TW201233725A - Epoxy resin composition and semiconductor-sealing material using the same - Google Patents
Epoxy resin composition and semiconductor-sealing material using the same Download PDFInfo
- Publication number
- TW201233725A TW201233725A TW100127977A TW100127977A TW201233725A TW 201233725 A TW201233725 A TW 201233725A TW 100127977 A TW100127977 A TW 100127977A TW 100127977 A TW100127977 A TW 100127977A TW 201233725 A TW201233725 A TW 201233725A
- Authority
- TW
- Taiwan
- Prior art keywords
- epoxy resin
- resin composition
- mass
- component
- total mass
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
Description
201233725 六、發明說明： 【發明所屬之技術領域】 本發明係關於適用於半導體封裝材料之環氧樹脂組成 物以及使用其之半導體封裝材料。本發明之半導體封裝材 料可使用於一次安裝用半導體封裝材料、二次安裝用之半 導體封裝材料之任一者中。 【先前技術】 環氧樹脂由於具有優異之電絕緣性、機械強度、耐熱 性、耐濕性、密著性等之材料特性，故已使用作爲如半導 體封裝材料之電性、電子零件之電絕緣用材料。 於該用途中使用之環氧樹脂組成物由於優異耐電壓性 、電絕緣性爲必要’因此通常使用無溶劑型之組成物，進 而使用作爲半導體封裝材料時，爲提高對封裝部位之塡充 性而要求爲低黏度。 以往’爲了降低環氧樹脂組成物之黏度，提出有丁基 縮水甘油醚 '苯基縮水甘油醚等之單縮水甘油醚、i，6-己 二醇二縮水甘油醚、新癸酸縮水甘油酯等之各種環氧樹脂 稀釋劑’調配有該環氧樹脂稀釋劑之環氧樹脂組成物之黏 度（25°C)爲 3 5 0 〜400cps 左右。 然而’上述環氧樹脂稀釋劑雖然對於減低環氧樹脂組 成物黏度顯示出一定效果，但該環氧樹脂組成物之硬化物 有耐熱性顯著降低、耐濕性、機械強度、電特性不充分等 之問題。又’由於環氧樹脂組成物之玻璃轉移溫度（Tg)低 201233725 如80〜105 °C左右，故有封裝時之焊球補強性差，於熱循 環試驗中有發生龜裂等之問題。 又’調配環氧樹脂稀釋劑時，亦有儲存安定性或硬化 性降低等問題。 爲解決上述問題，於專利文獻1中，藉由使用特定量 (具體而言’對於環氧樹之1〇〇質量份爲50〜150質量份） 之特定環氧系化合物（具體爲1，4-環己烷二甲醇二縮水甘 油醚）作爲環氧樹脂稀釋劑，而可提供低黏度、不使硬化 性降低、具備優異耐熱性、耐電壓性、電絕緣性、耐濕性 、機械強度、接著性之環氧樹脂組成物。 然而，專利文獻1中記載之環氧樹脂組成物，由於使 用酸酐系硬化劑作爲硬化劑，故無法達成在半導體封裝材 料尤其是二次安裝用半導體封中材料中所要求之在低溫短 時間內硬化。半導體封裝材料，尤其是二次安裝用半導體 封裝材料中，由於係使用於在搭載了電容晶片構件等之其 他安裝構件等之基板上之安裝，爲了防止基板上之構造物 之熱損傷，而要求在低溫短時間硬化，具體而言，要求在 1 5 0 °C以下於數分鐘內硬化，但使用酸酐系硬化劑作爲硬 化劑時，無法達成此要求。 且，由於使用酸酐系硬化劑作爲硬化劑，故有半導體 封裝材料之可使用壽命（可用時間）短的問題。 於專利文獻2中雖揭示含有1,4-己烷二甲醇二縮水甘 油醚作爲必須成分之環氧樹脂組成物，但該環氧樹脂組成 物由於以1，4-己烷二甲醇二縮水甘油醚及氫化雙酚A二縮201233725 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to an epoxy resin composition suitable for a semiconductor package material and a semiconductor package material using the same. The semiconductor package material of the present invention can be used in any of a semiconductor package material for primary mounting and a semiconductor package material for secondary mounting. [Prior Art] Epoxy resin has been used as electrical insulation of electrical and electronic parts such as semiconductor packaging materials because of its excellent electrical insulating properties, mechanical strength, heat resistance, moisture resistance, and adhesion properties. Use materials. The epoxy resin composition used in this application is required for excellent voltage resistance and electrical insulation. Therefore, a solvent-free composition is generally used, and when used as a semiconductor packaging material, the adhesion to the package portion is improved. The requirement is low viscosity. In the past, in order to reduce the viscosity of the epoxy resin composition, monoglycidyl ether such as butyl glycidyl ether 'phenyl glycidyl ether, i,6-hexanediol diglycidyl ether, and glycidyl neodecanoate were proposed. Etc. Various epoxy resin thinners The viscosity (25 ° C) of the epoxy resin composition formulated with the epoxy resin diluent is about 305 to 400 cps. However, the above epoxy resin thinner exhibits a certain effect on reducing the viscosity of the epoxy resin composition, but the cured product of the epoxy resin composition has remarkably reduced heat resistance, moisture resistance, mechanical strength, insufficient electrical properties, and the like. The problem. Further, since the glass transition temperature (Tg) of the epoxy resin composition is as low as 201233725, such as about 80 to 105 °C, the solder ball has poor adhesion during packaging, and cracks occur in the heat cycle test. In addition, when the epoxy resin thinner is formulated, there are problems such as storage stability or reduction in hardenability. In order to solve the above problem, in Patent Document 1, a specific epoxy compound (specifically 1, 4) is used by using a specific amount (specifically, '50 to 150 parts by mass for 1 part by mass of the epoxy tree). -cyclohexanedimethanol diglycidyl ether) as an epoxy resin thinner, provides low viscosity, does not reduce hardenability, and has excellent heat resistance, voltage resistance, electrical insulation, moisture resistance, mechanical strength, A subsequent epoxy resin composition. However, since the epoxy resin composition described in Patent Document 1 uses an acid anhydride-based curing agent as a curing agent, it is not possible to achieve a low temperature and a short time required for a semiconductor encapsulating material, particularly a material for secondary mounting semiconductor encapsulation. hardening. The semiconductor package material, particularly the semiconductor package material for secondary mounting, is used for mounting on a substrate on which another mounting member such as a capacitor wafer member is mounted, and is required to prevent thermal damage of the structure on the substrate. It is required to harden at a low temperature for a short period of time. Specifically, it is required to be hardened in a few minutes at 150 ° C or lower, but this cannot be achieved when an acid anhydride-based curing agent is used as a curing agent. Further, since an acid anhydride-based curing agent is used as the curing agent, there is a problem that the semiconductor package material has a short service life (available time). Patent Document 2 discloses an epoxy resin composition containing 1,4-hexanedimethanol diglycidyl ether as an essential component, but the epoxy resin composition is 1,4-hexane dimethanol diglycidyl Ether and hydrogenated bisphenol A condensate
S -6- 201233725 水甘油醚之混合物爲環氧樹脂成分，故黏度高，於使用作 爲半導體封裝時，對封裝部位之塡充性差。 [先前技術文獻] [專利文獻] [專利文獻1]特開平8- 1 274 1號公報 [專利文獻2]特開平6-1 36092號公報 【發明內容】 [發明欲解決之問題] 本發明係爲解決上述以往技術之問題點，其目的係提 供低黏度、可於低溫短時間硬化、具有優異耐熱性、耐電 壓性、電絕緣性、耐濕性、機械強度、密著性且封裝時之 焊球補強性優異而且可使用壽命長之環氧樹脂組成物，以 及使用其之半導體封裝材料。 [用以解決問題之手段] 爲達成上述目的，本發明提供一種環氧樹脂組成物’ 其係由（A)環氧樹脂、（B)l，4-環己烷二甲醇二縮水甘油醚 、（C)咪唑系潛在性硬化劑、及（D)酚樹脂所組成’其特徵 爲 前述（B)l，4-環己烷二甲醇二縮水甘油醚之含量相對於 前述（A)環氧樹脂及前述（B)l，4-環己烷二甲醇二縮水甘油 醚之合計質量爲0.5〜80質量％ ’前述（C)咪哩系潛在性硬 化劑之含量相對於環氧樹脂組成物全部成分之合計質量爲 201233725 5〜25質量％，前述（D)酚樹脂之含量相對於環氧樹脂組成 物全部成分之合計質量爲0.5〜25質量％。 本發明之環氧樹脂組成物較好含有液狀環氧樹脂作爲 前述（A)環氧樹脂。 本發明之環氧樹脂組成物亦可進而含有（E)硼酸酯化 合物。 本發明之環氧樹脂組成物亦可進而含有（F)二氧化矽 塡充劑。 本發明之環氧樹脂組成物亦可進而含有（G)矽烷偶合 劑。 又，本發明提供使用本發明之環氧樹脂組成物之半導 體封裝材料。 [發明效果] 本發明之環氧樹脂組成物於常溫（2 5 °C )之黏度爲低如 6000mPa . s以下，爲作業性良好。 本發明之環氧樹脂組成物於低溫短時間硬化性優異， 於1 50°C以下之溫度加熱數分鐘即可硬化。 又，本發明之環氧樹脂組成物於常溫（25 °C )之儲存安 定性良好，可使用時間長。 又，本發明之環氧樹脂組成物於封裝時之焊球補強性 優異’可抑制熱循環試驗中之龜裂發生。 利用該等特性，本發明之環氧樹脂組成物可較好地使 用於一次安裝用或二次安裝用之半導體封裝材料之半導體S -6- 201233725 The mixture of glyceryl ether is an epoxy resin component, so it has a high viscosity. When used as a semiconductor package, it has poor adhesion to the package. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. In order to solve the above problems of the prior art, the object is to provide low viscosity, low temperature hardening at a low temperature, excellent heat resistance, voltage resistance, electrical insulation, moisture resistance, mechanical strength, adhesion, and packaging. An epoxy resin composition which is excellent in solder ball reinforcement and has a long service life, and a semiconductor encapsulating material using the same. [Means for Solving the Problems] In order to achieve the above object, the present invention provides an epoxy resin composition which is obtained from (A) an epoxy resin, (B) 1, 4-cyclohexane dimethanol diglycidyl ether, (C) an imidazole-based latent curing agent, and (D) a phenol resin composed of the above-mentioned (B) 1,4-cyclohexanedimethanol diglycidyl ether content relative to the aforementioned (A) epoxy resin And the total mass of the above (B) l,4-cyclohexanedimethanol diglycidyl ether is 0.5 to 80% by mass. The content of the (C) miloxime latent hardener is relative to the total composition of the epoxy resin composition. The total mass is 201233725 5 to 25% by mass, and the total mass of the (D) phenol resin is 0.5 to 25% by mass based on the total mass of all the components of the epoxy resin composition. The epoxy resin composition of the present invention preferably contains a liquid epoxy resin as the above (A) epoxy resin. The epoxy resin composition of the present invention may further contain (E) a borate ester compound. The epoxy resin composition of the present invention may further contain (F) cerium oxide lanthanum. The epoxy resin composition of the present invention may further contain (G) a decane coupling agent. Further, the present invention provides a semiconductor encapsulating material using the epoxy resin composition of the present invention. [Effect of the Invention] The epoxy resin composition of the present invention has a low viscosity at room temperature (25 ° C) of, for example, 6000 mPa·s or less, and is excellent in workability. The epoxy resin composition of the present invention is excellent in low-temperature short-term hardenability, and can be cured by heating at a temperature of 150 ° C or lower for several minutes. Further, the epoxy resin composition of the present invention has good storage stability at room temperature (25 ° C) and can be used for a long period of time. Further, the epoxy resin composition of the present invention is excellent in solder ball reinforcement at the time of encapsulation, and the occurrence of cracks in the heat cycle test can be suppressed. With these characteristics, the epoxy resin composition of the present invention can be preferably used for a semiconductor of a semiconductor package material for primary mounting or secondary mounting.
