TW201446873A - Epoxy resin composition for optical semiconductor reflectors, thermosetting resin composition, lead frame, sealed optical semiconductor element, and optical semiconductor device - Google Patents
Epoxy resin composition for optical semiconductor reflectors, thermosetting resin composition, lead frame, sealed optical semiconductor element, and optical semiconductor device Download PDFInfo
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- TW201446873A TW201446873A TW103116086A TW103116086A TW201446873A TW 201446873 A TW201446873 A TW 201446873A TW 103116086 A TW103116086 A TW 103116086A TW 103116086 A TW103116086 A TW 103116086A TW 201446873 A TW201446873 A TW 201446873A
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/93—Batch processes
- H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
- H01L24/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
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- 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
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- 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
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- 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
- H01L2224/48257—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 die pad of the item
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- 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
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
Abstract
Description
本發明係有關於例如使由光半導體元件發出之光反射之作為反射器(反射部)之形成材料的光半導體反射器用環氧樹脂組成物、光半導體裝置用熱硬化性樹脂組成物及使用其製得之光半導體裝置用引線框、密封型光半導體元件以及光半導體裝置。 The present invention relates to an epoxy resin composition for an optical semiconductor reflector, a thermosetting resin composition for an optical semiconductor device, and a use thereof, which are used as a material for forming a reflector (reflecting portion) for reflecting light emitted from an optical semiconductor element. A lead frame, a sealed optical semiconductor element, and an optical semiconductor device for the obtained optical semiconductor device.
以往，裝載光半導體元件而成之光半導體裝置係構成如下：以圖1所示為例，在由第一板部1及第二板部2構成之金屬引線框上裝載光半導體元件3，且以包圍上述光半導體元件3周圍之方式，進一步以填埋第一板部1與第二板部2間之方式，形成有由樹脂材料構成之光反射用之反射器4。又，使用必要時含有螢光體之矽氧樹脂等透明樹脂，對裝載在由上述金屬引線框與反射器4之內周面形成之凹部5上的光半導體元件3進行樹脂密封，藉此形成密封樹脂層6。在圖1中，7、8係電性連接金屬引線框及光半 導體元件3之接合線，且係依需要設置。 Conventionally, an optical semiconductor device in which an optical semiconductor element is mounted is configured as follows. As shown in FIG. 1 , an optical semiconductor device 3 is mounted on a metal lead frame including a first plate portion 1 and a second plate portion 2, and A reflector 4 for light reflection made of a resin material is further formed so as to surround the periphery of the optical semiconductor element 3 so as to fill the space between the first plate portion 1 and the second plate portion 2. Moreover, the optical semiconductor element 3 mounted on the concave portion 5 formed on the inner circumferential surface of the metal lead frame and the reflector 4 is resin-sealed by using a transparent resin such as a fluorinated resin containing a phosphor, if necessary, to form a resin. The resin layer 6 is sealed. In Figure 1, the 7 and 8 series are electrically connected to the metal lead frame and the light half. The bonding wires of the conductor elements 3 are provided as needed.
在如此之光半導體裝置中，近年來，使用以環氧樹脂等為代表之熱硬化性樹脂，例如，藉由轉移成形等成形製造上述反射器4。又，以往，在上述熱硬化性樹脂中混合氧化鈦作為白色顏料，且反射由上述光半導體元件3發出之光(參照專利文獻1)。 In such an optical semiconductor device, in recent years, a thermosetting resin typified by an epoxy resin or the like is used, and the reflector 4 is molded by, for example, transfer molding. In addition, in the above-mentioned thermosetting resin, titanium oxide is mixed as a white pigment, and light emitted from the optical semiconductor element 3 is reflected (see Patent Document 1).
專利文獻1：日本特開2011-258845號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-258845
但是，如上所述地使用氧化鈦作為白色顏料形成反射器時，雖然關於初期之光反射率毫無問題可實現高光反射率，卻有在一段時間之使用下該光反射率降低之問題。如此一來，在長期發揮高光反射率，即，長期耐光性方面尚嫌不足，且關於該長期耐光性強烈希望進一步提高。 However, when a reflector is formed using titanium oxide as a white pigment as described above, although high light reflectance can be achieved without any problem with respect to the initial light reflectance, there is a problem that the light reflectance is lowered under a period of use. As a result, it is not sufficient to exhibit high-light reflectance for a long period of time, that is, long-term light resistance, and it is strongly desired to further improve the long-term light resistance.
本發明係鑒於如此情形而作成者，其目的在於提供一種不只具高初期光反射率且具優異之長期耐光性之光半導體裝置用熱硬化性樹脂組成物及使用其製得之光半導體裝置用引線框、密封型光半導體元件以及光半導體裝置。 The present invention has been made in view of the above circumstances, and an object of the invention is to provide a thermosetting resin composition for an optical semiconductor device having high initial light reflectance and excellent long-term light resistance, and an optical semiconductor device using the same. A lead frame, a sealed optical semiconductor element, and an optical semiconductor device.
為達成上述目的，本發明係以含有下述(A)至(C)之光半導體裝置用熱硬化性樹脂組成物為第1要旨。 In order to achieve the above object, the present invention is the first aspect of the thermosetting resin composition for an optical semiconductor device comprising the following (A) to (C).
(A)熱硬化性樹脂。 (A) Thermosetting resin.
(B)能帶間隙(禁制帶)為3.3至5.5eV之白色顏料。 (B) A white pigment having a gap (forbidden band) of 3.3 to 5.5 eV.
(C)無機質填充劑。 (C) Inorganic filler.
另一方面，本發明係以藉由下述測量方法(x)測出之光反射率降低度(α2-α1)在-5至0之範圍內的光半導體反射器用環氧樹脂組成物為要旨。 On the other hand, the present invention is based on the epoxy resin composition for an optical semiconductor reflector having a light reflectance reduction degree (α2-α1) measured by the following measurement method (x) in the range of -5 to 0. .
(x)使用以預定之硬化條件(條件：175℃×2分鐘之成形+175℃×3小時硬化)製作而成之厚度1mm的試驗片，測量在室溫(25℃)下之波長600nm的光反射率(α1)，並且在藉110℃之熱板加熱該試驗片之狀態下，以1W/cm2之強度照射波長436nm之光15分鐘後，測量在室溫(25℃)下之波長600nm的光反射率(α2)。 (x) A test piece having a thickness of 1 mm prepared by predetermined hardening conditions (condition: 175 ° C × 2 minutes of forming + 175 ° C × 3 hours hardening) was measured, and the wavelength of 600 nm at room temperature (25 ° C) was measured. The light reflectance (α1), and the light having a wavelength of 436 nm was irradiated with an intensity of 1 W/cm 2 for 15 minutes in a state where the test piece was heated by a hot plate at 110 ° C, and the wavelength at room temperature (25 ° C) was measured. Light reflectance at 600 nm (α2).
又，本發明係以光半導體裝置用引線框為第2要旨，該光半導體裝置用引線框係用以只在厚度方向之一面上裝載光半導體元件之板狀光半導體裝置用引線框，其具有互相隔著間隙配置之數個板部，並在上述間隙中形成反射器而成，且該反射器係使用上述第1要旨之光半導體裝置用熱硬化性樹脂組成物填充並經硬化而成者。本發明又以一光半導體裝置用引線框為第3要旨，該光半導體裝置用引線框係具有光半導體元件裝載區域並形成反射器而成的立體狀光半導體裝置用引線框，且該反射器以其本身之至少一部份包圍元件裝載區域周圍之狀態形成；又，上述 反射器係使用上述第1要旨之光半導體裝置用熱硬化性樹脂組成物形成。 Further, the present invention is directed to a lead frame for an optical semiconductor device, which is a lead frame for a plate-shaped optical semiconductor device in which an optical semiconductor element is mounted on only one surface in a thickness direction, and has a lead frame for an optical semiconductor device. The reflector is formed by forming a plurality of plate portions with a gap therebetween, and the reflector is formed by hardening a resin composition using the thermosetting resin composition of the optical semiconductor device according to the first aspect. . The present invention is directed to a lead frame for an optical semiconductor device, wherein the lead frame of the optical semiconductor device has a lead frame for a three-dimensional optical semiconductor device in which an optical semiconductor element mounting region is formed and a reflector is formed, and the reflector Formed by at least a portion of itself surrounding the loading area of the component; The reflector is formed of a thermosetting resin composition for an optical semiconductor device according to the first aspect of the invention.
又，本發明係以光半導體裝置為第4要旨，該光半導體裝置係由其一面上具有用以裝載光半導體元件之元件裝載區域的板部互相隔著間隙配置，且在上述元件裝載區域之預定位置上裝載光半導體元件而成者，又，該光半導體裝置係在上述間隙中形成反射器而成，且該反射器係使用上述第1要旨之光半導體裝置用熱硬化性樹脂組成物填充並經硬化而成者。本發明又以一光半導體裝置為第5要旨，該光半導體裝置係於光半導體裝置用引線框的預定位置上裝載光半導體元件而成者，前述光半導體裝置用引線框係具有光半導體元件裝載區域並形成反射器而成，且該反射器以其本身之至少一部份包圍元件裝載區域周圍之狀態形成；又，上述反射器係使用上述第1要旨之光半導體裝置用熱硬化性樹脂組成物形成。 Further, the present invention is directed to an optical semiconductor device in which a plate portion having a component mounting region on which an optical semiconductor element is mounted is disposed with a gap therebetween, and is disposed in the component loading region. When the optical semiconductor device is mounted on the predetermined position, the optical semiconductor device is formed by forming a reflector in the gap, and the reflector is filled with a thermosetting resin composition for the optical semiconductor device according to the first aspect. And it is hardened. According to a fifth aspect of the invention, the optical semiconductor device is characterized in that the optical semiconductor device is mounted on a predetermined position of a lead frame for an optical semiconductor device, and the lead frame for the optical semiconductor device has an optical semiconductor device mounted thereon. The reflector is formed in a region, and the reflector is formed in a state in which at least a portion of the reflector surrounds the component mounting region; and the reflector is composed of a thermosetting resin using the optical semiconductor device according to the first aspect. Object formation.
又，本發明係以密封型光半導體元件為第6要旨，該密封型光半導體元件係在背面形成數個連接用電極而成之光半導體元件的側面上，形成由上述第1要旨之光半導體裝置用熱硬化性樹脂組成物構成之反射器，且藉密封層被覆上述光半導體元件上部之發光面或受光面而成。本發明又以使上述第6要旨之密封型光半導體元件透過其連接用電極裝載在配線電路板之預定位置而成的光半導體裝置為第7要旨。 Further, the present invention is a sixth aspect of the invention, in which a sealed optical semiconductor device is formed on a side surface of an optical semiconductor device in which a plurality of connection electrodes are formed on a back surface, and an optical semiconductor according to the first aspect is formed. The device is formed of a reflector made of a thermosetting resin composition, and is covered with a light-emitting surface or a light-receiving surface of the upper portion of the optical semiconductor element by a sealing layer. In the present invention, the optical semiconductor device in which the sealed optical semiconductor device of the sixth aspect is mounted on a predetermined position of the wiring board through the connection electrode is the seventh object.
