JPH02227451A - Filler for resins and liquid epoxy resin composition - Google Patents
Filler for resins and liquid epoxy resin compositionInfo
- Publication number
- JPH02227451A JPH02227451A JP4743389A JP4743389A JPH02227451A JP H02227451 A JPH02227451 A JP H02227451A JP 4743389 A JP4743389 A JP 4743389A JP 4743389 A JP4743389 A JP 4743389A JP H02227451 A JPH02227451 A JP H02227451A
- Authority
- JP
- Japan
- Prior art keywords
- less
- weight
- inorganic powder
- epoxy resin
- particle size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 title claims abstract description 17
- 239000000945 filler Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 229920005989 resin Polymers 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002026 crystalline silica Inorganic materials 0.000 claims abstract description 4
- 239000005350 fused silica glass Substances 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 11
- 229920000647 polyepoxide Polymers 0.000 abstract description 11
- 239000011342 resin composition Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 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 4
- 238000000034 method Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- -1 glycidyl ester Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-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
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【発明の詳細な説明】
〈発明の利用分野〉
本発明は、樹脂用充填材及び液状エポキシ樹脂組成物、
詳しくは、良好な成形性を有すると共に機械的強度と熱
的強度に優れた電子部品封止用の液状エポキシ樹脂組成
物に関する。[Detailed Description of the Invention] <Field of Application of the Invention> The present invention provides fillers for resins and liquid epoxy resin compositions,
Specifically, the present invention relates to a liquid epoxy resin composition for encapsulating electronic components that has good moldability and excellent mechanical strength and thermal strength.
〈従来の技術〉
液状エポキシ樹脂は、電気絶縁性、耐湿性に優れている
ため、電気、電子部品の絶縁材料として広（使用されて
いる。<Prior Art> Liquid epoxy resin has excellent electrical insulation and moisture resistance, and is therefore widely used as an insulating material for electrical and electronic parts.
しかし、従来の液状エポキシ樹脂組成物では、加熱硬化
時の反応収縮によるクラックの発生が問題になると同時
に注型する素子や接着面である基板等との熱膨張係数の
差により硬化物にクラックが発生する問題点があった。However, with conventional liquid epoxy resin compositions, cracks occur due to reaction shrinkage during heat curing, and at the same time cracks occur in the cured product due to the difference in thermal expansion coefficient between the casting element and the adhesive surface of the substrate. There were problems that occurred.
これらの問題点を改善すべく内部応力を和らげるため可
撓性付与剤の添加や硬化条件の緩和などの方法が提案さ
れてきたが十分ではなかった。また、樹脂組成物自体の
熱膨張係数を小さくするため無機質充填材の高充填など
が試みられているが、この場合は樹脂組成物自体が高粘
度となり成形不良となる。そこで、アルコキシシランで
表面処理された球状シリカを用いての高充填も試みられ
たが（特開昭６１−２９６０２０号公報）が、これもま
た粘度が上昇し望ましくない。そのため粘度を上昇させ
ることなく硬化物の機械的強度と耐熱衝撃性を満足させ
る液状エポキシ樹脂組成物の出現が待たれていた。In order to alleviate these problems, methods such as adding a flexibility imparting agent and relaxing curing conditions have been proposed to relieve internal stress, but these methods have not been sufficient. Further, in order to reduce the thermal expansion coefficient of the resin composition itself, attempts have been made to increase the filling of inorganic fillers, but in this case, the resin composition itself becomes highly viscous, resulting in poor molding. Therefore, high filling using spherical silica surface-treated with alkoxysilane has been attempted (Japanese Unexamined Patent Publication No. 61-296020), but this also increases the viscosity and is undesirable. Therefore, the emergence of a liquid epoxy resin composition that satisfies the mechanical strength and thermal shock resistance of a cured product without increasing viscosity has been awaited.
