JP2013241584A - Flame-retardant aqueous coating composition, and flame-retardant coating film and building board using the same - Google Patents
Flame-retardant aqueous coating composition, and flame-retardant coating film and building board using the same Download PDFInfo
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本発明は、難燃性水系塗料組成物、該難燃性水系塗料組成物を用いて得られる難燃性塗膜、及び該難燃性塗膜を備える建築板に関し、特には、難燃性が良好な塗膜を形成することができる難燃性水系塗料組成物に関するものである。 The present invention relates to a flame-retardant water-based coating composition, a flame-retardant coating film obtained using the flame-retardant water-based coating composition, and a building board provided with the flame-retardant coating film. Relates to a flame retardant water-based paint composition capable of forming a good coating film.
防災上の安全確保の為、戸建住宅等に使用される窯業建材ボード等には厳しい防火基準が設けられ、難燃性又は不燃性が求められている。建材ボードに難燃性を付与させる方法の一つとして、建材ボードに難燃性塗料を塗装する方法が挙げられる。特に、作業衛生面や安全性、環境への負荷の点から、水系の難燃性塗料が広く用いられている。例えば、特許文献１には、難燃剤とアクリル樹脂系エマルションとを含有する水系難燃性塗料が開示されている。 In order to ensure safety for disaster prevention, strict fire prevention standards are set for ceramic building materials boards used in detached houses and the like, and flame retardancy or incombustibility is required. One method for imparting flame retardancy to a building material board is to apply a flame retardant paint to the building material board. In particular, water-based flame retardant paints are widely used from the viewpoint of occupational hygiene, safety, and environmental load. For example, Patent Document 1 discloses a water-based flame retardant paint containing a flame retardant and an acrylic resin emulsion.
しかしながら、従来の難燃性塗料から得られる塗膜では、十分な難燃性が得られるものの、水蒸気透過度が高い。そのため、建材等に水蒸気が出入りし易くなり、建材板が反りやすくなるという不具合が起こりやすくなっていた。また、作業性の面から、塗膜の凍結融解安定性が求められる場合もある。 However, a coating film obtained from a conventional flame retardant paint has a high water vapor transmission rate although sufficient flame retardancy is obtained. For this reason, water vapor easily enters and exits the building material and the like, and the problem that the building material plate is easily warped is likely to occur. Moreover, the freeze-thaw stability of a coating film may be calculated | required from the surface of workability | operativity.
本発明の目的は、建築物や建材等に、難燃性が良好な塗膜を形成することができる難燃性水系塗料組成物を提供することにある。また、本発明の他の目的は、難燃性が良好で、且つ水蒸気を透過しにくい塗膜、並びに該塗膜を備えた建築板を提供することにある。 The objective of this invention is providing the flame-retardant water-based coating composition which can form a coating film with favorable flame retardance on a building, a building material, etc. Another object of the present invention is to provide a coating film having good flame retardancy and hardly transmitting water vapor, and a building board provided with the coating film.
本発明者らは、前述の課題を解決するために種々検討を行った結果、水系バインダー樹脂に難燃剤を配合することで、優れた難燃性を有する塗膜を得ることができ、建築物や建材に難燃性を付与できることを見出した。 As a result of various studies to solve the above-mentioned problems, the present inventors can obtain a coating film having excellent flame retardancy by blending a flame retardant with an aqueous binder resin, and a building. And found that it can impart flame retardancy to building materials.
即ち、本発明の難燃性水系塗料組成物は、（Ａ）水系バインダー樹脂及び（Ｂ）難燃剤を含有することを特徴とする。 That is, the flame-retardant water-based coating composition of the present invention is characterized by containing (A) a water-based binder resin and (B) a flame retardant.
本発明の難燃性水系塗料組成物の好適例においては、更に、（Ｃ）無機系層状化合物を含有する。 In the suitable example of the flame-retardant water-based coating composition of this invention, (C) inorganic type layered compound is contained further.
本発明の難燃性水系塗料組成物の他の好適例においては、前記（Ｃ）無機系層状化合物が、非膨潤性層状珪酸塩及び膨潤性層状珪酸塩よりなる群から選択される少なくとも１種の化合物である。 In another preferable example of the flame-retardant water-based coating composition of the present invention, the (C) inorganic layered compound is at least one selected from the group consisting of a non-swellable layered silicate and a swellable layered silicate. It is a compound of this.
本発明の難燃性水系塗料組成物の他の好適例において、前記無機系層状化合物は、アスペクト比が１０〜１０００である。 In another preferable example of the flame-retardant water-based coating composition of the present invention, the inorganic layered compound has an aspect ratio of 10 to 1,000.
本発明の難燃性水系塗料組成物の他の好適例においては、前記（Ｂ）難燃剤が、ハロゲン系難燃剤であり、難燃助剤としてアンチモン系化合物を更に含有する。 In another preferable example of the flame retardant water-based paint composition of the present invention, the flame retardant (B) is a halogen flame retardant, and further contains an antimony compound as a flame retardant aid.
本発明の難燃性水系塗料組成物の他の好適例においては、前記（Ａ）水系バインダー樹脂が、アクリル樹脂であり、エマルションの形態で用いられる。 In another preferable example of the flame-retardant water-based coating composition of the present invention, the (A) water-based binder resin is an acrylic resin and is used in the form of an emulsion.
本発明の難燃性水系塗料組成物の他の好適例においては、前記アクリル樹脂が、アクリルシリコーン樹脂である。 In another preferable example of the flame-retardant water-based coating composition of the present invention, the acrylic resin is an acrylic silicone resin.
本発明の難燃性水系塗料組成物の他の好適例においては、前記アクリル樹脂は、ガラス転移温度が３０〜６０℃である。 In another preferable example of the flame-retardant water-based coating composition of the present invention, the acrylic resin has a glass transition temperature of 30 to 60 ° C.
本発明の難燃性水系塗料組成物の他の好適例においては、更に、シランカップリング剤を含む。 In another preferred embodiment of the flame retardant water-based coating composition of the present invention, a silane coupling agent is further included.
また、本発明の難燃性塗膜は、上記の難燃性水系塗料組成物を基材に塗布し、成膜させることにより得られる難燃性塗膜であることを特徴とし、該難燃性塗膜の４０℃／９０％ＲＨ条件下での水蒸気透過度が、５０ｇ／ｍ２／Ｄａｙ以下であることが好ましい。更に、本発明の建築板は、上記の難燃性塗膜を備えることを特徴とする。 The flame-retardant coating film of the present invention is a flame-retardant coating film obtained by applying the flame-retardant aqueous coating composition on a substrate and forming a film, The water vapor permeability of the water-soluble coating film under the 40 ° C./90% RH condition is preferably 50 g / m 2 / Day or less. Furthermore, the building board of this invention is equipped with said flame-retardant coating film, It is characterized by the above-mentioned.
本発明の難燃性水系塗料組成物によれば、建築物や建材等に、難燃性が良好な塗膜を形成することができる難燃性水系塗料組成物を提供することができる。また、該難燃性水系塗料組成物を用いることで、難燃性が良好な塗膜、並びに該塗膜を備えた建築板を提供することができる。 According to the flame-retardant water-based paint composition of the present invention, it is possible to provide a flame-retardant water-based paint composition capable of forming a coating film having good flame retardancy on a building or building material. Moreover, by using this flame-retardant water-based coating composition, it is possible to provide a coating film having good flame retardancy and a building board provided with the coating film.
以下に、本発明の難燃性水系塗料組成物を詳細に説明する。本発明の難燃性水系塗料組成物は、（Ａ）水系バインダー樹脂及び（Ｂ）難燃剤を含有することを特徴とし、建築物や建材等に、難燃性が良好で、且つ水蒸気を透過しにくい塗膜を形成することができる。なお、本発明における水系塗料組成物とは、水を主溶媒として用いる塗料組成物を指し、具体的には、水系塗料組成物の溶媒成分に占める水の含有量が５０質量％以上である塗料組成物である。水系塗料組成物の溶媒成分に占める水の含有量は、９０質量％以上であることが好ましい。 Below, the flame-retardant water-based coating composition of this invention is demonstrated in detail. The flame-retardant water-based paint composition of the present invention is characterized by containing (A) a water-based binder resin and (B) a flame retardant, and has good flame retardancy and permeates water vapor to buildings and building materials. It is possible to form a coating film that is difficult to resist. The water-based paint composition in the present invention refers to a paint composition using water as a main solvent, and specifically, a paint whose water content in the solvent component of the water-based paint composition is 50% by mass or more. It is a composition. The content of water in the solvent component of the aqueous coating composition is preferably 90% by mass or more.
