JP4334727B2 - Heated paving material with excellent peeling prevention - Google Patents
Heated paving material with excellent peeling prevention Download PDFInfo
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- JP4334727B2 JP4334727B2 JP2000111361A JP2000111361A JP4334727B2 JP 4334727 B2 JP4334727 B2 JP 4334727B2 JP 2000111361 A JP2000111361 A JP 2000111361A JP 2000111361 A JP2000111361 A JP 2000111361A JP 4334727 B2 JP4334727 B2 JP 4334727B2
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- 239000000463 material Substances 0.000 title claims description 24
- 230000002265 prevention Effects 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 claims description 32
- -1 alkenyl succinic anhydride Chemical compound 0.000 claims description 25
- 239000010426 asphalt Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229940014800 succinic anhydride Drugs 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 6
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 description 15
- 229920001281 polyalkylene Polymers 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
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- 238000000034 method Methods 0.000 description 7
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- 229920001577 copolymer Polymers 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
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- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical group CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-UHFFFAOYSA-N 3-dodec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCC=CC1CC(=O)OC1=O WVRNUXJQQFPNMN-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 0 COC=NCC* Chemical compound COC=NCC* 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
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- 235000019738 Limestone Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- WDGVXEICRJAKEZ-UHFFFAOYSA-N butanedioic acid;furan-2,5-dione Chemical compound O=C1OC(=O)C=C1.OC(=O)CCC(O)=O WDGVXEICRJAKEZ-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- BELZJFWUNQWBES-UHFFFAOYSA-N caldopentamine Chemical compound NCCCNCCCNCCCNCCCN BELZJFWUNQWBES-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000006028 limestone Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- RUSNFULRUJHOPI-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCNCCN RUSNFULRUJHOPI-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は加熱型舗装材料に関し、特に骨材と瀝青質との間に優れた剥離防止性を付与できる加熱型舗装材料の製造方法に関するものである。
