JPH04100862A - Asphalt substitute composition - Google Patents
Asphalt substitute compositionInfo
- Publication number
- JPH04100862A JPH04100862A JP21845990A JP21845990A JPH04100862A JP H04100862 A JPH04100862 A JP H04100862A JP 21845990 A JP21845990 A JP 21845990A JP 21845990 A JP21845990 A JP 21845990A JP H04100862 A JPH04100862 A JP H04100862A
- Authority
- JP
- Japan
- Prior art keywords
- asphalt
- petroleum
- composition
- resin
- substitute composition
- 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
- 239000010426 asphalt Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000003208 petroleum Substances 0.000 claims description 29
- 239000003245 coal Substances 0.000 claims description 4
- 239000000025 natural resin Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 230000035515 penetration Effects 0.000 abstract description 9
- 230000005484 gravity Effects 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 239000004793 Polystyrene Substances 0.000 abstract description 4
- 229920002223 polystyrene Polymers 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000000638 solvent extraction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 239000003921 oil Substances 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000002372 labelling Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- 229920004939 Cariflex™ Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 238000009835 boiling 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Road Paving Structures (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔従来技術〕
英国特許第１ 、２２６ 、２３４号明細書には、コー
ルタール留出油中に存在している不飽和炭化水素を複数
重合させて得られた、例えばクマロンインデン樹脂（ａ
）およびモノビニル芳香族から得られたセグメントと共
役結合をもつジエンから得られたセグメントよりなるブ
ロック ポリマー（ｂ）よりなる道路舗装用組成物が開
示されている。Detailed Description of the Invention [Prior Art] British Patent Nos. 1, 226, 234 discloses that the unsaturated hydrocarbons present in coal tar distillate are Coumarone indene resin (a
) and a block polymer (b) comprising a segment obtained from a monovinyl aromatic and a diene having a conjugated bond.
また、特開昭５．！ｌ−１８３７５９号公報には（イ）
石油樹脂又はクマロンインデン樹脂、（ロ）パラフィン
系潤滑油留分て１００℃の動粘度が１０〜６０ｃｓｔの
フルフラールまたはフェノール溶剤で抽出された芳香族
油、（ハ）ＳＢＲラテックスよりなる舗装用結合組成物
が開示されている。Also, JP-A-5. ! Publication No. l-183759 includes (a)
A pavement bond consisting of a petroleum resin or coumaron indene resin, (b) an aromatic oil extracted with a furfural or phenol solvent that is a paraffinic lubricating oil fraction and has a kinematic viscosity of 10 to 60 cst at 100°C, and (c) SBR latex. Compositions are disclosed.
しかしながら、これらの組成物は、いずれも耐水性、レ
オロジー性状、自己結着性（骨材との接着性を含め、成
形品としたときの一体性が強い）等において充分満足で
きるものではない。However, none of these compositions is fully satisfactory in terms of water resistance, rheological properties, self-adhesiveness (strong integrity when formed into a molded product, including adhesion to aggregate), etc.
本発明は、アスファルトと同様の耐水性、レオロジー性
状、自己結着性を有し、かつ大へん透明性の高いアスフ
ァルト代替用組成物を提供することを目的とするもので
ある。An object of the present invention is to provide a composition for replacing asphalt that has water resistance, rheological properties, and self-binding properties similar to those of asphalt, and is highly transparent.
本発明は。 The present invention is.
（Ａ）石油系溶剤抽出油 約５０〜７０重量％
（Ｃ）熱可塑性ゴム 約０．５〜５重量％
（Ｄ）ナフテン酸 約０．３〜４重量％
よりなるアスファルト代替用組成物に関する。(A) Petroleum solvent extracted oil approximately 50-70% by weight
(C) Thermoplastic rubber approximately 0.5-5% by weight
(D) Naphthenic acid approximately 0.3-4% by weight
The present invention relates to an asphalt replacement composition comprising:
これにより、本発明の組成物は、ＪＩＳ Ｋ２２０７
石油アスファルト中のストレートアスファルト・グレー
ド４０〜１２０の規格のアスファルトのすへでに対する
代替品として有用であり、かつ、アスファルトでは得ら
れないすぐれた性質を示す。As a result, the composition of the present invention conforms to JIS K2207
It is useful as a substitute for straight asphalt grades 40-120 in petroleum asphalt, and exhibits excellent properties not available with asphalt.
前記石油系溶剤抽出油（Ａ）は、昭和４６年１１月３０
日石油連盟発行、「石油製品のできるまで」第１ｏｔ頁
、図６−１「−船釣な潤滑油製造工程Ｊに記載されてい
るとおり、原油から潤滑油を製造する過程において、溶
剤抽出によって得られる芳香族およびナフテン分に富ん
だ油状物質であり、一般に沸点（大気圧下）３５０°Ｃ
以上、粘度５〜１００ｃｓｔ／ １００℃、好ましくは
３０ｃｓｔ−１ｏＯｃｓｔ／ １００”Ｃ１針入度（Ｊ
Ｉ Ｓ Ｋ２２０７）１０００以上、軟化点（、Ｊ
Ｉ Ｓ Ｋ２２０７） ２０’Ｃ以下のものであり、
とくに芳香族とナフテン分の合計が４５−ｔ％以上（環
分析による）を占め、引火点が２２０℃以上のものが好
ましい。The petroleum solvent extracted oil (A) was produced on November 30, 1971.
