WO2017122964A1 - Polyester fiber, preparation method therefor, and tire cord comprising same - Google Patents

Polyester fiber, preparation method therefor, and tire cord comprising same Download PDF

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Publication number
WO2017122964A1
WO2017122964A1 PCT/KR2017/000146 KR2017000146W WO2017122964A1 WO 2017122964 A1 WO2017122964 A1 WO 2017122964A1 KR 2017000146 W KR2017000146 W KR 2017000146W WO 2017122964 A1 WO2017122964 A1 WO 2017122964A1
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Prior art keywords
polyester fiber
treatment liquid
fiber
tire cord
polyester
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PCT/KR2017/000146
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French (fr)
Korean (ko)
Inventor
한석종
안덕중
박진경
유성중
박두진
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(주)효성
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Priority to CN201780005345.8A priority Critical patent/CN108431328B/en
Priority to TR2018/07702T priority patent/TR201807702T1/en
Publication of WO2017122964A1 publication Critical patent/WO2017122964A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • 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
    • D06M13/395—Isocyanates
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone 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
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof

Definitions

  • the present invention is a secondary treatment liquid comprising a phenolic resin epoxidized on polyester fibers and a copolymer of maleic anhydride-polybutadiene (Riccobond 7004, hereinafter referred to as 'maleic anhydride polybutadiene')
  • the present invention relates to a treated polyester fiber, a method for manufacturing the same, and a tire cord including the same, wherein the adhesive is an environmentally friendly adhesive that does not use environmentally harmful substances such as resorcinol, formalin, and ammonia.
  • Tire reinforcements generally represented by polyethylene terephthalate (polyester), have excellent mechanical strength, modulus of elasticity, dimensional stability and heat resistance, which are important properties of rubber reinforcements, such as rubber composites such as tires, It is widely used as a reinforcing material for belts or hoses.
  • polyethylene terephthalate polyethylene terephthalate
  • dimensional stability dimensional stability
  • heat resistance which are important properties of rubber reinforcements, such as rubber composites such as tires
  • It is widely used as a reinforcing material for belts or hoses.
  • higher performance reinforcement materials due to the high performance of automobiles, the development of driving roads, and the severe use of rubber composite materials.
  • the surface of the polyester fiber is inert, the adhesion to rubber is not good, so a method of improving the adhesion of the fiber to rubber by treating the surface of the epoxy and diisocyanate compounds has been studied for a long time.
  • the fibers are treated with a primary treatment liquid composed of epoxy and diisocyanate or parachlorophenol-based resins, and then secondary treatment with general resorcinol-formalin latex (hereinafter referred to as ⁇ ) ''.
  • ⁇ general resorcinol-formalin latex
  • the degree of reaction may vary depending on outdoor conditions such as temperature or humidity, or the application state of RFL may vary according to an oil or fiber property, which may cause non-uniformity of final tire cord properties.
  • the use of chemicals such as resorcinol, formalin, ammonia and the like can cause environmental problems.
  • a polyethylene terephthalate fiber is first treated with a mixture of epoxy and blocked isocyanate, and a polyol and an aromatic polyaldehyde are used to prepare a RFL by replacing the resorcinol-formalin resin.
  • a method for producing a polyethylene terephthalate tire cord that is secondary treated to impart adhesion is proposed.
  • this method can prepare environmentally friendly adhesives by not using environmentally harmful substances such as resorcinol and formalin, but acetic acid and ethanol are not dissolved in water because the polyalcohol and aromatic aldehydes are not dissolved in water.
  • the adhesive liquid should be prepared in an organic solvent such as a solvent, and the time for the reaction of the adhesive liquid is also long, and the reactivity of the polyphenol and the aromatic aldehyde is relatively low, so that the adhesive strength of the tire cord treated with the adhesive liquid may be low. have.
  • the international patent WO2014 / 091376 A1 discloses an environmentally friendly adhesive liquid that can replace the resorcinol-formalin resin using water-soluble acrylic resin (BASF, Acrodur 950) and glycerol epoxy (Nagase Chemtex, EX-313). I'm proposing.
  • This method has the advantage of expressing adhesion even at low Dip Pick Up (DPU) in the case of fibers having a reactor such as nylon 66 and rayon by the reaction of acrylic resin and epoxy, but the surface is inert like polyethylene terephthalate. In case of having a low adhesive strength.
  • DPU Dip Pick Up
  • the pH should be sensitively adjusted at the time of preparation, and when the pH is not adjusted, coagulum is generated by reaction with latex, and thus adhesives cannot be used. .
  • RFL which is a secondary treatment liquid
  • resorcinol, formalin, ammonia, etc. which are environmentally harmful substances
  • Formalin is registered as a primary carcinogen, and ammonia causes odors. Therefore, the use of resorcinol and formalin in 2019 will be banned in accordance with the REACH regulations in Europe and the United States, and the development of eco-friendly secondary treatment liquid that does not use such environmentally harmful substances is required. It is a reality.
  • the present invention relates to a polyester fiber treated with an environmentally friendly adhesive liquid on the surface of the polyester fiber, a method of manufacturing the same and a tire cord including the same.
  • Polyester fiber which can manufacture high performance tire cord which can improve the adhesive force, reduce the rigidity of tire cord, improve heat resistance and fatigue resistance, and prevent the peeling phenomenon of rubber and fiber generated at high speed of tire running, its manufacturing method and
  • An object of the present invention is to provide a tire cord including the same.
  • the present invention comprises the steps of preparing a first treatment liquid comprising a blocked diisocyanate and an epoxy compound; Passing through the primary treatment liquid while applying a tensile force to the polyester twisted cord; Drying and heat-treating the fibers having passed through the primary treatment liquid; Passing the heat treated polyester fiber through a secondary treatment liquid comprising an epoxidized phenolic resin and a maleic hydride polybutadiene copolymer; And it provides a method for producing a polyester fiber comprising the step of drying and stabilizing the fiber passed through the secondary treatment liquid.
  • the epoxidized phenol resin and maleic hydride polybutadiene copolymer is preferably 1: 1 to 5: 1 by weight.
  • the present invention also provides a polyester tire cord, which is produced by the above production method and has the following physical properties.
  • the polyester fiber according to the present invention is a maleic anhydride- which can increase the binding force between the epoxidized phenolic resin and rubber latex and the epoxidized phenolic resin and rubber latex which can interact with rubber as a secondary treatment liquid.
  • a maleic anhydride- which can increase the binding force between the epoxidized phenolic resin and rubber latex and the epoxidized phenolic resin and rubber latex which can interact with rubber as a secondary treatment liquid.
  • the secondary treatment solution used in the present invention can be used immediately after mixing, it does not require a reaction aging time and does not use any environmental regulatory substances in the preparation of the treatment solution.
  • the degree and enabling the uniform treatment liquid to be attached it is possible to reduce the manufacturing processability and the production cost, and to provide the treatment liquid for the polyester fiber with improved quality uniformity.
  • the present invention provides a polyester fiber, a manufacturing method thereof and a tire cord comprising the same.
