JPH01250411A - Antifungal formed product and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title formed product excellent in durability, without impairing the physical properties inherent in the fiber, free from drop-off in the antifungal nature due to washing, by dispersing, in a special state, a mixture comprising specific antifungal powder and an organopolysiloxane in a fiber. CONSTITUTION:A mixture comprising (A) powder consisting of simple substance or compound of silver, zinc, lead or iron, solid at 25 deg.C under 1atm., all >=100 deg.C in decomposition, melting and boiling temperatures, with an average particle size of <=5mu and (B) an organopolysiloxane having a viscosity of >=1,000cst at 25 deg.C is incorporated into a polymer melt and kneaded between the completion of the polymerization for the polymer and the delivery of said polymer. Thence, the resulting melt is delivered through a delivery hole, thus obtaining the objective formed product with said mixture dispersed in the formed product >=200 deg.C in melting point and the component B extended in the longitudinal direction of said formed product to apparently from a phase of island state along with communicating channels randomly in sectional direction at a specified ratio per specified length between the islands.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antibacterial molded article, and more particularly to an antibacterial synthetic molded article having antibacterial activity and excellent washing durability.

(Prior Art) Polyester and/or polyamide fibers are widely used in various clothing such as uniforms, Japanese clothing, and sports clothing, bedding products, interior/living products, and the like.

On the other hand, various bacteria and molds live in our living environment, and they find suitable places to breed. The surface of the human body is no exception; bacteria thrive in humid areas. Many of the diseases currently called skin disorders are thought to be caused by the abnormal proliferation of bacteria on the skin surface. In addition, these bacteria breed on sweat-moistened clothing, causing deterioration and deterioration of fibers, and emitting a foul odor that causes discomfort. In particular, synthetic fibers lack the property of absorbing sweat, so when wearing such fibers, microorganisms grow on sweaty skin, clothing, etc., causing decomposition and producing a sweaty odor. Therefore, in order to suppress the growth of microorganisms on delicate surfaces, it has been desired to develop a polyester fiber product that is clean, does not emit a bad odor, is comfortable, and is safe.

There was a time when organic tin and organic mercury compounds were used to impart antibacterial properties to fibers, but the toxicity of these compounds has become a problem and the use of most of them is now prohibited.

As a post-processing method for imparting antibacterial properties to fibers, silicone quaternary ammonium salts and the like have conventionally been used as particularly safe antibacterial fungicides. For example, Japanese Patent Application Laid-Open No. 57-51874 discloses a carpet in which an organosilicone quaternary ammonium salt is adsorbed and a method for producing the same.

However, silicone-based quaternary ammonium salts have a strong bonding force with cellulose fibers and exhibit antibacterial properties that are durable against washing, but they do not form strong bonds with synthetic fibers and have a temporary antibacterial effect. We are only getting things that show performance.

Furthermore, it has long been known that metal compounds such as silver, copper, and zinc that elute silver ions, copper ions, and zinc ions exhibit antibacterial properties. For example, aqueous solutions of silver nitrate and steel sulfate have been widely used as disinfectants and disinfectants. However, in liquid form, it is inconvenient to handle and its uses are limited.

Therefore, if metal ions such as silver, copper, and zinc are retained in a polymer, it can be expected to be used as an antibacterial substance in a wide range of fields. For example, a method of dispersing and mixing metal compounds such as silver, copper, and zinc in a polymer to form fibers was published in Japanese Patent Application Laid-Open No. 54
-147220. Further, a method of adding and mixing zeolite solid particles exchanged with silver ions and iron ions to an organic polymer is proposed in JP-A-59-133235.

However, with these methods, it is thought that the metal compound has a considerable effect on the polymer, and the usable range is severely limited, and the processability in the fiberization process, especially single fiber breakage during spinning, and pack filter clogging. Problems such as a shortened pack life due to this, and frequent fluffing of drawn yarns occur.

In addition, apart from these process problems, looking at the development of antibacterial performance, it is difficult to simply contain metal ions in the polymer, which is effective for antibacterial action on the fiber surface. Due to insufficient sustained release properties, the absolute level of antibacterial effect is low, and a sufficient combined effect cannot be expected.

