JPH0484444A - Conductive paste - Google Patents

Conductive paste

Info

Publication number
JPH0484444A
JPH0484444A JP2200102A JP20010290A JPH0484444A JP H0484444 A JPH0484444 A JP H0484444A JP 2200102 A JP2200102 A JP 2200102A JP 20010290 A JP20010290 A JP 20010290A JP H0484444 A JPH0484444 A JP H0484444A
Authority
JP
Japan
Prior art keywords
parts
conductive paste
epoxy resin
compound
aluminum
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
JP2200102A
Other languages
Japanese (ja)
Inventor
Tokuo Kurokawa
徳雄 黒川
Toshiyuki Sato
俊行 佐藤
Teru Okunoyama
奥野山 輝
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 JP2200102A priority Critical patent/JPH0484444A/en
Publication of JPH0484444A publication Critical patent/JPH0484444A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10WGENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00Interconnections or connectors in packages
    • H10W72/30Die-attach connectors
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistors
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits
    • H05K3/321Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits by conductive adhesives

Landscapes

  • Die Bonding (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

PURPOSE:To obtain high speed curing conductive paste having excellent adhesive properties and no void by employing aluminum compound having an organic group, silicone compound having an OH group directly coupled to Si or a hydrolyzable group, organosilane compound and conductive powder as indispensable ingredients as epoxy resin, curing catalyst. CONSTITUTION:22 parts of epoxy resin YL980 (trade name of Yuka Shell Bpoxy Co.), 4 parts of phenylglycidylether, 0.5 part of aluminum trisacetylacetonate, 0.5 part of diphenyldiethoxysilane and 73 parts of silver powder are mixed, and kneaded by three rolls to manufacture conductive paste (A) in an embodiment 1. In a second embodiment 2, 22 parts of the epoxy resin YL, 4 parts of phenylglycidylether, 0.5 part of aluminum trisethylacetate, 0.5 part of diphenylmethoxysilane and 73 parts of silver powder are mixed, and kneaded by three rolls to manufacture conductive paste (B).

Description

【発明の詳細な説明】 [発明の目的] (産業上の利用分野) 本発明は、半導体装置の組立て(アッセンブリ)や各種
部品類の接着等に使用する導電性ベーストに関し、半導
体ベレットの大型化とアッセンブリ工程の短縮化に対応
できるとともに、配線の腐蝕断線を起さず、接着性にも
優れた導電性ペーストに関する。
[Detailed Description of the Invention] [Objective of the Invention] (Industrial Application Field) The present invention relates to a conductive base used for assembling semiconductor devices and adhering various parts, etc. The present invention relates to a conductive paste that can shorten the assembly process, does not cause corrosion or disconnection of wiring, and has excellent adhesive properties.

(従来の技術) リードフレーム上の所定部分に、IC,LSI等の半導
体チップを接続する工程は、素子の長期信頼性に影響を
与える重要な工程の1つである。
(Prior Art) The process of connecting a semiconductor chip such as an IC or LSI to a predetermined portion on a lead frame is one of the important processes that affects the long-term reliability of the device.

従来から、この接続方法としてチップのシリコン面をリ
ードフレーム上の金メツキ面に加熱圧着するというAu
−3i共晶法が主流であった。 しかし、近年の貴金属
、特に金の高騰を契機として、樹脂封止型半導体装置で
はAu−8i共晶法から、導電性ペースト(接着剤)を
使用する方法等に急速に移行しつつある。
Conventionally, this connection method involves heating and pressing the silicon surface of the chip to the gold-plated surface of the lead frame.
-3i eutectic method was the mainstream. However, with the rise in the price of precious metals, particularly gold, in recent years, resin-sealed semiconductor devices are rapidly shifting from the Au-8i eutectic method to methods using conductive paste (adhesive).

