JPS6235434B2 - - Google Patents
Info
- Publication number
- JPS6235434B2 JPS6235434B2 JP5152382A JP5152382A JPS6235434B2 JP S6235434 B2 JPS6235434 B2 JP S6235434B2 JP 5152382 A JP5152382 A JP 5152382A JP 5152382 A JP5152382 A JP 5152382A JP S6235434 B2 JPS6235434 B2 JP S6235434B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- flowability
- epoxy resin
- resin powder
- 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
- 239000000843 powder Substances 0.000 claims description 38
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 17
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 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 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 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
- 238000000034 method Methods 0.000 description 3
- 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 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- -1 curing accelerators Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-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
- 239000006185 dispersion Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Description
本発明は、常態でのブロツキングがなく、溶融
時粘度が低く流れ性の高い含浸用に好適なエポキ
シ樹脂粉末組成物に関するものである。
エポキシ樹脂粉末を用いて例えばコイルの電磁
線を含浸固着する方法として、コイルを該粉末の
溶融温度以上に加熱し、該粉末を散布または吹付
ける方法がある。この場合、含浸性を上げる手段
として低分子量、あるいは結晶性の樹脂、硬化剤
を用い溶融時粘度を下げることにより、流れ性を
付与することが考えられる。しかし、これらの樹
脂や硬化剤は低分子量とすると融点が低くなる傾
向があり、一方結晶性成分は溶融混合されること
により結晶性が崩れ、融点降下を起こし、粉末と
した後ブロツキングの発生原因となる。
従来、かかるブロツキングを防止する方法とし
て、樹脂粉末に種々の無機充填剤をドライブレン
ドする企みもなされているが、溶融時における粘
度が高くなり流れ性が低下し、その結果含浸性が
損われるという欠点があつた。換言すれば、樹脂
粉末のブロツキング防止性と流れ性は本来相反す
る性質のものであり、両者を兼備させることは非
常に困難であり、未だ実用的に満足しうるものが
得られていないのが実状である。
本発明者達は、このような実状に鑑み、流れ性
を低下させることなく、ブロツキングを防止しう
るエポキシ樹脂粉末組成物を鋭意研究の結果、基
本となる流れ性のよいエポキシ樹脂粉末に２種の
特定成分を所定割合で配合することにより目的を
達成しうることを見出し、本発明に至つたもので
ある。
すなわち、本発明は加熱温度150℃での溶融粘
度が0.2〜20ポイズであり、且つ後述の試験条件
での流れ性試験において熱鋼板上を10cm流れるの
に要する時間が20秒以内である、硬化剤を含む溶
融時低粘度で流れ性のよいエポキシ樹脂粉末100
重量部に対して、樹脂酸あるいは有機酸で表面処
理した平均粒子径30〜100mμの炭酸カルシウム
１〜10重量部および平均粒子径70μ以下の次の式
The present invention relates to an epoxy resin powder composition suitable for impregnation, which is free from blocking in the normal state, has a low viscosity when melted, and has high flowability. As a method of impregnating and fixing electromagnetic radiation in a coil using epoxy resin powder, for example, there is a method of heating the coil to a temperature higher than the melting temperature of the powder and then scattering or spraying the powder. In this case, as a means of increasing impregnating properties, it may be possible to impart flowability by lowering the viscosity when melted by using a low molecular weight or crystalline resin or curing agent. However, when these resins and curing agents have low molecular weights, their melting points tend to decrease.On the other hand, when crystalline components are melted and mixed, their crystallinity collapses, causing