In addition, a method of attaching a composite of copper, silver, or zinc compounds and casein to the fiber surface in a water-insoluble state was disclosed in Japanese Patent Application Laid-open No. 5.
No. 6-12347. By making this fiber insoluble in water, it is possible to prevent the composite from falling off when washed with water, but in order to make it insolubilized with gas-in, it is necessary to use formalin.
There is a fear that formalin may be released.

On the other hand, polyester and/or polyamide fibers have become indispensable as clothing materials due to their excellent performance, but their surface properties are insufficient depending on the intended use, so there has been a desire to improve their quality. Particularly in the case of sportswear, socks, etc., fibers must have the ability to withstand intense exercise and abrasion, and conventional synthetic fibers are prone to excessive frictional force being applied to the fibers during situations such as sliding. Time,
Also, when subjected to repeated wear, holes were likely to form.

As a means to improve this, a method has generally been used in which the surface of the fabric is treated with a silicone-based finishing agent using a post-processing method to lower the frictional resistance and suppress the frictional heat generation. Although this method provides good initial performance, it has been found that it does not reach a sufficient level of durability. Especially when worn for a long time] If the fiber is worn for a long time, the post-processing agent on the fiber surface will continue to fall off, and in the case of 1.
l, the question is: it was alive. In addition, when the number of washings increased, the same undesirable phenomenon occurred in rj1. Under these circumstances, there has been an increasing demand for the development of durable, abrasion-resistant synthetic fibers in the clothing field, such as training wear and socks.

(Problems to be Solved by the Present Invention) The purpose of the present invention is to provide fibers made of polyester and/or polyamide without impairing their original physical properties, and without deteriorating their antibacterial and antifungal properties even after washing with water or hot water. friction,
To provide an antibacterial molded article that has excellent durability against abrasion and maintains abrasion resistance and washing resistance.

(Means for Solving the Problems) The molded product of the present invention is a thermoplastic molded product having a melting point of 200°C or higher, such as polyester and/or polyamide, containing silver, zinc, lead, or the like having an average particle size of 5 microns or less. A powder of iron alone or a compound (hereinafter abbreviated as antibacterial powder) and an organic polysiloxane having a viscosity of 1000 centistokes or more at 25°C are dispersed, and in particular, the organic polysiloxane is in a specific dispersion state. It relates to a molded product that is dispersed so that

Furthermore, in the method of the present invention, a mixture of antibacterial powder and organic polysiloxane is added to the molten polymer fluid after polymerization is completed and immediately before molding and discharging, and the mixture is kneaded and then discharged from the discharge hole to form a molded product. It is about the method.

Hereinafter, the molded article of the present invention and its manufacturing method will be explained in detail.

In the present invention, a molded article refers to a linear article typified by fibers,
This term includes film-like objects, tape-like objects, pipe-like objects, various containers, and any other molded objects.
For convenience, the following will explain the case of fibers that require strict manufacturing conditions as an example.

It is desirable that the antibacterial powder used in the present invention has an average particle size of 5 μm or less. If the particle size exceeds 5 μm, it is difficult to use because it tends to cause fuzz and yarn breakage if the filter gets clogged during melt spinning. In particular, when considering the use of these fibers in various clothing materials and bedding products that require a single fiber fineness of around 1 denier, the increase in the particle size of the added powder is due to the increase in the particle size during spinning and drawing. This is not preferred due to process problems such as thread breakage. Therefore, the antibacterial powder used in the present invention preferably has an average particle size of 5 μm or less, more preferably 1 μm or less.

If there is no convenient commercially available product, an antibacterial powder with the desired average particle size can be obtained by stirring or crushing a powdered substance at the level of a regular reagent using a vibration mill, ball mill, etc., or using a crusher. . At this time, by charging the antibacterial substance to be crushed and the organic polysiloxane into a crusher at the same time and stirring and crushing, it is convenient that the antibacterial powder is uniformly dispersed in the organic polysiloxane at the same time.

