CN1727539A - Polyester multi-filament yarn for tire cord - Google Patents
Polyester multi-filament yarn for tire cord Download PDFInfo
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- CN1727539A CN1727539A CNA2005100743734A CN200510074373A CN1727539A CN 1727539 A CN1727539 A CN 1727539A CN A2005100743734 A CNA2005100743734 A CN A2005100743734A CN 200510074373 A CN200510074373 A CN 200510074373A CN 1727539 A CN1727539 A CN 1727539A
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- 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
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/48—Tyre cords
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
-
- 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
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
- D02G3/28—Doubled, plied, or cabled threads
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2501/00—Application field
- D07B2501/20—Application field related to ropes or cables
- D07B2501/2046—Tire cords
-
- 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
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
- D10B2505/022—Reinforcing materials; Prepregs for tyres
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S57/00—Textiles: spinning, twisting, and twining
- Y10S57/902—Reinforcing or tire cords
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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)
- Artificial Filaments (AREA)
- Tires In General (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
The invention discloses a polyester multifilament yarn used as tyre reinforcing element and an immersion cord made with the same. The polyester multifilament yarn comprises polyethyleneterephthalate in an amount of not less than 90% by mole, and has an intrinsic viscosity of 0.7~1.2, a toughness of 5.5-8.5g/d, and a difference of middle elongation percentage E0 and E1 (E1-E0) of not less than 6%. The obtained filament yarn and immersion cord exhibits balanced high elastic modulus and low contraction rate and has excellent dimensional stability and fatigue resistance, thus they can be used to reinforce rubber products like tyre.
Description
The application is dividing an application of Chinese patent application 00121404.7 (applying date being on July 19th, 2000).
The present invention relates to a kind of high-modulus, the industrial polyester multi-filament yarn of low-shrinkage and the polyfiber yarn immersion cord of formation thereof of the reinforcement as tire.More particularly, even the present invention relates to a kind of good spatial stability and the polyester multi-filament yarn of fatigue resistance and polyfiber yarn immersion cord of formation thereof that at high temperature also can keep.In addition, the invention still further relates to a kind of method that is used to produce this polyester multi-filament yarn and polyfiber yarn immersion cord.
One of application on the typical functions that fiber had is a reinforcing rubber article, as tire.The example of the fiber that uses as reinforcement comprises nylon, polyester, artificial fibre etc.Wherein polyester fiber contains phenyl ring in its molecular structure, has certain rigid.Correspondingly, the cotton tyre cord of being produced by polyester yarn shows high elastic modulus and the less flat spot with superior fatigue resistance, creep resisting ability and durability.Because these better physical performances, polyester is widely used as rubber, particularly the reinforcement of tire.
Although these advantages are arranged, common polyester tire cord is having significant disadvantages aspect the sidewall impression that reduces the list radial tire.Simultaneously, industrial polyester line also needs the stability of room for improvement so that replace the artificial fibre that is used for radial always.In this, present research intention has the high strength of par and the polyester fiber of high elastic modulus at exploitation and artificial fibre.
The technology that increases heat endurance in polyester fiber has been found that, as United States Patent (USP) 4,101,525 and 4,195, the production that 025 (being all people such as Davis) disclosed a kind of polyester tire cord, promptly under the condition of steam, in the high-speed spinning process, pull out the undrawn yarn of high orientation and obtain the stretching silk thread of high orientation, the bull stretching silk thread that particularly contains the polyethylene terephthalate of at least 85 moles of %, the Denier numerical value scope from 1 to 20 of every rhizoid line, work in the time of 150 ℃ loss be from 0.004 to 0.02lb.in, and the bull silk thread that stretches is immersed in the rubber solutions.
The another kind of prior art relevant with cotton tyre cord can disclose clear 61-12952 from Japan Patent and obtain, it has disclosed a kind of technology of producing cotton tyre cord, this technology comprises the following steps: that with intrinsic viscosity be 1.0, diethylene glycol content is 1.0 moles of %, carboxyl-content is that the polyester of 10 equivalents/106 grams spins under 2000～2500 meters/minute spinning speed, obtains the undrawn yarn line; This undrawn yarn line stretches in the time of about 160 ℃; In the time of 210～240 ℃, silk thread is heat-treated, and silk thread is dipped in the common rubber solutions.In this technology, temperature is lower than 100～450 ℃ temperature range of spinning jet nozzle just.Yet the cotton tyre cord of Sheng Chaning has relatively poor physical characteristic thus.For example, cotton tyre cord in the absorption peak temperature range of pars amorpha from 148～154 ℃, drying shrinkage from 3.3 to 5%, toughness is at least 7.0g/d.
About high tenacity and low-shrinkage, as previously mentioned, the developmental research of the filamental thread that is used for cotton tyre cord that carries out provides the method for producing the undrawn yarn line of high orientation and high-crystallinity in heavily stressed spinning down, and the characteristic of giving silk thread high tenacity and low-shrinkage under high draw ratio by stretching.
