JPH05280011A - Method of fixing sand in pavement process - Google Patents
Method of fixing sand in pavement processInfo
- Publication number
- JPH05280011A JPH05280011A JP10239692A JP10239692A JPH05280011A JP H05280011 A JPH05280011 A JP H05280011A JP 10239692 A JP10239692 A JP 10239692A JP 10239692 A JP10239692 A JP 10239692A JP H05280011 A JPH05280011 A JP H05280011A
- Authority
- JP
- Japan
- Prior art keywords
- sand
- water
- parts
- prepolymer
- compound
- 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
- 239000004576 sand Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 14
- 238000005507 spraying Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- -1 isocyanate compound Chemical class 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 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
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C5/00—Pavings made of prefabricated single units
- E01C5/003—Pavings made of prefabricated single units characterised by material or composition used for beds or joints; characterised by the way of laying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C3/00—Foundations for pavings
- E01C3/003—Foundations for pavings characterised by material or composition used, e.g. waste or recycled material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Architecture (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Road Paving Structures (AREA)
- Polyurethanes Or Polyureas (AREA)
- Road Repair (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、舗装工事における砂の
固定方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for fixing sand in pavement work.
【0002】[0002]
【従来の技術】各種の舗装工事において、舗装面にイン
ターロッキングブロック、カラー平板または石材等の敷
材を敷設する場合、これらの敷材が敷設後、外力により
破壊されることが無いように、敷材の下層地盤に敷砂を
施したり、敷材の目地に目地砂を施こしたりして、上下
方向または水平方向のクッション材としている。しかし
ながら、砂にはこれ自体に粘着性が無い。したがって単
に下層地盤や目地に砂を撒いただけでは降雨、振動また
は風等の要因により砂が流失または移動してクッション
性が失われ、またその他の不都合が生じる。この問題を
具体例をもって説明すると、下記のようなものがある。 (具体例1)舗装面に10度以上の勾配がある場合、強
度2500mm/hr以上の降雨があると水流により敷
砂および目地砂が流されてクッション性が失われる。 (具体例2)舗装面が交通量の多い車道または大型車両
の通行するコンテナヤードである場合、振動により敷砂
および目地砂が移動してクッション性が失われる。 (具体例3)舗装面が商店街に面している場合、風によ
り目地砂が店内に舞い込んで店内の陳列商品を汚損す
る。 (具体例4)舗装面がプールサイドである場合、洗浄水
により目地砂が洗い出されて裸足による歩行に支障を来
し、また目地砂がプールの中に流れ込む虞がある。2. Description of the Related Art In laying interlocking blocks, colored flat plates, or stones on a pavement surface in various types of pavement work, such laying materials should not be destroyed by external force after laying. The lower layer ground of the floor covering is covered with sand or the joints of the floor covering are covered with joint sand to form a vertical or horizontal cushioning material. However, sand itself is not tacky. Therefore, if sand is simply sprinkled on the lower ground or joints, the sand may be washed away or moved due to factors such as rainfall, vibration or wind, and the cushioning property may be lost, and other inconvenience may occur. This problem will be described below with a specific example. (Specific Example 1) When the pavement surface has a gradient of 10 degrees or more, if there is rainfall with a strength of 2500 mm / hr or more, the flow sand causes the bed sand and the joint sand to be washed away, and the cushioning property is lost. (Specific Example 2) When the pavement surface is a road with a large amount of traffic or a container yard through which large vehicles pass, the cushioning property is lost due to the movement of the set sand and joint sand. (Specific Example 3) When the pavement surface faces the shopping street, the joint sand is blown into the store by the wind and the displayed products in the store are contaminated. (Specific Example 4) When the paved surface is poolside, the joint water may be washed out by the cleaning water, which may hinder walking with bare feet, and the joint sand may flow into the pool.
