JP2005314177A - Spherical ferrite particle for radio wave absorbing material and its manufacturing method, and resin composition for semiconductor sealing containing ferrite particles - Google Patents
Spherical ferrite particle for radio wave absorbing material and its manufacturing method, and resin composition for semiconductor sealing containing ferrite particles Download PDFInfo
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- JP2005314177A JP2005314177A JP2004135148A JP2004135148A JP2005314177A JP 2005314177 A JP2005314177 A JP 2005314177A JP 2004135148 A JP2004135148 A JP 2004135148A JP 2004135148 A JP2004135148 A JP 2004135148A JP 2005314177 A JP2005314177 A JP 2005314177A
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 122
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 14
- 239000011358 absorbing material Substances 0.000 title abstract 2
- 238000007789 sealing Methods 0.000 title abstract 2
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
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- 229910052753 mercury Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 6
- 239000011029 spinel Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
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- 125000003700 epoxy group Chemical group 0.000 description 13
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
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- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-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
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
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- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Soft Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
本発明は、電波吸収材用球状フェライト粒子、その製造方法および球状フェライト粒子を含む半導体封止用樹脂組成物に関し、詳しくは、体積固有抵抗値が高く、細孔が極めて少なく、且つ、粒子サイズが1〜45μmの範囲で自由に制御できると共に、高い透磁率を有する、電波吸収材用として樹脂分散系において特に有効な球状フェライト粒子、その製造方法および球状フェライト粒子を含む半導体封止用樹脂組成物に関する。 The present invention relates to spherical ferrite particles for radio wave absorbers, a method for producing the same, and a resin composition for semiconductor encapsulation containing the spherical ferrite particles. Specifically, the volume resistivity is high, the pores are extremely small, and the particle size. Can be freely controlled in the range of 1 to 45 μm, and has a high magnetic permeability and is particularly effective in a resin dispersion for a radio wave absorber, a method for producing the same, and a resin composition for semiconductor encapsulation containing the spherical ferrite particles Related to things.
フェライト粒子、例えば、Mn−Zn系フェライトは、主に10kHzから30MHzの周波数で高い透磁率を示し、また、Ni−Zn系フェライトは、主に30MHzから300MHzの周波数で高い透磁率を示すため、各周波数領域の電波吸収材として使用される。そして、最近の電子機器の小型化に伴い、高周波数領域におけるフェライトの磁気損失の改善、すなわち、抵抗の低さに起因する渦電流損失の改善が図られている。 Ferrite particles, for example, Mn—Zn based ferrite mainly exhibits high magnetic permeability at a frequency of 10 kHz to 30 MHz, and Ni—Zn based ferrite mainly exhibits high magnetic permeability at a frequency of 30 MHz to 300 MHz. Used as a radio wave absorber in each frequency range. With the recent miniaturization of electronic devices, improvement of ferrite magnetic loss in a high frequency region, that is, improvement of eddy current loss due to low resistance has been attempted.
例えば、式:(MO)100−X(Fe2O3)X(但し、Mは、Li、Mg、Ni、Cu、Zn、Mn、CaおよびFeから選ばれる少なくとも1種の金属であり、Xは45〜95モル%である。)で示されるフェライトから成り、平均粒径が1〜45μmであり、BET比表面積が0.2m2/g以下であり、水銀圧入法による細孔容積が0.05ml/g以下である電波吸収材用球状フェライト粒子が知られている。
しかしながら、上記の球状フェライト粒子は、体積固有抵抗値が108〜1010Ωcm程度で十分高いものとは言えず、高周波数領域における磁気損失の改善、すなわち、抵抗の低さに起因する渦電流損失の改善が十分とはいえず、封止剤用添加物として使用した場合、環境の影響を受けやすく、信頼性に問題がある。 However, the spherical ferrite particles have a volume resistivity of about 10 8 to 10 10 Ωcm and cannot be said to be sufficiently high. Improvement of magnetic loss in a high frequency region, that is, eddy current due to low resistance Loss cannot be improved sufficiently, and when used as an additive for a sealant, it is easily affected by the environment and has a problem in reliability.
本発明は、上記の実情に鑑みなされたものであり、その目的は、体積固有抵抗値が高く、細孔が極めて少なく、且つ、粒子サイズが1〜45μmの範囲で自由に制御できると共に、高周波数領域での電磁波吸収性能に優れた電波吸収材用球状フェライト粒子、その製造方法、および、電波吸収材用球状フェライト粒子を含む半導体封止用樹脂組成物を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is that the volume resistivity value is high, the number of pores is extremely small, and the particle size can be freely controlled in the range of 1 to 45 μm. An object of the present invention is to provide a spherical ferrite particle for a radio wave absorber excellent in electromagnetic wave absorption performance in the frequency domain, a method for producing the same, and a resin composition for semiconductor encapsulation containing the spherical ferrite particle for a radio wave absorber.
本発明者等は、種々検討を重ねた結果、次の様な知見を得た。すなわち、フェライト粒子の表面にAl及び/又はSiを含有する金属酸化物表層部を形成した球状フェライト粒子によれば、平均粒径が1〜45μmの範囲で自由に制御でき、BET比表面積が0.2m2/g以下であり、水銀圧入法による細孔容積が0.05ml/g以下で細孔が極めて少ないことに加えて、体積固有抵抗が1×1011Ωcm以上であることにより、高周波数領域における磁気損失、すなわち、抵抗の低さに起因する渦電流損失の問題が解消される。 As a result of various studies, the present inventors have obtained the following knowledge. That is, according to the spherical ferrite particles in which the metal oxide surface layer containing Al and / or Si is formed on the surface of the ferrite particles, the average particle size can be freely controlled in the range of 1 to 45 μm, and the BET specific surface area is 0. .2 m 2 / g or less, the pore volume by mercury intrusion method is 0.05 ml / g or less, and in addition to extremely few pores, the volume resistivity is 1 × 10 11 Ωcm or more. The problem of eddy current loss due to magnetic loss in the frequency domain, that is, low resistance is solved.
本発明は、上記の知見に基づき完成されたものであり、その第1の要旨は、Li、Mg、Ni、Cu、Zn、Mn、Ca、Co、Zr、Sn、Ba及びTiから選ばれる1種または2種以上の金属元素をFe元素100モルに対して60モル以下含有し、且つ、スピネル構造を有するフェライト粒子であって、その表層部にSiO2、Al2O3及びTiO2から選ばれる1種または2種以上の金属酸化物を有し、金属酸化物の含有量がフェライト100重量部に対して1〜30重量部であり、平均粒径が1〜45μmであり、体積固有抵抗が1×1011Ωcm以上であり、BET比表面積が0.2m2/g以下であり、水銀圧入法による細孔容積が0.05ml/g以下である電波吸収材用の球状フェライト粒子に存する。 The present invention has been completed based on the above findings, and the first gist thereof is selected from Li, Mg, Ni, Cu, Zn, Mn, Ca, Co, Zr, Sn, Ba and Ti. Ferrite particles containing 60 mol or less of seed or two or more metal elements with respect to 100 mol of Fe element, and having a spinel structure, the surface layer portion being selected from SiO 2 , Al 2 O 3 and TiO 2 The metal oxide content is 1 to 30 parts by weight with respect to 100 parts by weight of ferrite, the average particle size is 1 to 45 μm, and the volume resistivity is 1 to 45 parts by weight. is a but 1 × 10 11 Ωcm or more, BET specific surface area of not more than 0.2 m 2 / g, resides in the spherical ferrite particles for radio wave absorption materials the pore volume by mercury porosimetry is less than 0.05 ml / g .
本発明の第2の要旨は、フェライト前駆体が分散している水性媒体中でフェノール類とアルデヒド類とを反応・硬化させるフェノール樹脂生成反応中に、Al2O3及び/又はSiO2の金属酸化物を添加して、フェライト前駆体とフェノール樹脂とから成る核部および金属酸化物とフェノール樹脂とから成る表層部から構成される複合体粒子を形成し、得られた複合体粒子を400〜700℃で加熱処理してフェノール樹脂を除去し、次いで、800〜1400℃で加熱処理してフェライト前駆体をフェライト化する球状フェライト粒子の製造方法に存する。 The second gist of the present invention is that a metal of Al 2 O 3 and / or SiO 2 is formed during a phenol resin formation reaction in which phenols and aldehydes are reacted and cured in an aqueous medium in which a ferrite precursor is dispersed. Oxides are added to form composite particles composed of a core portion composed of a ferrite precursor and a phenol resin and a surface layer portion composed of a metal oxide and a phenol resin, and the resulting composite particles are 400 to 400 It exists in the manufacturing method of the spherical ferrite particle which heat-processes at 700 degreeC, removes a phenol resin, and then heat-processes at 800-1400 degreeC, and ferritizes a ferrite precursor.
