JP2022120431A - Composition for foamable fireproof coating and method for producing foamable fireproof coating layer by using the same - Google Patents
Composition for foamable fireproof coating and method for producing foamable fireproof coating layer by using the same Download PDFInfo
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- JP2022120431A JP2022120431A JP2021017329A JP2021017329A JP2022120431A JP 2022120431 A JP2022120431 A JP 2022120431A JP 2021017329 A JP2021017329 A JP 2021017329A JP 2021017329 A JP2021017329 A JP 2021017329A JP 2022120431 A JP2022120431 A JP 2022120431A
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- resistant coating
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- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、発泡性耐火塗料用組成物及びそれを用いた発泡性耐火塗膜の製造方法に係り、より詳しくは、塗膜形成性に優れ、厚い塗膜を容易に形成できる発泡性耐火塗料用組成物、及び、それを用いて、火災等により基材表面の温度が上昇すると分解し発泡して不燃性の気泡含有断熱層を形成し更に高温になって有機成分が分解した後にも残存して耐火性を示し得る発泡性耐火塗膜を製造する方法に関する。 TECHNICAL FIELD The present invention relates to a foamable fire-resistant coating composition and a method for producing a foamable fire-resistant coating film using the same, and more particularly, to a foamable fire-resistant coating that has excellent coating film-forming properties and can easily form a thick coating film. and a composition using the same that decomposes and foams when the temperature of the base material surface rises due to a fire or the like to form an incombustible bubble-containing heat insulating layer and remains even after the organic component is decomposed at a high temperature. The present invention relates to a method for producing an intumescent fire resistant coating that can be rendered fire resistant by heating.
発泡性耐火塗料は、プラスチック類、繊維強化プラスチック（ＦＲＰ）、壁紙、無機質ボード、木材、合板、モルタル、コンクリート、鉄鋼等の表面に塗布されて発泡性耐火塗膜を形成し、それらを火災から保護する、或いは延焼を遅延させ被害を軽減させる目的で使用される。 Foaming fire-resistant paints are applied to the surfaces of plastics, fiber reinforced plastics (FRP), wallpaper, inorganic boards, wood, plywood, mortar, concrete, steel, etc. to form a foaming fire-resistant coating, which protects them from fire. Used to protect or slow the spread of fire to reduce damage.
このような発泡性耐火塗料としては、発泡剤としてりん酸塩、炭化剤として多価アルコール類又は糖類、無機物の粉末、及び高分子樹脂からなる塗料用組成物から形成された発泡性耐火塗料が知られている（例えば、特許文献１を参照）。しかし、これらの発泡性耐火塗料から形成された塗膜は、一定温度での耐火性能は優れているものの、基材への接着性及び柔軟な基材への追従性が不十分なものであった。 As such a foaming fire-resistant coating, there is a foaming fire-resistant coating formed from a coating composition comprising a phosphate as a foaming agent, a polyhydric alcohol or sugar as a carbonizing agent, an inorganic powder, and a polymer resin. known (see, for example, Patent Literature 1). However, the coating films formed from these foaming fire-resistant paints have excellent fire resistance performance at a constant temperature, but their adhesiveness to substrates and conformability to flexible substrates are insufficient. rice field.
また、プラスチック類、繊維強化プラスチック（ＦＲＰ）、壁紙、無機質ボード、木材、合板、モルタル、コンクリート等の基材のほかに、柔軟性のある基材、例えば、紙、布、繊維、ゴム等の防火に用いることができる発泡性耐火塗膜を形成し得る塗料用組成物として、アクリル樹脂エマルジョンと、りん系難燃剤と、被覆剤と、炭化剤と、難燃性充填剤とを含有する発泡性耐火塗料用組成物が広く用いられている（例えば、特許文献２を参照）。しかし、これらの塗料用組成物は粘度が低いために塗装時に液だれし易く塗装性が満足できるものではなく、また形成された塗膜は、柔軟な基材への追従性は向上しているものの高温度に対する耐火性が不十分なものであった。 In addition to base materials such as plastics, fiber reinforced plastics (FRP), wallpaper, inorganic boards, wood, plywood, mortar, concrete, etc., flexible base materials such as paper, cloth, fiber, rubber, etc. As a coating composition capable of forming a foamable fire-resistant coating that can be used for fire prevention, a foaming composition containing an acrylic resin emulsion, a phosphorus-based flame retardant, a coating agent, a carbonizing agent, and a flame-retardant filler. fire-resistant paint compositions are widely used (see, for example, Patent Document 2). However, since these coating compositions have low viscosities, they tend to drip during coating, and the coating properties are not satisfactory, and the formed coating film has improved conformability to flexible substrates. However, the fire resistance against high temperatures was insufficient.
発泡性耐火塗料の耐熱性を向上させるためには、塗膜及び耐熱層を更に厚くすることが有効であるが、従来の発泡性耐火塗料は、一回の塗装では充分な厚さの塗膜を形成することができないのが実状であった。本発明は、一回の塗装で充分な厚さの発泡性耐火塗膜を形成することができる発泡性耐火塗料用組成物を提供することを目的とする。 In order to improve the heat resistance of the foaming fire-resistant paint, it is effective to make the coating film and the heat-resistant layer thicker, but the conventional foaming fire-resistant paint has a sufficient thickness in one coating. It was the actual situation that it was not possible to form An object of the present invention is to provide a foamable fire-resistant coating composition capable of forming a sufficiently thick foamable fire-resistant coating film in a single application.
