JP2002097270A - Imide based olygomer having acid anhydride at terminal, and resin composition having curing property - Google Patents
Imide based olygomer having acid anhydride at terminal, and resin composition having curing propertyInfo
- Publication number
- JP2002097270A JP2002097270A JP2000288631A JP2000288631A JP2002097270A JP 2002097270 A JP2002097270 A JP 2002097270A JP 2000288631 A JP2000288631 A JP 2000288631A JP 2000288631 A JP2000288631 A JP 2000288631A JP 2002097270 A JP2002097270 A JP 2002097270A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- acid anhydride
- component
- terminal
- imide
- 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.)
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Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、末端に酸無水物
基を有するイミド系オリゴマ−及び該イミド系オリゴマ
−をエポキシ樹脂硬化剤として含有するエポキシ樹脂組
成物に関し、さらに詳しくはエポキシ樹脂との相溶性に
優れ有機溶媒の使用を実質的に必要とせずエポキシ樹脂
硬化剤として好適なイミド系オリゴマ−、および破断応
力や曲げ弾性率が小さいなど低応力の硬化物を与える硬
化性エポキシ樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an imide oligomer having an acid anhydride group at a terminal and an epoxy resin composition containing the imide oligomer as a curing agent for an epoxy resin. An imide-based oligomer which is excellent in compatibility and practically does not require the use of an organic solvent and is suitable as an epoxy resin curing agent, and a curable epoxy resin composition which provides a cured product having low stress such as low breaking stress and low flexural modulus. About.
【０００２】[0002]
【従来の技術】近年、ダイオ−ド、トランジスタ、Ｉ
Ｃ、ＬＳＩ等の半導体装置は、一般的には熱硬化性樹脂
を用いて封止されている。中でもエポキシ樹脂は、経済
性、性能の上でバランスがとれているため、一般的に使
用されている。そして、半導体装置の実装は表面実装へ
と移行している。表面実装においては、半導体装置はハ
ンダ浴に直接浸漬されるハンダ浸漬方式や半田リフロ−
方式が採用されている。この際に高温にさらされるた
め、パッケ−ジ全体に急激に大きな応力がかかり、封止
剤にクラックが入る。このため、エポキシ樹脂には、硬
化物として低応力であることが要求される。2. Description of the Related Art In recent years, diodes, transistors, I
Semiconductor devices such as C and LSI are generally sealed using a thermosetting resin. Among them, epoxy resins are generally used because they are balanced in economy and performance. The mounting of semiconductor devices has shifted to surface mounting. In surface mounting, the semiconductor device is soldered by a solder immersion method in which the semiconductor device is immersed directly in a solder bath.
The method is adopted. At this time, since the package is exposed to a high temperature, a large stress is suddenly applied to the entire package, and the sealant is cracked. For this reason, the epoxy resin is required to have a low stress as a cured product.
【０００３】このエポキシ樹脂の問題を解決するため、
ブタジエンゴムやシリコ−ンゴム粒子をエポキシ樹脂組
成物中に分散させたり、アルキレン基、ブタジエン基、
あるいはシリコ−ン基をエポキシ樹脂分子中に導入した
ものや、これらの基を硬化剤分子中に導入したものが提
案されている。しかし、これらは、分散性、相溶性が劣
るため、不均質な相分離構造を有する硬化物を与え、十
分な低応力を付与することが困難である。In order to solve the problem of the epoxy resin,
Dispersing butadiene rubber or silicone rubber particles in an epoxy resin composition, alkylene group, butadiene group,
Alternatively, those in which a silicone group is introduced into an epoxy resin molecule and those in which these groups are introduced into a curing agent molecule have been proposed. However, since these have poor dispersibility and compatibility, it is difficult to provide a cured product having an inhomogeneous phase separation structure and to apply a sufficiently low stress.
【０００４】また、封止材を流動性のある一液性とし
て、常温など比較的低温でボンディングならびにディッ
ピングして、浸透圧で半導体やダイオ−ド等を封止する
方式が行われており、この場合には、液状のエポキシ樹
脂と半固形もしくは固形のフェノ−ルノボラック硬化剤
あるいは液状の酸無水物、アミン、アミド等の硬化剤が
用いられている。このような半固形もしくは固形のフェ
ノ−ルノボラック樹脂を用いる封止材は、流動性が悪
く、溶剤を用いたものは硬化後、封止材中に溶剤が取り
込まれるため性能に悪影響を及ぼす。[0004] Further, there is a method in which a sealing material is made into a liquid one-part liquid and bonded and dipped at a relatively low temperature such as room temperature to seal a semiconductor or a diode by osmotic pressure. In this case, a liquid epoxy resin and a semi-solid or solid phenol-novolak hardener or a hardener such as a liquid acid anhydride, an amine or an amide are used. A sealing material using such a semi-solid or solid phenol novolak resin has poor fluidity, and a solvent using a solvent has a bad influence on performance because the solvent is taken into the sealing material after curing.
