JPH0380174B2 - - Google Patents
Info
- Publication number
- JPH0380174B2 JPH0380174B2 JP59033185A JP3318584A JPH0380174B2 JP H0380174 B2 JPH0380174 B2 JP H0380174B2 JP 59033185 A JP59033185 A JP 59033185A JP 3318584 A JP3318584 A JP 3318584A JP H0380174 B2 JPH0380174 B2 JP H0380174B2
- Authority
- JP
- Japan
- Prior art keywords
- curable resin
- ceramic
- fine particles
- mixture
- molded product
- 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
Links
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 239000000919 ceramic Substances 0.000 claims description 20
- 239000010419 fine particle Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- 239000000057 synthetic resin Substances 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 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 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920003261 Durez Polymers 0.000 description 1
- -1 PR-900 Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】
本発明は、耐熱性硬化性樹脂成形品の製造法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a heat-resistant curable resin molded article.
更に詳しくは、セラミツク微粒子を分散させ、
耐熱性を改善した硬化性樹脂成形品の製造法に関
する。 More specifically, by dispersing ceramic fine particles,
This invention relates to a method for producing a curable resin molded product with improved heat resistance.
フエノール樹脂、エポキシ樹脂、フラン樹脂な
どの硬化性樹脂は、ガラス繊維や各種の充填剤を
配合して成形した場合でも、その成形品の熱変形
温度はそれ程高いものではなく、例えばフエノー
ル樹脂成形品は高々約260℃程度であり、またエ
ポキシ樹脂成形品は約150℃程度である。もつと
も、アルミナ、炭化けい素、窒化ホウ素、酸化チ
タンなどのセラミツク粉末を充填剤として用いた
場合には、その成形品の熱変形温度を更に向上さ
せることができると考えられるが、これらのセラ
ミツク粉末は比重が大きいため成形品中に良く分
散されず、部分的に偏在するので、成形品全体と
しては結局その耐熱性を向上させることができな
い。 Even when curable resins such as phenolic resins, epoxy resins, and furan resins are molded with glass fibers and various fillers, the heat distortion temperature of the molded products is not that high; for example, phenolic resin molded products is about 260°C at most, and about 150°C for epoxy resin molded products. However, if ceramic powder such as alumina, silicon carbide, boron nitride, or titanium oxide is used as a filler, it is thought that the heat distortion temperature of the molded product can be further improved. Since it has a large specific gravity, it is not well dispersed in the molded product and is unevenly distributed in some parts, so that the heat resistance of the molded product as a whole cannot be improved.
本発明者は、これらのセラミツク粉末を用いて
硬化性樹脂成形品の耐熱性を向上させるべく種々
検討の結果、セラミツクの微粉末を超音波により
分散せしめることにより、かかる課題が有効に解
決されることを見出した。 As a result of various studies aimed at improving the heat resistance of curable resin molded products using these ceramic powders, the present inventor has found that such problems can be effectively solved by dispersing fine ceramic powder using ultrasonic waves. I discovered that.
従つて、本発明は耐熱性硬化性樹脂成形品の製
造法に係り、この耐熱性硬化性樹脂成形品の製造
は、液状硬化性樹脂およびセラミツクス微粒子の
混合物を、合成樹脂製かごを介して浸漬浴中の成
形型内に仕込み、浸漬浴中に設置した超音波発生
装置から発生する超音波を該混合物に照射し、セ
ラミツクス微粒子を液状硬化性樹脂中に良好に分
散させながら、硬化性樹脂の硬化を行うことによ
つて行われる。 Therefore, the present invention relates to a method for producing a heat-resistant curable resin molded article, and the production of the heat-resistant curable resin molded article involves dipping a mixture of a liquid curable resin and ceramic fine particles through a synthetic resin basket. The mixture is placed in a mold in a bath, and the mixture is irradiated with ultrasonic waves generated from an ultrasonic generator placed in the immersion bath, and the ceramic fine particles are well dispersed in the liquid curable resin. This is done by curing.
