JPH10120764A - Epoxy resin grout - Google Patents
Epoxy resin groutInfo
- Publication number
- JPH10120764A JPH10120764A JP30859996A JP30859996A JPH10120764A JP H10120764 A JPH10120764 A JP H10120764A JP 30859996 A JP30859996 A JP 30859996A JP 30859996 A JP30859996 A JP 30859996A JP H10120764 A JPH10120764 A JP H10120764A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- parts
- mixture
- curing agent
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 53
- 239000011440 grout Substances 0.000 title abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000003085 diluting agent Substances 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 11
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 abstract description 11
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 230000020169 heat generation Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- -1 heterocyclic diamine Chemical class 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Working Measures On Existing Buildindgs (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高速道路、鉄道等
の橋脚の耐震補強工事に用いられるエポキシ樹脂注入材
に関し、特に橋脚等の補強の為に、橋脚とこれに巻き付
けられた鋼板との間隙に注入充填して、これらを強固に
接着固定するエポキシ樹脂注入材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin injection material used for seismic reinforcement of bridges such as highways and railways, and more particularly to a method for reinforcing a bridge such as a bridge pier with a steel plate wound around the bridge pier. The present invention relates to an epoxy resin injection material that is injected into a gap and firmly adheres and fixes them.
【０００２】[0002]
【従来の技術】近年、地震などの災害から高速道路、鉄
道等の橋脚を守るために、これらの耐震補強の必要性が
指摘されている。そのため、これらの耐震補強の工法と
して既存のコンクリート橋脚構造物に対し、数ｃｍの隙
間をもたせて補強用鋼板を固定し、この隙間にエポキシ
樹脂を注入充填して硬化接着し、橋脚自体の強度を上げ
る耐震補強工事が行われている。2. Description of the Related Art In recent years, it has been pointed out that seismic reinforcement is required for protecting piers of expressways and railways from disasters such as earthquakes. Therefore, as a method of seismic reinforcement, a steel plate for reinforcement is fixed to the existing concrete pier structure with a gap of several centimeters, and epoxy resin is injected into this gap and hardened and bonded, and the strength of the pier itself is strengthened. Seismic reinforcement work is being carried out.
【０００３】ところで、これらの工法において使用され
るエポキシ樹脂に求められる特性としては、低粘度、高
強度（特に圧縮強度）、適切なポットライフ等が上げら
れ、注入に際しては、四季を通して作業するために、外
気温、躯体温度等の影響を受けにくいことも重要であ
る。The properties required of the epoxy resin used in these methods include low viscosity, high strength (especially compressive strength), an appropriate pot life, and the like. In addition, it is also important that it is hardly affected by the outside air temperature and the body temperature.
【０００４】このような目的にあったエポキシ樹脂とし
て、例えば、低温時の硬化性を得るために特開昭６３−
６３７１６に開示されるような、エポキシ樹脂とメルカ
プタン系硬化剤との組み合わせからなるエポキシ樹脂組
成物や、複素環状ジアミン硬化剤との組み合わせからな
るエポキシ樹脂組成物が用いられてきた。また、高強度
を得るためには芳香族ポリアミン硬化剤との組み合わせ
からなるエポキシ樹脂が用いられてきた。As an epoxy resin for such a purpose, for example, Japanese Patent Application Laid-Open No.
An epoxy resin composition composed of a combination of an epoxy resin and a mercaptan-based curing agent and an epoxy resin composition composed of a combination of a heterocyclic diamine curing agent, as disclosed in US Pat. No. 63716, have been used. In order to obtain high strength, an epoxy resin comprising a combination with an aromatic polyamine curing agent has been used.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、メルカ
プタン系硬化剤を用いた場合は、高強度が得られないこ
と、ポットライフが短いため注入時の粘度が上昇してし
まうこと、硬化時の発熱が大きいため樹脂の焦げ付きが
発生してしまう（特に夏期）ことなどの問題があり、ま
た、複素環状ジアミン硬化剤を用いた場合は、硬化物の
収縮が大きいことや、硬化物が脆いこと、被着体との接
着性が悪いこと等の問題があった。さらに、芳香族ポリ
アミン系硬化剤を用いた場合は、硬化速度の立ち上がり
が遅く、最終的な樹脂強度も低い値に留まってしまい必
要とされる強度が得られない、という問題があった。However, when a mercaptan-based curing agent is used, high strength cannot be obtained, the pot life is short, the viscosity at the time of pouring increases, and heat generation during curing does not occur. The large size causes problems such as scorching of the resin (especially in summer). In addition, when a heterocyclic diamine curing agent is used, the cured product has a large shrinkage, the cured product is brittle, and There were problems such as poor adhesion to the body. Further, when an aromatic polyamine-based curing agent is used, there is a problem that the rise of the curing speed is slow and the final resin strength remains at a low value, and the required strength cannot be obtained.
