WO2013100212A1 - Method for manufacturing an aramid composite - Google Patents

Method for manufacturing an aramid composite Download PDF

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Publication number
WO2013100212A1
WO2013100212A1 PCT/KR2011/010128 KR2011010128W WO2013100212A1 WO 2013100212 A1 WO2013100212 A1 WO 2013100212A1 KR 2011010128 W KR2011010128 W KR 2011010128W WO 2013100212 A1 WO2013100212 A1 WO 2013100212A1
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WO
WIPO (PCT)
Prior art keywords
aramid
thermoplastic resin
fabric
aramid fabric
resin molding
Prior art date
Application number
PCT/KR2011/010128
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French (fr)
Korean (ko)
Inventor
한인식
Original Assignee
코오롱인더스트리(주)
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Application filed by 코오롱인더스트리(주) filed Critical 코오롱인더스트리(주)
Priority to PCT/KR2011/010128 priority Critical patent/WO2013100212A1/en
Publication of WO2013100212A1 publication Critical patent/WO2013100212A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to a method for producing an aramid composite, specifically relates to a method for producing an aramid composite excellent in tensile strength and impact strength is bonded to each other with excellent adhesive strength of the aramid fabric and the thermoplastic resin molding.
  • the aramid composite refers to a molded article in which the aramid fabric and the thermoplastic resin molded article are integrally bonded.
  • extreme sports which risk adventure and enjoy adventure, have become popular. Examples of such extreme sports include inline skating, rock climbing, mountain biking, wakeboarding, and the like.
  • Such protective equipment is manufactured using a general polymer resin such as nylon or polyester resin.
  • a general polymer resin such as nylon or polyester resin.
  • a product using the general polymer resin has a low impact resistance, it is not enough to protect the body from an external shock, if the situation is severe damage to the product was damaged.
  • the strength when used for a long time there is a problem that the strength is lowered, the safety performance falls.
  • aramid fabric In addition to such sporting goods, other conventional protective equipment materials, such as bumpers, which can minimize life and property damage in the event of a vehicle crash, are coated on aramid fabric by coating a polypropylene resin solution on the aramid fabric.
  • Aramid composites having a structure in which a polypropylene resin layer has been formed and adhered have been used.
  • the conventional aramid composite has no chemical structure functional group of the polypropylene resin, the interfacial adhesion between the aramid fabric and the polypropylene resin layer is poor, and the tensile strength and the impact strength of the aramid composite are greatly reduced. There was a problem.
  • the present invention is to provide a method for improving the adhesion strength between the aramid fabric and the thermoplastic resin molding constituting the aramid composite.
  • the aramid fabric when preparing the aramid composite bonded to the aramid fabric and the thermoplastic resin molding, the aramid fabric is immersed in the epoxy solution (Dipping) to impregnate the epoxy solution in the aramid fabric, then the epoxy solution By adhering the impregnated aramid fabric and the thermoplastic resin molding, the interfacial adhesion strength of the aramid fabric and the thermoplastic resin molding is improved.
  • the present invention further improves the adhesion strength between the aramid fabric and the thermoplastic resin molding by modifying the surface of the aramid fabric impregnated with the epoxy solution before bonding the aramid fabric impregnated with the epoxy solution and the thermoplastic resin molding.
  • thermoplastic resin molding adhered to the aramid fabric is heat-treated at the crystallization temperature of the thermoplastic resin constituting the thermoplastic resin molding to isothermally crystallize the thermoplastic resin to improve the crystallinity of the thermoplastic resin affecting the physical properties of the composite material.
  • the adhesion strength between the aramid fabric and the thermoplastic resin molding is further improved.
  • the aramid composite prepared by the present invention is excellent in the adhesive strength between the aramid fabric and the thermoplastic resin molding. Therefore, the aramid composite prepared by the present invention is excellent in tensile strength and impact strength is useful as a safety protective equipment material for sports and bumpers.
  • the aramid fabric is composed of aramid fibers, but depending on the use of the aramid composite may be configured by appropriately mixing the carbon fibers as a secondary component with the aramid fibers as a main component for improving the high compression.
  • the carbon fiber is preferably mixed and used in less than 50% by weight relative to the total weight of the aramid fabric.
  • the aramid fibers are produced by the following process. That is, a process for producing a wholly aromatic polyamide polymer by polymerizing an aromatic diamine and an aromatic dieside halide in a polymerization solvent containing N-methyl-2-pyrrolidone, dissolving this polymer in a concentrated sulfuric acid solvent to prepare a spinning dope. The process is completed by spinning the spinning dope through the spinneret and then solidifying the spinning material to produce a filament, and washing the filament with water, drying and heat treatment.
  • Aramid fibers prepared as described above will have a tensile strength of 20 ⁇ 28g / d and an elastic modulus of 400 ⁇ 1200g / d.
  • the protective pads When aramid fibers having these properties are used to make protective equipment such as helmets, knee pads and elbow pads, the protective pads have excellent impact strength and tensile strength to protect the body from injuries during sports activities. If it is applied to, etc., it can protect the life and property in the event of a traffic accident due to its excellent impact resistance strength.
  • the aramid fabric is produced using aramid fibers produced by the method described above.
  • the aramid fabric the aramid fibers may be aramid fabric woven by applying to warp and weft.
  • the aramid fabric may be plain, twill or satin tissue. Such a structure is formed with a warp and weft uniformly bent, so that when subjected to external force, it provides excellent impact resistance and tensile strength by uniformly dispersing the external force throughout the fabric.
  • the aramid fabric may be a mixed aramid fabric prepared by mixing the carbon fiber and the aramid fiber as described above.
  • the mixed aramid fabric can be prepared by mixing the aramid fibers and carbon fibers in the weft and warp appropriately.
  • it may be a mixed aramid fabric in which aramid yarn is applied to the warp yarn and carbon fiber is applied to the weft yarn, and may be a mixed aramid fabric in which carbon fiber is applied to the warp yarn and aramid fiber is applied to the warp yarn.
  • it may be an aramid fabric which applied the aramid yarn to the warp yarn and the carbon fiber and the aramid fiber to the weft alternately, it is not necessarily limited to these.
  • the aramid fabric is preferably 10 to 40 / / fabric density in the warp direction and weft direction respectively. If the fabric density in the warp direction and weft direction is less than 10 bones / inch, sufficient impact strength and tensile strength may not be obtained, whereas when the fabric density in the warp direction and weft direction exceeds 40 bones / inch, excessive density Due to this, weaving is lowered and bending is not easy, so moldability may be degraded.
  • the aramid fabric is preferably having a surface density of 130 ⁇ 500g / m2. If the surface density is lower than the above range, the space may be generated in the fabric and thus the impact strength may be reduced. If the surface density is higher than the above range, the fabrication may not be easy and the production efficiency may be greatly reduced.
  • the aramid fabric may include an aramid laminate in which the aramid fabric is laminated in several layers.
  • the protective equipment can more fully protect the body and property from strong external shocks.
  • the present invention includes modifying the surface of the aramid fabric impregnated with the epoxy solution prior to bonding the aramid fabric impregnated with the epoxy solution and the thermoplastic resin molding.