【０００２】
【従来の技術】
従来からアスファルト、タール、ピッチ等の瀝青質は各種骨材と配合され道路舗装材料、防水材料に使用されている。
しかし、これらの瀝青質は骨材との親和性がなく、瀝青質が骨材から剥離し易い性質を有しており、雨水等の水の作用によって瀝青質が剥離するという現象が生じる。
この現象は更に運搬用車両の大型化等にも伴い、アスファルト舗装等の道路舗装材の耐久性に悪影響を及ぼしている。
このような問題を解決するため、例えば特公昭５５−３８９９３号公報では瀝青質にアルキルヒドロキシアミンを主成分とする化合物を添加する方法、特公昭５５−３８９９５号公報では高級脂肪族ポリアミン及びその誘導体を使用する方法、また特公昭５７−５１７４５号公報ではシラン化合物を添加する方法等が提案されている。
【０００３】
【発明が解決しようとする課題】
しかし、従来提案された方法はいずれも効果の面で不十分であり、未だ実用的に満足できる骨材との剥離防止性に優れた瀝青質が得られていないのが現状である。
従って本発明は剥離防止性に優れた加熱型アスファルト舗装材料の製造方法を確立することが課題である。
【０００４】
【課題を解決するための手段】
本発明者らは上記課題を解決するために鋭意研究した結果、瀝青質と骨材との剥離防止効果に極めて優れた添加剤を見い出し本発明に到達したものである。
即ち本発明は、基材として各種骨材と瀝青質等から成る加熱型舗装材料を製造するに際して、 下記一般式（ａ）
Ｈ２Ｎ〔（ＣＨ２）ｍＮＨ〕ｎ（ＣＨ２）ｍＮＨ２ （ａ）
（但し、ｍは２又は３の整数、ｎは１〜８の整数を示す）
で表されるポリアルキレンポリアミン１モルと、炭素数８〜２２の飽和もしくは不飽和脂肪酸１モル〜（ｎ＋１）モルとを反応させて得られる縮合物（Ａ）と下記一般式（Ｂ）
で表されるアルケニル無水コハク酸（Ｂ）とを（Ａ）：（Ｂ）＝９０：１０〜１０：９０重量部の配合によって得られる反応組成物（Ｉ）、
および酸価５〜１００のカルボキシル基を有する変性ポリオレフィン樹脂（ＩＩ）とを（Ｉ）：（ＩＩ）＝１００：０〜１０：９０（重量％）の割合で配合した組成物を瀝青質に対し０．０５〜５．０重量％添加することを特徴とする剥離防止性に優れた加熱型舗装材料を製造する方法を提供するものである。
以下本発明を詳細に説明する。
【０００５】
本発明において、前記一般式（ａ）
Ｈ２Ｎ〔（ＣＨ２）ｍＮＨ〕ｎ（ＣＨ２）ｍＮＨ２ （ａ）
で表されるポリアルキレンポリアミンは、ｎが１から８の範囲であることが必須で、例示するとジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタアミン、ペンタエチレンヘキサミン、オクタエチレンノナミン等のポリエチレンポリアミンやジプロピレントリアミン、トリプロピレンテトラミン、テトラプロピレンペンタアミン、ペンタプロピレンヘキサミン等を挙げることができるが、ｎが４〜６を有することが効果の点で最も好ましい。
【０００６】
前記ポリアルキレンポリアミンと反応させる炭素数８〜２２の飽和もしくは不飽和脂肪酸としてはカプリン酸、椰子脂肪酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、オレイン酸、リノール酸、トール油脂肪酸等いずれでも効果的であるが、炭素数が１６〜１８のパルミチン酸、ステアリン酸、オレイン酸、リノール酸等の飽和もしくは不飽和脂肪酸であることが効果の点で最も好ましい。
【０００７】
また前記ポリアルキレンポリアミン１モルに対して、炭素数８〜２２の飽和もしくは不飽和脂肪酸を１モル〜（ｎ＋１）モルの範囲で反応させるが、ポリアルキレンポリアミンのｎが１〜３である場合はポリアルキレンポリアミン１モルに対して脂肪酸を１〜２モル、ｎが４〜６である場合はポリアルキレンポリアミン１モルに対して脂肪酸を２〜３モル、ｎが７〜８である場合はポリアルキレンポリアミン１モルに対して脂肪酸を２〜４モル反応させることが効果的である。
【０００８】
また、前記縮合物（Ａ）とアルケニル無水コハク酸（Ｂ）との配合によって得られる反応組成物（Ｉ）を得るための下記一般式（Ｂ）
また、アルケニル基の炭素数は８〜１００の範囲であるが、効果的には１０〜６０の範囲が好ましく、特に好ましくは１２〜３０の範囲である。
【０００９】
次に、本発明に係わる前記反応組成物（Ｉ）を得るための縮合物（Ａ）とアルケニル無水コハク酸（Ｂ）との配合割合は、（Ａ）：（Ｂ）＝９０：１０〜１０：９０重量部であるが、本発明の趣旨とするところの剥離防止効果の面からは（Ａ）：（Ｂ）＝７０：３０〜４０：６０重量部の範囲がより好ましい。
【００１０】
また本発明に使用される酸価５〜１００のカルボキシル基を有する変性ポリオレフィン樹脂としては、酸化ポリエチレンワックス、酸化ポリプロピレンワックス、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体、エチレン−（無水）マレイン酸共重合体、プロピレン−（無水）マレイン酸共重合体、エチレン−（無水）イタコン酸共重合体及びこれらの２種以上の混合物等を例示できるが、いずれも酸価が５〜１００ｍｇＫＯＨ／ｇの範囲であることが必須条件であり、特に酸価が２０〜５０ｍｇＫＯＨ／ｇであることが剥離防止効果の点で好ましいし、且つ変性ポリオレフィン樹脂が酸化ポリエチレンワックスおよび酸化ポリプロピレンワックスであることが最も好ましい。
【００１１】
更に本発明に係わる組成物である、前記ポリアルキレンポリアミン１モルと炭素数８〜２２の飽和もしくは不飽和脂肪酸１モル〜（ｎ＋１）モルとを反応させて得られる縮合物（Ａ）とアルケニル無水コハク酸（Ｂ）との反応組成物（Ｉ）と酸価５〜１００のカルボキシル基を有する変性ポリオレフィン樹脂（ＩＩ）との配合割合は（Ｉ）：（ＩＩ）＝１００：０〜１０：９０（重量％）の範囲であるが、（Ｉ）：（ＩＩ）＝８０：２０〜４０：６０（重量％）の配合割合であることが特に効果的である。