【0003】これらの問題に対処するため、従来は、や
むを得ず砂にセメントを混入して砂を固定している。ま
た敷砂については砂を上下2層の織布の間に挾み込んで
固定する方法がある。しかしながら前者の方法には、セ
メントの混入により砂を用いた本来の理由であるクッシ
ョン性が失われてしまう問題があり、またこの方法を目
地砂に用いた場合には敷材の表面を汚して美観を損なう
虞がある。また後者の方法には、これを目地砂に利用す
ることができない問題がある。In order to deal with these problems, conventionally, unavoidably, cement is mixed into sand to fix the sand. As for the spread sand, there is a method in which the sand is sandwiched between two upper and lower woven fabrics and fixed. However, the former method has a problem in that the cushioning property which is the original reason for using sand is lost due to the mixing of cement, and when this method is used for joint sand, the surface of the flooring material is soiled. There is a risk of spoiling the aesthetics. In addition, the latter method has a problem that it cannot be used as joint sand.
【0004】[0004]
【発明が解決しようとする課題】本発明は以上の点に鑑
み、敷砂または目地砂を、これらによるクッション性を
維持した状態で固定する舗装工事における砂の固定方法
を提供することを目的とする。SUMMARY OF THE INVENTION In view of the above points, the present invention has an object to provide a method for fixing sand in paving work for fixing the spread sand or the joint sand in a state where the cushioning property thereof is maintained. To do.
【0005】[0005]
【課題を解決するための手段】上記目的を達成するた
め、本発明の固定方法は、1末端に2個以上のヒドロキ
シル基を有し、分子量1,000〜20,000のポリ
オキシアルキレン鎖を有する化合物と、そのヒドロキシ
ル基数と同モル以上のポリイソシアネート化合物とを反
応させて得られる水溶性プレポリマーを水に3.0〜
7.0%の濃度で均一に溶解せしめたものを、敷砂また
は目地砂に散布して樹脂化層を形成することを特徴とす
る。In order to achieve the above object, the immobilization method of the present invention comprises a polyoxyalkylene chain having two or more hydroxyl groups at one end and having a molecular weight of 1,000 to 20,000. The water-soluble prepolymer obtained by reacting the compound having with a polyisocyanate compound having the same or more moles as the number of hydroxyl groups is added to water in an amount of 3.0 to
What was made to melt | dissolve uniformly at the density | concentration of 7.0% is sprayed on the spread sand or the joint sand, and it is characterized by forming a resin-ized layer.
【0006】[0006]
【作用】本発明の固定方法は、上記組成の水溶性プレポ
リマーを主材とする散布材を敷砂または目地砂に散布し
て砂をクッション性を持たせた状態で固定する。散布材
はイソシアネート化合物よりなる水溶性プレポリマーを
水和重合反応によりゴム状化する如く製造したものであ
り、水溶性プレポリマーを水に均一に溶解させて散布材
とし、この散布材を砂に散布して、砂の表面にその水和
重合反応によるゴム状の樹脂化被膜を形成する。またそ
の水溶性による粘性の低下を利用して砂に浸透させ、砂
の表面から或る程度の深さ迄の層を構成する砂粒子を固
化させてゴム状の樹脂化層を形成する。上記水溶性プレ
ポリマーは水和重合反応により砂粒子と強力に付着す
る。したがって砂の流失または移動に対して大きな抵抗
力を発揮する。また形成された樹脂化層は水溶性プレポ
リマーの水和重合反応時に発泡を伴い、この発泡が独立
気泡であって断熱性を有しているために、霜柱や凍上を
効果的に防止する。上記水溶性プレポリマーは任意の水
に溶解して均一な濃度の溶液となる。水和重合反応は通
常、5〜30分程度の時間で調製される。このとき過剰
な水は全て固結体の中に包合される。上記水溶性プレポ
リマーの本発明における可使濃度は、プレポリマー固形
分で3.0〜7.0%であり、この濃度を調整すること
により任意の強度を得ることができる。濃度が2.0%
以下の場合は固結しないが、3.0〜7.0%の範囲内
であるとゴム状の樹脂化皮膜および樹脂化層が形成され
る。樹脂化皮膜および樹脂化層は雨水を吸って膨潤す
る。濃度が7.0%を越えると粘度が高過ぎて均一な散
