TWI632180B - Composition for reflective material and optical semiconductor light-emitting device using the same - Google Patents

Composition for reflective material and optical semiconductor light-emitting device using the same Download PDF

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TWI632180B
TWI632180B TW102140827A TW102140827A TWI632180B TW I632180 B TWI632180 B TW I632180B TW 102140827 A TW102140827 A TW 102140827A TW 102140827 A TW102140827 A TW 102140827A TW I632180 B TWI632180 B TW I632180B
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meth
acrylate
mass
composition
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TW201431920A (en
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岩崎猛
森晴彥
小川大地
小幡寬
村上友良
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日商出光興產股份有限公司
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0058—Processes relating to semiconductor body packages relating to optical field-shaping elements

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本發明係關於一種組成物，其係含有(A)：氧化鋅、(B)：球狀二氧化矽、及(C)：黏度為1~1,000mPa．s之鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物。 The present invention relates to a composition comprising (A): zinc oxide, (B): spherical cerium oxide, and (C): viscosity of 1 to 1,000 mPa. The s bond has an adamantyl group or a substituted adamantyl (meth) acrylate compound.

Description

反射材料用組成物及使用此組成物之光半導體發光裝置 Composition for reflective material and optical semiconductor light-emitting device using the same

本發明係關於可較好地使用作為光半導體用反射材料的原料之組成物及其硬化物，以及使用該等之光半導體發光裝置。 The present invention relates to a composition which can be preferably used as a raw material for a reflective material for an optical semiconductor, a cured product thereof, and an optical semiconductor light-emitting device using the same.

利用近年已普及之發光二極體(LED)等之光半導體的發光裝置通常係藉由將光半導體(LED)固定於使合成樹脂在導線框架中一體成形成凹形狀而成之成形體的導線框架上，且以環氧樹脂或聚矽氧樹脂等之密封材料予以密封而製造。 A light-emitting device using an optical semiconductor such as a light-emitting diode (LED) which has been widely used in recent years is usually a wire obtained by fixing a photo-semiconductor (LED) to a molded body in which a synthetic resin is integrally formed into a concave shape in a lead frame. The frame is made of a sealing material such as epoxy resin or polyoxymethylene resin.

至於反射材料用之材料，專利文獻1中已揭示將氧化鈦顏料調配於丙烯酸酯樹脂等之熱硬化性樹脂中而成之材料。然而，氧化鈦除了近紫外線區域之光的反射率低以外，由於有光觸媒功能，故長期間暴露於LED等之光半導體時會有使樹脂劣化之可能性。 As a material for a reflective material, Patent Document 1 discloses a material obtained by blending a titanium oxide pigment with a thermosetting resin such as an acrylate resin. However, in addition to the low reflectance of light in the near-ultraviolet region, titanium oxide has a photocatalytic function, so that it may be deteriorated when exposed to an optical semiconductor such as an LED for a long period of time.

且，專利文獻2中揭示有白色顏料係使用氮化硼粒子之反射材料組成物，但由於液體黏度容易上升而損及液體流動性，故會發生導線框架成形體翹曲或未填充 之問題。 Further, Patent Document 2 discloses that a white pigment is a reflective material composition using boron nitride particles. However, since the liquid viscosity is liable to rise and the liquid fluidity is impaired, the lead frame formed body is warped or unfilled. The problem.

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

[專利文獻1]日本特開2006-156704號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-156704

[專利文獻2]日本特開2012-69794號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-69794

本發明之目的係提供一種可提供反射率或耐熱性高之光半導體用的反射材料之材料，且係可減低發光裝置製造時可能發生之導線框架成形體之翹曲或未填充之材料。 SUMMARY OF THE INVENTION An object of the present invention is to provide a material for providing a reflective material for an optical semiconductor having high reflectance or heat resistance, and to reduce warpage or unfilled material of a lead frame formed body which may occur during manufacture of a light-emitting device.

依據本發明，提供以下之組成物等。 According to the present invention, the following composition and the like are provided.

1.一種組成物，其係含有下述(A)、(B)及(C)：(A)：氧化鋅、(B)：球狀二氧化矽、(C)：黏度為1~1,000mPa．s之鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物。 A composition comprising the following (A), (B) and (C): (A): zinc oxide, (B): spherical cerium oxide, (C): viscosity of 1 to 1,000 mPa . The s bond has an adamantyl group or a substituted adamantyl (meth) acrylate compound.

2.如1所記載之組成物，其中相對於(A)、(B)及(C)之合計100質量份，(A)的含量為1~80質量份，(B)的含量為10~90質量份。 2. The composition according to 1, wherein the content of (A) is 1 to 80 parts by mass, and the content of (B) is 10 to 100 parts by mass based on the total of (A), (B) and (C). 90 parts by mass.

3.如1所記載之組成物，其係進一步含有下述(D)、(E)及(F)之中的至少1者，且相對於 (A)、(B)及(C)與(D)、(E)及(F)之合計100質量份，(A)的含量為1~80質量份，(B)的含量為10~90質量份：(D)：(甲基)丙烯酸或具有極性基之單官能(甲基)丙烯酸酯化合物、(E)：(C)及(D)以外之單官能(甲基)丙烯酸酯化合物、(F)：多官能(甲基)丙烯酸酯化合物。 3. The composition according to 1, further comprising at least one of the following (D), (E) and (F), and 100 parts by mass of (A), (B) and (C) and (D), (E) and (F), the content of (A) is 1 to 80 parts by mass, and the content of (B) is 10 to 90 parts. Parts by mass: (D): (meth)acrylic acid or a monofunctional (meth) acrylate compound having a polar group, (E): a monofunctional (meth) acrylate compound other than (C) and (D), (F): a polyfunctional (meth) acrylate compound.

4.如1~3中任一項所記載之組成物，其中前述球狀二氧化矽係經丙烯酸矽烷表面處理。 4. The composition according to any one of 1 to 3, wherein the spherical cerium oxide is surface-treated with decyl acrylate.

5.如1~4中任一項所記載之組成物，其中前述球狀二氧化矽之一次粒子平均粒徑為0.1~100μm。 5. The composition according to any one of 1 to 4, wherein the spherical cerium oxide has a primary particle average particle diameter of 0.1 to 100 μm.

6.一種硬化物，其係使如1~5中任一項所記載之組成物硬化者。 A cured product obtained by curing the composition according to any one of 1 to 5.

7.一種反射材料，其係使用如6所記載之硬化物者。 A reflective material which is a cured product as described in 6.

8.一種光半導體發光裝置，其係含有如7所記載之反射材料者。 An optical semiconductor light-emitting device comprising the reflective material as described in 7.

依據本發明，可提供一種可提供反射率或耐熱性高之光半導體用反射材料之材料，且係可降低發光裝置製造時可能發生之框架成形體之翹曲或未填充之材料。 According to the present invention, it is possible to provide a material which can provide a reflective material for an optical semiconductor having high reflectance or heat resistance, and which can reduce warpage or unfilled material of a frame formed body which may occur during manufacture of a light-emitting device.

10‧‧‧導線框架 10‧‧‧ lead frame

20‧‧‧半導體元件搭載用基板 20‧‧‧Semiconductor component mounting substrate

21‧‧‧反射材料 21‧‧‧Reflective materials

30‧‧‧光半導體裝置 30‧‧‧Optical semiconductor devices

31‧‧‧光半導體元件 31‧‧‧Optical semiconductor components

32‧‧‧金屬線 32‧‧‧Metal wire

33‧‧‧密封樹脂 33‧‧‧ Sealing resin

34‧‧‧螢光體 34‧‧‧Fertior

圖1係顯示本發明之光半導體元件搭載用基板、及光半導體裝置之一實施形態之概略剖面圖，(a)係導線框架之剖面圖，(b)係光半導體元件搭載用基板之剖面圖，(c)係光半導體裝置之剖面圖。 1 is a schematic cross-sectional view showing an embodiment of an optical semiconductor element mounting substrate and an optical semiconductor device according to the present invention, wherein (a) is a cross-sectional view of a lead frame, and (b) is a cross-sectional view of a substrate for mounting an optical semiconductor element. (c) is a cross-sectional view of an optical semiconductor device.

圖2係顯示本發明之光半導體元件搭載用基板、及光半導體裝置之另一實施形態之概略剖面圖，(a)係導線框架之剖面圖，(b)係光半導體元件搭載用基板之剖面圖，(c)係光半導體裝置之剖面圖。 2 is a schematic cross-sectional view showing another embodiment of the optical semiconductor element mounting substrate and the optical semiconductor device of the present invention, wherein (a) is a cross-sectional view of the lead frame, and (b) is a cross section of the optical semiconductor element mounting substrate. Figure (c) is a cross-sectional view of an optical semiconductor device.

〔組成物〕 [composition]

本發明之組成物係含(A)：氧化鋅、(B)：球狀二氧化矽、及(C)：黏度為1~1,000mPa．s之鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物者。 The composition of the present invention comprises (A): zinc oxide, (B): spherical cerium oxide, and (C): viscosity of 1 to 1,000 mPa. The s bond has an adamantyl group or a substituted adamantyl (meth) acrylate compound.

藉由於組成物中含有氧化鋅，可提高使用組成物作為光半導體用之反射材料的原料時之反射率、耐熱性、耐光性。 By containing zinc oxide in the composition, the reflectance, heat resistance, and light resistance when the composition is used as a raw material of a reflective material for an optical semiconductor can be improved.

以往作為白色顏料使用之氧化鈦，除了近紫外線區域之光的反射率低以外，由於有光觸媒功能，故長期間暴露於LED等之光半導體時會有使樹脂劣化之可能性，然而本發明之組成物由於係不含氧化鈦而含氧化鋅者故無此問題。 In the conventional titanium oxide used as a white pigment, the reflectance of light in the near-ultraviolet region is low, and the photocatalytic function is used. Therefore, when exposed to an optical semiconductor such as an LED for a long period of time, the resin may be deteriorated. The composition does not have such a problem since it contains zinc oxide and does not contain titanium oxide.

且，酯鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物之黏度低，藉由與氧化鋅組合使用可保持組成物之流動性，且可提高成形時之填充性。 Further, the (meth) acrylate compound having an adamantyl group or a substituted adamantyl group having a low viscosity can maintain the fluidity of the composition by using it in combination with zinc oxide, and can improve filling during molding. Sex.

氧化鋅之體積平均粒徑並無特別限制，但基於放熱性或耐熱性之觀點，較好為0.1~100μm。更好為0.1~50μm，又更好為1~20μm。體積平均粒徑可以藉雷射光繞射法之粒度分佈測定中之D50求出。 The volume average particle diameter of zinc oxide is not particularly limited, but is preferably from 0.1 to 100 μm from the viewpoint of heat dissipation or heat resistance. More preferably, it is 0.1 to 50 μm, and more preferably 1 to 20 μm. The volume average particle diameter can be determined by D50 in the particle size distribution measurement by the laser light diffraction method.

