JPWO2007088758A1 - Polyamide fiber, fabric and fiber product comprising the same - Google Patents

Abstract

[Problem] To provide a polyamide crimped yarn, a polyamide-structured bulky processed yarn, a polyamide-covering elastic yarn, etc., having both the excellent antifungal properties and good color development properties. An additive having at least an antifungal property is contained in an amount of 0.05 to 3% by weight, and the additive comprises an inorganic component and an organic component.

Description

  The present invention relates to a polyamide fiber having excellent antifungal properties and excellent color developability, a fabric and a fiber product comprising the polyamide fiber, and more specifically, a polyamide fiber having such characteristics, The present invention relates to crimped yarn made of the fiber, polyamide-structured bulky processed yarn, polyamide-covering elastic yarn, various fabrics made of these fibers or various yarns, fiber products, inner wear, down shells, and the like.

In addition, in the present invention, the description will mainly explain the antifungal property, but the antifungal performance referred to in the present invention is generally in common with the performance called antibacterial performance or algal control performance, The polyamide fiber, fabric, and fiber product of the present invention can have antibacterial performance or anti-algae performance.
For example, when the textile product according to the present invention is used for a camisole, the antifungal effect exhibits a good antibacterial effect. In the case of a camisole, the main focus is on the antibacterial effect.

  For example, when the textile product according to the present invention is used in a fishing net, it exhibits a good anti-algae effect as well as a fungicidal effect. In the case of a fishing net, the main focus is on the anti-algae effect. Therefore, the polyamide fiber of the present invention, crimped yarn made of the fiber, polyamide-structured bulky processed yarn, polyamide-based covering elastic yarn, various fabrics made of these fibers or various yarns, textile products, inner wear, down shell Can be expressed and described as having antifungal, antibacterial and / or antialgal properties adapted to the application in each practical application. Therefore, the polyamide fiber of the present invention, crimped yarn made of the fiber, polyamide-structured bulky processed yarn, polyamide-based covering elastic yarn, various fabrics made of these fibers or various yarns, textile products, inner wear, down shell Can be used in a similar configuration even in the field where antibacterial and / or algal resistance is required, and the technical field of the present invention has such antibacterial and / or algal resistance. It also relates to the requested technical field.

  In recent years, lifestyle changes have increased the desire for cleanliness, and an increasing number of consumers are seeking products and products having functions such as fungicides, antibacterials, algae, and mites. The needs are the same for textile products and products, and fibers having various fungicidal and antibacterial functions have been proposed in response to consumer demands.

  In general, there are many fungicides and antibacterial agents for synthetic resins (Non-patent Document 1), and agents that are effective against target bacteria, fungi, and algae are selected and used as necessary. Yes.

  For example, a fiber in which a silver-based inorganic antibacterial agent is kneaded has been proposed (Patent Document 1).

  Also, a polyamide fiber kneaded with zinc oxide (antibacterial agent) has been proposed (Patent Document 2).

  However, these inorganic antibacterial agents are effective against bacteria, but have no effect on fungi and algae. In addition, these proposed technologies contain a thiazole compound having no mercapto group as a coloring preventing agent in Patent Document 1 for the problem of yellowing (coloring) of a fiber product caused by adding an antibacterial agent. An improvement technique such as treatment with a treatment liquid and treatment of the surface of zinc oxide with a coupling agent is also proposed in Patent Document 2.

  In addition, a nitrile compound, a pyridine compound, a haloalkylthio compound, an organic iodo compound, a thiazole compound, and a compound selected from the group consisting of a benzimidazole compound, a bacterium, a fungus, an algae, A molded article and fiber effective for ticks have been proposed (Patent Document 3).

  However, according to various studies by the present inventors, yellowing (coloring) occurs when a mixed compound of these organic components is contained in a polyamide resin to form a fiber. This yellowing, especially in the case of apparel, requires whiteness, so if the fiber itself is yellowed, the color will become dull even after dyeing and the color developability will not be solved. It is a problem that must not be.

  On the other hand, polyamide fibers are suitably used for innerwear such as lingerie, foundation, and underwear, and downshells such as down jackets and sleeping bags due to moderate water absorption and soft touch. In the case of inner wear, since whiteness is required, the fact that the fiber itself is yellowed is a problem that must be solved because the color becomes dull even after dyeing and the color developability deteriorates. Moreover, this yellowing is a similar problem even in the case of down shell applications where fashionability is required.

In addition, feathers used for down shells are collected from waterfowl such as goose and duck, and are characterized by being warm, plump, light, and highly hygroscopic. . However, while feathers have these features, they contain fat. When this fat grows mold, it smells and has a unique feathery odor. As a measure against mold, there is known a method of applying a fungicide to the fabric by post-processing. However, when used for many years, the fungicide applied to the surface peels off due to friction and the effect cannot be obtained. There is.
JP-A-6-272173 JP 2001-55627 A JP 9-157111 A “Bacteria and fungicide dictionary”, Japanese Society for Antibacterial and Fungus, 1994

  The object of the present invention is to solve the conventional problems as described above and to have a good balance of two properties of antifungal and coloring properties, a crimped yarn comprising the fiber, a polyamide-based structure bulky We provide processed yarns, polyamide covering elastic yarns, fabrics and textile products, innerwear, and down shells.

  More specifically, polyamide fibers having excellent antifungal, antibacterial, algal and anticoloring properties, crimped yarns composed of the fibers, polyamide-structured bulky processed yarns, polyamide-covering elastic yarns, fabrics and textile inner products Wear and down shell.

  The above-described object is achieved by using the following polyamide fiber, crimped yarn made of the fiber, polyamide-structured bulky processed yarn, polyamide-covering elastic yarn, fabric, textile product, inner wear, and downshell.

(1) An additive having at least 0.05 to 3% by weight of an additive having antifungal performance, wherein the additive is a treatment for supporting an organic component on the surface of an inorganic oxide, and The polyamide fiber, wherein the organic component is a mixed organic component containing a combination of at least two of imidazole compounds, pyridine compounds, thiazoline compounds, halogen compounds, and haloalkylthio compounds.

(2) The above additive, wherein the additive comprises 97 to 99.9% by weight of the inorganic component and 0.1 to 3% by weight of the organic component with respect to the additive weight. (1) The polyamide fiber as described.

(3) The polyamide fiber as described in (1) or (2) above, wherein the inorganic component is a metal oxide.

(4) The polyamide fiber as described in (3) above, wherein the metal oxide is zinc oxide or titanium oxide.

(5) The polyamide fiber according to any one of (1) to (4) above, wherein the polyamide fiber is a polyamide crimped yarn.

(6) In a structurally bulky processed yarn composed of two or more filament yarns, at least one filament yarn is the polyamide fiber according to any one of (1) to (4) above. Polyamide-based bulky processed yarn.

(7) A polyamide-based covering elastic yarn, wherein an elastic fiber is used for the core yarn, and the polyamide fiber according to any one of the above (1) to (4) is used for the coated yarn of the core yarn.

(8) A polyamide fiber fabric comprising at least 30% by weight of the polyamide fiber according to any one of (1) to (4) above.

(9) A polyamide fiber product comprising at least 30% by weight of the polyamide fiber according to any one of (1) to (4) above.

(10) Inner wear comprising at least part of the polyamide fiber according to any one of (1) to (4) above.

(11) A down shell comprising at least a part of the polyamide fiber according to any one of (1) to (4).

  According to the present invention described above, polyamide fiber having excellent antifungal performance and good color developability, crimped yarn made of the fiber, polyamide-based bulky processed yarn, polyamide-based covering elastic yarn, fabric , Textile products, innerwear and down shells can be obtained.

FIG. 1 is an explanatory diagram showing an example of a false twisting machine that can be used to manufacture a false twist crimped yarn that is an embodiment of the present invention. FIG. 2 is an explanatory diagram showing an example of a taslan processing machine that can be used to manufacture a taslan processed yarn that is one embodiment of the present invention. FIG. 3 is an explanatory diagram showing an example of a covering processing machine that can be used to manufacture a covering yarn that is one embodiment of the present invention. FIG. 4 is a trace of a photograph of the surface of the down shell and the state of feathers tested in Example 77 to be described later, and FIG. 4 (a) is a trace of a photograph of the surface of the down shell. (B) is a trace of a photograph of a down shell broken and taken of the goose. FIG. 5 is a trace of a photograph of the surface of the down shell and the state of feathers tested in Comparative Example 30 described below, and FIG. 5 (a) is a trace of a photograph of the surface of the down shell taken. (B) is a trace of a photograph of a down shell broken and taken of the goose.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyamide POY package 2 Feed roller 3 Hot plate heating apparatus 4 Twisting apparatus 5 Feed roller 6 Polyamide crimped yarn package 21 Filament package 22 used as core yarn Filament packages 23 and 24 used as sheath yarn Feed roller 25 Air turbulence processing Equipment (Taslan nozzle)
26 Take-up roller 27 Polyamide structure bulky processed yarn package 31 Elastic fiber package 32, 34 Feed roller 33 H-type bobbin 35 wound with polyamide filament Polyamide covering elastic yarn package 36 Elastic fiber yarn 37 Polyamide filament yarn 38 Polyamide type Covering elastic yarn α 71 types of fungal medium (after 28 days)
β Down shell surface state of the embodiment of the present invention (fabric)
γ Example of the present invention Down shell content (feathers)

  Hereinafter, the polyamide fiber and the like of the present invention will be described in more detail.

