JPH05271636A - One-pack epoxy resin adhesive - Google Patents
One-pack epoxy resin adhesiveInfo
- Publication number
- JPH05271636A JPH05271636A JP10620592A JP10620592A JPH05271636A JP H05271636 A JPH05271636 A JP H05271636A JP 10620592 A JP10620592 A JP 10620592A JP 10620592 A JP10620592 A JP 10620592A JP H05271636 A JPH05271636 A JP H05271636A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- parts
- block copolymer
- styrene block
- copolymer resin
- 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.)
- Pending
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、密着性と強靱性を付加
した一液型エポキシ樹脂接着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type epoxy resin adhesive having added adhesion and toughness.
【０００２】[0002]
【従来の技術】エポキシ樹脂は、優れた特性を有してい
るので、接着剤、塗料、複合材料等のバインダーとして
幅広い分野に利用されている。2. Description of the Related Art Epoxy resins have excellent properties and are therefore used in a wide range of fields as binders for adhesives, paints, composite materials and the like.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、エポキ
シ樹脂は、耐衝撃性、耐剥離接着力などの可撓性に欠点
があり、これを改良する目的で、液状ジエンポリマー、
ウレタン樹脂、シリコーン樹脂などの可撓性付与剤の添
加も検討されているが、相溶性が悪かったり、耐熱性の
低下などの問題があった。However, epoxy resins have drawbacks in flexibility such as impact resistance and peeling resistance, and in order to improve these, liquid diene polymers,
The addition of flexibility-imparting agents such as urethane resins and silicone resins has also been investigated, but there were problems such as poor compatibility and reduced heat resistance.
【０００４】なかでも、可撓性、耐候性、密着性及び耐
熱性などの点から、スチレンブロック共重合体樹脂の添
加混合も検討されているが、相溶性が悪く、均一な分散
体を得ることは困難であった。Among them, addition and mixing of a styrene block copolymer resin have been studied from the viewpoints of flexibility, weather resistance, adhesion and heat resistance, but the compatibility is poor and a uniform dispersion is obtained. It was difficult.
【０００５】本発明の目的は、可撓性と耐熱性を兼ね備
えているスチレンブロツク共重合体樹脂のエポキシ樹脂
への混入を可能にして、密着性と強靱性を付加した一液
型エポキシ樹脂接着剤を提供することにある。It is an object of the present invention to bond a styrene block copolymer resin having both flexibility and heat resistance to an epoxy resin, thereby adhering a one-pack type epoxy resin to which adhesion and toughness are added. To provide the agent.
【０００６】[0006]
【課題を解決するための手段】本発明は、エポキシ樹脂
と潜在性硬化剤の混合物１００重量部に対して、予めス
チレンブロック共重合体樹脂を有機過酸化物の存在下で
加熱して分子を切断して得られた低分子化ゴム成分を３
〜３０重量部含有させた一液型エポキシ樹脂接着剤であ
る。According to the present invention, 100 parts by weight of a mixture of an epoxy resin and a latent curing agent is preliminarily heated with a styrene block copolymer resin in the presence of an organic peroxide to remove molecules. Cut the low molecular weight rubber component obtained by cutting to 3
It is a one-pack type epoxy resin adhesive containing about 30 parts by weight.
【０００７】本発明のエポキシ樹脂とは、ビスフェノー
ルＡ型、ビスフェノールＦ型、ノボラック型、脂環型、
グリシジルアミン型、水添ビスフェノールＡ型などのエ
ポキシ樹脂、あるいはＮＢＲやウレタン樹脂などの可撓
性成分で変性されたエポキシ樹脂を用いることができ
る。また、ポリエチレングリコール、ポリプロピレング
リコール、ネオペンチルグリコール、１，６ヘキサンジ
オール、トリメチロールプロパンなどのグリシジルエー
テルである反応性希釈剤を上記エポキシ樹脂に混入して
用いることもできる。The epoxy resin of the present invention means bisphenol A type, bisphenol F type, novolac type, alicyclic type,
Epoxy resins such as glycidyl amine type and hydrogenated bisphenol A type, or epoxy resins modified with a flexible component such as NBR and urethane resin can be used. Further, a reactive diluent which is a glycidyl ether such as polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,6 hexanediol and trimethylolpropane can be mixed with the epoxy resin and used.