Published by the Japan Petroleum Federation, "How petroleum products are made", page 1, Figure 6-1 "-Lubricating oil manufacturing process J", in the process of manufacturing lubricating oil from crude oil, solvent extraction is used. The resulting oil is rich in aromatics and naphthenes and generally has a boiling point (at atmospheric pressure) of 350°C.
Above, viscosity 5-100cst/100℃, preferably 30cst-1oOcst/100"C1 penetration (J
IS K2207) 1000 or more, softening point (, J
IS K2207) 20'C or less,
In particular, it is preferable that the total amount of aromatics and naphthenes is 45-t% or more (according to ring analysis) and the flash point is 220° C. or higher.
前記石油系、石炭系および／または天然系樹脂（Ｂ）は
、石油、石炭および／または天然物を出発物質とする固
体樹脂で、一般に分子量約２００〜３０００の重合物で
、脂肪族、芳香族および／または環状化合物の１元ない
し３元（共）重合物である。石油系樹脂としては、Ｃ１
〜Ｃ３の石油樹脂、テルペンおよび／またはフェノール
樹脂等を挙げることができ、石炭系樹脂としてはクマロ
ンインデン樹脂、キシレン樹脂等を挙げることができ、
また天然系樹脂としては各種樹脂酸エステルを挙げるこ
とができる。いずれも軟化点（環球式） ８０〜１８０
°Ｃ５比重１．０以上、針入度１０以下のものが好まし
い。The petroleum-based, coal-based and/or natural-based resin (B) is a solid resin made from petroleum, coal and/or natural products as a starting material, and is generally a polymer having a molecular weight of about 200 to 3000, and has aliphatic and aromatic properties. and/or a mono- to tertiary (co)polymer of cyclic compounds. As petroleum resin, C1
~C3 petroleum resins, terpene and/or phenol resins, etc. can be mentioned, and examples of the coal-based resins include coumaron indene resins, xylene resins, etc.
Further, examples of the natural resin include various resin acid esters. All have a softening point (ring and ball type) of 80 to 180
It is preferable to have a specific gravity of 1.0 or more at °C5 and a penetration of 10 or less.
前記熱可塑性ゴム（Ｃ）としては、末端セグメントとし
てポリスチレンセグメントを有し。The thermoplastic rubber (C) has a polystyrene segment as an end segment.
ゴム成分セグメントとしては、例えばポリブタジェンセ
グメント、ポリイソプレンセグメント、ポリエチレン・
ブチレンセグメント等を有する鎖状または枝状ブロック
共重合体であって、代表的なものとしてはＳＢＳ （ス
チレン−ブタジェン−スチレンブロック共！！合体）、
５ｚｓ（スチレン−イソプレン−スチレンブロック共重
合体）、５ＥＢＳ （スチレン−エチレン／ブチレン−
スチレンブロック共重合体）等を挙げることができる。Examples of rubber component segments include polybutadiene segments, polyisoprene segments, and polyethylene segments.
A chain or branched block copolymer having butylene segments, etc. Typical examples include SBS (styrene-butadiene-styrene block combination!!),
5zs (styrene-isoprene-styrene block copolymer), 5EBS (styrene-ethylene/butylene-
styrene block copolymer), etc.
分子量は８ＸＩＯ４以上、ポリスチレン含量１０〜５（
ｈｔ％、比重０．９以上のものが好ましい。Molecular weight is 8XIO4 or more, polystyrene content 10-5 (
ht% and specific gravity of 0.9 or more.
前記（Ａ）成分と（Ｂ）成分は親和性が高く任意の割合
で混合するので、（Ａ）５０〜７０ｗｔ％と（Ｂ）２５
〜４５ｗｔ％を混合して、針入度と軟化点のみについて
は、針入度４０−１２０．軟化点４０〜５５というアス
ファルトと同一の物性を達成することができるが、この
（Ａ）と（Ｂ）の混合物は感温性が大きすぎ、常温付近
における伸度が小さすぎ、また低温では脆すぎるという
欠点がある。The components (A) and (B) have a high affinity and can be mixed at any ratio, so (A) 50 to 70 wt% and (B) 25
~45wt% was mixed, and the penetration and softening point alone were 40-120. Although it is possible to achieve the same physical properties as asphalt with a softening point of 40 to 55, this mixture of (A) and (B) is too sensitive to temperature, has too little elongation at room temperature, and is brittle at low temperatures. There is a drawback that it is too much.
前記熱可塑性ゴム（Ｃ）の０．５〜５ｗｔ％の添加は、
（Ａ） ＋（Ｂ）の混合物の欠点を補い。The addition of 0.5 to 5 wt% of the thermoplastic rubber (C) is
Compensate for the defects of the mixture of (A) + (B).
感温性を低下させ、常温付近での伸度を大きくし、低温
での脆性を改善する。また、（Ｃ）は（Ａ）と（Ｂ）の
混合物に対する相溶性がすぐれているので相分離を生ず
ることがない。Reduces temperature sensitivity, increases elongation near room temperature, and improves brittleness at low temperatures. Furthermore, since (C) has excellent compatibility with the mixture of (A) and (B), no phase separation occurs.
