KR20190114462A - A method of coating expanded polystyrene resin particles expanded graphite and a non-incombustible molded product formed by the above-mentioned method and forming a coating film which expands when heated - Google Patents

A method of coating expanded polystyrene resin particles expanded graphite and a non-incombustible molded product formed by the above-mentioned method and forming a coating film which expands when heated Download PDF

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KR20190114462A
KR20190114462A KR1020180037211A KR20180037211A KR20190114462A KR 20190114462 A KR20190114462 A KR 20190114462A KR 1020180037211 A KR1020180037211 A KR 1020180037211A KR 20180037211 A KR20180037211 A KR 20180037211A KR 20190114462 A KR20190114462 A KR 20190114462A
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expanded graphite
expanded
resins
coating
particles
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KR102149238B1 (en
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김재천
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22After-treatment of expandable particles; Forming foamed products
    • C08J9/224Surface treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009Use of pretreated compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • C08J9/365Coating

Abstract

The present invention foams expandable polystyrene (EPS) resin particles, oxidizes the surface with ozone to modify the hydrophobic particles to be hydrophilic and to enhance adhesion, stirs the expanded graphite at a pressure of 0.005 to 0.1 MPa to mold by forming a solid coating on the surface layer of the resin particles without damaging the expanded graphite particles, and forms a coating film that expands upon heating on the molded article, thus it is possible to produce a semi-non-combustible polystyrene (styrofoam) foam, thereby contributing to fire prevention.

Description

팽창흑연을 발포한 폴리스티렌 수지 입자에 코팅하는 방법 및 상기 발법으로 제조되는 가열하면 팽창하는 도막을 형성한 불연성 성형물 {A method of coating expanded polystyrene resin particles expanded graphite and a non-incombustible molded product formed by the above-mentioned method and forming a coating film which expands when heated}A method of coating expanded polystyrene resin particles expanded graphite and a non-incombustible molded product formed by the above method of coating expanded graphite with expanded polystyrene resin particles and forming a coating film which expands upon heating prepared by the above method. -mentioned method and forming a coating film which expands when heated}

본 발명은 발포성폴리스티렌(Expandable Polystyrene 이하' EPS'라 칭한다)수지 입자를 발포하고 팽창흑연을 발포한 폴리스티렌 수지 입자에 코팅하여 도막을 형성한 폴리스티렌 폼에 관한 것으로, 팽창율(Expansion rato) 20ml/g - 500ml/g 이며, 입도직경이 20mesh - 300mesh 인 팽창흑연을 EPS를 발포한 입자에 코팅하는 방법 및 팽창흑연 도막이 형성된 폴리스티렌 폼(스티로폼)을 얻기 위한 것이다. 보다 상세하게는 중합을 완료한 소수성인 EPS 입자를 발포한 후 오존으로 산화하여 친수성으로 개질하고 팽창율(Expansion rato) 20ml/g - 500ml/g 이며, 입도직경이 20mesh - 300mesh 인 팽창흑연을 파라핀을 매질로 하여 0.005MPa ~ 0.1MPa의 압력으로 코팅한 후 성형하고 가열하면 팽창하는 도막을 성형물에 형성시켜 불연성의 폴리스티렌 폼(스티로폼)을 수득하는 팽창흑연을 발포한 폴리스티렌 수지 입자에 코팅하는 방법에 관한 발명이다.The present invention relates to a polystyrene foam in which a coating film is formed by foaming expanded polystyrene (hereinafter referred to as EPS ') resin particles and coating expanded polystyrene resin particles with expanded graphite, wherein the expansion ratio is 20 ml / g- 500ml / g and a method of coating expanded graphite having a particle size of 20mesh-300mesh on EPS-foamed particles and a polystyrene foam (styrofoam) in which an expanded graphite coating film is formed. More specifically, after the completion of the polymerization, the hydrophobic EPS particles are foamed and then oxidized with ozone to be modified hydrophilicly.Expansion rato is 20ml / g-500ml / g, and the expanded graphite having a particle size of 20mesh-300mesh is paraffin. A method of coating expanded polystyrene resin particles on expanded polystyrene resin particles obtained by coating a pressure medium of 0.005 MPa to 0.1 MPa as a medium, then forming and heating to form an expanded coating film in the molding to obtain a non-combustible polystyrene foam (styrofoam). Invention.

발포성폴리스티렌(EPS)은 스티로폼의 원료 물질인 스티렌의 중합체로 직경 약 0.2mm - 1.5mm의 원구형 수지입자이다. 입자 내부에는 발포성 가스가 함유되어 있으며 소정의 온도로 가열하여 입자를 80배 이상 발포하고 발포한 입자를 숙성시키고, 증기로 성형한 성형품을 통상 스티로폼이라 한다.Expandable polystyrene (EPS) is a polymer of styrene, a raw material of styrofoam, and is a spherical resin particle having a diameter of about 0.2 mm to 1.5 mm. A foaming gas is contained inside the particles, and the foamed gas is heated to a predetermined temperature to foam the particles 80 times or more, to mature the foamed particles, and a molded article formed by steam is usually called styrofoam.

