TW201428043A - Composition for reflective material, and optical semiconductor light-emitting device produced using same - Google Patents
Composition for reflective material, and optical semiconductor light-emitting device produced using same Download PDFInfo
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- TW201428043A TW201428043A TW102135516A TW102135516A TW201428043A TW 201428043 A TW201428043 A TW 201428043A TW 102135516 A TW102135516 A TW 102135516A TW 102135516 A TW102135516 A TW 102135516A TW 201428043 A TW201428043 A TW 201428043A
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- Taiwan
- Prior art keywords
- optical semiconductor
- meth
- acrylate
- semiconductor element
- reflective material
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000004065 semiconductor Substances 0.000 title claims description 115
- 230000003287 optical effect Effects 0.000 title claims description 113
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ITUWQZXQRZLLCR-UHFFFAOYSA-N n,n-dioctadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCCCC ITUWQZXQRZLLCR-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- JKBYAWVSVVSRIX-UHFFFAOYSA-N octadecyl 2-(1-octadecoxy-1-oxopropan-2-yl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)SC(C)C(=O)OCCCCCCCCCCCCCCCCCC JKBYAWVSVVSRIX-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- FQZYTYWMLGAPFJ-OQKDUQJOSA-N tamoxifen citrate Chemical compound [H+].[H+].[H+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.C=1C=CC=CC=1C(/CC)=C(C=1C=CC(OCCN(C)C)=CC=1)/C1=CC=CC=C1 FQZYTYWMLGAPFJ-OQKDUQJOSA-N 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FFIUNPRXUCRYFU-UHFFFAOYSA-N tert-butyl pentaneperoxoate Chemical compound CCCCC(=O)OOC(C)(C)C FFIUNPRXUCRYFU-UHFFFAOYSA-N 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- WFYHNNDLDSVRPI-UHFFFAOYSA-N tert-butylperoxy 6-[(2-methylpropan-2-yl)oxyperoxycarbonyloxy]hexyl carbonate Chemical compound C(C)(C)(C)OOOC(=O)OCCCCCCOC(=O)OOOC(C)(C)C WFYHNNDLDSVRPI-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Led Device Packages (AREA)
Abstract
Description
本發明係有關可適合作為光半導體用之反射材原料使用之組成物及其硬化物及使用此等之光半導體發光裝置。 The present invention relates to a composition which can be suitably used as a material for a reflective material for an optical semiconductor, a cured product thereof, and an optical semiconductor light-emitting device using the same.
又，本發明係有關光半導體元件搭載用基板及光半導體裝置。 Moreover, the present invention relates to an optical semiconductor element mounting substrate and an optical semiconductor device.
使用近年普及之發光二極體(LED)等之光半導體的發光裝置，通常將光半導體(LED)固定於將合成樹脂於導線架上，以凹形狀進行一體成形所成之成形體的導線架上，再以環氧樹脂或聚矽氧樹脂等之封裝材料封裝來製造。 A light-emitting device using an optical semiconductor such as a light-emitting diode (LED) which has been widely used in recent years, usually a photo-semiconductor (LED) is fixed to a lead frame of a molded body in which a synthetic resin is integrally formed on a lead frame and formed in a concave shape. Further, it is manufactured by encapsulating an epoxy resin or a polyoxymethylene resin.
反射材用之材料例如專利文獻1中揭示在丙烯酸酯樹脂等之熱硬化性樹脂中調配氧化鈦顏料的材料。但是使用具有代表性的白色顏料，即氧化鈦時，液體的黏度容易上升，影響液體的流動性，在導線架上形成樹脂成形體時，導線架會產生變形或未充填。 A material for a reflective material, for example, Patent Document 1 discloses a material in which a titanium oxide pigment is blended in a thermosetting resin such as an acrylate resin. However, when a representative white pigment, that is, titanium oxide, is used, the viscosity of the liquid easily rises, affecting the fluidity of the liquid, and when the resin molded body is formed on the lead frame, the lead frame may be deformed or unfilled.
又，專利文獻2揭示使用氮化硼粒子之白色 顏料的反射材組成物，但是與氧化鈦同樣，液體的黏度容易上升，影響液體的流動性，因此，導線架成形體上會產生變形或未充填的問題。 Further, Patent Document 2 discloses white using boron nitride particles The composition of the reflective material of the pigment is similar to that of titanium oxide, and the viscosity of the liquid tends to increase, which affects the fluidity of the liquid. Therefore, there is a problem that the lead frame molded body is deformed or not filled.
[先行技術文獻] [Advanced technical literature]
[專利文獻] [Patent Literature]
[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
[發明概要] [Summary of the Invention]
本發明之目的係提供反射率或耐熱性高之光半導體用之反射材的材料，且可降低發光裝置製造時所產生之導線架成形體之變形或未充填的材料。 SUMMARY OF THE INVENTION An object of the present invention is to provide a material for a reflective material for an optical semiconductor having high reflectance or heat resistance, and to reduce deformation or unfilled material of a lead frame formed body which is produced at the time of manufacture of a light-emitting device.
又，本發明之另外目的係提供具備反射率或耐熱性高之反射材的光半導體元件搭載用基板及光半導體裝置。 Moreover, another object of the present invention is to provide an optical semiconductor element mounting substrate and an optical semiconductor device including a reflective material having high reflectance or heat resistance.
又，本發明之另外目的係提供使用可降低光半導體元件搭載用基板製造時所產生之導線架成形體之變形或未充填之反射材之光半導體元件搭載用基板及光半導體裝置。 Moreover, another object of the present invention is to provide an optical semiconductor element mounting substrate and an optical semiconductor device using a reflective material which can reduce deformation or unfilled of a lead frame molded body which is produced when the optical semiconductor element mounting substrate is manufactured.
依據本發明時，可提供以下之組成物等。 According to the invention, the following compositions and the like can be provided.
1.一種組成物，其特徵係含有氧化鋯、球狀二氧化矽、及黏度為1~1000mPa．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。 1. A composition characterized by containing zirconium oxide, spherical ceria, and having a viscosity of from 1 to 1000 mPa. The s bond has an adamantyl group or a substituted adamantyl (meth) acrylate compound.
2.如上述第1項之組成物，其中前述球狀二氧化矽經丙烯醯基矽烷表面處理。 2. The composition according to the above item 1, wherein the spherical cerium oxide is surface-treated with acrylonitrile decane.
3.如上述第1或2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。 3. The composition according to the above item 1 or 2, wherein the spherical cerium oxide has a primary particle average particle diameter of 0.1 to 100 μm.
4.一種硬化物，其特徵係由含有金剛烷骨架之(甲基)丙烯酸樹脂所構成，且含有氧化鋯與球狀二氧化矽。 A cured product comprising a (meth)acrylic resin containing an adamantane skeleton and comprising zirconia and spherical ruthenium dioxide.
5.一種反射材，其特徵係使用上述第4項的硬化物。 A reflective material characterized by using the cured product of the above item 4.
6.一種光半導體發光裝置，其特徵係含有如上述第5項的反射材。 An optical semiconductor light-emitting device characterized by comprising the reflective material according to item 5 above.
又，依據本發明時，可提供以下光半導體元件搭載用基板及光半導體裝置等。 Moreover, according to the present invention, the following optical semiconductor element mounting substrate, optical semiconductor device, and the like can be provided.
7.一種光半導體元件搭載用基板，其特徵係具有由導線架及反射材所構成之凹部的光半導體元件搭載用基板，前述反射材為含有氧化鋯與球狀二氧化矽，且以鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯為單體的樹脂成形體所構成。 7. A substrate for mounting an optical semiconductor element, comprising: a substrate for mounting an optical semiconductor element having a concave portion formed of a lead frame and a reflective material, wherein the reflective material contains zirconia and spherical ruthenium dioxide, and is bonded A (meth) acrylate having an adamantyl group or a substituted adamantyl group is a resin molded body of a monomer.
8.一種光半導體裝置，其特徵係具備：具有由導線架及反射材所構成之凹部的光半導體元件搭載用基板、搭載於前述光半導體元件搭載基板之凹部之導線架上的光半導體元件及覆蓋前述光半導體元件的封裝樹脂的光半導體裝置，前述反射材為含有氧化鋯與球狀二氧化矽，且以鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯為單體的樹脂成形體所構成。 An optical semiconductor device comprising: an optical semiconductor element mounting substrate having a concave portion formed of a lead frame and a reflective material; and an optical semiconductor element mounted on a lead frame of the concave portion of the optical semiconductor element mounting substrate; An optical semiconductor device covering the encapsulating resin of the optical semiconductor element, wherein the reflective material is a (meth) acrylate containing zirconium oxide and spherical cerium oxide bonded with an adamantyl group or a substituted adamantyl group. It is composed of a single resin molded body.
9.一種光半導體元件搭載用基板，其特徵係由2個導線架及於前述2個導線架之間的反射材所構成的光半導體元件搭載用基板，前述反射材為含有氧化鋯與球狀二氧化矽，且以鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯為單體的樹脂成形體所構成。 9. A substrate for mounting an optical semiconductor element, characterized in that the substrate for optical semiconductor element mounting comprising two lead frames and a reflective material between the two lead frames, the reflective material containing zirconia and spherical Cerium oxide is composed of a resin molded body in which adamantyl group or a substituted adamantyl group (meth) acrylate is bonded as a monomer.
10.一種光半導體裝置，其特徵係具備：由2個導線架及於前述2個導線架之間的反射材所構成的光半導體元件搭載用基板、搭載於前述光半導體元件搭載基板之導線架上的光半導體元件及覆蓋前述光半導體元件的封裝樹脂的光半導體裝置，前述反射材為含有氧化鋯與球狀二氧化矽，且以鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯為單體的樹脂成形體所構成。 10. An optical semiconductor device comprising: an optical semiconductor element mounting substrate comprising two lead frames and a reflective material between the two lead frames; and a lead frame mounted on the optical semiconductor element mounting substrate In the optical semiconductor device and the optical semiconductor device covering the encapsulating resin of the optical semiconductor device, the reflective material is composed of zirconia and spherical cerium oxide, and an adamantyl group or a substituted adamantyl group is bonded ( The methyl acrylate is a resin molded body of a monomer.