しかし、導電性ペーストを使用する方法は、ボイドの発
生、耐湿性、耐加水分解性等に問題があり、アルミニウ
ム電極の腐蝕を促進し、断線不良の原因となる場合が多
く、素子の信頼性はAu −3i共晶法に比べて劣って
いた。
However, the method of using conductive paste has problems such as the generation of voids, moisture resistance, and hydrolysis resistance, which promotes corrosion of the aluminum electrode and often causes disconnection, which reduces the reliability of the element. was inferior to the Au-3i eutectic method.

(発明が解決しようとするNM> また、近年、IC,LSIやLED等の半導体チップの
大型化に伴い、ペレットクラックの発生や接着力の低下
が問題となっており、またアッセンブリ工程の短縮化を
9指して、高速硬化できる導電性ペーストの開発が強く
要望されていた。
(NM that the invention aims to solve) In addition, in recent years, as semiconductor chips such as ICs, LSIs, and LEDs have become larger, pellet cracks and decreased adhesive strength have become problems, and the assembly process has become shorter. 9, there was a strong demand for the development of a conductive paste that could be cured at high speed.

本発明は、上記の事情に鑑みてなされたもので、半導体
チップの大型化、アッセンブリ工程の短縮化に対応する
とともに、配線の腐蝕断線がなく、接着性に優れ、ボイ
ドの発生がない高速硬化性の導電性ペーストを提供しよ
うとするものである。
The present invention has been made in view of the above circumstances, and is compatible with the increase in the size of semiconductor chips and the shortening of the assembly process, and also has no corrosion or disconnection of wiring, excellent adhesiveness, and fast curing with no voids. The present invention aims to provide a highly conductive paste.

[発明の構成コ (J1!題を解決するための手段と作用)本発明者らは
、上記の目的を達成しようと鋭意研究を重ねた結果、後
述する組成の導を性ペーストが接着性に優れ、ボイドの
発生がなく低応力であることを見いだし、本発明を完成
したものである。
[Structure of the Invention (J1! Means and Effects for Solving the Problem) The inventors of the present invention have conducted intensive research to achieve the above object, and as a result, they have discovered that the adhesive paste has adhesive properties based on the composition described below. The present invention was completed based on the discovery that the material is excellent, has no voids, and has low stress.

すなわち、本発明は、 (A)エポキシ樹脂、 (B)硬化触媒として <a )有機基を有するアルミニウム化合物及び(b)
Siに直結したOH基若しくは加水分解性基を分子内に
1個以上有する、シリコーン化合物又はオルガノシラン
化合物、 (C)導電性粉末 を必須成分とすることを特徴とする導電性ペーストであ
る。
That is, the present invention comprises (A) an epoxy resin, (B) an aluminum compound having an organic group as a curing catalyst, and (b)
A conductive paste characterized by containing as essential components a silicone compound or an organosilane compound having one or more OH groups or hydrolyzable groups directly connected to Si in the molecule, and (C) conductive powder.

以下、本発明の詳細な説明する。The present invention will be explained in detail below.

本発明に用いる(A>エポキシ樹脂としては、例えばエ
ピコート827,828,834゜1001.1002
.1007.1009 <シェル化学社製、商品名)、
DER330,331332,334,335,336
,337゜660(ダウ・ケミカル社製、商品名)、ア
ラルダイトGY250.260,280,6071゜6
084.6097.6099 (チバガイギー社製、商
品名>、EPI−’REZ510.5101(JONE
  DABNEY社製、商品名)、エピクロン810.
1000,1010.3010(大日本インキ化学工業
社製、商品名)、地竜化社製EPシリーズ等が挙げられ
、これらは単独又は2種以上使用することができる。 
また、これらのエポキシ樹脂の高純度タイプ品や希釈剤
として使用される単官能エポキシ樹脂類も含まれる。
Examples of the epoxy resin used in the present invention (A>epoxy resin include Epicoat 827, 828, 834° 1001, 1002
.. 1007.1009 <Manufactured by Shell Chemical Co., Ltd., trade name),
DER330, 331332, 334, 335, 336
, 337°660 (manufactured by Dow Chemical Company, trade name), Araldite GY250.260, 280, 6071°6
084.6097.6099 (manufactured by Ciba Geigy, product name>, EPI-'REZ510.5101 (JONE
Manufactured by DABNEY, product name), Epicron 810.
1000, 1010.3010 (manufactured by Dainippon Ink & Chemicals, trade name), EP series manufactured by Jiryuka Co., Ltd., etc., and these can be used alone or in combination of two or more.
Also included are high-purity types of these epoxy resins and monofunctional epoxy resins used as diluents.