According to prior art, the silk thread of producing under high-speed spinning or stretching condition has improved fatigue resistance, is uneven and elongation but difficult point is the strand length of pars amorpha.The result has the coexistence of lax strand to produce a large amount of losses of toughness.Therefore, these silk threads have obvious defects aspect tensile property, and this is because the physical property between the silk thread ectonexine has very big difference, and the bigger physical property variation that shows is because the defective of its microstructure.In addition, by intrinsic viscosity be 1.0 or the silk thread of higher high-viscosity polymer production show limited low shrinkage factor.The silk thread of high orientation stretching has the restrictive two phase structure to crystallization and pars amorpha before the transition process that has experienced cotton tyre cord.And the yarn of high orientation is when heat-treating in being dipped into rubber solutions, along with the deterioration of the inhomogeneities of strand and destroyed crystalline portion, causes intensity decreases.As a result, owing to will bear a series of last handling process, the easier damage of polyester multi-filament yarn.For example, have two bursts of initial draw line that obtain at least through first and second twisted formation cords, subsequently described cord is dipped in the rubber solutions, and merges the rubber-based that forms tire, in these processes, silk thread may change the fracture of concurrent subchain estranged to some extent on physical property.
In fact, because draw line has experienced serious alteration on physical property and molecular structure, for the drawn polyester fiber yarn is used on the cotton tyre cord, importantly to make draw line have the equilibrium of more uniform molecular chain structure and high elastic modulus and low-shrinkage, rather than provide the draw line of high tenacity and low-shrinkage, thereby produced the present invention.
Therefore, one object of the present invention is exactly to overcome the problem that runs in the above-mentioned prior art, and is provided for the polyester multi-filament yarn of cotton tyre cord, and this polyester multi-filament yarn even behind heat ageing still keeps good heat endurance and fatigue resistance.
Another object of the present invention just provides the cotton tyre cord that forms with described polyester multi-filament yarn.
A further object of the invention just provides the method that a kind of production is used for the polyester multi-filament yarn of cotton tyre cord.
In order to achieve the above object, at first, when making draw line, must get rid of the inhomogeneous factor of the molecular chain structure that causes in the silk thread as much as possible, and the high elastic modulus and the low-shrinkage of equilibrium are provided for yarn.Secondly, in immersion process, even in the tire production of strictness, drawing also allows the variation of a homogeneous texture, so that under the hot conditions of tire, promptly when the automobilism tire rotated, the distortion of the cotton tyre cord of the dipping that is obtained was as much as possible little.Tire has fabulous durability as a result.
In other words, in the process of production draw line, the uneven factor of the strand that causes yarn to be reduced to minimumly, be controlled at the parameter that the molecular chain structure of the cotton tyre cord of draw line and dipping in immersion process and the tire production changes simultaneously.
There are many factors can cause the strand of polyester yarn inhomogeneous.For example, from the process of the polyester that is melted to fusion before nozzle is extruded of mylar, the intrinsic viscosity of mylar and fusion temperature are influential to the molecular weight distribution of fusion, and influential to the required retention time of nozzle to the polymer flow of fusion.When the polymer of fusion was extruded from nozzle, the quantity of nozzle and diameter were playing an important role aspect the uniformity of decision gained yarn.In the process after extruding, as quenching process and winding process, quenching temperature and winding speed will cause the variation of the ectonexine structure of the line of extruding from nozzle (following indication is " extruding line "), thereby internal outer field strand produces significantly influence.Extruding in the line process by batching to stretch, described influence factor comprises the directed and fracture of strand.When heat treatment, should consider the relax level of strand.Therefore, the formation of homogeneous texture is subjected to from the polymer melted to the melt spinning in the strand, quenching (quenching temperature) and be stretched to the influence that heat treatment etc. is distributed in the various factors in the different phase process.Because these factors are to be mutually related, the draw line that therefore will produce the strand homogeneous texture just must be carried out suitable combination to these factors.
Essentially, in order to obtain the homogeneous texture of strand, process conditions to the crucial operating procedure of uniformity of molecular chain structure are set the probability of inhomogeneities is reduced to minimum mode.For example, preferably reduce to the retention time of polymer melted and filtration step minimum.Quenching step after the spinning is owing to the inhomogeneities that changes suddenly can reduce widely by transferring sudden change to gradual change.And owing to the strand inhomogeneities that produces that stretches can solve by stretching under low draw ratio condition.In addition, strand has been stablized in heat treatment.
Therefore, when satisfying the condition of difficult operating process, obtain the present invention.
According to an aspect of the present invention, providing by the polyethylene terephthalate that contains at least 90 moles of %, intrinsic viscosity is the process of 0.7～1.2 polyester resin production polyester multi-filament yarn, comprises the following steps: under 290 ℃ or lower temperature described mylar fusing; Filter the mylar of this fusion, filtering retention time is 10 minutes or lower; The resin of filtering molten is extruded spinning by the nozzle that 250～500 holes are arranged, and wherein the diameter range in each hole on the nozzle is from 0.5 to 1.2mm, and draw ratio is 2 to 5; At 100～195 ℃, directly interior to extruding line quenching just: as to be at its glass transition temperature (Tg) or more to carry out under the low temperature with the secondary quenching of quenching air to yarn apart from the zone of following 50mm of nozzle or longer distance; At spinning stress is to take off yarn under 0.3g/d or the bigger condition; Be 1.3 or the bigger condition yarn that stretches and take off with total drawing ratio, and yarn is heat-treated at 150～230 ℃.
Term " filtration retention time " is meant fusion with herein the meaning resin moves to the time that the nozzle nose end is spent from spiral one end of extruder.
According to a further aspect in the invention, the polyester fiber that is used for cotton tyre cord yarn is provided, this yarn comprises the polyethylene terephthalate of at least 90 moles of %, and having intrinsic viscosity is 0.70～1.2, toughness is 5.5～8.5g/d, and the middle rate variance (E0-E1) that extends between middle percentage elongation E0 and E1 reaches 6% or bigger.Middle percentage elongation E0 is the percentage elongation under 4.5g/d load, and middle percentage elongation E1 is under the load of 0.01g/d, through the middle percentage elongation under 4.5g/d load after 177 ℃ the heat treatment in 10 minutes.Yarn preferably has 0.65 or bigger amorphous orientation function, and final modulus is 15g/d or lower.
