CA2126328C - High modulus polyester yarn for tire cords and composites - Google Patents
High modulus polyester yarn for tire cords and composites Download PDFInfo
- Publication number
- CA2126328C CA2126328C CA002126328A CA2126328A CA2126328C CA 2126328 C CA2126328 C CA 2126328C CA 002126328 A CA002126328 A CA 002126328A CA 2126328 A CA2126328 A CA 2126328A CA 2126328 C CA2126328 C CA 2126328C
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- Canada
- Prior art keywords
- yarn
- drawn
- undrawn
- tenacity
- shrinkage
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
Abstract
Yarns are prepared by spinning PEN or other semi-crystalline polyester polymers made from similarly rigid monomer combinations to a state of optimum amorphous orientation and crystallinity.
This is accomplished by selection of process par-ameters to form an undrawn polyester yarn of birefringence at least 0.030. The spun yarn is then hot drawn to a total draw ratio of between 1.5/1 and 6.0/1 with the resulting drawn semi-crystalline polyester yarn having Tg greater than 100°C and a melting point elevation at least 8°C. The preferred yarn has a tenacity at least 6.5 g/d; dimensional stability (EASL + Shrinkage) of less than 5 %, and shrinkage 4 % or less. The resulting yarn exhibits surprisingly high modulus and tenacity together with low shrin-kage when compared to prior art yarns.
This is accomplished by selection of process par-ameters to form an undrawn polyester yarn of birefringence at least 0.030. The spun yarn is then hot drawn to a total draw ratio of between 1.5/1 and 6.0/1 with the resulting drawn semi-crystalline polyester yarn having Tg greater than 100°C and a melting point elevation at least 8°C. The preferred yarn has a tenacity at least 6.5 g/d; dimensional stability (EASL + Shrinkage) of less than 5 %, and shrinkage 4 % or less. The resulting yarn exhibits surprisingly high modulus and tenacity together with low shrin-kage when compared to prior art yarns.
Description
KC~1.~U\:E:f~.y~l1'~:\CIiL:\_'~' _..
"~___.,~3..~1~'"~~3~'.,...1'~~'31"Wiu4,a'?U :3~WF~ - +.~J SJ '?:3a:.i-1'r~~~:N
BIO~I D~ODUhUS pOLYTr8TE3'~t Y~1 p0lt T~Rg CORZlB ~D~D CO~ED09IT$$
1. ~~ og ~~ zrrv~r~rzoN t Thin invention relates to polyethyl~ne aaphthalate (PEN) multifilament yarn and other yarns ' grade from eim,ilarly rigid monomer combinations with extremely high modulua, good tenacity, and low shrinkage particularly useful for the textile reinforcement of tires. The P8N yarn of this invention provides enhanced modulus and dimensional stability when compared to conventionally processed p$N yarns. A
1o process for production of the mufti-filament PST yarn ie an aspect of this invention.
a. ~~~~~ OF RELATED ART
Currently, polyethylene terephthalate (PET>
' filaments are co~nonZy used in industrial applicatiane i5 including radial tire bodies, conveyor belts, seat baits, V belts and hoeing. However, higher modulus and dimenBional stability is preferred in more demanding applications such ae bodies of monoply high pertornance tires and ie required in the belts oP radial paesez~ger 2o tires. Dimensional stability is defined ae the darn oL
the elongation at ~.5 g/d (39.7 mN/dtex) and shrinkage, U.9. Patent 3,516,832 to Bhima et ai. provides rubber articles rein.torced with PEN of good dimensional stability and. tenacity and U.6. Patent 3,929,18Q to 25 Kawase et al. provides a tire with PEN used as a carcass reinforcement. However, these patents are concerned with conventionally processed PBN of low undrawn birefringence and hence do not achieve the full property potential of this material ae ie the object of 3o this invention. The ~eame is true of British Pa.tant .._ 1,445,464 to Hamana et al. which teaches optimized drawing of conventionally spun PBN. U.S. Patent 4,OOO,a39 to Hamana et al, provides a process for producing a high melting point, heat resistant undrawn :5~..~::~-''~~'~.; ' t ~'4.~r.=r: ~- AMENDED SHE~_- .__ _..
' v , +-l;i 89 '?:3~J~i~l4C,p: it ri ItW . W~. : ~t~yll. E'\CI IE\ .'' ..._. , ,~... _ _., 'B . E~? . 8'3 .' ,...18 ::3.-',~ ~ 8O-~ , ~:..U 3uC8 ~. _ z~zs32s a pEN for electrically insulating fabrics. Since these materials were prepared under high stress conditions favoring high. cryetallinity or at least highly nucleated structures, they lack drawability and s cannot attain. high moduZus for the applications contemplated herein. A product for the same application is provided i,n U. S . 4, 001, 4'79 to Hama.na et ai . , which is concerned with partially oriented yarns of high elongation arid low tenacity.
14 BUI~ARY OR THE ~jVFNTION
The: yarns of thi~ invention are prepared by spinning PAN or other semi-crystalline polyester polymers made: from similarly rigid monomer combinations to a state off' optimum amorphous orientation and 13 crystallini.t~~. The invention is accomplished by selection of process parameters to form an uadrawn polyester yarn of birefringence at least: 0.030. The spun yarn is then hots drawn to a total draw ratio of between x.5/1 and 6.0/1 with the resulting drawn eemi-2o crystalline ~~olyeeter yarn having Tg greater than 100°C
and a melting pciat elevation at least ~''C. The preferred yarn has a tenacity at leant 6.5 g/d (5'7.4 mN/dtex), diatenrioaal stability (ERBL f Shrinkage) of lees than 5~, sad shrinkage 4~ or less.
25 They resulting yarn exhibits surprisingly high modulue and tenacity together with low ~hrinkage when compared to ~~rior art yarns.
B,~~z~R nAQC~RIpTION OF TEL DFtlltR_ INGS
Fic~. 1 represents a comparison of modules at 30 a tenacity o!: 6.2 g/d (54.7 mN/dtex) for the Pa~N yarns of Examples ~'~. and ~ .
DSSCFtIISTION OF T ~ PRTs~'ERRED EMBODTMENT
ThE~ polyester multifilament yarn of the .
present inve=ition provides high modules, high. , .._ 3s dimensional ~~tability and good tenacity, characterietj.ce which are extremely desirable when this material ie j.ncorporated as fibrous reinforcement into rubber cornpo~iitee such as tires. PEN multifilament AMENDED SHEET
fvCV: ~u~:EYA-v11 E\CHE:;y'J _~ ,,~_~_..-''3-.1~-'"'3'3 ~;~...1~'3'?'.''t3U4 u'?U 3oEi8 ~ +4~ 89 '?:3~94~~E~:~:/I E
., 21~~~2~
yarns or other yarns of polyester polymers made Irom similarly rigid monomer combinations can be used advantageously to reinforce two parts of a radial passenger tine, the carca9s and the belt. Currently, s passenger tine carcasses are reinforced primarily by polyethylene terephthalate. Two tire characteristics xhich are cox~troiled by the carcass cord property of dimensional e~tability (modulue at a given shrinkage) are sidewall indentations and tire handling. The high 1o modulus and d.imeneional stability of the P$N or other polyester yarns of this invention relative to ~BT and prior art p~ yarns means that tires with carcasses reinforced with the yarns of thin invention will exhibit lower' eidewall indentation and betCer handling is behavior. The. yarns of this invention are also a desirable reinforcement material because of their high glass transition temperature (Tgy greater than 100°C, i . a . 1~ 0°C for P$N, compared to a Tg Qf 80°C for PST .
Ths high Tg will result in lower cord heat generation z0 over a widex temperature range relative to P$T tires, resulting in longer tire lifetimes and overall cooler tire operating temperatures. zn addition, since modulus tends to drop precipitou~ly at temperatures above Tg, the yarns of this invention will maintain modulus over Zs a wider temperature range than PST. All of the above mentioned advantages will be of critical importaac~e when yarns of this invention are used to reinforce high performance tires since this application requires low cord heat generation and high modulue, especially at 30 elevated operating temperatures characteristic of high speed perfora;ance driving.
