WO2007123059A1 - Fibre de polyester réticulé résistante à la chaleur et corde de fibres de polyester réticulé résistante à la chaleur - Google Patents

Fibre de polyester réticulé résistante à la chaleur et corde de fibres de polyester réticulé résistante à la chaleur Download PDF

Info

Publication number
WO2007123059A1
WO2007123059A1 PCT/JP2007/058138 JP2007058138W WO2007123059A1 WO 2007123059 A1 WO2007123059 A1 WO 2007123059A1 JP 2007058138 W JP2007058138 W JP 2007058138W WO 2007123059 A1 WO2007123059 A1 WO 2007123059A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester fiber
heat
resistant
elastic modulus
polyester
Prior art date
Application number
PCT/JP2007/058138
Other languages
English (en)
Japanese (ja)
Inventor
Shigenori Nagahara
Kenji Yoshino
Yasushi Aikawa
Original Assignee
Toyo Boseki Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006114325A external-priority patent/JP2007284828A/ja
Priority claimed from JP2006114326A external-priority patent/JP2007284829A/ja
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Publication of WO2007123059A1 publication Critical patent/WO2007123059A1/fr

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0042—Reinforcements made of synthetic materials
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
    • D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M14/32—Polyesters
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Definitions

  • the present invention relates to a heat-resistant crosslinked polyester fiber and a heat-resistant crosslinked polyester fiber cord. Specifically, it has dimensional stability and heat resistance, and more specifically, tire cords, belt materials, canvas, screens that can maintain mechanical properties (storage elastic modulus) in the middle temperature range from room temperature.
  • the present invention provides a heat-resistant cross-linked polyester fiber useful for industrial material applications such as, and a heat-resistant bridge-type polyester fiber cord useful for industrial material applications such as tire cords and belt materials.
  • nylon fibers such as nylon fibers, rayon fibers, and polyester fibers have been used for tire cords as fiber reinforcing materials for tires.
  • nylon fibers When nylon fibers are used for tire cords, they have high toughness and good adhesion to rubber, but their elongation is relatively large, so that they are inferior in dimensional stability and easily cause a flat spot phenomenon.
  • rayon fibers when used for tire cords, the strength is lower than that of the nylon fiber tire cords. Therefore, when used for tire carcass members, the amount used must be increased, resulting in tire weight. There is a disadvantage that increases. Furthermore, there are concerns about the future supply of pulp, which is the raw material for rayon fibers. For this reason, attention has been paid to the use of high-strength polyester fibers as tire cords that are excellent in dimensional stability as materials to compensate for the disadvantages of both.
  • a run-flat tire is a tire that can travel at a predetermined speed for a certain distance even if the tire punctures during high-speed driving and the tire internal pressure becomes OKPa.
  • This run-flat tire has a side reinforcement type that is reinforced by placing a relatively hard rubber layer with a crescent-shaped cross section on the inner surface of the carcass over the shoulder area and the beat part force of the tire sidewall, and in the tire air chamber.
  • Core tie with an annular core made of metal or synthetic resin attached to the rim Is known.
  • This inner side reinforcement type supports the load by the inherent rigidity of the sidewall reinforced with a reinforced rubber layer when the tire punctures and the air escapes during driving, and is capable of traveling over a predetermined distance.
  • frictional heat is generated due to contact with the road surface, and the internal temperature of the tire may be 200 ° C or higher, and extremely high even locally.
  • the main cause of tire failure is deterioration due to heat generation. Therefore, particularly in the case of runflat tires, heat-resistant rayon fibers, aramide fibers, steel, and the like are used as carcass members.
  • Nylon fibers and polyester fibers can be mass-produced by melt spinning, and are advantageous in terms of price and suitable for industrial materials.
  • the melting point of nylon 6 is 215-220.
  • C nylon 66 is 250-260.
  • the melting point of C positive ethylene terephthalate is 255-260.