a drop in their melting points, which is the cause of blocking after powdering. becomes. Conventionally, as a method to prevent such blocking, attempts have been made to dry blend various inorganic fillers with resin powder, but it is said that the viscosity when melted increases and flowability decreases, resulting in impregnating properties. There were flaws. In other words, the anti-blocking property and flowability of resin powder are originally contradictory properties, and it is extremely difficult to achieve both, and the reason why a practically satisfactory product has not yet been obtained is that This is the actual situation. In view of these circumstances, the inventors of the present invention have conducted extensive research into epoxy resin powder compositions that can prevent blocking without reducing flowability, and have developed two types of basic epoxy resin powders that have good flowability. The inventors have discovered that the object can be achieved by blending specific components in predetermined proportions, leading to the present invention. That is, the present invention is a hardened material that has a melt viscosity of 0.2 to 20 poise at a heating temperature of 150°C, and that the time required to flow 10 cm over a hot steel plate in a flowability test under the test conditions described below is 20 seconds or less. Epoxy resin powder 100 with low viscosity and good flowability when melted
1 to 10 parts by weight of calcium carbonate with an average particle size of 30 to 100 mμ surface-treated with resin acid or organic acid and the following formula with an average particle size of 70 μm or less
【式】（R1：エチレン基、
プロピレン基、R2およびR3：分子量約170〜270
の炭化水素残基）で表わされる長鎖脂肪族ポリア
ミド１〜10重量部をドライブレンドしてなるエポ
キシ樹脂粉末組成物に関するものである。
本発明において、硬化剤を含む溶融時低粘度で
流れ性のよいエポキシ樹脂粉末とは、加熱温度
150℃での溶融粘度が0.2〜20ポイズ、好ましくは
0.6〜10ポイズが実用的である。
ここでいう流れ性とは、例えば所定傾斜角度並
びに樹脂粉末の溶融温度以上に設定した熱板上
に、ペレツト状に成型した試料粉末を置き、溶融
した後に所定時間内に流れた距離あるいは所定距
離を流れるのに要した時間で表わされるものであ
る。以下、本発明において流れ性試験とは、次の
条件で試験したものを示しており、上記エポキシ
樹脂粉末としては、熱鋼板上を10cm流れるのに要
する時間が20秒以内の流れ性のよい粉末が用いら
れる。
試験条件：長さ20cmの脱脂鋼板を30度に傾斜し、
表面温度を150℃に設定する。試料粉末は0.25
ｇを圧力20Kg／cm2でプレスした径13mmψのペレ
ツトを用いる。
このような溶融時低粘度で流れ性のよいエポキ
シ樹脂粉末を得るために用いる固形エポキシ樹脂
としては、トリスグリシジルイソシアヌレートな
どの結晶性エポキシ樹脂、あるいはビスフエノー
ルＡ型エポキシ樹脂などが挙げられ、また硬化剤
としてはジアミノジフエニルメタン、メタフエニ
レンジアミンなどのアミン類、無水テトラヒドロ
フタル酸、エチレングリコールビストリメリテイ
トなどの酸無水物、ジシアンジアミド、イミダゾ
ール類など挙げられる。
エポキシ樹脂粉末は、上記のエポキシ樹脂、硬
化剤の他に必要に応じて硬化促進剤、充填剤、顔
料などの各種添加剤を配合し、撹拌釜、混練ロー
ル、押出機等により撹拌混合あるいは溶融混合し
た後粉砕して、通常60メツシユパス、好ましくは
150メツシユパスの粉末が用いられるが、この基
本となる粉末は前述のようにブロツキングが発生
し易いものである。
本発明においては、上記エポキシ樹脂粉末100
重量部に対して、ブロツキング防止その他の機能
を与えるため、樹脂酸あるいは有機酸で表面処理
した平均粒子径30〜100mμの炭酸カルシウム１
〜10重量部がドライブレンドされる。樹脂酸とし
てはジテルペン酸、アビエチン酸、ピマル酸、桂
皮酸、安息香酸など、有機酸としてはステアリン
酸、パルミチン酸、オレイン酸、リノール酸など
が使用され、これらの酸で表面処理された所定粒
子径の炭酸カルシウムは、エポキシ樹脂粉末への
分散および相溶性がよく、比較的粘度を上げるこ
とが少なく、また流れ性を低下させることが少な
いという機能を与える。
かかる表面処理をしていない炭酸カルシウムで
は、樹脂粉末への分散および相溶性が悪く、ブロ