依據本發明時，可提供反射率或耐熱性高之光半導體用反射材的材料，且可減低發光裝置製造時所產生之導線架成形體之變形或未充填的材料。 According to the present invention, it is possible to provide a material for a reflective material for an optical semiconductor having high reflectance or heat resistance, and it is possible to reduce deformation or unfilled material of a lead frame formed body which is produced at the time of manufacture of a light-emitting device.
又，依據本發明時，可提供具備反射率或耐熱性高之反射材的光半導體元件搭載用基板及光半導體裝置。 Moreover, according to the present invention, it is possible to provide an optical semiconductor element mounting substrate and an optical semiconductor device including a reflecting material having a high reflectance or heat resistance.
又，可提供一種使用可減低發光半導體元件搭載用基板製造時所產生之導線架成形體之變形或未充填的反射材之光半導體元件搭載用基板及光半導體裝置。 In addition, it is possible to provide an optical semiconductor element mounting substrate and an optical semiconductor device using a reflective material which can reduce distortion or unfilled of the lead frame molded body which is produced when the light emitting semiconductor element mounting substrate is manufactured.
10‧‧‧導線架 10‧‧‧ lead frame
20‧‧‧光半導體元件搭載用基板 20‧‧‧Microsemiconductor component mounting substrate
21‧‧‧反射材 21‧‧‧Reflective material
30‧‧‧光半導體裝置 30‧‧‧Optical semiconductor devices
31‧‧‧光半導體元件 31‧‧‧Optical semiconductor components
32‧‧‧接合線 32‧‧‧bonding line
33‧‧‧封裝樹脂 33‧‧‧Packaging resin
34‧‧‧螢光體 34‧‧‧Fertior
[圖1]係表示本發明之光半導體元件搭載用基板及光半導體裝置之實施形態之概略剖面圖，(a)係導線架之剖面圖，(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]表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外之實施形態的概略剖面圖，(a)係導線架之剖面圖，(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。 FIG. 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有氧化鋯、球狀二氧化矽及黏度為1~1000mPa．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(以下也稱為「化合物(A)」)者。 The composition of the present invention contains zirconia, spherical ceria and has a viscosity of 1 to 1000 mPa. The s bond is an adamantyl group or a substituted adamantyl (meth) acrylate compound (hereinafter also referred to as "compound (A)").
組成物中含有氧化鋯，將組成物作為光半導體用之反射材的原料使用時，可提高反射率、耐熱性、耐光性。 When the composition contains zirconia and the composition is used as a raw material of a reflective material for an optical semiconductor, reflectance, heat resistance, and light resistance can be improved.
以往作為白色顏料使用之氧化鈦，在紫外線區域之光的反射率低，且具有光觸媒功能，因此長期間曝露於LED等之光半導體時，樹脂可能劣化，但是本發明之組成物不含氧化鈦，而含有氧化鋯者，故無此種問題。 Titanium oxide used as a white pigment has a low reflectance of light in an ultraviolet region and has a photocatalytic function. Therefore, when exposed to an optical semiconductor such as an LED for a long period of time, the resin may be deteriorated, but the composition of the present invention does not contain titanium oxide. There is no such problem, but it contains zirconia.
組成物中之氧化鋯的含量係相對於化合物(A)、氧化鋯及球狀二氧化矽之合計100質量份，或後述之任意成分(化合物(B)、(C)、(D))存在時，相對於化合物(A) 、氧化鋯及球狀二氧化矽與此等之合計100質量份，較佳為1~80質量份，更佳為5~75質量份，又更佳為10~75質量份。 The content of the zirconia in the composition is 100 parts by mass based on the total of the compound (A), zirconia, and spheroidal cerium oxide, or any component (the compound (B), (C), (D)) described later. Relative to compound (A) The total amount of the zirconia and the spheroidal cerium oxide is 100 parts by mass, preferably 1 to 80 parts by mass, more preferably 5 to 75 parts by mass, still more preferably 10 to 75 parts by mass.
本發明之組成物更含有球狀二氧化矽(SiO2)。氧化鋯在液中易沈澱，可使用的量受限，但是調配黏度較低之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，此外再組合球狀二氧化矽使用，可提高組成物中之無機物之含量，可更提高反射率、耐熱性、耐光性。 The composition of the present invention further contains spherical cerium oxide (SiO 2 ). Zirconium oxide is easily precipitated in liquid, and the amount that can be used is limited, but the ester having a lower viscosity is bonded with an adamantyl group or a substituted adamantyl (meth) acrylate compound, in addition to a spherical shape. When cerium oxide is used, the content of the inorganic substance in the composition can be increased, and the reflectance, heat resistance, and light resistance can be further improved.
又，可保持組成物之流動性，提高成形時之充填性。 Moreover, 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係藉由雷射繞射測定，例如為0.1~100μm，較佳為0.5~70μm，更佳為1~50μm。藉此，可提高球狀二氧化矽之充填性。 The primary particle average particle diameter of the spherical ceria is measured by laser diffraction, and is, for example, 0.1 to 100 μm, preferably 0.5 to 70 μm, more preferably 1 to 50 μm. Thereby, the filling property of the spherical cerium oxide can be improved.
球狀二氧化矽較佳為經丙烯醯基矽烷表面處理。球狀二氧化矽之表面的羥基，與丙烯醯基矽烷反應，進行有機修飾(改性)，可提高球狀二氧化矽之潤濕性，組成物中，可容易混合球狀二氧化矽與有機成分(化合物(A)~(D))。其中，「丙烯醯基矽烷(表面處理)」包括甲基丙烯醯基矽烷(表面處理)。 The spherical cerium oxide is preferably surface treated with acrylonitrile decane. The hydroxyl group on the surface of the spherical cerium oxide is reacted with acrylonitrile decane to be organically modified (modified) to improve the wettability of the spherical cerium oxide. In the composition, the spherical cerium oxide can be easily mixed. Organic component (compounds (A) to (D)). Here, "propylene decyl decane (surface treatment)" includes methacryl decyl decane (surface treatment).
組成物中之球狀二氧化矽之含量係相對於化合物(A)、氧化鋯、及球狀二氧化矽之合計100質量份，或後述任意成分(化合物(B)、(C)、(D))存在時，相對於化合物(A)、氧化鋯及球狀二氧化矽與此等之合計100質量份，較佳為10~90質量份，更佳為20~85質量份，又更佳 為30~80質量份。 The content of the spherical cerium oxide in the composition is 100 parts by mass based on the total of the compound (A), zirconia, and spheroidal cerium oxide, or an optional component (the compound (B), (C), (D). When it is present, it is preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass, more preferably, based on 100 parts by mass of the total of the compound (A), zirconia and spheroidal cerium oxide. It is 30 to 80 parts by mass.
化合物(A)提供玻璃轉化溫度較高的聚合物，因此含有於組成物中，將組成物作為光半導體用反射材的原料使用時，可提高耐熱性、耐光性。 Since the compound (A) provides a polymer having a high glass transition temperature, it is contained in the composition, and when the composition is used as a raw material of a reflective material for an optical semiconductor, heat resistance and light resistance can be improved.
經取代之金剛烷基係指，包含於金剛烷基之氫原子被羥基等取代者。例如有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、雙金剛烷基、二甲基金剛烷基等。 The substituted adamantyl group means a hydrogen atom contained in an adamantyl group substituted with a hydroxyl group or the like. For example, there are 1-hydroxyadamantyl, 2-hydroxyadamantyl, 1-methyladamantyl, 2-methyladamantyl, bisadamantyl, dimethyladamantyl and the like.
金剛烷基或經取代之金剛烷基，較佳為金剛烷基，更佳為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(A)具體而言，例如有1-金剛烷基丙烯酸酯、2-金剛烷基丙烯酸酯、1-金剛烷基甲基丙烯酸酯、2-金剛烷基甲基丙烯酸酯等，較佳為金剛烷基甲基丙烯酸酯，更佳為1-金剛烷基甲基丙烯酸酯。金剛烷基進行酯鍵結的(甲基)丙烯酸酯化合物可單獨使用一種或組合二種以上使用。 Specific examples of the compound (A) include 1-adamantyl acrylate, 2-adamantyl acrylate, 1-adamantyl methacrylate, 2-adamantyl methacrylate, etc., preferably Adamantyl methacrylate, more preferably 1-adamantyl methacrylate. The (meth) acrylate compound in which the adamantyl group is ester-bonded may be used alone or in combination of two or more.
化合物(A)之黏度較佳為1~1000mPa．s，更佳為1~500mPa．s，又更佳為1~100mPa．s。如此，在組成物中調配黏度較低之化合物(A)，可提高氧化鋯與球狀二氧化矽之充填性。又，可使填料進行高充填，更提高反射率、耐熱性、耐光性。 The viscosity of the compound (A) is preferably from 1 to 1000 mPa. s, more preferably 1~500mPa. s, and more preferably 1~100mPa. s. Thus, the compound (A) having a low viscosity can be blended in the composition to improve the filling property of zirconia and spherical cerium oxide. Moreover, the filler can be highly filled, and the reflectance, heat resistance, and light resistance can be further improved.
黏度可藉由例如流變儀(Rheometer)或旋轉式黏度計測定。 The viscosity can be measured by, for example, a rheometer or a rotary viscometer.
又，本發明之組成物可含有作為任意成分之 化合物(A)以外之其他的聚合性丙烯酸酯化合物等。 Further, the composition of the present invention may contain as an optional component A polymerizable acrylate compound other than the compound (A).
此等任意成分例如有(甲基)丙烯酸、或具有極性基之單官能(甲基)丙烯酸酯化合物(以下也稱為「化合物(B)」)；化合物(A)，(B)以外之單官能(甲基)丙烯酸酯化合物(以下也稱為「化合物(C)」)；多官能(甲基)丙烯酸酯化合物(以下也稱為「化合物(D)」)等。 These optional components are, for example, (meth)acrylic acid or a monofunctional (meth) acrylate compound having a polar group (hereinafter also referred to as "compound (B)"); a compound other than the compound (A) or (B) A functional (meth) acrylate compound (hereinafter also referred to as "compound (C)"); a polyfunctional (meth) acrylate compound (hereinafter also referred to as "compound (D)").