  • C when the inside of the tire generates heat at 200 ° C or higher, the adhesive interface with the rubber begins to break down, and the strength, dimensional stability and mechanical properties suddenly decrease. Therefore, not only the carcass member for run-flat tires but also belts and other fabric cords are similarly restricted or unsuitable for applications requiring heat resistance.
  • polyester fibers made of copolymerized polyethylene terephthalate are less expensive than rayon fibers.
  • they are provided with functions of heat resistance and mechanical properties, their use is expanded and commercially available. It is advantageous.
  • polyethylene naphthalate fibers or nylon fibers made of copolymerized polyethylene naphthalate are similarly given heat resistance and mechanical properties.
  • Polyester fiber cords such as copolyester fibers that provide dimensional stability, durability, thermal properties, and the like, and methods for producing the same (see Patent Documents 13 to 17) are disclosed.
  • a fiber made of a copolymerized polyester fiber having excellent dimensional stability, high strength, durability and the like used for a carcass member belt material is produced by a known method in the art, but is particularly preferable. Examples of the method include methods described in Patent Documents 19 and 20.
  • Patent Document 1 Japanese Patent Laid-Open No. 55-166235
  • Patent Document 2 Japanese Patent Laid-Open No. 54-6051
  • Patent Document 3 Japanese Patent Laid-Open No. 7-166419
  • Patent Document 4 JP-A-7-166420
  • Patent Document 5 Japanese Patent Laid-Open No. 58-23916
  • Patent Document 6 Japanese Patent Application Laid-Open No. 5-163612
  • Patent Document 7 Japanese Patent Laid-Open No. 10-168661
  • Patent Document 8 Japanese Patent Laid-Open No. 10-168655
  • Patent Document 9 Japanese Patent Laid-Open No. 2003-193331
  • Patent Document 10 JP-A-2-99667
  • Patent Document 11 JP-A-2-127562
  • Patent Document 12 JP-A-3-59168
  • Patent Document 13 Japanese Unexamined Patent Publication No. 2001-115354
  • Patent Document 14 JP-A-5-71033
  • Patent Document 15 JP-A-5-59627
  • An object of the present invention is to maintain the excellent dimensional stability, high strength, and durability of a polyester fiber having copolyester strength, and in particular, to maintain heat resistance and mechanical properties at medium temperature and high temperature range.
  • polyester undrawn yarn and Z or drawn yarn obtained by melt-spinning a polymer such as a copolyester cable have at least 2 unsaturated bonds.
  • Polyester fibers obtained by melt spinning a polymer having copolyester strength are impregnated with aliphatic and Z or alicyclic compounds having at least two unsaturated bonds. Irradiated with actinic rays to form heat-resistant cross-linked fibers, (2) and then twisted into cords, and (3) polyester fibers obtained by melt spinning a polymer that has copolyester strength Polyester fiber cords are impregnated with aliphatic and Z or alicyclic compounds having at least two unsaturated bonds and irradiated with actinic rays to withstand resistance.
  • Polyester fiber and Z or polyester fiber cord obtained by melt-spinning a polymer made of copolymerized polyester fiber are treated with a carrier agent in advance, and then (2) or (3 ) By obtaining the code.
  • the present invention is as follows.
  • a heat-resistant cross-linked polyester characterized by a ratio E 'ZE
  • polyester fiber obtained by melt spinning the copolyester is impregnated with aliphatic and Z or alicyclic compounds having at least two unsaturated bonds and irradiated with active light, and then the fiber cord and 6.
  • the heat-resistant crosslinked polyester fiber cord as described in 5 above.
  • Polyester fiber cords such as polyester fibers obtained by melt spinning a copolyester are aliphatic and Z or fat having at least two unsaturated bonds. 6. The heat-resistant crosslinked polyester fiber cord according to 5 above, wherein the cyclic compound is impregnated and irradiated with actinic rays.
  • Polyester fibers and Z or polyester fiber cords are pretreated with a carrier agent, and then impregnated with aliphatic and Z or alicyclic compounds having at least two unsaturated bonds and irradiated with actinic rays.
  • the present invention relates to storage elastic modulus E 'at 100 ° C and storage at 250 ° C in dynamic viscoelasticity measurement.
  • the ratio of elastic modulus E, ratio E 'ZE, is 10 or less.
  • the present invention provides a re-ester fiber, and includes at least a part of the above-mentioned heat-resistant cross-linked polyester fiber, and has a storage elastic modulus E ′ at 250 ° C. and 250 in dynamic viscoelasticity measurement.