また、発泡性耐火塗料の塗膜の耐火性を更に向上させるためには、塗膜は、多くの有機物の分界点以上に加熱されて塗膜の有機物が分解され始めた後まで耐火性を示す必要がある。本発明は、耐火塗膜が、加熱されると気泡含有耐火層を形成し、有機成分が分解し始めた後までも耐火性を示し得る発泡性耐火塗料用組成物及びそれを用いた発泡性耐火塗膜の製造方法を提供することを目的とする。 In addition, in order to further improve the fire resistance of the coating film of the foaming fire-resistant paint, the coating film is heated above the demarcation point of many organic substances, and the coating film exhibits fire resistance until after the organic substances in the coating film begin to decompose. There is a need. The present invention provides a composition for a foamable fire-resistant coating that forms a fire-resistant layer containing air bubbles when the fire-resistant coating is heated and exhibits fire resistance even after the organic component begins to decompose, and foaming properties using the same. It is an object of the present invention to provide a method for producing a fire resistant coating.
本発明は、かかる課題を解決するためになされたものであって、本発明の発泡性耐火塗料用組成物は、発泡性耐火塗料用組成物の全体を１００質量％とすると、発泡剤２５～５０質量％と、高分子樹脂水性エマルジョン１５～４０質量％と、炭化剤５～１５質量％と、無機顔料８～１８質量％と、水又は／及び有機溶媒から選ばれる溶媒１０～３０質量％と、その他の添加剤２～８質量％とを含み、前記塗料用組成物のずり速度０．１（ｌ／ｓ）における粘度が５００～１０００（Ｐａ・Ｓ、２３℃）であり、ずり速度１００（ｌ／ｓ）における粘度が１０～１００（Ｐａ・Ｓ、２３℃）であることを特徴とする。 The present invention has been made to solve such problems, and the composition for foaming fire-resistant coating of the present invention comprises 25 to 25 foaming agents when the entire composition for foaming fire-resistant coating is 100% by mass. 50% by mass, 15 to 40% by mass of a polymer resin aqueous emulsion, 5 to 15% by mass of a carbonizing agent, 8 to 18% by mass of an inorganic pigment, and 10 to 30% by mass of a solvent selected from water and/or an organic solvent. and 2 to 8% by mass of other additives, and the coating composition has a viscosity of 500 to 1000 (Pa S, 23 ° C.) at a shear rate of 0.1 (l / s), and a shear rate It is characterized by having a viscosity of 10 to 100 (Pa·S, 23° C.) at 100 (l/s).
前記発泡剤が、ポリりん酸アンモニウム、ポリりん酸２アンモニウム、りん酸２アンモニウム、りん酸アンモニウム、又はりん酸メラミン等のリン系発泡剤から選ばれる１以上であり、高分子樹脂エマルジョンの高分子樹脂が、アクリル系樹脂、シリコーン系樹脂、及び酢酸ビニル樹脂等から選ばれる１以上であり、炭化剤が多価アルコール、デキストリン、又は糖類等から選ばれる１以上であることが好ましい。 The foaming agent is one or more selected from phosphorus-based foaming agents such as ammonium polyphosphate, diammonium polyphosphate, diammonium phosphate, ammonium phosphate, and melamine phosphate, and the polymer of the polymer resin emulsion is Preferably, the resin is one or more selected from acrylic resins, silicone resins, vinyl acetate resins, and the like, and the carbonizing agent is one or more selected from polyhydric alcohols, dextrin, sugars, and the like.
前記無機顔料が、金属酸化物であることが好ましい。
前記添加剤が、アルカリ性増粘剤を含みうる。
前記発泡剤の平均粒径が、２０マイクロメーター以下であることが好ましい。
It is preferable that the inorganic pigment is a metal oxide.
Said additive may comprise an alkaline thickening agent.
It is preferable that the average particle size of the foaming agent is 20 micrometers or less.
また、発泡性耐火塗膜の製造方法は、請求項１乃至５のいずれか１項に記載の発泡性耐火塗料用組成物を、撹拌しながら吹き付け塗装することを特徴とする。
発泡性耐火塗料用組成物を、ずり速度１０～５００（ｌ／ｓ）で撹拌しながら吹き付け塗装して製造することが好ましい。
A method for producing a foamable fire-resistant coating film is characterized by spray coating the foamable fire-resistant coating composition according to any one of claims 1 to 5 while stirring.
It is preferable to manufacture the foamable fire-resistant paint composition by spray coating while stirring at a shear rate of 10 to 500 (l/s).
本発明の発泡性耐火塗料用組成物は、固体成分と、水又は／及び有機溶媒からなる液体成分と、を含み、一般の耐火塗料用組成物と比較すると固体成分に対して液体成分が少ないペースト状であって、ずり速度０．１（ｌ／ｓ）における粘度が５００乃至１０００（Ｐａ・Ｓ、２３℃）であり、ずり速度１００（ｌ／ｓ）における粘度が１０乃至１００（Ｐａ・Ｓ、２３℃）のチキソトロピー性を有するペースト状である。 The foamable fire-resistant coating composition of the present invention contains a solid component and a liquid component consisting of water and/or an organic solvent, and the liquid component is less than the solid component compared to general fire-resistant coating compositions. It is a paste, has a viscosity of 500 to 1000 (Pa·S, 23°C) at a shear rate of 0.1 (l/s), and a viscosity of 10 to 100 (Pa·s) at a shear rate of 100 (l/s). S, 23° C.) thixotropic paste.