Compounds such as silver, zinc, lead and iron have been used for sterilization, preservatives, and
It has been empirically recognized that it has a herbicidal effect. For example, zinc chloride was announced by Burnett in 1838 to have a wood preservative effect. Zinc iodide is also used for topical disinfection. Lead oxide was used to prevent the corrosion of ship bottoms and the adhesion of seaweed and shellfish, and ferrous sulfate was used as the first chemical herbicide λ in 1851 for purposes other than wood preservatives. Silver compounds such as silver nitrate and silver fluoride are used as eye drops and anti-suppurants. (Chemistry of anti-bacterial and anti-mold, Sankyo Publishing) The first research on the bactericidal effect of metals is said to have occurred in 1893 when the botanist Naegeli discovered that a trace amount of copper ion at 0.1 ppI11 could kill Aomhidro. There is (
Industrial Materials, Vol. 35, No. 3).

In other words, the metal ions released from the metal compound have antibacterial properties, but more specifically, the metal ions pass through the bacterial cell wall and combine with the -SH group of the enzyme inside the cell, thereby killing the enzyme. It is said to reduce the activity and stop the metabolic function of bacteria, leading to death (a Giken report (
1960) Sakae Toyoda).

Generally, the disinfecting power of metals is in the order of mercury, silver, copper, lead, zinc, and iron. Among these, mercury compounds are highly toxic not only to microorganisms but also to the human body, compared to other metals, and are a substance that has caused social problems such as land pollution, so their use is currently severely restricted. In comparison, other metals, such as silver, zinc, lead, and iron, are said to have little effect on the human body in small amounts, although they are delicate and have great sterilizing power. Rather, zinc and iron are essential elements that are indispensable for the normal physiological functions of the human body, and
Silver compounds are even used in various pharmaceutical products.

In this way, compounds of silver, zinc, lead, and iron were selected as the most suitable substances for the purpose of the present invention because they are not harmful to the human body and exhibit excellent sterilizing effects by releasing trace amounts of metal ions. It was done.

However, surprisingly, it has been found that fibers obtained by simply dispersing copper or copper compound powder in a polymer do not exhibit sufficient antibacterial performance.

Methods for testing antibacterial performance include (1) shake flask method, (2) bacterial count measurement method, and (3) halo test method.For example, in the case of shake flask method, the sterilization rate is 70% or more. It is said that it has sufficient antibacterial properties. If the sterilization rate is less than 70%, the antibacterial performance will be insufficient, and microorganisms will proliferate and putrefaction will occur, creating a sweaty odor on the fibers, and the deodorizing effect will not be as noticeable. Therefore, as an antibacterial fiber product, it must be said that it is a defective product.

When antibacterial powder was simply dispersed in a polymer and made into fibers, the sterilization rate was only 30 to 40%, which was insufficient for antibacterial fibers. The reason for this is thought to be that in order for the fiber to exhibit its antibacterial effect, a trace amount of metal ions must always be present on the surface of the fiber, and simply dispersing antibacterial powder into the resin This seems to be because the metal ions released from the antibacterial powder cannot be smoothly released to the fiber surface if the antibacterial powder is used alone.

As a model test to support this assumption, we investigated the antibacterial properties of fibers by simply attaching the same amount of antibacterial powder as the amount added to the polymer to the fiber surface, and found sufficient performance. The estimation seems correct. However, if it is simply attached to the fiber surface, it naturally tends to fall off during use, and cannot be used as the antibacterial fiber having the washing durability of the present invention.

On the other hand, with regard to abrasion resistance, which is a weak point of synthetic fibers, in the conventional post-processing method using silicone compounds, the frictional antiflux agent adheres only to the fiber surface, so durability was not sufficient, and polyester fibers In the case of fibers, the emulsifying activator contained in the processing agent makes it easier for disperse dyes to migrate and sublimate, which often causes problems with fastness.

We have been conducting extensive research on how to make it possible to achieve antibacterial performance with sufficient washing durability and abrasion resistance with sufficient washing durability using fibers in which antibacterial powder is dispersed in polymers. As a result, it was discovered for the first time that by coexisting an organic polysiloxane with specific physical properties in a polymer together with antibacterial powder, excellent durable antibacterial performance and durable wear resistance can be achieved. It was.

It is very important that this organic polysiloxane needs to exhibit fluidity at room temperature, and at the same time, it must exhibit fluidity at 25℃.
must have a viscosity of at least 1000 centistokes. Furthermore, 0.0% organic polysiloxane was added.
1! Contained in the fiber at 1% to 10% by weight, more preferably 1.0% to 10% by weight,
And, although the dispersed state of the organic polysiloxane forms an apparently island-like independent phase, the islands are not completely separated, but have communication paths randomly connecting the islands in the cross-sectional direction. It has been found that the dispersion greatly contributes to the effects of the present invention.

