EP1234065B1 - Polypropylene fiber and preparation thereof - Google Patents
Polypropylene fiber and preparation thereof Download PDFInfo
- Publication number
- EP1234065B1 EP1234065B1 EP00973247A EP00973247A EP1234065B1 EP 1234065 B1 EP1234065 B1 EP 1234065B1 EP 00973247 A EP00973247 A EP 00973247A EP 00973247 A EP00973247 A EP 00973247A EP 1234065 B1 EP1234065 B1 EP 1234065B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- set forth
- polypropylene
- fiber
- index
- fibers
- 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
Links
- 239000000835 fiber Substances 0.000 title claims description 74
- 239000004743 Polypropylene Substances 0.000 title claims description 44
- 229920001155 polypropylene Polymers 0.000 title claims description 44
- -1 Polypropylene Polymers 0.000 title claims description 43
- 238000002360 preparation method Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims description 28
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 238000002074 melt spinning Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 description 49
- 238000009960 carding Methods 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical class CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical class C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Chemical class 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Chemical class CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 206010046543 Urinary incontinence Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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
- 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
- D01F6/06—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 from polypropylene
Definitions
- the present invention relates, in general, to a polypropylene fiber and, more particularly, to a polypropylene fiber which is useful as a material for non-woven fabrics, thereby allowing the non-woven fabrics to be smooth and excellent in strength and providing workability and physical properties for the non-woven fabrics during after-processes. Also, the present invention is concerned with a method for preparing such fibers.
- staple fibers are prepared from polyolefin polymers, they have to undergo a series of processes: the polyolefin polymers are generally compounded with some amount of additives and the resulting mixtures are melt-extruded in ordinary commercial processes to give fibers, which are crimped and cut into predetermined lengths.
- polyolefin staples When being applied for the making of non-woven fabrics, polyolefin staples are typically processed in a carding machine to give non-woven webs which are then thermally bonded.
- a pair of calender rollers, ultrasonification, or hot air is usually used.
- polypropylene filaments or staples are arranged after opening and carding processes, and bridged to afford webs. These webs are thermally bonded with the aid of a calender roller with diamond or delta type patterns to produce non-woven fabrics which are industrially useful in various fields.
- hot air may be utilized instead of calender rollers. In this case, after being allowed to undergo a carding process, webs are bonded to give non-woven fabrics by means of hot air which is circulated in a porous drum.
- Polypropylene non-woven fabrics find numerous applications in the disposable diaper, diaper for patients suffering from urinary incontinence, hygienic band, mask, and medical fabric industries. Although not demanding strength as high as that of woven fabrics, the non-woven fabrics used in these purposes have to be soft and satisfy the requirement of safety to skin because they are in direct contact with the skin.
- the strength of non-woven fabrics varies depending on their preparation processes as well as on physical properties of material fibers.
- non-woven fabric producing manufacturers generally try to make high production speed.
- the high production speed demands more excellent physical properties for the fibers for non-woven fabrics.
- EP-0518316 discloses a stretched molded article of ultra-high-molecular-weight polypropylene having an intrinsic viscosity [ ⁇ ] of at least 4 dl/g, which has a degree of orientation of not less than 0.930 when obtained as a degree of orientation by an X-ray diffraction half-width, two or more of peak positions (melting points) within the temperature region of not lower than 180°C when measured by a differential scanning calorimeter, and an amount of output energy of not less than 1 kgfm/g after 10-time repetition under a load of 50% of the breaking strength.
- EP-0518316 also discloses a process for the preparation of a stretched molded article of ultra-high- molecular-weight polypropylene having a large amount of output energy comprising the steps of :
- polypropylene fibers for non-woven fabrics which can be applied to high-speed carding machines and guarantee the excellent strength and softness of the non-woven fabrics after thermal bonding.
- a polypropylene fiber which is obtained from an isotactic polypropylene homopolymer with an isotactic index of 90 to 99 % through melt-spinning or through drawing after melt-spinning, and shows two differential scanning calorimeter (DSC) endothermic peaks between 155 and 170 °C, said fiber having a melt index (MI c ) of 16.5 to 80.0 and a polydispersity index (PI c ) of 2.1 to 5.7.