  The first aspect of the polyamide fiber of the present invention contains at least 0.05 to 3% by weight of an additive having antifungal performance, and the additive is formed by supporting an organic component on the surface of an inorganic oxide. The organic component is a mixed organic component containing a combination of at least two of imidazole compounds, pyridine compounds, thiazoline compounds, halogen compounds, and haloalkylthio compounds. It is what.

  Alternatively, in the second aspect of the thermoplastic fiber of the present invention, the additive is 97 to 99.9% by weight of the inorganic component and 0.1 to 3% by weight of the organic component with respect to the weight of the additive. It is characterized by comprising.

  It is important that the additive used in the present invention has at least fungicidal performance.

  Here, having fungicidal performance generally means that it acts on at least fungi among organisms such as bacteria, fungi, and algae. In particular, in the present invention, JIS Z 2911 (2000) “mold resistance test”. According to the “Method”, among the fungi, at least Aspergillus niger, Aspergillus terreus, Eurotium tonophilum, Penicillium citrinum, Penicillium citrinum. oryzae), Cladosporium (Cladosporiu) cladosporeoides), Aureobasidium pullulans, Gliocladium viren, Chaetomium bulosum, Fusarium moniform (Fusarium moniform) Is.

That is, the term “additive having fungicidal performance” or “organic component having fungicidal performance” as used in the present invention refers to an additive or organic component having a function of acting on the above-mentioned fungus. “Acting” means that an additive or an organic component is spread thinly over a 3 cm × 3 cm region on an inorganic salt agar medium, and 0.5 ml of the fungal mixed spore solution is sprinkled on the mixture, and the temperature is 28 It means that it can be determined that the growth of mycelia is not observed when cultured for 28 days in an environment of ± 2 ° C. and humidity of 85% RH or higher. The structure of the inorganic salt agar medium is not particularly specified, but KH ₂ PO ₄ , K ₂ HPO ₄ , MgSO ₄ .7H ₂ O, NH ₄ NO ₃ , NaCl, FeSO ₄ .7H ₂ O, ZnSO _4. It is composed of 7H ₂ O, MnSO ₄ · 7H ₂ O, agar, and pure water.

  Such an antifungal performance is such that the additive is configured so as to exhibit the antifungal performance as a whole, or when the additive is composed of a plurality of components, some of the components are The additive may be imparted with antifungal performance by having antifungal performance.

  Here, having an algal control effect generally means acting on at least algae among organisms such as bacteria, fungi and algae. Algae are all living organisms that use water for photosynthesis, except moss, ferns, and seed plants that live on land. Floating algae in ponds and green plants that adhere to the inside of aquarium walls. , Green that covers the bark, and blue-green on the wall of the building in a humid place on the north side. For example, Anacytis nidulans, Anacytis montana, Anacytis samarli, Anabenena sp. Chlorella vulgaris, Cladophora glomerata, Chlamydomonas reinhardii, Chlorococcum sp., Caloros palix arietina, Cylindrocapsa sp., Chlorella emersonii, Hormiumu sp., Mesotinacea, Mesotinica sp. sp.), Osslatria lutea, Prolococcus sp., Cyttonema hofmannii, Batracospermum sp. Brandia Species (Hidenbrandia sp.), Seisathrix sp. , Act on Zygogonium sp.

  That is, the term “algae-proofing” as used in the present invention means that an additive or an organic component is spread thinly over a 3 cm × 3 cm region on an inorganic salt agar medium, and the fungal mixed spore solution is placed in a 0. It means that it can be judged that hyphal growth is not observed when cultured for 5 days in an environment of a temperature of 28 ± 2 ° C. and a humidity of 85% RH or more over 5 ml.

The structure of the inorganic salt agar medium is not particularly limited, but KH ₂ PO ₄ , K ₂ HPO ₄ , MgSO ₄ .7H ₂ O, NH ₄ NO ₃ , NaCl, FeSO ₄ .7H ₂ O, ZnSO _4. It is composed of 7H ₂ O, MnSO ₄ · 7H ₂ O, agar, and pure water.

  The additive used in the present invention is present as fine solid particles that are well dispersed in the polyamide fiber, and the thermoplastic fibers are well dispersed in fine particles. In the present invention, it is possible to provide a good high level of fungicidal performance that is stable in the length direction. It has the role of achieving performance.

  Here, having antibacterial performance generally means acting on at least bacteria among organisms such as bacteria, fungi, and algae. For example, it acts on Staphylococcus aureus ATCC 6538P and Klebsiella pneumoniae ATCC 4352. In other words, in accordance with the quantitative antibacterial test method for textile products established by the Japan Textile Evaluation Technology Council, JIS L 1902 (2002) “Antimicrobial test method and antibacterial effect of textile products” 10.1 (bacterial solution absorption) Law).

  Since the above-mentioned additive can stably exhibit a good fungicidal effect in the fiber length direction by using the organic component and the inorganic component as described above, the addition amount thereof is relatively at least. It can exhibit a good fungicidal effect, and according to the various findings of the present inventors, it is good when the content of the additive is about 0.05 to 3% by weight in the total fiber weight A mildewproofing effect can be obtained. That is, it is possible to obtain both the organic component and the inorganic component successfully and maintain the original performance of the inorganic component, while also obtaining the fungicidal effect as a whole at an appropriate level. Too much emphasis on moldiness should avoid excessive use of organic components.

  According to the present invention, as described above, it is one important point that the content of the additive can be about 0.05 to 3% by weight in the total weight of the fiber. When the amount is less than% by weight, the effect of antifungal performance is generally weak, and it is difficult to obtain the desired effect in a good and stable manner throughout the fiber. On the other hand, if it exceeds 3% by weight, the antifungal performance is saturated, and on the other hand, not only the cost is increased, but also the mechanical properties such as the strength of the fiber are lowered, and the manufacturing process of the fiber itself In addition, when processing the fiber into a fabric by a high-order processing process, problems such as wear of guides and the like occur, which is not preferable. According to the knowledge of the present inventors, it is more preferably 0.1 to 2% by weight.

  From the viewpoints described above, the additive used in the present invention is important to be configured by using a combination of an organic component and an inorganic component in a well-balanced manner based on their respective roles. The inorganic component is preferably formed in a ratio of 97 to 99.9% by weight and the organic component in a ratio of 0.1 to 3% by weight. When the inorganic component is less than 97% by weight (when the organic component exceeds 3%), problems such as yellowing of the fiber and a decrease in fiber strength may occur due to polymer alteration. In addition, when the inorganic component exceeds 99.9% by weight (when the organic component is less than 0.1%), the antifungal performance tends to be low, and it is difficult to obtain the desired effect of the present invention. This is not preferable because it is in a direction subject to restrictions in use.

  The organic component constituting the additive used in the present invention allows the additive to retain antifungal performance, and as described above, it is important that the organic component act on a specific fungus. In the present invention, as such an organic component, a mixed organic component containing a combination of at least two of imidazole compounds, pyridine compounds, thiazoline compounds, halogen compounds, and haloalkylthio compounds is used. More preferably, it is a mixed organic component including a combination of at least two or more organic components among a pyridine-based compound, a haloalkylthio compound, and a halogen-based compound. Furthermore, it is preferably a mixed organic component containing all of an imidazole compound, a pyridine compound, a thiazoline compound, a halogen compound, and a haloalkylthio compound. In the case of only one kind, the antibacterial spectrum against bacteria, fungi, and algae is narrow and resistance is likely to occur, so by using a mixture of organic components, the antibacterial spectrum is wide and more effective fungicidal performance can be realized. It is. In addition to the above organic components, for example, a thiazole compound, an organic iodo compound, a nitrile compound, a triazine compound, an aldehyde compound, a carboxylic acid compound, or a pyrithione compound can be used in combination.

  The imidazole compound is not particularly limited, and examples thereof include 2- (4-thiazolyl) benzimidazole and methyl 2-benzimidazole carbamate. They have a broad antimicrobial spectrum for fungi. Moreover, it does not specifically limit as a pyridine type compound, For example, Na-pyridine thiol-1-oxide, Zn-pyridine thiol-1-oxide, 2,3,5,6-tetrachloro-4- ( Methylsulfonyl) pyridine and the like. They have a broad antibacterial spectrum against bacteria and fungi.

  The thiazoline-based compound is not particularly limited, and examples thereof include 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-n-octylisothiazolin-3-one, 2- (Thiocyanomethylthio) benzothiazole, 1,2-benzisothiazolin-3-one and the like. They have a broad antibacterial spectrum against bacteria and fungi. Examples of the halogen compound include diiodomethyl paratolyl sulfone and 3-iodo-2-propynyl butyl carbamate. They have a broad antimicrobial spectrum for fungi. Examples of haloalkylthio compounds include N-fluorodichloromethylthio) phthalimide, N-dimethyl-N′-phenyl-N ′ (fluorodichloromethylthio) -sulfamide, N-dichlorofluorodichloromethylthio) -N, N-dimethyl-Np. -Trisulfamide is mentioned. They have a broad antibacterial spectrum against fungi and algae.

  In addition, when an organic component is contained alone in a fiber that needs to be molded at a high temperature, the added amount that is effective for bacteria, fungi, algae, etc. even if the organic component is decomposed to some extent is 0.1% to the fiber. Although it is necessary to add more than% by weight, in this case, yellowing tends to occur remarkably. Therefore, in order to have an effect on bacteria, fungi, algae, etc. and reduce yellowing, the content of the organic component or organic component mixture is 0.1% by weight or less based on the total weight of the fiber, and the antibacterial property is reduced. It is effective to support the inorganic component. Therefore, in order to have the effect of bacteria, fungi, algae, etc. and reduce yellowing, the content of the organic component or organic component mixture is 0.1% by weight or less based on the total weight of the fiber, and the antibacterial property is reduced. It is effective to support the inorganic component.

