JP2513529B2 - Method of manufacturing filler for sealing electronic parts - Google Patents
Method of manufacturing filler for sealing electronic partsInfo
- Publication number
- JP2513529B2 JP2513529B2 JP2249747A JP24974790A JP2513529B2 JP 2513529 B2 JP2513529 B2 JP 2513529B2 JP 2249747 A JP2249747 A JP 2249747A JP 24974790 A JP24974790 A JP 24974790A JP 2513529 B2 JP2513529 B2 JP 2513529B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon dioxide
- dioxide particles
- filler
- electronic component
- sealing
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
【発明の詳細な説明】 （１）発明の目的 ［産業上の利用分野］ 本発明は、電子部品封止用充填材の製造方法に関し、
特に、熱硬化性樹脂に対して分散せしめられた二酸化珪
素粒子の少なくとも一部の表面に対し少なくとも１つの
凹部が形成されてなる電子部品封止用充填材の製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention [Industrial field of use] The present invention relates to a method for producing a filler for sealing electronic parts,
In particular, the present invention relates to a method for producing an electronic component sealing filler in which at least one concave portion is formed on at least a part of the surface of silicon dioxide particles dispersed in a thermosetting resin.
［従来の技術］ 従来、この種の電子部品封止用充填材としては、熱硬
化性樹脂（たとえばエポキシ樹脂など）に対し無機質と
して二酸化珪素粒子を分散せしめてなるものが提案され
ていた。[Prior Art] Heretofore, as a filler for sealing electronic parts of this type, there has been proposed one in which silicon dioxide particles are dispersed as an inorganic substance in a thermosetting resin (for example, an epoxy resin).
［解決すべき問題点］ しかしながら、従来の電子部品封止用充填材では、熱
硬化性樹脂に対し無機質として分散された二酸化珪素粒
子が破砕状であったので、電子部品（たとえば半導体素
子）を封止したときの応力を低減せしめるために熱硬化
性樹脂に比べて熱膨張係数の小さい二酸化珪素粒子の配
合量を増加せしめると、（ｉ）溶融粘度が増加してしま
う欠点があり、ひいては（ii）成形性が低下してしまい
かつ弾性率の増加などをまねく欠点があった。[Problems to be Solved] However, in the conventional filler for sealing electronic parts, since the silicon dioxide particles dispersed as an inorganic substance in the thermosetting resin are crushed, the electronic part (for example, semiconductor element) is If the compounding amount of silicon dioxide particles having a smaller thermal expansion coefficient than that of the thermosetting resin is increased in order to reduce the stress at the time of sealing, there is a drawback that (i) the melt viscosity increases, and eventually ( ii) There was a defect that the moldability was lowered and the elastic modulus was increased.
それ故、従来の電子部品封止用充填材では、熱硬化性
樹脂に対し無機質として分散された二酸化珪素粒子を球
状とすることにより溶融粘度を低減せしめることも提案
されていたが、（iii）球状の二酸化珪素粒子の配合量
が増加し過ぎると、電子部品を封止したのちの機械的強
度が低下してしまう欠点があった。Therefore, in the conventional filler for sealing electronic parts, it has been proposed to reduce the melt viscosity by making the silicon dioxide particles dispersed as an inorganic substance into the thermosetting resin spherical, but (iii) If the compounding amount of the spherical silicon dioxide particles is excessively increased, there is a drawback that the mechanical strength after sealing the electronic component is lowered.
そこで、本発明は、これらの欠点を除去する目的で、
熱硬化性樹脂に分散された二酸化珪素粒子の少なくとも
一部の表面に少なくとも１つの凹部を形成してなる電子
部品封止用充填材の製造方法を提供せんとするものであ
る。Therefore, the present invention aims to eliminate these disadvantages,
It is intended to provide a method for producing a filler for encapsulating electronic components, which comprises forming at least one recess on the surface of at least a part of silicon dioxide particles dispersed in a thermosetting resin.
（２）発明の構成 ［問題点の解決手段］ 本願発明の要旨は、熱硬化性樹脂に対し、二酸化珪素
粒子を分散せしめてなる電子部品封止用充填材の製造方
法において、所定の形状の二酸化珪素粒子の表面を、フ
ッ素を含有する溶液中にてエッチング処理することを特
徴とする電子部品封止用充填材の製造方法である。(2) Configuration of the Invention [Means for Solving Problems] The gist of the present invention is to provide a method for producing an electronic component sealing filler, which comprises silicon dioxide particles dispersed in a thermosetting resin, having a predetermined shape. A method for producing a filling material for sealing electronic parts, characterized in that the surface of silicon dioxide particles is subjected to an etching treatment in a solution containing fluorine.