-8- S 201233725 封裝材料。 【實施方式】 以下，針對本發明詳細加以說明。 本發明之環氧樹脂組成物含有以下所示（A)〜（D)成分 作爲必須成分》 (A)成分：環氧樹脂 (A)成分之環氧樹脂係作爲本發明環氧樹脂組成物之 主劑的成分。 (A)成分的環氧樹脂較好在常溫爲液狀，但即使在常 溫爲固體者，亦可利用其他液狀環氧樹脂或稀釋劑稀釋成 顯示液狀而使用。 具體例示有雙酚A型環氧樹脂、溴化雙酚A型環氧 樹脂、雙酚F型環氧樹脂、聯苯型環氧樹脂、酚醛清漆型 環氧樹脂、脂環式環氧樹脂、萘型環氧樹脂、醚系或聚醚 系環氧樹脂、含有環氧乙烷環之具丁二烯、矽氧環氧共聚 物樹脂等。 尤其，作爲液狀之環氧樹脂，例示有雙酸A型環氧樹 脂之平均分子量約400以下者；如對-縮水甘油氧基苯基 二甲基參雙酚A二縮水甘油醚之分支狀多官能基雙酚a 型環氧樹脂；雙酚F型環氧樹脂；酚酚醛清漆型環氧樹脂 之平均分子量約570以下者；如乙烯基（3,4_環己烯）二氧 化物、3,4-環氧基環己基羧酸（3,4 -環氧基環己基）甲酯、己 -9- 201233725 二酸雙（3,4-環氧基-6-甲基環己基甲基）酯、2-(3,4-環 環己基）5，1-螺（3,4-環氧基環己基）-間-二噁烷之脂環 氧樹脂；如3,3’，5,5’-四甲基_4,4’-二縮水甘油氧基聯 聯苯型環氧樹脂；如六氫苯二甲酸二縮水甘油酯、3-六氫苯二甲酸二縮水甘油酯、六氫對苯二甲酸二縮水 酯之縮水甘油酯型環氧樹脂；如二縮水甘油基苯胺、 水甘油基甲苯胺、三縮水甘油基-對-胺基苯酚、四縮 油基-間-二甲苯二胺 '四縮水甘油基雙（胺基甲基）環 之縮水甘油基胺型環氧樹脂；以及1，3-二縮水甘油基. 基-5-乙基乙內醯脲之乙內醯脲型環氧樹脂；含有環烷 環氧樹脂。又亦可使用1，3-雙（3-縮水甘油氧基丙 1，1，3,3-四甲基二矽氧烷之具有矽骨架之環氧樹脂。 ，亦例示有如（聚）乙二醇二縮水甘油醚、（聚）丙二醇 水甘油醚、丁二醇二縮水甘油醚、新戊二醇二縮水甘 之二環氧化合物；如三羥甲基丙烷三縮水甘油醚、甘 縮水甘油醚之三環氧化合物等。 亦可倂用於常溫非爲固體之超高黏性環氧樹脂， 此種環氧樹脂，例示有高分子量之雙酚A型環氧樹脂 醛清漆環氧樹脂、四溴雙酚A型環氧樹脂等。該等可 在常溫爲液體之環氧樹脂及/或稀釋劑並調節流動性 用。 使用於常溫非爲固體之超高黏性環氧樹脂時，較 合低黏度之環氧樹脂例如（聚）乙二醇二縮水甘油醚、 丙二醇二縮水甘油醚、丁二醇二縮水甘油醚、新戊二 氧基 式環 苯之 甲基 甘油 二縮 水甘 己烷 -5-甲 環之 基）- 再者 二縮 油醚 油三 至於 、酚 組合 而使 好組 (聚） 醇二-8- S 201233725 Packaging material. [Embodiment] Hereinafter, the present invention will be described in detail. The epoxy resin composition of the present invention contains the following (A) to (D) components as essential components. (A) component: epoxy resin of the epoxy resin (A) component is used as the epoxy resin composition of the present invention. The ingredients of the main agent. The epoxy resin of the component (A) is preferably liquid at normal temperature. However, even if it is solid at normal temperature, it may be diluted with a liquid epoxy resin or a diluent to form a liquid. Specific examples include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, A naphthalene type epoxy resin, an ether type or a polyether type epoxy resin, a butadiene or a hafnoxy epoxy copolymer resin containing an oxirane ring. In particular, as the liquid epoxy resin, an average molecular weight of a diacid A-type epoxy resin of about 400 or less is exemplified; for example, a branch of p-glycidoxyphenyl dimethyl bisphenol A diglycidyl ether Polyfunctional bisphenol a type epoxy resin; bisphenol F type epoxy resin; phenol novolac type epoxy resin having an average molecular weight of about 570 or less; such as vinyl (3,4_cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl)methyl ester, hex-9- 201233725 diacid bis(3,4-epoxy-6-methylcyclohexylmethyl Ester epoxy resin of 2-(3,4-cyclohexyl)5,1-spiro(3,4-epoxycyclohexyl)-m-dioxane; such as 3, 3', 5, 5'-tetramethyl-4,4'-diglycidoxy-linked biphenyl type epoxy resin; such as diglycidyl hexahydrocarbonate, hexahydrophthalic acid diglycidyl ester, hexahydrogen a glycidyl ester type epoxy resin of dihydroterephthalate; such as diglycidylaniline, hydroglycidylamine, triglycidyl-p-aminophenol, tetra-condensate-m-xylene Amine 'tetraglycidyl double (amino group Yl) rings glycidyl amine type epoxy resins; and a 1,3-glycidyl type epoxy acyl acyl urea of the hydantoin ethyl 5-ethyl glycidyl group;. A cycloalkyl-containing epoxy resin. It is also possible to use an epoxy resin having a fluorene skeleton of 1,3-bis(3-glycidoxypropane 1,1,3,3-tetramethyldioxane), and is also exemplified as (poly)ethylene Alcohol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl epoxide; such as trimethylolpropane triglycidyl ether, glycidyl ether The third epoxy compound, etc. It can also be used for ultra-high viscosity epoxy resin which is not solid at room temperature. This epoxy resin is exemplified by high molecular weight bisphenol A epoxy aldehyde varnish epoxy resin, four Bromobisphenol A type epoxy resin, etc. These can be used as liquid epoxy resin and/or diluent at room temperature to adjust fluidity. When used in ultra-high viscosity epoxy resin which is not solid at room temperature, it is more suitable. Low-viscosity epoxy resins such as (poly)ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentadienyl cyclic benzene methyl glycerol diglycidyl- 5-Acyclic group) - In addition, the bis-oleyl ether oil is three, and the phenol combination is good. (Poly) glycol di
