TWI654255B - Heat-curable polysilicon composition, chip soldering material, and optical semiconductor device - Google Patents

Heat-curable polysilicon composition, chip soldering material, and optical semiconductor device

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TWI654255B
TWI654255B TW106138366A TW106138366A TWI654255B TW I654255 B TWI654255 B TW I654255B TW 106138366 A TW106138366 A TW 106138366A TW 106138366 A TW106138366 A TW 106138366A TW I654255 B TWI654255 B TW I654255B
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Taiwan
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organic
heat
component
siloxane
optical semiconductor
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TW106138366A
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Chinese (zh)
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TW201829630A (en
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平野大輔
小材利之
小內諭
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日商信越化學工業股份有限公司
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    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
    • 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
    • H01L2224/481—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
    • H01L2224/01—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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Led Device Packages (AREA)
  • Silicon Polymers (AREA)
  • Die Bonding (AREA)

Abstract

本發明之課題為，提供一種加熱硬化型聚矽氧組成物，其係賦予克服了因氧阻礙導致之表面部分的未硬化之硬化物。 　　本發明之解決手段為，一種加熱硬化型聚矽氧組成物，其特徵為含有下列(A)～(D)： 　　(A)有機(聚)矽氧烷，係於分子中具有至少1個以下述一般式(1)所表示之構造：100質量份、 (B)有機過氧化物，係包含二醯基過氧化物或過氧酯：0.1～30質量份、 　　(C)有機氫聚矽氧烷，係於一分子中含有至少2個鍵結於矽原子的氫原子：0.1～20質量份、 　　(D)鉑系觸媒：成為0.01～1,000ppm之量。An object of the present invention is to provide a heat-curable polysiloxane composition which imparts an unhardened hardened material to a surface portion which is overcome by an oxygen barrier. The solution of the present invention is a heat-curable polysiloxane composition, which is characterized by containing the following (A) to (D): (A) an organic (poly) siloxane, which has at least one or less in the molecule The structure represented by the general formula (1): 100 parts by mass, (B) Organic peroxide, which contains difluorenyl peroxide or peroxyester: 0.1 to 30 parts by mass, (C) Organic hydrogen polysiloxane, which contains at least 2 bonds to silicon in one molecule Atomic hydrogen atom: 0.1 to 20 parts by mass, (D) Platinum catalyst: An amount of 0.01 to 1,000 ppm.

Description

加熱硬化型聚矽氧組成物、芯片焊接材料及光半導體裝置Heat-curable polysilicon composition, chip soldering material, and optical semiconductor device

[0001] 本發明係關於加熱硬化型聚矽氧組成物、由該組成物所構成之芯片焊接材料及使用有該芯片焊接材料之硬化物的光半導體裝置。[0001] The present invention relates to a heat-curable polysiloxane composition, a chip soldering material composed of the composition, and an optical semiconductor device using the cured product of the chip soldering material.

[0002] 由於發光二極體(LED)等之光半導體元件具有電力消耗量少之優異的特性，因此對於戶外照明用途或汽車用途之光半導體裝置的適用逐漸增加。如此之光半導體裝置，一般是將來自散發藍色光、近紫外光或紫外光的光半導體發光元件所發出的光，藉由作為波長轉換材料的螢光體來進行波長轉換，以得到偽白色的發光裝置。如此之光半導體裝置中，光半導體元件係使用芯片焊接材料而被接著並固定於框體。 　　[0003] 作為光半導體元件用芯片焊接材料組成物，以往，多使用有包含接著性或機械強度優異的雙酚A型環氧樹脂，與無UV吸收之環氧樹脂，例如氫化雙酚A型環氧樹脂或脂環式環氧樹脂，與硬化劑及硬化觸媒的組成物。然而，伴隨著LED元件之亮度及輸出變高，因來自LED元件之紫外光、熱等而產生接著層之變色及裂縫的問題。 　　[0004] 因此，提案有使用聚矽氧樹脂作為光半導體元件用芯片焊接材料中之環氧樹脂的替代(專利文獻1、2)。聚矽氧樹脂之硬化機構雖廣，但主要是採用使用有鉑觸媒的SiH基與烯基之加成反應。此時，在提昇與基材之接著性的目的下，添加具有(甲基)丙烯基或環氧基等之接著性提昇劑的情況居多。接著性提昇劑係若添加量少則缺乏接著性，但，若過多則對於硬化後物性的影響變大，例如，由於會造成硬度之降低等而無法多量使用。 　　[0005] 另一方面，雖具有利用了使用有作為接著性官能基之甲基丙烯基等的過氧化物硬化之事例(專利文獻3、4)，但有著因氧導致之硬化阻礙而表面之硬化性變差的問題。又，在以UV照射來使甲基丙烯基等進行硬化時也會產生因氧導致之硬化阻礙，因此，提案有藉由加成硬化來解決該影響的方法(專利文獻5)，但，如此之方法，實際上必須進行UV硬化與熱硬化兩者，因此，對於需要如無法進行UV照射般之複雜的裝置設計之部位的適用係為困難。 [先前技術文獻] [專利文獻] 　　[0006] 　　[專利文獻1] 日本特開2004-186168號公報 　　[專利文獻2] 日本特開2006-342200號公報 　　[專利文獻3] 日本特開2008-074982號公報 　　[專利文獻4] 日本特開2016-108456號公報 　　[專利文獻5] 日本特開2013-203794號公報[0002] Since optical semiconductor devices such as light emitting diodes (LEDs) have excellent characteristics of low power consumption, their applications to optical semiconductor devices for outdoor lighting applications or automotive applications are increasing. Such an optical semiconductor device generally converts light emitted from an optical semiconductor light-emitting element that emits blue light, near-ultraviolet light, or ultraviolet light to a wavelength conversion material using a phosphor as a wavelength conversion material to obtain a pseudo-white color. Luminescent device. In such an optical semiconductor device, the optical semiconductor element is bonded and fixed to the housing using a die-bonding material. [0003] As a chip soldering material composition for an optical semiconductor element, conventionally, a bisphenol A type epoxy resin containing excellent adhesion and mechanical strength and an epoxy resin having no UV absorption, such as hydrogenated bisphenol A type, have been used in many cases. Composition of epoxy resin or alicyclic epoxy resin, hardener and hardening catalyst. However, as the brightness and output of the LED element become higher, problems such as discoloration and cracks of the bonding layer occur due to ultraviolet light and heat from the LED element. [0004] Therefore, it has been proposed to use a silicone resin as an epoxy resin in a chip soldering material for an optical semiconductor device (Patent Documents 1 and 2). Although the curing mechanism of polysiloxane resin is wide, the addition reaction of SiH group and alkenyl group using platinum catalyst is mainly used. In this case, for the purpose of improving the adhesion to the substrate, it is often the case that an adhesion improver having a (meth) acryl group, an epoxy group, or the like is added. If the amount of the adhesiveness enhancer is small, the adhesiveness is insufficient, but if it is excessively large, the effect on the physical properties after hardening becomes large. For example, it cannot be used in a large amount due to a decrease in hardness and the like. [0005] On the other hand, although there are cases where a peroxide is used for curing using a methacryl group or the like as an adhesive functional group (Patent Documents 3 and 4), there is a problem that the surface is hardened by the hardening caused by oxygen. The problem of poor sclerosis. In addition, when methacryl and the like are hardened by UV irradiation, a hardening hindrance due to oxygen also occurs. Therefore, a method for solving this effect by addition hardening has been proposed (Patent Document 5). This method actually requires both UV hardening and heat hardening. Therefore, it is difficult to apply to a part requiring a complicated device design such as UV irradiation. [Prior Art Document] [Patent Document] [0006] [Patent Document 1] Japanese Patent Laid-Open No. 2004-186168 [Patent Document 2] Japanese Patent Laid-Open No. 2006-342200 [Patent Document 3] Japanese Patent Laid-Open No. 2008-074982 Gazette [Patent Document 4] Japanese Patent Laid-Open No. 2016-108456 [Patent Document 5] Japanese Patent Laid-Open No. 2013-203794