ツキング防止効果も悪く、かつ流れ性も極度に低
下する。また、表面処理を施してある炭酸カルシ
ウムであつても、平均粒子径が100mμ以上であ
ると、樹脂粉末への分散が悪く、かつ樹脂粉末粒
子表面を改質できないためブロツキングを防止で
きず、30mμ以下では樹脂粉末組成物の溶融時粘
度が上がり本発明の目的には適さない。さらに、
表面処理した平均粒子径が30〜100mμの炭酸カ
ルシウムであつても、配合量が１重量部以下では
添加の効果が薄く、10重量部以上ではブロツキン
グは防止できるが、溶融時粘度が上がり、流れ性
が大きく低下する。
本発明の目的のためには、上記表面処理した炭
酸カルシウムの配合のみでは不十分であり、さら
に流れ性、分散性等を付与する成分として平均粒
子径70μ以下の長鎖脂肪族ポリアミド１〜10重量
部が同時にドライブレンドされる。この場合前記
ポリアミド粉末は、基本となるエポキシ樹脂粉末
の種類にもよるが、前記表面処理炭酸カルシウム
の添加量の0.4〜５倍の範囲で使用するのが好ま
しい。この長鎖脂肪酸ポリアミドは、式
[Formula] (R 1 : ethylene group, propylene group, R 2 and R 3 : molecular weight approximately 170-270
The present invention relates to an epoxy resin powder composition obtained by dry blending 1 to 10 parts by weight of a long-chain aliphatic polyamide (hydrocarbon residue). In the present invention, the epoxy resin powder containing a hardening agent and having low viscosity and good flowability when melted is defined as
Melt viscosity at 150℃ is 0.2~20 poise, preferably
0.6 to 10 poise is practical. Flowability here means, for example, the distance that a sample powder formed into a pellet is placed on a hot plate set at a predetermined inclination angle and at a temperature higher than the melting temperature of the resin powder, and the distance it flows within a predetermined time after melting, or the predetermined distance. It is expressed as the time required for the flow to occur. Hereinafter, in the present invention, the flowability test refers to a test conducted under the following conditions. is used. Test conditions: A 20cm long degreased steel plate is tilted at 30 degrees.
Set the surface temperature to 150℃. Sample powder is 0.25
Pellets with a diameter of 13 mmψ are used, which are obtained by pressing the pellets at a pressure of 20 Kg/cm 2 . Solid epoxy resins used to obtain such epoxy resin powders with low viscosity and good flowability when melted include crystalline epoxy resins such as trisglycidyl isocyanurate, bisphenol A type epoxy resins, and the like. Examples of the curing agent include amines such as diaminodiphenylmethane and metaphenylenediamine, acid anhydrides such as tetrahydrophthalic anhydride and ethylene glycol bistrimeritate, dicyandiamide, and imidazoles. Epoxy resin powder is made by blending various additives such as curing accelerators, fillers, and pigments as necessary in addition to the epoxy resin and curing agent mentioned above, and then stirring and mixing or melting the mixture using a stirring pot, kneading roll, extruder, etc. After mixing and grinding, usually 60 mesh passes, preferably
A 150 mesh pass powder is used, but this basic powder is prone to blocking as described above. In the present invention, the above epoxy resin powder 100
Calcium carbonate with an average particle size of 30 to 100 mμ, surface-treated with resin acid or organic acid to provide anti-blocking and other functions per part by weight.
