TW201609949A - Curable resin composition and cured product thereof, substrate for mounting optical semiconductor element, and optical semiconductor device - Google Patents
Curable resin composition and cured product thereof, substrate for mounting optical semiconductor element, and optical semiconductor device Download PDFInfo
- Publication number
- TW201609949A TW201609949A TW104124643A TW104124643A TW201609949A TW 201609949 A TW201609949 A TW 201609949A TW 104124643 A TW104124643 A TW 104124643A TW 104124643 A TW104124643 A TW 104124643A TW 201609949 A TW201609949 A TW 201609949A
- Authority
- TW
- Taiwan
- Prior art keywords
- resin composition
- compound
- epoxy resin
- group
- curable epoxy
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- 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
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/02—Containers; Seals
- H01L23/06—Containers; Seals characterised by the material of the container or its electrical properties
- H01L23/08—Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
-
- 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
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector 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
- H01L2224/32221—Disposition the layer connector 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
- H01L2224/32245—Disposition the layer connector 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
-
- 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
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Abstract
Description
本發明係關於硬化性環氧樹脂組成物及其硬化物、具有由該硬化物所形成的反射體的光半導體元件搭載用基板、以及具有該基板和光半導體元件的光半導體裝置。本案主張2014年7月31日於日本申請的日本特願2014-157197號的優先權，此處引用其內容。 The present invention relates to a curable epoxy resin composition and a cured product thereof, an optical semiconductor element mounting substrate having a reflector formed of the cured product, and an optical semiconductor device including the substrate and the optical semiconductor element. The priority of Japanese Patent Application No. 2014-157197, filed on Jan. 31,,,,,,,,,,,
近年來，在各種屋內或屋外顯示板、影像讀取用光源、交通號誌、大型顯示器用單元等方面，逐漸採用以光半導體元件(LED元件)為光源的發光裝置(光半導體裝置)。作為這種光半導體裝置，一般而言，在基板(光半導體元件搭載用基板)上搭載光半導體元件，進一步用透明的密封材密封該光半導體元件的光半導體裝置逐漸普及。對於這種光半導體裝置中的基板，為了提高從光半導體元件所發出的光的導出效率，而形成了使光反射用的構件(反射體)。 In recent years, light-emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources have been increasingly used in various indoor and outdoor display panels, light sources for image reading, traffic signals, and units for large displays. As such an optical semiconductor device, an optical semiconductor device is mounted on a substrate (an optical semiconductor element mounting substrate), and an optical semiconductor device in which the optical semiconductor device is further sealed with a transparent sealing material is gradually spread. In the substrate of such an optical semiconductor device, a member (reflector) for reflecting light is formed in order to increase the efficiency of light emission from the optical semiconductor element.
對上述反射體要求具有高光反射性。目前，作為上述反射體的構成材，已知有：使無機填料等分散在以對酞酸單元為必要的構成單元的聚醯胺樹脂(聚苯二甲基醯胺樹脂)中的樹脂組成物等(參照專利文獻1~3)。 The above reflector is required to have high light reflectivity. At the present time, as a constituent material of the above-mentioned reflector, a resin composition in which an inorganic filler or the like is dispersed in a polyamide resin (polyphenylene phthalamide resin) which is a constituent unit which is a constituent unit for a phthalic acid unit is known. Etc. (refer to Patent Documents 1 to 3).
此外，作為上述反射體的構成材，除上述外，例如，已知有：以特定比例含有包含環氧樹脂的熱硬化性樹脂、和折射率1.6-3.0的無機氧化物的光反射用硬化性環氧樹脂組成物(參照專利文獻4)。另外，已知有：含有熱硬化性樹脂成分、和1個以上的填充劑成分，將熱硬化性樹脂成分整體的折射率和各填充劑成分的折射率的差、及由各填充劑成分的體積比例所算出的參數控制在特定範圍內的光反射用硬化性環氧樹脂組成物(參照專利文獻5)。 In addition, as a constituent material of the above-mentioned reflector, for example, it is known that a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0 are contained in a specific ratio. Epoxy resin composition (refer to Patent Document 4). In addition, it is known that the thermosetting resin component and one or more filler components are contained, and the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the respective filler components are known. The parameter calculated by the volume ratio is controlled by a curable epoxy resin composition for light reflection within a specific range (see Patent Document 5).
專利文獻1 日本特開2000-204244號公報 Patent Document 1 Japanese Patent Laid-Open Publication No. 2000-204244
專利文獻2 日本特開2004-75994號公報 Patent Document 2 Japanese Patent Laid-Open Publication No. 2004-75994
專利文獻3 日本特開2006-257314號公報 Patent Document 3 Japanese Patent Laid-Open Publication No. 2006-257314
專利文獻4 日本特開2010-235753號公報 Patent Document 4 Japanese Patent Laid-Open Publication No. 2010-235753
專利文獻5 日本特開2010-235756號公報 Patent Document 5 Japanese Patent Laid-Open Publication No. 2010-235756
儘管如此，專利文獻1~3記載的由上述聚醯胺樹脂而成的反射體，特別是在以高輸出功率的藍色光半導體或白色光半導體為光源的發光裝置中，有因從光半導體元件所發出的光或熱而伴隨時間經過產生黃變等而劣化，不能維持充分的光反射性這樣的問題。另外，隨著無鉛焊料的採用，也產生了在發光裝置製造之際的 回流步驟(焊料回流步驟)中的加熱溫度變得更高的趨勢中，上述反射體也因在這樣的製造步驟中施加的熱而伴隨時間經過而劣化，光反射性降低這樣的問題。 In addition, the reflector made of the above-mentioned polyimide resin described in Patent Documents 1 to 3 is particularly used in a light-emitting device using a high-power blue-light semiconductor or a white light semiconductor as a light source. The emitted light or heat is deteriorated with yellowing or the like with the passage of time, and the problem of sufficient light reflectivity cannot be maintained. In addition, with the adoption of lead-free solder, it also occurs at the time of manufacture of the light-emitting device. In the tendency that the heating temperature in the reflow step (solder reflow step) becomes higher, the above-mentioned reflector is also deteriorated with time due to heat applied in such a manufacturing step, and the light reflectivity is lowered.
此外，在專利文獻4、5記載的包含光反射用硬化性環氧樹脂組成物的硬化物的反射體中，使用了異三聚氰酸三環氧丙酯作為上述熱硬化性樹脂的主成分，耐熱性不充分，產生了因從光半導體元件所發出的熱或回流步驟中的熱，而光反射性伴隨時間經過而降低這樣的問題。 Further, in the reflector including the cured product of the curable epoxy resin composition for light reflection described in Patent Documents 4 and 5, triglycidyl isocyanurate is used as a main component of the thermosetting resin. The heat resistance is insufficient, and there is a problem that the light reflectivity decreases with time due to heat generated from the optical semiconductor element or heat in the reflow step.
另外，上述反射體，除了要求上述耐熱性、耐光性外，在施加由切削加工或溫度變化(例如，在如回流步驟的非常高溫下的加熱、或冷溫循環等)等所形成的應力的情況下，也要求難以發生龜裂(crack)(有將這種特性稱為「耐龜裂性」的情況)等、強韌。因為若反射體發生龜裂，則光反射性降低(即，光導出效率降低)，變得難以擔保發光裝置的可靠性。 Further, in addition to the above-mentioned heat resistance and light resistance, the above-mentioned reflector is subjected to stress generated by cutting processing or temperature change (for example, heating at a very high temperature such as a reflow step, or a cold temperature cycle). In the case, it is also required to be strong and hard to crack (it is called "crack resistance"). When the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it becomes difficult to secure the reliability of the light-emitting device.
因此，現狀係要求可以形成即使遭受更高輸出功率、短波長的光或高溫也不會發生劣化或龜裂產生等的不良狀況，光反射性難以伴隨時間經過而降低的反射體，且耐熱性及耐光性優異而且強韌的材料。 Therefore, in the current situation, it is required to form a reflector which does not cause deterioration or cracking even when subjected to light of a higher output, a short wavelength, or a high temperature, and it is difficult for the light reflectivity to be lowered with time, and the heat resistance is improved. And a material that is excellent in light resistance and strong.
由此，本發明的目的在於提供能形成具有高反射率(光反射性)、耐熱性優異的硬化物的硬化性環氧樹脂組成物。此外，本發明的另一目的還在於提供能形成耐光性優異、強韌的硬化物的硬化性環氧樹脂組成物。 Therefore, an object of the present invention is to provide a curable epoxy resin composition capable of forming a cured product having high reflectance (light reflectivity) and excellent heat resistance. Further, another object of the present invention is to provide a curable epoxy resin composition capable of forming a cured product excellent in light resistance and toughness.
此外，本發明的另一目的在於提供具有高反射率、耐熱性優異的硬化物。此外，本發明的另一目的還在於提供耐光性優異、強韌的硬化物。 Further, another object of the present invention is to provide a cured product having high reflectance and excellent heat resistance. Further, another object of the present invention is to provide a cured product which is excellent in light resistance and strong.
另外，本發明的另一目的在於提供具有耐熱性優異、具有高反射率的反射體的光半導體元件搭載用基板。此外，本發明的另一目的還在於提供具有耐光性優異、強韌的反射體的光半導體元件搭載用基板。 In addition, another object of the present invention is to provide an optical semiconductor element mounting substrate having a reflector having excellent heat resistance and high reflectance. Further, another object of the present invention is to provide a substrate for mounting an optical semiconductor element having a reflector excellent in light resistance and strong.
另外，本發明的另一目的在於提供光的導出效率高、耐久性高的光半導體裝置。 Further, another object of the present invention is to provide an optical semiconductor device having high light extraction efficiency and high durability.
本發明人，為了解決上述課題而深入檢討，結果發現一種含有脂環式環氧化合物、特定的異三聚氰酸衍生物、無機填充劑、硬化劑、和硬化促進劑的硬化性環氧樹脂組成物，含有一定量以上的前述異三聚氰酸衍生物及無機填充劑的硬化性環氧樹脂組成物能形成反射率高、耐熱性優異的硬化物，特別是，作為供形成光半導體元件搭載用基板及具有該基板的光半導體裝置中的反射體用的樹脂組成物(反射體形成用樹脂組成物)是有用的。本發明係基於這些知識所完成者。 The present inventors have intensively reviewed in order to solve the above problems, and as a result, found a curable epoxy resin containing an alicyclic epoxy compound, a specific isocyanuric acid derivative, an inorganic filler, a hardener, and a hardening accelerator. In the composition, the curable epoxy resin composition containing a certain amount or more of the isomeric cyanuric acid derivative and the inorganic filler can form a cured product having high reflectance and excellent heat resistance, and particularly, as an optical semiconductor element for forming A resin composition (a resin composition for forming a reflector) for a reflector in a mounting substrate and an optical semiconductor device having the substrate is useful. The present invention is based on the completion of such knowledge.
即，本發明提供一種硬化性環氧樹脂組成物，其包含：脂環式環氧化合物(A)、下述式(1)所表示的異三聚氰酸一烯丙基二環氧丙酯化合物(B)、無機填充劑(C)、硬化劑(D)、和硬化促進劑(E)，
[式(1)中，R1及R2表示氫或者碳數1~8的烷基]，其特徵為：化合物(B)的含量係相對於脂環式環氧化合物(A)和化合物(B)的總量(100重量%)為50~95重量%，且無機填充劑(C)的含量係相對於前述硬化性環氧樹脂組成物的總量(100重量%)為30~95重量%。 [In the formula (1), R 1 and R 2 represent hydrogen or an alkyl group having 1 to 8 carbon atoms], and the compound (B) is contained in an amount relative to the alicyclic epoxy compound (A) and the compound ( The total amount (100% by weight) of B) is 50 to 95% by weight, and the content of the inorganic filler (C) is 30 to 95% by weight based on the total amount (100% by weight) of the curable epoxy resin composition. %.
另外，提供一種前述硬化性環氧樹脂組成物，其進一步包含白色顏料(F)，且白色顏料(F)的含量係相對於無機填充劑(C)及白色顏料(F)的合計量為3~40重量%。 Further, the present invention provides a curable epoxy resin composition further comprising a white pigment (F), and the content of the white pigment (F) is 3 in total with respect to the inorganic filler (C) and the white pigment (F). ~40% by weight.
