JPH0439509B2 - - Google Patents
Info
- Publication number
- JPH0439509B2 JPH0439509B2 JP13267884A JP13267884A JPH0439509B2 JP H0439509 B2 JPH0439509 B2 JP H0439509B2 JP 13267884 A JP13267884 A JP 13267884A JP 13267884 A JP13267884 A JP 13267884A JP H0439509 B2 JPH0439509 B2 JP H0439509B2
- Authority
- JP
- Japan
- Prior art keywords
- methacrylate
- ethyl acrylate
- adhesion
- copolymer
- perfluoroalkyl
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- -1 2-(perfluorononenyloxy)ethyl acrylate Chemical compound 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000000181 anti-adherent effect Effects 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- ZSNIHLUNWYRJFH-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2-methylidenedecanoic acid Chemical compound OC(=O)C(=C)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZSNIHLUNWYRJFH-UHFFFAOYSA-N 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 10
- 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 7
- 239000003960 organic solvent Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- ADLOXQRLQCVRTM-UHFFFAOYSA-N 2-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoronon-1-enoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ADLOXQRLQCVRTM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KNBIXDXLOIHINH-UHFFFAOYSA-N 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoic acid Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(O)=O KNBIXDXLOIHINH-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
産業上の利用分野
本発明は付着防止剤、更に詳しくは樹脂、就中
エポキシ樹脂の付着防止剤に関する。
また、本発明の付着防止剤はエポキシ樹脂等の
樹脂の付着のみを防止するものでなく、その他の
接着性の強い樹脂、潤滑油、水等のもれ防止、付
着防止などの機能を有し、印刷インキの付着防止
剤、精密機械の防食、防錆、撥水撥油剤等の種々
の用途に有用である。
従来の技術
セラミツクコンデンサー、ケミカルコンデンサ
ー、フイルムコンデンサー等の表面は、防湿、美
観および保護の観点から主としてエポキシ樹脂等
の樹脂により被覆されている。
一般にエポキシ樹脂等の樹脂の被覆によりコン
デンサーのリード線にエポキシ樹脂等の樹脂が付
着するが、集積回路技術進歩に伴う電子機器の小
型軽量化のために、コンデンサー自身も正確な寸
法精度が要求され、上記リード部分へのエポキシ
樹脂等の樹脂の付着も全く起こらないことが要求
されている。
上記リード線への付着を防止するために、従来
種々の付着防止剤が使用されている。例えば、シ
リコーン系のもの、あるいはフツ素系のもの（特
開昭56−53116号公報および特開昭55−116782号
公報）が例示される。
発明が解決しようとする問題点
しかしながら、シリコーン系の付着防止剤は、
エポキシ樹脂等の樹脂の付着防止性が低いばかり
でなく、ハンダ特性が悪く、リード線に残つたシ
リコーン系付着防止剤のために導電不良が生じる
欠点を有している。
フツ素系の付着防止剤は低い臨界表面張力のた
めに付着防止力に優れ、かつハンダ特性も優れて
いる。しかしながら、これらの付着防止剤はフロ
ン系以外の有機溶媒、例えばトルエン、キシレン
等に可溶なものが多く、エポキシ樹脂等の樹脂が
これらの有機溶媒に溶解されて塗布されることか
ら、付着防止剤がエポキシ樹脂被覆剤に溶け込
み、ラインでの大量作業中にコンデンサー表面の
均一な塗膜の形成を阻害し、塗りむらまたは塗装
不良が起こる欠点を有する。
本発明は上記欠点を改良して、エポキシ樹脂等
の樹脂の付着防止性に優れ、ハンダ特性にも優
れ、かつ、キシレン、ベンゼン等のエポキシ樹脂
等の樹脂の溶媒に不溶のフツ素系樹脂を含有する
付着防止剤を提供する。
問題点を解決するための手段
即ち本発明の要旨は、一般式(1)：
（式中、ＲはＨもしくはCH3，RfはC3〜12F5〜23
のペルフルオロアルケニル基を示す）で表わされ
る２−（ペルフルオロアルケニルオキシ）エチル
アクリレートもしくはメタクリレートおよび一般
式(2)：
（式中、Ｒは前記と同意義、Rf′はC6〜12F13〜25
のペルフルオロアルキル基を示す）で表わされる
２−（ペルフルオロアルキル）エチルアクリレー
トもしくはメタクリレートを反応させて得られる
共重合体を含有する付着防止剤に存する。
本発明に用いる２−（ペルフルオロアルケニル
