JP2004204144A - Epoxy-based curable resin composition for repair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an epoxy-based curable resin composition which is suitably used to fill and repair a cracked part or a defective part of ceramic, a metal or concrete. <P>SOLUTION: This curable resin composition contains an epoxy resin of a bisphenol type, a urethane-modified epoxy resin and alumina. A content of alumina is 100-900 pts. wt. based on the sum of the epoxy resin of the bisphenol type and the urethane-modified epoxy resin being 100 pts. wt. The composition is cured by a specific polyamine. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１８】
ここで、Ａはポリアミンから２つのアミノ基を除去した骨格を表し、Ｒは２価の有機であり、ｔは１〜１０の数である、
で表わされる化合物からなる硬化剤１０〜４０重量部を混合することを特徴とする硬化物の製造法によって達成される。
【００１９】
本発明によれば、本発明の上記目的および利点は、第３に、本発明の上記エポキシ硬化性樹脂組成物と上記硬化剤とを分離された状態で含有する、金属補修用キットまたは土木補修用キットによって達成される。
【００２０】
最後に、本発明によれば、本発明の上記目的および利点は、本発明の上記エポキシ系硬化性樹脂組成物１００重量部と上記硬化剤１０〜４０重量部とを混合し、得られた混合物を硬化する前に補修を必要とする箇所に施しそしてその箇所で硬化せしめることを特徴とする補修方法によって達成される。
【００２１】
【発明の好ましい実施態様】
以下、本発明について詳述する。先ず、本発明のエポキシ系硬化性樹脂組成物（以下、本発明の組成物ということがある）について説明する。
【００２２】
本発明の組成物は、上記の如く、ビスフェノール型エポキシ樹脂、ウレタン変性エポキシ樹脂およびアルミナを含有してなる。ビスフェノール型エポキシ樹脂としては、例えばビスフェノールＡ型エポキシ樹脂およびビスフェノールＦ型エポキシ樹脂が好ましく用いられる。これらは単独であるいは２種以上一緒に用いることができる。
【００２３】
ビスフェノール型エポキシ樹脂としては、例えば下記式（１）
【００２４】
【化５】

【００２５】
ここで、Ａはビスフェノールから２つの水酸基を除いた骨格を表わしており、ｍは０〜１の数である、
【００２６】
で表わされる化合物が好ましく用いられる。ビスフェノールＡ型エポキシ樹脂は、上記式（１）において、ＡがビスフェノールＡから２つの水酸基を除去した骨格であるものであり、ビスフェノールＦ型エポキシ樹脂は、ＡがビスフェノールＦから２つの水酸基を除去した骨格であるものである。これらのビスフェノール型エポキシ樹脂は、例えば旭電化工業（株）のＥＰ−４１００、ＥＰ−４９０１あるいは油化シェルエポキシ（株）のエピコート８２８などの市販品として入手しうる。
【００２７】
ウレタン変性エポキシ樹脂としては、例えばウレタン変性ビスフェノールＡ型エポキシ樹脂およびウレタン変性ビスフェノールＦ型エポキシ樹脂が好ましく用いられる。これらは単独であるいは２種以上一緒に用いることができる。
【００２８】
ウレタン変性ビスフェノール樹脂としては、例えば下記式（２）
【００２９】
【化６】

【００３０】
ここで、Ａの定義は上記式（１）に同じであり、Ｂは２価の有機基であり、ｎおよびｑはそれぞれ独立に、０〜１の数である、
【００３１】
で表わされる化合物が好ましく用いられる。ウレタン変性エポキシ樹脂は、上記式（２）において、ＡがビスフェノールＡから２つの水酸基を除去した骨格であるものであり、ビスフェノールＦ型エポキシ樹脂はＡがビスフェノールＦから２つの水酸基を除去した骨格のものである。
【００３２】
また、上記式（２）において、Ｂは２価の有機基であり、例えばポリエチレングリコール、ポリプロピレングリコールの如きポリアルキレングリコール１モルとトルエンジイソシアネートの如き芳香族ジイソシアネート２モルとの反応生成物であるジイソシアネート化合物から２つのイソシアネート基を除去した骨格を挙げることができる。これらのうち、下記式
【００３３】
【化７】