布が困難になる。According to the fixing method of the present invention, a sprinkling material mainly composed of the water-soluble prepolymer having the above-mentioned composition is sprinkled on the spread sand or the joint sand, and the sand is fixed in a cushioned state. The spraying material is produced by making a water-soluble prepolymer composed of an isocyanate compound into a rubber by a hydration polymerization reaction.The water-soluble prepolymer is uniformly dissolved in water to give a spraying material, and the spraying material is applied to sand. By spraying, a rubber-like resinized film is formed on the surface of the sand by the hydration polymerization reaction. Further, the decrease in viscosity due to the water solubility is used to penetrate the sand to solidify the sand particles forming a layer from the surface of the sand to a certain depth to form a rubber-like resin layer. The water-soluble prepolymer strongly adheres to the sand particles by the hydration polymerization reaction. Therefore, a great resistance is exerted against the loss or movement of sand. In addition, the formed resin layer accompanies foaming during the hydration polymerization reaction of the water-soluble prepolymer, and since the foaming is closed cells and has a heat insulating property, frost columns and frost heave are effectively prevented. The water-soluble prepolymer is dissolved in any water to form a solution having a uniform concentration. The hydration polymerization reaction is usually prepared in about 5 to 30 minutes. At this time, all excess water is included in the solidified body. The usable concentration of the water-soluble prepolymer in the present invention is 3.0 to 7.0% in terms of the solid content of the prepolymer, and any strength can be obtained by adjusting this concentration. Concentration is 2.0%
In the following cases, it does not solidify, but within the range of 3.0 to 7.0%, a rubber-like resinized film and resinized layer are formed. The resinized film and the resinized layer absorb rainwater and swell. If the concentration exceeds 7.0%, the viscosity becomes too high, and it becomes difficult to uniformly spray.
【0007】本発明の実施に用いる水溶性プレポリマー
は、末端に2個以上のヒドロキシル基を有し、分子量
1,000〜20,000のポリアルキレン鎖を有する
化合物(以下、ポリアルキレンオキサイド化合物と称す
る)と、そのビドロキシル基数と同モル数以上のポリイ
ソシアネート化合物とを、30〜120℃、30分〜7
日間、必要に応じてジプチルチンジラワレートまたはト
リエチレンジアミンの如き触媒を使用して反応させ、ポ
リアルキレンオキサイド化合物の両端にイソシアネート
基を導入することにより得られる。水溶性プレポリマー
は、常温で液状またはペースト状である。水溶性プレポ
リマーを水に添加してから固結するまでの時間は、アミ
ン化合物の如き塩基性物質を加えることにより早くさ
せ、酸クロライド化合物の如き酸性物質を加えることに
より遅くすることが可能である。The water-soluble prepolymer used in the practice of the present invention has a compound having two or more hydroxyl groups at the end and a polyalkylene chain having a molecular weight of 1,000 to 20,000 (hereinafter referred to as a polyalkylene oxide compound). And a polyisocyanate compound having the same number of moles or more as the number of vidroxyl groups, at 30 to 120 ° C. for 30 minutes to 7
It is obtained by introducing a isocyanate group at both ends of a polyalkylene oxide compound by reacting for a day with a catalyst such as diptyltin dilaurate or triethylenediamine, if necessary. The water-soluble prepolymer is liquid or paste at room temperature. The time from the addition of the water-soluble prepolymer to water to the solidification can be accelerated by adding a basic substance such as an amine compound and delayed by adding an acidic substance such as an acid chloride compound. is there.
