS59100715A - Antimicrobial synthetic fiber - Google Patents

Abstract

PURPOSE:Antimicrobial synthetic fibers, containing a specific amount of poly-p- vinylphenol, having improved lasting antimicrobial action without causing disorder in the skin, and suitable for clothing, e.g. socks and stockings and underwear, etc. and medical use in hospitals and carpets, etc. CONSTITUTION:Antimicrobial synthetic fibers containing 0.1-30wt% poly-p- vinylphenol of the formula (n is preferably an integer 10-200). Preferably, the fiber fineness of the synthetic fibers is preferably <=20 deniers, and the strength is >=2.5g/denier. Polyethylene terephthalate or polybutylene terephthalate, etc. is used as the polyester.

Description

[Detailed description of the invention] The present invention relates to a synthetic W A4u with antibacterial properties.

Polyamides or saturated olopolyesters such as polyethylene terephthalate and polybutylene terephthalate have many excellent properties and are used in many fields such as clothing fibers, industrial fibers, and films. Improvements in its properties are expected to further expand its applications. Particularly in recent years, as interest in the hygiene of clothing and the like has increased, there has been an increasing demand for stain-proofing, deodorizing, and antibacterial properties. For example, athlete's foot and other fungi tend to adhere to and accumulate metabolites such as sweat, sebum, and grime, especially the soles of the feet, which are prone to high humidity due to socks and shoes.

Parasitic 1-1 breeding between the toes, etc. Moreover, once infected, complete treatment is difficult. It is also known that microorganisms are likely to grow in car vents, especially on the backs and undersides of chests of drawers, sideboards, etc., and it is not easy to prevent the growth of these microorganisms, which pose a hygiene problem. Therefore, it has become desirable to improve the function of the fiber itself and impart antibacterial properties.

Traditionally, techniques for imparting antibacterial properties have involved coating or periodically spraying molded textile products with antibacterial agents, or resins containing antibacterial agents, adhesives, etc. was. Although these coating and spray methods have direct effects, they have poor durability against washing, etc. There have also been reports of cases where antibacterial agents transferred to the skin of people who come into contact with the textile products, causing skin disorders.

Given these circumstances, there is a desire to develop a technology that imparts antibacterial properties that is sustainable and that does not cause skin damage due to antibacterial agents. It is conceivable to blend an antibacterial agent into the polymer. For example, JP-A-45-25386 and JP-A-45-11837 disclose that a naphthiomate antifungal agent or the like is blended with naphthiomate L5 and then spun.

However, it is said that even in this case, if the number of washings increases, the antifungal agent will fall off and the antibacterial performance will be insufficient. On the other hand, in the case of synthetic polymers such as polyamides and saturated polyesters, the melt-molding temperature reaches 260-330°C, so ordinary antibacterial agents are blended during melt-molding. Otherwise, the antibacterial agent would thermally decompose, making it completely unusable. Furthermore, the synthetic fibers used for clothing, inch bags, etc. have a small single yarn fineness of 1.5 y/de and a strength of 2.5 y/de or more, preferably 1. < is 3g/de
Although the above is desired, in order to satisfy such physical properties, it is necessary that the antibacterial agent used has an affinity for the synthetic polymer.

From this perspective, there has been a demand for the development of antibacterial additives that do not thermally decompose even at high temperatures of 260 to 330°C and have good affinity with synthetic polymers. I had not yet seen it.

The inventors of the present invention have conducted intensive studies to realize the above-mentioned demands of the industry, and as a result, they have discovered that it is suitable to use poly-bara vinyl phenol as an antibacterial additive, and have arrived at the present invention. This is what I did. That is, the present invention
It is an antibacterial synthetic fiber characterized by containing 0.1 to 30% by weight of rose vinyl phenol.

In the present invention, synthetic fibers are fibers made of synthetic polymers with fiber-forming properties, such as polyamide fibers and polyester fibers, among which saturated polyester fibers are particularly desirable.

