JP3996418B2 - Method for producing coating layer - Google Patents
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- JP3996418B2 JP3996418B2 JP2002090838A JP2002090838A JP3996418B2 JP 3996418 B2 JP3996418 B2 JP 3996418B2 JP 2002090838 A JP2002090838 A JP 2002090838A JP 2002090838 A JP2002090838 A JP 2002090838A JP 3996418 B2 JP3996418 B2 JP 3996418B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、床の基材の表面に滑り難い塗膜層を作製するための方法に係り、特に限定されるものではないが、例えば工場内等の床であって水に濡れる機会が多く、水に濡れた場合に滑り易くなるような床表面に、滑り難い塗膜層を設けるのに適した塗膜層の作製方法に関する。
【０００２】
【従来の技術】
例えば、表面に塗膜層を有する床材の滑り止め方法として、従来より、スプレーダストを利用して塗膜表面に凹凸を形成する方法、塗布した表面に骨材を混入する方法、塗料中に骨材や高分子パウダーを混入する方法（特開平８−２１７，９９４、特開平９−８７，５４７号の各公報）等が知られており、また、鉱物材料からなる床材の表面にレーザーでマイクロ クレータの形の微***を統計的に分布させても設ける方法（特表平１１−５０５，１８５号公報）や、薬液でエッチングする方法（特許第２，５７４，６４６号公報）等も知られている。
【０００３】
しかしながら、塗膜表面に凹凸を形成したり、骨材を散布する方法においては、形成される塗膜表面がザラザラになって平滑性が無くなり、耐汚染性が著しく低下するという問題があり、また、塗料中に骨材や高分子パウダーを混入させた場合にも、同様に平滑性が無くなるほか、散布物の均一性が乏しく塗膜外観を著しく低下させるという問題がある。また、レーザーでマイクロ クレータの形の微***を設ける方法では処理できる基材の大きさに制限があるほか、床被覆材の施設現場では作業が困難であるという問題があり、更に、薬液でエッチングする方法については基材が石やタイル等の鉱物材料に限られるほか、薬液の危険性や、中和後の洗浄水の廃棄処理が面倒であるという問題がある。
【０００４】
また、塗膜を多孔質化する方法として、樹脂を水不溶性有機溶剤に分散又は溶解させて得られた樹脂液と平均粒子径１μｍ以下の水溶性無機塩粒子と、平均粒子径１μｍ以下の顔料とを混合して得られた有機溶剤系塗料を基材に塗装し、次いで有機溶剤を揮発させて乾燥塗膜又は硬化塗膜を得たのち、その塗膜中の水溶性無機塩粒子を水により溶出させる方法が提案されている（特開2001-179,173号公報）。
【０００５】
しかしながら、この方法により多孔質化される塗膜については、基材に関して金属、コンクリート、ガラス等の無機質やプラスチック、木材、繊維、塗膜等の有機質、及びこれらの物が組み合わさったものが使用できると説明されているものの、上記の塗料中に骨材や高分子パウダーを混入する方法と同様に、空孔が塗膜内部から基材表面にまで達し、塗膜強度等の塗膜物性が顕著に低下するため、表面に塗膜層を有する床材の滑り止めの方法としては適さない。
【０００６】
【発明が解決しようとする課題】
そこで、本発明者らは、形成される塗膜層の塗膜外観、密着性、塗膜強度等の塗膜物性を低下させることなく、滑り止め性、特に湿潤時の滑り止め性に優れ、しかも、現場施工も容易である滑り難い塗膜層の作製方法について鋭意検討した結果、基材表面に塗布した後に上記水性散布材を散布し、塗膜形成材層が乾燥又は硬化した後に上記水性散布材を除去することにより、基材表面に滑り難い塗膜層を容易に作製できることを見出し、本発明を完成した。
【０００７】
従って、本発明の目的は、形成される塗膜層の塗膜外観、密着性、塗膜強度等の塗膜物性を低下させることなく、滑り止め性、特に湿潤時の滑り止め性に優れ、しかも、現場施工も容易である塗膜層の作製方法を提供することにある。
【０００８】
【課題を解決するための手段】
すなわち、本発明は、床の基材表面に水に対して不溶性若しくは難溶性の塗膜形成材を塗布し、塗布された塗膜形成材層が乾燥し又は硬化する前に、この塗膜形成材層の表面に、水溶性固体物質、水溶性液体物質、水溶性固体物質及び／又は水溶性液体物質の水性溶液又は水性懸濁液、及び水から選ばれた、前記塗膜形成材層中に溶解しない性質を有する水性散布材を散布し、塗膜形成材層を乾燥又は硬化させた後に上記水性散布材を除去し、表面に面積率が３％以上５０％以下で平均径が１μｍ以上１，０００μｍ以下の多数の微***を有する塗膜層を形成する、滑り難い塗膜層の作製方法である。
【０００９】
本発明において、基材表面に塗布される水に対して不溶性若しくは難溶性の塗膜形成材については、水に対して不溶性若しくは難溶性であり、基材表面に塗布されて塗膜層を形成するものであればどのようなものでもよい。
【００１０】
ここで、本発明で用いる塗膜形成材としては、従来より塗料成分の１つとして用いられている各種の樹脂成分、例えば非架橋タイプの樹脂や、自己架橋性あるいは硬化剤による外部架橋性の架橋タイプの樹脂等を挙げることができるほか、これらの樹脂成分にアルコール系、炭化水素系、ケトン系、エステル系等の溶剤や、流動性調整剤、硬化触媒、紫外線吸収剤、熱安定剤、開始剤等の補助剤や、着色顔料、体質顔料、防触顔料、金属顔料等の顔料や、染料等その他の成分を配合したものを挙げることができ、この塗膜形成材は一液型に配合されても、また、二液型に配合されてもよい。
【００１１】
上記非架橋タイプの樹脂としては、具体的には、エポキシ樹脂、ポリエステル樹脂、アクリル樹脂、ビニル系共重合体、塩化ビニル樹脂、酢酸ビニル掛脂、塩化ビニル−酢酸ビニル樹脂共重合体、繊維素樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ナイロン、ＡＢＳ樹脂、ポリカーボネート、フェノール樹脂、フッ素樹脂、シリコーン樹脂等やこれらの変性樹脂等を例示することができる。
【００１２】
また、上記架橋タイプの樹脂としては、具体的には、アミノ硬化型アクリル樹脂、アミノ硬化型ポリエステル樹脂、（ブロック）ポリイソシアネート硬化型アクリル樹脂、（ブロック）ポリイソシアネート硬化型ポリエステル樹脂、無水酸硬化型エポキシ樹脂、多酸硬化型エポキシ樹脂、加水分解性シリル基含有樹脂、酸化硬化型アルキド樹脂、活性エネルギー線硬化型樹脂等を例示することができる。
【００１３】
