KR102438624B1 - Semi-incombustible resin composition for FRP pultrusion - Google Patents
Semi-incombustible resin composition for FRP pultrusion Download PDFInfo
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Abstract
본 발명은 FRP 그레이팅 인발성형용 준불연성의 수지조성물에 관한것이며 특히, 선박용 FRP 그레이팅(grating)이 갖추어야 하는 강도, 내구성, 표면인화성 등의 물리 화학적 특성을 만족시키는 및 이를 이용하여 제조한 선박용 FRP 그레이팅(grating)을 제조하기 위한 FRP 인발성형용 준불연성의 수지조성물에 관한 것이며. 불포화폴리에스테르수지, 염소화폴리염화비닐수지, 상용화제, 섬유카플링제, 복합난연제, 복합억연제, 경화제, 촉진제, 보조결합제 및 강화보조재로 아라미드 단섬유로 조성된다.
본 발명의 FRP 그레이팅 인발성형용 준불연성의 수지조성물은 인발성형 FRP 그레이팅의 제작에 적합한 수지조성물이며, 이로부터 제작된 인발성형 FRP 그레이팅은 내구성, 표면인화성, 불연성 등의 물리 화학적 특성이 선박용 FRP 그레이팅에 적합하여 강도 및 방화 등이 요구되는 선박의 통행로, 사다리, 플랫트폼 시설에 유리하게 적용될 수 있는 특징을 지니고 있다. The present invention relates to a semi-incombustible resin composition for pultrusion molding of FRP gratings, and in particular, FRP gratings for ships that satisfy physicochemical properties such as strength, durability, and surface flammability that FRP gratings for ships must have, and are manufactured using the same. It relates to a semi-incombustible resin composition for FRP pultrusion for manufacturing (grating). Unsaturated polyester resin, chlorinated polyvinyl chloride resin, compatibilizer, fiber coupling agent, composite flame retardant, composite flame retardant, hardener, accelerator, auxiliary binder and reinforcing auxiliary material are composed of short aramid fibers.
The semi-incombustible resin composition for pultrusion molding of FRP gratings of the present invention is a resin composition suitable for the production of pultrusion-molded FRP gratings, and the pultrusion-formed FRP gratings produced therefrom have physical and chemical properties such as durability, surface flammability, and non-combustibility. It has characteristics that can be advantageously applied to passageways, ladders, and platform facilities of ships that require strength and fire protection.
Description
본 발명은 FRP(Fiber Reinforced Plastic) 인발성형용 준불연성 수지조성물에 관한 것이며, 구체적으로는 선박용 FRP 그레이팅(grating) 제작에 적합한 FRP 인발성형용 준불연성의 수지조성물에 관한 것이다.The present invention relates to a semi-incombustible resin composition for FRP (Fiber Reinforced Plastic) pultrusion, and more specifically, to a semi-noncombustible resin composition for FRP pultrusion suitable for manufacturing FRP gratings for ships.
일반적으로 그레이팅(grating)은 주물이나 스텐레스 스틸 등의 금속재질 등으로 격자형태로 제작되어 도로변이나 공원, 인도 등의 배수관 뚜껑으로 설치하고 있으며, 건축, 플랜트, 선박 등에서는 상판, 발판, 계단 등으로 사용되고 있다.In general, gratings are manufactured in a grid form with metal materials such as casting or stainless steel, and are installed as the lids of drain pipes on roadsides, parks, and sidewalks. is being used
근래 들어 금속 그레이팅(grating)은 철강재료의. 가격 상승 등으로 인하여 기존의 금속재료 보다 우수한 비강성, 비탄성율을 가지며 부식에 강하고 내피로성이 뛰어난 섬유강화복합재료(Fiber Reinforced Plastic)로 제작한 FRP그레이팅을 사용하고 있으며, 그 사용량도 점차 증가되고 있는 추세이다.In recent years, metal grating has been used in steel materials. Due to price increase, etc., FRP grating made of Fiber Reinforced Plastic, which has superior specific rigidity and specific modulus than existing metal materials, is strong against corrosion and has excellent fatigue resistance, is being used, and its usage is gradually increasing. there is a trend
섬유강화복합재료인 FRP(Fiber Reinforced Plastic)는 자동차, 항공, 전자, 건설, 스포츠 레저 및 국방 산업 등과 관련하여 산업재료로서 각광을 받고 있으며, 성형공정에서 그 조성을 비교적 자유롭게 변화시킬 수 있는 특징이 있기 때문에 다양한 용도에 부합되는 물성을 창출할 수 있다는 장점을 지니고 있지만, 선택하는 섬유보강재, 수지종류 및 성형공법에 따라 FRP(Fiber Reinforced Plastic)의 물성이 크게 변화하기 때문에 사용용도에 따라 고려할 문제점에 대한 연구개발이 진행되고 있다.FRP (Fiber Reinforced Plastic), a fiber-reinforced composite material, is in the spotlight as an industrial material in relation to automobile, aviation, electronics, construction, sports leisure and defense industries, etc. Therefore, it has the advantage of being able to create properties that are suitable for various uses, but since the properties of FRP (Fiber Reinforced Plastic) vary greatly depending on the fiber reinforcement material, resin type, and molding method selected, there are problems to be considered depending on the use. R&D is in progress.