オキシ）エチルアクリレートもしくはメタクリレ
ートは、ペルフルオロオレフインおよび２−ヒド
ロキシエチルアクリレートもしくはメタクリレー
トを非水溶媒中、塩基性触媒の存在下に脱弗酸反
応させることによつて調製するのが一般的な方法
であるが（反応温度は通常約10〜50℃である）、
これに限定されるものではない。
この反応に使用するペルフルオロオレフインは
例えば、ヘキサフルオロプロペンのようなフルオ
ロオレフインを弗素イオン（弗素イオン源；弗化
アルカリ、酸性弗化アルカリ等）の存在下、スル
ホラン類（例えばスルホラン、メチルスルホラン
等）を溶媒としてオリゴメル化することによつて
容易に得ることができる（例えば、特公昭57−
2697号公報参照）。
好ましいペルフルオロオレフンはC3〜12F5〜23の
ペルフルオロアルケン、就中、ヘキサフルオロプ
ロペンの二量体または三量体である。
このようなペルフルオロオレフインと２−ヒド
ロキシエチルアクリレートもしくはメタクリレー
トを非水溶媒（例えばジエチルエーテル、テトラ
ヒドロフラン、アセロニトリル、ジグリム、Ｎ，
Ｎ−ジメチルホルムアミドおよび／またはジメチ
ルカルビトール等）中、塩基性触媒の存在下に反
応させる。
塩基性触媒は脱弗酸反応を促進し、生成する弗
酸を吸収する作用をする水溶性のもので、好適な
触媒としてはトリエチルアミン、トリメチルアミ
ン、炭酸ナトリウムおよび／または炭酸カリウム
等が例示される。
また、本発明に使用する２−（ペルフルオロア
ルキル）エチルアクリレートもしくはメタクリレ
ートとして特に好適なものは、CH2＝CHCOOC2
H4C8F17，CH2＝Ｃ（CH3）COOC2H4C8F17，
CH2＝CHCOOC2H4C7F15およびCH2＝Ｃ（CH3）
COOC2H4C7F15等である。
上記の一般式(1)で表わされる２−（ペルフルオ
ロアルケニルオキシ）エチルアクリレートもしく
はメタクリレートおよび一般式(2)で表わされる２
−（ペルフルオロアルキル）エチルアクリレート
もしくはメタクリレートは通常、重量比約20：１
〜約１：20、特に好ましくは約10：１〜約１：10
で反応させる。
この反応は通常、窒素ガス等の不活性ガス雰囲気
下、反応成分の反応性や反応方式等に応じて約70
〜100℃で約４〜24時間おこなう。
反応方式は特に限定的ではなく、溶液重合、塊
状重合、懸濁重合、乳化重合、放射線重合等いず
れであつてもよいが、特に好適な方式は溶液重合
法である。
溶液重合は、上記反応成分を適当な有機溶媒に
溶解させ、有機過酸化物（例えばベンゾイルパー
オキサイド、ジ−ｔ−ブチルペルオキシド、ｔ−
ブチルペルイソブチレート、アゾ化合物、例えば
２，2′−アゾビスイソブチロニトリル、メチル−
２，2′−アゾビスイソブチレート等）を添加する
か、電離性放射線を照射しておこなう。好適な有
機溶媒はトリクロロトリフルオロエタン、テトラ
クロロジフルオロエタン、メタキシレンヘキサフ
ルオライド、パラキシレンヘキサフルオライド等
のフツ素系有機溶媒である。
共重合体の好ましい重量平均分子量は約5000〜
約20000である。
このようにして得られる共重合体は通常、約
0.5重量％以上、特に約1.0〜2.0重量％に希釈して
付着防止剤として使用に供される。希釈溶媒とし
て好ましいものは上記のフツ素系有機溶剤であ
る。
以下、本発明を実施例によつて説明する。
実施例
実施例 １
攪拌機、温度計、還流冷却器および滴下漏斗を
備えたフラスコ（200ml）に２−ヒドロキシエチ
ルメタクリレート0.11mol、C9−ペルフルオロオ
レフイン0.1molおよびアセトニトリル50mlを入
れ、室温で攪拌しながらトリエチルアミン
0.11molを徐々に滴下し、さらに攪拌を２〜３時
間続行後、反応混合物を水１中に滴下した。
分離した下層を２〜３回水洗し、無水硫酸ナト
リウムで脱水後、減圧蒸留（105〜115℃／６mm
Hg）によつて淡黄色の２−（ペルフルオロノネニ
ルオキシ）エチルメタクリレートを収率80％で得
た〔IR：νC-H（飽和）2600，2400cm-1，νC=O1730
cm-1，νC-F1320〜1170cm-1，νC-H（不飽和）3000cm
−１，νC=C1640cm-1；1Ｈ−NMR（内部基準TMS）：
δCH2＝6.13，5.57ppm（ｓ），〓CH2CH24.3ppm
（ｔ）；〓CH31.9ppm；n20.5 D1.3627〕。
得られた２−（ペルフルオロノネニルオキシ）
エチルメタクリレート３ｇおよび２−（ペルフル
オロオクチル）エチルアクリレート30ｇをメタキ
シレンヘキサフルオライド66ｇに溶解させ、この
溶液を密閉可能なガラス容器（150ml）に入れ、
ベンゾイルパーオキサイド0.5ｇを添加し、容器
内の気相を窒素ガスで置換し、密閉して70℃で24
時間静置し、共重合体含有メタキシレンヘキサフ
ルオライド溶液90ｇを調製した。
実施例２および３
２−（ペルフルオロノネニルオキシ）エチルメ
タクリレートおよび２−（ペルフルオロオクチル）
エチルアクリレートの反応重量比を10：２または
10：１に変える以外は実施例１と同様にして共重
合体含有メタキシレンヘキサフルオライド溶液を
調製した。
実施例 ４〜６
２−ヒドロキシエチルメタクリレートの代りに
２−ヒドロキシエチルアクリレートを使用する以
外は実施例１と同様にして、淡黄色の２−（ペル
フルオロノネニルオキシ）エチルアクリレート
（79〜90℃／0.5mmHg）を85％の収率で得〔IR：
νC-H（飽和）2600，2400cm-1，νC=O1740cm-1，νC-F
1320〜1160cm-1，νC-H（不飽和）3000cm-1，νC=C
1640cm-1；1Ｈ−NMR（内部基準TMS）：δCH2Ｃ
＝CH＝6.7〜5.6ppm(m)，δCH2CH24.3ppm(t)；
n20.5 D1.3480〕、これに２−（ペルフルオロオクチ
ル）エチルアクリレートを反応させて、共重合体
含有メタキシレンヘキサフルオライド溶液を調製
した。
付着防止性試験
上記実施例１〜６で得られた試料を同一の溶媒
を用いて１％または0.5％に希釈した付着防止剤
のエポキシ樹脂に対する付着防止性を調べ、結果
を表−１に示す。
比較例１および２