~10 parts by weight are dry blended. Diterpenic acid, abietic acid, pimaric acid, cinnamic acid, benzoic acid, etc. are used as resin acids, and stearic acid, palmitic acid, oleic acid, linoleic acid, etc. are used as organic acids, and predetermined particles surface-treated with these acids are used. Calcium carbonate having a large diameter has good dispersibility and compatibility with the epoxy resin powder, and provides the functions of relatively little increase in viscosity and little decrease in flowability. Calcium carbonate that has not undergone such surface treatment has poor dispersion and compatibility with resin powder, poor anti-blocking effect, and extremely poor flowability. In addition, even if calcium carbonate is surface-treated, if the average particle diameter is 100 mμ or more, it will not disperse well into the resin powder and the surface of the resin powder particles cannot be modified, making it impossible to prevent blocking. Below this, the viscosity of the resin powder composition upon melting increases, making it unsuitable for the purpose of the present invention. moreover,
Even with surface-treated calcium carbonate with an average particle size of 30 to 100 mμ, the effect of addition is weak if the amount is less than 1 part by weight, and blocking can be prevented if it is more than 10 parts by weight, but the viscosity increases when melted, causing flow. performance is greatly reduced. For the purpose of the present invention, it is insufficient to incorporate only the surface-treated calcium carbonate, and in addition, as a component that imparts flowability, dispersibility, etc., long-chain aliphatic polyamide 1 to 10 with an average particle diameter of 70μ or less is used. The weight parts are dry blended simultaneously. In this case, the polyamide powder is preferably used in an amount of 0.4 to 5 times the amount of the surface-treated calcium carbonate, although it depends on the type of the basic epoxy resin powder. This long chain fatty acid polyamide has the formula
【式】（R1：エチレン基、
プロピレン基、R2およびR3：分子量約170〜270
の炭化水素残基）で表わされ、平均粒子径70μ以
下のものを用いることによつて、前記炭酸カルシ
ウム粒子およびエポキシ樹脂粉末によく分散し、
表面に介在して流れ性を向上させることができ
る。配合量が１重量部以下では流れ性を付与する
のに充分でなく、10重量部以上では接着力、電気
的特性などの他の特性が低下する恐れがある。
本発明のエポキシ樹脂粉末組成物は、基本成分
である硬化剤を含む溶融時低粘度で流れ性のよい
エポキシ樹脂粉末の特性を低下させることなく、
ブロツキング性を改良し、しかも流れ性を低下さ
せることがないため、コイル、積層板、化粧板等
の含浸用として特に有用である。
以下、本発明を実施例および比較例により説明
する。なお、文中の部は重量部を示す。
実施例１〜２、比較例１〜３
ブロム化ビスフエノール型エポキシ樹脂（ダウ
ケミカル社製、商品名XD809400）100部に、無水
テトラヒドロフタル酸30部および２―ウンデシル
イミダゾール0.3部を配合し、押出機により溶融
混合押出した後粉砕して150メツシユパスの粉末
(A)を製造した。この粉末(A)は、150℃での溶融粘
度2.0ポイズで、流れ性試験では熱鋼板上を10cm
流れるのに13秒を要し、30℃雰囲気では10mm以上
の凝集物の発生が見られた。
次に、この粉末(A)に、白艶華CCR（白石工業
社製、有機酸表面処理炭酸カルシウムの商品名、
平均粒子径80mμ）、アクロワツクスＣ（グリコ
ケミカル社製、長鎖脂肪酸ポリアミドの商品名、
平均粒子径50μ以下）およびアエロジル＃380
（日本アエロジル社製、超微粒子状無水シリカの
商品名、平均粒子径7mμ）の所定量をドライブ
レンドし、その試験結果を第１表に示した。
なお、表中のブロツキング性の判断基準は次の
表示に基いて示した。
〇印：30℃雰囲気でブロツキングの発生が見ら
れない。
△印：30℃雰囲気で１〜５mmの凝集物が発生
×印：30℃雰囲気で５mm以上の凝集物が発生
また、流れ性は本文中の試験方法に従つて熱鋼
板上を10cm流れるのに要した秒数で示した。[Formula] (R 1 : ethylene group, propylene group, R 2 and R 3 : molecular weight approximately 170-270
By using particles with an average particle size of 70 μm or less, they are well dispersed in the calcium carbonate particles and epoxy resin powder,
It can be interposed on the surface to improve flowability. If the amount is less than 1 part by weight, it is not sufficient to impart flowability, and if it is more than 10 parts by weight, other properties such as adhesive strength and electrical properties may deteriorate. The epoxy resin powder composition of the present invention contains a curing agent as a basic component and has low viscosity and good flowability when melted, without reducing the properties of the epoxy resin powder.