It is presumed that due to the formation of this dispersed state, the copper ions released from the antibacterial powder contained in the polymer are transported to the fiber surface without being trapped in the polymer. The coexistence of antibacterial powder and organic polysiloxane, which is fluid at room temperature, creates a system in which copper ions, which exhibit a bactericidal effect, are semi-permanently released to the fiber surface through the organic borinoxane in the fiber. It's okay.

Incidentally, since organic polysiloxane is insoluble in water and has sufficient water resistance, a major feature of the organic polysiloxane is that its antibacterial effect is maintained without any deterioration in performance even after washing in hot water, which is an important feature of the present invention. This is one of the effects.

On the other hand, organic polysiloxane has been recognized to have the effect of lowering the frictional resistance on the fiber surface and suppressing frictional heat generation, and is often used in post-processing methods, but its water resistance is insufficient and its durability is limited. There was a problem. In the present invention, it has been found that since organic borine loxane is contained inside the fiber, it is satisfactory in both wear resistance and durability. Further, since the organic polysiloxane is contained in the fiber without using an auxiliary agent such as an emulsifier that would adversely affect the color fastness, no deterioration in the color fastness occurs at all.

In order to exhibit wear resistance, although organic polysiloxane forms an independent phase with an apparent island state in the fiber, the islands are not completely separated, but at a certain rate per a certain fiber length. A structure having communication paths connecting islands randomly in the cross-sectional direction is very effective. This communication path in the cross-sectional direction is thought to play the role of gradually releasing organic polysiloxane accumulated in the inner layer of the fiber from a filling site to the surface layer of the fiber, and this point is important for durability. This is considered to be an important point that exerts the function of wear resistance. If the content of organic polysiloxane in the fiber is too small, the number of communication paths in the cross-sectional direction will be very small, making it difficult to exhibit effective performance, and the content is preferably 1% by weight or more.

For the first time, by dispersing a mixture of antibacterial powder and organic polysiloxane into fibers, it is possible to maintain antibacterial properties that are durable against washing and abrasion resistance that are durable against washing. became.

As the organic polysiloxane referred to in the present invention, various organic silicone compounds can be used, but those that are difficult to volatilize at the spinning temperature of polyester and/or polyamide are preferred. In particular, it is desirable that the weight loss rate when heat treated at 150° C. for 24 hours is 1% or less. Specific examples include dimethylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, etc.
Use alone or in combination.

The viscosity of the organic polysiloxane is preferably 1,000 centistokes or more, preferably 3,000 centistokes or more, and more preferably 5,000 centistokes or more at 25°C. When it was less than 1000 centistokes, there was a tendency for the antibacterial properties after washing with hot water to decrease somewhat.

The reason for this has not been elucidated, but when the viscosity of organic polysoloxane is below a certain value, the migration of organic borinoxane itself increases, making it easier to be extracted from the fiber during hot water washing, and the amount present on the fiber surface decreases. It is presumed that this is because they are coming to Japan. In addition, when the viscosity of organopolysiloxane decreases, phase separation from the polymer progresses further, improving spinnability and
Not only does stretchability deteriorate over time, but organic polysiloxane contained in polymers undergoes heat history during the process of manufacturing textile products, and as a result, migrates to the fiber surface, which affects the texture of textile products. Undesirable.

As for the amount added to the fiber, a mixture with a weight ratio of antibacterial powder and organic polynoloxane of 5.95 to 70:30 is added, and the amount of antibacterial powder to the fiber is 0.1 to 10.
% by weight, 0.1-10% by weight as organic polysiloxane
Preferably distributed. When the amount of antibacterial powder added is small, the amount of organic polysiloxane added is increased to activate the sustained release of steel ions to the fiber surface, and conversely, the amount of antibacterial powder added is large. In some cases, the amount of organic polysiloxane added may be small. The antibacterial performance improves as the amount added increases, but on the other hand, the fluff and yarn breakage rate during the fiberization process are not large, and the mixing ratio of antibacterial powder and organic polysiloxane within the above range depending on the specified denier. It is necessary to adjust the amount added to the fiber.