本発明においては、基材表面に上記塗膜形成材を塗布し、乾燥し又は硬化する前の塗膜形成材層を形成せしめるが、この基材表面には、通常の塗料の場合と同様に、吸い込み防止や付着性向上等を目的に、上記塗膜形成材層を形成する前の基材表面に予めシーラーやプライマー等の下地層を形成し、この下地層の上に塗膜形成材層を形成してもよく、また、必要により最上層となる塗膜形成材層を形成する前に、この塗膜形成材と同じ又は異なる塗膜形成材を塗布して複数層の塗膜層を形成するようにしてもよい。
【００１４】
ここで、基材表面への塗膜形成材の塗布方法については、従来より知られている公知の塗装手段を採用することができ、例えば、スプレー塗装、ローラー塗装、刷毛塗装、コテ塗装、バーコーター塗装等を挙げることができる。
【００１５】
本発明において、水性散布材として塗膜形成材層の表面に散布する水溶性固体物質については、それが上記塗膜形成材層中に溶解せず、また、塗膜形成材層が乾燥し又は硬化した後に水等を散布して容易に除去できるものであり、更に、望ましくは水性散布材を除去した後の塗膜層に平均径１μm以上の微***を形成できるものであれば特に制限はないが、好ましく平均粒径が１０００μｍ以下であるのがよく、より好ましくは１μ以上５００μｍ以下、更により好ましくは５μｍ以上２００μｍ以下であるのがよい。水溶性固体物質の平均粒径が１０００μｍを超えると、塗膜形成材層については、より厚い膜厚が必要となり、不経済であると共に、塗膜の外観が著しく低下し、反対に、水溶性固体物質の平均粒径が１μm未満では、形成される微***の大きさが小さく、滑り止め効果があまり期待できなくなると共に、塗膜層の経時的摩耗により滑り止め効果が持続する期間が短くなるため好ましくない。
【００１６】
このような水溶性固体物質としては、無機の水溶性固体物質として、弱酸と弱塩基、弱酸と強塩基、及び強酸と弱塩基の中和により得られる塩があり、例えば、塩酸、硫酸、炭酸等の無機酸及びその誘導体からなる群から選ばれた１種又は２種以上の酸化合物と、ナトリウム、カリウム等のアルカリ金属やカルシウム、マグネシウム等のアルカリ土類金属等の金属類の水酸化物や、アンモニウム化合物等からなる群から選ばれた１種又は２種以上のアルカリ化合物との塩が好ましく、具体的には、塩化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、酢酸ナトリウム、塩化マグネシウム、塩化カルシウム等が挙げられ、また、有機の水溶性固体物質として合成、半合成及び天然の水溶性高分子があり、具体的には、合成水溶性高分子としてポリビニルアルコールやその誘導体、ポリ（メタ）アクリル酸アルカリ塩、（メタ）アクリル酸やそのエステル共重合物のアルカリ塩、アクリル酸やマレイン酸の共重合物のアルカリ塩、ポリビニルピロリドン等を例示でき、半合成水溶性高分子としてメチルセルロース、エチルセルロース、ＣＭＣ、ヒドロキシアルキルセルロース、でんぷん誘導体等を例示でき、また、天然水溶性高分子としてでんぷん、ゼラチン、寒天、海草類、植物粘質物、タンパク質等を例示することができる。
【００１７】
また、上記水溶性液体物質については、上記塗膜形成材層中に溶解しないものであればよく、具体的には、メタノール、エタノール、イソプロピルアルコール、ブタノール等の低級アルコール類や、アセトン、メチルエチルケトン等の低級ケトン類や、ジメチルエーテル、メチルエチルエーテル等の低級エーテル類や、エチレングリコール、グリセリン等の多価アルコール類や、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル等のアルキレングリコールのアルキルエーテル類や、アミン類等が挙げられる。これらの水溶性液体物質を使用する際において、使用する水溶性液体物質の粘性が高い場合には、噴霧可能な粘度範囲にまで水等で希釈して使用することが好ましく、また、使用する水溶性液体物質が低沸点物質や揮発し易い物質であって使用環境の温度が高いような場合には、蒸発性や揮発性を抑制するために揮発性の低い水溶性液体や水溶性液体物質に可溶な水溶性固体物質等を添加してもよい。
【００１８】
また、水性散布材として用いる水溶性固体物質及び／又は水溶性液体物質の水性溶液又は水性懸濁液は、上記水溶性固体物質や水溶性液体物質を散布し易い水性溶液や水性懸濁液の状態にしたものであり、水溶性固体物質及び水溶性液体物質から選ばれた１種又は２種以上の物質を水に溶解し、あるいは、懸濁させて調製される。また、溶解性向上や粘性調整等の目的で、アルカリ性化合物や酸性化合物等を添加することもできる。
【００１９】
更に、水性散布材として使用される水については、通常の工業用水等でよく、必要に応じて、上記水溶性固体物質及び水溶性液体物質から選ばれた少量の物質を添加してもよい。
【００２０】
本発明においては、基材表面に上記塗膜形成材を塗布して塗膜形成材層を形成した後、形成された塗膜形成材層が乾燥し又は硬化する前に、この塗膜形成材層の表面に上記水性散布材を散布するが、そのタイミングについては、散布された水性散布材の飛沫粒子が乾燥し又は硬化する前の塗膜形成材層の表面に止まり、この飛沫粒子の一部が塗膜形成材層の表面から層内に入り込んで塗膜形成層の表面に断面略々Ｕ形状の微***を形成せしめると共に、水性散布材の飛沫粒子が塗膜形成材層中に完全には埋没しないタイミングであればよく、通常は、使用する塗膜形成材及び水性散布材の種類に応じて予め散布テストを行って決定すればよい。また、同様に、その散布量についても、形成された塗膜形成材層の種類や散布される水性散布材の種類、更には、最終的に形成される滑り難い塗膜層に必要とする微***の面積率、単位面積当りの微***の個数等により異なるが、予め予備試験を行って決定するのがよい。
【００２１】
このようにして乾燥し又は硬化する前の塗膜形成材層の表面に水性散布材を散布したのち、上記塗膜形成材層を乾燥し又は硬化させ、その後に上記水性散布材を除去して滑り難い塗膜層を得る。
ここで、塗膜形成材層を乾燥し又は硬化させる方法については、通常はその環境温度下に放置しておけばよいが、必要により温風等の手段で加温してもよい。また、水性散布材を除去する方法についても、特に制限はないが、好ましくは、水性散布材が水溶性固体物質、水溶性液体物質、又はこれら水溶性固体物質及び／又は水溶性液体物質の水性溶液又は水性懸濁液である場合には、水によりこれら水溶性固体物質及び／又は水溶性液体物質を溶出させて水性散布材を除去するのがよく、また、水性散布材が水である場合には、単純にこの水を蒸発させて除去するのがよい。
【００２２】
