JPS62197456A - Bituminous composition - Google Patents
Bituminous compositionInfo
- Publication number
- JPS62197456A JPS62197456A JP3900986A JP3900986A JPS62197456A JP S62197456 A JPS62197456 A JP S62197456A JP 3900986 A JP3900986 A JP 3900986A JP 3900986 A JP3900986 A JP 3900986A JP S62197456 A JPS62197456 A JP S62197456A
- Authority
- JP
- Japan
- Prior art keywords
- component
- copolymerization reaction
- cyclopentadiene
- precursor
- reaction product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 19
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims abstract 2
- -1 cyclopentadiene compound Chemical class 0.000 claims description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract 3
- 229930195733 hydrocarbon Natural products 0.000 abstract 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract 3
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229910052697 platinum Inorganic materials 0.000 abstract 1
- 229910052703 rhodium Inorganic materials 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000010426 asphalt Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- DVIVBQJVHLJFFS-UHFFFAOYSA-N 3-cyclopenta-1,3-dien-1-ylfuran-2,5-dione Chemical compound O=C1OC(=O)C(C=2CC=CC=2)=C1 DVIVBQJVHLJFFS-UHFFFAOYSA-N 0.000 description 3
- MRXYVJPLZLBJLH-UHFFFAOYSA-N cyclopenta-1,3-diene;styrene Chemical compound C1C=CC=C1.C=CC1=CC=CC=C1 MRXYVJPLZLBJLH-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は歴青組成物に関し、さらに詳しくは、比較的高
温下で接着力の経時的低下が少ない歴青組成物に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a bituminous composition, and more particularly to a bituminous composition whose adhesive strength does not decrease over time at relatively high temperatures.
［従来技術］
建築物、構造物または各種材料の防水材、防錆材、封止
材などとして、アスファルト、ピッチなどの歴青物質を
基材とした組成物、すなわち歴青組成物が使用されてい
る。この歴青組成物において、配合されるべき他の成分
としては、従来いわゆる石油樹脂が知られている。この
ような石油樹脂としては、例えば、ジシクロペンタジェ
ン系樹脂、脂肪族炭化水素樹脂、芳香族炭化水素樹脂な
どがある。[Prior Art] Compositions based on bituminous substances such as asphalt and pitch, that is, bituminous compositions, are used as waterproofing materials, rust prevention materials, sealing materials, etc. for buildings, structures, and various materials. ing. In this bituminous composition, a so-called petroleum resin is conventionally known as another component to be blended. Examples of such petroleum resins include dicyclopentadiene resins, aliphatic hydrocarbon resins, and aromatic hydrocarbon resins.
［発明が解決しようとする問題点］
上述したような石油樹脂は基材である歴青物質との相溶
性が良好で容易に均一な組成物を与えるが、しかし、得
られた歴青組成物は、とくに比較的高温下でその接着力
が経時的に低下しやすいという問題があった。[Problems to be Solved by the Invention] Petroleum resins as described above have good compatibility with the bituminous material that is the base material and can easily provide a uniform composition; however, the resulting bituminous composition has a problem in that its adhesive strength tends to decrease over time, especially at relatively high temperatures.
本発明は、従来のかかる問題を解消し、とくに５０°Ｃ
以上の高温下における接着力の経時的低下が少ない歴青
組成物の提供を目的とする。The present invention solves the conventional problems and particularly
The object of the present invention is to provide a bituminous composition whose adhesive strength does not decrease over time at the above high temperatures.
［問題点を解決するための手段］
本発明者らは、上記目的を達成すべく鋭意研究を重ねた
結果、歴青物質に配合されるべき石油樹脂成分として、
従来の石油樹脂に代えて、石油樹脂として、特定の成分
の共重合反応生成物の本素添加物を採用したとぎに優れ
た効果が得られることを見出して本発明を完成するに到
った。[Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have found that the petroleum resin component to be added to the bituminous material is as follows:
We have completed the present invention by discovering that superior effects can be obtained by using the present additive, which is a copolymerization reaction product of specific components, as a petroleum resin in place of conventional petroleum resins.
