JP4163334B2 - Anti-slip pavement method - Google Patents

Description

〔式中Ｒ ^１ およびＲ ^２ は、同一または異なる炭素数１〜５のアルキル基、Ｘ ^１ およびＸ ^２ は一方が水素で他方がＮＨ _２ 、Ｘ ^３ は水素または−ＳＲ ^３ （Ｒ ^３ は炭素数１〜５のアルキル基）である。〕で示される含硫芳香族ジアミン及びジエチルトルエンジアミンを含み、ゲルタイムが３０秒以上、３００秒以下に調整された二成分型ポリウレタン樹脂を傾斜面に塗布し、塗布層がゲル化する前に骨材を散布する傾斜面の防滑舗装方法、
（２）二成分型ポリウレタン樹脂のゲルタイムが６０秒以上、１８０秒以下に調整された（１）記載の防滑舗装方法、
（３）傾斜面に、プライマー層および／または防水層を設け、次いで請求項１又は２のいずれかに記載の防滑舗装層を形成させ、さらに防滑舗装層上に保護層および／またはトップコート層を設ける防滑舗装方法、
（４）保護層が二成分型ポリウレタン樹脂を塗布して設けたものであり、トップコート層が無黄変性アクリルウレタン塗料を塗布して設けたものである（３）記載の防滑舗装方法、
である。
【０００７】
【発明の実施の形態】
本発明で使用するポリウレタン樹脂はゲルタイムが３０秒以上、３００秒以下のものである必要がある。その３０秒以上でなければならない理由は、３０秒以下では樹脂の塗布と骨材散布作業との間に時間的な余裕が得られず、仮に樹脂塗布と骨材散布を同時に行い、防滑舗装材が得られたとしても、この超速硬化樹脂は骨材との接着性に乏しく、得られる防滑層の骨材に対するグリップ性が劣るため車走行の繰り返しによって骨材の欠落が生じてしまうからである。この点を考慮した場合、より好ましいゲルタイムは６０秒以上である。
また３００秒以下でなければならない理由としては、ゲルタイム３００秒以上の樹脂をスロープ面に吹き付けた場合、垂れが生じて均一な膜厚の防滑舗装層が得られないことと、実用強度発現までの養生が必要になってくることが挙げられる。この点を考慮した場合、より好ましいゲルタイムは１８０秒以下である。
なお、本発明におけるゲルタイムとは、２５℃の室内において垂直に保持したモルタル製下地材に、約６５℃に加熱したポリウレタンエラストマー原液を二成分圧送・混合機（ガスマー社製 Ｈ−２０００）を用いて、約２ｋｇ／ｍ²吹き付け、垂れ流動性が消失するまでの時間をいう。
本発明の二成分型ポリウレタン樹脂は、イソシアネート成分と活性水素成分とを反応させることにより得られる。
【０００８】
イソシアネート成分は、有機イソシアネートまたはイソシアネート基の一部を、たとえば分子量１００〜１０,０００のポリオールと反応させて得られる部分プレポリマーであるが、必要に応じて可塑剤または難燃剤を添加しても良い。
このようにして調製したウレタン樹脂は初期ゲルタイムが３０秒以上、３００秒以下に調製されているので、吹き付け後骨材を散布するための時間的余裕がある上、駐車場構造体にある１／４勾配程度のスロープ面でも垂れない硬化性があり、なおかつ該エラストマーと散布した骨材の接着性が優れるので重車両が走行しても骨材の欠落・離脱がおこらない防滑舗装層となる。
イソシアネート成分を構成する有機イソシアンートとしては、例えば２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネートおよびその混合物(ＴＤＩ）、ジフェニルメタン−４，４’ジイソシアネート（ＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、ジシクロヘキシルメタンジイソシアネート（水素化ＭＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、水素化キシリレンジイソシアネート（ＨＸＤＩ）、粗製ＭＤＩ（ｃ−ＭＤＩ）およびこれらのイソシアネート類のイソシアヌレート化変性品、カルボジイミド変性品などがあげられる。
これらの有機ポリイソシアネートのうちＭＤＩ、ｃ−ＭＤＩおよびその変性品が特に好ましい。
これらの有機ポリイソシアネートはそのままイソシアネート成分として使用することも出来るが、イソシアネート基の一部をポリオールと例えば窒素気流中７０〜８０℃で数時間加熱して得た部分プレポリマーとして使用することも出来る。
【０００９】
部分プレポリマーの製造に使用できるポリオールには水、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールにエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドの１種または２種以上を付加重合して得たポリエーテルポリオールがある。そのほかにはポリテトラメチレンエーテルグリコール、ヒマシ油、ポリカーボネートポリオール等がある。
部分プレポリマーの製造には、前記ポリオールの他にプロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコールおよびこれらの混合物、エチレングリコール、ジエチレングリコール、１，３−ブチレングリコール、分子量１，０００未満のポリエーテルポリオール、分子量１，０００未満のポリテトラメチレンエーテルグリコールなどの低分子量ポリオールが使用出来る。
部分プレポリマーの製造に使用することができるポリオールは、前記ポリオールの単独または２種以上の混合物であるが、その分子量が６０〜５，０００程度のものが好ましい。
イソシアネート成分のＮＣＯ重量％は、製造時の有機イソシアネートと活性水素化合物の種類とモル比によって決定されるが、本発明に使用するプレポリマーの好ましいＮＣＯ％は１０〜２０程度である。
【００１０】
活性水素成分は、分子量１００〜１０，０００程度のポリオールと鎖延長剤として前記一般式（１）で示される含硫芳香族ジアミンを含み、必要により他の助剤、たとえば有機金属触媒、着色剤、難燃剤、消泡剤、可塑剤、充填剤、シランカップリング剤などを含んでいてもよい。
活性水素成分の調製に使用されるポリオールには水、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールにエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドの１種または２種以上を付加重合して得たポリエーテルポリオールがある。そのほかにはポリテトラメチレンエーテルグリコール、ヒマシ油、ポリカーボネートポリオール、アミノ基末端ポリオキシアルキレンポリオール等が挙げられる。
本発明に使用される活性水素成分には、鎖延長剤として一般式（１）
【化３】

