JP3635147B2 - Road pavement resin composition - Google Patents
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- JP3635147B2 JP3635147B2 JP08028296A JP8028296A JP3635147B2 JP 3635147 B2 JP3635147 B2 JP 3635147B2 JP 08028296 A JP08028296 A JP 08028296A JP 8028296 A JP8028296 A JP 8028296A JP 3635147 B2 JP3635147 B2 JP 3635147B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/10—Homopolymers or copolymers of propene
- C09D123/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Description
【０００１】
【産業上の利用分野】
本発明は、車道、歩道、公園および広場などの不透水型の舗装、透水性舗装および排水性舗装のカラー化に好適なバインダ組成物である。本発明の組成物は、淡黄色・透明でかつ自然環境下の劣化での変色もほとんどなく、また、耐水性、自己粘着性が高くバインダとしての強度も大きいことから、天然骨材、カラー骨材および顔料などと混合することで耐久性に優れたカラー舗装材料、明色舗装材料および自然色舗装材料を提供することが可能である。
【０００２】
【従来の技術および問題点】
従来、道路舗装用のバインダとしては主として舗装用アスファルトが用いられていた。しかし、交通量の増大に伴い流動わだち掘れなどが顕著となり、これに対応するためにアスファルトにＳＢＳ、ＳＥＢＳ、ＥＥＡ、ＳＢＲ、ＢＲ、ＣＲなどのゴムや熱可塑性エラストマを添加した改質アスファルトも使用されるようになっている。
【０００３】
近年、環境、社会的ニーズが変り、都市部等における安全性向上、美化のためバスレーン、公園、遊歩道、トンネル内舗装などのカラー化、明色化が増えつつある。また、環境問題として地下水の不足、河川の濫乱、洪水などの抑制のため道路舗装の透水化が注目されている。
さらには、車道の水はねの防止や雨天時の視認性の向上などを目的に、排水性舗装の適用事例が増大している。なお、排水性舗装用混合物では、空隙率が２０％前後であることから骨材の飛散抵抗性を高める必要があり、特に、７０℃以上の軟化点、２００ｋｇｆ・ｃｍ以上のタフネス、１００ｋｇｆ・ｃｍ以上のテナシティーを有する排水性舗装用改質アスファルトが使用されている。参考までに記すが、舗装用石油アスファルトの軟化点は５５．０℃以下、通常の改質アスファルトの軟化点は７０．０℃以下である。
また、高粘度改質アスファルトを含め、従来技術はアスファルトを主体としており、それ自体が黒色であるためカラー化が困難であった。
なお、カラー化を目的としたアスファルトに代わるものの１つとして、特開平４−１００８６２号公報に示されるものがある。これには石油系溶剤抽出油、石油系、石炭系および／または天然系樹脂、熱可塑性ゴム、ナフテン酸からなる組成物が開示されている。
【０００４】
しかし、組成物単体の物性が通常の舗装用アスファルトと同等であるため、重交通道路や車道の排水性舗装には適さない。このことは、同公報に示される舗装用混合物の動的安定度が４２０〜１，０５０回／ｍｍであることからも理解できる。ちなみに、改質アスファルトを用いた混合物の設計と施工の手引き（（社）日本アスファルト協会）の表−４．１に示される動的安定度の目標値は、交通量に応じて、１，０００〜５，０００回／ｍｍとなっている。すなわち、交通量が多い地域では、１，０００回／ｍｍ程度の動的安定度では流動わだち掘れが生じてしまうことを示唆している。
一方、特開平５−２６２９２１号公報には、熱可塑性エラストマと粘着性付与樹脂からなる組成物が示されている。当該組成物は、軟化点が高く、１，１３０〜３，５００程度の動的安定度が得られるものの、骨材の飛散抵抗性を考慮しなければならない車道の排水性舗装を対象とした検討はなされていない。また、当該組成物は、通常のアスファルトのようにあらかじめ溶融しておいて骨材に添加混合するのではなく、固形のまま骨材に添加混合するもので、少量の混合物を製造する場合には適している。
さらには、アスファルトを用いないカラー混合物用のバインダは、▲１▼黒色の舗装用アスファルトなどに比べると着色性に優れるものの、黄褐色や暗黄緑色など有色で、無色透明からはほど遠いものであり、白色顔料や淡い色の顔料と組み合わせた場合や、顔料を使用せずに骨材の色を生かそうとした場合などには、十分な発色が得られない、▲２▼第２０回日本道路会議論文集ｐ．５９６〜ｐ．５９７に示されるように、自然環境下では早期に劣化し変色してしまう欠点を有している。
【０００５】
本発明は、上記の問題点などに鑑み、重交通道路の不透水型の舗装、透水性舗装および排水性舗装のカラー化に適したバインダとしての特性を有すると同時に、あらかじめ溶融しておいて骨材に添加混合する方式、および固形のまま骨材に添加混合する方式のどちらでも使用できる、淡黄色・透明でかつ自然環境下の劣化で変色がほとんどない道路舗装用樹脂組成物を提供するものである。
また、本発明は、非晶性ポリオレフィンを使用する事により、従来品に比べて低粘度で作業性、骨材との混和性がよく、劣化しにくい利点がある。
【０００６】
【課題を解決するための手段】
本発明は上記の問題点を解決するために、
非晶性ポリオレフィンを含む樹脂組成物により解決した。
具体例として、
１。非晶性ポリオレフィンを含む樹脂組成物
２。（ａ）非晶性ポリオレフィン １００重量部
（ｂ）粘着性付与剤 ３０〜２００重量部