PSIf multifilameat yarns and other polyester yarns of thi~ invention can also be used to reinforce the belts of radial passenger tires and the carcaes~ee . w 35 of radial truck tires. Currently steel ie used for these applications since B$T possesses insufficient strength and modulus for a gives cord diameter. The high modulue of PEN relative to PST, and the additional AMENDED SHEET
RC~.~U'~:EF'.'-~IIE:\CH~\~'y ~... "~_-_.,~'3.1,.'~-~:3~',".,.1'3;_3a3':8(1-~
;~~?W35F~8 ~ +~~9 8J '~:39;3,~~(i5;# r __ 212638 modulus advan,tageg of th~ P$N of this invention will make pSN an ideal material to be used as a steel substitute.
The polyethylene naphthalate yarn of the s invention contains at least 90 aiol percent polyethylene naphthalate. Ia a preferred embodiment, the polyester is substantially all polyethylene naphthalate.
Alternatively, the polyester may incorporate as copolymer unite minor amounts of units derived from one l0 or more eater-forming ingredients other than ethylene glycol and 2,6 naphthy~,ene dicarboxylic acid or their derivatives.
Illustrative examples of other ester forming ingredient~ which may be copolymerized with the 1s polyethylene r~aphthalate unite include glycole such as 1,3-prvpanediol, 1,4-butanediol, 1,6-hexanadivl, etc., and dicarboxylic acids such as terephthalic acid, isophthalic acid, hexahydroterephthalic acid, etilbeae dicarboxylic acid, bibenzoic acid, adipic acid, eebacic 2o acid, azelaic acid, etc.
Other polyester yarns of the invention can be prepared to contain polyester polymer made from suitable combinations of rigid and flexible monomers providing the resulting polymer is melt-epinnable, is is ~emi-crystalline, and has a Tg greater than 100°.
Exampler of rigid monoa~ars include dicarboxylic acids such ae ~,6-r~aphthaleae dicarboxyliC acid, 2,7-naphthale;4e dicarboxylic acid, Biphenyl dicarboxylic ~~cid, etilbene dicarboxylic acid and 3o terephthalic ~~cid; dihydroxy compounds such as hydroquinone, biphenol, p-xylene glycol, 2,4 cyclohexanedimethanol, neopentylene glycol; and hydroxycarbox,~rlic acid such as P-hydroxybenzoic acid and 7-hydroxy~-~-naphthvic acid. Examples of flexible 3S monomers inchide dicarboxylic aside such ae oxalic acid, euccini~: acid, adipic acid, sebacic acid, and dihydroxy corny?ounds such as ethylene glycol, 1,3 AMENDED SHEET
S~lF~ '~ o ~.1~t ~~~.~: ~' RC~.W )\:l~t-'.ylll_Ey\Ct(L:\''v _.. "____.,':ivJ-y'~J:3.~"v.lJ'3-~":810~,5'?u :3:~Ett3 ~ +~1-~ f3J '_';3f3;i4~lE:;p:# ti ~12632g propanediol, 1,4 butanediol, 1,6 hexaned:.ol. It is important that the thermal stability of the polymer above its melting point be sufficient to allow melt processing without excessive degradation.
s 'rhs mufti-filament yarn of the present invention coranonly possesses a denier per fila,~ent of about 1 tv 20 (e. g. about 3 to iG), and commonly consists of about 6 to 600 continuous filaments (e. g.
about 20 to 400 continuous filaments). The denier per filament and the number of continuous filaments present in the yarn m~,y be varied widely as will be apparent to those skilled in the art.
Th~s mufti-filament yarn is particularly suited for us~,e in industrial applications wherein high is strength paly~eeter fibers have bees utilized in the prior art. ' The fibers are particularly suited for use in . environatenta where elevated temperatures (e.g. 100°Cy I
are encountered. Not only.dvea the fila,mentaxy material 2o provide enhanned rnodulus but it undergoes a very low degree of ahr:.nkage for a high modulue r-Lbrous thermoplastic.
The unexpected dimensional stability advantage seems to originate from the foxznatior_ of a 2s unique rnorpho:Logy during spinning which arises from the cryetallizati«n of highly oriented amorphous regions characte-rized by as undrar~m birefringence of at least 0.03, preferaJ5ly 0.03 to C.30. This crystallization occurs in either the drawing stage or the spinning 30 stage depending oa the level of stress imposed during spinning. =f f:oo much stress is applied during spinning, tha undrawn yarae tend to Lack drawability and character:lstically exhibit melting points greater than 290°C fox' PEN. The characterization parameters ~-35 referred to hsarein may conveniently be determined by testing the muitifilament yarn which consists of s~ubetantially parallel filaments.
1. BIREBRINGBNCB - Birefringence was AMENDED SHEET
~~J
~ a 1 lu as extinction band is not visible the purple colored ha.-:~:
should be used for this measurement.
2. DENSITY - Densities were determined in a n-heptane/carbon tetrachloride density gradient colu:~r. a~
23°C. The gradient column was prepared and calibrated according to ASTM D1505-68.
"~___.,~3..~1~'"~~3~'.,...1'~~'31"Wiu4,a'?U :3~WF~ - +.~J SJ '?:3a:.i-1'r~~~:N
BIO~I D~ODUhUS pOLYTr8TE3'~t Y~1 p0lt T~Rg CORZlB ~D~D CO~ED09IT$$
1. ~~ og ~~ zrrv~r~rzoN t Thin invention relates to polyethyl~ne aaphthalate (PEN) multifilament yarn and other yarns ' grade from eim,ilarly rigid monomer combinations with extremely high modulua, good tenacity, and low shrinkage particularly useful for the textile reinforcement of tires. The P8N yarn of this invention provides enhanced modulus and dimensional stability when compared to conventionally processed p$N yarns. A
1o process for production of the mufti-filament PST yarn ie an aspect of this invention.
a. ~~~~~ OF RELATED ART
Currently, polyethylene terephthalate (PET>
' filaments are co~nonZy used in industrial applicatiane i5 including radial tire bodies, conveyor belts, seat baits, V belts and hoeing. However, higher modulus and dimenBional stability is preferred in more demanding applications such ae bodies of monoply high pertornance tires and ie required in the belts oP radial paesez~ger 2o tires. Dimensional stability is defined ae the darn oL
the elongation at ~.5 g/d (39.7 mN/dtex) and shrinkage, U.9. Patent 3,516,832 to Bhima et ai. provides rubber articles rein.torced with PEN of good dimensional stability and. tenacity and U.6. Patent 3,929,18Q to 25 Kawase et al. provides a tire with PEN used as a carcass reinforcement. However, these patents are concerned with conventionally processed PBN of low undrawn birefringence and hence do not achieve the full property potential of this material ae ie the object of 3o this invention. The ~eame is true of British Pa.tant .._ 1,445,464 to Hamana et al. which teaches optimized drawing of conventionally spun PBN. U.S. Patent 4,OOO,a39 to Hamana et al, provides a process for producing a high melting point, heat resistant undrawn :5~..~::~-''~~'~.; ' t ~'4.~r.=r: ~- AMENDED SHE~_- .__ _..
' v , +-l;i 89 '?:3~J~i~l4C,p: it ri ItW . W~. : ~t~yll. E'\CI IE\ .'' ..._. , ,~... _ _., 'B . E~? . 8'3 .' ,...18 ::3.-',~ ~ 8O-~ , ~:..U 3uC8 ~. _ z~zs32s a pEN for electrically insulating fabrics. Since these materials were prepared under high stress conditions favoring high. cryetallinity or at least highly nucleated structures, they lack drawability and s cannot attain. high moduZus for the applications contemplated herein. A product for the same application is provided i,n U. S . 4, 001, 4'79 to Hama.na et ai . , which is concerned with partially oriented yarns of high elongation arid low tenacity.