In addition, if the amount of organic polysiloxane added is too small, the number of communication channels that connect the islands in the cross-sectional direction of the organic borinoxane, which is highly dispersed in the polymer, will be extremely small, and the copper ions and the organic borinoxane will be transferred to the fiber surface. As a result, the effects of the present invention are significantly reduced. For example, in the case of polyester fibers, a specific method for determining the state of formation of communication channels is to immerse the fibers in a 1/10 normal alkaline solution and treat at 98°C, and then soak the fiber surface in a predetermined amount of beer. This can be determined by turning off the fiber and observing the fiber surface with a scanning electron microscope.

The polyester in the present invention is a polyester whose main component is polyethylene terephthalate or polybutylene terephthalate, including terephthalic acid, isophthalic acid, naphthalene 2,6 dicarboxylic acid, phthalic acid, α, β
-(4-carboxyphenoxy)ethane, 4.4°-dicarboxydiphenyl, aromatic nocarboxylic acids such as 5-sodium sulfoisophthalic acid, or adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid, or esters thereof, and diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimetatool, polyethylene glycol, polytetramethylene glycol, etc. A polyester capable of forming molded articles such as fibers synthesized from compounds, in particular, 80 mol% or more of the constituent units are
In particular, a polyester in which 90 mol% or more is polyethylene terephthalate units or polybutylene terephthalate units is preferred, and it is desirable that the melting point is 200° C. or higher. If the melting point is low, its use as a fiber material for clothing etc. will be somewhat limited due to insufficient heat resistance, etc., which is not preferable. Polyester also contains small amounts of additives, such as matting agents such as titanium oxide,
It may also contain antioxidants, optical brighteners, stabilizers, ultraviolet absorbers, and the like.

The polyamide is a polyamide whose main component is nylon 6, nylon 6.6, or meta-xylene diamine nylon, and may be a copolyamide containing a small amount of a third component, but it is preferable to maintain a melting point of 200°C or higher. .

The present invention can be made into shapes similar to pentagonal or hexagonal shapes by high-order processing such as false twisting and crimp processing, or into trilobal, T-shaped, quadrilobal, pentagonal, or hexagonal shapes by using irregular cross-section nozzles during spinning. leaf shape, 7 leaf shape, 8
The effects of the present invention can be sufficiently exhibited even when used in a leaf shape, a multi-leaf shape, or various cross-sectional shapes. Furthermore, even in the case of composite fibers with a so-called core-sheath structure or dorsal-ventral structure, it is preferable that a portion of the polymer to which the mixture of antibacterial powder and organic polysiloxane is added accounts for 20% or more of the cross-sectional area of the fiber. It goes without saying that the effects of the present invention can be fully exhibited if a portion of the polymer is present on the fiber surface layer.

Next, an example of manufacturing the antibacterial fiber of the present invention as described above will be explained. A method in which a mixture of antibacterial powder and organic polysiloxane is added after polymerization of polyester polymer is completed and immediately before spinning, then kneaded and then extruded through a nozzle hole to form fibers causes problems such as lower polymer viscosity, side reactions, and decomposition of plasticizers. This is preferable because it does not generate. If a step of forming into a pellet shape is performed immediately after the completion of polymerization, a mixture of antibacterial powder and organic polysiloxane may be added to the polymerization vessel after completion of polymerization, and after kneading and stirring, it may be pelletized, but it is preferable. It is preferable to feed a predetermined amount of the mixture into a polymer melt fluid during spinning, knead it with a static mixer, and then extrude it from a spinning nozzle hole to form fibers. This is because when the mixture is added to a polymerization kettle and then kneaded and stirred to form pellets, the viscosity of the polymer decreases, it is difficult to uniformly disperse the mixture, and furthermore, contamination occurs in the polymerization kettle. Problems etc. arise.

It is not preferable to add the mixture together with the monomer before polymerization because problems such as side reactions may occur.

In a continuous process where molten polymer is continuously fed and discharged from a spinning nozzle without pelletizing after completion of polymerization, antibacterial powder and organic polysiloxane are added to the molten polymer flow immediately before spinning. blend,
It is preferable to feed a fixed amount of the mixture, then knead it with a static mixer, and then discharge it from a spinning nozzle.