【０００６】そのため、本発明では上記の課題を解決
し、橋脚などの補強工法における作業環境、特に外気及
び被着体の温度に左右されることなく、必要特性を満足
させるようなエポキシ樹脂注入材を提供することを目的
とする。Therefore, the present invention solves the above-mentioned problems and provides an epoxy resin injection material that satisfies the required characteristics without being affected by the working environment, particularly the outside air and the temperature of the adherend, in a reinforcing method such as a bridge pier. The purpose is to provide.
【０００７】[0007]
【課題を解決するための手段】上記の課題を解決するた
め、請求項１では（Ａ）ビスフェノール型エポキシ樹
脂、もしくは（Ａ）ビスフェノール型エポキシ樹脂と
（Ｂ）反応性希釈剤の混合物から構成される主剤に対
し、（Ｃ）ポリアミドアミン及び（Ｄ）芳香族変性アミ
ンの混合物から構成される硬化剤を添加して構成される
エポキシ樹脂注入材を用いるようにした。また、請求項
２では、（Ａ）ビスフェノール型エポキシ樹脂、もしく
は（Ａ）ビスフェノール型エポキシ樹脂と（Ｂ）反応性
希釈剤の混合物から構成される主剤に対し、（Ｃ）ポリ
アミドアミン、（Ｄ）芳香族変性アミン、及び（Ｅ）脂
肪族変性ポリアミンの混合物から構成される硬化剤を添
加して構成されるエポキシ樹脂注入材を用いるようにし
た。In order to solve the above-mentioned problems, the present invention comprises (A) a bisphenol-type epoxy resin or a mixture of (A) a bisphenol-type epoxy resin and (B) a reactive diluent. An epoxy resin injecting material constituted by adding a curing agent composed of a mixture of (C) polyamidoamine and (D) aromatic-modified amine to the main agent is used. Further, in claim 2, (C) polyamidoamine, (D) a bisphenol-type epoxy resin, or (C) a main component composed of a mixture of bisphenol-type epoxy resin and (B) a reactive diluent. An epoxy resin injection material composed by adding a curing agent composed of a mixture of an aromatic modified amine and (E) an aliphatic modified polyamine was used.
【０００８】本発明に使用される（Ａ）ビスフェノール
型エポキシ樹脂としては、下記一般式（１）で示される
主鎖にビスフェノール骨格を有し、分子の末端及び／ま
たは側鎖にエポキシ基を持つ化合物が上げられる。こら
れのビスフェノール型エポキシ樹脂として好ましいもの
としては、ビスフェノールＡ型エポキシ樹脂が上げられ
る。The bisphenol type epoxy resin (A) used in the present invention has a bisphenol skeleton in the main chain represented by the following general formula (1) and has an epoxy group at the terminal and / or side chain of the molecule. The compound is raised. Preferred examples of the bisphenol-type epoxy resin include bisphenol A-type epoxy resins.
【０００９】[0009]
【化１】 （ＲはＨまたはＣＨ３ｎは平均で０〜２）Embedded image (R is H or CH 3 n is 0-2 on average)
【００１０】また、本発明に使用される（Ａ）ビスフェ
ノール型エポキシ樹脂の粘度は、２〜１５Ｐａ・ｓ（２
５℃）の範囲が適当である。１５Ｐａ・ｓよりも高粘度
であると被着体間の隙間への充填が困難になったり、
（Ｂ）の反応性希釈剤を多量に使用する必要が生じ、硬
化物の強度が低下する場合がある。The viscosity of the bisphenol type epoxy resin (A) used in the present invention is 2 to 15 Pa · s (2
(5 ° C.). If the viscosity is higher than 15 Pa · s, it becomes difficult to fill the gap between the adherends,
It becomes necessary to use a large amount of the reactive diluent (B), and the strength of the cured product may decrease.
【００１１】本発明に使用される（Ａ）ビスフェノール
型エポキシ樹脂の具体例としては、商品名エピコート＃
８０６、＃８０７、＃８２７、＃８２８（以上、油化シ
ェルエポキシ社製）、商品名エポミックＲ１３９、Ｒ１
４０（以上、三井石油化学工業社製）、商品名アラルダ
イトＧＹ−２５０、ＧＹ−２６０（以上、日本チバガイ
ギー社製）など汎用のビスフェノール型エポキシ樹脂が
挙げられ、求める粘度により種々の選択が可能である。A specific example of the bisphenol type epoxy resin (A) used in the present invention is a product name Epicoat #
806, # 807, # 827, # 828 (all manufactured by Yuka Shell Epoxy Co., Ltd.), trade names EPOMIC R139, R1
For example, general-purpose bisphenol-type epoxy resins such as No. 40 (manufactured by Mitsui Petrochemical Industry Co., Ltd.) and trade names Araldite GY-250 and GY-260 (manufactured by Nippon Ciba Geigy) can be used. is there.