【0008】本発明において使用するポリアルキレンオ
キサイド化合物とは、活性水素を有する化合物にアルキ
レンオキサイドを長鎖状に付加反応させて得られる末端
に2個以上のヒドロキシル基を有する化合物である。活
性水素を有する化合物には、エチレングリコール、グリ
セリン、トリメチロールプロパン、トリメチロールエタ
ン、ペンタエリスリトール、ソルビトール、シユークロ
ーズ、メチルグルコシドの如きポリオール類、エチレン
ジアミン、ジエチレントリアミン、メチルアミンの如き
アミン類、トール油、ロジン酸、アジピン酸、ヒマシ油
の如きカルポン酸やエステル類、およびアルデヒドと他
の化合物(例えばオレフイン、芳香性炭化水素等)の反
応により得られる2個以上のヒドロキシル基を有する化
合物等がある。これらの活性水素を有する化合物に対し
て、主としてエチレンオキサイド、従として他のアルキ
レンオキサイドを付加反応させて得られる化合物、また
はこれらの混合物は優れた水溶性を示す。ポリイソシア
ネート化合物との反応により得られるプレポリマーは水
溶性および水溶液の粘度の点で、プレポリマー水溶液を
土壌に散布するに際して、目的地層域への浸透性を損な
わない程度の長さのポリアルキレンオキサイド鎖を持つ
範囲が望ましく、あるいは分散剤、可溶化剤等を添加す
ることにより、同様の浸透性を附与することが可能であ
る範囲のポリアルキレンオキサイド鎖および分子量範囲
を取る必要がある。したがってポリオールの分子量とし
ては、ポリエチレングリコールの場合、分子量1,00
0〜20,000、望ましくは1,000〜4,000
の範囲が適当である。他のポリアルキレンオキサイド化
合物においても略同様である。本発明において、プレポ
リマーの合成における反応割合はポリアルキレンオキサ
イド化合物1モル(重量)に対して、ポリイソシアネー
ト化合物2〜8モル(重量)であるが、この割合はポリ
アルキレンオキサイド化合物分子中のヒドロキシル基の
数個により選択される。濃度は、反応の結果得られるプ
レポリマーの分子量の大きさが水溶液の粘度をを著しく
高めず、かつ水溶性を妨げない範囲で決定される。本発
明において使用するポリイソシアネート化合物とは、有
機化合物を母体とする2個以上のイソシアネート基を有
する化合物であり、例えば、トリレンジイソシアネー
ト、ジフエニルメタンジイソシアネート、ジフエニルジ
イソシアネート、ナフタリンジイソシアネート、キシリ
レンジイソシアネート、ヘキサメチレンジイソシアネー
ト等の如きジイソシアネート化合物、トリフエニルメタ
ントリイソシアネート等の如きトリイソシアネート化合
物である。また、本発明において使用するアルキレンオ
キサイド類には、エチレンオキサイド、プロピレンオキ
サイド、プチレンオキサイド、スチレンオキサイドおよ
びエピクロールヒドリン等がある。The polyalkylene oxide compound used in the present invention is a compound having two or more hydroxyl groups at the terminal, which is obtained by adding a long chain of alkylene oxide to a compound having active hydrogen. Compounds having active hydrogen include ethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose, polyols such as methylglucoside, amines such as ethylenediamine, diethylenetriamine and methylamine, tall oil. , Rosin acid, adipic acid, carponic acid and esters such as castor oil, and compounds having two or more hydroxyl groups obtained by the reaction of aldehyde with other compounds (eg, olefin, aromatic hydrocarbon, etc.) . A compound obtained by mainly addition-reacting ethylene oxide, and secondarily another alkylene oxide, or a mixture thereof with these compounds having active hydrogen shows excellent water solubility. The prepolymer obtained by the reaction with the polyisocyanate compound has a water solubility and a viscosity of the aqueous solution, and when the prepolymer aqueous solution is sprayed on the soil, the polyalkylene oxide has such a length as not to impair the permeability to the destination layer area. A range having a chain is preferable, or it is necessary to take a polyalkylene oxide chain and a molecular weight range of a range capable of imparting similar penetrability by adding a dispersant, a solubilizing agent and the like. Therefore, as for the molecular weight of the polyol, in the case of polyethylene glycol, the molecular weight is 100
0 to 20,000, preferably 1,000 to 4,000
The range is appropriate. The same applies to other polyalkylene oxide compounds. In the present invention, the reaction ratio in the synthesis of the prepolymer is 2 to 8 mol (weight) of the polyisocyanate compound with respect to 1 mol (weight) of the polyalkylene oxide compound. Selected by several groups. The concentration is determined in such a range that the molecular weight of the prepolymer obtained as a result of the reaction does not significantly increase the viscosity of the aqueous solution and does not hinder the water solubility. The polyisocyanate compound used in the present invention is a compound having two or more isocyanate groups having an organic compound as a base, and examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate and xylylene diisocyanate. , A diisocyanate compound such as hexamethylene diisocyanate, and a triisocyanate compound such as triphenylmethane triisocyanate. The alkylene oxides used in the present invention include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and epichlorhydrin.