- MI c melt index
- PI c polydispersity index
- a method for preparing polypropylene fibers comprising the steps of: (a) melting in an extruder an isotactic polypropylene homopolymer with an isotactic index of 90-99 %, a melting index (MI a ) of 10.0-40.0, preferably 10.0-25.0 and a polydispersity index ( PI a ) of 2.5-6.0, preferably 2.8-5.0 and more preferably 3.5-4.3 to give a molten polymer which has a melt index (MI b ) with the ratio of MI b /MI a ranging from 1.01 to 1.50 and a polydispersity index (PI b ) narrower by 10 % or less than the PI a; (b) spinning the molten polymer and controlling the quenching condition after the spinning to produce fibers with a melting index (MI c ) of 16.5-80.0 and a polydispersity index (PI c ) narrower by 20% or
- the present invention pertains to polypropylene fibers which are prepared from polypropylene homopolymers with an isotactic index of 90 to 99% by melt-spinning or by melt-spinning and drawing and have two differential scanning calorimeter (DSC) endothermic peaks in the range from 155 to 170 °C.
- the polypropylene fibers of the present invention show a primary endothermic peak at 160 ⁇ 3 °C and a secondary endothermic peak at 165 ⁇ 3 °C.
- non-woven fabrics are prepared from the polypropylene fibers of the present invention by thermal bonding, the above physical properties allow the non-woven fabrics to be smooth with excellent strength. This advantage is believed to result from the fact that, while the fibers thermally fused due to the heat or the heat and the pressure between rolls are solidified again, rapid recrystallization occurs in the regions which are high in melting points.
- Useful as materials to prepare the fibers of the present invention are polypropylene homopolymers with an isotactic index of 90 to 99 %.
- the polypropylene fibers of the present invention have a melt index (MI c ) of 16.5-80.0, which is preferably 1.65-7.50 times as large as that (MI a ) of the material isotactic polypropylene.
- the polypropylene fibers of the present invention range, in polydispersity index (PI c ), from 2.1 to 5.7 and, preferably from 3.5 to 4.3 with a value being narrower by 20 % than the PI a of the material isotactic polypropylene.
- PI c polydispersity index
- the isotactic polypropylene used in the present invention preferably ranges, in melt index (MI a ), from 10 to 40 and, in polydispersity index (PI a ), from 2.5 to 6.0.
- a stabilizer or an antioxidant is preferably formulated at an amount of 0.03 to 2.0 wt%, preferably 0.03 to 0.7 wt% and more preferably 0.03 to 0.4 wt%.
- a deoxidant agent such as a colorant, metal carboxylates, etc.
- the metal carboxylate available in the present invention is selected from the group consisting of nickel salts of 2-ethyl hexanoic acid, caprylic acid, decanoic acid, and dodecanoic acid, Fe, Co, Ca and Ba salts of 2-ethyl hexanoic acid, and combinations thereof.
- the deoxidant agent or the colorant calcium stearate, which is usually used to prepare polypropylene homopolymers in petrochemical plants, may be selected.
- a variety of additives available in the present invention may be referred to European patent No. 279,511.
- the isotactic polypropylene useful in the present invention preferably has a melt index (MI a ) of 10 to 40.
- MI a melt index
- the isotactic polypropylene has an MI a of greater than 40, the resulting fibers are not suitable for non-woven fabrics in terms of strength. Further, incompletion frequently occurs in the fulfillment of quenching after the spinning, leading to fusion between neighboring fibers.
- the fibers of the present invention include those which are obtained through melting, spinning, solidifying and taking-up processes as well as those which are obtained through a drawing process after melting and spinning processes and necessarily have undergone the processes of crimping, thermal fixing and cutting into staples.
- the fibers which experience melt-spinning are almost identical to those which further experience drawing in MI, PI and DSC endothermic peak.
- the material polymer is melted in an extruder to give a molten polymer which has a melt index (MI b ) with the ratio of MI b /MI a ranging from 1.01 to 1.50 and a polydispersity index (PI b ) being narrower by 10 % than PI a and more preferably by 5 %.
- MI b melt index
- PI b polydispersity index
- a preferable PI b falls in the range of 2.4 to 5.0.
- the polymer which has undergone an MI change in the extruding process is allowed to be secondarily changed in MI.