【００１２】次に、本発明に使用できる（Ｂ）の反応性
希釈剤は、（Ａ）のエポキシ樹脂の粘度や硬化物の物性
を調整するために使用される。この反応性希釈剤として
は、例えば下記一般式（２）、（３）、（４）で示され
るようなアルキルモノグリシジルエーテルやアルキレン
ジグリシジルエーテルが挙げられる。具体的には例え
は、商品名ＹＥＤ１１１、ＹＥＤ１１６、ＹＥＤ１２
２、ＹＥＤ２０５、ＹＥＤ２１６（以上、油化シェルエ
ポキシ社製）、商品名デナコールＥＸ−１１１、ＥＸ−
１２１、ＥＸ−１４１、ＥＸ−１４６、ＥＸ−２１１、
ＥＸ−２１２（ナガセ化成工業社製）などが挙げられ、
好ましくは、１，６ヘキサジオールジグリシジルエーテ
ルのような２官能以上のタイプのものである。Next, the reactive diluent (B) that can be used in the present invention is used for adjusting the viscosity of the epoxy resin (A) and the physical properties of the cured product. Examples of the reactive diluent include alkyl monoglycidyl ethers and alkylenediglycidyl ethers represented by the following general formulas (2), (3) and (4). Specifically, for example, trade names YED111, YED116, YED12
2, YED205, YED216 (all manufactured by Yuka Shell Epoxy Co., Ltd.), trade names Denacol EX-111, EX-
121, EX-141, EX-146, EX-211,
EX-212 (manufactured by Nagase Kasei Kogyo) and the like,
Preferably, it is a bifunctional or higher type such as 1,6 hexadiol diglycidyl ether.
【００１３】[0013]
【化２】 （ｎは１〜２０の整数）Embedded image (N is an integer from 1 to 20)
【００１４】[0014]
【化３】 （ｎは１〜２０の整数）Embedded image (N is an integer from 1 to 20)
【００１５】[0015]
【化４】 （ｎは１〜９の整数）Embedded image (N is an integer from 1 to 9)
【００１６】次に、上記（Ａ）のエポキシ樹脂と（Ｂ）
の反応性希釈剤との混合比は、使用する（Ａ）のエポキ
シ樹脂の種類によって異なるが、（Ａ）：（Ｂ）が、７
０：３０〜１００：０（重量部）であることが好まし
い。（Ｂ）の反応性希釈剤の混合比が３０重量％を越え
ると、硬化物の樹脂強度が小さくなり、初期硬化性も悪
くなるといった不具合が生じる。Next, the epoxy resin (A) and (B)
The mixing ratio with the reactive diluent varies depending on the type of the epoxy resin (A) used.
The ratio is preferably from 0:30 to 100: 0 (parts by weight). When the mixing ratio of the reactive diluent (B) is more than 30% by weight, the resin strength of the cured product becomes small and the initial curability becomes poor.
【００１７】次に、本発明に使用できる硬化剤は、
（Ｃ）ポリアミドアミン、（Ｄ）芳香族変性アミン、
（Ｅ）脂肪族変性ポリアミンであり、（Ｃ）のポリアミ
ドアミンは、主として硬化樹脂の脆性を抑え可撓性の付
与を目的に用いるもので、合成脂肪酸、天然脂肪酸のカ
ルボン酸とポリエチレンポリアミン等に代表されるエチ
レンアミンとの反応生成物であり、これらは原料の種類
や合成時の温度勾配、反応時間により種々のものが得ら
れる。具体的には、粘度や反応性から例えば、商品名ト
ーマイド＃２３５Ａ、＃２３５Ｒ、＃２４１、＃２４
５、＃２４６１（以上、富士化成工業社製）、商品名ア
ンカマイド３７５Ａ、４００、５０６（以上、ＡＣＩジ
ャパンリミテッド社製）、商品名ＡＣＲハードナーＨ４
５１０（旭電化工業社製）などが挙げられ、好ましくは
トーマイド＃２４６１である。Next, the curing agent that can be used in the present invention is:
(C) polyamidoamine, (D) aromatic modified amine,
(E) an aliphatic modified polyamine, and the polyamidoamine (C) is used mainly for the purpose of suppressing the brittleness of the cured resin and imparting flexibility, and is used as a synthetic fatty acid, a carboxylic acid of a natural fatty acid and a polyethylene polyamine. It is a typical reaction product with ethyleneamine, and various products can be obtained depending on the type of raw materials, the temperature gradient during synthesis, and the reaction time. More specifically, for example, trade names Tomide # 235A, # 235R, # 241, # 24
5, # 2461 (above, manufactured by Fuji Kasei Kogyo Co., Ltd.), trade names Ankamide 375A, 400, 506 (above, manufactured by ACI Japan Limited), trade name: ACR Hardener H4
510 (manufactured by Asahi Denka Kogyo KK) and the like, and preferably Tomide # 2461.
