JPH03227408A - Conjugate fiber of core-sheath type - Google Patents

Abstract

PURPOSE:To obtain conjugate fiber of core-sheath type having excellent anti-bacterial properties and heat retaining and accumulating properties containing metallic copper and other metals in the sheath component in a specific ratio and containing fine particles of far infrared ray-emitting ceramics the core component. CONSTITUTION:For instance, the aimed conjugate fiber of core-sheath type is composed of (A) a sheath component composed of (i) fine particles of metallic copper or a compound of said copper and (ii) at least one species of metal having ionization tendency different from copper or a compound of said metal in an amount of 0.1-10wt.% in total of (i)+(ii) and (iii) 0.1-10wt.% polyester compound having <=10 deg.C melting point and >=10 poise viscosity at 25 deg.C and a weight ratio of (i)+(ii):(iii)=5-80:20-95 and (B) a core component contains 5-35wt.% fine particles of far infrared ray emitting ceramics.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a core-sheath type composite fiber that has antibacterial properties and excellent heat retention and heat storage properties due to its far-infrared radiation effect.

[Conventional technology]

Conventionally, the far infrared emissivity at 30℃ is 4.5 to 30μ
In this area, a core-sheath type composite fiber can be obtained by adding ceramics having far-infrared radiation properties of 65% or more on average and spinning a polymer as a core component, for example, in JP-A-63
-92720, JP 631112444, JP 63-203873, JP 1'-20
It is disclosed in Japanese Patent No. 7456. Further, ceramic or zeolite fine particles bound to metal ions such as silver or steel are used as substances having antibacterial and deodorizing effects, and these are added to the fiber-forming polymer. That is, JP-A-62-210973, JP-A-1-11.
This method has been proposed in Japanese Patent Publication No. 7744, Japanese Unexamined Patent Publication No. 1-221242, and the like.

[Problem to be solved by the invention]

However, fibers containing fine particles with good far-infrared radiation do not have sufficient antibacterial properties, while fibers containing fine particles of metal compounds such as steel and silver, which have excellent antibacterial properties, do not have sufficient heat retention effects. The drawback is that it cannot be achieved. In particular, products such as undershirts made of fibers containing fine particles with good far-infrared radiation have good heat retention, which creates an environment where bacteria can easily grow during use, making them superior to regular textile products. Antibacterial properties are also required. The purpose of the present invention is to significantly suppress the proliferation of bacteria that tends to be a problem with conventional textile products containing fine particles with good far-infrared radiation, and to provide heat-retaining and antibacterial properties that do not easily deteriorate even after repeated washing. The purpose of the present invention is to provide a composite fiber with excellent properties.

[Means to solve the problem]

