JP5553749B2 - Amorphous siliceous powder, production method and use thereof - Google Patents
Amorphous siliceous powder, production method and use thereof Download PDFInfo
- Publication number
- JP5553749B2 JP5553749B2 JP2010512008A JP2010512008A JP5553749B2 JP 5553749 B2 JP5553749 B2 JP 5553749B2 JP 2010512008 A JP2010512008 A JP 2010512008A JP 2010512008 A JP2010512008 A JP 2010512008A JP 5553749 B2 JP5553749 B2 JP 5553749B2
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- JP
- Japan
- Prior art keywords
- powder
- pyridine
- siliceous powder
- amorphous siliceous
- amorphous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000843 powder Substances 0.000 title claims description 152
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 161
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 81
- 239000004065 semiconductor Substances 0.000 claims description 48
- 238000003795 desorption Methods 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 36
- 239000003822 epoxy resin Substances 0.000 claims description 35
- 239000003566 sealing material Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 19
- 239000011342 resin composition Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 239000008393 encapsulating agent Substances 0.000 description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
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- 235000012239 silicon dioxide Nutrition 0.000 description 9
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- -1 curing accelerators Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
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- 229910001882 dioxygen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XHCVSVGGSQSNRB-UHFFFAOYSA-N C#C.[O-][N+]#N Chemical compound C#C.[O-][N+]#N XHCVSVGGSQSNRB-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
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- 239000005077 polysulfide Substances 0.000 description 1
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- 150000008117 polysulfides Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XQQWBPOEMYKKBY-UHFFFAOYSA-H trimagnesium;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O XQQWBPOEMYKKBY-UHFFFAOYSA-H 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- 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
-
- 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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Silicon Compounds (AREA)
- Sealing Material Composition (AREA)
- Glanulating (AREA)
Description
本発明は、非晶質シリカ質粉末、その製造方法及び用途に関する。 The present invention relates to an amorphous siliceous powder, a method for producing the same, and an application thereof.
近年、地球環境保全への意識の高まりから、半導体素子の封止に用いられる半導体封止材には、環境負荷の大きいアンチモン化合物や臭素化エポキシ樹脂などの有害な難燃剤を使用せずに難燃性を付与すること、鉛を含有しない鉛フリーハンダへの耐熱性を付与することなどが求められている。半導体封止材は主に、エポキシ樹脂、フェノール樹脂硬化剤、硬化促進剤、無機質充填材などから構成されるが、上記のような要求特性を満たすために、エポキシ樹脂、フェノール樹脂などに芳香環を多く含む難燃性、及び耐熱性の高い構造のものを適用する方法、無機質充填材を高充填する方法などがとられている。しかし、これらの方法では、半導体封止材の封止時の粘度が上昇する傾向にある。 In recent years, due to increasing awareness of global environmental conservation, it is difficult to use semiconductor flame retardants such as antimony compounds and brominated epoxy resins, which have a large environmental impact, in semiconductor encapsulants used for encapsulating semiconductor elements. It is required to impart flammability and to impart heat resistance to lead-free solder that does not contain lead. Semiconductor encapsulants are mainly composed of epoxy resins, phenol resin curing agents, curing accelerators, inorganic fillers, etc. In order to satisfy the above required characteristics, epoxy rings, phenol resins, etc. have aromatic rings. For example, a method of applying a structure having a high flame retardancy and high heat resistance, a method of highly filling an inorganic filler, and the like are taken. However, these methods tend to increase the viscosity at the time of sealing the semiconductor sealing material.
一方、電子機器の小型軽量化、高性能化の要求に対応して、半導体の内部構造は、素子の薄型化、金線の小径化、ロングスパン化、及び配線ピッチの高密度化が急速に進展している。このような半導体を、高粘度化した半導体封止材を用いて封止すると、金線変形、金線切断、半導体素子の傾斜、狭隙未充填などの不良を増大させる結果となる。このため、半導体封止材には、難燃性を有し、かつ、封止時の粘度を低下させ、成形不良を低減することが強く求められている。 On the other hand, in response to demands for smaller and lighter electronic devices and higher performance, the internal structure of semiconductors is rapidly becoming thinner, gold wires having a smaller diameter, longer spans, and higher wiring pitches. It is progressing. When such a semiconductor is sealed with a semiconductor sealing material having a high viscosity, defects such as gold wire deformation, gold wire cutting, inclination of the semiconductor element, and narrow gap unfilling result. For this reason, the semiconductor encapsulant is strongly required to have flame retardancy, to reduce the viscosity at the time of encapsulation, and to reduce molding defects.
これらの要求を満たすべく、半導体封止材に使用するエポキシ樹脂やフェノール樹脂硬化剤を改良する手法などによって、低粘度化を図り、成形性を向上させるといった手法がとられている(特許文献1、及び2参照)。また、硬化促進剤の改良としては、エポキシ樹脂の硬化開始温度を上昇させる目的で、硬化性を抑制する成分を用いて反応性の基質を保護する、いわゆる潜在化と呼ばれる手法がとられている(特許文献3、及び4参照)。
無機質充填材の改良としては、高充填しても封止材の粘度が上昇しないように、粒度分布を調整する方法などがとられている(特許文献5、及び6参照)。しかしながら、これらの手法では低粘度効果、成形性向上効果は十分ではなく、無機質充填材を高充填でき、かつ封止時の粘度を低下させ、成形性を更に向上させた半導体封止材は未だない。In order to satisfy these requirements, a technique has been adopted in which the viscosity is reduced and the moldability is improved by a technique of improving an epoxy resin or a phenol resin curing agent used for a semiconductor sealing material (Patent Document 1). And 2). As an improvement of the curing accelerator, for the purpose of increasing the curing start temperature of the epoxy resin, a so-called latent method is employed in which a reactive substrate is protected using a component that suppresses curability. (See Patent Documents 3 and 4).
As an improvement of the inorganic filler, a method of adjusting the particle size distribution or the like has been adopted so that the viscosity of the sealing material does not increase even when the filler is highly filled (see Patent Documents 5 and 6). However, these methods do not provide a low-viscosity effect and a moldability-improving effect, and a semiconductor encapsulant that can be highly filled with an inorganic filler, has a reduced viscosity at the time of sealing, and has further improved the moldability. Absent.
本発明の目的は、無機質充填材を高充填しても、封止時の粘度が低く、成形性を更に向上させた半導体封止材を提供することであり、その調製に好適な非晶質シリカ質粉末及びその製造方法を提供することである。 An object of the present invention is to provide a semiconductor sealing material that has a low viscosity at the time of sealing even when highly filled with an inorganic filler and has further improved moldability, and is suitable for its preparation. It is to provide a siliceous powder and a method for producing the same.
本発明は、非晶質シリカ質粉末にピリジンを吸着させた後の、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比であるL/Bが0.8以下であり、150℃以上550℃未満の加熱時におけるピリジンの総脱離量Aに占める、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bの割合である(B/A)×100%が20%以上であり、かつAl 2 O 3 を0.1〜20質量%含有することを特徴とする非晶質シリカ質粉末である。
また、本発明においては、非晶質シリカ質粉末にピリジンを吸着させた後の、150℃以上550℃未満の加熱時におけるピリジンの総脱離量Aに占める、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bの割合、(B/A)×100%が20%以上であることが好ましい。
また、本発明の非晶質シリカ質粉末は、比表面積が0.5〜45m2/g、平均粒子径が0.1〜60μm、平均球形度が0.80以上であることが好ましい。
また、本発明は、本発明の非晶質シリカ質粉末を含有する無機質粉末である。
本発明にあっては、前記無機質粉末は、本発明以外の非晶質シリカ質粉末及び/又はアルミナ質粉末であることが好ましい。
In the present invention, the amount of pyridine desorbed during heating at 450 ° C. or higher and lower than 550 ° C. after pyridine is adsorbed on amorphous siliceous powder, and pyridine desorption during heating at 150 ° C. or higher and lower than 250 ° C. the ratio of the Hanareryou B L / B is Ri der 0.8, to the total desorption amount a of pyridine at heating of less than 0.99 ° C. or higher 550 ° C., during the heating of less than 0.99 ° C. or higher 250 ° C. Amorphous siliceous material characterized in that (B / A) × 100%, which is the ratio of pyridine elimination amount B, is 20% or more and contains 0.1 to 20% by mass of Al 2 O 3 It is a powder.
Further, in the present invention, heating at 150 ° C. or more and less than 250 ° C. in the total amount of pyridine desorption A at the time of heating at 150 ° C. or more and less than 550 ° C. after adsorption of pyridine to the amorphous siliceous powder. It is preferable that (B / A) × 100% of the pyridine elimination amount B at the time is 20% or more.
The amorphous siliceous powder of the present invention preferably has a specific surface area of 0.5 to 45 m 2 / g, an average particle diameter of 0.1 to 60 μm, and an average sphericity of 0.80 or more.
Further, the present invention is an inorganic powder containing the amorphous siliceous powder of the present invention.
In the present invention, the inorganic powder is preferably an amorphous siliceous powder and / or an alumina powder other than the present invention.
さらに、本発明は、原料シリカ質粉末とAl源物質とを含む混合物を、バーナーで形成した火炎中に噴射し、非晶質シリカ質粉末を製造した後、温度60〜150℃、相対湿度60〜90%の雰囲気下で15〜30分保持することを特徴とする非晶質シリカ質粉末の製造方法である。 Furthermore, in the present invention, after a mixture containing raw material siliceous powder and Al source material is injected into a flame formed by a burner to produce amorphous siliceous powder, the temperature is 60 to 150 ° C. and the relative humidity is 60. It is a manufacturing method of amorphous siliceous powder characterized by holding for 15 to 30 minutes in an atmosphere of ˜90%.
