JP3798230B2 - Asphalt emulsifying dispersant - Google Patents
Asphalt emulsifying dispersant Download PDFInfo
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- JP3798230B2 JP3798230B2 JP2000204688A JP2000204688A JP3798230B2 JP 3798230 B2 JP3798230 B2 JP 3798230B2 JP 2000204688 A JP2000204688 A JP 2000204688A JP 2000204688 A JP2000204688 A JP 2000204688A JP 3798230 B2 JP3798230 B2 JP 3798230B2
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- asphalt
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- emulsifying dispersant
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0053—Water-soluble polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、アスファルトを乳化する際に用いられるアスファルト乳化分散剤、及び、それを用いて得られるセメント混合性、骨材混合性、耐久性に優れる水中油滴型アスファルト乳剤組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
アスファルトは道路舗装、防水・接着材料、鉄道軌道の敷設等に広く使用されている。しかし、アスファルトは常温においては非常に粘性が高いため作業性が極めて悪い。そこで、常温での所望の作業性を確保するために、適当な乳化剤及び水を用いて水中油滴型の乳剤組成物の形態として流動性を向上し使用する技術がある。水中油滴型の乳剤用の乳化剤としては、アニオン性乳化剤、カチオン性乳化剤、ノニオン性乳化剤または両性乳化剤が知られており、それぞれの用途により使い分けられている。
【０００３】
また、一般道路、運動場、駐車場等に使用される舗装用常温混合物（以下、合材と称す）では強度や耐久性、対摩耗性が求められるため、骨材として砂、砂利、セメント、フィラー等とアスファルト乳剤の混合物が用いられる。
【０００４】
しかし、従来のアニオン性乳化剤、カチオン性乳化剤、ノニオン性乳化剤または両性乳化剤等を用いたアスファルト乳剤組成物では、砂、砂利、セメント、フィラー等の骨材との混合性が十分ではなく、混合中に乳剤組成物が分離したり凝集したりして作業性に優れる合材の製造に難点があり、強度や耐久性に問題があった。
【０００５】
これらの問題を解決するために、乳化剤と、発泡剤や分散剤の併用が検討されている（特開平１１−１２０１６号公報）。しかし、発泡剤の併用は骨材混合性が改良されるものの、合材中に気泡による空隙が残り、強度や耐久性を満足するものとは言えない。また、分散剤として、ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩やポリアクリル酸ナトリウム塩が挙げられているが、これらの分散剤ではアスファルトの乳化を阻害する作用があり、また十分なセメント混合性や骨材混合性が得られない。
【０００６】
【発明が解決しようとする課題】
本発明は、セメント混合性、骨材混合性、耐久性に優れる水中油滴型アスファルト乳剤組成物を得ることのできるアスファルト乳化分散剤を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明は、炭素数２〜３のオキシアルキレン基（以下ＡＯと称す）を平均で２〜３００モル有するビニル系単量体（ａ）の１種以上と、カルボキシル基、スルホン酸基、アミド基またはこれらの水溶性塩を有するビニル系単量体（ｂ）の１種以上とを重合して得られる水溶性共重合体を含有するアスファルト乳化分散剤を提供する。
【０００８】
また、本発明はアスファルト、前記本発明のアスファルト乳化分散剤及び水を含有する水中油滴型アスファルト乳剤組成物を提供する。
【０００９】
【発明の実施の形態】
単量体（ａ）において、炭素数２〜３のＡＯとはエチレンオキシド基とプロピレンオキシド基であり、本発明の水溶解性物質を構成する共重合体の構造体には炭素数２〜３のＡＯが必須である。これらのＡＯの付加形態は、炭素数２または３のＡＯの単独付加、あるいはランダム付加、ブロック付加、交互付加のいずれも用いる事ができる。
【００１０】