According to a further aspect in the invention, provide a kind of by at least two strands of twisted cords that form of polyester fiber yarn, the polyester polyfiber yarn immersion cord of this cord being handled with the isocyanates of block and resorcinol formaldehyde emulsion (REL) and making, wherein this cord satisfies following characteristic:
I) toughness is 5.0g/d or bigger,
Ii) spatial stability sex index (E
4.5+ SR) be lower than 7.0%,
Iii) fracture elongation is 9% or bigger,
Poor (E1-E0) of percentage elongation is 3% or lower iv).
The present invention relates to be used for the polyester fiber yarn of cotton tyre cord, its strand is uniformly, and has the high elastic modulus and the low-shrinkage of coordination, and good spatial stability and fatigue resistance.According to the present invention, the mylar that is suitable for producing the polyester fiber yarn contains the polyethylene terephthalate of 90 moles of % at least, and to have intrinsic viscosity be 0.7-1.2, is preferably 0.7-0.9.
With the fusing of described resin, filter and extrude spinning by nozzle.Being melted in when being lower than 290 ℃ of mylar carried out, and preferably is lower than 288 ° ℃, and preferred temperature is between 285-288.In filter process, the filtration retention time of the resin of fusion is 10 minutes or still less, preferred 8 minutes or still less.Described nozzle has 250-500 hole, and the diameter range in each hole is from 0.5 to 1.2mm, and the draw ratio in hole is 2 to 5.
Secondly, extrude line and will pass through first quenching process, wherein line is passed through a direct quenching zone, and maintain the temperature at 100-195 ℃, so that make the line that does not stretch have 0.3g/d or higher spinning stress apart from nozzle bottom 50mm or longer distance.
Then, carry out secondary quenching process, wherein by extruding line and be cured processing being equal to or less than polymer glass conversion temperature (Tg) with the quenching air.
Thereafter draw line is not carried out stretch processing between the Tg of this polymer temperature and crystallized temperature.
At last, with described draw line 150-230 ℃ of heat treatment.
Polyester fiber yarn of the present invention contains preferred 90 moles of %, the more preferably polyethylene terephthalate of 95 moles of %.Correspondingly, the copolyesters content range of other non-polyethylene terephthalate is being less than or equal to 10 moles of %, is preferably 5 moles of % or lower.
Except that polyethylene terephthalate, useful in the present invention copolyesters can be by glycol, as ethylene glycol, 1, ammediol, 1,4-butanediol, 1,6-hexylene glycol and dicarboxylic acids generate as M-phthalic acid, own dihydro terephthalic acid (TPA), adipic acid, cebasic acid and azelaic acid.
The polyester fiber yarn of the present invention fineness of every line usually is the 3-5 Denier, but for a person skilled in the art clearly, this value can change in relative broad range.
When polyester fiber yarn of the present invention joined in rubber such as the tire as reinforcement fabric, this yarn can make rubber show good spatial stability and toughness.Therefore, the polyester fiber yarn can replace being widely used at present the artificial fibre on the list radial tire effectively.In addition, polyester fiber yarn of the present invention can also satisfy the requirement of the spatial stability of further improvement polyester.
At first, when cord extremely shrinks in solidification process, the elastic modelling quantity of cord will reduce significantly.Secondly, the contraction of cord and the uniformity of tire have confidential relation.In fact, accordingly the comparison between elastic modelling quantity under the high temperature and dry the contraction is very important for cotton tyre cord.Middle percentage elongation E
4.5(is percentage elongation under the 4.5g/d in load) and the E after the free shrink (wearing out) during at certain curing temperature
4.5Growth be used as the measurement of compliance.In the factor of all decision tire operability, the elastic modelling quantity under the high temperature is one of most important parameter.
Polyester multi-filament yarn of the present invention is made up of the continuous filament of 200-500 root usually, and the fineness of every rhizoid is the 3-5 Denier, but this value can in very large range change.
When using as polyfiber yarn immersion cord, polyester multi-filament yarn of the present invention can be equal to mutually with the common artificial fibre as the reinforcement material of tire.Particularly, even polyester multi-filament yarn of the present invention uses as technical fabric usually because it also has toughness and pliability and low-shrinkage under 100 ℃ or higher hot conditions.
The raw material that is suitable for as production multi-filament yarn of the present invention is to have intrinsic viscosity (η) to be 0.7-1.2, the polyester of preferred 0.7-0.9.Intrinsic viscosity can be calculated by following formula, uses the Oswald viscosimeter, the relative viscosity (η of the 8g sample solution during by definite 25 ℃ in the 100ml o-chlorphenol
γ) calculate.
η＝0.042η
γ+0.2634
Wherein:
The drop time of t=solution (second),
t
0The drop time of=o-chlorphenol (second),
Density (the gram per centimeter of d=solution
3) and
d
0Density (the gram per centimeter of=o-chlorphenol
3).
If of a sort molecular weight, because the polymerisation amount and the intrinsic viscosity of polymer have same notion, then the structural stability of polymerisation amount and polymer and fatigue resistance are closely related.The molecular weight that is exactly polymer in more detail is more little, and the structural stability of polymer is just good more.On the other hand, the molecular weight of polymer is big more, and the fatigue resistance of polymer is good more.In the present invention, good structural stability can be guaranteed by the polymer that use has an intrinsic viscosity of low relatively from 0.7 to 1.2.Simultaneously, by at 288 ℃ or lower, particularly the spinning polymer makes the reduction of fatigue resistance reach minimum 285-288 ℃ the time, thereby has avoided the minimizing of molecular weight.
