EP0677601B1 - PET-Fasern mit verbessertem Bausch und Verfahren zu ihrer Herstellung - Google Patents

PET-Fasern mit verbessertem Bausch und Verfahren zu ihrer Herstellung Download PDF

Info

Publication number
EP0677601B1
EP0677601B1 EP95105498A EP95105498A EP0677601B1 EP 0677601 B1 EP0677601 B1 EP 0677601B1 EP 95105498 A EP95105498 A EP 95105498A EP 95105498 A EP95105498 A EP 95105498A EP 0677601 B1 EP0677601 B1 EP 0677601B1
Authority
EP
European Patent Office
Prior art keywords
pet
fibre
weight
additives
fibre according
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP95105498A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0677601A1 (de
Inventor
Werner Dipl.-Ing. Kaegi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inventa AG fuer Forschung und Patentverwertung
Uhde Inventa Fischer AG
Original Assignee
EMS Inventa AG
Inventa AG fuer Forschung und Patentverwertung
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 EMS Inventa AG, Inventa AG fuer Forschung und Patentverwertung filed Critical EMS Inventa AG
Publication of EP0677601A1 publication Critical patent/EP0677601A1/de
Application granted granted Critical
Publication of EP0677601B1 publication Critical patent/EP0677601B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow 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
    • 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