したがって、塗料用組成物を、高速撹拌して粘性が低下した状態で吹き付け塗装すると、塗料用組成物が基材に塗布されて静止した時に短時間で粘性が増大するので、基材が傾斜していても塗膜の偏りや液垂れが起こらず、一回の塗装で乾燥膜厚が０．５～２ｍｍ程度になるように厚塗りしても、均一な塗膜を形成することができる。
また、本発明に係る発泡性耐火塗膜は、基材に対する付着強度、均一発泡性、耐タレ性、耐割れ性、耐脱落性、及び耐剥離性などに優れた発泡性耐火塗膜を形成できるという特徴を有する。
Therefore, if the coating composition is agitated at high speed and then spray-coated in a state where the viscosity is lowered, the viscosity increases in a short period of time when the coating composition is applied to the substrate and stands still, which causes the substrate to tilt. Even if the coating film is unevenly distributed or drips, it is possible to form a uniform coating film even if it is applied thickly so that the dry film thickness is about 0.5 to 2 mm in one coating.
In addition, the foamable fire-resistant coating film according to the present invention forms a foamable fire-resistant coating film that is excellent in adhesion strength to a substrate, uniform foamability, sagging resistance, cracking resistance, falling-off resistance, peeling resistance, etc. It has the characteristic of being able to
更に、無機顔料として金属酸化物を用いた本発明の発泡性耐火塗膜は、加熱されて高温で分解する時に、リン系の発泡剤から発生するりん酸誘導体と金属酸化物とからりん酸の金属塩を生成する。
特に、無機顔料として白色顔料である酸化チタン又は酸化亜鉛を使用した本発明の発泡性耐火塗膜は、発泡剤が熱分解して生成したりん酸誘導体と、酸化チタン又は酸化亜鉛と、が反応して、高温安定性に優れ鉄鋼の表面保護材としても使用されるリン酸チタン（Ｔｉ３（ＰＯ３）２）又はりん酸亜鉛（Ｚｎ３（ＰＯ３）２）を生成して気泡含有断熱層を形成する。
Furthermore, the foamable fire-resistant coating film of the present invention using a metal oxide as an inorganic pigment produces phosphoric acid from the phosphoric acid derivative generated from the phosphorus-based foaming agent and the metal oxide when heated and decomposed at a high temperature. Produces metal salts.
In particular, in the foamable fire-resistant coating film of the present invention using titanium oxide or zinc oxide, which is a white pigment, as an inorganic pigment, a phosphoric acid derivative generated by thermal decomposition of the foaming agent reacts with titanium oxide or zinc oxide. As a result, titanium phosphate (Ti 3 (PO 3 ) 2 ) or zinc phosphate (Zn 3 (PO 3 ) 2 ), which has excellent high-temperature stability and is also used as a surface protection material for steel, is produced to form a bubble-containing thermal insulation. form a layer.
本発明の発泡性耐火塗膜は、ＪＩＳ Ａ １３０４に示す標準曲線に基づいて加熱昇温された２００℃～６００℃の電気炉雰囲気中（１００℃間隔）に１時間放置したところ、２００℃乃至３００℃から発泡が始まって、３００℃～５００℃にかけて炭化剤が炭化されて分解され、１０～２０倍に膨張して気泡含有断熱層を形成した（図１を参照）。更に６００℃において有機物（炭素）が分解されて白色化した後も、多孔性の気泡含有断熱層を形成して維持することができた。 The foamable fire-resistant coating film of the present invention was left for 1 hour in an electric furnace atmosphere (100° C. interval) heated to 200° C. to 600° C. based on the standard curve shown in JIS A 1304. Foaming started from 300° C., and the carbonizing agent was carbonized and decomposed from 300° C. to 500° C., expanded 10 to 20 times, and formed a bubble-containing heat insulating layer (see FIG. 1). Furthermore, even after organic matter (carbon) was decomposed at 600° C. and turned white, a porous, bubble-containing heat insulating layer could be formed and maintained.
火災が発生し室内の温度が約５００℃に達すると、高温で可燃性ガスが発生し引火してフラッシュオーバーという爆発的な燃焼が発生し、延焼が急加速される。本発明の気泡含有断熱層は６００℃でも維持されて高温の火焔の進入を防ぐので火災の発生及び延焼を大幅に遅らせることができるという優れた効果を有する。 When a fire breaks out and the indoor temperature reaches about 500°C, flammable gas is generated at a high temperature and ignites, causing an explosive combustion called flashover, and the spread of the fire is rapidly accelerated. The air-bubble-containing heat insulating layer of the present invention is maintained even at 600° C. and prevents high-temperature flames from entering, so it has an excellent effect of significantly delaying the occurrence and spread of fire.
以下に、添付図面を参照しながら本発明の発泡性耐火塗料用組成物及び発泡性耐火塗膜の製造方法を詳細に説明する。
本発明の発泡性耐火塗料用組成物は、（Ａ）発泡剤、（Ｂ）高分子樹脂エマルジョン、（Ｃ）炭化剤、（Ｄ）無機顔料、（Ｅ）溶媒、及び（Ｆ）その他の添加物を含有する。
BEST MODE FOR CARRYING OUT THE INVENTION The composition for foaming fire-resistant paint and the method for producing a foaming fire-resistant coating film of the present invention will be described in detail below with reference to the accompanying drawings.
