WO2012132975A1 - ゴム補強用ポリエステル繊維及びその製造方法 - Google Patents

ゴム補強用ポリエステル繊維及びその製造方法 Download PDF

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WO2012132975A1
WO2012132975A1 PCT/JP2012/056911 JP2012056911W WO2012132975A1 WO 2012132975 A1 WO2012132975 A1 WO 2012132975A1 JP 2012056911 W JP2012056911 W JP 2012056911W WO 2012132975 A1 WO2012132975 A1 WO 2012132975A1
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fiber
polyester
rubber
polyester fiber
ton
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PCT/JP2012/056911
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English (en)
French (fr)
Japanese (ja)
Inventor
尾崎　大介
慎太郎 嶋田
冬樹 寺阪
諭司 長瀬
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帝人ファイバー株式会社
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Priority claimed from JP2011078798A external-priority patent/JP5542084B2/ja
Priority claimed from JP2011078799A external-priority patent/JP5542085B2/ja
Priority claimed from JP2011081895A external-priority patent/JP2012214934A/ja
Priority claimed from JP2011081892A external-priority patent/JP2012214933A/ja
Priority claimed from JP2011081894A external-priority patent/JP2012214659A/ja
Application filed by 帝人ファイバー株式会社 filed Critical 帝人ファイバー株式会社
Priority to CN201280016980.3A priority Critical patent/CN103620109B/zh
Priority to KR1020137028710A priority patent/KR101917900B1/ko
Publication of WO2012132975A1 publication Critical patent/WO2012132975A1/ja

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • 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 rubber reinforcing fiber, and more particularly to a rubber reinforcing polyester fiber excellent in adhesiveness after high-temperature dynamic fatigue and a method for producing the same.
  • Polyester fibers represented by polyethylene terephthalate and its derivatives have excellent mechanical and physical properties, physical and chemical properties, are industrially mass-produced, and have a wide range of useful applications including industrial materials.
  • Fiber In particular, polyester fibers having high strength and excellent dimensional stability are very suitable materials for reinforcing rubber materials such as tires, belts, hoses and the like, and recently, higher performance is required.
  • a belt cord such as a V-belt is required to have a high modulus for maintenance-free operation, and a further large fatigue resistance is required for a large-sized high load wrapped belt cord.
  • tire cords there is a demand for lower shrinkage, higher modulus for improved ride comfort, and improved fatigue resistance for operation of large tires in order to improve yield during tire molding. .
  • polyester fiber compared to rayon, which is another general-purpose rubber reinforcing fiber, polyester fiber has properties of low modulus and large shrinkage ratio, though it is high strength. Therefore, in order to increase the modulus and decrease the shrinkage rate of the polyester fiber, a method of starting from a highly oriented undrawn yarn and drawing it is used (Patent Document 1, Patent Document 2, etc.). Furthermore, in order to further improve the spinnability, improvements such as devising a spinning oil are being continued even now (Patent Document 3, etc.).
  • polyester fibers have a molecular structure with low polarity, they basically have a problem with respect to adhesion to rubber. Therefore, a resorcin-formalin-latex (RFL) adhesive is generally used as an adhesive between polyester fiber and rubber, and further improvements are being studied.
  • RFL resorcin-formalin-latex
  • a two-bath treatment method in which fibers are pretreated with an adhesion improver before being treated with an RFL adhesive is widely employed.
  • a pretreated polyester fiber in which an adhesion improver is previously applied in a spinning process is known as a method for dealing with this two-bath treatment method by improving the polyester fiber side.
  • Patent Document 4 and Patent Document 5 In any method, the polyester fiber obtained by these conventional methods has a problem that it is still unsatisfactory in the adhesion after high-temperature dynamic fatigue in rubber particularly required for a belt or the like.
  • the present invention is to provide a polyester fiber for reinforcing rubber and a method for producing the same excellent in adhesion after high-temperature dynamic fatigue in adhesion to rubber.
  • the polyester fiber for rubber reinforcement of the present invention is a fiber made of polyester having ethylene terephthalate as a main repeating unit and an intrinsic viscosity of 0.85 or more, and the amount of terminal carboxyl groups in the fiber is 20 equivalents / ton or more, X A long period by small-angle diffraction is 9 to 12 nm, and a surface treatment agent having an epoxy group is attached to the fiber surface.
  • the amount of terminal carboxyl groups on the fiber surface is 10 equivalent / ton or less
  • the crystal size in the fiber transverse axis direction is 35 to 80 nm 2
  • the amount of terminal methyl groups in the fiber is 2 equivalent / ton or less.
  • the content of titanium oxide in the fiber is 0.05 to 3% by weight and the epoxy index on the fiber surface is 1.0 ⁇ 10 ⁇ 3 equivalent / kg or less.
  • Another method for producing a polyester fiber of the present invention is a method for producing a spinning oil containing an alkaline curing catalyst by melt-discharging a polyethylene terephthalate polymer having an intrinsic viscosity of 0.9 or more and a terminal carboxyl group amount of 15 equivalents / ton or more. After the application, the film is taken up at a speed of 2000 to 6000 m / min and then stretched, and then a finishing oil containing an epoxy compound is applied and aged.
  • the aging treatment temperature is preferably in the range of 20 to 50 ° C.
  • the aging treatment time is preferably 50 hours or more
  • the epoxy curing catalyst is preferably an amine compound.
  • a rubber fiber-reinforced polyester fiber having excellent adhesion after high-temperature dynamic fatigue and a method for producing the same for bonding to rubber.
  • the polyester fiber for reinforcing rubber of the present invention is a fiber made of polyester having ethylene terephthalate as a main repeating unit.
  • the repeating unit contains 80 mol% or more with respect to all the dicarboxylic acid components which comprise polyester. Particularly preferred is a polyester containing 90 mol% or more.
  • it may be a copolymer containing an appropriate third component.
  • the intrinsic viscosity of the polyester fiber needs to be 0.85 or more, and preferably 1.10 or less. Further, the range of 0.89 to 1.05 is preferable, and the range of 0.90 to 1.00 is particularly preferable. When the intrinsic viscosity is less than 0.85, the strength of the polyester fiber is not sufficient, and the strength reduction particularly in the rubber vulcanization process cannot be sufficiently suppressed.
  • the polyester fiber for reinforcing rubber of the present invention needs to have a long period of 9 to 12 nm by X-ray small angle diffraction.
