TW201402634A - Curable epoxy resin composition - Google Patents

Curable epoxy resin composition Download PDF

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TW201402634A
TW201402634A TW102120043A TW102120043A TW201402634A TW 201402634 A TW201402634 A TW 201402634A TW 102120043 A TW102120043 A TW 102120043A TW 102120043 A TW102120043 A TW 102120043A TW 201402634 A TW201402634 A TW 201402634A
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resin composition
epoxy resin
curable epoxy
acrylic polymer
group
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TW102120043A
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TWI579312B (en
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Hirose Suzuki
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Daicel Corp
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    • 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
    • C08G59/26—Di-epoxy compounds heterocyclic
    • 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
    • C08G59/40—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • 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

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Led Device Packages (AREA)

Abstract

The present invention is intended to provide a curable epoxy resin composition capable of forming a cured article having high heat resistance, light resistance and thermal shock resistance, and in particular, advancing high temperature electrification characteristic and moisture/reflow resistance of a photo semiconductor device. The curable epoxy resin composition according to the present invention is characterized by including an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B) represented by following Formula (1), and a hydrogenated trimellitic anhydride (C) represented by following Formula (2). [wherein, R1, R2 independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.] [wherein, R11 to R13 independently represent a hydrogen atom or an alkyl group. R14 represents a hydrogen atom or a counter ion.]

Description

硬化性環氧樹脂組成物 Curable epoxy resin composition

本發明涉及硬化性環氧樹脂組成物、將該硬化性環氧樹脂組成物硬化所製得的硬化物、及利用該硬化性環氧樹脂組成物的硬化物封裝光半導體元件的光半導體裝置。 The present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, and an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the curable epoxy resin composition.

近年來，正在發展光半導體裝置的高輸出化，在這種光半導體裝置中被覆光半導體元件的樹脂(封裝材)，要求高耐熱性、耐光性。過去，作為用於形成耐熱性高的封裝材的封裝劑，例如，已知有包含異三聚氰酸單烯丙基二縮水甘油酯(monoally diglycidyl isocyanurate)與雙酚A型環氧樹脂的組成物(參照專利文獻1)。然而，在使用上述組成物作為高輸出的藍色、白色光半導體用的封裝劑的情況下，因從光半導體元件所發出的光及熱持續造成封裝材的著色，而吸收了本來要被輸出的光，結果，產生了從光半導體裝置所輸出的光的光度隨著時間經過而降低的問題。 In recent years, the output of optical semiconductor devices has been increasing, and the resin (packaging material) that covers the optical semiconductor device in such an optical semiconductor device requires high heat resistance and light resistance. In the past, as an encapsulant for forming a heat-resistant packaging material, for example, a composition comprising monoally diglycidyl isocyanurate and a bisphenol A type epoxy resin is known. (refer to Patent Document 1). However, when the above composition is used as a high-output encapsulant for blue and white photo-semiconductors, the light and heat generated from the optical semiconductor element continue to cause coloring of the encapsulant, and the absorption is originally intended to be output. As a result, the problem that the luminosity of the light output from the optical semiconductor device decreases as time passes is generated.

作為形成具有高耐熱性及耐光性、難以變黃的硬化物(封裝材)的封裝劑，已知有：3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯、3,4-環氧環己基甲基(3,4- 環氧)環己烷羧酸酯、及ε-己內酯的加成物、1,2,8,9-二環氧檸檬烯等具有脂環骨架之液狀脂環式環氧樹脂。但是，這些脂環式環氧樹脂的硬化物不耐各種應力，在施加如冷熱循環(週期性地重複加熱及冷卻)的熱衝撃的情況下，會產生發生龜裂(裂紋)等問題。 As an encapsulant for forming a cured product (packaging material) having high heat resistance and light resistance and being difficult to yellow, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate is known. Acid ester, 3,4-epoxycyclohexylmethyl (3,4- A liquid alicyclic epoxy resin having an alicyclic skeleton such as an epoxy group of a cyclohexane carboxylate and an ε-caprolactone adduct or a 1,2,8,9-diepoxylimene. However, the cured product of these alicyclic epoxy resins is not resistant to various stresses, and when hot pressing such as a cycle of cooling and heating (repetitive heating and cooling is repeated periodically), problems such as occurrence of cracks (cracks) occur.

又，光半導體裝置(例如，表面安裝型的光半導體裝置)，一般會經歷為了利用焊接將光半導體裝置的電極接合在配線基板的回流製程(reflow process)。近年來，作為當作接合材的焊料，變得使用熔點高的無鉛焊料，使得回流製程的加熱處理變得更高溫(例如，尖峰溫度為240~260℃)。這種狀況下，在過去的光半導體裝置中，會因回流製程的加熱處理而產生如：封裝材從光半導體裝置的導線框(lead frame)剝離、封裝材發生龜裂等的劣化問題。 Further, an optical semiconductor device (for example, a surface mount type optical semiconductor device) generally undergoes a reflow process for bonding electrodes of an optical semiconductor device to a wiring substrate by soldering. In recent years, as a solder used as a bonding material, a lead-free solder having a high melting point has been used, so that the heat treatment of the reflow process is made higher (for example, the peak temperature is 240 to 260 ° C). In such a situation, in the conventional optical semiconductor device, the deterioration of the package material from the lead frame of the optical semiconductor device and the cracking of the package material occur due to the heat treatment of the reflow process.

因此，光半導體裝置中的封裝材，除了高耐熱性、耐光性以外，還要求即使在施加熱衝擊的情況下仍難以發生龜裂的特性(有時稱為「耐熱衝擊性」)、及即使在回流製程中受到加熱處理時仍難以發生龜裂或剝離的特性。尤其是近年來，基於確保封裝材更高可靠性的觀點，要求：即使在使光半導體裝置，在高濕條件下放置一定時間(例如，在30℃、70%RH的條件下168小時；在60℃、60%RH的條件下40小時等)吸濕後，經回流製程加熱處理的情況下，仍難以發生上述的龜裂或剝離(有時稱這種特性為「耐吸濕回流性」)。 Therefore, in addition to high heat resistance and light resistance, the package material in the optical semiconductor device is required to have a property of being less likely to be cracked even when a thermal shock is applied (sometimes referred to as "thermal shock resistance"), and even It is still difficult to crack or peel when subjected to heat treatment in the reflow process. In particular, in recent years, based on the viewpoint of ensuring higher reliability of the package material, it is required to leave the optical semiconductor device under high-humidity conditions for a certain period of time (for example, 168 hours at 30 ° C, 70% RH; 60 ° C, 60% RH, 40 hours, etc.) After moisture absorption, the above-mentioned cracking or peeling is hard to occur in the case of heat treatment by a reflow process (this characteristic is sometimes referred to as "water absorption reflow resistance") .

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1 日本特開2000-344867號公報 Patent Document 1 Japanese Patent Laid-Open Publication No. 2000-344867

因此，本發明的目的係提供一種硬化性環氧樹脂組成物，其能形成具有高耐熱性、耐光性、及耐熱衝擊性，尤其是能使光半導體裝置在高溫下的通電特性及耐吸濕回流性提升的硬化物。 Accordingly, an object of the present invention is to provide a curable epoxy resin composition capable of forming high heat resistance, light resistance, and thermal shock resistance, and in particular, capable of energizing characteristics and moisture absorption reflow of an optical semiconductor device at a high temperature. Sexually enhanced hardened matter.

又，本發明的其他目的係提供一種硬化物，其可具有高耐熱性、耐光性、及耐熱衝擊性，尤其是能使光半導體裝置在高溫下的通電特性及耐吸濕回流性提升。 Further, another object of the present invention is to provide a cured product which can have high heat resistance, light resistance, and thermal shock resistance, and in particular, can improve electric conduction characteristics and moisture absorption reflow resistance of an optical semiconductor device at a high temperature.

又，本發明的其他目的在於提供一種光半導體裝置，其在高溫下的通電特性優良，還可抑制在被保管在高濕條件下後，經回流製程加熱處理的情況下的光度降低等的劣化，耐久性及品質高。 Further, another object of the present invention is to provide an optical semiconductor device which is excellent in electric conduction characteristics at a high temperature, and can suppress deterioration of luminosity or the like in the case of heat treatment by a reflow process after being stored in a high-humidity condition. , high durability and quality.

本發明人，為了解決上述課題而銳意檢討，結果發現：含有脂環式環氧化合物、異三聚氰酸單烯丙基二縮水甘油酯化合物、及氫化偏苯三酸酐或其衍生物的硬化性環氧樹脂組成物，能形成具有高耐熱性、耐光性、及耐熱衝擊性，尤其是能使光半導體裝置在高溫下的通電特性及耐吸濕回流性提升的硬化物，而完成了本發明。 The present inventors have intensively reviewed in order to solve the above problems, and as a result, have found that a curable epoxy compound containing an alicyclic epoxy compound, a isocyanuric acid monoallyl diglycidyl ester compound, and a hydrogenated trimellitic anhydride or a derivative thereof The resin composition can form a cured product having high heat resistance, light resistance, and thermal shock resistance, and in particular, an electric current characteristic and an improved moisture absorption reflow resistance of an optical semiconductor device can be improved, and the present invention has been completed.

即，本發明提供一種硬化性環氧樹脂組成物，其特徵為包含：脂環式環氧化合物(A)、由下述式(1) That is, the present invention provides a curable epoxy resin composition characterized by comprising: an alicyclic epoxy compound (A), which is represented by the following formula (1)

[式中，R1、R2分別表示氫原子或碳數1~8的烷基。] In the formula, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

表示的異三聚氰酸單烯丙基二縮水甘油酯化合物(B)、及由下述式(2) The isocyanuric acid monoallyl diglycidyl ester compound (B) represented by the following formula (2)

[式中，R11~R13分別表示氫原子或烷基。R14表示氫原子或對離子。] [wherein R 11 to R 13 each represent a hydrogen atom or an alkyl group. R 14 represents a hydrogen atom or a counter ion. ]

表示的氫化偏苯三酸酐(C)。 Hydrogenated trimellitic anhydride (C) represented.

進一步地，提供一種前述硬化性環氧樹脂組成物，其中脂環式環氧化合物(A)係具有環氧環己烷基的化合物。 Further, there is provided a curable epoxy resin composition according to the invention, wherein the alicyclic epoxy compound (A) is a compound having an epoxycyclohexane group.

進一步地，提供一種前述硬化性環氧樹脂組成物，其中脂環式環氧化合物(A)係由下述式(I-1)表示的化合物 Further, a curable epoxy resin composition is provided, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (I-1)

進一步地，提供一種前述硬化性環氧樹脂組成物，其包含在分子內具有2個以上的環氧基的矽氧烷衍生物。 Further, there is provided a curable epoxy resin composition comprising a fluorene oxide derivative having two or more epoxy groups in a molecule.

進一步地，提供一種前述硬化性環氧樹脂組成物，其包含脂環式聚酯樹脂。 Further, a curable epoxy resin composition comprising the alicyclic polyester resin is provided.

進一步地，提供一種前述硬化性環氧樹脂組成物，其包含橡膠粒子。 Further, there is provided a curable epoxy resin composition comprising rubber particles.

進一步地，提供一種前述硬化性環氧樹脂組成物，其包含溶解度參數(Fedors法)為19.5~21.5[MPa1/2]的核殼型丙烯酸聚合物(acrylic polymer)粒子。 Further, there is provided a curable epoxy resin composition comprising a core-shell type acrylic polymer particle having a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa 1/2 ].

進一步地，提供一種前述硬化性環氧樹脂組成物，其中構成前述核殼型丙烯酸聚合物粒子的核的丙烯酸聚合物的玻璃轉移溫度為60~120℃，構成殼的丙烯酸聚合物的玻璃轉移溫度為60~120℃。 Further, there is provided a curable epoxy resin composition, wherein an acrylic polymer constituting a core of the core-shell type acrylic polymer particles has a glass transition temperature of 60 to 120 ° C, and a glass transition temperature of the acrylic polymer constituting the shell It is 60~120 °C.

進一步地，提供一種前述硬化性環氧樹脂組成物，其中相對於脂環式環氧化合物(A)100重量份，前述核殼型丙烯酸聚合物粒子的含有量為1~30重量份。 Further, the curable epoxy resin composition is characterized in that the content of the core-shell type acrylic polymer particles is from 1 to 30 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A).

進一步地，提供一種前述硬化性環氧樹脂組成物，其包含硬化劑(D)及硬化促進劑(E)。 Further, there is provided a curable epoxy resin composition comprising a hardener (D) and a hardening accelerator (E).

進一步地，提供一種前述硬化性環氧樹脂組成物，其包含硬化觸媒(F)。 Further, a curable epoxy resin composition comprising the hardening catalyst (F) is provided.

又，本發明提供一種硬化物，係將前述硬化性環氧樹脂組成物硬化所製得。 Further, the present invention provides a cured product obtained by curing the curable epoxy resin composition.

進一步地，提供一種前述硬化性環氧樹脂組成物，其係光半導體封裝用樹脂組成物。 Further, a curable epoxy resin composition which is a resin composition for photo-semiconductor encapsulation is provided.

又，本發明提供一種光半導體裝置，係利用前述硬化性環氧樹脂組成物的硬化物來封裝光半導體元件。 Moreover, the present invention provides an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the curable epoxy resin composition.

本發明的硬化性環氧樹脂組成物，由於具有上述構成，因此能藉由使該樹脂組成物硬化，來形成可具有高耐熱性、耐光性、及耐熱衝擊性，尤其是能使光半導體裝置在高溫下的通電特性及耐吸濕回流性提升的硬化物。因此，在使用本發明的硬化性環氧樹脂組成物作為光半導體封裝用樹脂組成物的情況下，能製得尤其是在高溫的嚴酷條件下難以發生光度降低等的劣化，進一步地，即使在高濕條件下保管後，經回流製程加熱處理的情況下仍難以發生光度降低等的劣化，耐久性及品質高的光半導體裝置。 Since the curable epoxy resin composition of the present invention has the above-described configuration, it can be formed by curing the resin composition to have high heat resistance, light resistance, and thermal shock resistance, and in particular, can be used for an optical semiconductor device. The electric property at high temperature and the cured product which is improved in moisture absorption reflow resistance. Therefore, when the curable epoxy resin composition of the present invention is used as a resin composition for photo-semiconductor encapsulation, deterioration of luminosity or the like is less likely to occur particularly under severe conditions of high temperature, and further, even in After storage under high-humidity conditions, it is difficult to cause deterioration of luminosity or the like in the case of heat treatment by a reflow process, and an optical semiconductor device having high durability and high quality.

100‧‧‧反射器(光反射用樹脂組成物) 100‧‧‧Reflector (resin composition for light reflection)

101‧‧‧金屬配線 101‧‧‧Metal wiring

102‧‧‧光半導體元件 102‧‧‧Optical semiconductor components

103‧‧‧接合線 103‧‧‧bonding line

104‧‧‧硬化物(封裝材) 104‧‧‧ hardened materials (packaging materials)

第1圖係顯示利用本發明的硬化性環氧樹脂組成物的硬化物封裝光半導體元件的光半導體裝置之一實施形態的概略圖。左側的圖(a)係斜視圖，右側的圖(b)係剖面圖。 Fig. 1 is a schematic view showing an embodiment of an optical semiconductor device in which an optical semiconductor device is encapsulated by a cured material of a curable epoxy resin composition of the present invention. Figure (a) on the left is a perspective view, and Figure (b) on the right is a cross-sectional view.

第2圖係實施例的焊料耐熱性試驗中之光半導體裝置的表面溫度曲線(surface temperature profile)(兩次加熱處理當中一次的加熱處理的溫度曲線)的一個例子。 Fig. 2 is an example of a surface temperature profile of a photo-semiconductor device in the solder heat resistance test of the embodiment (a temperature profile of heat treatment for one of the two heating processes).

用於實施發明的形態 Form for implementing the invention <硬化性環氧樹脂組成物> <Curable epoxy resin composition>

本發明的硬化性環氧樹脂組成物，係至少包含以下成分的樹脂組成物：脂環式環氧化合物(A)、由下述式(1) The curable epoxy resin composition of the present invention is a resin composition containing at least the following components: an alicyclic epoxy compound (A), and the following formula (1)

[式中，R1、R2分別表示氫原子或碳數1~8的烷基。] In the formula, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

表示的異三聚氰酸單烯丙基二縮水甘油酯化合物(B)、及由下述式(2) The isocyanuric acid monoallyl diglycidyl ester compound (B) represented by the following formula (2)

[式中，R11~R13分別表示氫原子或烷基。R14表示氫原子或對離子。] [wherein R 11 to R 13 each represent a hydrogen atom or an alkyl group. R 14 represents a hydrogen atom or a counter ion. ]

表示的氫化偏苯三酸酐(C)。 Hydrogenated trimellitic anhydride (C) represented.

[脂環式環氧化合物(A)] [Cycloaliphatic epoxy compound (A)]

本發明的硬化性環氧樹脂組成物中的脂環式環氧化合物(A)，係在分子內(一分子中)至少具有脂環(脂肪族環)構造及環氧基的化合物。作為上述脂環式環氧化合物(A)，具體而言，可舉出：(i)具有以構成脂環之鄰接的2 個碳原子及氧原子所構成之環氧基(脂環環氧基)的化合物；(ii)環氧基直接以單鍵鍵結在脂環的化合物等。但是，脂環式環氧化合物(A)，係不包含後述之在分子內具有2個以上的環氧基之矽氧烷衍生物者。 The alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic ring) structure and an epoxy group in a molecule (in one molecule). Specific examples of the alicyclic epoxy compound (A) include (i) having a contiguous structure constituting an alicyclic ring. a compound having an epoxy group (alicyclic epoxy group) composed of a carbon atom and an oxygen atom; (ii) a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond. However, the alicyclic epoxy compound (A) does not include a nonoxyl derivative having two or more epoxy groups in the molecule to be described later.

作為上述之(i)具有以構成脂環之鄰接的2個碳原子及氧原子所構成之環氧基(脂環環氧基)的化合物，能從周知或慣用者當中任意地選擇來使用。其中，作為上述脂環環氧基，較佳為環氧環己烷基。 The compound (i) having an epoxy group (alicyclic epoxy group) composed of two carbon atoms and an oxygen atom adjacent to each other in the alicyclic ring can be arbitrarily selected from known or used. Among them, the alicyclic epoxy group is preferably an epoxycyclohexane group.

作為上述之(i)具有以構成脂環之鄰接的2個碳原子及氧原子所構成之環氧基的化合物，基於透明性、耐熱性的觀點，較佳為具有環氧環己烷基的化合物，特佳為，由下述式(I)表示的化合物(脂環式環氧化合物)。 The compound (i) having an epoxy group composed of two carbon atoms and oxygen atoms adjacent to each other in the alicyclic ring is preferably an epoxycyclohexane group from the viewpoint of transparency and heat resistance. The compound is particularly preferably a compound represented by the following formula (I) (alicyclic epoxy compound).

上述式(I)中，X表示單鍵或連接基團(具有1個以上原子之2價的基)。作為上述連接基團，可舉出例如：2價的烴基、羰基、醚鍵、酯鍵、碳酸酯基、醯胺基、及由複數個上述基團連接而成的基團等。 In the above formula (I), X represents a single bond or a linking group (having a divalent group of one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine group, and a group obtained by linking a plurality of the above groups.

作為上述式(I)中的X為單鍵的脂環式環氧化合物，可舉出3,4,3’,4’-二環氧雙環己烷等。 The alicyclic epoxy compound in which X in the above formula (I) is a single bond may, for example, be 3,4,3',4'-diepoxybicyclohexane.

作為上述2價的烴基，可舉出：碳數為1~18之直鏈或支鏈狀的伸烷基、2價的脂環式烴基等。作為碳數為1~18之直鏈或支鏈狀的伸烷基，可舉出例如：亞甲基、甲基亞甲基、二甲基亞甲基、伸乙基、伸丙基、 三亞甲基等。作為上述2價的脂環式烴基，可舉出例如：1,2-伸環戊基、1,3-伸環戊基、亞環戊基、1,2-伸環己基、1,3-伸環己基、1,4-伸環己基、亞環己基等2價的伸環烷基(包含亞環烷基)等。 Examples of the divalent hydrocarbon group include a linear or branched alkylene group having a carbon number of 1 to 18, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylidene group, and a propyl group. Trimethylene and the like. The divalent alicyclic hydrocarbon group may, for example, be a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-extended cyclohexyl group, or a 1,3- A divalent cycloalkyl group (including a cycloalkylene group) such as a cyclohexyl group, a 1,4-cyclohexylene group or a cyclohexylene group.

作為上述連接基團X，特佳為含有氧原子的連接基團，具體而言，可舉出：-CO-、-O-CO-O-、-COO-、-O-、-CONH-；由複數個上述連接基團連接而成的基團；由1個或2個以上的上述連接基團與1個或2個以上的2價的烴基連接而成的基團等。作為2價的烴基，可舉出上述例示者。 The linking group X is particularly preferably a linking group containing an oxygen atom, and specific examples thereof include -CO-, -O-CO-O-, -COO-, -O-, -CONH-; a group obtained by linking a plurality of the above-mentioned linking groups; a group obtained by linking one or two or more of the above-mentioned linking groups to one or two or more divalent hydrocarbon groups. Examples of the divalent hydrocarbon group include the above-mentioned examples.

作為由上述式(I)表示的脂環式環氧化合物的代表例，可舉出由下述式(I-1)~(I-10)表示的化合物等。又，下述式(I-5)、(I-7)中的l、m分別表示1~30的整數。下述式(I-5)中的R係碳數1~8的伸烷基，可舉出：亞甲基、伸乙基、伸丙基、伸異丙基、伸丁基、伸異丁基、s-伸丁基、伸戊基、伸己基、伸庚基、伸壬基等直鏈或支鏈狀伸烷基。它們當中，較佳為亞甲基、伸乙基、伸丙基、伸異丙基等碳數1~3的直鏈或支鏈狀伸烷基。下述式(I-9)、(I-10)中的n1~n6分別表示1~30的整數。 Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10). Further, l and m in the following formulas (I-5) and (I-7) each represent an integer of 1 to 30. In the following formula (I-5), R is an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an exoethyl group, a propyl group, an isopropyl group, a butyl group, and an extended butyl group. A straight or branched alkyl group such as a benzyl group, an s-butylene group, a pentyl group, a hexyl group, a heptyl group or a decyl group. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methylene group, an ethyl group, a propyl group and an isopropyl group is preferable. In the following formulas (I-9) and (I-10), n1 to n6 each represent an integer of 1 to 30.

作為上述(ii)環氧基直接以單鍵鍵結在脂環的化合物，可舉出例如由下述式(II)表示的化合物。 The compound represented by the following formula (II) is exemplified as the compound in which the (ii) epoxy group is directly bonded to the alicyclic ring by a single bond.