比較のため以下の式を有する重合体（10重量％
CCl2FCClF2溶液）により、付着防止性を調べた。
結果を表−１に示す。
INDUSTRIAL FIELD OF APPLICATION The present invention relates to an anti-adhesive agent, and more particularly to an anti-adhesive agent for resins, especially epoxy resins. In addition, the anti-adhesion agent of the present invention not only prevents the adhesion of resins such as epoxy resins, but also has functions such as preventing leakage and adhesion of other highly adhesive resins, lubricating oil, water, etc. It is useful for various uses such as adhesion prevention agent for printing ink, anticorrosion and rust prevention for precision machinery, and water and oil repellent. BACKGROUND ART The surfaces of ceramic capacitors, chemical capacitors, film capacitors, etc. are mainly coated with resin such as epoxy resin from the viewpoints of moisture resistance, aesthetics, and protection. Generally, resin such as epoxy resin adheres to the capacitor lead wire due to coating with resin such as epoxy resin, but due to the miniaturization and weight reduction of electronic devices due to advances in integrated circuit technology, accurate dimensional accuracy is required for the capacitor itself. It is also required that resin such as epoxy resin not adhere to the lead portion at all. Conventionally, various anti-adhesion agents have been used to prevent adhesion to the lead wires. For example, silicone-based materials or fluorine-based materials (JP-A-56-53116 and JP-A-55-116782) are exemplified. Problems to be solved by the invention However, silicone-based anti-adhesion agents
Not only does it have poor adhesion prevention properties for resins such as epoxy resins, but it also has poor solder properties and has the drawback of poor conductivity due to the silicone adhesion preventive agent remaining on the lead wires. Fluorine-based anti-adhesion agents have low critical surface tension, so they have excellent anti-adhesion properties and also have excellent solder properties. However, many of these anti-adhesion agents are soluble in organic solvents other than fluorocarbons, such as toluene and xylene, and since resins such as epoxy resins are dissolved in these organic solvents and applied, it is difficult to prevent adhesion. This has the disadvantage that the agent dissolves in the epoxy resin coating, hindering the formation of a uniform coating film on the surface of the capacitor during bulk work on the line, and causing uneven coating or coating defects. The present invention improves the above-mentioned drawbacks by producing a fluorine-based resin that has excellent adhesion prevention properties for resins such as epoxy resins, excellent solder properties, and is insoluble in solvents for resins such as xylene and benzene. Provided is an anti-adhesive agent containing. Means for solving the problem, that is, the gist of the present invention is the general formula (1): (In the formula, R is H or CH 3 , R f is C 3-12 F 5-23
