KR20190121738A - Expandable Graphite Coated Expandable Polystyrene Resin Particles - Google Patents
Expandable Graphite Coated Expandable Polystyrene Resin Particles Download PDFInfo
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- KR20190121738A KR20190121738A KR1020190130421A KR20190130421A KR20190121738A KR 20190121738 A KR20190121738 A KR 20190121738A KR 1020190130421 A KR1020190130421 A KR 1020190130421A KR 20190130421 A KR20190130421 A KR 20190130421A KR 20190121738 A KR20190121738 A KR 20190121738A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3442—Mixing, kneading or conveying the foamable material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
- B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
- B29K2105/048—Expandable particles, beads or granules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2707/00—Use of elements other than metals for preformed parts, e.g. for inserts
- B29K2707/04—Carbon
Abstract
Description
본 발명은 팽창흑연을 코팅하여 불연성을 확보하는 발포성 폴리스티렌( Expandable Polystyrene 이하' EPS'라 칭한다) )수지입자를 수득하기 위한 것으로 팽창율(Expansion rato)이 20ml/g ~ 500ml/g이며, 입도직경이 20mesh ~ 300mesh인 팽창흑연을 직경 0.2mm ~ 1.5mm의 EPS 입자에 접착 코팅하여 불연성을 확보하기 팽창흑연이 코팅된 발포성 폴리스티렌 수지입자에 관한 것으로 소수성(hydrophobicity)인 EPS 입자의 표면층을 산화시켜 EPS 표면층이 친수성을 갖도록 하여 팽창 흑연을 용이하게 EPS에 코팅시킨 팽창흑연을 코팅한 발포성 폴리스티렌 수지입자 및 그 입자를 이용한 불연성이 부여된 성형품을 얻기 위한 것이다.The present invention is to obtain expandable polystyrene (hereinafter referred to as 'EPS') resin particles by coating the expanded graphite to ensure incombustibility, the expansion ratio (Expansion rato) is 20ml / g ~ 500ml / g, the particle size 20mm ~ 300mesh expanded graphite is adhered to 0.2mm ~ 1.5mm diameter EPS particles to secure non-combustibility Expanded graphite coated foamed polystyrene resin particles oxidized the surface layer of hydrophobic EPS particles by EPS oxidation The present invention provides an expandable polystyrene resin particle coated with expanded graphite coated with expanded graphite with EPS having such hydrophilicity and a non-combustible molded article using the particles.
보다 상세하게는 중합을 완료한 EPS 입자를 오존화된 공기로 표면층을 산화시켜 개질화시킨 EPS 입자에 염화파라핀과 팽창흑연을 투입하고 극성 유기용매를 분사하며 0.005MPa ~ 0.1MPa의 압력 하에서 1~30rpm으로 1 ~ 5분 교반하면서 EPS 입자에 접착 코팅하는 것이다.More specifically, the paraffin and swelled graphite are injected into the modified EPS particles by oxidizing the surface layer with ozoneized air, and the expanded EPS particles are sprayed with a polar organic solvent and sprayed with a polar organic solvent. Adhesive coating on the EPS particles while stirring at 30rpm for 1-5 minutes.
상기에서 팽창흑연은 연소를 차단하는 팽창율이 20ml/g ~ 500 ml/g이며, 입도직경이 20mesh ~ 300mesh인 물성을 갖는 것이 바람직하다.In the above expanded graphite, the expansion ratio to block combustion is 20ml / g ~ 500 ml / g, it is preferable to have a physical property of the particle size diameter 20mesh ~ 300mesh.
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 방전처리하여 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 팽창흑연과 분산제 이소시아네이트를 혼합한 접착제를 제조하여 EPS 입자를 발포하고 성형한 스티로폼에 도포하는 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 strongly coating a heat insulating material, a flame retardant material, and functional materials on the surface layer of the expanded foamed resin particle modified by discharging the low temperature plasma. Korean Patent No. 1448051 discloses a method of forming a caramel by mixing and reacting sugar and phosphoric acid, preparing an adhesive mixed with expanded graphite and a dispersant isocyanate, and foaming EPS particles and applying the molded styrofoam.
