JP4010420B2 - Epoxy resin filler and method for producing the same - Google Patents
Epoxy resin filler and method for producing the same Download PDFInfo
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- JP4010420B2 JP4010420B2 JP2004236421A JP2004236421A JP4010420B2 JP 4010420 B2 JP4010420 B2 JP 4010420B2 JP 2004236421 A JP2004236421 A JP 2004236421A JP 2004236421 A JP2004236421 A JP 2004236421A JP 4010420 B2 JP4010420 B2 JP 4010420B2
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- 239000000945 filler Substances 0.000 title claims description 35
- 239000003822 epoxy resin Substances 0.000 title claims description 34
- 229920000647 polyepoxide Polymers 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 108
- 239000000377 silicon dioxide Substances 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 53
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 52
- 125000000524 functional group Chemical group 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000002296 dynamic light scattering Methods 0.000 claims description 11
- 239000011229 interlayer Substances 0.000 claims description 11
- 239000011810 insulating material Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005452 bending Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 3
- 238000013001 point bending Methods 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 238000004381 surface treatment Methods 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 108010015046 cell aggregation factors Proteins 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、エポキシ樹脂用充填材及びその製造方法に関する。 The present invention relates to a filler and a method of manufacturing the same epoxy resin.
シリカ粉末はエポキシ樹脂の充填材として使用されている。たとえば、多層配線板の層間絶縁材においては、その線熱膨張係数低減させるために、エポキシ樹脂にシリカ粉末を充填したものが使用されている。線熱膨張係数を低減させるには、エポキシ樹脂中にシリカ粉末をより均一に分散させ、樹脂との密着性を高めることが重要なことであり、従来よりシリカ粉末をシランカップリング剤で表面処理するなどの様々な工夫が行われている（例えば特許文献１）。しかし、まだ十分とはいえない。すなわち、従来のシランカップリング剤による処理方法では、凝集粒子が多く発生するので、エポキシ樹脂に充填したときに分散不良を起こし、樹脂との密着強度を十分に高めることができなかった。この解決ポイントは、表面処理を施すときに、シランカップリング剤の液滴ないしは自己縮合性による凝集要因をいかにして軽減するかである。
本発明の目的は、曲げ強さの増大効果の大きいエポキシ樹脂用充填材、特に多層配線板の層間絶縁材用の充填材と、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 filler for an epoxy resin , particularly a filler for an interlayer insulating material of a multilayer wiring board, which has a large effect of increasing bending strength, and a method for manufacturing the same.
本発明は、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン又は３−メルカプトプロピルトリメトキシシランからなる結合性官能基含有シランカップリング剤で表面処理されたシリカ粉末からなり、以下の方法で測定された曲げ強さが１２５．６〜１５７．１Ｎ／ｍｍ２であることを特徴とするエポキシ樹脂用充填材である。
（曲げ強さの測定方法）
ビスフェノールＡ型液状エポキシ樹脂３１．５ｇと、４，４−ジアミンジフェニルメタン９ｇと、エポキシ樹脂用充填材１３．５ｇとを、自公転混合機を用いて自転６００ｒｐｍ、公転２０００ｒｐｍで５分間混合し、得られた混合物をステンレス製の型に流し込み、真空度０．１Ｐａで５分間脱泡した後、２００℃で２時間保持して硬化させ、得られた硬化体から試験片（長さ８０ｍｍ、幅１０ｍｍ、厚さ４ｍｍ）を切り出し、室温下で測定された３点曲げ強さ。
The present invention comprises a silica powder surface-treated with a binding functional group-containing silane coupling agent comprising 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane, An epoxy resin filler characterized by having a flexural strength measured by the following method of 125.6 to 157.1 N / mm 2 .
(Measurement method of bending strength)
31.5 g of bisphenol A type liquid epoxy resin, 9 g of 4,4-diaminediphenylmethane, and 13.5 g of filler for epoxy resin were mixed for 5 minutes at a rotation speed of 600 rpm and a rotation speed of 2000 rpm using a rotation mixer. pouring mixture into a stainless steel mold, after 5 minutes degassed vacuum 0.1 Pa, it was cured by holding for 2 hours at 200 ° C., the test piece from the obtained cured product (length 80 mm, width 10mm , Thickness 4 mm), and the three-point bending strength measured at room temperature.