14 BUI~ARY OR THE ~jVFNTION
The: yarns of thi~ invention are prepared by spinning PAN or other semi-crystalline polyester polymers made: from similarly rigid monomer combinations to a state off' optimum amorphous orientation and 13 crystallini.t~~. The invention is accomplished by selection of process parameters to form an uadrawn polyester yarn of birefringence at least: 0.030. The spun yarn is then hots drawn to a total draw ratio of between x.5/1 and 6.0/1 with the resulting drawn eemi-2o crystalline ~~olyeeter yarn having Tg greater than 100°C
and a melting pciat elevation at least ~''C. The preferred yarn has a tenacity at leant 6.5 g/d (5'7.4 mN/dtex), diatenrioaal stability (ERBL f Shrinkage) of lees than 5~, sad shrinkage 4~ or less.
25 They resulting yarn exhibits surprisingly high modulue and tenacity together with low ~hrinkage when compared to ~~rior art yarns.
B,~~z~R nAQC~RIpTION OF TEL DFtlltR_ INGS
Fic~. 1 represents a comparison of modules at 30 a tenacity o!: 6.2 g/d (54.7 mN/dtex) for the Pa~N yarns of Examples ~'~. and ~ .
DSSCFtIISTION OF T ~ PRTs~'ERRED EMBODTMENT
ThE~ polyester multifilament yarn of the .
present inve=ition provides high modules, high. , .._ 3s dimensional ~~tability and good tenacity, characterietj.ce which are extremely desirable when this material ie j.ncorporated as fibrous reinforcement into rubber cornpo~iitee such as tires. PEN multifilament AMENDED SHEET
fvCV: ~u~:EYA-v11 E\CHE:;y'J _~ ,,~_~_..-''3-.1~-'"'3'3 ~;~...1~'3'?'.''t3U4 u'?U 3oEi8 ~ +4~ 89 '?:3~94~~E~:~:/I E
., 21~~~2~
yarns or other yarns of polyester polymers made Irom similarly rigid monomer combinations can be used advantageously to reinforce two parts of a radial passenger tine, the carca9s and the belt. Currently, s passenger tine carcasses are reinforced primarily by polyethylene terephthalate. Two tire characteristics xhich are cox~troiled by the carcass cord property of dimensional e~tability (modulue at a given shrinkage) are sidewall indentations and tire handling. The high 1o modulus and d.imeneional stability of the P$N or other polyester yarns of this invention relative to ~BT and prior art p~ yarns means that tires with carcasses reinforced with the yarns of thin invention will exhibit lower' eidewall indentation and betCer handling is behavior. The. yarns of this invention are also a desirable reinforcement material because of their high glass transition temperature (Tgy greater than 100°C, i . a . 1~ 0°C for P$N, compared to a Tg Qf 80°C for PST .
Ths high Tg will result in lower cord heat generation z0 over a widex temperature range relative to P$T tires, resulting in longer tire lifetimes and overall cooler tire operating temperatures. zn addition, since modulus tends to drop precipitou~ly at temperatures above Tg, the yarns of this invention will maintain modulus over Zs a wider temperature range than PST. All of the above mentioned advantages will be of critical importaac~e when yarns of this invention are used to reinforce high performance tires since this application requires low cord heat generation and high modulue, especially at 30 elevated operating temperatures characteristic of high speed perfora;ance driving.
PSIf multifilameat yarns and other polyester yarns of thi~ invention can also be used to reinforce the belts of radial passenger tires and the carcaes~ee . w 35 of radial truck tires. Currently steel ie used for these applications since B$T possesses insufficient strength and modulus for a gives cord diameter. The high modulue of PEN relative to PST, and the additional AMENDED SHEET
RC~.~U'~:EF'.'-~IIE:\CH~\~'y ~... "~_-_.,~'3.1,.'~-~:3~',".,.1'3;_3a3':8(1-~
;~~?W35F~8 ~ +~~9 8J '~:39;3,~~(i5;# r __ 212638 modulus advan,tageg of th~ P$N of this invention will make pSN an ideal material to be used as a steel substitute.
The polyethylene naphthalate yarn of the s invention contains at least 90 aiol percent polyethylene naphthalate. Ia a preferred embodiment, the polyester is substantially all polyethylene naphthalate.
Alternatively, the polyester may incorporate as copolymer unite minor amounts of units derived from one l0 or more eater-forming ingredients other than ethylene glycol and 2,6 naphthy~,ene dicarboxylic acid or their derivatives.
Illustrative examples of other ester forming ingredient~ which may be copolymerized with the 1s polyethylene r~aphthalate unite include glycole such as 1,3-prvpanediol, 1,4-butanediol, 1,6-hexanadivl, etc., and dicarboxylic acids such as terephthalic acid, isophthalic acid, hexahydroterephthalic acid, etilbeae dicarboxylic acid, bibenzoic acid, adipic acid, eebacic 2o acid, azelaic acid, etc.
Other polyester yarns of the invention can be prepared to contain polyester polymer made from suitable combinations of rigid and flexible monomers providing the resulting polymer is melt-epinnable, is is ~emi-crystalline, and has a Tg greater than 100°.
Exampler of rigid monoa~ars include dicarboxylic acids such ae ~,6-r~aphthaleae dicarboxyliC acid, 2,7-naphthale;4e dicarboxylic acid, Biphenyl dicarboxylic ~~cid, etilbene dicarboxylic acid and 3o terephthalic ~~cid; dihydroxy compounds such as hydroquinone, biphenol, p-xylene glycol, 2,4 cyclohexanedimethanol, neopentylene glycol; and hydroxycarbox,~rlic acid such as P-hydroxybenzoic acid and 7-hydroxy~-~-naphthvic acid. Examples of flexible 3S monomers inchide dicarboxylic aside such ae oxalic acid, euccini~: acid, adipic acid, sebacic acid, and dihydroxy corny?ounds such as ethylene glycol, 1,3 AMENDED SHEET
S~lF~ '~ o ~.1~t ~~~.~: ~' RC~.W )\:l~t-'.ylll_Ey\Ct(L:\''v _.. "____.,':ivJ-y'~J:3.~"v.lJ'3-~":810~,5'?u :3:~Ett3 ~ +~1-~ f3J '_';3f3;i4~lE:;p:# ti ~12632g propanediol, 1,4 butanediol, 1,6 hexaned:.ol. It is important that the thermal stability of the polymer above its melting point be sufficient to allow melt processing without excessive degradation.
s 'rhs mufti-filament yarn of the present invention coranonly possesses a denier per fila,~ent of about 1 tv 20 (e. g. about 3 to iG), and commonly consists of about 6 to 600 continuous filaments (e. g.
about 20 to 400 continuous filaments). The denier per filament and the number of continuous filaments present in the yarn m~,y be varied widely as will be apparent to those skilled in the art.
Th~s mufti-filament yarn is particularly suited for us~,e in industrial applications wherein high is strength paly~eeter fibers have bees utilized in the prior art. ' The fibers are particularly suited for use in . environatenta where elevated temperatures (e.g. 100°Cy I
are encountered. Not only.dvea the fila,mentaxy material 2o provide enhanned rnodulus but it undergoes a very low degree of ahr:.nkage for a high modulue r-Lbrous thermoplastic.
The unexpected dimensional stability advantage seems to originate from the foxznatior_ of a 2s unique rnorpho:Logy during spinning which arises from the cryetallizati«n of highly oriented amorphous regions characte-rized by as undrar~m birefringence of at least 0.03, preferaJ5ly 0.03 to C.30. This crystallization occurs in either the drawing stage or the spinning 30 stage depending oa the level of stress imposed during spinning. =f f:oo much stress is applied during spinning, tha undrawn yarae tend to Lack drawability and character:lstically exhibit melting points greater than 290°C fox' PEN. The characterization parameters ~-35 referred to hsarein may conveniently be determined by testing the muitifilament yarn which consists of s~ubetantially parallel filaments.
1. BIREBRINGBNCB - Birefringence was AMENDED SHEET
~~J
~ a 1 lu as extinction band is not visible the purple colored ha.-:~:
should be used for this measurement.
2. DENSITY - Densities were determined in a n-heptane/carbon tetrachloride density gradient colu:~r. a~
23°C. The gradient column was prepared and calibrated according to ASTM D1505-68.