（式中Ｒ^１、Ｒ^２、Ｒ^３、Ｘ^１、Ｘ^２およびＸ^３は前記と同意義）で示される含硫芳香族ジアミンを配合することができる。一般式（１）中、Ｒ^１、Ｒ^２およびＲ^３で示される炭素数１〜５のアルキル基としては、たとえば、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｎ−ペンチル等が挙げられるが、メチルおよびエチルが好ましい。この一般式（１）で示される含硫芳香族ジアミンの具体例としては、たとえば１−エチルチオ−ジアミノベンゼン、５−メチルチオ−ジアミノトルエン、５−エチルチオ−ジアミノトルエン、５−イソプロピルチオ−ジアミトルエン、５−エチルチオ−ジアミノエチルベンゼン、５−メチルチオ−ジアミノエチルベンゼン、３，５ジメチルチオ−ジアミノトルエン、３，５−ジエチルチオ−ジアミノトルエン、３，５ジメチルチオ−ジアミノベンゼン、３，５−ジエチルチオ−ジアミノベンゼン、３，５−ジメチルチオ−ジアミノエチルベンゼン、３，５−ジエチルチオ−ジアミノエチルベンゼンなどが挙げられる。
【００１１】
これらの含硫芳香族ジアミンは単独または２種以上の混合物として使用できる。
上記の含硫芳香族ジアミン以外にジエチルトルエンジアミン（ＤＥＴＤＡ）を配合する。さらにエチレングリコール、プロピレングリコール、１，４−ブタンジオールなどのアルカンジオール、エチレンジアミンなどの脂肪族系アミン化合物、ジエタノールアミンやトリエタノールアミンなどの低分子量アルカノールアミン、グリセリンやトリメチロールプロパンなどの低分子量ポリオール、その他いわゆる架橋剤と呼ばれるものを鎖延長剤として併用出来る。エラストマーの硬化性、物性などの観点から、含硫芳香族ジアミンとＤＥＴＤＡの併用が好ましい。ここでＤＥＴＤＡの使用量は全芳香族ジアミン中の全アミノ基の３０ｍｏｌ％以下にするのが望ましい。ＤＥＴＤＡのアミノ基が３０ｍｏｌ％以上となると初期ゲルタイムが極度に短くなることがあり、また骨材散布作業性が悪くなるほか、エラストマーと骨材との接着性が低下することがあるからである。以上に示した鎖延長剤はポリオール１００重量部に対して５〜５０重量部が適している。また活性水素成分の製造に使用する有機金属化合物はイソシアネート成分との反応促進剤であり、オクチル酸鉛、ジブチル錫ジラウレートなど公知のウレタン用触媒が使用可能である。その中で水に起因する発泡現象を防止するため、また安全性の面からオクチル酸ビスマスの使用が好ましい。
【００１２】
さらに助剤としての着色剤、難燃剤、可塑剤、充填剤、消泡剤、安定剤、シランカップリング剤は、イソシアネート成分、活性水素成分のそれぞれに添加することも可能である。着色剤としては例えばカーボンブラック、ベンガラ、酸化クロム、酸化チタン等の無機および有機系を使用する事が出来る。
可塑剤としては例えばジオクチルフタレート（ＤＯＰ）等のフタル酸エステル系、ジオクチルアジペート（ＤＯＡ）等のアジピン酸エステル系を、また難燃剤としてはリン系、ハロゲン系を単独または混合して使用出来る。
安定剤としては耐熱安定剤、紫外線吸収剤、耐候安定剤を単独または組み合わせて使用できる。アルコキシシランカップリング剤としては一般公知のものが使用出来るが、反応基としてイソシアネート基またはエポキシ基を持ったシラン化合物が好ましい。
【００１３】
本発明の防滑舗装層は、通常コンクリート、モルタル、アスコンなどの傾斜した基体上に形成される。防滑舗装層形成に先立ち、基体上にプライマーおよび／または防水層を設けてもよい。その上に本発明の二成分ポリウレタン樹脂が塗布され、ゲル化する前に骨材が散布されて防滑舗装層が形成される。この防滑舗装層上に必要により保護層および／またはトップコート層を設けてもよい。プライマーとしては、一液湿気硬化型ウレタンプライマーが適しているが、これに限定されるものではない。防水層として適しているものは、自体公知の常温超速硬化型ポリウレタン樹脂をスプレー塗装して得られるものである。たとえば、イソシアネート末端ウレタンポリマーを主成分とする主剤と、ポリエーテルポリオールを主成分とする硬化剤の二成分を、高圧または低圧圧送吹き付け装置（例：ガスマー社製 Ｈ−２０００、ユニプル社製 Ｇ−４１など）を用いて塗布するもので、ゲルタイムは５〜３０秒である。この防水層の塗膜物性は、ＪＩＳ Ａ６０２１に定める規格に適合するものであることが望ましい。
【００１４】
本発明の防滑舗装方法は、イソシアネート成分および活性水素成分の二成分を圧送、混合、塗布し、樹脂層がゲル化するまでに骨材を散布することにより行われる。二成分の混合の形式としては、衝突混合、スタティック混合、ダイナミック混合などがあり、その装置としては前記防水層の形成で用いたと同じものが使用しうる。ポリウレタン樹脂の使用量は特に限定されないが、通常０．５〜５ｋｇ／ｍ^２、好ましくは１〜３ｋｇ／ｍ^２である。
二成分型ポリウレタン樹脂から得られるエラストマーは、Ｄ硬度が４５以上、ＪＩＳ Ｋ６３０１に記載の引張り強度が１０ＭＰａ以上、及び伸び率が１５０％以上であることが望ましい。
本発明の防滑舗装方法に使用する骨材としては材質、粒径など特に制限はないが粒径０．５〜３ｍｍの珪砂、焼成アルミナまたはゴムチップなどが仕上がり性、耐久性などの点から好ましい。また骨材の散布方法（手段）についても特に制限はなく、手撒き散布しても良いし、エアー吹きできる機械を用いてもよい。この骨材の使用量は、その材質、粒径などにより異なるが、通常１〜５ｋｇ／ｍ^２、好ましくは１．５〜３．０ｋｇ／ｍ^２である。この防滑舗装層は通常１５分経つとほぼ完全に硬化し、その上を歩くことができる状態となる。保護層の形成には、防滑舗装層に用いた二成分型ポリウレタン樹脂を好適に使用することができる。トップコート層は紫外線照射による防滑舗装層の変色を防止する目的で使用されるものであり、無黄変型アクリルウレタンなどの公知の塗料を使用することができる。
【００１５】
【実施例】
次ぎに本発明の実施例、比較例、評価試験をあげて本発明をさらに具体的に説明する。
１．使用した原材料
・Ｌ−Ｍ：４，４’−ジフェニルメタンジイソシアネート（ＮＣＯ％ ３３.７）（ＢＡＳＦ社製 ルプラネートＭ）
・Ｌ−ＭＭ１０３：カルボジイミド変性液状ＭＤＩ（ＮＣＯ％ ２９.０） （ＢＡＳＦ社製 ルプラネートＭＭ−１０３）
・ポリオール１：２官能ポリプロピレングリコール（ＥＯ；０％）、水酸基価５６（武田薬品工業製 タケラックＰ−２１）
・ポリオール２：３官能ポリプロピレングリコール（ＥＯ；０％）、水酸基価５６（武田薬品工業製 アクトコール７９−５６）
・ポリオール３：２官能ポリプロピレングリコール（ＥＯ；０％）、水酸基価３８（武田薬品工業製 タケラックＰ−２３）
・ポリオール４：２官能ポリプロピレングリコール（ＥＯ；１５％）、水酸基価４６（武田薬品工業製 アクトコールＭＦ−１６）
・ポリオール５：３官能ポリプロピレングリコール（ＥＯ；１５％）、水酸基価３４（武田薬品工業製 アクトコールＴＥ−５０００）
・１，４ＢＧ：１，４−ブタンジオール
【００１６】
・ポリエーテルポリアミン１：２官能ポリエーテルアミン、水酸基価５６（末端アミノ基を活性水素１個として換算)
・ポリエーテルポリアミン２：３官能ポリエーテルアミン、水酸基価５６（末端アミノ基を活性水素１個として換算)
・含硫ジアミン化合物１：３，５−ジメチルチオ−２，４−ジアミノトルエンと３，５−ジメチルチオ−２，６−ジアミノトルエンの混合物
・含硫ジアミン化合物２：３，５−ジエチルチオ−２，４−ジアミノトルエンと３，５−ジエチルチオ−２，６−ジアミノトルエンの混合物
・ＤＥＴＤＡ：３，５ジエチル−２，４−トルエンジアミンと３，５−ジエチル−２，６−トルエンジアミンの混合物
・ＭＯＣＡ：３，３’−ジクロロ−４，４’−ジアミノジフェニルメタン
・顔料：酸化チタン
・耐候安定剤：ヒンダードフェーノール系酸化防止剤とヒンダードアミン系紫外線吸収剤の混合物（チバガイギー社製 チヌビンＢ−７５）
・消泡剤：非シリコン系消泡剤（ビックケミー社製 ＢＹＫ−０６５）
・硬化触媒１：オクチル酸ビスマス（Ｂｉを２０％含有)
・硬化触媒２：オクチル酸鉛（Ｐｂを２０％含有)
・ＤＯＰ：ジオクチルフタレート
・ＴＭＣＰＰ：トリスモノクロロプロピルフォスフェート
