TWI589617B - Epoxy resin composition for sealing and electronic component device - Google Patents

Epoxy resin composition for sealing and electronic component device Download PDF

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TWI589617B
TWI589617B TW105100581A TW105100581A TWI589617B TW I589617 B TWI589617 B TW I589617B TW 105100581 A TW105100581 A TW 105100581A TW 105100581 A TW105100581 A TW 105100581A TW I589617 B TWI589617 B TW I589617B
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epoxy resin
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TW201619230A (en
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田中賢治
濱田光祥
古澤文夫
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日立化成股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/40Macromolecules 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
    • C08G59/62Alcohols or phenols
    • C08G59/621Phenols
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/20Macromolecules 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 epoxy compounds used
    • C08G59/22Di-epoxy compounds
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293Organic, e.g. plastic
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293Organic, e.g. plastic
    • H01L23/295Organic, e.g. plastic containing a filler
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • C08L2203/206Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

密封用環氧樹脂組成物及電子零件裝置 Sealing epoxy resin composition and electronic component device

本發明係關於一種密封用環氧樹脂組成物、及具備以該密封用環氧樹脂組成物密封的元件之電子零件裝置。 The present invention relates to an epoxy resin composition for sealing and an electronic component device including an element sealed with the epoxy resin composition for sealing.

自過去至今,在電晶體、IC(積體電路)等電子零件密封之領域中,廣泛使用密封用環氧樹脂組成物。該理由為環氧樹脂在電特性、耐濕性、耐熱性、機械特性、與嵌件品之黏著性等可達到平衡之故。特別是鄰甲酚酚醛清漆型環氧樹脂與酚醛清漆型酚硬化劑之組合,上述特性可達到優良平衡,故成為密封用組成物的基底樹脂之主流。 Since the past, the epoxy resin composition for sealing has been widely used in the field of sealing electronic components such as transistors and ICs (integrated circuits). The reason for this is that the epoxy resin can be balanced in electrical properties, moisture resistance, heat resistance, mechanical properties, adhesion to inserts, and the like. In particular, the combination of an o-cresol novolac type epoxy resin and a novolac type phenol hardener has an excellent balance of the above characteristics, and thus is a mainstream of a base resin for a sealing composition.

隨著近年電子機器的小型化、輕量化、高性能化,安裝之高密度化也進行著,電子零件裝置由過去進行針插入型(pin insertion type)之封裝逐漸變為進行表面安裝型(surface mount type)之封裝。將半導體裝置裝配至電路板時,在過去的針插入型封裝中,因將針插入電路板後,是由電路板背面進行焊接, 故封裝體不會直接暴露在高溫下。然而,在表面安裝型封裝中,因半導體裝置全體是以焊料浴或回焊裝置等進行處理,故封裝體會暴露於焊接溫度。此結果,在封裝體吸濕時,於焊接時吸濕水分會急劇膨脹,產生黏著界面剝離或封裝體龜裂,而會有著安裝時之封裝可靠度降低的問題。 In recent years, the miniaturization, weight reduction, and high performance of electronic devices have increased, and the density of mounting has also increased. The electronic component devices have gradually changed from being packaged in a pin insertion type to surface mounting. Mount type). When mounting a semiconductor device to a circuit board, in the conventional pin insertion type package, since the pin is inserted into the circuit board, it is soldered from the back side of the circuit board. Therefore, the package is not directly exposed to high temperatures. However, in the surface mount package, since the entire semiconductor device is processed by a solder bath or a reflow device, the package is exposed to the soldering temperature. As a result, when the package absorbs moisture, moisture absorption during the soldering will rapidly expand, causing peeling of the adhesive interface or cracking of the package, and there is a problem that the package reliability at the time of mounting is lowered.

作為解決上述問題之對策,為了減低半導體裝置內部的吸濕水分,會使用將IC進行防濕綑包、或安裝至電路板前預先充分乾燥IC後使用等方法。但這些方法手續較為繁雜且成本亦高。 In order to reduce the moisture absorption in the semiconductor device, a method of preventing the wet moisture in the semiconductor device from being used for moisture-proof packaging or sufficiently drying the IC before mounting on the circuit board may be used. However, these methods are complicated and costly.

作為其他對策,可舉出增加密封用環氧樹脂組成物中之填充劑的含有量之方法。但此方法中,雖可減低半導體裝置內之密封部分的吸濕水分,但有著引起密封用環氧樹脂組成物流動性大幅降低的問題。若密封用環氧樹脂組成物的流動性降低,會產生於成形時發生金線流動、空隙(void)、針孔(pin hole)等問題。 As another measure, a method of increasing the content of the filler in the epoxy resin composition for sealing can be mentioned. However, in this method, although the moisture absorption moisture of the sealed portion in the semiconductor device can be reduced, there is a problem that the fluidity of the epoxy resin composition for sealing is largely lowered. When the fluidity of the epoxy resin composition for sealing is lowered, problems such as gold wire flow, voids, and pin holes occur during molding.

又,於日本特開平06-224328號公報中,已揭示將添加於環氧樹脂的填充劑之粒度分布設為在特定範圍之半導體密封用樹脂組成物。若依據該半導體密封用樹脂組成物,則會不損失流動性地增加填充劑的含有量,而改善熱膨脹特性、熱傳導特性、耐吸濕性及彎曲強度。 In the Japanese Patent Publication No. 06-224328, the resin composition for semiconductor encapsulation in which the particle size distribution of the filler added to the epoxy resin is within a specific range has been disclosed. According to the resin composition for semiconductor encapsulation, the content of the filler is increased without losing fluidity, and the thermal expansion property, heat conduction property, moisture absorption resistance, and bending strength are improved.

且,於日本特開平09-165433號公報中,已揭示一種環氧樹脂之製造方法,是在使多元酚類與環氧 鹵丙烷進行反應來製造環氧樹脂之方法中,作為多元酚類,使用二羥基二苯甲酮與其他的多元酚類之混合物。該發明中,在環氧樹脂之合成階段,使用二羥基二苯甲酮,將藉此所得之環氧樹脂與苯酚酚醛清漆樹脂或二氧化矽粉末等一起混合後調製出環氧樹脂組成物。該環氧樹脂組成物成為硬化性、流動性優良,且無結晶性。 Further, in Japanese Laid-Open Patent Publication No. H09-165433, a method for producing an epoxy resin is disclosed in which a polyhydric phenol and an epoxy are used. In the method in which a halogenated propane is reacted to produce an epoxy resin, a mixture of dihydroxybenzophenone and other polyhydric phenols is used as the polyhydric phenol. In the invention, in the synthesis stage of the epoxy resin, the epoxy resin obtained by mixing the epoxy resin obtained with the phenol novolak resin or the ceria powder is prepared by using dihydroxybenzophenone. The epoxy resin composition is excellent in curability and fluidity, and has no crystallinity.

已知上述特開平09-165433號公報的發明中,雖提高硬化性及流動性,但會有在高溫中與金屬的黏著性降低之情況。由耐回焊性提高之觀點來看,期待改善在高溫中與金屬之黏著性。 In the invention of the above-mentioned Japanese Patent Publication No. Hei 09-165433, although the curability and fluidity are improved, the adhesion to metal at a high temperature may be lowered. From the viewpoint of improvement in reflow resistance, it is expected to improve adhesion to metals at high temperatures.

本發明係有鑑於上述狀況所成者,以提供在高溫中與金屬的黏著性高且耐回焊性優良的密封用環氧樹脂組成物、及具備藉此密封之元件的電子零件裝置為課題。 In view of the above-mentioned circumstances, the present invention provides an epoxy resin composition for sealing which is excellent in adhesion to metals at high temperatures and excellent in reflow resistance, and an electronic component device including the element to be sealed thereby. .

本發明係關於以下者。 The present invention relates to the following.

(1)一種密封用環氧樹脂組成物,其含有(A)於1分子中含有2個以上環氧基之環氧樹脂、(B)硬化劑、及(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物。 (1) An epoxy resin composition for sealing comprising (A) an epoxy resin containing two or more epoxy groups in one molecule, (B) a curing agent, and (C) having one in one molecule The above benzophenone derivative of a phenolic hydroxyl group.

(2)前述(1)所記載之密封用環氧樹脂組成物,其中前述(C)於1分子中具有1個以上的酚性羥基之二 苯甲酮衍生物的含有率為0.1質量%以上且1.0質量%以下。 (2) The epoxy resin composition for sealing according to the above (1), wherein the (C) has one or more phenolic hydroxyl groups in one molecule. The content of the benzophenone derivative is 0.1% by mass or more and 1.0% by mass or less.

(3)前述(1)或(2)所記載之密封用環氧樹脂組成物,其中進一步含有(D)矽烷化合物。 (3) The epoxy resin composition for sealing according to (1) or (2) above which further contains (D) a decane compound.

(4)前述(1)~(3)中任1項所記載之密封用環氧樹脂組成物,其中進一步含有(E)硬化促進劑。 (4) The epoxy resin composition for sealing according to any one of (1) to (3) further comprising (E) a curing accelerator.

(5)前述(1)~(4)中任1項所記載之密封用環氧樹脂組成物,其中進一步含有(F)無機填充劑。 (5) The epoxy resin composition for sealing according to any one of (1) to (4) further comprising (F) an inorganic filler.

(6)一種電子零件裝置,其具備藉由前述(1)~(5)中任1項所記載之密封用環氧樹脂組成物所密封之元件。 (6) An electronic component device comprising an element sealed by the sealing epoxy resin composition according to any one of the above items (1) to (5).

若依據本發明,可提供在高溫中與金屬之黏著性高且耐回焊性優良之密封用環氧樹脂組成物、及具備藉此密封之元件的電子零件裝置。 According to the present invention, it is possible to provide an epoxy resin composition for sealing which is excellent in adhesion to metal at a high temperature and excellent in reflow resistance, and an electronic component device including the element to be sealed thereby.

〔實施發明之形態〕 [Formation of the Invention]

以下對於本發明做詳細說明。 The invention will be described in detail below.

且,本說明書中之「~」表示將其前後所記載之數值分別作為最小值及最大值來包含的範圍。又,本說明 書中之組成物中的各成分的量,於組成物中相當於各成分的物質存在複數個時,若無特別說明,則表示存在於組成物中之該複數物質的合計量。 Further, "~" in the present specification means a range including the numerical values described before and after the minimum value and the maximum value. Again, this description The amount of each component in the composition in the book, when there are a plurality of substances corresponding to the respective components in the composition, unless otherwise specified, indicates the total amount of the plural substances present in the composition.

<密封用環氧樹脂組成物> <Epoxy resin composition for sealing>

本發明的密封用環氧樹脂組成物為含有(A)於1分子中含有2個以上環氧基之環氧樹脂、(B)硬化劑、及(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物。本發明的密封用環氧樹脂組成物在室溫(25℃)是固體。 The epoxy resin composition for sealing of the present invention contains (A) an epoxy resin containing two or more epoxy groups in one molecule, (B) a curing agent, and (C) one or more in one molecule. A benzophenone derivative of a phenolic hydroxyl group. The epoxy resin composition for sealing of the present invention is a solid at room temperature (25 ° C).

以下對於構成本發明的密封用環氧樹脂組成物之各成分作說明。 Hereinafter, each component constituting the epoxy resin composition for sealing of the present invention will be described.

〔(A)環氧樹脂〕 [(A) Epoxy Resin]

本發明中所使用的(A)於1分子中含有2個以上環氧基之環氧樹脂,只要是一般使用於密封用環氧樹脂組成物者即可,並無特別限制。例如,可舉出以苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、具有三苯基甲烷骨架的環氧樹脂為首且是將苯酚、甲酚、二甲酚、間苯二酚、兒茶酚、雙酚A、雙酚F、α-萘酚、β-萘酚、二羥基萘等酚類與甲醛、乙醛、丙醛、苯甲醛、水楊醛等具有醛基的化合物在酸性觸媒下進行縮合或共縮合後所得之酚醛清漆樹脂進行環氧化者;經烷基取代、經芳香環取代或未取代之雙酚A、雙酚F、雙酚S、聯苯酚、硫二苯酚等之二縮水甘油基醚;芪(stilbene)型環氧樹脂;氫醌型環氧樹脂;藉由鄰苯二甲酸、二聚 物酸等多元酸與環氧氯丙烷之反應所得之縮水甘油基酯型環氧樹脂;藉由二胺基二苯基甲烷、異三聚氰酸等多胺與環氧氯丙烷之反應所得之縮水甘油胺型環氧樹脂;二環戊二烯與酚類之共縮合樹脂的環氧化物;具有萘環之環氧樹脂;由酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成之酚‧芳烷基樹脂;萘酚‧芳烷基樹脂等芳烷基型酚樹脂的環氧化物;三羥甲基丙烷型環氧樹脂;萜烯改性環氧樹脂;將烯烴鍵結以過乙酸等過酸進行氧化所得之線狀脂肪族環氧樹脂;脂環族環氧樹脂等。這些可單獨使用1種或組合2種以上使用。 The epoxy resin (A) which contains two or more epoxy groups in one molecule used in the present invention is not particularly limited as long as it is generally used for a sealing epoxy resin composition. For example, a phenol novolak type epoxy resin, an o-cresol novolac type epoxy resin, an epoxy resin having a triphenylmethane skeleton, and phenol, cresol, xylenol, and isophthalene are mentioned. Phenols, catechol, bisphenol A, bisphenol F, α -naphthol, β -naphthol, dihydroxynaphthalene and other phenols with formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. The phenolic varnish resin obtained by condensation or co-condensation of the compound under an acidic catalyst is subjected to epoxidation; bisphenol A substituted by an alkyl group, substituted or unsubstituted by an aromatic ring, bisphenol F, bisphenol S, biphenol, a diglycidyl ether such as thiodiphenol; a stilbene type epoxy resin; a hydroquinone type epoxy resin; a reaction of a polybasic acid such as phthalic acid or a dimer acid with epichlorohydrin a glycidyl ester type epoxy resin; a glycidylamine type epoxy resin obtained by reacting a polyamine such as diaminodiphenylmethane or isomeric cyanuric acid with epichlorohydrin; dicyclopentadiene and Epoxides of co-condensation resins of phenols; epoxy resins having naphthalene rings; by phenols and dimethoxy groups Phenol aralkyl resin synthesized from p-xylene or bis(methoxymethyl)biphenyl; epoxide of aralkyl type phenol resin such as naphthol ‧ aralkyl resin; trimethylolpropane ring Oxygen resin; terpene-modified epoxy resin; linear aliphatic epoxy resin obtained by oxidizing an olefin with a peracid such as peracetic acid; an alicyclic epoxy resin or the like. These may be used alone or in combination of two or more.

其中,由兼顧流動性與硬化性之觀點來看,較佳是含有聯苯型環氧樹脂,且其是經烷基取代、經芳香環取代或未取代的聯苯酚之二縮水甘油基醚,由硬化性觀點來看,較佳是含有酚醛清漆型環氧樹脂,由耐熱性及低反翹性的觀點來看,較佳是含有萘型環氧樹脂及/或三苯基甲烷型環氧樹脂,由兼顧流動性與難燃性的觀點來看,較佳是含有雙酚F型環氧樹脂,且其是經烷基取代、經芳香環取代或未取代之雙酚F的二縮水甘油基醚,由兼顧流動性與回焊性的觀點來看,較佳是含有硫二苯酚型環氧樹脂,且其是經烷基取代、經芳香環取代或未取代的硫二苯酚之二縮水甘油基醚,由兼顧硬化性與難燃性的觀點來看,較佳是含有酚‧芳烷基樹脂的環氧化物,且其是由經烷基取代、經芳香環取代或未取代的酚與雙(甲氧基甲基)聯苯所合成,由兼顧保存安定 性與難燃性的觀點來看,較佳是含有萘酚‧芳烷基樹脂的環氧化物,且其是經烷基取代、經芳香環取代或未取代的萘酚類與二甲氧基對二甲苯所合成。 Among them, from the viewpoint of achieving both fluidity and hardenability, a biphenyl type epoxy resin is preferably contained, and it is a diglycidyl ether of an alkyl group-substituted, aromatic ring-substituted or unsubstituted biphenol. From the viewpoint of curability, it is preferable to contain a novolac type epoxy resin, and it is preferable to contain a naphthalene type epoxy resin and/or a triphenylmethane type epoxy resin from the viewpoint of heat resistance and low anti-warpage property. The resin preferably has a bisphenol F type epoxy resin and is a diglycidyl group which is substituted by an alkyl group, substituted by an aromatic ring or unsubstituted bisphenol F, from the viewpoint of achieving both fluidity and flame retardancy. The ether is preferably a thiodiphenol type epoxy resin which is a thiodiphenol type epoxy resin which is an alkyl substituted, an aromatic ring substituted or unsubstituted thiodiphenol condensed water, from the viewpoint of balance between fluidity and reflowability. The glyceryl ether is preferably an epoxide containing a phenol ‧ aralkyl resin from the viewpoint of achieving both hardenability and flame retardancy, and is a phenol substituted by an alkyl group, substituted by an aromatic ring or unsubstituted Synthesized with bis(methoxymethyl)biphenyl From the viewpoint of properties and flame retardancy, an epoxide containing a naphthol ‧ aralkyl resin is preferred, and it is an alkyl substituted, aromatic ring substituted or unsubstituted naphthol and dimethoxy group. Synthesized by p-xylene.