  • Method for producing a polyester fiber of the present invention comprises the steps of preparing a primary treatment liquid containing a blocked diisocyanate and an epoxy compound; Passing through the primary treatment liquid while applying a tensile force to the polyester yarn cord; Drying and heat-treating the fibers having passed through the primary treatment liquid; Passing the heat treated polyester fiber through a secondary treatment liquid comprising an epoxidized phenol resin and a Maleic Anhydride-Polybutadiene copolymer; And drying and stabilizing the fibers passing through the secondary treatment liquid.
  • the present invention uses a primary treatment liquid mainly composed of blocked isocyanates and epoxy to bond polyester fibers and rubber. Thereafter, a rubber latex is added to the mixed solution of the epoxidized phenolic resin and the maleic anhydride-polybutadiene copolymer to treat the polyester fiber with a secondary treatment solution capable of interacting with the rubber.
  • the secondary treatment solution may include a maleic anhydride polybutadiene copolymer in order to increase the bonding strength of the rubber latex and the epoxidized phenol resin.
  • the polyester fiber according to the present invention and the secondary treatment liquid consisting of the epoxidized phenol and maleic hydride polybutadiene copolymer and latex as follows.
  • a secondary treatment solution 0.5 to 10% by weight of epoxidized phenolic resin, 0.1 to 3% by weight maleic hydride polybutadiene copolymer, based on 100% by weight of the secondary treatment solution, vinylpyridine latex 15 To 20% by weight, and 0 to 5% by weight of styrene-butadiene latex.
  • the epoxidized phenolic resin serves to interact with the rubber.
  • Such epoxidized phenolic resin is a bisphenol-A and epichlorohydrin, a noble and epichlorohydrin, or a high molecular weight polyisocyanate at the end of the epoxy resin synthesized from resol and epichlorohydrin, and organic such as butanol It can be prepared by dispersing in a solvent.
  • the polymerized epoxy is synthesized by addition polymerization of a novolac or resol to a liquid epoxy resin synthesized using bisphenol-A and epichlorohydrin, and then an isocyanate blocked with resorcinol, phenol, caprolactam or the like is prepared.
  • a mixed solution may be prepared by applying a very strong shearing force while mixing a novolak or a resol-type epoxy and phenol resin together with water, a co-solvent, and a dispersant and heating. This mixed solution has a uniform dispersibility in the form of small particles and can be maintained in a stable state by the dispersant during the cooling process.
  • a co-solvent may be used alcohols or ether glycol (Glycol Ether).
  • the epoxidized phenol resin preferably contains 0.5 to 10% by weight based on 100% by weight of the secondary treatment liquid.
  • content of the epoxy compound is less than 0.5% by weight, it is difficult to express sufficient adhesiveness to the fiber by providing sufficient reactivity to the fiber, and when it exceeds 10% by weight, the workability is decreased due to the high rigidity and the fatigue resistance of the cord is reduced. In addition, manufacturing costs will increase.
  • the epoxidized phenol resin and the maleic anhydride-polybutadiene copolymer are preferably 1: 1 to 5: 1 by weight. If it is out of the above range, not only sufficient adhesion is not expressed, but also the rigidity is so high that fatigue resistance, which is one of the main required characteristics of the tire cord, is degraded, resulting in deterioration of tire durability.
  • the content of the vinylpyridine latex is preferably 15 to 20% by weight based on 100% by weight of the primary treatment solution, and when the content of the vinylpyridine latex is 15% by weight or less, sufficient adhesion with rubber may not be expressed. If it is more than 20% by weight, the initial adhesive strength is increased, but the latex layer is formed thick, which may cause peeling phenomenon in the latex layer at a high temperature, and the stiffness is increased due to the high adhesion amount, thereby reducing the fatigue resistance. May cause deterioration in workability or increase in final product defects.
  • the polyester fiber thus prepared is a mixture of epoxidized phenolic resins and rubber latexes that can interact with rubber and maleic anhydride-polybutadiene copolymers that can increase the bonding strength of the epoxidized phenolic resins and rubber latex.
  • the secondary treatment solution used in the present invention can be used immediately after mixing, it does not require a reaction aging time, and does not use any environmental regulatory substances in the preparation of the treatment solution.
  • the secondary treatment solution used in the present invention can be used immediately after mixing, it does not require a reaction aging time, and does not use any environmental regulatory substances in the preparation of the treatment solution.
  • the primary treatment solution was prepared by mixing 96.5 wt% water, 0.5 wt% epoxy compound, 1.0 wt% diisocyanate, 1.5 wt% vinylpyridine latex, and 0.5 wt% heat resistant additive. It was prepared by adjusting as shown in Table 1.
  • the twisted yarn cord produced by using 1500 denier 2ply of polyester fiber for tire cords as 37 (Twist / 10cm) and 37 (Twist / 10cm) soft water was immersed in the primary treatment liquid while applying a tension of 0.1 g / d. Passed through, dried at 160 ° C. for 2 minutes and heat treated at 245 ° C.
  • the polyester fiber was further subjected to the binding treatment between the epoxidized phenol resin (Allnex Corp. VPW-1942), vinylpyridine latex and styrene-butadiene latex, and the epoxidized phenolic resin and rubber latex. It was made into a polyester tire cord by being impregnated into an adhesive solution consisting of an increaseable maleic hydride polybutadiene copolymer (Ricobond 7004 from Cray Valley), followed by drying at 160 ° C. and stabilization at 245 ° C.
  • an adhesive solution consisting of an increaseable maleic hydride polybutadiene copolymer (Ricobond 7004 from Cray Valley), followed by drying at 160 ° C. and stabilization at 245 ° C.
  • a polyethylene terephthalate tire cord was manufactured in the same manner as in Example 1, except that the content of the secondary treatment liquid composition was adjusted as shown in Table 1 below.
  • Example 2 Secondary liquid composition (% by weight) water 76.5 75.0 77.5 76.5 77.5 Caustic soda 0.1 0.4 - - - Resorcinol 2.4 3.0 - - - formalin 0.8 1.2 - - - Epoxylated Phenolic Resin - - 2.5 2.5 4.0 Ricobond7004 - - - 1.0 1.0 Vinyl pyridine latex 20.0 17.5 20.0 17.5 15.0 SBR Latex - 2.5 - 2.5 2.5 ammonia 0.2 0.4 - - - - -
  • the cord As a method of showing the adhesive strength between the heat treated cord and the rubber, the cord is placed in a rubber block and vulcanized at a pressure of 50 kgf / cm 2 at 160 ° C. for 20 minutes (initial) or 170 ° C. for 60 minutes (heat resistance). Adhesion is measured at a tensile rate of 200 m / min using an elongation type tensile tester. The same test was carried out 10 times to obtain an average value. Other methods were performed according to ASTM D4776-98.
  • a measure of the resistance value against external stress of the heat treatment cord which simulates tire running conditions.
  • the evaluation of the disc fatigue resistance was evaluated using Ueshima Seisakusho Co., Ltd. FT-6110. Fatigue test conditions were 6% tensile and 12% compression. After 8 hours of fatigue at 120 ° C at 2500rpm, the cord was collected and the strength was measured. Cord strength measurement method was carried out according to the ASTM D885 method.