式(II)中，R’係從p價的醇除去p個-OH的基，p、n表示自然數。作為p價的醇[R’-(OH)p]，可舉出：2,2-雙(羥甲基)-1-丁醇等的多元醇等(碳數1~15的醇等)。p較佳為1~6，n較佳為1~30。在p為2以上的情況，在各自的( )內(圓括弧內)的基之n可以是相同的也可以是不同的。作為上述化合物，具體而言，可舉出：2,2-雙(羥甲基)-1-丁醇的1,2-環氧-4-(2-環氧乙基)環己烷加成物、商品名「EHPE3150」(DAICEL(股)製)等。 In the formula (II), R' is a group in which p-OH groups are removed from a p-valent alcohol, and p and n represent natural numbers. The p-valent alcohol [R'-(OH) p ] may, for example, be a polyol such as 2,2-bis(hydroxymethyl)-1-butanol or the like (an alcohol having 1 to 15 carbon atoms). p is preferably from 1 to 6, and n is preferably from 1 to 30. In the case where p is 2 or more, n of the bases in the respective ( ) (in parentheses) may be the same or different. Specific examples of the above compound include 1,2-epoxy-4-(2-epoxyethyl)cyclohexane addition of 2,2-bis(hydroxymethyl)-1-butanol. The product name is "EHPE3150" (DAICEL system).

在本發明的硬化性環氧樹脂組成物中，脂環式環氧化合物(A)係能單獨使用一種或組合兩種以上來使用。又，作為上述脂環式環氧化合物(A)，亦能使用例如：商品名「CELLOXIDE 2021P」、「CELLOXIDE 2081」(以上，DAICEL(股)製)等市售品。 In the curable epoxy resin composition of the present invention, the alicyclic epoxy compound (A) can be used singly or in combination of two or more. In addition, as the alicyclic epoxy compound (A), for example, commercially available products such as "CELLOXIDE 2021P" and "CELLOXIDE 2081" (above, DAICEL) can be used.

作為上述脂環式環氧化合物(A)，特佳為由上述式(I-1)表示的3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯、商品名「CELLOXIDE 2021P」(DAICEL(股)製)。 The alicyclic epoxy compound (A) is particularly preferably 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate represented by the above formula (I-1). The product name is "CELLOXIDE 2021P" (DAICEL (share) system).

本發明的硬化性環氧樹脂組成物中的脂環式環氧化合物(A)的含有量(調配量)並未特別限定，但相 對於硬化性環氧樹脂組成物(100重量%)，較佳為10~95重量%，更佳為15~90重量%，又更佳為20~85重量%。若脂環式環氧化合物(A)的含有量超出上述範圍，則硬化物的耐熱性及耐光性可能變得不足。 The content (mixing amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but the phase The curable epoxy resin composition (100% by weight) is preferably 10 to 95% by weight, more preferably 15 to 90% by weight, still more preferably 20 to 85% by weight. When the content of the alicyclic epoxy compound (A) is outside the above range, the heat resistance and light resistance of the cured product may become insufficient.

又，本發明的硬化性環氧樹脂組成物中的脂環式環氧化合物(A)的含有量(調配量)並未特別限定，但在本發明的硬化性環氧樹脂組成物包含硬化劑(D)作為必要成分的情況下，相對於硬化性環氧樹脂組成物(100重量%)，較佳為10~90重量%，更佳為15~80重量%，又更佳為20~70重量%。另一方面，在本發明的硬化性環氧樹脂組成物包含硬化觸媒(F)作為必要成分的情況下，脂環式環氧化合物(A)的含有量(調配量)，相對於硬化性環氧樹脂組成物(100重量%)，較佳為25~95重量%，更佳為30~90重量%，又更佳為35~90重量%。 In addition, the content (mixing amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but the curable epoxy resin composition of the present invention contains a hardener. (D) In the case of an essential component, it is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, still more preferably 20 to 70%, based on the curable epoxy resin composition (100% by weight). weight%. On the other hand, when the curable epoxy resin composition of the present invention contains a curing catalyst (F) as an essential component, the content (adjusted amount) of the alicyclic epoxy compound (A) is relative to the curability. The epoxy resin composition (100% by weight) is preferably 25 to 95% by weight, more preferably 30 to 90% by weight, still more preferably 35 to 90% by weight.

脂環式環氧化合物(A)的含有量(調配量)相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物的總量(全環氧化合物)(100重量%)並未特別限定，但較佳為20~95重量%，更佳為30~92重量%，又更佳是40~90重量%。脂環式環氧化合物(A)的含有量低於20重量%，則硬化物的耐熱性、耐光性、耐熱衝擊性、耐吸濕回流性可能降低。 The content (adjusted amount) of the alicyclic epoxy compound (A) is not related to the total amount (all epoxy compound) (100% by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. It is particularly limited, but is preferably 20 to 95% by weight, more preferably 30 to 92% by weight, still more preferably 40 to 90% by weight. When the content of the alicyclic epoxy compound (A) is less than 20% by weight, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be lowered.

[異三聚氰酸單烯丙基二縮水甘油酯化合物(B)] [Iso-cyanuric acid monoallyl diglycidyl ester compound (B)]

本發明的硬化性環氧樹脂組成物中的異三聚氰酸單烯丙基二縮水甘油酯化合物(B)，係由下述式(1)表示的化 合物。異三聚氰酸單烯丙基二縮水甘油酯化合物(B)，尤其是擔負使硬化物的韌性提高、使耐熱衝擊性或耐吸濕回流性(尤其是在吸濕後的回流製程的加熱處理中的耐龜裂性(難以產生龜裂的特性))提高的任務。 The isocyanuric acid monoallyl diglycidyl ester compound (B) in the curable epoxy resin composition of the present invention is represented by the following formula (1) Compound. The isocyanuric acid monoallyl diglycidyl ester compound (B) is particularly responsible for improving the toughness of the cured product, and imparting thermal shock resistance or moisture absorption reflow resistance (especially heat treatment after reflow treatment after moisture absorption) The task of improving crack resistance (characteristics that are difficult to produce cracks).

上述式(1)中，R1及R2分別表示氫原子或碳數1~8的烷基。作為碳數1~8的烷基，可舉出例如：甲基、乙基、丙基、異丙基、丁基、異丁基、s-丁基、戊基、己基、庚基、辛基等直鏈或支鏈狀的烷基。其中，較佳為甲基、乙基、丙基、異丙基等碳數1~3的直鏈或支鏈狀的烷基。上述式(1)中的R1及R2特佳為氫原子。 In the above formula (1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. A straight or branched alkyl group. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. R 1 and R 2 in the above formula (1) are particularly preferably a hydrogen atom.

作為異三聚氰酸單烯丙基二縮水甘油酯化合物(B)的代表例，可舉出：異三聚氰酸單烯丙基二縮水甘油酯、1-烯丙基-3,5-雙(2-甲基環氧丙基)異三聚氰酸酯、異三聚氰酸1-(2-甲基丙烯基)-3,5-二縮水甘油酯、1-(2-甲基丙烯基)-3,5-雙(2-甲基環氧丙基)異三聚氰酸酯等。又，異三聚氰酸單烯丙基二縮水甘油酯化合物(B)能單獨使用一種或組合兩種以上來使用。 Typical examples of the isocyanuric acid monoallyl diglycidyl ester compound (B) include isocyanuric acid monoallyl diglycidyl ester and 1-allyl-3,5- Bis(2-methylepoxypropyl)isomeric cyanurate, 1-(2-methylpropenyl)-3,5-diglycidyl isocyanate, 1-(2-methyl Propenyl)-3,5-bis(2-methylepoxypropyl)isocyanate or the like. Further, the isocyanuric acid monoallyl diglycidyl ester compound (B) can be used alone or in combination of two or more.

又，上述異三聚氰酸單烯丙基二縮水甘油酯化合物(B)亦可添加醇或酸酐等與環氧基反應的化合物進行預先改性來使用。 Further, the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) may be used by previously adding a compound which reacts with an epoxy group such as an alcohol or an acid anhydride.

上述異三聚氰酸單烯丙基二縮水甘油酯化合物(B)的含有量(調配量)，並未特別限定，但相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物的總量(100重量%)，較佳為5~60重量%，更佳為8~55重量%，又更佳為10~50重量%。若異三聚氰酸單烯丙基二縮水甘油酯化合物(B)的含有量超過60重量%，則異三聚氰酸單烯丙基二縮水甘油酯化合物(B)之硬化性環氧樹脂組成物中的溶解性可能降低，而對硬化物的物性造成不良影響。另一方面，若異三聚氰酸單烯丙基二縮水甘油酯化合物(B)的含有量低於5重量%，則硬化物的耐熱衝擊性或耐吸濕回流性可能會降低。 The content (adjusted amount) of the above isomeric cyanuric acid monoallyl diglycidyl ester compound (B) is not particularly limited, but is a compound having an epoxy group contained in the curable epoxy resin composition. The total amount (100% by weight) is preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight. If the content of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) exceeds 60% by weight, the hardening epoxy resin of the isocyanuric acid monoallyl diglycidyl ester compound (B) The solubility in the composition may be lowered, which adversely affects the physical properties of the cured product. On the other hand, when the content of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) is less than 5% by weight, the thermal shock resistance or moisture absorption reflow resistance of the cured product may be lowered.

又，異三聚氰酸單烯丙基二環氧丙酯化合物(B)的含有量(調配量)相對於脂環式環氧化合物(A)與異三聚氰酸單烯丙基二縮水甘油酯化合物(B)的合計量(100重量%)並未特別限定，但較佳為5~60重量%，更佳為8~55重量%，又更佳為10~50重量%。若異三聚氰酸單烯丙基二縮水甘油酯化合物(B)的含有量超過60重量%，則異三聚氰酸單烯丙基二縮水甘油酯化合物(B)之硬化性環氧樹脂組成物中的溶解性可能降低，而對硬化物的物性造成不良影響。另一方面，若異三聚氰酸單烯丙基二縮水甘油酯化合物(B)的含有量低於5重量%，則硬化物的耐熱衝擊性或耐吸濕回流性可能會降低。 Further, the content (mixing amount) of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) is relative to the alicyclic epoxy compound (A) and the isomeric cyanuric acid monoallyl dimethyl condensed water. The total amount (100% by weight) of the glyceride compound (B) is not particularly limited, but is preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight. If the content of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) exceeds 60% by weight, the hardening epoxy resin of the isocyanuric acid monoallyl diglycidyl ester compound (B) The solubility in the composition may be lowered, which adversely affects the physical properties of the cured product. On the other hand, when the content of the isomeric cyanuric acid monoallyl diglycidyl ester compound (B) is less than 5% by weight, the thermal shock resistance or moisture absorption reflow resistance of the cured product may be lowered.

[氫化偏苯三酸酐(C)] [Hydrogenated trimellitic anhydride (C)]

本發明的硬化性環氧樹脂組成物中的氫化偏苯三酸酐(C)，係由下述式(2)表示的化合物(環己烷-1,2,4-三羧 酸-1,2-酐或其衍生物)。氫化偏苯三酸酐(C)，尤其是擔負使硬化物的耐熱衝擊性或耐吸濕回流性(尤其是在吸濕後的回流製程的加熱處理中的耐龜裂性(難以產生龜裂的特性)或電極剝離難以發生的特性)提高的任務。 The hydrogenated trimellitic anhydride (C) in the curable epoxy resin composition of the present invention is a compound represented by the following formula (2) (cyclohexane-1,2,4-tricarboxylate) Acid-1,2-anhydride or a derivative thereof). Hydrogenated trimellitic anhydride (C), in particular, is responsible for the thermal shock resistance or moisture repellency of the cured product (especially the crack resistance (characteristic of cracking) in the heat treatment of the reflow process after moisture absorption) or the electrode The task of improving the characteristics that are difficult to occur).

上述式(2)中的R11~R13(R11、R12、及R13)分別表示氫原子或烷基。作為上述烷基，可舉出例如：甲基、乙基、丙基、異丙基、丁基、異丁基、s-丁基、戊基、己基、庚基、辛基等碳數1~8的烷基(直鏈或支鏈狀的烷基)等。其中，作為上述R11~R13，較佳為氫原子、碳數1~3的烷基，更佳為氫原子。特佳為R11~R13皆為氫原子。 R 11 to R 13 (R 11 , R 12 and R 13 ) in the above formula (2) each represent a hydrogen atom or an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. An alkyl group (linear or branched alkyl group) of 8. In particular, the above R 11 to R 13 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom. Particularly preferably, R 11 to R 13 are each a hydrogen atom.

上述式(2)中的R14表示氫原子或對離子(對陽離子(counter cation))。上述對離子，係藉由R14為氫原子的氫化偏苯三酸酐(C)及鹼性化合物所形成的鹽中、因上述鹼性化合物所引起的對離子(羧酸離子的對離子)。作為上述鹼性化合物，可舉出周知或慣用的鹼，並未特別限定，但可舉出例如：氫氧化鈉、氫氧化鉀、氫氧化鋰、氨等無機鹼；甲胺、二甲胺、三乙胺、乙胺、n-丙胺、單乙醇胺、三乙醇胺、吡啶等有機鹼等。 R 14 in the above formula (2) represents a hydrogen atom or a counter ion (counter cation). The counter ion is a counter ion (a counter ion of a carboxylic acid ion) caused by the above basic compound in a salt formed by hydrogenation of trimellitic anhydride (C) and a basic compound in which R 14 is a hydrogen atom. The basic compound is not particularly limited as long as it is a conventionally known or customary base, and examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia; methylamine and dimethylamine. An organic base such as triethylamine, ethylamine, n-propylamine, monoethanolamine, triethanolamine or pyridine.

本發明的硬化性環氧樹脂組成物中的氫化偏苯三酸酐(C)，能單獨使用一種，亦能組合兩種以上使用。 The hydrogenated trimellitic anhydride (C) in the curable epoxy resin composition of the present invention may be used alone or in combination of two or more.

氫化偏苯三酸酐(C)，能利用周知或慣用方法製造，其製造方法並未特別限定，但例如，能藉由利用周知慣用的方法將由下述式(2’)表示的化合物(偏苯三酸酐或其衍生物)氫化(核氫化)來製造。又，在本發明中，作為氫化偏苯三酸酐(C)，能使用商品名「H-TMAn」(三菱化學(股)製)等市售品。 The hydrogenated trimellitic anhydride (C) can be produced by a known method or a conventional method, and the production method is not particularly limited. For example, a compound represented by the following formula (2') (trimellitic anhydride or a derivative thereof) can be used by a conventionally known method. ) Hydrogenation (nuclear hydrogenation) to manufacture. In the present invention, a commercially available product such as "H-TMAn" (manufactured by Mitsubishi Chemical Corporation) can be used as the hydrogenated trimellitic anhydride (C).

[式(2’)中，R11~R14與前述相同。] [In the formula (2'), R 11 to R 14 are the same as described above. ]

氫化偏苯三酸酐(C)的含有量(調配量)並未特別限定，但相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物總量(100重量份)，較佳為0.1~60重量份，更佳為1~50重量份，又更佳為10~45重量份。若氫化偏苯三酸酐(C)的含有量超過60重量份，則可能硬化物著色而色相惡化。另一方面，若氫化偏苯三酸酐(C)的含有量低於0.1重量份，則硬化物的耐熱衝擊性或耐吸濕回流性可能降低。 The content (adjusted amount) of the hydrogenated trimellitic anhydride (C) is not particularly limited, but is preferably 0.1 to 60 with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. The parts by weight are more preferably 1 to 50 parts by weight, still more preferably 10 to 45 parts by weight. When the content of the hydrogenated trimellitic anhydride (C) exceeds 60 parts by weight, the cured product may be colored and the hue may be deteriorated. On the other hand, when the content of the hydrogenated trimellitic anhydride (C) is less than 0.1 part by weight, the thermal shock resistance or moisture absorption reflow resistance of the cured product may be lowered.

[硬化劑(D)] [hardener (D)]

本發明的硬化性環氧樹脂組成物亦可包含硬化劑(D)。上述硬化劑(D)，係具有使具有環氧基的化合物硬 化之作用的化合物。作為上述硬化劑(D)，能使用周知或慣用硬化劑作為環氧樹脂用硬化劑。作為上述硬化劑(D)，其中較佳為在25℃下為液狀的酸酐，可舉出例如：甲基四氫酞酸酐、甲基六氫酞酸酐、十二烯基琥珀酸酐、甲基內亞甲基四氫酞酸酐等。又，對於例如酞酸酐、四氫酞酸酐、六氫酞酸酐、甲基環己烯二羧酸酐等在常溫(約25℃)下為固體狀的酸酐，亦能藉由使其溶解於在常溫(約25℃)下為液狀的酸酐而作成液狀的混合物，而適合作為本發明中的硬化劑(D)使用。又，硬化劑(D)能單獨使用一種或組合兩種以上來使用。如上述，作為上述硬化劑(D)，基於硬化物的耐熱性、耐光性、耐龜裂性的觀點，較佳為飽和單環烴二羧酸的酐(亦包含烷基等取代基鍵結於環者)。又，硬化劑(D)係不含上述氫化偏苯三酸酐(C)者。 The curable epoxy resin composition of the present invention may also contain a hardener (D). The above hardener (D) has a compound having an epoxy group hard a compound that acts. As the curing agent (D), a known or conventional curing agent can be used as the curing agent for the epoxy resin. The curing agent (D) is preferably an acid anhydride which is liquid at 25 ° C, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, and methyl group. Internal methylene tetrahydrophthalic anhydride and the like. Further, for example, an acid anhydride which is solid at room temperature (about 25 ° C) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylcyclohexene dicarboxylic anhydride can be dissolved in the normal temperature. It is a liquid mixture in the form of a liquid acid anhydride (about 25 ° C), and is suitably used as the curing agent (D) in the present invention. Further, the curing agent (D) can be used singly or in combination of two or more. As described above, the curing agent (D) is preferably an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including a substituent such as an alkyl group) from the viewpoint of heat resistance, light resistance, and crack resistance of the cured product. Yu Huan). Further, the curing agent (D) is one which does not contain the above-mentioned hydrogenated trimellitic anhydride (C).

又，在本發明中，作為硬化劑(D)，亦能使用商品名「Rikacid MH-700」(新日本理化(股)製)、「Rikacid MH-700F」(新日本理化(股)製)、商品名「HN-5500」(日立化成工業(股)製)等市售品。 In the present invention, as the curing agent (D), the product name "Rikacid MH-700" (manufactured by Nippon Chemical and Chemical Co., Ltd.) and "Rikacid MH-700F" (manufactured by Nippon Chemical and Chemical Co., Ltd.) can be used. Commercial product such as "HN-5500" (Hitachi Chemical Industry Co., Ltd.).

硬化劑(D)的含有量(調配量)並未特別限定，但相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物總量(100重量份)，較佳為0~100重量份，更佳為0~50重量份。若含有量高於100重量份，則可能硬化物著色而色相惡化。 The content (adjusted amount) of the curing agent (D) is not particularly limited, but is preferably 0 to 100 with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. The parts by weight are more preferably 0 to 50 parts by weight. If the content is more than 100 parts by weight, the cured product may be colored and the hue may be deteriorated.

本發明的硬化性環氧樹脂組成物中的氫化偏苯三酸酐(C)及硬化劑(D)的含有量的合計(合計含有 量)並未特別限定，但相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物總量(100重量份)，較佳為10~100重量份，更佳為20~75重量份。更具體而言，相對於硬化性環氧樹脂組成物所含之全部的具有環氧基的化合物中一當量的環氧基，較佳為以成為0.5~1.5當量的比例使用。若上述合計含有量低於10重量份，則硬化變得不充分，有硬化物的強韌性降低的傾向。另一方面，若上述合計含有量高於100重量份，則可能硬化物著色而色相惡化。 The total content of the hydrogenated trimellitic anhydride (C) and the curing agent (D) in the curable epoxy resin composition of the present invention (total of The amount is not particularly limited, but is preferably 10 to 100 parts by weight, more preferably 20 to 75 parts by weight, based on the total amount of the epoxy group-containing compound (100 parts by weight) contained in the curable epoxy resin composition. Share. More specifically, it is preferable to use one equivalent of the epoxy group in the epoxy group-containing compound contained in the curable epoxy resin composition in a ratio of 0.5 to 1.5 equivalents. When the total content is less than 10 parts by weight, the curing tends to be insufficient, and the toughness of the cured product tends to decrease. On the other hand, when the total content is more than 100 parts by weight, the cured product may be colored and the hue may be deteriorated.

又，在使用硬化劑(D)的情況下，相對於氫化偏苯三酸酐(C)及硬化劑(D)的含有量的合計(合計含有量)(100重量%)，氫化偏苯三酸酐(C)的比例並未特別限定，但較佳為10重量%以上(例如，10~100重量%)，更佳為20重量%以上(例如，20~100重量%)，又更佳為30重量%以上。若氫化偏苯三酸酐(C)的比例低於10重量%，則硬化物的耐熱衝擊性或耐吸濕回流性可能降低。 In addition, when the curing agent (D) is used, the ratio of hydrogenated trimellitic anhydride (C) is proportional to the total (the total content) of the hydrogenated trimellitic anhydride (C) and the curing agent (D) (100% by weight). It is not particularly limited, but is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20% by weight or more (for example, 20 to 100% by weight), still more preferably 30% by weight or more. If the proportion of the hydrogenated trimellitic anhydride (C) is less than 10% by weight, the thermal shock resistance or moisture absorption reflow resistance of the cured product may be lowered.

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

本發明的硬化性環氧樹脂組成物，亦可包含硬化促進劑(E)。上述硬化促進劑(E)，係當具有環氧基的化合物因氫化偏苯三酸酐(C)或硬化劑(D)而硬化時，具有促進硬化速度的功能的化合物。作為硬化促進劑(E)，能使用周知或慣用的硬化促進劑，可舉出例如：1,8-二氮雜雙環[5.4.0]十一碳-7烯(DBU)或其鹽(例如，酚鹽、辛酸鹽、p-甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽)；1,5-二氮雜雙環[4.3.0]壬-5烯(DBN)或其鹽(例如，酚鹽、辛酸鹽、 p-甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽)；苄基二甲基胺、2,4,6-參(二甲基胺基甲基)苯酚、N,N-二甲基環己胺等3級胺；2-乙基-4-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑等咪唑類；磷酸酯、三苯基膦等膦類；四苯基鏻四(p-甲苯基)硼酸鹽等鏻化合物；辛酸鋅或辛酸錫等有機金屬鹽；金屬螯合物等。硬化促進劑(E)，能單獨使用一種或組合兩種以上來使用。 The curable epoxy resin composition of the present invention may further contain a hardening accelerator (E). The hardening accelerator (E) is a compound having a function of promoting the curing rate when the compound having an epoxy group is cured by hydrogenation of trimellitic anhydride (C) or a curing agent (D). As the hardening accelerator (E), a known or conventional hardening accelerator can be used, and examples thereof include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or a salt thereof (for example) , phenate, octanoate, p-toluenesulfonate, formate, tetraphenylborate); 1,5-diazabicyclo[4.3.0]non-5ene (DBN) or a salt thereof (for example Phenol, octoate, P-tosylate, formate, tetraphenyl borate); benzyldimethylamine, 2,4,6-glucos(dimethylaminomethyl)phenol, N,N-dimethyl a tertiary amine such as cyclohexylamine; an imidazole such as 2-ethyl-4-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphine such as a phosphate ester or a triphenylphosphine; An anthracene compound such as tetraphenylphosphonium tetrakis(p-tolyl)borate; an organic metal salt such as zinc octylate or tin octylate; a metal chelate compound or the like. The hardening accelerator (E) can be used alone or in combination of two or more.