このようにして基材表面に最終的に形成される滑り難い塗膜層については、この塗膜層の表面に形成された微***の平均直径が１μｍ以上１，０００μｍ以下、好ましくは５〜２００μｍ程度であるのがよく、また、微***の個数が２０個／ｃｍ2以上２０，０００個／ｃｍ 2 以下、好ましくは５０個／ｃｍ2以上２０，０００個／ｃｍ2以下、より好ましくは５００個／ｃｍ2以上１０，０００個／ｃｍ2以下であるのがよく、更に、微***の面積率が３％以上５０％以下、好ましくは１０％以上５０％以下であるのがよい。この塗膜層の表面に形成される微***の平均直径が１μｍより小さいと滑り止め性が劣り、反対に、１，０００μｍより大きくなると塗膜層の外観が損なわれる虞があり、また、微***の個数が２０個／ｃｍ2より少ないと滑り止め性が劣り、反対に、２０，０００個／ｃｍ2より多くなると塗膜層の外観が損なわれる虞があり、更に、微***の面積率が３％より低いと滑り止め性が劣り、反対に、５０％より高くなると塗膜層の外観が損なわれる虞がある。
【００２３】
また、この塗膜層のデュロメータ硬さ（JIS K6253「加硫ゴムの硬さ試験方法」に準拠）については、特に制限はないが、例えば基材がコンクリートの場合では５０以上、好ましくは７０以上であるのがよい。この塗膜層のデュロメータ硬さが５０未満では比較的柔らかくて歩行感に劣り、しかも、汚れ易いという問題がある。
【００２４】
本発明の方法により作成される塗膜層には、その表面に所定の平均直径、個数及び面積率の微***が形成されるので、特に塗膜層が水で濡れている時には、これらの微***が塗膜層上を移動する人の靴底、自動車のタイヤ、運搬用台車等との間で表面張力を発揮し、その際の吸盤効果により優れた滑り止め効果を発揮するものと考えられる。それ故、本発明の滑り難い塗膜層は、例えば、合成樹脂、セラミック、金属、コンクリート、ガラス等で形成された床材の表面に設けることにより、滑り難い床材とすることができるほか、旧塗膜の床等の表面に形成されて優れた効果を発揮する。
【００２５】
【発明の実施の形態】
以下、実施例、比較例、及び試験例に基づいて、本発明の好適な実施の形態を具体的に説明する。
【００２６】
実施例１
フレキシブルボード（30cm×30cm×3mm）上に、エポキシ樹脂系２液型プライマー〔アトミクス(株)製商品名：フロアトップ#800プライマー〕０．２kg/m2を塗布し、３時間乾燥させた。その後に床用無溶剤２液型エポキシ樹脂塗料〔アトミクス(株)製商品名：フロアトップ#8000〕１kg/m2を塗布し、２０℃で約３時間放置して乾燥直前に、水性散布材の水溶性固体物質として１００メッシュの篩を通して得られた平均粒径７０μmのポリビニルピロリドン（BASF社製商品名：ルビスコールK30パウダー）１０．５g/m2を散布した。更にその後、２０℃、６５%の温度湿度条件下に２４時間乾燥し、硬化させた後、形成された塗膜層の表面を水で十分洗浄して水溶性固体物質を溶出させ、次いで２０℃、６５%の温度湿度条件下に７日間乾燥させ、実施例１の試験用塗膜層を得た。
【００２７】
得られた実施例１の試験用塗膜層について、その表面をデジタルHDマイクロスコープVH7000型（キーエンス社製）を使用し、倍率１５０倍で観察して写真撮影した後、以下に示す方法により塗膜層の表面に観察された微***の平均直径、個数及び面積率を測定し、次いで、以下に示す方法により塗膜層の滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００２８】
塗膜層の表面に観察された微***の平均直径は、単位面積(cm2)当りに観察された各微***の直径を測定してその平均値を算出して求め、また、微***の個数は、単位面積(cm2)当りに観察された微***の個数として求め、更に、微***の面積率は、単位面積(cm2)当りに観察された微***の面積の合計を百分率で示した。
【００２９】
〔滑り抵抗性（BPN値）〕
塗膜層の滑り抵抗性（BPN値）は、試験用塗膜層の全面に水がいきわたるように湿潤させ、英国式滑り抵抗性試験機（BSI Testing Service社製商品名：ポータブル・スキッドレジスタンステスター）を用いて湿潤時のＢＰＮ値を測定し、（社）日本道路協会発行「アスファルト舗装要綱」第173頁（1997年改訂版第12刷）の「7-2 歩行者系道路舗装の選定 ［解説］(3)」に記載されたＢＰＮ値４０以上（湿潤状態）を基準にして評価した。
【００３０】
〔耐摩耗性〕
中心に８mmの小孔を有する１０cm×１０cmの大きさのスレート板を用い、その表面に上記実施例１と同様にして塗膜層を形成し、更に７日間乾燥して試験板を作製した。得られた試験板について、摩耗試験機（テレダインテーバー社製）を使用し、摩耗輪(CS-17)片側加重１kg、１００回転の条件で塗膜層の摩耗量を測定し、◎：摩耗量５０mg以下、○：摩耗量５０mg超２００mg以下、△：摩耗量２００mg超５００mg以下、及び×：摩耗量５００mg超の４段階評価により評価した。
【００３１】
〔外観〕
拡散昼光の下で塗膜層の外観を目視で観察し、水性散布材の散布を行わなかった塗膜層の表面と比較して、◎：同等、○：やや劣る、△：劣る、及び、×：かなり劣るの４段階評価により評価した。
【００３２】
〔密着性〕
JIS A6909-6.10の付着強さ試験に準じて測定を行い、◎：付着強さ２MPa超、○：付着強さ1MPa以上２MPa未満、△：付着強さ０．５MPa以上１MPa未満、及び、×：付着強さ０．５MPa未満の４段階評価により評価した。
【００３３】
実施例２
水性散布材の水溶性固体物質として平均粒径（長軸測定）１４０μmの炭酸水素ナトリウム（市販１級試薬）を用い、塗膜形成材層の表面に８g/m2の割合で散布した以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた実施例２の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００３４】
実施例３
プライマーとしてウレタン系１液湿気硬化プライマー〔アトミクス(株)製商品名：プライマーU〕０．２kg/m2を用い、また、塗膜形成材として床用硬化ウレタン樹脂塗料〔アトミクス(株)製商品名：フロアトップU#100 NEO〕１．３kg/m2を用い、塗布後２０℃で約２時間放置して乾燥直前に水性散布材（水溶性固体物質：ルビスコールK30パウダー）を散布した以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた実施例３の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００３５】
実施例４
プライマーとしてアクリルシリコーン系樹脂〔鐘淵化学工業(株)製商品名カネカゼムラックYC-1505をキシレンで固形分濃度20%に希釈し、この希釈物１００重量部に対して２重量部のスズ系触媒を添加したもの〕０．２kg/m2を用い、また、塗膜形成材として無機−有機ハイブリッド樹脂クリヤー塗料〔アトミクス(株)製：無溶剤シリコン系複合樹脂〕２００g/m2を用い、塗布後２０℃で約１時間放置して乾燥直前に、水性散布材として水道水８９g/m2を散布した以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた実施例４の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００３６】