另外，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)係由包含具有環氧環己烷(cyclohexene oxide)基的化合物、下述式(II)
[式(II)中，R’係從p價的醇的構造式去除p個羥基(-OH)的基(p價的有機基)，p、n分別表示自然數] [In the formula (II), R' is a group in which p hydroxyl groups (-OH) are removed from the structural formula of a p-valent alcohol (p-valent organic group), and p and n represent natural numbers, respectively]
所表示的化合物、及氫化芳香族環氧丙基醚系環氧化合物的群組所選出的至少1者。 At least one selected from the group consisting of a compound and a hydrogenated aromatic epoxidopropyl ether epoxy compound.
另外，提供一種前述硬化性環氧樹脂組成物，其中，具有環氧環己烷基的化合物係下述式(I)所表示的化合物：
[式(I)中，X表示單鍵或者連結基(具有1個以上原子的二價的基)]。 In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms)].
另外，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)係下述式(I-1)所表示的化合物：
另外，提供一種前述硬化性環氧樹脂組成物，其係轉移成型用或者壓縮成型用樹脂組成物。 Further, a curable epoxy resin composition which is a resin composition for transfer molding or compression molding is provided.
另外，提供一種前述硬化性環氧樹脂組成物，其係反射體形成用樹脂組成物。 Further, a curable epoxy resin composition which is a resin composition for forming a reflector is provided.
此外，本發明提供一種硬化物，其係藉由使前述硬化性環氧樹脂組成物硬化來得到。 Further, the present invention provides a cured product obtained by hardening the curable epoxy resin composition.
此外，本發明提供一種光半導體元件搭載用基板，其具有由前述硬化性環氧樹脂組成物的硬化物所形成的反射體。 Moreover, the present invention provides a substrate for mounting an optical semiconductor element having a reflector formed of a cured product of the curable epoxy resin composition.
此外，本發明提供一種光半導體裝置，其具有前述光半導體元件搭載用基板、和搭載在該基板的光半導體元件。 Furthermore, the present invention provides an optical semiconductor device including the optical semiconductor element mounting substrate and an optical semiconductor element mounted on the substrate.
即，本發明涉及以下內容。 That is, the present invention relates to the following.
[1]一種硬化性環氧樹脂組成物，其包含：脂環式環氧化合物(A)、下述式(1)所表示的異三聚氰酸一烯丙基二環氧丙酯化合物(B)、無機填充劑(C)、硬化劑(D)、和硬化促進劑(E)，
[式(1)中，R1及R2表示氫或者碳數1~8的烷基] [In the formula (1), R 1 and R 2 represent hydrogen or an alkyl group having 1 to 8 carbon atoms]
其特徵為：化合物(B)的含量係相對於脂環式環氧化合物(A)和化合物(B)的總量(100重量%)為50~95重量%，且無機填充劑(C)的含量係相對於前述硬化性環氧樹脂組成物的總量(100重量%)為30~95重量%。 It is characterized in that the content of the compound (B) is 50 to 95% by weight based on the total amount (100% by weight) of the alicyclic epoxy compound (A) and the compound (B), and the inorganic filler (C) The content is 30 to 95% by weight based on the total amount (100% by weight) of the curable epoxy resin composition.
[2]如[1]記載的硬化性環氧樹脂組成物，其還包含白色顏料(F)，且白色顏料(F)的含量係相對於無機填充劑(C)及白色顏料(F)的合計量為3~40重量%。 [2] The curable epoxy resin composition according to [1], which further contains a white pigment (F), and the content of the white pigment (F) is relative to the inorganic filler (C) and the white pigment (F). The total amount is 3 to 40% by weight.
[3]如[1]或[2]記載的硬化性環氧樹脂組成物，其中，前述脂環式環氧化合物(A)係由選自由具有環氧環己烷基的化合物、下述式(II)所表示的化合物、及氫化芳香族環氧丙基醚系環氧化合物組成的群組所選出的至少1者，
[式(II)中，R’係從p價的醇的構造式去除p個羥基(-OH)的基(p價的有機基)，p、n分別表示自然數]。 In the formula (II), R' is a group in which p hydroxyl groups (-OH) (p-valent organic groups) are removed from the structural formula of a p-valent alcohol, and p and n each represent a natural number].
[4]如[3]記載的硬化性環氧樹脂組成物，其中，前述具有環氧環己烷基的化合物係下述式(I)所表示的化合物
[式(I)中，X表示單鍵或者連結基(具有1個以上原子的二價的基)]。 In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms)].
[5]如[1]至[4]中任一項記載的硬化性環氧樹脂組成物，其中，前述脂環式環氧化合物(A)係下述式(I-1)所表示的化合物
[6]如[1]至[5]中任一項記載的硬化性環氧樹脂組成物，其中，前述硬化劑(D)係選自由甲基四氫酞酸酐、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、酞酸酐、四氫酞酸酐、六氫酞酸酐、及甲基環己烯二羧酸酐組成的群組的至少一者。 [6] The curable epoxy resin composition according to any one of [1], wherein the curing agent (D) is selected from the group consisting of methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride. At least one of the group consisting of dodecenyl succinic anhydride, methyl endomethylene tetrahydrophthalic anhydride, decanoic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic anhydride.
[7]如[1]至[6]中任一項記載的硬化性環氧樹脂組成物，其中，脂環式環氧化合物(A)的含量係相對於硬化性環氧樹脂組成物的總量為0.3~10重量%。 [7] The curable epoxy resin composition according to any one of [1] to [6] wherein the content of the alicyclic epoxy compound (A) is relative to the total of the curable epoxy resin composition. The amount is 0.3 to 10% by weight.
[8]如[1]至[7]中任一項記載的硬化性環氧樹脂組成物，其中，相對於脂環式環氧化合物(A)和化合物(B)的總量，脂環式環氧化合物(A)的用量為5~50重量%。 [8] The curable epoxy resin composition according to any one of [1] to [7], wherein the alicyclic ring type is the alicyclic type with respect to the total amount of the alicyclic epoxy compound (A) and the compound (B). The epoxy compound (A) is used in an amount of 5 to 50% by weight.
[9]如[1]至[8]中任一項記載的硬化性環氧樹脂組成物，其中，前述硬化劑(D)的用量係相對於硬化性環氧樹脂組成物中所包含的具有環氧基的化合物的總量(100重量份)為50~200重量份。 [9] The curable epoxy resin composition according to any one of [1] to [8] wherein the curing agent (D) is used in an amount relative to the curable epoxy resin composition. The total amount (100 parts by weight) of the epoxy group-containing compound is 50 to 200 parts by weight.
[10]如[1]至[9]中任一項記載的硬化性環氧樹脂組成物，其中，前述硬化促進劑(E)係選自由1,8-二氮雜雙環[5.4.0]十一烯-7、及其鹽；1,5-二氮雜雙環[4.3.0]壬烯-5、及其鹽；3級胺；咪唑類；鏻化合物；有機金屬鹽；金屬嵌合劑所組成的群組的至少一種。 [10] The curable epoxy resin composition according to any one of [1], wherein the hardening accelerator (E) is selected from 1,8-diazabicyclo [5.4.0] Undecene-7, and its salts; 1,5-diazabicyclo[4.3.0]nonene-5, and salts thereof; tertiary amines; imidazoles; antimony compounds; organometallic salts; metal chimeric agents At least one of the group consisting of.
[11]如[1]至[10]中任一項記載的硬化性環氧樹脂組成物，其中，前述硬化促進劑(E)的用量係相對於硬化性環氧樹脂組成物中所包含的具有環氧基的化合物的總量(100重量份)為0.05~5重量份。 [11] The curable epoxy resin composition according to any one of [1], wherein the curing accelerator (E) is used in an amount relative to the curable epoxy resin composition. The total amount (100 parts by weight) of the compound having an epoxy group is 0.05 to 5 parts by weight.
[12]如[1]至[11]中任一項記載的硬化性環氧樹脂組成物，其中，前述無機填充劑(C)係氧化矽。 [12] The curable epoxy resin composition according to any one of [1] to [11] wherein the inorganic filler (C) is cerium oxide.
[13]如[2]至[12]中任一項記載的硬化性環氧樹脂組成物，其中，前述白色顏料(F)係選自由無機氧化物及無機中空粒子所組成的群組的至少一種。 [13] The curable epoxy resin composition according to any one of [2], wherein the white pigment (F) is at least selected from the group consisting of inorganic oxides and inorganic hollow particles. One.
[14]如[2]至[13]中任一項記載的硬化性環氧樹脂組成物，其中，合併前述無機填充劑(C)和白色顏料(F)的用量係相對於硬化性環氧樹脂組成物的總量為60~95重量%。 [14] The curable epoxy resin composition according to any one of [2] to [13] wherein the inorganic filler (C) and the white pigment (F) are combined in an amount relative to the curable epoxy The total amount of the resin composition is 60 to 95% by weight.
[15]如[1]至[14]中任一項記載的硬化性環氧樹脂組成物，其係轉移成型用或者壓縮成型用樹脂組成物。 [15] The curable epoxy resin composition according to any one of [1] to [14] which is a resin composition for transfer molding or compression molding.
[16]如[1]至[15]中任一項記載的硬化性環氧樹脂組成物，其係反射體形成用樹脂組成物。 [16] The curable epoxy resin composition according to any one of [1] to [15] which is a resin composition for forming a reflector.
[17]一種硬化物，其係藉由使如[1]至[16]中任一項記載的硬化性環氧樹脂組成物硬化來得到。 [17] A cured product obtained by curing the curable epoxy resin composition according to any one of [1] to [16].
[18]一種光半導體元件搭載用基板，其具有由如[17]記載的硬化性環氧樹脂組成物的硬化物所形成的反射體。 [18] A substrate for mounting an optical semiconductor element, comprising a reflector formed of a cured product of the curable epoxy resin composition according to [17].
[19]一種光半導體裝置，其具有如[18]記載的光半導體元件搭載用基板、和搭載在該基板的光半導體元件。 [19] An optical semiconductor device comprising the optical semiconductor element mounting substrate according to [18], and an optical semiconductor device mounted on the substrate.
由於本發明的硬化性環氧樹脂組成物具有上述構成，因此使該硬化性環氧樹脂組成物硬化所得到的硬化物具有高光反射性，另外，由於耐熱性及耐光性優異，而且因強韌而難以產生龜裂，因此光反射性難以伴隨時間經過而降低。因此，本發明的硬化性環氧樹脂組成物能較佳地用於光半導體裝置相關的各種用途，特別是作為LED封裝用的光反射用硬化性樹脂組成物。另外，由於包含本發明的硬化性環氧樹脂組成物(光反射用硬化性樹脂組成物)的硬化物的反射體(反射材)能夠長期持續發揮高光反射性，因此至少具備光半導體元件和上述反射體的光半導體裝置(發光裝置)作為長壽命的光半導體裝置，能發揮高可靠性。 Since the curable epoxy resin composition of the present invention has the above-described configuration, the cured product obtained by curing the curable epoxy resin composition has high light reflectivity, is excellent in heat resistance and light resistance, and is tough. However, it is difficult to generate cracks, and thus it is difficult for light reflectance to decrease with time. Therefore, the curable epoxy resin composition of the present invention can be preferably used for various applications related to optical semiconductor devices, and is particularly useful as a light-reflecting curable resin composition for LED packaging. In addition, since the reflector (reflecting material) containing the cured product of the curable epoxy resin composition (curable resin composition for light reflection) of the present invention can exhibit high light reflectivity for a long period of time, it is provided with at least the optical semiconductor element and the above. The optical semiconductor device (light-emitting device) of the reflector can exhibit high reliability as a long-life optical semiconductor device.