上記のＡＯを導入した共重合体は水溶性のものであり、カルボキシル基、スルホン酸基、アミド基もしくはこれらの水溶性塩の１種または２種以上を含有するものが用いられる。水溶性塩としてはナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等の金属塩や、アンモニウム塩、トリエタノールアミン塩、ジエタノールアミン塩、モノエタノールアミン塩等が挙げられる。
【００１１】
本発明の水溶性共重合体としては、アルケニルエーテルや下記の一般式（Ａ）で表される単量体（ａ）の１種以上と、無水マレイン酸共重合体や下記一般式（Ｂ）で表される化合物及び下記一般式（Ｃ）で表わされる化合物から選ばれる１種以上との共重合体が挙げられる。
【００１２】
【化３】
（式中、
Ｒ1及びＲ2：水素原子またはメチル基、
ｍ１：０〜２の数、
ＡＯ：炭素数２〜３のオキシアルキレン基、
ｎ：２〜３００の数、
Ｘ：水素原子または炭素数１〜３のアルキル基
を示し、ｎ個のＡＯは同一でも異なっていても良い。）
【００１４】
【化４】
（式中、
Ｒ3及びＲ6：水素原子またはメチル基、
Ｒ4及びＲ5：水素原子、メチル基または(ＣＨ2)m2ＣＯＯＭ2、
Ｍ1、Ｍ2及びＹ：水素原子または陽イオン基（好ましくは、アルカリ金属、アルカリ土類金属、アンモニウム基、アミノ基または置換アルキルアンモニウム基由来の陽イオン基）
ｍ２：０〜２の整数、
を示す。）。
【００１６】
一般式（Ａ）で示される単量体としては、ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール及び、メトキシポリエチレングリコール、メトキシポリエチレンポリプロピレングリコール、エトキシポリエチレングリコール、エトキシポリエチレンポリプロピレングリコール、プロポキシポリエチレングリコール、プロポキシポリエチレンポリプロピレングリコール等の片末端アルキル基封鎖型ポリアルキレングリコールとアクリル酸またはメタクリル酸とのエステル化合物や、アクリル酸またはメタクリル酸へのエチレンオキシド、プロピレンオキシド付加物が挙げられる。ポリアルキレングリコールのアルキレンオキシド付加モル数は２〜３００であり、製造面から片末端アルキル基封鎖型が好ましい。
【００１７】
また、一般式（Ｂ）で示される単量体としては、不飽和モノカルボン酸系と不飽和ジカルボン酸系が挙げられる。不飽和モノカルボン酸系単量体としては、アクリル酸、メタクリル酸、クロトン酸及びこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩が挙げられる。また不飽和ジカルボン酸系単量体としては、無水マレイン酸、マレイン酸、無水イタコン酸、イタコン酸、無水シトラコン酸、シトラコン酸、フマル酸、またはこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩が挙げられる。
【００１８】
また、一般式（Ｃ）で示される単量体としては、アリルスルホン酸、メタリルスルホン酸、またはこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩が挙げられる。
【００１９】
本発明に関わる共重合体は公知の方法で製造する事ができる。この製造方法の例として、特開昭５９−１６２１６３号公報３〜４頁、特開昭６２−７０２５０号公報４〜５頁、特開昭６２−７８１３７号公報４〜５頁等に例示の溶媒重合法が挙げられる。即ち、適当な溶媒中で、上記単量体（Ａ）、（Ｂ）及び（Ｃ）を組み合わせて重合することによって製造可能である。
【００２０】
例えば水や炭素数１〜４の低級アルコール中、過硫酸アンモニウム、過酸化水素等の重合開始剤の存在下、必要ならば亜硫酸水素ナトリウムやメルカプトエタノール等を添加し、窒素雰囲気下５０〜１００℃で０．５〜１０時間反応させれば良い。尚、本発明を損なわない範囲で、他の共重合可能な単量体を共重合しても良い。こうした単量体としては、アクリロニトリル、アクリルアミド、メタクリルアミド、スチレン等が挙げられる。
【００２１】
また、ＡＯの平均付加モル数２〜３００の範囲がアスファルト乳剤組成物のセメント混合性、骨材混合性、耐久性に優れ、１００〜２００が特に優れる。
【００２２】
更に、一般式（Ａ）のｎが１００〜２００と一般式（Ａ）のｎが２〜５０との併用のように、異なる分布のＡＯの重合体を併用するとセメント混合性の点でより好ましい。
【００２３】
本発明の水溶性共重合体において、単量体（ａ）と単量体（ｂ）の重合比率は、モル比で単量体（ａ）／単量体（ｂ）＝０．１／１００〜２００／１００であることが、アスファルト乳剤組成物のセメント混合性、骨材混合性、耐久性に優れ、単量体（ａ）／単量体（ｂ）＝１０／１００〜１００／１００の範囲が特に優れる。
【００２４】