상기한 FRP 그레이팅은 성형방법에 따라 몰드 FRP 그레이팅(Molded FRP Grating)과 인발 FRP 그레이팅(Pultruded FRP Grating)으로 구분되며, 인발 FRP 그레이팅의 성형공정에서 인발공정은 섬유 보강재의 배향을 특정한 방향으로 유지할 수 있을 뿐만 아니라 보강재에 장력이 주어진 상태에서 함침수지가 경화 또는 응고되므로 다른 성형공정에 의한 제품보다 기계적 특성이 우수하여 섬유강화 복합재료의 성형공정으로 관심이 집중되고 있다.The above-mentioned FRP grating is divided into molded FRP grating and pultruded FRP grating according to the molding method. In addition, since the impregnated resin hardens or solidifies when tension is applied to the reinforcing material, the mechanical properties are superior to products made by other molding processes, and thus, attention is focused on the molding process of fiber-reinforced composite materials.
인발성형 FRP와 관련한 선행기술로 예를 들면, 특허문헌1에 FRP 절연봉을 인발성형 수지를 제조함에 있어서, 에폭시 수지에 아크릴산 또는 메타아크릴산을 첨가하여 반응시키되 (메타)아크릴산/에폭시 수지의 당량비를 1 ~ 1.5로 촉매와 함께 첨가하고 드롭핑 반응시켜서 산가 20이하의 비닐에스테르 수지 바인더를 제조하는 단계와, 상기 비닐에스테르 수지 바인더에 스티렌모노머 및 아크릴모노머를 첨가하여 반응시키는 단계, 그리고 여기에 열가소성 수지 및 첨가제를 첨가하는 단계를 포함하는 것을 특징으로 하는 F.R.P 절연봉 인발성형품 제조용 비닐에스테르 수지의 제조방법을 개시하고 있으며, 특허문헌 2에 에폭시 주제 35 ~ 40 중량부, 에폭시 경화제 35 ~ 40 중량부, 내부이형제 0.5 ~ 1.2 중량부, 표면처리제 0.3 ~ 0.6중량부, 수산화알루미늄 14 ~ 18 중량부, 수산화마그네슘 0.4 ~ 3.1 중량부, 멜라민 0.3～2.0 중량부 및 적인 3.0 ~ 4.0 중량부를 배합하여 제조된 에폭시수지조성물을 제조하고 상기 수지조성물에 유리섬유, 탄소섬유 또는 아라미드섬유 중 어느 하나를 함침한 후 인발성형하여 제조된 것을 특징으로 하는 난연성 FRP 제품을 개시하고 있다.In the prior art related to pultrusion-molded FRP, for example, in the manufacture of a pultrusion-molded resin for an FRP insulating rod in Patent Document 1, acrylic acid or methacrylic acid is added to the epoxy resin to react with (meth)acrylic acid/epoxy resin equivalent ratio Preparing a vinyl ester resin binder having an acid value of 20 or less by adding 1 to 1.5 together with a catalyst and performing a dropping reaction, adding and reacting a styrene monomer and an acrylic monomer to the vinyl ester resin binder, and a thermoplastic resin thereto And it discloses a method for producing a vinyl ester resin for manufacturing an F.R.P insulation bar pultrusion molded article, characterized in that it comprises the step of adding an additive, and in Patent Document 2, 35 to 40 parts by weight of an epoxy base material, 35 to 40 parts by weight of an epoxy curing agent, An epoxy prepared by mixing 0.5 to 1.2 parts by weight of an internal release agent, 0.3 to 0.6 parts by weight of a surface treatment agent, 14 to 18 parts by weight of aluminum hydroxide, 0.4 to 3.1 parts by weight of magnesium hydroxide, 0.3 to 2.0 parts by weight of melamine, and 3.0 to 4.0 parts by weight of red red Disclosed is a flame retardant FRP product, characterized in that the resin composition is prepared and the resin composition is impregnated with any one of glass fiber, carbon fiber, or aramid fiber, and then pultruded.