作為前述聯苯型環氧樹脂,例如可舉出下述一般式(I)所示之環氧樹脂等。 The biphenyl type epoxy resin may, for example, be an epoxy resin represented by the following general formula (I).

一般式(I)中,R1~R8各獨立表示氫原子或碳數1~10的取代或未取代的一價烴基。R1~R8可全相同或相異。n表示0~3的整數。 In the general formula (I), R 1 to R 8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R 1 ~ R 8 may all be the same or different. n represents an integer from 0 to 3.

上述一般式(I)所示之聯苯型環氧樹脂可藉由對聯苯酚化合物使環氧氯丙烷以公知方法進行反應而得。 The biphenyl type epoxy resin represented by the above general formula (I) can be obtained by reacting epichlorohydrin with a biphenol compound in a known manner.

作為一般式(I)中之R1~R8,例如可各自獨立地舉出氫原子;甲基、乙基、丙基、丁基、異丙基、異丁基、第三丁基等碳數1~10的烷基;乙烯基、烯丙基、丁烯基等碳數1~10的烯基等。其中各自獨立地以氫原子或甲基為佳。 As R 1 to R 8 in the general formula (I), for example, a hydrogen atom may be independently mentioned; a carbon such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a tributyl group; An alkyl group having 1 to 10 carbon atoms; an alkenyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group, and a butenyl group. Each of them is preferably a hydrogen atom or a methyl group.

作為如此之環氧樹脂,例如可舉出將4,4’-雙(2,3-環氧基丙氧基)聯苯或4,4’-雙(2,3-環氧基丙氧基)-3,3’,5,5’-四甲基聯苯作為主成分的環氧樹脂、使環氧氯丙烷與4,4’-聯苯酚或4,4’- (3,3’,5,5’-四甲基)聯苯酚進行反應所得之環氧樹脂等。 As such an epoxy resin, for example, 4,4'-bis(2,3-epoxypropoxy)biphenyl or 4,4'-bis(2,3-epoxypropoxy group) can be mentioned. )-3,3',5,5'-tetramethylbiphenyl as the main component of epoxy resin, making epichlorohydrin and 4,4'-biphenol or 4,4'- An epoxy resin obtained by reacting (3,3',5,5'-tetramethyl)biphenol.

其中以將4,4’-雙(2,3-環氧基丙氧基)-3,3’,5,5’-四甲基聯苯作為主成分的環氧樹脂為佳。作為如此之環氧樹脂,作為市售品,可取得三菱化學股份有限公司(舊日本環氧樹脂股份有限公司)製之商品名YX-4000。 Among them, an epoxy resin containing 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl as a main component is preferred. As such a commercially available product, a trade name YX-4000 manufactured by Mitsubishi Chemical Corporation (formerly Japan Epoxy Resin Co., Ltd.) can be obtained.

使用上述聯苯型環氧樹脂時,為了發揮其性能,其含有率設為環氧樹脂全量中20質量%以上為佳,30質量%以上為較佳,50質量%以上為更佳。 When the biphenyl type epoxy resin is used, the content thereof is preferably 20% by mass or more based on the total amount of the epoxy resin, more preferably 30% by mass or more, and still more preferably 50% by mass or more.

作為前述硫二苯酚型環氧樹脂,例如可舉出下述一般式(II)所示之環氧樹脂等。 The thiodiphenol type epoxy resin may, for example, be an epoxy resin represented by the following general formula (II).

一般式(II)中,R1~R8各獨立表示氫原子或碳數1~10的取代或未取代的一價烴基。R1~R8可全相同或相異。n表示0~3的整數。 In the general formula (II), R 1 to R 8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R 1 ~ R 8 may all be the same or different. n represents an integer from 0 to 3.

上述一般式(II)所示硫二苯酚型環氧樹脂可藉由對硫二苯酚化合物使環氧氯丙烷以公知方法進行反應而得。 The thiodiphenol type epoxy resin represented by the above general formula (II) can be obtained by reacting epichlorohydrin with a thiodiphenol compound by a known method.

作為一般式(II)中之R1~R8,例如可各自獨立地舉出氫原子;甲基、乙基、丙基、丁基、異丙基、 異丁基、第三丁基等碳數1~10的烷基;乙烯基、烯丙基、丁烯基等碳數1~10的烯基等。其中各自獨立地以氫原子、甲基或第三丁基為佳。 As R 1 to R 8 in the general formula (II), for example, a hydrogen atom may be independently mentioned; a carbon such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group; An alkyl group having 1 to 10 carbon atoms; an alkenyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group, and a butenyl group. Each of them is preferably a hydrogen atom, a methyl group or a tert-butyl group.

作為如此之環氧樹脂,例如可舉出將4,4’-二羥基二苯基硫醚的二縮水甘油基醚作為主成分之環氧樹脂、將2,2’,5,5’-四甲基-4,4’-二羥基二苯基硫醚的二縮水甘油基醚作為主成分之環氧樹脂、將2,2’-二甲基-4,4’-二羥基-5,5’-二-第三丁基二苯基硫醚的二縮水甘油基醚作為主成分之環氧樹脂等。 Examples of such an epoxy resin include an epoxy resin containing diglycidyl ether of 4,4′-dihydroxydiphenyl sulfide as a main component, and 2,2′,5,5′-four. Epoxy resin as a main component of diglycidyl ether of methyl-4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-dihydroxy-5,5 An epoxy resin or the like having a diglycidyl ether of '-di-t-butyldiphenyl sulfide as a main component.

其中以將2,2’-二甲基-4,4’-二羥基-5,5’-二-第三丁基二苯基硫醚的二縮水甘油基醚作為主成分之環氧樹脂為佳。作為如此之環氧樹脂,作為市售品,可取得新日鐵化學股份有限公司製之商品名YSLV-120TE。 The epoxy resin containing diglycidyl ether of 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di-t-butyldiphenyl sulfide as a main component is good. As such a commercially available product, a trade name of YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd. can be obtained.

使用上述硫二苯酚型環氧樹脂時,為了發揮其性能,該含有率設為環氧樹脂全量中20質量%以上為佳,以30質量%以上為較佳,以50質量%以上為更佳。 When the thiodiphenol type epoxy resin is used, the content is preferably 20% by mass or more based on the total amount of the epoxy resin, preferably 30% by mass or more, and more preferably 50% by mass or more. .

作為前述雙酚F型環氧樹脂,例如可舉出下述一般式(III)所示環氧樹脂等。 Examples of the bisphenol F-type epoxy resin include an epoxy resin represented by the following general formula (III).

一般式(III)中,R1~R8各獨立表示氫原子或碳數1~10的取代或未取代的一價烴基。R1~R8可全相同或相異。n表示0~3的整數。 In the general formula (III), R 1 to R 8 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R 1 ~ R 8 may all be the same or different. n represents an integer from 0 to 3.

上述一般式(III)所示雙酚F型環氧樹脂可藉由對雙酚F化合物使環氧氯丙烷以公知方法進行反應而得。 The bisphenol F type epoxy resin represented by the above formula (III) can be obtained by reacting epichlorohydrin with a bisphenol F compound by a known method.

作為一般式(III)中之R1~R8,例如可各自獨立地舉出氫原子;甲基、乙基、丙基、丁基、異丙基、異丁基、第三丁基等碳數1~10的烷基;乙烯基、烯丙基、丁烯基等碳數1~10的烯基等。其中各自獨立地以氫原子或甲基為佳。 As R 1 to R 8 in the general formula (III), for example, a hydrogen atom may be independently mentioned; a carbon such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a third butyl group; An alkyl group having 1 to 10 carbon atoms; an alkenyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group, and a butenyl group. Each of them is preferably a hydrogen atom or a methyl group.

作為如此之環氧樹脂,例如可舉出將4,4’-亞甲基雙(2,6-二甲基苯酚)的二縮水甘油基醚作為主成分之環氧樹脂、將4,4’-亞甲基雙(2,3,6-三甲基苯酚)的二縮水甘油基醚作為主成分之環氧樹脂、將4,4’-亞甲基雙酚的二縮水甘油基醚作為主成分之環氧樹脂等。其中以將4,4’-亞甲基雙(2,6-二甲基苯酚)的二縮水甘油基醚作為主成分之環氧樹脂為佳。作為如此之環氧樹脂,作為市售品,可取得新日鐵化學股份有限公司製之商品名YSLV-80XY。 Examples of such an epoxy resin include an epoxy resin containing 4,4′-methylenebis(2,6-dimethylphenol) diglycidyl ether as a main component, and 4, 4'. - an epoxy resin containing methylene bis(2,3,6-trimethylphenol) diglycidyl ether as a main component, and diglycidyl ether of 4,4'-methylene bisphenol as a main component Ingredients such as epoxy resin. Among them, an epoxy resin containing a diglycidyl ether of 4,4'-methylenebis(2,6-dimethylphenol) as a main component is preferred. As such a commercially available product, a trade name of YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. can be obtained.

使用上述雙酚F型環氧樹脂時,為了發揮其性能,其含有率設為環氧樹脂全量中20質量%以上為佳,以30質量%以上為較佳,以50質量%以上為更佳。 When the bisphenol F-type epoxy resin is used, the content is preferably 20% by mass or more based on the total amount of the epoxy resin, preferably 30% by mass or more, and more preferably 50% by mass or more. .

作為前述酚醛清漆型環氧樹脂,例如可舉出下述一般式(IV)所示環氧樹脂等。 Examples of the novolak-type epoxy resin include an epoxy resin represented by the following general formula (IV).

一般式(IV)中,R各獨立表示以氫原子或選自碳原子、氫原子、氧原子之元素所構成的碳數1~10的取代或未取代之一價基,n表示0~10的整數。 In the general formula (IV), R each independently represents a substituted or unsubstituted one valent group having a hydrogen atom or an element selected from a carbon atom, a hydrogen atom and an oxygen atom, and n represents 0 to 10. The integer.

上述一般式(IV)所示酚醛清漆型環氧樹脂為藉由對酚醛清漆型酚樹脂使環氧氯丙烷進行反應而得。 The novolac type epoxy resin represented by the above general formula (IV) is obtained by reacting epichlorohydrin with a novolac type phenol resin.

作為上述一般式(IV)中之R,各自獨立地以氫原子;甲基、乙基、丙基、丁基、異丙基、異丁基等碳數1~10的烷基;甲氧基、乙氧基、丙氧基、丁氧基等碳數1~10的烷氧基為佳,以氫原子或甲基為較佳。n以0~3的整數為佳。 As the R in the above general formula (IV), each independently has a hydrogen atom; a methyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group; An alkoxy group having 1 to 10 carbon atoms such as an ethoxy group, a propoxy group or a butoxy group is preferred, and a hydrogen atom or a methyl group is preferred. n is preferably an integer from 0 to 3.

上述一般式(IV)所示酚醛清漆型環氧樹脂中,以鄰甲酚酚醛清漆型環氧樹脂為佳。作為如此之環氧樹脂,作為市售品,可取得大日本墨水化學工業股份有限公司製之商品名N500P-1。 Among the novolac type epoxy resins represented by the above general formula (IV), an o-cresol novolac type epoxy resin is preferred. As such a commercially available product, the product name N500P-1 manufactured by Dainippon Ink Chemical Industry Co., Ltd. can be obtained.

使用酚醛清漆型環氧樹脂時,為了發揮其性能,其含有率設為環氧樹脂全量中20質量%以上為佳,以30質量%以上為更佳。 When the novolac type epoxy resin is used, the content thereof is preferably 20% by mass or more based on the total amount of the epoxy resin, and more preferably 30% by mass or more.

作為前述萘型環氧樹脂,例如可舉出下述一般式(V)所示環氧樹脂等。作為前述三苯基甲烷型環氧樹脂,例如可舉出下述一般式(VI)所示環氧樹脂等。 Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (V). Examples of the triphenylmethane-type epoxy resin include an epoxy resin represented by the following general formula (VI).

一般式(V)中,R1~R3各獨立表示碳數1~12的取代或未取代之一價烴基。R1~R3可全相同或相異。p為1或0,m及n各獨立為0~11的整數,(m+n)為1~11的整數,且以使(m+p)成為1~12的整數的方式選擇p、m及n。i表示0~3的整數,j表示0~2的整數,k表示0~4的整數。 In the general formula (V), R 1 to R 3 each independently represent a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. R 1 to R 3 may all be the same or different. p is 1 or 0, m and n are each an integer of 0 to 11, and (m+n) is an integer of 1 to 11, and p and m are selected such that (m+p) becomes an integer of 1 to 12. And n. i represents an integer from 0 to 3, j represents an integer from 0 to 2, and k represents an integer from 0 to 4.

作為上述一般式(V)中之R1~R3,可各自獨立地舉出甲基、乙基、丙基、丁基、異丙基、異丁基、第三丁基等碳數1~10的烷基;乙烯基、烯丙基、丁烯基等碳數1~10的烯基等。其中以甲基為較佳。 R 1 to R 3 in the above general formula (V) may each independently represent a carbon number of a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a third butyl group. An alkyl group of 10; an alkenyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group or a butenyl group; and the like. Among them, a methyl group is preferred.

一般式(VI)中,R各獨立表示氫原子或碳數1~10的取代或未取代的一價烴基。n表示1~10的整數。 In the general formula (VI), R each independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer from 1 to 10.

作為上述一般式(VI)中之R,可各自獨立地舉出氫原子;甲基、乙基、丙基、丁基、異丙基、異丁基、第三丁基等碳數1~10的烷基;乙烯基、烯丙基、丁烯基等碳數1~10的烯基等。其中以氫原子或甲基為較佳。n以0~3的整數為佳。 As R in the above general formula (VI), a hydrogen atom may be independently mentioned; a carbon number of 1 to 10 such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a third butyl group; An alkyl group; an alkenyl group having 1 to 10 carbon atoms such as a vinyl group, an allyl group or a butenyl group; and the like. Among them, a hydrogen atom or a methyl group is preferred. n is preferably an integer from 0 to 3.

作為前述一般式(V)所示萘型環氧樹脂,可舉出將m個構成單位及n個構成單位無規地含有之無規共聚物、交互地含有之交互共聚物、規則地含有之共聚物、嵌段狀地含有之嵌段共聚物。可單獨使用這些中任1種,或組合2種以上使用。 The naphthalene type epoxy resin represented by the above general formula (V) includes a random copolymer which is randomly contained in m constituent units and n constituent units, and an interactive copolymer which is alternately contained and which is regularly contained. a copolymer, a block copolymer containing the block. These may be used alone or in combination of two or more.

又,作為前述一般式(VI)所示三苯基甲烷型環氧樹脂並無特別限制,但以水楊醛型環氧樹脂為佳。 Further, the triphenylmethane type epoxy resin represented by the above general formula (VI) is not particularly limited, but a salicylaldehyde type epoxy resin is preferred.

這些萘型環氧樹脂及三苯基甲烷型環氧樹脂可單獨使用任1種或組合兩者使用。使用萘型環氧樹脂及 三苯基甲烷型環氧樹脂之至少一方時,為了發揮其性能,其含有率以環氧樹脂全量中合計量為20質量%以上時為佳,以30質量%以上者為較佳,以50質量%以上為更佳。 These naphthalene type epoxy resins and triphenylmethane type epoxy resins may be used singly or in combination of two or more. Using naphthalene type epoxy resin and When at least one of the triphenylmethane type epoxy resins is used, the content thereof is preferably 20% by mass or more based on the total amount of the epoxy resin, and preferably 30% by mass or more, and 50% or more. More than % by mass is more preferable.

作為前述酚‧芳烷基樹脂的環氧化物,例如可舉出下述一般式(VII)所示環氧樹脂或下述一般式(VIII)所示環氧樹脂等。 Examples of the epoxide of the phenol ‧ aralkyl resin include an epoxy resin represented by the following general formula (VII) or an epoxy resin represented by the following general formula (VIII).

一般式(VII)中,R1~R4各獨立表示氫原子或碳數1~12的取代或未取代之一價烴基。R1~R4可全部相同或相異。R5各獨立表示碳數1~12的取代或未取代之一價烴基。存在複數個R5時,可全部相同或相異。i表示0~3的整數,n表示0~10的整數。 In the general formula (VII), R 1 to R 4 each independently represent a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. R 1 to R 4 may all be the same or different. R 5 each independently represents a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. When there are a plurality of R 5 , they may all be the same or different. i represents an integer from 0 to 3, and n represents an integer from 0 to 10.

一般式(VIII)中,R1~R8各獨立表示氫原子或碳數1~12的取代或未取代之一價烴基。R1~R8可全部相同或相異。R9各獨立表示碳數1~12的取代或未取代之一價烴基。存在複數個R9時,可全部相同或相異。i表示0~3的整數,n表示0~10的整數。 In the general formula (VIII), R 1 to R 8 each independently represent a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. R 1 to R 8 may all be the same or different. R 9 each independently represents a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. When there are a plurality of R 9 , they may all be the same or different. i represents an integer from 0 to 3, and n represents an integer from 0 to 10.