組成物中之氧化鋅含量，相對於(A)、(B)及(C)之合計100質量份，或存在有後述之任意成分(D)、(E)及(F)時係相對於(A)、(B)及(C)與(D)、(E)及(F)之合計100質量份，較好為1~80質量份，更好為5~75質量份，又更好為10~75質量份。 The content of zinc oxide in the composition is relative to 100 parts by mass of (A), (B), and (C), or when any of the components (D), (E), and (F) described later are present ( 100 parts by mass of A), (B) and (C) and (D), (E) and (F), preferably 1 to 80 parts by mass, more preferably 5 to 75 parts by mass, more preferably 10 to 75 parts by mass.

且，上述組成物中之氧化鋅含量亦可為3~50質量份或5~40質量份。 Further, the zinc oxide content in the above composition may be 3 to 50 parts by mass or 5 to 40 parts by mass.

本發明之組成物進而含有球狀二氧化矽(SiO2)。氧化鋅在液體中容易沉澱使可使用量受限，藉由組合球狀二氧化矽使用，可使組成物中之無機物含量變得更多，可進一步提高材料強度、反射率、耐熱性、耐光性。 The composition of the present invention further contains spherical cerium oxide (SiO 2 ). Zinc oxide is easily precipitated in a liquid to limit the amount of use, and by combining spherical cerium oxide, the inorganic content in the composition can be made more, and the material strength, reflectance, heat resistance, and light resistance can be further improved. Sex.

此外，可保持組成物之流動性，且提高成形時之填充性。 Further, the fluidity of the composition can be maintained, and the filling property at the time of molding can be improved.

球狀二氧化矽之一次粒子平均粒徑利用雷射繞射測定時，為例如0.1~100μm，較好為0.5~70μm，更好 為1~50μm。藉此，可提高球狀二氧化矽之填充性。 When the average particle diameter of the primary particles of the spherical cerium oxide is measured by laser diffraction, it is, for example, 0.1 to 100 μm, preferably 0.5 to 70 μm, more preferably It is 1~50μm. Thereby, the filling property of the spherical cerium oxide can be improved.

球狀二氧化矽較好經丙烯酸矽烷表面處理。藉由使球狀二氧化矽之表面羥基與丙烯酸矽烷反應進行有機修飾，可提高球狀二氧化矽之潤濕性，而可提高球狀二氧化矽對組成物之有機成分(化合物(C)及任意成分(D)、(E)及(F))中之分散性，且可提高硬化物強度。 The spherical cerium oxide is preferably surface treated with decyl acrylate. By organically modifying the surface hydroxyl group of the spherical cerium oxide with decyl acrylate, the wettability of the spherical cerium oxide can be improved, and the organic component of the spherical cerium oxide composition can be improved (compound (C) And the dispersibility in any of the components (D), (E) and (F)), and the strength of the cured product can be improved.

組成物中之球狀二氧化矽含量，相對於(A)、(B)及(C)之合計100質量份，或存在有後述之任意成分(D)、(E)及(F)時，係相對於(A)、(B)及(C)與(D)、(E)及(F)之合計100質量份，為例如10~90質量份，較好為20~85質量份，更好為30~80質量份。組成物中之球狀二氧化矽含量相對於上述合計質量份未達10質量份時，無法確保材料強度，多於90質量份時會損及流動性。 When the content of the spherical cerium oxide in the composition is 100 parts by mass based on the total of (A), (B) and (C), or when any of the components (D), (E) and (F) described later are present, It is, for example, 10 to 90 parts by mass, preferably 20 to 85 parts by mass, based on 100 parts by mass of the total of (A), (B) and (C) and (D), (E) and (F), more preferably Good for 30 to 80 parts by mass. When the content of the spherical cerium oxide in the composition is less than 10 parts by mass based on the total mass portion, the material strength cannot be ensured, and when it is more than 90 parts by mass, the fluidity is impaired.

且，上述組成物中之球狀二氧化矽含量亦可為40~88質量份或50~86質量份。 Further, the spherical cerium oxide content in the above composition may be 40 to 88 parts by mass or 50 to 86 parts by mass.

本發明之組成物進一步含有黏度為1~1,000mPa．s之鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物(以下亦稱為「化合物(C)」)。 The composition of the present invention further contains a viscosity of 1 to 1,000 mPa. The s bond is an adamantyl group or a substituted adamantyl (meth) acrylate compound (hereinafter also referred to as "compound (C)").

化合物(C)由於可獲得玻璃轉移點高之聚合物，故藉由含於組成物中，在使用組成物作為光半導體用之反射材料的原料時，可提高耐熱性、耐光性。 Since the compound (C) can obtain a polymer having a high glass transition point, when it is contained in a composition, when a composition is used as a raw material of a reflective material for an optical semiconductor, heat resistance and light resistance can be improved.

所謂經取代之金剛烷基係指以羥基等取代基取代金剛烷基中所含之氫原子者。列舉為例如1-羥基金剛烷基、2-羥基金剛烷基、1-甲基金剛烷基、2-甲基金剛烷基、聯金剛烷基、二甲基金剛烷基等。 The substituted adamantyl group means a group in which a hydrogen atom contained in an adamantyl group is substituted with a substituent such as a hydroxyl group. For example, it is 1-hydroxyadamantyl, 2-hydroxyadamantyl, 1-methyladamantyl, 2-methyladamantyl, diadamantyl, dimethyladamantyl and the like.

金剛烷基或經取代之金剛烷基較好為金剛烷基，更好為1-金剛烷基。 The adamantyl group or the substituted adamantyl group is preferably an adamantyl group, more preferably a 1-adamantyl group.

化合物(C)具體列舉為丙烯酸1-金剛烷酯、丙烯酸2-金剛烷酯、丙烯酸2-甲基-2-金剛烷酯、丙烯酸2-乙基-2-金剛烷酯、丙烯酸3-羥基-1-金剛烷酯、甲基丙烯酸1-金剛烷酯、甲基丙烯酸2-金剛烷酯、甲基丙烯酸2-甲基-2-金剛烷酯、甲基丙烯酸2-乙基-2-金剛烷酯、甲基丙烯酸3-羥基-1-金剛烷酯等，較好為甲基丙烯酸金剛烷酯，更好為甲基丙烯酸1-金剛烷酯。酯鍵結有金剛烷基之(甲基)丙烯酸酯化合物可單獨使用一種，亦可組合兩種以上使用。 The compound (C) is specifically exemplified by 1-adamantyl acrylate, 2-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 3-hydroxy-acrylic acid- 1-adamantyl ester, 1-adamantyl methacrylate, 2-adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantane methacrylate The ester, 3-hydroxy-1-adamantyl methacrylate or the like is preferably an adamantyl methacrylate, more preferably 1-adamantyl methacrylate. The (meth) acrylate compound in which the adamantyl group is bonded to the adamantyl group may be used singly or in combination of two or more.

化合物(C)之黏度較好為1~1,000mPa．s，更好為1~500mPa．s，又更好為1~100mPa．s。藉由於組成物中調配上述黏度低之化合物(C)，可提高氧化鋅與球狀二氧化矽之填充性。 The viscosity of the compound (C) is preferably from 1 to 1,000 mPa. s, better 1~500mPa. s, and better is 1~100mPa. s. The filling property of zinc oxide and spherical cerium oxide can be improved by blending the above-mentioned compound (C) having a low viscosity in the composition.

黏度可利用例如流變計或旋轉式黏度計測定。 Viscosity can be measured using, for example, a rheometer or a rotary viscometer.

組成物中之化合物(C)含量相對於(A)、(B)及(C)之合計100質量份為例如1~30質量份，較好為2~20質量份，更好為3~10質量份。 The content of the compound (C) in the composition is, for example, 1 to 30 parts by mass, preferably 2 to 20 parts by mass, more preferably 3 to 10 parts by mass per 100 parts by mass of the parts (A), (B) and (C). Parts by mass.

此外，本發明之組成物亦可含化合物(C)以 外之其他聚合性丙烯酸酯化合物等作為任意成分。 Further, the composition of the present invention may also contain the compound (C). Other polymerizable acrylate compounds and the like are optional components.

作為該等任意成分舉例為例如(甲基)丙烯酸、或具有極性基之單官能(甲基)丙烯酸酯化合物(以下亦稱為「化合物(D)」)；化合物(C)、(D)以外之單官能(甲基)丙烯酸酯化合物(以下亦稱為「化合物(E)」)；多官能(甲基)丙烯酸酯化合物(以下亦稱為「化合物(F)」)等。 Examples of the optional components include, for example, (meth)acrylic acid or a monofunctional (meth)acrylate compound having a polar group (hereinafter also referred to as "compound (D)"); and other than the compounds (C) and (D). A monofunctional (meth) acrylate compound (hereinafter also referred to as "compound (E)"); a polyfunctional (meth) acrylate compound (hereinafter also referred to as "compound (F)").

本發明之組成物中之化合物(C)~(F)之合計含量，以化合物(A)~(F)之合計作為100質量份，較好為1~40質量份，更好為5~30質量份，又更好為10~20質量份。 The total content of the compounds (C) to (F) in the composition of the present invention is 100 parts by mass, preferably 1 to 40 parts by mass, more preferably 5 to 30, based on the total of the compounds (A) to (F). The mass part is preferably 10 to 20 parts by mass.

本發明之組成物中之化合物(C)之含量，以化合物(C)、(D)、(E)及(F)之合計作為100質量%，較好為10~70質量%，更好為15~60質量%，又更好為20~50質量%。 The content of the compound (C) in the composition of the present invention is 100% by mass, preferably 10% to 70% by mass, based on the total of the compounds (C), (D), (E) and (F), more preferably 15 to 60% by mass, and more preferably 20 to 50% by mass.

化合物(D)為(甲基)丙烯酸、或具有極性基之單官能(甲基)丙烯酸酯化合物。並非鍵結有金剛烷基或經取代之金剛烷基者，不與化合物(C)重複。化合物(D)由於具有極性，故藉由於組成物中含有，從而與具有極性之金屬表面等形成氫鍵等而提高密著性，且，藉由存在極性基，而提高潤濕性。又，烷二醇基亦有能參與密著性賦予之情況，但烷二醇(甲基)丙烯酸酯係不包含於化合物(D)者。 The compound (D) is (meth)acrylic acid or a monofunctional (meth) acrylate compound having a polar group. It is not bonded to the adamantyl group or the substituted adamantyl group, and is not repeated with the compound (C). Since the compound (D) has a polarity, it is contained in the composition to form a hydrogen bond with a metal surface having a polarity or the like to improve adhesion, and the presence of a polar group enhances wettability. Further, the alkanediol group may also participate in the adhesion imparting, but the alkanediol (meth)acrylate is not included in the compound (D).

至於具有極性基之(甲基)丙烯酸酯化合物 列舉為例如酯鍵結有包含碳、氫以外之原子的取代基之(甲基)丙烯酸酯化合物，至於取代基可列舉為羥基、環氧基、縮水甘油醚基、四氫糠基、異氰酸酯基、羧基、烷氧基矽烷基、磷酸酯基、內酯基、氧雜環丁烷基、四氫吡喃基、胺基等。 As for a (meth) acrylate compound having a polar group For example, a (meth) acrylate compound having a substituent bonded to an atom other than carbon or hydrogen is exemplified, and examples of the substituent include a hydroxyl group, an epoxy group, a glycidyl ether group, a tetrahydroindenyl group, and an isocyanate group. A carboxyl group, an alkoxyalkyl group, a phosphate group, a lactone group, an oxetanyl group, a tetrahydropyranyl group, an amine group or the like.

