TW201833167A - Curable resin composition for light reflection and cured product thereof and optical semiconductor device - Google Patents

Curable resin composition for light reflection and cured product thereof and optical semiconductor device Download PDF

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TW201833167A
TW201833167A TW107102203A TW107102203A TW201833167A TW 201833167 A TW201833167 A TW 201833167A TW 107102203 A TW107102203 A TW 107102203A TW 107102203 A TW107102203 A TW 107102203A TW 201833167 A TW201833167 A TW 201833167A
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resin composition
curable resin
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weight
light reflection
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鈴木弘世
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日商大賽璐股份有限公司
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Priority claimed from JP2017009859A external-priority patent/JP6929069B2/en
Priority claimed from JP2017009860A external-priority patent/JP2018119032A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
    • C08L83/04—Polysiloxanes
    • 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
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

An object of the present invention is to provide a curable resin composition for light reflection with which a reflector by compression molding having higher light reflectivity and being excellent in heat resistance and light resistance can be produced. The present invention provides a curable resin composition for light reflection which comprises an alicyclic epoxy compound (A), a rubber particle other than silicone rubber particle (B), a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H), further comprises a curing agent (E) and a curing accelerator (F), or a curing catalyst (G), and is liquid at 25 DEG C.

Description

光反射用硬化性樹脂組成物及其硬化物，以及光半導體裝置  Curing resin composition for light reflection and cured product thereof, and optical semiconductor device  

本發明係關於光反射用硬化性樹脂組成物及其硬化物以及具備由該硬化物所形成的反射器及光半導體元件之光半導體裝置。本案係主張2017年1月23日在日本提出申請的特願2017-009859及特願2017-009860的優先權，援用其內容。 The present invention relates to a curable resin composition for light reflection and a cured product thereof, and an optical semiconductor device including a reflector and an optical semiconductor element formed of the cured product. The case is based on the priority of Japanese Patent Application No. 2017-009859 and Japanese Patent Application No. 2017-009860 filed on January 23, 2017 in Japan.

近年，各種屋內或屋外的顯示板、影像讀取用光源、交通信號、大型顯示器用單元等，正朝以光半導體元件(LED元件)為光源的發光裝置(光半導體裝置)的採用進展。作為如此的光半導體裝置，一般流行在基板(光半導體元件安裝用基板)上安裝光半導體元件，再將該光半導體元件藉由透明密封材密封而成的光半導體裝置。如此的光半導體裝置的基板，為了提高從光半導體元件發出的光的取出效率，形成有用以反射光的構件(反射器)。 In recent years, various types of indoor and outdoor display panels, light sources for image reading, traffic signals, and units for large displays have been progressing toward the adoption of light-emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources. As such an optical semiconductor device, an optical semiconductor device in which an optical semiconductor element is mounted on a substrate (an optical semiconductor element mounting substrate) and the optical semiconductor element is sealed by a transparent sealing material is generally used. In the substrate of such an optical semiconductor device, in order to improve the extraction efficiency of light emitted from the optical semiconductor element, a member (reflector) for reflecting light is formed.

上述反射器，被要求具有高的光反射性。 傳統上作為上述反射器的構成材料，已知有例如以對苯二甲酸單元為必要構成單元的聚醯胺樹脂(聚鄰苯二甲醯胺樹脂)中，分散有無機填充劑等的樹脂組成物等(參考專利文獻1至3)。 The above reflector is required to have high light reflectivity. Conventionally, as a constituent material of the above-mentioned reflector, for example, a resin composition in which an inorganic filler or the like is dispersed in a polyamide resin (polyphthalamide resin) having a terephthalic acid unit as a constituent unit is known. Etc. (refer to Patent Documents 1 to 3).

而且，作為上述反射器的構成材料，其他已知有例如含有特定比例之包含環氧樹脂的熱硬化性樹脂與折射率1.6至3.0的無機氧化物的光反射用熱硬化性樹脂組成物(參考專利文獻4)。再者，已知有例如含有熱硬化性樹脂成分及1個以上的填充劑成分、熱硬化性樹脂成分全部的折射率與各填充劑成分的折射率的差及由各填充劑成分的體積比例算出的參數控制於特定範圍的光反射用熱硬化性樹脂組成物(參考專利文獻5)。而且，已知有脂環式環氧化合物中調配橡膠粒子及白色顏料的光反射用硬化性樹脂組成物(參考專利文獻6)。 Further, as a constituent material of the above-mentioned reflector, for example, a thermosetting resin composition for light reflection containing a thermosetting resin containing an epoxy resin in a specific ratio and an inorganic oxide having a refractive index of 1.6 to 3.0 is known (refer to Patent Document 4). In addition, for example, a difference between the refractive index of each of the thermosetting resin component, the one or more filler components, and the thermosetting resin component and the refractive index of each filler component, and the volume ratio of each filler component are known. The calculated parameter is controlled by a thermosetting resin composition for light reflection in a specific range (refer to Patent Document 5). In addition, a curable resin composition for light reflection in which rubber particles and a white pigment are blended in an alicyclic epoxy compound is known (refer to Patent Document 6).

[先前技術文獻]  [Previous Technical Literature]   [專利文獻]  [Patent Literature]  

專利文獻1：特開2000-204244號公報 Patent Document 1: JP-A-2000-204244

專利文獻2：特開2004-75994號公報 Patent Document 2: JP-A-2004-75994

專利文獻3：特開2006-257314號公報 Patent Document 3: JP-A-2006-257314

專利文獻4：特開2010-235753號公報 Patent Document 4: JP-A-2010-235753

專利文獻5：特開2010-235756號公報 Patent Document 5: JP-A-2010-235756

專利文獻6：國際公開WO2013/002052號小冊 Patent Document 6: International Publication WO2013/002052

由上述的專利文獻1至6記載的材料所製作的反射器，於以高輸出的藍色光半導體、白色光半導體為光源的光半導體裝置，因從半導體元件發出的光、熱而隨時間發生黃變等的劣化，有光反射性隨時間降低的問題。再者，伴隨無鉛焊料的採用，發光裝置製造時的回焊步驟(焊料回焊步驟)之加熱溫度有變得更高的傾向，於如此的製造步驟，因施加的熱量使上述反射器隨時間劣化，也發生光反射性降低的問題。 The reflector produced by the materials described in the above-mentioned Patent Documents 1 to 6 is an optical semiconductor device using a high-output blue light semiconductor or a white light semiconductor as a light source, and yellow occurs with time due to light and heat emitted from the semiconductor element. Deterioration of the change, there is a problem that the light reflectivity decreases with time. Furthermore, with the use of lead-free solder, the heating temperature of the reflow step (solder reflow step) in the manufacture of the light-emitting device tends to be higher, and in such a manufacturing step, the reflector is made to be time-dependent due to the applied heat. Deterioration also causes a problem that the light reflectivity is lowered.

所以，現況是要求即使對更高輸出、短波長的光或高溫，光反射性亦不易隨時間降低之耐熱性及耐光性佳的材料。 Therefore, the current situation requires a material which is excellent in heat resistance and light resistance which is not easily reduced with time even for higher output, short-wavelength light or high temperature.

而且，上述反射器，一般藉由將形成該反射器用的材料(樹脂組成物)進行轉移成形、壓縮成型而製造。但是，傳統的形成反射器用的樹脂組成物，因大多為適用於轉移成形者，由該樹脂組成物所形成的反射器雖然耐熱性佳，但由壓縮成型所形成的反射器大多耐熱性比較差。 Further, the reflector is generally produced by transfer molding and compression molding of a material (resin composition) for forming the reflector. However, the conventional resin composition for forming a reflector is often suitable for transfer molding, and the reflector formed of the resin composition is excellent in heat resistance, but the reflector formed by compression molding is often poor in heat resistance. .

而且，為了提高專利文獻1至6記載的材料所形成的反射器的反射率、耐熱性而增加無機填充劑的填充量時，組成物的黏度上升而變成固體狀態，也有藉由壓縮成型之形成變困難的問題。 Further, when the reflectance and heat resistance of the reflector formed by the materials described in Patent Documents 1 to 6 are increased and the filling amount of the inorganic filler is increased, the viscosity of the composition is increased to become a solid state, and compression molding is also formed. Difficult problem.

所以，本發明的第1目的，在於提供藉由壓縮成型，可形成具有高光反射性且耐熱性及耐光性佳、 光反射性不易隨時間降低的硬化物之光反射用硬化性樹脂組成物。 In view of the above, a first object of the present invention is to provide a curable resin composition for light reflection which has high light reflectivity, is excellent in heat resistance and light resistance, and has a light reflectance which is less likely to decrease with time.

而且，本發明的另一第1目的，在於提供藉由壓縮成型之生產性佳、具有高光反射性且耐熱性及耐光性佳、光反射性不易隨時間降低的硬化物。 Further, another first object of the present invention is to provide a cured product which is excellent in productivity by compression molding, has high light reflectivity, is excellent in heat resistance and light resistance, and is difficult to reduce light reflectivity with time.

再者，本發明的又一第1目的，在於提供光的亮度不易隨時間降低、信賴性高的光半導體裝置。 Further, another first object of the present invention is to provide an optical semiconductor device in which the luminance of light is less likely to decrease with time and the reliability is high.

而且，也要求於製造光半導體裝置的蝕刻步驟，以反射器構成的基板不易在蝕刻液(例如鹼性溶液)溶出的特性。基板表面在蝕刻液溶出時，光反射性降低(亦即光的取出效率降低)，變得不易確保發光裝置的信賴性。 Further, it is also required to perform an etching step of the optical semiconductor device in which the substrate formed of the reflector is less likely to be eluted in an etching liquid (for example, an alkaline solution). When the surface of the substrate is eluted by the etching liquid, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it becomes difficult to ensure the reliability of the light-emitting device.

所以，本發明的第2目的，在於提供藉由壓縮成型可形成具有高光反射性且耐熱性及耐光性佳、光反射性不易隨時間降低、在蝕刻液不易溶出的硬化物之光反射用硬化性樹脂組成物。 Therefore, a second object of the present invention is to provide a light reflection hardening which can form a cured product which has high light reflectivity, is excellent in heat resistance and light resistance, and has low light reflectivity with time, and is hard to be eluted in an etching liquid by compression molding. Resin composition.

而且，本發明的另一第2目的，在於提供藉由壓縮成型之生產性佳、具有高光反射性且耐熱性及耐光性佳、光反射性不易隨時間降低、在蝕刻液不易溶出的硬化物。 Further, another object of the present invention is to provide a cured product which is excellent in productivity by compression molding, has high light reflectivity, is excellent in heat resistance and light resistance, is less likely to decrease in light reflectivity with time, and is less likely to be eluted in an etching liquid. .

再者，本發明的又一第2目的，在於提供光的亮度不易隨時間降低、信賴性高的光半導體裝置。 Further, another object of the present invention is to provide an optical semiconductor device in which the luminance of light is less likely to decrease with time and the reliability is high.

再者，於上述反射器，被要求於施加因切割加工、溫度變化(例如回焊步驟般非常高溫下的加熱、冷熱循環等)等應力的情況，不易發生裂痕(龜裂)(如此的特性有時稱為「耐龜裂性」)等之強韌性。反射器發生裂痕時， 光反射性降低(亦即光的取出效率降低)，變得不易確保發光裝置的信賴性。 Further, in the above reflector, it is required to apply a stress such as a cutting process or a temperature change (for example, heating at a very high temperature such as a reflow step, a cold cycle, or the like), and cracks (cracks) are unlikely to occur (such characteristics) Sometimes called "crack resistance" and so on. When the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it becomes difficult to ensure the reliability of the light-emitting device.

再者，於上述反射器成形時，也要求成形物不易發生彎曲的特性。反射器成形物發生彎曲時，損害尺寸安定性，光半導體裝置的品質降低。 Further, at the time of molding the above-mentioned reflector, it is also required that the molded article is less likely to be bent. When the reflector molded article is bent, the dimensional stability is impaired, and the quality of the optical semiconductor device is lowered.

本案發明人為了解決上述本發明的第1課題進行專心檢討的結果，發現包含特定的環氧化合物、聚矽氧橡膠(silicone rubber)粒子以外的橡膠粒子、無機填充劑、白色顏料、以及應力緩和劑，又包含硬化劑及硬化促進劑或硬化觸媒，且在25℃為液狀的硬化性樹脂組成物，可形成即使增加無機填充劑或白色顏料的填充量亦可壓縮成型、具有高光反射性且耐熱性及耐光性佳、光反射性不易隨時間降低的硬化物。 In order to solve the above-described first problem of the present invention, the inventors of the present invention found that a specific epoxy compound, rubber particles other than silicone rubber particles, an inorganic filler, a white pigment, and stress relaxation were found. The agent further comprises a hardening agent, a hardening accelerator or a curing catalyst, and is a liquid curable resin composition at 25° C., and can be formed into a compression molding type with high light reflection even if the filling amount of the inorganic filler or the white pigment is increased. A cured product which is excellent in heat resistance and light resistance, and whose light reflectance is not easily lowered with time.

再者，為了解決上述本發明的第2課題進行專心檢討的結果，發現包含脂環式環氧化合物(A)、聚矽氧橡膠粒子以外的橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化劑(E)、硬化促進劑(F)、應力緩和劑(H)、分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)、分子內具有2個以上環氧基的矽氧烷衍生物(J)、以及脂環式聚酯樹脂(K)之在25℃為液狀的光反射用硬化性樹脂組成物，或包含脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化觸媒(G)、應力緩和劑(H)、分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)、分子內具有2個以上 環氧基的矽氧烷衍生物(J)、以及脂環式聚酯樹脂(K)之在25℃為液狀的光反射用硬化性樹脂組成物，可形成即使增加無機填充劑或白色顏料的填充量亦可壓縮成型、具有高光反射性且耐熱性及耐光性佳、光反射性不易隨時間降低、在蝕刻液不易溶出的硬化物。本發明，係基於該等發現而完成者。 In addition, as a result of intensive review of the second problem of the present invention, it was found that rubber particles (B), white pigment (C), and inorganic materials other than the alicyclic epoxy compound (A) and the polyoxyethylene rubber particles were contained. Filler (D), hardener (E), hardening accelerator (F), stress relieving agent (H), isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, intramolecular A siloxane composition (J) having two or more epoxy groups and a viscous resin composition for light reflection at 25 ° C in an alicyclic polyester resin (K), or an alicyclic ring Oxygen compound (A), rubber particles (B), white pigment (C), inorganic filler (D), curing catalyst (G), stress relieving agent (H), and one or more oxirane rings in the molecule The isocyanuric acid derivative (I), the decane derivative (J) having two or more epoxy groups in the molecule, and the alicyclic polyester resin (K) are liquid-reflective at 25 ° C. The curable resin composition can be formed by compression molding even if the filling amount of the inorganic filler or the white pigment is increased, has high light reflectivity, and is excellent in heat resistance and light resistance, and is difficult to reflect light. A cured product that is less likely to dissolve in the etching solution as time passes. The present invention has been completed based on these findings.

亦即，本發明的第1態樣，提供特徵為含有脂環式環氧化合物(A)、聚矽氧橡膠粒子以外的橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、及應力緩和劑(H)，又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)之在25℃為液狀的光反射用硬化性樹脂組成物。 That is, the first aspect of the present invention provides a rubber particle (B), a white pigment (C), and an inorganic filler (D) which are characterized by containing an alicyclic epoxy compound (A) or a polyoxyxylene rubber particle. And the stress relaxation agent (H) further contains a curing agent (E), a curing accelerator (F), or a curing catalyst (G), which is a liquid-reflecting curable resin composition at 25 ° C.

而且，本發明的第2態樣，提供特徵為含有脂環式環氧化合物(A)、聚矽氧橡膠粒子以外的橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)、分子內具有2個以上環氧基的矽氧烷衍生物(J)、及脂環式聚酯樹脂(K)，又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)之在25℃為液狀的光反射用硬化性樹脂組成物。 Further, the second aspect of the present invention provides a rubber particle (B), a white pigment (C), an inorganic filler (D), and the like, which are characterized by containing an alicyclic epoxy compound (A) or a polyoxyxylene rubber particle. a stress relaxation agent (H), an isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, a decane derivative (J) having two or more epoxy groups in the molecule, and a fat The ring-shaped polyester resin (K) further contains a curing agent (E), a curing accelerator (F) or a curing catalyst (G), which is a liquid-reflecting curable resin composition at 25 ° C.

於前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，前述應力緩和劑(H)可為選自聚矽氧橡膠粒子(H1)及聚矽氧油(silicone oil)(H2)所成群的至少1種。 In the first aspect or the second aspect of the curable resin composition for light reflection, the stress relieving agent (H) may be selected from the group consisting of polyoxyethylene rubber particles (H1) and silicone oil ( H2) At least one of the groups.

於前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，前述聚矽氧橡膠粒子(H1)可為表面具備聚矽氧樹脂(silicone resin)的交聯之聚二甲基矽氧烷。 In the first aspect or the second aspect of the curable resin composition for light reflection, the polyoxyxylene rubber particles (H1) may be a crosslinked polydimethyl group having a silicone resin on its surface. Oxane.

於前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，前述聚矽氧油(H2)可為環氧當量3000至15000的具有下述式(1)所示的構造的聚伸烷基醚改質聚矽氧化合物。 In the first aspect or the second aspect of the light-reflecting resin composition for light reflection, the polyfluorene oxide oil (H2) may have a structure represented by the following formula (1) having an epoxy equivalent of from 3,000 to 15,000. A polyalkylene ether modified polyoxime compound.

[式中，x為80至140的整數，y為1至5的整數，z為5至20的整數。R9為碳數2或3的伸烷基。A為具有下述式(1a)所示的構造的聚伸烷基醚基。 [wherein, x is an integer of 80 to 140, y is an integer of 1 to 5, and z is an integer of 5 to 20. R 9 is an alkylene group having 2 or 3 carbon atoms. A is a polyalkylene ether group having a structure represented by the following formula (1a).

(式中，a及b分別獨立為0至40的整數。B為氫原子或甲基。)] (wherein, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group.)]

於前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，前述橡膠粒子(B)可由以(甲基)丙烯酸酯為必要單體成分的聚合物所構成，表面具有羥基及/或羧基，前述橡膠粒子(B)的平均粒徑為10至500nm，最大粒徑為50至1000nm。 In the first aspect or the second aspect of the curable resin composition for light reflection, the rubber particles (B) may be composed of a polymer having (meth) acrylate as an essential monomer component, and having a hydroxyl group on the surface thereof. / or a carboxyl group, the rubber particles (B) have an average particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm.

於前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，前述脂環式環氧化合物(A)可為具有氧化環己烯基的化合物。 In the first aspect or the second aspect of the curable resin composition for light reflection, the alicyclic epoxy compound (A) may be a compound having cyclohexene oxide.

於前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，前述脂環式環氧化合物(A)可包含下述式(I-1) 所示的化合物。 In the first aspect or the second aspect of the curable resin composition for light reflection, the alicyclic epoxy compound (A) may include the following formula (I-1) The compound shown.

於前述第2態樣的光反射用硬化性樹脂組成物，前述異氰脲酸衍生物(I)可為下述式(III-1) [式(III-1)中，R7及R8為相同或不同，表示氫原子或碳數1至8的烷基]所示的化合物。 In the curable resin composition for light reflection according to the second aspect, the isocyanuric acid derivative (I) may be the following formula (III-1) In the formula (III-1), R 7 and R 8 are the same or different and represent a compound represented by a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

於前述第2態樣的光反射用硬化性樹脂組成物，前述脂環式聚酯樹脂(K)可為主鏈具有脂環的脂環式聚酯樹脂。 In the curable resin composition for light reflection according to the second aspect, the alicyclic polyester resin (K) may be an alicyclic polyester resin having an alicyclic ring as a main chain.

於前述第1態樣或第2態樣的光反射用硬 化性樹脂組成物，前述白色顏料(C)可為選自氧化鈦、氧化鋯、氧化鋅及硫酸鋇所成群的至少1種；前述無機填充劑(D)，可為選自氧化矽、氧化鋁、氮化矽、氮化鋁及氮化硼所成群的至少1種。 In the first aspect or the second aspect of the light-reflecting curable resin composition, the white pigment (C) may be at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate; The inorganic filler (D) may be at least one selected from the group consisting of cerium oxide, aluminum oxide, cerium nitride, aluminum nitride, and boron nitride.

前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，可為轉移成形用或壓縮成型用樹脂組成物。 The light-reflecting resin composition for light reflection of the first aspect or the second aspect may be a resin composition for transfer molding or compression molding.

前述第1態樣或第2態樣的光反射用硬化性樹脂組成物，可為反射器形成用樹脂組成物。 The curable resin composition for light reflection of the first aspect or the second aspect may be a resin composition for forming a reflector.

而且，本發明提供前述第1態樣或第2態樣的光反射用硬化性樹脂組成物的硬化物。 Furthermore, the present invention provides a cured product of the curable resin composition for light reflection of the first aspect or the second aspect.

而且，本發明提供特徵為至少具備光半導體元件及由前述第1態樣或第2態樣的光反射用硬化性樹脂組成物的硬化物所構成的反射器的光半導體裝置。 Furthermore, the present invention provides an optical semiconductor device comprising a reflector including at least an optical semiconductor element and a cured product of the curable resin composition for light reflection of the first aspect or the second aspect.

本發明的第1態樣的光反射用硬化性樹脂組成物，因具有上述構成，藉由壓縮成型可形成具有高光反射性且耐熱性及耐光性佳、光反射性不易隨時間降低的硬化物。因此，可提供光的亮度不易隨時間降低、信賴性高的光半導體裝置。 The light-reflecting resin composition for light reflection according to the first aspect of the present invention has the above-described configuration, and can form a cured product having high light reflectivity, excellent heat resistance and light resistance, and low light reflectivity with time due to compression molding. . Therefore, it is possible to provide an optical semiconductor device in which the luminance of light is less likely to decrease with time and the reliability is high.

而且，本發明的第2態樣的硬化性樹脂組成物，因具有上述構成，藉由壓縮成型可形成具有高光反射性且耐熱性及耐光性佳、光反射性不易隨時間降低、在蝕刻液不易溶出的硬化物。因此，可提供光的亮度不易隨時間降低、信賴性高的光半導體裝置。 Further, the curable resin composition of the second aspect of the present invention has the above-described configuration, and can have high light reflectivity by compression molding, and is excellent in heat resistance and light resistance, and light reflectance is less likely to decrease with time. Hardened material that is not easily dissolved. Therefore, it is possible to provide an optical semiconductor device in which the luminance of light is less likely to decrease with time and the reliability is high.

100‧‧‧白色反射器 100‧‧‧White reflector

101‧‧‧金屬配線(電極) 101‧‧‧Metal wiring (electrode)

102‧‧‧光半導體元件的安裝區域 102‧‧‧Installation area of optical semiconductor components

103‧‧‧封裝基板 103‧‧‧Package substrate

104‧‧‧連接銲線 104‧‧‧Connected wire

105‧‧‧光半導體元件的密封材料 105‧‧‧ Sealing materials for optical semiconductor components

106‧‧‧晶粒結著 106‧‧‧Grain

107‧‧‧光半導體元件 107‧‧‧Optical semiconductor components

108‧‧‧散熱器 108‧‧‧ radiator

109‧‧‧陰極標記 109‧‧‧cathode marking

第1圖係表示本發明的光半導體元件安裝用基板之一例的示意圖。左側的圖(a)為斜視圖，右側的圖(b)為剖面圖。 Fig. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention. Figure (a) on the left is a perspective view, and Figure (b) on the right is a cross-sectional view.

第2圖係表示本發明的光半導體裝置的一例的示意圖。 Fig. 2 is a schematic view showing an example of an optical semiconductor device of the present invention.

第3圖係表示本發明的光半導體裝置的另一例的示意圖(剖面圖；具有散熱器的情況)。 Fig. 3 is a schematic view showing a further example of the optical semiconductor device of the present invention (a cross-sectional view; a case having a heat sink).

第4圖係表示本發明的光半導體裝置的又一例的示意圖(具有散熱器(放熱片)的情況)。左側的圖(a)為上視圖，右側的圖(b)為(a)之A-A’剖面圖。 Fig. 4 is a schematic view showing still another example of the optical semiconductor device of the present invention (in the case of having a heat sink (heat radiating sheet)). The figure (a) on the left side is the upper view, and the figure (b) on the right side is the A-A' sectional view of (a).

〈光反射用硬化性樹脂組成物〉  <Curing Resin Composition for Light Reflection>  

本發明的第1態樣的光反射用硬化性樹脂組成物(有只稱為「本發明的第1態樣的硬化性樹脂組成物」的情況)，係含有脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)及應力緩和劑(H)，又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)之在25℃為液狀的硬化性樹脂組成物。換言之，本發明的第1態樣的光反射用硬化性樹脂組成物，係包含脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、硬化劑(E)及硬化促進劑(F)作為必要成分之在25℃為液狀的硬化性樹脂組成物，或包含脂環式環氧化合物(A)、橡膠粒 子(B)、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)及硬化觸媒(G)作為必要成分之在25℃為液狀的硬化性樹脂組成物。 In the first aspect of the present invention, the curable resin composition for light reflection (in the case of the "curable resin composition of the first aspect of the present invention") is an alicyclic epoxy compound (A). ), rubber particles (B), white pigment (C), inorganic filler (D) and stress relieving agent (H), and further contain a hardener (E) and a hardening accelerator (F) or a hardening catalyst (G) It is a liquid curable resin composition at 25 °C. In other words, the curable resin composition for light reflection according to the first aspect of the present invention includes the alicyclic epoxy compound (A), the rubber particles (B), the white pigment (C), and the inorganic filler (D). The stress relaxation agent (H), the hardener (E), and the hardening accelerator (F) are essential constituents of a curable resin composition which is liquid at 25 ° C or contain an alicyclic epoxy compound (A) and rubber particles. (B), a white pigment (C), an inorganic filler (D), a stress relieving agent (H), and a curing catalyst (G) are essential components of a curable resin composition which is liquid at 25 ° C.

而且，本發明的第2態樣的光反射用硬化性樹脂組成物(有只稱為「本發明的第2態樣的硬化性樹脂組成物」的情況)，係含有脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)、分子內具有2個以上環氧基的矽氧烷衍生物(J)及脂環式聚酯樹脂(K)、又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)之在25℃為液狀的硬化性樹脂組成物。再者，前述分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)有稱為「異氰脲酸衍生物(I)」的情況。而且，分子內具有2個以上環氧基的矽氧烷衍生物(J)有稱為「矽氧烷衍生物(J)」的情況。 In addition, the curable resin composition for light reflection according to the second aspect of the present invention (in the case of the "curable resin composition of the second aspect of the present invention") is an alicyclic epoxy compound. (A), rubber particles (B), white pigment (C), inorganic filler (D), stress relieving agent (H), isocyanuric acid derivative having one or more oxirane rings in the molecule (I) a decane derivative (J) having two or more epoxy groups in the molecule, and an alicyclic polyester resin (K), a hardener (E), a hardening accelerator (F) or a hardening catalyst ( G) is a liquid curable resin composition at 25 ° C. In addition, the isocyanuric acid derivative (I) having one or more oxirane rings in the molecule may be referred to as "isocyanuric acid derivative (I)". Further, the decane derivative (J) having two or more epoxy groups in the molecule may be referred to as "a siloxane derivative (J)".

換言之，本發明的第2態樣的硬化性樹脂組成物，係包含脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化劑(E)、硬化促進劑(F)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)作為必要成分之在25℃為液狀的光反射用硬化性樹脂組成物，或包含脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化觸媒(G)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)作為必要成分之在25℃為液狀的硬化性樹脂組成物。再者，本發明的第1態樣或第2態樣的硬 化性樹脂組成物(有只稱為「本發明的硬化性組成物」的情況)，除上述必要成分外，依需要亦可包含其他成分。再者，本發明的第1態樣或第2態樣的硬化性樹脂組成物，可使用作為藉由加熱使其硬化之能夠轉化為硬化物的熱硬化性組成物(熱硬化性環氧樹脂組成物)。 In other words, the curable resin composition according to the second aspect of the present invention includes the alicyclic epoxy compound (A), the rubber particles (B), the white pigment (C), the inorganic filler (D), and the curing agent ( E), a hardening accelerator (F), a stress relieving agent (H), an isocyanuric acid derivative (I), a decane derivative (J), and an alicyclic polyester resin (K) as essential components 25° C. is a liquid curable resin composition for light reflection, or contains an alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), and hardening catalyst ( G), stress relieving agent (H), isocyanuric acid derivative (I), decane derivative (J) and alicyclic polyester resin (K) as essential components, liquid hardening at 25 ° C Resin composition. In addition, the curable resin composition of the first aspect or the second aspect of the present invention (in the case of only the "curable composition of the present invention") may be contained as needed in addition to the above-mentioned essential components. Other ingredients. Further, in the first aspect or the second aspect of the curable resin composition of the present invention, a thermosetting composition (thermosetting epoxy resin) which can be converted into a cured product by curing by heating can be used. Composition)).

再者，於本說明書，所謂「光反射用硬化性樹脂組成物」，係指能夠形成具有光反射性的硬化物之硬化性樹脂組成物。具體而言例如以能夠形成對波長450nm的光之反射率為50%以上(特別是80%以上)的硬化物之硬化性樹脂組成物為佳。 In the present specification, the term "curable resin composition for light reflection" means a curable resin composition capable of forming a cured product having light reflectivity. Specifically, for example, a curable resin composition capable of forming a cured product having a reflectance of light having a wavelength of 450 nm of 50% or more (particularly 80% or more) is preferable.

本發明的第1態樣或第2態樣的硬化性樹脂組成物，藉由在25℃為液體，有適用於壓縮成型的傾向，其硬化物(反射器)具有光反射性佳且耐熱性及耐光性佳的傾向。再者，於本說明書，所謂「在25℃為液體」係指於常壓、在25℃測定的黏度為1000000mPa‧s以下(較理想為800000mPa‧s以下)。再者，上述黏度，例如可使用數位黏度計(型號「DVU-EII型」、(股)TOKIMEC公司製)，在轉子：標準1°34’×R24、溫度：25℃、旋轉數：0.5至10rpm的條件下測定。 The curable resin composition of the first aspect or the second aspect of the present invention has a tendency to be suitable for compression molding by being liquid at 25 ° C, and the cured product (reflector) has excellent light reflectivity and heat resistance. And the tendency to light resistance is good. In the present specification, the phrase "liquid at 25 ° C" means a viscosity measured at 25 ° C under normal pressure of 1,000,000 mPa ‧ s or less (more preferably 800,000 mPa ‧ s or less). Further, as the viscosity, for example, a digital viscometer (model "DVU-EII type", manufactured by TOKIMEC Co., Ltd.) can be used, and the rotor: standard 1° 34' × R24, temperature: 25 ° C, rotation number: 0.5 to Measured under conditions of 10 rpm.

在25℃為液體的本發明的第1態樣或第2態樣的硬化性樹脂組成物，例如藉由使用在25℃為液體的成分作為成分(例如脂環式環氧化合物(A)、液狀的應力緩和劑(H)、硬化劑(E)、硬化促進劑(F)、硬化觸媒(G))而容易製得。再者，作為上述成分，亦可使用在25℃為固體的 成分，但其含量調整為使本發明的硬化性樹脂組成物在25℃成為液狀。而且，橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、固體的應力緩和劑(H)等在25℃為固體的成分的含量，藉由調整在無損本發明的效果的範圍內，也可容易製得。 The curable resin composition of the first aspect or the second aspect of the present invention which is liquid at 25 ° C, for example, by using a component which is liquid at 25 ° C as a component (for example, an alicyclic epoxy compound (A), The liquid stress relieving agent (H), the curing agent (E), the curing accelerator (F), and the curing catalyst (G) are easily produced. Further, as the above-mentioned component, a component which is solid at 25 ° C may be used, but the content thereof is adjusted so that the curable resin composition of the present invention becomes liquid at 25 °C. Further, the content of the component which is solid at 25 ° C, such as the rubber particles (B), the white pigment (C), the inorganic filler (D), and the solid stress relieving agent (H), is adjusted without impairing the effects of the present invention. Within the scope, it can also be easily produced.

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

本發明的第1態樣或第2態樣的硬化性樹脂組成物的必要成分之脂環式環氧化合物(脂環式環氧樹脂)(A)，係分子內(一分子中)至少具有脂環(脂肪族烴環)構造及環氧基(環氧乙烷基)的化合物，可使用習知至慣用的脂環式環氧化合物。但是，於本發明的第2態樣的硬化性樹脂組成物，從脂環式環氧化合物(A)中排除對應異氰脲酸衍生物(I)及矽氧烷衍生物(J)者。作為脂環式環氧化合物(A)，更具體者例如(i)具有構成脂環的鄰接的2個碳原子與氧原子所構成的環氧基(脂環式環氧基)之化合物、(ii)具有以直接單鍵結合於脂環的環氧基的化合物。 The alicyclic epoxy compound (alicyclic epoxy resin) (A) which is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention has at least one molecule (in one molecule) As the alicyclic (aliphatic hydrocarbon ring) structure and the epoxy group (oxiranyl group), a conventional to conventional alicyclic epoxy compound can be used. However, in the curable resin composition of the second aspect of the present invention, the corresponding isocyanuric acid derivative (I) and the decane derivative (J) are excluded from the alicyclic epoxy compound (A). More specifically, as the alicyclic epoxy compound (A), for example, (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring, Ii) a compound having an epoxy group bonded directly to the alicyclic ring by a single bond.

作為上述(i)具有脂環式環氧基之化合物，可使用分子內具有1個以上脂環式環氧基的習知至慣用的化合物，無特別限制。作為上述脂環式環氧基，在硬化性樹脂組成物的硬化性及硬化物(反射器)的耐熱性及耐光性(特別是耐紫外線性)的觀點，較理想為氧化環己烯基。特別是在硬化物(反射器)的耐熱性及耐光性(特別是耐紫外線性)的觀點，較理想為分子內具有2個以上氧化環己烯基 的化合物，更理想為下述式(I)所示的化合物。 As the compound (i) having an alicyclic epoxy group, a conventional to conventional compound having one or more alicyclic epoxy groups in the molecule can be used, and it is not particularly limited. The alicyclic epoxy group is preferably cyclohexene oxide in view of curability of the curable resin composition, heat resistance of the cured product (reflector), and light resistance (particularly, ultraviolet resistance). In particular, in view of heat resistance and light resistance (particularly ultraviolet resistance) of the cured product (reflector), a compound having two or more cyclohexene oxide groups in the molecule is preferable, and more preferably, it is the following formula (I). ) the compound shown.

式(I)中，X表示單鍵或連結基(具有1個以上原子的2價基)。作為上述連結基，例如2價的烴基、碳-碳雙鍵的一部分或全部被環氧基化的伸烯基(有稱為「環氧基化伸烯基」的情況)、羰基、醚鍵、酯鍵、碳酸酯基、醯胺基及該等複數個連結而成的基等。再者，在構成式(I)之環己烷環(氧化環己烯基)的碳原子的1個以上，可鍵結烷基等取代基。 In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). The above-mentioned linking group is, for example, a divalent hydrocarbon group or an alkenyl group in which a part or all of a carbon-carbon double bond is epoxidized (in the case of an "epoxylated alkenyl group"), a carbonyl group or an ether bond. And an ester bond, a carbonate group, a guanamine group, and a plurality of such linked groups. In addition, one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide) of the formula (I) may be bonded to a substituent such as an alkyl group.

作為式(I)中的X為單鍵的化合物，例如(3,4,3’,4’-二環氧基)雙環己烷等。 The compound in which X in the formula (I) is a single bond is, for example, (3,4,3',4'-dicyclooxy)bicyclohexane or the like.

作為上述2價烴基，例如碳數1至18的直鏈或分支鏈狀的伸烷基、2價的脂環式烴基等。作為碳數1至18的直鏈或分支鏈狀的伸烷基，例如亞甲基、甲基亞甲基、二甲基亞甲基、伸乙基、伸丙基、三亞甲基等。作為上述2價的脂環式烴基，例如1,2-伸環戊基、1,3-伸環戊基、亞環戊基、1,2-伸環己基、1,3-伸環己基、1,4-伸環己基、亞環己基等伸環烷基(包含亞環烷基)等。 The divalent hydrocarbon group is, for example, a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group or the like. As the linear or branched alkylene group having 1 to 18 carbon atoms, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group, a trimethylene group or the like. The divalent alicyclic hydrocarbon group is, for example, a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a cyclohexylene group or the like cycloalkyl group (including a cycloalkylene group).

作為上述碳-碳雙鍵的一部分或全部被環氧基化的伸烯基(環氧基化伸烯基)中之伸烯基，例如伸乙烯基、伸丙烯基、1-伸丁烯基、2-伸丁烯基、伸丁二烯基、伸戊烯基、伸己烯基、伸庚烯基、伸辛烯基等碳數2至8的直鏈或分支鏈狀的伸烯基等。特別是作為上述環氧基化 伸烯基，較理想為碳-碳雙鍵的全部被環氧基化的伸烯基，更理想為碳-碳雙鍵的全部被環氧基化的碳數2至4的伸烯基。 An alkenyl group in an alkenyl group (epoxylated alkenyl group) which is epoxidized as a part or the whole of the above carbon-carbon double bond, for example, a vinyl group, a propenyl group, a 1-butenyl group a 2- or less-butenyl group, a butadienyl group, a pentenyl group, a hexenylene group, a heptenyl group, a exemplified alkenyl group, and the like, and a linear or branched alkenyl group having 2 to 8 carbon atoms; Wait. In particular, the epoxy group-extended alkenyl group is preferably an epoxy group-extended alkenyl group in which all of the carbon-carbon double bonds are epoxidized, and more preferably the carbon number of the carbon-carbon double bond is epoxidized. 2 to 4 of an alkenyl group.

作為上述X之連結基，特別理想為含有氧原子的連結基，具體者例如-CO-、-Ｏ-CO-O-、-COO-、-O-、-CONH-、環氧基化伸烯基；該等基複數個連結而成的基；該等基的1個或2個以上與2價烴基的1個或2個以上連結而成的基等。作為2價烴基，例如上述例示者。 As the linking group of X described above, a linking group containing an oxygen atom is particularly preferable, and specific examples thereof include -CO-, -O-CO-O-, -COO-, -O-, -CONH-, and epoxidized alkylene. A group in which a plurality of these groups are linked; a group in which one or two or more of the groups are bonded to one or two or more of the divalent hydrocarbon groups. The divalent hydrocarbon group is, for example, the above-exemplified.

作為上述式(I)所示化合物的代表例，例如下述式(I-1)至(I-10)所示的化合物、2,2-雙(3,4-環氧基環己烷-1-基)丙烷、1,2-雙(3,4-環氧基環己烷-1-基)乙烷、1,2-環氧基-1,2-雙(3,4-環氧基環己烷-1-基)乙烷、雙(3,4-環氧基環己基甲基)醚等。再者，下述式(I-5)、(I-7)中的l、m，分別表示1至30的整數。下述式(I-5)中的R為碳數1至8的伸烷基，例如亞甲基、伸乙基、伸丙基、伸異丙基、伸丁基、伸異丁基、s-伸丁基、伸戊基、伸己基、伸庚基、伸辛基等直鏈或分支鏈狀的伸烷基。該等之中，較理想為亞甲基、伸乙基、伸丙基、伸異丙基等碳數1至3的直鏈或分支鏈狀的伸烷基。下述式(I-9)、(I-10)中的n1至n6分別表示1至30的整數。 As a representative example of the compound represented by the above formula (I), for example, a compound represented by the following formulas (I-1) to (I-10), 2,2-bis(3,4-epoxycyclohexane- 1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxy Cyclohexane-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl)ether, and the like. Further, l and m in the following formulae (I-5) and (I-7) each represent an integer of 1 to 30. R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, such as methylene, ethyl, propyl, isopropyl, butyl, isobutyl, s. - a straight or branched chain alkyl group such as a butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methylene group, an ethyl group, a propyl group, and an isopropyl group is preferable. N1 to n6 in the following formulae (I-9) and (I-10) each represent an integer of 1 to 30.

作為上述(ii)具有以直接單鍵結合於脂環的環氧基的化合物，例如下述式(II)所示的化合物(環氧樹脂)。 As the compound (ii) having an epoxy group bonded directly to the alicyclic ring by a single bond, for example, a compound (epoxy resin) represented by the following formula (II).

上述式(II)中，R1表示p價的有機基。p表示1至20的整數。作為p價的有機基，例如具有從後述的具有p個羥基的有機化合物的構造式除去p個羥基所形成的構造的p價的有機基等。 In the above formula (II), R 1 represents a p-valent organic group. p represents an integer of 1 to 20. The p-valent organic group is, for example, a p-valent organic group having a structure in which p hydroxyl groups are removed from a structural formula of an organic compound having p hydroxyl groups, which will be described later.

式(II)中，q表示1至50的整數。再者，p為2以上的整數的情況，複數的q可為相同，亦可為不同。式(II)之q的和(總和)為3至100的整數。 In the formula (II), q represents an integer of 1 to 50. Further, when p is an integer of 2 or more, the plural q may be the same or different. The sum (sum) of q of the formula (II) is an integer of from 3 to 100.

式(II)中，R2為式中所示的環己烷環上的取代基，表示以下述式(IIa)至(IIc)所示的基之任一者。上述環己烷環上的R2的鍵結位置雖無特別限制，但通常於與氧原子鍵結的環己烷環的2個碳原子的位置為1位、2位的情況為4位或5位的碳原子。而且，式(II)所示的化合物具有複數個環己烷環的情況，各環己烷環的R2的鍵結位置，可為相同，亦可為不同。式(II)的R2的至少之一為式(IIa)所示的基(環氧基)。再者，式(II)所示的化合物具有2個以上的R2的情況，複數個R2可為相同，亦可為不同。 In the formula (II), R 2 is a substituent on the cyclohexane ring represented by the formula, and represents any one of the groups represented by the following formulas (IIa) to (IIc). The bonding position of R 2 on the above cyclohexane ring is not particularly limited, but is usually 4 positions in the case where the position of the two carbon atoms of the cyclohexane ring bonded to the oxygen atom is 1 position or 2 positions. 5-position carbon atom. Further, when the compound represented by the formula (II) has a plurality of cyclohexane rings, the bonding positions of R 2 in each cyclohexane ring may be the same or different. At least one of R 2 of the formula (II) is a group (epoxy group) represented by the formula (IIa). Further, when the compound represented by the formula (II) has two or more R 2 's, the plurality of R 2 's may be the same or different.

-CH=CH2 (IIb) -CH=CH 2 (IIb)

式(IIc)中，R3表示氫原子、取代或無取代的烷基、取代或無取代的烷基羰基、或取代或無取代的芳香基羰基。作為上述烷基，例如甲基、乙基、正丙基、異丙基、丁基、異丁基、s-丁基、t-丁基、戊基、己基、辛基、2-乙基己基等碳數1至20的直鏈或分支鏈狀的烷基等。作為上述烷基羰基，例如甲基羰基(乙醯基)、乙基羰基、正丙基羰基、異丙基羰基、正丁基羰基、異丁基羰基、s-丁基羰基、t-丁基羰基等碳數1至20的直鏈或分支鏈狀的烷基羰基等。作為上述芳香基羰基，例如苯基羰基(苯甲醯基)、1-萘基羰基、2-萘基羰基等碳數6至20的芳香基羰基。 In the formula (IIc), R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. As the above alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl A linear or branched alkyl group having a carbon number of 1 to 20 or the like. As the above alkylcarbonyl group, for example, methylcarbonyl (ethinyl), ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, s-butylcarbonyl, t-butyl A linear or branched alkylcarbonyl group having 1 to 20 carbon atoms such as a carbonyl group. The above arylcarbonyl group is, for example, an arylcarbonyl group having 6 to 20 carbon atoms such as a phenylcarbonyl group (benzimidyl group), a 1-naphthylcarbonyl group or a 2-naphthylcarbonyl group.

上述烷基、烷基羰基、芳香基羰基可具有的取代基，例如碳數0至20(更理想為碳數0至10)的取代基等。作為上述取代基，例如氟原子、氯原子、溴原子、碘原子等鹵素原子；羥基；甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基等烷氧基(較理想為C1-6烷氧基，更理想為C1-4烷氧基)；烯丙氧基等烯氧基(較理想為C2-6烯氧基，更理想為C2-4烯氧基)；乙醯氧基、丙醯氧基、(甲基)丙烯醯氧基等醯氧基(較理想為C1-12醯氧基)；硫醇基；甲硫基、乙硫基等烷硫基(較理想為C1-6烷硫基，更理想為C1-4烷硫基)；烯丙硫基等烯硫基(較理想為C2-6烯硫 基，更理想為C2-4烯硫基)；羧基；甲氧基羰基、乙氧基羰基、丙氧基羰基、丁氧基羰基等烷氧基羰基(較理想為C1-6烷氧基-羰基)；胺基；甲基胺基、乙基胺基、二甲基胺基、二乙基胺基等單或二-烷基胺基(較理想為單或二-C1-6烷基胺基)；乙醯基胺基、丙醯基胺基等醯基胺基(較理想為C1-11醯基胺基)；乙基氧雜環丁烷氧基等含有氧雜環丁烷基的基；乙醯基、丙醯基等醯基；側氧基(oxo)；此等的2個以上依需要隔著C1-6伸烷基結合而成的基等。而且，作為上述芳香基羰基可具有的取代基，例如上述取代或無取代的烷基，上述取代或無取代的烷基羰基。 The substituent which the above-mentioned alkyl group, alkylcarbonyl group, or arylcarbonyl group may have, for example, a substituent having a carbon number of from 0 to 20 (more preferably from 0 to 10 carbon atoms). Examples of the above substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxyl group; and an alkyl group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group. An oxy group (preferably a C 1-6 alkoxy group, more preferably a C 1-4 alkoxy group); an alkenyloxy group such as an allyloxy group (preferably a C 2-6 alkenyloxy group, more preferably C) 2-4 alkenyloxy); an oxiranyloxy group (preferably a C 1-12 decyloxy group) such as an ethoxycarbonyl group, a propyl decyloxy group or a (meth) acryloxy group; a thiol group; a methylthio group; , an alkylthio group such as an ethylthio group (preferably a C 1-6 alkylthio group, more preferably a C 1-4 alkylthio group); an allylthio group such as an allylthio group (preferably a C 2-6 alkene sulfide) More preferably, it is a C 2-4 alkenyl group; a carboxyl group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group or a butoxycarbonyl group (preferably a C 1-6 alkoxy group) Alkyl-carbonyl); an amine group; a mono- or di-alkylamino group such as a methylamino group, an ethylamino group, a dimethylamino group or a diethylamino group (preferably a mono- or di-C 1-6) alkylamino); acetylsalicylic group, a propyl group and the like acyl acyl group (more desirably C 1-11 acyl group); ethyloxetane Oxetanyl group-containing alkyl group; acetyl, propionyl and the like acyl acyl; oxo (oxo); these two or more as needed via a C 1-6 alkylene bonded Base and so on. Further, as the substituent which the above arylcarbonyl group may have, for example, the above-mentioned substituted or unsubstituted alkyl group, the above substituted or unsubstituted alkylcarbonyl group.