上述一般式(VII)所示酚‧芳烷基樹脂的環氧化物為可藉由對於經烷基取代、經芳香環取代或未取代之酚與二甲氧基對二甲苯所合成之酚‧芳烷基樹脂使環氧氯丙烷以公知方法進行反應而得。又,上述一般式(VIII)所示含有伸聯苯基骨架之酚‧芳烷基樹脂的環氧化物為可藉由對於經烷基取代、芳香環取代或未取代的酚與雙(甲氧基甲基)聯苯所合成之酚‧芳烷基樹脂使環氧氯丙烷以公知方法進行反應而得。 The epoxide of the phenol ‧ aralkyl resin represented by the above general formula (VII) is a phenol synthesized by an alkyl group-substituted, aromatic-substituted or unsubstituted phenol and dimethoxy-p-xylene The aralkyl resin is obtained by reacting epichlorohydrin in a known manner. Further, the epoxide of the phenol ‧ aralkyl resin containing a biphenyl skeleton represented by the above general formula (VIII) is phenol and bis(methoxy) which may be substituted by an alkyl group, an aromatic ring or an unsubstituted group The phenol ‧ aralkyl resin synthesized from the methyl group) biphenyl is obtained by reacting epichlorohydrin in a known manner.

作為一般式(VII)中之R1~R5及一般式(VIII)中之R1~R9所示碳數1~12的取代或未取代的一價烴基,例如可舉出甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二基等鏈狀烷基;環戊基、環己基、環庚基、環戊烯基、環己烯基等環狀烷基;苯甲基、苯乙基等由芳 基取代之烷基;由甲氧基取代之烷基、由乙氧基取代之烷基、由丁氧基取代之烷基等由烷氧基取代之烷基;胺基烷基、二甲基胺基烷基、二乙基胺基烷基等由胺基取代之烷基;由羥基取代之烷基;苯基、萘基、聯苯基等無取代芳基;甲苯基、二甲基苯基、乙基苯基、丁基苯基、第三丁基苯基、二甲基萘基等由烷基取代之芳基;甲氧基苯基、乙氧基苯基、丁氧基苯基、第三丁氧基苯基、甲氧基萘基等由烷氧基取代之芳基;二甲基胺基、二乙基胺基等由胺基取代之芳基;由羥基取代之芳基等。 The substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R 1 to R 5 in the general formula (VII) and R 1 to R 9 in the general formula (VIII) may, for example, be a methyl group. Ethyl, propyl, isopropyl, n-butyl, t-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl and the like chain alkyl; cyclopentyl, cyclohexyl a cyclic alkyl group such as a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; an alkyl group substituted with an aryl group such as a benzyl group or a phenethyl group; an alkyl group substituted by a methoxy group, substituted with an ethoxy group; An alkyl group substituted with an alkoxy group such as an alkyl group substituted with a butoxy group; an alkyl group substituted with an amine group such as an aminoalkyl group, a dimethylaminoalkyl group or a diethylaminoalkyl group; An alkyl group substituted by a hydroxyl group; an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group; a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, a t-butylphenyl group, and a second group; An aryl group substituted with an alkyl group such as a methylnaphthyl group; a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, a tert-butoxyphenyl group, a methoxynaphthyl group or the like substituted by an alkoxy group An aryl group; a dimethylamino group, a diethylamino group or the like substituted by an amine group An aryl group; an aryl group substituted by a hydroxyl group or the like.

其中作為一般式(VII)中之R1~R4及一般式(VIII)中之R1~R8,各自獨立地以氫原子或甲基為佳。作為一般式(VII)中的R5及一般式(VIII)中的R9以甲基為佳。 Wherein in the formula (VII) as a general formula of R 1 ~ R 4 and the general formula (VIII) R 1 ~ R 8 , are each independently a hydrogen atom or a methyl group is preferred. R 5 in the general formula (VII) and R 9 in the general formula (VIII) are preferably a methyl group.

一般式(VII)及一般式(VIII)中之i各獨立表示0~3的整數,以0或1為佳。 Each of i in the general formula (VII) and the general formula (VIII) independently represents an integer of 0 to 3, preferably 0 or 1.

又,一般式(VII)及一般式(VIII)中之n各獨立表示0~10的整數,平均為6以下時為較佳。作為如此之環氧樹脂,作為市售品,一般式(VII)可取得日本化藥股份有限公司製之商品名NC-2000L,一般式(VIII)可取得日本化藥股份有限公司製之商品名NC-3000S。 Further, in the general formula (VII) and the general formula (VIII), n each independently represents an integer of 0 to 10, and an average of 6 or less is preferable. As a commercially available product, the general formula (VII) can be obtained from the product name NC-2000L manufactured by Nippon Kayaku Co., Ltd., and the general formula (VIII) can be obtained from the product name of Nippon Kayaku Co., Ltd. NC-3000S.

使用酚‧芳烷基樹脂時,為了發揮其性能,其含有率設為環氧樹脂全量中20質量%以上為佳,以30質量%以上為較佳。 When the phenol aralkyl resin is used, the content thereof is preferably 20% by mass or more based on the total amount of the epoxy resin, and more preferably 30% by mass or more.

又,由兼顧難燃性與耐回焊性、流動性之觀點來看,含有上述一般式(I)所示環氧樹脂者為佳,其中以上述一般式(VIII)的R1~R8為氫原子且上述一般式(I)的R1~R8為氫原子且n=0為較佳。又,特別是其含有質量比為一般式(I)/一般式(VIII)=50/50~5/95為佳,以40/60~10/90為較佳,以30/70~15/85為更佳。作為滿足如此之含有質量比之化合物,作為市售品,可取得CER-3000L(日本化藥股份有限公司製之商品名)等。 Moreover, it is preferable to contain the epoxy resin represented by the above general formula (I) from the viewpoint of achieving both flame retardancy, reflow resistance, and fluidity, and R 1 to R 8 of the above general formula (VIII). It is a hydrogen atom and R 1 to R 8 of the above general formula (I) are a hydrogen atom and n = 0 is preferred. Further, in particular, the mass ratio thereof is generally (I) / general formula (VIII) = 50/50 to 5/95, preferably 40/60 to 10/90, and 30/70 to 15/. 85 is better. As a commercially available product, CER-3000L (trade name manufactured by Nippon Kayaku Co., Ltd.) or the like can be obtained as a commercially available product.

作為萘酚‧芳烷基樹脂的環氧化物,例如可舉出下述一般式(IX)所示環氧樹脂等。 Examples of the epoxide of the naphthol aralkyl resin include an epoxy resin represented by the following general formula (IX).

一般式(IX)中,R各獨立表示碳數1~12的取代或未取代之一價烴基。複數個R可全部相同或相異。i表示0~3的整數,X各獨立表示具有芳香環之二價有機基,n表示0~10的整數。 In the general formula (IX), R each independently represents a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. A plurality of Rs may all be the same or different. i represents an integer of 0 to 3, X each independently represents a divalent organic group having an aromatic ring, and n represents an integer of 0 to 10.

上述一般式(IX)所示萘酚‧芳烷基樹脂的環氧化物可藉由對於經烷基取代、經芳香環取代或未取代的萘酚與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯 所合成之萘酚‧芳烷基樹脂使環氧氯丙烷以公知方法進行反應而得。 The epoxide of the naphthol ‧ aralkyl resin represented by the above general formula (IX) can be obtained by using an alkyl substituted, an aromatic ring substituted or unsubstituted naphthol and dimethoxy p-xylene or bis (A) Oxymethyl)biphenyl The naphthol ‧ aralkyl resin synthesized is obtained by reacting epichlorohydrin in a known manner.

X例如可各自獨立地舉出伸苯基、伸聯苯基、伸萘基等伸芳基;由甲伸苯基等烷基取代之伸芳基;由烷氧基取代之伸芳基;由芳烷基取代之伸芳基;由苯甲基、苯乙基等芳烷基所得之二價基;苯二甲基等含有伸芳基之二價基等。其中由兼顧難燃性及保存安定性之觀點來看,各自獨立地為伸苯基或伸聯苯基較佳。 X, for example, each independently exhibits an extended aryl group such as a phenyl group, a phenylene group or a naphthyl group; an aryl group substituted with an alkyl group such as a methylphenyl group; and an aryl group substituted with an alkoxy group; An aralkyl group-substituted aryl group; a divalent group derived from an aralkyl group such as a benzyl group or a phenethyl group; a divalent group having an extended aryl group such as benzenedimethyl group; and the like. Among them, from the viewpoint of achieving both flame retardancy and storage stability, each of them is preferably a phenylene group or a phenylene group.

作為一般式(IX)中之R,例如可各自獨立地舉出甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二基等鏈狀烷基;環戊基、環己基、環庚基、環戊烯基、環己烯基等環狀烷基;苯甲基、苯乙基等由芳基取代之烷基;由甲氧基取代之烷基、由乙氧基取代之烷基、由丁氧基取代之烷基等由烷氧基取代之烷基;胺基烷基、二甲基胺基烷基、二乙基胺基烷基等由胺基取代之烷基;由羥基取代之烷基;苯基、萘基、聯苯基等無取代芳基;甲苯基、二甲基苯基、乙基苯基、丁基苯基、第三丁基苯基、二甲基萘基等由烷基取代之芳基;甲氧基苯基、乙氧基苯基、丁氧基苯基、第三丁氧基苯基、甲氧基萘基等由烷氧基取代之芳基;二甲基胺基、二乙基胺基等由胺基取代之芳基;由羥基取代之芳基等。其中作為一般式(IX)中之R,各自獨立地以甲基為佳,作為i以1或2為佳。作 為如此之一般式(IX),例如可舉出下述一般式(X)或(XI)所示萘酚‧烷基樹脂的環氧化物。 As R in the general formula (IX), for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl, hexyl, octyl may be independently mentioned. a chain alkyl group such as a fluorenyl group, a fluorenyl group, a tetradecyl group or the like; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; a benzyl group, a phenethyl group, etc. Alkyl-substituted alkyl group; alkyl group substituted by methoxy group, alkyl group substituted by ethoxy group, alkyl group substituted by butoxy group, alkyl group substituted by alkoxy group; aminoalkyl group, dimethyl group An alkyl group substituted with an amine group such as an aminoalkyl group or a diethylaminoalkyl group; an alkyl group substituted by a hydroxyl group; an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group; a tolyl group and a dimethylbenzene group; An aryl group substituted with an alkyl group such as ethyl, ethylphenyl, butylphenyl, tert-butylphenyl or dimethylnaphthyl; methoxyphenyl, ethoxyphenyl, butoxyphenyl An aryl group substituted with an alkoxy group such as a tert-butoxyphenyl group or a methoxynaphthyl group; an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group; and an aryl group substituted by a hydroxyl group; Wait. Among them, as R in the general formula (IX), each is preferably a methyl group, and i is preferably 1 or 2. Make As such a general formula (IX), for example, an epoxide of a naphthol ‧ alkyl resin represented by the following general formula (X) or (XI) can be given.

n表示0~10的整數,平均以6以下為較佳。作為下述一般式(X)所示環氧樹脂,作為市售品,可舉出新日鐵化學股份有限公司製之商品名ESN-375。作為下述一般式(XI)所示環氧樹脂,作為市售品,可舉出新日鐵化學股份有限公司製之商品名ESN-175。 n represents an integer of 0 to 10, and an average of 6 or less is preferable. The epoxy resin shown by the following general formula (X) is a commercial item, and the brand name ESN-375 by Nippon Steel Chemical Co., Ltd. is mentioned. The epoxy resin shown by the following general formula (XI) is a commercial item, and the brand name ESN-175 by Nippon Steel Chemical Co., Ltd. is mentioned.

使用上述萘酚‧芳烷基樹脂的環氧化物時,為了發揮其性能,其含有率設為環氧樹脂全量中20質量%以上為佳,以30質量%以上為較佳,以50質量%以上為更佳。 When the epoxide of the naphthol ‧ aralkyl resin is used, the content thereof is preferably 20% by mass or more based on the total amount of the epoxy resin, more preferably 30% by mass or more, and 50% by mass. The above is better.

一般式(X)中,X各獨立表示具有芳香環之二價有機基,n表示0~10的整數。 In the general formula (X), X each independently represents a divalent organic group having an aromatic ring, and n represents an integer of 0 to 10.

一般式(XI)中,X各獨立表示具有芳香環之二價有機基,n表示0~10的整數。 In the general formula (XI), X each independently represents a divalent organic group having an aromatic ring, and n represents an integer of 0 to 10.

上述聯苯型環氧樹脂、硫二苯酚型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、萘型環氧樹脂、三苯基甲烷型環氧樹脂、酚‧芳烷基樹脂的環氧化物及萘酚‧芳烷基樹脂的環氧化物可單獨使用任1種或組合2種以上使用。組合這些2種以上使用時,含有率合計設為環氧樹脂全量中50質量%以上者為佳,以60質量%以上為較佳,以80質量%以上為更佳。其中以將聯苯型環氧樹脂於環氧樹脂全量中設為50質量%以上者為佳,以60質量%以上為較佳,以80質量%以上為更佳。再者,併用聯苯型環氧樹脂以外的上述環氧樹脂為佳。 The above biphenyl type epoxy resin, thiodiphenol type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, naphthalene type epoxy resin, triphenylmethane type epoxy resin, phenol ‧ aralkyl The epoxide of the base resin and the epoxide of the naphthol ‧ aralkyl resin may be used alone or in combination of two or more. When these two or more types are used in combination, the content ratio is preferably 50% by mass or more based on the total amount of the epoxy resin, more preferably 60% by mass or more, and still more preferably 80% by mass or more. In particular, the biphenyl type epoxy resin is preferably 50% by mass or more based on the total amount of the epoxy resin, more preferably 60% by mass or more, and still more preferably 80% by mass or more. Further, it is preferred to use the above epoxy resin other than the biphenyl type epoxy resin.

〔(B)硬化劑〕 [(B) hardener]

於本發明所使用的(B)硬化劑,只要是一般使用於密封用環氧樹脂組成物者即可,並無特別限定。例如可舉出苯酚、甲酚、間苯二酚、兒茶酚、雙酚A、雙酚F、苯基苯酚、硫二苯酚、胺基苯酚、α-萘酚、β-萘酚、二羥基萘等酚類與甲醛、苯甲醛、水楊醛等具有醛基之化合物在酸性觸媒下進行縮合或共縮合所得之酚醛清漆型酚樹脂;由酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成之酚‧芳烷基樹脂、萘酚‧芳烷基樹脂等芳烷基型酚樹脂;酚酚醛清漆結構與酚‧芳烷基結構以無規、嵌段或交互進行重複的共聚合型酚‧芳烷基樹 脂;對苯二甲基及/或間苯二甲基改性酚樹脂;三聚氰胺改性酚樹脂;萜烯改性酚樹脂;二環戊二烯改性酚樹脂;環戊二烯改性酚樹脂;多環芳香環改性酚樹脂等。這些可單獨使用1種或組合2種以上使用。 The (B) curing agent used in the present invention is not particularly limited as long as it is generally used for a sealing epoxy resin composition. Examples thereof include phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, thiodiphenol, aminophenol, α -naphthol, β -naphthol, and dihydroxy group. a novolac type phenol resin obtained by condensing or co-condensing a phenol having a aldehyde group such as naphthalene with formaldehyde, benzaldehyde or salicylaldehyde under an acidic catalyst; and a phenol or dimethoxy-p-xylene or a double Aromatic phenolic resin such as phenol ‧ aralkyl resin synthesized by (methoxymethyl) biphenyl, naphthol ‧ aralkyl resin; phenol novolac structure and phenol ‧ aralkyl structure in random, embedded a copolymerized phenol aralkyl resin which is repeated in stages or alternately; a p-xylylene and/or m-xylylene modified phenol resin; a melamine-modified phenol resin; a terpene-modified phenol resin; Diene modified phenol resin; cyclopentadiene modified phenol resin; polycyclic aromatic ring modified phenol resin. These may be used alone or in combination of two or more.

其中由流動性、難燃性及耐回焊性的觀點來看,以酚‧芳烷基樹脂、共聚合型酚‧芳烷基樹脂及萘酚‧芳烷基樹脂為佳,由耐熱性、低膨脹率及低反翹性之觀點來看,以三苯基甲烷型酚樹脂為佳,由硬化性的觀點來看,以酚醛清漆型酚樹脂為佳。以含有這些酚樹脂之至少1種為佳。 Among them, from the viewpoints of fluidity, flame retardancy and reflow resistance, phenol ‧ aralkyl resin, copolymerized phenol ‧ aralkyl resin and naphthol ‧ aralkyl resin are preferred, and heat resistance, From the viewpoint of low expansion ratio and low anti-warpage property, a triphenylmethane type phenol resin is preferred, and a novolak type phenol resin is preferred from the viewpoint of hardenability. It is preferred to contain at least one of these phenol resins.