Spinning jet nozzle used in this invention has 250-500 hole, and the diameter in each hole is 0.5-1.2mm, preferred 0.8-1.0mm, and draw ratio is 2-5, preferred 3-5.Spinning process is with after 4 spinning, and the form of 2 incidental loopings realizes, the preferable range of the number in the hole on every nozzle is 120 to 250.In this case, behind quenching, implement twice spinning.For the once spinning of after 2 spinning, implementing 2 incidental loopings, on preferred every nozzle 250-450 hole arranged.
In order to obtain high directed not draw line, importantly the spinning stress of draw line is not brought up to 0.3g/d or higher.The influence of amount of tension degree when this is subjected to extruding line and through the quenching air its cooling is reached glass transition temperature.In addition, level of stretch depends on discharge rate, the environment temperature under the nozzle and the quenching air themperature in spinning speed, each hole.
Therefore, the degree of drawing of draw line is not reached with quenching air cooling by the line of extruding from spinning head that the temperature of any decides below the glass transition temperature.In the present invention, even except improve the spinning stress under the same spinning speed by the environment temperature under the control nozzle, also provide a kind of spinning speed is extruded the line drawing deformation velocity with increase technology that improves.Except the frequency of the fabric that will cut off or rupture reduce to minimum, this technology makes that the spinning stress of draw line improves, and produces high directed not draw line.
According to the present invention, extrude line directly under the nozzle quenching zone of 50mm or longer distance cool off for the first time, preferred quenching zone can expand under the nozzle 50mm to the range points of 250mm, the more preferably range points of 50mm-150mm, and maintain the temperature at 100-195 ℃, preferred 100-180 ℃, more preferably 100-150 ℃.
Usually,, make it reach nozzle temperature or higher temperature, reducing the not directed quantity of draw line, draw line not is stretched with the high draw ratio of the line that produces high tenacity thereby reach with gas under the sleeve pipe heated nozzle.Yet the line of gained has high percent thermal shrinkage.When keeping sleeve pipe at high temperature, if spinning is to carry out under high speed to improve spatial stability, rapid deformation gradient will appear in polymer, thereby causes that through regular meeting fiber is cut off or ruptures, and causes the unexpected decline of production efficiency.
After first cooling procedure is finished, filamental thread is carried out the secondary cooling processing with the quenching air.Cooling is preferably carried out between the glass transition temperature of polymer at 20 ℃, preferably at 40-50 ℃.In this temperature range, the difference of the freezing point temperature of fiber ectonexine can reduce.Correspondingly, because the toughness that structural difference causes between fiber ectonexine minimizing can be reduced to minimum.In addition, the minimizing of deformable polymer gradient has improved its spinning characteristic, makes that the deformation gradient in the polymer yarn of heavily stressed fusion of down being spinned out by nozzle reduces, thereby the probability that makes physical characteristic heterogeneous and fracture of wire occurs is reduced to minimum.
If when quenching, heterogeneity occurred in the fiber, after stretching, will reduce the toughness of line significantly, make and use low viscosity polymer in fact can not reach good spatial stability and high tenacity.
In the present invention, the line of La Shening can be not 0.3g/d or higher with spinning stress, and the mode that is preferably 0.5-0.8g/d is reeled.The speed of reeling is 2500m/min or higher, more preferably 2700-3500m/min.Then, the line of reeling is stretched with lower draw ratio, the temperature range never glass transition temperature of draw line arrives crystallization temperature.
The multistage drawing process of preferred in the present invention use.Because the crystallization temperature of the high directed not draw line that the high-speed spinning process produces is hanged down 10 ℃ or lower than the crystallization temperature of the not draw line that is obtained by the low speed spinning process usually, draft temperature preferably is adjusted to 120 ℃ or lower, more preferably 70-120 ℃, most preferably 70-100 ℃.For example,, before the strand orientation, formed fine crystal grain, reduced the degree of drawing of line if draft temperature surpasses 120 ℃, and under opposite extreme situations, the fracture strand.On the other hand, be to carry out being lower than under 70 ℃ the situation if stretch, strand has then lost its flexibility, thus the efficient that causes stretching reduces.
To have toughness at least at the yarn of 5.0g/d in order providing, total draw ratio should to be controlled at 1.3: 1-2.0: 1, preferred 1.3: 1-1.6: 1.For example, when total draw ratio was lower than 1.3: 1, the toughness of gained fiber was very poor.And if draw ratio surpasses 2.0: 1,, just can not obtain high-modulus value and low-shrinkage because the ratio that toughness reduces is very big.
For multistage drawing process, in first drawing zone, stretch preferably reach total drawing ratio 70% or low slightly.For example, if the draw ratio of finishing in first drawing zone surpasses 70% of total drawing ratio, the strand of winding reaches the required time interval of a kind of fibre structure will be so short, to such an extent as to the part strand still keeps twining.Because the defective of structure, the strand of winding has improved hot shrinkage.
In the present invention, the high orientation that produces by the high-speed spinning process not draw line many distinctive advantages are arranged.For example, after stretching, when heat-treating under given conditions, draw line is not transformed into the characteristic that is similar to liquid form rather than shrinks, and this has just reduced the shrinkage of polyfiber yarn immersion cord widely.