2-(perfluoroalkenyloxy)ethyl acrylate or methacrylate represented by (representing a perfluoroalkenyl group) and general formula (2): (In the formula, R has the same meaning as above, R f ' is C 6-12 F 13-25
The anti-adhesion agent contains a copolymer obtained by reacting 2-(perfluoroalkyl)ethyl acrylate or methacrylate represented by the following perfluoroalkyl group. 2-(Perfluoroalkenyloxy)ethyl acrylate or methacrylate used in the present invention is prepared by subjecting perfluoroolefin and 2-hydroxyethyl acrylate or methacrylate to a dehydrofluoric acid reaction in the presence of a basic catalyst in a nonaqueous solvent. (The reaction temperature is usually about 10-50℃)
It is not limited to this. The perfluoroolefin used in this reaction is, for example, a fluoroolefin such as hexafluoropropene in the presence of fluorine ions (a fluoride ion source; alkali fluoride, acidic alkali fluoride, etc.), and a sulfolane compound (e.g. sulfolane, methylsulfolane, etc.). can be easily obtained by oligomerization using a solvent (for example,
(See Publication No. 2697). Preferred perfluoroolefins are dimers or trimers of C3-12F5-23 perfluoroalkenes, especially hexafluoropropenes . Such perfluoroolefins and 2-hydroxyethyl acrylate or methacrylate are mixed in a non-aqueous solvent (e.g. diethyl ether, tetrahydrofuran, aceronitrile, diglyme, N,
The reaction is carried out in N-dimethylformamide and/or dimethylcarbitol, etc.) in the presence of a basic catalyst. The basic catalyst is a water-soluble catalyst that promotes the dehydrofluoric acid reaction and absorbs the generated hydrofluoric acid. Examples of suitable catalysts include triethylamine, trimethylamine, sodium carbonate and/or potassium carbonate. Furthermore, a particularly suitable 2-(perfluoroalkyl)ethyl acrylate or methacrylate used in the present invention is CH 2 =CHCOOC 2
H 4 C 8 F 17 , CH 2 = C(CH 3 ) COOC 2 H 4 C 8 F 17 ,
CH2 = CHCOOC2H4C7F15 and CH2 = C ( CH3 )
COOC 2 H 4 C 7 F 15 etc. 2-(perfluoroalkenyloxy)ethyl acrylate or methacrylate represented by general formula (1) above and 2-(perfluoroalkenyloxy)ethyl acrylate or methacrylate represented by general formula (2)
-(perfluoroalkyl)ethyl acrylate or methacrylate typically in a weight ratio of about 20:1
~about 1:20, particularly preferably about 10:1 to about 1:10
React with. This reaction is usually carried out under an inert gas atmosphere such as nitrogen gas, depending on the reactivity of the reaction components and the reaction method.
