WO2012060491A1 - Water-soluble flame-retardant composition - Google Patents
Water-soluble flame-retardant composition Download PDFInfo
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- WO2012060491A1 WO2012060491A1 PCT/KR2010/007780 KR2010007780W WO2012060491A1 WO 2012060491 A1 WO2012060491 A1 WO 2012060491A1 KR 2010007780 W KR2010007780 W KR 2010007780W WO 2012060491 A1 WO2012060491 A1 WO 2012060491A1
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- flame retardant
- water
- retardant composition
- guanidine
- phosphate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
Definitions
- the present invention relates to a water-soluble flame retardant composition which is flame-retardant to the surface of the substrate of the combustible material in order to improve the flame retardancy so that the combustible materials such as wood, wallpaper, curtains and the like do not burn easily during a fire.
- Combustible materials such as wood, wallpaper, curtains, and the like are easily burned in the event of a fire, thereby increasing the risk of fire.
- a flame retardant material is developed to prevent (burn) the surface of the combustible material by suppressing and preventing combustion, and flame retardant treatment of the combustible material using the flame retardant material prevents the combustion of fire easily.
- Flame-retardant material for such a flame retardant is provided in various ways, such as Patent Documents 1 to 3.
- Patent No. 10-0865176 In the flame retardant treatment method using the water-soluble flame retardant composition, Patent No. 10-0865176, Patent Document No. 10-0865176, and a flame retardant composition prepared by the method, the aqueous magnesium magnesium phosphate solution, bentonite, soybean oil, baking powder, emulsifier It provides a flame retardant treatment method using a flame retardant composition prepared by the titanium magnesium ammonium phosphate-bentonite-based flame retardant composition, a preparation method, and the method comprising a base containing oleic acid, dimethylamine, and magnesium ammonium phosphate aqueous solution,
- the titanium magnesium phosphate ammonium-bentonite-based flame retardant composition is a flame retardant synergistic effect by the phosphorus and nitrogen, magnesium hydroxide, titanium, bentonite, baking powder, etc.
- the flame retardant composition is 85 to 99% by weight aqueous solution of magnesium ammonium phosphate, silane Water-soluble flame retardant composition consisting of 0.1 to 5.0% by weight of the adhesive, 0.1 to 5.0% by weight of boric acid, 0.1 to 10.0% by weight of borax, and 0.1 to 10.0% by weight of ammonium phosphate, using the method and a flame retardant composition prepared by the method A flame retardant treatment method is provided, and the water-soluble flame retardant composition is excellent in flame retardancy, water resistance, heat resistance and abrasion resistance due to phosphorus, nitrogen, magnesium, zinc, borax, and boric acid, as well as excellent antiseptic and insect repellent effects.
- thermoplastic compositions comprising the same, and methods for producing such compositions, do not contain halogen or substantially contain halogen.
- flame retardant compositions and flame retardant thermoplastic compositions containing the same are provided. In particular, it is free of halogen or substantially free of halogen, and (i) at least one high charring polymer; (ii) at least one low volatility phosphate ester; And (iii) a blend of at least one compound that splits off high volatile phosphorus-containing fragments. It also provides a technique for thermoplastic flame retardant compositions comprising the above flame retardant compositions blended with at least one thermoplastic resin, preferably polystyrene resin.
- Patent Document 1 Domestic Patent Registration No. 10-0865176 (Registration Date 2008.10.17).
- Patent Document 2 2. Domestic Patent Registration No. 10-0893948 (Registration date 2009.04.10).
- Patent Document 3 Korean Laid-Open Patent Publication No. 10-2009-006054 (published date 2009.01.14).
- the water-soluble flame retardant composition which is coated on the surface of the substrate made of a combustible material and is burned (carbonized) first, before the substrate is burned during combustion, forms a carbon film to suppress the development of combustion (carbonization), It is intended to provide a water soluble flame retardant composition comprising 25% guanidine phosphate system to delay.
- the water-soluble flame retardant composition of the present invention for achieving the above object is composed of 11.61 to 45.4% by weight of flame retardant, 0.1 to 15% by weight of 25% guanidine phosphate, and the remaining solvent, the solvent is water, ethyl alcohol, iso A mixture of one or two or more selected from propyl alcohol and n-methylpyrrolidone is used.
- the flame retardant is guanidine phosphate (Guanidine phosphate), ammonium phosphate (basic ammonium phosphate dibasic), monochloroacetic acid (Monochloroacetic acid), guanidine carbonate (Guanidine carbonate), ethylene diamine (Ethylenediamine), disodinium octaborate tetrahydrate (Disodium Octaborate) tetrahydrate).
- the water-soluble flame retardant composition 49.6 to 89.19 weight% of water; 0.2 to 5.0 weight percent of guanidine phosphate; 8.0-16.0 weight percent of ammonium phosphate dibasic; 1.0-2.0 wt% of ammonium chloride; 0.4 to 2.4 wt% monochloroacetic acid; 0.1 to 2.0 wt% of guanidine carbonate; 0.01 to 3.0% by weight of ethylene diamine; 1 to 5% by weight of disodium octaborate tetrahydrate; It consists of 0.1-15% by weight of 25% guanidine phosphate.
- the 25% guanidine phosphate system is one of polyethylenediamine-guanidine phosphate, polypropylenediamine-guanidine phosphate, polybutylenediamine-guanidine phosphate, polypentanediamine-guanidine phosphate, polyhexamethylenediamine-guanidine phosphate, or The mixture which selected and mixed 2 or more types is used.
- the water-soluble flame retardant composition made as described above may be applied to the surface of the flammable material by spraying to perform flame retardant treatment or to immerse the flammable material to perform flame retardant treatment, and used as a flame retardant (coating) treatment on the surface of the flammable material.
- the coating layer burns before combustion of the substrate before combustion to form a carbon film to suppress the development of combustion.