또 특허문헌 3에 45 ~ 55 중량%의 비스페놀 A 에폭시수지, 36 ~ 44중량%의 산무수물계 경화제, 4.5 ~ 5.5중량%의 수산화알루미늄, 2.7 ~ 3.7중량%의 흑색안료, 1.35 ~ 1.65중량%의 이형제 및 0.45 ~ 0.55중량%의 탄소 나노 튜브를 포함하여 이루어지는 인발용 수지를 소재로 하여 수직 인발 공법에 의해 화살대를 제조하되 상기 인발용 수지를 구성하는 상기 수산화알루미늄, 상기 흑색안료 및 상기 이형제를 포함하는 첨가제는 550∼650cps의 점도를 가지는 것을 특징으로 하는 인발용 수지를 이용한 화살대 제조방법을 개시하고 있으며, 상기 선행기술들은 인발성형 FRP 그레이팅 기술과는 직접적인 관련성이 적다고 하겠다.In addition, in Patent Document 3, 45 to 55% by weight of bisphenol A epoxy resin, 36 to 44% by weight of an acid anhydride-based curing agent, 4.5 to 5.5% by weight of aluminum hydroxide, 2.7 to 3.7% by weight of black pigment, 1.35 to 1.65% by weight An arrowhead is prepared by a vertical drawing method using a drawing resin comprising a release agent and 0.45 to 0.55 wt% of carbon nanotubes as a material, and the aluminum hydroxide, the black pigment and the release agent constituting the drawing resin are used. The additive included discloses a method for manufacturing an arrowhead using a pultrusion resin, characterized in that it has a viscosity of 550 to 650cps, and the prior art has little direct relevance to pultrusion-molded FRP grating technology.
본 발명의 발명자는 인발성형 선박용 FRP 그레이팅이 갖추어야 하는 물리화학적 특성 및 불연성 등을 만족하는 FRP 인발용 준불연성의 수지조성물을 조성함으로써 본 발명을 완성하였다. The inventor of the present invention has completed the present invention by composing a semi-non-combustible resin composition for drawing FRP that satisfies the physicochemical properties and non-combustibility that FRP gratings for pultrusion ships must have.
본 발명에서 해결하고자 하는 과제는 FRP(Fiber Reinforced Plastic) 그레이팅 인발성형용 준불연성 수지조성물의 제공에 관한 것이며, 구체적으로는 선박용 FRP 그레이팅 제작에 적합한 FRP 인발성형용 준불연성의 수지조성물의 제공을 목적으로 하는 것이다.The problem to be solved in the present invention relates to the provision of a semi-incombustible resin composition for FRP (Fiber Reinforced Plastic) grating pultrusion, and specifically, the purpose of providing a semi-noncombustible resin composition for FRP pultrusion suitable for manufacturing FRP grating for ships. will do it with
보다 구체적으로는 선박용 FRP 그레이팅(grating)이 갖추어야 하는 강도, 내구성, 표면인화성 등의 물리 화학적 특성을 만족시키는 FRP 인발성형용 준불연성의 수지조성물 및 이를 이용하여 제조한 선박용 FRP 그레이팅(grating)의 제공을 목적으로 하는 것이다.More specifically, a semi-incombustible resin composition for FRP pultrusion that satisfies physicochemical properties such as strength, durability, and surface flammability that FRP gratings for ships must have, and FRP gratings for ships manufactured using the same. is intended for
본 발명에서 과제의 해결수단으로 FRP 그레이팅 인발성형용 준불연성 수지조성물은 불포화폴리에스테르수지, 염소화폴리염화비닐수지, 상용화제로 무수말레인산 크라프트 폴리염화비닐공중합체 또는 무수말레인산변성폴리프로필렌, 섬유카플링제로 3-글리시톡시프로필트리메톡시실란 또는 (3-메타크릴옥시프로필)트리메톡시실란, 복합난연제, 복합억연제, 경화제, 촉진제, 보조결합재 및 강화보조재로 일정길이의 아라미드 단섬유를 포함하여 조성되는 것으로 이루어진다.As a means of solving the problem in the present invention, the semi-incombustible resin composition for pultrusion molding with FRP grating is unsaturated polyester resin, chlorinated polyvinyl chloride resin, maleic anhydride kraft polyvinyl chloride copolymer or maleic anhydride-modified polypropylene as compatibilizer, and fiber coupling agent 3 -Glycytoxypropyltrimethoxysilane or (3-methacryloxypropyl)trimethoxysilane, composite flame retardant, composite flame retardant, hardener, accelerator, auxiliary binder and reinforcing auxiliary material, including short aramid fibers of a certain length made to become