また、本発明の水溶性共重合体の重量平均分子量（ゲルパーミエーションクロマトグラフィー法／標準物質ポリスチレンスルホン酸ナトリウム換算／水系）は５，０００〜１００，０００の範囲がアスファルト乳剤組成物のセメント混合性、骨材混合性、耐久性の観点から特に優れる。また、単量体（ａ）、（ｂ）と共重合可能な単量体を含有してもよい。
【００２５】
本発明の水溶性共重合体の乳化分散剤中の含有量は好ましくは０．１〜１００重量％であり、またこの共重合体のアスファルト乳剤組成物中の含有量は使用目的により異なるが、好ましくは０．０５〜１０重量％であり、更に好ましくは０．１〜５重量％である。
【００２６】
本発明のアスファルト乳化分散剤を用いたアスファルト乳剤組成物が、セメント混合性、骨材混合性、耐久性に優れるメカニズムは必ずしも明確ではないが、本発明の水溶性共重合体がセメントや骨材の表面に吸着して保護コロイド的な機能を発揮し、セメントの反応やセメントとアスファルト乳剤の反応、及び骨材とアスファルト乳剤の反応を抑制するため、混合性が向上するものと予想される。また、混合性が良好となることから、セメントや骨材とアスファルト乳剤とが均一に混合され、道路施工時の敷固めが十分に行われ、耐久性に優れた舗装が可能となると考えられる。
【００２７】
本発明に用いられる水溶性共重合体とアニオン性乳化剤、カチオン性乳化剤、ノニオン性乳化剤または両性乳化剤を併用することによりアスファルトの乳化性能を更に高めることができる。
【００２８】
アニオン性乳化剤としては、脂肪酸、アルキルサルフェート、アルキルエーテルサルフェート、アルキルベンゼンスルホン酸、アルキルリン酸またはそれらの塩等を挙げることができる。カチオン性乳化剤としては、アルキルアミン、アルキルポリアミン、アミドアミン、アルキルイミダゾリン等のアミンの鉱酸または低級カルボン酸塩、４級アンモニウム塩等を挙げることができる。両性乳化剤としては、酢酸ベタイン、アミドベタイン、スルホベタイン、イミダゾリウムベタイン、アミンオキシド等を挙げることができる。ノニオン性乳化剤としては、ソルビタンエステル、ソルビタンエステルのＡＯ付加物、長鎖アルコールのエチレンオキシド付加物、アルキルフェノールのエチレンオキシド付加物、アルキルグルコシド等を挙げることができる。
【００２９】
水溶性共重合体と他の乳化剤との併用比率は使用目的により異なるが、好ましくは重量比で水溶性共重合体／乳化剤＝０．１／９９．９〜９９．９／０．１であり、さらに好ましくは０．５／９９．５〜５０／５０、より好ましくは１／９９〜３０／７０である。
【００３０】
本発明のアスファルト乳化分散剤は、アスファルトを乳化する際に予め水と混合して、アスファルトに添加することが望ましいが、本発明の乳化分散剤の一部を、乳剤組成物と骨材を混合する合材製造時に添加することも可能である。
【００３１】
本発明のアスファルト乳化分散剤は、アスファルト乳剤の貯蔵安定性を改善する目的で水溶性高分子を併用することができる。この水溶性高分子としては、ポリビニルアルコール、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、カチオン化セルロース、ガム類を挙げることができる。さらに、施工後の骨材とアスファルトの接着性を向上させる目的でタンニン、没食子酸等のフェノール系化合物を添加することもできる。
【００３２】
本発明のアスファルト乳化分散剤の添加量は、アスファルトと水の合計重量に対し好ましくは０．０２〜１０重量％、更に好ましくは０．０５〜５重量％である。
【００３３】
本発明の水中油滴型アスファルト乳剤組成物は、アスファルト、本発明のアスファルト乳化分散剤及び水を含有するものである。
【００３４】
本発明で用いられるアスファルトとしては、ストレートアスファルト、カットバックアスファルト、ブローンアスファルト、セミブローンアスファルト、ポリマー改質アスファルト、天然ビチューメン、再生アスファルト等を挙げることができる。
【００３５】
水中油滴型アスファルト乳剤組成物におけるアスファルト及び水の含有量は、乳剤の貯蔵安定性及び道路舗装体の強度と耐久性の観点から、アスファルトの含有量が好ましくは４０〜８０重量％であり、更に好ましくは５０〜７５重量％であり、水の含有量が好ましくは２０〜６０重量％であり、さらに好ましくは２５〜５０重量％である。
【００３６】
本発明のアスファルト乳剤組成物は、コロイドミル、ホモジナイザー、ラインミキサー等の乳化機により製造することができる。
【００３７】
【実施例】
表１〜３に実施例及び比較例に使用した本発明のアスファルト乳化分散剤の組成を示す。
【００３８】
【表１】
【表２】
【表３】
（水溶性共重合体の製造）
表１〜２（実施例１〜２１）の共重合体は、特開昭５９−１６２１６３号公報３〜４頁の記載の方法にて製造した。また、表１〜２中の共重合体の分子量はゲルパーミエーションクロマトグラフィー法／ポリスチレンスルホン酸ナトリウム換算による分子量から求めた重量平均分子量である。表１〜３においてＥＯはエチレンオキシド、ＰＯはプロピレンオキシドを表し、括弧の次の数字は平均付加モル数を表す。また、ＰＯＥはポリオキシエチレンの略であり、ＥＯｐはエチレンオキシド平均付加モル数である。Ｍｗは重量平均分子量である。