  • the long period by X-ray small-angle diffraction here is a crystal
  • This long period in the rubber fiber-reinforced polyester fiber of the present invention indicates that the interval between crystals is short. As a result, the number of tie molecules directly connecting the crystals increases, and the strength retention rate of the fibers in the rubber when used as a rubber reinforcing fiber can be kept high.
  • the amount of terminal carboxyl groups in the fiber polymer is larger than the conventional amount, it is possible to obtain sufficient durability by accompanying the surface treatment such as epoxy treatment. Further, by setting the long period of the fiber in such a range, the physical properties of the fiber are suitable for rubber reinforcing fibers having a high modulus and a low shrinkage rate.
  • the long cycle In order to set the long cycle to 12 nm or less in this way, it can be obtained by spinning at high speed, and the value of this long cycle becomes large at low speed spinning. Also, there is a limit to high-speed spinning, and the range of 9 nm is the lower limit as the long period. Further, the long period by X-ray small angle diffraction is preferably in the range of 10 nm to 11 nm.
  • the polyester fiber for rubber reinforcement of the present invention preferably has a crystal size in the fiber transverse axis direction (a direction perpendicular to the fiber spinning direction) in the range of 35 to 80 nm 2 .
  • the polyester fiber of the present invention has a short period of 12 nm or less, which is the crystal interval of the fiber vertical axis, but the crystal size is also necessary to make a high strength fiber.
  • the horizontal axis of the fiber is preferably grown to 35 nm 2 or more. However, if the crystal size is too large, the fiber becomes stiff and fatigue properties are lowered, so that it is preferably 80 nm 2 or less.
  • the crystal size in the fiber transverse axis direction is preferably in the range of 40 to 70 nm 2 .
  • the tie molecules easily develop in the fiber horizontal axis direction, so that a three-dimensional structure is constructed in the vertical and horizontal directions of the fiber.
  • the fiber is particularly suitable for reinforcement.
  • the loss factor Tan ⁇ of the fiber is lowered. As a result, the amount of heat generated under repeated stress can be suppressed, and the adhesive performance after applying repeated stress can be kept high, which makes the fiber particularly preferred for rubber reinforcement applications.
  • the rubber fiber-reinforced polyester fiber of the present invention requires that the total amount of carboxyl groups in the polymer be 20 equivalents / ton or more, and that a surface treatment agent having an epoxy group be attached to the fiber surface.
  • the amount of carboxyl groups of the polymer is 15 equivalents / ton or less for the purpose of improving its heat deterioration resistance, Furthermore, it was a common-sense technique to keep it ideally 10 equivalent / ton or less.
  • the polyester fiber for rubber reinforcement has a high necessity for maintaining adhesion to rubber in addition to maintaining the strength of the fiber, and the long period due to X-ray small angle diffraction is as small as 9 to 12 nm as in the polyester fiber of the present invention.
  • the present inventors have found that when an epoxy treatment is performed on the surface, a carboxyl group amount of 20 equivalent / ton or more is most suitable for rubber reinforcement. Further, the amount of carboxyl groups in the polymer is preferably 40 equivalents / ton or less, more preferably 30 equivalents / tons or less, and most preferably 21 to 25 equivalents / tons as the upper limit of the terminal carboxyl group amount. .
  • the surface treatment agent having an epoxy group is attached to the surface of the polyester fiber for rubber reinforcement of the present invention.
  • the surface treatment agent preferably contains an epoxy compound which is one or a mixture of two or more epoxy compounds having two or more epoxy groups in one molecule.
  • halogen-containing epoxies are preferable, and examples thereof include those obtained by synthesis with epichlorohydrin polyhydric alcohol or polyhydric phenol, such as glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether.
  • Compounds such as sorbitol polyglycidyl ether and ethylene glycol diglycidyl ether are preferred.
  • the adhesion amount of the surface treatment agent containing such an epoxy compound to the fiber surface is 0.05 to 1.5% by weight, preferably 0.10 to 1.0% by weight.
  • the surface treatment agent may be mixed with a smoothing agent, an emulsifier, an antistatic agent, other additives, and the like as necessary.
  • the polyester fiber for reinforcing rubber to which the surface treatment agent having an epoxy group of the present invention is attached preferably has an epoxy index on the fiber surface of 1.0 ⁇ 10 ⁇ 3 equivalent / kg or less. Further, the epoxy index per kg of the surface-treated polyester fiber is preferably 0.01 ⁇ 10 ⁇ 3 to 0.5 ⁇ 10 ⁇ 3 equivalent / kg.
  • the epoxy index of the fiber surface is high, there is a tendency that there are many unreacted epoxy compounds, for example, a large amount of viscous scum is generated in the twisting process, and the processability of the fiber decreases. , Problems such as twisted yarn and the like that lead to deterioration of product quality occur.
  • the rubber fiber-reinforced polyester fiber of the present invention is such that a surface treatment agent having an epoxy group is attached thereto, but it is preferable that an epoxy curing catalyst is further attached to the fiber surface.
  • the epoxy curing catalyst is a curing agent that cures the epoxy compound that is an essential component of the present invention.
  • preferable epoxy curing catalysts include amine compounds, and among them, aliphatic amine compounds are preferable. More preferably, it is an amine compound obtained by adding 2 to 20 moles of ethylene oxide and / or propylene oxide to an aliphatic amine having 4 to 22 carbon atoms.
  • the amount of terminal carboxyl groups on the surface (raw yarn surface) of the rubber reinforcing polyester fiber of the present invention is preferably 10 equivalents / ton or less.
  • the amount of carboxyl groups of the entire polymer in the polyester fiber for rubber reinforcement of the present invention is 20 equivalents / ton or more as described above, but as the amount of carboxyl groups on the fiber surface by reaction with the epoxy compound adhering to the fiber surface. It is preferable that it is less than 10 equivalent / ton.
  • the polyester fiber for rubber reinforcement of the present invention can have extremely excellent adhesive performance. At this time, if the amount of terminal carboxyl groups on the fiber surface remains too much, the heat resistance and adhesiveness tend to decrease.