本発明の第3の要旨は、上記球状フェライト粒子とバインダー樹脂とから成ることを特徴とする半導体封止用樹脂組成物存する。 According to a third aspect of the present invention, there is provided a resin composition for encapsulating a semiconductor comprising the spherical ferrite particles and a binder resin.
本発明によれば、球状を呈し、体積固有抵抗値が1×1011Ωcm以上と高く、BET比表面積が0.2m2/g以下で、および、細孔容積が0.05ml/g以下で細孔をほとんど有しない構造を有するために、高周波数領域における磁気損失、すなわち、抵抗の低さに起因する渦電流損失を改善することが出来、封止剤用添加物として使用した場合、環境の影響を受けることがなく、電波吸収材として有用である。 According to the present invention, it is spherical and has a high volume resistivity of 1 × 10 11 Ωcm or more, a BET specific surface area of 0.2 m 2 / g or less, and a pore volume of 0.05 ml / g or less. Since it has a structure with few pores, it can improve magnetic loss in the high frequency range, that is, eddy current loss due to low resistance, and when used as an additive for sealant, And is useful as a radio wave absorber.
以下、本発明を詳細に説明する。本発明の球状フェライト粒子は、Li、Mg、Ni、Cu、Zn、Mn、Ca、Co、Zr、Sn、Ba及びTiから選ばれる1種または2種以上の金属元素をFe元素100モルに対して60モル以下含有し、且つ、スピネル構造を有するフェライト粒子であって、その表層部にAl2O3及び/又はSiO2の金属酸化物を有する。 Hereinafter, the present invention will be described in detail. The spherical ferrite particles of the present invention contain one or more metal elements selected from Li, Mg, Ni, Cu, Zn, Mn, Ca, Co, Zr, Sn, Ba and Ti with respect to 100 mol of Fe element. Ferrite particles having a spinel structure and having a metal oxide of Al 2 O 3 and / or SiO 2 in the surface layer.
スピネル構造を有するフェライト粒子を構成するFe元素以外の金属元素として、Li、Mg、Ni、Cu、Zn、Mn、Ca、Co、Zr、Sn、Ba及びTiが挙げられ、中でも、Mg、Ni、Cu、ZnおよびMnが好ましい。 Examples of metal elements other than the Fe element constituting the ferrite particles having the spinel structure include Li, Mg, Ni, Cu, Zn, Mn, Ca, Co, Zr, Sn, Ba, and Ti. Among these, Mg, Ni, Cu, Zn and Mn are preferred.
スピネル構造を有するフェライト粒子におけるLi、Mg、Ni、Cu、Zn、Mn、Ca、Co、Zr、Sn、Ba及びTiから選ばれる1種または2種以上の金属元素の量は、Fe元素100モルに対して60モル以下、好ましくは2〜55モルである。60モルを超える場合は、得られる球状フェライト粒子の磁化値が不十分となり、キャリアが飛散したり、感光体に付着してしまう問題がある。 The amount of one or more metal elements selected from Li, Mg, Ni, Cu, Zn, Mn, Ca, Co, Zr, Sn, Ba and Ti in the ferrite particles having a spinel structure is 100 mol of Fe element. The amount is 60 mol or less, preferably 2 to 55 mol. When the amount exceeds 60 mol, the magnetization value of the obtained spherical ferrite particles becomes insufficient, and there is a problem that carriers are scattered or attached to the photoreceptor.
球状フェライト粒子を構成する表層部は、Al2O3及び/又はSiO2の金属酸化物を含有する。球状フェライト粒子中の金属酸化物の量は、フェライト100重量部に対して通常1〜30重量部、好ましくは2〜20重量部である。金属酸化物の量が1重量部の場合は、体積固有抵抗が1×1011Ωcm未満と成る場合がある。また、30重量部を超える場合は、球状フェライト粒子の磁化値が不十分となり、キャリアが飛散したり、感光体に付着してしまう問題がある。なお、球状フェライト粒子の組成およびその含有量は、無機粒子の通常の分析法、例えば、X線回析分析法およびX線光電子分析法によって測定することが出来る。 Surface portion constituting the spherical ferrite particles containing Al 2 O 3 and / or SiO 2 metal oxide. The amount of the metal oxide in the spherical ferrite particles is usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight with respect to 100 parts by weight of ferrite. When the amount of the metal oxide is 1 part by weight, the volume resistivity may be less than 1 × 10 11 Ωcm. On the other hand, when the amount exceeds 30 parts by weight, there is a problem that the magnetization value of the spherical ferrite particles becomes insufficient, and carriers are scattered or attached to the photoreceptor. In addition, the composition and content of the spherical ferrite particles can be measured by a usual analysis method for inorganic particles, for example, an X-ray diffraction analysis method and an X-ray photoelectron analysis method.
球状フェライト粒子の平均粒子径は、通常1〜45μm、好ましくは10〜45μmである。平均粒子径が1μm未満の場合は、感光体への飛散が起こり、また、45μmを超える場合は、高画質化を達成することが困難になる。 The average particle diameter of the spherical ferrite particles is usually 1 to 45 μm, preferably 10 to 45 μm. When the average particle diameter is less than 1 μm, scattering to the photoreceptor occurs, and when it exceeds 45 μm, it is difficult to achieve high image quality.
球状フェライト粒子の体積固有抵抗は、通常1×1011Ωcm以上、好ましくは1×1011〜1×1015Ωcm、より好ましくは、1×1012〜1×1015Ωcmの範囲である。1×1011Ωcm未満の場合には、キャリアが感光体の画像部へ付着したり、潜像電荷がキャリアを介して逃げ、潜像の乱れや画像の欠損等を生じたりする等の問題がある。なた、1×1015Ωcmを超える場合は、ベタ印刷での白抜け等の問題が生じる場合がある。 The volume resistivity of the spherical ferrite particles is usually 1 × 10 11 Ωcm or more, preferably 1 × 10 11 to 1 × 10 15 Ωcm, and more preferably 1 × 10 12 to 1 × 10 15 Ωcm. If it is less than 1 × 10 11 Ωcm, there are problems such as the carrier adhering to the image area of the photoconductor or the latent image charge escaping through the carrier, resulting in disturbance of the latent image or image loss. is there. However, if it exceeds 1 × 10 15 Ωcm, problems such as white spots in solid printing may occur.
球状フェライト粒子のBET比表面積は、0.2m2/g以下、好ましくは0.15m2/g以下である。BET比表面積が0.2m2/gを超える場合は、帯電の環境安定性が悪くなる。また、後述の水銀圧入法による細孔容積は、0.05ml/g以下、好ましくは0.01ml/g以下である。細孔容積が0.05ml/gを超える場合は、帯電の環境安定性が悪くなる。BET比表面積、細孔容積の下限は特に制限されないが、測定機の測定精度の点から、通常、BET比表面積は0.01m2/g程度、細孔容積は0.001ml/g程度である。 The BET specific surface area of the spherical ferrite particles is 0.2 m 2 / g or less, preferably 0.15 m 2 / g or less. When the BET specific surface area exceeds 0.2 m 2 / g, the environmental stability of charging is deteriorated. Moreover, the pore volume by the mercury intrusion method to be described later is 0.05 ml / g or less, preferably 0.01 ml / g or less. When the pore volume exceeds 0.05 ml / g, the environmental stability of charging is deteriorated. The lower limits of the BET specific surface area and pore volume are not particularly limited, but from the viewpoint of measurement accuracy of the measuring instrument, the BET specific surface area is usually about 0.01 m 2 / g and the pore volume is about 0.001 ml / g. .
球状フェライト粒子の球形度(l/w)は、通常1.0〜1.5、好ましくは1.0〜1.3であり、真比重は、通常4.0〜6.0、好ましくは4.5〜5.7であり、嵩密度は、通常2.0〜3.0g/ml、好ましくは2.1〜2.7g/mlである。 The sphericity (l / w) of the spherical ferrite particles is usually 1.0 to 1.5, preferably 1.0 to 1.3, and the true specific gravity is usually 4.0 to 6.0, preferably 4 The bulk density is usually 2.0 to 3.0 g / ml, preferably 2.1 to 2.7 g / ml.