本發明人等為得到除了高初期光反射率亦具優 異長期耐光性之光半導體裝置用熱硬化性樹脂組成物而反覆專心檢討。在該研究過程中，想起由與習知不同之觀點特定白色顏料，且著眼於物性之一的能帶間隙，依據該物性，反覆深入研究。結果，發現當使用能帶間隙(禁制帶)為3.3至5.5eV之範圍內者作為白色顏料時，因在上述能帶間隙之範圍內，則例如可抑制由光半導體元件發出之光之吸收，亦可抑制白色顏料本身之著色，以維持高光反射率，從而得到可作為不僅具高初期光反射率且具優異長期耐光性之反射器形成材料的熱硬化性樹脂組成物。 The present inventors have excellent in addition to high initial light reflectance. The hetero-long-term light-resistant optical semiconductor device is repeatedly reviewed with a thermosetting resin composition. In the course of this research, a band gap which is specific to a white pigment which is different from the conventional viewpoint and which focuses on one of the physical properties is considered, and based on the physical property, it is further studied in depth. As a result, it has been found that when a band gap (forbidden band) is used as a white pigment in the range of 3.3 to 5.5 eV, the absorption of light emitted from the optical semiconductor element can be suppressed, for example, within the range of the above band gap. It is also possible to suppress the coloring of the white pigment itself, and to maintain the high light reflectance, thereby obtaining a thermosetting resin composition which can be used as a reflector forming material having high initial light reflectance and excellent long-term light resistance.
如所述，本發明係含有前述熱硬化性樹脂(A)、具有特定能帶間隙(禁制帶)之白色顏料(B)、及無機質填充劑(C)之光半導體裝置用熱硬化性樹脂組成物。因此，不僅可具有高初期光反射率，亦可具有優異長期耐光性。故以使用上述光半導體裝置用熱硬化性樹脂組成物形成反射器而成之光半導體裝置來看，可得到信賴性高之光半導體裝置。 As described above, the present invention is composed of a thermosetting resin containing a thermosetting resin (A), a white pigment (B) having a specific band gap (forbidden band), and an inorganic filler (C). Things. Therefore, it is possible to have not only high initial light reflectance but also excellent long-term light resistance. Therefore, in view of the optical semiconductor device in which the reflector is formed using the thermosetting resin composition for an optical semiconductor device, an optical semiconductor device having high reliability can be obtained.
又，上述白色顏料(B)與無機填充劑(C)之合計含有比例在特定範圍內，且白色顏料(B)之含有比例在特定範圍內時，可具有更優異之長期耐光性。 In addition, when the total content ratio of the white pigment (B) and the inorganic filler (C) is within a specific range, and the content ratio of the white pigment (B) is within a specific range, it is possible to have more excellent long-term light resistance.
1‧‧‧第一板部 1‧‧‧First Board
2‧‧‧第二板部 2‧‧‧ Second Board
3‧‧‧光半導體元件 3‧‧‧Optical semiconductor components
4,11,15‧‧‧反射器 4,11,15‧‧‧ reflector
5‧‧‧凹部 5‧‧‧ recess
6‧‧‧密封樹脂層 6‧‧‧ sealing resin layer
7,8,12‧‧‧接合線 7,8,12‧‧‧bonding line
10‧‧‧金屬引線框 10‧‧‧Metal lead frame
16‧‧‧密封層 16‧‧‧ Sealing layer
17‧‧‧連接用電極(凸塊) 17‧‧‧Connecting electrodes (bumps)
圖1係示意性顯示光半導體裝置之構造的截面圖。 1 is a cross-sectional view schematically showing the configuration of an optical semiconductor device.
圖2係示意性顯示光半導體裝置之另一構造的俯視圖。 2 is a plan view schematically showing another configuration of an optical semiconductor device.
圖3係上述示意性顯示光半導體裝置另一構造之圖2的X-X'箭頭指向截面圖。 Fig. 3 is a cross-sectional view taken along line XX' of Fig. 2 showing another configuration of the optical semiconductor device.
圖4係示意性顯示密封型光半導體元件之構造之截面圖。 Fig. 4 is a cross-sectional view schematically showing the configuration of a sealed type optical semiconductor element.
如前所述，本發明之光半導體裝置用熱硬化性樹脂組成物(以下，稱為「熱硬化性樹脂組成物」)係例如作為圖1所示之光半導體裝置或圖2及圖3所示之光半導體裝置，圖4所示之密封型光半導體元件之反射器4、11、15形成材料使用者，且係使用熱硬化性樹脂(A成分)、特定之白色顏料(B成分)及無機填充劑(C成分)得到者，又，通常，作成液狀、或片狀、粉末狀、或打錠該粉末形成之錠狀而供反射器4、11、15形成材料使用。 As described above, the thermosetting resin composition for an optical semiconductor device of the present invention (hereinafter referred to as "thermosetting resin composition") is, for example, an optical semiconductor device as shown in FIG. 1 or FIGS. 2 and 3 In the optical semiconductor device shown in FIG. 4, the reflectors 4, 11, and 15 of the sealed optical semiconductor device shown in FIG. 4 are formed of a material user, and a thermosetting resin (component A) and a specific white pigment (component B) are used. The inorganic filler (component C) is usually obtained by forming a material in the form of a liquid, a sheet, a powder, or a tablet in which the powder is formed, and the reflectors 4, 11, and 15 are formed.
<A：熱硬化性樹脂> <A: Thermosetting resin>
上述熱硬化性樹脂(A成分)可舉環氧樹脂、矽氧樹脂等為例。該等熱硬化性樹脂可單獨或合併使用。 The thermosetting resin (component A) may, for example, be an epoxy resin or a silicone resin. These thermosetting resins may be used singly or in combination.
上述環氧樹脂可舉例如：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、酚系酚醛清漆型環氧樹脂及甲酚酚醛清漆型環氧樹脂等之酚醛清漆型環氧樹脂、異三聚氰酸單環氧丙酯、異三聚氰酸二環氧丙酯、異三聚氰酸三環氧丙酯、海因環氧樹脂等之含氮環環氧樹脂、氫化雙酚A型環氧樹脂、氫化雙酚F型環氧樹脂、脂肪 族環氧樹脂、矽氧變性環氧樹脂、環氧丙基醚型環氧樹脂、烷基取代雙酚等之二環氧丙基醚、藉由二胺苯甲烷及異三聚氰酸等之聚胺與表氯醇反應製得之環氧丙基胺型環氧樹脂、藉由過乙酸等之過酸氧化烯烴鍵製得之線狀脂肪族及脂環式環氧樹脂、低吸水率硬化體型之主流聯苯型環氧樹脂、二環環型環氧樹脂、萘型環氧樹脂等。該等環氧樹脂可單獨或合併2種以上使用。該等環氧樹脂中，由具優異透明性及耐變色性方面來看，宜單獨或合併使用脂環式環氧樹脂，或具有異三聚氰酸三環氧丙酯等之異三聚氰酸酯環構造者。由同樣理由來看，苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、甲基四氫鄰苯二甲酸、降冰片烯二酸、甲基降冰片烯二酸等之二羧酸之二環氧丙基酯亦是合適的。又，亦可舉具有芳香環氫化之脂環式構造之核氫化三苯六甲酸、核氫化焦蜜石酸等環氧丙基酯等為例。 Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, and cresol novolac epoxy resin. Nitrogen-containing varnish type epoxy resin, iso-glycidyl mono-glycidyl propyl ester, diglycidyl isocyanate, triglycidyl isocyanurate, hydantoin and the like Ring epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, fat Group of epoxy resin, epoxy modified epoxy resin, epoxy propyl ether type epoxy resin, alkyl substituted bisphenol and other diglycidyl ether, by diaminophenylmethane and iso-cyanuric acid A epoxidized propylamine type epoxy resin obtained by reacting a polyamine with epichlorohydrin, a linear aliphatic and alicyclic epoxy resin obtained by oxidizing an olefin bond by a peracid such as peracetic acid, and a low water absorption hardening The main form of biphenyl type epoxy resin, bicyclic ring type epoxy resin, naphthalene type epoxy resin and the like. These epoxy resins may be used alone or in combination of two or more. Among these epoxy resins, in view of excellent transparency and discoloration resistance, it is preferred to use an alicyclic epoxy resin alone or in combination, or a isomeric cyanide having a triglycidyl isocyanurate or the like. Acid ester ring constructor. For the same reason, dicarboxylic acid such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, norbornene diacid, methylnorbornene diacid, etc. Diethylene glycidyl acid esters are also suitable. Further, examples thereof include nuclear hydrogenated triphenyl hexacarboxylic acid having an alicyclic structure of an aromatic ring hydrogenation, and a glycidyl ester such as nuclear hydrogenated pyrophoric acid.
上述環氧樹脂在常溫可為固形或液狀，但是，一般而言，使用之環氧樹脂之平均環氧當量宜為90至1000，又，為固形時，由處理性之方便性之觀點來看，軟化點宜為50至160℃。即，環氧當量過小時，有時熱硬化性樹脂組成硬化物會脆化。又，環氧當量過大時，可看到熱硬化性樹脂組成硬化物之玻璃轉移溫度(Tg)降低之傾向。 The epoxy resin may be solid or liquid at normal temperature, but in general, the epoxy resin used has an average epoxy equivalent of 90 to 1000, and when it is solid, it is treated from the viewpoint of handling convenience. Look, the softening point should be 50 to 160 °C. That is, when the epoxy equivalent is too small, the cured product of the thermosetting resin composition may be embrittled. Further, when the epoxy equivalent is too large, the glass transition temperature (Tg) of the cured product of the thermosetting resin composition tends to decrease.
使用上述環氧樹脂作為熱硬化性樹脂(A成分)時，通常，使用硬化劑。上述硬化劑可舉酐系硬化劑、異三聚氰酸衍生物系硬化劑等為例。該等硬化劑可單獨或合併2種以上使用。該等硬化劑中，由耐熱性及耐光性之觀 點來看，宜使用酐系硬化劑。 When the above epoxy resin is used as the thermosetting resin (component A), a curing agent is usually used. The curing agent may, for example, be an anhydride-based curing agent or a different isocyanuric acid derivative-based curing agent. These hardeners can be used individually or in combination of 2 or more types. Among these hardeners, the viewpoint of heat resistance and light resistance From the point of view, it is preferred to use an anhydride hardener.