（Ａ）水系バインダー樹脂
本発明の難燃性水系塗料組成物に使用できる水系バインダー樹脂は、水に溶解する水溶性樹脂又は水中に分散可能な合成樹脂であり、溶液又はエマルションのいずれの形態で用いてもよいが、耐水性の点から、エマルションの形態で用いるのが好ましい。なお、合成樹脂が水中に分散状態にあるものを「合成樹脂系エマルション」ともいう。
(A) Water-based binder resin The water-based binder resin that can be used in the flame-retardant water-based coating composition of the present invention is a water-soluble resin that dissolves in water or a synthetic resin that can be dispersed in water, and is in any form of a solution or an emulsion. Although it may be used, it is preferably used in the form of an emulsion from the viewpoint of water resistance. A synthetic resin dispersed in water is also referred to as a “synthetic resin emulsion”.
上記水溶性樹脂としては、例えば、アクリル樹脂、シリコーン樹脂、アクリルシリコーン樹脂、フッ素樹脂、エポキシ樹脂、ビニル樹脂、フェノール樹脂、ウレタン樹脂、メラミン樹脂、ケトン樹脂等が挙げられる。また、これら樹脂は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。更に、これら樹脂は、他の樹脂成分で変性されていてもよい。また更に、これら水溶性樹脂中に架橋剤を添加してもよい。 Examples of the water-soluble resin include acrylic resin, silicone resin, acrylic silicone resin, fluorine resin, epoxy resin, vinyl resin, phenol resin, urethane resin, melamine resin, and ketone resin. Moreover, these resin may be used individually by 1 type, and may be used in combination of 2 or more type. Furthermore, these resins may be modified with other resin components. Furthermore, a crosslinking agent may be added to these water-soluble resins.
上記合成樹脂系エマルションとしては、例えば、アクリル樹脂系エマルション、ウレタン樹脂系エマルション、フッ素樹脂系エマルション、ポリスチレン樹脂系エマルション、塩化ビニル樹脂系エマルション等が挙げられるが、耐候性と取り扱いの容易さの点からアクリル樹脂系エマルションが好ましい。また、これら合成樹脂系エマルション中に架橋剤を添加してもよい。ここで、アクリル樹脂系エマルションとは、「（メタ）アクリルモノマーの重合体」のエマルション又は「（メタ）アクリルモノマーと他のモノマーとの共重合体」のエマルションを意味する。 Examples of the synthetic resin emulsion include acrylic resin emulsions, urethane resin emulsions, fluororesin emulsions, polystyrene resin emulsions, vinyl chloride resin emulsions, etc., but are weather resistant and easy to handle. To acrylic resin emulsions are preferred. Moreover, you may add a crosslinking agent in these synthetic resin type | system | group emulsions. Here, the acrylic resin emulsion means an emulsion of “polymer of (meth) acrylic monomer” or an emulsion of “copolymer of (meth) acrylic monomer and other monomer”.
上記合成樹脂系エマルションについては、既に公知となっている通常の合成手法を利用することによって調製できる。例えば、アクリル樹脂系エマルションの場合、アクリル酸エステル及びメタクリル酸エステルの内の少なくとも１種を含有する（メタ）アクリルモノマーと、必要に応じてその他のモノマーとを、乳化剤又は分散安定剤の存在下で、水中にて攪拌下乳化重合して得られる。また、合成樹脂系エマルションは、調製後、必要に応じて、中和されてもよいし、合成樹脂系エマルション中に含まれる合成樹脂を変性してもよい。 About the said synthetic resin type | system | group emulsion, it can prepare by utilizing the normal synthesis method already known. For example, in the case of an acrylic resin-based emulsion, a (meth) acrylic monomer containing at least one of acrylic acid ester and methacrylic acid ester and, if necessary, other monomers are added in the presence of an emulsifier or a dispersion stabilizer. And obtained by emulsion polymerization in water with stirring. In addition, the synthetic resin emulsion may be neutralized as necessary after preparation, or the synthetic resin contained in the synthetic resin emulsion may be modified.
アクリル樹脂系エマルションの調製に使用できる（メタ）アクリルモノマーとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｉ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸シクロへキシル等のアクリル酸又はメタクリル酸の炭素数１〜１８のアルキルエステル又はシクロアルキルエステル；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸エトキシブチル等のアクリル酸又はメタクリル酸の炭素数２〜１８のアルコキシアルキルエステル；アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸等のカルボキシル基含有不飽和モノマー；２−ヒドロキシエチル（メタ）アクリレート、２−又は３−ヒドロキシプロピル（メタ）アクリレート等のアクリル酸又はメタクリル酸の炭素数２〜８のヒドロキシアルキルエステル；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等の含窒素アルキル（メタ）アクリレート；アクリルアミド、メタクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド等の重合性アミド；グリシジル（メタ）アクリレート等のエポキシアクリレート等が挙げられ、（メタ）アクリルモノマー以外のモノマーとしては、例えば、アリルグリシジルエーテル等のエポキシ基含有不飽和モノマー、酢酸ビニル、スチレン、及びアクリロニトリル等が挙げられる。なお、アクリル樹脂系エマルションが、（メタ）アクリルモノマーと他のモノマーとの共重合体のエマルションであり、他のモノマーが少なくともスチレンを含む場合、該共重合体を構成するモノマー（単量体）全体に占めるスチレンの割合は、５０質量％以上であることが好ましく、５０〜９８質量％の範囲が更に好ましい。該スチレンの割合が５０質量％以上であると、塗膜の耐水蒸気透過性が良好となる傾向がある。 Examples of (meth) acrylic monomers that can be used for preparing acrylic resin emulsions include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl (meth) acrylate. , N-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate n -C1-C18 alkyl ester or cyclo of acrylic acid or methacrylic acid such as octyl, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Alkyl ester; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methacrylic acid ethoxybutyl; carboxyl group-containing unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid; C2-C8 hydroxyalkyl ester of acrylic acid or methacrylic acid such as 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, Nitrogen-containing alkyl (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Dimethyl Polymerizable amides such as minoethyl (meth) acrylamide; epoxy acrylates such as glycidyl (meth) acrylate, and the like. Examples of monomers other than (meth) acrylic monomers include epoxy group-containing unsaturated monomers such as allyl glycidyl ether, Examples include vinyl acetate, styrene, and acrylonitrile. In addition, when the acrylic resin emulsion is an emulsion of a copolymer of a (meth) acrylic monomer and another monomer, and the other monomer contains at least styrene, the monomer (monomer) constituting the copolymer The proportion of styrene in the whole is preferably 50% by mass or more, and more preferably in the range of 50 to 98% by mass. When the proportion of styrene is 50% by mass or more, the water vapor permeability resistance of the coating film tends to be good.
乳化重合反応は、例えば、乳化剤の存在下において水媒体中で攪拌下に所定温度にてモノマー及び重合開始剤を一括、或いは連続的に供給することにより行われる。 The emulsion polymerization reaction is performed, for example, by supplying the monomer and the polymerization initiator all at once or at a predetermined temperature with stirring in an aqueous medium in the presence of an emulsifier.
上記乳化剤として、例えば、ラウリン酸ナトリウム等の脂肪酸塩、ラウリル硫酸ナトリウム等の高級アルコール硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシノニルフェニルエーテルスルホン酸アンモニウム、ポリオキシエチレン−ポリオキシプロピレングリコールエーテル硫酸塩、更には、スルホン酸基又は硫酸エステル基と重合性の炭素−炭素不飽和二重結合を分子中に有する、いわゆる反応性乳化剤等のアニオン性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンノニルフェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン−ポリオキシプロピレンブロックコポリマー、又はこれらの化合物の骨格と重合性の炭素−炭素不飽和二重結合を分子中に有する反応性ノニオン性界面活性剤等のノニオン性界面活性剤；アルキルアミン塩、第４級アンモニウム塩等のカチオン性界面活性剤；（変性）ポリビニルアルコール等を挙げることができる。 Examples of the emulsifier include fatty acid salts such as sodium laurate, higher alcohol sulfates such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfate, polyoxynonylphenyl ether Ammonium sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, and a so-called reactive emulsifier having a sulfonic acid group or a sulfate ester group and a polymerizable carbon-carbon unsaturated double bond in the molecule. Anionic surfactant: polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene butyl ester Copolymer, or nonionic surfactants such as reactive nonionic surfactants having a skeleton of these compounds and a polymerizable carbon-carbon unsaturated double bond in the molecule; alkylamine salts, quaternary ammonium salts, etc. (Modified) polyvinyl alcohol and the like.