對式(II)所示的化合物之R2的全部量(100莫耳%)而言，式(IIa)所示的基(環氧基)的比例，雖無特別限制，但以40莫耳%以上(例如40至100莫耳%)較理想，更理想為60莫耳%以上，又更理想為80莫耳%以上。上述比例為40莫耳%以上時，有更提高硬化物的耐熱性、耐光性、機械特性等的傾向。再者，上述比例，可藉由例如1H-NMR光譜測定、環氧乙烷氧濃度測定等算出。 The entire amount (100 mole%) R of the compound of formula (II) shown in FIG. 2, the proportion of formula (IIa) of group (epoxy group) as shown, is not particularly limited, but 40 mole More than % (for example, 40 to 100 mol%) is more preferably 60 mol% or more, and still more desirably 80 mol% or more. When the ratio is 40 mol% or more, the heat resistance, light resistance, mechanical properties, and the like of the cured product tend to be improved. Further, the above ratio can be calculated by, for example, 1 H-NMR spectrum measurement, oxirane oxygen concentration measurement, or the like.

式(II)所示的化合物，雖無特別限制，但可藉由例如以分子內具有p個羥基的有機化合物[R1(OH)p]作為引發劑(亦即以該化合物的羥基(活性氫)作為出發點)，使1,2-環氧基-4-乙烯基環己烷(3-乙烯基-4-氧雜雙環[4.1.0]庚烷)開環聚合(陽離子聚合)，然後藉由氧化劑進行環氧基化而製造。 The compound represented by the formula (II) is not particularly limited, but may be, for example, an organic compound having a p-hydroxy group in the molecule [R 1 (OH) p ] as an initiator (that is, a hydroxyl group of the compound (active) Hydrogen) as a starting point, ring-opening polymerization (cationic polymerization) of 1,2-epoxy-4-vinylcyclohexane (3-vinyl-4-oxabicyclo[4.1.0]heptane), and then It is produced by epoxidation by an oxidizing agent.

作為上述分子內具有p個羥基的有機化合 物[R1(OH)p]，例如甲醇、乙醇、丙醇、丁醇、戊醇、己醇、辛醇等脂肪族醇；乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、二丙二醇、1,3-丁二醇、1,4-丁二醇、戊二醇、1,6-己二醇、新戊二醇、新戊二醇酯、環己二甲醇、丙三醇、二丙三醇、聚丙三醇、三羥甲基丙烷、季戊四醇、二季戊四醇、氫化雙酚A、氫化雙酚F、氫化雙酚S等多價醇；聚乙烯醇、聚乙酸乙烯酯部分水解物、澱粉、丙烯酸聚醇樹脂、苯乙烯-烯丙醇共聚合樹脂、聚酯聚醇、聚己內酯聚醇、聚丙烯聚醇、聚丁二醇、聚碳酸酯聚醇類、具有羥基的聚丁二烯、纖維素、纖維素乙酸酯、纖維素乙酸酯丁酸酯、羥基乙基纖維素等纖維素系聚合物等具有羥基的寡聚物或聚合物等。 As the organic compound [R 1 (OH) p ] having p hydroxyl groups in the above molecule, for example, an aliphatic alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol or octanol; ethylene glycol, diethyl Glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol , neopentyl glycol ester, cyclohexanedimethanol, glycerol, diglycerol, polyglycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S Polyvalent alcohol; polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, acrylic polyol resin, styrene-allyl alcohol copolymer resin, polyester polyol, polycaprolactone polyol, polypropylene polyol , polytetramethylene glycol, polycarbonate polyalcohol, polybutadiene having hydroxyl group, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, etc. An oligomer or polymer having a hydroxyl group or the like.

上述1,2-環氧基-4-乙烯基環己烷，可藉由習知至慣用的方法製造，雖無特別限制，但例如可藉由對丁二烯的二聚反應所得之4-乙烯基環己烯，使用過氧化乙酸等氧化劑進行部分環氧基化而得。而且，作為1,2-環氧基-4-乙烯基環己烷，可使用市售品。 The above 1,2-epoxy-4-vinylcyclohexane can be produced by a conventionally known method, and is not particularly limited, but can be obtained, for example, by dimerization of butadiene. Vinylcyclohexene is obtained by partial epoxidation using an oxidizing agent such as peracetic acid. Further, as the 1,2-epoxy-4-vinylcyclohexane, a commercially available product can be used.

而且，作為上述氧化劑，可使用過氧化氫、有機過氧化酸等習知至慣用的氧化劑，並無特別限制，作為有機過氧化酸，例如過氧化甲酸、過氧化乙酸、過氧化安息香酸、三氟過氧化乙酸等。其中，過氧化乙酸因工業上能夠便宜取得，且安定度也高，所以較理想。 Further, as the oxidizing agent, a conventional to conventional oxidizing agent such as hydrogen peroxide or an organic peroxy acid can be used, and it is not particularly limited as an organic peroxyacid such as peroxyformic acid, peracetic acid, peroxidized benzoic acid, or the like. Fluorine peracetic acid or the like. Among them, peracetic acid is preferable because it can be obtained industrially inexpensively and has high stability.

再者，上述開環聚合及環氧基化，更具體者例如可根據特開昭60-161973號公報記載的習知慣用方 法實施。 In addition, the ring-opening polymerization and the epoxidation can be carried out, for example, in accordance with a conventional method described in JP-A-60-161973.

式(II)所示化合物的換算標準聚苯乙烯的重量平均分子量雖無特別限制，但較佳為300至100000，更佳為1000至10000。重量平均分子量為300以上時，有提高硬化物的機械強度、耐熱性、耐光性的傾向。另一方面，重量平均分子量為100000以下時，黏度不會變得太高，容易維持成形時的流動性低的傾向。再者，重量平均分子量係藉由凝膠滲透層析(GPC)法測定。 The weight average molecular weight of the converted standard polystyrene of the compound represented by the formula (II) is not particularly limited, but is preferably from 300 to 100,000, more preferably from 1,000 to 10,000. When the weight average molecular weight is 300 or more, the mechanical strength, heat resistance, and light resistance of the cured product tend to be improved. On the other hand, when the weight average molecular weight is 100,000 or less, the viscosity does not become too high, and the fluidity at the time of molding tends to be low. Further, the weight average molecular weight is determined by a gel permeation chromatography (GPC) method.

式(II)所示化合物的環氧基當量(環氧當量)雖無特別限制，但較佳為50至1000，更佳為100至500。環氧當量為50以上時，有硬化物不易變脆的傾向。另一方面，環氧當量為1000以下時，有提高硬化物的機械強度的傾向。再者，環氧當量係根據JIS K7236：2001測定。 The epoxy equivalent (epoxy equivalent) of the compound of the formula (II) is not particularly limited, but is preferably from 50 to 1,000, more preferably from 100 to 500. When the epoxy equivalent is 50 or more, the cured product tends to be less likely to become brittle. On the other hand, when the epoxy equivalent is 1000 or less, the mechanical strength of the cured product tends to increase. Further, the epoxy equivalent is measured in accordance with JIS K7236:2001.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物，脂環式環氧化合物(A)可使用單獨1種，亦可組合2種以上使用。而且，脂環式環氧化合物(A)可藉由習知至慣用的方法製造，亦可使用例如商品名「CELLOXIDE 2021P」、「CELLOXIDE 2081」、「EHPE 3150」(以上(股)DAICEL公司製)等市售品。 In the first aspect or the second aspect of the present invention, the alicyclic epoxy compound (A) may be used alone or in combination of two or more. Further, the alicyclic epoxy compound (A) can be produced by a conventionally known method, and for example, "CELLOXIDE 2021P", "CELLOXIDE 2081", and "EHPE 3150" (manufactured by DAICEL Co., Ltd.) can also be used. ) and other commercial products.

脂環式環氧化合物(A)，從調配時及注模時等的操作性的點，以常溫(25℃)下呈現液狀者較佳。而且，即使常溫(25℃)下為固體的脂環式環氧化合物(A)，只要是調配後呈現液狀者，亦可含有。 The alicyclic epoxy compound (A) is preferably a liquid at room temperature (25 ° C) from the viewpoint of operability at the time of preparation and injection molding. In addition, even if the alicyclic epoxy compound (A) which is solid at normal temperature (25 ° C) is liquid after being formulated, it may be contained.

其中，本發明的第1態樣或第2態樣的硬 化性樹脂組成物，從更提高硬化物(反射器)的光反射性、耐熱性及耐光性的觀點，以至少包含(i)具有脂環式環氧基之化合物較佳，以更包含(ii)具有以直接單鍵結合於脂環的環氧基的化合物更佳。 In addition, the curable resin composition of the first aspect or the second aspect of the present invention contains at least (i) from the viewpoint of further improving the light reflectivity, heat resistance and light resistance of the cured product (reflector). The alicyclic epoxy group-containing compound is preferred to further comprise (ii) a compound having an epoxy group which is directly bonded to the alicyclic ring by a single bond.

本發明的第1態樣的硬化性樹脂組成物之脂環式環氧化合物(A)的含量(調配量)雖無特別限制，但是對硬化性樹脂組成物(100重量%)而言，較理想為1.5至60重量%，更理想為2至50重量%，又更理想為5至40重量%。藉由使脂環式環氧化合物(A)的含量為1.5重量%以上，有更提高硬化物(反射器)的耐熱性(特別是耐黃變性)及耐光性(特別是耐紫外線性)的傾向。另一方面，藉由使脂環式環氧化合物(A)的含量為60重量%以下，可減少硬化物(反射器)的線膨脹係數，有抑制光半導體元件安裝用基板之引線架翹曲等缺陷發生的傾向。 The content (mixing amount) of the alicyclic epoxy compound (A) of the curable resin composition of the first aspect of the invention is not particularly limited, but the curable resin composition (100% by weight) is more It is desirably from 1.5 to 60% by weight, more desirably from 2 to 50% by weight, still more preferably from 5 to 40% by weight. When the content of the alicyclic epoxy compound (A) is 1.5% by weight or more, the heat resistance (especially yellowing resistance) and light resistance (particularly, ultraviolet resistance) of the cured product (reflector) are further improved. tendency. On the other hand, when the content of the alicyclic epoxy compound (A) is 60% by weight or less, the linear expansion coefficient of the cured product (reflector) can be reduced, and the lead frame warpage of the substrate for mounting the optical semiconductor element can be suppressed. The tendency for defects to occur.

本發明的第2態樣的硬化性樹脂組成物之脂環式環氧化合物(A)的含量(調配量)雖無特別限制，但是對硬化性樹脂組成物(100重量%)而言，較理想為0.1至60重量%，更理想為0.3至50重量%，又更理想為0.5至40重量%。藉由使脂環式環氧化合物(A)的含量為0.1重量%以上，有更提高硬化物(反射器)的耐熱性(特別是耐黃變性)及耐光性(特別是耐紫外線性)的傾向。另一方面，藉由使脂環式環氧化合物(A)的含量為60重量%以下，可減少線膨脹係數，有抑制光半導體元件安裝用基板之引線架翹曲等缺陷發生的傾向。 The content (adjusted amount) of the alicyclic epoxy compound (A) of the curable resin composition of the second aspect of the present invention is not particularly limited, but the curable resin composition (100% by weight) is more It is desirably from 0.1 to 60% by weight, more desirably from 0.3 to 50% by weight, still more preferably from 0.5 to 40% by weight. When the content of the alicyclic epoxy compound (A) is 0.1% by weight or more, the heat resistance (especially yellowing resistance) and light resistance (particularly, ultraviolet resistance) of the cured product (reflector) are further improved. tendency. On the other hand, when the content of the alicyclic epoxy compound (A) is 60% by weight or less, the linear expansion coefficient can be reduced, and defects such as warpage of the lead frame of the optical semiconductor element mounting substrate can be suppressed.

對包含於本發明的第1態樣的硬化性樹脂組成物之具有環氧基的化合物全部量(100重量%)而言，脂環式環氧化合物(A)的比例雖無特別限制，但較理想為50重量%以上(例如50至100重量%)，更理想為60重量%以上，又更理想為80重量%以上，特佳為90重量%以上。藉由使上述比例為50重量%以上，有更提高硬化物(反射器)的耐熱性及耐光性的傾向。 The total amount (100% by weight) of the epoxy group-containing compound of the curable resin composition of the first aspect of the present invention is not particularly limited as long as the ratio of the alicyclic epoxy compound (A) is It is preferably 50% by weight or more (for example, 50 to 100% by weight), more preferably 60% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more. When the ratio is 50% by weight or more, the heat resistance and light resistance of the cured product (reflector) tend to be improved.

對包含於本發明的第2態樣的硬化性樹脂組成物之具有環氧基的化合物全部量(100重量%)而言，脂環式環氧化合物(A)的比例雖無特別限制，但以例如1至90重量%較理想，更理想為5至80重量%，又更理想為10至70重量%。藉由使其在上述範圍內，有更提高硬化物(反射器)的耐熱性及耐光性的傾向。再者，作為包含於本發明的第2態樣的硬化性樹脂組成物之具有環氧基的化合物，例如脂環式環氧化合物(A)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)、具有環氧基的應力緩和劑(H)(環氧基改質聚矽氧油等)等。 The total amount (100% by weight) of the epoxy group-containing compound of the curable resin composition of the second aspect of the present invention is not particularly limited as long as the ratio of the alicyclic epoxy compound (A) is It is preferably, for example, 1 to 90% by weight, more preferably 5 to 80% by weight, still more preferably 10 to 70% by weight. When it is in the above range, the heat resistance and light resistance of the cured product (reflector) tend to be improved. Further, as the epoxy group-containing compound contained in the curable resin composition of the second aspect of the present invention, for example, an alicyclic epoxy compound (A), an isocyanuric acid derivative (I), and an oxygen-oxygen group An alkane derivative (J), a stress relieving agent (H) having an epoxy group (epoxy modified polyoxyxene oil, etc.), and the like.

再者，於本說明書，對包含於本發明的第1態樣或第2態樣的硬化性樹脂組成物之各成分(例如脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化劑(E)、硬化促進劑(F)、硬化觸媒(G)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)、脂環式聚酯樹脂(K)等)的含量，可分別從記載的範圍內適當選擇，使合計成為100重量%。 In addition, in the present specification, each component of the curable resin composition contained in the first aspect or the second aspect of the present invention (for example, an alicyclic epoxy compound (A), a rubber particle (B), and a white color Pigment (C), inorganic filler (D), hardener (E), hardening accelerator (F), hardening catalyst (G), stress relieving agent (H), isocyanuric acid derivative (I), hydrazine The content of the oxane derivative (J), the alicyclic polyester resin (K), and the like can be appropriately selected from the range described, and the total amount is 100% by weight.

[聚矽氧橡膠粒子以外的橡膠粒子(B)] [Rubber particles other than polyoxyethylene rubber particles (B)]

本發明的第1態樣或第2態樣的硬化性樹脂組成物的必要成分之聚矽氧橡膠粒子以外的橡膠粒子(B)(以下有只稱為「橡膠粒子(B)」的情況)，係具有橡膠彈性的聚矽氧橡膠粒子以外的粒子。本發明的第1態樣的硬化性樹脂組成物，藉由將橡膠粒子(B)與脂環式環氧化合物(A)、白色顏料(C)、無機填充劑(D)及應力緩和劑(H)組合使用，有藉由壓縮成型所形成的硬化物的光反射性、耐熱性、耐光性及耐龜裂性皆優的傾向。而且，本發明的第2態樣的硬化性樹脂組成物，藉由將橡膠粒子(B)與脂環式環氧化合物(A)、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)、及脂環式聚酯樹脂(K)組合使用，有藉由壓縮成型所形成的硬化物的光反射性、耐熱性、耐光性及耐龜裂性皆優的傾向。 Rubber particles (B) other than the polyoxyethylene rubber particles which are essential components of the curable resin composition of the first aspect or the second aspect of the present invention (hereinafter referred to as "rubber particles (B)") It is a particle other than the rubber-elastic polyoxyethylene rubber particle. The curable resin composition according to the first aspect of the present invention comprises rubber particles (B), an alicyclic epoxy compound (A), a white pigment (C), an inorganic filler (D), and a stress relieving agent ( H) In combination, there is a tendency that the cured product formed by compression molding has excellent light reflectivity, heat resistance, light resistance, and crack resistance. Further, the curable resin composition of the second aspect of the present invention is characterized in that the rubber particles (B) and the alicyclic epoxy compound (A), the white pigment (C), the inorganic filler (D), and the stress are alleviated. The agent (H), the isocyanuric acid derivative (I), the decane derivative (J), and the alicyclic polyester resin (K) are used in combination, and the light reflection of the cured product formed by compression molding is used. The tendency to be excellent in properties, heat resistance, light resistance and crack resistance.

作為橡膠粒子(B)，只要是聚矽氧橡膠粒子以外者即無特別限制，可使用習知至慣用的橡膠粒子，例如粒子狀NBR(丙烯腈-丁二烯橡膠)、反應性末端羧基的NBR(CTBN)、無金屬NBR、粒子狀SBR(苯乙烯-丁二烯橡膠)等橡膠粒子。作為橡膠粒子(B)，從容易得到分散性良好且韌性提高(耐龜裂性提高)等效果的觀點，以具有橡膠彈性的核部分與包覆該核部分的至少1層殼層所構成的具有多層構造(核殼構造)的橡膠粒子(以下有稱為「核殼型粒子」的情況)較理想。橡膠粒子(B)，從硬化物的耐熱性及 耐光性更為提高的觀點，特別是以(甲基)丙烯酸酯為必要單體成分的聚合物構成之表面具有作為可與脂環式環氧化合物(A)等具有環氧基的化合物反應的官能基之羥基及/或羧基(羥基及羧基的任一者或兩者)的橡膠粒子較理想。亦即，橡膠粒子(B)，係由以(甲基)丙烯酸酯為必要單體成分的聚合物(丙烯酸系聚合物)所構成之核殼型橡膠粒子為特佳。再者，於本發明的第1態樣或第2態樣的硬化性樹脂組成物，橡膠粒子(B)可使用單獨1種，亦可組合2種以上使用。 The rubber particles (B) are not particularly limited as long as they are polyoxo rubber particles, and conventionally used rubber particles such as particulate NBR (acrylonitrile-butadiene rubber) and reactive terminal carboxyl groups can be used. Rubber particles such as NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). The rubber particles (B) are composed of a core portion having rubber elasticity and at least one shell layer covering the core portion, from the viewpoint of easily obtaining effects such as good dispersibility and improvement in toughness (improvement in crack resistance). It is preferable that rubber particles having a multilayer structure (core-shell structure) (hereinafter referred to as "core-shell particles") are preferable. From the viewpoint of further improving the heat resistance and light resistance of the cured product, the rubber particles (B) have a surface composed of a polymer having a (meth) acrylate as an essential monomer component, and have an alicyclic epoxy resin. The rubber particles of the hydroxyl group and/or the carboxyl group (either or both of the hydroxyl group and the carboxyl group) of the functional group reactive with the epoxy group-containing compound such as the compound (A) are preferred. In other words, the rubber particles (B) are particularly preferably core-shell type rubber particles composed of a polymer (acrylic polymer) having (meth) acrylate as an essential monomer component. In addition, the rubber particles (B) may be used alone or in combination of two or more kinds in the first embodiment or the second aspect of the curable resin composition.

於橡膠粒子(B)為核殼型橡膠粒子的情況，構成上述具有橡膠彈性的核部分的聚合物，只要是聚矽氧化合物以外即無特別限制，但較理想為包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等(甲基)丙烯酸酯為必要單體成分的聚合物。構成上述具有橡膠彈性的核部分的聚合物，其他亦可包含例如苯乙烯、α-甲基苯乙烯等芳香族乙烯；丙烯腈、甲基丙烯腈等腈；丁二烯、異戊二烯等共軛二烯；乙烯、丙烯、異丁烯等α-烯烴等作為單體成分。 In the case where the rubber particles (B) are core-shell type rubber particles, the polymer constituting the rubber-elastic core portion is not particularly limited as long as it is a polyoxonium compound, but preferably contains (meth)acrylic acid. A (meth) acrylate such as an ester, ethyl (meth)acrylate or butyl (meth)acrylate is a polymer of an essential monomer component. The polymer constituting the rubber-elastic core portion may contain, for example, aromatic ethylene such as styrene or α-methylstyrene; nitrile such as acrylonitrile or methacrylonitrile; butadiene, isoprene, etc. A conjugated diene; an α-olefin such as ethylene, propylene or isobutylene is used as a monomer component.

其中，構成上述具有橡膠彈性的核部分的聚合物，作為單體成分，以包含(甲基)丙烯酸酯與選自芳香族乙烯、腈及共軛二烯所成群的1種或2種以上之組合較理想。亦即，作為構成上述核部分的聚合物，例如(甲基)丙烯酸酯/芳香族乙烯、(甲基)丙烯酸酯/共軛二烯等二元共聚物；(甲基)丙烯酸酯/芳香族乙烯/共軛二烯等三元共聚物 等。 In the above, the polymer constituting the core portion having the rubber elasticity is one or more selected from the group consisting of (meth) acrylate and a group selected from the group consisting of aromatic vinyl, nitrile and conjugated diene. The combination is ideal. That is, as the polymer constituting the core portion, for example, a binary copolymer such as (meth) acrylate/aromatic ethylene or (meth) acrylate/conjugated diene; (meth) acrylate/aromatic a terpolymer such as an ethylene/conjugated diene or the like.

構成上述核部分的聚合物，亦可含有例如二乙烯基苯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、馬來酸二烯丙酯、氰脲酸三烯丙酯、鄰苯二甲酸二烯丙酯、丁二醇二(甲基)丙烯酸酯等分子內具有2個以上反應性官能基的反應性交聯單體作為其他單體成分。 The polymer constituting the core portion may also contain, for example, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diallyl maleate, cyanurate A reactive crosslinking monomer having two or more reactive functional groups in a molecule such as propyl ester, diallyl phthalate or butanediol di(meth)acrylate is used as another monomer component.

上述核部分，其中由(甲基)丙烯酸酯/芳香族乙烯的二元共聚物(特別是(甲基)丙烯酸丁酯/苯乙烯)或(甲基)丙烯酸酯/芳香族乙烯/其他單體的三元共聚物(特別是(甲基)丙烯酸丁酯/苯乙烯/二乙烯基苯)構成的核部分，在可容易調整核殼型橡膠粒子的折射率的點較理想。 The above-mentioned core portion, wherein a binary copolymer of (meth) acrylate/aromatic ethylene (particularly butyl (meth) acrylate / styrene) or (meth) acrylate / aromatic vinyl / other monomer The core portion composed of a terpolymer (particularly, butyl (meth)acrylate/styrene/divinylbenzene) is preferable in that the refractive index of the core-shell type rubber particles can be easily adjusted.

構成上述核部分的聚合物的玻璃轉化溫度雖無特別限制，但較理想為-100至10℃，更理想為-80至-10℃，又更理想為-60至-20℃。藉由使上述聚合物的玻璃轉化溫度為上述範圍內，有提高硬化物的耐龜裂性的傾向。再者，構成上述核部分的聚合物的玻璃轉化溫度，係指藉由下述Fox式算出的計算值(參考Bull.Am.Phys.Soc.,1(3)123(1956))。下述Fox式中，Tg表示構成核部分的聚合物的玻璃轉化溫度(單位：K)，Wi表示對構成核部分的聚合物的構成單體的全部量而言單體i的重量比例。而且，Tgi表示單體i的單獨聚合物的玻璃轉化溫度(單位：K)。下述Fox式係表示構成核部分的聚合物為單體1、單體2...及單體n的共聚物的情況的方程式。 The glass transition temperature of the polymer constituting the above-mentioned core portion is not particularly limited, but is desirably -100 to 10 ° C, more desirably -80 to -10 ° C, and still more desirably -60 to -20 ° C. When the glass transition temperature of the above polymer is within the above range, the crack resistance of the cured product tends to be improved. Further, the glass transition temperature of the polymer constituting the core portion refers to a calculated value calculated by the following Fox equation (refer to Bull. Am. Phys. Soc., 1 (3) 123 (1956)). In the following Fox formula, Tg represents the glass transition temperature (unit: K) of the polymer constituting the core portion, and W i represents the weight ratio of the monomer i to the total amount of constituent monomers of the polymer constituting the core portion. Moreover, Tg i represents the glass transition temperature (unit: K) of the individual polymer of monomer i. The following Fox formula shows an equation in the case where the polymer constituting the core portion is a copolymer of monomer 1, monomer 2, and monomer n.

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

上述單獨聚合物的玻璃轉化溫度，可採用各種文獻記載的值，可採用例如「Polymer Handbook第3版」(Johm Wiley & Sons公司發行)記載的值。再者，對於文獻沒有記載者，可採用將單體藉由通常的方法聚合所得之單獨聚合物藉由DSC方法測定的玻璃轉化溫度的值。 The glass transition temperature of the above-mentioned individual polymer can be a value described in various documents, and for example, a value described in "Polymer Handbook 3rd Edition" (published by Johm Wiley & Sons Co., Ltd.) can be used. Further, for those not described in the literature, the value of the glass transition temperature measured by the DSC method of a single polymer obtained by polymerizing a monomer by a usual method can be used.

上述核部分，可用通常使用的方法製造，例如將上述單體藉由乳化聚合法聚合的方法等製造。於乳化聚合法，可將上述單體的全部量一起放入進行聚合，亦可將上述單體的一部分聚合後，其餘部分再連續或間歇添加進行聚合，再者亦可利用使用種子粒子的聚合方法。 The above-mentioned core portion can be produced by a commonly used method, for example, a method in which the above monomer is polymerized by an emulsion polymerization method or the like. In the emulsion polymerization method, the entire amount of the above monomers may be put together for polymerization, or a part of the above monomers may be polymerized, and the remainder may be continuously or intermittently added for polymerization, and further polymerization using seed particles may be used. method.

再者，作為橡膠粒子(B)，於使用不具有核殼構造的粒子的情況，可使用例如只由上述核部分構成的橡膠粒子等。 Further, as the rubber particles (B), in the case of using particles having no core-shell structure, for example, rubber particles composed only of the above-described core portion can be used.

構成核殼型橡膠粒子的殼層的聚合物，較理想為與上述構成核部分的聚合物不同種的聚合物(具有不同的單體組成的聚合物)。而且，如上述，上述殼層以具有作為可與脂環式環氧化合物(A)等具有環氧基的化合物反應的官能基之羥基及/或羧基較理想。藉此，特別是在與脂環式環氧化合物(A)的界面可提高接著性，對於包含使具有該殼層的核殼型橡膠粒子的硬化性樹脂組成物硬化而成的硬化物，可發揮良好的耐龜裂性。而且，可防止硬化物的玻璃轉化溫度降低。 The polymer constituting the shell layer of the core-shell type rubber particles is preferably a polymer (a polymer having a different monomer composition) different from the polymer constituting the core portion described above. Further, as described above, the shell layer preferably has a hydroxyl group and/or a carboxyl group which is a functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). In this way, in particular, the interface with the alicyclic epoxy compound (A) can improve the adhesion, and the cured product containing the curable resin composition of the core-shell type rubber particles having the shell layer can be cured. Play good crack resistance. Moreover, the glass transition temperature of the cured product can be prevented from decreasing.

構成上述殼層的聚合物，較理想為包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯等 (甲基)丙烯酸酯為必要單體成分的聚合物。例如於使用丙烯酸丁酯作為上述核部分之(甲基)丙烯酸酯的情況，作為構成殼層的聚合物的單體成分，以使用例如丙烯酸丁酯以外的(甲基)丙烯酸酯(例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、甲基丙烯酸丁酯等)較理想。作為(甲基)丙烯酸酯以外之可包含的單體成分，例如苯乙烯、α-甲基苯乙烯等芳香族乙烯；丙烯腈、甲基丙烯腈等腈等。於核殼型橡膠粒子，作為構成殼層的單體成分，較理想為包含(甲基)丙烯酸酯與上述單體單獨或2種以上的組合，特別是至少包含芳香族乙烯，在可容易調整核殼型橡膠粒子的折射率的點較理想。 The polymer constituting the shell layer is preferably a polymer containing a (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate as a necessary monomer component. . For example, in the case of using butyl acrylate as the (meth) acrylate of the above-mentioned core portion, as a monomer component of the polymer constituting the shell layer, for example, a (meth) acrylate other than butyl acrylate (for example, (A) is used. Methyl acrylate, ethyl (meth) acrylate, butyl methacrylate, etc.) are preferred. Examples of the monomer component other than the (meth) acrylate include aromatic vinyl such as styrene or α-methylstyrene; and nitriles such as acrylonitrile and methacrylonitrile. The core-shell type rubber particles preferably contain a (meth) acrylate and the above monomers alone or in combination of two or more kinds, and particularly contain at least aromatic ethylene, and can be easily adjusted. The point of the refractive index of the core-shell type rubber particles is ideal.

再者，構成上述殼層的聚合物，作為單體成分，為了形成可與脂環式環氧化合物(A)等具有環氧基的化合物反應的官能基之羥基及/或羧基，以包含含有羥基的單體(例如(甲基)丙烯酸2-羥基乙酯等(甲基)丙烯酸羥基烷酯等)、含有羧基的單體(例如(甲基)丙烯酸等α,β-不飽和酸；馬來酸酐等α,β-不飽和酸酐等)較理想。 In addition, the polymer constituting the shell layer contains, as a monomer component, a hydroxyl group and/or a carboxyl group which can form a functional group reactive with a compound having an epoxy group such as an alicyclic epoxy compound (A). a monomer having a hydroxyl group (for example, a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate) or a monomer having a carboxyl group (for example, an α,β-unsaturated acid such as (meth)acrylic acid; An α,β-unsaturated acid anhydride such as an anhydride or the like is preferable.

構成上述殼層的聚合物，作為單體成分，與(甲基)丙烯酸酯一起，以包含選自上述單體的1種或2種以上之組合較理想。亦即，上述殼層，例如由(甲基)丙烯酸酯/芳香族乙烯/(甲基)丙烯酸羥基烷酯、(甲基)丙烯酸酯/芳香族乙烯/α,β-不飽和酸等三元共聚物等構成的殼層較理想。 The polymer constituting the shell layer is preferably one or a combination of two or more selected from the above monomers together with the (meth) acrylate as the monomer component. That is, the shell layer is made of, for example, (meth) acrylate/aromatic ethylene/hydroxyalkyl (meth) acrylate, (meth) acrylate/aromatic ethylene/α, β-unsaturated acid, etc. A shell layer composed of a copolymer or the like is preferred.

而且，構成上述殼層的聚合物，作為其他 單體成分，與核部分同樣除了上述單體外亦可含有二乙烯基苯、(甲基)丙烯酸烯丙酯、乙二醇二(甲基)丙烯酸酯、馬來酸二烯丙酯、氰脲酸三烯丙酯、鄰苯二甲酸二烯丙酯、丁二醇二(甲基)丙烯酸酯等分子內具有2個以上反應性官能基的反應性交聯單體。 Further, the polymer constituting the shell layer may contain, as the other monomer component, divinylbenzene, allyl (meth)acrylate, or ethylene glycol di(methyl) in addition to the above-mentioned monomers. Acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butanediol di(meth)acrylate, etc. having more than two reactive functional groups in the molecule Reactive crosslinking monomer.

構成上述殼層的聚合物的玻璃轉化溫度雖無特別限制，但較理想為20至200℃，更理想為40至180℃，又更理想為60至160℃。藉由使上述聚合物的玻璃轉化溫度為20℃以上，有提高硬化物的耐熱性及耐光性的傾向。另一方面，藉由使上述聚合物的玻璃轉化溫度為200℃以下，有提高橡膠粒子(B)的分散性及硬化物的耐龜裂性的傾向。再者，構成上述殼層的聚合物的玻璃轉化溫度，係指藉由上述Fox式算出的計算值，例如可與上述構成核的聚合物的玻璃轉化溫度同樣測定。 The glass transition temperature of the polymer constituting the above shell layer is not particularly limited, but is preferably from 20 to 200 ° C, more preferably from 40 to 180 ° C, still more preferably from 60 to 160 ° C. When the glass transition temperature of the above polymer is 20° C. or higher, the heat resistance and light resistance of the cured product tend to be improved. On the other hand, when the glass transition temperature of the above polymer is 200 ° C or lower, the dispersibility of the rubber particles (B) and the crack resistance of the cured product tend to be improved. Further, the glass transition temperature of the polymer constituting the shell layer is a calculated value calculated by the above-mentioned Fox formula, and can be measured, for example, in the same manner as the glass transition temperature of the polymer constituting the core.

核殼型橡膠粒子，可將上述核部分藉由殼層包覆而得。作為上述核部分藉由殼層包覆的方法，例如於藉由上述方法所得之具有橡膠彈性的核部分的表面，藉由塗佈構成殼層的聚合物進行包覆的方法；藉由上述方法所得之具有橡膠彈性的核部分為樹幹成分，構成殼層的各成分為樹枝成分之接枝聚合的方法等。 The core-shell type rubber particles can be obtained by coating the core portion with a shell layer. a method of coating the core portion by a shell layer, for example, a surface of a rubber-elastic core portion obtained by the above method, by coating a polymer constituting the shell layer; The obtained rubber-elastic core portion is a trunk component, and each component constituting the shell layer is a graft polymerization method of a branch component.

橡膠粒子(B)的平均粒徑，無特別限制，較理想為10至500nm，更理想為20至400nm。而且，橡膠粒子(B)的最大粒徑，無特別限制，較理想為50至1000nm，更理想為100至800nm。藉由平均粒徑為500nm以 下(或最大粒徑為1000nm以下)，提高硬化物中橡膠粒子(B)的分散性，有提高耐龜裂性的傾向。另一方面，藉由平均粒徑為10nm以上(或最大粒徑為50nm以上)，有提高硬化物的耐龜裂性的傾向。 The average particle diameter of the rubber particles (B) is not particularly limited, but is preferably from 10 to 500 nm, more preferably from 20 to 400 nm. Further, the maximum particle diameter of the rubber particles (B) is not particularly limited, and is preferably from 50 to 1,000 nm, more preferably from 100 to 800 nm. When the average particle diameter is 500 nm or less (or the maximum particle diameter is 1000 nm or less), the dispersibility of the rubber particles (B) in the cured product is improved, and the crack resistance tends to be improved. On the other hand, when the average particle diameter is 10 nm or more (or the maximum particle diameter is 50 nm or more), the crack resistance of the cured product tends to be improved.

橡膠粒子(B)的折射率，無特別限制，較理想為1.40至1.60，更理想為1.42至1.58。而且，橡膠粒子(B)的折射率與包含該橡膠粒子(B)的硬化性樹脂組成物(本發明的第1態樣或第2態樣的硬化性樹脂組成物)硬化所得之硬化物的折射率的差為±0.03以內較理想。藉由折射率的差為±0.03以內，確保硬化物的優異光反射性，有保持光半導體裝置的高亮度的傾向。 The refractive index of the rubber particles (B) is not particularly limited, and is preferably 1.40 to 1.60, more preferably 1.42 to 1.58. Further, the refractive index of the rubber particles (B) and the curable resin composition (the first aspect or the second aspect of the curable resin composition of the present invention) containing the rubber particles (B) are cured. The difference in refractive index is preferably within ±0.03. When the difference in refractive index is within ±0.03, excellent light reflectivity of the cured product is ensured, and the high luminance of the optical semiconductor device tends to be maintained.

橡膠粒子(B)的折射率，例如將橡膠粒子(B)1g注模於模具，在210℃、4MPa下壓縮成型，得到厚度1mm的平板，從所得之平板切出縱20mm×橫6mm的測試片，使用單溴萘作為中間液，在稜鏡與該測試片密合的狀態下，使用多波長阿貝折射率計(商品名「DR-M2」、(股)Atago公司製)，於20℃藉由測定鈉D線的折射率而求得。 For the refractive index of the rubber particles (B), for example, 1 g of the rubber particles (B) is injection molded into a mold, and compression-molded at 210 ° C and 4 MPa to obtain a flat plate having a thickness of 1 mm, and a test of 20 mm in length × 6 mm in width is cut out from the obtained flat plate. A monobromide was used as an intermediate liquid, and a multi-wavelength Abbe refractometer (trade name "DR-M2", manufactured by Atago Co., Ltd.) was used in a state in which the crucible was in close contact with the test piece. °C is obtained by measuring the refractive index of the sodium D line.

本發明的第1態樣或第2態樣的硬化性樹脂組成物的硬化物的折射率，例如從藉由下述硬化物的項目記載的加熱硬化方法所得之硬化物，切出縱20mm×橫6mm×厚度1mm的測試片，使用單溴萘作為中間液，在稜鏡與該測試片密合的狀態下，使用多波長阿貝折射率計(商品名「DR-M2」、(股)Atago公司製)，於20℃藉由測定鈉D 線的折射率而求得。 The refractive index of the cured product of the curable resin composition of the first aspect or the second aspect of the present invention is, for example, 20 mm in length from the cured product obtained by the heat curing method described in the item of the following cured product. A test piece having a width of 6 mm × a thickness of 1 mm was used as an intermediate liquid, and a multi-wavelength Abbe refractometer (trade name "DR-M2", (share) was used in a state in which the crucible was in close contact with the test piece. Atago Co., Ltd. was obtained by measuring the refractive index of the sodium D line at 20 °C.

本發明的第1態樣的硬化性樹脂組成物中橡膠粒子(B)的含量(調配量)，無特別限制，但對硬化性樹脂組成物(100重量%)而言，較理想為0.05至20重量%，更理想為0.1至15重量%，又更理想為0.2至10重量%。藉由橡膠粒子(B)的含量為0.05重量%以上，有硬化物的光反射性、耐熱性及耐光性更佳的傾向。而且，硬化物的耐龜裂性有提高的傾向。另一方面，藉由橡膠粒子(B)的含量為20重量%以下，有更提高硬化物的耐熱性及耐光性的傾向。 The content (adjusted amount) of the rubber particles (B) in the curable resin composition of the first aspect of the present invention is not particularly limited, but is preferably 0.05 to 100% by weight of the curable resin composition (100% by weight). 20% by weight, more desirably 0.1 to 15% by weight, still more preferably 0.2 to 10% by weight. When the content of the rubber particles (B) is 0.05% by weight or more, the light reflectivity, heat resistance, and light resistance of the cured product tend to be better. Further, the crack resistance of the cured product tends to be improved. On the other hand, when the content of the rubber particles (B) is 20% by weight or less, the heat resistance and light resistance of the cured product tend to be improved.

本發明的第2態樣的硬化性樹脂組成物中橡膠粒子(B)的含量(調配量)，無特別限制，但對硬化性樹脂組成物(100重量%)而言，較理想為0.01至20重量%，更理想為0.05至15重量%，又更理想為0.1至10重量%。藉由橡膠粒子(B)的含量為上述範圍內，有提高硬化物的耐龜裂性、耐熱性及耐光性更佳的傾向。 The content (mixing amount) of the rubber particles (B) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is preferably 0.01 to 100% by weight of the curable resin composition (100% by weight). 20% by weight, more desirably 0.05 to 15% by weight, still more desirably 0.1 to 10% by weight. When the content of the rubber particles (B) is within the above range, the crack resistance, heat resistance, and light resistance of the cured product tend to be improved.

本發明的第1態樣或第2態樣的硬化性樹脂組成物中橡膠粒子(B)的含量(調配量)，無特別限制，但對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為0.5至30重量份，更理想為1至20重量份。藉由橡膠粒子(B)的含量為上述範圍內，有提高硬化物的耐龜裂性、耐熱性及耐光性更佳的傾向。亦即，藉由橡膠粒子(B)的含量為0.5重量份以上，有硬化物的光反射性、耐熱性及耐光性更佳的傾向。而且，硬化 物的耐龜裂性有提高的傾向。另一方面，藉由橡膠粒子(B)的含量為30重量份以下，有更提高硬化物的耐熱性及耐光性的傾向。 The content (mixing amount) of the rubber particles (B) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is an epoxy group contained in the curable resin composition. The total amount of the compound is preferably from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight. When the content of the rubber particles (B) is within the above range, the crack resistance, heat resistance, and light resistance of the cured product tend to be improved. In other words, when the content of the rubber particles (B) is 0.5 parts by weight or more, the light reflectivity, heat resistance, and light resistance of the cured product tend to be better. Further, the crack resistance of the cured product tends to be improved. On the other hand, when the content of the rubber particles (B) is 30 parts by weight or less, the heat resistance and light resistance of the cured product tend to be improved.

[白色顏料(C)] [white pigment (C)]

本發明的第1態樣或第2態樣的硬化性樹脂組成物的必要成分之白色顏料(C)，主要具有對硬化物(反射器)賦予高反射性，而且減少其線膨脹率的作用。作為白色顏料(C)，可使用習知至慣用的白色顏料，無特別限制，例如玻璃、黏土、雲母、滑石、高嶺土(Kaolin)、禾樂石(Halloysite)、沸石、酸性白土、活性白土、勃姆石(Baohmite)、假勃姆石、無機氧化物、金屬鹽[例如鹼土類金屬鹽等]等的無機白色顏料；苯乙烯系樹脂、苯並胍胺系樹脂、尿素-甲醛系樹脂、三聚氰胺-甲醛系樹脂、醯胺系樹脂等樹脂顏料等的有機白色顏料(塑膠顏料等)；具有中空構造(氣球構造)的中空粒子等。 The white pigment (C) which is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention mainly has high reflectivity to the cured product (reflector) and reduces the linear expansion ratio thereof. . As the white pigment (C), a conventionally customary white pigment can be used without particular limitation, such as glass, clay, mica, talc, kaolin, halloysite, zeolite, acid clay, activated clay, Inorganic white pigments such as Baohmite, pseudo-boehmite, inorganic oxides, metal salts (for example, alkaline earth metal salts, etc.); styrene resins, benzoguanamine resins, urea-formaldehyde resins, An organic white pigment (such as a plastic pigment) such as a resin pigment such as a melamine-formaldehyde resin or a guanamine resin; or a hollow particle having a hollow structure (balloon structure).

作為白色顏料(C)，為了提高反射器的反射率，以使用折射率高的白色顏料較理想，例如折射率1.5以上的白色顏料較理想。但是，具有中空構造的白色顏料，因內部(核)包含低折射率的氣體，表面反射率非常大，故殼部分可為由折射率低於1.5的材料構成。再者，例示作為白色顏料(C)之物中，有關對應於無機填充劑(D)者，折射率1.5以上者作為白色顏料(C)，折射率低於1.5者為無機填充劑(D)。 As the white pigment (C), in order to increase the reflectance of the reflector, a white pigment having a high refractive index is preferably used, and for example, a white pigment having a refractive index of 1.5 or more is preferable. However, a white pigment having a hollow structure has a surface reflectance which is very large because the inner (core) contains a gas having a low refractive index, so that the shell portion may be composed of a material having a refractive index of less than 1.5. Further, as the white pigment (C), those having a refractive index of 1.5 or more are used as the white pigment (C), and those having a refractive index of less than 1.5 are inorganic fillers (D). .

作為上述無機氧化物，例如氧化鋁、氧化鎂、氧化銻、氧化鈦[例如金紅石型氧化鈦、銳鈦礦型氧化鈦、板鈦礦型氧化鈦等]、氧化鋯、氧化鋅等。而且，作為上述鹼土類金屬鹽，例如碳酸鎂、碳酸鈣、碳酸鋇、矽酸鎂、矽酸鈣、氫氧化鎂、磷酸鎂、磷酸氫鎂、硫酸鎂、硫酸鈣、硫酸鋇等。而且，作為鹼土類金屬鹽以外的金屬鹽，例如矽酸鋁、氫氧化鋁、硫化鋅等。 Examples of the inorganic oxide include alumina, magnesia, cerium oxide, titanium oxide (for example, rutile-type titanium oxide, anatase-type titanium oxide, brookite-type titanium oxide, etc.), zirconium oxide, zinc oxide, and the like. Further, examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium citrate, calcium citrate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, barium sulfate, and the like. Further, as the metal salt other than the alkaline earth metal salt, for example, aluminum ruthenate, aluminum hydroxide, zinc sulfide, or the like.

作為上述中空粒子，無特別限制，例如由無機玻璃[例如矽酸鈉玻璃、矽酸鋁玻璃、硼矽酸鈉玻璃、石英等]、氧化矽、氧化鋁等金屬氧化物、碳酸鈣、碳酸鋇、碳酸鎳、矽酸鈣等金屬鹽等無機物所構成的無機中空粒子(也包含火山灰球(shirasu balloon)等天然物)；苯乙烯系樹脂、丙烯酸系樹脂、聚矽氧系樹脂、丙烯酸-苯乙烯系樹脂、氯乙烯系樹脂、偏二氯乙烯系樹脂、醯胺系樹脂、胺酯系樹脂、酚系樹脂、苯乙烯-共軛二烯系樹脂、丙烯酸-共軛二烯系樹脂、烯烴系樹脂等聚合物(也包含該等聚合物的交聯物)等的有機物所構成的有機中空粒子；由無機物與有機物的混成材料所構成的無機-有機中空粒子等。再者，上述中空粒子，可為由單一的材料所構成者，亦可為由2種以上材料所構成者。而且，上述中空粒子的中空部(中空粒子的內部空間)可為真空狀態，亦可充滿介質，但是特別在提高反射率的觀點，以充滿折射率低的介質(例如氮氣、氬氣等不活性氣體、空氣等)的中空粒子較理想。 The hollow particles are not particularly limited, and examples thereof include inorganic glass (for example, sodium citrate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.), metal oxides such as cerium oxide and aluminum oxide, calcium carbonate, and cesium carbonate. Inorganic hollow particles (including natural materials such as shirasu balloons) composed of inorganic substances such as nickel carbonate and calcium citrate; styrene resin, acrylic resin, polyoxyn resin, acrylic acid-benzene Ethylene resin, vinyl chloride resin, vinylidene chloride resin, guanamine resin, amine ester resin, phenol resin, styrene-conjugated diene resin, acrylic acid-conjugated diene resin, olefin An organic hollow particle composed of an organic substance such as a polymer such as a resin (including a crosslinked product of the polymer); an inorganic-organic hollow particle composed of a mixture of an inorganic substance and an organic substance. Further, the hollow particles may be composed of a single material or may be composed of two or more materials. Further, the hollow portion (the inner space of the hollow particles) of the hollow particles may be in a vacuum state or may be filled with a medium, but in particular, in the viewpoint of improving the reflectance, a medium having a low refractive index (for example, nitrogen, argon or the like) is inactive. Hollow particles of gas, air, etc. are preferred.