本発明の球状フェライト粒子は、上述の様に体積固有抵抗が高いため、高周波数領域における磁気損失を抑制することが出来る。さらに、フェライト粒子に非磁性粒子を混合すると、通常、比透磁率の低下が起こるが、意外にも、本発明の球状フェライト粒子は、従来の球状フェライト粒子と同等以上の比透磁率を有し、その結果、電波吸収能にも優れている。 Since the spherical ferrite particles of the present invention have a high volume resistivity as described above, magnetic loss in a high frequency region can be suppressed. Furthermore, when non-magnetic particles are mixed with ferrite particles, the relative permeability usually decreases, but surprisingly, the spherical ferrite particles of the present invention have a relative permeability equal to or higher than that of conventional spherical ferrite particles. As a result, the radio wave absorption ability is also excellent.
本発明の球状フェライト粒子の表層部は、エポキシ樹脂、フェノール樹脂およびシリコーン樹脂から選ばれた少なくとも1種の樹脂で被覆されていてもよい。樹脂で球状フェライト粒子の表層部を被覆することにより、体積固有抵抗が高くなることに加えて、封止材中に充填した場合、粘性が低下して流動性が向上し、その結果、球状フェライト粒子の充填量を高くすることが出来る。 The surface layer portion of the spherical ferrite particles of the present invention may be coated with at least one resin selected from an epoxy resin, a phenol resin, and a silicone resin. By covering the surface layer of spherical ferrite particles with resin, the volume resistivity is increased, and when filled in a sealing material, the viscosity is lowered and the fluidity is improved. The filling amount of particles can be increased.
エポキシ樹脂としては、1分子中に2個以上のエポキシ基を有し、且つ、エポキシ当量が200以上であるエポキシ樹脂が挙げられ、具体的には、ビスフェノールA型エポキシ樹脂、ノボラック型エポキシ樹脂、ハロゲン化エポキシ樹脂、グリシジルエステル型エポキシ樹脂などが挙げられる。 Examples of the epoxy resin include epoxy resins having two or more epoxy groups in one molecule and having an epoxy equivalent of 200 or more. Specifically, bisphenol A type epoxy resins, novolac type epoxy resins, Examples thereof include halogenated epoxy resins and glycidyl ester type epoxy resins.
エポキシ当量は、通常200〜600g/当量、好ましくは200−500g/当量である。1分子中のエポキシ基が2個未満の場合は、フェライト粒子との接着性が不十分となる。半導体封止材用として使用する場合、エポキシ樹脂組成物の低粘度化を考慮すると、1分子中のエポキシ基の上限は3である。エポキシ当量が200g/当量未満の場合は、エポキシ樹脂組成物の成形時の流動性が良くない。600g/当量を超える場合は、得られる成形体のパッキング性が不十分となる。 The epoxy equivalent is usually 200 to 600 g / equivalent, preferably 200 to 500 g / equivalent. When the number of epoxy groups in one molecule is less than 2, the adhesion with the ferrite particles is insufficient. When used as a semiconductor encapsulant, the upper limit of epoxy groups in one molecule is 3 in view of lowering the viscosity of the epoxy resin composition. When the epoxy equivalent is less than 200 g / equivalent, the fluidity during molding of the epoxy resin composition is not good. When it exceeds 600 g / equivalent, the packing property of the obtained molded article becomes insufficient.
フェノール樹脂としては、フェノールとホルマリンのモル比で通常1/1〜1/3の範囲にあるレゾ−ル系のフェノール樹脂が挙げられ、そのOH当量は、通常150g/当量以上、好ましくは180g/当量〜300g/当量である。OH当量が150g/当量未満の場合は、得られた成型体の吸水率が高く、且つ、パッキング性も悪くなる。 Examples of the phenolic resin include resole phenolic resins usually having a molar ratio of phenol to formalin in the range of 1/1 to 1/3, and the OH equivalent thereof is usually 150 g / equivalent or more, preferably 180 g / equivalent. Equivalent to 300 g / equivalent. When the OH equivalent is less than 150 g / equivalent, the water absorption of the obtained molded product is high and the packing property is also deteriorated.
シリコーン樹脂としては、3官能性単位と2官能性単位とのモル比率が通常100:0〜60:40、好ましくは100:0〜70:30であるシリコーン樹脂が挙げられる。モル比率が上記範囲外の場合は、樹脂組成物の流動性が悪く、パッキング性も悪くなる。また、エポキシ変性またはアクリル変性のシリコーン樹脂も使用することが出来る。 Examples of the silicone resin include silicone resins in which the molar ratio of trifunctional units to bifunctional units is usually 100: 0 to 60:40, preferably 100: 0 to 70:30. When the molar ratio is outside the above range, the fluidity of the resin composition is poor and the packing property is also poor. Epoxy-modified or acrylic-modified silicone resins can also be used.
樹脂被覆量は、フェライト粒子に対し通常0.1〜10重量%、好ましくは0.2〜5重量%である。樹脂被覆量が0.1重量%未満の場合は、エポキシ樹脂との相溶性の改善が不十分であり、樹脂組成物の流動性の改善も不十分である。10重量%を超える場合は、フェライト粒子の充填量を高めることが困難となり、フェライト粒子の機能を十分に発揮することが難しくなる。 The resin coating amount is usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the ferrite particles. When the resin coating amount is less than 0.1% by weight, the improvement of the compatibility with the epoxy resin is insufficient, and the improvement of the fluidity of the resin composition is also insufficient. When it exceeds 10% by weight, it is difficult to increase the filling amount of the ferrite particles, and it becomes difficult to sufficiently exhibit the function of the ferrite particles.
次に、球状フェライト粒子の製造方法について説明する。球状フェライト粒子は、フェライト前駆体が分散している水性媒体中でフェノール類とアルデヒド類とを反応・硬化させるフェノール樹脂生成反応中に、Al2O3及び/又はSiO2の金属酸化物を添加して、金属酸化物とフェノール樹脂とから成る表層部およびフェライト前駆体の核部とから成る複合体粒子を形成し、得られた複合体粒子を400〜700℃で加熱処理してフェノール樹脂を除去し、次いで、800〜1400℃で加熱処理してフェライト前駆体をフェライト化して得られる。 Next, a method for producing spherical ferrite particles will be described. Spherical ferrite particles are added with Al 2 O 3 and / or SiO 2 metal oxides during the phenol resin formation reaction in which phenols and aldehydes are reacted and cured in an aqueous medium in which ferrite precursors are dispersed. Then, composite particles composed of a surface layer portion made of a metal oxide and a phenol resin and a core portion of a ferrite precursor are formed, and the obtained composite particles are heated at 400 to 700 ° C. to obtain a phenol resin. It is then removed and then heat treated at 800 to 1400 ° C. to obtain a ferrite precursor that is made into a ferrite.
使用するフェライト前駆体は、芯粒子を構成する元素の供給源であって、例えば、Li、Mg、Ni、Cu、Zn、Mn、Ca、Fe等の酸化物、水酸化物、シュウ酸塩、炭酸塩などの粒子が挙げられる。また、Fe元素の供給源としては、Fe2O3粒子が挙げられる。各元素の供給源は、水に溶解せず、水によって変質、変性しないものであればよく、各元素の酸化物粒子が好ましい。フェライト前駆体は、目的とするフェライト粒子の組成比率になる様に、例えば、Li2O、Li2CO3、MgO、NiO、CuO、ZnO、MnO、Mn3O4、CaO、CoO、ZrO2、SnO2、BaO、TiO2等とFe2O3の各粒子を混合して使用する。 The ferrite precursor to be used is a supply source of elements constituting the core particles, for example, oxides such as Li, Mg, Ni, Cu, Zn, Mn, Ca, Fe, hydroxide, oxalate, Examples of the particles include carbonates. Further, Fe 2 O 3 particles may be mentioned as a source of Fe element. The supply source of each element may be any element as long as it does not dissolve in water and is not altered or modified by water, and oxide particles of each element are preferable. For example, Li 2 O, Li 2 CO 3 , MgO, NiO, CuO, ZnO, MnO, Mn 3 O 4 , CaO, CoO, and ZrO 2 are used so that the ferrite precursor has the desired composition ratio of ferrite particles. , SnO 2 , BaO, TiO 2 and the like and Fe 2 O 3 particles are mixed and used.