대한민국 공개특허 10-2016-0134452호에는 팽창에 의하여 발포가 일어나 부피가 약 500배로 확대된 팽창된 흑연을, 코팅제에 첨가하여 팽창된 흑연을 첨가한 불연성 도막 코팅제와 그 제조방법 및 용도에 관한 제조 방법을 개시하고 있다.Korean Unexamined Patent Publication No. 10-2016-0134452 discloses a non-flammable coating coating agent comprising a expanded graphite having a volume expanded to about 500 times by expansion due to expansion, and expanded graphite added to the coating agent, and a manufacturing method and a use thereof. 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 선행 기술은 EPS 입자를 80배-100배로 발포하여 의도하는 기능성 물질들을 코팅하고 성형하는 기술들이다 예를 들어서 EPS를 80배 발포하면 80배의 부피로 단면적이 커진 저밀도의 스티렌 발포입자에 기능성 물질들을 접착제를 사용하여 코팅하고 성형하는 기술이므로 코팅하는 제조 공정이 비경제적이며 최종물성이 균일하지못하고 관련 법 규정에 미달하는 문제점이 있었다.Such prior art is a technique of coating and forming the intended functional materials by foaming the EPS particles 80 times to 100 times. For example, when foaming 80 times the EPS, low density styrene foam particles having a large cross-sectional area of 80 times are expanded. Because of the technology of coating and molding functional materials using an adhesive, there is a problem that the manufacturing process of coating is uneconomical and the final properties are not uniform and fall short of the relevant legal regulations.
본 발명은 위와 같은 종래 기술들의 문제점을 해결한 것으로 중합을 완료한 EPS 입자에 오존화 된 공기를 주입하여 표면층을 산화하여 개질 하고 극성유기용매의 존제하에서 파라핀을 매질로 팽창흑연 분말을 EPS 입자에 접착 코팅하는 단계로 팽창흑연이 코팅된 수지입자를 수득하고 발포 성형하여 불연성의 단열재를 생산하는 것이다.The present invention solves the problems of the prior art as described above by injecting ozonized air into the polymerized EPS particles to oxidize and modify the surface layer and expand the expanded graphite powder into EPS particles in the presence of a polar organic solvent. In the adhesive coating step, the expanded graphite coated resin particles are obtained and foamed to produce a non-combustible heat insulating material.
본 발명의 목적은 소수성인 EPS 입자를 오존화된 공기로 산화하여 친수성으로 개질시켜 코팅성을 향상시켜 팽창흑연을 EPS 입자에 접착 코팅하는 방법에 그 목적이 있다.An object of the present invention is to oxidize the hydrophobic EPS particles with ozonated air to modify the hydrophilicity to improve the coating properties to adhesively coat the expanded graphite on the EPS particles.
본 발명의 또 다른 목적은 극성 유기용매의 존제하에서 상전이(PCM)물질인 파라핀을 매질로 사용하여 입자의 파손없이 팽창흑연을 EPS 입자에 접착 코팅시킨 팽창흑연이 코팅된 EPS 입자를 얻는데 그 목적이 있다.It is another object of the present invention to obtain expanded graphite coated EPS particles in which expanded graphite is adhesively coated onto EPS particles without breakage of the particles by using paraffin, which is a phase change (PCM) material, as a medium in the presence of a polar organic solvent. have.
본 발명의 또 다른 목적은 팽창흑연이 코팅된 EPS를 발포 성형하고 성형체 표면층에 팽창흑연을 도포하여 물성이 더 향상된 제품을 얻는데 그 목적이 있다. It is still another object of the present invention to obtain a product having improved physical properties by foam molding EPS coated with expanded graphite and applying expanded graphite to a molded surface layer.
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 오존에 노출하여 입자 표면층을 산화시켜서 친수성으로 개질함으로서 팽창흑연과의 접착 코팅이 용이하도록 한다.Since the EPS particles are hydrophobic and have a property of repelling the adhesive coating of hydrophilic expanded graphite, the present invention facilitates adhesive coating with expanded graphite by modifying the hydrophilicity by oxidizing the particle surface layer by exposing the EPS particles to ozone.