・プライマー１：下地処理用一液湿気硬化型ウレタンプライマー（ＮＶ５０）（武田薬品工業製 タケネートＦ−５２６）
・プライマー２：防水層/防滑舗装層間用一液湿気硬化型ウレタンプライマー（ＮＶ２５）（武田薬品工業製 タケネートＭ−４０２Ｐ）
・防滑骨材：４号／５号＝１／１重量の混合珪砂
・トップコート：２液硬化型アクリルウレタン塗料（武田薬品工業製ＵＰトップ６２０）
【００１７】
２．イソシアネート成分Ａ−１〜Ａ−３の調製
Ａ−１
Ｌ−ＭＭ１０３（５８１ｇ）にポリオール１（４１９ｇ）を加え、窒素気流下８０℃で３時間撹拌しながら反応させ、ＮＣＯ％１５、粘度１０００ｍＰａ.ｓ／２５℃、比重１．０７（２５℃）の部分プレポリマーを得た。
Ａ−２
Ｌ−Ｍ（３４４ｇ）にポリオール１（４３８ｇ）を加え、窒素気流下８０℃で３時間撹拌しながら反応させた後にＬ−ＭＭ１０３（１８ｇ）およびＴＭＣＰＰ（２００ｇ）を加え、ＮＣＯ％１０、粘度７５０ｍＰａ．ｓ／２５℃、比重１．１５（２５℃）の部分プレポリマーを得た。
Ａ−３
Ｌ−Ｍ（３９１ｇ）にポリオール２（８３ｇ）とポリオール３（３３２ｇ）を加え、窒素気流下８０℃で３時間撹拌しながら反応させた後に、Ｌ−ＭＭ１０３（４４ｇ）およびＤＯＰ（１５０ｇ）を加え、ＮＣＯ％１３、粘度５００ｍＰａ．ｓ／２５℃、比重１．０８（２５℃）の部分プレポリマーを得た。
【００１８】
３．活性水素成分Ｂ−１〜Ｂ−１０の調製
Ｂ−１
含硫ジアミン化合物１（３０２ｇ）にポリオール１（６６９ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（３ｇ）、消泡剤（１ｇ）、硬化触媒１（５ｇ）を順次添加、撹拌を行ない粘度６１０ｍＰａ.ｓ／２５℃、比重１．０６の混合レジンを得た。
Ｂ−２
含硫ジアミン化合物２（３４４ｇ）にポリオール１（６２７ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（３ｇ）、消泡剤（１ｇ）、硬化触媒１（５ｇ）を順次添加、撹拌を行ない粘度６５０ｍＰａ.ｓ／２５℃、比重１．０６の混合レジンを得た。
Ｂ−３
含硫ジアミン化合物２（２７４ｇ）にＤＥＴＤＡ（５０ｇ）およびポリオール１（６４７ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（３ｇ）、消泡剤（１ｇ）、硬化触媒１（５ｇ）を順次添加、撹拌を行ない、粘度６００ｍＰａ．ｓ／２５℃、比重１．０６の混合レジンを得た。このときレジン中の全芳香族ジアミン中のＤＥＴＤＡ当量％は１９．８であった。
【００１９】
Ｂ−４
含硫ジアミン化合物２（２４６ｇ）にＤＥＴＤＡ（７０ｇ）およびポリオール１（６５５ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（３ｇ）、消泡剤（１ｇ）、硬化触媒１（５ｇ）を順次添加、撹拌を行ない、粘度４８０ｍＰａ．ｓ／２５℃、比重１．０５の混合レジンを得た。このときレジン中の全芳香族ジアミン中のＤＥＴＤＡ当量％は２７．９であった。
Ｂ−５
含硫ジアミン化合物２（２４９）にポリオール１（７２２ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（３ｇ）、消泡剤（１ｇ）、硬化触媒２（５ｇ）を順次添加、撹拌を行ない粘度６２０ｍＰａ．ｓ／２５℃、比重１．０７の混合レジンを得た。
Ｂ−６
含硫ジアミン化合物２（２０４ｇ）にＤＥＴＤＡ（１００ｇ）およびポリオール１（６６７ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（３ｇ）、消泡剤（１ｇ）、硬化触媒１（５ｇ）を順次添加、撹拌を行ない、粘度４６０ｍＰａ．ｓ／２５℃、比重１．０６の混合レジンを得た。このときレジン中の全芳香族ジアミン中のＤＥＴＤＡ当量％は３９．９であった。
Ｂ−７
ＤＥＴＤＡ（２４７ｇ）にポリオール１（７２４ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（３ｇ）、消泡剤（１ｇ）、硬化触媒１（５ｇ）を順次添加、撹拌を行ない、粘度５５０ｍＰａ．ｓ／２５℃、比重１．０５の混合レジンを得た。
Ｂ−８
ＤＥＴＤＡ（１６０ｇ）にポリオール１（２０ｇ）とポリオール４（７８９ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（５ｇ）、消泡剤（１ｇ）、硬化触媒２（５ｇ）を順次添加、撹拌を行ない、粘度５００ｍＰａ．ｓ／２５℃、比重１．０５の混合レジンを得た。
【００２０】
Ｂ−９
ＤＥＴＤＡ（１７５ｇ）にポリオール１（２０ｇ）とポリオール４（７６０ｇ）および１，４ＢＧ（９ｇ）を加え、３０分間高速ディスパーで撹拌した後、顔料（２０ｇ）、耐候安定剤（５ｇ）、消泡剤（１ｇ）、硬化触媒２（１０ｇ）を順次添加、撹拌を行ない、粘度４９０ｍＰａ．ｓ／２５℃、比重１．０５の混合レジンを得た。
Ｂ−１０
ポリオール５（１５０ｇ）にＭＯＣＡ（１５０ｇ）を加え、９０℃で１時間加熱溶解し、冷却後高速ディスパーで撹拌しながら、ＤＥＴＤＡ（３０ｇ）、ポリオール１（２０ｇ）、ポリオール４（５８７ｇ）、１，４ＢＧ（３２ｇ）を順次加え、さらに顔料（２０ｇ）、耐候安定剤（５ｇ）、消泡剤（１ｇ）、硬化触媒２（５ｇ）を順次添加、撹拌を行ない、粘度１５００ｍＰａ．ｓ／２５℃、比重１．０７の混合レジンを得た。
このとき、レジン中の全芳香族ジアミン中のＤＥＴＤＡ当量％は２３．０であった。
上記Ｂ−１〜Ｂ−１０調製の原料および得られた組成物の物性を〔表２〕に示した。
【００２１】
４．ポリウレタン樹脂Ｃ−１〜Ｃ−１０の調製
Ｃ−１
主剤として７０℃に加熱したＡ−１、硬化剤として６０℃に加熱したＢ−１をそれぞれガスマー社製 Ｈ２０００を用いて圧送し、プロブラーガンにて離型フィルム上に約２ｋｇ／ｍ^２吹き付けを行った。なお、このときのゲルタイムは１５０秒であった。また得られたエラストマーを２５℃下で７日間硬化養生したのち脱型し、ＪＩＳ Ｋ６２５３記載のタイプＤデュロメータにてＤ硬度を測定したところ５８であった。また、ＪＩＳ Ｋ６３０１記載の引張物性試験を行ったところ引張強度２２ＭＰａ、伸び率２４０％であった。
Ｃ−２
主剤として７０℃に加熱したＡ−１、硬化剤として６０℃に加熱したＢ−２をそれぞれガスマー社製 Ｈ２０００を用いて圧送し、プロブラーガンにてＣ−１と同様にして吹き付けを行った。このときゲルタイムは１８０秒であった。またＣ−１と同様に物性試験を行ったところ、Ｄ硬度６５、引張強度２７ＭＰａ、伸び率２００％であった。
Ｃ−３
主剤として７０℃に加熱したＡ−１、硬化剤として６０℃に加熱したＢ−３を用い、同様に圧送、吹き付けを行った。このときゲルタイムは６０秒であった。また同様に物性試験を行ったところ、Ｄ硬度６０、引張強度２４ＭＰａ、伸び率１９０％であった。
Ｃ−４
主剤として７０℃に加熱したＡ−１、硬化剤として６０℃に加熱したＢ−４を用い、同様に圧送、吹き付けを行った。このときゲルタイムは４０秒であった。また同様に物性試験を行ったところ、Ｄ硬度６２、引張強さ２０ＭＰａ、伸び率２５０％であった。
Ｃ−５
主剤として６０℃に加熱したＡ−３、硬化剤として６０℃に加熱したＢ−５を用い、同様に圧送、吹き付けを行った。このときゲルタイムは２００秒であった。また同様にして物性試験を行ったところ、Ｄ硬度４５、引張強さ１５ＭＰａ、伸び率３００％であった。
【００２２】
Ｃ−６
主剤として７０℃に加熱したＡ−１、硬化剤として６０℃に加熱したＢ−６を用い、同様に圧送、吹き付けを行った。このときゲルタイムは１５秒であった。また同様にして物性試験を行ったところ、Ｄ硬度６０、引張強さ２４ＭＰａ、伸び率１９０％であった。
Ｃ−７
主剤として７０℃に加熱したＡ−１、硬化剤として６０℃に加熱したＢ−７を用い、同様に圧送、吹き付けを行った。このときゲルタイムは３秒であった。また同様にして物性試験を行ったところ、Ｄ硬度６０、引張強さ２３ＭＰａ、伸び率２１０％であった。
Ｃ−８