又，在本發明中，作為硬化促進劑(E)，亦能使用商品名「U-CAT SA 506」、「U-CAT SA 102」、「U-CAT 5003」、「U-CAT 18X」、「12XD」(開發品)(以上，SAN-APRO(股)製)；「TPP-K」、「TPP-MK」(以上，北興化學工業(股)製)；商品名「PX-4ET」(日本化學工業(股)製)等市售品。 Further, in the present invention, as the curing accelerator (E), the trade names "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", and the like can be used. "12XD" (developed product) (above, SAN-APRO (share) system); "TPP-K", "TPP-MK" (above, Beixing Chemical Industry Co., Ltd.); trade name "PX-4ET" ( Commercial products such as the Japan Chemical Industry Co., Ltd.).

上述硬化促進劑(E)的含有量(調配量)並未特別限定，相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物的總量(100重量份)，較佳為0.01~5重量份，更佳為0.03~3重量份，又更佳為0.03~2重量份。若硬化促進劑(E)的含有量低於0.01重量份，則硬化促進效果可能變得不充分。另一方面，若硬化促進劑(E)的含有量超過5重量份，則可能硬化物著色而色相惡化。 The content (adjusted amount) of the hardening accelerator (E) is not particularly limited, and is preferably 0.01 with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. ~5 parts by weight, more preferably 0.03 to 3 parts by weight, still more preferably 0.03 to 2 parts by weight. When the content of the hardening accelerator (E) is less than 0.01 parts by weight, the hardening promoting effect may be insufficient. On the other hand, when the content of the hardening accelerator (E) exceeds 5 parts by weight, the cured product may be colored and the hue may be deteriorated.

[硬化觸媒(F)] [hardening catalyst (F)]

本發明的硬化性環氧樹脂組成物，亦可進一步(例如取代硬化劑(D)及硬化促進劑(E))包含硬化觸媒(F)。上述硬化觸媒(F)係具有開始及/或促進具有環氧基的化合物的硬化反應之功能的化合物。作為上述硬化觸媒(F)並未 特別限定，但可舉出藉由施加紫外線照射或加熱處理來產生陽離子活性種(cationic species)，使聚合開始的陽離子觸媒(陽離子聚合開始劑)。又，硬化觸媒(F)能單獨使用一種，或能組合兩種以上使用。 The curable epoxy resin composition of the present invention may further contain a curing catalyst (F) (for example, a substituted curing agent (D) and a curing accelerator (E)). The above-mentioned curing catalyst (F) is a compound having a function of starting and/or promoting a hardening reaction of a compound having an epoxy group. As the above hardening catalyst (F) Although it is especially limited, a cationic catalyst (cationic polymerization initiator) which generates a cationic active species by application of ultraviolet irradiation or heat treatment and starts polymerization can be mentioned. Further, the curing catalyst (F) may be used singly or in combination of two or more.

作為利用紫外線照射來產生陽離子活性種的陽離子觸媒，可舉出例如：六氟銻酸鹽、五氟羥基銻酸鹽、六氟磷酸鹽、六氟砷酸鹽等。作為上述的陽離子觸媒，亦能適宜地使用例如：商品名「UVACURE1590」(DAICEL CYTEC(股)製)；商品名「CD-1010」、「CD-1011」、「CD-1012」(以上，美國SARTOMER製)；商品名「Irgacure 264」(Ciba Japan(股)製)；商品名「CTI-1682」(日本曹達(股)製)等市售品。 Examples of the cationic catalyst that generates a cationic active species by ultraviolet irradiation include hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, and hexafluoroarsenate. As the above-mentioned cationic catalyst, for example, the product name "UVACURE 1590" (manufactured by DAICEL CYTEC Co., Ltd.); trade names "CD-1010", "CD-1011", and "CD-1012" can be suitably used (above, American SARTOMER system; trade name "Irgacure 264" (manufactured by Ciba Japan Co., Ltd.); and commercial product such as "CTI-1682" (made by Japan Soda Co., Ltd.).

作為利用施加加熱處理來產生陽離子活性種的陽離子觸媒，可舉出例如：芳基重氮鹽、芳基碘鎓鹽、芳基鋶鹽、丙二烯-離子配位化合物等，能適宜地使用商品名「PP-33」、「CP-66」、「CP-77」(ADEKA(股)製)；商品名「FC-509」(3M製)；商品名「UVE1014」(G.E.製)；商品名「San-Aid SI-60L」、「San-Aid SI-80L」、「San-Aid SI-100L」、「San-Aid SI-110L」、「San-Aid SI-150L」(三新化學工業(股)製)；商品名「CG-24-61」(Ciba Japan製)等市售品。進一步地，亦可為鋁或鈦等金屬和乙醯乙酸或二酮類的螯合物與三苯基矽醇等矽醇形成的化合物，或，鋁或鈦等金屬和乙醯乙酸或二酮類的螯合物與雙酚S等酚類形成的化合物。 Examples of the cationic catalyst that generates a cationically active species by applying a heat treatment include an aryldiazonium salt, an aryl iodonium salt, an arylsulfonium salt, a propadiene-ionic complex compound, and the like. The trade names "PP-33", "CP-66", "CP-77" (made by ADEKA), the trade name "FC-509" (made by 3M), and the product name "UVE1014" (made by GE); Trade names "San-Aid SI-60L", "San-Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-110L", "San-Aid SI-150L" (Sanshin Chemical Industrial (stock) system; a commercial item such as "CG-24-61" (manufactured by Ciba Japan). Further, it may be a compound of a metal such as aluminum or titanium and a chelate compound of acetonitrile acetic acid or a diketone and a sterol such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and acetonitrile acetic acid or diketone. A compound of a chelate compound and a phenol such as bisphenol S.

硬化觸媒(F)的含有量(調配量)並未特別限定，相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物的總量(100重量份)，較佳為0.01~15重量份，更佳為0.01~12重量份，又更佳為0.05~10重量份，特佳為0.05~8重量份。能藉由在上述範圍內使用硬化觸媒(F)，來製得耐熱性、耐光性、透明性優良的硬化物。 The content (adjusted amount) of the curing catalyst (F) is not particularly limited, and is preferably 0.01% based on the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight. By using the curing catalyst (F) within the above range, a cured product excellent in heat resistance, light resistance, and transparency can be obtained.

[脂環式聚酯樹脂] [Cycloester Polyester Resin]

本發明的硬化性環氧樹脂組成物，亦可進一步包含脂環式聚酯樹脂。藉由含有上述脂環式聚酯樹脂，尤其是硬化物的耐熱性、耐光性提升，存在更加抑制光半導體裝置的光度降低的傾向。上述脂環式聚酯樹脂係至少具有脂環構造(脂肪族環構造)的聚酯樹脂。尤其是基於提升硬化物的耐熱性、耐光性的觀點，上述脂環式聚酯樹脂較佳為在主鏈具有脂環(脂環構造)的脂環式聚酯樹脂。 The curable epoxy resin composition of the present invention may further comprise an alicyclic polyester resin. When the alicyclic polyester resin is contained, in particular, heat resistance and light resistance of the cured product are improved, and the illuminance of the optical semiconductor device is further suppressed from decreasing. The alicyclic polyester resin is a polyester resin having at least an alicyclic structure (aliphatic ring structure). In particular, the alicyclic polyester resin is preferably an alicyclic polyester resin having an alicyclic ring (alicyclic structure) in the main chain, from the viewpoint of heat resistance and light resistance of the cured product.

作為脂環式聚酯樹脂中的脂環構造並未特別限定，但可舉出例如：單環烴構造或交聯環烴構造(例如，二環系烴等)等。其中，特佳為脂環骨架(碳-碳鍵)全部以碳-碳單鍵所構成的飽和單環烴構造或飽和交聯環烴構造。又，上述脂環式聚酯樹脂中的脂環構造，可只導入構成脂環式聚酯樹脂之來自二羧酸的構成單元與來自二醇的構成單元中任一者，亦可兩者皆導入，並未特別限定。 The alicyclic structure in the alicyclic polyester resin is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure or a crosslinked cyclic hydrocarbon structure (for example, a bicyclic hydrocarbon). Among them, a saturated monocyclic hydrocarbon structure or a saturated crosslinked cyclic hydrocarbon structure in which all of the alicyclic skeleton (carbon-carbon bond) is composed of a carbon-carbon single bond is particularly preferable. Further, the alicyclic structure in the alicyclic polyester resin may be introduced into only one of a constituent unit derived from a dicarboxylic acid and a constituent unit derived from a diol which constitute an alicyclic polyester resin, or both. Import is not particularly limited.

上述脂環式聚酯樹脂具有來自具有脂環構造的單體成分之構成單元。作為具有上述脂環構造的單 體，可舉出周知或慣用的具有脂環構造的二醇或二羧酸，並未特別限定，但可舉出例如：1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、4-甲基-1,2-環己烷二羧酸、腐殖酸(himic acid)、1,4-十氫萘二羧酸、1,5-十氫萘二羧酸、2,6-十氫萘二羧酸、2,7-十氫萘二羧酸等具有脂環構造的二羧酸(亦包含酸酐等衍生物)等；1,2-環戊二醇、1,3-環戊二醇、1,2-環戊二甲醇、1,3-環戊二甲醇、雙(羥甲基)三環[5.2.1.0]癸烷等5元環二醇、1,2-環己烷二醇、1,3-環己烷二醇、1,4-環己烷二醇、1,2-環己烷二甲醇、1,3-環己烷二甲醇、1,4-環己烷二甲醇、2,2-雙-(4-羥基環己基)丙烷等6元環二醇、氫化雙酚A等具有脂環構造的二醇(亦包含它們的衍生物)等。 The above alicyclic polyester resin has a constituent unit derived from a monomer component having an alicyclic structure. As a single having the above alicyclic structure The diol or dicarboxylic acid having a condensed ring structure which is known or conventionally used is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid and 1,3-cyclohexane. Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, humic acid, 1,4-decahydronaphthalene dicarboxylic acid, a dicarboxylic acid having an alicyclic structure such as 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid (including a derivative such as an acid anhydride) ; 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentanemethanol, 1,3-cyclopentanemethanol, bis(hydroxymethyl)tricyclo[5.2.1.0] 5-membered cyclohexane such as decane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1 a 6-membered cyclic diol such as 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or 2,2-bis-(4-hydroxycyclohexyl)propane, or hydrogenated bisphenol A having an alicyclic structure Glycols (including their derivatives) and the like.

上述脂環式聚酯樹脂，亦可具有來自不具有脂環構造的單體成分之構成單元。作為上述不具有脂環構造的單體成分，可舉出例如：對酞酸、異酞酸、酞酸、萘二羧酸等芳香族二羧酸(亦包含酸酐等衍生物)；己二酸、癸二酸、壬二酸、琥珀酸、富馬酸、馬來酸等脂肪族二羧酸(亦包含酸酐等衍生物)；乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、3-甲基戊二醇、二乙二醇、3-甲基-1,5-戊二醇、2-甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、苯二甲基二醇、雙酚A的環氧乙烷加成物、雙酚A的環氧丙烷加成物等二醇(亦包含它們的衍生物)等。又，上述不具有脂環構造的二羧酸或二醇鍵結有適當的取代基(例如，烷 基、烷氧基、鹵素原子等)者，亦包含在不具有脂環構造的單體。 The alicyclic polyester resin may have a constituent unit derived from a monomer component having no alicyclic structure. Examples of the monomer component having no alicyclic structure include aromatic dicarboxylic acids such as p-citric acid, isophthalic acid, decanoic acid, and naphthalene dicarboxylic acid (including derivatives such as acid anhydrides); and adipic acid. , adipic acid, sebacic acid, succinic acid, fumaric acid, maleic acid and other aliphatic dicarboxylic acids (including derivatives such as acid anhydride); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3- Propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol Alcohol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl- A diol (including a derivative thereof) such as 1,3-propanediol, benzene dimethyl glycol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A. Further, the above dicarboxylic acid or diol having no alicyclic structure is bonded with an appropriate substituent (for example, an alkane A group having no alicyclic structure is also included in the group, alkoxy group, halogen atom or the like.

具有脂環之單體單元相對於構成上述脂環式聚酯樹脂的總單體單元(總單體成分)(100莫耳%)的比例並未特別限定，較佳為10莫耳%以上(例如，10~80莫耳%)，更佳為25~70莫耳%，又更佳為30~60莫耳%。若具有脂環的單體單元的比例低於10莫耳%，則硬化物的耐熱性、耐光性、耐熱衝擊性、耐吸濕回流性可能會降低。 The ratio of the monomer unit having an alicyclic ring to the total monomer unit (total monomer component) (100 mol%) constituting the alicyclic polyester resin is not particularly limited, and is preferably 10 mol% or more ( For example, 10 to 80 mol%), more preferably 25 to 70 mol%, and even more preferably 30 to 60 mol%. When the proportion of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be lowered.

作為上述脂環式聚酯樹脂，特佳為包含至少一種以上的由下述式(3)~(5)表示的構成單元之脂環式聚酯樹脂。 The alicyclic polyester resin is particularly preferably an alicyclic polyester resin containing at least one or more constituent units represented by the following formulas (3) to (5).

[式中，R3表示直鏈、支鏈、或環狀的碳數2~15的伸烷基。又，R4~R7各自獨立地表示氫原子、或直鏈或支鏈狀的碳數1~4的烷基，從R4~R7所選出的兩個可鍵結而形成環。] [wherein, R 3 represents a linear, branched, or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 4 to R 7 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R 4 to R 7 may be bonded to form a ring. ]

[式中，R3表示直鏈、支鏈、或環狀的碳數2~15的伸烷基。又，R4~R7各自獨立地表示氫原子、或直鏈或支鏈狀的碳數1~4的烷基，從R4~R7所選出的兩個可鍵結而形成環。] [wherein, R 3 represents a linear, branched, or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 4 to R 7 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R 4 to R 7 may be bonded to form a ring. ]

[式中，R3表示直鏈、支鏈、或環狀的碳數2~15的伸烷基。又，R4~R7各自獨立地表示氫原子、或直鏈或支鏈狀的碳數1~4的烷基，從R4~R7所選出的兩個可鍵結而形成環。] [wherein, R 3 represents a linear, branched, or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 4 to R 7 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two selected from R 4 to R 7 may be bonded to form a ring. ]

作為由上述式(3)~(5)表示的構成單元的較佳具體例，可舉出例如，由下述式(6)表示的來自4-甲基-1,2-環己烷二羧酸及乙二醇的構成單元。具有該構成單元的脂環式聚酯樹脂，例如，可藉由將甲基六氫酞酸酐與乙二醇聚縮合來製得。 Preferred examples of the structural unit represented by the above formulas (3) to (5) include, for example, 4-methyl-1,2-cyclohexanedicarboxylate represented by the following formula (6). A constituent unit of acid and ethylene glycol. The alicyclic polyester resin having such a constituent unit can be obtained, for example, by polycondensing methyl hexahydrophthalic anhydride with ethylene glycol.

又，作為由上述式(3)~(5)表示的構成單元的其他較佳具體例，可舉出例如：由下述式(7)表示的來自1,4-環己烷二羧酸及新戊二醇的構成單元。具有該構成單元的脂環式聚酯樹脂，例如，可藉由將1,4-環己烷二羧酸與新戊二醇聚縮合來製得。 In addition, as another preferable specific example of the structural unit represented by the above formula (3) to (5), for example, 1,4-cyclohexanedicarboxylic acid represented by the following formula (7) and A constituent unit of neopentyl glycol. The alicyclic polyester resin having such a constituent unit can be obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid with neopentyl glycol.

在上述脂環式聚酯樹脂具有由上述式(3)~(5)表示的構成單元的情況下，該構成單元的含有量的合計量(合計含有量；構成該構成單元的總單體單元)並未特別限定，但相對於脂環式聚酯樹脂的總構成單元(100莫耳%；構成脂環式聚酯樹脂的總單體單元)，較佳為20莫耳%以上(例如，20~100莫耳%)，更佳為50~100莫耳%，又更佳為80~100莫耳%。若由上述式(3)~(5)表示的構成單元的含有量低於20莫耳%，則硬化物的耐熱性、耐光性、耐熱衝擊性、耐吸濕回流性可能降低。 In the case where the alicyclic polyester resin has the constituent units represented by the above formulas (3) to (5), the total content of the constituent units (the total content; the total monomer unit constituting the constituent unit) It is not particularly limited, but is preferably 20 mol% or more with respect to the total constituent unit (100 mol%; total monomer unit constituting the alicyclic polyester resin) of the alicyclic polyester resin (for example, 20~100% by mole), more preferably 50~100% by mole, and even more preferably 80~100% by mole. When the content of the constituent unit represented by the above formulas (3) to (5) is less than 20 mol%, heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be lowered.

上述脂環式聚酯樹脂的數量平均分子量並未特別限定，但較佳為300~100000，更佳為300~30000。 若脂環式聚酯樹脂的數量平均分子量低於300，則硬化物的強韌性不足，耐熱衝擊性或耐吸濕回流性可能降低。另一方面，若脂環式聚酯樹脂的數量平均分子量超過100000，則與氫化偏苯三酸酐(C)或硬化劑(D)的相溶性降低，硬化物的透明性可能降低。又，脂環式聚酯樹脂的數量平均分子量，例如，能利用GPC(凝膠滲透層析)法，測定出以標準聚苯乙烯換算的值。 The number average molecular weight of the above alicyclic polyester resin is not particularly limited, but is preferably from 300 to 100,000, more preferably from 300 to 30,000. If the number average molecular weight of the alicyclic polyester resin is less than 300, the toughness of the cured product is insufficient, and the thermal shock resistance or the moisture absorption reflow resistance may be lowered. On the other hand, when the number average molecular weight of the alicyclic polyester resin exceeds 100,000, the compatibility with the hydrogenated trimellitic anhydride (C) or the curing agent (D) is lowered, and the transparency of the cured product may be lowered. Further, the number average molecular weight of the alicyclic polyester resin can be measured, for example, by a GPC (gel permeation chromatography) method in terms of standard polystyrene.

又，上述脂環式聚酯樹脂能單獨使用一種或組合兩種以上使用。 Further, the alicyclic polyester resin may be used alone or in combination of two or more.

上述脂環式聚酯樹脂，並未特別限定，能利用周知或慣用方法製造。更詳細而言，例如，可藉由利用常用的方法使上述二羧酸與二醇聚縮合來製得上述脂環式聚酯樹脂，亦可藉由利用常用的方法使上述的二羧酸的衍生物(酸酐、酯、酸鹵化物等)與二醇聚縮合來製得上述脂環式聚酯樹脂。 The alicyclic polyester resin is not particularly limited and can be produced by a known method or a conventional method. More specifically, for example, the above alicyclic polyester resin can be obtained by polycondensing the above dicarboxylic acid with a diol by a usual method, and the above dicarboxylic acid can also be obtained by a usual method. The above-mentioned alicyclic polyester resin is obtained by polycondensation of a derivative (an acid anhydride, an ester, an acid halide, etc.) with a diol.

又，上述脂環式聚酯樹脂的含有量(調配量)相對於脂環式環氧化合物(A)100重量份並未特別限定，但較佳為5~50重量份，更佳為10~45重量份，又更佳為15~40重量份。若脂環式聚酯樹脂的含有量低於5重量份，則硬化物的耐熱性、耐光性、耐熱衝擊性、耐吸濕回流性可能變得不足。另一方面，若脂環式聚酯樹脂的含有量超過50重量份，則硬化物的耐熱衝擊性、耐吸濕回流性可能降低。 Further, the content (adjusted amount) of the alicyclic polyester resin is not particularly limited, and is preferably 5 to 50 parts by weight, more preferably 10 parts, per 100 parts by weight of the alicyclic epoxy compound (A). 45 parts by weight, more preferably 15 to 40 parts by weight. When the content of the alicyclic polyester resin is less than 5 parts by weight, the heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be insufficient. On the other hand, when the content of the alicyclic polyester resin exceeds 50 parts by weight, the thermal shock resistance and moisture absorption reflow resistance of the cured product may be lowered.

[在分子內具有2個以上的環氧基的矽氧烷衍生物] [a siloxane derivative having two or more epoxy groups in the molecule]

本發明的硬化性環氧樹脂組成物，亦可進一步包含在分子內(一分子中)具有2個以上的環氧基的矽氧烷衍生物。藉由使其含有上述在分子內具有2個以上的環氧基的矽氧烷衍生物，尤其是能使硬化物的耐熱性、耐光性進一步提升至高水準。 The curable epoxy resin composition of the present invention may further contain a oxoxane derivative having two or more epoxy groups in a molecule (in one molecule). By containing the above-described oxoxane derivative having two or more epoxy groups in the molecule, the heat resistance and light resistance of the cured product can be further improved to a high level.

作為上述在分子內具有2個以上的環氧基的矽氧烷衍生物中的矽氧烷骨架(Si-O-Si骨架)，並未特別限定，但可舉出例如：環狀矽氧烷骨架；直鏈狀矽酮、或籠型或梯型的聚矽倍半氧烷(polysilsesqioxane)等聚矽氧烷骨架等。其中，作為上述矽氧烷骨架，基於使硬化物的耐熱性、耐光性提升、抑制光半導體裝置的光度降低的觀點，較佳為環狀矽氧烷骨架、直鏈狀矽酮骨架。即，作為在分子內具有2個以上的環氧基的矽氧烷衍生物，較佳為在分子內具有2個以上的環氧基的環狀矽氧烷、在分子內具有2個以上的環氧基的直鏈狀矽酮。又，在分子內具有2個以上的環氧基的矽氧烷衍生物能單獨使用一種或組合兩種以上來使用。 The oxime skeleton (Si-O-Si skeleton) in the oxoxane derivative having two or more epoxy groups in the molecule is not particularly limited, and examples thereof include a cyclic oxirane. Skeleton; linear fluorenone, or a polyoxane skeleton such as a cage or ladder type polysilsesqioxane. In particular, the naphthene skeleton is preferably a cyclic oxime skeleton or a linear fluorenone skeleton from the viewpoint of improving heat resistance and light resistance of the cured product and suppressing reduction in luminosity of the optical semiconductor device. In other words, the oxoxane derivative having two or more epoxy groups in the molecule is preferably a cyclic siloxane having two or more epoxy groups in the molecule, and two or more molecules in the molecule. A linear fluorenone of an epoxy group. In addition, the oxoxane derivative having two or more epoxy groups in the molecule may be used alone or in combination of two or more.

