US20150203993A1 - Method for producing fibers having a low surface energy and fibers, yarns and textiles having a low surface energy - Google Patents

Method for producing fibers having a low surface energy and fibers, yarns and textiles having a low surface energy Download PDF

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Publication number
US20150203993A1
US20150203993A1 US14/276,532 US201414276532A US2015203993A1 US 20150203993 A1 US20150203993 A1 US 20150203993A1 US 201414276532 A US201414276532 A US 201414276532A US 2015203993 A1 US2015203993 A1 US 2015203993A1
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United States
Prior art keywords
surface energy
low surface
fibers
spinning
thermoplastic polymer
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Abandoned
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US14/276,532
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English (en)
Inventor
Yi Jen Tu
Kuo Chung Wu
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Shinkong Synthetic Fibers Corp
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Shinkong Synthetic Fibers Corp
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Assigned to SHINKONG SYNTHETIC FIBERS CORPORATION reassignment SHINKONG SYNTHETIC FIBERS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TU, YI JEN, WU, KUO CHUNG
Publication of US20150203993A1 publication Critical patent/US20150203993A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • D01D5/08—Melt spinning methods
    • 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
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • 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
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
    • 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
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component

Definitions

  • the present application is directed to a production method of fibers, and specifically to a production method of fibers having a low surface energy.
  • the existing textiles having a low surface energy are usually produced by a processing procedure of applying a low surface energy aid to a fabric, such as by means of coating, dipping, padding, etc., to allow the low surface energy aid to adsorb onto the fabric, and then fixing the aid onto the fabric at a heating temperature of about 100 ⁇ 210° C.
  • TW Patent Application No. 098110619 discloses a production method of yarns having water repellency, wherein the yarns to be treated are allowed to pass through a reagent vessel containing a water repellent agent, and then pass through a heat treatment unit to fixing the water repellent agent on the yarns to be treated to form yarns having water repellency.
  • said method requires movement through a reagent vessel unit and a heat treatment unit in a series.
  • the water repellent agent is scorched on the heat treatment unit due to the heat.
  • the water repellent agent since the water repellent agent only adsorbs onto the surface of the yarns, it may transfer to other yarns which are not desired to become water repellent during subsequent treatments (such as yarn binding treatment).
  • Chinese Patent Publication No. CN101984154 discloses a production method of a water repellent polyester fiber, wherein the water repellent agent is directly added into the spinning finishing oil, and thereby the water repellent agent directly adsorbs onto the fiber surface during a melting spinning procedure in order to prepare fibers having water repellency.
  • the water repellent agent adsorbing onto the fiber surface is prone to adhering on the hot plate after heating, scorched fouling (which cannot be easily cleaned and scratched) is produced. This not only leads to hot plate equipment damage, but the textile properties are also affected owing to a non-uniform heating of fiber.
  • the inventors of the present application studied and conducted experiments to provide fibers having a low surface energy and a production method thereof, thereby improving the disadvantages existing in the known spinning production techniques and producing fibers having excellent liquid repellency and anti-fouling effect at low production costs.
  • a production method of fibers having a low surface energy comprises the following steps:
  • thermoplastic polymer containing 0.1 ⁇ 30 wt % of a lower surface energy additive
  • thermoplastic polymer as a spinning raw material to melt spinning, followed by drawing and false twist processing to produce fibers with a surface tension of between 25 ⁇ 72 dyne/cm.
  • a production method of fibers having a low surface energy comprises the following steps:
  • thermoplastic polymer containing 0.1 ⁇ 30 wt % of a lower surface energy additive
  • thermoplastic polymer as a spinning raw material to melt spinning, drawing and setting to produce a fully drawn yarn (FDY) with a surface tension of between 25 ⁇ 72 dyne/cm.
  • a production method of fibers having a low surface energy comprises the following steps:
  • thermoplastic polymer containing 0.1 ⁇ 30 wt % of a lower surface energy additive
  • thermoplastic polymer as a spinning raw material to melt spinning, multi-stage drawing and setting to produce a high tenacity yarn (HTY) with a surface tension of between 25 ⁇ 72 dyne/cm.
  • HTY high tenacity yarn