〈発明が解決しようとする課題〉
本発明者らは、上記の問題点を解決すべく種々検討した
結果、特定の粒度構成からなる球状無機質粉末と破砕無
機質粉末とを特定量配合することによって、成形性に優
れ、かつ機械的強度が低下しない液状エポキシ樹脂組成
物が得られることを見出し、本発明を完成した。<Problems to be Solved by the Invention> As a result of various studies to solve the above problems, the present inventors have found that by blending a specific amount of spherical inorganic powder and crushed inorganic powder having a specific particle size configuration, The present invention was completed based on the discovery that a liquid epoxy resin composition with excellent moldability and no decrease in mechanical strength can be obtained.
く課題を解決するための手段〉 すなわち、本発明は、以下を要旨とするものである。Means to solve problems〉 That is, the present invention has the following gist.
１、下記の粒度構成を有する球状無機質粉末（ａ）と破
砕無機質粉末（ｂ）とをｉａ） ／ （ｂ）の重量比が
９／１〜５１５の割合で含有してなることを特徴とする
樹脂用充填材。1. It is characterized by containing spherical inorganic powder (a) and crushed inorganic powder (b) having the following particle size structure at a weight ratio of ia)/(b) of 9/1 to 515. Filler for resin.
平均粒径１２〜２０μで、２μ以下の含有量が７〜１５
重量％、１２μ以下が３５〜５０重量％、２４μ以下が
６０〜７５重量％、４５μ以上が６重量％以下。The average particle size is 12 to 20μ, and the content of 2μ or less is 7 to 15
35 to 50% by weight is 12μ or less, 60 to 75% by weight is 24μ or less, and 6% by weight or less is 45μ or more.
平均粒径８〜２５μで、２μ以下の含有量が５〜１５重
量％、１２μ以下が３０〜６０重量％、２４μ以下が５
０〜８５重量％。The average particle size is 8 to 25μ, the content of 2μ or less is 5 to 15% by weight, the content of 12μ or less is 30 to 60% by weight, and the content of 24μ or less is 5% by weight.
0-85% by weight.
２、無機質粉末の材質が結晶質シリカ、溶融シリカ、ア
ルミナ、炭酸カルシウム、窒化ケイ素、炭化ケイ素、窒
化アルミニウム又は窒化硼素であることを特徴とする請
求項ｌ記載の樹脂用充填材。2. The resin filler according to claim 1, wherein the material of the inorganic powder is crystalline silica, fused silica, alumina, calcium carbonate, silicon nitride, silicon carbide, aluminum nitride, or boron nitride.
３、請求項１又は２記載の樹脂用充填材を６０〜８０容
量％含有してなることを特徴とする液状エポキシ樹脂組
成物。3. A liquid epoxy resin composition containing 60 to 80% by volume of the resin filler according to claim 1 or 2.
以下、本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明の球状無機質粉末（ａ）又は破砕無機質粉末（ｂ
ｌの材質としては、結晶質シリカ、溶融シリカ、アルミ
ナ、炭酸カルシウム、窒化ケイ素、炭化ケイ素、窒化ア
ルミニウム、窒化硼素等があげられるがこれに限られた
ものではない。Spherical inorganic powder (a) or crushed inorganic powder (b) of the present invention
Examples of the material for l include, but are not limited to, crystalline silica, fused silica, alumina, calcium carbonate, silicon nitride, silicon carbide, aluminum nitride, and boron nitride.