  • the polyester fiber for rubber reinforcement of the present invention has a terminal methyl group amount in the fiber of 2 equivalent / ton or less. Furthermore, it is preferable that no terminal methyl group is contained. This is because the methyl group in the polyester polymer has low reactivity and does not react with the epoxy group. Such terminal methyl groups in the polyester polymer are often attributed to dimethyl terephthalate in the raw material. Therefore, it is preferable that the polyester fiber for rubber reinforcement of the present invention is made of a polyester polymer by a direct weight method (direct esterification method) not using dimethyl terephthalate. When there is no or little terminal methyl group in the polymer constituting the fiber, high reactivity with the epoxy group in the surface treatment agent is ensured, and it is possible to ensure high adhesion and surface protection performance. Become.
  • the titanium oxide content in the fiber is preferably in the range of 0.05 to 3% by weight.
  • the inclusion of titanium oxide is often avoided because it leads to a decrease in yarn-making properties due to foreign matters.
  • such a small amount of titanium oxide is used to maintain the strength of the final product. It is preferable to contain in.
  • titanium oxide content is less than 0.05% by weight, the smoothing effect to disperse the stress acting between the roller and the fiber in the drawing process tends to be insufficient, and the high strength of the fiber finally obtained Tend to be disadvantageous.
  • titanium oxide acts as a foreign substance inside the polymer, tends to impair stretchability, and tend to lower the strength of the fiber finally obtained.
  • the strength of the polyester fiber for reinforcing rubber according to the present invention is preferably in the range of 4.0 to 10.0 cN / dtex. Further, it is preferably 5.0 to 9.5 cN / dtex. When the strength is too low, of course, when the strength is too high, the durability in rubber tends to be inferior as a result. For example, if production is performed at the very high strength, the yarn is likely to be broken in the yarn making process, and the quality stability as an industrial fiber tends to be problematic.
  • the dry heat shrinkage rate of the fiber at 180 ° C. is preferably 1 to 15%. If the dry heat shrinkage is too high, the dimensional change during processing tends to be large, and the dimensional stability of a molded product using fibers tends to be poor.
  • the physical properties of the fiber before cutting may be in the above range, for example, the dry heat shrinkage value is in the range of 1 to 15%. It is preferable that
  • the single yarn fineness of the polyester fiber of the present invention is preferably from 0.1 to 100 dtex / filament from the viewpoint of yarn production.
  • rubber reinforcing fibers such as hoses and belts, and industrial material fibers are preferably 1 to 20 dtex / filament from the viewpoint of strength, heat resistance and adhesiveness.
  • the total fineness is not particularly limited, but is preferably 10 to 10,000 dtex, and particularly preferably 250 to 6000 dtex for rubber reinforcing fibers such as hoses and belts and industrial material fibers.
  • As the total fineness for example, it is also preferable to perform 2 to 10 double yarns in the middle of spinning or drawing, or after the end of each, so that two fibers of 1000 dtex are combined into a total fineness of 2000 dtex.
  • Such a polyester fiber for reinforcing rubber according to the present invention can be obtained, for example, by another polyester fiber manufacturing method according to the present invention.
  • a polyethylene terephthalate polymer having an intrinsic viscosity of 0.9 or more and a terminal carboxyl group amount of 15 equivalents / ton or more is melt-discharged and a spinning oil containing an epoxy curing catalyst is applied. , 2000 to 6000 m / min, and then stretched, then applied with a finishing oil containing an epoxy compound and aged.
  • the main repeating unit of polyester is ethylene terephthalate.
  • the content of the main repeating unit of the polyester is preferably such that the repeating unit is contained in an amount of 80 mol% or more, particularly 90 mol%, based on all dicarboxylic acid components constituting the polyester. It is preferable that it is the polyester containing above. Moreover, if it is a small amount in the polyester polymer, it may be a copolymer containing an appropriate third component.
  • the intrinsic viscosity of this polyester polymer needs to be 0.9 or more, more preferably 0.93 to 1.10, and particularly preferably 0.95 to 1.07. If the intrinsic viscosity is less than 0.9, the strength of the polyester fiber obtained by melt spinning is lowered, and it becomes difficult to obtain a high strength polyester fiber.
  • the method for producing a polyester fiber of the present invention is characterized in that the intrinsic viscosity of the polymer is 0.9 or more and the terminal carboxyl group amount of the polymer is as high as 15 equivalents / ton or more.
  • the upper limit is preferably 30 equivalents / ton or less, and the terminal carboxyl group amount in the polymer stage is preferably in the range of 16 to 25 equivalents / ton, and particularly preferably in the range of 18 to 23 equivalents / ton. .
  • it has been considered essential that the amount of terminal carboxyl groups is small in high-strength polyester fibers for rubber reinforcement. For this reason, polymers having a large amount of terminal carboxyl groups were frequently used even though productivity was low.
  • the present inventors have noted that in the durability in rubber fiber composites, the adhesion between rubber and fiber is important as well as the fiber strength, and the amount of terminal carboxyl groups is adjusted to such a high range. , Spinning at a high speed of 2000 to 6000 m / min, and by combining other requirements, that is, high speed spinning and optimal epoxy treatment, it has been achieved that a more optimal polyester fiber for reinforcing rubber can be obtained. . Furthermore, in the production method of the present invention, since it is not necessary to forcibly reduce the amount of terminal carboxyl groups, the yield and productivity during polymer polymerization can be improved, and the production cost of the polymer and thus the fiber can be reduced. became.
  • polymerization method of the polyester polymer melt-spun there are currently a DMT method (transesterification method) made from dimethyl terephthalate and ethylene glycol and a direct weight method (direct esterification method) made from terephthalic acid and ethylene glycol.
  • a DMT method transesterification method
  • direct weight method direct esterification method
  • polyethylene terephthalate produced by the DMT method has, as its end group, a methyl group end resulting from dimethyl terephthalate in addition to the carboxyl group essential in the present invention.
  • the polyester polymer is a polyester polymer that does not have a terminal methyl group and is made by a straight weight method. It is preferable. By using a straight-weight polyester polymer, it becomes possible to secure the reactivity between the carboxyl group and the epoxy group on the fiber surface at a higher level.
  • the titanium oxide content in the polymer is preferably in the range of 0.05 to 3% by weight. If the titanium oxide content is less than 0.05% by weight, the smoothing effect for dispersing the stress acting between the roller and the fiber tends to be insufficient in the drawing process after fiberizing, and finally. It tends to be disadvantageous for increasing the strength of the resulting fiber. On the other hand, when the content is more than 3%, titanium oxide acts as a foreign substance inside the polymer, impairs stretchability, and tends to decrease the strength of the finally obtained fiber.