本発明のエポキシ樹脂用充填材においては、結合性官能基含有シランカップリング剤が、３−グリシドキシプロピルトリメトキシシランであり、曲げ強さが１３０Ｎ／ｍｍ２以上であること、及びエポキシ樹脂用充填材が、多層配線板の層間絶縁材の充填材であること、から選ばれた実施態様の少なくとも一つであることが好ましい。 In the filler for epoxy resin of the present invention , the binding functional group-containing silane coupling agent is 3-glycidoxypropyltrimethoxysilane, the bending strength is 130 N / mm 2 or more, and the epoxy resin use filler, it is the filler of an interlayer insulating material of the multilayer wiring board is preferably at least one selected embodiments from.
また、本発明は、１００〜３５０℃の温度下、含水率０．５質量％以下のシリカ粉末を浮遊させ、これと、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン又は３−メルカプトプロピルトリメトキシシランからなる結合性官能基含有シランカップリング剤の濃度が０．０５〜２体積％である窒素又は空気のガスとを、接触させることを特徴とするエポキシ樹脂用充填材の製造方法である。この発明においては、以下の１式、２式の条件を満たすこと、及び結合性官能基含有シランカップリング剤が３−グリシドキシプロピルトリメトキシシランであること、から選ばれた実施態様の少なくとも一つであることが好ましい。 In addition, the present invention floats a silica powder having a water content of 0.5% by mass or less at a temperature of 100 to 350 ° C., and 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, or An epoxy resin filler comprising contacting nitrogen or air gas having a binding functional group-containing silane coupling agent comprising 3-mercaptopropyltrimethoxysilane with a concentration of 0.05 to 2% by volume. It is a manufacturing method. In the present invention, the following equation (1) satisfying the two formulas condition, and that the binding functional group-containing silane coupling agent is 3-glycidoxypropyltrimethoxysilane, at least in selected embodiments from One is preferable.
０．５≦ＤＡｔ／ＤＡｓ≦２．５ ・・・（１）
１．０≦ＤＭｔ／ＤＭｓ≦１．５ ・・・（２）
ＤＡｔ：結合性官能基含有シランカップリング剤処理後のシリカ粉末の動的光散乱法による体積平均径
ＤＡｓ：結合性官能基含有シランカップリング剤処理前のシリカ粉末の動的光散乱法による体積平均径
ＤＭｔ：結合性官能基含有シランカップリング剤処理後のシリカ粉末の動的光散乱法による最頻径
ＤＭｓ：結合性官能基含有シランカップリング剤処理前のシリカ粉末の動的光散乱法による最頻径
0.5 ≦ DAt / DAs ≦ 2.5 (1)
1.0 ≦ DMt / DMs ≦ 1.5 (2)
DAt: Volume average diameter of silica powder after treatment with binding functional group-containing silane coupling agent by dynamic light scattering method DAs: Volume of silica powder before treatment with binding functional group-containing silane coupling agent by dynamic light scattering method Average diameter DMt: Mode diameter by dynamic light scattering of silica powder after treatment with silane coupling agent containing binding functional group DMs: Dynamic light scattering method of silica powder before treatment with silane coupling agent containing binding functional group Mode diameter
本発明によれば、凝集の小さいシリカ粉末からなるエポキシ樹脂用充填材、特に多層配線板の層間絶縁材の充填材と、その製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the filler for epoxy resins which consists of silica powder with small aggregation, especially the filler of the interlayer insulation material of a multilayer wiring board, and its manufacturing method are provided.
本発明のエポキシ樹脂用充填材は、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン又は３−メルカプトプロピルトリメトキシシランからなる結合性官能基含有シランカップリング剤（以下、単に「結合性官能基含有シランカップリング剤」という。）によって処理されたシリカ粉末からなり、上記方法で測定された曲げ強さが１２５．６〜１５７．１Ｎ／ｍｍ ２ を示すものである。結合性官能基含有シランカップリング剤の処理量は、シリカ粉末１００質量部あたり、０．１〜３質量部であることが好ましい。本発明のエポキシ樹脂用充填材は、例えば本発明のエポキシ樹脂用充填材の製造方法によって製造することができる。 The filler for epoxy resin of the present invention is a bonding functional group-containing silane coupling agent (hereinafter simply referred to as 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane). It is made of silica powder treated with “binding functional group-containing silane coupling agent”) , and the bending strength measured by the above method is 125.6 to 157.1 N / mm 2 . The treatment amount of the binding functional group-containing silane coupling agent is preferably 0.1 to 3 parts by mass per 100 parts by mass of the silica powder. The filler for epoxy resins of this invention can be manufactured, for example with the manufacturing method of the filler for epoxy resins of this invention.