また、乳化重合反応に使用できる重合開始剤としては、過硫酸アンモニウム、過硫酸ナトリウム及び過硫酸カリウム等の過硫酸塩、過酸化水素水、２，２’−アゾビス（２−アミノジプロパン）ハイドロクロライド、４，４’−アゾビス−シアノバレリックアシッド及び２，２’−アゾビス（２−メチルブタンアミドオキシム）ジハイドロクロライドテトラハイドレート等のアゾ系化合物、ｔ−ブチルハイドロパーオキサイド等の水性ラジカル重合開始剤並びにこれらの混合物が挙げられる。このような重合開始剤は、還元剤と組み合わせ、レドックス系重合開始剤を形成することができる。そのような還元剤としては、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、チオ硫酸ナトリウム及びホルムアルデヒドスルホン酸塩等のアルカリ金属塩、並びにアンモニウム塩、Ｌ−アスコルビン酸及び酒石酸等のカルボン酸類が挙げられる。 Examples of the polymerization initiator that can be used for the emulsion polymerization reaction include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, hydrogen peroxide, 2,2′-azobis (2-aminodipropane) hydrochloride. , 4,4′-azobis-cyanovaleric acid, 2,2′-azobis (2-methylbutanamidooxime) dihydrochloride tetrahydrate and other azo compounds, t-butyl hydroperoxide and other aqueous radical polymerization Initiators as well as mixtures thereof are mentioned. Such a polymerization initiator can be combined with a reducing agent to form a redox polymerization initiator. Such reducing agents include alkali metal salts such as sulfites, hydrogen sulfites, pyrosulfites, sodium thiosulfate and formaldehyde sulfonate, and carboxylic acids such as ammonium salts, L-ascorbic acid and tartaric acid. .
乳化重合反応には、必要に応じて連鎖移動剤を使用することができる。その連鎖移動剤としては、例えば、ラウリルメルカプタン、ｎ−ブチルメルカプタン、ｔ−ブチルメルカプタン、オクチルメルカプタン及びｎ−ドデシルメルカプタン等のアルキルメルカプタン、チオグリコール酸−２−エチルヘキシル、２−メチル−ｔ−ブチルチオフェノール、並びにα−メチルスチレンダイマー等を挙げることができる。 A chain transfer agent can be used in the emulsion polymerization reaction as necessary. Examples of the chain transfer agent include alkyl mercaptans such as lauryl mercaptan, n-butyl mercaptan, t-butyl mercaptan, octyl mercaptan and n-dodecyl mercaptan, 2-ethylhexyl thioglycolate, 2-methyl-t-butylthio Phenol and α-methylstyrene dimer can be mentioned.
本発明の難燃性水系塗料組成物において、上記水系バインダー樹脂がアクリル樹脂である場合、アクリル樹脂のガラス転移温度（以下、Ｔｇともいう）は、３０〜６０℃であることが好ましい。Ｔｇが３０℃未満である場合には、気温によって塗膜が軟化し、塗膜の粘着感や汚染物質の付着等によって塗膜が汚染されるため適さない。一方、Ｔｇが６０℃を超える場合には、塗膜を硬化させた際に建材等の被塗物の膨張に追従できなくなり、塗膜の剥離が起こり易くなる。アクリル樹脂系エマルションを用いる場合、アクリル樹脂のＴｇが３０℃〜６０℃になるように、エチレン性不飽和単量体を組み合わせることが好適である。なお、Ｔｇの値は、一般に用いられるＦＯＸ式を用いて算出されるものをいう。 In the flame-retardant water-based paint composition of the present invention, when the water-based binder resin is an acrylic resin, the glass transition temperature (hereinafter also referred to as Tg) of the acrylic resin is preferably 30 to 60 ° C. When Tg is less than 30 ° C., the coating film is softened by the air temperature, and the coating film is contaminated due to adhesion of the coating film or adhesion of contaminants. On the other hand, when Tg exceeds 60 ° C., it becomes impossible to follow the expansion of an object to be coated such as a building material when the coating film is cured, and the coating film easily peels off. When an acrylic resin emulsion is used, it is preferable to combine ethylenically unsaturated monomers so that the acrylic resin has a Tg of 30 ° C to 60 ° C. In addition, the value of Tg means what is calculated using the FOX formula generally used.
本発明の難燃性水系塗料組成物において、上記水系バインダー樹脂がアクリル樹脂である場合、アクリル樹脂の酸価は、１５ｍｇＫＯＨ／ｇ以上であることが好ましく、１５〜１００ｍｇＫＯＨ／ｇであることが更に好ましい。酸価が１５ｍｇＫＯＨ／ｇ以上の場合、塗膜の耐水蒸気透過性が良好となる傾向がある。一方、酸価が１００ｍｇＫＯＨ／ｇを超えると、塗膜の耐水性が悪くなる傾向がある。 In the flame-retardant water-based coating composition of the present invention, when the water-based binder resin is an acrylic resin, the acid value of the acrylic resin is preferably 15 mgKOH / g or more, and more preferably 15 to 100 mgKOH / g. preferable. When the acid value is 15 mgKOH / g or more, the water vapor permeability resistance of the coating film tends to be good. On the other hand, when the acid value exceeds 100 mgKOH / g, the water resistance of the coating film tends to deteriorate.
上記アクリル樹脂系エマルションのうち、耐ブロッキング性の観点から、少なくとも（メタ）アクリルモノマーと加水分解性シリル基を有する単量体とを共重合することによって得ることのできるアクリルシリコーン樹脂のエマルションが好ましい。ここで、加水分解性シリル基を有する単量体としては、例えば、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、β−（メタ）アクリロキシエチルトリメトキシシラン、β−（メタ）アクリロキシエチルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジプロポキシシラン、γ−（メタ）アクリロキシブチルフェニルジメトキシシラン、γ−（メタ）アクリロキシプロピルジメチルメトキシシラン、及びγ−（メタ）アクリロキシプロピルジエチルメトキシシラン等が挙げられる。 Among the acrylic resin emulsions, from the viewpoint of blocking resistance, an emulsion of an acrylic silicone resin that can be obtained by copolymerizing at least a (meth) acryl monomer and a monomer having a hydrolyzable silyl group is preferable. . Here, examples of the monomer having a hydrolyzable silyl group include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and β- (meth) acryloxyethyl. Trimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyl Examples include dipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, and γ- (meth) acryloxypropyldiethylmethoxysilane.
上記アクリルシリコーン樹脂の重合において、加水分解性シリル基を有する単量体の配合量は、使用される単量体の合計中、０．２質量％以上１５．０質量％以下が好ましく、０．５質量％以上１２．０質量％以下が更に好ましく、０．５質量％〜３質量％が一層好ましい。加水分解性シリル基を有する単量体の配合量が０．２質量％より少ないと、耐ブロッキング性等が十分に得られない場合があり、１５．０質量％を超えると、膜が脆くなる傾向がある。 In the polymerization of the acrylic silicone resin, the blending amount of the monomer having a hydrolyzable silyl group is preferably 0.2% by mass or more and 15.0% by mass or less in the total of the monomers used. 5 mass% or more and 12.0 mass% or less are still more preferable, and 0.5 mass%-3 mass% are still more preferable. If the blending amount of the monomer having a hydrolyzable silyl group is less than 0.2% by mass, blocking resistance or the like may not be sufficiently obtained. If the amount exceeds 15.0% by mass, the film becomes brittle. Tend.
（Ｂ）難燃剤
本発明の難燃性水系塗料組成物に使用できる難燃剤としては、例えば、金属水酸化物、リン系難燃剤、ハロゲン系難燃剤、窒素系難燃剤、シリコン系難燃剤が挙げられる。
(B) Flame retardant Examples of the flame retardant that can be used in the flame retardant aqueous coating composition of the present invention include metal hydroxides, phosphorus flame retardants, halogen flame retardants, nitrogen flame retardants, and silicon flame retardants. Can be mentioned.
上記金属水酸化物としては、例えば、水酸化アルミニウム、水酸化マグネシウム等が挙げられる。リン酸系難燃剤としては、例えば、トリフェニルホスフェート、トリクレジルホスフェート、ジフェニルクレジルフォスフェート、トリス（トリブロモネオペンチル）ホスフェート等の有機リン系難燃剤や、赤リン、三塩化リン、五塩化リン、ポリリン酸アンモニウム等の無機リン系難燃剤が挙げられる。 Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide. Examples of phosphoric acid flame retardants include organic phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, tris (tribromoneopentyl) phosphate, red phosphorus, phosphorus trichloride, five Examples include inorganic phosphorus flame retardants such as phosphorus chloride and ammonium polyphosphate.