作為前述酚‧芳烷基樹脂,例如可舉出下述一般式(XII)所示樹脂。 The phenol aralkyl resin may, for example, be a resin represented by the following general formula (XII).

一般式(XII)中,R各獨立表示碳數1~12的取代或未取代之一價烴基。複數個R可全部相同或相異。i各獨立表示0~3的整數,X各獨立表示具有芳香環之二價有機基,n表示0~10的整數。 In the general formula (XII), R each independently represents a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. A plurality of Rs may all be the same or different. i each independently represents an integer of 0 to 3, X each independently represents a divalent organic group having an aromatic ring, and n represents an integer of 0 to 10.

作為上述一般式(XII)中之R,例如可各自獨立地舉出甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二基等 鏈狀烷基;環戊基、環己基、環庚基、環戊烯基、環己烯基等環狀烷基;苯甲基、苯乙基等由芳基取代之烷基;由甲氧基取代之烷基、由乙氧基取代之烷基、由丁氧基取代之烷基等由烷氧基取代之烷基;胺基烷基、二甲基胺基烷基、二乙基胺基烷基等由胺基取代之烷基;由羥基取代之烷基;苯基、萘基、聯苯基等未取代芳基;甲苯基、二甲基苯基、乙基苯基、丁基苯基、第三丁基苯基、二甲基萘基等由烷基取代之芳基;甲氧基苯基、乙氧基苯基、丁氧基苯基、第三丁氧基苯基、甲氧基萘基等由烷氧基取代之芳基;二甲基胺基、二乙基胺基等由胺基取代之芳基;由羥基取代之芳基等。 As R in the above general formula (XII), for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl, hexyl, etc. may be independently mentioned. Xinji, Yanji, Twelve, etc. a chain alkyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; an alkyl group substituted with an aryl group such as a benzyl group or a phenethyl group; Alkyl-substituted alkyl group, alkyl group substituted by ethoxy group, alkyl group substituted by butoxy group, etc.; alkyl group substituted by alkoxy group; aminoalkyl group, dimethylaminoalkyl group, diethylamine An alkyl group substituted with an amine group; an alkyl group substituted by a hydroxyl group; an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group; a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butyl group An aryl group substituted with an alkyl group such as a phenyl group, a t-butylphenyl group or a dimethylnaphthyl group; a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, a third butoxyphenyl group, An aryl group substituted with an alkoxy group such as a methoxynaphthyl group; an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group; an aryl group substituted with a hydroxyl group; and the like.

其中作為一般式(XII)中的R,各自獨立地以甲基為佳。又,一般式(XII)中之i各獨立表示0~3的整數,以1或2為佳。 Among them, as R in the general formula (XII), each is preferably a methyl group. Further, i in the general formula (XII) independently represents an integer of 0 to 3, preferably 1 or 2.

上述一般式(XII)中之X,各獨立表示具有芳香環之基。例如可各自獨立地舉出伸苯基、伸聯苯基、伸萘基等伸芳基;甲伸苯基等由烷基取代之伸芳基;由烷氧基取代之伸芳基;由苯甲基、苯乙基等芳烷基所得之二價基;由芳烷基取代之伸芳基;苯二甲基等含有伸芳基之二價基等。 X in the above general formula (XII) each independently represents a group having an aromatic ring. For example, an aryl group such as a stretching phenyl group, a stretching phenyl group or a stretching naphthyl group; an exoaryl group substituted by an alkyl group such as a phenyl group; an exoaryl group substituted by an alkoxy group; a divalent group obtained by an aralkyl group such as a methyl group or a phenethyl group; an extended aryl group substituted by an aralkyl group; a divalent group having an extended aryl group such as benzodimethyl group; and the like.

其中由兼顧難燃性、流動性與硬化性之觀點來看,X各自獨立地以取代或未取代的伸苯基為佳,例如作為上述一般式(XII),可舉出下述一般式(XIII)所示酚‧芳烷基樹脂。又由兼顧難燃性與耐回焊性之觀點來 看,X各自獨立地以取代或未取代的伸聯苯基為佳,例如作為上述一般式(XII),可舉出下述一般式(XIV)所示酚‧芳烷基樹脂。 In view of the viewpoints of compatibility with flame retardancy, fluidity, and hardenability, each of X is preferably a substituted or unsubstituted phenyl group. For example, the above general formula (XII) includes the following general formula ( Phenol aralkyl resin shown in XIII). From the point of view of both flame retardancy and reflow resistance It is preferable that each of X is a substituted or unsubstituted biphenyl group. For example, the above formula (XII) includes a phenol ‧ aralkyl resin represented by the following general formula (XIV).

n表示0~10的整數,平均以6以下為較佳。 n represents an integer of 0 to 10, and an average of 6 or less is preferable.

一般式(XIII)中,n表示0~10的整數。 In the general formula (XIII), n represents an integer of 0 to 10.

一般式(XIV)中,n表示0~10的整數。 In the general formula (XIV), n represents an integer of 0 to 10.

作為上述一般式(XIII)所示酚‧芳烷基樹脂,作為市售品,可舉出三井化學股份有限公司製之商品名XLC。作為一般式(XIV)所示含有伸聯苯基骨架之酚‧芳烷基樹脂,作為市售品,可舉出明和化成股份有限公司製之商品名MEH-7851。 The phenol aralkyl resin represented by the above general formula (XIII) is commercially available from Mitsui Chemicals Co., Ltd. under the trade name XLC. The phenol aralkyl resin containing a bisphenylene skeleton represented by the general formula (XIV) is commercially available, and the product name MEH-7851 manufactured by Mingwa Chemical Co., Ltd. is mentioned.

使用上述酚‧芳烷基樹脂時,為了發揮其性能,其含有率設為硬化劑全量中20質量%以上者為佳,以30質量%以上為較佳,50質量%以上為更佳。 When the phenol aralkyl resin is used, the content thereof is preferably 20% by mass or more based on the total amount of the curing agent, more preferably 30% by mass or more, and still more preferably 50% by mass or more.

作為前述萘酚‧芳烷基樹脂,例如可舉出下述一般式(XV)所示樹脂。 The naphthol ‧ aralkyl resin may, for example, be a resin represented by the following general formula (XV).

一般式(XV)中,R各獨立表示碳數1~12的取代或未取代之一價烴基。複數個R可全部相同或相異。i各獨立表示0~3的整數,X各獨立表示具有芳香環之二價有機基,n表示0~10的整數。 In the general formula (XV), R each independently represents a substituted or unsubstituted one-valent hydrocarbon group having 1 to 12 carbon atoms. A plurality of Rs may all be the same or different. i each independently represents an integer of 0 to 3, X each independently represents a divalent organic group having an aromatic ring, and n represents an integer of 0 to 10.

作為上述一般式(XV)中的R,例如可各自獨立地舉出甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二基等鏈狀烷基;環戊基、環己基、環庚基、環戊烯基、環己烯基等環狀烷基;苯甲基、苯乙基等由芳基取代之烷基;由甲氧基取代之烷基、由乙氧基取代之烷基、由丁氧基取代之烷基等由烷氧基取代之烷基;胺基烷基、二甲基胺基烷基、二乙基胺基烷基等由胺基取代之烷基;由羥基取代之烷基;苯基、萘基、聯苯基等無取代芳基;甲苯基、二甲基苯基、乙基苯基、丁基苯基、第三丁基苯基、二甲基萘基等由烷基取代之芳基;甲氧基苯基、乙氧基苯基、丁氧基苯基、第三丁氧基苯基、甲氧基萘基 等由烷氧基取代之芳基;二甲基胺基、二乙基胺基等由胺基取代之芳基;由羥基取代之芳基等。 As R in the above general formula (XV), for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a third butyl group, a pentyl group, a hexyl group, or the like may be independently mentioned. a chain alkyl group such as an octyl group, a decyl group or a dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; a benzyl group, a phenethyl group or the like An aryl-substituted alkyl group; an alkyl group substituted by a methoxy group; an alkyl group substituted by an ethoxy group; an alkyl group substituted by a butoxy group; An alkyl group substituted with an amine group such as an aminoalkyl group or a diethylaminoalkyl group; an alkyl group substituted by a hydroxyl group; an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group; a tolyl group or a dimethyl group; An aryl group substituted with an alkyl group such as phenyl, ethylphenyl, butylphenyl, tert-butylphenyl or dimethylnaphthyl; methoxyphenyl, ethoxyphenyl, butoxybenzene Base, tert-butoxyphenyl, methoxynaphthyl An aryl group substituted with an alkoxy group; an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group; an aryl group substituted with a hydroxyl group; and the like.

其中作為一般式(XV)中的R,以甲基為佳。又,一般式(XV)中的i各獨立表示0~3的整數,以1或2為佳。 Among them, as R in the general formula (XV), a methyl group is preferred. Further, i in the general formula (XV) independently represents an integer of 0 to 3, preferably 1 or 2.

上述一般式(XV)中的X各獨立表示具有芳香環之二價有機基。例如可各自獨立地舉出伸苯基、伸聯苯基、伸萘基等伸芳基;甲伸苯基等由烷基取代之伸芳基;由烷氧基取代之伸芳基;由芳烷基取代之伸芳基;由苯甲基、苯乙基等芳烷基所得之二價基;苯二甲基等含有伸芳基之二價基等。其中由保存安定性與難燃性之觀點來看,X各自獨立地以取代或未取代的伸苯基及伸聯苯基為佳,以伸苯基為較佳,例如作為上述一般式(XV),可舉出下述一般式(XVI)及(XVII)所示萘酚‧芳烷基樹脂。 X in the above general formula (XV) each independently represents a divalent organic group having an aromatic ring. For example, an aryl group such as a stretching phenyl group, a stretching phenyl group or a stretching naphthyl group; an exoaryl group substituted by an alkyl group such as a phenyl group; an exoaryl group substituted by an alkoxy group; An alkyl-substituted aryl group; a divalent group obtained from an aralkyl group such as a benzyl group or a phenethyl group; a divalent group having an extended aryl group such as benzodimethyl group; and the like. From the viewpoints of preservation stability and flame retardancy, X is preferably each independently substituted or unsubstituted phenyl and phenyl, and phenyl is preferred, for example, as the above general formula (XV). The naphthol ‧ aralkyl resin represented by the following general formulas (XVI) and (XVII) can be mentioned.

n表示0~10的整數,平均以6以下為較佳。 n represents an integer of 0 to 10, and an average of 6 or less is preferable.

一般式(XVI)中,n表示0~10的整數。 In the general formula (XVI), n represents an integer of 0-10.

一般式(XVII)中,n表示0~10的整數。 In the general formula (XVII), n represents an integer of 0 to 10.

作為上述一般式(XVI)所示萘酚‧芳烷基樹脂,作為市售品,可舉出新日鐵化學股份有限公司製之商品名SN-475。作為上述一般式(XVII)所示萘酚‧芳烷基樹脂,作為市售品,可舉出新日鐵化學股份有限公司製之商品名SN-170。 As a commercially available product, a naphthol ‧ aralkyl resin represented by the above general formula (XVI) is SN-475 manufactured by Nippon Steel Chemical Co., Ltd. As a commercially available product, a naphthol ‧ aralkyl resin represented by the above general formula (XVII) is SN-170, manufactured by Nippon Steel Chemical Co., Ltd.

使用上述萘酚‧芳烷基樹脂時,為了發揮其性能,其含有率設為硬化劑全量中20質量%以上者為佳,以30質量%以上為較佳,以50質量%以上為更佳。 When the naphthol ‧ aralkyl resin is used, the content thereof is preferably 20% by mass or more based on the total amount of the curing agent, preferably 30% by mass or more, and more preferably 50% by mass or more. .

上述一般式(XII)所示酚‧芳烷基樹脂、一般式(XV)所示萘酚‧芳烷基樹脂由難燃性的觀點來看,以其一部或全部與苊烯(acenaphthylene)預先進行混合者為佳。苊烯可由將苊(acenaphthene)進行脫氫而得,亦可使用市售品。又,亦可使用苊烯的聚合物或苊烯與其他芳香族烯烴之聚合物來取代苊烯。 The phenol aralkyl resin represented by the above general formula (XII) and the naphthol ‧ aralkyl resin represented by the general formula (XV) are one or all of them and acenaphthylene from the viewpoint of flame retardancy. It is better to mix in advance. The terpene can be obtained by dehydrogenating acenaphthene, and a commercially available product can also be used. Further, a terpene polymer or a polymer of a terpene and another aromatic olefin may be used instead of the terpene.

作為得到苊烯的的聚合物或苊烯與其他芳香族烯烴之聚合物的方法,可舉出自由基聚合、陽離子聚合、陰離子聚合等。又,聚合時可使用過去公知之觸媒,但亦可不使用觸媒而僅加熱進行。此時,聚合溫度以80℃~160℃為佳,以90℃~150℃為較佳。所得之苊烯的聚合物或苊烯與其他芳香族烯烴之聚合物的軟化點以 60℃~150℃為佳,以70℃~130℃為較佳。60℃以上時,成形時滲染會被抑制而有著成形性優良之傾向,150。℃以下時,與樹脂之相溶性有著提高之傾向。 Examples of the method for obtaining a polymer of a terpene or a polymer of a terpene and another aromatic olefin include radical polymerization, cationic polymerization, anionic polymerization, and the like. Further, a conventionally known catalyst may be used for the polymerization, but it may be heated only without using a catalyst. In this case, the polymerization temperature is preferably from 80 ° C to 160 ° C, and more preferably from 90 ° C to 150 ° C. The softening point of the obtained terpene polymer or the polymer of the terpene and other aromatic olefins 60 ° C ~ 150 ° C is preferred, 70 ° C ~ 130 ° C is preferred. When it is 60 ° C or more, the bleeding during molding is suppressed and the formability is excellent, 150. When it is below °C, the compatibility with the resin tends to increase.

作為與苊烯共聚合之其他芳香族烯烴,可舉出苯乙烯、α-甲基苯乙烯、茚、苯並噻吩、苯並呋喃、乙烯萘、乙烯聯苯或彼等之烷基取代體等。又,除上述芳香族烯烴以外,在對本發明的效果無阻礙之範圍內,可併用脂肪族烯烴。作為脂肪族烯烴,可舉出(甲基)丙烯酸及其酯、馬來酸酐、衣康酸酐、富馬酸及該等之酯等。這些脂肪族烯烴之使用量以聚合單體全量中20質量%以下為佳,以9質量%以下為較佳。 Examples of the other aromatic olefin copolymerized with terpene include styrene, α -methylstyrene, anthracene, benzothiophene, benzofuran, vinylnaphthalene, ethylenebiphenyl or alkyl substituents thereof. . Further, in addition to the above aromatic olefin, an aliphatic olefin may be used in combination within a range not inhibiting the effects of the present invention. Examples of the aliphatic olefin include (meth)acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid, and the like. The amount of use of these aliphatic olefins is preferably 20% by mass or less based on the total amount of the polymerizable monomers, and preferably 9% by mass or less.

作為硬化劑的一部或全部與苊烯之預先混合方法,可進行將硬化劑及苊烯分別粉碎為微細狀後直接在固體狀態下以混合器等進行混合之方法、將兩成分均勻溶解於會溶解兩成分之溶劑後除去溶劑之方法、在硬化劑及/或苊烯之軟化點以上的溫度將兩者熔融混合之方法等。這些方法中,以可得到均勻混合物且較少不純物混入的熔融混合法為佳。藉由前述方法可製造出預備混合物(苊烯改性硬化劑)。 As a method of pre-mixing one or all of the curing agent with the terpene, the curing agent and the terpene may be separately pulverized into a fine form, and then directly mixed in a solid state by a mixer or the like, and the two components may be uniformly dissolved. A method in which a solvent of both components is dissolved, a solvent is removed, and a method of melt-mixing the two at a temperature equal to or higher than a softening point of the curing agent and/or terpene. Among these methods, a melt mixing method in which a homogeneous mixture is obtained and less impurities are mixed is preferred. A preliminary mixture (terpene-modified hardener) can be produced by the aforementioned method.

進行熔融混合時的溫度條件,若為硬化劑及/或苊烯之軟化點以上的溫度即可並無限制。具體以100℃~250℃為佳,以120℃~200℃為更佳。又,熔融混合只要是將兩者混合至均勻即可,混合時間並無限制,但以1小時~20小時為佳,以2小時~15小時為較 佳。預先混合硬化劑與苊烯時,於混合中苊烯進行聚合或與硬化劑進行反應亦無妨。 The temperature conditions at the time of melt mixing are not limited as long as it is a temperature higher than the softening point of the curing agent and/or terpene. Specifically, it is preferably 100 ° C to 250 ° C, and more preferably 120 ° C to 200 ° C. Further, the melt mixing may be carried out by mixing the two to be uniform, and the mixing time is not limited, but it is preferably from 1 hour to 20 hours, and from 2 hours to 15 hours. good. When the hardener and the terpene are mixed in advance, it is also possible to polymerize or react with the hardener in the mixing.