すなわち１本発明の歴青組成物は、歴青物質に、シクロ
ペンタジェン系化合物とビニル置換芳香族炭化水素との
共重合反応生成物の水素添加物またはシクロペンタジェ
ン系化合物と不飽和ジカルボン酸もしくはその無水物と
の共重合反応生成物の水素添加物を配合してなることを
特徴とする。That is, 1 the bituminous composition of the present invention comprises a bituminous substance, a hydrogenated product of a copolymerization reaction product of a cyclopentadiene compound and a vinyl-substituted aromatic hydrocarbon, or a cyclopentadiene compound and an unsaturated dicarboxylic acid. Alternatively, it is characterized by containing a hydrogenated product of a copolymerization reaction product with an anhydride thereof.
［ｊＬ体的説明］
本発明の歴青組成物は、第１の成分として歴青物質を、
第２の成分として、特定の石油樹脂、すなわち、シクロ
ペンタジェン系化合物とビニル置換芳香族炭化水素との
共重合反応生成物の水素添加物（以下、（Ａ）成分と略
称することがある。）またはシクロペンタジェン系化合
物と不飽和ジカルボン酸もしくはその無水物との共重合
反応生成物の水素添加物（以下、ＣＢ）成分と略称する
ことがある。）を含有するものである。[jL Physical Description] The bituminous composition of the present invention contains a bituminous substance as the first component,
The second component is a hydrogenated product of a copolymerization reaction product of a specific petroleum resin, ie, a cyclopentadiene compound and a vinyl-substituted aromatic hydrocarbon (hereinafter sometimes abbreviated as component (A)). ) or a hydrogenated product (hereinafter referred to as CB) component of a copolymerization reaction product of a cyclopentadiene compound and an unsaturated dicarboxylic acid or its anhydride. ).
まず、第１の成分である歴青物質としては。First, as for the bituminous substance which is the first component.
とくに限定されるものではなく、例えば、ストレートア
スファルト、ブローンアスファルト、セミプローンアス
ファルト、溶剤脱歴アスファルトなどの石油アスファル
ト；石油ピッチ；石炭タール；石炭ピッチなどをあげる
ことができる。The material is not particularly limited, and examples thereof include petroleum asphalt such as straight asphalt, blown asphalt, semi-prone asphalt, and solvent deasphalted asphalt; petroleum pitch; coal tar; and coal pitch.
ついで、第２の成分、すなわち、（Ａ）成分および（Ｂ
）成分の前駆体である共重合反応生成物において、シク
ロペンタジェン系化合物としては、たとえば、シクロペ
ンタジェン、メチルシクロペンタジェン、エチルシクロ
ペンタジェンあるいはこれらの二量体、二量体、共二征
体等があげられる。Then, the second components, namely (A) component and (B
) In the copolymerization reaction product which is a precursor of the component, examples of the cyclopentadiene compound include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, or dimers, dimers, and codimers thereof. Examples include subjugation.
そして、ビニル置換芳香族炭化水素としては、たとえば
スチレン、α−メチルスチレン、ビニルトルエン、イソ
プロペニルベンゼン等があｔプられる。Examples of vinyl-substituted aromatic hydrocarbons include styrene, α-methylstyrene, vinyltoluene, and isopropenylbenzene.
また、不飽和ジカルボン酸としては、たとえば、マレイ
ン酸、シトラコン酸、イタコン酸等があげられ、不飽和
ジカルボン酸無水物としては。Further, examples of unsaturated dicarboxylic acids include maleic acid, citraconic acid, itaconic acid, etc., and examples of unsaturated dicarboxylic acid anhydrides.
前記各種の不飽和ジカルボン酸の無水物があげられる。Examples include anhydrides of the various unsaturated dicarboxylic acids mentioned above.
なお、上記（Ａ）成分および（Ｂ）成分の前駆体となる
共重合反応生成物のうち、とくに好ましいものとしては
、それぞれ、シクロペンタジェンとスチレンとの共重合
反応生成物およびシクロペンタジェンと無水マレイン酸
との共重合反応生成物をあげることができる。Among the copolymerization reaction products that serve as precursors for the components (A) and (B), particularly preferred are the copolymerization reaction products of cyclopentadiene and styrene and the copolymerization reaction products of cyclopentadiene and styrene, respectively. Examples include copolymerization reaction products with maleic anhydride.