【００１８】（Ｄ）の芳香族変性アミンは主として樹脂
強度の向上を目的に用いるもので、メタフェニレンジア
ミンやメチレンジアニリンなどの共融混合化や、樹脂ア
ダクトにより液状化されたものの使用が可能である。具
体的には、例えば、商品名フジキュアーＦＸＭ−８２３
Ｆ（富士化成工業社製）、エピキュアー＃１５１（油化
シェルエポキシ社製）、商品名ＡＣＲハードナーＨ３
１、Ｈ３４８６（以上、旭電化工業社製）、商品名アン
カミンＬＯ、ＬＯＳ、ＬＶ、ＬＶＳ（以上、ＡＣＩジャ
パンリミテッド社製）などが挙げられ、好ましくはフジ
キュアーＦＸＭ８２３Ｆである。The aromatic-modified amine (D) is used mainly for the purpose of improving the strength of the resin, and may be eutectic-mixed such as metaphenylenediamine or methylenedianiline, or liquefied by a resin adduct. It is. Specifically, for example, a product name “Fujicure FXM-823”
F (manufactured by Fuji Kasei Kogyo), Epi Cure # 151 (manufactured by Yuka Shell Epoxy), trade name: ACR Hardener H3
1, H3486 (above, manufactured by Asahi Denka Kogyo KK), trade names Ankamin LO, LOS, LV, LVS (above, manufactured by ACI Japan Limited) and the like, and preferably Fuji Cure FXM823F.
【００１９】（Ｅ）の脂肪族変性ポリアミンは主として
低温硬化性の向上を目的に用いるもので、下記一般式
（４）で表されるポリエチレンポリアミンの樹脂アダク
ト化、マンニッヒ変性、もしくは促進剤としてフェノー
ル類を添加したものが挙げられる。さらには粘度調整、
反応性の制御のため、ベンジルアルコールなどの添加も
可能である。具体的には、例えば、商品名フジキュアー
ＦＸＫ８３０、ＦＸＳ８５０、ＦＸＳ８５３（以上、富
士化成工業社製）、商品名ＡＣＲハードナーＨ３７２
５、Ｈ３８９３、Ｈ３８９４（以上、旭電化工業社
製）、商品名アンカミン１７８４、２０２１（以上、Ａ
ＣＩジャパンリミテッド社製）、商品名バーサミンＦ
８、Ｉ−３７６（以上、ヘンケル白水社製）などが挙げ
られ、好ましくはフジキュアーＦＸＳ８５３である。The aliphatic modified polyamine (E) is mainly used for the purpose of improving the low-temperature curability, and is a resin adduct of a polyethylene polyamine represented by the following general formula (4), a Mannich modification, or phenol as an accelerator. And the like. Furthermore, viscosity adjustment,
For controlling the reactivity, addition of benzyl alcohol or the like is also possible. Specifically, for example, trade names: Fuji Cure FXK830, FXS850, FXS853 (all manufactured by Fuji Kasei Kogyo Co., Ltd.), trade name: ACR Hardener H372
5, H3893, H3894 (all manufactured by Asahi Denka Kogyo Co., Ltd.), trade names Ankamin 1784, 2021 (all, A
CI Japan Limited), trade name Versamine F
8, I-376 (all manufactured by Henkel Hakusui Co., Ltd.) and the like, and preferably Fujicure FXS853.
【００１９】[0019]
【化５】 （ｎは１〜３の整数）Embedded image (N is an integer of 1 to 3)
【００２０】これらの硬化剤のうち（Ｃ）と（Ｄ）を混
合して使用する場合は、外気温度が１０℃以上のときに
有効に使用でき、また、（Ｃ）と（Ｄ）さらに（Ｅ）を
併用すると外気温度が５℃以下になる作業環境において
も有効に使用できる。When these curing agents (C) and (D) are used as a mixture, they can be effectively used when the outside air temperature is 10 ° C. or higher, and (C) and (D) When used together with E), it can be used effectively even in a work environment where the outside air temperature is 5 ° C. or less.
【００２１】ここで、（Ｃ）と（Ｄ）を混合して使用す
る場合は、（Ｃ）のポリアミドアミンと（Ｄ）の芳香族
変性アミンの混合比は両者の合計量を１００（重量部）
とした場合、前者：後者の比が、３０：７０〜７０：３
０（重量％）であり、好ましくは（Ｃ）：（Ｄ）＝４
５：５５〜５５：４５（重量％）である。（Ｃ）のポリ
アミドアミンが３０重量％未満であると硬化性が悪くな
り、硬化樹脂が脆いものとなる。反対に（Ｄ）の芳香族
変性アミンが３０重量％未満であると可使時間が短くな
り、樹脂強度が大幅に低下する。When (C) and (D) are used as a mixture, the mixing ratio of the polyamidoamine of (C) and the aromatic modified amine of (D) is 100 (parts by weight). )
When the ratio of the former: the latter is 30:70 to 70: 3
0 (% by weight), preferably (C) :( D) = 4
5:55 to 55:45 (% by weight). If the polyamidoamine of (C) is less than 30% by weight, the curability will be poor and the cured resin will be brittle. On the other hand, when the aromatic modified amine (D) is less than 30% by weight, the pot life becomes short, and the resin strength is greatly reduced.