[發明所欲解決之課題] 　　[0007] 本發明係鑑於上述情事而完成者，其目的為，提供一種加熱硬化型聚矽氧組成物，其係可賦予克服了因氧阻礙導致之表面部分的未硬化之硬化物。又，其目的為，提供一種由該組成物所構成的芯片焊接材料。進而，其目的為，提供一種具有該芯片焊接材料之硬化物的光半導體裝置。 [用以解決課題之手段] 　　[0008] 為了解決上述課題，依據本發明， 　　提供一種加熱硬化型聚矽氧組成物，其特徵為含有下列(A)～(D)： 　　(A)有機(聚)矽氧烷，係於分子中具有至少1個以下述一般式(1)所表示之構造：100質量份、[式中，m為0、1、2之任一者，R1 為氫原子、苯基或鹵化苯基，R2 為氫原子或甲基，R3 為可取代或非取代且相同或相異之碳原子數1～12之1價之有機基，Z1 為-R4 -、 -R4 -O-、-R4 (CH3 )2 Si-O-(R4 為可取代或非取代且相同或相異之碳原子數1～10之2價之有機基)之任一者，Z2 為氧原子或是可取代或非取代且相同或相異之碳原子數1～10之2價之有機基]， 　　(B)有機過氧化物，係包含選自由二醯基過氧化物、過氧酯之1種以上：0.1～30質量份、 　　(C)有機氫聚矽氧烷，係於一分子中含有至少2個鍵結於矽原子的氫原子：0.1～20質量份、 　　(D)鉑系觸媒：相對於(A)成分，以(D)成分中之鉑的質量換算計，成為0.01～1,000ppm之量。 　　[0009] 本發明之加熱硬化型聚矽氧組成物係藉由進行(甲基)丙烯基之過氧化物所致的硬化、與SiH基和不飽和基之加成反應之兩者的硬化，而成為賦予克服了因氧阻礙導致之表面部分的未硬化之硬化物者。 　　[0010] 又，於此情況中，較佳係，前述(A)成分之有機(聚)矽氧烷之Z1 為-R4 -，Z2 為氧原子。 　　[0011] 又，於此情況中，較佳係，前述(A)成分之有機(聚)矽氧烷之Z1 為-R4 -O-或-R4 (CH3 )2 Si-O-，Z2 為可取代或非取代且相同或相異之碳原子數1～10之2價之有機基。 　　[0012] 若為包含如此之Z1 、Z2 的組合之(A)成分的加熱硬化型聚矽氧組成物，則在(B)成分進行分解時所產生的游離基與(A)成分會有效地進行反應，而可得到接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。 　　[0013] 又，較佳係，前述(A)成分之有機(聚)矽氧烷係於構成該有機(聚)矽氧烷的全矽氧烷單位中具有0.1mol%以上之(SiO2 )單位者。 　　[0014] 若為包含如此之(A)成分的加熱硬化型聚矽氧組成物，則在(B)成分進行分解時所產生的游離基與(A)成分會更有效地進行反應，而可進一步得到接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。 　　[0015] 又，於本發明中係提供一種芯片焊接材料，其特徵為由前述加熱硬化型聚矽氧組成物所構成者。 　　[0016] 本發明之加熱硬化型聚矽氧組成物係可賦予接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物，因此，可適宜使用作為芯片焊接材料。 　　[0017] 又，於本發明中係提供一種光半導體裝置，其特徵為具有將前述芯片焊接材料硬化所得之硬化物者。 　　[0018] 具有將由如此之本發明之加熱硬化型聚矽氧組成物所構成的芯片焊接材料硬化所得之硬化物的光半導體裝置，係成為可靠性高的光半導體裝置。 [發明效果] 　　[0019] 本發明之加熱硬化型聚矽氧組成物係藉由進行(甲基)丙烯基之過氧化物所致的硬化、與SiH基和不飽和基之加成反應之兩者的硬化，而可賦予克服了因氧阻礙導致之表面部分的未硬化之接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。具有將由如此之本發明之加熱硬化型聚矽氧組成物所構成的芯片焊接材料硬化所得之硬化物的光半導體裝置，係成為可靠性高的光半導體裝置。[Problems to be Solved by the Invention] [0007] The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a heat-curable polysilicone composition which can overcome the surface portion caused by oxygen barrier. Unhardened hardened material. Another object is to provide a chip soldering material composed of the composition. Furthermore, it aims at providing the optical semiconductor device which has the hardened | cured material of this die-bonding material. [Means for Solving the Problems] [0008] In order to solve the problems described above, according to the present invention, a heat-curable polysiloxane composition is provided, which is characterized by containing the following (A) to (D): (A) organic (poly) ) Siloxane has at least one structure represented by the following general formula (1) in the molecule: 100 parts by mass, [Wherein m is any of 0, 1 , 2 and R 1 is a hydrogen atom, a phenyl group or a halogenated phenyl group, R 2 is a hydrogen atom or a methyl group, and R 3 is a substituted or non-substituted and the same or a same phase A monovalent organic group having 1 to 12 carbon atoms, Z 1 is -R 4- , -R 4 -O-, -R 4 (CH 3 ) 2 Si-O- (R 4 is substitutable or non- Any of the substituted and identical or different divalent organic groups having 1 to 10 carbon atoms), Z 2 is an oxygen atom or a replaceable or non-substituted and identical or different carbon group having 1 to 10 carbon atoms Divalent organic group], (B) an organic peroxide containing one or more selected from the group consisting of a difluorenyl peroxide and a peroxy ester: 0.1 to 30 parts by mass, (C) an organohydrogenpolysiloxane, Based on one molecule containing at least two hydrogen atoms bonded to silicon atoms: 0.1 to 20 parts by mass, (D) Platinum catalyst: Conversion of the mass of platinum in the (D) component with respect to the (A) component The amount is 0.01 to 1,000 ppm. [0009] The heat-curable polysiloxane composition of the present invention is hardened by performing a (meth) acryl-based peroxide, and hardened by an addition reaction with SiH groups and unsaturated groups, It becomes a person who imparts an unhardened hardened material that overcomes the surface portion caused by oxygen barrier. [0010] In this case, it is preferable that Z 1 of the organic (poly) siloxane of the component (A) is -R 4- , and Z 2 is an oxygen atom. [0011] In this case, it is preferable that Z 1 of the organic (poly) siloxane of the aforementioned (A) component is -R 4 -O- or -R 4 (CH 3 ) 2 Si-O- Z 2 is a divalent organic group having 1 to 10 carbon atoms which may be substituted or non-substituted and which is the same or different. [0012] If it is a heat-curable polysiloxane composition containing the component (A) of such a combination of Z 1 and Z 2 , free radicals generated when the component (B) is decomposed and the component (A) The reaction proceeds efficiently, and a hardened product having excellent adhesion strength and workability and excellent heat resistance, light resistance, and crack resistance can be obtained. [0013] Preferably, the organic (poly) siloxane of the component (A) is (SiO 2 ) in an amount of 0.1 mol% or more in a persiloxane unit constituting the organic (poly) siloxane. Unit person. [0014] If it is a heat-curable polysiloxane composition containing such (A) component, the free radical generated when the (B) component is decomposed will react with the (A) component more efficiently, and the Further, a cured product having excellent adhesion strength and workability and excellent heat resistance, light resistance, and crack resistance was obtained. [0015] In the present invention, a chip soldering material is provided, which is characterized by being composed of the aforementioned heat-curable polysiloxane composition. [0016] The heat-curable polysiloxane composition of the present invention can provide a cured product having excellent adhesion strength and workability, and excellent heat resistance, light resistance, and crack resistance. Therefore, it can be suitably used as a chip soldering material. [0017] In the present invention, there is provided an optical semiconductor device including a hardened product obtained by hardening the chip soldering material. [0018] An optical semiconductor device having a cured product obtained by hardening a chip soldering material composed of the heat-curable polysiloxane composition of the present invention is a highly reliable optical semiconductor device. [Effects of Invention] [0019] The heat-curable polysiloxane composition of the present invention is a two-component hardening caused by (meth) acrylic peroxide, and an addition reaction with SiH group and unsaturated group. It can be hardened, and it can provide a hardened product that has excellent bonding strength and workability overcoming the unhardened surface portion due to oxygen barrier, and is excellent in heat resistance, light resistance, and crack resistance. An optical semiconductor device having a hardened product obtained by hardening a die-bonding material composed of the heat-curable polysiloxane composition of the present invention is a highly reliable optical semiconductor device.