【００１２】
本発明に使用される組成物は、下記により容易に得ることができる。
まず、前記ポリアルキレンポリアミンと高級脂肪酸とを苛性ソーダ又は苛性カリ等のアルカリ触媒下、公知の方法で縮合反応（脱水反応）を行いポリアルキレンポリアミン脂肪酸アマイド、または更にアルキル／アルケニルイミダゾリン化合物まで縮合させた縮合物を得る。
次いでこの縮合物と前記アルケニル無水コハク酸とを配合し加熱下、混合することにより反応組成物を得る。
尚、ここで得られる反応組成物は、ポリアルキレンポリアミン脂肪酸アマイド、または更にアルキル／アルケニルイミダゾリン化合物にまで縮合させた化合物中に有する一級アミノ基および／または二級アミノ基とアルケニル無水コハク酸との開環付加反応で生成するアルケニルコハク酸モノ（またはジ）アマイド化合物や、またはポリアルキレンポリアミン脂肪酸アマイド、または更にアルキル／アルケニルイミダゾリン化合物にまで縮合させた化合物中に有する一級アミノ基とアルケニル無水コハク酸とのイミド化反応によって生成するアルケニルコハク酸イミド化合物等である。
【００１３】
かくして得られた本発明に使用される組成物は、瀝青質と骨材との間に極めて優れた剥離防止性を与えることが可能である。
即ち本発明の趣旨とするところは、前記本発明に係わる特定の反応組成物（Ｉ）と酸価５〜１００のカルボキシル基を有する変性ポリオレフィン樹脂（ＩＩ）とを特定の割合で配合して使用することであり、本発明の根幹をなすものである。
従来このような提案はされておらず極めて重大な発見と言える。
本発明に使用される組成物が骨材と瀝青質との間の剥離防止効果に優れる理由は理論的に解明していないが、前記本発明に係わるアルケニルコハク酸誘導体である反応組成物（Ｉ）や変性ポリオレフィン樹脂（ＩＩ）が骨材表面に複雑に作用し、骨材表面と瀝青質との親和性を高め、効果を発揮しているものと類推している。
【００１４】
本発明に係わる組成物の加熱瀝青質に対する添加量は０．０５〜５．０重量％であるが、好ましくは０．３〜３．０重量％である。
５．０重量％を越える使用は効果的には変わらないが経済的に不利となる。
【００１５】
また、本発明に係わる組成物の瀝青質への添加（混合）方法は、例えば１００〜２５０℃に加熱溶融したアスファルト類に撹拌しながら添加するとか、また改質瀝青質を使用する場合は予め改質瀝青質を製造しておき、後本発明の組成物を添加する等の方法でもよい。
次に本発明を実施例により説明するが、本発明はその趣旨を越えない限り以下の実施例に限定されるものではない。
【００１６】
【実施例】
［本発明の組成物の合成例］
１．本発明の組成物（１）の合成
温度計、窒素ガス導入管、および冷却管を備えた検水管付き１Ｌ四つ口フラスコにオレイン酸５６０ｇ（２モル）とペンタエチレンヘキサミン２３２ｇ（１モル）を仕込み、窒素ガスを導入しながら徐々に昇温し、１８０℃で３時間脱水反応を行いペンタエチレンヘキサミンのジオレイン酸アマイドを得た。次に２４０℃まで昇温し、同温度で５時間脱水反応を行いイミダゾリン化合物であるジ−ヘプタデセニルイミダゾリン化合物を合成した。
次に別のフラスコに、得られたジ−ヘプタデセニルイミダゾリン化合物５０重量％（２００ｇ）と直鎖状α−ドデセニル無水コハク酸５０重量％（２００ｇ）を仕込み、１３０℃で６０分間撹拌し、ドデセニルコハク酸アミド化合物を得た。
次いで、酸化ポリエチレンワックス（軟化点１３０℃、酸価３０、分子量４，０００）２００ｇを加え１６０℃で３０分混合し冷却後、淡黄褐色フレーク状の本発明の組成物（１）を得た。
【００１７】
２．本発明の組成物（２）〜（１３）の合成
前記本発明の組成物（１）の合成例に準じ、表１−１および表１−２に記載した本発明に係わる本発明の組成物（２）〜（１３）を作製した。
【００１８】
［剥離防止効果の測定］
１．試験方法
本発明の効果を確認するために、アスファルト舗装要綱（日本道路公団発行）記載のアスファルト皮膜の剥離試験方法、粗骨材と舗装用石油アスファルトの接着性についての静的評価方法に準じて試験を行った。
１３ｍｍフルイを通過し９．５ｍｍフルイに止まる粒度の愛知県産安山岩、長野県産花崗岩及び大船渡産石灰岩各１００ｇを採取し良く洗浄した後、３００ｍｌの金属製容器に入れ１１０℃の温度で一定量になるまで乾燥させる。
次に予め１５０℃に保った恒温乾燥器に入れて１時間加熱し試験用砕石を得る。一方、溶融した石油アスファルト（針入度６０〜８０）に前記合成例で得た本発明の組成物を添加し混合した後、１８０℃の恒温乾燥器の中で所定時間（２４時間及び１６８時間）加熱する。
次いで加熱処理物の５．５ｇを前記で得た砕石に加え、アスファルトが完全に砕石表面を被覆するように１．５〜２分間激しくかき混ぜ、剥離防止性評価用試料を作製する。
作製した試料を８０℃に保った恒温水槽に３０分間浸漬したのち、水槽から引き上げて直ちに水道水で冷却する。
次いで、浸漬処理後の試料のアスファルト被膜の剥離状態を、剥離面積率の標本写真を参考にして１個づづ５％刻みに観察する。
剥離面積率は肉眼判定で、試料２０個の剥離面積率の平均を少数第１位を四捨五入し表す（但し、うすい半透明の部分は皮膜されていないものとする）。
【００１９】
２．実施例１〜実施例１８
前記剥離防止効果の測定方法に従い、本発明の組成物（１）〜（１３）を添加した場合の試料の剥離面積率を求め、実施例１〜実施例１８を得た。
結果を表３に記載したが、本発明の組成物を添加したアスファルト組成物は骨材から殆ど剥離していない。
【００２０】
３．比較例１〜比較例８