【００４２】
（アスファルト乳剤組成物の製造）
針入度８０〜１００のストレートアスファルトを１４５℃に加熱溶融した。５５℃の温水に、表１に示す水溶性共重合体及び乳化剤を所定の比率で計７．５重量％（アスファルト乳剤組成物に対して３重量％）を溶解し乳化分散剤を準備した。前記溶融アスファルト６０重量部と乳化分散剤４０重量部を同時にコロイドミル（５０００ｒｐｍ）に通してアスファルト乳剤組成物を得た。得られたアスファルト乳剤組成物を室温まで冷却した後、セメント混合性、混合状態及び残留安定度を以下の方法で測定した。その結果を表４に示す。
【００４３】
（セメント混合性）
社団法人日本道路協会編、「舗装試験法便覧」（平成５年１２月２０日、第６版）４９７頁のセメント混合性試験方法に従い測定した。測定値が小さいほどセメントとアスファルト乳剤組成物の混合性が良好である。
【００４４】
（残留安定度）
「舗装試験法便覧」５０７頁のマーシャル安定度試験方法により供試体を作成し、水浸強度と非水浸強度との比を残留安定度とした。残留安定度が高いほど耐久性が良好である。養生条件は、２０℃気中で２８日間養生した後、水浸強度測定用供試体は２０℃水中７日間養生し、非水浸強度測定用供試体は２０℃気中７日間養生した。
【００４５】
（混合状態）
舗装用常温アスファルト混合物製造の際の混合状態を骨材の混合性として評価した。すなわち、６号砕石３５重量部、細砂４２重量部、スクリーニングス６重量部、普通ポルトランドセメント７重量部、アスファルト乳剤組成物１０重量部、比較例１１では更に発泡剤（アルミニウム粉末Ｃ−２５０、中島金属箔粉工業（株））０．２重量部を、モルタルミキサーに投入し２分間混合しアスファルト合材を製造した。１バッチの練り混ぜ量は１０ｋｇである。練り上がり直後のミキサー中の合材（表面の直径約３０ｃｍ）の混合状態を目視にて観察し、６号砕石とそれ以外の成分の分離が無く均一に混合した状態を「良い」、１〜１０個の砕石が分離した状態を「普通」、１１個以上の砕石が分離した状態を「悪い」として３段階評価をした。
【００４６】
【表４】
【発明の効果】
表４から明らかなように、本発明のアスファルト乳化分散剤は、乳剤組成物のセメント混合性を飛躍的に改良すると共に、骨材混合性をも改善しアスファルト合材の作業性を良好にする。さらに、本発明のアスファルト乳化分散剤で乳化したアスファルト乳剤組成物を用いた舗装用合材の残留安定度は極めて高く、耐久性に優れる道路舗装体を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an asphalt emulsifying dispersant used for emulsifying asphalt, and an oil-in-water asphalt emulsion composition excellent in cement mixing property, aggregate mixing property, and durability obtained by using the asphalt emulsifying dispersant.
[0002]
[Prior art and problems to be solved by the invention]
Asphalt is widely used for road paving, waterproofing / adhesive materials, railroad track laying and so on. However, since asphalt is very viscous at room temperature, workability is extremely poor. Therefore, in order to ensure the desired workability at room temperature, there is a technique of improving the fluidity and using it as a form of an oil-in-water emulsion composition using an appropriate emulsifier and water. As an emulsifier for an oil-in-water emulsion, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, or an amphoteric emulsifier is known, and is properly used depending on each use.