That is, in the present invention, the sheath component contains metallic copper or copper compound fine particles (A) and a mixture fine particle consisting of one or more metals or copper compound fine particles (B) having different ionization tendency from copper, and the core component contains far infrared rays. Radioactive ceramic particles (C)
(A) and (B) contain a total of 0.
It is a core-sheath type composite fiber characterized in that (C) is present in the core component at a ratio of 1 to 10% by weight and 5 to 35% by weight. In particular, in the present invention, metal copper or its compound fine particles (A) in the sheath component (hereinafter sometimes simply referred to as component (A)) and metal or copper compound fine particles (B) having a different ionization tendency from copper (hereinafter referred to as component (A)) are used. It has an excellent antibacterial effect, which may be simply referred to as component (B), and an excellent heat-retaining effect, which is due to the far-infrared emitting ceramic fine particles (C) in the core component (hereinafter, sometimes simply referred to as component (C)). When combined, it becomes a composite fiber with synergistically improved antibacterial properties and heat retention properties. Furthermore, the sheath component contains a material having a melting point lower than 10°C,
A polyester compound (D
) (hereinafter sometimes simply referred to as (D) component) is 0.
Contained in a proportion of 1 to 10% by weight, (A) + (B)
: When (D) is 5-80:95-20, the antibacterial properties are dramatically improved, and the antibacterial properties are characterized by little deterioration even after repeated hot water washing. Examples of the polymer constituting the core-sheath composite fiber of the present invention include polyalkylene terephthalate having an alkylene group having 2 to 8 carbon atoms, such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate, and isophthalic acid , polyalkylene terephthalate copolymers made by copolymerizing aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid and sepatic acid, alkylene oquinodo adducts of hisphenols, or condensates thereof, etc. polyester, 6-nylon, 6-nylon, 6-nylon, etc.
10-nylon, 109-nylon, 11-nylon,
Thermoplastic polymers such as polyamides such as 12-nylon, polyolefins such as polyethylene, polypropylene, and ethylene copolymers, solvent-soluble polymers such as polyacrylonitrile, acrylic polymers, polyvinyl alcohol, vinyl chloride polymers, and polyurethane, etc. One type or two or more types of polymers selected from these can be mentioned, and these polymers may be appropriately combined to form the core component and the sheath component. In the present invention, inter alia,
It is preferable to use polyester or polyamide as the sheath component. If antibacterial performance is particularly important, liquid polyester is blended into the sheath component as described later, so it is recommended to use a polyester polymer as the sheath component polymer. desirable. In the present invention, (, A
) The component is fine particles of metallic copper or its compound, and examples of the compound include copper inorganic compounds such as cupric oxide. Component (B) is fine particles of metals or compounds thereof that have a different ionization tendency from copper. Examples of such metals include metals such as silver, aluminum, zinc, and iron. Examples include oxides and chlorides of these metals. Solid particles such as metal ion-exchanged zeolite, alumina, and cordierite may be used as components (A) and (B), but these may cause single fiber breakage during spinning and filter clogging. , may cause fluff. In the present invention, metallic copper is used as the component (A), and (
It is particularly desirable to use metallic silver as component B). These components (A) and (B) have an average particle diameter of 00
It is preferable to use fine particles pulverized to about 5 to 5 microns. Thin fibers with a large position difference tend to cause filter clogging and fluff breakage during spinning, and especially when considering application to various clothing materials, bedding products, etc., fine denier yarn with a single fiber denier of around 1 denier is recommended. However, if the particle size becomes large, thread breakage during drawing will become more severe, which is not preferable. Therefore, components (A) and (B) used in the present invention preferably have an average particle size of 1 micron or less. (^) As an ingredient, for example, fine metallic copper powder, such as MFP powder manufactured by Mitsui Kinzoku Mining Co., Ltd., has high purity, spherical particles, and a sharp particle size distribution, and is suitable for kneading into fibers. This is convenient for dispersing the crowd. In addition, it is important that the sheath component contains components (A) and (B) in a total of 0.1-10% by weight, preferably 3-10% by weight. If the amount is too high, fluff and yarn breakage rate will increase in the fiberizing process, so the content of these components must be adjusted according to the specified denier. Also, the weight ratio of component (A) and component (B) is (A)/
(B)=1-20 is preferable, and 7-15 is especially preferable. In the present invention, in order to maintain the antibacterial effect efficiently and over a long period of time, the sheath component contains a polyester compound (D) (hereinafter referred to as , sometimes simply referred to as component (D))
It is desirable that the amount of 0.1 to 10% by weight is present. If the viscosity of this polyester compound is too low, there is a tendency for the antibacterial level after hot water washing to decrease somewhat. The exact reason for this is unknown at present, but it is probably because when the viscosity of component (D) becomes too low, the compound itself becomes more likely to migrate, and when washed in hot water, it is slightly removed from the fibers. It is presumed that this is because it becomes easier to use, or that the water resistance slightly decreases. (D)
As an ingredient, for example, product name A manufactured by Adeka Argus Co., Ltd.
Polyester plasticizer commercially available as DK CIZER series or manufactured by Dainippon Ink Chemical Co., Ltd.
Polyester plasticizers commercially available under the trade name POLYCIZER series are preferably used. Among the polyester compounds, sebacic acid as the acid component,
It is appropriate to use a material containing anopic acid and phthalic acid as main components, with an appropriately selected glycol component, both in terms of cost and physical properties. The smaller the total content of component (A) and component (B), the more the component (D) is present in the sheath component. When component (B) is contained in a large amount, it is sufficient to allow it to be present in a small amount, and it is desirable to control it within the range of <0.1 to 10% by weight as described above. If it is outside this range, it may be difficult to develop a good antibacterial effect, and the fiber properties tend to be poor. Furthermore, in the present invention, (A
) ↑ (B) : (D) It is desirable that the ratio is 5 to 80 and 95 to 20. In order to make the most of the effect of component (D), it is desirable to use polyester or polyamide, particularly polyester, as the polymer for the sheath component. Next, in the present invention, it is necessary that the core component of the composite fiber contains 5 to 35% by weight of far-infrared emitting ceramic fine particles (C) (hereinafter sometimes simply referred to as component (C)). be. Component (C) includes, for example, alumina (AIto3), silica (SiO), magnesia (
MgO), mullite (1~2A1.Island/5iOt), zirconia (ZrO,), norcosand (zrJ41Qt)