  • titanium oxide in the polymer is often avoided because it leads to a decrease in yarn-making property due to foreign matters.
  • the polyester polymer used in the present invention is solid-phase polymerized. This is because in the production method of the present invention, the intrinsic viscosity at least in the polymer stage is required to be increased to 0.9 or more in the stage before melt spinning.
  • the method for producing a polyester fiber of the present invention it is necessary to take up the polyester polymer as described above at a high speed of 2000 to 6000 m / min, and then to stretch it.
  • the fiber becomes a partially oriented yarn in the stage before stretching, and becomes a polyester fiber having a high modulus and a low shrinkage by combining with subsequent stretching.
  • the productivity can be improved.
  • the discharge amount of the polyester polymer from the spinneret is preferably in the range of 420 g / min to 1800 g / min, and more preferably in the range of 500 g / min to 1000 g / min from the viewpoint of productivity.
  • the spinning draft (polymer discharge linear speed from the die / take-off speed) upon discharging the polymer is preferably in the range of 500 to 4000, more preferably 1000 to 2500.
  • the production method of the present invention it is essential to spin at a high speed, but it is preferable to pass through a heated spinning cylinder at a temperature equal to or higher than the melt polymer temperature immediately after discharge from the spinneret.
  • the length of the heated spinning cylinder is preferably 10 to 500 mm. Since the polymer immediately after being discharged from the spinneret is easily oriented and single yarn breakage is likely to occur, it is preferable to use the heated spinning cylinder to delay the cooling.
  • the spun yarn that has passed through the heated spinning cylinder is preferably cooled by blowing cold air of 30 ° C. or lower. Furthermore, it is preferable that it is a cold wind of 25 degrees C or less.
  • the polyester fiber obtained by high-speed spinning in this way has a long period of 12 nm or less by X-ray small angle diffraction.
  • the melt spinning speed In order to reduce the long period in this way, it is preferable to increase the melt spinning speed. In the case of low speed spinning, the value of the long period becomes large.
  • the lower limit of the long period is preferably about 9 nm.
  • the long period by this X-ray small angle diffraction is preferably in the range of 10 nm to 11 nm.
  • the long period is the distance between crystals in the polyester polymer in the longitudinal direction of the fiber (the direction in which the fiber is spun).
  • this long period is small, it has shown that the space
  • the number of tie molecules that directly connect the crystals to each other without breaking the molecules increases, and in the rubber when used as a rubber reinforcing fiber
  • the strength maintenance rate of the fiber can be kept high. For this reason, even in the case of the production method of the present application in which the amount of terminal carboxyl groups in the polymer is spun under a condition higher than before, sufficient durability can be obtained by accompanying the surface treatment such as epoxy treatment. Become. Further, when the length is within such a long period, the physical properties of the fiber are suitable for rubber reinforcing fibers having a high modulus and a low shrinkage rate.
  • the polyester fiber may be temporarily wound from a take-up roller and may be drawn by a so-called separate drawing method, but the so-called direct drawing in which undrawn yarn is continuously supplied from the take-up roller to the drawing process. It is preferable to stretch by the method.
  • the stretching conditions are one-stage or multi-stage stretching, and the stretching load factor is preferably 60 to 95%.
  • the drawing load factor is the ratio of the tension at the time of drawing to the tension at which the fiber actually breaks.
  • the preheating temperature at the time of drawing is preferably carried out at a temperature not lower than 20 ° C. below the glass transition point of the polyester undrawn yarn and not higher than 20 ° C. below the crystallization start temperature.
  • the draw ratio depends on the spinning speed, it is preferable to carry out the drawing at a draw ratio that gives a draw load ratio of 60 to 95% with respect to the breaking draw ratio.
  • the heat setting temperature at the time of enshrining is in the range of 170 to 270 ° C.
  • the polyester fiber production method of the present invention is premised on pretreated polyester fibers, and as a pretreatment method, after melt discharge of the polymer, a spinning oil containing an epoxy curing catalyst is applied, and then After taking up at high speed and then stretching, a finishing oil containing an epoxy compound is applied and heat-treated.
  • the epoxy curing catalyst contained in the spinning oil immediately after melt spinning may be any epoxy curing agent that cures the epoxy compound contained in the subsequent finishing oil, and is preferably an alkaline curing catalyst, particularly an amine compound. It is preferable that More specifically, for example, an amine compound obtained by adding 2 to 20 moles of ethylene oxide and / or propylene oxide to an aliphatic amine having 4 to 22 carbon atoms, such as an aliphatic amine compound, is most suitable.
  • the above-mentioned epoxy curing catalyst as a spinning oil
  • those used as usual spinning oil for polyester fibers such as a smoothing agent, an emulsifier, and an antistatic agent as other spinning oil constituents.
  • this spinning oil does not contain an epoxy compound.
  • More specific other components include mineral oil as a smoothing agent, fatty acid esters, emulsifiers as higher alcohols or ethylene oxide (EO) adducts, antistatic agents as anionic and cationic ones. Surfactant etc. can be mentioned.
  • the proportion of each component of the spinning oil is 3 to 20% by weight of an epoxy curing catalyst (amine compound, etc.), 30 to 80% by weight of a smoothing agent, 20 to 70% by weight of an emulsifier, and 100% by weight of other additives. Such a combination is preferable.
  • the rubber reinforcing fiber of the present invention can be obtained by another method for producing a polyester fiber of the present invention as described above. Furthermore, in order to use it for rubber reinforcement, it is also preferable to use the polyester fiber for rubber reinforcement of the present invention as a multifilament, twist it and use it in the form of a cord. In such a polyester fiber cord for reinforcing rubber, the multifilament fiber is twisted, whereby the strength utilization rate is averaged and the fatigue property in rubber is improved.
  • the number of twists is preferably in the range of 50 to 1000 turns / m, and it is also preferable that the cords are obtained by combining the lower and upper twists.
  • K T ⁇ D 1/2 (T is the number of twists per 10 cm, D is the fineness of the twisted cord) is preferably 990 to 2500.
  • the number of filaments constituting the yarn before being further combined is 50 to 3000.
  • the strength tends to be insufficient.