[0003]
In addition, normal temperature mixture for paving (hereinafter referred to as “mixed material”) used for general roads, playgrounds, parking lots, etc. requires strength, durability, and wear resistance. Therefore, aggregates such as sand, gravel, cement, filler Etc. and a mixture of asphalt emulsions are used.
[0004]
However, asphalt emulsion compositions using conventional anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers, amphoteric emulsifiers, etc. are not sufficiently mixed with aggregates such as sand, gravel, cement, filler, etc. In addition, the emulsion composition is separated or agglomerated, which makes it difficult to produce a composite material having excellent workability, and there are problems in strength and durability.
[0005]
In order to solve these problems, the combined use of an emulsifier and a foaming agent or a dispersant has been studied (Japanese Patent Application Laid-Open No. 11-12016). However, the combined use of the foaming agent improves the mixing ability of the aggregate, but voids due to bubbles remain in the composite, and it cannot be said that the strength and durability are satisfied. In addition, naphthalene sulfonic acid formalin condensate sodium salt and polyacrylic acid sodium salt are mentioned as dispersants, but these dispersants have an action of inhibiting emulsification of asphalt, and have sufficient cement mixing properties and bones. The material mixability is not obtained.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide an asphalt emulsifying dispersant capable of obtaining an oil-in-water type asphalt emulsion composition excellent in cement mixing property, aggregate mixing property and durability.
[0007]
[Means for Solving the Problems]
The present invention includes at least one vinyl monomer (a) having an average of 2 to 300 moles of an oxyalkylene group having 2 to 3 carbon atoms (hereinafter referred to as AO), a carboxyl group, a sulfonic acid group, and an amide group. Alternatively, an asphalt emulsifying dispersant containing a water-soluble copolymer obtained by polymerizing one or more vinyl monomers (b) having these water-soluble salts is provided.
[0008]
The present invention also provides an oil-in-water asphalt emulsion composition containing asphalt, the asphalt emulsifying dispersant of the present invention and water.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the monomer (a), AO having 2 to 3 carbon atoms is an ethylene oxide group and a propylene oxide group, and the copolymer structure constituting the water-soluble substance of the present invention has 2 to 3 carbon atoms. AO is essential. As these AO addition forms, single addition, random addition, block addition, or alternate addition of AO having 2 or 3 carbon atoms can be used.
[0010]
The above-mentioned copolymer into which AO is introduced is water-soluble, and one containing one or more of carboxyl groups, sulfonic acid groups, amide groups or water-soluble salts thereof is used. Examples of water-soluble salts include metal salts such as sodium salts, potassium salts, calcium salts, and magnesium salts, ammonium salts, triethanolamine salts, diethanolamine salts, and monoethanolamine salts.
[0011]
Examples of the water-soluble copolymer of the present invention include one or more of alkenyl ether and monomer (a) represented by the following general formula (A), maleic anhydride copolymer and the following general formula (B). And a copolymer with one or more selected from compounds represented by the following general formula (C).
[0012]
[Chemical 3]
(Where
R 1 and R 2 : hydrogen atom or methyl group,
m1 is a number from 0 to 2,
AO: an oxyalkylene group having 2 to 3 carbon atoms,
n: number from 2 to 300,
X: A hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the n AOs may be the same or different. )
[0014]
[Formula 4]
(Where
R 3 and R 6 : hydrogen atom or methyl group,
R 4 and R 5 : a hydrogen atom, a methyl group or (CH 2 ) m2 COOM 2 ,
M 1 , M 2 and Y: hydrogen atom or cationic group (preferably a cationic group derived from an alkali metal, alkaline earth metal, ammonium group, amino group or substituted alkylammonium group)
m2: an integer from 0 to 2,
Indicates. ).
[0016]
Examples of the monomer represented by the general formula (A) include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, methoxy polyethylene glycol, methoxy polyethylene polypropylene glycol, ethoxy polyethylene glycol, ethoxy polyethylene polypropylene glycol, propoxy polyethylene glycol, and propoxy polyethylene. Examples thereof include ester compounds of one-end alkyl group-blocked polyalkylene glycol such as polypropylene glycol and acrylic acid or methacrylic acid, and ethylene oxide or propylene oxide adducts to acrylic acid or methacrylic acid. The number of moles of alkylene oxide added to the polyalkylene glycol is 2 to 300, and the one-end alkyl group-blocked type is preferable from the viewpoint of production.