Definitions

  • Polyethylene terephthalate fibers are known for their excellent physical properties and good physiological properties for all types of textiles in used on a large scale.
  • polyethylene terephthalate can also meet special requirement profiles be adjusted.
  • Such fibers are defined with Features, e.g. as filling fibers for sleeping bags, quilts, padding and similar applications.
  • Filling fibers are e.g. through special types of crimp, such as the so-called Helix shapes, through optimized crimp formation, through special fiber stiffness, e.g. through high crystallization, through alloying of other polymers or is sought with selected fiber cross-sections. she are mostly surface treated, e.g. siliconized to smooth the unwanted Avoid sticking of the fibers and a soft grip to achieve.
  • a filling fiber e.g. a PET staple fiber for filling pillows, blankets, sleeping bags, upholstery, etc.
  • the bulk is that on that Fiber weight related volume of a filling fleece made from it defined wing loading.
  • a high (bending) stiffness of the individual fibers is required for optimal building behavior Precondition, what gives them a large elastic return force.
  • the fibers In order for this to be effective in the fleece bandage, the fibers must The number, angle and shape of sheets should be optimized so that they are as bulky as possible support each other. Not about recovery after a load to hinder by friction, the fibers are also siliconized on the surface, which creates the necessary smoothness and a soft grip to let.
  • DE 31 03 192 describes an alkali metal salt of an aromatic Sulfonic acid as a crystallization accelerator for injection molding PES types, its advantages with very small quantities only used for PES fiber can be obtained if stretched immediately after spinning, i.e. With the so-called spin-stretch process is used. Besides, it is known that alkali metal sulfate groups the moisture retention in the polyester increase. This property is undesirable for fill and wadding fibers.
  • Plasticizers can increase the chain mobility of the polyester so far order states that are more easily crystallizable when solidified can train. It will be a during the cooling process extensive orientation not only enabled, but also completed.
  • plasticizers usually deteriorate the mechanical properties all impact resistance, they also tend to migrate.
  • EP 194 808 describes various polyester resins with improved demolding properties due to increased crystallization rate. she contain up to 10 pbw of inorganic nucleating agents, metal salts of Carboxylic acids, up to 150 GT reinforcing fiber and 0.3 to 10 GT Plasticizer based on esters, as well as 1 to 30 GT impact modifier per 100 GT polyester resin.
  • the upper limit is for the nucleating agent and the ester compound if possible 2.0% by weight.
  • Such use-related additives are known in the art, inter alia. Matting agents, pigments, stabilizers, UV brighteners, dirt-repellent and flame retardant additives. Of the latter, phosphorus compounds are preferred used. There are phosphorinane compounds in a special way proven.
  • a proportion of the phosphorinane compound SANDOFLAM® is particularly advantageous 5085 between 3.0 and 10.0% by weight, preferably between 4.0 and 7.0 % By weight.
  • processing-related additives are in particular Glycols, preferably mono-, di- and triethylene glycol for adjustment to name the viscosity, ethylene glycol being particularly preferred.
  • ester compounds which according to the invention must preferably be present in amounts of only 0.1 to 0.3% by weight and particularly preferably only 0.15 to 0.25% by weight, are per se as plasticizers for PET injection molding -Recipes known. However, you need to do this in a significantly higher Concentration range, namely 0.3 to 10.0 GT per 100 GT polyester resin, are used (EP 194 808).
  • nucleating agents that are suitable for PET also called nucleating agents are, for example, in the "Taschenbuch der Kunststoff-Additive", Carl Hanser Verlag, 3rd edition 1990, page 899.
  • the nucleating agents used according to the invention are either inert, inorganic substances with an average particle size of less than 10 ⁇ m, preferably less than 1 ⁇ m, for example talc, kaolin, chalk, carbon black, graphite, quartz powder (SiO 2 ) and inorganic pigments, for example TiO 2 , BaSO 4 , ZnS, or suitable monomeric organic compounds such as salts of carboxylic acids, benzophenone or alkali metal alkyl sulfonates, or finally selected organic polymers such as polyethylene, polypropylene, copolymers of ethylene and unsaturated carboxylic acids or copolymers of styrene derivatives with dienes. (R. Vieweg, L.
  • the organic compounds or the polymers can be used alone or together with inorganic nucleating agents.
  • the nucleating agents preferred according to the invention are the types of matting agents used for the production of PET spin granules, in particular titanium dioxide. They are used in amounts of 0.01 to 2.0, preferably 0.1 to 1.5% by weight.
  • Preferred PET spin granules have a melting point of at least 250 ° C., measured by means of DSC at a heating rate of 20 ° C./minute.
  • the invention also relates to a method for producing a PET staple fiber according to claim 11, characterized in that a polyethylene terephthalate with a relative viscosity (RV) between 1.45 and 1.68 (measured 1% in m-cresol at 20 ° C) mixed with all additives and additives, mixed, then spun and subsequently stretched.
  • RV relative viscosity
  • the additives and additives are used with suitable ones Devices dosed into the extruder or into the PET melt, if not before, e.g. were added to the granules.
  • the invention further relates to PET staple fibers with improved bulk properties and improved recovery, which is achieved by this method can be produced, and the use of ester compounds of formula I. for the production of PET staple fibers with improved bulk properties and improved resilience.
  • Figure 1 summarizes the results of the bulking test according to Examples 1 to 7 manufactured PET fibers together. It is shown that for a maximum Don't just build the additive concentration in an optimal range must lie, but that for the building return force, which with the Crystallinity is correlated, also the molecular weight or the relative viscosity of the polyester is decisive.
  • the additives according to the invention show curved active surfaces with ridge formation. Bausch's initial height behaves in the area examined and resilience partially counteracting. Only in a defined one Area around point G you get both high values for the initial construction as well as for the return force. These complex relationships in the invention Area are compared to the previous state of knowledge new and unexpected.
  • EG mono-ethylene glycol
  • Ethoxylated bisphenol A, lauric acid and butyltinic acid are placed at 22 ° C and heated to 160 ° C with nitrogen flushing and stirring.
  • the pressure is reduced to approx. 7500 Pa (approx. 56 mm Hg).
  • the water of reaction which forms is removed from the mixture for about 6 hours until the acid number has dropped below 5 mg KOH / g.
  • the product is a slightly yellowish, clear liquid with a viscosity of approx. 410 mPas and a density of approx. 1000 kg / m 3 (both at 25 ° C).
  • Standard PET granules matted with 0.4% TiO 2 (relative viscosity 1.60 / 1% solution in m-cresol at 20 ° C.) were melted on a melt spinning machine and, according to Table 1, ethylene glycol (EG) and bidieol were separated metered the granulate inlet of the extruder (EG and Bidieol are not miscible).
  • Hollow threads were pressed out of a special nozzle plate with 380 bores at a temperature of 262 ° C., cooled with blown air, drawn off at 1000 m / min and placed in a jug.
  • the void fraction of the undrawn threads was approx. 25% (ie the inside diameter was 50% of the outside diameter), the relative viscosity 1.50.
  • the spinning material was then drawn about 3.5 times on a fiber line, then crimped, siliconized, heat-set and cut into staple fibers which had a final titer of 6.5 dtex and a tensile strength of 3.5 cN / dtex at 55% elongation at break.
  • a filler fleece made from it showed bulk values that were significantly higher than those of a commercially available hollow fiber. Building return and crystallinity of the finished fiber Examples 1 2nd 3rd 4th 5 6 7 Experimental A B / E C.
  • the glass transition point only fluctuated by a maximum in all variants 0.5 ° C.
  • An additional test with 2% by weight of bidieol resulted in a reduction in the Glass transition temperature around 3.5 ° C, combined with a clear Building deterioration.
  • Viscosity (1%, m-cresol) 1.50 1.48 Melting point (DSC, 20 ° C / min) 252.0 251.5 Crystallinity (%, from DSC) 49 49 Starting bulk (mm) 126 127 Spring force (%) 86 85 LOI (% O 2 ) 24.4 32.7 / 33.7 **)
  • the PET fiber according to Example 8 according to the invention advantageously fulfills Way the requirements for flame retardancy with high at the same time Bulking and resilience and also after a fiber melting point of at least 250 ° C according to the DSC measurement conditions mentioned above.
  • a fleece with a defined basis weight is produced by means of a card or card and the resulting fleece height is measured under a defined load of 0.9 to 10 p / cm 2 .
  • the fleece height is a measure of the bulk of the fiber.
  • the initial bulk (Ab) is the initial fleece height under 0.9 p / cm 2 load.
  • the resilience (R) is also measured below 0.9 p / cm 2 after the maximum load on the fleece and a defined waiting time and is expressed in% of the initial bulk.