本発明のエポキシ樹脂用充填材の製造方法は、１００〜３５０℃の温度下、含水率０．５質量％以下のシリカ粉末を浮遊させた状態で、結合性官能基含有シランカップリング剤の濃度が０．０５〜２体積％である窒素又は空気のガスと接触させるものである。本発明で重要なことは、表面処理されるシリカ粉末（以下、シリカ粉末原料ともいう。）の含水率であり、含水率が０．５質量％をこえると、結合性官能基含有シランカップリング剤の縮合反応がシリカ表面で起こりやすくなり、シリカ粉末同士を凝集させる恐れが高くなる。含水率の下限については、特に制約はないが、０．０１質量％であることが好ましい。含水率の調整は、例えばシリカ粉末原料を１００℃以上の加熱ガスで浮遊状態にしながら加熱処理することによって行うことができる。含水率はカールフィッシャー法によって測定することができる。 The method for producing an epoxy resin filler according to the present invention includes a concentration of a binding functional group-containing silane coupling agent in a state where silica powder having a water content of 0.5% by mass or less is suspended at a temperature of 100 to 350 ° C. Is brought into contact with nitrogen or air gas of 0.05 to 2% by volume. What is important in the present invention is the water content of the surface-treated silica powder (hereinafter also referred to as a silica powder raw material). When the water content exceeds 0.5% by mass, the binding functional group-containing silane coupling is performed. The condensation reaction of the agent tends to occur on the silica surface, and the risk of agglomerating the silica powder increases. Although there is no restriction | limiting in particular about the minimum of a moisture content, It is preferable that it is 0.01 mass%. The moisture content can be adjusted, for example, by subjecting the silica powder raw material to a heat treatment while being floated with a heating gas of 100 ° C. or higher. The water content can be measured by the Karl Fischer method.
シリカ粉末原料の粒径は、最大粒径４μｍ以下、体積平均径０．０１〜１μｍ、平均球形度０．９以上であることが好ましい。平均球形度は、次のようにして測定することができる。 The particle size of the silica powder raw material is preferably a maximum particle size of 4 μm or less, a volume average diameter of 0.01 to 1 μm, and an average sphericity of 0.9 or more. The average sphericity can be measured as follows.
実体顕微鏡、例えば「モデルＳＭＺ−１０型」（ニコン社製）、走査型電子顕微鏡、透過型電子顕微鏡等にて撮影した粒子像を画像解析装置、例えば（日本アビオニクス社製など）に取り込み、写真から粒子の投影面積（Ａ）と周囲長（ＰＭ）を測定する。周囲長（ＰＭ）に対応する真円の面積を（Ｂ）とすると、その粒子の真円度はＡ／Ｂとして表示できる。そこで、試料粒子の周囲長（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として算出される。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する。 A particle image taken with a stereomicroscope such as “Model SMZ-10” (Nikon Corporation), a scanning electron microscope, a transmission electron microscope or the like is taken into an image analysis apparatus such as Nihon Avionics Co., Ltd. To measure the projected area (A) and perimeter (PM) of the particles. When the area of a perfect circle corresponding to the perimeter (PM) is (B), the roundness of the particle can be displayed as A / B. Therefore, assuming a perfect circle having the same circumference as the sample particle (PM), PM = 2πr and B = πr 2 , so that B = π × (PM / 2π) 2 , and each particle Is calculated as sphericity = A / B = A × 4π / (PM) 2 . The sphericity of 200 arbitrary particles thus obtained is obtained, and the average value is defined as the average sphericity.
本発明において、シリカ粉末原料の表面処理は、シリカ粉末原料を浮遊させた状態で結合性官能基含有シランカップリング剤を含む窒素又は空気のガスと接触させることによって行われる。結合性官能基含有シランカップリング剤を液滴で処理したのでは、凝集粒子の生成を抑制することはできない。結合性官能基含有シランカップリング剤のガス濃度は、０．０５〜２体積％、好ましくは０．２〜１．５体積％である。０．０５体積％未満では、結合性官能基含有シランカップリング剤による十分な表面処理ができず、また２体積％をこえると、結合性官能基含有シランカップリング剤が局所的に反応して、自己縮合による凝集を引き起こす恐れがある。結合性官能基含有シランカップリング剤を含むガスの調製は、窒素又は空気のガスに、ガス化させた結合性官能基含有シランカップリング剤を混合することによって行うことができる。 In the present invention, the surface treatment of the silica powder raw material is performed by bringing the silica powder raw material into contact with a nitrogen or air gas containing a binding functional group-containing silane coupling agent in a suspended state. If the binding functional group-containing silane coupling agent is treated with droplets, formation of aggregated particles cannot be suppressed. The gas concentration of the binding functional group-containing silane coupling agent is 0.05 to 2% by volume, preferably 0.2 to 1.5% by volume. If it is less than 0.05% by volume, bonding functional group can not sufficiently surface treatment with silane coupling agent containing, also when more than 2% by volume, bonding functional group-containing silane coupling agent is locally reaction , May cause aggregation due to self-condensation. The gas containing the binding functional group-containing silane coupling agent can be prepared by mixing the gasified binding functional group-containing silane coupling agent with nitrogen or air gas .