具有極性基之(甲基)丙烯酸酯化合物之具體例列舉為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯(例如，商品名：4-HBA，日本化成公司製)、環己烷二甲醇單(甲基)丙烯酸酯(例如，商品名：CHMMA，日本化成公司製)、(甲基)丙烯酸縮水甘油酯、丙烯酸4-羥基丁酯縮水甘油醚(例如，商品名：4-HBAGE，日本化成公司製)、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸2-異氰酸酯基乙酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、2-(甲基)丙烯醯氧基乙基磷酸酯、雙(2-(甲基)丙烯醯氧基乙基)磷酸酯、KAYAMER PM-2、KAYAMER PM-21(商品名，日本化藥公司製)、γ-丁內酯(甲基)丙烯酸酯、(甲基)丙烯酸(3-甲基-3-氧雜環丁酯)、(甲基)丙烯酸(3-乙基-3-氧雜環丁酯)、(甲基)丙烯酸四氫糠酯、(甲基)丙烯 酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯等。 Specific examples of the (meth) acrylate compound having a polar group are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( 4-hydroxybutyl methacrylate (for example, trade name: 4-HBA, manufactured by Nippon Kasei Co., Ltd.), cyclohexanedimethanol mono(meth) acrylate (for example, trade name: CHMMA, manufactured by Nippon Kasei Co., Ltd.) , glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether (for example, trade name: 4-HBAGE, manufactured by Nippon Kasei Co., Ltd.), tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid 2-Iocyanate ethyl ester, 2-(methyl) propylene methoxyethyl succinic acid, 2-(methyl) propylene methoxyethyl hexahydrophthalic acid, 3-(methyl) propylene oxime Propyltrimethoxydecane, 3-(meth)acryloxypropylmethyldimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(A Acryloxypropylmethyldiethoxydecane, 2-(methyl)propenyloxyethyl phosphate, bis(2-(methyl)propenyloxyethyl)phosphate, KAYAMER PM-2, KAYAMER PM-21 Name, manufactured by Nippon Kayaku Co., Ltd.), γ-butyrolactone (meth) acrylate, (meth)acrylic acid (3-methyl-3-oxetanyl), (meth)acrylic acid (3-ethylidene) 3-oxetane), tetrahydrofurfuryl (meth)acrylate, (meth) propylene Dimethylaminoethyl methacrylate, diethylaminoethyl (meth) acrylate, and the like.

本發明中，作為化合物(D)，可單獨使用選自前述(甲基)丙烯酸及前述具有極性基之(甲基)丙烯酸酯化合物中之一種，或亦可組合兩種以上使用。 In the present invention, the compound (D) may be used alone or in combination of two or more kinds selected from the group consisting of the above (meth)acrylic acid and the above-mentioned (meth)acrylate compound having a polar group.

本發明之組成物中之化合物(D)之含量，基於密著性之觀點，以化合物(C)、(D)、(E)及(F)之合計作為100質量%時，較好為1~40質量%，更好為5~35質量%，又更好為10~30質量%。 The content of the compound (D) in the composition of the present invention is preferably 1 in terms of 100% by mass based on the total of the compounds (C), (D), (E) and (F). ~40% by mass, more preferably 5 to 35% by mass, and even more preferably 10 to 30% by mass.

化合物(E)為化合物(C)、(D)以外之單官能(甲基)丙烯酸酯化合物。藉由於本發明之組成物中含有化合物(E)，可調整黏度或硬化物硬度，且，可抑制龜裂發生。 The compound (E) is a monofunctional (meth) acrylate compound other than the compounds (C) and (D). By containing the compound (E) in the composition of the present invention, the viscosity or the hardness of the cured product can be adjusted, and cracking can be suppressed.

化合物(F)係(C)以外之多官能(甲基)丙烯酸酯化合物。基於機械強度或硬化速度之觀點，在不妨礙本發明效果之範圍內亦可於組成物中含有化合物(C)、(D)及(E)以外之多官能(甲基)丙烯酸酯化合物。 The compound (F) is a polyfunctional (meth) acrylate compound other than (C). From the viewpoint of mechanical strength or curing rate, a polyfunctional (meth) acrylate compound other than the compounds (C), (D) and (E) may be contained in the composition insofar as the effects of the present invention are not impaired.

作為化合物(C)、(D)以外之(甲基)丙烯酸酯化合物(化合物(E)、(F))，列舉為例如選自由(甲基)丙烯酸酯改質之聚矽氧油、具有脂肪族烴基之(甲基)丙烯酸酯、數平均分子量400以上之聚烷二醇(甲基)丙烯酸酯、胺基甲酸酯丙烯酸酯、環氧丙烯酸酯及聚酯丙烯酸酯所組成群中之至少一種的(甲基)丙烯酸酯化合物。化合物(E)可選擇使用該等中之單官能(甲 基)丙烯酸酯化合物。又，化合物(F)可選擇使用該等中之多官能(甲基)丙烯酸酯化合物。 Examples of the (meth) acrylate compound (compounds (E) and (F)) other than the compound (C) and (D) are, for example, selected from the group consisting of polyoxyphthalic acid modified by (meth) acrylate and having fat. a hydrocarbon group-based (meth) acrylate, a polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more, a urethane acrylate, an epoxy acrylate, and a polyester acrylate. A (meth) acrylate compound. Compound (E) can be selected to use monofunctional ones (A) Base) acrylate compound. Further, the compound (F) may be selected from the polyfunctional (meth) acrylate compounds in the above.

本發明中使用之(甲基)丙烯酸酯改質之聚矽氧油係末端具有丙烯酸基及/或甲基丙烯酸基，且較好骨架中含二烷基聚矽氧烷之化合物。該(甲基)丙烯酸酯改質之聚矽氧油大多情況係二甲基聚矽氧烷之改質物，但亦可代替甲基藉由苯基或甲基以外之烷基取代之二烷基聚矽氧烷骨架中之烷基之全部或一部份。甲基以外之烷基列舉為乙基、丙基等。該種化合物之市售品可使用一末端反應性聚矽氧油(例如X-22-174DX、X-22-2426、X-22-2475)、兩末端反應性聚矽氧油(例如X-22-164A、X-22-164C、X-22-164E)(以上為信越化學工業公司製，均為商品名)、甲基丙烯酸酯改質之聚矽氧油(例如BY16-152D、BY16-152、BY16-152C)(以上為Toray．Dow Corning公司製，均為商品名)等。 The (meth) acrylate-modified polyoxyxene oil used in the present invention has an acrylic group and/or a methacryl group at the terminal, and preferably a compound containing a dialkyl polysiloxane in the skeleton. The (meth) acrylate-modified polyoxygenated oil is mostly a modified product of dimethyl polyoxyalkylene, but may be substituted for a dialkyl group in which a methyl group is substituted by an alkyl group other than a phenyl group or a methyl group. All or part of the alkyl group in the polyoxyalkylene skeleton. The alkyl group other than the methyl group is exemplified by ethyl, propyl and the like Commercially available products of this type of compound can be used with a one-end reactive polyoxygenated oil (for example, X-22-174DX, X-22-2426, X-22-2475) and a two-terminal reactive polyoxygenated oil (for example, X-). 22-164A, X-22-164C, X-22-164E) (The above are manufactured by Shin-Etsu Chemical Co., Ltd., all of which are trade names), and methacrylate-modified polyoxygenated oils (such as BY16-152D, BY16- 152, BY16-152C) (The above are manufactured by Toray. Dow Corning Co., Ltd., all of which are trade names).

且，作為(甲基)丙烯酸酯改質之聚矽氧油，亦可使用具有丙烯醯氧基烷基末端或甲基丙烯醯氧基烷基末端之聚二烷基矽氧烷。具體列舉為甲基丙烯醯氧基丙基末端聚二甲基矽氧烷、(3-丙烯醯氧基-2-羥基丙基)末端聚二甲基矽氧烷、由丙烯醯氧基末端環氧乙烷二甲基矽氧烷(A嵌段)及環氧乙烷(B嵌段)所成之ABA型三嵌段共聚物、甲基丙烯醯氧基丙基末端分支之聚二甲基矽氧烷等。 Further, as the (meth) acrylate-modified polyoxyxene oil, a polydialkyl decane having an acryloxyalkyl end or a methacryloxyalkyl end may also be used. Specifically exemplified by methacryloxypropyl propyl terminal polydimethyl methoxy oxane, (3-propenyl oxy-2-hydroxypropyl) terminal polydimethyl methoxy olefin, propylene oxy end ring ABA type triblock copolymer composed of oxyethylene dimethyl methoxy oxane (A block) and ethylene oxide (B block), polymethic group of methacryloxypropyl end group Oxane and the like.

本發明中使用之具有脂肪族烴基之(甲基) 丙烯酸酯係對自脂肪族烴化合物去除氫原子之殘基鍵結(甲基)丙烯酸酯基之化合物。 (meth) having an aliphatic hydrocarbon group used in the present invention An acrylate is a compound which removes a (meth) acrylate group of a residue of a hydrogen atom from an aliphatic hydrocarbon compound.

本發明中使用之衍生出具有脂肪族烴基之(甲基)丙烯酸酯之脂肪族烴化合物較好為烷類，基於本發明之硬化物物性之觀點，更好為碳數12以上之烷類。 The aliphatic hydrocarbon compound derived from the (meth) acrylate having an aliphatic hydrocarbon group used in the present invention is preferably an alkane, and more preferably an alkyl group having 12 or more carbon atoms from the viewpoint of the physical properties of the cured product of the present invention.

本發明中使用之具有脂肪族烴基之(甲基)丙烯酸酯中，(甲基)丙烯酸酯基之數並無特別限制，可為1個亦可為複數個。(甲基)丙烯酸酯基之數為1個時，脂肪族烴基較好為烷基，更好為碳數12以上(較好為碳數12~24，更好為碳數12~18)之直鏈烷基。(甲基)丙烯酸酯基之數為2時，脂肪族烴基較好為伸烷基，更好為碳數12以上(較好碳數12~24，更好為碳數12~18)之直鏈伸烷基。 In the (meth) acrylate having an aliphatic hydrocarbon group used in the present invention, the number of the (meth) acrylate groups is not particularly limited, and may be one or plural. When the number of (meth) acrylate groups is one, the aliphatic hydrocarbon group is preferably an alkyl group, more preferably a carbon number of 12 or more (preferably, a carbon number of 12 to 24, more preferably a carbon number of 12 to 18). Linear alkyl. When the number of (meth) acrylate groups is 2, the aliphatic hydrocarbon group is preferably an alkylene group, more preferably a carbon number of 12 or more (preferably having a carbon number of 12 to 24, more preferably a carbon number of 12 to 18). Chain alkyl.