［作用］ 本発明にかかる電子部品封止用充填材は、上述の［問
題点の解決手段］の欄に明示したごとく、熱硬化性樹脂
に対し無機質として分散された二酸化珪素粒子の少なく
とも一部の表面に少なくとも１つの凹部が形成されてい
るので、 （ｉ）二酸化珪素粒子の比表面積を拡張して溶媒粘度を
抑制しかつ硬化後の機械的強度を改善する作用 をなし、ひいては （ii）流動性，作業性ならびに耐摩耗性を改善する作用 をなす。[Operation] The electronic component sealing filler according to the present invention has at least a part of silicon dioxide particles dispersed as an inorganic substance in a thermosetting resin, as clearly shown in the above section of [Means for Solving Problems]. Since at least one recess is formed on the surface of (i), it has the function of (i) expanding the specific surface area of silicon dioxide particles to suppress the solvent viscosity and improving the mechanical strength after curing, and (ii) It functions to improve fluidity, workability and wear resistance.
さらに、本発明によれば、二酸化珪素粒子が外周面の
滑らかな球状であって、かつ、15％以上の二酸化珪素粒
子の外周面に曲面状の凹部が形成されているので、 （iii）充填材の表面に鋭角（角状）の凹凸部がなく、
充填材の表面において熱硬化性樹脂との非接触部が存在
することがなく、その結果、封止材として高い機械的強
度が得られる。Furthermore, according to the present invention, since the silicon dioxide particles have a smooth spherical outer peripheral surface and the curved surface-shaped recesses are formed on the outer peripheral surface of 15% or more of the silicon dioxide particles, (iii) filling The surface of the material has no irregularities with sharp angles (cornered),
There is no non-contact portion with the thermosetting resin on the surface of the filler, and as a result, high mechanical strength as a sealing material can be obtained.
また、特に本発明の製造方法によれば、原料が球状ま
たは破砕状のいずれであっても、二酸化珪素粒子の表面
をエッチング処理するので、前述のような充填材を製造
することが容易である。Further, in particular, according to the production method of the present invention, regardless of whether the raw material is spherical or crushed, the surface of the silicon dioxide particles is subjected to an etching treatment, so that it is easy to produce the filler as described above. .
［実施例］ 次に、本発明にかかる電子部品封止用充填材につい
て、その好ましい実施例を挙げ、具体的に説明する。[Examples] Next, the electronic component sealing filler according to the present invention will be specifically described with reference to its preferred examples.
（実施例） まず、本発明にかかる電子部品封止用充填材の一実施
例について、その構成および作用を詳細に説明する。(Example) First, the configuration and action of an example of the electronic component sealing filler according to the present invention will be described in detail.
本発明にかかる電子部品封止用充填材は、熱硬化性樹
脂（たとえばエポキシ樹脂）と、熱硬化性樹脂に対して
無機質として分散された二酸化珪素粒子とを備えてい
る。The electronic component sealing filler according to the present invention includes a thermosetting resin (for example, an epoxy resin) and silicon dioxide particles dispersed as an inorganic substance in the thermosetting resin.
二酸化珪素粒子は、非晶質二酸化珪素粒子あるいは結
晶質二酸化珪素粒子もしくはそれらの混合物であって、
表面形状が球状もしくは破砕状であり、その径が0.1μ
ｍ〜200μｍ（好ましくは１μｍ〜５μｍ）である。二
酸化珪素粒子は、少なくとも一部の表面に対し深さが径
の1/10000〜1/10（好ましくは1/1000〜1/100）で幅およ
び長さが径の1/10000〜9999/10000（好ましくは1/1000
〜9/10）である凹部がエッチング処理によって少なくと
も１つ形成されている。二酸化珪素粒子の少なくとも一
部が球状とされておれば、応力を低減せしめるために二
酸化珪素粒子の配合量を増加せしめたとき、溶融粘度の
増加を抑制することができるので、好ましい。ちなみ
に、二酸化珪素粒子が破砕状である場合、角部が除去さ
れておれば、応力を低減せしめるために二酸化珪素粒子
の配合量を増加せしめたとき、同様に、溶融粘度の増加
を抑制することができるので、好ましい。The silicon dioxide particles are amorphous silicon dioxide particles or crystalline silicon dioxide particles or a mixture thereof,
The surface shape is spherical or crushed, and the diameter is 0.1μ
m to 200 μm (preferably 1 μm to 5 μm). The silicon dioxide particles have a depth of 1/10000 to 1/10 (preferably 1/1000 to 1/100) of the diameter and a width and length of 1/10000 to 9999/10000 with respect to at least a part of the surface. (Preferably 1/1000
At least one recessed portion of 9 to 10) is formed by etching. It is preferable that at least a part of the silicon dioxide particles is spherical, because an increase in melt viscosity can be suppressed when the compounding amount of the silicon dioxide particles is increased in order to reduce the stress. By the way, when the silicon dioxide particles are in a crushed state, if the corners are removed, when increasing the compounding amount of the silicon dioxide particles to reduce the stress, the increase of the melt viscosity is similarly suppressed. Is preferred, which is preferable.