본 발명에 따른 FRP 그레이팅 인발성형용 준불연성 수지조성물의 일 실시형태는 불포화폴리에스테르수지 100중량부에 대하여, 염소화폴리염화비닐수지 3 ~ 7중량부, 상용화제로 무수말레인산 크라프트 폴리염화비닐공중합체 또는 무수말레인산변성폴리프로필렌 8 ~ 12중량부, 섬유카플링제로 3-글리시톡시프로필트리메톡시실란 또는 (3-메타크릴옥시프로필)트리메톡시실란 5 ~ 10중량부, 복합난연제로 DOPO(HCA) 8 ~ 12중량부, 브롬계 난연제 8 ~ 12중량부 및 인계 난연제 3 ~ 5중량부, 복합억연제로 수산화알루미늄 3 ~ 5중량부, 수산화마그네슘 3 ~ 5중량부, Zinc-Borate 3 ~ 5중량부, 경화제로 MEKPO 0.8 ~ 1.2중량부, 촉진제로 코발트계 금속비누 0.8 ~ 1.2중량부, 보조결합제로 아세트산 또는 말레익산 0.1 ~ 0.2 중량부 및 강화보조재로 1 ~ 3㎜ 길이의 아라미드 단섬유 3 ~ 7중량부를 포함하여 조성되는 것으로 이루어진다.An embodiment of the semi-incombustible resin composition for pultrusion molding FRP grating according to the present invention is based on 100 parts by weight of the unsaturated polyester resin, 3 to 7 parts by weight of a chlorinated polyvinyl chloride resin, a kraft polyvinyl chloride copolymer of maleic anhydride as a compatibilizer, or 8 to 12 parts by weight of maleic anhydride-modified polypropylene, 5 to 10 parts by weight of 3-glycitoxypropyltrimethoxysilane or (3-methacryloxypropyl)trimethoxysilane as a fiber coupling agent, DOPO (HCA) as a composite flame retardant 8 to 12 parts by weight, 8 to 12 parts by weight of a bromine-based flame retardant and 3 to 5 parts by weight of a phosphorus-based flame retardant, 3 to 5 parts by weight of aluminum hydroxide as a composite flame retardant, 3 to 5 parts by weight of magnesium hydroxide, 3 to 5 parts by weight of zinc-borate Part, 0.8 ~ 1.2 parts by weight of MEKPO as a curing agent, 0.8 ~ 1.2 parts by weight of a cobalt-based metal soap as an accelerator, 0.1 ~ 0.2 parts by weight of acetic acid or maleic acid as an auxiliary binder, and 3 ~ 3 mm long aramid fibers as a reinforcing auxiliary material It consists of a composition including 7 parts by weight.
상기 본 발명에 따른 FRP 그레이팅 인발성형용 준불연성 수지조성물은 상용화제로 무수말레인산 크라프트 폴리염화비닐공중합체 또는 무수말레인산변성폴리프로필렌을 조성성분으로 배합하여 열경화성수지인 불포화폴리에스테르수지와 열가소성수지인 염소화폴리염화비닐수지의 균일한 혼합을 도모하는 것으로 이루어진다.The semi-incombustible resin composition for pultrusion of FRP grating according to the present invention is a thermosetting resin unsaturated polyester resin and a thermoplastic resin chlorinated poly by mixing maleic anhydride kraft polyvinyl chloride copolymer or maleic anhydride-modified polypropylene as a compatibilizer. It consists in aiming at uniform mixing of the vinyl chloride resin.
또한 본 발명은 섬유카플링제로 3-글리시톡시프로필트리메톡시실란 또는 (3-메타크릴옥시프로필)트리메톡시실란를 조성성분으로 배합하여 섬유강화재에 수지조성물의 함침성을 향상시키는 것으로 이루어진다.In addition, the present invention consists of improving the impregnability of the resin composition in the fiber reinforcement by blending 3-glycitoxypropyltrimethoxysilane or (3-methacryloxypropyl)trimethoxysilane as a component as a fiber coupling agent.
본 발명에 따른 또 다른 과제 해결수단으로는 선박용 인발성형 FRP 그레이팅(grating)은 섬유보강재 공급공정, 섬유보강재를 상기한 본 발명의 FRP 인발성형용 준불연성 수지조성물에 함침시키는 함침공정, 수지 함침 섬유보강재를 몰드를 통과시키면서 인발시키는 인발공정, 인발된 수지 함침 섬유보강재를 경화시키는 경화공정 및 경화된 수지 함침 섬유보강재를 일정하게 컷팅하는 절단공정을 포함하여 제조되 것으로 이루어진다.As another problem solving means according to the present invention, the pultrusion molding FRP grating for ships is a fiber reinforcement material supply process, an impregnation process of impregnating the fiber reinforcement material into the semi-incombustible resin composition for FRP pultrusion molding of the present invention, resin impregnated fiber It is manufactured including a drawing process of drawing the reinforcing material while passing it through a mold, a curing process of hardening the drawn resin-impregnated fiber reinforcing material, and a cutting process of constantly cutting the cured resin-impregnated fiber reinforcing material.