【００３４】
で表わされるオキシプロピレン繰返し単位の数が好ましくは１０〜１００、より好ましくは２０〜９０、特に好ましくは３０〜８０のポリオキシプロピレンとトルエンジイソシアネートとの反応生成物に由来する骨格が好ましい。
【００３５】
上記式（２）で表されるウレタン変性エポキシ樹脂としては、例えば下記式
【００３６】
【化８】

【００３７】
ここで、ｍは０〜１の数であり、ｎ１およびｎ２の合計は５０〜６０である、
【００３８】
で表わされる化合物が好ましく用いられる。これらのウレタン変性エポキシ樹脂は、例えば旭電化工業（株）のアデカレジンＥＰＵ−７８−１１等の市販品として入手できる。
【００３９】
アルミナとしては、例えば平均粒径５〜１００μｍ、好ましくは１０〜８０μｍの凝集粒子が好ましく用いられる。
【００４０】
アルミナは予めシランカップリング剤で表面処理して用いることができる。予め表面処理したアルミナを用いることにより、アルミナを高含有割合で含む場合にも、樹脂成分とのなじみがよく、硬化前の例えば貯蔵中に分離したり、沈積したりすることを容易に避けることができるようになる。
【００４１】
シランカップリング剤としては、エポキシシランが好ましく用いられる。エポキシシランとしては、例えば２−（３，４−エポキシシクロヘキシル）エチルトリ（Ｃ₁〜Ｃ₄アルコキシ）シラン、γ−グリシドキシプロピルトリ（Ｃ₁〜Ｃ₄アルコキシ）シラン、γ−グリシドキシプロピルＣ₁〜Ｃ₂アルキルジ（Ｃ₁〜Ｃ₄アルコキシ）シランを挙げることができる。
【００４２】
さらに具体的には、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシランを挙げることができる。
【００４３】
上記のうち、γ−グリシドキシプロピルトリ（Ｃ₁〜Ｃ₄アルコキシ）シランが好ましく、γ−グリシドキシプロピルトリ（メトキシまたはエトキシ）シランが特に好ましい。
【００４４】
本発明の組成物は、アルミナを上記ビスフェノール型エポキシ樹脂とウレタン変性エポキシ樹脂の合計１００重量部当り１００〜９００重量部、好ましくは１５０〜７００重量部、さらに好ましくは２００〜６００重量部、特に好ましくは２５０〜５００重量部で含有する。
【００４５】
また、ビスフェノール型エポキシ樹脂とウレタン変性エポキシ樹脂の割合は、両者の合計１００重量部において前者が１０〜９０重量部そして後者が９０〜１０重量部が好ましい。
【００４６】
本発明の組成物は、場合により硬化物の耐磨耗性をさらに向上させるために、例えば第２酸化鉄粒子、シリカ粒子、ステンレス粉およびシリコンカーバイトウイスカーよりなる群から選ばれる少なくとも１種の他の粒子をアルミナ１００重量部に対し１００重量部以下でさらに含有することができる。上記他の粒子は例えば平均粒径０．５〜３００μｍのものが好ましく用いられる。
【００４７】
本発明の組成物は、ポリアミンからなる硬化剤と混合せしめることにより、硬化させることができる。本発明の組成物を硬化させるためのジアミンとしては、下記式（３）
【００４８】
【化９】

【００４９】
ここで、Ａはポリアミンから２つのアミノ基を除去した骨格を表し、Ｒは２価の有機であり、ｔは１〜１０の数である、
で表わされる化合物が好ましく用いられる。
【００５０】
上記式（３）中、Ａはポリアミンから２つのアミノ基を除去した骨格であり、Ｒは２価の有機基であり、ジカルボン酸から２つのカルボキシル基を除去した骨格に相当する。
【００５１】
骨格Ａとしては、例えばジエチレントリアミン、トリエチレンテトラミンの如きポリアミンまたはｍ−キシリレンジアミンの如きキシリレンジアミンに由来するものが好ましく、骨格Ｒとしては下記式
【００５２】
【化１０】