二酸化珪素粒子の径が0.1μｍ〜200μｍとされている
根拠は、（ｉ）0.1μｍ未満となると、微細化のために
製造コストが高騰することにあり、更に（ii）200μｍ
を超えると電子部品の封止のために使用されたとき充填
密度を確保できず熱伝導性ならびに機械的強度が低下す
ることにある。The reason why the diameter of the silicon dioxide particles is 0.1 μm to 200 μm is that (i) if it is less than 0.1 μm, the manufacturing cost will increase due to miniaturization, and (ii) 200 μm
If it exceeds, the filling density cannot be ensured when used for sealing electronic parts, and the thermal conductivity and mechanical strength are reduced.
二酸化珪素粒子の少なくとも一部の表面に対して形成
された凹部の深さが二酸化珪素粒子の径の1/10000〜1/1
0とされている根拠は、（ｉ）1/10000未満となると、実
質的に球状となってしまい比表面積が増加せず電子部品
を封止したのちの機械的強度が低下してしまうことにあ
る、また（ii）1/10を超えると、実質的に破砕状となっ
て比表面積が増加し過ぎ溶融粘度が増加してしまうこと
にある。The depth of the recess formed on the surface of at least part of the silicon dioxide particles is 1/10000 to 1/1 of the diameter of the silicon dioxide particles.
The rationale for being 0 is that (i) when it is less than 1/10000, it becomes substantially spherical, the specific surface area does not increase, and the mechanical strength after sealing the electronic component decreases. On the other hand, (ii) If it exceeds 1/10, it may be in a substantially crushed state and the specific surface area may be excessively increased to increase the melt viscosity.
二酸化珪素粒子の少なくとも一部の表面に対して形成
された凹部の幅および長さが二酸化珪素粒子の径の1/10
000〜9999/10000とされている根拠は、（ｉ）1/10000未
満となると、実質的に球状となってしまい比表面積が増
加せず電子部品を封止したのちの機械的強度が低下して
しまうことにある、また（ii）9999/10000を超えると、
実質的に破砕状となって比表面積が増加し過ぎ溶融粘度
が増加してしまうことにある。The width and length of the recess formed on the surface of at least a part of the silicon dioxide particle is 1/10 of the diameter of the silicon dioxide particle.
The rationale for 000 to 9999/10000 is that (i) when it is less than 1/10000, it becomes substantially spherical, the specific surface area does not increase, and the mechanical strength after sealing electronic components decreases. If (ii) 9999/10000 is exceeded,
This is because it becomes substantially crushed and the specific surface area increases too much to increase the melt viscosity.
二酸化珪素粒子の少なくとも一部の表面に対して形成
された凹部は、曲面（特に球面ないし楕円体面）であれ
ば、好ましい。The concave portion formed on at least a part of the surface of the silicon dioxide particle is preferably a curved surface (particularly spherical surface or ellipsoidal surface).
（製造方法） また、本発明にかかる電子部品封止用充填材の一実施
例について、その製造方法を簡単に説明する。(Manufacturing Method) A manufacturing method of an embodiment of the electronic component sealing filler according to the present invention will be briefly described.
本発明にかかる電子部品封止用充填材では、まず、
（ｉ）破砕状の二酸化珪素粒子を適宜のエッチング液中
で撹拌することにより、二酸化珪素粒子の表面をエッチ
ング処理し、二酸化珪素粒子の少なくとも一部の表面に
対し凹部を少なくとも１つ形成し、あるいは（ii）球状
の二酸化珪素粒子を適宜のエッチング溶液中で撹拌する
ことにより、二酸化珪素粒子の表面をエッチング処理
し、二酸化珪素の少なくとも一部の表面に対し凹部を少
なくとも１つ形成し、あるいは（iii）破砕状の二酸化
珪素粒子と球状の二酸化珪素粒子とを適宜のエッチング
液中で撹拌することにより、二酸化珪素粒子の表面をエ
ッチング処理し、二酸化珪素の少なくとも一部の表面に
対し凹部を少なくとも１つ形成している。エッチング液
は、フッ素を含有する溶液（たとえばフッ化水素酸溶液
あるいはフッ化アンモニウム溶液など）を採用すればよ
い。フッ化水素酸溶液は、フッ化水素の濃度が１〜49重
量％であることが好ましい。フッ化アンモニウム溶液、
フッ化アンモニウムの濃度が１〜45重量％であることが
好ましい。In the electronic component sealing filler according to the present invention, first,
(I) The crushed silicon dioxide particles are stirred in an appropriate etching solution to etch the surface of the silicon dioxide particles to form at least one concave portion on at least a part of the surface of the silicon dioxide particles, Or (ii) the spherical silicon dioxide particles are stirred in an appropriate etching solution to etch the surface of the silicon dioxide particles to form at least one recess on at least a part of the surface of the silicon dioxide, or (Iii) The crushed silicon dioxide particles and the spherical silicon dioxide particles are agitated in an appropriate etching solution to etch the surface of the silicon dioxide particles to form recesses on at least part of the surface of the silicon dioxide. At least one is formed. A solution containing fluorine (for example, a hydrofluoric acid solution or an ammonium fluoride solution) may be adopted as the etching solution. The hydrofluoric acid solution preferably has a hydrogen fluoride concentration of 1 to 49% by weight. Ammonium fluoride solution,
It is preferable that the concentration of ammonium fluoride is 1 to 45% by weight.
