JPS595018A - Manufacturing method for epoxy resin molded products - Google Patents
Manufacturing method for epoxy resin molded productsInfo
- Publication number
- JPS595018A JPS595018A JP11177683A JP11177683A JPS595018A JP S595018 A JPS595018 A JP S595018A JP 11177683 A JP11177683 A JP 11177683A JP 11177683 A JP11177683 A JP 11177683A JP S595018 A JPS595018 A JP S595018A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- accelerator
- molded product
- organic acid
- epoxy
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 30
- 229920000647 polyepoxide Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000203 mixture Substances 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000011550 stock solution Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- -1 BF4e Chemical class 0.000 claims description 2
- 238000010292 electrical insulation Methods 0.000 claims description 2
- 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 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 5
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012690 ionic polymerization Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012212 insulator 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
- NOUDDDRYIOHXHS-UHFFFAOYSA-N 3-chloropropane-1,1-diol Chemical compound OC(O)CCCl NOUDDDRYIOHXHS-UHFFFAOYSA-N 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ADZAAKGRMMGJKM-UHFFFAOYSA-N oxiran-2-ylmethyl nitrate Chemical compound [O-][N+](=O)OCC1CO1 ADZAAKGRMMGJKM-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
この発明は、構成要素として液状のエポキシ注型樹脂原
液と有機酸無水物硬化剤と促進剤と充填材と場合によっ
ては可とう性付与剤とを別の二つの貯蔵容器の中に成分
として準備し、これらを注型の直前に混合し、そして型
の中に一諸に注入して硬化させる屋内電気絶縁部品のた
めのエポキシ樹脂モールド成型品の製造方法であって、
一つの容器では有機酸無水物と充填材との混合液が調合
され、また他の容器ではエポキシ樹脂原液に、促進剤と
してつぎの一般的構造式
％式％
ただし、Ｍは周期表の第５主グループの原子、特にＮお
よびＰ 、、Ｒｔ ｔ ４ ｓ Ｒｓ及びＲ４は同一の
又は異なる脂肪族又は芳香族又は複素環又はアリル脂肪
族の基であって、さらに別の４原子を含むことができる
、ＸｅＩｔｉ ＣＩＯ，Ｂ ｒθ、Ｊｅ、Ｆｅ、Ｎｏ、
ｅ。[Detailed description of the invention] [Technical field to which the invention pertains] This invention comprises a liquid epoxy casting resin stock solution, an organic acid anhydride curing agent, an accelerator, a filler, and in some cases a flexibility imparting agent as constituent elements. Epoxy resin molding for indoor electrical insulation parts by preparing and as ingredients in two separate storage containers, mixing them immediately before casting, and pouring them all together into a mold and curing. A method for manufacturing a product,
In one container, a mixture of organic acid anhydride and filler is prepared, and in another container, the epoxy resin stock solution is added as an accelerator with the general structural formula %, where M is the fifth compound of the periodic table. The atoms of the main group, in particular N and P , Rt t 4 s Rs and R4, are the same or different aliphatic or aromatic or heterocyclic or arylaliphatic radicals and may contain further 4 atoms. Can, XeIti CIO, B rθ, Je, Fe, No,
e.
Ｃｌｏｇ のような陰イオン又はアセテートのような
有機酸基又はＢＦ４ｅ、ＰＦｅｅのような錯陰イオン、
であって、これらの基又はその内の二つの基が中心原子
以外に相互にも結合されることもでき、又は３価の中心
原子が環状組織の中に組込まれ、場合にょシこの環状組
織が多重結合を有することもてきる０
の第４オニウム塩が添加されるものにかかわる。An anion such as Clog or an organic acid group such as acetate or a complex anion such as BF4e, PFee, in which these groups or two groups thereof are bonded to each other as well as to the central atom. It also concerns those in which a trivalent central atom is incorporated into a ring structure and, in some cases, a quaternary onium salt is added, which ring structure may also have multiple bonds.