本發明之組成物中之化合物(A)之含量係化合物(A)、(B)、(C)及(D)之合計100質量%，較佳為10~70質量%，更佳為15~60質量%，又更佳為20~50質量%。 The content of the compound (A) in the composition of the present invention is 100% by mass, preferably 10 to 70% by mass, more preferably 15% by weight based on the total of the compounds (A), (B), (C) and (D). 60% by mass, and more preferably 20 to 50% by mass.
化合物(B)係(甲基)丙烯酸或具有極性基之單官能(甲基)丙烯酸酯化合物。化合物(B)係具有極性，因此在組成物中含有時，形成具有極性之金屬表面等與氫鍵結等，提高密著性，又，因極性基之存在，而提高潤濕性。又，有時伸烷基二醇基(ALKYLENE GLYCOL)也與賦予密著性有關係，但是伸烷基二醇(甲基)丙烯酸酯不包含於化合物(B)中。 The compound (B) is a (meth)acrylic acid or a monofunctional (meth) acrylate compound having a polar group. Since the compound (B) has a polarity, when it is contained in the composition, a metal surface having a polarity or the like is formed to bond with hydrogen or the like to improve adhesion, and the wettability is improved by the presence of a polar group. Further, the alkyl diol group (ALKYLENE GLYCOL) may also be associated with the adhesion, but the alkyl diol (meth) acrylate is not contained in the compound (B).
具有極性基之(甲基)丙烯酸酯化合物，例如含有碳、氫以外之原子的取代基進行酯鍵結的(甲基)丙烯酸酯化合物，取代基例如有羥基、環氧基、縮水甘油醚基、四氫呋喃甲基、異氰酸酯基、羧基、烷氧基矽烷基、磷酸酯基、內酯基、氧雜環丁基(oxetanyl)、四氫吡喃基、胺基等。 a (meth) acrylate compound having a polar group, for example, a (meth) acrylate compound having a substituent bonded to a substituent other than carbon or hydrogen, and a substituent such as a hydroxyl group, an epoxy group or a glycidyl ether group , tetrahydrofuranmethyl, isocyanate, carboxyl, alkoxyalkyl, phosphate, lactone, oxetanyl, tetrahydropyranyl, amine, and the like.
具有極性基之(甲基)丙烯酸酯化合物之具體例，例如有2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基) 丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯(例如有商品名：4-HBA、日本化成(股)製)、環己烷二甲醇單(甲基)丙烯酸酯(例如有商品名：CHMMA、日本化成(股)製)、縮水甘油基(甲基)丙烯酸酯、4-羥基丁基丙烯酸酯縮水甘油醚(例如有商品名：4-HBAGE、日本化成(股)製)、四氫呋喃甲基(甲基)丙烯酸酯、2-異氰酸基乙基(isocyanatoethyl)(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基乙基六氫苯二甲酸、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、二(2-(甲基)丙烯醯氧基乙基)磷酸酯、KAYAMER PM-21(商品名、日本化藥(股)製)、γ-丁基內酯(甲基)丙烯酸酯、(甲基)丙烯酸(3-甲基-3-氧雜環丁基)酯、(甲基)丙烯酸(3-乙基-3-氧雜環丁基)酯、四氫呋喃甲基(甲基)丙烯酸酯、二甲基胺基乙基(甲基)丙烯酸酯、二乙基胺基乙基(甲基)丙烯酸酯等。 Specific examples of the (meth) acrylate compound having a polar group include, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (methyl) Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (for example, trade name: 4-HBA, manufactured by Nippon Kasei Co., Ltd.), cyclohexane dimethanol (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., tetrahydrofuran methyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl Succinic acid, 2-(methyl) propylene oxiranyl ethyl hexahydrophthalic acid, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propylene Methyldimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3-(methyl)propenyloxypropylmethyldiethoxydecane, 2-( Methyl) propylene methoxyethyl phosphate, bis(2-(methyl) propylene oxyethyl) phosphate, KAYAMER PM-21 (trade name, manufactured by Nippon Kayaku Co., Ltd.), γ-butyl A lactone (meth) acrylate, (meth) acrylate (3-methyl-3-oxa) Cyclobutyl)ester, (3-ethyl-3-oxetanyl) (meth)acrylate, tetrahydrofuranmethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate , diethylaminoethyl (meth) acrylate, and the like.
本發明中，化合物(B)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組合二種以上使用。 In the present invention, the compound (B) may be used alone or in combination of two or more 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(B)之含量，從密著性的觀點，相對於化合物(A)、(B)、(C)及(D)之合計100質量%，較佳為1~40質量%，更佳為5~35質量%，又更佳為10~30質量%。 The content of the compound (B) in the composition of the present invention is preferably 100% by mass, preferably 1%, based on the total of the compounds (A), (B), (C) and (D). 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass.
化合物(C)係化合物(A)、(B)以外之單官能(甲基)丙烯酸酯化合物。本發明之組成物中，含有化合物(C)，主要是賦予柔軟性，可抑制龜裂之發生等。 The compound (C) is a monofunctional (meth) acrylate compound other than the compounds (A) and (B). The composition of the present invention contains the compound (C), and mainly imparts flexibility, and can suppress the occurrence of cracks and the like.
化合物(D)係多官能(甲基)丙烯酸酯化合物。從機械強度的觀點，在不阻礙本發明效果的範圍內，在組成物中可含有化合物(A)~(C)以外之多官能(甲基)丙烯酸酯化合物。 The compound (D) is a polyfunctional (meth) acrylate compound. From the viewpoint of mechanical strength, a polyfunctional (meth) acrylate compound other than the compounds (A) to (C) may be contained in the composition within a range not inhibiting the effects of the present invention.
化合物(A)、(B)以外之(甲基)丙烯酸酯化合物(化合物(C)、(D))例如有選自(甲基)丙烯酸酯改性聚矽氧油、具有長鏈脂肪族烴基之(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、環氧基丙烯酸酯及聚酯丙烯酸酯所成群之至少一種的(甲基)丙烯酸酯化合物。化合物(C)可選擇使用此等中單官能(甲基)丙烯酸酯化合物。又，化合物(D)可選擇使用此等中多官能(甲基)丙烯酸酯化合物。 The (meth) acrylate compound (compounds (C), (D)) other than the compound (A) or (B) is, for example, selected from a (meth) acrylate-modified polysiloxane oil having a long-chain aliphatic hydrocarbon group. At least one of a (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. (Meth) acrylate compound. Compound (C) may optionally employ such a monofunctional (meth) acrylate compound. Further, the compound (D) may optionally use such a polyfunctional (meth) acrylate compound.
本發明用之(甲基)丙烯酸酯改性聚矽氧油係在末端具有丙烯醯基及/或甲基丙烯醯基，較佳為骨架中含有二烷基聚矽氧烷的化合物。此(甲基)丙烯酸酯改性聚矽氧油，大部分為二甲基聚矽氧烷的變性物，取代甲基，而藉由苯基或甲基以外之烷基，在二烷基聚矽氧烷骨架中之烷基之全部或一部分可被取代。甲基以外之烷基，例如有乙基、丙基等。這種化合物之市售品，可使用單末端反應性聚矽氧油(例如有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(股)製、均為商品名)、甲基丙烯酸酯改性聚矽氧油(例如BY16-152D、BY16-152、BY16-152C)(以上為東麗Dowcorning(股)製、均為商品名)等。 The (meth) acrylate-modified polyoxyxene oil used in the present invention has a propylene fluorenyl group and/or a methacryl fluorenyl group at the terminal, and preferably a compound containing a dialkyl polysiloxane in the skeleton. The (meth) acrylate-modified polyoxyxene oil, which is mostly a denatured product of dimethyl polyoxyalkylene, which is substituted by a methyl group, and which is polymerized by a dialkyl group by an alkyl group other than a phenyl group or a methyl group. All or a portion of the alkyl group in the oxoxane skeleton may be substituted. The alkyl group other than a methyl group is, for example, an ethyl group, a propyl group or the like. Commercially available compounds of this type may be used as single-end reactive polyoxyxides (for example, X-22-174DX, X-22-2426, X-22-2475), and reactive polyoxyxides at both ends (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), methacrylate-modified polyoxyxides (such as BY16-152D, BY16-152, BY16-152C) (above Toray Dowcorning (shares), all of which are trade names).
又，(甲基)丙烯酸酯改性聚矽氧油，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。具體而言，例如有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、丙烯醯氧基末端環氧乙烷聚二甲基矽氧烷(A嵌段(block))及環氧乙烷(B嵌段)所構成之ABA型三嵌段共聚合物、甲基丙烯醯氧基丙基末端分支聚二甲基矽氧烷等。 Further, as the (meth) acrylate-modified polysiloxane, a polydialkyl decane having an acryloxyalkyl end or a methacryloxyalkyl end may be used. Specifically, there are, for example, methacryloxypropyl propyl terminal polydimethyl methoxy olefin, (3-propylene fluorenyloxy-2-hydroxypropyl) terminal polydimethyl methoxy oxane, propylene fluorenyloxy group. ABA type triblock copolymer composed of terminal ethylene oxide polydimethyl siloxane (A block) and ethylene oxide (B block), methacryloxypropyl propyl group The terminal branch is polydimethyloxane or the like.
此等中，從硬化物之密著性的觀點，較佳為使用(3-丙烯醯氧基-2-羥基丙基)末端聚二甲基矽氧烷、丙烯醯氧基末端環氧乙烷聚二甲基矽氧烷(A嵌段(block))及環氧乙烷(B嵌段)所構成之ABA型三嵌段共聚合物。 Among these, from the viewpoint of the adhesion of the cured product, it is preferred to use (3-propenyloxy-2-hydroxypropyl) terminal polydimethyl siloxane, propylene oxime terminal ethylene oxide. An ABA type triblock copolymer composed of polydimethyl siloxane (A block) and ethylene oxide (B block).