When kneading using a static mixer? The important thing is that it is necessary to knead using a static mixer with a certain number of elements or more. Currently, there are several types of static mixers in practical use, but for example, the Kenics company's 180° left and right twisted blades are arranged 90° apart and pass through n elements.
When using a layer-dividing static mixer, it is necessary to use a mixer with 15 or more elements.If the number of elements is less than 15, uniform kneading of the additive and polymer will not be sufficient, resulting in breakage during spinning. As the occurrence of yarn and fluff winding increases, the drawability also decreases, which is unfavorable in terms of process efficiency.In order to improve process efficiency, it is recommended that the number of elements be 15 or more elements, that is, 215 layers or more, at the minimum. It is desirable that the number of elements be 20 or more, that is, 210 or more layers.

21 when using a static mixer other than Turnix
Needless to say, it is necessary to use a mixer with the number of elements set to correspond to division into five or more layers. Hi-Mixer manufactured by Toshiku Co., Ltd. and Charles Andross (C
For example, the Ross ISG mixer manufactured by Harless & Ross has 4 layer divisions when passing through n elements.
``Since the layer is divided, the number of elements is required to be 8 or more elements, more preferably 10 elements or more.

An example of the manufacturing process of the present invention is shown in FIG. Melt extruder 1
The extruded polymer melt stream is measured by a measuring device 2 in a predetermined amount. On the other hand, the mixture of antibacterial powder and organic polysiloxane is fed by an additive feeder 4, weighed in a predetermined amount by a meter 3, and then added to the polymer melting line. Thereafter, the mixture and the polymer are kneaded in a static mixer equipped with a predetermined number of elements, and are discharged from the spinneret pack 6 to form fibers. The static mixer may be placed in the polymer line or within the spinneret pack.

Alternatively, it may be installed separately in the polymer line and in the spinneret pack.

(Effects of the Invention) The molded article of the present invention disperses a mixture of antibacterial powder and organic polysiloxane in fibers in order to effectively use trace amounts of metal ions having a bactericidal effect released from antibacterial powder. This has made it possible to create synthetic molded products that retain excellent antibacterial properties.

In addition, the antibacterial and antifungal properties do not deteriorate even after frequent washing, cleaning, and washing, and can be used in the clothing field, such as socks that require washing resistance, to suppress the growth of bacteria and have deodorizing effects. It is.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. The evaluation of the bactericidal effect, washing conditions, and abrasion resistance in the Examples was performed by the following test method.

<Measurement of sterilization rate> Performed by shake flask method. The bacterial species used is Staphylococcus aureus.
Using a FDA209P), add a predetermined amount of the test bacterial solution into an Erlenmeyer flask, add 1.5 g of the measurement sample piece, shake 8 [1 rpm x lhr 25°C], and then determine the number of viable bacteria in the flask. After culturing and measuring, the sterilization rate was calculated.

A: Number of bacteria per 1 m2 in Erlenmeyer flask after shaking B:
Number of bacteria per 1 mA in an Erlenmeyer flask before shaking (washing test method) Performed according to JIS L0217-103 method, adding and dissolving 2 g of laundry detergent in water 112 at a liquid temperature of 40°C and washing. Make it into a liquid. The sample and load cloth are put into this washing liquid so that the bath ratio is 1:30, and the operation is started. After treatment for 5 minutes, the operation is stopped, the sample and the loaded cloth are dehydrated using a dehydrator, and then the washing liquid is replaced with fresh water at room temperature, rinsed for 2 minutes at the same bath ratio, and air-dried. The above operation was repeated 10 times (1) to obtain a measurement sample after IHL.

<Evaluation of abrasion resistance> After creating a raw silk taffeta fabric with a fabric weight of 100 g/cm' using drawn yarn of 75d-36f,
aber type Abrasion Te5ter
Using a worn wheel C5-10, 1000 rpm under the condition of 70 rpm.
The weight loss rate of the fabric was measured.