実施例５
水性散布材として水溶性液体物質の水溶液（グリセリン50重量%水溶液）を用い、塗膜形成材層の表面に１２g/m2の割合で散布した以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた実施例５の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００３７】
実施例６
水性散布材として水溶性固体物質の水溶液（炭酸水素ナトリウム5重量%水溶液）を用い、塗膜形成材層の表面に８g/m2の割合で散布した以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた実施例６の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００３８】
実施例７
水性散布材の散布量を５g/m2とした以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた実施例７の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００３９】
実施例８
水性散布材の散布量を２０g/m2とした以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた実施例８の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００４０】
比較例１
水性散布材の散布を行わなかった以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた比較例１の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００４１】
比較例２
水性散布材の水溶性固体物質として平均粒径１．２mmの水溶性物質被覆ビーズ（乾燥したガラスビーズの表面をヒドロキシエチルセルロースで被覆したもの）２７０g/m2を用いた以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた比較例２の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００４２】
比較例３
水性散布材の散布量を１．６g/m2とした以外は、上記実施例１と同様にして試験用塗膜層を作製した。
得られた比較例３の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００４３】
比較例４
水性散布材として水溶性液体物質の水溶液（グリセリン10重量%水溶液）を用い、塗膜形成材を塗布した後６時間後に塗膜形成材層の表面に１３．３g/m2の割合で散布した以外は、上記実施例５と同様にして試験用塗膜層を作製した。
得られた比較例４の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００４４】
比較例５
上記実施例１の場合と同様に塗膜形成材を塗布し、水性散布材を散布することなく２０℃で２４時間乾燥させて硬化させ、形成された塗膜層の表面にスポンジを用いて(株)ハイパーテック・ジャパン輸入の市販品「スリップバスター」（主成分はリン酸フッ化アンモニウムの水系溶液）を塗布し、乾燥しないうちに塗膜層の表面をスポンジで時々擦り、３０分間保持したのちに５重量%-重曹水溶液で中和し、水で十分洗浄して７日間乾燥させ、試験用塗膜層を作製した。
得られた比較例５の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００４５】
比較例６
上記実施例１の場合と同様に塗膜形成材を塗布し、その後直ちに形成された塗膜形成材層の表面に珪砂５号〔北日本産業(株)製〕３，０００g/m2を散布し、２４時間乾燥させた後に固着していない珪砂を除去し、次いで再び床用無溶剤２液型エポキシ樹脂塗料〔アトミクス(株)製フロアトップ#8000〕０．２kg/m2を塗布し、更に７日間乾燥させて試験用塗膜層を作製した。
得られた比較例６の試験用塗膜層について、上記実施例１と同様に、その微***の平均直径、個数及び面積率を測定し、次いで滑り抵抗性（BPN値）、外観、耐摩耗性、及び密着性を調べた。
結果を表１に示す。
【００４６】
【表１】
なお、表１において、塗膜形成材及び水性散布材における略号は下記の通りである。
E-FT：床用無溶剤２液型エポキシ樹脂塗料〔アトミクス(株)製商品名：フロアトップ#8000〕
PVP：ポリビニルピロリドン（BASF社製商品名：ルビスコールK30パウダー）
SHC：炭酸水素ナトリウム（NaHCO3；市販１級試薬）
U-FT：床用硬化ウレタン樹脂塗料〔アトミクス(株)製商品名：フロアトップ U#100 NEO〕
HCS：無機−有機ハイブリッド樹脂クリヤー塗料〔アトミクス(株)製：無溶剤シリコン系複合樹脂〕
G-50：グリセリン50重量%水溶液
SHC-5：炭酸水素ナトリウム5重量%水溶液
C-GB：水溶性物質被覆ビーズ
G-10：グリセリン10重量%水溶液
SL-BR：(株)ハイパーテック・ジャパン輸入の市販品「スリップバスター」
SS-5：珪砂５号〔北日本産業(株)製〕
【００４８】
【発明の効果】
本発明によれば、形成される塗膜層の塗膜外観、密着性、塗膜強度等の塗膜物性を低下させることなく、また、使用される塗膜形成材の種類に依存することなく、優れた滑り止め性、特に湿潤時の滑り止め性が得られ、しかも、現場施工も容易であり、特に床材の用途に好適な滑り難い塗膜層を作製することができる。[0001]
BACKGROUND OF THE INVENTION
The present inventionFloorIt relates to a method for producing a coating film layer that is difficult to slip on the surface of a substrate, and is not particularly limited.For example, when a floor is in a factory or the like, there are many opportunities to get wet with water. Suitable for providing a non-slip coating layer on the floor surface that is easy to slipPaintedHow to make a membrane layerTo the lawRelated.