しかしながら、（Ａ）＋ （Ｂ）＋ （Ｃ）の組成物で
は、いまだアスファルトの有する自己結着性、耐水性に
はほど遠いものである。すなわち、（Ａ）＋ （Ｂ）＋
（ｃ）の組成物について水浸マーシャル試験（６０’
Ｃの水中に最高１４日浸漬したのち、圧縮試験を行うも
のである）を行うと、６０°Ｃの水中に数時間浸漬した
だけで、供試体の試験片（供試体の組成、例、Ａ６１．
（ｈｔ％＋Ｂ３４．８ｗｔ％＋Ｃ４，２ｕｔ％＝ １０
０ｗｔ％の組成物５．５ｗｔ％と骨材およびフィラー計
９４ 、５ｔｉｔ％）は完全に崩壊し、とても力学試験
などができる状態ではなかった。However, the composition (A) + (B) + (C) is still far from having the self-binding properties and water resistance that asphalt has. That is, (A) + (B) +
Water immersion Marshall test (60'
A compression test is performed after being immersed in water at 60°C for up to 14 days. ．．
(ht%+B34.8wt%+C4,2ut%=10
The composition (5.5 wt %, total aggregate and filler (94%, 5 tit %)) completely disintegrated and was not in a condition that could be subjected to mechanical tests.
これに対して、少量のナフテン駿（Ｄ）を添加するとお
どろくべきことに、前述の崩壊現象は全くおこらず、力
学試験を行った結果も、アスファルトと較べて全く遜色
のないものであった。On the other hand, when a small amount of naphthene (D) was added, surprisingly, the above-mentioned disintegration phenomenon did not occur at all, and the results of mechanical tests were also comparable to asphalt.
前記ナフテンａ （Ｄ）は石油原油中に含まれるナフテ
ン環をもつカルボン准類を総称するものであり、化学構
造上単一の化合物ではなく、主として飽和単環カルボン
酸類、飽和二環カルボン酸類および脂肪族カルボン酸類
を含む。ナフテン環は主として、５，６．７員環である
。Naphthene a (D) is a general term for carboxylic derivatives with a naphthene ring contained in petroleum crude oil, and is not a single compound in terms of chemical structure, but mainly saturated monocyclic carboxylic acids, saturated bicyclic carboxylic acids, and saturated bicyclic carboxylic acids. Contains aliphatic carboxylic acids. Naphthene rings are primarily 5-, 6-, and 7-membered rings.
本発明のナフテン酸としてはとくに酸価５０〜３００ｍ
ｇ ＫＯ）Ｉ／ ｇ、引火点（ＣＯＣ）１５０℃以上が
好ましい。The naphthenic acid of the present invention has an acid value of 50 to 300 m.
gKO)I/g, flash point (COC) preferably 150°C or higher.
ナフテン酸の添加量は４ｗｔ％をこえるとその効果はほ
とんど向上せず、場合によっては他の性状に悪影響を与
える場合がある。ナフテン酸の好ましい添加量は０．４
〜３．７υｔ％とくに好ましい範囲は０．５〜３ 、５
ｗｔ％である。If the amount of naphthenic acid added exceeds 4 wt%, the effect will hardly improve, and in some cases, other properties may be adversely affected. The preferred amount of naphthenic acid added is 0.4
~3.7υt% A particularly preferable range is 0.5~3,5
It is wt%.
本発明組成物は、石油アスファルトの代替品であるので
、石油アスファルトについて説明し、ついで本発明組成
物の性質について説明する。Since the composition of the present invention is a substitute for petroleum asphalt, petroleum asphalt will be described first, and then the properties of the composition of the present invention will be described.
石油アスファルトの種類はストレートアスファルト、ブ
ローンアスファルトおよび防水工事用アスファルトの三
種類であるが最も需要の大きいものは針入度４０〜針人
度１２０のストレートアスファルトであって、これが全
体の約９０％を占める。There are three types of petroleum asphalt: straight asphalt, blown asphalt, and asphalt for waterproofing work, but the one with the highest demand is straight asphalt with a penetration level of 40 to 120, which accounts for about 90% of the total. occupy
これらはＪＩＳ Ｋ２２０７ｒ石油アスファルト」お
よび、日本道路協会規格「舗装用石油アスファルト」（
「舗装要綱−昭和６３年版」のＰ、２７参照）にその性
状、範囲が規格・表示されている（両者の記載内容はま
ったく同一である。）。These are "JIS K2207r petroleum asphalt" and the Japan Road Association standard "petroleum asphalt for paving" (
The characteristics and range are specified and indicated in the "Pavement Guidelines - 1986 Edition", page 27) (the contents of both are exactly the same).
なお規格にはないが、次の性質／性能はアスファルトに
とって重要である。Although not included in the standards, the following properties/performances are important for asphalt:
イ、 アスファルトは必ず加熱され、溶融されて使用さ
れる。その場合、加熱貯蔵
タンクあるいは溶解ガマの中などで。B. Asphalt must be heated and melted before use. In that case, in a heated storage tank or melting pot.