- the water-soluble flame retardant composition is an environmentally friendly flame retardant that is excellent in heat, water, low toxicity, and fire resistance, does not cause environmental pollution, and is simple to manufacture, and is applied to the surface of the combustible material by spraying or brushing. Coating) or by immersing the combustible material in the water-soluble flame retardant composition so that the water-soluble flame retardant composition is impregnated in the combustible material, and flame retardant to various substrates is possible and has a simple advantage. As a result, it is possible to lower the unit cost of the water-soluble flame retardant composition, lower the flame retardant treatment cost, and flame retardant treatment on various substrates.
- a flame retardant is applied by coating (coating) with a sprayer or a brush on the surface of an object made of a combustible material such as paper, wood, fiber or the like.
- This water-soluble flame retardant composition is composed of a flame retardant, a mixture of 25% guanidine phosphate and a solvent, the composition ratio of 11.61 to 45.4% by weight of flame retardant, 0.1 to 15% by weight of 25% guanidine phosphate and the remaining solvent.
- the solvent may be water, ethyl alcohol, isopropyl alcohol, or one of n-methylpyrrolidone, or a mixture of two or more selected may be used.
- the flame retardant is guanidine phosphate (Guanidine phosphate), ammonium phosphate (basic ammonium phosphate dibasic), monochloroacetic acid (Monochloroacetic acid), guanidine carbonate (Guanidine carbonate), ethylene diamine (Ethylenediamine), disodinium octaborate tetrahydrate (Disodium Octaborate) or a mixture consisting of tetrahydrate, or guanidine phosphate, ammonium phosphate dibasic, ammonium chloride, monochloroacetic acid, guanidine carbonate, ethylene diamine Ethylenediamine) and disodium octaborate tetrahydrate.
- the disodinium octaborate tetrahydrate (DOT) penetrates into the interior of the substrate and remains in a bonded state with the substrate, thereby forming a heat insulation layer in the interior of the substrate during a fire, thereby exhibiting a flame retardant effect.
- the 25% guanidine phosphate-based water-soluble flame retardant composition which forms a flame retardant layer formed on the surface of the combustible material during combustion is burned (carbonized) by burning (carbonizing) before the substrate burns (burns) in case of a fire.
- Polyethylenediamine-guanidine phosphate poly (ethylenediamine-guanidine phosphate), polypropylenediamine-guanidine phosphate, polybutylenediamine-guanidine phosphate poly (buthylenediamine-guanidine phosphate) Pentanediamine-guanidine phosphate poly (pentanediamine-guanidine phosphate), polyhexamethylenediamine-guanidine phosphate poly (hexamethylenediamine-guanidine phosphate) may be selected and used, or two or more selected mixtures may be used.
- the water-soluble flame retardant composition made as described above is coated on the substrate of the combustible material so that the coating material is first burned (carbonized) to form a carbon coating before the substrate is burned (burned) at the time of fire to suppress the development of combustion (flame).
- Table 1 Composition ratio of water soluble flame retardant composition division Composition ratio (% by weight) water 49.6 ⁇ 89.2 resist Guanidine phosphate 0.2 ⁇ 5.0 Ammonium phosphate dibasic 8.0-16.0 Ammonium chloride 1.0-2.0 Monochloroacetic acid 0.4-2.4 Guanidine carbonate 0.1-2.0 Ethylenediamine 0-3.0 Disodium Octaborate Tetrahydrate 1-5 25% Guanidine Phosphate 0.1-15
- Example 2 water 89.2 wt% 69.6 wt% 49.6 wt% Guanidine phosphate 0.2 wt% 2.5 wt% 5 wt% Ammonium phosphate dibasic 8.0 wt% 12 wt% 16 wt% Ammonium chloride 1.0 wt% 1.5 wt% 2 wt% Monochloroacetic acid 0.4 wt% 1.4 wt% 2.4 wt% Guanidine carbonate 0.1 wt% 1.0 wt% 2 wt% Ethylenediamine - 1.5 wt% 3 wt% Disodium Octaborate Tetrahydrate 1.0 wt% 3 wt% 5 wt% 25% Guanidine Phosphate 0.1 wt% 7.5 wt% 15 wt%
Abstract
The present invention relates to a water-soluble, flame-retardant composition for enhancing the flame resistance of a basic material by coating the composition on the surface thereof, to reduce damage in case of a fire. The water-soluble, flame-retardant composition of the present invention comprises: 49.6-89.19 wt% of water; 0.2-5.0 wt% of guanidine phosphate; 8.0-16.0 wt% of ammonium phosphate dibasic; 1.0-2.0 wt% of ammonium chloride; 0.4-2.4 wt% of monochloroacetic acid; 0.1-2.0 wt% of guanidine carbonate; 0.01-3.0 wt% of ethylenediamine; 1-5 wt% of disodium octaborate tetrahydrate; and 0.1-15 wt% of 25% guanidine phosphate-based flame retardant.
Description
본 발명은 화재발생시 나무, 벽지, 커튼 등과 같은 가연성 물질들이 쉽게 연소하지 않도록 난연성을 향상시키기 위하여 가연성 물질의 기재 표면에 방염처리를 하는 수용성 난연제 조성물에 관한 것이다. The present invention relates to a water-soluble flame retardant composition which is flame-retardant to the surface of the substrate of the combustible material in order to improve the flame retardancy so that the combustible materials such as wood, wallpaper, curtains and the like do not burn easily during a fire.
나무, 벽지, 커튼, 등의 가연성 물질들은 화재발생시 쉽게 연소함으로써 화재위험성이 크다.Combustible materials such as wood, wallpaper, curtains, and the like are easily burned in the event of a fire, thereby increasing the risk of fire.
이러한 가연성 물질의 연소를 방지하기 위하여 가연성 물질의 표면에 도포(코팅)하여 연소를 억제, 방지하는 난연성 물질이 개발되고, 상기 난연성 물질을 이용하여 가연성 물질을 방염처리 함으로써 화재발생시 쉽게 연소하지 못하도록 하고 있다.In order to prevent the combustion of the combustible material, a flame retardant material is developed to prevent (burn) the surface of the combustible material by suppressing and preventing combustion, and flame retardant treatment of the combustible material using the flame retardant material prevents the combustion of fire easily. have.
이러한 방염처리를 위한 난연성 물질은 특허문헌 1 내지 3 등과 같이 다양하게 제공되어 있다.Flame-retardant material for such a flame retardant is provided in various ways, such as Patent Documents 1 to 3.