本発明における(B)硬化触媒としては、(a )有機
基を有するアルミニウム化合物および(b)Siに直結
したOH基若しくは加水分解性基を分子内に1個以上有
する、シリコーン化合物又はオルガノシラン化合物が併
用される。
The curing catalyst (B) in the present invention includes (a) an aluminum compound having an organic group, and (b) a silicone compound or an organosilane compound having one or more OH groups or hydrolyzable groups directly connected to Si in the molecule. are used together.

(a)有機基を有するアルミニウム化合物としては、例
えばメチル基、エチル基、イソプロピル基などのアルキ
ル基、ベンジル基などの芳香族基、メトキシ基、エトキ
シ基などのアルコキシ基、フェノキシ基、アセトオキシ
基などアシルオキシ基、アセチルアセトンなどの有機基
を有する化合物であり、具体的にはトリイソプロポキシ
アルミニウム、ジイソプロポキシアセトオキシアルミニ
ウム、アルミニウムトリスアセチルアセトネート、アル
ミニウムトリスエチルアセトアセテート、トリエチルア
ルミニウム等が挙げられ、これらは単独もしくは2種以
上混合して用いる。
(a) Examples of aluminum compounds having organic groups include alkyl groups such as methyl, ethyl and isopropyl groups, aromatic groups such as benzyl, alkoxy groups such as methoxy and ethoxy groups, phenoxy groups, acetoxy groups, etc. It is a compound having an organic group such as an acyloxy group or acetylacetone, and specific examples thereof include triisopropoxyaluminum, diisopropoxyacetoxyaluminum, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, triethylaluminum, etc. are used alone or in combination of two or more.

また(b )分子内に1個以上の81に直結したOH基
もしくは加水分解性基を有するシリコーン化合物又はオ
ルガノシラン化合物は次のものである。
Further, (b) silicone compounds or organosilane compounds having one or more OH groups or hydrolyzable groups directly connected to 81 in the molecule are as follows.

そのシリコーン化合物は、そのシロキサン骨格が直鎖状
又は分岐状のいずれであってもよく、直鎖状のものは次
の一般式 (但し、式中R’ 、R’は水素原子、アルキル基、芳
香族基、不飽和アルキル基、ハロアルキル基、OH基、
またはアルコキシル基などの加水分解性基を表す)で示
されるものであり、OH基もしくは加水分解性基を分子
内に1個以上含んでいなければならない、 これらのシ
リコーン化合物は単一の分子量である必要はなく、分子
量が低分子1体から高分子量体のどのようなものでも用
いることができる。
The silicone compound may have a linear or branched siloxane skeleton, and those having a linear structure have the following general formula (wherein R', R' are hydrogen atoms, alkyl groups, aromatic group, unsaturated alkyl group, haloalkyl group, OH group,
or a hydrolyzable group such as an alkoxyl group), and must contain one or more OH group or hydrolyzable group in the molecule.These silicone compounds have a single molecular weight. It is not necessary to have one, and any substance having a molecular weight ranging from a single low molecular weight substance to a high molecular weight substance can be used.