  In the first aspect of the polyamide fiber of the present invention, the additive is an additive formed by supporting an organic component on the surface of an inorganic oxide, and the organic component is an imidazole compound, a pyridine compound, It is a mixed organic component containing a combination of at least two of a thiazoline compound, a halogen compound, and a haloalkylthio compound.

  A second aspect of the polyamide fiber of the present invention is characterized in that the additive comprises 0.1 to 3% by weight of the organic component based on the weight of the additive. As a method for measuring the amount of organic component, for example, the organic component can be measured by high performance liquid chromatography.

The inorganic component constituting the additive used in the present invention is not particularly limited. For example, metal oxides such as zinc oxide, titanium oxide, magnesium oxide, silicon dioxide, aluminum silicate, aluminum oxide, tin oxide, silver zeolite, Zirconium carbide, silicon carbide, carbon black, or the like can be used. Of these, metal oxides are preferable. Furthermore, a metal oxide having antibacterial performance is preferable. Examples of such metal oxides include zinc oxide, titanium oxide, tin oxide, and silver zeolite. In particular, zinc oxide or titanium oxide is more preferable because it has good dispersibility in fibers and can be processed with a small particle size. However, since zinc oxide and titanium oxide have a photocatalytic reaction, there may be problems such as a decrease in strength in a portion exposed to light or discoloration in the case of a textile product dyed for clothing or the like. Furthermore, although zinc oxide is trace amount, since it elutes in water, the problem that zinc oxide elutes by a dyeing | staining process and performance falls is also considered. Therefore, in order to suppress active oxygen and prevent degradation of the polymer, coloring due to deterioration, decrease in strength, and elution, the surface of the inorganic particles may be, for example, silicone, surfactant, Al ₂ O ₃ , SiO ₂ , ZnO, TiO. It is preferable to use it coated with ₂ or the like, and by covering the surface, secondary aggregation of the inorganic particles can be prevented, and a synergistic effect for further improving dispersibility can be obtained. Here, the “surfactant” refers to a substance that suppresses inorganic component active oxygen and has a function of preventing decomposition, deterioration, or elution of the polymer.

  Conventionally, inorganic particles having a photocatalytic action, such as zinc oxide and titanium oxide, have been completely covered with inorganic particles as a method for suppressing photocatalytic activity. Can be preferably used. As a method for partially covering the surface of inorganic component particles, a so-called wet method in which a coupling agent is added while stirring a slurry of inorganic particles in water or non-aqueous solvent may be used. A so-called dry method in which the coupling agent is sprayed or dripped while stirring the zinc oxide powder at high speed with a mixer or the like may be used, and a coupling agent carried with an inert gas such as nitrogen is introduced into the reaction vessel containing the zinc oxide powder. In addition, a so-called gas phase method for coating may be used.

  Here, the “coupling agent” may be a silane coupling agent, that is, a silane coupling agent having a vinyl group, a mercapto group, an amino group, or the like, and a titanium system other than the silane coupling agent, Other coupling agents such as aluminum-based, zirconium-based, zircoaluminate-based, or silane may be used.

  The additive formed by supporting the organic component on the surface of the inorganic component is obtained by dry blending the organic component with the inorganic component, preferably the inorganic component such as the inorganic particle having the photocatalyst-suppressing partial coating. be able to.

In a second embodiment of the polyamide fiber of the present invention, the additive comprises 97 to 99.9% by weight of the inorganic component based on the weight of the additive. As a method for measuring the amount of inorganic components, about 10 g of a polyamide fiber sample is precisely weighed, placed in a refractory container such as a crucible, burned with a gas burner, ashed in a furnace at 750 ° C. for 2 hours, and the amount of ash is measured. The conversion value of the amount of inorganic components in the fiber sample can be calculated. If a metal oxide is used as an inorganic component, about 1 g of a polyamide sample is accurately weighed, thermally decomposed with nitric acid, sulfuric acid and perchloric acid, and heated and concentrated until white smoke of sulfuric acid is produced. Dissolve in sulfuric acid to 25 cm ³ . About this solution, a metal substance can be measured by ICP emission spectroscopic analysis, the metal oxide in a polyamide fiber sample can be specified, and a converted value can be calculated.

  In the present invention, the polyamide is preferably polycaprolactam (nylon 6) or polyhexamethylene adipamide (nylon 66) from the viewpoint of production cost and fiber strength retention, and dispersibility of inorganic components such as zinc oxide and titanium oxide. In view of the above, polycaprolactam is more preferable.

  The polyamide fiber according to the present invention may contain the above-mentioned additive having antifungal performance by blending the polyamide resin pellet with an additive having antifungal performance and melting the polyamide resin pellet. A method of blending and melting master pellets containing an additive having an antifungal property, a method of adding an additive having an antifungal property to a polyamide resin in a molten state, and a step before or during the polymerization of the polyamide resin A method of adding an additive having antifungal properties to the raw material or the reaction system can be used, and any method may be used as long as both can be mixed uniformly.

  The method for producing the polyamide fiber of the present invention is not particularly limited, but it may be produced by spinning by a general melt spinning method, except that the additive is particularly added as described above. Can do.

  For example, in the case of filament production, polyamide resin pellets are melted, discharged from a spinneret discharge hole, the yarn is cooled, an oil agent is applied, and after entanglement treatment, taken up by the first roller at a speed of 1000 m / min or more. Then, after hot drawing through the second roller and winding at a speed of 3000 m / min or higher, the polyamide pellets are melted, discharged from the spinneret discharge holes, the yarn is cooled, and then the oil agent After the entanglement treatment, it is taken up by the first roller at a speed of 1000 m / min or more, and is wound substantially at a speed of 3000 m / min or more via the second roller without being stretched, or a polyamide resin. 2 steps of melting the pellet, discharging from the spinneret discharge hole, cooling the yarn, applying oil, winding up at a speed of 1000 m / min or less, and then stretching And the like. For example, in the case of staple production, raw cotton is produced by cutting after drawing, and then spinning and winding.

  The method for producing the polyamide crimped yarn of the present invention is not particularly limited, but it is a general crimp in itself except that a polyamide fiber added with an additive having at least an antifungal property is used. It can be produced by a processing method (false twisting method, indentation crimping method, fluid indentation crimping method by heating fluid, etc.).

  For example, in the case of false twisted yarn, FIG. 1 is an explanatory view showing an example of a false twist processing machine that can be used to manufacture a false twist crimped yarn that is one embodiment of the present invention. With a false twisting machine, a heater and false twisting spindle are installed between two pairs of rollers, and the polyamide filament is continuously twisted, heat-set, and untwisted, giving good stretch and irregular three-dimensional The structure is generated and wound up. The twisting mechanism is not particularly limited, and includes a hollow spinner method, a frictional direct twisting method (triaxial circumscribed method, inscribed cylindrical method), a belt nip method, and the like.

  When producing false twisted yarn, first, polyamide filaments are taken from a polyamide POY (partially oriented yarn) package 1 and a hot plate heating device 3 and a twisting device 4 are used between the feed roller 2 and the feed roller 5. And twisted into a polyamide crimped yarn package 6.

  The method for producing the polyamide-structured bulky processed yarn of the present invention is not particularly limited, but in the structurally bulky processed yarn composed of two or more filament yarns, at least one filament yarn is at least anti-proof. Other than using a polyamide fiber to which an additive having fungicidal properties is added, it can be produced by a general structural bulky processing method. The polyamide-based structural bulky yarn referred to in the present invention refers to a structural bulky processed yarn using at least a part of the polyamide fiber yarn according to the present invention.

  For example, in the case of Taslan (registered trademark) processed yarn, two filaments are supplied from different feed rollers at different speeds by the Taslan processing machine shown in FIG. It is wound and produced with slack.

  FIG. 2 is an explanatory view showing an example of a taslan processing machine that can be used to manufacture a taslan processed yarn according to an embodiment of the present invention. In FIG. Each is supplied to an air turbulence processing device (taslan nozzle) 25 via a feed roller 23, and simultaneously, a sheath yarn is supplied from a filament package 22 serving as a sheath yarn to the air turbulence processing device 25 via a feed roller 24. Here, two feed rollers 23 and 24 are used. However, one or a plurality of feed rollers are not limited, and it is preferable to provide a speed difference between the two feed rollers. The yarn supplied to 23 becomes the core yarn.

  These yarns are supplied to an air turbulent flow processing device (Taslan nozzle) 25 in an overfeed state with the take-up roller 26, and the phase in the length direction of the multifilaments is shifted by the compressed air, and the fiber length is partially increased. A structurally bulky processed yarn having a loop shape is formed by forming a difference and converging. Thereafter, the bulky processed yarn is heated by a heater (not shown) as necessary, and is wound around a polyamide-based bulky processed yarn package 27 via a take-up roller 26.

  Two or more polyamide filaments to which an additive having antifungal performance is added may be used or one may be used when forming the above polyamide-structured bulky processed yarn. Moreover, it is good also considering the polyamide filament which added the additive which has antifungal performance as a sheath or a core. In addition, if a polyamide filament to which at least one additive having fungicidal properties is added is used, the partner yarn is not particularly limited to the polyamide filament, but a polyester filament, a polylactic acid filament, a trimethylene terephthalate filament, Polybutylene terephthalate filaments, and the fiber cross-sectional shape of these filaments may be Y-shaped, T-shaped, hollow, flat, cross-shaped and irregularly shaped.