在上述在分子內具有2個以上的環氧基的矽氧烷衍生物係具有2個以上的環氧基的環狀矽氧烷的情況，形成矽氧烷環的Si-O單元的數目(與形成矽氧烷環的矽原子的數目相等)並未特別限定，但基於使硬化物的耐熱性、耐光性提升的觀點，較佳為2~12，更佳為4~8。 In the case where the oxoxane derivative having two or more epoxy groups in the molecule is a cyclic siloxane having two or more epoxy groups, the number of Si-O units forming a siloxane ring ( The number of the ruthenium atoms forming the oxime ring is not particularly limited. From the viewpoint of improving the heat resistance and light resistance of the cured product, it is preferably 2 to 12, more preferably 4 to 8.

上述在分子內具有2個以上的環氧基的矽氧烷衍生物的重量平均分子量並未特別限定，但基於使硬化物的耐熱性、耐光性提升的觀點，較佳為100~3000，更佳為180~2000。 The weight average molecular weight of the above-described oxirane derivative having two or more epoxy groups in the molecule is not particularly limited, but is preferably from 100 to 3,000, more preferably from the viewpoint of improving heat resistance and light resistance of the cured product. Good for 180~2000.

上述在分子內具有2個以上的環氧基的矽氧烷衍生物之一分子中的環氧基的數目，只要是2個以上的話便未特別限定，但基於使硬化物的耐熱性、耐光性提升的觀點，較佳為2~4個(2個、3個、或4個)。 The number of the epoxy groups in the molecule of one of the oxoxane derivatives having two or more epoxy groups in the molecule is not particularly limited as long as it is two or more, but the heat resistance and light resistance of the cured product are based on The viewpoint of sexual improvement is preferably 2 to 4 (2, 3, or 4).

上述在分子內具有2個以上的環氧基的矽氧烷衍生物的環氧當量(依照JIS K7236)，並未特別限定，但基於使硬化物的耐熱性、耐光性提升的觀點，較佳為180~400，更佳為240~400，又更佳為240~350。 The epoxy equivalent of the above-described oxoxane derivative having two or more epoxy groups in the molecule is not particularly limited, and is preferably based on the viewpoint of improving the heat resistance and light resistance of the cured product. It is 180~400, more preferably 240~400, and even more preferably 240~350.

上述在分子內具有2個以上的環氧基的矽氧烷衍生物中的環氧基，並未特別限定，但基於使硬化物的耐熱性、耐光性提升的觀點，較佳為以構成脂肪族環的鄰接的2個碳原子及氧原子所構成的環氧基(脂環環氧基)，其中，特佳為環氧環己烷基。 The epoxy group in the oxoxane derivative having two or more epoxy groups in the molecule is not particularly limited, but is preferably composed of fat based on the viewpoint of improving heat resistance and light resistance of the cured product. An epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom of the group ring is particularly preferably an epoxycyclohexane group.

作為上述在分子內具有2個以上的環氧基的矽氧烷衍生物，具體而言，可舉出例如：2,4-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,4,6,6,8,8-六甲基-環四矽氧烷、4,8-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,2,4,6,6,8-六甲基-環四矽氧烷、2,4-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-6,8-二丙基-2,4,6,8-四甲基-環四矽氧烷、4,8-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,6-二丙基-2,4,6,8-四甲基-環四矽氧烷、2,4,8-三[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,4,6,6,8-五甲基-環四矽氧烷、2,4,8-三[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-6-丙基-2,4,6,8-四甲基-環四矽氧烷、2,4,6,8-四[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,4,6,8-四甲基-環 四矽氧烷、在分子內具有2個以上的環氧基的矽倍半氧烷等。更具體而言，可舉出例如：由下述式表示的在分子內具有2個以上的環氧基的環狀矽氧烷等。 Specific examples of the oxoxane derivative having two or more epoxy groups in the molecule include 2,4-di[2-(3-{oxabicyclo[4.1.0]g Base}) ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]g Base}) ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetraoxane, 2,4-di[2-(3-{oxabicyclo[4.1.0]g Base}) ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxabicyclo[4.1] .0]heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,8-tri[2-(3- {oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-tri[2-(3- {oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,6,8-tetra[ 2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclo Tetraoxane, a sesquisesquioxane having two or more epoxy groups in the molecule, and the like. More specifically, for example, a cyclic siloxane having two or more epoxy groups in the molecule represented by the following formula may be mentioned.

又，作為上述在分子內具有2個以上的環氧基的矽氧烷衍生物，亦能使用例如在特開2008-248169號公報所記載的含有脂環環氧基的矽酮樹脂、或在特開2008-19422號公報所記載的在一分子中具有至少2個環氧官能性基的有機聚矽倍半氧烷樹脂等。 In addition, as the oxime derivative having two or more epoxy groups in the molecule, for example, an oxiranone resin containing an alicyclic epoxy group described in JP-A-2008-248169, or An organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule as described in JP-A-2008-19422.

作為上述在分子內具有2個以上的環氧基的矽氧烷衍生物，亦能使用例如在分子內具有2個以上 的環氧基的環狀矽氧烷之商品名「X-40-2678」(信越化學工業(股)製)、商品名「X-40-2670」(信越化學工業(股)製)、商品名「X-40-2720」(信越化學工業(股)製)等市售品。 As the above-described oxoxane derivative having two or more epoxy groups in the molecule, for example, it is possible to use, for example, two or more molecules in the molecule. The product name "X-40-2678" (manufactured by Shin-Etsu Chemical Co., Ltd.), the trade name "X-40-2670" (manufactured by Shin-Etsu Chemical Co., Ltd.), and the product of the epoxy group-containing cyclic alkane. Commercial products such as "X-40-2720" (Shin-Etsu Chemical Co., Ltd.).

上述在分子內具有2個以上的環氧基的矽氧烷衍生物的含有量(調配量)並未特別限定，但相對於硬化性環氧樹脂組成物所含之具有環氧基的化合物總量(100重量%)，較佳為5~60重量%，更佳為8~55重量%，又更佳為10~50重量%，特佳為15~40重量%。若在分子內具有2個以上的環氧基的矽氧烷衍生物的含有量低於5重量%，則硬化物的耐熱性、耐光性可能變得不足。另一方面，若在分子內具有2個以上的環氧基的矽氧烷衍生物的含有量超過60重量%，則硬化物的耐熱衝擊性、耐吸濕回流性可能降低。 The content (adjusted amount) of the above-described oxoxane derivative having two or more epoxy groups in the molecule is not particularly limited, but is a total of the compound having an epoxy group contained in the curable epoxy resin composition. The amount (100% by weight) is preferably 5 to 60% by weight, more preferably 8 to 55% by weight, still more preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight. When the content of the oxoxane derivative having two or more epoxy groups in the molecule is less than 5% by weight, the heat resistance and light resistance of the cured product may be insufficient. On the other hand, when the content of the oxoxane derivative having two or more epoxy groups in the molecule exceeds 60% by weight, the thermal shock resistance and moisture absorption reflow resistance of the cured product may be lowered.

又，上述在分子內具有2個以上的環氧基的矽氧烷衍生物的含有量(調配量)相對於脂環式環氧化合物(A)100重量份並未特別限定，但較佳為10~200重量份，更佳為20~180重量份，又更佳為30~150重量份，特佳為35~145重量份。若在分子內具有2個以上的環氧基的矽氧烷衍生物的含有量低於10重量份，則硬化物的耐熱性、耐光性、耐熱衝擊性、耐吸濕回流性可能變得不足。另一方面，若在分子內具有2個以上的環氧基的矽氧烷衍生物的含有量超過200重量份，則硬化物的耐熱衝擊性、耐吸濕回流性可能降低。 In addition, the content (adjusted amount) of the oxirane derivative having two or more epoxy groups in the molecule is not particularly limited, and is preferably limited to 100 parts by weight of the alicyclic epoxy compound (A). 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, still more preferably 30 to 150 parts by weight, particularly preferably 35 to 145 parts by weight. When the content of the oxoxane derivative having two or more epoxy groups in the molecule is less than 10 parts by weight, heat resistance, light resistance, thermal shock resistance, and moisture absorption reflow resistance of the cured product may be insufficient. On the other hand, when the content of the decane derivative having two or more epoxy groups in the molecule exceeds 200 parts by weight, the thermal shock resistance and moisture repellency of the cured product may be lowered.

[橡膠粒子] [Rubber particles]

本發明的硬化性環氧樹脂組成物亦可進一步包含橡膠粒子。作為上述橡膠粒子，可舉出例如：粒子狀NBR(丙烯腈-丁二烯橡膠)、反應性末端羧基NBR(CTBN)、無金屬NBR、粒子狀SBR(苯乙烯-丁二烯橡膠)等橡膠粒子。作為上述橡膠粒子，較佳為具有包含具橡膠彈性的核部分、及至少1層被覆該核部分的殼層的多層構造(核殼構造)的橡膠粒子。上述橡膠粒子，特佳以(甲基)丙烯酸酯作為必要單體成分的聚合物(polymer)所構成，在表面具有羥基及/或羧基(羥基及羧基的任一者或兩者)作為可與脂環式環氧化合物(A)等具有環氧基的化合物反應的官能基。在上述橡膠粒子的表面不存在羥基及/或羧基的情況，因冷熱循環等的熱衝擊，導致硬化物白濁而透明性降低，故而不佳。 The curable epoxy resin composition of the present invention may further comprise rubber particles. Examples of the rubber particles include rubbers such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). particle. The rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) including a core portion having rubber elasticity and a shell layer covering at least one layer of the core portion. The rubber particles are particularly preferably composed of a polymer having a (meth) acrylate as an essential monomer component, and have a hydroxyl group and/or a carboxyl group (either or both of a hydroxyl group and a carboxyl group) as a surface. A functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). When the hydroxyl group and/or the carboxyl group are not present on the surface of the rubber particles, the cured product is turbid due to thermal shock such as a heat cycle, and the transparency is lowered, which is not preferable.

上述橡膠粒子中構成具有橡膠彈性的核部分的聚合物，並未特別限定，但較佳為以(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等(甲基)丙烯酸酯作為必要的單體成分。除此之外，上述構成具有橡膠彈性的核部分的聚合物，亦可包含例如苯乙烯、α-甲基苯乙烯等芳香族乙烯、丙烯腈、甲基丙烯腈等腈、丁二烯、異戊二烯等共軛二烯、乙烯、丙烯、異丁烯等作為單體成分。 The polymer constituting the core portion having rubber elasticity in the rubber particles is not particularly limited, but is preferably methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate ( Methyl) acrylate is an essential monomer component. In addition, the polymer constituting the rubber-elastic core portion may contain, for example, an aromatic vinyl such as styrene or α-methylstyrene, a nitrile such as acrylonitrile or methacrylonitrile, butadiene or the like. A conjugated diene such as pentadiene, ethylene, propylene or isobutylene is used as a monomer component.

其中，上述構成具有橡膠彈性的核部分的聚合物，作為單體成分，較佳為與(甲基)丙烯酸酯一起，將選自包含芳香族乙烯、腈及共軛二烯的群組的一種或 兩種以上組合者。即，作為上述構成核部分的聚合物，可舉出例如：(甲基)丙烯酸酯/芳香族乙烯、(甲基)丙烯酸酯/共軛二烯等二元共聚物；(甲基)丙烯酸酯/芳香族乙烯/共軛二烯等三元共聚物等。又，上述構成核部分的聚合物，亦可包含聚二甲基矽氧烷或聚苯基甲基矽氧烷等矽酮或聚胺基甲酸酯等。 Here, the polymer constituting the core portion having rubber elasticity is preferably a monomer component selected from the group consisting of aromatic vinyl, nitrile and conjugated diene together with (meth) acrylate. or Two or more combinations. In other words, examples of the polymer constituting the core portion include a binary copolymer such as (meth) acrylate/aromatic ethylene or (meth) acrylate/conjugated diene; and (meth) acrylate. a terpolymer such as an aromatic vinyl/conjugated diene or the like. Further, the polymer constituting the core portion may include an anthrone or a polyurethane such as polydimethyl siloxane or polyphenylmethyl siloxane.

上述構成核部分的聚合物，作為其他的單體成分，亦可含有二乙烯苯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、馬來酸二烯丙酯、三聚氰酸三烯丙酯、酞酸二烯丙酯、丁二醇二丙烯酸酯等在一單體(一分子)中含有具有2個以上的反應性官能基的反應***聯單體。 The polymer constituting the core portion may contain, as another monomer component, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diallyl maleate, The trially crosslinked monomer having two or more reactive functional groups is contained in one monomer (one molecule) such as triallyl cyanurate, diallyl citrate, butanediol diacrylate.

上述橡膠粒子的核部分，其中，由(甲基)丙烯酸酯/芳香族乙烯的二元共聚物(尤其是丙烯酸丁酯/苯乙烯)所構成的核部分，基於能容易地調整橡膠粒子的折射率的觀點為較佳。 a core portion of the above rubber particles, wherein a core portion composed of a (meth) acrylate/aromatic ethylene binary copolymer (particularly butyl acrylate/styrene) is capable of easily adjusting the refractive index of the rubber particles. The rate of view is preferred.

上述構成橡膠粒子的核部分的聚合物的玻璃轉移溫度並未特別限定，但較佳為低於60℃(例如，-150℃以上、低於60℃)，更佳為-150~15℃，又更佳為-100~0℃。若上述聚合物的玻璃轉移溫度為60℃以上，則硬化物的耐龜裂性(對各種應力難以產生龜裂的特性)可能降低。又，上述構成核部分的聚合物的玻璃轉移溫度意指利用後述的Fox公式所算出的計算值，例如，能與後述的核殼型丙烯酸聚合物粒子中的丙烯酸聚合物(核)的玻璃轉移溫度同樣地測定。 The glass transition temperature of the polymer constituting the core portion of the rubber particles is not particularly limited, but is preferably lower than 60 ° C (for example, -150 ° C or higher and lower than 60 ° C), more preferably -150 to 15 ° C. More preferably -100~0 °C. When the glass transition temperature of the above polymer is 60° C. or higher, the crack resistance of the cured product (characteristic in which cracking is unlikely to occur for various stresses) may be lowered. In addition, the glass transition temperature of the polymer constituting the core portion is a calculated value calculated by the Fox equation described later, and can be, for example, a glass transition of an acrylic polymer (nucleus) in the core-shell type acrylic polymer particles to be described later. The temperature was measured in the same manner.

上述橡膠粒子的核部分，能以通常使用的方法製造，例如，能藉由將上述單體利用乳化聚合法聚合的方法等來製造。在乳化聚合法中，可將上述單體的總量一次性加入而聚合，亦可在將上述單體的一部分聚合後，將剩下的部分連續地或間斷地添加而聚合，還可使用晶種粒子的聚合方法。 The core portion of the rubber particles can be produced by a usual method, and can be produced, for example, by a method in which the above monomer is polymerized by an emulsion polymerization method. In the emulsion polymerization method, the total amount of the above monomers may be added in one time for polymerization, or after a part of the above monomers is polymerized, the remaining portion may be continuously or intermittently added to be polymerized, and crystals may also be used. A method of polymerizing particles.

上述構成橡膠粒子的殼層的聚合物，較佳為與上述構成核部分的聚合物為異種的聚合物。又如上述，上述殼層較佳為具有羥基及/或羧基作為可與脂環式環氧化合物(A)等具有環氧基的化合物反應的官能基。藉此，尤其是能使在與脂環式環氧化合物(A)的界面的接著性提升，對於使包含具有該殼層的橡膠粒子的硬化性環氧樹脂組成物硬化而成之硬化物，能使其發揮優良的耐龜裂性。又，亦能防止硬化物的玻璃轉移溫度降低。 The polymer constituting the shell layer of the rubber particles is preferably a polymer which is different from the polymer constituting the core portion. Further, as described above, the shell layer preferably has a hydroxyl group and/or a carboxyl group as a functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). In this way, in particular, it is possible to improve the adhesion to the interface with the alicyclic epoxy compound (A), and to harden the curable epoxy resin composition containing the rubber particles having the shell layer. It can make it perform excellent crack resistance. Further, it is also possible to prevent the glass transition temperature of the cured product from decreasing.

上述構成殼層的聚合物，較佳為包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等(甲基)丙烯酸酯作為必要的單體成分。例如，在使用丙烯酸丁酯作為上述核部分中的(甲基)丙烯酸酯的情況，作為構成殼層的聚合物的單體成分，較佳為使用丙烯酸丁酯以外的(甲基)丙烯酸酯(例如，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、甲基丙烯酸丁酯等)。作為除了(甲基)丙烯酸酯以外還可包含的單體成分，可舉出例如：苯乙烯、α-甲基苯乙烯等芳香族乙烯、丙烯腈、甲基丙烯腈等腈等。在上述橡膠粒子中，作為構成殼層的單體成分，較佳為與(甲基)丙烯酸酯一起，包含單獨的上述單體、或 組合兩種以上的上述單體，尤其是至少包含芳香族乙烯，在能容易調整上述橡膠粒子的折射率方面為較佳。 The polymer constituting the shell layer preferably contains a (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate as an essential monomer component. For example, when butyl acrylate is used as the (meth) acrylate in the core portion, it is preferred to use a (meth) acrylate other than butyl acrylate as a monomer component of the polymer constituting the shell layer. For example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl methacrylate, etc.). Examples of the monomer component which may be contained in addition to the (meth) acrylate include aromatic vinyl such as styrene or α-methylstyrene, nitrile such as acrylonitrile or methacrylonitrile. In the rubber particles, as the monomer component constituting the shell layer, it is preferable to contain the above-mentioned monomer alone or together with the (meth) acrylate. It is preferred to combine two or more kinds of the above monomers, in particular, at least aromatic vinyl, and to easily adjust the refractive index of the rubber particles.

進一步地，上述構成殼層的聚合物，作為單體成分，為了形成作為可與脂環式環氧化合物(A)等具有環氧基的化合物反應的官能基的羥基及/或羧基，較佳為含有：含有羥基的單體(例如，(甲基)丙烯酸2-羥基乙酯等之(甲基)丙烯酸羥基烷酯等)或含有羧基的單體(例如，(甲基)丙烯酸等的α,β-不飽和酸、馬來酸酐等的α,β-不飽和酸酐等)。 Further, the polymer constituting the shell layer is preferably a monomer component, and is preferably a hydroxyl group and/or a carboxyl group which is a functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). The monomer contains a hydroxyl group-containing monomer (for example, a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate) or a carboxyl group-containing monomer (for example, α such as (meth)acrylic acid. , α-β-unsaturated acid anhydride such as β-unsaturated acid or maleic anhydride, etc.).

上述橡膠粒子中的構成殼層的聚合物，作為單體成分，較佳為與(甲基)丙烯酸酯一起，包含選自上述單體的一種、或組合兩種以上。即，上述殼層，較佳為例如由(甲基)丙烯酸酯/芳香族乙烯/(甲基)丙烯酸羥基烷酯、(甲基)丙烯酸酯/芳香族乙烯/α,β-不飽和酸等三元共聚物等所構成的殼層。 The polymer constituting the shell layer in the rubber particles preferably contains one or a combination of two or more kinds selected from the above monomers together with the (meth) acrylate. That is, the shell layer is preferably made of, for example, (meth) acrylate/aromatic ethylene/hydroxyalkyl (meth) acrylate, (meth) acrylate/aromatic ethylene/α, β-unsaturated acid, or the like. a shell composed of a terpolymer or the like.

又，上述構成殼層的聚合物，作為其他的單體成分，與核部分同樣地，除了上述單體以外還可含有二乙烯苯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、馬來酸二烯丙酯、三聚氰酸三烯丙酯、酞酸二烯丙酯、丁二醇二丙烯酸酯等一單體(一分子)中具有2個以上的反應性官能基的反應***聯單體。 Further, the polymer constituting the shell layer may contain, as the other monomer component, divinylbenzene, allyl (meth)acrylate, or ethylene glycol dihydrate in addition to the above-mentioned monomers. More than two reactions in one monomer (one molecule) such as acrylate, diallyl maleate, triallyl cyanurate, diallyl citrate, butanediol diacrylate Reactive cross-linking monomer of a functional group.

上述構成橡膠粒子的殼層的聚合物的玻璃轉移溫度並未特別限定，但較佳為60~120℃，更佳為70~115℃。若上述聚合物的玻璃轉移溫度低於60℃，則硬化物的耐熱性可能降低。另一方面，若上述聚合物的 玻璃轉移溫度超過120℃，則硬化物的耐龜裂性可能降低。又，上述構成殼層的聚合物的玻璃轉移溫度意指利用後述的Fox公式所算出的計算值，例如，能與後述的核殼型丙烯酸聚合物粒子中的丙烯酸聚合物(核)的玻璃轉移溫度同樣地測定。 The glass transition temperature of the polymer constituting the shell layer of the rubber particles is not particularly limited, but is preferably 60 to 120 ° C, more preferably 70 to 115 ° C. If the glass transition temperature of the above polymer is lower than 60 ° C, the heat resistance of the cured product may be lowered. On the other hand, if the above polymer When the glass transition temperature exceeds 120 ° C, the crack resistance of the cured product may be lowered. In addition, the glass transition temperature of the polymer constituting the shell layer is a calculated value calculated by the Fox equation described later, and can be, for example, a glass transition of an acrylic polymer (nucleus) in a core-shell type acrylic polymer particle to be described later. The temperature was measured in the same manner.

上述橡膠粒子(具有核殼構造的橡膠粒子)，可藉由利用殼層被覆上述核部分來製得。作為以殼層被覆上述核部分的方法，能舉出例如：藉由在以上述方法所製得的具有橡膠彈性的核部分的表面，塗布構成殼層的共聚物來被覆的方法；以利用上述方法所製得的具有橡膠彈性的核部分作為主鏈成分、以構成殼層的各成分作為側鏈成分而進行接枝聚合的方法等。 The rubber particles (rubber particles having a core-shell structure) can be obtained by coating the core portion with a shell layer. The method of coating the core portion with the shell layer may, for example, be a method of coating a copolymer constituting the shell layer by coating the surface of the rubber-elastic core portion obtained by the above method; The core portion having a rubber elasticity obtained by the method is a main chain component, and a method of graft-polymerizing a component constituting the shell layer as a side chain component.