またオルガノシラン化合物としては、次の一般式 %式% (但し、式中R3,R’ 、R’ 、R’はアルキル基
、芳香族基、アルコキシル基などの加水分解性基、OH
基を表し、R3−R6のうち少なくとも1個はOH基も
しくは加水分解性基である)で示されるものである。 
これらのオルガノシラン化合物は単独又は2種以上混合
して使用することができる。
Organosilane compounds can also be used as organosilane compounds according to the following general formula:
(at least one of R3-R6 is an OH group or a hydrolyzable group).
These organosilane compounds can be used alone or in combination of two or more.

本発明に用いる(C)導電性粉末としては、例えば銀粉
末、表面に銀層を有する粉末等が使用される。
As the conductive powder (C) used in the present invention, for example, silver powder, powder having a silver layer on the surface, etc. are used.

本発明の導電性ペーストは、上述したエポキシ樹脂、硬
化触媒および導電性粉末を混合するが、必要に応じて粘
度調整用の溶剤、消泡則、カップリング剤、その他の添
加剤を配合することができる。 その溶剤としては、ジ
オキサン、ヘキサノン、ベンゼン、トルエン、ソルベン
トナフサ、工業用ガソリン、酢酸セロソルブ、エチルセ
ロソルブ、ブチルセロソルブアセテート、ブチルカルピ
トールアセテート、ジメチルホルムアミド、ジメチルア
セトアミド、N〜メチルピロリドン等が挙げられ、これ
らは単独もしくは2種以上混合して使用することができ
る。
The conductive paste of the present invention is made by mixing the above-mentioned epoxy resin, curing catalyst, and conductive powder, but if necessary, a solvent for viscosity adjustment, an antifoaming agent, a coupling agent, and other additives may be added. I can do it. Examples of the solvent include dioxane, hexanone, benzene, toluene, solvent naphtha, industrial gasoline, cellosolve acetate, ethyl cellosolve, butyl cellosolve acetate, butyl carpitol acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. These can be used alone or in combination of two or more.

本発明の導電性ペーストは、常法に従い上述した各成分
を十分混合した後、更に例えば三本ロールによる混練処
理し、その後減圧脱泡して製造することができる。
The conductive paste of the present invention can be produced by thoroughly mixing the above-mentioned components according to a conventional method, and then kneading the mixture using, for example, three rolls, followed by degassing under reduced pressure.

こうして製造された導電性ペーストを用いて半導体ペレ
ットとリードフレームを接着固定した後、ワイヤボンデ
ィングを行い、次いで封止樹脂で封止して半導体装置を
製造することができる。 この半導体装置は、(a)ア
ルミニウム化合物と、(b )シリコーン化合物または
シラン化合物とが併用されて硬化触媒として働くことに
より、200℃で導電性ペーストを加熱硬化訃せても、
大型チップの反り変形がなく、半導体チップは密接に固
着され、また優れたワイヤボンディングを得ることかで
きる。
After adhesively fixing the semiconductor pellet and the lead frame using the conductive paste manufactured in this way, wire bonding is performed, and then the semiconductor device is manufactured by sealing with a sealing resin. In this semiconductor device, (a) an aluminum compound and (b) a silicone compound or a silane compound are used in combination to act as a curing catalyst, so that even if the conductive paste is heated and cured at 200°C,
There is no warping of large chips, the semiconductor chips are closely fixed, and excellent wire bonding can be obtained.

(実施例) 次に本発明を実施例によって説明するが、本発明は以下
の実施例によって限定されるものではない、 以下の実
施例および比較例において1部」とは特に説明のない限
り「重量部」を意味する。
(Example) Next, the present invention will be explained by Examples, but the present invention is not limited by the following Examples. Parts by weight.

実施例 1 エポキシ樹脂YL980 (油化シェルエポキシ社製、
商品名)22部、フェニルグリシジルエーテル4部、ア
ルミニウムトリスアセチルアセトネート0.5部、ジフ
ェニルジェトキシシラン0.5部、および銀粉末73部
を混合し、三本ロールで混練して導電性ペースト(A>
を製造した。
Example 1 Epoxy resin YL980 (manufactured by Yuka Shell Epoxy Co., Ltd.,
22 parts of product name), 4 parts of phenylglycidyl ether, 0.5 parts of aluminum trisacetylacetonate, 0.5 parts of diphenyljethoxysilane, and 73 parts of silver powder were mixed and kneaded with three rolls to form a conductive paste. (A>
was manufactured.