３。（ａ）非晶性ポリオレフィン １００重量部
（ｃ）液状ポリマー １〜３０重量部
４。（ａ）非晶性ポリオレフィン １００重量部
（ｂ）粘着性付与剤 ３０〜２００重量部
（ｃ）液状ポリマー １〜３０重量部
からなる道路舗装用樹脂組成物を提供することで解決した。
【０００７】
本発明の（ａ）非晶性ポリオレフィンは特に限定されないが、以下に示すものが好のましい。プロピレン成分を５０重量％以上含む、結晶性ポリプロピレン製造の際に副生するアタクチックポリプロピレンを用いてもよいし、また、原料から所定のプロピレン成分を含有するポリプロピレンやプロピレンと他のα−オレフィンとの共重合体を目的生産して用いることができる。目的生産する場合、例えば、塩化マグネシウムに担持したチタン担持型触媒とトリエチルアルミニウムを用いて水素の存在下で重合したものを用いることができる。供給安定性および品質安定性の観点からは、目的生産された所定の非晶性ポリオレフィンを使用するのが好ましい。また、ブテン−１を５０重量％以下でかつプロピレンとブテン−１成分の合計が５０重量％以上の非晶性ポリオレフィンも好適である。さらに、上記非晶性ポリオレフィンは、数平均分子量が１，０００〜２０，０００、好ましくは１，５００〜１５，０００である。
また、エチレンを３０重量％以下でかつプロピレンとエチレン成分の合計が５０重量％以上の非晶性ポリオレフィンも好適である。さらに、上記非晶性ポリオレフィンは数平均分子量が１，０００〜２０，０００、好ましくは１，５００〜１５，０００である。
【０００８】
具体的には、上記範囲のプロピレン含有量および分子量を有するポリプロピレン、プロピレン・エチレン共重合体、プロピレン・ブテン−１共重合体、プロピレン、ブテン−１およびエチレンの３元共重合体、プロピレンとヘキセン−１、オクテン−１または２−メチルペンテン−１との共重合体などプロピレン及び／又はブテン−１成分が主成分である非晶性ポリオレフィンが挙げられる。これらのうち、プロピレン・エチレン共重合体については、エチレン含有量が０〜３０重量％で、好ましくは１〜２０重量％である。エチレン含有量が３０重量％より大きい場合は、柔らかくなりすぎ、また、表面粘着性が大きすぎて道路舗装バインダとして使用するのが難しい。
【０００９】
さらに、本発明の非晶性ポリオレフィンは、沸騰ｎ−ヘプタン不溶分、すなわち沸騰ｎ−ヘプタンによるソックスレー抽出不溶分が７０重量％以下が好ましい。本発明の非晶性ポリオレフィンにおいて、沸騰ｎ−ヘプタン不溶分が上記範囲より多いと道路舗装用バインダとして使用した時に、オープンタイムが短すぎたり、舗装後の肉やせや、接着強度の経時変化が生じるなどの不都合があり好ましくない。本発明における非晶性ポリオレフィンとしては、例えば、宇部レキセン社製のウベタックＡＰＡＯなどを用いることができる。
【００１０】
本発明の（ｂ）粘着性付与剤とは天然ロジン（ガムロジン、ウッドロジン、トール油ロジンなど）、変性ロジン（重合ロジン、水添ロジンなど）、クマロン・インデン樹脂、テルペン系樹脂、脂肪族・脂環族・芳香族などの石油樹脂、フェノール系樹脂などを使用することができる。これらの粘着性付与剤のうち、非晶性ポリオレフィンと比較的相溶性のよい石油樹脂および／またはテルペン系樹脂、および、これらの水添物が好適に用いられる。さらに好ましくは脂肪族・脂環族共重合を含む脂肪族系石油樹脂である。
これらの配合割合は（ａ）非晶性ポリオレフィン１００重量部に対して３０−２００重量部、好ましくは５０−１５０重量部である。配合割合が３０重量部未満では１６０℃の粘度が高くなり、舗装作業性が悪くなったり、骨材である石との接着が悪くなり、動的安定性が悪くなるなどの問題がある。２００重量部を超えると、低温での、柔軟性がなくなり、クラックの発生などの問題がある。
【００１１】
本発明の（ｃ）液状ポリマーとしては、液状ポリブテン、液状ポリブタジエンなどがある。これらの内では液状ポリブテンが好ましい。
液状ポリブテンの配合量は、（ａ）非晶性ポリオレフィン１００重量部に対して１−３０重量部、好ましくは２−１５重量部である。１重量部未満では骨材に対する粘着性が弱く問題である。３０重量部を超えると粘着性が強く、施工面の粘着が出たり、施工性が悪くなるなどの問題がある。
本発明の組成物は構成により以下の特徴がある。
（１）非晶性ポリオレフィンが主成分の場合。
粘度の割に軟化点が高く、高い動的安定性が得られる。
（２）非晶性ポリオレフィンと粘着付与剤との場合。
施工、混合に好適な粘度が選択でき、骨材への接着性よい。
（３）非晶性ポリオレフィンと液状ポリマ−との場合。
粘度の調製が容易にでき、低温特性がよく、柔軟性がある。また、骨材への接着性もよい。
（４）非晶性ポリオレフィン、粘着付与剤、液状ポリマ−の場合。
（２），（３）の特徴を持ち低温で柔軟性があり、骨材への接着性もよい。
【００１２】
本発明の組成物をカラー化する際には、公知の顔料、例えば酸化鉄（Ｆｅ2 Ｏ3 ）や、酸化クロム（Ｃｒ2 Ｏ3 ）などが添加される。
また、混合物とする場合は、クレー・タルク・炭酸カルシウムなどの充填材、砕石・砂利・スラグ・人工骨材などの粗骨材、および天然砂・人工砂などの細骨材を使用することができる。これらは用途により、適量配合される。
また、本発明の組成物に少量の熱可塑性樹脂及び／又は熱可塑性エラストマーを添加することができる。例えばＬＤＰＥなどの低融点樹脂が好ましい。
【００１３】
本発明の組成物と顔料、充填材、骨材との配合は通常のアスファルト舗装用混合物製造用のプラントにより１４０℃〜２００℃、好ましくは１６０℃〜１８０℃で行われる。
この際、本発明の組成物の包装材（例えば、７〜２０μｍのＬＤＰＥフィルムで組成物に対して約０．２〜１．５重量％）を除くことなく組成物の一部として使用することもできる。
【００１４】
【実施例および比較例】