本發明用之具有長鏈脂肪族烴基之(甲基)丙烯酸酯係由長鏈脂肪族烴化合物中除去氫原子之殘基，與(甲基)丙烯酸酯基鍵結的化合物。 The (meth) acrylate having a long-chain aliphatic hydrocarbon group used in the present invention is a compound in which a residue of a hydrogen atom is removed from a long-chain aliphatic hydrocarbon compound and bonded to a (meth) acrylate group.
可衍生本發明用之具有長鏈脂肪族烴基之(甲基)丙烯酸酯之脂肪族烴化合物，較佳為烷烴，從本發明之硬化物之密著性的觀點，較佳為碳數12以上之烷烴。 The aliphatic hydrocarbon compound of the (meth) acrylate having a long-chain aliphatic hydrocarbon group used in the present invention may be derived, preferably an alkane, and preferably has a carbon number of 12 or more from the viewpoint of adhesion of the cured product of the present invention. Alkanes.
由本發明之硬化物之密著性的觀點，長鏈脂肪族烴基更佳為碳數12以上之脂肪族烴基。使用含有碳數12以上 之長鏈脂肪族烴基的(甲基)丙烯酸酯時，本發明之組成物可提供密著性優異的硬化物。 From the viewpoint of the adhesion of the cured product of the present invention, the long-chain aliphatic hydrocarbon group is more preferably an aliphatic hydrocarbon group having 12 or more carbon atoms. Use a carbon number of 12 or more In the case of a long-chain aliphatic hydrocarbon group (meth) acrylate, the composition of the present invention can provide a cured product excellent in adhesion.
本發明用之具有長鏈脂肪族烴基之(甲基)丙烯酸酯中，(甲基)丙烯酸酯基之數無特別限定，可為1個或複數個。(甲基)丙烯酸酯基之數為1個時，長鏈脂肪族烴基較佳為長鏈烷基，更佳為碳數12以上(較佳為碳數12~24、更佳為碳數12~18)的烷基。(甲基)丙烯酸酯基之數為2個時，長鏈脂肪族烴基較佳為長鏈伸烷基，更佳為碳數12以上(較佳為碳數12~24、更佳為碳數12~18)之伸烷基。 In the (meth) acrylate having a long-chain 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 long-chain aliphatic hydrocarbon group is preferably a long-chain 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) ~18) alkyl group. When the number of (meth) acrylate groups is two, the long-chain aliphatic hydrocarbon group is preferably a long-chain alkyl group, more preferably a carbon number of 12 or more (preferably, a carbon number of 12 to 24, more preferably a carbon number). 12~18) alkylene.
碳數12以上的烷基之具體例，例如有十二烷基(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(icosyl)、三十烷基(triacontyl)及三十四烷基等。碳數12以上之烷基可為來自聚丁二烯或聚異戊二烯等之聚合物之氫化物的烷基。碳數12以上之伸烷基之具體例，例如有由上述烷基中除去氫原子之2價殘基。 Specific examples of the alkyl group having 12 or more carbon atoms include, for example, dodecyl group (containing lauryl group), tridecyl group, tetradecyl group, hexadecyl group, octadecyl group (containing stearyl group), and Ecosyl, triacontyl and tridecyl groups. The alkyl group having a carbon number of 12 or more may be an alkyl group derived from a hydride of a polymer of polybutadiene or polyisoprene or the like. Specific examples of the alkylene group having 12 or more carbon atoms include, for example, a divalent residue in which a hydrogen atom is removed from the above alkyl group.
具有長鏈脂肪族烴基之(甲基)丙烯酸酯之具體例，例如有氫化聚丁二烯二(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、或十八烷基(Stearyl)甲基丙烯酸等。 Specific examples of the (meth) acrylate having a long-chain aliphatic hydrocarbon group, for example, hydrogenated polybutadiene di(meth)acrylate, hydrogenated polyisoprene di(meth)acrylate, etc. An acrylic or methacrylic compound of a diene or hydrogenated polyisoprene skeleton, or stearyl methacrylate or the like.
藉由使用數平均分子量400以上之聚伸烷基二醇(甲基)丙烯酸酯，本發明之組成物可提供韌性或密著 性優異的硬化物。本發明所用之數平均分子量400以上之聚伸烷基二醇(甲基)丙烯酸酯中，(甲基)丙烯酸酯基之數無特別限定，可為1個或複數個。 The composition of the present invention can provide toughness or adhesion by using a polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more. Excellent hardened material. 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以上之聚伸烷基二醇(甲基)丙烯酸酯之具體例，例如有聚乙二醇二(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、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯等。此等之中，從韌性或密著性的觀點，較佳為聚乙二醇二(甲基)丙烯酸酯。 Specific examples of the polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more include, for example, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol. Di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, and the like. Among these, from the viewpoint of toughness or adhesion, polyethylene glycol di(meth)acrylate is preferred.
該化合物之數平均分子量，從韌性或密著性的觀點及與(A)成分之相溶性的觀點，較佳為400~10000，更佳為450~5000，又更佳為500~3000。 The number average molecular weight of the compound is preferably from 400 to 10,000, more preferably from 450 to 5,000, still more preferably from 500 to 3,000, from the viewpoint of toughness or adhesion and compatibility with the component (A).
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，從耐光性的觀點，較佳為具有脂肪族骨架者，該化合物之數平均分子量，從韌性或密著性的觀點及與(A)成分之相溶性的觀點，較佳為100~100000，更佳為500~80000，又更佳為1000~50000。 The urethane acrylate, the epoxy acrylate, and the polyester acrylate which can be used in the present invention are preferably those having an aliphatic skeleton from the viewpoint of light resistance, the number average molecular weight of the compound, from toughness or The viewpoint of the adhesion and the compatibility with the component (A) is preferably from 100 to 100,000, more preferably from 500 to 80,000, still more preferably from 1,000 to 50,000.
其他，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(C)、(D))之具體例，例如有乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、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、甲氧基聚乙烯甲基丙烯酸酯等 之烷氧基聚伸烷基二醇(甲基)丙烯酸酯、環氧乙烷改性雙酚A二(甲基)丙烯酸酯、環氧丙烷改性雙酚A二(甲基)丙烯酸酯、環氧氯丙烷改性雙酚A二(甲基)丙烯酸酯、環氧丙烷改性甘油三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、參(丙烯醯氧基乙基)三聚異氰酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯等。 Other examples of the monofunctional or polyfunctional (meth) acrylate compound (compounds (C), (D)) which can be used in the present invention are, for example, ethylene glycol di(meth)acrylate or propylene glycol di( Methyl) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, Neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate or polypropylene glycol di(meth)acrylate, methoxypolyethylene methacrylate having a number average molecular weight of less than 400 Wait Alkoxy polyalkylene glycol (meth) acrylate, ethylene oxide modified bisphenol A di(meth) acrylate, propylene oxide modified bisphenol A di(meth) acrylate, Epichlorohydrin-modified bisphenol A di(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane Tetrakis (meth) acrylate, dipentaerythritol hexa (meth) acrylate, stilbene (propylene oxyethyl) trimeric isocyanate, methoxy polyethylene glycol (meth) acrylate, and the like.
本發明中，化合物(C)可單獨使用或組合二種以上使用上述單官能(甲基)丙烯酸酯化合物。 In the present invention, the compound (C) may be used singly or in combination of two or more kinds thereof using the above-mentioned monofunctional (meth) acrylate compound.
本發明之組成物中之化合物(C)之含量，從韌性或密著性的觀點，相對於化合物(A)、(B)、(C)及(D)之合計100質量%，較佳為10~80質量%，更佳為15~75質量%，又更佳為20~70質量%。 The content of the compound (C) in the composition of the present invention is preferably 100% by mass based on the total of the compounds (A), (B), (C) and (D) from the viewpoint of toughness or adhesion. 10 to 80% by mass, more preferably 15 to 75% by mass, and still more preferably 20 to 70% by mass.
本發明中，化合物(D)可單獨使用或組合二種以上使用上述多官能(甲基)丙烯酸酯化合物。 In the present invention, the compound (D) may be used singly or in combination of two or more kinds thereof using the above polyfunctional (meth) acrylate compound.
本發明之組成物中之化合物(D)之含量，從不阻礙本發明之效果的觀點，相對於化合物(A)、(B)、(C)及(D)之合計100質量%，較佳為0.1~70質量%，更佳為0.5~60質量%，又更佳為1~50質量%。 The content of the compound (D) in the composition of the present invention is preferably 100% by mass based on the total of the compounds (A), (B), (C) and (D) from the viewpoint of not inhibiting the effects of the present invention. It is 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, still more preferably 1 to 50% by mass.
將本發明之組成物以光或熱聚合得到硬化物。為了促進聚合反應，組成物中可含有聚合起始劑。聚合起始劑無特別限定，例如有自由基聚合起始劑。 The composition of the present invention is polymerized by light or heat to obtain a cured product. In order to promote the polymerization reaction, a polymerization initiator may be contained in the composition. The polymerization initiator is not particularly limited, and examples thereof include a radical polymerization initiator.
自由基聚合起始劑無特別限定，例如有酮過氧化物類、氫過氧化物類、二醯基過氧化物類、二烷基過氧化物類 、過氧酮縮醇類、烷基過氧酸酯類(alkyl perester：過氧酸酯類)、過氧碳酸酯類等。 The radical polymerization initiator is not particularly limited, and examples thereof include ketone peroxides, hydroperoxides, dimercapto peroxides, and dialkyl peroxides. And peroxyketals, alkyl peresters (peroxyesters), peroxycarbonates, and the like.
酮過氧化物類之具體例有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 peroxidation. Things and so on.
氫過氧化物類之具體例有1,1,3,3-四甲基丁基氫過氧化物、枯烯氫過氧化物、t-丁基氫過氧化物、p-萜烷氫過氧化物、二異丙基苯氫過氧化物等。 Specific examples of hydroperoxides include 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and p-decane hydroperoxide. , diisopropylbenzene hydroperoxide, and the like.
二醯基過氧化物類之具體例有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、m-甲苯醯基苯甲醯基過氧化物、琥珀酸過氧化物等。 Specific examples of the dimercapto peroxides include diisobutyl hydrazino peroxide, bis-3,5,5-trimethylhexanol peroxide, dilauroyl peroxide, and benzoyl peroxide. , m-tolylbenzyl benzhydryl peroxide, succinic acid peroxide, and the like.