100‧‧‧反射體 100‧‧‧ reflector
101‧‧‧金屬配線 101‧‧‧Metal wiring
102‧‧‧光半導體元件的搭載區域 102‧‧‧Mounting area of optical semiconductor components
103‧‧‧接合導線 103‧‧‧bonding wire
104‧‧‧光半導體元件的密封材 104‧‧‧ Sealing material for optical semiconductor components
105‧‧‧晶粒接合材 105‧‧‧Grade joints
106‧‧‧光半導體元件 106‧‧‧Optical semiconductor components
第1圖係顯示本發明的光半導體元件搭載用基板之一例的概略圖。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 example of a substrate for mounting an optical semiconductor element 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圖係顯示本發明的光半導體裝置之一例的概略圖(剖面圖)。 Fig. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention.
本發明的硬化性環氧樹脂組成物含有脂環式環氧化合物(A)、下述式(1)所表示的異三聚氰酸一烯丙基二環氧丙酯化合物(B)
[式(1)中，R1及R2表示氫或者碳數1~8的烷基]、無機填充劑(C)、硬化劑(D)、和硬化促進劑(E)作為必要成分，其特徵為：化合物(B)的含量係相對於脂環式環氧化合物(A)和化合物(B)的總量(100重量份)為50重量%以上95重量%以下，且無機填充劑(C)的含量係相對於前述硬化性環氧樹脂組成物的總量(100重量%)為30重量%以 上95重量%以下。本發明的硬化性環氧樹脂組成物，除了上述必要成分以外，可以依需要而含有其他的成分。 [In the formula (1), R 1 and R 2 represent hydrogen or an alkyl group having 1 to 8 carbon atoms], an inorganic filler (C), a curing agent (D), and a curing accelerator (E) are essential components. The content of the compound (B) is 50% by weight or more and 95% by weight or less based on the total amount (100 parts by weight) of the alicyclic epoxy compound (A) and the compound (B), and the inorganic filler (C) The content is 30% by weight or more and 95% by weight or less based on the total amount (100% by weight) of the curable epoxy resin composition. The curable epoxy resin composition of the present invention may contain other components as needed in addition to the above-mentioned essential components.
構成本發明的硬化性環氧樹脂組成物的脂環式環氧化合物(A)係分子內(1分子內)至少具有脂環(脂肪族環)構造和環氧基的化合物。更具體而言，脂環式環氧化合物(A)，係例如，包含：(i)具有以構成脂環的鄰接的2個碳原子和氧原子所構成的環氧基(有稱為「脂環環氧基」的情況)的化合物；(ii)環氧基係直接以單鍵鍵結於脂環上的化合物；及(iii)氫化芳香族環氧丙基醚系環氧化合物等。 The alicyclic epoxy compound (A) constituting 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 the molecule (within one molecule). More specifically, the alicyclic epoxy compound (A), for example, comprises: (i) an epoxy group having two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring (referred to as "fat" a compound of the case of a cycloepoxy group; (ii) a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond; and (iii) a hydrogenated aromatic epoxidized propyl ether epoxy compound.
作為(i)具有用構成脂環的鄰接的2個碳原子和氧原子所構成的環氧基(脂環環氧基)的化合物，係能夠從公知或慣用者當中任意地選擇使用。其中，上述化合物較佳為具有用構成環己烷環的鄰接的2個碳原子和氧原子所構成的環氧基，即，具有環氧環己烷基的化合物(脂環式環氧化合物)。 (i) A compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring can be arbitrarily selected from known or customary. Among them, the above compound preferably has an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting a cyclohexane ring, that is, a compound having an epoxycyclohexane group (alicyclic epoxy compound). .
作為(i)具有用構成脂環的鄰接的2個碳原子和氧原子所構成的環氧基(脂環環氧基)的化合物，特別是在耐熱性、耐光性方面上，較佳為用下述式(I)所表示的脂環式環氧化合物(脂環式環氧樹脂)。 (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring, and particularly preferably used for heat resistance and light resistance. An alicyclic epoxy compound (alicyclic epoxy resin) represented by the following formula (I).
式(I)中，X表示單鍵或者連結基(具有1個以上原子的二價的基)。作為上述連結基，例如，可舉出：二價的烴基、碳-碳雙鍵的一部分或者全部被環氧化的伸烯基、羰基、醚鍵、酯鍵、碳酸酯基、醯胺基、它們複數個連結而成的基等。又，烷基等的取代基可以鍵結於式(I)中的構成環己烷環(環氧環己烷基)的碳原子中的1個以上。 In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenyl group in which a part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine group, and the like. A plurality of connected bases, etc. Further, a substituent such as an alkyl group may be bonded to one or more of the carbon atoms constituting the cyclohexane ring (epoxycyclohexane group) in the formula (I).
作為式(I)中的X係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 of the X-based single bond in the formula (I) may, for example, be 3,4,3',4'-diepoxybicyclohexane or the like.
作為上述二價的烴基，例如，可舉出：碳數為1~18的直鏈或分枝鏈狀的伸烷基、二價的脂環式烴基等。作為碳數為1~18的直鏈或者分枝鏈狀的伸烷基，例如，可舉出：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。作為二價的脂環式烴基，例如，可舉出：1,2-伸環戊基、1,3-伸環戊基、環亞戊基、1,2-伸環己基、1,3-伸環己基、1,4-伸環己基、環亞己基等的二價的伸環烷基(包含環亞烷基)等。 Examples of the divalent hydrocarbon group include a linear or branched chain alkyl group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched chain 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 so on. 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 cycloalkylene group (including a cycloalkylene group) such as a cyclohexyl group, a 1,4-cyclohexylene group or a cyclohexylene group.
作為上述碳-碳雙鍵的一部分或者全部被環氧化的伸烯基(有稱為「環氧化伸烯基」的情況)中的伸烯基，例如，可舉出：伸乙烯基、伸丙烯基、1-伸丁烯基、2-伸丁烯基、伸丁二烯基、伸戊烯基、伸己烯基、伸庚烯基、伸辛烯基等的碳數2~8的直鏈或者分枝鏈狀的伸烯基。特別是，作為上述環氧化伸烯基，較佳為碳-碳雙鍵全部被環氧化的伸烯基，更佳為碳-碳雙鍵全部被環氧化的碳數2~4的伸烯基。 Examples of the extended alkenyl group in the case of the alkenyl group which is epoxidized in part or all of the carbon-carbon double bond (in the case of "epoxidized alkenyl group") include, for example, a vinyl group and a propylene group. Carbon, 2 to 8 straight, 1-butenyl, 2-butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, etc. Chain or branched chain extended alkenyl group. In particular, as the epoxidized alkenyl group, an alkenyl group in which all of the carbon-carbon double bonds are epoxidized, and more preferably an alkenyl group having 2 to 4 carbon atoms which are all epoxidized by carbon-carbon double bonds .
作為上述連結基X，特別是，較佳為含有氧原子的連結基，具體而言，可舉出：-CO-、-O-CO-O-、-COO-、-O-、-CONH-、環氧化伸烯基；複數個這些基連結而成的基；這些基中的1個或2個以上與1個或2個以上的二價的烴基連結而成基等。作為二價的烴基，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-. An epoxidized alkenyl group; a group in which a plurality of these groups are bonded; one or two or more of these groups are bonded to one or two or more divalent hydrocarbon groups to form a group. The divalent hydrocarbon group is exemplified above.
作為用上述式(I)所表示的脂環式環氧化合物的代表例，可舉出：用下述式(I-1)~(I-10)所表示的化合物、雙(3,4-環氧環己基甲基)醚、1,2-雙(3,4-環氧環己烷-1-基)乙烷、1,2-環氧基-1,2-雙(3,4-環氧環己烷-1-基)乙烷、2,2-雙(3,4-環氧環己烷-1-基)丙烷等。作為這些化合物，例如，能夠使用：商品名「CELLOXIDE 2021P」、「CELLOXIDE 2081」(DAICEL(股)製)等的市售品。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之伸烷基，可舉出：亞甲基、伸乙基、伸丙基、異伸丙基、伸丁基、異伸丁基、第二伸丁基、伸戊基、伸己基、伸庚基、伸辛基等的直鏈或者分枝鏈狀伸烷基。它們當中，較佳為亞甲基、伸乙基、伸丙基、異伸丙基等的碳數1~3的直鏈或者分枝鏈狀伸烷基。又，下述式(I-9)、(I-10)中的n1~n6分別表示1~30的整數。又，雙(3,4-環氧環己基甲基)醚，例如，能夠利用國際公開第2014/181787號記載的方法，或是根據它的方法製造。 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), and bis(3,4-). Epoxycyclohexylmethyl)ether, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4- Epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, and the like. As such a compound, for example, a commercial item such as "CELLOXIDE 2021P" or "CELLOXIDE 2081" (manufactured by DAICEL Co., Ltd.) can be used. 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 exo-propyl group, a butyl group, and an isobutylene group. a straight chain or a branched chain alkyl group having a base, a second butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a linear or branched chain alkyl group having 1 to 3 carbon atoms such as a methylene group, an exoethyl group, a propyl group or an exo-propyl group is preferable. Further, n1 to n6 in the following formulas (I-9) and (I-10) each represent an integer of 1 to 30. Further, bis(3,4-epoxycyclohexylmethyl)ether can be produced, for example, by the method described in International Publication No. 2014/181787 or by the method thereof.
作為(ii)環氧基係直接以單鍵鍵結於脂環上的化合物，例如，可舉出用下述式(II)所表示的的化合物。 (ii) The compound which the epoxy group is directly bonded to the alicyclic ring by a single bond, for example, the compound represented by the following formula (II) is mentioned.
式(II)中，R’係從p價的醇去除p個-OH的基，p、n分別表示自然數。作為p價的醇[R’-(OH)p]，例如，可舉出碳數1~15的醇等，更具體而言，可舉出：2,2-雙(羥甲基)-1-丁醇等的多元醇等。p較佳為1~6，n較佳為1~30。在p為2以上的情況下，各()內(圓括弧內)的基中的n可以相同也可以不同。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-環氧基-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' removes p-OH groups from the p-valent alcohol, and p and n each represent a natural number. Examples of the p-valent alcohol [R'-(OH) p ] include an alcohol having 1 to 15 carbon atoms, and more specifically, 2,2-bis(hydroxymethyl)-1. a polyol such as butanol or the like. p is preferably from 1 to 6, and n is preferably from 1 to 30. When p is 2 or more, n in each of the bases (in the parentheses) may be the same or different. Specific examples of the above compound include 1,2-epoxy-4-(2-epoxyethyl)cyclohexane of 2,2-bis(hydroxymethyl)-1-butanol. The product name is "EHPE3150" (DAICEL system).
作為(iii)氫化芳香族環氧丙基醚系環氧化合物，例如，可舉出：將2,2-雙[4-(2,3-環氧丙氧基)環己基]丙烷、2,2-雙[3,5-二甲基-4-(2,3-環氧丙氧基)環己基]丙烷等的雙酚A型環氧化合物氫化的化合物(核加氫雙酚A型環氧化合物)；將雙[o,o-(2,3-環氧丙氧基)環己基]甲烷、雙[o,p-(2,3-環氧丙氧基)環己基]甲烷、雙[p,p-(2,3-環氧丙氧基)環己基]甲烷、雙[3,5-二甲基-4-(2,3-環氧丙氧基)環己基]甲烷等的雙酚F型環氧化合物氫化的化合物(核加氫雙酚F型環氧化合物)；加氫雙酚型環氧化合物；加氫酚酚醛型環氧化合物；加氫甲酚酚醛型環氧化合物；雙酚A的甲酚酚醛型環氧化合物的加氫環氧化合 物；加氫萘型環氧化合物；由三酚甲烷所得到的環氧化合物的加氫環氧化合物等。 Examples of the (iii) hydrogenated aromatic epoxidopropyl ether epoxy compound include 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2, Hydrogenated compound of bisphenol A type epoxy compound such as 2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (nuclear hydrogenated bisphenol A ring) Oxygen compound); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, double [p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, etc. Bisphenol F type epoxy compound hydrogenated compound (nuclear hydrogenated bisphenol F type epoxy compound); hydrogenated bisphenol type epoxy compound; hydrogenated phenol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound Hydrogenation of bisphenol A cresol novolac epoxy compound a hydrogenated naphthalene type epoxy compound; a hydrogenated epoxy compound of an epoxy compound obtained from trisphenol methane; and the like.