3. MELTING POINT - Melting points were determined with a Perkin-Elmer*Differential Scanning Calorimeter (DSC) from the maxima of the endotherm resulting from scanning a 10 mg sample at 20°C per minute. Tg is to be taken under the same experimental conditions as the inflection point in the change heat capacity associated with the glass transition temperature. Melting point evaluation for drawn yarns ( ~'~ Tm) is defined as:
~1 _ X11 where Tml is the melting point of the drawn yarn of interest and Tmll is the melting point of a yarn which is pre-melted and rapidly cooled in the DSC before 2o analysis.
~1 _ X11 where Tml is the melting point of the drawn yarn of interest and Tmll is the melting point of a yarn which is pre-melted and rapidly cooled in the DSC before 2o analysis.
4. INTRINSIC VISCOSITY - Intrinsic viscosity (IV) of the polymer and yarn is a convenient measure of the degree of polymerization and molecular weight. I~~~ is determined by measurement of relative solution viscosity (~ r) in a mixture of phenol and tetrachloroethane (60/40 by weight) solvents. ~ r is the ratio of the flow tire of a PEN/solvent solution to the flow time of pure solvent through a standard capillary. IV is calculated by extrapolation of relative solution viscosity data to a 3o concentration of zero.
5. PHYSICAL PROPERTIES - The tensile properties referred to herein were determined through the utilization of an Instron*tensile tester using a 10 inc!~
gauge length and a strain rate of 120 percent per minute. All tensile measurements were made at roots temperature. Dimensional stability refers to the level of stress achieved at a given shrinkage. In the tire * trademark RCV: VU\ : EI~~ X111 EVCHf:'~ ''? " , .___ _..~'3 .1..~ »9'~ .' ,...19 '35":
8U4 , 5_'U 308 -~ +49 89 ''.'3J94-~E~S : t! 1 (>
_.
z the level of stress achieved at a given shrinkage. In the tire indu,etry, dimensional stability is defined ae the sum of elongation at a specified load plus shrinkage. Fc~r the present case, the elongation at a s ap~cified load (EASL) is derived from the initial modulue data using the following equation:
EA6L - 454/Modulus (g/d) It ig well known that tenacity and madulue increase with, increasing draw-ratio. while higher io tenacity per se ie almost always highly desirable, the high extensicn ratios are often net achievable due to yarn quality problems or to excessive shrinkage.
Materials of this invention po~sees high levels of modulus for a given level of tenacity. This ie is quantified as the LT parameter, by ratioing L-5 to _ tenacity as follows:
LT ~~ ((L-5)4/T5.16) 1000 L-5 or~LA9$-5 is a measure of modulue defiaad ae load in g/d at 5f elongation. The materials of this Zo invention have LT at lea~t 25. If L-5 ig not measurable because of yarn elongatione less than 5~ the yarns will be pre-relaxed at elevated temperatures before testing .
to increase elongation beyond 5~.
Shrinkage values were determined is 25 accordance~with ATM D885 after one minute at 177°C
employing a constraining force o~ 0.05 g/denier (0.44 mN/dtex)-.
2dentified hereafter ie a description of a process which has been found to be capable of forming 30 the improved ,yarn of the present invention. Tha yarn product claimed hereafter ie not to be limited by the parameters of the process which followra.
The melt-epinnable poly~eter it supplied to an extrusion ~spinaerette at a temperature above its ~~-3s melting point and below the temperature at which the polymer d~gradee substantially. The residexlce time at this stage is kept to a minimum and the temperature should not ri;ae above 350°C, preferably 320°C.
AMENDED SHEET
~r ~~.'~~~=~r°.i ___...~~.._.__._..._~.~._~.._._.. _.._.._..
RC1.VO\:EP:~-11l'E~:CHE\_~~ _, ,.~__~..~'3-.1..~.~3~~"...1'~~3F',y8G4,5'?G
35E~$ , +4J 8:J '?899~1~t~5:#Ll 21263~~
The extruded filaments then traverse a conventional yarn solidification $vne where quench air impinges on the spun yarn thereby freezing in dea:irabia internal structural features and preventing the filaments fro:a fusing to one another. Tha solidification zone preferably comprises (a) a retarded cooling zone ca~mprising a gaseous atmosphere heated at a te~aperature to at least 150°C, preferably 150 to 500°C, and (b) ~a cooling zone adjacent to said rstarded to cooling sons wh,erain said yarn is rapidly cooled and solidified in a. blown air atmosphere. The ksy to the current proceso~ is to adjust processing conditions to aohievv a highly oriented undrawn yarn of birafringenee at last 0.03 a,nd an elevated melting point of ~-Z5°C, is preferably 3-23°C. For pEN a malting point of 265 to 290°C, prafsrab.ly 268 to 288°C must be achieved. Ono skilled in the art can aehiavo this by adjusting the following eondi,tiona: length and temperature of the retarded eoolin.g tone adjacent to the spinnorstte, 2o diameter of ths. apron~rette holes, method of blowing the q~,iench, gue~nah air velocity, and drawdown in the solidifioation ions. The speed of withdrawal of the yarn from the aoiidification zone is an important parameter affecaing the stress on the spun fiber, and 25 should ba adjus;ted to yi~ld the desired ' characteristics,. Tha spur: yarn is then drawn by conventioAal means in either a continuous or non-continuous process to yield a drawn yarn with Tg greater than iC~o°c and a melting point elevation at 30 least 8°c, preferably 8 to 15°C. ~t is preferred to have the following drawn yarn properties: tenacity at least s.5 g/d (57.4 mN/dtox), preferably at least 7.5 g/d (66.Z mN/dt.ax): dimensional stability (EA3L +
shrinkage) of less than 5~~ and shrinkage of a~ .or , .._ 3s leas.
y Ei~ - ( CondPnRATIVE ) ~'A~~~EN~ undrawn yarn was produced by axtxvding AMENDED SHEET
~ w'~ s ~ -.~.
[tCV.~U\:E:E~ yii-E\CHE:\.'? _.. ~,~___..-~:i"E?,.=3:3~'"~.i''3::3',_'';~~:~,~~-'~~ ~vESfi -» +~[~i f3;3 '?:39,31_1~~:;:N[w ._ ' ' Jr ' 2~2G328 3Z filaments through a spinnerette with orifices of length 0.042 in~ch$s (o.107cm) and of width 0.021 inches (0.053 cm) at a. thruput or 23.2 cc/min. The filaments were soiiditied, in an air quenching column and'taken up at winder spaed,s of 305 m/min.
This yarn was drawn in two stages using conventional heated rolls. The undrawn yarn properties, drawn yarn propartieo, and drawing conditions are gumr~arised in Table I.
to The yarn of this example, which was prepared conventionally from an undrawn yarn of 0 n m o.Io04, possesses poorer modulus than the yarns of this invention as evidenced by LT less than 25. Also'the dimensional stability parameter (EA8L + shrinkage) of i3 8.3 is higher than that of yarns of this invention, indicating poorer dimensional stability (see Exnmpl~
zii) .
TAB I , A. UNDRAW~T Yet 20 ~ n 0.004 Tmnacity (g/d) 0.6 (5.3 mN%dtex) Modulus (g/d) 18.6 (164 mN/dtex) Tm (°C) 268 25 ~. DRAW N YARN
Dr aw Ratio 6 . 3 Roll 1 (C) 140 Roll 2 (~C) 157 Roll 3 (C) RT
n 0.426 Tenacit;Y (g/d) 6.Z (54.? mN/dtsx) Modulus (g/d) 176 (1553 mN/dtox) Tm (C) 272 , .._ 35 Shrinka~~e (~) 5.7 EASL + ;shrink (~) 8.3 d Tm(C) ?
AMENDED SHEET
RCb: VU':Et~~ 'ill E:\CHN\~'~ '- ""__~~:3-.,.-~"r~~; _' "..1';_57":till-1. ,-p'i(1 :3:iEif3 - +~l~j 8~) '?:3~1JV4F~:~: # 13 -..' '_ ~_ ~ 2.~~632g to ~~i,PLB II
PEN yarns were produced by extruding seven filaments through a gpiru~erette with orifices' of length s 0.036 inches (0.091 cm) and width of 0.016 inches ( 4 . O G 1 cm) a t a thruput of 9 . 6 c;1~3 /min . The f i l amen t s were solidified in an air quenching calum~ and taken up at winder speedy ranging from ??C-5000 m/min.;Theae yarns were drawn in two stages using a heating pate it to draw zone two. The undrawn yarn properties, drawn yarn properties, and' drawing conditions are suuanarized ir.
