WO2011099292A1 - 無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物 - Google Patents
無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物 Download PDFInfo
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Definitions
- a liquid epoxy resin composition for semiconductor encapsulation comprising cyanate ester, epoxy resin, inorganic filler, dihydrazide compound, etc.
- An invention using an amine curing agent for a composite composition containing an acid ester and an epoxy resin has been proposed, and heat using a latent curing agent containing an imidazole component in a cyanate ester and an epoxy resin.
- Many cyanate ester-epoxy composite resin compositions such as a curable resin composition (Patent Document 3) have been proposed, but these compositions take not only low productivity but also heat resistance. Is insufficient, or the requirements for low dielectric constant and low dielectric loss tangent (tan ⁇ ) cannot be satisfied.
- the present inventors have found that a cyanate ester-epoxy containing a polyfunctional cyanate ester, a polyfunctional liquid epoxy resin, and an amine-based latent curing agent.
- the present inventors have found that the composite resin composition is good and have reached the present invention.
- the polyfunctional cyanate ester which is the component (A) used in the present invention is not particularly limited, and examples thereof include compounds represented by the following general formula (3).
- General formula (3) In the above formula, n is 0.5 to 20, R is an unsubstituted or fluorine-substituted divalent hydrocarbon group, R ′ and R ′′ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. is there.
- R is an unsubstituted or fluorine-substituted methylene group, or Of the compounds represented by the formula (where n is an integer of 1 to 12) and the prepolymer of the compound represented by the general formula (3), or the compound of the general formula (4), the following It is a prepolymer of a compound represented by the general formula (5).
- epoxy resins may be those internally crosslinked by a terminal isocyanate prepolymer, or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). Good.
- the amine-based latent curing agent that is the component (C) used in the present invention is preferably an active hydrogen-containing amine-based latent curing agent because of excellent reactivity.
- This amine-based latent curing agent is particularly modified by reacting (a-1) a polyamine compound and (a-2) an epoxy compound, (a) having one or more amino groups having active hydrogen in the molecule.
- a latent curing agent containing an amine and (b) a phenol resin is preferable.
- polyamine compounds in the present invention, in particular, (1) a diamine having two primary or secondary amino groups having different reactivity in the molecule, and / or (2) an intramolecular Having two or more primary or secondary amino groups, and one of them reacts with an epoxy group, the reactivity of the remaining primary or secondary amino group with the epoxy group due to its steric hindrance
- a polyamine compound selected from an aromatic polyamine, an alicyclic polyamine, and an aliphatic polyamine that reduces the adhesion of the cyanate ester-epoxy resin composition of the present invention in a cured product It is preferable because not only the properties but also the physical properties of the cured product can be improved.
- a polyamine having two or more primary and secondary amino groups in combination is used as the component (a-1), (a-2) It is preferable to use as the component (a) a modified polyamine obtained by reacting the component with an amount such that the epoxy equivalent is 0.5 to 2 equivalents, particularly 0.8 to 1.5 equivalents.
- the component (a-1) different modified amines such as a combination of a modified amine obtained using the polyamine corresponding to the above (1) and a modified amine obtained using an imidazole compound are used.
- a compound and / or an imidazole compound can be used in combination.
- the phenol resin as component (b) used in the present invention is a phenol resin synthesized from phenols and aldehydes.
- the phenols include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, hydroquinone.
- the amine-based latent curing agent as the component (C) used in the present invention is a guanidine compound, and the cyanate-epoxy resin composition of the present invention is excellent in stability even if the blending amount is small. Is preferable.
- guanidine compounds include compounds represented by the following general formula.
- n in the above formula represents an integer of 0 to 5
- R 1 represents an amino group or an unsubstituted or fluorine-substituted monovalent hydrocarbon group.
- R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the amount of the component (C) used in the cyanate ester-epoxy resin composition of the present invention is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). In particular, the amount is preferably 5 to 50 parts by mass.
- the total amount of the component (A), the component (B) and the component (C) is preferably 30% by mass or more in the cyanate ester-epoxy resin composition of the present invention.
- ⁇ Linear expansion coefficient> A cylindrical cured product having a diameter of 4 mm was prepared, and a DSC chart was measured using a differential scanning calorimeter TMA6220 manufactured by SII Nanotechnology, with a heating rate of 2 ° C./min and a scanning temperature range of 20 to 250 ° C. The linear expansion coefficients on the low temperature side (30 to 80 ° C.) and the high temperature side (170 to 220 ° C.) were shown.