【0009】[0009]
【実施例】先ず、水溶性プレポリマーの合成例を説明す
る。 (合成例1)平均分子量3,000のエチレンオキサイ
ド/プロピレンオキサイドの重量比が85/15の共重
合体ジオール200部とトリレンジイソシアネート5
2.2部を90℃で3時間反応させて水溶性プレポリマ
ーを得た。この水溶性プレポリマーは室温で液状であ
り、また密封状態では経時変化の少ない安定な化合物で
ある。 (合成例2)平均分子量1,000のポリオキシエチレ
ングリコール694部とトリレンジイソシアネート30
6部とを90℃で2時間反応させて水溶性プレポリマー
を得た。 (合成例3)平均分子量2,000のポリオキシエチレ
ングリコール780部とキシレンジイソシアネート22
0部とを90℃で2時間半反応させて水溶性プレポリマ
ーを得た。 (合成例4)平均分子量2,000のポリオキシエチレ
ングリコール748部とヘキサメチレンジイソシアネー
ト252部とを70℃で5時間反応させて水溶性プレポ
リマーを得た。EXAMPLES First, a synthesis example of a water-soluble prepolymer will be described. (Synthesis Example 1) 200 parts of a copolymer diol having an average molecular weight of 3,000 and a weight ratio of ethylene oxide / propylene oxide of 85/15 and tolylene diisocyanate 5
2.2 parts were reacted at 90 ° C. for 3 hours to obtain a water-soluble prepolymer. This water-soluble prepolymer is a stable compound which is liquid at room temperature and has little change with time in a sealed state. (Synthesis example 2) 694 parts of polyoxyethylene glycol having an average molecular weight of 1,000 and tolylene diisocyanate 30
6 parts were reacted at 90 ° C. for 2 hours to obtain a water-soluble prepolymer. (Synthesis Example 3) 780 parts of polyoxyethylene glycol having an average molecular weight of 2,000 and xylene diisocyanate 22
0 part was reacted at 90 ° C. for 2 hours and 30 minutes to obtain a water-soluble prepolymer. (Synthesis Example 4) A water-soluble prepolymer was obtained by reacting 748 parts of polyoxyethylene glycol having an average molecular weight of 2,000 with 252 parts of hexamethylene diisocyanate at 70 ° C for 5 hours.
【0010】(合成例5)グリセリンにチレンオキサイ
ドとプロピレンオキサイドとを35モル:6モルの割合
で付加反応させて得られた平均分子量2,000の共重
合体ポリオール740部とトリレンジイソシアネート2
60部とを90℃で2時間反応させて水溶性プレポリマ
ーを得た。 (合成例6)平均分子量4,000のポリオキシエチレ
ングリコール822部とトリレンジイソシアネート17
8部とを90℃で3時間反応させて水溶性プレポリマー
を得た。 (合成例7)エチレングルコールにエチレンオキサイド
とプロピレンオキサイドとを72モル:14モルの割合
で付加反応させて得られた平均分子量4,000の共重
合体ポリオール843部とキシレンジイソシアネート1
57部とを70℃で3時間反応させて水溶液性プレポリ
マーを得た。 (合成例8)グリセリンにエチレンオキサイドとプロピ
レンオキダイドとを126モル:41モルの割合で付加
反応させて得られた平均分子量8,000の共重合体ポ
リオール889部とヘキサメチレンジイソシアネート1
11部とを70℃で5時間反応させて水溶性プレポリマ
ーを得た。(Synthesis Example 5) 740 parts of a copolymer polyol having an average molecular weight of 2,000 obtained by addition reaction of glycerin with thylene oxide and propylene oxide at a ratio of 35 mol: 6 mol and tolylene diisocyanate 2
A water-soluble prepolymer was obtained by reacting 60 parts with 90 ° C. for 2 hours. (Synthesis Example 6) 822 parts of polyoxyethylene glycol having an average molecular weight of 4,000 and tolylene diisocyanate 17
A water-soluble prepolymer was obtained by reacting 8 parts with 90 ° C. for 3 hours. (Synthesis Example 7) 843 parts of a copolymer polyol having an average molecular weight of 4,000 obtained by addition reaction of ethylene oxide and propylene oxide with ethylene glycol at a ratio of 72 mol: 14 mol and xylene diisocyanate 1
57 parts was reacted at 70 ° C. for 3 hours to obtain an aqueous prepolymer. (Synthesis Example 8) 889 parts of a copolymer polyol having an average molecular weight of 8,000 obtained by addition-reacting glycerin with ethylene oxide and propylene oxidide at a ratio of 126 mol: 41 mol and hexamethylene diisocyanate 1
A water-soluble prepolymer was obtained by reacting 11 parts with 70 ° C. for 5 hours.
