JP2000068294A - Thermosetting resin adhesive - Google Patents

Thermosetting resin adhesive

Info

Publication number
JP2000068294A
JP2000068294A JP25455698A JP25455698A JP2000068294A JP 2000068294 A JP2000068294 A JP 2000068294A JP 25455698 A JP25455698 A JP 25455698A JP 25455698 A JP25455698 A JP 25455698A JP 2000068294 A JP2000068294 A JP 2000068294A
Authority
JP
Japan
Prior art keywords
adhesive
thermosetting resin
imidazole
trade name
manufactured
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
Application number
JP25455698A
Other languages
Japanese (ja)
Inventor
Minoru Hara
実 原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Chemical Corp
Original Assignee
Toshiba Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toshiba Chemical Corp filed Critical Toshiba Chemical Corp
Priority to JP25455698A priority Critical patent/JP2000068294A/en
Publication of JP2000068294A publication Critical patent/JP2000068294A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/102—Material of the semiconductor or solid state bodies
    • H01L2924/1025—Semiconducting materials
    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]

Landscapes

  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Die Bonding (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a one-pack thermosetting resin adhesive which can be used at assembling of electronic devices and exhibits high adhesive strength and a quick curing property at high temperatures. SOLUTION: A thermosetting resin adhesive has a distinctive feature such that the adhesive contains (A) 40 wt.% or higher polyfunctional epoxy resin having 150 epoxy equivalent or less. (B) 3 wt.% or higher modified imidazole which is added as a curing agent, and (C) 1 wt.% or higher titanate compound which is added as a catalyst as essential ingredients.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、一液性の熱硬化性
樹脂接着剤に関するものであり、電子デバイスのアッセ
ンブリ用の接着剤として好適に適用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-part thermosetting resin adhesive and is suitably applied as an adhesive for assembling electronic devices.

【０００２】[0002]

【従来の技術】例えば、半導体チップなどの電子部品
を、アルミナ基板など回路基板の所定箇所に搭載するた
めの一液性接着剤として、エポキシ樹脂系のさまざまな
絶縁ペーストが使用されている。2. Description of the Related Art Various epoxy resin-based insulating pastes have been used as one-part adhesives for mounting electronic components such as semiconductor chips on predetermined portions of a circuit board such as an alumina board.

【０００３】[0003]

【発明が解決しようとする課題】しかしながら、従来の
エポキシ樹脂系の一液性接着剤では、200 ℃以上での加
熱時の強度が弱く、半田リフローのような高温での耐熱
信頼性が低かった。また、一液性接着剤として硬化時間
の短縮化も問題とされている。このため、半田リフロー
による一括接続が容易であり、かつ耐熱信頼性の高い一
液性接着剤が望まれていた。However, the conventional epoxy resin-based one-part adhesive has low strength when heated at 200 ° C. or higher, and has low heat resistance at high temperatures such as solder reflow. . Also, shortening the curing time as a one-part adhesive has been problematic. For this reason, a one-part adhesive which can be easily connected by solder reflow and has high heat resistance and reliability has been desired.

【０００４】本発明は、電子デバイスのアッセンブリ用
接着剤の半田リフローなどにおける上記問題点を解決す
ることを目的とするもので、高温での高接着力、速硬化
の一液性熱硬化性樹脂接着剤を提供するものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in solder reflow of an adhesive for assembly of an electronic device and the like. An adhesive is provided.

【０００５】[0005]

【課題を解決するための手段】本発明者は、上記問題点
を解決しようと鋭意研究を重ねた結果、後述する組成の
樹脂接着剤が上記目的を達成できることを見いだし、本
発明を完成させたものである。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a resin adhesive having the composition described below can achieve the above object, and has completed the present invention. Things.