本発明でいう球状無機質粉末（ａｌとは、溶射法、合成
法等で製造された針状度（長・短の長さ比）の平均値が
１．３以下のものをいう。その平均粒径は１２〜２０μ
である。また、２μ以下の粒子の含有量が７重量％、１
２μ以下の粒子の含有量が３５重量％、２４μ以下の粒
子の含有量が６０重量％より少ないと樹脂組成物自体の
粘度は低くなるがクランク発生率が高（なる。一方、２
μ以下の粒子の含有量が１５重量％、１２ｐ以下の粒子
の含有量が５０重量％、２４μ以下の粒子の含有・量が
７５重量％、４５μ以上の粒子の含有量が６重量％をこ
えるとクラック発生率は低くなるが、樹脂組成物自体の
粘度が高くなる。好ましくは、平均粒径が１４〜１７μ
で、２μ以下の粒子の含有量が１０〜１２重量％、１２
μ以下の粒子の含有量が４０〜４４重量％、２４μ以下
の粒子の含有量が６３〜６７重量％、４５μ以上の粒子
が５重量％以下である。なお、最大粒径は７４μである
。In the present invention, spherical inorganic powder (al refers to powder with an average value of acicularity (long/short length ratio) of 1.3 or less produced by a thermal spraying method, a synthesis method, etc.). The diameter is 12~20μ
It is. In addition, the content of particles of 2μ or less is 7% by weight, 1
If the content of particles of 2μ or less is less than 35% by weight and the content of particles of 24μ or less is less than 60% by weight, the viscosity of the resin composition itself will be low, but the cranking rate will be high (on the other hand, 2
The content of particles smaller than μ is 15% by weight, the content of particles smaller than 12p is 50% by weight, the content/amount of particles smaller than 24μ is 75% by weight, and the content of particles larger than 45μ exceeds 6% by weight. Although the crack occurrence rate decreases, the viscosity of the resin composition itself increases. Preferably, the average particle size is 14-17μ
and the content of particles of 2μ or less is 10 to 12% by weight, 12
The content of particles smaller than μ is 40 to 44% by weight, the content of particles smaller than 24μ is 63 to 67% by weight, and the content of particles larger than 45μ is 5% by weight or less. Note that the maximum particle size is 74μ.
本発明でいう破砕無機質粉末（ｂｌとは、粉砕機等で粉
砕されたものであればいかなるものでもよい。The crushed inorganic powder (BL) used in the present invention may be any powder as long as it has been crushed using a crusher or the like.
その平均粒径は８〜２５μである。２μ以下の粒子の含
有量が５重量％、１２μ以下の粒子の含有量が３０重量
％、２４μ以下の粒子の含有量が５０重量％より少ない
と樹脂組成物自体の粘度は低くなるがクランク発生率が
高くなる。一方、２μ以下の粒子の含有量が１５重貴簡
、１２μ以下の粒子の含有量が６０重量％、２４μ以下
の粒子の含有量が８５重量％をこえるとクラック発生率
は低くなるが樹脂組成物自体の粘度が高くなる。Its average particle size is 8-25μ. If the content of particles of 2μ or less is less than 5% by weight, the content of particles of 12μ or less is 30% by weight, and the content of particles of 24μ or less is less than 50% by weight, the viscosity of the resin composition itself will be low, but cranking will occur. rate becomes higher. On the other hand, if the content of particles of 2μ or less exceeds 15 weight%, the content of particles of 12μ or less exceeds 60% by weight, and the content of particles of 24μ or less exceeds 85% by weight, the crack occurrence rate decreases, but the resin composition The viscosity of the substance itself increases.
好ましくは、平均粒径が１２〜１７μで、２μ以下の粒
子の含有量が８〜１１重量％、１２μ以下の粒子の含有
量が４０〜５０重量％、２４μ以下の粒子の含有量が６
５〜７５重量％である。なお、最大粒径は１５０μであ
る。Preferably, the average particle size is 12 to 17μ, the content of particles of 2μ or less is 8 to 11% by weight, the content of particles of 12μ or less is 40 to 50% by weight, and the content of particles of 24μ or less is 6% by weight.
It is 5 to 75% by weight. Note that the maximum particle size is 150μ.
次に、球状無機質粉末＋８）と破砕無機質粉末（ｂｌの
混合割合について説明する。両者の混合割合は（ａ）／
（ｂ）の重量比で９７１〜５１５である。該比が９／ｌ
をこえるとクランクの発生率が高くなり、また５７５未
満では樹脂組成物自体の粘度が高くなる。Next, the mixing ratio of spherical inorganic powder +8) and crushed inorganic powder (bl) will be explained.The mixing ratio of both is (a)/
The weight ratio of (b) is 971 to 515. The ratio is 9/l
If it exceeds 575, the incidence of cranking will increase, and if it is less than 575, the viscosity of the resin composition itself will increase.