ハロゲン系難燃剤としては、例えば、臭素系難燃剤や塩素系難燃剤が挙げられ、臭素系難燃剤には、例えば、テトラブロモジフェニルオキサイド、オクタブロモジフェニルオキサイド及びデカブロモジフェニルオキサイド等のブロモジフェニルオキサイド系難燃剤や、ビス（ペンタブロモフェニル）エーテル（ＤＢＤＰＯ、別名：デカブロモジフェニルエーテル）、テトラブロモビスフェノールＡ（ＴＢＡ）、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、ヘキサブロモシクロドデカン、ヘキサブロモベンゼン、ビストリブロモフェノキシエタン、トリブロモフェノール、エチレンビステトラブロモフタルイミド、ＴＢＡポリカーボネートオリゴマー、ＴＢＡエポキシオリゴマー、並びに臭素化ポリスチレン等が挙げられる。また、塩素系難燃剤には、例えば、塩素化ポリフェニル、塩素化パラフィン、塩素化ナフタレン、パークロロシクロペンタデカン（デクロランプラス）、及びクロレンド酸が挙げられる。 Examples of the halogen-based flame retardant include bromine-based flame retardant and chlorine-based flame retardant. Examples of the brominated flame retardant include bromodiphenyl oxide such as tetrabromodiphenyl oxide, octabromodiphenyl oxide, and decabromodiphenyl oxide. Flame retardants, bis (pentabromophenyl) ether (DBDPO, also known as decabromodiphenyl ether), tetrabromobisphenol A (TBA), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, hexa Bromocyclododecane, hexabromobenzene, bistribromophenoxyethane, tribromophenol, ethylenebistetrabromophthalimide, TBA polycarbonate oligomer, TBA epoxy oligomer, brominated polystyrene, etc. It is. In addition, examples of the chlorinated flame retardant include chlorinated polyphenyl, chlorinated paraffin, chlorinated naphthalene, perchlorocyclopentadecane (dechlorane plus), and chlorendic acid.
窒素系難燃剤としては、例えば、炭酸アンモニウムやメラミンシアヌレートが挙げられる。シリコン系難燃剤としては、シリコーン樹脂やシリコーン系化合物が挙げられる。 Examples of the nitrogen-based flame retardant include ammonium carbonate and melamine cyanurate. Silicone flame retardants include silicone resins and silicone compounds.
これらの難燃剤は、単独で用いても良いが、複数種類を組み合わせることでより高い難燃効果を得ることができる。例えば、ハロゲン系難燃剤とリン系難燃剤、リン系難燃剤と窒素系難燃剤、金属水酸化物とハロゲン系難燃剤またはリン系難燃剤の組み合わせがより高い相乗効果をもたらすことが知られている。 These flame retardants may be used alone, but a higher flame retardant effect can be obtained by combining a plurality of types. For example, it is known that a combination of a halogen-based flame retardant and a phosphorus-based flame retardant, a phosphorus-based flame retardant and a nitrogen-based flame retardant, a metal hydroxide and a halogen-based flame retardant or a phosphorus-based flame retardant provides a higher synergistic effect. Yes.
本発明の難燃性水系塗料組成物において、難燃剤の配合量は、樹脂１００質量部に対して、３５〜１２０質量部であることが好ましい。該難燃性の配合量が３５質量部より少ないと、塗膜の難燃性が十分得られない場合があり、一方、１２０質量部より多いと、塗膜の強度が低下する。 In the flame-retardant water-based coating composition of the present invention, the blending amount of the flame retardant is preferably 35 to 120 parts by mass with respect to 100 parts by mass of the resin. When the flame retardant compounding amount is less than 35 parts by mass, the flame retardancy of the coating film may not be sufficiently obtained. On the other hand, when it exceeds 120 parts by mass, the strength of the coating film decreases.
また、アンチモン系化合物やホウ酸系化合物のような難燃助剤を上記難燃剤と組み合わせて用いることにより、難燃性を更に向上させることも出来る。アンチモン系化合物としては、例えば、三酸化アンチモン、五酸化アンチモン、アンチモン酸ナトリウム等が挙げられる。ホウ酸系化合物としては、例えば、ホウ酸亜鉛、ホウ酸ソーダ等が挙げられる。 In addition, flame retardancy can be further improved by using a flame retardant aid such as an antimony compound or a boric acid compound in combination with the flame retardant. Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, and the like. Examples of boric acid compounds include zinc borate and sodium borate.
なお、本発明の難燃性水系塗料組成物が難燃剤と難燃助剤の両者を含む場合、難燃剤と難燃助剤の質量比は、難燃剤：難燃助剤＝１：１〜１０：１が好ましく、２：１〜６：１が特に好ましい。 In addition, when the flame retardant water-based coating composition of the present invention includes both a flame retardant and a flame retardant aid, the mass ratio of the flame retardant and the flame retardant aid is flame retardant: flame retardant aid = 1: 1 to 1. 10: 1 are preferred, and 2: 1 to 6: 1 are particularly preferred.
本発明の難燃性水系塗料組成物においては、ハロゲン系難燃剤とアンチモン系化合物を組み合わせることが好ましく、これらを併用することで、耐水蒸気透過性を損なうことなく、難燃性を大幅に向上できる。 In the flame-retardant water-based paint composition of the present invention, it is preferable to combine a halogen-based flame retardant and an antimony compound. By using these in combination, flame retardancy is significantly improved without impairing water vapor permeability. it can.
（Ｃ）無機系層状化合物
本発明の難燃性水系塗料組成物は、更に無機系層状化合物を含有することが好ましい。無機系層状化合物は、結晶層が互いに積み重なって層状構造を有する無機化合物であり、塗膜形成の際に塗料組成物中の無機系層状化合物が互いに重なり合って積層し、塗膜の耐水蒸気透過性を向上させる効果が発揮され、耐湿性を向上できる。また、被塗物の燃焼時等に発生する可燃性ガスや有毒性ガスに対して優れた遮蔽効果が発揮され、火災の延焼や有毒性ガスによるガス中毒等に対して有効に作用する。
(C) Inorganic layered compound It is preferable that the flame-retardant water-based coating composition of the present invention further contains an inorganic layered compound. The inorganic layered compound is an inorganic compound having a layered structure in which crystal layers are stacked on each other, and the layered inorganic layered compounds in the coating composition are stacked on top of each other when forming a coating film. The effect which improves is improved, and moisture resistance can be improved. In addition, it has an excellent shielding effect against flammable gas and toxic gas generated during combustion of the object to be coated, etc., and acts effectively on fire spread and gas poisoning due to toxic gas.
上記無機系層状化合物は、単位結晶層が互いに積み重なって層状構造を有する化合物であるが、ここで層状構造とは、原子が共有結合等によって強く結合し密に配列した面（層）が、ファン・デル・ワールス力等の弱い結合力によって平行に積み重なった構造をいう。無機系層状化合物は、劈開性を有しており、本発明に使用できる無機系層状化合物は、粒径が５〜６０μｍであることが好ましく、また、アスペクト比（長径／厚み）は、１０〜５０００であることが好ましい。粒径及び／又はアスペクト比が上記特定した範囲内であると、上述の耐水蒸気透過性の向上に対して優れた効果を発揮でき、また、遮蔽効果を向上できる。無機系層状化合物のアスペクト比が１０未満では、耐水蒸気透過性が十分に得られない場合もあり、また、アスペクト比が５０００を超えると、塗料の分散安定性が低下する。また、アスペクト比は、１０〜１０００であることが更に好ましい。アスペクト比が１０〜１０００の範囲内であると、更に塗膜の凍結融解安定性が良好となり、寒暖の差が大きい条件においても、塗膜が割れにくい特徴を示す。なお、無機系層状化合物の粒径については、レーザー回折法等を用いた一般的な手法によって測定することができる。また、アスペクト比については、走査電子顕微鏡（ＳＥＭ）を用いて求めることができる。具体的には、ＳＥＭで無機系層状化合物を観察し、任意に抽出した５０〜１００個の無機系層状化合物の粒子に対して、それぞれの長径及び厚みの幅を計測した後、それぞれの粒子のアスペクト比を求め、その平均値を求める方法が挙げられる。 The inorganic layered compound is a compound having a layered structure in which unit crystal layers are stacked on each other. Here, the layered structure is a surface (layer) in which atoms are strongly bonded by a covalent bond or the like and closely arranged. -A structure that is stacked in parallel by a weak binding force such as a Del Waals force. The inorganic layered compound has cleavage properties, and the inorganic layered compound that can be used in the present invention preferably has a particle size of 5 to 60 μm, and an aspect ratio (major axis / thickness) of 10 to 10 μm. It is preferably 5000. When the particle size and / or aspect ratio is within the above-specified range, it is possible to exert an excellent effect on the above-described improvement in water vapor permeability and to improve the shielding effect. If the aspect ratio of the inorganic layered compound is less than 10, sufficient water vapor resistance may not be obtained. If the aspect ratio exceeds 5,000, the dispersion stability of the coating is lowered. The aspect ratio is more preferably 10 to 1000. When the aspect ratio is in the range of 10 to 1,000, the freeze-thaw stability of the coating film is further improved, and the coating film is difficult to crack even under conditions where the temperature difference is large. The particle size of the inorganic layered compound can be measured by a general method using a laser diffraction method or the like. The aspect ratio can be determined using a scanning electron microscope (SEM). Specifically, the inorganic stratiform compound was observed with an SEM, and after arbitrarily measuring 50 to 100 inorganic stratiform compound particles, the width of each major axis and thickness was measured. There is a method of obtaining an aspect ratio and obtaining an average value thereof.