上層と下層で著しく性質が異なるもの、すなわち組成分
の分離（相分離）が生
じるものであっては好ましくない。It is not preferable that the upper layer and the lower layer have significantly different properties, that is, a layer that causes compositional separation (phase separation).
口、載荷時間の増大とともに、そのステイフネスは低下
し、載荷時間が短くなれ
ばスティフネスは大きくなる（温度−
定の場合）。As the loading time increases, the stiffness decreases, and as the loading time decreases, the stiffness increases (in the case of constant temperature).
スティフネスとは、一般の弾性体にお けるヤング率または弾性係数に相当す るもので、アスファルトおよびアスフ ァルト混合物の材料定数である。アス ファルトおよびアスファルト混合物の 性状は、温度と載荷時間によって影響 されるため、温度が低く載荷時間が短 いほどスティフネスは大きくなる。Stiffness is the characteristic of general elastic bodies. Young's modulus or elastic modulus Asphalt and asphalt is the material constant of the walt mixture. As of phalt and asphalt mixtures Properties are affected by temperature and loading time temperature and short loading time. The higher the stiffness, the greater the stiffness.
ハ、舗装という用途をめざしている限りは、骨材、フィ
ラーおよび顔料等と混合し
た加熱アスファルト混合物において、
実用上さしつかえないであろうと判断
されるだけの力学的強度や耐水性を発
揮しなければならない。C. As long as the intended use is paving, heated asphalt mixtures mixed with aggregates, fillers, pigments, etc. must exhibit mechanical strength and water resistance that are judged to be acceptable for practical use. It won't happen.
これらの評価試験とは舗装要綱Ｐ、１７０〜Ｐ、１７ｇ
の中に紹介されている以下の混合物力学試験である。These evaluation tests are pavement guidelines P, 170-P, 17g.
The following mixture mechanics tests are introduced in .
マーシャル試験 （６０℃で行う一種の圧縮試験
）で車輪を走行させる）
本発明は、前述の特定配合による組成物であって、この
組成物によって針入度４０〜１２０のストレートアスフ
ァルトの代替品であり。The present invention is a composition according to the above-mentioned specific formulation, which can be used as a substitute for straight asphalt with a penetration degree of 40 to 120. can be.
１、 Ｊ Ｉ Ｓ Ｋ２２０７規格、および道路協会
規格にすへて適合する。1. Fully compliant with JIS K2207 standards and Road Association standards.
２、加熱貯蔵中において相分離を生じない。2. No phase separation occurs during heat storage.
３、温度−粘度曲線やスティフネスー時間曲線はストレ
ートアスファルトとほとんど同じである。3. The temperature-viscosity curve and stiffness-time curve are almost the same as straight asphalt.
４、各種混合物力学試験の結果はストレートアスファル
トと同程度か、それ以上の好ましい結果を示す。4. The results of various mixture mechanics tests show that the results are comparable to or even better than straight asphalt.
という点で充分ストレートアスファルトの長所を備えて
いると、みることができる。In this respect, it can be seen as having all the advantages of straight asphalt.
本発明の組成物は、明色舗装（車道１歩道。The composition of the present invention is applied to light-colored pavement (roadway 1 sidewalk).
プレイグラウンド、飛行場、護岸、堤防、ダム等）、明
色歩行用ブロック（工場成型品等）、エマルジョン前駆
体（舗装用および各種工業用等）、低コスト明色接着剤
（例、封筒ノリ、）レキシブルガラス等）等として有用
である。playgrounds, airports, sea walls, embankments, dams, etc.), light-colored walking blocks (factory molded products, etc.), emulsion precursors (for pavements and various industrial uses, etc.), low-cost light-colored adhesives (e.g., envelope glue, ) is useful as flexible glass, etc.).
本発明で使用する（Ａ）、（Ｂ）、（Ｃ）。 (A), (B), (C) used in the present invention.
（Ｄ）の各成分はつぎのとおりである。Each component of (D) is as follows.
Ａ成分
昭和シェル石油■製 ”ＢＳ Ｅｘｔｒａｃｔ”芳香族
分１９重量％、ナフテン分２７重量％引火点２５４℃、
１００℃粘度５２ｃｓｔ出典：特公昭５８−１３０９８
号公報
「アスファルト改質用ゴム系添加剤」
（シェル石油ＫＫ出願）
Ｂ成分
三井石油化学■製 ″ベトロジン：ｔ１５０”芳香族系
石油樹脂
軟化点（環球式）１５０℃、比重１．０７Ｃ成分（熱可
塑性ゴム）
シェル化学■製 ”Ｃａｒｉｆｌｅｘ ＴＲｌｌ０Ｉ”
分子量１．７ Ｘ １０５、ポリスチレン量３０ｗｔ％
比重０．９４
Ｄ成分（ナフテン酸）
三共油化工業■製 “ＳＮＡ １８５”酸価１８７ （
ｍｇＫＯＭ ｇ ＞
引火点１６０℃
本発明における試験方法はつぎのとおりである。Component A "BS Extract" manufactured by Showa Shell Sekiyu■ Aromatic content 19% by weight, Naphthene content 27% by weight Flash point 254℃,
100℃ viscosity 52 cst Source: Tokuko Sho 58-13098
Publication "Rubber additive for asphalt modification" (Applied by Shell Sekiyu KK) Component B manufactured by Mitsui Petrochemicals "Vetrozin: t150" aromatic petroleum resin softening point (ring and ball system) 150℃, specific gravity 1.07C component ( Thermoplastic rubber) “Cariflex TRll0I” manufactured by Shell Kagaku ■
Molecular weight 1.7 x 105, polystyrene content 30wt%
Specific gravity 0.94 Component D (naphthenic acid) “SNA 185” manufactured by Sankyo Yuka Kogyo ■ Acid value 187 (
mgKOM g > flash point 160°C The test method in the present invention is as follows.