최근에는 불연성이 높은 스티로폼 단열재가 요구되고 있는 실정으로 불연성을 향상시키기 위한 다양한 방식의 노력이 시도되고 있으며, 스티렌 중합공정 및 압출 공정에서 수지입자 내부에 불연성 물질을 분산시키거나 EPS 입자를 증기로 가열하여 발포하고 발포입자에 난연성 또는 방염성 물질을 코팅하여 성형하는 제조방법들이 있다.In recent years, various types of efforts have been made to improve non-combustibility, and styrofoam insulation materials having high incombustibility are required. In the styrene polymerization process and extrusion process, non-combustible materials are dispersed inside resin particles or EPS particles are heated by steam. By foaming and coating the flame-retardant or flame-retardant material on the foam particles there is a manufacturing method.

본 발명자의 대한민국 특허 제1300627호에는 발포성 폴리스티렌 수지입자를 저온플라즈마를 방전 처리하여 개질 된 발포성 수지 입자 표면층에 단열재와 난연재와 기능성 물질들을 강력하게 밀착 코팅하여 단열성이 우수한 발포성 폴리스티렌 수지 입자를 제조하는 기술이 개시되어 있으며 대한민국 특허 제1494801호에는 설탕과 인산을 혼합 반응시켜서 캐러멜을 형성 시키고 팽창흑연 분산제 이소시아네이트를 혼합한 접착제를 제조하는 방법을 개시하고 있다.Korean Patent No. 1300627 of the present inventors discloses a technique for producing expanded polystyrene resin particles having excellent thermal insulation properties by coating a foamed polystyrene resin particle with a low-temperature plasma by discharging the insulating material, a flame-retardant material, and a functional material on the surface layer of the modified foamed resin particle. Korean Patent No. 1448051 discloses a method of preparing an adhesive in which caramel is formed by mixing and reacting sugar and phosphoric acid, and an expanded graphite dispersant isocyanate is mixed.

대한민국 공개특허 10-2016-0134452호에는 팽창에 의하여 발포가 일어나 부피가 약 500배로 확대된 팽창된 흑연을, 분쇄하고 코팅제에 첨가하여 팽창된 흑연을 첨가한 코팅제와 그 제조방법 및 용도에 관한 제조 방법을 개시하고 있다.Korean Patent Laid-Open Publication No. 10-2016-0134452 discloses a coating agent containing swelled graphite, expanded to about 500 times the volume by expansion, and added to the coating agent, and a method for producing the coating agent and its manufacturing method. A method is disclosed.

대한민국 공개특허 10-2011-0065707 스티렌계 폴리머 내에 실리콘계 분말 및 팽창질석 분말을 포함하는 것임을 특징으로 하는 난연성 발포성 폴리스티렌 수지입자의 제조방법을 개시하고 있다.Korean Patent Laid-Open Publication No. 10-2011-0065707 Disclosed is a method for preparing a flame-retardant expandable polystyrene resin particle, characterized in that it comprises a silicon-based powder and expanded vermiculite powder in a styrene-based polymer.

이와 같은 종래의 다양한 선행 기술들은 팽창시킨 흑연 분말을 코팅제와 혼합하거나 팽창 흑연에 각종 무기물 및 금속 비금속을 열경화성 수지에 혼합하여 코팅제를 제조하여 사용하는 방법이므로 팽창흑연의 팽창력이 미약하고 소수성인 EPS 입자에 접착 코팅하기 곤란하며 코팅한 분말들이 쉽게 떨어지므로 최종 물성이 난연재료(난연3급) 성능에 미달하는 문제점과 제조 공정이 비경제적이었다.These various prior arts are methods of preparing expanded coatings by mixing expanded graphite powder with a coating agent or by mixing various inorganic and metal non-metals with thermosetting resins in expanded graphite, thereby expanding and expanding the expanded graphite powder. It is difficult to adhesively coat and the coated powders easily fall off, so the final physical properties of the flame retardant material (flame retardant 3) performance and the manufacturing process was uneconomical.

본 발명은 위와 같은 종래 기술들의 문제점을 해결한 것으로 중합을 완료한 EPS 입자를 발포한 후 오존으로 산화하여 친수성으로 개질하고 탄소함량 92% 이상 인 팽창흑연을 파손 없는 압력으로 코팅하는 단계로 성형한 후 성형물에 팽창흑연을 다시 도포하여 가열하면 팽창하는 도막을 형성시키고 불연성의 폴리스티렌 발포폼(스티로폼)에 관한 발명이다.The present invention is to solve the problems of the prior art as described above by foaming the completed EPS particles and oxidized with ozone to modify the hydrophilicity and to form the expanded graphite having a carbon content of more than 92% by coating a pressure without damage The present invention relates to a non-flammable polystyrene foam (styrofoam), after which expanded graphite is again applied to a molding to form a coating film which expands upon heating.