The foamable fire-resistant coating composition of the present invention comprises (A) a foaming agent, (B) a polymer resin emulsion, (C) a carbonizing agent, (D) an inorganic pigment, (E) a solvent, and (F) other additives. contains things.
本発明の発泡性耐火塗料用組成物においては、顔料として８～１８質量％（発泡性耐火塗料用組成物全体の質量を１００質量％とする、質量％は以下同じ。）（Ｄ）無機顔料を用いることが好ましい。無機顔料は、発泡性耐火塗膜及び基材の有機物が熱分熱するような高温においても残存して気泡含有断熱層を形成することができる。 In the foamable fire-resistant paint composition of the present invention, 8 to 18% by mass of pigment (assuming that the mass of the entire foamable fire-resistant paint composition is 100% by mass, mass% is the same below.) (D) Inorganic pigment is preferably used. The inorganic pigment can remain even at high temperatures at which the expandable refractory coating film and the organic matter of the base material heat up to form a heat insulating layer containing air bubbles.
本発明の発泡性耐火塗料用組成物における無機顔料としては、酸化チタン、酸化亜鉛（亜鉛華）、酸化第２鉄（弁柄）、酸化第２銅、及び２酸化マンガン（黒色）等の金属酸化物の顔料を挙げることができる。また、塩基性炭酸銅（緑青）のような複合酸化物も含めることができる。なお、色調を調節するために、有機顔料を添加することは妨げない。 Inorganic pigments in the foamable fire-resistant coating composition of the present invention include metals such as titanium oxide, zinc oxide (zinc white), ferric oxide (rouge), cupric oxide, and manganese dioxide (black). Mention may be made of oxide pigments. Complex oxides such as basic copper carbonate (patina) can also be included. In addition, in order to adjust a color tone, adding an organic pigment is not prevented.
たとえば、白色顔料である酸化チタン又は酸化亜鉛を使用した本発明の発泡性耐火塗膜は、発泡剤が熱分解して生成したりん酸誘導体及び金属酸化物が反応して安定なリン酸チタン（Ｔｉ３（ＰＯ３）２）又はりん酸亜鉛（Ｚｎ３（ＰＯ３）２）を生成し、気泡含有断熱層を形成する。また、酸化第２鉄はバラ色のりん酸第２鉄を、酸化銅は生成条件によって異なるが、青色系の色のりん酸化物を形成する。 For example, the foamable fire-resistant coating film of the present invention using titanium oxide or zinc oxide, which is a white pigment, is composed of stable titanium phosphate ( Ti 3 (PO 3 ) 2 ) or zinc phosphate (Zn 3 (PO 3 ) 2 ) to form a bubble-containing thermal barrier. Further, ferric oxide forms rose-colored ferric phosphate, and copper oxide forms bluish-colored phosphate, depending on the production conditions.
本発明の発泡性耐火塗料用組成物において（Ａ）発泡剤としては、ポリりん酸アンモニウム、りん酸アンモニウム、ポリりん酸２アンモニウム、りん酸２アンモニウム、りん酸２水素１アンモニウム、りん酸１水素２アンモニウム、メタりん酸アンモニウム、りん酸メラミン、ポリりん酸メラミン、メタりん酸メラミン、りん酸グアニジン、正りん酸、ポリりん酸、及び亜りん酸等を含むりん系難燃剤等を例示することができるが、本発明の（Ａ）発泡剤は、本発明に利用できるりん系発泡剤であれば特に制限されず、いずれのりん系発泡剤も用いることができる。 In the foamable fire-resistant coating composition of the present invention, the foaming agent (A) includes ammonium polyphosphate, ammonium phosphate, diammonium polyphosphate, diammonium phosphate, monoammonium dihydrogen phosphate, and monohydrogen phosphate. Phosphorus-based flame retardants, including diammonium, ammonium metaphosphate, melamine phosphate, melamine polyphosphate, melamine metaphosphate, guanidine phosphate, orthophosphoric acid, polyphosphoric acid, and phosphorous acid, etc. However, the (A) foaming agent of the present invention is not particularly limited as long as it is a phosphorus-based foaming agent that can be used in the present invention, and any phosphorus-based foaming agent can be used.
本発明の発泡性耐火塗料用組成物における（Ｂ）高分子樹脂エマルジョンは、高分子樹脂原料を水に分散した公知のものであり、通常、水を４０％～５０％含んでいる。高分子樹脂としては本発明に利用できるものであれば特に制限されないが、アクリル系樹脂、シリコーン系樹脂、及び酢酸ビニル系樹脂等を例示することができる。 The polymer resin emulsion (B) in the foamable fire-resistant coating composition of the present invention is a known emulsion in which polymer resin raw materials are dispersed in water, and usually contains 40% to 50% water. The polymer resin is not particularly limited as long as it can be used in the present invention, and acrylic resins, silicone resins, vinyl acetate resins, and the like can be exemplified.
より詳しくは、アクリル系樹脂としてメタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸２エチルヘキシル、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２エチルヘキシル、アクリロニトリル、メタクリロニトリル、アクリルアミド等のアクリル系モノマーから形成されるホモポリマー又はコポリマー等を挙げることができるが、これらの高分子樹脂に限定されるものではない。 More specifically, acrylic resins such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, Examples include homopolymers or copolymers formed from acrylic monomers such as methacrylonitrile and acrylamide, but are not limited to these polymer resins.