本発明の（Ａ）成分および（Ｂ）成分は上記の共重合反
応生成物の水素添加物であり、この（Ａ）成分および（
Ｂ）成分は例えば次のようにして製造することができる
。Component (A) and component (B) of the present invention are hydrogenated products of the above-mentioned copolymerization reaction products, and this component (A) and (
Component B) can be produced, for example, as follows.
すなわち、まず、シクロペンタジェン系化合物とビニル
：ｄ換芳香族炭化水素または不飽和ジカルボン酸もしく
はその無水物とを共重合させて（Ａ）および（Ｂ）成分
の前駆体である共重合反応生成物を得る。この工程は具
体的には、上記の各出発原料をキシレン等の芳香族炭化
水素溶媒に混合し、温度２２０〜３２０°Ｃ１好ましく
は２５０〜３００℃で、１〜８時間、好ましくは１．５
〜５時間加熱する０反応終了後に溶媒を除去すればよい
。That is, first, a cyclopentadiene compound and a vinyl: d-substituted aromatic hydrocarbon or an unsaturated dicarboxylic acid or its anhydride are copolymerized to produce a copolymerization reaction that is a precursor of components (A) and (B). get something Specifically, this step involves mixing each of the above starting materials in an aromatic hydrocarbon solvent such as xylene, at a temperature of 220 to 320°C, preferably 250 to 300°C, for 1 to 8 hours, preferably 1.5
The solvent may be removed after the reaction is heated for ~5 hours.
こうして得られた（Ａ）および（Ｂ）成分の前駆体は、
未だその構造についての定説がなく、基本的にはシクロ
ペンタジェン系化合物とビニル置換芳香族炭化水素との
共重合体およびシクロペンタジェン系化合物と不飽和ジ
カルボン酸もしくはその無水物との共重合体であると推
定されるものの、それ以外にシクロペンタジェン系化合
物のホモポリマーをも含んでいる可能性がある。ともあ
れ、好ましい（Ａ）成分前駆体はシクロペンタジェン系
化合物に由来するモノマ一単位の含有率が８０〜３０重
縫％、好ましくは６０〜４０重量％であり、軟化点が４
０〜１６０℃、好ましくは７０−１４０℃であり、臭素
価が３０〜１１０ｇ／１００ｇ、好ましくは４０〜７０
ｇ７１００ｇである。また、好ましい（Ｂ）成分前駆体
は、シクロペンタジェン系モノマーに由来するモノマ一
単位の含有率が９０〜３０重（１１％、好ましくは８０
〜４０玉呈％であり、不飽和ジカルボン酸またはその無
水物に山来するモノマ一単位の含有率が１０〜７０重量
％、好ましくは２０〜６０重量％であり、軟化点が６０
〜２００℃、好ましくは９０−１８０℃であり、臭素価
が１０〜２００ｇ／１００ｇ、好ましくは５０〜１３０
ｇ／１００ｇであり、酸価が１００〜５００＋ｓｇＫＯ
Ｈ／ｇ、好ましくは２００ｍｇＫＯＨ／ｇである。The precursors of components (A) and (B) thus obtained are:
There is still no established theory about its structure, and basically it is a copolymer of a cyclopentadiene compound and a vinyl-substituted aromatic hydrocarbon, or a copolymer of a cyclopentadiene compound and an unsaturated dicarboxylic acid or its anhydride. Although it is presumed that it is, there is a possibility that it also contains homopolymers of cyclopentadiene-based compounds. In any case, the preferable component (A) precursor has a monomer unit content derived from a cyclopentadiene compound of 80 to 30% by weight, preferably 60 to 40% by weight, and a softening point of 4.
0 to 160°C, preferably 70 to 140°C, and a bromine number of 30 to 110g/100g, preferably 40 to 70
It is 7100g. In addition, the preferable component (B) precursor has a monomer unit content derived from a cyclopentadiene monomer of 90 to 30 weights (11%, preferably 80 weights).