フェライト前駆体の粒子形態は、立方体状、多面体状、球状、針状、板状などのいずれの形態でもよい。平均粒子径は、複合体粒子の平均粒子径よりも小さい粒子であればよく、通常0.01〜5.0μm、好ましくは0.1〜2.0μmである。フェライト前駆体の平均粒子径が0.01μm未満の場合は、複合体粒子中のフェライト前駆体の含有量が低くなり、球状フェライト粒子の磁化値が不十分となる。また、5.0μmを超える場合は、複合体粒子およびフェライト粒子の球形度が悪化する。 The particle form of the ferrite precursor may be any form such as a cube, polyhedron, sphere, needle, or plate. The average particle diameter may be a particle smaller than the average particle diameter of the composite particles, and is usually 0.01 to 5.0 μm, preferably 0.1 to 2.0 μm. When the average particle diameter of the ferrite precursor is less than 0.01 μm, the content of the ferrite precursor in the composite particles becomes low, and the magnetization value of the spherical ferrite particles becomes insufficient. On the other hand, when it exceeds 5.0 μm, the sphericity of the composite particles and the ferrite particles deteriorates.
フェライト前駆体は、組成の均一性を高めるために、必要に応じて、仮焼成する。仮焼成は、通常700〜1000℃で1〜4時間程度行う。 The ferrite precursor is temporarily fired as necessary in order to improve the uniformity of the composition. Temporary baking is normally performed at 700-1000 degreeC for about 1-4 hours.
添加する金属酸化物粒子としては、SiO2、Al2O3およびそれらの混合物を使用する。平均粒子径は、通常0.01〜5.0μm、好ましくは、0.1〜2.0μmの範囲である。金属酸化物粒子の平均粒子径が0.01μm未満の場合は、体積固有抵抗値を高めることが不十分であり、また、5.0μmを超える場合は、複合体粒子およびフェライト粒子の表面が凹凸になったり、球形度が悪化する。 As metal oxide particles to be added, SiO 2 , Al 2 O 3 and a mixture thereof are used. The average particle size is usually 0.01 to 5.0 μm, preferably 0.1 to 2.0 μm. When the average particle diameter of the metal oxide particles is less than 0.01 μm, it is insufficient to increase the volume resistivity, and when it exceeds 5.0 μm, the surfaces of the composite particles and the ferrite particles are uneven. Or sphericity deteriorates.
フェライト前駆体および金属酸化物粒子は、親油化処理粒子が好ましい。未親油化処理のフェライト前駆体を使用した場合、優れた球形度を有する複合体粒子を得ることが困難となることがある。また、未親油化処理の金属酸化物粒子を使用した場合は、金属酸化物粒子が複合体粒子表層にしっかりと埋め込まれず、複合体粒子と遊離してしまうことがある。 The ferrite precursor and metal oxide particles are preferably lipophilic particles. When a non-lipophilic ferrite precursor is used, it may be difficult to obtain composite particles having excellent sphericity. When metal oxide particles that have not been oleophilicized are used, the metal oxide particles may not be firmly embedded in the surface of the composite particle and may be separated from the composite particle.
親油化処理としては、フェライト前駆体および金属酸化物粒子をシラン系カップリング剤、チタネート系カップリング剤などのカップリング剤で処理する方法、界面活性剤を含む水性媒体中にフェライト前駆体および金属酸化物粒子を分散させ、粒子表面に界面活性剤を吸着させる方法などが挙げられる。 As the oleophilic treatment, a method of treating a ferrite precursor and metal oxide particles with a coupling agent such as a silane coupling agent or a titanate coupling agent, a ferrite precursor in an aqueous medium containing a surfactant, and Examples include a method of dispersing metal oxide particles and adsorbing a surfactant on the particle surface.
シラン系カップリング剤としては、疎水性基、エポキシ基、アミノ基を有するものが挙げられ、これらは単独でまたは必要に応じ2種以上組み合わせて使用される。 Examples of the silane coupling agent include those having a hydrophobic group, an epoxy group, and an amino group, and these may be used alone or in combination of two or more as required.
疎水性基を有するシラン系カップリング剤としては、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニルトリス(β−メトキシ)シラン等が挙げられる。エポキシ基を有するシラン系カップリング剤としては、γ−グリシドキシプロピルメチルジメトキシシラン、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)トリメトキシシラン等が挙げられる。アミノ基を有するシラン系カップリング剤としては、γ−アミノプロピルトリメトキシシラン、N−β−(アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−β−(アミノエチル)−γ−アミノプロピルメチルジメトキシシラン、N−フェニル−γ−アミノプロピルトリメトキシシラン等が挙げられる。 Examples of the silane coupling agent having a hydrophobic group include vinyltrichlorosilane, vinyltriethoxysilane, and vinyltris (β-methoxy) silane. Examples of the silane coupling agent having an epoxy group include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) trimethoxysilane, and the like. Examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropyl. Examples include methyldimethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane.
チタネート系カップリング剤としては、イソプロピルトリイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルトリス(ジオクチルピロホスフェート)チタネート等が挙げられる。 Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and the like.
界面活性剤としては、特に制限はなく、公知の界面活性剤を使用することができる。例えば、フェライト前駆体や金属酸化物粒子および当該粒子表面に有する水酸基と結合可能な官能基を有するものが挙げられ、イオン性で言えば、カチオン性またはアニオン性のものが好ましい。これらは単独でまたは必要に応じ2種以上組み合わせて用いられる。 There is no restriction | limiting in particular as surfactant, A well-known surfactant can be used. Examples thereof include ferrite precursors and metal oxide particles and those having a functional group capable of binding to a hydroxyl group on the particle surface. In terms of ionicity, cationic or anionic ones are preferable. These may be used alone or in combination of two or more as required.
上述のフェライト前駆体および金属酸化物粒子の親油化処理中、フェノール樹脂との接着性を考慮すると、アミノ基またはエポキシ基を有するシラン系カップリング剤による親油化処理が好ましい。 In view of the adhesion with the phenol resin during the lipophilic treatment of the ferrite precursor and the metal oxide particles, the lipophilic treatment with a silane coupling agent having an amino group or an epoxy group is preferable.
親油化処理剤の量は、フェライト前駆体または金属酸化物粒子に対して0.1〜5.0重量%が好ましい。0.1重量%未満の場合は、親油化処理が不十分なために目的のフェライト粒子含有量を有する複合体粒子を得ることが困難であり、また、金属酸化物粒子が複合体粒子にしっかりと埋め込まれないことがある。一方、5.0重量%を超える場合は、生成した複合体粒子同志の凝集が生じ、複合体粒子の粒子サイズの制御が困難になる。 The amount of the oleophilic treatment agent is preferably 0.1 to 5.0% by weight with respect to the ferrite precursor or metal oxide particles. If it is less than 0.1% by weight, it is difficult to obtain composite particles having the desired ferrite particle content due to insufficient lipophilic treatment, and the metal oxide particles become composite particles. It may not be firmly embedded. On the other hand, when it exceeds 5.0% by weight, the produced composite particles are aggregated, and it becomes difficult to control the particle size of the composite particles.
球状フェライト粒子の製造は、まず、フェライト前駆体および塩基性触媒の存在下でフェノール類とアルデヒド類とを水性媒体中で反応させてフェライト前駆体とフェノール樹脂とから成る球状の核部を調製し、そして、反応途中で金属酸化物粒子を添加することにより、金属酸化物粒子とフェノール樹脂とから成る表層部を調製して、核部と表層部とを有する複合体粒子を形成する。 In the production of spherical ferrite particles, first, a spherical core composed of a ferrite precursor and a phenol resin is prepared by reacting a phenol and an aldehyde in an aqueous medium in the presence of a ferrite precursor and a basic catalyst. Then, by adding metal oxide particles during the reaction, a surface layer portion composed of the metal oxide particles and the phenol resin is prepared, and composite particles having a core portion and a surface layer portion are formed.
複合体粒子中のフェライト前駆体および金属酸化物粒子の含有量は、通常80〜98重量%である。含有量が80重量%未満の場合は、フェノール樹脂が多いため加熱処理時において、フェライト樹脂を除去するエネルギーが多く必要となり好ましくない。また、98重量%を超える場合は、加熱処理前の複合体粒子の強度が弱くなり、加熱処理時に粒子が破壊することがある。 The content of the ferrite precursor and the metal oxide particles in the composite particles is usually 80 to 98% by weight. When the content is less than 80% by weight, since there is a large amount of phenol resin, a large amount of energy for removing the ferrite resin is required during the heat treatment, which is not preferable. On the other hand, if it exceeds 98% by weight, the strength of the composite particles before the heat treatment becomes weak, and the particles may be destroyed during the heat treatment.