【００５３】
で表わされるダイマー酸に由来するものが好ましい。
【００５４】
上記式（３）で表される化合物としては、例えば下記式（３）−１
H₂NC₂H₄NHC₂H₄NH-(CO-R¹-CONHC₂H₄NHC₂H₄NH)_t-H
【００５５】
ここで、Ｒ¹はダイマー酸に由来する骨格であり、ｔは４〜５の数である、
で表わされるポリアミンおよび下記式（３）−２
【００５６】
【化１１】

【００５７】
ここで、Ｒ²はダイマー酸に由来する骨格であり、ｎは０．５〜３の数である、で表わされるジアミンを好ましいものとして挙げることができる。
【００５８】
硬化剤としては、上記式（３）−１で表されるポリアミンと上記式（３）−２で表されるジアミンとを組合せて用いるのが好ましく、とりわけ上記式（３）−２で表されるジアミンが両者の合計１００重量部に基づいて１０〜９０重量部の組合せで用いるのが特に好ましい。
【００５９】
本発明の組成物は、組成物１００重量部当り上記硬化剤１０〜４０重量部、好ましくは１１〜３０重量部、より好ましくは１２〜２５重量部と混合することにより、硬化物に変換される。
【００６０】
本発明の組成物の硬化剤の混合物は、硬化する前に補修を必要とする箇所例えばセラミック、金属、コンクリート等の欠損部や亀裂部に、例えば塗布あるいは充填等により施して、その場で硬化させることにより、強固な硬化物に変換されるので、補修を必要とする箇所を修復することができる。
【００６１】
本発明の組成物は、できるだけ硬化物とする直前に硬化剤と混合するのが好ましい。
【００６２】
そのような混合物の調製は、本発明によれば、本発明の組成物と硬化剤を分離された状態で、例えば別個の異なる容器に充填された状態で、含有するキットにより、有利に行うことができる。かかるキットは、例えば金属補修用としてあるいは土木補修用として用いられる。
【００６３】
【実施例】
実施例１
ビスフェノール型エポキシ樹脂（旭電化工業（株）製品、アデカレジンＥＰ−４１００）２０重量部、ウレタン変性エポキシ樹脂（旭電化工業（株）製品、ＥＰＵ−７８−１１）８０重量部およびシランカップリング剤（γ−グリシドキシプロピルトリメトキシシラン）で表面処理された平均粒径１１μｍのアルミナ粉末（住友化学工業（株）製品、ＡＬ−３３）３３１重量部を、ニーダー中で５０分間混練して組成物を得た。
【００６４】
この組成物１００重量部を、前記式（３）−１で表されるポリアミン（旭電化工業（株）製品、ＥＨ−６４５）４．８７重量部および前記式（３）−２で表されるジアミン（旭電化工業（株）製品、ＥＨ−３０３）１１．３７重量部と混練し硬化性樹脂組成物を得た。
【００６５】
一方、長さ１００ｍｍ、幅２５ｍｍ、厚さ１．５ｍｍのステンレス＃３０４板から長さ方向一端から１．５ｍｍの部分を厚さ０．１ｍｍ切削したものを２枚（アルカリ洗滌水中、３０分間超音波処理し、流水で５分間洗滌し、乾燥したもの）準備した。
【００６６】
切削部分を上方にしてその１枚を平板上に載置し、切削部分以外の部分（厚さ１．５ｍｍの部分）の上に、厚さ１．５ｍｍのステンレス板を重ねた。他方、厚さ０．３ｍｍの銅板の上に厚さ１．５ｍｍのステンレス板を重ね合せたものを、前記ステンレス板の切削部位に隣接させた。かくして形成された凹部に、前記硬化性樹脂組成物０．５６ｇを充填したのち、この充填物を、切削部分を持つもう一方のステンレス板の切削部位で覆うように、前記銅板上に重ね合せたステンレス板上に載置した。
【００６７】
かくして得られた組み立て物の上に、長さ１００ｍｍ、幅２５ｍｍ、厚さ１．５ｍｍのステンレス板５枚を重ね、さらにその上に荷重約０．５ｋｇを負荷した。このような組立ての状態を図１に示した。この状態で、表１に記載の時間、３０℃で放置したのち、各試験片についてＪＩＳ Ｋ ６８５０に従い引張剪断強さを測定した。この試験片は、図１において上記切削部を含む２枚のステンレス板（１）とこの切削部における硬化した組成物（４）とからなる。
【００６８】
別に、上記硬化性樹脂組成物を、縦２５ｍｍ、横２０ｍｍ、深さ１４ｍｍのアクリル枠に充填し、３０℃で５日間放置した。得られた硬化物の下面について、縦２５ｍｍ方向に幅１２ｍｍの＃６００研磨紙で６００往復研磨した（スガ試験機（株）製品、ＮＵＳ−ＩＳＯ−３磨耗試験機使用）。ＪＩＳ Ｈ ８５０３に従い、磨耗量を試験前後の重量差から求めた。これらの結果を表３に示した。
【００６９】
【表１】