Since it improves blocking properties and does not reduce flowability, it is particularly useful for impregnating coils, laminates, decorative boards, etc. The present invention will be explained below with reference to Examples and Comparative Examples. Note that parts in the text indicate parts by weight. Examples 1 to 2, Comparative Examples 1 to 3 30 parts of tetrahydrophthalic anhydride and 0.3 parts of 2-undecylimidazole were blended with 100 parts of brominated bisphenol type epoxy resin (manufactured by Dow Chemical Company, trade name: XD809400), After melting and extruding the mixture using an extruder, it is pulverized into a powder of 150 mesh passes.
(A) was manufactured. This powder (A) has a melt viscosity of 2.0 poise at 150℃, and in a flowability test, it was
It took 13 seconds to flow, and in an atmosphere of 30°C, aggregates larger than 10 mm were observed. Next, to this powder (A), Hakuenka CCR (manufactured by Shiraishi Kogyo Co., Ltd., a trade name of organic acid surface-treated calcium carbonate),
average particle diameter 80 mμ), Acrowax C (manufactured by Glyco Chemical Co., Ltd., trade name of long chain fatty acid polyamide,
average particle size 50μ or less) and Aerosil #380
(manufactured by Nippon Aerosil Co., Ltd., trade name of ultrafine particulate anhydrous silica, average particle size 7 mμ) was dry blended in a predetermined amount, and the test results are shown in Table 1. In addition, the criteria for judging the blocking property in the table are shown based on the following display. ○: No blocking observed in 30°C atmosphere. △ mark: Aggregates of 1 to 5 mm are generated in an atmosphere of 30°C. × mark: Agglomerates of 5 mm or more are generated in an atmosphere of 30°C.Furthermore, the flowability was determined by flowing 10 cm over a hot steel plate according to the test method in the text. Expressed in seconds.
【表】
実施例３〜４、比較例４〜５
ビスフエノールＡ型エポキシ樹脂（油化シエル
エポキシ社製、商品名エピコート＃1002）100部
に、トリスグリシジルイソシアヌレート20部およ
びエチレングリコールビストリメリテイト70部を
配合し、混練ロールで溶融混合した後粉砕して
150メツシユパスの粉末(B)を製造した。この粉末
(B)は、150℃での溶融粘度5.8ポイズで、流れ性試
験では熱鋼板上を10cm流れるのに15秒を要し、30
℃雰囲気では５mm以上の凝集物の発生が見られ
た。
次に、この粉末(B)に、白艶華Ｔ―DD（白石工
業社製、樹脂酸表処理炭酸カルシウムの商品名、
平均粒子径40mμ）、ブリリアント1500（白石工
業社製、表面無処理炭酸カルシウムの商品名、平
均粒子径150mμ）およびアクロワツクスＣの所
定量をドライブレンドし、その試験結果を第２表
に示した。なお、表中のブロツキング性および流
れ性は、第１表の試験方法と同様にして行なつた
ものである。[Table] Examples 3 to 4, Comparative Examples 4 to 5 To 100 parts of bisphenol A type epoxy resin (manufactured by Yuka Ciel Epoxy Co., Ltd., trade name Epicote #1002), 20 parts of trisglycidyl isocyanurate and ethylene glycol bistrimeritate. Blend 70 parts, melt and mix with a kneading roll, and then crush.