上記無機系層状化合物の具体例としては、層状珪酸塩、層状グラファイト、層状カルコゲン化物、層状ハイドロタルサイト化合物、層状リチウムアルミニウム複合水酸化物、層状リン酸ジルコニウム系化合物等を挙げることができるが、耐水性、耐久性、取り扱い易さの点から、層状珪酸塩が好ましい。ここで、「カルコゲン化物」とは、ＩＶ族（Ｔｉ，Ｚｒ，Ｈｆ）、Ｖ族（Ｖ，Ｎｂ，Ｔａ）及び／又はＶＩ族（Ｍｏ，Ｗ）元素のジカルコゲン化物であって、式ＭＸ2（Ｍは上記元素、Ｘはカルコゲン（Ｓ，Ｓｅ，Ｔｅ）を示す。）で表わされるものをいう。 Specific examples of the inorganic layered compound include layered silicate, layered graphite, layered chalcogenide, layered hydrotalcite compound, layered lithium aluminum composite hydroxide, layered zirconium phosphate compound, and the like. A layered silicate is preferable from the viewpoint of water resistance, durability, and ease of handling. Here, the “chalcogenide” is a dichalcogenide of a group IV (Ti, Zr, Hf), group V (V, Nb, Ta) and / or group VI (Mo, W) element, which has the formula MX 2 (M represents the above element, and X represents chalcogen (S, Se, Te)).
上記層状珪酸塩は、一般に、シリカの四面体層の上部に、アルミニウムやマグネシウム等を中心金属にした八面体層を有する２層構造を有するタイプ（１：１型構造）と、シリカの四面体層が、アルミニウムやマグネシウム等を中心金属にした八面体層を両側から挟んでなる３層構造を有するタイプ（２：１型構造）等に分類される。 The layered silicate is generally a type having a two-layer structure (1: 1 type structure) having an octahedral layer having aluminum, magnesium, or the like as a central metal on a silica tetrahedral layer, and a silica tetrahedral. The layer is classified into a type having a three-layer structure (2: 1 type structure) in which an octahedral layer having aluminum or magnesium as a central metal is sandwiched from both sides.
１：１型構造の層状珪酸塩としては、例えば、カオリナイトやハロイサイト等のカオリン鉱物が挙げられる。 Examples of the layered silicate having a 1: 1 type structure include kaolin minerals such as kaolinite and halloysite.
２：１型構造の層状珪酸塩は、層電荷の違いによって分類される。例えば、層電荷をほとんど持たないものとしてタルクやパイロフィライトが挙げられ、層電荷を有するものとしては、スメクタイト族（サポナイト、ヘラクライト、モンモリロナイト等）、バーミキュライト、雲母族（金雲母、白雲母、絹雲母等）等が挙げられる。 2: 1 type layered silicates are classified by the difference in layer charge. For example, talc and pyrophyllite are mentioned as those having almost no layer charge, and those having layer charge include smectite group (saponite, heraclite, montmorillonite, etc.), vermiculite, mica group (phlogopite, muscovite, silk Mica etc.).
上記層状珪酸塩には、天然に産出される天然物の他に、人工的に合成されて得られる合成物がある。合成物としては、例えば、フッ素金雲母（ＫＭｇ３ＡｌＳｉ３Ｏ１０Ｆ）、カリウム四ケイ素雲母（ＫＭｇ２．５Ｓｉ４Ｏ１０Ｆ２）、ナトリウム四ケイ素雲母（ＮａＭｇ２．５Ｓｉ４Ｏ１０Ｆ２）、ナトリウムテニオライト（ＮａＭｇ２ＬｉＳｉ４Ｏ１０Ｆ２）及びリチウムテニオライト（ＬｉＭｇ２ＬｉＳｉ４Ｏ１０Ｆ２）等の合成雲母、ナトリウムヘクトライト（Ｎａ０．３３Ｍｇ２．６７Ｌｉ０．３３Ｓｉ４．０Ｏ１０（ＯＨ又はＦ）２）、リチウムヘクトライト（Ｌｉ０．３３Ｍｇ２．６７Ｌｉ０．３３Ｓｉ４．０Ｏ１０（ＯＨ又はＦ）２）及びサポナイト（Ｎａ０．３３Ｍｇ２．６７ＡｌＳｉ４．０Ｏ１０（ＯＨ）２）等の合成スメクタイトが挙げられる。本発明では、天然物、合成物をそれぞれ単独で用いても良いし、組み合わせて用いても良い。 The layered silicate includes synthetic products obtained by artificial synthesis in addition to naturally occurring natural products. Examples of the composite include fluorine phlogopite (KMg 3 AlSi 3 O 10 F), potassium tetrasilicon mica (KMg 2.5 Si 4 O 10 F 2 ), and sodium tetrasilicon mica (NaMg 2.5 Si 4 O 10). F 2 ), synthetic mica such as sodium teniolite (NaMg 2 LiSi 4 O 10 F 2 ) and lithium teniolite (LiMg 2 LiSi 4 O 10 F 2 ), sodium hectorite (Na 0.33 Mg 2.67 Li 0 .33 Si 4.0 O 10 (OH or F) 2 ), lithium hectorite (Li 0.33 Mg 2.67 Li 0.33 Si 4.0 O 10 (OH or F) 2 ) and saponite (Na 0 Synthetic smectites such as .33 Mg 2.67 AlSi 4.0 O 10 (OH) 2 ). In the present invention, natural products and synthetic products may be used alone or in combination.
上記層状珪酸塩には、水と接触すると結晶の層間に水分子を吸着して膨潤し、延いては劈開し、バラバラになって水中に分散する膨潤性層状珪酸塩と、水と接触しても変化のない非膨潤性層状珪酸塩とがある。本発明の難燃性水系塗料組成物において、無機系層状化合物として膨潤性層状珪酸塩を用いた場合、無機系層状化合物の分散性が良好で沈降し難く、塗装作業性が良好な傾向を示す。 In contact with water, the layered silicate swells by adsorbing water molecules between the layers of the crystals, and then cleaves and dissociates and disperses in water. There is also a non-swellable layered silicate that does not change. In the flame retardant water-based coating composition of the present invention, when a swellable layered silicate is used as the inorganic layered compound, the dispersibility of the inorganic layered compound is good and the sedimentation is difficult, and the coating workability tends to be good. .
膨潤性層状珪酸塩の例としては、天然物ではハロイサイトやスメクタイトが挙げられ、合成物では、上述の合成雲母、又は上述の合成スメクタイトが挙げられる。 Examples of the swellable layered silicate include halloysite and smectite for natural products, and examples of the synthetic product include the above-described synthetic mica or the above-described synthetic smectite.
本発明の難燃性水系塗料組成物において、無機系層状化合物の配合量は、樹脂１００質量部に対して、２〜２００質量部であることが好ましい。 In the flame-retardant water-based coating composition of the present invention, the amount of the inorganic layered compound is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the resin.
（Ｄ）シランカップリング剤
本発明の難燃性水系塗料組成物は、更にシランカップリング剤を含有することが好ましい。シランカップリング剤を用いることによって、架橋密度が高まり、耐水性が向上する傾向がある。シランカップリング剤としては、公知のものを制限なく、使用することが出来る。なお、シランカップリング剤の配合量は、樹脂１００質量部に対して、０．３〜５質量部であることが好ましい。該シランカップリング剤の配合量が０．３質量部未満であると、シランカップリング剤の添加効果が得られにくく、一方、５質量部を超えると、塗膜が割れやすくなる傾向がある。
(D) Silane coupling agent It is preferable that the flame-retardant water-based coating composition of this invention contains a silane coupling agent further. By using a silane coupling agent, there exists a tendency for a crosslinking density to increase and for water resistance to improve. Any known silane coupling agent can be used without limitation. In addition, it is preferable that the compounding quantity of a silane coupling agent is 0.3-5 mass parts with respect to 100 mass parts of resin. When the blending amount of the silane coupling agent is less than 0.3 parts by mass, it is difficult to obtain the effect of adding the silane coupling agent, and when it exceeds 5 parts by mass, the coating film tends to break.
本発明の難燃性水系塗料組成物には、上記成分以外に、公知の塗料用添加剤を、本発明に対して影響を及ぼさない範囲で適宜配合することができる。その代表例としては、顔料、湿潤剤、分散剤、乳化剤、増粘剤、沈降防止剤、皮張り防止剤、たれ防止剤、消泡剤、色分かれ防止剤、レベリング剤、乾燥剤、可塑剤、防カビ剤、抗菌剤、殺虫剤、防腐剤、光安定化剤、紫外線吸収剤、帯電防止剤及び導電性付与剤等が挙げられる。顔料としては、着色顔料、体質顔料及び金属粉顔料等が挙げられ、塗膜の着色やツヤ、塗装作業性、塗膜の強度、物性等に応じて適宜選択して使用する。 In addition to the above-mentioned components, a known paint additive can be appropriately blended in the flame-retardant water-based paint composition of the present invention within a range that does not affect the present invention. Typical examples include pigments, wetting agents, dispersants, emulsifiers, thickeners, anti-settling agents, anti-skinning agents, anti-sagging agents, antifoaming agents, anti-color separation agents, leveling agents, drying agents, and plasticizers. , Antifungal agents, antibacterial agents, insecticides, preservatives, light stabilizers, ultraviolet absorbers, antistatic agents and conductivity-imparting agents. Examples of the pigment include coloring pigments, extender pigments, metal powder pigments, and the like, which are appropriately selected and used according to the coloring and gloss of the coating film, the coating workability, the strength of the coating film, the physical properties, and the like.