[Example 1 [η] = T+0 of 0.65d12/g (intrinsic viscosity measured using a Huberohde viscometer in a constant temperature bath at 30°C using an equal volume mixed solvent of phenol and tetrachloroethane)
Polyethylene terephthalate containing 145% by weight of yO was extruded using a 30φ extruder, and silver oxide powder, which is an antibacterial powder, and dimethylpolysiloxane having a viscosity of 5000 centistokes at 25°C were added to the molten polymer line at a weight ratio of 145% by weight of yO. The 30+70 mixture was stirred and pulverized in a vibrating mill for 10 hours, and then absolutely dried at 120°C.

After drying, the mixture was 5% by weight based on the polymer flow, ie, 1.5% by weight of silver oxide powder and 3% by weight of dimethylpolysiloxane.
．． The mixture was injected to a concentration of 5% by weight, then kneaded using a 42-element static mixer manufactured by Ternis Co., Ltd., and spun through a round hole nozzle. The spun yarn was drawn under normal conditions using a roller plate method to obtain a 75 denier 3
A multifilament with 6 filaments was obtained. When a knitted fabric was prepared and its antibacterial properties were measured before and after washing 10 times, the sterilization rate was 92.0% after washing and over 99.5% after washing, indicating excellent antibacterial properties.

In addition, when a woven fabric was prepared and its abrasion resistance was examined using a Taber type abrasion tester, it was found that the abrasion resistance was much improved compared to ordinary polyester fabric.

Furthermore, after dyeing the fabric using the following process, the color fastness was examined, and it was found that the light fastness, washing fastness, and rubbing fastness were all grade 5, with no classification at all.

Dyeing method Dye; Dianix Red BN-
3E (CI Disperse Red127)
5% VT dispersion aid; Disper (manufactured by Senkai Kagaku Kogyo) Ig/CpH! lit preparation; ammonium sulfate Ig/+2
Acetic acid (48%) l
cc/(1 bath ratio, 1:3 (1 temperature: 130" x 60 minutes reduction cleaning Hydrosulfide; 1g/ρ amine
Rajin;
Ig/2NaOHIg/& Bath ratio 1:30 Temperature 80°C x 20 minutes Light fastness, according to JIS L-0842 Evaluate color change and fading of the sample by carbon arc lamp Washing fastness, according to JIS L-0844 Evaluate the degree of contamination and discoloration using ester and cotton cloth as the additive cloth.Abrasion fastness: Evaluate the degree of contamination of the cotton cloth after rubbing 100 times with a load of 200g using a Gakushin type abrasion fastness tester according to JIS L-0849. Evaluation [Examples 2 to 5] In Examples 2.3.4.5, zinc oxide,
Fibers were obtained in the same manner as in Example 1 using zinc chloride, lead oxide, and iron chloride. Both antibacterial performance and abrasion performance were good.

[Comparative Example 1] Polyethylene terephthalate to which 45% by weight of TlOtO of 0.65d12/g was added was extruded using a 30φ extruder. The spun yarn was drawn under normal conditions to obtain a multifilament yarn of 75 denier and 36 filaments. When we investigated the antibacterial performance, the initial performance sterilization rate was 2.
．． 5%, the sterilization rate after washing was -5.8%, and no antibacterial performance was observed.

In addition, when we investigated the abrasion resistance of textiles, we found that the weight loss rate was 1
It was 8.5%.

[Comparative Example 2] A drawn yarn of 75 denier 36 filaments containing 0.03% by weight of zinc oxide powder and 0.07% by weight of dimethylpolysiloxane as antibacterial powders was added to polyethylene terephthalate in the same manner as in Example 1. Obtained.

When the antibacterial performance was examined, the initial performance sterilization rate was 30.3%, and the post-washing sterilization rate was 20.0%, which was an insufficient level for antibacterial performance. Furthermore, when the abrasion resistance was examined, the weight loss rate was similar to that of normal polyethylene terephthalate fibers.

[Example 6] Polyester fibers were obtained in the same manner as in Example 3 using zinc chloride powder as antibacterial powder. In Example 6, a mixture of antibacterial powder and 10,000 centistocarbon dimethylpolysiloxane at a weight ratio of 5G:50 was added to polyester in an amount of 2.0% by weight, that is, 1.0 layers of antibacterial powder were added. %, and dimethylpolysiloxane was added so as to be 1.0% by weight. In Example 7, a mixture with a weight ratio of 70:30 was added to polyester in an amount of 2.0% by weight, that is, 1.4% by weight of antibacterial powder and 0.6% by weight of dimethylpolysiloxane. . All had good antibacterial performance.