本発明の充填材が使用される樹脂としては、尿素樹脂、
メラミン樹脂、フェノール樹脂、エポキシ樹脂、不飽和
ポリエステル、アルキド樹脂、ポリフェニレンサルファ
イドなどがあげられるが、液状エポキシ樹脂が好適であ
る。本発明において、充填材の配合量を全エポキシ樹脂
組成物に対し６０〜８０容量％としたのは、６０容量％
未満ではクラックの発生率が高くなり、一方、８０容量
％をこえると、樹脂組成物自体の粘度が高く成形性が悪
くなるからである。Examples of resins for which the filler of the present invention is used include urea resin,
Examples include melamine resin, phenol resin, epoxy resin, unsaturated polyester, alkyd resin, polyphenylene sulfide, and liquid epoxy resin is preferred. In the present invention, the blending amount of the filler is 60 to 80% by volume based on the total epoxy resin composition, which means 60% by volume.
If it is less than 80% by volume, the crack generation rate will be high, whereas if it exceeds 80% by volume, the viscosity of the resin composition itself will be high and the moldability will be poor.
本発明に用いる液状エポキシ樹脂は、−Ｍに液状のエポ
キシ樹脂として知られているものであればいかなるもの
であってもよく、例えば、ビスフェノール型エポキシ樹
脂、脂環型エポキシ樹脂、ノボラック型エポキシ樹脂、
複素環型エポキシ樹脂、グリシジルエステル型エポキシ
樹脂などがあげられ、これらは難燃化のため、臭素等に
より置換されていてもよい０本発明では以上の群より選
ばれる少なくとも１種以上が使用される。これらの中で
も、高温における電気特性及び耐湿性が良好なノボラッ
ク型エポキシ樹脂が好ましい。The liquid epoxy resin used in the present invention may be any one known as a liquid epoxy resin, such as bisphenol type epoxy resin, alicyclic type epoxy resin, novolak type epoxy resin. ,
Examples include heterocyclic epoxy resins and glycidyl ester type epoxy resins, which may be substituted with bromine or the like for flame retardancy.In the present invention, at least one selected from the above group is used. Ru. Among these, novolak-type epoxy resins are preferred because they have good electrical properties and moisture resistance at high temperatures.
エポキシ樹脂硬化剤としては、−ｍに知られているもの
であればいかなるものであってもよく、例えば、ポリカ
ルボン酸無水物、アミン、フェノール樹脂、ポリアミド
、ジシアンジアミド、ＥＦｆｆ−アミン錯体、イミダゾ
ール等があげられる。The epoxy resin curing agent may be any known one, such as polycarboxylic anhydride, amine, phenolic resin, polyamide, dicyandiamide, EFff-amine complex, imidazole, etc. can be given.
ポリカルボン酸無水物としては、メチルテトラヒドロ無
水フタル酸、メチルへキサヒドロ無水フタル酸、メチル
エンドメチルテトラヒドロ無水フタル酸などの液状二塩
基酸無水物のばか無水フタル酸、ヘキサヒドロ無水フタ
ル酸、テトラヒドロ無水フタル酸、無水トリメリット酸
、無水ピロメリット酸、ベンゾフェノンテトラカルボン
酸無水物、ポリアゼライン酸無水物などである。アミン
としては、トリエチレンテトラミン、イソホロンジアミ
ン、メタフェニレンジアミン、ジアミノジフェニルメタ
ン、トリス−ジメチル７ミノエチルフエノール等である
。また、イミダゾールとしては、２−メチル−４−エチ
ルイミダゾール、１−ベンジル−２−メチルイミダゾー
ル、２−メチルイミダゾール、イミダゾール塩などがあ
る。Examples of polycarboxylic anhydrides include liquid dibasic acid anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylendomethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride. acids, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, polyazelaic anhydride, etc. Examples of the amine include triethylenetetramine, isophoronediamine, metaphenylenediamine, diaminodiphenylmethane, tris-dimethyl7minoethylphenol, and the like. Examples of imidazole include 2-methyl-4-ethylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, and imidazole salts.