【００７０】
【表２】

【００７１】
【表３】

【００７２】
実施例２〜８および比較例１、２
実施例１における組成物および硬化剤を、それぞれ表１および表２に記載の組成物および硬化剤を表３に示した組合せに変えた他は、実施例１と同様に行った。結果を表３に示した。
【００７３】
【発明の効果】
本発明によれば、例えば金属、セラミック、コンクリートの亀裂部や欠損部に充填して補修するために好適に使用することができ、作業性に優れ、被補修部への接着強度、耐磨耗性あるいは耐久性に優れしかも比較的短時間の硬化でも加工性を持つ硬化物を与えることのできるエポキシ系硬化性組成物が得られる。本発明のこの組成物は、補修現場において容易に使用することができる。
【図面の簡単な説明】
【図１】本発明の組成物から、引張剪断力を測定するための硬化試験片の作成および組立てを示す概略断面図である。
【符号の説明】
１ 一端から１．５ｍｍの部分を厚さ０．１ｍｍ切削したステンレス板
２ 厚さ１．５ｍｍのステンレス板
３ 厚さ０．３ｍｍの鋼板
４ 硬化した組成物[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an epoxy-based curable resin composition, a method for producing a cured product, a kit for producing a cured product for repair, and a repair method. More specifically, an epoxy-based curable resin composition which gives a cured product excellent in adhesive strength, abrasion resistance and durability for repairing cracks and defects in ceramics, metals, concrete, etc. The present invention relates to a manufacturing method, a kit, and a repair method for the product.
[0002]
[Prior art]
Epoxy resin-based repair agents containing epoxy resin as a main component have the property of being cured by being mixed with a curing agent when used, so they are widely used as a metal repair agent for emergency treatment in various industries, mainly for industrial use. Has been awarded.
[0003]
Patent Document 1 discloses an abrasion-resistant repair agent in which a matrix composed of an epoxy resin, a curing agent, and ceramic cotton is mixed with particles having abrasion resistance having a higher specific gravity than the epoxy resin. This repair agent is characterized by using a ceramic cotton matrix to prevent sedimentation or separation of abrasion-resistant particles having a large specific gravity during the epoxy resin curing process and to prevent drooling. I do.
[0004]
Conventional epoxy resin-based repairing agents, including such repairing agents, are too viscous and may cause cavities inside the repair due to air bubbles mixed during mixing during filling repair, making it difficult to repair details down Had the problem that
[0005]
In addition, epoxy resin-based repair agents have problems such as poor reliability due to low adhesive strength, poor workability due to high viscosity, and easy difference in quality after construction due to the skill of workers. There has been a strong need in the art for the development of an epoxy resin-based repairing agent that solves these problems and is excellent in productivity, reliability, quality, etc., and suitable for filling and repairing.
[0006]
[Patent Document 1]
JP-A-61-188427
[Problems to be solved by the invention]
An object of the present invention is to provide a novel epoxy-based curable resin composition having excellent workability.
[0008]
Another object of the present invention is to provide an epoxy-based curable resin composition that is suitably used for filling and repairing cracks and defects in ceramics, metals, and concrete.
[0009]
Still another object of the present invention is to provide a cured product in a repaired part having a shear strength, for example, 70 N / cm ² or more that can withstand processing, for example, cutting or polishing, in a relatively short time, for example, 3 hours after construction on site. It is another object of the present invention to provide an epoxy-based curable composition that can exhibit high shear strength, for example, 700 N / cm ² or more after a long time.
[0010]
Still another object of the present invention is to provide an epoxy-based curable resin composition which gives a cured product having excellent adhesion strength to a repaired part, abrasion resistance and durability.
[0011]
Still another object of the present invention is to provide a method for producing a cured product having the above-mentioned excellent performance from the epoxy-based curable resin composition of the present invention.
[0012]
Still another object of the present invention is to provide a metal repair kit and a civil engineering repair kit suitable for repairing a cured product from the epoxy-based curable resin composition of the present invention, particularly suitable for on-site preparation. Is to do.
[0013]
Still another object of the present invention is to provide a repair method for repairing a defective portion or the like by using the epoxy-based curable resin composition of the present invention.
[0014]
Still other objects and advantages of the present invention will become apparent from the following description.
[0015]
[Means for Solving the Problems]
According to the present invention, the above objects and advantages of the present invention are as follows. First, the present invention comprises a bisphenol-type epoxy resin, a urethane-modified epoxy resin and alumina, and the content of alumina is the same as that of the bisphenol-type epoxy resin and the urethane-modified epoxy resin. Achieved by a curable resin composition that is 100 to 900 parts by weight per 100 parts by weight of total resin.
[0016]
According to the present invention, the above object and advantages of the present invention are, secondly, 100 parts by weight of the above-mentioned epoxy-based curable resin composition of the present invention and the following formula (3).
[0017]
Embedded image