특허문헌 1인 등록특허 등록번호 10-0865176호의 수용성 난연제 조성물, 그 제조방법, 및 그 제조방법에 의해 제조된 난연제 조성물을 이용한 난연 처리 방법에서는, 인산티탄마그네슘 수용액, 벤토나이트, 콩기름, 베이킹파우더, 유화제, 올레인산, 디메틸아민을 포함한 염기, 및 인산마그네슘암모늄 수용액으로 이루어지는 인산티탄마그네슘암모늄-벤토나이트계 난연제 조성물, 그 제조방법, 및 그 제조방법에 의해 제조된 난연제 조성물을 이용한 난연 처리 방법을 제공하고 있으며, 상기 인산티탄마그네슘암모늄-벤토나이트계 난연제 조성물은 인과 질소, 그리고 수산화마그네슘, 티탄, 벤토나이트, 베이킹파우더 등에 의한 난연성 상승효과와 단일약품으로 여러 종류의 건축재에 난연 처리를 할 수 있어 경제적이고, 내열, 내수, 저독성, 내화기능이 우수하고, 환경공해를 유발하지 않는 친환경적인 난연제로서 그 성능이 뛰어나며, 인체에 무해하다고 기재하고 있다.In the flame retardant treatment method using the water-soluble flame retardant composition, Patent No. 10-0865176, Patent Document No. 10-0865176, and a flame retardant composition prepared by the method, the aqueous magnesium magnesium phosphate solution, bentonite, soybean oil, baking powder, emulsifier It provides a flame retardant treatment method using a flame retardant composition prepared by the titanium magnesium ammonium phosphate-bentonite-based flame retardant composition, a preparation method, and the method comprising a base containing oleic acid, dimethylamine, and magnesium ammonium phosphate aqueous solution, The titanium magnesium phosphate ammonium-bentonite-based flame retardant composition is a flame retardant synergistic effect by the phosphorus and nitrogen, magnesium hydroxide, titanium, bentonite, baking powder, etc. and can be flame-retardant treatment of various types of building materials as a single chemical, economical, heat-resistant, water-resistant , Low toxicity, fireproof And an eco-friendly flame retardant that does not cause environmental pollution, its excellent performance, discloses that it is harmless to the human body.
특허문헌 2인 등록특허 등록번호 10-0893948호의 수용성 난연제 조성물, 그 제조방법 및 그 제조방법에 의해 제조된 난연제 조성물을 이용한 난연 처리방법에서는, 난연제 조성물이 인산마그네슘암모늄 수용액 85 ~ 99중량%, 실란접착제 0.1 ~ 5.0 중량%, 붕산 0.1 ~ 5.0 중량%, 붕사 0.1 ~ 10.0 중량%, 및 인산암모늄 0.1 ~ 10.0 중량%로 이루어진 수용성 난연제 조성물, 그 제조방법 및 그 제조방법에 의해 제조된 난연제 조성물을 이용한 난연 처리방법이 제공되어 있으며, 상기 수용성 난연제 조성물은 인, 질소, 마그네슘, 아연, 붕사, 및 붕산의 성분으로 인해 난연성, 내수성, 내열성 및 내마모성이 우수한 장점이 있을 뿐만 아니라 방부, 방충의 효과가 우수하고, 환경공해를 유발하지 않으며, 인체에 무해하며, 또한, 단일 난연제 조성물을 이용하여 목재, 무늬목부착MDF, 무늬목우레탄코팅MDF, 또는 PVC필름부착MDF 등의 여러 종류의 건축자재에 난연 처리를 할 수 있어 경제적이고, 연기 및 유독가스의 발생을 감소시키고 연소확산을 막아 인명과 재산의 피해를 줄일 수 있고, 수입대체효과가 클 것으로 기대된다고 기재하고 있다.In the flame-retardant treatment method using the water-soluble flame retardant composition, Patent No. 10-0893948, Patent No. 10-0893948, flame retardant composition prepared by the method and the production method, the flame retardant composition is 85 to 99% by weight aqueous solution of magnesium ammonium phosphate, silane Water-soluble flame retardant composition consisting of 0.1 to 5.0% by weight of the adhesive, 0.1 to 5.0% by weight of boric acid, 0.1 to 10.0% by weight of borax, and 0.1 to 10.0% by weight of ammonium phosphate, using the method and a flame retardant composition prepared by the method A flame retardant treatment method is provided, and the water-soluble flame retardant composition is excellent in flame retardancy, water resistance, heat resistance and abrasion resistance due to phosphorus, nitrogen, magnesium, zinc, borax, and boric acid, as well as excellent antiseptic and insect repellent effects. It does not cause environmental pollution, is harmless to the human body, and also, using a single flame retardant composition, wood, wood veneer MDF, It is economical because it can be flame-retardant to various kinds of building materials such as veneer urethane coated MDF or PVC film with PVC film, and it can reduce the generation of smoke and toxic gas and prevent the spread of combustion, which can reduce the damage of life and property. The import substitution effect is expected to be large.
특허문헌 3인 공개특허 공개번호 10-2009-006054호의 할로겐을 포함하지 않는 난연제 조성물들, 이를 포함하여 구성되는 열가소성 조성물들 및 이러한 조성물들의 제조방법에서는, 할로겐을 포함하지 않거나 할로겐을 실질적으로 포함하지 않는 난연제 조성물들 그리고 이를 함유하는 난연 열가소성 조성물들에 관한 기술이 제공되어 있다. 특히, 할로겐을 포함하지 않거나 할로겐을 실질적으로 포함하지 않으며, (i) 적어도 하나의 고 탄화 폴리머(high charring polymer); (ii) 적어도 하나의 저 휘발성 포스페이트 에스테르; 및 (iii) 고 휘발성 인-함유 프래그먼트(fragment)를 분리시키는(split off) 적어도 하나의 화합물의 블렌드를 포함하여 구성되는 난연제 조성물에 대한 기술을 제공하고 있다. 아울러 적어도 하나의 열가소성 레진, 바람직하게는 폴리스티렌 레진과 블렌딩된 상술한 난연제 조성물들을 포함하여 구성되는 열가소성 난연 조성물에 대한 기술을 제공하고 있다.Flame-retardant compositions that do not contain halogen, Patent No. 10-2009-006054 of Patent Document 3, thermoplastic compositions comprising the same, and methods for producing such compositions, do not contain halogen or substantially contain halogen. And flame retardant compositions and flame retardant thermoplastic compositions containing the same are provided. In particular, it is free of halogen or substantially free of halogen, and (i) at least one high charring polymer; (ii) at least one low volatility phosphate ester; And (iii) a blend of at least one compound that splits off high volatile phosphorus-containing fragments. It also provides a technique for thermoplastic flame retardant compositions comprising the above flame retardant compositions blended with at least one thermoplastic resin, preferably polystyrene resin.