結合性官能基含有シランカップリング剤の中でも、３−グリシドキシプロピルトリメトキシシランが最適である。 Among the binding functional group-containing silane coupling agents , 3-glycidoxypropyltrimethoxysilane is most suitable.
本発明のようにシリカ粉末原料を表面処理するためには、シリカ粉末原料を浮遊させることが必要となる。その方法を例示すれば、ステンレス製円筒容器の外周にはリボンヒーター等のヒーターが、下方の入口にはガスを均一に供給するための例えば２０μｍのステンレス製網が、更には上方の出口には粉末が系外へ飛散しないように例えばろ布が、それぞれ設けられてなる処理容器に、その内温を１００℃以上に保持してシリカ粉末原料を投入し、処理容器の下方から窒素ガス等のキャリアガスを供給してシリカ粉末原料を浮遊させる一方、処理容器の下方からは結合性官能基含有シランカップリング剤を含むガスを供給し、シリカ粉末原料と接触させる方法である。また、ミキサーなどの攪拌装置でシリカ粉末原料を攪拌して浮遊状態を形成しておき、この場に結合性官能基含有シランカップリング剤を含むガスを送り込む方法であってもよい。いずれの場合であっても、結合性官能基含有シランカップリング剤を含むガスは、例えば内温２００〜３００℃に加熱された電気釜に結合性官能基含有シランカップリング剤を滴下してガス化させ、それを窒素又は空気のガスと混合することよって製造することができる。結合性官能基含有シランカップリング剤のガス濃度は、窒素又は空気のガスの流量を一定にしておき、結合性官能基含有シランカップリング剤の電気釜への供給速度によって調整することができる。 In order to surface-treat the silica powder raw material as in the present invention, it is necessary to float the silica powder raw material. For example, a heater such as a ribbon heater is provided on the outer periphery of the stainless steel cylindrical container, a stainless steel net of, for example, 20 μm for uniformly supplying gas to the lower inlet, and further, an upper outlet is provided with the upper outlet. In order to prevent the powder from scattering out of the system, for example, a filter cloth is provided in each of the processing containers, and the silica powder raw material is charged while maintaining the internal temperature at 100 ° C. or higher. In this method, a carrier gas is supplied to float the silica powder raw material, while a gas containing a binding functional group-containing silane coupling agent is supplied from below the processing vessel and brought into contact with the silica powder raw material. Moreover, the silica powder raw material may be stirred with a stirring device such as a mixer to form a floating state, and a gas containing a binding functional group-containing silane coupling agent may be fed into this place. In any case, the gas containing the binding functional group-containing silane coupling agent is obtained by dropping the binding functional group-containing silane coupling agent into an electric kettle heated to an internal temperature of 200 to 300 ° C., for example. And can be produced by mixing it with nitrogen or air gas . Gas concentration of binding functional group-containing silane coupling agent, the flow rate of nitrogen or air gases leave the constant can be adjusted by the feed rate to the electric kettle bonding functional group-containing silane coupling agent.
浮遊状態のシリカ原料粉末と結合性官能基含有シランカップリング剤を含む窒素又は空気のガスとの接触は、温度１００〜３５０℃で行われる。その理由は、結合性官能基含有シランカップリング剤ガスの凝縮を防ぐこと、及び結合性官能基含有シランカップリング剤とシリカ粉末の反応副生物である水分を、シリカ粉末表面に吸着させないためである。接触温度の上限を３５０℃としたのは、結合性官能基含有シランカップリング剤の分解を防ぐためである。特に好ましい接触温度は１８０〜２５０℃である。接触時間は１．０〜１０ｓｅｃであることが好ましい。 Contact between the floating silica raw material powder and a nitrogen or air gas containing a binding functional group-containing silane coupling agent is performed at a temperature of 100 to 350 ° C. The reason for this is to prevent condensation of the binding functional group-containing silane coupling agent gas, and to prevent moisture, which is a reaction byproduct of the binding functional group-containing silane coupling agent and silica powder, from adsorbing to the silica powder surface. is there. The reason why the upper limit of the contact temperature is 350 ° C. is to prevent decomposition of the binding functional group-containing silane coupling agent . A particularly preferred contact temperature is 180 to 250 ° C. The contact time is preferably 1.0 to 10 seconds.