本発明外の比較化合物および比較組成物の作製を表２の如く行い、次いで実施例と同様な方法で比較化合物および比較組成物を添加した場合、また無添加の場合の試料の剥離面積率を求め比較例１〜比較例８を得た。
結果を表３中に示した。
【００２１】
【発明の効果】
表３に示すように、本発明の組成物（１）〜本発明の組成物（１３）は、歴青質に対し０．０５〜５．０重量％添加することにより、歴青質と骨材との間に極めて優れた剥離防止性を発揮させることができ、従って骨材が瀝青質と剥離することのない加熱型舗装材料を提供できる。
【００２２】
【表１−１】
【表１−２】
【表２】
【表３】
BACKGROUND OF THE INVENTION
The present invention relates to a heating-type pavement material, and more particularly to a method for producing a heating-type pavement material capable of imparting excellent peeling prevention properties between aggregate and bitumen.
[0002]
[Prior art]
Conventionally, bituminous materials such as asphalt, tar and pitch are blended with various aggregates and used in road paving materials and waterproofing materials.
However, these bituminous materials have no affinity for aggregates, and the bituminous materials have a property of being easily peeled off from the aggregates, and a phenomenon occurs in which the bituminous materials are peeled off by the action of water such as rain water.
This phenomenon also has an adverse effect on the durability of road pavement materials such as asphalt pavement as the transportation vehicle becomes larger.
In order to solve such a problem, for example, Japanese Patent Publication No. 55-38993 discloses a method of adding a compound containing alkylhydroxyamine as a main component to bitumen, and Japanese Patent Publication No. 55-38995 discloses a higher aliphatic polyamine and its derivatives. In addition, Japanese Patent Publication No. 57-51745 proposes a method of adding a silane compound.
[0003]
[Problems to be solved by the invention]
However, none of the methods proposed so far are insufficient in terms of effect, and the bituminous material having excellent anti-peeling properties from the aggregate has not been obtained yet.
Accordingly, it is an object of the present invention to establish a method for producing a heated asphalt pavement material that is excellent in anti-peeling properties.
[0004]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors have found an additive that is extremely excellent in the effect of preventing peeling of bituminous material and aggregate, and have reached the present invention.
That is, the present invention provides the following general formula (a) when producing a heating type pavement material composed of various aggregates and bitumen as a base material.
H 2 N [(CH 2 ) mNH] n (CH 2 ) mNH 2 (a)
(However, m is an integer of 2 or 3, and n is an integer of 1 to 8.)