[0021] 本發明者為了達成上述目的而進行了努力探討的結果，發現若是以含有下述(A)～(D)成分者為特徵之加熱硬化型聚矽氧組成物，則藉由進行(甲基)丙烯基之過氧化物所致的硬化、與SiH基和不飽和基之加成硬化之兩者的硬化，而成為即使不進行UV照射亦可賦予克服了因氧阻礙導致之表面部分的未硬化之硬化物的加熱硬化型聚矽氧組成物，因而完成本發明。以下，針對本發明之加熱硬化型聚矽氧組成物、芯片焊接材料及光半導體裝置來詳細地說明。 　　[0022] 亦即，本發明係 　　提供一種加熱硬化型聚矽氧組成物，其特徵為含有下列(A)～(D)： 　　(A)有機(聚)矽氧烷，係於分子中具有至少1個以下述一般式(1)所表示之構造：100質量份、[式中，m為0、1、2之任一者，R1 為氫原子、苯基或鹵化苯基，R2 為氫原子或甲基，R3 為可取代或非取代且相同或相異之碳原子數1～12之1價之有機基，Z1 為-R4 -、 -R4 -O-、-R4 (CH3 )2 Si-O-(R4 為可取代或非取代且相同或相異之碳原子數1～10之2價之有機基)之任一者，Z2 為氧原子或是可取代或非取代且相同或相異之碳原子數1～10之2價之有機基]， 　　(B)有機過氧化物，係包含選自由二醯基過氧化物、過氧酯之1種以上：0.1～30質量份、 　　(C)有機氫聚矽氧烷，係於一分子中含有至少2個鍵結於矽原子的氫原子：0.1～20質量份、 　　(D)鉑系觸媒：相對於(A)成分，以(D)成分中之鉑的質量換算計，成為0.01～1,000ppm之量。 　　[0023] (A)成分：有機(聚)矽氧烷 　　(A)成分之有機(聚)矽氧烷係於分子中具有至少1個以下述一般式(1)所表示之構造的有機(聚)矽氧烷。另外，於本發明中，有機(聚)矽氧烷係指於1分子中矽氧烷鍵(-Si-O-Si-)為1個的有機矽氧烷，及/或於1分子中包含2個以上之矽氧烷鍵的有機聚矽氧烷。[式中，m為0、1、2之任一者，R1 為氫原子、苯基或鹵化苯基，R2 為氫原子或甲基，R3 為可取代或非取代且相同或相異之碳原子數1～12之1價之有機基，Z1 為-R4 -、 -R4 -O-、-R4 (CH3 )2 Si-O-(R4 為可取代或非取代且相同或相異之碳原子數1～10之2價之有機基)之任一者，Z2 為氧原子或是可取代或非取代且相同或相異之碳原子數1～10之2價之有機基]。 　　[0024] 作為(A)成分之有機(聚)矽氧烷中之Z1 、Z2 的組合，較佳係Z1 為-R4 -，Z2 為氧原子者，或Z1 為-R4 -O-或 -R4 (CH3 )2 Si-O-，Z2 為可取代或非取代且相同或相異之碳原子數1～10之2價之有機基者。若為包含如此之(A)成分的加熱硬化型聚矽氧組成物，則在(B)成分進行分解時所產生的游離基與(A)成分會有效地進行反應，而可得到接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。 　　[0025] 又，較佳係於構成(A)成分之有機(聚)矽氧烷的全矽氧烷單位中具有0.1mol%以上之(SiO2 )單位。若為包含如此之(A)成分的加熱硬化型聚矽氧組成物，則在(B)成分進行分解時所產生的游離基與(A)成分會更有效地進行反應，而可進一步得到接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。 　　[0026] 進而，較佳係，(A)成分之有機(聚)矽氧烷為於分子中具有至少1個以下述一般式(2)所表示之構造者。若為包含如此之(A)成分的加熱硬化型聚矽氧組成物，則在(B)成分進行分解時所產生的游離基與(A)成分會更有效地進行反應，而可得到接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。(式中，m、R1 、R2 、R3 、R4 係與上述相同)。 　　[0027] 較佳係，(A)成分之有機(聚)矽氧烷為在25℃下之黏度為5mPa･s以上的液體或固體之分支狀或三維網狀構造的有機聚矽氧烷。 　　[0028] 於上述式(1)中，作為以R3 所示之鍵結於矽原子的可取代或非取代且相同或相異的碳原子數1～12之1價之有機基，較佳係可列舉碳原子數1～8左右者，具體而言係可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、新戊基、己基、環己基、辛基、壬基、癸基等之烷基、苯基、基、茬基、萘基等之芳基、苄基、苯乙基、苯丙基等之芳烷基、乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、己烯基、環己烯基、辛烯基等之烯基，或將此等之基之氫原子的一部分或全部以氟、溴、氯等之鹵素原子、氰基等取代後者，例如：氯甲基、氯丙基、溴乙基、三氟丙基等之鹵素取代烷基或氰乙基等。 　　[0029] 以下，例示(A)成分之有機(聚)矽氧烷。[0030] 又，作為(A)成分之有機(聚)矽氧烷，可例示下述式所示之MA單位、M單位、Q單位以MA：M：Q=1：4：6之比例被包含，且分子量以聚苯乙烯換算重量平均分子量計為5,000之有機聚矽氧烷、[0031] 下述式所示之MA-D單位、D單位、T單位為MA-D：D：T=2：6：7之比例，且分子量以聚苯乙烯換算重量平均分子量計為3500之有機聚矽氧烷等。[0032] 又，作為(A)成分之有機(聚)矽氧烷，可例示具有下述所示之構造的有機(聚)矽氧烷等。(式中，p=18，q=180)。 　　[0033](式中，t=18，u=180)。 　　[0034] 作為如此之(A)成分的合成方法，例如，使下述所示之有機氫矽烷，(式中，m、R1 、R2 、R3 、Z1 係與上述相同)， 　　較佳係下式所示之化合物，(式中，m、R1 、R2 、R3 、Z1 、Z2 係與上述相同)， 　　更具體而言係藉由將1,3-雙(3-甲基丙烯醯氧丙基)四甲基二矽氧烷與1,1,3,3-四甲基二矽氧烷在酸觸媒存在下進行平衡化反應所得之(3-甲基丙烯醯氧丙基)-1,1,3,3-四甲基二矽氧烷、與包含脂肪族不飽和基(可列舉例如乙烯性不飽和基、及乙炔性不飽和基)的有機(聚)矽氧烷在鉑觸媒存在下進行氫化矽烷化反應則為佳，雖藉由此方法可製造適於本發明者，但並不限制於前述之合成方法。又，包含脂肪族不飽和基之有機(聚)矽氧烷係可藉由包含具有脂肪族不飽和基之有機烷氧基矽烷的烷氧基矽烷之(共)水解縮合等周知的方法進行製造，亦可使用市售者。 　　[0035] 此等之(A)成分係可單一，亦可併用2種以上。 　　[0036] 另外，於(A)成分中，可在調整組成物之黏度或硬化物之硬度等的目的下，添加如以下所示般之包含聚矽氧的反應性稀釋劑，或不含聚矽氧的反應性稀釋劑。 　　[0037] 作為包含聚矽氧的反應性稀釋劑係可列舉具有下述構造之有機聚矽氧烷。如此之包含聚矽氧的反應性稀釋劑係可單一，亦可併用2種以上。 　　[0038] 作為不含聚矽氧的反應性稀釋劑係有如以H2 C=CGCO2 R5 所示般之(甲基)丙烯酸酯類，於上述式中，G為氫、鹵素、或1～約4個之碳原子的烷基；R5 係選自由具有1～約16個之碳原子的烷基、環烷基、烯基、環烯基、烷芳基、芳烷基或芳基，該等之任一者係可因應需要而以矽烷、矽、氧、鹵素、羰基、羥基、酯、羧酸、脲、胺基甲酸酯、胺甲酸酯、胺、醯胺、硫、磺酸酯、碸等取代或遮斷。 　　[0039] 作為反應性稀釋劑之特別理想之更詳細的(甲基)丙烯酸酯類係有如聚乙二醇二(甲基)丙烯酸酯、乙氧基化雙酚-A(甲基)丙烯酸酯(“EBIPA”或“EBIPMA”)般之雙酚-A二(甲基)丙烯酸酯、四氫呋喃(甲基)丙烯酸酯及二(甲基)丙烯酸酯、香茅基丙烯酸酯及香茅基甲基丙烯酸酯、羥丙基(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯(“HDDA”或“HDDMA”)、三羥甲基丙烷三(甲基)丙烯酸酯、四氫二環戊二烯基(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三丙烯酸酯(“ETTA”)、三乙二醇二丙烯酸酯及三乙二醇二甲基丙烯酸酯(“TRIEGMA”)、異莰基丙烯酸酯及異莰基甲基丙烯酸酯、以及與該等相應之丙烯酸酯。當然，該等之(甲基)丙烯酸酯類的組合亦可作為反應性稀釋劑使用。 　　[0040] 作為添加反應性稀釋劑時之添加量，相對於本發明之加熱硬化型聚矽氧組成物量，較佳為0.01～40質量%之範圍，更佳為0.05～20質量%之範圍。 　　[0041] (B)包含選自由二醯基過氧化物、過氧酯之1種以上的有機過氧化物 　　(B)成分之包含選自由二醯基過氧化物、過氧酯之1種以上的有機過氧化物係在將本發明之加熱硬化型聚矽氧組成物成形為所期望的形狀之後，施加加熱處理來藉由交聯反應使其硬化所需而摻合的成分，依據目的之連接溫度、連接時間、使用期限等而適當選擇。 　　[0042] 有機過氧化物，就兼具高反應性與長使用期限的觀點而言，較佳係半衰期10小時之溫度為40℃以上，且半衰期1分鐘之溫度為200℃以下，更佳係半衰期10小時之溫度為60℃以上，且半衰期1分鐘之溫度為180℃以下。 　　[0043] 作為二醯基過氧化物係可列舉例如：異丁基過氧化物、2,4-二氯苯甲醯基過氧化物、3,5,5-三甲基己醯基過氧化物、辛醯基過氧化物、月桂醯基過氧化物、硬脂醯基過氧化物、琥珀酸過氧化物、苯甲醯基過氧甲苯及苯甲醯基過氧化物。 　　[0044] 作為過氧酯係可列舉例如：基過氧新癸酸酯、1,1,3,3-四甲基丁基過氧新癸酸酯、1-環己基-1-甲基乙基過氧新癸酸酯、t-己基過氧新癸酸酯、t-丁基過氧特戊酸酯、1,1,3,3-四甲基丁基過氧-2-乙基己酸酯、2,5-二甲基-2,5-雙(2-乙基己醯基過氧)己烷、1-環己基-1-甲基乙基過氧-2-乙基己酸酯、t-己基過氧-2-乙基己酸酯、t-丁基過氧-2-乙基己酸酯、t-丁基過氧異丁酸酯、1,1-雙(t-丁基過氧)環己烷、t-己基過氧異丙基單碳酸酯、t-丁基過氧-3,5,5-三甲基己酸酯、t-丁基過氧月桂酸酯、2,5-二甲基-2,5-雙(m-甲醯基過氧)己烷、t-丁基過氧異丙基單碳酸酯、t-丁基過氧-2-乙基己基單碳酸酯、t-己基過氧苯甲酸酯、t-丁基過氧乙酸酯及雙(t-丁基過氧)六氫對苯二甲酸酯。 　　[0045] 該等可1種單獨或者組合2種以上來使用。 　　[0046] 作為其他有機過氧化物係可列舉：二烷基過氧化物、過氧二碳酸酯、過氧縮酮、氫過氧化物、矽烷基過氧化物等。亦可將該等之有機過氧化物與選自由上述二醯基過氧化物、過氧酯之1種以上組合，來作為(B)成分之有機過氧化物使用。 　　[0047] 作為二烷基過氧化物係可列舉例如：α,α’-雙(t-丁基過氧)二異丙基苯、二異丙苯過氧化物、2,5-二甲基-2,5-雙(t-丁基過氧)己烷及t-丁基基過氧化物。 　　[0048] 作為過氧二碳酸酯係可列舉例如：二-n-丙基過氧二碳酸酯、二異丙基過氧二碳酸酯、雙(4-t-丁基環己基)過氧二碳酸酯、二-2-乙氧基甲氧基過氧二碳酸酯、雙(2-乙基己基過氧)二碳酸酯、二甲氧基丁基過氧二碳酸酯及雙(3-甲基-3-甲氧基丁基過氧)二碳酸酯。 　　[0049] 作為過氧縮酮係可列舉例如：1,1-雙(t-己基過氧)-3,3,5-三甲基環己烷、1,1-雙(t-己基過氧)環己烷、1,1-雙(t-丁基過氧)-3,3,5-三甲基環己烷、1,1-(t-丁基過氧)環十二烷及2,2-雙(t-丁基過氧)癸烷。 　　[0050] 作為氫過氧化物係可列舉例如：二異丙基苯氫過氧化物及異丙苯氫過氧化物。 　　[0051] 作為矽烷基過氧化物係可列舉例如：t-丁基三甲基矽烷基過氧化物、雙(t-丁基)二甲基矽烷基過氧化物、t-丁基三乙烯基矽烷基過氧化物、雙(t-丁基)二乙烯基矽烷基過氧化物、參(t-丁基)乙烯基矽烷基過氧化物、t-丁基三烯丙基矽烷基過氧化物、雙(t-丁基)二烯丙基矽烷基過氧化物及參(t-丁基)烯丙基矽烷基過氧化物。 　　[0052] (B)成分之添加量，相對於(A)成分之有機(聚)矽氧烷合計量100質量份，為0.1～30質量份，較佳為0.5～20質量份。添加量未達0.1質量份時，反應無法充分進行，恐有無法得到目的之硬化物的硬度之虞。超過30質量份時，除了有無法得到所期望之硬化後的物性，亦即充分的耐熱性、耐裂縫性的可能性以外，亦恐有著色發生之虞，而成為變色的原因。又，(B)成分超過30質量份時，黏度明顯降低，而有變得不能作為芯片焊接材料使用的情況。 　　[0053] (C)於一分子中含有至少2個鍵結於矽原子的氫原子之有機氫聚矽氧烷 　　(C)成分之有機氫聚矽氧烷係發揮作為交聯劑的作用之成分，其與(A)成分產生氫化矽烷化反應，而有助於本組成物之硬化。該有機氫聚矽氧烷係於一分子中具有至少2個鍵結於矽原子的氫原子(亦即，SiH基)，較佳為具有3～500個，更佳為3～200個，特佳為3～150個。一分子中之矽原子數(或聚合度)，可使用較佳為2～200個，更佳為3～150個者。前述之SiH基可位於分子鏈末端及分子鏈非末端之任一位置，亦可位於此兩者。 　　[0054] 作為此有機氫聚矽氧烷中之鍵結於矽原子之基的具體例係可列舉例如：甲基、乙基、丙基、丁基、戊基、己基等之烷基；環戊基、環己基等之環烷基；苯基、基、茬基等之芳基；苄基、苯乙基等之芳烷基；3,3,3-三氟丙基、3-氯丙基等之鹵化烷基等之不具有脂肪族不飽和鍵之非取代或取代之1價烴基等，較佳為烷基及芳基，特佳為甲基及苯基。 　　[0055] (C)成分之於23℃時之黏度較佳為0.5～100,000 mPa･s，尤其是以10～5,000mPa･s為佳。如此之有機氫聚矽氧烷之分子構造並無特別限定，可列舉例如：直鏈狀、分支鏈狀、具有一部分分支之直鏈狀、環狀、三維網狀等。該有機氫聚矽氧烷係可為由單一種之矽氧烷單位所構成的均聚物，亦可為由2種以上之矽氧烷單位所構成的共聚物，亦可為該等之混合物。 　　[0056] 作為該有機氫聚矽氧烷係可列舉例如：1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基環四矽氧烷、甲基氫矽氧烷環狀聚合物、甲基氫矽氧烷･二甲基矽氧烷環狀共聚物、分子鏈兩末端二甲基氫矽氧基封鎖二甲基聚矽氧烷、分子鏈兩末端三甲基矽氧基封鎖甲基氫聚矽氧烷、分子鏈兩末端三甲基矽氧基封鎖二甲基矽氧烷･甲基氫矽氧烷共聚物、分子鏈兩末端二甲基氫矽氧基封鎖二甲基矽氧烷･甲基氫矽氧烷共聚物、兩末端三甲基矽氧基封鎖甲基氫矽氧烷･二苯基矽氧烷共聚物、兩末端三甲基矽氧基封鎖甲基氫矽氧烷･二苯基矽氧烷･二甲基矽氧烷共聚物、兩末端二甲基氫矽氧烷基封鎖甲基氫矽氧烷･二甲基矽氧烷･二苯基矽氧烷共聚物、由(CH3 )2 HSiO1/2 單位與 (CH3 )3 SiO1/2 單位與SiO4/2 單位所構成之共聚物、由 (CH3 )2 HSiO1/2 單位與SiO4/2 單位所構成之共聚物、由 (CH3 )2 HSiO1/2 單位與SiO4/2 單位與(C6 H5 )3 SiO1/2 單位所構成之共聚物等。該等當中，較佳係含有(C)成分中之矽氧烷單位全體之1mol%以上之二甲基矽氧烷單位者，更佳係含有1～100mol%者。 　　[0057] 於本組成物中，(C)成分之含量，相對於(A)成分100質量份，為0.1～20質量份，較佳為0.5～20質量份，特佳為1～10質量份。 　　[0058] 若(C)成分之含量未達0.1質量份，則本組成物難以充分硬化，而引起硬化物表面無法固化的情況。若超過20質量份，則本組成物因(B)成分而不會硬化，而因過氧化物導致之硬化性能下降。另外，此(C)成分之摻合量，亦可依據上述的理由，以(C)成分中之鍵結於矽原子的氫原子(亦即，SiH基)相對於本組成物中之全含烯基之有機(聚)矽氧烷中之鍵結於矽原子的烯基之總量的莫耳比－在(A)成分以外之成分不具有前述烯基的情況時係(B)成分中之鍵結於矽原子的氫原子相對於(A)成分中之鍵結於矽原子的烯基的莫耳比－成為0.01～4.0mol/mol，較佳為0.05～2.5mol/mol，特佳為0.1～1.0mol/mol的方式摻合。 　　[0059] (D)鉑系觸媒 　　(D)成分之鉑系觸媒係用以促進本組成物之硬化的觸媒，可列舉例如鉑及鉑化合物，作為具體例係可列舉：氯鉑酸、氯鉑酸之醇溶液、鉑之烯烴錯合物、鉑之烯基矽氧烷錯合物、鉑之羰基錯合物等。本組成物中之(D)成分之含量係可為有效量，具體而言，相對於(A)成分，(D)成分中之鉑金屬成分以鉑換算計，成為質量基準0.01～1,000ppm，較佳為0.1～500ppm之量。 　　[0060] 其他成分 　　本發明之加熱硬化型聚矽氧組成物亦可包含在特定的用途中如期望般之改變硬化或未硬化特性的其他成分。例如，可包含達約20質量%之量之如(甲基)丙烯醯氧基丙基三甲氧基矽烷、三烷基－或三烯丙基－異氰脲酸酯、環氧丙氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷等般之接著促進劑。作為其他任意成分，可包含達約30質量%之量的非(甲基)丙烯酸聚矽氧稀釋劑或可塑劑。作為非(甲基)丙烯酸聚矽氧類係可列舉具有100～500csp之黏度的三甲基矽烷基末端化油、及聚矽氧橡膠。非(甲基)丙烯酸聚矽氧類係可包含如乙烯基般之共硬化性基。 　　[0061] 又，亦可以提昇本發明之加熱硬化型聚矽氧組成物的強度、黏度調整、搖變性賦予等作為目的，進一步摻合氣相二氧化矽、奈米氧化鋁等之無機質填充劑。亦可因應需要，而於本發明之加熱硬化型聚矽氧組成物中，摻合染料、顏料、難燃劑等。 　　[0062] 又，亦可在改善作業性的目的下，添加溶劑等來使用。溶劑之種類並無特別限制，可使用將硬化前之加熱硬化型聚矽氧組成物溶解，使前述無機質填充劑等良好地分散，並提供均勻的芯片焊接材料或接著劑等之溶劑。該溶劑之摻合比例係只要因應於使用芯片焊接材料等之作業條件、環境、使用時間等而適當調整即可。溶劑亦可併用2種以上。作為如此之溶劑係可列舉：丁基卡必醇乙酸酯、卡必醇乙酸酯、甲基乙基酮、α-萜品醇、及賽路蘇乙酸酯等。 　　[0063] 又，亦可於本發明之組成物中摻合接著性提昇劑。作為接著性提昇劑係可例示矽烷偶合劑或其之寡聚物、具有與矽烷偶合劑相同之反應性基之聚矽氧等。 　　[0064] 作為接著性提昇劑，較佳係於分子內具有1個以上之含環氧之基的矽烷化合物或矽氧烷化合物。例如，可例示含有環氧基之矽烷偶合劑或其水解縮合物等。作為含有環氧基之矽烷偶合劑或其水解縮合物係可列舉：環氧丙氧基丙基三甲氧基矽烷、環氧丙氧基丙基三乙氧基矽烷等之矽烷化合物或其水解縮合物等。 　　[0065] 接著性提昇劑係為了提昇本發明之加熱硬化型聚矽氧組成物及其硬化物之對於基材的接著性而摻合於該組成物的任意成分。在此，基材係指金、銀、銅、鎳等之金屬材料、氧化鋁、氮化鋁、氧化鈦等之陶瓷材料、聚矽氧樹脂、環氧樹脂等之高分子材料。接著性提昇劑係可1種單獨亦可組合2種以上而使用。 　　[0066] 接著性提昇劑之摻合量，相對於上述(A)成分與(B)之合計100質量份，較佳為1～30質量份，更佳為5～20質量份。若該摻合量為5～20質量份，則本發明之加熱硬化型聚矽氧組成物及其硬化物對於基材之接著性會有效地提昇，又，不易著色。 　　[0067] 作為接著性提昇劑之適宜的具體例，雖可列舉如下，但並不限定於該等。[0068][0069](a、r為0～50之整數，b、s、t為1～50之整數)。 　　[0070] 又，為了確保使用期限，可摻合3-甲基-1-十二炔-3-醇、1-乙炔基環己醇、3,5-二甲基-1-己炔-3-醇等之加成反應控制劑。 　　[0071] 為了抑制硬化物之著色、氧化劣化等的發生，可於本發明之加熱硬化型聚矽氧組成物中摻合2,6-二-t-丁基-4-甲酚等之以往周知的抗氧化劑。又，為了賦予對於光劣化之抵抗性，亦可於本發明之加熱硬化型聚矽氧組成物中摻合受阻胺系安定劑等之光安定劑。 　　[0072] 本發明之加熱硬化型聚矽氧組成物係可藉由將上述各成分，使用周知的混合方法，例如，混合機、輥機等來進行混合而製造。又，本發明之加熱硬化型聚矽氧組成物係使用旋轉黏度計，例如，E型黏度計，以23℃測定的黏度為10～1,000,000mPa･s，尤其是以100～ 1,000,000mPa･s為佳。 　　[0073] 本發明之加熱硬化型聚矽氧組成物係可在周知的硬化條件下藉由周知的硬化方法而硬化。具體而言，通常可藉由以80～200℃，較佳為100～160℃進行加熱，而使該組成物硬化。加熱時間可為0.5分鐘～5小時左右，尤其是1分鐘～3小時左右。可依據與作業條件、生產性、發光元件或框體耐熱性之平衡而適當選定。 　　[0074] 本發明之加熱硬化型聚矽氧組成物係藉由進行(甲基)丙烯基之過氧化物所致的硬化、與SiH基和不飽和基之加成反應之兩者的硬化，而成為可賦予克服了因氧阻礙導致之表面部分的未硬化之硬化物。又，本發明之加熱硬化型聚矽氧組成物係可賦予接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。 　　[0075] 又，於本發明中係提供一種芯片焊接材料，其係由上述本發明之加熱硬化型聚矽氧組成物所構成者。尤其，可列舉可使用於將半導體元件連接於配線板的芯片焊接材料。 　　[0076] 本發明之加熱硬化型聚矽氧組成物係可適宜用於將LED晶片固定於封裝。又，亦可適宜用於其他有機電致發光元件(有機EL)、雷射二極體、及LED陣列等之光半導體元件。 　　[0077] 本發明之加熱硬化型聚矽氧組成物係可賦予透明性高，接著強度及作業性優異，且耐熱性、耐光性及耐裂縫性優異的硬化物。因而，若為由上述加熱硬化型聚矽氧組成物所構成之芯片焊接材料，則可適宜使用作為用以將LED晶片搭載於配線板的芯片焊接材料。 　　[0078] 將芯片焊接材料進行塗佈的方法並無特別限制，可列舉例如：旋轉塗佈、印刷、及壓縮成形等。芯片焊接材料的厚度只要適當選擇即可，通常為5～50μm，尤其為10～30μm。例如，可藉由使用分配裝置，以23℃之溫度、0.5～5kgf/cm2 之壓力進行吐出而容易地塗佈。又，藉由使用沖壓裝置，或將特定量之芯片焊接材料轉印於基板亦可容易進行。 　　[0079] 光半導體元件之搭載方法並無特別限制，可列舉例如芯片焊接器。決定芯片焊接材料之厚度的要素係除了前述之芯片焊接材料的黏度以外，亦可列舉光半導體元件之壓接荷重、壓接時間、壓接溫度。此等條件係只要因應於光半導體元件的外形形狀、目的之芯片焊接材料厚度而適當選擇即可，壓接荷重一般為1gf以上、1kgf以下。較佳為10gf以上、100gf以下。若為1gf以上之壓接荷重，則可將芯片焊接材料進行充分壓接。又，若使用1kgf以下之壓接荷重，則不會對光半導體元件表面的發光層造成損害。壓接時間係只要與工程之生產性兼顧而適當選擇即可，一般為超過0msec、1sec以下。較佳為1msec以上、30msec。若為1sec以下，則就生產性之點而言為佳。壓接溫度並無特別限制，雖依芯片焊接材料的使用溫度範圍即可，但一般而言，較佳為15℃以上、100℃以下。於芯片焊接器之壓接載台無加溫設備的情況，只要是在室溫附近之溫度範圍下使用即可。若為15℃以上，則由於芯片焊接材料之黏度不會變得過高而可充分壓接。若為100℃以下，則由於芯片焊接材料之硬化不會開始，因此可達到目的之芯片焊接材料的厚度。 　　[0080] 進而，於本發明中係提供一種光半導體裝置，其係具有將上述本發明之芯片焊接材料硬化所得之硬化物者。 　　[0081] 本發明之光半導體裝置，由於具有將由本發明之加熱硬化型聚矽氧組成物所構成的芯片焊接材料硬化所得之硬化物，因此成為具有克服了表面部分之未硬化之耐熱性、耐光性及耐裂縫性優異的硬化物之光半導體裝置。 　　[0082] 本發明之光半導體裝置係可藉由在將由本發明之加熱硬化型聚矽氧組成物所構成的芯片焊接材料塗佈於基板之後，依據以往周知的方法，將光半導體元件進行芯片焊接而製造。 　　[0083] 以下，針對本發明之光半導體裝置之一樣態，參照附圖來進行說明。第1圖係顯示具有將由本發明之加熱硬化型聚矽氧組成物所構成的芯片焊接材料硬化所得之硬化物的光半導體裝置之一例的剖面圖。第1圖所示之光半導體裝置10係於封裝基板之框體1的第1引線電極3上，具有將由本發明之加熱硬化型聚矽氧組成物所構成的芯片焊接材料硬化所得之硬化物5，並於此硬化物5上搭載有光半導體元件2者。此光半導體元件2之電極係藉由金線6而與第1引線電極3電連接。又，此光半導體元件2之電極係藉由金線7而與第2引線電極4電連接。又，此光半導體元件2係以密封樹脂8加以密封。 　　