Because the crystallization of directed amorphous strand, when heating, extension and the performance of shrinking are considered to the result of the difference of elongation.Correspondingly, the present invention has utilized the mechanism of action of extending and shrinking aspect the reduction contraction.
Go deep into repeatedly and conscientious studying intensively by the inventor, found that,, in drawing process, should not occur by thermogenetic crystallization in order to increase the elongation property that is similar to water the biglyyest.In order to reach this purpose, will be stretching under the temperature that is lower than draw line crystallization temperature not, carry out with lower draw ratio.Under the situation by heat generation crystallization, before drawing process, directed pars amorpha is transformed into crystalline portion, and the extension that the therefore common pars amorpha owing to directed that takes place is transformed into directional crystal changes no longer generation.Have only contraction still to take place, this is owing to the isotropic of amorphous strand that appears at pars amorpha causes, and causes doing the increase of shrinking.
Characteristics of the present invention are exactly the heat treatment draw line.Because will almost be to finish directed line fully to heat-treat, the structure of this line be main relevant with temperature.Heat treatment is to carry out between 150-230 ℃, preferably between 150-180 ℃.For example,, will between pars amorpha and crystalline portion, obvious limit occur, make the orientation amount of crystalline portion when pars amorpha reduces, to increase widely if temperature is higher than 210 ℃.As a result, because improper crystal growing can not be reduced to minimumly in ensuing immersion process, cause physical property to degenerate.When heat-treating, described line can with 2% or more amount be lax.
Usually, when draw line did not stretch, as the crystallization of strand and the result of orientation, draw line did not obtain the nature and characteristic of the yarn of final production.In the drawing process be oriented in crystallization and pars amorpha all can occur, and the tensile stress of pars amorpha is than the height of crystalline portion.
The method according to this invention can the production intrinsic viscosity be 0.7-1.2, preferred 0.7-0.9, toughness is 5.5-8.5g/d, more preferably 5.5-7.5g/d, and poor (E1-E0) of the middle percentage elongation between middle percentage elongation E0 and the E1 can reach 6% or higher, preferred 6-15%, more preferably 6-10%.
Because above-mentioned character is interrelated, for the cotton tyre cord with ideal characterisitics is provided, filamental thread must satisfy all described characteristics.Particularly, poor (E1-E0) of middle percentage elongation must guarantee 6% or bigger scope in, it is to understand one of inhomogeneity most important index of strand when the production draw line, and strand can continue to change equably in ensuing immersion and tire production like this.In this scope, the molecular chain structure of draw line will be transformed into uniform structure in the high temperature immersion process under the high stretching condition.If the difference of E1-E0 is lower than 6%,, in molecular chain structure, may occur inhomogeneous when immersion process is when carrying out under the high stretching condition of high temperature.
When the amorphous orientation function (fa) of line up to 0.65 the time, allow the toughness of line in immersion process, to continue improvement.More preferably line has the amorphous degree of orientation of 0.65-0.8.In addition, more even for the molecular chain structure that makes line in immersion process, the final modulus that preferably sets line is in 15g/d or lower scope.
It is because the heat in stretching and the heat treatment process causes that major part in the line is assembled stress.In order to reduce these stress, United States Patent (USP) 4,101,515 and 4,195, the 052 orientation amount that has disclosed pars amorpha is reduced to 0.6.Yet,,, and, be difficult for obtaining elastomeric character owing to connect the reduction of molecule ratio because the strand that plane of crystal folds and a large amount of defectives of grain boundary can not discharge affined amorphous strand fully even in this case.
Fiber of the present invention is on the basis of 1000-2000 Denier filament, will carry out twisted formation cord more than two strands fiber, then cord is immersed among common binder solution such as the REL (resorcinol formaldehyde emulsion).After the drying, the cord that soaks under stretching condition, is heat-treated with suitable temperature, next cord is normally feared the cord that fire obtains flooding.Term " polyfiber yarn immersion cord " is meant the cord of warp thread cord composition dipping with the meaning herein.In the cord of dipping, weft yarn is just in order to guarantee the distance between the warp cord.Therefore, the characteristic of dipping cord mainly shows by the warp thread cord.The present invention also is like this.
It is 7% or lower that the cotton tyre cord that filamental thread obtained of the application of the invention has the spatial stability sex index, preferred 6%, toughness is 5.0g/d or bigger, preferred 5.5～7.5g/d, fracture elongation is 9% or bigger, 15-20% preferably, and the difference of the middle percentage elongation between the E0-E1 can reach 3% or still less, preferably 2% or still less, more preferably 1% or still less.
Even owing at high temperature still can keep good spatial stability and fatigue resistance, polyfiber yarn immersion cord of the present invention can be used for rubber, as tire.
Above-mentioned physical characteristic is measured according to following method:
-toughness and percentage elongation: adopt the long sample of 250mm, in environment temperature is that 25 ° of C, 65%RH, draw speed are under the 300mm/min, use low speed extension type TENSILE STRENGTH tester to test, tester can be buied with 1017 (1983) of JIS-L from Istron Co., Ltd.
Middle percentage elongation (the E of-line
4.5): the extension value when load is 4.5g/d on the extension curve of load that obtains with TENSILE STRENGTH tester JIS-L 1017.E0 is the middle percentage elongation when load is 4.5g/d, and E1 is to be under the 0.01g/d in load, 177 ℃ of heat treatments after 10 minutes, and the middle percentage elongation when load is 4.5g/d.