上述酐系硬化劑可舉例如：苯二甲酐、馬來酐、琥珀酐、三苯六甲酐、焦蜜石酐、萘-1,4,5,8-四羧酸二酐及其核氫化物、六氫鄰苯二甲酐、3-甲基六氫鄰苯二甲酐、4-甲基六氫鄰苯二甲酐、四氫鄰苯二甲酐、3-甲基四氫鄰苯二甲酐、4-甲基四氫鄰苯二甲酐、甲基降冰片烯二酐、環己烷-1,2,3-三羧酸-2,3-酐及其位置異構物、環己烷-1,2,3,4-四羧酸-3,4-酐及其位置異構物、降冰片烯二酐、戊二酐、二甲基戊二酐、二乙基戊二酐、甲基六氫鄰苯二甲酐、甲基四氫鄰苯二甲酐等。該等酐系硬化劑可單獨或合併2種以上使用。又，具有該等酐作為飽和脂肪鏈骨架、不飽和脂肪鏈骨架、或矽氧骨架之端基或側鏈之寡聚物亦可單獨或合併2種以上，及合併上述酐使用。該等酐系硬化劑中，宜使用苯二甲酐、六氫鄰苯二甲酐、3-甲基六氫鄰苯二甲酐、4-甲基六氫鄰苯二甲酐、四氫鄰苯二甲酐、3-甲基四氫鄰苯二甲酐、4-甲基四氫鄰苯二甲酐。又，酐系硬化劑宜使用無色或淡黃色之酐系硬化劑。又，亦可併用上述酐之水解物的羧酸。 Examples of the anhydride-based curing agent include phthalic anhydride, maleic anhydride, succinic anhydride, trimellitic anhydride, pyrogalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and their nuclear hydrogenation. , hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydroortylene Dimethyl anhydride, 4-methyltetrahydrophthalic anhydride, methylnorbornene dianhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride and its positional isomers, Cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride and its positional isomers, norbornene dianhydride, glutaric anhydride, dimethyl glutaric anhydride, diethyl pentane Anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like. These anhydride-based curing agents may be used singly or in combination of two or more. Further, the oligomer having such an anhydride as a saturated aliphatic chain skeleton, an unsaturated aliphatic chain skeleton, or an end group or a side chain of a fluorene skeleton may be used singly or in combination of two or more kinds thereof, and the above-mentioned anhydride may be used in combination. Among these anhydride-based hardeners, phthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, tetrahydroortho Phthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride. Further, as the anhydride-based curing agent, a colorless or pale yellow anhydride-based curing agent is preferably used. Further, a carboxylic acid of the hydrolyzate of the above anhydride may be used in combination.
又，上述三聚氰酸衍生物系硬化劑可舉例如：1,3,5-三(1-羧甲基)三聚氰酸酯、1,3,5-三(2-羧乙基)三聚氰酸酯、1,3,5-三(3-羧丙基)三聚氰酸酯、1,3-二(2-羧乙基)三聚氰酸酯等。該等三聚氰酸衍生物系硬化劑可單獨或合併2種以上使用。又，三聚氰酸衍生物系硬化劑宜使用無色或淡黃色之硬化劑。 Further, the cyanuric acid derivative-based curing agent may, for example, be 1,3,5-tris(1-carboxymethyl) cyanurate or 1,3,5-tris(2-carboxyethyl). Cyanurate, 1,3,5-tris(3-carboxypropyl) cyanurate, 1,3-bis(2-carboxyethyl) cyanurate, and the like. These cyanuric acid derivative-based curing agents may be used singly or in combination of two or more kinds. Further, as the cyanuric acid derivative-based hardener, a colorless or pale yellow hardener is preferably used.
在此，上述環氧樹脂與上述硬化劑之混合比例宜設定成，相對環氧樹脂中之環氧基1當量，使硬化劑中可與環氧基反應之活性基(酐基或羧基)為0.4至1.4當量，更佳是0.6至1.2當量。即，這是因為活性基過少時，可看到熱硬化性樹脂組成物之硬化速度變慢，且其硬化物之玻璃轉移溫度(Tg)降低之傾向，且活性基過多時可看到耐濕性降低之傾向。 Here, the mixing ratio of the epoxy resin and the curing agent is preferably set to be 1 equivalent to the epoxy group in the epoxy resin, and the reactive group (anhydride group or carboxyl group) which can react with the epoxy group in the curing agent is From 0.4 to 1.4 equivalents, more preferably from 0.6 to 1.2 equivalents. In other words, when the amount of the active group is too small, the curing rate of the thermosetting resin composition is slow, and the glass transition temperature (Tg) of the cured product tends to decrease, and when the active group is too much, moisture resistance is observed. The tendency to reduce sexuality.
又，依據其目的及用途，可單獨或合併2種以上使用上述酐系硬化劑及三聚氰酸衍生物系硬化劑以外之其他環氧樹脂用硬化劑，例如，酚系硬化劑、胺系硬化劑、藉醇部份酯化上述酐系硬化劑等之硬化劑。又，使用該等硬化劑時，其混合比例亦可以上述環氧樹脂與硬化劑之混合比例(當量比)為準。 In addition, depending on the purpose and the use, it is possible to use a curing agent for an epoxy resin other than the above-mentioned anhydride-based curing agent and cyanuric acid derivative-based curing agent, for example, a phenol-based curing agent or an amine system, alone or in combination of two or more kinds. A hardener or a hardener which partially esterifies the above-mentioned anhydride-based hardener with an alcohol. Further, when these curing agents are used, the mixing ratio thereof may be based on the mixing ratio (equivalent ratio) of the epoxy resin and the curing agent.
其次，說明使用上述矽氧樹脂作為上述熱硬化性樹脂(A成分)之情形。上述矽氧樹脂至少含有觸媒，具體而言，含有觸媒及矽氧樹脂。上述觸媒係例如促進矽氧樹脂之反應使矽氧樹脂硬化之硬化觸媒，較佳是促進後述之矽氧樹脂之矽氫化反應且藉由氫矽加成使矽氧樹脂硬化之矽氫化觸媒。又，上述觸媒含有過渡金屬，且上述過渡金屬可舉例如白金、鈀、銠等之白金屬元素，且較佳為白金。具體而言，在觸媒含有白金時，觸媒可舉例如：白金黑、氯化白金、氯化白金酸等之無機白金；例如，白金-烯烴錯合物、白金-羰基錯合物、白金-乙醯乙酸等之白金錯合物等，且較佳為白金錯合物。更具體而言，白金錯合 物可舉例如：白金-乙烯矽氧烷錯合物、白金-四甲基二乙烯二矽氧烷錯合物、白金-羰基環乙烯甲基矽氧烷錯合物、白金-二乙烯四甲基二矽氧烷錯合物、白金-環乙烯甲基矽氧烷錯合物、白金-辛醛/辛醇錯合物等。又，上述觸媒具有與後述矽氧樹脂區別地混合之態樣，或包含於矽氧樹脂中作為構成矽氧樹脂之成分之態樣。 Next, the case where the above-mentioned epoxy resin is used as the above-mentioned thermosetting resin (component A) will be described. The above-mentioned epoxy resin contains at least a catalyst, and specifically contains a catalyst and a silicone resin. The catalyst is, for example, a curing catalyst which promotes the reaction of the epoxy resin to harden the epoxy resin, and is preferably a hydrogenation catalyst which promotes the hydrogenation reaction of the neodymium resin described later and hardens the epoxy resin by hydroquinone addition. Media. Further, the catalyst contains a transition metal, and the transition metal may, for example, be a white metal element such as platinum, palladium or rhodium, and is preferably platinum. Specifically, when the catalyst contains platinum, the catalyst may, for example, be inorganic platinum such as platinum black, chlorinated platinum or chlorinated white gold; for example, platinum-olefin complex, platinum-carbonyl complex, platinum a platinum complex or the like of etodolacetic acid or the like, and preferably a platinum complex. More specifically, platinum is wrong For example, platinum-vinyloxane complex, platinum-tetramethyldivinyldioxane complex, platinum-carbonylcyclovinylmethyloxane complex, platinum-divinyltetramethyl A quinone oxime complex, a platinum-cyclovinyl methyl oxime complex, a platinum-octanal/octanol complex, and the like. Further, the catalyst has a state of being mixed differently from the above-described oxime resin, or is contained in the oxime resin as a component constituting the oxime resin.
上述觸媒中之過渡金屬之含有比例(濃度)，相對矽氧樹脂全體，宜為0.1至500ppm，較佳為0.15至100ppm，更佳為0.2至50ppm，且特佳為0.3至10ppm。 The content ratio (concentration) of the transition metal in the above catalyst is preferably from 0.1 to 500 ppm, preferably from 0.15 to 100 ppm, more preferably from 0.2 to 50 ppm, and particularly preferably from 0.3 to 10 ppm, based on the entire epoxy resin.
上述矽氧樹脂係藉觸媒促進反應且硬化之硬化性矽氧樹脂，且可舉1階段硬化型矽氧樹脂、2階段硬化型矽氧樹脂等之熱硬化性矽氧樹脂等為例。 The above-mentioned oxime resin is a curable oxime resin which promotes the reaction and hardens by a catalyst, and examples thereof include a thermosetting oxime resin such as a one-stage curable oxime resin and a two-stage curable oxime resin.
上述2階段硬化型矽氧樹脂具有2階段之反應機構，且係在1階段之反應中B階段化(半硬化)，且在2階段之反應中C階段化(完全硬化)之熱硬化性矽氧樹脂。又，上述B階段係熱硬化性矽氧樹脂在可溶於溶劑之A階段與完全硬化之C階段間之狀態，且在稍微進行硬化及凝膠化，且在溶劑中膨潤，但未完全溶解，並且藉加熱軟化但未熔融之狀態。 The two-stage hardening type oxime resin has a two-stage reaction mechanism, and is a B-stage (semi-hardening) in a one-stage reaction, and a C-stage (completely hardened) thermosetting 矽 in a two-stage reaction. Oxygen resin. Further, the above-mentioned B-stage thermosetting epoxy resin is in a state of being soluble in the A phase of the solvent and the C phase of the complete hardening, and is slightly hardened and gelled, and is swollen in a solvent, but is not completely dissolved. And softened but not melted by heat.
上述1階段硬化型矽氧樹脂具有1階段之反應機構，且係在1階段之反應中完全硬化之熱硬化性矽氧樹脂。上述1階段硬化型矽氧樹脂可舉日本特開2012-124428號公報揭示之加成反應硬化型聚有機聚矽氧烷為例。具體而言，加成反應硬化型聚有機聚矽氧烷，例如，含有含乙 烯系不飽和烴基矽化合物及含矽氫基矽化合物。 The above-described one-stage hardening type oxime resin has a one-stage reaction mechanism and is a thermosetting oxime resin which is completely cured in the one-stage reaction. The above-described one-stage hardening type oxime resin is exemplified by an addition reaction-curable polyorganopolyoxyalkylene disclosed in JP-A-2012-124428. Specifically, the addition reaction hardening polyorganopolyoxyalkylene, for example, contains B An ethylenically unsaturated hydrocarbon based hydrazine compound and a hydrazine-containing hydrazine-containing compound.