[0018]
Here, A represents a skeleton obtained by removing two amino groups from a polyamine, R is a divalent organic, and t is a number of 1 to 10.
Is obtained by mixing 10 to 40 parts by weight of a curing agent comprising a compound represented by the formula:
[0019]
According to the present invention, the above object and advantages of the present invention are, thirdly, a metal repair kit or civil engineering repair containing the epoxy curable resin composition of the present invention and the above curing agent in a separated state. Achieved by the kit.
[0020]
Finally, according to the present invention, the above objects and advantages of the present invention are achieved by mixing 100 parts by weight of the epoxy-based curable resin composition of the present invention with 10 to 40 parts by weight of the above curing agent, and the resulting mixture is obtained. This is achieved by a repair method characterized in that the material is applied to the area in need of repair before it is hardened and then hardened there.
[0021]
Preferred Embodiment of the Invention
Hereinafter, the present invention will be described in detail. First, the epoxy-based curable resin composition of the present invention (hereinafter, sometimes referred to as the composition of the present invention) will be described.
[0022]
As described above, the composition of the present invention comprises a bisphenol-type epoxy resin, a urethane-modified epoxy resin, and alumina. As the bisphenol type epoxy resin, for example, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are preferably used. These can be used alone or in combination of two or more.
[0023]
As the bisphenol type epoxy resin, for example, the following formula (1)
[0024]
Embedded image

[0025]
Here, A represents a skeleton obtained by removing two hydroxyl groups from bisphenol, and m is a number from 0 to 1.
[0026]
The compound represented by is preferably used. The bisphenol A type epoxy resin has a structure in which A in formula (1) above is obtained by removing two hydroxyl groups from bisphenol A, and the bisphenol F type epoxy resin has A in which two hydroxyl groups are removed from bisphenol F. It is a skeleton. These bisphenol-type epoxy resins can be obtained as commercial products such as EP-4100 and EP-4901 of Asahi Denka Kogyo KK or Epicoat 828 of Yuka Shell Epoxy KK.
[0027]
As the urethane-modified epoxy resin, for example, a urethane-modified bisphenol A epoxy resin and a urethane-modified bisphenol F epoxy resin are preferably used. These can be used alone or in combination of two or more.
[0028]
As the urethane-modified bisphenol resin, for example, the following formula (2)
[0029]
Embedded image

