WO2021019741A1 - Adhesive set - Google Patents

Adhesive set Download PDF

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Publication number
WO2021019741A1
WO2021019741A1 PCT/JP2019/030072 JP2019030072W WO2021019741A1 WO 2021019741 A1 WO2021019741 A1 WO 2021019741A1 JP 2019030072 W JP2019030072 W JP 2019030072W WO 2021019741 A1 WO2021019741 A1 WO 2021019741A1
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Prior art keywords
liquid
adhesive
meth
group
epoxy resin
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PCT/JP2019/030072
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French (fr)
Japanese (ja)
Inventor
昌大 松永
陽介 藤安
雅史 大治
崇司 川守
Original Assignee
昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to PCT/JP2019/030072 priority Critical patent/WO2021019741A1/en
Priority to TW109125857A priority patent/TW202112992A/en
Priority to PCT/JP2020/029218 priority patent/WO2021020506A1/en
Priority to JP2021535422A priority patent/JPWO2021020506A1/ja
Publication of WO2021019741A1 publication Critical patent/WO2021019741A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • This disclosure relates to an adhesive set.
  • a two-component adhesive using a (meth) acrylic monomer is known (for example, Patent Document 1).
  • the polymerization of the (meth) acrylic monomer generally proceeds by a redox catalyst system formed by a polymerization initiator and a reducing agent, and as a result, the polymerization of the (meth) acrylic monomer proceeds.
  • the adhesive cures.
  • One aspect of the present invention is to provide a two-component adhesive which has sufficient curability at room temperature and suppresses dripping when applied to an adherend.
  • One aspect of the present invention is a first liquid containing an acrylic monomer having two or more (meth) acryloyl groups and an epoxy resin having two or more epoxy groups, and any of an epoxy group and a (meth) acryloyl group.
  • an adhesive set comprising a second liquid containing a curing agent containing a compound having a nucleophilic reactive group that originally reacts.
  • a two-component adhesive which has sufficient curability at room temperature and suppresses dripping when applied to an adherend.
  • the adhesive set according to one aspect of the present invention may have excellent characteristics in terms of good ejection property from a nozzle or the like and a sufficiently long pot life.
  • (meth) acryloyl means acryloyl or methacryloyl, and the same applies to other similar expressions.
  • the adhesive set according to one embodiment is a two-component adhesive composed of a first liquid and a second liquid.
  • the first liquid contains an acrylic monomer having two or more (meth) acryloyl groups and an epoxy resin having two or more epoxy groups.
  • the second liquid contains a curing agent containing a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group.
  • the acrylic monomer is a bifunctional or higher functional compound having an acryloyl group, a methacryloyl group, or both of them.
  • the number of (meth) acryloyl groups contained in the acrylic monomer may be 2 to 4.
  • the acrylic monomer may be, for example, a poly (meth) acrylate of an aliphatic polyol.
  • poly (meth) acrylates of aliphatic polyols include diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and the like.
  • bifunctional (meth) acrylic monomers such as polyethylene polypropylene glycol di (meth) acrylates, trifunctional (meth) acrylic monomers such as trimethylolpropane tri (meth) acrylates and pentaerythritol tri (meth) acrylates, and Examples thereof include tetrafunctional (meth) acrylic monomers such as ditrimethylolpropane tetra (meth) acrylate.
  • acrylic monomers include tris (2- (meth) acryloyloxyethyl) isocyanurate, 2,2'-di (meth) acryloyloxydiethyl phosphate, and ethylene oxide-modified di (meth) acrylate. Can be mentioned. These acrylic monomers can be used alone or in combination of two or more.
  • the acrylic monomer may have two or more (meth) acryloyl groups and an epoxy group.
  • a compound having two or more (meth) acryloyl groups and one or more epoxy groups is classified as an acrylic monomer.
  • the acrylic monomer may be a compound having two or more (meth) acryloyl groups and no epoxy group.
  • the epoxy resin may be a bifunctional or higher epoxy resin.
  • the number of epoxy groups contained in the epoxy resin may be 2 to 4.
  • epoxy resins include diglycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and hydrogenated bisphenol A type epoxy resin; phenol novolac.
  • Novolak type epoxy resin such as type epoxy resin and cresol novolac type epoxy resin
  • biphenyl type epoxy resin such as biphenyl type epoxy resin and biphenyl aralkyl type epoxy resin
  • polybasic acid for example, phthalic acid, dimer acid
  • epichlorohydrin examples thereof include a glycidyl ester type epoxy resin which is a reaction product; a glycidyl amine type epoxy resin which is a reaction product of an amine compound (for example, p-aminophenol, diaminodiphenylmethane, isocyanuric acid) and epichlorohydrin; and an aliphatic epoxy resin.
  • the epoxy resin may further have a (meth) acryloyl group.
  • a compound having two or more epoxy groups and one (meth) acryloyl group is classified as an epoxy resin.
  • the epoxy resin may be a compound having two or more epoxy groups and no (meth) acryloyl group.
  • the first liquid may further contain a monofunctional acrylic monomer having one (meth) acryloyl group, a monofunctional epoxy resin having one epoxy group, or both of them.
  • the content of the acrylic monomer having two or more (meth) acryloyl groups in the first liquid is the total amount of the acrylic monomer having two or more (meth) acryloyl groups and the epoxy resin having two or more epoxy groups. It may be 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, or 40 to 60% by mass.
  • the total amount of the acrylic monomer having two or more (meth) acryloyl groups and the epoxy resin having two or more epoxy groups is 50 to 100% by mass and 60 to 100% by mass with respect to the amount of the first liquid. , 70-100% by mass, 80-100% by mass, 85-100% by mass or 90-100% by mass.