また、本発明は、本発明の非晶質シリカ質粉末を樹脂中に含有する樹脂組成物である。前記樹脂としては、エポキシ樹脂が好ましい。
さらに、本発明は、これらの樹脂組成物を用いた半導体封止材である。Moreover, this invention is a resin composition which contains the amorphous siliceous powder of this invention in resin. As the resin, an epoxy resin is preferable.
Furthermore, this invention is a semiconductor sealing material using these resin compositions.
本発明によれば、流動性、粘度特性、及び成形性に優れた樹脂組成物、さらには、該樹脂組成物を用いた半導体封止材が提供される。また、前記樹脂組成物を調製するのに好適な非晶質シリカ質粉末が提供される。 According to the present invention, a resin composition excellent in fluidity, viscosity characteristics, and moldability, and a semiconductor encapsulant using the resin composition are provided. Moreover, an amorphous siliceous powder suitable for preparing the resin composition is provided.
以下、本発明を詳細に説明する。
本発明の非晶質シリカ質粉末は、ピリジンを吸着させて、加熱脱離させた際に、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比、L/Bが0.8以下である非晶質シリカ質粉末である。
シリカの構造中、例えば−O−Si−O−Al−O−Si−O−のように、Siの位置にAlが置換すると、Siの配位数とAlの配位数との違いから、その点が固体酸点であるルイス酸点(電子対受容体)となる。また、このルイス酸点にH2O(水)が結合すると、ブレンステッド酸点(プロトン供与体)となる。塩基性物質であるピリジンは、非晶質シリカ質粉末の表面のこれら酸点に結合し、強く結合したピリジンほど、加熱した際に、より高温で脱離する。非晶質シリカ質粉末の場合、結晶質に比べ構造がランダムであるため、酸強度(脱離温度)に分布が生じるが、概ね150℃〜250℃の加熱温度で脱離するピリジンがブレンステッド酸点と結合したもの、450℃〜550℃の加熱温度で脱離するピリジンがルイス酸点と結合したものと考えられる。Hereinafter, the present invention will be described in detail.
When the amorphous siliceous powder of the present invention adsorbs pyridine and heat desorbs it, the desorption amount L of pyridine during heating at 450 ° C. or higher and lower than 550 ° C. and 150 ° C. or higher and lower than 250 ° C. It is an amorphous siliceous powder having a ratio of pyridine desorption amount B during heating, L / B of 0.8 or less.
In the structure of silica, for example, -O-Si-O-Al-O-Si-O-, when Al is substituted at the position of Si, from the difference between the coordination number of Si and the coordination number of Al, That point becomes a Lewis acid point (electron pair acceptor) which is a solid acid point. Further, when H 2 O (water) is bonded to this Lewis acid point, it becomes a Bronsted acid point (proton donor). Pyridine, which is a basic substance, binds to these acid sites on the surface of the amorphous siliceous powder, and the more strongly bound pyridine is desorbed at a higher temperature when heated. In the case of amorphous siliceous powder, since the structure is random compared to crystalline, the acid strength (desorption temperature) is distributed, but pyridine desorbed at a heating temperature of about 150 ° C. to 250 ° C. is Bronsted. It is considered that a pyridine bonded with an acid point and a pyridine desorbed at a heating temperature of 450 ° C. to 550 ° C. are bonded with a Lewis acid point.
ピリジンを吸着させて、加熱した際に、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比、L/Bが0.8以下であるということは、ブレンステッド酸点の量がルイス酸点の量よりも1.25倍以上多いことを意味する。このような非晶質シリカを使用した場合、後述する理由により、流動性、粘度特性、及び成形性に優れた封止材を調製することが可能となる。逆に、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比、L/Bが0.8を超える場合、ブレンステッド酸点の量がルイス酸点の量に比べ1.25倍未満であることを意味し、流動性、粘度特性、及び成形性に優れた封止材を調製しにくくなる。 When pyridine is adsorbed and heated, the ratio of pyridine desorption amount L when heated at 450 ° C. or higher and lower than 550 ° C. and pyridine desorption amount B when heated at 150 ° C. or higher and lower than 250 ° C., L That / B is 0.8 or less means that the amount of Bronsted acid points is 1.25 times or more than the amount of Lewis acid points. When such amorphous silica is used, a sealing material excellent in fluidity, viscosity characteristics, and moldability can be prepared for the reasons described later. Conversely, the ratio of the pyridine desorption amount L when heated at 450 ° C. or higher and lower than 550 ° C. and the pyridine desorption amount B when heated at 150 ° C. or higher and lower than 250 ° C., L / B exceeds 0.8. In this case, it means that the amount of Bronsted acid points is less than 1.25 times the amount of Lewis acid points, and it becomes difficult to prepare a sealing material excellent in fluidity, viscosity characteristics, and moldability.
本発明による効果の発現理由を説明すれば以下のとおりである。すなわち、半導体封止材には、非晶質シリカ質粉末以外に、エポキシ樹脂、フェノール樹脂硬化剤、及び硬化促進剤が主たる成分として使用される。半導体封止材を一般的な熱硬化温度(成形温度)である150℃〜200℃程度に加熱すると、硬化促進剤によりフェノール樹脂硬化剤のプロトンが引き抜かれ、エポキシ樹脂とフェノール樹脂硬化剤とのアニオン重合連鎖反応が進行し、封止材が熱硬化していく。本発明の非晶質シリカ質粉末を使用した場合、加熱により、ブレンステッド酸点からプロトンが放出される。このプロトンはアニオン重合末端に結合し、重合連鎖反応が一時停止する結果、封止材の熱硬化が遅延するという現象が起こる。すなわち、本発明の非晶質シリカ質粉末により、封止材の熱硬化を潜在化することが可能になり、成形時の流動性、及び粘度特性に優れた封止材を調製することができる。450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比、L/Bが0.8以下の場合のみ、潜在化効果が顕著に発現する。このようなメカニズムのもと、非晶質シリカ質粉末へ潜在性を付与した事例は、これまでに存在しない。 The reason for the manifestation of the effect of the present invention will be described as follows. That is, an epoxy resin, a phenol resin curing agent, and a curing accelerator are used as main components in the semiconductor sealing material, in addition to the amorphous siliceous powder. When the semiconductor sealing material is heated to about 150 ° C. to 200 ° C., which is a general thermosetting temperature (molding temperature), the proton of the phenol resin curing agent is extracted by the curing accelerator, and the epoxy resin and the phenol resin curing agent The anionic polymerization chain reaction proceeds, and the sealing material is thermally cured. When the amorphous siliceous powder of the present invention is used, protons are released from the Bronsted acid point by heating. This proton is bonded to the anionic polymerization terminal, and as a result of the polymerization chain reaction being temporarily stopped, a phenomenon occurs in which the thermosetting of the sealing material is delayed. That is, the amorphous siliceous powder of the present invention makes it possible to latentize the thermosetting of the encapsulant, and it is possible to prepare an encapsulant excellent in fluidity and viscosity characteristics during molding. . Ratio of pyridine desorption amount L during heating at 450 ° C. or more and less than 550 ° C. and pyridine desorption amount B during heating at 150 ° C. or more and less than 250 ° C., only when L / B is 0.8 or less, The latent effect appears remarkably. Under such a mechanism, there has never been a case where a potential has been imparted to an amorphous siliceous powder.
一方、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比、L/Bが0.8を超える場合、上述のような、非晶質シリカ質粉末のブレンステッド酸点からのプロトン放出による封止材の潜在化が発現しにくいばかりでなく、ルイス酸点に、エポキシ樹脂、あるいはフェノール樹脂中の酸素が配位結合し、逆に、非晶質シリカ質粉末の流動を阻害し、封止材の流動性、及び粘度特性が悪化してしまうため好ましくない。好ましいL/B比は、0.7以下、さらに好ましくは、0.6以下である。 On the other hand, the ratio of pyridine desorption amount L during heating at 450 ° C. or more and less than 550 ° C. and pyridine desorption amount B during heating at 150 ° C. or more and less than 250 ° C., where L / B exceeds 0.8 As mentioned above, not only is the sealing material latent due to proton emission from the Bronsted acid point of the amorphous siliceous powder difficult to develop, but also the Lewis acid point has oxygen in the epoxy resin or phenol resin. Are not preferable because they are coordinated and, conversely, inhibit the flow of the amorphous siliceous powder and deteriorate the fluidity and viscosity characteristics of the sealing material. The preferred L / B ratio is 0.7 or less, more preferably 0.6 or less.
非晶質シリカ質粉末からのピリジンの脱離温度、及び脱離量は以下のような手順で測定することができる。
(1)ピリジン溶液の調製:分光分析用ピリジン7.91gを500mlメスフラスコに秤取り、分光分析用n−ヘプタンで定容する。次に、このピリジン溶液1mlを200mlメスフラスコに取り、n−ヘプタンで定容する。
(2)非晶質シリカ質粉末へのピリジンの吸着:あらかじめ、大気中200℃で2時間加熱して乾燥させ、過塩素酸マグネシウム乾燥剤とともにデシケーター中で放冷しておいた非晶質シリカ質粉末4.00gを、25mlメスフラスコに精秤する。このメスフラスコに、前記ピリジン溶液20mlを入れ、3分間振り混ぜる。このメスフラスコを25℃に設定した恒温槽に入れて2時間保持し、ピリジンを非晶質シリカ質粉末に吸着させる。
(3)非晶質シリカ質粉末の洗浄:非晶質シリカ質粉末に物理的に吸着したピリジンを洗浄するため、恒温槽より取り出したメスフラスコを振り混ぜ、10分間静置し、非晶質シリカ質粉末を沈降させる。ピリジン溶液の上澄みを捨て、分光分析用n−ヘプタン約20mlを加えた後、メスフラスコを振り混ぜ、10分間静置する。上澄み液を紫外可視分光光度計の測定セルに入れ、波長190〜340nm域の吸光度を測定し、251nmのピリジンの吸収を確認する。n−ヘプタンの上澄み液にピリジンの吸収が確認されなくなるまで、このn−ヘプタンによる洗浄操作を繰り返す。ピリジンの吸収が確認されなくなったら、上澄み液を捨て、メスフラスコの上部より、10分間、100ml/分の流量で乾燥窒素ガスを吹き込みながら、非晶質シリカ質粉末を室温で乾燥させる。
(4)ピリジン脱離温度、脱離量の測定:乾燥した非晶質シリカ質粉末10mgを、ダブルショットパイロライザーの試料カップに精秤し、熱分解装置で加熱しながら、ピリジンのマススペクトルをモニターし、ピリジンの脱離温度と脱離量を測定する。ピリジンの脱離量比は、得られたプロファイルの面積比から算出することができる。The desorption temperature and desorption amount of pyridine from the amorphous siliceous powder can be measured by the following procedure.