碳數12以上之烷基之具體例列舉為十二烷基(包含月桂基)、十三烷基、十四烷基、十六烷基、十八烷基(包含硬脂基)、二十烷基、三十烷基及四十烷基等。碳數12以上之烷基及伸烷基亦可為源自聚丁二烯或聚異戊二烯等聚合物之氫化物的烷基及伸烷基。碳數12以上之伸烷基之具體例列舉為自上述烷基去除氫原子之2價殘基。 Specific examples of the alkyl group having 12 or more carbon atoms are exemplified by dodecyl group (containing lauryl group), tridecyl group, tetradecyl group, hexadecyl group, octadecyl group (containing stearyl group), and twenty Alkyl, triacontyl and tetradecyl, and the like. The alkyl group and the alkylene group having a carbon number of 12 or more may also be an alkyl group and an alkylene group derived from a hydride of a polymer such as polybutadiene or polyisoprene. Specific examples of the alkylene group having 12 or more carbon atoms are exemplified by the removal of a divalent residue of a hydrogen atom from the above alkyl group.

具有脂肪族烴基之(甲基)丙烯酸酯之具體例列舉為(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸十四烷酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十烷酯、 (甲基)丙烯酸三十烷酯、(甲基)丙烯酸四十烷酯等，或氫化聚丁二烯二(甲基)丙烯酸酯、氫化聚異戊二烯二(甲基)丙烯酸酯等之具有氫化聚丁二烯或氫化聚異戊二烯骨架之丙烯酸或甲基丙烯酸化合物。 Specific examples of the (meth) acrylate having an aliphatic hydrocarbon group are exemplified by lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, and (meth)acrylic acid. Hexadecane ester, stearyl (meth)acrylate, eicosanyl (meth)acrylate, Triacontyl (meth)acrylate, tetradecyl (meth)acrylate, or the like, or hydrogenated polybutadiene di(meth)acrylate, hydrogenated polyisoprene di(meth)acrylate, etc. An acrylic or methacrylic compound having a hydrogenated polybutadiene or hydrogenated polyisoprene backbone.

藉由使用數平均分子量400以上之聚烷二醇(甲基)丙烯酸酯，本發明之組成物可獲得韌性優異之硬化物。本發明中使用之數平均分子量400以上之聚烷二醇(甲基)丙烯酸酯中，(甲基)丙烯酸酯基之數並無特別限制，可為1個亦可為複數個。 By using a polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more, the composition of the present invention can obtain a cured product excellent in toughness. In the polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more used in the present invention, the number of (meth) acrylate groups is not particularly limited, and may be one or plural.

數平均分子量400以上之聚烷二醇(甲基)丙烯酸酯之具體例列舉為聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、乙氧化三羥甲基丙烷三(甲基)丙烯酸酯、乙氧化季戊四醇四(甲基)丙烯酸酯等。該等中，就韌性或密著性之觀點而言，以聚乙二醇二(甲基)丙烯酸酯較佳。 Specific examples of the polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more are exemplified by polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(a). Acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, pentoxide tetraol tetra(meth)acrylate, and the like. Among these, polyethylene glycol di(meth)acrylate is preferable from the viewpoint of toughness or adhesion.

該化合物之數平均分子量，就韌性或密著性之觀點而言，以及就與(C)及(D)成分之相溶性之觀點而言，較好為400~10,000，更好為450~5,000，又更好為500~3,000。 The number average molecular weight of the compound is preferably from 400 to 10,000, more preferably from 450 to 5,000, from the viewpoint of toughness or adhesion, and from the viewpoint of compatibility with the components (C) and (D). And better for 500~3,000.

本發明中可使用之胺基甲酸酯丙烯酸酯、環氧基丙烯酸酯、聚酯丙烯酸酯，就耐光性之觀點而言，較好為不含芳香族基者，該化合物之數平均分子量，就韌性或與(C)及(D)成分之相溶性之觀點而言，較好為100~100,000，更好為500~80,000，又更好為 1,000~50,000。 The urethane acrylate, the epoxy acrylate, and the polyester acrylate which can be used in the present invention are preferably those having no aromatic group, the number average molecular weight of the compound, from the viewpoint of light resistance. From the viewpoint of toughness or compatibility with the components (C) and (D), it is preferably from 100 to 100,000, more preferably from 500 to 80,000, and even more preferably 1,000~50,000.

此外，本發明中可使用之單官能或多官能(甲基)丙烯酸酯化合物(化合物(E)、(F))之具體例列舉為數平均分子量未達400之聚乙二醇二(甲基)丙烯酸酯或聚丙二醇二(甲基)丙烯酸酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異癸酯、己內酯(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、2-乙基己基二甘醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸三氟乙酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙氧化新戊二醇二(甲基)丙烯酸酯、丙氧化新戊二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、乙氧化己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、2-甲基-1,8-辛二醇二(甲基)丙烯酸酯、 丙三醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇丙烯酸加成物、2-羥基-3-丙烯醯氧基丙基(甲基)丙烯酸酯、乙氧化氫化雙酚A二(甲基)丙烯酸酯、丙氧化氫化雙酚A二(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、乙氧化丙三醇(甲基)丙烯酸酯、丙氧化丙三醇(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、乙氧化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧化三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、乙氧化季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、乙氧化異氰尿酸三(甲基)丙烯酸酯、ε-己內酯改質之參(2-丙烯醯氧基乙基)異氰尿酸酯等。 Further, specific examples of the monofunctional or polyfunctional (meth) acrylate compound (compounds (E), (F)) which can be used in the present invention are exemplified as polyethylene glycol di(methyl) having a number average molecular weight of less than 400. Acrylate or polypropylene glycol di(meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, Isoamyl methacrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxy Diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, methoxy polyethylene glycol (A Acrylate, methoxydipropylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, ethylene glycol Di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(methyl) ) C Acid ester, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(methyl) Acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, hexylene oxide di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10- Decanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, Glycerol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, hydroxypivalic acid neopentyl glycol acrylic acid adduct, 2-hydroxy-3-propenyloxypropyl (Meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, hydrogen peroxide hydrogenated bisphenol A di(meth)acrylate, glycerol tri(meth)acrylate, ethoxylated Alcohol (meth) acrylate, propoxylated glycerol (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylation Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentoxide tetraol tetraoxide (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated isocyanuric acid tri(meth) acrylate, ε-caprolactone modified ginseng ( 2-propenyloxyethyl)isocyanurate or the like.

本發明中，化合物(E)可單獨使用上述單官能(甲基)丙烯酸酯化合物中之一種，或可組合兩種以上使用。 In the present invention, the compound (E) may be used singly or in combination of two or more kinds of the above-mentioned monofunctional (meth) acrylate compounds.

本發明之組成物中之化合物(E)之含量，就韌性或密著性之觀點而言，以化合物(C)、(D)、(E)及(F)之合計作為100質量%時，較好為10~80質量%，更好為15~75質量%，又更好為20~70質量%。 When the content of the compound (E) in the composition of the present invention is 100% by mass based on the total of the compounds (C), (D), (E) and (F) from the viewpoint of toughness or adhesion, It is preferably from 10 to 80% by mass, more preferably from 15 to 75% by mass, even more preferably from 20 to 70% by mass.

本發明中，化合物(F)可單獨使用上述多官能(甲基)丙烯酸酯化合物中之一種，或可組合兩種以上使用。 In the present invention, the compound (F) may be used singly or in combination of two or more kinds of the above polyfunctional (meth) acrylate compounds.

本發明之組成物中之化合物(F)之含量，就不妨礙本發明效果之觀點而言，以化合物(C)、(D)、(E)及(F)之合計作為100質量%時，較好為0.1~70質量%，更好為0.5~60質量%，又更好為1~50質量%。 When the content of the compound (F) in the composition of the present invention is 100% by mass based on the total of the compounds (C), (D), (E) and (F), the total amount of the compound (C), (D), (E) and (F) is not impaired. It is preferably from 0.1 to 70% by mass, more preferably from 0.5 to 60% by mass, even more preferably from 1 to 50% by mass.

藉由熱使本發明之組成物聚合可獲得硬化物。為促進聚合反應，組成物中亦可含有聚合起始劑。聚合起始劑並無特別限制，列舉為例如自由基聚合起始劑。 A cured product can be obtained by polymerizing the composition of the present invention by heat. In order to promote the polymerization reaction, the composition may also contain a polymerization initiator. The polymerization initiator is not particularly limited and is exemplified by, for example, a radical polymerization initiator.

自由基聚合起始劑並無特別限制，列舉為例如酮過氧化物類、過氧化氫類、二醯基過氧化物類、二烷基過氧化物類、過氧縮酮類、烷基過酯類(過氧基酯類)、過氧基碳酸酯類等。 The radical polymerization initiator is not particularly limited, and examples thereof include ketone peroxides, hydrogen peroxides, dimercapto peroxides, dialkyl peroxides, peroxyketals, and alkyl groups. Esters (peroxyesters), peroxycarbonates, and the like.

酮過氧化物類之具體例列舉為甲基乙基酮過氧化物、甲基異丁基酮過氧化物、乙醯基丙酮過氧化物、環己酮過氧化物、甲基環己酮過氧化物等。 Specific examples of the ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetyl ketone peroxide, cyclohexanone peroxide, and methyl cyclohexanone. Oxide, etc.

過氧化氫類之具體例列舉為1,1,3,3-四甲基丁基過氧化氫、異丙苯基過氧化氫、第三丁基過氧化氫、對-薄荷烷過氧化氫、二異丙基苯過氧化氫等。 Specific examples of the hydrogen peroxides include 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, t-butyl hydroperoxide, p-menthane hydrogen peroxide, Diisopropylbenzene hydrogen peroxide and the like.

二醯基過氧化物類之具體例列舉為二異丁醯基過氧化物、雙-3,5,5-三甲基己醇過氧化物、二月桂醯基過氧化物、二苯甲醯基過氧化物、間-甲苯基苯甲醯基過氧化物、琥珀酸過氧化物等。 Specific examples of the dimercapto peroxides are diisobutyl hydrazino peroxide, bis-3,5,5-trimethylhexanol peroxide, dilauroyl peroxide, and benzoyl peroxide. Oxide, m-tolyl benzhydryl peroxide, succinic peroxide, and the like.

二烷基過氧化物類之具體例列舉為二-異丙苯基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧基)己烷、1,3-雙(第三丁基過氧基異丙基)己烷、第三丁基異 丙苯基過氧化物、二第三丁基過氧化物、二第三己基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧基)己烯-3等。 Specific examples of the dialkyl peroxides are bis-isopropylphenyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3. - bis(t-butylperoxyisopropyl)hexane, tert-butyl iso Propyl phenyl peroxide, di-tert-butyl peroxide, di-thylhexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3 Wait.