  • the curing agent contained in the second liquid is a component that cures a mixture (adhesive) of the first liquid and the second liquid by reacting with an epoxy resin, an acrylic monomer, or both of them.
  • the curing agent contains at least a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group. This compound may have 2 to 4 or 2 to 3 nucleophilic reactive groups.
  • the nucleophilic reactive group may be, for example, an aliphatic amino group or a thiol group. From the viewpoint of reactivity with the (meth) acryloyl group, the nucleophilic reactive group may be an aliphatic amino group.
  • examples of compounds having an aliphatic amino group include aliphatic amine compounds having two or more primary aliphatic amino groups, such as 1,3-bisaminomethylcyclohexane and 1,6-hexanediamine. Can be mentioned.
  • Examples of commercially available products of compounds having an aliphatic amino group include jER Cure 3080 (manufactured by Mitsubishi Chemical Corporation, trade name).
  • the curing agent contained in the second liquid may further contain a compound that substantially reacts only with the epoxy resin.
  • a compound that substantially reacts only with the epoxy resin examples include aromatic amine compounds.
  • the content of the compound having a nucleophilic reactive group in the second liquid is 30 to 100% by mass, 40 to 100% by mass, 50 to 100% by mass, 60 to 100% by mass, based on the amount of the second liquid. It may be 70 to 100% by mass, 80 to 100% by mass, 85 to 100% by mass, or 90 to 100% by mass.
  • the first liquid, the second liquid, or both of them may further contain an inorganic filler.
  • an inorganic filler By blending the inorganic filler, dripping when applied to the adherend can be suppressed more effectively.
  • inorganic fillers include silica particles, calcium carbonate particles, and glass beads.
  • the silica particles may be, for example, an unmodified silica filler, or a silica filler chain-modified with an alkyl chain, a (meth) acryloyl group, or the like.
  • the content of the inorganic filler in the first liquid may be 0 to 30% by mass, 0 to 20% by mass, or 0 to 15% by mass with respect to the amount of the first liquid.
  • the content of the inorganic filler in the second liquid may be 0 to 30% by mass, 0 to 20% by mass, or 0 to 15% by mass with respect to the amount of the second liquid.
  • the content of the inorganic filler in the first liquid and the content of the inorganic filler in the second liquid may be the same or different.
  • the first liquid, the second liquid, or both of them may further contain a silane coupling agent.
  • the silane coupling agent may be, for example, a compound having a hydrolyzable silyl group and a functional group that reacts with at least one of an acrylic monomer, an epoxy resin or a curing agent.
  • the hydrolyzable silyl group is, for example, a group having a silicon atom and 1 to 3 alkoxy groups bonded to the silicon atom.
  • the number of carbon atoms of the alkoxy group bonded to the silicon atom may be, for example, 1 to 4.
  • Examples of a functional group that reacts with at least one of an acrylic monomer or an epoxy resin include an amino group such as a primary amino group and a secondary amino group, an epoxy group, a mercapto group, and a (meth) acryloyl group. ..
  • an amino group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a primary amino group and a secondary amino group
  • an epoxy group such as a mercapto group
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
  • KBM-303 KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-502, KBM-503, KBE-502, KBE-503.
  • the content of the silane coupling agent in the first liquid may be 0 to 5% by mass or 0 to 3% by mass with respect to the amount of the first liquid.
  • the content of the silane coupling agent in the second liquid may be 0 to 5% by mass or 0 to 3% by mass with respect to the amount of the second liquid.
  • the first liquid, the second liquid, or both of them may further contain other components if necessary.
  • other components include pigments (eg carbon black, titanium oxide particles), and elastomers.
  • both the first liquid and the second liquid may contain a pigment.
  • both the first liquid and the second liquid may contain a pigment, in which case the pigment contained in the first liquid and the pigment contained in the second liquid may be different.
  • the adhesive set contains a pigment in this way, when the first liquid and the second liquid are mixed, the mixed state of the first liquid and the second liquid can be visualized. By putting the mixed liquid of the first liquid and the second liquid in a mixed state in which the pigment is sufficiently uniformly dispersed, a better adhesive force tends to be obtained.
  • the adhesive set exemplified above is desired to have two or more adherends and an adhesive layer for adhering them by adhering the adherends to each other with an adhesive which is a mixture of the first liquid and the second liquid. It is used to obtain an adhesive of.
  • the adherend may be, for example, a molded body of metal such as steel, iron, copper, tinplate, aluminum, stainless steel, resin, or carbon fiber reinforced plastic (CFRP).
  • CFRP carbon fiber reinforced plastic
  • the two or more adherends can be molded bodies of the same or different materials from each other.
  • the method of obtaining an adhesive having two adherends using an adhesive set is, for example, arranging the two adherends with a gap, and the first liquid and the first liquid in the gap between the two adherends. It involves injecting a second solution and curing an adhesive that is a mixture of the first and second solutions.
  • the first liquid and the second liquid may be mixed substantially at the same time as being injected into the gap between the two adherends, or may be mixed and then injected between the two adherends.
  • the first liquid and the second liquid, or a mixture (adhesive) thereof, are injected between the two adherends using, for example, a mixing nozzle.
  • the method of obtaining an adhesive is to apply an adhesive which is a mixture of the first liquid and the second liquid on one adherend, and to sandwich the applied adhesive between one adherend and the other. It may include affixing the adherend to the adherend and then curing the adhesive. As the adhesive cures, it forms an adhesive layer that intervenes between the two adherends and adheres them.
  • the mixing ratio of the first liquid and the second liquid is determined by considering the stoichiometric ratio of the reaction between the acrylic monomer and epoxy resin contained in the first liquid and the curing agent contained in the second liquid. Adjusted to cure properly.