발명에 따른 FRP 그레이팅 인발성형용 준불연성 수지조성물로부터 제조된 선박용 인발성형 FRP 그레이팅(grating)은 강도, 내구성, 표면인화성, 불연성 등의 물리 화학적 특성이 선박용 그레이팅(grating)이 요구하는 물리적 특성을 만족시키므로 선박에서 화재방지 등이 필요한 여러 설비에 적용할 수가 있다.The pultrusion-molded FRP grating for ships manufactured from the semi-non-combustible resin composition for pultrusion molding of FRP gratings according to the invention has physical and chemical properties such as strength, durability, surface flammability, and non-combustibility to satisfy the physical properties required for a marine grating. Therefore, it can be applied to various facilities requiring fire prevention, etc. on ships.
본 발명에 따른 FRP 그레이팅 인발성형용 준불연성 수지조성물은 섬유보강재에 인발용 수지조성물의 함침성을 향상 및 아라미드 단섬유의 강화보강재에 의해 인발성형에 의해 제작된 FRP(Fiber Reinforced Plastic)의 강도를 향상시키는 효과를 나타낸다.The semi-incombustible resin composition for pultrusion molding for FRP grating according to the present invention improves the impregnation property of the resin composition for pultrusion in the fiber reinforcement material and increases the strength of FRP (Fiber Reinforced Plastic) produced by pultrusion molding with the reinforcing reinforcing material of short aramid fibers. shows an improvement effect.
또한 내구성, 표면인화성, 불연성 등의 물리 화학적 특성이 선박용 FRP 그레이팅(FRP Grating)에 적합하여 강도 및 방화 등이 요구되는 선박의 통행로, 사다리, 플랫트폼 시설에 유리하게 적용될 수 있는 특징을 지니고 있다.In addition, physical and chemical properties such as durability, surface flammability, and non-combustibility are suitable for FRP gratings for ships, so they can be advantageously applied to passageways, ladders, and platform facilities of ships that require strength and fire protection.
도 1은 인발성형 FRP 그레이팅의 제작공정을 개략적으로 나타낸 도면1 is a view schematically showing the manufacturing process of pultrusion-formed FRP grating
이하에서는 본 발명을 실시하기 위한 구체적 내용과 <실시예> 및 <시험예>에 의해 보다 구체적으로 설명하지만 아래 기재 내용 및 실시예의 기재에 의해 본 발명이 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to specific contents and <Examples> and <Test Examples> for carrying out the present invention, but the present invention is not limited by the contents and examples described below.
본 발명에 따른 FRP 그레이팅 인발성형용 준불연성 수지조성물은 불포화폴리에스테르수지 100중량부에 대하여, 염소화폴리염화비닐수지 3 ~ 7중량부, 상용화제로 무수말레인산 크라프트 폴리염화비닐공중합체 또는 무수말레인산변성폴리프로필렌 8 ~ 12중량부, 섬유카플링제로 3-글리시톡시프로필트리메톡시실란 또는 (3-메타크릴옥시프로필)트리메톡시실란 5 ~ 10중량부, 복합난연제로 DOPO(HCA) 8 ~ 12중량부, 브롬계 난연제 8 ~ 12중량부 및 인계 난연제 3 ~ 5중량부, 복합억연제로 수산화알루미늄 3 ~ 5중량부, 수산화마그네슘 3 ~ 5중량부, Zinc-Borate 3 ~ 5중량부, 경화제로 MEKPO 0.8 ~ 1.2중량부, 촉진제로 코발트계 금속비누 0.8 ~ 1.2중량부, 보조결합제로 아세트산 또는 말레익산 0.1 ~ 0.2 중량부 및 강화보조재로 1 ~ 3㎜ 길이의 아라미드 단섬유 3 ~ 7중량부를 포함하여 조성되는 것으로 이루어진다.The semi-incombustible resin composition for pultrusion molding for FRP grating according to the present invention contains 3 to 7 parts by weight of a chlorinated polyvinyl chloride resin, 3 to 7 parts by weight of a chlorinated polyvinyl chloride resin, a kraft polyvinyl chloride copolymer of maleic anhydride or a maleic anhydride-modified poly with respect to 100 parts by weight of the unsaturated polyester resin. 8 to 12 parts by weight of propylene, 5 to 10 parts by weight of 3-glycitoxypropyltrimethoxysilane or (3-methacryloxypropyl)trimethoxysilane as a fiber coupling agent, 8 to 12 parts by weight of DOPO (HCA) as a composite flame retardant Parts, 8 to 12 parts by weight of bromine-based flame retardant and 3 to 5 parts by weight of phosphorus-based flame retardant, 3 to 5 parts by weight of aluminum hydroxide as a composite flame retardant, 3 to 5 parts by weight of magnesium hydroxide, 3 to 5 parts by weight of zinc-borate, and 3 to 5 parts by weight of a curing agent 0.8 to 1.2 parts by weight of MEKPO, 0.8 to 1.2 parts by weight of cobalt-based metal soap as an accelerator, 0.1 to 0.2 parts by weight of acetic acid or maleic acid as an auxiliary binder and 3 to 7 parts by weight of short aramid fibers having a length of 1 to 3 mm as a reinforcing auxiliary material.