【００２２】次に、上記（Ｃ）と（Ｄ）さらに（Ｅ）を
併用する場合には、これらの混合割合は（Ｃ）と（Ｄ）
ならびに（Ｅ）の全体量を１００（重量部）とした場合
（Ｃ）が１０〜４０（重量％）、（Ｄ）が１０〜３０
（重量％）、（Ｅ）が３０〜７０（重量％）の範囲内で
構成され、特に（Ｃ）：（Ｄ）：（Ｅ）＝１５〜２５：
１５〜２５：５５〜６５（重量％）であることが好まし
い。（Ｃ）のポリアミドアミンが１０重量％未満である
と硬化物の可撓性が小さくなるため、脆くなり、また、
４０重量％を越えると硬化物の強度が低下する。また、
（Ｄ）の芳香族変性アミンが１０重量％未満であると樹
脂強度が低下し、３０重量％を越えると低温時硬化性が
大幅に悪くなる。（Ｅ）の脂肪族変性ポリアミンが３０
重量％未満であると低温時硬化性が悪くなり、７０重量
％越えると可使時間が短くなり、樹脂強度も低下する。Next, when the above (C), (D) and (E) are used together, their mixing ratio is (C) and (D)
Further, when the total amount of (E) is 100 (parts by weight), (C) is 10 to 40 (% by weight), and (D) is 10 to 30 (% by weight).
(% By weight) and (E) are within the range of 30 to 70 (% by weight), and particularly (C) :( D) :( E) = 15 to 25:
It is preferably 15 to 25: 55 to 65 (% by weight). When the polyamidoamine of (C) is less than 10% by weight, the flexibility of the cured product is reduced, so that the cured product becomes brittle.
If it exceeds 40% by weight, the strength of the cured product will be reduced. Also,
If the aromatic modified amine (D) is less than 10% by weight, the resin strength is reduced, and if it exceeds 30% by weight, the curability at low temperature is significantly deteriorated. When the aliphatic modified polyamine of (E) is 30
When the amount is less than 70% by weight, the curability at low temperature becomes poor, and when the amount exceeds 70% by weight, the pot life becomes short and the resin strength also decreases.
【００２３】次に、（Ａ）のエポキシ樹脂単独、もしく
は（Ａ）のエポキシ樹脂と（Ｂ）の反応性希釈剤の混合
物として構成される主剤と、上記した（Ｃ）＋（Ｄ）ま
たは（Ｃ）＋（Ｄ）＋（Ｅ）から構成される硬化剤との
混合比は、前者１００重量部に対して後者３０〜８０重
量部が適当である。この範囲を逸脱すると初期硬化性が
悪くなり、樹脂強度が低下する。Next, the epoxy resin of (A) alone or the main agent constituted as a mixture of the epoxy resin of (A) and the reactive diluent of (B) is combined with the above-mentioned (C) + (D) or ( The mixing ratio with the curing agent composed of (C) + (D) + (E) is suitably from 30 to 80 parts by weight with respect to 100 parts by weight of the former. If the ratio is out of this range, the initial curability will deteriorate, and the resin strength will decrease.
【００２４】本発明はさらに、必要に応じて各種添加剤
を加えることができる。例えば、充填材、着色剤、安定
剤であり、こられは、本発明の目的を逸脱しない程度に
任意に添加することができる。In the present invention, various additives can be added as required. For example, a filler, a colorant, and a stabilizer, which can be arbitrarily added without departing from the purpose of the present invention.
【００２５】次に、本発明のエポキシ樹脂注入材を製造
する際の行程を説明する。本剤及び硬化剤とも原料を秤
量し、室温にて均一になるまで混合を行うことにより調
製され、必要と有れば加熱混合も可能である。Next, a process for producing the epoxy resin injection material of the present invention will be described. Both the present agent and the curing agent are prepared by weighing the raw materials and mixing them at room temperature until they are uniform. If necessary, heat mixing is also possible.