The increment of-middle percentage elongation: E1-E0
The middle percentage elongation and the increment thereof of-polyfiber yarn immersion cord: the same step of T1 Repeated Line Tl.
The final modulus of-line: on toughness-percentage elongation curve, can obtain fracture elongation (E (%)) and the suitably increase of the toughness between point (E-2.4) (Δ T (g/d)).Final modulus is calculated with following formula.
The drying shrinkage of-cord (SR): its value is calculated according to following formula, wherein I
0Be when placing it in 25 ℃, 65%RH surpassed after 24 hours, at the cord length that the constantly acting load value records during for 20g, I
1Be with it under the effect of constantly acting load 20g, be placed in 150 ℃ the stove after 30 minutes the length of cord.
-thermal stability index: the middle percentage elongation of cord adds drying shrinkage
-amorphous orientation function (fa): calculate according to following formula (1):
Wherein:
Δ n
cThe intrinsic birefringence (0.220) of=crystal
Δ n
aThe intrinsic birefringence (0.275) of=amorphous body.Intrinsic birefringence (Δ n) can be calculated according to following formula (2), measures the delay that the interference fringe by sample obtains by being installed in Berek compensator on the petrographic microscope,
Δn＝R/d (2)
Wherein:
D=sample thickness (nm)
R=postpones (nm).
-degree of crystallinity (x
c): with density (ρ, the unit: g/cm of line
3) determine according to following formula.
ρ
c(g/cm
3)＝1.445
ρ
a(g/cm
3)＝1.335
Density (ρ) can be passed through the density gradient column method, in the time of 25 ℃, utilizes normal heptane and carbon tetrachloride to measure.
-spinning stress:, measure the stress between the lube plant and first godet roller by means of tension gage.
Can understand the present invention better by the embodiment that lists below, but these embodiment do not limit the present invention.
Embodiment 1 to 5 and Comparative Examples 1 to 4
The intrinsic viscosity that will prepare by the solid polymerization effect be 0.65 polyester scraps, under the condition of appointment, carry out melt spinning by the spinning head that 300 holes (diameter in hole is 0.60mm) are arranged in table 1.Is to filter in 8 minutes the resin of fusion to filter retention time.The sleeve pipe that a 200mm is long is placed on the tight below of spinning head, so that the various temperature conditions shown in the table 1 to be provided.At quench area, when draw line not is removed with the speed of 3000m/min,, be to be cured effect under the condition of 0.6m/sec in translational speed with 40 ℃ secondary quenching air.Then, draw line does not stretch with godet roller in the two-step stretch process of 80 ℃ and 100 ℃ (total drawing ratio is 1.60 times).On godet roller, with line in all temps heat treatment as shown in table 1.When slack 2% the time, the thin silk thread of 1000 Denier is wound onto on the filament winding machine.
The physical characteristic of the line that obtains from each embodiment is listed in the table 2.
It is twisted and for the second time twisted that two strands that will obtain from each embodiment carry out the first time respectively in 480TPM, and be immersed among 245 ℃ the REL and obtain polyfiber yarn immersion cord.The physical characteristic of polyfiber yarn immersion cord is as shown in table 3 below.
Table 1
| Sequence number | The intrinsic viscosity of chip | The spinning temperature (℃) | First quenching temperature (℃) | The spinning stress (g/d) of draw line not | Heat treatment temperature (℃) |
| Embodiment 1 | 0.75 | 282 | 100 | 0.35 | 190 |
| Embodiment 2 | 0.75 | 282 | 190 | 0.32 | 190 |
| Embodiment 3 | 0.85 | 284 | 150 | 0.42 | 200 |
| Embodiment 4 | 0.85 | 284 | 195 | 0.40 | 200 |
| Embodiment 5 | 0.95 | 288 | 150 | 0.55 | 200 |
| Comparative Examples 1 | 0.70 | 295 | 250 | 0.25 | 230 |
| Comparative Examples 2 | 0.95 | 300 | 250 | 0.34 | 230 |
| Comparative Examples 3 | 0.95 | 300 | 320 | 0.32 | 230 |
| Comparative Examples 4 | 1.10 | 305 | 320 | 0.41 | 230 |
Table 2
| Sequence number | Toughness (g/d) | Fracture elongation (%) | Final modulus (g/d) | Amorphous body degree of orientation (fa) | The intrinsic viscosity of line | The increment (%) of middle percentage elongation |
| Embodiment 1 | 5.8 | 15.8 | 2.5 | 0.81 | 0.71 | 11.8 |
| Embodiment 2 | 5.8 | 15.5 | 2.0 | 0.78 | 0.70 | 13.2 |
| Embodiment 3 | 7.0 | 16.0 | 12.0 | 0.75 | 0.82 | 10.5 |
| Embodiment 4 | 7.0 | 16.0 | 10.8 | 0.69 | 0.82 | 8.1 |
| Embodiment 5 | 7.0 | 15.8 | 12.9 | 0.75 | 0.92 | 6.9 |
| Comparative Examples 1 | 5.4 | 12.9 | 26.6 | 0.62 | 0.64 | 4.2 |
| Comparative Examples 2 | 6.8 | 12.2 | 32.0 | 0.64 | 0.88 | 5.7 |
| Comparative Examples 3 | 6.9 | 12.5 | 32.8 | 0.64 | 0.88 | 5.3 |
| Comparative Examples 4 | 7.5 | 12.3 | 34.9 | 0.63 | 0.95 | 4.8 |
Table 3
| Sequence number | The physical characteristic of polyfiber yarn immersion cord | The increment (%) of middle percentage elongation | Remarks | |||
| Toughness (g/d) | E 4.5 | SR | ES | |||
| Embodiment 1 | 5.2 | 3.5 | 2.3 | 5.8 | 2.6 | - |
| Embodiment 2 | 5.2 | 3.5 | 2.5 | 6.0 | 2.3 | - |
| Embodiment 3 | 6.2 | 3.5 | 2.8 | 6.3 | 2.6 | - |
| Embodiment 4 | 6.2 | 3.5 | 3.0 | 6.5 | 2.8 | - |
| Embodiment 5 | 6.3 | 3.5 | 3.1 | 6.6 | 3.0 | - |
| Comparative Examples 1 | 4.7 | 3.5 | 3.0 | 6.5 | 3.8 | The toughness of line reduces greatly |
| Comparative Examples 2 | 5.3 | 3.5 | 4.0 | 7.5 | 5.6 | |
| Comparative Examples 3 | 5.5 | 3.5 | 4.0 | 7.5 | 5.3 | |
| Comparative Examples 4 | 5.9 | 3.5 | 4.3 | 7.8 | 5.2 | |
In sum, the data that obtain from embodiment and Comparative Examples show: fiber yarn of the present invention and polyfiber yarn immersion cord also have the high elastic modulus and the low-shrinkage of coordination except having good spatial stability and fatigue resistance.Conclusion is that fiber yarn of the present invention and polyfiber yarn immersion cord can be as the reinforcements of rubber such as tire.