S -10- 201233725 縮水甘油醚之二環氧化合物；如三羥甲基丙烷三縮水甘油 醚、甘油三縮水甘油醚之三環氧化合物等。 使用稀釋劑時，可使用非反應性稀釋劑及反應性稀釋 劑任一者，但較好爲反應性稀釋劑。本說明書中，反應性 稀釋劑意指具有1個環氧基、於常溫具有較低黏度之化合 物，因應目的，除環氧基以外，亦可具有其他聚合性官能 基例如乙烯基、烯丙基等烯基；或亦可具有丙烯醯基、甲 基丙烯醯基等不飽和羧酸殘基。該種反應性稀釋劑例示有 如正丁基縮水甘油醚、2-乙基己基縮水甘油醚、苯基縮水 甘油醚、甲苯基縮水甘油醚、對-第二丁基苯基縮水甘油 醚、氧化苯乙烯、α-氧化蒎烯之單環氧化合物；如烯丙 基縮水甘油醚、甲基丙烯酸縮水甘油酯、1-乙烯基-3,4-環 氧基環己烷之具有其他官能基之單環氧化合物等。 作爲（Α)成分之環氧樹脂，可單獨使用亦可倂用2種 以上。環氧樹脂本身較好於常溫爲液狀。其中較好爲液狀 雙酚型環氧樹脂、液狀胺基苯酚型環氧樹脂、矽氧改質環 氧樹脂、萘型環氧樹脂。進而更好爲液狀雙酚Α型環氧樹 脂、液狀雙酚F型環氧樹脂、對-胺基苯酚型液狀環氧樹 脂、1，3 -雙（3 -縮水甘油氧基丙基）四甲基二矽氧烷。 (B)成分：1,4-環己烷二甲醇二縮水甘油醚 作爲（B)成分之1，4-環己烷二甲醇二縮水甘油醚（以下 簡稱爲「DME」）爲1,4-環己烷二甲醇與表氯醇在50〜150 °C左右加熱下脫鹽酸而調製之環氧系化合物，係作爲環氧 -11 - 201233725 樹脂稀釋劑而添加。 又，不使用表氯醇，而使用烯烴化合物作爲原料，利 用過氧化氫實施環氧化之程序亦可製造DME。以該種程序 製造之DME之氯濃度低如l〇〇ppm以下，而可較好地使用 作爲環氧樹脂稀釋劑。 DME與丁基縮水甘油醚、苯基縮水甘油醚等之單縮水 甘油醚、1，6 -己二醇二縮水甘油醚、新癸酸縮水甘油酯之 以往的環氧樹脂稀釋劑不同，由於反應性高，且由於可抑 制因添加所致之反應性降低，故不損及耐熱性、耐濕性、 機械強度、電特性之硬化物特性，而可降低環氧樹脂組成 物之黏度。 本發明之環氧樹脂組成物中，作爲（B)成分之DME含 量，相對於（A)成分之環氧樹脂與作爲（B)成分之DME之 合計質量，爲0.5〜80質量％。若未達0.5質量％，則因環 氧樹脂稀釋劑之添加所致之效果變不足，無法使環氧樹脂 組成物之常溫（25°C )黏度成爲6000mPa · s以下。 另一方面，若超過80質量％，則引起玻璃轉移溫度 (Tg)或密著性降低等之對硬化物特性產生不良影響。 作爲（B)成分之DME含量，相對於（A)成分之環氧樹 脂與作爲（B)成分之DME之合計質量，較好爲1〜70質量 %，更好爲5〜6 2.5質量％。 (C)成分：咪唑系潛在性硬化劑 (C)成分之咪唑系潛在性硬化劑爲環氧樹脂之硬化劑S -10- 201233725 Diepoxide compound of glycidyl ether; such as trimethylolpropane triglycidyl ether, triglyceride of glycerol triglycidyl ether, and the like. When a diluent is used, either a non-reactive diluent or a reactive diluent can be used, but a reactive diluent is preferred. In the present specification, the reactive diluent means a compound having one epoxy group and having a lower viscosity at normal temperature, and may have other polymerizable functional groups such as a vinyl group, an allyl group in addition to the epoxy group for the purpose. An alkenyl group; or an unsaturated carboxylic acid residue such as an acryloyl group or a methacryl group. Such reactive diluents are exemplified by n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-t-butylphenyl glycidyl ether, benzoic acid. a monoepoxy compound of ethylene or α-oxylated decene; such as allyl glycidyl ether, glycidyl methacrylate, 1-vinyl-3,4-epoxycyclohexane having other functional groups Epoxy compounds, etc. The epoxy resin as the (Α) component may be used alone or in combination of two or more. The epoxy resin itself is preferably liquid at normal temperature. Among them, a liquid bisphenol type epoxy resin, a liquid aminophenol type epoxy resin, a rhodium oxide modified epoxy resin, and a naphthalene type epoxy resin are preferable. Further, it is preferably a liquid bisphenol quinone type epoxy resin, a liquid bisphenol F type epoxy resin, a p-aminophenol type liquid epoxy resin, and a 1,3-bis(3-glycidoxypropyl group). ) Tetramethyldioxane. (B) component: 1,4-cyclohexanedimethanol diglycidyl ether as the component (B), 1,4-cyclohexanedimethanol diglycidyl ether (hereinafter abbreviated as "DME") is 1,4- An epoxy compound prepared by removing hydrochloric acid by heating cyclohexanedimethanol and epichlorohydrin at a temperature of from 50 to 150 ° C is added as an epoxy-11 - 201233725 resin diluent. Further, DME can be produced by using an olefin compound as a raw material without using epichlorohydrin, and a procedure of performing epoxidation using hydrogen peroxide. The DME produced by this procedure has a chlorine concentration as low as l〇〇ppm or less, and can be preferably used as an epoxy resin diluent. DME is different from the conventional epoxy resin diluents such as monoglycidyl ether such as butyl glycidyl ether and phenyl glycidyl ether, 1,6-hexanediol diglycidyl ether and glycidyl neodecanoate. Since the reactivity is high and the reactivity due to the addition is suppressed, the viscosity of the epoxy resin composition can be lowered without impairing the properties of the cured product of heat resistance, moisture resistance, mechanical strength, and electrical properties. In the epoxy resin composition of the present invention, the DME content of the component (B) is from 0.5 to 80% by mass based on the total mass of the epoxy resin of the component (A) and the DME as the component (B). When the amount is less than 0.5% by mass, the effect of the addition of the epoxy resin diluent is insufficient, and the ordinary temperature (25 ° C) viscosity of the epoxy resin composition cannot be made 6000 mPa · s or less. On the other hand, when it exceeds 80% by mass, the glass transition temperature (Tg) or the adhesion is lowered, which adversely affects the properties of the cured product. The DME content of the component (B) is preferably from 1 to 70% by mass, more preferably from 5 to 65% by mass, based on the total mass of the epoxy resin of the component (A) and the DME as the component (B). (C) Component: Imidazole-based latent curing agent (I) The imidazole-based latent curing agent is an epoxy resin hardener.