脂環式環氧化合物(A)能夠單獨使用，或者組合2種以上使用。上述當中，作為脂環式環氧化合物(A)，特佳為用上述式(I-1)所表示的3,4-環氧環己基甲基(3,4-環氧基)環己烷羧酸酯、商品名「CELLOXIDE 2021P」。 The alicyclic epoxy compound (A) can be used singly or in combination of two or more. Among the above, as the alicyclic epoxy compound (A), 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane represented by the above formula (I-1) is particularly preferred. Carboxylic acid ester, trade name "CELLOXIDE 2021P".
此外，相對於脂環式環氧化合物(A)和異三聚氰酸一烯丙基二環氧丙酯(B)的總量(100重量%)，脂環式環氧化合物(A)的用量(含量)較佳為5~50重量%，更佳為10~50重量%，再較佳為20~50重量%，特佳為30~50重量%。在脂環式環氧化合物(A)的用量小於5重量%下，有回流後的反射率降低的情況。另一方面，若脂環式環氧化合物(A)的用量超過50重量%，則有硬化物的強韌性降低，變得容易發生龜裂的情況。 Further, the alicyclic epoxy compound (A) is based on the total amount (100% by weight) of the alicyclic epoxy compound (A) and the isoallyl propylene glycol monoglycidyl acrylate (B). The amount (content) is preferably from 5 to 50% by weight, more preferably from 10 to 50% by weight, still more preferably from 20 to 50% by weight, particularly preferably from 30 to 50% by weight. When the amount of the alicyclic epoxy compound (A) is less than 5% by weight, the reflectance after reflow may be lowered. On the other hand, when the amount of the alicyclic epoxy compound (A) is more than 50% by weight, the toughness of the cured product is lowered, and cracking tends to occur.
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)的含量(摻合量)係相較於硬化性環氧樹脂組成物的總量(100重量%)較佳為0.3~10重量%，更佳為0.3~7重量%，再較佳為0.5~5重量%。若脂環式環氧化合物(A)的含量小於0.3重量%，則有摻合物(硬化性環氧樹脂組成物)的流動性不足而在轉移成型下成為未填充的情況，有硬化物的耐熱性及耐候性(耐黃變性)變得不充分的傾向。另一方面，若脂環式環氧化合物(A)的含量超過10重量%，則有硬化物的線膨脹係數變大，變得容易在其與導線框之間產生翹曲的情況。 The content (admixture amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is preferably in comparison with the total amount (100% by weight) of the curable epoxy resin composition. 0.3 to 10% by weight, more preferably 0.3 to 7% by weight, still more preferably 0.5 to 5% by weight. When the content of the alicyclic epoxy compound (A) is less than 0.3% by weight, the blend (curable epoxy resin composition) may have insufficient fluidity and may be unfilled under transfer molding, and may have a cured product. Heat resistance and weather resistance (yellowing resistance) tend to be insufficient. On the other hand, when the content of the alicyclic epoxy compound (A) exceeds 10% by weight, the linear expansion coefficient of the cured product becomes large, and it is likely to cause warpage between the lead ring frame and the lead frame.
構成本發明的硬化性環氧樹脂組成物的異三聚氰酸一烯丙基二環氧丙酯化合物(B)，係用下述一般式(1)表示。 The isomeric isocyanurate compound (B) which constitutes the curable epoxy resin composition of the present invention is represented by the following general formula (1).
上述式(1)中，R1及R2係相同或者不同，表示氫原子或者碳數1~8的烷基。 In the above formula (1), R 1 and R 2 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
作為碳數1~8的烷基，例如，可舉出：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、戊基、己基、庚基、辛基等的直鏈或分枝鏈狀的烷基。其中，較佳為甲基、乙基、丙基、異丙基等的碳數1~3的直鏈或分枝鏈狀的烷基。上述式(1)中的R1及R2特佳為氫原子。 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, a second butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. A linear or branched chain alkyl group having the same or the like. Among them, a linear or branched chain 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.
作為異三聚氰酸一烯丙基二環氧丙酯化合物(B)的代表性例子，可舉出：異三聚氰酸一烯丙基二環氧丙酯、異三聚氰酸1-烯丙基-3,5-雙(2-甲基環氧丙基)酯、異三聚氰酸1-(2-甲基丙烯基)-3,5-二環氧丙酯、異三聚氰酸1-(2-甲基丙烯基)-3,5-雙(2-甲基環氧丙基)酯等。又，異三聚氰酸一烯丙基二環氧丙酯化合物(B)能夠單獨使用，或者組合2種以上使用。 As a representative example of the isoallyl cyanurate compound (B), an isomeric isocyanate, an isomeric cyanuric acid, and an isocyanuric acid 1- Allyl-3,5-bis(2-methylepoxypropyl) ester, 1-(2-methylpropenyl)-3,5-diglycidyl isocyanate, heterotrimerization 1-(2-Methylpropenyl)-3,5-bis(2-methylepoxypropyl)cyanate or the like. Further, the isomeric isocyanurate compound (B) can be used singly or in combination of two or more.
此外，相對於脂環式環氧化合物(A)和異三聚氰酸一烯丙基二環氧丙酯化合物(B)的總量(100重量%)，異三聚氰酸一烯丙基二環氧丙酯化合物(B)的用量(含量)為50~95重量%，較佳為50~90重量%，更佳為50~80重量%，再較佳為50~70重量%。在異三聚氰酸一烯丙基二環氧丙酯化合物(B)的用量小於50重量%下，有硬化物的強韌性降低，變得容易產生龜裂的傾向。另一方面，若異三聚氰酸一烯丙基二環氧丙酯化合物(B)的用量超過95重量%，則有回流後的反射率降低的傾向。 Further, isopropyl cyanurate is an allyl group relative to the total amount (100% by weight) of the alicyclic epoxy compound (A) and the isoallyl propylene glycol monoglycidyl acrylate compound (B). The amount (content) of the diglycidyl ester compound (B) is from 50 to 95% by weight, preferably from 50 to 90% by weight, more preferably from 50 to 80% by weight, still more preferably from 50 to 70% by weight. When the amount of the monoallyl cyanurate compound (B) is less than 50% by weight, the toughness of the cured product is lowered, and cracking tends to occur. On the other hand, when the amount of the isomeric isocyanurate compound (B) exceeds 95% by weight, the reflectance after reflow tends to decrease.
藉由含有本發明的硬化性環氧樹脂組成物的必要成分的無機填充劑(C)，無機填充劑(C)擔任使成形性提升的任務。作為無機填充劑(C)，能夠使用公知或慣用的無機填充劑(C)，沒有特別的限定，但例如，可舉出：氧化矽、氧化鋁等。從成形性的觀點來看，作為無機填充劑(C)，較佳為氧化矽(特別是氧化矽填料)。無機填充劑(C)的平均粒徑較佳為1~100μm。又，在本說明書中，無機填充劑(C)中不含下述白色顏料(F)。此外，上述平均粒徑意指用雷射繞射-散射法測定的粒度分布中的累計值50%處的粒徑(中位數徑)。 The inorganic filler (C) containing the inorganic filler (C) which is an essential component of the curable epoxy resin composition of the present invention serves as a task for improving moldability. As the inorganic filler (C), a known or customary inorganic filler (C) can be used, and it is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, and the like. From the viewpoint of moldability, as the inorganic filler (C), cerium oxide (especially cerium oxide filler) is preferred. The average particle diameter of the inorganic filler (C) is preferably from 1 to 100 μm. Further, in the present specification, the inorganic filler (C) does not contain the following white pigment (F). Further, the above average particle diameter means a particle diameter (median diameter) at a cumulative value of 50% in the particle size distribution measured by a laser diffraction-scattering method.
無機填充劑(C)的用量(含量)係相對於硬化性環氧樹脂組成物的總量(100重量%)為30~95重量%，較佳為40~85重量%。若無機填充劑(C)的用量低於30重量%，則不減低硬化物的線膨脹係數，有硬化物的強度不足的傾向。另一方面，在無機填充劑(C)的用量為超過95重量%的量下，無法進行物理性填充。 The amount (content) of the inorganic filler (C) is 30 to 95% by weight, preferably 40 to 85% by weight based on the total amount (100% by weight) of the curable epoxy resin composition. When the amount of the inorganic filler (C) is less than 30% by weight, the linear expansion coefficient of the cured product is not reduced, and the strength of the cured product tends to be insufficient. On the other hand, when the amount of the inorganic filler (C) is more than 95% by weight, physical filling cannot be performed.
構成本發明的硬化性環氧樹脂組成物的硬化劑(D)，係擔任使具有環氧基的化合物硬化的任務。作為硬化劑(D)，能夠使用公知或慣用的硬化劑作為環氧樹脂用硬化劑。作為硬化劑(D)，例如，可舉出：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、酞酸酐、四氫酞酸酐、六氫酞酸酐、甲基環己烯二羧酸酐等。又，硬化劑(D)能夠單獨使用，或者組合2種以上使用。作為硬化劑(D)，在耐熱性、耐光性、耐龜裂性的觀點上，特別是，較佳為飽和單環烴二元酸的酐(也包含烷基等的取代基鍵結於環上者)。 The curing agent (D) constituting the curable epoxy resin composition of the present invention serves as a task for hardening a compound having an epoxy group. As the curing agent (D), a known or conventional curing agent can be used as the curing agent for the epoxy resin. Examples of the curing agent (D) include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methyl endomethylenetetrahydrophthalic anhydride, decanoic anhydride, and tetrahydrogen. Anthracene anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, and the like. Further, the curing agent (D) can be used singly or in combination of two or more. As the curing agent (D), in view of heat resistance, light resistance, and crack resistance, in particular, an anhydride of a saturated monocyclic hydrocarbon dibasic acid (a substituent including an alkyl group or the like is bonded to the ring) is preferable. The above).
此外，在本發明中，作為硬化劑(D)，也能夠使用商品名「Rikacid MH-700」(新日本理化(股)製)、商品名「HN-5500」(日立化成工業(股)製)等的市售品。 In addition, in the present invention, the product name "Rikacid MH-700" (manufactured by Shin-Nihon Chemicals Co., Ltd.) and the trade name "HN-5500" (Hitachi Chemical Industry Co., Ltd.) can be used as the curing agent (D). And other commercial products.
硬化劑(D)的用量(含量)沒有特別的限定，但相對於硬化性環氧樹脂組成物中所包含的具有環氧基的化合物的總量(100重量份)，較佳為50~200重量份，更佳為100~145重量份。更具體而言，較佳為以本發明的硬化性環氧樹脂組成物中含有之全部具有環氧基的化合物中的環氧基每1當量，按照0.5~1.5當量的比例使用。若硬化劑(D)的用量低於50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，若硬化劑(D)的用量超過200重量份，則有硬化物著色而色相惡化的情況。 The amount (content) of the hardener (D) is not particularly limited, but is preferably 50 to 200 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 100 to 145 parts by weight. More specifically, the epoxy group in the compound having an epoxy group contained in the curable epoxy resin composition of the present invention is preferably used in an amount of from 0.5 to 1.5 equivalents per equivalent of the epoxy group. When the amount of the curing agent (D) is less than 50 parts by weight, the curing becomes insufficient, and the toughness of the cured product tends to decrease. On the other hand, when the amount of the curing agent (D) exceeds 200 parts by weight, the cured product may be colored and the hue may be deteriorated.