本発明においては、シリカ粉末原料の含水率、結合性官能基含有シランカップリング剤のガス濃度、処理（接触）温度等の条件を制御し、上記１式、２式の関係を満たすことが特に好ましい。最頻径の比（ＤＭｔ／ＤＭｓ）及び体積平均径の比（ＤＡｔ／ＤＡｓ）は、表面処理前後においてシリカ粉末が凝集によって粒度変化した程度を表す指標であり、これらの値が小さいほど表面処理されたシリカ粉末は凝集していないことを示すものである。 In the present invention, the water content of the silica powder source, the gas concentration of the binding functional group-containing silane coupling agent, treatment (contact) to control the conditions such as temperature, the equation (1), to meet the two equations related particularly preferable. The ratio of the mode diameter (DMt / DMs) and the ratio of volume average diameter (DAt / DAs) are indices indicating the degree of change in the particle size of the silica powder due to aggregation before and after the surface treatment. This indicates that the silica powder is not agglomerated.
動的光散乱法による粒度分布測定は、例えば測定装置として日機装社製「マイクロトラックＵＰＡ１５０」を用い、試料を例えばメチエチルケトン、トルエン、エタノール等から選ばれた有機溶媒に分散させてスラリー化して行われる。本発明においては、表面処理前後の粒度分布変化をみているので、有機溶媒の種類には影響は受けないが、表面処理前後の測定では同じ有機溶媒を用いる必要がある。最頻径、体積平均径は、得られた粒度分布の結果から、測定装置が自動計算してくる。 For the particle size distribution measurement by the dynamic light scattering method, for example, “Microtrac UPA150” manufactured by Nikkiso Co., Ltd. is used as a measuring device, and the sample is dispersed in an organic solvent selected from, for example, methyl ethyl ketone, toluene, ethanol, etc., and slurried. Done. In the present invention, since the change in the particle size distribution before and after the surface treatment is observed, the type of the organic solvent is not affected, but the same organic solvent must be used in the measurement before and after the surface treatment. The mode diameter and volume average diameter are automatically calculated from the obtained particle size distribution result.
本発明のエポキシ樹脂用充填材は、同一充填量においては、従来のシリカ充填材を用いた場合よりも曲げ強さを２０％以上をも向上させることが容易となる。また、エポキシ樹脂との密着性が向上するので、特に多層配線板の層間絶縁材用充填材として好適となり、層間絶縁材の線熱膨張係数を大幅に低減する。配合の一例を示せば、エポキシ樹脂１００質量部に対し、エポキシ樹脂用充填材が２５〜２５０質量部である。とくに、多層配線板の層間絶縁材用充填材の配合の一例を示せば、エポキシ樹脂１００質量部に対し、エポキシ硬化剤が３０〜５０質量部、エポキシ樹脂の有機溶媒が３０〜１００質量部、エポキシ樹脂用充填材が２５〜２５０質量部である。このような組成物（ワニス）を配線板上に塗布し、加熱処理を施すことで層間絶縁材となる。 Epoxy resin filling material of the present invention, in the same loading, it becomes easy to improve the 20% or more flexural strength than with a conventional silica filler. In addition, since the adhesion with the epoxy resin is improved, it is particularly suitable as a filler for an interlayer insulating material of a multilayer wiring board, and the linear thermal expansion coefficient of the interlayer insulating material is greatly reduced. One example of a formulation, relative to 100 parts by weight of epoxy resin, epoxy resin filler is 25 to 250 parts by weight. In particular, One example of a formulation of a multi-layer wiring board interlayer insulating material for a filler, relative to 100 parts by weight of epoxy resin, epoxy hardener 30 to 50 parts by weight, the organic solvent of the epoxy resin 30 to 100 parts by weight The epoxy resin filler is 25 to 250 parts by mass. Such a composition (varnish) is applied onto a wiring board and subjected to heat treatment to form an interlayer insulating material.