-12- S 201233725 。使用咪唑系潛在性硬化劑作爲環氧樹脂之硬化劑之理由 ，爲可使低溫短時.間硬化性優異，可在1 50°c以下之溫度 加熱數分鐘即可硬化。 且藉由使用咪唑系潛在性硬化劑，可使環氧樹脂組成 物於常溫（2 5 °C )之儲存安定性變良好，可增長可使用壽命 〇 至於咪唑系潛在性硬化劑，可使用公知之咪唑系潛在 性硬化劑。至於具體例，有P N 2 3、P N 4 0、P N - Η (商品名， 均爲味之素FineTech公司製）。且，舉例有亦稱爲微膠囊 化咪唑之於胺化合物之環氧加成物之羥基上經加成反應者 ，例如可以 NOVACURE HX-3 08 8、NOVACURE HX-3941 、HX-3 742、HX-3 722(商品名，均爲旭化成FineTech公司 製）等獲得。 又，上述咪唑系潛在性硬化劑中，可使用任一種，亦 可倂用2種以上。 本發明之環氧樹脂組成物中，作爲（C)成分之咪唑系 潛在性硬化劑之含量，相對於環氧樹脂組成物之全部成分 合計質量，爲5〜25質量％。 若未達5質量％，則低溫短時間硬化性變差，無法在 150°C以下以數分鐘之加熱而硬化。另一方面，若超過25 質量％，則環氧樹脂組成物之常溫（25 °C )之儲存安定性降 低，可使用壽命縮短。 作爲（C)成分之咪唑系潛在性硬化劑之含量，相對於 環氧樹脂組成物之全部成分合計質量，較好爲5.6〜24.3 -13- 201233725 質量％。 (D)成分：酚樹脂 作爲（D)成分之酚樹脂係爲達成環氧樹脂組成物之均 一硬化而添加者。本發明之環氧樹脂組成物藉由使用咪唑 系潛在性硬化劑作爲環氧樹脂之硬化劑，而使低溫短時間 硬化性優異，在1 50 °C以下加熱數分鐘即可硬化，但於低 溫短時間硬化時，易使硬化變不均一，使硬化物外觀惡化 ，而產生損及硬化物密著性等之問題。 作爲酚樹脂，可自使用作爲環氧樹脂之硬化劑使用者 廣範圍選擇。具體而言，舉例有烯丙基丙烯酸酚樹脂（例 如MEH8005 (商品名，明和化成工業公司製））等。 本發明之環氧樹脂組成物中，作爲（D)成分之酚樹脂 含量，相對於環氧樹脂組成物全部成分之合計質量，爲 0.5〜25質量％。 若未達1質量％，則於低溫短時間硬化時，硬化便不 均一，而使硬化物外觀惡化，產生損及硬化物密著性等問 題。 另一方面，若超過20質量％，則環氧樹脂組成物之常 溫（25 °C )之儲存安定性降低，而縮短可使用壽命。 作爲（D)成分之酚樹脂含量，相對於環氧樹脂組成物 全部成分之合計質量，較好爲1〜20.1質量％。 本發明之環氧樹脂組成物，除上述（A)〜（D)成分以外 ’亦可依據需要含有以下將述及之成分。-12- S 201233725. The reason why an imidazole-based latent curing agent is used as a curing agent for an epoxy resin is that it can be excellent in low-temperature short-time hardening property, and can be cured by heating at a temperature of 150 ° C or lower for several minutes. Moreover, by using an imidazole-based latent curing agent, the storage stability of the epoxy resin composition at normal temperature (25 ° C) can be improved, and the service life can be increased to the imidazole-based latent curing agent. Imidazole is a latent hardener. Specific examples include P N 2 3, P N 4 0, and P N - Η (trade names, all manufactured by Ajinomoto FineTech Co., Ltd.). Further, an addition reaction of a hydroxyl group of an epoxy compound of an amine compound, which is also referred to as microencapsulated imidazole, for example, NOVACURE HX-3 08 8 , NOVACURE HX-3941, HX-3 742, HX is exemplified. -3 722 (trade name, all manufactured by Asahi Kasei FineTech Co., Ltd.). Further, any of the above-mentioned imidazole-based latent curing agents may be used alone or in combination of two or more. In the epoxy resin composition of the present invention, the content of the imidazole-based latent curing agent as the component (C) is 5 to 25% by mass based on the total mass of all the components of the epoxy resin composition. If it is less than 5% by mass, the low-temperature short-time hardenability is deteriorated, and it cannot be cured by heating at 150 ° C or lower for several minutes. On the other hand, when it exceeds 25% by mass, the storage stability at room temperature (25 °C) of the epoxy resin composition is lowered, and the service life can be shortened. The content of the imidazole-based latent curing agent as the component (C) is preferably 5.6 to 24.3 - 13 to 201233725 mass% based on the total mass of all the components of the epoxy resin composition. (D) component: phenol resin The phenol resin as the component (D) is added to achieve uniform hardening of the epoxy resin composition. The epoxy resin composition of the present invention is excellent in low-temperature short-time hardenability by using an imidazole-based latent curing agent as a curing agent for an epoxy resin, and can be hardened by heating at 150 ° C for several minutes, but at a low temperature. When it hardens in a short time, it is easy to make the hardening uneven, and the appearance of a hardened material deteriorates, and there exists a problem which damages the hardening property adhesives, etc.. As a phenol resin, it can be widely used as a curing agent for epoxy resins. Specifically, an allyl acrylate phenol resin (e.g., MEH8005 (trade name, manufactured by Megumi Chemical Co., Ltd.)) or the like is exemplified. In the epoxy resin composition of the present invention, the content of the phenol resin as the component (D) is from 0.5 to 25% by mass based on the total mass of all the components of the epoxy resin composition. When the amount is less than 1% by mass, the curing is not uniform at a low temperature for a short period of time, and the appearance of the cured product is deteriorated, which may cause damage to the cured product. On the other hand, when it exceeds 20% by mass, the storage stability at room temperature (25 °C) of the epoxy resin composition is lowered, and the service life is shortened. The phenol resin content of the component (D) is preferably from 1 to 20.1% by mass based on the total mass of all the components of the epoxy resin composition. The epoxy resin composition of the present invention may contain, in addition to the above components (A) to (D), components which will be described below as needed.
S -14- 201233725 (E)成分：硼酸酯化合物 本發明之環氧樹脂組成物，爲提高常溫（25 °C )之儲存 安定性，及增長可使用壽命，亦可含有硼酸酯化合物作爲 (E) 成分。 至於（E)成分之硼酸酯化合物可使用例如2,2’-氧基雙 (5,5’-二甲基-1，3,2-氧雜硼戊烷）、硼酸三甲酯、硼酸三乙 酯、硼酸三正丙酯、硼酸三異丙酯、硼酸三正丁酯、硼酸 三戊酯、硼酸三烯丙酯、硼酸三己酯、硼酸三環己酯、硼 酸三辛酯、硼酸三壬酯 '硼酸三癸酯、硼酸三-十二烷酯 、硼酸三-十六烷酯、硼酸三-十八烷酯、參（2·乙基己氧基 )硼烷、雙（1，4,7，10-四氧雜Η--烷基）（1，4,7，10，13-五氧雜 十四烷基）（1,4,7_三氧雜十一烷基）硼烷、硼酸三苄酯、硼 酸三苯酯、硼酸三-鄰-甲苯酯 '硼酸三-間-甲苯酯、三乙 醇胺硼酸酯。 含有硼酸酯化合物作爲（Ε)成分時，相對於環氧樹脂 組成物之全部成分合計質量，較好爲〇·〇5〜5質量％，更 好爲0.1〜3質量％，再更好爲0.5〜1.5質量％。 (F) 成分：二氧化矽塡充劑 本發明之環氧樹脂組成物，爲了樹脂組成物之黏度調 節或提高樹脂組成物之硬化物之耐熱性、耐濕性，亦可含 有二氧化矽塡充劑作爲（F)成分。 含有二氧化矽塡充劑作爲（F)成分時，相對於環氧樹 -15- 201233725 脂組成物之全部成分合計質量，較好爲5〜80質量％，更 好爲15〜70質量％，再更好爲20〜65質量％。 作爲（F)成分之二氧化矽塡充劑之形狀並無特別限制 ’可使用粒狀、粉末狀' 鱗片狀等任一形態。 又，作爲（F)成分之二氧化矽塡充劑，依據需要亦可 爲施以表面處理者。例如亦可爲於粒子表面形成氧化皮膜 者。 作爲（F)成分之二氧化矽塡充劑之平均粒徑（不爲粒狀 時’爲其平均最大直徑）並無特別限制，但就對封裝部位 之塡充性變良好之觀點而言，較好爲0.01〜30μιη，更好 爲0.05〜20μιη，再更好爲0.1〜1〇μηι。 (G)成分：矽烷偶合劑 本發明之環氧樹脂組成物，爲提高硬化物之密著性， 亦可含有矽烷偶合劑作爲（G)成分。 含有矽烷偶合劑作爲（G)成分時，相對於環氧樹脂組 成物之全部成分合計質量，較好爲0.01〜10質量％，更好 爲0.05〜5質量％，再更好爲0.1〜3質量％。 本發明之環氧樹脂組成物亦可依據需要含有上述（Α) 〜（G)成分以外之成分。該等成分之具體例，可調配塡充 劑、勻化劑、著色劑、離子捕捉劑、消泡劑、抗氧化劑、 難燃劑等。各調配劑之種類、調配量爲一般使用者。 (環氧樹脂組成物之調製）S -14-201233725 (E) Component: Borate compound The epoxy resin composition of the present invention may also contain a borate compound as a storage stability at room temperature (25 ° C) and an increase in service life. (E) Ingredients. As the borate ester compound of the component (E), for example, 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborolane), trimethyl borate, boric acid can be used. Triethyl ester, tri-n-propyl borate, tri-isopropyl borate, tri-n-butyl borate, triamyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, boric acid Tridecyl ester 'tridecyl borate, tri-dodecyl borate, tri-hexadecane borate, tri-octadecyl borate, ginseng (2 · ethylhexyloxy) borane, double (1, 4,7,10-tetraoxaindole-alkyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxadecyl)boron Alkane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate 'tri-m-cresyl borate, triethanolamine borate. When the boric acid ester compound is contained as the (Ε) component, the total mass of all the components of the epoxy resin composition is preferably 5 to 5 mass%, more preferably 0.1 to 3 mass%, more preferably 0.5 to 1.5% by mass. (F) Component: cerium oxide filling agent The epoxy resin composition of the present invention may contain cerium oxide for the purpose of adjusting the viscosity of the resin composition or improving the heat resistance and moisture resistance of the cured product of the resin composition. The filler is used as the component (F). When the cerium oxide-containing filler is contained as the component (F), the total mass of all the components of the epoxy resin -15 to 201233725 is preferably from 5 to 80% by mass, more preferably from 15 to 70% by