[Example 8] Polyethylene terephthalate having an η of 0.65 was extruded using an extruder, and the polymer was fed into a molten polymer line with zinc chloride powder, which is an antibacterial powder, and dimethylpolysiloxane of 1 (1,000 centistokes). The weight ratio is 50:50
The mixture was injected at a concentration of 2% by weight based on the polymer, and then kneaded with a 42-element static mixer manufactured by Ternis Co., Ltd. The polymer was used as a sheath component, and the polymer was extruded from a separate extruder. η] = 0.65 polyethylene terephthalate as the core component, core/sheath = 30150
Core-sheath composite spinning was performed using a round hole nozzle with a weight ratio of L/D=2.0. Stretched by normal method, 75 denier 3
A multifilament drawn yarn with 6 filaments was prepared. It was found that a sufficient level of antibacterial performance was maintained.

[Example 9] Nylon 6 (brand 1013B) polymer manufactured by Koube Industries, Ltd. was melt-extruded using an extruder, and copper chloride particles and dimethylpolysiloxane of 10,000 centistokes were added to the molten polymer line at 25°C. After preliminarily drying the mixture at a weight ratio of 1:1 at 120°C, the mixture was 2% by weight or 1% by weight of zinc chloride based on the polymer flow.
% by weight, dimethylpolysiloxane was injected to a concentration of 1% by weight, and then kneaded with a 42-element static mixer manufactured by Ternis Co., Ltd., spun through a round hole nozzle, and then continuously stretched and then wound up. . The antibacterial performance of the obtained 75 denier 36 filament multifilament was good.

[Example 10] Using a polybutylene terephthalate (trade name: Tubadol 5008) polymer manufactured by Mitsubishi Kasei Corporation, fibers were formed in the same manner as in Example 6. Antibacterial performance was good.

[Example 11] The antibacterial powder was a mixture of silver oxide powder and zinc chloride powder,
Fibers were obtained in the same manner as in Example 1. Both antibacterial performance and abrasion resistance performance were good.

[Comparative Example 3] A fiber was formed in the same manner as in Example 6 using dimethylpolysiloxane having a viscosity of 500 centistokes at 25°C. The antibacterial performance decreased significantly after washing. Furthermore, single yarn breakage occurred frequently during spinning and drawing.

[Comparative Example 4] A taffeta fabric was produced using a drawn polyethylene terephthalate 50 denier 36 filament yarn.

Zinc chloride powder and urethane resin were mixed, and the mixture was coated on a taffeta fabric so that the copper chloride content was 1% by weight. The texture of the m product was slightly hard and poor texture. As a result of measuring the antibacterial performance, the initial performance was sufficient with a sterilization rate of 95.0%, but after 10 HL of washing, the coated antibacterial powder fell off severely and the performance decreased to a sterilization rate of 50%.

Margin below

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of the manufacturing process of the present invention. l; Melt extruder 2:3; Weighing machine 4; Additive supply machine 5; Static mixer 6; Spinneret pack Patent applicant RiRashi Co., Ltd.

Claims (2)

[Claims] (1) Powder of single or compound silver, zinc, lead, or iron with an average particle size of 5 microns or less, which is solid at 25°C and 1 atm, and has a decomposition temperature, melting temperature, and boiling temperature of 100°C or higher. and an organic polysiloxane having a viscosity of 1000 centistokes or more at 25°C is dispersed in a thermoplastic molding having a melting point of 200°C or more, and the organic polysiloxane extends in the length direction of the molding. It is characterized by forming apparently independent phases in the form of islands, and randomly connecting the islands in the cross-sectional direction at a constant rate per a certain length of the molded article. antibacterial molded product. (2) Powder of single or compound silver, zinc, lead, or iron with an average particle size of 5 microns or less, which is solid at 25°C and 1 atm, and whose decomposition temperature, melting temperature, and boiling temperature are all 100°C or higher. and an organic polysiloxane having a viscosity of 1000 centistokes or more at 25° C. is added to the molten fluid with the polymer after completion of polymerization and immediately before molding and discharging, kneaded, and then discharged from the discharge hole. A method for producing an antibacterial molded article, characterized in that it is made into a molded article.