[0030]
Here, the definition of A is the same as in the above formula (1), B is a divalent organic group, and n and q are each independently a number from 0 to 1.
[0031]
The compound represented by is preferably used. The urethane-modified epoxy resin has a structure in which A in formula (2) above is obtained by removing two hydroxyl groups from bisphenol A, and the bisphenol F type epoxy resin has a structure in which A is obtained by removing two hydroxyl groups from bisphenol F. Things.
[0032]
In the above formula (2), B is a divalent organic group. For example, diisocyanate which is a reaction product of 1 mol of a polyalkylene glycol such as polyethylene glycol or polypropylene glycol and 2 mol of an aromatic diisocyanate such as toluene diisocyanate A skeleton obtained by removing two isocyanate groups from a compound can be given. Of these, the following formula:
Embedded image

[0034]
The skeleton derived from the reaction product of polyoxypropylene and toluene diisocyanate having preferably 10 to 100, more preferably 20 to 90, and particularly preferably 30 to 80 the number of oxypropylene repeating units represented by
[0035]
As the urethane-modified epoxy resin represented by the above formula (2), for example, the following formula:
Embedded image

[0037]
Here, m is a number of 0 to 1, and the sum of n1 and n2 is 50 to 60.
[0038]
The compound represented by is preferably used. These urethane-modified epoxy resins can be obtained as commercial products such as Adeka Resin EPU-78-11 manufactured by Asahi Denka Kogyo KK.
[0039]
As alumina, for example, aggregated particles having an average particle size of 5 to 100 μm, preferably 10 to 80 μm are preferably used.
[0040]
Alumina can be used after surface treatment with a silane coupling agent in advance. By using alumina which has been surface-treated in advance, even if it contains a high content of alumina, it is well compatible with the resin component, and it is easy to avoid separation or sedimentation before curing, for example, during storage. Will be able to
[0041]
Epoxysilane is preferably used as the silane coupling agent. Examples of the epoxysilane include 2- (3,4-epoxycyclohexyl) ethyltri (C ₁ -C ₄ alkoxy) silane, γ-glycidoxypropyltri (C ₁ -C ₄ alkoxy) silane, γ-glycidoxypropyl C ₁ -C ₂ alkyldi (C ₁ -C ₄ alkoxy) silanes can be mentioned.
[0042]
More specifically, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane Silane can be mentioned.
[0043]
Of the above, γ-glycidoxypropyltri (C ₁ -C ₄ alkoxy) silane is preferred, and γ-glycidoxypropyltri (methoxy or ethoxy) silane is particularly preferred.
[0044]
The composition of the present invention comprises alumina in an amount of 100 to 900 parts by weight, preferably 150 to 700 parts by weight, more preferably 200 to 600 parts by weight, particularly preferably 200 to 600 parts by weight per 100 parts by weight of the bisphenol-type epoxy resin and the urethane-modified epoxy resin in total. Is contained at 250 to 500 parts by weight.
[0045]
Further, the ratio of the bisphenol-type epoxy resin to the urethane-modified epoxy resin is preferably 10 to 90 parts by weight and 90 to 10 parts by weight of the latter in a total of 100 parts by weight.
[0046]
The composition of the present invention may contain at least one kind selected from the group consisting of, for example, ferric oxide particles, silica particles, stainless steel powder, and silicon carbide whiskers in order to further improve the abrasion resistance of the cured product. Other particles may be further contained in an amount of 100 parts by weight or less based on 100 parts by weight of alumina. As the other particles, those having an average particle size of 0.5 to 300 μm are preferably used.
[0047]
The composition of the present invention can be cured by mixing with a curing agent comprising a polyamine. As the diamine for curing the composition of the present invention, the following formula (3)
[0048]
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[0049]
Here, A represents a skeleton obtained by removing two amino groups from a polyamine, R is a divalent organic, and t is a number of 1 to 10.
The compound represented by is preferably used.
[0050]
In the above formula (3), A is a skeleton obtained by removing two amino groups from a polyamine, and R is a divalent organic group, and corresponds to a skeleton obtained by removing two carboxyl groups from a dicarboxylic acid.
[0051]
The skeleton A is preferably derived from a polyamine such as diethylenetriamine or triethylenetetramine or a xylylenediamine such as m-xylylenediamine, and the skeleton R is represented by the following formula:
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[0053]
Those derived from the dimer acid represented by are preferred.
[0054]
As the compound represented by the above formula (3), for example, the following formula (3) -1
H ₂ NC ₂ H ₄ NHC ₂ H ₄ NH- (CO-R ¹ -CONHC ₂ H ₄ NHC ₂ H ₄ NH) _t -H
[0055]
Here, R ¹ is a skeleton derived from dimer acid, and t is a number of 4 to 5,