二烷基過氧化物類之具體例有二枯烯基過氧化物、2,5-二甲基-2,5-二(t-丁基過氧基)己烷、1,3-雙(t-丁基過氧基異丙基)己烷、t-丁基枯烯基過氧化物、二-t-丁基過氧化物、二-t-己基過氧化物、2,5-二甲基-2,5-二(t-丁基過氧基)己烯-3等。 Specific examples of the dialkyl peroxides are dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 1,3-double ( T-butylperoxyisopropyl)hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl Base-2,5-di(t-butylperoxy)hexene-3 and the like.
過氧酮縮醇類之具體例有1,1-二(t-己基過氧基-3,5,5-三甲基)環己烷、1,1-二-t-己基過氧基環己烷、1,1-二-t-丁基過氧基-2-甲基環己烷、1,1-二-t-丁基過氧基環己烷、2,2-二(t-丁基過氧基)丁烷、4,4-雙t-丁基過氧基戊酸丁酯等。 Specific examples of peroxyketals include 1,1-di(t-hexylperoxy-3,5,5-trimethyl)cyclohexane and 1,1-di-t-hexylperoxy ring. Hexane, 1,1-di-t-butylperoxy-2-methylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di(t- Butylperoxy)butane, 4,4-di-t-butylperoxypentanoic acid butyl ester and the like.
烷基過氧酸酯類(alkyl perester：過氧酸酯類)之具體例有1,1,3,3-四甲基丁基過氧基新癸酸酯(decanoate) 、α-枯烯基過氧基新癸酸酯、t-丁基過氧基新癸酸酯、t-己基過氧基新戊酸酯、t-丁基過氧基新戊酸酯、t-己基過氧基戊酸酯、t-丁基過氧基戊酸酯、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯、t-戊基過氧基-2-乙基己酸酯、t-丁基過氧基-2-乙基己酸酯、t-丁基過氧基異丁酸酯、二-t-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、t-戊基過氧基3,5,5-三甲基己酸酯、t-丁基過氧基-3,5,5-三甲基己酸酯、t-丁基過氧基乙酸酯、t-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(Hexanoyl)過氧基己烷、t-己基過氧基-2-乙基己酸酯、t-己基過氧基異丙基單碳酸酯、t-丁基過氧基月桂酸酯、t-丁基過氧基異丙基單碳酸酯、t-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 alkyl peresters (peroxyesters) are 1,1,3,3-tetramethylbutylperoxy neodecanoate (decanoate). , α- cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, t -hexylperoxyvalerate, t-butylperoxyvalerate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-pentyl Oxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxy hexahydro Terephthalate, 1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanoate, t-pentylperoxy 3,5,5- Trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate , dibutylperoxytrimethyl adipate, 2,5-dimethyl-2,5-di-2-ethylhexylyl (Hexanoyl) peroxy hexane, t-hexyl peroxygen 2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxylaurate, t-butylperoxyisopropylmonocarbonate, t- Butylperoxy-2-ethylhexylmonocarbonate, 2,5-dimethyl-2,5-di-benzoylperoxy hexane, and the like.
過氧碳酸酯類之具體例有二-n-丙基過氧基二碳酸酯、二異丙基氧基碳酸酯、二-4-t-丁基環己基過氧基碳酸酯、二-2-乙基己基過氧基碳酸酯、二-sec-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、t-戊基過氧基異丙基碳酸酯、t-丁基過氧基異丙基碳酸酯、t-丁基過氧基-2-乙基己基碳酸酯、1,6-雙(t-丁基過氧基羧氧基)己烷等。 Specific examples of the peroxycarbonate are di-n-propylperoxydicarbonate, diisopropyloxycarbonate, di-4-t-butylcyclohexylperoxycarbonate, and di-2. -ethylhexylperoxycarbonate, di-sec-butylperoxycarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Ester, diisopropyloxydicarbonate, t-pentylperoxyisopropyl carbonate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethyl Hexyl carbonate, 1,6-bis(t-butylperoxycarboxyoxy)hexane, and the like.
自由基聚合起始劑也可使用光自由基聚合起始劑。光自由基聚合起始劑之市售品，可使用例如 IRGACURE(註冊商標)651(IRGACURE 651)、IRGACURE(註冊商標)184(IRGACURE 184)、DAROCUR(註冊商標)1173(DAROCUR 1173)、IRGACURE(註冊商標)2959(IRGACURE 2959)、IRGACURE(註冊商標)127(IRGACURE 127)、IRGACURE(註冊商標)907(IRGACURE 907)、IRGACURE(註冊商標)369(IRGACURE 369)、IRGACURE(註冊商標)379(IRGACURE 379)、DAROCUR(註冊商標)TPO(DAROCUR TPO)、IRGACURE(註冊商標)819(IRGACURE 819)、IRGACURE(註冊商標)784(IRGACURE 784)等(均為商品名、BASF公司製)。 A photoradical polymerization initiator can also be used as the radical polymerization initiator. A commercially available product of a photoradical polymerization initiator, for example, IRGACURE (registered trademark) 651 (IRGACURE 651), IRGACURE (registered trademark) 184 (IRGACURE 184), DAROCUR (registered trademark) 1173 (DAROCUR 1173), IRGACURE (registered trademark) 2959 (IRGACURE 2959), IRGACURE (registered trademark) 127 (IRGACURE 127), IRGACURE (registered trademark) 907 (IRGACURE 907), IRGACURE (registered trademark) 369 (IRGACURE 369), IRGACURE (registered trademark) 379 (IRGACURE 379), DAROCUR (registered trademark) TPO (DAROCUR TPO), IRGACURE (registered trademark) 819 (IRGACURE 819), IRGACURE (registered trademark) 784 (IRGACURE 784), etc. (all trade names, manufactured by BASF Corporation).
本發明中，上述之自由基聚合起始劑可單獨或組合二種以上使用。 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係相對於化合物(A)、(B)、(C)及(D)之合計100質量份，較佳為0.01~10質量份，更佳為0.1~5質量份。 The content of the radical polymerization initiator in the composition of the present invention is 100 parts by mass, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the total of the compounds (A), (B), (C) and (D). Good is 0.1~5 parts by mass.
本發明之組成物中，在不影響本發明之效果的範圍內，可再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、靜電防止劑、滑劑、脫膜劑、難燃劑等之任意的添加劑。此等添加劑可使用公知者。 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, a static preventive agent, a slip agent, and a release agent within a range that does not impair the effects of the present invention. Any additive such as a film or a flame retardant. These additives can be used by a known person.
抗氧化劑例如有酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、維他命系抗氧化劑、內酯系抗氧化劑、胺系抗氧化劑等。 Examples of the antioxidant include 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.
酚系抗氧化劑例如有四[亞甲基-3-(3,5-二-t-丁基-4-羥基苯基)丙酸酯]甲烷、β-(3,5-二-t-丁基-4-羥基苯基)丙酸十八烷酯、1,3,5-三甲基-2,4,6-三(3,5-二-t-丁基-4-羥基苄基)苯、三(3,5-二-t-丁基-4-羥基苄基)三聚異氰酸酯、三[(3,5-二-t-丁基-4-羥基苯基)丙醯氧基乙基]三聚異氰酸酯、2,6-二-t-丁基-4-甲基酚、3,9-雙[1,1-二甲基-2-{β-(3-t-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]十一烷、三(2,6-二甲基-3-羥基-4-t-丁基苄基)三聚異氰酸酯等，例如有IRGANOX 1010、IRGANOX 1076、IRGANOX 1330、IRGANOX 3114、IRGANOX 3125、IRGANOX 3790(以上為BASF公司製)、CYANOX 1790(Cyanamid公司製)、SUMILIZER BHT、SUMILIZER GA-80(以上為住友化學(股)製)等之市售品(均為商品名)。 The phenolic antioxidant is, for example, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, β-(3,5-di-t-butyl) Octadecyl 4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) Benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)trimeric isocyanate, tris[(3,5-di-t-butyl-4-hydroxyphenyl)propoxyl Trimeric isocyanate, 2,6-di-t-butyl-4-methylphenol, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl- 4-hydroxy-5-methylphenyl)propenyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tris(2,6-dimethyl -3-hydroxy-4-t-butylbenzyl)trimeric isocyanate, and the like, for example, IRGANOX 1010, IRGANOX 1076, IRGANOX 1330, IRGANOX 3114, IRGANOX 3125, IRGANOX 3790 (above, BASF), CYANOX 1790 (Cyanamid) Commercial products, such as the company's products, SUMILIZER BHT, and SUMILIZER GA-80 (above the Sumitomo Chemical Co., Ltd.) (all are trade names).
磷系抗氧化劑可使用例如有三(2,4-二-t-丁基苯基)亞磷酸酯、2-[[2,4,8,10-四(1,1-二甲基乙基)二苯並[d，f][1,3,2]二氧雜phosphepine6-基]氧基]-N,N-雙[2-[[2,4,8,10-四(1,1-二甲基乙基)二苯並[d,f][1,3,2]二氧雜phosphepine-6-基]氧基]-乙基]乙胺(ethanamine)、環狀新戊烷四(二(2,6-二-t-丁基-4-甲基苯基))亞磷酸酯、二(十八烷基)季戊四醇二亞磷酸酯等，例如有IRGAFOS 168、IRGAFOS 12、IRGAFOS 38(以上為BASF公司製)、ADK STAB 329K、ADK STAB PEP36、ADK STAB PEP-8(以上為(股)ADEKA製)、Sandstab P-EPQ(Clariant公司製)、Weston 618、Weston 619G、Weston 624(以上為GE公司 製)等之市售品(均為商品名)。 As the phosphorus-based antioxidant, for example, tris(2,4-di-t-butylphenyl)phosphite, 2-[[2,4,8,10-tetra(1,1-dimethylethyl)) can be used. Dibenzo[d,f][1,3,2]dioxaphosphepine6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetra(1,1- Dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6-yl]oxy]-ethyl]ethylamine (ethanamine), cyclic neopentane tetra ( Bis(2,6-di-t-butyl-4-methylphenyl)) phosphite, di(octadecyl)pentaerythritol diphosphite, etc., for example, IRGAFOS 168, IRGAFOS 12, IRGAFOS 38 ( The above is made by BASF), ADK STAB 329K, ADK STAB PEP36, ADK STAB PEP-8 (above is made by ADEKA), Sandstab P-EPQ (made by Clariant), Weston 618, Weston 619G, Weston 624 (above) GE Commercial products (all product names).