[0084] 作為第1圖之光半導體裝置10之製造方法係可例示以下的方法。 　　首先，於封裝基板之框體1的第1引線電極3上，定量轉印由本發明之加熱硬化型聚矽氧組成物所構成的芯片焊接材料，並於其上搭載光半導體元件2。接著，使芯片焊接材料加熱硬化而成為硬化物5。接著，將光半導體元件2之電極與第1引線電極3使用金線6來電連接，並將光半導體元件2之電極與第2引線電極4使用金線7來電連接，而得到搭載有光半導體元件2的封裝基板。接著，定量塗佈密封樹脂8，將所塗佈之密封樹脂，在周知的硬化條件下，藉由周知的硬化方法硬化，藉此而可將封裝基板密封。作為具有將本發明之芯片焊接材料硬化所得之硬化物的光半導體裝置係可列舉例如：LED、半導體雷射、光電二極體、光電晶體、太陽能電池、CCD等。 [實施例] 　　[0085] 以下雖顯示實施例與比較例來具體地說明本發明，但本發明並不限定於下述實施例。 　　[0086] (實施例1～8、比較例1～5) 　　準備下述成分，調製出表1、2所示之組成之聚矽氧組成物。 (A-1) 　　由下述矽氧烷單位所構成，以MA：M：Q=1：4：6之比例，分子量以GPC所致之聚苯乙烯換算的重量平均分子量計為5,000，25℃下為固體的有機聚矽氧烷、 　　[0087] (A-2) 　　以下述構造式所表示之25℃之黏度為7mPa･s的有機矽氧烷[0088] (B-1) 　　作為二醯基過氧化物係直接使用有Di-(3-methylbenzoyl) peroxide, Benzoyl(3-methylbenzoyl)peroxide and Dibenzol peroxide之40%二甲苯溶液(商品名：NYPER BMT-K40，日本油脂股份有限公司製)。 　　[0089] (B-2) 　　作為過氧酯係直接使用有t-Butyl peroxybenzoate(商品名：PERBUTYL Z，日本油脂股份有限公司製)。 　　[0090] (C)交聯劑 　　由下述矽氧烷單位所構成， 　　M：(CH3 )3 SiO1/2 D：(CH3 )2 SiO2/2 DH ：(CH3 )SiHO2/2 以M：D：DH =2：32：66所表示之25℃之黏度為150 mPa･s之直鏈狀有機聚矽氧烷 　　[0091] (D)鉑系觸媒： 　　鉑含量為0.5質量%之鉑1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之甲苯溶液 　　[0092] 其他任意成分 　　黏度調整劑：氣相二氧化矽(商品名REOLOSIL DM-30S Tokuyama公司製) 　　接著性提昇劑：於側鏈含有環氧基之環狀聚矽氧油(商品名：X-40-2670，信越化學工業股份有限公司製) 　　反應控制劑：3-甲基-1-十二炔-3-醇 　　[0093] [0094] [硬度之測定] 　　將所得之組成物倒入2mm厚度之單元，以150℃×2小時的條件進行硬化，而調製出硬化物。其後，藉由上島製作所製硬度計型號D來測定硬度。 　　[0095] [表面黏性之評估] 　　將所得之組成物倒入鋁培養皿，以150℃×2小時的條件在大氣下進行硬化，而調製出硬化物。以指觸評估所得之硬化物的表面黏性。 　　[0096] [光半導體封裝之製作] 　　分別準備：作為LED用封裝基板係具有載置光半導體元件之凹部，並於其底部設置有鍍銀的第1引線電極與第2引線電極之LED用封裝基板[SMD5050(I-CHIUN PRECISION INDUSTRY CO.,公司製、樹脂部PPA(聚鄰苯二甲醯胺))]；作為光半導體元件係Bridgelux公司製BXCD33。 　　[0097] 使用芯片焊接器(ASM公司製 AD-830)，於封裝基板之鍍銀的第1引線電極，藉由沖壓而定量轉印表1、2所示之各組成物，並於其上搭載光半導體元件。此時之光半導體元件之搭載條件係壓接時間13msec、壓接荷重60gf，不使用加溫裝置而在室溫25℃之環境下進行。接著，將封裝基板投入烘箱使各芯片焊接材料進行加熱硬化(實施例1～8、比較例2及比較例4為150℃、4小時，比較例1為170℃、1小時)。接著，將光半導體元件之電極與第1引線電極使用金線(田中電子工業公司製 FA 25μm)來電連接，並將光半導體元件之電極與第2引線電極使用金線(田中電子工業公司製 FA 25μm)來電連接。藉此，得到搭載有光半導體元件之LED用封裝基板各1片(以封裝數計為120個)。 　　[0098] 以上述方式，來製作芯片焊接材料不同之光半導體封裝，並使用於以下之試驗中。 　　[0099] [晶片抗剪試驗] 　　將以上述方法所得之光半導體封裝當中的10個，在25℃之室內，使用黏結強度試驗機(Dage公司製 Series4000)來進行晶片抗剪強度之測定，將所得之測定值的平均值以MPa表示。 　　[0100] [因氧導致之表面硬化阻礙之評估] 　　於以上述方法所得之光半導體封裝中，在25℃之室內，以前端尖銳的針，摩蹭晶片周邊，確認因氧導致之表面硬化阻礙之有無。 　　將所得之結果顯示於表3、4。 　　[0101] [0102] 如表3所示般，於使用有滿足本發明之範圍的加熱硬化型聚矽氧組成物作為芯片焊接材料的實施例1～實施例8中，任一例皆可得到高硬度、無表面黏性、克服了因氧阻礙導致之表面部分的未硬化之硬化物。進而，晶片抗剪測定的結果，得知可製造接著力高且可靠性高的光半導體裝置。 　　[0103] 另一方面，於不含C、D成分的比較例1、2中，雖任一例皆為高硬度，且觀測到高晶片抗剪，但具有表面黏性，而確認有因氧導致之表面硬化阻礙。另外，如由比較例2所明瞭般，此表面硬化阻礙即使是增加過氧化物的量亦無法防止。在B成分之量為過剩的情況(比較例3)係黏度顯著降低，而無法沖壓。又，在C成分為過剩的情況(比較例4)，因氧導致之表面硬化阻礙雖可防止，但成為晶片抗剪降低的結果。於不含B成分，而僅以鉑觸媒來硬化的比較例5中，硬度顯著降低，又，因黏度上昇而成為無法沖壓。 　　[0104] 另外，本發明並不限定於上述實施形態。上述實施形態係為例示，具有與記載於本發明之申請專利範圍中的技術性思想實質上相同的構造，且達成相同的作用效果者，任一者皆包含於本發明之技術範圍。[0021] As a result of diligent research in order to achieve the above object, the inventors have found that if a heat-curable polysiloxane composition characterized by containing the following components (A) to (D) is used, ( Hardening due to (meth) acrylic peroxide and hardening with the addition hardening of SiH group and unsaturated group, so that even if UV irradiation is not performed, the surface portion due to oxygen barrier can be overcome The heat-curable polysiloxane composition of the uncured hardened material has thus completed the present invention. Hereinafter, the heat-curable polysiloxane composition, die-bonding material, and optical semiconductor device of the present invention will be described in detail. [0022] That is, the present invention provides a heat-curable polysiloxane composition, which is characterized by containing the following (A) to (D): (A) an organic (poly) siloxane having at least 1 structure represented by the following general formula (1): 100 parts by mass, [Where m is any one of 0, 1, 2 and R 1 Is a hydrogen atom, phenyl or halogenated phenyl, R 2 Is a hydrogen atom or a methyl group, R 3 Is a monovalent organic group having 1 to 12 carbon atoms, which may be substituted or unsubstituted, and which is the same or different, Z 1 For -R 4 -, -R 4 -O-, -R 4 (CH 3 ) 2 Si-O- (R 4 Is a substituted or unsubstituted, divalent organic group of 1 to 10 carbon atoms having the same or different carbon numbers), Z 2 Is an oxygen atom or a bivalent organic group having 1 to 10 carbon atoms, which may be substituted or non-substituted and has the same or different carbon numbers], (B) an organic peroxide, which is selected from the group consisting of One or more kinds of oxygen esters: 0.1 to 30 parts by mass, (C) organohydrogen polysiloxane, containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule: 0.1 to 20 parts by mass, (D) Platinum-based catalyst: 0.01 to 1,000 ppm based on the mass conversion of platinum in the (D) component with respect to the (A) component. [0023] Component (A): Organic (poly) siloxane of organic (poly) siloxane (A) component is an organic (poly) siloxane having at least one structure represented by the following general formula (1) in the molecule ) Siloxane. In addition, in the present invention, the organic (poly) siloxane refers to an organosiloxane having one siloxane bond (-Si-O-Si-) in one molecule, and / or is contained in one molecule Organopolysiloxane with two or more siloxane bonds. [Where m is any one of 0, 1, 2 and R 1 Is a hydrogen atom, phenyl or halogenated phenyl, R 2 Is a hydrogen atom or a methyl group, R 3 Is a monovalent organic group having 1 to 12 carbon atoms, which may be substituted or unsubstituted, and which is the same or different, Z 1 For -R 4 -, -R 4 -O-, -R 4 (CH 3 ) 2 Si-O- (R 4 Is a substituted or unsubstituted, divalent organic group of 1 to 10 carbon atoms having the same or different carbon numbers), Z 2 Is an oxygen atom or a divalent organic group having 1 to 10 carbon atoms, which may be substituted or unsubstituted and has the same or different carbon atoms]. [0024] Z in Organic (Poly) siloxane as (A) Component 1 ,Z 2 Combination, preferably Z 1 For -R 4 -,Z 2 An oxygen atom, or Z 1 For -R 4 -O- or -R 4 (CH 3 ) 2 Si-O-, Z 2 It is a bivalent organic group having 1 to 10 carbon atoms which may be substituted or unsubstituted and which has the same or different carbon atoms. In the case of a heat-curable polysiloxane composition containing the component (A), the free radicals generated when the component (B) is decomposed will effectively react with the component (A), and the bonding strength and A hardened product having excellent workability and excellent heat resistance, light resistance, and crack resistance. [0025] In addition, it is preferable that the persiloxane unit in the organic (poly) siloxane constituting the component (A) 2 )unit. In the case of a heat-curable polysiloxane composition containing the component (A), the free radicals generated when the component (B) is decomposed and the component (A) react more effectively, and furthermore, A hardened product which is excellent in strength and workability and is excellent in heat resistance, light resistance, and crack resistance. [0026] Furthermore, it is preferable that the organic (poly) siloxane of the component (A) has at least one structure represented by the following general formula (2) in the molecule. In the case of the heat-curable polysiloxane composition containing the component (A), the free radicals generated when the component (B) is decomposed and the component (A) react more effectively, and the bonding strength can be obtained. A hardened product having excellent workability and excellent heat resistance, light resistance, and crack resistance. (Where m, R 1 , R 2 , R 3 , R 4 (Same as above). [0027] Preferably, the organic (poly) siloxane of the component (A) is a branched or three-dimensional network structure of a liquid or solid having a viscosity of 5 mPa · s or higher at 25 ° C. [0028] In the above formula (1), as R 3 The monovalent organic group having 1 to 12 carbon atoms, which may be substituted or unsubstituted and having the same or different carbon atoms, which is bonded to the silicon atom shown, preferably one having about 1 to 8 carbon atoms, specifically, Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, decyl, etc. Alkyl, phenyl, Aryl, stubyl, naphthyl, aryl, benzyl, phenethyl, phenylpropyl, aralkyl, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, Alkenyl groups such as cyclohexenyl, octenyl, etc., or a part or all of the hydrogen atoms of these groups may be replaced by halogen atoms such as fluorine, bromine, chlorine, cyano, etc., such as chloromethyl, chloro Halogen substituted alkyl, cyanoethyl, etc. of propyl, bromoethyl, trifluoropropyl and the like. [0029] Hereinafter, the organic (poly) siloxane of the component (A) is exemplified. [0030] As the organic (poly) siloxane as the component (A), MA units, M units, and Q units represented by the following formula can be exemplified by a ratio of MA: M: Q = 1: 4: 6. Including organopolysiloxanes having a molecular weight of 5,000 in terms of polystyrene equivalent weight average molecular weight, [0031] The MA-D unit, D unit, and T unit shown in the following formula are MA-D: D: T = 2: 6: 7, and the molecular weight is 3500 in terms of polystyrene-equivalent weight average molecular weight. Organic polysiloxane. [0032] Examples of the organic (poly) siloxane as the component (A) include an organic (poly) siloxane having a structure shown below. (Where p = 18, q = 180). [0033] (Where t = 18, u = 180). [0034] As a method for synthesizing such a component (A), for example, an organohydrosilane shown below is used, (Where m, R 1 , R 2 , R 3 ,Z 1 Are the same as above), preferably a compound represented by the following formula, (Where m, R 1 , R 2 , R 3 ,Z 1 ,Z 2 Is the same as above), and more specifically, by combining 1,3-bis (3-methacryloxypropyl) tetramethyldisilazane with 1,1,3,3-tetramethyldisiloxane (3-Methacryloxypropyl) -1,1,3,3-tetramethyldisilazane obtained by equilibration reaction of siloxane in the presence of an acid catalyst, and containing an aliphatic unsaturated group (For example, ethylenically unsaturated groups and acetylene unsaturated groups) organic (poly) siloxanes are preferably subjected to a hydrosilylation reaction in the presence of a platinum catalyst. The inventor is not limited to the aforementioned synthetic method. The organic (poly) siloxane containing an aliphatic unsaturated group can be produced by a known method such as (co) hydrolytic condensation of an alkoxysilane containing an organic alkoxysilane having an aliphatic unsaturated