実施例１
シリカ粉末原料（注：動的光散乱法による体積平均径ＤＡｓが０．２９μｍ、最頻径ＤＭｓが０．０５μｍであるもの。）の１５ｋｇを上記処理容器（寸法：直径６００ｍｍ円筒）に投入し、下方から８００ＮＬ／ｍｉｎの窒素を送給して浮遊させる一方、処理容器の内温を２２０℃になるように加熱し２０分間保持した。これによって、シリカ粉末原料の含水率は０．２質量％となった。この加熱・浮遊状態の場に結合性官能基含有シランカップリング剤を含む窒素ガスを供給して処理を行った。用いた結合性官能基含有シランカップリング剤は、３−グリシドキシプロピルトリメトキシシラン（信越化学工業社製「ＫＢＭ−４０３」）であり、これの２５０ｇを２５ｇ／ｍｉｎで供給することで、供給した全ガス量に対する結合性官能基含有シランカップリング剤のガス濃度を０．２６体積％とした。結合性官能基含有シランカップリング剤ガスとシリカ粉末の接触時間は７．１ｓｅｃであり、結合性官能基含有シランカップリング剤の処理量はシリカ粉末１００質量部あたり１．３質量部であった。表面処理後のシリカ粉末について、動的光散乱法による粒度分布を測定した。その結果を表１に示す。
Example 1
15 kg of silica powder raw material (Note: Volume average diameter DAs by dynamic light scattering method is 0.29 μm and mode diameter DMs is 0.05 μm) is put into the above processing container (dimension: diameter 600 mm cylinder). While 800 NL / min of nitrogen was fed from below and floated, the internal temperature of the processing vessel was heated to 220 ° C. and held for 20 minutes. Thereby, the moisture content of the silica powder raw material became 0.2 mass%. Nitrogen gas containing a binding functional group-containing silane coupling agent was supplied to the heated / floating state for treatment. The binding functional group-containing silane coupling agent used was 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), and 250 g of this was supplied at 25 g / min. The gas concentration of the binding functional group-containing silane coupling agent relative to the total amount of gas supplied was 0.26% by volume. The contact time between the binding functional group-containing silane coupling agent gas and the silica powder was 7.1 sec, and the treatment amount of the binding functional group-containing silane coupling agent was 1.3 parts by mass per 100 parts by mass of the silica powder. . About the silica powder after surface treatment, the particle size distribution by the dynamic light scattering method was measured. The results are shown in Table 1.
実施例２
３−グリシドキシプロピルトリメトキシシラン５００ｇを５０ｇ／ｍｉｎで供給することで、供給した全ガス量に対する結合性官能基含有シランカップリング剤ガスの濃度を０．５１体積％とし、結合性官能基含シランカップリング剤の処理量をシリカ粉末１００質量部あたり２．７質量部としたこと以外は、実施例１と同様の方法で表面処理シリカ粉末を製造した。
Example 2
By supplying 500 g of 3-glycidoxypropyltrimethoxysilane at 50 g / min, the concentration of the binding functional group-containing silane coupling agent gas with respect to the total amount of gas supplied is 0.51% by volume, and the binding functional group A surface-treated silica powder was produced in the same manner as in Example 1 except that the amount of the silane- containing coupling agent treated was 2.7 parts by mass per 100 parts by mass of the silica powder.
実施例３
結合性官能基含有シランカップリング剤として、３−アミノプロピルトリエトキシシラン（信越化学工業社製「ＫＢＥ−９０３」）を用いたこと以外は、実施例１と同様の方法で表面処理シリカ粉末を製造した。
Example 3
The surface-treated silica powder was treated in the same manner as in Example 1 except that 3-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the binding functional group-containing silane coupling agent. Manufactured.
実施例４
結合性官能基含有シランカップリング剤として、３−メルカプトプロピルトリメトキシシラン（信越化学工業社製「ＫＢＭ−８０３」）を用いたこと以外は、実施例１と同様の方法で表面処理シリカ粉末を製造した。
Example 4
The surface-treated silica powder was treated in the same manner as in Example 1 except that 3-mercaptopropyltrimethoxysilane (“KBM-803” manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the binding functional group-containing silane coupling agent. Manufactured.
比較例１
３−グリシドキシプロピルトリメトキシシラン２０００ｇを２００ｇ／ｍｉｎの速度で供給し、供給した全ガス量に対する結合性官能基含有シランカップリング剤ガスの濃度を２．１体積％とし、結合性官能基含有シランカップリング剤の処理量をシリカ粉末１００質量部あたり５．３質量部としたこと以外は、実施例１と同様の方法で表面処理シリカ粉末を製造した。
Comparative Example 1
2000 g of 3-glycidoxypropyltrimethoxysilane was supplied at a rate of 200 g / min, the concentration of the binding functional group-containing silane coupling agent gas with respect to the total amount of gas supplied was 2.1 % by volume, and the binding functional group A surface-treated silica powder was produced in the same manner as in Example 1 except that the amount of the silane coupling agent contained was 5.3 parts by mass per 100 parts by mass of the silica powder.
