WO2017082639A1 - Composition de revêtement ignifuge - Google Patents

Composition de revêtement ignifuge Download PDF

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Publication number
WO2017082639A1
WO2017082639A1 PCT/KR2016/012894 KR2016012894W WO2017082639A1 WO 2017082639 A1 WO2017082639 A1 WO 2017082639A1 KR 2016012894 W KR2016012894 W KR 2016012894W WO 2017082639 A1 WO2017082639 A1 WO 2017082639A1
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WO
WIPO (PCT)
Prior art keywords
weight
epoxy resin
flame retardant
coating composition
phosphate
Prior art date
Application number
PCT/KR2016/012894
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English (en)
Korean (ko)
Inventor
한상현
엄경일
정석희
Original Assignee
주식회사 케이씨씨
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 케이씨씨 filed Critical 주식회사 케이씨씨
Priority to CN201680063923.9A priority Critical patent/CN108603053B/zh
Priority to SG11201803262QA priority patent/SG11201803262QA/en
Priority to MYPI2018000625A priority patent/MY188861A/en
Priority to TR2018/06404T priority patent/TR201806404T1/tr
Publication of WO2017082639A1 publication Critical patent/WO2017082639A1/fr
Priority to SA518391473A priority patent/SA518391473B1/ar
Priority to HK18113792.3A priority patent/HK1254539A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present invention relates to a foamed refractory paint composition.
  • Oil fires generated from offshore structures, plants, etc. are characterized by a sharp rise in temperature during fires to about 945 ° C within 5 minutes.
  • a hardening type epoxy-based refractory paint is mainly used as a refractory paint in the field where oil fire may occur
  • a conventional refractory paint has a disadvantage in that a large amount of harmful gas is released when the coating film is expanded.
  • the solvent-free epoxy refractory paint proposed in U.S. Patent No. 4,529,467 is a foam layer formed by forming zinc (Zn) with small pores in the char when the paint expands in a fire. It has been suggested that can be improved. However, if the zinc is used in an excessive amount, there is a problem in that the coating film does not expand and conversely, the thermal insulation performance may drop.
  • U.S. Patent No. 5,108,832 proposes an epoxy-based refractory paint having excellent bendability by synthesizing an epoxy resin having excellent bendability.
  • an epoxy resin was synthesized using an epoxy monomer having a chain structure, and a fireproof paint was prepared using the same, and flexural properties were predicted through a low temperature cycle test.
  • U.S. Patent No. 6,096,812 proposes that the use of hydrophobic fumed silica lowers the density of the coated coating, thereby securing fire resistance while reducing the amount of paint used.
  • US Patent Application No. 1997-999536 has been disclosed a fire-resistant coating paint that can exhibit a low fired performance while reducing the density of the coating film by using a hydrophobic fumed silica based on the epoxy resin .
  • the phosphorus-based flame retardant used in the present invention has a TTP (Triphenyl phosphate) content of at least 21 wt% and a pyrolysis temperature of less than 250 ° C. Since TPP is evaporated at a lower temperature than the epoxy resin cured with a low molecular weight material, the initial foaming is improved. However, when the TPP content is large, there is a problem that the gaseous hazard is increased and the long-term fire resistance is lowered.
  • TTP Triphenyl phosphate
  • the present invention comprises an epoxy resin, a cured resin, a flame retardant, a blowing agent, an acid catalyst and a fiber, and in particular, by using a flame retardant having a triphenyl phosphate content of 20% by weight or less and a pyrolysis temperature of 250 ° C or higher, the gas hazard is reduced and the foamed layer
  • a flame retardant having a triphenyl phosphate content of 20% by weight or less and a pyrolysis temperature of 250 ° C or higher, the gas hazard is reduced and the foamed layer
  • the technical problem is to provide a foamed refractory coating composition which provides flexibility to the carbonized layer and prevents cracks from occurring in the carbonized layer, thereby improving long-term fire resistance.
  • the foamable refractory coating composition of the present invention is based on a total of 100% by weight, 10 to 25% by weight epoxy resin, 10 to 15% by weight curable resin, 10 to 20% by weight flame retardant, 3 to 10% by weight foaming agent, 20 to 40 acid catalyst
  • a foamable refractory coating composition comprising 3% by weight and 3 to 10% by weight of fiber, wherein the flame retardant has a triphenyl phosphate content of 20% by weight or less and a pyrolysis temperature of 250 ° C or more.
  • the foamable refractory coating composition of the present invention has a low TPP content, thereby reducing gas harmfulness, giving flexibility to the foamed layer at a thermal decomposition temperature of 250 ° C. or higher, and preventing cracks in the carbonized layer, thereby improving long-term fire resistance performance. have.
  • gas harmfulness it is more than 12 minutes when measured by gas hazard test method (KSF 2271), and fire resistance is measured by fire resistance test method (UL 1709). Exert.