- CE-1 Bifunctional cyanate ester (manufactured by Lonza; PrimasetLeCy, bisphenol E type cyanate ester), CE-2: polyfunctional cyanate ester (manufactured by Lonza; Primaset PT-30, phenol novolac type cyanate ester, average functional group number 7.3), EP-1: Bifunctional epoxy resin (manufactured by ADEKA Corporation; EP-4100L, bisphenol F type epoxy resin, epoxy equivalent 170) EP-2: Trifunctional epoxy resin (manufactured by ADEKA Corporation; EP-3950S, aminophenol type epoxy resin, epoxy equivalent 95) DICY: Dicyandiamide (manufactured by ADEKA Corporation; EH-3636AS) SiO 2 : Silica filler (Electrochemical Industry Co., Ltd .; FB-950)
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Abstract
Description
一般式(3)
但し、上式中のnは0.5~20、Rは、非置換又はフッ素置換の2価の炭化水素基であり、R’及びR”は水素原子又は炭素数1~4のアルキル基である。
一般式(4)
但し、上式中のR1は、非置換又はフッ素置換の2価の炭化水素基、-O-、-S-、又は単結合を表し、R2及びR3は、それぞれ独立して非置換又は1~4個のアルキル基で置換されているフェニレン基である。上記プレポリマーとしては、例えば一般式(4)の化合物の全部又は一部が3量化した物が挙げられる。
特に、Rが、非置換又はフッ素置換のメチレン基、若しくは、下記の基
で表される化合物(ここで、nは1~12の整数)、及び、前記一般式(3)で表される化合物のプレポリマー、又は、前記一般式(4)の化合物の内、下記の一般式(5)で表される化合物のプレポリマーである。
一般式(5)
但し、上式中のR5は、基:
(ここで、R10、R11はそれぞれ独立して、水素原子又は非置換若しくはフッ素置換のメチル基である)、又は、基:
であり、上式中のnは4~12の整数、前記式(5)中のR6、R7、R8及びR9はそれぞれ独立して、水素原子又は非置換若しくはフッ素置換のメチル基である。
式(1)
但し、上式中のAiは成分iのシアネート基数、Xiは成分iの含有割合(質量%)である。
式(2)
但し、上式中のBkは成分kのエポキシ基数、Ykは成分kの含有割合(質量%)である。
イソホロンジアミン352gと、アデカレジンEP-4100E((株)ADEKAの商品名;エポキシ当量が190のビスフェノールA型エポキシ樹脂)580g(イソホロンジアミン1モルに対するアデカレジンEP-4100Eのエポキシ当量は1.47)とを反応させて、変性ポリアミンを得た。得られた変性ポリアミン100gに対してフェノール樹脂30gを仕込み、180~190℃、30~40トールで1時間かけて脱溶媒を行い、潜在性硬化剤(EH-1)を得た。
[実施例1,2及び比較例1-3]
ブルックフィールドE型回転粘度計を用いて、5rpmで25℃における粘度を測定した。
各測定温度に保たれた熱盤上に、得られた組成物を0.5g滴下し、スパチュラ等でかき混ぜながら流動性がなくなるまでの時間を測定した。
SIIナノテクノロジーズ社製の示差走査熱量計DSC6220を用い、昇温速度を10℃/分、走査温度範囲を25~250℃として、DSCチャートを測定した。更に、2次昇温を同条件で行い、熱容量の変曲点からガラス転移点を測定した。
直径4mmの円柱状硬化物を作製し、SIIナノテクノロジーズ社製の示差走査熱量計TMA6220を用いて、昇温速度を2℃/分、走査温度範囲を20~250℃としてDSCチャートを測定し、低温側(30~80℃)及び高温側(170~220℃)の線膨張係数を示した。
1mm厚の硬化板を作製し、アジレント・テクノロジー社製のRFインピーダンス/マテリアル・アナライザE4991Aを用いて、各周波数における誘電率εと誘電正接tanδを測定した。
実施例1及び比較例1についてのみ、5mm×20mm×0.2mmの板状硬化物を作製し、エー・アンド・デイ社製の動的粘弾性自動測定器であるレオバイブロンDDV-01FPを用いて、昇温速度2℃/分、走査温度範囲-100~250℃として動的粘弾性を測定した。その結果を〔図1〕に示した。
CE-1:2官能シアン酸エステル(ロンザ社製;PrimasetLeCy、ビスフェノールE型シアン酸エステル)、
CE-2:多官能シアン酸エステル(ロンザ社製;PrimasetPT-30、フェノールノボラック型シアン酸エステル、平均官能基数7.3)、
EP-1:2官能エポキシ樹脂((株)ADEKA社製;EP-4100L、ビスフェノールF型エポキシ樹脂、エポキシ当量170)
EP-2:3官能エポキシ樹脂((株)ADEKA社製;EP-3950S、アミノフェノール型エポキシ樹脂、エポキシ当量95)