在本發明的硬化性環氧樹脂組成物中，硬化促進劑(E)係在利用硬化劑(D)硬化具有環氧基的化合物之際，具有促進硬化速度的功能的化合物。作為硬化促進劑(E)，能夠使用公知或慣用的硬化促進劑，沒有特別的限定，但例如，可舉出：1,8-二氮雜雙環[5.4.0]十一烯-7(DBU)、及其鹽(例如，酚鹽、辛酸鹽、對甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽)；1,5-二氮雜雙環[4.3.0]壬烯-5(DBN)、及其鹽(例如，酚鹽、辛酸鹽、對甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽)；苄基二甲胺、2,4,6-三(二甲胺基甲基)酚、N,N-二甲基環己胺等的3級胺；2-乙基-4-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑等的咪唑類；磷酸酯、三苯基膦等的膦類；四苯基鏻四(對甲苯基)硼酸酯等的鏻化合物；辛酸錫、辛酸鋅等的有機金屬鹽；金屬鉗合劑等。又，硬化促進劑(E)能夠單獨使用，或者組合2種以上使用。 In the curable epoxy resin composition of the present invention, the curing accelerator (E) is a compound having a function of promoting the curing rate when the epoxy group-containing compound is cured by the curing agent (D). A known or conventional hardening accelerator can be used as the curing accelerator (E), and is not particularly limited. For example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) can be mentioned. And its salts (for example, phenates, octanoates, p-toluenesulfonates, formates, tetraphenylborates); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) And its salts (for example, phenates, octanoates, p-toluenesulfonates, formates, tetraphenylborates); benzyldimethylamine, 2,4,6-tris(dimethylamino) a quaternary amine such as phenol or N,N-dimethylcyclohexylamine; 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 tetra(p-tolyl)borate; an organic metal salt such as tin octylate or zinc octylate; or a metal chelating agent. Further, the curing accelerator (E) can be used singly or in combination of two or more.
此外，在本發明中，作為硬化促進劑(E)，也能夠使用商品名「U-CAT SA 506」、「U-CAT SA 102」、「U-CAT 5003」、「U-CAT 18X」、「12XD(開發品)」(以上，Sun Apollo(股)製)、商品名「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)等的市售品。 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, Sun Apollo (share) system), trade name "TPP-K", "TPP-MK" (above, Beixing Chemical Industry Co., Ltd.), trade name "PX-4ET" (commercial products such as the Japan Chemical Industry Co., Ltd.).
硬化促進劑(E)的用量(含量)沒有特別的限定，但相對於硬化性環氧樹脂組成物中所包含的具有環氧基的化合物的總量(100重量份)，較佳為0.05~5重量 份，更佳為0.1~3重量份，再較佳為0.2~3重量份，特佳為0.25~2.5重量份。若硬化促進劑(E)的用量低於0.05重量份，則有硬化促進效果變得不充分的情況。另一方面，硬化促進劑(E)的用量超過5重量份，則有硬化物著色而色相惡化的情況。 The amount (content) of the hardening accelerator (E) is not particularly limited, but is preferably 0.05 to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the curable epoxy resin composition. 5 weight The portion is more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 2.5 parts by weight. When the amount of the curing accelerator (E) is less than 0.05 parts by weight, the curing acceleration effect may be insufficient. On the other hand, when the amount of the curing accelerator (E) is more than 5 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的白色顏料(F)，相對於將上述硬化性環氧樹脂組成物硬化所得到的硬化物，擔任使其發揮高光反射性的任務。作為白色顏料(F)，能夠使用公知或慣用的白色顏料，沒有特別的限定，例如，可舉出：玻璃、黏土、雲母、滑石、高嶺石(高嶺土)、埃洛石(halloysite)、沸石、酸性白土、活性白土、勃姆石(boehmite)、擬勃姆石(pseudoboehmite)、無機氧化物、鹼土類金屬鹽等的金屬鹽等的無機白色顏料；苯乙烯系樹脂、苯并胍胺系樹脂、脲-福馬林系樹脂、三聚氰胺-福馬林系樹脂、醯胺系樹脂等的樹脂顏料等的有機白色顏料(塑膠顏料等)；具有中空構造(氣球構造)的中空粒子等。這些白色顏料能夠單獨使用，或者組合2種以上使用。 The white pigment (F) of the curable epoxy resin composition of the present invention has a task of exhibiting high light reflectivity with respect to the cured product obtained by curing the curable epoxy resin composition. As the white pigment (F), a known or conventional white pigment can be used, and it is not particularly limited, and examples thereof include glass, clay, mica, talc, kaolinite (kaolin), halloysite, and zeolite. Inorganic white pigment such as acid white clay, activated clay, boehmite, pseudoboehmite, inorganic oxide, alkaline earth metal salt, etc.; styrene resin, benzoguanamine resin An organic white pigment (such as a plastic pigment) such as a urea-formalin resin, a resin pigment such as a melamine-formalin resin or a guanamine resin, or a hollow particle having a hollow structure (balloon structure). These white pigments can be used singly or in combination of two or more.
白色顏料(F)的用量(含量)係相對於無機填充劑(C)及白色顏料(F)的合計量(100重量%)較佳為3~40重量%，更佳為10~30重量%。若白色顏料(F)的用量低於3重量%，則初期反射率降低而變得不適合作為反射體材料。另一方面，若白色顏料(F)的用量超過40重量%，則有流動性降低而成為未填充的傾向。 The amount (content) of the white pigment (F) is preferably from 3 to 40% by weight, more preferably from 10 to 30% by weight, based on the total amount (100% by weight) of the inorganic filler (C) and the white pigment (F). . When the amount of the white pigment (F) is less than 3% by weight, the initial reflectance is lowered and it becomes unsuitable as a reflector material. On the other hand, when the amount of the white pigment (F) exceeds 40% by weight, the fluidity tends to decrease and it tends to be unfilled.
此外，合併無機填充劑(C)和白色顏料(F)的用量(含量)係相對於硬化性環氧樹脂組成物的總量(100重量%)較佳為60~95重量%，更佳為70~90重量%。若無機填充劑(C)和白色顏料(F)的合計量係相對於硬化性環氧樹脂組成物的總量(100重量%)低於60重量%，則在線膨脹係數變大成形為導線框的情況下，有產生翹曲的傾向，另一方面，若超過95重量%，則有流動性變差而變得容易產生未填充的傾向。 Further, the amount (content) of the inorganic filler (C) and the white pigment (F) is preferably 60 to 95% by weight, more preferably 60 to 95% by weight based on the total amount of the curable epoxy resin composition. 70~90% by weight. When the total amount of the inorganic filler (C) and the white pigment (F) is less than 60% by weight based on the total amount (100% by weight) of the curable epoxy resin composition, the coefficient of linear expansion becomes large and is formed into a lead frame. In the case of warping, the warpage tends to occur. On the other hand, when it exceeds 95% by weight, the fluidity is deteriorated and the unfilling tends to occur.
作為上述無機氧化物，例如，可舉出：氧化鎂、氧化銻、氧化鈦(金紅石(rutile)型氧化鈦、銳鈦礦(anatase)型氧化鈦、板鈦礦(brookite)型氧化鈦)、氧化鋯、氧化鋅、氧化矽(二氧化矽)等。此外，作為上述鹼土類金屬鹽，例如，可舉出：碳酸鎂、碳酸鈣、碳酸鋇、矽酸鎂、矽酸鈣、氫氧化鎂、磷酸鎂、磷酸氫鎂、硫酸鎂、硫酸鈣、硫酸鋇等。此外，作為鹼土類金屬鹽以外的金屬鹽，例如，可舉出：矽酸鋁、氫氧化鋁、硫化鋅等。 Examples of the inorganic oxide include magnesium oxide, cerium oxide, titanium oxide (rutile type titanium oxide, anatase type titanium oxide, and brookite type titanium oxide). Zirconium oxide, zinc oxide, cerium oxide (cerium oxide), and the like. Further, examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium citrate, calcium citrate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, and sulfuric acid. Hey. In addition, examples of the metal salt other than the alkaline earth metal salt include aluminum niobate, aluminum hydroxide, and zinc sulfide.
作為上述中空粒子，沒有特別的限定，例如，可舉出：由無機玻璃(例如，矽酸鈉玻璃、鋁矽酸玻璃、硼矽酸鈉玻璃、石英等)、碳酸鈣、碳酸鋇、碳酸鎳、矽酸鈣等的金屬鹽等的無機物所構成的無機中空粒子(也包含火山灰微粒子等的天然物)；由苯乙烯系樹脂、丙烯酸系樹脂、矽酮系樹脂、丙烯酸-苯乙烯系樹脂、氯乙烯系樹脂、偏氯乙烯系樹脂、醯胺系樹脂、胺基甲酸酯系樹脂、酚系樹脂、苯乙烯-共軛二烯系樹脂、丙烯酸 -共軛二烯系樹脂、烯烴系樹脂等的聚合物(也包含這些聚合物的交聯體)等的有機物所構成的有機中空粒子；由無機物和有機物的混合材料所構成的無機-有機中空粒子等。又，上述中空粒子可以是由單一材料所構成者，也可以是由2種以上材料所構成者。此外，上述中空粒子的中空部(中空粒子的內部的空間)可以是真空狀態，也可以充滿介質，特別是在反射率提升的觀點上，較佳為充滿折射率低的介質(例如，氮、氬等的惰性氣體或空氣等)的中空粒子。 The hollow particles are not particularly limited, and examples thereof include inorganic glass (for example, sodium citrate glass, aluminosilicate glass, sodium borosilicate glass, quartz, etc.), calcium carbonate, barium carbonate, and nickel carbonate. Inorganic hollow particles (including natural materials such as pozzolan microparticles) composed of inorganic substances such as metal salts such as calcium citrate; and styrene resins, acrylic resins, fluorenone resins, acrylic acid-styrene resins, Vinyl chloride resin, vinylidene chloride resin, guanamine resin, urethane resin, phenol resin, styrene-conjugated diene resin, acrylic acid -organic hollow particles composed of an organic material such as a conjugated diene resin or an olefin resin (including a crosslinked product of these polymers); an inorganic-organic hollow composed of a mixed material of an inorganic material and an organic material; Particles, etc. Further, the hollow particles may be composed of a single material, or may be composed of two or more materials. Further, the hollow portion (the space inside the hollow particles) of the hollow particles may be in a vacuum state or may be filled with a medium, and particularly preferably a medium having a low refractive index (for example, nitrogen, from the viewpoint of improving reflectance). Hollow particles such as an inert gas such as argon or air.
又，白色顏料(F)可以是實施了公知或慣用的表面處理(例如，利用金屬氧化物、矽烷偶合劑、鈦偶合劑、有機酸、多元醇、矽酮等的表面處理劑的表面處理等)者。藉由實施這樣的表面處理，有能夠使硬化性環氧樹脂組成物中的白色顏料(F)與其他成分的相溶性或分散性提升的情況。 Further, the white pigment (F) may be subjected to a known or conventional surface treatment (for example, surface treatment using a surface treatment agent such as a metal oxide, a decane coupling agent, a titanium coupling agent, an organic acid, a polyhydric alcohol or an anthrone). )By. By carrying out such a surface treatment, it is possible to improve the compatibility or dispersibility of the white pigment (F) in the curable epoxy resin composition with other components.
其中，作為白色顏料(F)，在取得性、耐熱性、耐光性的觀點上，較佳為無機氧化物、無機中空粒子，更佳為從包含氧化鋁、氧化鎂、氧化銻、氧化鈦、氧化鋯、氧化矽、及無機中空粒子的群組所選出的1種以上的白色顏料。特別是，作為白色顏料(F)，在具有較高折射率的方面上，較佳為氧化鈦。 In particular, the white pigment (F) is preferably an inorganic oxide or an inorganic hollow particle from the viewpoint of availability, heat resistance, and light resistance, and more preferably contains alumina, magnesia, cerium oxide, titanium oxide, or the like. One or more kinds of white pigments selected from the group consisting of zirconia, yttria, and inorganic hollow particles. In particular, as the white pigment (F), titanium oxide is preferred in terms of having a high refractive index.
白色顏料(F)的形狀沒有特別的限定，例如，可舉出：球狀、破碎狀、纖維狀、針狀、鱗片狀、晶鬚狀等。其中，在白色顏料(F)的分散性的觀點上，較佳為球狀的白色顏料，特佳為真球狀的白色顏料(例如，長寬比為1.2以下的球狀的白色顏料)。 The shape of the white pigment (F) is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fibrous shape, a needle shape, a scaly shape, and a whisker shape. Among them, from the viewpoint of dispersibility of the white pigment (F), a spherical white pigment is preferable, and a white pigment having a true spherical shape (for example, a spherical white pigment having an aspect ratio of 1.2 or less) is preferable.