Incubate at ~100℃ for about 4 to 24 hours. The reaction method is not particularly limited and may be any of solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, etc., but a particularly preferred method is solution polymerization. Solution polymerization involves dissolving the above reaction components in a suitable organic solvent and adding an organic peroxide (e.g. benzoyl peroxide, di-t-butyl peroxide, t-
Butyl perisobutyrate, azo compounds such as 2,2'-azobisisobutyronitrile, methyl-
2,2'-azobisisobutyrate, etc.) or irradiation with ionizing radiation. Suitable organic solvents are fluorine-based organic solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane, metaxylene hexafluoride, paraxylene hexafluoride, and the like. The preferred weight average molecular weight of the copolymer is about 5000~
Approximately 20,000. The copolymers thus obtained are typically about
It is used as an anti-adhesive agent when diluted to 0.5% by weight or more, particularly about 1.0 to 2.0% by weight. Preferred diluent solvents are the above-mentioned fluorine-based organic solvents. Hereinafter, the present invention will be explained with reference to Examples. Examples Example 1 A flask (200 ml) equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel was charged with 0.11 mol of 2-hydroxyethyl methacrylate, 0.1 mol of C9 -perfluoroolefin and 50 ml of acetonitrile, and the mixture was stirred at room temperature. triethylamine
0.11 mol was gradually added dropwise, stirring was continued for 2 to 3 hours, and then the reaction mixture was added dropwise to water 1. The separated lower layer was washed with water 2-3 times, dehydrated with anhydrous sodium sulfate, and then distilled under reduced pressure (105-115℃/6mm
Pale yellow 2-(perfluorononenyloxy)ethyl methacrylate was obtained in a yield of 80% using Hg) [IR: ν CH (saturated) 2600, 2400 cm -1 , ν C=O 1730
cm -1 , ν CF 1320 to 1170 cm -1 , ν CH (unsaturated) 3000 cm
−1 , ν C=C 1640cm −1 ; 1 H-NMR (internal standard TMS):
δ CH2 =6.13, 5.57ppm (s), 〓CH 2 CH 2 4.3ppm
(t); 〓CH 3 1.9ppm; n 20.5 D 1.3627]. The obtained 2-(perfluorononenyloxy)
Dissolve 3 g of ethyl methacrylate and 30 g of 2-(perfluorooctyl)ethyl acrylate in 66 g of meta-xylene hexafluoride, place this solution in a sealable glass container (150 ml),
Add 0.5g of benzoyl peroxide, replace the gas phase in the container with nitrogen gas, seal it, and incubate at 70℃ for 24 hours.
The mixture was allowed to stand for a period of time to prepare 90 g of a copolymer-containing meta-xylene hexafluoride solution. Examples 2 and 3 2-(perfluorononenyloxy)ethyl methacrylate and 2-(perfluorooctyl)
The reaction weight ratio of ethyl acrylate is 10:2 or
A copolymer-containing metaxylene hexafluoride solution was prepared in the same manner as in Example 1 except that the ratio was changed to 10:1. Examples 4-6 Pale yellow 2-(perfluorononenyloxy)ethyl acrylate (79-90°C/ 0.5 mmHg) was obtained in 85% yield [IR:
ν CH (saturated) 2600, 2400cm -1 , ν C=O 1740cm -1 , ν CF
1320～1160cm -1 , ν CH (unsaturated) 3000cm -1 , ν C=C
1640cm -1 ; 1H -NMR (internal standard TMS): δCH 2 C
=CH=6.7~5.6ppm (m) , δCH2CH24.3ppm ( t) ;
n 20.5 D 1.3480], was reacted with 2-(perfluorooctyl)ethyl acrylate to prepare a copolymer-containing meta-xylene hexafluoride solution. Anti-adhesion test The anti-adhesion properties of the anti-adhesion agents prepared by diluting the samples obtained in Examples 1 to 6 above to 1% or 0.5% with the same solvent to epoxy resin were investigated, and the results are shown in Table 1. . Comparative Examples 1 and 2 For comparison, a polymer having the following formula (10% by weight)
CCl 2 FCClF 2 solution) was used to investigate the anti-adhesion properties.
The results are shown in Table-1.
【表】
発明の効果
本発明付着防止剤はエポキシ樹脂等の樹脂の付
着を有効に防止する。また、ハンダ特性も極めて
よい。さらに通常の有機溶媒に溶出せず、エポキ
シ樹脂等の樹脂塗膜への悪影響は殆んどない。[Table] Effects of the Invention The anti-adhesion agent of the present invention effectively prevents the adhesion of resins such as epoxy resins. Also, the solder properties are extremely good. Furthermore, it does not dissolve in ordinary organic solvents and has almost no adverse effect on resin coatings such as epoxy resins.