(1) Preparation of pyridine solution: 7.91 g of pyridine for spectroscopic analysis is weighed into a 500 ml volumetric flask, and the volume is measured with n-heptane for spectroscopic analysis. Next, 1 ml of this pyridine solution is placed in a 200 ml volumetric flask and made up to volume with n-heptane.
(2) Adsorption of pyridine on amorphous siliceous powder: Amorphous silica previously heated in air at 200 ° C. for 2 hours to dry and allowed to cool in a desiccator with a magnesium perchlorate desiccant 4.00 g of fine powder is precisely weighed into a 25 ml volumetric flask. Add 20 ml of the pyridine solution to the volumetric flask and shake for 3 minutes. This volumetric flask is placed in a thermostatic bath set at 25 ° C. and held for 2 hours to adsorb pyridine onto the amorphous siliceous powder.
(3) Washing of amorphous siliceous powder: In order to wash pyridine physically adsorbed on amorphous siliceous powder, shake the volumetric flask taken out from the thermostatic bath and let it stand for 10 minutes. The siliceous powder is allowed to settle. After discarding the supernatant of the pyridine solution and adding about 20 ml of n-heptane for spectroscopic analysis, the volumetric flask is shaken and allowed to stand for 10 minutes. The supernatant is put into a measurement cell of an ultraviolet-visible spectrophotometer, the absorbance in the wavelength range of 190 to 340 nm is measured, and the absorption of 251 nm pyridine is confirmed. This washing operation with n-heptane is repeated until no absorption of pyridine is confirmed in the supernatant of n-heptane. When absorption of pyridine is no longer confirmed, the supernatant is discarded, and the amorphous siliceous powder is dried at room temperature while blowing dry nitrogen gas from the top of the volumetric flask at a flow rate of 100 ml / min for 10 minutes.
(4) Measurement of pyridine desorption temperature and desorption amount: Weighing 10 mg of dried amorphous siliceous powder into a sample cup of a double shot pyrolyzer and heating the mass spectrum of pyridine while heating with a pyrolyzer. Monitor and measure the desorption temperature and desorption amount of pyridine. The ratio of elimination of pyridine can be calculated from the area ratio of the obtained profile.
なお、物理的に吸着したピリジンの有無の確認に使用する紫外可視分光光度計を例示すれば、島津製作所社製商品名「紫外可視分光光度計 モデルUV−1800」である。測定には、石英ガラス製10mm厚のセルを使用した。
ピリジン溶液を調製するのに用いる試薬を例示すれば、和光純薬工業社製ピリジン(分光分析用グレード)、及びn−ヘプタン(分光分析用グレード)である。
また、非晶質シリカ質粉末に吸着したピリジンの脱離温度、及び脱離量の測定に使用する装置を例示すれば、熱分解装置、FRONTIER LAB社製商品名「ダブルショットパイロライザー モデルPY−2020D」、GC/MS測定装置、Agilent社製商品名「GC/MSD モデル6890/5973」である。
熱分解炉の測定条件は、昇温速度:25℃/分で50〜700℃に昇温、ITF温度:150〜300℃に昇温、測定モード:EGA TEMP PROGである。GC/MSの測定条件は、カラム:UADTM−2.5N(液相なし)0.15mmφ×2.5m、オーブン温度:300℃、注入口温度:280℃、測定モード:SIM、スプリット比:30対1、モニターイオン:m/z=52、79である。なお、モニターイオン52と79の脱離量の和をピリジンの脱離量とした。An example of an ultraviolet-visible spectrophotometer used for confirming the presence of physically adsorbed pyridine is “Ultraviolet-visible spectrophotometer model UV-1800” manufactured by Shimadzu Corporation. For the measurement, a 10 mm thick cell made of quartz glass was used.
Examples of the reagent used to prepare the pyridine solution are pyridine (spectral analysis grade) and n-heptane (spectral analysis grade) manufactured by Wako Pure Chemical Industries, Ltd.
Further, as an example of an apparatus used for measuring the desorption temperature of pyridine adsorbed on amorphous siliceous powder and the amount of desorption, a thermal decomposition apparatus, a product name “Double Shot Pyrolyzer Model PY-” manufactured by FRONTIER LAB 2020D ”, GC / MS measuring device, trade name“ GC / MSD model 6890/5973 ”manufactured by Agilent.
The measurement conditions of the pyrolysis furnace are: temperature increase rate: 25 ° C./min to 50 to 700 ° C., ITF temperature: 150 to 300 ° C., measurement mode: EGA TEMP PROG. The GC / MS measurement conditions were as follows: Column: UADTM-2.5N (no liquid phase) 0.15 mmφ × 2.5 m, oven temperature: 300 ° C., inlet temperature: 280 ° C., measurement mode: SIM, split ratio: 30 Pair 1, monitor ions: m / z = 52, 79. The sum of the desorption amounts of monitor ions 52 and 79 was defined as the desorption amount of pyridine.
ピリジンの脱離量は微量であるため、絶対量を厳密に定量することは難しいが、上記測定方法で測定したアバンダンス(abundance:存在率)を基にすると、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比や、150℃以上550℃未満の加熱時におけるピリジンの総脱離量Aと150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比を、正確に求めることが可能となる。ピリジンが吸着・脱離しない場合、アバンダンスは0となり、吸着・脱離量が多いほどアバンダンスが大きくなる。本発明のような流動性、粘度特性、及び成形性の向上効果を発現させるためには、150℃以上250℃未満の加熱時におけるピリジンの脱離量アバンダンスの最大値が100以上、好ましくは200以上である必要がある。アバンダンスの最大値が100未満の場合、L/B比が所定の値を満たしていても、本発明の効果が発現しにくくなる。
なお、アバンダンスとは、上記測定法から一義的に得られる数値である。Since the amount of pyridine desorbed is very small, it is difficult to accurately determine the absolute amount. However, based on the abundance measured by the above measurement method, heating at 450 ° C. or higher and lower than 550 ° C. The ratio of the pyridine desorption amount L to 150 ° C. or more and less than 250 ° C. and the pyridine desorption amount B to 150 ° C. or more and less than 550 ° C. The ratio with the amount of pyridine desorption B during heating at a temperature lower than 250 ° C. can be accurately determined. When pyridine does not adsorb / desorb, the abundance is 0, and the abundance increases as the amount of adsorption / desorption increases. In order to exhibit the effect of improving fluidity, viscosity characteristics, and moldability as in the present invention, the maximum value of the pyridine elimination amount abundance upon heating at 150 ° C. or more and less than 250 ° C. is preferably 100 or more, preferably Must be 200 or more. When the maximum value of abundance is less than 100, even if the L / B ratio satisfies a predetermined value, the effect of the present invention is hardly exhibited.
The abundance is a numerical value uniquely obtained from the above measurement method.
本発明のような非晶質シリカ質粉末の流動性、粘度特性、及び成形性の向上効果は、非晶質シリカ質粉末が次の条件にあるときに助長される。すなわち、150℃以上550℃未満の加熱時におけるピリジンの総脱離量Aに占める、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bの割合、(B/A)×100%が20%以上であることである。前述したように、半導体封止材の一般的な熱硬化温度(成形温度)は150℃〜200℃程度であり、250℃以上550℃未満の加熱時におけるピリジンの脱離量は、プロトン放出による半導体封止材の潜在化に寄与しにくいばかりでなく、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lは、逆に、非晶質シリカ質粉末の流動を阻害し、封止材の流動性、及び粘度特性が悪化してしまうため好ましくない。このため、150℃以上550℃未満の加熱時におけるピリジンの総脱離量Aに占める、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bの割合、(B/A)×100%は20%以上である方が好ましい。この割合が25%以上、より好ましくは30%以上であると、成形時の流動性、及び粘度特性向上が特に顕著となる。 The effect of improving the fluidity, viscosity characteristics, and moldability of the amorphous siliceous powder as in the present invention is promoted when the amorphous siliceous powder is under the following conditions. That is, the ratio of the pyridine desorption amount B during heating at 150 ° C. or more and less than 250 ° C. in the total desorption amount A of pyridine during heating at 150 ° C. or more and less than 550 ° C., (B / A) × 100% It is 20% or more. As described above, the general thermosetting temperature (molding temperature) of the semiconductor encapsulant is about 150 ° C. to 200 ° C., and the amount of pyridine desorption during heating at 250 ° C. or more and less than 550 ° C. is due to proton emission. Not only is it difficult to contribute to latent semiconductor encapsulants, but the amount of pyridine desorption L during heating at 450 ° C. or higher and lower than 550 ° C., on the contrary, inhibits the flow of amorphous siliceous powder and seals. Since the fluidity | liquidity of a material and a viscosity characteristic will deteriorate, it is unpreferable. Therefore, the ratio of the pyridine desorption amount B during heating at 150 ° C. or more and less than 250 ° C. in the total desorption amount A of pyridine during heating at 150 ° C. or more and less than 550 ° C., (B / A) × 100% Is preferably 20% or more. When this proportion is 25% or more, more preferably 30% or more, the improvement in fluidity and viscosity characteristics at the time of molding becomes particularly remarkable.