【０００８】潜在性硬化剤としては、ジシアンジアミド
の他、ルイス酸錯体、イミダゾール化合物、有機酸ヒド
ラジド、ジアミノマレオニトリル、メラミンおよびその
誘導体、ポリアミン塩、アミンイミド化合物、マイクロ
カプセル化硬化剤など、従来公知のものを種々選択して
用いることができる。その混合量はエポキシ系樹脂の量
およびその反応当量に応じて決定される。As the latent curing agent, other than dicyandiamide, Lewis acid complex, imidazole compound, organic acid hydrazide, diaminomaleonitrile, melamine and its derivatives, polyamine salt, amine imide compound, microencapsulating curing agent, etc., which are conventionally known. Various items can be selected and used. The mixing amount is determined according to the amount of epoxy resin and its reaction equivalent.
【０００９】スチレンブロック共重合体樹脂としては、
スチレン−ブタジエン共重合体樹脂（ＳＢ）、スチレン
−ブタジエン−スチレンブロック共重合体樹脂（ＳＢ
Ｓ）、スチレン−イソプレン−スチレンブロック共重合
体樹脂（ＳＩＳ）、スチレン−エチレン−ブタジエン−
スチレンブロック共重合体樹脂（ＳＥＢＳ）が挙げら
れ、例えばシェル化学(株)製の「カリフレックスＴＲ１
１０１」、「クレイトンＧ１６５２」など、旭化成工業
(株)製の「タフプレン３１５」、「タフテックＭ−１９
１３」などが市販されている。As the styrene block copolymer resin,
Styrene-butadiene copolymer resin (SB), styrene-butadiene-styrene block copolymer resin (SB
S), styrene-isoprene-styrene block copolymer resin (SIS), styrene-ethylene-butadiene-
Examples of the styrene block copolymer resin (SEBS) include "Califlex TR1" manufactured by Shell Chemical Co., Ltd.
"101", "Clayton G1652", etc. Asahi Kasei
"Toughprene 315" manufactured by Co., Ltd., "Tuftec M-19"
13 ”and the like are commercially available.
【００１０】有機過酸化物としては、ベンゾイルパーオ
キサイド、メチルエチルケトンパーオキサイド、ジクミ
ルパーオキサイド、クメンハイドロッパーオキサイド、
ジブチルパーオキサイド、ｔ−ブチルパーオキシベンゾ
ェード、１，３−ビス（ｔ−ブチルパーオキシイソプロ
ビル）ベンゼンなどがある。As the organic peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, cumene hydroperoxide,
Examples include dibutyl peroxide, t-butyl peroxybenzode, and 1,3-bis (t-butyl peroxyisoprovir) benzene.
【００１１】本発明では、予め上記スチレンブロック共
重合体樹脂と上記有機過酸化物とを溶媒（例、ジメチル
ホルムアミド）に溶解し、１２０℃〜２００℃に加熱
し、ゴム分子を酸化的に切断して得られる低分子化ゴム
成分を、前記エポキシ樹脂と潜在性硬化剤の混合物１０
０重量部に対して、３〜３０重量部添加混合する。添加
量が３重量部以下では本発明の効果が認められず、３０
重量部以上の添加混合は、相溶性の点で望ましくない。In the present invention, the styrene block copolymer resin and the organic peroxide are dissolved in a solvent (eg, dimethylformamide) in advance and heated to 120 ° C. to 200 ° C. to oxidatively cut rubber molecules. The low molecular weight rubber component obtained by the above is used as a mixture 10 of the epoxy resin and the latent curing agent.