  • a polyester fiber cord is provided.
  • Polyester fibers that also have copolyester strength are impregnated with aliphatic and Z or alicyclic compounds having at least two unsaturated bonds, and then irradiated onto the surface layer of the polyester fibers by irradiation with electron beams, ⁇ rays, etc.
  • the cross-linking reaction between compounds with unsaturated bonds existing and the cross-linking reaction between compounds with unsaturated bonds penetrating inside or inside suppresses the fluidity of the amorphous and crystalline parts due to heating in the middle and high temperature range. As described above, the mechanical properties can be maintained and the shape can be maintained even at a temperature higher than the melting point temperature.
  • polyester fibers gradually decrease in mechanical properties (storage elastic modulus ⁇ ') due to heating at a temperature of about 100 ° C. This is because the non-crystalline part has a large thermal motion due to heating. As the temperature rises further, the partial crystal force easily breaks down and the mechanical properties further decline, and as a result, fluidity is exhibited and this temperature is defined as the melting temperature. When the temperature reaches the melting point or higher, the shape cannot be maintained due to thermal fluidity.
  • the storage elastic modulus E ′ does not significantly decrease in the melting point temperature range of 255 to 260 ° C. of the polyester fiber and does not melt at higher temperatures. As a result, the shape can be held.
  • the present invention is useful as a run-flat tire cord member that particularly requires heat resistance, mechanical properties, and the like, and also provides heat resistance to functional fibers other than copolymerized polyester fibers by the method of the present invention.
  • Application development is also possible.
  • the present invention is a heat-resistant cross-linking type that retains mechanical properties (storage elastic modulus) in the middle and high temperature range from room temperature to heat and can retain its shape without being melted by heat at a temperature equal to or higher than the melting point of the copolymer polyester.
  • Polyester fiber that is, the ratio of the storage elastic modulus E 'at 100 ° C and the storage elastic modulus E at 250 ° C in dynamic viscoelasticity measurement, E' / E, is less than 10
  • a thermally crosslinkable polyester fiber is provided.
  • the ratio of the storage modulus E ′ at 100 ° C. to the storage modulus E at 250 ° C. in the dynamic viscoelasticity measurement is at least partially including the above heat-resistant crosslinked polyester fiber.
  • E '/ E the value of
  • a heat-resistant cross-linked polyester fiber cord is provided.
  • the copolyester particularly the aromatic copolyester in the present invention is a polycondensate of an aromatic dicarboxylic acid component and a diol component, and is not particularly limited, including known ones. Further, an unsaturated group-containing polyester obtained by reacting with a glycidyl group-containing unsaturated compound using a polyester acid terminal may be used.
  • Aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid Examples include 5-sodium sulfophthalic acid. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferred.
  • Diol components include ethylene glycol, diethylene glycol, triethylene glycol
  • Aliphatic diols such as cornole, trimethylene glycol, tetramethylene glycol, propylene glycol, otaethylene glycol, decanmethylene glycol, polyethylene glycol
  • alicyclic diols such as cyclohexanediol and cyclohexanedimethanol
  • aromatic diols such as naphthalenediol, bisphenol A, and resorcin. Of these, aliphatic diols such as ethylene glycol and trimethylene glycol are preferred.
  • the aromatic dicarboxylic acid component and the diol component are each composed of a single monomer, and may be a copolyester composed of three or more kinds. Further, it may be a blend of two or more types of aromatic polyester resin.
  • the aromatic polyester can be obtained by polycondensing a reaction product of an aromatic dicarboxylic acid component and Z or an ester-forming derivative thereof with a diol component, which does not require special polymerization conditions, into a polyester. Can be synthesized by any method employed.
  • the polymerization equipment can be batch or continuous. Furthermore, after the polyester obtained in the liquid phase polycondensation step is granulated and pre-crystallized, it can be subjected to solid phase polymerization in an inert gas atmosphere or under reduced pressure under a temperature below the melting point.