さらに、本発明のような流動性、粘度特性、及び成形性の向上効果は、非晶質シリカ質粉末の比表面積が0.5〜45m2/g、平均粒子径が0.1〜60μm、及び平均球形度が0.80以上の条件にあるときにさらに助長される。
非晶質シリカ質粉末の比表面積が0.5m2/g未満だと、エポキシ樹脂、及びフェノール樹脂硬化剤と非晶質シリカ質粉末表面との接触面積が小さすぎ、プロトン放出による潜在化効果が発現しにくい。一方、比表面積が45m2/gを超えると、非晶質シリカ質粉末が小さい粒子を多量に含むか、粒子表面の一部または全部に凹凸があることを意味し、半導体封止材を用いて半導体をパッケージングする際の封止材の粘度が上昇するため、成形性が損なわれてしまう。好ましい比表面積の範囲は、0.6〜20m2/g、さらに好ましくは0.7〜10m2/gである。
また、非晶質シリカ質粉末の平均粒子径が0.1μm未満でも、同様に、半導体封止材を用いて半導体をパッケージングする際の封止材の粘度が上昇するため、成形性が損なわれてしまうため好ましくない。逆に、平均粒子径が60μmを超える場合、半導体チップに傷をつけてしまう問題や、凹凸のない均質なパッケージが得られないという問題が発生してしまう。好ましい平均粒子径の範囲は、2〜55μmであり、さらに好ましい範囲は、3〜50μmの範囲である。また、最大粒子径は、196μm以下であることが好ましく、さらに好ましくは128μm以下である。
さらに、本発明の非晶質シリカ質粉末の平均球形度は、0.80以上が好ましく、0.85以上がより好ましい。Furthermore, the improvement effect of fluidity | liquidity, a viscosity characteristic, and a moldability like this invention is that the specific surface area of an amorphous siliceous powder is 0.5-45 m < 2 > / g, an average particle diameter is 0.1-60 micrometers, Further, it is further promoted when the average sphericity is in a condition of 0.80 or more.
If the specific surface area of the amorphous siliceous powder is less than 0.5 m 2 / g, the contact area between the epoxy resin and phenol resin curing agent and the amorphous siliceous powder surface is too small, and the latent effect by proton release Is difficult to express. On the other hand, when the specific surface area exceeds 45 m 2 / g, it means that the amorphous siliceous powder contains a large amount of small particles or there are irregularities on part or all of the particle surface, and a semiconductor encapsulant is used. As a result, the viscosity of the sealing material when packaging the semiconductor is increased, so that the moldability is impaired. The range of a preferable specific surface area is 0.6-20 m < 2 > / g, More preferably, it is 0.7-10 m < 2 > / g.
In addition, even when the average particle size of the amorphous siliceous powder is less than 0.1 μm, the viscosity of the sealing material when packaging the semiconductor using the semiconductor sealing material similarly increases, so that the moldability is impaired. It is not preferable because it is lost. On the other hand, when the average particle diameter exceeds 60 μm, there arises a problem that the semiconductor chip is scratched or a uniform package without unevenness cannot be obtained. A preferred average particle size range is 2 to 55 μm, and a more preferred range is 3 to 50 μm. The maximum particle size is preferably 196 μm or less, more preferably 128 μm or less.
Furthermore, the average sphericity of the amorphous siliceous powder of the present invention is preferably 0.80 or more, and more preferably 0.85 or more.
本発明の非晶質シリカ質粉末の平均粒子径は、レーザー回折散乱法による粒度測定に基づいて測定する。測定機にはシーラス社製商品名「シーラスグラニュロメーター モデル920」を用い、水に非晶質シリカ質粉末を分散させ、さらに超音波ホモジナイザーで200Wの出力で1分間分散処理してから測定する。なお、粒度分布測定は、粒子径チャンネルが0.3、1、1.5、2、3、4、6、8、12、16、24、32、48、64、96、128、及び192μmにて行った。測定した粒度分布において、累積質量が50%となる粒子径が平均粒子径、累積質量が100%となる粒子径が最大粒子径である。 The average particle size of the amorphous siliceous powder of the present invention is measured based on particle size measurement by a laser diffraction scattering method. The product name “Cirrus Granurometer Model 920” manufactured by Cirrus Co., Ltd. is used as a measuring machine. Amorphous siliceous powder is dispersed in water and further subjected to dispersion treatment with an ultrasonic homogenizer at an output of 200 W for 1 minute. . In the particle size distribution measurement, the particle diameter channels were adjusted to 0.3, 1, 1.5, 2, 3, 4, 6, 8, 12, 16, 24, 32, 48, 64, 96, 128, and 192 μm. I went. In the measured particle size distribution, the particle size at which the cumulative mass is 50% is the average particle size, and the particle size at which the cumulative mass is 100% is the maximum particle size.
本発明の非晶質シリカ質粉末の比表面積は、BET法による比表面積測定に基づいて測定する。比表面積測定機として、マウンテック社製商品名「マックソーブ モデルHM−1208」を用いて測定する。 The specific surface area of the amorphous siliceous powder of the present invention is measured based on the specific surface area measurement by the BET method. As a specific surface area measuring device, measurement is performed using a product name “Maxsorb Model HM-1208” manufactured by Mountec.
本発明の非晶質シリカ質粉末は、他の無機質粉末に混合しても、その効果を発現させることができる。無機質粉末中の本発明の非晶質シリカ質粉末の含有率は、2質量%以上であることが好ましく、さらには5質量%以上であることが好ましい。無機質粉末の種類としては、本発明以外の非晶質シリカ質粉末及び/又はアルミナ質粉末であることが好ましい。これらの粉末は単独で用いてもよく、また二種類混合してもよい。半導体封止材の熱膨張率を低くする場合や、金型の摩耗性を低減する場合には無機質粉末として非晶質シリカ質粉末が選択され、半導体封止材の熱伝導性を付与する場合には無機質粉末としてアルミナ質粉末が選択される。なお非晶質シリカ質粉末は、後記の方法で測定された非晶質率の値で95%以上であることが好ましく、97%以上がより好ましい。 Even if the amorphous siliceous powder of the present invention is mixed with other inorganic powder, the effect can be exhibited. The content of the amorphous siliceous powder of the present invention in the inorganic powder is preferably 2% by mass or more, and more preferably 5% by mass or more. The inorganic powder is preferably an amorphous siliceous powder and / or an alumina powder other than the present invention. These powders may be used alone or in combination. When reducing the thermal expansion coefficient of the semiconductor encapsulant, or when reducing the wear of the mold, when amorphous siliceous powder is selected as the inorganic powder and imparting the thermal conductivity of the semiconductor encapsulant Alumina powder is selected as the inorganic powder. The amorphous siliceous powder is preferably 95% or more and more preferably 97% or more in terms of the amorphous ratio measured by the method described later.
本発明の非晶質シリカ質粉末は、下記方法で測定された非晶質率が95%以上であることが好ましく、97%以上がより好ましい。非晶質率は、粉末X線回折装置(例えばRIGAKU社製商品名「モデルMini Flex」)を用い、CuKα線の2θが26°〜27.5°の範囲においてX線回折分析を行い、特定回折ピークの強度比から測定する。シリカ粉末の場合、結晶質シリカは、26.7°に主ピークが存在するが、非晶質シリカではピークは存在しない。非晶質シリカと結晶質シリカが混在していると、結晶質シリカの割合に応じた26.7°のピーク高さが得られるので、結晶質シリカ標準試料のX線強度に対する試料のX線強度の比から、結晶質シリカ混在比(試料のX線回折強度/結晶質シリカのX線回折強度)を算出し、式、非晶質率(%)=(1−結晶質シリカ混在比)×100から非晶質率を求める。 The amorphous siliceous powder of the present invention preferably has an amorphous ratio measured by the following method of 95% or more, more preferably 97% or more. The amorphous ratio is specified by X-ray diffraction analysis using a powder X-ray diffractometer (for example, trade name “Model Mini Flex” manufactured by RIGAKU) in the range of 2θ of CuKα ray of 26 ° to 27.5 °. Measured from the intensity ratio of diffraction peaks. In the case of silica powder, crystalline silica has a main peak at 26.7 °, but amorphous silica has no peak. When amorphous silica and crystalline silica are mixed, a peak height of 26.7 ° corresponding to the ratio of crystalline silica can be obtained, so the X-ray of the sample relative to the X-ray intensity of the crystalline silica standard sample From the intensity ratio, the crystalline silica mixture ratio (X-ray diffraction intensity of the sample / X-ray diffraction intensity of the crystalline silica) is calculated, and the formula, amorphous ratio (%) = (1-crystalline silica mixture ratio) Obtain the amorphous ratio from x100.
本発明の非晶質シリカ質粉末、無機質粉末、及びアルミナ質粉末の平均球形度は0.80以上であることが好ましく、0.85以上がより好ましい。これによって、本発明の樹脂組成物の粘度を低下させ、成形性も向上させることができる。平均球形度は、実体顕微鏡(例えばニコン社製商品名「モデルSMZ−10型」)等にて撮影した粒子像を画像解析装置(例えばマウンテック社製商品名「MacView」)に取り込み、写真から粒子の投影面積(A)と周囲長(PM)から測定する。周囲長(PM)に対応する真円の面積を(B)とすると、その粒子の球形度はA/Bとなるので、試料の周囲長(PM)と同一の周囲長を持つ真円を想定すると、PM=2πr、B=πr2であるから、B=π×(PM/2π)2となり、個々の粒子の球形度は、球形度=A/B=A×4π/(PM)2となる。このようにして得られた任意の粒子200個の球形度を求め、その平均値を平均球形度とした。
上記以外の球形度の測定方法として、粒子像分析装置(例えば、シスメックス社製;商品名「モデルFPIA−3000」)にて、定量的に自動計測された個々の粒子の円形度から、式:球形度=(円形度)2により換算して求めることができる。The average sphericity of the amorphous siliceous powder, inorganic powder and alumina powder of the present invention is preferably 0.80 or more, and more preferably 0.85 or more. Thereby, the viscosity of the resin composition of this invention can be reduced and a moldability can also be improved. The average sphericity is obtained by taking a particle image taken with a stereomicroscope (for example, trade name “Model SMZ-10” manufactured by Nikon Corporation) into an image analysis apparatus (for example, trade name “MacView” manufactured by Mountec Co., Ltd.). Measured from the projected area (A) and the perimeter (PM). If the area of a perfect circle corresponding to the perimeter (PM) is (B), the sphericity of the particle is A / B, so a perfect circle having the same perimeter as the perimeter (PM) of the sample is assumed. Then, since PM = 2πr and B = πr 2 , B = π × (PM / 2π) 2 , and the sphericity of each particle is sphericity = A / B = A × 4π / (PM) 2 . Become. The sphericity of 200 arbitrary particles thus obtained was determined, and the average value was defined as the average sphericity.