  • the fineness is too large, it becomes too thick and flexibility cannot be obtained, and sticking between single yarns tends to occur during spinning, and it tends to be difficult to produce stable fibers.
  • the polyester fiber for reinforcing rubber of the present invention is provided with an RFL (resorcin / formalin / latex) adhesive for fiber / rubber on its surface.
  • RFL resorcin / formalin / latex
  • the polyester fiber for rubber reinforcement of the present invention that has been subjected to adhesion treatment can be made into a fiber / rubber composite by being embedded and vulcanized in unvulcanized rubber, and is optimally used as a belt or hose that is a rubber material. be able to.
  • Such a polyester fiber for reinforcing rubber of the present invention has a high adhesive property by reacting the carboxyl group terminal in the polymer with the epoxy group in the surface treatment agent while maintaining the physical properties of high modulus and low shrinkage. Yes.
  • the fiber has a high intrinsic viscosity, a long period in the fiber axis direction, and excellent durability. Adhesive durability in rubber due to the synergistic effect of the surface protection effect of the epoxy group and carboxyl group terminal on the fiber surface. It was an extremely excellent fiber. Therefore, especially the polyester fiber for reinforcing rubber of the present invention can maintain a high level of adhesion and fatigue resistance with the rubber even after bending fatigue in the rubber, and adhesion after high temperature dynamic fatigue.
  • polyester fiber for rubber reinforcement.
  • high modulus and low shrinkage are ensured while ensuring high fatigue resistance even under high load dynamic strain. It also has maintenance-free performance due to its rate, and was able to satisfy various required characteristics at a high level.
  • polyester fiber for reinforcing rubber of the present invention is suitably used as a fiber-reinforced composite in various forms such as cords, woven fabrics, and short fibers.
  • a fiber cord when a fiber cord is formed by twisting, it can be used as a hose reinforcing cord or a belt reinforcing cord.
  • the polyester fiber of the present invention When used as a hose reinforcing cord, it has high adhesiveness while maintaining physical properties of high modulus and low shrinkage. It is a fiber with a long long period and excellent durability, and a fiber cord with extremely excellent adhesion durability in the hose matrix due to the synergistic effect of the surface protection effect by the epoxy group and carboxyl group terminal on the fiber surface Become.
  • the fiber cord for reinforcing a hose using the polyester fiber of the present invention can maintain a high level of adhesion and fatigue resistance with the matrix even after bending fatigue in the hose matrix. It becomes a hose reinforcing fiber cord having excellent adhesion after fatigue.
  • Such a fiber cord for reinforcing a hose is optimally used as various hoses, particularly as a rubber hose.
  • the hose is preferably a fiber reinforced hose composed of the above-described hose reinforcing fiber cord made of the polyester fiber and rubber or resin.
  • a hose is a rubber hose, for example, it can be manufactured as follows. First, the obtained fiber cord is disposed at a predetermined angle on the inner layer made of tube rubber so as to have a predetermined density by a braider. Next, after an interlayer rubber sheet is disposed thereon, the fiber cord is again disposed by a blader, and this is performed a predetermined number of times. Finally, after an outer layer made of a cover rubber for protecting the outer reinforcing fiber is disposed, this is steam vulcanized in, for example, a steam vulcanizer to form a rubber hose. Furthermore, the fiber cord is preferably disposed in a spiral structure.
  • the polyester fiber of the present invention has low shrinkage and excellent dimensional stability, has excellent adhesion to rubber, and has improved fatigue resistance. Such a hose using the polyester fiber of the present invention can satisfy the above requirements at a high level.
  • polyester fiber for rubber reinforcement of the present invention is also suitably used as a fiber material for belt reinforcement.
  • the belt reinforcing fiber material is preferably a belt reinforcing fiber material used as a cord by twisting the obtained polyester fiber into a multifilament. Or it is also preferable that it is the fiber material for belt reinforcement which uses the obtained polyester fiber as a textile form.
  • the warp constituting the woven fabric is preferably a yarn made of the polyester fiber of the present invention.
  • the yarn is preferably in the form of the above fiber cord.
  • the polyester fiber of the present invention as described above is twisted, and 1000 to 1500 yarns are arranged as warps, and polyamide fibers or polyvinyl alcohol are arranged on them. It is preferable that a non-twisted yarn of a synthetic fiber such as a fiber or a twisted yarn having a twisting coefficient of 5000 or less is woven while being arranged as a weft to obtain a belt reinforcing fiber material.
  • the woven structure of this fabric is not particularly limited.
  • the twill or satin structure enhances the strength when stretched, can generate high tension with less stretch when used as a belt base fabric, and generates noise during belt running. Is particularly preferable because it can be reduced, and is preferably used for a belt such as a conveyor belt.
  • These woven fabrics are preferably provided with an adhesive on the surface thereof in the same manner as the above fiber cords.
  • an RFL adhesive treatment agent for rubber reinforcement applications can be treated.
  • the fiber material for belt reinforcement of the present invention that has been subjected to adhesion treatment can be molded by embedding in an unvulcanized rubber and vulcanizing.
  • the polyester fiber of the present invention has high adhesiveness while maintaining physical properties of high modulus and low shrinkage. Moreover, it is a fiber excellent in durability, and is extremely excellent in adhesion durability in a matrix. Therefore, the fiber material for belt reinforcement containing the polyester fiber of the present invention can maintain a high level of adhesion and fatigue resistance with the matrix even after bending fatigue in the matrix, It becomes a fiber material for belt reinforcement having excellent adhesion after dynamic fatigue.
  • a fiber / matrix composite that involves movements such as bending and high-speed rotation of V-belts, etc.
  • high modulus and low shrinkage are ensured while ensuring high fatigue resistance even under high load dynamic strain conditions. It also has maintenance-free properties due to its rate, and can satisfy various required characteristics at a high level.
  • FIG. 1 shows a longitudinal sectional view of the obtained V-belt 1.
  • the V-belt may be a belt of a type in which the rubber cloth 2 woven with natural fiber or synthetic fiber yarn exists only on the upper surface or the lower surface of the belt.
  • the core wire 3 made of the polyester fiber of the present invention is embedded in the adhesive rubber layer 4 adjacent to the compressed rubber layer 5. Short fibers 6 are mixed in the compressed rubber layer 5 in the belt width direction.