主剤として６０℃に加熱したＡ−２、硬化剤として６０℃に加熱したＢ−８を用い、同様に圧送、吹き付けを行った。このときゲルタイムは１５秒であった。また２５℃下で７日間硬化養生したのち脱型し、ＪＩＳ Ａ６０２１に準じ物性試験を行ったところ、引張強さ１０ＭＰａ、伸び率６５０％でＪＩＳ Ａ６０２１に規定される塗膜性能を有する超速硬化性中硬質エラストマーであった（Ｄ硬度２５）。
Ｃ−９
主剤として６０℃に加熱したＡ−３、硬化剤として６０℃に加熱したＢ−９を用い、同様に圧送、吹き付けを行った。このときゲルタイムは１０秒であった。またＣ−１と同様にして物性試験を行ったところ、Ｄ硬度３８、引張強さ１４ＭＰａ、伸び率４５０％であった。
Ｃ−１０
主剤として６０℃に加熱したＡ−３、硬化剤として７０℃に加熱したＢ−１０を用い、同様に圧送、吹き付けを行った。このときゲルタイムは３３０秒であった。また同様にして物性試験を行ったところ、Ｄ硬度１７、引張強さ７ＭＰａ、伸び率５００％であった。
上記Ｃ−１〜Ｃ−１０の調製原料および得られたエラストマーの物性を〔表３〕に示した。
【００２３】
参考例１
プライマー１をローラー刷毛にて１５０ｇ／ｍ^２塗布した基体（モルタル板）に、室温下（２５℃）でガスマー社製 Ｈ−２０００を用いて、樹脂Ｃ−１を１．５ｋｇ／ｍ^２吹き付け塗布し、１２０秒後に骨材２．５ｋｇ／ｍ^２をリシンガン（空気圧５ｋｇ／ｃｍ^２）を用いて散布した。さらに１０分後に樹脂Ｃ−１を０．５ｋｇ／ｍ^２吹き付け塗布して、３日間養生を行ない防滑舗装層Ｄ−１を得た。
参考例２
参考例１と同様にして樹脂Ｃ−２を１．５ｋｇ／ｍ^２吹き付け塗布し、１５０秒後に骨材２．５ｋｇ／ｍ^２を散布した。さらに１０分後に樹脂Ｃ−２を０．５ｋｇ／ｍ^２吹き付け塗布して、３日間養生を行い、防滑舗装層Ｄ−２を得た。
参考例３
参考例１と同様の基体に、防水層として樹脂Ｃ−６を、室温下（２５℃）にガスマー社製 Ｈ−２０００を用いて１．０ｋｇ／ｍ^２吹き付け塗布し、３時間硬化養生を行った後に、プライマー２を１５０ｇ／ｍ^２塗布した。層間プライマー２が乾燥した後に樹脂Ｃ−２を１．５ｋｇ／ｍ^２吹き付け塗布し、１５０秒後に骨材２．５ｋｇ／ｍ^２を散布し、さらに樹脂Ｃ−２を０．５ｋｇ／ｍ^２吹き付け塗布した。その上にトップコートを２００ｇ／ｍ^２エアレススプレー塗布して複合防滑舗装層Ｄ−３を得た。
【００２４】
実施例１
参考例１と同様の基体に、室温下（２５℃）で樹脂Ｃ−３を１．５ｋｇ／ｍ^２吹き付け塗布し、５０秒後に骨材２．５ｋｇ／ｍ^２を散布し、さらに樹脂Ｃ−３を０．５ｋｇ／ｍ^２吹き付け塗布して、防滑舗装層Ｄ−４を得た。
実施例２
参考例１と同様の基体に、室温下（２５℃）で樹脂Ｃ−４を１．５ｋｇ／ｍ^２吹き付け塗布し、３０秒後に骨材２．５ｋｇ／ｍ^２を散布し、さらに樹脂Ｃ−４を０．５ｋｇ／ｍ^２吹き付け塗布して防滑舗装層Ｄ−５を得た。
参考例４
参考例１と同様の基体に、室温下（２５℃）で樹脂Ｃ−５を１．５ｋｇ／ｍ^２吹き付け塗布し、１８０秒後に骨材２．５ｋｇ／ｍ^２を散布し、さらに樹脂Ｃ−５を０．５ｋｇ／ｍ^２吹き付け塗布して防滑舗装層Ｄ−６を得た。
【００２５】
比較例１
参考例１と同様の基体に、室温下で樹脂Ｃ−６を１．５ｋｇ／ｍ^２吹き付け塗布して１０秒後に骨材２．５ｋｇ／ｍ^２をリシンガンを用いて散布し、さらに樹脂Ｃ−６を０．５ｋｇ／ｍ^２吹き付け塗布して防滑舗装層Ｄ−７を得た。
比較例２
参考例１と同様の基体に、室温下で樹脂Ｃ−７を１．５ｋｇ／ｍ^２吹き付け塗布すると同時に骨材２．５ｋｇ／ｍ^２をリシンガンを用いて散布し、さらに樹脂Ｃ−７を０．５ｋｇ／ｍ^２吹き付け塗布して防滑舗装層Ｄ−８を得た。
比較例３
参考例１と同様の基体に、室温下で樹脂Ｃ−８を１．５ｋｇ／ｍ^２吹き付け塗布して５秒以内に骨材２．５ｋｇ／ｍ^２をリシンガンを用いて散布し、さらに樹脂Ｃ−８を０．５ｋｇ／ｍ^２吹き付け塗布して、防滑舗装層Ｄ−９を得た。
【００２６】
比較例４
樹脂１と同様の基体に、室温下で樹脂Ｃ−９を１．５ｋｇ／ｍ^２吹き付け塗布して５秒以内に骨材２．５ｋｇ／ｍ^２をリシンガンを用いて散布し、さらに樹脂Ｃ−９を０．５ｋｇ／ｍ^２吹き付け塗布して、防滑舗装層Ｄ−１０を得た。
比較例５
参考例１と同様の基体に、室温下で樹脂Ｃ−１０を１．５ｋｇ／ｍ^２吹き付け塗布して、３００秒後に骨材２．５ｋｇ／ｍ^２をリシンガンを用いて散布し、さらに樹脂Ｃ−１０を０．５ｋｇ／ｍ^２吹き付け塗布して防滑舗装層Ｄ−１１を得た。防滑舗装層全体の構成を〔表４〕に示した。
【００２７】
評価試験
評価項目、評価方法および結果
（１）骨材散布作業性
防滑舗装層を調製するにあたって、ポリウレタンエラストマーを吹き付けた後、防滑骨材を散布するまでの時間（オープンタイム）が６０秒以上確保出来るものを◎、３０秒確保できるものを○、オープンタイムが３０秒以上確保出来ず、エラストマー吹き付けと骨材散布をほぼ同時に行う必要のあるものを×として評価した。その結果を〔表４〕に示した。
防滑舗装層Ｄ−１、Ｄ−２、Ｄ−３およびＤ−６はポリウレタンエラストマー吹き付け後、骨材散布までの充分な時間的余裕が確保出来た。Ｄ−４およびＤ−５もある程度の時間が取れたが、それ以外は該エラストマー吹き付けと骨材散布をほぼ同時に行わなければならなかった。
【００２８】
（２）傾斜面での垂れ性
基体を１／４勾配になるように傾けたものに、各防滑舗装層を施工した際、吹き付け塗布したポリウレタンエラストマーが垂れることなく、所定の厚みを付けることが出来るものを◎、やや垂れが起こるものの、外観上問題のないものを○、垂れが著しく、下方に吹き付けたエラストマーの溜まりが生じるものを×とした。その結果を〔表４〕に示した。
防滑舗装層Ｄ−１、Ｄ−２、Ｄ−３およびＤ−６はやや垂れる傾向が見られるが、外観上は特に問題なく、傾斜面上部と下部での防滑舗装層の厚みがほぼ均一であり○であった。またＤ−１１については骨材散布後も舗装層の垂れが著しく、傾斜下方に溜まりが出来てしまった。
【００２９】
（３）耐加重摩耗性
耐加重摩耗性は『床加重摩耗試験機』を用いて評価した。
この試験機は、供試体に硬度６０のウレタン車輪（φ１５０ｍｍ）で最大１．５トンの垂直圧縮加重を与えると同時に、最速１２回／分のねじり負荷を与えることの出来る装置である。
各防滑舗装層に、加重５００ｋｇｆ（約３５ｋｇｆ／ｃｍ^２）、速度４回／分の圧縮ねじり負荷を繰り返し与え、防滑骨材の欠落・離脱の有無、異常摩耗や舗装層破断の有無を見ることで、耐久性比較を行った。
防滑舗装層調製後、室温下で３日間養生を行ったものを供試体とし、３００回の圧縮ねじり負荷を与えた後でも防滑骨材の著しい欠落・離脱やエラストマーの破断等の異常が認められなかった舗装層を◎、１００〜３００回の圧縮ねじり負荷で異常が認められた舗装層を○、５０〜１００回で異常が認められた舗装層を×、５０回以下で異常が認められた舗装層を××とした。その結果を〔表４〕に示した。
防滑舗装層Ｄ−１、Ｄ−２、Ｄ−３はエラストマーと骨材との接着性が良好で、かつ強靱であるため３００回の圧縮ねじりを行った後でも、著しい骨材の欠落・離脱やエラストマー部分の破断は認められなかった。
Ｄ−４、Ｄ−５はＤ−１、Ｄ−２、Ｄ−３に比べるとエラストマーと骨材の接着性が多少劣るため、欠落・離脱が目立つものの、舗装層そのものに破断や異常摩耗は認められなかった。
Ｄ−６はエラストマーと骨材との接着性はＤ−１、Ｄ−２、Ｄ−３とほぼ同レベルであり、骨材の欠落・離脱は少ないが、エラストマー自身の強度がやや低いため、３００回の負荷で一部破断が認められた。
それに対してＤ−７、Ｄ−８、Ｄ−９、Ｄ−１０はエラストマーと骨材の接着性が悪いため骨材の欠落・離脱が著しく、またＤ−１１は骨材の接着性は比較的良好であったが、エラストマー部分に破断や異常摩耗が認められた。
【００３０】
（４）耐繰り返し疲労
ＪＡＳＳ８（１９９３）の「メンブレン防水層の性能評価試験方法」に記載されている疲労試験方法（Ｂ１形試験体）に準じて実施した。区分として疲労Ｂ３に該当する舗装層を◎、疲労Ｂ２に該当する舗装層を○とした。その結果を〔表４〕に示した。
いずれの防滑舗装層も繰り返し疲労性は良好であったが、特にＤ−３が優れていた。
（５）滑り抵抗性
ＪＩＳ Ａ１４０７に準じて滑り抵抗係数の測定を行った。一般的に滑りにくいとされる０．４以上の舗装層を○、０．４以下の舗装層を×とした。その結果を〔表４〕に示した。
【００３１】
【表１】