[선행기술문헌][Preceding technical literature]
(특허문헌 1) 1. 국내 등록특허 등록번호 10-0865176호(등록일자 2008.10.17).(Patent Document 1) 1. Domestic Patent Registration No. 10-0865176 (Registration Date 2008.10.17).
(특허문헌 2) 2. 국내 등록특허 등록번호 10-0893948호(등록일자 2009.04.10).(Patent Document 2) 2. Domestic Patent Registration No. 10-0893948 (Registration date 2009.04.10).
(특허문헌 3) 3. 국내 공개특허 공개번호 10-2009-006054(공개일자 2009.01.14).(Patent Document 3) 3. Korean Laid-Open Patent Publication No. 10-2009-006054 (published date 2009.01.14).
본 발명은 화재발생시 가연성 물질들로 이루어진 기재의 연소시 탄소피막을 형성하여 연소되는 것을 방지하거나 지연시키기 위한 가연성 물질의 방염처리를 위한 수용성 난연제 조성물을 제공하고자 하는데 목적이 있다.It is an object of the present invention to provide a water-soluble flame retardant composition for flame retardant treatment of a combustible material for preventing or delaying combustion by forming a carbon film upon combustion of a substrate made of combustible materials during a fire.
즉, 가연성 물질로 이루어진 기재의 표면에 코팅되어 연소시 기재가 연소하기 전에 코팅물질인 수용성 난연제 조성물이 먼저 연소(탄화)되어 탄소피막을 형성하여 연소(탄화)의 전개를 억제하여 연소의 억제 및 지연을 시키도록 25% 구아니딘 인산염계를 포함하는 수용성 난연제 조성물을 제공하고자 한다.That is, the water-soluble flame retardant composition, which is coated on the surface of the substrate made of a combustible material and is burned (carbonized) first, before the substrate is burned during combustion, forms a carbon film to suppress the development of combustion (carbonization), It is intended to provide a water soluble flame retardant composition comprising 25% guanidine phosphate system to delay.
상기 목적을 달성하기 위한 본 발명인 수용성 난연제 조성물은, 11.61~45.4 중량%의 방염제와, 0.1~15 중량%의 25% 구아니딘 인산염계와, 나머지 용매로 이루어지고, 상기 용매는 물, 에틸알코올, 이소프로필 알코올, n-메틸피로리돈 중 1종 또는 2종 이상을 선택하여 혼합한 혼합물을 사용한다.The water-soluble flame retardant composition of the present invention for achieving the above object is composed of 11.61 to 45.4% by weight of flame retardant, 0.1 to 15% by weight of 25% guanidine phosphate, and the remaining solvent, the solvent is water, ethyl alcohol, iso A mixture of one or two or more selected from propyl alcohol and n-methylpyrrolidone is used.
상기 방염제는 구아니딘 포스페이트(Guanidine phosphate), 암모늄 포스페이트(Ammonium phosphate dibasic), 모노클로로아세틱 에시드(Monochloroacetic acid), 구아니딘 카보네이트(Guanidine carbonate), 에틸렌 디아민(Ethylenediamine), 디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate)로 이루어진 혼합물이다.The flame retardant is guanidine phosphate (Guanidine phosphate), ammonium phosphate (basic ammonium phosphate dibasic), monochloroacetic acid (Monochloroacetic acid), guanidine carbonate (Guanidine carbonate), ethylene diamine (Ethylenediamine), disodinium octaborate tetrahydrate (Disodium Octaborate) tetrahydrate).
즉, 수용성 난연제 조성물, 물 49.6~89.19 중량%와; 구아니딘 포스페이트(Guanidine phosphate) 0.2~5.0 중량%와; 암모늄 포스페이트(Ammonium phosphate dibasic) 8.0~16.0 중량%와; 암모늄 클로라이드(Ammonium chloride) 1.0~2.0 중량%와; 모노클로로아세틱 에시드(Monochloroacetic acid) 0.4~2.4 중량%와; 구아니딘 카보네이트(Guanidine carbonate) 0.1~2.0 중량%와; 에틸렌 디아민(Ethylenediamine) 0.01~3.0 중량%와; 디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate) 1~5 중량%와; 25% 구아니딘 인산염계 0.1~15 중량%로 이루어진다.That is, the water-soluble flame retardant composition, 49.6 to 89.19 weight% of water; 0.2 to 5.0 weight percent of guanidine phosphate; 8.0-16.0 weight percent of ammonium phosphate dibasic; 1.0-2.0 wt% of ammonium chloride; 0.4 to 2.4 wt% monochloroacetic acid; 0.1 to 2.0 wt% of guanidine carbonate; 0.01 to 3.0% by weight of ethylene diamine; 1 to 5% by weight of disodium octaborate tetrahydrate; It consists of 0.1-15% by weight of 25% guanidine phosphate.
상기 25% 구아니딘 인산염계는, 폴리에틸렌디아민-구아니딘 포스페이트, 폴리프로필렌디아민-구아니딘 포스페이트, 폴리부틸렌디아민-구아니딘 포스페이트, 폴리펜탄디아민-구아니딘 포스페이트, 폴리헥사메틸렌디아민-구아니딘 포스페이트 중 1종을 사용하거나 또는 2종 이상을 선택하여 혼합한 혼합물을 사용한다.The 25% guanidine phosphate system is one of polyethylenediamine-guanidine phosphate, polypropylenediamine-guanidine phosphate, polybutylenediamine-guanidine phosphate, polypentanediamine-guanidine phosphate, polyhexamethylenediamine-guanidine phosphate, or The mixture which selected and mixed 2 or more types is used.