  The method for producing the polyamide-based covering elastic yarn of the present invention is not particularly limited. However, as described above, the method is generally general except that a polyamide fiber to which an additive having fungicidal performance is added is used. Can be manufactured by a typical covering process. The polyamide-based covering elastic yarn referred to in the present invention refers to a covering elastic yarn using at least a part of the polyamide fiber yarn according to the present invention.

  For example, in the case of double covering yarn, the elastic fiber of the core yarn is stretched 2 to 4 times between two rollers, and the coated yarn wound on the upper and lower hollow bobbins (added at least an additive having antifungal performance) Polyamide fiber) is produced by wrapping it twice in such a manner that the upper and lower rotational directions are opposite to cancel the torque. In the case of a single covering yarn, a coated yarn (polyamide fiber to which an additive having at least fungicidal performance is added) wound around a hollow bobbin is wound in a spiral shape.

  FIG. 3 is an explanatory diagram showing an example of a covering processing machine that can be used to manufacture a covering yarn that is one embodiment of the present invention. In FIG. 3, an elastic fiber yarn 36 serving as a core yarn is supplied from an elastic fiber package 31, stretched between two feed rollers 32 and 34, and supplied from an H-type bobbin 33 around which a polyamide filament is wound. A polyamide filament yarn 37 is wound spirally. The polyamide covering elastic yarn 38 around which the polyamide filament yarn is wound is wound around the polyamide covering elastic yarn package 35.

  Elastic fibers include polyurethane elastic fibers (spandex), polyester elastomer elastic fibers, polyamide elastomer elastic fibers, polyolefin elastomer elastic fibers, natural rubber fibers, synthetic rubber fibers, and butadiene fibers. The heat setting property and durability may be selected as appropriate. More preferred are polyurethane-based elastic fibers, polyolefin-based elastomer elastic fibers, and polyamide-based elastomer elastic fibers.

  What is necessary is just to select suitably the thickness of the elastic fiber, the number of twists, and the draft (elongation rate between 2 rollers) according to the characteristic and use of an elastic fiber.

  For example, in the case of stockings, polyurethane elastic fibers are preferably used as elastic fibers. The thickness varies depending on the setting of the tightening pressure of the stocking, but generally only needs to be about 8 to 33 dtex to achieve the durability, transparency, and stretch properties that are required characteristics of the stocking. When it is less than 8 dtex, not only durability and stretchability become insufficient, but also troubles such as core yarn breakage frequently occur during the production of covering elastic yarn or knitting. On the other hand, if it exceeds 33 dtex, the tightening pressure becomes high, the coarseness (softness is lowered) and the transparency are also lowered. Further, the covering twist number may be designed in consideration of the fineness, shrinkage rate, product texture, and durability of the coated yarn. For example, in the case of a single covering elastic yarn having a fineness of the coated yarn of 11 dtex, it is preferable to set 1800 to 2400 T / m as a guide. The draft may be determined in consideration of the tightening pressure and durability of the product. For example, when the fineness of the polyurethane elastic yarn is 18 dtex, it is preferable to determine with a draft magnification of 2.4 to 3.5 times as a guide.

  In the case of inner use and outer use, similarly, the type of elastic fiber, the thickness of the elastic fiber, the number of covering twists, and the draft are appropriately selected according to the desired properties such as the stretchability of the product.

  The method for producing the innerwear of the present invention is not particularly limited. However, as described above, the additive itself is added to the polyamide fiber as described above. Can be manufactured by a method of creating a knitted fabric and sewing it into an innerwear product.

  Specific knitted fabric creation methods include molded product knitting machines (flat knitting machines (flat knitting machines, cotton knitting machines), circular knitting machines / sock knitting machines), fabric knitting machines (weft knitting machines, warp knitting machines). Machine). The structure of the knitted fabric is not particularly limited. For example, in the case of a weft knitting, a flat knitting (tengu), a rubber knitting (rib knitting), a pearl knitting (garter knitting), a double knitting (smooth knitting) ), Flat organization change organization (parent-child tengu, Kanoko edition, Hen Lingbon, floating edition, single jacquard, accordion edition, lace edition, spliced yarn edition, pile edition, rope edition, intarsia edition, etc.), rubber organization change organization ( Needle-free rubber knitting, head knitting, double knitting, swing knitting, double jacquard knitting, single bag knitting, milan rib, double picket, blister, etc., double-sided knitting change organization (eight lock, single picket, mock milan, ponchiroma Etc.). In the case of warp knitting, there are tricot (Denby knitting, cord knitting, atlas knitting, etc.) and Raschel knitting.

  According to various findings of the present inventors, the knitted fabric for innerwear according to the present invention has the desired effect of the present invention by using the polyamide fiber in an amount of 30% by weight or more. Is important above. Generally, innerwear is rarely composed of only a single material, and is used in combination according to the purpose, such as natural fiber, semi-synthetic fiber, and synthetic fiber. Therefore, when the amount of polyamide fiber is less than 30% by weight, the fungicidal performance cannot be sufficiently obtained, which is not preferable. The upper limit is 100% by weight.

  The method for dyeing the knitted fabric for innerwear according to the present invention is not particularly limited, but can be dyed by a general method. Moreover, you may add the functional process which does not impair this performance.

  Specific examples of the innerwear of the present invention include a foundation (body suit, bra, girdle, garter belt, waist nipper, bust pad, hip pad, side pad), lingerie (camisole, petticoat, slip, brass slip, tuck pants, Teddy), underwear (underwear) (shirt, shorts, bottom).

  The method for producing the down shell of the present invention is not particularly limited. However, as described above, the additive itself is added to the polyamide filament, and the method for producing the down shell itself is a general production method (weaving a fabric with a loom). Produced, sewn and made into a down shell product).

  According to the various knowledge of the present inventors, the fabric for down shell according to the present invention uses 30% by weight or more of the above polyamide filaments in order to have the desired effect of the present invention. It is.

The down shell of the present invention can be obtained by using the polyamide fiber of the present invention for warp and / or weft. The method of tailoring the woven fabric can be performed by a known method. In general, warp yarns are first arranged in a creel and warped, wound around a beam, and then the yarn wound around the beam is glued and dried to prepare the warp yarn. Next, the warp yarn is passed through the weave of the loom, and the weft yarn is driven into the fabric. There are various types of looms such as a shuttle loom, an air jet loom, and a water jet loom. There are several weaving structures such as plain weave, twill, and satin depending on how the weft is driven. Any one can be selected according to the purpose. In applications where softness and ease of movement are required, such as down jackets, a method of reducing the thickness of the fabric is effective. The basis weight at this time is preferably 50 g / cm ² or more, and the tear strength is preferably 1 kgf or more. In order to obtain a tear strength of 1 kgf or more, a method of weaving into a lip structure is effective. The obtained woven fabric may be used as it is, or may be subjected to refining, dyeing, and heat setting. Dyeing can be performed using an acid dye used for dyeing ordinary polyamide fibers, and is performed by treating in a hot water bath at 90 ° C. or higher for about 60 to 90 minutes.

  A method for preparing a down shell obtained by using the polyamide fabric of the present invention can also be performed by a known method. In addition, it is preferable to perform calendering in order to prevent the feathers packed in the down shell from coming out, suppress air permeability, and prevent molds existing in the air from adhering to the feathers. The calendering can be performed at any stage of the dyeing finishing process, but is preferably performed after dyeing. Moreover, resin processing can also be carried out to the textile single side | surface or both surfaces as needed. To obtain desired properties such as water repellency, moisture permeability and waterproofing, etc. by processing with water repellent, urethane resin, acrylic resin, silicon resin, etc. by coating method, laminating method, dust absorption method, pad method, etc. Can do.

  The down shell of the present invention is used for a down jacket, a sleeping bag, a duvet, a heat insulating case, a hat, a glove, and the like. Moreover, what is packed in the down shell is not limited to feathers, and various types of claw cotton such as cotton, acrylic, or polyester may be used.

  The fabric of the present invention is produced by an ordinary method as described in, for example, “Fiber Encyclopedia” (Maruzen Co., Ltd., p. 146 to 187).

  According to the various findings of the present inventors, the use of the polyamide fiber in an amount of 30% by weight or more is important for making a fabric having the desired effect of the present invention. In general, fabrics are rarely composed of only a single material, and are used in combination according to the purpose, such as natural fibers, semi-synthetic fibers, and synthetic fibers. Therefore, if it is less than 30% by weight, it is not preferable because the fungicide performance cannot be sufficiently obtained. The upper limit is 100% by weight.

  The textile product of the present invention can be dyed and processed into a textile product or the like by an ordinary method as described in, for example, “Encyclopedia of Fibers” (Maruzen Co., p. 188-211). In that case, the mixing ratio is the same as that in the case of the above-mentioned fabric.

  The textile product according to the present invention, for example, stockings, tights, socks, innerwear, outerwear, sportswear, uniforms, work clothes, duvets, duvet covers, curtains, carpets, filters, taking advantage of its good fungicidal performance Industrial sheets, artificial leather, bags, towels, material ropes, fishing nets, draining nets, laundry nets, mosquito nets, uniforms, work clothes, gloves, feathers, sleeping bags, etc.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, the following method was used for the measuring method in an Example.