Landscapes

  • 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)
  • Nonwoven Fabrics (AREA)
EP95105498A 1994-04-14 1995-04-12 PET-Fasern mit verbessertem Bausch und Verfahren zu ihrer Herstellung Expired - Lifetime EP0677601B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4412969A DE4412969C1 (de) 1994-04-14 1994-04-14 PET-Fasern mit verbessertem Bausch und Verfahren zu ihrer Herstellung
DE4412969 1994-04-14

Publications (2)

Publication Number Publication Date
EP0677601A1 EP0677601A1 (de) 1995-10-18
EP0677601B1 true EP0677601B1 (de) 1998-07-08

Family

ID=6515450

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95105498A Expired - Lifetime EP0677601B1 (de) 1994-04-14 1995-04-12 PET-Fasern mit verbessertem Bausch und Verfahren zu ihrer Herstellung

Country Status (8)

Country Link
EP (1) EP0677601B1 (enrdf_load_stackoverflow)
CN (1) CN1118819A (enrdf_load_stackoverflow)
CZ (1) CZ92695A3 (enrdf_load_stackoverflow)
DE (2) DE4412969C1 (enrdf_load_stackoverflow)
RU (1) RU95105412A (enrdf_load_stackoverflow)
SK (1) SK46995A3 (enrdf_load_stackoverflow)
TW (1) TW268050B (enrdf_load_stackoverflow)
ZA (1) ZA952345B (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5763538A (en) * 1996-10-28 1998-06-09 E. I. Du Pont De Nemours And Company Process for making an oriented polyester article having improved hydrolytic stability
BR0209814A (pt) * 2001-05-17 2004-06-01 Milliken & Co Fibras de polipropileno de baixo encolhimento, trançados produzidos destas, e métodos de fabricação das mesmas
JP4027728B2 (ja) * 2002-06-21 2007-12-26 帝人ファイバー株式会社 ポリエステル系短繊維からなる不織布
KR100687032B1 (ko) * 2006-04-14 2007-02-26 주식회사 효성 카펫용 3차원 크림프 폴리에틸렌테레프탈레이트멀티필라멘트
US8223899B2 (en) 2007-03-23 2012-07-17 Qualcomm Incorporated Methods and apparatus for initial acquisition gain control in a communication system
WO2012057105A1 (ja) * 2010-10-27 2012-05-03 帝人ファイバー株式会社 バイオマス由来ポリエステル短繊維およびそれからなる湿式不織布
KR101968793B1 (ko) * 2011-12-22 2019-04-12 쓰리엠 이노베이티브 프로퍼티즈 컴파니 멜트 블로잉 공정, 저수축 멜트 블로운 중합체 섬유 및 섬유질 구조, 및 멜트 블로잉할 수 있는 중합체 조성물
CN108276566A (zh) * 2017-12-26 2018-07-13 江阴赛胜新材料有限公司 降低pet结晶速率的生产方法
CN115948818B (zh) * 2023-01-12 2025-01-28 广东秋盛资源股份有限公司 并列型复合纤维及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE663082A (enrdf_load_stackoverflow) * 1964-04-27
US3772137A (en) * 1968-09-30 1973-11-13 Du Pont Polyester pillow batt
EP0194808B1 (en) * 1985-03-08 1989-05-17 Unitika Ltd. Polyester resin composition for forming an impact resistant article
BR8805884A (pt) * 1987-11-13 1989-08-01 Du Pont Enchimento de fibra de poliester;processo aperfeicoado para a preparacao de enchimento de fibra de poliester;processo aperfeicoado para a preparacao de enchimento de poliester alisado;batedura composta essencialmente por enchimento de fibra de poliester;e artigo de mobilia ou de vestuario preenchido
DE4039857A1 (de) * 1990-10-19 1992-04-23 Inventa Ag Verfahren und vorrichtung zur direkten, kontinuierlichen modifizierung von polymerschmelzen