Acid components constituting saturated polynisder and 1. Terephthalic acid, inphthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenylsulfone dicarboxylic acid,
Diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid? Aromatic dicarboxylic acids such as methyl terephthalic acid, methyl isophthalic acid, etc., succinic acid, adipic acid, sepatic acid, decanedicarboxylic acid.

aliphatic dicarboxylic acids such as toticandicarboxylic acid,
Alicyclic dicarboxylic acids such as cyclohexanecarboxylic acid, ε-oxycarboxylic acid.

Examples include oxycarboxylic acids such as oxybenzoic acid and hydroxyethoxybenzoic acid, among which aromatic dicarboxylic acids are preferred, and terephthalic acid is particularly preferred.
,stomach. In addition, in the above saturated polyester, when the acid component is a dicarboxylic acid, the glycol component [eg, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexane dimethylol, etc. Among these, ethylene glycol and tetramethylene glycol are particularly preferred.

It is also possible to use polyoxyalkylene glycols as part of the glycol component, for example polyoxyethylene glycol.

Examples include polyoxypropylene glycol, polyoxytetramethylene glycol, and copolymers thereof.

When using polyoxyal rangercol, its average molecular weight is preferably 500 to 5000, more preferably [
7 (is 600-4000, particularly preferably 1.< is 800-3
000, and the amount used is 5 to 5 in the copolymerized polyester.
The copolymerized amount is about 85% by weight, preferably about 10 to 80% by weight, more preferably about 15 to 75% by weight. The copolymerized polyester obtained by copolymerizing this polyoxyalkyleg glycol is preferably a block copolymer.

The saturated polyester may also have a content within a range that is substantially thermoplastic (e.g., within the range of total acid component).

1 molar ratio or less), trifunctional or higher functional compounds such as trimethyp-lua'l=pan, pesotaerythritol, trimellitic acid, pyromellitic acid, etc., and monofunctional compounds such as benzoylbenzoic acid, diphenylcarboxylic acid, etc. may be copolymerized. Additives, such as colorants, if necessary.

Contains matting agents, stabilizers, flame retardants, antistatic agents, etc. It can be expressed by equation (1).

Here, n may be an integer of 3 or more, but the preferable value of n is 10 to 200 from the viewpoint of blendability into synthetic polymers and washing resistance. , P expressed by the tit formula
In order to impart flame retardancy to VP, hydrogen atoms in the benzene ring or straight chain portion may be partially substituted with a halogen or halide such as chlorine or bromine. Further, it may have a structure in which the hydrogen atom in the straight chain portion is substituted with a methyl group or the like.

Furthermore, PVP may contain ethyne propylene, styrene, etc. as a copolymerization component.

In the present invention, such PVP is added to the synthetic polymer at zero
．． Add 1 to 30% by weight. If the amount added is less than 0.1 parts by weight, it is difficult to achieve antibacterial effects, and if the added amount exceeds 30 parts by weight, it becomes extremely difficult to form #2 fibers in the synthetic polymer. Particularly preferred 1. from the viewpoint of antibacterial properties and physical properties of the resulting fibers. The amount added is J to 15% by weight. Such PvP is added to the synthetic polymer in a molten state during the molding of the synthetic volifoo (7).The synthetic polymer that has once solidified into powder is remelted using an extruder, etc., and then molded. It may be added at the same time.The time during which the synthetic polymer and PVP coexist at a high temperature of 280°C or higher, that is, the residence time, is particularly important.For example, when PvP is added to polyester at 1.280°C. When stirred for more than 5 minutes, the viscosity of polyester becomes significantly higher than 1.
This makes it extremely difficult to form fibers by melt molding. From this, it is presumed that the PVP used in the present invention is simply mixed into the polyester and is causing some kind of chemical interaction. Therefore, in the present invention, the preferred condition for adding PVP is to keep the melting residence time of the synthetic polymer within 5 minutes.

Furthermore, it is most preferable (2) The melting residence time is within 3 minutes.1. Usually, the synthetic polymer powder is remelted using an extruder, etc. (2. The melting residence time in the fiber manufacturing equipment is 4 minutes or less.) When using the PvP used in the present invention in normal equipment, the amount added is kept to about 1% by weight or less, the temperature is also set low, and the extra-goo is stirred and kneaded. Unless measures are taken to reduce the effect, it is not possible to form good fibers.1- Even with these measures, it is not easy to maintain the spinning condition stably over a period of more than several days. do not have.