過氧縮酮類之具體例列舉為1,1-二第三己基過氧基-3,3,5-三甲基環己烷、1,1-二第三己基過氧基環己烷、1,1-二第三丁基過氧基-2-甲基環己烷、1,1-二第三丁基過氧基環己烷、2,2-二(第三丁基過氧基)丁烷、4,4-雙(第三丁基過氧基)戊酸丁酯等。 Specific examples of the peroxyketals are 1,1-di-t-hexylperoxy-3,3,5-trimethylcyclohexane and 1,1-di-t-hexylperoxycyclohexane. 1,1-di-t-butylperoxy-2-methylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di(t-butylperoxy Butane, butyl 4,4-bis(t-butylperoxy)pentanoate, and the like.

烷基過酯類(過氧酯類)之具體例列舉為1,1,3,3-四甲基丁基過氧基新癸酸酯、α-異丙苯基過氧基新癸酸酯、第三丁基過氧基新癸酸酯、第三己基過氧基新癸酸酯、第三丁基過氧基新庚酸酯、第三己基過氧基特戊酸酯、第三丁基過氧基特戊酸酯、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯、第三戊基過氧基-2-乙基己酸酯、第三丁基過氧基-2-乙基己酸酯、第三丁基過氧基異丁酸酯、二第三丁基過氧基六氫對苯二甲酸酯、1,1,3,3-四甲基丁基過氧基-3,5,5-三甲基己酸酯、第三戊基過氧基3,5,5-三甲基己酸酯、第三丁基過氧基-3,5,5-三甲基己酸酯、第三丁基過氧基乙酸酯、第三丁基過氧基苯甲酸酯、二丁基過氧基三甲基己二酸酯、2,5-二甲基-2,5-二-2-乙基己醯基過氧基己烷、第三己基過氧基-2-乙基己酸酯、第三己基過氧基異丙基單碳酸酯、第三丁基過氧基月桂酸酯、第三丁基過氧基異丙基單碳酸酯、第三丁基過氧基-2-乙基己基單碳酸酯、2,5-二甲基-2,5-二苯甲醯基過氧基己烷等。 Specific examples of the alkyl peresters (peroxy esters) are 1,1,3,3-tetramethylbutylperoxy neodecanoate and α-cumylperoxy neodecanoate. , t-butylperoxy neodecanoate, third hexylperoxy neodecanoate, tert-butylperoxy neoheptanoate, third hexylperoxy pivalate, third butyl Base peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, third amyl peroxy-2-ethylhexanoate, Tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy isobutyrate, di-t-butylperoxy hexahydroterephthalate, 1,1,3 , 3-tetramethylbutylperoxy-3,5,5-trimethylhexanoate, third amyl peroxy 3,5,5-trimethylhexanoate, tert-butyl Oxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, dibutylperoxytrimethylhexyl Acid ester, 2,5-dimethyl-2,5-di-2-ethylhexylperoxy hexane, third hexylperoxy-2-ethylhexanoate, third hexylperoxy Isopropyl monocarbonate, tert-butylperoxy laurate, tert-butyl Peroxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-dibenzoylperoxy hexane, etc. .

過氧基碳酸酯類之具體例列舉為二正丙基過 氧基二碳酸酯、二異丙基過氧基碳酸酯、二-4-第三丁基環己基過氧基碳酸酯、二-2-乙基己基過氧基碳酸酯、二第二丁基過氧基碳酸酯、二-3-甲氧基丁基過氧基二碳酸酯、二-2-乙基己基過氧基二碳酸酯、二異丙基氧基二碳酸酯、第三戊基過氧基異丙基碳酸酯、第三丁基過氧基異丙基碳酸酯、第三丁基過氧基-2-乙基己基碳酸酯、1,6-雙(第三丁基過氧基羧基氧基)己烷等。 Specific examples of peroxy carbonates are listed as di-n-propyl groups. Oxydicarbonate, diisopropylperoxycarbonate, di-4-t-butylcyclohexylperoxycarbonate, di-2-ethylhexylperoxycarbonate, di-tert-butyl Peroxycarbonate, bis-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, diisopropyloxydicarbonate, third amyl Peroxyisopropyl carbonate, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, 1,6-bis (t-butylperoxy) Carboxyoxy)hexane and the like.

本發明中，上述自由基聚合起始劑可單獨使用或組合兩種以上使用。 In the present invention, the above-mentioned radical polymerization initiators may be used singly or in combination of two or more.

本發明之組成物中之自由基聚合起始劑之含量相對於化合物(C)、(D)、(E)及(F)之合計100質量份，較好為0.01~10質量份，更好為0.1~5質量份。 The content of the radical polymerization initiator in the composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the total of the compounds (C), (D), (E) and (F). It is 0.1 to 5 parts by mass.

本發明之組成物中，在不妨礙本發明效果之範圍內亦可進一步含有抗氧化劑或光安定劑、紫外線吸收劑、可塑劑、無機填充材、著色劑、抗靜電劑、滑劑、脫模劑、難燃劑、調平劑、消泡劑等任意之添加劑。該等添加劑可使用習知者。 The composition of the present invention may further contain an antioxidant or a light stabilizer, an ultraviolet absorber, a plasticizer, an inorganic filler, a colorant, an antistatic agent, a lubricant, and a mold release, without departing from the effects of the present invention. Any additives such as a solvent, a flame retardant, a leveling agent, and an antifoaming agent. These additives can be used by conventional practitioners.

至於抗氧化劑列舉為酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、維生素系抗氧化劑、內酯系抗氧化劑、胺系抗氧化劑等。 The antioxidant is exemplified by a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a vitamin-based antioxidant, a lactone-based antioxidant, and an amine-based antioxidant.

酚系抗氧化劑列舉為肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]甲烷、β-(3,5-二第三丁基-4-羥基苯基)丙酸硬脂酸酯、1,3,5-三甲基-2,4,6-參(3,5-二第三丁基-4-羥基苄基)苯、參(3,5-二第三丁基-4-羥基 苄基)異氰尿酸酯、參[(3,5-二第三丁基-4-羥基苯基)丙醯氧基乙基]異氰尿酸酯、2,6-二第三丁基-4-甲基苯酚、3,9-雙[1,1-二甲基-2-{β-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]-2,4,8,10-四氧雜螺[5,5]十一碳烷、參(2,6-二甲基-3-羥基-4-第三丁基苄基)異氰尿酸酯等，可使用例如Irganox 1010、Irganox 1035、Irganox 1076、Irganox 1098、Irganox 1135、Irganox 1330、Irganox 1425 WL、Irganox 1520 L、Irganox 1726、Irganox 245、Irganox 259、Irganox 3114、Irganox 3125、Irganox 3790、Irganox 5057、Irganox s565(以上為BASF公司製)、Adeka stab AO-20、Adeka stab AO-30、Adeka stab AO-40、Adeka stab AO-50、Adeka stab AO-60、Adeka stab AO-80(以上為ADEKA公司製)、BHT(武田藥品工業公司製)、CYANOX 1790(Cytec公司製)、SUMILIZER GP、SUMILIZER GM、SUMILIZER GS及SUMILIZER GA-80(以上為住友化學公司製)等市售品(均為商品名)。 The phenolic antioxidants are exemplified by hydrazine [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, β-(3,5-di-t-butyl- 4-hydroxyphenyl)propionic acid stearate, 1,3,5-trimethyl-2,4,6-glucosin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, ginseng (3,5-di-t-butyl-4-hydroxyl Benzyl)isocyanurate, ginseng [(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxyethyl]isocyanurate, 2,6-di-t-butyl 4-methylphenol, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxyl} Ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, ginseng (2,6-dimethyl-3-hydroxy-4-tributylbenzyl) For cyanurate or the like, for example, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1425 WL, Irganox 1520 L, Irganox 1726, Irganox 245, Irganox 259, Irganox 3114, Irganox 3125, Irganox 3790, Irganox 5057, Irganox s565 (above made by BASF), Adeka stab AO-20, Adeka stab AO-30, Adeka stab AO-40, Adeka stab AO-50, Adeka stab AO-60, Adeka stab AO- 80 (the above is made by ADEKA), BHT (made by Takeda Pharmaceutical Co., Ltd.), CYANOX 1790 (made by Cytec), SUMILIZER GP, SUMILIZER GM, SUMILIZER GS, and SUMILIZER GA-80 (above, Sumitomo Chemical Co., Ltd.) Products (all product names).

磷系抗氧化劑列舉為參(2,4-二第三丁基苯基)亞磷酸酯、2-[[2,4,8,10-肆(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜磷雜環庚烷-6-基]氧基]-N,N-雙[2-[[2,4,8,10-肆(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜磷雜環庚烷-6-基]氧基]-乙基]乙胺、環狀新戊烷四基雙(2,6-二第三丁基-4-甲基苯基)亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯等，可使用例如IRGAFOS 168、 IRGAFOS 12、IRGAFOS 38(以上為BASF公司製)、Adeka stab 329K、Adeka stab PEP-36、Adeka stab PEP-8、Adeka stab HP-10、Adeka stab 2112、Adeka stab 260、Adeka stab 522A(以上為ADEKA公司製)、Sandstab P-EPQ(Clariant公司製)、Weston 618、Weston 619G、Weston 624(以上為GE公司製)等市售品(均為商品名)。 Phosphorus antioxidants are listed as ginseng (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-fluorene (1,1-dimethylethyl) diphenyl. And [d,f][1,3,2]dioxaphosphol-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-肆( 1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphospholane-6-yl]oxy]-ethyl]ethylamine, cyclic Neopentane tetrakis(2,6-di-t-butyl-4-methylphenyl)phosphite, distearyl pentaerythritol diphosphite, etc., for example, IRGAFOS 168, IRGAFOS 12, IRGAFOS 38 (above made by BASF), Adeka stab 329K, Adeka stab PEP-36, Adeka stab PEP-8, Adeka stab HP-10, Adeka stab 2112, Adeka stab 260, Adeka stab 522A (above ADEKA) Commercial products (all manufactured by the company), Sandstab P-EPQ (made by Clariant), Weston 618, Weston 619G, Weston 624 (made by GE Corporation) (all are trade names).

硫系抗氧化劑列舉為二月桂基硫代二丙酸酯、二硬脂基硫代二丙酸酯、二肉荳蔻基硫代二丙酸酯、月桂基硬脂基硫代二丙酸酯、季戊四醇肆(3-十二烷基硫代丙酸酯)、季戊四醇肆(3-月桂基硫代丙酸酯)等，可使用例如Adeka stab AO-412S、Adeka stab AO-23、Adeka stab AO-503A(以上為ADEKA公司製)、DSTP[YOSITOMI]、DLTP[YOSITOMI]、DLTOIB、DMTP[YOSITOMI](以上為API Co.Ltd.公司製)、Seenox 412S(SHIPRO化成公司製)、Cyanox 1212(Cyanamide公司製)；SUMILIZER TP-D、SUMILIZER TPS、SUMILIZER TPM、SUMILIZER TPL-R(住友化學公司製)等市售品(均為商品名)。 The sulfur-based antioxidants are exemplified by dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, Pentaerythritol lanthanum (3-dodecyl thiopropionate), pentaerythritol lanthanum (3-lauryl thiopropionate), and the like, for example, Adeka stab AO-412S, Adeka stab AO-23, Adeka stab AO- can be used. 503A (above, ADEKA), DSTP [YOSITOMI], DLTP [YOSITOMI], DLTOIB, DMTP [YOSITOMI] (above, API Co. Ltd.), Seenox 412S (SHIPRO Chemical Co., Ltd.), Cyanox 1212 (Cyanamide) Company-made); commercially available products (all trade names) such as SUMILIZER TP-D, SUMILIZER TPS, SUMILIZER TPM, and SUMILIZER TPL-R (manufactured by Sumitomo Chemical Co., Ltd.).