【０００６】即ち、本発明は、（Ａ）エポキシ当量150
以下の多官能エポキシ樹脂、（Ｂ）硬化剤としてイミダ
ゾール変性物および（Ｃ）触媒としてチタネート系化合
物を必須成分とし、樹脂接着剤全体に対して、（Ａ）の
多官能エポキシ樹脂が40重量％以上、（Ｂ）のイミダゾ
ール変性物が3 重量％以上、（Ｃ）のチタネート系化合
物が1 重量％以上の割合で含有することを特徴とする熱
硬化性樹脂接着剤である。That is, the present invention relates to (A) an epoxy equivalent of 150
The following polyfunctional epoxy resin, (B) an imidazole modified product as a curing agent and a titanate compound as a catalyst (C) are essential components, and the polyfunctional epoxy resin of (A) is 40% by weight based on the whole resin adhesive. As described above, the thermosetting resin adhesive is characterized in that the imidazole-modified product (B) is contained in a proportion of 3% by weight or more and the titanate compound (C) is contained in a proportion of 1% by weight or more.

【０００７】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.

【０００８】本発明に用いる（Ａ）多官能エポキシ樹脂
としては、エポキシ当量が150 以下のエポキシ樹脂を使
用する。具体的なものとして、p-グリシジルアミノフェ
ノール型エポキシ［例えば、ＥＬＭ−１００（住友化学
社製、商品名），Ｅｐ６３０（油化シエルエポキシ社
製、商品名）］、ビスフェノールＦテトラグリシジルア
ミン型エポキシ［例えば、Ｅｐ６０４（油化シエルエポ
キシ社製、商品名）］、テトラグリシジル−m-キシレン
ジアミン［例えば、ＴＥＴＲＡＤ−Ｘ（三菱瓦斯化学社
製、商品名）］等が挙げられる。この多官能エポキシ樹
脂を用いることにより、樹脂硬化後の架橋ネットワーク
をより密にすることができ、このための多官能エポキシ
樹脂の配合割合は、熱硬化性樹脂接着剤全体に対して40
〜94重量％とすることが望ましい。またこの多官能エポ
キシ樹脂には、エポキシ当量が150を超えない程度に、
ビスフェノールＡ型エポキシ樹脂、環状脂肪族エポキシ
樹脂など、従来絶縁ペーストに使用されていたエポキシ
樹脂を併用することができる。As the polyfunctional epoxy resin (A) used in the present invention, an epoxy resin having an epoxy equivalent of 150 or less is used. Specific examples include p-glycidylaminophenol type epoxy [for example, ELM-100 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Ep630 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.)], bisphenol F tetraglycidylamine type epoxy [For example, Ep604 (trade name, manufactured by Yuka Ciel Epoxy)], tetraglycidyl-m-xylene diamine [eg, TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Company)] and the like. By using this polyfunctional epoxy resin, the crosslinked network after resin curing can be made denser, and the compounding ratio of the polyfunctional epoxy resin is 40% based on the entire thermosetting resin adhesive.
It is desirably about 94% by weight. Also, this polyfunctional epoxy resin has an epoxy equivalent not exceeding 150,
Epoxy resins conventionally used in insulating pastes, such as bisphenol A type epoxy resins and cycloaliphatic epoxy resins, can be used in combination.

【０００９】本発明の（Ｂ）硬化剤として用いるイミダ
ゾール変性物は、イミダゾール系化合物のアダクトであ
り、変性されるイミダゾール化合物としては2-メチルイ
ミダゾール、2-エチル4-メチルイミダゾール、2-フェニ
ル−4-メチルイミダゾール、2-フェニル−4-メチル−5-
ヒドロキシメチルイミダゾール等が挙げられ、また変性
はヒドロキシ安息香酸、フタル酸、イソシアヌル酸等の
酸や、シアノエチル、トリアジン等が挙げられる。具体
的な銘柄には、例えば、キュアダクトＰ−１０９０／Ｌ
−６１Ｂ（四国化成社製、商品名）等が挙げられる。イ
ミダゾール変性物を用いることにより、速硬化を実現す
ることができ、このイミダゾールとイミダゾール変性物
の配合割合は、熱硬化性樹脂接着剤全体に対して3 〜40
重量％用いることが望ましい。The modified imidazole used as the curing agent (B) of the present invention is an adduct of an imidazole compound, and the imidazole compound to be modified is 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole. 4-methylimidazole, 2-phenyl-4-methyl-5-
Hydroxymethyl imidazole and the like can be mentioned, and modifications include acids such as hydroxybenzoic acid, phthalic acid and isocyanuric acid, cyanoethyl, triazine and the like. Specific brands include, for example, Cureduct P-1090 / L
-61B (trade name, manufactured by Shikoku Chemicals) and the like. By using the imidazole-modified product, rapid curing can be realized, and the mixing ratio of the imidazole and the imidazole-modified product is 3 to 40 with respect to the entire thermosetting resin adhesive.
It is desirable to use% by weight.