대한민국 특허 제1300627호Republic of Korea Patent No. 1300627 대한민국 특허 제1494801호Republic of Korea Patent No.1494801 대한민국 공개특허 제10-2016-0134452호Republic of Korea Patent Publication No. 10-2016-0134452 대한민국 공개특허 제10-2011-0065707호Republic of Korea Patent Publication No. 10-2011-0065707

본 발명의 목적은 EPS 수지 입자를 발포하고 오존으로 산화 개질하여 접착력을 강화하고 팽창흑연을 견고하게 코팅하여 불연성을 확보하는데 그 목적이 있다.An object of the present invention is to foam the EPS resin particles and oxidatively modify with ozone to enhance adhesion and firmly coat the expanded graphite to ensure nonflammability.

본 발명의 또 다른 목적은 무기물질 금속 비철금속을 포함시키지 않고 탄소 함량 92%의 팽창흑연을 입자의 파손 없이 0.005Mpa - 0.1Mpa 저 압력으로 코팅하여 팽창력을 유지시켜 열원으로부터 불연성을 확보하는데 그 목적이 있다.It is another object of the present invention to maintain non-flammability from the heat source by coating the expanded graphite having a carbon content of 92% and low pressure 0.005Mpa-0.1Mpa without breaking the inorganic metal and non-ferrous metal to maintain the expansion force have.

본 발명의 또 다른 목적은 상기의 EPS 수지 입자를 성형하고 성형물을 팽창 흑연으로 도포하여 가열하면 팽창하는 도막을 형성시켜서 불연성의 폴리스티렌 발포폼(스티로폼)을 확보하는데 그 목적이 있다.Another object of the present invention is to form a coating film that expands when the above-mentioned EPS resin particles are molded and the molded product is coated with expanded graphite and heated to secure a non-combustible polystyrene foam (styrofoam).

본 발명의 목적은 EPS 수지 입자를 발포하고 오존으로 산화 개질하여 접착력을 강화하고 팽창흑연을 견고하게 코팅하여 불연성을 확보하는데 그 목적이 있다.An object of the present invention is to foam the EPS resin particles and oxidatively modify with ozone to enhance adhesion and firmly coat the expanded graphite to ensure nonflammability.

본 발명의 또 다른 목적은 무기물질 금속 비철금속을 포함시키지 않고 탄소 함량 92%의 팽창흑연을 입자의 파손 없이 0.005 Mpa - 0.1 Mpa 저 압력으로 코팅하여 팽창력을 유지시켜 열원으로부터 불연성을 확보하는데 그 목적이 있다.It is another object of the present invention to maintain non-flammability from a heat source by coating the expanded graphite having a carbon content of 92% without breaking the inorganic metal non-ferrous metal at low pressure 0.005 Mpa-0.1 Mpa without breaking the particles to maintain the expansion force have.

본 발명의 또 다른 목적은 상기의 EPS 수지 입자를 성형하고 성형물을 팽창 흑연으로 도포하여 가열하면 팽창하는 도막을 형성시켜서 불연성의 폴리스티렌 발포폼(스티로폼)을 확보하는데 그 목적이 있다.Another object of the present invention is to form a coating film that expands when the above-mentioned EPS resin particles are molded and the molded product is coated with expanded graphite and heated to secure a non-combustible polystyrene foam (styrofoam).

본 발명에서 사용하는 발포성 폴리스티렌(EPS, Expandable Polystyrene)수지 입자는 통상적으로 스티렌 단독 중합체 혹은 공중합체를 기초수지로 하고 여기에 발포제로 부탄 또는 펜탄 가스를 함유하고 있다. Expandable Polystyrene (EPS) resin particles used in the present invention are generally based on styrene homopolymers or copolymers, and contain butane or pentane gas as a blowing agent.

EPS 입자는 소수성이므로 친수성인 팽창흑연의 접착 코팅을 반발하는 성질이 있어 본 발명은 EPS 입자를 발포하고 오존으로 개질하여 입자 표면층을 산화시켜 친수성으로 개질함으로서 팽창흑연의 접착 코팅이 용이하도록 한다.Since the EPS particles are hydrophobic, they have a property of repelling the adhesive coating of hydrophilic expanded graphite, and thus, the present invention makes the adhesive coating of expanded graphite easy by foaming the EPS particles and modifying them with ozone to oxidize the particle surface layer.

상기의 오존은 산소분자(O2)가 분해되어 3개의 산소원자가 결합한 물질로서 3개의 산소원자가 4가지 형상의 공명 구조로 결합된 형태로 존재한다.The ozone is a substance in which oxygen molecules (O 2 ) are decomposed to combine three oxygen atoms, and three oxygen atoms are present in the form of four resonance structures.

오존은 불소 다음으로 강력한 산화력을 가지며 유무기물과의 반응성은 산화력에 의한 것이다. 오존의 발생은 통상 산소에 물리, 화학적인 에너지를 가해 오존으로 변화시키는 것인데 무성 방전법, 전해법, 광화학법, 방사선 조사법 등으로부터 발생시킬 수 있다. Ozone has the strongest oxidizing power after fluorine and its reactivity with organic matter is due to its oxidizing power. Ozone is usually generated by applying physical and chemical energy to oxygen and changing it to ozone. The ozone can be generated from a silent discharge method, an electrolysis method, a photochemical method, or a radiation method.