  • the surface modification treatment of the aramid fabric is a plasma treatment method for irradiating a plasma on the aramid fabric surface, a corona discharge treatment method for corona discharge treatment of the aramid fabric surface, or the aramid fabric is dipped in a coupling agent solution and dried or a coupling agent Coupling agent treatment such as coating or spraying the solution on aramid fabric and drying is used.
  • a silane compound of Formula 1 or a metal compound represented by Formula 2 may be used as the coupling agent.
  • Y- (R) n-SiX 3 (Y is one functional group selected from halogen atom, epoxy group, amino group, mercapto group, vinyl group, acryloyl group, R is a hydrocarbon group, X is the same or different alkoxy group , n is an integer of 0 or 1)
  • M (OR ') m, where m is an integer of 3 or 4, R' is a straight or branched alkyl group of 1 to 8 carbon atoms, and M is titanium or zirconium
  • the silane coupling agent represented by the formula (1) has a functional group, it can easily form various bonds with the bonding surface, thereby improving the adhesive strength between the aramid fabric and the thermoplastic resin molded product.
  • the metal oxide-based coupling agent represented by Chemical Formula 2 contains a metal such as titanium or zirconium, adjacent atoms may be easily charged, thereby increasing the bonding force between the aramid fabric and the thermoplastic resin molding. Therefore, it serves to improve the adhesive strength.
  • 3-glycidoxylpropyltrimethoxysilane which is a silane coupling agent, or zirconium ethoxide, which is a metal oxide coupling agent, is added to an aqueous solution of ethanol at a concentration of 1% by weight.
  • the aramid fabric surface when the aramid fabric surface is treated with oxygen as a reaction gas, the aramid fabric surface may generate a large amount of oxygen reactor, and the oxygen reactor may have high affinity with a coupling agent, thereby adhering. The strength can be greatly improved.
  • the plasma treatment process may be carried out under a nitrogen atmosphere and a reduced pressure of 100 to 3000 watts and irradiation time of 5 to 30 minutes. If the work rate is too low or the irradiation time is too short, less reactors may be produced, whereas if the work rate is too high or the irradiation time is too long, the aramid fabric may be damaged. Meanwhile, the plasma treatment process may be performed in a nitrogen atmosphere to prevent the reduction of the reactor generated on the aramid fabric surface after the plasma treatment, and the plasma treatment process may be performed under reduced pressure to prevent the introduction of moisture.
  • a high AC voltage is applied between two electrodes while maintaining room temperature and normal pressure to induce corona discharge, and a sample having a voltage of 1,000 to 50,000 V after placing the sample between the two electrodes and
  • the irradiation time of 1 to 60 minutes may be carried out through a process of corona treatment of the surface of the aramid fabric.
  • thermoplastic resin solution is coated on the fabric impregnated with the epoxy solution, and then heat-treated at an appropriate crystallization temperature to express the crystallinity of the coated thermoplastic resin to the maximum.
  • the method of forming and adhering a thermoplastic resin molded on a single phase, etc. can be used.
  • the surface-impregnated fabric first impregnated with an epoxy solution and then coated with a thermoplastic resin solution may be used to improve interfacial adhesion strength.
  • thermoplastic resin molding on a fabric impregnated with an epoxy solution and then heat treating the thermoplastic resin constituting the thermoplastic molding may be used.
  • thermoplastic resin molded product when the thermoplastic resin molded product is subjected to isothermal crystallization by heat treatment at the crystallization temperature of the thermoplastic resin constituting the thermoplastic resin molded product, more crystal regions (transition crystal regions) are formed at the interface between the aramid fabric and the thermoplastic resin molding, so that the mechanical properties of the aramid composite are This is further improved.
  • thermoplastic resin molded article is a molded article such as a film made of polypropylene resin.
  • Para-phenylenediamine, an aromatic diamine, and terephthaloyl dichloride, an aromatic dieside chloride were polymerized in an N-methyl-2-pyrrolidone polymerization solvent to prepare a poly paraphenylene terephthalamide polymer.
  • a concentrated sulfuric acid solvent was dissolved in a spinning dope, and the spinning dope was spun through a spinneret and solidified to prepare a wholly aromatic aramid filament of 1,500 deniers.
  • the wholly aromatic aramid filaments were applied to warp and weft yarns to weave into plain weave to produce aramid fabrics having a density of 180 g / m 2.
  • an aramid laminate was prepared by laminating 28 aramid fabrics prepared as described above, and then dipping them in a methanol / epoxy (8: 2) solution and drying them at 240 ° C. to impregnate the epoxy solution.
  • Aramid laminates were prepared.
  • 3-glycidoxylpropyltrimethoxysilane which is a silane-based binder
  • a binder composition is prepared by immersion for minutes, followed by heat treatment at a temperature of 100 ° C. for 24 hours.
  • a polypropylene resin solution is coated on the surface of the aramid laminate surface modified as described above with a thickness of 50 ⁇ m, and then heat-treated at 110 ° C. for 4 hours to isothermally crystallize the coated polypropylene resin to form an aramid composite. Prepared.
  • Para-phenylenediamine, an aromatic diamine, and terephthaloyl dichloride, an aromatic dieside chloride were polymerized in an N-methyl-2-pyrrolidone polymerization solvent to prepare a poly paraphenylene terephthalamide polymer.
  • a concentrated sulfuric acid solvent was dissolved in a spinning dope, and the spinning dope was spun through a spinneret and solidified to prepare a wholly aromatic aramid filament of 1,500 deniers.
  • the wholly aromatic aramid filaments were applied to warp and weft yarns to weave into plain weave to produce aramid fabrics having a density of 180 g / m 2.
  • the phenol resin was dissolved in a methanol solvent to immerse the aramid fabric in an impregnation composition having a phenol resin content of 56% by weight, followed by drying to remove the methanol solvent to remove the aramid prep having a phenol resin content of 20%. Got a leg.
  • the aramid prepreg was laminated with 28 sheets, and cured at a pressure of 150 ° C. to prepare an aramid laminate.
  • the aramid laminate prepared as described above was immersed in a methanol / epoxy (8: 2) solution to prepare an aramid laminate impregnated with an epoxy resin at 240 ° C.
  • the surface of the aramid laminate impregnated with an epoxy resin was oxygen-treated and subjected to plasma treatment under a 1,500 watt power and 15 minutes of irradiation time to prepare an aramid laminate with the surface modified.
  • a polypropylene resin solution is coated on the surface of the aramid laminate surface modified as described above with a thickness of 50 ⁇ m, and then heat-treated at 110 ° C. for 4 hours to isothermally crystallize the coated polypropylene resin to form an aramid composite. Prepared.
  • An aramid composite was prepared in the same manner as in Example 1 except that the step of immersing the aramid laminate in an epoxy solution was omitted.
  • An aramid composite was prepared in the same manner as in Example 2, except that the step of immersing the aramid laminate in the epoxy solution was omitted.
  • Adhesion strength (gf / 5cm) by peel test at 1f load cell and speed condition of 100 / mm according to ASTM D903 using aramid composites (samples) prepared in Examples and Comparative Examples ) was measured.