【００１０】本発明に用いる（Ｃ）のチタネート系化合
物は、触媒として用いるもので、チタン酸アルキルエス
テルを主成分とするものである。具体的には、Ｓ−１８
１（日本曹達社製、商品名）等が挙げられる。その配合
量は、樹脂組成物全体に対して1 重量％以上である。チ
タネート系化合物を用いることにより、加熱時の強度を
強固なものにすることができる。[0010] The titanate compound (C) used in the present invention is used as a catalyst and contains an alkyl titanate as a main component. Specifically, S-18
1 (manufactured by Nippon Soda Co., Ltd., trade name) and the like. The compounding amount is 1% by weight or more based on the whole resin composition. By using a titanate-based compound, the strength during heating can be increased.

【００１１】上記した（Ａ）多官能エポキシ樹脂、
（Ｂ）イミダゾール変性物および（Ｃ）チタネート系化
合物をそれぞれ特定量、常法により混合して本発明の熱
硬化性樹脂接着剤が得られる。The above-mentioned (A) a polyfunctional epoxy resin,
The thermosetting resin adhesive of the present invention can be obtained by mixing (B) the imidazole-modified product and (C) the titanate-based compound in specific amounts in a usual manner.

【００１２】[0012]

【作用】本発明に係る接着剤によれば、特定の多官能エ
ポキシ樹脂、イミダゾール変性物およびチタネート系化
合物を特定量用いることにより、速硬化でかつ加熱時に
おける高い接着力という要件を満たすことができた。ま
た、ゲル時間が150 ℃で1 分以下という速硬化性を有す
るものとすることができた。According to the adhesive of the present invention, by using a specific amount of a specific polyfunctional epoxy resin, a modified imidazole and a titanate-based compound, it is possible to satisfy the requirements of fast curing and high adhesive strength when heated. did it. Also, the gel was able to have a fast-curing property with a gel time of 1 minute or less at 150 ° C.

【００１３】[0013]

【発明の実施の形態】以下、本発明の実施例によって具
体的に説明するが、本発明は、これらの実施例によって
限定されるものではない。なお、「％」とは、特に説明
のない限り「重量％」を意味する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to embodiments, but the present invention is not limited to these embodiments. In addition, "%" means "% by weight" unless otherwise specified.

【００１４】実施例１ エポキシ当量150 以下の多官能エポキシ樹脂としてＥＬ
Ｍ−１００（住友化学社製、商品名）を40％、硬化剤と
してイミダゾール変性物のキュアダクトＰ−１０９０／
Ｌ−６１Ｂ（四国化成社製、商品名）を5 ％、触媒とし
てＳ−１８１（日本曹達社製、商品名）を1 ％、そして
無機フィラーとしてＳＯ２５Ｒ（龍森社製、商品名）を
54％を用いて熱硬化性樹脂接着剤を得た。この接着剤に
ついて、接着強度、ゲル化時間を評価したものを表１に
示す。Example 1 As a polyfunctional epoxy resin having an epoxy equivalent of 150 or less, EL
M-100 (manufactured by Sumitomo Chemical Co., Ltd., trade name) 40%, cure duct P-1090 /
5% of L-61B (trade name, manufactured by Shikoku Chemicals), 1% of S-181 (trade name, manufactured by Nippon Soda Co., Ltd.) as a catalyst, and SO25R (trade name, manufactured by Tatsumori Corporation) as an inorganic filler.
A thermosetting resin adhesive was obtained using 54%. Table 1 shows the evaluation results of the adhesive strength and the gel time of this adhesive.