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 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 ~ 18kv 교류고압을 가하면 방전영역에서 오존이 발생된다. 무성방전법의 오존발생은 공기를 사용한 경우, 10g ~ 35g/m3, 산소를 사용할 경우에는 50g ~ 150g/m3의 오존을 얻을 수 있고 소비 전력은 수냉식 냉각수 온도 25℃의 경우 산소를 주입할 때 10 ~ 13 kwh/kg-O3이며, 공기를 주입할 때는 15 ~ 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, blows air or oxygen, and applies high voltage of 6kv to 18kv to the electrode to generate ozone in the discharge region. do. The ozone generation of silent discharge method can obtain ozone of 10g ~ 35g / m3 when using air, and 50g ~ 150g / m3 when using oxygen, and the power consumption is 10 when injecting oxygen at water-cooled cooling water temperature of 25 ℃. ~ 13 kwh / kg-O 3 and 15 to 20 kwh / kg-O 3 when injecting air. 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 발생된다Ozone is generated by the following reaction
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
[오존 발생장치 및 본 발명의 EPS 오존처리 시스템][Ozone Generator and EPS Ozone Treatment System of the Present Invention]
팽창흑연은 천연 인편흑연을 산성재료로 화학 처리를 하여 흑연의 층간에 산성화합물을 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 acidic material to infiltrate acidic compound between layers of graphite and is dried. When it is heated above 150 ℃, it can decompose and generate gas and expand 20 times to 500 times of volume. It is commonly called Expandable Graphite.
팽창흑연은 가열에 의해 팽창하면서 발포층이 열원을 차단하는 작용을 하므로 팽창율(Expansion rato)이 20ml/g ~ 500 ml/g인 팽창흑연 중에서 선택하여 사용할 수 있으며 바람직한 팽창율은 100ml/g ~ 300ml/g이고, 입도는 20mesh ~ 300mesh 이다. 팽창흑연은 고압 또는 충격 등에 의해 입자가 파손되면 팽창하는 물성이 상실되므로 본 발명의 목적을 달성할 수 없다.Expanded graphite expands by heating and the foam layer blocks the heat source, so it can be selected from expanded graphite having an expansion rate of 20 ml / g to 500 ml / g, and the preferred expansion rate is 100 ml / g to 300 ml /. g and the particle size is 20mesh ~ 300mesh. Expanded graphite is unable to achieve the object of the present invention because the expanded physical properties are lost when the particles are damaged by high pressure or impact.
본 발명은 EPS 입자 100중량부에 대하여 팽창흑연 1 ~ 50 중량부를 접착 코팅할 수 있으며 바람직하게는 10 ~ 25 중량부를 접착 코팅한다. 이 범위를 초과하면 물성의 증진이 미약하고, 경제성이 떨어지므로 탄소함량 92% (Carbon Content), 팽창율(Expansion rate) 200ml/g ~ 500ml/g, 입도(Particle distribution) 80 mesh 이상의 팽창흑연을 사용하는 것이 바람직하다.The present invention may adhesively coat 1 to 50 parts by weight of expanded graphite with respect to 100 parts by weight of EPS particles, preferably 10 to 25 parts by weight of adhesive coating. 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 200ml / g to 500ml / g, Particle distribution 80 mesh or more is used. It is desirable to.
본 발명에서 사용하는 파라핀은 고체의 탄화수소 혼합물이며 에테르나 벤젠 에스테르에 녹는 물질로 윤활성과 흡착성이 우수하다. 극성유기 용매에 용해되며 팽창흑연을 EPS에 접합 코팅하는 단계에서 EPS 입자 표면층에 침투 코팅된다. 파라핀은 염화파라핀, 고형파라핀, 유동파라핀 중에서 선택하여 1종 단독 또는 2종 이상 혼합하여 1 ~ 30 중량부 사용하며 바람직하게는 5 ~ 15중량부를 사용한다.Paraffin used in the present invention is a solid hydrocarbon mixture, a substance soluble in ether or benzene esters, and excellent in lubricity and adsorption. It is dissolved in a polar organic solvent and permeate coated on the EPS particle surface layer in the step of joint coating the expanded graphite to EPS. Paraffin is selected from the paraffin chloride, solid paraffin, liquid paraffin selected from one kind or mixed two or more kinds to use 1 to 30 parts by weight, preferably 5 to 15 parts by weight.
극성 유기 용매는 EPS와 파라핀 및 팽창흑연을 접착 코팅하는 용매작용을 한다.Polar organic solvents act as solvents for the adhesive coating of EPS with paraffins and expanded graphite.