維生素系抗氧化劑列舉為生育酚、2,5,7,8-四甲基-2-(4’,8’,12’-三甲基十三烷基)香豆素-6-醇等，可使用例如IRGANOX E201(BASF公司製)等市售品。內酯系抗氧化劑可使用日本特開平7-233160號公報、日本特開平7-247278號公報所記載者。且，亦可使用HP-136 (商品名，BASF公司製，化合物名：5,7-二第三丁基-3-(3,4-二甲基苯基)-3H-苯并呋喃-2-酮)等。 The vitamin antioxidants are listed as tocopherol, 2,5,7,8-tetramethyl-2-(4',8',12'-trimethyltridecyl)coumarin-6-ol, etc. Commercial products such as IRGANOX E201 (manufactured by BASF Corporation) can be used. For the lactone-based antioxidant, those described in JP-A-H07-233160 and JP-A-H07-247278 can be used. Also, you can use HP-136 (trade name, manufactured by BASF Corporation, compound name: 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one).

胺系抗氧化劑可列舉為IRGASTAB FS 042(BASF公司製)、GENOX EP(CROMPTON公司製，化合物名：二烷基-N-甲基胺氧化物)等市售品(均為商品名)。 The amine-based antioxidants are commercially available products (all trade names) such as IRGASTAB FS 042 (manufactured by BASF Corporation) and GENOX EP (manufactured by CROMPTON Co., Ltd., compound name: dialkyl-N-methylamine oxide).

該等抗氧化劑可單獨使用，或可組合兩種以上使用。 These antioxidants may be used singly or in combination of two or more.

本發明之組成物中之抗氧化劑含量，基於不妨礙本發明效果之觀點，相對於化合物(C)、(D)、(E)及(F)之合計100質量份，較好為0.005~5質量份，更好為0.02~2質量份。 The antioxidant content in the composition of the present invention is preferably from 0.005 to 5 parts by mass based on 100 parts by mass of the total of the compounds (C), (D), (E) and (F), based on the viewpoint of not impairing the effects of the present invention. The mass fraction is more preferably 0.02 to 2 parts by mass.

作為光安定系可使用紫外線吸收劑或受阻胺系光安定劑等習知者，但較好為受阻胺系光安定劑。受阻胺系光安定劑之具體例列舉為雙(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、1,2,2,6,6-五甲基-4-哌啶基癸二酸甲酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、N,N’-雙(2,2,6,6-四甲基-4-哌啶基)-N,N’-二甲醯基六亞甲基二胺、二丁基胺．1,3,5-三嗪．N,N’-雙(2,2,6,6-四甲基-4-哌啶基)-1,6-六亞甲基二胺與N-(2,2,6,6-四甲基-4-哌啶基)丁基胺脂之聚縮合物、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、琥珀酸二甲酯與 4-羥基-2,2,6,6-四甲基-1-哌啶乙醇之聚合物、烯烴(C20-24).馬來酸酐.4-胺基-2,2,6,6-四甲基哌啶共聚物等，且可使用例如Adeka stab LA-77、Adeka stab LA-57、Adeka stab LA-52、Adeka stab LA-62、Adeka stab LA-67、Adeka stab LA-68、Adeka stab LA-63、Adeka stab LA-94、Adeka stab LA-94、Adeka stab LA-82、Adeka stab LA-87、Adeka stab LA-502 XP、Adeka stab LA-63 P、Adeka stab LA-81(以上為ADEKA公司製)、Tinuvin 111 FDL、Tinuvin 123、Tinuvin 144、Tinuvin 440、Tinuvin 662、Tinuvin 744、Tinuvin 765、Tinuvin 770DF、Tinuvin 783 FDL、Tinuvin 791 FB、Tinuvin XT 833、Tinuvin XT 850 FF、Tinuvin XT 855 FF、Chimassorb 2020、Chimassorb 119、Chimassorb 944、Uvinul 4050 FF、Uvinul 5050 H(以上為BASF公司製)、Hostavin N30(Hoechst公司製)、CYASORB UV-3346、CYASORB UV-3526(以上為Cytec公司製)、Uval 299(GLC公司製)、及Sanduvor PR-31(Clariant公司製)等市售品(均為商品名)。 As the light stabilizer, a known person such as an ultraviolet absorber or a hindered amine light stabilizer can be used, but a hindered amine light stabilizer is preferred. A specific example of a hindered amine light stabilizer is bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl) )-4-hydroxyphenyl]methyl]butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 1,2,2 , 6,6-pentamethyl-4-piperidinyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'- Bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dimethylhydrazine hexamethylenediamine, dibutylamine. 1,3,5-triazine. N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl Polycondensate of phenyl-4-piperidinyl)butylamine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2 ,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-4- Piperidinyl)imido}], dimethyl succinate and Polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, olefin (C20-24). Maleic anhydride. 4-Amino-2,2,6,6-tetra Methylpiperidine copolymer or the like, and for example, Adeka stab LA-77, Adeka stab LA-57, Adeka stab LA-52, Adeka stab LA-62, Adeka stab LA-67, Adeka stab LA-68, Adeka stab can be used. LA-63, Adeka stab LA-94, Adeka stab LA-94, Adeka stab LA-82, Adeka stab LA-87, Adeka stab LA-502 XP, Adeka stab LA-63 P, Adeka stab LA-81 (above ADEKA Corporation), Tinuvin 111 FDL, Tinuvin 123, Tinuvin 144, Tinuvin 440, Tinuvin 662, Tinuvin 744, Tinuvin 765, Tinuvin 770DF, Tinuvin 783 FDL, Tinuvin 791 FB, Tinuvin XT 833, Tinuvin XT 850 FF, Tinuvin XT 855 FF, Chimassorb 2020, Chimassorb 119, Chimassorb 944, Uvinul 4050 FF, Uvinul 5050 H (above, manufactured by BASF), Hostavin N30 (manufactured by Hoechst), CYASORB UV-3346, CYASORB UV-3526 (above, Cytec) Commercial products such as Uval 299 (manufactured by GLC Corporation) and Sanduvor PR-31 (manufactured by Clariant Co., Ltd.) (all trade names).

紫外線吸收劑之具體例列舉為2-(2H-苯并***-2-基)-對-甲酚、2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚、2-[5-氯-(2H)-苯并***-2-基]-4-甲基-6-(第三丁基)苯酚、2-(2H-苯并***-2-基)-4,6-二(第三戊基)苯酚、2-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚、2,2’-亞甲基雙[6-(2H-苯 并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚]、3-(3-(2H-苯并***-2-基)-5-第三丁基-4-羥基苯基)丙酸酯與聚乙二醇300之反應產物、2-(2H-苯并***-2-基)-6-十二烷基-4-甲基苯酚、2,2-雙{[2-氰基-3,3-二苯基丙烯醯氧基]甲基}丙烷-1,3-二基-雙(2-氰基-3,3-二苯基丙烯酸酯)、2-氰基-3,3-二苯基丙烯酸乙酯、2-氰基-3,3-二苯基丙烯酸2-乙基己酯、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-(己氧基)苯酚、八苯偶姻、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2-乙基己基-4-甲氧基桂皮酸酯、2,4-二第三丁基苯基-3,5-二第三丁基-4-羥基苯甲酸酯等，可使用例如Adeka stab LA-31、Adeka stab LA-32、Adeka stab LA-36、Adeka stab LA-29、Adeka stab LA-46、Adeka stab LA-F70、Adeka stab 1413(以上為ADEKA公司製)、Tinuvin P、Tinuvin 234、Tinuvin 326、Tinuvin 328、Tinuvin 329、Tinuvin 360、Tinuvin 213、Tinuvin 571、Uvinul 3030、Uvinul 3035、Uvinul 3039、Tinuvin B 75、Tinuvin PUR 866、Tinuvin 1577 ED、Chimassorb 81、Uvinul 3049、Uvinul 3050、Uvinul 3088、Tinuvin 120(以上為BASF公司製)等市售品(均為商品名)。 Specific examples of the ultraviolet absorber are exemplified by 2-(2H-benzotriazol-2-yl)-p-cresol and 2-(2H-benzotriazol-2-yl)-4,6-bis (1). -methyl-1-phenylethyl)phenol, 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(t-butyl)phenol, 2 -(2H-benzotriazol-2-yl)-4,6-di(tripentyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3 ,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzene And triazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 3-(3-(2H-benzotriazol-2-yl)-5- Reaction product of tributyl-4-hydroxyphenyl)propionate with polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol , 2,2-bis{[2-cyano-3,3-diphenylpropenyloxy]methyl}propane-1,3-diyl-bis(2-cyano-3,3-diphenyl) Acrylate), ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-(4,6-diphenyl 1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, octabenzoin, 2,2'-dihydroxy-4,4'-dimethoxybenzonitrile Ketone, 2,2',4,4'-tetrahydroxybenzophenone, 2-ethylhexyl-4-methoxycinnamate, 2,4-di-t-butylphenyl-3,5- As the di-tert-butyl-4-hydroxybenzoate or the like, for example, Adeka stab LA-31, Adeka stab LA-32, Adeka stab LA-36, Adeka stab LA-29, Adeka stab LA-46, Adeka stab can be used. LA-F70, Adeka stab 1413 (above manufactured by ADEKA), Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 360, Tinuvin 213, Tinuvin 571, Uvinul 3030, Uvinul 30 35. Commercial products (all trade names) such as Uvinul 3039, Tinuvin B 75, Tinuvin PUR 866, Tinuvin 1577 ED, Chimassorb 81, Uvinul 3049, Uvinul 3050, Uvinul 3088, and Tinuvin 120 (manufactured by BASF Corporation).

該等光安定劑可單獨使用，或可組合兩種以上使用。 These light stabilizers may be used singly or in combination of two or more.

本發明之組成物中之光安定劑含量，基於不妨礙本發明效果之觀點，相對於化合物(C)、(D)、(E)及 (F)之合計100質量份，較好為0.005~5質量份，更好為0.02~2質量份。 The content of the photosensitizer in the composition of the present invention is based on the viewpoint of not impairing the effects of the present invention, relative to the compounds (C), (D), (E) and The total of (F) is 100 parts by mass, preferably 0.005 to 5 parts by mass, more preferably 0.02 to 2 parts by mass.

本發明之組成物亦可例如90重量%以上、95重量%以上、98重量%以上、99重量%以上、100重量%係由氧化鋅、球狀二氧化矽、化合物(C)、及任意之化合物(D)、(E)、(F)所成。 The composition of the present invention may be, for example, 90% by weight or more, 95% by weight or more, 98% by weight or more, 99% by weight or more, or 100% by weight, based on zinc oxide, spherical cerium oxide, compound (C), and any of them. Compound (D), (E), (F).