통상적으로 무성방전법이 가장 널리 이용되며, 무성방전법은 1쌍의 전극 사이에 유리나 세라믹 같은 유전체를 끼우고 공기나 산소를 불어넣고, 전극에 6kv

Figure pat00001
18kv 교류고압을 가하면 방전영역에서 오존이 발생된다. 무성방전법의 오존발생은 공기를 사용한 경우, 10g
Figure pat00002
35 g/m3, 산소를 사용할 경우에는 50g
Figure pat00003
150 g/m3의 오존을 얻을 수 있고 소비 전력은 수냉식 냉각수 온도 25℃의 경우 산소를 주입 할 때 10
Figure pat00004
13 kwh/kg-O3 이며, 공기를 주입할 때는 15
Figure pat00005
20 kwh/kg-O3이다. 오존 발생장치는 넓게 분류하여 원형의 동축 원통형과 판상의 평판형이 있으며, 본 발명에서는 산업용에 널리 사용하고 있는 무성방전법의 동축원통형의 전극구조를 사용하였다.In general, the silent discharge method is most widely used. The silent discharge method inserts a dielectric such as glass or ceramic between a pair of electrodes and blows air or oxygen into the electrode.
Figure pat00001
Applying 18kv AC high pressure produces ozone in discharge area. Ozone generation by silent discharge method is 10g when air is used
Figure pat00002
35 g / m3, 50 g when using oxygen
Figure pat00003
Ozone of 150 g / m3 can be obtained and the power consumption is 10 when injecting oxygen for water-cooled coolant temperature 25 ℃
Figure pat00004
13 kwh / kg-O3, 15 when injecting air
Figure pat00005
20 kwh / kg-O3. The ozone generating apparatus is broadly classified into a circular coaxial cylindrical shape and a plate-like flat plate type. In the present invention, a coaxial cylindrical electrode structure of a silent discharge method widely used in industrial applications is used.

다음 반응식에 의하여 오존이 발생된다.Ozone is generated by the following reaction formula.

O2 + e- -> O + O + e- O 2 + e - -> O + O + e -

O2 + e- -> O2 + O 2 + e -- > O 2 +

O + O2 +M -> O3 + M O + O 2 + M-> O 3 + M

O2 + O2 -> O3 + O O 2 + O 2- > O 3 + O

팽창흑연은 천연 인편흑연을 산성재료로 화학 처리를 하여 흑연의 층간에 산성 화합물을 침투시켜 건조한 것으로 150℃ 이상으로 가열하면 분해되어 가스를 발생하면서 체적의 20배 ~ 500배로 팽창이 될 수 있으며 이를 통상적으로 팽창흑연 (Expandable Graphite)이라 한다.Expanded graphite is chemically treated with natural flake graphite with an acidic material to infiltrate the acidic compound between layers of graphite, and is dried. When it is heated above 150 ℃, it can decompose and generate gas and expand to 20 ~ 500 times of volume. It is commonly called Expandable Graphite.

본 발명에서 팽창흑연을 사용하는 목적은 가열에 의해 20-500배로 팽창하는 탄소 발포층이 열원을 차단하여 폴리스티렌 폼의 연소를 방해하는 작용을 활용하는 것이므로 팽창흑연은 팽창율(Expansion rato) 20ml/g - 500ml/g 인 팽창흑연 중에서 선택하여 사용할 수 있으며 바람직한 팽창율은 20ml/g - 300ml/g 이고, 바람직한 입도는 60mesh - 200mesh 이다.In the present invention, the purpose of using expanded graphite is to expand the 20-500 times by heating to utilize the action of blocking the combustion of the polystyrene foam by blocking the heat source to expand the graphite is expanded expansion (Expansion rato) 20ml / g -500ml / g of expanded graphite can be selected and used, the preferred expansion ratio is 20ml / g-300ml / g, the preferred particle size is 60mesh-200mesh.

본 발명에서 팽창흑연이 고압 또는 충격 등에 의해 파손되거나 팽창성이 없는 무기물질 및 금속 비철금속들이 10중량부 이상 포함 되면 팽창하는 물성이 감소되고 발명이 의도하는 목적을 달성할 수 없으므로 0.005Mpa - 0.1Mpa의 저 압력으로 교반하여 팽창흑연 입자의 파손 없어야 하며 탄소 함량92% 이상인 팽창 흑연을 사용 한다 접착성 수지는 열가소성 수지 및 열가소성으로 조절하여 사용 한다.In the present invention, when the expanded graphite is damaged by high pressure or impact or the like, and contains more than 10 parts by weight of inorganic materials and non-expandable non-expandable metals, the expanded physical properties are reduced and the intention of the invention cannot be achieved. Therefore, 0.005Mpa-0.1Mpa Agitate at low pressure to avoid breakage of expanded graphite particles and use expanded graphite with a carbon content of more than 92%. Adhesive resins are controlled by thermoplastic resins and thermoplastics.