  • the production method of fibers having a low surface energy of the present invention can shorten processing time and reduce equipment volume and costs, since the low surface energy additive is added into the spinning raw materials at the spinning raw material stage and it is unnecessary to pass through a reagent vessel of water repellent agent and a heat treatment unit in series as required by D 1 .
  • the low surface energy additive is incorporated into the spinning raw materials at the spinning raw material stage in the present invention, and thus the application of the water repellent agent onto the yarn surface during a subsequent processing as required by D 1 can be omitted, thereby avoiding a poor situation caused by heating a water repellent to scorch when yarns pass through a heat treatment unit.
  • the scorching resulting from heating the water repellent agent to adhere onto a hot plate during a latter spinning processing as required by D 2 can be also omitted. Further, since the prepared fibers have a surface tension of 25 ⁇ 72 dyne/cm, they have excellent liquid repellency and anti-fouling effect.
  • FIG. 1 is an illustrative FIGURE showing a measurement of a water droplet contact angle of a textile.
  • the spinning raw materials can be thermoplastic polymers such as polyesters, polyamides or polyolefins, etc.
  • polyester polymers can be polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), cationic dyeable polyester, recycled PET, BioPET and polylactic acid (PLA), etc.
  • polyamides can be nylon 6, nylon 66 and nylon 46, etc.
  • examples of polyolefin polymers can be polyethylene (PE), polypropylene (PP), etc.
  • the present invention adds a specific low surface energy additive to the aforementioned thermoplastic polymer before melting spinning said thermoplastic polymer. Considering that the low surface energy additive added into the thermoplastic polymer should be free from deterioration at a high temperature during melting spinning procedure, the present invention selects fluorine-series additives with a high thermal resistance, such as the fluorine-series low surface energy aid of model FC-L624 produced by GOULSTON company.
  • a low surface energy additive is added into a thermoplastic polymer in an amount of 0.1 wt % ⁇ 30 wt %.
  • the amount of a low surface energy additive is lower than 0.1 wt %, the effect for reducing the surface energy of fibers is insufficient.
  • the amount of a low surface energy additive is higher than 30 wt %, the costs relatively increase and the production becomes difficult, even though the effect for reducing the surface energy of fibers is good.
  • thermoplastic polymer containing 0.1 wt % ⁇ 30 wt % of a low surface energy additive as a spinning raw material can be obtained by: adding 0.1 wt % ⁇ 30 wt %, based on the total amounts of the monomers, of a low surface energy additive to the monomers, followed by polymerization in the process of using monomers; or alternatively, blending thermoplastic polymer particles containing a specific amount (such as 1 ⁇ 60 wt %) of a low surface energy additive with thermoplastic polymer particles free of a low surface energy additive such that the concentration of the low surface energy additive is 0.1 ⁇ 30 wt % after blending.
  • the production method of fibers having a low surface energy of the present invention allows a thermoplastic polymer containing 0.1 ⁇ 30 wt % of a low surface energy additive to eject from a spinneret of a spinning machine in a mono spinning or composite spinning manner at a molten state; wind at a spinning rate of 2500 ⁇ 3500 m/min (in the case of producing partially oriented yarn (POY)) or at a spinning rate of 3500 ⁇ 6000 m/min (in the case of producing high oriented yarn (HOY)); and then false twist at a winding rate of 100 ⁇ 1300 m/min and at a hot plate temperature of 60 ⁇ 400° C.
  • DTY or air false twist at a winding rate of 100 ⁇ 800 m/min and at a hot plate temperature of 60 ⁇ 400° C. (ATY) to produce fibers having a low surface energy.
  • the production method of fibers having a low surface energy of the present invention also allows a thermoplastic polymer containing 0.1 ⁇ 30 wt % of a low surface energy additive to eject from a spinneret of a spinning machine in a mono spinning or composite spinning manner at a molten state, and melting spin, draw and set at a spinning rate of 1000 ⁇ 6000 m/min, drawing ratio of 1.0 ⁇ 10, drawing temperature of 25 ⁇ 200° C. and setting temperature of 60 ⁇ 260° C. to produce a fully drawn yarn (FDY) having a surface tension of between 25 ⁇ 72 dyne/cm.
  • FDY fully drawn yarn
  • the production method of fibers having a low surface energy of the present invention also allows a thermoplastic polymer containing 0.1 ⁇ 30 wt % of a low surface energy additive to eject from a spinneret of a spinning machine in a mono spinning or composite spinning manner at a molten state, and multi-stage draw the thermoplastic polymer at a spinning rate of 1000 ⁇ 6000 m/min, drawing temperature of 25 ⁇ 200° C. and setting temperature of 60 ⁇ 260° C., with a total drawing ratio of 1.0 ⁇ 10, to produce a high tenacity yarn (HTY) having a surface tension of between 25 ⁇ 72 dyne/cm.
  • HTY high tenacity yarn