Also Published As

Publication number Publication date
DE4412969C1 (de) 1995-06-22
TW268050B (enrdf_load_stackoverflow) 1996-01-11
ZA952345B (en) 1995-12-20
SK46995A3 (en) 1995-11-08
DE59502718D1 (de) 1998-08-13
RU95105412A (ru) 1997-02-10
EP0677601A1 (de) 1995-10-18
CN1118819A (zh) 1996-03-20
CZ92695A3 (en) 1995-11-15

Similar Documents

Publication Publication Date Title
EP0503421B1 (de) Mit Carbodiimiden modifizierte Polyesterfasern und Verfahren zu ihrer Herstellung
DE69637284T2 (de) Verbesserungen von sulfonatgruppen enthaltenden polyestern, die mit basischen farbstoffen färbbar sind
DE69932231T2 (de) Glatte polyesterfaser
DE69834838T2 (de) Fasern für elektrische beflockung und elektrisch beflockte artikeln
DE3930845A1 (de) Mit carbodiimiden modifizierte polyesterfasern und verfahren zu ihrer herstellung
DE10051578B4 (de) Verfahren zur Herstellung eines aus der Schmelze ersponnenen Polyesterfaserprodukts und Polyesterfaserprodukt hergestellt nach dem Verfahren
DE2827289A1 (de) Mischpolymerisate aus lactiden und glykoliden und verfahren zu deren herstellung
DE69229854T2 (de) Schwer entflammbare pillarme Polyesterfasern
DE69216047T2 (de) Thermoplastische Zusammensetzung und daraus hergestellte Vliesstoffe
EP0677601B1 (de) PET-Fasern mit verbessertem Bausch und Verfahren zu ihrer Herstellung
DE69003547T2 (de) Verfahren zur Herstellung von mit Röntgenstrahlen entdeckbaren Spandexfasern und diese Fasern.
DE69031949T2 (de) Polyesterfaser
WO2010034471A1 (de) Flammhemmende hohlfaser mit silikonfreier weichgriffausrüstung
DE68918796T2 (de) Polyether-ester Block-Copolymer und daraus hergestellte Fäden.
EP0779382B1 (de) Hydrolysebeständige Polyesterfasern und -filamente, Masterbatches und Verfahren zur Herstellung von Polyesterfasern und -filamenten
EP1637633A1 (de) Polyesterfasern, Verfahren zu deren Herstellung und deren Verwendung
WO2010040500A1 (de) Superabsorbierende bikomponentenfaser
DE19951067B4 (de) Polyesterfasern mit verminderter Pillingneigung sowie Verfahren zu ihrer Herstellung
EP0987353B1 (de) Polyesterfasern und -filamente sowie Verfahren zu deren Herstellung
EP0630995A2 (de) Multifilament-Garn aus Polyäthylennaphthalat und Verfahren zu seiner Herstellung
EP2758567B1 (de) Pillarme polyesterfaser
DE69806466T2 (de) Cellulosefasern aus flüssigkristallinen ursprung mit bedeutender bruchdehnung und verfahren zu ihre herstellung
EP1177233B1 (de) Fadenbildende polyester und copolyester und verfahren zu deren herstellung
DE69610894T2 (de) Orientierte Polyamidfasern und Verfahren zu ihrer Herstellung
DE2158552A1 (de) Faserbildende Polyamidmassen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR LI NL

17P Request for examination filed

Effective date: 19950921

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

17Q First examination report despatched

Effective date: 19970915

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR LI NL

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59502718

Country of ref document: DE

Date of ref document: 19980813

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990430

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991101

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991231

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19991101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000201