  • the foamable refractory coating composition of the present invention is based on a total of 100% by weight, 10 to 25% by weight epoxy resin, 10 to 15% by weight curable resin, 10 to 20% by weight flame retardant, 3 to 10% by weight foaming agent, 20 to 40 acid catalyst
  • a foamable refractory coating composition comprising 3% by weight and 3 to 10% by weight of fiber, wherein the flame retardant has a triphenyl phosphate content of 20% by weight or less and a pyrolysis temperature of 250 ° C or more.
  • the epoxy resin used in the composition of the present invention allows the coating film to adhere to the subject, and the cured coating film exhibits durability at room temperature.
  • the coating film is changed to a flow state to enable the coating film to expand properly when gas is generated, and serves as a skeleton of the foamed carbonized layer.
  • an epoxy resin a bisphenol A epoxy resin, a bisphenol F epoxy resin, a flame retardant epoxy resin, a novolak type epoxy resin, a polyfunctional amine epoxy resin, a cycloaliphatic epoxy resin can be used, and preferably a bisphenol A type epoxy resin. At least one selected from resins and bisphenol F-type epoxy resins can be used.
  • the weight average molecular weight of the epoxy resin may be 150 to 900, preferably 200 to 800, the equivalent may be 75 to 450 g / eq, preferably 100 to 400 g / eq.
  • the foamable refractory paint composition of the present invention may comprise 10 to 25% by weight of epoxy resin, such as 15 to 23% by weight. If it is less than 10% by weight, the adhesion of the coating film may be degraded due to lack of resin content, and if it exceeds 25% by weight, the foaming rate of the coating film is inhibited in case of fire, and thus it may not exhibit sufficient fire resistance.
  • the curing resin used in the composition of the present invention is used to cure the epoxy resin.
  • the cured resin includes an amide obtained by polymerizing a polyethylene amine, a fatty acid dimer and a fatty acid monomer having a viscosity of 200 to 800 cps, an amine value of 300 to 600 mgKOH / g, and an active hydrogen equivalent of 50 to 200 g / eq.
  • Amido amine resins can be used.
  • Synthesis of the resin is as follows. First, a polyethylene amine, a fatty acid dimer, a fatty acid monomer mixture is heated to 200 ° C. to carry out a condensation reaction, and reacted until the acid value of the reactant is 1-5. Preferably, in this step, the molar ratio of amine / acid can be reacted to be 1.2 to 2.0. If the molar ratio is less than 1.2, it is difficult to apply paint due to its high viscosity. If it is 2.0 or more, unreacted amine is present. Realization of physical properties becomes difficult.
  • the polyethylene amine may be used one or a mixture of ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, fatty acid dimers and monomers are soybean oil fatty acid, tall oil fatty acid, castor oil fatty acid, rice bran oil As monomers and dimers prepared from the group consisting of fatty acids, amani oil fatty acids, coconut oil fatty acids, lauryl acid and linoleic acid, one or more selected from these may be mixed and used, preferably tall oil fatty acid monomers and dimers may be used. Can be.
  • the acid value of the reactant is 1 to 5 or less
  • heating can be completed to obtain an amide or amido amine resin produced.
  • the obtained resin has a viscosity of 200 to 800 cps, an amine value of 300 to 600 mgKOH / g, and active hydrogen. It is preferable that the equivalent is 50 to 200 g / eq, hardenability can be maximized within the above physical properties.
  • the foamable refractory paint composition of the present invention may comprise 10 to 15% by weight of curable resin, such as 11 to 14% by weight. If the content of the cured resin is less than 10% by weight, the adhesion of the coating may be reduced. If the content is more than 15% by weight, the content of the cured resin may be high, resulting in coating defects such as amine brushing.
  • Phosphorus-based flame retardant used in the composition of the present invention controls the thermal decomposition rate of the cured coating film serves to give the flexibility of the initial foamed carbonized layer.
  • the content of TPP Triphenyl phosphate
  • the pyrolysis temperature was less than 250 ° C.
  • the TPP is vaporized at a lower temperature than the epoxy resin cured with a low molecular weight material to improve the initial foaming, but when the TPP content is large, there is a problem that the gaseous hazard is increased and the long-term fire resistance performance is lowered.
  • the TPP content can be reduced to reduce the gas detrimental properties.
  • an additional phosphorus flame retardant having a thermal decomposition temperature of 250 ° C. or more that is, a heat loss of less than 5% at 250 ° C.
  • it slows down the thermal decomposition rate of the cured coating film, imparts flexibility to the foam layer, and cracks in the carbonized layer.
  • Phosphorus-based flame retardant included in the foamable refractory paint composition of the present invention may be a triphenyl phosphate (TPP) content of 20% by weight or less, pyrolysis temperature of 250 °C or more (that is, less than 5% heating loss at 250 °C). .
  • TPP triphenyl phosphate