상기와 같이 이루어진 수용성 난연제 조성물은 가연성 물질에 스프레이방식으로 표면에 도포하여 방염처리를 하거나 가연성 물질을 침지시켜 방염처리를 할 수 있으며, 상기 가연성 물질의 표면에 방염(코팅)처리로 사용된 25% 구아니딘 인산염계를 포함하는 수용성 난연제 조성물은 연소시 코팅층이 기재의 연소 전에 먼저 연소하여 탄소 피막을 형성하여 연소의 전개를 억제한다.The water-soluble flame retardant composition made as described above may be applied to the surface of the flammable material by spraying to perform flame retardant treatment or to immerse the flammable material to perform flame retardant treatment, and used as a flame retardant (coating) treatment on the surface of the flammable material. In water-soluble flame retardant compositions comprising guanidine phosphate-based, the coating layer burns before combustion of the substrate before combustion to form a carbon film to suppress the development of combustion.
또한, 수용성 난연제 조성물은 내열, 내수, 저독성, 내화기능이 우수하고, 환경공해를 유발하지 않는 친환경적인 난연제로 그 제조가 간단하고, 가연성 물질의 표면에 스프레이방식 또는 붓 칠과 같은 방식으로 도포(코팅)처리를 하거나 가연성 물질을 수용성 난연제 조성물에 침지하여 수용성 난연제 조성물이 가연성 물질에 함침되도록 함으로써 다양한 기재에 대하여 방염처리가 가능하고, 간단한 장점을 가진다. 이로 인하여 수용성 난연제 조성물의 단가를 낮추고, 방염처리비용을 낮추는 동시에 다양한 기재에 방염처리가 가능하다.In addition, the water-soluble flame retardant composition is an environmentally friendly flame retardant that is excellent in heat, water, low toxicity, and fire resistance, does not cause environmental pollution, and is simple to manufacture, and is applied to the surface of the combustible material by spraying or brushing. Coating) or by immersing the combustible material in the water-soluble flame retardant composition so that the water-soluble flame retardant composition is impregnated in the combustible material, and flame retardant to various substrates is possible and has a simple advantage. As a result, it is possible to lower the unit cost of the water-soluble flame retardant composition, lower the flame retardant treatment cost, and flame retardant treatment on various substrates.
상기와 같이 수용성 난연제 조성물의 단가와 방염처리비용을 낮출 수 있음으로 화재예방을 위하여 누구나 쉽게 방염처리를 할 수 있으며, 화재로부터 보호를 받을 수 있을 것으로 기대된다.As described above, it is possible to lower the unit cost and flame retardant treatment cost of the water-soluble flame retardant composition, so that anyone can easily flame retardant for fire prevention, and is expected to be protected from fire.
본 발명의 바람직한 실시 예를 상세히 설명하도록 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.It will be described in detail a preferred embodiment of the present invention. Prior to this, terms or words used in the present specification and claims should not be construed as being limited to the common or dictionary meanings, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that it can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.
따라서, 본 명세서에 기재된 실시 예의 구성은 본 발명의 가장 바람직한 일 실시 예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형 예들이 있을 수 있음을 이해하여야 한다.Therefore, the configuration of the embodiments described herein is only one of the most preferred embodiments of the present invention and does not represent all of the technical idea of the present invention, various equivalents and modifications that can replace them at the time of the present application It should be understood that there may be
본 발명의 수용성 난연제 조성물은 종이, 목재, 섬유 등과 같은 가연성 물질로 이루어지는 물건의 표면에 스프레이어 또는 붓 등으로 도포(코팅)하여 방염처리를 하는 것이다.In the water-soluble flame retardant composition of the present invention, a flame retardant is applied by coating (coating) with a sprayer or a brush on the surface of an object made of a combustible material such as paper, wood, fiber or the like.
이러한 수용성 난연제 조성물은, 방염제와 25% 구아니딘 인산염계와 용매의 혼합물로 이루어지며, 그 구성비는 방염제 11.61~45.4 중량%와, 25% 구아니딘 인산염계 0.1~15 중량%와 나머지 용매로 이루어진다.This water-soluble flame retardant composition is composed of a flame retardant, a mixture of 25% guanidine phosphate and a solvent, the composition ratio of 11.61 to 45.4% by weight of flame retardant, 0.1 to 15% by weight of 25% guanidine phosphate and the remaining solvent.
상기 용매는 물 또는 에틸알코올 또는 이소프로필 알코올 또는 n-메틸피로리돈 중 어느 하나인 1종을 사용하거나 또는 2종 이상을 선택하여 혼합한 혼합물을 사용할 수 있다.The solvent may be water, ethyl alcohol, isopropyl alcohol, or one of n-methylpyrrolidone, or a mixture of two or more selected may be used.
상기 방염제는 구아니딘 포스페이트(Guanidine phosphate), 암모늄 포스페이트(Ammonium phosphate dibasic), 모노클로로아세틱 에시드(Monochloroacetic acid), 구아니딘 카보네이트(Guanidine carbonate), 에틸렌 디아민(Ethylenediamine), 디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate)로 이루어진 혼합물이거나, 또는 구아니딘 포스페이트(Guanidine phosphate), 암모늄 포스페이트(Ammonium phosphate dibasic), 암모늄 클로라이드(Ammonium chloride), 모노클로로아세틱 에시드(Monochloroacetic acid), 구아니딘 카보네이트(Guanidine carbonate), 에틸렌 디아민(Ethylenediamine), 디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate)로 이루어진다.The flame retardant is guanidine phosphate (Guanidine phosphate), ammonium phosphate (basic ammonium phosphate dibasic), monochloroacetic acid (Monochloroacetic acid), guanidine carbonate (Guanidine carbonate), ethylene diamine (Ethylenediamine), disodinium octaborate tetrahydrate (Disodium Octaborate) or a mixture consisting of tetrahydrate, or guanidine phosphate, ammonium phosphate dibasic, ammonium chloride, monochloroacetic acid, guanidine carbonate, ethylene diamine Ethylenediamine) and disodium octaborate tetrahydrate.