  • Aramid composite prepared according to the present invention is excellent in tensile strength and impact strength is useful as sports protective equipment material or safety protective equipment material such as helmet, knee protector, elbow protector.

Abstract

The present invention relates to a method for manufacturing an aramid composite, in which, when an aramid composite, which is formed of aramid fabric and thermoplastic resin molding material bonded to each other, is manufactured, the aramid fabric is dipped into an epoxy solution to be impregnated with the epoxy solution and then the aramid fabric impregnated with the epoxy solution is bonded to the thermoplastic resin molding material. The aramid composite manufactured by the present invention has excellent bond strength between the aramid fabric and the thermoplastic resin molding material. Accordingly, the aramid composite manufactured by the present invention has excellent tensile strength and impact strength and thus is an effective material for protective gear for both sports and safety.

Description

아라미드 복합체의 제조방법Method for preparing aramid complex
본 발명은 아라미드 복합체의 제조방법에 관한 것으로서, 구체적으로는 아라미드 원단과 열가소성 수지 성형물이 뛰어난 접착강도로 서로 접착되어 인장강도 및 충격강도가 우수한 아라미드 복합체의 제조방법에 관한 것이다.The present invention relates to a method for producing an aramid composite, specifically relates to a method for producing an aramid composite excellent in tensile strength and impact strength is bonded to each other with excellent adhesive strength of the aramid fabric and the thermoplastic resin molding.
본 발명에 있어서, 아라미드 복합체는 아라미드 원단과 열가소성 수지 성형물이 일체로 접착된 성형체를 의미한다.In the present invention, the aramid composite refers to a molded article in which the aramid fabric and the thermoplastic resin molded article are integrally bonded.
일반적으로, 스포츠 활동을 하다 보면 사람들은 늘 부상의 위험에 노출된다.In general, sports activities always expose people to risk of injury.
특히, 스키, 스노우보드, 롤러블레이드 등 격렬한 스포츠를 즐기는 사람들은 타박상, 찰과상, 골절상 등의 부상의 위험에 노출되는 경우가 많아진다.In particular, people who enjoy intense sports such as skiing, snowboarding, and rollerblading are often exposed to the risk of injury such as bruises, abrasions, and fractures.
최근에는, 생명의 위험을 무릅쓰고 모험을 즐기는 익스트림 스포츠가 크게 유행하고 있다. 이러한 익스트림 스포츠의 예로는 인라인 스케이트, 암벽 등반, 산악자전거, 웨이크 보드 등을 열거할 수 있다. In recent years, extreme sports, which risk adventure and enjoy adventure, have become popular. Examples of such extreme sports include inline skating, rock climbing, mountain biking, wakeboarding, and the like.
이러한 익스트림 스포츠를 즐기다 보면, 크고 작은 부상을 입게 되는 경우가 많아지는데, 예를 들면 인라인 스케이팅은 아스팔트와 같은 딱딱한 지면에서 빠르게 운동하기 때문에 넘어질 경우, 낙상 등으로 인해 관절 부위나 머리에 타박상 및 골절상을 입을 수 있다. 이와 같은 안전사고를 방지하기 위해 헬멧, 무릎 보호대 및 팔꿈치 보호대 등과 같은 보호장비를 착용하게 된다.Enjoying these extreme sports often leads to large and small injuries, such as inline skating, which quickly moves on hard ground, such as asphalt, if you fall down, bruises and fractures in your joints or head due to falls, etc. You can wear In order to prevent such safety accidents, protective equipment such as helmets, knee pads and elbow pads are worn.
이러한 보호장비는 나일론 또는 폴리에스테르 수지와 같은 일반 고분자 수지를 사용하여 제조하게 된다. 그러나, 이러한 일반 고분자 수지를 적용한 제품은 내충격성이 떨어져 외부 충격으로부터 신체를 충분히 보호하지 못하고 심할 경우 제품이 파손되어 큰 부상을 입는 실정이었다. 또한, 장기간 사용할 경우 강도가 저하되어 안전성능이 떨어지는 문제점이 있었다.Such protective equipment is manufactured using a general polymer resin such as nylon or polyester resin. However, such a product using the general polymer resin has a low impact resistance, it is not enough to protect the body from an external shock, if the situation is severe damage to the product was damaged. In addition, when used for a long time there is a problem that the strength is lowered, the safety performance falls.
이와 같은 스포츠 용품만이 아니라 차량 충돌시 인명과 재산 피해를 최소화 할 수 있는 범퍼 등 다른 종래의 보호장비용 소재로는 아라미드 원단상에 폴리프로필렌 수지 용액을 코팅하는 방법등으로 아라미드 원단 상에 필름상의 폴리프로필렌 수지층이 형성, 접착된 구조의 아라미드 복합체가 사용되어 왔다.In addition to such sporting goods, other conventional protective equipment materials, such as bumpers, which can minimize life and property damage in the event of a vehicle crash, are coated on aramid fabric by coating a polypropylene resin solution on the aramid fabric. Aramid composites having a structure in which a polypropylene resin layer has been formed and adhered have been used.
그러나, 상기 종래의 아라미드 복합체는 폴리프로필렌 수지의 화학구조상 작용기가 없기 때문에 아라미드 원단과 폴리프로필렌 수지층의 계면간 접착성이 떨어져 이들간의 접착강도는 물론 아라미드 복합체의 인장강도 및 충격강도가 크게 저하되는 문제점이 있었다.However, since the conventional aramid composite has no chemical structure functional group of the polypropylene resin, the interfacial adhesion between the aramid fabric and the polypropylene resin layer is poor, and the tensile strength and the impact strength of the aramid composite are greatly reduced. There was a problem.
이와 같은 종래 문제점들을 해결할 수 있도록, 본 발명에서는 아라미드 복합체를 구성하는 아라미드 원단과 열가소성 수지 성형물의 계면간 접착강도를 향상시키는 방법을 제공하고자 한다.In order to solve such a conventional problem, the present invention is to provide a method for improving the adhesion strength between the aramid fabric and the thermoplastic resin molding constituting the aramid composite.
이와 같은 과제를 달성하기 위해서, 본 발명에서는 아라미드 원단과 열가소성 수지 성형물이 접착된 아라미드 복합체를 제조할 때 상기 아라미드 원단을 에폭시 용액에 침지(Dipping)시켜 아라미드 원단내에 에폭시 용액을 함침시킨 다음, 에폭시 용액이 함침된 아라미드 원단과 열가소성 수지 성형물을 접착함으로써 아라미드 원단과 열가소성 수지 성형물의 계면 접착강도를 향상시킨다.In order to achieve the above object, in the present invention, when preparing the aramid composite bonded to the aramid fabric and the thermoplastic resin molding, the aramid fabric is immersed in the epoxy solution (Dipping) to impregnate the epoxy solution in the aramid fabric, then the epoxy solution By adhering the impregnated aramid fabric and the thermoplastic resin molding, the interfacial adhesion strength of the aramid fabric and the thermoplastic resin molding is improved.