Table II.
Visual inspection of the data in this example illustrates that for yarns drawn to a~;given 13 tenacity, modulus increases with increasing spinning speed and with drawn and undraam melting point. This is reflected in the increasing LT parameter with' iacreaeiag spinning speed.~Undrawr. birefringence alone ~ie not Sufficient to characterize the yarns of this .
2o invention. Since this parameter is insensitive to morphological cl~angee which occur at high spirir.ing stresses, both melting point ane~ birefringence mu~c be used to detirte the scope of this invention. In ordex zo compare the data of thie~ example with that of , 25 comparative Example I, the modulua values of Table IZ were interpolated to 6.2 g/d (54.'1 mN/dtex), tenacitp sad plotted ve epi:v-~ing speed (Fig. 1.) . This ana7,yeie clearly shows the advar_tagea of the yarns of this invention relative to prior art yarns.
i AMENDED SHEET
_ s . . _.
~yy~ ~ ~ ~ : ~ w i' i ~~.. sue:-fZC~ . ~ U\ : ~:IyA-Vl( ~\CttL\ ''' _ , ...____':S=~1~' w'.):i ~~ ,...
t'~;_:~t~.~: apt , a-'(1 3nt~8 ~ +-t J 8a '?a3;J,)~t-~EiS : it t-1-r o ~ N x o c .-.
O h ~ N c'~ u'T O Q1 h ~ cr7 r-1 ~ N E-~ !'7 ~D ~ C1 C~; L!7 O ~ r ~D r-, r1 r-i x :V M vD u'! c~1 00 N tn et ~T N
O ~ ~ N
OI O
O c~"~ O
fh c' t~ M M ~ O I v' a 7 t~
~a V ~ o~ E-a ~' I ~ ~ N N I N ~ N
-' ~--i f~i N ~J l0 v0 r-~ I ~ C' O I
O ~D V7 N M ~ u7 ,- I
C7 ~ N ~-a -I h N ~-~
p . . L'7 v~ O u'7 r1 N .-. .-.
C~'7 tl7 O ~ 0 n ~-~ ~ C N Q' p O Q1 O p ~ N ri ~.
N h -~ O ~ ~D sD N v0 N vl; ~.C ..~
~ r ~ O O ~- N
C ~ o ~~ o ~~, -M ~ ~ th v O r v V 8 h N H a o a q. It1 r~-I ,.~ o ~~
N ,.i N r.., 'w ~ ri C; N 'a' ~ Ol ids In p~ ~ N M V~.
N x ~ ~ a~ N N N c~ a~ r .--( ~ f''7 O tT ri N ~ ~ O N
C~-~ G~.n H ~ Cl~ O I ~ s1; u7 C-~ C N v0 M vf'7 a' ~ 01 ~ 'C
N ~ f'7 O ~ m C1 O ~., ~ N :\; -a .,~~. f 1 ~ C ~"'~ ri N ~T ~D V_7 N N N L7 L~ l~ ra I c~ ~- -- o a O r~ ~ O ~ .~.
p m n Ca H ~ N ~ c' u'7 u7 O O N N Qt ~ cx ~r ', H N ~ O t~'7 N ~ N H t'7 N .-~ N ~t'7 r ~ N r- ~-I
r-a ~-I .~'.,. N C L'7 L(7 N 01 N eT Q' vC .-~~
~ ri O
N N
rl ~0' f"7 n M N vG ~~ O O l0 ~ :'~ dD ~~~ O ~
,- ~-' ~ N F- f'~I ~' ~ CO t.'1 tD ... ~ e1' i~' O
C~'t '-' M r~ C N ~ W Cf7 N N yt'7 C' M r.
c a~ ~'7 0 ~ o r O tf7 N ~ C
r, . N C'~ ,.-.
Q '-i ~' N
O u'7 O O . ,M. ~ c~ ~ ~, N N
~ N H M ~' ~ r~d h M ~..~ ~ ~ nr Cl f~': r~i .~." :~: ~ s!7 t!7 r-1 l17 N P"i C7 .--s GJ CJ O r~~ N
'_L" b \ '-' -- _ _ ro -. ~ ar a U U ''~ 't! ~ '-' y' °... °.~ ~' d, b b ~ b C~ tT ~O ~ N ~ ~-' ~ b~
V ~
b c H ~ H A a ~' ~ ~ a a c '~
AMENDED SHEET
r ~ V i 7 lf~. i~.
_e.~. _... .._._.
.. .. ~~ .., .. - ;--1J F31) _:3:~J4-~t~,;: p i:~
RCS . 1W,\ : E~F'.~ v~ll E:',C'HE\ ''J .... , .~___.,~:3~-,t,' -:~'~ ,:
,...1~~ ~'~~.~' ~'.'_;~ v'~'u :3:;GH - _ ~sXAMPLB I2I
Then undrawn yarns of Exar~~ple II spun at X70 m/min a.-~d 4oc~0 m/min were drawn to their ultimate limit.
s The: 770 m/min sample was drawn in ore stage using an oven in the draw zone and the 4000 rr./rnin sample waB di:awn in two stages using a heated plate in the second di:aw zone.
ThE; drawn yarn properties and drawing io conditions are summarized in Table III. This example shows that ttie yarns of this invention poesegs extremely hic_~h modulue, high tenacity, and low shrinkage ma~.ing them desirable for in-rubber applications.
is TAHLF III
A~RAWN YARN
-u~ s~&.$ ~rn/min) ,~Q 4000 2o Draw Ratio 5 . 9 Z . 0 Roll 1 I;Cl 120 95 Oven ( C ) 17 0 _ _ Roll 2 I:C) RT ~ RT
Heating Plate (C) -- 24a 2s Roll 3 (Cl -- RT
Ten-acit~~ tg/d) (mN/dtex) 10,3 (90.9) 7.6 (67.1) Modulua (g/d) (mN/dtex) 362 (3204) 4?7 (3680) Shrinkac; a ( ~r ) 3 . 5 c 1 30 EASL + 6~'.:rink ( ~ ) 4 . 8 <2 .1 L-5 (g/C;) (mN/dtex) B.3 (73.3) ?.5 (66.2) EXAMPLE ~ , .._ 3s This: example shows that undrawn yarns of high birefringence, rnodulue, and melting point can be produced at e~pinning speeds slower than those of Bxample II, thereby yielding a more commercially AMENDED SHEET
RCS.\.(>\:E-ayysD'C:\CHH\''? ....., ,.'___.,'Bvl'y:j'3 y,,...F;)~3;i":fi)4y''() :3W1t3 - +v;3 E3J '?a3:),)~C-CE~:~:N1E~
._ ' y rJ 2126~32~
feasible process for those lacking high speed capabilities. P~1 yarns were produced by extru3ing seven f~.lamerite through a epinnerette with orifices of length 0.069 inches sad width 0.030 inches at a thruput s of 9.6 cc/mix:. The filaments ware eolidi~ied in an air quenching column and taken up at winder speeds ranging from 410 m/m!.n to 2500 m/min. The properties of these yarns are sur;rnarized in Table zv.
'x'~LFi V
~~~,-~,rp 9PE8D fM/M~N~
~n 0..178 0.159 0.192 0.232 0.233 0.226 is Tenac i,ty ~ 2 . 1 2 . 0 2 . 6 3 . 8 4 . 0 4 . 5 tg/d) (mN/dtex)(18.5) (1~.~) (22~9) (33.5) (35.3) (39.7) Modulue 64 58 63 114 143 158 (g/d) (mN/dtex) (565) (512) (556) (1006) (1x62) (1395) °C) 269 267 Z68 279 291 292 AMENDED SHEET
~' P
. _....
gauge length and a strain rate of 120 percent per minute. All tensile measurements were made at roots temperature. Dimensional stability refers to the level of stress achieved at a given shrinkage. In the tire * trademark RCV: VU\ : EI~~ X111 EVCHf:'~ ''? " , .___ _..~'3 .1..~ »9'~ .' ,...19 '35":
8U4 , 5_'U 308 -~ +49 89 ''.'3J94-~E~S : t! 1 (>
_.
z the level of stress achieved at a given shrinkage. In the tire indu,etry, dimensional stability is defined ae the sum of elongation at a specified load plus shrinkage. Fc~r the present case, the elongation at a s ap~cified load (EASL) is derived from the initial modulue data using the following equation:
EA6L - 454/Modulus (g/d) It ig well known that tenacity and madulue increase with, increasing draw-ratio. while higher io tenacity per se ie almost always highly desirable, the high extensicn ratios are often net achievable due to yarn quality problems or to excessive shrinkage.
