WO2020115928A1 - Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne - Google Patents

Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne Download PDF

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Publication number
WO2020115928A1
WO2020115928A1 PCT/JP2019/021950 JP2019021950W WO2020115928A1 WO 2020115928 A1 WO2020115928 A1 WO 2020115928A1 JP 2019021950 W JP2019021950 W JP 2019021950W WO 2020115928 A1 WO2020115928 A1 WO 2020115928A1
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WIPO (PCT)
Prior art keywords
antibacterial
glass
weight
fiber
antibacterial fiber
Prior art date
Application number
PCT/JP2019/021950
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English (en)
Japanese (ja)
Inventor
宏治 齋藤
裕介 佐藤
Original Assignee
興亜硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 興亜硝子株式会社 filed Critical 興亜硝子株式会社
Priority to CN201980002401.1A priority Critical patent/CN111542654A/zh
Priority to US16/613,854 priority patent/US20210332502A1/en
Priority to JP2020504742A priority patent/JP6707725B1/ja
Priority to KR1020197032995A priority patent/KR102243796B1/ko
Priority to EP19798520.3A priority patent/EP3683341A4/fr
Publication of WO2020115928A1 publication Critical patent/WO2020115928A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
    • D10B2101/06—Glass
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial

Definitions

  • Patent Document 1 a method of producing such an antibacterial fiber, a method of fixing an antibacterial glass composition (glass particles) on the surface of a fiber substrate of synthetic fiber or natural fiber, and a method of dispersing the antibacterial glass composition in the fiber substrate There is a method (Patent Document 1).
  • an antibacterial fiber containing a thermoplastic resin and an antibacterial glass as a blending component and having an average diameter of the antibacterial fiber in the range of 1 to 50 ⁇ m The antibacterial fiber has a core portion and a sheath portion, and the content of the antibacterial glass in the core portion is Q1 (% by weight) with respect to the total amount of the antibacterial fiber.
  • Q1 and Q2 are antibacterial fibers satisfying a predetermined relational expression.
  • the thermoplastic resin is any one or more of polyester resin, polyamide resin and polyolefin resin.
  • the antibacterial glass can be more uniformly dispersed in the resin component, so that an excellent antibacterial effect can be obtained.
  • the antibacterial glass is selected from phosphoric acid antibacterial glass and borosilicate glass.
  • the reason for this is that if the phosphoric acid type antibacterial glass or borosilicate type glass absorbs the surrounding moisture and releases the antibacterial active ingredient while absorbing the water, the antibacterial action is prevented while preventing the discoloration of the thermoplastic resin. This is because the elution amount of the antibacterial active ingredient such as silver ions in the functional fiber can be adjusted within a suitable range.
  • the content of Ag 2 O is set within the range of 0.2 to 5% by weight.
  • the reason for this is that if the content of Ag 2 O is 0.2% by weight or more, sufficient antibacterial properties can be exhibited.
  • the content of Ag 2 O is more preferably 0.5 to 4% by weight, and further preferably 0.8 to 3.5% by weight.
  • the content of ZnO is preferably in the range of 2 to 60% by weight based on the total amount.
  • the reason for this is that if the content of ZnO is 2% by weight or more, the effect of preventing yellowing and the effect of improving antibacterial properties are easily exhibited, while the content of ZnO is 60% by weight. This is because when the value is the following, the transparency of the antibacterial glass is unlikely to decrease and the mechanical strength is easily secured. Therefore, the content of ZnO is more preferably in the range of 5 to 50% by weight, and further preferably in the range of 10 to 40% by weight.
  • the elution rate of the antibacterial ions from the antibacterial glass is preferably set to a value within the range of 1 ⁇ 10 2 to 1 ⁇ 10 5 mg/Kg/24Hr.
  • the reason for this is that when the elution rate of such antibacterial ions is less than 1 ⁇ 10 2 mg/Kg/24 Hr, the antibacterial property may be significantly reduced, while the elution rate of such antibacterial ions is 1 ⁇ 10 2. This is because if it exceeds 5 mg/Kg/24 Hr, it may be difficult to exert the antibacterial effect for a long time, or the transparency of the obtained antibacterial fiber may decrease.
  • the volume average particle diameter of the antibacterial glass is 0.1 ⁇ m or more, mixing/dispersion in the resin component is easy, light scattering is suppressed, or transparency is easily secured.
  • the volume average particle diameter of the antibacterial glass is 5.0 ⁇ m or less, the antibacterial fiber is easily dispersed in the resin component, and the mechanical strength of the antibacterial fiber is easily secured. Therefore, more specifically, the volume average particle diameter of the antibacterial glass is more preferably set to a value within the range of 0.5 to 4.0 ⁇ m, and is set to a value within the range of 1.0 to 3.0 ⁇ m.
  • the volume average particle diameter (D50) of the antibacterial glass is the particle size distribution obtained by using a laser type particle counter (based on JIS Z 8852-1) or a sedimentation type particle size distribution meter, or It can be calculated from the particle size distribution obtained by performing image processing based on an electron micrograph of antibacterial glass.
  • the specific surface area of the antibacterial glass is more preferably in the range of 15,000 to 200,000 cm 2 /cm 3 , and even more preferably in the range of 18,000 to 150,000 cm 2 /cm 3. ..
  • the specific surface area (cm 2 /cm 3 ) of the antibacterial glass can be obtained from the results of particle size distribution measurement. Assuming that the antibacterial glass is spherical, the measured data of the particle size distribution is used to measure the unit volume (cm 3 ) Surface area (cm 2 ).
  • the number average secondary particle diameter of the agglomerated silica as an external additive is preferably set to a value within the range of 1 to 15 ⁇ m.
  • the reason for this is that if the number average secondary particle diameter of the external additive is a value of 1 ⁇ m or more, the dispersibility of the antibacterial glass 10 becomes good, light scattering is suppressed, and transparency can be secured.
  • the number average secondary particle size of the external additive is 15 ⁇ m or less, it is easy to mix/disperse and handle in the resin component, and when producing an antibacterial fiber or an antibacterial film, This is because it is easy to secure surface smoothness, transparency, and mechanical strength.
  • the thickness t of the sheath portion of the antibacterial fiber 1 is preferably set to a value within the range of 0.7 to 49.7 ⁇ m.
  • the reason for this is that by setting the thickness of the sheath portion to a value within this range, sufficient antibacterial properties can be maintained from the initial stage to a long period. Therefore, the thickness of the sheath portion is more preferably set to a value within the range of 1 to 45 ⁇ m, further preferably set to a value within the range of 5 to 40 ⁇ m.
  • the thickness of the sheath portion can be obtained by actually measuring several points t (for example, 5 points) with an electron microscope or a micrometer and taking the average value thereof.