group. , Can also be used commercially. [0035] These (A) components may be used singly or in combination of two or more. [0036] In the component (A), for the purpose of adjusting the viscosity of the composition or the hardness of the hardened material, a reactive diluent containing polysiloxane or a polymer containing no polysiloxane may be added as shown below. Silicone reactive diluent. [0037] Examples of the reactive diluent system including polysiloxane include an organic polysiloxane having the following structure. Such a reactive diluent containing polysiloxane may be used singly or in combination of two or more. [0038] As a reactive diluent without polysiloxane, such as H 2 C = CGCO 2 R 5 As shown (meth) acrylates, in the above formula, G is hydrogen, halogen, or an alkyl group of 1 to about 4 carbon atoms; R 5 Is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkaryl group, an aralkyl group, or an aryl group having 1 to about 16 carbon atoms, and any of them Silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, carbamate, carbamate, amine, amidine, sulfur, sulfonate, amidine, etc. are substituted or blocked. [0039] More detailed (meth) acrylates which are particularly desirable as reactive diluents are, for example, polyethylene glycol di (meth) acrylate, ethoxylated bisphenol-A (meth) acrylate ("EBIPA" or "EBIPMA") bisphenol-A di (meth) acrylate, tetrahydrofuran (meth) acrylate and di (meth) acrylate, citronella acrylate and citronella methyl Acrylate, hydroxypropyl (meth) acrylate, hexanediol di (meth) acrylate ("HDDA" or "HDDMA"), trimethylolpropane tri (meth) acrylate, tetrahydrobicyclo Pentadienyl (meth) acrylate, ethoxylated trimethylolpropane triacrylate ("ETTA"), triethylene glycol diacrylate, and triethylene glycol dimethacrylate ("TRIEGMA" ), Isofluorenyl acrylate and isofluorenyl methacrylate, and corresponding acrylates. Of course, these (meth) acrylate combinations can also be used as a reactive diluent. [0040] The amount added as a reactive diluent is preferably in the range of 0.01 to 40% by mass, and more preferably in the range of 0.05 to 20% by mass, relative to the amount of the heat-curable polysiloxane composition of the present invention. [0041] (B) one or more organic peroxides containing a component selected from the group consisting of a difluorenyl peroxide and a peroxy ester (B) one or more components containing a component selected from the group consisting of a difluorenyl peroxide and a peroxy ester After forming the heat-curable polysiloxane composition of the present invention into a desired shape, the organic peroxide is a component which is required to be hardened by a cross-linking reaction by applying a heat treatment, depending on the purpose. The connection temperature, connection time, and usage period are appropriately selected. [0042] From the standpoint of having both high reactivity and long service life, the organic peroxide is preferably a temperature with a half-life of 10 hours at 40 ° C. or higher and a half-life of 1 minute at 200 ° C. or lower, more preferably The temperature at half-life of 10 hours is above 60 ° C, and the temperature at half-life of 1 minute is below 180 ° C. [0043] Examples of the difluorenyl peroxide system include isobutyl peroxide, 2,4-dichlorobenzylidene peroxide, and 3,5,5-trimethylhexanoyl peroxide. Compounds, octyl methoxide, lauryl methoxide, stearyl methoxide, succinic acid peroxide, benzamyl peroxytoluene and benzamyl peroxide. [0044] Examples of the peroxyester system include: Peroxynedecanoate, 1,1,3,3-tetramethylbutylperoxynedecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanate, t-hexyl peroxy Oxyneodecanate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2 , 5-bis (2-ethylhexylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethyl Hexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexyl Peroxyisopropylmonocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5 -Double (m- (Methylaminoperoxy) hexane, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, t- Butyl peroxyacetate and bis (t-butylperoxy) hexahydroterephthalate. [0045] These can be used alone or in combination of two or more. [0046] Examples of other organic peroxides include dialkyl peroxides, peroxydicarbonates, peroxyketals, hydroperoxides, and silane-based peroxides. These organic peroxides may be used in combination with one or more kinds selected from the above-mentioned difluorenyl peroxide and peroxyester as the organic peroxide of the component (B). [0047] Examples of the dialkyl peroxide system include α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, and 2,5-dimethyl. -2,5-bis (t-butylperoxy) hexane and t-butyl Based peroxide. [0048] Examples of the peroxydicarbonate system include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, and bis (4-t-butylcyclohexyl) peroxydicarbonate. Carbonate, di-2-ethoxymethoxyperoxydicarbonate, bis (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, and bis (3-methyl Propyl-3-methoxybutylperoxy) dicarbonate. [0049] Examples of the peroxyketal system include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1,1-bis (t-hexylperoxy). ) Cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane and 2 , 2-bis (t-butylperoxy) decane. [0050] Examples of the hydroperoxide system include diisopropylbenzene hydroperoxide and cumene hydroperoxide. [0051] Examples of the silane-based peroxide system include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, and t-butyltrivinyl. Silyl peroxide, bis (t-butyl) divinylsilyl peroxide, ginseng (t-butyl) vinylsilyl peroxide, t-butyltriallylsilyl peroxide , Bis (t-butyl) diallyl silyl peroxide and ginseng (t-butyl) allyl silyl peroxide. [0052] The added amount of the component (B) is 0.1 to 30 parts by mass, and preferably 0.5 to 20 parts by mass based on 100 parts by mass of the total organic (poly) siloxane content of the component (A). When the addition amount is less than 0.1 parts by mass, the reaction cannot proceed sufficiently, and there is a possibility that the hardness of the intended hardened material may not be obtained. When it exceeds 30 parts by mass, in addition to the possibility that desired physical properties after hardening, that is, sufficient heat resistance and crack resistance may not be obtained, there is a possibility that coloration may occur and cause discoloration. When the component (B) exceeds 30 parts by mass, the viscosity is remarkably reduced, and it may not be used as a die-bonding material. (C) an organohydrogenpolysiloxane (C) component containing at least two organohydrogenpolysiloxanes (C) in a molecule, which function as a crosslinking agent It causes a hydrosilylation reaction with the component (A), and contributes to the hardening of the composition. The organic hydrogen polysiloxane has at least 2 hydrogen atoms (ie, SiH groups) bonded to silicon atoms in one molecule, preferably 3 to 500, more preferably 3 to 200, and It is preferably 3 to 150. The number of silicon atoms (or degree of polymerization) in one molecule can be preferably 2 to 200, more preferably 3 to 150. The aforementioned SiH group may be located at either the end of the molecular chain and the non-terminal end of the molecular chain, or both. [0054] Specific examples of the group in which the organic hydrogen polysiloxane is bonded to a silicon atom include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; Cycloalkyl, such as pentyl, cyclohexyl; phenyl, Aryl groups such as phenyl groups, stubyl groups, etc .; aralkyl groups such as benzyl, phenethyl, etc .; halogenated alkyl groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, etc. have no aliphatic unsaturated The unsubstituted or substituted monovalent hydrocarbon group and the like are preferably an alkyl group and an aryl group, and particularly preferably a methyl group and a phenyl group. [0055] The viscosity of the component (C) at 23 ° C. is preferably 0.5 to 100,000 mPa ･ s, particularly preferably 10 to 5,000 mPa ･ s. The molecular structure of such an organohydrogenpolysiloxane is not particularly limited, and examples thereof include linear, branched, linear, partially branched, cyclic, and three-dimensional network. The organohydrogenpolysiloxane system may be a homopolymer composed of a single type of silicone unit, or a copolymer composed of two or more types of silicone units, or a mixture of these. . [0056] Examples of the organic hydrogen polysiloxane include 1,1,3,3-tetramethyldisilaxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and methyl Hydroxysilane cyclic polymer, methylhydrosiloxane, dimethylsiloxane cyclic copolymer, dimethylhydrosiloxane at both ends of the molecular chain blocking dimethylpolysiloxane, molecular chain Trimethylsiloxy blocks both ends of methylhydropolysiloxane, trimethylsiloxy blocks both ends of dimethylsiloxane, methylhydrosiloxane copolymers, dimethyl two ends of molecular chain Hydroxysiloxy blocked dimethylsiloxanes ･ methylhydrosiloxane copolymer, trimethylsiloxy blocked dimethylsiloxanes diphenylsiloxane copolymer, both ends Methylsiloxy blocked methylhydrosiloxane, diphenylsiloxane, dimethylsiloxane copolymer, dimethylhydrosiloxane blocked at both ends, methylhydrosiloxane, dimethyl Siloxane-diphenylsiloxane copolymer, from (CH 3 ) 2 HSiO 1/2 Unit with (CH 3 ) 3 SiO 1/2 Units and SiO 4/2 Copolymer composed of units, composed of (CH 3 ) 2 HSiO 1/2 Units and SiO 4/2 Copolymer composed of units, composed of (CH 3 ) 2 HSiO 1/2 Units and SiO 4/2 Unit with (C 6 H 5 ) 3 SiO 1/2 Copolymers made up of units, etc. Among these, those containing 1 mol% or more of dimethylsiloxane units in the total siloxane units in the component (C) are more preferable, and those containing 1 to 100 mol% are more preferable. [0057] In the present composition, the content of the component (C) is 0.1 to 20 parts by mass, preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (A). . [0058] When the content of the component (C) is less than 0.1 parts by mass, it is difficult to sufficiently harden the composition, and the surface of the hardened material may not be cured. If it exceeds 20 parts by mass, the composition will not be hardened due to the component (B), and the hardening performance due to peroxide will be reduced. In addition, the blending amount of the component (C) can also be based on the reason