次いで、少なくとも一部の表面に少なくとも１つの凹
部が形成された二酸化珪素粒子が、熱硬化性樹脂に対し
適宜の割合で配合される。Next, the silicon dioxide particles having at least one concave portion formed on at least a part of the surface thereof are mixed with the thermosetting resin in an appropriate ratio.
以上により、本発明にかかる電子部品封止用充填材
は、製造される。As described above, the electronic component sealing filler according to the present invention is manufactured.
（具体例） 加えて、本発明にかかる電子部品封止用充填材の理解
を促進するために、具体的な数値などを挙げて説明す
る。(Specific Example) In addition, in order to facilitate understanding of the filler for encapsulating electronic components according to the present invention, specific numerical values and the like will be described.
実施例１ 走査型電子顕微鏡により観察した粒子構造が第２図
（ａ）および第３図（ａ）に示したごとく球状であっ
て、マイクロトラックによって測定した平均粒径が20μ
ｍである二酸化珪素粒子1kgを、第１図に示した容器11
に収容しておき、撹拌容器12に収容された25重量％のフ
ッ化水素酸溶液20中に対し計量装置13を介して200g/
分の割合で投入しつつ、撹拌容器12に配設されたテフロ
ン性の撹拌子15を回転装置14によって回転駆動した。こ
れにより、撹拌容器12中のフッ化水素酸溶液は、300回
／分以上の回転速度で撹拌された。ちなみに、撹拌容器
12には、スクラバ18が配設されており、大気中へ放出さ
れるフッ化水素酸の微粒子を捕収した。Example 1 The particle structure observed by a scanning electron microscope was spherical as shown in FIGS. 2 (a) and 3 (a), and the average particle size measured by Microtrac was 20 μm.
1 kg of silicon dioxide particles having a diameter of m is used for the container 11 shown in FIG.
200 g / 25 g of the 25 wt% hydrofluoric acid solution 20 contained in the stirring container 12 via the measuring device 13.
The Teflon stirrer 15 disposed in the stirring container 12 was rotationally driven by the rotating device 14 while being charged at a rate of min. As a result, the hydrofluoric acid solution in the stirring container 12 was stirred at a rotation speed of 300 times / minute or more. By the way, a stirring container
A scrubber 18 is arranged at 12 to collect fine particles of hydrofluoric acid released into the atmosphere.
撹拌を10分間継続したのち、エッチング処理された二
酸化珪素粒子は、フッ化水素酸溶液とともに、撹拌容器
12の下端部に取付けられた排水管16から開閉弁17を開放
して排出されたのち、セラミックフィルタに与えられて
フッ化水素酸溶液から分離された。After stirring for 10 minutes, the silicon dioxide particles that have been subjected to the etching treatment are mixed with the hydrofluoric acid solution in a stirring container.
After opening and closing the on-off valve 17 from the drainage pipe 16 attached to the lower end of 12 and discharging, it was given to the ceramic filter and separated from the hydrofluoric acid solution.
フッ化水素酸溶液から分離された二酸化珪素粒子は、
付着されたエッチング液（すなわちフッ化水素酸溶液）
が十分に除去されるまで、純水によって洗浄された。そ
ののち、二酸化珪素粒子は、スプレードライヤーによっ
て乾燥された。The silicon dioxide particles separated from the hydrofluoric acid solution are
Attached etchant (ie hydrofluoric acid solution)
Was washed with pure water until it was completely removed. After that, the silicon dioxide particles were dried by a spray dryer.
乾燥ののち、二酸化珪素粒子の比表面積を測定したと
ころ、第１表のとおりであった。また、走査型電子顕微
鏡によって二酸化珪素粒子の粒子構造を観察したとこ
ろ、第２図（ｂ）および第３図（ｂ）に示したとおりで
あり、15％以上の二酸化珪素粒子に深さが約２〜３μｍ
で幅および長さが約３〜20μｍである曲面状の凹部が形
成されていた。After drying, the specific surface area of the silicon dioxide particles was measured and found to be as shown in Table 1. The particle structure of the silicon dioxide particles was observed with a scanning electron microscope, and it was as shown in FIGS. 2 (b) and 3 (b), and the depth was about 15% or more of the silicon dioxide particles. 2-3 μm
, A curved concave portion having a width and a length of about 3 to 20 μm was formed.