本発明に用いる硬化促進剤は、一般にエポキシ樹脂の硬
化促進剤として使用されているものであればいかなるも
のであってもよく、例えば、ベンジルジメチルアミン、
トリスジメチルアミノメチルフェノール等の各種アミン
、トリフェニルホスフィン、トリシクロヘキシルホスフ
ィン、トリブチルホスフィン、メチルジフェニルホスフ
ィン等の各種ホスフィン、２−メチルイミダゾール、２
−エチル−４−メチルイミダゾール、１−シアノエチル
−２−エチル−４−メチルイミダゾール等のイミダゾー
ル類があげられ、これらから成る群より選ばれる少なく
とも１種のものが使用される。The curing accelerator used in the present invention may be any one that is generally used as a curing accelerator for epoxy resins, such as benzyldimethylamine,
Various amines such as trisdimethylaminomethylphenol, various phosphines such as triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine, 2-methylimidazole, 2
Examples include imidazoles such as -ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole, and at least one selected from the group consisting of these is used.
以上の他、必要に応じて、シラン系カップリング剤、チ
タネート系カップリング剤等のカップリング剤、三酸化
アンチモン等の難燃剤、カーボンブラック等の顔料、ワ
ックス類等の離型剤、シリコーンオイル等の可撓性付与
剤を配合してもよい。In addition to the above, if necessary, coupling agents such as silane coupling agents and titanate coupling agents, flame retardants such as antimony trioxide, pigments such as carbon black, mold release agents such as waxes, silicone oil, etc. A flexibility imparting agent such as the like may also be blended.
〈実施例〉 次に、本発明を実施例をあげて更に具体的に説明する。<Example> Next, the present invention will be described in more detail with reference to Examples.
実１韮」〜１３−」Ｊ灯」Ｖヱｌ
高温火炎中を通すことにより第１表に示す球状シリカ粉
末を得た。また、振動ミルを使用し第１表に示す破砕シ
リカ粉末を得た。第１表に示した充填材を第３表に示す
割合で配合し、第２表で示した割合で、液状エポキシ樹
脂、硬化剤、硬化促進剤と共に万能混合機、ニーダ−等
を用いて真空下で混合して液状エポキシ樹脂組成物を得
た。Spherical silica powder shown in Table 1 was obtained by passing it through a high temperature flame. Further, using a vibration mill, crushed silica powder shown in Table 1 was obtained. The fillers shown in Table 1 are mixed in the proportions shown in Table 3, and the mixture is mixed with liquid epoxy resin, curing agent, curing accelerator, etc. in the proportions shown in Table 2 using a universal mixer, kneader, etc. A liquid epoxy resin composition was obtained by mixing below.
これらの樹脂各組成物を１５０℃で５時間硬化して試験
片を作製した。その粘度及び曲げ強度とクラック発生率
の測定結果を第３表に示す。Each of these resin compositions was cured at 150° C. for 5 hours to prepare test pieces. Table 3 shows the measurement results of the viscosity, bending strength, and crack occurrence rate.
（測定法）
（１） 粘度ｌ】粘度計（東京計器社製）で３°コー
ンを用い温度４５℃で測定した。(Measurement method) (1) Viscosity l] Measured using a 3° cone with a viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a temperature of 45°C.
（２）曲げ強度：ＪＩＳ−に−６９１１に準する方法で
測定した。(2) Bending strength: Measured according to JIS-6911.
（３） クランク発生率：試験片１００個を一１５０
〜２６０℃の冷熱サイクルに１０回か
け（割れた個数／１００）ｘｌＯＯで
クランク発生率を求めた。(3) Crank occurrence rate: 100 test pieces = 150
The crack occurrence rate was determined by 10 cycles of heating and cooling at ~260°C (number of cracks/100) x lOO.
（４） 粒度分布及び平均粒径：粒度分布測定装置（
シーラス社製、モデル７１５）を用
いて測定した。また粒度分布の累積重
量％が５θ％のときの粒径を平均粒径
とした。(4) Particle size distribution and average particle size: Particle size distribution measuring device (
The measurement was performed using a model 715 (manufactured by Cirrus Corporation). Further, the particle size when the cumulative weight % of the particle size distribution was 5θ% was defined as the average particle size.