  • the volume ratio of the first liquid to the second liquid may be 0.5 to 5.0.
  • Curing conditions are adjusted so that the adhesive cures properly.
  • the adhesive may be cured in an environment of 10 to 40 ° C.
  • the curing time is adjusted, for example, between 1 hour and 1 week.
  • the adhesive may be heated, in which case the heating temperature may be, for example, 40-120 ° C.

Abstract

Disclosed is an adhesive set comprising a first fluid, which comprises an acrylic monomer having two or more (meth)acryloyl groups and an epoxy resin having two or more epoxy groups, and a second fluid, which comprises a curing agent comprising a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth)acryloyl group.

Description

接着剤セットAdhesive set
　本開示は、接着剤セットに関する。 This disclosure relates to an adhesive set.
　従来、接着剤の一種として、（メタ）アクリル系モノマーを用いた二液型接着剤が知られている（例えば特許文献１）。（メタ）アクリル系モノマーを用いた従来の二液型接着剤の場合、一般に、重合開始剤と還元剤とで形成されるレドックス触媒系によって（メタ）アクリル系モノマーの重合が進行し、その結果、接着剤が硬化する。 Conventionally, as a kind of adhesive, a two-component adhesive using a (meth) acrylic monomer is known (for example, Patent Document 1). In the case of a conventional two-component adhesive using a (meth) acrylic monomer, the polymerization of the (meth) acrylic monomer generally proceeds by a redox catalyst system formed by a polymerization initiator and a reducing agent, and as a result, the polymerization of the (meth) acrylic monomer proceeds. , The adhesive cures.
特開２０１３－１１７０１１号公報Japanese Unexamined Patent Publication No. 2013-117011
　本発明の一側面は、室温で十分な硬化性を有するとともに、被着体に塗布されたときの液だれが抑制された二液型接着剤を提供する。 One aspect of the present invention is to provide a two-component adhesive which has sufficient curability at room temperature and suppresses dripping when applied to an adherend.
　本発明の一側面は、２個以上の（メタ）アクリロイル基を有するアクリルモノマー、及び２個以上のエポキシ基を有するエポキシ樹脂を含有する第一液と、エポキシ基及び（メタ）アクリロイル基のいずれもと反応する求核性反応基を有する化合物を含む硬化剤を含有する第二液と、を備える、接着剤セットを提供する。 One aspect of the present invention is a first liquid containing an acrylic monomer having two or more (meth) acryloyl groups and an epoxy resin having two or more epoxy groups, and any of an epoxy group and a (meth) acryloyl group. Provided is an adhesive set comprising a second liquid containing a curing agent containing a compound having a nucleophilic reactive group that originally reacts.
　本発明の一側面によれば、室温で十分な硬化性を有するとともに、被着体に塗布されたときの液だれが抑制された二液型の接着剤が提供される。本発明の一側面に係る接着剤セットは、ノズル等からの良好な吐出性、及び十分に長い可使時間の点でも優れた特性を有し得る。 According to one aspect of the present invention, there is provided a two-component adhesive which has sufficient curability at room temperature and suppresses dripping when applied to an adherend. The adhesive set according to one aspect of the present invention may have excellent characteristics in terms of good ejection property from a nozzle or the like and a sufficiently long pot life.
　以下、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。本明細書中、（メタ）アクリロイルは、アクリロイル又はメタクリロイルを意味し、これはその他の類似表現についても同様である。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the present specification, (meth) acryloyl means acryloyl or methacryloyl, and the same applies to other similar expressions.
　一実施形態に係る接着剤セットは、第一液及び第二液から構成される二液型の接着剤である。第一液は、２個以上の（メタ）アクリロイル基を有するアクリルモノマー、及び２個以上のエポキシ基を有するエポキシ樹脂を含有する。第二液は、エポキシ基及び（メタ）アクリロイル基のいずれもと反応する求核性反応基を有する化合物を含む硬化剤を含有する。 The adhesive set according to one embodiment is a two-component adhesive composed of a first liquid and a second liquid. The first liquid contains an acrylic monomer having two or more (meth) acryloyl groups and an epoxy resin having two or more epoxy groups. The second liquid contains a curing agent containing a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group.
　アクリルモノマーは、アクリロイル基、メタクリロイル基又はこれらの両方を有する２官能以上の化合物である。アクリルモノマーが有する（メタ）アクリロイル基の数は２～４であってもよい。 The acrylic monomer is a bifunctional or higher functional compound having an acryloyl group, a methacryloyl group, or both of them. The number of (meth) acryloyl groups contained in the acrylic monomer may be 2 to 4.
　アクリルモノマーは、例えば、脂肪族ポリオールのポリ（メタ）アクリレートであってもよい。脂肪族ポリオールのポリ（メタ）アクリレートの例としては、ジエチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、及びポリエチレンポリプロピレングリコールジ（メタ）アクリレート等の二官能（メタ）アクリルモノマー、トリメチロールプロパントリ（メタ）アクリレート、及びペンタエリスルトールトリ（メタ）アクリレート等の三官能（メタ）アクリルモノマー、並びに、ジトリメチロールプロパンテトラ（メタ）アクリレート等の四官能（メタ）アクリルモノマーが挙げられる。アクリルモノマーの他の例としては、トリス（２－（メタ）アクリロイルオキシエチル）イソシアヌレート、２，２’－ジ（メタ）アクリロイロキシジエチルホスフェート、及びエチレンオキサイド変性リン酸ジ（メタ）アクリレートが挙げられる。これらのアクリルモノマーは、１種単独で又は２種以上を組み合わせて用いることができる。 The acrylic monomer may be, for example, a poly (meth) acrylate of an aliphatic polyol. Examples of poly (meth) acrylates of aliphatic polyols include diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and the like. And bifunctional (meth) acrylic monomers such as polyethylene polypropylene glycol di (meth) acrylates, trifunctional (meth) acrylic monomers such as trimethylolpropane tri (meth) acrylates and pentaerythritol tri (meth) acrylates, and Examples thereof include tetrafunctional (meth) acrylic monomers such as ditrimethylolpropane tetra (meth) acrylate. Other examples of acrylic monomers include tris (2- (meth) acryloyloxyethyl) isocyanurate, 2,2'-di (meth) acryloyloxydiethyl phosphate, and ethylene oxide-modified di (meth) acrylate. Can be mentioned. These acrylic monomers can be used alone or in combination of two or more.