２、参考試験
・針入度指数、ＰＩ
針入度Ｐｅｎおよび軟化点ＴＲ＆Ｂから次式で計算され
る。2. Reference test - Penetration index, PI Calculated from the penetration Pen and softening point TR&B using the following formula.
アスファルト系材料の感温性を示す。Indicates the temperature sensitivity of asphalt-based materials.
＋側になるほど感温性が低くなり、 −側になるほど感温性が高くなる。The more it goes to the + side, the lower the temperature sensitivity becomes. The temperature sensitivity becomes higher as it goes to the − side.
出典（例）
土木材料アスファルト（井守出版）
Ｐ、３４〜３５
・６０℃粘度
アスファルト協会規格ＪＡＡ−００ト
フラース脆化点 Ｊ Ｉ Ｓ Ｋ２２０７・アスフ
ァルテン量
石油学会規格ＪＰＩ−５Ｓ −２２
・数平均分子量
・貯蔵安定性（又は加熱貯蔵安定性）
試料を入れた容器を高温で長期間（例１６０℃Ｘ５日間
）放置する。組成物の異なる成分が反発する（相溶性が
悪い）ときは、般に上層と下層に分離を生じるから、こ
れを検査すれば分離の程度（すなわち相溶性の良、不良
）がわかる。Source (example) Civil engineering material asphalt (Imori Publishing) P, 34-35 ・60℃ viscosity Asphalt Association standard JAA-00 Toffras embrittlement point JIS K2207 ・Asphaltene amount Petroleum Institute standard JPI-5S-22 ・Number average molecular weight・Storage Stability (or Heat Storage Stability) A container containing a sample is left at a high temperature for a long period of time (Example 160°C for 5 days). When different components of a composition repel each other (poor compatibility), separation generally occurs between the upper and lower layers, and by examining this, the degree of separation (that is, good or bad compatibility) can be determined.
この場合、
上層の軟化点−下層の軟化点＝軟化点変化（”Ｃ）であ
る。なお、針入度変化が１００に近いほど軟化点変化の
絶対値がＯに近いほど分離の少い組成物であると云うこ
とができる。In this case, the softening point of the upper layer - the softening point of the lower layer = softening point change ("C). In addition, the closer the penetration change is to 100, the closer the absolute value of the softening point change is to O, the less separation occurs in the composition. It can be said that it is a thing.
・スチフネス（ステイフネス）−前述のとおり、
・作業温度
舗装混合物を作るときの温度で、経験上甚今（アスファ
ルトと骨材を混合する）は、アスファルトの粘度が１８
０±２０ ｃＳｔのとき粒皿佐（混合物をローラー又は
ハンマーで締固める）は、
アスファルトの粘度が３００±３０ ｃｓｔのときであ
る。・Stiffness - As mentioned above, ・Working temperature At the temperature when making the pavement mixture, from experience (mixing asphalt and aggregate), the viscosity of asphalt is 18
When the asphalt viscosity is 300±30 cst, the asphalt viscosity is 300±30 cst.
３、舗装用混合物試験
・マーシャル安定度試験
舗装試験法便覧 ３−７−１法（Ｐ、５０６）又はＡ
ＳＴＭ Ｄ−１５５９
供試体（φ１０ａｎＸ高さ６．３５ｃｓ）を６０°Ｃの
水中に一定期間養生したのち取出して。3. Pavement mixture test/Marshall stability test Pavement test method manual 3-7-1 method (P, 506) or A
STM D-1559 specimen (φ10an x height 6.35cs) was cured in water at 60°C for a certain period of time and then taken out.
これを圧縮して試験する。This is compressed and tested.
・動的安定度ＤＳ
ホイールトラッキング試験（６０℃）で測定される一種
の安定度、車輪通過回数／ｍであられし、大きいほど、
わだち掘れに対する抵抗が大きい。・Dynamic stability DS A type of stability measured by wheel tracking test (60℃), the number of wheel passes/m, the larger the
Great resistance to rutting.
・ラベリングすりヘリ量
ラベリング試験（−１０°Ｃ）でチェーンでたたかれた
供試体のすりヘリ量を断面積（ａＪ）で示す。この値が
小さいほど低温でのたわみ性がすぐれているといわれる
。・Labeling edge amount The amount of abrasion edge of the specimen hit with a chain in the labeling test (-10°C) is shown in cross-sectional area (aJ). It is said that the smaller this value, the better the flexibility at low temperatures.