（混合物の製造）
各種性状試験に供する混合物は、１６０℃に溶融した当該樹脂組成物をあらかじめ１７０℃に加熱し空練りした骨材に投入、混合して製造するか、または常温固形の当該樹脂組成物（１５ｃｍ角程度）をあらかじめ１８０℃に加熱し空練りした骨材に投入混合して製造する。なお、顔料を添加する場合は、樹脂組成物投入直前に常温のまま投入する。
（試験方法）
１．バインダ性状試験
針入度試験・軟化点試験・伸度試験はＪＩＳ Ｋ ２２０７に、６０℃粘度試験は（社）日本道路協会舗装試験法便覧３−５−１１に、タフネス・テナシティ試験は（社）日本道路協会舗装試験法便覧３−５−１７に準拠して実施。
２．マーシャル安定度試験
（社）日本道路協会舗装試験法便覧３−７−１に準拠して実施。
３．ホイールトラッキング試験
（社）日本道路協会舗装試験法便覧３−７−３に準拠して実施。
４．カンタブロ試験
日本道路公団試験方法ＪＨＳ ２３１−１９９２に準拠して実施。
５．着色性の評価
作製直後の供試体の色彩を目視観察し、既存のカラー用バインダを用いた混合物との比較により評価。
６．褪色性の評価
本発明品をバインダとした供試体と市販カラー舗装用バインダを用いた供試体を屋外暴露し、両者の色の変化を目視観察により比較して評価。
７．施工試験
（１）施工性
アスファルトフィニッシャ、鉄輪ローラおよびタイヤローラを用いて試験施工を実施し、通常の混合物の施工性との比較により評価。
（２）施工後の表面の状態
通常の混合物の表面の状態との目視観察による比較により評価。
（材料）
（１）非晶性ポリオレフィン
▲１▼ＵＴ２７１５
宇部レキセン（株）製、プロピレン／ブテン−１共重合体
数平均分子量＝４，５００、成分比 プロピレン６５重量％、
ブテン−１、３５重量％
１９０℃での溶融粘度＝１，５００ｃｐｓ
▲２▼ＵＴ２３０４
宇部レキセン（株）製、プロピレン／エチレン共重合体
数平均分子量＝３，２００、成分比 プロピレン９２重量％、エチレン８重量％１９０℃での溶融粘度＝４５０ｃｐｓ
（２）粘着性付与剤
マルカレッツＴ−１００Ａ
丸善石油化学（株）製、脂肪族系石油樹脂
（３）液状ポリマー
ＨＶ−１９００
日本石油化学（株）製、ポリブテン
（４）骨材
砕石、細砂などを混合し、下記表１の合成粒度を持つ骨材を調整した。
【００１５】
【表１】
（５）顔料
酸化クロム（Ｃｒ2 Ｏ3 ）
【００１７】
（実施例）
実施例１
ＵＴ２７１５ ３０重量部
ＵＴ２３０４ １５重量部
マルカレッツＴ−１００Ａ ５０重量部
ＨＶ−１９００ ５重量部
実施例２
ＵＴ２７１５ ３０重量部
ＵＴ２３０４ ２０重量部
マルカレッツＴ−１００Ａ ５０重量部
実施例３
ＵＴ２７１５ ６０重量部
ＵＴ２３０４ ３０重量部
ＨＶ−１９００ １０重量部
実施例４
ＵＴ２７１５ ４０重量部
ＵＴ２３０４ ６０重量部
を１６０℃で加熱溶融混合し、本発明組成物を得た。この組成物と舗装用石油アスファルト６０−８０、改質II型アスファルト（製品名：ＴＲファルトＳ）および排水性舗装用改質アスファルト（ポーラスファルト）の性状を表−２に示す。
【００１８】
【表２】
実施例５
１６０℃に溶融した実施例１で調整した組成物５．２重量部、１７０℃に加熱した骨材（密粒）９３．８重量部および常温の顔料酸化クロム（Ｃｒ2 Ｏ3 ）１．０重量部を用い、室内試験用のアスファルト混合物製造装置で混合物を製造し、混合物性状試験、着色性の評価を実施。
【００２０】
実施例６
１６０℃に溶融した実施例１で調整した組成物４．８重量部、１７０℃に加熱した骨材（排水性）９４．２重量部および常温の顔料酸化クロム（Ｃｒ2 Ｏ3 ）１．０重量部を用い、室内試験用のアスファルト混合物製造装置で混合物を製造し、混合物性状試験、着色性の評価を実施。
【００２１】
実施例７
常温固形の実施例１で調整した組成物（１５ｃｍ角）５．２重量部、１８０℃に加熱した骨材（密粒）９３．８重量部および常温の顔料酸化クロム（Ｃｒ2 Ｏ3 ）１．０重量部を用い、室内試験用のアスファルト混合物製造装置で混合物を製造し、混合物性状試験、着色性の評価を実施。
【００２２】
実施例８
常温固形の実施例１で調整した組成物（１５ｃｍ角）４．８重量部、１８０℃に加熱した骨材（排水性）９４．２重量部および常温の顔料酸化クロム（Ｃｒ2 Ｏ3 ）１．０重量部を用い、室内試験用のアスファルト混合物製造装置で混合物を製造し、混合物性状試験、着色性の評価を実施。
【００２３】
実施例９
１６０℃に溶融した実施例２で調整した組成物５．２重量部、１７０℃に加熱した骨材（蜜粒）９３．８重量部および常温の顔料酸化クロム（Ｃｒ2 Ｏ3 ）１．０重量部を用い、室内試験用のアスファルト混合物製造装置で混合物を製造し、混合物性状試験、着色性の評価を実施。
【００２４】
実施例１０
１６０℃に溶融した実施例３で調整した組成物５．２重量部、１７０℃に加熱した骨材（蜜粒）９３．８重量部および常温の顔料酸化クロム（Ｃｒ2 Ｏ3 ）１．０重量部を用い、室内試験用のアスファルト混合物製造装置で混合物を製造し、混合物性状試験、着色性の評価を実施。
【００２５】
実施例１１
１６０℃に溶融した実施例４で調整した組成物５．２重量部、１７０℃に加熱した骨材（蜜粒）９３．８重量部および常温の顔料酸化クロム（Ｃｒ2 Ｏ3 ）１．０重量部を用い、室内試験用のアスファルト混合物製造装置で混合物を製造し、混合物性状試験、着色性の評価を実施。
【００２６】
【表３】
比較例１
樹脂組成物を改質II型アスファルト（製品名：ＴＲファルトＳ）に変えた以外は、実施例２と同様に実施。
【００２８】
比較例２
樹脂組成物を高粘度改質アスファルト（製品名：ポーラスファルト）に変えた以外は、実施例３と同様に実施。
【００２９】
比較例３
樹脂組成物を特開平４−１００８６２号公報実施例１の（ロ）組成物（製品名：メローファルト）に変えた以外は、実施例２と同様に実施。
【００３０】