【0011】(合成例9)エチレングルコールにエチレ
ンオキサイドとプロピレンオキサイドとを240モル:
77モルの割合で付加反応させて得られた平均分子量1
5,000の共重合体ポリオール925部とトリレンジ
イソシアネート75部とを90℃で4時間反応させて水
溶液性プレポリマーを得た。 (合成例10)ソルビトールにエチレンオキサイドとプ
ロピレンオキサイドとを77モル:10モルの割合で付
加反応させて得られた平均分子量4,000の共重合体
ポリオール657部とキシレンジイソシアネート343
部とを90℃で3時間反応させて水溶液性プレポリマー
を得た。 (合成例11)ソルビトールにエチレンオキサイドとプ
ロピレンオキサイドとを110モル:20モルの割合で
付加反応させて得られた平均分子量6,000の共重合
体ポリオール754部とヘキサメチレンジイソシアネー
ト246部とを70℃で6時間反応させて水溶液性プレ
ポリマーを得た。 (合成例12)平均分子量4,000のヒマシ油エチレ
ンオキサイド付加物800部とトリレンジイソシアネー
ト200部とを90℃で4時間反応させて水溶性プレポ
リマーを得た。(Synthesis Example 9) 240 mol of ethylene oxide and propylene oxide in ethylene glycol:
Average molecular weight 1 obtained by addition reaction at a ratio of 77 mol
925 parts of 5,000 copolymer polyols and 75 parts of tolylene diisocyanate were reacted at 90 ° C. for 4 hours to obtain an aqueous prepolymer. (Synthesis Example 10) 657 parts of a copolymer polyol having an average molecular weight of 4,000 obtained by addition-reacting sorbitol with ethylene oxide and propylene oxide at a ratio of 77 mol: 10 mol, and xylene diisocyanate 343.
This was reacted with 90 parts at 90 ° C. for 3 hours to obtain an aqueous prepolymer. (Synthesis Example 11) 70 parts of 754 parts of a copolymer polyol having an average molecular weight of 6,000 and 246 parts of hexamethylene diisocyanate obtained by addition-reacting sorbitol with ethylene oxide and propylene oxide at a ratio of 110 mol: 20 mol. An aqueous prepolymer was obtained by reacting at 6 ° C for 6 hours. (Synthesis Example 12) 800 parts of a castor oil ethylene oxide adduct having an average molecular weight of 4,000 and 200 parts of tolylene diisocyanate were reacted at 90 ° C. for 4 hours to obtain a water-soluble prepolymer.
【0012】つぎに上記具体例にしたがって実施例を説
明する。 (具体例1への対応)勾配20度の斜面に敷砂を厚さ3
cmで敷設して転圧し、合成例1の水溶性プレポリマー
5部と水95部を混合撹拌した散布材を一様に散布し
た。単位面積当りの散布量は2.0l/m2 とした。次
いでインターロッキングブロックを敷設し、更に目地砂
を充填し、水溶性プレポリマー5部と水95部を混合撹
拌した散布材を1.5l/m2 の割合で一様に散布し
た。散布後1時間放置した後、斜面に一様な散水を継続
して与えたところ、砂の流失および移動は全く見られな
かった。水溶性プレポリマーと水の重合反応による層の
厚さは約5mmであった。なお散布材が固まる前にブロ
ックの上面は清掃しておく(以下の例も同じ)。 (具体例2への対応)交通量の多い車道または大型車両
の通行するコンテナヤードを想定して敷砂を厚さ3cm
で敷設して転圧し、水溶性プレポリマー5部と水95部
を混合撹拌した散布材を2.0l/m2 の割合で一様に
散布した。次いでインターロッキングブロックを敷設
し、更に目地砂を充填し、水溶性プレポリマー5部と水
95部を混合撹拌した散布材を1.0〜1.5l/m2
の割合で一様に散布した。散布後1時間養生させたとこ
ろ、敷砂および目地砂の移動は見られなかった。水溶性
プレポリマーと水の重合反応による層の厚さは5〜7m
mであった。Next, examples will be described according to the above specific examples. (Correspondence to specific example 1) The thickness of the sand is 3 on the slope with a gradient of 20 degrees.