実施例Ｉ
Ｊ Ｉ Ｓ Ｋ２２０７ストレートアスフアルトおよ
び日本道路協会規格舗装用石油アスファルトの
グレード ４０〜６０
グレード ６０〜８０
グレード ８０〜１００
グレード １００〜１２０
に相当する代替品をつぎの組成により作成した。Example I Substitute products corresponding to grades 40-60, 60-80, 80-100, and 100-120 of JIS K2207 straight asphalt and Japan Road Association standard petroleum asphalt for paving were prepared with the following compositions.
（イ）グレード４０〜６０代替品
組成（イ）： Ａ：抽 出 油
Ｂ：樹 脂
Ｃ：熱可塑性ゴム
Ｄ＝ナフテン酸
５４．２ｗｔ％
４１．５ｗｔ％
０、ｋｔ％
３．５すｔ％
第１表
（ロ）
グレード６０〜８０代替品
組成（ロ）： Ａ：抽 出 油
Ｂ：樹 脂
Ｃ：熱可塑性ゴム
Ｄ：ナフテン酸
６０．５ｗｔ％
３４ 、５ｗｔ％
４ 、２ｔｉｔ％
０．８υｔ％
（ハ）グレード８０〜ｉｏｏ代替品
組成（ハ）： Ａ：抽 出 油
Ｂ：樹 脂
Ｃ：熱可塑性ゴム
Ｄ：ナフテン酸
６６．０ｗｔ％
２９．５％ｌｔ％
２．５ｗｔ％
２．０ｗｔ％
第２表
第３表
（ニ）グレード１００〜１２０代替品
Ｂ：樹 脂
Ｃ：熱可塑性ゴム
Ｄ：ナフテン酸
第４表
２５．５ｗｔ％
４．５υｔ％
０．５ｗｔ％
実施例２
実用上よく用いられる石油アスファルト６０〜８０と８
０〜１００およびそれらに対応する実施例１の組成（ロ
）、組成（ハ）、市販類似品Ａ、Ｈについて規格試験、
参考試験、混合物試験を行い、その結果を第５表および
第１図〔スチフネス−時間曲線・Ｓ−を線図（温度１５
℃）〕に示す。(A) Grade 40-60 substitute composition (A): A: Extracted oil B: Resin C: Thermoplastic rubber D = Naphthenic acid 54.2wt% 41.5wt% 0, kt% 3.5st% Table 1 (b) Grade 60-80 substitute product composition (b): A: Extracted oil B: Resin C: Thermoplastic rubber D: Naphthenic acid 60.5wt% 34, 5wt% 4, 2tit% 0.8υt % (c) Grade 80 to ioo substitute composition (c): A: Extracted oil B: Resin C: Thermoplastic rubber D: Naphthenic acid 66.0wt% 29.5%lt% 2.5wt% 2.0wt % Table 2 Table 3 (d) Grade 100-120 Substitute B: Resin C: Thermoplastic rubber D: Naphthenic acid Table 4 25.5wt% 4.5υt% 0.5wt% Example 2 Good in practical use Petroleum asphalt used 60-80 and 8
0 to 100 and the corresponding composition (b) and composition (c) of Example 1, standard tests for commercially available similar products A and H,
A reference test and a mixture test were conducted, and the results are shown in Table 5 and Figure 1 [Stiffness-Time Curve/S-Diagram (Temperature 15
°C)].
通常の石油アスファルトの規格値、経験値カーらみて、
はずれている値あるいは問題である値番こついて本印で
示した。Considering the standard values and empirical values of ordinary petroleum asphalt,
Values that are out of place or problematic value numbers are indicated with a real seal.
（以下余白）
〔考 察〕
１）本発明組成物は該当する石油アスファルトにきわめ
て近い（−船釣性状および温度粘度関係）。(The following is a blank space) [Discussion] 1) The composition of the present invention is extremely close to the corresponding petroleum asphalt (-shipping properties and temperature-viscosity relationship).
２）特に加熱貯蔵中の分離がみられない。2) No separation is observed especially during heating storage.
３）スチフネス−時間の関係を示すいわゆる「レオロジ
ー性状」も石油アスファルトによく似かよっている（第
１図参照）。3) The so-called "rheological properties" indicating the relationship between stiffness and time are also very similar to petroleum asphalt (see Figure 1).
４）舗装混合物としての性状も高温耐流動性（６０℃）
において石油アスファルトと同程度以上。4) Properties as a pavement mixture also have high temperature flow resistance (60℃)
The same level or higher than that of petroleum asphalt.
また低温たわみ性（−１０℃）において石油アスファル
トよりかなりすぐれているという結果を示した。Furthermore, the results showed that it was considerably superior to petroleum asphalt in low-temperature flexibility (-10°C).
更に耐水性（６０℃×１４日間水中）においてもストレ
ートアスファルトと同程度以上の結果となった。Furthermore, the water resistance (submerged in water at 60°C for 14 days) was at least as good as that of straight asphalt.
５）市販品はさまざまな点で問題があり、良かったのは
低温たわみ性（−１０℃）くらいなものであった。とり
わけ耐水性が非常に悪い。5) Commercially available products had problems in various respects, and the only good ones were low-temperature flexibility (-10°C). Especially the water resistance is very poor.