  • fibers with a circle, a non-circle or composite cross section can be formed by melt spinning depending on the demands.
  • dyed fibers can be produced by dope dyeing or piece-dyeing.
  • the processing conditions for dope dyeing and piece-dyeing can be those disclosed by commonly known techniques.
  • filament products or staple products having a low surface energy can be produced depending on the demands.
  • the fibers having a low surface energy produced by the production method of the present invention can be solely composed of yarns having a low surface energy or further be composited with other fibers to form yarns having a low surface energy.
  • the fibers having a low surface energy or the yarns having a low surface energy prepared as stated above can be used for preparation of prepare related textiles by textile techniques known in the industry.
  • the surface tensions of common liquid are as following: water 72 dyne/cm, wine 45 dyne/cm, milk 43 dyne/cm, peanut oil 40 dyne/cm, olive oil 32 dyne/cm, gasoline 28 dyne/cm.
  • the fibers having a low surface energy, yarns having a low surface energy and textiles of the present invention have good liquid repellency toward these liquids for their surface tensions of between 25 ⁇ 72 dyne/cm.
  • DTY false twist processing procedure
  • the thus produced fibers are woven to form textiles, and the surface tension value, water droplet contact angle and water repellent test characteristic were measured. The results are shown in Table 1.
  • FC-L624 fluorine-series low surface energy additive
  • FC-L624 fluorine-series low surface energy additive
  • FC-L624 fluorine-series low surface energy additive
  • FC-L624 fluorine-series low surface energy additive
  • ATY air false twist processing
  • DTY false twist processing procedure
  • the thus produced fibers are woven to become textiles, and the surface tension value, water droplet contact angle and water repellent test characteristic were measured. The results are shown in Table 1.
  • False twisted yarns prepared from 75D/72F of polyethylene terephthalate pass through a reagent vessel containing a fluorine-series low surface energy additive (FC-L624, produced by GOULSTON company) in order that the low surface energy additive adsorbs onto the surface thereof.
  • FC-L624 fluorine-series low surface energy additive
  • a heat treatment was conducted by a heat roller at 150° C. to allow the low surface energy additive to fix on the false twisted yarns and form false twisted yarns having a low surface energy.
  • the thus produced fibers are woven to form textiles, and the surface tension value, water droplet contact angle and water repellent test characteristic are measured. The results were shown in Table 1.
  • Polyethylene terephthalate as a spinning raw material was melt spun at 288° C. and a spinning rate of 3000 m/min, and the thus obtained spun yarns were oiled with spinning finishing oil containing a fluorine-series low surface energy additive (FC-L624, produced by GOULSTON company) (oiling ratio: 0.6%), followed by a false twist processing procedure (DTY) at a winding rate of 600 m/min, a hot plate temperature of 230° C. and a drawing ratio of 1.67 to produce fibers having water repellency.
  • FC-L624 fluorine-series low surface energy additive
  • DTY false twist processing procedure
  • the thus produced fibers are woven to form textiles, and the surface tension value, water droplet contact angle and water repellent test characteristic were measured. The results are shown in Table 1.
  • a 0.5 cc of water droplet was dropped on the surface of the textiles obtained from examples and comparative examples, and the contact angle ( ⁇ ) between the water droplet and textile was measured, as shown in FIG. 1 .
  • Inks with different surface tensions were respectively used to brush ink traces of about 10 cm of length on the textiles obtained from examples and comparative examples, and the ink traces were observed to confirm whether they shrink and form ink droplet within 2 seconds. If it happens, an ink of a lower surface tension was subsequently used to brush a trace and the trace was then observed. The procedure was repeated until an ink trace does not shrink and form an ink droplet, and this is the corresponding surface tension the textile possesses.
  • the textiles obtained from examples and comparative examples were cut into a size of 180 mm ⁇ 180 mm and the specimens were fixed at hoops located on a base in a manner that the surfaces for water repellent test face upside at a declination angle of 45 degrees. 250 cc of water was flowed over the textile surface in 30 seconds. The specimens were unloaded from the base and slightly patted. The assessment was conducted according to FTTS-FA-011.
  • the heating units used in the examples and comparative examples were observed to evaluate the scorched fouling in accordance with the following manner:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Multicomponent Fibers (AREA)
US14/276,532 2014-01-20 2014-05-13 Method for producing fibers having a low surface energy and fibers, yarns and textiles having a low surface energy Abandoned US20150203993A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TW103102027 2014-01-20
TW103102027A TWI513808B (zh) 2014-01-20 2014-01-20 A method for manufacturing a low surface energy fiber