【０００５】さらに、通常の酸無水物、アミン、アミド
系の硬化剤を用いて無溶剤型の封止材を構成すると、均
一な硬化性樹脂組成物が得られないとか信頼性が劣ると
いう問題がある。このような問題点を解決するために、
流動性があって相溶性があり、硬化物が低応力を示す硬
化剤が必要になってきている。[0005] Further, when a solventless encapsulant is formed by using a usual acid anhydride, amine or amide-based curing agent, a uniform curable resin composition cannot be obtained or the reliability is poor. There is. In order to solve such problems,
There is a need for a curing agent that is fluid and compatible, and that shows a low stress in the cured product.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、無溶
剤型の硬化性樹脂組成物を与え得る、流動性があって相
溶性があり、硬化物が低応力を示す硬化剤を提供するこ
とである。また、この発明の他の目的は、無溶剤型で硬
化物が低応力を示す硬化性樹脂組成物を提供することで
ある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a hardening agent which can provide a solventless curable resin composition, has fluidity and compatibility, and has a cured product having low stress. That is. Another object of the present invention is to provide a curable resin composition which is a solventless type and whose cured product exhibits low stress.
【０００７】[0007]
【課題を解決するための手段】すなわち、この発明は、
下記式That is, the present invention provides:
The following formula
【０００８】[0008]
【化２】 ［式中、Ａは非対称芳香族又は脂環式テトラカルボン酸
二無水物残基で、Ｂはジアミノポリシロキサン残基であ
る。］で示されるイミド単位を有し、Ａ成分とＢ成分と
の組成比（Ａ／Ｂ）が１．２〜５の範囲内にあり末端に
酸無水物基を有するイミド系オリゴマ−に関する。Embedded image Wherein A is an asymmetric aromatic or alicyclic tetracarboxylic dianhydride residue, and B is a diaminopolysiloxane residue. And an imide-based oligomer having a composition ratio (A / B) of the component A and the component B in the range of 1.2 to 5 and having an acid anhydride group at a terminal.
【０００９】また、この発明は、非対称芳香族又は脂環
式テトラカルボン酸二無水物（Ａ成分）を一旦エステル
化剤、特に炭素数４以下の一級アルコ−ルを用いてハ−
フエステル化し、得られた反応液にジアミノポリシロキ
サン（Ｂ成分）を各成分の組成比（Ａ／Ｂ）が１．２〜
５の範囲内となるように加え、最終的に１３０℃以上で
２５０℃未満の温度にてワンポット反応にて脱水反応さ
せ、実質的に溶媒が残存しない条件で製造してなる末端
に酸無水物基を有するイミド系オリゴマ−に関する。The present invention also relates to a method for preparing an asymmetric aromatic or alicyclic tetracarboxylic dianhydride (component A) by using an esterifying agent, particularly a primary alcohol having 4 or less carbon atoms.
The diaminopolysiloxane (component B) was added to the resulting reaction solution at a composition ratio (A / B) of 1.2 to 1.2.
5 and finally subjected to a dehydration reaction in a one-pot reaction at a temperature of 130 ° C. or more and less than 250 ° C., and acid anhydrides at the terminals produced under conditions in which substantially no solvent remains. The present invention relates to an imide-based oligomer having a group.
【００１０】さらに、この発明は、前記の末端に酸無水
物残基を有するイミド系オリゴマ−およびエポキシ樹脂
を含有する硬化性樹脂組成物に関する。Further, the present invention relates to a curable resin composition containing an imide oligomer having an acid anhydride residue at the terminal and an epoxy resin.
【００１１】この発明における非対称芳香族又は脂環式
テトラカルボン酸二無水物としては、２，３，３’，
４’−ビフェニルテトラカルボン酸二無水物等の非対称
芳香族テトラカルボン酸二無水物や、対称芳香族テトラ
カルボン酸二無水物の水素還元化物、例えばジシクロヘ
キシル−３，３’４，４’−テトラカルボン酸二無水物
［３，３’，４，４’−ビフェニルテトラカルボン酸テ
トラメチルを水素還元−加圧加熱加水分解−無水化して
得られる。］、下記式The asymmetric aromatic or alicyclic tetracarboxylic dianhydride in the present invention includes 2,3,3 ',
Asymmetric aromatic tetracarboxylic dianhydrides such as 4'-biphenyltetracarboxylic dianhydride and hydrogenated products of symmetric aromatic tetracarboxylic dianhydrides, for example, dicyclohexyl-3,3'4,4'-tetra Carboxylic acid dianhydride [obtained by hydrogen reduction-hydrogenation under pressure-hydrolysis-hydrogenation of tetramethyl 3,3 ', 4,4'-biphenyltetracarboxylate]. ], The following formula
【００１２】[0012]
【化３】 で示される脂環式テトラカルボン酸二無水物等が挙げら
れる。Embedded image And an alicyclic tetracarboxylic dianhydride.