3 to 30 parts by weight are added and mixed with 0 parts by weight. If the addition amount is 3 parts by weight or less, the effect of the present invention is not recognized, and
Addition and mixing of more than parts by weight is not desirable in terms of compatibility.
【００１２】本発明では、上記各成分の他に、必要に応
じて、通常の溶媒（揮発性溶剤、高沸点溶剤、可塑剤な
ど）、充填剤（炭酸カルシウムなどの無機質フィラ
ー）、チキソ性付与剤、カップリング剤、安定剤などの
添加剤の混合使用もあり得る。In the present invention, in addition to the above components, if necessary, ordinary solvents (volatile solvents, high boiling point solvents, plasticizers, etc.), fillers (inorganic fillers such as calcium carbonate), and thixotropic properties are imparted. There may be mixed use of additives such as agents, coupling agents and stabilizers.
【００１３】[0013]
【実施例】以下実施例に従って説明する。なお、部は重
量部を示す。 実施例１ １．低分子化ゴム成分の製造 還流装置と温度計を備えた三つ口１リットルフラスコ
に、スチレン−エチレン−ブタジエン−スチレンブロッ
ク共重合体樹脂（ＳＥＢＳ）のクレイトンＧ−１６５２
（シェル化学社製）３０部と溶媒のＮ，Ｎ−ジメチルホ
ルムアミド（ＤＭＦ）３００部を入れ８０℃に加熱して
溶解した後に、ベンゾイルパーオキサイド１０部を入れ
て、撹拌しながら３０分間要して１５０℃まで昇温し、
１５０℃で２時間撹拌し続けて低分子化反応を進行させ
た。反応液を撹拌しながら室温まで放置冷却した後に、
１００部の水と５００部のトルエンで、分液ロートにて
抽出分離した。更にトルエン層を１０００部の水と３０
０部の飽和食塩溶液で洗い、エバポレーターで濃縮し
て、低分子化ＳＥＢＳ成分の２０％トルエン溶液を得
た。これを低分子化ＳＥＢＳとする。EXAMPLES Examples will be described below. In addition, a part shows a weight part. Example 1 1. Production of low molecular weight rubber component In a three-necked 1 liter flask equipped with a reflux device and a thermometer, styrene-ethylene-butadiene-styrene block copolymer resin (SEBS), Kraton G-1652.
After adding 30 parts (manufactured by Shell Chemical Co.) and 300 parts of N, N-dimethylformamide (DMF) as a solvent and heating to 80 ° C. to dissolve, 10 parts of benzoyl peroxide were added and stirring was carried out for 30 minutes. Up to 150 ° C,
Stirring was continued for 2 hours at 150 ° C. to promote the molecular weight reduction reaction. After cooling the reaction solution to room temperature with stirring,
The mixture was extracted and separated with 100 parts of water and 500 parts of toluene using a separating funnel. Further, add 1000 parts of water and 30 parts of toluene layer.
It was washed with 0 part of a saturated sodium chloride solution and concentrated by an evaporator to obtain a 20% toluene solution of a low molecular weight SEBS component. This is called low molecular weight SEBS.
【００１４】２．一液型エポキシ樹脂接着剤の製造 上記１で得た低分子化ＳＥＢＳ成分の２０％トルエン溶
液を５０部、ビスフェノールＡ型の液状エポキシ樹脂で
あるエピコート８２８（油化シェルエポキシ社製）１０
０部、ジシアンジアミド６部、イミダゾール３部をプラ
ネタリーにて１０分間撹拌し、更に１０mmHgに減圧撹拌
してトルエンを除去し、実施例１の接着剤とした。2. Manufacture of one-pack type epoxy resin adhesive 50 parts of 20% toluene solution of the low molecular weight SEBS component obtained in 1 above, Epicoat 828 (manufactured by Yuka Shell Epoxy Co.) which is a bisphenol A type liquid epoxy resin 10
0 parts, 6 parts of dicyandiamide, and 3 parts of imidazole were stirred in a planetary for 10 minutes, and further stirred under reduced pressure to 10 mmHg to remove toluene to obtain an adhesive of Example 1.