【００３２】
【表２】

【００３３】
【表３）】

【００３４】
【表４】

【００３５】
【発明の効果】
本発明に使用する二成分型ポリウレタン樹脂は塗布後のゲルタイムが３０秒以上３００秒以下に調整されているため、スロープ面にも容易に施工が可能であり、なおかつ骨材の散布作業性に優れる。またこのポリウレタンエラストマーは高い硬度と強度を有しており、得られる防滑舗装層は強靱で、骨材との接着性に優れた強固なものとなる。[0001]
BACKGROUND OF THE INVENTION
The present invention is an outdoor or built-in parking lot structure that is excellent in load / running durability, anti-slip property, wear resistance, oil resistance, water resistance, foundation stretchability, workability, and curability, heavy vehicle travel zone, Used for other passages that require anti-slip propertiesInclined surfaceAnti-slipDressIt is about the law.
[0002]
[Prior art]
With the rapid increase in the number of vehicles such as passenger cars in recent years, a shortage of parking spaces has become a problem. In particular, in the city center, it is extremely difficult to secure a dedicated parking lot, so many of them use anti-skid paving on the rooftop of the building, inside the building, underground, etc., and use it as a parking lot. In this case, the pavement layer is required to have performances such as a waterproof function having a base expansion / contraction followability, a toughness capable of withstanding heavy wear during vehicle passage, and an anti-slip property.
The general specification of the pavement layer currently in use is that asconal or concrete having a thickness of about 5 cm is placed on the asphalt waterproofing material as a press pavement layer.
The problem with this specification is that the weight of the holding pavement layer is large, so it is necessary to increase the design load of the beams and columns of the building, and it is necessary to remove the holding pavement layer when repairing the waterproof layer, For example, the construction will be a major issue.
In order to solve these problems, specifications have been implemented in which aggregate is combined with fiber reinforced thermosetting plastic (FRP) as a pavement layer, and a polymer composition having an elongation of 30% or more as a waterproof layer. In this specification, since the total thickness of the pavement layer is a thin film of about 1 to 5 mm, it is possible to reduce the weight of the design of the building, and it is easy to identify and repair leak points, but there are many processes. The construction itself requires a lot of time, especially in winter construction, because a longer curing time is needed to develop practical strength, so it is unavoidable to prohibit the use of a long time when renovating the parking lot. It is a fact. In addition, in terms of performance, it is difficult to ensure adhesion between urethane as a waterproof layer and FRP as an anti-slip layer, and there is also a drawback that the waterproof layer often breaks due to weighted wear.
[0003]
Moreover, the specification etc. which mix | blended aggregate with hard urethane resin as an antiskid pavement layer, and combined the medium hard or soft urethane which the coating-film physical property which conforms to JISA6021 as a waterproofing layer are implemented. This specification has advantages such as lighter building design load, easy identification and repair of leak points, good weight and running durability, but still requires a large number of processes and requires a relatively long curing time. Therefore, the problems in terms of construction period have not been solved.
In order to shorten the construction period, specifications for applying a two-component ultra-fast curing polyurethane elastomer using a special sprayer (impact mixing method, static mixing method, etc .: H2000 made by Gasmer, G-41 made by Unipre) have also been implemented. Yes. As an anti-slip pavement method in this case, embossing with the same resin is performed, but the anti-slip effect is low, and the surface slip resistance value is particularly low when wet, so there is a high risk of slip accidents.
As another method of applying a two-component ultra-fast curing polyurethane elastomer using a special sprayer to form an anti-slip pavement layer, there is also a method of spraying and finishing aggregates such as silica sand at the same time as the elastomer is sprayed. . Specifically, the aggregate is sprayed by hand or lysing gun at the same time as the elastomer is sprayed or just before gelation after spraying. However, since the gel time of the resin used so far is as short as 5 to 30 seconds, the workability of spraying the aggregate (securing the open time) is poor, and the adhesion between the polyurethane elastomer and the aggregate is not sufficiently secured. For this reason, there is a drawback that the anti-slip property cannot be maintained because the aggregate is missing or detached while the vehicle is repeatedly running.
In order to improve the dispersion workability of the aggregate and the adhesion between the two-component polyurethane elastomer and the aggregate, there is a method using a less reactive amine compound such as a halogen-containing diaminobenzene as a chain extender. The hardness and strength of the cured product are low, and aggregates are lost or detached due to repeated running of the vehicle.
[0004]
The same applies to paving layers used for factory aisle floors and platforms that carry and unload heavy objects with forklifts, automated guided vehicles, etc., as well as anti-slip, toughness, base stretchability, chemical resistance, and design. Performance such as sex is required.
As a general anti-slip pavement layer of these factory floor pavements, a combination of epoxy resin and hard aggregate is often used. As a pavement method, for example, a method of spraying hard aggregate after application of epoxy resin and applying the same epoxy resin as a protective layer after curing, a resin mortar premixed with epoxy resin and hard aggregate, iron, rake, etc. There is a method of applying by.
The problem with this specification is that the elongation at break of the epoxy resin used is as small as a few percent, and it cannot follow movements such as cracks and vibrations of the frame, so cracks occur in the pavement layer, and falling objects For example, the resistance to impact is weak, the onset of practical strength is slow in construction in winter, and long-term curing is required after construction.
In addition, many pavement materials and pavement methods are used in which a methyl methacrylate resin and a hard aggregate, which have a rapid development of practical strength, are used instead of an epoxy resin. However, in this case as well, the base expansion / contraction followability is insufficient, and the problem of cracks has not been solved.
Recently, in place of the above-mentioned pavement method, a pavement method in which a composition comprising a hard urethane elastomer having a D hardness of 60 to 80 and an elongation of 50 to 200% and a hard aggregate is applied with a trowel, rake or the like is also employed. ing. This specification has toughness equivalent to that of epoxy resin and methyl methacrylate resin, and has advantages such as excellent load-resistant wear resistance, base stretchability, and impact resistance. Practical strength development is slow, and problems in terms of construction remain unresolved.
[0005]
[Problems to be solved by the invention]
The object of the present invention is to adjust the gelation time of the fast-cure polyurethane elastomer to be sprayed, so that there is a time allowance between the elastomer spraying and the aggregate spraying work, and the adhesiveness between the elastomer and the aggregate is excellent. In addition, the present invention provides a lightweight, high-strength, high-elongation anti-skid pavement layer that does not sag on the slope surface and that exhibits practical strength in a few hours even at low temperatures, and a method for its construction.
[0006]
  The present inventors solve the above problems by an antiskid pavement layer obtained by spraying aggregate before the two-component polyurethane resin layer whose gel time is adjusted to 30 seconds or more and 300 seconds or less is gelled. The present invention was completed by further research based on the knowledge.
That is, the present invention
(1)It comprises an isocyanate component and an active hydrogen component, and the active hydrogen component is a general formula (1) as a chain extender.
[Chemical 1]

[In the formula, R ¹ And R ² Are the same or different alkyl groups having 1 to 5 carbon atoms, X ¹ And X ² One is hydrogen and the other is NH ₂ , X ³ Is hydrogen or -SR ³ (R ³ Is an alkyl group having 1 to 5 carbon atoms. A sulfur-containing aromatic diamine and diethyltoluenediamine represented byTwo-component polyurethane resin with gel time adjusted to 30 seconds or more and 300 seconds or lessIs applied to the inclined surface, and the coating layer isScatter aggregate before gellingAnti-slip pavement method for inclined surfaces,
(2) The antiskid pavement according to (1), wherein the gel time of the two-component polyurethane resin is adjusted to 60 seconds or more and 180 seconds or less.Method,
(3)On the inclined surface,Providing a primer layer and / or a waterproof layer;ThenClaim 1Or 2To form an antiskid pavement layer as described in any of the above.On the anti-slip pavement layerAnti-skid pavement method for providing a protective layer and / or top coat layer,
(4) The protective layer is provided by applying a two-component polyurethane resin, and the top coat layer is provided by applying a non-yellowing acrylic urethane paint (3)The slip-proof paving method described,
It is.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The polyurethane resin used in the present invention must have a gel time of 30 seconds or more and 300 seconds or less. The reason why it must be 30 seconds or more is that if it is 30 seconds or less, there is no time margin between the resin application and the aggregate spraying work. Even if obtained, this super fast-curing resin has poor adhesion to the aggregate, and the resulting anti-slip layer has poor grip on the aggregate, so the aggregate may be lost due to repeated running of the vehicle. . In consideration of this point, a more preferable gel time is 60 seconds or more.
The reason why it must be 300 seconds or less is that when a resin having a gel time of 300 seconds or more is sprayed onto the slope surface, dripping occurs and an antiskid pavement layer with a uniform film thickness cannot be obtained, and until the development of practical strength. It is mentioned that curing is necessary. In consideration of this point, a more preferable gel time is 180 seconds or less.
The gel time in the present invention means that a polyurethane elastomer stock solution heated to about 65 ° C. is used as a base material made of mortar held vertically in a room at 25 ° C. using a two-component pumping / mixing machine (H-2000 manufactured by Gasmer). About 2kg / m²Time until spraying and dripping fluidity disappears.
The two-component polyurethane resin of the present invention can be obtained by reacting an isocyanate component and an active hydrogen component.
[0008]
The isocyanate component is a partial prepolymer obtained by reacting a part of an organic isocyanate or isocyanate group with, for example, a polyol having a molecular weight of 100 to 10,000, but if necessary, a plasticizer or a flame retardant may be added. good.
Since the urethane resin thus prepared is prepared with an initial gel time of 30 seconds or more and 300 seconds or less, there is a time margin for spraying the aggregate after spraying, and there is a 1/2 in the parking lot structure. It has a curability that does not sag even on a slope surface of about 4 gradients, and has excellent adhesion between the elastomer and the dispersed aggregate, so that it becomes a slip-proof pavement layer in which aggregates are not lost or detached even when a heavy vehicle travels.
Examples of the organic isocyanate constituting the isocyanate component include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof (TDI), diphenylmethane-4,4 ′ diisocyanate (MDI), and xylylene diisocyanate (XDI). , Dicyclohexylmethane diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate (HXDI), crude MDI (c-MDI), and isocyanurate-modified products of these isocyanates And carbodiimide-modified products.
Of these organic polyisocyanates, MDI, c-MDI and modified products thereof are particularly preferred.
These organic polyisocyanates can be used as an isocyanate component as they are, but can also be used as a partial prepolymer obtained by heating a part of isocyanate groups with a polyol, for example, at 70 to 80 ° C. for several hours in a nitrogen stream. .
[0009]
Polyols that can be used in the production of the partial prepolymer include water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, polyhydric alcohols such as pentaerythritol, and one or more alkylene oxides such as ethylene oxide and propylene oxide. There is a polyether polyol obtained by addition polymerization. Other examples include polytetramethylene ether glycol, castor oil, and polycarbonate polyol.
For the production of the partial prepolymer, in addition to the polyol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and mixtures thereof, ethylene glycol, diethylene glycol, 1,3-butylene glycol, molecular weight less than 1,000 Low molecular weight polyols such as polyether polyol and polytetramethylene ether glycol having a molecular weight of less than 1,000 can be used.
Although the polyol which can be used for manufacture of a partial prepolymer is the said polyol individually or in mixture of 2 or more types, the thing whose molecular weight is about 60-5,000 is preferable.
The NCO% by weight of the isocyanate component is determined by the kind and molar ratio of the organic isocyanate and the active hydrogen compound at the time of production, but the preferred NCO% of the prepolymer used in the present invention is about 10-20.
[0010]
The active hydrogen component includes a polyol having a molecular weight of about 100 to 10,000 and a sulfur-containing aromatic diamine represented by the general formula (1) as a chain extender, and if necessary, other auxiliary agents such as an organometallic catalyst and a colorant. , Flame retardants, antifoaming agents, plasticizers, fillers, silane coupling agents and the like may be included.
The polyol used for the preparation of the active hydrogen component is water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, polyhydric alcohols such as pentaerythritol, and one or more alkylene oxides such as ethylene oxide and propylene oxide. There is a polyether polyol obtained by addition polymerization. Other examples include polytetramethylene ether glycol, castor oil, polycarbonate polyol, and amino group-terminated polyoxyalkylene polyol.
The active hydrogen component used in the present invention has a general formula (1) as a chain extender.
[Chemical 3]