本発明の発泡性耐火塗料用組成物における（Ｃ）炭化剤としては、多価アルコール、デキストリン、糖類、及びペンタエリスリトール、ジペンタエリスリトール、ポリペンタエリスリトール、ソルビトール、イノシトール等の公知の多価アルコール類を例示することができる。
本発明の発泡性耐火塗料用組成物は更に、トルエン、キシレン、などの有機溶媒、水、およびアルコール類等の（Ｅ）溶媒を加えることができる。
発泡性耐火塗料用組成物においては、更に必要に応じて、当分野で通常用いられている重合開始剤、増粘剤、消泡剤、防腐剤、分散剤等の（Ｆ）その他の添加物を含有することができる。
The carbonizing agent (C) in the foamable fire-resistant paint composition of the present invention includes polyhydric alcohols, dextrins, sugars, and known polyhydric alcohols such as pentaerythritol, dipentaerythritol, polypentaerythritol, sorbitol and inositol. can be exemplified.
The foamable fire-resistant coating composition of the present invention can further contain (E) solvents such as organic solvents such as toluene and xylene, water, and alcohols.
In the foamable fire-resistant paint composition, if necessary, (F) other additives such as polymerization initiators, thickeners, antifoaming agents, preservatives, dispersants, etc. that are commonly used in the art can contain
また、本発明の発泡性耐火塗料用組成物は、例えば（Ａ）発泡剤、（Ｂ）高分子樹脂エマルジョン、（Ｃ）炭化剤、（Ｄ）無機顔料、及び（Ｆ）その他の添加物に、（Ｅ）溶媒を添加し撹拌して製造することができる。（Ｅ）溶媒を添加する方法としては、（Ｅ）溶媒に（Ａ）発泡剤、（Ｂ）高分子樹脂エマルジョン、（Ｃ）炭化剤、（Ｄ）無機顔料、及び（Ｆ）その他の添加物を一括又は別々に添加し、次いで撹拌機等により混合、均一分散させればよい。 In addition, the foamable fire-resistant coating composition of the present invention contains, for example, (A) a foaming agent, (B) a polymer resin emulsion, (C) a carbonizing agent, (D) an inorganic pigment, and (F) other additives. , (E) can be prepared by adding a solvent and stirring. (E) As a method of adding a solvent, (E) a solvent may be added with (A) a blowing agent, (B) a polymer resin emulsion, (C) a carbonizing agent, (D) an inorganic pigment, and (F) other additives. may be added together or separately, and then mixed and uniformly dispersed using a stirrer or the like.
本発明の発泡性耐火塗料用組成物は、ずり速度０．１（ｌ／ｓ）における粘度が５００乃至１０００（Ｐａ・Ｓ、２３℃）であり、ずり速度１００（ｌ／ｓ）における粘度が１０乃至１００（Ｐａ・Ｓ、２３℃）であることが好ましい。本発明の発泡性耐火塗料用組成物の粘度は、（Ｅ）溶媒の量を調節するか、（Ｆ）その他の添加物としてアルカリ性増粘剤を添加することによって調節することができる。 The foamable fire-resistant coating composition of the present invention has a viscosity of 500 to 1000 (Pa S, 23° C.) at a shear rate of 0.1 (l/s), and a viscosity at a shear rate of 100 (l/s) is It is preferably 10 to 100 (Pa·S, 23°C). The viscosity of the foamable fire-resistant coating composition of the present invention can be adjusted by (E) adjusting the amount of solvent or (F) adding an alkaline thickener as another additive.
本発明の発泡性耐火塗料用組成物はチキソトロピー性を有する。したがって、塗料用組成物を高速で撹拌して粘性を低下させた状態で吹き付け塗装すると、塗料用組成物が基材に塗布されて静止した時に粘性が増大するので、例えば基材が傾斜して設置されていても塗膜の偏りや液垂れが起こらず、一回の塗装で乾燥膜厚が０．５～２ｍｍ以上になるように厚塗りして均一な塗膜を得ることができる。 The foamable fire-resistant coating composition of the present invention has thixotropic properties. Therefore, if the coating composition is agitated at high speed to reduce the viscosity and then spray-coated, the viscosity increases when the coating composition is applied to the substrate and stands still. Even if it is installed, unevenness of the coating film and dripping do not occur, and a uniform coating film can be obtained by applying a thick coating so that the dry film thickness is 0.5 to 2 mm or more in one coating.
基材に吹き付け塗布された発泡性耐火塗料用組成物は、多くの場合は表面張力によって平滑な塗面を形成するが、用いる発泡性耐火塗料用組成物の粘度が特に高い場合には、生成した塗膜の表面に小さな凹凸が残ることもある。この凹凸は、美しく風情があるものであるが、凹凸が好ましくない場合には、発泡性耐火塗料用組成物の粘度を下げるなどの対応が必要である。 A foaming fire-resistant coating composition spray-coated on a substrate often forms a smooth coating surface due to surface tension. Small irregularities may remain on the surface of the applied coating film. The unevenness is beautiful and tasteful, but if the unevenness is not desirable, it is necessary to reduce the viscosity of the foamable fire-resistant coating composition.