  • the polyester tire cord according to the present invention shows that the adhesion and fatigue resistance are improved as compared with the comparative example without addition of the maleic hydride polybutadiene copolymer. Can be.

Abstract

The present invention relates to a polyester fiber treated with an eco-friendly secondary treatment liquid, the polyester fiber containing an epoxidized phenolic resin, a maleic anhydride-polybutadiene copolymer, and vinylpyridine latex and styrene-butadiene latex, to a preparation method therefor, and to a tire cord, whereby a high-functional tire cord that can prevent a delamination phenomenon between rubber and fiber, which occurs at the time of high-speed driving of tire, can be prepared by improving the adhesive force, heat resistance, and fatigue resistance of the tire cord.

Description

폴리에스테르 섬유, 이의 제조방법 및 이를 포함하는 타이어 코드Polyester fiber, preparation method thereof and tire cord comprising same
본 발명은 폴리에스테르 섬유에 에폭시화된 페놀 수지와 말레익안하이드라이드폴리부타디엔(Maleic Anhydride-Polybutadiene, Ricobond 7004,이하 ‘말레익안하이드라이드폴리부타디엔’이라 함) 공중합체를 포함하는 2차 처리액으로 처리한 폴리에스테르 섬유, 이의 제조방법 및 이를 포함하는 타이어 코드에 관한 것으로, 상기 접착제는 레소시놀, 포르말린, 암모니아 등의 환경 유해물질을 사용하지 않는 친환경 접착제이며 이를 사용함에 따라서 타이어 코드의 접착력, 내열성 및 내피로성을 향상시켜, 타이어 고속 주행시 발생되는 고무와 섬유의 박리현상을 방지할 수 있는 고성능 타이어 코드를 제조할 수 있다.The present invention is a secondary treatment liquid comprising a phenolic resin epoxidized on polyester fibers and a copolymer of maleic anhydride-polybutadiene (Riccobond 7004, hereinafter referred to as 'maleic anhydride polybutadiene') The present invention relates to a treated polyester fiber, a method for manufacturing the same, and a tire cord including the same, wherein the adhesive is an environmentally friendly adhesive that does not use environmentally harmful substances such as resorcinol, formalin, and ammonia. By improving the heat resistance and fatigue resistance, it is possible to manufacture a high-performance tire cord that can prevent the peeling of the rubber and fibers generated during high-speed running of the tire.
일반적으로 폴리에틸렌테레프탈레이트(Polyethyleneterephthalate, 이하 폴리에스테르)로 대표되는 타이어 보강재는 고무보강재가 가져야 할 중요한 특성인 우수한 기계적 강도, 탄성 계수, 치수 안정성 및 내열성을 가지고 있기 때문에 고무 합성재, 예를 들어 타이어, 벨트 또는 호스 등을 위한 보강재로 널리 이용되고 있다. 그러나 자동차의 고성능화, 주행 도로의 발전, 고무 합성재 사용조건의 가혹화 등에 따라서 더욱 고성능화된 보강소재의 필요성이 대두되어져 왔다. 그러나 폴레에스테르 섬유의 표면이 불활성이기 때문에 고무와의 접착력이 좋지 않으므로 에폭시 및 디이소시아네이트 화합물을 섬유의 표면에 처리하여 고무에 대한 섬유의 접착성을 개량하는 방법이 오랫동안 연구되어 왔다.Tire reinforcements, generally represented by polyethylene terephthalate (polyester), have excellent mechanical strength, modulus of elasticity, dimensional stability and heat resistance, which are important properties of rubber reinforcements, such as rubber composites such as tires, It is widely used as a reinforcing material for belts or hoses. However, there has been a need for higher performance reinforcement materials due to the high performance of automobiles, the development of driving roads, and the severe use of rubber composite materials. However, because the surface of the polyester fiber is inert, the adhesion to rubber is not good, so a method of improving the adhesion of the fiber to rubber by treating the surface of the epoxy and diisocyanate compounds has been studied for a long time.
이러한 폴리에스테르 섬유의 접착방법에는 에폭시 및 디이소시아네이트 또는 파라 클로로페놀계 수지로 이루어진 1차 처리액으로 섬유를 처리한 후, 일반적인 레소시놀-포르말린 라텍스(이하에서 ‘’라 한다)로 2차 처리하는 방법이 알려져 있다. 그러나 상기 방법에서 사용되는 RFL의 경우에는 레소시놀과 포르말린을 반응시켜 레소시놀-포르말린 수지를 만들기 위하여 가성소다 촉매 하에서 일정 시간동안 반응이 필요하며, 레소시놀-포르말린 수지와 고무라텍스의 반응을 통하여 RFL을 조제하기 위해서 24시간 정도의 반응숙성시간이 필요하게 된다. 따라서, 온도 또는 습도 등의 외기조건에 따라서 반응정도가 달라지게 되거나, 유제나 섬유 특성에 따라서 RFL의 도포상태가 달라지게 되어 최종 타이어코드 물성의 불균일성을 야기할 수 있다. 또한, 레소시놀, 포르말린, 암모니아 등의 화학물질을 사용함으로써 환경 문제를 야기할 수 있기 때문에 다른 물질을 사용한 접착 연구가 진행되고 있다.In the method of bonding the polyester fibers, the fibers are treated with a primary treatment liquid composed of epoxy and diisocyanate or parachlorophenol-based resins, and then secondary treatment with general resorcinol-formalin latex (hereinafter referred to as ``) ''. How to do is known. However, in the case of RFL used in the above method, a reaction is required for a certain time under a caustic soda catalyst to make resorcinol-formaline react to form resorcinol-formalin resin, and reaction of resorcinol-formalin resin with rubber latex. Reaction maturation time of about 24 hours is required to prepare RFL. Therefore, the degree of reaction may vary depending on outdoor conditions such as temperature or humidity, or the application state of RFL may vary according to an oil or fiber property, which may cause non-uniformity of final tire cord properties. In addition, the use of chemicals such as resorcinol, formalin, ammonia and the like can cause environmental problems.
미국특허 제 2014/0308864 A1에서는 폴리에틸렌테레프탈레이트 섬유에 에폭시와 블로킹된 이소시아네이트(Isocyanate)의 혼합액으로 1차 처리하고 폴리알콜과 방향족 폴리알데히드를 사용하여 레소시놀-포르말린 수지를 대체하여 RFL을 조제하여 2차처리하여 접착력을 부여하는 폴리에틸렌테레프탈레이트 타이어 코드를 제조하는 방법을 제안하고 있다. 그러나, 이 방법은 기존 레소시놀, 포르말린 등의 환경 유해물질을 사용하지 않음으로써 친환경적인 접착액을 조제할 수는 있으나, 사용된 폴리알콜과 방향족 알데히드가 물에 용해가 되지 않음으로써 아세트산, 에탄올 등의 유기용제에 접착액을 조제하여야 하며, 또한 접착액 반응을 위한 시간도 길어지며, 폴리페놀과 방향족 알데히드의 반응성이 상대적으로 낮아 상기 접착액으로 처리된 타이어 코드의 접착력도 낮을 수 있는 단점이 있다.In US Patent No. 2014/0308864 A1, a polyethylene terephthalate fiber is first treated with a mixture of epoxy and blocked isocyanate, and a polyol and an aromatic polyaldehyde are used to prepare a RFL by replacing the resorcinol-formalin resin. A method for producing a polyethylene terephthalate tire cord that is secondary treated to impart adhesion is proposed. However, this method can prepare environmentally friendly adhesives by not using environmentally harmful substances such as resorcinol and formalin, but acetic acid and ethanol are not dissolved in water because the polyalcohol and aromatic aldehydes are not dissolved in water. The adhesive liquid should be prepared in an organic solvent such as a solvent, and the time for the reaction of the adhesive liquid is also long, and the reactivity of the polyphenol and the aromatic aldehyde is relatively low, so that the adhesive strength of the tire cord treated with the adhesive liquid may be low. have.