  • the use example of the fiber cord using the polyester fiber of the present invention is not limited to the type of V-belt as shown in FIG. 1, but a wrapped type V in which a rubber cloth 2 covers the entire circumference of the belt. 2 may be used as a core of a belt, or as a core of a V-ribbed belt 8 having a plurality of ribs 7 in the longitudinal direction of the belt in the compressed rubber layer 5 as shown in FIG. .
  • the belt reinforcing fiber material may be a woven fabric.
  • the above polyester fiber is twisted, and 1000 to 1500 yarns are arranged as warps, and these are polyamide fiber, polyester fiber, or A non-twisted yarn of a synthetic fiber such as polyvinyl alcohol fiber or a twisted yarn having a twist coefficient of 5000 or less is arranged as a weft while weaving to obtain a reinforcing base fabric that becomes a desired belt reinforcing fiber material.
  • the weave structure is preferably a twill structure or a satin structure.
  • the strength at the time of constant elongation is increased, and when used as a belt base fabric, high tension can be generated with a small amount of stretch, and noise generation during belt running is reduced. Can be made.
  • it is suitably used as a belt such as a conveyor belt.
  • the belt reinforcing fiber material using the polyester fiber of the present invention can be a fiber / polymer composite belt using a polymer such as rubber or resin.
  • the polymer is preferably a rubber elastic body.
  • the above-described polyester fiber used for reinforcement is excellent in heat resistance and dimensional stability, so that the composite is very excellent in moldability.
  • it is optimal for reinforcing a rubber belt, and is suitably used for, for example, a V belt or a conveyor belt.
  • polyester fiber for rubber reinforcement of the present invention can be suitably used as a short fiber for rubber reinforcement.
  • the short fiber for reinforcing rubber comprising the polyester fiber of the present invention solves such problems, and becomes a short fiber for reinforcing rubber having excellent reinforcing effect and improved bending fatigue resistance.
  • the fiber length of the short fiber for reinforcing rubber using the polyester fiber of the present invention is preferably 0.3 to 10.0 mm. If it is less than 0.3 mm, the reinforcing effect by short fibers tends to be difficult to obtain, and if it is longer than 10.0 mm, the short fibers tend to be entangled with each other and do not tend to be uniformly dispersed in the rubber.
  • the single yarn fineness of the polyester short fiber is preferably 0.1 to 100 dtex / piece. Further, from the viewpoint of strength, heat resistance and adhesiveness, it is preferably 1 to 20 dtex / piece.
  • Such a polyester fiber for reinforcing rubber can be obtained by cutting the polyester fiber of the present invention obtained by spinning and stretching as described above into a predetermined length.
  • This short polyester fiber for reinforcing rubber has a surface treatment agent with an epoxy group attached to the fiber surface, but as a manufacturing method, surface treatment is performed at the long fiber stage from the viewpoint of operability. Then, it is preferable to employ a method of cutting thereafter.
  • the surface treating agent having an epoxy group contains the above-described epoxy compound.
  • the polyester reinforcing short fiber for rubber reinforcement is provided with an RFL (resorcin / formalin / latex) adhesive for fiber / rubber on its surface.
  • the cutting from the long fiber to the short fiber can be performed either before or after the application of the RFL adhesive, but from the viewpoint of operability, the cutting is preferably performed after the application of the RFL adhesive.
  • the bonded polyester short fiber for reinforcing rubber of the present invention is kneaded into an unvulcanized rubber, embedded in the short fiber and then vulcanized to obtain a more suitable fiber / rubber composite. it can.
  • Such a short polyester fiber for reinforcing rubber comprising the polyester fiber of the present invention has high adhesiveness while maintaining high modulus and low shrinkage properties suitable for matrix reinforcement. Moreover, it is a fiber excellent in durability, and becomes a short fiber extremely excellent in adhesion durability in rubber.
  • these short polyester fibers for reinforcing rubber can maintain a high level of adhesion and fatigue resistance to the rubber even after bending fatigue in the rubber. It is an excellent polyester short fiber for reinforcing rubber. Especially as a fiber / rubber composite with movement such as bending and high-speed rotation, it has high modulus and low shrinkage while ensuring high fatigue resistance even in the state of high load dynamic strain. In addition to maintenance-free, it can satisfy various required characteristics at a high level.
  • the rubber reinforcing polyester short fibers obtained in this way can be made into a molded article having excellent strength and durability when used with rubber.
  • an unvulcanized rubber and rubber reinforcing short fibers are kneaded with a kneader or the like, dispersed, and then vulcanized to obtain a short fiber reinforced rubber molded product. Since the obtained molded product is excellent in strength and fatigue resistance, it can be optimally used as various rubber products such as belts, hoses and tires.
  • Intrinsic viscosity The diluted solution which melt
  • Amount of terminal carboxyl group 40.00 grams of a polyester sample powdered using a pulverizer and 100 ml of benzyl alcohol were added to a flask, and the polyester sample was placed in a nitrogen stream at 215 ⁇ 1 ° C for 4 minutes. Dissolved in benzyl alcohol. After dissolution, the sample solution is cooled to room temperature, and then an appropriate amount of a 0.1% by weight phenol red benzyl alcohol solution is added, and titration is quickly performed with a N normal sodium hydroxide benzyl alcohol solution, causing discoloration. The amount of dripping up to was Aml.
  • the benzyl alcohol used here was obtained by distilling a reagent-grade product and storing it in a light-shielding bottle.
  • N normal sodium hydroxide solution of benzyl alcohol a solution obtained by titrating with a sulfuric acid solution having a known concentration in advance by a conventional method and obtaining the normality N accurately was used.
  • Titanium oxide content The content of each element was measured using a fluorescent X-ray apparatus (Rigaku Corporation 3270E type) and subjected to quantitative analysis.
  • a fluorescent X-ray apparatus (Rigaku Corporation 3270E type) and subjected to quantitative analysis.
  • a test molded body having a flat surface was prepared under a pressure condition of 7 MPa while the sample was heated to 260 ° C. for 2 minutes with a compression press machine with a polyester fiber resin polymer.
  • the X-ray diffraction measurement of the polyester composition / fiber was performed using an X-ray diffractometer (RINT-TTR3 manufactured by Rigaku Corporation, Cu-K ⁇ ray, tube voltage: 50 kV, current 300 mA, parallel beam method).