実施例３
実施例１組成（ロ）を５．５ｗｔ％含有させた舗装用ア
スファルト混合物〔密粒度アスコン（１３）、空隙率４
％前後〕で直径Ｌｏａｎ、高さ６．３５ｃｍの締固め供
試体を作り、これを屋外の日なた箇所におかれた水を見
たした水槽の内部および近傍に静置して３年間観測した
。Example 3 Paving asphalt mixture containing 5.5 wt% of Example 1 composition (b) [Dense particle size Ascon (13), porosity 4
Compacted specimens with diameter Loan and height 6.35 cm were made with a diameter of 6.35 cm, and they were placed in or near a water tank placed outdoors in the sun and observed for 3 years. did.
水の中および外におかれた供試体のどちらも特に外観、
形状の変化はなく全く問題点は発見できなかった。Specimens placed both in and out of water are particularly sensitive to external appearance.
There was no change in shape and no problems were found.
（実験期間 １９８７年７月２６日
〜１９９０年７月２５日）
果〕
１、組成からも理解されるようにアスファルトン（アス
ファルト中のｎ−へブタン不溶解分で、分子量１０００
〜ｉｏｏ、ｏｏｏ）の黒色固体を含有していないのでき
わめて透明度高＜、シたがって
（イ）そのまま骨材と混合すると、骨材の色あいがほと
んどそのままでてくるので、〔効
いわゆる自然色舗装が得られる。(Experiment period: July 26, 1987 to July 25, 1990) Results: 1. As understood from the composition, asphaltone (the n-hebutane insoluble portion of asphalt, with a molecular weight of 1000
Since it does not contain any black solids (ioo, ooo), it has extremely high transparency. (a) If you mix it with aggregate as it is, the color of the aggregate will remain almost as it is, so it is possible to create the so-called natural color pavement. is obtained.
（ロ）少量の顔料を用いることによって明るいあざやか
な色彩の舗装が得られる。(b) By using small amounts of pigments, bright and vividly colored pavements can be obtained.
（ハ）ストレートアスファルトとまったく変わらない性
状／性能を示すため車道に
用いることができる（車道の明色化）。(c) It can be used for roadways because it exhibits properties and performance that are completely the same as straight asphalt (lightening of roadways).
Ｃ二）従来ストレートアスファルトによって実施されて
きた舗装箇所ならばすべて
本発明組成物によって明色／着色化す
ることが可能である。C2) All paved areas that have conventionally been done with straight asphalt can be lightened/colored with the composition of the present invention.
例、車道、歩道、プレイグラウンド、
飛行場、護岸、堤防、ダム
（ホ）明るい色彩が得られることによって多くの場合、
太陽熱を吸収せず、少くと
も約５℃は舗装体温度を低くさせる。Examples: roadways, sidewalks, playgrounds, airfields, seawalls, levees, dams (e) Bright colors often result in
It does not absorb solar heat and lowers the pavement temperature by at least about 5°C.
そのため従来問題であったアスファル ト舗装の高温での流動現象を非常に低 減できる。Therefore, asphalt, which was a problem in the past, Extremely low flow phenomena at high temperatures on road pavement. It can be reduced.
などの効果が発揮できる。Effects such as this can be achieved.
２、本発明組成物は、構成成分の種類および割合の双方
においてバランスがとれているので加熱貯蔵中に分離す
ることがない（石油アスファルトなみの相安定性を示す
）。2. Since the composition of the present invention is well-balanced in both the types and proportions of the constituent components, it does not separate during heated storage (it exhibits phase stability comparable to that of petroleum asphalt).
３、本発明の組成物は、スチフネス−時間の関係におい
て同一グレードの石油アスファルトのそれとほとんど変
らないカーブを示す。すなわちレオロジー的にも石油ア
スファルトときわめて類似した性質を示している。3. The composition of the present invention exhibits a stiffness-time curve that is almost unchanged from that of petroleum asphalt of the same grade. In other words, rheologically, it exhibits properties extremely similar to petroleum asphalt.
４、舗装混合物としての性状をみると、高温での耐流動
性をみるマーシャル安定度試験（６０℃、水中）、ホイ
ールトラッキング試験（６０℃、重交通条件下）におい
てはストレートアスファルトと同等程度以上の値を示し
ている。4. Looking at the properties as a pavement mixture, it is equivalent to or better than straight asphalt in the Marshall stability test (60°C, underwater), which measures flow resistance at high temperatures, and the wheel tracking test (60°C, under heavy traffic conditions). shows the value of
また、低温での耐キレッ性（たわみ性）をみるラベリン
グ試験においてはストレートアスファルトより概してす
ぐれた値を示した。In addition, in labeling tests to check sharpness resistance (flexibility) at low temperatures, it generally showed better values than straight asphalt.
５、 とくにこの種の結合材は耐水性が問題であるが、
本発明組成物は６０℃×１４日間のマーシャル安定度や
屋外水中３年間の浸漬試験で良好な結果を示しているこ
とを確認した。5. Water resistance is a particular problem with this type of binding material, but
It was confirmed that the composition of the present invention showed good results in Marshall stability at 60° C. for 14 days and immersion test in outdoor water for 3 years.