), chromium oxide (CrtOs), titanium oxide (TiO
t), spinel (MgO'AltOs), ferrite (FeO!-Fe3O3)% cordierite (MgO・A
One or more compounds selected from the group of oxide ceramics such as I*Os・5i02), carbide ceramics such as zircon carbide (Zr0), and nitride ceramics such as titanium nitride (TiN). Mention may be made of fine particles. The shape of the compound added to the polymer is such that it has a particle size that does not interfere with spinning, and generally has an average particle size of about 20 microns or less, preferably in the range of 0.2 to 5 microns. However, if the particle size is too small, agglomeration of particles will occur and dispersibility will deteriorate, so a particle size of 0.1 micron or less may not be preferable. If the amount added is small, the far-infrared radiation effect will not be sufficient. On the other hand, if the amount added is too large, spinnability decreases, adhesiveness with the sheath component polymer decreases, or sufficient stretchability cannot be obtained, making it impossible to obtain high fiber strength. Furthermore, a heat stabilizer and a light stabilizer may be added to the core-sheath type composite III of the present invention. The cross-sectional shape of the core-sheath type composite fiber of the present invention may be a circular cross-section, a modified cross-section, a concentric circle or an eccentric circle depending on the relationship between the core and sheath, and may have a hollow portion. The composite ratio (weight ratio) of the core to the sheath is not particularly limited, but it is suitably 5 to 40%, since the effect can be achieved even with a small amount of the sheath component. An example of the cross-sectional shape of the core-sheath type composite fiber of the present invention is as shown in FIG. , 2 represents a core component containing far-infrared emitting ceramic fine particles (C) component. As long as the core-sheath type composite fiber of the present invention satisfies the above-mentioned structural requirements, conventionally known methods can be used for manufacturing the fiber. Specifically, for the sheath component, (A)
The component (B) and the component (B) are mixed with the component (D) as necessary, and this is added, for example, after the completion of polymerization of the polyester polymer and immediately before spinning, and the component (C) is added in a different melt system. Possible methods include spinning a composite material with a core component polymer. Regarding the method of adding component (C) to the polymer,
Any stage from the time of the polymerization reaction to just before spinning can be selected. The core-sheath type composite fiber of the present invention obtained in this way can be made into filament yarn or spun yarn from stable fiber to make a woven or knitted fabric. It can also be used as a fiber web or fiber-entangled nonwoven fabric, or as paper or paper-like material made by dispersing short fibers in water. In the resulting fabric, the effects of components (A), (B), and (C) are expressed synergistically, and it has excellent antibacterial properties and heat retention properties, and can be used as underwear, socks, and gloves. , sheets, futon sides, padded cotton, bandages,
It can be applied to various things such as skin patch base fabric, hot carpet, and Zabuton. (Examples) Next, embodiments of the present invention will be described using specific examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, parts and percentages in the examples refer to weight. Example 1 Using a core-sheath composite spinning machine with two melting systems, polyethylene terephthalate with [η) = 0.62 and zirconia ceramic (ZrOt) tO with an average particle diameter of about 0.6 microns were added as the core component. % and 0.5% phosphoric acid ester heat stabilizer were used as the sheath component.
2 mol% copolymerization of 2゛-bis(p-hydroxyphenyl)propane/ethylene oxide 2 mol adduct [η]
-0.6 g of polyethylene terephthalate was mixed with 1% of metal steel fine particles with an average particle size of 0.3 microns and metal silver with an average particle size of 05 microns as antibacterial additives (#: Silver-9
．． Using a chip containing 1) and 08% of a phosphoric acid ester thermal stabilizer, melt spinning was carried out at a composite ratio of I:1, a spinning temperature of 295°C, and a winding speed of 1 at 200 m/min. The obtained core-sheath composite fiber was drawn 3.5 times, crimped, heat-set, and cut into a length of 51 mm to obtain staple fiber Ei (1) with a fineness of 2.5 denier. Similarly, stable fibers (2) having irregular cross-section fibers having a fineness of 6 denier as shown in FIG. 1 (4) were obtained. Next, 65 parts of Staple Fiber 'a (1), 35 parts of Rayon Stable Fiber A with a fineness of 2 denier and a fiber length of 51 mm were blended to make a spun yarn, which was woven into a hand-woven fabric and dyed. I used woven fabric to sew the geodetic patterns for bedclothes and quilts. On the other hand, the stable fiber (2) was hung on card and used as padding for futons to make mattresses and comforters. For comparison, we made mattresses and comforters for nightwear using conventional plain woven fabrics using polyester fibers and stuffed cotton. A sensory test was conducted using both futons by 10 testers who randomly selected the state of odor caused by sweat and heat retention. As a result, the futon of the example had almost no odor after one month and had excellent heat retention, but the futon of the comparative example started to have a peculiar odor. Ta. Example 2 As a sheath component, a polyester plasticizer (polyester with a viscosity of I00 poise exhibiting fluidity at 25°C, manufactured by Adeka Argus Chemical Co., Ltd.: PN-350) was used in an amount equal to the weight of the mixed metal fine particles.
) Composite fibers were produced in the same manner as in Example 1 except that conjugate fibers were blended. A knitted fabric was prepared using this fiber as a multifilament yarn, and its antibacterial properties were measured before and after washing 10 times.The sterilization rate by the shake flask method was excellent at over 85% both before and after washing. Example 3 A core-sheath composite spinning machine with two melting systems was used, and 6-nylon chips to which 25% of Zircosand ceramic (ZrOt Siow) with an average particle diameter of 0.6 microns was added as a core component were used. 2 mol% 5 as a sheath component
~ Metallic copper with an average particle size of 0.5 microns and iron oxide with an average particle size of 0.5 microns are mixed in 9:1 of polyethylene terephthalate copolymerized with sodium sulfoisophthalic acid.
Using chips containing 1% of the polyester plasticizer used in Example 2 and 1% of the polyester plasticizer used in Example 2, spinning was carried out at a composite ratio of 1:1, a spinning temperature of 290° C., and a winding speed of 1,200 m/min. The obtained core-sheath type composite fiber was drawn 3.3 times and heat-set to obtain a filament yarn having a fineness of 2.5 denier. This filament yarn was subjected to false twisting and used as a filament yarn to knit socks. On the other hand, for comparison, socks were similarly knitted using ordinary nylon filament processed yarn. Both types of socks were worn by 10 people on one foot, and odor generation, heat retention, etc. were compared. As a result, the products of Examples had almost no odor even when worn all day long, and had excellent heat retention. Furthermore, even though wearing and washing were repeated for one month, the effect of suppressing odor generation continued. Furthermore, the fibers of the examples could be dyed clearly, and their process passability, weavability, etc. were the same as those of ordinary nylon fibers.