【００１５】比較例１ エポキシ樹脂としてビスフェノールＡのＹＬ９８０（油
化シェルエポキシ社製、商品名）を40％、硬化剤として
イミダゾール変性品のキュアダクトＰ−１０９０／Ｌ−
６１Ｂ（四国化成社製、商品名）を5 ％、触媒としてチ
タネート系化合物のＳ−１８１（日本曹達社製、商品
名）を1 ％、そして無機フィラーとしてＳＯ２５Ｒ（龍
森社製、商品名）を54％を用いて熱硬化性樹脂接着剤を
得た。この接着剤について、実施例と同様の方法で接着
強度、ゲル化時間を評価したものを表１に示す。Comparative Example 1 Bisphenol A YL980 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) as an epoxy resin was 40%, and a curing agent, imidazole-modified cure duct P-1090 / L-, was used as a curing agent.
5% of 61B (trade name, manufactured by Shikoku Chemicals), 1% of a titanate compound S-181 (trade name, manufactured by Nippon Soda Co., Ltd.) as a catalyst, and SO25R (trade name, manufactured by Tatsumori Co., Ltd.) as an inorganic filler. Was used to obtain a thermosetting resin adhesive. Table 1 shows the evaluation results of the adhesive strength and the gel time of this adhesive in the same manner as in the examples.

【００１６】比較例２ エポキシ当量150 以下の多官能エポキシ樹脂としてＥＬ
Ｍ−１００（住友化学社製、商品名）を40％、硬化剤と
してイミダゾール変性品のキュアダクトＰ−１０９０／
Ｌ−６１Ｂ（四国化成社製、商品名）を2 ％、触媒とし
てチタネート系化合物のＳ−１８１（日本曹達社製、商
品名）を1 ％、そして無機フィラーとしてＳＯ２５Ｒ
（龍森社製、商品名）を57％を用いて熱硬化性樹脂接着
剤を得た。この接着剤について、実施例と同様の方法で
接着強度、ゲル化時間を評価したものを表１に示す。Comparative Example 2 EL was used as a polyfunctional epoxy resin having an epoxy equivalent of 150 or less.
M-100 (manufactured by Sumitomo Chemical Co., Ltd., trade name) 40%, cure duct P-1090 / imidazole modified product as a curing agent
2% L-61B (trade name, manufactured by Shikoku Chemicals), 1% titanate compound S-181 (trade name, manufactured by Nippon Soda Co., Ltd.) as a catalyst, and SO25R as an inorganic filler.
(Tatsumori Co., Ltd., trade name) was used to obtain a thermosetting resin adhesive. Table 1 shows the evaluation results of the adhesive strength and the gel time of this adhesive in the same manner as in the examples.

【００１７】比較例３ エポキシ当量150 以下の多官能エポキシ樹脂としてＥＬ
Ｍ−１００（住友化学社製、商品名）を40％、硬化剤と
してイミダゾール変性品のキュアダクトＰ−１０９０／
Ｌ−６１Ｂ（四国化成社製、商品名）を5 ％、そして無
機フィラーとしてＳＯ２５Ｒ（龍森社製、商品名）を55
％を用いて熱硬化性樹脂接着剤を得た。この接着剤につ
いて、実施例と同様の方法で接着強度、ゲル化時間を評
価したものを表１に示す。Comparative Example 3 EL was used as a polyfunctional epoxy resin having an epoxy equivalent of 150 or less.
M-100 (manufactured by Sumitomo Chemical Co., Ltd., trade name) 40%, cure duct P-1090 / imidazole modified product as a curing agent
5% of L-61B (trade name, manufactured by Shikoku Chemicals) and 55% of SO25R (trade name, manufactured by Tatsumori) as an inorganic filler.
% Was used to obtain a thermosetting resin adhesive. Table 1 shows the evaluation results of the adhesive strength and the gel time of this adhesive in the same manner as in the examples.