A. Mold resistance (hereinafter referred to as mold resistance)
The following 71 bacteria were used as molds (fungi). The test bacterial solution by wet method is evenly spread on the culture surface and the test piece (5 cm x 5 cm), and cultured in an inorganic salt agar medium at a temperature of 29 ± 1 ° C and a humidity of 90% ± 5% RH for 28 days. It was evaluated by a five-step evaluation. Two points or less were accepted.
1 point: No bacteria are generated in the area of the surface of the test piece (fabric) on which the bacteria are sprinkled,
2 points: Developed in an area of 10% or less in the surface area of the test piece on which the bacteria were sprinkled,
3 points: Developed in the area of more than 10% and 30% or less in the area of the surface of the test piece on which the bacteria were sprinkled,
4 points: Developed in the area of more than 30% and less than 60% in the area of the surface of the test piece on which the bacteria were sprinkled,
5 points: Developed in a region exceeding 60% in the area of the surface of the test piece on which the bacteria were sprinkled (complete growth).

  The inorganic salt agar medium was prepared by heating the following components at 121 ° C. for 20 minutes and adjusting the pH of the solution to 6.0 to 6.5 with 0.01 N NaOH.

a) Medium composition component name and content KH ₂ PO ₄ : 0.7 g
K ₂ HPO ₄ : 0.7 g
MgSO ₄ · 7H ₂ O: 1.0 g
NaCl: 0.005g
FeSO ₄ · _7H 2 O: 0.002g
ZnSO ₄ · 7H ₂ O: 0.002 g
MnSO ₄ · 7H ₂ O: 0.001 g
Agar: 15g
Pure water: 1000ml

b) Test bacterial solution Mixed spore solution: An aqueous solution obtained by removing agar from the medium is added to the spore, adjusted to 10 ⁶ ± 200,000 cells / mL, and mixed in equal amounts.
Wetting liquid: Sodium laurate 0.05 g / L

c) Test fungi (fungi)
Alta Alternaria Arutanata (Alternaria alternata), Aspergillus niger (Aspergillus niger), Aspergillus oryzae (Aspergillus oryzae), Aspergillus flavus (Aspergillus flavus), Aspergillus Bashikara (Aspergillus versicolor), Aspergillus fumigatus (Aspergillus humigatus), Aspergillus terreus (Aspergillus terreus), Aspergillus restrictus, Aspergillus ochraceus, Aspergillus candidas (Aspergillus) s candidus, Alternaria tenuis, Alcaligenes faecalis (Alcaligenes faecalis), Alternaria brasicum (Calida), Aureobasidium pulsium (Aureobasidium pulsium) , Cladosporium cladosporoides, cladosporium sphaerospermum, cladosporium herboram rium herbarum), Cladosporium Rejinae (Cladosporium resinae), Karubararia lunata (Curvularia lunata), Doresshira male tiger line (Drechslera australiensis), Epikokkamu Paparasen (Epicoccum purpurascens), Yurochiumu Tanefiramu (Eurotium tonophilum), Yurochiumu rubrum (Eurotium rybrum), Yurochiumu Eurotium chevaleri, Eurotium amsterodami, Fusarium semitectum, Fusarium oxysporum (Fus) arium oxysporum), Fusarium solani, Fusarium roseum, Fusarium moniforme, Fusarium moniforme, Fusarium proliferatum, Fusarium proliferatum, Gliocladium virens, Monilia fructigena, Monilia nigra, Mucor racemosus, Myrotice balcaria hecium verrucaria), Mucor Supinessensu (Mucor spinescens), Nigurosupora oryzae (Nigrospora oryzae), Nigurosupora Suferika (Nigrospora sphaerica), Neurospora Sutofira (Neurospora sitophila), Penicillium free Kuen task (Penicillium frequentance), Penicillium chair Randy cam (Penicillium islandicum) , Penicillium citrinum, Pullularia pullulans, Penicillium expansum, Penicillium Kuropiamu (Penicillium cyclopium), Penicillium Shitoreobiride (Penicillium citreo-viride), Penicillium Fanikyurozamu (Penicillium funiculosum), Penicillium nigricans (Penicillium nigricans), Penicillium Rirashinamu (Penicillium lilacinum), Pesutarotia Adasuta (Pestalotia adusta), Pesutarotia Negurekuta (Pestalotia neglecta), Forma citricarpa, Fora terrestrius, Fora glomerata, Rhizopus Gurikansu (Rhizopus nigricans), Rhizopus oryzae (Rhizopus oryzae), Rhizopus stroke Nifa (Rhizopus storonifer), Rhizopus solani (Rhizopus sorani), Sedosuporiumu Apio Cum arm (Scedosporium apiospermum), Trichoderma feet down Min tag Luffy test (Trichophyton mentagrophytes), Trichoderma Trichoderma viride, Trichoderma koningii, Trichoderma T-1, Trichoderma harzianum, Urocradium aturo Lamb (Ulocladium atrum), Walemia sebi (Wallemia sevi)

B. Fungus, algae resistance (hereinafter referred to as fungicidal and algal resistant)
As fungi (fungi), 71 bacteria shown below and 27 algae shown below were used as algae. The test bacterial solution by wet method is evenly spread on the culture surface and the test piece (5 cm x 5 cm), and cultured in an inorganic salt agar medium at a temperature of 29 ± 1 ° C and a humidity of 90% ± 5% RH for 28 days. It was evaluated by a five-step evaluation. Two points or less were accepted.
1 point: No bacteria are generated in the area of the surface of the test piece (fabric) on which the bacteria are sprinkled,
2 points: Developed in an area of 10% or less in the surface area of the test piece on which the bacteria were sprinkled,
3 points: Developed in the area of more than 10% and 30% or less in the area of the surface of the test piece on which the bacteria were sprinkled,
4 points: Developed in the area of more than 30% and less than 60% in the area of the surface of the test piece on which the bacteria were sprinkled,
5 points: Over 60% of the area of the surface of the test piece on which the bacteria were sprinkled (complete growth).

  The inorganic salt agar medium was prepared by heating the following components at 121 ° C. for 20 minutes and adjusting the pH of the solution to 6.0 to 6.5 with 0.01 N NaOH.

a) Medium composition component name and content KH ₂ PO ₄ : 0.7 g
K ₂ HPO ₄ : 0.7 g
MgSO ₄ · 7H ₂ O: 1.0 g
NaCl: 0.005g
FeSO ₄ · _7H 2 O: 0.002g
ZnSO ₄ · 7H ₂ O: 0.002 g
MnSO ₄ · 7H ₂ O: 0.001 g
Agar: 15g
Pure water: 1000ml

b) Test bacterial solution Mixed spore solution: An aqueous solution obtained by removing agar from the medium is added to the spore, adjusted to 10 ⁶ ± 200,000 cells / mL, and mixed in equal amounts.
Wetting liquid: Sodium laurate 0.05 g / L

c) Test fungi (fungi)
Alta Alternaria Arutanata (Alternaria alternata), Aspergillus niger (Aspergillus niger), Aspergillus oryzae (Aspergillus oryzae), Aspergillus flavus (Aspergillus flavus), Aspergillus Bashikara (Aspergillus versicolor), Aspergillus fumigatus (Aspergillus humigatus), Aspergillus terreus (Aspergillus terreus), Aspergillus restrictus, Aspergillus ochraceus, Aspergillus candidas (Aspergillus) s candidus, Alternaria tenuis, Alcaligenes faecalis (Alcaligenes faecalis), Alternaria brasicum (Calida), Aureobasidium pulsium (Aureobasidium pulsium) , Cladosporium cladosporoides, cladosporium sphaerospermum, cladosporium herboram rium herbarum), Cladosporium Rejinae (Cladosporium resinae), Karubararia lunata (Curvularia lunata), Doresshira male tiger line (Drechslera australiensis), Epikokkamu Paparasen (Epicoccum purpurascens), Yurochiumu Tanefiramu (Eurotium tonophilum), Yurochiumu rubrum (Eurotium rybrum), Yurochiumu Eurotium chevaleri, Eurotium amsterodami, Fusarium semitectum, Fusarium oxysporum (Fus) arium oxysporum), Fusarium solani, Fusarium roseum, Fusarium moniforme, Fusarium moniforme, Fusarium proliferatum, Fusarium proliferatum, Gliocladium virens, Monilia fructigena, Monilia nigra, Mucor racemosus, Myrotice balcaria hecium verrucaria), Mucor Supinessensu (Mucor spinescens), Nigurosupora oryzae (Nigrospora oryzae), Nigurosupora Suferika (Nigrospora sphaerica), Neurospora Sutofira (Neurospora sitophila), Penicillium free Kuen task (Penicillium frequentance), Penicillium chair Randy cam (Penicillium islandicum) , Penicillium citrinum, Pullularia pullulans, Penicillium expansum, Penicillium Kuropiamu (Penicillium cyclopium), Penicillium Shitoreobiride (Penicillium citreo-viride), Penicillium Fanikyurozamu (Penicillium funiculosum), Penicillium nigricans (Penicillium nigricans), Penicillium Rirashinamu (Penicillium lilacinum), Pesutarotia Adasuta (Pestalotia adusta), Pesutarotia Negurekuta (Pestalotia neglecta), Forma citricarpa, Fora terrestrius, Fora glomerata, Rhizopus Gurikansu (Rhizopus nigricans), Rhizopus oryzae (Rhizopus oryzae), Rhizopus stroke Nifa (Rhizopus storonifer), Rhizopus solani (Rhizopus sorani), Sedosuporiumu Apio Cum arm (Scedosporium apiospermum), Trichoderma feet down Min tag Luffy test (Trichophyton mentagrophytes), Trichoderma Trichoderma viride, Trichoderma koningii, Trichoderma T-1, Trichoderma harzianum, Urocradium aturo Lamb (Ulocladium atrum), Walemia sebi (Wallemia sevi)

d) Test algae Anacytis nidulans, Anacytis montana, Anacytis summere, Anabaena sp. us, Anxtrod Barkali (Chlorella vulgaris), Cladophora glomerata, Chlamydomonas reinhardii, Chlorococcum spi (Chrorococcum sp.) ina), Cylindrocapsa sp., Chlorella emersonii, Hormidium sp. No., Mesotinacea sp. sp.), Osslatria lutea, Prolococcus sp., Cyttonema hofmannii, Batracosperm sp. Hiddenbrandia sp., Sehithrix sp., Tribonea sp., Trentaporia odata, Trenteporia entrea Species (Zygogonuim sp.)