[0002]
[Prior art]
For example, having a coating layer on the surfaceFlooringConventionally, as a non-slip method, a method of forming irregularities on the coating film surface using spray dust, a method of mixing aggregate on the coated surface, a method of mixing aggregate or polymer powder in the paint ( JP-A-8-217,994, JP-A-9-87,547) are known, and are made of mineral materials.FlooringA method of providing micro-crater-shaped micro-holes on the surface of the metal surface even if statistically distributed (Japanese Patent Publication No. 11-505,185) or a method of etching with a chemical (Patent No. 2,574,646) Publications) and the like are also known.
[0003]
However, in the method of forming irregularities on the coating film surface or spraying aggregate, there is a problem that the coating film surface to be formed becomes rough and loses smoothness, and the stain resistance is remarkably reduced. Even when aggregates or polymer powders are mixed in the paint, there is a problem in that the smoothness is similarly lost, and the uniformity of the sprayed matter is poor and the appearance of the coating film is remarkably lowered. In addition, there is a problem that the size of the substrate that can be processed is limited by the method of forming micro craters in the form of a laser with a laser, and it is difficult to work at the floor covering material facility site. In addition to the use of mineral materials such as stones and tiles, there are problems with the risk of chemicals and the disposal of wash water after neutralization.
[0004]
As a method for making the coating film porous, a resin liquid obtained by dispersing or dissolving a resin in a water-insoluble organic solvent, water-soluble inorganic salt particles having an average particle diameter of 1 μm or less, and a pigment having an average particle diameter of 1 μm or less. The organic solvent-based paint obtained by mixing with a base material is coated on a substrate, and then the organic solvent is volatilized to obtain a dry coating film or a cured coating film, and then water-soluble inorganic salt particles in the coating film are washed with water. Has been proposed (Japanese Patent Laid-Open No. 2001-179,173).
[0005]
However, the coating film made porous by this method uses inorganic materials such as metal, concrete, glass, etc., organic materials such as plastic, wood, fiber, coating film, and a combination of these materials. Although it is explained that it can be done, the pores reach from the inside of the paint film to the surface of the base material, and the physical properties of the paint film, such as the paint film strength, are the same as the method of mixing aggregate and polymer powder in the paint. Has a coating layer on the surface because it is significantly reducedFlooringIt is not suitable as a non-slip method.
[0006]
[Problems to be solved by the invention]
Therefore, the present inventors have excellent anti-slip properties, particularly anti-slip properties when wet, without lowering the coating film properties such as coating film appearance, adhesion, coating film strength, etc. Moreover, as a result of intensive investigations on a method for producing a non-slip coating layer that is easy to construct on site, the aqueous coating material is sprayed after being applied to the surface of the substrate, and the aqueous layer after the coating film forming material layer is dried or cured. It was found that by removing the spraying material, it was possible to easily produce a non-slip coating layer on the surface of the substrate, and the present invention was completed.
[0007]
Therefore, the object of the present invention is excellent in anti-slip properties, particularly anti-slip properties when wet, without deteriorating the coating film properties such as coating film appearance, adhesion, and coating film strength of the coating layer formed. Moreover, site construction is easy.PaintIt is to provide a method for producing a film layer.
[0008]
[Means for Solving the Problems]
That is, the present inventionFloorWater-insoluble or sparingly soluble film-forming material is applied to the surface of the substrate, and before the applied film-forming material layer is dried or cured, Selected from solid substances, water-soluble liquid substances, water-soluble solid substances and / or aqueous solutions or suspensions of water-soluble liquid substances, and water, Has the property of not dissolving in the coating film forming material layerAfter spraying the aqueous spraying material and drying or curing the coating film forming material layer, the aqueous spraying material is removed.And a coating layer having a large number of micro holes having an area ratio of 3% to 50% and an average diameter of 1 μm to 1,000 μm on the surface.This is a method for producing a non-slip coating layer..
[0009]
In the present invention, the film-forming material that is insoluble or hardly soluble in water applied to the substrate surface is insoluble or hardly soluble in water, and is applied to the substrate surface to form a coating film layer. Anything can be used.
[0010]
Here, as the coating film forming material used in the present invention, various resin components conventionally used as one of paint components, for example, non-crosslinking type resins, self-crosslinking properties, or external crosslinking properties by a curing agent are used. In addition to cross-linking type resins, these resin components include alcohol-based, hydrocarbon-based, ketone-based, ester-based solvents, fluidity modifiers, curing catalysts, ultraviolet absorbers, heat stabilizers, Examples include auxiliary agents such as initiators, pigments such as coloring pigments, extender pigments, anti-corrosion pigments, metal pigments, and other ingredients such as dyes. Even if it mix | blends, you may mix | blend in a two-pack type.
[0011]
Specific examples of the non-crosslinking type resin include epoxy resin, polyester resin, acrylic resin, vinyl copolymer, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate resin copolymer, and fiber base. Examples thereof include resin, polyethylene resin, polypropylene resin, nylon, ABS resin, polycarbonate, phenol resin, fluororesin, silicone resin, and modified resins thereof.
[0012]
Specific examples of the crosslinking type resin include amino curable acrylic resins, amino curable polyester resins, (block) polyisocyanate curable acrylic resins, (block) polyisocyanate curable polyester resins, and acid anhydride curable resins. Examples thereof include a type epoxy resin, a polyacid curable epoxy resin, a hydrolyzable silyl group-containing resin, an oxidation curable alkyd resin, and an active energy ray curable resin.
[0013]
In the present invention, the coating film forming material is applied to the surface of the base material, and a coating film forming material layer before being dried or cured is formed. For the purpose of preventing inhalation and improving adhesion, a base layer such as a sealer or a primer is previously formed on the surface of the base material before forming the coating film forming material layer, and the coating film forming material layer is formed on the base layer. In addition, before forming a coating film forming material layer as the uppermost layer, if necessary, a plurality of coating film layers can be formed by applying the same or different coating film forming material as this coating film forming material. You may make it form.
[0014]
Here, with respect to the method for applying the coating film forming material to the substrate surface, conventionally known coating means can be employed, such as spray coating, roller coating, brush coating, iron coating, bar coating, and the like. Examples include coater coating.