mass. More preferably, it is 20 to 65 mass%. The shape of the cerium oxide filling agent as the component (F) is not particularly limited, and any form such as a granular or powdery scaly shape can be used. Further, the cerium oxide filling agent as the component (F) may be subjected to a surface treatment as needed. For example, it may be an oxide film formed on the surface of the particles. The average particle diameter of the cerium oxide filling agent as the component (F) (the average diameter of the granules when it is not in the form of granules) is not particularly limited, but from the viewpoint of the improvement in the chargeability of the package portion, It is preferably 0.01 to 30 μm, more preferably 0.05 to 20 μm, and even more preferably 0.1 to 1 μm. (G) component: decane coupling agent The epoxy resin composition of the present invention may contain a decane coupling agent as the component (G) in order to improve the adhesion of the cured product. When the decane coupling agent is contained as the component (G), the total mass of all the components of the epoxy resin composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, still more preferably 0.1 to 3 by mass. %. The epoxy resin composition of the present invention may contain components other than the above (Α) to (G) components as needed. Specific examples of such components may be formulated with a hydrazine, a homogenizing agent, a coloring agent, an ion scavenger, an antifoaming agent, an antioxidant, a flame retardant, and the like. The type and amount of each formulation are normal users. (modulation of epoxy resin composition)
S -16- 201233725 本發明之環氧樹脂組成物係將上述之（A)〜（D)成分以 及依據需要之上述（E)〜（G)成分以及塡充劑等之任意成分 混合、攪拌而調製。混合攪拌可使用輥硏磨機進行，但當 然不限定於此。於作爲（A)成份之環氧樹脂爲固體時，較 好利用加熱等予以液狀化或流動化後混合。 可同時混合各成分，於先混合一部份成分，之後混合 剩餘成分等進行適當變更亦無妨。 以下，針對本發明之環氧樹脂組成物之特性加以描述 〇 本發明之環氧樹脂組成物於常溫（25 °C )之黏度低如 6000 mPa· s以下，於半導體封裝材料等用途使用時之作 業性良好。 本發明之環氧樹脂組成物於常溫（2 5 °C )之黏度較好爲 5500 mPa. s以下，更好爲4000 mPa. s以下，再更好爲 3 000 mPa · s 以下。 本發明之環氧樹脂組成物於低溫短時間硬化性優異， 於150°C以下之溫度加熱數分鐘（例如在120°C加熱3分鐘） 即可硬化》 本發明之環氧樹脂組成物於後述實施例中記載之順序 測定之膠凝時間較好爲1 80秒以下，更好爲90秒以下， 又更好爲60秒以下。 又，本發明之環氧樹脂組成物於常溫（25 °C )之儲存安 定性良好，可使用壽命長。具體而言，在25 °C、濕度50% 之環境中保存48小時後之黏度小於保存前黏度之1.2倍 -17- 201233725 ，較好保存1 68小時後之黏度小於保存前黏度之1.2倍。 又，本發明之環氧樹脂組成物之密著性優異，藉後述 實施例中記載之順序測定之剝離強度爲1 〇kg以上，較好 爲15kg以上，更好爲17kg以上。 又，本發明之環氧樹脂組成物之玻璃轉移溫度（Tg)爲 1 20 °C以上，故封裝時焊球補強性優異，於熱循環試驗（例 如重複自-40 °C至125 °C之熱循環之耐久性試驗）中之龜裂 發生受到抑制。本發明之環氧樹脂組成物之玻璃轉移溫度 (Tg)較好爲125°C以上，更好爲130°C以上。 依據該等特性，本發明之環氧樹脂組成物可較好地使 用作爲一次安裝用或二次安裝用半導體封裝材料。 本發明之環氧樹脂組成物亦可較好地使用於接著劑或 黏晶劑。 [實施例] 以下，利用實施例詳細說明本發明，但本發明不限定 於該等。 (實施例1〜1 4、比較例1〜4) 以成爲下表所示調配比例之方式，使用輥硏磨機混練 原料而調製實施例1〜1 4、比較例1〜4之環氧樹脂組成物 °又’表中各組成相關數値表示質量份。 且，表中之記號分別表示如下"S-16-201233725 The epoxy resin composition of the present invention is obtained by mixing and stirring the above components (A) to (D) and optionally the components (E) to (G) and the chelating agent. modulation. The mixing and stirring can be carried out using a roll honing machine, but it is not limited thereto. When the epoxy resin as the component (A) is a solid, it is preferably liquidized or fluidized by heating or the like and then mixed. The components may be mixed at the same time, and a part of the components may be mixed first, and then the remaining components may be mixed and appropriately changed. Hereinafter, the characteristics of the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention has a low viscosity at room temperature (25 ° C) as low as 6000 mPa·s or less, and is used in applications such as semiconductor packaging materials. Good workability. The viscosity of the epoxy resin composition of the present invention at a normal temperature (25 ° C) is preferably 5,500 mPa·s or less, more preferably 4,000 mPa·s or less, and even more preferably 3 000 mPa·s or less. The epoxy resin composition of the present invention is excellent in low-temperature short-time hardening property, and is heated at a temperature of 150 ° C or lower for several minutes (for example, heating at 120 ° C for 3 minutes) to be cured. The epoxy resin composition of the present invention will be described later. The gelation time measured in the order described in the examples is preferably 1 to 80 seconds or less, more preferably 90 seconds or less, still more preferably 60 seconds or less. Further, the epoxy resin composition of the present invention has good storage stability at room temperature (25 ° C) and can have a long service life. Specifically, the viscosity after storage for 48 hours in an environment of 25 ° C and a humidity of 50% is less than 1.2 times the viscosity before storage -17-201233725, and the viscosity after storage for 1 68 hours is less than 1.2 times that before storage. Further, the epoxy resin composition of the present invention is excellent in adhesion, and the peel strength measured by the procedure described in the examples below is 1 〇 kg or more, preferably 15 kg or more, more preferably 17 kg or more. Moreover, the glass transition temperature (Tg) of the epoxy resin composition of the present invention is 1 20 ° C or more, so that the solder ball is excellent in encapsulation during packaging, and is subjected to a thermal cycle test (for example, repeating from -40 ° C to 125 ° C) The occurrence of cracks in the durability test of thermal cycle is suppressed. The glass transition temperature (Tg) of the epoxy resin composition of the present invention is preferably 125 ° C or higher, more preferably 130 ° C or higher. According to these characteristics, the epoxy resin composition of the present invention can be preferably used as a semiconductor package material for primary mounting or secondary mounting. The epoxy resin composition of the present invention can also be preferably used in an adhesive or a die bond. [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto. (Examples 1 to 14 and Comparative Examples 1 to 4) Epoxy resins of Examples 1 to 14 and Comparative Examples 1 to 4 were prepared by kneading raw materials using a roll honing machine so as to have a mixing ratio as shown in the following table. The composition ° and the number of each component in the table represent the mass parts. And, the symbols in the table respectively indicate the following "
環氧樹脂：雙酚A型環氧樹脂、製品名EXA8 5 0CRP • 18 -Epoxy resin: bisphenol A type epoxy resin, product name EXA8 5 0CRP • 18 -
S 201233725 ，DIC股份有限公司製造 DME : 1，4-環己烷二甲醇二縮水甘油醚，製品名 ZX1658GS，新日鐵化學股份有限公司 潛在性硬化劑（咪唑系潛在性硬化劑）：微膠囊型咪唑（含有 咪唑成分與雙酚A型環氧樹脂），製品名HX3742，旭化成 電子材料股份有限公司製 酚樹脂：烯丙基丙烯酸酚樹脂，製品名MEH8005，明和化 成股份有限公司製 酸酐系硬化劑：（製品名：HN-5500，日立化成工業股份有 限公司製） 針對所調製之環氧樹脂組成物實施以下評價。 (硬化物外觀） 將評價用試料以與接著於聚醯亞胺薄膜上之矽晶片（2 x20x0.75mm)之長邊側相接之方式塗佈i〇mg所得之試驗片 放入烘箱中，在1 20°C加熱3分鐘，使環氧樹脂組成物硬 化。目視觀察加熱後之硬化物外觀。於硬化物上未見到皴 紋、柚子皮等之外觀不良或顏色不均之情況記爲〇，於硬 化物上見到皺紋、柚子皮等之外觀不良或顏色不均之情況 (黏度、可使用壽命） 使用EMD型黏度計（東京計器公司製，機器名：TV-22) ， 在液溫 25 °C 、 lrpm 測定 剛調製 後之評 價用試 料之黏 -19- 201233725 度（初期黏度）。 隨後，將評價用試料裝入密閉容器中， 50%之環境中保存48小時之時點測定黏度· 後之黏度小於初期黏度之1.2倍時記爲〇， 時記爲X。 又，將評價用試料裝入密閉容器中，3 50%之環境中保存168小時之時點測定黏度 時後之黏度小於初期黏度之1.2倍時記爲〇 上時記爲X。 (膠凝時間） 在120°C之熱板上，供給5mg±lmg之環 ，利用攪拌棒描繪圓之方式進行攪拌，測定 攪拌邊使攪拌棒向上拉離時拉絲成爲5mm 間。 (密著性） 於玻璃環氧基板上印刷評價用試料，於 2mmx2mm之矽晶片。將其在150±2t之熱風 化5分鐘。將其作爲試驗片，使用dage公 黏晶測試機「DAGE4000」對矽晶片施加荷 晶片時之強度（剝離強度）。設爲n= 1 0，以其 查値。 玻璃轉移溫度（Tg):針對在120°C加熱硬化 在25°C、濕度 保存48小時 爲1.2倍以上 E 2 5 °C、濕度 。保存1 6 8小 ，爲1 . 