上述含乙烯系不飽和烴基矽化合物可舉例如在分子內具有2個以上之乙烯基之含乙烯基聚有機矽氧烷，且較佳為兩端乙烯聚二甲基矽氧烷。 The vinyl-containing unsaturated hydrocarbon-based ruthenium compound may, for example, be a vinyl-containing polyorganosiloxane having two or more vinyl groups in the molecule, and is preferably a two-end ethylene polydimethyl siloxane.
上述含矽氫基矽化合物可舉例如在分子內具有2個以上之乙烯基之含矽氫基聚有機矽氧烷，且較佳為兩端矽氫聚二甲基矽氧烷、兩端矽氫封鎖甲基氫矽氧烷-二甲基矽氧烷共聚物等。 The above-mentioned ruthenium-containing ruthenium-containing ruthenium compound may, for example, be a ruthenium-containing hydrogen-containing polyorganosiloxane having two or more vinyl groups in the molecule, and is preferably a ruthenium hydrogen polydimethyl siloxane at both ends, and both ends are ruthenium. Hydrogen blocked methyl hydroquinone-dimethyl oxa oxide copolymer and the like.
上述2階段硬化型矽氧樹脂可舉具有縮合反應與加成反應之2反應系之縮合反應、加成反應硬化型矽氧樹脂等為例。如此之縮合反應、加成反應硬化型矽氧樹脂含有觸媒，且可舉例如：含有矽烷醇兩端聚矽氧烷、含烯基三烷氧基矽烷、有機氫聚矽氧烷、縮合觸媒及矽氫化觸媒之第1縮合反應、加成反應硬化型矽氧樹脂，例如，含有矽烷醇基兩端聚矽氧烷、含乙烯系不飽和烴基矽化合物、有機氫聚矽氧烷、縮合觸媒及矽氫化觸媒之第2縮合反應、加成反應硬化型矽氧樹脂，例如，含有兩端矽烷醇型聚矽氧油、含烯基二烷氧烷基矽烷、有機氫聚矽氧烷、縮合觸媒及矽氫化觸媒之第3縮合反應、加成反應硬化型矽氧樹脂，例如，含有在1分子中具有至少2個矽烯基之有機聚矽氧烷、在1分子中具有至少2個矽氫基之有機聚矽氧烷、矽氫化觸媒及硬化延遲劑之第4縮合反應、加成反應硬化型矽氧樹脂， 例如，含有在1分子中合併具有至少2乙烯系不飽和烴基與至少2矽氫基之第1有機聚矽氧烷、不含乙烯系不飽和烴基且在1分子中具有至少2矽氫基之第2有機聚矽氧烷、矽氫化觸媒及矽氫化抑制劑之第5縮合反應、加成反應硬化型矽氧樹脂，例如，含有在1分子中合併具有至少2乙烯系不飽和烴基與至少2矽氫基之第1有機聚矽氧烷、不含乙烯系不飽和烴基且在1分子中具有至少2矽氫基之第2有機聚矽氧烷、矽氫化抑制劑、及矽氫化觸媒之第6縮合反應、加成反應硬化型矽氧樹脂，例如，含有矽化合物及硼化合物或鋁化合物之第7縮合反應、加成反應硬化型矽氧樹脂，例如，含有聚鋁矽氧烷及矽烷耦合劑之第8縮合反應、加成反應硬化型矽氧樹脂。 The two-stage hardening type oxime resin is exemplified by a condensation reaction of a reaction system having a condensation reaction and an addition reaction, an addition reaction-curable oxime resin, and the like. Such a condensation reaction or an addition reaction-curable oxime resin contains a catalyst, and examples thereof include a decyl alcohol-containing polyoxy siloxane, an alkenyl group-containing trialkoxy decane, an organic hydrogen polyoxy siloxane, and a condensation contact. The first condensation reaction and the addition reaction-curing type anthracene resin of the catalyst and the rhodium hydrogenation catalyst include, for example, a decyl alcohol group-terminated polyoxyalkylene, an ethylenically unsaturated hydrocarbon group-containing compound, and an organic hydrogen polyoxyalkylene. The second condensation reaction of the condensation catalyst and the rhodium hydrogenation catalyst, and the addition reaction-curing type oxygen resin, for example, a decyl alcohol type polyoxyxane oil, an alkenyl group-containing dialkyloxyalkyl decane, and an organic hydrogen polyfluorene. The third condensation reaction of the oxyalkylene, the condensation catalyst, and the ruthenium hydrogenation catalyst, and the addition reaction-type oxime resin, for example, an organopolysiloxane having at least two nonenyl groups in one molecule, in one molecule a fourth polycondensation reaction of an organic polyoxane having at least two hydrogen groups, a hydrogenation catalyst of a ruthenium hydrogenation catalyst, and a hardening retarder; and an addition reaction type hardening type epoxy resin; For example, it contains a first organopolyoxyalkylene having at least 2 ethylenically unsaturated hydrocarbon groups and at least 2 hydrogen groups in one molecule, no ethylenically unsaturated hydrocarbon group, and at least 2 hydrogen groups in one molecule. The fifth condensation reaction of the second organopolyoxane, the rhodium hydrogenation catalyst, and the rhodium hydrogenation inhibitor, and the addition reaction hardening type oxygen resin, for example, contain at least two ethylenically unsaturated hydrocarbon groups in one molecule and at least a hydrogen-based first organopolyoxane, a second organopolyoxyalkylene having no ethylenically unsaturated hydrocarbon group and having at least two hydrogen groups in one molecule, a hydrazine hydrogenation inhibitor, and a hydrazine hydrogenation catalyst The sixth condensation reaction or the addition reaction-curable oxygen-containing resin, for example, a seventh condensation reaction containing a ruthenium compound, a boron compound or an aluminum compound, or an addition reaction-curable oxime resin, for example, a polyaluminoxane and The eighth condensation reaction of the decane coupling agent and the addition reaction hardening type oxirane resin.
該等縮合反應、加成反應硬化型矽氧樹脂可單獨或合併2種以上使用。 These condensation reaction and the addition reaction-hardening type oxime resin can be used individually or in combination of 2 or more types.
上述縮合反應、加成反應硬化型矽氧樹脂可較佳地舉上述第2縮合反應、加成反應硬化型矽氧樹脂為例，具體而言，詳細記載於日本特開2010-265436號公報，例如，含有矽烷醇基兩端聚二甲基矽氧烷、乙烯三甲氧基矽烷、(3-環氧丙氧基丙基)三甲氧基矽烷、二甲基聚矽氧烷-co-甲基氫聚矽氧烷，羥化四甲基銨及白金-羰基錯合物。具體而言，為調製上述第2縮合反應、加成反應硬化型矽氧樹脂，例如，可藉由首先，一次添加縮合原料之含乙烯 系不飽和烴基矽化合物及含乙烯系不飽和烴基矽化合物，及縮合觸媒，接著，添加加成原料之有機氫聚矽氧烷，然後，添加矽氫化觸媒(加成觸媒)來調製。 The condensation reaction and the addition reaction-curable oxime resin are preferably exemplified by the second condensation reaction and the addition reaction-curable oxime resin, and are specifically described in Japanese Laid-Open Patent Publication No. 2010-265436. For example, a decyl alcohol-containing polydimethyl oxane, ethylene trimethoxy decane, (3-glycidoxypropyl) trimethoxy decane, dimethyl polyoxy siloxane - co-methyl Hydrogen polyoxyalkylene, hydroxylated tetramethylammonium and platinum-carbonyl complex. Specifically, in order to prepare the second condensation reaction or the addition reaction-curing type oxime resin, for example, the ethylene containing the condensation raw material may be added at a time. An unsaturated hydrocarbon-based ruthenium compound and an ethylenically unsaturated hydrocarbon-based ruthenium compound, and a condensation catalyst, followed by addition of an organic hydrogen polyoxyalkylene as an addition raw material, followed by addition of a ruthenium hydrogenation catalyst (addition catalyst) .
<B：特定之白色顏料> <B: Specific white pigment>
與上述A成分一起使用之特定白色顏料(B成分)係使用能帶間隙(禁制帶)為3.3至5.5eV之白色顏料。該能帶間隙係指由該結晶之帶構造中價電子帶上端到傳導帶下端間之能量差，且係在各單體、化合物其結晶系中固有之值。作為具有上述特定範圍之能帶間隙之白色顏料(B成分)，具體而言，單體可舉鑽石(能帶間隙5.5eV，折射率2.4)為例，氧化物可舉例如：氧化鋅(能帶間隙3.3eV，折射率2.0)、氧化鋯(ZrO2)(能帶間隙4至5eV，折射率2.1)、氧化鈰(能帶間隙3.4eV，折射率2.2)、氧化錫(I)(能帶間隙3.8eV，折射率2.0)、氧化鎳(能帶間隙4eV，折射率2.2)、氧化鋁(能帶間隙5eV，折射率1.8)等。又，氮化物可舉例如：氮化鉀(能帶間隙3.4eV，折射率2.4)、氮化矽(能帶間隙5eV，折射率2.0)、氮化硼(六方晶)(能帶間隙5eV，折射率1.8)等。此外，硫化物可舉硫化鋅(鐵鋅礦)(能帶間隙3.9eV，折射率2.4)等為例。又，不僅由長期耐光性亦由初期光反射率之觀點來看，折射率宜為2.0至3.0。又，由著色少、化學安定性、安全性、包含價格之容易取得性、及生產性之觀點來看，宜使用氧化鋅、氧化鋯(ZrO2)，且氧化鋯使用單斜晶之氧化鋯是特佳的。又，其中，由流動性之觀點來看，宜使用平均粒徑為0.01至50μm者，且更佳是使用0.01至30μm者。又，上述平 均粒徑例如可使用雷射繞射散射式粒度分布計測量。又，由光反射率之觀點來看，白色顏料包含之不純物中Fe2O3之含量宜為0.01質量%以下。 The specific white pigment (component B) used together with the above component A is a white pigment having a band gap (forbidden band) of 3.3 to 5.5 eV. The band gap refers to the difference in energy between the upper end of the valence band of the crystal structure and the lower end of the conduction band, and is a value inherent in the crystal system of each monomer or compound. As a white pigment (component B) having the energy band gap of the above specific range, specifically, the monomer may be exemplified by a diamond (band gap: 5.5 eV, refractive index: 2.4), and the oxide may, for example, be zinc oxide. Band gap 3.3eV, refractive index 2.0), zirconia (ZrO 2 ) (band gap 4 to 5eV, refractive index 2.1), yttrium oxide (band gap 3.4eV, refractive index 2.2), tin oxide (I) A gap of 3.8 eV, a refractive index of 2.0), a nickel oxide (band gap of 4 eV, a refractive index of 2.2), an alumina (band gap of 5 eV, a refractive index of 1.8), and the like. Further, examples of the nitride include potassium nitride (band gap: 3.4 eV, refractive index: 2.4), tantalum nitride (band gap: 5 eV, refractive index: 2.0), and boron nitride (hexagonal crystal) (band gap: 5 eV). Refractive index 1.8) and so on. Further, the sulfide may be exemplified by zinc sulfide (iron-zinc ore) (band gap: 3.9 eV, refractive index: 2.4). Further, the refractive index is preferably not less than 2.0 to 3.0 from the viewpoint of long-term light resistance and initial light reflectance. Further, zinc oxide, zirconium oxide (ZrO 2 ), and monoclinic zirconia using zirconium oxide are preferable from the viewpoints of less coloring, chemical stability, safety, ease of availability, and productivity. It is especially good. Further, among them, from the viewpoint of fluidity, it is preferred to use an average particle diameter of 0.01 to 50 μm, and more preferably 0.01 to 30 μm. Further, the above average particle diameter can be measured, for example, by a laser diffraction scattering type particle size distribution meter. Further, from the viewpoint of light reflectance, the content of Fe 2 O 3 in the impurities contained in the white pigment is preferably 0.01% by mass or less.