【００１３】この発明におけるジアミノポリシロキサン
としては、下記式 Ｈ2Ｎ−Ｒ−［Ｓｉ（Ｒ1）（Ｒ2）−Ｏ−］n−Ｓｉ（Ｒ
3）（Ｒ4）−Ｒ−ＮＨ2 （ただし、式中のＲは炭素数２〜６個のメチレン基また
はフェニレン基からなる２価の炭化水素残基を示し、Ｒ
1、Ｒ2、Ｒ3及びＲ4は炭素数１〜５個の低級アルキル基
又はフェニル基を示し、nは３〜６０の整数を示す。）
で示されるジアミノポリシロキサンが挙げられる。The diaminopolysiloxane used in the present invention is represented by the following formula: H 2 N—R— [Si (R 1 ) (R 2 ) —O—] n—Si (R
3 ) (R 4 ) —R—NH 2 (where R represents a divalent hydrocarbon residue comprising a methylene group or a phenylene group having 2 to 6 carbon atoms;
1 , R 2 , R 3 and R 4 each represent a lower alkyl group having 1 to 5 carbon atoms or a phenyl group, and n represents an integer of 3 to 60. )
The diaminopolysiloxane shown by these is mentioned.
【００１４】前記ジアミノポリシロキサンの具体的化合
物の例としてはα，ω−ビス（２−アミノエチル) ポリ
ジメチルシロキサン、α，ω−ビス（３−アミノプロピ
ル)ポリジメチルシロキサン、α，ω−ビス（４−アミ
ノフェニル) ポリジメチルシロキサン、α，ω−ビス
（４−アミノ−３−メチルフェニル) ポリジメチルシロ
キサン、α，ω−ビス（３−アミノプロピル) ポリジフ
ェニルシロキサン、α，ω−ビス（４−アミノブチル)
ポリジメチルシロキサンなどが挙げられる。この発明に
おいては、発明の効果を損なわない範囲内でジアミノポ
リシロキサンの一部を他の種類のジアミンで置き換えて
もよい。Examples of the specific compound of the diaminopolysiloxane include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (4-amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis ( 4-aminobutyl)
And polydimethylsiloxane. In the present invention, a part of the diaminopolysiloxane may be replaced with another kind of diamine as long as the effects of the present invention are not impaired.
【００１５】この発明の末端に酸無水物残基を有するイ
ミド系オリゴマ−は、好適には前記の非対称芳香族又は
脂環式テトラカルボン酸二無水物（Ａ成分）を一旦エス
テル化剤、特に炭素数４以下の一級アルコ−ルを用い
て、好適には０．５〜２４時間程度還流した後反応混合
物を冷却してハ−フエステル化し、得られた反応液にジ
アミノポリシロキサン（Ｂ成分）を両成分の組成比（Ａ
／Ｂ）が１．２〜５、特に１．５〜３の範囲内となるよ
うに加え、不活性ガス流通下、初期においてハ−フエス
テル化用の一級アルコ−ルを留去し、最終的に１３０℃
以上で２５０℃未満の温度、特に１６０〜２１０℃に
て、０．５〜２４時間程度攪拌下に加熱するワンポット
反応にて脱水反応させた後、反応混合物を冷却して実質
的に溶媒が残存しない反応物として得ることができる。The imide oligomer having an acid anhydride residue at the terminal of the present invention is preferably an esterifying agent for the above-mentioned asymmetric aromatic or alicyclic tetracarboxylic dianhydride (component A), especially an esterifying agent. After refluxing for about 0.5 to 24 hours using a primary alcohol having 4 or less carbon atoms, the reaction mixture is cooled and half-esterified, and diaminopolysiloxane (component (B)) is added to the obtained reaction solution. With the composition ratio of both components (A
/ B) is in the range of 1.2 to 5, especially 1.5 to 3, and the primary alcohol for half esterification is distilled off at the beginning under the flow of inert gas. 130 ° C
After a dehydration reaction in a one-pot reaction where the mixture is heated under stirring at a temperature of less than 250 ° C., in particular, 160 to 210 ° C. for about 0.5 to 24 hours, the reaction mixture is cooled to substantially leave the solvent. Can be obtained as unreacted reactants.