열경화성 수지는 가열로 인해 경화된 수지의 결합이 팽창흑연의 팽창력을 억제하는 문제점이 있다 발포한 EPS 입자 100중량부에 대하여 팽창흑연 1 ~ 50 중량부(고형분 30%)를 코팅할 수 있으며 바람직하게는 10 ~ 25 중량부를 접착 코팅한다. 이 범위를 초과하면 물성의 증진이 미약하고, 경제성이 떨어지므로 탄소함량 92% (Carbon Content), 팽창율(Expansion rate) 20ml/g ~ 300ml/g, 입도(Particle distribution) 60 mesh 이상의 팽창흑연을 사용하는 것이 바람직하다.Thermosetting resin has a problem that the bonding of the cured resin due to heating to suppress the expansion force of the expanded graphite may be coated with 1 to 50 parts by weight (30% solids) of expanded graphite with respect to 100 parts by weight of expanded EPS particles. Adhesive coating 10 to 25 parts by weight. If this range is exceeded, the improvement of physical properties is inferior and the economic efficiency is low. Therefore, expanded carbon of 92% (Carbon Content), Expansion rate 20ml / g ~ 300ml / g, Particle distribution 60 mesh or more is used. It is desirable to.

팽창 흑연을 파손 없이 코팅하기 위하여 윤활성이 우수한 매질을 사용할 수 있으며 예를 들어서 파라핀을 사용 할 수 있으며 파라핀은 고체의 탄화수소 혼합물이며 에테르나 벤젠 에스테르에 녹는 물질로 윤활성과 흡착성이 우수하다 팽창흑연을 EPS에 접합 코팅하는 단계에서 투입되며 팽창흑연 입자 표면에 코팅 된다.In order to coat the expanded graphite without damage, it is possible to use an excellent lubricity medium. For example, paraffin may be used. Paraffin is a solid hydrocarbon mixture and is soluble in ether or benzene ester. It is added in the step of coating coating on the coated graphite particle surface.

파라핀은 염화파라핀, 고형파라핀, 유동파라핀 중에서 선택하여 1종 단독 또는 2종 이상 혼합하여 사용할 수 있다 발포한 EPS 입자 100중량부에 대하여 1 -20 중량부 사용하며 바람직하게는 5 ~ 15 중량부 사용한다. Paraffin may be used alone or in combination of two or more by selecting from paraffin chloride, solid paraffin, and liquid paraffin. 1 to 20 parts by weight based on 100 parts by weight of expanded EPS particles are used, and preferably 5 to 15 parts by weight. do.

본 발명에서 사용하는 접착성 수지(고형분 30%)는 팽창 흑연을 EPS 입자에 접착 시킬 수 있는 물성이며 열가소성이면 제한 없이 선택하여 사용 할 수 있으며The adhesive resin (solid content 30%) used in the present invention is a physical property capable of adhering expanded graphite to EPS particles and can be used without limitation as long as it is thermoplastic.

예를 들어서 아크릴수지, 폴리에틸렌수지, 폴리프로필렌수지, 폴리스티렌수지, 초산비닐수지, 불소수지, 염화비닐수지, 폴리아미드수지, 아세틸수지, 폴리카보네이트수지 ABS수지 등이 있다.Examples include acrylic resins, polyethylene resins, polypropylene resins, polystyrene resins, vinyl acetate resins, fluorine resins, vinyl chloride resins, polyamide resins, acetyl resins, polycarbonate resins and ABS resins.

이들 중, 1종 또는 2종 이상을 혼합하여 발포한 EPS 입자 100중량부에 대하여 1 - 50 중량부 사용 할 수 있으며 바람직하게는 1중량부 - 30중량부를 사용하며 Among them, 1 to 50 parts by weight may be used with respect to 100 parts by weight of EPS particles foamed by mixing one or two or more kinds, and preferably 1 part by weight to 30 parts by weight.

1. 직경 0.2mm-1.5mm의 EPS 입자를 발포하고 숙성 시키는 단계;1. Foaming and aging EPS particles 0.2mm-1.5mm in diameter;

2.오존화 된 공기로 발포 된 EPS 입자를 산화하여 친수성으로 개질하여 접착력을 강화 시키는 단계;2.oxidizing EPS particles foamed with ozoneized air to modify them to hydrophilic to enhance adhesion;

3. 상기 발포 입자에 팽창흑연과 파라핀 및 접착성수지를 투입하고 0.005 MPa - 0.1 MPa로 1 - 10rpm 으로 코팅하는 단계;3. Adding expanded graphite, paraffin and adhesive resin to the foamed particles and coating at 1-10 rpm with 0.005 MPa-0.1 MPa;

4. 팽창흑연이 코팅된 EPS 입자를 건조하는 단계;4. drying the expanded graphite coated EPS particles;

5. 건조된 수지입자를 성형기에 투입하고 증기를 가하여 성형하는 단계;5. The dried resin particles are introduced into a molding machine and molded by adding steam;

6. 성형품 표면층에 팽창흑연을 도포하여 가열하면 20 - 500배 팽창하는 도막을 형성하는 단계로 본 발명은 완성 된다.6. The present invention is completed by forming a coating film which expands by 20 to 500 times when the expanded graphite is applied to the molded article surface layer and heated.