【Effect of the invention】

The present invention uses metallic copper or its compound fine particles (A) as a sheath component.
By containing copper and fine particles of a metal or its compound having a different ionization tendency (B), and containing far-infrared emitting ceramic fine particles (C) in the core component, the heat retention effect of conventional far-infrared emitting fibers is further strengthened. However, it is possible to improve antibacterial properties, which have not been sufficiently achieved with such fibers, and the antibacterial properties are maintained for a long period of time.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of the cross-sectional shape of the core-sheath type composite fiber of the present invention. 1: Sheath component containing antibacterial substance ('A) component and (B) component; 2; Core component containing far-infrared emitting ceramic fine particles (C) component.

Claims (2)

[Claims] (1) The sheath component contains metal copper or its compound fine particles (A) and the mixture fine particles consisting of one or more types of metal or copper compound fine particles (B) that have a different ionization tendency from copper, and the core component contains far-infrared emitting ceramic fine particles. Contains (C),
A core-sheath type characterized in that (A) and (B) are present in the sheath component in a total amount of 0.1 to 10% by weight, and (C) is present in the core component in a total amount of 5 to 35% by weight. Composite fiber. (2) The sheath component further contains a polyester compound (D) having a melting point lower than 10°C and a viscosity of 10 poise or more at 25°C in a proportion of 0.1 to 10% by weight, and
The composite fiber according to claim (1), wherein (A)+(B):(D) is 5-80:95-20.