[0017]
Examples of the monomer represented by the general formula (B) include unsaturated monocarboxylic acid and unsaturated dicarboxylic acid. Examples of the unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, and alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts thereof. The unsaturated dicarboxylic acid monomer includes maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, fumaric acid, or alkali metal salts, alkaline earth metal salts, ammonium thereof. Salts and amine salts.
[0018]
In addition, examples of the monomer represented by the general formula (C) include allyl sulfonic acid, methallyl sulfonic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts thereof.
[0019]
The copolymer according to the present invention can be produced by a known method. Examples of this production method include the solvents exemplified in JP-A-59-162163, pages 3-4, JP-A-62-70250, pages 4-5, JP-A-62-78137, pages 4-5 and the like. A polymerization method is mentioned. That is, it can be produced by polymerizing the monomers (A), (B) and (C) in a suitable solvent.
[0020]
For example, in water or a lower alcohol having 1 to 4 carbon atoms, in the presence of a polymerization initiator such as ammonium persulfate or hydrogen peroxide, sodium hydrogen sulfite or mercaptoethanol is added if necessary, and a nitrogen atmosphere is used at 50 to 100 ° C. What is necessary is just to make it react for 0.5 to 10 hours. In addition, other copolymerizable monomers may be copolymerized as long as the present invention is not impaired. Such monomers include acrylonitrile, acrylamide, methacrylamide, styrene and the like.
[0021]
Moreover, the range of the average added mole number of AO of 2 to 300 is excellent in cement mixing property, aggregate mixing property and durability of the asphalt emulsion composition, and 100 to 200 is particularly excellent.
[0022]
Furthermore, it is more preferable in terms of cement mixing properties to use a polymer of AO having a different distribution in combination as in the case where n in the general formula (A) is 100 to 200 and n is 2 to 50 in the general formula (A). .
[0023]
In the water-soluble copolymer of the present invention, the polymerization ratio of the monomer (a) to the monomer (b) is monomer (a) / monomer (b) = 0.1 / 100 in molar ratio. ~ 200/100, the asphalt emulsion composition is excellent in cement mixing property, aggregate mixing property, and durability, and monomer (a) / monomer (b) = 10/100 to 100/100 The range is particularly excellent.
[0024]
The weight average molecular weight of the water-soluble copolymer of the present invention (gel permeation chromatography method / standard substance sodium polystyrene sulfonate equivalent / water system) is in the range of 5,000 to 100,000. It is particularly excellent from the viewpoints of properties, aggregate mixing properties, and durability. Moreover, you may contain the monomer copolymerizable with monomer (a) and (b).
[0025]
The content of the water-soluble copolymer of the present invention in the emulsifying dispersant is preferably 0.1 to 100% by weight, and the content of this copolymer in the asphalt emulsion composition varies depending on the purpose of use. Preferably it is 0.05 to 10 weight%, More preferably, it is 0.1 to 5 weight%.
[0026]
The mechanism by which the asphalt emulsion composition using the asphalt emulsifying dispersant of the present invention is excellent in cement mixing property, aggregate mixing property and durability is not necessarily clear, but the water-soluble copolymer of the present invention is cement or aggregate. It is expected to improve the mixing property by adsorbing to the surface of the steel and exhibiting a protective colloid function and suppressing the reaction of cement, the reaction of cement and asphalt emulsion, and the reaction of aggregate and asphalt emulsion. In addition, since the mixability is good, it is considered that cement, aggregate, and asphalt emulsion are uniformly mixed, and the road is sufficiently solidified at the time of road construction, so that pavement with excellent durability is possible.
[0027]
The combined use of the water-soluble copolymer used in the present invention with an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, or an amphoteric emulsifier can further enhance the emulsifying performance of asphalt.
[0028]
Examples of the anionic emulsifier include fatty acids, alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonic acids, alkyl phosphoric acids, or salts thereof. Examples of the cationic emulsifier include mineral acids of amines such as alkylamines, alkylpolyamines, amidoamines, and alkylimidazolines, lower carboxylic acid salts, and quaternary ammonium salts. Examples of amphoteric emulsifiers include betaine acetate, amide betaine, sulfobetaine, imidazolium betaine, and amine oxide. Examples of nonionic emulsifiers include sorbitan esters, AO adducts of sorbitan esters, ethylene oxide adducts of long chain alcohols, ethylene oxide adducts of alkylphenols, alkyl glucosides, and the like.