【００１６】前記のハ−フエステル化するエステル化剤
としては、アルコ−ル性ＯＨ基を１個有する化合物、例
えば、メタノ−ル、エタノ−ル、イソプロパノ−ル、ブ
タノ−ル、エチルセロソルブ、ブチルセロソルブ、プロ
ピレングリコ−ルエチルエ−テル、エチルカルビト−ル
等、特に炭素数４以下である脂肪族アルコ−ルが挙げら
れる。前記の炭素数４以下である脂肪族アルコ−ル等の
エステル化剤の使用量は、テトラカルボン酸二無水物１
００重量部に対して２０〜１０００重量部程度であるこ
とが好ましい。Examples of the esterifying agent for the half esterification include compounds having one alcoholic OH group, for example, methanol, ethanol, isopropanol, butanol, ethyl cellosolve, butyl cellosolve. And aliphatic alcohols having 4 or less carbon atoms, especially, propylene glycol ethyl ether and ethyl carbitol. The amount of the above-mentioned esterifying agent such as an aliphatic alcohol having 4 or less carbon atoms is determined by the amount of tetracarboxylic dianhydride 1
It is preferably about 20 to 1000 parts by weight based on 00 parts by weight.
【００１７】この発明の硬化性樹脂組成物は、エポキシ
樹脂に、前記の末端に酸無水物基を有するイミド系オリ
ゴマ−を硬化剤として混合して得られる。前記のエポキ
シ樹脂としては、１分子中に２つ以上のエポキシ基を有
するものはすべて含まれる。具体的には、エポキシ当量
が１００〜１０００程度であって、分子量が３００〜５
０００程度である液状のエポキシ樹脂が好ましい。例え
ば、ビスフェノ−ルＡ型やビスフェノ−ルＦ型のエポキ
シ樹脂（油化シェル社製：エピコ−ト８０６、エピコ−
ト８２５、エピコ−ト８２８など）、フェノ−ルノボラ
ック型エポキシ樹脂、クレゾ−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、トリフェノ−ルメ
タン型エポキシ樹脂、トリフェノ−ルプロパンエポキシ
樹脂等のトリフェノ−ルアルカン型エポキシ樹脂、ビフ
ェニル型エポキシ樹脂、ビフェニル骨格を含有しないフ
ェノ−ルアラルキル型エポキシ樹脂、複素環型エポキシ
樹脂、ナフタレン環含有エポキシ樹脂、スチルベン型エ
ポキシ樹脂などを挙げることができる。これらのうちの
１種又は２種以上を使用することができる。また、これ
らの中ではビスフェノ−ルＡ型エポキシ樹脂、ビスフェ
ノ−ルＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、
スチルベン型エポキシ樹脂等が好ましい。The curable resin composition of the present invention is obtained by mixing an epoxy resin with an imide oligomer having an acid anhydride group at a terminal as a curing agent. The above-mentioned epoxy resin includes all those having two or more epoxy groups in one molecule. Specifically, the epoxy equivalent is about 100 to 1000 and the molecular weight is 300 to 5
A liquid epoxy resin of about 000 is preferred. For example, a bisphenol A type or a bisphenol F type epoxy resin (manufactured by Yuka Shell Co., Ltd .: Epicoat 806, Epicoat
825, epicoat 828), novolak epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, triphenol alkane epoxy such as triphenol methane epoxy resin and triphenol propane epoxy resin. Resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins not containing a biphenyl skeleton, heterocyclic type epoxy resins, naphthalene ring-containing epoxy resins, stilbene type epoxy resins, and the like can be given. One or more of these can be used. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin,
Stilbene type epoxy resins and the like are preferred.
【００１８】この発明において硬化性樹脂組成物には、
エポキシ樹脂および前記末端に酸無水物基を有するイミ
ド系オリゴマ−と共に他の硬化剤および硬化促進触媒を
含有させてもよい。このような、硬化剤としては、脂環
式酸無水物、フェノ−ルノボラック樹脂等が挙げられ
る。硬化促進触媒としては、ヒドラジド類、イミダゾ−
ル類等が挙げられる。特に、この発明においては、無溶
剤系硬化性樹脂組成物を得るために、油化シェルエポキ
シ社製の脂環式酸無水物型硬化剤（ＹＨ３０６）が好適
である。In the present invention, the curable resin composition includes:
Other curing agents and curing acceleration catalysts may be contained together with the epoxy resin and the imide-based oligomer having an acid anhydride group at the terminal. Examples of such a curing agent include alicyclic acid anhydrides and phenol novolak resins. Hydrazides, imidazo-
And the like. In particular, in the present invention, in order to obtain a solvent-free curable resin composition, an alicyclic acid anhydride type curing agent (YH306) manufactured by Yuka Shell Epoxy is suitable.