(Where R¹, R², R³, X¹, X²And X³Can be blended with a sulfur-containing aromatic diamine represented by the same meaning as described above. In general formula (1), R¹, R²And R³Examples of the alkyl group having 1 to 5 carbon atoms represented by: include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl and the like, and methyl and ethyl are preferable. Specific examples of the sulfur-containing aromatic diamine represented by the general formula (1) include, for example, 1-ethylthio-diaminobenzene, 5-methylthio-diaminotoluene, 5-ethylthio-diaminotoluene, 5-isopropylthio-diatoluene, 5 -Ethylthio-diaminoethylbenzene, 5-methylthio-diaminoethylbenzene, 3,5 dimethylthio-diaminotoluene, 3,5-diethylthio-diaminotoluene, 3,5 dimethylthio-diaminobenzene, 3,5-diethylthio-diaminobenzene, 3,5 -Dimethylthio-diaminoethylbenzene, 3,5-diethylthio-diaminoethylbenzene and the like.
[0011]
  These sulfur-containing aromatic diamines can be used alone or as a mixture of two or more.
  Other than the above sulfur-containing aromatic diaminesToEthyltoluenediamine (DETDA)Is blended. furtherAlkanediols such as ethylene glycol, propylene glycol, 1,4-butanediol, aliphatic amine compounds such as ethylenediamine, low molecular weight alkanolamines such as diethanolamine and triethanolamine, low molecular weight polyols such as glycerin and trimethylolpropane, etc. What is called a cross-linking agentTheCan be used as a chain extender.From the viewpoint of the curability and physical properties of the elastomer, a combination of sulfur-containing aromatic diamine and DETDA is preferable. Here, the amount of DETDA used is desirably 30 mol% or less of the total amino groups in the wholly aromatic diamine. This is because when the amino group of DETDA is 30 mol% or more, the initial gel time may be extremely shortened, the workability of the aggregate spraying may be deteriorated, and the adhesiveness between the elastomer and the aggregate may be lowered. The chain extender shown above is suitably 5 to 50 parts by weight per 100 parts by weight of polyol. The organometallic compound used for the production of the active hydrogen component is a reaction accelerator with the isocyanate component, and known urethane catalysts such as lead octylate and dibutyltin dilaurate can be used. Among them, the use of bismuth octylate is preferable in order to prevent foaming due to water and from the viewpoint of safety.
[0012]
Further, a colorant, a flame retardant, a plasticizer, a filler, an antifoaming agent, a stabilizer, and a silane coupling agent as auxiliary agents can be added to each of the isocyanate component and the active hydrogen component. As the colorant, for example, inorganic and organic systems such as carbon black, bengara, chromium oxide, and titanium oxide can be used.
Examples of the plasticizer include phthalate esters such as dioctyl phthalate (DOP), and adipate esters such as dioctyl adipate (DOA), and the flame retardants can be used alone or in combination.
As the stabilizer, a heat stabilizer, an ultraviolet absorber, and a weather stabilizer can be used alone or in combination. As the alkoxysilane coupling agent, generally known ones can be used, but a silane compound having an isocyanate group or an epoxy group as a reactive group is preferable.
[0013]
The antiskid pavement layer of the present invention is usually made of concrete, mortar, ascon, etc.InclinedFormed on a substrate. Prior to the formation of the anti-skid pavement layer, a primer and / or a waterproof layer may be provided on the substrate. On top of that, the two-component polyurethane resin of the present invention is applied, and aggregates are dispersed before gelation to form an antiskid pavement layer. If necessary, a protective layer and / or a top coat layer may be provided on the anti-skid pavement layer. As the primer, a one-component moisture-curing urethane primer is suitable, but is not limited thereto. What is suitable as a waterproof layer is obtained by spray-coating a room temperature super-fast curing polyurethane resin known per se. For example, two components, ie, a main component mainly composed of an isocyanate-terminated urethane polymer and a curing agent mainly composed of a polyether polyol, are sprayed at high or low pressure (for example, H-2000 manufactured by Gasmer, G- manufactured by Unipur) 41 etc.), and the gel time is 5 to 30 seconds. It is desirable that the physical properties of the waterproof layer conform to the standards defined in JIS A6021.
[0014]
  Anti-slip pavement of the present inventionDressing methodIs carried out by pumping, mixing, and applying two components of an isocyanate component and an active hydrogen component, and spraying the aggregate until the resin layer is gelled. Examples of the two-component mixing method include collision mixing, static mixing, and dynamic mixing, and the same apparatus as that used in the formation of the waterproof layer can be used. Although the usage-amount of a polyurethane resin is not specifically limited, Usually 0.5-5 kg / m², Preferably 1 to 3 kg / m²It is.
  The elastomer obtained from the two-component polyurethane resin preferably has a D hardness of 45 or more, a tensile strength described in JIS K6301 of 10 MPa or more, and an elongation of 150% or more.
Anti-slip pavement of the present inventionMethodThere are no particular restrictions on the material and particle size of the aggregate used in the above, but silica sand, calcined alumina or rubber chips having a particle size of 0.5 to 3 mm are preferred from the standpoints of finish and durability. Also, there is no particular limitation on the method (means) of applying the aggregate, and it may be applied by hand or a machine capable of blowing air may be used. The amount of aggregate used varies depending on the material, particle size, etc., but is usually 1-5 kg / m.², Preferably 1.5 to 3.0 kg / m²It is. This anti-skid pavement layer usually hardens almost completely after 15 minutes and is ready to walk on it. For the formation of the protective layer, the two-component polyurethane resin used for the anti-skid pavement layer can be suitably used. The top coat layer is used for the purpose of preventing discoloration of the anti-skid pavement layer due to ultraviolet irradiation, and a known paint such as non-yellowing acrylic urethane can be used.
[0015]
【Example】
Next, the present invention will be described more specifically with reference to examples, comparative examples and evaluation tests of the present invention.
1. Raw materials used
LM: 4,4'-diphenylmethane diisocyanate (NCO% 33.7) (BAPL Corporation Lupranate M)
L-MM103: Carbodiimide-modified liquid MDI (NCO% 29.0) (BAPL Corporation Lupranate MM-103)
Polyol 1: Bifunctional polypropylene glycol (EO; 0%), hydroxyl value 56 (Takelac P-21, Takeda Pharmaceutical Company Limited)
Polyol 2: trifunctional polypropylene glycol (EO; 0%), hydroxyl value 56 (Accor 79-56, Takeda Pharmaceutical Company Limited)
Polyol 3: Bifunctional polypropylene glycol (EO; 0%), hydroxyl value 38 (Takelac P-23, Takeda Pharmaceutical Company Limited)
Polyol 4: Bifunctional polypropylene glycol (EO; 15%), hydroxyl value 46 (Accor MF-16, manufactured by Takeda Pharmaceutical Company Limited)
Polyol 5: Trifunctional polypropylene glycol (EO; 15%), hydroxyl value 34 (Accor TE-5000 manufactured by Takeda Pharmaceutical Co., Ltd.)
・ 1,4BG: 1,4-butanediol
[0016]
-Polyether polyamine 1: bifunctional polyether amine, hydroxyl value 56 (converted with one terminal hydrogen group as active hydrogen)
-Polyether polyamine 2: Trifunctional polyether amine, hydroxyl value 56 (converted with one terminal hydrogen group as active hydrogen)
-Sulfur-containing diamine compound 1: mixture of 3,5-dimethylthio-2,4-diaminotoluene and 3,5-dimethylthio-2,6-diaminotoluene
Sulfur-containing diamine compound 2: a mixture of 3,5-diethylthio-2,4-diaminotoluene and 3,5-diethylthio-2,6-diaminotoluene
DETDA: a mixture of 3,5 diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine
MOCA: 3,3'-dichloro-4,4'-diaminodiphenylmethane
・ Pigment: Titanium oxide
-Weathering stabilizer: A mixture of a hindered phenol-based antioxidant and a hindered amine-based ultraviolet absorber (Cinubain B-75 manufactured by Ciba Geigy)
Antifoaming agent: Non-silicone antifoaming agent (BYK-065 manufactured by BYK Chemie)
Curing catalyst 1: bismuth octylate (containing 20% Bi)
Curing catalyst 2: lead octylate (containing 20% Pb)
・ DOP: Dioctylphthalate
-TMCPP: Tris monochloropropyl phosphate
Primer 1: One-component moisture-curing urethane primer (NV50) for surface treatment (Takenate F-526, Takeda Pharmaceutical Co., Ltd.)
Primer 2: One-part moisture-curing urethane primer (NV25) for waterproof / skid pavement layers (Takenate M-402P, Takeda Pharmaceutical Co., Ltd.)
-Anti-slip aggregate: No. 4/5 No. 1/1 mixed silica sand
Top coat: Two-component curable acrylic urethane paint (UP Top 620 manufactured by Takeda Pharmaceutical Company Limited)
[0017]
2. Preparation of isocyanate components A-1 to A-3
A-1
Polyol 1 (419 g) was added to L-MM103 (581 g) and allowed to react with stirring at 80 ° C. for 3 hours under a nitrogen stream, and NCO% 15, viscosity 1000 mPa · s / 25 ° C., specific gravity 1.07 (25 ° C.). A partial prepolymer was obtained.
A-2
After adding polyol 1 (438 g) to LM (344 g) and reacting with stirring at 80 ° C. for 3 hours under a nitrogen stream, L-MM103 (18 g) and TMCPP (200 g) were added, NCO% 10 and viscosity 750 mPa . A partial prepolymer having an s / 25 ° C. and a specific gravity of 1.15 (25 ° C.) was obtained.
A-3
After adding polyol 2 (83 g) and polyol 3 (332 g) to LM (391 g) and reacting with stirring at 80 ° C. for 3 hours under a nitrogen stream, L-MM103 (44 g) and DOP (150 g) were added. , NCO% 13, viscosity 500 mPa.s. A partial prepolymer having an s / 25 ° C. and a specific gravity of 1.08 (25 ° C.) was obtained.
[0018]
3. Preparation of active hydrogen components B-1 to B-10
B-1
After adding polyol 1 (669 g) to sulfur-containing diamine compound 1 (302 g) and stirring with a high speed disper for 30 minutes, pigment (20 g), weathering stabilizer (3 g), antifoaming agent (1 g), and curing catalyst 1 (5 g) ) Were sequentially added and stirred to obtain a mixed resin having a viscosity of 610 mPa.s / 25 ° C. and a specific gravity of 1.06.
B-2
After adding polyol 1 (627 g) to sulfur-containing diamine compound 2 (344 g) and stirring with a high-speed disper for 30 minutes, pigment (20 g), weathering stabilizer (3 g), antifoaming agent (1 g), and curing catalyst 1 (5 g) ) Were sequentially added and stirred to obtain a mixed resin having a viscosity of 650 mPa.s / 25 ° C. and a specific gravity of 1.06.
B-3
After adding DETDA (50 g) and polyol 1 (647 g) to sulfur-containing diamine compound 2 (274 g) and stirring with a high speed disper for 30 minutes, pigment (20 g), weather stabilizer (3 g), antifoaming agent (1 g), Curing catalyst 1 (5 g) was sequentially added and stirred, and the viscosity was 600 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.06 was obtained. At this time, the DETDA equivalent% in the wholly aromatic diamine in the resin was 19.8.
[0019]
B-4
After adding DETDA (70 g) and polyol 1 (655 g) to the sulfur-containing diamine compound 2 (246 g) and stirring with a high-speed disper for 30 minutes, a pigment (20 g), a weather resistance stabilizer (3 g), an antifoaming agent (1 g), Curing catalyst 1 (5 g) was sequentially added and stirred, and the viscosity was 480 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.05 was obtained. At this time, the DETDA equivalent% in the wholly aromatic diamine in the resin was 27.9.
B-5
After adding polyol 1 (722 g) to sulfur-containing diamine compound 2 (249) and stirring with a high speed disper for 30 minutes, pigment (20 g), weathering stabilizer (3 g), antifoaming agent (1 g), curing catalyst 2 (5 g) ) In this order and stirring, the viscosity is 620 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.07 was obtained.
B-6
After adding DETDA (100 g) and polyol 1 (667 g) to sulfur-containing diamine compound 2 (204 g) and stirring with a high-speed disper for 30 minutes, pigment (20 g), weather stabilizer (3 g), antifoaming agent (1 g), Curing catalyst 1 (5 g) was sequentially added and stirred, and the viscosity was 460 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.06 was obtained. At this time, the DETDA equivalent% in the wholly aromatic diamine in the resin was 39.9.
B-7
Add polyol 1 (724g) to DETDA (247g) and stir with high speed disper for 30 minutes, then add pigment (20g), weathering stabilizer (3g), antifoaming agent (1g), and curing catalyst 1 (5g) in this order. , The viscosity is 550 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.05 was obtained.
B-8