作為三苯基甲烷型酚樹脂,例如可舉出下述一般式(XVIII)所示酚樹脂等。 Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XVIII).

一般式(XVIII)中,R各獨立表示氫原子或碳數1~10的取代或未取代之一價烴基,n表示0~10的整數。 In the general formula (XVIII), R each independently represents a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.

作為上述一般式(XVIII)中的R,例如可各自獨立地舉出氫原子;甲基、乙基、丙基、丁基、異丙基、第三丁基等烷基;乙烯基、烯丙基、丁烯基等烯基;鹵化烷基;由胺基取代之烷基;由氫硫基取代之烷基等。其中作為R,各自獨立地以甲基、乙基等烷基或氫原子為佳,以甲基或氫原子為較佳。 As R in the above general formula (XVIII), for example, a hydrogen atom may be independently mentioned; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a tributyl group; a vinyl group; An alkenyl group such as a butyl group; a halogenated alkyl group; an alkyl group substituted by an amine group; an alkyl group substituted by a thiol group; Among them, R is preferably an alkyl group such as a methyl group or an ethyl group or a hydrogen atom, and a methyl group or a hydrogen atom is preferred.

使用三苯基甲烷型酚樹脂時,為了發揮其性能,其含有率設為硬化劑全量中30質量%以上時為佳,以50質量%以上為較佳。 When the triphenylmethane type phenol resin is used, the content thereof is preferably 30% by mass or more based on the total amount of the curing agent, and preferably 50% by mass or more.

作為酚醛清漆型酚樹脂,例如可舉出下述一般式(XIX)所示酚樹脂等酚醛清漆型酚樹脂、甲酚酚醛清漆樹脂等。其中以下述一般式(XIX)所示酚醛清漆型酚樹脂為佳。 Examples of the novolak-type phenol resin include a novolac type phenol resin such as a phenol resin represented by the following general formula (XIX), and a cresol novolak resin. Among them, a novolac type phenol resin represented by the following general formula (XIX) is preferred.

一般式(XIX)中,R各獨立表示氫原子或碳數1~10的取代或未取代之一價烴基,n表示0~10的整數。 In the general formula (XIX), R each independently represents a hydrogen atom or a substituted or unsubstituted one-valent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.

作為上述一般式(XIX)中的R,例如可各自獨立地舉出氫原子;甲基、乙基、丙基、丁基、異丙基、第三丁基等烷基;乙烯基、烯丙基、丁烯基等烯基;鹵化烷基;由胺基取代之烷基;由氫硫基取代之烷基等。其中作為R,各自獨立地以甲基、乙基等烷基或氫原子為佳,以氫原子為較佳。 As R in the above general formula (XIX), for example, a hydrogen atom may be independently mentioned; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or a tributyl group; a vinyl group; An alkenyl group such as a butyl group; a halogenated alkyl group; an alkyl group substituted by an amine group; an alkyl group substituted by a thiol group; Among them, R is preferably an alkyl group such as a methyl group or an ethyl group or a hydrogen atom, and a hydrogen atom is preferred.

n表示0~10的整數,平均值為0~8為佳。 n represents an integer from 0 to 10, and an average value of 0 to 8 is preferred.

作為前述一般式(XIX)所示酚醛清漆型酚樹脂,作為市售品,可舉出明和化成股份有限公司製之商品名H-100。 The novolac type phenol resin represented by the above-mentioned general formula (XIX) is a commercial product, and the product name H-100 by the company of Minghe Chemical Co., Ltd. is mentioned.

使用酚醛清漆型酚樹脂時,為了發揮其性能,其含有率設為硬化劑全量中30質量%以上為佳,以50質量%以上為較佳。 When a novolac type phenol resin is used, the content thereof is preferably 30% by mass or more, and preferably 50% by mass or more, in order to exhibit the performance.

作為共聚合型酚‧芳烷基樹脂,例如可舉出下述一般式(XX)所示酚樹脂。 The phenol resin represented by the following general formula (XX) is exemplified as the copolymerized phenol aralkyl resin.

一般式(XX)中,R各獨立表示氫原子、碳數1~12的取代或未取代之一價烴基或羥基。複數個R可全部相同或相異。又X各獨立表示具有芳香環之二價基。n及m各獨立表示0~10的整數。 In the general formula (XX), R each independently represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms or a hydroxyl group. A plurality of Rs may all be the same or different. Further, X each independently represents a divalent group having an aromatic ring. n and m each independently represent an integer of 0 to 10.

作為上述一般式(XX)中的R,例如可各自獨立地舉出氫原子;甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二基等鏈狀烷基;環戊基、環己基、環庚基、環戊烯基、環己烯基等環狀烷基;苯甲基、苯乙基等由芳基取代之烷基;由甲氧基取代之烷基、由乙氧基取代之烷基、由丁氧基取代之烷基等由烷氧基取代之烷基;胺基烷基、二甲基胺基烷基、二乙基胺基烷基等由胺基取代之烷基;由羥基取代之烷基;苯基、萘基、聯苯基等無取代芳基;甲苯基、二甲基苯基、乙基苯基、丁基苯基、 第三丁基苯基、二甲基萘基等由烷基取代之芳基;甲氧基苯基、乙氧基苯基、丁氧基苯基、第三丁氧基苯基、甲氧基萘基等由烷氧基取代之芳基;二甲基胺基、二乙基胺基等由胺基取代之芳基;由羥基取代之芳基等。其中作為R,各自獨立地以氫原子或甲基為佳。 As R in the above general formula (XX), for example, a hydrogen atom may be independently mentioned; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group, and pentyl group. a chain alkyl group such as a hexyl group, an octyl group, a decyl group or a dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group or a cyclohexenyl group; a benzyl group or a phenyl group; An alkyl group substituted with an aryl group; an alkyl group substituted by a methoxy group, an alkyl group substituted by an ethoxy group, an alkyl group substituted by a butoxy group, or the like, an alkyl group substituted by an alkoxy group; an aminoalkyl group; An alkyl group substituted with an amine group such as a dimethylaminoalkyl group or a diethylaminoalkyl group; an alkyl group substituted by a hydroxyl group; an unsubstituted aryl group such as a phenyl group, a naphthyl group or a biphenyl group; a tolyl group; Dimethylphenyl, ethylphenyl, butylphenyl, An aryl group substituted with an alkyl group such as a butyl phenyl group or a dimethyl naphthyl group; a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, a tert-butoxyphenyl group, a methoxy group An aryl group substituted with an alkoxy group such as a naphthyl group; an aryl group substituted with an amine group such as a dimethylamino group or a diethylamino group; an aryl group substituted with a hydroxyl group; and the like. Among them, as R, each independently has a hydrogen atom or a methyl group.

又,n及m各獨立表示0~10的整數,平均以6以下為較佳。 Further, n and m each independently represent an integer of 0 to 10, and an average of 6 or less is preferable.

作為上述一般式(XX)中的X,例如可舉出伸苯基、伸聯苯基、伸萘基等伸芳基;甲伸苯基等由烷基取代之伸芳基;由烷氧基取代之伸芳基;由芳烷基取代之伸芳基;由苯甲基、苯乙基等芳烷基所得之二價基;苯二甲基等含有伸芳基之二價基等。其中由保存安定性與難燃性之觀點來看,以取代或未取代之伸苯基或伸聯苯基為佳。作為一般式(XX)所示化合物,作為市售品,可取得HE-510(Air Water股份有限公司製之商品名)等。 Examples of X in the above general formula (XX) include an extended aryl group such as a stretched phenyl group, a stretched biphenyl group, or an extended naphthyl group; an alkyl group substituted with an alkyl group; and an alkoxy group; a substituted aryl group; an extended aryl group substituted by an aralkyl group; a divalent group obtained from an aralkyl group such as a benzyl group or a phenethyl group; a divalent group having an extended aryl group such as benzodimethyl group; and the like. Among them, a substituted or unsubstituted phenyl group or a biphenyl group is preferred from the viewpoints of preservation stability and flame retardancy. As a compound represented by the general formula (XX), as a commercial product, HE-510 (trade name, manufactured by Air Water Co., Ltd.) or the like can be obtained.

作為前述一般式(XX)所示共聚合型酚‧芳烷基樹脂,可舉出將m個構成單位及n個構成單位以無規方式含有之無規共聚物、以交互方式含有之交互共聚物、以規則方式含有之共聚物、以嵌段狀方式含有之嵌段共聚物。這些可使用單獨任1種或組合2種以上使用。 The copolymerized phenol aralkyl resin represented by the above general formula (XX) includes a random copolymer containing m constituent units and n constituent units in a random manner, and interactively copolymerized. The copolymer, the copolymer contained in a regular manner, and the block copolymer contained in a block form. These may be used alone or in combination of two or more.

使用共聚合型酚‧芳烷基樹脂時,為了發揮其性能,其含有率設為硬化劑全量中30質量%以上時為佳,以50質量%以上為較佳。 In the case of using a copolymerized phenol aralkyl resin, the content is preferably 30% by mass or more based on the total amount of the curing agent, and preferably 50% by mass or more.

上述酚‧芳烷基樹脂、萘酚‧芳烷基樹脂、三苯基甲烷型酚樹脂、酚醛清漆型酚脂及共聚合型酚‧芳烷基樹脂可單獨使用任1種或組合2種以上使用。組合2種以上使用時的含有率設為酚樹脂全量中合計50質量%以上時為佳,以60質量%以上為較佳,80質量%以上為更佳。 The phenol aralkyl resin, the naphthol aralkyl resin, the triphenylmethane phenol resin, the novolak phenol resin, and the copolymerized phenol aralkyl resin may be used alone or in combination of two or more. use. When the content of the phenol resin is 50% by mass or more in total, the content is preferably 60% by mass or more, and more preferably 80% by mass or more.

〔(C)二苯甲酮衍生物〕 [(C) benzophenone derivative]

本發明的密封用環氧樹脂組成物含有(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物。藉此得到在高溫與金屬之黏著性高且耐回焊性優良的密封用環氧樹脂組成物。 The epoxy resin composition for sealing of the present invention contains (C) a benzophenone derivative having one or more phenolic hydroxyl groups in one molecule. Thereby, a sealing epoxy resin composition having high adhesion to a metal at a high temperature and excellent reflow resistance is obtained.

本發明中所使用的(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物只要是於取代或未取代之二苯甲酮、萘基苯基酮、二萘酮、呫噸酮(xanthone)、芴酮(fluorenone)等的芳香環上直接結合1個以上羥基者即可,並無特別限制。(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物可單獨使用1種或亦可組合2種以上使用。 (C) a benzophenone derivative having one or more phenolic hydroxyl groups in one molecule used in the present invention as long as it is a substituted or unsubstituted benzophenone, naphthyl phenyl ketone or dinaphthone It is not particularly limited as long as one or more hydroxyl groups are directly bonded to an aromatic ring such as xanthone or fluorenone. (C) The benzophenone derivative which has one or more phenolic hydroxyl groups in one molecule may be used alone or in combination of two or more.

具體而言,可舉出鄰羥基二苯甲酮、間羥基二苯甲酮、對羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-正辛氧基二苯甲酮、2-羥基-4-烯丙氧基二苯甲酮、2,4-二羥基二苯甲酮、4,4’-二羥基二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,3,4-三羥基二苯甲酮、 2,2’,4,4’-四羥基二苯甲酮、2,3,4,4’-四羥基二苯甲酮、2,3,3’,4,4’,5-六羥基二苯甲酮及其位置異構物或取代體等。由熱應力減低(在回焊溫度的彈性率減低)的觀點來看,以鄰羥基二苯甲酮、間羥基二苯甲酮、對羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮為佳,進一步由黏著性提高的觀點來看,以2,4-二羥基二苯甲酮、4,4’-二羥基二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮為佳。 Specific examples thereof include o-hydroxybenzophenone, m-hydroxybenzophenone, p-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-n-octyl group. Oxybenzophenone, 2-hydroxy-4-allyloxybenzophenone, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,2'- Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,3',4,4',5-hexahydroxydi Benzophenone and its positional isomers or substituents. From the viewpoint of reduced thermal stress (decreased elastic modulus at reflow temperature), o-hydroxybenzophenone, m-hydroxybenzophenone, p-hydroxybenzophenone, 2-hydroxy-4-methoxy Benzophenone, 2-hydroxy-4-octyloxybenzophenone is preferred, and further, from the viewpoint of improved adhesion, 2,4-dihydroxybenzophenone, 4,4'-dihydroxyl Benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone are preferred.

本發明中所使用的(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物之總含有率為密封用環氧樹脂組成物中0.1質量%以上,以1.0質量%以下為佳。在0.1質量%以上時,有充分發揮發明效果之傾向,在1.0質量%以下時,有充分維持密封用環氧樹脂組成物之硬度的傾向。 The total content of the (B) benzophenone derivative having one or more phenolic hydroxyl groups in one molecule used in the present invention is 0.1% by mass or more and 1.0% by mass in the epoxy resin composition for sealing. The following is better. When it is 0.1% by mass or more, the effect of the invention is sufficiently exhibited, and when it is 1.0% by mass or less, the hardness of the epoxy resin composition for sealing tends to be sufficiently maintained.

本發明中,(A)環氧樹脂與(B)硬化劑及(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物的當量比,即(B)硬化劑及(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物中的總羥基數相對於(A)環氧樹脂中之環氧基數之比((B)硬化劑及(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物中的總羥基數/(A)環氧樹脂中的環氧基數)並無特別限定。為了將各未反應部分抑制為最少,設定前述當量比為0.5以上且2.0以下之範圍為佳,以0.6以上且 1.3以下為較佳。為了得到成形性優良的密封用環氧樹脂組成物,設定為0.8以上且1.2以下之範圍為更佳。 In the present invention, (A) an epoxy resin and (B) a curing agent and (C) an equivalent ratio of a benzophenone derivative having one or more phenolic hydroxyl groups in one molecule, that is, (B) a curing agent and (C) ratio of the total number of hydroxyl groups in the benzophenone derivative having one or more phenolic hydroxyl groups in one molecule to the number of epoxy groups in the epoxy resin (A) (B) hardener and C) The total number of hydroxyl groups in the benzophenone derivative having one or more phenolic hydroxyl groups in one molecule / (A) The number of epoxy groups in the epoxy resin) is not particularly limited. In order to minimize each unreacted portion, it is preferable to set the above-described equivalent ratio to be 0.5 or more and 2.0 or less, and to be 0.6 or more. 1.3 is preferred below. In order to obtain a sealing epoxy resin composition excellent in moldability, a range of 0.8 or more and 1.2 or less is more preferable.