[0015]
In the present invention, the water-soluble solid substance sprayed on the surface of the coating film forming material layer as an aqueous spraying material does not dissolve in the coating film forming material layer, and the coating film forming material layer is dried or There is no particular limitation as long as it can be easily removed by spraying water after curing, and more preferably fine holes with an average diameter of 1 μm or more can be formed in the coating layer after removing the aqueous spray material. However, the average particle diameter is preferably 1000 μm or less, more preferably 1 μm or more and 500 μm or less, and even more preferably 5 μm or more and 200 μm or less. If the average particle size of the water-soluble solid substance exceeds 1000 μm, a thicker film thickness is required for the coating film forming material layer, which is uneconomical and the appearance of the coating film is significantly reduced. If the average particle size of the solid material is less than 1 μm, the size of the micropores formed is small and the anti-slip effect cannot be expected so much, and the period in which the anti-slip effect lasts due to wear of the coating layer over time is shortened. Therefore, it is not preferable.
[0016]
Examples of such water-soluble solid substances include inorganic water-soluble solid substances such as weak acids and weak bases, weak acids and strong bases, and salts obtained by neutralization of strong acids and weak bases, such as hydrochloric acid, sulfuric acid, and carbonic acid. Hydroxides of one or more acid compounds selected from the group consisting of inorganic acids such as and the like and derivatives thereof, and alkali metals such as sodium and potassium, and metals such as alkaline earth metals such as calcium and magnesium Or a salt with one or more alkali compounds selected from the group consisting of ammonium compounds and the like, specifically, sodium chloride, sodium carbonate, sodium bicarbonate, sodium acetate, magnesium chloride, calcium chloride In addition, there are synthetic, semi-synthetic and natural water-soluble polymers as organic water-soluble solid substances, specifically, synthetic water-soluble polymers. Examples include polyvinyl alcohol and derivatives thereof, poly (meth) acrylic acid alkali salts, alkali salts of (meth) acrylic acid and ester copolymers thereof, alkali salts of acrylic acid and maleic acid copolymers, polyvinylpyrrolidone, and the like. Examples of semi-synthetic water-soluble polymers include methyl cellulose, ethyl cellulose, CMC, hydroxyalkyl cellulose, starch derivatives, etc., and examples of natural water-soluble polymers include starch, gelatin, agar, seaweed, plant mucilage, proteins, etc. Can do.
[0017]
The water-soluble liquid substance may be any substance that does not dissolve in the coating film-forming material layer. Specifically, lower alcohols such as methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, etc. Lower ketones, lower ethers such as dimethyl ether and methyl ethyl ether, polyhydric alcohols such as ethylene glycol and glycerol, alkyl ethers of alkylene glycol such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether, amines And the like. When using these water-soluble liquid substances, when the viscosity of the water-soluble liquid substance to be used is high, it is preferable to dilute with water or the like up to a sprayable viscosity range. If the volatile liquid substance is a low-boiling point substance or a substance that easily volatilizes and the temperature of the usage environment is high, a low-volatility water-soluble liquid or water-soluble liquid substance should be used in order to suppress evaporation and volatility. A soluble water-soluble solid substance or the like may be added.
[0018]
In addition, an aqueous solution or suspension of a water-soluble solid substance and / or a water-soluble liquid substance used as an aqueous spray material is an aqueous solution or suspension that is easy to spray the water-soluble solid substance or water-soluble liquid substance. In this state, it is prepared by dissolving or suspending one or more substances selected from water-soluble solid substances and water-soluble liquid substances in water. Moreover, an alkaline compound, an acidic compound, etc. can also be added for the purpose of improving solubility or adjusting viscosity.
[0019]
Further, the water used as the aqueous spraying material may be ordinary industrial water or the like, and a small amount of material selected from the above water-soluble solid material and water-soluble liquid material may be added as necessary.
[0020]
In the present invention, after the coating film forming material is applied to the surface of the substrate to form the coating film forming material layer, the coating film forming material is formed before the formed coating film forming material layer is dried or cured. The aqueous spraying material is sprayed on the surface of the layer, but the timing of the spraying of the sprayed aqueous spraying material stops on the surface of the coating film forming material layer before it is dried or hardened. The part penetrates into the layer from the surface of the coating film forming layer to form a microhole having a substantially U-shaped cross section on the surface of the coating film forming layer, and the spray particles of the aqueous spray material are completely in the coating film forming material layer. It is sufficient that the timing is not buried, and it is usually determined by conducting a spraying test in advance according to the type of coating film forming material and aqueous spraying material to be used. Similarly, with respect to the amount of spraying, the type of coating film forming material layer formed, the type of aqueous spraying material sprayed, and the minute amount required for the non-slip coating film finally formed. Although it depends on the area ratio of holes, the number of micro holes per unit area, etc., it is preferable to perform a preliminary test in advance.
[0021]
After spraying the aqueous spraying material on the surface of the coating film forming material layer before drying or curing in this way, the coating film forming material layer is dried or cured, and then the aqueous spraying material is removed. A non-slip coating layer is obtained.
Here, the method of drying or curing the coating film forming material layer is usually allowed to stand at the environmental temperature, but may be heated by means such as warm air if necessary. Further, the method for removing the aqueous spraying material is not particularly limited, but preferably the aqueous spraying material is a water-soluble solid substance, a water-soluble liquid substance, or an aqueous solution of these water-soluble solid substance and / or water-soluble liquid substance. In the case of a solution or an aqueous suspension, it is preferable to elute these water-soluble solid substances and / or water-soluble liquid substances with water to remove the aqueous spray material, and when the aqueous spray material is water. It is better to simply evaporate the water and remove it.
[0022]
Thus, about the non-slip coating film finally formed on the surface of the substrate, the average diameter of the microholes formed on the surface of the coating layer is 1 μm or more and 1,000 μm or less, preferably 5 to 200 μm. The number of micro holes is 20 / cm.2more than20,000 / cm 2 Less than, Preferably 50 / cm2More than 20,000 pieces / cm2Or less, more preferably 500 pieces / cm210,000 pieces / cm2The area ratio of micro holes should be 3% or more.50% or lessPreferably, it is 10% or more and 50% or less. If the average diameter of the fine holes formed on the surface of the coating layer is less than 1 μm, the anti-slip property is inferior. On the other hand, if it exceeds 1,000 μm, the appearance of the coating layer may be impaired. The number of holes is 20 / cm2If it is less, the slip resistance is inferior, on the contrary, 20,000 / cm2If the amount is more, the appearance of the coating layer may be impaired. Further, if the area ratio of the microholes is lower than 3%, the anti-slip property is inferior. On the other hand, if it exceeds 50%, the appearance of the coating layer is impaired. There is a fear.