本発明で使用される塩基性触媒としては、通常のフェノール樹脂製造に使用される塩基性触媒が挙げられる。例えば、アンモニア水、ヘキサメチレンテトラミン及びジメチルアミン、ジエチルトリアミン、ポリエチレンイミン等のアルキルアミンが挙げられる。塩基性触媒のフェノール類に対する量(モル比)は、通常0.02〜0.7である。モル比が0.02未満の場合は、反応が十分に進まず、また、0.7を超える場合は、過剰な塩基性触媒が反応溶液中に多く残り、排水処理の負荷を増大させるので好ましくない。 As a basic catalyst used by this invention, the basic catalyst used for normal phenol resin manufacture is mentioned. Examples thereof include aqueous ammonia, hexamethylenetetramine, and alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine. The amount (molar ratio) of the basic catalyst to the phenol is usually 0.02 to 0.7. When the molar ratio is less than 0.02, the reaction does not proceed sufficiently, and when it exceeds 0.7, a large amount of excess basic catalyst remains in the reaction solution, which increases the wastewater treatment load. Absent.
本発明で使用されるフェノール類としては、フェノールの他、m−クレゾール、p−tert−ブチルフェノール、o−プロピルフェノール、レゾルシノール、ビスフェノールA等のアルキルフェノール類、ベンゼン核、アルキル基の一部または全部が塩素原子または臭素原子で置換されたハロゲン化フェノール類などのフェノール性水酸基を有する化合物などが挙げられ、これらは単独でまたは必要に応じ2種以上組み合わせて使用される。中でも、フェノールが好ましい。 As phenols used in the present invention, in addition to phenol, alkylphenols such as m-cresol, p-tert-butylphenol, o-propylphenol, resorcinol, bisphenol A, benzene nucleus, and a part or all of alkyl groups are included. Examples thereof include compounds having a phenolic hydroxyl group such as halogenated phenols substituted with a chlorine atom or a bromine atom, and these are used alone or in combination of two or more as required. Of these, phenol is preferred.
本発明で使用されるアルデヒド類としては、ホルマリン又はパラホルムアルデヒドの何れかの形態のホルムアルデヒド及びフルフラール等が挙げられ、これらは単独でまたは必要に応じ2種以上組み合わせて使用される。中でも、ホルムアルデヒドが好ましい。アルデヒド類のフェノール類に対する量(モル比)は、通常1〜4、好ましくはは1.2〜3である。モル比が1未満の場合は、粒子が形成し難かったり、形成したとしても樹脂の硬化が進行し難いために生成する粒子の強度が弱かったりする。また、モル比が4を超える場合は、反応後に水性媒体中に残留する未反応のアルデヒド類量が増加するので好ましくない。 Examples of the aldehydes used in the present invention include formaldehyde and furfural in any form of formalin or paraformaldehyde, and these are used alone or in combination of two or more as required. Of these, formaldehyde is preferable. The amount (molar ratio) of aldehydes to phenols is usually 1 to 4, preferably 1.2 to 3. When the molar ratio is less than 1, the particles are difficult to form, and even if they are formed, the curing of the resin is difficult to proceed, and the strength of the generated particles is weak. On the other hand, when the molar ratio exceeds 4, the amount of unreacted aldehydes remaining in the aqueous medium after the reaction increases, which is not preferable.
上述のフェノール類とアルデヒド類とを反応・硬化させるフェノール樹脂生成反応の温度は、通常70〜90℃である。そして、反応・硬化した後、40℃以下に冷却して球状複合体粒子を含む水分散液を得る。 The temperature of the phenol resin formation reaction in which the above phenols and aldehydes are reacted / cured is usually 70 to 90 ° C. And after reaction and hardening, it cools to 40 degrees C or less, and obtains the water dispersion liquid containing a spherical composite particle.
次に、得られた水分散液を濾過、遠心分離等の定法に従って固液を分離した後、乾燥してフェライト前駆体および金属酸化物粒子とフェノール樹脂から成る球状複合体粒子を得る。 Next, the obtained aqueous dispersion is separated into solid and liquid according to conventional methods such as filtration and centrifugation, and then dried to obtain spherical composite particles composed of a ferrite precursor, metal oxide particles, and a phenol resin.
フェノール樹脂生成反応においては、必要により、懸濁安定剤を存在させてもよい。懸濁安定剤としては、カルボキシメチルセルロース、ポリビニルアルコールの様な親水性有機化合物、フッ化カルシウムの様なフッ素化合物、硫酸カルシウム等の水に不溶性の無機塩類などが挙げられ、これらは単独でまたは必要に応じ2種以上組み合わせて使用する。 In the phenol resin formation reaction, a suspension stabilizer may be present if necessary. Examples of the suspension stabilizer include hydrophilic organic compounds such as carboxymethyl cellulose and polyvinyl alcohol, fluorine compounds such as calcium fluoride, and water-insoluble inorganic salts such as calcium sulfate. These may be used alone or as necessary. Two or more types are used in combination depending on the condition.
次に、得られた球状複合体粒子を加熱処理してフェノール樹脂を除去する。加熱処理の温度は、フェノール樹脂が分解する温度、すなわち、400〜700℃、好ましくは500〜600℃である。加熱処理の温度が700℃を超える場合は、粒子間の凝集が生じ、粒度分布が広くなる。また、400℃未満の場合は、フェノール樹脂が十分に分解除去されない。加熱処理時間は、加熱温度によっても変わるが、通常2〜8時間程度である。2時間未満の場合は、フェノール樹脂の分解が不十分で樹脂の除去が不十分となる。また一方、8時間を超える場合は、処理時間自体が長くなり過ぎ、効率的でない。 Next, the obtained spherical composite particles are heat-treated to remove the phenol resin. The temperature of heat processing is the temperature which a phenol resin decomposes | disassembles, ie, 400-700 degreeC, Preferably it is 500-600 degreeC. When the temperature of the heat treatment exceeds 700 ° C., aggregation between particles occurs and the particle size distribution becomes wide. Moreover, when it is less than 400 degreeC, a phenol resin is not fully decomposed and removed. The heat treatment time varies depending on the heating temperature, but is usually about 2 to 8 hours. In the case of less than 2 hours, the phenol resin is not sufficiently decomposed and the resin is not sufficiently removed. On the other hand, if it exceeds 8 hours, the processing time itself becomes too long, which is not efficient.
加熱処理炉としては、固定式、回転式など何れの処理機でもよい。粒子同志の凝集を防ぐ点からは、回転式のものが好ましい。加熱処理の雰囲気は、フェノール樹脂を分解し、炭素として残存させない点を考慮して、酸化雰囲気が好ましい。酸化雰囲気としては、空気を加熱処理炉内に流せばよく、その流量は、通常1L/min以上である。1L/min未満の場合は、熱処理炉内に樹脂の分解ガスが充満し、その結果、炭素が残存することがある。 The heat treatment furnace may be any processing machine such as a fixed type or a rotary type. From the viewpoint of preventing aggregation of particles, a rotary type is preferable. The atmosphere of the heat treatment is preferably an oxidizing atmosphere in consideration of not decomposing the phenol resin and leaving it as carbon. As the oxidizing atmosphere, air may be flowed into the heat treatment furnace, and the flow rate is usually 1 L / min or more. If it is less than 1 L / min, the heat treatment furnace may be filled with resin decomposition gas, and as a result, carbon may remain.