〔(D)矽烷化合物〕 [(D) decane compound]

本發明的成形材料可含有(D)矽烷化合物。所謂(D)矽烷化合物為環氧基矽烷、氫硫基矽烷、胺基矽烷、烷基矽烷、脲矽烷、乙烯矽烷等各種矽烷系化合物。若要例示這些,可舉出乙烯三氯矽烷、乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯參(β-甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基二甲基甲氧基矽烷、γ-甲基丙烯醯氧基丙基二甲基乙氧基矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、γ-丙烯醯氧基丙基三乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基二甲基甲氧基矽烷、γ-環氧丙氧基丙基二甲基乙氧基矽烷、乙烯三乙醯氧基矽烷、γ-氫硫基丙基三甲氧基矽烷、γ-氫硫基丙基三乙氧基矽烷、雙(三乙氧基矽烷基丙基)四硫醚、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-〔雙(β-羥基乙基)〕胺基丙基三乙氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三乙氧基矽 烷、N-(三甲氧基矽烷基丙基)伸乙基二胺、異氰酸酯丙基三甲氧基矽烷、異氰酸酯丙基三乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、二苯基矽烷二醇、三苯基甲氧基矽烷、三苯基乙氧基矽烷、三苯基矽烷醇、N-β-(N-乙烯苯甲基胺基乙基)-γ-胺基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷、六甲基二矽烷、γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基三乙氧基矽烷、2-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、N-(3-三乙氧基矽烷基丙基)苯基亞胺、3-(3-(三乙氧基矽烷基)丙基胺基)-N,N-二甲基丙醯胺、N-三乙氧基矽烷基丙基-β-丙胺酸甲酯、3-(三乙氧基矽烷基丙基)二氫-3,5-呋喃二酮、雙(三甲氧基矽烷基)苯等矽烷系化合物;1H-咪唑、2-烷基咪唑、2,4-二烷基咪唑、4-乙烯咪唑等咪唑化合物與γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷等γ-環氧丙氧基丙基烷氧基矽烷之反應物的咪唑系矽烷化合物。這些可單獨使用1種或組合2種以上使用。 The molding material of the present invention may contain (D) a decane compound. The (D) decane compound is various decane-based compounds such as epoxy decane, hydrothiodecane, amino decane, alkyl decane, urea decane, and vinyl decane. To exemplify these, examples include ethylene trichlorodecane, ethylene trimethoxy decane, ethylene triethoxy decane, ethylene ginseng ( β -methoxyethoxy) decane, and γ -methyl propylene methoxy propyl group. Trimethoxydecane, γ -methacryloxypropyltriethoxydecane, γ -methacryloxypropylmethyldimethoxydecane, γ -methacryloxypropylpropyl Diethoxy decane, γ -methyl propylene methoxypropyl dimethyl methoxy decane, γ -methyl propylene methoxy propyl dimethyl ethoxy decane, γ - propylene methoxy propylene Trimethoxy decane, γ -propylene methoxypropyl triethoxy decane, β- (3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ -glycidoxypropyltrimethyl Oxydecane, γ -glycidoxypropyltriethoxydecane, γ -glycidoxypropylmethyldimethoxydecane, γ -glycidoxypropylmethyldiethoxylate Base decane, γ -glycidoxypropyl dimethyl methoxy decane, γ -glycidoxypropyl dimethyl ethoxy decane, ethylene triethoxy decane, γ -hydrogenthio Propyl three Silane group, γ - mercapto propyltriethoxysilane Silane, bis (triethoxysilylpropyl silicon alkyl) tetrasulfide, γ - aminopropyl trimethoxy Silane, γ - aminopropyl three Silane ethoxy, γ - [bis (β - hydroxyethyl) amino] propyltriethoxysilane Silane, N- β - (aminoethyl) - γ - aminopropyl triethoxysilane Silane, N-(trimethoxydecylpropyl) ethylene ethylamine, isocyanate propyl trimethoxy decane, isocyanate propyl triethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, two Methyl dimethoxy decane, dimethyl diethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, Diphenyldecanediol, triphenylmethoxydecane, triphenylethoxydecane, triphenylstanol, N- β- (N-vinylbenzylaminoethyl) -amine Propyltrimethoxydecane, γ -chloropropyltrimethoxydecane, hexamethyldioxane, γ -anilinopropyltrimethoxydecane, γ -anilinopropyltriethoxydecane, 2-triethyl Oxyalkylene-N-( 1,3-Dimethyl-butylene)propylamine, 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine, N-(3-triethoxy) Base propyl propyl) phenylimine, 3-(3-(triethoxydecyl)propylamino)-N,N-dimethylpropanamide, N-triethoxydecyl propyl a decane compound such as methyl-β-alanine methyl ester, 3-(triethoxydecylpropyl)dihydro-3,5-furandione or bis(trimethoxydecyl)benzene; 1H-imidazole, Imidazole compound such as 2-alkylimidazole, 2,4-dialkylimidazole or 4-vinylimidazole with γ -glycidoxypropyltrimethoxydecane, γ -glycidoxypropyltriethoxy An imidazole-based decane compound of a reaction product of γ -glycidoxypropyl alkoxy decane such as decane. These may be used alone or in combination of two or more.

含有(D)矽烷化合物時,(D)矽烷化合物之總含有率由成形性及流動性之觀點來看,以密封用環氧樹脂組成物中0.06質量%以上且2質量%以下為佳, 以0.1質量%以上且0.75質量%以下為較佳,以0.2質量%以上且0.7質量%以下為更佳。在0.06質量%以上時,有抑制流動性降低之傾向,在2質量%以下時,有抑制空隙等成形不良產生的傾向。 When the (D) decane compound is contained, the total content of the (D) decane compound is preferably 0.06 mass% or more and 2 mass% or less in terms of moldability and fluidity. It is preferably 0.1% by mass or more and 0.75% by mass or less, more preferably 0.2% by mass or more and 0.7% by mass or less. When it is 0.06 mass% or more, the fluidity tends to be lowered, and when it is 2 mass% or less, molding defects such as voids tend to be suppressed.

於本發明的密封用環氧樹脂組成物可添加(D)矽烷化合物以外之過去公知之偶合劑。例如可舉出異丙基三異硬脂醯基鈦酸酯、異丙基參(二辛基焦磷酸基)鈦酸酯、異丙基三(N-胺基乙基-胺基乙基)鈦酸酯、四辛基雙(二(十三烷基)亞磷酸基)鈦酸酯、四(2,2-二烯丙氧基甲基-1-丁基)雙(二(十三烷基))亞磷酸酯鈦酸酯、雙(二辛基焦磷酸基)氧基乙酸酯鈦酸酯、雙(二辛基焦磷酸基)伸乙基鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基二甲基丙烯醯基異硬脂醯基鈦酸酯、異丙基異硬脂醯基二丙烯醯基鈦酸酯、異丙基三(二辛基磷酸基)鈦酸酯、異丙基三枯烯基苯基鈦酸酯、四異丙基雙(二辛基亞磷酸基)鈦酸酯等鈦酸酯系偶合劑、鋁螯合物類、鋁/鋯系化合物等。這些可單獨使用1種或組合2種以上使用。 In the epoxy resin composition for sealing of the present invention, a conventionally known coupling agent other than the (D) decane compound may be added. For example, isopropyl triisostearate titanate, isopropyl ginate (dioctylpyrophosphate) titanate, isopropyl tris(N-aminoethyl-aminoethyl) Titanate, tetraoctylbis(di(tridecyl)phosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di(tridecane) Base)) phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)extended ethyl titanate, isopropyltrioctylidene titanium Acid ester, isopropyl dimethyl propylene decyl isostearyl decyl titanate, isopropyl isostearyl decyl bis propylene decyl titanate, isopropyl tris(dioctyl phosphate) titanic acid Titrate coupling agent such as ester, isopropyl tricumyl phenyl titanate or tetraisopropyl bis(dioctylphosphite) titanate, aluminum chelate compound, aluminum/zirconium compound Wait. These may be used alone or in combination of two or more.

(D)矽烷化合物以外之偶合劑的總含有率由成形性及黏著性之觀點來看,以密封用環氧樹脂組成物中0.06質量%以上且2質量%以下為佳,以0.1質量%以上且0.75質量%以下為較佳,以0.2質量%以上且0.7質量%以下為更佳。在0.06質量%以上時有可抑制流動 性之降低傾向,在2質量%以下時有可抑制空隙等成形不良產生的傾向。 (D) The total content of the coupling agent other than the decane compound is preferably 0.06 mass% or more and 2 mass% or less, and more preferably 0.1 mass% or more, from the viewpoint of moldability and adhesiveness. Further, it is preferably 0.75 mass% or less, more preferably 0.2 mass% or more and 0.7 mass% or less. When it is 0.06 mass% or more, it can suppress flow When the amount is less than 2% by mass, the molding failure such as voids tends to be suppressed.

〔(E)硬化促進劑〕 [(E) hardening accelerator]

本發明的密封用環氧樹脂組成物可含有(E)硬化促進劑。作為使用於本發明之(E)硬化促進劑,只要為一般使用於密封用環氧樹脂組成物,即可無特別限制地使用。 The epoxy resin composition for sealing of the present invention may contain (E) a curing accelerator. The (E) hardening accelerator to be used in the present invention is not particularly limited as long as it is generally used for the epoxy resin composition for sealing.

例如可舉出1,8-二氮雜雙環〔5.4.0〕十一碳烯-7、1,5-二氮雜雙環〔4.3.0〕壬烯-5、5,6-二丁基胺基-1,8-二氮雜雙環〔5.4.0〕十一碳烯-7等環脒化合物及對於這些化合物加成馬來酸酐、1,4-苯醌、2,5-甲苯醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌等醌化合物、重氮苯基甲烷、酚樹脂等具有π鍵之化合物所成而具有分子內極化之化合物;苯甲基二甲基胺、三乙醇胺、二甲基胺基乙醇、參(二甲基胺基甲基)苯酚等三級胺類及彼等之衍生物;2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七烷基咪唑等咪唑類及彼等之衍生物;三丁基膦、甲基二苯基膦、三苯基膦、參(4-甲基苯基)膦、二苯基膦、苯基膦等第三膦類及對於這些第三膦類加成馬來酸酐、上述醌化合物、重氮苯基甲烷、酚樹脂等具有π鍵的化合物所成而具有分子內極化之磷化合物;四苯基鏻四苯基硼酸、四苯基鏻乙基三苯基硼酸、四丁基鏻四丁基硼 酸等四取代鏻‧四取代硼酸;2-乙基-4-甲基咪唑‧四苯基硼酸、N-甲基嗎啉‧四苯基硼酸等四苯基硼鹽及彼等之衍生物等。可單獨使用彼等之1種或組合2種以上使用。 For example, 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5,5,6-dibutylamine can be mentioned. a cyclic oxime compound such as keto-1,8-diazabicyclo[5.4.0]undecene-7 and addition of maleic anhydride, 1,4-benzoquinone, 2,5-toluene, 1 to these compounds , 4-naphthoquinone, 2,3-dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3 a compound having a molecular weight of ytterbium compound such as dimethoxy-1,4-benzoquinone or phenyl-1,4-benzoquinone, a compound having a π bond such as diazophenylmethane or a phenol resin a tertiary amine such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, and derivatives thereof; 2-methylimidazole, 2- Imidazoles such as phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole, and derivatives thereof; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, and ginseng a third phosphine such as (4-methylphenyl)phosphine, diphenylphosphine or phenylphosphine, or a maleic anhydride, a hydrazine compound, a diazophenylmethane or a phenol resin added to the third phosphine π bond a phosphorus compound having an intramolecular polarization formed by a compound; a tetrasubstituted anthracene tetrasubstituted boronic acid such as tetraphenylphosphonium tetraphenylboronic acid, tetraphenylphosphonium ethyltriphenylboronic acid or tetrabutylphosphonium tetrabutylborate; Tetraphenylboronic acid such as 2-ethyl-4-methylimidazole‧tetraphenylboronic acid, N-methylmorpholine or tetraphenylboronic acid, and derivatives thereof. These may be used alone or in combination of two or more.

作為使用於第三膦類與醌化合物之加成物的第三膦類,並無特別限制。例如可舉出二丁基苯基膦、丁基二苯基膦、乙基二苯基膦、三苯基膦、參(4-甲基苯基)膦、參(4-乙基苯基)膦、參(4-丙基苯基)膦、參(4-丁基苯基)膦、參(異丙基苯基)膦、參(第三丁基苯基)膦、參(2,4-二甲基苯基)膦、參(2,6-二甲基苯基)膦、參(2,4,6-三甲基苯基)膦、參(2,6-二甲基-4-乙氧基苯基)膦、參(4-甲氧基苯基)膦、參(4-乙氧基苯基)膦等具有芳基之第三膦類。由成形性之觀點來看以三苯基膦為佳。 The third phosphine used as an adduct of the third phosphine and the hydrazine compound is not particularly limited. For example, dibutylphenylphosphine, butyl diphenylphosphine, ethyl diphenylphosphine, triphenylphosphine, ginseng (4-methylphenyl) phosphine, and ginseng (4-ethylphenyl) are mentioned. Phosphine, ginseng (4-propylphenyl)phosphine, ginseng (4-butylphenyl)phosphine, cis (isopropylphenyl)phosphine, ginseng (t-butylphenyl)phosphine, ginseng (2,4 -Dimethylphenyl)phosphine, ginseng (2,6-dimethylphenyl)phosphine, ginseng (2,4,6-trimethylphenyl)phosphine, ginseng (2,6-dimethyl-4) a third phosphine having an aryl group such as -ethoxyphenyl)phosphine, stilbene (4-methoxyphenyl)phosphine, ginseng (4-ethoxyphenyl)phosphine or the like. From the viewpoint of formability, triphenylphosphine is preferred.

又,作為使用於第三膦類與醌化合物之加成物的醌化合物,並無特別限制。例如可舉出鄰苯醌、對苯醌、聯苯醌、1,4-萘醌、蒽醌等。由耐濕性或保存安定性的觀點來看以對苯醌為佳。 Further, the ruthenium compound used as an adduct of the third phosphine and the ruthenium compound is not particularly limited. For example, o-benzoquinone, p-benzoquinone, biphenyl fluorene, 1,4-naphthoquinone, anthracene, etc. are mentioned. Phenylhydrazine is preferred from the viewpoint of moisture resistance or preservation stability.

(E)硬化促進劑的含有量只要是可達到硬化促進效果的量即可,並無特別限制。具體為相對於(A)環氧樹脂、(B)硬化劑、(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物之合計量100質量份而言,以0.1質量份以上且10質量份以下為佳,以0.3質量份以上且5質量份以下為更佳。在0.1質量份以上時, 可在短時間使其硬化,在10質量份以下時,可適切地抑制硬化速度而有著得到良好成形品之傾向。 (E) The content of the hardening accelerator is not particularly limited as long as it is an amount capable of achieving a hardening promoting effect. Specifically, it is 0.1 part by mass based on 100 parts by mass of (A) epoxy resin, (B) hardener, and (C) benzophenone derivative having one or more phenolic hydroxyl groups in one molecule. It is preferably 10 parts by mass or more and more preferably 0.3 parts by mass or more and 5 parts by mass or less. When it is 0.1 parts by mass or more, It can be hardened in a short time, and when it is 10 mass parts or less, the hardening speed can be suitably suppressed and the favorable molded product tends to be acquired.

〔(F)無機填充劑〕 [(F) Inorganic Filler]

本發明的密封用環氧樹脂組成物可含有(F)無機填充劑。使用於本發明之(F)無機填充劑是為了減低吸濕性、線膨脹係數、提高熱傳導性及提高強度而被添加於密封用環氧樹脂組成物者,只要是一般使用於密封用環氧樹脂組成物者即可,並無特別限制。例如可舉出熔融二氧化矽、結晶二氧化矽、氧化鋁、鋯石(矽酸鋯)、矽酸鈣、碳酸鈣、鈦酸鉀、碳化矽、氮化矽、氮化鋁、氮化硼、氧化鈹、氧化鋯、鋯石(矽酸鋯)、鎂橄欖石、滑石、尖晶石、模來石(mullite)、二氧化鈦等粉體,或將這些球形化之珠子、玻璃纖維等。這些可單獨使用1種或組合2種以上使用。 The epoxy resin composition for sealing of the present invention may contain (F) an inorganic filler. The inorganic filler (F) used in the present invention is added to the epoxy resin composition for sealing in order to reduce hygroscopicity, linear expansion coefficient, thermal conductivity, and strength, as long as it is generally used for sealing epoxy. The resin composition is not particularly limited. For example, molten cerium oxide, crystalline cerium oxide, aluminum oxide, zircon (zirconium silicate), calcium silicate, calcium carbonate, potassium titanate, tantalum carbide, tantalum nitride, aluminum nitride, boron nitride Powders such as cerium oxide, zirconium oxide, zircon (zirconium silicate), forsterite, talc, spinel, mullite, titanium dioxide, or the like, or spheroidized beads, glass fibers, and the like. These may be used alone or in combination of two or more.

其中由線膨脹係數減低之觀點來看以熔融二氧化矽為佳,由高熱傳導性之觀點來看以氧化鋁為佳,由在成形時之流動性及模具摩耗性的觀點來看,填充劑形狀以球形為佳。特別由成本與性能之平衡的觀點來看,以球狀熔融二氧化矽為佳。 Among them, molten cerium oxide is preferred from the viewpoint of a reduction in linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity, and from the viewpoint of fluidity at the time of molding and mold wearability, a filler The shape is preferably spherical. In particular, from the viewpoint of the balance between cost and performance, it is preferred to melt the cerium oxide in a spherical shape.

無機填充劑之平均粒徑(D50)以0.1μm~50μm為佳,以10μm~30μm為較佳。將前述平均粒徑設定在0.1μm以上時,可抑制密封用環氧樹脂組成物的黏度上昇,若設為50μm以下時,可減低樹脂成分與無機充墳劑之分離。因此,在上述平均粒徑之範圍內 時,可防止硬化物成為不均一、硬化物特性產生偏差、對狹隘之空隙間之填充性降低。 The average particle diameter (D50) of the inorganic filler is preferably from 0.1 μm to 50 μm , more preferably from 10 μm to 30 μm . When the average particle diameter is set to 0.1 μm or more, the viscosity of the epoxy resin composition for sealing can be suppressed from increasing, and when it is 50 μm or less, the separation between the resin component and the inorganic filling agent can be reduced. Therefore, when it is in the range of the above average particle diameter, it is possible to prevent the cured product from being uneven, the deterioration of the properties of the cured product, and the decrease in the filling property between the narrow gaps.

且,體積平均粒徑(D50)係在粒徑分布中,由小粒徑側描繪體積累積分布曲線時,成為累積50體積%之粒徑。可藉由在含有界面活性劑之精製水中分散試料,並使用雷射繞射式粒度分布測定裝置(例如,(股)島津製作所製SALD-3000J)進行測定。 Further, the volume average particle diameter (D50) is a particle size distribution, and when the volume cumulative distribution curve is drawn from the small particle diameter side, the particle diameter is 50% by volume. The measurement can be carried out by dispersing the sample in the purified water containing the surfactant and using a laser diffraction type particle size distribution measuring apparatus (for example, SALD-3000J manufactured by Shimadzu Corporation).