[0023]
The durometer hardness of this coating layer (based on JIS K6253 “Method for testing hardness of vulcanized rubber”) is not particularly limited. For example, when the base material is concrete, it is 50 or more, preferably 70 or more. It is good to be. If the durometer hardness of the coating layer is less than 50, there is a problem that it is relatively soft and inferior in walking feeling, and moreover, it tends to get dirty.
[0024]
Since the coating layer prepared by the method of the present invention has micro holes with a predetermined average diameter, number and area ratio formed on the surface thereof, these micro layers are particularly wet when the coating layer is wet with water. It is considered that the hole exerts surface tension between the shoe sole of a person moving on the coating layer, an automobile tire, a carriage for transportation, etc., and an excellent anti-slip effect due to the suction cup effect at that time . Therefore, the non-slip coating layer of the present invention is formed of, for example, synthetic resin, ceramic, metal, concrete, glass, etc.FlooringIt is hard to slip by providing on the surface ofFlooringIn addition, it is formed on the surface of the old paint film or the like and exhibits excellent effects.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described specifically based on examples, comparative examples, and test examples.
[0026]
Example 1
On a flexible board (30cm x 30cm x 3mm), epoxy resin two-component primer [Atomics Co., Ltd. product name: Floor Top # 800 Primer] 0.2kg / m2Was applied and dried for 3 hours. After that, solvent-free two-component epoxy resin paint for flooring (trade name: Floor Top # 8000, manufactured by Atomics Co., Ltd.) 1 kg / m2And then left at 20 ° C. for about 3 hours and immediately before drying, polyvinyl pyrrolidone having an average particle diameter of 70 μm obtained as a water-soluble solid substance of an aqueous spraying material through a sieve of 100 mesh (trade name: BARBISH, manufactured by BASF) K30 powder) 10.5g / m2Sprayed. Further, after drying and curing for 24 hours under 20 ° C. and 65% temperature and humidity conditions, the surface of the formed coating layer is sufficiently washed with water to elute the water-soluble solid substance, and then 20 ° C. The film was dried for 7 days under a temperature and humidity condition of 65% to obtain the test coating layer of Example 1.
[0027]
Using the digital HD microscope VH7000 type (manufactured by Keyence), the surface of the obtained coating film for test of Example 1 was photographed by observing at a magnification of 150 times, and then coated by the method shown below. Measure the average diameter, number, and area ratio of micro-holes observed on the surface of the film layer, and then use the following methods to determine the slip resistance (BPN value), appearance, wear resistance, and adhesion of the coating layer. I investigated.
The results are shown in Table 1.
[0028]
The average diameter of the microholes observed on the surface of the coating layer is the unit area (cm2) The diameter of each microhole observed per unit is measured and the average value is calculated and obtained.The number of microholes is the unit area (cm2), And the area ratio of the microholes is the unit area (cm2) The total area of the microholes observed per unit is shown as a percentage.
[0029]
[Slip resistance (BPN value)]
The slip resistance (BPN value) of the paint film layer is moistened so that water spreads over the entire surface of the test paint film layer, and an English-style slip resistance tester (BSI Testing Service, product name: Portable Skid Resistance Tester) ) To measure the BPN value when wet, "7-2 Selection of pedestrian road pavement", page 173 of the "Asphalt Pavement Summary" published by the Japan Road Association (revised 12th edition of 1997) [ [Explanation] The evaluation was made based on the BPN value of 40 or more (wet state) described in (3).
[0030]
(Abrasion resistance)
Using a slate plate having a size of 10 cm × 10 cm having a small hole of 8 mm in the center, a coating layer was formed on the surface in the same manner as in Example 1 above, and further dried for 7 days to prepare a test plate. Using the abrasion tester (manufactured by Teledyne Taber Co., Ltd.), the amount of abrasion of the coating layer was measured under the conditions of a wear wheel (CS-17) 1-side load of 1 kg and 100 rotations. The amount was evaluated by a four-step evaluation, with an amount of 50 mg or less, ◯: abrasion amount exceeding 50 mg and 200 mg or less, Δ: abrasion amount exceeding 200 mg and 500 mg or less, and x: abrasion amount exceeding 500 mg.
[0031]
〔appearance〕
The appearance of the coating layer was visually observed under diffuse daylight, and compared with the surface of the coating layer that was not sprayed with an aqueous spray, ◎: equivalent, ○: slightly inferior, Δ: inferior, and , X: Evaluation was performed by four-level evaluation, which was considerably inferior.
[0032]
[Adhesion]
Measured according to JIS A6909-6.10 adhesion strength test, ◎: Adhesion strength over 2 MPa, ○: Adhesion strength 1 MPa to less than 2 MPa, △: Adhesion strength 0.5 MPa to less than 1 MPa, and ×: Evaluation was made by a four-step evaluation with an adhesion strength of less than 0.5 MPa.
[0033]
Example 2
Sodium bicarbonate (commercial first grade reagent) with an average particle size (major axis measurement) of 140 μm was used as the water-soluble solid substance of the aqueous spraying material, and 8 g / m was applied to the surface of the film-forming material layer.2A test coating layer was prepared in the same manner as in Example 1 except that the coating layer was sprayed at a ratio of.
For the test coating layer obtained in Example 2, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0034]
Example 3
Urethane-based one-component moisture-curing primer (trade name: Primer U, manufactured by Atomics Co., Ltd.) 0.2 kg / m as a primer2In addition, cured urethane resin paint for floors (trade name: Floor Top U # 100 NEO, manufactured by Atomics Co., Ltd.) 1.3 kg / m2A coating layer for testing was conducted in the same manner as in Example 1 except that after application, the sample was left at 20 ° C. for about 2 hours and was sprayed with an aqueous spray material (water-soluble solid substance: rubiscol K30 powder) immediately before drying. Was made.
For the test coating layer obtained in Example 3, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, followed by slip resistance (BPN value), appearance, and abrasion resistance. The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0035]
Example 4
Acrylic silicone resin as a primer [trade name Kanekazemulac YC-1505 manufactured by Kaneka Chemical Industry Co., Ltd. is diluted with xylene to a solid content concentration of 20%, and 2 parts by weight of tin based on 100 parts by weight of this diluted product Catalyst added) 0.2kg / m2In addition, an inorganic-organic hybrid resin clear paint [manufactured by Atomics Co., Ltd .: solventless silicon composite resin] 200 g / m as a coating film forming material2After application, leave at 20 ° C for about 1 hour and immediately before drying, tap water 89g / m as an aqueous spray2A test coating layer was prepared in the same manner as in Example 1 except that was sprayed.