- the MI change at a quenching step is determined depending on the temperature of the delayed quenched region, the atmosphere, the temperature, speed and quantity of quenching air.
- U.S. Pat. No. 4,193,961 describes the use of delay quenching and quenching air, which may also be referred to other documents, for example, M. Ahmed "Polypropylene Fibers-Science and Technology" sponsored by Society of Plastics Engineers, Inc.
- the fibers which experience the quenching step are preferably controlled to have a melt index (MI c ) 1.65-7.50 times as large as the melt index (MI a ) of the material polymer and a polydispersity index (PI c ) narrower by 20 % or less than that (PI a ) of the material polymer (that is, amounts to 0.80x,PI a or wider).
- the fibers preferably range, in PI c , from 2.1 to 5.7, more preferably from 2.3 to 4.5 and most preferably from 3.0 to 4.0.
- the strength of the grey yarns is deteriorated.
- the making of non-woven fabrics from the grey yarns suffers from poor workability because the non-woven fabrics are apt to be contaminated with card clothing and partially melted on the calender roll.
- the yarn has a too greatly decreased molecular weight and the quenching effect after the spinning from a nozzle is decreased to generate fusion between yarns.
- the yarns are used to make non-woven fabrics after being forcibly prepared in spite of the above conditions, much powder is generated from the poor yarns in an opening and a carding process, having a negative influence on the making process.
- heat-vulnerable portions of the poor yarns are melt out upon calendering, making dirty the surface of the calender roll which plays a role in the final thermal bonding of the non-woven fabrics.
- the strength of the grey yarn is improved, but it is difficult for such grey yarns to improve the thermal bonding index (hereinafter referred to as "TBI") to a desired extent. That is, the non-woven fabrics obtained show low TBI and feel harsh to the touch. Although the strength or TBI of the non-woven fabrics can be improved by increasing the temperature of the calender roll or the thermal bonding area, the non-woven fabrics still remain harsh.
- TBI thermal bonding index
- non-woven fabrics Upon the making of non-woven fabrics, their machine direction orientation and cross direction strengths vary depending on the kinds and arrangements of carding machines. Differences may be found in the machine direction and cross direction strengths of the non-woven fabrics which have passed through carding machines if these machines are manufactured by different manufacturers. Even in the carding machines manufactured by the same manufacturers, the non-woven fabrics show different physical properties in dependence on the shape and material of carding clothing and the presence of random rolls. In addition, the non-woven fabrics are different in plan weight, depending on the requirements for the after-process. The measured strength values of the non-woven fabrics represent simple tenacity and their units are characteristically different from one company to another.
- the simple tenacity is unsuitable to determine whether the physical properties of the non-woven fabrics are improved.
- the structure and inherent physical properties of the yarn or staple can be compared as to the influence on the non-woven fabrics by reference to the bonding indexes of the non-woven fabrics prepared although a difference may exist in kinds or arrangements of the carding machines.
- TBI In accurately determining the influence of the physical properties of yarns or staples on the non-woven fabrics thereof, therefore, the concept of TBI is recognized as very proper. A detail of TBI is described in an article concerning Polypropylene Fibres and Textiles, reported in the Fourth International Conference held by The Plastics and Rubber Institute. Indeed, TBI is introduced in the present invention as the most valuable parameter to comparatively determine the influence of the physical properties of yarns or staples on the non-woven fabrics.
- the non-woven fabrics can be made which are 2.0 or higher in TBI with good softness.
- DSC endothermic Peaks fiber samples were sufficiently washed to remove oiling agents. After being dried for 30 min in the air, the samples were vacuum-dried for 1 hour in a decicater and cut into a length of 2-4 mm. The cut samples of 5mg were put on a measuring pan which was then subjected to thermal analysis using the Perkin Elmer 7 series Thermal Analysis System in which the temperature was elevated at a rate of 5 °C/min from 30 °C to 190 °C, so as to obtain endothermic curves. Other conditions of this measurement were accorded with ASTM 3418-82 method.
- Fig. 1 shows two apparent DSC endothermic peaks of the fiber according to the present invention and Fig. 2 shows that a secondary DSC endothermic peak appears in a shoulder form of a primary DSC endothermic peak.