実施例 2 エポキシ樹脂YL980 (前出)22部、フェニルグ
リシジルエーテル4部、アルミニウムトリスエチルアセ
テート0.5部、ジフェニルジメトキシシラン0.5部
、および銀粉末73部を混合し、更に三本ロールで混練
して導電性ペースト(B)を製造した。
Example 2 22 parts of epoxy resin YL980 (mentioned above), 4 parts of phenylglycidyl ether, 0.5 parts of aluminum trisethyl acetate, 0.5 parts of diphenyldimethoxysilane, and 73 parts of silver powder were mixed, and further mixed with three rolls. The mixture was kneaded to produce a conductive paste (B).

実施例 3 エポキシ樹脂エピコート807(油化シェルエポキシ樹
脂、商品名)22部、フェニルグリシジルエーテル3部
、アルミニウムトリスエチルアセトアセテート0,5部
、5H6018(トーレ・ダウコーニング社製商品名、
Si −OH基を有する)0.5部、および銀粉末74
部を混合し、更に三本ロールで混練して導電性ペースト
(C)を製造した。
Example 3 22 parts of epoxy resin Epicoat 807 (oiled shell epoxy resin, trade name), 3 parts of phenyl glycidyl ether, 0.5 parts of aluminum trisethyl acetoacetate, 5H6018 (trade name, manufactured by Torre Dow Corning)
0.5 part of Si-OH group) and 74 parts of silver powder
The components were mixed and further kneaded using three rolls to produce a conductive paste (C).

比較例 市販のエポキシIII脂ベースの溶剤型半導体用導電性
接着列(D)を入手した。
Comparative Example A commercially available epoxy III resin-based solvent-based conductive adhesive array (D) for semiconductors was obtained.

実施例1〜3および比較例で得た導電性ペースト(A)
、(B)、(C)および導電性接着剤(D)を用いて半
導体チップとリードフレームとを接着硬化させて固定し
た。 これらについて接着強度、ボイドの有無、チップ
の反りの試験を行った。 その結果を第1表に示したが
いずれも本発明が優れており、本発明の顕著な効果が認
められな。
Conductive paste (A) obtained in Examples 1 to 3 and comparative example
, (B), (C) and a conductive adhesive (D), the semiconductor chip and the lead frame were adhesively cured and fixed. These were tested for adhesive strength, presence of voids, and chip warpage. The results are shown in Table 1, and the present invention was superior in all cases, and no significant effect of the present invention was observed.

第 表 (単位) [発明の効果] 以上の説明および第1表から明らかなように、本発明の
導電性ペーストは、接着性に優れ、配線の腐蝕断線がな
く、ボイドの発生やチップの反りが少なく、高速硬化性
のもので、半導体チ・yブの大型化、アッセンブリ工程
の短縮化に対応する信頼性の高い半導体装置を製造する
ことができる。
Table (Units) [Effects of the Invention] As is clear from the above explanation and Table 1, the conductive paste of the present invention has excellent adhesive properties, does not cause corrosion or disconnection of wiring, and does not cause voids or chip warpage. It has a small amount of oxidation and hardens at a high speed, so it is possible to manufacture highly reliable semiconductor devices that can accommodate larger semiconductor chips and shorter assembly processes.

特許出願人 東芝ケミカル株式会社 代理人   弁理士 諸1)英ニや2.1□・4 *1 *2 :銀メツキを施したリードフレーム(銅系)上に4X1
21111のシリコン素子を接着し、それぞれの温度で
プッシュプルゲージを用いて測定しな。
Patent applicant: Toshiba Chemical Co., Ltd. agent Patent attorney Miscellaneous 1) Einiyara 2.1□・4 *1 *2: 4X1 on a silver-plated lead frame (copper-based)
Glue 21111 silicon elements and measure using a push-pull gauge at each temperature.