The present invention narrates in the mode of introducing, and it is narrative should understanding employed technical terms, rather than to its restriction.The present invention can carry out many improvement and variation according to above-mentioned technology.Therefore, these improvement and variation also drop in the protection domain of appending claims, and the present invention can realize in the mode in addition that specification is described.
Claims (5)
1. be used for the polyester fiber yarn of cotton tyre cord, this yarn comprises the polyethylene terephthalate of at least 90 moles of %, and to have intrinsic viscosity be 0.7～1.2, and toughness is 5.5-8.5g/d; Poor (E1-E0) of the middle percentage elongation between middle percentage elongation E0 and E1 reaches 6% or bigger, percentage elongation E0 is to be the percentage elongation of 4.5g/d in load wherein, middle percentage elongation E1 is when load is 0.01g/d, 177 ℃ of heat treatments after 10 minutes, in load is the percentage elongation of 4.5g/d, and it is 0.65 or bigger that wherein said yarn has amorphous orientation function (fa).
2. according to the polyester fiber yarn of claim 1, toughness scope wherein is 5.5 to 7.5g/d.
3. according to the polyester fiber yarn of claim 1, the difference E1-E0 of middle percentage elongation wherein is 6-15%.
4. according to the polyester fiber yarn of claim 3, the difference E1-E0 of middle percentage elongation wherein is 6-10%
5. according to the polyester fiber yarn of claim 1, it is 15g/d or lower that wherein said yarn has final modulus.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990031513A KR100571214B1 (en) | 1999-07-31 | 1999-07-31 | Polyester multifilamentary yarn for tire cords, dipped cord and production thereof |
| KR31513/1999 | 1999-07-31 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001214047A Division CN1247834C (en) | 1999-07-31 | 2000-07-19 | Polyester polyfiber yarn, immersion cord for lyre cord fabric and its producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1727539A true CN1727539A (en) | 2006-02-01 |
| CN1727539B CN1727539B (en) | 2011-05-25 |
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ID=19605905
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005100743734A Expired - Fee Related CN1727539B (en) | 1999-07-31 | 2000-07-19 | Polyester multi-filament yarn for tire cord |
| CN2005100743749A Expired - Fee Related CN1727540B (en) | 1999-07-31 | 2000-07-19 | Polyester polyfiber yarn immersion cord |
| CNB001214047A Expired - Fee Related CN1247834C (en) | 1999-07-31 | 2000-07-19 | Polyester polyfiber yarn, immersion cord for lyre cord fabric and its producing method |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005100743749A Expired - Fee Related CN1727540B (en) | 1999-07-31 | 2000-07-19 | Polyester polyfiber yarn immersion cord |
| CNB001214047A Expired - Fee Related CN1247834C (en) | 1999-07-31 | 2000-07-19 | Polyester polyfiber yarn, immersion cord for lyre cord fabric and its producing method |
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| Country | Link |
|---|---|
| KR (1) | KR100571214B1 (en) |
| CN (3) | CN1727539B (en) |
| ID (1) | ID26686A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476184A (en) * | 2016-08-02 | 2019-03-15 | 大陆轮胎德国有限公司 | For the product made of elastomeric material, it is preferred for the enhancement layer and Pneumatic vehicle tire of Pneumatic vehicle tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101384759B (en) * | 2006-02-16 | 2012-03-14 | 株式会社Duel | multifilament and manufacturing method thereof, yarn and manufacturing method thereof |
| KR100687033B1 (en) * | 2006-04-14 | 2007-02-26 | 주식회사 효성 | Polyethyleneterephthalate multifilament with high tenacity for industrial use |
| WO2008156334A1 (en) | 2007-06-20 | 2008-12-24 | Kolon Industries, Inc. | Drawn poly(ethyleneterephthalate) fiber, poly(ethyleneterephthalate) tire-cord, their preparation method and tire comprising the same |
| KR101228128B1 (en) | 2008-03-31 | 2013-01-31 | 코오롱인더스트리 주식회사 | Drawn poly(ethyleneterephthalate) fiber, tire-cord and tire comprising the same |
| CN101978104B (en) * | 2008-03-31 | 2013-01-02 | 可隆工业株式会社 | Undrawn polyethylene terephthalate (pet) fiber, drawn pet fiber, and tire-cord comprising the same |