A condensate (A) obtained by reacting 1 mol of a polyalkylene polyamine represented by the formula (1) with 1 to (n + 1) mol of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and the following general formula (B)
A reaction composition (I) obtained by blending (A) :( B) = 90: 10 to 10:90 parts by weight with alkenyl succinic anhydride (B) represented by:
And a modified polyolefin resin (II) having a carboxyl group having an acid value of 5 to 100 in a ratio of (I) :( II) = 100: 0 to 10:90 (% by weight) The present invention provides a method for producing a heated pavement material excellent in peeling prevention, characterized by adding 0.05 to 5.0% by weight.
The present invention will be described in detail below.
[0005]
In the present invention, the general formula (a)
H 2 N [(CH 2 ) mNH] n (CH 2 ) mNH 2 (a)
In the polyalkylene polyamine represented by the formula, it is essential that n is in the range of 1 to 8, for example, polyethylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, octaethylenenonamine, and dipropylene. Triamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine and the like can be mentioned, but n is most preferably 4 to 6 in view of the effect.
[0006]
The saturated or unsaturated fatty acid having 8 to 22 carbon atoms to be reacted with the polyalkylene polyamine is capric acid, coconut fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, tall oil fatty acid However, a saturated or unsaturated fatty acid such as palmitic acid, stearic acid, oleic acid, linoleic acid or the like having 16 to 18 carbon atoms is most preferable in view of the effect.
[0007]
In addition, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms is reacted in a range of 1 mol to (n + 1) mol with respect to 1 mol of the polyalkylene polyamine, and when n of the polyalkylene polyamine is 1 to 3 1 to 2 moles of fatty acid per mole of polyalkylene polyamine, 2 to 3 moles of fatty acid per mole of polyalkylene polyamine when n is 4 to 6 and polyalkylene when n is 7 to 8 It is effective to react 2 to 4 moles of fatty acid with respect to 1 mole of polyamine.
[0008]
Further, the following general formula (B) for obtaining a reaction composition (I) obtained by blending the condensate (A) with an alkenyl succinic anhydride (B)
Moreover, although carbon number of an alkenyl group is the range of 8-100, the range of 10-60 is effective effectively, Especially preferably, it is the range of 12-30.
[0009]
Next, the blending ratio of the condensate (A) and the alkenyl succinic anhydride (B) for obtaining the reaction composition (I) according to the present invention is as follows: (A) :( B) = 90: 10-10 However, the range of (A) :( B) = 70: 30 to 40:60 parts by weight is more preferable from the viewpoint of the effect of preventing peeling as intended by the present invention.
[0010]
Examples of the modified polyolefin resin having a carboxyl group having an acid value of 5 to 100 used in the present invention include oxidized polyethylene wax, oxidized polypropylene wax, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene- ( Anhydrous) maleic acid copolymer, propylene- (anhydrous) maleic acid copolymer, ethylene- (anhydrous) itaconic acid copolymer, a mixture of two or more of these, and the like. It is an essential condition that it is in the range of 100 mgKOH / g, and it is particularly preferable that the acid value is 20 to 50 mgKOH / g from the viewpoint of anti-peeling effect, and the modified polyolefin resin is oxidized polyethylene wax and oxidized polypropylene wax. Most preferred.
[0011]
Furthermore, the condensate (A) obtained by reacting 1 mol of the above polyalkylene polyamine with 1 mol to (n + 1) mol of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, which is a composition according to the present invention, and alkenyl anhydride The blending ratio of the reaction composition (I) with succinic acid (B) and the modified polyolefin resin (II) having a carboxyl group having an acid value of 5 to 100 is (I) :( II) = 100: 0 to 10:90. Although it is in the range of (% by weight), it is particularly effective that the mixing ratio is (I) :( II) = 80: 20 to 40:60 (% by weight).
[0012]
The composition used in the present invention can be easily obtained as follows.
First, the polyalkylene polyamine and higher fatty acid are condensed using a known method in the presence of an alkali catalyst such as caustic soda or caustic potash, and then condensed to a polyalkylene polyamine fatty acid amide, or further to an alkyl / alkenyl imidazoline compound. Get things.
Subsequently, this condensate and the alkenyl succinic anhydride are blended and mixed under heating to obtain a reaction composition.