C. Antibacterial properties In accordance with the quantitative antibacterial test method for textile products established by the Japan Textile Evaluation Technology Council, JIS L 1902 (2002) “Antimicrobial test method for textile products / antibacterial effect” 10.1 (bacterial solution absorption) According to the above method, the measurement was performed using at least Staphylococcus aureus ATCC 6538P and Klebsiella pneumoniae ATCC 4352 as bacteria. An activity value of 2.2 or more and a bactericidal activity value of 0 or more were judged to be antibacterial.

D. YI value X, Y, and Z values are measured and calculated using a Σ80 color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. Evaluation was made according to the following criteria.
YI value = (1.28X-1.26Z) / Y
A: YI value less than 5,
○: YI value of 5 or more and less than 10,
Δ: YI value of 10 or more and less than 20;
×: YI value 20 or more

E. Color developability The color developability was evaluated by 5 inspectors consisting of skilled developers and evaluated according to the following criteria.
A: Very good color developability,
○: Slightly good color development
Δ: Slightly poor color development,
×: poor color development

F. Thread-making property The number of yarn breaks that occurred in the spinning process was counted, and the number of yarn breaks during 1t fiber spinning was evaluated according to the following criteria.
A: Less than one yarn break,
○: thread breakage 1 time or more and less than 3 times,
Δ: Thread breakage 3 times or more and less than 6 times,
X: 6 or more thread breaks.

G. 98% sulfuric acid relative viscosity 0.25 g of fiber was dissolved in 25 ml of 98% sulfuric acid and measured at 25 ° C. using an Ostwald viscometer.

Examples 1-10
Zinc oxide (“ZNOUVE” manufactured by Mitsui Mining & Smelting Co., Ltd., organic silicon compound micro-deposited powder) 99% by weight as an inorganic component and a partial coating for suppressing photocatalyst, and 10 types of mixtures shown in Table 1 as organic components are selected. The total amount of the mixture was used at 1% by weight, and antifungal agents A to J were obtained as additives in which the organic component mixture was supported on the zinc oxide by dry blending. The obtained fungicides A to J were kneaded so as to be 2.0% by weight with respect to nylon 6 having 98% sulfuric acid relative viscosity of 2.7 to produce master pellets.

  The obtained master pellet was blended with nylon 6 pellet of 98% sulfuric acid relative viscosity 2.7, and the mixed pellet was adjusted so that the fungicide content in the fiber was 0.15% by weight. The obtained mixed pellet is melted at a spinning temperature of 260 ° C., discharged from a spinneret having a round discharge hole with a hole diameter of 0.2 mm, cooled by cooling air from one direction, and for fibers mainly composed of fatty acid esters. After supplying oil by applying 1% by weight to the fiber at a position 1800 mm from the spinneret and applying entanglement, the second goded roller (non-heated roller) is passed through 3300 m / min. 150 ° C. heating roller) was wound through 4500 m / min to obtain a nylon 6 fiber yarn of 33 dtex 26 filaments.

  The obtained nylon 6 fiber yarn is put on a cylinder knitting machine (cage diameter 3.5 inches, number of needles 240, NE450W manufactured by Eikoh Industries Co., Ltd.) to create a cylinder knitted fabric with one yarn supply, and the YI value Was measured. The obtained tubular knitted fabric is dyed at 98 ° C. for 60 minutes using 1% by weight of an acid dye (Nylosan Blue N-GFL 167%, manufactured by Sandos) to prevent mold, antibacterial, and fungi. Was measured. The results are shown in Table 2.

  In all the levels, the color developability after dyeing was good without dullness.

Comparative Examples 1 and 2
Yarn production was performed in the same manner as in Example 1 except that zinc oxide (manufactured by Hakusuitec Co., Ltd.) and silver-based inorganic antibacterial agent “NOVALON” (manufactured by Toagosei Co., Ltd.) were used as additives, and a nylon 6 fiber yarn of 33 dtex 26 filament Obtained. A cylindrical knitted fabric was prepared from the obtained nylon 6 fiber yarn in the same manner as in Example 1, the YI value was measured, and further dyed to measure the antifungal property, antibacterial property, and antifungal property. The results are shown in Table 2. In all the levels, the color development after dyeing was good without any dullness.

  As is clear from Table 2, the polyamide fiber according to the present invention is a fiber having a low YI value and excellent whiteness, and has excellent color developability, antifungal properties, antibacterial properties, and antifungal properties after dyeing. Yes. On the other hand, additives that do not have fungicidal properties (generally zinc oxide used as an antibacterial agent and silver-based inorganic antibacterial agents) were inferior in fungicide and fungicidal properties.

Examples 11-16, Comparative Examples 3-5
The mold was made in the same manner as in Example 1 except that the types of fungicides were A to C, and the addition amount was 1% by weight, 2% by weight, and 3.5% by weight in the fiber, respectively. A nylon 6 fiber yarn was obtained. A cylindrical knitted fabric is prepared from the obtained nylon 6 fiber yarn in the same manner as in Example 1, the YI value is measured, and further dyeing is performed, and the antifungal property, antibacterial property, antifungal property, and coloring property are measured. did. The results are shown in Table 3.

Examples 17-19
Use nylon 66 with 98% sulfuric acid relative viscosity 2.9 instead of nylon 6 and melt fungicides A to C at a spinning temperature of 290 ° C. to 0.15% by weight of nylon 66 in the fiber. A nylon 66 fiber yarn of 33 dtex 26 filaments was obtained in the same manner as in Example 1 except that. A cylindrical knitted fabric was prepared from the obtained nylon 66 fiber yarn in the same manner as in Example 1, and the YI value, antifungal property, and antibacterial property were measured. However, the antifungal, antibacterial and antifungal properties were performed on undyed products (scouring and removing the oil for fiber).

Comparative Example 6
Yarn production was carried out in the same manner as in Example 1 except that only nylon 6 pellets with 98% sulfuric acid relative viscosity 2.7 (antifungal addition amount 0%) were obtained to obtain nylon 6 fiber yarns of 33 dtex 26 filaments. A cylindrical knitted fabric is prepared from the obtained nylon 6 fiber yarn in the same manner as in Example 1, the YI value is measured, and further dyed to give fungicidal properties, antibacterial properties, fungicidal properties, and color development properties. It was measured. The results are shown in Table 3.

  As is apparent from Table 3, the thermoplastic fiber in the present invention is a fiber having a low YI value and excellent whiteness, and is excellent in color development, antifungal, antibacterial and antifungal properties after dyeing. Yes. On the other hand, Comparative Examples 3 to 5 in which the content was out of the range had a high YI value and slightly turned yellow, and the coloring property after dyeing was dull. In the case of Comparative Examples 3 to 5, yarn breakage frequently occurred during yarn production, and yarn breakage occurred frequently especially after 5 days of yarn production. Deep scratches were found when observing the fiber guide. When the content is large, it can be seen that a lot of fungicides are present on the surface of the fiber, so that it occurs and accelerates yarn breakage. Moreover, the comparative example 6 did not have antifungal property, antibacterial property, and antifungal property.

[Example with false twisted yarn]
Examples 20-29
The master pellets of fungicides A to J produced in Examples 1 to 10 were blended with nylon 6 pellets of 98% sulfuric acid relative viscosity 2.7 and mixed to a fungicide content of 0.15% by weight. The pellet was prepared. The obtained mixed pellet was melted at a spinning temperature of 260 ° C., discharged from a spinneret having a round discharge hole having a hole diameter of 0.2 mm, cooled by cooling air from one direction, and a hydrous oil (polyether as a main component). After the oil is fed at a concentration of 10%) and entangled, the second goded roller (non-heated roller) 4500 m / min is passed through the first goded roller (non-heated roller) without substantially stretching. To obtain a nylon 6 filament POY of 41 dtex 26 filaments.

  Using the obtained nylon 6 filament POY as a false twister, IVF805 (manufactured by Ishikawa Seisakusho Co., Ltd.), processing speed 500 m / min, draw ratio 1.2 times, heater temperature 170 ° C., D / Y ratio 1.7 ( Untwisting tension / twisting tension = 1.04) and false twisting were performed to obtain 33 dtex 26 filament nylon 6 false twisted yarn. The obtained nylon 6 false twisted yarn is put on a cylinder knitting machine (cage diameter 3.5 inches (88.9 mm), number of needles 240, NE450W manufactured by Eikoh Industries, Ltd.) and is knitted in a single yarn. The ground is knitted and dyed at 98 ° C. for 60 minutes using 1% by weight of an acid dye (Nylosan Blue N-GFL 167%, manufactured by Sandos). Antifungal property, YI value, antibacterial property, antifungal property Was measured. The results are shown in Table 4.