본 발명에 따른 상기 불포화폴리에스테르수지는 일반적으로 FRP 에 적용하는 불포화폴리에스테르수지 모두가 가능하고, 구체적으로는 이소프탈산과 다가알코올로부터 제조되는 이소프탈산계 수지 또는 에폭시 수지 말단에 불포화폴리에스테르기를 갖는 비스페놀형 비닐에스테르 수지를 사용하는 것이 바람직하며, 미원화학, 태원화학, 애경화학 등에서 널리 시판되고 있다.The unsaturated polyester resin according to the present invention can be any of the unsaturated polyester resins generally applied to FRP, and specifically, an isophthalic acid-based resin prepared from isophthalic acid and polyhydric alcohol or an epoxy resin having an unsaturated polyester group at the end. It is preferable to use a bisphenol-type vinyl ester resin, and it is widely marketed in Miwon Chemical, Taewon Chemical, Aekyung Chemical, and the like.
본 발명에 따른 염소화폴리염화비닐(Chlorinated Polyvinylchloride CPVC)수지는 폴리염화비닐(PVC)수지의 최대 약점인 내열성, 내식성을 향상시킨 수지로써 화재에 노출시 불이 잘 붙지 않는 불연성이므로 화재예방을 위하여 불연성이 요구되는 구역의 선박용 FRP 그레이팅에 적합하다. Chlorinated polyvinylchloride CPVC resin according to the present invention is a resin with improved heat resistance and corrosion resistance, which are the greatest weaknesses of polyvinyl chloride (PVC) resin. It is suitable for FRP grating for ships in this required area.
상기 염소화 폴리염화비닐(CPVC) 수지는 잘 알려진 공지된 방법에 따라 폴리염화비닐(PVC)을 염소화시켜 제조하며, 불연특성을 위하여 염소함량 65 ~ 72중량% 범위의 염소화 폴리염화비닐(CPVC)수지로 조성된다.The chlorinated polyvinyl chloride (CPVC) resin is prepared by chlorinating polyvinyl chloride (PVC) according to a well-known method, and a chlorinated polyvinyl chloride (CPVC) resin having a chlorine content of 65 to 72% by weight for nonflammable properties. is composed of
본 발명에 따른 상용화제는 불포화폴리에스테르수지와 염소화폴리염화비닐(CPVC)수지를 균일하게 혼합하는 작용을 하며, 불포화폴리에스테르수지 100중량부에 대하여 8 ~ 12중량부를 배합하는 것으로 이루어진다.The compatibilizer according to the present invention functions to uniformly mix the unsaturated polyester resin and the chlorinated polyvinyl chloride (CPVC) resin, and consists of mixing 8 to 12 parts by weight based on 100 parts by weight of the unsaturated polyester resin.
상기 상용화제로 무수말레인산 크라프트 폴리염화비닐공중합체 또는 무수말레인산변성폴리프로필렌가 조성되며, 바람직하게는 무수말레인산 크라프트 폴리염화비닐공중합체가 조성된다.As the compatibilizer, maleic anhydride kraft polyvinyl chloride copolymer or maleic anhydride-modified polypropylene is composed, and preferably maleic anhydride kraft polyvinyl chloride copolymer is composed.
본 발명에 따른 섬유카플링제는 FRP(Fiber Reinforced Plastic)에 일반적으로 채용되는 섬유로빙(Roving)과 섬유매트(Mat)로 이루어진 섬유보강재와 본 발명의 수지조성물 간의 함침성과 함께 친화성을 향상시켜 섬유보강재의 박리현상을 방지하는 효과를 나타낸다.The fiber coupling agent according to the present invention improves affinity with the impregnation property between the fiber reinforcing material consisting of fiber roving and fiber mat generally employed in FRP (Fiber Reinforced Plastic) and the resin composition of the present invention to improve the fiber It shows the effect of preventing the peeling phenomenon of the reinforcing material.
상기 섬유카플링제로 3-글리시톡시프로필트리메톡시실란 또는 (3-메타크릴옥시프로필)트리메톡시실란를 불포화폴리에스테르수지 100중량부에 대하여 5 ~ 10중량부로 배합하는 것으로 이루어진다.The fiber coupling agent consists of mixing 5 to 10 parts by weight of 3-glycitoxypropyltrimethoxysilane or (3-methacryloxypropyl)trimethoxysilane based on 100 parts by weight of the unsaturated polyester resin.