described above, with the hydrogen atom (that is, SiH group) bonded to the silicon atom in the component (C) relative to the total content of the composition Molar ratio of the total amount of alkenyl groups bonded to silicon atoms in the organic (poly) silane of alkenyl groups-when components other than (A) components do not have the aforementioned alkenyl groups, they are in (B) components The molar ratio of the hydrogen atom bonded to the silicon atom to the alkenyl group bonded to the silicon atom in the component (A) becomes 0.01 to 4.0 mol / mol, preferably 0.05 to 2.5 mol / mol, particularly preferably Blend in a manner of 0.1 to 1.0 mol / mol. (D) Platinum-based catalyst (D) The platinum-based catalyst is a catalyst used to promote hardening of the composition, and examples thereof include platinum and platinum compounds. Specific examples include chloroplatinic acid. , Alcohol solution of chloroplatinic acid, olefin complex of platinum, alkenylsiloxane complex of platinum, carbonyl complex of platinum, etc. The content of the component (D) in the composition may be an effective amount. Specifically, the platinum metal component in the component (D) is in terms of platinum and becomes 0.01 to 1,000 ppm by mass in terms of (A) component. The amount is preferably 0.1 to 500 ppm. [0060] Other Ingredients The heat-curable polysiloxane composition of the present invention may contain other ingredients that change the hardened or unhardened properties as desired in specific applications. For example, it may be contained in an amount of up to about 20% by mass such as (meth) acryloxypropyltrimethoxysilane, trialkyl- or triallyl-isocyanurate, glycidoxypropyl Adhesives such as trimethoxysilane and vinyltrimethoxysilane. As other optional components, a non- (meth) acrylic polysiloxane diluent or a plasticizer may be contained in an amount of about 30% by mass. Examples of non- (meth) acrylic polysiloxanes include trimethylsilyl-terminated oils having a viscosity of 100 to 500 csp, and polysiloxane rubbers. The non- (meth) acrylic polysiloxane may contain a co-curable group such as a vinyl group. [0061] In addition, it is also possible to improve the strength, viscosity adjustment, and imparting shaking properties of the heat-curable polysiloxane composition of the present invention, and further blend inorganic fillers such as fumed silica, nano-alumina, and the like. . If necessary, dyes, pigments, flame retardants, etc. may be blended in the heat-curable polysiloxane composition of the present invention. [0062] A solvent or the like may be added for the purpose of improving workability. The type of the solvent is not particularly limited, and a solvent can be used that dissolves the heat-curable polysiloxane composition before curing, disperses the inorganic filler and the like well, and provides a uniform die-bonding material or adhesive. The blending ratio of the solvent may be appropriately adjusted in accordance with the working conditions, environment, use time, and the like of the die-bonding material. The solvent may be used in combination of two or more kinds. Examples of such a solvent system include butyl carbitol acetate, carbitol acetate, methyl ethyl ketone, α-terpineol, and threonyl acetate. [0063] Further, an adhesion promoter may be blended in the composition of the present invention. Examples of the adhesiveness-improving agent include a silane coupling agent or an oligomer thereof, and a polysiloxane having the same reactive group as the silane coupling agent. [0064] As the adhesion improver, it is preferably a silane compound or a siloxane compound having one or more epoxy-containing groups in the molecule. For example, an epoxy group-containing silane coupling agent or a hydrolyzed condensate thereof can be exemplified. Examples of the epoxy group-containing silane coupling agent or a hydrolyzed condensate thereof include a silane compound such as glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, and the like, or a hydrolysis condensation thereof. Things. [0065] The adhesiveness improving agent is an optional component incorporated in the heat-curable polysiloxane composition and the cured product of the present invention to improve the adhesion to the substrate. Here, the substrate means a metal material such as gold, silver, copper, nickel, a ceramic material such as alumina, aluminum nitride, and titanium oxide, a polymer material such as a silicone resin, and an epoxy resin. The adhesiveness-improving agent may be used alone or in combination of two or more. [0066] The blending amount of the adhesion promoter is preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass based on 100 parts by mass of the total of the components (A) and (B). If the blending amount is 5 to 20 parts by mass, the adhesiveness of the heat-curable polysiloxane composition and the cured product of the present invention to the substrate is effectively improved, and coloring is not easy. [0067] Although suitable specific examples of the adhesion promoter are listed below, they are not limited to these. [0068] [0069] (a, r are integers from 0 to 50, and b, s, and t are integers from 1 to 50). [0070] In order to ensure the life span, 3-methyl-1-dodecyn-3-ol, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyne-3 may be blended. -Addition reaction controlling agent such as alcohol. [0071] In order to suppress the occurrence of coloration and oxidative deterioration of the cured product, 2,6-di-t-butyl-4-cresol and the like may be blended in the heat-curable polysiloxane composition of the present invention. Well-known antioxidants. In order to provide resistance to light deterioration, a light stabilizer such as a hindered amine-based stabilizer may be added to the heat-curable polysiloxane composition of the present invention. [0072] The heat-curable polysiloxane composition of the present invention can be produced by mixing the above-mentioned components using a known mixing method, for example, a mixer, a roll, or the like. In addition, the heat-curable polysiloxane composition of the present invention uses a rotational viscometer, for example, an E-type viscometer, and the viscosity measured at 23 ° C is 10 to 1,000,000 mPa ･ s, especially 100 to 1,000,000 mPa ･ s. good. [0073] The heat-curable polysiloxane composition of the present invention can be hardened by a known hardening method under known hardening conditions. Specifically, the composition is usually hardened by heating at 80 to 200 ° C, preferably 100 to 160 ° C. The heating time may be about 0.5 minutes to 5 hours, especially about 1 minute to 3 hours. It can be appropriately selected according to the balance with the working conditions, productivity, heat resistance of the light-emitting element or the housing. [0074] The heat-curable polysiloxane composition of the present invention is hardened by performing a (meth) acrylic-based peroxide, and hardened by an addition reaction with SiH groups and unsaturated groups, It becomes an unhardened hardened material that can overcome the surface part caused by oxygen barrier. In addition, the heat-curable polysiloxane composition of the present invention can provide a cured product having excellent adhesion strength and workability, and excellent heat resistance, light resistance, and crack resistance. [0075] In the present invention, a chip soldering material is provided, which is composed of the heat-curable polysiloxane composition of the present invention. In particular, a chip soldering material that can be used to connect a semiconductor element to a wiring board is mentioned. [0076] The heat-curable polysiloxane composition of the present invention can be suitably used for fixing an LED chip to a package. In addition, it can be suitably used for other optical semiconductor devices such as organic electroluminescence elements (organic EL), laser diodes, and LED arrays. [0077] The heat-curable polysiloxane composition of the present invention can provide a hardened product having high transparency, excellent bonding strength and workability, and excellent heat resistance, light resistance, and crack resistance. Therefore, if it is a chip soldering material which consists of the said heat-hardening type | mold polysiloxane composition, it can use suitably as a chip soldering material for mounting an LED chip on a wiring board. [0078] The method of applying the die-bonding material is not particularly limited, and examples thereof include spin coating, printing, and compression molding. The thickness of the die-bonding material may be appropriately selected, and is usually 5 to 50 μm, and particularly 10 to 30 μm. For example, by using a dispensing device, at a temperature of 23 ° C, 0.5 to 5 kgf / cm 2 The pressure is discharged and applied easily. In addition, it can be easily performed by using a stamping device or transferring a specific amount of die-bonding material to a substrate. [0079] The method of mounting the optical semiconductor element is not particularly limited, and examples thereof include a die bonder. The factors that determine the thickness of the die-bonding material are, in addition to the viscosity of the die-bonding material described above, the crimping load, crimping time, and crimping temperature of the optical semiconductor element. These conditions may be appropriately selected depending on the shape of the optical semiconductor element and the thickness of the chip soldering material for the purpose, and the crimping load is generally 1 gf or more and 1 kgf or less. It is preferably 10 gf or more and 100 gf or less. If it is a crimping load of 1 gf or more, the chip soldering material can be sufficiently crimped. In addition, if a compression bonding load of 1 kgf or less is used, the light emitting layer on the surface of the optical semiconductor element is not damaged. The crimping time may be appropriately selected in consideration of the productivity of the process, and generally exceeds 0 msec and 1 sec. It is preferably 1 msec or more and 30 msec. When it is 1 sec or less, it is preferable from the viewpoint of productivity. There is no particular limitation on the crimping temperature. Although the temperature range of the chip soldering material can be used, it is generally preferably 15 ° C or higher and 100 ° C or lower. In