국제 특허 WO 2014/091429 A1에서는 폴리글리세롤 에폭시(RASCHIG社 GE100)를 사용하고 폴리아민을 사용함으로써 레소시놀-포르말린 수지를 대체하는 접착액 제조방법이 제안되어 있다. 하지만 이 방법은 아라미드 섬유와 같이 표면이 극히 불활성이고, 결정화도가 매우 높아 에폭시의 내부침투가 이루어지지 않는 소재에 과량의 에폭시를 묻혀 접착력을 발현하는 방법이며, 폴리에틸렌테레프탈레이트에 적용할 경우에는 에폭시 침투량이 높아지게 되어 강성이 높아짐에 따라 공정성 저하, 내피로도 저하 등의 단점이 발생할 수 있다. 또한, 접착고무의 특성에 따라 접착력 편차가 심하게 발생하는 단점도 있다.International patent WO 2014/091429 A1 proposes a method for preparing an adhesive solution to replace resorcinol-formalin resin by using polyglycerol epoxy (RAS100, GE100) and polyamine. However, this method is an inert surface such as aramid fiber, and the crystallinity is very high, the method of expressing the adhesive force by embedding excess epoxy in the material that does not penetrate the epoxy, the epoxy penetration amount when applied to polyethylene terephthalate As the stiffness increases, the disadvantages such as lowering of fairness and lowering of fatigue may occur. In addition, there is a disadvantage in that the adhesive force deviation occurs badly depending on the characteristics of the adhesive rubber.
또한 국제 특허 WO2014/091376 A1에서는 수용성 아크릴 수지(BASF社, Acrodur 950)와 글리세롤 에폭시(Nagase Chemtex社, EX-313)를 사용하여 레소시놀-포르말린 수지를 대체할 수 있는 친환경적인 접착액에 대해 제안하고 있다. 이 방법은 아크릴 수지와 에폭시의 반응에 의해 나일론66, 레이온과 같은 반응기를 가진 섬유의 경우에 낮은 Dip Pick Up(DPU)에서도 접착력을 발현할 수 있다는 장점이 있으나, 폴리에틸렌테레프탈레이트와 같이 표면이 불활성인 경우 접착력이 낮은 단점이 있다. 또한, 아크릴 수지의 높은 반응성으로 인하여 조제 시에 pH를 염기성으로 민감하게 조절하여야 하며, pH 조절을 하지 않을 경우에는 라텍스와 반응에 의하여 응집물(Coagulum)이 발생하여 접착액을 사용할 수 없다는 단점이 있다.In addition, the international patent WO2014 / 091376 A1 discloses an environmentally friendly adhesive liquid that can replace the resorcinol-formalin resin using water-soluble acrylic resin (BASF, Acrodur 950) and glycerol epoxy (Nagase Chemtex, EX-313). I'm proposing. This method has the advantage of expressing adhesion even at low Dip Pick Up (DPU) in the case of fibers having a reactor such as nylon 66 and rayon by the reaction of acrylic resin and epoxy, but the surface is inert like polyethylene terephthalate. In case of having a low adhesive strength. In addition, due to the high reactivity of the acrylic resin, the pH should be sensitively adjusted at the time of preparation, and when the pH is not adjusted, coagulum is generated by reaction with latex, and thus adhesives cannot be used. .
통상적으로 2차 처리액인 RFL 조제시, 환경 유해 물질인 레소시놀, 포르말린, 암모니아 등을 사용하고 있다. 포르말린은 1차 발암물질로 등록되어 있으며, 암모니아는 악취 등을 유발하고 있다. 따라서 유럽 및 미국 등 전 세계적으로 REACH등의 규제에 의거하여 2019년 레소시놀 및 포르말린 사용을 금지할 예정으로 있으며, 이런 환경 유해 물질을 사용하지 않는 친환경적인 2차 처리액의 개발이 요구되어 지고 있는 것이 현실이다.Typically, when preparing RFL, which is a secondary treatment liquid, resorcinol, formalin, ammonia, etc., which are environmentally harmful substances, are used. Formalin is registered as a primary carcinogen, and ammonia causes odors. Therefore, the use of resorcinol and formalin in 2019 will be banned in accordance with the REACH regulations in Europe and the United States, and the development of eco-friendly secondary treatment liquid that does not use such environmentally harmful substances is required. It is a reality.
본 발명은 폴리에스테르 섬유의 표면에 환경 친화적인 접착액을 처리한 폴리에스테르 섬유, 이의 제조방법 및 이를 포함하는 타이어 코드에 관한 것으로, 반응성이 없는 폴리에스테르 섬유 표면에 반응성을 부여하여 고무와 섬유 간의 접착력을 높이고, 타이어 코드의 강성을 낮추고 내열성 및 내피로성을 향상시켜, 타이어 고속 주행시 발생되는 고무와 섬유의 박리현상을 방지할 수 있는 고성능 타이어 코드를 제조할 수 있는 폴리에스테르 섬유, 이의 제조방법 및 이를 포함하는 타이어 코드를 제공하는 것을 목적으로 한다.The present invention relates to a polyester fiber treated with an environmentally friendly adhesive liquid on the surface of the polyester fiber, a method of manufacturing the same and a tire cord including the same. Polyester fiber which can manufacture high performance tire cord which can improve the adhesive force, reduce the rigidity of tire cord, improve heat resistance and fatigue resistance, and prevent the peeling phenomenon of rubber and fiber generated at high speed of tire running, its manufacturing method and An object of the present invention is to provide a tire cord including the same.
상기한 목적을 달성하기 위하여, 본 발명은 블록킹된 디이소시아네이트 및 에폭시 화합물을 포함하는 1차 처리액을 제조하는 단계; 폴리에스테르 연사코드에 인장력을 가하면서 상기 1차 처리액에 통과시키는 단계; 상기 1차 처리액을 통과한 섬유를 건조 및 열처리하는 단계; 열처리된 폴리에스테르 섬유를 에폭시화된 페놀수지와 말레익안하이드라이드폴리부타디엔 공중합체를 포함하는 2차 처리액에 통과시키는 단계; 및 상기 2차 처리액을 통과한 섬유를 건조시키고 안정화시키는 단계를 포함하는 폴리에스테르 섬유의 제조방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of preparing a first treatment liquid comprising a blocked diisocyanate and an epoxy compound; Passing through the primary treatment liquid while applying a tensile force to the polyester twisted cord; Drying and heat-treating the fibers having passed through the primary treatment liquid; Passing the heat treated polyester fiber through a secondary treatment liquid comprising an epoxidized phenolic resin and a maleic hydride polybutadiene copolymer; And it provides a method for producing a polyester fiber comprising the step of drying and stabilizing the fiber passed through the secondary treatment liquid.