- Fig. 3 is an endothermic curve showing that only one DSC endothermic peak appears in a conventional fiber.
- Denier of Yarn and Staple measured using Vibroskop, manufactured by Lenzing.
- MI Melt Index
- PI Polydispersity Index
- Isotactic Index (I.I.): a polypropylene homopolymer sample was cut into a length of 5 mm, washed with water, and dried at 105 °C for 1 hour in an oven. After taking about 5g and then being accurately weighed, a portion of the dried sample was boiled for about 5 hours in heptane for extraction. After completion of the extraction, the sample was sufficiently washed with water, dried at 105 °C for 1 hour in an oven and then weighed. The weights measured before and after the extraction were substituted in the following equation to yield the isotactic index.
- Isotactic Index ( % ) Weight After Extraction Weight Before Extraction ⁇ 100
- TBI ( MD ⁇ CD ) 1 / 2 ⁇ 20 Plan Weight
- MD is a machine direction strength (kg/50 mm)
- CD is a cross direction strength (kg/50 mm)
- plan weight is a weight per area of a non-woven fabric.
- Softness the feeling to the touch was graded: 1 very harsh; 2 harsh; 3 ordinary; 4 soft; 5 very soft.
- MI isotactic polypropylene homopolymers with an isotatic index of 97% and MI as indicated in Table 1, below, containing an antioxidant and stabilizer at an amount of 0.09 wt%, were melt-spun at an extruder temperature from 250 to 290 °C while the heating in the range from the extruder to the nozzle was controlled in the range of 285-310 °C by means of a heating medium to allow the melt to have MI b as indicated in Table 1, below.
- a bypass was set to take the samples
- the melt was extruded at a spinning rate of 1,500 m/min through a spinneret, passed through a heat reserving zone for delayed quenching and then quenched to afford primary yarns of 2.4 deniers, which had Mic, PIc and DSC endothermic peaks as shown in Table 1.
- the primary yarns thus obtained were collected in a bundle and drawn at a drawing ratio of 1.5 times while being crimped in a crimper, following cutting them to staples 40 mm long.
- the staples were applied to the carding machines according to manufacturers.
- the upper roll used for the preparation of non-woven fabrics was of a diamond type with a sealing area amounting to 22 % while the calender roll performed its function at 147 °C with a pressure of 95 kg/cm.
- the non-woven fabrics which are prepared by thermally bonding the isotactic polypropylene homopolymer fibers having two DSC endothermic peaks in accordance with the present invention, show excellent strength in addition to being soft. Also, the non-woven fabrics can be produced in high speed carding machines. Consequently, the present invention allows the production of high quality non-woven fabrics with a high yield.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-1999-0049610A KR100401246B1 (ko) | 1999-11-10 | 1999-11-10 | 폴리올레핀 섬유의 제조방법 |
KR9949610 | 1999-11-10 | ||
KR2000013319 | 2000-03-16 | ||
KR10-2000-0013319A KR100401248B1 (ko) | 2000-03-16 | 2000-03-16 | 폴리프로필렌 섬유 및 그 제조방법 |
PCT/KR2000/001270 WO2001034884A2 (en) | 1999-11-10 | 2000-11-07 | Polypropylene fiber and preparation thereof |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1234065A2 EP1234065A2 (en) | 2002-08-28 |
EP1234065A4 EP1234065A4 (en) | 2005-06-15 |
EP1234065B1 true EP1234065B1 (en) | 2006-03-22 |
Family
ID=26636302