믹서기는 팽창흑연의 파손을 방지하기 위하여 0.005 MPa ~ 0.1MPa 압력으로 가동하였고 직경 1m 길이 1.5m 의 원통형이며 통이 회전하여 충격이 약한 텀블러형 믹서기를 사용하였다. The mixer was operated at 0.005 MPa ~ 0.1MPa pressure to prevent breakage of expanded graphite, and a tumble mixer was used, which was cylindrical with a diameter of 1m and a length of 1.5m and the cylinder was rotated.

본 발명의 최종 목적은 수득한 EPS 발포 입자를 1차) 통상적인 비드법 으로 성형하면 다소 불안정한 준불연성이 형성되므로 The final object of the present invention is to form a somewhat unstable quasi-incombustibility of the obtained EPS foam particles formed by primary) conventional bead method

2차) 성형물 표면층에 팽창흑연을 도포하고 가열에 팽창하는 도막을 형성하여 불연성을 형성 시키려는 것이 본 발명의 최종 목적이다 상기와 같이 팽창 흑연을 도포함에 있어, 분사하여 도포하거나, 도색방법으로 도포하거나 또는 팽창흑연을 머금은 상하 롤러 사이로 폼을 통과시키며 도포하거나 또는 성형품을 팽창흑연에 함침 하는 방법 등으로 팽창 흑연 도막을 형성시킬 수 있으며 Second) It is the final object of the present invention to apply expanded graphite to the surface layer of the molding and to form a non-combustible film by forming a coating film that expands upon heating. In the application of the expanded graphite as described above, by spraying or applying the coating method Alternatively, the expanded graphite coating film may be formed by applying a foam between the upper and lower rollers with expanded graphite or impregnating the molded product with the expanded graphite.

바람직하게는 팽창 흑연을 접착제에 혼합하여 성형품에 도포하는 방법으로 경제적이고 효율적이며 목적은 성형품 표면에 팽창흑연의 도막을 형성하여 함유시키는 것이다.Preferably, the expanded graphite is mixed with an adhesive and applied to a molded article, which is economical and efficient, and an object thereof is to form and contain a coated graphite film on the molded article surface.

본 발명은 팽창율(Expansion rato)이 20ml/g - 500ml/g 인 팽창흑연을 0.005 MPa - 0.1 MPa의 압력으로 파손 없이 입자에 코팅하고 또한, 윤활성이 우수한 파라핀을 용질로 사용함으로써, 폴리스티렌 폼의 팽창력을 극대화하였으며, 성형물이 가열하면 팽창하는 도막을 형성시킴으로써 불연성 뛰어난 본 발명의 폴리스티렌 폼(스티로폼)은 화재 예방에 크게 기여 할 수 있다. The present invention provides an expansion force of polystyrene foam by coating expanded particles having an expansion ratio of 20 ml / g-500 ml / g at a pressure of 0.005 MPa-0.1 MPa without damage and by using paraffin having excellent lubricity as a solute. The polystyrene foam (styrofoam) of the present invention having excellent non-combustibility by forming a coating film that expands when the molding is heated can greatly contribute to fire prevention.

기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다. 또한, 본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 실시예들을 본문에 상세하게 설명하고자 한다. 그러나 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, All terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art, and are not construed in ideal or excessively formal meanings unless expressly defined in this application. Do not. In addition, the present invention may be variously modified and may have various forms, and exemplary embodiments will be described in detail in the text. However, this is not intended to limit the invention to the specific form disclosed,

본 발명의 사상 및 기술범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 그리고, 본 발명의 발포한 EPS 수지입자와 이를 성형한 성형물 표면층에 팽창흑연을 도포하여 가열하면 20 - 300배로 팽창하는 도막을 형성하여 성형물의 연소를 방지하려는 의도와 목적에 부합하면 다소 변형된 다른 도포방법들도 본 발명의 범위 안에 있다. 이하, 본 발명의 실시예에서 제조된 발포성 폴리스티렌을 발포 성형한 발포폼(스티로폼)의 불연 물성 등에 대하여 설명하나, 본 발명의 범위는 실시예의 범위에 한정되지 아니하며 실시예로 부터 뒷받침되는 모든 범위를 포함한다고 할 수 있다.It is to be understood that all changes, equivalents, and substitutes included in the spirit and scope of the present invention are included. In addition, the expanded EPS resin particles of the present invention and the expanded graphite is coated on the surface layer of the molded article to form a coating film which expands by 20 to 300 times when heated to prevent the combustion of the molded article. Coating methods are also within the scope of the present invention. Hereinafter, the non-combustible properties of the foamed foam (styrofoam) foam-molded foamed polystyrene prepared in the embodiment of the present invention, but the scope of the present invention is not limited to the scope of the embodiment and all the ranges supported by the embodiment It can be said to include.