또한, 본 발명에서는 에폭시 용액이 함침된 아라미드 원단과 열가소성 수지 성형물을 접착하기 이전에 에폭시 용액이 함침된 아라미드 원단 표면을 개질 처리하여 아라미드 원단과 열가소성 수지 성형물의 계면간 접착강도를 더욱 향상시킨다.In addition, the present invention further improves the adhesion strength between the aramid fabric and the thermoplastic resin molding by modifying the surface of the aramid fabric impregnated with the epoxy solution before bonding the aramid fabric impregnated with the epoxy solution and the thermoplastic resin molding.
또한, 본 발명에서는 아라미드 원단상에 접착되는 열가소성 수지 성형물을 열가소성 수지 성형물을 구성하는 열가소성 수지의 결정화 온도로 열처리하여 상기 열가소성 수지를 등온 결정화시켜 복합재의 물성에 영향을 미치는 열가소성 수지의 결정화도를 향상 시켜 아라미드 원단과 열가소성 수지 성형물의 계면간 접착강도를 더욱 향상시킨다.In addition, in the present invention, the thermoplastic resin molding adhered to the aramid fabric is heat-treated at the crystallization temperature of the thermoplastic resin constituting the thermoplastic resin molding to isothermally crystallize the thermoplastic resin to improve the crystallinity of the thermoplastic resin affecting the physical properties of the composite material. The adhesion strength between the aramid fabric and the thermoplastic resin molding is further improved.
본 발명으로 제조된 아라미드 복합체는 아라미드 원단과 열가소성 수지 성형물간의 접착강도가 우수하다. 그로인해, 본 발명으로 제조된 아라미드 복합체는 인장강도 및 충격강도가 우수하여 스포츠용 및 범퍼 등 안전용 보호장비 소재로 유용하다.The aramid composite prepared by the present invention is excellent in the adhesive strength between the aramid fabric and the thermoplastic resin molding. Therefore, the aramid composite prepared by the present invention is excellent in tensile strength and impact strength is useful as a safety protective equipment material for sports and bumpers.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에 따른 아라미드 복합체의 제조방법은 아라미드 원단과 열가소성 수지 성형물이 접착된 아라미드 복합체를 제조함에 있어서, 상기 아라미드 원단을 에폭시 용액에 침지(Dipping)시켜 아라미드 원단내에 에폭시 용액을 함침시킨 다음, 에폭시 용액이 함침된 아라미드 원단과 열가소성 수지 성형물을 접착시키는 것을 특징으로 한다.In the method for producing an aramid composite according to the present invention in preparing an aramid composite bonded to the aramid fabric and the thermoplastic resin molding, by dipping the aramid fabric in an epoxy solution (Dipping) impregnated with an epoxy solution in the aramid fabric, then an epoxy solution The impregnated aramid fabric and the thermoplastic resin molding are bonded to each other.
상기 아라미드 원단은 아라미드 섬유로 구성되나, 아라미드 복합체의 용도에 따라서는 고압축성 향상을 위해 주성분인 아라미드 섬유에 보조성분인 탄소섬유를 적절하게 혼합하여 구성될 수도 있다.The aramid fabric is composed of aramid fibers, but depending on the use of the aramid composite may be configured by appropriately mixing the carbon fibers as a secondary component with the aramid fibers as a main component for improving the high compression.
이 경우 탄소섬유는 아라미드 원단 전체중량 대비 50중량% 미만으로 혼합, 사용하는 것이 바람직하다.In this case, the carbon fiber is preferably mixed and used in less than 50% by weight relative to the total weight of the aramid fabric.
상기, 아라미드 섬유는 다음과 같은 공정에 의해 제조된다. 즉, 방향족 디아민과 방향족 디에시드 할라이드를 N-메틸-2-피롤리돈을 포함하는 중합용매 중에서 중합시킴으로써 전 방향족 폴리아미드 중합체를 제조하는 공정, 이 중합체를 농황산 용매에 용해시켜 방사 도프를 제조하는 공정, 상기 방사 도프를 방사 구금을 통해 방사한 후 방사물을 응고시켜 필라멘트를 제조하는 공정, 및 상기 필라멘트를 수세, 건조 및 열처리하는 공정을 수행하여 완성된다.The aramid fibers are produced by the following process. That is, a process for producing a wholly aromatic polyamide polymer by polymerizing an aromatic diamine and an aromatic dieside halide in a polymerization solvent containing N-methyl-2-pyrrolidone, dissolving this polymer in a concentrated sulfuric acid solvent to prepare a spinning dope. The process is completed by spinning the spinning dope through the spinneret and then solidifying the spinning material to produce a filament, and washing the filament with water, drying and heat treatment.
상술한 바와 같이 제조된 아라미드 섬유는 20 ~ 28g/d의 인장 강도 및 400~1200g/d의 탄성률을 가지게 된다. 이러한 물성을 갖는 아라미드 섬유를 헬멧, 무릎 보호대 및 팔꿈치 보호대 등과 같은 보호장비를 만드는데 사용할 경우, 상기 보호장비는 충격강도 및 인장 강도가 우수하여 스포츠 활동 중 부상으로부터 신체를 안전하게 보호할 수 있으며, 자동차 범퍼 등에 적용이 될 경우 우수한 내충격도 강도로 인하여 교통사고 발생시 인명 및 재산을 보호할 수 있다.Aramid fibers prepared as described above will have a tensile strength of 20 ~ 28g / d and an elastic modulus of 400 ~ 1200g / d. When aramid fibers having these properties are used to make protective equipment such as helmets, knee pads and elbow pads, the protective pads have excellent impact strength and tensile strength to protect the body from injuries during sports activities. If it is applied to, etc., it can protect the life and property in the event of a traffic accident due to its excellent impact resistance strength.
상기 아라미드 원단은, 상술한 방법으로 제조된 아라미드 섬유를 이용하여 제조한다. 특히 상기 아라미드 원단은, 상기 아라미드 섬유가 경사 및 위사에 적용되어 직조된 아라미드 직물일 수 있다.The aramid fabric is produced using aramid fibers produced by the method described above. In particular, the aramid fabric, the aramid fibers may be aramid fabric woven by applying to warp and weft.
상기 아라미드 직물은 평직(plain), 능직(twill) 또는 주자직(satin) 조직일 수 있다. 이러한 조직은 경사 및 위사가 일정하게 굴곡을 이루면서 형성되어 있기 때문에 외력을 받을 경우, 외력을 균일하게 직물 전체로 분산시킴에 따라 우수한 내충격성 및 인장 강도를 제공한다.The aramid fabric may be plain, twill or satin tissue. Such a structure is formed with a warp and weft uniformly bent, so that when subjected to external force, it provides excellent impact resistance and tensile strength by uniformly dispersing the external force throughout the fabric.
한편, 상기 아라미드 원단은 상술한 바와 같이 탄소 섬유와 아라미드 섬유를 혼합시켜 제조한 혼합 아라미드 원단일 수 있다. 상기 혼합 아라미드 원단은 상기 위사 및 경사에 아라미드 섬유 및 탄소 섬유를 적절하게 혼합시켜 제조할 수 있다.On the other hand, the aramid fabric may be a mixed aramid fabric prepared by mixing the carbon fiber and the aramid fiber as described above. The mixed aramid fabric can be prepared by mixing the aramid fibers and carbon fibers in the weft and warp appropriately.