なお、本発明の難燃性水系塗料組成物は、上記水系バインダー樹脂及び難燃剤と、必要に応じて適宜選択される各種成分とを混合することにより調製できるが、本発明の難燃性水系塗料組成物は、使用される成分を主剤と硬化剤に分け、使用の直前に主剤と硬化剤を混合して調製する混合タイプであってもよい。混合タイプである場合、混合は常温で行われ、混合機を適宜使用できる。 The flame retardant water-based paint composition of the present invention can be prepared by mixing the water-based binder resin and the flame retardant and various components appropriately selected as necessary. The coating composition may be a mixed type prepared by dividing the components used into a main agent and a curing agent and mixing the main agent and the curing agent immediately before use. In the case of a mixing type, mixing is performed at room temperature, and a mixer can be used as appropriate.
また、本発明の難燃性水系塗料組成物は、シーラー、特に下塗塗料として塗装されることが好ましく、これにより、難燃性が確実に向上できる。 Moreover, it is preferable that the flame retardant water-based coating composition of the present invention is applied as a sealer, particularly as a base coating, whereby the flame retardancy can be reliably improved.
次に、本発明の難燃性塗膜を詳細に説明する。本発明の難燃性塗膜は、上述の難燃性水系塗料組成物を被塗物、より具体的には基材に塗布し、成膜させることにより得られる難燃性塗膜であるが、該難燃性塗膜の４０℃／９０％ＲＨ条件下での水蒸気透過度は、５０ｇ／ｍ２／Ｄａｙ以下であることが好ましい。 Next, the flame retardant coating film of the present invention will be described in detail. The flame-retardant coating film of the present invention is a flame-retardant coating film obtained by applying the above-mentioned flame-retardant water-based coating composition to an object to be coated, more specifically, a substrate, and forming a film. The water vapor permeability of the flame retardant coating film at 40 ° C./90% RH is preferably 50 g / m 2 / Day or less.
ここで、上記難燃性水系塗料組成物を塗布する方法としては、従来公知の塗布方法を特に制限無く使用することができる。具体的には、ディッピング法、スピンコート法、フローコート法、ロールコート法、スプレーコート法、ブレードコート法及びエアーナイフコート法等が挙げられる。このうち、膜厚の制御を容易に行うことができることから、スプレーコート法、及びロールコート法が好ましい。 Here, as a method for applying the flame retardant aqueous coating composition, a conventionally known application method can be used without any particular limitation. Specific examples include a dipping method, a spin coating method, a flow coating method, a roll coating method, a spray coating method, a blade coating method, and an air knife coating method. Among these, the spray coating method and the roll coating method are preferable because the film thickness can be easily controlled.
また、上記被塗物としては、主に建築物や、建材等の基材が挙げられる。建材としては、例えば、窯業系サイディングボード、フレキシブルボードや、珪酸カルシウム板、石膏スラグバーライト板、木片セメント板、石綿セメント板、パルプセメント板、プレキャストコンクリート板、軽量気泡コンクリート（ＡＬＣ）板及び石膏ボード等の無機建材板、並びにアルミニウム、鉄及びステンレス等の金属建材板等が代表的なものとして挙げられる。被塗物の表面性状は、特に制限はなく、表面が平滑なものであっても、凹凸形状を有するものであってもよいが、好ましくは微細な凹凸があるものが、塗膜の接着性を良くする点で好ましい。 Moreover, as said coating object, base materials, such as a building and a building material, are mainly mentioned. Examples of building materials include ceramic siding boards, flexible boards, calcium silicate boards, gypsum slag bar light boards, wood chip cement boards, asbestos cement boards, pulp cement boards, precast concrete boards, lightweight cellular concrete (ALC) boards, and gypsum. Representative examples include inorganic building material plates such as boards, and metal building material plates such as aluminum, iron, and stainless steel. The surface property of the object to be coated is not particularly limited, and the surface property may be smooth or may have an uneven shape. It is preferable in terms of improving.
上記難燃性水系塗料組成物の塗布量は、塗布する被塗物の種類や用途に応じて適宜調整することができるが、乾燥膜厚が１０〜１２０μｍになるような量が好ましい。また、それに応じて、被装物表面に形成される塗膜の膜厚は、塗布量に依存している。 The coating amount of the flame retardant aqueous coating composition can be appropriately adjusted according to the type and application of the object to be coated, but is preferably such that the dry film thickness is 10 to 120 μm. Accordingly, the film thickness of the coating film formed on the surface of the object depends on the coating amount.
また、上記難燃性水系塗料組成物の成膜は、該難燃性水系塗料組成物を塗布した後、常温下、又は適度な加温下でこれを放置し、乾燥させることによって行われる。 The film formation of the flame retardant water-based coating composition is performed by applying the flame retardant water-based coating composition and then allowing it to stand at room temperature or under moderate heating and drying.
本発明の難燃性塗膜は、４０℃／９０％ＲＨ条件下での水蒸気透過度が、５０ｇ／ｍ２／Ｄａｙ以下であることが好ましい。上記無機系層状化合物を含む難燃性水系塗料組成物を用いることによって、水蒸気透過度を上記特定した範囲内に調整することができる。なお、４０℃／９０％ＲＨ条件下での水蒸気透過度は、ＪＩＳ Ｋ７１２９Ａに規定の感湿センサー法に準拠して測定できるが、かかる感湿センサー法では、被塗物から分離された塗膜（単離膜）に対して、水蒸気透過度を測定することができる。４０℃／９０％ＲＨ条件下での水蒸気透過度が、５０ｇ／ｍ２／Ｄａｙを超えると、水蒸気の透過性が高くなり過ぎ、建材等の被塗物が反りやすくなる。 The flame-retardant coating film of the present invention preferably has a water vapor permeability of 50 g / m 2 / Day or less under 40 ° C./90% RH conditions. By using a flame retardant water-based paint composition containing the inorganic layered compound, the water vapor permeability can be adjusted within the specified range. In addition, although the water vapor transmission rate on 40 degreeC / 90% RH conditions can be measured based on the humidity sensor method prescribed | regulated to JISK7129A, in this moisture sensor method, the coating film isolate | separated from to-be-coated material Water vapor permeability can be measured for (isolated membrane). When the water vapor permeability under the condition of 40 ° C./90% RH exceeds 50 g / m 2 / Day, the water vapor permeability becomes too high, and the object to be coated such as building materials tends to warp.
次に、本発明の建築板を詳細に説明する。本発明の建築板は、上述の難燃性塗膜を備えることを特徴とし、該難燃性塗膜は、例えば、上述の建材板上に形成されている。 Next, the building board of this invention is demonstrated in detail. The building board of the present invention is provided with the above-mentioned flame retardant paint film, and this flame retardant paint film is formed on the above-mentioned building material board, for example.
また、上記難燃性水系塗料組成物は、上述したように、下塗塗料として塗装されることが好ましいため、本発明の建築板は、上記難燃性塗膜上に上塗塗膜を形成させることもできる。上塗塗膜は、上記難燃性水系塗料組成物と同様の方法によって形成できる。 In addition, since the flame retardant water-based paint composition is preferably applied as an undercoat as described above, the building board of the present invention forms a top coat on the flame retardant paint. You can also. The top coat film can be formed by the same method as that for the flame retardant water-based paint composition.
ここで、上塗塗膜の形成に使用できる塗料には、公知の上塗塗料が使用できる。該上塗塗料の成分には、アクリル樹脂、フェノール樹脂、尿素樹脂、エポキシ樹脂、ウレタン樹脂、ポリエステル樹脂、アルキド樹脂、アミノアルキド樹脂、ニトリルゴム、ポリクロロプレン、メラミン樹脂、ケイ素樹脂、シリコーン樹脂、アクリルシリコーン樹脂、フッ素樹脂、ポリブテン樹脂、ポリアミド樹脂、ビニル樹脂、塩素化オレフィン樹脂、スチレン・ブタジエン共重合樹脂、エチレン−酢酸ビニル共重合樹脂、クマロン樹脂、シリコーンゴム及び塩化ゴム等が挙げられる。 Here, as the paint that can be used for forming the top coat film, a known top coat paint can be used. The components of the top coat include acrylic resin, phenol resin, urea resin, epoxy resin, urethane resin, polyester resin, alkyd resin, aminoalkyd resin, nitrile rubber, polychloroprene, melamine resin, silicon resin, silicone resin, acrylic silicone Examples thereof include resins, fluororesins, polybutene resins, polyamide resins, vinyl resins, chlorinated olefin resins, styrene / butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, coumarone resins, silicone rubber, and chlorinated rubber.