上述特定白色顏料(B成分)之混合比例，相對熱硬化性樹脂組成物全體，宜為3至50體積%，更佳為5至30體積%。即，B成分之含有比例過小時，可看到難以得到充分光反射性、特別優異之初期光反射率的傾向。B成分之含有比例過大時，可看到因顯著增黏使藉摻混等製作熱硬化性樹脂組成物產生困難之可能性。 The mixing ratio of the specific white pigment (component B) is preferably from 3 to 50% by volume, and more preferably from 5 to 30% by volume based on the total of the thermosetting resin composition. In other words, when the content ratio of the component B is too small, it is difficult to obtain sufficient light reflectivity and particularly excellent initial light reflectance. When the content ratio of the component B is too large, it is possible to cause difficulty in producing a thermosetting resin composition by blending or the like due to remarkably thickening.
<C：無機填充劑> <C: Inorganic filler>
與上述A至B成分一起使用之無機填充劑(C成分)可舉例如：石英玻璃粉末、滑石、熔融二氧化矽粉末或結晶性二氧化矽粉末等之二氧化矽粉末、氧化鋁粉末、氮化鋁粉末、氮化矽粉末。特別地，由線膨脹係數減少等觀點來看，宜使用熔融二氧化矽粉末，且由高填充性及高流動性之觀點來看，特佳是使用熔融球狀二氧化矽粉末。又，無機填充劑(C成分)係在上述特定白色顏料(B成分)以外。關於上述無機填充劑(C成分)之粒徑及其分布，宜考慮使上述白色顏料(B成分)之粒徑及其分布之組合，在藉由轉移成形等成形熱硬化性樹脂組成物時之毛邊減至最少。具體而言，無機填充劑(C成分)之平均粒徑宜為5至100μm，特佳為10至80μm。又，與前述相同，上述平均粒徑例如可使用雷射繞射散射式粒度分布計測量。 The inorganic filler (component C) to be used together with the above components A to B may, for example, be a cerium oxide powder such as quartz glass powder, talc, molten cerium oxide powder or crystalline cerium oxide powder, alumina powder or nitrogen. Aluminum powder, tantalum nitride powder. In particular, molten cerium oxide powder is preferably used from the viewpoint of reduction in linear expansion coefficient, etc., and it is particularly preferable to use molten spherical cerium oxide powder from the viewpoint of high filling property and high fluidity. Further, the inorganic filler (component C) is other than the specific white pigment (component B). In the particle size of the inorganic filler (component C) and the distribution thereof, it is preferable to use a combination of the particle diameter and the distribution of the white pigment (component B) to form a thermosetting resin composition by transfer molding or the like. The burrs are minimized. Specifically, the inorganic filler (component C) preferably has an average particle diameter of 5 to 100 μm, particularly preferably 10 to 80 μm. Further, as described above, the above average particle diameter can be measured, for example, by a laser diffraction scattering type particle size distribution meter.
又，就上述無機填充劑(C成分)之含有比例而 言，上述特定白色顏料(B成分)與無機填充劑(C成分)之合計含有比例宜設定為熱硬化性樹脂組成物全體之10至90體積%。更佳是60至90體積%，且特佳是65至85體積%。即，上述合計含有比例過小時，可看到產生在成形時發生翹曲等之問題。又，合計含有比例過大時，可看到摻混混合成分時，對摻混機施加大負載，且不可能摻混之傾向，結果，可看到製作成形材料之熱硬化性樹脂組成物困難之傾向。 Moreover, the content ratio of the above inorganic filler (component C) In general, the total content of the specific white pigment (component B) and the inorganic filler (component C) is preferably 10 to 90% by volume based on the total amount of the thermosetting resin composition. More preferably, it is 60 to 90% by volume, and particularly preferably 65 to 85% by volume. In other words, when the total content ratio is too small, it is found that warpage or the like occurs during molding. Further, when the total content ratio is too large, it can be seen that when the mixed component is blended, a large load is applied to the blender, and the tendency to blend is not obtained. As a result, it is difficult to form a thermosetting resin composition for forming the molded material. tendency.
又，上述特定白色顏料(B成分)與無機填充劑(C成分)之混合比例，由初期光反射率之觀點來看，以體積比計，(C成分)/(B成分)=1至36是較佳的，且特佳是2至30。即，B成分與C成分之混合比例在上述範圍外，且體積比過小時，可看到熱硬化性樹脂組成物之熔融黏度上升而使摻混困難的傾向，且體積比過大時，可看到熱硬化性樹脂組成物之初期光反射率降低的傾向。 Further, the mixing ratio of the specific white pigment (component B) and the inorganic filler (component C) is (C component) / (component B) = 1 to 36 by volume ratio from the viewpoint of initial light reflectance. It is preferred, and particularly preferably 2 to 30. In other words, when the mixing ratio of the component B and the component C is outside the above range, and the volume ratio is too small, the melt viscosity of the thermosetting resin composition is increased to make the blending tendency difficult, and when the volume ratio is too large, it can be seen. The light reflectance tends to decrease at the initial stage of the thermosetting resin composition.
<其他添加劑> <Other additives>
又，本發明之熱硬化性樹脂組成物，除了上述A至C成分以外，可依需要混合硬化促進劑、脫模劑、矽烷化合物。又，可適當混合變性劑(可塑劑)、抗氧化劑、阻燃劑、脫泡劑、均染劑、紫外線吸收劑等之各種添加劑。 Further, in the thermosetting resin composition of the present invention, in addition to the above components A to C, a curing accelerator, a releasing agent, and a decane compound may be mixed as needed. Further, various additives such as a denaturant (plasticizer), an antioxidant, a flame retardant, a defoaming agent, a leveling agent, and an ultraviolet absorber can be appropriately mixed.
上述硬化促進劑可在上述熱硬化性樹脂(A成分)為環氧樹脂之情形中使用，且硬化促進劑可舉例如：1,8-二氮二環[5.4.0]十一烯-7、三伸乙二胺、三-2,4,6-二乙胺甲苯酚、N,N-二甲苄胺、N,N-二甲胺苯、N,N-二甲胺環己烷等之3級胺類，2-乙基-4-甲基咪唑、2-甲基咪唑等咪 唑類，三苯膦、四苯膦、四苯鏻四氟硼酸鹽、四苯鏻四苯硼酸酯、四-n-丁鏻溴、四苯鏻溴、甲基三丁鏻二甲磷酸鹽、四苯鏻-o,o-二乙磷二硫代酸鹽、四-n-丁鏻-o,o-二乙磷二硫代酸鹽等之磷化合物，三伸乙二銨辛羧酸鹽等4級銨鹽，有機金屬鹽類、及其衍生物等。該等硬化促進劑可單獨或合併2種以上使用。該等硬化促進劑中，宜使用3級胺類、咪唑類、磷化合物。其中，為得到著色少之硬化物，使用磷化合物是特佳的。 The hardening accelerator may be used in the case where the above thermosetting resin (component A) is an epoxy resin, and the hardening accelerator may, for example, be 1,8-diazabicyclo[5.4.0]undecene-7. , triamethylenediamine, tris-2,4,6-diethylamine cresol, N,N-dimethylbenzylamine, N,N-dimethylamine benzene, N,N-dimethylamine cyclohexane, etc. Grade 3 amines, 2-ethyl-4-methylimidazole, 2-methylimidazole, etc. Azole, triphenylphosphine, tetraphenylphosphine, tetraphenylphosphonium tetrafluoroborate, tetraphenylphosphonium tetraphenyl borate, tetra-n-butyl bromide, tetraphenylphosphonium bromide, methyl tributyl phosphonium dicarboxylate , tetraphenylphosphonium-o,o-diethylphosphoric dithioate, tetra-n-butylphosphonium-o,o-diethylphosphoric dithioate, etc., triamethylene succinate Grade 4 ammonium salts such as salts, organic metal salts, and derivatives thereof. These hardening accelerators can be used individually or in combination of 2 or more types. Among these hardening accelerators, a tertiary amine, an imidazole or a phosphorus compound is preferably used. Among them, in order to obtain a cured product having little coloring, it is particularly preferable to use a phosphorus compound.
上述硬化促進劑之含量，相對於上述熱硬化性樹脂(A成分)宜設定為0.001至8重量%，更佳為0.01至5重量%。即，這是因為硬化促進劑之含量過少時，有時得不到充分硬化促進效果，且硬化促進劑之含量過多時，可看到製得之硬化物產生變色之傾向。 The content of the above-mentioned hardening accelerator is preferably 0.001 to 8% by weight, and more preferably 0.01 to 5% by weight based on the thermosetting resin (component A). In other words, when the content of the curing accelerator is too small, a sufficient curing acceleration effect may not be obtained, and when the content of the curing accelerator is too large, the cured product obtained tends to be discolored.
上述脫模劑可使用各種脫模劑，但是使用具有醚鍵之脫模劑特別好，可舉具有以下述通式(1)表示之構造式的脫模劑為例。 In the above-mentioned mold release agent, various mold release agents can be used, but a mold release agent having an ether bond is particularly preferable, and a mold release agent having a structural formula represented by the following general formula (1) can be exemplified.