2倍以 氧樹脂組成物 自供給後至邊 以下爲止之時 該試料上載置 乾燥機加熱硬 司製之萬能型 重，測定剝離 平均値作爲檢 3分鐘之硬化S 201233725 , DME manufactures DME : 1,4-cyclohexane dimethanol diglycidyl ether, product name ZX1658GS, Nippon Steel Chemical Co., Ltd. latent hardener (imidazole-based latent hardener): microcapsule Type imidazole (containing imidazole component and bisphenol A epoxy resin), product name HX3742, phenol resin made by Asahi Kasei Electronic Materials Co., Ltd.: allyl acrylate phenol resin, product name MEH8005, Minghe Chemical Co., Ltd. Agent: (product name: HN-5500, manufactured by Hitachi Chemical Co., Ltd.) The following evaluation was performed on the prepared epoxy resin composition. (Appearance of the cured product) The test piece obtained by coating the test sample with the long side of the tantalum wafer (2 x 20 x 0.75 mm) on the polyimide film was placed in an oven. The epoxy resin composition was hardened by heating at 1200 ° C for 3 minutes. The appearance of the cured product after heating was visually observed. The case where the appearance of the crepe, the grapefruit skin, or the like is not observed on the cured product, and the color unevenness is recorded as 〇, and the appearance of wrinkles, grapefruit peel, etc., which is poor in appearance or color unevenness, is observed on the cured product (viscosity, Service life) Using an EMD type viscometer (manufactured by Tokyo Keiki Co., Ltd., machine name: TV-22), the viscosity of the evaluation sample immediately after preparation was measured at a liquid temperature of 25 ° C and 1 rpm to -19 - 201233725 degrees (initial viscosity). Subsequently, the evaluation sample was placed in a sealed container, and the viscosity was measured at 50 hours in an environment of 50%, and the viscosity was less than 1.2 times the initial viscosity, and it was recorded as X. Further, when the sample for evaluation was placed in a sealed container and the viscosity was measured at a temperature of 168 hours in an environment of 390 hours, it was less than 1.2 times the initial viscosity, and it was recorded as X when it was marked as 〇. (gelling time) A ring of 5 mg ± 1 mg was supplied to a hot plate at 120 ° C, and the mixture was stirred by means of a stir bar, and the wire was pulled up to 5 mm when the stirring bar was pulled upward. (Adhesiveness) The sample for evaluation was printed on a glass epoxy substrate, and the wafer was placed at 2 mm x 2 mm. It was weathered for 5 minutes at 150 ± 2 t. This was used as a test piece, and the strength (peeling strength) when a wafer was applied to a tantalum wafer using a dage male bonded crystal tester "DAGE4000". Set to n= 1 0 to check it. Glass transition temperature (Tg): heat hardened at 120 ° C. At 25 ° C, humidity for 48 hours, 1.2 times or more E 2 5 ° C, humidity. The storage of 1 6 8 small, 1.2 times the oxygen resin composition from the time of supply to the side until the time of the sample is placed on the dryer to heat the hard system of the universal weight, the measurement of the peeling average 値 as a test 3 minutes of hardening
-20- S 201233725 物，使用真空理公司製之TM3000，利用TMA法測定玻璃 轉移溫度。 [表1] 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 實施 例6 實施 例7 (Α)環氧樹脂 75.0 62.0 50.0 22.5 52.8 51.5 TBIDME 41.5 46.0 50.0 36.5 25.0 50.0 50.0 (c)潛在性硬化劑 25.0 59.0 90.0 86.0 82.5 85.8 88.0 (咪唑成分） (8.33) (19.67) (30) P8.67) (27.5) (28.6) (29.3) (環氧樹脂成分） (16.67) (39.33) (60) (57.33) (55) (57.2) (58.7) (D)酚樹脂 7.5 9.0 10.0 7.5 5.5 2.0 6.0 酸酐系硬化劑 〇 〇 〇 硬化物外觀 〇 〇 〇 〇 黏度[mPa · s] 738 1038 1477 2401 4150 1182 1306 膠凝時間[秒] 86 46 28 21 16 22 23 密著性[kg] 17 23 23 23 25 23 23 Tg[°C] 139 140 140 138 141 140 140 可使用壽命 (48小時後） 〇 〇 〇 〇 〇 〇 〇 可使用壽命 (168小時後） 〇 〇 〇 〇 X 〇 〇 實施例1 (Β)成分 31.1質量％ (相對於（Α)(包含（C)之環氧樹脂成分）、（Β)成分之合計質 量） (C) 成分（咪唑成分）5.6質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％ -21 - 201233725 (相對於環氧樹脂組成物全部成分之合計質量） 實施例2 (B) 成分 31.2質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）11_2質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例3 (B) 成分 31.2質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15.0質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例4 (B) 成分 31.3質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）18.8質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％-20- S 201233725, using the TM3000 manufactured by Vacuum Chemical Co., Ltd., the glass transition temperature was measured by the TMA method. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (Α) epoxy resin 75.0 62.0 50.0 22.5 52.8 51.5 TBIDME 41.5 46.0 50.0 36.5 25.0 50.0 50.0 (c) Potential Hardener 25.0 59.0 90.0 86.0 82.5 85.8 88.0 (imidazole component) (8.33) (19.67) (30) P8.67) (27.5) (28.6) (29.3) (epoxy resin composition) (16.67) (39.33) (60) (57.33) (55) (57.2) (58.7) (D) Phenolic resin 7.5 9.0 10.0 7.5 5.5 2.0 6.0 Anhydride-based hardener 〇〇〇 hardened product appearance 〇〇〇〇 viscosity [mPa · s] 738 1038 1477 2401 4150 1182 1306 Gel time [sec] 86 46 28 21 16 22 23 Adhesion [kg] 17 23 23 23 25 23 23 Tg[°C] 139 140 140 138 141 140 140 Service life (after 48 hours) 〇〇〇 〇〇〇〇 service life (after 168 hours) 〇〇〇〇X 〇〇Example 1 (Β) component 31.1% by mass (relative to (Α) (including (C) epoxy resin component), (Β) (total mass of ingredients) (C) Component (imidazole component) 5.6% by mass (relative to the total mass of all components of the epoxy resin composition) (D) Component: 5 mass% - 21 - 201233725 (total mass of all components of the epoxy resin composition) Example 2 (B) Component 31.2% by mass (relative to (A) (epoxy resin containing (C) (C) Component (imidazole component) 11_2% by mass (to the total mass of all components of the epoxy resin composition) (D) Component 5 mass% (relative to epoxy resin composition) Example 3 (B) Component 31.2% by mass (relative to (A) (including (C) epoxy resin component), (B) total mass) (C) Component (imidazole component) 15.0% by mass (to the total mass of all the components of the epoxy resin composition) (D) Component: 5% by mass (to the total mass of all components of the epoxy resin composition) Example 4 (B) Component: 13.3% by mass ( (A) (including the epoxy resin component of (C)) and the total mass of the component (B)) (C) Component (imidazole component) 18.8% by mass (to the total mass of all the components of the epoxy resin composition) (D) Ingredient 5 mass%
S -22- 201233725 (相對於環氧樹脂組成物全部成分之合計質量） 實施例5 (B) 成分 31.2質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）24.3質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分5質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例6 (B) 成分 31.2質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質4) (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分1.0質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例7 (B) 成分 3 1.2質量％ (相對於（A)(包含（C)之環氧樹脂成分）' (B)成分之合^十胃 量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） -23- 201233725 (D)成分 3.1質量％ (相對於環氧樹脂組成物全部成分之合計質量） [表2] 實施 例8 實施 例9 實施 例10 實施 例11 實施 例12 實施 例13 例14 (A)環氧樹脂 38.5 31.0 24.0 92.0 84.0 20.0 • (B)DME 41.5 37.0 33.0 8.0 16.0 80.0 100 (C)潛在性硬化劑 79.5 76.5 74.0 90.0 90.0 90.0 90.0 (咪唑成分） (26.5) (25.5) (24.7) (30.0) (30.0) (30.0) (30.0) (環氧樹脂成分） (53.0) (51.0) (49.3) (60.0) (60.0) (60.0) (60.0) (D)酚樹脂 16.5 25.0 33.0 10.0 10.0 10.0 10.0 酸酐系硬化劑 硬化物外觀 〇 〇 〇 〇 〇 〇 〇 黏度[mPa · s] 1957 2607 3528 5505 3327 1026 653 膠凝時間[秒] 36 60 71 25 28 31 38 密著性[kg] 23 23 26 23 23 21 18 Tg[°C] 140 138 136 142 142 134 131 可使用壽命 (48小時後） 〇 〇 〇 〇 〇 〇 〇 可使用壽命 (168小時後） 〇 〇 X 〇 〇 〇 〇 實施例8 (B) 成分 31.2質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 9.4質量％ (相對於環氧樹脂組成物全部成分之合計質量）S -22-201233725 (Total mass of all components of the epoxy resin composition) Example 5 (B) Component 31.2% by mass (relative to (A) (including (C) epoxy resin component), (B) (C) Component (imidazole component) 24.3% by mass (to the total mass of all components of the epoxy resin composition) (D) Component 5 mass% (relative to the total mass of all components of the epoxy resin