再者，白色顏料(C)，可為實施習知至慣用 的表面處理[例如藉由金屬氧化物、矽烷偶合劑、鈦偶合劑、有機酸、聚醇、聚矽氧等表面處理劑之表面處理等]者。藉由實施如此的表面處理，有提高與硬化性樹脂組成物之其他成分的相溶性、分散性的情況。 Further, the white pigment (C) may be a surface treatment which is conventionally used (for example, a surface treatment agent such as a metal oxide, a decane coupling agent, a titanium coupling agent, an organic acid, a polyalcohol or a polyoxyl oxide). Processing, etc.]. By carrying out such a surface treatment, it is possible to improve the compatibility and dispersibility with other components of the curable resin composition.

其中，作為白色顏料(C)，在取得性、耐熱性、耐光性的觀點以及硬化物(反射器)的高反射率及添加量對光反射性之提升比例的觀點，較理想為無機氧化物、無機中空粒子，又更理想為氧化鋁、氧化鎂、氧化銻、氧化鈦、氧化鋯、氧化鋅、硫酸鋇、無機中空粒子，又更理想為氧化鈦、氧化鋯、氧化鋅、硫酸鋇。特別是作為白色顏料(C)，在具有更高折射率的點，較理想為氧化鈦。 Among them, as the white pigment (C), from the viewpoints of availability, heat resistance, and light resistance, and the high reflectance of the cured product (reflector) and the ratio of the added amount to the light reflectance, the inorganic oxide is preferable. Further, the inorganic hollow particles are more preferably alumina, magnesia, cerium oxide, titanium oxide, zirconium oxide, zinc oxide, barium sulfate or inorganic hollow particles, and more preferably titanium oxide, zirconium oxide, zinc oxide or barium sulfate. In particular, as the white pigment (C), at a point having a higher refractive index, titanium oxide is preferred.

白色顏料(C)的形狀，無特別限制，例如球狀、破碎狀、纖維狀、針狀、鱗片狀等。其中，在分散性的觀點，球狀的氧化鈦較理想，特別是真球狀的氧化鈦(例如長寬比為1.2以下的球狀的氧化鈦)較理想。 The shape of the white pigment (C) is not particularly limited, and is, for example, spherical, broken, fibrous, needle-like, scaly, or the like. Among them, spherical titanium oxide is preferable from the viewpoint of dispersibility, and in particular, true spherical titanium oxide (for example, spherical titanium oxide having an aspect ratio of 1.2 or less) is preferable.

白色顏料(C)的中心粒徑，無特別限制，在提高硬化物(反射器)的光反射性的觀點，較理想為0.1至50μm。特別是使用氧化鈦作為白色顏料(C)的情況，該氧化鈦的中心粒徑，無特別限制，較理想為0.1至50μm，更理想為0.1至30μm，又更理想為0.1至20μm，特別理想為0.1至10μm，最理想為0.1至5μm。另一方面，於使用中空粒子(特別是無機中空粒子)作為白色顏料(C)的情況，該中空粒子的中心粒徑，無特別限制，較理想為0.1至50μm，更理想為0.1至30μm。再者，上述中心粒徑， 係指雷射繞射‧散射法測定的粒徑分佈之積分值50%的粒徑(中間值直徑)。 The center particle diameter of the white pigment (C) is not particularly limited, and is preferably from 0.1 to 50 μm from the viewpoint of improving the light reflectivity of the cured product (reflector). In particular, when titanium oxide is used as the white pigment (C), the central particle diameter of the titanium oxide is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm, still more preferably 0.1 to 20 μm, and particularly preferably It is 0.1 to 10 μm, and most desirably 0.1 to 5 μm. On the other hand, in the case where hollow particles (particularly inorganic hollow particles) are used as the white pigment (C), the central particle diameter of the hollow particles is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm. Further, the above-mentioned center particle diameter means a particle diameter (median diameter) of 50% of the integral value of the particle diameter distribution measured by the laser diffraction ‧ scattering method.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物，白色顏料(C)可使用單獨1種，亦可組合2種以上使用。而且，白色顏料(C)可藉由習知至慣用的方法製造，亦可使用例如商品名「SR-1」、「R-42」、「R-45M」、「R-650」、「R-32」、「R-5N」、「GTR-100」、「R-62N」、「R-7E」、「R-44」、「R-3L」、「R-11P」、「R-21」、「R-25」、「TCR-52」、「R-310」、「D-918」、「FTR-700」(以上堺化學工業(股)製)、商品名「TIPAQUE CR-50」、「CR-50-2」、「CR-60-2」、「CR-63」、「CR-80」、「CR-90」、「CR-90-2」、「CR-93」、「CR-95」、「CR-97」(以上石原產業(股)製)、商品名「JR-301」、「JR-403」、「JR-405」、「JR-600A」、「JR-605」、「JR-600E」、「JR-603」、「JR-805」、「JR-806」、「JR-701」、「JRNC」、「JR-800」、「JR」(以上TEJKA(股)製)、商品名「TR-600」、「TR-700」、「TR-750」、「TR-840」、「TR-900」(以上富士鈦工業(股)製)、商品名「KR-310」、「KR-380」、「KR-380N」、「ST-410WB」、「ST-455」、「ST-455WB」、「ST-457SA」、「ST-457EC」、「ST-485SA15」、「ST-486SA」、「ST-495M」(以上鈦工業(股)製)等金紅石型氧化鈦；商品名「A-110」、「TCA-123E」、「A-190」、「A-197」、「SA-1」、「SA-1L」、「SSP系列」、「CSB系列」(以上堺化學工業(股)製)、商品名「JA-1」、「JA-C」、「JA-3」(以上TEIKA(股)製)、商品名「KA-10」、「KA-15」、「KA-20」、 「STT-65C-S」、「STT-30EHJ」(以上鈦工業(股)製)、商品名「DCF-T-17007」、「DCF-T-17008」、「DCF-T-17050」(以上Resinocolor工業(股)製)等銳鈦礦型氧化鈦等的市售品。 In the first aspect or the second aspect of the present invention, the white pigment (C) may be used alone or in combination of two or more. Further, the white pigment (C) can be produced by a conventional to conventional method, and for example, the trade names "SR-1", "R-42", "R-45M", "R-650", "R" can also be used. -32", "R-5N", "GTR-100", "R-62N", "R-7E", "R-44", "R-3L", "R-11P", "R-21" ""R-25", "TCR-52", "R-310", "D-918", "FTR-700" (above the Chemical Industry Co., Ltd.), and the product name "TIPAQUE CR-50" , "CR-50-2", "CR-60-2", "CR-63", "CR-80", "CR-90", "CR-90-2", "CR-93", " CR-95", "CR-97" (above Ishihara Industry Co., Ltd.), trade name "JR-301", "JR-403", "JR-405", "JR-600A", "JR-605" "JR-600E", "JR-603", "JR-805", "JR-806", "JR-701", "JRNC", "JR-800", "JR" (above TEJKA) )), product name "TR-600", "TR-700", "TR-750", "TR-840", "TR-900" (above Fuji Titanium Industry Co., Ltd.), trade name "KR -310", "KR-380", "KR-380N", "ST-410WB", "ST-455", "ST-455WB" , rutile-type titanium oxide such as "ST-457SA", "ST-457EC", "ST-485SA15", "ST-486SA", "ST-495M" (manufactured by Titanium Industry Co., Ltd.); -110", "TCA-123E", "A-190", "A-197", "SA-1", "SA-1L", "SSP Series", "CSB Series" (above 堺Chemical Industry) )), product name "JA-1", "JA-C", "JA-3" (above TEIKA), trade name "KA-10", "KA-15", "KA-20" "STT-65C-S", "STT-30EHJ" (manufactured by Titanium Industries Co., Ltd.), trade names "DCF-T-17007", "DCF-T-17008", "DCF-T-17050" (Available from Resinocolor Industries Co., Ltd.) and other commercial products such as anatase type titanium oxide.

其中，作為白色顏料(C)，特別在提高硬化物(反射器)的光反射性及耐黃變性的觀點，以商品名「R-62N」、「CR-60」、「DCF-T-17007」、「DCF-T-17008」、「DCF-T-17050」、「FTR-700」較理想。 Among them, as the white pigment (C), in particular, from the viewpoint of improving the light reflectivity and yellowing resistance of the cured product (reflector), the trade names are "R-62N", "CR-60", and "DCF-T-17007". "DCF-T-17008", "DCF-T-17050" and "FTR-700" are ideal.

本發明的第1態樣或第2態樣的硬化性樹脂組成物之白色顏料(C)的含量(調配量)雖無特別限制，但對硬化性樹脂組成物(100重量%)而言，較理想為0.1至50重量%，更理想為1至40重量%，又更理想為5至35重量%。藉由白色顏料(C)的含量為0.1重量%以上，有更提高硬化物(反射器)的光反射性的傾向。而且，有更提高耐熱性(特別是耐黃變性)及耐光性(特別是耐紫外線性)的傾向。另一方面，藉由白色顏料(C)的含量為50重量%以下，提高硬化物(反射器)的成形性，有更適合量產的傾向。 The content (mixing amount) of the white pigment (C) of the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but for the curable resin composition (100% by weight), It is preferably from 0.1 to 50% by weight, more desirably from 1 to 40% by weight, still more preferably from 5 to 35% by weight. When the content of the white pigment (C) is 0.1% by weight or more, the light reflectivity of the cured product (reflector) tends to be increased. Further, there is a tendency to further improve heat resistance (particularly, yellowing resistance) and light resistance (particularly, ultraviolet resistance). On the other hand, when the content of the white pigment (C) is 50% by weight or less, the formability of the cured product (reflector) is improved, and it is more suitable for mass production.

本發明的第1態樣的硬化性樹脂組成物之白色顏料(C)的含量(調配量)雖無特別限制，但對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為3至400重量份，更理想為10至350重量份，又更理想為30至300重量份。藉由白色顏料(C)的含量為3重量份以上，有更提高硬化物(反射器)的光反射性的傾向。而且，有更提高耐熱性(特別是耐黃變性)及耐光性(特別是耐紫外線性)的傾向。另一方面，藉由白色 顏料(C)的含量為400重量份以下，提高成形性，有更適合量產的傾向。 The content (mixing amount) of the white pigment (C) of the curable resin composition of the first aspect of the present invention is not particularly limited, but the total amount of the epoxy group-containing compound contained in the curable resin composition is 100. It is preferably from 3 to 400 parts by weight, more preferably from 10 to 350 parts by weight, still more preferably from 30 to 300 parts by weight, based on parts by weight. When the content of the white pigment (C) is 3 parts by weight or more, the light reflectivity of the cured product (reflector) tends to be increased. Further, there is a tendency to further improve heat resistance (particularly, yellowing resistance) and light resistance (particularly, ultraviolet resistance). On the other hand, when the content of the white pigment (C) is 400 parts by weight or less, the moldability is improved, and it tends to be more suitable for mass production.

本發明的第2態樣的硬化性樹脂組成物之白色顏料(C)的含量(調配量)，無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為10至600重量份，更理想為30至500重量份，又更理想為30至400重量份。藉由白色顏料(C)的含量為10重量份以上，有更提高硬化物(反射器)的光反射性的傾向。而且，有更提高耐熱性(特別是耐黃變性)及耐光性(特別是耐紫外線性)的傾向。另一方面，藉由白色顏料(C)的含量為600重量份以下，提高硬化物(反射器)的成形性，有更適合量產的傾向。 The content (mixing amount) of the white pigment (C) of the curable resin composition of the second aspect of the present invention is not particularly limited, and the total amount of the epoxy group-containing compound contained in the curable resin composition is 100% by weight. It is preferably from 10 to 600 parts by weight, more desirably from 30 to 500 parts by weight, still more preferably from 30 to 400 parts by weight. When the content of the white pigment (C) is 10 parts by weight or more, the light reflectivity of the cured product (reflector) tends to be increased. Further, there is a tendency to further improve heat resistance (particularly, yellowing resistance) and light resistance (particularly, ultraviolet resistance). On the other hand, when the content of the white pigment (C) is 600 parts by weight or less, the formability of the cured product (reflector) is improved, and it is more suitable for mass production.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物包含氧化鈦的情況，氧化鈦對白色顏料(C)及無機填充劑(D)的總量(100重量%)的比例，無特別限制，在硬化物(反射器)的耐熱性(耐黃變性)與光反射性平衡的觀點，較理想為5至70重量%，更理想為10至60重量%。藉由氧化鈦的比例為5重量%以上，有更提高硬化物(反射器)的光反射性的傾向。而且，有提高耐熱性(特別是耐黃變性)及耐光性(特別是耐紫外線性)的傾向。另一方面，藉由氧化鈦的比例為70重量%以下，提高硬化物(反射器)的成形性，有更適合量產的傾向。 When the curable resin composition of the first aspect or the second aspect of the present invention contains titanium oxide, the ratio of titanium oxide to the total amount (100% by weight) of the white pigment (C) and the inorganic filler (D) It is not particularly limited, and is preferably from 5 to 70% by weight, more preferably from 10 to 60% by weight, from the viewpoint of heat resistance (yellowing resistance) of the cured product (reflector) and light reflection balance. When the proportion of titanium oxide is 5% by weight or more, the light reflectivity of the cured product (reflector) tends to be increased. Further, there is a tendency to improve heat resistance (especially yellowing resistance) and light resistance (particularly, ultraviolet resistance). On the other hand, the ratio of the titanium oxide is 70% by weight or less, and the formability of the cured product (reflector) is improved, which tends to be more suitable for mass production.

[無機填充劑(D)] [Inorganic Filler (D)]

本發明的第1態樣或第2態樣的硬化性樹脂組成物，除了白色顏料(C)外，包含無機填充劑(D)作為必要成分。無機填充劑(D)，主要於硬化性樹脂組成物藉由壓縮成型而形成的情況，賦予所形成的硬化物良好的耐熱性及耐光性(特別是良好的耐熱性)。而且，具有減少硬化物(反射器)的線膨脹率的作用。而且，隨無機填充劑(D)的種類，也有可對硬化物(反射器)賦予良好的光反射性的情況。 The curable resin composition of the first aspect or the second aspect of the present invention contains an inorganic filler (D) as an essential component in addition to the white pigment (C). The inorganic filler (D) is mainly formed when the curable resin composition is formed by compression molding, and imparts excellent heat resistance and light resistance (especially good heat resistance) to the formed cured product. Moreover, it has the effect of reducing the linear expansion ratio of the cured product (reflector). Further, depending on the type of the inorganic filler (D), it is also possible to impart good light reflectivity to the cured product (reflector).

作為無機填充劑(D)，可使用習知至慣用的無機填充劑，無特別限制，例如氧化矽、氧化鋁、鋯石、矽酸鈣、磷酸鈣、碳酸鈣、碳酸鎂、碳化矽、氮化矽、氮化鋁、氮化硼、氫氧化鋁、氧化鐵、氧化鋅、氧化鋯、氧化鎂、氧化鈦、氧化鋁、硫酸鈣、硫酸鋇、鎂橄欖石、塊滑石(steatite)、尖晶石、黏土、高嶺土、白雲石、羥基磷灰石、霞石、方石英、矽灰石、矽藻土、滑石等的粉末或此等的成型體(例如球形化的珠粒等)等。而且，作為無機填充劑(D)，例如在上述無機填充劑實施習知至慣用的表面處理者。其中，作為無機填充劑(D)，在硬化物(反射器)的耐熱性(特別是耐黃變性)、耐光性及流動性的觀點，較理想為氧化矽、氧化鋁、氮化矽、氮化鋁、氮化硼，更理想為氧化矽(氧化矽填充劑)。 As the inorganic filler (D), a conventional to conventional inorganic filler can be used without particular limitation, such as cerium oxide, aluminum oxide, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, strontium carbide, nitrogen. Antimony, aluminum nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, forsterite, stataite, tip Powders such as spar, clay, kaolin, dolomite, hydroxyapatite, nepheline, cristobalite, apatite, diatomaceous earth, talc, or the like (or spheroidized beads, etc.). Further, as the inorganic filler (D), for example, a conventionally used surface treatment agent is applied to the above inorganic filler. Among them, the inorganic filler (D) is preferably cerium oxide, aluminum oxide, cerium nitride, or nitrogen from the viewpoints of heat resistance (especially yellowing resistance), light resistance, and fluidity of the cured product (reflector). Aluminum or boron nitride is more preferred as cerium oxide (cerium oxide filler).

作為氧化矽，無特別限制，可使用例如熔融氧化矽、結晶氧化矽、高純度合成氧化矽等習知至慣用的氧化矽。再者，作為氧化矽，可使用習知至慣用的表面處理[例如藉由金屬氧化物、矽烷偶合劑、鈦偶合劑、有機 酸、聚醇、聚矽氧等表面處理劑之表面處理等]者。 The cerium oxide is not particularly limited, and conventionally used cerium oxide such as molten cerium oxide, crystalline cerium oxide, or high-purity synthetic cerium oxide can be used. Further, as the cerium oxide, a conventional to conventional surface treatment [for example, surface treatment by a surface treatment agent such as a metal oxide, a decane coupling agent, a titanium coupling agent, an organic acid, a polyhydric alcohol or a polyfluorene oxide, etc.] can be used. By.

氧化矽的形狀，無特別限制，例如粉體、球狀、破碎狀、纖維狀、針狀、鱗片狀等。其中，在分散性的觀點，球狀的氧化矽較理想，特別是真球狀的氧化矽(例如長寬比為1.2以下的球狀氧化矽)較理想。 The shape of the cerium oxide is not particularly limited, and examples thereof include a powder, a spherical shape, a crushed shape, a fibrous shape, a needle shape, and a scaly shape. Among them, spherical yttrium oxide is preferable from the viewpoint of dispersibility, and particularly true spherical yttrium oxide (for example, spherical yttrium oxide having an aspect ratio of 1.2 or less) is preferable.

氧化矽的中心粒徑，無特別限制，在提高硬化物(反射器)的光反射性的觀點，較理想為0.1至50μm，更理想為0.1至30μm。再者，上述中心粒徑，係指雷射繞射‧散射法測定的粒徑分佈之積分值50%的粒徑(中間值直徑)。 The center particle diameter of cerium oxide is not particularly limited, and is preferably from 0.1 to 50 μm, more preferably from 0.1 to 30 μm, from the viewpoint of improving the light reflectivity of the cured product (reflector). Further, the above-mentioned center particle diameter means a particle diameter (median diameter) of 50% of the integral value of the particle diameter distribution measured by the laser diffraction ‧ scattering method.

再者，於本發明的第1態樣或第2態樣的硬化性樹脂組成物，無機填充劑(D)，可使用單獨1種，亦可組合2種以上使用。而且，無機填充劑(D)，可藉由習知至慣用的方法製造，亦可使用例如商品名「FB-910」、「FB-940」、「FB-950」、「FB-105」、「FB-105FD」、「FB-5D」、「FB-8S」、「FB-7SDC」、「FB-5SDC」、「FB-3SDC」、「FB-9FDC」、「FB-7FDC」、「FB-5FDC」、「FB-970FD」、「FB-975FD」、「FB-950FD」、「FB-40RFD」等FB系列；商品名「DAW-03DC」、「DAW-0525」、「DAW-1025」等DAW系列；商品名「SGP」(以上Denka(股)製)、商品名「HF-05」((股)TOKUYAMA製)、商品名「10μm SE-CC5」((股)Admatex製)、商品名「MSR-2212」、「MSR-25」(以上(股)龍森製)、商品名「HS-105」、「HS-106」、「HS-107」(以上(股)MICRON公司製)等市售品。 In addition, the inorganic filler (D) may be used alone or in combination of two or more kinds in the first embodiment or the second aspect of the curable resin composition. Further, the inorganic filler (D) can be produced by a conventionally known method, and for example, the trade names "FB-910", "FB-940", "FB-950", "FB-105", or the like can be used. "FB-105FD", "FB-5D", "FB-8S", "FB-7SDC", "FB-5SDC", "FB-3SDC", "FB-9FDC", "FB-7FDC", "FB" FB series such as -5FDC, "FB-970FD", "FB-975FD", "FB-950FD", "FB-40RFD"; trade names "DAW-03DC", "DAW-0525", "DAW-1025" DAW series; trade name "SGP" (manufactured by Denka Co., Ltd.), trade name "HF-05" (manufactured by TOKUYAMA), trade name "10μm SE-CC5" (manufactured by Admatex), and products "MSR-2212", "MSR-25" (above (Ren)), trade name "HS-105", "HS-106", "HS-107" (manufactured by MICRON Corporation) And other commercial products.

本發明的第1態樣或第2態樣的硬化性樹脂組成物之無機填充劑(D)的含量(調配量)，無特別限制，對硬化性樹脂組成物(100重量%)而言，較理想為10至90重量%，更理想為13至75重量%，又更理想為15至70重量%，再更理想為20至70重量%。藉由無機填充劑(D)的含量為10重量%以上，於硬化性樹脂組成物藉由壓縮成型而形成的情況，有更提高所形成的硬化物的耐熱性及耐光性(特別是良好的耐熱性)的傾向。而且，硬化物(反射器)的線膨脹係數變低，有不易發生使用該反射器的光半導體元件安裝用基板之引線架翹曲等缺陷的傾向。另一方面，藉由無機填充劑(D)的含量為90重量%以下，提高硬化物(反射器)的成型性，有更適合量產的傾向。 The content (mixing amount) of the inorganic filler (D) of the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, and for the curable resin composition (100% by weight), It is preferably from 10 to 90% by weight, more desirably from 13 to 75% by weight, still more preferably from 15 to 70% by weight, still more preferably from 20 to 70% by weight. When the content of the inorganic filler (D) is 10% by weight or more, when the curable resin composition is formed by compression molding, the heat resistance and light resistance of the formed cured product are further improved (especially good) The tendency of heat resistance). Further, the linear expansion coefficient of the cured product (reflector) tends to be low, and there is a tendency that defects such as warpage of the lead frame of the optical semiconductor element mounting substrate using the reflector tend to occur. On the other hand, when the content of the inorganic filler (D) is 90% by weight or less, the moldability of the cured product (reflector) is improved, and it is more suitable for mass production.

本發明的第1態樣的硬化性樹脂組成物之無機填充劑(D)的含量(調配量)，無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為10至1500重量份，更理想為50至1200重量份，又更理想為70至1000重量份。藉由無機填充劑(D)的含量為10重量份以上，於硬化性樹脂組成物藉由壓縮成型而形成的情況，有提高所形成的硬化物的耐熱性及耐光性(特別是良好的耐熱性)的傾向。而且，硬化物(反射器)的線膨脹係數變低，有不易發生使用該反射器的光半導體元件安裝用基板之引線架翹曲等缺陷的傾向。另一方面，藉由無機填充劑(D)的含量為1500重量份以下，因硬化性樹脂組成物具有良好的流動性，有抑制成型(特別是轉 移成形)時的未填充等問題的傾向。 The content (adjusted amount) of the inorganic filler (D) of the curable resin composition of the first aspect of the present invention is not particularly limited, and the total amount of the epoxy group-containing compound contained in the curable resin composition is 100. It is preferably from 10 to 1,500 parts by weight, more preferably from 50 to 1200 parts by weight, still more preferably from 70 to 1000 parts by weight, based on parts by weight. When the content of the inorganic filler (D) is 10 parts by weight or more, when the curable resin composition is formed by compression molding, heat resistance and light resistance (especially good heat resistance) of the formed cured product are improved. Sexuality. Further, the linear expansion coefficient of the cured product (reflector) tends to be low, and there is a tendency that defects such as warpage of the lead frame of the optical semiconductor element mounting substrate using the reflector tend to occur. On the other hand, when the content of the inorganic filler (D) is 1,500 parts by weight or less, the curable resin composition has good fluidity, and tends to suppress problems such as unfilling during molding (particularly, transfer molding).

本發明的第2態樣的硬化性樹脂組成物之無機填充劑(D)的含量(調配量)，無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為10至1500重量份，更理想為50至1200重量份，又更理想為100至1000重量份。藉由無機填充劑(D)的含量為10重量份以上，於硬化性樹脂組成物藉由壓縮成型而形成的情況，有提高所形成的硬化物的耐熱性及耐光性(特別是良好的耐熱性)的傾向。而且，硬化物(反射器)的線膨脹係數變低，有不易發生使用該反射器的光半導體元件安裝用基板之引線架翹曲等缺陷的傾向。另一方面，藉由無機填充劑(D)的含量為1500重量份以下，提高硬化物(反射器)的成形性，有更適合量產的傾向。 The content (adjusted amount) of the inorganic filler (D) of the curable resin composition of the second aspect of the present invention is not particularly limited, and the total amount of the epoxy group-containing compound contained in the curable resin composition is 100. It is preferably from 10 to 1,500 parts by weight, more preferably from 50 to 1200 parts by weight, still more preferably from 100 to 1000 parts by weight, based on parts by weight. When the content of the inorganic filler (D) is 10 parts by weight or more, when the curable resin composition is formed by compression molding, heat resistance and light resistance (especially good heat resistance) of the formed cured product are improved. Sexuality. Further, the linear expansion coefficient of the cured product (reflector) tends to be low, and there is a tendency that defects such as warpage of the lead frame of the optical semiconductor element mounting substrate using the reflector tend to occur. On the other hand, when the content of the inorganic filler (D) is 1,500 parts by weight or less, the formability of the cured product (reflector) is improved, and it is more suitable for mass production.

本發明的第1態樣或第2態樣的硬化性樹脂組成物之白色顏料(C)及無機填充劑(D)的最大粒徑，無特別限制，較理想為200μm以下，更理想為185μm以下，又更理想為175μm以下，特別理想為150μm以下。上述最大粒徑為200μm以下時，比使用最大粒徑超過200μm的白色顏料或無機填充劑的情況，硬化性樹脂組成物藉由壓縮成型而形成的硬化物，有耐熱性、耐光性及耐龜裂性(特別是良好的耐熱性)更佳的傾向。而且，藉由使用最大粒徑小的白色顏料及無機填充劑，變成可增加此等的含量，有更提高硬化物的光反射性、耐熱性及耐光性的傾向。上述最大粒徑的下限，例如為0.01μm以上。再者，上述 最大粒徑，係包含於本發明的硬化性樹脂組成物的白色顏料(C)及無機填充劑(D)全體的最大粒徑。上述最大粒徑，係指雷射繞射‧散射法測定的粒徑分佈之最大粒徑。 The maximum particle diameter of the white pigment (C) and the inorganic filler (D) of the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is preferably 200 μm or less, more preferably 185 μm. Hereinafter, it is more preferably 175 μm or less, and particularly preferably 150 μm or less. When the maximum particle diameter is 200 μm or less, when a white pigment or an inorganic filler having a maximum particle diameter of more than 200 μm is used, the cured resin composition is cured by compression molding, and has heat resistance, light resistance, and turtle resistance. Cracking (especially good heat resistance) is a better tendency. Further, by using a white pigment having a small maximum particle diameter and an inorganic filler, the content of these pigments can be increased, and the light reflectivity, heat resistance, and light resistance of the cured product tend to be improved. The lower limit of the above maximum particle diameter is, for example, 0.01 μm or more. In addition, the maximum particle diameter is the maximum particle diameter of the white pigment (C) and the inorganic filler (D) which are contained in the curable resin composition of the present invention. The above maximum particle diameter refers to the maximum particle diameter of the particle size distribution measured by the laser diffraction ‧ scattering method.

[硬化劑(E)] [hardener (E)]

本發明的第1態樣或第2態樣的硬化性樹脂組成物之硬化劑(E)，係具有藉由與脂環式環氧化合物(A)、作為應力緩和劑(H)之後述的環氧基改質聚矽氧油、又本發明的第2態樣的情況為異氰脲酸衍生物(I)、矽氧烷衍生物(J)等具有環氧基的化合物反應而使硬化性樹脂組成物硬化的作用的化合物。作為硬化劑(E)，可使用習知至慣用的硬化劑，無特別限制，例如酸酐類(酸酐系硬化劑)、胺類(胺系硬化劑)、聚醯胺樹脂、咪唑類(咪唑系硬化劑)、聚硫醇類(聚硫醇系硬化劑)、酚類(酚系硬化劑)、聚羧酸類、二氰基二醯胺類、有機酸醯肼類(organic acid hydrazide)等。 The curing agent (E) of the curable resin composition of the first aspect or the second aspect of the present invention is described later with the alicyclic epoxy compound (A) and the stress relieving agent (H). In the case of the epoxy-modified polyoxime oil and the second aspect of the present invention, a compound having an epoxy group such as an isocyanuric acid derivative (I) or a decyl alkane derivative (J) is reacted to harden A compound which acts to harden the resin composition. As the curing agent (E), a conventional to conventional curing agent can be used without particular limitation, and examples thereof include an acid anhydride (an acid anhydride curing agent), an amine (an amine curing agent), a polyamide resin, and an imidazole (imidazole). A curing agent), a polythiol (polythiol-based curing agent), a phenol (phenolic curing agent), a polycarboxylic acid, a dicyanodiamide, an organic acid hydrazide or the like.

作為硬化劑(E)的酸酐類(酸酐系硬化劑)，可使用習知至慣用的酸酐系硬化劑，無特別限制，例如甲基四氫鄰苯二甲酸酐(4-甲基四氫鄰苯二甲酸酐、3-甲基四氫鄰苯二甲酸酐等)、甲基六氫鄰苯二甲酸酐(4-甲基六氫鄰苯二甲酸酐、3-甲基六氫鄰苯二甲酸酐等)、十二烯基琥珀酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、鄰苯二甲酸酐、馬來酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基環己烯二羧酸酐、均苯四甲酸酐、偏苯三酸酐、二苯甲酮四羧酸酐、納迪克酸酐(nadic anhydride)、甲基納迪克酸 酐、氫化甲基納迪克酸酐、4-(4-甲基-3-戊烯基)四氫鄰苯二甲酸酐、琥珀酸酐、己二酸酐、癸二酸酐、十二烷二酸酐、甲基環己烯四羧酸酐、乙烯基醚-馬來酸酐共聚物、烷基苯乙烯-馬來酸酐共聚物等。其中，在可有效率地調製均勻的硬化性樹脂組成物的觀點、容易與脂環式環氧化合物(A)混合成為在25℃為液狀的混合物(硬化劑組成物)的觀點，以在25℃為液狀的酸酐[例如甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、十二烯基琥珀酸酐、甲基內亞甲基四氫鄰苯二甲酸酐等]較理想。另一方面，對於在25℃為固體狀的酸酐，藉由例如使其溶解於在25℃為液狀的酸酐而成為液狀的混合物，有提高作為本發明的第1態樣或第2態樣的硬化性樹脂組成物之硬化劑(E)的處理性的傾向。作為酸酐系硬化劑，在硬化物的耐熱性、光反射性的觀點，較理想為飽和單環烴二羧酸酐(也包含烷基等取代基鍵結於環者)。 As the acid anhydride (an acid anhydride-based curing agent) of the curing agent (E), a conventional to conventional acid anhydride-based curing agent can be used without particular limitation, such as methyltetrahydrophthalic anhydride (4-methyltetrahydroortholine). Phthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic acid) Methyl anhydride, etc.), dodecenyl succinic anhydride, methyl endomethylene tetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid Anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecane dianhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether - Maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, and the like. In view of the fact that it is possible to efficiently prepare a uniform curable resin composition, it is easy to mix with the alicyclic epoxy compound (A) to form a liquid mixture (curing agent composition) at 25° C. 25 ° C is a liquid acid anhydride [such as methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl endomethylene tetrahydrophthalic anhydride, etc. ] is ideal. On the other hand, the acid anhydride which is solid at 25 ° C is, for example, dissolved in a liquid-like acid anhydride at 25 ° C to form a liquid mixture, which is improved as the first aspect or the second aspect of the present invention. The handleability of the hardener (E) of the curable resin composition tends to be. The acid anhydride-based curing agent is preferably a saturated monocyclic hydrocarbon dicarboxylic anhydride (including a substituent such as an alkyl group bonded to the ring) from the viewpoint of heat resistance and light reflectivity of the cured product.

作為硬化劑(E)的胺類(胺系硬化劑)，可使用習知至慣用的胺系硬化劑，無特別限制，例如伸乙基二胺、二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、二伸丙基二胺、二乙基胺基丙基胺、聚伸丙基三胺等脂肪族聚胺；烯二胺、異佛酮二胺、雙(4-胺基-3-甲基二環己基)甲烷、二胺基二環己基甲烷、雙(胺基甲基)環己烷、N-胺基乙基哌嗪、3,9-雙(3-胺基丙基)-3,4,8,10-四氧雜螺環[5,5]十一烷等的脂環式聚胺；間-伸苯基二胺、對-伸苯基二胺、伸甲苯基-2,4-二胺、伸甲苯基-2,6-二胺、伸均三苯基-2,4- 二胺、3,5-二乙基伸甲苯基-2,4-二胺、3,5-二乙基伸甲苯基-2,6-二胺等單核聚胺；伸聯苯基二胺、4,4-二胺基二苯基甲烷、2,5-伸萘基二胺、2,6-伸萘基二胺等芳香族聚胺等。 As the amine (amine-based curing agent) of the curing agent (E), a conventional to conventional amine-based curing agent can be used without particular limitation, such as ethylene diamine, di-ethyltriamine, and tri-ethyl ester. Aliphatic polyamines such as tetraamine, tetra-ethylpentamine, di-propyldiamine, diethylaminopropylamine, poly-propyltriamine; enediamine, isophoronediamine, bis ( 4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 3,9-bis (3) An alicyclic polyamine such as -aminopropyl)-3,4,8,10-tetraoxaspiro[5,5]undecane; m-phenylenediamine, p-phenylene Amine, tolyl-2,4-diamine, tolyl-2,6-diamine, stilbene-2,4-diamine, 3,5-diethyl-tolyl-2,4 a mononuclear polyamine such as diamine or 3,5-diethyl-tolyl-2,6-diamine; phenyldiamine, 4,4-diaminodiphenylmethane, 2,5-extension An aromatic polyamine such as naphthyldiamine or 2,6-anaphthyldiamine.

作為硬化劑(E)的酚類(酚系硬化劑)，可使用習知至慣用的酚系硬化劑，無特別限制，例如酚醛型酚樹脂、酚醛型甲酚樹脂、對二甲苯改質酚樹脂、對二甲苯‧間二甲苯改質酚樹脂等芳烷基樹脂、萜(terpene)改質酚樹脂、二環戊二烯改質酚樹脂、三酚丙烷等。 As the phenol (phenolic curing agent) of the curing agent (E), a conventional to conventional phenolic curing agent can be used without particular limitation, such as a novolac type phenol resin, a novolac type cresol resin, and a p-xylene modified phenol. An aralkyl resin such as a resin, a p-xylene/m-xylene-modified phenol resin, a terpene-modified phenol resin, a dicyclopentadiene-modified phenol resin, or a trisphenol propane.

作為硬化劑(E)的聚醯胺樹脂，例如分子內具有1級胺基及2級胺基的任一者或兩者的聚醯胺樹脂等。 The polyamine resin which is the curing agent (E) is, for example, a polyamide resin having one or both of a primary amine group and a secondary amine group in the molecule.

作為硬化劑(E)的咪唑類(咪唑系硬化劑)，可使用習知至慣用的咪唑系硬化劑，無特別限制，例如2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、1-苯甲基-2-甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2-甲基咪唑鎓異氰脲酸酯、2-苯基咪唑鎓異氰脲酸酯、2,4-二氰基-6-[2-甲基咪唑基-(1)]-乙基-s-三嗪、2,4-二氰基-6-[2-乙基-4-甲基咪唑基-(1)]-乙基-s-三嗪等。 As the imidazole (imidazole-based curing agent) of the curing agent (E), a conventional to conventional imidazole-based curing agent can be used without particular limitation, such as 2-methylimidazole or 2-ethyl-4-methylimidazole. 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyano Base ethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate , 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-dicyandiamide -6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-dicyano-6-[2-ethyl-4-methylimidazolyl-(1 )]-ethyl-s-triazine and the like.

作為硬化劑(E)的聚硫醇類(聚硫醇系硬化劑)，例如液狀的聚硫醇、聚硫化物樹脂等。 The polythiol (polythiol-based curing agent) as the curing agent (E) is, for example, a liquid polythiol or a polysulfide resin.

作為硬化劑(E)的聚羧酸類(聚羧酸系硬化劑)，例如己二酸、癸二酸、偏苯三酸、含有羧基的聚酯等。 The polycarboxylic acid (polycarboxylic acid-based curing agent) as the curing agent (E) is, for example, adipic acid, sebacic acid, trimellitic acid, or a carboxyl group-containing polyester.

其中，作為硬化劑(E)，在硬化物的耐熱性、耐光性、光反射性的觀點，較理想為酸酐類(酸酐系硬化劑)。再者，於本發明的第1態樣或第2態樣的硬化性樹脂組成物，硬化劑(E)，可使用單獨1種，亦可組合2種以上使用。而且，硬化劑可藉由習知至慣用的方法製造，亦可使用例如商品名「RIKACID MH-700」、「RIKACID MH-700F」、「RIKACID MH-700G」、「RIKACID TH」、「RIKACID HH」、「RIKACID HNA-100」(以上新日本理化(股)製)；商品名「HN-5500」(日立化成工業(股)製)；商品名「H-TMAn-S」、「H-TMAn」(以上三菱氣體化學(股)製)；商品名「YH1120」(三菱化學(股)製)等市售品。 In particular, the curing agent (E) is preferably an acid anhydride (an acid anhydride-based curing agent) from the viewpoint of heat resistance, light resistance, and light reflectivity of the cured product. In addition, the curing agent (E) of the first aspect or the second aspect of the present invention may be used alone or in combination of two or more. Further, the curing agent can be produced by a conventionally known method, and for example, "RIKACID MH-700", "RIKACID MH-700F", "RIKACID MH-700G", "RIKACID TH", "RIKACID HH" can also be used. "RIKACID HNA-100" (above New Japan Physical and Chemical Co., Ltd.); trade name "HN-5500" (Hitachi Chemical Industry Co., Ltd.); trade name "H-TMAn-S", "H-TMAn (The above Mitsubishi Gas Chemical Co., Ltd.); the commercial name "YH1120" (Mitsubishi Chemical Co., Ltd.) and other commercial products.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物含有硬化劑(E)的情況，硬化劑(E)的含量(調配量)，無特別限制，對硬化性樹脂組成物(100重量%)而言，較理想為1至40重量%，更理想為3至35重量%，又更理想為5至30重量%。藉由硬化劑(E)的含量為1重量%以上，變得更充分硬化，有提高硬化物的耐龜裂性的傾向。另一方面，藉由硬化劑(E)的含量為40重量%以下，更抑制著色，有容易得到色相佳的硬化物(反射器)的傾向。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains the curing agent (E), the content (adjusted amount) of the curing agent (E) is not particularly limited, and the curable resin composition is not particularly limited. (100% by weight), more preferably 1 to 40% by weight, still more preferably 3 to 35% by weight, still more preferably 5 to 30% by weight. When the content of the curing agent (E) is 1% by weight or more, the curing is more sufficiently performed, and the crack resistance of the cured product tends to be improved. On the other hand, when the content of the curing agent (E) is 40% by weight or less, coloring is further suppressed, and a cured product (reflector) having a good hue tends to be easily obtained.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物含有硬化劑(E)的情況，硬化劑(E)的含量(調配量)，無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物全部量100重量份而言，較理想為40至200重量份，更理想為50至150重量份。更具體者，於使用酸 酐類作為硬化劑(E)的情況，對包含於本發明的第1態樣或第2態樣的硬化性樹脂組成物的全部具有環氧基的化合物的環氧基1當量而言，以使用成為0.5至1.5當量的比例較理想。藉由硬化劑(E)的含量為40重量份以上，變得更充分硬化，有提高硬化物的耐龜裂性的傾向。另一方面，藉由硬化劑(E)的含量為200重量份以下，更抑制著色，有容易得到色相佳的硬化物(反射器)的傾向。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains the curing agent (E), the content (adjusted amount) of the curing agent (E) is not particularly limited, and is included in the curable resin. The total amount of the epoxy group-containing compound of the composition is preferably from 40 to 200 parts by weight, more preferably from 50 to 150 parts by weight, per 100 parts by weight. More specifically, when an acid anhydride is used as the curing agent (E), the epoxy group of the compound having an epoxy group in the curable resin composition of the first aspect or the second aspect of the present invention is used. In terms of 1 equivalent, it is preferably used in a ratio of 0.5 to 1.5 equivalents. When the content of the curing agent (E) is 40 parts by weight or more, the curing is more sufficiently performed, and the crack resistance of the cured product tends to be improved. On the other hand, when the content of the curing agent (E) is 200 parts by weight or less, coloring is further suppressed, and a cured product (reflector) having a good hue tends to be easily obtained.

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

本發明的第1態樣或第2態樣的硬化性樹脂組成物，可包含硬化促進劑(F)。硬化促進劑(F)係在包含於本發明的第1態樣或第2態樣的硬化性樹脂組成物的具有環氧基的化合物(例如脂環式環氧化合物(A)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)、作為應力緩和劑(H)之後述的環氧基改質聚矽氧油)與硬化劑(E)等硬化劑反應時，具有促進其反應速度的功能的化合物。作為硬化促進劑(F)，可使用習知至慣用的硬化促進劑，例如1,8-二氮雜雙環[5.4.0]十一烯-7(DBU)或其鹽(例如酚鹽、辛酸鹽、對-甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽等)、1,5-二氮雜雙環[4.3.0]壬烯-5(DBN)或其鹽(例如酚鹽、辛酸鹽、對-甲苯磺酸鹽、甲酸鹽、四苯基硼酸鹽等)；苯甲基二甲基胺、2,4,6-三(二甲基胺基甲基)酚、N,N-二甲基環己基胺基等3級胺；2-乙基-4-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑等咪唑；磷酸酯、三苯基膦等膦類；四苯基鏻四(對-甲苯基)硼酸鹽等鏻 化合物；辛酸鋅、辛酸錫等有機金屬鹽；金屬螫合物等。 The curable resin composition of the first aspect or the second aspect of the present invention may contain a curing accelerator (F). The hardening accelerator (F) is an epoxy group-containing compound (for example, an alicyclic epoxy compound (A) or an isocyanurate contained in the curable resin composition of the first aspect or the second aspect of the present invention. When the acid derivative (I), the decane derivative (J), and the epoxy-modified polyoxyxene oil described later as the stress relieving agent (H) react with a curing agent such as a curing agent (E), it promotes A compound whose function is the speed of reaction. As the hardening accelerator (F), a conventional to conventional hardening accelerator such as 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (for example, phenolate or octanoic acid) can be used. Salt, p-toluenesulfonate, formate, tetraphenylborate, etc.), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (for example, phenate, octanoic acid) Salt, p-toluenesulfonate, formate, tetraphenylborate, etc.; benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N - a tertiary amine such as dimethylcyclohexylamine; an imidazole such as 2-ethyl-4-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole; a phosphate, triphenyl a phosphine such as a phosphine; an anthracene compound such as tetraphenylphosphonium tetra(p-tolyl)borate; an organic metal salt such as zinc octylate or tin octylate; a metal chelate.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物，硬化促進劑(F)可使用單獨1種，亦可組合2種以上使用。 In the first embodiment or the second aspect of the present invention, the curing accelerator (F) may be used alone or in combination of two or more.

而且，硬化促進劑(F)可藉由習知至慣用的方法製造，亦可使用例如商品名「U-CAT SA 506」、「U-CAT SA 102」、「U-CAT 5003」、「U-CAT 18X」、「12XD」(開發品)(以上SANAPRO(股)製)；商品名「TPP-K」、「TPP-MK」(以上北興化學工業(股)製)；商品名「PX-4ET」(日本化學工業(股)製)等市售品。 Further, the hardening accelerator (F) can be produced by a conventional to conventional method, and for example, "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U" can also be used. -CAT 18X", "12XD" (developed product) (above SANAPRO); trade name "TPP-K", "TPP-MK" (above Beixing Chemical Industry Co., Ltd.); trade name "PX- Commercial products such as 4ET" (Japan Chemical Industry Co., Ltd.).

於本發明的第1態樣或第2態樣的硬化性樹脂組成物含有硬化促進劑(F)的情況，硬化促進劑(F)的含量(調配量)無特別限制，對硬化性樹脂組成物(100重量%)而言，較理想為0.0001至5重量%，更理想為0.001至1重量%。藉由硬化促進劑(F)的含量為0.0001重量%以上，有更有效率地進行反應的傾向。另一方面，藉由硬化促進劑(F)的含量為5重量%以下，更提高硬化性樹脂組成物的保存性，更抑制著色，有容易得到色相佳的硬化物(反射器)的傾向。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains the curing accelerator (F), the content (mixing amount) of the curing accelerator (F) is not particularly limited, and is composed of a curable resin. The amount (100% by weight) is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight. When the content of the curing accelerator (F) is 0.0001% by weight or more, the reaction tends to proceed more efficiently. On the other hand, when the content of the curing accelerator (F) is 5% by weight or less, the storage property of the curable resin composition is further improved, and coloring is further suppressed, and a cured product (reflector) having a good hue tends to be easily obtained.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物含有硬化促進劑(F)的情況，硬化促進劑(F)的含量(調配量)無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為0.05至15重量份，更理想為0.1至12重量份，又更理想 為0.2至10重量份，特別理想為0.25至8重量份。藉由硬化促進劑(F)的含量為0.05重量份以上，有能夠更有效率地進行反應的傾向。另一方面，藉由硬化促進劑(F)的含量為15重量份以下，更提高硬化性樹脂組成物的保存性，更抑制著色，有容易得到色相佳的硬化物(反射器)的傾向。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains the curing accelerator (F), the content (adjusted amount) of the curing accelerator (F) is not particularly limited, and is included in the curability. The total amount of the epoxy group-containing compound of the resin composition is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 12 parts by weight, still more preferably 0.2 to 10 parts by weight, particularly preferably 100 parts by weight, more preferably 0.25 to 8 parts by weight. When the content of the curing accelerator (F) is 0.05 parts by weight or more, the reaction tends to proceed more efficiently. On the other hand, when the content of the curing accelerator (F) is 15 parts by weight or less, the storage stability of the curable resin composition is further improved, and coloring is further suppressed, and a cured product (reflector) having a good hue tends to be easily obtained.