  • the polymerization catalyst is not particularly limited as long as it has a desired catalytic activity, but an antimony compound, a titanium compound, a germanium compound, and an aluminum compound are preferably used. When these catalysts are used alone or in combination of two or more, the amount used is 0.002 to 0.1 mol% based on the aromatic carboxylic acid component constituting the polyester. preferable.
  • the intrinsic viscosity (IV) of the copolyester in the present invention is preferably 0.6 or more, more preferably 0.8 or more. If IV is 0.6 or less, the intended strength and inertia cannot be obtained.
  • the amount of carboxy terminal group of the aromatic polyester is preferably 50 eqZton or less, more preferably 30 eqZton or less. If it exceeds 50eqZton, polyester When used as a cord, durability is deteriorated due to the occurrence of hydrolysis by an amine compound entering from rubber, which is not preferable.
  • the copolymerized polyester is used as a yarn under the usual melt spinning conditions. Then, it can be obtained by, for example, thermal stretching by a spin draw method of stretching.
  • the thermal stretching is performed by one-stage stretching at a high magnification or multi-stage stretching of two or more stages.
  • the heating method includes a method using a superheated roll, superheated steam, a heat plate, a heat box or the like, and is not particularly limited.
  • polyester fibers those excellent in dimensional stability, high strength and durability manufactured for industrial materials such as a reinforcing material for rubber products such as tires can be preferably used.
  • the undrawn yarn and Z or drawn yarn of the copolyester fiber thus obtained are impregnated with an aliphatic and Z or alicyclic compound having at least two unsaturated bonds, Polyester fibers with unsaturated compounds present on the surface and Z or inside of the polyester fibers are produced batchwise or continuously.
  • a heat-resistant crosslinked fiber cord can be obtained by the following method.
  • aliphatic and Z or alicyclic compounds having at least two unsaturated bonds using a drawn fiber of copolymer polyester fiber obtained by melt spinning a polymer having copolyester strength Is made into polyester fiber with aliphatic and Z or cycloaliphatic compounds present in the polyester fiber, then irradiated with actinic rays to form crosslinked polyester fiber, and then used as a cord with a ring twisting machine or straight twisting machine.
  • a heat-resistant crosslinked fiber and a heat-resistant crosslinked fiber cord can be obtained by the following method. That is, (1) at least two unsaturated bonds using a drawn yarn of a copolyester fiber obtained by melt spinning a polymer having copolyester strength After impregnating with the aliphatic and Z or alicyclic compound possessed to make the polyester fiber a polyester fiber with the aliphatic and Z or alicyclic compound present, actinic rays are irradiated to form a crosslinked polyester fiber.
  • Polyester fibers and / or polyester fiber cords are pretreated with a carrier agent, impregnated with aliphatic and Z or alicyclic compounds having at least two unsaturated bonds, and then irradiated with actinic rays to crosslink polyester.
  • a carrier agent impregnated with aliphatic and Z or alicyclic compounds having at least two unsaturated bonds, and then irradiated with actinic rays to crosslink polyester.
  • a raw cord can be formed by a ring twisting machine or a straight twisting machine by a conventional method.
  • the standard raw cord is 10 ⁇ per 10cm: After applying the LOO twist (lower twist), combine multiple yarns, and the opposite side is 10 ⁇ per 10cm: the twist (upper twist) And
  • the aliphatic and Z or alicyclic compounds having at least two unsaturated bonds used in the present invention are compounds capable of proceeding radical polymerization reaction by irradiation with ultraviolet rays, electron beams, ⁇ rays, etc.
  • Unsaturated group in one molecule consisting of attalyloyl group, methacryloyl group, itaconol group, maleolyl group, fumaroyl group, crotoyl group, attalyloylamino group, methacryloylamino group, cinnamoyl group, vinyl group, aryl group, styryl group, etc.