【００１５】比較例１ 実施例１において、低分子化ＳＥＢＳ成分の２０％トル
エン溶液の代わりに、クレイトンＧ１６５２の２０％ト
ルエン溶液を用いた以外は、同様にして、比較例１の接
着剤とした。Comparative Example 1 An adhesive of Comparative Example 1 was prepared in the same manner as in Example 1, except that a 20% toluene solution of Kraton G1652 was used in place of the 20% toluene solution of the low molecular weight SEBS component. ..
【００１６】実施例２ 実施例１において、クレイトンＧ−１６５２の代わり
に、スチレン−ブタジエン−スチレン共重合体樹脂（Ｓ
ＢＳ）のカリフレックスＴＲ１１０１（シェル化学社
製）を併用した以外は同様にして、低分子化ＳＢＳ成分
の２０％トルエン溶液を得て、これを使用して同様にし
て実施例２の接着剤とした。Example 2 In Example 1, instead of Kraton G-1652, a styrene-butadiene-styrene copolymer resin (S
(BS) Califlex TR1101 (manufactured by Shell Chemical Co., Ltd.) was also used in the same manner as above to obtain a 20% toluene solution of a low molecular weight SBS component, which was used in the same manner as the adhesive of Example 2. did.
【００１７】比較例２ 実施例２において、低分子化ＳＢＳ成分の２０％トルエ
ン溶液の代わりに、カリフレックスＴＲ１１０１の２０
％トルエン溶液を用いた以外は同様にして、比較例２の
接着剤とした。Comparative Example 2 In Example 2, 20% of Califlex TR1101 was used instead of the 20% toluene solution of the low molecular weight SBS component.
% Toluene solution was used in the same manner as the adhesive of Comparative Example 2.
【００１８】次に、上記実施例１と２及び比較例１と２
の性能を次の様に測定してその結果を表１に示す。Next, the above Examples 1 and 2 and Comparative Examples 1 and 2
Was measured as follows, and the results are shown in Table 1.
【００１９】相溶性：ＪＩＳ Ｋ６８３３「接着剤の一
般試験方法」に準じて、試料をガラス板上にガラス棒で
均一に薄く塗布し、粗粒子の有無を目視で観察した。Compatibility: According to JIS K6833 "General Test Method for Adhesives", a sample was uniformly and thinly coated on a glass plate with a glass rod, and the presence or absence of coarse particles was visually observed.
【００２０】耐衝撃性強さ：ＪＩＳ Ｋ７１１１「硬質
プラスチックのシャルピー衝撃試験方法」に準じて６号
試験片を作成し、１２０℃で１時間硬化後の２０℃にお
けるシャルピー強度〔kg・cm／cm2〕を測定した。Impact resistance strength: No. 6 test piece was prepared in accordance with JIS K7111 "Charpy impact test method for hard plastics", and after curing at 120 ° C for 1 hour, Charpy strength at 20 ° C [kg · cm / cm]. 2 ] was measured.
【００２１】剥離接着強さ：ＪＩＳ Ｋ６８５４「接着
剤の剥離接着強さ試験方法」に準じて、厚さ０．５mmの
アルミ板同士を接着し、１２０℃で１時間硬化後の２０
℃及び８０℃に於けるＴ型剥離強度〔kgf／２５mm〕を
測定した。Peel adhesion strength: According to JIS K6854 "Peel adhesion strength test method for adhesives", aluminum plates having a thickness of 0.5 mm are adhered to each other and cured at 120 ° C for 1 hour to give 20.
The T-type peel strength [kgf / 25 mm] at ℃ and 80 ℃ was measured.