The reaction composition obtained here is a polyalkylene polyamine fatty acid amide, or a primary amino group and / or a secondary amino group in a compound condensed to an alkyl / alkenyl imidazoline compound and an alkenyl succinic anhydride. Primary amino groups and alkenyl succinic anhydrides in alkenyl succinic mono (or di) amide compounds produced by ring-opening addition reactions, or polyalkylene polyamine fatty acid amides, or compounds further condensed to alkyl / alkenyl imidazoline compounds An alkenyl succinimide compound produced by an imidization reaction with
[0013]
The composition used in the present invention thus obtained can provide an extremely excellent anti-peeling property between the bituminous material and the aggregate.
That is, the gist of the present invention is that the specific reaction composition (I) according to the present invention and the modified polyolefin resin (II) having a carboxyl group having an acid value of 5 to 100 are blended at a specific ratio. And forms the basis of the present invention.
Such a proposal has not been made so far and can be said to be a very important discovery.
The reason why the composition used in the present invention is excellent in the anti-peeling effect between aggregate and bituminous has not been clarified theoretically, but the reaction composition (I) is an alkenyl succinic acid derivative according to the present invention. ) And modified polyolefin resin (II) act on the surface of the aggregate in a complex manner, increasing the affinity between the surface of the aggregate and the bituminous material and analogizing it.
[0014]
The amount of the composition according to the present invention to be added to the heated bitumen is 0.05 to 5.0% by weight, preferably 0.3 to 3.0% by weight.
Use over 5.0% by weight does not change effectively but is economically disadvantageous.
[0015]
In addition, the method of adding (mixing) the composition according to the present invention to bitumen is, for example, adding to a bitumen heated and melted at 100 to 250 ° C. with stirring, or when using a modified bitumen in advance. The modified bituminous may be manufactured, and the method of adding the composition of the present invention later may be used.
EXAMPLES Next, although an Example demonstrates this invention, this invention is not limited to a following example, unless the meaning is exceeded.
[0016]
【Example】
[Synthesis Example of Composition of the Present Invention]
1. 560 g (2 mol) of oleic acid and 232 g (1 mol) of pentaethylenehexamine were added to a 1 L four-necked flask equipped with a test tube equipped with a synthesis thermometer, a nitrogen gas introduction tube, and a cooling tube of the composition (1) of the present invention. The temperature was gradually raised while introducing and introducing nitrogen gas, and a dehydration reaction was carried out at 180 ° C. for 3 hours to obtain dioleic acid amide of pentaethylenehexamine. Next, the temperature was raised to 240 ° C., and a dehydration reaction was performed at the same temperature for 5 hours to synthesize an imidazoline compound, di-heptadecenyl imidazoline compound.
Next, in another flask, 50% by weight (200 g) of the obtained di-heptadecenylimidazoline compound and 50% by weight of linear α-dodecenyl succinic anhydride (200 g) were charged and stirred at 130 ° C. for 60 minutes. The dodecenyl succinic acid amide compound was obtained.
Subsequently, 200 g of oxidized polyethylene wax (softening point 130 ° C., acid value 30, molecular weight 4,000) was added, mixed at 160 ° C. for 30 minutes and cooled, and then a light tan flake-like composition (1) of the present invention was obtained. .
[0017]
2. Synthesis of Compositions (2) to (13) of the Invention According to the synthesis examples of the composition (1) of the invention, the compositions of the invention according to the invention described in Table 1-1 and Table 1-2. (2) to (13) were produced.
[0018]
[Measurement of peeling prevention effect]
1. Test method In order to confirm the effect of the present invention, according to the asphalt pavement outline (issued by Japan Highway Public Corporation) asphalt film peeling test method, the static evaluation method for adhesion between coarse aggregate and paving petroleum asphalt A test was conducted.
100g each of Aichi Prefecture Andesite, Nagano Prefecture Granite and Ofunato Limestone passing through 13mm sieve and stopping at 9.5mm sieve, washed well, then placed in a 300ml metal container and fixed amount at 110 ° C Allow to dry.
Next, it is placed in a constant temperature drier previously maintained at 150 ° C. and heated for 1 hour to obtain a crushed stone for testing. On the other hand, after the composition of the present invention obtained in the above synthesis example was added to and mixed with molten petroleum asphalt (penetration 60 to 80), it was kept in a constant temperature dryer at 180 ° C. for a predetermined time (24 hours and 168 hours). ) Heat.