白色顏料(F)的中心粒徑，沒有特別的限定，在光反射性提升的觀點上，較佳為0.1~50μm。特別是，在使用無機氧化物作為白色顏料(F)的情況下，該無機氧化物的中心粒徑沒有特別的限定，但較佳為0.1~50μm，更佳為0.1~30μm，再較佳為0.1~20μm，特佳為0.1~10μm，最佳為0.1~5μm。另一方面，在使用中空粒子(特別是無機中空粒子)作為白色顏料(F)的情況下，該中空粒子的中心粒徑沒有特別的限定，但較佳為0.1~50μm，更佳為0.1~30μm。又，上述中心粒徑意指用雷射繞射-散射法測定的粒度分布中的累計值50%處的粒徑(中位數徑)。 The center particle diameter of the white pigment (F) is not particularly limited, and is preferably from 0.1 to 50 μm from the viewpoint of improving light reflectivity. In particular, when an inorganic oxide is used as the white pigment (F), the central particle diameter of the inorganic oxide is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, still more preferably 0.1 to 20 μm, particularly preferably 0.1 to 10 μm, and most preferably 0.1 to 5 μm. On the other hand, when hollow particles (especially inorganic hollow particles) are used as the white pigment (F), the central particle diameter of the hollow particles is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 0.1. 30 μm. Further, the above-mentioned center particle diameter means a particle diameter (median diameter) at 50% of the cumulative value in the particle size distribution measured by the laser diffraction-scattering method.
又，白色顏料(F)能夠利用公知或慣用的製造方法製造。此外，作為白色顏料(F)，也能夠使用市售品，例如，能夠使用：商品名「SR-1」、「R-42」、「R-45M」、「R-650」、「R-32」、「R-5N」、「GTR-100」、「R-62N」、「R-7E」、「R-44」、「R-3L」、「R-11P」、「R-21」、「R-25」、「TCR-52」、「R-310」、「D-918」、「FTR-700」(以上，堺化學工業(股)製)、商品名「Tipaque CR-50」、「CR-50-2」、「CR-60」、「CR-60-2」、「CR-63」、「CR-80」、「CR-90」、「CR-90-2」、「CR-93」、「CR-95」、「CR-97」(以上，石原產業(股)製)、商品名「JR-301」、「JR-403」、「JR-405」、「JR-600A」、「JR-605」、「JR-600E」、「JR-603」、「JR-805」、「JR-806」、「JR-701」、「JRNC」、「JR-800」、「JR」(以上，TAYCA(股)製)、商品名「TR-600」、「TR-700」、「TR-750」、「TR-840」、 「TR-900」(以上，富士TITAN工業(股)製)、商品名「KR-310」、「KR-380」、「KR-380N」(以上，TITAN工業(股)製)、商品名「ST-410WB」、「ST-455」、「ST-455WB」、「ST-457SA」、「ST-457EC」、「ST-485SA15」、「ST-486SA」、「ST-495M」(以上，TITAN工業(股)製)等的金紅石型氧化鈦；商品名「A-110」、「TCA-123E」、「A-190」、「A-197」、「SA-1」、「SA-1L」、「SSP系列」、「CSB系列」(以上，堺化學工業(股)製)、商品名「JA-1」、「JA-C」、「JA-3」(以上，TAYCA(股)製)、商品名「KA-10」、「KA-15」、「KA-20」、「STT-65C-S」、「STT-30EHJ」(以上，TITAN工業(股)製)等的銳鈦型氧化鈦等。 Further, the white pigment (F) can be produced by a known or customary production method. Further, as the white pigment (F), a commercially available product can also be used. For example, the product names "SR-1", "R-42", "R-45M", "R-650", and "R- can be used. 32", "R-5N", "GTR-100", "R-62N", "R-7E", "R-44", "R-3L", "R-11P", "R-21" "R-25", "TCR-52", "R-310", "D-918", "FTR-700" (above, 堺Chemical Industries Co., Ltd.), trade name "Tipaque CR-50" , "CR-50-2", "CR-60", "CR-60-2", "CR-63", "CR-80", "CR-90", "CR-90-2", " CR-93", "CR-95", "CR-97" (above, Ishihara Industry Co., Ltd.), trade name "JR-301", "JR-403", "JR-405", "JR- 600A", "JR-605", "JR-600E", "JR-603", "JR-805", "JR-806", "JR-701", "JRNC", "JR-800", " JR" (above, TAYCA (share) system), trade name "TR-600", "TR-700", "TR-750", "TR-840", "TR-900" (above, Fuji Titan Industrial Co., Ltd.), trade name "KR-310", "KR-380", "KR-380N" (above, TITAN Industrial Co., Ltd.), trade name " ST-410WB, ST-455, ST-455WB, ST-457SA, ST-457EC, ST-485SA15, ST-486SA, ST-495M (above, TITAN) Rutile-type titanium oxide such as industrial (stock) system; trade names "A-110", "TCA-123E", "A-190", "A-197", "SA-1", "SA-1L" "SSP Series", "CSB Series" (above, 堺Chemical Industries Co., Ltd.), trade names "JA-1", "JA-C", "JA-3" (above, TAYCA) ) Anatase type such as "KA-10", "KA-15", "KA-20", "STT-65C-S", "STT-30EHJ" (above, TITAN Industrial Co., Ltd.) Titanium oxide, etc.
本發明的硬化性環氧樹脂組成物，可以在不損害本發明的效果的範圍下，包含脂環式環氧化合物(A)以外的環氧化合物(有稱為「其他的環氧化合物」的情況)。作為上述其他的環氧化合物，可舉出公知或慣用的環氧化合物，沒有特別的限定，但例如，可舉出：芳香族環氧丙基醚系環氧化合物[例如，雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚型環氧化合物、酚酚醛型環氧化合物、甲酚酚醛型環氧化合物、雙酚A的甲酚酚醛型環氧化合物、萘型環氧化合物、由三酚甲烷所得到的環氧化合物等]等的芳香族環氧化合物等。又，其他的環氧化合物能夠單獨使用1種，也能夠組合2種以上使用。 The curable epoxy resin composition of the present invention may contain an epoxy compound other than the alicyclic epoxy compound (A) (referred to as "other epoxy compound"), without impairing the effects of the present invention. Happening). The above-mentioned other epoxy compound is not particularly limited as long as it is a known or customary epoxy compound, and examples thereof include an aromatic epoxy propyl ether epoxy compound (for example, a bisphenol A ring). Oxygen compound, bisphenol F type epoxy compound, bisphenol type epoxy compound, phenol novolak type epoxy compound, cresol novolac type epoxy compound, cresol novolac type epoxy compound of bisphenol A, naphthalene type epoxy compound An aromatic epoxy compound such as an epoxy compound obtained from trisphenol methane or the like. In addition, one type of the other epoxy compounds may be used alone or two or more types may be used in combination.
本發明的硬化性環氧樹脂組成物，除了上述之外，能夠在不損害本發明的效果的範圍下使用各種添加劑。作為添加劑，例如，能夠使用消泡劑、調平劑、γ-環氧丙氧基丙基三甲氧基矽烷或3-巰基丙基三甲氧基矽烷等的矽烷偶合劑、抗氧化劑、脫模劑、界面活性劑、阻燃劑、紫外線吸收劑、離子吸附體、螢光體等的慣用的添加劑。 In addition to the above, the curable epoxy resin composition of the present invention can use various additives without departing from the effects of the present invention. As the additive, for example, an antifoaming agent, a leveling agent, a decane coupling agent such as γ-glycidoxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane, an antioxidant, and a releasing agent can be used. Conventional additives such as surfactants, flame retardants, ultraviolet absorbers, ion adsorbents, and phosphors.
本發明的硬化性環氧樹脂組成物沒有特別的限定，能夠根據需要在加熱的狀態下藉由摻合及混練上述各成分來調製。上述混練的方法沒有特別的限定，例如，能夠使用溶解器、均化器等的各種混合器、揑合器、輥機、珠磨機、自公轉式攪拌裝置等的公知或慣用的混練手段。 The curable epoxy resin composition of the present invention is not particularly limited, and can be prepared by blending and kneading the above components in a heated state as needed. The kneading method is not particularly limited. For example, various known mixers such as a dissolver and a homogenizer, a kneader, a roll mill, a bead mill, and a self-propagating stirring device can be used.
在本發明的硬化性環氧樹脂組成物係在室溫(例如，25℃)下以固體得到的情況下，該硬化性環氧樹脂組成物，特別是，能較佳地作為轉移成型用樹脂組成物或壓縮成型用樹脂組成物使用。具體而言，例如，在調製本發明的硬化性環氧樹脂組成物之際成型為平板狀，從而能作為這些轉移成型或壓縮成型用樹脂組成物使用。此外，在本發明的硬化性環氧樹脂組成物係在室溫(例如，25℃)下以黏土狀得到的情況下，該硬化性環氧樹脂組成物能作為壓縮成型用樹脂組成物使用，另一方面，對於作為轉移成型用樹脂組成物，可以進行加熱處理(例如，在25℃下24小時、或者40℃下5小時等)。 In the case where the curable epoxy resin composition of the present invention is obtained as a solid at room temperature (for example, 25 ° C), the curable epoxy resin composition can be preferably used as a resin for transfer molding. The composition or the resin composition for compression molding is used. Specifically, for example, when the curable epoxy resin composition of the present invention is prepared, it is formed into a flat plate shape, and can be used as a resin composition for transfer molding or compression molding. Further, when the curable epoxy resin composition of the present invention is obtained in the form of a clay at room temperature (for example, 25 ° C), the curable epoxy resin composition can be used as a resin composition for compression molding. On the other hand, the resin composition for transfer molding can be subjected to heat treatment (for example, at 25 ° C for 24 hours or at 40 ° C for 5 hours, etc.).
又，也能夠進一步加熱本發明的硬化性環氧樹脂組成物，使該硬化性環氧樹脂組成物中的具有環氧基的化合物的一部分反應，從而得到B階化的硬化性環氧樹脂組成物(B階狀態的硬化性環氧樹脂組成物)。 Further, the curable epoxy resin composition of the present invention can be further heated, and a part of the epoxy group-containing compound in the curable epoxy resin composition can be reacted to obtain a B-staged curable epoxy resin composition. (a hardening epoxy resin composition in a B-stage state).
利用加熱使本發明的硬化性環氧樹脂組成物(或者B階狀態的硬化性環氧樹脂組成物)硬化，從而能夠得到對模具(例如，轉移成型用模具、壓縮成型用模具等)的脫模性優異，具有高反射率，耐熱性及耐光性優異，而且強韌的硬化物(有稱為「本發明的硬化物」的情況)。硬化之際的加熱溫度(硬化溫度)沒有特別的限定，但較佳為100~200℃，更佳為150~190℃。此外，在硬化之際加熱的時間(加熱時間)沒有特別的限定，但較佳為40~300秒鐘，更佳為60~120秒鐘。在硬化溫度和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產生因熱分解所形成的黃變，間隔時間(tact time)變長而生產性降低，因此皆不佳。硬化條件視各種條件而定，例如，能根據在提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拉長硬化時間等來適宜調整。此外，加熱硬化處理可以用1階段(例如，僅轉移成型階段)進行，例如，也可以在轉移成型後以後熟化(post cure)(2次硬化)用烘箱等進一步加熱。 By curing the curable epoxy resin composition of the present invention (or the curable epoxy resin composition in the B-stage state) by heating, it is possible to obtain a mold (for example, a mold for transfer molding, a mold for compression molding, etc.). It is excellent in moldability, has high reflectance, is excellent in heat resistance and light resistance, and is a tough cured product (in the case of "the cured product of the present invention"). The heating temperature (hardening temperature) at the time of hardening is not particularly limited, but is preferably 100 to 200 ° C, more preferably 150 to 190 ° C. Further, the heating time (heating time) at the time of hardening is not particularly limited, but is preferably 40 to 300 seconds, more preferably 60 to 120 seconds. When the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening becomes insufficient, and conversely, when it is higher than the upper limit of the above range, yellowing due to thermal decomposition occurs, and the interval time ( Tact time) is long and productivity is low, so it is not 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. Further, the heat hardening treatment may be carried out in one stage (for example, only the transfer molding stage), and for example, post curing (second hardening) may be further heated in an oven or the like after transfer molding.