상기 디소디늄 옥타보레이트 테트라하이드레이트(DOT)는 기재의 내부에 침투되어 기재와 결합되어 있는 상태로 존재하여, 화재발생 시 기재 내부에서 단열층을 형성하여 방염효과를 나타낸다. The disodinium octaborate tetrahydrate (DOT) penetrates into the interior of the substrate and remains in a bonded state with the substrate, thereby forming a heat insulation layer in the interior of the substrate during a fire, thereby exhibiting a flame retardant effect.
상기 25% 구아니딘 인산염계는, 가연성 물질의 연소시 표면에 형성된 방염층을 형성하는 수용성 난연제 조성물이 화재발생시 기재가 연소(타기) 전에 먼저 연소(탄화)되어 탄소피막을 형성함으로써 연소(불길)의 전개를 억제 하는 성분으로, 폴리에틸렌디아민-구아니딘 포스페이트 poly(ethylenediamine-guanidine phosphate), 폴리프로필렌디아민-구아니딘 포스페이트 poly(propylenediamine-guanidine phosphate), 폴리부틸렌디아민-구아니딘 포스페이트 poly(buthylenediamine-guanidine phosphate), 폴리펜탄디아민-구아니딘 포스페이트 poly(pentanediamine-guanidine phosphate), 폴리헥사메틸렌디아민-구아니딘 포스페이트 poly(hexamethylenediamine-guanidine phosphate) 중 어느 하나를 선택하여 사용하거나, 또는 2 이상을 선택하여 혼합한 혼합물을 사용할 수 있다.The 25% guanidine phosphate-based water-soluble flame retardant composition which forms a flame retardant layer formed on the surface of the combustible material during combustion is burned (carbonized) by burning (carbonizing) before the substrate burns (burns) in case of a fire. Polyethylenediamine-guanidine phosphate poly (ethylenediamine-guanidine phosphate), polypropylenediamine-guanidine phosphate, polybutylenediamine-guanidine phosphate poly (buthylenediamine-guanidine phosphate) Pentanediamine-guanidine phosphate poly (pentanediamine-guanidine phosphate), polyhexamethylenediamine-guanidine phosphate poly (hexamethylenediamine-guanidine phosphate) may be selected and used, or two or more selected mixtures may be used.
상기와 같이 이루어진 수용성 난연제 조성물이 가연성 물질의 기재에 코팅되어 화재발생시 기재가 연소(타기) 전에 코팅물질이 먼저 연소(탄화)되어 탄소피막을 형성함으로써 연소(불길)의 전개를 억제한다.The water-soluble flame retardant composition made as described above is coated on the substrate of the combustible material so that the coating material is first burned (carbonized) to form a carbon coating before the substrate is burned (burned) at the time of fire to suppress the development of combustion (flame).
이러한 25% 구아니딘 인산염계 중 폴리에틸렌디아민-구아니딘 포스페이트의 합성의 예를 설명하면,An example of the synthesis of polyethylenediamine-guanidine phosphate in this 25% guanidine phosphate system
에틸렌디아민(ethylenediamine) 1몰(mol)과 구아니딘 포스페이트(guanidine phosphate) 1몰(mol)을 150℃로 9시간 가열하여 폴리에틸렌디아민-구아니딘 포스페이트 poly(ethylenediamine-guanidine phosphate)를 획득하고, 여기에 물(증류수(H2O))을 첨가하여 25% 폴리에틸렌디아민-구아니딘 포스페이트 poly(ethylenediamine-guanidine phosphate)를 얻는다.1 mol of ethylenediamine and 1 mol of guanidine phosphate were heated to 150 ° C. for 9 hours to obtain polyethylenediamine-guanidine phosphate poly (ethylenediamine-guanidine phosphate). Distilled water (H 2 O)) is added to give 25% polyethylenediamine-guanidine phosphate poly (ethylenediamine-guanidine phosphate).
상기 수용성 난연제 조성물의 구성비를 표로 나타내면,When the composition ratio of the said water-soluble flame retardant composition is shown in a table | surface,
표 1 수용성 난연제 조성물의 구성비
Table 1 Composition ratio of water soluble flame retardant composition
| 구분 | 구성비(중량%) | |
| 물 | 49.6~89.2 | |
| 방염제 | 구아니딘 포스페이트(Guanidine phosphate) | 0.2~5.0 |
| 암모늄 포스페이트(Ammonium phosphate dibasic) | 8.0~16.0 | |
| 암모늄 클로라이드(Ammonium chloride) | 1.0~2.0 | |
| 모노클로로아세틱 에시드(Monochloroacetic acid) | 0.4~2.4 | |
| 구아니딘 카보네이트(Guanidine carbonate) | 0.1~2.0 | |
| 에틸렌 디아민(Ethylenediamine) | 0~3.0 | |
| 디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate) | 1~5 | |
| 25% 구아니딘 인산염계 | 0.1~15 | |
| division | Composition ratio (% by weight) | |
| water | 49.6 ~ 89.2 | |
| resist | Guanidine phosphate | 0.2 ~ 5.0 |
| Ammonium phosphate dibasic | 8.0-16.0 | |
| Ammonium chloride | 1.0-2.0 | |
| Monochloroacetic acid | 0.4-2.4 | |
| Guanidine carbonate | 0.1-2.0 | |
| Ethylenediamine | 0-3.0 | |
| Disodium Octaborate Tetrahydrate | 1-5 | |
| 25% Guanidine Phosphate | 0.1-15 | |
이하, 실시예를 통하여 본 발명의 수용성 난연제 조성물에 대하여 설명한다.Hereinafter, the water-soluble flame retardant composition of the present invention will be described through Examples.
아래 표 2와 같이 실시예 1 내지 3으로 이루어진 수용성 난연제 조성물을 제조하였다.To prepare a water-soluble flame retardant composition consisting of Examples 1 to 3 as shown in Table 2.