上述橡膠粒子的平均粒徑並未特別限定，但較佳為10~500nm，更佳為20~400nm。又，上述橡膠粒子的最大粒徑並未特別限定，但較佳為50~1000nm，更佳為100~800nm。若平均粒徑超過500nm，或是，若最大粒徑超過1000nm，則硬化物中的橡膠粒子的分散性降低，耐龜裂性可能降低。另一方面，若平均粒徑低於10nm，或是，若最大粒徑低於50nm，則可能變得難以獲得硬化物的耐龜裂性提升的效果。 The average particle diameter of the rubber particles is not particularly limited, but is preferably from 10 to 500 nm, more preferably from 20 to 400 nm. Further, the maximum particle diameter of the rubber particles is not particularly limited, but is preferably from 50 to 1,000 nm, more preferably from 100 to 800 nm. When the average particle diameter exceeds 500 nm, or if the maximum particle diameter exceeds 1000 nm, the dispersibility of the rubber particles in the cured product is lowered, and the crack resistance may be lowered. On the other hand, when the average particle diameter is less than 10 nm, or if the maximum particle diameter is less than 50 nm, it may become difficult to obtain an effect of improving the crack resistance of the cured product.

上述橡膠粒子的折射率並未特別限定，但較佳為1.40~1.60，更佳為1.42~1.58。又，橡膠粒子的折射率和將包含該橡膠粒子的硬化性環氧樹脂組成物(本發明的硬化性環氧樹脂組成物)硬化所製得的硬化物的折射率之差，較佳為±0.03以內。若折射率的差超過± 0.03，則硬化物的透明性降低，有時會發生白濁，存在光半導體裝置的光度降低的傾向，可能使光半導體裝置的功能消失。 The refractive index of the rubber particles is not particularly limited, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.58. Further, the difference in refractive index between the refractive index of the rubber particles and the cured product obtained by curing the curable epoxy resin composition (the curable epoxy resin composition of the present invention) containing the rubber particles is preferably ± Within 0.03. If the difference in refractive index exceeds ± When 0.03 is used, the transparency of the cured product is lowered, and white turbidity may occur, and the illuminance of the optical semiconductor device may be lowered, and the function of the optical semiconductor device may be lost.

橡膠粒子的折射率，例如，能藉由以下方式求得：將1g橡膠粒子澆鑄至模具，在210℃、4MPa下壓縮成形，製得厚度1mm的平板，從所製得的平板切出長20mm×寬6mm的試片，在使用單溴萘作為中間液而使稜鏡與該試片密著的狀態下，使用多波長阿貝折射計(商品名「DR-M2」，ATAGO(股)製)測定在20℃、鈉D線下的折射率。 The refractive index of the rubber particles can be determined, for example, by casting 1 g of rubber particles into a mold, and compression-molding at 210 ° C and 4 MPa to obtain a flat plate having a thickness of 1 mm, and cutting the length of the flat plate by 20 mm. In a test piece having a width of 6 mm, a multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by ATAGO Co., Ltd.) is used in a state where ruthenium is used as an intermediate liquid and the ruthenium is adhered to the test piece. The refractive index at 20 ° C under the sodium D line was measured.

本發明的硬化性環氧樹脂組成物的硬化物的折射率，例如，能藉由以下方式求得：從利用下述硬化物的項目所記載的加熱硬化方法所製得的硬化物，切出長20mm×寬6mm×厚1mm的試片，在使用單溴萘作為中間液而使稜鏡與該試片密著的狀態下，使用多波長阿貝折射計(商品名「DR-M2」，ATAGO(股)製)測定在20℃、鈉D線下的折射率。 The refractive index of the cured product of the curable epoxy resin composition of the present invention can be obtained, for example, by cutting out the cured product obtained by the heat curing method described in the item of the following cured product. In a test piece having a length of 20 mm, a width of 6 mm, and a thickness of 1 mm, a multi-wavelength Abbe refractometer (trade name "DR-M2") is used in a state where ruthenium is used as an intermediate liquid and the ruthenium is adhered to the test piece. ATAGO (manufactured by ATAGO Co., Ltd.) measured the refractive index at 20 ° C under the sodium D line.

本發明的硬化性環氧樹脂組成物中的上述橡膠粒子的含有量(調配量)並未特別限定，但相對於硬化性環氧樹脂組成物中所含之具有環氧基的化合物的總量(100重量份)，較佳為0.5~30重量份，更佳為1~20重量份。若橡膠粒子的含有量低於0.5重量份，則存在硬化物的耐龜裂性降低的傾向。另一方面，若橡膠粒子的含有量超過30重量份，則存在硬化物的耐熱性降低的傾向。 The content (adjusted amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but is based on the total amount of the epoxy group-containing compound contained in the curable epoxy resin composition. (100 parts by weight), preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight. When the content of the rubber particles is less than 0.5 parts by weight, the crack resistance of the cured product tends to decrease. On the other hand, when the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends to decrease.

[核殼型丙烯酸聚合物粒子] [core-shell acrylic polymer particles]

本發明的硬化性環氧樹脂組成物，亦可進一步包含利用Fedors法所算出的在25℃下的溶解度參數(δ)(稱為「溶解度參數(Fedors法)」)為19.5~21.5[MPa1/2]的核殼型丙烯酸聚合物粒子(有時簡稱為「核殼型丙烯酸聚合物粒子」)。本發明的硬化性環氧樹脂組成物，藉由含有上述核殼型丙烯酸聚合物粒子，而有能形成尤其是在室溫下的操作性優良、耐吸濕性(例如，在高溫條件下使其吸濕後，即使在回流製程中進行加熱處理時仍難以發生龜裂或光半導體裝置從導線框(lead frame)剝離的特性)優良的硬化物的傾向。 The curable epoxy resin composition of the present invention may further contain a solubility parameter (δ) at 25 ° C calculated by the Fedors method (referred to as "solubility parameter (Fedors method)") of 19.5 to 21.5 [MPa 1 /2 ] core-shell type acrylic polymer particles (sometimes referred to simply as "core-shell type acrylic polymer particles"). The curable epoxy resin composition of the present invention contains the core-shell type acrylic polymer particles, and is excellent in handleability, particularly moisture absorption at room temperature (for example, under high temperature conditions). After moisture absorption, even when heat treatment is performed in the reflow process, it is difficult to cause cracking or the characteristics of the optical semiconductor device to be peeled off from the lead frame.

又，上述核殼型丙烯酸聚合物粒子，例如，在硬化性環氧樹脂組成物中包含無機螢光體微粒子等無機微粒子的情況，亦產生即使是在加熱樹脂組成物之際仍可維持上述無機微粒子的良好分散狀態的效果。因此，若使用上述核殼型丙烯酸聚合物粒子，則可不如過去般添加氧化矽填料等觸變劑(thixotropic agent)提高樹脂組成物黏度，而維持無機微粒子(尤其是，無機螢光體微粒子)的良好分散狀態，因此能將本發明的硬化性環氧樹脂組成物作成低黏度，在此情況下，能發揮優良的作業性。 In addition, when the core-shell type acrylic polymer particles contain inorganic fine particles such as inorganic phosphor fine particles in the curable epoxy resin composition, the inorganic particles can be maintained even when the resin composition is heated. The effect of a good dispersion state of the microparticles. Therefore, when the core-shell type acrylic polymer particles are used, it is possible to increase the viscosity of the resin composition by adding a thixotropic agent such as a cerium oxide filler, and to maintain inorganic fine particles (especially, inorganic phosphor particles). Since the curable epoxy resin composition of the present invention has a low viscosity, it is possible to exhibit excellent workability.

上述核殼型丙烯酸聚合物粒子具有包含核、被覆該核的單層或多層的殼層(殼)的核殼構造，上述核及殼層皆利用丙烯酸聚合物(以丙烯酸系單體作為必要的單量體成分的聚合物)所構成的聚合物粒子。又， 在本說明書中，有時將構成上述核殼型丙烯酸聚合物粒子的核的丙烯酸聚合物稱為「丙烯酸聚合物(核)」，將構成上述核殼型丙烯酸聚合物粒子的殼的丙烯酸聚合物稱為「丙烯酸聚合物(殼)」。在上述核殼型丙烯酸聚合物粒子中，並未特別限定，但較佳為丙烯酸聚合物(核)與丙烯酸聚合物(殼)具有不同的組成。 The core-shell type acrylic polymer particles have a core-shell structure comprising a core, a shell layer (shell) covering a single layer or a plurality of layers of the core, and the core and the shell layer are all made of an acrylic polymer (with an acrylic monomer as a necessity) Polymer particles composed of a single component polymer). also, In the present specification, the acrylic polymer constituting the core of the core-shell type acrylic polymer particles may be referred to as "acrylic polymer (core)", and the acrylic polymer constituting the shell of the core-shell type acrylic polymer particles may be used. It is called "acrylic polymer (shell)". The core-shell type acrylic polymer particles are not particularly limited, but it is preferred that the acrylic polymer (core) and the acrylic polymer (shell) have different compositions.

上述核殼型丙烯酸聚合物粒子之利用Fedors法所算出的在25℃下的溶解度參數(δ)(稱為「溶解度參數(Fedors法)」)為19.5~21.5[MPa1/2]，較佳為19.7~21.3[MPa1/2]，更佳為20.0~21.0[MPa1/2]。若上述核殼型丙烯酸聚合物粒子的溶解度參數(Fedors法)低於19.5[MPa1/2]，則有與脂環式環氧化合物(A)的相溶性降低、無機微粒子的分散性降低的傾向。另一方面，若上述核殼型丙烯酸聚合物粒子的溶解度參數(Fedors法)超過21.5[MPa1/2]，則有與脂環式環氧化合物(A)的相溶性降低，無機微粒子的分散性降低的傾向。上述核殼型丙烯酸聚合物粒子的溶解度參數(Fedors法)，係例如，能藉由算出丙烯酸聚合物(核)、丙烯酸聚合物(殼)的溶解度參數(Fedors法)，將它們加權平均來算出。又，上述核殼型丙烯酸聚合物粒子的溶解度參數(Fedors法)係利用構成核殼型丙烯酸聚合物粒子的單體的組成來控制。 The solubility parameter (δ) at 25 ° C (referred to as "solubility parameter (Fedors method)) calculated by the Fedors method of the core-shell type acrylic polymer particles is 19.5 to 21.5 [MPa 1/2 ], preferably It is 19.7 to 21.3 [MPa 1/2 ], more preferably 20.0 to 21.0 [MPa 1/2 ]. When the solubility parameter (Fedors method) of the core-shell type acrylic polymer particles is less than 19.5 [MPa 1/2 ], the compatibility with the alicyclic epoxy compound (A) is lowered, and the dispersibility of the inorganic fine particles is lowered. tendency. On the other hand, when the solubility parameter (Fedors method) of the core-shell type acrylic polymer particles exceeds 21.5 [MPa 1/2 ], compatibility with the alicyclic epoxy compound (A) is lowered, and dispersion of inorganic fine particles is caused. The tendency to reduce sexuality. The solubility parameter (Fedors method) of the core-shell type acrylic polymer particles can be calculated, for example, by calculating the solubility parameter (Fedors method) of an acrylic polymer (core) or an acrylic polymer (shell), and weighting the average . Further, the solubility parameter (Fedors method) of the core-shell type acrylic polymer particles is controlled by the composition of the monomers constituting the core-shell type acrylic polymer particles.

上述丙烯酸聚合物(核)的玻璃轉移溫度並未特別限定，較佳為60~120℃，更佳為70~110℃，又更佳為80~100℃。若丙烯酸聚合物(核)的玻璃轉移溫度低於60℃，則硬化物的耐熱性可能降低。另一方面，若丙 烯酸聚合物(核)的玻璃轉移溫度超過120℃，則硬化物的耐龜裂性(對各種應力難以產生龜裂的特性)可能降低。又，丙烯酸聚合物(核)的玻璃轉移溫度意指由下述Fox的公式所算出的計算值(參照Bull.Am.Phys.Soc.,1(3)123(1956))。下述Fox的公式中，Tg表示丙烯酸聚合物的玻璃轉移溫度(單位：K)，Wi表示單體i相對於構成丙烯酸聚合物的單體總量的重量分率。又，Tgi表示單體i的均聚合物的玻璃轉移溫度(單位：K)。下述Fox的公式表示丙烯酸聚合物為單體1、單體2、...及單體n的共聚物的情況的公式。 The glass transition temperature of the above acrylic polymer (core) is not particularly limited, but is preferably 60 to 120 ° C, more preferably 70 to 110 ° C, and still more preferably 80 to 100 ° C. If the glass transition temperature of the acrylic polymer (core) is lower than 60 ° C, the heat resistance of the cured product may be lowered. On the other hand, when the glass transition temperature of the acrylic polymer (core) exceeds 120 ° C, the crack resistance of the cured product (characteristic that cracking is unlikely to occur for various stresses) may be lowered. Further, the glass transition temperature of the acrylic polymer (core) means a calculated value calculated by the following formula of Fox (refer to Bull. Am. Phys. Soc., 1 (3) 123 (1956)). In the formula of the following Fox, Tg represents the glass transition temperature (unit: K) of the acrylic polymer, and W i represents the weight fraction of the monomer i with respect to the total amount of the monomers constituting the acrylic polymer. Further, Tg i represents the glass transition temperature (unit: K) of the homopolymer of the monomer i. The formula of the following Fox formula represents a formula in the case where the acrylic polymer is a copolymer of monomer 1, monomer 2, ... and monomer n.

1/Tg=W1/Tg1+W2/Tg2+...+Wn/Tgn 1/Tg=W 1 /Tg 1 +W 2 /Tg 2 +...+W n /Tg n

上述均聚合物的玻璃轉移溫度，能採用各種文獻記載的值，例如，能採用「POLYMER HANDBOOK第3版」(John Wiley & Sons.Inc.發行)記載的值。又，針對文獻未記載者，能採用利用常法聚合單體所製得的均聚合物之利用DSC法所測定的玻璃轉移溫度的值。 The glass transition temperature of the above homopolymer can be a value described in various documents. For example, the value described in "POLYMER HANDBOOK 3rd Edition" (issued by John Wiley & Sons. Inc.) can be used. Further, for those not described in the literature, the value of the glass transition temperature measured by the DSC method using a homopolymer obtained by polymerizing a monomer by a normal method can be used.

又，丙烯酸聚合物(核)的玻璃轉移溫度，可利用構成丙烯酸聚合物(核)的單體的組成來控制。 Further, the glass transition temperature of the acrylic polymer (core) can be controlled by the composition of the monomer constituting the acrylic polymer (core).

上述丙烯酸聚合物(殼)的玻璃轉移溫度並未特別限定，較佳為60~120℃，更佳為70~115℃。若丙烯酸聚合物(殼)的玻璃轉移溫度低於60℃，則硬化物的耐熱性可能降低。另一方面，若丙烯酸聚合物(殼)的玻璃轉移溫度超過120℃，則硬化物的耐龜裂性可能降低。又，丙烯酸聚合物(殼)的玻璃轉移溫度意指由上述Fox的公式所算出的值，能與丙烯酸聚合物(核)的玻璃轉移 溫度同樣地算出。又，丙烯酸聚合物(殼)的玻璃轉移溫度，可利用構成丙烯酸聚合物(殼)的單體的組成來控制。 The glass transition temperature of the above acrylic polymer (shell) is not particularly limited, but is preferably 60 to 120 ° C, more preferably 70 to 115 ° C. If the glass transition temperature of the acrylic polymer (shell) is lower than 60 ° C, the heat resistance of the cured product may be lowered. On the other hand, if the glass transition temperature of the acrylic polymer (shell) exceeds 120 ° C, the crack resistance of the cured product may be lowered. Further, the glass transition temperature of the acrylic polymer (shell) means a value calculated from the above formula of Fox, and can be transferred to a glass of an acrylic polymer (core). The temperature is calculated in the same manner. Further, the glass transition temperature of the acrylic polymer (shell) can be controlled by the composition of the monomers constituting the acrylic polymer (shell).

上述核殼型丙烯酸聚合物粒子中的丙烯酸聚合物(核)的玻璃轉移溫度與丙烯酸聚合物(殼)的玻璃轉移溫度的差(丙烯酸聚合物(殼)的玻璃轉移溫度[℃]-丙烯酸聚合物(核)的玻璃轉移溫度[℃])，並未特別限定，但較佳為-5~60℃，更佳為0~55℃。藉由將上述玻璃轉移溫度的差控制在上述範圍，硬化時的硬化性環氧樹脂組成物的接著性提高，硬化物的耐吸濕回流性提高，進一步地，有硬化物的耐熱性提高的傾向。 The difference between the glass transition temperature of the acrylic polymer (core) in the above-mentioned core-shell type acrylic polymer particles and the glass transition temperature of the acrylic polymer (shell) (glass transition temperature of the acrylic polymer (shell) [°C] - polymerization of acrylic acid The glass transition temperature [°C] of the substance (core) is not particularly limited, but is preferably -5 to 60 ° C, more preferably 0 to 55 ° C. By controlling the difference in the glass transition temperature to the above range, the adhesion of the curable epoxy resin composition at the time of curing is improved, and the moisture absorption reflow resistance of the cured product is improved, and the heat resistance of the cured product tends to be improved. .

上述丙烯酸聚合物(核)、丙烯酸聚合物(殼)，係分別以丙烯酸系單體(acrylic monomer)作為必要的單體成分所構成的丙烯酸聚合物。 The acrylic polymer (core) and the acrylic polymer (shell) are acrylic polymers each having an acrylic monomer as an essential monomer component.

作為構成上述丙烯酸聚合物(核)、丙烯酸聚合物(殼)的丙烯酸系單體，可舉出例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸n-丙酯、(甲基)丙烯酸i-丙酯、(甲基)丙烯酸n-丁酯、(甲基)丙烯酸i-丁酯、(甲基)丙烯酸t-丁酯、(甲基)丙烯酸n-己酯、(甲基)丙烯酸n-庚酯、(甲基)丙烯酸n-辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸n-壬酯、(甲基)丙烯酸i-壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二基酯、(甲基)丙烯酸十八基酯等(甲基)丙烯酸烷酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸t-丁基環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸三環[5.2.1.02.6]癸-8-基酯、(甲基)丙烯酸二環戊二烯酯等具有脂肪族環的(甲基)丙烯酸 酯；(甲基)丙烯酸苯酯、；(甲基)丙烯酸芐酯等具有芳香族環的(甲基)丙烯酸酯；(甲基)丙烯酸N-甲基-2,2,6,6-四甲基哌啶酯等具有雜環的(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、單(甲基)丙烯酸甘油酯(glycerol mono(meth)acrylate)等具有羥基的(甲基)丙烯酸酯；(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯等具有環氧基的(甲基)丙烯酸酯；(甲基)丙烯酸N,N-二甲基胺基乙酯等具有胺基的(甲基)丙烯酸酯；(甲基)丙烯酸；(甲基)丙烯醯胺等。又，在本說明書中「(甲基)丙烯酸」意指丙烯酸及/或甲基丙烯酸(丙烯酸及甲基丙烯酸當中任一者或兩者)。 Examples of the acrylic monomer constituting the acrylic polymer (core) or the acrylic polymer (shell) include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid n-. Propyl ester, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-(meth)acrylate Hexyl ester, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylic acid (meth)acrylic acid alkyl ester such as i-nonyl ester, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate; cyclohexyl (meth) acrylate, T-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 2.6 ]non-8-yl (meth)acrylate, dicyclopentyl (meth)acrylate (meth) acrylate having an aliphatic ring such as a dienlate; (meth) acrylate having an aromatic ring such as phenyl (meth) acrylate; or benzyl (meth) acrylate; (meth)acrylic acid (methyl) having a heterocyclic ring such as N-methyl-2,2,6,6-tetramethylpiperidinyl ester Acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth) (meth)acrylate having a hydroxyl group such as acrylate; (meth)acrylate having an epoxy group such as glycidyl (meth)acrylate or methyl glycidyl (meth)acrylate; (meth)acrylic acid (Meth) acrylate having an amine group such as N,N-dimethylaminoethyl ester; (meth)acrylic acid; (meth)acrylamide or the like. In the present specification, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid (either or both of acrylic acid and methacrylic acid).

作為構成上述丙烯酸聚合物(核)、丙烯酸聚合物(殼)的單體，亦能併用丙烯酸系單體以外的單體。作為上述丙烯酸系單體以外的單體，可舉出例如：苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯單體；丙烯腈、甲基丙烯腈等氰化乙烯單體；巴豆酸、衣康酸、富馬酸、馬來酸等具有羧基的單體；乙烯基吡啶、乙烯醇、乙烯基咪唑、乙烯基吡咯酮、乙酸乙烯酯、1-乙烯基咪唑等乙烯單體；衣康酸單甲酯、衣康酸單乙酯、衣康酸單丙酯、衣康酸單丁酯、衣康酸二甲酯、衣康酸二乙酯、衣康酸二丙酯、衣康酸二丁酯等衣康酸酯；富馬酸單甲酯、富馬酸單乙酯、富馬酸單丙酯、富馬酸單丁酯、富馬酸二甲酯、富馬酸二乙酯、富馬酸二丙酯、富馬酸二丁酯等富馬酸酯；馬來酸單甲酯、馬來酸單乙 酯、馬來酸單丙酯、馬來酸單丁酯、馬來酸二甲酯、馬來酸二乙酯、馬來酸二丙酯、馬來酸二丁酯等馬來酸酯等。 As the monomer constituting the acrylic polymer (core) or the acrylic polymer (shell), a monomer other than the acrylic monomer can also be used in combination. Examples of the monomer other than the acrylic monomer include an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene; and an ethylene cyanide monomer such as acrylonitrile or methacrylonitrile; a monomer having a carboxyl group such as crotonic acid, itaconic acid, fumaric acid or maleic acid; an ethylene monomer such as vinylpyridine, vinyl alcohol, vinylimidazole, vinylpyrrolidone, vinyl acetate or 1-vinylimidazole Itaconic acid monomethyl ester, itaconic acid monoethyl ester, itaconic acid monopropyl ester, itaconic acid monobutyl ester, methiconine dimethyl ester, diethyl itaconate, dipropyl itaconate, Itaconate such as dibutyl itaconate; monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, dimethyl fumarate, fumaric acid Fumarate such as diethyl ester, dipropyl fumarate and dibutyl fumarate; monomethyl maleate, monoethyl maleate Ester, maleic acid monopropyl ester, maleic acid monobutyl ester, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate and the like maleate.

又，作為構成上述丙烯酸聚合物(核)、丙烯酸聚合物(殼)的單體，亦能使用具有2個以上的聚合性官能基(例如，脂肪族碳-碳雙鍵等)的多官能性單體。作為上述多官能性單體，可舉出例如：二乙烯苯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、馬來酸二烯丙酯、三聚氰酸三烯丙酯、苯二甲酸二烯丙酯、丁二醇二丙烯酸酯等。 Further, as the monomer constituting the acrylic polymer (core) or the acrylic polymer (shell), polyfunctionality having two or more polymerizable functional groups (for example, an aliphatic carbon-carbon double bond or the like) can also be used. monomer. Examples of the polyfunctional monomer include divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diallyl maleate, and cyanuric acid. Allyl ester, diallyl phthalate, butanediol diacrylate, and the like.