本発明の発泡性耐火塗膜は、ＪＩＳ Ａ １３０４に示す標準曲線に基づいて加熱昇温させた２００℃～６００℃（１００℃間隔）の電気炉中に１時間放置したところ、２００℃～３００℃から発泡が始まって、３００℃～５００℃にかけて厚さが１０～２０倍に膨張して気泡を含有する断熱層を形成し、更に、炭化剤が炭化され分解された６００℃においても、多孔性の気泡含有断熱層を維持することができるという効果を有する。 The foamable fire-resistant coating film of the present invention was left for 1 hour in an electric furnace heated to 200 ° C to 600 ° C (100 ° C interval) based on the standard curve shown in JIS A 1304. Foaming starts from 300°C to 500°C and expands to a thickness of 10 to 20 times to form a heat insulating layer containing air bubbles. It has the effect of being able to maintain a thermal insulation layer containing air bubbles.
特に、無機顔料として白色顔料である酸化チタン又は酸化亜鉛を使用した本発明の発泡性耐火塗膜は、発泡剤が熱分解して生成したりん酸根とチタン又は亜鉛とが反応して安定なリン酸チタン（Ｔｉ３（ＰＯ３）２）又はりん酸亜鉛（Ｚｎ３（ＰＯ３）２）を生成し、気泡含有断熱層を形成することができる。 In particular, the foamable fire-resistant coating film of the present invention using titanium oxide or zinc oxide, which is a white pigment, as an inorganic pigment is a stable phosphoric acid radical produced by pyrolysis of the foaming agent and titanium or zinc react with each other. Titanium oxide (Ti 3 (PO 3 ) 2 ) or zinc phosphate (Zn 3 (PO 3 ) 2 ) can be produced to form a bubble-containing thermal barrier.
［製造例１］
発泡剤として平均粒径１５がマイクロメーター以下のポリりん酸アンモニウム（たとえばクラリアントケミカルズ株式会社、ＡＰ ４２２ 平均粒径１５マイクロメーター）３３．９質量部、ジペンタエリスリトール９．１質量部、メタクリル酸エチル エマルジョン（５０％） ２０．７質量部、酸化亜鉛 （粒径＜１マイクロメーター）１３．４質量部、水 １９．０質量部、添加剤 ３．９質量部を混合し、撹拌して発泡性耐火塗料用組成物を製造した。ずり速度０．１（ｌ／ｓ）における粘度が６８０（Ｐａ・Ｓ、２３℃）であり、ずり速度１００（ｌ／ｓ）における粘度が４７（Ｐａ・Ｓ、２３℃）であった。
[Production Example 1]
33.9 parts by mass of ammonium polyphosphate having an average particle size of 15 micrometers or less (e.g. Clariant Chemicals Co., Ltd., AP 422 average particle size of 15 micrometers), 9.1 parts by mass of dipentaerythritol, and ethyl methacrylate as a blowing agent 20.7 parts by mass of emulsion (50%), 13.4 parts by mass of zinc oxide (particle size < 1 micrometer), 19.0 parts by mass of water, and 3.9 parts by mass of additive are mixed and stirred to form foam. A fire resistant coating composition was produced. The viscosity was 680 (Pa·S, 23°C) at a shear rate of 0.1 (l/s) and 47 (Pa·S, 23°C) at a shear rate of 100 (l/s).
［比較製造例１］
実施例１と同様に、但し水４０質量部を加えて比較製造例１の発泡性耐火塗料用組成物製造した。
[Comparative Production Example 1]
A foamable fire-resistant coating composition of Comparative Production Example 1 was produced in the same manner as in Example 1, except that 40 parts by mass of water was added.
［実施例１］
製造例１で製造した発泡性耐火塗料用組成物を、回転翼付きの撹拌機で撹拌翼を毎分２００回転で撹拌させながら、石膏ボードの基材に、１．０Ｋｇ／ｍ２の割合で吹き付け塗装し、乾燥膜厚０．５１ｍｍの発泡性耐火塗膜を得た。
[Example 1]
The foamable fire-resistant paint composition produced in Production Example 1 was applied to a gypsum board base material at a rate of 1.0 kg/m 2 while stirring the agitating blade with a rotary blade agitator at 200 revolutions per minute. Spray coating was applied to obtain a foamable fireproof coating film having a dry film thickness of 0.51 mm.
［比較例１］
比較製造例１で製造した発泡性耐火塗料用組成物を、撹拌機で撹拌翼を毎分２００回転で撹拌しながら石膏ボードの基材に１．０Ｋｇ／ｍ２の割合で吹き付け塗装した。しかし、比較製造例１で製造した発泡性耐火塗料用組成物は、粘度が低すぎて液だれし、充分な厚さの塗膜を形成することができなかった。
[Comparative Example 1]
The foamable fire-resistant paint composition produced in Comparative Production Example 1 was spray-coated onto a gypsum board substrate at a rate of 1.0 kg/m 2 while stirring with a stirrer with a stirring blade at 200 rpm. However, the foamable fire-resistant paint composition produced in Comparative Production Example 1 had too low a viscosity and dripped, failing to form a sufficiently thick coating film.