~40% by weight, the content of monomer units that are present in the unsaturated dicarboxylic acid or its anhydride is 10 to 70% by weight, preferably 20 to 60% by weight, and the softening point is 60% by weight.
~200°C, preferably 90-180°C, and a bromine number of 10-200g/100g, preferably 50-130
g/100g, and the acid value is 100 to 500+sgKO
H/g, preferably 200 mgKOH/g.
ついで、このようにして得られた各共重合反応生成物を
水素添加することにより目的とする（Ａ）成分および（
Ｂ）成分を製造する。具体的には、シクロヘキサン等の
炭化水素等の溶媒中で、あるいは溶媒を使用せずに、Ｎ
ｉ、Ｐｄ。Next, each copolymerization reaction product obtained in this way is hydrogenated to obtain the desired component (A) and (
B) Produce the ingredients. Specifically, N
i, Pd.
Ｃｏ 、ＰＬ 、Ｒｈ系触媒の存在下に、温度１３０〜
３００℃、好ましくは１５０〜２６０℃に、１〜７時間
、好ましくは２〜５時間加熱しながら、前記（Ａ）成分
前駆体または（Ｂ）成分前駆体と水素とを接触させる。In the presence of Co, PL, Rh catalyst, the temperature is 130~
The (A) component precursor or (B) component precursor is brought into contact with hydrogen while heating at 300° C., preferably 150 to 260° C., for 1 to 7 hours, preferably 2 to 5 hours.
得られる（Ａ）成分および（Ｂ）成分は、前記各前駆体
の構造自体定説がないのであるから、シクロペンタジェ
ン系化合物とビニル置換芳香族炭化水素または不飽和ジ
カルボン酸もしくはその無水物との共重合反応生成物の
水素添加物の外にシクロペンタジェン系化合物のホモポ
リマーの水素添加物をも含んでいる可能性がある。The resulting components (A) and (B) are composed of a cyclopentadiene compound and a vinyl-substituted aromatic hydrocarbon or an unsaturated dicarboxylic acid or its anhydride, since there is no established structure of each of the precursors. In addition to the hydrogenated product of the copolymerization reaction product, it may also contain the hydrogenated product of the homopolymer of the cyclopentadiene compound.
本発明の歴青組成物は、前述した第１の成分である歴青
物質に上記第２の成分である（Ａ）成分または（Ｂ）成
分を配合して得られるものである。これらの配合比はと
くに限定されるものではないが、例えば、歴青物質１０
０重量部に対し。The bituminous composition of the present invention is obtained by blending component (A) or component (B), which is the second component, with the bituminous substance, which is the first component. The blending ratio of these substances is not particularly limited, but for example, 10 parts of bituminous material
Based on 0 parts by weight.
（Ａ）成分または（Ｂ）成分が５〜１００重量部、とく
に、１０〜７０重量部となるように設定することが好ま
しい。It is preferable to set the amount of component (A) or component (B) to 5 to 100 parts by weight, particularly 10 to 70 parts by weight.
また、この歴青組成物には、上述した第１および第２の
成分のほかに、必要に応じて熱可塑性ゴムを配合するこ
とができる。このような熱可塑性ゴムとしては１例えば
、ポリブタジェンゴム（ＢＲ）、ポリイソプレンゴム（
ＩＲ）、ポリクロロプレンゴム（ＣＲ）、ポリスチレン
−ブタジェンゴム（ＳＢＲ）、ポリアクリロニトリル−
ブタジェンゴム（ＮＢＲ）、ポリイソブチレン−イソプ
レンゴム（Ｉ Ｉ Ｒ） 、 スチレン−ブタジェン−
スチレンゴム（Ｓ Ｂ Ｓ）などがあげられる。Moreover, in addition to the above-mentioned first and second components, a thermoplastic rubber can be blended into this bituminous composition as needed. Examples of such thermoplastic rubbers include polybutadiene rubber (BR) and polyisoprene rubber (BR).
IR), polychloroprene rubber (CR), polystyrene-butadiene rubber (SBR), polyacrylonitrile-
Butadiene rubber (NBR), polyisobutylene-isoprene rubber (IIR), styrene-butadiene-
Examples include styrene rubber (SBS).