液状の硬化性樹脂としては、主剤100重量部当
り約10〜30重量部の硬化剤を配合したものが用い
られ、具体的には市販品、例えば住友デユレズ製
品の硬化剤HP−45 10phr配合スミライトレジン
PR−900などのフエノール樹脂、油化シエル製品
の硬化剤エピキユアZ20phr配合エピコート828な
どのエポキシ樹脂などを用いることができる。 The liquid curable resin used is one containing approximately 10 to 30 parts by weight of a curing agent per 100 parts by weight of the base resin, and specifically, commercially available products such as Sumitomo Durez's curing agent HP-45 10 phr. light resin
Phenol resins such as PR-900, epoxy resins such as Epicoat 828 containing the curing agent Epicure Z20phr of Yuka Shell products, etc. can be used.
これらの液状硬化性樹脂に分散させるセラミツ
ク微粒子としては、アルミナ、炭化けい素、窒化
ホウ素、酸化チタンなどの微粉末、好ましくは金
属酸化物の微粒子が用いられる。微粒子の粒径分
布は、例えばアルミナの場合約0.02μm以下であ
りかつそれの約90％以上が約0.01μm以下である
ようなものが用いられる。これより大きい粒径分
布の微粒子が用いられると、それの比重が大きい
ため超音波を用いても液状樹脂中に良く分散せ
ず、また成形された成形品が破壊する起点とな
る。 As the ceramic fine particles to be dispersed in these liquid hardening resins, fine powders of alumina, silicon carbide, boron nitride, titanium oxide, etc., preferably fine particles of metal oxides are used. The particle size distribution of the fine particles used is, for example, in the case of alumina, about 0.02 μm or less and about 90% or more of the particles being about 0.01 μm or less. If fine particles with a particle size distribution larger than this are used, their specific gravity is so high that they will not be well dispersed in the liquid resin even when ultrasonic waves are used, and will also become a starting point for the molded article to break.
かかる粒径分布のセラミツク微粉末は、硬化し
た樹脂との良好な接着性を保持させるために、液
状樹脂中への分散に先立つてシラン系またはチタ
ン系カツプリング剤で表面処理をしておくことが
望ましい。この表面処理は、カツプリング剤の水
溶液中にセラミツク微粒子を浸漬、撹拌すること
により行われる。 In order to maintain good adhesion to the cured resin, ceramic fine powder with such a particle size distribution may be surface-treated with a silane-based or titanium-based coupling agent prior to dispersion into the liquid resin. desirable. This surface treatment is carried out by immersing the ceramic fine particles in an aqueous solution of the coupling agent and stirring.
セラミツク微粉末は、成形された成形品中約40
〜70容積％を占めるような割合で用いられる。こ
れ以下の割合では、成形品に十分な耐熱性改善の
効果が得られず、一方これ以上の割合で用いられ
ると、全体的にセラミツクの性質が増えるため加
工性が悪くなる。 Ceramic fine powder is about 40% of the molded product.
It is used in a proportion that accounts for ~70% by volume. If the proportion is less than this, a sufficient effect of improving the heat resistance of the molded product will not be obtained, while if the proportion is greater than this, the properties of the ceramic will increase as a whole, resulting in poor processability.
以上のような粒径分布および配合割合のセラミ
ツク微粒子は、超音波によつて液状硬化性樹脂中
に分散させ、その良好な分散状態を保持したまま
硬化させ、成形する。 Ceramic fine particles having the particle size distribution and blending ratio as described above are dispersed in a liquid curable resin by ultrasonic waves, cured and molded while maintaining a good dispersion state.