예를 들어, 경사에 아라미드 원사를 적용하고 위사에 탄소 섬유를 적용한 혼합 아라미드 직물일 수 있고, 경사에 탄소 섬유를 적용하고 위사에 아라미드 섬유를 적용한 혼합 아라미드 직물일 수 있다. 또한, 경사에 아라미드 원사를 적용하고 위사에 탄소 섬유와 아라미드 섬유를 교대로 적용한 아라미드 직물일 수도 있지만, 반드시 이들에 한정되는 것은 아니다.For example, it may be a mixed aramid fabric in which aramid yarn is applied to the warp yarn and carbon fiber is applied to the weft yarn, and may be a mixed aramid fabric in which carbon fiber is applied to the warp yarn and aramid fiber is applied to the warp yarn. Moreover, although it may be an aramid fabric which applied the aramid yarn to the warp yarn and the carbon fiber and the aramid fiber to the weft alternately, it is not necessarily limited to these.
상기 아라미드 직물은 경사방향 및 위사방향의 직물밀도가 각각 10~40본/인 것이 바람직하다. 만일, 상기 경사방향 및 위사방향의 직물밀도가 10본/인치 미만일 경우 충분한 충격강도 및 인장 강도를 얻을 수 없고, 반면 상기 경사방향 및 위사방향의 직물밀도가 40본/인치를 초과할 경우 과도한 밀도로 인해 제직성이 저하되고 굽힘 등이 용이하지 않아 성형성이 떨어질 수 있다.The aramid fabric is preferably 10 to 40 / / fabric density in the warp direction and weft direction respectively. If the fabric density in the warp direction and weft direction is less than 10 bones / inch, sufficient impact strength and tensile strength may not be obtained, whereas when the fabric density in the warp direction and weft direction exceeds 40 bones / inch, excessive density Due to this, weaving is lowered and bending is not easy, so moldability may be degraded.
또한, 상기 아라미드 직물은 130~500g/㎡의 면밀도를 갖는 것이 바람직하다. 만일, 면밀도가 상기 범위보다 낮은 경우에는 직물에 공간이 생성됨으로써 충격강도가 떨어질 수 있고, 면밀도가 상기 범위보다 높은 경우에는 직물의 제조가 용이하지 않음으로써 생산 효율이 크게 저하될 수 있다.In addition, the aramid fabric is preferably having a surface density of 130 ~ 500g / ㎡. If the surface density is lower than the above range, the space may be generated in the fabric and thus the impact strength may be reduced. If the surface density is higher than the above range, the fabrication may not be easy and the production efficiency may be greatly reduced.
상기 아라미드 원단은 상기 아라미드 직물이 여러 겹으로 적층된 아라미드 적층재를 포함할 수 있다. 상기 아라미드 적층재를 극한 스포츠용 보호장비 및 자동차 범퍼 등 제조에 사용할 경우, 상기 보호장비는 강한 외부 충격으로부터 신체 및 재산을 더욱 충분히 보호할 수 있기 때문이다.The aramid fabric may include an aramid laminate in which the aramid fabric is laminated in several layers. When the aramid laminate is used in the manufacture of extreme sports protective equipment and automobile bumpers, the protective equipment can more fully protect the body and property from strong external shocks.
한편, 본 발명은 에폭시 용액이 함침된 아라미드 원단과 열가소성 수지 성형물을 접착하기 이전에 에폭시 용액이 함침된 아라미드 원단 표면을 개질 처리하는 것을 포함한다.On the other hand, the present invention includes modifying the surface of the aramid fabric impregnated with the epoxy solution prior to bonding the aramid fabric impregnated with the epoxy solution and the thermoplastic resin molding.
에폭시 수지가 함침된 아라미드 원단을 표면 개질 처리하게 되면 아라미드 원단과 열가소성 수지 성형물간의 개면간 접착력이 더욱 개선되는 효과가 있다.Surface modification treatment of the aramid fabric impregnated with the epoxy resin has an effect of further improving the adhesion between the aramid fabric and the thermoplastic resin molding.
상기 아라미드 원단의 표면 개질 처리는 아라미드 원단 표면에 플라스마를 조사해 주는 플라즈마 처리방식이나, 아라미드 원단 표면을 코로나 방전 처리해 주는 코로나 방전 처리방식이나, 아라미드 원단을 커플링제 용액에 침지시킨 후 건조해 주거나 커플링제 용액을 아라미드 원단에 코팅 또는 스프레이한 후 건조해 주는 커플링제 처리방식 등이 사용된다.The surface modification treatment of the aramid fabric is a plasma treatment method for irradiating a plasma on the aramid fabric surface, a corona discharge treatment method for corona discharge treatment of the aramid fabric surface, or the aramid fabric is dipped in a coupling agent solution and dried or a coupling agent Coupling agent treatment such as coating or spraying the solution on aramid fabric and drying is used.
상기 커플링제로는 하기 화학식 1의 실란계 화합물 또는 화학식 2로 표시되는 금속화합물 등이 사용될 수 있다.As the coupling agent, a silane compound of Formula 1 or a metal compound represented by Formula 2 may be used.
[화학식 1][Formula 1]
Y-(R)n-SiX3(Y는 할로겐 원자, 에폭시기, 아미노기, 머캅토기, 비닐기, 아크릴로일기로부터 선택된 1종의 관능기이고, R은 탄화수소기이며, X는 동일하거나 상이한 알콕시기이고, n은 0 또는 1의 정수이다)Y- (R) n-SiX 3 (Y is one functional group selected from halogen atom, epoxy group, amino group, mercapto group, vinyl group, acryloyl group, R is a hydrocarbon group, X is the same or different alkoxy group , n is an integer of 0 or 1)
[화학식 2][Formula 2]
M(OR')m(여기서, m은 3 또는 4의 정수이고, R'는 직쇄형 또는 분지형 탄소수 1 내지 8의 알킬기이며, M은 티탄늄(Ti) 또는 지르코늄(Zr)이다)M (OR ') m, where m is an integer of 3 or 4, R' is a straight or branched alkyl group of 1 to 8 carbon atoms, and M is titanium or zirconium
상기 화학식 1로 표시되는 실란계 커플링제는 관능기를 가짐에 따라 접합면과 쉽게 다양한 결합을 형성할 수 있기 때문에 아라미드 원단과 열가소성수지 성형물 사이의 접착 강도를 향상시키는 역할을 한다.Since the silane coupling agent represented by the formula (1) has a functional group, it can easily form various bonds with the bonding surface, thereby improving the adhesive strength between the aramid fabric and the thermoplastic resin molded product.
상기 화학식 2로 표시되는 금속산화물계 커플링제는 티탄늄 또는 지르코늄과 같은 금속을 함유함에 따라 인접한 원자는 쉽게 하전을 띠게 될 수 있고, 이에 따라 아라미드 원단과 열가소성 수지 성형물 사이의 결합력을 증가시킬 수 있기 때문에 접착 강도를 향상시키는 역할을 한다.As the metal oxide-based coupling agent represented by Chemical Formula 2 contains a metal such as titanium or zirconium, adjacent atoms may be easily charged, thereby increasing the bonding force between the aramid fabric and the thermoplastic resin molding. Therefore, it serves to improve the adhesive strength.