본 발명에 따른 복합난연제는 DOPO(HCA), 브롬계 난연제 및 인계 난연제를 병용하여 조성되며, 복합억연제 역시 수산화알루미늄, 수산화마그네슘 및 Zinc-Borate를 병용하여 조성하는 것으로 이루어지며, 경화제로 MEKPO 및 촉진제로 코발트계 금속비누를 배합하는 것으로 이루어진다.The composite flame retardant according to the present invention is composed of DOPO (HCA), a bromine-based flame retardant and a phosphorus-based flame retardant, and the composite flame retardant is also composed of aluminum hydroxide, magnesium hydroxide and zinc-borate in combination, and MEKPO and It consists of blending a cobalt-based metal soap as an accelerator.
상기 본 발명에 따른 복합난연제, 복합억연제, 경화제로 및 촉진제는 널리 시판하고 있는 성분이므로 본 발명이 속하는 기술분야의 숙련자이면 쉽게 구입하여 본 발명에 적용할 수가 있어 구체적인 설명은 생략한다.Since the composite flame retardant, composite flame retardant, curing agent and accelerator according to the present invention are widely marketed components, those skilled in the art to which the present invention pertains can easily purchase it and apply it to the present invention, so detailed descriptions will be omitted.
본 발명에 따른 상기 보조결합제는 커플링제로서 사용되는 유기 실란 화합물의 가수분해를 촉진하여 커플링제의 결합력을 증진시키는 역할을 하며, 불포화폴리에스테르수지 100중량부에 대하여 아세트산 또는 말레익산 0.1 ~ 0.2 중량부로 조성되는 것이 바람직하다The auxiliary binder according to the present invention serves to promote the hydrolysis of the organic silane compound used as the coupling agent to enhance the bonding strength of the coupling agent, and 0.1 to 0.2 weight of acetic acid or maleic acid based on 100 parts by weight of the unsaturated polyester resin It is preferable to consist of wealth
본 발명에 따른 상기 강화보조재로 5 ~ 14㎛의 직경 및 1 ~ 3㎜ 길이의 아라미드 단섬유를 배합하며, 아라미드 단섬유는 일 방향으로 공급되는 섬유로빙(Roving)에 대하여 다 방향으로 분산되어 FRP의 강도를 보다 향상시키는 작용을 한다.As the reinforcing auxiliary material according to the present invention, short aramid fibers having a diameter of 5 to 14 μm and a length of 1 to 3 mm are blended, and the short aramid fibers are dispersed in multiple directions with respect to the fiber roving supplied in one direction to FRP. It works to further improve the strength of
상기 아라미드 단섬유의 길이는 1 ~ 3㎜가 바람직하며, 상기 범위를 벗어나면 성형조성물의 점도 상승 및 단섬유의 분산성에 문제가 발생하여 성형성에 문제점이 있을 수 있다.The length of the short aramid fibers is preferably 1 to 3 mm, and if it is out of the above range, there may be problems in moldability by increasing the viscosity of the molding composition and dispersibility of the short fibers.
그리고 본 발명은 FRP 그레이팅 인발성형용 준불연성 수지조성물을 이용하여 제조되는 인발성형 FRP 그레이팅을 포함하며, 인발성형 FRP 그레이팅은 잘 알려진 FRP 인발성형공정에 의해 FRP 그레이팅 제조를 위한 부분품으로 FRP 성형물을 제조하고, 제조된 FRP 성형물으로부터 조립 등에 의해 FRP 그레이팅을 제조하는 것으로 이루어진다.And the present invention includes a pultrusion-formed FRP grating manufactured using a semi-incombustible resin composition for pultrusion molding of FRP gratings, and the pultrusion-formed FRP grating is a well-known FRP pultrusion molding process to manufacture FRP gratings as parts for manufacturing FRP gratings. and manufacturing the FRP grating by assembling or the like from the manufactured FRP molding.