After adding polyol 1 (20 g) and polyol 4 (789 g) to DETDA (160 g) and stirring with a high speed disper for 30 minutes, pigment (20 g), weathering stabilizer (5 g), antifoaming agent (1 g), curing catalyst 2 (5 g) was added sequentially and stirred, and the viscosity was 500 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.05 was obtained.
[0020]
B-9
After adding polyol 1 (20 g), polyol 4 (760 g) and 1,4BG (9 g) to DETDA (175 g) and stirring with a high speed disper for 30 minutes, pigment (20 g), weathering stabilizer (5 g), antifoaming agent (1 g) and curing catalyst 2 (10 g) were sequentially added and stirred, and the viscosity was 490 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.05 was obtained.
B-10
MOCA (150 g) was added to polyol 5 (150 g), heated and dissolved at 90 ° C. for 1 hour, and after cooling, stirring with a high-speed disper, DETDA (30 g), polyol 1 (20 g), polyol 4 (587 g), 1, 4BG (32 g) was added sequentially, and a pigment (20 g), a weathering stabilizer (5 g), an antifoaming agent (1 g), and a curing catalyst 2 (5 g) were sequentially added and stirred, and the viscosity was 1500 mPa.s. A mixed resin having an s / 25 ° C. and a specific gravity of 1.07 was obtained.
At this time, DETDA equivalent% in the wholly aromatic diamine in the resin was 23.0.
The raw materials for the preparation of B-1 to B-10 and the physical properties of the obtained composition are shown in [Table 2].
[0021]
4). Preparation of polyurethane resins C-1 to C-10
C-1
A-1 heated to 70 ° C. as the main agent and B-1 heated to 60 ° C. as the curing agent were respectively pumped using a gasmer H2000, and about 2 kg / m on the release film with a probler gun.²I sprayed. The gel time at this time was 150 seconds. The obtained elastomer was cured and cured at 25 ° C. for 7 days, then demolded, and the D hardness measured by a type D durometer described in JIS K6253 was 58. Further, when the tensile property test described in JIS K6301 was conducted, the tensile strength was 22 MPa and the elongation was 240%.
C-2
A-1 heated to 70 ° C. as the main agent and B-2 heated to 60 ° C. as the curing agent were respectively pumped using a gasmer H2000, and sprayed in the same manner as C-1 with a prober gun. . At this time, the gel time was 180 seconds. Moreover, when the physical-property test was done similarly to C-1, it was D hardness 65, tensile strength 27MPa, and elongation 200%.
C-3
Using A-1 heated to 70 ° C. as the main agent and B-3 heated to 60 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 60 seconds. Similarly, when a physical property test was performed, the D hardness was 60, the tensile strength was 24 MPa, and the elongation was 190%.
C-4
Using A-1 heated to 70 ° C. as the main agent and B-4 heated to 60 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 40 seconds. Similarly, when a physical property test was conducted, the D hardness was 62, the tensile strength was 20 MPa, and the elongation was 250%.
C-5
Using A-3 heated to 60 ° C. as the main agent and B-5 heated to 60 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 200 seconds. Similarly, the physical property test was conducted. As a result, the D hardness was 45, the tensile strength was 15 MPa, and the elongation was 300%.
[0022]
C-6
Using A-1 heated to 70 ° C. as the main agent and B-6 heated to 60 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 15 seconds. Similarly, the physical property test was conducted. As a result, the D hardness was 60, the tensile strength was 24 MPa, and the elongation was 190%.
C-7
Using A-1 heated to 70 ° C. as the main agent and B-7 heated to 60 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 3 seconds. Similarly, the physical properties were tested. As a result, the D hardness was 60, the tensile strength was 23 MPa, and the elongation was 210%.
C-8
Using A-2 heated to 60 ° C. as the main agent and B-8 heated to 60 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 15 seconds. Further, after curing and curing at 25 ° C. for 7 days, the mold was removed and subjected to a physical property test in accordance with JIS A6021. As a result, the coating film performance defined in JIS A6021 with a tensile strength of 10 MPa and an elongation of 650% was obtained. It was a medium-hard elastomer (D hardness 25).
C-9
Using A-3 heated to 60 ° C. as the main agent and B-9 heated to 60 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 10 seconds. When the physical properties were tested in the same manner as C-1, the D hardness was 38, the tensile strength was 14 MPa, and the elongation was 450%.
C-10
Using A-3 heated to 60 ° C. as the main agent and B-10 heated to 70 ° C. as the curing agent, pressure feeding and spraying were similarly performed. At this time, the gel time was 330 seconds. Similarly, the physical properties were tested. As a result, the D hardness was 17, the tensile strength was 7 MPa, and the elongation was 500%.
Table 3 shows the physical properties of the raw materials for C-1 to C-10 and the obtained elastomer.
[0023]
  referenceExample 1
  Primer 1 with roller brush 150g / m²On the coated substrate (mortar plate), resin C-1 was added to 1.5 kg / m at room temperature (25 ° C.) using H-2000 manufactured by Gasmer.²After spraying, aggregate 2.5kg / m after 120 seconds²Rishin Gun (Air pressure 5kg / cm²). After 10 minutes, resin C-1 was added at 0.5 kg / m.²After spray coating, curing was performed for 3 days to obtain an antiskid pavement layer D-1.
referenceExample 2
  referenceResin C-2 is 1.5 kg / m as in Example 1.²Spray applied and aggregate 2.5 kg / m after 150 seconds²Sprayed. After 10 minutes, resin C-2 was added at 0.5 kg / m.²After spraying and curing, curing was performed for 3 days to obtain an antiskid pavement layer D-2.
referenceExample 3
  reference1.0 kg / m using the same substrate as in Example 1, resin C-6 as a waterproof layer, and G-mer H-2000 at room temperature (25 ° C.)²After spray coating and curing for 3 hours, primer 2 is 150 g / m²Applied. After the interlayer primer 2 is dried, the resin C-2 is 1.5 kg / m.²Spray applied and aggregate 2.5 kg / m after 150 seconds²And 0.5kg / m of resin C-2²Spray applied. Top coat 200g / m on top²By applying airless spray, a composite anti-skid pavement layer D-3 was obtained.
[0024]
Example1
  referenceOn the same substrate as in Example 1, 1.5 kg / m of resin C-3 at room temperature (25 ° C.)²Spray applied and aggregate 2.5 kg / m after 50 seconds²And 0.5 kg / m of resin C-3²By spray coating, an antiskid pavement layer D-4 was obtained.
Example2
  referenceOn the same substrate as in Example 1, 1.5 kg / m of resin C-4 at room temperature (25 ° C.)²Apply by spraying and after 30 seconds aggregate 2.5kg / m²And 0.5 kg / m of resin C-4²By spray coating, an antiskid pavement layer D-5 was obtained.
referenceExample4
referenceOn the same substrate as in Example 1, 1.5 kg / m of resin C-5 at room temperature (25 ° C.)²After spray application, aggregate 2.5 kg / m after 180 seconds²And 0.5kg / m of resin C-5²The anti-skid pavement layer D-6 was obtained by spray coating.
[0025]
  Comparative Example 1
  referenceOn the same substrate as in Example 1, 1.5 kg / m of resin C-6 at room temperature.²Aggregate 2.5 kg / m 10 seconds after spraying²Is sprayed using a ricin gun, and further resin C-6 is 0.5 kg / m.²The anti-skid pavement layer D-7 was obtained by spray coating.
Comparative Example 2
  referenceOn the same substrate as in Example 1, 1.5 kg / m of resin C-7 at room temperature.²At the same time as spray application, aggregate 2.5kg / m²Is sprayed using a ricin gun, and further resin C-7 is 0.5 kg / m.²By spray coating, an antiskid pavement layer D-8 was obtained.
Comparative Example 3
  referenceOn the same substrate as in Example 1, 1.5 kg / m of resin C-8 at room temperature.²Aggregate 2.5kg / m within 5 seconds after spraying²Is sprayed with a ricin gun, and further resin C-8 is 0.5 kg / m.²By spray coating, an antiskid pavement layer D-9 was obtained.
[0026]
Comparative Example 4
  1.5 kg / m of resin C-9 on the same substrate as that of resin 1 at room temperature²Aggregate 2.5kg / m within 5 seconds after spraying²Is sprayed using a ricin gun, and further resin C-9 is 0.5 kg / m.²By spray coating, an antiskid pavement layer D-10 was obtained.
Comparative Example 5
  referenceOn the same substrate as in Example 1, 1.5 kg / m of resin C-10 at room temperature.²After spraying, aggregate 2.5kg / m after 300 seconds²Is sprayed using a ricin gun, and further resin C-10 is 0.5 kg / m.²The anti-skid pavement layer D-11 was obtained by spraying. The composition of the entire anti-slip pavement layer is shown in [Table 4].
[0027]
Evaluation test
Evaluation items, evaluation methods and results
(1) Aggregate application workability
When preparing an anti-slip pavement layer, after spraying polyurethane elastomer, the time until spraying anti-slip aggregate (open time) can be secured for 60 seconds or more ◎, 30 seconds can be secured ○, open time 30 An evaluation was made as x when the elastomer could not be secured for more than 2 seconds and the elastomer spraying and aggregate spraying had to be performed almost simultaneously. The results are shown in [Table 4].
Anti-skid pavement layers D-1, D-2, D-3 and D-6 were able to secure sufficient time until spraying the aggregate after spraying polyurethane elastomer. D-4 and D-5 also took some time, but otherwise the elastomer spraying and aggregate spraying had to be performed almost simultaneously.
[0028]
(2) Sag on an inclined surface
When each anti-skid pavement layer is applied to a base inclined to a ¼ gradient, the sprayed polyurethane elastomer does not sag and can be given a predetermined thickness. Although there was no problem in appearance, the symbol “◯” was given, and the symbol “x” was marked when dripping was significant and the elastomer sprayed downward was generated. The results are shown in [Table 4].
Anti-skid pavement layers D-1, D-2, D-3 and D-6 tend to sag slightly, but there is no particular problem in appearance, and the thickness of the anti-skid pavement layer at the top and bottom of the inclined surface is almost uniform. Yes. In addition, as for D-11, the pavement layer drastically drastically after the aggregate was sprayed, and a pool was formed below the slope.
[0029]
(3) Load-resistant wear resistance
The load wear resistance was evaluated using a “floor load wear tester”.
This tester is a device that can apply a vertical compression load of a maximum of 1.5 tons with a urethane wheel (φ150 mm) having a hardness of 60 to the specimen, and at the same time a torsional load of 12 times / min.
Each anti-slip pavement layer has a load of 500 kgf (about 35 kgf / cm²), A torsional load was repeatedly applied at a speed of 4 times / min, and the durability was compared by checking for the presence or absence of slippery aggregates and the presence of abnormal wear or pavement layer breakage.
After preparing the anti-skid pavement layer, the specimen was cured at room temperature for 3 days, and even after 300 times of compressive torsional load, abnormal slip-off aggregates and abnormalities such as breakage of the elastomer were observed. No pavement layer, ◎, pavement layer in which abnormality was found in compression torsion load of 100 to 300 times, x in pavement layer in which abnormality was found in 50 to 100 times, and abnormality was found in 50 times or less. The pavement layer was XX. The results are shown in [Table 4].
Anti-skid pavement layers D-1, D-2, D-3 have good adhesion between elastomer and aggregate and are tough. No breakage of the elastomer part was observed.
D-4 and D-5 are somewhat inferior in adhesion between the elastomer and the aggregate compared to D-1, D-2, and D-3. I was not able to admit.
D-6 has almost the same level of adhesion between the elastomer and the aggregate as D-1, D-2 and D-3, and there is little loss or detachment of the aggregate, but the strength of the elastomer itself is somewhat low. Partial breakage was observed at 300 loads.
On the other hand, D-7, D-8, D-9, and D-10 have poor adhesion between the elastomer and the aggregate, so the loss and detachment of the aggregate is remarkable, and D-11 has a comparison of the adhesion of the aggregate. The elastomer part was broken and abnormally worn.
[0030]
(4) Resistance to repeated fatigue
It was carried out according to the fatigue test method (B1 type test body) described in “Performance Evaluation Test Method for Membrane Waterproof Layer” of JASS8 (1993). As a classification, the pavement layer corresponding to fatigue B3 was marked ◎, and the pavement layer corresponding to fatigue B2 was marked ◯. The results are shown in [Table 4].
All of the anti-skid pavement layers were repeatedly fatigued, but D-3 was particularly excellent.
(5) Slip resistance
The slip resistance coefficient was measured according to JIS A1407. In general, a pavement layer of 0.4 or more, which is generally considered to be difficult to slide, was rated as “○”, and a pavement layer of 0.4 or less as “x”. The results are shown in [Table 4].
[0031]
[Table 1]