[硬化觸媒(G)] [hardening catalyst (G)]

本發明的第1態樣或第2態樣的硬化性樹脂組成物之硬化觸媒(G)，係具有藉由引發及/或促進脂環式環氧化合物(A)、作為應力緩和劑(H)之後述的環氧基改質聚矽氧油、又本發明的第2態樣的情況為異氰脲酸衍生物(I)、矽氧烷衍生物(J)等陽離子聚合性化合物的硬化反應(聚合反應)，而使硬化性樹脂組成物硬化的作用的化合物。作為硬化觸媒(G)，無特別限制，例如藉由施以光照射、加熱處理而發生陽離子物種、引發聚合之陽離子聚合引發劑(光陽離子聚合引發劑、熱陽離子聚合引發劑等)、路易斯酸‧胺錯合物、布氏酸鹽類、咪唑類等。 The curing catalyst (G) of the curable resin composition of the first aspect or the second aspect of the present invention has an alicyclic epoxy compound (A) as a stress relieving agent by initiating and/or promoting ( H) The epoxy-modified polyoxyxane oil to be described later and the second aspect of the present invention are a cationically polymerizable compound such as an isocyanuric acid derivative (I) or a decane derivative (J). A compound which hardens the reaction (polymerization reaction) and hardens the curable resin composition. The curing catalyst (G) is not particularly limited, and for example, a cationic species, a cationic polymerization initiator (photocationic polymerization initiator, a thermal cationic polymerization initiator, etc.), and a Lewis acid are generated by light irradiation or heat treatment. Amine complex, Buchrate, imidazole, and the like.

作為硬化觸媒(G)的光陽離子聚合引發劑，例如六氟銻酸鹽、五氟羥基銻酸鹽、六氟磷酸鹽、六氟砷酸鹽等，更具體者例如三芳香基硫鎓六氟磷酸鹽(例如對-苯基硫苯基二苯基硫鎓六氟磷酸鹽等)、三芳香基硫鎓六氟銻酸鹽等的硫鎓鹽(特別是三芳香基硫鎓鹽)；二芳香基錪六氟磷酸鹽、二芳香基錪六氟銻酸鹽、雙(十二烷基苯基)錪四(五氟苯基)硼酸鹽、錪[4-(4-甲基苯基-2-甲基丙基)苯 基]六氟磷酸鹽等錪鹽；四氟鏻六氟磷酸鹽等鏻鹽；N-己基吡啶鎓四氟硼酸鹽等吡啶鎓鹽等。而且，作為光陽離子聚合引發劑，可使用例如商品名「UVACURE1590」(Daicel-Cytec(股)製)；商品名「CD-1010」、「CD-1011」、「CD-1012」(以上美國SARTOMER製)；商品名「IRGACURE264」(BASF公司製)；商品名「CIT-1682」(日本曹達(股)製)等市售品較理想。 a photocationic polymerization initiator as a curing catalyst (G), such as hexafluoroantimonate, pentafluorohydroxy decanoate, hexafluorophosphate, hexafluoroarsenate or the like, more specifically, for example, triarylsulfonium a sulfonium salt such as a fluorophosphate (for example, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate) or a triarylsulfonium hexafluoroantimonate (particularly a triarylsulfonium salt); Diarylsulfonium hexafluorophosphate, diarylsulfonium hexafluoroantimonate, bis(dodecylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, 錪[4-(4-methylphenyl) a phosphonium salt such as -2-methylpropyl)phenyl]hexafluorophosphate; a phosphonium salt such as tetrafluorophosphonium hexafluorophosphate; a pyridinium salt such as N-hexylpyridinium tetrafluoroborate; Further, as the photocationic polymerization initiator, for example, the trade name "UVACURE 1590" (manufactured by Daicel-Cytec Co., Ltd.); trade names "CD-1010", "CD-1011", "CD-1012" (above US SARTOMER) can be used. The product name "IRGACURE264" (manufactured by BASF Corporation); the commercial name "CIT-1682" (made by Japan's Soda Co., Ltd.) is preferable.

作為硬化觸媒(G)的熱陽離子聚合引發劑，例如芳香基二偶氮鹽、芳香基錪鹽、芳香基硫鎓鹽、連烯烴-離子錯合物(allene-ion complex)等，可使用商品名「PP-33」、「CP-66」、「CP-77」(以上(股)ADEKA製)；商品名「FC-509」(3M製)；商品名「UVE1014」(G.E.製)；商品名「SUNAID SI-60L」、「SUNAID SI-80L」、「SUNAID SI-100L」、「SUNAID SI-110L」、「SUNAID SI-150L」(以上三新化學工業(股)製)；商品名「CG-24-61」(BASF公司製)等市售品較理想。再者，作為熱陽離子聚合引發劑，例如鋁、鈦等金屬與乙醯基乙酸或二酮類的螫合物與三苯基矽烷醇等矽烷醇的化合物，或鋁、鈦等金屬與乙醯基乙酸或二酮類的螫合物與雙酚A等酚類的化合物等。 As the thermal cationic polymerization initiator of the curing catalyst (G), for example, an aromatic diazo salt, an aromatic sulfonium salt, an aryl sulfonium salt, an allene-ion complex, or the like can be used. Product name "PP-33", "CP-66", "CP-77" (manufactured by ADEKA); trade name "FC-509" (3M system); product name "UVE1014" (GE system); Product name "SUNAID SI-60L", "SUNAID SI-80L", "SUNAID SI-100L", "SUNAID SI-110L", "SUNAID SI-150L" (above Sanshin Chemical Industry Co., Ltd.); Commercial products such as "CG-24-61" (made by BASF) are ideal. Further, as the thermal cationic polymerization initiator, for example, a compound of a metal such as aluminum or titanium, a chelating compound of acetylacetic acid or a diketone, a decyl alcohol such as triphenyl decyl alcohol, or a metal such as aluminum or titanium and acetamidine. A compound of a acetic acid or a diketone and a phenolic compound such as bisphenol A or the like.

作為硬化觸媒(G)的路易斯酸‧胺錯合物，可使用習知至慣用的路易斯酸‧胺錯合物，無特別限制，例如BF3‧正-己基胺、BF3‧單乙基胺、BF3‧苯甲基胺、BF3‧二乙基胺、BF3‧哌啶、BF3‧三乙基胺、BF3‧苯胺、BF4‧正-己基胺、BF4‧單乙基胺、BF4‧苯甲基胺、BF4‧ 二乙基胺、BF4‧哌啶、BF4‧三乙基胺、BF4‧苯胺、PF5‧乙基胺、PF5‧異丙基胺、PF5‧丁基胺、PF5‧十二烷基胺、PF5‧苯甲基胺、AsF5‧十二烷基胺等。 As the Lewis acid ‧ amine complex of the hardening catalyst (G), a conventional to conventional Lewis acid ‧ amine complex can be used without particular limitation, such as BF 3 ‧ n-hexylamine, BF 3 ‧ monoethyl Amine, BF 3 ‧ benzylamine, BF 3 ‧ diethylamine, BF 3 ‧ piperidine, BF 3 ‧ triethylamine, BF 3 ‧ aniline, BF 4 ‧ n-hexylamine, BF 4 ‧ single B Amine, BF 4 ‧ benzylamine, BF 4 ‧ diethylamine, BF 4 ‧ piperidine, BF 4 ‧ triethylamine, BF 4 ‧ aniline, PF 5 ‧ ethylamine, PF 5 ‧ isopropyl Amine, PF 5 ‧ butylamine, PF 5 ‧ dodecylamine, PF 5 ‧ benzylamine, AsF 5 ‧ dodecylamine, and the like.

作為硬化觸媒(G)的布氏酸鹽類，可使用習知至慣用的布氏酸鹽類，無特別限制，例如脂肪族硫鎓鹽、芳香族硫鎓鹽、錪鹽、鏻鹽等。 As the sulphuric acid salt of the curing catalyst (G), conventionally known conventional sulfonic acid salts can be used, and are not particularly limited, and examples thereof include aliphatic sulfonium salts, aromatic sulfonium salts, barium salts, barium salts, and the like. .

作為硬化觸媒(G)的咪唑類，可使用習知至慣用的咪唑類，無特別限制，例如2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、1-苯甲基-2-甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2-甲基咪唑鎓異氰脲酸酯、2-苯基咪唑鎓異氰脲酸酯、2,4-二氰基-6-[2-甲基咪唑基-(1)]-乙基-s-三嗪、2,4-二氰基-6-[2-乙基-4-甲基咪唑基-(1)]-乙基-s-三嗪等。 As the imidazoles of the hardening catalyst (G), conventionally used imidazoles can be used without particular limitation, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-undecylimidazole. , 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl -2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-dicyano-6-[2- Methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-dicyano-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s - Triazine and the like.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物中，硬化觸媒(G)可使用單獨1種，亦可組合2種以上使用。再者，如上述，作為硬化觸媒(G)，可使用市售品。 In the first embodiment or the second aspect of the present invention, the curing catalyst (G) may be used alone or in combination of two or more. Further, as described above, a commercially available product can be used as the curing catalyst (G).

於本發明的第1態樣或第2態樣的硬化性樹脂組成物含有硬化觸媒(G)的情況，硬化觸媒(G)的含量(調配量)無特別限制，對硬化性樹脂組成物(100重量%)而言，較理想為0.0001至5重量%，更理想為0.001至1重 量%。藉由使用上述範圍內的硬化觸媒(G)，可得到耐熱性、耐光性佳的硬化物。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains the curing catalyst (G), the content (adjusted amount) of the curing catalyst (G) is not particularly limited, and is composed of a curable resin. The amount (100% by weight) is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight. By using the curing catalyst (G) in the above range, a cured product excellent in heat resistance and light resistance can be obtained.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物含有硬化觸媒(G)的情況，本發明的硬化性樹脂組成物之硬化觸媒(G)的含量(調配量)無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為0.0001至15重量份，更理想為0.01至12重量份，又更理想為0.05至10重量份，特別理想為0.05至8重量份。藉由使用上述範圍內的硬化觸媒(G)，可得到耐熱性、耐光性佳的硬化物。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains the curing catalyst (G), the content (setting amount) of the curing catalyst (G) of the curable resin composition of the present invention It is not particularly limited, and is preferably 0.0001 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, even more preferably 100 parts by weight, based on the total amount of the epoxy group-containing compound contained in the curable resin composition. It is 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight. By using the curing catalyst (G) in the above range, a cured product excellent in heat resistance and light resistance can be obtained.

[應力緩和劑(H)] [stress mitigator (H)]

本發明的第1態樣或第2態樣的硬化性樹脂組成物的必要成分之應力緩和劑(H)，係可緩和硬化物中的內部應力的化合物。本發明的第1態樣或第2態樣的硬化性樹脂組成物，藉由應力緩和劑(H)與脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)，又於本發明的第2態樣的情況為異氰脲酸衍生物(I)、矽氧烷衍生物(J)、脂環式聚酯樹脂(K)組合使用，即使增加白色顏料(C)、無機填充劑(D)的填充量，亦可進行壓縮成型，且有藉由壓縮成型所形成的硬化物的光反射性、耐熱性及耐光性佳的傾向。而且，藉由應力緩和劑(H)緩和硬化物的內部應力，可減少藉由壓縮成型之形成物的翹曲。 The stress relieving agent (H) which is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention is a compound which can alleviate the internal stress in the cured product. The first aspect or the second aspect of the curable resin composition of the present invention comprises a stress relaxation agent (H), an alicyclic epoxy compound (A), rubber particles (B), and a white pigment (C). In the case of the inorganic filler (D), in the second aspect of the present invention, the isocyanuric acid derivative (I), the decane derivative (J), and the alicyclic polyester resin (K) are used in combination. Even if the filling amount of the white pigment (C) or the inorganic filler (D) is increased, compression molding can be performed, and the cured product formed by compression molding tends to have good light reflectivity, heat resistance, and light resistance. Further, by suppressing the internal stress of the cured product by the stress relieving agent (H), warpage of the formed product by compression molding can be reduced.

作為上述應力緩和劑(H)，無特別限制，例 如聚矽氧橡膠粒子(H1)、聚矽氧油(H2)、液狀橡膠成分(H3)、熱塑性樹脂(H4)等。 The stress relieving agent (H) is not particularly limited, and examples thereof include polyasoxy rubber particles (H1), polyoxyxane oil (H2), liquid rubber component (H3), and thermoplastic resin (H4).

作為上述聚矽氧橡膠粒子(H1)，無特別限制，例如由聚甲基矽氧烷、聚甲基苯基矽氧烷等聚矽氧烷所構成者。 The polyoxyethylene rubber particles (H1) are not particularly limited, and are composed of, for example, polyoxymethane such as polymethyl siloxane or polymethylphenyl siloxane.

而且，構成聚矽氧橡膠粒子(H1)的聚矽氧烷，較理想為交聯者。作為交聯的聚矽氧烷，無特別限制，例如藉由矽烷醇基等的縮合反應、巰基矽烷基與乙烯基矽烷基的自由基反應、乙烯基矽烷基與羥基矽烷基(SiH基)的加成反應等進行交聯的聚矽氧烷，從反應性、反應步驟的觀點，以使含有乙烯基的有機聚矽氧烷與有機氫聚矽氧烷在鉑系觸媒的存在下進行加成反應而交聯的聚矽氧烷較理想。 Further, the polyoxyalkylene which constitutes the polyoxyethylene rubber particles (H1) is preferably a cross-linker. The crosslinked polyoxyalkylene is not particularly limited, and is, for example, a condensation reaction by a decyl alcohol group or the like, a radical reaction of a mercaptoalkyl group with a vinyl fluorenyl group, a vinyl decyl group and a hydroxy decyl group (SiH group). The polyoxyalkylene which is crosslinked by an addition reaction or the like is added in the presence of a platinum-based catalyst from the viewpoint of reactivity and a reaction step in the presence of a platinum-based organic polysiloxane and an organic hydrogen polyoxyalkylene. The polyoxyalkylene which is reacted and crosslinked is preferred.

而且，上述聚矽氧橡膠粒子(H1)，從與樹脂組成物的溶合、分散性的提高及分散後樹脂組成物的黏度調整的觀點，亦可經表面處理。表面處理的態樣無特別限制，例如用甲基丙烯酸甲酯包覆的聚矽氧橡膠粒子、聚矽氧樹脂包覆的聚矽氧橡膠粒子等。 Further, the above-mentioned polyoxyxylene rubber particles (H1) may be subjected to surface treatment from the viewpoints of improvement in dissolving and dispersibility of the resin composition and viscosity adjustment of the resin composition after dispersion. The surface treatment state is not particularly limited, and examples thereof include polyoxyethylene rubber particles coated with methyl methacrylate, polyoxyethylene rubber particles coated with polyoxymethylene resin, and the like.

上述聚矽氧橡膠粒子(H1)的平均粒徑(d50)無特別限制，較理想為0.1至100μm，更理想為0.5至50μm。而且，上述聚矽氧橡膠粒子(H1)的最大粒徑無特別限制，較理想為0.1至250μm，更理想為0.1至150μm。藉由平均粒徑為100μm以下(或最大粒徑為250μm以下)，有更提高硬化物的耐龜裂性的傾向。另一方面，藉由平均粒徑為0.1μm以上(或最大粒徑為0.1μm以上)，有更提高 上述聚矽氧橡膠粒子(H1)的分散性的傾向。 The average particle diameter (d 50 ) of the above polyoxyxylene rubber particles (H1) is not particularly limited, but is preferably from 0.1 to 100 μm, more preferably from 0.5 to 50 μm. Further, the maximum particle diameter of the above polyoxyxylene rubber particles (H1) is not particularly limited, but is preferably 0.1 to 250 μm, more preferably 0.1 to 150 μm. When the average particle diameter is 100 μm or less (or the maximum particle diameter is 250 μm or less), the crack resistance of the cured product tends to be increased. On the other hand, when the average particle diameter is 0.1 μm or more (or the maximum particle diameter is 0.1 μm or more), the dispersibility of the above polyoxyxylene rubber particles (H1) tends to be increased.

而且，上述聚矽氧橡膠粒子(H1)的形狀無特別限制，從提高操作性的觀點，以球狀較理想。 Further, the shape of the above polyoxyxene rubber particles (H1) is not particularly limited, and is preferably spherical in terms of improving workability.

作為上述聚矽氧橡膠粒子(H1)，從藉由壓縮成型可形成光反射性、耐熱性及耐光性佳的硬化物的觀點，以經交聯的聚矽氧烷所構成者或此等的表面以聚矽氧樹脂包覆者較理想，其中從樹脂成分與聚矽氧橡膠樹脂(H1)的相溶性的觀點，經交聯的聚矽氧烷的表面以聚矽氧樹脂包覆者特別理想。 The polyoxyxylene rubber particles (H1) are formed of crosslinked polyoxyalkylene or the like from the viewpoint of forming a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding. The surface is preferably coated with a polyoxyl resin, wherein the surface of the crosslinked polyoxyalkylene is coated with a polyoxyl resin from the viewpoint of the compatibility of the resin component with the polyoxyethylene rubber resin (H1). ideal.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物，聚矽氧橡膠粒子(H1)可使用單獨1種，亦可組合2種以上使用。而且，上述聚矽氧橡膠粒子(H1)，可藉由習知至慣用的方法製造，其製造方法，例如可使用特開平7-196815號公報記載的方法製造的聚矽氧橡膠粒子，或可使用商品名「KMP-600」、「KMP-601」、「KMP-602」、「KMP-605」、「X-52-7030」、「KMP-597」、「KMP-598」、「KMP-594」、「X-52-875」、「KMP-590」、「KMP-701」(以上信越化學工業(股)製)等市售品。 In the first aspect or the second aspect of the present invention, the polyoxyxylene rubber particles (H1) may be used alone or in combination of two or more. Further, the above-mentioned polyoxyethylene rubber particles (H1) can be produced by a conventionally known method, and the production method thereof can be, for example, polyfluorene rubber particles produced by the method described in JP-A-7-196815, or Use the trade names "KMP-600", "KMP-601", "KMP-602", "KMP-605", "X-52-7030", "KMP-597", "KMP-598", "KMP-" 594", "X-52-875", "KMP-590", "KMP-701" (above Shin-Etsu Chemical Co., Ltd.) and other commercial products.

作為上述聚矽氧油(H2)，無特別限制，例如非改質聚矽氧油、改質聚矽氧油等。 The polyoxyxane oil (H2) is not particularly limited, and examples thereof include non-modified polyoxyphthalic acid oils, modified polyoxygenated oils, and the like.

作為非改質聚矽氧油，無特別限制，例如聚二甲基矽氧烷型、聚甲基氫矽氧烷型、聚甲基苯基矽氧烷型等。 The non-modified polyfluorene oxide oil is not particularly limited, and examples thereof include a polydimethylsiloxane type, a polymethylhydroquinane type, a polymethylphenyloxane type, and the like.

作為改質聚矽氧油，無特別限制，可使用 例如對環氧樹脂具有反應性的反應性聚矽氧油、對環氧樹脂不具有反應性的無反應性聚矽氧油的任一種。作為反應性聚矽氧油，例如胺基改質型、環氧基改質型、羧基改質型、甲醇改質型、甲基丙烯酸改質型、硫醇改質型、酚改質型等。作為非反應性聚矽氧油，例如聚伸烷基醚改質型、甲基苯乙烯基改質型、烷基改質型、脂肪酸酯改質型、烷氧基改質型、氟改質型等。而且，反應性聚矽氧油，可具有非反應性改質基，例如聚伸烷基醚-胺基改質型聚矽氧油、聚伸烷基醚-環氧基改質型聚矽氧油等，其中以與環氧化合物(A)，又於本發明的第2態樣的情況為異氰脲酸衍生物(I)、矽氧烷衍生物(J)等具有環氧基的化合物具有反應性，可控制流動性、黏度的聚伸烷基醚-環氧基改質型聚矽氧油較理想。 The modified polyoxygenated oil is not particularly limited, and any of reactive non-reactive oxygenated oil which is reactive with an epoxy resin and non-reactive polyoxygenated oil which is not reactive with an epoxy resin can be used. As the reactive polyoxyxene oil, for example, an amine-based modified type, an epoxy-modified type, a carboxyl-modified type, a methanol-modified type, a methacrylic modified type, a thiol-modified type, a phenol-modified type, or the like . As a non-reactive polysulfonated oil, for example, polyalkylene ether modified type, methylstyryl modified type, alkyl modified type, fatty acid ester modified type, alkoxy modified type, fluorine modified Quality and so on. Moreover, the reactive polyoxyxene oil may have a non-reactive modified group, such as a polyalkylene ether-amine modified polyoxyxide oil, a polyalkylene ether-epoxy modified polyoxyl An oil or the like, which is an epoxy group-containing compound, such as an isocyanuric acid derivative (I) or a decyl alkane derivative (J), in the case of the epoxy compound (A) and the second aspect of the invention. A polyalkylene ether-epoxy modified polyoxyxide oil which is reactive and can control fluidity and viscosity is preferred.

作為上述聚矽氧油(H2)，從藉由壓縮成型可形成光反射性、耐熱性及耐光性佳的硬化物的觀點，以聚伸烷基醚-環氧基改質型聚矽氧油較理想，特別是環氧當量3000至15000的具有下述式(1)所示構造的聚伸烷基醚改質聚矽氧化合物(以下有稱為「聚伸烷基醚改質聚矽氧化合物(1)」的情況)較理想。 As the polyfluorene oxide (H2), a polyether alkyl ether-epoxy modified polyoxyxide oil is obtained from the viewpoint of forming a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding. More preferably, in particular, a polyalkylene ether modified polyxanthene compound having a structure represented by the following formula (1) having an epoxy equivalent of from 3,000 to 15,000 (hereinafter referred to as "polyalkylene ether modified polyoxyl oxide" The case of the compound (1)" is preferred.

上述式(1)中，R9為碳數2或3的伸烷基。作為碳數2或3的伸烷基，例如甲基亞甲基、二甲基亞甲基、伸乙基、伸丙基、三亞甲基等，以三亞甲基較理想。 In the above formula (1), R 9 is an alkylene group having 2 or 3 carbon atoms. As the alkylene group having 2 or 3 carbon atoms, such as methylmethylene, dimethylmethylene, ethylidene, propylidene or trimethylene, it is preferred to use a trimethylene group.

上述式(1)中，x表示80至140的整數。 In the above formula (1), x represents an integer of 80 to 140.

上述式(1)中，y表示1至5的整數。於y為2以上的整數的情況，y所附的括號內的構造，分別可為相同，亦可為不同。 In the above formula (1), y represents an integer of 1 to 5. In the case where y is an integer of 2 or more, the structures in parentheses attached to y may be the same or different.

上述式(1)中，z表示5至20的整數。再者，z所附的括號內的構造，分別可為相同，亦可為不同。 In the above formula (1), z represents an integer of 5 to 20. Furthermore, the configurations in parentheses attached to z may be the same or different.

上述式(1)中，A為具有下述式(1a)所示構造的聚伸烷基醚基。 In the above formula (1), A is a polyalkylene ether group having a structure represented by the following formula (1a).

上述式(1a)中，a及b分別獨立為0至40的整數。藉由a為40以下，有提高硬化物的耐水性的傾向。 In the above formula (1a), a and b are each independently an integer of 0 to 40. When a is 40 or less, there is a tendency to improve the water resistance of the cured product.

另一方面，藉由b為40以下，有提高硬化性樹脂組 成物的流動性的傾向。 On the other hand, when b is 40 or less, the fluidity of the curable resin composition tends to be improved.

a及b的合計，無特別限制，較理想為1至80的整數。藉由a及b的合計為該範圍，變得容易控制硬化物的耐水性、硬化性樹脂組成物的流動性。 The total of a and b is not particularly limited, and is preferably an integer of from 1 to 80. When the total of a and b is in this range, it is easy to control the water resistance of the cured product and the fluidity of the curable resin composition.

上述式(1a)中，B為氫原子或甲基。從硬化物的耐水性的觀點，B為甲基較理想。 In the above formula (1a), B is a hydrogen atom or a methyl group. From the viewpoint of water resistance of the cured product, B is preferably a methyl group.

上述式(1)之各構造單元的加成形式，只要是式(1)中的2個三甲基矽烷基存在於兩末端即可，可為無規則型，亦可為嵌段型。而且，上述式(1a)之各構造單元的加成形式，只要是B存在於末端即可，可為無規則型，亦可為嵌段型。而且，上述式(1)、(1a)之各構造單元的排列順序，也無特別限制。 The addition form of each structural unit of the above formula (1) may be either a random type or a block type as long as the two trimethyldecyl groups in the formula (1) are present at both ends. Further, the addition form of each structural unit of the above formula (1a) may be a random type or a block type as long as B is present at the end. Further, the order of arrangement of the respective structural units of the above formulas (1) and (1a) is not particularly limited.

上述聚伸烷基醚改質聚矽氧化合物(1)的環氧當量，如上述為3000至15000，較理想為4000至15000，更理想為5000至13000。藉由環氧當量為3000以上，有更提高硬化物內部的應力緩和的傾向。另一方面，藉由環氧當量為15000以下，有更提高與樹脂的相溶性的傾向。 The epoxy equivalent of the above polyalkylene ether-modified polyoxyl compound (1) is, as described above, from 3,000 to 15,000, more preferably from 4,000 to 15,000, still more preferably from 5,000 to 13,000. When the epoxy equivalent is 3,000 or more, the stress inside the cured product tends to be more moderated. On the other hand, when the epoxy equivalent is 15,000 or less, the compatibility with the resin tends to be further improved.

再者，聚伸烷基醚改質聚矽氧化合物(1)的環氧當量，可根據JIS K 7236：2001測定。 Further, the epoxy equivalent of the polyalkylene ether-modified polysiloxane (1) can be measured in accordance with JIS K 7236:2001.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物，聚矽氧油(H2)可使用單獨1種，亦可組合2種以上使用。而且，上述聚矽氧油(H2)可藉由習知至慣用的方法製造，可使用例如藉由特開2008-201904號公報記載的方法製造的聚矽氧油(H2)，或可使用商品名「SF8421」 (Toray-Dow Corning(股)製)、商品名「Y-19268」(日本Momentive Performance Materials(同)製)等市售品。 In the first aspect or the second aspect of the present invention, the polyoxygenated oil (H2) may be used alone or in combination of two or more. Further, the above-mentioned polyoxygenated oil (H2) can be produced by a conventionally known method, and for example, a polyoxygenated oil (H2) produced by the method described in JP-A-2008-201904, or a commercially available product can be used. Commercial products such as "SF8421" (Toray-Dow Corning Co., Ltd.) and trade name "Y-19268" (made by Japan Momentive Performance Materials).

作為上述液狀橡膠成分(H3)，無特別限制，例如聚丁二烯、順丁烯二酸化聚丁二烯、丙烯酸化聚丁二烯、甲基丙烯酸化聚丁二烯、環氧基化聚丁二烯、丙烯腈丁二烯橡膠、羧基末端丙烯腈丁二烯橡膠、胺基末端丙烯腈丁二烯橡膠、乙烯基末端丙烯腈丁二烯橡膠、苯乙烯丁二烯橡膠等。 The liquid rubber component (H3) is not particularly limited, and examples thereof include polybutadiene, maleic polybutadiene, acrylated polybutadiene, methacrylated polybutadiene, and epoxy group polymerization. Butadiene, acrylonitrile butadiene rubber, carboxyl terminal acrylonitrile butadiene rubber, amine terminal acrylonitrile butadiene rubber, vinyl terminal acrylonitrile butadiene rubber, styrene butadiene rubber, and the like.

上述液狀橡膠成分(H3)，可使用單獨1種，亦可組合2種以上使用。 The liquid rubber component (H3) may be used alone or in combination of two or more.

作為上述熱塑性樹脂(H4)，無特別限制，例如聚醯亞胺樹脂、聚醯胺樹脂、聚醚醯亞胺樹脂、聚酯樹脂、聚酯醯亞胺樹脂、苯氧基樹脂、聚碸樹脂、聚醚碸樹脂、聚苯硫醚樹脂、聚醚酮樹脂等。該等之中，從耐熱性的觀點，以苯氧基樹脂、聚醯亞胺樹脂較理想。該等熱塑性樹脂，可使用單獨1種，亦可組合2種以上使用。 The thermoplastic resin (H4) is not particularly limited, and examples thereof include, for example, a polyimide resin, a polyamide resin, a polyether phthalimide resin, a polyester resin, a polyester phthalimide resin, a phenoxy resin, and a polyfluorene resin. , polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, and the like. Among these, from the viewpoint of heat resistance, a phenoxy resin or a polyimide resin is preferred. These thermoplastic resins may be used alone or in combination of two or more.

上述熱塑性樹脂(H4)的玻璃轉化溫度(Tg)，無特別限制，較理想為200℃以下。 The glass transition temperature (Tg) of the thermoplastic resin (H4) is not particularly limited, but is preferably 200 ° C or lower.

上述應力緩和劑(H)，可使用單獨1種，亦可組合2種以上使用。 The above-mentioned stress relieving agent (H) may be used alone or in combination of two or more.

作為上述應力緩和劑(H)，從藉由壓縮成型可形成光反射性、耐熱性及耐光性佳的硬化物的觀點，以選自聚矽氧橡膠粒子(H1)及聚矽氧油(H2)所成群的至少1種較理想，特別是作為聚矽氧橡膠粒子(H1)，以表面具備聚矽氧樹脂 的交聯的聚二甲基矽氧烷較理想，作為聚矽氧油(H2)，以聚伸烷基醚改質聚矽氧化合物(1)較理想。 The stress relaxation agent (H) is selected from the group consisting of polyoxyxylene rubber particles (H1) and polyoxygenated oil (H2) from the viewpoint of forming a cured product excellent in light reflectivity, heat resistance and light resistance by compression molding. It is preferable that at least one of the groups is formed, in particular, as the polyoxyxylene rubber particles (H1), a crosslinked polydimethyl siloxane having a polyoxyxylene resin on the surface is preferable, and it is preferably used as a polyoxyxylene oil ( H2), it is preferred to modify the polyoxymethylene compound (1) with a polyalkylene ether.

本發明的第1態樣的硬化性樹脂組成物之應力緩和劑(H)的含量(調配量)，無特別限制，對脂環式環氧化合物(A)100重量份而言，較理想為1至200重量份，更理想為5至150重量份，又更理想為8至120重量份。藉由應力緩和劑(H)的含量為1重量份以上，即使增加白色顏料(C)、無機填充劑(D)的填充量仍可進行壓縮成型，而且有更提高所成形的硬化物的光反射性、耐熱性及耐光性的傾向。而且，成形品的翹曲被緩和，有提高尺寸安定性的傾向。另一方面，藉由應力緩和劑(H)的含量為200重量份以下，有更提高硬化性樹脂組成物的硬化性的傾向。 The content (mixing amount) of the stress relieving agent (H) of the curable resin composition of the first aspect of the invention is not particularly limited, and is preferably 100 parts by weight of the alicyclic epoxy compound (A). 1 to 200 parts by weight, more desirably 5 to 150 parts by weight, still more preferably 8 to 120 parts by weight. When the content of the stress relieving agent (H) is 1 part by weight or more, even if the filling amount of the white pigment (C) or the inorganic filler (D) is increased, compression molding can be performed, and light of the formed cured product can be further improved. The tendency to reflect, heat and light resistance. Further, the warpage of the molded article is alleviated, and the dimensional stability tends to be improved. On the other hand, when the content of the stress relieving agent (H) is 200 parts by weight or less, the curability of the curable resin composition tends to be increased.

本發明的第2態樣的硬化性樹脂組成物之應力緩和劑(H)的含量(調配量)，無特別限制，對脂環式環氧化合物(A)100重量份而言，較理想為1至250重量份，更理想為5至230重量份，又更理想為10至200重量份。藉由應力緩和劑(H)的含量為1重量份以上，即使增加白色顏料(C)、無機填充劑(D)的填充量，仍可進行壓縮成型，而且有更提高所成形的硬化物的光反射性、耐熱性及耐光性的傾向。而且，成形品的翹曲被緩和，有提高尺寸安定性的傾向。另一方面，藉由應力緩和劑(H)的含量為250重量份以下，有更提高硬化性樹脂組成物的硬化性的傾向。 The content (mixing amount) of the stress relieving agent (H) in the curable resin composition of the second aspect of the present invention is not particularly limited, and is preferably 100 parts by weight of the alicyclic epoxy compound (A). 1 to 250 parts by weight, more desirably 5 to 230 parts by weight, still more preferably 10 to 200 parts by weight. When the content of the stress relieving agent (H) is 1 part by weight or more, even if the filling amount of the white pigment (C) or the inorganic filler (D) is increased, compression molding can be performed, and the formed cured product can be further improved. The tendency of light reflectivity, heat resistance and light resistance. Further, the warpage of the molded article is alleviated, and the dimensional stability tends to be improved. On the other hand, when the content of the stress relieving agent (H) is 250 parts by weight or less, the curability of the curable resin composition tends to be increased.

本發明的第2態樣的硬化性樹脂組成物之應力緩和劑(H)的含量(調配量)，無特別限制，對包含於硬 化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為1至200重量份，更理想為5至150重量份，又更理想為8至120重量份。藉由應力緩和劑(H)的含量為1重量份以上，即使增加白色顏料(C)、無機填充劑(D)的填充量，仍可進行壓縮成型，而且有更提高所成形的硬化物的光反射性、耐熱性及耐光性的傾向。而且，成形品的翹曲被緩和，有提高尺寸安定性的傾向。另一方面，藉由應力緩和劑(H)的含量為200重量份以下，有更提高硬化性樹脂組成物的硬化性的傾向。 The content (mixing amount) of the stress relieving agent (H) in the curable resin composition of the second aspect of the present invention is not particularly limited, and the total amount of the epoxy group-containing compound contained in the curable resin composition is 100. It is preferably from 1 to 200 parts by weight, more preferably from 5 to 150 parts by weight, still more preferably from 8 to 120 parts by weight, based on parts by weight. When the content of the stress relieving agent (H) is 1 part by weight or more, even if the filling amount of the white pigment (C) or the inorganic filler (D) is increased, compression molding can be performed, and the formed cured product can be further improved. The tendency of light reflectivity, heat resistance and light resistance. Further, the warpage of the molded article is alleviated, and the dimensional stability tends to be improved. On the other hand, when the content of the stress relieving agent (H) is 200 parts by weight or less, the curability of the curable resin composition tends to be increased.

對本發明的第1態樣或第2態樣的硬化性樹脂組成物(100重量%)而言，應力緩和劑(H)的含量無特別限制，較理想為0.1至20重量%，更理想為0.3至18重量%，又更理想為0.5至15重量%。藉由應力緩和劑(H)的含量為0.1重量%以上，即使增加白色顏料(C)、無機填充劑(D)的填充量，仍可進行壓縮成型，且有更提高所成形的硬化物的光反射性、耐熱性及耐光性的傾向。而且，成形品的翹曲被緩和，有提高尺寸安定性的傾向。另一方面，藉由應力緩和劑(H)的含量為20重量%以下，有更提高硬化性樹脂組成物的硬化性的傾向。 The content of the stress relieving agent (H) in the first aspect or the second aspect of the curable resin composition (100% by weight) of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably From 0.3 to 18% by weight, still more preferably from 0.5 to 15% by weight. When the content of the stress relieving agent (H) is 0.1% by weight or more, even if the filling amount of the white pigment (C) or the inorganic filler (D) is increased, compression molding can be performed, and the formed cured product can be further improved. The tendency of light reflectivity, heat resistance and light resistance. Further, the warpage of the molded article is alleviated, and the dimensional stability tends to be improved. On the other hand, when the content of the stress relieving agent (H) is 20% by weight or less, the curability of the curable resin composition tends to be increased.

本發明的第1態樣的硬化性樹脂組成物，亦可再包含脂環式環氧化合物(A)以外的環氧化合物(有稱為「其他環氧化合物」的情況)。作為上述其他環氧化合物，可使用分子內具有1個以上環氧基(環氧乙烷環)的習知至慣用的化合物，無特別限制，例如芳香族環氧化合物(芳香 族環氧樹脂)、脂肪族環氧化合物(脂肪族環氧樹脂)、雜環式環氧化合物(雜環式環氧樹脂)、分子內具有1個以上環氧基的矽氧烷衍生物等。上述其他環氧化合物，可使用單獨1種，亦可組合2種以上使用。 The curable resin composition of the first aspect of the present invention may further contain an epoxy compound other than the alicyclic epoxy compound (A) (the case of "other epoxy compound"). As the other epoxy compound, a conventional to conventional compound having one or more epoxy groups (oxirane rings) in the molecule can be used, and is not particularly limited, and examples thereof include an aromatic epoxy compound (aromatic epoxy resin). An aliphatic epoxy compound (aliphatic epoxy resin), a heterocyclic epoxy compound (heterocyclic epoxy resin), a fluorene derivative having one or more epoxy groups in the molecule, and the like. The above-mentioned other epoxy compounds may be used alone or in combination of two or more.

作為上述雜環式環氧化合物，例如分子內具有1個以上環氧基的異氰脲酸衍生物等。於本發明的硬化性樹脂組成物包含上述異氰脲酸衍生物的情況，有提高硬化物的對電極黏合性、耐熱性、耐吸濕回焊性的傾向。 The heterocyclic epoxy compound is, for example, an isocyanuric acid derivative having one or more epoxy groups in its molecule. When the curable resin composition of the present invention contains the above-mentioned isocyanuric acid derivative, it tends to improve the electrode adhesion, heat resistance, and moisture reflow resistance of the cured product.

[分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)] [Isocyanuric acid derivative (I) having one or more oxirane rings in the molecule]

本發明的第2態樣的硬化性樹脂組成物的必要成分之異氰脲酸衍生物(I)，係異氰脲酸衍生物，是分子內至少具有1個以上環氧乙烷環的化合物。藉由本發明的第2態樣的硬化性樹脂組成物包含異氰脲酸衍生物(I)，提高硬化物的光反射性、耐熱性、耐光性，藉由上述應力緩和劑(H)、後述的矽氧烷衍生物(J)、脂環式聚酯樹脂(K)同時包含於硬化性樹脂組成物，更提高硬化物的光反射性、耐熱性、耐光性。異氰脲酸衍生物(I)的分子內所具有的環氧乙烷環的數目只要是1個以上即可，無特別限制，較理想為1至6個，更理想為1至3個。 The isocyanuric acid derivative (I) which is an essential component of the curable resin composition of the second aspect of the present invention is an isocyanuric acid derivative which is a compound having at least one oxirane ring in the molecule. . The curable resin composition according to the second aspect of the present invention contains the isocyanuric acid derivative (I), and improves the light reflectivity, heat resistance, and light resistance of the cured product, and the stress relieving agent (H) is described later. The decane derivative (J) and the alicyclic polyester resin (K) are simultaneously contained in the curable resin composition, and the light reflectivity, heat resistance, and light resistance of the cured product are further improved. The number of the oxirane rings in the molecule of the isocyanuric acid derivative (I) is not particularly limited as long as it is one or more, and is preferably from 1 to 6, more preferably from 1 to 3.

作為異氰脲酸衍生物(I)，例如下述式(III)所示的化合物。 The isocyanuric acid derivative (I) is, for example, a compound represented by the following formula (III).

式(III)中，R4至R6為相同或不同，表示氫原子或1價有機基。但是，R4至R6的至少一者為含有環氧基的1價有機基。作為上述1價有機基，例如1價脂肪族烴基(例如烷基、烯基等)；1價芳香族烴基(例如芳香基等)；1價雜環基；脂肪族烴基、脂環式烴基、及2個以上芳香族烴基結合所形成的1價基等。再者，1價有機基可具有取代基(例如羥基、羧基、鹵原子等取代基)。作為含有環氧基的1價有機基，例如環氧基、環氧丙基、2-甲基環氧基丙基、氧化環己烯基等後述含有環氧基的1價有機基。 In the formula (III), R 4 to R 6 are the same or different and each represents a hydrogen atom or a monovalent organic group. However, at least one of R 4 to R 6 is a monovalent organic group containing an epoxy group. The monovalent organic group is, for example, a monovalent aliphatic hydrocarbon group (for example, an alkyl group or an alkenyl group); a monovalent aromatic hydrocarbon group (for example, an aromatic group); a monovalent heterocyclic group; an aliphatic hydrocarbon group or an alicyclic hydrocarbon group; And a monovalent group formed by combining two or more aromatic hydrocarbon groups. Further, the monovalent organic group may have a substituent (for example, a substituent such as a hydroxyl group, a carboxyl group or a halogen atom). Examples of the monovalent organic group containing an epoxy group include an epoxy group-containing monovalent organic group which will be described later, such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group or a cyclohexene oxide group.

特別是式(III)之R4至R6為相同或不同，為下述式(IIIa)所示的基或下述式(IIIb)所示的基，R4至R6的至少一者為式(IIIa)所示的基較理想。 In particular, R 4 to R 6 of the formula (III) are the same or different and are a group represented by the following formula (IIIa) or a group represented by the following formula (IIIb), and at least one of R 4 to R 6 is The group represented by the formula (IIIa) is preferred.

上述式(IIIa)及式(IIIb)中的R7及R8，可為相同或不同，表示氫原子或碳數1至8的烷基。作為碳數 1至8的烷基，例如甲基、乙基、丙基、異丙基、丁基、異丁基、s-丁基、戊基、己基、庚基、辛基等直鏈或分支鏈狀的烷基。其中以甲基、乙基、丙基、異丙基等碳數1至3的直鏈或分支鏈狀的烷基較理想。式(IIIa)及式(IIIb)中的R7及R8為氫原子特別理想。 R 7 and R 8 in the above formula (IIIa) and formula (IIIb) may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As the alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or the like, or Branched chain alkyl. Among them, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or an isopropyl group is preferred. R 7 and R 8 in the formula (IIIa) and the formula (IIIb) are particularly preferably a hydrogen atom.

更具體者，作為上述異氰脲酸衍生物(I)，例如下述式(III-1)所示的化合物、下述式(III-2)所示的化合物、下述式(III-3)所示的化合物等。 More specifically, the isocyanuric acid derivative (I) is, for example, a compound represented by the following formula (III-1), a compound represented by the following formula (III-2), and the following formula (III-3). ) the compound shown and the like.

上述式(III-1)至(III-3)中，R7及R8可為相 同或不同，表示與式(IIIa)及式(IIIb)相同者。 In the above formulae (III-1) to (III-3), R 7 and R 8 may be the same or different and represent the same as those of the formula (IIIa) and the formula (IIIb).

作為上述式(III-1)所示化合物的代表例，例如單烯丙基二環氧丙基異氰脲酸酯、1-烯丙基-3,5-雙(2-甲基環氧基丙基)異氰脲酸酯、1-(2-甲基丙烯基)-3,5-二環氧丙基異氰脲酸酯、1-(2-甲基丙烯基)-3,5-雙(2-甲基環氧基丙基)異氰脲酸酯等。 As a representative example of the compound represented by the above formula (III-1), for example, monoallyl epoxypropyl isocyanurate, 1-allyl-3,5-bis(2-methyl epoxy group) Propyl)isocyanurate, 1-(2-methylpropenyl)-3,5-diepoxypropyl isocyanurate, 1-(2-methylpropenyl)-3,5- Bis(2-methylepoxypropyl)isocyanurate or the like.

作為上述式(III-2)所示化合物的代表例，例如二烯丙基單環氧丙基異氰脲酸酯、1,3-二烯丙基-5-(2-甲基環氧基丙基)異氰脲酸酯、1,3-雙(2-甲基丙烯基)-5-環氧丙基異氰脲酸酯、1,3-雙(2-甲基丙烯基)-5-(2-甲基環氧基丙基)異氰脲酸酯等。 As a representative example of the compound represented by the above formula (III-2), for example, diallyl monoepoxypropyl isocyanurate, 1,3-diallyl-5-(2-methyl epoxy group) Propyl)isocyanurate, 1,3-bis(2-methylpropenyl)-5-epoxypropyl isocyanurate, 1,3-bis(2-methylpropenyl)-5 -(2-Methylepoxypropyl) isocyanurate or the like.

作為上述式(III-3)所示化合物的代表例，例如三環氧丙基異氰脲酸酯、三(2-甲基環氧基丙基)異氰脲酸酯等。 Representative examples of the compound represented by the above formula (III-3) include, for example, trisethoxypropyl isocyanurate and tris(2-methyl epoxypropyl) isocyanurate.

再者，上述異氰脲酸衍生物(I)，亦可添加醇、酸酐等與環氧基反應的化合物預先進行改質後使用。 Further, the isocyanuric acid derivative (I) may be added or modified by adding a compound which reacts with an epoxy group, such as an alcohol or an acid anhydride, in advance.

其中，作為異氰脲酸衍生物(I)，從硬化物的光反射性、耐熱性、及溶解性的觀點，較理想為上述式(III-1)至(III-3)所示的化合物，更理想為上述式(III-1)所示的化合物。再者，於本發明的第2態樣的硬化性樹脂組成物，異氰脲酸衍生物(I)可使用單獨1種，亦可組合2種以上使用。再者，作為異氰脲酸衍生物(I)，可使用例如商品名「TEPIC」(日產化學工業(股)製)；商品名「MA-DGIC」、「DA-MGIC」(以上四國化成工業(股)製)等市售品。 In particular, the isocyanuric acid derivative (I) is preferably a compound represented by the above formula (III-1) to (III-3) from the viewpoints of light reflectivity, heat resistance, and solubility of the cured product. More preferably, it is a compound represented by the above formula (III-1). In addition, the isocyanuric acid derivative (I) may be used singly or in combination of two or more kinds in the curable resin composition of the second aspect of the invention. In addition, as the isocyanuric acid derivative (I), for example, the trade name "TEPIC" (manufactured by Nissan Chemical Industries Co., Ltd.); the trade name "MA-DGIC" and "DA-MGIC" can be used (the above four countries are formed) Commercial products such as industrial (stock) system.

本發明的第2態樣的硬化性樹脂組成物之異氰脲酸衍生物(I)的含量(調配量)，無特別限制，對硬化性樹脂組成物(100重量%)而言，較理想為0.05至15重量%，更理想為0.1至10重量%，又更理想為0.3至5重量%。藉由異氰脲酸衍生物(I)的含量為上述範圍內，可得到耐熱性及耐光性佳的硬化物。 The content (adjusted amount) of the isocyanuric acid derivative (I) of the curable resin composition of the second aspect of the present invention is not particularly limited, and is preferably a curable resin composition (100% by weight). It is 0.05 to 15% by weight, more desirably 0.1 to 10% by weight, still more preferably 0.3 to 5% by weight. When the content of the isocyanuric acid derivative (I) is within the above range, a cured product excellent in heat resistance and light resistance can be obtained.