  • glycol dimetatalate examples include (ethylene, diethylene, triethylene) glycol dimetatalate, polyethylene glycol dimetatalate, 1, 3 butylene glycol dimetatalate, 1, 4 butanediol dimetatalate, 1, 6 Xanthandiol dimetatalylate, 1,9-nonanediol dimetatalylate, neopentyl dallicol dimetatalylate, trimethylolpropane tri (meth) acrylate, trimethylol methane (meth) acrylate, tetramethylol methane tetra acrylate, Pentaerythritol tetraatalylate, dipentaerythritol pentaatalylate, bisphenol in one molecule
  • examples thereof include, but are not limited to, epoxyacrylates obtained by (meth) atalylating an aliphatic or alicyclic group having a Nord A skeleton.
  • the concept for maintaining the storage elastic modulus E 'in the high temperature range from the normal temperature according to the present invention is how to reduce the thermal motion due to the heating temperature of the crystalline part and the amorphous part.
  • the surface layer formed on the polyester fiber and fiber cord acts as a thermal noria layer by the cross-linking reaction, and a small amount of unsaturated compound inside the polyester fiber and cord is impregnated.
  • the polyester structure (non-crystalline part and crystalline part) It is presumed that the thermal motility due to heating is suppressed to a small extent, and that is why the storage elastic modulus E ′ is maintained without significantly decreasing.
  • the crosslinking reactivity of unsaturated compounds becomes important, and in the present invention, unsaturated compounds having an unsaturated group functional group number of more than ⁇ , particularly preferably an unsaturated functional group number of 3 or more are preferred.
  • -(R) group-containing (meth) atalylate compounds can be preferably used.
  • the ultraviolet rays, electron beams, ⁇ rays, etc. can be used, and in order to advance the crosslinking reaction of the impregnated unsaturated compounds, electrons having excellent permeability are used. Lines and gamma rays can be preferably used.
  • ultraviolet rays for cross-linking the surface layer can be used and are not limited.
  • the type and amount of the radical polymerization initiator are not limited.
  • a preferable viscosity of the unsaturated compound used in the present invention can be used in the range of 5 to LOOOcps at room temperature (25 ° C), but it may be heated to such an extent that the compound does not volatilize. Yes. Furthermore, it is preferable to warm up to the vicinity of the glass transition point of the aromatic copolyester so that the compound is actively impregnated into the polyester fiber.
  • the conditions for impregnating the polyester fiber and fiber cord with the unsaturated compound are not particularly limited, but it is preferable to immerse in a warm bath at 30 to L00 ° C for about 3 to 15 minutes.
  • Polyester fiber and fiber cord attached to the fiber cord can be It is preferable that the thickness after removal of the polyester fiber and the fiber cord surface layer after cross-linking is: m or more, preferably 4 m or more. When the thickness of the surface layer is 1 m or less, it is disadvantageous because the crosslinking density is insufficient and the heat resistance is insufficient.
  • a carrier agent in order to improve the permeability when the copolymerized polyester fiber and the copolymerized polyester fiber cord are impregnated with an unsaturated compound.
  • the use of a carrier agent is preferably recommended in order to improve the permeability when an unsaturated compound is impregnated into a polyester fiber that has already been twisted and corded.
  • the overlap caused by twisting of polyester fibers tends to be insufficient for unsaturated compound permeability, and as a result, the heat resistance due to insufficient crosslinking due to insufficient permeability for unsaturated compounds is prevented. It is to do.
  • carrier agent examples include 1,2,4-trichlorodiethylbenzene, orthodichlorobenzene, orthophenylphenol, diethyl ether, methylnaphthalene, butyl benzoate, dimethyl terephthalate, and methyl salicylate.
  • Carriers are exemplified, and in the case of spray treatments where immersion treatment and spraying treatment are preferred, the carrier treatment is preferably heated and treated before 100 ° C.
  • the impregnated compound is impregnated with actinic rays such as ultraviolet rays, electron beams, and ⁇ rays.
  • actinic rays such as ultraviolet rays, electron beams, and ⁇ rays.
  • An electron beam or ⁇ - ray that is irradiated and generates a radical reaction to be crosslinked and has a particularly high transmittance of irradiation energy among actinic rays can be preferably used.
  • the irradiation energy of the active rays, 50 ⁇ : LOOOOKGy is preferably irradiated with an electron beam at 1000 ⁇ 6000KG y crosslinking.