여기서, 상기 에폭시화된 페놀 수지와 말레익안하이드라이드폴리부타디엔 공중합체는 중량비로 1:1 내지 5:1인 것이 바람직하다.Here, the epoxidized phenol resin and maleic hydride polybutadiene copolymer is preferably 1: 1 to 5: 1 by weight.
또한, 본 발명은 상기 제조방법으로 제조되고, 하기의 물성을 가지는 것을 특징으로 하는 폴리에스테르 타이어 코드도 제공한다.The present invention also provides a polyester tire cord, which is produced by the above production method and has the following physical properties.
(1) H-테스트로 측정된 고무와의 초기 접착력이 16kgf 이상이며, 내열 접착력이 10kgf 이상(1) Initial adhesion with rubber measured by H-test is 16kgf or more, heat resistance adhesion is 10kgf or more
(2) 디스크 유형의 피로 시험기를 이용하여 측정된 피로 시험 실시 후 섬유의 강력잔존율이 60% 이상(2) The strength of fiber remaining more than 60% after the fatigue test measured by the disk type fatigue tester
본 발명에 따른 폴리에스테르 섬유는 2차 처리액으로 고무와의 상호작용을 할 수 있는 에폭시화된 페놀 수지 및 고무 라텍스와 상기 에폭시화된 페놀 수지와 고무라텍스의 결합력을 증가시킬 수 있는 Maleic Anhydride-Polybutadiene 공중합체의 혼합물을 이용하여 처리함으로써, 높은 내열 접착력과 고무 커버리지 및 우수한 내열특성, 내피로성을 발현할 수 있으며, 이로 인하여 고성능 타이어의 제조가 가능하다.The polyester fiber according to the present invention is a maleic anhydride- which can increase the binding force between the epoxidized phenolic resin and rubber latex and the epoxidized phenolic resin and rubber latex which can interact with rubber as a secondary treatment liquid. By treating with a mixture of polybutadiene copolymers, high heat adhesion, rubber coverage, excellent heat resistance, and fatigue resistance can be exhibited, which makes it possible to manufacture high-performance tires.
또한, 본 발명에서 사용하는 2차 처리액은 혼합 후에 바로 사용이 가능하기때문에 반응 숙성시간이 필요하지 않고, 처리액 제조 시에 환경규제물질을 전혀 사용하지 않음으로써, 친환경적이며 외부 환경에 따른 영향도를 최소화하여 균일한 처리액의 부착을 가능하게 함으로써, 제조공정성 및 생산 비용을 절감할 수 있고 품질 균일성이 향상된 폴리에스테르 섬유용 처리액을 제공할 수 있다.In addition, since the secondary treatment solution used in the present invention can be used immediately after mixing, it does not require a reaction aging time and does not use any environmental regulatory substances in the preparation of the treatment solution. By minimizing the degree and enabling the uniform treatment liquid to be attached, it is possible to reduce the manufacturing processability and the production cost, and to provide the treatment liquid for the polyester fiber with improved quality uniformity.
도 1은 본 발명의 2차 처리액의 말레익안하이드라이드폴리부타디엔 공중합체(Ricobond 7004)의 화학구조이다.1 is a chemical structure of maleic hydride polybutadiene copolymer (Ricobond 7004) of the secondary treatment solution of the present invention.
이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
본 발명은 폴리에스테르 섬유, 이의 제조방법 및 이를 포함하는 타이어 코드를 제공한다.The present invention provides a polyester fiber, a manufacturing method thereof and a tire cord comprising the same.
본 발명의 폴리에스테르 섬유의 제조방법은, 본 발명은 블록킹된 디이소시아네이트 및 에폭시 화합물을 포함하는 1차 처리액을 제조하는 단계; 폴리에스테르연사코드에 인장력을 가하면서 상기 1차 처리액에 통과시키는 단계; 상기 1차 처리액을 통과한 섬유를 건조 및 열처리하는 단계; 열처리된 폴리에스테르 섬유를 에폭시화된 페놀 수지와 Maleic Anhydride-Polybutadiene 공중합체를 포함하는 2차 처리액에 통과시키는 단계; 및 상기 2차 처리액을 통과한 섬유를 건조시키고 안정화시키는 단계를 포함한다.Method for producing a polyester fiber of the present invention, the present invention comprises the steps of preparing a primary treatment liquid containing a blocked diisocyanate and an epoxy compound; Passing through the primary treatment liquid while applying a tensile force to the polyester yarn cord; Drying and heat-treating the fibers having passed through the primary treatment liquid; Passing the heat treated polyester fiber through a secondary treatment liquid comprising an epoxidized phenol resin and a Maleic Anhydride-Polybutadiene copolymer; And drying and stabilizing the fibers passing through the secondary treatment liquid.
본 발명은 폴리에스테르 섬유와 고무와의 접착을 위하여 블록킹된 이소시아네이트 및 에폭시를 주성분으로 하는 1차 처리액을 사용한다. 이후에 에폭시화된 페놀 수지와 Maleic Anhydride-Polybutadiene 공중합체의 혼합액에 고무 라텍스를 첨가하여 고무와의 상호작용을 할 수 있는 2차 처리액을 폴리에스테르 섬유에 처리한다.The present invention uses a primary treatment liquid mainly composed of blocked isocyanates and epoxy to bond polyester fibers and rubber. Thereafter, a rubber latex is added to the mixed solution of the epoxidized phenolic resin and the maleic anhydride-polybutadiene copolymer to treat the polyester fiber with a secondary treatment solution capable of interacting with the rubber.
먼저, 1차 처리액을 제조하기 위하여, 1차 처리액 100중량%를 기준으로 블록킹된 디이소시아네이트 0.5 내지 4.0중량%, 에폭시 화합물 0.3 내지 1.5중량%, 비닐피리딘라텍스 0.5 내지 1.5중량%, 내열첨가제 0.3 내지 0.6중량% 및 나머지는 물을 포함한다.First, in order to prepare a primary treatment solution, 0.5 to 4.0 wt% of diisocyanate blocked, based on 100 wt% of the primary treatment solution, 0.3 to 1.5 wt% epoxy compound, 0.5 to 1.5 wt% vinylpyridine latex, heat additive 0.3 to 0.6% by weight and the balance comprises water.
이때, 상기 2차 처리액은 고무 라텍스와 에폭시화된 페놀 수지의 결합력을 증가시키기 위하여, 말레익안하이드라이드폴리부타디엔 공중합체를 포함할 수 있다.At this time, the secondary treatment solution may include a maleic anhydride polybutadiene copolymer in order to increase the bonding strength of the rubber latex and the epoxidized phenol resin.