【００２６】次に、本発明のエポキシ樹脂注入材を使用
する際の行程について説明する。混合攪拌機に規定配合
量の本剤及び硬化剤を入れ、充分均一に混合した注入材
を予め下地処理のなされている被着構造体に対し、注入
ポンプを用いて注入する。この際混合後の注入材には可
使時間があるので、特に一度に多量の混合を行った場合
は可使時間に留意し素早い作業が必要となる。また混
合、注入作業に際しては、気泡の混入が硬化樹脂の強度
低下の原因となるので気泡の混入をなるべく抑える必要
がある。Next, a process for using the epoxy resin injection material of the present invention will be described. A prescribed mixing amount of the present agent and the curing agent are put into a mixing stirrer, and an injection material mixed sufficiently uniformly is injected into an adhered structure which has been previously subjected to a base treatment by using an injection pump. At this time, since the injection material after mixing has a pot life, it is necessary to pay attention to the pot life and perform a quick operation, especially when a large amount is mixed at once. In addition, in the mixing and pouring operations, it is necessary to suppress the mixing of air bubbles as much as possible because the mixing of air bubbles causes a reduction in the strength of the cured resin.
【００２７】[0027]
【実施例】表１及び表２に示すような配合割合（重量
部）からなるエポキシ樹脂組成物について下記に示すよ
うな評価試験を実施した。評価基準としては表３に示す
ような首都高速道路公団の補修用エポキシ樹脂施工基準
におけるエポキシ樹脂品質確認試験規格値を用いた。た
だし規格値の存在しないものに関しては、表４に示す評
価基準を適用した。EXAMPLES The following evaluation tests were carried out on epoxy resin compositions having the mixing ratios (parts by weight) shown in Tables 1 and 2. As the evaluation standard, an epoxy resin quality confirmation test standard value in the repair epoxy resin application standard of the Metropolitan Expressway Public Corporation shown in Table 3 was used. However, the evaluation criteria shown in Table 4 were applied to those having no standard value.
【００２８】評価試験 （１）粘度測定（作業性）：主剤及び硬化剤を混合後、
ただちにＢＨ型回転粘度計により測定した。 （２）可使時間：主剤及び硬化剤を混合した後、時間と
共に変化する温度を測定し、時間−温度曲線（硬化発熱
曲線）を得た。この曲線において急激な温度上昇が始ま
るまでの時間の７０％、もしくは温度の立ち上がりが明
確でない場合、最高発熱温度までの時間の５０％をもっ
て可使時間とした。 （３）圧縮強度：ＪＩＳ−Ｋ−６９１１（熱硬化性プラ
スチック一般試験方法）に準じて試験を行った。ただし
試験片の形状は一辺２０±０．５ｍｍの立方体とした。 （４）最高発熱温度：前述した硬化発熱曲線におけるピ
ーク温度を最高発熱温度とした。 （５）硬化性：主剤及び硬化剤を混合した後、２４時間
放置後の表面硬化性をタックの残り具合により評価し
た。Evaluation Test (1) Viscosity measurement (workability): After mixing the main agent and the curing agent,
It was immediately measured with a BH-type rotational viscometer. (2) Pot life: After mixing the main agent and the curing agent, the temperature changing with time was measured to obtain a time-temperature curve (curing heat generation curve). In this curve, the pot life was defined as 70% of the time until the rapid rise in temperature, or 50% of the time to the maximum heat generation temperature when the rise in temperature was not clear. (3) Compressive strength: The test was performed according to JIS-K-6911 (General thermosetting plastic test method). However, the shape of the test piece was a cube having a side of 20 ± 0.5 mm. (4) Maximum heat generation temperature: The peak temperature in the above-mentioned curing heat generation curve was defined as the maximum heat generation temperature. (5) Curability: After mixing the main agent and the curing agent, the surface curability after standing for 24 hours was evaluated based on the remaining tack.
【００２９】これら試験時の環境温度ならびに硬化条件
は表５の通りである。これらの試験結果を表６及び表７
に示す。この試験結果から明らかなように、請求項１に
関しては実施例１〜７、好ましくは実施例２の配合物を
用いることにより発熱を抑えながら、かつ高強度を得る
ことが出来ることを見出した。また請求項２に関しては
実施例１〜７、好ましくは実施例２の配合物を用いるこ
とにより低温時の作業性に優れ、かつ良好な硬化性、強
度を得ることが出来る事を見出した。Table 5 shows the environmental temperature and curing conditions during these tests. Tables 6 and 7 show the results of these tests.
Shown in As is clear from the test results, it has been found that the use of the blends of Examples 1 to 7, preferably Example 2 enables high strength to be obtained while suppressing heat generation. Further, with respect to claim 2, it has been found that by using the compositions of Examples 1 to 7, preferably Example 2, excellent workability at low temperatures and good curability and strength can be obtained.