比較例４
樹脂組成物を特開平５−２６２９２１号公報実施例２に示される組成物（製品名：パンハード）に変えた以外は、実施例４と同様に実施。
【００３１】
（試験結果のまとめ）
試験の結果を整理して以下に示す。
（１）実施例１に示した組成物の軟化点は１０８℃で、舗装用石油アスファルト６０−８０、改質II型アスファルトおよび高粘度改質アスファルトに比べ高い値を示しており、優れた耐流動性などが期待できる。
（２）実施例１に示した組成物の伸度は１００＋で、舗装用石油アスファルト６０−８０と同等な値を示しており、優れたひびわれ抵抗性が期待できる。
（３）実施例１に示した組成物のタフネスは２８６ｋｇｆ・ｃｍで、排水性舗装用アスファルトと同程度の値を示している。
（４）実施例１に示した組成物のテナシティは１５８ｋｇｆ・ｃｍで、排水性舗装用アスファルトと同程度の値を示している。
（５）実施例２と４および実施例３と５の結果から実施例１に示した組成物は、溶融して使用しても常温固形で使用しても、同等の性状の混合物を製造することが可能である。
（６）実施例１に示した組成物を密粒度の混合物に使用した場合は、比較例１、３、４を用いたものと同程度のマーシャル安定度を示す。
（７）実施例１に示した組成物を密粒度の混合物に使用した場合は、比較例１、３、４を用いたものに比べ１，０００〜４，５００回／ｍｍ程度大きな動的安定度を示しており、優れた耐流動性などが期待できる。
（８）実施例１に示した組成物を排水性の混合物に使用した場合は、比較例２を用いたものと同程度の安定度を示す。
（９）実施例１に示した組成物を排水性の混合物に使用した場合は、比較例２を用いたものに比べ２，０００回／ｍｍ程度大きな動的安定度を示しており、優れた耐流動性などが期待できる。
（１０）実施例１に示した組成物を排水性の混合物に使用した場合は、比較例２を用いたものと同程度のカンタブロ損失量を示しており、アスファルトをベースとする排水性舗装用改質アスファルトと同等の骨材飛散抵抗性が期待できる。
（１１）実施例１に示した組成物を使用した場合は、比較例１、２に比べ優れた着色性を示す。また、比較例３、４に比べても優れた着色性を示す。
（１２）実施例１に示した組成物を使用した場合は、比較例３、４に比べ優れた褪色抵抗性を示している。
【００３２】
（試験施工）
【００３３】
実施例１２
常温固形の実施例１で調整した組成物（１５ｃｍ角）５．２重量部および１８０℃に加熱した骨材（密粒）９３．８重量部および顔料１．０重量部を用い、アスファルト合材工場の混合物製造装置により混合物を製造し、試験施工を実施。
【００３４】
実施例１３
常温固形の実施例１で調整した組成物（１５ｃｍ角）４．８重量部および１８０℃に加熱した骨材（排水性）９４．２重量部および顔料１．０重量部を用い、アスファルト合材工場の混合物製造装置により混合物を製造し、試験施工を実施。
【００３５】
比較例５
樹脂組成物をあらかじめ加熱溶融した改質II型アスファルト（製品名：ＴＲファルトＳ）に変えた以外は、実施例６と同様に実施。
【００３６】
比較例６
樹脂組成物をあらかじめ加熱溶融した高粘度改質アスファルト（製品名：ポーラスファルト）に変えた以外は、実施例７と同様に実施。
【００３７】
（試験施工結果）
１．施工性
実施例１に示した組成物を使用した混合物の施工性は、改質II型アスファルトおよび排水性舗装用改質アスファルトを使用した混合物の施工性と同等であった。
２．表面の状態
施工後の表面の状態は、改質II型アスファルトおよび排水性舗装用改質アスファルトを使用した混合物の表面の状態と同様のものであった。
【００３８】
【発明の効果】
本発明は、従来のアスファルト舗装およびカラーバインダを用いた舗装と同等以上の強度特性を有し、なおかつ優れた着色性および褪色性を有する道路舗装用樹脂組成物を提供するものである。本発明による混合物は、特に動的安定度が大きくおよびカンタブロ損失量が小さいことから、最近重要視されているバスレーンなどの重交通道路のカラー化、排水性舗装のカラー化に適用した場合に、優れた供用性が期待できる樹脂組成物である。
また、本発明品は、通常のアスファルトと同様に溶融して加熱骨材に混合できるほか、常温固形の状態で加熱骨材に混合することもできるため、大量の混合物を供給することにも、専用の貯蔵タンクなどを使用せずに少量の混合物を供給することにも対応が可能である。[0001]
[Industrial application fields]
The present invention is a binder composition suitable for coloring impervious pavements such as roadways, sidewalks, parks, and plazas, permeable pavements, and drainage pavements. The composition of the present invention is light yellow and transparent, hardly undergoes discoloration due to deterioration in the natural environment, and has high water resistance, self-adhesiveness and high strength as a binder. It is possible to provide a color pavement material, a light color pavement material and a natural color pavement material which are excellent in durability by mixing with a material and a pigment.