  • the long-period interval is measured by a conventionally known method using an X-ray small angle scattering measurement apparatus, that is, a black line from a meridional interference diffraction line obtained by irradiating at a right angle to the fiber axis using a Cu-K ⁇ ray having a wavelength of 1.54 mm. It calculated using a formula (unit: nm 2 ).
  • the crystal size in the horizontal axis direction of the fiber was determined from the X-ray wide angle diffraction using the shiraru equation from the valence width of the (010) (100) intensity distribution curve of the equator scan.
  • Epoxy index (EI) The polyester fiber after the heating treatment was measured for an epoxy index (EI: number of epoxy equivalents per kg of fiber) according to JIS K-7236.
  • This evaluation method is a dynamic deflection test, and is an evaluation method called a so-called shoeshine test.
  • the belt dimensional change rate (%) is obtained by dividing the difference between the belt outer peripheral length immediately after vulcanization and the V belt outer peripheral length after 30 days by the belt outer peripheral length immediately after vulcanization. Calculated.
  • Shoeshine measurement (2) evaluation of adhesion performance with rubber after dynamic fatigue of belt
  • a V-belt with a polyester fiber core and a base fabric reinforcement belt are attached to a pulley with a diameter of 50 mm by applying a load of 50 kg / 2.54 cm (inch), and repeatedly stretched and compressed for 30000 cycles at a temperature of 100 ° C. for 5 hours. Added fatigue.
  • the plies of the belt after stretching and compression fatigue were peeled at a speed of 300 mm / min, and the resulting average peel adhesive strength (N / 2.54 cm (inch)) was determined as the adhesive strength after high-temperature dynamic fatigue.
  • Example 1 (A) Adjustment of spinning oil 65 parts of glycerin triolate, 12 parts of POE (10) laurylamino ether, 8 parts of POE (20) hardened castor oil ether, 12 parts of POE (20) hardened castor oil triole, POE (8) 10 parts of an oil composition consisting of 2 parts of oleyl phosphate Na and 1 part of antioxidant was heated to 50 ° C.
  • polyester fiber Manufacture of polyester fiber
  • the intrinsic viscosity of the chip after solid-phase polymerization is 1.03, the terminal carboxyl group amount is 20 equivalents / ton, and the terminal methyl group amount is 0 equivalent / tons.
  • a polyester fiber of 384 filaments was obtained by a melt spinning method under the conditions of a spinning draft 1777 using a polyethylene terephthalate chip obtained by a straight weight method having a titanium oxide content of 0.05 wt%.
  • the spinning oil prepared by the above method is 0.4 parts of the oil agent attached to 100 parts of the fiber (the amount of the aliphatic amine compound component attached). 0.048 wt%), and then taken up by the first roller at 60 ° C., stretched 1.25 times between the first roller and the second roller at 60 ° C. Second-stage stretching is performed so that the total stretching ratio is 1.43 times between the two rollers and the third roller at 180 ° C., and then the stretching ratio is 1.0 times between the third roller and the fourth roller.
  • the finished oil prepared by the above method is applied by a roller type oil agent application method so that the oil agent adhesion amount is 0.2 parts by weight (epoxy compound component adhesion amount 0.12% by weight) with respect to 100 parts of the fiber.
  • the oil agent adhesion amount is 0.2 parts by weight (epoxy compound component adhesion amount 0.12% by weight) with respect to 100 parts of the fiber.
  • the resulting fiber has mechanical properties of an intrinsic viscosity of 0.91, a fineness of 1130 dtex, a strength of 6.9 cN / dtex, and an elongation of 12%, and the terminal carboxyl group content is 22 equivalents / ton, Period is 10 nm, fiber surface end carboxyl group amount is 7 equivalent / ton, fiber horizontal axis direction crystal size is 45 nm 2 , terminal methyl group amount is 0 equivalent / ton, titanium oxide content is 0.05 wt%, surface epoxy group The amount was 0.1 ⁇ 10 ⁇ 3 equivalent / kg.
  • the fiber thus obtained was subjected to aging treatment at a temperature of 30 ° C. for 360 hours. Despite the high spinning speed, the amount of scum generated in the production process was small.
  • the obtained polyester fiber was subjected to a lower twist of 470 times / m, and then two of them were put together and subjected to an upper twist of 470 times / m to obtain a cord of resorcin / formalin / latex adhesive liquid (RFL liquid). ) And subjected to tension heat treatment at 240 ° C. for 2 minutes to obtain a treated cord.
  • RTL liquid resorcin / formalin / latex adhesive liquid
  • polyester fibers and cords were as follows: strength was 134 N, elongation was 13%, load elongation at 44 N was 3.9%, and 177 ° C. dry yield was 2.7%.
  • Example 1 The same as in Example 1 except that the terminal carboxyl group of the chip after solid-phase polymerization in Example 1 was changed from 20 equivalent / ton to 9 equivalent / ton and the polyester chip having a terminal methyl group amount of 5 equivalent / ton was used.
  • Tables 1 and 2 show the physical properties of the obtained polyester fiber and treatment cord and the adhesion evaluation results.
  • Example 1 although the amount of terminal carboxyl groups of the fiber was as small as 18 equivalents / ton, normal peel adhesion was obtained and the heat-resistant strength maintenance rate was sufficient. However, the adhesion after dynamic fatigue (shoeshine measurement) was inferior.
  • Comparative Example 2 Unlike Comparative Example 1, the same procedure as in Comparative Example 1 was performed, except that a non-amine-based spinning oil was used without removing an epoxy compound and removing the amine component from the spinning oil. Tables 1 and 2 show the physical properties of the obtained polyester fiber and treatment cord and the adhesion evaluation results. Compared with Comparative Example 1, the adhesion after dynamic fatigue (shoeshine measurement) was inferior.
  • Example 2 The same procedure as in Example 1 was performed except that the aging treatment at 30 ° C. for 360 hours in Example 1 was changed to the heat treatment at 60 ° C. for 80 hours. Since heat treatment was carried out without aging treatment, the amount of scum generated in the production process was rather large. Tables 1 and 2 show the physical properties of the obtained polyester fiber and treatment cord and the adhesion evaluation results.