DICY:ジシアンジアミド((株)ADEKA社製;EH-3636AS)
SiO2:シリカフィラー(電気化学工業(株)社製;FB-950)
Claims (14)
- 前記(B)成分である多官能液状エポキシ樹脂が、N,N-ビス(2,3-エポキシプロピル)-4-(2,3-エポキシプロポキシ)-2-メチルアニリン、N,N-ビス(2,3-エポキシプロピル)-4-(2,3-エポキシプロポキシ)アニリン、及び、N,N,N’,N’-テトラ(2,3-エポキシプロピル)-4,4’-ジアミノジフェニルメタンの中から選ばれる少なくとも1種を50~100質量%含む、請求項1に記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記(C)成分であるアミン系潜在性硬化剤が活性水素含有アミン系潜在性硬化剤である、請求項1又は2に記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記(C)成分であるアミン系潜在性硬化剤が、(a-1)ポリアミン化合物及び(a-2)エポキシ化合物を反応させてなる(a)分子内に活性水素を持つアミノ基を1個以上有する変性アミン、及び、(b)フェノール樹脂を含有してなる潜在性硬化剤である、請求項3に記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記(a-1)ポリアミン化合物が、(1)分子内にそれぞれ反応性を異にする2個の第1級又は第2級アミノ基を有するジアミン、(2)分子内に2個以上の第1級又は第2級アミノ基を有し、その1個がエポキシ基と反応した場合、その立体障害により残りの第1級又は第2級アミノ基のエポキシ基との反応性が低下する芳香族ポリアミン、(3)脂環式ポリアミン及び(4)脂肪族ポリアミンからなる群の中から選択された少なくとも1種である、請求項4に記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記(a-2)であるエポキシ化合物が、分子内にエポキシ基を2個以上有するポリグリシジルエーテル化合物である、請求項4又は5に記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記(a)成分である変性ポリアミンが、(a-1)成分が1モルとなる量に対し、(a-2)成分0.5~2当量となる量使用して反応させて得られた変性ポリアミンである、請求項4~6の何れかに記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記(b)成分であるフェノール系樹脂の数平均分子量が750~1200である、請求項4~7の何れかに記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- (a)成分である変性ポリアミン100質量部に対し、(b)成分であるフェノール樹脂を10~100質量部使用する、請求項4~8の何れかに記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記グアニジン化合物が、アセトグアナミン、ベンゾグアナミン、及びジシアンジアミドの中から選ばれた少なくとも一種のグアニジン化合物である、請求項10に記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物。
- 前記(A)成分である多官能シアン酸エステルが、下記一般式(3)で表される化合物、及び、下記一般式(4)で表される化合物のプレポリマーからなる群の中から選択される少なくとも1種の化合物及び/又はプレポリマーである、請求項1~11の何れかに記載された無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物;
一般式(3):
但し、上式中のnは0.5~20、Rは、非置換又はフッ素置換の2価の炭化水素基、R’及びR”は水素原子又は炭素数1~4のアルキル基である;
下記一般式(4):
但し、上式中のR1は、非置換又はフッ素置換の2価の炭化水素基、又は-O-、-S-、若しくは単結合を表し、R2及びR3は、それぞれ独立に、非置換又は1~4個のアルキル基で置換されたフェニレン基である。 - 請求項1~12の何れかに記載された樹脂組成物を、重合硬化させてなることを特徴とする硬化物。
- 請求項1~12の何れかに記載された樹脂組成物を、型内で硬化させることを特徴とする硬化物の製造方法。
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06256744A (ja) * | 1993-03-04 | 1994-09-13 | Kanegafuchi Chem Ind Co Ltd | 接着剤組成物 |
JPH07304968A (ja) * | 1994-03-15 | 1995-11-21 | Toray Ind Inc | マイクロカプセル型硬化剤、その製造法、熱硬化性樹脂組成物、プリプレグおよび繊維強化複合材料 |
JPH09100349A (ja) * | 1995-10-02 | 1997-04-15 | Shin Etsu Chem Co Ltd | 熱硬化性樹脂組成物 |
JPH09279121A (ja) * | 1996-04-15 | 1997-10-28 | Hitachi Chem Co Ltd | 接着剤組成物および該組成物からなる接続部材 |