かかる製造方法は西ドイツ国特許公告第３００３４７６
号公報により知られている。この２容器法においては促
進剤がエポキシ樹脂原液に添加されるので、エポキシ結
合において第４オニウム塩が室温又は９０ ’Ｃまでの
温度では実ｖＡＫ全くないし極く僅かしかイオンの重合
を生ぜしめないという利点が利用される。これにより良
好な貯蔵期間と良好な処理条件と特に経済的な成形時間
とを有する２液樹脂注型システムが得られる。こうして
有機酸無水物と充填材との混合液もエポキシ樹脂と促進
剤との混合液も問題なく処理され、かつ比較的高い温度
で貯蔵される。しかしながらこの公知の方法において促
進剤として用いられる成る型の第４オニウム塩はその当
時の考え方によれば注型樹脂混合液の硬化の際にそのま
ま組織の中に含まれて残り、かつ硬化した樹脂と硬化剤
との成型品と結合しない〇
５−
それ故に例えば温度が上昇したときにこの化合物のマイ
グレーションが排除できないので、そうなれば場合によ
ｐ成型品の周囲に腐食が発生することがあり、またかか
るオニウム塩はさらに荷電した粒子を含むので、運転時
に絶縁物に電圧が加わったときにこの粒子の電界に沿っ
た移動又は整列が生じる可能性がある。そうなれば絶縁
抵抗が低下することがある。Such a manufacturing method is described in West German Patent Publication No. 3003476.
It is known from the publication No. In this two-vessel method, accelerators are added to the epoxy resin stock solution so that the quaternary onium salt in the epoxy bond produces no or very little ionic polymerization at room temperature or temperatures up to 90'C. This advantage is utilized. This results in a two-component resin casting system with a good shelf life, good processing conditions and particularly economical molding times. In this way, mixtures of organic acid anhydrides and fillers as well as mixtures of epoxy resins and promoters can be processed without problems and stored at relatively high temperatures. However, according to the thinking at that time, the quaternary onium salt of the type used as an accelerator in this known method remained contained in the structure during the curing of the casting resin mixture, and remained in the hardened resin. 〇5- Therefore, for example, when the temperature rises, migration of this compound cannot be excluded, and if this happens, corrosion may occur around the p-molded product. , and since such onium salts further contain charged particles, movement or alignment of these particles along the electric field can occur when a voltage is applied to the insulator during operation. If this happens, insulation resistance may decrease.
本発明は、これまで西ドイツ国特許公告第３００３４７
６号公報にもとづき製造された成型品及び絶縁物におけ
るマイグレーションをさらに本質的に完全防止すること
を目的とする。The present invention was previously disclosed in West German Patent Publication No. 300347
Another object of the present invention is to essentially completely prevent migration in molded products and insulators manufactured based on Publication No. 6.
この目的は頭記の製造方法においてこの発明にもとづき
、促進剤の中心原子の置換基の少なくとも一つ又は中心
原子にょ９形成された複素環組織がエポキシ樹脂と有機
酸無水物との混合液に反応しうる少なくとも一つの基を
有することにょυ達成される。含浸樹脂の硬化の際に発
生する網目構 ６−
造の中にこの基を介して促進剤化合物を固定することが
可能である。こうして促進剤のマイグレーションが防止
される。This purpose is achieved by using the above-mentioned manufacturing method based on the present invention, in which at least one of the substituents of the central atom of the accelerator or the heterocyclic structure formed on the central atom is added to the mixed solution of the epoxy resin and the organic acid anhydride. This is achieved by having at least one reactive group. It is possible to fix the promoter compound via this group in the network structure that occurs during curing of the impregnating resin. In this way migration of accelerator is prevented.
促進剤がエポキシ基又は水酸基を有するのが特に有利で
ある。なぜならばこれらの基により、問題なく調合され
かつ比較的高い温度で貯蔵されうる貯蔵安定性の良いエ
ポキシ樹脂と促進剤との混合液が得られる。促進剤が水
酸基とエポキシ基とを有するときも、このことが当ては
まる。It is particularly advantageous if the promoter has epoxy or hydroxyl groups. These groups provide storage-stable epoxy resin and accelerator mixtures that can be formulated without problems and stored at relatively high temperatures. This also applies when the promoter has hydroxyl and epoxy groups.
他の適切な反応力のある基は、メルカプタン基（ＳＨ）
又はカルボキシル基（Ｃ０ＯＨ）又はアミノないしイミ
ノ基（ＮＨｔ、ＮＨ）でアリ、これらは単独に又は混っ
て存在しうる〇
この発明にもとづく二容器注型法に対してエポキシ樹脂
原液への添加に適した第４オニウム塩は例えばつぎのよ
うなものである：適切な第３級アミンないしホスフィン
の置換生成物９例えばトリブチルアミン、ジメチルベン
ジルアミン、１．２ジメチルイミダゾール、ピリジン、
結合を有するトリフェニールホスフィン例工ばエピクロ
ールヒドリン、エビブロムヒドリン、２．３ジヒドロキ
シプロピルクロライド、２３ジヒドロキシブロビルプロ
マイド、又はエポキシ結合ないしポリエポキシ結合のハ
ロゲン酸付加生成物。Other suitable reactive groups are mercaptan groups (SH)
or a carboxyl group (C0OH) or an amino or imino group (NHt, NH), which may be present alone or in combination. Suitable quaternary onium salts are, for example: substitution products of suitable tertiary amines or phosphines, eg tributylamine, dimethylbenzylamine, 1.2 dimethylimidazole, pyridine,
Triphenylphosphine having a bond, such as epichlorohydrin, ebibromohydrin, 2.3 dihydroxypropyl chloride, 23 dihydroxybrobyl bromide, or a halogen acid addition product of an epoxy bond or a polyepoxy bond.