【００３０】[0030]
【発明の効果】以上説明したように、（Ａ）ビスフェノ
ール型エポキシ樹脂、もしくは（Ａ）ビスフェノール型
エポキシ樹脂と（Ｂ）反応性希釈剤の混合物から構成さ
れる主剤に対し、（Ｃ）ポリアミドアミン及び（Ｄ）芳
香族変性アミンの混合物から構成される硬化剤を添加し
て構成されるエポキシ樹脂組成物を用いることにより、
硬化時の急激な発熱（６０℃以下）を抑えつつかつ高圧
縮強度、適切な可使時間と作業性を得ることが可能であ
る。よって、このエポキシ樹脂組成物は春夏秋期の橋脚
補強用エポキシ樹脂として必要充分な特性を有している
といえる。As described above, (A) a bisphenol-type epoxy resin, or (C) a polyamidoamine with respect to a main component composed of a mixture of a bisphenol-type epoxy resin and (B) a reactive diluent. And (D) using an epoxy resin composition constituted by adding a curing agent composed of a mixture of aromatic modified amines,
It is possible to suppress rapid heat generation (60 ° C. or less) at the time of curing and obtain high compressive strength, appropriate working life and workability. Therefore, it can be said that this epoxy resin composition has necessary and sufficient properties as an epoxy resin for reinforcing a pier in spring, summer and autumn.
【００３１】また、（Ａ）ビスフェノール型エポキシ樹
脂、もしくは（Ａ）ビスフェノール型エポキシ樹脂と
（Ｂ）反応性希釈剤の混合物から構成される主剤に対
し、（Ｃ）ポリアミドアミン、（Ｄ）芳香族変性アミ
ン、及び（Ｅ）脂肪族変成アミンの混合物から構成され
る硬化剤を添加して構成されるエポキシ樹脂組成物を用
いることにより低温時硬化性と同時に高圧縮強度、さら
には低温時においても作業性を損なうことのない低い粘
度を得ることが可能である。よって、このエポキシ樹脂
組成物は冬期の橋脚補強用エポキシ樹脂として必要充分
な特性を有しているといえる。In addition, (C) polyamidoamine, (D) aromatic compound, and (A) bisphenol type epoxy resin, or (A) a main component composed of a mixture of bisphenol type epoxy resin and (B) reactive diluent. By using an epoxy resin composition composed by adding a curing agent composed of a mixture of a modified amine and (E) an aliphatic modified amine, the composition has a high compressive strength at the same time as a curability at a low temperature, and even at a low temperature. It is possible to obtain a low viscosity without impairing workability. Therefore, it can be said that this epoxy resin composition has necessary and sufficient properties as an epoxy resin for reinforcing a pier in winter.
【００３２】このように単独の硬化剤成分では達成しき
れない補強用エポキシ樹脂注入材としての必要特性を、
２成分もしくは３成分の硬化剤を適切な配合割合で用い
ることにより充分に達成されることが見出された。 As described above, the necessary properties as a reinforcing epoxy resin injection material that cannot be achieved by a single curing agent component are as follows:
It has been found that this can be sufficiently achieved by using a two- or three-component curing agent in an appropriate compounding ratio.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井上 学 東京都八王子市狭間町1456番地 株式会社 スリーボンド内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Manabu Inoue 1456, Hazamacho, Hachioji-shi, Tokyo Three Bond Co., Ltd.
Claims (2)
もしくは（Ａ）ビスフェノール型エポキシ樹脂と（Ｂ）
反応性希釈剤の混合物から構成される主剤１００重量部
に対し、（Ｃ）ポリアミドアミン及び（Ｄ）芳香族変性
アミンの混合物から構成される硬化剤を３０〜８０重量
部を添加して構成されるエポキシ樹脂組成物であって、
前記（Ａ）：（Ｂ）の混合比が、７０：３０〜１００：
０（重量部）及び（Ｃ）：（Ｄ）の混合比が、３０：７
０〜７０：３０（重量部）であることを特徴とするエポ
キシ樹脂注入材。(1) a bisphenol type epoxy resin,
Or (A) bisphenol type epoxy resin and (B)
30 to 80 parts by weight of a curing agent composed of a mixture of (C) polyamidoamine and (D) aromatic modified amine is added to 100 parts by weight of a main agent composed of a mixture of reactive diluents. Epoxy resin composition,
The mixing ratio of (A) :( B) is 70:30 to 100:
0 (parts by weight) and the mixing ratio of (C) :( D) is 30: 7
0 to 70:30 (parts by weight).