For this reason, when producing the synthetic fiber of the present invention, even if the synthetic polymer powder is remelted using an extruder or the like to produce the fiber, once the synthetic polymer is melted, PVP and the It is most preferable to devise the addition equipment so that the coexistence residence time with the synthetic polymer melt is 0.5 to 3 minutes. Among the synthetic fibers of the present invention, polyester fibers have particularly excellent antibacterial properties.
, has the additional effects of high strength and excellent bending abrasion durability. What should be further noted is that when ordinary antibacterial fibers are dyed or washed, the antibacterial agent tends to fall off the fiber surface and its performance deteriorates, but the fibers of the present invention do not have this tendency. This means that it is almost impossible to observe.

The synthetic fibers of the present invention can be suitably used for clothing such as socks and underwear, and for medical purposes in hospitals. Furthermore, when used for the inch rear of carpet Ql, it can be preferably used because of its excellent fatigue resistance. Furthermore, the fibers of the present invention may be used alone, or may be used in combination with other tIl fibers while maintaining antibacterial properties.

The present invention will be explained below with reference to Examples.

In the examples, antifungal performance was determined by the following method.

Sabouraud medium was placed in a Petri dish with an inner diameter of Ej, 9>, and a sample of athlete's foot fungus (Trichophyton, Mentagraphite) was added on top of it, and a stockinette fabric made of yarn for evaluation was cut out to a diameter of 3 crn. 28℃, 70℃
%RHW and cultured for 10 days, and the size of the inhibition zone around the sample was measured. Further, parts in the examples represent parts by weight, and the intrinsic viscosity was determined from the value measured at 35° C. using a mixed solvent of tetrachloroethane and phenol in a ratio of 4:6 as the solvent.

Example 1 Polyethylene terephthalate with an intrinsic viscosity of 0.7 was
Heating at ℃ for 4 hours 1- After drying, use an extruder (
1) Extrude it as a molten polymer at about 290°C, pass it through a polymer conduit, and then meter it out with a gear pump (5) (through 2 spinning packs and discharge the polymer from a spinneret. approx. 20,000) at 220℃ in another extruder +Ill
to melt. The PvP extruded from this extruder is metered by a gear pump (B), and then added to and mixed with the molten polyethylene terephthalate polymer immediately before the gear pump (5). The polymer residence time from the gear pump to the spinneret is 1 minute and 45 seconds.

Further, the temperature from the gear pump to the spinneret is kept at 295°C by a heating medium. The mixture of polyethylene terephthalate and PVP fed by gear pump (3) was 4 oy per minute, and the PVP metered by gear pump 03) was 22 oy per minute. The spinneret has 24 holes, each hole has a diameter of 0,3 FF! / m96. Bottle containing PvP discharged from the mouthpiece? !
The ethylene terephthalate filament was wound on a spinning winder at 500 m/min to obtain an undrawn yarn. Next, this undrawn yarn was heated to 80°C and stretched 3.5 times 12 times, and further stretched 18 times.
Heat treatment was performed at 0°C. The yarn spinning evaluation was carried out over a period of 5 days, and good drawn yarn was obtained without any particular problems. This drawn yarn had a strength of 4.81 i'/de and an elongation of 28, and had good yarn physical properties. These yarns were knitted into stockinette fabrics to obtain SO samples. Furthermore, this knitted fabric is 2
Sample S1 was obtained by adding synthetic detergent to water at 5° C. and stirring for 100 hours. The results of evaluating the antifungal performance of these samples are shown in the table below.

80 5 parts by weight No bacterial strain growth 81 p 25°C x 100 hours
〃Comparative Example I PVP was not used (i.e. extruder (f
1 and the gear pump).
As in Example 1, 1. The strength of the drawn yarn obtained is 4.7 f.
/de, the elongation was 32 inches. These yarns were knitted into a knitted fabric to obtain a sample. The evaluation results of the antifungal performance of this sample were as follows.