[0002]
[Prior art and problems]
Conventionally, asphalt for paving has been mainly used as a binder for road paving. However, with the increase in traffic volume, fluid rubbing has become prominent, and in order to respond to this, modified asphalt added with rubber such as SBS, SEBS, EEA, SBR, BR, CR and thermoplastic elastomer is also used. It has come to be.
[0003]
In recent years, environmental and social needs have changed, and colorization and lightening of bus lanes, parks, promenades, and tunnel pavements are increasing for safety improvement and beautification in urban areas. Also, as an environmental problem, the permeation of road pavement is attracting attention in order to control groundwater shortages, river floods, floods, etc.
Furthermore, the application of drainage pavement is increasing for the purpose of preventing water splashes on the roadway and improving visibility in rainy weather. In addition, in the drainage pavement mixture, since the porosity is around 20%, it is necessary to increase the scattering resistance of the aggregate. In particular, the softening point of 70 ° C. or higher, the toughness of 200 kgf · cm or higher, 100 kgf · cm A modified asphalt for drainage pavement having the above tenacity is used. As mentioned for reference, the softening point of petroleum asphalt for paving is 55.0 ° C. or lower, and the softening point of ordinary modified asphalt is 70.0 ° C. or lower.
In addition, the prior art, including high viscosity modified asphalt, is mainly made of asphalt, and it is difficult to color because it is black in itself.
One alternative to asphalt for the purpose of colorization is disclosed in Japanese Patent Laid-Open No. 4-100862. This discloses a composition comprising petroleum solvent extract oil, petroleum, coal and / or natural resin, thermoplastic rubber, and naphthenic acid.
[0004]
However, since the physical properties of the composition alone are equivalent to ordinary asphalt for paving, it is not suitable for drainage paving on heavy traffic roads and roadways. This can be understood from the fact that the dynamic stability of the mixture for paving shown in the publication is 420 to 1,050 times / mm. By the way, the target value of dynamic stability shown in Table-4.1 of the design and construction guide (Japan Asphalt Association) of the mixture using modified asphalt is 1,000 according to the traffic volume. ˜5,000 times / mm. In other words, it suggests that in areas where there is a lot of traffic, fluid rutting will occur with a dynamic stability of about 1,000 times / mm.
On the other hand, JP-A-5-262921 shows a composition comprising a thermoplastic elastomer and a tackifying resin. Although the composition has a high softening point and a dynamic stability of about 1,130 to 3,500 is obtained, it is considered for drainage pavement on roadways that must consider the scattering resistance of aggregates Has not been made. In addition, the composition is not added to and mixed with the aggregate in advance as usual asphalt, but is added to and mixed with the aggregate as it is solid. Are suitable.
In addition, binders for color mixtures that do not use asphalt are excellent in colorability compared to (1) black paving asphalt, but are colored in yellowish brown or dark yellowish green and far from colorless and transparent. When it is combined with a white pigment or a light color pigment, or when trying to make use of the color of the aggregate without using a pigment, sufficient color development cannot be obtained. (2) 20th Japan Road Conference proceedings p. 596-p. As shown in 597, there is a disadvantage that the color deteriorates and discolors quickly in a natural environment.
[0005]
In view of the above-described problems, the present invention has characteristics as a binder suitable for coloring impervious pavement, permeable pavement, and drainage pavement on heavy traffic roads, and at the same time, is melted in advance. Provided is a resin composition for road pavement that is light yellow, transparent and has almost no discoloration due to deterioration in the natural environment, which can be used in both the method of adding and mixing to the aggregate and the method of adding and mixing to the aggregate as it is solid. Is.
In addition, the use of amorphous polyolefin has the advantage that the present invention has a lower viscosity, better workability, better miscibility with aggregates, and is less susceptible to deterioration.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the present invention
This was solved by a resin composition containing amorphous polyolefin.
As a specific example,
1. Resin composition 2 containing amorphous polyolefin. (A) Amorphous polyolefin 100 parts by weight (b) Tackifier 30-200 parts by weight 3 (A) Amorphous polyolefin 100 parts by weight (c) Liquid polymer 1-30 parts by weight 4 (A) Amorphous polyolefin 100 parts by weight (b) Tackifier 30-200 parts by weight (c) Liquid polymer It was solved by providing a road pavement resin composition comprising 1-30 parts by weight.
[0007]
The (a) amorphous polyolefin of the present invention is not particularly limited, but the following are preferred. Atactic polypropylene containing 50% by weight or more of the propylene component and produced as a by-product in the production of crystalline polypropylene may be used, and polypropylene or propylene containing a predetermined propylene component from raw materials and other α-olefins These copolymers can be produced and used for the purpose. For the purpose of production, for example, a catalyst obtained by polymerizing in the presence of hydrogen using a titanium-supported catalyst supported on magnesium chloride and triethylaluminum can be used. From the viewpoint of supply stability and quality stability, it is preferable to use a predetermined amorphous polyolefin produced for the purpose. Also suitable is an amorphous polyolefin having 50% by weight or less of butene-1 and 50% by weight or more of the total of propylene and butene-1 components. Furthermore, the amorphous polyolefin has a number average molecular weight of 1,000 to 20,000, preferably 1,500 to 15,000.
Also suitable are amorphous polyolefins having ethylene of 30% by weight or less and the total of propylene and ethylene components of 50% by weight or more. Further, the amorphous polyolefin has a number average molecular weight of 1,000 to 20,000, preferably 1,500 to 15,000.
[0008]
Specifically, polypropylene having a propylene content and molecular weight within the above ranges, propylene / ethylene copolymer, propylene / butene-1 copolymer, propylene, butene-1 and ethylene terpolymer, propylene and hexene -1, octene-1 or 2-methylpentene-1 and the like, and amorphous polyolefins whose main components are propylene and / or butene-1 components. Among these, the propylene / ethylene copolymer has an ethylene content of 0 to 30% by weight, preferably 1 to 20% by weight. When the ethylene content is larger than 30% by weight, the surface becomes too soft and the surface tackiness is too large to be used as a road pavement binder.