예를들면 디메틸포름아마이드(Dimethylformamide), 디메틸아세트아마이드(Dimethylacetamide), 아세트산(aceticacide), 에탄올(ethanol), 아세톤(Acetone), 메탄올(methanol), 에틸아세테이트(Ethylacetate)가 있으며, 이들 중 1종 단독 또는 2종 이상 혼합하여 0.1 ~ 15중량부를 사용하며 바람직하게는 1 ~ 5중량부를 사용한다.For example, dimethylformamide, dimethylacetamide, acetic acid, ethanol, acetone, methanol, ethylacetate, one of these alone Or by mixing two or more kinds, using 0.1 to 15 parts by weight, preferably 1 to 5 parts by weight.
오존화된 공기로 발포성 폴리스티렌 수지입자를 산화 개질하고 팽창흑연을 코팅하는 제조공정은 다음과 같다.The production process of oxidatively modifying expandable polystyrene resin particles with ozonated air and coating expanded graphite is as follows.
1. ESP 저장 사이로에서 정량 배출된 발포성 폴리스티렌(EPS) 수지입자를 밀폐된 원통형 텀블러형 믹서기에 투입하고 1 ~ 30 rpm으로 교반하며 준비하는 단계. 1. A step of preparing expanded polystyrene (EPS) resin particles quantitatively discharged between ESP storage cells into a closed cylindrical tumbler mixer and stirring at 1 to 30 rpm.
2. 콤프레샤 (압력 3 ~ 4Kgf/cm2) 와 After cooler Air Filter 냉동건조장치로 이루어진 장치를 경유한 건조한 공기를 1쌍의 전극 사이에 세라믹 유전체를 끼운 오존 발생 장치의 전극 사이로 불어 넣고, 오존 발생 장치에 6kv～18kv 교류 고압을 가하면 공기가 방전영역을 통과하면서 오존화된 공기를 믹서기에 주입하여 오존의 존제에서 EPS 표면을 산화 개질시키는 단계.2. Blow dry air through a device consisting of a compressor (pressure 3 ~ 4kgf / cm 2 ) and After cooler Air Filter freeze-drying device between the electrodes of an ozone generator with a ceramic dielectric sandwiched between a pair of electrodes. When 6kv ~ 18kv AC high pressure is applied to the device, air is passed through the discharge zone and ozonated air is injected into the blender to oxidize and modify the EPS surface in the presence of ozone.
3. 개질된 EPS 입자에 염화파라핀과 팽창흑연을 투입하고 극성 유기용매를 분사하며 압축강도 0.005MPa ~ 0.1MPa을 유지하며 1 ~ 30rpm으로 1 ~ 5분 교반하여 코팅하고 배출하는 단계.3. Put paraffin chloride and expanded graphite into modified EPS particles, spray polar organic solvent, maintain compressive strength of 0.005MPa ~ 0.1MPa, and stir for 1 ~ 5 minutes at 1 ~ 30rpm to coat and discharge.
4. 배출 코팅된 EPS 입자를 40도 이하의 온도에서 1 ~ 60분 건조하는 단계.4. Drying the discharge coated EPS particles at a temperature of 40 degrees or less for 1 to 60 minutes.
5. 건조 양생된 수지입자에 접착성 수지가 분사되고 40도 이하의 온도로 건조하고 분진과 불량품을 선별하는 단계.5. Drying The adhesive resin is sprayed onto the cured resin particles, dried to a temperature of 40 degrees or less, and the dust and defective products are sorted out.
믹서기는 팽창흑연의 파손을 방지하기 위하여 0.005 MPa ~ 0.1MPa 압축강도로 가동하였고 직경 1m 길이 1.5m의 원통형이며 통이 회전하는 텀블러형 믹서기를 사용하였다. The mixer was operated with 0.005 MPa ~ 0.1MPa compressive strength to prevent breakage of expanded graphite and used a cylindrical, tumbler type mixer with a diameter of 1m and a length of 1.5m.
믹서기를 회전시키면 코팅체인 EPS와 피코팅체인 팽창흑연 파라핀이 중력에 의하여 수직 낙하 하면서 혼합되며 극성유기용매가 분사되며 접착 코팅이 개시된다.When the mixer is rotated, the coated EPS and the coated graphite paraffin are mixed while being vertically dropped by gravity, the polar organic solvent is injected, and the adhesive coating is started.