As a method for measuring sphericity other than the above, from the circularity of each particle automatically and quantitatively measured by a particle image analyzer (for example, product name “Model FPIA-3000” manufactured by Sysmex Corporation), a formula: Sphericality = (circularity) 2 can be obtained by conversion.
次に、本発明の非晶質シリカ質粉末の製造方法について説明する。
本発明の製造方法は、原料シリカ質粉末とAl源物質とを含む混合物を、バーナーで形成した火炎中に噴射し、非晶質シリカ質粉末を製造した後、温度60〜150℃、相対湿度60〜90%の雰囲気下で15〜30分保持することを特徴とする非晶質シリカ質粉末の製造方法である。原料シリカ質粉末とAl源物質とを含む混合物をバーナーで形成した火炎中に噴射し、原料シリカ質粉末の溶融(非晶質化)、球状化を行うとほぼ同時に、シリカ質粉末の表面にAl源物質を融着させ、−O−Si−O−Al−O−Si−O−構造を形成させた後、温度60〜150℃、相対湿度60〜90%の雰囲気下で15〜30分保持し、150℃以上250℃未満の加熱時におけるピリジンの脱離量B、および450℃以上550℃未満の加熱時におけるピリジンの脱離量Lの調整を行う。これにより、初めて、本発明の特徴を備えた非晶質シリカ質粉末を製造することができる。Next, the manufacturing method of the amorphous siliceous powder of the present invention will be described.
In the production method of the present invention, a mixture containing a raw siliceous powder and an Al source material is injected into a flame formed by a burner to produce an amorphous siliceous powder, and then a temperature of 60 to 150 ° C. and a relative humidity. This is a method for producing an amorphous siliceous powder, characterized by holding for 15 to 30 minutes in an atmosphere of 60 to 90%. When a mixture containing raw material siliceous powder and Al source material is injected into a flame formed by a burner and the raw material siliceous powder is melted (amorphized) and spheroidized, almost simultaneously with the surface of the siliceous powder. After fusing the Al source material to form an —O—Si—O—Al—O—Si—O— structure, the temperature is 60 to 150 ° C. and the relative humidity is 60 to 90% in an atmosphere of 15 to 30 minutes. The amount of pyridine desorbed during heating at 150 ° C. or higher and lower than 250 ° C. and the amount of pyridine desorbed during heating at 450 ° C. or higher and lower than 550 ° C. are adjusted. Thereby, for the first time, an amorphous siliceous powder having the characteristics of the present invention can be produced.
原料シリカ質粉末とAl源物質とを含む混合物を火炎に噴射し、溶融、融着、球状化し、捕集する装置としては、例えばバーナーを備えた炉体に捕集装置が接続されたものが使用される。炉体は、開放型または密閉型、あるいは縦型、横型のいずれであっても良い。捕集装置には、重力沈降室、サイクロン、バッグフィルター、電気集塵機等の一つ以上が設けられ、その捕集条件を調整することによって、製造した非晶質シリカ質粉末を捕集することができる。その一例を示せば、特開平11−57451号公報、特開平11−71107号公報などである。非晶質シリカ質粉末を温度60〜150℃、相対湿度60〜90%の雰囲気下で15〜30分保持するためには、例えば、上記捕集装置に、スチームを供給するラインを設置し、所望の温度、相対湿度になるようにスチーム温度、及びスチーム供給量を調整すればよい。保持時間を調整するためには、上記捕集装置から非晶質シリカ質粉末を系外に排出する排出弁の開閉時間を所望の時間になるように調整すればよい。 As a device for injecting a mixture containing raw material siliceous powder and Al source material into a flame, melting, fusing, spheronizing and collecting, for example, a device having a collector connected to a furnace body equipped with a burner used. The furnace body may be an open type or a closed type, or a vertical type or a horizontal type. The collection device is provided with one or more of a gravity settling chamber, a cyclone, a bag filter, an electrostatic precipitator, etc., and the produced amorphous siliceous powder can be collected by adjusting the collection conditions. it can. For example, JP-A-11-57451, JP-A-11-71107, and the like. In order to hold the amorphous siliceous powder in an atmosphere having a temperature of 60 to 150 ° C. and a relative humidity of 60 to 90% for 15 to 30 minutes, for example, a line for supplying steam is installed in the collecting device, What is necessary is just to adjust steam temperature and a steam supply amount so that it may become desired temperature and relative humidity. In order to adjust the holding time, the open / close time of the discharge valve for discharging the amorphous siliceous powder out of the system from the collecting device may be adjusted to a desired time.
原料シリカ質粉末とAl源物質とを含む混合物を、バーナーで形成した火炎中に噴射した直後は、高温火炎の影響により、−O−Si−O−Al−O−Si−O−構造の酸点のタイプは、ほとんどがルイス酸、一部が火炎形成に用いた可燃性ガスの燃焼ガスに含まれるH2Oが結合したブレンステッド酸に変化しており、ピリジンの吸着脱離量比、L/Bは0.8超の関係にある。したがって、本発明の製造方法のような処理をしていない非晶質シリカ質粉末では、潜在化効果による成形時の流動性、及び粘度特性が向上しない。
加湿保持の湿度が60%未満、または保持時間が15分未満であると、ルイス酸のブレンステッド酸への変化が十分でなく、ピリジン脱離量比L/Bを0.8以下にコントロールすることができない。また湿度が90%を超えるか、保持時間が30分を超えると、非晶質シリカ質粉末が凝集してしまい、半導体封止材の成形性が低下するため好ましくない。
より好ましい加湿湿度は65〜85%、加湿時間は20〜25分の範囲である。同様に、加湿温度が60℃未満だとH2Oが結合しにくく、ルイス酸のブレンステッド酸への変化が十分でない結果、ピリジン脱離量比L/Bを0.8以下にコントロールすることができない。一方、保持温度が150℃を超えても、温度が高すぎH2Oが結合しにくいため、L/Bを0.8以下にすることができない。60〜150℃の温度範囲に保持した場合のみ、L/B比を0.8以下に調整することが可能となる。より好ましい保持温度は70〜120℃、さらに好ましくは75〜100℃の範囲である。Immediately after the mixture containing the raw siliceous powder and the Al source material is injected into the flame formed by the burner, an acid having the structure of -O-Si-O-Al-O-Si-O- is caused by the influence of the high-temperature flame. The type of the point is changed to Bronsted acid combined with H 2 O contained in the combustion gas of the combustible gas mostly used as the Lewis acid, and the pyridine adsorption / desorption ratio, L / B has a relationship of more than 0.8. Therefore, the amorphous siliceous powder not subjected to the treatment as in the production method of the present invention does not improve the flowability and viscosity characteristics during molding due to the latent effect.
When the humidity of the humidified holding is less than 60% or the holding time is less than 15 minutes, the change of the Lewis acid to the Bronsted acid is not sufficient, and the pyridine elimination amount ratio L / B is controlled to 0.8 or less. I can't. On the other hand, if the humidity exceeds 90% or the holding time exceeds 30 minutes, the amorphous siliceous powder is aggregated and the moldability of the semiconductor sealing material is lowered, which is not preferable.
More preferable humidification humidity is 65 to 85%, and the humidification time is in the range of 20 to 25 minutes. Similarly, when the humidification temperature is less than 60 ° C., H 2 O hardly binds and the change of Lewis acid to Bronsted acid is not sufficient, and as a result, the pyridine elimination ratio L / B is controlled to 0.8 or less. I can't. On the other hand, even if the holding temperature exceeds 150 ° C., the temperature is too high and H 2 O is difficult to bond, so L / B cannot be made 0.8 or less. The L / B ratio can be adjusted to 0.8 or less only when the temperature is maintained in the temperature range of 60 to 150 ° C. A more preferable holding temperature is in the range of 70 to 120 ° C, more preferably 75 to 100 ° C.
原料シリカ質粉末には、高純度珪石、高純度珪砂、石英、水晶など天然に産出するシリカ含有鉱物の粉末や、沈降シリカ、シリカゲルなど合成法により製造された高純度シリカ粉末などを使用することができるが、コストや入手のしやすさを考慮すると、珪石粉末が最も好ましい。珪石粉末は、振動ミル、ボールミルなどの粉砕機で粉砕された、様々な粒子径のものが市販されており、所望の非晶質シリカ質粉末の粒子径が得られるように、適宜粒子径を選択すればよい。 The raw siliceous powder should be silica-containing mineral powders such as high-purity silica, high-purity silica sand, quartz and quartz, and high-purity silica powder produced by synthetic methods such as precipitated silica and silica gel. However, in view of cost and availability, silica powder is most preferable. Silica powder is commercially available in various particle sizes that have been pulverized by a pulverizer such as a vibration mill and a ball mill. The particle size is appropriately adjusted so that the desired particle size of amorphous siliceous powder can be obtained. Just choose.