曲面状の凹部の形成された二酸化珪素粒子が15％以上
であることにより、電子部品封止材としての機械的強度
が、従来の球状充填材を用いた場合より格段と向上す
る。When the silicon dioxide particles having the curved concave portions are 15% or more, the mechanical strength as the electronic component sealing material is significantly improved as compared with the case where the conventional spherical filler is used.
以上によりエッチング処理された二酸化珪素粒子70重
量％は、20重量％のエポキシ樹脂と10重量％のフェノー
ル樹脂とともに、ニーダ中に投入して混練された。混練
物は、直径1mm〜2mm程度まで粉砕してタブレットとされ
たのち、流動性の評価試験に供された。また、混練物
は、10mm×10mm×80mmの試料片とされたのち、機械的強
度の評価試験に供された。70% by weight of the silicon dioxide particles that had been subjected to the etching treatment as described above were put into a kneader and kneaded together with 20% by weight of an epoxy resin and 10% by weight of a phenol resin. The kneaded product was crushed into tablets each having a diameter of about 1 mm to 2 mm, and then subjected to a fluidity evaluation test. Further, the kneaded product was made into a 10 mm × 10 mm × 80 mm sample piece, and then subjected to an evaluation test of mechanical strength.
流動性の評価試験は、流動検査装置（いわゆる“フロ
ーテスター”）によって実行された。すなわち、流動検
査装置では、タブレットが試料として充填された状態で
シリンダを周囲から160℃に加熱しつつ、ピストンによ
ってシリンダ中のタブレットに一定の圧力（ここでは10
kgf/cm2）が加えられた。これに伴なって、試料（すな
わちタブレット）は、シリンダ内で溶融され、シリンダ
に配設されたダイの細孔から押し出された。そのときの
ピストン移動速度から溶融粘度が求められ、流動性の評
価に供された。その結果は、第１表に示すとおりであっ
た。The flowability evaluation test was carried out by means of a flow tester (so-called "flow tester"). That is, in the flow inspection apparatus, while heating the cylinder from the surroundings to 160 ° C. with the tablet filled with the sample as a sample, a constant pressure (here 10
kgf / cm 2 ) was added. Along with this, the sample (ie tablet) was melted in the cylinder and extruded through the pores of the die arranged in the cylinder. The melt viscosity was obtained from the piston moving speed at that time, and the melt viscosity was evaluated. The results are shown in Table 1.
機械的強度の評価試験は、10mm×10mm×80mmの試料片
の３点曲げ強さを測定することによって実行された。そ
の結果は、第１表に示すとおりであった。The mechanical strength evaluation test was carried out by measuring the three-point bending strength of a 10 mm x 10 mm x 80 mm specimen. The results are shown in Table 1.
比較例１ 走査型電子顕微鏡により観察した粒子構造が第２図
（ａ）および第３図（ａ）に示したごとく球状で あって、マイクロトラックによって測定した平均粒径が
20μｍである二酸化珪素粒子70重量％は、エッチング処
理されることなく、20重量％のエポキシ樹脂と10重量％
のフェノール樹脂とともにニーダ中に投入して混練さ
れ、実施例１と同様の流動性および機械的強度の評価試
験に供された。Comparative Example 1 The particle structure observed by a scanning electron microscope was spherical as shown in FIGS. 2 (a) and 3 (a). The average particle size measured by Microtrac is
70% by weight of silicon dioxide particles having a size of 20 μm are 20% by weight of epoxy resin and 10% by weight without being etched.
It was put into a kneader together with the phenol resin of No. 1 and kneaded, and then subjected to the same evaluation test of fluidity and mechanical strength as in Example 1.
その結果は、第１表に示したとおりであった。ちなみ
に、二酸化珪素粒子の比表面積も、第１表に示したとお
り、実施例１と同様に計測された。The results are as shown in Table 1. Incidentally, the specific surface area of the silicon dioxide particles was also measured as in Example 1 as shown in Table 1.
実施例２ 走査型電子顕微鏡により観察した粒子構造が第４図
（ａ）および第５図（ａ）に示したごとく破砕状であっ
て、マイクロトラックによって測定した平均粒径が15μ
ｍである二酸化珪素粒子1kgを、第１図に示した容器11
に収容しておき、撹拌容器12に収容された25重量％のフ
ッ化水素酸溶液20中に対し計量装置13を介して200g/
分の割合で投入しつつ、撹拌容器12に配設されたテフロ
ン性の撹拌子15を回転装置14によって回転駆動した。こ
れにより、撹拌容器12中のフッ化水素酸溶液は、300回
／分以上の回転速度で撹拌された。ちなみに、撹拌容器
12には、スクラバ18が配設されており、大気中へ放出さ
れるフッ化水素酸の微粒子を捕収した。Example 2 The particle structure observed by a scanning electron microscope was crushed as shown in FIGS. 4 (a) and 5 (a), and the average particle size measured by Microtrac was 15 μm.