エポキシ樹脂原液に添加される促進剤の量はその有効率
に関係し、エポキシ樹脂原液をもとにして約０．０５な
いし３０重ｉチの範囲にある。エポキシ樹脂原液には第
４オニウム塩以外に充填材や場合によっては可撓性付与
剤を添加することもできる。注型樹脂としてこの目的に
適したすべてのエポキシ樹脂システムが考慮されるなら
ば、同様のことが有機酸無水物硬化剤にもあてはまる。The amount of accelerator added to the epoxy resin stock solution is related to its effectiveness and ranges from about 0.05 to 30 parts based on the epoxy resin stock solution. In addition to the quaternary onium salt, a filler and, in some cases, a flexibility imparting agent may be added to the epoxy resin stock solution. The same applies to organic anhydride hardeners, considering all epoxy resin systems suitable for this purpose as casting resins.
つぎにこの発明にもとづき計画されたエポキシ樹脂と促
進剤との混合液の効果を第１ないし４表に記載の実験結
果にもとづき詳細に説明する。Next, the effects of the mixed solution of epoxy resin and accelerator planned based on the present invention will be explained in detail based on the experimental results shown in Tables 1 to 4.
第 １ 表
第１表は、符号Ａで表わされる成る特定のエポキシ樹脂
、すなわちエポキシ当量が１７４±２で。Table 1 Table 1 shows a particular epoxy resin, designated by the symbol A, having an epoxy equivalent weight of 174±2.
粘度が２５℃で５０００±５００ミリパス力ル秒である
ビスフェノールＡのグリシジルニーテルト、促進剤とし
て用いられた符号１及び２で表わされる４基から成る化
合物との混合液を開放した容器の中に薄い層で貯蔵した
ときの貯蔵安定性を集成したものである。この場合には
つぎの促進剤が問題となる：
１）１メチルイミダゾール（１モル）とエピブロムヒド
リン（１モル）との置換生成物、２）１モル３．４エポ
キシシクロヘキシルメチル ９−
−（３，４−エポキシ）シクロヘキサンカルボン酸塩と
１モル臭酸から成る付加生成物を含む１メチルイミダゾ
ール（１モル）の置換生成物。A mixture of glycidyl nitrate of bisphenol A having a viscosity of 5000 ± 500 mPa/sec at 25°C and a compound consisting of four groups represented by symbols 1 and 2 used as an accelerator was placed in an open container. It is a combination of storage stability when stored in a thin layer. In this case, the following promoters are of concern: 1) the substitution product of 1 methylimidazole (1 mol) and epibromohydrin (1 mol), 2) 1 mol 3.4 epoxycyclohexylmethyl 9- -( Substitution product of 1 methylimidazole (1 mole) with an addition product consisting of 3,4-epoxy)cyclohexanecarboxylate and 1 mole hydrochloric acid.
これら化合物のイオンの重合に関する効果が小さいこと
は第１表から明らかである。It is clear from Table 1 that the effects of these compounds on ionic polymerization are small.
第２表には、エポキシ樹脂Ａの１００重量部と可撓性付
与剤例えばポリグリコールの１２重量部と促進剤１０３
重量部との混合液を熱絶縁した容器の中に入れたときす
なわち断熱条件下での温度挙動を示す。Table 2 shows 100 parts by weight of epoxy resin A, 12 parts by weight of a flexibilizing agent such as polyglycol and 103 parts by weight of an accelerator.
It shows the temperature behavior when a mixture of parts by weight is placed in a thermally insulated container, that is, under adiabatic conditions.
第 ２ 表
１０−
第２表からこのエポキシ樹脂と促進剤との混合液のすぐ
れた安定性が明らかであシ、実際的にイオンの重合が起
き′Ｃいないことがわかる。Table 2 - From Table 2, the excellent stability of this mixture of epoxy resin and accelerator is evident, and it can be seen that virtually no ionic polymerization occurs.