  • the crosslinking reaction does not proceed sufficiently, so heat resistance cannot be obtained and the storage elastic modulus E 'cannot be maintained, and the formed crosslinking reaction layer becomes brittle when irradiated with lOOOOKGy or more. Furthermore, the polyester is further decomposed and the strength properties are deteriorated, which may make it difficult to maintain the storage elastic modulus E '. /.
  • this ratio is 5 or more, the heat resistance of the polyester fiber cord is insufficient, and the mechanical properties are deteriorated and the shape is difficult to maintain. More preferably, the ratio of storage elastic modulus E 'E' /
  • E ′ is preferably within 2.
  • a sample obtained by the immersion treatment was set on a tray and irradiated with an electron beam.
  • the electron beam was irradiated evenly on the front and back, and the irradiation amount was the sum of them.
  • JIS-L1017 the fineness was measured after leaving in a room where temperature and humidity were controlled at 20 ° C and 65% RH for 24 hours.
  • JIS-L1017 it was measured in a tensile tester after being left for 24 hours in a room controlled at 20 ° C and 65% RH.
  • the thickness of the surface layer was determined by subtracting the thickness of the polyester fiber before impregnation from the thickness power of the impregnated and crosslinked polyester fiber.
  • polyester fiber After being immersed for 5 minutes in a bath made of pentaerythritol tetratalate (viscosity 342cps, 25 ° C) at room temperature, The required impregnated polyester fibers were squeezed with a roller and placed in a required amount tray, and irradiated with an electron beam with a total electron energy of 6000 kgy. Using the obtained electron beam cross-linked polyester fiber, measurement was performed by each measurement method.
  • Example 1 The polyester fiber used in Example 1 was preliminarily treated with a 100 ° C. warm-mouthed benzene carrier for 5 minutes, and then treated and measured in the same manner as in Example 2.
  • Electron beam cross-linking obtained by obtaining an impregnated polyester fiber in the same manner as in Example 1 except that pentaerythritol tetraatalylate was switched to trimethylolpropane tritalylate, and irradiating with an electron beam in the same manner as in Example 1. 7 pieces measured with each measuring method using the polyester fiber.
  • the bath temperature comprising trimethylolpropane tritalate was heated to 70 ° C. and treated in the same manner as in Example 3 and measured.
  • the polyester fiber used in Example 1 was measured for the state of fiber without compound impregnation treatment or electron beam crosslinking.
  • a polyester fiber stretched at a stretch ratio of 1.6 to obtain 5 cNZdtex was obtained.
  • the necessary amount of the polyester fiber was placed in a tray and irradiated with an electron beam with a total electron energy of lOOOKGy.
  • the obtained electron beam cross-linked polyester fiber was used and measured by each measuring method.
  • PETA Pentaerisuri
  • TMPA Tri-Met mouthpiece, Rubropan Triacre
  • DA-MGIC diallyl monoglycidyl isocyanurate
  • Example 2 Two pieces of the electron beam cross-linked polyester fiber obtained in Example 1 were twisted to obtain a raw cord of 1440 dtex Z2 and a twist number of 43 ⁇ 43 (tZl0 cm), and measurement was performed by each measurement method.
  • Example 2 Using the electron beam cross-linked polyester fiber obtained in Example 2, the raw cord was measured in the same manner as in Example 6.
  • Example 4 Using the electron beam cross-linked polyester fiber obtained in Example 4, the raw cord was measured in the same manner as in Example 6.
  • Example 6 Only the necessary measurement was performed on the polyester fiber which had been treated and crosslinked in the same manner as in Example 1 except that trimethylolpropane tritalylate was used and the immersion condition was a 70 ° C. bath. Next, measurement was performed using raw cords in the same manner as in Example 6.
  • Example 1 Twist the polyester fibers used in Example 1 and immerse the raw cord made of 1440dtexZ2 and twist number 43 X 43 (tZlOcm) in advance with a black mouth benzene carrier heated at 100 ° C for 5 minutes, and then Then, the sample was immersed in a trimethylolpropane tritalylate at 70 ° C for 5 minutes and irradiated with an electron beam with an electron energy of 6000KGy. The obtained electron beam cross-linked polyester fiber cord was measured by each measuring method.