　アクリルモノマーが、２個以上の（メタ）アクリロイル基と、エポキシ基とを有していてもよい。本明細書において、２個以上の（メタ）アクリロイル基と、１個以上のエポキシ基とを有する化合物は、アクリルモノマーに分類される。アクリルモノマーが、２個以上の（メタ）アクリロイル基を有し、エポキシ基を有しない化合物であってもよい。 The acrylic monomer may have two or more (meth) acryloyl groups and an epoxy group. In the present specification, a compound having two or more (meth) acryloyl groups and one or more epoxy groups is classified as an acrylic monomer. The acrylic monomer may be a compound having two or more (meth) acryloyl groups and no epoxy group.
　エポキシ樹脂は、二官能以上のエポキシ樹脂であればよい。エポキシ樹脂が有するエポキシ基の数が２～４であってもよい。 The epoxy resin may be a bifunctional or higher epoxy resin. The number of epoxy groups contained in the epoxy resin may be 2 to 4.
　エポキシ樹脂の例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、及び水添ビスフェノールＡ型エポキシ樹脂等のジグリシジルエーテル型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；ビフェニル型エポキシ樹脂、及びビフェニルアラルキル型エポキシ樹脂等のビフェニル型エポキシ樹脂；多塩基酸（例えばフタル酸、ダイマー酸）とエピクロルヒドリンとの反応生成物であるグリシジルエステル型エポキシ樹脂；アミン化合物（例えばｐ－アミノフェノール、ジアミノジフェニルメタン、イソシアヌル酸）とエピクロルヒドリンとの反応生成物であるグリシジルアミン型エポキシ樹脂；並びに脂肪族エポキシ樹脂が挙げられる。 Examples of epoxy resins include diglycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and hydrogenated bisphenol A type epoxy resin; phenol novolac. Novolak type epoxy resin such as type epoxy resin and cresol novolac type epoxy resin; biphenyl type epoxy resin such as biphenyl type epoxy resin and biphenyl aralkyl type epoxy resin; polybasic acid (for example, phthalic acid, dimer acid) and epichlorohydrin Examples thereof include a glycidyl ester type epoxy resin which is a reaction product; a glycidyl amine type epoxy resin which is a reaction product of an amine compound (for example, p-aminophenol, diaminodiphenylmethane, isocyanuric acid) and epichlorohydrin; and an aliphatic epoxy resin.
　エポキシ樹脂が、（メタ）アクリロイル基を更に有していてもよい。本明細書において、２個以上のエポキシ基と、１個の（メタ）アクリロイル基とを有する化合物は、エポキシ樹脂に分類される。エポキシ樹脂が、２個以上のエポキシ基を有し、（メタ）アクリロイル基を有しない化合物であってもよい。 The epoxy resin may further have a (meth) acryloyl group. In the present specification, a compound having two or more epoxy groups and one (meth) acryloyl group is classified as an epoxy resin. The epoxy resin may be a compound having two or more epoxy groups and no (meth) acryloyl group.
　第一液が、１個の（メタ）アクリロイル基を有する単官能アクリルモノマー、１個のエポキシ基を有する単官能エポキシ樹脂、又はこれらの両方を更に含有してもよい。 The first liquid may further contain a monofunctional acrylic monomer having one (meth) acryloyl group, a monofunctional epoxy resin having one epoxy group, or both of them.
　第一液における２個以上の（メタ）アクリロイル基を有するアクリルモノマーの含有量は、２個以上の（メタ）アクリロイル基を有するアクリルモノマー及び２個位以上のエポキシ基を有するエポキシ樹脂の合計量に対して、１０～９０質量％、２０～８０質量％、３０～７０質量％、又は４０～６０質量％であってもよい。２個以上の（メタ）アクリロイル基を有するアクリルモノマー及び２個位以上のエポキシ基を有するエポキシ樹脂の合計量は、第一液の量に対して、５０～１００質量％、６０～１００質量％、７０～１００質量％、８０～１００質量％、８５～１００質量％又は９０～１００質量％であってもよい。 The content of the acrylic monomer having two or more (meth) acryloyl groups in the first liquid is the total amount of the acrylic monomer having two or more (meth) acryloyl groups and the epoxy resin having two or more epoxy groups. It may be 10 to 90% by mass, 20 to 80% by mass, 30 to 70% by mass, or 40 to 60% by mass. The total amount of the acrylic monomer having two or more (meth) acryloyl groups and the epoxy resin having two or more epoxy groups is 50 to 100% by mass and 60 to 100% by mass with respect to the amount of the first liquid. , 70-100% by mass, 80-100% by mass, 85-100% by mass or 90-100% by mass.