1 kg of silicon dioxide particles having a diameter of m is used for the container 11 shown in FIG.
200 g / 25 g of the 25 wt% hydrofluoric acid solution 20 contained in the stirring container 12 via the measuring device 13.
The Teflon stirrer 15 disposed in the stirring container 12 was rotationally driven by the rotating device 14 while being charged at a rate of min. As a result, the hydrofluoric acid solution in the stirring container 12 was stirred at a rotation speed of 300 times / minute or more. By the way, a stirring container
A scrubber 18 is arranged at 12 to collect fine particles of hydrofluoric acid released into the atmosphere.
撹拌を10分間継続したのち、エッチング処理された二
酸化珪素粒子は、フッ化水素酸溶液とともに、撹拌容器
12の下端部に取付けられた排水管16から開閉弁17を開放
して排出されたのち、セラミックに与えられてフッ化水
素酸溶液から分離された。After stirring for 10 minutes, the silicon dioxide particles that have been subjected to the etching treatment are mixed with the hydrofluoric acid solution in a stirring container.
After opening and closing the on-off valve 17 from the drain pipe 16 attached to the lower end of 12 and discharging, it was given to the ceramic and separated from the hydrofluoric acid solution.
フッ化水素酸溶液から分離された二酸化珪素粒子は、
付着されたエッチング液（すなわちフッ化水素酸溶液）
が十分に除去されるまで、純水によって洗浄された。そ
ののち、二酸化珪素粒子は、スプレードライヤーによっ
て乾燥された。The silicon dioxide particles separated from the hydrofluoric acid solution are
Attached etchant (ie hydrofluoric acid solution)
Was washed with pure water until it was completely removed. After that, the silicon dioxide particles were dried by a spray dryer.
乾燥ののち、二酸化珪素粒子の比表面積を測定したと
ころ、第１表のとおりであった。また、走査型電子顕微
鏡によって二酸化珪素粒子の粒子構造を観察したとこ
ろ、第４図（ｂ）および第５図（ｂ）に示したとおりで
あり、15％以上の二酸化珪素粒子に深さが約0.1〜１μ
ｍで幅および長さが約0.1〜５μｍである曲面状の凹部
が形成されていた。After drying, the specific surface area of the silicon dioxide particles was measured and found to be as shown in Table 1. The particle structure of the silicon dioxide particles was observed with a scanning electron microscope, and it was as shown in FIGS. 4 (b) and 5 (b), and the depth was about 15% or more of the silicon dioxide particles. 0.1 ~ 1μ
A curved concave portion having a width and a length of about 0.1 to 5 μm was formed.
曲面状の凹部の形成された二酸化珪素粒子が15％以上
であることにより、電子部品封止材としての機械的強度
が、従来の球状充填材を用いた場合より格段と向上す
る。When the silicon dioxide particles having the curved concave portions are 15% or more, the mechanical strength as the electronic component sealing material is significantly improved as compared with the case where the conventional spherical filler is used.
以上によりエッチング処理された二酸化珪素粒子70重
量％は、20重量％のエポキシ樹脂と10重量％のフェノー
ル樹脂とともに、ニーダ中に投入して混練された。混練
物は、直径1mm〜2mm程度まで粉砕してタブレットとされ
たのち、流動性の評価試験に供された。また、混練物
は、10mm×10mm×80mmの試料片とされたのち、機械的強
度の評価試験に供された。70% by weight of the silicon dioxide particles that had been subjected to the etching treatment as described above were put into a kneader and kneaded together with 20% by weight of an epoxy resin and 10% by weight of a phenol resin. The kneaded product was crushed into tablets each having a diameter of about 1 mm to 2 mm, and then subjected to a fluidity evaluation test. Further, the kneaded product was made into a 10 mm × 10 mm × 80 mm sample piece, and then subjected to an evaluation test of mechanical strength.
流動性の評価試験は、流動検査装置（いわゆる“フロ
ーテスター”）によって実行された。すなわち、流動検
査装置では、タブレットが試料として充填された状態で
シリンダを周囲から160℃に加熱しつつ、ピストンによ
ってシリンダ中のタブレットに一定の圧力（ここでは10
kgf/cm2）が加えられた。これに伴なって、試料（すな
わちタブレット）は、シリンダ内で溶融され、シリンダ
に配設されたダイの細孔から押し出された。そのときの
ピストン移動速度から溶融粘度が求められ、流動性の評
価に供された。その結果は、第１表に示すとおりであっ
た。The flowability evaluation test was carried out by means of a flow tester (so-called "flow tester"). That is, in the flow inspection apparatus, while heating the cylinder from the surroundings to 160 ° C. with the tablet filled with the sample as a sample, a constant pressure (here 10
kgf / cm 2 ) was added. Along with this, the sample (ie tablet) was melted in the cylinder and extruded through the pores of the die arranged in the cylinder. The melt viscosity was obtained from the piston moving speed at that time, and the melt viscosity was evaluated. The results are shown in Table 1.