  • the phosphorus-based flame retardant used in the present invention is triphenyl phosphate (TPP), isopropylated triphenyl phosphate, tricresyl phosphate, butylated triphenyl phosphate aryl phosphates such as phosphate, cresyl diphenyl phosphate, and isopropyl phenyl diphenyl phosphate; Bisphosphates such as resorcinol bis (diphenyl phosphate) (RDP) and bisphenol A bis (diphenyphosphate) (BDP); Either one can be used.
  • TPP triphenyl phosphate
  • RDP resorcinol bis
  • BDP bisphenol A bis
  • the aryl phosphate may be used isopropylated triphenyl phosphate having a TPP content of 5 to 10%, and the bisphosphate, Resorcinol bis (diphenyl phosphate) having a TPP content of less than 5% )) Or BDP (Bisphenol-A bis (diphenyl phosphate)) can be used.
  • the mixing weight ratio may be 1: 0.5 to 1: 3, preferably 1: 0.5 to 1: 1.5, but is not limited thereto.
  • the foamable refractory coating composition of the present invention may include 10 to 20% by weight, such as 13 to 18% by weight of a flame retardant. If it is less than 10% by weight, the flame retardancy of the coating film may be insufficient to burn well, and thus it may not sufficiently exhibit fire resistance. If the content exceeds 20% by weight, the melt viscosity of the coating film becomes low, and the carbonized layer is easily broken due to excessive foaming, so that the heat shielding performance cannot be exerted, and the TPP content is high, so that the desired level of gas hazard reduction effect and fire resistance performance cannot be obtained. .
  • the foaming agent used in the composition of the present invention is exposed to high temperature heat to soften / liquefy the cured coating film and decompose at the time when the carbonized layer is formed, thereby generating a large amount of gas, causing the carbonized layer to swell by having a fine pore layer.
  • the blowing agent may be selected from the group consisting of melamine, urea, glycine, and combinations thereof.
  • the foamable refractory coating composition of the present invention may include 3 to 10% by weight, such as 5 to 10% by weight of the blowing agent. If the content is less than 3% by weight, the paint may fail to expand, which may lower the thermal insulation performance. If the content is more than 10% by weight, the paint may expand too much, causing cracks in the carbonized layer, which may cause a decrease in strength. Can be.
  • the acid catalyst used in the composition of the present invention is decomposed at a time when the cured coating is softened by exposure to high temperature heat to promote the formation of a carbonized layer, and at the same time, decomposed and generated gas swells (expands) the carbonized layer. do.
  • the acid catalyst may be selected from the group consisting of ammonium phosphate, melamine polyphosphate, melamine monophosphate, melamine bisphosphate, and combinations thereof.
  • the foamable refractory coating composition of the present invention may include 20 to 40% by weight of an acid catalyst, such as 27 to 35% by weight. If it is less than 20% by weight, the formation of a carbonized layer is insufficient to ensure fire resistance, and if it exceeds 40% by weight, the carbonized layer may be easily broken due to excessive foaming, thereby lowering thermal insulation performance.
  • an acid catalyst such as 27 to 35% by weight.
  • the fiber used in the composition of the present invention (1) has a high specific surface area to provide thixotropy to the paint to prevent flow during coating, and (2) thin and long fibers are evenly distributed in the cured coating film to act as a reinforcing material. (3) Control the foaming rate during foaming as the cured coating film is softened by heat when fire occurs, and adjusts the foaming rate by supplementing the strength of the foamed carbonized layer by reacting with an acid catalyst and preventing cracks. It serves to keep it.
  • the fibers may be selected from the group consisting of ceramic fibers, mineral wool, carbon fibers, kevlar, and combinations thereof.
  • aluminosilicate fiber or magnesium silicate fiber may be used as the ceramic fiber
  • synthetic glass (silicate) fiber may be used as the mineral wool.
  • PAN-based carbon fibers may be used as the carbon fibers
  • para-aramid synthetic fibers may be used as the kevlar.
  • the foamable refractory coating composition of the present invention may comprise 3 to 10% by weight of fiber, such as 3 to 8% by weight. If it is less than 3% by weight, the ratio of fibers is low to show the crack prevention effect of the carbonized layer, and if it is more than 10% by weight, the fiber content is too high, which impairs the painting workability due to the increase in the viscosity of the paint, and the paint does not expand. The lower the heat shield performance can be reduced.
  • the foamable refractory coating composition of the present invention may further include one or more additives selected from the group consisting of dispersants, antifoaming agents, colorants, thickeners, pigments and curing catalysts in order to achieve optimum coating and coating performance.
  • the foamable refractory paint composition of the present invention may include 5 to 15% by weight of an additive. If it is less than 5% by weight is not desired to disperse the coating may be bubbles in the coating film, if it exceeds 15% by weight it may be the adhesion performance of the coating film is degraded.