本發明之組成物可以特定之量比混合氧化鋅、球狀二氧化矽、上述之(甲基)丙烯酸酯化合物而調製。混合方法並無特別限制，可使用攪拌機(混練機)等任意之習知手段。且，可在常溫、冷卻下、或加熱下，於常壓、減壓下、或加壓下混合。 The composition of the present invention can be prepared in a specific amount by mixing zinc oxide, spherical cerium oxide, or the above (meth) acrylate compound. The mixing method is not particularly limited, and any conventional means such as a mixer (kneading machine) can be used. Further, it may be mixed under normal pressure, under reduced pressure, or under heating at normal pressure, reduced pressure, or under pressure.

本發明之組成物可獲得可見光區域之反射率高之白色性優異、耐熱性及耐光性優異且黃變少、且與周邊構件(尤其是導線框架)之密性優異之硬化物，可較好地使用作為光半導體用之反射材料的原料。 The composition of the present invention can obtain a cured product having a high reflectance in a visible light region, excellent whiteness, excellent heat resistance and light resistance, and little yellowing, and is excellent in adhesion to peripheral members (especially a lead frame). A raw material used as a reflective material for an optical semiconductor is used.

〔硬化物〕 [hardened matter]

本發明之硬化物係由含金剛烷骨架之(甲基)丙烯酸樹脂構成之含氧化鋅、球狀二氧化矽者。 The cured product of the present invention is a zinc oxide-containing or spherical cerium oxide composed of a (meth)acrylic resin containing an adamantane skeleton.

含金剛烷骨架之(甲基)丙烯酸樹脂係含金剛烷基或經取代金剛烷基之(甲基)丙烯酸樹脂，經取代金剛烷基可如針對本發明之組成物之上述說明。 The (meth)acrylic resin containing an adamantane skeleton is a (meth)acrylic resin containing an adamantyl group or a substituted adamantyl group, and the substituted adamantyl group can be as described above for the composition of the present invention.

氧化鋅及球狀二氧化矽係分別如針對本發明之組成物之上述說明。 Zinc oxide and spheroidal cerium oxide are as described above for the composition of the present invention, respectively.

本發明之硬化物可藉由熱使上述說明之本發明組成物硬化獲得。硬化條件可考慮所使用之聚合起始劑的分解特性等適當決定。 The cured product of the present invention can be obtained by hardening the above-described composition of the present invention by heat. The curing conditions can be appropriately determined in consideration of the decomposition characteristics of the polymerization initiator used and the like.

本發明之硬化物可較好地利用作為例如光半導體發光裝置用之反射材料等。 The cured product of the present invention can be preferably used as, for example, a reflective material for an optical semiconductor light-emitting device.

〔反射材料〕 [reflective material]

可使用截至目前所說明之本發明之組成物或本發明之硬化物作為反射材料。 As the reflective material, the composition of the present invention or the cured product of the present invention as described so far can be used.

使用使本發明之組成物硬化獲得之硬化物的反射材料即使長時間使用反射率亦不會降低，在可見光區域之反射率高，且與周邊構件之密著性優異。 The reflective material using the cured product obtained by curing the composition of the present invention does not lower the reflectance for a long period of time, has a high reflectance in the visible light region, and is excellent in adhesion to peripheral members.

本發明之反射材料可使用本發明之組成物進行轉注成形(transfer molding)或壓縮成形而製造。 The reflective material of the present invention can be produced by transfer molding or compression molding using the composition of the present invention.

轉注成形時，可使用轉注成形機，在例如在成形壓力5~20N/mm2、成形溫度100~190℃以成形時間30~500秒，較好在成形溫度130~180℃以成形時間30~180秒成形。壓縮成形時，可使用壓縮成形機，在例如成形溫度100~190℃以成形時間30~600秒，較好在成形溫度130~160℃以成形時間30~300秒成形。任一成形法均亦可在例如150~185℃進行後硬化0.5~24小時。 In the case of transfer molding, a transfer molding machine can be used, for example, at a molding pressure of 5 to 20 N/mm 2 , a molding temperature of 100 to 190 ° C, and a molding time of 30 to 500 seconds, preferably a molding temperature of 130 to 180 ° C for a molding time of 30 to 30 °. Formed in 180 seconds. In the compression molding, a compression molding machine can be used, for example, at a molding temperature of 100 to 190 ° C for a molding time of 30 to 600 seconds, preferably at a molding temperature of 130 to 160 ° C for a molding time of 30 to 300 seconds. Any of the forming methods may be post-hardened at, for example, 150 to 185 ° C for 0.5 to 24 hours.

此外，亦可藉液狀樹脂射出成形、***成形等獲得成形體。 Further, a molded body can be obtained by injection molding, insert molding, or the like of liquid resin.

另外，以轉注成形、壓縮成形、液狀樹脂射出成形、 嵌入成形(insert molding)等使本發明之組成物成形時，亦可進行預聚合。 In addition, it is formed by transfer molding, compression molding, liquid resin injection molding, When the composition of the present invention is molded by insert molding or the like, prepolymerization can also be carried out.

本發明之反射材料在可見光區域之反射率高，即使長時間使用反射率之下降亦小。本發明之反射材料在波長450nm之光反射率，其初期值較好為85%以上，更好為90%以上，又更好為95%以上，在150℃經1,000小時之劣化試驗後之光反射率亦可達到較好80%以上，更好85%以上，又更好90%以上。又，光反射率係以實施例中記載之方法求出。 The reflective material of the present invention has a high reflectance in the visible light region, and has a small decrease in reflectance even when used for a long period of time. The light reflectance of the reflective material of the present invention at a wavelength of 450 nm is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, and light after degradation test at 150 ° C for 1,000 hours. The reflectance can also be better than 80%, more preferably 85% or more, and more preferably 90% or more. Further, the light reflectance was determined by the method described in the examples.

〔光半導體發光裝置〕 [Optical semiconductor light-emitting device]

本發明之光半導體發光裝置包含上述說明之本發明之反射材料。光半導體發光裝置之其他構成可為習知者。 The optical semiconductor light-emitting device of the present invention comprises the above-described reflective material of the present invention. Other configurations of the optical semiconductor light-emitting device can be known.

利用圖式進一步說明本發明之光半導體元件搭載用基板、及光半導體裝置。圖1係顯示本發明之光半導體元件搭載用基板、及光半導體裝置之一實施形態之概略剖面圖。 The optical semiconductor element mounting substrate and the optical semiconductor device of the present invention will be further described with reference to the drawings. 1 is a schematic cross-sectional view showing an embodiment of an optical semiconductor element mounting substrate and an optical semiconductor device according to the present invention.

圖1(a)顯示導線框架10。 Figure 1 (a) shows the lead frame 10.

圖1(b)顯示將作為反射材料21之樹脂成形體成形於圖1(a)之導線框架10上之光半導體元件搭載用基板20。光半導體元件搭載用基板20具有由由導線框架10及反射材料21所成之底面，與由反射材料21所成之內周側面所構成之凹部。構成反射材料21之樹脂成形體係使含有氧化鋅、球狀二氧化矽、黏度為 1~1,000mPa．s之鍵結有金剛烷基或經取代金剛烷基之(甲基)丙烯酸酯化合物之組成物硬化而成者。 Fig. 1(b) shows an optical semiconductor element mounting substrate 20 in which a resin molded body as the reflective material 21 is molded on the lead frame 10 of Fig. 1(a). The optical semiconductor element mounting substrate 20 has a concave portion formed by the bottom surface formed by the lead frame 10 and the reflective material 21 and the inner peripheral side surface formed by the reflective material 21. The resin molding system constituting the reflective material 21 contains zinc oxide, spherical cerium oxide, and has a viscosity of 1~1,000mPa. The bond of s is formed by hardening a composition of an adamantyl group or a substituted (meth) acrylate compound of adamantyl group.

圖1(c)顯示於圖1(b)之光半導體元件搭載用基板之導線框架上搭載光半導體元件31，以金屬線32黏合光半導體元件31與未搭載光半導體元件31之另一方的導線框架，且以透明樹脂(密封樹脂)33密封凹部而成之光半導體裝置30。密封樹脂之內部亦可含有用於使藍色等發光轉換成白色之螢光體34。 1(c) shows that the optical semiconductor element 31 is mounted on the lead frame of the optical semiconductor element mounting substrate of FIG. 1(b), and the other of the optical semiconductor element 31 and the optical semiconductor element 31 are bonded by the metal wire 32. The frame and the optical semiconductor device 30 in which the concave portion is sealed with a transparent resin (sealing resin) 33. The inside of the sealing resin may also contain a phosphor 34 for converting light such as blue into white.

且，顯示本發明之光半導體元件搭載用基板、及光半導體裝置之另一實施形態之概略剖面圖。 Further, a schematic cross-sectional view showing another embodiment of the optical semiconductor element mounting substrate and the optical semiconductor device of the present invention is shown.

圖2(a)係顯示導線框架10。 Figure 2 (a) shows the lead frame 10.

圖2(b)係顯示在圖2(a)之導線框架10之間使作為反射材料21之樹脂成形體成型而成之光半導體元件搭載用基板20。光半導體元件搭載用基板20具備導線框架10、與在導線框架10之間之反射材料21。 (b) of FIG. 2 shows an optical semiconductor element mounting substrate 20 in which a resin molded body as the reflective material 21 is molded between the lead frames 10 of FIG. 2(a). The optical semiconductor element mounting substrate 20 includes a lead frame 10 and a reflective material 21 between the lead frames 10 .

圖2(c)顯示具備圖2(b)之光半導體元件搭載用基板之光半導體裝置30。將光半導體元件31搭載於導線框架10上，藉由黏合金屬線32電連接後，以轉注成形或壓縮成形等方法使由透明密封樹脂33所成之密封樹脂部一次硬化成型，進行光半導體元件31之密封後，藉切割而單片化。密封樹脂之內部亦可含有用於將藍色等發光轉換成白色之螢光體34。 FIG. 2(c) shows an optical semiconductor device 30 including the substrate for mounting an optical semiconductor element of FIG. 2(b). After the optical semiconductor element 31 is mounted on the lead frame 10 and electrically connected by the bonding wire 32, the sealing resin portion formed of the transparent sealing resin 33 is once hardened by a method such as transfer molding or compression molding to perform optical semiconductor element. After the seal of 31, it is singulated by cutting. The inside of the sealing resin may also contain a phosphor 34 for converting light such as blue into white.

光半導體元件搭載用基板之各部尺寸．形狀並無特別限制，可適當設定。 The dimensions of each part of the substrate for mounting an optical semiconductor element. The shape is not particularly limited and can be appropriately set.

密封樹脂(密封材)係由例如環氧樹脂、聚矽氧樹脂、丙烯酸酯樹脂等構成。 The sealing resin (sealing material) is made of, for example, an epoxy resin, a polyoxymethylene resin, an acrylate resin or the like.

〔實施例〕 [Examples]

以下列舉本發明之實施例更詳細加以說明，但本發明並不受該等實施例之限制。 The embodiments of the present invention are described in more detail below, but the present invention is not limited by the examples.