Claims (1)
のペルフルオロアルケニル基を示す）で表わされ
る２−（ペルフルオロアルケニルオキシ）エチル
アクリレートもしくはメタクリレートおよび一般
式(2)： （式中、Ｒは前記と同意義、Rf′はC6〜12F13〜25
のペルフルオロアルキル基を示す）で表わされる
２−（ペルフルオロアルキル）エチルアクリレー
トもしくはメタクリレートを反応させて得られる
共重合体を含有する付着防止剤。 ２ 共重合体が、２−（ペルフルオロアルケニル
オキシ）エチルアクリレートもしくはメタクリレ
ートおよび２−（ペルフルオロアルキル）エチル
アクリレートもしくはメタクリレートを約20：１
〜約１：20の重量比で溶液重合させて得られるポ
リマーである第１項記載の付着防止剤。 ３ 共重合体が、２−（ペルフルオロノネニルオ
キシ）エチルアクリレートもしくはメタクリレー
トおよび２−（ペルフルオロオクチル）アクリレ
ートもしくはメタクリレートを約20：１〜約１：
20の重量比で溶液重合させて得られるポリマーで
ある第１項記載の付着防止剤。 ４ 共重合体の重量平均分子量が約5000〜約
20000である第１項記載の付着防止剤。[Claims] 1 General formula (1): (In the formula, R is H or CH 3 , R f is C 3-12 F 5-23
2-(perfluoroalkenyloxy)ethyl acrylate or methacrylate represented by (representing a perfluoroalkenyl group) and general formula (2): (In the formula, R has the same meaning as above, R f ' is C 6-12 F 13-25
An anti-adhesion agent containing a copolymer obtained by reacting 2-(perfluoroalkyl)ethyl acrylate or methacrylate represented by (representing a perfluoroalkyl group). 2 The copolymer contains 2-(perfluoroalkenyloxy)ethyl acrylate or methacrylate and 2-(perfluoroalkyl)ethyl acrylate or methacrylate in a ratio of about 20:1.
The anti-adhesive agent according to claim 1, which is a polymer obtained by solution polymerization in a weight ratio of ˜1:20. 3. The copolymer contains 2-(perfluorononenyloxy)ethyl acrylate or methacrylate and 2-(perfluorooctyl)acrylate or methacrylate in a ratio of about 20:1 to about 1:1.
2. The anti-adhesion agent according to item 1, which is a polymer obtained by solution polymerization at a weight ratio of 20 to 20. 4 The weight average molecular weight of the copolymer is about 5000 to about
20,000, the anti-adhesion agent according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13267884A JPS6112777A (en) | 1984-06-26 | 1984-06-26 | Anti-adhesion agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13267884A JPS6112777A (en) | 1984-06-26 | 1984-06-26 | Anti-adhesion agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6112777A JPS6112777A (en) | 1986-01-21 |
| JPH0439509B2 true JPH0439509B2 (en) | 1992-06-29 |
Family
ID=15086946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13267884A Granted JPS6112777A (en) | 1984-06-26 | 1984-06-26 | Anti-adhesion agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6112777A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613855B1 (en) | 1997-04-09 | 2003-09-02 | Sanyo Chemical Industries, Ltd. | Polymerizable resin, and cured resins, insulators, components of electrical appliances, and electrical appliances made by using the same |
| JP5439743B2 (en) * | 2007-10-11 | 2014-03-12 | ユニマテック株式会社 | Water and oil repellent |
| JP5171452B2 (en) * | 2008-07-22 | 2013-03-27 | Ａｇｃセイミケミカル株式会社 | Resin adhesion prevention composition for electronic parts |
| CN102264858A (en) * | 2009-01-07 | 2011-11-30 | Agc清美化学股份有限公司 | Resin adhesion inhibitor for electronic components, and electronic member and electronic component comprising same |
| CN102471405B (en) * | 2009-08-20 | 2014-06-25 | Agc清美化学股份有限公司 | Fluoroalkyl group-containing n-substituted (meth)acrylamide compound, polymer thereof, and use thereof |
-
1984
- 1984-06-26 JP JP13267884A patent/JPS6112777A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6112777A (en) | 1986-01-21 |
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