  • the foamable refractory paint composition of the present invention has a gas hazard of 12 minutes or more when measured by the gas hazard test method (KSF 2271), and has a fire resistance when measured by the fire test method (UL 1709) without using a separate reinforcing material (mesh). Over time, it is possible to reduce the risk of suffocation in case of fire by improving the release of harmful gas when the film expands in case of fire, so that it is possible to control oil or gas such as offshore structures or plants, Effective as a fireproof paint.
  • Epoxy resin Bisphenol A resin, equivalent weight 182 ⁇ 192g / eq, viscosity 11,000 ⁇ 14,000cps, color Max.25 APHA, hydrolyzable chlorine content Max.300 ppm, weight average molecular weight 100 ⁇ 400
  • Curing Resin Amide Resin, Viscosity 300 ⁇ 600cps, Color (#G) Max.11, Amine Value 400 ⁇ 500 mgKOH / g, Active Hydrogen Equivalent 50 ⁇ 150 g / eq
  • Foaming agent melamine
  • Phosphorus flame retardant # 1 liquid: isopropylated triphenyl phosphate (TPP content> 21 wt%, pyrolysis temperature below 250 ° C (less than TGA heating loss 5%))
  • Phosphorus flame retardant # 2 liquid: isopropylated triphenyl phosphate (TPP content 10 wt% or less, pyrolysis temperature 250 °C or more (TGA heating loss 5% or less), viscosity 60-80 cps)
  • Phosphorus flame retardant # 3 liquid: RDP (TPP content less than 5% by weight, pyrolysis temperature 250 ° C or more (TGA heating loss 5% or less), viscosity 600 cps)
  • Fiber # 1 Aluminosilicate Fiber (diameter 1 ⁇ 2.5 ⁇ m, length about 5,000 ⁇ m, melting point 1,760 °C)
  • Fiber # 2 Magnesium Silicate Fiber (Diameter 2-3 ⁇ m, Melting Point 1,500 ⁇ 1,550 °C)
  • Fiber # 3 mineral wool (diameter 6 ⁇ m (number average), length 650 ⁇ 150 ⁇ m, melting point 1,000 °C)
  • Fiber # 4 Carbon Fiber (diameter 7 ⁇ m, length 3 mm, specific gravity 1.8)
  • Curing catalyst tris- (dimethylaminomethyl) phenol
  • Dispersant A solution of salts of unsaturated polyamine amides and acidic polyesters
  • the fire resistance test was conducted using the Rapid Rise Fire Tests of Protection Materials for Structural Steel (UL1709), which simulated the heating temperature of oil fires on steel structures. This heating curve is characterized by heating up to 1,093 ° C within 5 minutes, and is a heating temperature graph which is the standard in oil fire test of steel structure internationally.
  • the evaluation method is to ensure the performance as a refractory structure when the average temperature of the cross-section at the end of the test is less than 538 °C and less than the maximum temperature of 649 °C sensor.
  • Table 1 shows the results of comparing the fire resistance performance with a test specimen coated with a mesh (Mesh free) paint (W10 ⁇ 49, ANSI Designation) without using a reinforcing material.
  • the gas hazard test was conducted according to the KSF 2271 test method.
  • the main test is to burn the specimen by applying heat to the refractory paint-coated specimen, collect the smoke generated, and send the smoke to the room where the mouse is located to measure the average stop time of the mouse. If the hazards of the gas improve, the average downtime of the mouse can be longer.
  • the evaluation criteria is more than 9 minutes.
  • Examples 1 to 3 of the foamable refractory coating composition of the present invention by using a liquid phosphorus flame retardant having a TPP content of 20% by weight or less, pyrolysis temperature of 250 °C or more, without the use of a reinforcing material (mesh) While satisfying the performance criteria, it was confirmed that the excellent gas harmful properties.
  • Comparative Examples 1 and 2 using a phosphorus-based flame retardant having a TPP content of 21% or more it was confirmed that the fire resistance was poor or the gas hazard was less than 9 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement ignifuge comprenant : une résine époxy ; une résine durcissable ; un retardateur ; un agent moussant ; un catalyseur acide ; et une fibre. En particulier, en utilisant un retardateur contenant une quantité inférieure ou égale à 20 % en poids de phosphate de triphényle et possédant une température de pyrolyse supérieure ou égale à 250 °C, la présente invention peut réduire la nocivité du gaz, conférer de la flexibilité à une couche de mousse et empêcher la formation de fissures dans une couche de carbonisation, ce qui permet d'améliorer la résistance au feu sur le long terme.
PCT/KR2016/012894 2015-11-12 2016-11-10 Composition de revêtement ignifuge WO2017082639A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201680063923.9A CN108603053B (zh) 2015-11-12 2016-11-10 发泡性耐火涂料组合物
SG11201803262QA SG11201803262QA (en) 2015-11-12 2016-11-10 Foamable fire resistant coating composition
MYPI2018000625A MY188861A (en) 2015-11-12 2016-11-10 Fire resistant coating composition
TR2018/06404T TR201806404T1 (tr) 2015-11-12 2016-11-10 Köpükleşebilen ateşe dayanıklı kaplama bileşimi.
SA518391473A SA518391473B1 (ar) 2015-11-12 2018-04-30 تركيبة طلاء مقاومة للحريق قابلة للإرغاء
HK18113792.3A HK1254539A1 (zh) 2015-11-12 2018-10-29 發泡性耐火塗料組合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0158792 2015-11-12
KR1020150158792A KR101729075B1 (ko) 2015-11-12 2015-11-12 발포성 내화도료 조성물