フェノール樹脂を除去した後、加熱処理(焼成)をしてフェライト化する。加熱処理の温度はフェライト組成によっても異なるが、通常800〜1400℃、好ましくは900〜1300℃である。加熱処理の温度が1400℃を超える場合は、粒子同士が焼結してしまい、粒度分布が広くなる欠点がある。また、800℃未満な場合は、フェライト化が不十分であり、磁束密度が不足する欠点がある。加熱処理時間は、加熱温度によっても変わるが、通常1〜10時間程度である。1時間未満の場合は、フェライト化が不十分となり、10時間を超える場合は、生産性が低下する。 After removing the phenol resin, it is ferritized by heat treatment (firing). Although the temperature of heat processing changes also with ferrite compositions, it is 800-1400 degreeC normally, Preferably it is 900-1300 degreeC. When the temperature of the heat treatment exceeds 1400 ° C., the particles are sintered with each other, and there is a disadvantage that the particle size distribution becomes wide. On the other hand, when the temperature is less than 800 ° C., there is a disadvantage that the ferrite formation is insufficient and the magnetic flux density is insufficient. The heat treatment time varies depending on the heating temperature, but is usually about 1 to 10 hours. If it is less than 1 hour, ferritization is insufficient, and if it exceeds 10 hours, productivity is lowered.
加熱処理(焼成)の雰囲気は、組成によって飽和磁化や電気抵抗値を所望の値にするために変えればよく、空気を流した酸化雰囲気下で行う場合、窒素ガス等の不活性ガスを流しながら処理を行う非酸化雰囲気下で行う場合、空気および窒素の混合ガスを流しながら行う場合などを適宜選択すればよい。ガスの流量は、通常1L/min以上である。1L/min未満の場合は、所望の飽和磁化や電気抵抗を得ることが困難である。 The atmosphere of the heat treatment (firing) may be changed depending on the composition in order to make the saturation magnetization and the electric resistance value a desired value. When performing in an oxidizing atmosphere in which air is passed, an inert gas such as nitrogen gas is allowed to flow. When the treatment is performed in a non-oxidizing atmosphere, a case where the treatment is performed while flowing a mixed gas of air and nitrogen may be appropriately selected. The gas flow rate is usually 1 L / min or more. If it is less than 1 L / min, it is difficult to obtain desired saturation magnetization and electrical resistance.
球状フェライト粒子は、エポキシ樹脂、フェノール樹脂およびシリコーン樹脂から選ばれた少なくとも1種の樹脂で被覆してもよい。この樹脂被覆は、球状フェライト粒子と樹脂と若干の溶剤とを攪拌機能を有する処理機により混合・攪拌して行う。処理機としては、ハイスピードミキサー(深江パウテック(株)製)、ヘンシェルミキサー(三井三(株)製)、CFグラニュレーター(フロイント産業(株)製)、バーチカル・グラニュレーター((株)パウレック製)、フロージェットグラニュレーター((株)大川原製作所製)、万能攪拌機((株)ダルトン製)、ナウタミキサー((株)ホソカワミクロン製)等が使用できる。 The spherical ferrite particles may be coated with at least one resin selected from an epoxy resin, a phenol resin, and a silicone resin. This resin coating is performed by mixing and stirring the spherical ferrite particles, the resin, and some solvent with a processing machine having a stirring function. High-speed mixer (Fukae Powtech Co., Ltd.), Henschel Mixer (Mitsui San Co., Ltd.), CF Granulator (Freund Sangyo Co., Ltd.), Vertical Granulator (Powrec Co., Ltd.) ), Flow jet granulator (manufactured by Okawara Manufacturing Co., Ltd.), universal stirrer (manufactured by Dalton Co., Ltd.), Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.), and the like.
球状フェライト粒子を樹脂で被覆するに際し、必要に応じて、各種の硬化剤を用いることが出来る。硬化剤としては、アミン類、酸無水物類、金属アルコキシド類、フェノールノボラック樹脂などが挙げられる。硬化剤の添加量は、樹脂に対して通常0.01〜5重量%である。0.01重量%未満の場合には、球状フェライト粒子同士が凝集してしまうことがある。また、5重量%を超える場合は、封止材として使用した場合に吸湿性の問題を生じることがある。 When coating the spherical ferrite particles with a resin, various curing agents can be used as necessary. Examples of the curing agent include amines, acid anhydrides, metal alkoxides, and phenol novolac resins. The addition amount of the curing agent is usually 0.01 to 5% by weight with respect to the resin. When the amount is less than 0.01% by weight, the spherical ferrite particles may aggregate. Moreover, when it exceeds 5 weight%, when it uses as a sealing material, the problem of a hygroscopic property may be produced.
次に、半導体封止用樹脂組成物について述べる。半導体封止用樹脂組成物は、球状フェライト粒子または樹脂被覆された球状フェライト粒子とバインダー樹脂とから成り、必要に応じて、フェノール樹脂系硬化剤、硬化促進剤、シリカ粉末を含んでいてもよい。 Next, the resin composition for semiconductor encapsulation will be described. The resin composition for encapsulating a semiconductor comprises spherical ferrite particles or resin-coated spherical ferrite particles and a binder resin, and may contain a phenol resin curing agent, a curing accelerator, and silica powder as necessary. .
バインダー樹脂としては、エポキシ樹脂が挙げられ、具体的には、ビスフェノールA型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂などが挙げられる。 Examples of the binder resin include epoxy resins. Specifically, bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, brominated bisphenol A type epoxy resins, brominated phenol novolac type epoxy resins, and the like. Is mentioned.
硬化剤としては、アミン類、酸無水物類、フェノールノボラック樹脂などが挙げられ、フェノールノボラック樹脂が好ましい。 Examples of the curing agent include amines, acid anhydrides, phenol novolac resins, and the like, and phenol novolac resins are preferable.
樹脂組成物中の球状フェライト粒子の含有量は、通常10〜50重量%、好ましくは20〜50重量%である。樹脂組成物中のシリカ粒子の含有量は、通常30重量%以下、好ましくは20重量%以下である。電波吸収性を考慮すると、球状フェライト粒子の含有量は多いほど好ましい。 The content of the spherical ferrite particles in the resin composition is usually 10 to 50% by weight, preferably 20 to 50% by weight. The content of silica particles in the resin composition is usually 30% by weight or less, preferably 20% by weight or less. Considering the radio wave absorptivity, the larger the content of the spherical ferrite particles, the better.
本発明に係る球状のフェライト粒子は、真球に近い球形度を有し、特定の粒度分布を有し、さらに、体積固有抵抗値が1×1011〜1×1015Ωcmと高く、BET比表面積が0.2m2/g以下で細孔容積が0.04ml/g以下であり、細孔をほとんど有しない構造をもつために、高い透磁率を有しているため、電波吸収材用材料として有用である。 The spherical ferrite particles according to the present invention have a sphericity close to a true sphere, have a specific particle size distribution, and have a high volume resistivity of 1 × 10 11 to 1 × 10 15 Ωcm and a BET ratio. Since the surface area is 0.2 m 2 / g or less, the pore volume is 0.04 ml / g or less, and the structure has few pores, it has a high magnetic permeability. As useful.
さらに、特定の樹脂を被覆した球状フェライト粒子および該フェライト粒子を含んだ半導体封止用樹脂組成物は溶融粘度も低く、フェライト粒子を高含有することが可能であり、高い信頼性と高い透磁率を有しているため、電波吸収材として有用である。 Furthermore, the spherical ferrite particles coated with a specific resin and the resin composition for semiconductor encapsulation containing the ferrite particles have a low melt viscosity, can contain a high amount of ferrite particles, and have high reliability and high magnetic permeability. Therefore, it is useful as a radio wave absorber.
以下、実施例により本発明を詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。なお、以下の方法でその特性を測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded. The characteristics were measured by the following method.
平均粒子径は、レーザー回折式粒度分布計(RODOS、SYMPATEC社製)により測定した。 The average particle size was measured with a laser diffraction particle size distribution meter (RODOS, manufactured by SYMPATEC).
かさ密度はJISK5101に記載の方法に従って測定した。 The bulk density was measured according to the method described in JISK5101.
球形度の測定は、走査型電子顕微鏡(S−800、日立製作所製)により球状複合体粒子をランダムに250個以上抽出し、平均長軸径lおよび平均短軸径wを求め、式:球形度=l/w(但し、lは球形複合体粒子の平均長軸径を示し、wは球形複合体粒子の平均短軸径を示す)によって算出した。 For the measurement of sphericity, 250 or more spherical composite particles are randomly extracted with a scanning electron microscope (S-800, manufactured by Hitachi, Ltd.), and an average major axis diameter l and an average minor axis diameter w are obtained. Degree = l / w (where l represents the average major axis diameter of the spherical composite particles and w represents the average minor axis diameter of the spherical composite particles).
BET比表面積は,窒素吸着法により測定した。 The BET specific surface area was measured by a nitrogen adsorption method.