本発明において、Al源物質は酸化アルミニウム粉末であることが好ましい。Al源物質としては、酸化アルミニウム、水酸化アルミニウム、硝酸アルミニウム、塩化アルミニウム、アルミニウム有機化合物などが挙げられる。なかでも、酸化アルミニウムが原料シリカ質粉末の融点と近いため、バーナーから噴射した際に原料シリカ質粉末の表面に融着しやすく、不純物含有率も少ないため最も好ましい。
また、酸化アルミニウム粉末の平均粒子径は0.01〜10μmであることが好ましい。平均粒子径が0.01μm未満だと粉末が凝集しやすく、シリカ質粉末と融着した際の組成が不均質になる傾向にあり、同様に10μmを超えてもシリカ質粉末と融着した際の組成が不均質になる。好ましい平均粒子径の範囲は、0.03〜8μm、さらに好ましくは0.05〜5μmである。
また、本発明の非晶質シリカ質粉末中のAl2O3の含有率は0.1〜20質量%であることが好ましい。Al2O3の含有率が0.1質量%未満だと、酸点の増加が十分でなく、逆に20質量%を超えると、非晶質シリカ質粉末の熱膨張率が大きくなりすぎ、本来の半導体封止材の機能に悪影響を与えてしまう。好ましいAl2O3の含有率は0.15〜18質量%、さらに好ましくは0.2〜15質量%である。In the present invention, the Al source material is preferably aluminum oxide powder. Examples of the Al source material include aluminum oxide, aluminum hydroxide, aluminum nitrate, aluminum chloride, and an aluminum organic compound. Especially, since aluminum oxide is close to the melting point of the raw material siliceous powder, it is most preferable because it is easily fused to the surface of the raw material siliceous powder when sprayed from a burner and the impurity content is small.
Moreover, it is preferable that the average particle diameter of an aluminum oxide powder is 0.01-10 micrometers. When the average particle size is less than 0.01 μm, the powder tends to aggregate, and the composition when fused with the siliceous powder tends to be heterogeneous. Similarly, when fused with the siliceous powder even when it exceeds 10 μm The composition becomes inhomogeneous. The range of a preferable average particle diameter is 0.03-8 micrometers, More preferably, it is 0.05-5 micrometers.
Further, the content of Al 2 O 3 amorphous siliceous powder of the present invention is preferably 0.1 to 20 mass%. If the content of Al 2 O 3 is less than 0.1% by mass, the increase in acid point is not sufficient. Conversely, if the content exceeds 20% by mass, the thermal expansion coefficient of the amorphous siliceous powder becomes too large, The function of the original semiconductor sealing material will be adversely affected. A preferable content of Al 2 O 3 is 0.15 to 18% by mass, and more preferably 0.2 to 15% by mass.
本発明の非晶質シリカ質粉末のAl2O3含有率(酸化物換算)は原子吸光分析法を用いて、下記のような手順で測定することができる。すなわち、非晶質シリカ質粉末1gを白金皿に精秤し、試薬特級フッ化水素酸、及び試薬特級過塩素酸をそれぞれ20ml、及び1ml加える。その白金皿を300℃に加熱されたサンドバス上に15分間静置してから室温まで冷却し、25mlメスフラスコに移しかえ純水で定容する。この溶液のAl量を、原子吸光光度計を用い検量線法により定量する。そのAl量をAl2O3に換算し非晶質シリカ質粉末中の含有率を算出する。原子吸光光度計を例示すれば、日本ジャーレルアッシュ社製商品名「原子吸光光度計 モデルAA−969」である。検量線を作成するのに用いる標準液を例示すれば、関東化学社製原子吸光用Al標準液(濃度1000ppm)である。なお、測定の際のフレームにはアセチレン−亜酸化窒素フレームを用い、波長309.3nmにおける吸光度を測定して定量する。The Al 2 O 3 content (oxide conversion) of the amorphous siliceous powder of the present invention can be measured by the following procedure using atomic absorption analysis. That is, 1 g of amorphous siliceous powder is precisely weighed in a platinum dish, and 20 ml and 1 ml of reagent special grade hydrofluoric acid and reagent special grade perchloric acid are added, respectively. The platinum dish is allowed to stand on a sand bath heated to 300 ° C. for 15 minutes, cooled to room temperature, transferred to a 25 ml volumetric flask, and fixed with pure water. The amount of Al in this solution is quantified by a calibration curve method using an atomic absorption photometer. The Al content is converted to Al 2 O 3 and the content in the amorphous siliceous powder is calculated. An example of an atomic absorption photometer is “Atom Absorption Photometer Model AA-969” manufactured by Nippon Jarrell-Ash. An example of a standard solution used for preparing a calibration curve is an Al standard solution for atomic absorption (concentration 1000 ppm) manufactured by Kanto Chemical. In addition, an acetylene-nitrous oxide flame is used for the measurement frame, and the absorbance at a wavelength of 309.3 nm is measured and quantified.
なお、本発明において、非晶質シリカ質粉末にピリジンを吸着、加熱脱離させた際のピリジンの脱離量、及び脱離温度は、原料シリカ質粉末の表面に融着させるAl源物質のサイズ、量、加湿保持条件、比表面積、平均粒子径などによって調整が可能である。
非晶質シリカ質粉末の比表面積、及び平均粒子径は、原料シリカ質粉末の粒度構成や火炎温度などによって調整が可能である。また、平均球形度、及び非晶質率は原料シリカ質粉末の火炎への供給量や火炎温度などによって調整可能である。さらには、融着させたAl源物質のサイズ、量、加湿保持条件、比表面積、平均粒子径などが異なる非晶質シリカ質粉末を種々製造しておき、それらの2種以上を適宜混合することによって、ピリジンを吸着、脱離させた際のピリジンの脱離量、脱離温度、比表面積、平均粒子径などが更に特定された非晶質シリカ質粉末を製造することもできる。In the present invention, the amount of pyridine desorbed and the desorption temperature when pyridine is adsorbed and desorbed by heating to the amorphous siliceous powder is determined by the Al source material fused to the surface of the raw siliceous powder. Adjustments can be made according to size, amount, humidification holding conditions, specific surface area, average particle size, and the like.
The specific surface area and the average particle diameter of the amorphous siliceous powder can be adjusted by the particle size constitution of the raw siliceous powder, the flame temperature, and the like. Further, the average sphericity and the amorphous ratio can be adjusted by the supply amount of the raw siliceous powder to the flame, the flame temperature, and the like. Furthermore, various amorphous siliceous powders having different sizes, amounts, humidification holding conditions, specific surface areas, average particle diameters, and the like of the fused Al source material are manufactured, and two or more of them are mixed as appropriate. Thus, it is possible to produce an amorphous siliceous powder in which the amount of pyridine desorbed, the desorption temperature, the specific surface area, the average particle diameter and the like when pyridine is adsorbed and desorbed are further specified.
本発明の樹脂組成物は、本発明の非晶質シリカ質粉末又は本発明の無機質粉末を樹脂中に含有する樹脂組成物である。樹脂組成物中の非晶質シリカ質粉末又は無機質粉末の含有率は10〜95質量%であり、さらに好ましくは30〜90質量%である。 The resin composition of the present invention is a resin composition containing the amorphous siliceous powder of the present invention or the inorganic powder of the present invention in a resin. The content of the amorphous siliceous powder or inorganic powder in the resin composition is 10 to 95% by mass, more preferably 30 to 90% by mass.
樹脂としては、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル、フッ素樹脂、ポリイミド、ポリアミドイミド、ポリエーテルイミド等のポリアミド、ポリブチレンテレフタレート、ポリエチレンテレフタレート等のポリエステル、ポリフェニレンスルフィド、芳香族ポリエステル、ポリスルホン、液晶ポリマー、ポリエーテルスルホン、ポリカーボネイト、マレイミド変成樹脂、ABS樹脂、AAS(アクリロニトリルーアクリルゴム・スチレン)樹脂、AES(アクリロニトリル・エチレン・プロピレン・ジエンゴム−スチレン)樹脂等を使用することができる。 Examples of the resin include epoxy resin, silicone resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyamide such as polyimide, polyamideimide, and polyetherimide, polyester such as polybutylene terephthalate and polyethylene terephthalate, polyphenylene sulfide , Aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, ABS resin, AAS (acrylonitrile-acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / diene rubber / styrene) resin, etc. can do.
これらの中、半導体封止材用の樹脂としては、1分子中にエポキシ基を2個以上有するエポキシ樹脂が好ましい。それを例示すれば、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、フェノール類とアルデヒド類のノボラック樹脂をエポキシ化したもの、ビスフェノールA、ビスフェノールF及びビスフェノールSなどのグリシジルエーテル、フタル酸やダイマー酸などの多塩基酸とエポクロルヒドリンとの反応により得られるグリシジルエステル酸エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、アルキル変性多官能エポキシ樹脂、β−ナフトールノボラック型エオキシ樹脂、1,6−ジヒドロキシナフタレン型エポキシ樹脂、2,7−ジヒドロキシナフタレン型エポキシ樹脂、ビスヒドロキシビフェニル型エポキシ樹脂、更には難燃性を付与するために臭素などのハロゲンを導入したエポキシ樹脂等である。中でも、耐湿性や耐ハンダリフロー性の点からは、オルソクレゾールノボラック型エポキシ樹脂、ビスヒドロキシビフェニル型エポキシ樹脂、ナフタレン骨格のエポキシ樹脂等が好適である。 Among these, as the resin for the semiconductor sealing material, an epoxy resin having two or more epoxy groups in one molecule is preferable. For example, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, epoxidized phenol and aldehyde novolak resin, glycidyl ether such as bisphenol A, bisphenol F and bisphenol S, phthalic acid and dimer Glycidyl ester acid epoxy resin, linear aliphatic epoxy resin, cycloaliphatic epoxy resin, heterocyclic epoxy resin, alkyl-modified polyfunctional epoxy resin obtained by reaction of polybasic acid such as acid and epochorohydrin, β -Naphthol novolac type epoxy resin, 1,6-dihydroxynaphthalene type epoxy resin, 2,7-dihydroxynaphthalene type epoxy resin, bishydroxybiphenyl type epoxy resin, and halogen such as bromine to impart flame retardancy It is introduced epoxy resin. Among these, from the viewpoint of moisture resistance and solder reflow resistance, orthocresol novolac type epoxy resins, bishydroxybiphenyl type epoxy resins, epoxy resins having a naphthalene skeleton, and the like are preferable.