[0009]
Further, the amorphous polyolefin of the present invention preferably has a boiling n-heptane insoluble content, that is, a Soxhlet extraction insoluble content by boiling n-heptane is 70% by weight or less. In the amorphous polyolefin of the present invention, if the boiling n-heptane insoluble content is more than the above range, when used as a road paving binder, the open time is too short, the paved meat thinning, and the adhesive strength changes over time. This is not preferable because of inconvenience such as occurrence. As an amorphous polyolefin in the present invention, for example, Ubetak APAO manufactured by Ube Lexen Co., Ltd. can be used.
[0010]
The (b) tackifier of the present invention is natural rosin (gum rosin, wood rosin, tall oil rosin, etc.), modified rosin (polymerized rosin, hydrogenated rosin, etc.), coumarone / indene resin, terpene resin, aliphatic / grease A cyclic / aromatic petroleum resin, a phenolic resin, or the like can be used. Of these tackifiers, petroleum resins and / or terpene resins that are relatively compatible with the amorphous polyolefin, and hydrogenated products thereof are preferably used. More preferred are aliphatic petroleum resins including aliphatic / alicyclic copolymerization.
These compounding ratios are 30-200 weight part with respect to 100 weight part of (a) amorphous polyolefin, Preferably it is 50-150 weight part. If the blending ratio is less than 30 parts by weight, the viscosity at 160 ° C. becomes high, so that there are problems such as poor pavement workability, poor adhesion with aggregate stones, and poor dynamic stability. When it exceeds 200 parts by weight, there is a problem that the flexibility is lost at a low temperature and cracks are generated.
[0011]
Examples of the liquid polymer (c) of the present invention include liquid polybutene and liquid polybutadiene. Of these, liquid polybutene is preferred.
The compounding quantity of liquid polybutene is 1-30 weight part with respect to 100 weight part of (a) amorphous polyolefin, Preferably it is 2-15 weight part. If it is less than 1 part by weight, the adhesiveness to the aggregate is weak, which is a problem. When it exceeds 30 parts by weight, the adhesiveness is strong, and there are problems such as adhesion on the construction surface and poor workability.
The composition of the present invention has the following characteristics depending on the constitution.
(1) When amorphous polyolefin is the main component.
The softening point is high for the viscosity, and high dynamic stability is obtained.
(2) In the case of an amorphous polyolefin and a tackifier.
Viscosity suitable for construction and mixing can be selected, and adhesion to aggregate is good.
(3) In the case of amorphous polyolefin and liquid polymer.
Viscosity can be easily adjusted, low temperature characteristics are good, and there is flexibility. Moreover, the adhesiveness to an aggregate is also good.
(4) In the case of amorphous polyolefin, tackifier, and liquid polymer.
It has the characteristics of (2) and (3), is flexible at low temperatures, and has good adhesion to aggregates.
[0012]
When coloring the composition of the present invention, a known pigment such as iron oxide (Fe 2 O 3 ) or chromium oxide (Cr 2 O 3 ) is added.
In addition, when making a mixture, use fillers such as clay, talc and calcium carbonate, coarse aggregates such as crushed stone, gravel, slag and artificial aggregates, and fine aggregates such as natural sand and artificial sand. it can. These are blended in appropriate amounts depending on the application.
Moreover, a small amount of thermoplastic resins and / or thermoplastic elastomers can be added to the composition of the present invention. For example, a low melting point resin such as LDPE is preferable.
[0013]
The composition of the present invention and the pigment, filler, and aggregate are blended at 140 to 200 ° C., preferably 160 to 180 ° C., by an ordinary asphalt pavement mixture production plant.
At this time, the packaging material of the composition of the present invention (for example, 7 to 20 μm LDPE film is used as a part of the composition without removing about 0.2 to 1.5% by weight based on the composition). You can also.
[0014]
Examples and Comparative Examples
(Production of mixture)
The mixture used for various property tests is manufactured by adding the resin composition melted at 160 ° C. to an aggregate that has been preheated to 170 ° C. and kneaded in advance, or is mixed at room temperature, or the resin composition (15 cm square) Grade) is heated to 180 ° C. in advance and mixed in the air-kneaded aggregate to produce. In addition, when adding a pigment, it adds at normal temperature immediately before resin composition addition.
(Test method)
1. Binder property test Needle penetration test, softening point test and elongation test are in JIS K 2207, 60 ° C viscosity test is in Japan Road Association pavement test method manual 3-5-11, and toughness tenacity test is in ) Carried out in accordance with Japan Road Association Pavement Test Method Handbook 3-5-17.
2. Marshall stability test (Company) Conducted in accordance with Japan Road Association Pavement Test Method Handbook 3-7-1.
3. Wheel tracking test (Company) Conducted according to Japan Road Association Pavement Test Method Handbook 3-7-3.
4). Cantablo test Carried out in accordance with Japan Highway Public Corporation test method JHS 231-1992.
5. Evaluation of colorability Visually observe the color of the specimen immediately after preparation and evaluate it by comparison with a mixture using an existing color binder.
6). Evaluation of fading property A specimen using the product of the present invention as a binder and a specimen using a commercially available color paving binder were exposed outdoors, and the color changes of both were compared and evaluated by visual observation.
7). Construction test (1) Workability Test construction was performed using asphalt finishers, iron wheel rollers and tire rollers, and evaluated by comparison with the workability of ordinary mixtures.
(2) Surface condition after construction Evaluated by comparison with the surface condition of a normal mixture by visual observation.