composition) Example 6 (B) Component: 31.2% by mass (Comparative to (A) (including (C) epoxy resin component) and (B) component) (C) Component (imidazole component) 15% by mass ( (D) Component: 1.0% by mass (to the total mass of all components of the epoxy resin composition) Example 7 (B) Component 3 1.2% by mass (relative to (A) (Including (C) epoxy resin component) '(B) component of the total amount of stomach weight) (C) Component (imidazole component) 15% by mass (to the total mass of all components of the epoxy resin composition) - 23- 201233725 (D) Composition 3.1% by mass (relative to the total composition of the epoxy resin composition) Quality) [Table 2] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 (A) Epoxy Resin 38.5 31.0 24.0 92.0 84.0 20.0 • (B) DME 41.5 37.0 33.0 8.0 16.0 80.0 100 (C) latent hardener 79.5 76.5 74.0 90.0 90.0 90.0 90.0 (imidazole component) (26.5) (25.5) (24.7) (30.0) (30.0) (30.0) (30.0) (epoxy resin composition) (53.0) (51.0 (49.3) (60.0) (60.0) (60.0) (60.0) (D) Phenolic Resin 16.5 25.0 33.0 10.0 10.0 10.0 10.0 Appearance of cured anhydride hardeners 〇〇〇〇〇〇〇 Viscosity [mPa · s] 1957 2607 3528 5505 3327 1026 653 Gel time [sec] 36 60 71 25 28 31 38 Adhesion [kg] 23 23 26 23 23 21 18 Tg[°C] 140 138 136 142 142 134 131 Service life (48 hours later) 〇〇〇〇〇〇〇 service life (after 168 hours) 〇〇X 〇〇〇〇Example 8 (B) Composition 31.2% by mass (relative to (A) (including (C) epoxy resin component) (B) Total mass of the components (B) (Imazole component) 15% by mass (relative to all components of the epoxy resin composition) Total mass) (D) Component 9.4% by mass (relative to the total mass of all components of the epoxy resin composition)
S -24- 201233725 實施例9 (B) 成分 31.1質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 14.7質量％ (相對於環氧樹脂組成物全部成分之合計質量.） 實施例1 0 (B) 成分 31.0質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 20.1質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例1 1 (B) 成分 5.0質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％ (相對於環氧樹脂組成物全部成分之合計質量） -25- 201233725 實施例1 2 (B) 成分 10.0質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例1 3 (B) 成分 50.0質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例1 4 (B) 成分 62.5質量°/。 (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分5質量％ (相對於環氧樹脂組成物全部成分之合計質量）S -24-201233725 Example 9 (B) Component 31.1% by mass (relative to (A) (including (C) epoxy resin component), (B) total mass) (C) Component (imidazole component) 15 % by mass (to the total mass of all components of the epoxy resin composition) (D) Component: 14.7% by mass (relative to the total mass of all components of the epoxy resin composition.) Example 1 0 (B) Component 31.0% by mass ( (A) (including the epoxy resin component of (C)) and the total mass of the component (B)) (C) component (imidazole component) 15 mass% (to the total mass of all components of the epoxy resin composition) (D) Component: 20.1% by mass (to the total mass of all the components of the epoxy resin composition) Example 1 1 (B) Component 5.0% by mass (relative to (A) (including (C) epoxy resin component), (B) Total mass of components (C) Component (imidazole component) 15% by mass (to the total mass of all components of the epoxy resin composition) (D) Component 5 mass% (relative to all components of the epoxy resin composition) Total quality) -25- 201233725 Example 1 2 (B) Composition 10.0% by mass ( (A) (including the epoxy resin component of (C)) and the total mass of the component (B)) (C) component (imidazole component) 15% by mass (to the total mass of all components of the epoxy resin composition) ( D) Component: 5% by mass (to the total mass of all components of the epoxy resin composition) Example 1 3 (B) Component: 50.0% by mass (relative to (A) (including (C) epoxy resin component), ( B) Total mass of the components) (C) Component (imidazole component) 15% by mass (to the total mass of all the components of the epoxy resin composition) (D) Component 5 mass% (relative to all components of the epoxy resin composition) Total mass) Example 1 4 (B) Composition 62.5 mass ° /. (Comparative mass with respect to (A) (including epoxy resin component (C)) and (B) component) (C) Component (imidazole component) 15% by mass (relative to the total mass of all components of the epoxy resin composition) (D) Component 5 mass% (relative to the total mass of all components of the epoxy resin composition)
S -26- 201233725 [表3] 比較例1 比較例2 比較例3 比較例4 (A)環氧樹脂 80.0 53.5 100.0 65.0 (B)DME 40.0 50.0 35 0 (C)潛在性硬化劑 12.5 85.0 90.0 30 0 (咪唑成分） (4.17) (28.3) (30.0) (10.0) (環氧樹脂成分） (8.33) _ (56.7) (60.0) (20.0) (D)酚樹脂 7.0 一 10.0 酸酐系硬化劑 _ 70.0 硬化物外觀 (外觀不良 ，色不均） 〇 黏度[mPa . s] 654 1148 6412 0.5 膠凝時間[秒] 180以上 未硬化 22 25 180以上 未硬化 密著性[kg] 一 23 Tg[°C] 139 142 160 可使用壽命 (48小時後） 〇 〇 〇 X 可使用壽命 (168小時後） 〇 〇 〇 - 比較例1 (B) 成分 3 1. 1質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）3.0質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 5質量％ (相對於環氧樹脂組成物全部成分之合計質量） •27- 201233725 比較例2 (B) 成分 31.2質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分 0質量％ (相對於環氧樹脂組成物全部成分之合計質量） 比較例3 (B) 成分 0質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質纛） (C) 成分（咪唑成分）15質量％ (相對於環氧樹脂組成物全部成分之合計質量） (D) 成分5質量％ (相對於環氧樹脂組成物全部成分之合計質量） 比較例4 (B )成分 2 9.1質量％ (相對於（A)(包含（C)之環氧樹脂成分）、（B)成分之合計質量） (C)成分（咪唑成分）5質量％ (相對於環氧樹脂組成物全部成分之合計質量） 比較例4爲使用微膠囊型咪唑作爲硬化促進劑時之通 常含量者，作爲硬化劑之酸酐系硬化劑相對於組成物中之 環氧樹脂成分以當量比計含有0.6當量。S -26- 201233725 [Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) Epoxy Resin 80.0 53.5 100.0 65.0 (B) DME 40.0 50.0 35 0 (C) Latent Hardener 12.5 85.0 90.0 30 0 (imidazole component) (4.17) (28.3) (30.0) (10.0) (epoxy resin composition) (8.33) _ (56.7) (60.0) (20.0) (D) phenol resin 7.0-10.0 anhydride hardener _ 70.0 Appearance of hardened material (poor appearance, uneven color) 〇 Viscosity [mPa . s] 654 1148 6412 0.5 Gel time [sec] 180 or more unhardened 22 25 180 or more uncured adhesion [kg] A 23 Tg [°C ] 139 142 160 Service life (after 48 hours) 〇〇〇X service life (after 168 hours) 〇〇〇 - Comparative Example 1 (B) Composition 3 1. 1% by mass (relative to (A) (contains ( (C) Epoxy resin component) and (B) total mass) (C) Component (imidazole component) 3.0% by mass (to the total mass of all components of the epoxy resin composition) (D) Component 5 mass% ( Relative mass of all components of the epoxy resin composition) • 27- 201233725 Comparative Example 2 (B) Composition 31.2% by mass (relative to ( A) (including the epoxy resin component of (C)) and the total mass of the component (B) (C) Component (imidazole component) 15% by mass (to the total mass of all components of the epoxy resin composition) (D) Component 0% by mass (to the total mass of all the components of the epoxy resin composition) Comparative Example 3 (B) Component 0% by mass (relative to (A) (including (C) epoxy resin component), (B) component (C) Component (imidazole component) 15% by mass (to the total mass of all components of the epoxy resin composition) (D) Component 5 mass% (relative to the total mass of all components of the epoxy resin composition) Comparative Example 4 (B) Component 2 9.1% by mass (relative to (A) (including (C) epoxy resin component) and (B) component total mass) (C) Component (imidazole component) 5 mass% ( The total mass of all the components of the epoxy resin composition) Comparative Example 4 is a general content when microcapsule-type imidazole is used as a curing accelerator, and an acid anhydride-based hardener as a curing agent is compared with the epoxy resin component in the composition. It is contained in an equivalent ratio of 0.6 equivalent.