상기 커플링제 용액으로는 실란계 커플링제인 3-글리시독실프로필트리메톡시실란(3-glycidoxylpropyltrimethoxysilane) 또는 금속산화물계 커플링제인 지르코늄 에톡사이드(Zirconium ethoxide)를 에탄올 수용액에 1중량% 농도로 첨가하는 방법등으로 제조한다.As the coupling agent solution, 3-glycidoxylpropyltrimethoxysilane, which is a silane coupling agent, or zirconium ethoxide, which is a metal oxide coupling agent, is added to an aqueous solution of ethanol at a concentration of 1% by weight. We make by method to do.
상기 플라즈마 처리 공정은 반응 기체로 산소를 이용하여 아라미드 원단 표면을 처리할 경우, 상기 아라미드 원단표면은 다량의 산소 반응기가 생성될 수 있고, 상기 산소 반응기는 커플링제와의 높은 친화력을 가짐에 따라 접착 강도를 크게 향상시킬 수 있다. In the plasma treatment process, when the aramid fabric surface is treated with oxygen as a reaction gas, the aramid fabric surface may generate a large amount of oxygen reactor, and the oxygen reactor may have high affinity with a coupling agent, thereby adhering. The strength can be greatly improved.
상기 플라즈마 처리 공정은 질소 분위기 및 감압 하에서 100 내지 3000 와트의 일률 및 5 ~ 30 분의 조사시간에서 수행될 수 있다. 만일, 상기 일률이 너무 낮거나 또는 조사시간이 너무 짧을 경우 반응기가 적게 생성될 수 있고, 반면 상기 일률이 너무 높거나 또는 조사시간이 너무 길 경우 아라미드 원단이 손상을 받을 수 있다. 한편, 플라즈마 처리 후 아라미드 원단 표면에 생성된 반응기의 감소를 방지하기 위해서 질소 분위기에서 플라즈마 처리 공정을 수행하고, 수분의 도입을 막기 위해서 감압 하에서 플라즈마 처리 공정을 수행할 수 있다.The plasma treatment process may be carried out under a nitrogen atmosphere and a reduced pressure of 100 to 3000 watts and irradiation time of 5 to 30 minutes. If the work rate is too low or the irradiation time is too short, less reactors may be produced, whereas if the work rate is too high or the irradiation time is too long, the aramid fabric may be damaged. Meanwhile, the plasma treatment process may be performed in a nitrogen atmosphere to prevent the reduction of the reactor generated on the aramid fabric surface after the plasma treatment, and the plasma treatment process may be performed under reduced pressure to prevent the introduction of moisture.
상기 코로나 방전 처리 공정은, 상온 및 상압을 유지한 상태에서 두 개의 전극 사이에 높은 교류전압을 인가하여 코로나 방전을 유도하고, 상기 두 개의 전극 사이에 시료를 위치시킨 후 1,000 ~ 50,000 V의 전압 및 1 ~ 60 분의 조사시간에서 아라미드 원단의 표면을 코로나 처리하는 공정을 통해 수행될 수 있다.In the corona discharge treatment process, a high AC voltage is applied between two electrodes while maintaining room temperature and normal pressure to induce corona discharge, and a sample having a voltage of 1,000 to 50,000 V after placing the sample between the two electrodes and The irradiation time of 1 to 60 minutes may be carried out through a process of corona treatment of the surface of the aramid fabric.
아라미드 원단과 열가소성 수지 성형물의 접착방법 중 일례로는, 에폭시 용액이 함침된 원단상에 열가소성 수지 용액을 코팅한 후 코팅된 열가소성 수지의 결정화도를 최대한으로 발현할 수 있는 적정 결정화 온도로 열처리하여 아라미드 원단상에 열가소성 수지 성형물을 형성 및 접착시키는 방법등이 사용될 수 있다.As an example of the method of adhering the aramid fabric and the thermoplastic resin molded article, the thermoplastic resin solution is coated on the fabric impregnated with the epoxy solution, and then heat-treated at an appropriate crystallization temperature to express the crystallinity of the coated thermoplastic resin to the maximum. The method of forming and adhering a thermoplastic resin molded on a single phase, etc. can be used.
보다 바람직하기로는 에폭시 용액이 함침된 원단을 먼저 표면개질 처리한 후 열가소성 수지 용액을 코팅하는 것이 계면 접착강도 향상에 좋다.More preferably, the surface-impregnated fabric first impregnated with an epoxy solution and then coated with a thermoplastic resin solution may be used to improve interfacial adhesion strength.
또 다른 접착방법 중 일례로는 에폭시 용액이 함침된 원단상에 열가소성 수지 성형물을 적층시킨 후 열가소성 수지 성형물을 구성하는 열가소성 수지의 결정화 온도로 열처리하는 방법도 사용될 수 있다.As another example of the bonding method, a method of laminating a thermoplastic resin molding on a fabric impregnated with an epoxy solution and then heat treating the thermoplastic resin constituting the thermoplastic molding may be used.
이와 같이 열가소성 수지 성형물은 열가소성 수지 성형물을 구성하는 열가소성 수지의 결정화 온도로 열처리하여 등온 결정화시키면 아라미드 원단과 열가소성 수지 성형물의 계면부분에 더 많은 결정영역(전이결정영역)이 형성되어 아라미드 복합체의 기계적 물성이 보다 더 향상된다.As such, when the thermoplastic resin molded product is subjected to isothermal crystallization by heat treatment at the crystallization temperature of the thermoplastic resin constituting the thermoplastic resin molded product, more crystal regions (transition crystal regions) are formed at the interface between the aramid fabric and the thermoplastic resin molding, so that the mechanical properties of the aramid composite are This is further improved.
열가소성 수지 성형물의 일례로는 폴리프로필렌 수지로 제조된 필름 등의 성형물 등이다.One example of the thermoplastic resin molded article is a molded article such as a film made of polypropylene resin.
이하, 실시예 및 비교실시예를 통하여 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail through Examples and Comparative Examples.
그러나, 본 발명은 하기 실시예에 의해 보호범위가 한정되는 것은 아니다.However, the present invention is not limited by the following examples.
실시예 1Example 1
방향족 디아민인 파라-페닐렌디아민과 방향족 디에시드클로라이드인 테레프탈로일 디클로라이드를 N-메틸-2-피롤리돈 중합용매 내에서 중합시켜 폴리 파라페닐렌테레프탈아미드 중합체를 제조하였고, 그 후 상기 중합체를 농황산 용매에 용해시켜 방사도프를 제조하고, 방사도프를 방사구금을 통해 방사한 후 응고시켜 1,500 데니어인 전방향족 아라미드 필라멘트를 제조하였다. 이어서, 상기 전방향족 아라미드 필라멘트를 경사 및 위사에 적용하여 평직으로 제직하여 180 g/㎡인 밀도를 갖는 아라미드 직물을 제조하였다. Para-phenylenediamine, an aromatic diamine, and terephthaloyl dichloride, an aromatic dieside chloride, were polymerized in an N-methyl-2-pyrrolidone polymerization solvent to prepare a poly paraphenylene terephthalamide polymer. Was dissolved in a concentrated sulfuric acid solvent to prepare a spinning dope, and the spinning dope was spun through a spinneret and solidified to prepare a wholly aromatic aramid filament of 1,500 deniers. Subsequently, the wholly aromatic aramid filaments were applied to warp and weft yarns to weave into plain weave to produce aramid fabrics having a density of 180 g / m 2.