此外，本發明的硬化性環氧樹脂組成物的硬化物的線膨脹係數沒有特別的限定，但較佳為 10~30ppm/℃，更佳為10~20ppm/℃，再較佳為11~18ppm/℃。若線膨脹係數超過30ppm/℃，則變得容易在其與導線框間產生翹曲。此外，若線膨脹係數小於10ppm/℃，則變得容易在其與導線框間產生翹曲，有因無機填充劑過多而流動性降低而產生成形不良(未填充)的傾向。又，上述線膨脹係數係按照JIS K7197測定。 Further, the linear expansion coefficient of the cured product of the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 10 to 30 ppm/° C., more preferably 10 to 20 ppm/° C., still more preferably 11 to 18 ppm/° C. If the coefficient of linear expansion exceeds 30 ppm/° C., it becomes easy to cause warpage between the lead frame and the lead frame. In addition, when the coefficient of linear expansion is less than 10 ppm/° C., warping tends to occur between the lead frame and the lead frame, and the fluidity is lowered due to excessive inorganic filler, and molding failure (unfilled) tends to occur. Further, the linear expansion coefficient is measured in accordance with JIS K7197.
本發明的硬化性環氧樹脂組成物，能較佳地用作供形成光半導體裝置中的光半導體元件的基板(光半導體元件搭載用基板)具有的反射體(光反射構件)用的材料(反射體形成用樹脂組成物)。藉由將本發明的硬化性環氧樹脂組成物用作反射體用樹脂組成物，能夠製造出具有對模具的脫模性優異因而生產性高，具有高反射率，耐熱性及耐光性優異，而且強韌的反射體的光半導體元件搭載用基板。 The curable epoxy resin composition of the present invention can be preferably used as a material for a reflector (light reflecting member) which is provided in a substrate (an optical semiconductor element mounting substrate) for forming an optical semiconductor element in an optical semiconductor device ( A resin composition for forming a reflector). By using the curable epoxy resin composition of the present invention as a resin composition for a reflector, it is possible to produce a mold having excellent mold release property, high productivity, high reflectance, and excellent heat resistance and light resistance. Further, the substrate for mounting an optical semiconductor element of a strong reflector is used.
本發明的光半導體元件搭載用基板係至少具有反射體的基板，該反射體係利用本發明的硬化性環氧樹脂組成物的硬化物(藉由使本發明的硬化性環氧樹脂組成物硬化所得到的硬化物)形成的。第1圖係顯示本發明的光半導體元件搭載用基板之一例的概略圖，(a)表示斜視圖，(b)表示剖面圖。第1圖中的100表示反射體，101表示金屬配線(導線框)，102表示光半導體元件的搭載區域。在本發明的光半導體元件搭載用基板中反射體100環狀地包圍光半導體元件的搭載區域102的周圍， 具有以該環的徑朝上方地擴大的方式傾斜的凹狀的形狀。本發明的光半導體元件搭載用基板，若為上述凹狀的形狀的內側表面至少是利用本發明的硬化性環氧樹脂組成物的硬化物所形成的話即可。 The substrate for mounting an optical semiconductor element according to the present invention is a substrate having at least a reflector, and the reflection system uses a cured product of the curable epoxy resin composition of the present invention (by curing the curable epoxy resin composition of the present invention) The resulting hardened material) is formed. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention, wherein (a) is a perspective view and (b) is a cross-sectional view. In the first drawing, 100 denotes a reflector, 101 denotes a metal wiring (a lead frame), and 102 denotes a mounting region of the optical semiconductor element. In the optical semiconductor element mounting substrate of the present invention, the reflector 100 surrounds the mounting region 102 of the optical semiconductor element in a ring shape, It has a concave shape which is inclined so that the diameter of the ring expands upward. In the substrate for mounting an optical semiconductor element of the present invention, the inner surface of the concave shape may be formed of at least a cured product of the curable epoxy resin composition of the present invention.
作為形成本發明的光半導體元件搭載用基板中的反射體的方法，能利用公知或慣用的成型方法，沒有特別的限定，例如，可舉出將本發明的硬化性環氧樹脂組成物(反射體形成用樹脂組成物)附加於轉移成型、壓縮成型、注塑成型、LIM成型(注塑成型)、利用分散器的壩(dam)成型等的各種成型方法等。 The method of forming the reflector in the substrate for mounting an optical semiconductor element of the present invention can be a known or conventional molding method, and is not particularly limited. For example, the curable epoxy resin composition of the present invention (reflection) The resin composition for bulk formation is added to various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), dam molding using a disperser, and the like.
具體而言，例如，能夠藉由將本發明的硬化性環氧樹脂組成物(反射體形成用樹脂組成物)注入既定的模具(轉移成型用模具、壓縮成型用模具等)內，加熱硬化來形成反射體。作為此時的加熱硬化條件，例如，能從上述的形成硬化物之際的條件適宜選擇。 Specifically, for example, the curable epoxy resin composition (resin composition for forming a reflector) of the present invention can be injected into a predetermined mold (transform molding mold, compression molding mold, etc.) and heat-hardened. Form a reflector. As the heat curing conditions at this time, for example, it can be appropriately selected from the conditions for forming the cured product described above.
藉由使用本發明的光半導體元件搭載用基板作為光半導體裝置的基板，對該基板搭載光半導體元件，來得到本發明的光半導體裝置。 By using the optical semiconductor element mounting substrate of the present invention as a substrate of an optical semiconductor device, an optical semiconductor device is mounted on the substrate to obtain an optical semiconductor device of the present invention.
本發明的光半導體裝置係至少具有本發明的光半導體元件搭載用基板、和搭載在該基板的光半導體元件的光半導體裝置。本發明的光半導體裝置，由於具有利用本發明的硬化性環氧樹脂組成物的硬化物所形成的反射體作為反射體，因此光的導出效率高，此外， 光度難以伴隨時間經過而降低等，耐久性也優異。第2圖係顯示本發明的光半導體裝置之一例的概略圖(剖面圖)。第2圖中的100表示反射體，102表示金屬配線(導線框)，103表示接合導線，104表示密封材，105表示晶粒接合材，106表示光半導體元件(LED元件)。在第2圖所示的光半導體裝置中，從光半導體元件106所發出的光係由反射體100的表面(反射面)反射，因此可高效率地導出來自光半導體元件106的光。又，如第2圖所示，本發明的光半導體裝置中的光半導體元件通常是利用透明的密封材(第2圖中的104)密封。 The optical semiconductor device of the present invention includes at least the optical semiconductor element mounting substrate of the present invention and an optical semiconductor device mounted on the optical semiconductor element of the substrate. In the optical semiconductor device of the present invention, since the reflector formed of the cured product of the curable epoxy resin composition of the present invention has a reflector as a reflector, the light extraction efficiency is high, and The luminosity is hard to be lowered with time passage, and the durability is also excellent. Fig. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention. In Fig. 2, 100 denotes a reflector, 102 denotes a metal wiring (lead frame), 103 denotes a bonding wire, 104 denotes a sealing material, 105 denotes a die bonding material, and 106 denotes an optical semiconductor element (LED element). In the optical semiconductor device shown in FIG. 2, the light emitted from the optical semiconductor element 106 is reflected by the surface (reflecting surface) of the reflector 100, so that light from the optical semiconductor element 106 can be efficiently extracted. Further, as shown in Fig. 2, the optical semiconductor element in the optical semiconductor device of the present invention is usually sealed by a transparent sealing material (104 in Fig. 2).
本發明的硬化性環氧樹脂組成物，不限於作為上述的反射體形成用樹脂組成物的用途，例如，也能夠用於接著劑、電氣絕緣材、積層板、塗層、印墨、塗料、封裝材、阻劑、複合材料、基材、薄片、薄膜、光學元件、光學透鏡、光學構件、光造形、電子紙、觸控面板、太陽能電池基板、光導波路、導光板、全像攝影記憶體等的其他各種用途上。 The curable epoxy resin composition of the present invention is not limited to the use as the above-described resin composition for forming a reflector, and can be used, for example, as an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, or the like. Packaging materials, resists, composite materials, substrates, sheets, films, optical components, optical lenses, optical components, optical shaping, electronic paper, touch panels, solar cell substrates, optical waveguides, light guides, holographic memory And other various uses.
以下，基於實施例而更詳細地說明本發明，但本發明不限於這些實施例。又，表1中的硬化性環氧樹脂組成物的各成分的摻合量的單位係重量份。此外，表1中的「填料量(wt%)」係相對於硬化性環氧樹脂組成物的總量，白色顏料和無機填充劑的含量的合計比例(重量%)。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. Moreover, the unit of the blending amount of each component of the curable epoxy resin composition in Table 1 is a part by weight. In addition, the "amount of filler (wt%)" in Table 1 is a total ratio (% by weight) of the content of the white pigment and the inorganic filler with respect to the total amount of the curable epoxy resin composition.
如表1所示，將異三聚氰酸衍生物(商品名「MA-DGIC」，四國化成工業(股)製)40重量份、脂環式環氧樹脂(商品名「Celloxide 2021P」，DAICEL(股)製)40重量份、硬化劑(商品名「Rikacid MH-700」，新日本理化(股)製)80重量份、硬化促進劑(商品名「Hishicolin PX-4ET」，日本化學工業(股)製)2重量份、抗氧化劑(商品名「HCA」，三光(股)製)2重量份、脫模劑(商品名「Licowax OP」，Clariant Japan(股)製)1重量份、脫模劑(商品名「Licowax PED191」，Clariant Japan(股)製)1重量份、白色顏料(商品名「FTR-700」，堺化學工業(股)製)200重量份、無機填充劑(商品名「FB-950」，電氣化學工業(股)製)700重量份放入行星式混合機，在80℃下加熱攪拌30分鐘後，冷卻所得到的混合物，從而得到黏土狀的硬化性環氧樹脂組成物。 As shown in Table 1, 40 parts by weight of an isocyanuric acid derivative (trade name "MA-DGIC", manufactured by Shikoku Chemicals Co., Ltd.) and an alicyclic epoxy resin (trade name "Celloxide 2021P", 40 parts by weight of a curing agent (trade name "Rikacid MH-700", manufactured by Nippon Chemical and Chemical Co., Ltd.), 80 parts by weight, and a hardening accelerator (trade name "Hishicolin PX-4ET", Japan Chemical Industry) (2) parts by weight, 2 parts by weight of an antioxidant (trade name "HCA", manufactured by Sanko Co., Ltd.), and 1 part by weight of a release agent (trade name "Licowax OP", manufactured by Clariant Japan Co., Ltd.) 1 part by weight of a release agent (trade name "Licowax PED191", manufactured by Clariant Japan Co., Ltd.), white pigment (trade name "FTR-700", manufactured by Sigma Chemical Industry Co., Ltd.), 200 parts by weight, and inorganic filler (product) 700 parts by weight of "FB-950", manufactured by Electrochemical Industry Co., Ltd., placed in a planetary mixer, heated and stirred at 80 ° C for 30 minutes, and then the obtained mixture was cooled to obtain a clay-like hardenable epoxy. Resin composition.
除了如表1所示變更硬化性環氧樹脂組成物的摻合組成以外，與實施例1同樣地進行以得到硬化性環氧樹脂組成物。 A curable epoxy resin composition was obtained in the same manner as in Example 1 except that the blending composition of the curable epoxy resin composition was changed as shown in Table 1.
對在實施例及比較例所得到的硬化性環氧樹脂組成物，實施下述的評價。又，在下述的評價中使用的各試驗片(硬化性環氧樹脂組成物的硬化物)係使用轉移成型機利用轉移成型來製作(硬化條件：180℃×180秒鐘)。成型後的硬化物係在150℃下進行4小時的後熟化。 The following evaluations were carried out on the curable epoxy resin compositions obtained in the examples and the comparative examples. Moreover, each test piece (hardened material of the curable epoxy resin composition) used for the following evaluation was produced by transfer molding using a transfer molding machine (curing conditions: 180 ° C × 180 seconds). The cured product after molding was subjected to post-aging at 150 ° C for 4 hours.