<실시예 1><Example 1>

제1단계First stage

중합이 완료된 발포성 폴리스티렌 입자를 스팀을 가하여 비드법으로 60배로 발포하고 5시간 숙성 하였다. The expanded polystyrene particles, which had been polymerized, were foamed 60 times by the bead method by applying steam, and aged for 5 hours.

제2단계 2nd step

숙성된 발포한 수지입자에 오존화 된 공기로 산화 개질하며 수지입자 100kg에 대하여 팽창흑연 35kg, 파라핀 5kg 을 믹서기에 투입하였다.Aged foamed resin particles were oxidatively reformed with ozonized air, and 35 kg of expanded graphite and 5 kg of paraffin were added to a mixer with respect to 100 kg of resin particles.

제3단계 3rd step

믹서기를 0.005 MPa - 0.1 MPa의 압력 1 - 10rpm 교반하며 초산비닐수지(고형분 30%) 15kg, 염화비닐수지 15kg을 분사하며 팽창 흑연을 코팅하였다.The mixer was coated with expanded graphite by spraying 15 kg of vinyl acetate resin (30% solids) and 15 kg of vinyl chloride resin with stirring at a pressure of 1-10 rpm with a pressure of 0.005 MPa-0.1 MPa.

제4단계 4th step

상기의 팽창흑연이 코팅된 수지입자를 40도 이하의 열풍으로 건조한 후 공지의 비드법으로 성형하여 성형품을(밀도20) 얻었다.The expanded graphite coated resin particles were dried with hot air of 40 degrees or less, and then molded by a known bead method to obtain a molded article (density 20).

<실시예 2><Example 2>

실시예 1과 동일하게 시행하되 공지의 비드법으로 성형하여 밀도가 20인 성형품을 얻었으며 성형품을 절단하여 표면에 팽창흑연 25kg과 초산비닐 수지수지(고형분 30%) 25kg을 도포하여 도막을 형성하였고 불연성을 측정하였다. The same procedure as in Example 1 was carried out, but a molded article having a density of 20 was obtained by molding using a known bead method. The molded article was cut to apply 25 kg of expanded graphite and 25 kg of vinyl acetate resin (30% solids) to form a coating film. Incombustibility was measured.

<비교예 1>Comparative Example 1

실시예 1과 동일한 방법으로 실시하였고 오존으로 EPS를 산화 개질하는 공정을 제외 하였다.It carried out in the same manner as in Example 1 except for the step of oxidatively reforming EPS with ozone.

<열방출시험><Heat release test>

실시예 1의 시료 및 실시예 2의 시료와 비교예 1의 시료로 폴리스티렌 발포 폼(스티로폼)을 제조한 상기의 시료들의 열방출 시험을 실시하였다. 시험은 건축물의 내장재료 및 구조의 연소성능 시험(KS F ISO 5660-1:2008)에 의하여 준불연자재 성능시험을 3회씩 하였으며, 상기 실시예 및 비교예에서 제조된 스티로폼 블록 시편을 사용하여 측정하였다.The heat release test of the sample which produced the polystyrene foam foam (styrofoam) with the sample of Example 1, the sample of Example 2, and the sample of Comparative Example 1 was performed. The test was performed three times of non-combustible material performance test by the combustion performance test (KS F ISO 5660-1: 2008) of the interior materials and structures of buildings, and measured using the styrofoam block specimens prepared in Examples and Comparative Examples. It was.

그 결과는 하기 [표 1]과 같다. The results are shown in the following [Table 1].

시험항목Test Items 실시예 1Example 1 실시예2Example 2 비교예 1Comparative Example 1 판정기준Criteria

열방출실험


Heat release experiment
총방출량(MJ/m²)Total emissions (MJ / m²) 77 55 1111 8 이하8 or less
열방출량이연속으로 200
kw/m²를초과하는시간(S)
Heat emission continuously 200
Time over kw / m² (S)
1212 66 1414 10 이하below 10
심재의 전부용융, 관통하
는 균열 및 구멍 등의 변화
Full melting of the heartwood, penetrating
Changes such as cracks and holes

없음

none

없음

none

없음

none

없을 것

No

상기 [표 1]에 나타난 바와 같이, 실시예 1 보다 실시예 2는 열방출량이 매우 낮게 나타나고 있으며 가열 후 3 - 5초부터 표면에 형성된 팽창 흑연의 도막이 70배로 팽창하며 불연층을 형성하며 성형품을 열원으로부터 보호하였다. 비교예1의 경우에는 총방출량이 판정기준치인 8MJ/m2를 초과하는 11MJ/m2를임을 알 수 있어 실시예 2에 비하여 불연성이 약한 것으로 확인되었다. As shown in [Table 1], Example 2 has a much lower heat release rate than Example 1, and the coating film of expanded graphite formed on the surface expands by 70 times from 3 to 5 seconds after heating to form a non-combustible layer. Protected from heat source. In Comparative Example 1, it was found that the total emission amount was 11 MJ / m 2 exceeding the determination standard value of 8 MJ / m 2 , and it was confirmed that the incombustibility was weaker than that in Example 2.