Materials of this invention po~sees high levels of modulus for a given level of tenacity. This ie is quantified as the LT parameter, by ratioing L-5 to _ tenacity as follows:
LT ~~ ((L-5)4/T5.16) 1000 L-5 or~LA9$-5 is a measure of modulue defiaad ae load in g/d at 5f elongation. The materials of this Zo invention have LT at lea~t 25. If L-5 ig not measurable because of yarn elongatione less than 5~ the yarns will be pre-relaxed at elevated temperatures before testing .
to increase elongation beyond 5~.
Shrinkage values were determined is 25 accordance~with ATM D885 after one minute at 177°C
employing a constraining force o~ 0.05 g/denier (0.44 mN/dtex)-.
2dentified hereafter ie a description of a process which has been found to be capable of forming 30 the improved ,yarn of the present invention. Tha yarn product claimed hereafter ie not to be limited by the parameters of the process which followra.
The melt-epinnable poly~eter it supplied to an extrusion ~spinaerette at a temperature above its ~~-3s melting point and below the temperature at which the polymer d~gradee substantially. The residexlce time at this stage is kept to a minimum and the temperature should not ri;ae above 350°C, preferably 320°C.
AMENDED SHEET
~r ~~.'~~~=~r°.i ___...~~.._.__._..._~.~._~.._._.. _.._.._..
RC1.VO\:EP:~-11l'E~:CHE\_~~ _, ,.~__~..~'3-.1..~.~3~~"...1'~~3F',y8G4,5'?G
35E~$ , +4J 8:J '?899~1~t~5:#Ll 21263~~
The extruded filaments then traverse a conventional yarn solidification $vne where quench air impinges on the spun yarn thereby freezing in dea:irabia internal structural features and preventing the filaments fro:a fusing to one another. Tha solidification zone preferably comprises (a) a retarded cooling zone ca~mprising a gaseous atmosphere heated at a te~aperature to at least 150°C, preferably 150 to 500°C, and (b) ~a cooling zone adjacent to said rstarded to cooling sons wh,erain said yarn is rapidly cooled and solidified in a. blown air atmosphere. The ksy to the current proceso~ is to adjust processing conditions to aohievv a highly oriented undrawn yarn of birafringenee at last 0.03 a,nd an elevated melting point of ~-Z5°C, is preferably 3-23°C. For pEN a malting point of 265 to 290°C, prafsrab.ly 268 to 288°C must be achieved. Ono skilled in the art can aehiavo this by adjusting the following eondi,tiona: length and temperature of the retarded eoolin.g tone adjacent to the spinnorstte, 2o diameter of ths. apron~rette holes, method of blowing the q~,iench, gue~nah air velocity, and drawdown in the solidifioation ions. The speed of withdrawal of the yarn from the aoiidification zone is an important parameter affecaing the stress on the spun fiber, and 25 should ba adjus;ted to yi~ld the desired ' characteristics,. Tha spur: yarn is then drawn by conventioAal means in either a continuous or non-continuous process to yield a drawn yarn with Tg greater than iC~o°c and a melting point elevation at 30 least 8°c, preferably 8 to 15°C. ~t is preferred to have the following drawn yarn properties: tenacity at least s.5 g/d (57.4 mN/dtox), preferably at least 7.5 g/d (66.Z mN/dt.ax): dimensional stability (EA3L +
shrinkage) of less than 5~~ and shrinkage of a~ .or , .._ 3s leas.
y Ei~ - ( CondPnRATIVE ) ~'A~~~EN~ undrawn yarn was produced by axtxvding AMENDED SHEET
~ w'~ s ~ -.~.
[tCV.~U\:E:E~ yii-E\CHE:\.'? _.. ~,~___..-~:i"E?,.=3:3~'"~.i''3::3',_'';~~:~,~~-'~~ ~vESfi -» +~[~i f3;3 '?:39,31_1~~:;:N[w ._ ' ' Jr ' 2~2G328 3Z filaments through a spinnerette with orifices of length 0.042 in~ch$s (o.107cm) and of width 0.021 inches (0.053 cm) at a. thruput or 23.2 cc/min. The filaments were soiiditied, in an air quenching column and'taken up at winder spaed,s of 305 m/min.
This yarn was drawn in two stages using conventional heated rolls. The undrawn yarn properties, drawn yarn propartieo, and drawing conditions are gumr~arised in Table I.
to The yarn of this example, which was prepared conventionally from an undrawn yarn of 0 n m o.Io04, possesses poorer modulus than the yarns of this invention as evidenced by LT less than 25. Also'the dimensional stability parameter (EA8L + shrinkage) of i3 8.3 is higher than that of yarns of this invention, indicating poorer dimensional stability (see Exnmpl~
zii) .
TAB I , A. UNDRAW~T Yet 20 ~ n 0.004 Tmnacity (g/d) 0.6 (5.3 mN%dtex) Modulus (g/d) 18.6 (164 mN/dtex) Tm (°C) 268 25 ~. DRAW N YARN
Dr aw Ratio 6 . 3 Roll 1 (C) 140 Roll 2 (~C) 157 Roll 3 (C) RT
n 0.426 Tenacit;Y (g/d) 6.Z (54.? mN/dtsx) Modulus (g/d) 176 (1553 mN/dtox) Tm (C) 272 , .._ 35 Shrinka~~e (~) 5.7 EASL + ;shrink (~) 8.3 d Tm(C) ?
AMENDED SHEET
RCb: VU':Et~~ 'ill E:\CHN\~'~ '- ""__~~:3-.,.-~"r~~; _' "..1';_57":till-1. ,-p'i(1 :3:iEif3 - +~l~j 8~) '?:3~1JV4F~:~: # 13 -..' '_ ~_ ~ 2.~~632g to ~~i,PLB II
PEN yarns were produced by extruding seven filaments through a gpiru~erette with orifices' of length s 0.036 inches (0.091 cm) and width of 0.016 inches ( 4 . O G 1 cm) a t a thruput of 9 . 6 c;1~3 /min . The f i l amen t s were solidified in an air quenching calum~ and taken up at winder speedy ranging from ??C-5000 m/min.;Theae yarns were drawn in two stages using a heating pate it to draw zone two. The undrawn yarn properties, drawn yarn properties, and' drawing conditions are suuanarized ir.
Table II.
Visual inspection of the data in this example illustrates that for yarns drawn to a~;given 13 tenacity, modulus increases with increasing spinning speed and with drawn and undraam melting point. This is reflected in the increasing LT parameter with' iacreaeiag spinning speed.~Undrawr. birefringence alone ~ie not Sufficient to characterize the yarns of this .
2o invention. Since this parameter is insensitive to morphological cl~angee which occur at high spirir.ing stresses, both melting point ane~ birefringence mu~c be used to detirte the scope of this invention. In ordex zo compare the data of thie~ example with that of , 25 comparative Example I, the modulua values of Table IZ were interpolated to 6.2 g/d (54.'1 mN/dtex), tenacitp sad plotted ve epi:v-~ing speed (Fig. 1.) . This ana7,yeie clearly shows the advar_tagea of the yarns of this invention relative to prior art yarns.
i AMENDED SHEET
_ s . . _.
~yy~ ~ ~ ~ : ~ w i' i ~~.. sue:-fZC~ . ~ U\ : ~:IyA-Vl( ~\CttL\ ''' _ , ...____':S=~1~' w'.):i ~~ ,...
t'~;_:~t~.~: apt , a-'(1 3nt~8 ~ +-t J 8a '?a3;J,)~t-~EiS : it t-1-r o ~ N x o c .-.