本發明的第2態樣的硬化性樹脂組成物之異氰脲酸衍生物(I)的含量(調配量)，無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為1至60重量份，更理想為1至50重量份，又更理想為1至30重量份。藉由異氰脲酸衍生物(I)的含量為上述範圍內，可得到耐熱性及耐光性佳的硬化物。 The content (adjusted amount) of the isocyanuric acid derivative (I) of the curable resin composition of the second aspect of the present invention is not particularly limited, and is an epoxy group-containing compound contained in the curable resin composition. The total amount is preferably from 1 to 60 parts by weight, more preferably from 1 to 50 parts by weight, still more preferably from 1 to 30 parts by weight, per 100 parts by weight. When the content of the isocyanuric acid derivative (I) is within the above range, a cured product excellent in heat resistance and light resistance can be obtained.

[分子內具有2個以上環氧基的矽氧烷衍生物(J)] [A halogenated alkane derivative having two or more epoxy groups in the molecule (J)]

本發明的第2態樣的硬化性樹脂組成物的必要成分之矽氧烷衍生物(J)，係分子內具有2個以上的環氧基，具有由矽氧烷鍵結(-Si-O-Si-)所構成的骨架的化合物(矽氧烷化合物)。矽氧烷衍生物(J)之矽氧烷骨架(-Si-O-Si-)，無特別限制，例如環狀矽氧烷骨架；鏈狀的聚矽氧、籠型、梯型的聚倍半矽氧烷等矽氧烷骨架。其中，作為上述矽氧烷骨架，在提高硬化物的光反射性、耐熱性、耐光性並抑制光半導體裝置的亮度降低的觀點，較理想為環狀矽氧烷骨架、鏈狀聚矽氧骨架。亦即，作為上述矽氧烷衍 生物(J)，以分子內具有2個以上環氧基的環狀矽氧烷、分子內具有2個以上環氧基的直鏈狀聚矽氧較理想。 The alkane derivative (J) which is an essential component of the curable resin composition of the second aspect of the present invention has two or more epoxy groups in the molecule and has a bond with a siloxane (-Si-O). -Si-) a compound of a skeleton (a siloxane compound). The oxoxane skeleton (-Si-O-Si-) of the decane derivative (J) is not particularly limited, and is, for example, a cyclic oxirane skeleton; a chain polyfluorene, a cage, or a ladder type A oxane skeleton such as a heptane. In particular, the above-described oxoxane skeleton is preferably a cyclic oxime skeleton or a chain polyfluorene skeleton from the viewpoint of improving light reflectivity, heat resistance, and light resistance of the cured product and suppressing reduction in luminance of the optical semiconductor device. . In other words, as the above-mentioned decane derivative (J), a cyclic siloxane having two or more epoxy groups in the molecule and a linear polyoxygen having two or more epoxy groups in the molecule are preferable.

於矽氧烷衍生物(J)為分子內具有2個以上環氧基的環狀矽氧烷的情況，形成該矽氧烷環的Si-O單元的數目(等於形成矽氧烷環的矽原子數目)，無特別限制，在提高硬化物的耐熱性、耐光性的觀點，較理想為2至12，更理想為4至8。 In the case where the decane derivative (J) is a cyclic siloxane having two or more epoxy groups in the molecule, the number of Si-O units forming the siloxane ring (equal to the oxime forming the siloxane ring) The number of atoms is not particularly limited, and is preferably from 2 to 12, more preferably from 4 to 8, from the viewpoint of improving the heat resistance and light resistance of the cured product.

矽氧烷衍生物(J)的重量平均分子量，無特別限制，在提高硬化物的耐熱性、耐光性的觀點，較理想為100至3000，更理想為180至2000。再者，矽氧烷衍生物(J)的上述重量平均分子量，係由藉由GPC(凝膠滲透層析)法測定的換算標準聚苯乙烯的分子量算出。 The weight average molecular weight of the decane derivative (J) is not particularly limited, and is preferably from 100 to 3,000, more preferably from 180 to 2,000, from the viewpoint of improving heat resistance and light resistance of the cured product. Further, the above weight average molecular weight of the halogenated alkane derivative (J) is calculated from the molecular weight of the converted standard polystyrene measured by a GPC (gel permeation chromatography) method.

矽氧烷衍生物(J)分子內所具有的環氧基的數目，只要是2個以上即可，無特別限制，在提高硬化物的耐熱性、耐光性的觀點，較理想為2至4個(2個、3個或4個)。 The number of the epoxy groups in the molecule of the siloxane derivative (J) is not particularly limited as long as it is two or more, and is preferably 2 to 4 from the viewpoint of improving heat resistance and light resistance of the cured product. (2, 3 or 4).

矽氧烷衍生物(J)的環氧當量，無特別限制，在提高硬化物的耐熱性、耐光性的觀點，較理想為180至2000，更理想為180至1500，又更理想為180至1000。再者，上述環氧當量，係根據JIS K7236測定的值。 The epoxy equivalent of the decane derivative (J) is not particularly limited, and is preferably from 180 to 2,000, more preferably from 180 to 1,500, still more preferably from 180 to 2,000, from the viewpoint of improving heat resistance and light resistance of the cured product. 1000. Further, the above epoxy equivalent is a value measured in accordance with JIS K7236.

矽氧烷衍生物(J)所具有的環氧基，無特別限制，在提高硬化物的耐熱性、耐光性的觀點，較理想為構成脂環的鄰接的2個碳原子與氧原子所構成的環氧基(脂環式環氧基)，其中特別理想為氧化環己烯基。 The epoxy group of the oxirane derivative (J) is not particularly limited, and is preferably composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring from the viewpoint of improving the heat resistance and light resistance of the cured product. The epoxy group (alicyclic epoxy group) is particularly preferably oxidized cyclohexenyl.

作為矽氧烷衍生物(J)，例如下述式(IV)所示的矽氧烷化合物。 The oxoxane derivative (J) is, for example, a oxoxane compound represented by the following formula (IV).

式(IV)中，Ra為相同或不同，表示含有環氧基的基或烷基。但是式(IV)之Ra的至少2個(例如2至4個)為含有環氧基的基。上述含有環氧基的基，係包含至少1個環氧基(環氧乙烷環)，例如具有烯基等碳-碳不飽和雙鍵的直鏈或分支鏈狀脂肪族烴基所具有的至少1個雙鍵為環氧基化的基、具有碳-碳不飽和雙鍵的環狀脂肪族烴基(例如環烯基；環己烯基乙基等環烯基烷基等)所具有的至少1個雙鍵為環氧基化的基等。更具體者，例如1,2-環氧基乙基(環氧基)、1,2-環氧基丙基、2,3-環氧基丙基(環氧丙基)、2,3-環氧基-2-甲基丙基(甲基環氧丙基)、3,4-環氧基丁基、3-環氧丙氧基丙基、3,4-環氧基環己基甲基、2-(3,4-環氧基環己基)乙基等。其中，以具有碳-碳不飽和雙鍵的環狀脂肪族烴基所具有的至少1個雙鍵為環氧基化的基較理想。作為上述烷基，例如甲基、乙基、正丙基、異丙基、丁基、己基、辛基、異辛基、癸基、十二烷基等碳數1至20的直鏈或分支鏈狀的烷基等。其中以碳數1至10的直鏈或分支鏈狀的烷基較理想。 In the formula (IV), R a is the same or different and represents an epoxy group-containing group or an alkyl group. However, at least two (for example, 2 to 4) of R a of the formula (IV) are an epoxy group-containing group. The epoxy group-containing group contains at least one epoxy group (oxirane ring), for example, at least a linear or branched aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond such as an alkenyl group. At least one double bond is an epoxy group, and a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond (for example, a cycloalkenyl group such as a cycloalkenyl group; a cycloalkenyl group such as a cyclohexenylethyl group) One double bond is an epoxy group or the like. More specifically, for example, 1,2-epoxyethyl (epoxy), 1,2-epoxypropyl, 2,3-epoxypropyl (epoxypropyl), 2,3- Epoxy-2-methylpropyl (methylepoxypropyl), 3,4-epoxybutyl, 3-glycidoxypropyl, 3,4-epoxycyclohexylmethyl , 2-(3,4-epoxycyclohexyl)ethyl, and the like. Among them, a group having at least one double bond of a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond is preferably an epoxy group. As the above alkyl group, for example, a linear or branched carbon number of 1 to 20 such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group or a dodecyl group. A chain alkyl group or the like. Among them, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred.

式(IV)中，n表示2至12的整數。特別是 在硬化物的耐熱衝擊性、光半導體裝置的耐回焊性及耐熱衝擊性的觀點，作為n，較理想為4至8，更理想為4或5。 In the formula (IV), n represents an integer of 2 to 12. In particular, from the viewpoint of the thermal shock resistance of the cured product, the reflow resistance of the optical semiconductor device, and the thermal shock resistance, n is preferably 4 to 8, more preferably 4 or 5.

作為矽氧烷衍生物(J)，更具體者例如2,4-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,4,6,6,8,8-六甲基-環四矽氧烷、4,8-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,2,4,6,6,8-六甲基-環四矽氧烷、2,4-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-6,8-二丙基-2,4,6,8-四甲基-環四矽氧烷、4,8-二[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,6-二丙基-2,4,6,8-四甲基-環四矽氧烷、2,4,8-三[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,4,6,6,8-五甲基-環四矽氧烷、2,4,8-三[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-6-丙基-2,4,6,8-四甲基-環四矽氧烷、2,4,6,8-四[2-(3-{氧雜雙環[4.1.0]庚基})乙基]-2,4,6,8-四甲基-環四矽氧烷、分子內具有2個以上環氧基的聚倍半矽氧烷等。又更具體者，例如下述式所示的分子內具有2個以上環氧基的環狀矽氧烷等。 As the decane derivative (J), more specifically, for example, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6, 8,8-hexamethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6, 6,8-hexamethyl-cyclotetraoxane, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8-dipropyl- 2,4,6,8-tetramethyl-cyclotetraoxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,6- Dipropyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,8-tri[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl -2,4,6,6,8-pentamethyl-cyclotetraoxane, 2,4,8-tri[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl ]-6-propyl-2,4,6,8-tetramethyl-cyclotetraoxane, 2,4,6,8-tetra[2-(3-{oxabicyclo[4.1.0]g a group of ethyl}-2,4,6,8-tetramethyl-cyclotetraoxane, a polysesquioxane having two or more epoxy groups in the molecule, and the like. More specifically, for example, a cyclic siloxane having two or more epoxy groups in the molecule represented by the following formula is used.

而且，作為矽氧烷衍生物(J)，可使用例如特開2008-248169號公報記載的含有脂環式環氧基的聚矽氧樹脂、特開2008-19422號公報記載的1分子中具有至少2個環氧基官能性基的有機聚倍半矽氧烷樹脂等。 In addition, as the fluorinated alkane derivative (J), for example, one of the molecules described in JP-A-2008-248169, which contains an alicyclic epoxy group-containing polyfluorene-oxygen resin, and JP-A-2008-19422 At least two epoxy-functional organic polysilsesquioxane resins and the like.

再者，於本發明的第2態樣的硬化性樹脂組成物，矽氧烷衍生物(J)可使用單獨1種，亦可組合2種以上使用。 In addition, the curable resin composition of the second aspect of the present invention may be used alone or in combination of two or more.

矽氧烷衍生物(J)，可取得例如分子內具有2個以上環氧基的環狀矽氧烷之商品名「X-40-2678」、「X-40-2670」、「X-40-2720」(以上信越化學工業(股)製) 等的市售品。而且，矽氧烷衍生物(J)，可藉由習知至慣用的方法製造。 The oxime derivative (J) can be obtained, for example, under the trade names "X-40-2678", "X-40-2670", and "X-40" of a cyclic oxirane having two or more epoxy groups in the molecule. -2720" (Shin-Etsu Chemical Industry Co., Ltd.) and other commercial products. Further, the decane derivative (J) can be produced by a conventional to conventional method.

本發明的第2態樣的硬化性樹脂組成物之矽氧烷衍生物(J)的含量(調配量)，無特別限制，對硬化性樹脂組成物(100重量%)而言，較理想為0.1至30重量%，更理想為0.5至20重量%，又更理想為1.0至10重量%。藉由控制矽氧烷衍生物(J)的含量為上述範圍內，硬化性樹脂組成物的觸變性變高，有更提高硬化物的耐熱性、耐光性及光反射性的傾向。 The content (adjusted amount) of the oxoxane derivative (J) of the curable resin composition of the second aspect of the invention is not particularly limited, and is preferably a curable resin composition (100% by weight). 0.1 to 30% by weight, more desirably 0.5 to 20% by weight, still more preferably 1.0 to 10% by weight. When the content of the siloxane derivative (J) is within the above range, the thixotropy of the curable resin composition is increased, and the heat resistance, light resistance, and light reflectivity of the cured product tend to be improved.

本發明的第2態樣的硬化性樹脂組成物之矽氧烷衍生物(J)的含量(調配量)，無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為5至99重量份，更理想為10至95重量份，又更理想為20至80重量份。藉由矽氧烷衍生物(J)的含量為5重量份以上，硬化性樹脂組成物的觸變性變高，有更提高硬化物的耐熱性、耐光性及光反射性的傾向。另一方面，藉由矽氧烷衍生物(J)的含量為150重量份以下，有更提高硬化物的耐熱衝擊性及接著性的傾向。 The content (adjusted amount) of the oxoxane derivative (J) of the curable resin composition of the second aspect of the present invention is not particularly limited, and all of the epoxy group-containing compounds contained in the curable resin composition are all The amount is preferably from 5 to 99 parts by weight, more preferably from 10 to 95 parts by weight, still more preferably from 20 to 80 parts by weight, per 100 parts by weight. When the content of the siloxane derivative (J) is 5 parts by weight or more, the thixotropy of the curable resin composition is increased, and the heat resistance, light resistance, and light reflectivity of the cured product tend to be improved. On the other hand, when the content of the oxoxane derivative (J) is 150 parts by weight or less, the thermal shock resistance and the adhesion property of the cured product tend to be improved.

[脂環式聚酯樹脂(K)] [Cycloaliphatic Polyester Resin (K)]

本發明的第2態樣的硬化性樹脂組成物之脂環式聚酯樹脂(K)，係至少具有脂環構造(脂肪族環構造)的聚酯樹脂。脂環式聚酯樹脂(K)，係擔任提高硬化物的耐熱性、耐光性、耐龜裂性，同時抑制朝蝕刻液的溶出(以下如此的特 性稱為「耐蝕刻液溶出性」)，以及抑制光半導體裝置的亮度降低之任務。特別是在提高硬化物的耐熱性、耐光性、耐龜裂性、耐蝕刻液溶出性的觀點，脂環式聚酯樹脂(K)係以主鏈具有脂環(脂環構造)的脂環式聚酯較理想。亦即，脂環式聚酯樹脂(K)，較理想為由構成脂環的碳原子的一部分或全部構成聚合物主鏈之聚酯樹脂。再者，脂環式聚酯樹脂(K)可使用單獨1種，亦可組合2種以上使用。 The alicyclic polyester resin (K) of the curable resin composition of the second aspect of the present invention is a polyester resin having at least an alicyclic structure (aliphatic ring structure). The alicyclic polyester resin (K) serves to improve the heat resistance, light resistance, and crack resistance of the cured product, and at the same time suppresses elution into the etching liquid (the following characteristics are referred to as "etching liquid resistance"). And the task of suppressing the decrease in brightness of the optical semiconductor device. In particular, the alicyclic polyester resin (K) has an alicyclic ring having an alicyclic ring (alicyclic structure) from the viewpoint of improving the heat resistance, light resistance, crack resistance, and etching resistance of the cured product. Polyester is preferred. That is, the alicyclic polyester resin (K) is preferably a polyester resin constituting a polymer main chain from a part or all of carbon atoms constituting the alicyclic ring. In addition, the alicyclic polyester resin (K) may be used alone or in combination of two or more.

作為脂環式聚酯樹脂(K)的脂環構造，無特別限制，例如單環烴構造、交聯環烴構造(例如二環系烴等)，特別是脂環(構成脂環的碳-碳鍵結)全部由碳-碳單鍵所構成之飽和單環烴構造、飽和交聯環烴構造較理想。而且，上述脂環式聚酯樹脂(K)的脂環構造，可只由來自二羧酸的構成單元與來自二醇的構成單元的任一方導入，亦可由兩方同時導入，無特別限制。 The alicyclic structure of the alicyclic polyester resin (K) is not particularly limited, and is, for example, a monocyclic hydrocarbon structure or a crosslinked cyclic hydrocarbon structure (for example, a bicyclic hydrocarbon), and particularly an alicyclic ring (carbon constituting an alicyclic ring). The carbon bond structure is preferably a saturated monocyclic hydrocarbon structure composed of a carbon-carbon single bond and a saturated crosslinked cyclic hydrocarbon structure. Further, the alicyclic structure of the alicyclic polyester resin (K) may be introduced only by one of the constituent units derived from the dicarboxylic acid and the constituent unit derived from the diol, or may be introduced simultaneously from both sides without particular limitation.

脂環式聚酯樹脂(K)，含有來自具有脂環構造的單體成分的構成單元。作為上述具有脂環構造的單體成分，例如具有習知至慣用的脂環構造的二醇、二羧酸，無特別限制，例如1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、4-甲基-1,2-環己烷二羧酸、腐植酸、1,4-十氫萘二羧酸、1,5-十氫萘二羧酸、2,6-十氫萘二羧酸、2,7-十氫萘二羧酸等具有脂環構造的二羧酸(包含酸酐等衍生物)等；1,2-環戊二醇、1,3-環戊二醇、1,2-環戊二甲醇、1,3-環戊二甲醇、雙(羥基甲基)三環[5.2.1.0]癸烷等5員環二醇；1,2-環己二醇、1,3-環己二醇、1,4-環己二醇、 1,2-環己二甲醇、1,3-環己二甲醇、1,4-環己二甲醇、2,2-雙(4-羥基環己基)丙烷等6員環二醇；氫化雙酚A等具有脂環構造的二醇(包含此等的衍生物)等。 The alicyclic polyester resin (K) contains a constituent unit derived from a monomer component having an alicyclic structure. The monomer component having an alicyclic structure, for example, a diol having a conventional to conventional alicyclic structure, or a dicarboxylic acid is not particularly limited, and examples thereof include 1,2-cyclohexanedicarboxylic acid and a 1,3-ring. Hexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, humic acid, 1,4-decahydronaphthalene dicarboxylic acid, 1,5 a dicarboxylic acid (including a derivative such as an acid anhydride) having an alicyclic structure such as decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid or 2,7-decahydronaphthalene dicarboxylic acid; and 1,2 - cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclopentanediethanol, 1,3-cyclopentanemethanol, bis(hydroxymethyl)tricyclo[5.2.1.0]nonane, etc. 5 Cyclohexane; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 6-membered ring diol such as 1,4-cyclohexanedimethanol or 2,2-bis(4-hydroxycyclohexyl)propane; diol having an alicyclic structure such as hydrogenated bisphenol A (including such derivatives), etc. .

脂環式聚酯樹脂(K)，亦可含有來自不具有脂環構造的單體成分的構成單元。作為上述不具有脂環構造的單體成分，無特別限制，例如對苯二甲酸、間苯二甲酸、鄰苯二甲酸、萘二甲酸等芳香族二羧酸(包含酸酐等衍生物)；己二酸、癸二酸、壬二酸、琥珀酸、反丁烯二酸、順丁烯二酸等脂肪族二羧酸(包含酸酐等衍生物)；乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、3-甲基戊二醇、二乙二醇、3-甲基-1,5-戊二醇、2-甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、苯二甲醇、雙酚A的環氧乙烷加成物、雙酚A的環氧丙烷加成物等二醇(包含此等的衍生物)等。再者，適合的取代基(例如烷基、烷氧基、鹵原子等)鍵結於上述不具有脂環構造的二羧酸、二醇者，亦包含於不具有脂環構造的單體成分。 The alicyclic polyester resin (K) may also contain a constituent unit derived from a monomer component having no alicyclic structure. The monomer component having no alicyclic structure is not particularly limited, and examples thereof include aromatic dicarboxylic acids (including derivatives such as acid anhydrides) such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid; Aliphatic dicarboxylic acids (including derivatives such as acid anhydrides) such as diacids, sebacic acid, sebacic acid, succinic acid, fumaric acid, maleic acid; ethylene glycol, propylene glycol, 1,2-propanediol , 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane Alcohol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl- A diol (including such a derivative) such as 2-ethyl-1,3-propanediol, benzenedimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A. Further, a suitable substituent (for example, an alkyl group, an alkoxy group, a halogen atom or the like) is bonded to the above-mentioned dicarboxylic acid or diol having no alicyclic structure, and is also contained in a monomer component having no alicyclic structure. .

對構成脂環式聚酯樹脂(K)的全部單體單元(全部單體成分)(100莫耳%)而言，具有脂環的單體單元的比例，無特別限制，以10莫耳%以上(例如10至80莫耳%)較理想，更理想為25至70莫耳%，又更理想為40至60莫耳%。具有脂環的單體單元的比例未達10莫耳%時，有硬化物的耐熱性、耐光性、耐龜裂性、耐蝕刻液溶出性降低的情況。 The ratio of the monomer unit having an alicyclic ring to all the monomer units (all monomer components) (100 mol%) constituting the alicyclic polyester resin (K) is not particularly limited, and is 10 mol%. The above (e.g., 10 to 80 mol%) is more desirable, more desirably 25 to 70 mol%, and still more desirably 40 to 60 mol%. When the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product may be lowered.

作為脂環式聚酯樹脂(K)，特別是以至少包含1種以上下述式(2)至(4)所示的構成單元的脂環式聚酯樹脂較理想。 The alicyclic polyester resin (K) is preferably an alicyclic polyester resin containing at least one or more constituent units represented by the following formulas (2) to (4).

(式中，R10表示直鏈、分支鏈或環狀的碳數2至15的伸烷基。而且，R11至R14分別獨立表示氫原子或直鏈狀或分支鏈狀的碳數1至4的烷基，選自R11至R14中的2個亦可鍵結形成環。) (wherein R 10 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 11 to R 14 each independently represent a hydrogen atom or a linear or branched carbon number 1 The alkyl group selected from 4 to 2 selected from R 11 to R 14 may also be bonded to form a ring.

(式中，R10表示直鏈、分支鏈或環狀的碳數2至15的伸烷基。而且，R11至R14分別獨立表示氫原子或直鏈狀或分支鏈狀的碳數1至4的烷基，亦可形成由選自R11至R14中之二者鍵結而成的環。) (wherein R 10 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 11 to R 14 each independently represent a hydrogen atom or a linear or branched carbon number 1 The alkyl group to 4 may also form a ring bonded by two selected from R 11 to R 14 .)

(式中，R10表示直鏈、分支鏈或環狀的碳數2至15的伸烷基。而且，R11至R14分別獨立表示氫原子或直鏈狀或分支鏈狀的碳數1至4的烷基，亦可形成由選自R11至R14中之二者鍵結而成的環。) (wherein R 10 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms. Further, R 11 to R 14 each independently represent a hydrogen atom or a linear or branched carbon number 1 The alkyl group to 4 may also form a ring bonded by two selected from R 11 to R 14 .)

作為上述式(2)至(4)所示的構成單元的較理想的具體例，例如下述式(5)所示來自4-甲基-1,2-環己二甲酸及乙二醇的構成單元。具有該構成單元的脂環式聚酯樹脂(K)，例如可藉由甲基六氫鄰苯二甲酸酐與乙二醇縮聚合而得。 Preferable specific examples of the constituent units represented by the above formulas (2) to (4) are, for example, those derived from 4-methyl-1,2-cyclohexanedicarboxylic acid and ethylene glycol represented by the following formula (5). Form the unit. The alicyclic polyester resin (K) having such a constituent unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride with ethylene glycol.

而且，作為上述式(2)至(4)所示的構成單元的其他較理想的具體例，例如下述式(6)所示來自1,4-環己二羧酸及新戊二醇的構成單元。具有該構成單元的脂環式聚酯樹脂(K)，例如可藉由1,4-環己二羧酸與新戊二醇縮聚 合而得。 Further, other preferable specific examples of the constituent units represented by the above formulas (2) to (4) are, for example, those derived from 1,4-cyclohexanedicarboxylic acid and neopentyl glycol represented by the following formula (6). Form the unit. The alicyclic polyester resin (K) having such a constituent unit can be obtained, for example, by condensation polymerization of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.

再者，脂環式聚酯樹脂(K)的末端構造，無特別限制，可為羥基、羧基，亦可為該等羥基、羧基被適當改質而成的構造(例如末端的羥基藉由單羧酸、酸酐進行酯化而成的構造、末端的羧基藉由醇進行酯化而成的構造等)。 Further, the terminal structure of the alicyclic polyester resin (K) is not particularly limited, and may be a hydroxyl group or a carboxyl group, or a structure in which the hydroxyl group and the carboxyl group are appropriately modified (for example, the terminal hydroxyl group is represented by a single A structure in which a carboxylic acid or an acid anhydride is esterified, a structure in which a terminal carboxyl group is esterified with an alcohol, or the like).

於脂環式聚酯樹脂(K)具有上述式(2)至(4)所示的構成單元的情況，該構成單元含量的合計量(合計含量；構成該構成單元的全部單體單元)，無特別限制，對脂環式聚酯樹脂(K)的全部構成單元(100莫耳%；構成脂環式聚酯樹脂(K)的全部單體單元)而言，較理想為20莫耳%以上(例如20至100莫耳%)，更理想為50至100莫耳%，又更理想為80至100莫耳%。上述式(2)至(4)所示的構成單元的含量未達20莫耳%時，有硬化物的耐熱性、耐光性、耐龜裂性、耐蝕刻液溶出性降低的情況。 In the case where the alicyclic polyester resin (K) has the constituent units represented by the above formulas (2) to (4), the total content of the constituent unit contents (the total content; all the monomer units constituting the constituent unit), It is not particularly limited, and it is preferably 20 mol% for all constituent units (100 mol%; all monomer units constituting the alicyclic polyester resin (K)) of the alicyclic polyester resin (K). The above (e.g., 20 to 100 mol%), more desirably 50 to 100 mol%, and still more desirably 80 to 100 mol%. When the content of the structural unit represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product may be lowered.

脂環式聚酯樹脂(K)的數量平均分子量，無特別限制，較理想為300至100000，更理想為300至30000。脂環式聚酯樹脂(K)的數量平均分子量未達300時，硬化物的強韌性不充分，有耐龜裂性、耐蝕刻液溶出性降低的情況。另一方面，脂環式聚酯樹脂(K)的數量平均 分子量超過100000時，與其他成分(例如硬化劑(E))的相溶性降低，對硬化物的機械物性有不良影響以及有耐龜裂性、耐蝕刻液溶出性降低的情況。再者，脂環式聚酯樹脂(K)的數量平均分子量，例如可藉由GPC(凝膠滲透層析)法測定作為換算標準聚苯乙烯的值。 The number average molecular weight of the alicyclic polyester resin (K) is not particularly limited, and is preferably from 300 to 100,000, more preferably from 300 to 30,000. When the number average molecular weight of the alicyclic polyester resin (K) is less than 300, the toughness of the cured product is insufficient, and the crack resistance and the etching resistance of the etching solution are lowered. On the other hand, when the number average molecular weight of the alicyclic polyester resin (K) exceeds 100,000, the compatibility with other components (for example, the hardener (E)) is lowered, the mechanical properties of the cured product are adversely affected, and the turtle is resistant. Cracking and etching solution resistance are reduced. Further, the number average molecular weight of the alicyclic polyester resin (K) can be measured, for example, by a GPC (gel permeation chromatography) method as a value of a standard polystyrene.

再者，脂環式聚酯樹脂(K)可使用單獨1種，亦可組合2種以上使用。 In addition, the alicyclic polyester resin (K) may be used alone or in combination of two or more.

脂環式聚酯樹脂(K)，無特別限制，可藉由習知至慣用的方法製造。更詳細者，例如脂環式聚酯樹脂(K)可將上述二羧酸與二醇藉由通常的方法縮聚合而得，亦可將上述二羧酸的衍生物(酸酐、酯、醯鹵化合物等)與二醇藉由通常的方法縮聚合而得。 The alicyclic polyester resin (K) is not particularly limited and can be produced by a conventional to conventional method. More specifically, for example, the alicyclic polyester resin (K) may be obtained by polycondensation of the above dicarboxylic acid and a diol by a usual method, or a derivative of the above dicarboxylic acid (anhydride, ester, hydrazine halide). The compound or the like is obtained by condensation polymerization with a diol by a usual method.

於本發明的第2態樣的硬化性樹脂組成物，脂環式聚酯樹脂(K)的調配量(含量)，無特別限制，於硬化劑(E)為必要成分的情況，對脂環式聚酯樹脂(K)與硬化劑(E)的合計量(100重量%)而言，較理想為1至60重量%，更理想為5至30重量%。脂環式聚酯樹脂(K)的調配量未達1重量%時，有硬化物的耐龜裂性、耐蝕刻液溶出性降低的情況。另一方面，脂環式聚酯樹脂(K)的調配量超過60重量%時，有硬化物的耐熱性降低的情況。 In the curable resin composition of the second aspect of the present invention, the amount (content) of the alicyclic polyester resin (K) is not particularly limited, and when the curing agent (E) is an essential component, the alicyclic ring is used. The total amount (100% by weight) of the polyester resin (K) and the hardener (E) is preferably from 1 to 60% by weight, more preferably from 5 to 30% by weight. When the amount of the alicyclic polyester resin (K) is less than 1% by weight, the crack resistance of the cured product and the elution resistance of the etching solution may be lowered. On the other hand, when the compounding amount of the alicyclic polyester resin (K) exceeds 60% by weight, the heat resistance of the cured product may be lowered.

另一方面，本發明的第2態樣的硬化性樹脂組成物中硬化觸媒(G)為必要成分的情況，脂環式聚酯樹脂(K)的調配量(含量)無特別限制，對脂環式聚酯樹脂(K)與硬化觸媒(G)的合計量(100重量%)而言，較理想為50至 99重量%，更理想為65至99重量%。脂環式聚酯樹脂(K)的調配量未達50重量%時，有硬化物的耐龜裂性、耐蝕刻液溶出性降低的情況。另一方面，脂環式聚酯樹脂(K)的調配量超過99重量%時，有硬化物的耐熱性降低的情況。 On the other hand, in the case where the curing catalyst (G) is a necessary component in the curable resin composition of the second aspect of the present invention, the amount (content) of the alicyclic polyester resin (K) is not particularly limited. The total amount (100% by weight) of the alicyclic polyester resin (K) and the hardening catalyst (G) is desirably 50 to 99% by weight, more desirably 65 to 99% by weight. When the amount of the alicyclic polyester resin (K) is less than 50% by weight, the crack resistance of the cured product and the elution resistance of the etching solution may be lowered. On the other hand, when the compounding amount of the alicyclic polyester resin (K) exceeds 99% by weight, the heat resistance of the cured product may be lowered.

於本發明的第2態樣的硬化性樹脂組成物，脂環式聚酯樹脂(K)的調配量(含量)無特別限制，對硬化性樹脂組成物(100重量%)而言，較理想為0.1至20重量%，更理想為0.3至10重量%。脂環式聚酯樹脂(K)的調配量未達0.1重量%時，有硬化物的耐龜裂性降低的情況。另一方面，脂環式聚酯樹脂(K)的調配量超過20重量%時，有硬化物的耐熱性降低的情況。 In the curable resin composition of the second aspect of the present invention, the amount (content) of the alicyclic polyester resin (K) is not particularly limited, and it is preferable for the curable resin composition (100% by weight). It is from 0.1 to 20% by weight, more desirably from 0.3 to 10% by weight. When the amount of the alicyclic polyester resin (K) is less than 0.1% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding amount of the alicyclic polyester resin (K) exceeds 20% by weight, the heat resistance of the cured product may be lowered.

另一方面，於本發明的第2態樣的硬化性樹脂組成物，脂環式聚酯樹脂(K)的調配量(含量)無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為1至60重量份，更理想為5至30重量份。脂環式聚酯樹脂(K)的調配量未達1重量份時，有硬化物的耐龜裂性降低的情況。另一方面，脂環式聚酯樹脂(K)的調配量超過60重量份時，有硬化物的耐熱性降低的情況。 On the other hand, in the curable resin composition of the second aspect of the present invention, the compounding amount (content) of the alicyclic polyester resin (K) is not particularly limited, and the epoxy resin composition is contained in the epoxy resin composition. The total amount of the compound of the base is preferably from 1 to 60 parts by weight, more preferably from 5 to 30 parts by weight, per 100 parts by weight. When the amount of the alicyclic polyester resin (K) is less than 1 part by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding amount of the alicyclic polyester resin (K) exceeds 60 parts by weight, the heat resistance of the cured product may be lowered.

[離型劑] [Release agent]

本發明的第1態樣或第2態樣的硬化性樹脂組成物，亦可再包含離型劑。藉由包含離型劑，變得容易藉由轉移成型、壓縮成型等使用模具的成型法之連續成型，能以高 生產性製造硬化物(反射器)。作為離型劑，可使用習知至慣用的離型劑，無特別限制，例如氟系離型劑(含有氟原子的化合物；例如氟油、聚四氟乙烯等)、聚矽氧系離型劑(聚矽氧化合物；例如聚矽氧油、聚矽氧蠟、聚矽氧樹脂、具有聚氧伸烷基單元的聚有機矽氧烷等)、蠟系離型劑(蠟類；例如巴西棕櫚蠟等植物蠟、羊毛蠟等動物蠟、石蠟等石蠟類、聚乙烯蠟、氧化聚乙烯蠟等)、高級脂肪酸及其鹽(例如金屬鹽)、高級脂肪酸酯、高級脂肪酸醯胺、礦物油等。 The curable resin composition of the first aspect or the second aspect of the present invention may further contain a release agent. By including a release agent, it is easy to continuously mold by a molding method using a mold such as transfer molding or compression molding, and a cured product (reflector) can be produced with high productivity. As the release agent, a conventional to conventional release agent can be used without particular limitation, such as a fluorine-based release agent (a compound containing a fluorine atom; for example, a fluorine oil, a polytetrafluoroethylene, etc.), and a polyfluorene-separation type. Agents (polyoxygen compounds; for example, polyoxygenated oils, polyoxyxylene waxes, polyoxyxylene resins, polyorganosiloxanes having polyoxyalkylene units, etc.), wax-based release agents (wax; for example, Brazil) Plant wax such as palm wax, animal wax such as wool wax, paraffin wax such as paraffin wax, polyethylene wax, oxidized polyethylene wax, etc.), higher fatty acid and its salt (such as metal salt), higher fatty acid ester, higher fatty acid guanamine, mineral Oil, etc.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物，離型劑可使用單獨1種，亦可組合2種以上使用。而且，離型劑可藉由習知至慣用的方法製造，亦可使用市售品。 In the first embodiment or the second aspect of the present invention, the release agent may be used alone or in combination of two or more. Further, the release agent can be produced by a conventional to conventional method, and a commercially available product can also be used.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物含有離型劑的情況，離型劑的含量(調配量)無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為1至12重量份，更理想為2至10重量份。藉由離型劑的含量為1重量份以上，有更提高硬化物(反射器)的離型性、更提高反射器的生產性的傾向。另一方面，藉由離型劑的含量為12重量份以下，有對光半導體元件安裝用基板之反射器的引線架可確保良好黏合性的傾向。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains a release agent, the content (the amount of the release agent) of the release agent is not particularly limited, and the ring is contained in the curable resin composition. The total amount of the compound of the oxy group is preferably from 1 to 12 parts by weight, more preferably from 2 to 10 parts by weight, per 100 parts by weight. When the content of the release agent is 1 part by weight or more, the release property of the cured product (reflector) is further improved, and the productivity of the reflector is further improved. On the other hand, when the content of the release agent is 12 parts by weight or less, the lead frame for the reflector of the substrate for mounting an optical semiconductor element tends to have good adhesion.

[抗氧化劑] [Antioxidants]

本發明的第1態樣或第2態樣的硬化性樹脂組成物，亦可包含抗氧化劑。藉由包含抗氧化劑，可能製造耐熱性(特別是耐黃變性)更佳的硬化物(反射器)。作為抗氧化劑，可使用習知至慣用的抗氧化劑，無特別限制，例如酚系抗氧化劑(酚系化合物)、受阻胺系抗氧化劑(受阻胺系化合物)、磷系抗氧化劑(磷系化合物)、硫系抗氧化劑(硫系化合物)等。 The curable resin composition of the first aspect or the second aspect of the present invention may further contain an antioxidant. By containing an antioxidant, it is possible to produce a cured product (reflector) which is more excellent in heat resistance (particularly, yellowing resistance). As the antioxidant, a conventional to conventional antioxidant can be used without particular limitation, and examples thereof include a phenolic antioxidant (phenolic compound), a hindered amine antioxidant (hindered amine compound), and a phosphorus antioxidant (phosphorus compound). A sulfur-based antioxidant (a sulfur-based compound) or the like.

作為酚系抗氧化劑，例如2,6-二第3丁基-對-甲酚、丁基化羥基苯甲醚、2,6-二第3丁基-對-乙基酚、硬脂基-β-(3,5-二第3丁基-4-羥基苯基)丙酸酯等單酚類；2,2’-亞甲基雙(4-甲基-6-第3丁基酚)、2,2’-亞甲基雙(4-乙基-6-第3丁基酚)、4,4’-硫代雙(3-甲基-6-第3丁基酚)、4,4’-亞丁基雙(3-甲基-6-第3丁基酚)、3,9-雙[11-二甲基-2-{β-(3-第3丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]2,4,8,10-四氧雜螺環[5.5]十一烷等雙酚類；1,1,3-三(2-甲基-4-羥基-5-第3丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二第3丁基-4-羥基苯甲基)苯、四[亞甲基-3-(3’,5’-二第3丁基-4’-羥基苯基)丙烯酸酯]甲烷、雙[3,3’-雙(4’-羥基-3’-第3丁基苯基)丁酸]二醇酯、1,3,5-(3’,5’-二第3丁基-4’-羥基苯甲基)-s-三嗪-2,4,6-(1H,3H,5H)三酮、生育酚等高分子型酚類等。 As the phenolic antioxidant, for example, 2,6-dibutyl butyl-p-cresol, butylated hydroxyanisole, 2,6-dibutylbutyl-p-ethylphenol, stearyl- Monophenols such as β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 2,2'-methylenebis(4-methyl-6-tert-butylphenol) , 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4, 4'-butylidene bis(3-methyl-6-tert-butylphenol), 3,9-bis[11-dimethyl-2-{β-(3-tert-butyl-4-hydroxy- Bisphenols such as 5-methylphenyl)propoxycarbonyl}ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane; 1,1,3-tris(2-A) 4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-3 butyl-4-hydroxybenzene Methyl)benzene, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)acrylate]methane, bis[3,3'-bis(4'- Hydroxy-3'-tributylphenyl)butyrate]diol, 1,3,5-(3',5'-di-3butyl-4'-hydroxybenzyl)-s-three A polymer phenol such as azine-2,4,6-(1H,3H,5H)trione or tocopherol.

作為受阻胺系抗氧化劑，例如雙(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]丁基丙二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸 酯、甲基-1,2,2,6,6-五甲基-4-哌啶基癸二酸酯、4-苯甲醯氧基-2,2,6,6-四甲基哌啶等。 As a hindered amine-based antioxidant, for example, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4 -hydroxyphenyl]methyl]butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl-1,2,2 6,6-pentamethyl-4-piperidinyl sebacate, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, and the like.

作為磷系抗氧化劑，例如亞磷酸三苯酯、亞磷酸二苯基異癸酯、亞磷酸苯基二異癸酯、亞磷酸三(壬基苯基)酯、二異癸基季戊四醇亞磷酸酯、亞磷酸三(2,4-二第3丁基苯基)酯、環狀新戊烷四基雙(十八烷基)亞磷酸酯、環狀新戊烷四基雙(2,4-二第3丁基苯基)亞磷酸酯、環狀新戊烷四基雙(2,4-二第3丁基-4-甲基苯基)亞磷酸酯、雙[2-第3丁基-6-甲基-4-{2-(十八烷氧基羰基)乙基}苯基]亞磷酸氫酯等亞磷酸酯類；9,10-二氫-9-氧-10-磷菲-10-氧化物、10-(3,5-二第3丁基-4-羥基苯甲基)-9,10-二氫-9-氧-10-磷菲-10-氧化物等氧磷菲氧化物類等。 As a phosphorus-based antioxidant, for example, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite , tris(2,4-di-3 butylphenyl) phosphite, cyclic neopentane tetrakis(bis-octadecyl) phosphite, cyclic neopentane tetrakisyl double (2,4- Dibutyl butyl phosphite, cyclic neopentyl tetrakis(2,4-di-3 butyl-4-methylphenyl) phosphite, bis[2- 3 butyl Phosphites such as -6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]phosphite; 9,10-dihydro-9-oxo-10-phosphan -10-oxide, 10-(3,5-di-3 butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxo-10-phosphaphene-10-oxide Phenanthrene oxides, etc.

作為硫系抗氧化劑，例如十二烷硫醇、3,3’-硫代二丙酸二月桂酯、3,3’-硫代二丙酸二肉荳蔻酯、3,3’-硫代二丙酸二硬脂酯等。 As a sulfur-based antioxidant, for example, dodecanethiol, 3,3'-dithiolongate dilaurate, 3,3'-thiodipropionate dimyristate, 3,3'-thiodi Distearyl propionate and the like.

於本發明的第1態樣或第2態樣的硬化性樹脂組成物，抗氧化劑可使用單獨1種，亦可組合2種以上使用。而且，抗氧化劑可藉由習知至慣用的方法製造，亦可使用例如商品名「Irganox1010」(BASF製、酚系抗氧化劑)；商品名「AO-60」、「AO-80」((股)ADEKA製、酚系抗氧化劑)；商品名「Irgafox168」(BASF製、磷系抗氧化劑)；商品名「Adekatab HP-10」、「Adekatab PEP-36」((股)ADEKA製、磷系抗氧化劑)；商品名「HCA」(三光(股)製、磷系抗氧化劑)等市售品。 The curable resin composition of the first aspect or the second aspect of the present invention may be used alone or in combination of two or more. Further, the antioxidant can be produced by a conventionally known method, and for example, the trade name "Irganox 1010" (manufactured by BASF, phenolic antioxidant); trade name "AO-60", "AO-80" (( ) ADEKA, phenolic antioxidants; trade name "Irgafox 168" (BASF, phosphorus antioxidant); trade name "Adekatab HP-10", "Adekatab PEP-36" (made by Adeka), phosphorus resistance Oxidizer); a commercial product such as "HCA" (manufactured by Sanko Co., Ltd., phosphorus-based antioxidant).

於本發明的第1態樣或第2態樣的硬化性樹脂組成物包含抗氧化劑的情況，抗氧化劑的的含量(調配量)無特別限制，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言，較理想為0.1至5重量份，更理想為0.5至3重量份。藉由抗氧化劑的的含量為0.1重量份以上，有效防止硬化物(反射器)的氧化，有更提高耐熱性、耐黃變性的傾向。藉由抗氧化劑的的含量為5重量份以下，抑制著色，有容易得到色相更好的反射器的傾向。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains an antioxidant, the content (adjusted amount) of the antioxidant is not particularly limited, and the epoxy resin composition is contained in the epoxy resin composition. The total amount of the compound of the base is preferably from 0.1 to 5 parts by weight, more preferably from 0.5 to 3 parts by weight, per 100 parts by weight. When the content of the antioxidant is 0.1 part by weight or more, oxidation of the cured product (reflector) is effectively prevented, and heat resistance and yellowing resistance tend to be further improved. When the content of the antioxidant is 5 parts by weight or less, coloring is suppressed, and a reflector having a better hue tends to be easily obtained.

[添加劑] [additive]

本發明的第1態樣或第2態樣的硬化性樹脂組成物，除上述成分以外，在無損本發明的效果的範圍下，亦可含有各種添加劑。作為上述添加劑，例如藉由含有乙二醇、二乙二醇、丙二醇、丙三醇等具有羥基的化合物(特別是脂肪族多價醇)，可使反應緩和進行。其他，在無損黏度、光反射性的範圍內，可使用消泡劑、調平劑、γ-環氧丙氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等矽烷偶合劑、界面活性劑、難燃劑、著色劑、離子吸附劑、紫外線吸收劑、光安定劑、螢光增白劑、白色顏料以外的顏料等慣用的添加劑。該等添加劑的含量無特別限制，可適當地選擇。 In addition to the above components, the curable resin composition of the first aspect or the second aspect of the present invention may contain various additives insofar as the effects of the present invention are not impaired. As the above-mentioned additive, for example, by containing a compound having a hydroxyl group (particularly an aliphatic polyvalent alcohol) such as ethylene glycol, diethylene glycol, propylene glycol or glycerin, the reaction can be relaxed. In addition, in the range of non-destructive viscosity and light reflectivity, an antifoaming agent, a leveling agent, a decane coupling agent such as γ-glycidoxypropyltrimethoxydecane or 3-mercaptopropyltrimethoxydecane may be used. Conventional additives such as surfactants, flame retardants, colorants, ion adsorbents, ultraviolet absorbers, light stabilizers, fluorescent whitening agents, and pigments other than white pigments. The content of the additives is not particularly limited and may be appropriately selected.

作為上述螢光增白劑，可使用習知至慣用的螢光增白劑。於本發明的第1態樣或第2態樣的硬化性 樹脂組成物包含螢光增白劑的情況，藉由壓縮成型所形成的硬化物，有光反射性、耐熱性、耐光性及耐龜裂性更佳的傾向。作為上述螢光增白劑，例如吡唑啉衍生物、二苯乙烯衍生物、三嗪衍生物、噻唑衍生物、苯並噻唑衍生物、氧雜蒽酮衍生物、三唑衍生物、噁唑衍生物、噻吩衍生物、香豆素衍生物、萘醯亞胺衍生物等。 As the above fluorescent whitening agent, a conventional to conventional fluorescent whitening agent can be used. In the case where the curable resin composition of the first aspect or the second aspect of the present invention contains a fluorescent whitening agent, the cured product formed by compression molding has light reflectivity, heat resistance, light resistance, and resistance. A tendency to be more cracked. As the above fluorescent whitening agent, for example, a pyrazoline derivative, a stilbene derivative, a triazine derivative, a thiazole derivative, a benzothiazole derivative, a xanthone derivative, a triazole derivative, an oxazole Derivatives, thiophene derivatives, coumarin derivatives, naphthoquinone derivatives, and the like.