[0032]
[Table 2]

[0033]
[Table 3]]

[0034]
[Table 4]

[0035]
【The invention's effect】
Since the two-component polyurethane resin used in the present invention is adjusted to have a gel time of 30 seconds or more and 300 seconds or less after application, it can be easily applied to the slope surface, and is excellent in the workability of spraying aggregates. . Moreover, this polyurethane elastomer has high hardness and strength, and the resulting anti-skid pavement layer is tough and strong with excellent adhesion to the aggregate.

Claims (4)

It comprises an isocyanate component and an active hydrogen component, and the active hydrogen component is a general formula (1) as a chain extender.

[Wherein R ¹ and R ² are the same or different alkyl groups having 1 to 5 carbon atoms, ^one of X ¹ and X ² is hydrogen and the other is NH ₂ , X ³ is hydrogen or —SR ³ (R ³ is carbon 1-5 alkyl groups). ] A two-component polyurethane resin containing a sulfur-containing aromatic diamine and diethyltoluenediamine represented by formula (1) and having a gel time adjusted to 30 seconds or more and 300 seconds or less is applied to the inclined surface, and the bone is formed before the coating layer is gelled. Anti-slip pavement method for sloping surfaces to spread material . The antiskid pavement method according to claim 1, wherein the gel time of the two-component polyurethane resin is adjusted to 60 seconds or more and 180 seconds or less. The inclined surface is provided with a primer layer and / or a waterproof layer, and then to form a non-slip paving layer according to claim 1 or 2, further provided with a coercive Mamoruso and / or topcoat layer to anti-slip paving layer Anti-slip pavement method. The anti-skid pavement method according to claim 3, wherein the protective layer is provided by applying a two-component polyurethane resin, and the top coat layer is provided by applying a non-yellowing acrylic urethane paint.