もしくは（Ａ）ビスフェノール型エポキシ樹脂と（Ｂ）
反応性希釈剤の混合物から構成される主剤１００重量部
に対し、（Ｃ）ポリアミドアミン及び（Ｄ）芳香族変性
アミン、（Ｅ）脂肪族変性ポリアミンの混合物から構成
される硬化剤を３０〜８０重量部を添加して構成される
エポキシ樹脂組成物であって、前記（Ａ）：（Ｂ）の混
合比が、７０：３０〜１００：０（重量部）及び（Ｃ）
と（Ｄ）ならびに（Ｅ）の混合割合が、前記（Ｃ）乃至
（Ｅ）の全体量を１００（重量部）とした場合、（Ｃ）
が２０〜４０（重量部）、（Ｄ）が１０〜３０（重量
部）、（Ｅ）が３０〜７０（重量部）の範囲内で構成さ
れることを特徴とするエポキシ樹脂注入材。2. A bisphenol type epoxy resin,
Or (A) bisphenol type epoxy resin and (B)
A curing agent composed of a mixture of (C) polyamidoamine, (D) aromatic-modified amine, and (E) aliphatic-modified polyamine is used in an amount of 30 to 80 parts by weight per 100 parts by weight of the main agent composed of a mixture of reactive diluents. An epoxy resin composition constituted by adding parts by weight, wherein the mixing ratio of (A) :( B) is 70:30 to 100: 0 (parts by weight) and (C).
When the mixing ratio of (D) and (E) is 100 (parts by weight), the total amount of (C) to (E) is (C)
20 to 40 (parts by weight), (D) within a range of 10 to 30 (parts by weight), and (E) within a range of 30 to 70 (parts by weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30859996A JP3440723B2 (en) | 1996-10-15 | 1996-10-15 | Epoxy resin injection material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30859996A JP3440723B2 (en) | 1996-10-15 | 1996-10-15 | Epoxy resin injection material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10120764A true JPH10120764A (en) | 1998-05-12 |
| JP3440723B2 JP3440723B2 (en) | 2003-08-25 |
Family
ID=17982984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30859996A Expired - Fee Related JP3440723B2 (en) | 1996-10-15 | 1996-10-15 | Epoxy resin injection material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3440723B2 (en) |
Cited By (12)
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|---|---|---|---|---|
| JP2002201802A (en) * | 2000-10-24 | 2002-07-19 | Ohbayashi Corp | Injection repair material for concrete body and method of repairing concrete body |
| KR100579793B1 (en) * | 1998-12-31 | 2006-08-31 | 에스케이케미칼주식회사 | Primer composition for construction |
| KR100855036B1 (en) * | 2006-10-25 | 2008-08-29 | 주식회사 일건건축사사무소 | Grout |
| CN100457824C (en) * | 2006-07-25 | 2009-02-04 | 长江水利委员会长江勘测规划设计研究院 | Green high-strength epoxy grouting material and its prepn |
| KR100979451B1 (en) * | 2009-12-02 | 2010-09-02 | (주)아해 | Polymer composition for solidification of radioactive waste materials |
| WO2015064191A1 (en) * | 2013-10-30 | 2015-05-07 | Dic株式会社 | Concrete repair material |
| CN105670229A (en) * | 2016-04-07 | 2016-06-15 | 主义 | Technology for preparing epoxy-resin-polymer grouting liquid |
| CN113604180A (en) * | 2021-08-11 | 2021-11-05 | 北京华腾新材料股份有限公司 | Low-temperature-resistant high-thixotropy epoxy daub and preparation method thereof |
| CN113637293A (en) * | 2021-08-30 | 2021-11-12 | 中海油能源发展股份有限公司 | Modified resin and application thereof in plugging agent, high-temperature plugging agent and application thereof in high-temperature abandoned well plugging |
| CN115386351A (en) * | 2022-07-29 | 2022-11-25 | 西安众海石油科技有限公司 | Retarding high-strength resin and preparation method thereof |
| JP2023146719A (en) * | 2022-03-29 | 2023-10-12 | 日本製鉄株式会社 | Gap filling material and gap repair method |
| CN117050272A (en) * | 2023-09-06 | 2023-11-14 | 北京密云水泥制品有限责任公司 | Curing agent for epoxy grouting material, preparation method thereof and epoxy grouting material |
-
1996
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| JP2002201802A (en) * | 2000-10-24 | 2002-07-19 | Ohbayashi Corp | Injection repair material for concrete body and method of repairing concrete body |
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| KR100855036B1 (en) * | 2006-10-25 | 2008-08-29 | 주식회사 일건건축사사무소 | Grout |
| KR100979451B1 (en) * | 2009-12-02 | 2010-09-02 | (주)아해 | Polymer composition for solidification of radioactive waste materials |
| WO2015064191A1 (en) * | 2013-10-30 | 2015-05-07 | Dic株式会社 | Concrete repair material |
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| JP2023146719A (en) * | 2022-03-29 | 2023-10-12 | 日本製鉄株式会社 | Gap filling material and gap repair method |
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| CN117050272A (en) * | 2023-09-06 | 2023-11-14 | 北京密云水泥制品有限责任公司 | Curing agent for epoxy grouting material, preparation method thereof and epoxy grouting material |
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| Publication number | Publication date |
|---|---|
| JP3440723B2 (en) | 2003-08-25 |
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