| EP2281932B8 (en) * | 2008-04-29 | 2016-10-12 | Kolon Industries, Inc. | Aramid tire cord and manufacturing method thereof |
| KR101552697B1 (en) * | 2010-06-30 | 2015-09-11 | 코오롱인더스트리 주식회사 | Method for manufacturing poly(ethyleneterephthalate) drawn fiber, poly(ethyleneterephthalate) drawn fiber and tire-cord |
| KR101812237B1 (en) * | 2011-09-27 | 2017-12-27 | 코오롱인더스트리 주식회사 | Method for manufacturing poly(ethyleneterephthalate) drawn fiber, poly(ethyleneterephthalate) drawn fiber and tire-cord |
| CN104160075B (en) * | 2011-12-30 | 2016-06-08 | 可隆工业株式会社 | Poly-(ethylene glycol terephthalate) oriented fibre, poly-(ethylene glycol terephthalate) tyre cord and its preparation method |
| CN102618946B (en) * | 2012-04-24 | 2015-10-21 | 可隆（南京）特种纺织品有限公司 | The manufacture method of polyethylene terephthalate drawn wire, polyethylene terephthalate drawn wire and tyre cord |
| CN102634858A (en) * | 2012-04-24 | 2012-08-15 | 可隆（南京）特种纺织品有限公司 | Manufacture method of polyethylene terephthalate drawn wire, tyre cord fabric and manufacture method thereof |
| KR101559517B1 (en) | 2014-01-16 | 2015-10-19 | 주식회사 효성 | Dimensionally stable polyester tire cord and method of manufacturing the same |
| ITUA20163301A1 (en) * | 2016-05-10 | 2017-11-10 | Bridgestone Corp | BELTS WITH METAL CANVAS FOR TIRES |
| KR102030360B1 (en) * | 2018-02-06 | 2019-10-10 | 효성첨단소재 주식회사 | Manufacturing Method For Tire Cord Fabric By Displaying Slit Site |
| CN109775405B (en) * | 2019-02-18 | 2020-06-09 | 平顶山神马帘子布发展有限公司 | Method for correcting pressure of double-roller friction type passive winding device for winding impregnated cord fabric |
| KR102166025B1 (en) | 2019-03-26 | 2020-10-15 | 효성첨단소재 주식회사 | Process for manufacturing high modulus low shrinkage polyethylene terephthalate fiber and the polyethylene terephthalate fiber manufactured thereby |
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| GB1278244A (en) * | 1968-10-11 | 1972-06-21 | Ici Ltd | Macrofilamentary yarns and rubber structures reinforced therewith |
| JPS57144106A (en) * | 1981-03-04 | 1982-09-06 | Toyo Tire & Rubber Co Ltd | Pneumatic tire of high uniformity |
| BR8907519A (en) * | 1988-07-05 | 1991-06-18 | Allied Signal Inc | PROCESS FOR THE PRODUCTION OF A DRAWN POLYETHYLENE TEREFTALATE YARN, YARN AND RESULTING PRODUCTS |
| US5067538A (en) * | 1988-10-28 | 1991-11-26 | Allied-Signal Inc. | Dimensionally stable polyester yarn for highly dimensionally stable treated cords and composite materials such as tires made therefrom |
| BR9102420A (en) * | 1990-06-14 | 1992-01-14 | Du Pont | POLYESTER MONOFILAMENTS TO REINFORCE TIRES |
| DE4126219A1 (en) * | 1991-08-08 | 1993-02-11 | Duerrwaechter E Dr Doduco | METHOD FOR PRODUCING CONTACT PLATES |
| KR930010802B1 (en) * | 1991-12-14 | 1993-11-11 | 주식회사 코오롱 | Method for preparation of polyester tyre cord or tyre cord yarn |
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| AU713003B2 (en) * | 1995-12-30 | 1999-11-18 | Kolon Industries, Inc. | Polyester filamentary yarn, polyester tire cord and production thereof |
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1999
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-
2000
- 2000-07-19 CN CN2005100743734A patent/CN1727539B/en not_active Expired - Fee Related
- 2000-07-19 CN CN2005100743749A patent/CN1727540B/en not_active Expired - Fee Related
- 2000-07-19 CN CNB001214047A patent/CN1247834C/en not_active Expired - Fee Related
- 2000-07-31 ID IDP20000646D patent/ID26686A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476184A (en) * | 2016-08-02 | 2019-03-15 | 大陆轮胎德国有限公司 | For the product made of elastomeric material, it is preferred for the enhancement layer and Pneumatic vehicle tire of Pneumatic vehicle tire |
| CN109476184B (en) * | 2016-08-02 | 2021-03-02 | 大陆轮胎德国有限公司 | Article made of elastomeric material, reinforcement layer preferably for a pneumatic vehicle tyre, and pneumatic vehicle tyre |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1727540A (en) | 2006-02-01 |
| CN1290772A (en) | 2001-04-11 |
| ID26686A (en) | 2001-02-01 |
| CN1727540B (en) | 2010-06-16 |
| CN1727539B (en) | 2011-05-25 |
| KR20010011919A (en) | 2001-02-15 |
| CN1247834C (en) | 2006-03-29 |
| KR100571214B1 (en) | 2006-04-13 |
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