상기 접착성 수지(고형분 35%)는 아크릴수지계, 올레핀계수지, 우레탄계수지, 폴리스티렌계수지, 초산비닐계수지, 에폭시계수지, 염화비닐계수지, 클로로프렌고무계수지, 폐놀계수지, 등이 있으며, 이들 중, 1종 또는 2종 이상을 혼합하여 EPS 중량에 대하여 0.1 ~ 15중량부를 분사할 수 있으며, 바람직하게는 1중량부 ~ 5중량이다.The adhesive resin (35% solids) is acrylic resins, olefin resins, urethane resins, polystyrene resins, vinyl acetate resins, epoxy resins, vinyl chloride resins, chloroprene rubber resins, phenolic resins, etc. Among these, 0.1-15 weight part can be sprayed with respect to EPS weight by mixing 1 type or 2 or more types, Preferably it is 1 weight part-5 weight parts.
한편 본 발명으로 완성된 EPS를 공지의 비드법으로 발포 성형한 성형품 표면에 접착성 수지와 혼합한 팽창흑연을 도포한 막을 형성시켜서 불연성과 단열성을 더 증진시킬 수 있다. On the other hand, by forming a film coated with expanded graphite mixed with an adhesive resin on the surface of the molded article foamed EPS of the present invention by a known bead method can further improve non-combustibility and thermal insulation.
성형품 중량에 대하여 팽창흑연 0.1 ~ 15중량부 도포할 수 있으며 바람직하게는 1 ~ 5중량부를 도포하며 접착성 수지는 상기의 접착성 수지를 사용하며 1종 또는 2종 이상을 혼합하여 성형품 중량에 대하여 0.1 ~ 15중량부를 혼합할 수 있으며, 바람직하게는 1중량부 ~ 5중량부이다.0.1 to 15 parts by weight of expanded graphite may be applied based on the weight of the molded article, preferably 1 to 5 parts by weight, and the adhesive resin is used as the adhesive resin, and one or two or more kinds thereof may be mixed to the weight of the molded article. 0.1-15 weight part can be mixed, Preferably it is 1 weight part-5 weight part.
본 발명은 EPS 표면층을 오존으로 산화시켜 친수성으로 개질하여 친수성인 팽창흑연과의 코팅성을 향상시키는 효과가 있다.The present invention has the effect of oxidizing the EPS surface layer with ozone to modify the hydrophilicity to improve the coating property with hydrophilic expanded graphite.
또한, 소수성이며 가연성인 EPS 입자의 표면을 산화시킴으로써 팽창흑연을 용이하게 EPS에 접착 코팅시킬 수 있고, 이로 인해 제품의 불량률을 줄일 수 있는 장점이 있다.In addition, by oxidizing the surface of the hydrophobic and flammable EPS particles, the expanded graphite can be easily coated on the EPS, thereby reducing the defective rate of the product.
또한, 윤활성이 우수한 극성 유기용매와 파라핀을 용질과 용매로 사용함으로써 팽창흑연을 EPS에 간단하게 코팅시킬 수 있어 코팅시간의 단축시키는 효과가 있다.In addition, by using a polar organic solvent and paraffin having excellent lubricity as a solute and a solvent, the expanded graphite can be easily coated on the EPS, thereby reducing the coating time.
이하, 본 발명의 실시예에서 제조된 발포성 폴리스티렌을 발포 성형한 스티로폼의 불연 물성 등에 대하여 설명하나, 본 발명의 범위는 실시예의 범위에 한정되지 아니하며 실시예로 부터 뒷받침되는 모든 범위를 포함한다고 할 수 있다.Hereinafter, the non-flammable properties of the 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 can be said to include all ranges supported by the embodiment. have.
<실시예 1><Example 1>
제1단계First stage
중합이 완료된 발포성 폴리스티렌 입자를 사일로에서 방출하여 직경 1,000mm 길이 2,000mm의 원통형 믹서기로 200Kg 정량 이송하여 오존화가 이루어진 공기를 주입하며 교반하여 EPS 입자를 산화시키고 개질한다.After the polymerization is completed, the expanded polystyrene particles are discharged from the silo and quantitatively transferred to 200 Kg in a cylindrical mixer having a diameter of 1,000 mm and a length of 2,000 mm to inject ozoneized air and stirred to oxidize and modify the EPS particles.