硫系抗氧化劑可使用例如二月桂基硫二丙酸酯、二(十八烷基)硫二丙酸酯、二(十四烷基：Myristyl)硫二丙酸酯、月桂基十八烷基硫二丙酸酯、季戊四醇四(3-十二烷基硫丙酸酯)、季戊四醇四(3-月桂基硫丙酸酯)等，例如有DSTP「吉富」、DLTP「吉富」、DLTOIB、DMTP「吉富」(以上為(股)API Corporation製)、Seenox 412S(Shipro化成(股)製)、Cyanox 1212(Cyanamid公司製)、SUMILIZER TP-D(住友化學(股)製)等之市售品(均為商品名)。 As the sulfur-based antioxidant, for example, dilaurylthiodipropionate, dioctadecylthiodipropionate, di(tetradecyl:Myristyl)thiodipropionate, lauryl octadecyl group can be used. Sulfur dipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), pentaerythritol tetrakis(3-lauryl thiopropionate), etc., for example, DSTP "Gifford", DLTP "Gifford", DLTOIB, DMTP Commercial products such as "Jifu" (manufactured by API Corporation), Seenox 412S (Shipro Chemical Co., Ltd.), Cyanox 1212 (Cyanamid), and SUMILIZER TP-D (Sumitomo Chemical Co., Ltd.) (all are product names).
維他命系抗氧化劑例如維他命E、2,5,7,8-四甲基-2(4’,8’,12’-三甲基十三烷基)苯並呋喃(coumarone)-6-醇等，可使用例如IRGANOX E201(BASF公司製)等之市售品。 Vitamin antioxidants such as vitamin E, 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)benzofuran-6-ol, etc. For example, a commercially available product such as IRGANOX E201 (manufactured by BASF Corporation) can be used.
內酯系抗氧化劑可使用日本特開平7-233160號公報、特開平7-247278號公報所記載者。又，HP-136(商品名、BASF公司製、化合物名：5,7-二-t-丁基-3-(3,4-二甲基苯基)-3H-苯並呋喃-2-酮)等。 For the lactone-based antioxidant, those described in JP-A-H07-233160 and JP-A-7-247278 can be used. Further, HP-136 (trade name, manufactured by BASF Corporation, compound name: 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one )Wait.
胺系抗氧化劑例如有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)等之市售品(均為商品名)。 Examples of the amine-based antioxidant include commercially available products (all trade names) such as IRGASTAB FS 042 (manufactured by BASF Corporation) and GENOX EP (manufactured by Crompton Corporation, compound name: dialkyl-N-methylamine oxide).
此等抗氧化劑可單獨使用或組合二種以上使用。 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之含量，從不阻礙本發 明之效果的觀點，相對於化合物(A)、(B)、(C)及(D)之合計100質量份，較佳為0.005~5質量份，更佳為0.02~2質量份。 The content of the antioxidant in the composition of the present invention never hinders the hair The viewpoint of the effect is preferably 0.005 to 5 parts by mass, more preferably 0.02 to 2 parts by mass, per 100 parts by mass of the total of the compounds (A), (B), (C) and (D).
光安定劑可使用紫外線吸收劑或受阻胺系光安定劑等任意者，較佳為受阻胺系光安定劑。具體例有ADK STAB LA-52、LA-57、LA-62、LA-63、LA-67、LA-68、LA-77、LA-82、LA-87、LA-94(以上為ADEKA製)、Tinuvin 123、144、440、662、765、770DF、Tinuvin XT 850 FF、Tinuvin XT 855 FF、Chimassorb 2020、119、944(以上為BASF公司製)、Hostavin N30(Hoechst公司製)、Cyasorb UV-3346、UV-3526(Cytec公司製)、Uval 299(GLC公司製)、Sanduvor PR-31(Clariant公司製)等(均為商品名)。 As the photostabilizer, any of an ultraviolet absorber or a hindered amine light stabilizer may be used, and a hindered amine light stabilizer is preferred. Specific examples are ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA-87, LA-94 (above, ADEKA) , Tinuvin 123, 144, 440, 662, 765, 770DF, Tinuvin XT 850 FF, Tinuvin XT 855 FF, Chimassorb 2020, 119, 944 (above, BASF), Hostavin N30 (made by Hoechst), Cyasorb UV-3346 UV-3526 (manufactured by Cytec Co., Ltd.), Uval 299 (manufactured by GLC Co., Ltd.), and Sanduvor PR-31 (manufactured by Clariant Co., Ltd.) (all are trade names).
紫外線吸收劑之具體例有ADKSTAB LA-31、ADKSTAB LA-32、ADKSTAB LA-36、ADKSTAB LA-29、ADKSTAB LA-46、ADKSTAB LA-F70、ADKSTAB 1413(以上為ADEKA公司製)、Tinuvin P、Tinuvin 234、Tinuvin 326、Tinuvin 328、Tinuvin 329、Tinuvin 213、Tinuvin 571、Tinuvin 1577ED、Chimassorb 81、Tinuvin 120(以上為BASF公司製)等。 Specific examples of the ultraviolet absorber include ADKSTAB LA-31, ADKSTAB LA-32, ADKSTAB LA-36, ADKSTAB LA-29, ADKSTAB LA-46, ADKSTAB LA-F70, ADKSTAB 1413 (above, ADEKA), Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 213, Tinuvin 571, Tinuvin 1577 ED, Chimassorb 81, Tinuvin 120 (manufactured by BASF Corporation, etc.).
此等光安定劑可單獨使用或組合二種以上使用。 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之含量，從不阻礙本發明之效果的觀點，相對於化合物(A)、(B)、(C)及(D)之合 計100質量份，較佳為0.005~5質量份，更佳為0.02~2質量份。 The content of the photosensitizer in the composition of the present invention is relative to the compound (A), (B), (C) and (D) from the viewpoint of not inhibiting the effects of the present invention. It 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，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%為氧化鋯、球狀二氧化矽、化合物(A)、及任意由化合物(B)、(C)、(D)所構成。 The composition of the present invention is, for example, 90% by weight or more, 95% by weight or more, 98% by weight or more, 99% by weight or more, and 100% by weight of zirconia, spherical cerium oxide, compound (A), and optionally compound ( B), (C), (D).
本發明之組成物可將氧化鋯、球狀二氧化矽及上述(甲基)丙烯酸酯化合物，以所定的量比混合而調製。混合方法無特別限定，可使用攪拌機(mixer)等任意公知手段。又，可在常溫、冷卻下或加熱下，常壓、減壓下或加壓下混合。 The composition of the present invention can be prepared by mixing zirconia, spherical cerium oxide and the above (meth) acrylate compound in a predetermined amount ratio. The mixing method is not particularly limited, and any known means such as a mixer can be used. Further, it may be mixed under normal pressure, under cooling or under heating under normal pressure, reduced pressure or under pressure.
本發明之組成物可提供可見光區域之反射率高，白色性優異，耐熱性及耐光性優異，較少變黃，且與周邊構件(特別是導線架)之密著性優異的硬化物，適合作為光半導體用之反射材原料使用。 The composition of the present invention can provide a cured product having a high reflectance in a visible light region, excellent whiteness, excellent heat resistance and light resistance, less yellowing, and excellent adhesion to peripheral members (especially lead frames). It is used as a material for a reflective material for an optical semiconductor.
[硬化物] [hardened material]
本發明之硬化物係由含有金剛烷骨架之(甲基)丙烯酸樹脂所構成，且含有氧化鋯與球狀二氧化矽者。 The cured product of the present invention is composed of a (meth)acrylic resin containing an adamantane skeleton, and contains zirconia and spherical ruthenium dioxide.
含有金剛烷骨架之(甲基)丙烯酸樹脂係含有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸樹脂，經取代之金剛烷基係如針對本發明之組成物，如上述說明者。 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 is as described for the composition of the present invention, as described above. .
氧化鋯及球狀二氧化矽分別係針對本發明之組成物，如上述說明者。 Zirconium oxide and spheroidal cerium oxide are respectively directed to the composition of the present invention, as described above.
本發明之硬化物，例如將上述說明之本發明的組成物進行聚合硬化而得。硬化係將組成物藉由光或熱聚合，使其硬化。硬化條件係考慮使用之聚合起始劑的分解特性等，來適當決定。 The cured product of the present invention is obtained, for example, by polymerizing and curing the composition of the present invention described above. The hardening system hardens the composition by light or heat polymerization. The curing conditions are appropriately determined in consideration of the decomposition characteristics of the polymerization initiator used and the like.
本發明之硬化物，例如適合作為光半導體用之反射材等使用。 The cured product of the present invention is suitably used, for example, as a reflective material for an optical semiconductor.
[反射材] [reflective material]
可使用上述說明之本發明之組成物或本發明之硬化物作為反射材。 The composition of the present invention described above or the cured product of the present invention can be used as the reflective material.
使用使本發明之組成物硬化而得之硬化物的反射材，即使長時間使用，反射率也不會降低，可見光區域之反射率高，與周邊構件之密著性優異。 When the reflective material obtained by hardening the composition of the present invention is used, the reflectance does not decrease even when used for a long period of time, and the reflectance in the visible light region is high, and the adhesion to the peripheral member is excellent.
本發明之反射材係使用本發明之組成物，可藉由轉移成形(transfer molding)或壓縮成形來製造。 The reflective material of the present invention can be produced by transfer molding or compression molding using the composition of the present invention.