本発明で使用するエポキシ樹脂は、エポキシ樹脂の硬化剤、又はエポキシ樹脂の硬化剤とエポキシ樹脂の硬化促進剤を含むものである。エポキシ樹脂の硬化剤としては、例えばフェノール、クレゾール、キシレノール、レゾルシノール、クロロフェノール、t−ブチルフェノール、ノニルフェノール、イソプロピルフェノール、及びオクチルフェノールからなる群から選ばれた1種又は2種以上の混合物をホルムアルデヒド、パラホルムアルデヒド又はパラキシレンとともに酸化触媒下で反応させて得られるノボラック型樹脂、ポリパラヒドロキシスチレン樹脂、ビスフェノールAやビスフェノールS等のビスフェノール化合物、ピロガロールやフロログルシノール等の3官能フェノール類、無水マレイン酸、無水フタル酸や無水ピロメリット酸等の酸無水物、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族アミン等を挙げることができる。
また、エポキシ樹脂と硬化剤との反応を促進させるためには、例えばトリフェニルホスフィン、ベンジルジメチルアミン、2−メチルイミダゾール等の硬化促進剤を使用することができる。The epoxy resin used in the present invention contains an epoxy resin curing agent or an epoxy resin curing agent and an epoxy resin curing accelerator. Examples of the epoxy resin curing agent include one or a mixture of two or more selected from the group consisting of phenol, cresol, xylenol, resorcinol, chlorophenol, t-butylphenol, nonylphenol, isopropylphenol, and octylphenol. Novolac resin obtained by reacting with formaldehyde or para-xylene under an oxidation catalyst, polyparahydroxystyrene resin, bisphenol compounds such as bisphenol A and bisphenol S, trifunctional phenols such as pyrogallol and phloroglucinol, maleic anhydride, Examples include acid anhydrides such as phthalic anhydride and pyromellitic anhydride, and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Can.
Moreover, in order to accelerate | stimulate reaction with an epoxy resin and a hardening | curing agent, hardening accelerators, such as a triphenylphosphine, benzyldimethylamine, 2-methylimidazole, can be used, for example.
本発明の樹脂組成物には、更に以下の成分を必要に応じて配合することができる。すなわち、低応力化剤として、シリコーンゴム、ポリサルファイドゴム、アクリル系ゴム、ブタジエン系ゴム、スチレン系ブロックコポリマーや飽和型エラストマー等のゴム状物質、各種熱可塑性樹脂、シリコーン樹脂等の樹脂状物質、更にはエポキシ樹脂、フェノール樹脂の一部又は全部をアミノシリコーン、エポキシシリコーン、アルコキシシリコーンなどで変性した樹脂などが挙げられる。シランカップリング剤として、γ−グリシドキシプロピルトリメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシシラン、アミノプロピルトリエトキシシラン、ウレイドプロピルトリエトキシシラン、N−フェニルアミノプロピルトリメトキシシラン等のアミノシラン、フェニルトリメトキシシラン、メチルトリメトキシシラン、オクタデシルトリメトキシシラン等の疎水性シラン化合物やメルカプトシランなどが挙げられる。表面処理剤として、Zrキレート、チタネートカップリング剤、アルミニウム系カップリング剤などが挙げられる。難燃助剤として、Sb2O3、Sb2O4、Sb2O5などが挙げられる。難燃剤として、ハロゲン化エポキシ樹脂やリン化合物などが挙げられる。着色剤として、カーボンブラック、酸化鉄、染料、顔料などが挙げられる。更には離型剤として、天然ワックス類、合成ワックス類、直鎖脂肪酸の金属塩、酸アミド類、エステル類、パラフィンなどが挙げられる。In the resin composition of the present invention, the following components can be further blended as necessary. That is, as a low stress agent, silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, rubbery substances such as styrene block copolymers and saturated elastomers, various thermoplastic resins, resinous substances such as silicone resins, Includes resins obtained by modifying part or all of an epoxy resin or phenol resin with amino silicone, epoxy silicone, alkoxy silicone, or the like. As silane coupling agents, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other epoxy silanes, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenyl Examples include aminosilanes such as aminopropyltrimethoxysilane, hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, and octadecyltrimethoxysilane, and mercaptosilane. Examples of the surface treatment agent include Zr chelate, titanate coupling agent, and aluminum coupling agent. Examples of the flame retardant aid include Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 and the like. Examples of flame retardants include halogenated epoxy resins and phosphorus compounds. Examples of the colorant include carbon black, iron oxide, dye, and pigment. Furthermore, examples of the releasing agent include natural waxes, synthetic waxes, metal salts of linear fatty acids, acid amides, esters, and paraffin.
本発明の樹脂組成物は、上記各材料の所定量をブレンダーやヘンシェルミキサー等によりブレンドした後、加熱ロール、ニーダー、一軸又は二軸押し出し機等により混練したものを冷却後、粉砕することによって製造することができる。 The resin composition of the present invention is produced by blending a predetermined amount of each of the above materials with a blender, a Henschel mixer, etc., then kneading with a heating roll, kneader, uniaxial or biaxial extruder, etc. can do.
本発明の半導体封止材は、樹脂組成物がエポキシ樹脂を含有するものであり、エポキシ樹脂の硬化剤とエポキシ樹脂の硬化促進剤とを含む組成物からなるものである。
本発明の半導体封止材を用いて半導体を封止するには、トランスファーモールド法、真空印刷モールド法等の常套の成形手段が採用される。In the semiconductor sealing material of the present invention, the resin composition contains an epoxy resin, and is composed of a composition containing an epoxy resin curing agent and an epoxy resin curing accelerator.
In order to seal the semiconductor using the semiconductor sealing material of the present invention, conventional molding means such as a transfer molding method and a vacuum printing molding method are employed.
以下、本発明の実施例によりさらに詳細に説明するが、これらに限定して解釈されるものではない。
実施例1〜8及び比較例1〜10
本発明の非晶質シリカ質粉末の製造に用いた原料は、キンセイマテック社製結晶シリカ粉末(SiO2含有率99.9質量%)、日本軽金属社製アルミナ粉末、及び水酸化アルミニウム粉末を使用した。各粉末の粉砕、分級を行うことにより粒度調整を行い、平均粒子径の異なる、種々の原料シリカ質粉末、及びAl源物質を準備した。これを、特開平11−57451号公報に記載された装置および、これらの捕集装置に、スチームを発生させるボイラー、及びスチームを供給するラインを設置し、所望の温度、及び相対湿度になるようにスチーム温度、及びスチーム供給量を調整できるようにした。本装置を用いて、上記原料を火炎中で溶融、融着、球状化、加湿保持処理し、表1及び表2に示される種々の非晶質シリカ質粉末を製造した。また、これらの粉末を適宜配合して表3及び表4に示される非晶質シリカ質粉末、及び無機質粉末を製造した。
なお、非晶質シリカ質粉末にピリジンを吸着、脱離させた際のピリジンの脱離量、及び脱離温度は、原料シリカ質粉末の表面に融着させるAl源物質のサイズ、量、加湿保持条件、比表面積、平均粒子径などを変更することによって調整した。
非晶質シリカ質粉末の比表面積、及び平均粒子径は、原料シリカ質粉末の粒度構成や火炎温度などによって調整し、非晶質シリカ質粉末の平均球形度、及び非晶質率は原料シリカ質粉末の火炎への供給量や火炎温度などによって調整した。なお、火炎の形成には、LPG、及び酸素ガスを用い、原料粉末をバーナーまで搬送するキャリアガスにも酸素ガスを使用した。この火炎の最高温度は約2000℃〜2300℃の範囲であった。
非晶質シリカ質粉末へのピリジンの吸着、および非晶質シリカ質粉末からのピリジンの脱離温度と脱離量の測定については、段落(0014)に記載の方法で行った。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention should not be construed as being limited thereto.
Examples 1-8 and Comparative Examples 1-10
The raw materials used for the production of the amorphous siliceous powder of the present invention are crystalline silica powder (SiO 2 content 99.9% by mass) manufactured by Kinsei Matech, alumina powder manufactured by Nippon Light Metal Co., and aluminum hydroxide powder. did. By adjusting the particle size by pulverizing and classifying each powder, various raw material siliceous powders and Al source materials having different average particle diameters were prepared. The apparatus described in Japanese Patent Laid-Open No. 11-57451, and a boiler for generating steam and a line for supplying steam are installed in the apparatus described in Japanese Patent Application Laid-Open No. 11-57451 so that a desired temperature and relative humidity are obtained. The steam temperature and steam supply amount can be adjusted. Using this apparatus, the raw materials were melted, fused, spheroidized, and humidified and retained in a flame to produce various amorphous siliceous powders shown in Tables 1 and 2. Further, these powders were appropriately blended to produce amorphous siliceous powders and inorganic powders shown in Tables 3 and 4.
The amount of pyridine desorbed and desorbed when pyridine is adsorbed and desorbed from the amorphous siliceous powder is determined by the size, amount, and humidification of the Al source material fused to the surface of the raw siliceous powder. It adjusted by changing holding conditions, a specific surface area, an average particle diameter, etc.
The specific surface area and average particle diameter of the amorphous siliceous powder are adjusted according to the particle size composition and flame temperature of the raw siliceous powder, and the average sphericity and amorphous ratio of the amorphous siliceous powder are the raw silica. It was adjusted according to the amount of powder supplied to the flame and the flame temperature. In addition, LPG and oxygen gas were used for formation of a flame, and oxygen gas was also used for the carrier gas which conveys raw material powder to a burner. The maximum temperature of this flame was in the range of about 2000 ° C to 2300 ° C.