【００１９】この発明において各成分の使用割合は、溶
剤を使用しないで比較的低温で組成物が液状に保たれる
割合を基準にして各成分の量が決められる。好適には、
エポキシ樹脂１００重量部に対して末端に酸無水物基を
有するイミド系オリゴマ−のシロキサン部の合計量が約
１０〜９０重量部であることが好ましい。また、例え
ば、脂環式酸無水物型硬化剤の場合、エポキシ樹脂のエ
ポキシの全量１当量に対して、硬化剤の官能基の全量が
０．９〜１．０当量であることが好ましい。In the present invention, the proportion of each component used is determined based on the proportion of the composition kept in a liquid state at a relatively low temperature without using a solvent. Preferably,
It is preferable that the total amount of the siloxane part of the imide-based oligomer having an acid anhydride group at the terminal is about 10 to 90 parts by weight based on 100 parts by weight of the epoxy resin. For example, in the case of an alicyclic acid anhydride type curing agent, the total amount of the functional groups of the curing agent is preferably 0.9 to 1.0 equivalent with respect to 1 equivalent of the total epoxy of the epoxy resin.
【００２０】この発明の硬化性樹脂組成物は、２５℃で
粘度が約１〜６００ポイズであることが作業性や溶液物
性、その封止材特性上などから適当である。The curable resin composition of the present invention preferably has a viscosity of about 1 to 600 poise at 25 ° C. from the viewpoint of workability, physical properties of the solution, and properties of the sealing material.
【００２１】この発明の硬化性樹脂組成物は、前記の組
成からなり粘度を有しているため、半導体素子、絶縁性
フィルムおよびその上に導体で形成されたパタ−ンを有
する電子部品に、乾燥膜の厚さが１０〜５００μｍ程度
となるようにスピンコ−ティング、スクリ−ン印刷、浸
漬法、スプレ−コ−トなどによって塗布した後、６５〜
１２０℃程度の温度で３０〜１２０分間程度、ついで１
２０〜２００℃程度の温度で２〜８時間分間程度の２段
階で加熱し硬化させて、曲げ弾性率が５０〜２９０ｋｇ
／ｍｍ2 の封止材を形成することが好ましい。Since the curable resin composition of the present invention has the above-mentioned composition and has a viscosity, it can be used for a semiconductor element, an insulating film, and an electronic component having a pattern formed of a conductor thereon. After being applied by spin coating, screen printing, dipping, spray coating, etc., so that the thickness of the dried film is about 10 to 500 μm,
At a temperature of about 120 ° C for about 30 to 120 minutes,
It is heated and cured in two stages of about 2 to 8 hours at a temperature of about 20 to 200 ° C., and has a flexural modulus of 50 to 290 kg.
/ Mm 2 is preferably formed.
【００２２】[0022]
【実施例】以下、実施例により、本発明のエポキシ樹脂
組成物の製造およびその硬化物の製造法について詳細説
明する。硬化剤の粘度は、Ｅ型粘度計を用いて６０℃で
測定した。実施例中の硬化物の曲げ弾性率は、ＴＯＹＯ
ＢＯＬＤＷＩＮ社製ＴＥＮＳＩＬＯＮ ＵＴＭ５Ｔを
用い、スパン幅５０ｍｍ、クロスヘッド速度２ｍｍ／ｍ
ｉｎの条件で測定した。EXAMPLES Hereinafter, the production of the epoxy resin composition of the present invention and the method of producing a cured product thereof will be described in detail with reference to examples. The viscosity of the curing agent was measured at 60 ° C. using an E-type viscometer. The flexural modulus of the cured product in the examples was TOYO.
Using BOLDWIN TENSILON UTM5T, span width 50 mm, crosshead speed 2 mm / m
It was measured under the conditions of "in".
【００２３】合成例１ 窒素置換した四つ口フラスコに、撹拌機、窒素導入管、
還流冷却器、共栓を取り付け、前記の大日本インキ化学
工業株式会社社製 エピクロン Ｂ４４００ ３７．９
０ｇ（１４３．４ｍｍｏｌ）、メタノ−ル５０ｇを入
れ、還流した。３時間後、室温まで冷却し、還流冷却器
を水分離器付きの還流冷却器に換え、消泡剤［ダウコ−
ニングアジア株式会社ＦＳアンチフォ−ム ＤＢ−１０
０］０．１０ｇ、ジアミノポリシロキサン［東レ・ダウ
コ−ニングシリコ−ン株式会社 ＢＹ１６−８５３Ｕ、
Ｒ＝Ｃ３Ｈ６、Ｒ１〜Ｒ４＝ＣＨ３、アミン価４５１］
６４．６８ｇ（７１．７１ｍｍｏｌ）を加え、１時間か
けてメタノ−ルを留去した。続けて１９０℃まで昇温
し、水を留去しながら、１時間反応させ、９７．８９ｇ
（収率９７．９０％）の茶褐色の粘調物を得た。この生
成物（ＳｉＢ）の６０℃での粘度は、３１１ｐｏｉｓｅ
であった。Synthesis Example 1 A nitrogen-substituted four-necked flask was charged with a stirrer, a nitrogen introducing tube,
Attach a reflux condenser and a stopper, and install the above-mentioned Epicron B4400 37.9 manufactured by Dainippon Ink and Chemicals, Inc.