轉移成形時，使用轉移成形機，例如可以成形壓力5~20N/mm2、成形溫度120~190℃、成形時間30~500秒、較佳為成形溫度150~185℃、成形時間30~180秒成形。壓縮成形時，可使用壓縮成形機，例如以成形溫度120~190℃、成形時間30~600秒、較佳為成形溫度130~160℃、成形時間30~300秒成形。上述任一成形法，可以150~185℃、0.5~24小時進行後硬化。 In the case of transfer molding, a transfer molding machine can be used, for example, a molding pressure of 5 to 20 N/mm 2 , a molding temperature of 120 to 190 ° C, a molding time of 30 to 500 seconds, a molding temperature of 150 to 185 ° C, and a molding time of 30 to 180 seconds. Forming. In the compression molding, a compression molding machine can be used, for example, at a molding temperature of 120 to 190 ° C, a molding time of 30 to 600 seconds, a molding temperature of 130 to 160 ° C, and a molding time of 30 to 300 seconds. Any of the above molding methods may be post-hardened at 150 to 185 ° C for 0.5 to 24 hours.
又，也可藉由液狀樹脂射出成形、插入成形、接合加工或塗佈加工、晶圓級封裝(WLP)之工法等得到 成形體。 Further, it can also be obtained by liquid resin injection molding, insert molding, bonding processing or coating processing, wafer level packaging (WLP), or the like. Shaped body.
此外，可藉由例如與UV硬化成形等之光硬化樹脂成形同樣的方法得到成形體。 Further, a molded body can be obtained by, for example, a method similar to the formation of a photocurable resin such as UV-curing.
又，將本發明之組成物以轉移成形、壓縮成形、液狀樹脂射出成形、插入成形、接合加工或塗佈加工、晶圓級封裝(WLP)等成形時，也可進行預備聚合。 Further, when the composition of the present invention is subjected to transfer molding, compression molding, liquid resin injection molding, insert molding, bonding processing or coating processing, or wafer level packaging (WLP) molding, preliminary polymerization may be performed.
本發明之反射材係可見光區域之反射率高，即使長時間使用，反射率之降低較小。本發明之反射材在波長450nm下之光反射率可達成初期值較佳為85%以上，更佳為90%以上，又更佳為95%以上，150℃、1000小時之劣化試驗後之光反射率，較佳為80%以上，更佳為85%以上，又更佳為90%以上。又，光反射率可藉由實施例所記載的方法求得。 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 can be preferably 85% or more, more preferably 90% or more, still more preferably 95% or more, and 150° C., 1000 hours after the deterioration test. The reflectance is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more. Further, the light reflectance can be obtained 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係含有上述說明之本發明之反射材。光半導體發光裝置之其他的構成可為公知者。 The optical semiconductor light-emitting device of the present invention contains the above-described reflective material of the present invention. Other configurations of the optical semiconductor light-emitting device can be known.
[光半導體元件搭載用基板] [Substrate for mounting optical semiconductor elements]
本發明之光半導體元件搭載用基板係具有由導線架及反射材所構成之凹部，反射材是由含有氧化鋯與球狀二氧化矽，且鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯作為單體之樹脂成形體所構成者。 The optical semiconductor element mounting substrate of the present invention has a concave portion composed of a lead frame and a reflective material, and the reflective material contains zirconia and spherical ruthenium dioxide, and is bonded with an adamantyl group or a substituted adamantyl group. The (meth) acrylate is composed of a resin molded body of a monomer.
又，另外的態樣係本發明之光半導體元件搭載用基板 係由2個導線架及位於2個導線架之間的反射材所構成，反射材含有氧化鋯與球狀二氧化矽，且由鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯作為單體之樹脂成形體所構成者。 In addition, the other aspect is the substrate for mounting an optical semiconductor element of the present invention. It consists of two lead frames and a reflective material between two lead frames. The reflective material contains zirconia and spherical ceria, and is bonded with adamantyl or substituted adamantyl (A) The acrylate is a resin molded body of a monomer.
反射材為含有氧化鋯與球狀二氧化矽，且由鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯作為單體之樹脂成形體所構成者時，可提高反射材之反射率及耐熱性，又，可減低光半導體元件搭載用構件製造時所產生之導線架(frame)成形體之變形及未充填。 When the reflective material is a resin molded body containing zirconia and spherical cerium oxide and a (meth) acrylate having an adamantyl group or a substituted adamantyl group bonded thereto as a monomer, the reflection can be improved. In addition, the reflectance and the heat resistance of the material can reduce the deformation and unfilling of the frame molded body which is generated when the optical semiconductor element mounting member is manufactured.
本發明中使用之含有氧化鋯與球狀二氧化矽，且以鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯作為單體之樹脂成形體，例如將含有氧化鋯、球狀二氧化矽與黏度為1~1000mPa．s之鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物的組成物(以下也稱為「本發明之組成物」)進行硬化、成形而得。 The resin molded body containing zirconia and spherical cerium oxide and having a (meth) acrylate bonded with an adamantyl group or a substituted adamantyl group as a monomer, for example, which will contain zirconia , spherical cerium oxide and viscosity of 1~1000mPa. The composition of the (meth) acrylate compound of the adamantyl group or the substituted adamantyl group (hereinafter also referred to as "the composition of the present invention") is bonded and formed.
[光半導體裝置] [Optical semiconductor device]
本發明之光半導體裝置係具備上述本發明之光半導體元件搭載用基板、搭載於光半導體元件搭載基板之導線架上的光半導體元件及被覆光半導體元件的封裝樹脂者。 The optical semiconductor device of the present invention includes the optical semiconductor element mounting substrate of the present invention, the optical semiconductor element mounted on the lead frame of the optical semiconductor element mounting substrate, and the encapsulating resin covering the optical semiconductor element.
使用圖面再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係表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 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)表示導線架10。 Figure 1 (a) shows the lead frame 10.
圖1(b)表示在圖1(a)之導線架10上，使作為反射材21之樹脂成形體成形的光半導體元件搭載用基板20。光半導體元件搭載用基板20具有由導線架10及反射材21所構成之底面與由反射材21所構成之內周側面所構成之凹部。構成反射材21之樹脂成形體係使含有氧化鋯、球狀二氧化矽及黏度為1~1000mPa．s之鍵結有金剛烷基或經取代之金剛烷基之(甲基)丙烯酸酯化合物的組成物硬化者。 Fig. 1 (b) shows an optical semiconductor element mounting substrate 20 in which a resin molded body as the reflecting 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 a bottom surface formed by the lead frame 10 and the reflection material 21 and an inner circumferential side surface formed of the reflective material 21. The resin forming system constituting the reflecting material 21 is made to contain zirconia, spherical cerium oxide and a viscosity of 1 to 1000 mPa. The composition of s is hardened by a composition of an adamantyl group or a substituted adamantyl (meth) acrylate compound.
圖1(c)係於圖1(b)之光半導體元件搭載用基板之導線架上搭載光半導體元件31，使用線(wire)32接合光半導體元件31與未搭載光半導體元件31之另一方之導線架，以透明樹脂(封裝樹脂)33封閉凹部的光半導體裝置30。封裝樹脂之內部可含有使藍色等之發光轉換成白色用的螢光體34。 1(c), the optical semiconductor element 31 is mounted on the lead frame of the optical semiconductor element mounting substrate of FIG. 1(b), and the optical semiconductor element 31 and the other optical semiconductor element 31 are not mounted by the wire 32. The lead frame is an optical semiconductor device 30 that closes the recess with a transparent resin (packaging resin) 33. The inside of the encapsulating resin may contain a phosphor 34 for converting light such as blue to white.
又，表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外之實施形態的概略剖面圖。 Moreover, 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)表示導線架10。 Figure 2 (a) shows the lead frame 10.
圖2(b)表示圖2(a)之導線架10之間，使作為反射材21之樹脂成形體成型的光半導體元件搭載用基板20。光半導體元件搭載用基板20具備導線架10與位於導線架10之間的反射材21。 2(b) shows the optical semiconductor element mounting substrate 20 in which the resin molded body of the reflecting 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 positioned between the lead frames 10 .
圖2(c)係表示具備圖2(b)之光半導體元件搭載用基板的光半導體裝置30。導線架10上搭載光半導體元件31， 藉由接合線32進行電連接後，以轉移成形或壓縮成形等的方法，將由透明封裝樹脂33所構成之封裝樹脂部，以一次硬化成形進行光半導體元件31之封閉後，藉由薄切(dicing)形成單片化。封裝樹脂之內部可含有使藍色等之發光轉換成白色用的螢光體34。 FIG. 2(c) shows an optical semiconductor device 30 including the optical semiconductor element mounting substrate of FIG. 2(b). The optical semiconductor component 31 is mounted on the lead frame 10, After the electrical connection is made by the bonding wires 32, the encapsulating resin portion made of the transparent encapsulating resin 33 is subjected to one-time hardening molding to close the optical semiconductor element 31 by transfer molding or compression molding, and then thin-cut ( Dicing) forms a singulation. The inside of the encapsulating resin may contain a phosphor 34 for converting light such as blue to white.
光半導體元件搭載用基板之各部份的尺寸、形狀無特別限定，可適當設定。 The size and shape of each portion of the substrate for mounting an optical semiconductor element are not particularly limited, and can be appropriately set.
作為反射材使用之樹脂成形體之成形可使用已知方法成形，較佳為轉移成形。藉此可確保高的生產性。 The molding of the resin molded body used as the reflecting material can be formed by a known method, and is preferably a transfer molding. This ensures high productivity.
轉移成形係使用轉移成形機，例如可以成形壓力5~20N/mm2、成形溫度120~190℃、成形時間30~500秒、較佳為成形溫度150~185℃、成形時間30~180秒成形。可再以例如150~185℃、0.5~24小時進行後硬化。 The transfer molding system uses a transfer molding machine, for example, a molding pressure of 5 to 20 N/mm 2 , a molding temperature of 120 to 190 ° C, a molding time of 30 to 500 seconds, a molding temperature of 150 to 185 ° C, and a molding time of 30 to 180 seconds. . The post-hardening can be carried out, for example, at 150 to 185 ° C for 0.5 to 24 hours.
光半導體元件無特別限定，可使用任意已知者。 The optical semiconductor element is not particularly limited, and any known one can be used.
封裝樹脂(封裝材)例如由環氧樹脂、聚矽氧樹脂、丙烯酸酯樹脂等所構成。 The encapsulating resin (packaging material) is composed of, for example, an epoxy resin, a polyoxymethylene resin, an acrylate resin, or the like.