６゜ アニオン乳剤、 カチオン乳剤。6゜ anionic emulsion, Cationic emulsion.
非イオン型 乳剤いずれを問わず水中油滴型（０／ｗｔｙｐｅ） の乳剤が簡単に製造できる （非常に乳化しゃ すい） ４、Non-ionic type Oil-in-water type (0/w type) regardless of emulsion emulsions can be easily produced. (very emulsified) water) 4,
第１図は、 スチフネス−時間曲線を （温度１５ ℃） 示す。 Figure 1 shows Stiffness-time curve (Temperature 15 ℃) show.
Claims (1)
石油系、石炭系約２５〜４５重量％ および／または天然系樹脂 （Ｃ）熱可塑性ゴム約０．５〜５重量％ （Ｄ）ナフテン酸約０．３〜４重量％ よりなるアスファルト代替用組成物。[Claims] 1. (A) Approximately 50 to 70% by weight of petroleum solvent extracted oil (B)
An asphalt substitute composition comprising approximately 25 to 45% by weight of petroleum-based or coal-based and/or natural resin (C) approximately 0.5 to 5% by weight of thermoplastic rubber (D) approximately 0.3 to 4% by weight of naphthenic acid. thing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21845990A JP2983590B2 (en) | 1990-08-20 | 1990-08-20 | Asphalt replacement composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21845990A JP2983590B2 (en) | 1990-08-20 | 1990-08-20 | Asphalt replacement composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04100862A true JPH04100862A (en) | 1992-04-02 |
| JP2983590B2 JP2983590B2 (en) | 1999-11-29 |
Family
ID=16720237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21845990A Expired - Lifetime JP2983590B2 (en) | 1990-08-20 | 1990-08-20 | Asphalt replacement composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2983590B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157917A (en) * | 1992-11-20 | 1994-06-07 | Nisshin Kasei Kk | Binder composition for colored pavement |
| ES2112754A1 (en) * | 1995-05-05 | 1998-04-01 | Bituminosos S A Probisa Prod | Process for manufacturing synthetic binders for paving in colour by means of hot and cold technology |
| KR20010067657A (en) * | 2001-03-02 | 2001-07-13 | 최명부 | The process of manufacturing the dehydrating agent for paving asphalt |
| CN102391612A (en) * | 2011-10-20 | 2012-03-28 | 河南万里路桥集团有限公司 | Anionic aqueous colorized road surface crack sealing material and preparation process thereof |
| WO2012104427A1 (en) * | 2011-02-03 | 2012-08-09 | Eurovia | Concrete sealing system |
| CN102851502A (en) * | 2012-04-26 | 2013-01-02 | 广州有色金属研究院 | Method for extracting and separating beryllium |
| CN103554933A (en) * | 2013-10-21 | 2014-02-05 | 长安大学 | High adhesion prime coat oil for cement stabilized macadam base and preparation method of high adhesion prime coat oil |
| CN114920486A (en) * | 2022-04-26 | 2022-08-19 | 山东英朗路桥工程股份有限公司 | Cold-patch agent and application method thereof in cold-patch mixture |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003639B (en) * | 2017-12-11 | 2020-11-20 | 江苏理想环球新材料有限公司 | Maintenance construction method for asphalt pavement cementation wearing course |
-
1990
- 1990-08-20 JP JP21845990A patent/JP2983590B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157917A (en) * | 1992-11-20 | 1994-06-07 | Nisshin Kasei Kk | Binder composition for colored pavement |
| JPH0726029B2 (en) * | 1992-11-20 | 1995-03-22 | 日進化成株式会社 | Binder composition for colored pavement |
| ES2112754A1 (en) * | 1995-05-05 | 1998-04-01 | Bituminosos S A Probisa Prod | Process for manufacturing synthetic binders for paving in colour by means of hot and cold technology |
| KR20010067657A (en) * | 2001-03-02 | 2001-07-13 | 최명부 | The process of manufacturing the dehydrating agent for paving asphalt |
| WO2012104427A1 (en) * | 2011-02-03 | 2012-08-09 | Eurovia | Concrete sealing system |
| FR2971270A1 (en) * | 2011-02-03 | 2012-08-10 | Eurovia | CONCRETE SEALING SYSTEM |
| FR2971269A1 (en) * | 2011-02-03 | 2012-08-10 | Eurovia | CONCRETE SEALING SYSTEM |
| CN102391612A (en) * | 2011-10-20 | 2012-03-28 | 河南万里路桥集团有限公司 | Anionic aqueous colorized road surface crack sealing material and preparation process thereof |
| CN102851502A (en) * | 2012-04-26 | 2013-01-02 | 广州有色金属研究院 | Method for extracting and separating beryllium |
| CN103554933A (en) * | 2013-10-21 | 2014-02-05 | 长安大学 | High adhesion prime coat oil for cement stabilized macadam base and preparation method of high adhesion prime coat oil |
| CN114920486A (en) * | 2022-04-26 | 2022-08-19 | 山东英朗路桥工程股份有限公司 | Cold-patch agent and application method thereof in cold-patch mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2983590B2 (en) | 1999-11-29 |
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