  • the polyester fibers obtained in Examples 1 to 5 retain the stored viscoelastic modulus E ′. Furthermore, even when the heat flow start temperature was 340 ° C, the polyester fiber was excellent in heat resistance with no heat flow and shape.
  • the uncrosslinked polyester fiber obtained in Comparative Example 1 gradually decreased in storage elastic modulus E ′ from 100 ° C. or higher, and had a melting point and Mechanical properties are not maintained at temperatures above the melting point.
  • the heat flow start temperature flowed around 255 ° C near the melting point, and it did not maintain its shape.
  • the polyester fiber obtained in Comparative Example 2 has a storage elastic modulus E ′ that gradually decreases from 100 ° C or higher, and has a mechanical strength at the melting point and above the melting point. Physical properties are not maintained.
  • the heat flow start temperature was around 264 ° C near the melting point, and it did not maintain its shape.
  • the polyester fiber cords obtained in Examples 6 to 10 retain the storage viscoelastic modulus E ′. Further, even when the heat flow starting temperature was 340 ° C, the polyester fiber cord had excellent heat resistance and no heat flow and the shape was maintained.
  • the polyester fiber cord obtained in Comparative Example 3 has a storage elastic modulus that gradually decreases from 130 ° C or higher. The physical properties are not maintained. In addition, the heat flow start temperature was around 255 ° C near the melting point, and it did not maintain its shape.
  • the polyester fiber cord obtained in Comparative Example 4 gradually decreased in storage modulus from 130 ° C or higher, and the mechanical properties were maintained at the melting point and above the melting point. Not. Also, the heat flow starting temperature flowed around 267 ° C near the melting point and did not retain its shape.
  • TMPA Tri-Met mouthpiece, Rubropan Triacre
  • the type polyester fiber cord can retain its mechanical properties and retain its shape even at a temperature higher than the melting point temperature.
  • FIG. 1 Storage elastic modulus E ′ of the heat-resistant crosslinked polyester fiber obtained in Example 1.
  • FIG. 2 is a storage elastic modulus E ′ of the heat-resistant crosslinked polyester fiber obtained in Example 4.
  • FIG. 3 is a storage elastic modulus E ′ of the polyester fiber of Comparative Example 1.
  • FIG. 4 is a storage elastic modulus E ′ of the crosslinked polyester fiber of Comparative Example 2.
  • FIG. 5 is a storage elastic modulus E ′ of the heat-resistant crosslinked polyester fiber cord obtained in Example 1.
  • FIG. 6 is a storage elastic modulus E ′ of the heat-resistant crosslinked polyester fiber cord obtained in Example 3.
  • FIG. 7 is a storage elastic modulus E ′ of the polyester fiber cord of Comparative Example 1.
  • FIG. 8 is a storage elastic modulus E ′ of the polyester fiber cord of Comparative Example 2.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne une fibre de polyester et une corde de fibres de polyester ayant une excellente résistance à la chaleur lesquelles peuvent conserver leurs propriétés mécaniques à des températures modérées et hautes et ne fondent pas à la chaleur tout en conservant leurs caractéristiques telles que la stabilité des dimensions, une résistance élevée et une durabilité élevée. La fibre de polyester et la corde de fibres de polyester sont utiles en tant que matières pour des éléments de ceinture et de carcasse de pneus. L'invention concerne précisément une fibre de polyester réticulé résistante à la chaleur laquelle est caractérisée en ce que le rapport entre le module de conservation à 100°C (E'100) et le module de conservation à 250°C (E'250), à savoir E'100/E'250, est inférieur ou égal à 10 lors d'une mesure de viscoélasticité dynamique. L'invention concerne également précisément une corde de fibres de polyester réticulé résistante à la chaleur laquelle est caractérisée en ce qu'elle contient au moins partiellement la fibre de polyester réticulé résistante à la chaleur et en ce que le rapport entre le module de conservation à 100°C (E'100) et le module de conservation à 250°C (E'250), à savoir E'100/E'250, est inférieur ou égal à 4 lors d'une mesure de viscoélasticité dynamique.
PCT/JP2007/058138 2006-04-18 2007-04-13 Fibre de polyester réticulé résistante à la chaleur et corde de fibres de polyester réticulé résistante à la chaleur WO2007123059A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-114326 2006-04-18
JP2006114325A JP2007284828A (ja) 2006-04-18 2006-04-18 耐熱性架橋型ポリエステル繊維
JP2006-114325 2006-04-18
JP2006114326A JP2007284829A (ja) 2006-04-18 2006-04-18 耐熱性架橋型ポリエステル繊維コード