　第二液に含まれる硬化剤は、エポキシ樹脂、アクリルモノマー、又はこれらの両方と反応することにより、第一液と第２液との混合物（接着剤）を硬化させる成分である。硬化剤は、少なくとも、エポキシ基及び（メタ）アクリロイル基のいずれもと反応する求核性反応基を有する化合物を含む。この化合物は、２～４個、又は２～３個の求核性反応基を有していてもよい。 The curing agent contained in the second liquid is a component that cures a mixture (adhesive) of the first liquid and the second liquid by reacting with an epoxy resin, an acrylic monomer, or both of them. The curing agent contains at least a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group. This compound may have 2 to 4 or 2 to 3 nucleophilic reactive groups.
　求核性反応基は、例えば、脂肪族アミノ基、又はチオール基であってもよい。（メタ）アクリロイル基との反応性の観点から、求核性反応基が脂肪族アミノ基であってもよい。脂肪族アミノ基を有する化合物の例としては、１，３－ビスアミノメチルシクロヘキサン、及び１，６－ヘキサンジアミンのような、２個以上の第一級脂肪族アミノ基を有する脂肪族アミン化合物が挙げられる。脂肪族アミノ基を有する化合物の市販品の例としては、ｊＥＲキュア３０８０（三菱ケミカル株式会社製、商品名）が挙げられる。 The nucleophilic reactive group may be, for example, an aliphatic amino group or a thiol group. From the viewpoint of reactivity with the (meth) acryloyl group, the nucleophilic reactive group may be an aliphatic amino group. Examples of compounds having an aliphatic amino group include aliphatic amine compounds having two or more primary aliphatic amino groups, such as 1,3-bisaminomethylcyclohexane and 1,6-hexanediamine. Can be mentioned. Examples of commercially available products of compounds having an aliphatic amino group include jER Cure 3080 (manufactured by Mitsubishi Chemical Corporation, trade name).
　第二液に含まれる硬化剤が、実質的にエポキシ樹脂のみと反応する化合物を更に含んでいてもよい。そのような化合物の例としては、芳香族アミン化合物が挙げられる。 The curing agent contained in the second liquid may further contain a compound that substantially reacts only with the epoxy resin. Examples of such compounds include aromatic amine compounds.
　第二液における求核性反応基を有する化合物の含有量は、第二液の量に対して、３０～１００質量％、４０～１００質量％、５０～１００質量％、６０～１００質量％、７０～１００質量％、８０～１００質量％、８５～１００質量％、又は９０～１００質量％であってもよい。 The content of the compound having a nucleophilic reactive group in the second liquid is 30 to 100% by mass, 40 to 100% by mass, 50 to 100% by mass, 60 to 100% by mass, based on the amount of the second liquid. It may be 70 to 100% by mass, 80 to 100% by mass, 85 to 100% by mass, or 90 to 100% by mass.
　第一液、第二液又はこれらの両方が、無機充填剤を更に含有していてもよい。無機充填剤の配合により、被着体に塗布されたときの液だれがより一層効果的に抑制され得る。無機充填剤の例としては、シリカ粒子、炭酸カルシウム粒子、及びガラスビーズが挙げられる。シリカ粒子は、例えば、未修飾シリカフィラであってもよいし、アルキル鎖若しくは（メタ）アクリロイル基等で鎖修されたシリカフィラであってもよい。 The first liquid, the second liquid, or both of them may further contain an inorganic filler. By blending the inorganic filler, dripping when applied to the adherend can be suppressed more effectively. Examples of inorganic fillers include silica particles, calcium carbonate particles, and glass beads. The silica particles may be, for example, an unmodified silica filler, or a silica filler chain-modified with an alkyl chain, a (meth) acryloyl group, or the like.
　第一液における無機充填剤の含有量は、第一液の量に対して、０～３０質量％、０～２０質量％、又は０～１５質量％であってもよい。第二液における無機充填剤の含有量は、第二液の量に対して、０～３０質量％、０～２０質量％、又は０～１５質量％であってもよい。第一液における無機充填剤の含有量と、第二液における無機充填剤の含有量とは、同じでも異なっていてもよい。 The content of the inorganic filler in the first liquid may be 0 to 30% by mass, 0 to 20% by mass, or 0 to 15% by mass with respect to the amount of the first liquid. The content of the inorganic filler in the second liquid may be 0 to 30% by mass, 0 to 20% by mass, or 0 to 15% by mass with respect to the amount of the second liquid. The content of the inorganic filler in the first liquid and the content of the inorganic filler in the second liquid may be the same or different.
　第一液、第二液又はこれらの両方が、シランカップリング剤を更に含有していてもよい。シランカップリング剤は、例えば、加水分解性シリル基と、アクリルモノマー、エポキシ樹脂又は硬化剤のうち少なくとも一つと反応する官能基とを有する化合物であってもよい。加水分解性シリル基は、例えば、ケイ素原子と、該ケイ素原子に結合した１～３個のアルコキシ基とを有する基である。ケイ素原子に結合したアルコキシ基の炭素数は、例えば１～４であってよい。アクリルモノマー又はエポキシ樹脂のうち少なくとも一方と反応する官能基の例としては、第一級アミノ基及び第二級アミノ基等のアミノ基、エポキシ基、メルカプト基、並びに（メタ）アクリロイル基が挙げられる。本明細書において、加水分解性シリル基及び（メタ）アクリロイル基を有する化合物は、シランカップリング剤に分類される。 The first liquid, the second liquid, or both of them may further contain a silane coupling agent. The silane coupling agent may be, for example, a compound having a hydrolyzable silyl group and a functional group that reacts with at least one of an acrylic monomer, an epoxy resin or a curing agent. The hydrolyzable silyl group is, for example, a group having a silicon atom and 1 to 3 alkoxy groups bonded to the silicon atom. The number of carbon atoms of the alkoxy group bonded to the silicon atom may be, for example, 1 to 4. Examples of a functional group that reacts with at least one of an acrylic monomer or an epoxy resin include an amino group such as a primary amino group and a secondary amino group, an epoxy group, a mercapto group, and a (meth) acryloyl group. .. In the present specification, compounds having a hydrolyzable silyl group and a (meth) acryloyl group are classified as silane coupling agents.