各實施例及比較例中獲得之硬化物之物性評價方法如下。 The physical property evaluation method of the cured product obtained in each of the examples and the comparative examples was as follows.

(1)光反射率測定 (1) Light reflectance measurement

使用安裝多用途(multi purpose)大型試料室單元(島津製作所公司製，商品名：MPC-2200)之自動分光光度計(島津製作所公司製，商品名：UV-2400PC)，測定硬化物試驗片之光反射率。測定硬化物試驗片之初期值的光反射率後，以烘箱(ADVANTEC公司製，商品名：DRJ433DA)，在150℃進行特定時間之加熱後，測定加熱後之硬化物試驗片之光反射率(%)。 An automatic spectrophotometer (manufactured by Shimadzu Corporation, trade name: UV-2400PC), which is a large-scale multi-purpose sample unit (product name: MPC-2200, manufactured by Shimadzu Corporation), was used to measure the cured test piece. Light reflectivity. After measuring the light reflectance of the initial value of the cured test piece, it was heated in an oven (manufactured by ADVANTEC Co., Ltd., trade name: DRJ433DA) at 150 ° C for a specific period of time, and then the light reflectance of the cured test piece after heating was measured ( %).

實施例1 Example 1

秤量20g甲基丙烯酸1-金剛烷酯(黏度：15mPa．s)作為化合物(C)(酯鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物)、10g丙烯酸4-羥基丁酯作為化合物(D)(具有極性基之單官能丙烯酸酯)、60g丙烯酸硬脂酯作為化合物(E)(化合物(C)、 (D)以外之單官能(甲基)丙烯酸酯化合物)、10g參(2-丙烯醯氧基乙基)異氰尿酸酯(FA-731A)作為化合物(F)(多官能(甲基)丙烯酸酯化合物)、1g之PERHEXA HC作為聚合起始劑，將該等混合獲得調配液。 Weigh 20g of 1-adamantyl methacrylate (viscosity: 15mPa.s) as compound (C) (ester-bonded with adamantyl or substituted adamantyl (meth) acrylate compound), 10g of acrylic acid 4 -hydroxybutyl ester as compound (D) (monofunctional acrylate having a polar group), 60 g of stearyl acrylate as compound (E) (compound (C), Monofunctional (meth) acrylate compound other than (D), 10 g of gin(2-propenyl methoxyethyl) isocyanurate (FA-731A) as compound (F) (polyfunctional (methyl)) An acrylate compound) and 1 g of PERHEXA HC were used as a polymerization initiator, and these were mixed to obtain a formulation liquid.

以使球狀二氧化矽(龍森股份有限公司製)75質量%、氧化鋅(堺化學工業公司製，商品名：氧化鋅1種)10質量%之比例調配於該調配液15質量%中，且使用自轉．公轉混練機(THINKY公司製造，商品名：AWATORY練太郎)進行混合及攪拌，獲得組成物。 In a ratio of 10% by mass of spheroidal cerium oxide (manufactured by Ronzo Co., Ltd.) and zinc oxide (manufactured by Daicel Chemical Co., Ltd., trade name: one type of zinc oxide) to 10% by mass of the compounding liquid, 15% by mass of the compounding liquid And use rotation. A mixing and kneading machine (manufactured by THINKY Co., Ltd., trade name: AWATORY) was mixed and stirred to obtain a composition.

接著，藉由轉注成形在150℃使該組成物成形，獲得硬化物。物性之評價結果示於表1。 Next, the composition was molded at 150 ° C by transfer molding to obtain a cured product. The evaluation results of physical properties are shown in Table 1.

甲基丙烯酸1-金剛烷酯之黏度係如下述測定。 The viscosity of 1-adamantyl methacrylate was determined as follows.

使用熔融黏彈性裝置(Physica MCR 301，Anton Paar公司製)，以下述條件，測定實施例、比較例中獲得之組成物之黏度(複黏度(complex viscosity))。 The viscosity (complex viscosity) of the composition obtained in the examples and the comparative examples was measured using a melt viscoelastic device (Physica MCR 301, manufactured by Anton Paar Co., Ltd.) under the following conditions.

測定法：錐板(cone-plate) Determination method: cone-plate (cone-plate)

板直徑：25mm ，溫度：25℃，剪斷速度：10s-1 Plate diameter: 25mm , temperature: 25 ° C, cutting speed: 10 s -1

實施例2 Example 2

除使用70質量%球狀二氧化矽、15質量份之氧化鋅以外，餘與實施例1同樣獲得組成物，使硬化物成形。物性之評價結果示於表1。 A cured product was obtained in the same manner as in Example 1 except that 70% by mass of spherical cerium oxide and 15 parts by mass of zinc oxide were used. The evaluation results of physical properties are shown in Table 1.

實施例3 Example 3

除使用65質量%球狀二氧化矽、20質量份之氧化鋅以外，餘與實施例1同樣獲得組成物，使硬化物成形。物性之評價結果示於表1。 A cured product was obtained in the same manner as in Example 1 except that 65 mass% of spherical cerium oxide and 20 parts by mass of zinc oxide were used. The evaluation results of physical properties are shown in Table 1.

比較例1 Comparative example 1

以球狀二氧化矽75質量%、氧化鈦10質量%之比例調配於實施例1中獲得之調配液15質量%中，且與實施例1同樣獲得組成物，使硬化物成形。物性之評價結果示於表1。 In a ratio of 75 mass% of spherical cerium oxide and 10 mass% of titanium oxide, 15% by mass of the preparation liquid obtained in Example 1 was obtained, and a composition was obtained in the same manner as in Example 1 to form a cured product. The evaluation results of physical properties are shown in Table 1.

比較例2 Comparative example 2

以球狀二氧化矽70質量%、氧化鈦15質量%之比例調配於實施例1中獲得之調配液15質量%中，獲得組成物。 The composition was obtained by blending the compounding liquid obtained in Example 1 with 15% by mass of spherical cerium oxide (70% by mass) and titanium oxide (15% by mass).

所得組成物之黏度高，流動性差，故無法成形而無法獲得硬化物。 The obtained composition has high viscosity and poor fluidity, so that it cannot be formed and a cured product cannot be obtained.

比較例3 Comparative example 3

以球狀二氧化矽65質量%、氧化鈦20質量%之比例調配於實施例1中獲得之調配液15質量%中，獲得組成物。 The composition was obtained by blending 15% by mass of the formulation liquid obtained in Example 1 at a ratio of 65% by mass of spherical cerium oxide and 20% by mass of titanium oxide.

所得組成物之黏度高，流動性差，故無法成形而無法獲得硬化物。 The obtained composition has high viscosity and poor fluidity, so that it cannot be formed and a cured product cannot be obtained.

〔產業上之可利用性〕 [Industrial Applicability]

本發明之組成物及硬化物可較好地使用作為光半導體發光裝置用之反射材料的原料。 The composition and the cured product of the present invention can be preferably used as a raw material of a reflective material for an optical semiconductor light-emitting device.

上述已經詳細說明數個本發明之實施形態及/或實施例，但熟悉本技藝者由本發明之新穎教示及效果在實質上不偏離下，可輕易地對該等例示的實施形態及/或實施例加入多種變更。據此，該等多種變更均包含於本發明之範圍中。 The embodiments and/or the embodiments of the present invention have been described in detail above, but the embodiments and/or implementations of the present invention can be readily made without departing from the spirit and scope of the invention. Add a variety of changes to the example. Accordingly, various modifications are intended to be included within the scope of the invention.

成為本申請案之巴黎優先權基礎之日本申請案說明書之全部內容於本文中加以援用。 The entire contents of the Japanese application specification which is the basis of the Paris priority of the present application are hereby incorporated by reference.

Claims (10)

一種組成物，其係含有下述(A)、(B)及(C)：(A)：氧化鋅、(B)：球狀二氧化矽、(C)：黏度為1~1,000mPa．s之金剛烷基或經取代之金剛烷基鍵結而成的(甲基)丙烯酸酯化合物，相對於(A)~(C)之合計100質量份，(A)的含量為1~80質量份、(B)的含量為10~90質量份。 A composition comprising the following (A), (B) and (C): (A): zinc oxide, (B): spherical cerium oxide, (C): viscosity of 1 to 1,000 mPa. The (meth) acrylate compound in which the adamantyl group or the substituted adamantyl group is bonded is 100 parts by mass based on the total of (A) to (C), and the content of (A) is 1 to 80 mass. The content of the portion (B) is 10 to 90 parts by mass. 如請求項1之組成物，其中，相對於(A)~(C)之合計100質量份，(A)的含量為5~75質量份、(B)的含量為20~85質量份。 The composition of the claim 1 wherein the content of (A) is 5 to 75 parts by mass and the content of (B) is 20 to 85 parts by mass based on 100 parts by mass of the total of (A) to (C). 如請求項1之組成物，其中，相對於(A)~(C)之合計100質量份，(A)的含量為10~75質量份、(B)的含量為30~80質量份。 The composition of the claim 1 wherein the content of (A) is 10 to 75 parts by mass and the content of (B) is 30 to 80 parts by mass based on 100 parts by mass of the total of (A) to (C). 如請求項1之組成物，其係進一步含有下述(D)、(E)及(F)之中的至少1者，且相對於(A)~(C)與(D)~(F)之合計100質量份，(A)的含量為1~80質量份、(B)的含量為10~90質量份：(D)：具有(甲基)丙烯酸或極性基之單官能(甲基)丙烯酸酯化合物、(E)：(C)及(D)以外的單官能(甲基)丙烯酸酯化合物、(F)：多官能(甲基)丙烯酸酯化合物。 The composition of claim 1 further comprising at least one of the following (D), (E) and (F), and relative to (A) to (C) and (D) to (F) 100 parts by mass in total, (A) is 1 to 80 parts by mass, and (B) is 10 to 90 parts by mass: (D): monofunctional (methyl) having (meth)acrylic acid or a polar group An acrylate compound, (E): a monofunctional (meth) acrylate compound other than (C) and (D), and (F): a polyfunctional (meth) acrylate compound. 如請求項4之組成物，其中，組成物之98重量%以上係(A)~(F)。 The composition of claim 4, wherein 98% by weight or more of the composition is (A) to (F). 如請求項1之組成物，其中，前述球狀二氧化矽係經丙烯酸矽烷表面處理。 The composition of claim 1, wherein the spherical cerium oxide is surface-treated with decyl acrylate. 如請求項1~6中任一項之組成物，其中，前述球狀二氧化矽之一次粒子平均粒徑為0.1~100μm。 The composition according to any one of claims 1 to 6, wherein the spherical cerium oxide has a primary particle average particle diameter of 0.1 to 100 μm. 一種硬化物，其係使如請求項1~7中任一項之組成物硬化者。 A hardened material which is capable of hardening a composition according to any one of claims 1 to 7. 一種反射材料，其係使用如請求項8之硬化物者。 A reflective material using the hardened material of claim 8. 一種光半導體發光裝置，其係含有如請求項9之反射材料者。 An optical semiconductor light-emitting device comprising the reflective material of claim 9.
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