제2단계 2nd step
오존에 의하여 개질된 수지 입자 100중량부에 대하여 팽창흑연 20중량부, 파라핀 10중량부를 투입하고 극성유기용매인 디메틸포름아마이드( Dimethylformamide) 2 중량부를 분사하여 0.005 MPa ~ 0.1 MPa로 5분간 교반하면서 EPS 입자에 팽창흑연을 접착 코팅한다.20 parts by weight of expanded graphite and 10 parts by weight of paraffin are added to 100 parts by weight of ozone-modified resin particles, and 2 parts by weight of dimethylformamide, a polar organic solvent, is sprayed and stirred at 0.005 MPa to 0.1 MPa for 5 minutes. Adhesive coating of expanded graphite on the particles.
제3단계 3rd step
제2단계의 팽창흑연이 코팅된 수지입자 100 중량부에 대하여 폐놀계수지 2중량부와 우레탄수지 1중량부를 코팅하고 40도 이하의 열풍으로 건조한 후 공지의 비드법으로 60배로 발포하고 성형하여 스티로폼을(밀도18) 얻었다. 2 parts by weight of waste phenolic resin and 1 part by weight of urethane resin were coated with respect to 100 parts by weight of the expanded graphite coated resin particles of the second step, dried with hot air of 40 degrees or less, and foamed and molded 60 times by a known bead method. (Density 18) was obtained.
<실시예 2><Example 2>
실시예 1과 동일하게 시행하되 공지의 비드법으로 발포, 성형하여 밀도가 20인 스티로폼을 얻었으며 표면에 팽창흑연이 포함된 접착성 수지 10중량부를 도포하였고 불연성을 측정하였다. In the same manner as in Example 1, foaming and molding were carried out using a known bead method to obtain a styrofoam having a density of 20. 10 parts by weight of an adhesive resin containing expanded graphite was coated on the surface thereof, and nonflammability was measured.
<비교예 1>Comparative Example 1
실시예 1과 동일한 방법으로 EPS 입자를 제조하되, EPS 입자 표면을 오존으로 산화처리하지 않고 EPS 입자에 팽창흑연을 접착 코팅하였고, 공지의 비드법으로 60배로 발포하고 성형하여 스티로폼을(밀도18) 얻었으며, 발포와 성형과정에서 팽창흑연의 분진이 발생하였다 .The EPS particles were prepared in the same manner as in Example 1, but the expanded graphite was adhesively coated on the EPS particles without oxidizing the surface of the EPS particles with ozone, and foamed and molded at 60 times by a known bead method to form styrofoam (density 18). Dust of expanded graphite was produced during foaming and molding.
<열방출시험><Heat Release Test>
실시예 1의 시료 및 실시예 2의 시료와 비교예 1의 시료로 발포성 스티로폼을 제조한 상기의 시료들의 열방출 시험을 실시하였다. 시험은 건축물의 내장재료 및 구조의 연소성능 시험(KS F ISO 5660-1:2008)에 의하여 성능시험을 3회씩 하였으며, 상기 실시예 및 비교예에서 제조된 스티로폼 블록 양면에 0.38mm 두께의 철판을 덧댄 시편을 사용하여 측정하였다.The heat release test of the sample of Example 1, the sample of Example 2, and the said sample which produced the foamed styrofoam with the sample of the comparative example 1 was performed. The test was performed three times by the performance test (KS F ISO 5660-1: 2008) of the building material and structure of the building, and a 0.38 mm thick iron plate was placed on both sides of the styrofoam block manufactured in Examples and Comparative Examples. Measured using padded specimens.
그 결과는 하기 [표 1]과 같다.The results are shown in the following [Table 1].