-28- S 201233725 (D)成分 0質量％ (相對於環氧樹脂組成物全部成分之合計質量） 實施例1〜1 4之環氧樹脂組成物確認爲硬化物外觀良 好，進行均一硬化。且於25°C之黏度爲6000mPa . s以下 。且，膠凝時間爲1 20秒以下，確認低溫短時間硬化性優 異。且，密著性良好，玻璃轉移溫度（T g)亦爲1 2 0 °C以上 。又，48小時保存後之可使用壽命亦良好。 (C)成份之含量爲5.6〜24.3質量％，（D)成分脂含量爲1〜 20.1質量％之實施例1〜4、6〜9、11〜14之168小時保 存後之可使用壽命亦良好。 另一方面，（C)成分之含量未達5質量％之比較例1之 環氧樹脂組成物，於膠凝時間評價中即使經過1 8 0秒亦未 硬化，確認低溫短時間硬化性差。因此，並未實施硬化物 外觀及密著性評價。未含（D)成分之比較例2之硬化物外 觀差，確認無法進行均一硬化。因此，未實施密著性評價 及玻璃轉移溫度測定。未含（B)成分之比較例3於20°C之 黏度高至超過6000mPa· s。未含（D)成分，而使用酸酐系 硬化劑，以作爲硬化促進劑使用時之通量含有微膠囊型咪 唑之比較例4，於膠凝化評價中即使經過1 8 0秒亦未硬化 ，確認低溫短時間硬化性差。至於其理由，認爲係因酸酐 系硬化劑之存在，使由咪唑之硬化作用延遲所致者。又， 由於確認到低溫短時間硬化性差，故實際上未進行密著性 評價。且，48小時保存後之可使用壽命差。因此未實施 1 68小時保存後之可使用壽命評價。 -29 --28-S 201233725 (D) Component 0% by mass (total mass of all components of the epoxy resin composition) The epoxy resin compositions of Examples 1 to 14 were confirmed to have a good appearance of the cured product, and were uniformly cured. And the viscosity at 25 ° C is 6000 mPa. s or less. Further, the gelation time was 1 20 seconds or less, and it was confirmed that the low-temperature short-time hardenability was excellent. Moreover, the adhesion is good, and the glass transition temperature (T g) is also above 120 °C. In addition, the service life after 48 hours of storage is also good. The content of the component (C) is 5.6 to 24.3% by mass, and the fat content of the component (D) is 1 to 20.1% by mass. The storage life of the examples 1 to 4, 6 to 9, 11 to 14 after 168 hours is good. . On the other hand, the epoxy resin composition of Comparative Example 1 in which the content of the component (C) was less than 5% by mass was not cured even after 180 hours in the evaluation of the gelation time, and it was confirmed that the low-temperature short-time hardenability was poor. Therefore, the appearance and adhesion evaluation of the cured product were not carried out. The cured product of Comparative Example 2 which did not contain the component (D) was poor in appearance, and it was confirmed that uniform hardening could not be performed. Therefore, the adhesion evaluation and the glass transition temperature measurement were not performed. Comparative Example 3, which did not contain the component (B), had a viscosity at 20 ° C of more than 6000 mPa·s. In the case of the (D) component, the acid anhydride-based curing agent was used, and the comparative example 4 containing the microcapsule-type imidazole when used as a curing accelerator was not cured even after 180 hours in the evaluation of gelation. It was confirmed that the low temperature and poor hardenability were poor. The reason for this is considered to be due to the delay of the hardening action of imidazole due to the presence of an acid anhydride-based hardener. Further, since it was confirmed that the low-temperature short-time hardenability was poor, the adhesion evaluation was not actually performed. Moreover, after 48 hours of storage, the service life is poor. Therefore, the service life evaluation after 1 68 hours of storage was not implemented. -29 -
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011021363A JP4965715B1 (en) | 2011-02-03 | 2011-02-03 | Epoxy resin composition and semiconductor sealing material using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201233725A true TW201233725A (en) | 2012-08-16 |
| TWI547520B TWI547520B (en) | 2016-09-01 |
Family
ID=46602309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100127977A TWI547520B (en) | 2011-02-03 | 2011-08-05 | Epoxy resin composition and semiconductor-sealing material using the same |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4965715B1 (en) |
| KR (1) | KR101819264B1 (en) |
| CN (1) | CN103328530B (en) |
| MY (1) | MY161359A (en) |
| TW (1) | TWI547520B (en) |
| WO (1) | WO2012105072A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072947A (en) * | 2013-03-26 | 2014-10-01 | 太阳油墨制造株式会社 | Epoxy resin composition, composition for filling in hole plugging, and printed wiring board using same |
| TWI582125B (en) * | 2013-01-17 | 2017-05-11 | Sekisui Chemical Co Ltd | Method for manufacturing hardened anisotropic conductive material, connecting structure and connecting structure for electronic parts |
| TWI602874B (en) * | 2012-12-27 | 2017-10-21 | 納美仕有限公司 | Liquid epoxy resin composition |
| TWI760225B (en) * | 2021-05-13 | 2022-04-01 | 大陸商蘇州震坤科技有限公司 | Encapsulating resin to reduce encapsulation delamination |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6340174B2 (en) * | 2013-07-30 | 2018-06-06 | ハリマ化成株式会社 | Conductive paste |
| CN104513455B (en) * | 2013-09-26 | 2017-01-11 | 常州市迪波电子材料有限公司 | Waterproof encapsulating material used in temperature sensors |
| JP2015209516A (en) * | 2014-04-28 | 2015-11-24 | 株式会社クラレ | Curable composition, and cured product |
| WO2015173906A1 (en) | 2014-05-14 | 2015-11-19 | 三菱電機株式会社 | Method for manufacturing semiconductor device |
| CN107109032B (en) * | 2014-11-26 | 2020-01-21 | 京瓷株式会社 | Resin composition for semiconductor encapsulation and semiconductor device |
| JP6800115B2 (en) | 2017-09-07 | 2020-12-16 | 信越化学工業株式会社 | Resin composition, resin film, semiconductor laminate, semiconductor laminate manufacturing method and semiconductor device manufacturing method |
| JP6754741B2 (en) | 2017-09-07 | 2020-09-16 | 信越化学工業株式会社 | Semiconductor laminates, methods for manufacturing semiconductor laminates, and methods for manufacturing semiconductor devices |
| CN107739598B (en) * | 2017-10-31 | 2021-01-26 | 南昌航空大学 | Permanent epoxy resin cementing agent |
| KR20220063596A (en) | 2020-11-10 | 2022-05-17 | 한국전기연구원 | Organic-nonorganic hybrid liquid insulating materials and their manufacturing method |
| CN113045864A (en) * | 2021-04-26 | 2021-06-29 | 上海方乾科技有限公司 | Halogen-free flame-retardant epoxy resin containing naphthalene ring structure and preparation method thereof |
| JP2022175617A (en) * | 2021-05-14 | 2022-11-25 | 住友化学株式会社 | Epoxy resin composition and cured material thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3454437B2 (en) * | 1992-10-02 | 2003-10-06 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | One-part epoxy resin adhesive composition with low viscosity and no solvent |
| JP3340882B2 (en) * | 1995-05-02 | 2002-11-05 | 日東電工株式会社 | Epoxy resin composition for encapsulating semiconductor element and resin-encapsulated semiconductor device |
| WO2006064736A1 (en) * | 2004-12-16 | 2006-06-22 | Daicel Chemical Industries, Ltd. | Thermosetting epoxy resin composition and use thereof |
| JP4775374B2 (en) * | 2005-11-25 | 2011-09-21 | 日立化成工業株式会社 | Liquid resin composition for electronic components and electronic component device |
| JP2007204669A (en) * | 2006-02-03 | 2007-08-16 | Asahi Kasei Chemicals Corp | Curing agent for epoxy resin, having specific small particle diameter particle size distribution and epoxy resin composition |
| JP2007246713A (en) * | 2006-03-16 | 2007-09-27 | Sumitomo Bakelite Co Ltd | One-pack type epoxy resin composition |
| JP4752565B2 (en) * | 2006-03-27 | 2011-08-17 | 大日本印刷株式会社 | Electronic pen form manufacturing method |
| JP5101860B2 (en) * | 2006-10-26 | 2012-12-19 | パナソニック株式会社 | Epoxy resin composition and semiconductor device |
| JP5556133B2 (en) * | 2009-03-31 | 2014-07-23 | 日立化成株式会社 | Liquid resin composition for electronic components and electronic component device |
-
2011
- 2011-02-03 JP JP2011021363A patent/JP4965715B1/en active Active
- 2011-08-02 CN CN201180065777.0A patent/CN103328530B/en active Active
- 2011-08-02 KR KR1020137019593A patent/KR101819264B1/en active IP Right Grant
- 2011-08-02 MY MYPI2013002887A patent/MY161359A/en unknown
- 2011-08-02 WO PCT/JP2011/067640 patent/WO2012105072A1/en active Application Filing
- 2011-08-05 TW TW100127977A patent/TWI547520B/en active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI602874B (en) * | 2012-12-27 | 2017-10-21 | 納美仕有限公司 | Liquid epoxy resin composition |
| TWI582125B (en) * | 2013-01-17 | 2017-05-11 | Sekisui Chemical Co Ltd | Method for manufacturing hardened anisotropic conductive material, connecting structure and connecting structure for electronic parts |
| CN104072947A (en) * | 2013-03-26 | 2014-10-01 | 太阳油墨制造株式会社 | Epoxy resin composition, composition for filling in hole plugging, and printed wiring board using same |
| TWI760225B (en) * | 2021-05-13 | 2022-04-01 | 大陸商蘇州震坤科技有限公司 | Encapsulating resin to reduce encapsulation delamination |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012105072A1 (en) | 2012-08-09 |
| KR101819264B1 (en) | 2018-01-16 |
| CN103328530A (en) | 2013-09-25 |
| CN103328530B (en) | 2016-01-13 |
| TWI547520B (en) | 2016-09-01 |
| MY161359A (en) | 2017-04-14 |
| KR20140009296A (en) | 2014-01-22 |
| JP4965715B1 (en) | 2012-07-04 |
| JP2012158730A (en) | 2012-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201233725A (en) | Epoxy resin composition and semiconductor-sealing material using the same | |
| TWI650370B (en) | Soft epoxy resin composition | |
| EP3127933B1 (en) | Heat-curable epoxy resin composition | |
| JPWO2009142065A1 (en) | Epoxy resin composition for sealing electronic parts | |
| TW201936776A (en) | One-component resin composition having better adhesive strength against stresses | |
| TW201233730A (en) | Semiconductor resin-molding material | |
| TW201925339A (en) | Curable composition based on fatty-acid modified epoxy resins and curing agents | |
| TWI707884B (en) | Resin composition | |
| TW201723073A (en) | Liquid epoxy resin composition | |
| WO2017057019A1 (en) | Epoxy resin composition | |
| JP5736122B2 (en) | Structural adhesive | |
| JP2012077214A (en) | Epoxy resin composition and semiconductor device using the same | |
| JP2000198831A (en) | Epoxy resin composition and sealing of lsi using the composition | |
| TWI542628B (en) | One-component type epoxy resin composition | |
| JP2016147946A (en) | Resin composition, film, substrate, semiconductor device, adhesive material for thermal transfer roll and office equipment | |
| EP3257898B1 (en) | Epoxy resin composition | |
| TWI593768B (en) | Film for package of pre-installed type semiconductor | |
| JP5593259B2 (en) | Liquid epoxy resin composition | |
| JP5647769B2 (en) | COF sealing resin composition | |
| JP5086678B2 (en) | Liquid semiconductor encapsulant and semiconductor device encapsulated using the same | |
| JP2015117361A (en) | Resin composition for semiconductor encapsulation | |
| JP7217865B2 (en) | Wafer level package encapsulation resin composition | |
| JP6837237B2 (en) | Die bonding agent | |
| JP2012056979A (en) | Epoxy resin composition | |
| JP2005350618A (en) | Liquefied epoxy resin composition and semiconductor device |