본 발명에 따른 폴리에스테르 섬유에 1차 처리액 및 상기 에폭시화된 페놀 및 말레익안하이드라이드폴리부타디엔 공중합체와 라텍스로 구성된 2차 처리액을 처리하는 단계에 대해 설명하면 다음과 같다.Referring to the step of treating the polyester fiber according to the present invention and the secondary treatment liquid consisting of the epoxidized phenol and maleic hydride polybutadiene copolymer and latex as follows.
방사 공정을 통하여 제조된 폴리에스테르 섬유를 연사 및 제직한 후, 열처리하는 단계에 대해 설명하면 다음과 같다. 제조된 타이어 코드용 원사를 다이렉트 연사기를 이용하여 Z방향으로 하연, S방향으로 상연 2합으로 연사한 후 제직기(Weaving Machine)를 이용하여 제직함으로써 생지(Raw Fabric)를 제조한다. 이렇게 제조된 타이어 코드용 생지는 열처리공정 중에서 블로킹된 이소시아네이트와 에폭시로 구성된 1차 처리액으로 처리된다. 이후에 건조영역에서 수분이 제거되며 건조온도는 140 내지 180℃가 바람직하며, 20 내지 150초 동안 건조된다. 이후에 160 내지 250℃ 온도에서 20 내지 150초 동안 열처리를 통하여 블록킹된 디이소시아네이트가 해리되어 반응성을 가짐으로 에폭시와 화학반응을 통하여 섬유 표면에 반응성을 부여하게 된다.When weaving and weaving the polyester fiber produced by the spinning process, the heat treatment will be described as follows. Raw fabric for a tire cord is twisted with a direct weaving machine in the lower direction in the Z direction and the upper edge in two in the S direction, and then weaved using a weaving machine to produce a raw fabric. The dough for tire cords thus prepared is treated with a primary treatment liquid composed of blocked isocyanates and epoxy during the heat treatment process. After the water is removed in the drying zone and the drying temperature is preferably 140 to 180 ℃, it is dried for 20 to 150 seconds. Thereafter, the diisocyanate blocked through heat treatment at a temperature of 160 to 250 ° C. for 20 to 150 seconds is dissociated to give reactivity to the fiber surface through chemical reaction with epoxy.
이후, 2차 처리액을 제조하기 위하여, 2차 처리액 100중량%를 기준으로 에폭시화된 페놀 수지 0.5 내지 10중량%, 말레익안하이드라이드폴리부타디엔 공중합체 0.1 내지 3중량%, 비닐피리딘라텍스 15 내지 20중량%, 스타이렌-부타디엔 라텍스 0 내지 5중량%를 포함한다.Then, to prepare a secondary treatment solution, 0.5 to 10% by weight of epoxidized phenolic resin, 0.1 to 3% by weight maleic hydride polybutadiene copolymer, based on 100% by weight of the secondary treatment solution, vinylpyridine latex 15 To 20% by weight, and 0 to 5% by weight of styrene-butadiene latex.
상기 에폭시화된 페놀 수지는 고무와의 상호작용을 할 수 있는 역할을 한다.The epoxidized phenolic resin serves to interact with the rubber.
이러한 에폭시화된 페놀 수지는 비스페놀-A와 에피클로로히드린, 노블락과 에피클로로히드린, 또는 레졸과 에피클로로히드린으로 합성된 에폭시수지에 고분자량의 폴리이소시아네이트를 말단에 결합시키고 부탄올 등의 유기 용매에 분산시켜 제조할 수 있다. 또는, 비스페놀-A와 에피클로로히드린을 사용하여 합성된 액상 에폭시수지에 노블락 또는 레졸 등을 부가중합하여 고분자의 에폭시를 합성한 이 후 레소시놀, 페놀, 카플로락탐 등으로 블록킹된 이소시아네이트를 말단에 결합시키고 부탄올 등의 유기 용매에 분산시켜 제조할 수 있다. 또 다른 합성 방법은 비스페놀-A와 에피클로로히드린을 사용하여 노볼락 또는 레졸 형태의 에폭시를 합성한 이 후 레소시놀 또는 레소시놀-포르말린 수지를 말단에 결합시키고 유기 용매에 분산시켜 제조할 수 있다. 상기의 합성방법 이외에도 노볼락 또는 레졸 형태의 에폭시와 페놀 수지를 물, 조용매(Co-solvent), 분산제와 함께 혼합한 후 가열하면서 매우 강한 전단력을 가하여 혼합액을 제조할 수 있다. 이 혼합액은 작은 입자상태로 균일한 분산성을 가지게 되며 냉각과정에서 분산제에 의해 안정한 상태로 유지될 수 있다. 이 때 조용제(Co-solvent)로는 알콜류 또는 에테르 글리콜(Glycol Ether)이 사용될 수 있다.Such epoxidized phenolic resin is a bisphenol-A and epichlorohydrin, a noble and epichlorohydrin, or a high molecular weight polyisocyanate at the end of the epoxy resin synthesized from resol and epichlorohydrin, and organic such as butanol It can be prepared by dispersing in a solvent. Alternatively, the polymerized epoxy is synthesized by addition polymerization of a novolac or resol to a liquid epoxy resin synthesized using bisphenol-A and epichlorohydrin, and then an isocyanate blocked with resorcinol, phenol, caprolactam or the like is prepared. It can be produced by binding to the terminal and dispersing in an organic solvent such as butanol. Another synthesis method is prepared by synthesizing a novolak or resol type epoxy using bisphenol-A and epichlorohydrin and then binding the resorcinol or resorcinol-formalin resin to the ends and dispersing it in an organic solvent. Can be. In addition to the synthesis method described above, a mixed solution may be prepared by applying a very strong shearing force while mixing a novolak or a resol-type epoxy and phenol resin together with water, a co-solvent, and a dispersant and heating. This mixed solution has a uniform dispersibility in the form of small particles and can be maintained in a stable state by the dispersant during the cooling process. At this time, a co-solvent may be used alcohols or ether glycol (Glycol Ether).
상기 에폭시화된 페놀 수지는 2차 처리액 100중량%를 기준으로 0.5 내지 10 중량% 포함하는 것이 바람직하다. 에폭시 화합물의 함량이 0.5중량% 미만일 경우에는 섬유에 충분한 반응성을 부여하여 고무와의 접착력을 발현하기 어려우며, 10중량%를 초과하는 경우에는 높은 강성으로 인하여 가공성이 저하되고 코드의 내피로 특성이 저하되며 제조비용도 높아지게 된다.The epoxidized phenol resin preferably contains 0.5 to 10% by weight based on 100% by weight of the secondary treatment liquid. When the content of the epoxy compound is less than 0.5% by weight, it is difficult to express sufficient adhesiveness to the fiber by providing sufficient reactivity to the fiber, and when it exceeds 10% by weight, the workability is decreased due to the high rigidity and the fatigue resistance of the cord is reduced. In addition, manufacturing costs will increase.