표 2
TABLE 2
| 구분 | 실시예 1 | 실시예 2 | 실시예 3 |
| 물 | 89.2 중량% | 69.6 중량% | 49.6 중량% |
| 구아니딘 포스페이트(Guanidine phosphate) | 0.2 중량% | 2.5 중량% | 5 중량% |
| 암모늄 포스페이트(Ammonium phosphate dibasic) | 8.0 중량% | 12 중량% | 16 중량% |
| 암모늄 클로라이드(Ammonium chloride) | 1.0 중량% | 1.5 중량% | 2 중량% |
| 모노클로로아세틱 에시드(Monochloroacetic acid) | 0.4 중량% | 1.4 중량% | 2.4 중량% |
| 구아니딘 카보네이트(Guanidine carbonate) | 0.1 중량% | 1.0 중량% | 2 중량% |
| 에틸렌 디아민(Ethylenediamine) | - | 1.5 중량% | 3 중량% |
| 디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate) | 1.0 중량% | 3 중량% | 5 중량% |
| 25% 구아니딘 인산염계 | 0.1 중량% | 7.5 중량% | 15 중량% |
| division | Example 1 | Example 2 | Example 3 |
| water | 89.2 wt% | 69.6 wt% | 49.6 wt% |
| Guanidine phosphate | 0.2 wt% | 2.5 wt% | 5 wt% |
| Ammonium phosphate dibasic | 8.0 wt% | 12 wt% | 16 wt% |
| Ammonium chloride | 1.0 wt% | 1.5 wt% | 2 wt% |
| Monochloroacetic acid | 0.4 wt% | 1.4 wt% | 2.4 wt% |
| Guanidine carbonate | 0.1 wt% | 1.0 wt% | 2 wt% |
| Ethylenediamine | - | 1.5 wt% | 3 wt% |
| Disodium Octaborate Tetrahydrate | 1.0 wt% | 3 wt% | 5 wt% |
| 25% Guanidine Phosphate | 0.1 wt% | 7.5 wt% | 15 wt% |
상기 실시예 1 내지 3과 같은 구성비로 수용성 난연제 조성물을 제조하고. 상기 제조된 수용성 난연제 조성물을 벽지, 천, 목재의 가연성 물질 기재에 함침되록 하여 방염처리 하고, 한국방염공사에서 실시하는 방염성 기준 KOFEIS 0201를 사용하여 실험을 하였으며, 그 결과는 아래의 표 3 내지 표 5와 같다.To prepare a water-soluble flame retardant composition in the same ratio as in Examples 1 to 3. The prepared water-soluble flame retardant composition was flameproofed by impregnating the flammable material base of wallpaper, cloth, and wood, and tested using the flame retardant standard KOFEIS 0201 carried out by Korea Fire Protection Corporation. The results are shown in Tables 3 to Table below. Same as 5.
표 3 수용성 난연제 조성물로 방염처리된 벽지에 대한 방염성 결과.
TABLE 3 Flame retardant results for wallpaper flame retarded with water soluble flame retardant composition.
| 시험항목 | 기준 | 실험결과 | ||
| 실시예 1 | 실시예 2 | 실시예 3 | ||
| 잔염시간(초) | 3 | 0 | 0 | 0 |
| 잔신시간(초) | 5 | 0 | 0 | 0 |
| 탄화면적(㎠) | 30 | 18.6 | 16.7 | 17.9 |
| 탄화길이(㎝) | 20 | 5.8 | 6.4 | 6.2 |
| 코일법(접염회수) | 3회 이상 | - | - | - |
| Test Items | standard | Experiment result | ||
| Example 1 | Example 2 | Example 3 | ||
| Afterglow time (sec) | 3 | 0 | 0 | 0 |
| Remaining time (sec) | 5 | 0 | 0 | 0 |
| Bullet area (㎠) | 30 | 18.6 | 16.7 | 17.9 |
| Carbonization Length (cm) | 20 | 5.8 | 6.4 | 6.2 |
| Coil Method (Recovery) | 3 or more times | - | - | - |
표 4 수용성 난연제 조성물로 방염처리된 천에 대한 방염성 결과.
Table 4 Flame retardant results for fabrics flame retarded with water soluble flame retardant composition.
| 시험항목 | 기준 | 실험결과 | ||
| 실시예 1 | 실시예 2 | 실시예 3 | ||
| 잔염시간(초) | 3 | 0 | 0 | 0 |
| 잔신시간(초) | 5 | 0 | 0 | 0 |
| 탄화면적(㎠) | 30 | 19.9 | 21.4 | 20.1 |
| 탄화길이(㎝) | 20 | 6.7 | 6.9 | 6.8 |
| 코일법(접염회수) | 3회 이상 | - | - | - |
| Test Items | standard | Experiment result | ||
| Example 1 | Example 2 | Example 3 | ||
| Afterglow time (sec) | 3 | 0 | 0 | 0 |
| Remaining time (sec) | 5 | 0 | 0 | 0 |
| Bullet area (㎠) | 30 | 19.9 | 21.4 | 20.1 |
| Carbonization Length (cm) | 20 | 6.7 | 6.9 | 6.8 |
| Coil Method (Recovery) | 3 or more times | - | - | - |
표 5 수용성 난연제 조성물로 방염처리된 목재에 대한 방염성 결과.
Table 5 Flame retardant results for wood fired with water soluble flame retardant composition.
| 시험항목 | 기준 | 실험결과 | ||
| 실시예 1 | 실시예 2 | 실시예 3 | ||
| 잔염시간(초) | 10 | 0 | 0 | 0 |
| 잔신시간(초) | 30 | 0 | 0 | 0 |
| 탄화면적(㎠) | 50 | 34.2 | 33.8 | 31.5 |
| 탄화길이(㎝) | 20 | 5.8 | 5.4 | 5.6 |
| 코일법(접염회수) | 3회 이상 | - | - | - |
| Test Items | standard | Experiment result | ||
| Example 1 | Example 2 | Example 3 | ||
| Afterglow time (sec) | 10 | 0 | 0 | 0 |
| Remaining time (sec) | 30 | 0 | 0 | 0 |
| Bullet area (㎠) | 50 | 34.2 | 33.8 | 31.5 |
| Carbonization Length (cm) | 20 | 5.8 | 5.4 | 5.6 |
| Coil Method (Recovery) | 3 or more times | - | - | - |
상기 각각의 기재들(벽지, 천, 목재)에 본 발명의 수용성 난연제 조성물로 방염처리 한 경우 방염성이 한국방염공사의 기준치에 부합됨을 알 수 있다.When each of the substrates (wall paper, cloth, wood) is flame retardant with the water-soluble flame retardant composition of the present invention it can be seen that the flame retardancy meets the standards of Korea Fire Protection Corporation.