【００２２】引張り剪断強さ：ＪＩＳ Ｋ６８５０「接
着剤の引張り接着強さ試験方法」に準じて、厚さ１．６
mmの鉄片同士を接着し、１２０℃で１時間硬化後の２０
℃における引張剪断強度〔kgf／cm2〕を測定した。Tensile shear strength: According to JIS K6850 "Test method for tensile adhesive strength of adhesive", thickness 1.6
mm pieces of iron are glued together, and after curing at 120 ° C for 1 hour, 20
The tensile shear strength [kgf / cm 2 ] at ° C was measured.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明の一液型エポキシ樹脂接着剤は、
可撓性と耐熱性を併ね備えているスチレンブロック共重
合体樹脂の低分子化物が混入されているので、相溶性が
良くて、剥離接着強さ及び引張り剪断強さのいずれの接
着強さも向上しているので、構造用接着剤として有用で
ある。The one-pack type epoxy resin adhesive of the present invention is
Low molecular weight compound of styrene block copolymer resin, which has both flexibility and heat resistance, is mixed, so compatibility is good, and both adhesive strength of peel adhesion and tensile shear strength are good. Since it is improved, it is useful as a structural adhesive.
Claims (1)
００重量部に対して、予めスチレンブロック共重合体樹
脂を有機過酸化物の存在下で加熱して分子を切断して得
られた低分子化ゴム成分を３〜３０重量部含有させたこ
とを特徴とする一液型エポキシ樹脂接着剤。1. A mixture 1 of an epoxy resin and a latent curing agent.
3 to 30 parts by weight of a low molecular weight rubber component obtained by previously heating a styrene block copolymer resin in the presence of an organic peroxide to cleave the molecule with respect to 00 parts by weight. A characteristic one-pack type epoxy resin adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10620592A JPH05271636A (en) | 1992-03-30 | 1992-03-30 | One-pack epoxy resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10620592A JPH05271636A (en) | 1992-03-30 | 1992-03-30 | One-pack epoxy resin adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05271636A true JPH05271636A (en) | 1993-10-19 |
Family
ID=14427664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10620592A Pending JPH05271636A (en) | 1992-03-30 | 1992-03-30 | One-pack epoxy resin adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05271636A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000026873A (en) * | 1998-10-23 | 2000-05-15 | 조민호 | Process for preparing epoxy resin reinforced by polytrimethylene terephthalate |
| CN1062288C (en) * | 1996-12-18 | 2001-02-21 | 閎邦实业股份有限公司 | Single-liquid type epoxy infusion for insulation coating of capacitor |
| US6316564B1 (en) | 1999-10-07 | 2001-11-13 | E. I. Du Pont De Nemours And Company | Acrylic block copolymer pigment dispersants containing heterocyclic groups |
| JP2014529900A (en) * | 2011-08-31 | 2014-11-13 | ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー | Method for impregnating air core reactor, impregnation air core reactor, and use of impregnation system |
| CN115895497A (en) * | 2022-12-13 | 2023-04-04 | 常州亚龙电子科技有限公司 | Epoxy adhesive tape for screen printing and preparation method thereof |
-
1992
- 1992-03-30 JP JP10620592A patent/JPH05271636A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062288C (en) * | 1996-12-18 | 2001-02-21 | 閎邦实业股份有限公司 | Single-liquid type epoxy infusion for insulation coating of capacitor |
| KR20000026873A (en) * | 1998-10-23 | 2000-05-15 | 조민호 | Process for preparing epoxy resin reinforced by polytrimethylene terephthalate |
| US6316564B1 (en) | 1999-10-07 | 2001-11-13 | E. I. Du Pont De Nemours And Company | Acrylic block copolymer pigment dispersants containing heterocyclic groups |
| JP2014529900A (en) * | 2011-08-31 | 2014-11-13 | ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー | Method for impregnating air core reactor, impregnation air core reactor, and use of impregnation system |
| US9403185B2 (en) | 2011-08-31 | 2016-08-02 | Huntsman International Llc | Impregnation of air core reactors |
| CN115895497A (en) * | 2022-12-13 | 2023-04-04 | 常州亚龙电子科技有限公司 | Epoxy adhesive tape for screen printing and preparation method thereof |
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