　シランカップリング剤の具体例としては、３－グリシジルオキシプロピルトリメトキシシラン、及び３－アミノプロピルトリメトキシシランが挙げられる。 Specific examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
　シランカップリング剤の市販品として、例えば、ＫＢＭ－３０３、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＥ－４０２、ＫＢＥ－４０３、ＫＢＭ－４８０３、ＫＢＭ－５０２、ＫＢＭ－５０３、ＫＢＥ－５０２、ＫＢＥ－５０３、ＫＢＭ－５１０３、ＫＢＭ－５８０３、ＫＢＭ－６０２、ＫＢＭ－６０３、ＫＢＭ－９０３、ＫＢＥ－９０３、ＫＢＥ－９１０３Ｐ、ＫＢＭ－５７３、ＫＢＭ－５７５、ＫＢＭ－８０２、及びＫＢＭ－８０３（以上、信越化学工業株式会社製、商品名）が入手可能である。 Commercially available products of the silane coupling agent include, for example, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-502, KBM-503, KBE-502, KBE-503. , KBM-5103, KBM-5803, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM-575, KBM-802, and KBM-803 (Shin-Etsu Chemical) (Product name) manufactured by Kogyo Co., Ltd. is available.
　第一液におけるシランカップリング剤の含有量は、第一液の量に対して、０～５質量％、又は０～３質量％であってもよい。第二液におけるシランカップリング剤の含有量は、第二液の量に対して、０～５質量％、又は０～３質量％であってもよい。 The content of the silane coupling agent in the first liquid may be 0 to 5% by mass or 0 to 3% by mass with respect to the amount of the first liquid. The content of the silane coupling agent in the second liquid may be 0 to 5% by mass or 0 to 3% by mass with respect to the amount of the second liquid.
　第一液、第二液又はこれらの両方が、必要によりその他の成分を更に含有してもよい。その他の成分の例としては、顔料（例えばカーボンブラック、酸化チタン粒子）、及びエラストマーが挙げられる。 The first liquid, the second liquid, or both of them may further contain other components if necessary. Examples of other components include pigments (eg carbon black, titanium oxide particles), and elastomers.
　第一液又は第二液のうち一方のみが顔料を含有していてもよい。又は、第一液及び第二液の両方が顔料を含有していてもく、その場合、第一液が含有する顔料と第二液が含有する顔料とが異なっていてもよい。このように接着剤セットが顔料を含むと、第一液と第二液とを混合したときに、第一液と第二液との混合状態を可視化できる。第一液と第二液との混合液を、顔料が十分に均一に分散するような混合状態とすることにより、より優れた接着力が得られる傾向にある。 Only one of the first liquid and the second liquid may contain a pigment. Alternatively, both the first liquid and the second liquid may contain a pigment, in which case the pigment contained in the first liquid and the pigment contained in the second liquid may be different. When the adhesive set contains a pigment in this way, when the first liquid and the second liquid are mixed, the mixed state of the first liquid and the second liquid can be visualized. By putting the mixed liquid of the first liquid and the second liquid in a mixed state in which the pigment is sufficiently uniformly dispersed, a better adhesive force tends to be obtained.
　以上例示された接着剤セットは、第一液及び第二液の混合物である接着剤によって被着体同士を接着して、２以上の被着体と、これらを接着する接着層とを有する所望の接着体を得るために用いられる。被着体は、例えば、鋼、鉄、銅、ブリキ、アルミニウム、ステンレス等の金属、樹脂、又は炭素繊維強化プラスチック（ＣＦＲＰ）の成形体であってもよい。２以上の被着体は、互いに同種又は異種の材料の成形体であることができる。 The adhesive set exemplified above is desired to have two or more adherends and an adhesive layer for adhering them by adhering the adherends to each other with an adhesive which is a mixture of the first liquid and the second liquid. It is used to obtain an adhesive of. The adherend may be, for example, a molded body of metal such as steel, iron, copper, tinplate, aluminum, stainless steel, resin, or carbon fiber reinforced plastic (CFRP). The two or more adherends can be molded bodies of the same or different materials from each other.
　接着剤セットを用いて２つの被着体を有する接着体を得る方法は、例えば、２つの被着体を隙間を空けて配置することと、２つの被着体間の隙間に第一液及び第二液を注入することと、第一液及び第二液の混合物である接着剤を硬化させることとを含む。第一液及び第二液は、２つの被着体間の隙間に注入されるのと略同時に混合されてもよいし、混合されてから２つの被着体間に注入されてもよい。第一液及び第二液、又はこれらの混合物（接着剤）が、例えばミキシングノズルを用いて２つの被着体間に注入される。 The method of obtaining an adhesive having two adherends using an adhesive set is, for example, arranging the two adherends with a gap, and the first liquid and the first liquid in the gap between the two adherends. It involves injecting a second solution and curing an adhesive that is a mixture of the first and second solutions. The first liquid and the second liquid may be mixed substantially at the same time as being injected into the gap between the two adherends, or may be mixed and then injected between the two adherends. The first liquid and the second liquid, or a mixture (adhesive) thereof, are injected between the two adherends using, for example, a mixing nozzle.