  • Q1 and Q2 satisfying such a relational expression it is preferable that Q1 is 0 or less than 1% by weight (excluding 0% by weight), and Q2 is within the range of 1 to 10% by weight. A value is preferable. Further, Q1 is more preferably 0 or less than 0.5% by weight, and Q2 is more preferably set to a value within the range of 1.5 to 9% by weight. Further, Q1 is more preferably 0 or less than 0.1% by weight, and Q2 is more preferably a value within the range of 2 to 8% by weight. This is because if the value of Q1 is within this range, the antibacterial effect of the antibacterial glass can be effectively obtained even when the average diameter of the antibacterial fiber is small. On the other hand, if Q2 has a value within this range, the content of the antibacterial glass with respect to the entire antibacterial fiber can be set within an appropriate range.
  • the tensile strength measured according to JIS L 1015 It is preferable to set (cN/dtex) to a value within the range of 3 to 50 cN/dtex. The reason for this is that if the tensile strength (cN/dtex) of the antibacterial fiber is less than 3 cN/dtex, the fiber may be broken during stretching, or the product may be torn when laundering the product using the antibacterial fiber.
  • the apparent weaving degree and the number of crimps of the antibacterial fiber are not particularly limited, and can be appropriately adjusted according to the application of the antibacterial fiber.
  • the apparent weaving degree of the antibacterial fiber can be appropriately adjusted according to the application, but it is preferably a value within the range of 0.1 to 50 dtex, for example, a value within the range of 0.5 to 30 dtex. Is more preferable, and a value within the range of 1 to 10 dtex is further preferable.
  • the number of crimps of the antibacterial fiber can be adjusted according to the application from the viewpoint of imparting elastic force, texture, etc., and the greater the number of crimps, the greater the elastic force.
  • the number of crimps of the antibacterial fiber is preferably 5 to 90 per 25 mm of fiber, and is preferably 50 to 90 for applications requiring elasticity.
  • miscellaneous goods include various brushes such as toothbrushes, scrubbing brushes, brushes, handbags, lunch mats, pen cases, wallets, eyeglass cases, eyeglass wipes, curtains, coasters, mouse pads, stuffed toys, and pet beds. ..
  • Examples of the filtration medium include filters for air conditioners, ventilation fans, air inlets and air purifiers, filters for water purification, and the like, and can be applied to household, industrial, automobile, and other filters.
  • Other uses include artificial hair, tents, light-shielding sheets such as grass sheets, soundproofing materials, sound absorbing materials, and cushioning materials.
  • (1)-1 Melting Step it is preferable that the glass raw materials are accurately weighed and uniformly mixed, and then melted using, for example, a glass melting furnace to prepare a glass melt.
  • a mixing machine such as a universal stirrer (planetary mixer), an alumina porcelain crusher, a ball mill, a propeller mixer.
  • a universal stirrer Is 100 rpm, the rotation number is 250 rpm, and the glass raw materials are preferably stirred and mixed under the conditions of 10 minutes to 3 hours.
  • the glass melting conditions for example, it is preferable to set the melting temperature to a value in the range of 1100 to 1500° C. and the melting time to a value in the range of 1 to 8 hours. The reason for this is that under such melting conditions, the production efficiency of the glass melt can be increased and the yellowing of the antibacterial glass at the time of production can be reduced as much as possible.
  • polyethylene terephthalate resin When polyethylene terephthalate resin is used as the main component as the thermoplastic resin, it is preferable to mix and disperse the polybutylene terephthalate resin. This is because hydrolysis of the polyethylene terephthalate resin, which is the main component, can be effectively suppressed, and a spinning stock solution in which the final concentration of antibacterial glass is uniformly dispersed can be obtained.
  • Step (4) Crimp step
  • the crimp step of step (4) is an optional step, the drawn yarn obtained in step (3) is guided to a crimp-applying device, and the yarn is false twisted to be bulky. Is a step of imparting elasticity and elasticity.
  • conventionally known methods and devices can be used.
  • a heating fluid crimping device that performs false twisting on the yarn by bringing the yarn into contact with the heating fluid.
  • the heating fluid crimp imparting device is a device for injecting a heating fluid such as steam onto a yarn to push the yarn together with the heating fluid into a compression adjusting section to impart crimp.
  • the antibacterial glass according to the antibacterial fiber of the present invention shows that the antibacterial glass is uniformly distributed in the entire antibacterial fiber from the EDX mapping image using the characteristic X-ray of the K ray of P element. It can be seen that there are a plurality of regions locally distributed with high concentration in the sheath portion. Further, from FIG. 4(b), it can be seen that the C element is not distributed at the location where the antibacterial fiber is distributed. Further, it can be seen from FIG. 4C that the O element is uniformly distributed.
  • antibacterial properties 1 Staphylococcus aureus
  • antibacterial properties 2 Escherichia coli
  • the number of bacteria (growth colony) before the test was 2.6 ⁇ 10 5 (individual/test piece) for both Staphylococcus aureus and E. coli.
  • the results obtained are shown in Table 1.
  • ⁇ The number of bacteria after the test is less than 1/10000 of the number of bacteria before the test.
  • ⁇ The number of bacteria after the test is 1/10000 or more and less than 1/1000 of the number of bacteria before the test.
  • B The number of bacteria after the test is 1/1000 or more and less than 1/100 of the number of bacteria before the test.
  • X The number of bacteria after the test is 1/100 or more of the number of bacteria before the test.
  • the antibacterial glass is not distributed over the entire antibacterial fiber, but there are a plurality of regions locally distributed in high concentration in the sheath portion. Also, from FIG. 5(b), it can be seen that the sheath portion is brighter and the C element is more distributed. Further, from FIG. 5(c), the core is brighter because of the O element of polyethylene terephthalate or polybutylene terephthalate contained in the core.
  • Example 4 the spinning solution for core part was composed of 0.5 part by weight of antibacterial glass, 95 parts by weight of polyethylene terephthalate resin having a number average molecular weight of 34,000, and 5 parts by weight of polybutylene terephthalate resin having a number average molecular weight of 26000.
  • an antibacterial fiber was produced in the same manner as in Example 1, and fiber evaluation and antibacterial evaluation were performed in the same manner as in Example 1. The results obtained are shown in Table 1. When the antibacterial fiber obtained in Example 4 was observed with a scanning electron microscope, it was confirmed that the antibacterial glass was more dispersed in the sheath portion of the antibacterial fiber.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Multicomponent Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Glass Compositions (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