［測定例］
電気炉を、ＪＩＳ Ａ １３０４に規定された標準曲線に基づいて２００℃、３００℃４００℃、５００℃、及び６００℃に加熱昇温させ、各電気炉中に実施例１で製造した発泡性耐火塗膜塗布片を１時間放置して変化を観察した。結果を図１に示す。
図１に示すように、本発明に係る発泡性耐火塗膜は、２００℃～３００℃で発泡を開始し、３００℃～５００℃で１０～２０倍に膨張し、膨張分解する。しかし炭素が分解した６００℃でも、気泡を有する気泡含有断熱層を維持した。
[Measurement example]
The electric furnace was heated to 200°C, 300°C, 400°C, 500°C, and 600°C based on the standard curve specified in JIS A 1304, and the intumescent refractory produced in Example 1 was placed in each electric furnace. The coated piece was allowed to stand for 1 hour to observe changes. The results are shown in FIG.
As shown in FIG. 1, the foamable fireproof coating film according to the present invention starts foaming at 200° C. to 300° C., expands 10 to 20 times at 300° C. to 500° C., and expands and decomposes. However, even at 600° C. where carbon was decomposed, the bubble-containing heat insulating layer with bubbles was maintained.
本発明は、かかる課題を解決するためになされたものであって、本発明の発泡性耐火塗料用組成物は、発泡性耐火塗料用組成物を１００質量％とすると、リン系発泡剤２５～５０質量％と、高分子樹脂エマルジョン１５～４０質量％と、炭化剤５～１５質量％と、金属酸化物の無機顔料８～１８質量％と、水又は／及び有機溶媒から選ばれる溶媒１０～３０質量％と、その他の添加剤２～８質量％とを含み、発泡性耐火塗料用組成物の、ずり速度０．１（ｌ／ｓ）における粘度が５００～１０００（Ｐａ・Ｓ、２３℃）であり、ずり速度１００（ｌ／ｓ）における粘度が１０～１００（Ｐａ・Ｓ、２３℃）であり、発泡性耐火塗料用組成物は、３００℃～５００℃に加熱されて多孔性の気泡含有断熱層を形成し、６００℃においても気泡含有断熱層を維持する塗膜を形成することを特徴とする。
The present invention has been made to solve such problems, and the foamable fire-resistant coating composition of the present invention contains 25 to 25% of a phosphorus-based foaming agent when the foamable fire-resistant coating composition is 100% by mass. 50% by mass, 15 to 40% by mass of polymer resin emulsion , 5 to 15% by mass of carbonizing agent, 8 to 18% by mass of metal oxide inorganic pigment, and a solvent selected from water and/or an organic solvent. 10 to 30% by mass and 2 to 8% by mass of other additives, and the viscosity of the foamable fire-resistant coating composition at a shear rate of 0.1 (l / s) is 500 to 1000 (Pa S, 23 ° C.), and the viscosity at a shear rate of 100 (l / s) is 10 to 100 (Pa S, 23 ° C.) . It is characterized by forming a porous heat insulating layer containing air bubbles and forming a coating film that maintains the heat insulating layer containing air bubbles even at 600°C .
前記リン系発泡剤が、ポリリン酸アンモニウム、ポリリン酸２アンモニウム、リン酸２アンモニウム、リン酸アンモニウム、又はリン酸メラミン等のリン系発泡剤から選ばれる１以上であり、高分子樹脂エマルジョンの高分子樹脂が、アクリル系樹脂、シリコーン系樹脂、及び酢酸ビニル系樹脂から選ばれる１以上であり、炭化剤が多価アルコール、デキストリン、又は糖類等から選ばれる１以上であることが好ましい。
The phosphorus-based foaming agent is one or more selected from phosphorus-based foaming agents such as ammonium polyphosphate, diammonium polyphosphate, diammonium phosphate, ammonium phosphate, and melamine phosphate, and the polymer of the polymer resin emulsion is Preferably, the resin is one or more selected from acrylic resins, silicone resins, and vinyl acetate resins, and the carbonizing agent is one or more selected from polyhydric alcohols, dextrin, sugars, and the like .
前記金属酸化物の無機顔料は、酸化チタン、酸化亜鉛、酸化第２鉄、酸化第２銅、２酸化マンガンを含む金属酸化物と、塩基性炭酸銅を含む複合酸化物と、から選ばれる１以上であることが好ましい。
前記添加剤が、アルカリ性増粘剤を含みうる。
前記発泡剤の平均粒径が、２０マイクロメーター以下であることが好ましい。
1. The metal oxide inorganic pigment is selected from metal oxides including titanium oxide, zinc oxide, ferric oxide, cupric oxide , and manganese dioxide, and composite oxides including basic copper carbonate. It is preferable that it is above .
Said additive may comprise an alkaline thickening agent.
It is preferable that the average particle size of the foaming agent is 20 micrometers or less.