'ro O-5 Example 2 95 parts of polyethylene terephthalate with an intrinsic viscosity of 0.7 was heated at 180°C for 4 hours, dried for 1 time, and then pvp (
5 parts of round-neck petroleum emg PVP #732 (i molecular weight approximately 20,000) were blended and extruded from an extruder at 295°C, and the number of holes was 24, the pore size was o, and the pore size was 3. A spinneret of /,,p was discharged. The average residence time of this Zolend product from passing through the melting zone of the extruder to exiting the spinneret was 4 minutes and 48 seconds. The filamentous material discharged from the spinneret and spinning at °C was wound up by a spinning winder at 500 m/min to obtain an undrawn yarn. Next, this undrawn yarn was stretched 3.5 times j-1 under heating at 80°C, and further heat-treated at 180°C. It was possible to evaluate yarn spinning for 4 hours, but after that, denier unevenness occurred frequently during the spinning process, and good drawn yarn could not be obtained. A good drawn yarn strength is 3.8 f/
de, and the elongation was 28 inches. The anti-odor and anti-bacterial performance of this sample showed good bacterial strain growth.

Examples 3 to 7 Comparative Examples 2 to 4 The evaluation results of polyester yarns obtained by changing the residence time and the amount of PVP added in Examples 1 and 2 are shown in the following table. Pv
When the amount of P added is within the range of 0.1 to 30% by weight, both the thread spinning process condition and antifungal properties are good, but when the amount of PVP added is 0.1 to 30% by weight.
If the ratio is less than 1, the antifungal properties will be poor, and if it exceeds 30, the fiber forming property will deteriorate and the process condition will deteriorate.

Example 8 Polyethylene terephthalate with an intrinsic viscosity of 0.7 was
Heating at ℃ for 4 hours [7 Drying 1. After that, extrude as a molten polymer at about 290 °C from an extruder (11).
After passing through the polymer conduit, the gear pump (A) is used to measure 1. The polymer is discharged from the spinneret through the spin pack. On the other hand, some of the hydrogen atoms of the benzene ring are brominated L7
pvp (made by Maruzen Oil Co., Ltd. MB type PHP)
#75123 (molecular weight approximately 40,000) is melted at 220°C in another extruder (II). This extruder (
The PvP extruded from Ill is metered by the gear pump 03) and then added to and mixed with the molten polyethylene terephthalate polymer immediately before the gear pump (5). The residence time of the polymer from the spinneret to the spinneret is 1 minute and 45 seconds. Moreover, the temperature from the gear pump (3) to the spinneret is maintained at 295° C. by a heating medium. The mixture of polyethylene phthalate and PVP metered by gear pump (A) was 40 S' per minute and the PvP metered by gear pump 031 was 22 per minute. The spinneret has 24 holes, and the diameter of the flower is 0.3 m/m12
(The filament of polyethylene terephthalate containing PVP discharged from the nozzle was 500 FF per minute.
Wind up the undrawn yarn on the spinning winder with +10. Next, this undrawn yarn was stretched 3.5 times while heating at 80°C,
Further heat treatment was performed at 180°C. The yarn spinning evaluation was carried out over a period of 3 days, and a good drawn yarn was obtained without any particular problems.

This drawn yarn had a strength of 3.9 f/de and an elongation of 28 degrees, and had good yarn physical properties. These yarns were knitted into stockinette fabric to obtain sample S2. Furthermore, this knitted fabric is 2
Sample S3 was obtained by adding synthetic detergent to water at 5° C. and stirring for 100 hours. The results of evaluating the antibacterial performance of these samples are shown in the table below.

Claims (1)

[Scope of Claims] 1. An antibacterial synthetic fiber characterized by containing poly-rose vinyl phenol in an amount of 0.61 to 30% by weight. 2. The antibacterial synthetic fiber according to claim 1, wherein synthetic m #4G is made of polyester. The antibacterial synthetic fiber according to claim 1 or 2, wherein the single fiber fineness is 20 denier or less. 4. The antibacterial synthetic fiber according to claim 1 + Ks 2 or 3, which has a strength of 2.5 f/de or more,
. 5. The antibacterial synthetic fiber according to claim 2, wherein the polyester is polyethylene terephthalate. 6. The antibacterial synthetic fiber according to claim 2, wherein the polyester is polybutylene terephthalate.