丙烯酸系聚合物相對於構成上述丙烯酸聚合物(核)的單體總量(100重量%)的比例並未特別限定，但較佳為70~100重量%。尤其是，上述丙烯酸聚合物(核)較佳為實質上只以丙烯酸系單體所構成的聚合物(例如，丙烯酸系單體相對於單體總量的比例為98~100重量%的聚合物)。作為構成上述丙烯酸聚合物(核)的單體，其中較佳為具有碳數1~4的烷基的(甲基)丙烯酸烷基酯，更佳為甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯。 The ratio of the acrylic polymer to the total amount (100% by weight) of the monomers constituting the acrylic polymer (core) is not particularly limited, but is preferably 70 to 100% by weight. In particular, the acrylic polymer (core) is preferably a polymer composed substantially only of an acrylic monomer (for example, a polymer having a ratio of an acrylic monomer to a total amount of monomers of 98 to 100% by weight) ). The monomer constituting the above acrylic polymer (core) is preferably an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate, butyl acrylate or the like. Butyl acrylate.

丙烯酸系單體相對於構成上述丙烯酸聚合物(殼)的單體總量(100重量%)的比例並未特別限定，但較佳為70~100重量%。尤其是上述丙烯酸聚合物(殼)較佳為實質上只以丙烯酸系單體所構成的聚合物(例如，丙烯酸系單體相對於單體總量的比例為98~100重量%的聚合物)。作為構成上述丙烯酸聚合物(殼)的單體，其中較 佳為具有碳數1~4的烷基的(甲基)丙烯酸烷基酯、(甲基)丙烯酸，更佳為甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、甲基丙烯酸。 The ratio of the acrylic monomer to the total amount (100% by weight) of the monomers constituting the acrylic polymer (shell) is not particularly limited, but is preferably 70 to 100% by weight. In particular, the acrylic polymer (shell) is preferably a polymer composed substantially only of an acrylic monomer (for example, a polymer having a ratio of an acrylic monomer to a total amount of monomers of 98 to 100% by weight) . As a monomer constituting the above acrylic polymer (shell), among them It is preferably an alkyl (meth)acrylate or a (meth)acrylic acid having an alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate, butyl acrylate, butyl methacrylate or methacrylic acid.

即，上述核殼型丙烯酸聚合物粒子，較佳為利用實質上只以丙烯酸系單體所構成的聚合物(例如，丙烯酸系單體相對於構成核殼型丙烯酸聚合物粒子的單體總量的比例為98~100重量%的聚合物)所構成的核殼型丙烯酸聚合物粒子。 That is, the core-shell type acrylic polymer particles are preferably a polymer composed of substantially only an acrylic monomer (for example, the total amount of the acrylic monomer relative to the monomers constituting the core-shell type acrylic polymer particles). The core-shell type acrylic polymer particles composed of a polymer having a ratio of 98 to 100% by weight.

作為上述構成丙烯酸聚合物(核)、丙烯酸聚合物(殼)的單體，若大量使用(甲基)丙烯腈等氰化乙烯單體，則因為該單體具有高極性，因此硬化物的吸濕性變得過高，有變得容易在回流製程產生龜裂發生或剝離等不良的傾向，故而不佳。又，作為上述構成丙烯酸聚合物(核)、丙烯酸聚合物(殼)的單體，若大量使用苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯單體，則硬化物變得容易著色，故而不佳。因此，氰化乙烯單體及芳香族乙烯單體相對於上述構成丙烯酸聚合物(核)(或丙烯酸聚合物(殼))的單體總量(100重量%)的比例，較佳為5重量%以下，更佳為2重量%以下，特佳為實質上不含有(不主動調配為單體成分)。 When a vinyl cyanide monomer such as (meth)acrylonitrile is used in a large amount as a monomer constituting the acrylic polymer (core) or the acrylic polymer (shell), since the monomer has high polarity, the cured product is sucked. The wetness is too high, and there is a tendency that cracking or peeling tends to occur in the reflow process, which is not preferable. In addition, when a large amount of an aromatic vinyl monomer such as styrene, α-methylstyrene or vinyltoluene is used as the monomer constituting the acrylic polymer (core) or the acrylic polymer (shell), the cured product becomes It is easy to color, so it is not good. Therefore, the ratio of the vinyl cyanide monomer and the aromatic vinyl monomer to the total amount (100% by weight) of the monomers constituting the acrylic polymer (core) (or acrylic polymer (shell)) is preferably 5 by weight. % or less, more preferably 2% by weight or less, and particularly preferably substantially not contained (not actively formulated as a monomer component).

又，上述核殼型丙烯酸聚合物粒子，基於抑制硬化物的著色或劣化的觀點，較佳為不含有丁二烯橡膠。又，上述核殼型丙烯酸聚合物粒子，基於相溶性或成本的觀點，較佳為不含有矽酮橡膠。 Further, the core-shell type acrylic polymer particles preferably do not contain butadiene rubber from the viewpoint of suppressing coloration or deterioration of the cured product. Further, the core-shell type acrylic polymer particles preferably do not contain an anthrone rubber from the viewpoint of compatibility or cost.

上述核殼型丙烯酸聚合物粒子中的丙烯酸聚合物(核)及丙烯酸聚合物(殼)的比例(重量比)[丙烯酸聚合物(核)/丙烯酸聚合物(殼)]並未特別限定，但較佳為1/0.1~1/200，更佳為1/0.3~1/120，又更佳為1/0.4~1/10。若丙烯酸聚合物(核)及丙烯酸聚合物(殼)的比例超出上述範圍，則難以獲得對接著體的接著力提升、由加熱所造成的快速增黏的效果，其結果，可能無法獲得如下的效果：提升硬化性環氧樹脂組成物的操作性、維持加熱時無機微粒子的良好分散性、提升硬化物的耐吸濕回流性(使其在高濕條件下吸濕後，即使當在回流製程中進行加熱處理時仍難以發生龜裂或從光半導體裝置的導線框剝離的特性)。 The ratio (weight ratio) of the acrylic polymer (core) and the acrylic polymer (shell) in the core-shell type acrylic polymer particles [acrylic polymer (core) / acrylic polymer (shell)] is not particularly limited, but It is preferably 1/0.1 to 1/200, more preferably 1/0.3 to 1/120, and still more preferably 1/0.4 to 1/10. When the ratio of the acrylic polymer (core) and the acrylic polymer (shell) is out of the above range, it is difficult to obtain an effect of improving the adhesion of the adherend and the rapid viscosity increase by heating, and as a result, the following may not be obtained. Effect: Improve the handleability of the curable epoxy resin composition, maintain good dispersion of inorganic fine particles during heating, and improve the moisture absorption reflow resistance of the cured product (after allowing it to absorb moisture under high humidity conditions, even when in the reflow process) When the heat treatment is performed, cracking or peeling from the lead frame of the optical semiconductor device is hard to occur.

作為上述核殼型丙烯酸聚合物粒子的特佳具體型態，可舉例如：以將具有碳數1~4的烷基的甲基丙烯酸烷基酯(尤其是，甲基丙烯酸甲酯、甲基丙烯酸丁酯)當作必要的單體成分之玻璃轉移溫度60~120℃的丙烯酸聚合物(核)作為核，以將具有碳數1~4的烷基的甲基丙烯酸烷基酯(尤其是，甲基丙烯酸甲酯、甲基丙烯酸丁酯)當作必要的單體成分之玻璃轉移溫度60~120℃、與丙烯酸聚合物(C)不同的單體組成的丙烯酸聚合物(殼)作為殼的核殼型丙烯酸聚合物粒子。上述丙烯酸聚合物(殼)，較佳為進一步包含具有羥基的單體(例如，具有羥基的(甲基)丙烯酸酯)及/或具有羧基的單體(例如，(甲基)丙烯酸)作為單體成分。又，上述殼可為單層，亦可為多層。具有碳數1~4的烷基的甲基丙烯酸烷基酯相對於上 述構成丙烯酸聚合物(核)的單體成分總量(100重量%)的比例，較佳為60重量%以上，更佳為80重量%以上。又，具有碳數1~4的烷基的甲基丙烯酸烷基酯相對於上述構成丙烯酸聚合物(殼)的單體成分總量(100重量%)的比例，較佳為60重量%以上，更佳為80重量%以上。 As a particularly preferred embodiment of the core-shell type acrylic polymer particles, for example, an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (especially, methyl methacrylate or methyl group) may be mentioned. Butyl acrylate) as an essential monomer component, an acrylic polymer (nucleus) having a glass transition temperature of 60 to 120 ° C as a core to form an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (especially , methyl methacrylate, butyl methacrylate) as a necessary monomer component, a glass transition temperature of 60 to 120 ° C, an acrylic polymer (shell) composed of a monomer different from the acrylic polymer (C) as a shell Core-shell type acrylic polymer particles. The above acrylic polymer (shell) preferably further comprises a monomer having a hydroxyl group (for example, a (meth) acrylate having a hydroxyl group) and/or a monomer having a carboxyl group (for example, (meth)acrylic acid) as a single Body composition. Further, the shell may be a single layer or a plurality of layers. An alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms relative to the upper The ratio of the total amount of the monomer components (100% by weight) constituting the acrylic polymer (core) is preferably 60% by weight or more, and more preferably 80% by weight or more. Further, the ratio of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms to the total amount of the monomer component (100% by weight) constituting the acrylic polymer (shell) is preferably 60% by weight or more. More preferably, it is 80% by weight or more.

上述核殼型丙烯酸聚合物粒子中的鹼金屬離子(例如，Na離子、K離子等)的含有量並未特別限定，但較佳為10ppm以下，更佳為5ppm以下，又更佳為1ppm以下。若鹼金屬離子的含有量超過10ppm，則硬化物的絕緣特性可能降低。上述鹼金屬離子的含有量，例如，能使用ICP發光分析裝置(ICP emission analyzing device)或離子層析儀(ion chromatography)等來測定。又，上述鹼金屬離子的含有量，例如，能利用聚合時的聚合開始劑或乳化劑的選擇來控制。 The content of the alkali metal ions (for example, Na ions, K ions, and the like) in the core-shell type acrylic polymer particles is not particularly limited, but is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less. . If the content of the alkali metal ions exceeds 10 ppm, the insulating properties of the cured product may be lowered. The content of the alkali metal ion can be measured, for example, by using an ICP emission analyzing device, an ion chromatography, or the like. Further, the content of the above alkali metal ion can be controlled, for example, by selection of a polymerization initiator or an emulsifier at the time of polymerization.

上述核殼型丙烯酸聚合物粒子的平均二次粒徑並未特別限定，但較佳為5~50μm。若平均二次粒徑低於5μm，則變得容易飛散容易引起靜電，而可能操作困難。另一方面，若平均二次粒徑超過50μm，則當使一次粒子分散時可能時間的負擔大。上述平均二次粒徑，例如，能使用掃瞄型電子顯微鏡(SEM)、穿透型電子顯微鏡(TEM)等電子顯微鏡測定。又，上述平均二次粒徑，例如，能利用造粒條件、乾燥條件(溫度、風量)等來控制。 The average secondary particle diameter of the core-shell type acrylic polymer particles is not particularly limited, but is preferably 5 to 50 μm . If the average secondary particle diameter is less than 5 μm , it becomes easy to fly and easily cause static electricity, which may be difficult to handle. On the other hand, if the average secondary particle diameter exceeds 50 μm , the burden of time may be large when the primary particles are dispersed. The average secondary particle diameter can be measured, for example, by an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Further, the average secondary particle diameter can be controlled, for example, by granulation conditions, drying conditions (temperature, air volume), and the like.

上述核殼型丙烯酸聚合物粒子的體積平均一次粒徑(Dv)並未特別限定，較佳為200nm以上，更佳 為500nm以上。又，上述核殼型丙烯酸聚合物粒子的體積平均一次粒徑，較佳為8μm以下，更佳為5μm以下，又更佳為1μm以下。若體積平均一次粒徑低於200nm，則維持無機微粒子的良好分散狀態可能變得困難。另一方面，若體積平均一次粒徑超過8μm，硬化物的透明性可能降低。上述體積平均一次粒徑，例如，能使用雷射繞射散射式粒度分布測定裝置(例如，商品名「LA-910W」，崛場製作所(股)製等)測定。又，上述體積平均一次粒徑，例如，能利用單體乳化時的條件等來控制。 The volume average primary particle diameter (Dv) of the core-shell type acrylic polymer particles is not particularly limited, but is preferably 200 nm or more, and more preferably 500 nm or more. Further, the volume average primary particle diameter of the core-shell type acrylic polymer particles is preferably 8 μm or less, more preferably 5 μm or less, still more preferably 1 μm or less. If the volume average primary particle diameter is less than 200 nm, it may become difficult to maintain a good dispersion state of the inorganic fine particles. On the other hand, if the volume average primary particle diameter exceeds 8 μm , the transparency of the cured product may be lowered. The volume average primary particle diameter can be measured, for example, by a laser diffraction scattering type particle size distribution measuring apparatus (for example, trade name "LA-910W", manufactured by Seisakusho Co., Ltd.). Moreover, the volume average primary particle diameter can be controlled, for example, by the conditions at the time of monomer emulsification.

上述核殼型丙烯酸聚合物粒子，能利用周知或慣用的核殼型聚合物粒子的製造方法製造。上述核殼型丙烯酸聚合物粒子能藉由以殼被覆核來製得，可舉出例如：在核的表面塗布構成殼的丙烯酸聚合物的方法、或以上述構成核的丙烯酸聚合物作為主鏈成分而將構成殼的丙烯酸聚合物(側鏈成分)接枝聚合的方法等。更具體而言，上述核殼型丙烯酸聚合物粒子，例如，能依照國際公開2010/090246所揭露的方法製造。 The core-shell type acrylic polymer particles can be produced by a known or conventional method for producing core-shell type polymer particles. The core-shell type acrylic polymer particles can be obtained by coating a core with a shell, and examples thereof include a method of coating an acrylic polymer constituting a shell on a surface of a core, or an acrylic polymer constituting a core as a main chain. A method of graft-polymerizing an acrylic polymer (side chain component) constituting a shell, and the like. More specifically, the core-shell type acrylic polymer particles described above can be produced, for example, according to the method disclosed in International Publication No. 2010/090246.

在本發明的硬化性環氧樹脂組成物中，上述核殼型丙烯酸聚合物粒子能單獨使用一種，或組合兩種以上使用。又，作為上述核殼型丙烯酸聚合物粒子，亦能使用商品名「Metablen KP-0917」、「Metablen KP-0930」、「Metablen KP-0950」(以上，三菱Rayon(股)製)等市售品。 In the curable epoxy resin composition of the present invention, the core-shell type acrylic polymer particles may be used singly or in combination of two or more. Further, as the core-shell type acrylic polymer particles, commercially available products such as "Metablen KP-0917", "Metablen KP-0930", and "Metablen KP-0950" (above, manufactured by Mitsubishi Rayon Co., Ltd.) can be used. Product.

相對於脂環式環氧化合物(A)100重量份，上述核殼型丙烯酸聚合物粒子的含有量(調配量)為1~30重量份，較佳為3~20重量份，更佳為5~15重量份。若核殼型丙烯酸聚合物粒子的含有量低於1重量份，則難以獲得核殼型丙烯酸聚合物粒子的添加效果，變得難以兼顧無機微粒子的良好分散狀態的維持及作業性。另一方面，若核殼型丙烯酸聚合物粒子的含有量超過30重量份，則有光半導體裝置的初期光度降低的傾向。 The content of the core-shell type acrylic polymer particles (adjusted amount) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). ~15 parts by weight. When the content of the core-shell type acrylic polymer particles is less than 1 part by weight, it is difficult to obtain the effect of adding the core-shell type acrylic polymer particles, and it is difficult to achieve both the maintenance of the favorable dispersion state of the inorganic fine particles and the workability. On the other hand, when the content of the core-shell type acrylic polymer particles exceeds 30 parts by weight, the initial luminosity of the optical semiconductor device tends to decrease.

[添加劑] [additive]

本發明的硬化性環氧樹脂組成物，除了上述之外，可在不損害本發明的效果的範圍內含有各種添加劑。若使其含有例如乙二醇、二乙二醇、丙二醇、甘油等具有羥基的化合物作為上述添加劑，則能使反應緩慢地進行。此外，在不損害黏度或透明性的範圍內，能使用矽酮系或氟系消泡劑、調平劑(leveling agent)、γ-縮水甘油氧基丙基三甲氧基矽烷或3-巰基丙基三甲氧基矽烷等矽烷偶合劑、界面活性劑、氧化矽、氧化鋁等無機填充劑、難燃劑、著色劑、抗氧化劑、紫外線吸收劑、離子吸附體、顏料、螢光體(例如，YAG系的螢光體微粒子、矽酸鹽系螢光體微粒子等無機螢光體微粒子)、脫模劑等慣用的添加劑。 In addition to the above, the curable epoxy resin composition of the present invention may contain various additives within a range not impairing the effects of the present invention. When a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol or glycerin is contained as the above additive, the reaction can be progressed slowly. Further, an anthrone or a fluorine-based antifoaming agent, a leveling agent, γ-glycidoxypropyltrimethoxydecane or 3-mercaptopropene can be used insofar as the viscosity or transparency is not impaired. a decane coupling agent such as a trimethoxy decane, a surfactant, an inorganic filler such as cerium oxide or aluminum oxide, a flame retardant, a colorant, an antioxidant, an ultraviolet absorber, an ion absorbing body, a pigment, and a phosphor (for example, A conventional additive such as a YAG-based phosphor fine particle, an inorganic phosphor fine particle such as a silicate-based phosphor fine particle, or a release agent.

<硬化性環氧樹脂組成物的製造方法> <Method for Producing Curable Epoxy Resin Composition>

本發明的硬化性環氧樹脂組成物，至少包含上述的脂環式環氧化合物(A)、異三聚氰酸單烯丙基二縮水甘油酯化合物(B)、及氫化偏苯三酸酐(C)即可，其製造方法(調 製方法)並未特別限定。具體而言，例如，能藉由以指定比例攪拌、混合各成分，依需要在真空下脫泡來調製，亦能藉由分別調製包含脂環式環氧化合物(A)、異三聚氰酸單烯丙基二縮水甘油酯化合物(B)等具有環氧基的化合物作為必要成分的組成物(有時稱為「環氧樹脂」)、與包含硬化劑(D)及硬化促進劑(E)、或硬化觸媒(F)作為必要成分的組成物(有時稱為「環氧硬化劑」)，以指定比例攪拌、混合該環氧樹脂及環氧硬化劑，依需要在真空下脫泡來調製。又，於此情況，氫化偏苯三酸酐(C)，可預先作為上述環氧樹脂及/或上述環氧硬化劑的構成成分調配，亦可在混合上述環氧樹脂及上述環氧硬化劑時作為上述環氧樹脂、上述環氧硬化劑以外的成分調配。氫化偏苯三酸酐(C)，通常，大多是作為上述環氧硬化劑的構成成分調配。 The curable epoxy resin composition of the present invention comprises at least the above-described alicyclic epoxy compound (A), isomeric cyanuric acid monoallyl diglycidyl ester compound (B), and hydrogenated trimellitic anhydride (C). Yes, its manufacturing method The method is not particularly limited. Specifically, for example, it can be prepared by stirring and mixing the components in a predetermined ratio, defoaming under vacuum as needed, and separately preparing the alicyclic epoxy compound (A) and iso-cyanuric acid. A composition having an epoxy group such as a monoallyl diglycidyl ester compound (B) as an essential component (sometimes referred to as "epoxy resin"), and a hardener (D) and a hardening accelerator (E) ) or a composition that hardens the catalyst (F) as an essential component (sometimes referred to as an "epoxy hardener"), and stirs and mixes the epoxy resin and epoxy hardener in a specified ratio, and takes off under vacuum as needed. Bubble to modulate. Further, in this case, the hydrogenated trimellitic anhydride (C) may be formulated as a constituent component of the epoxy resin and/or the epoxy curing agent in advance, or may be used as the ring when the epoxy resin and the epoxy curing agent are mixed. The oxygen resin and the components other than the epoxy hardener are blended. The hydrogenated trimellitic anhydride (C) is usually blended as a constituent component of the epoxy hardener.

調製上述環氧樹脂時的攪拌、混合時的溫度並未特別限定，但較佳為30~150℃，更佳為35~130℃。又，調製上述環氧硬化劑時的攪拌、混合時的溫度並未特別限定，但較佳為30~100℃，更佳為35~80℃。攪拌、混合能使用周知的裝置，例如自轉公轉型混合機、行星式混合機、捏合機、溶解器(dissolver)等。 The temperature at the time of stirring and mixing in preparing the above epoxy resin is not particularly limited, but is preferably 30 to 150 ° C, more preferably 35 to 130 ° C. Further, the temperature during stirring and mixing in preparing the epoxy curing agent is not particularly limited, but is preferably 30 to 100 ° C, more preferably 35 to 80 ° C. For the stirring and mixing, a well-known apparatus such as a self-rotating mixer, a planetary mixer, a kneader, a dissolver, or the like can be used.

尤其是，在本發明的硬化性環氧樹脂組成物包含上述脂環式聚酯樹脂的情況下，基於獲得均勻組成物的觀點，較佳為藉由以下方式來調製：將脂環式聚酯樹脂與氫化偏苯三酸酐(C)預先混合而製得它們的混合物(脂環式聚酯樹脂與氫化偏苯三酸酐(C)的混合物) 後，將硬化促進劑(E)、其他添加劑調配至該混合物而調製環氧硬化劑，接下來，將該環氧硬化劑與另外調製的環氧樹脂混合。進一步地，在本發明的硬化性環氧樹脂組成物包含硬化劑(D)的情況下，較佳為藉由以下方式來調製：將脂環式聚酯樹脂、氫化偏苯三酸酐(C)及硬化劑(D)預先混合而製得它們的混合物(脂環式聚酯樹脂、氫化偏苯三酸酐(C)及硬化劑(D)的混合物)後，將硬化促進劑(E)、其他添加劑調配至該混合物而調製環氧硬化劑，接下來，將該環氧硬化劑與另外調製的環氧樹脂混合。將上述脂環式聚酯樹脂及氫化偏苯三酸酐(C)(或者是，脂環式聚酯樹脂、氫化偏苯三酸酐(C)及硬化劑(D))混合時的溫度並未特別限定，但較佳為60~130℃，更佳為90~120℃。混合時間並未特別限定，但較佳為30~100分鐘，更佳為45~80分鐘。混合，並未特別限定，但較佳為在氮氣體環境下進行。又，對於混合，能使用上述周知的裝置。 In particular, in the case where the curable epoxy resin composition of the present invention contains the above alicyclic polyester resin, it is preferably prepared by the following method from the viewpoint of obtaining a uniform composition: an alicyclic polyester The resin is premixed with hydrogenated trimellitic anhydride (C) to prepare a mixture thereof (a mixture of an alicyclic polyester resin and a hydrogenated trimellitic anhydride (C)) Thereafter, the curing accelerator (E) and other additives are blended to the mixture to prepare an epoxy curing agent, and then the epoxy curing agent is mixed with the separately prepared epoxy resin. Further, in the case where the curable epoxy resin composition of the present invention contains the hardener (D), it is preferably prepared by alicyclic polyester resin, hydrogenated trimellitic anhydride (C), and a hardener. (D) premixing to prepare a mixture thereof (a mixture of an alicyclic polyester resin, a hydrogenated trimellitic anhydride (C), and a hardener (D)), and then blending a hardening accelerator (E) and other additives into the mixture. The epoxy hardener is prepared, and then the epoxy hardener is mixed with an additionally prepared epoxy resin. The temperature at which the alicyclic polyester resin and the hydrogenated trimellitic anhydride (C) (or the alicyclic polyester resin, the hydrogenated trimellitic anhydride (C), and the curing agent (D)) are mixed is not particularly limited, but is preferably 60 to 130 ° C, more preferably 90 to 120 ° C. The mixing time is not particularly limited, but is preferably from 30 to 100 minutes, more preferably from 45 to 80 minutes. The mixing is not particularly limited, but it is preferably carried out under a nitrogen atmosphere. Further, for the mixing, the above-described well-known device can be used.