O h ~ N c'~ u'T O Q1 h ~ cr7 r-1 ~ N E-~ !'7 ~D ~ C1 C~; L!7 O ~ r ~D r-, r1 r-i x :V M vD u'! c~1 00 N tn et ~T N
O ~ ~ N
OI O
O c~"~ O
fh c' t~ M M ~ O I v' a 7 t~
~a V ~ o~ E-a ~' I ~ ~ N N I N ~ N
-' ~--i f~i N ~J l0 v0 r-~ I ~ C' O I
O ~D V7 N M ~ u7 ,- I
C7 ~ N ~-a -I h N ~-~
p . . L'7 v~ O u'7 r1 N .-. .-.
C~'7 tl7 O ~ 0 n ~-~ ~ C N Q' p O Q1 O p ~ N ri ~.
N h -~ O ~ ~D sD N v0 N vl; ~.C ..~
~ r ~ O O ~- N
C ~ o ~~ o ~~, -M ~ ~ th v O r v V 8 h N H a o a q. It1 r~-I ,.~ o ~~
N ,.i N r.., 'w ~ ri C; N 'a' ~ Ol ids In p~ ~ N M V~.
N x ~ ~ a~ N N N c~ a~ r .--( ~ f''7 O tT ri N ~ ~ O N
C~-~ G~.n H ~ Cl~ O I ~ s1; u7 C-~ C N v0 M vf'7 a' ~ 01 ~ 'C
N ~ f'7 O ~ m C1 O ~., ~ N :\; -a .,~~. f 1 ~ C ~"'~ ri N ~T ~D V_7 N N N L7 L~ l~ ra I c~ ~- -- o a O r~ ~ O ~ .~.
p m n Ca H ~ N ~ c' u'7 u7 O O N N Qt ~ cx ~r ', H N ~ O t~'7 N ~ N H t'7 N .-~ N ~t'7 r ~ N r- ~-I
r-a ~-I .~'.,. N C L'7 L(7 N 01 N eT Q' vC .-~~
~ ri O
N N
rl ~0' f"7 n M N vG ~~ O O l0 ~ :'~ dD ~~~ O ~
,- ~-' ~ N F- f'~I ~' ~ CO t.'1 tD ... ~ e1' i~' O
C~'t '-' M r~ C N ~ W Cf7 N N yt'7 C' M r.
c a~ ~'7 0 ~ o r O tf7 N ~ C
r, . N C'~ ,.-.
Q '-i ~' N
O u'7 O O . ,M. ~ c~ ~ ~, N N
~ N H M ~' ~ r~d h M ~..~ ~ ~ nr Cl f~': r~i .~." :~: ~ s!7 t!7 r-1 l17 N P"i C7 .--s GJ CJ O r~~ N
'_L" b \ '-' -- _ _ ro -. ~ ar a U U ''~ 't! ~ '-' y' °... °.~ ~' d, b b ~ b C~ tT ~O ~ N ~ ~-' ~ b~
V ~
b c H ~ H A a ~' ~ ~ a a c '~
AMENDED SHEET
r ~ V i 7 lf~. i~.
_e.~. _... .._._.
.. .. ~~ .., .. - ;--1J F31) _:3:~J4-~t~,;: p i:~
RCS . 1W,\ : E~F'.~ v~ll E:',C'HE\ ''J .... , .~___.,~:3~-,t,' -:~'~ ,:
,...1~~ ~'~~.~' ~'.'_;~ v'~'u :3:;GH - _ ~sXAMPLB I2I
Then undrawn yarns of Exar~~ple II spun at X70 m/min a.-~d 4oc~0 m/min were drawn to their ultimate limit.
s The: 770 m/min sample was drawn in ore stage using an oven in the draw zone and the 4000 rr./rnin sample waB di:awn in two stages using a heated plate in the second di:aw zone.
ThE; drawn yarn properties and drawing io conditions are summarized in Table III. This example shows that ttie yarns of this invention poesegs extremely hic_~h modulue, high tenacity, and low shrinkage ma~.ing them desirable for in-rubber applications.
is TAHLF III
A~RAWN YARN
-u~ s~&.$ ~rn/min) ,~Q 4000 2o Draw Ratio 5 . 9 Z . 0 Roll 1 I;Cl 120 95 Oven ( C ) 17 0 _ _ Roll 2 I:C) RT ~ RT
Heating Plate (C) -- 24a 2s Roll 3 (Cl -- RT
Ten-acit~~ tg/d) (mN/dtex) 10,3 (90.9) 7.6 (67.1) Modulua (g/d) (mN/dtex) 362 (3204) 4?7 (3680) Shrinkac; a ( ~r ) 3 . 5 c 1 30 EASL + 6~'.:rink ( ~ ) 4 . 8 <2 .1 L-5 (g/C;) (mN/dtex) B.3 (73.3) ?.5 (66.2) EXAMPLE ~ , .._ 3s This: example shows that undrawn yarns of high birefringence, rnodulue, and melting point can be produced at e~pinning speeds slower than those of Bxample II, thereby yielding a more commercially AMENDED SHEET
RCS.\.(>\:E-ayysD'C:\CHH\''? ....., ,.'___.,'Bvl'y:j'3 y,,...F;)~3;i":fi)4y''() :3W1t3 - +v;3 E3J '?a3:),)~C-CE~:~:N1E~
._ ' y rJ 2126~32~
feasible process for those lacking high speed capabilities. P~1 yarns were produced by extru3ing seven f~.lamerite through a epinnerette with orifices of length 0.069 inches sad width 0.030 inches at a thruput s of 9.6 cc/mix:. The filaments ware eolidi~ied in an air quenching column and taken up at winder speeds ranging from 410 m/m!.n to 2500 m/min. The properties of these yarns are sur;rnarized in Table zv.
'x'~LFi V
~~~,-~,rp 9PE8D fM/M~N~
~n 0..178 0.159 0.192 0.232 0.233 0.226 is Tenac i,ty ~ 2 . 1 2 . 0 2 . 6 3 . 8 4 . 0 4 . 5 tg/d) (mN/dtex)(18.5) (1~.~) (22~9) (33.5) (35.3) (39.7) Modulue 64 58 63 114 143 158 (g/d) (mN/dtex) (565) (512) (556) (1006) (1x62) (1395) °C) 269 267 Z68 279 291 292 AMENDED SHEET
~' P
. _....
Claims (10)
1. A process for production of a drawn polyester yarn of enhanced modulus and good to tenacity, comprising:
(a) extruding a molten crystallizable polyester polymer having Tg greater than 100°C and having an intrinsic viscosity of 0.6 or greater through a shaped extrusion orifice having a plurality of openings to form a molten spun yarn, (b) solidifying the spun yarn by passing through a solidification zone, (c) withdrawing the solidified yarn at a sufficient undrawn take-up speed to form a partially oriented yarn of birefringence of at least 0.030, and (d) hot drawing the yarn to a fatal draw ratio of at least 1.5/1 to form a drawn yarn.
(a) extruding a molten crystallizable polyester polymer having Tg greater than 100°C and having an intrinsic viscosity of 0.6 or greater through a shaped extrusion orifice having a plurality of openings to form a molten spun yarn, (b) solidifying the spun yarn by passing through a solidification zone, (c) withdrawing the solidified yarn at a sufficient undrawn take-up speed to form a partially oriented yarn of birefringence of at least 0.030, and (d) hot drawing the yarn to a fatal draw ratio of at least 1.5/1 to form a drawn yarn.
2. The process of Claim 1 wherein the spun yarn is solidified by passing through a solidification zone which comprises (a) a retarded cooling zone comprising a gaseous atmosphere heated at a temperature of at least 150°C, and (b) a cooling zone adjacent to said retarded cooling zone wherein said yarn is rapidly cooled and solidified in a blown air atmosphere.
3. The process of Claim 1 or Claim 2 wherein the undrawn take-up speed is 400 to 450p m/min and the undrawn birefringence is 0.030 to 0.30.