Comparative Examples 7 and 8
As an additive, zinc oxide (manufactured by Hakusui Tech Co., Ltd.) (Comparative Example 7), silver-based inorganic antibacterial agent “NOVALON” (manufactured by Toagosei Co., Ltd.) (Comparative Example 8) was used to produce yarn as in Example 20, A 41 decitex 26 filament nylon 6 filament POY was obtained. The obtained nylon 6 filament POY was evaluated in the same manner as in Example 1 by false twisting, knitting, and dyeing. The results are shown in Table 4.

Examples 30 to 35, Comparative Examples 9 to 11
Yarn production was carried out in the same manner as in Example 20 except that the amounts of the fungicides A to C were changed to 1% by weight, 2% by weight and 3.5% by weight, respectively, to obtain a nylon 6 filament POY of 41 decitex 26 filaments. It was. The obtained nylon 6 filament POY was false twisted, knitted and dyed in the same manner as in Example 20 to evaluate the antifungal property, antibacterial property and antifungal property. Furthermore, the yarn forming property was also evaluated. The results are shown in Table 5.

  Nylon 6 filament POY to which 3.5% by weight of fungicides A to C is added (Comparative Examples 9 to 11) has many yarn breaks, and the fibers are yellowed, and cannot be used as a fabric or textile product. Met.

Comparative Example 12
Yarn production was carried out in the same manner as in Example 20 except that only nylon 6 pellets with 98% sulfuric acid relative viscosity 2.7 (antifungal addition amount 0%) were obtained to obtain nylon 6 filament POY of 41 dtex 26 filaments. The obtained nylon 6 filament POY was evaluated by performing false twisting, knitting, and dyeing in the same manner as in Example 20. The results are shown in Table 5. Since antifungal performance was poor, antibacterial and antifungal properties were not evaluated.

[Example of bulky processed yarn]
Examples 36-45
Master pellets produced in Examples 1 to 10 and nylon 6 pellets having 98% sulfuric acid relative viscosity of 2.7 were blended so as to have a fungicide content of 0.15% by weight to prepare mixed pellets. The obtained mixed pellet is melted at a spinning temperature of 260 ° C., discharged from a spinneret having a round discharge hole with a hole diameter of 0.2 mm, cooled by cooling air from one direction, and for fibers mainly composed of fatty acid esters. After supplying oil by applying 1% by weight to the fiber at a position 1800 mm from the spinneret and applying entanglement, the second goded roller (non-heated roller) is passed through 3300 m / min. 150 ° C. heating roller) was wound through 4500 m / min to obtain nylon 6 filament of 78 dtex 52 filament.

Using the obtained nylon 6 filaments as core yarn and sheath yarn, Taslan processing machine AT-2 (manufactured by Aiki Seisakusho), processing speed 350 m / min, sheath yarn overfeed rate 7%, core yarn A Taslan processed yarn was obtained by setting the overfeed rate to 35% and the pressure supply amount of the air turbulent processing nozzle to 7 kg / cm ² . The obtained taslan processed yarn is put on a cylindrical knitting machine (cable diameter 3.5 inch (88.9 mm), number of needles 240, NE450W manufactured by Eikoku Sangyo Co., Ltd.), and a cylindrical knitted fabric is knitted with one yarn. Then, dyeing treatment was performed at 98 ° C. for 60 minutes using 1% by weight of an acidic dye (Nylosan Blue N-GFL 167%, manufactured by Sandos Co., Ltd.), and antifungal, antibacterial and antifungal properties were measured. In the above, after knitting, the YI value was measured before dyeing, and the color developability was evaluated after dyeing. The results are shown in Table 6.

Comparative Examples 13 and 14
Yarn production was carried out in the same manner as in Example 36 except that zinc oxide (manufactured by Hakusui Tech Co., Ltd.) and silver-based inorganic antibacterial agent “NOVALON” (manufactured by Toagosei Co., Ltd.) were used as additives, and a nylon 6 filament of 78 dtex 52 filament was obtained. . The obtained nylon 6 filament was subjected to taslan processing, knitting and dyeing in the same manner as in Example 36 and evaluated. The results are shown in Table 6.

Examples 46-51, Comparative Examples 15-17
Yarn production was carried out in the same manner as in Example 37 except that the amounts of the fungicides A to C were changed to 1% by weight, 2% by weight, and 3.5% by weight, respectively, to obtain nylon 6 filaments of 78 dtex 52 filaments. . The obtained nylon 6 filament was subjected to taslan processing, knitting and dyeing in the same manner as in Example 36 and evaluated. Furthermore, the yarn forming property was also evaluated. The results are shown in Table 7. Nylon 6 filaments (Comparative Examples 15 to 17) to which 3.5% by weight of fungicides A to C are added have many yarn breaks, the fibers are yellowed, and the color development is inferior. As it was not usable.

Comparative Example 18
Yarn production was carried out in the same manner as in Example 37 except that only nylon 6 pellets having a 98% sulfuric acid relative viscosity of 2.7 (the addition amount of the fungicide was 0%) were obtained to obtain nylon 6 filaments of 78 dtex 52 filaments. The obtained nylon 6 filament POY was subjected to taslan processing, knitting, and dyeing in the same manner as in Example 36 and evaluated. The results are shown in Table 6. Since the thing of this comparative example 18 was inferior in antifungal performance, it did not carry out to antibacterial property and antifungal prevention property evaluation.

Example 52
Using the nylon 6 filament obtained in Example 37 as the core yarn and the nylon 6 filament obtained in Comparative Example 18 as the sheath yarn, processing was performed in the same manner as above to obtain a taslan processed yarn. The obtained taslan processed yarn is put on a cylindrical knitting machine (cable diameter 3.5 inch (88.9 mm), number of needles 240, NE450W manufactured by Eikoku Sangyo Co., Ltd.), and a cylindrical knitted fabric is knitted with one yarn. Then, dyeing treatment was performed at 98 ° C. for 60 minutes using 1% by weight of an acidic dye (Nylosan Blue N-GFL 167%, manufactured by Sandos Co., Ltd.), and antifungal, antibacterial and antifungal properties were measured.
Antifungal property 0 point, bacteriostatic value of Staphylococcus aureus:> 4.1, bactericidal activity value:> 1.5, bacteriostatic activity value of Klebsiella pneumoniae:> 4.5, bactericidal activity value:> 1.4

[Example of covering elastic yarn]
Examples 53-62
Master pellets produced in Examples 1 to 10 and nylon 6 pellets of 98% sulfuric acid relative viscosity 2.7 were blended so that the fungicide content was 0.15% by weight to prepare mixed pellets. . The obtained mixed pellet is melted at a spinning temperature of 260 ° C., discharged from a spinneret having a round discharge hole with a hole diameter of 0.2 mm, cooled by cooling air from one direction, and for fibers mainly composed of fatty acid esters. After supplying oil by applying 1% by weight to the fiber at a position 1800 mm from the spinneret and applying entanglement, the second goded roller (non-heated roller) is passed through 3300 m / min. 150 ° C. heating roller) was wound through 4500 m / min to obtain nylon 6 filament of 11 decitex 5 filament.

  The obtained nylon 6 filament was subjected to ICM-300S (manufactured by Ishikawa Seisakusho) as a covering processing machine, Lycra (registered trademark) T-178C 20 dtex (manufactured by Operontex) as an elastic fiber, and draft ratio 2.9. Double, the number of covering twists was set to 2000 T / m, and S-twisted and Z-twisted single covering elastic yarns were obtained (nylon 6 filament mixture ratio 80%).

  The obtained covering elastic yarn is super four knitting machine (number of needles: 400) manufactured by Nagata Seiki Co., Ltd., and S knitting single covering elastic yarn and Z twisting single covering elastic yarn alternately. , And knit the leg knitted fabric of pantyhose only with covering yarn. It is a usual method as pantyhose. Scouring and dyeing (98 ° C. × 20 min, dye: Nylon Yellow E-RPL140 (0.25% owf), Nylon Red EG (0.27% owf), Nylon Blue EG-L 250% (0.10 owf), Sandos Co., Ltd.), finishing and stencil set (steam set, 105 ° C. × 60 sec) to obtain a pantyhose product, and the antifungal, antibacterial and antialgal properties were measured. The results are shown in Table 8.

Comparative Examples 19 and 20
Yarn production was carried out in the same manner as in Example 53 except that zinc oxide (manufactured by Hakusuitec Co., Ltd.) and silver-based inorganic antibacterial agent “NOVALON” (manufactured by Toagosei Co., Ltd.) were used as additives, and 11 decitex 5 filament nylon 6 filaments were obtained. . Using the obtained nylon 6 filament, a covering yarn and a pantyhose product were produced and evaluated in the same manner as in Example 54. The results are shown in Table 8.

Examples 63-68, Comparative Examples 21-23
Yarn production was carried out in the same manner as in Example 54 except that the amounts of the fungicides A to C were changed to 1% by weight, 2% by weight and 3.5% by weight, respectively, to obtain 11 decitex 5 filament nylon 6 filaments. . Using the obtained nylon 6 filament, a covering yarn and a pantyhose product were produced and evaluated in the same manner as in Example 54. Furthermore, the yarn forming property was also evaluated. The results are shown in Table 9.