Claims (5)
- 수용성 난연제 조성물에 있어서,In the water-soluble flame retardant composition,상기 난연제 조성물은, 11.61~45.4 중량%의 방염제와, 0.1~15 중량%의 25% 구아니딘 인산염계와, 나머지 용매로 이루어진 것을 특징으로 하는 수용성 난연제 조성물. The flame retardant composition is 11.61 to 45.4% by weight of flame retardant, 0.1 to 15% by weight of 25% guanidine phosphate-based, the water-soluble flame retardant composition, characterized in that consisting of the remaining solvent.
- 제1항에 있어서,The method of claim 1,상기 용매는 물, 에틸알코올, 이소프로필 알코올, n-메틸피로리돈 중 1종 또는 2종 이상의 선택하여 혼합한 혼합물임을 특징으로 하는 수용성 난연제 조성물. The solvent is a water-soluble flame retardant composition, characterized in that the mixture of one or two or more selected from water, ethyl alcohol, isopropyl alcohol, n-methylpyrrolidone.
- 제1항에 있어서,The method of claim 1,상기 방염제는 구아니딘 포스페이트(Guanidine phosphate), 암모늄 포스페이트(Ammonium phosphate dibasic), 모노클로로아세틱 에시드(Monochloroacetic acid), 구아니딘 카보네이트(Guanidine carbonate), 에틸렌 디아민(Ethylenediamine), 디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate)로 이루어진 혼합물인 것으로 특징으로 하는 수용성 난연제 조성물.The flame retardant is guanidine phosphate (Guanidine phosphate), ammonium phosphate (basic ammonium phosphate dibasic), monochloroacetic acid (Monochloroacetic acid), guanidine carbonate (Guanidine carbonate), ethylene diamine (Ethylenediamine), disodinium octaborate tetrahydrate (Disodium Octaborate) Water-soluble flame retardant composition, characterized in that the mixture consisting of.
- 수용성 난연제 조성물에 있어서,In the water-soluble flame retardant composition,상기 난연제 조성물은, The flame retardant composition,물 49.6~89.19 중량%와;49.6-89.19 weight% of water;구아니딘 포스페이트(Guanidine phosphate) 0.2~5.0 중량%와;0.2 to 5.0 weight percent of guanidine phosphate;암모늄 포스페이트(Ammonium phosphate dibasic) 8.0~16.0 중량%와;8.0-16.0 weight percent of ammonium phosphate dibasic;암모늄 클로라이드(Ammonium chloride) 1.0~2.0 중량%와;1.0-2.0 wt% of ammonium chloride;모노클로로아세틱 에시드(Monochloroacetic acid) 0.4~2.4 중량%와;0.4 to 2.4 wt% monochloroacetic acid;구아니딘 카보네이트(Guanidine carbonate) 0.1~2.0 중량%와;0.1 to 2.0 wt% of guanidine carbonate;에틸렌 디아민(Ethylenediamine) 0.01~3.0 중량%와;0.01 to 3.0% by weight of ethylene diamine;디소디늄 옥타보레이트 테트라하이드레이트(Disodium Octaborate tetrahydrate) 1~5 중량%와;1 to 5% by weight of disodium octaborate tetrahydrate;25% 구아니딘 인산염계 0.1~15 중량%로 이루어진 것을 특징으로 하는 수용성 난연제 조성물. A water-soluble flame retardant composition comprising 25% guanidine phosphate 0.1-15% by weight.
- 제1항 또는 제4항에 있어서,The method according to claim 1 or 4,상기 25% 구아니딘 인산염계는,The 25% guanidine phosphate system,폴리에틸렌디아민-구아니딘 포스페이트, 폴리프로필렌디아민-구아니딘 포스페이트, 폴리부틸렌디아민-구아니딘 포스페이트, 폴리펜탄디아민-구아니딘 포스페이트, 폴리헥사메틸렌디아민-구아니딘 포스페이트 중 1종 또는 2종 이상을 선택하여 혼합한 혼합물임을 특징으로 하는 수용성 난연제 조성물.1, 2 or more selected from polyethylenediamine-guanidine phosphate, polypropylenediamine-guanidine phosphate, polybutylenediamine-guanidine phosphate, polypentanediamine-guanidine phosphate, and polyhexamethylenediamine-guanidine phosphate. A water-soluble flame retardant composition.
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| KR10-2010-0109003 | 2010-11-04 | ||
| KR1020100109003A KR101192453B1 (en) | 2010-11-04 | 2010-11-04 | Flame retardant composition soluble in water |
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| US11865394B2 (en) | 2017-12-03 | 2024-01-09 | Mighty Fire Breaker Llc | Environmentally-clean biodegradable water-based concentrates for producing fire inhibiting and fire extinguishing liquids for fighting class A and class B fires |
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| US11826592B2 (en) | 2018-01-09 | 2023-11-28 | Mighty Fire Breaker Llc | Process of forming strategic chemical-type wildfire breaks on ground surfaces to proactively prevent fire ignition and flame spread, and reduce the production of smoke in the presence of a wild fire |
| US11911643B2 (en) | 2021-02-04 | 2024-02-27 | Mighty Fire Breaker Llc | Environmentally-clean fire inhibiting and extinguishing compositions and products for sorbing flammable liquids while inhibiting ignition and extinguishing fire |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101192453B1 (en) | 2012-10-18 |
| KR20120047445A (en) | 2012-05-14 |
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