機械的強度の評価試験は、10mm×10mm×80mmの試料片
の３点曲げ強さを測定することによって実行された。そ
の結果は、第１表に示すとおりであった。The mechanical strength evaluation test was carried out by measuring the three-point bending strength of a 10 mm x 10 mm x 80 mm specimen. The results are shown in Table 1.
比較例２ 走査型電子顕微鏡により観察した粒子構造が第４図
（ａ）および第５図（ａ）に示したごとく破砕状であっ
て、マイクロトラックによって測定した平均粒径が15μ
ｍである二酸化珪素粒子70重量％は、エッチング処理さ
れることなく、20重量％のエポキシ樹脂と10重量％のフ
ェノール樹脂とともにニーダ中に投入して混練され、実
施例２と同様の流動性および機械的強度の評価試験に供
された。Comparative Example 2 The particle structure observed by a scanning electron microscope was crushed as shown in FIGS. 4 (a) and 5 (a), and the average particle size measured by Microtrac was 15 μm.
70% by weight of silicon dioxide particles, which is m, was put into a kneader together with 20% by weight of an epoxy resin and 10% by weight of a phenol resin without being subjected to etching treatment, and kneaded to obtain the same fluidity and It was subjected to a mechanical strength evaluation test.
その結果は、第１表に示したとおりであった。ちなみ
に、二酸化珪素粒子の比表面積も、第１表に示したとお
り、実施例２と同様に計測された。The results are as shown in Table 1. Incidentally, the specific surface area of the silicon dioxide particles was also measured as in Example 2 as shown in Table 1.
実施例1,2と比較例1,2との比較 実施例1,2と比較例1,2との比較結果から明らかなごと
く、本発明によれば、溶融粘度を実質的に維持しつつ、
二酸化珪素粒子の比表面積を少なくとも約10％増加で
き、かつ硬化後の機械的強度（ここでは３点曲げ強さ）
を少なくとも約20％増加できた。Comparison between Examples 1 and 2 and Comparative Examples 1 and 2 As is clear from the comparison results between Examples 1 and 2 and Comparative Examples 1 and 2, according to the present invention, while substantially maintaining the melt viscosity,
The specific surface area of silicon dioxide particles can be increased by at least about 10%, and the mechanical strength after curing (here, 3-point bending strength)
Could be increased by at least about 20%.
（３）発明の効果 上述より明らかなように、本発明にかかる電子部品封
止用充填材は、上述の［問題点の解決手段］の欄に明示
したごとく、熱硬化性樹脂に対し無機質として分散され
た二酸化珪素粒子の少なくとも一部の表面に少なくとも
１つの凹部が形成されているので、 （ｉ）二酸化珪素粒子の比表面積を拡張して溶融粘度を
抑制しかつ硬化後の機械的強度を改善できる効果 を有し、併せて （ii）流動性，作業性ならびに耐摩耗性を改善できる効
果 を有する。(3) Effects of the invention As is clear from the above, the electronic component sealing filler according to the present invention is an inorganic substance to the thermosetting resin, as clearly shown in the above section of "Means for solving problems". Since at least one recess is formed on the surface of at least a part of the dispersed silicon dioxide particles, (i) the specific surface area of the silicon dioxide particles is expanded to suppress the melt viscosity, and the mechanical strength after curing is increased. It has the effect of being able to improve, and also has the effect of (ii) improving the fluidity, workability and wear resistance.
さらに、本発明によれば、二酸化珪素粒子が外周面の
滑らかな球状であって、かつ15％以上の二酸化珪素粒子
の外周面に曲面状の凹部が形成されているので、（ii
i）充填材の表面に鋭角（角状）の凹凸部がなく、充填
材の表面において熱硬化性樹脂との非接触部が存在する
ことがなく、その結果、封止材として高い機械的強度が
得られる。Furthermore, according to the present invention, since the silicon dioxide particles have a smooth spherical outer peripheral surface, and 15% or more of the silicon dioxide particles have curved concave portions formed on the outer peripheral surface, (ii)
i) The surface of the filling material has no irregularities with an acute angle (corner), and there is no non-contact portion with the thermosetting resin on the surface of the filling material, resulting in high mechanical strength as a sealing material. Is obtained.
また、特に本発明の方法によれば、原料が球状または
破砕状のいずれであっても、二酸化珪素粒子の表面をエ
ッチング処理するので、前述のような充填材を製造する
ことが容易である。Further, in particular, according to the method of the present invention, the surface of the silicon dioxide particles is subjected to the etching treatment regardless of whether the raw material is spherical or crushed. Therefore, it is easy to manufacture the above-mentioned filler.