It was laid by cm and rolled, and the spray material obtained by mixing and stirring 5 parts of the water-soluble prepolymer of Synthesis Example 1 and 95 parts of water was uniformly sprayed. The amount of spray per unit area was 2.0 l / m 2 . Next, an interlocking block was laid, further filled with joint sand, and 5 parts of the water-soluble prepolymer and 95 parts of water were mixed and stirred, and the spray material was uniformly sprayed at a rate of 1.5 l / m 2 . After leaving for 1 hour after spraying, when uniform water spray was continuously applied to the slope, no runoff or migration of sand was observed. The thickness of the layer formed by the polymerization reaction of the water-soluble prepolymer and water was about 5 mm. Note that the top surface of the block should be cleaned before the spreading material hardens (the same applies to the following examples). (Correspondence to specific example 2) Assuming a container yard where a road with a large amount of traffic or a large vehicle passes, the sand is 3 cm thick.
Was laid and rolled, and 5 parts of the water-soluble prepolymer and 95 parts of water were mixed and stirred, and the spray material was uniformly sprayed at a rate of 2.0 l / m 2 . Next, an interlocking block was laid, and further, joint sand was filled, and a spray material obtained by mixing and stirring 5 parts of the water-soluble prepolymer and 95 parts of water was 1.0 to 1.5 l / m 2.
Was evenly sprayed. After curing for 1 hour after spraying, no movement of paved sand or joint sand was observed. The thickness of the layer formed by the polymerization reaction of the water-soluble prepolymer and water is 5 to 7 m.
It was m.
【0013】(具体例3への対応)舗装面にインターロ
ッキングブロックを敷設し、目地砂を充填し、水溶性プ
レポリマー5部と水95部を混合撹拌した散布材を1.
5l/m2 の割合で一様に散布したところ、風に因る砂
の吹き上がりは皆無であった。 (具体例4への対応)プールサイドにインターロッキン
グブロックを敷設し、目地砂を充填し、水溶性プレポリ
マー5部と水95部を混合撹拌した散布材を1.0l/
m2 の割合で一様に散布した。散布後1時間放置した
後、舗装面に一様な散水を継続して与えたところ、砂の
流失および移動は全く見られなかった。(Correspondence to Specific Example 3) An interlocking block was laid on the pavement surface, filled with joint sand, and 5 parts of the water-soluble prepolymer and 95 parts of water were mixed and agitated.
When sprayed uniformly at a rate of 5 l / m 2 , no sand was blown up by the wind. (Correspondence to Specific Example 4) An interlocking block was laid on the pool side, filled with joint sand, and mixed with 5 parts of the water-soluble prepolymer and 95 parts of water, and the mixture was stirred at 1.0 l /
It was sprayed uniformly at a rate of m 2 . After leaving for 1 hour after spraying, when uniform watering was continuously given to the pavement surface, no runoff or migration of sand was observed.
【0014】[0014]
【発明の効果】本発明は次の効果を奏する。すなわち、
所定の組成の水溶性プレポリマーを主材とする散布材を
敷砂または目地砂に散布して砂をクッション性を持たせ
た状態で固定するものであって、敷砂または目地砂を、
これらによるクッション性を維持した状態で固定するこ
とができる。The present invention has the following effects. That is,
A method of spraying a spraying material mainly composed of a water-soluble prepolymer having a predetermined composition on a bed sand or a joint sand to fix the sand in a state of having a cushioning property, and the bed sand or the joint sand,
It is possible to fix them while maintaining the cushioning property.