JPH09291268A (ja) * | 1996-04-26 | 1997-11-11 | Hitachi Chem Co Ltd | 接着剤組成物および該組成物からなる接続部材 |
JP2008214567A (ja) * | 2007-03-07 | 2008-09-18 | Adeka Corp | エポキシ樹脂用硬化剤組成物及びそれを用いた硬化性エポキシ樹脂組成物 |
WO2009001658A1 (ja) * | 2007-06-22 | 2008-12-31 | Adeka Corporation | 一液型シアネート-エポキシ複合樹脂組成物 |
JP2009013205A (ja) * | 2007-06-29 | 2009-01-22 | Adeka Corp | 一液型シアネート−エポキシ複合樹脂組成物 |
WO2009047885A1 (ja) * | 2007-10-09 | 2009-04-16 | Adeka Corporation | 一液型シアネート-エポキシ複合樹脂組成物、その硬化物及びその製造方法、並びにそれを用いた封止用材料及び接着剤 |
WO2009157147A1 (ja) * | 2008-06-27 | 2009-12-30 | 株式会社Adeka | 一液型シアネート-エポキシ複合樹脂組成物 |
WO2010086932A1 (ja) * | 2009-01-29 | 2010-08-05 | 株式会社Adeka | 一液型シアン酸エステル-エポキシ複合樹脂組成物 |
JP2010180352A (ja) * | 2009-02-06 | 2010-08-19 | Denso Corp | 迅速光硬化性エポキシ系接着剤組成物及び接合方法 |
WO2011036836A1 (ja) * | 2009-09-25 | 2011-03-31 | 株式会社Adeka | 無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4360649A (en) * | 1980-04-30 | 1982-11-23 | Sumitomo Chemical Company, Limited | Curable composition |
EP0350232A3 (en) * | 1988-07-04 | 1991-04-10 | Somar Corporation | Penetrable, epoxy resin composition |
JPH0699676B2 (ja) * | 1989-04-28 | 1994-12-07 | ソマール株式会社 | 硬化歪発生の抑制されたエポキシ樹脂組成物を用いる接着方法 |
JPH0337264A (ja) * | 1989-07-04 | 1991-02-18 | Mitsubishi Gas Chem Co Inc | シアン酸エステル系樹脂硬化物の製造法 |
JPH10212364A (ja) * | 1996-11-26 | 1998-08-11 | Ajinomoto Co Inc | 積層板用プリプレグ及びこれを用いたプリント配線板の製造方法 |
JP2000191776A (ja) * | 1998-12-24 | 2000-07-11 | Mitsubishi Gas Chem Co Inc | シアン酸エステル・コ−プレポリマー |
KR20020087287A (ko) * | 2001-05-15 | 2002-11-22 | 삼성전기주식회사 | 시아네이트 에스테르-함유 절연조성물, 이로부터 제조된 절연필름 및 절연필름을 갖는 다층인쇄회로기판 |
JP2004175925A (ja) * | 2002-11-27 | 2004-06-24 | Mitsubishi Gas Chem Co Inc | プリプレグ及び積層板 |
US7557169B2 (en) * | 2003-07-07 | 2009-07-07 | Dow Global Technologies, Inc. | Capping isocyanate prepolymer or polyisocyanate/polyether polyol or polyamine mixture |
JP4534716B2 (ja) * | 2004-10-26 | 2010-09-01 | 日立化成工業株式会社 | 回路接続材料並びに回路端子の接続構造体及び接続方法 |
JP2006286852A (ja) * | 2005-03-31 | 2006-10-19 | Sumitomo Bakelite Co Ltd | 樹脂組成物、樹脂層、樹脂層付きキャリア材料および回路基板 |
CN102150261A (zh) * | 2008-09-11 | 2011-08-10 | 住友电木株式会社 | 半导体装置及用于半导体装置的树脂组合物 |
-
2010
- 2010-02-12 JP JP2010028945A patent/JP5603610B2/ja active Active
-
2011
- 2011-02-10 KR KR1020127020500A patent/KR101888703B1/ko active IP Right Grant
- 2011-02-10 CN CN201180008920.2A patent/CN102906149B/zh active Active