[0029]
The combined ratio of the water-soluble copolymer and the other emulsifier varies depending on the purpose of use, but is preferably water-soluble copolymer / emulsifier = 0.1 / 99.9 to 99.9 / 0.1 by weight ratio. More preferably, it is 0.5 / 99.5 to 50/50, more preferably 1/99 to 30/70.
[0030]
The asphalt emulsifying dispersant of the present invention is preferably mixed with water in advance when emulsifying asphalt and added to the asphalt. However, a part of the emulsifying dispersant of the present invention is mixed with the emulsion composition and the aggregate. It is also possible to add at the time of manufacturing the composite material.
[0031]
The asphalt emulsifying dispersant of the present invention can be used in combination with a water-soluble polymer for the purpose of improving the storage stability of the asphalt emulsion. Examples of the water-soluble polymer include polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, cationized cellulose, and gums. Furthermore, phenolic compounds such as tannin and gallic acid can be added for the purpose of improving the adhesion between the aggregate after construction and asphalt.
[0032]
The addition amount of the asphalt emulsifying dispersant of the present invention is preferably 0.02 to 10% by weight, more preferably 0.05 to 5% by weight, based on the total weight of asphalt and water.
[0033]
The oil-in-water asphalt emulsion composition of the present invention contains asphalt, the asphalt emulsifying dispersant of the present invention and water.
[0034]
Examples of the asphalt used in the present invention include straight asphalt, cutback asphalt, blown asphalt, semi-blown asphalt, polymer-modified asphalt, natural bitumen, and regenerated asphalt.
[0035]
The content of asphalt and water in the oil-in-water asphalt emulsion composition is preferably 40 to 80% by weight from the viewpoint of storage stability of the emulsion and strength and durability of the road pavement, More preferably, it is 50 to 75% by weight, and the water content is preferably 20 to 60% by weight, and more preferably 25 to 50% by weight.
[0036]
The asphalt emulsion composition of the present invention can be produced by an emulsifier such as a colloid mill, a homogenizer, or a line mixer.
[0037]
【Example】
Tables 1 to 3 show the compositions of the asphalt emulsifying dispersant of the present invention used in Examples and Comparative Examples.
[0038]
[Table 1]
[Table 2]
[Table 3]
(Production of water-soluble copolymer)
The copolymers shown in Tables 1 and 2 (Examples 1 to 21) were produced by the method described in JP-A No. 59-162163, pages 3 to 4. Moreover, the molecular weight of the copolymer in Tables 1-2 is a weight average molecular weight calculated | required from the molecular weight by gel permeation chromatography method / sodium polystyrenesulfonate conversion. In Tables 1 to 3, EO represents ethylene oxide, PO represents propylene oxide, and the number in parentheses represents the average number of moles added. POE is an abbreviation for polyoxyethylene, and EOp is the average number of moles of ethylene oxide added. Mw is a weight average molecular weight.
[0042]
(Production of asphalt emulsion composition)
Straight asphalt with a penetration of 80 to 100 was heated and melted at 145 ° C. A total of 7.5% by weight (3% by weight based on the asphalt emulsion composition) of the water-soluble copolymer and the emulsifier shown in Table 1 was dissolved in 55 ° C. warm water at a predetermined ratio to prepare an emulsifying dispersant. 60 parts by weight of the molten asphalt and 40 parts by weight of the emulsifying dispersant were simultaneously passed through a colloid mill (5000 rpm) to obtain an asphalt emulsion composition. After the obtained asphalt emulsion composition was cooled to room temperature, cement mixing property, mixing state and residual stability were measured by the following methods. The results are shown in Table 4.
[0043]
(Cement mixing)
Measured according to the cement mixing test method, page 497, “Handbook of Pavement Test Methods” (December 20, 1993, 6th edition) edited by Japan Road Association. The smaller the measured value, the better the mixability between the cement and the asphalt emulsion composition.
[0044]
(Residual stability)
A specimen was prepared by the Marshall stability test method on page 507 of “Handbook of Pavement Test Method”, and the ratio of water immersion strength to non-water immersion strength was defined as residual stability. The higher the residual stability, the better the durability. The curing conditions were as follows: after curing for 28 days in the atmosphere at 20 ° C., the specimen for water immersion strength measurement was cured for 7 days in 20 ° C. water, and the specimen for non-water immersion strength measurement was cured for 7 days in the air at 20 ° C.