これらの熱可塑性ゴムは、上記歴青物質１００重量部に
対し、θ〜３０重量部、とくに１−１０重量部程度配合
されることが好ましい。These thermoplastic rubbers are preferably blended in an amount of θ to 30 parts by weight, particularly about 1 to 10 parts by weight, per 100 parts by weight of the bituminous substance.
なお、本発明の歴青物質は、上述した各成分を例えばダ
ルトンミキサー、ニーダ−などにより、８０−１８０℃
で１５〜６０分間混練することにより容易に製造するこ
とができる。The bituminous material of the present invention can be prepared by mixing the above-mentioned components at 80-180°C using, for example, a Dalton mixer or kneader.
It can be easily produced by kneading for 15 to 60 minutes.
［実施例］ 調製例１（（Ａ）成分の調製） 窒素で置換した攪拌機付き重合反応容器内に。[Example] Preparation Example 1 (Preparation of component (A)) In a polymerization reaction vessel with a stirrer purged with nitrogen.
キシレン（溶媒）１００ｇとシクロペンタジェン１００
ｇとスチレン１００ｇとを仕込み、２６０℃に加熱して
攪拌しながら２時間共重合反応を行なった。100g xylene (solvent) and 100g cyclopentadiene
g and 100 g of styrene were charged, and a copolymerization reaction was carried out for 2 hours while heating to 260° C. and stirring.
反応終了後、キシレンを除去して（Ａ）成分前駆体であ
るシクロペンタジェン−スチレン共重合反応生成物１８
０ｇを得た。このシクロペンタジェン−スチレン共重合
反応生成物の軟化点は９１℃であり、七ツマ一単位とし
てのスチレンの含有率は５０重量％であり、臭素価は５
６ｇ／１００ｇであり、酸価はｌ■ｇＫＯＨ／ｇ以下で
あり、ガードナー色相は８であった。After the reaction is completed, xylene is removed to obtain the cyclopentadiene-styrene copolymerization reaction product 18, which is the precursor of component (A).
Obtained 0g. The softening point of this cyclopentadiene-styrene copolymerization reaction product is 91°C, the content of styrene as one unit is 50% by weight, and the bromine number is 5.
6 g/100 g, the acid value was 1 g KOH/g or less, and the Gardner hue was 8.
しかるのち、窒素で置換した攪拌機付き反応容器に、上
記により得られた（Ａ）成分前駆体１００ｇとシクロヘ
キサン（溶媒）１００ｇとＰｄ触媒５ｇ（０，５重量％
のＰｄ金属を担持）とを装入し、水素を圧入して３０
ｋｇ／ ａｍ２Ｇとし、２００℃に加熱して攪拌下に４
時間水添反応を行なった。Thereafter, 100 g of the component (A) precursor obtained above, 100 g of cyclohexane (solvent), and 5 g of Pd catalyst (0.5% by weight) were placed in a reaction vessel equipped with a stirrer and purged with nitrogen.
Pd metal supported) was charged, hydrogen was injected under pressure, and 30
kg/am2G, heated to 200℃ and stirred for 4 hours.
The hydrogenation reaction was carried out for hours.
反応終了後に溶媒、触媒等を除去してシクロペンタジェ
ン−スチレン共重合反応生成物の水素添加物、すなわち
（Ａ）成分１００ｇを得た。After the reaction was completed, the solvent, catalyst, etc. were removed to obtain 100 g of a hydrogenated product of the cyclopentadiene-styrene copolymerization reaction product, that is, component (A).
この（Ａ）成分は、軟化点が１０９℃であり、臭素化が
５．１ｇ／１００ｇであり、芳香環水素添加度が３４％
であり、ガードナー色相が１以下であった。なお、酸価
は１ｍｇＫＯＨ／ｇ以下であった。This component (A) has a softening point of 109°C, bromination of 5.1g/100g, and a degree of aromatic ring hydrogenation of 34%.
and the Gardner hue was 1 or less. Note that the acid value was 1 mgKOH/g or less.