使用硬化性環氧樹脂組成物，成形30mm×30mm×3mm厚的試驗片(硬化物)，使用分光光度計，進行上述試驗片的波長460nm的反射率測定。將結果顯示在表1。 Using a curable epoxy resin composition, a test piece (cured product) having a thickness of 30 mm × 30 mm × 3 mm was formed, and the reflectance of the test piece at a wavelength of 460 nm was measured using a spectrophotometer. The results are shown in Table 1.
測定裝置：分光光度計UV-2450島津製作所(股)製 Measuring device: Spectrophotometer UV-2450 Shimadzu Manufacturing Co., Ltd.
使用與在初期反射率的評價中使用者同樣的試驗片(硬化物；30mm×30mm×3mm厚)，將該試驗片放入150℃的乾燥機放置1000小時後，進行460nm的反射率的測定。將結果顯示在表1。 The test piece (cured material; 30 mm × 30 mm × 3 mm thick) similar to the user in the evaluation of the initial reflectance was used, and the test piece was placed in a dryer at 150 ° C for 1000 hours, and then the reflectance at 460 nm was measured. . The results are shown in Table 1.
使用與在初期反射率的評價中使用者同樣的試驗片(硬化物；30mm×30mm×3mm厚)，將該試驗片通過回流爐(商品名「UNI-5016F」，日本Antom(股)製，溫度條件：260℃×10sec)5次後，進行460nm的反射率的測定。將結果顯示在表1。 The test piece (cured material; 30 mm × 30 mm × 3 mm thick) similar to the user in the evaluation of the initial reflectance was used, and the test piece was passed through a reflow furnace (trade name "UNI-5016F", manufactured by Antom, Japan). After the temperature conditions: 260 ° C × 10 sec) 5 times, the reflectance at 460 nm was measured. The results are shown in Table 1.
各試驗的結果，將都滿足下述(1)~(3)者判定為○(良好)。另一方面，在不滿足下述(1)~(3)中任一者的情況下判定為X(不良)。 As a result of each test, those who satisfy the following (1) to (3) are judged as ○ (good). On the other hand, if any of the following (1) to (3) is not satisfied, it is determined as X (bad).
(1)初期反射率為95%以上 (1) The initial reflectance is 95% or more
(2)150℃ 1000h後反射率為80%以上 (2) After 150h at 1000°C, the reflectivity is above 80%
(3)回流260℃ 10sec 5次後反射率為95%以上 (3) After reflowing at 260 ° C for 10 sec 5 times, the reflectance is 95% or more
將結果顯示在表1的「綜合判定」欄。 The results are displayed in the "Comprehensive Decision" column of Table 1.
以下顯示表1記載的硬化性環氧樹脂組成物的構成成分的說明。 The constituent components of the curable epoxy resin composition described in Table 1 are shown below.
MA-DGIC：商品名「MA-DGIC」(異三聚氰酸一烯丙基二環氧丙酯，四國化成工業(股)製) MA-DGIC: trade name "MA-DGIC" (I-allyl diglycidyl isocyanurate, manufactured by Shikoku Chemical Industry Co., Ltd.)
2021P：商品名「Celloxide 2021P」(3,4-環氧環己基甲基(3,4-環氧基)環己烷羧酸酯)，DAICEL(股)製) 2021P: trade name "Celloxide 2021P" (3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate), manufactured by DAICEL Co., Ltd.)
雙(3,4-環氧環己基甲基)醚：依照國際公開第2014/181787號記載的方法製造者。 Bis(3,4-epoxycyclohexylmethyl)ether: Manufacturer according to the method described in International Publication No. 2014/181787.
EHPE3150：商品名「EHPE3150」(2,2-雙(羥甲基)-1-丁醇的1,2-環氧基-4-(2-環氧乙基)環己烷加成物，DAICEL(股)製) EHPE3150: Trade name "EHPE3150" (2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct, DAICEL (share) system)
YX8040：商品名「YX8040」(氫化雙酚A型環氧樹脂，三菱化學(股)製) YX8040: trade name "YX8040" (hydrogenated bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Corporation)
ST-4000D：商品名「ST-4000D」(氫化雙酚A型環氧樹脂，新日鐵住金化學(股)製) ST-4000D: Trade name "ST-4000D" (hydrogenated bisphenol A epoxy resin, Nippon Steel & Sumitomo Chemical Co., Ltd.)
MH-700：商品名「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: trade name "Rikacid MH-700" (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Nippon Chemical and Chemical Co., Ltd.)
Rikacid TH：商品名「Rikacid TH」(1,2,3,6-四氫酞酸酐，新日本理化(股)製) Rikacid TH: trade name "Rikacid TH" (1,2,3,6-tetrahydrophthalic anhydride, Nippon Chemical and Chemical Co., Ltd.)
PX-4ET：商品名「Hishicolin PX-4ET」(四-正丁基鏻-o,o-二乙基偶磷基二硫磺酸酯，日本化學工業(股)製) PX-4ET: trade name "Hishicolin PX-4ET" (tetra-n-butyl fluorene-o, o-diethylphosphinodithiosulfonate, manufactured by Nippon Chemical Industry Co., Ltd.)
HCA：商品名「HCA」(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)，三光(股)製) HCA: trade name "HCA" (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), Sanguang (share) system)
Licowax OP：商品名「Licowax OP」(二十八酸的部分皂化酯蠟，Clariant Japan(股)製) Licowax OP: trade name "Licowax OP" (partially saponified ester wax of octadecanoic acid, manufactured by Clariant Japan Co., Ltd.)
PED 191：商品名「Licowax PED191」(氧化聚乙烯蠟，Clariant Japan(股)製) PED 191: trade name "Licowax PED191" (oxidized polyethylene wax, manufactured by Clariant Japan Co., Ltd.)
FTR-700：商品名「FTR-700」(氧化鈦，堺化學工業(股)製) FTR-700: trade name "FTR-700" (titanium oxide, 堺Chemical Industry Co., Ltd.)
FB-950：商品名「FB-950」(氧化矽，電氣化學工業(股)製) FB-950: trade name "FB-950" (manganese oxide, electric chemical industry (stock) system)
本發明的硬化性樹脂組成物，例如，也能夠用於接著劑、電氣絕緣材、積層板、塗層、印墨、塗料、封裝材、阻劑、複合材料、基材、薄片、薄膜、光學元件、光學透鏡、光學構件、光造形、電子紙、觸控面板、太陽能電池基板、光導波路、導光板、全像攝影記憶體等的各種用途上。特別是，本發明的硬化性樹脂組成物能較佳地用作反射體形成用樹脂組成物。 The curable resin composition of the present invention can also be used, for example, as an adhesive, an electrical insulating material, a laminate, a coating, an ink, a coating, a packaging, a resist, a composite, a substrate, a sheet, a film, and an optical. Various uses such as components, optical lenses, optical components, optical shaping, electronic paper, touch panels, solar cell substrates, optical waveguides, light guides, and holographic memory. In particular, the curable resin composition of the present invention can be preferably used as a resin composition for forming a reflector.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014157197A JP2017171696A (en) | 2014-07-31 | 2014-07-31 | Curable resin composition, cured product, sealing material, and semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201609949A true TW201609949A (en) | 2016-03-16 |
Family
ID=55217432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104124643A TW201609949A (en) | 2014-07-31 | 2015-07-30 | Curable resin composition and cured product thereof, substrate for mounting optical semiconductor element, and optical semiconductor device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2017171696A (en) |
| TW (1) | TW201609949A (en) |
| WO (1) | WO2016017531A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018119032A (en) * | 2017-01-23 | 2018-08-02 | 株式会社ダイセル | Curable resin composition for light reflection and cured product thereof, and optical semiconductor device |
| WO2018135558A1 (en) * | 2017-01-23 | 2018-07-26 | 株式会社ダイセル | Curable resin composition for optical reflection, cured product thereof, and optical semiconductor device |
| JP6929069B2 (en) * | 2017-01-23 | 2021-09-01 | 株式会社ダイセル | Curable resin composition for light reflection, its cured product, and optical semiconductor device |
| KR102140259B1 (en) * | 2018-01-11 | 2020-07-31 | 주식회사 엘지화학 | Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649218B (en) * | 2011-07-13 | 2016-05-11 | 株式会社大赛璐 | Curable epoxy resin composition |
| CN104204024A (en) * | 2012-03-27 | 2014-12-10 | 住友电木株式会社 | Resin composition for reflecting light, substrate for mounting optical semiconductor element, and optical semiconductor device |
| JP6046497B2 (en) * | 2013-01-09 | 2016-12-14 | 株式会社ダイセル | Curable epoxy resin composition |
-
2014
- 2014-07-31 JP JP2014157197A patent/JP2017171696A/en active Pending
-
2015
- 2015-07-23 WO PCT/JP2015/071008 patent/WO2016017531A1/en active Application Filing
- 2015-07-30 TW TW104124643A patent/TW201609949A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016017531A1 (en) | 2016-02-04 |
| JP2017171696A (en) | 2017-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5945537B2 (en) | Curable resin composition for light reflection and optical semiconductor device | |
| TWI511996B (en) | Curable epoxy resin composition | |
| JP5829893B2 (en) | Curable epoxy resin composition | |
| JP5797110B2 (en) | Curable epoxy resin composition | |
| JP5918699B2 (en) | Curable epoxy resin composition and optical semiconductor device using the same | |
| TW201348283A (en) | Curable epoxy resin composition | |
| CN102952370A (en) | Epoxy resin composition for optical semiconductor device and optical semiconductor device using the same | |
| TW201609949A (en) | Curable resin composition and cured product thereof, substrate for mounting optical semiconductor element, and optical semiconductor device | |
| TWI525859B (en) | A white hardening composition for an optical semiconductor device, a molded body for an optical semiconductor device, and an optical semiconductor device | |
| KR20140009202A (en) | Curable epoxy resin composition | |
| JP6174836B2 (en) | Curable epoxy resin composition for molding white reflector and cured product thereof, substrate for mounting optical semiconductor element, and optical semiconductor device | |
| WO2017131152A1 (en) | Curable epoxy resin composition for white reflectors, cured product thereof, substrate for mounting optical semiconductor element, and optical semiconductor device | |
| WO2017138487A1 (en) | Curable epoxy resin composition for white reflector and cured product of same, substrate for mounting optical semiconductor element, optical semiconductor device, and manufacturing method | |
| TW201833167A (en) | Curable resin composition for light reflection and cured product thereof and optical semiconductor device | |
| WO2017138491A1 (en) | Curable resin composition for reflecting light, cured product thereof, and optical semiconductor device | |
| JP5899281B2 (en) | White curable composition for optical semiconductor device, method for producing white curable composition for optical semiconductor device, molded article for optical semiconductor device, and optical semiconductor device | |
| WO2015146988A1 (en) | Thermosetting resin composition, cured product thereof, optical semiconductor element mounting substrate, and optical semiconductor device | |
| JP2016222865A (en) | Curable epoxy resin composition for white reflector and cured article thereof, substrate for mounting optical semiconductor element and optical semiconductor device | |
| JP2019108457A (en) | Light-reflecting thermosetting resin tablet, optical semiconductor element mounting board, method for manufacture thereof, and optical semiconductor device | |
| WO2013145607A1 (en) | Resin composition for reflecting light, substrate for mounting optical semiconductor element, and optical semiconductor device | |
| JP2016222866A (en) | Curable epoxy resin composition for white reflector and cured article thereof, substrate for mounting optical semiconductor element and optical semiconductor device | |
| JP2017141414A (en) | Curable resin composition for light reflection and cured product thereof, and optical semiconductor device | |
| JP2017141411A (en) | Curable resin composition for light reflection and cured product thereof, and optical semiconductor device | |
| JP2017155145A (en) | Curable epoxy resin composition for optical material | |
| TW201402635A (en) | Curable epoxy resin composition |