L'invention concerne une fibre antibactérienne dans laquelle la teneur en verre antibactérien dans la partie centrale est amenée à être inférieure à la teneur en verre antibactérien dans la partie gaine, ce qui permet à la quantité ajoutée de verre antibactérien d'être faible et, en outre, à la fibre de présenter des propriétés antibactériennes supérieures. L'invention concerne également un procédé efficace de fabrication d'une telle fibre antibactérienne. La fibre antibactérienne comprend une résine thermoplastique et du verre antibactérien comme composants ajoutés, le diamètre moyen de la fibre antibactérienne est défini pour être une valeur comprise entre 1 et 50 µm, et la fibre antibactérienne comprend une partie centrale et une partie gaine. Lorsque la teneur en verre antibactérien dans la partie centrale par rapport à la quantité totale de la fibre antibactérienne est définie comme Q1 (en % en poids), et la teneur en verre antibactérien dans la partie gaine par rapport à la quantité totale de la fibre antibactérienne est définie comme Q2 (en % en poids), Q1 et Q2 satisfont l'expression relationnelle (1) : Q1 < Q2.
PCT/JP2019/021950 2018-12-04 2019-06-03 Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne WO2020115928A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201980002401.1A CN111542654A (zh) 2018-12-04 2019-06-03 抗菌性纤维和抗菌性纤维的制造方法
US16/613,854 US20210332502A1 (en) 2018-12-04 2019-06-03 Antibacterial fiber and method for producing antibacterial fiber
JP2020504742A JP6707725B1 (ja) 2018-12-04 2019-06-03 抗菌性繊維及び抗菌性繊維の製造方法
KR1020197032995A KR102243796B1 (ko) 2018-12-04 2019-06-03 항균성 섬유 및 항균성 섬유의 제조 방법
EP19798520.3A EP3683341A4 (fr) 2018-12-04 2019-06-03 Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018227219 2018-12-04
JP2018-227219 2018-12-04