調製例２（（Ｂ）ｒ：＆分の調製）
窒素で置換した攪拌機イ４き重合反応容器内に、キシレ
ン（溶媒）４０ｇとシクロペンタジェン１００ｇと無水
マレイン酸３５ｇとを仕込み、２６０°Ｃに加熱して攪
拌しながら３時間共重合反応を行なった。Preparation Example 2 ((B) Preparation of r: & minutes) 40 g of xylene (solvent), 100 g of cyclopentadiene, and 35 g of maleic anhydride were charged into a polymerization reaction vessel equipped with a stirrer and replaced with nitrogen, and heated at 260°C. The copolymerization reaction was carried out for 3 hours while heating and stirring.
反応終了後、キシレンを除去して（Ｂ）成分前駆体であ
るシクロペンタジェン−無水マレイン酸共重合反応生成
物１２７ｇを得た。このシクロペンタジェン−無水マレ
イン酸共重合反応生成物の軟化点は１４２℃であり、モ
ノマ一単位としてのシクロペンタジェンの含有率は７５
重量％であり、臭素価は６４ｇ／１００ｇであり、酸価
は２３３１℃ｇＫＯＨ／ ｇであり、ガードナー色相は
１８以上であった。窒素で置換した攪拌機付き反応容器
に、上記により得られた（Ｂ）成分１００ｇとテトラヒ
ドロフラン（溶６Ｍ） １００ ｇとＰｄ触媒５ｇ（０
，５重量％のＰｄ金属を担持）とを装入し、水素を圧入
して３０ｇ／ｃｍ”Ｇとし、２００℃に加熱して攪拌下
に３．５時間水添反応を行なった。After the reaction was completed, xylene was removed to obtain 127 g of a cyclopentadiene-maleic anhydride copolymerization reaction product, which was a precursor of component (B). The softening point of this cyclopentadiene-maleic anhydride copolymerization product is 142°C, and the content of cyclopentadiene as a monomer unit is 75°C.
% by weight, the bromine number was 64 g/100 g, the acid value was 2331°C gKOH/g, and the Gardner hue was 18 or more. In a reaction vessel equipped with a stirrer and purged with nitrogen, 100 g of component (B) obtained above, 100 g of tetrahydrofuran (6M solution), and 5 g of Pd catalyst (0
, supporting 5% by weight of Pd metal), hydrogen was press-injected to give a pressure of 30 g/cm''G, and the hydrogenation reaction was carried out under stirring at 200° C. for 3.5 hours.
反応終了後に溶媒、触媒等を除去してシクロペンタジェ
ン−無水マレイン酸共重合反応生成物の水素添加物、す
なわち（Ｂ）成分１０１ｇを得た。After the reaction was completed, the solvent, catalyst, etc. were removed to obtain 101 g of a hydrogenated product of the cyclopentadiene-maleic anhydride copolymerization reaction product, that is, component (B).
この（Ｂ）成分は、軟化点が１５８°Ｃであり。This component (B) has a softening point of 158°C.
臭素価が１６ｇ／１００ｇであり、酸価が２３０ｒｉｇ
／ Ｋ ＯＨ／ ｇであり、ガードナー色相が１６であ
った。Bromine number is 16g/100g and acid number is 230rig
/KOH/g, and the Gardner hue was 16.
実施例１〜５および比較例１〜３
歴青物質として石油アスファルト（ストレートアスファ
ルト、針入度６５．軟化点４８．５℃）を、石油樹脂と
して上記調製例１．２で得られた（Ａ）成分と（Ｂ）成
分および表示の各物質を、また、熱可塑性ゴムとしてス
チレン−ブタジェン−スチレンゴムをそれぞれ表示付配
合し、クルトンミキサーを使用して１５０℃において３
０分間混練して歴青組成物を調製した。Examples 1 to 5 and Comparative Examples 1 to 3 Petroleum asphalt (straight asphalt, penetration degree 65, softening point 48.5°C) was used as the bituminous substance, and petroleum resin obtained in Preparation Example 1.2 (A ), component (B), and each of the indicated substances, as well as styrene-butadiene-styrene rubber as a thermoplastic rubber, were blended with the indicated ingredients, and mixed at 150°C using a crouton mixer.
A bituminous composition was prepared by kneading for 0 minutes.