細孔容積は、水銀圧入式オートポア9220(島津製作所製)で測定した値で示した。 The pore volume was indicated by a value measured with a mercury intrusion autopore 9220 (manufactured by Shimadzu Corporation).
体積固有抵抗値は、ハイレジスタンスメーター4329A(商品名、横河ヒュ−レットパッカード社製)で測定した値を用いた。 As the volume resistivity value, a value measured with a high resistance meter 4329A (trade name, manufactured by Yokogawa Hewlett-Packard Company) was used.
比透磁率は、球状フェライト粒子を60vol%熱可塑性エラストマ-(シェルクレイトンG1657)にロール混練により充填する。得られた混練物を中空円柱(外形7mm内径3mm、厚さ1.0±0.1mm)に成形し ネットワークアナライザ8720D(ヒューレットパッカード社製)を用いて、同軸管Sパラメータ法により測定した。500MHzでの比透磁率(μr’)値が2.5以上の場合、電波吸収性能が優れている。 The specific permeability is such that spherical ferrite particles are filled into 60 vol% thermoplastic elastomer (Shell Kraton G1657) by roll kneading. The obtained kneaded material was formed into a hollow cylinder (outer diameter 7 mm, inner diameter 3 mm, thickness 1.0 ± 0.1 mm) and measured by a coaxial tube S-parameter method using a network analyzer 8720D (manufactured by Hewlett-Packard Company). When the relative permeability (μr ′) value at 500 MHz is 2.5 or more, the radio wave absorption performance is excellent.
信頼性は次の様に測定した。半導体封止用樹脂組成物を死闘して幅10mm×長さ10mm×厚さ0.5mmの成形体を作り、その表面に太さ25μmのアルミニウム線を100μmの間隔で2本並べた。相対湿度85%、温度120℃の圧力容器の中で2本のアルミニウム線に直流30Vのバイアス電圧を負荷し、30時間試験を行った。電気抵抗が急激に低下したり、アルミニウム線の腐食など外観の異常を観察した。評価を表1の3段階で示した。 Reliability was measured as follows. A molded body having a width of 10 mm, a length of 10 mm, and a thickness of 0.5 mm was made by struggling with the resin composition for semiconductor encapsulation, and two aluminum wires with a thickness of 25 μm were arranged on the surface at intervals of 100 μm. In a pressure vessel having a relative humidity of 85% and a temperature of 120 ° C., a bias voltage of DC 30V was loaded on two aluminum wires, and the test was performed for 30 hours. Appearance abnormalities such as a sudden drop in electrical resistance and corrosion of aluminum wires were observed. The evaluation is shown in the three stages of Table 1.
流動性は、高化式フローテスターを使用して測定した、樹脂組成物の175℃の溶融粘度によって評価した。 The fluidity was evaluated by the melt viscosity at 175 ° C. of the resin composition measured using a Koka flow tester.
実施例1:
ヘンシェルミキサー内にFe2O348.5mol%、NiO20.6mol%、CuO10.4mol%、ZnO20.5mol%の割合で合計量1kgの前駆体を仕込み十分に攪拌し、エポキシ基を有するシラン系カップリング剤KBM−403(商品名:信越化学工業製)10gを添加混合して前駆体の粒子表面をエポキシ基を有するシラン系カップリング剤で親油化処理した。
Example 1:
A silane-based cup having an epoxy group, charged with a precursor of a total amount of 1 kg at a ratio of 48.5 mol% Fe 2 O 3, 20.6 mol% NiO, 10.4 mol% CuO and 20.5 mol% ZnO in a Henschel mixer 10 g of a ring agent KBM-403 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed, and the surface of the precursor particles was oleophilicized with a silane coupling agent having an epoxy group.
別に、同様にしてシリカ(SiO2)粒子(エクセリカSE−1;平均粒径1.8μm)1kgにエポキシ基を有するシラン系カップリング剤KBM−403;7.5gを添加混合して、金属酸化物の粒子表面をエポキシ基を有するシランカップリング剤で親油化処理した。 Separately, 7.5 g of a silane coupling agent KBM-403 having an epoxy group was added to 1 kg of silica (SiO 2 ) particles (Excelica SE-1; average particle size 1.8 μm) and mixed to form a metal oxide. The particle surface of the product was oleophilicized with a silane coupling agent having an epoxy group.
次いで、1Lのフラスコに、フェノール105g、37%ホルマリン120g、親油化処理されてた前駆体1Kg、25%アンモニア水37gおよび水140gを仕込み、攪拌しながら60分間で70℃に上昇させた後、粒子表面がエポキシ基を有するシラン系カップリング剤で処理されたシリカ粒子70gを添加し、同温度で60分間反応させた後、30分かけて85℃まで昇温した。同温度で120分間反応・硬化させることにより、フェノール樹脂とシリカ粒子とからなる表層部と、フェノール樹脂とフェライト前駆体からなる核部を有する複合体粒子を得た。 Next, 105 g of phenol, 120 g of 37% formalin, 1 kg of oleophilic precursor, 37 g of 25% aqueous ammonia and 140 g of water were charged into a 1 L flask, and the temperature was raised to 70 ° C. over 60 minutes with stirring. Then, 70 g of silica particles treated with a silane coupling agent having an epoxy group on the particle surface was added, reacted at the same temperature for 60 minutes, and then heated to 85 ° C. over 30 minutes. By reacting and curing at the same temperature for 120 minutes, composite particles having a surface layer portion composed of a phenol resin and silica particles and a core portion composed of a phenol resin and a ferrite precursor were obtained.
次に、フラスコ内の内容物を30℃に冷却し、上澄み液を除去した後、沈殿物を濾過し、通風乾燥機で80℃で7時間乾燥し、複合体粒子を得た。 Next, after the contents in the flask were cooled to 30 ° C. and the supernatant was removed, the precipitate was filtered and dried at 80 ° C. for 7 hours with an air dryer to obtain composite particles.
得られた複合体粒子は、平均粒径30μmで、前駆体とシリカ粒子との含有量が88.8重量%、細孔容積は0.001ml/gであった。 The obtained composite particles had an average particle size of 30 μm, a content of the precursor and silica particles of 88.8% by weight, and a pore volume of 0.001 ml / g.
得られた複合体粒子を内容量10Lの回転式熱処理炉内に入れ、空気を3L/minの流量で流しながら、加熱処理炉内温度を2時間で600℃に上げ、同温度で4時間加熱処理(加熱処理・)してフェノール樹脂を除去した。続いて、温度を2時間で1000℃まで上げ、同温度で4時間加熱処理(加熱処理II)してフェライト化を行った。その後、室温まで冷却した後、取り出し、球状のフェライト粒子を得た。 The obtained composite particles are put into a rotary heat treatment furnace having an internal volume of 10 L, and the temperature in the heat treatment furnace is raised to 600 ° C. in 2 hours while flowing air at a flow rate of 3 L / min, and heated at the same temperature for 4 hours. The phenol resin was removed by treatment (heat treatment). Subsequently, the temperature was raised to 1000 ° C. in 2 hours, and heat treatment (heat treatment II) was performed at the same temperature for 4 hours to perform ferrite formation. Then, after cooling to room temperature, it took out and obtained spherical ferrite particles.
得られた球状フェライト粒子は、平均粒径が26μmで、BET比表面積が0.02m2/gで、細孔容積は0.007ml/gで、体積固有抵抗は3.8×1014Ωcmであった。 The obtained spherical ferrite particles had an average particle size of 26 μm, a BET specific surface area of 0.02 m 2 / g, a pore volume of 0.007 ml / g, and a volume resistivity of 3.8 × 10 14 Ωcm. there were.
実施例2〜5、比較例1:
実施例1において、フェライト前駆体の種類、親油化処理剤の種類および量、その他反応条件を変えた以外は、実施例1と同様にして複合体粒子を得た。この時の製造条件および諸特性を表1に示す。
Examples 2-5, Comparative Example 1:
In Example 1, composite particles were obtained in the same manner as in Example 1 except that the type of ferrite precursor, the type and amount of the lipophilic agent, and other reaction conditions were changed. The production conditions and various characteristics at this time are shown in Table 1.
次いで、実施例1において複合体粒子の種類、加熱処理Iおよび加熱処理IIの条件を変えた以外は、実施例1と同様にして球状フェライト粒子を得た。この時の製造条件および諸特性を表2に、得られた球状フェライト粒子の諸特性を表3に示す。 Next, spherical ferrite particles were obtained in the same manner as in Example 1 except that the type of composite particles, the conditions of the heat treatment I and the heat treatment II were changed in Example 1. The production conditions and various characteristics at this time are shown in Table 2, and the various characteristics of the obtained spherical ferrite particles are shown in Table 3.