또한, 상기 에폭시화된 페놀 수지와 Maleic Anhydride-Polybutadiene 공중합체는 중량비로 1:1 내지 5:1인 것이 바람직하다. 만약, 상기 범위를 벗어나게 되면 충분한 접착력이 발현되지 않을 뿐만 아니라, 강성이 너무 높아 타이어 코드의 주요 요구 특성 중 하나인 내피로성이 떨어지게 되어 타이어 내구성이 떨어지는 결과를 초래하게 된다.In addition, the epoxidized phenol resin and the maleic anhydride-polybutadiene copolymer are preferably 1: 1 to 5: 1 by weight. If it is out of the above range, not only sufficient adhesion is not expressed, but also the rigidity is so high that fatigue resistance, which is one of the main required characteristics of the tire cord, is degraded, resulting in deterioration of tire durability.
상기 비닐피리딘 라텍스의 함량은 1차 처리액 100중량%를 기준으로 15 내지 20중량%인 것이 바람직하며, 비닐피리딘 라텍스의 함량이 15중량% 이하인 경우에는 고무와의 충분한 접착력을 발현할 수 없으며, 20중량% 이상인 경우에는 초기접착력은 상승되지만 라텍스층이 두껍게 형성되어 고온에서 라텍스층에서의 박리현상이 발생할 수 있으며 높은 부착량으로 인하여 강성이 증가하게 되어 내피로성이 저하되며, 또한 열처리 설비 롤러에 라텍스가 부착되어 작업성이 저하되거나 최종 제품의 불량이 증가하게 된다.The content of the vinylpyridine latex is preferably 15 to 20% by weight based on 100% by weight of the primary treatment solution, and when the content of the vinylpyridine latex is 15% by weight or less, sufficient adhesion with rubber may not be expressed. If it is more than 20% by weight, the initial adhesive strength is increased, but the latex layer is formed thick, which may cause peeling phenomenon in the latex layer at a high temperature, and the stiffness is increased due to the high adhesion amount, thereby reducing the fatigue resistance. May cause deterioration in workability or increase in final product defects.
이와 같이 제조된 폴리에스테르 섬유는 고무와의 상호작용을 할 수 있는 에폭시화된 페놀 수지 및 고무 라텍스와 상기 에폭시화된 페놀 수지와 고무라텍스의 결합력을 증가시킬 수 있는 Maleic Anhydride-Polybutadiene 공중합체의 혼합물을 이용하여 처리함으로써, 높은 내열 접착력과 고무 커버리지 및 우수한 내열특성, 내피로성을 발현할 수 있으며, 이로 인하여 고성능 타이어의 제조가 가능하다.The polyester fiber thus prepared is a mixture of epoxidized phenolic resins and rubber latexes that can interact with rubber and maleic anhydride-polybutadiene copolymers that can increase the bonding strength of the epoxidized phenolic resins and rubber latex. By treating with, high heat adhesive strength, rubber coverage, excellent heat resistance, and fatigue resistance can be expressed, and thus high performance tires can be manufactured.
또한, 본 발명에서 사용하는 2차 처리액은 혼합 후에 바로 사용이 가능하기때문에 반응 숙성시간이 필요하지 않고, 처리액 제조 시에 환경규제물질을 전혀 사용하지 않음으로써, 타이어코드 친환경 접착액이며 외부 환경에 따른 영향도를 최소화하여 균일한 처리액의 부착을 가능하게 함으로써, 제조공정성 및 생산 비용을 절감할 수 있고 품질 균일성이 향상된 폴리에스테르 섬유용 처리액을 제공할 수 있다.In addition, since the secondary treatment solution used in the present invention can be used immediately after mixing, it does not require a reaction aging time, and does not use any environmental regulatory substances in the preparation of the treatment solution. By minimizing the influence of the environment to enable uniform deposition of the treatment solution, it is possible to reduce the manufacturing processability and production cost, and to provide a treatment solution for the polyester fiber with improved quality uniformity.
이하, 본 발명을 실시예를 통해 구체적으로 설명하나, 하기 실시예 및 실험예는 본 발명의 한 형태를 예시하는 것에 불과할 뿐이며, 본 발명의 범위가 하기 실시예 및 실험예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of Examples, but the following Examples and Experimental Examples are only illustrative of one embodiment of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples. .
실시예 1Example 1
1차 처리액은 물 96.5중량%, 에폭시 화합물 0.5중량%, 디이소시아네이트 1.0 중량%, 비닐피리딘라텍스 1.5중량% 및 내열첨가제 0.5중량%를 혼합하여 제조하였으며, 2차 처리액은 조성물의 함량을 하기 표 1과 같이 조절하여 제조하였다. 타이어코드용 폴리에스테르 섬유 1500데니어 2ply를 상연수 37(Twist/10cm), 하연수 37(Twist/10cm) 으로 하여 생산된 연사코드를 0.1g/d의 장력을 가하면서 상기 1차처리액에 침지시켜 통과시키고, 건조영역에서 160℃로 2분간 건조시키고 245℃로 열처리하였다. 상기 열처리과정을 거친 폴리에스테르 섬유는 다시 2차 처리액인 에폭시화된 페놀 수지(Allnex社 VPW-1942) 및 비닐피리딘라텍스와 스타이렌-부타디엔 라텍스 및 상기 에폭시화된 페놀 수지와 고무라텍스의 결합력을 증가시킬 수 있는 말레익안하이드라이드폴리부타디엔 공중합체(Cray Valley社의 Ricobond 7004) 혼합물로 구성된 접착제 용액에 함침된 후에 160℃ 온도에서 건조하고, 245℃ 온도에서 안정화함으로써 폴리에스테르 타이어 코드로 제조되었다.The primary treatment solution was prepared by mixing 96.5 wt% water, 0.5 wt% epoxy compound, 1.0 wt% diisocyanate, 1.5 wt% vinylpyridine latex, and 0.5 wt% heat resistant additive. It was prepared by adjusting as shown in Table 1. The twisted yarn cord produced by using 1500 denier 2ply of polyester fiber for tire cords as 37 (Twist / 10cm) and 37 (Twist / 10cm) soft water was immersed in the primary treatment liquid while applying a tension of 0.1 g / d. Passed through, dried at 160 ° C. for 2 minutes and heat treated at 245 ° C. After the heat treatment process, the polyester fiber was further subjected to the binding treatment between the epoxidized phenol resin (Allnex Corp. VPW-1942), vinylpyridine latex and styrene-butadiene latex, and the epoxidized phenolic resin and rubber latex. It was made into a polyester tire cord by being impregnated into an adhesive solution consisting of an increaseable maleic hydride polybutadiene copolymer (Ricobond 7004 from Cray Valley), followed by drying at 160 ° C. and stabilization at 245 ° C.
실시예 2 비교예 1,2 및 3Example 2 Comparative Examples 1,2 and 3
2차 처리액 조성물의 함량을 하기 표 1과 같이 조절한 것을 제외하고는, 실시예 1과 동일한 과정으로 폴리에틸렌테레프탈레이트 타이어 코드를 제조하였다.A polyethylene terephthalate tire cord was manufactured in the same manner as in Example 1, except that the content of the secondary treatment liquid composition was adjusted as shown in Table 1 below.