本発明は、かかる課題を解決するためになされたものであって、本発明の発泡性耐火塗料用組成物は、発泡性耐火塗料用組成物を１００質量％とすると、リン系発泡剤２５～５０質量％と、高分子樹脂エマルジョン１５～４０質量％と、炭化剤５～１５質量％と、酸化亜鉛、酸化第２鉄、酸化第２銅、２酸化マンガンからなる金属酸化物と、塩基性炭酸銅を含む複合酸化物と、から選ばれる１以上の金属酸化物の無機顔料８～１８質量％と、水又は／及び有機溶媒から選ばれる溶媒１０～３０質量％と、その他の添加剤２～８質量％とを含み、発泡性耐火塗料用組成物の、ずり速度０．１（ｌ／ｓ）における粘度が５００～１０００（Ｐａ・Ｓ、２３℃）であり、ずり速度１００（ｌ／ｓ）における粘度が１０～１００（Ｐａ・Ｓ、２３℃）であり、発泡性耐火塗料用組成物は、３００℃～５００℃に加熱されて多孔性の気泡含有断熱層を形成し、６００℃においても気泡含有断熱層を維持する塗膜を形成することを特徴とする。
The present invention has been made to solve such problems, and the foamable fire-resistant coating composition of the present invention contains 25 to 25% of a phosphorus-based foaming agent when the foamable fire-resistant coating composition is 100% by mass. 50% by mass, 15 to 40% by mass of a polymer resin emulsion, 5 to 15% by mass of a carbonizing agent , a metal oxide composed of zinc oxide, ferric oxide, cupric oxide, and manganese dioxide, and basicity A composite oxide containing copper carbonate, 8 to 18% by mass of an inorganic pigment of one or more metal oxides selected from, 10 to 30% by mass of a solvent selected from water or / and an organic solvent, and other additives 2 ~ 8% by mass, the foamable fire-resistant coating composition has a viscosity of 500 to 1000 (Pa S, 23 ° C.) at a shear rate of 0.1 (l / s), and a shear rate of 100 (l / s) has a viscosity of 10 to 100 (Pa·S, 23°C), and the foamable fire-resistant coating composition is heated to 300°C to 500°C to form a porous, bubble-containing heat insulating layer, and heated to 600°C. is also characterized by forming a coating film that maintains a bubble-containing heat insulating layer.
Claims (7)
発泡剤２５質量％乃至５０質量％（発泡性耐火塗料用組成物を１００質量％する）と、
高分子樹脂エマルジョン１５質量％乃至４０質量％と、
炭化剤５質量％乃至１５質量％と、
無機顔料８質量％乃至１８質量％と、
水又は／及び有機溶媒から選ばれる溶媒１０質量％乃至３０質量％と、
その他の添加剤２質量％乃至８質量％と、を含み、
前記塗料用組成物のずり速度０．１（ｌ／ｓ）における粘度が５００乃至１０００（Ｐａ・Ｓ、２３℃）であり、ずり速度１００（ｌ／ｓ）における粘度が１０乃至１００（Ｐａ・Ｓ、２３℃）であることを特徴とする発泡性耐火塗料用組成物。 The composition for foaming fire-resistant paint is
25% by mass to 50% by mass of a foaming agent (100% by mass of the foamable fire-resistant coating composition);
15% by mass to 40% by mass of a polymer resin emulsion;
5% by mass to 15% by mass of a carbonizing agent;
8% by mass to 18% by mass of an inorganic pigment,
10% by mass to 30% by mass of a solvent selected from water and / and organic solvents;
2% to 8% by mass of other additives,
The viscosity of the coating composition at a shear rate of 0.1 (l / s) is 500 to 1000 (Pa · S, 23 ° C.), and the viscosity at a shear rate of 100 (l / s) is 10 to 100 (Pa · S, 23° C.).
前記高分子樹脂エマルジョンの高分子樹脂が、アクリル系樹脂、シリコーン系樹脂、及び酢酸ビニル系樹脂から選ばれる１以上であり、
前記炭化剤が多価アルコール、デキストリン、又は糖類から選ばれる１以上であることを特徴とする請求項１に記載の発泡性耐火塗料用組成物。 The foaming agent is one or more selected from ammonium polyphosphate, diammonium polyphosphate, diammonium phosphate, ammonium phosphate, or melamine phosphate,
the polymer resin of the polymer resin emulsion is one or more selected from acrylic resins, silicone resins, and vinyl acetate resins;
2. The foamable fire-resistant paint composition according to claim 1, wherein the carbonizing agent is one or more selected from polyhydric alcohols, dextrin, and sugars.
7. The production of the foamable fire-resistant coating film according to claim 6, wherein the foamable fire-resistant coating composition is spray-coated while being stirred at a shear rate of 10 (l/s) to 500 (l/s). Method.
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| JP2005113002A (en) * | 2003-10-08 | 2005-04-28 | Kikusui Chemical Industries Co Ltd | Water-based foaming/fire-retarding coating |
| JP2007169496A (en) * | 2005-12-22 | 2007-07-05 | Shin Etsu Chem Co Ltd | Foamable fireproof coating |
| JP2008013648A (en) * | 2006-07-05 | 2008-01-24 | Sk Kaken Co Ltd | Foaming fireproof coating |
| JP2009197125A (en) * | 2008-02-21 | 2009-09-03 | Nisshin Chem Ind Co Ltd | Coating composition for car interior material and car interior material |
| JP2017039893A (en) * | 2015-08-21 | 2017-02-23 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Aqueous flame retardant coating composition for coating housing material side face |
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| JP2005113002A (en) * | 2003-10-08 | 2005-04-28 | Kikusui Chemical Industries Co Ltd | Water-based foaming/fire-retarding coating |
| JP2007169496A (en) * | 2005-12-22 | 2007-07-05 | Shin Etsu Chem Co Ltd | Foamable fireproof coating |
| JP2008013648A (en) * | 2006-07-05 | 2008-01-24 | Sk Kaken Co Ltd | Foaming fireproof coating |
| JP2009197125A (en) * | 2008-02-21 | 2009-09-03 | Nisshin Chem Ind Co Ltd | Coating composition for car interior material and car interior material |
| JP2017039893A (en) * | 2015-08-21 | 2017-02-23 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Aqueous flame retardant coating composition for coating housing material side face |
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