第１図は、かかる分散および硬化に用いられる
装置の一態様を示す断面図であり、液状硬化性樹
脂およびセラミツク微粒子の混合物１が成形型２
内に仕込まれ、超音波発生装置（例えば海上電機
株式会社製）３を底部に設置した水槽４内の水５
中に合成樹脂製かご６を介して浸漬する。前記混
合物中のセラミツク微粒子は、この装置から発生
される超音波によつて液状硬化性樹脂中に良好に
分散され、必要に応じて用いられる投込みヒータ
ー７による加熱により、所定の硬化温度で硬化す
る。なお、合成樹脂製かごは、成形型を直接超音
波発生装置の上に設置すると発振子が劣化するの
で、それを防止するために、任意の孔径、例えば
10mm程度の孔径の孔を有するものなどが用いられ
る。 FIG. 1 is a sectional view showing one embodiment of the apparatus used for such dispersion and curing, in which a mixture 1 of liquid curable resin and ceramic fine particles is placed in a mold 2.
Water 5 in a water tank 4 in which an ultrasonic generator (for example, manufactured by Kaiyo Denki Co., Ltd.) 3 is installed at the bottom.
It is immersed in the container via a synthetic resin basket 6. The ceramic fine particles in the mixture are well dispersed in the liquid curable resin by ultrasonic waves generated from this device, and cured at a predetermined curing temperature by heating with an immersion heater 7, which is used as needed. do. In addition, if the synthetic resin cage is placed directly on the ultrasonic generator, the oscillator will deteriorate, so in order to prevent this, it is necessary to use a synthetic resin cage with an arbitrary hole diameter, e.g.
Those having holes with a hole diameter of about 10 mm are used.
このように超音波を用いることにより、セラミ
ツク微粒子の液状硬化性樹脂への分散から成形を
一貫して行なうことができ、その結果得られた硬
化した樹脂成形品は、フエノール樹脂の場合約
300〜400℃（第２図参照）、またエポキシ樹脂の
場合約200〜300℃迄熱変形温度が上昇するという
効果をもたらす。このような効果は、セラミツク
の微粒子を硬化した樹脂成形品中に良好に分散さ
せたため、一種のハイブリツド効果が現われたも
のと考えられる。 By using ultrasonic waves in this way, it is possible to perform molding from the dispersion of ceramic fine particles into liquid curable resin, and the resulting cured resin molded product is approximately
This has the effect of increasing the heat distortion temperature to 300-400°C (see Figure 2), or to about 200-300°C in the case of epoxy resins. This effect is thought to be due to the fact that fine ceramic particles were well dispersed in the cured resin molded product, resulting in a kind of hybrid effect.
従つて、本発明に係る耐熱性硬化性樹脂成形品
は、より高い耐熱性が要求される用途、例えばフ
エノール樹脂の場合には絶縁キヤツプ、コネクタ
ー、マイクロスイツチ、コインスプール、整流子
などに成形し、それぞれ好適に使用することがで
きる。 Therefore, the heat-resistant curable resin molded product of the present invention can be used for applications requiring higher heat resistance, such as insulating caps, connectors, micro switches, coin spools, commutators, etc. in the case of phenolic resin. , each can be suitably used.
次に、実施例について本発明の効果を説明す
る。 Next, the effects of the present invention will be explained with reference to Examples.
実施例
前記住友デユレス製品のフエノール樹脂に、シ
ラン系カツプリング剤で表面処理された平均粒径
0.01μmのアルミナ微粒子を全体に対し40〜70容
積％の割合で加え、撹拌した後、図示された態様
に従つて、分散および硬化を行なつた。即ち、撹
拌混合物を成形型内に注型し、超音波で分散させ
ながら、90℃に１時間保持した。Example Average particle size of the phenolic resin of the Sumitomo Duress product surface treated with a silane coupling agent
Alumina fine particles of 0.01 μm were added at a ratio of 40 to 70% by volume to the whole, stirred, and then dispersed and hardened according to the illustrated embodiment. That is, the stirred mixture was poured into a mold and held at 90° C. for 1 hour while being dispersed using ultrasonic waves.