the case where there is no heating device on the crimping stage of the chip soldering device, it can be used in a temperature range near room temperature. If it is 15 ° C. or higher, the viscosity of the die-bonding material does not become excessively high, and sufficient pressure bonding can be performed. If it is below 100 ° C, the hardening of the chip soldering material will not start, so the thickness of the target chip soldering material can be achieved. [0080] Furthermore, in the present invention, there is provided an optical semiconductor device having a hardened product obtained by hardening the chip soldering material of the present invention. [0081] The optical semiconductor device of the present invention has a hardened product obtained by hardening a chip soldering material composed of the heat-curable polysiloxane composition of the present invention, and therefore has heat resistance that overcomes the unhardened surface portion, An optical semiconductor device of a cured product excellent in light resistance and crack resistance. [0082] The optical semiconductor device of the present invention can be coated with a chip soldering material composed of the heat-curable polysiloxane composition of the present invention on a substrate, and then the optical semiconductor element can be chipped according to a conventionally known method. Manufactured by welding. [0083] Hereinafter, the state of the optical semiconductor device of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of an optical semiconductor device having a cured product obtained by curing a die-bonding material composed of a heat-curable polysiloxane composition of the present invention. The optical semiconductor device 10 shown in FIG. 1 is provided on the first lead electrode 3 of the housing 1 of the package substrate, and has a hardened product obtained by hardening a chip soldering material composed of the heat-curable polysiloxane composition of the present invention. 5, and an optical semiconductor element 2 is mounted on the hardened body 5. The electrode of the optical semiconductor element 2 is electrically connected to the first lead electrode 3 through a gold wire 6. The electrode of the optical semiconductor element 2 is electrically connected to the second lead electrode 4 through a gold wire 7. The optical semiconductor element 2 is sealed with a sealing resin 8. [0084] The manufacturing method of the optical semiconductor device 10 shown in FIG. 1 is exemplified by the following method. First, a chip soldering material composed of the heat-curable polysiloxane composition of the present invention is quantitatively transferred onto the first lead electrode 3 of the casing 1 of the package substrate, and an optical semiconductor element 2 is mounted thereon. Next, the die-bonding material is heat-hardened to become a cured product 5. Next, the electrode of the optical semiconductor element 2 and the first lead electrode 3 are electrically connected using a gold wire 6, and the electrode of the optical semiconductor element 2 and the second lead electrode 4 are electrically connected using a gold wire 7 to obtain a mounted optical semiconductor element. 2 package substrate. Next, the sealing resin 8 is quantitatively applied, and the applied sealing resin is cured by a known curing method under known curing conditions, thereby sealing the package substrate. Examples of the optical semiconductor device having a hardened product obtained by hardening the chip soldering material of the present invention include LEDs, semiconductor lasers, photovoltaic diodes, photovoltaic crystals, solar cells, and CCDs. [Examples] Although the present invention is specifically described below by showing examples and comparative examples, the present invention is not limited to the following examples. [Examples 1 to 8 and Comparative Examples 1 to 5] The following components were prepared, and a polysiloxane composition having the composition shown in Tables 1 and 2 was prepared. (A-1) is composed of the following siloxane units, An organopolysiloxane based on the weight average molecular weight of polystyrene converted by GPC of 5,000 in terms of the ratio of MA: M: Q = 1: 4: 6, and a solid at 25 ° C, [0087] (A -2) Organosiloxane having a viscosity of 7 mPa ･ s at 25 ° C. expressed by the following structural formula (B-1) As a dihydrazyl peroxide system, a 40% xylene solution of Di- (3-methylbenzoyl) peroxide, Benzoyl (3-methylbenzoyl) peroxide and Dibenzol peroxide (trade name: NYPER BMT) -K40, manufactured by Japan Oil & Fat Co., Ltd.). (B-2) As the peroxyester system, t-Butyl peroxybenzoate (trade name: PERBUTYL Z, manufactured by Nippon Oil & Fat Co., Ltd.) is directly used. (C) The cross-linking agent is composed of the following siloxane units, M: (CH 3 ) 3 SiO 1/2 D: (CH 3 ) 2 SiO 2/2 D H : (CH 3 SiHO 2/2 Take M: D: D H = 2: Linear organopolysiloxane with a viscosity of 150 mPa ･ s at 25 ° C as indicated by 32:32:66. [0091] (D) Platinum catalyst: Platinum 1,3-platinum content is 0.5% by mass Toluene solution of divinyl-1,1,3,3-tetramethyldisilaxane complex [0092] Viscosity adjuster for other optional ingredients: fumed silica (trade name REOLOSIL DM-30S manufactured by Tokuyama Corporation) ) Adhesive enhancer: cyclic polysiloxane oil containing an epoxy group in the side chain (trade name: X-40-2670, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Reaction control agent: 3-methyl-1-deca Diacetyl-3-ol [Measurement of Hardness] The obtained composition was poured into a unit having a thickness of 2 mm, and was cured at 150 ° C for 2 hours to prepare a cured product. Thereafter, the hardness was measured by a durometer model D made by Kamishima Co., Ltd. [Evaluation of Surface Tackiness] The obtained composition was poured into an aluminum petri dish, and was cured in the atmosphere at 150 ° C for 2 hours to prepare a cured product. The surface adhesion of the obtained hardened product was evaluated by finger touch. [Production of Optical Semiconductor Package] Prepare separately: LED package substrates having recesses on which optical semiconductor elements are placed, and provided with silver-plated first lead electrodes and second lead electrodes on the bottom thereof. Substrate [SMD5050 (I-CHIUN PRECISION INDUSTRY CO., Company, resin part PPA (polyphthalamide))]; BXCD33 manufactured by Bridgelux as an optical semiconductor device. [0097] Using a die bonder (AD-830 manufactured by ASM), the silver-plated first lead electrode of the package substrate was quantitatively transferred by stamping to each of the compositions shown in Tables 1 and 2 and applied thereon. Mounted with optical semiconductor elements. The mounting conditions of the optical semiconductor device at this time were a crimping time of 13 msec and a crimping load of 60 gf. The heating was performed at a room temperature of 25 ° C without using a heating device. Next, the package substrate was put into an oven to heat-harden each chip solder material (Examples 1 to 8, Comparative Example 2 and Comparative Example 4 were 150 ° C and 4 hours, and Comparative Example 1 was 170 ° C and 1 hour). Next, the electrodes of the optical semiconductor element and the first lead electrode were electrically connected using gold wires (FA 25 μm manufactured by Tanaka Electronics Industry Co., Ltd.), and the electrodes of the optical semiconductor elements and the second lead electrodes were gold wires (FA manufactured by Tanaka Electronics Industry Co., Ltd.). 25μm) incoming call connection. Thereby, one piece of an LED package substrate (120 packages in terms of number of packages) on which an optical semiconductor element is mounted is obtained. [0098] In the manner described above, optical semiconductor packages with different chip soldering materials were fabricated and used in the following tests. [Wafer Shear Test] Ten of the optical semiconductor packages obtained by the above method were used to measure the wafer shear strength using a bond strength tester (Series 4000 manufactured by Dage Corporation) in a room at 25 ° C. The average of the obtained measured values is expressed in MPa. [0100] [Evaluation of Surface Hardening Obstruction Due to Oxygen] In the optical semiconductor package obtained by the above method, a 25 ° C. room with a sharp tip at the tip was used to rub the periphery of the wafer to confirm the surface hardening obstacle due to oxygen. Whether it is. The obtained results are shown in Tables 3 and 4. [0101] [0103] As shown in Table 3, in Examples 1 to 8 in which a heat-curable polysiloxane composition that satisfies the scope of the present invention was used as a chip soldering material, high hardness, The surface is tacky and overcomes the unhardened surface of the surface due to oxygen barrier. Furthermore, as a result of wafer shear measurement, it was found that an optical semiconductor device with high adhesion and high reliability can be manufactured. [0103] On the other hand, in Comparative Examples 1 and 2 that do not contain the C and D components, although both of them have high hardness and high wafer shear is observed, they have surface stickiness, and it is confirmed that they are caused by oxygen. Its surface hardening hinders. In addition, as is clear from Comparative Example 2, this surface hardening prevention cannot be prevented even by increasing the amount of peroxide. In the case where the amount of the B component is excessive (Comparative Example 3), the viscosity is significantly reduced, and it is impossible to punch. In the case where the C component is excessive (Comparative Example 4), the prevention of the surface hardening due to oxygen can be prevented, but the result is that the shear resistance of the wafer is reduced. In Comparative Example 5, which did not contain the B component and was hardened only with a platinum catalyst, the hardness was significantly reduced, and it became impossible to press due to the increase in viscosity. [0104] The present invention is not limited to the above embodiments. The above-mentioned embodiment is an example, and any one having a structure that is substantially the same as the technical idea described in the patent application scope of the present invention and achieves the same effect is included in the technical scope of the present invention.