Next, 5.5 g of the heat-treated product is added to the crushed stone obtained above, and the mixture is vigorously stirred for 1.5 to 2 minutes so that the asphalt completely covers the crushed stone surface, thereby preparing a sample for evaluating peeling prevention.
The prepared sample is immersed in a constant temperature water bath maintained at 80 ° C. for 30 minutes, then pulled up from the water bath and immediately cooled with tap water.
Next, the peeled state of the asphalt film of the sample after the immersion treatment is observed in increments of 5% one by one with reference to the specimen photograph of the peeled area ratio.
The peeled area ratio is determined by naked eye, and the average peeled area ratio of 20 samples is rounded off to the first decimal place (provided that the thin translucent part is not coated).
[0019]
2. Examples 1 to 18
According to the measurement method of the peeling prevention effect, the peeling area ratio of the sample when the compositions (1) to (13) of the present invention were added was obtained, and Examples 1 to 18 were obtained.
Although the result was described in Table 3, the asphalt composition which added the composition of this invention hardly peeled from the aggregate.
[0020]
3. Comparative Examples 1 to 8
The comparative compound and comparative composition outside the present invention were prepared as shown in Table 2, and then the peeled area ratio of the sample when the comparative compound and the comparative composition were added in the same manner as in the Examples and when they were not added As a result, Comparative Examples 1 to 8 were obtained.
The results are shown in Table 3.
[0021]
【The invention's effect】
As shown in Table 3, the composition (1) of the present invention to the composition (13) of the present invention was added in an amount of 0.05 to 5.0% by weight to the bituminous, so that the bitumen and bone Therefore, it is possible to provide a heat-type pavement material that can exhibit extremely excellent anti-peeling properties with the material, and therefore does not peel the aggregate from the bituminous material.
[0022]
[Table 1-1]
[Table 1-2]
[Table 2]
[Table 3]
Claims (1)
下記一般式（ａ）
Ｈ２Ｎ〔（ＣＨ２）ｍＮＨ〕ｎ（ＣＨ２）ｍＮＨ２ （ａ）
（但し、ｍは２又は３の整数、ｎは１〜８の整数を示す）
で表されるポリアルキレンポリアミン１モルと、炭素数８〜２２の飽和もしくは不飽和脂肪酸１モル〜（ｎ＋１）モルとを反応させて得られる縮合物（Ａ）と、下記一般式（Ｂ）
で表されるアルケニル無水コハク酸（Ｂ）とを（Ａ）：（Ｂ）＝９０：１０〜１０：９０重量部の配合によって得られる反応組成物（Ｉ）、
および酸価５〜１００のカルボキシル基を有する変性ポリオレフィン樹脂（ＩＩ）とを（Ｉ）：（ＩＩ）＝１００：０〜１０：９０（重量％）の割合で配合した組成物を瀝青質に対し０．０５〜５．０重量％添加することを特徴とする剥離防止性に優れた加熱型舗装材料を製造する方法。When manufacturing heated pavement materials composed of various aggregates and bitumen as the base material,
The following general formula (a)
H 2 N [(CH 2 ) mNH] n (CH 2 ) mNH 2 (a)
(However, m is an integer of 2 or 3, and n is an integer of 1 to 8.)
And a condensate (A) obtained by reacting 1 mol of a polyalkylenepolyamine represented by the formula (1) to 1 mol to (n + 1) mol of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, and the following general formula (B)
A reaction composition (I) obtained by blending (A) :( B) = 90: 10 to 10:90 parts by weight with alkenyl succinic anhydride (B) represented by:
And a modified polyolefin resin (II) having a carboxyl group having an acid value of 5 to 100 in a ratio of (I) :( II) = 100: 0 to 10:90 (% by weight) A method for producing a heated pavement material excellent in peeling prevention, characterized by adding 0.05 to 5.0% by weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000111361A JP4334727B2 (en) | 2000-03-09 | 2000-03-09 | Heated paving material with excellent peeling prevention |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000111361A JP4334727B2 (en) | 2000-03-09 | 2000-03-09 | Heated paving material with excellent peeling prevention |
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| Publication Number | Publication Date |
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| JP2001254015A JP2001254015A (en) | 2001-09-18 |
| JP4334727B2 true JP4334727B2 (en) | 2009-09-30 |
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