And a polyamine represented by the following formula (3) -2:
[0056]
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[0057]
Here, R ² is a skeleton derived from dimer acid, and n is a number of 0.5 to 3, and a diamine represented by the following formula can be mentioned as a preferable example.
[0058]
As the curing agent, it is preferable to use a combination of the polyamine represented by the above formula (3) -1 and the diamine represented by the above formula (3) -2, and particularly preferably represented by the above formula (3) -2. It is particularly preferred that the diamine is used in a combination of 10 to 90 parts by weight based on a total of 100 parts by weight of both.
[0059]
The composition of the present invention is converted into a cured product by mixing with 10 to 40 parts by weight of the above curing agent, preferably 11 to 30 parts by weight, more preferably 12 to 25 parts by weight per 100 parts by weight of the composition. .
[0060]
The mixture of the curing agent of the composition of the present invention is applied to a portion requiring repair before curing, for example, a defective portion or a crack portion of ceramic, metal, concrete, or the like, for example, by application or filling, and cured in place. By doing so, it is converted into a hard cured product, so that it is possible to repair a portion that needs repair.
[0061]
It is preferable that the composition of the present invention is mixed with a curing agent as soon as possible before forming a cured product.
[0062]
The preparation of such a mixture is, according to the invention, advantageously effected by means of a kit containing the composition of the invention and the curing agent in a separate state, for example, filled in separate containers. Can be. Such a kit is used, for example, for metal repair or civil engineering repair.
[0063]
【Example】
Example 1
20 parts by weight of a bisphenol-type epoxy resin (Adeka Resin EP-4100, a product of Asahi Denka Kogyo Co., Ltd.), 80 parts by weight of a urethane-modified epoxy resin (EPU-78-11, a product of Asahi Denka Kogyo Co., Ltd.), and a silane coupling agent ( 331 parts by weight of alumina powder (AL-33, manufactured by Sumitomo Chemical Co., Ltd.) having an average particle size of 11 μm and surface-treated with γ-glycidoxypropyltrimethoxysilane) is kneaded in a kneader for 50 minutes to obtain a composition. Got.
[0064]
100 parts by weight of this composition are represented by 4.87 parts by weight of a polyamine represented by the formula (3) -1 (a product of Asahi Denka Kogyo KK, EH-645) and represented by the formula (3) -2. The mixture was kneaded with 11.37 parts by weight of a diamine (product of Asahi Denka Kogyo KK, EH-303) to obtain a curable resin composition.
[0065]
On the other hand, two pieces of a stainless steel # 304 plate having a length of 100 mm, a width of 25 mm, and a thickness of 1.5 mm and having a thickness of 1.5 mm cut from a 1.5 mm portion from one end in the length direction (alkaline washing water for more than 30 minutes) Sonicated, washed with running water for 5 minutes, and dried).
[0066]
One of the cut portions was placed on a flat plate with the cut portion facing upward, and a stainless steel plate having a thickness of 1.5 mm was stacked on a portion other than the cut portion (a portion having a thickness of 1.5 mm). On the other hand, a stainless steel plate having a thickness of 1.5 mm was superimposed on a copper plate having a thickness of 0.3 mm, and was made adjacent to a cut portion of the stainless steel plate. After filling the thus formed concave portion with 0.56 g of the curable resin composition, the filled material was overlaid on the copper plate so as to be covered with a cut portion of another stainless plate having a cut portion. Placed on a stainless steel plate.
[0067]
Five stainless plates having a length of 100 mm, a width of 25 mm, and a thickness of 1.5 mm were stacked on the assembly thus obtained, and a load of about 0.5 kg was applied thereon. FIG. 1 shows such an assembled state. In this state, after leaving at 30 ° C. for the time shown in Table 1, the tensile shear strength of each test piece was measured according to JIS K 6850. This test piece is composed of two stainless steel plates (1) including the above-mentioned cut portion in FIG. 1 and a cured composition (4) in the cut portion.
[0068]
Separately, the curable resin composition was filled in an acrylic frame having a length of 25 mm, a width of 20 mm and a depth of 14 mm, and left at 30 ° C. for 5 days. The lower surface of the obtained cured product was polished 600 times reciprocally with # 600 abrasive paper having a width of 12 mm in the vertical direction of 25 mm (using a NUS-ISO-3 abrasion tester manufactured by Suga Test Machine Co., Ltd.). According to JIS H8503, the amount of wear was determined from the difference in weight before and after the test. Table 3 shows the results.
[0069]
[Table 1]