（５）４５μ以上の粒子量：湿式ＪＩＳ篩法にて測定し
た。(5) Amount of particles of 45μ or more: Measured by wet JIS sieving method.
（６）針状度；画像処理装置５ＰＩＣＡ（日本アビオニ
クス社製）で測定した。(6) Acicularity: Measured using an image processing device 5PICA (manufactured by Nippon Avionics Co., Ltd.).
第２表
注）
エピコート８２８：ビスフェノールＡジグリシジルエー
テル
（油化シェルエポキシ■商品名）
ＨＮ−５５００：メチルへキサヒドロ無水フタル酸
（日立化成工業■商品名）
ＤＭＰ−３０：ジメチルアミノメチルフェノール
〈発明の効果〉
本発明によれば、成形性と強度特性に優れた液状エポキ
シ樹脂組成物を得ることができる。Table 2 Note) Epicote 828: Bisphenol A diglycidyl ether (Oilized shell epoxy ■Product name) HN-5500: Methylhexahydrophthalic anhydride (Hitachi Chemical ■Product name) DMP-30: Dimethylaminomethylphenol (Invention) Effect> According to the present invention, a liquid epoxy resin composition having excellent moldability and strength properties can be obtained.
特 許 出 願 人 電気化学工業株式会社Special permission Out wish Man Denki Kagaku Kogyo Co., Ltd.
Claims (1)
砕無機質粉末（ｂ）とを（ａ）／（ｂ）の重量比が９／
１〜５／５の割合で含有してなることを特徴とする樹脂
用充填材。 〔球状無機質粉末（ａ）〕 平均粒径１２〜２０μで、２μ以下の含有量が７〜１５
重量％、１２μ以下が３５〜５０重量％、２４μ以下が
６０〜７５重量％、４５μ以上が６重量％以下。 〔破砕無機質粉末（ｂ）〕 平均粒径８〜２５μで、２μ以下の含有量が５〜１５重
量％、１２μ以下が３０〜６０重量％、２４μ以下が５
０〜８５重量％。 ２、無機質粉末の材質が結晶質シリカ、溶融シリカ、ア
ルミナ、炭酸カルシウム、窒化ケイ素、炭化ケイ素、窒
化アルミニウム又は窒化硼素であることを特徴とする請
求項１記載の樹脂用充填材。 ３、請求項１又は２記載の樹脂用充填材を６０〜８０容
量％含有してなることを特徴とする液状エポキシ樹脂組
成物。[Claims] 1. Spherical inorganic powder (a) and crushed inorganic powder (b) having the following particle size structure are mixed in a weight ratio of (a)/(b) of 9/
A filler for resin characterized by containing the filler in a ratio of 1 to 5/5. [Spherical inorganic powder (a)] Average particle size 12-20μ, content of 2μ or less is 7-15
35 to 50% by weight is 12μ or less, 60 to 75% by weight is 24μ or less, and 6% by weight or less is 45μ or more. [Crushed inorganic powder (b)] Average particle size is 8 to 25μ, content of 2μ or less is 5 to 15% by weight, 12μ or less is 30 to 60% by weight, and 24μ or less is 5% by weight.