4. The process of Claims 1 or 2 for production of a drawn polyethylene naphthalate yarn wherein the molten polyester polymer extruded in step (a) is polyethylene naphthalate and in step (c) the partially oriented undrawn yarn has a melting point elevation of 1-25°C.
5. The process of claim 4 wherein the undrawn take-up speed is 400 to 4500 m/min., the undrawn birefringence is 0.030 to 0.30, and the melting point elevation of the partially oriented yarn is 3-23°C.
6. A drawn semi-crystalline polyester multifilament yarn having Tg greater than 100°C a melting point elevation at least 9°C and an undrawn birefringence of at least 0.03.
7. The drawn yarn of claim 6 having tenacity at least 6.5 g/d (57.4 mN/dtex), dimensional stability (EASL + shrinkage) of less than 5%, and shrinkage of 4%
or less.
or less.
8. The drawn yarn of claim 7 which is polyethylene naphthalate.
9. The drawn polyethylene naphthalate yarn of claim 8 wherein the melting point elevation is 9 to 15°C, the modulus is at least 280 g/d (2470 mN/dtex) and the tenacity is at least 7.5 g/d (66.2 mN/dtex)
10. A drawn semi-crystalline polyester multifilament yarn having Tg greater than 100°C, a melting point elevation at least 9°C, a tenacity of at least 7.5 g/d, dimensional stability (EASL + shrinkage) of less than 5%, and shrinkage of 4% or less.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82279992A | 1992-01-21 | 1992-01-21 | |
| US07/822,799 | 1992-01-21 | ||
| PCT/US1992/011063 WO1993014252A1 (en) | 1992-01-21 | 1992-12-22 | High modulus polyester yarn for tire cords and composites |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2126328A1 CA2126328A1 (en) | 1993-07-22 |
| CA2126328C true CA2126328C (en) | 2002-05-21 |
Family
ID=25237011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002126328A Expired - Fee Related CA2126328C (en) | 1992-01-21 | 1992-12-22 | High modulus polyester yarn for tire cords and composites |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0623179B2 (en) |
| JP (1) | JP2629075B2 (en) |
| CN (1) | CN1051586C (en) |
| AU (1) | AU3331293A (en) |
| BR (1) | BR9207038A (en) |
| CA (1) | CA2126328C (en) |
| DE (1) | DE69213474T3 (en) |
| ES (1) | ES2091589T5 (en) |
| MX (1) | MX9300142A (en) |
| TR (1) | TR28032A (en) |
| TW (1) | TW224960B (en) |
| WO (1) | WO1993014252A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4320593A1 (en) * | 1993-06-22 | 1995-01-05 | Akzo Nobel Nv | Multifilament yarn made of polyethylene naphthalate and process for its manufacture |
| KR100402839B1 (en) * | 2001-05-10 | 2003-10-22 | 주식회사 효성 | Polyethylene naphtalate fiber of high strength |
| DE10140774B4 (en) * | 2001-08-20 | 2004-08-12 | Metzeler Automotive Profile Systems Gmbh | molded hose |
| CN1302163C (en) * | 2003-08-22 | 2007-02-28 | 株式会社晓星 | High tenacity polyethylene-2,6-naphthalate fibers |
| JP4616658B2 (en) * | 2005-01-31 | 2011-01-19 | 帝人ファイバー株式会社 | Non-woven |
| JP4928308B2 (en) * | 2007-02-28 | 2012-05-09 | 帝人ファイバー株式会社 | Polyethylene naphthalate fiber for industrial materials and production method thereof |
| RU2429397C1 (en) * | 2007-07-03 | 2011-09-20 | Дзе Гейтс Корпорейшн | Drive belt |
| 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 |
| FR2971187B1 (en) * | 2011-02-03 | 2013-03-08 | Michelin Soc Tech | SOLDER COMPOSITE REINFORCEMENT OF A SELF-ADHERING RUBBER POLYMER LAYER |
| FR2971188B1 (en) | 2011-02-03 | 2013-03-08 | Michelin Soc Tech | SOLDER COMPOSITE REINFORCEMENT OF A SELF-ADHERING RUBBER POLYMER LAYER |
| CN102851782B (en) * | 2011-06-30 | 2016-05-04 | 上海杰事杰新材料(集团)股份有限公司 | A kind of polyamide industrial yarn and manufacture method thereof for tyre framework material |
| JP2017053060A (en) * | 2015-09-08 | 2017-03-16 | 株式会社ブリヂストン | Manufacturing method of pef raw yarn, pef raw yarn and tire |
| CN112281272A (en) * | 2020-10-15 | 2021-01-29 | 联新（开平）高性能纤维有限公司 | Polyester cord fabric warp with ultrahigh strength and dimensional stability as well as preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3616832A (en) * | 1968-12-24 | 1971-11-02 | Teijin Ltd | Rubber articles reinforced with filaments |
| US3564835A (en) † | 1969-03-12 | 1971-02-23 | Du Pont | High tenacity tire yarn |
| US4026973A (en) † | 1973-08-31 | 1977-05-31 | Teijin Limited | Process for preparing heat-resistant aromatic polyester filaments |
| JPS5615321B2 (en) * | 1973-09-20 | 1981-04-09 | ||
| GB1445464A (en) * | 1973-10-19 | 1976-08-11 | Teijin Ltd | Method of producing a polyethylene-2,6-naphthalate yarn |
| JPS62156312A (en) † | 1985-12-26 | 1987-07-11 | Teijin Ltd | Polyester fiber |
| JP2914385B2 (en) * | 1988-07-05 | 1999-06-28 | アライド―シグナル・インコーポレーテッド | Dimensionally stable polyester yarn for high tenacity treatment cord |
| JP2861335B2 (en) * | 1990-08-31 | 1999-02-24 | 東洋紡績株式会社 | Method for producing naphthalate polyester fiber |
| JP2954391B2 (en) * | 1991-05-22 | 1999-09-27 | 帝人株式会社 | Polyethylene naphthalate fiber and method for producing the same |
-
1992
- 1992-12-22 DE DE69213474T patent/DE69213474T3/en not_active Expired - Fee Related
- 1992-12-22 ES ES93901119T patent/ES2091589T5/en not_active Expired - Lifetime
- 1992-12-22 CA CA002126328A patent/CA2126328C/en not_active Expired - Fee Related
- 1992-12-22 BR BR9207038A patent/BR9207038A/en not_active IP Right Cessation
- 1992-12-22 WO PCT/US1992/011063 patent/WO1993014252A1/en active IP Right Grant
- 1992-12-22 AU AU33312/93A patent/AU3331293A/en not_active Abandoned
- 1992-12-22 JP JP5512461A patent/JP2629075B2/en not_active Expired - Fee Related
- 1992-12-22 EP EP93901119A patent/EP0623179B2/en not_active Expired - Lifetime
-
1993
- 1993-01-13 MX MX9300142A patent/MX9300142A/en not_active IP Right Cessation
- 1993-01-19 TW TW082100327A patent/TW224960B/zh active
- 1993-01-20 TR TR00065/93A patent/TR28032A/en unknown
- 1993-01-21 CN CN93101268A patent/CN1051586C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69213474D1 (en) | 1996-10-10 |
| JP2629075B2 (en) | 1997-07-09 |
| EP0623179A1 (en) | 1994-11-09 |
| MX9300142A (en) | 1994-07-29 |
| WO1993014252A1 (en) | 1993-07-22 |
| DE69213474T3 (en) | 2001-08-23 |
| AU3331293A (en) | 1993-08-03 |
| CA2126328A1 (en) | 1993-07-22 |
| EP0623179B1 (en) | 1996-09-04 |
| ES2091589T5 (en) | 2001-05-16 |
| TR28032A (en) | 1995-12-11 |
| EP0623179B2 (en) | 2001-02-14 |
| BR9207038A (en) | 1995-12-05 |
| CN1078508A (en) | 1993-11-17 |
| DE69213474T2 (en) | 1997-02-06 |
| CN1051586C (en) | 2000-04-19 |
| JPH06511293A (en) | 1994-12-15 |
| TW224960B (en) | 1994-06-11 |
| ES2091589T3 (en) | 1996-11-01 |
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