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00973247A Expired - Lifetime EP1234065B1 (en) | 1999-11-10 | 2000-11-07 | Polypropylene fiber and preparation thereof |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP1234065B1 (es) |
CN (1) | CN1174129C (es) |
AU (1) | AU768809B2 (es) |
BR (1) | BR0010462B1 (es) |
CA (1) | CA2372453C (es) |
DE (1) | DE10084374B4 (es) |
DK (1) | DK175963B1 (es) |
ES (1) | ES2237983B1 (es) |
GB (1) | GB2365438B (es) |
LU (1) | LU90849B1 (es) |
MX (1) | MXPA02001814A (es) |
MY (1) | MY120636A (es) |
WO (1) | WO2001034884A2 (es) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104389040B (zh) * | 2014-10-28 | 2016-03-09 | 湖北博韬合纤有限公司 | 轻质gmt板专用聚丙烯短纤维加工工艺 |
KR102251754B1 (ko) * | 2019-12-24 | 2021-05-12 | 도레이첨단소재 주식회사 | 기계적 강도가 향상된 부직포 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO131514C (es) * | 1968-07-04 | 1975-06-18 | Montedison Spa | |
JPS509810A (es) * | 1973-06-04 | 1975-01-31 | ||
JP3070694B2 (ja) * | 1991-06-11 | 2000-07-31 | 三井化学株式会社 | 超高分子量ポリプロピレン延伸成形体およびその製造方法 |
JP2948948B2 (ja) * | 1991-07-08 | 1999-09-13 | 宇部日東化成 株式会社 | 熱接着性繊維 |
TW275076B (es) * | 1992-12-02 | 1996-05-01 | Hoechst Ag | |
US5529845A (en) * | 1994-06-13 | 1996-06-25 | Montell North America Inc. | Fibers suitable for the production of nonwoven fabrics having improved strength and softness characteristics |
JP3554433B2 (ja) * | 1996-04-10 | 2004-08-18 | 特種製紙株式会社 | 湿式電子写真方式用被記録シート |
JPH10195714A (ja) * | 1996-12-27 | 1998-07-28 | Mitsui Chem Inc | ポリプロピレン製繊維 |
US6416699B1 (en) * | 1999-06-09 | 2002-07-09 | Fina Technology, Inc. | Reduced shrinkage in metallocene isotactic polypropylene fibers |
-
2000
- 2000-10-18 MY MYPI20004879A patent/MY120636A/en unknown
- 2000-11-07 CN CNB008024685A patent/CN1174129C/zh not_active Expired - Lifetime
- 2000-11-07 EP EP00973247A patent/EP1234065B1/en not_active Expired - Lifetime
- 2000-11-07 MX MXPA02001814A patent/MXPA02001814A/es active IP Right Grant
- 2000-11-07 DE DE10084374T patent/DE10084374B4/de not_active Expired - Fee Related
- 2000-11-07 BR BRPI0010462-0A patent/BR0010462B1/pt not_active IP Right Cessation
- 2000-11-07 WO PCT/KR2000/001270 patent/WO2001034884A2/en active IP Right Grant
- 2000-11-07 CA CA002372453A patent/CA2372453C/en not_active Expired - Fee Related
- 2000-11-07 ES ES200250025A patent/ES2237983B1/es not_active Expired - Fee Related
- 2000-11-07 GB GB0121728A patent/GB2365438B/en not_active Expired - Fee Related
- 2000-11-07 AU AU11778/01A patent/AU768809B2/en not_active Ceased
-
2001
- 2001-09-25 DK DK200101392A patent/DK175963B1/da not_active IP Right Cessation
- 2001-10-10 LU LU90849A patent/LU90849B1/en active
Also Published As
Publication number | Publication date |
---|---|
DE10084374T1 (de) | 2002-11-07 |
GB2365438A (en) | 2002-02-20 |
GB0121728D0 (en) | 2001-10-31 |
DE10084374B4 (de) | 2006-04-06 |
MY120636A (en) | 2005-11-30 |
BR0010462B1 (pt) | 2011-03-22 |
MXPA02001814A (es) | 2002-09-24 |
DK200101392A (da) | 2001-09-25 |
CN1174129C (zh) | 2004-11-03 |
CA2372453A1 (en) | 2001-05-17 |
AU768809B2 (en) | 2004-01-08 |
WO2001034884A3 (en) | 2001-10-18 |
DK175963B1 (da) | 2005-09-19 |
WO2001034884A2 (en) | 2001-05-17 |
AU1177801A (en) | 2001-06-06 |
GB2365438B (en) | 2003-07-16 |
ES2237983A1 (es) | 2005-08-01 |
CN1335901A (zh) | 2002-02-13 |
LU90849B1 (en) | 2002-01-24 |
EP1234065A2 (en) | 2002-08-28 |
BR0010462A (pt) | 2003-07-08 |
EP1234065A4 (en) | 2005-06-15 |
ES2237983B1 (es) | 2006-11-01 |
CA2372453C (en) | 2004-06-08 |
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