  Nylon 6 filaments (Comparative Examples 21 to 23) to which 3.5% by weight of fungicides A to C are added have many yarn breaks, the fibers are yellowed, and the color developability is poor. As it was not usable.

Comparative Example 24
Yarn production was carried out in the same manner as in Example 54 except that only nylon 6 pellets with 98% sulfuric acid relative viscosity 2.7 (antifungal addition amount 0%) were obtained, and 11 decitex 5 filament nylon 6 filaments were obtained. Using the obtained nylon 6 filament, a covering yarn and a pantyhose product were produced and evaluated in the same manner as in Example 53. Furthermore, the yarn forming property was also evaluated. The results are shown in Table 9. Since antifungal performance was poor, antibacterial and antifungal properties were not evaluated.

[Example of inner wear]
Examples 69-71
The nylon 6 fiber yarns obtained in Examples 1 to 3 were knitted into a double-sided smooth knitted fabric (110 g / m < ² > per unit weight) with a 42 gauge 30 inch double circular knitting machine, and the YI value was measured. The obtained knitted fabric is scoured and subjected to intermediate setting at 190 ° C., and dyeing treatment is carried out at 98 ° C. for 60 minutes using 1% by weight of an acid dye (Nylosan Blue N-GFL 167%, manufactured by Sandos) at 160 ° C. Final set and knitted fabric was created. Sewed to the slip as inner wear. The resulting slip was measured for antifungal and antibacterial properties. The results are shown in Table 10.

Example 72
40% nylon 6 fiber yarn obtained in Example 1, 40% nylon 6 yarn obtained in Comparative Example 6, polyurethane fiber yarn (Lycra (registered trademark) T-127C 44 dtex manufactured by Operontex) 20 % Knitted fabric (Bare Tengu) was created. Sewed on the girdle as inner wear. The results are shown in Table 11.

Examples 73-75
30% nylon 6 fiber yarn obtained in Examples 1-3, 10% nylon 6 yarn obtained in Comparative Example 6, 50% cotton, 10% polyurethane fiber yarn (tricot) It was created. Sewn shorts as inner wear. About the obtained shorts, antifungal and antibacterial properties were measured. The results are shown in Table 11.

Comparative Example 25
A knitted fabric (tricot) of 40% nylon 6 fiber yarn obtained in Comparative Example 6, 50% cotton, and 10% polyurethane fiber yarn was prepared. Sewn shorts as inner wear. About the obtained shorts, antifungal and antibacterial properties were measured. The results are shown in Table 11.

[Example of down shell]
Examples 76-78
The 600 nylon 6 fiber yarns obtained in Examples 1 to 3 were warped and wound around a beam, and then the yarn wound around the beam was glued and dried to prepare a warp yarn.

Next, the warp yarn is passed through a water jet loom loom (ZW303 type, manufactured by Tsudakoma Kogyo Co., Ltd.), and the obtained nylon 6 fiber yarn is driven into the weft yarn. The density is 182 warps / inch, weft 142 A plain woven fabric with a lip structure was prepared so as to have a book / inch (weaving speed 450 m / min), and the YI value was measured. The obtained woven fabric was scoured, subjected to intermediate setting at 190 ° C., and dyed at 95 ° C. for 60 minutes using 1% by weight of an acidic dye (Nylosan Blue N-GFL 167%, manufactured by Sandos). Thereafter, calendering was performed, and the color developability, antifungal property, and antifungal property were measured on the fabric having a basis weight of 40 g / m ² and a tearing strength of 15 N. The results are shown in Table 12.

  In addition, a 4 cm × 4 cm bag was sewed from the woven fabric prepared at this time, and 1 g of feathers (goose) was packed therein to create a down shell. This down shell was measured for antifungal properties. In addition, about antifungal property, it measured about the surface and the feather of the content of the bag.

  In any of Examples 76 to 78, the antifungal property, the antifungal property, and the coloring property after dyeing were good without dullness. Moreover, as shown in FIG. 4, not only the surface of the down shell but also the feathers (goose) in the down shell did not grow and exhibited good fungicidal properties. 4A is a diagram obtained by tracing a photograph of the surface of the down shell, and FIG. 4B is a diagram obtained by tracing a photograph obtained by photographing the goose in the down shell. Moldy mildew is not observed.

Comparative Examples 26 and 27
Yarn production was performed in the same manner as in Example 75 except that zinc oxide (manufactured by Hakusuitec Co., Ltd.) and silver-based inorganic antibacterial agent “NOVALON” (manufactured by Toagosei Co., Ltd.) were used as additives, and nylon 6 fiber yarn of 33 dtex 26 filaments Got. Using the obtained nylon 6 fiber yarn, a woven fabric was prepared in the same manner as in Example 75, the YI value was measured, dyed and processed, and the coloring property, antifungal property, and antifungal property were measured.

  Further, in the same manner as in Example 76, a down-proof fabric was prepared, and the antifungal property was measured. The results are shown in Table 12. In all the levels, the antibacterial property and the coloring property after dyeing were good without dullness.

Comparative Example 28
A yarn was produced in the same manner as in Example 75 except that the additive was changed to 0% to obtain a nylon 6 fiber yarn of 33 dtex 26 filaments. A woven fabric was prepared from the obtained nylon 6 fiber yarn in the same manner as in Example 75, the YI value was measured, dyed and processed, and the coloring property and fungicidal property were measured.

  Further, in the same manner as in Example 76, a down-proof fabric was prepared, and the antifungal property was measured. In addition, about antifungal property, it measured about the surface and the feather of the content of the bag. As shown in FIG. 5, mold grew on the surface of the down shell, and the evaluation resulted in 5 points and growth of 60% or more of the whole. Furthermore, when observing the goose in the down shell, mold grew around the feather shaft. FIG. 5A is a diagram obtained by tracing a photograph of the surface of the down shell, and FIG. 5B is a diagram obtained by tracing a photograph obtained by photographing the goose in the down shell. Also shows a black grain, indicating that mold is breeding.

  That is, in the case where a textile product (down shell) using the fabric (woven fabric) of the present invention is used, not only the fungicidal properties against 71 types of fungi but also the feathers or the like in which the fungi can propagate are encased. It can also be seen that fungicidal properties can be obtained. As a result, not only can mold be prevented from breeding in the down shell, but also the mold-specific odor can be suppressed.

  In the present invention, the description has been given mainly on the antifungal property. However, the antifungal performance referred to in the present invention is generally common with the performance called antibacterial performance or antialgal performance. That is, the antibacterial performance or the anti-algae performance also includes the polyamide fiber of the present invention, a crimped yarn made of the fiber, a polyamide-based bulky processed yarn, a polyamide-based covering elastic yarn, a fabric, a textile product, an inner wear, and a down wear A shell can be used together.

  For example, when the fiber product of the present invention is used in a fishing net, it exhibits a good anti-algae effect as well as a fungicidal effect. is there.

  For example, when the textile product of the present invention is used for inner wear, it exhibits a good antibacterial effect as well as an antifungal effect. In the case of inner wear, the main focus is on the antibacterial effect.

  Therefore, in each practical use such as the polyamide fiber of the present invention, crimped yarn made of the fiber, polyamide-structured bulky processed yarn, polyamide-covering elastic yarn, fabric, textile product, inner wear, down shell, etc. The polyamide fiber of the present invention can be expressed and described as having antifungal, antibacterial and / or antialgal properties adapted to its use, and the crimped yarn comprising the fiber, Polyamide-based bulky processed yarns, polyamide-covering elastic yarns, fabrics, textiles, innerwear and downshells are not limited to the technical field where fungicidal performance is attracting attention, but antibacterial and / or algal resistance is required. Also in the field, it can be used in the same aspect of the invention. Therefore, those in the field of use are also included in the present invention. Thus, in the examples, the antifungal and antibacterial properties and antibacterial properties are also evaluated as evaluation items.

Claims (11)

  Containing at least 0.05 to 3% by weight of an additive having fungicidal performance, the additive being an additive obtained by carrying an organic component on the surface of an inorganic component, wherein the organic component is A polyamide fiber, which is a mixed organic component containing a combination of at least two of imidazole compounds, pyridine compounds, thiazoline compounds, halogen compounds, and haloalkylthio compounds.   The additive comprises 97 to 99.9% by weight of the inorganic component and 0.1 to 3% by weight of the organic component based on the weight of the additive. Polyamide fiber.   The polyamide fiber according to claim 1 or 2, wherein the inorganic component is a metal oxide.   The polyamide fiber according to claim 3, wherein the metal oxide is zinc oxide or titanium oxide.   The polyamide fiber according to any one of claims 1 to 4, wherein the polyamide fiber is a polyamide crimped yarn.   A structural bulky processed yarn composed of two or more filament yarns, wherein at least one filament yarn is the polyamide fiber according to any one of claims 1 to 4,   A polyamide-based covering elastic yarn, wherein an elastic fiber is used for the core yarn, and the polyamide fiber according to any one of claims 1 to 4 is used for the coated yarn of the core yarn.   A polyamide fiber fabric comprising at least 30% by weight of the polyamide fiber according to any one of claims 1 to 4.   A polyamide fiber product comprising at least 30% by weight of the polyamide fiber according to any one of claims 1 to 4.   An innerwear comprising at least a part of the polyamide fiber according to claim 1.   A down shell comprising at least a part of the polyamide fiber according to claim 1.

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