Publications (1)

Publication Number Publication Date
WO2007123059A1 true WO2007123059A1 (fr) 2007-11-01

Family

ID=38624960

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/058138 WO2007123059A1 (fr) 2006-04-18 2007-04-13 Fibre de polyester réticulé résistante à la chaleur et corde de fibres de polyester réticulé résistante à la chaleur

Country Status (1)

Country Link
WO (1) WO2007123059A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54133546A (en) * 1978-04-10 1979-10-17 Teijin Ltd Manufacturing of crosslinked polyester molded article
WO2002002356A1 (fr) * 2000-07-03 2002-01-10 Bridgestone Corporation Pneumatique
WO2005111297A1 (fr) * 2004-05-18 2005-11-24 Toyo Boseki Kabushiki Kaisha Cordons de polyester de renforcement pour caoutchoucs et procede de fabrication de ceux-ci
JP2006265745A (ja) * 2005-03-22 2006-10-05 Toyobo Co Ltd タイヤコード用ポリエステル繊維材料
WO2006118143A1 (fr) * 2005-04-28 2006-11-09 Toyo Boseki Kabushiki Kaisha Fibre de polyester et cordon en fibres de polyester reticules resistants a la chaleur
JP2006322083A (ja) * 2005-05-17 2006-11-30 Toyobo Co Ltd タイヤキャッププライコード用ポリエステル繊維材料の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54133546A (en) * 1978-04-10 1979-10-17 Teijin Ltd Manufacturing of crosslinked polyester molded article
WO2002002356A1 (fr) * 2000-07-03 2002-01-10 Bridgestone Corporation Pneumatique
WO2005111297A1 (fr) * 2004-05-18 2005-11-24 Toyo Boseki Kabushiki Kaisha Cordons de polyester de renforcement pour caoutchoucs et procede de fabrication de ceux-ci
JP2006265745A (ja) * 2005-03-22 2006-10-05 Toyobo Co Ltd タイヤコード用ポリエステル繊維材料
WO2006118143A1 (fr) * 2005-04-28 2006-11-09 Toyo Boseki Kabushiki Kaisha Fibre de polyester et cordon en fibres de polyester reticules resistants a la chaleur
JP2006322083A (ja) * 2005-05-17 2006-11-30 Toyobo Co Ltd タイヤキャッププライコード用ポリエステル繊維材料の製造方法

Similar Documents

Publication Publication Date Title
JP3768389B2 (ja) ポリエステルフィラメント糸、ポリエステルタイヤコード及びその製造方法
JP2008038295A (ja) 高耐熱ポリエステルディップコードおよびその製造方法
JP4617945B2 (ja) タイヤコード用ポリエステル繊維材料
CN1273658C (zh) 纺丝性优异的高强度聚2，6－萘二甲酸乙二酯纤维
KR101602385B1 (ko) 형태안정성이 우수한 폴리에틸렌테레프탈레이트 딥코드, 이의 제조방법 및 이를 포함하는 타이어
US11807054B2 (en) Polyester tire cord and radial tire using same
WO2006118143A1 (fr) Fibre de polyester et cordon en fibres de polyester reticules resistants a la chaleur
JP2007303056A (ja) 高耐熱ポリエステル繊維材料、タイヤコード、ディップコード、および高耐熱ポリエステル繊維材料の製造方法
KR101878787B1 (ko) 형태안정성이 우수한 폴리에틸렌테레프탈레이트 타이어 코드, 이의 제조방법 및 이를 포함하는 타이어
KR20150097126A (ko) 형태안정성이 우수한 폴리에틸렌테레프탈레이트 딥코드, 이의 제조방법 및 이를 포함하는 타이어
JP2007284829A (ja) 耐熱性架橋型ポリエステル繊維コード
WO2007123059A1 (fr) Fibre de polyester réticulé résistante à la chaleur et corde de fibres de polyester réticulé résistante à la chaleur
JP2006307381A (ja) 耐熱性架橋型ポリエステル繊維
JP2977679B2 (ja) 芯鞘型複合繊維およびその製造方法
KR101551425B1 (ko) 고강력 폴리에스터 원사 및 타이어코드의 제조방법
JP2006256600A (ja) 空気入りラジアルタイヤ
KR102001061B1 (ko) 내크리프성이 우수한 폴리에틸렌테레프탈레이트 타이어 코드
JP2007284828A (ja) 耐熱性架橋型ポリエステル繊維
KR20170082891A (ko) 내피로성이 우수한 모터사이클용 타이어용 폴리에틸렌테레프탈레이트 딥코드의 제조방법
KR20170091968A (ko) 내피로도가 우수한 폴리에틸렌테레프탈레이트 코드의 제조방법
JP2006307382A (ja) 耐熱性架橋型ポリエステル繊維コード
JP2006265744A (ja) ゴム補強用繊維材料およびその製造方法
KR100584695B1 (ko) 폴리에틸렌-2,6-나프탈레이트 섬유를 이용한 고성능래디얼 타이어
JP2008260804A (ja) 耐熱性架橋型ポリエステル組成物及びポリエステル繊維材料
JPH09256220A (ja) ゴム補強用ポリエステル繊維

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07741574

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07741574

Country of ref document: EP

Kind code of ref document: A1