For the test coating layer obtained in Example 4, the average diameter, number and area ratio of the micropores were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0036]
Example 5
An aqueous solution of water-soluble liquid substance (glycerin 50% by weight aqueous solution) is used as an aqueous spraying material, and 12 g / m is applied to the surface of the film-forming material layer.2A test coating layer was prepared in the same manner as in Example 1 except that the coating layer was sprayed at a ratio of.
For the test coating layer obtained in Example 5, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0037]
Example 6
As an aqueous spraying material, an aqueous solution of water-soluble solid substance (5% by weight aqueous sodium hydrogen carbonate solution) is used, and 8 g / m is applied to the surface of the coating film forming material layer.2A test coating layer was prepared in the same manner as in Example 1 except that the coating layer was sprayed at a ratio of.
For the test coating layer obtained in Example 6, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0038]
Example 7
5g / m of water-dispersed material2A test coating layer was prepared in the same manner as in Example 1 except that.
For the test coating layer of Example 7 obtained, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0039]
Example 8
20g / m of water spray2A test coating layer was prepared in the same manner as in Example 1 except that.
For the test coating layer obtained in Example 8, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0040]
Comparative Example 1
A test coating layer was prepared in the same manner as in Example 1 except that the aqueous spray material was not sprayed.
For the test coating layer obtained in Comparative Example 1, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0041]
Comparative Example 2
270 g / m of water-soluble substance-coated beads having an average particle diameter of 1.2 mm as a water-soluble solid substance for aqueous spray materials (the surface of dried glass beads coated with hydroxyethyl cellulose)2A test coating layer was prepared in the same manner as in Example 1 except that was used.
For the test coating layer obtained in Comparative Example 2, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0042]
Comparative Example 3
1.6g / m of water-dispersed material2A test coating layer was prepared in the same manner as in Example 1 except that.
For the test coating layer obtained in Comparative Example 3, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0043]
Comparative Example 4
An aqueous solution of a water-soluble liquid substance (glycerin 10% by weight aqueous solution) was used as an aqueous spraying material.2A test coating layer was prepared in the same manner as in Example 5 except that the coating layer was sprayed at a ratio of.
For the test coating layer of Comparative Example 4 obtained, the average diameter, number and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0044]
Comparative Example 5
In the same manner as in Example 1, the coating film forming material was applied, dried and cured at 20 ° C. for 24 hours without spraying the aqueous spray material, and a sponge was used on the surface of the formed coating film layer ( A commercial product "Slip Buster" imported by Hypertech Japan Co., Ltd. was applied (the main component was an aqueous solution of ammonium phosphate fluoride), and the surface of the coating layer was occasionally rubbed with a sponge before being dried and held for 30 minutes. Thereafter, it was neutralized with a 5% by weight aqueous sodium bicarbonate solution, thoroughly washed with water and dried for 7 days to prepare a test coating layer.
For the test coating layer of Comparative Example 5 obtained, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0045]
Comparative Example 6
A coating film forming material was applied in the same manner as in Example 1 above, and immediately after that, on the surface of the formed film forming material layer, silica sand No. 5 [made by Kita Nippon Sangyo Co., Ltd.] 3,000 g / m2After drying for 24 hours, the unfixed silica sand is removed, and then again a solvent-free two-component epoxy resin paint for flooring (Floor Top # 8000 manufactured by Atomics Co., Ltd.) 0.2 kg / m2Was further dried for 7 days to produce a test coating layer.
For the test coating layer of Comparative Example 6 obtained, the average diameter, number, and area ratio of the microholes were measured in the same manner as in Example 1 above, and then slip resistance (BPN value), appearance, wear resistance The adhesiveness and adhesion were examined.
The results are shown in Table 1.
[0046]
[Table 1]
In Table 1, abbreviations for the coating film forming material and the aqueous spray material are as follows.
E-FT: Solvent-free, two-component epoxy resin paint for flooring (Atomics Co., Ltd. product name: Floortop # 8000)
PVP: Polyvinyl pyrrolidone (BASF brand name: Rubiscol K30 powder)
SHC: Sodium bicarbonate (NaHCOThree; Commercial grade 1 reagent)
U-FT: Cured urethane resin paint for floors (Atomics Co., Ltd. product name: Floor top U # 100 NEO)
HCS: Inorganic-organic hybrid resin clear paint [Atomics Co., Ltd .: Solvent-free silicone composite resin]
G-50: 50% by weight aqueous solution of glycerin
SHC-5: Sodium bicarbonate 5 wt% aqueous solution
C-GB: Water-soluble substance coated beads
G-10: 10% by weight aqueous solution of glycerin
SL-BR: "Slip Buster", a commercial product imported by Hypertech Japan
SS-5: Silica sand No.5 [made by Kita Nippon Sangyo Co., Ltd.]
[0048]
【The invention's effect】
According to the present invention, without lowering the coating film properties such as coating film appearance, adhesion and coating film strength of the coating film layer to be formed, and without depending on the type of coating film forming material used. Excellent anti-slip properties, especially when wet, and easy on-site construction.FlooringIt is possible to produce a non-slip coating layer suitable for use in the above.
Claims (6)
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| JP2002090838A JP3996418B2 (en) | 2002-03-28 | 2002-03-28 | Method for producing coating layer |
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| JP5154065B2 (en) * | 2006-11-21 | 2013-02-27 | アイカ工業株式会社 | Coating material composition |
| FR2937181B1 (en) * | 2008-10-10 | 2011-01-14 | Commissariat Energie Atomique | SURFACE STRUCTURING OF THIN LAYERS BY LOCALIZED EJECTION OF IMMISCIBLE LIQUID. |
| NO2750604T3 (en) | 2015-06-25 | 2018-03-03 | ||
| PL3415316T3 (en) | 2017-06-13 | 2020-10-05 | Hymmen GmbH Maschinen- und Anlagenbau | Method and device for producing a structured surface |
| JP6875252B2 (en) | 2017-10-26 | 2021-05-19 | 信越化学工業株式会社 | Method of drying polyimide paste and method of manufacturing high photoelectric conversion efficiency solar cell |
| CN109926292A (en) * | 2017-12-18 | 2019-06-25 | 惠州市长润发涂料有限公司 | A kind of method of the open UV paint of coating on woodenware |
| DE102019206431A1 (en) | 2019-05-03 | 2020-11-05 | Hymmen GmbH Maschinen- und Anlagenbau | Method for producing a structure on a surface |
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