　接着体を得る方法が、一方の被着体上に第一液及び第二液の混合物である接着剤を塗布することと、塗布された接着剤を間に挟みながら一方の被着体と他方の被着体とを貼り合わせることと、その後、接着剤を硬化させることとを含んでいてもよい。接着剤が硬化することによって、２つの被着体の間に介在し、これらを接着する接着層が形成される。 The method of obtaining an adhesive is to apply an adhesive which is a mixture of the first liquid and the second liquid on one adherend, and to sandwich the applied adhesive between one adherend and the other. It may include affixing the adherend to the adherend and then curing the adhesive. As the adhesive cures, it forms an adhesive layer that intervenes between the two adherends and adheres them.
　第一液と第二液との混合比は、第一液に含まれるアクリルモノマー及びエポキシ樹脂と第二液に含まれる硬化剤との反応の化学量論比等を考慮して、接着剤が適切に硬化するように調整される。例えば、第二液に対する第一液の体積比が、０．５～５．０であってもよい。 The mixing ratio of the first liquid and the second liquid is determined by considering the stoichiometric ratio of the reaction between the acrylic monomer and epoxy resin contained in the first liquid and the curing agent contained in the second liquid. Adjusted to cure properly. For example, the volume ratio of the first liquid to the second liquid may be 0.5 to 5.0.
　硬化条件は、接着剤が適切に硬化するように調整される。例えば、１０～４０℃の環境下で接着剤を硬化してもよい。硬化時間は、例えば１時間～１週間の間で調整される。接着剤を加熱してもよく、その場合の加熱温度は例えば４０～１２０℃であってもよい。 Curing conditions are adjusted so that the adhesive cures properly. For example, the adhesive may be cured in an environment of 10 to 40 ° C. The curing time is adjusted, for example, between 1 hour and 1 week. The adhesive may be heated, in which case the heating temperature may be, for example, 40-120 ° C.
　以下、実施例を挙げて本発明についてより具体的に説明する。ただし、本発明は以下の実施例に限られない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
１．接着剤セットの調製
　以下の各原料を用いて、表１に示す組成の第一液及び第二液を調製した。
（１）アクリルモノマー
・１，６－ヘキサンジオールジアクリレート（ビスコート２３０、新中村化学工業株式会社）
（２）エポキシ樹脂
・ビスフェールＦ型エポキシ樹脂（ＥＰＩＣＬＯＮ８３０、ＤＩＣ株式会社）
（３）硬化剤
・１，３－ビスアミノメチルシクロヘキサン
・脂肪族アミン系硬化剤（ｊＥＲキュア３０８０、三菱ケミカル株式会社）
（４）フィラー（無機充填剤）
・シリカ粒子（アエロジル２００Ｖ、日本アエロジル株式会社）
（５）シランカップリング剤
・３－グリシジルオキシプロピルトリメトキシシラン（ＫＢＭ－４０３、信越化学工業株式会社）
・３－アミノプロピルトリメトキシシラン（ＫＢＭ－９０３、信越化学工業株式会社）
（６）エラストマー
・メチルメタクリレート－ブチルアクリレート－メチルメタクリレートのトリブロック共重合体（クラリティＬＡ３３２０、株式会社クラレ）
・両末端アクリレートポリマー（ＸＭＡＰ　ＲＣ１１０Ｃ、株式会社カネカ） 1. 1. Preparation of Adhesive Set Using the following raw materials, the first liquid and the second liquid having the compositions shown in Table 1 were prepared.
(1) Acrylic monomer, 1,6-hexanediol diacrylate (Viscoat 230, Shin Nakamura Chemical Industry Co., Ltd.)
(2) Epoxy resin / Bisfer F type epoxy resin (EPICLON830, DIC Corporation)
(3) Hardener, 1,3-bisaminomethylcyclohexane, aliphatic amine-based hardener (jER Cure 3080, Mitsubishi Chemical Corporation)
(4) Filler (inorganic filler)
・ Silica particles (Aerosil 200V, Nippon Aerosil Co., Ltd.)
(5) Silane coupling agent 3-glycidyloxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.)
・ 3-Aminopropyltrimethoxysilane (KBM-903, Shin-Etsu Chemical Co., Ltd.)
(6) Elastomer-Methylmethacrylate-Butylacrylate-Methylmethacrylate Triblock Copolymer (Clarity LA3320, Kuraray Co., Ltd.)
-Both end acrylate polymers (XMAP RC110C, Kaneka Corporation)
２．評価
（１）液だれ
　スタティックミキサーを用いて第一液と第二液とを体積比２：１で混合し、形成された接着剤を、垂直に立てたアルミニウム板上に塗布した。塗布後の接着剤混合物の液だれの状態を観察し、塗布の時点から１．０ｍｍ以上の液だれが発生するまでの時間を測定した。測定結果から、以下の評価基準で各接着剤セットを評価した。
Ａ：３０分以上
Ｂ：１０分を超えて３０分未満
Ｃ：１０分以内 2. 2. Evaluation (1) Liquid dripping The first liquid and the second liquid were mixed at a volume ratio of 2: 1 using a static mixer, and the formed adhesive was applied onto an aluminum plate standing vertically. The state of dripping of the adhesive mixture after application was observed, and the time from the time of application to the occurrence of dripping of 1.0 mm or more was measured. From the measurement results, each adhesive set was evaluated according to the following evaluation criteria.