[0045]
(Mixed state)
The mixing state at the time of producing the room temperature asphalt mixture for pavement was evaluated as the mixing property of the aggregate. That is, 35 parts by weight of crushed stone No. 6, 42 parts by weight of fine sand, 6 parts by weight of screenings, 7 parts by weight of ordinary Portland cement, 10 parts by weight of asphalt emulsion composition, and in Comparative Example 11, a foaming agent (aluminum powder C-250, Nakajima Metal Foil Powder Industry Co., Ltd. (0.2 part by weight) was put into a mortar mixer and mixed for 2 minutes to produce an asphalt mixture. The mixing amount for one batch is 10 kg. The state of mixing of the mixture (surface diameter of about 30 cm) in the mixer immediately after kneading is visually observed, and the state of uniform mixing without separation of No. 6 crushed stone and other components is “good”. Three-stage evaluation was performed, assuming that the state in which 10 crushed stones were separated was “normal” and the state in which 11 or more crushed stones were separated was “bad”.
[0046]
[Table 4]
【The invention's effect】
As is apparent from Table 4, the asphalt emulsifying dispersant of the present invention dramatically improves the cement mixing property of the emulsion composition and also improves the aggregate mixing property, thereby improving the workability of the asphalt mixture. . Furthermore, the residual stability of the pavement mixture using the asphalt emulsion composition emulsified with the asphalt emulsifying dispersant of the present invention is extremely high, and a road pavement excellent in durability can be obtained.
Claims (4)
Ｒ 1 及びＲ 2 ：水素原子またはメチル基、
ｍ１：０〜２の数、
ＡＯ：炭素数２〜３のオキシアルキレン基、
ｎ：２〜３００の数、
Ｘ：水素原子または炭素数１〜３のアルキル基
を示し、ｎ個のＡＯは同一でも異なっていても良い。）
Ｒ 3 及びＲ 6 ：水素原子またはメチル基、
Ｒ 4 及びＲ 5 ：水素原子、メチル基または ( ＣＨ 2 ) m2 ＣＯＯＭ 2 、
Ｍ 1 、Ｍ 2 及びＹ：水素原子または陽イオン基、
ｍ２：０〜２の整数、
を示す。） One or more vinyl monomers (a) represented by the following general formula (A) having an average of 2 to 300 moles of an oxyalkylene (hereinafter referred to as AO) group having 2 to 3 carbon atoms, a carboxyl group, One or more vinyl monomers selected from a compound represented by the following general formula (B) and a compound represented by the following general formula (C) having a sulfonic acid group, an amide group or a water-soluble salt thereof ( An asphalt emulsifying dispersant containing a water-soluble copolymer obtained by polymerizing at least one of b).
R 1 and R 2 : hydrogen atom or methyl group,
m1 is a number from 0 to 2,
AO: an oxyalkylene group having 2 to 3 carbon atoms,
n: number from 2 to 300,
X: a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
The n AOs may be the same or different. )
R 3 and R 6 : hydrogen atom or methyl group,
R 4 and R 5 : hydrogen atom, methyl group or ( CH 2 ) m 2 COOM 2 ,
M 1 , M 2 and Y: hydrogen atom or cationic group,
m2: an integer from 0 to 2,
Indicates. )
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|---|---|---|---|
| JP2000204688A JP3798230B2 (en) | 2000-07-06 | 2000-07-06 | Asphalt emulsifying dispersant |
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| CN102234436A (en) * | 2010-04-23 | 2011-11-09 | 中国石油化工股份有限公司 | Frost resistant emulsified bitumen and preparation method thereof |
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| CN102234433B (en) * | 2010-04-23 | 2012-12-26 | 中国石油化工股份有限公司 | Frost-resistant emulsified asphalt for roads and preparation method thereof |
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| CN104140527A (en) * | 2013-12-09 | 2014-11-12 | 天津康泽威科技有限公司 | Preparation method of serialized slow-breaking and quick-setting type cationic asphalt emulsifier |
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| CN102234436A (en) * | 2010-04-23 | 2011-11-09 | 中国石油化工股份有限公司 | Frost resistant emulsified bitumen and preparation method thereof |
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