於本發明的第1態樣的硬化性樹脂組成物含有脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化劑(E)、硬化促進劑(F)及應力緩和劑(H)的情況，由脂環式環氧化合物(A)、橡膠粒子(B)、硬化劑(E)、硬化促進劑(F)及應力緩和劑(H)所構成的混合物在25℃的黏度無特別限制，較理想為5000mPa‧s以下。再者，本發明的第1態樣的硬化性樹脂組成物可包含乙二醇等上述脂肪族多價醇，於該情況，上述混合物係由脂環式環氧化合物(A)、橡膠粒子(B)、硬化劑(E)、硬化促進劑(F)、應力緩和劑(H)及脂肪族多價醇所構成的混合物。 The curable resin composition according to the first aspect of the present invention contains an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing agent (E), and In the case of the hardening accelerator (F) and the stress relieving agent (H), the alicyclic epoxy compound (A), the rubber particles (B), the hardener (E), the hardening accelerator (F), and the stress relieving agent ( H) The viscosity of the mixture formed at 25 ° C is not particularly limited, and is preferably 5,000 mPa ‧ or less. Furthermore, the curable resin composition of the first aspect of the present invention may contain the above aliphatic polyvalent alcohol such as ethylene glycol. In this case, the mixture is composed of an alicyclic epoxy compound (A) and rubber particles ( B), a mixture of a hardener (E), a hardening accelerator (F), a stress relieving agent (H), and an aliphatic polyvalent alcohol.

於本發明的第2態樣的硬化性樹脂組成物含有脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化劑(E)、硬化促進劑(F)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)的情況，由脂環式環氧化合物(A)、橡膠粒子(B)、硬化劑(E)、硬化促進劑(F)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)所構成的混合物在25℃的黏度無特別限制，較理想為5000mPa‧s 以下。再者，本發明的第2態樣的硬化性樹脂組成物可包含乙二醇等上述脂肪族多價醇，於該情況，上述混合物為由脂環式環氧化合物(A)、橡膠粒子(B)、硬化劑(E)、硬化促進劑(F)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)及脂肪族多價醇所構成的混合物。 The curable resin composition according to the second aspect of the present invention contains the alicyclic epoxy compound (A), the rubber particles (B), the white pigment (C), the inorganic filler (D), and the curing agent (E). An alicyclic ring in the case of a hardening accelerator (F), a stress relieving agent (H), an isocyanuric acid derivative (I), a decane derivative (J), and an alicyclic polyester resin (K) Oxygen compound (A), rubber particles (B), hardener (E), hardening accelerator (F), stress relieving agent (H), isocyanuric acid derivative (I), and decane derivative (J) The viscosity of the mixture of the alicyclic polyester resin (K) at 25 ° C is not particularly limited, and is preferably 5,000 mPa ‧ or less. Furthermore, the curable resin composition of the second aspect of the present invention may contain the above aliphatic polyvalent alcohol such as ethylene glycol. In this case, the mixture is composed of an alicyclic epoxy compound (A) and rubber particles ( B), hardener (E), hardening accelerator (F), stress relieving agent (H), isocyanuric acid derivative (I), decane derivative (J) and alicyclic polyester resin (K And a mixture of aliphatic polyvalent alcohols.

另一方面，於本發明的第1態樣的硬化性樹脂組成物含有脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化觸媒(G)及應力緩和劑(H)的情況，由脂環式環氧化合物(A)、橡膠粒子(B)、硬化觸媒(G)及應力緩和劑(H)所構成的混合物在25℃的黏度無特別限制，較理想為5000mPa‧s以下。於本發明的第2態樣的硬化性樹脂組成物含有脂環式環氧化合物(A)、橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、硬化觸媒(G)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)的情況，由脂環式環氧化合物(A)、橡膠粒子(B)、硬化觸媒(G)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)所構成的混合物在25℃的黏度無特別限制，較理想為5000mPa‧s以下。再者，於本說明書，上述4種混合物在25℃的黏度，有總稱為「樹脂黏度」的情況。 On the other hand, the curable resin composition according to the first aspect of the present invention contains an alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), and hardened contact. In the case of the medium (G) and the stress relieving agent (H), a mixture of the alicyclic epoxy compound (A), the rubber particles (B), the curing catalyst (G), and the stress relieving agent (H) is 25 The viscosity of °C is not particularly limited, and is preferably less than 5000 mPa‧s. The curable resin composition according to the second aspect of the present invention contains an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), and a curing catalyst (G). , a stress relaxation agent (H), an isocyanuric acid derivative (I), a decane derivative (J), and an alicyclic polyester resin (K), which are composed of an alicyclic epoxy compound (A), Rubber particles (B), hardening catalyst (G), stress relieving agent (H), isocyanuric acid derivative (I), decane derivative (J) and alicyclic polyester resin (K) The viscosity of the mixture at 25 ° C is not particularly limited, and is preferably 5,000 mPa ‧ or less. In addition, in the present specification, the viscosity of the above-mentioned four kinds of mixtures at 25 ° C is collectively referred to as "resin viscosity".

上述樹脂黏度，係常壓、在25℃測定的黏度。上述樹脂黏度，較理想為5000mPa‧s以下，更理想為4000mPa‧s以下，又更理想為3500mPa‧s以下，特 別理想為3000mPa‧s以下。上述樹脂黏度為5000mPa‧s以下時，與樹脂黏度超過5000mPa‧s的情況比較，硬化性樹脂組成物藉由壓縮成型所形成的硬化物，有耐熱性、耐光性及耐龜裂性(特別是耐熱性)更佳的傾向。而且，藉由較低的上述樹脂黏度，可增加白色顏料(C)、無機填充劑(D)等其他成分的含量，有更提高硬化物的光反射性、耐熱性及耐光性的傾向。上述樹脂黏度的黏度的下限，例如為100mPa‧s以上。再者，上述樹脂黏度，例如可使用數位黏度計(型號「DVU-EII型」、(股)TOKIMEC公司製)，在轉子：標準1°34’×R24、溫度：25℃、旋轉數：0.5至10rpm的條件下測定。 The above resin viscosity is a normal pressure and a viscosity measured at 25 °C. The resin viscosity is preferably 5,000 mPa ‧ or less, more preferably 4,000 mPa ‧ s or less, still more preferably 3,500 mPa ‧ s or less, and particularly preferably 3,000 mPa ‧ s or less. When the resin viscosity is 5,000 mPa ‧ s or less, the cured resin composition has heat resistance, light resistance, and crack resistance (especially when it is more than 5000 mPa ‧ s.) Heat resistance) is a better tendency. Further, by lowering the resin viscosity, the content of other components such as the white pigment (C) and the inorganic filler (D) can be increased, and the light reflectivity, heat resistance, and light resistance of the cured product tend to be improved. The lower limit of the viscosity of the above resin viscosity is, for example, 100 mPa·s or more. Further, for the resin viscosity, for example, a digital viscometer (model "DVU-EII type", (stock) TOKIMEC) can be used, and the rotor: standard 1° 34' × R24, temperature: 25 ° C, rotation number: 0.5 Measured to 10 rpm.

上述樹脂黏度，例如作為使用的成分(例如於本發明的第1態樣的情況為脂環式環氧化合物(A)、硬化劑(E)、硬化促進劑(F)、硬化觸媒(G)及液狀的應力緩和劑(H)，於本發明的第2態樣的情況為脂環式環氧化合物(A)、硬化劑(E)、硬化促進劑(F)、硬化觸媒(G)、液狀的應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)及脂環式聚酯樹脂(K)等)，藉由使用在25℃為液體的成分較易達成。再者，作為上述成分亦可使用在25℃為固體的成分，其含量則以使上述樹脂黏度為5000mPa‧s以下之方式調整。而且，在無損本發明效果的範圍內可藉由調整橡膠粒子(B)、固體的應力緩和劑(H)的含量而容易達成。 The resin viscosity is, for example, a component to be used (for example, in the case of the first aspect of the invention, the alicyclic epoxy compound (A), the curing agent (E), the curing accelerator (F), and the curing catalyst (G) And the liquid stress relieving agent (H), in the second aspect of the invention, is an alicyclic epoxy compound (A), a curing agent (E), a curing accelerator (F), and a curing catalyst ( G), liquid stress relieving agent (H), isocyanuric acid derivative (I), decane derivative (J) and alicyclic polyester resin (K), etc., by use at 25 ° C It is easier to achieve a liquid component. Further, as the above component, a component which is solid at 25 ° C may be used, and the content thereof may be adjusted so that the resin viscosity is 5,000 mPa ‧ s or less. Further, it is easy to achieve by adjusting the content of the rubber particles (B) and the solid stress relieving agent (H) within the range in which the effects of the present invention are not impaired.

再者，本發明的第1態樣或第2態樣的硬化性樹脂組成物，亦可為藉由加熱使該硬化性樹脂組成物 的脂環式環氧化合物(A)及硬化劑(E)的一部分反應所得之B階段化的硬化性樹脂組成物(B階段狀態的硬化性樹脂組成物)。 In addition, the curable resin composition of the first aspect or the second aspect of the present invention may be an alicyclic epoxy compound (A) and a hardener (E) which are made of the curable resin composition by heating. A part of the B-staged curable resin composition (the curable resin composition in the B-stage state) obtained by the reaction.

如上述，本發明的第1態樣或第2態樣的硬化性樹脂組成物，因硬化後的光反射性、耐熱性及耐光性佳，特別是可使用作為轉移成型用樹脂組成物、壓縮成型用樹脂組成物較理想。其中，本發明的第1態樣或第2態樣的硬化性樹脂組成物，因藉由壓縮成型所形成的硬化物(反射器)的光反射性、耐熱性及耐光性特佳，作為壓縮成型用樹脂組成物特別理想。 As described above, the curable resin composition of the first aspect or the second aspect of the present invention is excellent in light reflectivity, heat resistance and light resistance after curing, and in particular, it can be used as a resin composition for transfer molding and compressed. The resin composition for molding is preferred. In the first aspect or the second aspect of the curable resin composition of the present invention, the cured product (reflector) formed by compression molding is particularly excellent in light reflectivity, heat resistance, and light resistance. The resin composition for molding is particularly preferable.

本發明的第1態樣或第2態樣的硬化性樹脂組成物，無特別限制，可將上述各成分，依需要在加熱狀態下藉由攪拌‧混合進行調製。再者，本發明的第1態樣或第2態樣的硬化性樹脂組成物，可使用預先將各成分預先混合而成者直接使用的1液系組成物，亦可使用例如將分別保管的2種以上成分在使用前以指定的比例混合後使用的多液系(例如2液系)組成物。上述攪拌‧混合的方法，無特別限制，例如可使用溶解器、均質器等各種攪拌器、捏合器、滾輪、珠磨機、自公轉式攪拌裝置等習知至慣用的攪拌‧混合手段。而且，攪拌‧混合後，可在真空下脫泡。 The curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, and the above components may be prepared by stirring and mixing in a heated state as needed. In addition, the first embodiment or the second aspect of the curable resin composition of the present invention can be used as a one-liquid composition which is directly used by mixing the components in advance, and can be stored separately, for example. A multi-liquid (for example, two-liquid) composition in which two or more components are mixed at a predetermined ratio before use. The method of stirring and mixing is not particularly limited. For example, various agitators, kneaders, rollers, bead mills, self-propagating stirring devices, and the like, which are conventionally used, such as a dissolver or a homogenizer, can be used. Moreover, after stirring and mixing, it can be defoamed under vacuum.

雖無特別限制，但是橡膠粒子(B)以預先分散於脂環式環氧化合物(A)中而成的組成物(該組成物有稱為「散佈橡膠粒子之環氧化合物」的情況)狀態進行調配較 理想。亦即，本發明的第1態樣的硬化性樹脂組成物，係以藉由混合上述散佈橡膠粒子之環氧化合物、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)、以及依需要的其他成分進行調製較理想。而且，本發明的第2態樣的硬化性樹脂組成物，係以藉由混合上述散佈橡膠粒子之環氧化合物、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、異氰脲酸衍生物(I)、矽氧烷衍生物(J)、脂環式聚酯樹脂(K)、硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)、以及依需要的其他成分進行調製較理想。藉由如此的調製方法，特別是可提高硬化性樹脂組成物中橡膠粒子(B)的分散性。但是，橡膠粒子(B)的調配方法，不限於上述方法，亦可為將其單獨調配的方法。 The rubber particles (B) are a composition in which the rubber particles (B) are dispersed in advance in the alicyclic epoxy compound (A) (the composition has a condition called "epoxy compound in which rubber particles are dispersed"). It is ideal to make the deployment. In other words, the curable resin composition according to the first aspect of the present invention is an epoxy compound, a white pigment (C), an inorganic filler (D), and a stress relieving agent (H) by mixing the rubber particles. It is preferred to prepare the hardener (E), the hardening accelerator (F) or the hardening catalyst (G), and other components as needed. Further, the curable resin composition according to the second aspect of the present invention is an epoxy compound, a white pigment (C), an inorganic filler (D), a stress relieving agent (H), and the like, which are mixed with the rubber particles. Isocyanuric acid derivative (I), decane derivative (J), alicyclic polyester resin (K), hardener (E) and hardening accelerator (F) or hardening catalyst (G), and It is desirable to modulate other components as needed. According to such a preparation method, in particular, the dispersibility of the rubber particles (B) in the curable resin composition can be improved. However, the method of blending the rubber particles (B) is not limited to the above method, and may be a method of separately arranging them.

(散佈橡膠粒子之環氧化合物) (epoxy compound with rubber particles dispersed)

上述散佈橡膠粒子之環氧化合物，可藉由使橡膠粒子(B)分散於脂環式環氧化合物(A)而得。再者，上述散佈橡膠粒子之環氧化合物之脂環式環氧化合物(A)，可為構成硬化性樹脂組成物的脂環式環氧化合物(A)的全部量，亦可為一部分的量。同樣地，上述散佈橡膠粒子之環氧化合物之橡膠粒子(B)，可為構成硬化性樹脂組成物的橡膠粒子(B)的全部量，亦可為一部分的量。 The epoxy compound in which the rubber particles are dispersed can be obtained by dispersing the rubber particles (B) in the alicyclic epoxy compound (A). In addition, the alicyclic epoxy compound (A) in which the epoxy compound of the rubber particles is dispersed may be the entire amount of the alicyclic epoxy compound (A) constituting the curable resin composition, or may be a part of the amount. . Similarly, the rubber particles (B) of the epoxy compound in which the rubber particles are dispersed may be the total amount of the rubber particles (B) constituting the curable resin composition, or may be a part of the amount.

上述散佈橡膠粒子之環氧化合物的黏度，例如可藉由併用反應性稀釋劑進行調整(亦即散佈橡膠粒子之環氧化合物亦可再包含反應性稀釋劑)。作為上述反應 性稀釋劑，可使用例如黏度(25℃)為200mPa‧s以下的脂肪族聚環氧丙基醚較理想。作為黏度(25℃)為200mPa‧s以下的脂肪族聚環氧丙基醚，例如環己二甲醇二環氧丙基醚、環己二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、三羥甲基丙烷三環氧丙基醚、聚丙二醇二環氧丙基醚等。 The viscosity of the epoxy compound in which the rubber particles are dispersed can be adjusted, for example, by using a reactive diluent in combination (that is, the epoxy compound in which the rubber particles are dispersed may further contain a reactive diluent). As the above reactive diluent, for example, an aliphatic polyepoxypropyl ether having a viscosity (25 ° C) of 200 mPa ‧ s or less can be preferably used. An aliphatic polyepoxypropyl ether having a viscosity (25 ° C) of 200 mPa ‧ or less, such as cyclohexane dimethanol diepoxypropyl ether, cyclohexanediol diepoxypropyl ether, neopentyl glycol bicyclo Oxypropyl propyl ether, 1,6-hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, polypropylene glycol diepoxypropyl ether, and the like.

上述反應性稀釋劑的使用量，可適當調整，無特別限制，對上述散佈橡膠粒子之環氧化合物的全部量100重量份而言，較理想為30重量份以下，更理想為25重量份以下(例如5至25重量份)。使用量為30重量份以下時，有容易得到強韌性(提高耐龜裂性)等所期望的性能的傾向。 The amount of the reactive diluent to be used is not particularly limited, and is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, based on 100 parts by weight of the total of the epoxy compound of the rubber particles. (for example, 5 to 25 parts by weight). When the amount used is 30 parts by weight or less, the desired properties such as toughness (increased crack resistance) are easily obtained.

上述散佈橡膠粒子之環氧化合物的製造方法，無特別限制，可使用習知至慣用的方法。例如脫水乾燥橡膠粒子(B)使其成為粉末後，與脂環式環氧化合物(A)混合，使其分散的方法；將橡膠粒子(B)的乳液與脂環式環氧化合物(A)直接混合，接著進行脫水的方法等。 The method for producing the epoxy compound in which the rubber particles are dispersed is not particularly limited, and a conventional to conventional method can be used. For example, a method in which the rubber particles (B) are dehydrated and dried to be a powder, and mixed with the alicyclic epoxy compound (A) to be dispersed; the emulsion of the rubber particles (B) and the alicyclic epoxy compound (A) Direct mixing, followed by a method of dehydration, and the like.

本發明的第1態樣或第2態樣的硬化性樹脂組成物在25℃的黏度，無特別限制，較理想為100至1000000mPa‧s，更理想為200至800000mPa‧s，又更理想為300至800000mPa‧s。另一方面，藉由25℃的黏度為100mPa‧s以上，提高注模時的操作性，有更提高硬化物的耐熱性及耐光性的傾向。另一方面，藉由25℃的黏度為1000000mPa‧s以下，提高注模時的操作性，有變得 不易在硬化物發生源自注模不良的缺陷之傾向。 The viscosity of the curable resin composition of the first aspect or the second aspect of the present invention at 25 ° C is not particularly limited, but is preferably from 100 to 1,000,000 mPa ‧ s, more preferably from 200 to 800 000 mPa ‧ s, still more preferably 300 to 800,000 mPa‧s. On the other hand, when the viscosity at 25 ° C is 100 mPa ‧ s or more, the workability at the time of injection molding is improved, and the heat resistance and light resistance of the cured product tend to be improved. On the other hand, when the viscosity at 25 ° C is 1,000,000 mPa ‧ s or less, the workability at the time of injection molding is improved, and it tends to be less likely to cause defects due to mold injection defects in the cured product.

〈硬化物〉  <hardened matter>  

本發明的第1態樣或第2態樣的硬化性樹脂組成物藉由加熱而使其硬化，可得到光反射性佳、耐熱性、耐光性及耐龜裂性佳之硬化物，又於本發明的第2態樣的情況，可得到抑制朝蝕刻液溶出之硬化物。再者，將本發明的第1態樣或第2態樣的硬化性樹脂組成物硬化而成的硬化物，亦即本發明的第1態樣或第2態樣的硬化性樹脂組成物的硬化物有稱為「本發明的硬化物」的情況。硬化時的加熱溫度(硬化溫度)無特別限制，較理想為50至200℃，更理想為80至180℃。而且，硬化時的加熱時間(硬化時間)無特別限制，較理想為60至1800秒，更理想為90至900秒。硬化溫度與硬化時間比上述範圍的下限值低的情況，硬化變得不充分，相反地比上述範圍的上限值高的情況，因發生熱分解造成之黃變，所以不理想。硬化條件隨各種條件而異，藉由例如提高硬化溫度時縮短硬化時間、降低硬化溫度時延長硬化時間等，可適當調整。而且，硬化處理，可在一階段(例如只有壓縮成型)進行，亦可例如在多階段(例如在壓縮成型後又在烤箱等再加熱作為後硬化(二次硬化))進行。而且，進行後硬化的情況，此時的加熱溫度，較理想為50至200℃，更理想為60至180℃，較理想係與硬化溫度相同程度的溫度。而且，進行後硬化的時間，較理想為0.5至10小時，更理想為1至8小時。 The curable resin composition of the first aspect or the second aspect of the present invention is cured by heating, and a cured product having excellent light reflectivity, heat resistance, light resistance, and crack resistance can be obtained. In the case of the second aspect of the invention, it is possible to obtain a cured product which suppresses elution into the etching liquid. Further, the cured product obtained by curing the first or second aspect of the curable resin composition of the present invention, that is, the first aspect or the second aspect of the curable resin composition of the present invention The cured product may be referred to as "the cured product of the present invention". The heating temperature (hardening temperature) at the time of hardening is not particularly limited, and is preferably 50 to 200 ° C, more preferably 80 to 180 ° C. Further, the heating time (hardening time) at the time of hardening is not particularly limited, and is preferably 60 to 1800 seconds, more preferably 90 to 900 seconds. When the hardening temperature and the hardening time are lower than the lower limit of the above range, the hardening is insufficient, and conversely, when it is higher than the upper limit of the above range, yellowing due to thermal decomposition occurs, which is not preferable. The curing conditions vary depending on various conditions, and can be appropriately adjusted by, for example, increasing the hardening temperature to shorten the hardening time, lowering the hardening temperature, and prolonging the hardening time. Further, the hardening treatment may be carried out in one stage (for example, only compression molding), or may be carried out, for example, in multiple stages (for example, after compression molding and reheating in an oven or the like as post-hardening (secondary hardening)). Further, in the case of post-hardening, the heating temperature at this time is preferably 50 to 200 ° C, more preferably 60 to 180 ° C, and more preferably the same temperature as the curing temperature. Moreover, the time for performing post-hardening is preferably from 0.5 to 10 hours, more preferably from 1 to 8 hours.

本發明的硬化物，具有高反射性、耐熱性及耐光性佳，又於本發明的第2態樣的情況，抑制朝蝕刻液的溶出。所以，上述硬化物不易劣化，反射率不易隨時間降低，於本發明的第2態樣的情況，蝕刻步驟的重量減少變少。所以，本發明的第1態樣或第2態樣的硬化性樹脂組成物，可使用作為LED封裝用途(LED封裝的構成材料，例如光半導體裝置之反射器材料、殼架材料等)、電子零件的接著用途、液晶顯示器用途(例如反射器等)、白色基板用墨水、密封劑等較理想。其中，可使用作為LED封裝用的硬化性樹脂組成物(特別是光半導體裝置之反射器用硬化性樹脂組成物(亦即反射器形成用硬化性樹脂組成物))特別理想。 The cured product of the present invention has high reflectivity, heat resistance and light resistance, and in the second aspect of the present invention, it suppresses elution into the etching liquid. Therefore, the cured product is less likely to deteriorate, and the reflectance is less likely to decrease with time. In the second aspect of the present invention, the weight reduction in the etching step is reduced. Therefore, the curable resin composition of the first aspect or the second aspect of the present invention can be used as an LED package (a constituent material of an LED package, for example, a reflector material of an optical semiconductor device, a frame material, etc.), and an electron. The subsequent use of the component, the use of the liquid crystal display (for example, a reflector, etc.), the ink for the white substrate, the sealant, and the like are preferable. Among them, a curable resin composition for LED packaging (particularly, a curable resin composition for a reflector of an optical semiconductor device (that is, a curable resin composition for forming a reflector)) is particularly preferable.

本發明的硬化物的反射率(初期反射率)，無特別限制，例如波長450nm的光的反射率為93%以上較理想，更理想為94%以上，又更理想為95%以上。特別是波長450至800nm的光的反射率為93%以上較理想，更理想為94%以上，又更理想為95%以上。 The reflectance (initial reflectance) of the cured product of the present invention is not particularly limited. For example, the reflectance of light having a wavelength of 450 nm is preferably 93% or more, more preferably 94% or more, still more preferably 95% or more. In particular, the reflectance of light having a wavelength of 450 to 800 nm is preferably 93% or more, more preferably 94% or more, still more preferably 95% or more.

本發明的硬化物在120℃加熱250小時後的波長450nm的光的反射率(有稱為「加熱老化後的反射率」的情況)對初期反射率的保持率([加熱老化後的反射率]/[初期反射率]×100)，無特別限制，較理想為80%以上，更理想為85%以上，又更理想為90%以上。特別是波長450至800nm的光的情況的保持率為80%以上，更理想為85%以上，又更理想為90%以上。根據本發明的第1態樣或第 2態樣的硬化性樹脂組成物，藉由壓縮成型所形成的硬化物，上述保持率能夠為90%以上。 The reflectance of light having a wavelength of 450 nm after heating at 120 ° C for 250 hours (in the case of "reflectance after heat aging"), the retention ratio of initial reflectance ([reflectance after heat aging] ] / [initial reflectance] × 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. In particular, the retention of light having a wavelength of 450 to 800 nm is 80% or more, more preferably 85% or more, still more preferably 90% or more. According to the first aspect of the invention or the curable resin composition of the second aspect, the cured product formed by compression molding can have a retention ratio of 90% or more.

本發明的硬化物經照射強度為10mW/cm2的紫外線250小時後對波長450nm的光的反射率(有稱為「紫外線老化後的反射率」的情況)對初期反射率的保持率([紫外線老化後的反射率]/[初期反射率]×100)，無特別限制，較理想為80%以上，更理想為85%以上，又更理想為90%以上。特別是波長450至800nm的光的情況，保持率較理想為80%以上，更理想為85%以上，又更理想為90%以上。 The reflectance of the cured product of the present invention to the light having a wavelength of 450 nm after being irradiated with ultraviolet rays having an intensity of 10 mW/cm 2 for 250 hours (in the case of "reflectance after ultraviolet aging"), the retention ratio of the initial reflectance ([ The reflectance after ultraviolet ray aging] / [initial reflectance] × 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. In particular, in the case of light having a wavelength of 450 to 800 nm, the retention ratio is desirably 80% or more, more desirably 85% or more, and still more desirably 90% or more.

再者，上述反射率，例如可將本發明的硬化物(厚度：3mm)作為測試片，使用分光光度計(商品名「分光光度計UV-2450」、(股)島津製作所製)進行測定。 In addition, the above-mentioned reflectance can be measured, for example, by using a spectrophotometer (trade name "Spectrophotometer UV-2450", manufactured by Shimadzu Corporation) as a test piece.

本發明的第2態樣之硬化物，在蝕刻液(例如鹼性溶液)不易溶出，即使使用作為光半導體裝置的反射器、基板的情況，在蝕刻步驟不易降低光反射性。本發明的第2態樣之硬化物，在11重量%的氫氧化鉀水溶液中經70℃、60分鐘處理後的重量減少率，無特別限制，較理想為1%以下，更理想為0.8%以下，又更理想為0.5%以下。根據本發明的第2態樣的硬化性樹脂組成物，藉由壓縮成型所形成的硬化物，上述重量減少率可為0.5%以下。 The cured product of the second aspect of the present invention is less likely to be eluted in an etching liquid (for example, an alkaline solution), and even when a reflector or a substrate as an optical semiconductor device is used, it is difficult to reduce light reflectivity in the etching step. The weight reduction rate of the cured product of the second aspect of the present invention after treatment at 70 ° C for 60 minutes in an aqueous solution of potassium hydroxide is not particularly limited, but is preferably 1% or less, more preferably 0.8%. Hereinafter, it is more preferably 0.5% or less. According to the curable resin composition of the second aspect of the present invention, the weight reduction rate can be 0.5% or less by the cured product formed by compression molding.

本發明的第1態樣或第2態樣的硬化性樹脂組成物為光半導體裝置之反射器用硬化性樹脂組成物的情況，本發明的第1態樣或第2態樣的硬化性樹脂組成物， 為形成光半導體裝置之光半導體元件的基板(光半導體元件安裝用基板)所具有的反射器(光反射構件)的用途所使用的成形材料(以模具等進行成型時使用的材料)。所以，藉由本發明的第1態樣或第2態樣的硬化性樹脂組成物進行成型(亦即使其硬化)，可製造具備具有高反射性、耐熱性及耐光性佳、並且耐龜裂性佳、又於本發明的第2態樣的情況為朝蝕刻液的溶出被抑制的具有反射器的高品質(例如高耐久性)的光半導體元件安裝用基板。再者，所謂反射器，係指於光半導體裝置，反射從光半導體元件發出的光，提高光的指向性及亮度，提高光的取出效率用的構件。至少具備由本發明的硬化物所形成的反射器之光半導體元件安裝用所使用的基板，有稱為「本發明的光半導體元件安裝用基板」的情況。 In the case where the curable resin composition of the first aspect or the second aspect of the present invention is a curable resin composition for a reflector of an optical semiconductor device, the first aspect or the second aspect of the present invention has a curable resin composition. A molding material (a material used for molding a mold or the like) used for a reflector (light reflecting member) of a substrate (optical semiconductor element mounting substrate) of an optical semiconductor device for forming an optical semiconductor device. Therefore, by molding (or even hardening) the curable resin composition of the first aspect or the second aspect of the present invention, it is possible to produce a film having high reflectivity, heat resistance, light resistance, and crack resistance. In the case of the second aspect of the present invention, it is a high-quality (for example, high durability) optical semiconductor element mounting substrate having a reflector that is suppressed in elution of the etching liquid. In addition, the term "reflector" refers to a member for reflecting light emitted from an optical semiconductor element in an optical semiconductor device, improving directivity and brightness of light, and improving light extraction efficiency. A substrate used for mounting an optical semiconductor element having at least a reflector formed of a cured product of the present invention may be referred to as a "substrate for mounting an optical semiconductor element of the present invention".

〈光半導體元件安裝用基板〉  <Optical semiconductor device mounting substrate>  

本發明的光半導體元件安裝用基板，係至少具備由本發明的硬化性樹脂組成物的硬化物(本發明的第1態樣或第2態樣的硬化性樹脂組成物硬化所得之硬化物)所形成的反射器(白色反射器)的基板。第1圖係表示本發明的光半導體元件安裝用基板之一例的示意圖，(a)表示斜視圖，(b)表示剖面圖。第1圖之100表示白色反射器，101表示金屬配線(引線架)，102表示光半導體元件的安裝區域，103表示封裝基板。再者，於封裝基板103，裝配有金屬配線101，又裝配有白色反射器100，於其中央(光半導體元件 的安裝區域102)，配置有光半導體元件107並經晶粒結著，光半導體元件107與封裝基板103上的金屬配線101之間用銲線連接。作為封裝基板103的材質，可使用樹脂、陶瓷等，亦可為與白色反射器相同者。本發明的光半導體元件安裝用基板之上側的白色反射器100，係呈環狀圍繞光半導體元件的安裝區域102的周圍，具有其環的直徑朝上方擴大的傾斜凹狀形狀。本發明的光半導體元件安裝用基板，只要上述凹狀的形狀的內側表面至少由本發明的硬化性樹脂組成物的硬化物形成即可。而且，如第1圖所示，金屬配線101圍繞的部分(102的下部)，有封裝基板103情況，亦有白色反射器100的情況(亦即第1圖之「100/103」係指可為白色反射器100，亦可為封裝基板103)。但是，本發明的光半導體元件安裝用基板，不限定於第1圖所示的態樣。 The substrate for mounting an optical semiconductor element of the present invention includes at least a cured product of the curable resin composition of the present invention (the cured product obtained by curing the curable resin composition of the first aspect or the second aspect of the present invention). A substrate of a reflector (white reflector) formed. Fig. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention, wherein (a) is a perspective view and (b) is a cross-sectional view. 100 in the first diagram denotes a white reflector, 101 denotes a metal wiring (lead frame), 102 denotes an attachment region of the optical semiconductor element, and 103 denotes a package substrate. Further, in the package substrate 103, the metal wiring 101 is mounted, and the white reflector 100 is mounted. At the center (the mounting region 102 of the optical semiconductor element), the optical semiconductor element 107 is disposed and bonded through the crystal grains. The element 107 is connected to the metal wiring 101 on the package substrate 103 by a bonding wire. As the material of the package substrate 103, a resin, a ceramic, or the like can be used, or the same as a white reflector. The white reflector 100 on the upper side of the optical semiconductor element mounting substrate of the present invention has a ring-shaped surrounding shape around the mounting region 102 of the optical semiconductor element, and has an inclined concave shape in which the diameter of the ring is enlarged upward. In the optical semiconductor element mounting substrate of the present invention, the inner surface of the concave shape may be formed of at least a cured product of the curable resin composition of the present invention. Further, as shown in Fig. 1, the portion around the metal wiring 101 (the lower portion of the 102) has the package substrate 103, and the white reflector 100 is also used (i.e., "100/103" in Fig. 1 means It is a white reflector 100, which may also be a package substrate 103). However, the substrate for mounting an optical semiconductor element of the present invention is not limited to the one shown in FIG.

作為形成本發明的光半導體元件安裝用基板之白色反射器的方法，可使用習知至慣用的成形方法(例如壓縮成型等)，無特別限制，例如將本發明的第1態樣或第2態樣的硬化性樹脂組成物，供轉移成型、壓縮成型、射出成型、LIM成型(射出成型)、藉由分配澆注之水壩成型等各種成型方法之方法等。作為形成反射器時的硬化條件，可從例如上述形成硬化物的條件等適當選擇。於本發明，其中，在可防止因劇烈硬化反應之發泡、緩和因硬化之應力應變而可提高韌性(耐龜裂性)的點，以分成多階段實施加熱處理、階段地進行硬化較理想。 As a method of forming the white reflector of the optical semiconductor element mounting substrate of the present invention, a conventional to conventional molding method (for example, compression molding) can be used without particular limitation, and for example, the first aspect or the second aspect of the present invention. The curable resin composition of the aspect is a method of various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by casting. The curing conditions at the time of forming the reflector can be appropriately selected from, for example, the conditions for forming the cured product described above. In the present invention, it is preferable to carry out heat treatment in a plurality of stages and to perform hardening in stages in order to prevent foaming due to severe hardening reaction and to alleviate stress (resistance to cracking) due to stress strain of hardening. .

使用本發明的光半導體元件安裝用基板，作為光半導體裝置的基板，藉由對該基板安裝光半導體元件，可得到本發明的光半導體裝置。 By using the optical semiconductor element mounting substrate of the present invention as a substrate of an optical semiconductor device, the optical semiconductor device of the present invention can be obtained by mounting an optical semiconductor element on the substrate.

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

本發明的光半導體裝置，係至少具備作為光源的光半導體元件及由本發明的第1態樣或第2態樣的硬化性樹脂組成物的硬化物構成的反射器(反射材料)的光半導體裝置。更具體者，本發明的光半導體裝置，係至少具有本發明的光半導體元件安裝用基板及安裝於該基板的光半導體元件的光半導體裝置。本發明的光半導體裝置，因具有本發明的第1態樣或第2態樣的硬化性樹脂組成物的硬化物所形成的反射器作為反射器，故光的亮度不易隨時間降低，信賴性高。第2圖係表示本發明的光半導體裝置的一例的示意圖(剖面圖)。第2圖之100表示白色反射器，101表示金屬配線(引線架)，103表示封裝基板、104表示連接銲線，105表示密封材料，106表示晶粒結著，107表示光半導體元件(LED元件)。於第2圖所示的光半導體裝置，因從光半導體元件107發出的光在白色反射器100的表面(反射面)反射，故能以高效率取出從光半導體元件107發出的光。如第2圖所示，本發明的光半導體裝置之光半導體元件，通常藉由透明的密封材料(第2圖之105)密封。 The optical semiconductor device of the present invention is an optical semiconductor device including at least an optical semiconductor element as a light source and a reflector (reflective material) composed of a cured product of a first or second aspect of the curable resin composition of the present invention. . More specifically, the optical semiconductor device of the present invention is an optical semiconductor device including at least the optical semiconductor element mounting substrate of the present invention and the optical semiconductor element mounted on the substrate. In the optical semiconductor device of the present invention, since the reflector formed of the cured product of the curable resin composition of the first aspect or the second aspect of the present invention is used as a reflector, the brightness of light is less likely to decrease with time, and reliability is obtained. high. Fig. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention. In Fig. 2, 100 denotes a white reflector, 101 denotes a metal wiring (lead frame), 103 denotes a package substrate, 104 denotes a bonding wire, 105 denotes a sealing material, 106 denotes a crystal grain, and 107 denotes an optical semiconductor element (LED element) ). In the optical semiconductor device shown in FIG. 2, since the light emitted from the optical semiconductor element 107 is reflected on the surface (reflecting surface) of the white reflector 100, the light emitted from the optical semiconductor element 107 can be taken out with high efficiency. As shown in Fig. 2, the optical semiconductor device of the optical semiconductor device of the present invention is usually sealed by a transparent sealing material (105 of Fig. 2).

第3、4圖係表示本發明的光半導體裝置的另一例的示意圖。第3、4圖之108表示散熱器(外殼散熱 器)，藉由具有如此的散熱器108，提高光半導體裝置的散熱效率。第3圖係散熱器的散熱路徑位在光半導體元件的正下方之例，第4圖係散熱器的散熱路徑位在光半導體裝置的橫方向之例[(a)表示上視圖，(b)表示(a)之A-A’剖面圖]。突出於第4圖之光半導體裝置的側面的散熱器108，有稱為散熱片的情況。而且，第4圖之109表示陰極標記。但是，本發明的光半導體裝置，不限定於第2至4圖所示的態樣。 3 and 4 are schematic views showing another example of the optical semiconductor device of the present invention. Reference numeral 108 in Figs. 3 and 4 denotes a heat sink (housing heat sink), and by having such a heat sink 108, heat dissipation efficiency of the optical semiconductor device is improved. Fig. 3 is an example in which the heat dissipation path of the heat sink is located directly under the optical semiconductor element, and Fig. 4 is an example in which the heat dissipation path of the heat sink is located in the lateral direction of the optical semiconductor device [(a) is a top view, (b) Indicates the A-A' profile of (a). The heat sink 108 which is protruded from the side surface of the optical semiconductor device of Fig. 4 has a case called a heat sink. Further, 109 of Fig. 4 denotes a cathode mark. However, the optical semiconductor device of the present invention is not limited to the ones shown in FIGS. 2 to 4.

[實施例] [Examples]

以下，基於實施例，更詳細說明本發明，但本發明不限定於該等實施例。再者，表1至6之硬化性樹脂組成物的各成分的調配量的單位為重量份。而且，表1至6之「-」係指不進行該成分的調配。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. In addition, the unit of the compounding quantity of each component of the hardening resin composition of Tables 1 to 6 is a weight part. Moreover, "-" in Tables 1 to 6 means that the composition of the component is not performed.

製造例1 Manufacturing example 1

(橡膠粒子的製造) (manufacture of rubber particles)

於附有回流冷卻器的1L聚合容器，放入離子交換水500g及二辛基磺基琥珀酸鈉0.68g，在氮氣氣流下一邊攪拌一邊升溫至80℃。在此處添加由相當於形成橡膠粒子的核部分用所需要量的約5重量%的丙烯酸丁酯9.5g、苯乙烯2.57g及二乙烯基苯0.39g所成的單體混合物，攪拌20分鐘使其乳化後，添加過氧二硫酸鉀9.5mg，攪拌1小時進行最初的種子聚合。然後，添加過氧二硫酸鉀180.5mg，攪拌5分鐘。此處，花費2小時連續添加由形成橡膠粒子 的核部分用所需要量之殘餘量(約95重量%的份)的丙烯酸丁酯180.5g、苯乙烯48.89g及二乙烯基苯7.33g溶解於二辛基磺基琥珀酸鈉0.95g所成的單體混合物，進行第2次種子聚合，然後熟成1小時，得到核部分。 Into a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were placed, and the mixture was heated to 80 ° C while stirring under a nitrogen gas stream. Here, a monomer mixture of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene, which is equivalent to about 5% by weight of a desired amount of the core portion forming the rubber particles, is added thereto, and stirred for 20 minutes. After emulsification, 9.5 mg of potassium peroxodisulfate was added, and the mixture was stirred for 1 hour to carry out initial seed polymerization. Then, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, it takes 2 hours to continuously add 180.5 g of butyl acrylate, 48.89 g of styrene, and 7.33 g of divinylbenzene in a residual amount (about 95% by weight) of the core portion forming the rubber particles. A monomer mixture of 0.95 g of sodium dioctylsulfosuccinate was subjected to a second seed polymerization, followed by aging for 1 hour to obtain a core portion.

然後，添加過氧二硫酸鉀60mg攪拌5分鐘，在此處花費30分鐘連續添加甲基丙烯酸甲酯60g、丙烯酸1.5g及甲基丙烯酸烯丙酯0.3g溶解於二辛基磺基琥珀酸鈉0.3g所成的單體混合物，進行種子聚合。然後，熟成1小時，形成包覆核部分的殼層。 Then, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes, and 60 g of methyl methacrylate, 1.5 g of acrylic acid and 0.3 g of allyl methacrylate were continuously added thereto for 30 minutes to be dissolved in sodium dioctylsulfosuccinate. 0.3 g of the resulting monomer mixture was subjected to seed polymerization. Then, it was aged for 1 hour to form a shell layer covering the core portion.

然後，冷卻至室溫(25℃)，藉由開孔120μm的塑膠製網過濾，得到包含具有核殼構造的橡膠粒子的乳膠。將所得之乳膠在負30℃下冷凍，用吸濾器進行脫水洗淨後，於60℃下送風乾燥一晝夜，得到橡膠粒子。所得之橡膠粒子的平均粒徑為108nm，最大粒徑為289nm。 Then, it was cooled to room temperature (25 ° C), and filtered through a plastic mesh having an opening of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The obtained latex was frozen at minus 30 ° C, dehydrated and washed with a suction filter, and then air-dried at 60 ° C for one day and night to obtain rubber particles. The obtained rubber particles had an average particle diameter of 108 nm and a maximum particle diameter of 289 nm.

再者，橡膠粒子的平均粒徑、最大粒徑，係使用以動態光散射法為測定原理的「NanotracTM」型的奈米追蹤粒徑分佈測定裝置(商品名「UPA-EX150」、日機裝(股)製)測定樣品，於所得之粒徑分佈曲線，以積分曲線為50%時點的粒徑之積分平均粒徑為平均粒徑，粒徑分佈測定結果的頻率(%)超過0.00%的時點的最大粒徑為最大粒徑。再者，作為上述樣品，係使用下述製造例2所得之散佈橡膠粒子之環氧化合物1重量份分散於四氫呋喃20重量份者。 In addition, the "Nanotrac TM " type nano tracking particle size distribution measuring apparatus (product name "UPA-EX150", Japanese machine using the dynamic light scattering method as the measuring principle is used for the average particle diameter and the maximum particle diameter of the rubber particles. The sample (measured) is used to measure the sample. In the obtained particle size distribution curve, the integrated average particle diameter of the particle diameter at the point where the integral curve is 50% is the average particle diameter, and the frequency (%) of the particle size distribution measurement result exceeds 0.00%. The maximum particle size at the time point is the maximum particle diameter. In addition, as the sample, 1 part by weight of the epoxy compound of the rubber particles obtained in the following Production Example 2 was dispersed in 20 parts by weight of tetrahydrofuran.

製造例2 Manufacturing Example 2

(散佈橡膠粒子之環氧化合物的製造) (Manufacture of epoxy compound with rubber particles)

製造例1所得之橡膠粒子5重量份，在氮氣氣流下，使用加溫至60℃狀態的溶解器，使其分散在商品名「CELLOXIDE 2021P」((3,4-環氧基)環己烷羧酸3,4-環氧基環己基甲酯、(股)DAICEL公司製)100重量份(1000rpm、60分鐘)，進行真空脫泡，得到散佈橡膠粒子之環氧化合物(25℃的黏度：1036mPa‧s)。 5 parts by weight of the rubber particles obtained in Production Example 1 were dispersed in a dissolver at a temperature of 60 ° C under a nitrogen gas flow to be dispersed under the trade name "CELLOXIDE 2021P" ((3,4-epoxy)cyclohexane). 100 parts by weight (1000 rpm, 60 minutes) of 3,4-epoxycyclohexylmethyl carboxylic acid (manufactured by DAICEL Co., Ltd.) was vacuum defoamed to obtain an epoxy compound in which rubber particles were dispersed (viscosity at 25 ° C: 1036mPa‧s).

再者，製造例2所得之散佈橡膠粒子之環氧化合物(5重量份的橡膠粒子分散於100重量份的CELLOXIDE 2021P者)在25℃的黏度，係使用數位黏度計(型號「DVU-EII型」、(股)TOKIMEC公司製)測定。 Further, the epoxy compound of the rubber particles obtained in Production Example 2 (5 parts by weight of rubber particles dispersed in 100 parts by weight of CELLOXIDE 2021P) was used at a viscosity of 25 ° C, and a digital viscometer (Model "DVU-EII type" was used. ", (share) TOKIMEC company system) measurement.

製造例3 Manufacturing Example 3

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

於具備攪拌機、溫度計及回流冷卻器的反應容器，放入1,4-環己烷二羧酸(東京化成工業(股)製)172重量份、新戊二醇(東京化成工業(股)製)208重量份、酞酸四丁酯(和光純藥工業(股)製)0.1重量份，加熱至160℃，再從160℃至250℃花費4小時升溫。然後，花費1小時，減壓至5mmHg，再減壓至0.3mmHg以下後，於250℃反應1小時，得到脂環式聚酯樹脂。 172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and neopentyl glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser. 208 parts by weight of 0.1 parts by weight of tetrabutyl phthalate (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 160 ° C, and further heated from 160 ° C to 250 ° C for 4 hours. Thereafter, the pressure was reduced to 5 mmHg for 1 hour, and the pressure was reduced to 0.3 mmHg or less, followed by reaction at 250 ° C for 1 hour to obtain an alicyclic polyester resin.

製造例4 Manufacturing Example 4

用表1、表2、表4及表5表示的調配比例(單位：重量份)，將商品名「RIKACID MH-700」(新日本理化(股)製)、商品名「HN-7200」(日立化成工業(股)製)、商品名「HN-5700」(日立化成工業(股)製)、商品名「U-CAT 18X」(SANAPRO(股)製)及乙二醇(和光純藥工業(股)製)，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Shinky(股)製)混合均勻並進行脫泡，得到硬化劑組成物(有稱為「K劑」的情況)。 The blending ratio (unit: parts by weight) indicated in Table 1, Table 2, Table 4, and Table 5, and the trade name "RIKACID MH-700" (manufactured by Shin-Nippon Chemical and Chemical Co., Ltd.) and the trade name "HN-7200" ( Hitachi Chemical Co., Ltd., the trade name "HN-5700" (Hitachi Chemical Industry Co., Ltd.), the trade name "U-CAT 18X" (SANAPRO), and ethylene glycol (Wako Pure Chemical Industries) (manufactured by the company), using a self-propelled stirring device (trade name "Defoaming Ryotaro AR-250", Shinky (manufactured by the company)), mixing and defoaming to obtain a hardener composition (referred to as "K agent" "Case).