成形品の熱変形温度を、ASTM Ｄ−648試験
片（12.7×12.7×127mm）について、その中央部
に荷重264psi（18.6Kg／cm2）をかけて、シリコン
油中で1/100インチ（0.254mm）の歪発生時の油温
として測定した。得られた結果は、第２図のグラ
フに示される。 The heat distortion temperature of the molded product was measured using an ASTM D-648 test piece (12.7 x 12.7 x 127 mm) at 1/100 inch (0.254 mm) in silicone oil by applying a load of 264 psi (18.6 Kg/cm 2 ) to the center of the specimen. mm) was measured as the oil temperature at the time of strain occurrence. The results obtained are shown in the graph of FIG.
第１図は、本発明に係る耐熱性硬化性樹脂成形
品を製造する装置の一態様を示す断面図である。
また、第２図は、アルミナ微粒子の分散割合と熱
変形温度との関係を示すグラフである。
（符号の説明）、１……液状硬化性樹脂−セラ
ミツク微粒子混合物、２……成形型、３……超音
波発生装置、４……水槽、５……水、６……合成
樹脂製かご、７……投込みヒーター。
FIG. 1 is a sectional view showing one embodiment of an apparatus for manufacturing a heat-resistant curable resin molded article according to the present invention.
Moreover, FIG. 2 is a graph showing the relationship between the dispersion ratio of fine alumina particles and the heat distortion temperature. (Explanation of symbols), 1...Liquid curable resin-ceramic fine particle mixture, 2...Mold, 3...Ultrasonic generator, 4...Water tank, 5...Water, 6...Synthetic resin basket, 7... Immersion heater.
Claims (1)
合物を、合成樹脂製かごを介して浸漬浴中の成形
型内に仕込み、浸漬浴中に設置した超音波発生装
置から発生する超音波を該混合物に照射し、セラ
ミツク微粒子を液状硬化性樹脂中に良好に分散さ
せながら、硬化性樹脂の硬化を行うことを特徴と
する、セラミツク微粒子を40〜70容積％の割合で
分散させた耐熱性硬化性樹脂成形品の製造法。1. A mixture of liquid curable resin and ceramic fine particles is placed into a mold in an immersion bath via a synthetic resin cage, and the mixture is irradiated with ultrasonic waves generated from an ultrasonic generator installed in the immersion bath. , a heat-resistant curable resin molded product with ceramic particles dispersed at a ratio of 40 to 70% by volume, characterized in that the curable resin is cured while the ceramic particles are well dispersed in the liquid curable resin. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59033185A JPS60177028A (en) | 1984-02-23 | 1984-02-23 | Molded article of heat-resistant curable resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59033185A JPS60177028A (en) | 1984-02-23 | 1984-02-23 | Molded article of heat-resistant curable resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60177028A JPS60177028A (en) | 1985-09-11 |
| JPH0380174B2 true JPH0380174B2 (en) | 1991-12-24 |
Family
ID=12379433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59033185A Granted JPS60177028A (en) | 1984-02-23 | 1984-02-23 | Molded article of heat-resistant curable resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60177028A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020008048A1 (en) | 2000-05-08 | 2002-01-24 | Ricoh Company, Ltd. | Method of and system for managing rack operation, method of and system for managing multistage rack, article conveyance and storage device, and computer product |
| JP3749243B2 (en) | 2001-09-03 | 2006-02-22 | 松下電器産業株式会社 | Semiconductor light emitting device, light emitting apparatus, and method for manufacturing semiconductor light emitting device |
| JP2006022198A (en) * | 2004-07-08 | 2006-01-26 | Sumitomo Bakelite Co Ltd | Thermosetting resin composition and its preparation method |
| JP2010093036A (en) * | 2008-10-08 | 2010-04-22 | Sumitomo Electric Ind Ltd | Superconducting coil, superconducting magnet, epoxy resin varnish and method for manufacturing them |
-
1984
- 1984-02-23 JP JP59033185A patent/JPS60177028A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60177028A (en) | 1985-09-11 |
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