比較例２
処理容器の内温を８０℃とし、加熱処理をせずにシリカ粉末原料の含水率を１．０質量％としたこと以外は、実施例１に準じて表面処理を行った。
Comparative Example 2
Surface treatment was performed according to Example 1 except that the internal temperature of the treatment container was 80 ° C. and the moisture content of the silica powder raw material was 1.0% by mass without heat treatment.
比較例３
３−グリシドキシプロピルトリメトキシシランをガス状ではなく液状で噴霧したこと以外は、実施例１に準じて表面処理を行った。
Comparative Example 3
Surface treatment was performed according to Example 1 except that 3-glycidoxypropyltrimethoxysilane was sprayed in a liquid rather than gaseous form.
上記で得られたシリカ粉末について、エポキシ樹脂用充填材としての評価試験を行った。試験は、ビスフェノールＡ型液状エポキシ樹脂３１．５ｇと、硬化剤として４，４−ジアミンジフェニルメタン９ｇと、エポキシ樹脂用充填材１３．５ｇとを、自公転混合機を用いて自転６００ｒｐｍ、公転２０００ｒｐｍで５分間混合し、得られた混合物をステンレス製の型に流し込み、真空度０．１Ｐａで５分間脱泡した後、２００℃で２時間保持して硬化させた。得られた硬化体を長さ８０ｍｍ、幅１０ｍｍ、厚さ４ｍｍに切り出して試験片とし、島津製作所社製「オートグラフＡＧ−２０００Ｄ」により室温３点曲げ強度を測定した。それらの結果を表１に示す。 The silica powder obtained above was subjected to an evaluation test as a filler for epoxy resin. In the test, 31.5 g of a bisphenol A type liquid epoxy resin, 9 g of 4,4-diaminediphenylmethane as a curing agent, and 13.5 g of a filler for epoxy resin were rotated at 600 rpm and 2,000 rpm using a revolving mixer. mixed for 5 minutes, it poured the resulting mixture into a stainless steel mold, after 5 minutes degassed vacuum 0.1 Pa, was cured by holding for 2 hours at 200 ° C.. The obtained cured product was cut into a length of 80 mm, a width of 10 mm, and a thickness of 4 mm to obtain a test piece, and the three-point bending strength at room temperature was measured by “Autograph AG-2000D” manufactured by Shimadzu Corporation. The results are shown in Table 1.
表１より、本発明のエポキシ樹脂用充填材によれば、曲げ強さが著しく増大する硬化体を製造することができた。この結果、硬化体の線熱膨張係数を大幅に低減するので、特に層間絶縁材の充填材として好適になることが示された。 From Table 1, according to the filler for epoxy resins of this invention, the hardening body which bending strength increases remarkably was able to be manufactured. As a result, it was shown that the linear thermal expansion coefficient of the cured body is greatly reduced, so that it is particularly suitable as a filler for interlayer insulating materials.
本発明のエポキシ樹脂用充填材は、特に多層配線板の層間絶縁材の充填材として用いることができる。 The filler for epoxy resin of the present invention can be used particularly as a filler for interlayer insulating materials of multilayer wiring boards.
Claims (6)
（曲げ強さの測定方法）
ビスフェノールＡ型液状エポキシ樹脂３１．５ｇと、４，４−ジアミンジフェニルメタン９ｇと、エポキシ樹脂用充填材１３．５ｇとを、自公転混合機を用いて自転６００ｒｐｍ、公転２０００ｒｐｍで５分間混合し、得られた混合物をステンレス製の型に流し込み、真空度０．１Ｐａで５分間脱泡した後、２００℃で２時間保持して硬化させ、得られた硬化体から試験片（長さ８０ｍｍ、幅１０ｍｍ、厚さ４ｍｍ）を切り出し、室温下で測定された３点曲げ強さ。 It consists of silica powder surface-treated with a binding functional group-containing silane coupling agent consisting of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane. An epoxy resin filler having a measured bending strength of 125.6 to 157.1 N / mm 2 .