(material)
(1) Amorphous polyolefin (1) UT2715
Ube Lexene Co., Ltd., propylene / butene-1 copolymer number average molecular weight = 4,500, component ratio propylene 65% by weight,
Butene-1, 35% by weight
Melt viscosity at 190 ° C. = 1,500 cps
(2) UT2304
Ube Lexene Co., Ltd., propylene / ethylene copolymer number average molecular weight = 3,200, component ratio propylene 92% by weight, ethylene 8% by weight Melt viscosity at 190 ° C. = 450 cps
(2) Tackifier, Markaretz T-100A
Maruzen Petrochemical Co., Ltd., aliphatic petroleum resin (3) liquid polymer HV-1900
Aggregate having a synthetic particle size shown in Table 1 below was prepared by mixing polybutene (4) aggregate crushed stone, fine sand, etc., manufactured by Nippon Petrochemical Co., Ltd.
[0015]
[Table 1]
(5) Pigment chromium oxide (Cr 2 O 3 )
[0017]
(Example)
Example 1
UT2715 30 parts by weight UT2304 15 parts by weight Marcarez T-100A 50 parts by weight HV-1900 5 parts by weight Example 2
UT2715 30 parts by weight UT2304 20 parts by weight Marcaretz T-100A 50 parts by weight Example 3
UT2715 60 parts by weight UT2304 30 parts by weight HV-1900 10 parts by weight Example 4
UT2715 40 parts by weight UT2304 60 parts by weight was heated, melted and mixed at 160 ° C. to obtain the composition of the present invention. Table 2 shows the properties of this composition and paving petroleum asphalt 60-80, modified type II asphalt (product name: TR Falto S), and drainage paving modified asphalt (porous falt).
[0018]
[Table 2]
Example 5
5.2 parts by weight of the composition prepared in Example 1 melted at 160 ° C., 93.8 parts by weight of aggregates (dense granules) heated to 170 ° C., and 1.0 chrome pigment oxide (Cr 2 O 3 ) at room temperature Using the parts by weight, the mixture was manufactured with an asphalt mixture manufacturing device for laboratory tests, and the properties of the mixture were tested and the colorability was evaluated.
[0020]
Example 6
4.8 parts by weight of the composition prepared in Example 1 melted at 160 ° C., 94.2 parts by weight of aggregate (drainage) heated to 170 ° C., and 1.0% of pigment chromium oxide (Cr 2 O 3 ) at room temperature Using the parts by weight, the mixture was manufactured with an asphalt mixture manufacturing device for laboratory tests, and the properties of the mixture were tested and the colorability was evaluated.
[0021]
Example 7
5.2 parts by weight of the composition (15 cm square) prepared in Example 1 which is solid at room temperature, 93.8 parts by weight of aggregate (dense granules) heated to 180 ° C., and pigment chromium oxide (Cr 2 O 3 ) 1 at room temperature Using 0.0 part by weight, the mixture was produced with an asphalt mixture production device for laboratory tests, and the property test of the mixture and the evaluation of the colorability were carried out.
[0022]
Example 8
4.8 parts by weight of the composition prepared in Example 1 which is solid at room temperature (15 cm square), 94.2 parts by weight of aggregate (drainage) heated to 180 ° C., and pigment chromium oxide (Cr 2 O 3 ) 1 at room temperature Using 0.0 part by weight, the mixture was produced with an asphalt mixture production device for laboratory tests, and the property test of the mixture and the evaluation of the colorability were carried out.
[0023]
Example 9
5.2 parts by weight of the composition prepared in Example 2 melted at 160 ° C., 93.8 parts by weight of aggregates (honey granules) heated to 170 ° C., and 1.0 chrome pigment oxide (Cr 2 O 3 ) at room temperature Using the parts by weight, the mixture was manufactured with an asphalt mixture manufacturing device for laboratory tests, and the properties of the mixture were tested and the colorability was evaluated.
[0024]
Example 10
5.2 parts by weight of the composition prepared in Example 3 melted at 160 ° C., 93.8 parts by weight of aggregate (honeycomb) heated to 170 ° C., and 1.0 chrome pigment oxide (Cr 2 O 3 ) at room temperature Using the parts by weight, the mixture was manufactured with an asphalt mixture manufacturing device for laboratory tests, and the properties of the mixture were tested and the colorability was evaluated.
[0025]
Example 11
5.2 parts by weight of the composition prepared in Example 4 melted at 160 ° C., 93.8 parts by weight of aggregate (honeycomb) heated to 170 ° C., and 1.0 chrome pigment oxide (Cr 2 O 3 ) at room temperature Using the parts by weight, the mixture was manufactured with an asphalt mixture manufacturing device for laboratory tests, and the properties of the mixture were tested and the colorability was evaluated.
[0026]
[Table 3]
Comparative Example 1
Performed in the same manner as in Example 2 except that the resin composition was changed to modified type II asphalt (product name: TR Palt S).
[0028]
Comparative Example 2
Performed in the same manner as in Example 3 except that the resin composition was changed to high-viscosity modified asphalt (product name: porous asphalt).
[0029]
Comparative Example 3
This was carried out in the same manner as in Example 2 except that the resin composition was changed to (b) composition (product name: Mellowphalt) in Example 1 of JP-A-4-100902.
[0030]
Comparative Example 4
This was carried out in the same manner as in Example 4 except that the resin composition was changed to the composition (product name: bread hard) shown in Example 2 of JP-A-5-262921.
[0031]
(Summary of test results)
The results of the test are summarized below.
(1) The softening point of the composition shown in Example 1 is 108 ° C., which is higher than that of paving petroleum asphalt 60-80, modified type II asphalt and high viscosity modified asphalt, and has excellent resistance to resistance. Liquidity can be expected.
(2) The elongation of the composition shown in Example 1 is 100+, indicating a value equivalent to that of petroleum asphalt 60-80 for paving, and excellent crack resistance can be expected.
(3) The toughness of the composition shown in Example 1 is 286 kgf · cm, which is the same value as the asphalt for drainage pavement.
(4) The tenacity of the composition shown in Example 1 is 158 kgf · cm, which is similar to that of drainage pavement asphalt.
(5) From the results of Examples 2 and 4 and Examples 3 and 5, the composition shown in Example 1 produces a mixture having the same properties regardless of whether it is melted and used at room temperature. It is possible.