第３表は第２表と同じエポキシ樹脂と促進剤との混合液
をガラス栓で密封した円錐形フラスコに入れて７０℃に
加熱した乾燥炉の中に比較的長期間保存したときの粘度
上昇を示す。Table 3 shows the increase in viscosity when the same mixture of epoxy resin and accelerator as in Table 2 was stored in a conical flask sealed with a glass stopper for a relatively long period of time in a drying oven heated to 70°C. shows.
第 ３ 表
すなわち、混合液の粘度は７０°Ｃで１０日間貯蔵した
後にも約２倍に増加したに過ぎなかった０充填材を加え
た混合液であれば粘度上昇はほとんど測定不能であろう
。Table 3 shows that the viscosity of the mixture increased only about twice after 10 days of storage at 70°C.The viscosity increase would be almost unmeasurable if the mixture had no filler added. .
最後に第４表に上記のエポキシ樹脂と促進剤との混合液
に注型のために必要な量として有機酸無水物硬化剤を１
００重量部添加したときのゲル化時間を示す。Finally, Table 4 shows the amount of organic acid anhydride curing agent required for casting into the mixture of the above epoxy resin and accelerator.
The gelation time is shown when 00 parts by weight are added.
第４表ニゲル化時間Ｈ
すなわちゲル化時間はエポキシ樹脂と促進剤との混合液
の貯蔵期間にはほとんど無関係である０筐た貯蔵中に促
進剤の反応度低下は生じない。Table 4: Gelling time H That is, the gelling time is almost unrelated to the storage period of the mixture of epoxy resin and accelerator.No reduction in the reactivity of the accelerator occurs during storage.
エポキシ樹脂モールド成形品の二容器注形法においては
、一つの容器では有機酸無水物と充填材との混合液が、
また他の容器ではエポキシ樹脂原液と促進剤との混合液
が調合される。促進剤としては、この発明にもとづき、
中心原子の置換基の少なくとも一つ又は中心原子により
形成された複素環組織がエポキシ樹脂と有機酸無水物と
の混合液に反応しうる基を有する第４オニウム塩が用い
られる。これによりエポキシ樹脂の硬化の際に発生する
網目構造の中にこの基を介して促進剤が固定されるので
、電気機器の運転時にこのモールド成型品のｇＡ度が上
昇しても、促進剤に含まれる原子又は荷電粒子のマイグ
レーションを生じる心配がなく、モールド成型品の周囲
における腐蝕の発生やモールド成型品自身の絶縁低下を
本質的に防止することができる。ま几がかる促進剤とエ
ポキシ樹脂原液との混合液は貯蔵安定性にすぐれてい＝
１３−In the two-container casting method for epoxy resin molded products, one container contains a mixed liquid of an organic acid anhydride and a filler.
In another container, a mixed solution of an epoxy resin stock solution and an accelerator is prepared. As the accelerator, based on this invention,
A quaternary onium salt is used in which at least one of the substituents of the central atom or the heterocyclic structure formed by the central atom has a group capable of reacting with the mixture of the epoxy resin and the organic acid anhydride. As a result, the accelerator is fixed through this group in the network structure that occurs when the epoxy resin is cured, so even if the gA degree of this molded product increases during the operation of electrical equipment, the accelerator will remain intact. There is no fear of migration of contained atoms or charged particles, and corrosion around the molded product and deterioration of the insulation of the molded product itself can be essentially prevented. The mixture of a flexible accelerator and an epoxy resin stock solution has excellent storage stability.