The adsorption of pyridine to the amorphous siliceous powder and the measurement of the desorption temperature and desorption amount of pyridine from the amorphous siliceous powder were performed by the method described in paragraph (0014).
得られた非晶質シリカ質粉末の非晶質率はいずれも99.5%以上であった。これらの粉末の比表面積、平均粒子径、平均球形度、ピリジン脱離温度、及び脱離量を測定し、450℃以上550℃未満の加熱時におけるピリジンの脱離量Lと、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bとの比L/B、および150℃以上550℃未満の加熱時におけるピリジンの総脱離量Aに占める、150℃以上250℃未満の加熱時におけるピリジンの脱離量Bの割合(B/A)×100%を算出した。結果を表3及び表4に示した。 The amorphous ratio of the obtained amorphous siliceous powder was 99.5% or more. The specific surface area, average particle diameter, average sphericity, pyridine desorption temperature, and desorption amount of these powders were measured, and the desorption amount L of pyridine during heating at 450 ° C. or more and less than 550 ° C., and 150 ° C. or more and 250 The ratio L / B of the pyridine desorption amount B during heating below 150 ° C. and the total pyridine desorption amount A during heating at 150 ° C. or higher and lower than 550 ° C., during heating at 150 ° C. or higher and lower than 250 ° C. The ratio of pyridine elimination amount B (B / A) × 100% was calculated. The results are shown in Tables 3 and 4.
得られた非晶質シリカ質粉末、及び無機質粉末の半導体封止材の充填材としての特性を評価した。すなわち、各粉末87.8部(質量部、以下同じ)に対し、ビフェニル型エポキシ樹脂(ジャパンエポキシレジン社製YX−4000H)5.9部、フェノールアラルキル樹脂(三井化学社製XLC−LL)5.1部、トリフェニルホスフィン0.2部、エポキシシランカップリング剤0.6部、カーボンブラック0.1部、及びカルナバワックス0.3部を加え、ヘンシェルミキサーにてドライブレンドした。その後、同方向噛み合い二軸押出混練機(スクリュー径D=25mm、ニーディングディスク長10Dmm、パドル回転数50〜120rpm、吐出量2.5kg/Hr、混練物温度99〜100℃)で加熱混練した。混練物(吐出物)をプレス機にてプレスして冷却した後、粉砕して半導体封止材を製造した。得られた半導体封止材の粘度特性(キュラストメータートルク)、成形性(ワイヤー変形率)及び流動性(スパイラルフロー)を以下に従って評価した。
それらの結果を表3及び表4に示した。The characteristics of the obtained amorphous siliceous powder and inorganic powder as a filler for a semiconductor sealing material were evaluated. That is, 5.9 parts of biphenyl type epoxy resin (YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.), phenol aralkyl resin (XLC-LL manufactured by Mitsui Chemicals Co., Ltd.) 5 for 87.8 parts (parts by mass, the same applies hereinafter) of each powder. .1 part, 0.2 part of triphenylphosphine, 0.6 part of epoxysilane coupling agent, 0.1 part of carbon black, and 0.3 part of carnauba wax were added and dry blended with a Henschel mixer. Thereafter, the mixture was heated and kneaded in the same direction meshing twin screw extrusion kneader (screw diameter D = 25 mm, kneading disk length 10 Dmm, paddle rotation speed 50 to 120 rpm, discharge amount 2.5 kg / Hr, kneaded material temperature 99 to 100 ° C.). . The kneaded product (discharged product) was pressed with a press and cooled, and then pulverized to produce a semiconductor encapsulant. The viscosity characteristics (curastometer torque), moldability (wire deformation rate) and fluidity (spiral flow) of the obtained semiconductor encapsulant were evaluated as follows.
The results are shown in Tables 3 and 4.
(1)粘度特性(キュラストメータートルク)
上記で得られた半導体封止材の粘度特性を次のようにして測定した。キュラストメーター(例えばJSRトレーディング社製商品名「キュラストメーター モデル3P−S型」)を用い、半導体封止材を110℃に加熱した際の30秒後のトルクを粘度指数とした。この値が小さいほど、粘度特性が良好であることを示す。(1) Viscosity characteristics (curastometer torque)
The viscosity characteristics of the semiconductor encapsulant obtained above were measured as follows. Using a curast meter (for example, trade name “Curast Meter Model 3P-S type” manufactured by JSR Trading Co., Ltd.), the torque after 30 seconds when the semiconductor encapsulant was heated to 110 ° C. was defined as the viscosity index. It shows that a viscosity characteristic is so favorable that this value is small.
(2)成形性(ワイヤー変形率)
上記で得られた半導体封止材の成形性をつぎのようにして測定した。BGA(Ball Grid Array)用基板に、ダイアタッチフィルムを介して、サイズ8mm×8mm×0.3mmの模擬半導体素子を2枚重ね、金ワイヤーで接続した。その後、各半導体封止材を使用し、トランスファー成形機を用いて、パッケージサイズ38mm×38mm×1.0mmに成形後、175℃で8時間アフターキュアし、BGA型半導体を作製した。半導体の金ワイヤーの部分を軟X線透過装置で観察し、金ワイヤー変形率を測定した。金ワイヤー変形率は、封止前のワイヤー最短距離Xおよび、封止後のワイヤーの最大変位量Yを測定し、(Y/X)×100(%)として求めた。この値は12本の金ワイヤー変形率の平均値とした。なお、金ワイヤーの径はφ30μm、平均長さは5mmである。トランスファー成形条件は、金型温度175℃、成形圧力7.4MPa、及び保圧時間90秒とした。この値が小さいほど、ワイヤー変形量が小さく、成形性が良好であることを示す。(2) Formability (wire deformation rate)
The moldability of the semiconductor encapsulant obtained above was measured as follows. Two simulated semiconductor elements having a size of 8 mm × 8 mm × 0.3 mm were stacked on a BGA (Ball Grid Array) substrate via a die attach film and connected by a gold wire. Thereafter, each semiconductor encapsulant was used and formed into a package size of 38 mm × 38 mm × 1.0 mm using a transfer molding machine, followed by after-curing at 175 ° C. for 8 hours to produce a BGA type semiconductor. The portion of the semiconductor gold wire was observed with a soft X-ray transmission device, and the deformation rate of the gold wire was measured. The gold wire deformation ratio was determined as (Y / X) × 100 (%) by measuring the shortest wire distance X before sealing and the maximum displacement Y of the wire after sealing. This value was the average of the deformation rates of 12 gold wires. The diameter of the gold wire is φ30 μm, and the average length is 5 mm. The transfer molding conditions were a mold temperature of 175 ° C., a molding pressure of 7.4 MPa, and a pressure holding time of 90 seconds. The smaller this value, the smaller the amount of wire deformation and the better the moldability.
(3)流動性(スパイラルフロー)
EMMI−I−66(Epoxy Molding Material Institute;Society of Plastic Industry)に準拠したスパイラルフロー測定用金型を取り付けたトランスファー成形機を用い、各半導体封止材のスパイラルフロー値を測定した。なお、トランスファー成形条件は、金型温度175℃、成形圧力7.4MPa、及び保圧時間120秒とした。この値が大きいほど、流動性が良好であることを示す。(3) Fluidity (spiral flow)
The spiral flow value of each semiconductor encapsulant was measured using a transfer molding machine equipped with a spiral flow measurement mold in accordance with EMMI-I-66 (Epoxy Molding Material Institute; Society of Plastic Industry). The transfer molding conditions were a mold temperature of 175 ° C., a molding pressure of 7.4 MPa, and a pressure holding time of 120 seconds. It shows that fluidity | liquidity is so favorable that this value is large.
実施例と比較例の対比から明らかなように、本発明の非晶質シリカ質粉末によれば、比較例よりも流動性、粘度特性、及び成形性に優れた樹脂組成物、特に半導体封止材を調製することができる。 As is clear from the comparison between the examples and the comparative examples, according to the amorphous siliceous powder of the present invention, the resin composition, particularly the semiconductor encapsulating, superior in fluidity, viscosity characteristics and moldability than the comparative examples. A material can be prepared.
本発明の非晶質シリカ質粉末は、自動車、携帯電子機器、パソコン、家庭電化製品等に使用される半導体封止材、半導体が搭載される積層板などの充填材として使用される。また、本発明の樹脂組成物は、半導体封止材の他に、ガラス織布、ガラス不織布、及びその他有機基材に含浸硬化させてなる、例えばプリント基板用のプリプレグや、各種エンジニアプラスチックス等として使用できる。
なお、2008年5月16日に出願された日本特許出願2008−129122号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。The amorphous siliceous powder of the present invention is used as a filler for semiconductor sealing materials used in automobiles, portable electronic devices, personal computers, home appliances, etc., and laminates on which semiconductors are mounted. Further, the resin composition of the present invention is obtained by impregnating and curing glass woven fabric, glass nonwoven fabric, and other organic base materials in addition to the semiconductor sealing material, for example, prepreg for printed circuit boards, various engineer plastics, etc. Can be used as
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-129122 filed on May 16, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.
Claims (8)
原料シリカ質粉末とAl源物質とを含む混合物を、バーナーで形成した火炎中に噴射し、非晶質シリカ質粉末を製造した後、温度60〜150℃、相対湿度60〜90%の雰囲気下で15〜30分保持することを特徴とする非晶質シリカ質粉末の製造方法。 A method for producing an amorphous siliceous powder according to claim 1 or 2,
After a mixture containing raw material siliceous powder and Al source material is injected into a flame formed by a burner to produce amorphous siliceous powder, the temperature is 60 to 150 ° C. and the relative humidity is 60 to 90%. For 15 to 30 minutes. A method for producing an amorphous siliceous powder, wherein
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