CH3．(CH3)k．CH2O(CHRm．CHRn．O)x．H．．．(1) CH 3 . (CH 3 )k. CH 2 O(CHRm.CHRn.O)x. H. . . (1)
[式(1)中，Rm、Rn係氫原子或1價烷基，且兩者可互相相同亦可不同。又，k係1至100之正數，x係1至100之正數。] In the formula (1), Rm and Rn are a hydrogen atom or a monovalent alkyl group, and the two may be the same or different from each other. Further, k is a positive number from 1 to 100, and x is a positive number from 1 to 100. ]
上述式(1)中，Rm、Rn係氫原子或1價烷基，較佳地，k係10至50之正數，且x係3至30之正數。更佳地，Rm及Rn係氫原子，k係28至48之正數，且x係5至20之正數。即，重覆數k之值過小時，脫模性降低，且重覆數x之值過小時， 分散性降低，因此可看到得不到安定之強度及脫模性的傾向。另一方面，這是因為重覆數k之值過大時，可看到熔點高，因此摻混困難，且在熱硬化性樹脂組成物之製造步驟中產生困難的傾向，又，重覆數x之值過大時，可看到脫模性降低之傾向。 In the above formula (1), Rm, Rn are a hydrogen atom or a monovalent alkyl group, preferably, k is a positive number of 10 to 50, and x is a positive number of 3 to 30. More preferably, Rm and Rn are hydrogen atoms, k is a positive number from 28 to 48, and x is a positive number from 5 to 20. That is, when the value of the number of repetitions k is too small, the mold release property is lowered, and the value of the number of repetitions x is too small. Since the dispersibility is lowered, it is seen that the strength and the mold release property of the stability are not obtained. On the other hand, this is because when the value of the number of repetitions k is too large, the melting point is high, so that it is difficult to blend, and it tends to be difficult in the production step of the thermosetting resin composition, and the number of repetitions x When the value is too large, the tendency of the mold release property to be lowered can be seen.
上述脫模劑之含量宜設定在熱硬化性樹脂組成物全體之0.001至3重量%之範圍內，更佳是設定在0.01至2重量%之範圍內。即，這是因為脫模劑之含量過少，或過多時，可看見造成硬化體之強度不足，或引起脫模性降低之傾向。 The content of the above-mentioned releasing agent is preferably set in the range of 0.001 to 3% by weight based on the entire thermosetting resin composition, and more preferably in the range of 0.01 to 2% by weight. That is, this is because when the content of the releasing agent is too small or too large, it is seen that the strength of the hardened body is insufficient or the mold release property is lowered.
上述矽烷化合物可舉矽烷耦合劑及矽烷等為例。上述矽烷耦合劑可舉例如：3-環氧丙氧基丙基甲基二甲氧矽烷、3-環氧丙氧基丙基三甲氧矽烷、3-環氧丙氧基丙基甲基二乙氧矽烷、3-環氧丙氧基丙基甲基乙氧矽烷、2-(3,4-環氧環己基)乙基三甲氧矽烷、3-巰丙基甲基二甲氧矽烷、3-巰丙基甲基三甲氧矽烷等。又，上述矽烷可舉例如：甲基三甲氧矽烷、二甲基二甲氧矽烷、苯基三甲氧矽烷、甲基三乙氧矽烷、二甲基二乙氧矽烷、苯基三乙氧矽烷、癸基三甲氧矽烷、三氟丙基三甲氧矽烷、己基甲基二矽氮烷、含水解性基之矽氧烷等。該等矽烷可單獨或合併2種以上使用。 The decane compound may be exemplified by a decane coupling agent, decane or the like. The above decane coupling agent may, for example, be 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethyl Oxane, 3-glycidoxypropylmethylethoxyoxane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3- Mercaptopropyltrimethoxyoxane and the like. Further, examples of the decane include methyltrimethoxy decane, dimethyl dimethoxy decane, phenyl trimethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, and phenyl triethoxy decane. Mercapto trimethoxy decane, trifluoropropyltrimethoxy decane, hexylmethyl diazonium alkane, hydrolyzable group-containing oxane, and the like. These decanes may be used singly or in combination of two or more.
上述變性劑(可塑劑)可舉矽氧類、醇類等為例。 The above-mentioned denaturing agent (plasticizer) may, for example, be an oxygen or an alcohol.
上述抗氧化劑可舉酚系化合物、胺系化合物、有機硫系化合物、磷系化合物等為例。 Examples of the antioxidant include a phenol compound, an amine compound, an organic sulfur compound, and a phosphorus compound.
上述阻燃劑可舉例如氫氧化鎂等之金屬氫氧化物、溴系阻燃劑、氮系阻燃劑、磷系阻燃劑等，亦可進一步使用三氧化銻等阻燃助劑。 The flame retardant may, for example, be a metal hydroxide such as magnesium hydroxide, a bromine-based flame retardant, a nitrogen-based flame retardant or a phosphorus-based flame retardant, or a flame retardant auxiliary such as antimony trioxide may be further used.
上述消泡劑可舉矽氧系等習知消泡劑為例。 The antifoaming agent may be exemplified by a conventional antifoaming agent such as an oxygen system.
<熱硬化性樹脂組成物> <Thermosetting resin composition>
本發明之熱硬化性樹脂組成物，例如，可如下地製造。即，可適當混合上述A至C成分，硬化促進劑及脫模劑，以及依需要使用之各種添加劑後，使用摻混機等熔融混合，接著，藉由冷卻該混合物且固化粉碎，可製造粉末狀之熱硬化性樹脂組成物。 The thermosetting resin composition of the present invention can be produced, for example, as follows. That is, the above-mentioned components A to C, the curing accelerator, the releasing agent, and various additives which are used as needed may be appropriately mixed, and then melt-mixed using a blender or the like, and then the mixture may be cooled and pulverized to produce a powder. A thermosetting resin composition.
又，作為，例如，藉由轉移成形或射出成形上述製得之熱硬化性樹脂組成物製得之硬化物，其光反射率宜在波長450至800nm中為80%以上，且更佳為90%以上。又，上限通常為100%。具體而言，上述硬化物之波長450nm中之光反射率宜為85至98%。上述光反射率例如可按如下方式測量。即，藉由預定硬化條件，例如，175℃×2分鐘之成形後，175℃×3小時之後硬化製作厚度1mm之熱硬化性樹脂組成物之硬化物，且藉由使用分光光度計(例如，日本分光公司製之分光光度計V-670)，可測量在室溫(25±10℃)在上述範圍內波長之上述硬化物的光反射率。 In addition, for example, a cured product obtained by transfer molding or injection molding of the thermosetting resin composition obtained above has a light reflectance of preferably 80% or more, and more preferably 90% in a wavelength of 450 to 800 nm. %the above. Also, the upper limit is usually 100%. Specifically, the light reflectance in the wavelength of 450 nm of the cured product is preferably from 85 to 98%. The above light reflectance can be measured, for example, as follows. That is, a cured product of a thermosetting resin composition having a thickness of 1 mm is hardened by a predetermined curing condition, for example, after 175 ° C × 2 minutes, and after 175 ° C × 3 hours, and by using a spectrophotometer (for example, A spectrophotometer V-670 manufactured by JASCO Corporation can measure the light reflectance of the cured product at a wavelength within the above range at room temperature (25 ± 10 ° C).
使用本發明之熱硬化性樹脂組成物之光半導體裝置係例如以如下方式製造。即，將金屬引線框設置在轉移成形機之模具內且使用上述熱硬化性樹脂組成物藉由轉移成形形成反射器。如此，製作以包圍光半導體元件裝 載區域周圍之方式形成環狀反射器而成之光半導體裝置用之金屬引線框。接著，將光半導體元件裝載在上述反射器內部之金屬引線框上的光半導體元件裝載區域，且使用接合線電性連接光半導體元件及金屬引線框。又，使用矽氧樹脂等對包含上述光半導體元件之反射器內側區域進行樹脂密封，藉以形成密封樹脂層。如此，例如，製作如圖1所示之立體狀(杯型)光半導體元件。如前所述，該光半導體裝置係構成如下：在由第一板部1及第二板部2組成之金屬引線框的第二板部2上裝載光半導體元件3，且以包圍上述光半導體元件3之周圍的方式，形成有由本發明之熱硬化性樹脂組成物構成之光反射用反射器4。又，在上述金屬引線框及反射器4之內周面所形成之凹部5中，形成密封光半導體元件3且具有透明性之密封樹脂層6。該密封樹脂層6可依需要含有螢光體。在圖1中，7、8係電性連接金屬引線框及光半導體元件3之接合線。 The optical semiconductor device using the thermosetting resin composition of the present invention is produced, for example, in the following manner. That is, a metal lead frame is placed in a mold of a transfer molding machine, and a reflector is formed by transfer molding using the above-described thermosetting resin composition. In this way, it is fabricated to surround the optical semiconductor component A metal lead frame for an optical semiconductor device in which a ring-shaped reflector is formed around the carrier region. Next, the optical semiconductor element is mounted on the optical semiconductor element mounting region on the metal lead frame inside the reflector, and the optical semiconductor element and the metal lead frame are electrically connected using a bonding wire. Moreover, the inner region of the reflector including the optical semiconductor element is resin-sealed using a silicone resin or the like to form a sealing resin layer. Thus, for example, a three-dimensional (cup type) optical semiconductor element as shown in FIG. 1 is produced. As described above, the optical semiconductor device is configured such that the optical semiconductor element 3 is mounted on the second plate portion 2 of the metal lead frame composed of the first plate portion 1 and the second plate portion 2, and surrounds the optical semiconductor. A light reflection reflector 4 composed of the thermosetting resin composition of the present invention is formed in a manner around the element 3. Further, in the recessed portion 5 formed on the inner circumferential surface of the metal lead frame and the reflector 4, a sealing resin layer 6 which seals the optical semiconductor element 3 and has transparency is formed. The sealing resin layer 6 may contain a phosphor as needed. In FIG. 1, 7, 8 are electrically connected to the bonding wires of the metal lead frame and the optical semiconductor element 3.
又，在本發明中，亦可使用各種基板取代上述圖1之金屬引線框。上述各種基板可舉有機基板、無機基板、撓性印刷基板等為例。又，亦可變更上述轉移成形，藉由射出成形形成反射器。 Further, in the present invention, various substrates may be used instead of the metal lead frame of Fig. 1 described above. Examples of the various substrates described above include an organic substrate, an inorganic substrate, and a flexible printed circuit board. Further, the above-described transfer molding may be changed, and the reflector may be formed by injection molding.