A: 30 minutes or more B: More than 10 minutes and less than 30 minutes C: Within 10 minutes
（２）室温硬化性
　スタティックミキサーを用いて第一液と第二液とを体積比２：１で混合し、形成された接着剤をアルミニウム板上に塗布した。塗布された接着剤を２５℃で１日養生した時点で、接着剤が硬化したか否かを目視で確認した。硬化が確認された接着剤を「Ａ」、硬化が確認されなかった接着剤を「Ｃ」と判定した。 (2) Room temperature curability The first liquid and the second liquid were mixed at a volume ratio of 2: 1 using a static mixer, and the formed adhesive was applied onto an aluminum plate. When the applied adhesive was cured at 25 ° C. for one day, it was visually confirmed whether or not the adhesive had hardened. The adhesive that was confirmed to be cured was determined to be "A", and the adhesive that was not confirmed to be cured was determined to be "C".
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (6)

  1. 　２個以上の（メタ）アクリロイル基を有するアクリルモノマー、及び２個以上のエポキシ基を有するエポキシ樹脂を含有する第一液と、
    　エポキシ基及び（メタ）アクリロイル基のいずれもと反応する求核性反応基を有する化合物を含む硬化剤を含有する第二液と、を備える、
    接着剤セット。     A first liquid containing an acrylic monomer having two or more (meth) acryloyl groups and an epoxy resin having two or more epoxy groups,
    A second solution containing a curing agent containing a compound having a nucleophilic reactive group that reacts with either an epoxy group or a (meth) acryloyl group.
    Adhesive set.
  2. 　前記求核性反応基が脂肪族アミノ基である、請求項１に記載の接着剤セット。 The adhesive set according to claim 1, wherein the nucleophilic reactive group is an aliphatic amino group.
  3. 　前記第一液又は前記第二液のうち少なくとも一方が無機充填剤を更に含有する、請求項１又は２に記載の接着剤セット。 The adhesive set according to claim 1 or 2, wherein at least one of the first liquid and the second liquid further contains an inorganic filler.
  4. 　前記第一液又は前記第二液のうち一方のみが顔料を更に含有する、請求項１～３のいずれか一項に記載の接着剤セット。 The adhesive set according to any one of claims 1 to 3, wherein only one of the first liquid and the second liquid further contains a pigment.
  5. 　前記第一液及び前記第二液がそれぞれ顔料を更に含有し、前記第一液が含有する顔料と前記第二液が含有する顔料とが異なる、請求項１～４のいずれか一項に記載の接着剤セット。 The invention according to any one of claims 1 to 4, wherein the first liquid and the second liquid each further contain a pigment, and the pigment contained in the first liquid and the pigment contained in the second liquid are different from each other. Adhesive set.
  6. 　２以上の被着体と、前記２以上の被着体を接着する接着層と、を有し、
    　前記接着層が、請求項１～５のいずれか一項に記載の接着剤セットによって形成された層である、接着体。     It has two or more adherends and an adhesive layer for adhering the two or more adherends.
    An adhesive body in which the adhesive layer is a layer formed by the adhesive set according to any one of claims 1 to 5.
PCT/JP2019/030072 2019-07-31 2019-07-31 Adhesive set WO2021019741A1 (en)

Priority Applications (4)

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PCT/JP2019/030072 WO2021019741A1 (en) 2019-07-31 2019-07-31 Adhesive set
TW109125857A TW202112992A (en) 2019-07-31 2020-07-30 Bonding agent set and bonded body
PCT/JP2020/029218 WO2021020506A1 (en) 2019-07-31 2020-07-30 Bonding agent set and bonded body
JP2021535422A JPWO2021020506A1 (en) 2019-07-31 2020-07-30

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2019/030072 WO2021019741A1 (en) 2019-07-31 2019-07-31 Adhesive set

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PCT/JP2020/029218 WO2021020506A1 (en) 2019-07-31 2020-07-30 Bonding agent set and bonded body

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0195176A (en) * 1987-09-03 1989-04-13 Texaco Dev Corp Epoxy adhesive
JPH09296027A (en) * 1996-05-07 1997-11-18 Toyo Ink Mfg Co Ltd Curable resin composition
JP2007518840A (en) * 2003-09-26 2007-07-12 イリノイ トゥール ワークス インコーポレイティド Adhesive composition
JP2012211244A (en) * 2011-03-31 2012-11-01 Aica Kogyo Co Ltd Epoxy resin adhesive composition
JP2017519869A (en) * 2014-06-17 2017-07-20 スリーエム イノベイティブ プロパティズ カンパニー Quick-curing epoxy adhesive composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051195A (en) * 1975-12-15 1977-09-27 Celanese Polymer Specialties Company Polyepoxide-polyacrylate ester compositions
JP3815694B2 (en) * 1995-02-27 2006-08-30 旭化成ケミカルズ株式会社 Adhesive for building structures
JPH08325358A (en) * 1995-06-02 1996-12-10 Toyo Ink Mfg Co Ltd Curable resin composition for building material of civil engineering work
JPH10182938A (en) * 1996-12-24 1998-07-07 Toyo Ink Mfg Co Ltd Curable resin composition and resin composition
JP2002275242A (en) * 2001-03-21 2002-09-25 Yokohama Rubber Co Ltd:The Low-temperature curable epoxy resin composition and adhesive using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0195176A (en) * 1987-09-03 1989-04-13 Texaco Dev Corp Epoxy adhesive
JPH09296027A (en) * 1996-05-07 1997-11-18 Toyo Ink Mfg Co Ltd Curable resin composition
JP2007518840A (en) * 2003-09-26 2007-07-12 イリノイ トゥール ワークス インコーポレイティド Adhesive composition
JP2012211244A (en) * 2011-03-31 2012-11-01 Aica Kogyo Co Ltd Epoxy resin adhesive composition
JP2017519869A (en) * 2014-06-17 2017-07-20 スリーエム イノベイティブ プロパティズ カンパニー Quick-curing epoxy adhesive composition

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