由流動性之觀點來看,無機填充劑之粒子形狀比起角形以球形為佳。又,無機填充劑之比表面積由流動性觀點來看,以0.1m2/g~10m2/g為佳,以0.5m2/g~6.0m2/g為較佳。 From the viewpoint of fluidity, the particle shape of the inorganic filler is preferably spherical in shape from the angle. Further, the ratio of the surface area of the inorganic filler viewpoint of fluidity to 0.1m 2 / g ~ 10m 2 / g is preferable, and 0.5m 2 /g~6.0m 2 / g is preferred.

無機填充劑之含有率由難燃性、成形性、吸濕性、線膨脹係數減低及強度提高的觀點來看,以密封用環氧樹脂組成物中70質量%以上且95質量%以下為佳。在70質量%以上時,有難燃性優良之傾向,在95質量%以下時,有流動性優良的傾向。 The content of the inorganic filler is preferably 70% by mass or more and 95% by mass or less based on the epoxy resin composition for sealing, from the viewpoints of reduction in flame retardancy, moldability, hygroscopicity, coefficient of linear expansion, and strength. . When it is 70% by mass or more, the flame retardancy tends to be excellent, and when it is 95% by mass or less, the fluidity tends to be excellent.

〔其他添加劑〕 [Other additives]

本發明的密封用環氧樹脂組成物除上述(A)環氧樹脂、(B)硬化劑、(C)二苯甲酮衍生物、(D)矽烷化合物、(E)硬化促進劑及(F)無機填充劑以外,亦可視必要含有以下例示之稱作陰離子交換體、脫模劑、難燃劑、著色劑、應力緩和劑的各種添加劑。但本發明之密封用環氧樹脂組成物中,並非限定於以下添加劑,視必要可追加本技術領域中所周知之各種添加劑。 The epoxy resin composition for sealing of the present invention comprises (A) an epoxy resin, (B) a hardener, (C) a benzophenone derivative, (D) a decane compound, (E) a hardening accelerator, and (F). In addition to the inorganic filler, various additives such as an anion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent exemplified below may be contained as necessary. However, the epoxy resin composition for sealing of the present invention is not limited to the following additives, and various additives known in the art may be added as necessary.

(陰離子交換體) (anion exchanger)

本發明的密封用環氧樹脂組成物中,以提高IC之耐濕性、高溫放置特性為目的,視必要可添加陰離子交換體。作為陰離子交換體並無特別限制,可使用過去公知者。例如可舉出水滑石類和選自鎂、鋁、鈦、鋯、鉍之元素的含水氧化物等。可單獨使用彼等之1種或組合2種類以上使用。其中亦以下述組成式(XXI)所示水滑石為佳。 In the epoxy resin composition for sealing of the present invention, an anion exchanger may be added as needed for the purpose of improving the moisture resistance and high-temperature placement characteristics of the IC. The anion exchanger is not particularly limited, and those known in the art can be used. For example, hydrotalcites and hydrous oxides selected from elements of magnesium, aluminum, titanium, zirconium, and hafnium may be mentioned. One type of these may be used alone or two or more types may be used in combination. Among them, hydrotalcite represented by the following composition formula (XXI) is preferred.

【化21】Mg1-xAlx(OH)2(CO3)x/2.mH2O‥‥(XXI) [Chem. 21] Mg 1-x Al x (OH) 2 (CO 3 ) x/2 . mH 2 O....(XXI)

組成式(XXI)中,0<X≦0.5,m表示正數。 In the composition formula (XXI), 0 < X ≦ 0.5, and m represents a positive number.

陰離子交換體之含有率為可捕捉鹵離子等陰離子的充分量即可,並無特別限定。具體為相對於(A)環氧樹脂100質量份而言,以0.1質量份以上且30質量份以下為佳,以1質量份以上且5質量份以下為更佳。 The content of the anion exchanger is not particularly limited as long as it can capture an anion such as a halide ion. Specifically, it is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin.

(脫模劑) (release agent)

於本發明的密封用環氧樹脂組成物中,視必要可含有脫模劑。作為脫模劑,使用相對於(A)環氧樹脂100質量份而言為0.01質量份以上且10質量份以下的氧化型或非氧化型的聚烯烴為佳,使用0.1質量份以上且5質量份以下為較佳。在0.01質量份以上時,有脫模性成為充分之傾向,在10質量份以下時,有黏著性優良之傾向。 In the epoxy resin composition for sealing of the present invention, a release agent may be contained as necessary. The amount of the oxidized or non-oxidized polyolefin is preferably 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the (A) epoxy resin, and 0.1 parts by mass or more and 5 parts by mass are used. The following are preferred. When the amount is 0.01 parts by mass or more, the mold release property tends to be sufficient, and when it is 10 parts by mass or less, the adhesiveness tends to be excellent.

作為氧化型或非氧化型之聚烯烴,可舉出Hoechst股份有限公司製之商品名H4或PE、PED系列等數平均分子量為500~10000左右之低分子量聚乙烯等。又,作為這些以外之脫模劑,例如可舉出棕櫚蠟、褐煤酸酯、褐煤酸、硬脂酸等。可單獨使用彼等之1種或組合2種以上使用。 Examples of the oxidized or non-oxidized polyolefin include a low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as H4, PE, and PED series, manufactured by Hoechst Co., Ltd. Further, examples of the release agent other than these include palm wax, montanic acid ester, montanic acid, and stearic acid. These may be used alone or in combination of two or more.

除氧化型或非氧化型之聚烯烴以外,併用其他脫模劑時,其含有率合計為相對於(A)環氧樹脂100質量份而言以0.1質量份以上且10質量份以下為佳,以0.5質量份以上且3質量份以下為較佳。 In addition to the oxidized or non-oxidized polyolefin, when the other release agent is used in combination, the total content thereof is preferably 0.1 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the (A) epoxy resin. It is preferably 0.5 parts by mass or more and 3 parts by mass or less.

(難燃劑) (flammable agent)

於本發明的密封用環氧樹脂組成物視必要可添加過去公知難燃劑。例如可舉出溴化環氧樹脂、三氧化銻、紅磷、氫氧化鋁、氫氧化鎂、氧化鋅等無機物及/或利用酚樹脂等熱硬化性樹脂等所覆蓋的紅磷、磷酸酯等磷化合物;三聚氰胺、三聚氰胺衍生物、三聚氰胺改性酚樹脂、具有三嗪環之化合物、三聚氰酸衍生物、異三聚氰酸衍生物等含有氮之化合物;環磷腈(cyclophosphazene)等含有磷及氮之化合物;氫氧化鋁、氫氧化鎂及下述組成式(XXII)所示複合金屬氫氧化物等。 In the epoxy resin composition for sealing of the present invention, a conventionally known flame retardant may be added as necessary. For example, an inorganic substance such as a brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide or zinc oxide, and/or a red phosphorus or a phosphate ester coated with a thermosetting resin such as a phenol resin may be used. Phosphorus compound; nitrogen-containing compound such as melamine, melamine derivative, melamine-modified phenol resin, compound having a triazine ring, cyanuric acid derivative, or isocyanuric acid derivative; A compound of phosphorus and nitrogen; aluminum hydroxide, magnesium hydroxide, and a composite metal hydroxide represented by the following composition formula (XXII).

【化22】p(M1 aOb).q(M2 cOd).r(M3 eOf).mH2O‥‥(XXII) [Chem. 22] p (M 1 a O b ). q(M 2 c O d ). r(M 3 e O f ). mH 2 O....(XXII)

組成式(XXII)中,M1、M2及M3表示彼此相異的金屬元素,a、b、c、d、e、f、p、q及m為正數,r為0或正數。 In the composition formula (XXII), M 1 , M 2 and M 3 represent metal elements different from each other, and a, b, c, d, e, f, p, q and m are positive numbers, and r is 0 or a positive number.

上述組成式(XXII)中的M1、M2及M3只要為彼此相異之金屬元素即可,並無特別限制。且,金屬元素的分類係以將典型元素設為A副族、將過渡元素設為B副族之長周期型周期表(出處:共立出版股份有限公司發行「化學大辭典4」1987年2月15日縮刷版第30刷)為準進行。 M 1 , M 2 and M 3 in the above composition formula (XXII) are not particularly limited as long as they are metal elements different from each other. In addition, the classification of metal elements is a long-period periodic table in which a typical element is a sub-group and a transition element is a sub-group B. (Source: Kyoritsu Publishing Co., Ltd. issued "Chemical Dictionary 4" February 1987 The 15th brushed version of the 30th brush) is subject to approval.

由難燃性之觀點來看,M1為選自第3周期的金屬元素、IIA族的鹼土類金屬元素、IVB族、IIB族、VIII族、IB族、IIIA族及IVA族所屬之金屬元素,M2為選自IIIB~IIB族的過渡金屬元素者為佳,M1為選自鎂、鈣、鋁、錫、鈦、鐵、鈷、鎳、銅及鋅,M2為選自鐵、鈷、鎳、銅及鋅為較佳。由流動性之觀點來看M1為鎂,M2為鋅或鎳,r=0者為佳。 From the viewpoint of flame retardancy, M 1 is a metal element selected from the third cycle, an alkaline earth metal element of Group IIA, a metal element belonging to Group IVB, Group IIB, Group VIII, Group IB, Group IIIA, and Group IVA. , M 2 is preferably a transition metal element selected from the group consisting of IIIB to IIB, M 1 is selected from the group consisting of magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M 2 is selected from iron, Cobalt, nickel, copper and zinc are preferred. From the viewpoint of fluidity, M 1 is magnesium, M 2 is zinc or nickel, and r = 0 is preferred.

p、q及r的莫耳比並無特別限制,以r=0且p/q為1/99~1/1時為佳。 The molar ratio of p, q and r is not particularly limited, and is preferably r=0 and p/q is 1/99 to 1/1.

又,可舉出氧化鋅、錫酸鋅、硼酸鋅、氧化鐵、氧化鉬、鉬酸鋅、二環戊二烯鐵等含有金屬元素之化合物等。可單獨使用彼等之1種或組合2種以上使用。 Further, examples thereof include compounds containing a metal element such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. These may be used alone or in combination of two or more.

難燃劑的含有率並無特別限制,相對於(A)環氧樹脂100質量份,以1質量份以上且30質量份以下為佳,以2質量份以上且15質量份以下為較佳。 The content of the flame retardant is not particularly limited, and is preferably 1 part by mass or more and 30 parts by mass or less, and preferably 2 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin.

(著色劑、應力緩和劑) (colorant, stress relieving agent)

又,本發明之密封用環氧樹脂組成物可含有碳黑、有機染料、有機顏料、氧化鈦、鉛丹、三氧化二鐵(red iron oxide)等著色劑。且作為其他添加劑,可視必要添加矽油或矽氧橡膠粉末等應力緩和劑等。 Further, the epoxy resin composition for sealing of the present invention may contain a coloring agent such as carbon black, an organic dye, an organic pigment, titanium oxide, lead dan or red iron oxide. Further, as other additives, a stress relieving agent such as eucalyptus oil or a silicone rubber powder may be added as necessary.

<密封用環氧樹脂組成物之調製> <Preparation of epoxy resin composition for sealing>

本發明的密封用環氧樹脂組成物只要可均勻地分散混合各種成分,則可由任意方法調製。作為一般手法,可舉出將預定添加量之成分藉由混合器等充分混合後,藉由輥混合機、押出機等熔融混煉後,冷卻並粉碎之方法。例如可由將上述成分以預定量均勻攪拌並混合,並預先於70℃~140℃加熱並以捏揉機、輥、擠出機等進行混煉、冷卻後進行粉碎等方法而得。若以合乎成形條件之尺寸及質量進行錠化則較容易使用。 The epoxy resin composition for sealing of the present invention can be prepared by any method as long as it can uniformly disperse and mix various components. As a general method, a method in which a predetermined amount of a component is sufficiently mixed by a mixer or the like, and then melt-kneaded by a roll mixer or an extruder, and then cooled and pulverized is mentioned. For example, the above components may be uniformly stirred and mixed in a predetermined amount, and heated in advance at 70 to 140 ° C, kneaded by a kneading machine, a roll, an extruder, or the like, cooled, and then pulverized. It is easier to use if it is ingots in accordance with the size and quality of the forming conditions.

<電子零件裝置> <Electronic parts device>

作為具備藉由本發明所得之密封用環氧樹脂組成物所密封之元件的電子零件裝置,可舉出於導線架、佈線完成的帶載體、電路板、玻璃、矽晶圓等支持構件上搭載半導體晶片、電晶體、二極體、閘流體等主動元件、電容器、電阻體、線圈等被動元件等元件,將必要部分以本發明的密封用環氧樹脂組成物進行密封的電子零件裝置等。 As an electronic component device including a component sealed by the epoxy resin composition for sealing obtained by the present invention, a semiconductor device can be mounted on a support member such as a lead frame or a tape carrier, a circuit board, a glass, or a germanium wafer. An active component such as a wafer, a transistor, a diode, or a thyristor, a passive component such as a capacitor, a resistor, or a coil, and the like, and an electronic component device in which a sealing epoxy resin composition of the present invention is required to be sealed.

作為如此電子零件裝置,例如可舉出於導線架上固定半導體元件,將銲墊(bond pad)等元件的 端子部與導線部以打線接合或凸塊連接後,使用本發明之密封用環氧樹脂組成物以轉移成形等方式進行密封而成的:DIP(Dual Inline Package,雙列直插封裝)、PLCC(Plastic Leaded Chip Carrier,塑料引線晶片載體)、QFP(Quad Flat Package,四面扁平封裝)、SOP(Small Outline Package,小輪廓封裝)、SOJ(Small Outline J-lead package,J腳形小輪廓封裝)、TSOP(Thin Small Outline Package,薄型小輪廓封裝)、TQFP(Thin Quad Flat Package,薄型四面扁平封裝)等一般的樹脂密封型IC;將以凸塊連接於帶載體之半導體晶片以本發明的密封用環氧樹脂組成物所密封之TCP(Tape Carrier Package,帶載體封裝);將於電路板或玻璃上所形成之電路上,以打線接合、覆晶接合(Flip Chip Bonding)、焊接等方式連接的半導體晶片、電晶體、二極體、閘流體等主動元件及/或電容器、電阻體、線圈等被動元件以本發明的密封用環氧樹脂組成物所密封之COB(Chip On Board,晶片直接封裝)模組、混合式IC或多晶片模組;於背面形成有電路板連接用端子之有機基板的表面上搭載元件,藉由凸塊或打線接合連接元件與形成於有機基板之電路後,以本發明的密封用環氧樹脂組成物將元件密封之BGA(Ball Grid Array,球柵陣列)、CSP(Chip Size Package,晶片尺寸 封裝)等。又,於印刷電路板亦可有效地使用本發明之密封用環氧樹脂組成物。 As such an electronic component device, for example, a semiconductor element can be fixed on a lead frame, and a component such as a bond pad can be used. After the terminal portion and the lead portion are connected by wire bonding or bumping, the sealing epoxy resin composition of the present invention is sealed by transfer molding or the like: DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package) A general resin-sealed IC such as a TSOP (Thin Small Outline Package) or a TQFP (Thin Quad Flat Package); a semiconductor wafer to be bonded to a carrier with a bump to seal the present invention TCP (Tape Carrier Package) sealed with an epoxy resin composition; connected to a circuit formed on a circuit board or glass by wire bonding, Flip Chip Bonding, soldering, etc. Active components such as semiconductor wafers, transistors, diodes, thyristors, and/or passive components such as capacitors, resistors, coils, etc., with the epoxy resin group for sealing of the present invention a COB (Chip On Board) module, a hybrid IC or a multi-chip module sealed by a substance; a component mounted on a surface of an organic substrate on which a terminal for circuit board connection is formed on the back surface, by bumps or wires After bonding the connecting member and the circuit formed on the organic substrate, the BGA (Ball Grid Array) and the CSP (Chip Size Package) are sealed by the sealing epoxy resin composition of the present invention. Package) and so on. Further, the epoxy resin composition for sealing of the present invention can be effectively used in a printed circuit board.

作為使用本發明的密封用環氧樹脂組成物進行密封元件之方法,低壓轉移成形法是最一般的,但亦可使用噴射成形法、壓縮成形法等。 As a method of sealing a member using the epoxy resin composition for sealing of the present invention, a low pressure transfer molding method is most common, but a spray molding method, a compression molding method, or the like may be used.

〔實施例〕 [Examples]

其次藉由實施例說明本發明,但本發明之範圍並未受到彼等實施例之限制。且,「%」若無特別說明時表示「質量%」。 The invention is illustrated by the following examples, but the scope of the invention is not limited by the examples. Further, "%" means "% by mass" unless otherwise specified.

<密封用環氧樹脂組成物之調製> <Preparation of epoxy resin composition for sealing>

將以下成分分別以下述表1~6所示質量份進行添加,在混煉溫度80℃,混煉時間10分鐘的條件下進行輥混煉,製作出實施例1~24及比較例1~24的密封用環氧樹脂組成物。且表中的空欄表示無添加。 The following components were each added in the mass parts shown in the following Tables 1 to 6, and kneaded at a kneading temperature of 80 ° C and a kneading time of 10 minutes to prepare Examples 1 to 24 and Comparative Examples 1 to 24; The seal is made of an epoxy resin composition. And the empty column in the table indicates no addition.