又，在與上述構造不同之光半導體裝置方面，可舉使用板狀光半導體裝置用引線框之光半導體裝置為例，譬如圖2及圖3(圖2之X-X'之截面圖)所示者。即，該光半導體裝置係構成如下：在互設間隔配置之金屬引線框10之厚度方向之一面的預定位置上，分別裝載光半導體元件 3，且在上述金屬引線框10間之間隙形成有由本發明熱硬化性樹脂組成物構成之光反射用反射器11。又，如圖3所示，於數個地方形成有在金屬引線框10之間隙填充本發明熱硬化性樹脂組成物再經硬化而成之反射器11。又，在圖2及圖3中，12係電性連接上述光半導體元件3及金屬引線框10之接合線。如此之光半導體裝置係將上述金屬引線框10設置在轉移成形機內，利用轉移成形，在設下間隔配置之金屬引線框10之間隙及與金屬引線框10之光半導體元件3裝載面相反之面所形成的凹部中，填充熱硬化性樹脂組成物，並且使之硬化，藉此分別形成反射器11。接著，將光半導體元件3裝載在成為金屬引線框10之預定位置的光半導體元件裝載區域後，使用接合線12電性連接光半導體元件3及金屬引線框10。如此即可製作出圖2及圖3所示之光半導體裝置。 Moreover, in the optical semiconductor device different from the above-described structure, an optical semiconductor device using a lead frame for a plate-shaped optical semiconductor device is exemplified, as shown in FIG. 2 and FIG. 3 (X-X' cross-sectional view of FIG. 2). Shower. In other words, the optical semiconductor device is configured such that optical semiconductor elements are respectively mounted at predetermined positions on one surface in the thickness direction of the metal lead frame 10 which are disposed at intervals. 3. A light reflection reflector 11 composed of the thermosetting resin composition of the present invention is formed in the gap between the metal lead frames 10. Further, as shown in FIG. 3, a reflector 11 in which a thermosetting resin composition of the present invention is filled in a gap between the metal lead frames 10 and then cured is formed in a plurality of places. Further, in FIGS. 2 and 3, the bonding wires of the optical semiconductor element 3 and the metal lead frame 10 are electrically connected to each other. In such an optical semiconductor device, the metal lead frame 10 is placed in a transfer molding machine, and the gap between the metal lead frame 10 disposed at a lower interval and the surface on which the optical semiconductor element 3 of the metal lead frame 10 is mounted is reversed by transfer molding. In the concave portion formed by the surface, the thermosetting resin composition is filled and hardened, whereby the reflector 11 is formed separately. Next, after the optical semiconductor element 3 is mounted on the optical semiconductor element mounting region which is a predetermined position of the metal lead frame 10, the optical semiconductor element 3 and the metal lead frame 10 are electrically connected by using the bonding wires 12. Thus, the optical semiconductor device shown in FIGS. 2 and 3 can be fabricated.
<密封型光半導體元件> <Sealed Optical Semiconductor Element>
使用本發明之熱硬化性樹脂組成物作為反射器形成材料之密封型光半導體元件顯示於圖4。即，該密封型光半導體元件係構成如下：在光半導體元件3之側面全面形成有由本發明熱硬化性樹脂組成物構成之光反射用反射器15，且進一步以密封層16被覆光半導體元件3之上部(發光面或受光面)。在圖中，17係連接用電極(凸塊)。又，上述密封層16係藉由環氧樹脂或矽氧樹脂，或者玻璃或陶瓷等無機材料形成，且上述密封層16可含有螢光體，亦可混合螢光體。 A sealed optical semiconductor element using the thermosetting resin composition of the present invention as a reflector forming material is shown in Fig. 4 . In other words, the sealed optical semiconductor device is configured such that the light reflecting reflector 15 composed of the thermosetting resin composition of the present invention is entirely formed on the side surface of the optical semiconductor device 3, and the optical semiconductor device 3 is further covered with the sealing layer 16. The upper part (light emitting surface or light receiving surface). In the figure, 17 series connection electrodes (bumps) are used. Further, the sealing layer 16 is formed of an epoxy resin, a silicone resin, or an inorganic material such as glass or ceramic, and the sealing layer 16 may contain a phosphor or may be a fluorescent material.
如此之密封型光半導體元件例如可按如下方式製造。即，在切割膠帶等之黏著面上，將倒裝晶片安裝型之光半導體(發光)元件3(例如，藍色LED晶片等)，在將設在與該發光面相反之面之連接用電極(凸塊)17埋入上述膠帶面中的狀態下，分開一定間隔地配置。接著，使用壓縮成形機、轉移成形機或射出成形機，且使用本發明之熱硬化性樹脂組成物包埋上述光半導體元件3之側面全面，及發光面。又，藉由乾燥機等進行後加熱，藉此使上述熱硬化性樹脂組成物之熱硬化反應結束且在光半導體元件3之側面全部上形成由本發明之熱硬化性樹脂組成物構成之光反射用反射器15。接著，藉由研磨去除在發光面上形成之反射器15使發光面暴露，且在藉橡膠材包圍周圍之狀態下澆鑄矽氧樹脂等之密封材在該暴露之發光面上，或在發光面上黏貼片狀之密封材而形成密封層16。接著，使用刀片切割機切割光半導體元件3間之中央線，使各個元件互相單片化。又，擴大延伸切割膠帶使黏著性降低，且使切割膠帶上形成反射器15之密封型光半導體元件3彼此完全分離，且單片化，藉此可製造圖4所示之密封型光半導體元件3。 Such a sealed optical semiconductor element can be manufactured, for example, as follows. In other words, a flip-chip mounted photo-semiconductor (light-emitting) element 3 (for example, a blue LED wafer or the like) is placed on an adhesive surface such as a dicing tape, and a connection electrode provided on a surface opposite to the light-emitting surface The (bumps) 17 are placed at a predetermined interval in a state where they are buried in the tape surface. Then, a compression molding machine, a transfer molding machine, or an injection molding machine is used, and the side surface of the optical semiconductor element 3 and the light-emitting surface are embedded by using the thermosetting resin composition of the present invention. In addition, after the post-heating by a dryer or the like, the thermosetting reaction of the thermosetting resin composition is completed, and light reflection by the thermosetting resin composition of the present invention is formed on all sides of the optical semiconductor element 3 A reflector 15 is used. Then, the reflector 15 formed on the light-emitting surface is removed by polishing to expose the light-emitting surface, and a sealing material such as a silicone resin is cast on the exposed light-emitting surface or on the light-emitting surface while surrounding the rubber material. A sealing layer 16 is formed by adhering a sheet-like sealing material. Next, the center line between the optical semiconductor elements 3 is cut using a blade cutter to singulate the respective elements. Further, the extended cut tape is enlarged to lower the adhesiveness, and the sealed type optical semiconductor elements 3 on which the reflector 15 is formed on the dicing tape are completely separated from each other and singulated, whereby the sealed type optical semiconductor element shown in Fig. 4 can be manufactured. 3.
使用如此製得之密封型光半導體元件3之構造的光半導體裝置可舉具有在形成配線電路板之電路的預定位置上，透過上述光半導體元件3之連接用電極17裝載而成之構造的光半導體裝置為例。 The optical semiconductor device having the structure of the sealed optical semiconductor device 3 thus obtained has light having a structure in which the connection electrode 17 is transmitted through the connection electrode 17 of the optical semiconductor element 3 at a predetermined position of the circuit for forming the wiring board. A semiconductor device is taken as an example.
實施例 Example
接著，一起說明實施例及比較例。但是，本發明不限於該等實施例。 Next, examples and comparative examples will be described together. However, the invention is not limited to the embodiments.
首先，在製作熱硬化性樹脂組成物之前，準備如下所示之各成分。 First, each component shown below is prepared before the thermosetting resin composition is produced.
[環氧樹脂] [Epoxy resin]
異三聚氰酸三環氧丙酯(環氧樹脂當量100) Triglycidyl isocyanate (epoxy equivalent 100)
[硬化性成分] [sclerosing ingredients]
4-甲基四氫鄰苯二甲酐(酐當量168) 4-methyltetrahydrophthalic anhydride (anhydride equivalent 168)
[白色顏料b1] [white pigment b1]
氧化鋅(能帶間隙3.3eV，折射率2.0，平均粒徑2.9μm)(HAKUSUI TECH公司製，1種氧化鋅) Zinc oxide (band gap 3.3 eV, refractive index 2.0, average particle diameter 2.9 μm) (manufactured by HAKUSUI TECH, 1 zinc oxide)
[白色顏料b2] [white pigment b2]
氧化鋯(ZrO2)(能帶間隙4至5eV，折射率2.1，平均粒徑4.3μm，Fe2O3含量0.001質量%，單斜晶)(第一稀元素化學工業公司製，SG氧化鋯) Zirconium oxide (ZrO 2 ) (band gap 4 to 5 eV, refractive index 2.1, average particle diameter 4.3 μm, Fe 2 O 3 content 0.001% by mass, monoclinic crystal) (first rare element chemical industry company, SG zirconia) )
[白色顏料b'] [white pigment b']
金紅石型氧化鈦(能帶間隙3.0eV，折射率2.7，單一粒徑0.2μm)(石原產業公司製，CR-97) Rutile-type titanium oxide (band gap 3.0 eV, refractive index 2.7, single particle size 0.2 μm) (manufactured by Ishihara Sangyo Co., Ltd., CR-97)
[無機填充劑] [Inorganic filler]
熔融球狀二氧化矽粉末(平均粒徑20μm) Melted spherical cerium oxide powder (average particle size 20 μm)
[硬化促進劑] [hardening accelerator]
四-n-丁鏻溴 Tetra-n-butane bromide
[脫模劑] [release agent]
C(碳數)>14，乙氧化醇/乙烯均聚物(丸菱油化工業公司 製，UNT750) C (carbon number)>14, ethoxylated alcohol/ethylene homopolymer (Maru Oil Chemical Industry Co., Ltd. System, UNT750)
[耦合劑] [Coupling agent]
3-環氧丙氧基丙基三甲氧矽烷(信越化學工業公司製，KBM-403) 3-glycidoxypropyltrimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
[實施例1至15，比較例1] [Examples 1 to 15, Comparative Example 1]
將後述表1至表3所示之各成分以同表地顯示之比例混合，進行藉捏合機熔融摻混(溫度100至130℃)，且在熟成後，冷卻至室溫(25℃)且粉碎，藉此製成作為目的之粉末狀熱硬化性樹脂組成物。 The components shown in Tables 1 to 3 to be described later are mixed in the same ratio as shown in the table, and melt-blended by a kneader (temperature: 100 to 130 ° C), and after aging, cooled to room temperature (25 ° C) and pulverized. Thereby, a powdery thermosetting resin composition as a target is produced.
使用如此製得之實施例及比較例之熱硬化性樹脂組成物，依據下述方法進行各種評價[初期光反射率、長期耐光性]之測量。其結果顯示於後述表1至表3中。 Using the thermosetting resin compositions of the examples and the comparative examples thus obtained, various evaluations [initial light reflectance and long-term light resistance] were measured in accordance with the following methods. The results are shown in Tables 1 to 3 which will be described later.