13-
Claims (1)
酸無水物硬化剤と促進剤と充填材とを別の二つの貯蔵容
器の中に成分として準備し、これらを注型の直前に混合
した上で型の中に一諸に注入して硬化させる屋内電気絶
縁部品のためのエポキシ樹脂モールド成型品の製造方法
であって、一つの容器では有機酸無水物と充填材との混
合液が調合され、また他の容器ではエポキシ樹脂原液に
促進剤としてつぎの一般的構造式 ただし、Ｍは周期表の第５主グループの原子、特にＮ及
びＰ 、 Ｒ＋ 、Ｒｔ −Ｒｓ及びＲ社同−の又は異
なる脂肪族又は芳香族又は複素環又はアリル脂肪族の基
であって、さらに別の４原子を含むことができる、 ＸｅＵＣＡ？θ、Ｂｒθ、 Ｊθ、 Ｆｅ、 ＮＯ，。 Ｃ１０４ｅのような陰イオン又はアセテートのような有
機酸基又はＢＦ４ｅ、ＰＦ６ｅのような錯陰イオン、 であって、これらの基又はその内の二つの基が中心原子
以外に相互にも結合されることもでき、又は３価の中心
原子が環状組織の中に組込まれ、場合によりこの環状組
織が多重結合を有することもでをる。 の第４オニウム塩が添加されるものにおいて、促進剤の
中心原子の置換基の少なくとも一つ又は中心原子により
形成された複素環組織がエポキシ樹脂と有機酸無水物と
の混合液に反応しうる少なくとも一つの基を有すること
を％徴とするエポキシ樹脂そ一ルド成型品の製造方法。 ２、特許請求の範囲第１項に記載の製造方法において、
促進剤がエポキシ基を有することを特徴とするエポキシ
樹脂モールド成型品の製造方法。 ３）特許請求の範囲第１項に記載の製造方法において、
促進剤が水酸基を有することを特徴とするエポキシ樹脂
モールド成型品の製造方法。 ４）特許請求の範８第１項から第３項までのいずれかに
記載の製造方法において、促進剤が異なる種類の反応し
うる基を有することを特徴とするエポキシ樹脂モールド
成型品の製造方法。[Claims] 1) A liquid epoxy casting resin stock solution, an organic acid anhydride curing agent, an accelerator, and a filler are prepared as components in two separate storage containers, and these are poured. A method for manufacturing an epoxy resin molded product for indoor electrical insulation parts, in which the organic acid anhydride and the filler are mixed immediately before molding, and then poured into the mold all at once and cured. In other containers, a mixture of epoxy resins is prepared as an accelerator with the following general structural formula: XeUCA? θ, Brθ, Jθ, Fe, NO,. An anion such as C104e or an organic acid group such as acetate or a complex anion such as BF4e, PF6e, in which these groups or two groups thereof are also bonded to each other in addition to the central atom. Alternatively, a trivalent central atom can be incorporated into a ring, which ring may optionally have multiple bonds. In those to which a quaternary onium salt is added, at least one of the substituents of the central atom of the promoter or the heterocyclic structure formed by the central atom can react with the mixture of the epoxy resin and the organic acid anhydride. A method for producing an epoxy resin solid molded product having at least one group. 2. In the manufacturing method according to claim 1,
A method for producing an epoxy resin molded product, characterized in that the accelerator has an epoxy group. 3) In the manufacturing method according to claim 1,
A method for producing an epoxy resin molded product, characterized in that the accelerator has a hydroxyl group. 4) A method for producing an epoxy resin molded product according to any one of claims 8, 1 to 3, wherein the accelerator has different types of reactive groups. .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE32236352 | 1982-06-22 | ||
| DE19823223635 DE3223635A1 (en) | 1982-06-22 | 1982-06-22 | Process for the production of cured plastic articles by casting |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS595018A true JPS595018A (en) | 1984-01-11 |
Family
ID=6166765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11177683A Pending JPS595018A (en) | 1982-06-22 | 1983-06-21 | Manufacturing method for epoxy resin molded products |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS595018A (en) |
| DE (1) | DE3223635A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103568341A (en) * | 2012-08-08 | 2014-02-12 | 西门子公司 | Method of modifying rate of temperature change of epoxy resin composition in resin container during casting process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56131621A (en) * | 1980-03-17 | 1981-10-15 | Matsushita Electric Ind Co Ltd | Epoxy resin composition |
| JPS5889617A (en) * | 1981-11-24 | 1983-05-28 | Denki Kagaku Kogyo Kk | Epoxy resin curing accelerator |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52125600A (en) * | 1976-04-14 | 1977-10-21 | Hitachi Ltd | Curing catalysts for epoxy resins |
| DE3003476B1 (en) * | 1980-01-29 | 1981-01-29 | Siemens Ag | Process for the production of hardened plastic moldings by casting |
-
1982
- 1982-06-22 DE DE19823223635 patent/DE3223635A1/en not_active Withdrawn
-
1983
- 1983-06-21 JP JP11177683A patent/JPS595018A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56131621A (en) * | 1980-03-17 | 1981-10-15 | Matsushita Electric Ind Co Ltd | Epoxy resin composition |
| JPS5889617A (en) * | 1981-11-24 | 1983-05-28 | Denki Kagaku Kogyo Kk | Epoxy resin curing accelerator |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103568341A (en) * | 2012-08-08 | 2014-02-12 | 西门子公司 | Method of modifying rate of temperature change of epoxy resin composition in resin container during casting process |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3223635A1 (en) | 1983-12-22 |
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