- 2011-02-10 WO PCT/JP2011/000753 patent/WO2011099292A1/ja active Application Filing
- 2011-02-10 US US13/578,064 patent/US9382459B2/en active Active
- 2011-02-11 TW TW100104619A patent/TWI567098B/zh active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06256744A (ja) * | 1993-03-04 | 1994-09-13 | Kanegafuchi Chem Ind Co Ltd | 接着剤組成物 |
JPH07304968A (ja) * | 1994-03-15 | 1995-11-21 | Toray Ind Inc | マイクロカプセル型硬化剤、その製造法、熱硬化性樹脂組成物、プリプレグおよび繊維強化複合材料 |
JPH09100349A (ja) * | 1995-10-02 | 1997-04-15 | Shin Etsu Chem Co Ltd | 熱硬化性樹脂組成物 |
JPH09279121A (ja) * | 1996-04-15 | 1997-10-28 | Hitachi Chem Co Ltd | 接着剤組成物および該組成物からなる接続部材 |
JPH09291268A (ja) * | 1996-04-26 | 1997-11-11 | Hitachi Chem Co Ltd | 接着剤組成物および該組成物からなる接続部材 |
JP2008214567A (ja) * | 2007-03-07 | 2008-09-18 | Adeka Corp | エポキシ樹脂用硬化剤組成物及びそれを用いた硬化性エポキシ樹脂組成物 |
WO2009001658A1 (ja) * | 2007-06-22 | 2008-12-31 | Adeka Corporation | 一液型シアネート-エポキシ複合樹脂組成物 |
JP2009013205A (ja) * | 2007-06-29 | 2009-01-22 | Adeka Corp | 一液型シアネート−エポキシ複合樹脂組成物 |
WO2009047885A1 (ja) * | 2007-10-09 | 2009-04-16 | Adeka Corporation | 一液型シアネート-エポキシ複合樹脂組成物、その硬化物及びその製造方法、並びにそれを用いた封止用材料及び接着剤 |
WO2009157147A1 (ja) * | 2008-06-27 | 2009-12-30 | 株式会社Adeka | 一液型シアネート-エポキシ複合樹脂組成物 |
WO2010086932A1 (ja) * | 2009-01-29 | 2010-08-05 | 株式会社Adeka | 一液型シアン酸エステル-エポキシ複合樹脂組成物 |
JP2010180352A (ja) * | 2009-02-06 | 2010-08-19 | Denso Corp | 迅速光硬化性エポキシ系接着剤組成物及び接合方法 |
WO2011036836A1 (ja) * | 2009-09-25 | 2011-03-31 | 株式会社Adeka | 無溶剤一液型シアン酸エステル-エポキシ複合樹脂組成物 |
Cited By (11)
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GB2500029B (en) * | 2012-03-07 | 2014-03-12 | Henkel Ireland Ltd | Curable compositions |
US20150175799A1 (en) * | 2012-06-08 | 2015-06-25 | Adeka Corporation | Curable resin composition, resin composition, resin sheet formed by using said curable resin composition and resin composition, and cured materials thereof |
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JPWO2017038603A1 (ja) * | 2015-09-04 | 2018-07-26 | 株式会社Adeka | 繊維強化プラスチック用樹脂組成物、その硬化物、該硬化物を含有する繊維強化プラスチック、及び該繊維強化プラスチックの製造方法 |
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CN112876903A (zh) * | 2021-03-07 | 2021-06-01 | 珠海英勇科技有限公司 | 一种低介电塞孔油墨及其制备方法 |
WO2022190746A1 (ja) * | 2021-03-08 | 2022-09-15 | 株式会社Adeka | 硬化性樹脂組成物、硬化物及び接着剤 |
CN113528071A (zh) * | 2021-08-23 | 2021-10-22 | 黑龙江省科学院石油化学研究院 | 一种低介电环氧胶及其制备方法 |
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