[0070]
[Table 2]

[0071]
[Table 3]

[0072]
Examples 2 to 8 and Comparative Examples 1 and 2
The procedure was performed in the same manner as in Example 1 except that the composition and the curing agent in Example 1 were changed to the combinations shown in Tables 1 and 2 respectively. The results are shown in Table 3.
[0073]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, it can be used suitably, for example, for filling and repairing a crack part or a defect part of metal, ceramic, and concrete, is excellent in workability, adhesive strength to a repaired part, and abrasion resistance. An epoxy-based curable composition which is excellent in heat resistance or durability and can provide a cured product having processability even after curing for a relatively short time is obtained. This composition of the present invention can be easily used at a repair site.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing the preparation and assembly of a cured test piece for measuring tensile shear force from the composition of the present invention.
[Explanation of symbols]
Reference Signs List 1 Stainless steel plate obtained by cutting a portion 1.5 mm from one end to a thickness of 0.1 mm 2 Stainless steel plate 1.5 mm thick 3 Steel plate 0.3 mm thick 4 Cured composition

Claims (13)

A curable resin composition comprising a bisphenol-type epoxy resin, a urethane-modified epoxy resin and alumina, and having an alumina content of 100 to 900 parts by weight per 100 parts by weight of the bisphenol-type epoxy resin and the urethane-modified epoxy resin in total. . 2. The composition according to claim 1, further comprising at least one other particle selected from the group consisting of ferric oxide particles, silica particles, stainless steel powder and silicon carbide whiskers in an amount of 100 parts by weight or less based on 100 parts by weight of alumina. Composition. The composition according to claim 1, wherein the bisphenol type epoxy resin is at least one selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. Bisphenol type epoxy resin has the following formula (1)

Here, A represents a skeleton obtained by removing two hydroxyl groups from bisphenol, and m is a number from 0 to 1.
The composition according to claim 1, which is represented by the formula: The composition according to claim 1, wherein the urethane-modified epoxy resin is at least one selected from the group consisting of a urethane-modified bisphenol A epoxy resin and a urethane-modified bisphenol F epoxy resin. The urethane-modified epoxy resin has the following formula (2)

Here, the definition of A is the same as in the above formula (1), B is a divalent organic group, and n and q are each independently a number from 0 to 1.
The composition according to claim 1, which is represented by the formula: The composition according to claim 1, wherein the alumina has been previously surface-treated with a silane coupling agent. A composition according to claim 7 silane coupling agent is γ- glycidoxypropyltrimethoxysilane (C ₁ -C ₄ alkoxy) silane. The following equation (3)

Here, A represents a skeleton obtained by removing two amino groups from a polyamine, R is a divalent organic, and t is a number of 1 to 10.
A curing agent for curing the composition according to claim 1, comprising at least one compound selected from the group consisting of compounds represented by the formula: 10. A method for producing a cured product, comprising mixing 100 parts by weight of the composition of claim 1 with 10 to 40 parts by weight of the curing agent of claim 9. A metal repair kit comprising the composition of claim 1 and the curing agent of claim 9 in a separated state. A civil engineering repair kit comprising the composition of claim 1 and the curing agent of claim 9 in a separated state. Mixing 100 parts by weight of the composition of claim 1 with 10 to 40 parts by weight of the curing agent of claim 9, applying the resulting mixture to a location requiring repair before curing and curing at that location. Repair method characterized by the following.

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