상기 FRP 인발성형공정은 알려진 FRP 인발성형기술이므로 본 발명이 속하는 가술분야의 숙련자이면 쉽게 채용할 수 있으며, 상기 FRP 인발성형을 간단하게 설명하면,Since the FRP pultrusion process is a known FRP pultrusion technique, it can be easily employed by those skilled in the art to which the present invention belongs.
a). 섬유로빙(Roving)과 섬유매트(Mat)로 이루어진 섬유보강재를 연속적으로 공급하는 섬유보강재 공급단계, b). 공급되는 섬유보강재에 수지를 함침시키는 함침단계, c). 함침된 섬유보강재를 성형가이드에 의해 가열된 금형으로 공급하여 금형을 통과하면서 열경화시키는 경화단계, d). 금형으로부터 배출되는 경화된 섬유보강재를 클램핑 풀러(clamping puller)에 의해 인발하는 인발단계, e). 인발공정에 의해 일정두께로 제조되는 FRP를 일정규격으로 절단하는 절단공정을 포함하는 것으로 이루어진다.a). A fiber reinforcement material supply step of continuously supplying a fiber reinforcement material consisting of fiber roving and fiber mat, b). Impregnation step of impregnating the resin to the supplied fiber reinforcement material, c). A curing step in which the impregnated fiber reinforcement is supplied to a mold heated by a molding guide and thermally cured while passing through the mold, d). A drawing step of drawing the hardened fiber reinforcement discharged from the mold by a clamping puller, e). It consists of including a cutting process of cutting the FRP manufactured to a certain thickness by the drawing process to a certain standard.
아래에서는 <실시예> 및 <시험예>를 통하여 본 발명의 FRP 그레이팅 인발성형용 준불연성 수지조성물에 하여 보다 구체적으로 설명하기로 한다.Hereinafter, the semi-incombustible resin composition for pultrusion molding of FRP grating of the present invention will be described in more detail through <Example> and <Test Example>.
<실시예> <Example>
시판 중인 내식성 불포화폴리에스테르수지인 에폭시수지 말단에 불포화폴리에스테르기를 갖는 비스페놀형 비닐에스테르 수지를 주성분으로 하여 아래 [표 1]에 제시한 배합비에 따라 교반기가 장착된 배합기에서 조성성분 들을 투입하고 균일하게 배합하여 FRP 인발성형용 준불연성 수지조성물을 조성한다.Commercially available corrosion-resistant unsaturated polyester resin, a bisphenol-type vinyl ester resin having an unsaturated polyester group at the end of the epoxy resin as the main component, according to the mixing ratio shown in [Table 1] below, the composition components are added in a blender equipped with a stirrer, and uniformly By mixing, a semi-incombustible resin composition for FRP pultrusion is formed.
그리고 상기 조성된 FRP 그레이팅 인발성형용 준불연성 수지조성물을 이용하여 알려진 FRP 그레이팅 인발성형기술에 의해 인발성형 FRP 그레이팅을 제조하였으며, 아래 <시험예>를 위하여 제조된 FRP 그레이팅을 일정규격으로 절단하여 시편을 제작하였다.And using the above-formed semi-incombustible resin composition for pultrusion molding of FRP grating, pultrusion-formed FRP grating was manufactured by known FRP grating pultrusion molding technology, and the FRP grating prepared for the following <Test Example> was cut to a certain standard and a specimen was produced.
<시험예 1> <Test Example 1>
<실시예>에 제작한 시편을 이용하여 본 발명에 따른 인발성형 FRP 그레이팅에 대한 기계적 특성을 시험하고, 그 결과를 아래 [표 2]에 나타내었다The mechanical properties of the pultrusion-formed FRP grating according to the present invention were tested using the specimen prepared in <Example>, and the results are shown in [Table 2] below.
<시험예 2> <Test Example 2>
<실시예>에 제작한 시편을 이용하여 FRP 그레이팅의 거동을 결정하는 중요한 요소인 압축시험(시험방법 KS B 5541:1985) 결과 및 화재방지용 불연성소재의 평가를 위한 가연성 시험결과를 아래 [표 3] 및 [표 4]로 각각 나타내었다.The results of the compression test (Test Method KS B 5541:1985), which are important factors determining the behavior of FRP gratings, using the specimens produced in <Example> and the flammability test results for evaluation of non-combustible materials for fire prevention are shown below [Table 3] ] and [Table 4], respectively.
상기 [표 2] 내지 [표 4]에 나타낸 시험결과는 선박용 인발성형 FRP 그레이팅에서 요구되는 강도, 내구성 및 화재방지를 위한 불연성 등의 특성을 만족시키므로 본 발명에 따른 FRP 인발성형용 준불연성 수지조성물은 선박용의 인발성형 FRP 그레이팅을 제조하는데 매우 유리한 특징을 지니고 있다.The test results shown in [Table 2] to [Table 4] satisfy the characteristics such as strength, durability, and non-combustibility for fire prevention required in the pultrusion molding for ships FRP grating, so the semi-incombustible resin composition for pultrusion molding for FRP according to the present invention has very advantageous characteristics for manufacturing pultrusion FRP gratings for ships.
Claims (5)
A semi-noncombustible pultrusion-molded FRP grating, characterized in that it is manufactured by FRP pultrusion using the semi-incombustible resin composition for pultrusion molding of the FRP grating according to claim 1 or 2.
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