Claims (1)
し、分子量1,000〜20,000のポリオキシアル
キレン鎖を有する化合物と、そのヒドロキシル基数と同
モル以上のポリイソシアネート化合物とを反応させて得
られる水溶性プレポリマーを水に3.0〜7.0%の濃
度で均一に溶解せしめたものを、敷砂または目地砂に散
布して樹脂化層を形成することを特徴とする舗装工事に
おける砂の固定方法。1. A reaction between a compound having two or more hydroxyl groups at one end and a polyoxyalkylene chain having a molecular weight of 1,000 to 20,000 and a polyisocyanate compound having the same or more moles as the number of hydroxyl groups. It is characterized in that the water-soluble prepolymer thus obtained is uniformly dissolved in water at a concentration of 3.0 to 7.0%, and is sprayed on the spread sand or joint sand to form a resinized layer. How to fix sand in pavement work.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4102396A JPH0718123B2 (en) | 1992-03-30 | 1992-03-30 | How to fix sand in pavement work |
AU32040/93A AU654755B2 (en) | 1992-03-30 | 1993-01-27 | A method of sand anchoring in pavement works |
DE19934302138 DE4302138A1 (en) | 1992-03-30 | 1993-01-27 | Anchoring sand for bedding and jointing paving slabs - by applying an aq. soln. of water-soluble isocyanate prepolymer based on polyether-poly:ol and poly:isocyanate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4102396A JPH0718123B2 (en) | 1992-03-30 | 1992-03-30 | How to fix sand in pavement work |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05280011A true JPH05280011A (en) | 1993-10-26 |
JPH0718123B2 JPH0718123B2 (en) | 1995-03-01 |
Family
ID=14326294
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4102396A Expired - Fee Related JPH0718123B2 (en) | 1992-03-30 | 1992-03-30 | How to fix sand in pavement work |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPH0718123B2 (en) |
AU (1) | AU654755B2 (en) |
DE (1) | DE4302138A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07158003A (en) * | 1993-12-02 | 1995-06-20 | Sumitomo Rubber Ind Ltd | Block-paved road and its construction method |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2398791B (en) * | 2001-11-02 | 2004-10-13 | John Thomas Liddy | Improved block paving sand |
ITVR20030092A1 (en) * | 2003-07-29 | 2005-01-30 | Barbarisi Arch Riccardo | LAYING SYSTEM OF PORPHYRY OR SIMILAR CUBES BY MEANS OF |
CN111363115B (en) * | 2018-12-25 | 2022-02-22 | 中国石油化工股份有限公司 | Water-soluble high polymer material and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5345340A (en) * | 1976-10-06 | 1978-04-24 | Shiyouji Tsukamoto | Adhesiveebacked tape |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1100747A (en) * | 1976-10-07 | 1981-05-12 | Chevron Research And Technology Company | Soil stabilization method and compositions |
ATE3440T1 (en) * | 1978-11-30 | 1983-06-15 | Imperial Chemical Industries Plc | SILICATE GELLING COMPOSITIONS FOR USE IN SOIL STABILIZATION, SEALING A SURFACE, OR MAKING A FOUNDRY SAND CASTING, METHODS OF USE OF SUCH COMPOSITIONS FOR THE SAID PURPOSES, AND MIXTURES FOR USE IN MAKING SUCH COMPOSITIONS. |
-
1992
- 1992-03-30 JP JP4102396A patent/JPH0718123B2/en not_active Expired - Fee Related
-
1993
- 1993-01-27 AU AU32040/93A patent/AU654755B2/en not_active Ceased
- 1993-01-27 DE DE19934302138 patent/DE4302138A1/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5345340A (en) * | 1976-10-06 | 1978-04-24 | Shiyouji Tsukamoto | Adhesiveebacked tape |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07158003A (en) * | 1993-12-02 | 1995-06-20 | Sumitomo Rubber Ind Ltd | Block-paved road and its construction method |
Also Published As
Publication number | Publication date |
---|---|
AU654755B2 (en) | 1994-11-17 |
DE4302138A1 (en) | 1993-10-07 |
JPH0718123B2 (en) | 1995-03-01 |
AU3204093A (en) | 1993-10-07 |
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