【００１８】[0018]

【表１】 ＊1 ：1 ｍｍ□シリコンチップとアルミナ基板との間に接着剤を挟み込み、150 ℃，2 分間で硬化させた後の230 ℃剪断試験で測定したものである。 ＊2 ：接着剤を150 ℃のホットプレート上で加熱し、硬化時間を測定したもので ある。[Table 1] * 1: Measured by a 230 ° C shear test after curing the adhesive at 150 ° C for 2 minutes with an adhesive sandwiched between the 1mm □ silicon chip and the alumina substrate. * 2: The curing time is measured by heating the adhesive on a hot plate at 150 ° C.

【００１９】[0019]

【発明の効果】以上の説明および表１から明らかなよう
に、本発明によれば、多官能エポキシ樹脂、イミダゾー
ルまたはイミダゾール変性物およびチタネート系化合物
を所定量混合することにより、加熱時の強度が増加し、
硬化時間を短縮することが可能な一液性の熱硬化性樹脂
接着剤を得ることができたものである。As is apparent from the above description and Table 1, according to the present invention, by mixing a predetermined amount of a polyfunctional epoxy resin, imidazole or a modified imidazole and a titanate compound, the strength during heating can be improved. Increase
Thus, a one-component thermosetting resin adhesive capable of shortening the curing time can be obtained.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 （Ａ）エポキシ当量150 以下の多官能エ
ポキシ樹脂、（Ｂ）硬化剤としてイミダゾール変性物お
よび（Ｃ）触媒としてチタネート系化合物を必須成分と
し、樹脂接着剤全体に対して、（Ａ）の多官能エポキシ
樹脂が40重量％以上、（Ｂ）のイミダゾール変性物が3
重量％以上、（Ｃ）のチタネート系化合物が1 重量％以
上の割合で含有することを特徴とする熱硬化性樹脂接着
剤。1. An essential component of (A) a polyfunctional epoxy resin having an epoxy equivalent of 150 or less, (B) a modified imidazole as a curing agent, and (C) a titanate-based compound as a catalyst. The polyfunctional epoxy resin of A) is at least 40% by weight, and the imidazole modified product of B) is 3% by weight.
A thermosetting resin adhesive characterized by containing at least 1% by weight of the titanate compound (C) in an amount of 1% by weight or more.
JP25455698A 1998-08-25 1998-08-25 Thermosetting resin adhesive Pending JP2000068294A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP25455698A JP2000068294A (en) 1998-08-25 1998-08-25 Thermosetting resin adhesive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP25455698A JP2000068294A (en) 1998-08-25 1998-08-25 Thermosetting resin adhesive

Publications (1)

Publication Number Publication Date
JP2000068294A true JP2000068294A (en) 2000-03-03

Family

ID=17266695

Family Applications (1)

Application Number Title Priority Date Filing Date
JP25455698A Pending JP2000068294A (en) 1998-08-25 1998-08-25 Thermosetting resin adhesive

Country Status (1)

Country Link
JP (1) JP2000068294A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030075949A (en) * 2002-03-22 2003-09-26 주식회사 원케미컬 Underfill resin composition
US7922860B2 (en) * 2005-03-18 2011-04-12 Konica Minolta Holdings, Inc. Manufacturing inkjet head by adhering with epoxy resins and alkyl imidazole
US7931352B2 (en) 2005-04-04 2011-04-26 Canon Kabushiki Kaisha Liquid discharge head and method for manufacturing the same
CN115304885A (en) * 2022-08-18 2022-11-08 湖南亿润新材料科技有限公司 Preparation method of medium-temperature cured high-Tg low-bromine epoxy resin prepreg

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030075949A (en) * 2002-03-22 2003-09-26 주식회사 원케미컬 Underfill resin composition
US7922860B2 (en) * 2005-03-18 2011-04-12 Konica Minolta Holdings, Inc. Manufacturing inkjet head by adhering with epoxy resins and alkyl imidazole
US7931352B2 (en) 2005-04-04 2011-04-26 Canon Kabushiki Kaisha Liquid discharge head and method for manufacturing the same
CN115304885A (en) * 2022-08-18 2022-11-08 湖南亿润新材料科技有限公司 Preparation method of medium-temperature cured high-Tg low-bromine epoxy resin prepreg

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