0-85% by weight. 2. The resin filler according to claim 1, wherein the material of the inorganic powder is crystalline silica, fused silica, alumina, calcium carbonate, silicon nitride, silicon carbide, aluminum nitride, or boron nitride. 3. A liquid epoxy resin composition containing 60 to 80% by volume of the resin filler according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4743389A JP2634663B2 (en) | 1989-02-28 | 1989-02-28 | Filler for resin and liquid epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4743389A JP2634663B2 (en) | 1989-02-28 | 1989-02-28 | Filler for resin and liquid epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02227451A true JPH02227451A (en) | 1990-09-10 |
| JP2634663B2 JP2634663B2 (en) | 1997-07-30 |
Family
ID=12775019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4743389A Expired - Lifetime JP2634663B2 (en) | 1989-02-28 | 1989-02-28 | Filler for resin and liquid epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2634663B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02228354A (en) * | 1989-03-01 | 1990-09-11 | Shin Etsu Chem Co Ltd | Epoxy resin composition for semiconductor encapsulation |
| JPH05206333A (en) * | 1992-01-27 | 1993-08-13 | Shin Etsu Chem Co Ltd | Epoxy resin composition for sealing semiconductor and hardened one thereof |
| JPH05235210A (en) * | 1991-08-02 | 1993-09-10 | Matsushita Electric Works Ltd | Epoxy resin molding material for sealing |
| JP2007070474A (en) * | 2005-09-07 | 2007-03-22 | Denki Kagaku Kogyo Kk | Inorganic powder and its use |
| JP2008088405A (en) * | 2006-09-07 | 2008-04-17 | Nitto Shinko Kk | Resin composition, heat conductive sheet, high heat conductive adhesive sheet with metal foil, and high heat conductive adhesive sheet with metal plate |
| WO2008078706A1 (en) * | 2006-12-22 | 2008-07-03 | Denki Kagaku Kogyo Kabushiki Kaisha | Amorphous silica powder, method for production thereof, and semiconductor sealing material |
| JP2008189818A (en) * | 2007-02-05 | 2008-08-21 | Nitto Denko Corp | Thermally conductive resin composition, thermal conductive sheet and method for producing the same |
| WO2009154186A1 (en) * | 2008-06-20 | 2009-12-23 | 電気化学工業株式会社 | Amorphous siliceous powder, process for production thereof, resin composition, and semiconductor encapsulation material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3404304B2 (en) | 1998-12-02 | 2003-05-06 | 株式会社日立製作所 | Epoxy resin composition and molded coil |
-
1989
- 1989-02-28 JP JP4743389A patent/JP2634663B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02228354A (en) * | 1989-03-01 | 1990-09-11 | Shin Etsu Chem Co Ltd | Epoxy resin composition for semiconductor encapsulation |
| JPH05235210A (en) * | 1991-08-02 | 1993-09-10 | Matsushita Electric Works Ltd | Epoxy resin molding material for sealing |
| JPH05206333A (en) * | 1992-01-27 | 1993-08-13 | Shin Etsu Chem Co Ltd | Epoxy resin composition for sealing semiconductor and hardened one thereof |
| JP2007070474A (en) * | 2005-09-07 | 2007-03-22 | Denki Kagaku Kogyo Kk | Inorganic powder and its use |
| JP2008088405A (en) * | 2006-09-07 | 2008-04-17 | Nitto Shinko Kk | Resin composition, heat conductive sheet, high heat conductive adhesive sheet with metal foil, and high heat conductive adhesive sheet with metal plate |
| WO2008078706A1 (en) * | 2006-12-22 | 2008-07-03 | Denki Kagaku Kogyo Kabushiki Kaisha | Amorphous silica powder, method for production thereof, and semiconductor sealing material |
| US8048817B2 (en) | 2006-12-22 | 2011-11-01 | Denki Kagaku Kogyo Kabushiki Kaisha | Amorphous silica powder, process for its production, and sealing material for semiconductors |
| JP5410095B2 (en) * | 2006-12-22 | 2014-02-05 | 電気化学工業株式会社 | Amorphous siliceous powder, method for producing the same, and semiconductor sealing material |
| JP2008189818A (en) * | 2007-02-05 | 2008-08-21 | Nitto Denko Corp | Thermally conductive resin composition, thermal conductive sheet and method for producing the same |
| WO2009154186A1 (en) * | 2008-06-20 | 2009-12-23 | 電気化学工業株式会社 | Amorphous siliceous powder, process for production thereof, resin composition, and semiconductor encapsulation material |
| US8592504B2 (en) | 2008-06-20 | 2013-11-26 | Denki Kagaku Kogyo Kabushiki Kaisha | Amorphous siliceous powder, process for production thereof, resin composition, and semiconductor encapsulation material |
| JP5526027B2 (en) * | 2008-06-20 | 2014-06-18 | 電気化学工業株式会社 | Amorphous siliceous powder, method for producing the same, resin composition, and semiconductor sealing material |
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|---|---|
| JP2634663B2 (en) | 1997-07-30 |
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