作為(A)環氧樹脂使用: 環氧樹脂1:環氧基當量196g/eq,融點106℃的聯苯型環氧樹脂(日本環氧樹脂股份有限公司製之商品名YX-4000)、 環氧樹脂2:環氧基當量240g/eq,軟化點96℃的含有伸聯苯基骨架之酚‧芳烷基型環氧樹脂(日本化藥股份有限公司製之商品名CER-3000L)、 環氧樹脂3:環氧基當量238g/eq,軟化點55℃的酚‧芳烷基型環氧樹脂(日本化藥股份有限公司製之商品名NC-2000L)、 環氧樹脂4:環氧基當量200g/eq,軟化點60℃的鄰甲酚酚醛清漆型環氧樹脂(大日本墨水化學工業股份有限公司製之商品名N500P-1)。 Used as (A) epoxy resin: Epoxy resin 1: biphenyl type epoxy resin having a melting point equivalent of 196 g/eq and a melting point of 106 ° C (trade name YX-4000, manufactured by Nippon Epoxy Resin Co., Ltd.), Epoxy resin 2: an epoxy group having an epoxy group equivalent of 240 g/eq and a phenolic aralkyl type epoxy resin having a diphenyl structure at a softening point of 96 ° C (trade name CER-3000L, manufactured by Nippon Kayaku Co., Ltd.), Epoxy resin 3: phenol ‧ aralkyl type epoxy resin having an epoxy equivalent of 238 g/eq and a softening point of 55 ° C (trade name NC-2000L, manufactured by Nippon Kayaku Co., Ltd.), Epoxy resin 4: an o-cresol novolac type epoxy resin (trade name: N500P-1, manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy group equivalent of 200 g/eq and a softening point of 60 °C.

作為(B)硬化劑使用:硬化劑1:羥基當量175g/eq,軟化點70℃的酚‧芳烷基樹脂(明和化成股份有限公司製之商品名MEH-7800)、硬化劑2:羥基當量106g/eq,軟化點83℃的苯酚酚醛清漆樹脂(明和化成股份有限公司製之商品名H-100)。 As the (B) curing agent: curing agent 1: phenol ‧ aralkyl resin having a hydroxyl group equivalent of 175 g/eq, a softening point of 70 ° C (trade name: MEH-7800, manufactured by Megumi Kasei Co., Ltd.), and hardener 2: hydroxyl equivalent 106 g/eq, phenol novolac resin (trade name: H-100, manufactured by Mingwa Kasei Co., Ltd.) having a softening point of 83 °C.

作為(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物(以下記為羥基二苯甲酮化合物)使用:羥基二苯甲酮化合物1:對羥基二苯甲酮、羥基二苯甲酮化合物2:鄰羥基二苯甲酮、羥基二苯甲酮化合物3:2-羥基-4-甲氧基二苯甲酮、羥基二苯甲酮化合物4:2,4-二羥基二苯甲酮、羥基二苯甲酮化合物5:4,4’-二羥基二苯甲酮。 (C) a benzophenone derivative having one or more phenolic hydroxyl groups in one molecule (hereinafter referred to as a hydroxybenzophenone compound): hydroxybenzophenone compound 1: p-hydroxybenzophenone Hydroxybenzophenone compound 2: o-hydroxybenzophenone, hydroxybenzophenone compound 3: 2-hydroxy-4-methoxybenzophenone, hydroxybenzophenone compound 4: 2,4- Dihydroxybenzophenone, hydroxybenzophenone compound 5: 4,4'-dihydroxybenzophenone.

又,作為在比較例中取代羥基二苯甲酮類所使用的材料,使用:酚化合物1:苯酚、酚化合物2:對甲酚、酚化合物3:兒茶酚、 酚化合物4:間苯二酚、酚化合物5:氫醌、二苯甲酮化合物1:二苯甲酮、二苯甲酮化合物2:對甲氧基二苯甲酮。 Further, as a material used for substituting the hydroxybenzophenone in the comparative example, phenol compound 1: phenol, phenol compound 2: p-cresol, phenol compound 3: catechol, Phenol compound 4: resorcinol, phenol compound 5: hydroquinone, benzophenone compound 1: benzophenone, benzophenone compound 2: p-methoxybenzophenone.

作為(D)矽烷化合物使用:矽烷化合物1:γ-環氧丙氧基丙基三甲氧基矽烷。 As the (D) decane compound: decane compound 1: γ -glycidoxypropyltrimethoxydecane.

作為(E)硬化促進劑使用:硬化促進劑1:三苯基膦與對苯醌之甜菜鹼型加成物。 As the (E) hardening accelerator: a hardening accelerator 1: a betaine-type adduct of triphenylphosphine and p-benzoquinone.

作為(F)無機填充劑使用:無機填充劑1:平均粒徑17.5μm、比表面積3.8m2/g之球狀熔融二氧化矽。 As the inorganic filler (F): inorganic filler 1: spherical molten cerium oxide having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m 2 /g.

作為其他添加成分,使用褐煤酸酯、碳黑。 As other added components, montanic acid ester and carbon black are used.

<評估> <evaluation>

將實施例及比較例之密封用環氧樹脂組成物藉由以下(1)~(7)之各種特性試驗進行評估。評估結果歸納顯示於下述表7~12。且,密封用環氧樹脂組成物之成形若無明文記載,則是藉由轉移成形機在模具溫度180℃,成形壓力6.9MPa,硬化時間90秒之條件下進行。又,後硬化是在180℃進行5小時。 The epoxy resin compositions for sealing of the examples and the comparative examples were evaluated by various characteristic tests of the following (1) to (7). The results of the evaluation are summarized in Tables 7 to 12 below. Further, the molding of the epoxy resin composition for sealing was carried out by a transfer molding machine under the conditions of a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-hardening was carried out at 180 ° C for 5 hours.

(1)螺旋流(spiral-flow) (1) Spiral flow (spiral-flow)

使用以EMMI-1-66為準之螺旋流(spiral-flow)測定用模具,將密封用環氧樹脂成形材料在上述條件下成形,求得流動距離(cm)。 Using a mold for spiral-flow measurement based on EMMI-1-66, the epoxy resin molding material for sealing was molded under the above conditions to obtain a flow distance (cm).

(2)高溫硬度 (2) high temperature hardness

將密封用環氧樹脂組成物在上述條件下成形於直徑50mm、厚度3mm之圓板上,成形後馬上使用Shore D型硬度計(上島製作所股份有限公司製之HD-1120(型號D))進行測定。 The epoxy resin composition for sealing was molded on a circular plate having a diameter of 50 mm and a thickness of 3 mm under the above-described conditions, and immediately after molding, a Shore D-type hardness tester (HD-1120 (Model D) manufactured by Ushimashima Co., Ltd.) was used. Determination.

(3)吸濕時高溫硬度 (3) High temperature hardness when moisture absorption

於(2)成形前,將密封用環氧樹脂組成物在25℃,50%RH之條件下放置72小時,其後成形後馬上使用Shore D型硬度計(上島製作所股份有限公司製之HD-1120(型號D))進行測定。 (2) Before the molding, the epoxy resin composition for sealing was allowed to stand at 25 ° C, 50% RH for 72 hours, and immediately after molding, a Shore D type hardness tester (HD-made by Ushimashima Co., Ltd.) was used. 1120 (Model D)) was measured.

(4)吸水率 (4) Water absorption rate

將以(2)成形之圓板在上述條件下進行後硬化後,以85℃,60%RH之條件下放置168小時,測定放置前後之質量變化,評估吸水率(質量%)={(放置後圓板質量-放置前圓板質量)/放置前圓板質量}×100。 After the (2) formed circular plate was post-hardened under the above conditions, it was allowed to stand at 85 ° C, 60% RH for 168 hours, and the mass change before and after the standing was measured to evaluate the water absorption rate (% by mass) = {(placement) The quality of the rear disc - the quality of the front disc placed) / the mass of the front disc placed} × 100.

(5)於260℃之彎曲彈性率(高溫彎曲試驗) (5) Flexural modulus at 260 ° C (high temperature bending test)

使用彎曲試驗機(A & D股份有限公司製之tensilon)進行以JIS-K-6911為準之3點彎曲試驗,在恆溫槽一邊保持於260℃,一邊由下述式求得彎曲彈性率(E)。測定係將密封用環氧樹脂組成物在上述條件下,使用成形為10mm、70mm、3mm之試驗片,以壓頭速度1.5mm/min之條件進行。 A three-point bending test based on JIS-K-6911 was carried out using a bending tester (tensilon manufactured by A & D Co., Ltd.), and the bending elastic modulus was obtained by the following formula while maintaining the temperature at 260 ° C. E). In the measurement, the epoxy resin composition for sealing was subjected to the test piece formed into 10 mm, 70 mm, and 3 mm under the above conditions, and the test was carried out under the conditions of a head speed of 1.5 mm/min.

(6)260℃中與金屬之黏著力測定(剪切強度測定) (6) Determination of adhesion to metal at 260 ° C (measurement of shear strength)

將密封用環氧樹脂組成物在上述條件下,於銅板或鍍銀之銅板上各成形為底面的直徑4mm、頂面的直徑3mm、高度4mm之尺寸,再進行後硬化,藉由黏結強度試驗機(Dage Japan股份有限公司製之4000系列),一邊將各種銅板之溫度保持在260℃,一邊測定在剪切速度50μm/s之剪切黏著力。 The sealing epoxy resin composition was formed into a copper plate or a silver plated copper plate under the above conditions to have a diameter of 4 mm on the bottom surface, a diameter of 3 mm on the top surface, and a height of 4 mm, and then post-hardened by a bond strength test. The machine (4000 series manufactured by Dage Japan Co., Ltd.) measured the shear adhesion at a shear rate of 50 μm /s while maintaining the temperature of various copper sheets at 260 °C.

(7)耐回焊性 (7) Reflow resistance

搭載8mm×10mm×0.4mm之矽氧晶片的外形尺寸為20mm×14mm×2mm之80針扁平封裝體(導線架材質:銅合金、晶粒焊墊部頂面及導線前端部鍍銀處理品)使用密封用環氧樹脂組成物在上述條件下成形並進行後硬化。將此在85℃,60%RH之條件下放置1週後,實施例1~16及比較例1~16在240℃進行回焊處理,實施例17~20及比較例17~20在230℃下進行回焊處理,實施例21~24及比較例21~24在220℃進行回焊處理。回焊處理後之密封封裝體中之樹脂/架框界面的剝離有無,是以超音波檢傷裝置(ultrasonic test equipment,日立建機股份有限公司製之HYE-FOCUS)進行觀察,並藉由相對於試驗封裝體數(5個)中產生剝離之封裝體數來評估。 An 80-pin flat package with an outer dimension of 20mm × 14mm × 2mm with a 8mm × 10mm × 0.4mm xenon wafer (lead frame material: copper alloy, top surface of the die pad and silver plated part at the tip end of the wire) The epoxy resin composition for sealing was molded under the above conditions and post-hardened. After leaving this at 85 ° C and 60% RH for one week, Examples 1 to 16 and Comparative Examples 1 to 16 were reflowed at 240 ° C, and Examples 17 to 20 and Comparative Examples 17 to 20 were at 230 ° C. The reflow process was carried out, and Examples 21 to 24 and Comparative Examples 21 to 24 were subjected to reflow treatment at 220 °C. Ultrasonic inspection device (ultrasonic test) for the peeling of the resin/frame interface in the sealed package after reflow processing Equipment, HYE-FOCUS, manufactured by Hitachi Construction Machinery Co., Ltd., was observed and evaluated by the number of packages which were peeled off relative to the number of test packages (5).

將上述(1)~(7)之特性,在相同環氧樹脂及硬化劑之組合下,比較實施例與比較例。例如將環氧樹脂1與2/硬化劑1之組合的實施例1~16與比較例1~16、環氧樹脂1與3/硬化劑1之組合的實施例17~20 與比較例17~20、環氧樹脂1與4/硬化劑2之組合的實施例21~24與比較例21~24作比較。 The characteristics of the above (1) to (7) were compared between the same epoxy resin and a curing agent, and the examples and comparative examples were compared. Examples 17 to 20 of the combination of Examples 1 to 16 and Comparative Examples 1 to 16 and Epoxy Resin 1 and 3/hardener 1 in which epoxy resin 1 and 2/hardener 1 are combined, for example. Examples 21 to 24 in combination with Comparative Examples 17 to 20, Epoxy Resin 1 and 4/hardener 2 were compared with Comparative Examples 21 to 24.

參照表7~12,添加羥基二苯甲酮化合物之實施例與比較例相比較,在260℃之剪切黏著力(銀及銅)較高,在85℃、60%RH之條件下放置1週後之回焊處理中,不會產生樹脂/架框界面之剝離而耐回焊性優良。 Referring to Tables 7 to 12, the examples in which the hydroxybenzophenone compound was added were compared with the comparative examples, and the shear adhesion at 260 ° C (silver and copper) was higher, and placed at 85 ° C and 60% RH. In the reflow treatment after the week, peeling of the resin/frame interface is not caused, and the reflow resistance is excellent.

羥基二苯甲酮化合物的比率為0.1質量%以下之實施例5,比相同環氧樹脂/硬化劑的組合之實施例1~4及6~16黏著力更低,僅顯現小小的發明效果,羥基二苯甲酮化合物的比率為1.0質量%以上的實施例23比相同環氧樹脂/硬化劑的組合之實施例21、22、24之硬度更降低。然而,任一實施例皆未產生樹脂/架框界面之剝離。 Example 5 in which the ratio of the hydroxybenzophenone compound was 0.1% by mass or less, and the adhesion of Examples 1 to 4 and 6 to 16 in combination with the same epoxy resin/hardener was lower, and only a small effect was exhibited. The hardness of Examples 21, 22, and 24 in which the ratio of the hydroxybenzophenone compound was 1.0% by mass or more was lower than that of the combination of the same epoxy resin/hardener. However, none of the examples produced peeling of the resin/frame interface.

另一方面,與本發明相異的組成之比較例未滿足本發明之目的。與實施例比較,比較例在260℃的剪切黏著力(銀及銅)為同等以下,在85℃、60%RH之條件下放置1週後之回焊處理中,大部分封裝體會產生樹脂/架框界面的剝離而耐回焊性較差。 On the other hand, a comparative example of a composition different from the present invention does not satisfy the object of the present invention. Compared with the examples, in the comparative example, the shear adhesion at 260 ° C (silver and copper) was equal to or less, and in the reflow treatment after being placed at 85 ° C and 60% RH for 1 week, most of the package produced resin. The peeling of the frame interface is poor and the reflow resistance is poor.

Claims (5)

一種電子零件裝置,其具備藉由下述密封用環氧樹脂組成物所密封之元件,該密封用環氧樹脂組成物含有(A)於1分子中含有2個以上環氧基之環氧樹脂、(B)硬化劑、(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物及(F)無機填充劑,前述(B)硬化劑是酚樹脂,前述(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物的含有率是0.1質量%以上且1.0質量%以下,前述(B)硬化劑及前述(C)於1分子中具有1個以上的酚性羥基之二苯甲酮衍生物中的總羥基數相對於前述(A)環氧樹脂中之環氧基數之比是0.5以上且2.0以下,前述(F)無機填充劑的含有率是70質量%以上且95質量%以下。 An electronic component device including an element sealed by the following epoxy resin composition for sealing, wherein the epoxy resin composition for sealing contains (A) an epoxy resin containing two or more epoxy groups in one molecule. (B) a curing agent, (C) a benzophenone derivative having one or more phenolic hydroxyl groups in one molecule, and (F) an inorganic filler, wherein the (B) curing agent is a phenol resin, and the above (C) The content of the benzophenone derivative having one or more phenolic hydroxyl groups in one molecule is 0.1% by mass or more and 1.0% by mass or less, and the (B) curing agent and the above (C) have one molecule. The ratio of the total number of hydroxyl groups in the benzophenone derivative of one or more phenolic hydroxyl groups to the number of epoxy groups in the epoxy resin (A) is 0.5 or more and 2.0 or less, and the above (F) inorganic filler The content ratio is 70% by mass or more and 95% by mass or less. 如申請專利範圍第1項之電子零件裝置,其中前述密封用環氧樹脂組成物更含有(D)矽烷化合物。 The electronic component device of claim 1, wherein the epoxy resin composition for sealing further contains (D) a decane compound. 如申請專利範圍第1項或第2項之電子零件裝置,其中前述密封用環氧樹脂組成物更含有(E) 硬化促進劑。 An electronic component device according to claim 1 or 2, wherein the epoxy resin composition for sealing further contains (E) Hardening accelerator. 如申請專利範圍第1項之電子零件裝置,其中,前述元件搭載於支持構件上。 The electronic component device of claim 1, wherein the component is mounted on a support member. 如申請專利範圍第1項之電子零件裝置,其中,前述元件是主動元件或被動元件。 The electronic component device of claim 1, wherein the aforementioned component is an active component or a passive component.
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