しかるのち、得られた溶融状態の歴青組成物を２５．４
Ｘ１５０ｍｍの綿布に２１の厚さとなるように塗布し、
この歴青組成物塗布面をモルタル板に圧着したのち、ギ
ヤーオーブンを用い以下に述べるような熱劣化促進試験
を行なった。すなわち、熱劣化促進条件は、
■ ７０℃において１６８時間保持
■ ７０℃において７２０時間保持
■ １００℃において１６８時間保持
の３種類とし、それぞれの温度で所定時間保持後に２５
°Ｃまで降温し、モルタル板を２５．４１ｍ幅に切断し
て試験片を作製した。ついで、各試験片について２０℃
における１８０°ビ一ル強度を測定し、結果を表中に示
した。なお、この測定は引張試験機（テンシロン）を使
用し、ＪＩＳ ＺＯ２３７に醇拠して行なった。Thereafter, the obtained bituminous composition in the molten state was heated to 25.4
Apply it to a 150mm x 150mm cotton cloth to a thickness of 21mm,
After the bituminous composition coated surface was pressed onto a mortar plate, a heat deterioration acceleration test as described below was conducted using a gear oven. In other words, there are three types of thermal deterioration acceleration conditions: (1) holding at 70°C for 168 hours, (2) holding at 70°C for 720 hours, and (2) holding at 100°C for 168 hours.
The temperature was lowered to °C, and the mortar plate was cut into a width of 25.41 m to prepare a test piece. Then, each test piece was heated to 20°C.
The 180° building strength was measured and the results are shown in the table. This measurement was carried out using a tensile tester (Tensilon) based on JIS ZO237.
［発明の効果］
以上の説明から明らかなように、本発明の歴青組成物は
、従来のものに比べて、とくに５０℃以上の比較的高温
下における接着強度の経時的低下が極めて小さいととも
に、その接着強度自体もはるかに高い優れたものである
。したがって、防水材、防錆剤、封止材などの素材とし
て有用であり、その工業的価値は大である。[Effects of the Invention] As is clear from the above description, the bituminous composition of the present invention exhibits extremely small decline in adhesive strength over time, especially at relatively high temperatures of 50°C or higher, compared to conventional compositions. , the adhesive strength itself is much higher and superior. Therefore, it is useful as a material for waterproof materials, rust preventives, sealants, etc., and its industrial value is great.
Claims (1)
素との共重合反応生成物の水素添加物またはシクロペン
タジエン系化合物と不飽和ジカルボン酸もしくはその無
水物との共重合反応生成物の水素添加物を配合してなる
ことを特徴とする歴青組成物。[Scope of Claims] A bituminous substance, a hydrogenated product of a copolymerization reaction product of a cyclopentadiene compound and a vinyl-substituted aromatic hydrocarbon, or a copolymerization product of a cyclopentadiene compound and an unsaturated dicarboxylic acid or its anhydride. A bituminous composition comprising a hydrogenated product of a polymerization reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3900986A JPS62197456A (en) | 1986-02-26 | 1986-02-26 | Bituminous composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3900986A JPS62197456A (en) | 1986-02-26 | 1986-02-26 | Bituminous composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62197456A true JPS62197456A (en) | 1987-09-01 |
| JPH0554870B2 JPH0554870B2 (en) | 1993-08-13 |
Family
ID=12541103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3900986A Granted JPS62197456A (en) | 1986-02-26 | 1986-02-26 | Bituminous composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62197456A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053409A1 (en) * | 2000-01-24 | 2001-07-26 | Total Raffinage Distribution S.A. | Coloured composition comprising a bituminous binder and uses thereof |
-
1986
- 1986-02-26 JP JP3900986A patent/JPS62197456A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053409A1 (en) * | 2000-01-24 | 2001-07-26 | Total Raffinage Distribution S.A. | Coloured composition comprising a bituminous binder and uses thereof |
| FR2804125A1 (en) * | 2000-01-24 | 2001-07-27 | Total Raffinage Distribution | An asphalt-free bituminous binder for providing colored road or pavement surfaces, comprises pigmented polymers and a plasticizer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0554870B2 (en) | 1993-08-13 |
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