これらの上塗塗料も難燃性を付与できるものが好ましく、また、燃焼時に有毒性ガス等の発生が少ない塗料が望まれる。なお、上塗り塗料には、上記成分の他、一般に用いられる顔料、具体例としては着色顔料、体質顔料及び金属粉顔料等が配合でき、更には、一般の塗料に用いられる添加剤等も使用できる。添加剤としては、上記難燃性水系塗料組成物で述べた塗料用添加剤が挙げられる。 These top coats are also preferably those that can impart flame retardancy, and paints that generate little toxic gas during combustion are desired. In addition to the above components, pigments that are generally used, specifically, coloring pigments, extender pigments, metal powder pigments, and the like can be blended in the top coat paint, and additives that are used in general paints can also be used. . Examples of the additive include paint additives described in the above flame-retardant water-based paint composition.
以下、実施例及び比較例を挙げて本発明を更に詳細に説明する。以下に示す塗料及び試験方法に従って試験を実施した。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The test was carried out according to the paints and test methods shown below.
１−１．アクリル樹脂系エマルションＥＭ１の調製例
撹拌装置、温度計、冷却管及び滴下装置を備えた反応器中に、イオン交換水２２質量部、ラテムルＰＤ−１０４（商品名、ポリオキシアルキレンアルケニルエーテル硫酸エステル塩：花王株式会社製、固形分２０質量％）０．８質量部をそれぞれ仕込み、反応器内部を窒素で置換しながら、８０℃まで昇温し、その後、過硫酸カリウム（重合開始剤）０．１質量部を加え、続いて、表１に示す処方に従い別容器で予め攪拌混合して調製した原料エマルションａ１を、表１に示す合計質量部で、３時間かけて連続滴下した。滴下終了後、これをさらに２時間８０℃に保持した後、４０℃に降温した。次いで２５質量％アンモニア水０．２６質量部でｐＨ９．０に調整し、消泡剤０．０２質量部、防腐剤０．０２質量部を加えて、加熱残分４８質量％のアクリル樹脂系エマルションＥＭ１を得た。なお、ＥＭ１中に含まれるアクリル樹脂は、アクリルシリコーン樹脂である。
1-1. Preparation Example of Acrylic Resin Emulsion EM1 In a reactor equipped with a stirrer, a thermometer, a condenser tube and a dropping device, 22 parts by mass of ion-exchanged water, Lateml PD-104 (trade name, polyoxyalkylene alkenyl ether sulfate ester salt) : Manufactured by Kao Corporation, solid content of 20% by mass), 0.8 parts by mass of each were charged, and the temperature inside the reactor was increased to 80 ° C. while replacing the interior with nitrogen, and then potassium persulfate (polymerization initiator) 0. 1 part by mass was added, and then a raw material emulsion a1 prepared by stirring and mixing in a separate container in advance according to the formulation shown in Table 1 was continuously added dropwise over 3 hours at a total part by mass shown in Table 1. After completion of dropping, this was further maintained at 80 ° C. for 2 hours, and then cooled to 40 ° C. Next, the pH is adjusted to 9.0 with 0.26 parts by mass of 25% by mass aqueous ammonia, 0.02 parts by mass of antifoaming agent and 0.02 parts by mass of preservative are added, and an acrylic resin emulsion having a heating residue of 48% by mass is added. EM1 was obtained. In addition, the acrylic resin contained in EM1 is an acrylic silicone resin.
１−２．アクリル樹脂系エマルションＥＭ２〜ＥＭ８の調製例
表２に示す配合処方を用いる以外は、アクリル樹脂系エマルションＥＭ１の調製例と同様の方法により、アクリル樹脂系エマルションＥＭ２〜ＥＭ８を調製した。なお、アクリル樹脂系エマルションＥＭ２〜ＥＭ８についても、加熱残分は４８質量％である。また、ＥＭ２〜ＥＭ７中に含まれるアクリル樹脂は、アクリルシリコーン樹脂であり、ＥＭ８中に含まれるアクリル樹脂は、（メタ）アクリルモノマーとスチレンとの共重合体である。
1-2. Preparation Examples of Acrylic Resin Emulsions EM2 to EM8 Acrylic resin emulsions EM2 to EM8 were prepared by the same method as the preparation examples of the acrylic resin emulsion EM1, except that the formulation shown in Table 2 was used. In addition, also about acrylic resin-type emulsion EM2-EM8, a heating residue is 48 mass%. Moreover, the acrylic resin contained in EM2-EM7 is an acrylic silicone resin, and the acrylic resin contained in EM8 is a copolymer of a (meth) acryl monomer and styrene.
なお、ガラス転移温度、酸価、加熱残分及び樹脂含有量（理論値）は、下記の方法で測定された。
＜ガラス転移温度＞
下記ＦＯＸ式を用いて、アクリル樹脂のガラス転移温度（Ｔｇ）を算出した。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・＋Ｗｉ／Ｔｇｉ＋・・・＋Ｗｎ／Ｔｇｎ
上記ＦＯＸ式において、Ｔｇは、ｎ種類のモノマーからなるポリマーのガラス転移温度（Ｋ）であり、Ｔｇ（１、２、ｉ、ｎ）は、各モノマーのホモポリマーのガラス転移温度（Ｋ）であり、Ｗ（１、２、ｉ、ｎ）は、各モノマーの質量分率であり、Ｗ１＋Ｗ２＋・・・＋Ｗｉ＋・・・＋Ｗｎ＝１である。
＜酸価＞
樹脂１ｇ中の遊離カルボン酸を中和するのに要する水酸化カリウムのｍｇ数を定量した。
＜加熱残分＞
エマルション１．０ｇをアルミカップに精秤し、これを１５０℃オーブンで３０分乾燥させた。乾燥後、残留物の質量を精秤し、元の質量に対する残留物の質量の割合を加熱残分（質量％）として求めた。
＜樹脂含有量（理論値）＞
原料エマルションの調製に使用されたモノマーから樹脂含有量（理論値）を求めた。
The glass transition temperature, acid value, heating residue, and resin content (theoretical value) were measured by the following methods.
<Glass transition temperature>
The glass transition temperature (Tg) of the acrylic resin was calculated using the following FOX equation.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
In the FOX formula, Tg is a glass transition temperature (K) of a polymer composed of n types of monomers, and Tg (1, 2, i, n) is a glass transition temperature (K) of a homopolymer of each monomer. Yes, W (1, 2, i, n) is the mass fraction of each monomer, and W1 + W2 +... + Wi +.
<Acid value>
The number of mg of potassium hydroxide required to neutralize free carboxylic acid in 1 g of resin was determined.
<Remaining heating>
1.0 g of the emulsion was precisely weighed into an aluminum cup and dried in a 150 ° C. oven for 30 minutes. After drying, the mass of the residue was precisely weighed, and the ratio of the mass of the residue to the original mass was determined as a heating residue (mass%).
<Resin content (theoretical value)>
The resin content (theoretical value) was determined from the monomers used for the preparation of the raw material emulsion.
２．水系塗料組成物の調製例
表３〜４に示す配合処方に従い、各原料を混合した後、公知の手法によって分散させて、実施例１〜１２及び比較例１に示す水系塗料組成物を調製した。
2. Preparation Examples of Water-Based Paint Composition According to the formulation shown in Tables 3 to 4, the raw materials were mixed and then dispersed by a known method to prepare water-based paint compositions shown in Examples 1 to 12 and Comparative Example 1. .
尚、表中に記載される原料の詳細を以下に示す。
＊１：Ｒ５Ｎ（酸化チタン、堺化学社製）
＊２：ＢＹＫ−１８１（分散剤、ビックケミー社製）
＊３：ＶＧ２（増粘剤、ローム＆ハース社製）
＊４：ＳＮ６１７（増粘剤、サンノプコ社製）
＊５：ＢＹＫ−０１８（消泡剤、ビックケミー社製）
＊６：プラネロンＤＢ１０２（ハロゲン系難燃剤、三井化学ファイン社製）
＊７：ピロガードＡＮ８００Ｔ（アンチモン系難燃助剤、第一工業製薬社製）
＊８：ＮＴＳ−５（無機系層状化合物（ナトリウム四ケイ素雲母、合成マイカ、平均粒子径１０〜１５μｍ、アスペクト比１５００）、トピー工業社製）
＊９：ＳＹＡ−４１Ｒ（無機系層状化合物（天然マイカ、平均粒子径４０〜４５μｍ、アスペクト比８０）、ヤマグチマイカ社製））
＊１０：ＫＢＭ−４０３（シランカップリング剤、信越シリコーン社製）
In addition, the detail of the raw material described in a table | surface is shown below.