実施例6:
Fe2O355.5mol%、MnO30.5mol%、ZnO14.0mol%の割合の前駆体をボールミルにて3時間混合した。得られた混合物を乾燥した後、900℃で1時間仮焼し、再びボールミルで粉砕した。得られた仮焼粒子1kgにエポキシ基を有するシラン系カップリング剤KBM−403(商品名:信越化学工業製)10gを添加混合してエポキシ基を有するシラン系カップリング剤で親油化処理した。次に、実施例1と同様にフェノール樹脂生成反応を行い、複合体粒子を得、さらに、表2に示す様に変更した他は実施例1と同様に加熱処理Iおよび加熱処理IIを行い、球状フェライト粒子を得た。この時の製造条件および諸特性を表1、表2および表3に、得られた球状フェライト粒子の諸特性を表4に示す。
Example 6:
Fe 2 O 3 55.5mol%, MnO30.5mol %, the precursor of the proportion of ZnO14.0Mol% were mixed for 3 hours in a ball mill. The obtained mixture was dried, calcined at 900 ° C. for 1 hour, and pulverized again with a ball mill. 10 g of the silane coupling agent KBM-403 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) having an epoxy group was added to 1 kg of the obtained calcined particles, and the mixture was oleophilicized with a silane coupling agent having an epoxy group. . Next, a phenol resin production reaction was performed in the same manner as in Example 1 to obtain composite particles, and heat treatment I and heat treatment II were performed in the same manner as in Example 1 except that the composite particles were changed as shown in Table 2. Spherical ferrite particles were obtained. The production conditions and characteristics at this time are shown in Tables 1, 2 and 3, and the characteristics of the obtained spherical ferrite particles are shown in Table 4.
比較例2:
実施例1と同じ割合で各前駆体をボールミルにて3時間混合した。混合物を乾燥した後、800℃で1時間仮焼成し、再びボールミルで粉砕した。得られた仮焼粒子1kgにポリビニルアルコール20gと水200gを加え、スラリー化した。得られたスラリーをスプレート゛ライヤ−で造粒および乾燥し、平均粒径35μmの複合体粒子を調製した。次に、得られた複合体粒子を回転式熱処理炉内に入れ、空気を3L/minで流しながら、加熱処理炉内温度を2時間で600℃に上げ、同温度で2時間加熱処理・を行いポリビニルアルコールを除去した。続いて、加熱処理炉内温度を3時間で1000℃に昇温し、同温度で4時間加熱処理IIし、フェライト粒子を得た。その特性を表4に示す。
Comparative Example 2:
Each precursor was mixed for 3 hours in a ball mill at the same ratio as in Example 1. The mixture was dried, calcined at 800 ° C. for 1 hour, and pulverized again with a ball mill. 20 kg of polyvinyl alcohol and 200 g of water were added to 1 kg of the obtained calcined particles to form a slurry. The resulting slurry was granulated and dried with a splat liner to prepare composite particles having an average particle size of 35 μm. Next, the obtained composite particles are put into a rotary heat treatment furnace, and the temperature in the heat treatment furnace is raised to 600 ° C. in 2 hours while flowing air at 3 L / min. The polyvinyl alcohol was removed. Subsequently, the temperature in the heat treatment furnace was raised to 1000 ° C. in 3 hours, and heat treatment II was performed at the same temperature for 4 hours to obtain ferrite particles. The characteristics are shown in Table 4.
実施例7:
<樹脂の被覆>
実施例1で得られた球状フェライト粒子1kgを万能攪拌機内に投入し、続いて、エポキシ当量が300g/当量のエポキシ樹脂(エピクロン5300−70:大日本インキ化学工業)14gとMEK(メチルエチルケトン)20gを添加して球状フェライト粒子の表面へエポキシ樹脂を被覆した。
得られたエポキシ樹脂被覆球状フェライト粒子は、平均粒径27μm、体積固有抵抗値4.2×1014Ωcmであった。
Example 7:
<Resin coating>
1 kg of the spherical ferrite particles obtained in Example 1 was put into a universal stirrer, and subsequently, 14 g of an epoxy resin having an epoxy equivalent of 300 g / equivalent (Epiclon 5300-70: Dainippon Ink and Chemicals) and 20 g of MEK (methyl ethyl ketone). Was added to coat the surface of the spherical ferrite particles with an epoxy resin.
The obtained epoxy resin-coated spherical ferrite particles had an average particle size of 27 μm and a volume resistivity of 4.2 × 10 14 Ωcm.
<半導体封止用樹脂組成物の製造>
得られたエポキシ樹脂被覆球状フェライト粒子40体積%、球状シリカ粉末(溶融シリカ:平均粒径10μm)21体積%、ポリエチレンワックス0.8体積%の割合で以下の樹脂成分とヘンシェルミキサーで混合した。次いで、温度95〜110℃に加熱した熱ロールで3分間溶融混合して冷却した後、10メッシュの篩いを通過させて粉末状の半導体封止用樹脂組成物を得た。
<Manufacture of resin composition for semiconductor encapsulation>
The obtained epoxy resin-coated spherical ferrite particles were mixed by a Henschel mixer at a ratio of 40 vol%, spherical silica powder (fused silica: average particle size 10 μm) 21 vol%, and polyethylene wax 0.8 vol%. Next, the mixture was cooled by melting and mixing for 3 minutes with a hot roll heated to a temperature of 95 to 110 ° C., and then passed through a 10-mesh sieve to obtain a powdery resin composition for encapsulating a semiconductor.
(樹脂組成)
ビフェニル型エポキシ樹脂(軟化点105℃、エポキシ当量192) 100部
フェノールアラルキル樹脂(軟化点60℃、水酸基当量169) 70部
臭素化ビスフェノールA型エポキシ樹脂(軟化点77℃、水酸基当量465) 8部
三酸化アンチモン 3部
カーボンブラック 0.5部
(Resin composition)
Biphenyl type epoxy resin (softening point 105 ° C., epoxy equivalent 192) 100 parts Phenol aralkyl resin (softening point 60 ° C., hydroxyl group equivalent 169) 70 parts Brominated bisphenol A type epoxy resin (softening point 77 ° C., hydroxyl group equivalent 465) 8 parts Antimony trioxide 3 parts Carbon black 0.5 parts
実施例8〜9、比較例3:
実施例7において、球状フェライト粒子の種類、被覆樹脂の種類および量を変えた以外は、実施例7と同様にして樹脂被覆球状フェライト粒子を得た。この時の製造条件および諸特性を表5に示す。
Examples 8-9, Comparative Example 3:
Resin-coated spherical ferrite particles were obtained in the same manner as in Example 7, except that the type of spherical ferrite particles and the type and amount of the coating resin were changed. Table 5 shows the manufacturing conditions and characteristics at this time.
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JPH01141822A (en) * | 1987-11-28 | 1989-06-02 | Toda Kogyo Corp | Conductive iron oxide particulate powder and its production |
JP2003318015A (en) * | 2002-04-24 | 2003-11-07 | Toda Kogyo Corp | Spherical ferrite particle for radio wave absorbent and method of manufacturing the same |
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2004
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JPS59228664A (en) * | 1983-06-10 | 1984-12-22 | Tdk Corp | Ferrite carrier for development in electrophotography |
JPH01141822A (en) * | 1987-11-28 | 1989-06-02 | Toda Kogyo Corp | Conductive iron oxide particulate powder and its production |
JP2003318015A (en) * | 2002-04-24 | 2003-11-07 | Toda Kogyo Corp | Spherical ferrite particle for radio wave absorbent and method of manufacturing the same |
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JP2008147403A (en) * | 2006-12-08 | 2008-06-26 | Sumitomo Electric Ind Ltd | Soft magnetic composite material |
WO2008140435A1 (en) * | 2007-05-14 | 2008-11-20 | Boris Nikolaevich Shukaylo | Composite material, production method, degradation method and device |
JP2009249673A (en) * | 2008-04-04 | 2009-10-29 | Tohoku Univ | Composite material, and method for manufacturing the same |
JP2010283379A (en) * | 2010-08-19 | 2010-12-16 | Sumitomo Electric Ind Ltd | Reactor |
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