150 mesh powder (B) was produced. This powder
(B) has a melt viscosity of 5.8 poise at 150°C, and in flowability tests, it took 15 seconds to flow 10 cm on a hot steel plate, and 30
In the ℃ atmosphere, the generation of aggregates of 5 mm or more was observed. Next, to this powder (B), Shiraenka T-DD (manufactured by Shiraishi Kogyo Co., Ltd., trade name of resin acid surface treated calcium carbonate,
Predetermined amounts of Acrowax C), Brilliant 1500 (manufactured by Shiraishi Kogyo Co., Ltd., trade name of surface-untreated calcium carbonate, average particle size 150 mμ), and Acrowax C were dry blended, and the test results are shown in Table 2. Note that the blocking properties and flow properties in the table were conducted in the same manner as the test method in Table 1.
【表】【table】
Claims (1)
であり、且つ下記試験条件での流れ性試験におい
て熱鋼板上を10cm流れるのに要する時間が20秒以
内である、硬化剤を含む溶融時低粘度で流れ性の
よいエポキシ樹脂粉末100重量部に対して、樹脂
酸あるいは有機酸で表面処理した平均粒子径30〜
100mμの炭酸カルシウム１〜10重量部および平
均粒子径70μ以下の次の式
【式】（R1：エチレン基、 プロピレン基、R2およびR3：分子量約170〜270
の炭化水素残基）で表わされる長鎖脂肪酸ポリア
ミド１〜10重量部をドライブレンドしてなるエポ
キシ樹脂粉末組成物。 記 試験条件：長さ20cmの脱脂鋼板を30度に傾斜し、
表面温度を150℃に設定する。試料粉末は0.25
ｇを圧力20Kg／cm2でプレスした径13mmψのペレ
ツトを用いる。[Scope of Claims] 1. The melt viscosity at a heating temperature of 150°C is 0.2 to 20 poise, and the time required to flow 10 cm over a hot steel plate in a flowability test under the following test conditions is within 20 seconds. For 100 parts by weight of epoxy resin powder containing a hardening agent and having low viscosity and good flowability when melted, the average particle size is 30~30% by surface treatment with resin acid or organic acid.
1 to 10 parts by weight of calcium carbonate of 100 mμ and an average particle size of 70 μ or less according to the following formula [Formula] (R 1 : ethylene group, propylene group, R 2 and R 3 : molecular weight approximately 170 to 270
An epoxy resin powder composition obtained by dry blending 1 to 10 parts by weight of a long-chain fatty acid polyamide (hydrocarbon residue). Test conditions: A degreased steel plate with a length of 20 cm is tilted at 30 degrees.
Set the surface temperature to 150℃. Sample powder is 0.25
Pellets with a diameter of 13 mmψ are used, which are obtained by pressing the pellets at a pressure of 20 Kg/cm 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5152382A JPS58167657A (en) | 1982-03-29 | 1982-03-29 | Epoxy resin powder composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5152382A JPS58167657A (en) | 1982-03-29 | 1982-03-29 | Epoxy resin powder composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58167657A JPS58167657A (en) | 1983-10-03 |
| JPS6235434B2 true JPS6235434B2 (en) | 1987-08-01 |
Family
ID=12889366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5152382A Granted JPS58167657A (en) | 1982-03-29 | 1982-03-29 | Epoxy resin powder composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58167657A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61151274A (en) * | 1984-12-25 | 1986-07-09 | Sumitomo Bakelite Co Ltd | Powder coating |
| JPH01129035A (en) * | 1987-11-12 | 1989-05-22 | Nitto Denko Corp | Production of powdery epoxy resin composition |
| JPH0673188A (en) * | 1992-04-17 | 1994-03-15 | Nitto Denko Corp | Production of powdery epoxy resin composition |
| US6103157A (en) * | 1997-07-02 | 2000-08-15 | Ciba Specialty Chemicals Corp. | Process for impregnating electrical coils |
-
1982
- 1982-03-29 JP JP5152382A patent/JPS58167657A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58167657A (en) | 1983-10-03 |
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