(6) When the composition shown in Example 1 is used in a mixture having a dense particle size, the same Marshall stability as that in Comparative Examples 1, 3, and 4 is exhibited.
(7) When the composition shown in Example 1 is used in a mixture having a dense particle size, the dynamic stability is about 1,000 to 4,500 times / mm greater than that using Comparative Examples 1, 3, and 4. The fluidity is shown, and excellent fluid resistance can be expected.
(8) When the composition shown in Example 1 is used in a drainage mixture, the stability is comparable to that using Comparative Example 2.
(9) When the composition shown in Example 1 was used in a drainage mixture, it showed a dynamic stability that was about 2,000 times / mm greater than that using Comparative Example 2 and was excellent. Fluid resistance can be expected.
(10) When the composition shown in Example 1 is used in a drainage mixture, it shows the same amount of cantabulo loss as that used in Comparative Example 2, and is for drainage pavement based on asphalt. Aggregate scattering resistance equivalent to modified asphalt can be expected.
(11) When the composition shown in Example 1 is used, excellent colorability is exhibited as compared with Comparative Examples 1 and 2. In addition, excellent colorability is exhibited as compared with Comparative Examples 3 and 4.
(12) When the composition shown in Example 1 is used, it shows superior fading resistance as compared with Comparative Examples 3 and 4.
[0032]
(Test construction)
[0033]
Example 12
Asphalt mixture was prepared by using 5.2 parts by weight of the composition (15 cm square) prepared in Example 1 which was solid at room temperature, 93.8 parts by weight of aggregate (dense granules) heated to 180 ° C., and 1.0 part by weight of pigment. Manufacture the mixture with the plant's mixture manufacturing equipment, and conduct the test construction.
[0034]
Example 13
Asphalt mixture was prepared by using 4.8 parts by weight of the composition (15 cm square) prepared in Example 1 which was solid at room temperature, 94.2 parts by weight of aggregate (drainage) heated to 180 ° C., and 1.0 part by weight of pigment. Manufacture the mixture with the plant's mixture manufacturing equipment, and conduct the test construction.
[0035]
Comparative Example 5
Performed in the same manner as in Example 6 except that the resin composition was changed to a modified type II asphalt (product name: TR Palt S) that had been heated and melted in advance.
[0036]
Comparative Example 6
Executed in the same manner as in Example 7 except that the resin composition was changed to high-viscosity modified asphalt (product name: porous falt) previously melted.
[0037]
(Test construction results)
1. Workability The workability of the mixture using the composition shown in Example 1 was equivalent to the workability of the mixture using the modified type II asphalt and the modified asphalt for drainage pavement.
2. Surface condition The surface condition after construction was the same as the surface condition of the mixture using modified type II asphalt and drainage pavement modified asphalt.
[0038]
【The invention's effect】
The present invention provides a resin composition for road pavement having strength characteristics equal to or higher than those of conventional asphalt pavement and pavement using a color binder, and having excellent coloring and fading properties. When the mixture according to the present invention is applied to colorization of heavy traffic roads such as bus lanes and drainage pavement, which have been emphasized recently, especially because of its large dynamic stability and small amount of cantabulo loss, It is a resin composition that can be expected to have excellent serviceability.
In addition, the product of the present invention can be melted and mixed with the heated aggregate in the same manner as normal asphalt, and can also be mixed with the heated aggregate in a solid state at room temperature. It is also possible to supply a small amount of mixture without using a dedicated storage tank.
Claims (5)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08028296A JP3635147B2 (en) | 1995-04-26 | 1996-04-02 | Road pavement resin composition |
| TW085104553A TW339387B (en) | 1996-04-02 | 1996-04-16 | Resin element for pavements |
| KR1019960012957A KR100441261B1 (en) | 1995-04-26 | 1996-04-25 | Resin composition for road pavement |
| CN96107397A CN1142516A (en) | 1995-04-26 | 1996-04-26 | Resin composition for road construction |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-101992 | 1995-04-26 | ||
| JP10199295 | 1995-04-26 | ||
| JP08028296A JP3635147B2 (en) | 1995-04-26 | 1996-04-02 | Road pavement resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0912787A JPH0912787A (en) | 1997-01-14 |
| JP3635147B2 true JP3635147B2 (en) | 2005-04-06 |
Family
ID=26421321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08028296A Expired - Fee Related JP3635147B2 (en) | 1995-04-26 | 1996-04-02 | Road pavement resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3635147B2 (en) |
| KR (1) | KR100441261B1 (en) |
| CN (1) | CN1142516A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004076553A1 (en) * | 2003-02-25 | 2004-09-10 | Toda Kogyo Corporation | Resin composition for pavement |
| US7611726B2 (en) | 2004-07-15 | 2009-11-03 | L'oréal | Shine-enhancing film formers |
| JP5705241B2 (en) * | 2011-01-18 | 2015-04-22 | 三井化学株式会社 | Adhesive resin composition and hot melt adhesive obtained therefrom |
| US10584247B2 (en) | 2012-12-28 | 2020-03-10 | Honeywell International Inc. | Methods for reducing asphalt pavement thickness |
| AU2019298225A1 (en) * | 2018-07-03 | 2021-01-28 | Dow Global Technologies Llc. | Olefin-based polymer compositions for flooring applications |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5810435B2 (en) * | 1974-11-25 | 1983-02-25 | フジコウサン カブシキガイシヤ | The best way to go about it |
-
1996
- 1996-04-02 JP JP08028296A patent/JP3635147B2/en not_active Expired - Fee Related
- 1996-04-25 KR KR1019960012957A patent/KR100441261B1/en not_active IP Right Cessation
- 1996-04-26 CN CN96107397A patent/CN1142516A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR960037754A (en) | 1996-11-19 |
| KR100441261B1 (en) | 2004-11-02 |
| JPH0912787A (en) | 1997-01-14 |
| CN1142516A (en) | 1997-02-12 |
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