0 g (143.4 mmol) and 50 g of methanol were added and refluxed. After 3 hours, the mixture was cooled to room temperature, and the reflux condenser was replaced with a reflux condenser with a water separator.
Ning Asia Co., Ltd. FS Anti-Form DB-10
0] 0.10 g, diaminopolysiloxane [Toray Dow Corning Silicone Co., Ltd. BY16-853U,
R = C3H6, R1 to R4 = CH3, amine value 451]
64.68 g (71.71 mmol) was added, and methanol was distilled off over 1 hour. Subsequently, the temperature was raised to 190 ° C., and the reaction was carried out for 1 hour while distilling off water.
A brown viscous substance (yield 97.90%) was obtained. The viscosity at 60 ° C. of the product (SiB) is 311 poise
Met.
【００２４】合成例２ 窒素置換した四つ口フラスコに、撹拌機、窒素導入管、
還流冷却器、共栓を取り付け、２，３，３’，４’−ビ
フェニルテトラカルボン酸二無水物（a−BPDA） ２
０．２３ｇ（６８．７６ｍｍｏｌ）、メタノ−ル３０ｇ
を入れ、還流した。３時間後、室温まで冷却し、還流冷
却器を水分離器付きの還流冷却器に換え、消泡剤（ダウ
コ−ニングアジア株式会社ＦＳアンチフォ−ム ＤＢ−
１００）０．０７ｇ、東レ・ダウコ−ニングシリコ−ン
株式会社アミノ変性シリコ−ンオイル ＢＹ１６−８５
３Ｕ（ＤＡＰＳｉ）（アミン価４５１）３１．０１ｇ
（３４．３８ｍｍｏｌ）を加え、１時間かけてメタノ−
ルを留去した。続けて１９０℃まで昇温し、水を留去し
ながら、１時間反応させ、４８．７５ｇ（収率９７．５
０％）の茶褐色の粘調物を得た。この生成物（ＳｉＡ）
の８０℃での粘度は、３９２ｐｏｉｓｅであった。Synthesis Example 2 A nitrogen-substituted four-necked flask was equipped with a stirrer, a nitrogen introducing tube,
Attach a reflux condenser and a stopper, and add 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) 2
0.23 g (68.76 mmol), methanol 30 g
And refluxed. After 3 hours, the mixture was cooled to room temperature, the reflux condenser was replaced with a reflux condenser with a water separator, and an antifoaming agent (Dow Corning Asia Co., Ltd. FS Antiform DB-
100) 0.07 g, Dow Corning Silicone Toray Co., Ltd. Amino-modified silicone oil BY16-85
31.01 g of 3U (DAPSi) (amine number 451)
(34.38 mmol) and methano-
Was distilled off. Subsequently, the temperature was raised to 190 ° C., and the reaction was carried out for 1 hour while distilling off water to obtain 48.75 g (yield 97.5).
(0%). This product (SiA)
Had a viscosity of 392 poise at 80 ° C.
【００２５】実施例１ 油化シェルエポキシ株式会社社製エピコ−ト８２８を１
００ｇ、合成例１で得たＳｉＢを２４ｇ、脂環式酸無水
物型硬化剤である油化シェルエポキシ株式会社社製エピ
キュアＹＨ３０６を１１６ｇ、硬化促進触媒（四国化成
工業株式会社社製キュアゾ−ル２Ｅ４ＭＺ）１ｇを混
合、均一とした後、アドバンテック社製ろ紙４０８（孔
径５μｍ）を用いてろ過し、真空脱法を行った。得られ
たエポキシ樹脂組成物（２５℃で約１００ポイズ）を、
金型に流し込み、１００℃で１時間、さらに１８０℃で
５時間硬化し、厚さ３ｍｍの硬化物を得た。この硬化物
の曲げ試験による破断応力は１３ｋｇ／ｍｍ2、破断ひ
ずみは７．２％、弾性率は２６８ｋｇ／ｍｍ2であっ
た。Example 1 Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.