비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 실시예 1Example 1 실시예 2Example 2
2차액조성(중량%)Secondary liquid composition (% by weight) 물water 76.576.5 75.075.0 77.577.5 76.576.5 77.577.5
가성소다Caustic soda 0.10.1 0.40.4 -- -- --
레소시놀Resorcinol 2.42.4 3.03.0 -- -- --
포르말린formalin 0.80.8 1.21.2 -- -- --
에폭시화페놀수지Epoxylated Phenolic Resin -- -- 2.52.5 2.52.5 4.04.0
Ricobond7004Ricobond7004 -- -- -- 1.01.0 1.01.0
비닐피리딘라텍스Vinyl pyridine latex 20.020.0 17.517.5 20.020.0 17.517.5 15.015.0
SBR 라텍스SBR Latex -- 2.52.5 -- 2.52.5 2.52.5
암모니아ammonia 0.20.2 0.40.4 -- -- --
실험예Experimental Example
실시예 1 내지 2, 비교예 1 내지 3에서 각각 제조된 폴리에스테르 타이어코드의 물성은 하기와 같은 방법을 이용하여 평가하였으며, 그 결과는 하기 표 2에 나타내었다.The physical properties of the polyester tire cords prepared in Examples 1 to 2 and Comparative Examples 1 to 3, respectively, were evaluated using the following method, and the results are shown in Table 2 below.
(a) 접착력(kgf) 평가방법: H-테스트(H-Test)(a) Evaluation method of adhesive force (kgf): H-Test
열처리 코드와 고무의 접착력을 나타내는 방법으로서, 코드를 고무블럭에 넣어 160℃, 20분(초기) 또는 170℃, 60분(내열)으로 50kgf/㎠의 압력으로 가류한 이후에, 인스트롱사의 저속 신장형 인장시험기를 이용하여 인장속도 200m/min로 접착력을 측정한다. 같은 시험을 10회 실시하여 평균값을 구하였다. 이 외 방법은 ASTM D4776-98에 따라 시행되었다.As a method of showing the adhesive strength between the heat treated cord and the rubber, the cord is placed in a rubber block and vulcanized at a pressure of 50 kgf / cm 2 at 160 ° C. for 20 minutes (initial) or 170 ° C. for 60 minutes (heat resistance). Adhesion is measured at a tensile rate of 200 m / min using an elongation type tensile tester. The same test was carried out 10 times to obtain an average value. Other methods were performed according to ASTM D4776-98.
(b) 내피로성 평가방법(b) Evaluation method of fatigue resistance
열처리 코드의 외부 응력에 대한 저항값을 나타내는 척도로서, 타이어 주행조건을 모사하여 실시한다. 본 발명에서 디스크 내피로도 평가는 우에시마社(Ueshima Seisakusho Co., Ltd.) FT-6110을 사용하여 평가하였다. 피로시험 조건은 인장 6%, 압축 12%로 실시하였으며 2500rpm으로 120℃에서 8시간 피로를 가한 이후에 코드를 채취하여 강력을 측정하여 피로 전 원강력에 대한 강력잔존율을 측정한다. 코드 강력 측정 방법은 ASTM D885방법에 준하여 실시하였다.A measure of the resistance value against external stress of the heat treatment cord, which simulates tire running conditions. In the present invention, the evaluation of the disc fatigue resistance was evaluated using Ueshima Seisakusho Co., Ltd. FT-6110. Fatigue test conditions were 6% tensile and 12% compression. After 8 hours of fatigue at 120 ° C at 2500rpm, the cord was collected and the strength was measured. Cord strength measurement method was carried out according to the ASTM D885 method.
비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 실시예 1Example 1 실시예 2Example 2
DPU (%)DPU (%) 2.72.7 3.13.1 2.52.5 2.62.6 2.82.8
초기접착력(Pull-out, kgf)Initial adhesive force (pull-out, kgf) 16.516.5 17.017.0 18.018.0 19.019.0 17.517.5
내열접착력(Pull-out, kgf)Pull-out, kgf 9.59.5 10.010.0 11.811.8 12.312.3 11.511.5
내피로도 (%)DiskEndo fatigue (%) Disk 62.362.3 60.160.1 69.169.1 74.774.7 70.070.0
상기 표 2의 시험 결과로 볼 때, 본 발명(실시예1,2)에 따른 폴리에스테르 타이어 코드는 말레익안하이드라이드폴리부타디엔 공중합체를 첨가하지 않은 비교예에 비하여 접착력 및 내피로도가 향상됨을 알 수 있다.As a result of the test results in Table 2, the polyester tire cord according to the present invention (Examples 1 and 2) shows that the adhesion and fatigue resistance are improved as compared with the comparative example without addition of the maleic hydride polybutadiene copolymer. Can be.

Claims (3)

  1. 블록킹된 디이소시아네이트 및 에폭시 화합물을 포함하는 1차 처리액을 제조하는 단계;Preparing a first treatment liquid comprising a blocked diisocyanate and an epoxy compound;
    폴리에스테르 연사코드에 인장력을 가하면서 상기 1차 처리액에 통과시키는 단계;Passing through the primary treatment liquid while applying a tensile force to the polyester twisted cord;
    상기 1차 처리액을 통과한 섬유를 건조 및 열처리하는 단계;Drying and heat-treating the fibers having passed through the primary treatment liquid;
    열처리된 폴리에스테르 섬유를 에폭시화된 페놀 수지 및 말레익안하이드라이드폴리부타디엔(Maleic Anhydride-Polybutadiene) 공중합체를 포함하는 2차 처리액에 통과시키는 단계; 및Passing the heat treated polyester fiber through a secondary treatment liquid comprising an epoxidized phenolic resin and a maleic anhydride-polybutadiene copolymer; And
    상기 2차 처리액을 통과한 섬유를 건조시키고 안정화시키는 단계를 포함하는 폴리에스테르 섬유의 제조방법.Method for producing a polyester fiber comprising the step of drying and stabilizing the fiber passed through the secondary treatment liquid.
  2. 제1항에 있어서,The method of claim 1,
    상기 에폭시화된 페놀 수지와 말레익안하이드라이드폴리부타디엔(Maleic Anhydride-Polybutadiene) 공중합체는 중량비로 1:1 내지 5:1인 것을 특징으로 하는 폴리에스테르 섬유의 제조방법.The epoxidized phenol resin and maleic anhydride polybutadiene (Maleic Anhydride-Polybutadiene) copolymer is a method of producing a polyester fiber, characterized in that 1: 1 to 5: 1 by weight.
  3. 제1항에 기재된 방법으로 제조된 폴리에스테르 섬유를 포함하고, 하기의 물성을 가지는 것을 특징으로 하는 폴리에스테르 타이어 코드.A polyester tire cord comprising the polyester fiber produced by the method according to claim 1 and having the following physical properties.
    (1) H-테스트로 측정된 고무와의 초기 접착력이 16kgf 이상이며, 내열 접착력이 10kgf 이상, (2) 디스크 유형의 피로 시험기를 이용하여 측정된 피로 시험 실시 후 섬유의 강력잔존율이 60% 이상(1) Initial adhesion with rubber measured by H-test is 16kgf or more, heat resistance 10kgf or more, and (2) 60% strength strength of fiber after fatigue test measured using a fatigue tester of disk type. More than
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