열방출실험
Heat release experiment
kw/m²를초과하는시간(S)Heat emission continuously 200
Time over kw / m² (S)
9
9
7
7
12
12
10 이하
below 10
는 균열 및 구멍 등의 변화Full melting of the heartwood, penetrating
Changes such as cracks and holes
없음
none
없음
none
부분 있음
Has part
없을 것
No
상기 [표 1]에 나타난 바와 같이, 실시예 1 및 2는 열발출량이 매우 낮게 나타나고 있으나, 비교예1의 경에는 8MJ/m2를 초과하는 것으로 나타났고, 또한, 실시예 1 및 2는 전체 두께에 걸친 용융 및 방화상 유해한 변형이 없었으나, 비교예 1의 경우 부분적으로 변형이 일어남을 확인할 수 있었다.As shown in [Table 1], Examples 1 and 2, but the amount of heat extraction is very low, but in the case of Comparative Example 1 was found to exceed 8MJ / m 2 , and Examples 1 and 2 were There was no harmful deformation in melting and fire prevention over the thickness, but in the case of Comparative Example 1 it could be confirmed that the deformation occurs in part.
Claims (3)
상기 접착성 수지는 파라핀을 포함하는 것을 특징으로 하는 팽창흑연이 코팅된 발포성 폴리스티렌 수지입자. The method of claim 1,
The adhesive resin is expanded graphite coated expandable polystyrene resin particles, characterized in that it comprises paraffin.
상기 파라핀은 염화파라핀, 고형파라핀, 및 유동파라핀 중에서 선택된 1종 단독 또는 2종 이상인 것을 특징으로 하는 팽창흑연이 코팅된 발포성 폴리스티렌 수지입자. The method of claim 2,
The paraffin is expanded graphite coated expandable polystyrene resin particles, characterized in that at least one selected from the group consisting of chlorinated paraffin, solid paraffin, and liquid paraffin.
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| KR20110065707A (en) | 2009-12-10 | 2011-06-16 | 주식회사 엘지화학 | Expandable polystyrene bead comprising silicone and expanded vermiculite, and method for preparing the same |
| KR20120022393A (en) * | 2010-09-02 | 2012-03-12 | 장용호 | Method of flame retardant to phosphorus flame retardant and expandable graphite using the expandable polystyrene foam and its expanded polystyrene foam |
| KR101300627B1 (en) | 2012-09-17 | 2013-08-28 | 김재천 | Surface modification by low-temperature plasma treatment expandable polystyrene resin particle fabrication method |
| KR101494801B1 (en) | 2013-12-10 | 2015-02-23 | 한국건설기술연구원 | Non-framable adhesive using sucrose phosphorolysis and expandable graphite and method thereof |
| KR20160134452A (en) | 2015-05-15 | 2016-11-23 | 민성기 | Incombustible film coating material containing expanded graphite and the manufacturing and using method of the same |
| KR20170010676A (en) * | 2015-07-20 | 2017-02-01 | 주식회사 쉘보드 | nonflammable firewall |
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2019
- 2019-10-21 KR KR1020190130421A patent/KR102108197B1/en active IP Right Review Request
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110065707A (en) | 2009-12-10 | 2011-06-16 | 주식회사 엘지화학 | Expandable polystyrene bead comprising silicone and expanded vermiculite, and method for preparing the same |
| KR20120022393A (en) * | 2010-09-02 | 2012-03-12 | 장용호 | Method of flame retardant to phosphorus flame retardant and expandable graphite using the expandable polystyrene foam and its expanded polystyrene foam |
| KR101300627B1 (en) | 2012-09-17 | 2013-08-28 | 김재천 | Surface modification by low-temperature plasma treatment expandable polystyrene resin particle fabrication method |
| KR101494801B1 (en) | 2013-12-10 | 2015-02-23 | 한국건설기술연구원 | Non-framable adhesive using sucrose phosphorolysis and expandable graphite and method thereof |
| KR20160134452A (en) | 2015-05-15 | 2016-11-23 | 민성기 | Incombustible film coating material containing expanded graphite and the manufacturing and using method of the same |
| KR20170010676A (en) * | 2015-07-20 | 2017-02-01 | 주식회사 쉘보드 | nonflammable firewall |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102464200B1 (en) | 2021-05-13 | 2022-11-07 | 주식회사 에스에이치에너지화학 | Organic, Inorganic hybrid Expandable polystyrene beads having non flammable insulation property and their manufacturing methods |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102108197B9 (en) | 2023-09-12 |
| KR102108197B1 (en) | 2020-05-07 |
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