00 g, 24 g of SiB obtained in Synthesis Example 1, 116 g of Epicur YH306 manufactured by Yuka Shell Epoxy Co., Ltd., which is an alicyclic acid anhydride type curing agent, and a curing acceleration catalyst (Curesol manufactured by Shikoku Chemical Industry Co., Ltd.) After mixing 1 g of 2E4MZ) to make uniform, the mixture was filtered using filter paper 408 (pore size: 5 μm) manufactured by Advantech Co., Ltd., and subjected to vacuum removal. The obtained epoxy resin composition (about 100 poise at 25 ° C.)
The mixture was poured into a mold and cured at 100 ° C. for 1 hour and further at 180 ° C. for 5 hours to obtain a cured product having a thickness of 3 mm. The cured product had a breaking stress of 13 kg / mm 2 , a breaking strain of 7.2% and an elastic modulus of 268 kg / mm 2 by a bending test.
【００２６】実施例２および比較例 表１の配合による以外は、実施例１と同様の手法により
エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成
物を用いて、実施例１と同様の手法により、硬化物につ
いて評価した。これらの結果を表１に示した。なお、実
施例２のエポキシ樹脂組成物の粘度は約２５℃で約１２
０ポイズであった。Example 2 and Comparative Example An epoxy resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 1 was used. Using the obtained epoxy resin composition, a cured product was evaluated in the same manner as in Example 1. The results are shown in Table 1. The viscosity of the epoxy resin composition of Example 2 was about 12 at about 25 ° C.
It was 0 poise.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】この発明によれば、以上のような構成を
有しているので、無溶剤型の硬化性樹脂組成物を与え
る、流動性があって双溶性があり、硬化物が低応力を示
す硬化剤をを得ることができる。また、この発明によれ
ば、無溶剤型で硬化物が低応力を示す硬化性樹脂組成物
を得ることができる。According to the present invention, having the above structure, a solvent-free curable resin composition is provided. Can be obtained. Further, according to the present invention, it is possible to obtain a non-solvent type curable resin composition in which a cured product exhibits low stress.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J036 AA01 AC01 AC02 AD07 AD08 AF06 AF07 AF08 AJ14 AK08 DA04 DB05 DB21 DC35 DC41 FB08 FB14 FB16 JA07 4J043 PA18 PB15 QB15 QB25 QB26 QB31 RA39 SA06 SA47 SA85 TA22 TA66 TB01 UA042 UA052 UA122 UA131 UA132 UB322 UB332 VA042 VA052 XA06 XB11 ZB01 ZB02 ZB50 4M109 AA01 BA01 CA07 CA10 CA12 EA02 EB02 EB04 EC04 EC10 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J036 AA01 AC01 AC02 AD07 AD08 AF06 AF07 AF08 AJ14 AK08 DA04 DB05 DB21 DC35 DC41 FB08 FB14 FB16 JA07 4J043 PA18 PB15 QB15 QB25 QB26 QB31 RA39 SA06 SA47 SA85 TA04 TA66UA01 UA01 UA132 UB322 UB332 VA042 VA052 XA06 XB11 ZB01 ZB02 ZB50 4M109 AA01 BA01 CA07 CA10 CA12 EA02 EB02 EB04 EC04 EC10
Claims (4)
二無水物残基で、Ｂはジアミノポリシロキサン残基であ
る。］で示されるイミド単位を有し、Ａ成分とＢ成分と
の組成比（Ａ／Ｂ）が１．２〜５の範囲内にあり末端に
酸無水物基を有するイミド系オリゴマ−。[Claim 1] The following formula: Wherein A is an asymmetric aromatic or alicyclic tetracarboxylic dianhydride residue, and B is a diaminopolysiloxane residue. An imide oligomer having an imide unit represented by the formula (I), wherein the composition ratio (A / B) of the component A and the component B is in the range of 1.2 to 5, and having an acid anhydride group at a terminal.
酸二無水物（Ａ成分）を一旦エステル化剤、特に炭素数
４以下の一級アルコ−ルを用いてハ−フエステル化し、
得られた反応液にジアミノポリシロキサン（Ｂ成分）を
各成分の組成比（Ａ／Ｂ）が１．２〜５の範囲内となる
ように加え、最終的に１３０℃以上で２５０℃未満の温
度にてワンポット反応にて脱水反応させ、実質的に溶媒
が残存しない条件で製造してなる末端に酸無水物基を有
するイミド系オリゴマ−。2. A half-esterification of an asymmetric aromatic or alicyclic tetracarboxylic dianhydride (component A) with an esterifying agent, particularly a primary alcohol having 4 or less carbon atoms,
Diaminopolysiloxane (component B) is added to the obtained reaction solution so that the composition ratio (A / B) of each component is in the range of 1.2 to 5, and finally 130 ° C or higher and lower than 250 ° C. An imide oligomer having an acid anhydride group at a terminal, which is produced under a condition in which a dehydration reaction is carried out by a one-pot reaction at a temperature and substantially no solvent remains.