在將上述脂環式聚酯樹脂及氫化偏苯三酸酐(C)(或者是，脂環式聚酯樹脂、氫化偏苯三酸酐(C)及硬化劑(D))混合後，並未特別限定，但可進一步施加適宜的化學處理(例如，添加氫或脂環式聚酯樹脂的末端改性等)等。又，在上述脂環式聚酯樹脂與氫化偏苯三酸酐(C)的混合物(或者是，脂環式聚酯樹脂、氫化偏苯三酸酐(C)及硬化劑(D)的混合物)中，氫化偏苯三酸酐(C)或硬化劑(D)的一部分亦可與上述脂環式聚酯樹脂(例如，脂環式聚酯樹脂的羥基等)反應。 The alicyclic polyester resin and the hydrogenated trimellitic anhydride (C) (or the alicyclic polyester resin, the hydrogenated trimellitic anhydride (C), and the curing agent (D)) are not particularly limited, but may be further applied. A suitable chemical treatment (for example, addition of hydrogen or an end modification of an alicyclic polyester resin, etc.) or the like. Further, in the mixture of the above alicyclic polyester resin and hydrogenated trimellitic anhydride (C) (or a mixture of an alicyclic polyester resin, a hydrogenated trimellitic anhydride (C) and a hardener (D), hydrogenated trimellitic anhydride (C) Or a part of the hardener (D) may be reacted with the above alicyclic polyester resin (for example, a hydroxyl group of an alicyclic polyester resin, etc.).

作為脂環式聚酯樹脂與硬化劑(D)的混合物，亦能使用例如：商品名「HN-7200」(日立化成工業(股)製)、商品名「HN-5700」(日立化成工業(股)製)等市售品。 As a mixture of the alicyclic polyester resin and the curing agent (D), for example, the trade name "HN-7200" (manufactured by Hitachi Chemical Co., Ltd.) and the trade name "HN-5700" (Hitachi Chemical Industry Co., Ltd.) can be used. Commercial products such as stocks).

<硬化物> <hardened matter>

能藉由使本發明的硬化性環氧樹脂組成物硬化，製得耐熱性、耐光性、及耐熱衝擊性優良，尤其是可使光半導體裝置在高溫下的通電特性及耐吸濕回流性提升的硬化物。硬化時的加熱溫度(硬化溫度)並未特別限定，但較佳為45~200℃，更佳為100~190℃，又更佳為100~180℃。又，硬化時加熱的時間(硬化時間)並未特別限定，但較佳為30~600分鐘，更佳為45~540分鐘，又更佳為60~480分鐘。在硬化溫度及硬化時間比上述範圍的下限值低的情況下，硬化變得不充分，相反的，在比上述範圍的上限值高的情況下，可能發生樹脂成分的分解，因此皆為不佳。硬化條件視各種條件而定，例如，能藉由在升高硬化溫度的情況下縮短硬化時間，在降低硬化溫度的情況下延長硬化時間等來適宜調整。 By curing the curable epoxy resin composition of the present invention, it is excellent in heat resistance, light resistance, and thermal shock resistance, and in particular, it can improve electric conduction characteristics and moisture absorption reflow resistance of an optical semiconductor device at a high temperature. Hardened material. The heating temperature (hardening temperature) at the time of hardening is not particularly limited, but is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, still more preferably 100 to 180 ° C. Further, the heating time (hardening time) at the time of hardening is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and still more preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit of the above range, the curing is insufficient. Conversely, when the curing temperature is higher than the upper limit of the above range, the decomposition of the resin component may occur, so that neither is good. The curing conditions are determined depending on various conditions. For example, the curing time can be shortened by increasing the curing temperature, and the curing time can be appropriately adjusted by lowering the curing temperature.

<光半導體封裝用樹脂組成物> <Resin composition for optical semiconductor encapsulation>

本發明的硬化性環氧樹脂組成物，能適合作為供封裝光半導體裝置中的光半導體(光半導體元件)用的樹脂組成物，即光半導體封裝用樹脂組成物使用。因用作上述光半導體封裝用樹脂組成物，而可製得利用具有高耐熱性、耐光性、及耐熱衝擊性，尤其是耐吸濕回流性優良的硬化物封裝之光半導體元件的光半導體裝置。上述光半導體裝置，即使是在具備高輸出、高輝度的光半導 體元件的情況下，光度仍難以隨著時間經過而降低，尤其是，即使是在被保管在高濕條件下後、經回流製程加熱的情況下，仍難以發生光度降低等的劣化。 The curable epoxy resin composition of the present invention can be suitably used as a resin composition for an optical semiconductor (optical semiconductor element) in a packaged optical semiconductor device, that is, a resin composition for optical semiconductor encapsulation. By using the resin composition for optical semiconductor encapsulation described above, an optical semiconductor device using an optical semiconductor device having high heat resistance, light resistance, and thermal shock resistance, particularly, a cured package having excellent moisture absorption reflow resistance can be obtained. The above optical semiconductor device is even in a light semiconductor having high output and high luminance In the case of a bulk element, it is difficult to reduce the illuminance with time, and in particular, even when it is stored under high-humidity conditions and heated by a reflow process, deterioration of luminosity or the like is less likely to occur.

<光半導體裝置> <Optical semiconductor device>

本發明的光半導體裝置係利用本發明的硬化性環氧樹脂組成物(光半導體封裝用樹脂組成物)的硬化物封裝光半導體元件的光半導體裝置。光半導體元件的封裝，係將以上述方法調製的硬化性環氧樹脂組成物注入指定的成形模具內，以指定的條件加熱硬化來進行。藉此，可製得利用硬化性環氧樹脂組成物的硬化物封裝光半導體元件的光半導體裝置。硬化溫度及硬化時間，能設定在與調製硬化物時同樣的範圍。 The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of a curable epoxy resin composition (resin composition for optical semiconductor encapsulation) of the present invention. The encapsulation of the optical semiconductor element is carried out by injecting the curable epoxy resin composition prepared by the above method into a predetermined molding die and heating and hardening under specified conditions. Thereby, an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of a curable epoxy resin composition can be obtained. The hardening temperature and the hardening time can be set in the same range as when the cured product is prepared.

本發明的硬化性環氧樹脂組成物並未限定於上述的光半導體元件的封裝用途，例如，亦能使用於：接著劑、電氣絕緣材、積層板、塗膜、印墨、塗料、封膠(sealant)、阻劑、複合材料、透明基材、透明片、透明薄膜、光學元件、光學透鏡、光學構件、光造型、電子紙、觸控面板、太陽能電池基板、光學波導(optical waveguide)、導光板、全像記憶體(holograph ic memory)等。 The curable epoxy resin composition of the present invention is not limited to the above-described packaging application of the optical semiconductor element, and can be used, for example, for an adhesive, an electrical insulating material, a laminate, a coating film, an ink, a coating, and a sealant. (sealant), resist, composite, transparent substrate, transparent sheet, transparent film, optical element, optical lens, optical member, optical molding, electronic paper, touch panel, solar cell substrate, optical waveguide, Light guide plate, holograph memory, etc.

實施例 Example

以下，基於實施例更詳細地說明本發明，但本發明並不受限於這些實施例。又，表1~4中的「-」意指不進行該成分的調配。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Further, "-" in Tables 1 to 4 means that the composition of the component is not performed.

製造例1 Manufacturing example 1 (橡膠粒子的製造) (manufacture of rubber particles)

在附加回流冷卻器的1L聚合容器，加入500g離子交換水、及0.68g二辛基磺基琥珀酸鈉，一邊在氮氣流下攪拌，一邊升溫至80℃。在此，一次添加相當於供形成橡膠粒子的核部分用的必要量之約5重量%份量之包含9.5g丙烯酸丁酯、2.57g苯乙烯、及0.39g二乙烯苯的單體混合物，攪拌20分鐘使其乳化後，添加9.5mg過氧二硫酸鉀，攪拌1小時進行最初的晶種聚合。接著，添加180.5mg過氧二硫酸鉀，攪拌5分鐘。在此，將使0.95g二辛基磺基琥珀酸鈉溶解於供形成核部分用的必要量之剩下部分(約95重量%份量)的180.5g丙烯酸丁酯、48.89g苯乙烯、7.33g二乙烯苯而成的單體混合物，花2小時連續地添加，進行第2次的晶種聚合，之後，熟成1小時而製得核部分。 Into a 1 L polymerization vessel to which a reflux condenser was attached, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were added, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. Here, a monomer mixture containing 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene, which is equivalent to about 5% by weight of the necessary amount for forming the core portion of the rubber particles, is added at a time, and stirred 20 After emulsification in a minute, 9.5 mg of potassium peroxodisulfate was added, and the mixture was stirred for 1 hour to carry out initial seed polymerization. Next, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.95 g of sodium dioctylsulfosuccinate was dissolved in 180.5 g of butyl acrylate, 48.89 g of styrene, and 7.33 g of the remainder (about 95% by weight) of the necessary amount for forming the core portion. The monomer mixture of divinylbenzene was continuously added for 2 hours, and the second seed crystal polymerization was carried out, followed by aging for 1 hour to obtain a core portion.

接下來，添加過氧二硫酸鉀60mg攪拌5分鐘，在此，將使0.3g二辛基磺基琥珀酸鈉溶解於60g甲基丙烯酸甲酯、1.5g丙烯酸、及0.3g甲基丙烯酸烯丙酯而成的單體混合物，花30分鐘連續地添加，進行晶種聚合。之後，熟成1小時，形成被覆核部分的殼層。 Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.3 g of sodium dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid, and 0.3 g of methacrylic acid. The monomer mixture obtained by esterification was continuously added for 30 minutes to carry out seed polymerization. Thereafter, the mixture was aged for 1 hour to form a shell layer of the core portion.

接下來，藉由冷卻至室溫(25℃)，使用孔徑120μm的塑膠製網過濾，來製得包含具有核殼構造的橡膠粒子的乳膠。將製得的乳膠於負30℃凍結，以吸引過濾器進行脫水洗淨後，於60℃進行送風乾燥一晝夜而製得橡膠粒子。所製得的橡膠粒子的平均粒徑為254nm，最大粒徑為486nm。 Next, a latex containing rubber particles having a core-shell structure was prepared by cooling to room temperature (25 ° C) and filtering using a plastic mesh having a pore size of 120 μm . The obtained latex was frozen at minus 30 ° C, and the filter was subjected to dehydration washing, and then air-dried at 60 ° C for a day and night to obtain rubber particles. The rubber particles thus obtained had an average particle diameter of 254 nm and a maximum particle diameter of 486 nm.

又，橡膠粒子的平均粒徑、最大粒徑，係使用以動態光散射法作為測定原理的「NanotracTM」形式的NANOTRACK粒度分布測定裝置(商品名「UPA-EX150」，日機裝(股)製)測定試料，在所得的粒度分布曲線中，將累積曲線來到50%時的粒徑之累積平均徑定為平均粒徑，將粒度分布測定結果的頻率(%)超過0.00%時的最大粒徑定為最大粒徑。又，作為上述試料，係使用使1重量份之在下述製造例2所製得的橡膠粒子分散環氧化合物分散於20重量份四氫呋喃者。 And average particle size of rubber particles, maximum particle size, particle-based using NANOTRACK "Nanotrac TM" form of a dynamic light scattering method as measurement principle distribution measuring apparatus (trade name "UPA-EX150", Nikkiso (shares) In the obtained particle size distribution curve, the cumulative average diameter of the particle diameter when the cumulative curve comes to 50% is defined as the average particle diameter, and the frequency (%) of the particle size distribution measurement result is greater than 0.00%. The particle size is set to the maximum particle size. In addition, as the sample, one part by weight of the rubber particle-dispersed epoxy compound obtained in the following Production Example 2 was dispersed in 20 parts by weight of tetrahydrofuran.

製造例2 Manufacturing Example 2 (橡膠粒子分散環氧化合物的製造) (Manufacture of rubber particle-dispersed epoxy compound)

使10重量份在製造例1製得的橡膠粒子，於在氮氣流下、加溫至60℃的狀態下，使用溶解器(1000rpm、60分鐘)，分散於70重量份商品名「CELLOXIDE 2021P」(3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯，DAICEL(股)製)，真空脫泡，製得橡膠粒子分散環氧化合物(在25℃的黏度：724mPa．s)。 10 parts by weight of the rubber particles obtained in Production Example 1 were dispersed in 70 parts by weight of a product name "CELLOXIDE 2021P" under a nitrogen gas flow and heated to 60 ° C using a dissolver (1000 rpm, 60 minutes). 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by DAICEL Co., Ltd., vacuum defoaming to obtain rubber particle-dispersed epoxy compound (viscosity at 25 ° C) : 724mPa.s).

又，在製造例2製得的橡膠粒子分散環氧化合物(使10重量份橡膠粒子分散於70重量份CELLOXIDE 2021P者)的黏度(在25℃的黏度)，係使用數位黏度計(商品名「DVU-EII型」、TOKIMEC(股)製)而測定。 In addition, the viscosity (the viscosity at 25 ° C) of the rubber particle-dispersed epoxy compound (the dispersion of 10 parts by weight of the rubber particles in 70 parts by weight of CELLOXIDE 2021P) obtained in Production Example 2 was carried out using a digital viscometer (trade name " Measured by DVU-EII type" and TOKIMEC (manufactured by TOKIMEC).

製造例3 Manufacturing Example 3 (核殼型丙烯酸聚合物粒子的製造) (Manufacture of core-shell type acrylic polymer particles)

在具備攪拌機、回流冷卻管、滴下幫浦、溫度控制裝置、及氮導入管的2升的可分離的燒瓶，加入585.0g離子交換水，進行攪拌。 In a 2-liter separable flask equipped with a stirrer, a reflux cooling tube, a drip pump, a temperature control device, and a nitrogen introduction tube, 585.0 g of ion-exchanged water was added and stirred.

另外，將453.5g甲基丙烯酸甲酯、71.5g甲基丙烯酸n-丁酯、5.25g二-2-乙基己基磺基琥珀酸銨、及262.5g離子交換水，利用均質機(25000rpm)乳化處理來調製單體混合物，將該單體混合物當中的10%投入上述燒瓶內，之後，在氮氣體環境下升溫至80℃。接下來，將預先調製的0.30g過硫酸銨的水溶液(使其溶解在15.0g離子交換水)一次加入上述燒瓶內，保持60分鐘，使晶種粒子形成。進一步地，在已形成晶種粒子的上述燒瓶內將剩下的單體混合物花180分鐘滴下，滴下後保持1小時，結束第1段的聚合。 Separately, 453.5 g of methyl methacrylate, 71.5 g of n-butyl methacrylate, 5.25 g of ammonium di-2-ethylhexylsulfosuccinate, and 262.5 g of ion-exchanged water were emulsified by a homogenizer (25,000 rpm). The monomer mixture was prepared by treatment, and 10% of the monomer mixture was placed in the flask, and then the temperature was raised to 80 ° C in a nitrogen atmosphere. Next, an aqueous solution of 0.30 g of ammonium persulfate prepared in advance (dissolved in 15.0 g of ion-exchanged water) was once added to the flask and held for 60 minutes to form seed crystal particles. Further, the remaining monomer mixture was dropped in the flask in which the seed particles were formed for 180 minutes, and left to stand for 1 hour to complete the polymerization in the first stage.

接下來，花90分鐘在上述燒瓶內滴下將219.3g甲基丙烯酸甲酯、5.7g甲基丙烯酸、2.25g二-2-乙基己基磺基琥珀酸銨、及112.5g離子交換水，利用均質機(25000rpm)乳化處理所製得的單體混合物，滴下後保持1小時，結束第2段的聚合，製得平均粒徑0.84μm的丙烯酸聚合物乳液。由上述丙烯酸聚合物乳液中的構成聚合物的丙烯酸聚合物的組成，利用第1段聚合形成的核成分的玻璃轉移溫度為90.6℃、溶解度參數(Fedors法)為20.45，利用第2段聚合形成的殼成分的玻璃轉移溫度為106.9℃、溶解度參數(Fedors法)為20.66。 Next, 219.3 g of methyl methacrylate, 5.7 g of methacrylic acid, 2.25 g of ammonium di-2-ethylhexylsulfosuccinate, and 112.5 g of ion-exchanged water were dropped in the flask over 90 minutes, and the mixture was homogenized. The monomer mixture obtained by the emulsification treatment (25,000 rpm) was kept for 1 hour after the dropwise addition, and the polymerization of the second stage was completed to obtain an acrylic polymer emulsion having an average particle diameter of 0.84 μm . The composition of the acrylic polymer constituting the polymer in the acrylic polymer emulsion is such that the core component formed by the first-stage polymerization has a glass transition temperature of 90.6 ° C and a solubility parameter (Fedors method) of 20.45, and is formed by the second-stage polymerization. The shell component had a glass transition temperature of 106.9 ° C and a solubility parameter (Fedors method) of 20.66.

將製得的丙烯酸聚合物乳液噴霧乾燥處理，製得核殼型丙烯酸聚合物粒子(丙烯酸聚合物粉體)。 The obtained acrylic polymer emulsion was spray-dried to obtain core-shell type acrylic polymer particles (acrylic polymer powder).

製造例4 Manufacturing Example 4 (脂環式聚酯樹脂的製造) (Manufacture of alicyclic polyester resin)

在具備攪拌機、溫度計、及回流冷卻器的反應容器，加入172重量份1,4-環己烷二羧酸(東京化成工業(股)製)、208重量份新戊二醇(東京化成工業(股)製)、及0.1重量份鈦酸四丁酯(和光純藥工業(股)製)，加熱至成為160℃，進一步花4小時從160℃升溫至250℃。接下來，花1小時減壓至5mmHg，進一步減壓至0.3mmHg以下後，在250℃下使其反應1小時，製得脂環式聚酯樹脂。 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 208 parts by weight of neopentyl glycol (Tokyo Chemical Industry Co., Ltd.) were added. (manufactured by the company), and 0.1 part by weight of tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 160 ° C, and further heated from 160 ° C to 250 ° C for 4 hours. Next, the pressure was reduced to 5 mmHg for 1 hour, and the pressure was further reduced to 0.3 mmHg or less, and then reacted at 250 ° C for 1 hour to obtain an alicyclic polyester resin.

在上述製得的脂環式聚酯樹脂的數量平均分子量係5,300。又，上述脂環式聚酯樹脂的數量平均分子量，係將使用凝膠滲透層析(GPC)測定的保持時間(保持容量)，利用以同一條件測定之已知分子量的標準聚苯乙烯的保持時間(保持容量)換算為聚苯乙烯的分子量而求得的值。具體而言，使用「HLC-8220GPC」(商品名，東曹(股)製)作為凝膠滲透層析裝置，使用2根「TSKgel G2000HHR」、「TSKgel G1000HHR」，及「Guard Column TSKgel HHR-L」(商品名，皆為東曹(股)製)合計4根作為管柱，使用微差折射率計作為檢出器，以移動相：四氫呋喃、測定溫度：40℃、流速：1mL/分的測定條件測定。 The alicyclic polyester resin obtained above had a number average molecular weight of 5,300. Further, the number average molecular weight of the alicyclic polyester resin is a retention time (holding capacity) measured by gel permeation chromatography (GPC), and is maintained by a standard polystyrene having a known molecular weight measured under the same conditions. The time (holding capacity) is a value obtained by converting the molecular weight of polystyrene. Specifically, "HLC-8220GPC" (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatography device, and two "TSKgel G2000H HR ", "TSKgel G1000H HR ", and "Guard Column TSKgel H" are used. HR- L" (product name, all manufactured by Tosoh Corporation) is used as a column, and a differential refractometer is used as a detector to move the phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / The measurement conditions were measured.

製造例5 Manufacturing Example 5 (環氧硬化劑的製造) (Manufacture of epoxy hardener)

以表1、表2所示的調配比例(單位：重量份)，將商品名「Rikacid MH-700」(硬化劑，新日本理化(股)製)、商品名「H-TMAn」(氫化偏苯三酸酐(環己烷-1,2,4-三羧酸-1,2-酐)，三菱化學(股)製)、商品名「U-CAT 18X」 (硬化促進劑，SAN-APRO(股)製)、在製造例4製得的脂環式聚酯樹脂、乙二醇(添加劑，和光純藥工業(股)製)，使用自公轉式攪拌裝置(THINKY(股)製，Awatori練太郎AR-250)均勻地混合，脫泡製得環氧硬化劑(有時稱為K劑)。 The product name "Rikacid MH-700" (hardener, manufactured by Nippon Chemical and Chemical Co., Ltd.) and the trade name "H-TMAn" (hydrogenated trimellitic anhydride) are listed in the ratios (unit: parts by weight) shown in Tables 1 and 2. (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride), manufactured by Mitsubishi Chemical Corporation, under the trade name "U-CAT 18X" (hardening accelerator, manufactured by SAN-APRO Co., Ltd.), alicyclic polyester resin obtained in Production Example 4, ethylene glycol (additive, manufactured by Wako Pure Chemical Industries, Ltd.), using a self-rotating stirring device (THINKY Co., Ltd., Awatori Rantaro AR-250) was uniformly mixed and defoamed to obtain an epoxy hardener (sometimes referred to as a K agent).

如表1、表2所示，實施例1~12中的環氧硬化劑包含氫化偏苯三酸酐，比較例1~9中的環氧硬化劑不包含氫化偏苯三酸酐。 As shown in Tables 1 and 2, the epoxy curing agents in Examples 1 to 12 contained hydrogenated trimellitic anhydride, and the epoxy curing agents in Comparative Examples 1 to 9 did not contain hydrogenated trimellitic anhydride.