(Measurement method of bending strength)
31.5 g of bisphenol A type liquid epoxy resin, 9 g of 4,4-diaminediphenylmethane, and 13.5 g of filler for epoxy resin were mixed for 5 minutes at a rotation speed of 600 rpm and a rotation speed of 2000 rpm using a rotation mixer. pouring mixture into a stainless steel mold, after 5 minutes degassed vacuum 0.1 Pa, it was cured by holding for 2 hours at 200 ° C., the test piece from the obtained cured product (length 80 mm, width 10mm , Thickness 4 mm), and the three-point bending strength measured at room temperature.
０．５≦ＤＡｔ／ＤＡｓ≦２．５ ・・・（１）
１．０≦ＤＭｔ／ＤＭｓ≦１．５ ・・・（２）
ＤＡｔ：結合性官能基含有シランカップリング剤処理後のシリカ粉末の動的光散乱法による体積平均径
ＤＡｓ：結合性官能基含有シランカップリング剤処理前のシリカ粉末の動的光散乱法による体積平均径
ＤＭｔ：結合性官能基含有シランカップリング剤処理後のシリカ粉末の動的光散乱法による最頻径
ＤＭｓ：結合性官能基含有シランカップリング剤処理前のシリカ粉末の動的光散乱法による最頻径 The following equation (1) manufacturing method according to claim 4, characterized by satisfying the two formulas conditions.
0.5 ≦ DAt / DAs ≦ 2.5 (1)
1.0 ≦ DMt / DMs ≦ 1.5 (2)
DAt: Volume average diameter of silica powder after treatment with binding functional group-containing silane coupling agent by dynamic light scattering method DAs: Volume of silica powder before treatment with binding functional group-containing silane coupling agent by dynamic light scattering method Average diameter DMt: Mode diameter by dynamic light scattering of silica powder after treatment with silane coupling agent containing binding functional group DMs: Dynamic light scattering method of silica powder before treatment with silane coupling agent containing binding functional group Mode diameter
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| CN102690496B (en) * | 2012-06-08 | 2014-03-26 | 苏州巨峰电气绝缘系统股份有限公司 | Nano modified epoxy vacuum pressure impregnation resin and preparation method thereof |
| KR20210044873A (en) * | 2018-09-14 | 2021-04-23 | 엔.이. 켐캣 가부시키가이샤 | Organic inorganic composite material |
| WO2023157542A1 (en) * | 2022-02-21 | 2023-08-24 | 味の素株式会社 | Resin composition |
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| GB8320086D0 (en) * | 1983-07-26 | 1983-08-24 | Ciba Geigy Ag | Spherical fused silica |
| JPH0260955A (en) * | 1988-08-26 | 1990-03-01 | Somar Corp | Resin composition suitable for forming interlayer insulation layer |
| JPH0726122A (en) * | 1993-07-06 | 1995-01-27 | Hitachi Chem Co Ltd | Epoxy resin composition for printed-wiring board |
| JPH0841294A (en) * | 1994-07-27 | 1996-02-13 | Shin Etsu Chem Co Ltd | Insulating resin paste and semiconductor apparatus |
| JP3978623B2 (en) * | 1997-06-10 | 2007-09-19 | 日立化成工業株式会社 | Multilayer wiring board |
| JPH1143320A (en) * | 1997-07-25 | 1999-02-16 | Toshiba Ceramics Co Ltd | Production of silica filler, composition for filler and its production |
| JP2000264619A (en) * | 1999-03-18 | 2000-09-26 | Hidehiro Kamiya | Siliceous powder and its production |
| JP4372331B2 (en) * | 2000-11-07 | 2009-11-25 | 電気化学工業株式会社 | Surface modification method of silica fine powder |
| JP4306951B2 (en) * | 2000-11-07 | 2009-08-05 | 電気化学工業株式会社 | Surface-treated fine spherical silica powder and resin composition |
| JP2002275356A (en) * | 2001-03-22 | 2002-09-25 | Denki Kagaku Kogyo Kk | Filler for epoxy resin, and epoxy resin composition |
| JP5037760B2 (en) * | 2001-07-03 | 2012-10-03 | 電気化学工業株式会社 | Epoxy resin varnish for resin substrates |
| JP3868272B2 (en) * | 2001-11-15 | 2007-01-17 | 電気化学工業株式会社 | Spherical inorganic powder and resin composition filled therewith |
| US20050011409A1 (en) * | 2001-12-25 | 2005-01-20 | Yasuhide Isobe | Inorganic oxide |
| JP3983234B2 (en) * | 2004-08-16 | 2007-09-26 | 電気化学工業株式会社 | Manufacturing method of toner external additive |
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