光半導體裝置之各部份的尺寸、形狀無特別限定，可適當設定。 The size and shape of each portion of the optical semiconductor device are not particularly limited and can be appropriately set.
[實施例] [Examples]
以下詳細說明本發明之實施例，本發明不受此等實施例所限定。 The embodiments of the present invention are described in detail below, and the present invention is not limited by the embodiments.
在各實施例及比較例中所得之硬化物的物性評估方法 係如下述。 Physical property evaluation method of cured product obtained in each of Examples and Comparative Examples It is as follows.
(1)光反射率測定 (1) Light reflectance measurement
使用安裝了多用途大型試樣室單元[(股)島津製作所製，商品名：「MPC-2200」]之自動記錄式分光光度計[(股)島津製作所製，商品名：「UV-2400PC」]，測定硬化物測試片的光反射率。測定硬化物測試片之初期值之光反射率後，在烘箱中以150℃加熱所定時間後，測定加熱後之硬化物測試片的光反射率。 An automatic recording spectrophotometer (manufactured by Shimadzu Corporation, product name: "UV-2400PC" manufactured by Shimadzu Corporation (manufactured by Shimadzu Corporation, product name: "MPC-2200") ], the light reflectance of the cured test piece was measured. After measuring the light reflectance of the initial value of the cured test piece, it was heated in an oven at 150 ° C for a predetermined period of time, and then the light reflectance of the cured test piece after heating was measured.
實施例1 Example 1
秤取化合物(A)(金剛烷基或經取代之金剛烷基進行酯鍵結之(甲基)丙烯酸酯化合物)為1-金剛烷基甲基丙烯酸酯(黏度：15mPa．s)20g、化合物(B)(具有極性基之單官能丙烯酸酯)為4-羥基丁基丙烯酸酯10g、化合物(C)(化合物(A)、(B)以外之單官能(甲基)丙烯酸酯化合物)為十八烷基丙烯酸酯60g、化合物(D)(多官能(甲基)丙烯酸酯化合物)為三(2-丙烯醯氧基乙基)三聚氰酸酯(isocyanurate)(FA731)10g、聚合起始劑為1,1-雙(3,3-二甲基丁基過氧)環己烷1g，將此等混合得到調配液。 Weighing compound (A) (adamantyl or substituted adamantyl group for ester-bonded (meth) acrylate compound) is 1-adamantyl methacrylate (viscosity: 15 mPa.s) 20 g, compound (B) (monofunctional acrylate having a polar group) is 10 g of 4-hydroxybutyl acrylate, and the compound (C) (monofunctional (meth) acrylate compound other than the compound (A), (B)) is ten 60 g of octadecyl acrylate and compound (D) (polyfunctional (meth) acrylate compound) are tris(2-propenyloxyethyl) isocyanurate (FA731) 10 g, polymerization initiation The agent was 1 g of 1,1-bis(3,3-dimethylbutylperoxy)cyclohexane, and these were mixed to obtain a formulation liquid.
此調配液15質量%中，添加球狀二氧化矽75質量%、氧化鋯(第一稀元素化學工業(股)製、商品名：UEP)10質量%，使用自轉、公轉混合器((股)thinky製、商品名：脫泡練太郎)混合攪拌得到組成物。 In the blending liquid, 15% by mass, spheroidal cerium oxide (75% by mass), zirconia (manufactured by the first rare element chemical industry, product name: UEP) was added in an amount of 10% by mass, and a self-rotating or revolving mixer was used. )Thinky system, trade name: defoaming Taro, mixing and stirring to obtain a composition.
其次，將此組成物藉由轉移成形，以150℃成形得到硬化物。物性之評價結果如表1所示。 Next, this composition was formed by transfer molding to form a cured product at 150 °C. The evaluation results of physical properties are shown in Table 1.
實施例2 Example 2
除了球狀二氧化矽使用70質量%，氧化鋯使用15質量份外，與實施例1同樣得到組成物，形成硬化物。物性之評價結果如表1所示。 A composition was obtained in the same manner as in Example 1 except that the spherical cerium oxide was used in an amount of 70% by mass and the zirconia was used in an amount of 15 parts by mass to form a cured product. The evaluation results of physical properties are shown in Table 1.
實施例3 Example 3
除了球狀二氧化矽使用65質量%，氧化鋯使用20質量份外，與實施例1同樣得到組成物，形成硬化物。物性之評價結果如表1所示。 A composition was obtained in the same manner as in Example 1 except that the spherical cerium oxide was used in an amount of 65% by mass and the zirconia was used in an amount of 20 parts by mass to form a cured product. The evaluation results of physical properties are shown in Table 1.
比較例1 Comparative example 1
在實施例1所得之配合液15質量%中，添加球狀二氧化矽75質量%、氧化鈦10質量%的比例，與實施例1同樣得到組成物，形成硬化物。物性之評價結果如表1所示。 In a ratio of 75 mass% of spherical ceria and 10 mass% of titanium oxide, the 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
在實施例1所得之配合液15質量%中，添加球狀二氧化矽70質量%、氧化鈦15質量%的比例，得到組成物。 In a proportion of 15% by mass of the compounding liquid obtained in Example 1, 70% by mass of spherical cerium oxide and 15% by mass of titanium oxide were added to obtain a composition.
所得之組成物的黏度高，流動性差，因此無法成形，也無法得到硬化物。 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
在實施例1所得之配合液15質量%中，添加球狀二氧化矽65質量%、氧化鈦20質量%的比例，得到組成物。 In the amount of 15% by mass of the compounding liquid obtained in Example 1, a ratio of spherical cerium oxide of 65% by mass and titanium oxide of 20% by mass was added to obtain a composition.
所得之組成物的黏度高，流動性差，因此無法成形，也無法得到硬化物。 The obtained composition has high viscosity and poor fluidity, so that it cannot be formed and a cured product cannot be obtained.
實施例4~6 Example 4~6
由實施例1~3所製造之組成物所所得之樹脂成形體作為反射材使用，製作如圖1(c)所示之光半導體裝置。 The resin molded body obtained from the compositions produced in Examples 1 to 3 was used as a reflective material to produce an optical semiconductor device as shown in Fig. 1 (c).
將實施例1~3所製造之組成物與導線架，以150℃進行轉移成形，得到具有凹部之光半導體元件搭載用基板。其次，凹部之導線架底面搭載光半導體元件，而光半導體元件與未搭載光半導體元件之另一方的導線架底面藉由線接合連接。然後，將聚矽氧樹脂填充於凹部，使硬化形成封裝樹脂(封裝材)，得到光半導體裝置。 The composition produced in each of Examples 1 to 3 and the lead frame were subjected to transfer molding at 150 ° C to obtain a substrate for mounting an optical semiconductor element having a concave portion. Next, the optical semiconductor element is mounted on the bottom surface of the lead frame of the concave portion, and the bottom surface of the lead frame of the other optical semiconductor element and the optical semiconductor element is not connected by wire bonding. Then, the polyoxyxylene resin is filled in the concave portion, and the encapsulating resin (encapsulating material) is formed by hardening to obtain an optical semiconductor device.
[產業上之可利用性] [Industrial availability]
本發明之組成物及硬化物適合作為光半導體 用之反射材的原料使用。 The composition and cured product of the present invention are suitable as an optical semiconductor It is used as a raw material for reflective materials.
本發明之光半導體元件搭載用基板及光半導體裝置適合作為照明、顯示器用光源、引導顯示板、車載照明、信號燈、緊急用燈、行動電話、錄影機等各種OA機器、電氣電子機器及零件、汽車零件等使用。 The optical semiconductor element mounting substrate and the optical semiconductor device of the present invention are suitable as various OA equipment, electrical and electronic equipment and parts such as illumination, display light source, guidance display panel, vehicle illumination, signal light, emergency light, mobile phone, video recorder, and the like. Use for car parts, etc.
上述略為詳細說明本發明之實施形態及/或實施例，但是熟悉該項技藝者由本發明之新穎的揭示及效果，在實質上不離本發明之技術內容，可容易對於此等例示之實施形態及/或實施例加以變更。因此，此等變更也包含於本發明之範圍內。 The embodiments and/or the embodiments of the present invention are described in detail above, but those skilled in the art will be able to readily embody the present invention without departing from the technical scope of the present invention. / or the embodiment is changed. Accordingly, such changes are also intended to be included within the scope of the present invention.
在此引用本案巴黎優先權基礎案之日本申請說明書的全部內容。 The entire contents of the Japanese application specification for the Paris priority basis of this case are cited here.
10‧‧‧導線架 10‧‧‧ lead frame
21‧‧‧反射材 21‧‧‧Reflective material
31‧‧‧光半導體元件 31‧‧‧Optical semiconductor components
32‧‧‧接合線 32‧‧‧bonding line
33‧‧‧封裝樹脂 33‧‧‧Packaging resin
34‧‧‧螢光體 34‧‧‧Fertior
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012219591 | 2012-10-01 | ||
| JP2012222544 | 2012-10-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201428043A true TW201428043A (en) | 2014-07-16 |
Family
ID=50434600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102135516A TW201428043A (en) | 2012-10-01 | 2013-10-01 | Composition for reflective material, and optical semiconductor light-emitting device produced using same |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW201428043A (en) |
| WO (1) | WO2014054256A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6359889B2 (en) * | 2014-06-23 | 2018-07-18 | 出光興産株式会社 | Thermosetting composition and method for producing thermosetting resin |
| JP6666947B2 (en) * | 2018-04-27 | 2020-03-18 | 出光興産株式会社 | Thermosetting composition and method for producing the thermosetting resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223704A (en) * | 1989-11-29 | 1991-10-02 | Mitsubishi Rayon Co Ltd | Optical element |
| JP5168337B2 (en) * | 2010-10-28 | 2013-03-21 | 大日本印刷株式会社 | Reflective material composition, reflector and semiconductor light emitting device |
-
2013
- 2013-09-27 WO PCT/JP2013/005768 patent/WO2014054256A1/en active Application Filing
- 2013-10-01 TW TW102135516A patent/TW201428043A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014054256A1 (en) | 2014-04-10 |
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