Publications (1)

Publication Number Publication Date
WO2020115928A1 true WO2020115928A1 (fr) 2020-06-11

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PCT/JP2019/021950 WO2020115928A1 (fr) 2018-12-04 2019-06-03 Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne

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US (1) US20210332502A1 (fr)
EP (1) EP3683341A4 (fr)
JP (1) JP6707725B1 (fr)
KR (1) KR102243796B1 (fr)
CN (1) CN111542654A (fr)
TW (1) TWI708750B (fr)
WO (1) WO2020115928A1 (fr)

Cited By (1)

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JP7030370B1 (ja) * 2021-08-26 2022-03-07 株式会社 維研 接触冷感機能を有する繊維製品

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CN113800772A (zh) * 2021-07-31 2021-12-17 广东金发科技有限公司 一种长效抗菌玻璃纤维、尼龙模塑组合物及其制备方法和应用
CN114687006B (zh) * 2022-04-12 2023-02-14 雅香丽化妆用品（深圳）有限公司 一种速干纤丝及其制备方法和牙刷
CN115262019B (zh) * 2022-07-05 2023-07-18 新凤鸣集团股份有限公司 一种抗菌抗黄变ZnO无锑聚酯纤维的制造方法
KR102647770B1 (ko) * 2023-03-20 2024-03-14 주식회사 케어마일 내구성과 유연성을 향상시킨 그래핀 함유 인조모발 및 그 제조방법

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EP3683341A1 (fr) 2020-07-22
TWI708750B (zh) 2020-11-01
US20210332502A1 (en) 2021-10-28
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