實施例1A Example 1A

首先，根據表1所示的調配配方(單位：重量份)，將製造例2所得之散佈橡膠粒子之環氧化合物、聚矽氧橡膠粒子(商品名「KMP-600」、信越化學工業(股)製))、氧化鈦(商品名「DCF-T-17050」、Resinocolor工業(股)製)及氧化矽(商品名「FB-970FD」、Denka(股)製)，使用溶解器混合均勻，藉由滾輪磨機，在指定條件下(滾輪間隔：0.2mm、旋轉數：25Hz、3次)進行熔融混練，得到混練物。 First, according to the formulation (unit: parts by weight) shown in Table 1, the epoxy compound and the polyoxynylene rubber particles (product name "KMP-600", Shin-Etsu Chemical Industry Co., Ltd.) of the rubber particles obtained in Production Example 2 were used. ))), titanium oxide (trade name "DCF-T-17050", manufactured by Resinocolor Industrial Co., Ltd.) and cerium oxide (trade name "FB-970FD", manufactured by Denka Co., Ltd.), which are uniformly mixed using a dissolver. The kneading was carried out by a roller mill under specified conditions (roller spacing: 0.2 mm, number of revolutions: 25 Hz, three times) to obtain a kneaded product.

然後，以成為如表1所示的調配配方(單位：重量份)之方式，將上述所得的混練物與製造例4所得之硬化劑組成物，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Shinky(股)製)混合均勻(2000rpm、5分鐘)並進行脫泡，得到硬化性樹脂組成物(硬化性環氧樹脂組成物)。 Then, the kneaded product obtained in the above-described kneaded product and the hardener composition obtained in Production Example 4 were used in a blending formulation (unit: parts by weight) as shown in Table 1, using a self-revolving stirring device (trade name "defoaming" Ryotaro AR-250" and Shinky Co., Ltd.) were uniformly mixed (2000 rpm, 5 minutes) and defoamed to obtain a curable resin composition (curable epoxy resin composition).

用由聚酯構成的離型膜夾著上述硬化性樹脂組成物，放入150℃的壓縮成型用模具內，以3.0MPa的壓力 進行加熱及加壓600秒使其硬化，然後藉由進行後硬化(150℃、5小時)，得到硬化物。 The curable resin composition was sandwiched between a release film made of a polyester, placed in a compression molding die at 150 ° C, and heated and pressurized at a pressure of 3.0 MPa for 600 seconds to be cured, and then cured. Hardened (150 ° C, 5 hours) to obtain a cured product.

實施例2A至9A、比較例1A至8A Examples 2A to 9A, Comparative Examples 1A to 8A

除硬化性樹脂組成物的組成，變更為表1、2所示的組成外，與實施例1A同樣調製硬化性樹脂組成物及硬化物。再者，於一部分的實施例及比較例，作為硬化性樹脂組成物的構成成分，使用表1、2所示的環氧化合物，取代或組合製造例2所得之散佈橡膠粒子之環氧化合物。 The curable resin composition and the cured product were prepared in the same manner as in Example 1A except that the composition of the curable resin composition was changed to the compositions shown in Tables 1 and 2. Further, in some of the examples and comparative examples, the epoxy compound shown in Tables 1 and 2 was used as a constituent component of the curable resin composition, and the epoxy compound of the rubber particles obtained in Production Example 2 was replaced or combined.

實施例10A Example 10A

根據表3所示的調配配方(單位：重量份)，將製造例2所得之散佈橡膠粒子之環氧化合物、聚矽氧橡膠粒子(商品名「KMP-600」、信越化學工業(股)製))、氧化鈦(商品名「DCF-T-17050」、Resinocolor工業(股)製)及氧化矽(商品名「FB-970FD」、Denka(股)製)，使用溶解器均勻混合後，藉由滾輪磨機在指定條件下(滾輪間隔：0.2mm、旋轉數：25Hz、3次)進行熔融混練，得到混練物。 According to the formulation (unit: parts by weight) shown in Table 3, the epoxy compound and the polyoxynylene rubber particles (product name "KMP-600", manufactured by Shin-Etsu Chemical Co., Ltd.) of the rubber particles obtained in Production Example 2 were prepared. )), titanium oxide (trade name "DCF-T-17050", manufactured by Resinocolor Industrial Co., Ltd.) and cerium oxide (trade name "FB-970FD", manufactured by Denka Co., Ltd.), which are uniformly mixed using a dissolver, and then borrowed The kneading was carried out by a roller mill under specified conditions (roller spacing: 0.2 mm, number of revolutions: 25 Hz, three times) to obtain a kneaded product.

然後，以成為如表3所示的調配配方(單位：重量份)之方式，將上述所得之混練物與硬化觸媒(商品名「SUNAID SI-100L」、三新化學工業(股)製)，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Shinky(股)製)混合均勻(2000rpm、5分鐘)並進行脫泡，得到硬化性樹脂組成物(硬化性環氧樹脂組成物)。 Then, the obtained kneaded material and the curing catalyst (trade name "SUNAID SI-100L", Sanshin Chemical Industry Co., Ltd.) were used as the formulation (unit: part by weight) as shown in Table 3. The mixture was uniformly mixed (2000 rpm, 5 minutes) using a self-propelled stirring device (trade name "Defoaming Ryotaro AR-250" or Shinky Co., Ltd.) to obtain a curable resin composition (curable epoxy). Resin composition).

用由聚構所成的離型膜夾著上述硬化性樹脂組成物，放入150℃的壓縮成型用模具內，以3.0MPa的壓力進行加熱及加壓600秒使其硬化，然後藉由進行後硬化(150℃、5小時)，得到硬化物。 The curable resin composition was sandwiched between the release film formed by the polymerization, placed in a compression molding die at 150 ° C, heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then cured. After hardening (150 ° C, 5 hours), a cured product was obtained.

實施例11A、12A、比較例9A至13A Examples 11A, 12A, Comparative Examples 9A to 13A

除硬化性樹脂組成物的組成，變更為表3所示的組成外，與實施例10A同樣調製硬化性樹脂組成物及硬化物。再者，於一部分的實施例及比較例，作為硬化性樹脂組成物的構成成分，使用表3所示的環氧化合物，取代或組合製造例2所得之散佈橡膠粒子之環氧化合物。 The curable resin composition and the cured product were prepared in the same manner as in Example 10A except that the composition of the curable resin composition was changed to the composition shown in Table 3. Further, in some of the examples and comparative examples, as the constituent components of the curable resin composition, the epoxy compound shown in Table 3 was used instead of or in combination with the epoxy compound of the rubber particles obtained in Production Example 2.

再者，實施例1A至12A、比較例1A至9A所得之硬化性樹脂組成物，在25℃為液狀。另一方面，比較例10A至13A所得之硬化性樹脂組成物，在25℃為固體。 Further, the curable resin compositions obtained in Examples 1A to 12A and Comparative Examples 1A to 9A were liquid at 25 °C. On the other hand, the curable resin compositions obtained in Comparative Examples 10A to 13A were solid at 25 °C.

實施例1B Example 1B

根據表4所示的調配配方(單位：重量份)，將製造例2所得之散佈橡膠粒子之環氧化合物、異氰脲酸衍生物(單烯丙基二環氧丙基異氰脲酸酯；商品名「MA-MGIC」、四國化成工業(股)製)、矽氧烷衍生物(分子內具有2個環氧基的矽氧烷衍生物；商品名「X-40-2678」)及應力緩和劑(聚矽氧橡膠粒子；商品名「KMP-600」、信越化學工業(股)製)，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、 Shinky(股)製)混合均勻，進行脫泡後製成混合物。再者，上述混合，為了溶解MA-DGIC，以在80℃攪拌1小時方式實施。 According to the formulation shown in Table 4 (unit: parts by weight), the epoxy compound of the rubber particles obtained in Production Example 2, an isocyanuric acid derivative (monoallyl epoxypropyl isocyanurate) ; trade name "MA-MGIC", manufactured by Shikoku Chemical Industry Co., Ltd.), a siloxane derivative (a oxane derivative having two epoxy groups in the molecule; trade name "X-40-2678") And a stress relieving agent (polyoxymethylene rubber particles; trade name "KMP-600", Shin-Etsu Chemical Co., Ltd.), using a self-propelled stirring device (trade name "Degassing Ritaro AR-250", Shinky (share) The system is uniformly mixed and defoamed to form a mixture. Further, the above mixing was carried out by stirring at 80 ° C for 1 hour in order to dissolve the MA-DGIC.

然後，根據表4所示的調配配方(單位：重量份)，將上述所得之混合物與白色顏料(氧化鈦；商品名「DCF-T-17050」、Resinocolor工業(股)製)、無機填充劑(氧化矽；商品名「FB-970FD」、Denka(股)製)使用溶解器混合均勻後，藉由滾輪磨機在指定條件下(滾輪間隔：0.2mm、旋轉數：25Hz、3次)進行熔融混練，得到混練物。 Then, according to the formulation (unit: parts by weight) shown in Table 4, the mixture obtained above and a white pigment (titanium oxide; trade name "DCF-T-17050", manufactured by Resinocolor Industrial Co., Ltd.), inorganic filler (Yttrium oxide; trade name "FB-970FD", manufactured by Denka Co., Ltd.) was uniformly mixed using a dissolver, and then subjected to a roller mill under specified conditions (roller spacing: 0.2 mm, number of revolutions: 25 Hz, three times) Melt and knead to obtain a kneaded product.

然後，以成為如表4所示的調配配方(單位：重量份)之方式，將上述所得之混練物與製造例4所得之硬化劑組成物，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Shinky(股)製)混合均勻(2000rpm、5分鐘)並進行脫泡，得到硬化性樹脂組成物(硬化性環氧樹脂組成物)。 Then, the kneaded material obtained in the above and the hardener composition obtained in Production Example 4 were used in a blending formulation (unit: parts by weight) as shown in Table 4, using a self-revolving stirring device (trade name "defoaming" Ryotaro AR-250" and Shinky Co., Ltd.) were uniformly mixed (2000 rpm, 5 minutes) and defoamed to obtain a curable resin composition (curable epoxy resin composition).

用由聚酯構成的離型膜夾著上述硬化性樹脂組成物，放入150℃的壓縮成型用模具內，以3.0MPa的壓力進行加熱及加壓600秒，然後藉由進行後硬化(150℃、5小時)，得到硬化物。 The curable resin composition was sandwiched between a release film made of a polyester, placed in a compression molding die at 150 ° C, heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then post-hardened (150). °C, 5 hours), a hardened material was obtained.

實施例2B至17B、比較例1B至12B Examples 2B to 17B, Comparative Examples 1B to 12B

除了光反射用硬化性樹脂組成物的調配組成，變更為表4或表5所示的組成外，與實施例1B同樣製得光反射用硬化性樹脂組成物及硬化物。再者，於一部分的實施例及比較例，作為硬化性樹脂組成物的構成成分，使用表4 或表5所示的環氧化合物，取代或組合製造例2所得之散佈橡膠粒子之環氧化合物。 The curable resin composition for light reflection and the cured product were obtained in the same manner as in Example 1B except that the composition of the curable resin composition for light reflection was changed to the composition shown in Table 4 or Table 5. Further, in some of the examples and comparative examples, as the constituent components of the curable resin composition, the epoxy compound shown in Table 4 or Table 5 was used instead of or in combination with the epoxy compound of the dispersed rubber particles obtained in Production Example 2. .

實施例18B Example 18B

根據表6所示的調配比例(單位：重量份)，將製造例2所得之散佈橡膠粒子之環氧化合物、異氰脲酸衍生物(單烯丙基二環氧丙基異氰脲酸酯；商品名「MA-MGIC」、四國化成工業(股)製)、矽氧烷衍生物(分子內具有2個環氧基的矽氧烷衍生物；商品名「X-40-2678」、信越化學工業(股)製)、應力緩和劑(聚矽氧橡膠粒子；商品名「KMP-600」、信越化學工業(股)製)及製造例3所得之脂環式聚酯樹脂，使用自公轉式攪拌裝置(商品名「脫泡練太郎AR-250」、Shinky(股)製)混合均勻並進行脫泡，製成混合物。再者，上述混合，為了溶解MA-DGIC，以在80℃攪拌1小時的方式實施。 According to the blending ratio (unit: parts by weight) shown in Table 6, the epoxy compound and the isocyanuric acid derivative (monoallyl epoxypropyl isocyanurate) dispersed in the rubber particles obtained in Production Example 2 were used. ; trade name "MA-MGIC", manufactured by Shikoku Chemicals Co., Ltd.), a siloxane derivative (a siloxane derivative having two epoxy groups in the molecule; trade name "X-40-2678", The alicyclic polyester resin obtained by the Shin-Etsu Chemical Co., Ltd., the stress relieving agent (polyoxyethylene rubber particles; the trade name "KMP-600", manufactured by Shin-Etsu Chemical Co., Ltd.), and the production example 3 are used. A revolving stirring device (trade name "Defoaming Ryotaro AR-250", manufactured by Shinky Co., Ltd.) was uniformly mixed and defoamed to prepare a mixture. Further, the above mixing was carried out so as to dissolve MA-DGIC at 80 ° C for 1 hour.

然後，根據表6所示的調配比例(單位：重量份)，將上述所得之混合物與白色顏料(氧化鈦；商品名「DCF-T-17050」、Resinocolor工業(股)製)、無機填充劑(氧化矽；商品名「FB-970FD」、Denka(股)製)，使用溶解器混合均勻後，藉由滾輪磨機在指定條件下(滾輪間隔：0.2mm、旋轉數：25Hz、3次)進行熔融混練，得到混練物。 Then, according to the blending ratio (unit: parts by weight) shown in Table 6, the mixture obtained above and a white pigment (titanium oxide; trade name "DCF-T-17050", manufactured by Resinocolor Industrial Co., Ltd.), inorganic filler (yttrium oxide; trade name "FB-970FD", manufactured by Denka Co., Ltd.), and uniformly mixed with a dissolver, and under a specified condition by a roller mill (roller interval: 0.2 mm, number of rotations: 25 Hz, 3 times) Melt kneading was carried out to obtain a kneaded product.

然後，以成為如表4所示的調配比例(單位：重量份)之方式，將上述所得之混練物與硬化觸媒(商品名「SUNAID SI-100L」、三新化學工業(股)製)，使用自公轉式攪拌裝置 (商品名「脫泡練太郎AR-250」、Shinky(股)製)混合均勻(2000rpm、5分鐘)並進行脫泡，得到硬化性樹脂組成物(硬化性環氧樹脂組成物)。 Then, the obtained kneaded material and the curing catalyst (trade name "SUNAID SI-100L", Sanshin Chemical Industry Co., Ltd.) were used as the blending ratio (unit: parts by weight) as shown in Table 4. The mixture was uniformly mixed (2000 rpm, 5 minutes) using a self-propelled stirring device (trade name "Defoaming Ryotaro AR-250" or Shinky Co., Ltd.) to obtain a curable resin composition (curable epoxy). Resin composition).

用由聚酯構成的離型膜夾著上述硬化性樹脂組成物，放入150℃的壓縮成型用模具內，以3.0MPa的壓力進行加熱及加壓600秒使其硬化，然後藉由進行後硬化(150℃、5小時)，得到硬化物。 The curable resin composition was sandwiched between a release film made of a polyester, placed in a compression molding die at 150 ° C, and heated and pressurized at a pressure of 3.0 MPa for 600 seconds to be cured, and then cured. Hardened (150 ° C, 5 hours) to obtain a cured product.

實施例19B、20B、比較例13B至18B Examples 19B, 20B, Comparative Examples 13B to 18B

除了光反射用硬化性樹脂組成物的調配組成，變更為表6所示的組成外，與實施例18B同樣製得光反射用硬化性樹脂組成物及硬化物。再者，於一部分的實施例及比較例，作為硬化性樹脂組成物的構成成分，使用表6所示的環氧化合物，取代或組合製造例2所得之散佈橡膠粒子之環氧化合物。 A light-reflecting curable resin composition and a cured product were obtained in the same manner as in Example 18B except that the composition of the curable resin composition for light reflection was changed to the composition shown in Table 6. In addition, in some examples and comparative examples, as the constituent components of the curable resin composition, the epoxy compound shown in Table 6 was used instead of or in combination with the epoxy compound of the rubber particles obtained in Production Example 2.

再者，實施例1B至20B、比較例1B至18B之硬化性樹脂組成物，在25℃的屬性(液狀或固體)表示於表4、表5及表6的「硬化性樹脂組成物的屬性」。 In addition, the properties of the curable resin compositions of Examples 1B to 20B and Comparative Examples 1B to 18B at 25 ° C (liquid or solid) are shown in Table 4, Table 5, and Table 6 of the "curable resin composition". Attributes".

〈評價〉  <Evaluation>  

對於實施例及比較例所得之硬化物，實施下述的評價。 The following evaluations were performed on the cured products obtained in the examples and the comparative examples.

[初期反射率] [Initial reflectance]

切割實施例及比較例所得之硬化物，製作長度30mm×寬度30mm×厚度3mm的測試片。然後，使用分光光度計(商品名「分光光度計UV-2450」、(股)島津製作所製)，測定各測試片對波長450nm的光之反射率(成為「初期反射率」)。結果表示於表1至6。 The cured product obtained in the examples and the comparative examples was cut to prepare a test piece having a length of 30 mm, a width of 30 mm, and a thickness of 3 mm. Then, a spectrophotometer (trade name "Spectrophotometer UV-2450", manufactured by Shimadzu Corporation) was used, and the reflectance (as "initial reflectance") of each test piece with respect to light having a wavelength of 450 nm was measured. The results are shown in Tables 1 to 6.

再者，只要是初期反射率為95%以上，作為光反射用材料可說是特別好。 Further, as long as the initial reflectance is 95% or more, it is particularly preferable as a material for light reflection.

[加熱老化前後的反射率保持率] [Reflection retention before and after heating aging]

使用已進行初期反射率的評價的測試片(硬化物；長度30mm×寬度30mm×厚度3mm)，將該測試片放入120℃的乾燥機，進行放置250小時的測試(耐熱測試)後，與初期反射率同樣測定波長450nm的光的反射率。然後藉由下述式，算出反射率保持率(加熱老化前後)。結果表示於表1至6。 Using a test piece (hardened material; length 30 mm × width 30 mm × thickness 3 mm) in which the initial reflectance was evaluated, the test piece was placed in a dryer at 120 ° C, and after being placed for 250 hours (heat resistance test), The initial reflectance also measured the reflectance of light having a wavelength of 450 nm. Then, the reflectance retention ratio (before and after heat aging) was calculated by the following formula. The results are shown in Tables 1 to 6.

[反射率保持率(加熱老化前後)]=([加熱老化後的反射率]/[初期反射率])×100 [Reflection retention rate (before and after heating aging)] = ([reflectance after heat aging] / [initial reflectance]) × 100

該反射率保持率越高，表示硬化物的耐熱性佳。再者，只要是120℃、250小時加熱後的反射率保持率為90%以上，作為光反射用材料可說是耐熱性特別好。 The higher the reflectance retention ratio, the better the heat resistance of the cured product. In addition, as long as the reflectance retention rate after heating at 120 ° C for 250 hours is 90% or more, it can be said that the material for light reflection is particularly excellent in heat resistance.

[紫外線老化前後的反射率保持率] [Reflection retention before and after UV aging]

使用已進行初期反射率的評價的測試片(硬化物；長度30mm×寬度30mm×厚度3mm)，對該測試片進行照射強度 10mW/cm2的紫外線250小時的測試(耐光測試)後，與初期反射率同樣測定波長450nm的光的反射率。然後藉由下述式，算出反射率保持率(紫外線老化前後)。結果表示於表1至6。 Using a test piece (cured material; length 30 mm × width 30 mm × thickness 3 mm) in which the initial reflectance was evaluated, the test piece was subjected to a test (light resistance test) of ultraviolet light having an irradiation intensity of 10 mW/cm 2 for 250 hours, and an initial stage. The reflectance was also measured for the reflectance of light having a wavelength of 450 nm. Then, the reflectance retention ratio (before and after ultraviolet aging) was calculated by the following formula. The results are shown in Tables 1 to 6.

[反射率保持率(紫外線老化前後)]=([紫外線老化後的反射率]/[初期反射率])×100 [Reflection retention rate (before and after UV aging)] = ([reflectance after ultraviolet aging] / [initial reflectance]) × 100

該反射率保持率越高，表示硬化物的耐光性佳。再者，只要是強度10mW/cm2、250小時照射後的反射率保持率為90%以上，作為光反射用材料可說是耐光性特別好。 The higher the reflectance retention ratio, the better the light resistance of the cured product. In addition, as long as the intensity is 10 mW/cm 2 and the reflectance retention after irradiation for 250 hours is 90% or more, it is said that the light-reflecting material is particularly excellent in light resistance.

[蝕刻測試] [etching test]

使用已進行初期反射率的評價的測試片(硬化物；長度30mm×寬度30mm×厚度3mm)，測定該測試片的重量(成為「初期重量」)後，浸漬於70℃的11重量%氫氧化鉀水溶液。60分鐘後取出測試片，用純水洗淨，測定60℃、30分鐘乾燥後的重量(成為「蝕刻測試後的重量」)。然後藉由下述式，算出重量維持率(%)。結果表示於表4至表6。 A test piece (cured material; length: 30 mm × width: 30 mm × thickness: 3 mm) having been evaluated for initial reflectance was used, and the weight of the test piece (becoming "initial weight") was measured, and then immersed in 11% by weight of hydroxide at 70 ° C. Potassium aqueous solution. After 60 minutes, the test piece was taken out, washed with pure water, and the weight after drying at 60 ° C for 30 minutes (being the "weight after etching test") was measured. Then, the weight maintenance ratio (%) was calculated by the following formula. The results are shown in Tables 4 to 6.

[重量維持率(%)]=([初期重量]-[蝕刻測試後的重量]/[初期重量])×100 [Weight maintenance ratio (%)] = ([Initial weight] - [weight after etching test] / [initial weight]) × 100

[切割加工時有無龜裂的評價(強韌性評價)] [Evaluation of cracking during cutting (strength and toughness evaluation)]

切割實施例及比較例所得之硬化物，製作長度5mm×寬度5mm×厚度3mm的測試片。於上述硬化物的切割加工，使用微切割機(商品名「BS-300CL」、Meiwafosis(股) 公司製)，切割加工時硬化物是否發生龜裂，使用數位顯微鏡(商品名「VHX-900」、(股)Keyence公司製)觀察、確認。於表1至6，表示每1個樣品製作10個測試片，以其中確認發生龜裂的測試片的個數[個/10個]作為評價結果。 The cured product obtained in the examples and the comparative examples was cut to prepare a test piece having a length of 5 mm, a width of 5 mm, and a thickness of 3 mm. In the cutting process of the above-mentioned cured product, a micro-cutting machine (trade name "BS-300CL", manufactured by Meiwafosis Co., Ltd.) was used, and the cured product was cracked during cutting, and a digital microscope (trade name "VHX-900" was used. , (shares) Keyence company) observation, confirmation. In Tables 1 to 6, it is shown that 10 test pieces were produced for each sample, and the number of test pieces [10 sheets] in which cracking occurred was confirmed as the evaluation result.

[回焊時有無龜裂的評價] [Evaluation of cracks during reflow]

對藉由上述切割加工所得之測試片(長度5mm×寬度5mm×厚度3mm)，使用回焊爐(商品名「UNI-5016F」、日本ANTOM(股)製)，以260℃為最高溫度維持5秒、全部回焊時間90秒實施回焊處理。然後，測試片是否因該回焊處理發生龜裂，使用數位顯微鏡(商品名「VHX-900」、(股)Keyence公司製)觀察、確認。於表1至6，表示每1個樣品進行10個測試片的回焊處理，以其中確認發生龜裂的測試片的個數[個/10個]作為評價結果。 The test piece (length 5 mm × width 5 mm × thickness 3 mm) obtained by the above-mentioned cutting process was maintained at a maximum temperature of 260 ° C using a reflow furnace (trade name "UNI-5016F", manufactured by ANTOM Co., Ltd.). The reflow process is performed in seconds and all reflow times of 90 seconds. Then, whether or not the test piece was cracked by the reflow process was observed and confirmed using a digital microscope (trade name "VHX-900", manufactured by Keyence Corporation). In Tables 1 to 6, the reflow process of 10 test pieces per sample was carried out, and the number of test pieces [10 sheets] in which cracking occurred was confirmed as the evaluation result.

然而，切割加工時已確認發生龜裂者，不進行回焊時有無發生龜裂之評價。 However, it was confirmed that cracking occurred during the cutting process, and whether or not cracking occurred during reflow was not performed.

[綜合判定] [Comprehensive judgment]

於表1至3，各測試的結果滿足下述(1)至(5)的每一項者，判定為○(良好)。另一方面，未滿足下述(1)至(5)的任一項的情況，判定為X(不良)。 In Tables 1 to 3, the results of the respective tests satisfy each of the following (1) to (5), and it is judged as ○ (good). On the other hand, in the case where any of the following (1) to (5) is not satisfied, it is determined that X (bad).

而且，於表4至6，各測試的結果，滿足下述(1)至(6)的每一項者，判定為○(良好)。另一方面，未滿足下述(1)至(6)的任一項的情況，判定為X(不良)。 Further, in Tables 4 to 6, the results of the respective tests satisfy each of the following (1) to (6), and it is judged as ○ (good). On the other hand, in the case where any of the following (1) to (6) is not satisfied, it is judged as X (bad).

(1)初期反射率：光反射率為95%以上 (1) Initial reflectance: light reflectance is 95% or more

(2)加熱老化前後的反射率保持率：反射率保持率為90%以上 (2) Reflectance retention rate before and after heating aging: reflectance retention rate is 90% or more

(3)紫外線老化前後的反射率保持率：反射率保持率為90%以上 (3) Reflectance retention rate before and after ultraviolet aging: reflectance retention rate is 90% or more

(4)切割加工時有無龜裂的評價：發生龜裂的個數為0個 (4) Evaluation of cracking during cutting: The number of cracks is 0

(5)回焊時有無龜裂的評價：發生龜裂的個數為0個 (5) Evaluation of cracking during reflow: the number of cracks is 0

(6)蝕刻測試：重量維持率為0.5%以下 (6) Etching test: weight maintenance rate is 0.5% or less

結果表示於表1至6的綜合判定欄。 The results are shown in the comprehensive decision column of Tables 1 to 6.

再者，關於表1至6所示的成分，說明如下。 Further, the components shown in Tables 1 to 6 will be described below.

(散佈橡膠粒子之環氧化合物) (epoxy compound with rubber particles dispersed)

製造例2所得之散佈橡膠粒子之環氧化合物 Epoxy compound of the dispersed rubber particles obtained in Production Example 2

(環氧化合物) (epoxy compound)

CELLOXIDE 2021P：商品名「CELLOXIDE 2021P」(3,4-環氧基)環己烷羧酸3,4-環氧基環己基甲酯)、(股)DAICEL公司製 CELLOXIDE 2021P: trade name "CELLOXIDE 2021P" (3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester), manufactured by DAICEL

EHPE3150：商品名「EHPE3150」(2,2-雙(羥基甲基)-1-丁醇的1,2-環氧基-4-(2-環氧乙烷基)環己烷加成物)、(股)DAICEL公司製 EHPE3150: trade name "EHPE3150" (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol) , (share) DAICEL company system

YD-128：商品名「YD-128」(雙酚A型環氧樹脂)、新日鐵化學(股)製 YD-128: trade name "YD-128" (bisphenol A epoxy resin), Nippon Steel Chemical Co., Ltd.

(異氰脲酸衍生物) (isocyanuric acid derivative)

TEPIC：商品名「TEPIC」(異氰脲酸三環氧丙酯)、日產化學工業(股)製 TEPIC: trade name "TEPIC" (triglycidyl isocyanurate), Nissan Chemical Industry Co., Ltd.

MA-DGIC：商品名「MA-MGIC」(單烯丙基二環氧丙基異氰脲酸酯)、四國化成工業(股)製 MA-DGIC: trade name "MA-MGIC" (monoallyl epoxypropyl isocyanurate), Shikoku Chemical Industry Co., Ltd.

DA-DGIC：商品名「DA-MGIC」(二烯丙基單環氧丙基異氰脲酸酯)、四國化成工業(股)製 DA-DGIC: trade name "DA-MGIC" (diallyl monoepoxypropyl isocyanurate), Shikoku Chemical Industry Co., Ltd.

(矽氧烷衍生物) (a halogen derivative)

X-40-2678：商品名「X-40-2678」(分子內具有2個環氧基的矽氧烷衍生物)、信越化學工業(股)製 X-40-2678: trade name "X-40-2678" (a cyclooxyl derivative having two epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd.

X-40-2720：商品名「X-40-2720」(分子內具有3個環氧基的矽氧烷衍生物)、信越化學工業(股)製 X-40-2720: trade name "X-40-2720" (a cyclooxygen derivative having three epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd.

X-40-2670：商品名「X-40-2670」(分子內具有4個環氧基的矽氧烷衍生物)、信越化學工業(股)製 X-40-2670: trade name "X-40-2670" (a cyclooxygen derivative having four epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd.

(硬化劑組成物) (hardener composition)

MH-700：商品名「RIKACID MH-700」(4-甲基六氫鄰苯二甲酸酐/六氫鄰苯二甲酸酐)、新日本理化(股)製 MH-700: trade name "RIKACID MH-700" (4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride), New Japan Physical and Chemical Co., Ltd.

HN-7200：商品名「HN-7200」(4-甲基六氫鄰苯二甲酸酐與脂環式聚酯樹脂的混合物)、日立化成工業(股)製 HN-7200: trade name "HN-7200" (mixture of 4-methylhexahydrophthalic anhydride and alicyclic polyester resin), manufactured by Hitachi Chemical Co., Ltd.

HN-5700：商品名「HN-5700」(4-甲基六氫鄰苯二甲酸酐/3-甲基六氫鄰苯二甲酸酐=70/30與脂環式聚酯樹脂的混合物)、日立化成工業(股)製 HN-5700: trade name "HN-5700" (4-methylhexahydrophthalic anhydride / 3-methylhexahydrophthalic anhydride = 70/30 mixture with alicyclic polyester resin), Hitachi Chemical Industry Co., Ltd.

18X：商品名「U-CAT 18X」(硬化促進劑)、SANAPRO(股)製 18X: Product name "U-CAT 18X" (hardening accelerator), SANAPRO (share) system

乙二醇：商品名「乙二醇」、和光純藥工業(股)製 Ethylene glycol: trade name "ethylene glycol", and Wako Pure Chemical Industries Co., Ltd.

(硬化觸媒) (hardening catalyst)

SUNAID SI-100L：商品名「SUNAID SI-100L」、三新化學工業(股)製 SUNAID SI-100L: trade name "SUNAID SI-100L", Sanshin Chemical Industry Co., Ltd.

(應力緩和劑) (stress mitigator)

KMP-600：商品名「KMP-600」(表面具備聚矽氧樹脂的交聯聚二甲基矽氧烷)、信越化學工業(股)製 KMP-600: trade name "KMP-600" (crosslinked polydimethyl siloxane with polyoxyl resin on the surface), Shin-Etsu Chemical Co., Ltd.

KMP-602：商品名「KMP-602」(表面具備聚矽氧樹脂的交聯聚二甲基矽氧烷)、信越化學工業(股)製 KMP-602: trade name "KMP-602" (crosslinked polydimethyl siloxane with polyoxyl resin on the surface), Shin-Etsu Chemical Co., Ltd.

SF8421：商品名「SF8421」(式(1)所示的聚伸烷基醚改質聚矽氧化合物)、Toray-Dow Corning(股)製 SF8421: trade name "SF8421" (polyalkylene ether modified polyoxyl compound represented by formula (1)), manufactured by Toray-Dow Corning Co., Ltd.

Y-19268：商品名「Y-19268」(式(1)所示的聚伸烷基醚改質聚矽氧化合物)、日本Momentive Performance Materials(同)製 Y-19268: trade name "Y-19268" (polyalkylene ether modified polyoxyl compound represented by formula (1)), Japan Momentive Performance Materials (same)

(白色顏料) (white pigment)

DCF-T-17050：商品名「DCF-T-17050」(氧化鈦、平均粒徑0.3μm、最大粒徑1μm)、Resinocolor工業(股)製 DCF-T-17050: trade name "DCF-T-17050" (titanium oxide, average particle size 0.3μm, maximum particle size 1μm), Resinocolor Industrial Co., Ltd.

氧化鈦：商品名「DCF-T-17050」(氧化鈦、平均粒徑0.3μm、最大粒徑1μm以下)、Resinocolor工業(股)製 Titanium oxide: trade name "DCF-T-17050" (titanium oxide, average particle diameter 0.3 μm, maximum particle diameter 1 μm or less), and Resinocolor Industrial Co., Ltd.

(無機填充劑) (inorganic filler)

FB-970FD：商品名「FB-970FD」(氧化矽、無表面處理、平均粒徑16.7μm、最大粒徑70μm)、Denka(股)製 FB-970FD: trade name "FB-970FD" (yttrium oxide, no surface treatment, average particle size 16.7μm, maximum particle size 70μm), Denka (share) system

DAW-1025：商品名「DAW-1025」(氧化鋁、平均粒徑7.9μm、最大粒徑32μm)、Denka(股)製 DAW-1025: trade name "DAW-1025" (alumina, average particle size 7.9 μm, maximum particle size 32 μm), manufactured by Denka Co., Ltd.

HF-05：商品名「HF-05」(氮化鋁、平均粒徑5μm、最大粒徑5μm)、(股)TOKUYAMA製 HF-05: trade name "HF-05" (aluminum nitride, average particle size 5 μm, maximum particle size 5 μm), (manufactured by TOKUYAMA)

氧化矽：商品名「FB-970FD」(氧化矽、無表面處理、平均粒徑16.7μm、最大粒徑70μm)、Denka(股)製 Yttrium oxide: trade name "FB-970FD" (yttrium oxide, no surface treatment, average particle size 16.7 μm, maximum particle size 70 μm), manufactured by Denka Co., Ltd.

氧化鋁：商品名「DAW-1025」(氧化鋁、平均粒徑7.9μm、最大粒徑32μm)、Denka(股)製 Alumina: trade name "DAW-1025" (alumina, average particle size 7.9 μm, maximum particle size 32 μm), manufactured by Denka Co., Ltd.

氮化鋁：商品名「HF-05」(氮化鋁、平均粒徑5μm、最大粒徑5μm)、(股)TOKUYAMA製 Aluminum nitride: trade name "HF-05" (aluminum nitride, average particle size 5 μm, maximum particle size 5 μm), (manufactured by TOKUYAMA)

以下附記上述說明的本發明的變型。 The modifications of the invention described above are attached below.

[1]特徵為含有脂環式環氧化合物(A)、聚矽氧橡膠粒子以外的橡膠粒子(B)、白色顏料(C)、無機填充劑(D)及應力緩和劑(H)，又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)之在25℃為液狀的光反射用硬化性樹脂組成物。 [1] characterized by containing an alicyclic epoxy compound (A), rubber particles (B) other than polyoxyxylene rubber particles, a white pigment (C), an inorganic filler (D), and a stress relieving agent (H), A curable resin composition for light reflection which is liquid at 25 ° C containing a curing agent (E), a curing accelerator (F) or a curing catalyst (G).

[2]特徵為含有脂環式環氧化合物(A)、聚矽氧橡膠粒 子以外的橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)、分子內具有2個以上環氧基的矽氧烷衍生物(J)及脂環式聚酯樹脂(K)，又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)之在25℃為液狀的光反射用硬化性樹脂組成物。 [2] The rubber particles (B) other than the alicyclic epoxy compound (A) and the polyoxyethylene rubber particles, the white pigment (C), the inorganic filler (D), the stress relieving agent (H), and the molecule An isocyanuric acid derivative (I) having one or more oxirane rings therein, a decane derivative (J) having two or more epoxy groups in the molecule, and an alicyclic polyester resin (K), Further, it contains a curing agent (E), a curing accelerator (F) or a curing catalyst (G), which is a liquid-reflecting curable resin composition at 25 ° C.

[3]如上述[1]或[2]記載之光反射用硬化性樹脂組成物，其於常壓、在25℃測定的黏度為1000000mPa‧s以下(較理想為800000mPa‧s以下)。 [3] The curable resin composition for light reflection according to the above [1] or [2], wherein the viscosity measured at 25 ° C under normal pressure is 1,000,000 mPa ‧ s or less (more preferably 800,000 mPa ‧ s or less).

[4]如上述[1]至[3]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式環氧化合物(A)包含選自(i)具有由構成脂環的鄰接的2個碳原子與氧原子所構成的環氧基(脂環式環氧基)之化合物及(ii)具有直接以單鍵結合於脂環的環氧基的化合物所成群的至少1種。 [4] The curable resin composition for light reflection according to any one of the above [1], wherein the alicyclic epoxy compound (A) is selected from (i) has a contiguous structure constituting an alicyclic ring. At least one of a group of an epoxy group (alicyclic epoxy group) composed of two carbon atoms and an oxygen atom and (ii) a compound having an epoxy group directly bonded to an alicyclic ring by a single bond .

[5]如上述[1]至[4]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式環氧化合物(A)包含具有氧化環己烯基的化合物。 [5] The curable resin composition for light reflection according to any one of the above [1], wherein the alicyclic epoxy compound (A) comprises a compound having cyclohexene oxide.

[6]如上述[1]至[5]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式環氧化合物(A)包含下述式(I)所示的化合物； [式(I)中，X表示單鍵或連結基(具有1個以上原子的2價基)；構成環己烷環(氧化環己烯基)的碳原子的1個以上可 與取代基(較理想為烷基)鍵結]。 [6] The curable resin composition for light reflection according to any one of the above [1], wherein the alicyclic epoxy compound (A) comprises a compound represented by the following formula (I); In the formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms); and one or more of the carbon atoms constituting the cyclohexane ring (cyclohexene oxide) may be substituted with a substituent ( More preferably an alkyl) linkage].

[7]如上述[6]記載之光反射用硬化性樹脂組成物，其中連結基為2價的烴基、碳-碳雙鍵的一部分或全部被環氧基化的伸烯基、羰基、醚鍵、酯鍵、碳酸酯基、醯胺基及該等複數個連結而成的基。 [7] The curable resin composition for light reflection according to the above [6], wherein the linking group is a divalent hydrocarbon group, or a part or all of a carbon-carbon double bond is an epoxy group-extended alkenyl group, a carbonyl group or an ether group. A bond, an ester bond, a carbonate group, a guanamine group, and a plurality of such linked groups.

[8]如上述[6]或[7]記載之光反射用硬化性樹脂組成物，其中上述式(I)所示的脂環式環氧化合物為選自下述式(I-1)至(I-10)所示的化合物、2,2-雙(3,4-環氧基環己烷-1-基)丙烷、1,2-雙(3,4-環氧基環己烷-1-基)乙烷、1,2-環氧基-1,2-雙(3,4-環氧基環己烷-1-基)乙烷及雙(3,4-環氧基環己基甲基)醚所成群的至少1種； [上述式(I-5)、(I-7)中的l、m，分別表示1至30的整數；上述式(I-5)中的R為碳數1至8的伸烷基(較理想為碳數1至3的直鏈或分支鏈狀的伸烷基)；上述式(I-9)、(I-10)中的n1至n6分別表示1至30的整數]。 [8] The curable resin composition for light reflection according to the above [6], wherein the alicyclic epoxy compound represented by the above formula (I) is selected from the following formula (I-1) to a compound represented by (I-10), 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane- 1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane and bis(3,4-epoxycyclohexyl) At least one of a group of methyl ethers; [l, m in the above formulae (I-5) and (I-7) respectively represent an integer of 1 to 30; and R in the above formula (I-5) is an alkylene group having 1 to 8 carbon atoms (more) It is preferably a linear or branched alkyl group having 1 to 3 carbon atoms; n1 to n6 in the above formulae (I-9) and (I-10) each represent an integer of 1 to 30].

[9]如上述[8]記載之光反射用硬化性樹脂組成物，其中脂環式環氧化合物(A)包含下述式(I-1)所示的化合物； [9] The curable resin composition for light reflection according to the above [8], wherein the alicyclic epoxy compound (A) comprises a compound represented by the following formula (I-1);

[10]如上述[1]至[9]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式環氧化合物(A)包含下述式(II)所示的化合物； [式(II)中，R1表示p價的有機基；p表示1至20的整數；q表示1至50的整數；p為2以上的整數的情況，複數的q可為相同，亦可為不同；式(II)之q的和(總和)為3至100的整數；R2表示下述式(IIa)至(IIc)所示的基之任一者；R2的至少一者為式(IIa)所示的基； [10] The curable resin composition for light reflection according to any one of the above [1], wherein the alicyclic epoxy compound (A) comprises a compound represented by the following formula (II); [In the formula (II), R 1 represents a p-valent organic group; p represents an integer of 1 to 20; q represents an integer of 1 to 50; and p is an integer of 2 or more, and the plural q may be the same or may be the same Is different; the sum (sum) of q of the formula (II) is an integer of from 3 to 100; R 2 represents any one of the groups represented by the following formulas (IIa) to (IIc); at least one of R 2 is a group represented by formula (IIa);

-CH=CH2 (IIb) -CH=CH 2 (IIb)

(式(IIc)中，R3表示氫原子、取代或無取代的烷基、取代或無取代的烷基羰基或取代或無取代的芳香基羰基)]。 (In the formula (IIc), R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group)].

[11]如上述[10]記載之光反射用硬化性樹脂組成物，其中對式(II)所示的化合物的R2的全部量(100莫耳%)而言式(IIa)所示的基的比例為40莫耳%以上(較理想為60莫耳%以上，更理想為80莫耳%以上)。 [11] The curable resin composition for light reflection according to the above [10], wherein the total amount (100 mol%) of R 2 of the compound represented by the formula (II) is represented by the formula (IIa). The ratio of the base is 40 mol% or more (more preferably 60 mol% or more, more desirably 80 mol% or more).

[12]如上述[10]或[11]記載之光反射用硬化性樹脂組成物，其中式(II)所示的化合物的換算標準聚苯乙烯的重量平均分子量為300至100000(較理想為1000至10000)。 [12] The curable resin composition for light reflection according to the above [10], wherein the compound represented by the formula (II) has a weight average molecular weight of 300 to 100,000 (preferably 1000 to 10000).

[13]如上述[10]至[12]中任一項記載之光反射用硬化性樹脂組成物，其中式(II)所示的化合物的環氧基的當量(環氧當量)為50至1000(較理想為100至500)。 The hardenable resin composition for light reflection of any one of the above-mentioned [10], wherein the epoxy group equivalent (epoxide equivalent) of the compound of the formula (II) is 50 to 1000 (preferably 100 to 500).

[14]如上述[1]至[13]中任一項記載之光反射用硬化性樹脂組成物，其中至少包含(i)具有脂環式環氧基之化合物。 [14] The curable resin composition for light reflection according to any one of the above [1], wherein at least (i) a compound having an alicyclic epoxy group is contained.

[15]如上述[14]記載之光反射用硬化性樹脂組成物，其中更包含(ii)具有直接以單鍵結合於脂環的環氧基的化合物。 [15] The curable resin composition for light reflection according to the above [14], which further comprises (ii) a compound having an epoxy group directly bonded to the alicyclic ring by a single bond.

[16]如上述[1]、[3]至[15]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式環氧化合物(A)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為1.5至60重量%(較理想為2至50重量%，更理想為5至40重量%)。 [16] The curable resin composition for light reflection according to any one of the above [1], wherein the content (adjusted amount) of the alicyclic epoxy compound (A) is hardened. The resin composition (100% by weight) is from 1.5 to 60% by weight (more desirably from 2 to 50% by weight, more desirably from 5 to 40% by weight).

[17]如上述[1]、[3]至[16]中任一項記載之光反射用硬化性樹脂組成物，其中對包含於硬化性樹脂組成物之具有環氧基的化合物的全部量(100重量%)而言脂環式環氧化合物(A)的比例為50重量%以上(較理想為60重量%以上，更理想為80重量%以上，特別理想為90重量%以上)。 The light-reflecting resin composition for light reflection according to any one of the above-mentioned [1], wherein the total amount of the epoxy group-containing compound contained in the curable resin composition is the same. (100% by weight) The ratio of the alicyclic epoxy compound (A) is 50% by weight or more (more preferably 60% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more).

[18]如上述[2]至[15]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式環氧化合物(A)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.1至60重量%(較理想為0.3至50重量%，更理想為0.5至40重量%)。 [18] The curable resin composition for light reflection according to any one of the above [2], wherein the content (adjusted amount) of the alicyclic epoxy compound (A) is a curable resin composition. (100% by weight) is from 0.1 to 60% by weight (more desirably from 0.3 to 50% by weight, more desirably from 0.5 to 40% by weight).

[19]如上述[2]至[15]、[18]中任一項記載之光反射用硬化性樹脂組成物，其中對包含於硬化性樹脂組成物之具有環氧基的化合物的全部量(100重量%)而言脂環式環氧化合物(A)的比例為1至90重量%(較理想為5至80重量%，更理想為10至70重量%)。 [19] The curable resin composition for light reflection according to any one of the above [1], wherein the total amount of the epoxy group-containing compound contained in the curable resin composition is the same. The ratio of the alicyclic epoxy compound (A) is from 1 to 90% by weight (more desirably from 5 to 80% by weight, more desirably from 10 to 70% by weight) (100% by weight).

[20]如上述[1]至[19]中任一項記載之光反射用硬化性樹脂組成物，其中聚矽氧橡膠粒子以外的橡膠粒子(B)(以下有只稱為「橡膠粒子(B)」的情況)係由具有橡膠彈性的核部分與包覆該核部分的至少1層的殼層所構成的具有多層構造(核殼構造)的橡膠粒子。 [20] The curable resin composition for light reflection according to any one of the above [1], wherein the rubber particles (B) other than the polyoxyxylene rubber particles (hereinafter referred to as "rubber particles" (hereinafter referred to as "rubber particles") In the case of B)", rubber particles having a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and a shell layer covering at least one layer of the core portion.

[21]如上述[1]至[20]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)係由以(甲基)丙烯酸酯為必要單體成分的聚合物所構成的橡膠粒子。 [21] The curable resin composition for light reflection according to any one of the above [1], wherein the rubber particles (B) are a polymer having (meth) acrylate as an essential monomer component. The rubber particles formed.

[22]如上述[1]至[21]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)為表面具有羥基及/或羧基 (羥基及羧基的任一者或兩者)的橡膠粒子。 The hardenable resin composition for light reflection according to any one of the above-mentioned [1], wherein the rubber particles (B) have a hydroxyl group and/or a carboxyl group (a hydroxyl group and a carboxyl group) or Both) rubber particles.

[23]如上述[1]至[22]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)的平均粒徑為10至500nm(較理想為20至400nm)。 [23] The curable resin composition for light reflection according to any one of the above [1], wherein the rubber particles (B) have an average particle diameter of 10 to 500 nm (more preferably 20 to 400 nm).