Claims (6)

a) 발포성 폴리스티렌 입자를 발포하여 교반기에 투입하는 단계;
b) 오존화된 공기를 교반기에 주입하여 발포한 발포성 폴리스티렌 입자를 산화 개질시킨 후 팽창흑연과 파라핀을 투입하는 단계;
c) 0.005Mpa - 0.1Mpa 압력으로 교반하며 열가소성 접착성 수지를 분사하여 발포한 EPS 입자에 팽창흑연을 코팅하고 건조하는 단계;
d) 상기 팽창흑연이 코팅된 발포한 EPS 입자를 성형한 후 상기 성형품 표면에 팽창 흑연을 도포하는 단계;
로 이루어진 성형물의 표면에 팽창 흑연을 도포하는 방법.
a) foaming the expandable polystyrene particles into a stirrer;
b) injecting ozonated air into a stirrer to oxidatively modify the expanded expandable polystyrene particles and then inflate expanded graphite and paraffin;
c) coating expanded graphite on the expanded EPS particles by spraying a thermoplastic adhesive resin with stirring at a pressure of 0.005 Mpa-0.1 Mpa and drying;
d) forming expanded EPS particles coated with the expanded graphite and then applying expanded graphite to the surface of the molded article;
Method of applying expanded graphite to the surface of the molding consisting of.
제1항에 있어서,
상기의 팽창흑연은 팽창율이 20ml/g - 500ml/g 이고, 입도직경이 20mesh - 300mesh 인 것을 특징으로 하는 성형물의 표면에 팽창 흑연을 도포하는 방법.
The method of claim 1,
The expanded graphite has a expansion rate of 20ml / g-500ml / g, the particle size of 20mesh-300mesh, the method of applying expanded graphite to the surface of the molding.
제1항에 있어서,
상기의 파라핀은 염화파라핀, 고형파라핀 및 유동파라핀 중에서 선택한 1종 단독 또는 2종 이상 혼합하여 1 - 20 중량부 사용하는 것을 특징으로 하는 성형물의 표면에 팽창 흑연을 도포하는 방법.
The method of claim 1,
The paraffin is a method for applying expanded graphite to the surface of the molding, characterized in that 1 to 20 parts by weight of one or a mixture of two or more selected from paraffin chloride, solid paraffin and liquid paraffin.
제1항에 있어서,
상기 열가소성 접착성 수지는 아크릴수지, 폴리에틸렌수지, 폴리프로필렌수지, 폴리스티렌수지, 초산비닐수지, 불소수지, 염화비닐수지, 폴리아미드수지, 아세틸수지, 폴리카보네이트수지 ABS수지 중에서 선택한 1종 단독 또는 2종 이상 혼합하여 사용하는 것을 특징으로 하는 성형물의 표면에 팽창 흑연을 도포하는 방법.
The method of claim 1,
The thermoplastic adhesive resin may be selected from acrylic resins, polyethylene resins, polypropylene resins, polystyrene resins, vinyl acetate resins, fluorine resins, vinyl chloride resins, polyamide resins, acetyl resins, and polycarbonate resins. The method of apply | coating expanded graphite to the surface of the molded object characterized by using the above mixing.
a) 발포성 폴리스티렌 입자를 발포하여 교반기에 투입하는 단계;
b) 오존화된 공기를 교반기에 주입하여 발포한 발포성 폴리스티렌 입자를 산화 개질시킨 후 팽창흑연과 파라핀을 투입하는 단계;
c) 0.005 Mpa -0.1 Mpa 압력으로 교반하며 열가소성 접착성 수지를 분사하여 발포한 EPS 입자에 팽창흑연을 코팅하고 건조하는 단계;
d) 상기 팽창흑연이 코팅된 발포한 EPS 입자를 성형한 후 상기 성형품 표면에 팽창 흑연을 도포하는 단계;
로 이루어진 표면에 팽창 흑연이 도포된 성형물.
a) foaming the expandable polystyrene particles into a stirrer;
b) injecting ozonated air into a stirrer to oxidatively modify the expanded expandable polystyrene particles and then inflate expanded graphite and paraffin;
c) coating expanded graphite on the expanded EPS particles by spraying thermoplastic adhesive resin with stirring at 0.005 Mpa -0.1 Mpa pressure and drying;
d) forming expanded EPS particles coated with the expanded graphite and then applying expanded graphite to the surface of the molded article;
Molded product coated with expanded graphite on the surface consisting of.
제5항에 있어서,
상기 성형물은 팽창흑연이 코팅된 발포한 폴리스티렌 수지 입자의 성형물 100중량부에 대하여 표면층에 1 - 50중량부의 탄소함량 90중량%인 팽창흑연과 1 - 50중량부의 접착성 수지로 도막을 형성하여 가열하면 20 - 300배로 팽창하는 도막을 형성한 성형물.
The method of claim 5,
The molding is heated by forming a coating film of expanded graphite having 1 to 50 parts by weight of carbon content of 90% by weight of carbon and 1 to 50 parts by weight of an adhesive resin with respect to 100 parts by weight of a molded product of expanded graphite coated foamed polystyrene resin particles. A molded article having a coating film which is expanded 20 to 300 times on the lower surface.
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