實施例1 Example 1

首先，以表1所示的調配比例(單位：重量份)，將商品名「CELLOXIDE 2021P」(脂環式環氧化合物，DAICEL(股)製)、及異三聚氰酸單烯丙基二縮水甘油酯(MA-DGIC，四國化成工業(股))，使用自公轉式攪拌裝置(THINKY(股)製，Awatori練太郎AR-250)均勻地混合，脫泡製作環氧樹脂。又，上述混合，係為了使MA-DGIC溶解而實施在80℃下攪拌1小時。 First, the product name "CELLOXIDE 2021P" (alicyclic epoxy compound, manufactured by DAICEL Co., Ltd.) and isomeric cyanuric acid monoallyl II are shown in the mixing ratio (unit: parts by weight) shown in Table 1. Glycidyl ester (MA-DGIC, Shikoku Chemical Industry Co., Ltd.) was uniformly mixed using a self-rotating stirring device (manufactured by THINKY Co., Ltd., Awatori Rantaro AR-250), and defoamed to produce an epoxy resin. Further, the above mixing was carried out by stirring at 80 ° C for 1 hour in order to dissolve the MA-DGIC.

接下來，以成為表1所示的調配比例(單位：重量份)，將在上述製得的環氧樹脂及在製造例5製得的環氧硬化劑，使用自公轉式攪拌裝置(商品名「Awatori練太郎AR-250」，THINKY(股)製)均勻地混合，脫泡製得硬化性環氧樹脂組成物。 Next, using the blending ratio (unit: parts by weight) shown in Table 1, the epoxy resin obtained in the above and the epoxy hardener obtained in Production Example 5 were used in a self-revolving stirring apparatus (trade name). "Awatori Ryotaro AR-250", manufactured by THINKY Co., Ltd.) was uniformly mixed and defoamed to obtain a curable epoxy resin composition.

進一步地，將在上述製得的硬化性環氧樹脂組成物澆鑄至第1圖所示的光半導體的導線框(lead frame)(InGaN元件，3.5mm×2.8mm)後，在120℃的烘箱(樹脂硬化烘箱)加熱5小時，藉以製得利用上述硬化性 環氧樹脂組成物的硬化物封裝光半導體元件的光半導體裝置。又，在第1圖中，100表示反射器(光反射用樹脂組成物)，101表示金屬配線，102表示光半導體元件，103表示接合線(bonding wire)，104表示硬化物(封裝材)。 Further, the curable epoxy resin composition obtained above was cast into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of the optical semiconductor shown in Fig. 1, and then oven at 120 ° C. (Resin hardened oven) heated for 5 hours, thereby making use of the above hardenability The cured product of the epoxy resin composition encapsulates the optical semiconductor device of the optical semiconductor element. In the first drawing, 100 denotes a reflector (resin composition for light reflection), 101 denotes a metal wiring, 102 denotes an optical semiconductor element, 103 denotes a bonding wire, and 104 denotes a cured product (packaging material).

實施例2~12、比較例1~9 Examples 2 to 12 and Comparative Examples 1 to 9

除了將硬化性環氧樹脂組成物的組成變更為表1、表2所示的組成以外，與實施例1同樣地進行，調製硬化性環氧樹脂組成物。又，在實施例11中，使用在製造例2製得的橡膠粒子分散環氧化合物作為環氧樹脂的構成成分。 The curable epoxy resin composition was prepared in the same manner as in Example 1 except that the composition of the curable epoxy resin composition was changed to the compositions shown in Tables 1 and 2. Further, in Example 11, the rubber particle-dispersed epoxy compound obtained in Production Example 2 was used as a constituent component of the epoxy resin.

又，與實施例1同樣地製作光半導體裝置。 Further, an optical semiconductor device was produced in the same manner as in the first embodiment.

實施例13 Example 13

首先，以表3所示的調配比例(單位：重量份)，將商品名「CELLOXIDE 2021P」(脂環式環氧化合物，DAICEL(股)製)、及異三聚氰酸單烯丙基二縮水甘油酯(MA-DGIC，四國化成工業(股))，使用自公轉式攪拌裝置(THINKY(股)製，Awatori練太郎AR-250)均勻地混合，脫泡製得環氧樹脂。又，上述混合，係為了使MA-DGIC溶解而實施在80℃下攪拌1小時。 First, the product name "CELLOXIDE 2021P" (alicyclic epoxy compound, manufactured by DAICEL Co., Ltd.) and isomeric cyanuric acid monoallyl II are shown in the mixing ratio (unit: parts by weight) shown in Table 3. Glycidyl ester (MA-DGIC, Shikoku Chemical Industry Co., Ltd.) was uniformly mixed using a self-rotating stirring device (manufactured by THINKY Co., Ltd., Awatori Rantaro AR-250), and defoamed to obtain an epoxy resin. Further, the above mixing was carried out by stirring at 80 ° C for 1 hour in order to dissolve the MA-DGIC.

接下來，以成為表3所示的調配比例(單位：重量份)，將在上述製得的環氧樹脂、商品名「H-TMAn」(氫化偏苯三酸酐，三菱化學(股)製)、及商品名「San-Aid SI-100L」(硬化觸媒，三新化學工業(股)製)使用自公轉式攪拌裝置(商品名「Awatori練太郎AR-250」， THINKY(股)製)均勻地混合，脫泡製得硬化性環氧樹脂組成物。 Next, the epoxy resin obtained in the above, the trade name "H-TMAn" (hydrogenated trimellitic anhydride, manufactured by Mitsubishi Chemical Corporation), and the product are obtained in the blending ratio (unit: parts by weight) shown in Table 3. "San-Aid SI-100L" (hardening catalyst, manufactured by Sanshin Chemical Industry Co., Ltd.) uses a self-propelled stirring device (trade name "Awatori Ryotaro AR-250", THINKY (manufactured by the company) is uniformly mixed and defoamed to obtain a curable epoxy resin composition.

進一步地，將在上述製得的硬化性環氧樹脂組成物澆鑄至第1圖所示的光半導體的導線框(InGaN元件，3.5mm×2.8mm)後，在120℃的烘箱(樹脂硬化烘箱)加熱5小時，藉以製得利用上述硬化性環氧樹脂組成物的硬化物封裝光半導體元件的光半導體裝置。 Further, the curable epoxy resin composition obtained above was cast into a lead frame (InGaN element, 3.5 mm × 2.8 mm) of the optical semiconductor shown in Fig. 1, and then oven at 120 ° C (resin hardened oven) After heating for 5 hours, an optical semiconductor device in which an optical semiconductor element is encapsulated by a cured product of the above-mentioned curable epoxy resin composition is obtained.

實施例14~23、比較例10~18 Examples 14 to 23 and Comparative Examples 10 to 18

除了將硬化性環氧樹脂組成物的組成變更為表3、表4所示的組成以外，與實施例13同樣地進行，調製硬化性環氧樹脂組成物。又，如表3所示，在實施例17、19中進一步調配在製造例4製得的脂環式聚酯樹脂。 The curable epoxy resin composition was prepared in the same manner as in Example 13 except that the composition of the curable epoxy resin composition was changed to the compositions shown in Tables 3 and 4. Further, as shown in Table 3, the alicyclic polyester resins obtained in Production Example 4 were further blended in Examples 17 and 19.

又，與實施例13同樣地進行製作光半導體裝置。 Further, an optical semiconductor device was produced in the same manner as in the thirteenth embodiment.

<評價> <evaluation>

針對在實施例及比較例製得的光半導體裝置，實施下述的評價試驗。 The following evaluation tests were carried out on the optical semiconductor devices manufactured in the examples and the comparative examples.

[通電試驗] [Power-on test]

使用總光束測定機測定在實施例及比較例製得的光半導體裝置的總光束，將它定為「0小時的總光束」。進一步地，測定在85℃的恆溫槽內100小時後、將40mA的電流流入光半導體裝置的總光束，將它定為「100小時後的總光束」。然後，從下式算出光度保持率。將結果顯示在表1~4的「光度保持率[%]」欄。 The total light beam of the optical semiconductor device manufactured in the examples and the comparative examples was measured using a total beam measuring machine, and it was designated as "total light beam of 0 hours". Further, after 100 hours in a constant temperature bath at 85 ° C, a total light beam of 40 mA of current was flowed into the optical semiconductor device, and it was designated as "total light beam after 100 hours". Then, the photometric retention ratio was calculated from the following formula. The results are shown in the "Photometric retention rate [%]" column of Tables 1 to 4.

{光度保持率(%)}={100小時後的總光束(lm)}/{0小時的總光束(lm)}×100 {Photometric retention rate (%)}={Total beam (100) after 100 hours}/{0 hours total beam (lm)}×100

[焊料耐熱性試驗] [Solder heat resistance test]

將在實施例及比較例製得的光半導體裝置(就各硬化性環氧樹脂組成物各使用2個)，在30℃、70%RH的條件下靜置192小時進行吸濕處理。接下來，將上述光半導體裝置放入回流爐，在下述加熱條件下進行加熱處理。之後，將上述光半導體裝置取出至室溫環境下放冷後，再次放入回流爐在同條件下進行加熱處理。即，在該焊料耐熱性試驗中，對光半導體裝置施加兩次由下述加熱條件所形成的熱履歷。 The optical semiconductor devices (two for each curable epoxy resin composition) obtained in the examples and the comparative examples were allowed to stand for 192 hours under conditions of 30° C. and 70% RH to perform moisture absorption treatment. Next, the above optical semiconductor device was placed in a reflow furnace, and heat treatment was performed under the following heating conditions. Thereafter, the optical semiconductor device was taken out to room temperature and allowed to cool, and then placed in a reflow furnace and heat-treated under the same conditions. That is, in the solder heat resistance test, the heat history formed by the following heating conditions was applied twice to the optical semiconductor device.

[加熱條件(光半導體裝置的表面溫度基準)] [Heating conditions (surface temperature reference of optical semiconductor device)]

(1)預備加熱：在150~190℃下、60~120秒 (1) Preheating: at 150~190°C, 60~120 seconds

(2)預備加熱後的正式加熱：在217℃以上、60~150秒，最高溫度260℃ (2) Formal heating after preliminary heating: above 217 ° C, 60 to 150 seconds, maximum temperature 260 ° C

但是，從預備加熱轉換至正式加熱時的升溫速度係控制在最大3℃/秒。 However, the temperature increase rate from the preliminary heating to the main heating is controlled to a maximum of 3 ° C / sec.

第2圖，係顯示由回流爐所造成的加熱時的光半導體裝置的表面溫度曲線(在兩次加熱處理當中一次的加熱處理中的溫度曲線)的一個例子。 Fig. 2 is a view showing an example of a surface temperature curve (temperature curve in one heat treatment of one of the two heat treatments) of the optical semiconductor device when heated by the reflow furnace.

之後，使用數位顯微鏡(商品名「VHX-900」，KEYENCE(股)製)觀察光半導體裝置，評價是否在硬化物發生長度90μm以上的龜裂，及是否發生電極剝離(硬化物從電極表面剝離)。將2個光半導體裝置當中、在硬化物發生長度90μm以上的龜裂的光半導體裝置的個數顯示在表1~4的「焊料耐熱性試驗[龜裂數]」欄，將發生電極剝離的光半導體裝置的個數顯示在表1~4的「焊料耐熱性試驗[電極剝離數]」欄。 After that, the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.) to evaluate whether cracks occurred in the cured product with a length of 90 μm or more, and whether or not electrode peeling occurred (hardened material from the electrode) Surface peeling). Among the two optical semiconductor devices, the number of cracked optical semiconductor devices having a cured product length of 90 μm or more is shown in the "solder heat resistance test [crack number]" column of Tables 1 to 4, and the electrode is generated. The number of the peeled optical semiconductor devices is shown in the "solder heat resistance test [electrode peeling number]" column of Tables 1 to 4.

[熱衝撃試驗] [Hot rush test]

對在實施例及比較例製得的光半導體裝置(就各硬化性環氧樹脂組成物各使用2個)，使用熱衝撃試驗機施予200次循環的熱衝撃，其中1次循環的熱衝撃係在-40℃的氣體環境下曝露30分鐘，接著在120℃的氣體環境下曝露30分鐘。之後，使用數位顯微鏡(商品名「VHX-900」，KEYENCE(股)製)觀察在光半導體裝置中的硬化物所產生的龜裂的長度，計算2個光半導體裝置當中在硬化物發生長度90μm以上的龜裂之光半導體裝置的個數。將結果顯示在表1~4的「熱衝撃試驗[龜裂數]」欄。 For the optical semiconductor devices (two for each of the curable epoxy resin compositions) obtained in the examples and the comparative examples, 200 cycles of thermal charge were applied using a hot stamping tester, wherein one cycle of thermal flushing was performed. It was exposed to a gas atmosphere at -40 ° C for 30 minutes, and then exposed to a gas atmosphere of 120 ° C for 30 minutes. Then, the length of the crack generated by the cured product in the optical semiconductor device was observed using a digital microscope (trade name "VHX-900", manufactured by KEYENCE Co., Ltd.), and the length of the cured product in the two optical semiconductor devices was calculated to be 90 μm. The number of the above-mentioned cracked light semiconductor devices. The results are shown in the "Hot Punch Test [Cracks]" column in Tables 1 to 4.

[綜合判定] [Comprehensive judgment]

各試驗的結果，將下述(1)~(4)皆符合者判定為○(良好)。另一方面，在下述(1)~(4)任一者不符合的情況下判定為×(不良)。 As a result of each test, the following (1) to (4) were all judged as ○ (good). On the other hand, when none of the following (1) to (4) does not match, it is judged as × (bad).

(1)通電試驗：光度保持率為90%以上 (1) Power-on test: luminosity retention rate is above 90%

(2)焊料耐熱性試驗：在硬化物發生長度90μm以上的龜裂之光半導體裝置的個數為0個 (2) Solder heat resistance test: The number of cracked optical semiconductor devices having a cured product length of 90 μm or more is 0

(3)焊料耐熱性試驗：發生電極剝離的光半導體裝置的個數為0個 (3) Solder heat resistance test: the number of optical semiconductor devices in which electrode peeling occurred was 0

(4)熱衝擊試驗：在硬化物發生長度90μm以上的龜裂之光半導體裝置的個數為0個 (4) Thermal shock test: the number of cracked optical semiconductor devices having a cured product length of 90 μm or more is 0

將結果顯示在表1~4的「綜合判定」欄。 The results are displayed in the "Comprehensive judgment" column of Tables 1 to 4.

又，在實施例、比較例使用的成分如下。 Moreover, the components used in the examples and comparative examples are as follows.

CELLOXIDE 2021P：3,4-環氧環己基甲基(3,4-環氧)環己烷羧酸酯，DAICEL(股)製 CELLOXIDE 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, manufactured by DAICEL

MA-DGIC：異三聚氰酸單烯丙基二縮水甘油酯，四國化成工業(股)製 MA-DGIC: Isopropyl cyanurate monoallyl diglycidyl ester, Siguo Chemical Industry Co., Ltd.

X-40-2678：在分子內具有2個環氧基的矽氧烷衍生物，信越化學工業(股)製 X-40-2678: a decane derivative having two epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

X-40-2720：在分子內具有3個環氧基的矽氧烷衍生物，信越化學工業(股)製 X-40-2720: a decane derivative having three epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

X-40-2670：在分子內具有4個環氧基之矽氧烷衍生物，信越化學工業(股)製 X-40-2670: a cyclooxygen derivative having 4 epoxy groups in the molecule, manufactured by Shin-Etsu Chemical Co., Ltd.

YD-128：雙酚A型環氧樹脂，新日鐵化學(股)製 YD-128: bisphenol A epoxy resin, Nippon Steel Chemical Co., Ltd.

MH-700(Rikacid MH-700)：4-甲基六氫酞酸酐/六氫酞酸酐=70/30，新日本理化(股)製 MH-700(Rikacid MH-700): 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30, New Japan Physical and Chemical Co., Ltd.

H-TMAn：氫化偏苯三酸酐，三菱化學(股)製 H-TMAn: hydrogenated trimellitic anhydride, Mitsubishi Chemical Corporation

U-CAT 18X：硬化促進劑，SAN-APRO(股)製 U-CAT 18X: Hardening accelerator, SAN-APRO (share) system

乙二醇：和光純藥工業(股)製 Ethylene glycol: Wako Pure Chemical Industries Co., Ltd.

San-Aid SI-100L：硬化觸媒，三新化學工業(股)製 San-Aid SI-100L: hardening catalyst, Sanxin Chemical Industry Co., Ltd.

試驗機器 Test machine

．樹脂硬化烘箱 . Resin hardening oven

ESPEC(股)製 GPHH-201 ESPEC (share) system GPHH-201

．恆溫槽 . Thermostat

ESPEC(股)製 小型高溫腔ST-120B1 ESPEC (stock) system small high temperature chamber ST-120B1

．總光束測定機 . Total beam measuring machine

OPTRONIC LABORATORIES公司製 多頻道分光放射測定系統(Multi-channel spectroradiometer)OL771 OPTRONIC LABORATORIES company Multi-channel spectroradiometer OL771

．熱衝撃試驗機 . Hot punching test machine

ESPEC(股)製 小型冷熱衝撃裝置TSE-11-A ESPEC (stock) system small hot and cold flushing device TSE-11-A

．回流爐 . Reflow furnace

日本ANTOM(股)製 UNI-5016F Japan ANTOM (share) system UNI-5016F

產業上的可利用性 Industrial availability

本發明的硬化性環氧樹脂組成物能適合作為光半導體封裝用樹脂組成物使用。本發明的硬化性環氧樹脂組成物，亦能使用在：接著劑、電氣絕緣材、積層板、塗膜、印墨、塗料、封膠、阻劑、複合材料、透明基材、透明片、透明薄膜、光學元件、光學透鏡、光學構件、光造型、電子紙、觸控面板、太陽能電池基板、光學波導、導光板、全像記憶體等。 The curable epoxy resin composition of the present invention can be suitably used as a resin composition for optical semiconductor encapsulation. The curable epoxy resin composition of the present invention can also be used in: an adhesive, an electrical insulating material, a laminate, a coating film, an ink, a coating, a sealant, a resist, a composite material, a transparent substrate, a transparent sheet, Transparent film, optical element, optical lens, optical member, light shape, electronic paper, touch panel, solar cell substrate, optical waveguide, light guide plate, holographic memory, and the like.

Claims (14)

一種硬化性環氧樹脂組成物，其特徵為包含：脂環式環氧化合物(A)、由下述式(1) [式中，R1、R2分別表示氫原子或碳數1~8的烷基]表示的異三聚氰酸單烯丙基二縮水甘油酯化合物(B)、及由下述式(2) [式中，R11~R13分別表示氫原子或烷基；R14表示氫原子或對離子]表示的氫化偏苯三酸酐(hydrogenated trimellitic anhydride)(C)。 A curable epoxy resin composition characterized by comprising: an alicyclic epoxy compound (A), which is represented by the following formula (1) In the formula, R 1 and R 2 each represent a heteropolycyanate monoallyl diglycidyl ester compound (B) represented by a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a formula (2) ) [wherein, R 11 to R 13 each represent a hydrogen atom or an alkyl group; and R 14 represents a hydrogenated trimellitic anhydride (C) represented by a hydrogen atom or a counter ion]. 如請求項1之硬化性環氧樹脂組成物，其中脂環式環氧化合物(A)係具有環氧環己烷基的化合物。 The curable epoxy resin composition of claim 1, wherein the alicyclic epoxy compound (A) is a compound having an epoxycyclohexane group. 如請求項1或2之硬化性環氧樹脂組成物，其中脂環式環氧化合物(A)係由下述式(I-1)表示的化合物 The curable epoxy resin composition according to claim 1 or 2, wherein the alicyclic epoxy compound (A) is a compound represented by the following formula (I-1) 如請求項1至3中任一項之硬化性環氧樹脂組成物，其還包含在分子內具有2個以上的環氧基的矽氧烷衍生物。 The curable epoxy resin composition according to any one of claims 1 to 3, which further comprises a decane derivative having two or more epoxy groups in the molecule. 如請求項1至4中任一項之硬化性環氧樹脂組成物，其還包含脂環式聚酯樹脂。 The curable epoxy resin composition according to any one of claims 1 to 4, which further comprises an alicyclic polyester resin. 如請求項1至5中任一項之硬化性環氧樹脂組成物，其還包含橡膠粒子。 The curable epoxy resin composition according to any one of claims 1 to 5, which further comprises rubber particles. 如請求項1至6中任一項之硬化性環氧樹脂組成物，其還包含溶解度參數(Fedors法)為19.5~21.5[MPa1/2]的核殼型丙烯酸聚合物(acrylic polymer)粒子。 The curable epoxy resin composition according to any one of claims 1 to 6, which further comprises a core-shell type acrylic polymer particle having a solubility parameter (Fedors method) of 19.5 to 21.5 [MPa 1/2 ]. . 如請求項7之硬化性環氧樹脂組成物，其中構成前述核殼型丙烯酸聚合物粒子的核的丙烯酸聚合物的玻璃轉移溫度為60~120℃，構成殼的丙烯酸聚合物的玻璃轉移溫度為60~120℃。 The curable epoxy resin composition of claim 7, wherein the acrylic polymer constituting the core of the core-shell type acrylic polymer particles has a glass transition temperature of 60 to 120 ° C, and the glass transition temperature of the acrylic polymer constituting the shell is 60~120 °C. 如請求項7或8之硬化性環氧樹脂組成物，其中相對於脂環式環氧化合物(A)100重量份，前述核殼型丙烯酸聚合物粒子的含有量為1~30重量份。 The curable epoxy resin composition according to claim 7 or 8, wherein the content of the core-shell type acrylic polymer particles is from 1 to 30 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A). 如請求項1至9中任一項之硬化性環氧樹脂組成物，其還包含硬化劑(D)及硬化促進劑(E)。 The curable epoxy resin composition according to any one of claims 1 to 9, which further comprises a hardener (D) and a hardening accelerator (E). 如請求項1至9中任一項之硬化性環氧樹脂組成物，其還包含硬化觸媒(F)。 The curable epoxy resin composition according to any one of claims 1 to 9, which further comprises a hardening catalyst (F). 一種硬化物，係將如請求項1至11中任一項之硬化性環氧樹脂組成物硬化所製得。 A cured product obtained by hardening a curable epoxy resin composition according to any one of claims 1 to 11. 如請求項1至11中任一項之硬化性環氧樹脂組成物，其係光半導體封裝用樹脂組成物。 The curable epoxy resin composition according to any one of claims 1 to 11, which is a resin composition for optical semiconductor encapsulation. 一種光半導體裝置，係利用如請求項13之硬化性環氧樹脂組成物的硬化物來封裝光半導體元件。 An optical semiconductor device in which an optical semiconductor element is encapsulated by using a cured product of the curable epoxy resin composition of claim 13.
TW102120043A 2012-06-08 2013-06-06 Curable epoxy resin composition TWI579312B (en)

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