[初期光反射率] [Initial light reflectance]
使用上述各熱硬化性樹脂組成物，利用預定之硬化條件(條件：175℃×2分鐘之成形+175℃×3小時硬化)製作厚度1mm之試驗片，使用該試驗片，測量在室溫(25℃)之光反射率。又，使用日本分光公司製之分光光度計V-670作為測量裝置，在室溫(25℃)測量波長450nm之光反射率。 Using each of the above thermosetting resin compositions, a test piece having a thickness of 1 mm was produced by using predetermined curing conditions (condition: 175 ° C × 2 minutes of forming + 175 ° C × 3 hours of hardening), and the test piece was used to measure at room temperature ( Light reflectance at 25 ° C). Further, a spectrophotometer V-670 manufactured by JASCO Corporation was used as a measuring device, and a light reflectance at a wavelength of 450 nm was measured at room temperature (25 ° C).
[長期耐光性] [Long-term light resistance]
使用與上述同樣地製成之各試驗片，在室溫(25℃)下測量波長600nm之光反射率。然後，在藉由110℃之熱板加熱該試驗片之狀態下，以1W/cm2之強度照射436nm之光15分鐘後，與上述同樣地測量波長600nm之光反射率(加速試驗)。又，算出在上述加速試驗前後之光反射率之降低度(加 熱、光照射後之光反射率-加熱、光照射前之光反射率)。又，測量時與上述同樣使用日本分光公司製之分光光度計V-670。就上述光反射率之降低度而言，關於實施例11至13、15，有測得、算出超過0之值，但是上述值為測量誤差，實質上在0以下，故表中記載為「0」。 The light reflectance at a wavelength of 600 nm was measured at room temperature (25 ° C) using each test piece prepared in the same manner as above. Then, the test piece was heated by a hot plate at 110 ° C, and light of 436 nm was irradiated with an intensity of 1 W/cm 2 for 15 minutes, and then light reflectance at a wavelength of 600 nm (acceleration test) was measured in the same manner as above. Further, the degree of decrease in the light reflectance before and after the above-described acceleration test (heating, light reflectance after light irradiation, heating, and light reflectance before light irradiation) was calculated. Further, in the measurement, a spectrophotometer V-670 manufactured by JASCO Corporation was used in the same manner as described above. With respect to the degree of reduction in the light reflectance, in Examples 11 to 13 and 15, the value exceeding 0 is measured and calculated, but the above value is a measurement error and is substantially 0 or less, so the table is described as "0. "."
由上述結果可得到，混合特定白色顏料而成之實施例品不僅具高初期光反射率，亦具長期耐光性之結果。 From the above results, it was found that the examples in which a specific white pigment was mixed not only had high initial light reflectance but also long-term light resistance.
相對於此，使用能帶間隙為特定範圍以外之小值之氧化鈦的比較例1品得到初期光反射率與實施例品同程 度之高測量結果，但是得到具不佳長期耐光性之結果。 On the other hand, in the comparative example 1 which has a small amount of titanium oxide having a band gap other than the specific range, the initial light reflectance was obtained in the same manner as the example. High measurement results, but the result is poor long-term light resistance.
[光半導體(發光)裝置之製作] [Production of Optical Semiconductor (Light Emitting) Device]
接著，使用打錠上述實施例品之粉末的錠狀熱硬化性樹脂組成物，製造圖1所示之構造的光半導體(發光)裝置。即，將具有銅(銀鍍敷)製之多數成對第一板部1及第二板部2之金屬引線框設置在轉移成形機之模具內，且使用上述熱硬化性樹脂組成物進行轉移成形(條件：175℃×2分鐘之成形+175℃×3小時硬化)，藉此在金屬引線框之預定位置形成圖1所示之反射器4。接著，裝載光半導體(發光)裝置(大小：0.5mm×0.5mm)3，且利用接合線7、8電性連接該光半導體元件3及上述金屬引線框，藉此製造具有反射器4、金屬引線框及光半導體元件3之單元。 Next, an optical semiconductor (light-emitting) device having the structure shown in Fig. 1 was produced by using a tablet-shaped thermosetting resin composition in which the powder of the above-mentioned example product was tableted. That is, a metal lead frame having a plurality of pairs of the first plate portion 1 and the second plate portion 2 made of copper (silver plating) is placed in a mold of a transfer molding machine, and transferred using the above-described thermosetting resin composition. Forming (condition: 175 ° C × 2 minutes of forming + 175 ° C × 3 hours of hardening), thereby forming the reflector 4 shown in Fig. 1 at a predetermined position of the metal lead frame. Next, an optical semiconductor (light-emitting) device (size: 0.5 mm × 0.5 mm) 3 is mounted, and the optical semiconductor element 3 and the above-described metal lead frame are electrically connected by bonding wires 7 and 8, thereby manufacturing a reflector 4 and a metal. The lead frame and the unit of the optical semiconductor element 3.
接著，在由上述金屬引線框與反射器4之內周面形成之凹部5中，填充矽氧樹脂(Shin-Etsu Silicone公司製，KER-2500)以對上述光半導體元件3進行樹脂密封(成形條件：150℃×4小時)，藉此形成透明密封樹脂層6，且就每個反射器加以切割進行單片化，製成圖1所示之光半導體(發光)裝置。製得之光半導體(發光)裝置得到具有高初期光反射率，且具優異長期耐光性之反射器4，並且具有高信賴性之良好光半導體(發光)裝置。 Then, a recessed portion 5 formed by the inner surface of the metal lead frame and the reflector 4 is filled with a silicone resin (KER-2500, manufactured by Shin-Etsu Silicone Co., Ltd.) to resin seal the optical semiconductor element 3 (formation). Condition: 150 ° C × 4 hours), whereby the transparent sealing resin layer 6 was formed, and each of the reflectors was cut and singulated to form an optical semiconductor (light-emitting) device shown in Fig. 1. The obtained optical semiconductor (light-emitting) device obtains a good optical semiconductor (light-emitting) device having a high initial light reflectance and excellent long-term light resistance, and having high reliability.
又，使用打錠上述實施例品之粉末的錠狀熱硬化性樹脂組成物，作為上述前述圖2及圖3所示之光半導體裝置及圖4所示之密封型光半導體元件之反射器11、15形成材料，依據前述之製造方法，製成圖2及圖3所示之光半導體 裝置及圖4所示之密封型光半導體元件。製得之光半導體裝置，與上述同樣地，得到具有高信賴性之良好光半導體裝置。另一方面，透過上述密封型光半導體元件之連接用電極裝載上述製得之密封型光半導體元件在形成配線電路板之電路之預定位置上，藉此製成光半導體裝置。製得之光半導體裝置，與上述同樣地，得到具有高信賴性之良好光半導體裝置。 Further, the ingot-shaped thermosetting resin composition in which the powder of the above-described example is applied is used as the reflector 11 of the above-described optical semiconductor device shown in Figs. 2 and 3 and the sealed optical semiconductor device shown in Fig. 4 And 15 forming materials, according to the above manufacturing method, the optical semiconductor shown in FIG. 2 and FIG. The device and the sealed optical semiconductor element shown in FIG. In the obtained optical semiconductor device, a good optical semiconductor device having high reliability was obtained in the same manner as described above. On the other hand, the sealing type optical semiconductor element obtained by the above-described sealing type optical semiconductor element is mounted on a predetermined position of a circuit for forming a wiring board, thereby forming an optical semiconductor device. In the obtained optical semiconductor device, a good optical semiconductor device having high reliability was obtained in the same manner as described above.
在上述實施例中，顯示本發明之具體形態，但是上述實施例只是舉例說明，不是限定地解釋。所屬技術領域中具有通常知識者了解之各種變形應在本發明之範圍內。 In the above embodiments, the specific embodiments of the present invention are shown, but the above embodiments are merely illustrative and not to be construed as limiting. Various modifications known to those of ordinary skill in the art are intended to be within the scope of the invention.
本發明之光半導體裝置用熱硬化性樹脂組成物作為反射由內建於光半導體裝置中之光半導體元件發出之光之反射器的形成材料是有用的。 The thermosetting resin composition for an optical semiconductor device of the present invention is useful as a material for forming a reflector for reflecting light emitted from an optical semiconductor element built in an optical semiconductor device.
1‧‧‧第一板部 1‧‧‧First Board
2‧‧‧第二板部 2‧‧‧ Second Board
3‧‧‧光半導體元件 3‧‧‧Optical semiconductor components
4‧‧‧反射器 4‧‧‧ reflector
5‧‧‧凹部 5‧‧‧ recess
6‧‧‧密封樹脂層 6‧‧‧ sealing resin layer
7,8‧‧‧接合線 7,8‧‧‧bonding line
Claims (17)
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| JP (1) | JP5825650B2 (en) |
| KR (1) | KR20160019407A (en) |
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| WO2017051838A1 (en) * | 2015-09-24 | 2017-03-30 | 日東電工株式会社 | Thermosetting resin composition for optical semiconductor devices, lead frame for optical semiconductor devices obtained using same, optical semiconductor device and optical semiconductor element |
| JP6883185B2 (en) * | 2015-09-24 | 2021-06-09 | 日東電工株式会社 | Thermosetting resin composition for opto-semiconductor devices and lead frames for opto-semiconductor devices, opto-semiconductor devices, opto-semiconductor devices obtained using the same. |
| EP4153686A1 (en) | 2020-05-19 | 2023-03-29 | BYK-Chemie GmbH | Thermoset polymer powder |
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| JP5421546B2 (en) * | 2007-07-05 | 2014-02-19 | 日立化成株式会社 | Thermosetting light reflecting resin composition, optical semiconductor element mounting substrate and optical semiconductor device using the resin composition |
| JP4623322B2 (en) * | 2007-12-26 | 2011-02-02 | 信越化学工業株式会社 | White thermosetting silicone resin composition for forming optical semiconductor case, optical semiconductor case and molding method thereof |
| JP5550230B2 (en) * | 2008-07-22 | 2014-07-16 | 日立化成株式会社 | Thermosetting resin composition, optical semiconductor element mounting substrate using the same, method for producing the same, and optical semiconductor device |
| JP5721969B2 (en) | 2010-06-11 | 2015-05-20 | 日東電工株式会社 | Epoxy resin composition for reflector of optical semiconductor device, lead frame for optical semiconductor device obtained using the same, and optical semiconductor device |
| JP2012175030A (en) * | 2011-02-24 | 2012-09-10 | Nitto Denko Corp | Resin composition for optical semiconductor element housing package and optical semiconductor light-emitting device obtained by using the same |
| JP5840377B2 (en) * | 2011-04-14 | 2016-01-06 | 日東電工株式会社 | Reflective resin sheet and method for manufacturing light-emitting diode device |
| JP5644831B2 (en) * | 2012-10-23 | 2014-12-24 | 日立化成株式会社 | Reflector manufacturing method and LED device |
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| WO2014199728A1 (en) | 2014-12-18 |
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