다음으로, 상기와 같이 제조된 아라미드 직물 28매를 적층하여 아라미드 적층채를 제조한 다음, 이를 메탄올/에폭시(8:2) 용액에 침지(dipping)한 후 240℃에서 건조하여 에폭시 용액이 함침된 아라미드 적층체를 제조하였다.Next, an aramid laminate was prepared by laminating 28 aramid fabrics prepared as described above, and then dipping them in a methanol / epoxy (8: 2) solution and drying them at 240 ° C. to impregnate the epoxy solution. Aramid laminates were prepared.
다음으로, 실란계 결합제인 3-글리시독실프로필트리메톡시실란 (3-glycidoxylpropyltrimethoxysilane)를 에탄올 수용액에 1 중량%의 농도로 첨가하여 결합제 조성물을 준비한 후, 상기 결합제 조성물에 상기 아라미드 적층재를 30 분 동안 침지시킨 후 100℃의 온도에서 24시간 동안 열처리하여 표면 개질된 아라미드 적층체를 제조하였다.Next, 3-glycidoxylpropyltrimethoxysilane, which is a silane-based binder, is added to an aqueous ethanol solution at a concentration of 1% by weight to prepare a binder composition, and then the aramid laminate is added to the binder composition. The surface-modified aramid laminate was prepared by immersion for minutes, followed by heat treatment at a temperature of 100 ° C. for 24 hours.
다음으로, 상기와 같이 표면개질된 아라미드 적층체 표면에 폴리프로필렌 수지 용액을 50㎛의 두께로 코팅한 다음, 110℃의 온도에서 4시간 동안 열처리하여 코팅된 폴리프로필렌 수지를 등온 결정화시켜 아라미드 복합체를 제조하였다.Next, a polypropylene resin solution is coated on the surface of the aramid laminate surface modified as described above with a thickness of 50 μm, and then heat-treated at 110 ° C. for 4 hours to isothermally crystallize the coated polypropylene resin to form an aramid composite. Prepared.
제조한 아라미드 복합체의 각종 물성을 평가한 결과는 표 1과 같았다.The results of evaluating various physical properties of the prepared aramid composite were as shown in Table 1.
실시예 2Example 2
방향족 디아민인 파라-페닐렌디아민과 방향족 디에시드클로라이드인 테레프탈로일 디클로라이드를 N-메틸-2-피롤리돈 중합용매 내에서 중합시켜 폴리 파라페닐렌테레프탈아미드 중합체를 제조하였고, 그 후 상기 중합체를 농황산 용매에 용해시켜 방사도프를 제조하고, 방사도프를 방사구금을 통해 방사한 후 응고시켜 1,500 데니어인 전방향족 아라미드 필라멘트를 제조하였다. 이어서, 상기 전방향족 아라미드 필라멘트를 경사 및 위사에 적용하여 평직으로 제직하여 180 g/㎡인 밀도를 갖는 아라미드 직물을 제조하였다.Para-phenylenediamine, an aromatic diamine, and terephthaloyl dichloride, an aromatic dieside chloride, were polymerized in an N-methyl-2-pyrrolidone polymerization solvent to prepare a poly paraphenylene terephthalamide polymer. Was dissolved in a concentrated sulfuric acid solvent to prepare a spinning dope, and the spinning dope was spun through a spinneret and solidified to prepare a wholly aromatic aramid filament of 1,500 deniers. Subsequently, the wholly aromatic aramid filaments were applied to warp and weft yarns to weave into plain weave to produce aramid fabrics having a density of 180 g / m 2.
이어서, 페놀 수지를 메탄올 용매에 용해시켜 페놀 수지의 함량이 56 중량%인 함침용 조성물에 상기 아라미드 직물을 침지(dipping)한 후 건조시켜 메탄올 용매를 제거하여 페놀 수지의 함유량이 20 %인 아라미드 프리프레그를 얻었다. 이어서, 상기 아라미드 프리프레그를 28 매로 적층 후 가압 및 150℃의 온도에서 경화시켜 아라미드 적층체를 제조하였다.Subsequently, the phenol resin was dissolved in a methanol solvent to immerse the aramid fabric in an impregnation composition having a phenol resin content of 56% by weight, followed by drying to remove the methanol solvent to remove the aramid prep having a phenol resin content of 20%. Got a leg. Subsequently, the aramid prepreg was laminated with 28 sheets, and cured at a pressure of 150 ° C. to prepare an aramid laminate.
다음으로, 상기와 같이 제조된 아라미드 적층체를 이를 메탄올/에폭시(8:2) 용액에 침지(dipping)한 후 240℃에서 에폭시 수지가 함침된 아라미드 적층체를 제조하였다.Next, the aramid laminate prepared as described above was immersed in a methanol / epoxy (8: 2) solution to prepare an aramid laminate impregnated with an epoxy resin at 240 ° C.
다음으로, 에폭시 수지가 함침된 아라미드 적층체 표면을 반응기체로 산소를 사용하고 1,500 와드 일률 및 15분의 조사시간 하에서 플라즈마 처리하여 표면이 개질된 아라미드 적층체를 제조하였다.Next, the surface of the aramid laminate impregnated with an epoxy resin was oxygen-treated and subjected to plasma treatment under a 1,500 watt power and 15 minutes of irradiation time to prepare an aramid laminate with the surface modified.
다음으로, 상기와 같이 표면개질된 아라미드 적층체 표면에 폴리프로필렌 수지 용액을 50㎛의 두께로 코팅한 다음, 110℃의 온도에서 4시간 동안 열처리하여 코팅된 폴리프로필렌 수지를 등온 결정화시켜 아라미드 복합체를 제조하였다.Next, a polypropylene resin solution is coated on the surface of the aramid laminate surface modified as described above with a thickness of 50 μm, and then heat-treated at 110 ° C. for 4 hours to isothermally crystallize the coated polypropylene resin to form an aramid composite. Prepared.
제조한 아라미드 복합체의 각종 물성을 평가한 결과는 표 1과 같았다.The results of evaluating various physical properties of the prepared aramid composite were as shown in Table 1.
비교실시예 1Comparative Example 1
아라미드 적층체를 에폭시 용액에 침지하는 공정을 생략한 것을 제외하고는 실시예 1과 동일한 방법으로 아라미드 복합체를 제조하였다.An aramid composite was prepared in the same manner as in Example 1 except that the step of immersing the aramid laminate in an epoxy solution was omitted.
제조한 아라미드 복합체의 각종 물성을 평가한 결과는 표 1과 같았다.The results of evaluating various physical properties of the prepared aramid composite were as shown in Table 1.
비교실시예 2Comparative Example 2
아라미드 적층체를 에폭시 용액에 침지하는 공정을 생략한 것을 제외하고는 실시예 2와 동일한 방법으로 아라미드 복합체를 제조하였다.An aramid composite was prepared in the same manner as in Example 2, except that the step of immersing the aramid laminate in the epoxy solution was omitted.