水物残基を有するイミド系オリゴマ−およびエポキシ樹
脂を含有する硬化性樹脂組成物。3. A curable resin composition comprising the imide-based oligomer having an acid anhydride residue at the terminal according to claim 1 or 2 and an epoxy resin.
３記載の硬化性樹脂組成物。4. The curable resin composition according to claim 3, further comprising a curing acceleration catalyst.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000288631A JP4374756B2 (en) | 2000-09-22 | 2000-09-22 | Imide oligomers having acid anhydride groups at the ends and curable resin compositions |
| TW90123191A TW574262B (en) | 2000-09-22 | 2001-09-20 | Imide based oligomer having acid anhydride at terminal, and resin composition having curing property |
| KR1020010058651A KR100791740B1 (en) | 2000-09-22 | 2001-09-21 | Imide oligomer having acid anhydride group at the terminal, and cured resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000288631A JP4374756B2 (en) | 2000-09-22 | 2000-09-22 | Imide oligomers having acid anhydride groups at the ends and curable resin compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002097270A true JP2002097270A (en) | 2002-04-02 |
| JP4374756B2 JP4374756B2 (en) | 2009-12-02 |
Family
ID=18772183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000288631A Expired - Fee Related JP4374756B2 (en) | 2000-09-22 | 2000-09-22 | Imide oligomers having acid anhydride groups at the ends and curable resin compositions |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4374756B2 (en) |
| KR (1) | KR100791740B1 (en) |
| TW (1) | TW574262B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005327973A (en) * | 2004-05-17 | 2005-11-24 | Sumitomo Bakelite Co Ltd | Resin composition, and semiconductor device produced by using the same |
| JP2005330356A (en) * | 2004-05-19 | 2005-12-02 | Sumitomo Bakelite Co Ltd | Resin composition and semiconductor apparatus made by using resin composition |
| WO2007052540A1 (en) * | 2005-11-01 | 2007-05-10 | Jsr Corporation | Photosensitive resin composition |
| WO2007061037A1 (en) * | 2005-11-25 | 2007-05-31 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic component and electronic component device |
| US9458279B2 (en) | 2008-06-02 | 2016-10-04 | Kaneka Corporation | Resin composition and use thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734736B (en) * | 2014-08-08 | 2022-04-19 | 东丽株式会社 | Adhesive for temporary bonding, adhesive layer, wafer processed body, and method for manufacturing semiconductor device using same |
| KR102671097B1 (en) * | 2017-05-31 | 2024-05-30 | 세키스이가가쿠 고교가부시키가이샤 | Curable resin composition, cured product, adhesive, adhesive film, coverlay film, and printed wiring board |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252703A (en) * | 1990-06-01 | 1993-10-12 | Ube Industries, Ltd. | Polyimidosiloxane resin and composition thereof and method of applying same |
| JPH1171457A (en) * | 1998-07-17 | 1999-03-16 | Ube Ind Ltd | Polyimidesiloxane |
-
2000
- 2000-09-22 JP JP2000288631A patent/JP4374756B2/en not_active Expired - Fee Related
-
2001
- 2001-09-20 TW TW90123191A patent/TW574262B/en not_active IP Right Cessation
- 2001-09-21 KR KR1020010058651A patent/KR100791740B1/en not_active IP Right Cessation
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005327973A (en) * | 2004-05-17 | 2005-11-24 | Sumitomo Bakelite Co Ltd | Resin composition, and semiconductor device produced by using the same |
| JP2005330356A (en) * | 2004-05-19 | 2005-12-02 | Sumitomo Bakelite Co Ltd | Resin composition and semiconductor apparatus made by using resin composition |
| JP4547988B2 (en) * | 2004-05-19 | 2010-09-22 | 住友ベークライト株式会社 | Resin composition and semiconductor device produced using resin composition |
| WO2007052540A1 (en) * | 2005-11-01 | 2007-05-10 | Jsr Corporation | Photosensitive resin composition |
| JP5018482B2 (en) * | 2005-11-01 | 2012-09-05 | Ｊｓｒ株式会社 | Photosensitive resin composition |
| WO2007061037A1 (en) * | 2005-11-25 | 2007-05-31 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic component and electronic component device |
| US8232355B2 (en) | 2005-11-25 | 2012-07-31 | Hitachi Chemical Co., Ltd. | Liquid resin composition for electronic components and electronic component device |
| US9458279B2 (en) | 2008-06-02 | 2016-10-04 | Kaneka Corporation | Resin composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100791740B1 (en) | 2008-01-04 |
| KR20020023662A (en) | 2002-03-29 |
| JP4374756B2 (en) | 2009-12-02 |
| TW574262B (en) | 2004-02-01 |
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