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US (1) US20150203993A1 (ja)
JP (1) JP2015137446A (ja)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109554788A (zh) * 2018-11-21 2019-04-02 桐乡市宏洋化纤有限公司 一种加弹机生产dty丝的工艺
WO2019216850A3 (en) * 2017-12-26 2019-12-12 Turkuaz Teksti̇l Diş Ti̇caret Li̇mi̇ted Şi̇rketi̇ Pes thread with wool-like appearance
US11883580B2 (en) 2016-12-21 2024-01-30 Boehringer Ingelheim International Gmbh Nebulizer and cartridge

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Publication number Priority date Publication date Assignee Title
CN107574498A (zh) * 2017-09-25 2018-01-12 安徽华祺汽车装饰有限公司 一种耐油污汽车坐垫的制备方法
CN109234834B (zh) * 2018-09-18 2020-12-29 武汉纺织大学 一种超疏水聚乳酸纤维的制备方法
CN110685046B (zh) * 2019-08-19 2022-04-22 浙江海洋大学 一种防污损抗疲劳的多股单丝混捻网线及其制备方法
CN112458556A (zh) * 2020-11-27 2021-03-09 宁波依兰布艺有限公司 耐久性拒水丙纶纤维的生产方法

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US3899563A (en) * 1971-12-06 1975-08-12 Allied Chem Synthetic fibers having improved soil and stain repellency
US20030001130A1 (en) * 2001-03-09 2003-01-02 3M Innovative Properties Company Water-and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties
US20100330861A1 (en) * 2009-06-25 2010-12-30 Techmer Pm, Llc Hydrophobic additive for use with fabric, fiber, and film
US20130005922A1 (en) * 2010-12-28 2013-01-03 E. I. Du Pont De Nemours And Company Fibers and yarns from a fluorinated polyester blend

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US4209610A (en) * 1975-06-30 1980-06-24 Frank Mares Partially fluorinated esters or amide/esters of benzene polycarboxylic acids, and dyeable pet and nylon fibers incorporating the same and process of making such fibers
US4219625A (en) * 1977-12-16 1980-08-26 Allied Chemical Corporation Fluorinated polyol esters

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Publication number Priority date Publication date Assignee Title
US3899563A (en) * 1971-12-06 1975-08-12 Allied Chem Synthetic fibers having improved soil and stain repellency
US20030001130A1 (en) * 2001-03-09 2003-01-02 3M Innovative Properties Company Water-and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties
US20100330861A1 (en) * 2009-06-25 2010-12-30 Techmer Pm, Llc Hydrophobic additive for use with fabric, fiber, and film
US20130005922A1 (en) * 2010-12-28 2013-01-03 E. I. Du Pont De Nemours And Company Fibers and yarns from a fluorinated polyester blend

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11883580B2 (en) 2016-12-21 2024-01-30 Boehringer Ingelheim International Gmbh Nebulizer and cartridge
WO2019216850A3 (en) * 2017-12-26 2019-12-12 Turkuaz Teksti̇l Diş Ti̇caret Li̇mi̇ted Şi̇rketi̇ Pes thread with wool-like appearance
CN109554788A (zh) * 2018-11-21 2019-04-02 桐乡市宏洋化纤有限公司 一种加弹机生产dty丝的工艺

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TW201529823A (zh) 2015-08-01
TWI513808B (zh) 2015-12-21
CN104790054A (zh) 2015-07-22
JP2015137446A (ja) 2015-07-30

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