:硬化後のシリコン素子の表面における反りを測定しな
: Measure the warpage on the surface of the silicon element after curing.

Claims (1)

【特許請求の範囲】 1(A)エポキシ樹脂、 (B)硬化触媒として (a)有機基を有するアルミニウム化合物及び (b)Siに直結したOH基若しくは加水分解性基を分
子内に1個以上有する、 シリコーン化合物又はオルガノシラン化合物、 (C)導電性粉末 を必須成分とすることを特徴とする導電性ペースト。
[Scope of Claims] 1 (A) an epoxy resin; (B) a curing catalyst; (a) an aluminum compound having an organic group; and (b) one or more OH groups or hydrolyzable groups directly connected to Si in the molecule. 1. A conductive paste comprising: a silicone compound or an organosilane compound; and (C) a conductive powder.
JP2200102A 1990-07-27 1990-07-27 Conductive paste Pending JPH0484444A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2200102A JPH0484444A (en) 1990-07-27 1990-07-27 Conductive paste

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2200102A JPH0484444A (en) 1990-07-27 1990-07-27 Conductive paste

Publications (1)

Publication Number Publication Date
JPH0484444A true JPH0484444A (en) 1992-03-17

Family

ID=16418877

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2200102A Pending JPH0484444A (en) 1990-07-27 1990-07-27 Conductive paste

Country Status (1)

Country Link
JP (1) JPH0484444A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258618A (en) * 1994-03-22 1995-10-09 Sumitomo Bakelite Co Ltd Conductive resin paste
WO2002091395A1 (en) * 2001-05-07 2002-11-14 Honeywell International Inc. Interface materials and methods of production and use thereof
US6605238B2 (en) 1999-09-17 2003-08-12 Honeywell International Inc. Compliant and crosslinkable thermal interface materials
WO2008133108A1 (en) 2007-04-17 2008-11-06 Asahi Kasei Chemicals Corporation Epoxy silicone and method for production thereof, and curable resin composition using the same and use thereof
JP2011520023A (en) * 2008-05-14 2011-07-14 ヘンケル コーポレイション Curable compositions and their use

Cited By (10)

* Cited by examiner, † Cited by third party
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JPH07258618A (en) * 1994-03-22 1995-10-09 Sumitomo Bakelite Co Ltd Conductive resin paste
US6605238B2 (en) 1999-09-17 2003-08-12 Honeywell International Inc. Compliant and crosslinkable thermal interface materials
US6706219B2 (en) 1999-09-17 2004-03-16 Honeywell International Inc. Interface materials and methods of production and use thereof
US6811725B2 (en) 2001-01-30 2004-11-02 Honeywell International Inc. Compliant and crosslinkable thermal interface materials
WO2002091395A1 (en) * 2001-05-07 2002-11-14 Honeywell International Inc. Interface materials and methods of production and use thereof
JP2004533705A (en) * 2001-05-07 2004-11-04 ハネウエル・インターナシヨナル・インコーポレーテツド Interface materials and their production and use
EP1763040A1 (en) * 2001-05-07 2007-03-14 Honeywell International Inc. Interface materials and methods of production and use thereof
WO2008133108A1 (en) 2007-04-17 2008-11-06 Asahi Kasei Chemicals Corporation Epoxy silicone and method for production thereof, and curable resin composition using the same and use thereof
US8222348B2 (en) 2007-04-17 2012-07-17 Asahi Kasei Chemicals Corporation Epoxy silicone and process for producing same, and curable mix composition using same and use thereof
JP2011520023A (en) * 2008-05-14 2011-07-14 ヘンケル コーポレイション Curable compositions and their use

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