Publications (1)

Publication Number Publication Date
WO2017082639A1 true WO2017082639A1 (fr) 2017-05-18

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Application Number Title Priority Date Filing Date
PCT/KR2016/012894 WO2017082639A1 (fr) 2015-11-12 2016-11-10 Composition de revêtement ignifuge

Country Status (8)

Country Link
KR (1) KR101729075B1 (fr)
CN (1) CN108603053B (fr)
HK (1) HK1254539A1 (fr)
MY (1) MY188861A (fr)
SA (1) SA518391473B1 (fr)
SG (1) SG11201803262QA (fr)
TR (1) TR201806404T1 (fr)
WO (1) WO2017082639A1 (fr)

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KR102237294B1 (ko) * 2019-06-26 2021-04-07 (주)수 캡슐형 소화약제를 이용한 2액형 초기화재진압용 에폭시계 도료 조성물 및 에어로졸형 에폭시계 도료 조성물
CN110951354B (zh) * 2019-10-24 2022-01-11 江苏兰陵高分子材料有限公司 一种非机械施工用环氧树脂基膨胀型钢结构防火涂料及其制备方法
CN110667203A (zh) * 2019-10-29 2020-01-10 东莞市海洲新材料科技有限公司 一种防火隔热金属板及其制备方法
KR20230027762A (ko) 2021-08-20 2023-02-28 신형일 소화캡슐을 포함하는 소화도료 조성물

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KR20110094006A (ko) * 2008-12-08 2011-08-19 알베마를 코포레이션 인계 난연제 및 이를 위한 적용분야
KR101115326B1 (ko) * 2011-07-20 2012-02-20 주식회사 범건축 종합건축사사무소 난연성을 갖는 에폭시 바닥마감재 도막의 형성방법 및 난연성을 갖는 에폭시 바닥마감재
KR20130044669A (ko) * 2011-10-24 2013-05-03 주식회사 케이씨씨 화재시 가스유해성이 개선된 무용제형 에폭시 내화 도료 조성물

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HK1254539A1 (zh) 2019-07-19
SA518391473B1 (ar) 2021-09-08
KR101729075B1 (ko) 2017-04-21
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