* 1: R5N (titanium oxide, manufactured by Sakai Chemical Co., Ltd.)
* 2: BYK-181 (dispersant, manufactured by Big Chemie)
* 3: VG2 (Thickener, manufactured by Rohm & Haas)
* 4: SN617 (Thickener, manufactured by San Nopco)
* 5: BYK-018 (antifoaming agent, manufactured by Big Chemie)
* 6: Planetron DB102 (halogen flame retardant, manufactured by Mitsui Chemicals Fine)
* 7: Pyroguard AN800T (antimony flame retardant aid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
* 8: NTS-5 (inorganic layered compound (sodium tetrasilicon mica, synthetic mica, average particle size 10-15 μm, aspect ratio 1500), manufactured by Topy Industries, Ltd.)
* 9: SYA-41R (inorganic layered compound (natural mica, average particle size 40-45 μm, aspect ratio 80), manufactured by Yamaguchi Mica))
* 10: KBM-403 (silane coupling agent, manufactured by Shin-Etsu Silicone)
３．塗膜形成
縦１０ｃｍ×横１０ｃｍ×厚さ１６ｍｍの大きさの窯業系建材（セメント質と繊維質とを主成分とする成型木片セメント板）及びポリプロピレン板を用意し、これらを基材試験片とした。
上述の実施例１〜１２及び比較例１の水系塗料組成物を、加熱残分が１０質量％になるように、水で希釈した後、上記２種類の基材試験片のそれぞれに、スプレーコート法にて、乾燥時の膜厚が８０〜１００μｍとなるように塗装し、１２０℃で４５分乾燥させて、塗膜を形成し、２種類の難燃性塗膜付き基材を得た。得られた塗膜に対して、下記の評価を行った。結果を表５〜６に示す。
3. Film formation 10cm long x 10cm wide x 16mm thick ceramic building materials (molded wood cement board with cement and fiber as main components) and polypropylene board are prepared as base material test pieces. did.
After diluting the water-based coating compositions of Examples 1 to 12 and Comparative Example 1 with water so that the heating residue is 10% by mass, each of the two types of substrate test pieces is spray coated. The film was coated by the method so that the film thickness at the time of drying would be 80 to 100 μm, and dried at 120 ° C. for 45 minutes to form a coating film to obtain two types of base materials with flame retardant coating film. The following evaluation was performed with respect to the obtained coating film. The results are shown in Tables 5-6.
４．塗膜評価
＜水蒸気透過度＞
ポリプロピレン板上に形成された塗膜を剥がし、膜厚７５μｍの単離膜を得た。ＪＩＳ Ｋ７１２９Ａに規定の感湿センサー法に準拠して、水蒸気透過度測定装置ＬＹＳＳＹ社製「ＰＥＲＭＥＡＢＩＬＩＴＹ ＴＥＳＴＥＲ Ｌ８０−５０００」を用い、４０℃／９０％ＲＨの条件下での水蒸気透過度を測定した。
＜発熱性試験＞
成型木片セメント板上に塗膜を形成して得られた難燃性塗膜付き基材について、コーンカロリーメーター（（株）東洋精機製作所製 ＣＯＮＥ ＩＩＩ）を用いて、ＩＳＯ５６６０に準拠した発熱性試験を行った。電気ヒーターで５０ｋＷ／ｍ２の輻射熱を２０分間放射した状態における発熱速度を測定し、得られた発熱速度を輻射熱放射時間で積分して総発熱量（ＭＪ／ｍ２）を算出した。総発熱量を下記の表５〜６に示す。
＜耐水性評価＞
成型木片セメント板上に塗膜を形成して得られた難燃性塗膜付き基材を２０℃の水に１０日間浸漬させた後、これを取り出して常温で乾燥させた。乾燥後の塗膜の外観を評価した。
◎：ふくれが全く認められない。
○：微小なふくれがわずかに認められる。
△：微小なふくれが認められる。
×：おおきなふくれが認められる。
＜凍結融解性＞
成型木片セメント板上に塗膜を形成して得られた難燃性塗膜付き基材に対して、凍結融解試験機（（株）マルイ製ＭＩＴ−１６８２−Ａ３型）を用い、凍結融解サイクルを３００回行い、試験後の塗膜状態を目視にて判定した。なお、凍結融解サイクルは、−２０℃の空気中で２時間の凍結段階と、２０℃の水中で１時間の融解段階とからなる。
○：塗膜にクラック及び剥離の両方が発生しない。
△：塗膜にクラック又は剥離が少し発生する。
×：塗膜にクラック又は剥離が顕著に発生する。
＜耐ブロッキング性＞
成型木片セメント板上に塗膜を形成して得られた難燃性塗膜付き基材を２枚用意した。次に、２枚の難燃性塗膜付き基材を６０℃の雰囲気中で１時間放置し、その後、塗膜が形成されている面同士を重ね合わせ、試験板を用意した。試験板上に、３００ｇ／ｃｍ２の荷重をかけ、その状態で６０℃の温度にて２４時間静置させ、その後、各難燃性塗膜付き基材を分離し、塗膜表面の状態を目視にて観察し、以下の評価基準に基づいて評価した。
（評価基準）
◎：変化なし
○：塗膜表面に艶変化のみがわずかに認められる。
△：塗膜の剥がれ部分がわずかに存在する。
×：塗膜の剥がれ部分が多数存在する。
4). Coating film evaluation <water vapor permeability>
The coating film formed on the polypropylene plate was peeled off to obtain an isolated film having a thickness of 75 μm. In accordance with the moisture sensitive sensor method defined in JIS K7129A, the water vapor transmission rate under the condition of 40 ° C./90% RH was measured using a “PERMEABILITY TESTER L80-5000” manufactured by LYSSY.
<Exothermic test>
About the base material with a flame-retardant coating film obtained by forming a coating film on a molded wood chip cement board, using a cone calorimeter (CONE III manufactured by Toyo Seiki Seisakusho Co., Ltd.), an exothermic test according to ISO5660 Went. The heat generation rate in a state where 50 kW / m 2 of radiant heat was emitted for 20 minutes with an electric heater was measured, and the total heat generation amount (MJ / m 2 ) was calculated by integrating the obtained heat generation rate with the radiant heat radiation time. The total calorific value is shown in Tables 5 to 6 below.
<Water resistance evaluation>
A substrate with a flame retardant coating film obtained by forming a coating film on a molded wood chip cement plate was immersed in water at 20 ° C. for 10 days, and then taken out and dried at room temperature. The appearance of the coating film after drying was evaluated.
A: No blistering is observed.
○: Slight minute blisters are observed.
(Triangle | delta): A minute blister is recognized.
X: Large blistering is recognized.
<Freeze-thaw property>
Freezing and thawing cycle is performed on a base material with a flame retardant coating film obtained by forming a coating film on a molded wood chip cement board using a freeze-thaw tester (MIT-682-A3 type manufactured by Marui Co., Ltd.). The coating state after the test was visually determined. The freeze-thaw cycle consists of a freezing stage for 2 hours in air at −20 ° C. and a melting stage for 1 hour in water at 20 ° C.
○: Neither crack nor peeling occurs in the coating film.
Δ: Some cracking or peeling occurs in the coating film.
X: A crack or peeling generate | occur | produces notably in a coating film.
<Blocking resistance>
Two base materials with a flame retardant coating film obtained by forming a coating film on a molded wood chip cement board were prepared. Next, two base materials with a flame retardant coating film were allowed to stand in an atmosphere of 60 ° C. for 1 hour, and then the surfaces on which the coating film was formed were overlapped to prepare a test plate. On the test plate, a load of 300 g / cm 2 was applied, and in that state, the plate was allowed to stand at a temperature of 60 ° C. for 24 hours. Thereafter, each substrate with a flame-retardant coating film was separated, and the state of the coating film surface was determined. It observed visually and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: No change B: Only slight gloss change is observed on the coating film surface.
Δ: There is a slight peeling portion of the coating film.
X: Many peeling parts of a coating film exist.
５．結果
本発明の難燃性水系塗料組成物は、難燃性に優れることに加え、吸湿量も一般的な水系塗料と比べて低く、耐水性にも優れるため、下塗り塗料として十分な性能を有しており、塗膜形成後の窯業建材板の反りもかなり軽減される。従って、本発明の難燃性水系塗料組成物によれば、被塗物の種類や用途の範囲が著しく広がる。
5. ResultsThe flame-retardant water-based paint composition of the present invention has sufficient flame retardant properties, has a low moisture absorption compared to general water-based paints, and is excellent in water resistance. Therefore, the warping of the ceramic building material board after the coating is formed is considerably reduced. Therefore, according to the flame-retardant water-based coating composition of the present invention, the types of coating objects and the range of applications are remarkably expanded.
Claims (11)
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