제조한 아라미드 복합체의 각종 물성을 평가한 결과는 표 1과 같았다.The results of evaluating various physical properties of the prepared aramid composite were as shown in Table 1.
표 1 아라미드 복합체의 물성평가 결과
구분 실시예 1 실시예 2 비교실시예 1 비교실시예 2
접착강도(gf/5㎝) 260 255 121 130
인장강도(N/5㎝) 5,640 6,885 2,430 2,800
충격강도(J/㎝) 23 28 13 17
Table 1 Physical property evaluation result of aramid complex
division Example 1 Example 2 Comparative Example 1 Comparative Example 2
Adhesive strength (gf / 5 ㎝) 260 255 121 130
Tensile Strength (N / 5㎝) 5,640 6,885 2,430 2,800
Impact strength (J / cm) 23 28 13 17
표 1의 각종물성은 아래와 같은 방법으로 평가하였다.Various physical properties of Table 1 were evaluated by the following method.
접착 강도(gf/5) 측정Adhesive strength (gf / 5) measurement
실시예 및 비교실시예에서 제조된 아라미드 복합체(시료)를 이용하여 ASTM D903의 규정에 따라 1f의 로드셀과 100/㎜분의 속도 조건에서 필 테스트(peel test)에 의해 접착 강도(gf/5㎝)를 측정하였다.Adhesion strength (gf / 5cm) by peel test at 1f load cell and speed condition of 100 / mm according to ASTM D903 using aramid composites (samples) prepared in Examples and Comparative Examples ) Was measured.
인장 강도 측정Tensile strength measurement
ASTM D 638 시험방법에 따라 경사방향 및 위사방향의 인장 강도(N/㎝)를 각각 측정한 후 이를 평균하여 구하였다.Tensile strength (N / cm) in the warp direction and the weft direction were measured and averaged according to the ASTM D 638 test method.
충격 강도 측정Impact strength measurement
ASTM D 256 시험방법에 따라 충격 강도(J/㎝)를 측정하였다.Impact strength (J / cm) was measured according to ASTM D 256 test method.
본 발명에 따라 제조된 아라미드 복합체는 인장강도 및 충격강도가 우수하여 헬멧, 무릎 보호대, 팔꿈치 보호대 등과 같은 스포츠용 보호장비 소재나 안전용 보호장비 소재로 유용하다.Aramid composite prepared according to the present invention is excellent in tensile strength and impact strength is useful as sports protective equipment material or safety protective equipment material such as helmet, knee protector, elbow protector.

Claims (5)

  1. 아라미드 원단과 열가소성 수지 성형물이 접착된 아라미드 복합체를 제조함에 있어서, 상기 아라미드 원단을 에폭시 용액에 침지(Dipping)시켜 아라미드 원단내에 에폭시 용액을 함침시킨 다음, 에폭시 용액이 함침된 아라미드 원단과 열가소성 수지 성형물을 접착시키는 것을 특징으로 하는 아라미드 복합체의 제조방법.In preparing the aramid composite bonded to the aramid fabric and the thermoplastic resin molding, the aramid fabric is immersed in an epoxy solution to impregnate the epoxy solution in the aramid fabric, and then the aramid fabric and the thermoplastic resin molding impregnated with the epoxy solution A method for producing an aramid composite, characterized in that the adhesion.
  2. 제1항에 있어서, 에폭시 용액이 함침된 아라미드 원단과 열가소성 수지 성형물을 접착하기 이전에 에폭시 용액이 함침된 아라미드 원단 표면을 개질 처리하는 것을 특징으로 하는 아라미드 복합체의 제조방법.The method of claim 1, wherein the surface of the aramid fabric impregnated with the epoxy solution is modified before bonding the aramid fabric impregnated with the epoxy solution and the thermoplastic resin molding.
  3. 제1항에 있어서, 아라미드 원단 표면의 개질처리는 플라즈마 처리방식, 코로나 방전처리 방식 및 커플링제 처리방식 중에서 선택된 1종의 방식으로 실시하는 것을 특징으로 하는 아라미드 복합체의 제조방법.The method for producing an aramid composite according to claim 1, wherein the modification of the surface of the aramid fabric is performed by one of the following methods: plasma treatment, corona discharge treatment, and coupling agent treatment.
  4. 제1항에 있어서, 에폭시 용액이 함침된 원단상에 열가소성 수지 용액을 코팅한 후 코팅된 열가소성 수지의 결정화 온도로 열처리하여 아라미드 원단상에 열가소성 수지 성형물을 형성 및 접착시키는 것을 특징으로 하는 아라미드 복합체의 제조방법.The method of claim 1, wherein the thermoplastic resin solution is coated on the fabric impregnated with the epoxy solution and then heat-treated at the crystallization temperature of the coated thermoplastic resin to form and adhere the thermoplastic resin molding on the aramid fabric. Manufacturing method.
  5. 제1항에 또는 제4항에 있어서, 열가소성 수지 성형물은 폴리프로필렌 필름인 것을 특징으로 하는 아라미드 복합체의 제조방법.The method for producing an aramid composite according to claim 1 or 4, wherein the thermoplastic resin molded product is a polypropylene film.
PCT/KR2011/010128 2011-12-27 2011-12-27 Method for manufacturing an aramid composite WO2013100212A1 (en)

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CN104313712A (en) * 2014-09-22 2015-01-28 宁波昊宇新材料股份有限公司 Preparation method for paper-plastic composite bag
CN104313713A (en) * 2014-09-22 2015-01-28 宁波昊宇新材料股份有限公司 Preparation method of high-strength paper-plastic compound bag
US11491742B2 (en) 2017-09-28 2022-11-08 Kolon Industries, Inc. Aramid fabric having excellent adhesion to polyurethane matrix resin and excellent tensile strength, method for producing same, aramid fabric prepreg comprising same and aramid fabric/thermoplastic polyurethane matrix resin composite comprising same

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JPH05138785A (en) * 1991-01-25 1993-06-08 British Petroleum Co Plc:The Reinforcing resin and composite material
JPH11335972A (en) * 1998-05-25 1999-12-07 Du Pont Toray Co Ltd Surface treating agent for aramid fiber, surface-treated aramid fiber, surface treatment of aramid fiber, and fiber-reinforced composite material
JP2003246016A (en) * 2001-12-20 2003-09-02 Asahi Kasei Corp Prepreg sheet and laminated structure
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Publication number Priority date Publication date Assignee Title
CN104313712A (en) * 2014-09-22 2015-01-28 宁波昊宇新材料股份有限公司 Preparation method for paper-plastic composite bag
CN104313713A (en) * 2014-09-22 2015-01-28 宁波昊宇新材料股份有限公司 Preparation method of high-strength paper-plastic compound bag
US11491742B2 (en) 2017-09-28 2022-11-08 Kolon Industries, Inc. Aramid fabric having excellent adhesion to polyurethane matrix resin and excellent tensile strength, method for producing same, aramid fabric prepreg comprising same and aramid fabric/thermoplastic polyurethane matrix resin composite comprising same

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