第１図は本発明にかかる電子部品封止用充填材の一実施
例を実験室で製造した製造装置を示すための構成図、第
２図（ａ）は本発明にかかる電子部品封止用充填材に含
まれた二酸化珪素粒子のエッチング処理前の粒子構造を
示すための写真、第２図（ｂ）は第２図（ａ）に示した
二酸化珪素粒子のエッチング処理後の粒子構造を示すた
めの写真、第３図（ａ）は本発明にかかる電子部品封止
用充填材に含まれた二酸化珪素粒子のエッチング処理前
の粒子構造を示すための写真、第３図（ｂ）は第３図
（ａ）に示した二酸化珪素粒子のエッチング処理後の粒
子構造を示すための写真、第４図（ａ）は本発明にかか
る電子部品封止用充填材に含まれた二酸化珪素粒子のエ
ッチング処理前の粒子構造を示すための写真、第４図
（ｂ）は第４図（ａ）に示した二酸化珪素粒子のエッチ
ング処理後の粒子構造を示すための写真、第５図（ａ）
は本発明にかかる電子部品封止用充填材に含まれた二酸
化珪素粒子のエッチング処理前の粒子構造を示すための
写真、第５図（ｂ）は第５図（ａ）に示した二酸化珪素
粒子のエッチング処理後の粒子構造を示すための写真で
ある。 11……容器 12……撹拌容器 13……計量装置 14……回転装置 15……撹拌子 16……排水管 17……開閉弁 18……スクラバFIG. 1 is a block diagram showing a manufacturing apparatus for manufacturing an embodiment of an electronic component sealing filler according to the present invention in a laboratory, and FIG. 2 (a) is an electronic component sealing according to the present invention. A photograph for showing the particle structure of the silicon dioxide particles contained in the filler before the etching treatment, and FIG. 2 (b) shows the particle structure of the silicon dioxide particles shown in FIG. 2 (a) after the etching treatment. 3 (a) is a photograph for showing the particle structure of silicon dioxide particles contained in the filler for sealing electronic parts according to the present invention before the etching treatment, and FIG. 3 (b) is a photograph for showing the particle structure. FIG. 3 (a) is a photograph showing the particle structure of the silicon dioxide particles after the etching treatment, and FIG. 4 (a) shows the silicon dioxide particles contained in the electronic component sealing filler according to the present invention. A photograph showing the grain structure before etching, FIG. 4 (b) is FIG. 4 (a). Pictures to indicate the grain structure after etching of the silicon dioxide particles shown, FIG. 5 (a)
Is a photograph showing the particle structure of silicon dioxide particles contained in the filler for sealing electronic parts according to the present invention before etching, and FIG. 5 (b) is the silicon dioxide shown in FIG. 5 (a). It is a photograph for showing a particle structure after etching processing of particles. 11 …… Vessel 12 …… Stirring vessel 13 …… Measuring device 14 …… Rotating device 15 …… Stirrer 16 …… Drain pipe 17 …… Opening / closing valve 18 …… Scrubber
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−315515（ＪＰ，Ａ) 特開 昭64−62362（ＪＰ，Ａ) 特開 昭59−81350（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-63-315515 (JP, A) JP-A-64-62362 (JP, A) JP-A-59-81350 (JP, A)
Claims (1)
散せしめてなる電子部品封止用充填材の製造方法におい
て、所定の形状の二酸化珪素粒子の表面を、フッ素を含
有する溶液中にてエッテング処理することを特徴とする
電子部品封止用充填材の製造方法。1. A method for producing a filler for electronic component encapsulation, comprising silicon dioxide particles dispersed in a thermosetting resin, wherein the surface of the silicon dioxide particles having a predetermined shape is immersed in a solution containing fluorine. A method for manufacturing a filling material for encapsulating electronic components, which comprises performing an etching process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2249747A JP2513529B2 (en) | 1990-09-19 | 1990-09-19 | Method of manufacturing filler for sealing electronic parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2249747A JP2513529B2 (en) | 1990-09-19 | 1990-09-19 | Method of manufacturing filler for sealing electronic parts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04130161A JPH04130161A (en) | 1992-05-01 |
| JP2513529B2 true JP2513529B2 (en) | 1996-07-03 |
Family
ID=17197617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2249747A Expired - Fee Related JP2513529B2 (en) | 1990-09-19 | 1990-09-19 | Method of manufacturing filler for sealing electronic parts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2513529B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080216704A1 (en) * | 2007-03-09 | 2008-09-11 | Fisher Controls International Llc | Conformal Coating |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5981350A (en) * | 1982-11-02 | 1984-05-11 | Matsushita Electronics Corp | Sealing resin |
| JPS63315515A (en) * | 1987-06-19 | 1988-12-23 | Ube Ind Ltd | Granulated magnesia substance and production thereof |
| JPS6462362A (en) * | 1987-09-03 | 1989-03-08 | Seitetsu Kagaku Co Ltd | Filler and polymer composition containing same |
-
1990
- 1990-09-19 JP JP2249747A patent/JP2513529B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04130161A (en) | 1992-05-01 |
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