  • Example 3 The same procedure as in Example 1 was performed except that the spinning speed of Example 1 was changed from 2800 m / min to 3200 m / min, the number of filaments was changed from 384 to 500 to adjust the physical properties, and the draw ratio was adjusted, and the final fineness was the same 1130 dtex, A polyester fiber having an intrinsic viscosity of 0.91 and a treated cord obtained by twisting the polyester fiber were obtained. Tables 3 and 4 show the physical properties and adhesion evaluation results of the obtained polyester fibers and treatment cords.
  • Example 4 Example 1 was carried out in the same manner as in Example 1 except that the spinning speed was 2500 m / min, the number of filaments was adjusted from 384 to 249 to adjust the physical properties, and the draw ratio was adjusted. The final fineness was the same, 1130 dtex, and the intrinsic viscosity was 0.91 polyester fiber and a treated cord obtained by twisting it were obtained. Table 3 and Table 4 show the physical properties of the obtained polyester fiber and treatment cord and the adhesion evaluation results.
  • Example 3 Unlike Example 1, an epoxy compound was not attached, and the same procedure as in Example 1 was carried out except that a non-amine type spinning oil was used in which the amine component was removed from the spinning oil. Table 3 and Table 4 show the physical properties of the obtained polyester fiber and treatment cord and the adhesion evaluation results. In addition to being inferior in adhesiveness (shoe shine measurement) after dynamic fatigue, the heat resistant strength maintenance rate in the rubber was also lowered.
  • the spinning oil prepared by the above method is 0.4 parts of the oil agent attached to 100 parts of the fiber (the amount of the aliphatic amine compound component attached). 0.048% by weight), and then taken up by the first roller at 100 ° C., stretched 3.0 times between the first roller and the second roller at 120 ° C., and then stretched to the first stage.
  • Second-stage stretching is performed so that the total stretching ratio is 5.0 times between the two rollers and the third roller at 190 ° C., and then the stretching ratio is 0.97 times between the third roller and the fourth roller.
  • the finished oil prepared by the above method is applied by a roller type oil agent application method so that the oil agent adhesion amount is 0.2 parts by weight (epoxy compound component adhesion amount 0.12% by weight) with respect to 100 parts of the fiber.
  • the oil agent adhesion amount is 0.2 parts by weight (epoxy compound component adhesion amount 0.12% by weight) with respect to 100 parts of the fiber.
  • the conditions other than the above were the same as in Example 1.
  • the spinning speed was low, and the amount of scum generated remained at a low level.
  • the obtained fiber has a mechanical property of a fineness of 1130 dtex, an intrinsic viscosity of 0.91, strength of 7.6 cN / dtex, elongation of 14%, and the amount of terminal carboxyl groups is 22 equivalents / ton.
  • the long period is 14 nm
  • the fiber surface end carboxyl group amount is 7 eq / ton
  • the fiber horizontal axis direction crystal size is 35 nm
  • the 2 end methyl group amount is 0 eq / ton
  • the titanium oxide content is 0.05 wt%
  • the surface epoxy was 0.1 ⁇ 10 ⁇ 3 equivalent / kg.
  • Table 3 and Table 4 show the physical properties of the obtained polyester fiber and treatment cord and the adhesion evaluation results.
  • this comparative example 4 has a long period of 14 nm and a large elongation, although there is no difference in strong elongation, the dry heat shrinkage rate and intermediate load elongation are also large, and the initial adhesive strength is equal. However, the heat-resistant cooperation maintenance ratio in rubber and the adhesion after dynamic fatigue (shoeshine measurement) were greatly inferior.
  • Example 5 The polyester fiber obtained in Example 1 was obtained by applying a lower twist of 470 times / m and then combining the two to obtain an upper twist of 470 times / m. The cord was then resorcin-formalin latex. Adhesion treatment was performed using an adhesive solution (RFL solution), and a heat treatment was performed at 240 ° C. for 2 minutes to form a treatment cord.
  • RNL solution adhesive solution
  • the obtained cord made of polyester fiber was molded into a hose using unvulcanized rubber, and then steam vulcanized at 153 ° C. for 35 minutes to obtain a rubber hose.
  • Table 5 shows the results of the fatigue evaluation of the rubber hose obtained.
  • Comparative Example 5 A rubber hose was made in the same manner as in Example 4 except that the fiber of Comparative Example 1 was used instead of the fiber obtained in Example 1, and the performance was evaluated. The results are also shown in Table 5.
  • Example 6 The polyester fiber obtained in Example 1 was used for twisting at a lower twist number of 200 T / m and an upper twist number of 120 T / m to obtain a cord (fiber material for belt reinforcement) of 1100 dtex / 2/3. After attaching epoxy / isocyanate as an adhesive treating agent to the cord, heat treatment was performed at 160 ° C. for 60 seconds and 245 ° C. for 80 seconds, and RFL (resorcin-formalin-latex) was further attached to the cord. Heat treatment was carried out at 60 ° C. for 60 seconds and 235 ° C. for 60 seconds. Using the obtained cord as a core wire, a V-belt 1 was prepared. Table 6 summarizes the results of the belt tension maintenance rate, belt dimensional change rate, and shoeshine measurement of the obtained V-belt.
  • Examples 7 and 8, Comparative Examples 6 to 9 A V-belt was evaluated in the same manner as in Example 6 except that the fibers of Examples 3 and 4 and Comparative Examples 1 to 4 were used instead of the fiber obtained in Example 1, and performance was evaluated. The results are shown in Tables 6 and 7 together.
  • this short polyester fiber for reinforcing rubber is blended with natural rubber and unvulcanized rubber mainly composed of styrene butadiene, and MS type pressure kneader (DS3-10MHHS, manufactured by Moriyama Seisakusho) is used. And kneaded for 3 minutes. The sheet was put out to an appropriate thickness so that the short fibers were oriented, a rubber sheet was formed by press vulcanization, a sample was cut out in the orientation direction of the short fibers to obtain a short fiber reinforced rubber molded product, and the performance was evaluated.
  • natural rubber and unvulcanized rubber mainly composed of styrene butadiene
  • MS type pressure kneader DS3-10MHHS, manufactured by Moriyama Seisakusho
  • Examples 10 and 11, Comparative Examples 10 to 13 A short fiber reinforced rubber molded product was obtained in the same manner as in Example 9 except that the fibers of Examples 3 and 4 and Comparative Examples 1 to 4 were used instead of the fiber obtained in Example 1, and the performance was evaluated. . The results are shown in Tables 8 and 9.

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