[0105][0105]

1‧‧‧框體1‧‧‧frame

2‧‧‧光半導體元件2‧‧‧Optical Semiconductor Element

3‧‧‧第1引線電極3‧‧‧ 1st lead electrode

4‧‧‧第2引線電極4‧‧‧ 2nd lead electrode

5‧‧‧芯片焊接材料(硬化物)5‧‧‧Chip soldering material (hardened)

6、7‧‧‧金線6, 7‧‧‧ gold wire

8‧‧‧密封樹脂8‧‧‧sealing resin

10‧‧‧光半導體裝置10‧‧‧Optical Semiconductor Device

[0020] 　　[第1圖] 係顯示本發明之光半導體裝置之一例的剖面圖。[0020] FIG. 1 is a cross-sectional view showing an example of an optical semiconductor device according to the present invention.

Claims (6)

一種加熱硬化型聚矽氧組成物，其特徵為含有下列(A)～(D)： 　　(A)有機(聚)矽氧烷，係於分子中具有至少1個以下述一般式(1)所表示之構造：100質量份，
Figure TWI654255B_C0001
[式中，m為0、1、2之任一者，R1為氫原子、苯基或鹵化苯基，R2為氫原子或甲基，R3為可取代或非取代且相同或相異之碳原子數1～12之1價之有機基，Z1為-R4-、 -R4-O-、-R4(CH3)2Si-O-(R4為可取代或非取代且相同或相異之碳原子數1～10之2價之有機基)之任一者，Z2為氧原子或是可取代或非取代且相同或相異之碳原子數1～10之2價之有機基]， 　　(B)有機過氧化物，係包含選自由二醯基過氧化物、過氧酯之1種以上：0.1～30質量份， 　　(C)有機氫聚矽氧烷，係於一分子中含有至少2個鍵結於矽原子的氫原子：0.1～20質量份， 　　(D)鉑系觸媒：相對於(A)成分，以(D)成分中之鉑的質量換算計，成為0.01～1,000ppm之量。A heat-curing polysiloxane composition, characterized by containing the following (A) ~ (D): (A) Organic (poly) siloxane, which has at least one molecule in the molecule by the following general formula (1) The structure of the representation: 100 parts by mass,
Figure TWI654255B_C0001
[In the formula, m is any one of 0, 1 , 2, R 1 is a hydrogen atom, a phenyl group, or a halogenated phenyl group, R 2 is a hydrogen atom or a methyl group, and R 3 is a substitutable or unsubstituted and the same or a phase Different monovalent organic groups with 1 to 12 carbon atoms, Z 1 is -R 4- , -R 4 -O-, -R 4 (CH 3 ) 2 Si-O- (R 4 is replaceable or non- Substituted and the same or different carbon atoms of 1 to 10 divalent organic groups) any one, Z 2 is an oxygen atom or can be substituted or unsubstituted and the same or different carbon atoms of 1 to 10 Divalent organic group], (B) Organic peroxides, including one or more selected from diacyl peroxides and peroxyesters: 0.1 to 30 parts by mass, (C) Organic hydrogen polysiloxane, Contains at least 2 hydrogen atoms bonded to silicon atoms in one molecule: 0.1-20 parts by mass, (D) Platinum catalyst: Relative to (A) component, converted to the mass of platinum in (D) component It is calculated as 0.01 to 1,000 ppm. 如請求項1之加熱硬化型聚矽氧組成物，其中，前述(A)成分之有機(聚)矽氧烷之Z1為-R4-，Z2為氧原子。The heat hardening type polysiloxane composition according to claim 1, wherein Z 1 of the organic (poly) siloxane of the aforementioned (A) component is -R 4- , and Z 2 is an oxygen atom. 如請求項1之加熱硬化型聚矽氧組成物，其中，前述(A)成分之有機(聚)矽氧烷之Z1為-R4-O-或-R4(CH3)2Si-O-，Z2為可取代或非取代且相同或相異之碳原子數1～10之2價之有機基。The heat-curing polysiloxane composition according to claim 1, wherein Z 1 of the organic (poly) siloxane of the aforementioned (A) component is -R 4 -O- or -R 4 (CH 3 ) 2 Si- O-, Z 2 is a divalent organic group having 1 to 10 carbon atoms that can be substituted or unsubstituted and has the same or different carbon atoms. 如請求項1至3中任一項之加熱硬化型聚矽氧組成物，其中，前述(A)成分之有機(聚)矽氧烷係於構成該有機(聚)矽氧烷的全矽氧烷單位中具有0.1mol%以上之(SiO2)單位者。The heat-curable polysiloxane composition according to any one of claims 1 to 3, wherein the organic (poly) siloxane of the aforementioned (A) component is based on the total silica constituting the organic (poly) siloxane Among the alkane units, there are 0.1 mol% or more (SiO 2 ) units. 一種芯片焊接材料，其特徵為由如請求項1至4中任一項之加熱硬化型聚矽氧組成物所構成者。A chip soldering material characterized by being composed of the heat-curing polysilicon composition according to any one of claims 1 to 4. 一種光半導體裝置，其特徵為具有將如請求項5之芯片焊接材料硬化所得之硬化物者。An optical semiconductor device characterized by having a hardened product obtained by hardening the die bonding material according to claim 5.
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