[24]如上述[1]至[23]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)的最大粒徑為50至1000nm(較理想為100至800nm)。 [24] The curable resin composition for light reflection according to any one of the above [1], wherein the rubber particles (B) have a maximum particle diameter of 50 to 1000 nm (preferably 100 to 800 nm).

[25]如上述[1]至[24]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)的折射率為1.40至1.60(較理想為1.42至1.58)。 [25] The curable resin composition for light reflection according to any one of [1] to [24] wherein the rubber particles (B) have a refractive index of 1.40 to 1.60 (preferably 1.42 to 1.58).

[26]如上述[1]至[25]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)的折射率與包含該橡膠粒子(B)的硬化性樹脂組成物硬化所得之硬化物的折射率的差為±0.03以內。 [26] The curable resin composition for light reflection according to any one of the above [1], wherein the refractive index of the rubber particles (B) and the curable resin composition containing the rubber particles (B) The difference in refractive index of the cured product obtained by hardening is within ±0.03.

[27]如上述[1]、[3]至[17]、[20]至[26]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.05至20重量%(較理想為0.1至15重量%，更理想為0.2至10重量%)。 [27] The curable resin composition for light reflection according to any one of the above [1], wherein the content of the rubber particles (B) is adjusted. The curable resin composition (100% by weight) is 0.05 to 20% by weight (preferably 0.1 to 15% by weight, more desirably 0.2 to 10% by weight).

[28]如上述[2]至[15]、[18]至[26]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.01至20重量%(較理想為0.05至15重量%，更理想為0.1至10重量%)。 [28] The curable resin composition for light reflection according to any one of the above aspects, wherein the content of the rubber particles (B) (adjusted amount) is hardened. The resin composition (100% by weight) is from 0.01 to 20% by weight (more desirably from 0.05 to 15% by weight, more desirably from 0.1 to 10% by weight).

[29]如上述[1]至[28]中任一項記載之光反射用硬化性樹脂組成物，其中橡膠粒子(B)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為0.5至30重量份(較理想為1至20重量份)。 The curable resin composition for light reflection according to any one of the above aspects, wherein the content (mixing amount) of the rubber particles (B) is contained in the curable resin composition. The total amount of the epoxy group-containing compound is from 0.5 to 30 parts by weight (more desirably from 1 to 20 parts by weight) per 100 parts by weight.

[30]如上述[1]至[29]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)為選自氧化鈦、氧化鋯、氧化鋅及硫酸鋇所成群的至少1種。 [30] The curable resin composition for light reflection according to any one of the above [1], wherein the white pigment (C) is selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate. At least one of them.

[31]如上述[1]至[30]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)為氧化鈦。 [31] The curable resin composition for light reflection according to any one of the above [1], wherein the white pigment (C) is titanium oxide.

[32]如上述[1]至[31]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)的中心粒徑為0.1至50μm。 [32] The curable resin composition for light reflection according to any one of the above [1], wherein the white pigment (C) has a central particle diameter of 0.1 to 50 μm.

[33]如上述[31]記載之光反射用硬化性樹脂組成物，其中氧化鈦的中心粒徑為0.1至50μm(較理想為0.1至30μm，更理想為0.1至20μm，特別理想為0.1至10μm，最理想為0.1至5μm)。 [33] The curable resin composition for light reflection according to the above [31], wherein the titanium oxide has a central particle diameter of 0.1 to 50 μm (preferably 0.1 to 30 μm, more desirably 0.1 to 20 μm, particularly preferably 0.1 to 0.1) 10 μm, most preferably 0.1 to 5 μm).

[34]如上述[1]至[33]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.1至50重量%(較理想為1至40重量%，更理想為5至35重量%)。 [34] The curable resin composition for light reflection according to any one of the above [1], wherein the content (mixing amount) of the white pigment (C) and the curable resin composition (100% by weight) It is from 0.1 to 50% by weight (more desirably from 1 to 40% by weight, more desirably from 5 to 35% by weight).

[35]如上述[1]、[3]至[17]、[20]至[27]、[29]至[34]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為3至400重量份(較理想為10至350重量份，更理想為30至300重量份)。 [35] The curable resin composition for light reflection according to any one of the above-mentioned [1], wherein the white pigment The content (the amount of the (C)) is 3 to 400 parts by weight (more preferably 10 to 350 parts by weight, more preferably 100 to 350 parts by weight, based on 100 parts by weight of the total of the epoxy group-containing compound contained in the curable resin composition. Ideally 30 to 300 parts by weight).

[36]如上述[2]至[15]、[18]至[26]、[28]至[34]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為10至600重量份(較理想為30至500重量份，更理想為30至400重量份)。 [36] The curable resin composition for light reflection according to any one of the above [2] to [15], wherein the white pigment (C) The content (the amount of the compound) is 10 to 600 parts by weight (more preferably 30 to 500 parts by weight, more preferably 30 to 30 parts by weight) based on 100 parts by weight of the total amount of the epoxy group-containing compound contained in the curable resin composition. 400 parts by weight).

[37]如上述[31]至[34]中任一項記載之光反射用硬化性樹脂組成物，其中對白色顏料(C)及無機填充劑(D)的總量(100重量%)而言氧化鈦的比例為5至70重量%(較理想為10至60重量%)。 [37] The curable resin composition for light reflection according to any one of the above [31], wherein the total amount (100% by weight) of the white pigment (C) and the inorganic filler (D) is The ratio of titanium oxide is 5 to 70% by weight (more desirably 10 to 60% by weight).

[38]如上述[1]至[37]中任一項記載之光反射用硬化性樹脂組成物，其中無機填充劑(D)為選自氧化矽、氧化鋁、氮化矽、氮化鋁及氮化硼所成群的至少1種。 [38] The curable resin composition for light reflection according to any one of the above [1], wherein the inorganic filler (D) is selected from the group consisting of cerium oxide, aluminum oxide, cerium nitride, and aluminum nitride. And at least one group of boron nitride.

[39]如上述[1]至[38]中任一項記載之光反射用硬化性樹脂組成物，其中無機填充劑(D)為氧化矽(氧化矽填充劑)。 [39] The curable resin composition for light reflection according to any one of the above [1], wherein the inorganic filler (D) is cerium oxide (cerium oxide filler).

[40]如上述[39]記載之光反射用硬化性樹脂組成物，其中氧化矽的中心粒徑為0.1至50μm(較理想為0.1至30μm)。 [40] The curable resin composition for light reflection according to the above [39], wherein the cerium oxide has a central particle diameter of 0.1 to 50 μm (preferably 0.1 to 30 μm).

[41]如上述[1]至[40]中任一項記載之光反射用硬化性樹脂組成物，其中無機填充劑(D)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為10至90重量%(較理想為13至75重量%，更理想為15至70重量%，又更理想為20至70重量%)。 [41] The curable resin composition for light reflection according to any one of the above [1], wherein the content (admixed amount) of the inorganic filler (D) and the curable resin composition (100 weight) %) is from 10 to 90% by weight (more desirably from 13 to 75% by weight, more desirably from 15 to 70% by weight, still more desirably from 20 to 70% by weight).

[42]如上述[1]、[3]至[17]、[20]至[27]、[29]至[35]、 [37]至[41]中任一項記載之光反射用硬化性樹脂組成物，其中無機填充劑(D)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為10至1500重量份(較理想為50至1200重量份，更理想為70至1000重量份)。 [42] The hardening for light reflection according to any one of the above [1], [3] to [17], [20] to [27], [29] to [35], [37] to [41] The resin composition in which the content (adjusted amount) of the inorganic filler (D) is 10 to 1500 parts by weight based on 100 parts by weight of the total amount of the epoxy group-containing compound contained in the curable resin composition (Comparative) It is desirably 50 to 1200 parts by weight, more desirably 70 to 1000 parts by weight).

[43]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]中任一項記載之光反射用硬化性樹脂組成物，其中無機填充劑(D)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為10至1500重量份(較理想為50至1200重量份，更理想為100至1000重量份)。 [43] The curable resin composition for light reflection according to any one of the above [2] to [15], [18] to [26], [28] to [34], [36] to [41] The content (adjusted amount) of the inorganic filler (D) is 10 to 1500 parts by weight (more preferably 50 to 100 parts by weight of the total amount of the epoxy group-containing compound contained in the curable resin composition) 1200 parts by weight, more desirably 100 to 1000 parts by weight).

[44]如上述[1]至[43]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)及無機填充劑(D)的最大粒徑為200μm以下(較理想為185μm以下，更理想為175μm以下，特別理想為150μm以下)。 [44] The light-reflecting resin composition for light reflection according to any one of the above [1], wherein the white pigment (C) and the inorganic filler (D) have a maximum particle diameter of 200 μm or less (preferably). It is 185 μm or less, more preferably 175 μm or less, and particularly preferably 150 μm or less.

[45]如上述[1]至[44]中任一項記載之光反射用硬化性樹脂組成物，其中白色顏料(C)及無機填充劑(D)的最大粒徑為0.01μm以上。 [45] The curable resin composition for light reflection according to any one of the above [1], wherein the white pigment (C) and the inorganic filler (D) have a maximum particle diameter of 0.01 μm or more.

[46]如上述[1]至[45]中任一項記載之光反射用硬化性樹脂組成物，其中硬化劑(E)為酸酐類(酸酐系硬化劑)。 [46] The curable resin composition for light reflection according to any one of [1] to [45] wherein the curing agent (E) is an acid anhydride (an acid anhydride type curing agent).

[47]如上述[1]至[46]中任一項記載之光反射用硬化性樹脂組成物，其中硬化劑(E)係在25℃為液狀的酸酐類(酸酐系硬化劑)。 The curable resin composition for light reflection according to any one of the above aspects, wherein the curing agent (E) is an acid anhydride (an acid anhydride-based curing agent) which is liquid at 25 °C.

[48]如上述[1]至[47]中任一項記載之光反射用硬化性樹脂組成物，其中硬化劑(E)為飽和單環烴二羧酸酐(也包含烷基等的取代基鍵結於環者)。 The hardening resin composition for light reflection of any one of the above-mentioned [1], wherein the hardening agent (E) is a saturated monocyclic hydrocarbon dicarboxylic anhydride (including a substituent such as an alkyl group). The key is in the ring).

[49]如上述[1]至[48]中任一項記載之光反射用硬化性樹脂組成物，其中硬化劑(E)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為1至40重量%(較理想為3至35重量%，更理想為5至30重量%)。 [49] The curable resin composition for light reflection according to any one of the above [1], wherein the content of the curing agent (E) (the amount of the curing agent) and the curable resin composition (100% by weight) In terms of 1 to 40% by weight (more desirably 3 to 35% by weight, more desirably 5 to 30% by weight).

[50]如上述[1]至[49]中任一項記載之光反射用硬化性樹脂組成物，其中硬化劑(E)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為40至200重量份(較理想為50至150重量份)。 [50] The curable resin composition for light reflection according to any one of the above [1] to [49] wherein the content (the amount of the curing agent (E)) is contained in the curable resin composition. The total amount of the epoxy group-containing compound is 40 to 200 parts by weight (more desirably 50 to 150 parts by weight) per 100 parts by weight.

[51]如上述[1]至[50]中任一項記載之光反射用硬化性樹脂組成物，其中硬化促進劑(F)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.0001至5重量%(較理想為0.001至1重量%)。 [51] The curable resin composition for light reflection according to any one of the above [1], wherein the content of the curing accelerator (F) (the amount of the curing) and the curable resin composition (100 weight) %) is 0.0001 to 5% by weight (more desirably 0.001 to 1% by weight).

[52]如上述[1]至[51]中任一項記載之光反射用硬化性樹脂組成物，其中硬化促進劑(F)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為0.05至15重量份(較理想為0.1至12重量份，更理想為0.2至10重量份，特別理想為0.25至8重量份)。 [52] The curable resin composition for light reflection according to any one of the above [1], wherein the content (mixing amount) of the curing accelerator (F) is included in the curable resin composition. The total amount of the epoxy group-containing compound is 0.05 to 15 parts by weight (more desirably 0.1 to 12 parts by weight, more desirably 0.2 to 10 parts by weight, particularly desirably 0.25 to 8 parts by weight) per 100 parts by weight.

[53]如上述[1]至[52]中任一項記載之光反射用硬化性樹脂組成物，其中硬化觸媒(G)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.0001至5重量%(較理想 為0.001至1重量%)。 [53] The curable resin composition for light reflection according to any one of the above [1], wherein a content (adjusted amount) of the curing catalyst (G) and a curable resin composition (100 weight) %) is 0.0001 to 5% by weight (more desirably 0.001 to 1% by weight).

[54]如上述[1]至[53]中任一項記載之光反射用硬化性樹脂組成物，其中硬化觸媒(G)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為0.0001至15重量份(較理想為0.01至12重量份，更理想為0.05至10重量份，特別理想為0.05至8重量份)。 [54] The curable resin composition for light reflection according to any one of the above [1], wherein the content (adjusted amount) of the curing catalyst (G) is contained in the curable resin composition. The total amount of the epoxy group-containing compound is 0.0001 to 15 parts by weight (preferably 0.01 to 12 parts by weight, more desirably 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight) per 100 parts by weight.

[55]如上述[1]至[54]中任一項記載之光反射用硬化性樹脂組成物，其中應力緩和劑(H)為選自聚矽氧橡膠粒子(H1)、聚矽氧油(H2)、液狀橡膠成分(H3)及熱塑性樹脂(H4)所成群的至少1種。 The curable resin composition for light reflection according to any one of the above aspects, wherein the stress relieving agent (H) is selected from the group consisting of polyoxyxene rubber particles (H1) and polyoxygenated oil. (H2), at least one of a group of the liquid rubber component (H3) and the thermoplastic resin (H4).

[56]如上述[1]至[55]中任一項記載之光反射用硬化性樹脂組成物，其中應力緩和劑(H)為選自聚矽氧橡膠粒子(H1)及聚矽氧油(H2)所成群的至少1種。 The curable resin composition for light reflection according to any one of the above aspects, wherein the stress relieving agent (H) is selected from the group consisting of polyoxyethylene rubber particles (H1) and polyoxygenated oil. (H2) At least one of the groups.

[57]如上述[55]或[56]記載之光反射用硬化性樹脂組成物，其中聚矽氧橡膠粒子(H1)為表面具備聚矽氧樹脂的交聯聚二甲基矽氧烷。 [57] The curable resin composition for light reflection according to the above [55], wherein the polyoxyxylene rubber particles (H1) are crosslinked polydimethylsiloxane having a polyoxyxylene resin on its surface.

[58]如上述[55]至[57]中任一項記載之光反射用硬化性樹脂組成物，其中聚矽氧橡膠粒子(H1)的平均粒徑(d50)為0.1至100μm(較理想為0.5至50μm)。 [58] The curable resin composition for light reflection according to any one of the above [5], wherein the polyanthracene rubber particles (H1) have an average particle diameter (d 50 ) of 0.1 to 100 μm (more) Ideally 0.5 to 50 μm).

[59]如上述[55]至[58]中任一項記載之光反射用硬化性樹脂組成物，其中聚矽氧橡膠粒子(H1)的最大粒徑為0.1至250μm(較理想為0.1至150μm)。 [59] The curable resin composition for light reflection according to any one of the above [5], wherein the polyfluorene oxide rubber particles (H1) have a maximum particle diameter of 0.1 to 250 μm (preferably 0.1 to 0.1) 150 μm).

[60]如上述[55]至[59]中任一項記載之光反射用硬化 性樹脂組成物，其中聚矽氧油(H2)為環氧當量3000至15000的具有下述式(1)所示構造的聚伸烷基醚改質聚矽氧化合物(以下有稱為「聚伸烷基醚改質聚矽氧化合物(1)」的情況)； [式中，x為80至140的整數，y為1至5的整數，z為5至20的整數；R9為碳數2或3的伸烷基(較理想為三亞甲基)；A為具有下述式(1a)所示構造的聚伸烷基醚基； (式中，a及b分別獨立為0至40的整數；B為氫原子或甲基(較理想為甲基))]。 [60] The curable resin composition for light reflection according to any one of the above [5], wherein the polyoxyphthalocene oil (H2) has an epoxy equivalent of from 3,000 to 15,000 and has the following formula (1). a polyalkylene ether modified polyxanthene compound of the structure shown (hereinafter referred to as "polyalkylene ether modified polyoxyl compound (1)"); Wherein x is an integer from 80 to 140, y is an integer from 1 to 5, z is an integer from 5 to 20; and R 9 is an alkylene group having 2 or 3 carbon atoms (preferably a trimethylene group); Is a polyalkylene ether group having a structure represented by the following formula (1a); (wherein, a and b are each independently an integer of 0 to 40; and B is a hydrogen atom or a methyl group (preferably a methyl group))].

[61]如上述[60]記載之光反射用硬化性樹脂組成物，其中a及b的合計為1至80的整數。 [61] The curable resin composition for light reflection according to the above [60], wherein a total of a and b is an integer of from 1 to 80.

[62]如上述[60]或[61]記載之光反射用硬化性樹脂組成物，其中聚伸烷基醚改質聚矽氧化合物(1)的環氧當量為4000至15000(較理想為5000至13000)。 [62] The curable resin composition for light reflection according to the above [60] or [61] wherein the polyalkylene ether modified polyoxonium compound (1) has an epoxy equivalent of from 4,000 to 15,000 (more preferably 5000 to 13000).

[63]如上述[1]、[3]至[17]、[20]至[27]、[29]至[35]、[37]至[42]、[44]至[62]中任一項記載之光反射用硬化性樹脂組成物，其中應力緩和劑(H)的含量(調配量)，對脂環式環氧化合物(A)100重量份而言為1至200重量份(較理想為5至150重量份，更理想為8至120重量份)。 [63] As in [1], [3] to [17], [20] to [27], [29] to [35], [37] to [42], [44] to [62] above A calendered resin composition for light reflection, wherein the content (the amount of the stress relieving agent (H)) is from 1 to 200 parts by weight per 100 parts by weight of the alicyclic epoxy compound (A) (Comparative) It is preferably 5 to 150 parts by weight, more preferably 8 to 120 parts by weight.

[64]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]中任一項記載之光反射用硬化性樹脂組成物，其中應力緩和劑(H)的含量(調配量)，對脂環式環氧化合物(A)100重量份而言為1至250重量份(較理想為5至230重量份，更理想為10至200重量份)。 [64] As described in any one of the above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62] The curable resin composition for light reflection, wherein the content (the amount of the stress relieving agent (H)) is from 1 to 250 parts by weight (preferably from 5 to 100 parts by weight of the alicyclic epoxy compound (A). 230 parts by weight, more desirably 10 to 200 parts by weight).

[65]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]中任一項記載之光反射用硬化性樹脂組成物，其中應力緩和劑(H)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為1至200重量份(較理想為5至150重量份，更理想為8至120重量份)。 [65] As in [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] above The curable resin composition for light reflection according to the above, wherein the content (the amount of the stress relieving agent (H)) is 100 parts by weight based on the total amount of the epoxy group-containing compound contained in the curable resin composition. It is 1 to 200 parts by weight (more desirably 5 to 150 parts by weight, more desirably 8 to 120 parts by weight).

[66]如上述[1]至[65]中任一項記載之光反射用硬化性樹脂組成物，其中對硬化性樹脂組成物(100重量%)而言應力緩和劑(H)的含量為相對於硬化性樹脂組成物(100重量%)為0.1至20重量%(較理想為0.3至18重量%，更理想為0.5至15重量%)。 [66] The curable resin composition for light reflection according to any one of the above [1], wherein the content of the stress relieving agent (H) is less than the curable resin composition (100% by weight). It is 0.1 to 20% by weight (more desirably 0.3 to 18% by weight, more desirably 0.5 to 15% by weight) with respect to the curable resin composition (100% by weight).

[67]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[66]中任一項記載之光反射用硬化性樹脂組成物，其中異氰脲酸衍生物(I)分子 內所具有的環氧乙烷環的數目為1至6個(較理想為1至3個)。 [67] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the preceding claims, wherein the number of oxirane rings in the molecule of the isocyanuric acid derivative (I) is from 1 to 6 (more preferably from 1 to 1) 3).

[68]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[67]中任一項記載之光反射用硬化性樹脂組成物，其中異氰脲酸衍生物(I)包含下述式(III)所示的化合物； [式(III)中，R4至R6為相同或不同，表示氫原子或1價有機基；但是，R4至R6的至少一者為含有環氧基的1價有機基]。 [68] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the preceding claims, wherein the isocyanuric acid derivative (I) comprises a compound represented by the following formula (III); [In the formula (III), R 4 to R 6 are the same or different and each represents a hydrogen atom or a monovalent organic group; however, at least one of R 4 to R 6 is a monovalent organic group having an epoxy group].

[69]如上述[68]記載之光反射用硬化性樹脂組成物，其中式(III)中，R4至R6為相同或不同，為下述式(IIIa)所示的基或下述式(IIIb)所示的基，R4至R6的至少一者為式(IIIa)所示的基； [69] The curable resin composition for light reflection according to the above [68], wherein R 4 to R 6 in the formula (III) are the same or different, and are a group represented by the following formula (IIIa) or the following a group represented by the formula (IIIb), at least one of R 4 to R 6 being a group represented by the formula (IIIa);

[上述式(IIIa)及式(IIIb)中的R7及R8，可為相同或不同，表示氫原子或碳數1至8的烷基(較理想為氫原子)]。 [R 7 and R 8 in the above formula (IIIa) and formula (IIIb) may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom)].

[70]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[69]中任一項記載之光反射用硬化性樹脂組成物，其中異氰脲酸衍生物(I)包含選自下述式(III-1)所示的化合物、下述式(III-2)所示的化合物及下述式(III-3)所示的化合物所成群的至少1種； [70] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The hardenable resin composition for light reflection according to any one of the invention, wherein the isocyanuric acid derivative (I) comprises a compound selected from the following formula (III-1), and the following formula (III-2) At least one of the compound shown and the compound represented by the following formula (III-3);

[上述式(III-1)、(III-2)及式(III-3)中的R7及R8，可為相同或不同，表示氫原子或碳數1至8的烷基(較理想為氫原子)]。 [R 7 and R 8 in the above formulas (III-1), (III-2) and (III-3) may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably) Is a hydrogen atom)].

[71]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36] 至[41]、[43]至[62]、[64]至[70]中任一項記載之光反射用硬化性樹脂組成物，其中異氰脲酸衍生物(I)為下述式(III-1) [式(III-1)中，R7及R8，可為相同或不同，表示氫原子或碳數1至8的烷基(較理想為氫原子)]所示的化合物。 [71] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The hardenable resin composition for light reflection according to any one of the above, wherein the isocyanuric acid derivative (I) is the following formula (III-1) [In the formula (III-1), R 7 and R 8 may be the same or different and represent a hydrogen atom or a compound having an alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom).

[72]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[71]中任一項記載之光反射用硬化性樹脂組成物，其中異氰脲酸衍生物(I)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.05至15重量%(較理想為0.1至10重量%，更理想為0.3至5重量%)。 [72] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the content (mixing amount) of the isocyanuric acid derivative (I) is 0.05 to 100% by weight of the curable resin composition (100% by weight) 15% by weight (more desirably 0.1 to 10% by weight, more desirably 0.3 to 5% by weight).

[73]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[72]中任一項記載之光反射用硬化性樹脂組成物，其中異氰脲酸衍生物(I)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為1至60重量份(較理想為1至50重量份，更理想為1至30重量份)。 [73] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the content (mixing amount) of the isocyanuric acid derivative (I) is a compound having an epoxy group contained in the curable resin composition. The total amount is from 1 to 60 parts by weight (more desirably from 1 to 50 parts by weight, more desirably from 1 to 30 parts by weight) per 100 parts by weight.

[74]如上述[2]至[15]、[18]至[26]、[28]至 [34]、[36]至[41]、[43]至[62]、[64]至[73]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)包含選自分子內具有2個以上環氧基的環狀矽氧烷及分子內具有2個以上環氧基的直鏈狀聚矽氧所成群的至少1種。 [74] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the oxoxane derivative (J) comprises a cyclic siloxane having two or more epoxy groups in the molecule and two molecules in the molecule. At least one of the above linear epoxy groups of the epoxy groups is present.

[75]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[74]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)為分子內具有2個以上環氧基的環狀矽氧烷。 [75] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the oxoxane derivative (J) is a cyclic siloxane having two or more epoxy groups in the molecule.

[76]如上述[75]記載之光反射用硬化性樹脂組成物，其中形成矽氧烷環的Si-O單元的數目為2至12(較理想為4至8)。 [76] The curable resin composition for light reflection according to the above [75], wherein the number of Si-O units forming a siloxane chain is 2 to 12 (preferably 4 to 8).

[77]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[76]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)的重量平均分子量為100至3000(較理想為180至2000)。 [77] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The hardenable resin composition for light reflection according to any one of the invention, wherein the siloxane derivative (J) has a weight average molecular weight of from 100 to 3,000 (preferably from 180 to 2,000).

[78]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[77]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)分子內所具有的環氧基的數目為2至4個(2個、3個或4個)。 [78] As described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the number of epoxy groups in the molecule of the siloxane derivative (J) is 2 to 4 (2, 3 or 4) ).

[79]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[78]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)的環氧當量為180至2000(較理想為180至1500，更理想為180至1000)。 [79] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the siloxane derivative (J) has an epoxy equivalent of from 180 to 2,000 (more preferably from 180 to 1,500, more preferably from 180 to 1,000).

[80]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36] 至[41]、[43]至[62]、[64]至[79]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)所具有的環氧基為構成脂環的鄰接的2個碳原子與氧原子所構成的環氧基(脂環式環氧基)(較理想為氧化環己烯基)。 [80] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the epoxy group of the siloxane derivative (J) is a ring composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. Oxy (alicyclic epoxy) (preferably cyclohexene oxide).

[81]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[80]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)包含下述式(IV)所示的矽氧烷化合物； [式(IV)中，Ra為相同或不同，表示含有環氧基的基或烷基(較理想為碳數1至10的直鏈或分支鏈狀的烷基)；但是式(IV)之Ra的至少2個(較理想為2至4個)為含有環氧基的基；n表示2至12(較理想為4至8，更理想為4或5)的整數]。 [81] As described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the oxoxane derivative (J) comprises a oxoxane compound represented by the following formula (IV); [In the formula (IV), R a is the same or different and represents an epoxy group-containing group or an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms); but the formula (IV) At least 2 (preferably 2 to 4) of R a are an epoxy group-containing group; n represents an integer of 2 to 12 (more preferably 4 to 8, more preferably 4 or 5).

[82]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[81]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)包含選自下述式所示的分子內具有2個以上環氧基的環狀矽氧烷所成群的至少1種。 [82] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the oxoxane derivative (J) comprises a cyclic oxirane having two or more epoxy groups selected from the group consisting of the following formulas. At least one of the groups.

[83]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[82]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)的含量(調配量)，對硬化性樹脂組成物(100重量%)而言為0.1至30重量%(較理想為0.5至20重量%，更理想為1.0至10重量%)。 [83] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the content (adjusted amount) of the siloxane derivative (J) is 0.1 to 30 for the curable resin composition (100% by weight) % by weight (preferably 0.5 to 20% by weight, more desirably 1.0 to 10% by weight).

[84]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[83]中任一項記載之光反射用硬化性樹脂組成物，其中矽氧烷衍生物(J)的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為5至99重量份(較理想為10至95重 量份，更理想為20至80重量份)。 [84] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ 83. The curable resin composition for light reflection according to any one of the invention, wherein the content (adjusted amount) of the siloxane derivative (J) is the total of the epoxy group-containing compound contained in the curable resin composition. The amount is 5 to 99 parts by weight (more desirably 10 to 95 parts by weight, more desirably 20 to 80 parts by weight) in terms of 100 parts by weight.

[85]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[84]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式聚酯樹脂(K)為主鏈具有脂環的脂環式聚酯樹脂。 [85] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ 84. The curable resin composition for light reflection according to any one of the invention, wherein the alicyclic polyester resin (K) is an alicyclic polyester resin having an alicyclic ring as a main chain.

[86]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[85]中任一項記載之光反射用硬化性樹脂組成物，其中對構成脂環式聚酯樹脂(K)的全部單體單元(全部單體成分)(100莫耳%)而言具有脂環的單體單元的比例為10莫耳%以上(例如10至80莫耳%)(較理想為25至70莫耳%，更理想為40至60莫耳%)。 [86] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ 85. The curable resin composition for light reflection according to any one of the invention, wherein the monomer unit (all monomer components) (100 mol%) constituting the alicyclic polyester resin (K) has a fat The proportion of the monomer units of the ring is 10 mol% or more (for example, 10 to 80 mol%) (more desirably 25 to 70 mol%, more desirably 40 to 60 mol%).

[87]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[86]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式聚酯樹脂(K)係包含選自下述式(2)至(4)所示的構成單元所成群的至少一種的脂環式聚酯樹脂； (式中，R10表示直鏈、分支鏈或環狀的碳數2至15的伸烷基；R11至R14分別獨立表示氫原子或直鏈狀或分支鏈狀的碳數1至4的烷基，選自R11至R14中的2個亦可鍵結形 成環) [87] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the preceding claims, wherein the alicyclic polyester resin (K) comprises a group of constituent units selected from the following formulas (2) to (4); At least one alicyclic polyester resin; (wherein R 10 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; and R 11 to R 14 each independently represent a hydrogen atom or a linear or branched carbon number of 1 to 4; The alkyl group selected from two of R 11 to R 14 may also be bonded to form a ring)

(式中，R10表示直鏈、分支鏈或環狀的碳數2至15的伸烷基；R11至R14分別獨立表示氫原子或直鏈狀或分支鏈狀的碳數1至4的烷基，選自R11至R14中的2個亦可鍵結形成環) (wherein R 10 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; and R 11 to R 14 each independently represent a hydrogen atom or a linear or branched carbon number of 1 to 4; The alkyl group selected from two of R 11 to R 14 may also be bonded to form a ring)

(式中，R10表示直鏈、分支鏈或環狀的碳數2至15的伸烷基；R11至R14分別獨立表示氫原子或直鏈狀或分支鏈狀的碳數1至4的烷基，選自R11至R14中的2個亦可鍵結形成環)。 (wherein R 10 represents a linear, branched or cyclic alkyl group having 2 to 15 carbon atoms; and R 11 to R 14 each independently represent a hydrogen atom or a linear or branched carbon number of 1 to 4; The alkyl group selected from two of R 11 to R 14 may also be bonded to form a ring).

[88]如上述[87]記載之光反射用硬化性樹脂組成物，其中脂環式聚酯樹脂(K)係包含下述式(5)所示的構成單元的脂環式聚酯樹脂。 [88] The condensed polyester resin (K) according to the above [87], wherein the alicyclic polyester resin (K) is an alicyclic polyester resin comprising a constituent unit represented by the following formula (5).

[89]如上述[87]或[88]記載之光反射用硬化性樹脂組成物，其中脂環式聚酯樹脂(K)係包含下述式(6)所示的構成單元的脂環式聚酯樹脂。 [89] The condensed polyester resin (K) according to the above [8] or [88], wherein the alicyclic polyester resin (K) is an alicyclic ring comprising a structural unit represented by the following formula (6) polyester resin.

[90]如上述[87]至[89]中任一項記載之光反射用硬化性樹脂組成物，其中上述式(2)至(4)所示的構成單元的含量的合計量(合計含量；構成該構成單元的全部單體單元)，對脂環式聚酯樹脂(K)的全部構成單元(100莫耳%；構成脂環式聚酯樹脂(K)的全部單體單元)而言為20莫耳%以上(例如20至100莫耳%)(較理想為50至100莫耳%，更理想為80至100莫耳%)。 [90] The curable resin composition for light reflection according to any one of the above [8] to [89], wherein the content of the constituent units represented by the above formulas (2) to (4) is a total amount (total content) The entire monomer unit constituting the constituent unit), for all the constituent units of the alicyclic polyester resin (K) (100 mol%; all the monomer units constituting the alicyclic polyester resin (K)) It is 20 mol% or more (for example, 20 to 100 mol%) (more desirably 50 to 100 mol%, more desirably 80 to 100 mol%).

[91]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[90]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式聚酯樹脂(K)的數量平均分子量為300至100000(較理想為300至30000)。 [91] As above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ 90. The curable resin composition for light reflection according to any one of the invention, wherein the alicyclic polyester resin (K) has a number average molecular weight of from 300 to 100,000 (more preferably from 300 to 30,000).

[92]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36] 至[41]、[43]至[62]、[64]至[91]中任一項記載之光反射用硬化性樹脂組成物，其中於硬化劑(E)為必要成分的情況，脂環式聚酯樹脂(K)的調配量(含量)，對脂環式聚酯樹脂(K)與硬化劑(E)的合計量(100重量%)而言為1至60重量%(較理想為5至30重量%)。 [92] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the above, wherein the curing agent (E) is an essential component, and the amount (content) of the alicyclic polyester resin (K) is alicyclic. The total amount (100% by weight) of the polyester resin (K) and the hardener (E) is from 1 to 60% by weight (more desirably from 5 to 30% by weight).

[93]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[91]中任一項記載之光反射用硬化性樹脂組成物，其中於硬化觸媒(G)為必要成分的情況，脂環式聚酯樹脂(K)的調配量(含量)，對脂環式聚酯樹脂(K)與硬化觸媒(G)的合計量(100重量%)而言為50至99重量%(較理想為65至99重量%)。 [93] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the above, wherein the curing agent (G) is an essential component, and the amount (content) of the alicyclic polyester resin (K) is adjusted to an alicyclic ring. The total amount (100% by weight) of the polyester resin (K) and the hardening catalyst (G) is from 50 to 99% by weight (more desirably from 65 to 99% by weight).

[94]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[93]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式聚酯樹脂(K)的調配量(含量)，對硬化性樹脂組成物(100重量%)而言為0.1至20重量%(較理想為0.3至10重量%)。 [94] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the amount (content) of the alicyclic polyester resin (K) is 0.1 to 100% by weight of the curable resin composition (100% by weight) 20% by weight (more desirably 0.3 to 10% by weight).

[95]如上述[2]至[15]、[18]至[26]、[28]至[34]、[36]至[41]、[43]至[62]、[64]至[94]中任一項記載之光反射用硬化性樹脂組成物，其中脂環式聚酯樹脂(K)的調配量(含量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為1至60重量份(較理想為5至30重量份)。 [95] as described above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [ The curable resin composition for light reflection according to any one of the invention, wherein the compounding amount (content) of the alicyclic polyester resin (K) is a compound having an epoxy group contained in the curable resin composition. The total amount is from 1 to 60 parts by weight (more desirably from 5 to 30 parts by weight) in terms of 100 parts by weight.

[96]如上述[1]至[95]中任一項記載之光反射用硬化性樹脂組成物，其中更包含離型劑。 [96] The curable resin composition for light reflection according to any one of the above [1] to [95], further comprising a release agent.

[97]如上述[96]記載之光反射用硬化性樹脂組成物，其中離型劑的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為1至12重量份(較理想為2至10重量份)。 [97] The curable resin composition for light reflection according to the above [96], wherein the content (the amount of the release agent) of the release agent is 100% by weight of the total amount of the epoxy group-containing compound contained in the curable resin composition. It is 1 to 12 parts by weight (more desirably 2 to 10 parts by weight).

[98]如上述[1]至[95]中任一項記載之光反射用硬化性樹脂組成物，其中更包含抗氧化劑。 [98] The curable resin composition for light reflection according to any one of the above [1] to [95], further comprising an antioxidant.

[99]如上述[98]記載之光反射用硬化性樹脂組成物，其中抗氧化劑的含量(調配量)，對包含於硬化性樹脂組成物的具有環氧基的化合物的全部量100重量份而言為0.1至5重量份(較理想為0.5至3重量份)。 [99] The curable resin composition for light reflection according to the above [98], wherein the content (the amount of the antioxidant) is 100 parts by weight based on the total amount of the epoxy group-containing compound contained in the curable resin composition. It is 0.1 to 5 parts by weight (preferably 0.5 to 3 parts by weight).

[100]如上述[1]至[99]中任一項記載之光反射用硬化性樹脂組成物，其中係轉移成形用或壓縮成型用硬化性樹脂組成物(較理想為壓縮成型用硬化性樹脂組成物)。 The curable resin composition for light reflection according to any one of the above aspects, wherein the curable resin composition for transfer molding or compression molding is preferably a curable resin for compression molding. Resin composition).

[101]如上述[1]至[100]中任一項記載之光反射用硬化性樹脂組成物，其中係反射器形成用硬化性樹脂組成物。 The curable resin composition for light reflection according to any one of the above aspects, wherein the curable resin composition for forming a reflector is a composition.

[102]如上述[1]至[101]中任一項記載之光反射用硬化性樹脂組成物的硬化物。 [102] The cured product of the curable resin composition for light reflection according to any one of the above [1] to [101].

[103]如上述[102]記載之硬化物，其中波長450nm的光的反射率(初期反射率)為93%以上(較理想為94%以上，更理想為95%以上)。 [103] The cured product according to the above [102], wherein the reflectance (initial reflectance) of light having a wavelength of 450 nm is 93% or more (more preferably 94% or more, more preferably 95% or more).

[104]如上述[102]或[103]記載之硬化物，其中在120℃加熱250小時後的波長450nm的光的反射率對初期反射率的保持率為80%以上(較理想為85%以上，更理想為 90%以上)。 [104] The cured product according to the above [102] or [103], wherein a reflectance of light having a wavelength of 450 nm after heating at 120 ° C for 250 hours has an initial reflectance retention ratio of 80% or more (more preferably 85%) More preferably, it is 90% or more).

[105]如上述[102]至[104]中任一項記載之硬化物，其中照射強度10mW/cm2的紫外線250小時後的波長450nm的光的反射率對初期反射率的保持率為80%以上(較理想為85%以上，更理想為90%以上)。 [105] The cured product according to any one of [102] to [104], wherein a reflectance of light having a wavelength of 450 nm after ultraviolet light having an irradiation intensity of 10 mW/cm 2 for 250 hours is maintained at an initial reflectance of 80. More than % (more preferably 85% or more, more preferably 90% or more).

[106]如上述[102]至[105]中任一項記載之硬化物，其中在11重量%的氫氧化鉀水溶液70℃、60分鐘處理後的重量減少率為1%以下(較理想為0.8%以下，更理想為0.5%以下)。 [106] The cured product according to any one of the above [10] to [105] wherein the weight reduction rate after treatment with a 11% by weight aqueous potassium hydroxide solution at 70 ° C for 60 minutes is 1% or less (preferably 0.8% or less, more preferably 0.5% or less).

[107]特徵為至少具備光半導體元件及由上述[101]記載的光反射用硬化性樹脂組成物的硬化物所構成的反射器的光半導體裝置。 [107] An optical semiconductor device comprising a reflector comprising at least an optical semiconductor element and a cured product of the curable resin composition for light reflection according to the above [101].

[產業上的利用可能性] [Industry use possibility]

本發明的硬化性樹脂組成物，特別是可以較理想使用作為光半導體裝置之光半導體元件的基板(光半導體元件安裝用基板)所具有的反射器(光反射構件)的用途所使用的成型材料(光反射用硬化性樹脂組成物)。 The curable resin composition of the present invention is particularly preferably a molding material used for the use of a reflector (light reflecting member) of a substrate (an optical semiconductor element mounting substrate) which is an optical semiconductor device of an optical semiconductor device. (curable resin composition for light reflection).

Claims (15)

一種光反射用硬化性樹脂組成物，其特徵為：含有脂環式環氧化合物(A)、聚矽氧橡膠粒子以外的橡膠粒子(B)、白色顏料(C)、無機填充劑(D)及應力緩和劑(H)，又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)，在25℃為液狀。  A curable resin composition for light reflection, comprising: an alicyclic epoxy compound (A), rubber particles (B) other than polyoxyethylene rubber particles, a white pigment (C), and an inorganic filler (D) And the stress relieving agent (H) further contains a hardener (E), a hardening accelerator (F) or a hardening catalyst (G), and is liquid at 25 ° C.   一種光反射用硬化性樹脂組成物，其特徵為：含有脂環式環氧化合物(A)、聚矽氧橡膠粒子以外的橡膠粒子(B)、白色顏料(C)、無機填充劑(D)、應力緩和劑(H)、分子內具有1個以上環氧乙烷環的異氰脲酸衍生物(I)、分子內具有2個以上環氧基的矽氧烷衍生物(J)及脂環式聚酯樹脂(K)，又含有硬化劑(E)及硬化促進劑(F)或硬化觸媒(G)，在25℃為液狀。  A curable resin composition for light reflection, comprising: an alicyclic epoxy compound (A), rubber particles (B) other than polyoxyethylene rubber particles, a white pigment (C), and an inorganic filler (D) , a stress relaxation agent (H), an isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, a decane derivative (J) having a two or more epoxy groups in the molecule, and a fat The cyclic polyester resin (K) further contains a hardener (E), a hardening accelerator (F) or a hardening catalyst (G), and is liquid at 25 ° C.   如申請專利範圍第1項或第2項所述之光反射用硬化性樹脂組成物，其中前述應力緩和劑(H)為選自聚矽氧橡膠粒子(H1)及聚矽氧油(H2)所成群的至少1種。  The curable resin composition for light reflection according to the above aspect, wherein the stress relieving agent (H) is selected from the group consisting of polyoxyethylene rubber particles (H1) and polyoxygenated oil (H2). At least one of the groups.   如申請專利範圍第3項所述之光反射用硬化性樹脂組成物，其中前述聚矽氧橡膠粒子(H1)為表面具備聚矽氧樹脂的經交聯之聚二甲基矽氧烷。  The curable resin composition for light reflection according to claim 3, wherein the polyoxyxylene rubber particles (H1) are crosslinked polydimethyl siloxane having a polyfluorene resin on its surface.   如申請專利範圍第3項或第4項所述之光反射用硬化性樹脂組成物，其中前述聚矽氧油(H2)為環氧當量3000至15000的具有下述式(1)所示構造的聚伸烷基醚改質聚矽氧化合物； 式中，x為80至140的整數，y為1至5的整數，z為5至20的整數；R 9為碳數2或3的伸烷基；A為具有下述式(1a)所示構造的聚伸烷基醚基； 式中，a及b分別獨立地為0至40的整數；B為氫原子或甲基。 The curable resin composition for light reflection according to claim 3, wherein the polyfluorene oxide oil (H2) has an epoxy equivalent of from 3,000 to 15,000 and has a structure represented by the following formula (1). Polyalkylene ether modified polyoxonium compound; Wherein x is an integer of 80 to 140, y is an integer of 1 to 5, z is an integer of 5 to 20; R 9 is an alkylene group having 2 or 3 carbon atoms; and A is a compound of the following formula (1a) a polyalkylene ether group of the structure shown; In the formula, a and b are each independently an integer of 0 to 40; and B is a hydrogen atom or a methyl group. 如申請專利範圍第1項至第5項中任一項所述之光反射用硬化性樹脂組成物，其中前述橡膠粒子(B)係由以(甲基)丙烯酸酯為必要單體成分的聚合物所構成，表面具有羥基及/或羧基，前述橡膠粒子(B)的平均粒徑為10至500nm，最大粒徑為50至1000nm。  The curable resin composition for light reflection according to any one of the first aspect, wherein the rubber particles (B) are polymerized by using (meth) acrylate as an essential monomer component. The composition has a hydroxyl group and/or a carboxyl group on the surface, and the rubber particles (B) have an average particle diameter of 10 to 500 nm and a maximum particle diameter of 50 to 1000 nm.   如申請專利範圍第1項至第6項中任一項所述之光反射用硬化性樹脂組成物，其中前述脂環式環氧化合物(A)為具有氧化環己烯基的化合物。  The curable resin composition for light reflection according to any one of the first to sixth aspect, wherein the alicyclic epoxy compound (A) is a compound having cyclohexene oxide.   如申請專利範圍第1項至第7項中任一項所述之光反射 用硬化性樹脂組成物，其中前述脂環式環氧化合物(A)包含下述式(I-1)所示的化合物 The curable resin composition for light reflection according to any one of the first aspect, wherein the alicyclic epoxy compound (A) comprises the following formula (I-1). Compound 如申請專利範圍第2項至第8項中任一項所述之光反射用硬化性樹脂組成物，其中前述異氰脲酸衍生物(I)為下述式(III-1)所示的化合物 式(III-1)中，R 7及R 8為相同或不同，表示氫原子或碳數1至8的烷基。 The curable resin composition for light reflection according to any one of the invention, wherein the isocyanuric acid derivative (I) is represented by the following formula (III-1). Compound In the formula (III-1), R 7 and R 8 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 如申請專利範圍第2項至第9項中任一項所述之光反射用硬化性樹脂組成物，其中前述脂環式聚酯樹脂(K)為主鏈具有脂環的脂環式聚酯樹脂。  The curable resin composition for light reflection according to any one of claims 2 to 9, wherein the alicyclic polyester resin (K) is an alicyclic polyester having an alicyclic ring as a main chain. Resin.   如申請專利範圍第1項至第10項中任一項所述之光反射用硬化性樹脂組成物，其中前述白色顏料(C)為選自氧化鈦、氧化鋯、氧化鋅及硫酸鋇所成群的至少1種；前述無機填充劑(D)為選自氧化矽、氧化鋁、氮化矽、氮化鋁及氮化硼所成群的至少1種。  The curable resin composition for light reflection according to any one of the preceding claims, wherein the white pigment (C) is selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate. At least one of the group; the inorganic filler (D) is at least one selected from the group consisting of cerium oxide, aluminum oxide, cerium nitride, aluminum nitride, and boron nitride.   如申請專利範圍第1項至第11項中任一項所述之光反 射用硬化性樹脂組成物，其係轉移成型用或壓縮成型用樹脂組成物。  The curable resin composition for light reflection according to any one of the items 1 to 11, which is a resin composition for transfer molding or compression molding.   如申請專利範圍第1項至第12項中任一項所述之光反射用硬化性樹脂組成物，其係反射器形成用樹脂組成物。  The curable resin composition for light reflection according to any one of claims 1 to 12, which is a resin composition for forming a reflector.   一種硬化物，係如申請專利範圍第1項至第13項中任一項所述之光反射用硬化性樹脂組成物的硬化物。  A cured product of the curable resin composition for light reflection according to any one of the items 1 to 13 of the invention.   一種光半導體裝置，其特徵為至少具備光半導體元件及由如申請專利範圍第14項所述之光反射用硬化性樹脂組成物的硬化物所構成的反射器。  An optical semiconductor device comprising at least an optical semiconductor element and a reflector comprising a cured product of a curable resin composition for light reflection according to claim 14.  
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