JPH0813870B2 - Fluorine-containing novolac type epoxy resin - Google Patents
Fluorine-containing novolac type epoxy resinInfo
- Publication number
- JPH0813870B2 JPH0813870B2 JP20331087A JP20331087A JPH0813870B2 JP H0813870 B2 JPH0813870 B2 JP H0813870B2 JP 20331087 A JP20331087 A JP 20331087A JP 20331087 A JP20331087 A JP 20331087A JP H0813870 B2 JPH0813870 B2 JP H0813870B2
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- JP
- Japan
- Prior art keywords
- epoxy resin
- type epoxy
- fluorine
- novolac type
- groups
- 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.)
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- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は耐熱性と撥水耐水性に優れた含フッ素ノボラ
ック型エポキシ樹脂およびその製造方法に関する。TECHNICAL FIELD The present invention relates to a fluorine-containing novolac type epoxy resin excellent in heat resistance and water / water repellency, and a method for producing the same.
従来の技術 従来から電気電子部品等の分野において特に封止剤と
して使用されている比較的耐熱性と耐水性に優れたノボ
ラック型エポキシ樹脂は通常、フェノール性ノボラック
とエピハロヒドリンをアルカリの存在下で反応させるこ
とによって調製されるために、この種のエポキシ樹脂に
は多量に副生するアルカリ塩が混入する。Conventional technology Conventionally, novolak type epoxy resins with relatively excellent heat resistance and water resistance, which have been used as sealants especially in the fields of electric and electronic parts, usually react phenolic novolac with epihalohydrin in the presence of alkali. The epoxy resin of this type is mixed with a large amount of by-produced alkali salt because it is prepared by the above.
また、この種のエポキシ樹脂は撥水性に劣るために封
止剤として使用した場合にわずかな隙間等から水分が侵
入する。Further, since this kind of epoxy resin is inferior in water repellency, when used as a sealant, water penetrates through a slight gap or the like.
このため、従来のノボラック型エポキシ樹脂を電気電
子部品等の封止剤等として使用した場合には、上記アル
カリ塩、侵入水分および空気中の酸素等が原因となって
該部品等に腐食をもたらすという問題があった。Therefore, when a conventional novolac type epoxy resin is used as a sealant for electric and electronic parts, etc., it causes corrosion of the parts due to the alkali salt, invading water, oxygen in the air, etc. There was a problem.
発明が解決しようとする問題点 本発明はこのような問題点を解決し、耐熱性と撥水耐
水性に優れたノボラック型エポキシ樹脂を提供するため
になされたものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has been made to solve such problems and provide a novolac type epoxy resin excellent in heat resistance and water / water repellency.
問題点を解決するための手段 即ち本発明は、次式： （式中、ｎは０〜18の数を示す） で表されるフェノール性ノボラックの−OH基の１〜95％
がペルフルオロアルケニルオキシ基−ORf（式中、RfはC
6F11またはC9F17を示す）によって置換され、残余の該
−OH基の実質的に全てがグリシジルエーテル基 によって置換されたことを特徴とする含フッ素ノボラッ
ク型エポキシ樹脂に関する。Means for Solving the Problems That is, the present invention has the following formula: (In the formula, n represents a number of 0 to 18) 1 to 95% of the -OH group of the phenolic novolac represented by
Is a perfluoroalkenyloxy group —ORf (wherein Rf is C
6 F 11 or C 9 F 17 ) and substantially all of the remaining --OH groups are glycidyl ether groups. It relates to a fluorine-containing novolac type epoxy resin characterized by being substituted by.
本発明による含フッ素ノボラック型エポキシ樹脂の基
材原料としては自体公知のフェノール性ノボラック、即
ちフェノール類とホルムアルデヒドを酸触媒の存在下で
反応させて得られるノボラックを適宜使用すればよい。
この場合、重合度は通常、２〜20、好ましくは２〜10で
ある。As a base material for the fluorine-containing novolac type epoxy resin according to the present invention, a phenolic novolac known per se, that is, a novolac obtained by reacting a phenol with formaldehyde in the presence of an acid catalyst may be appropriately used.
In this case, the degree of polymerization is usually 2 to 20, preferably 2 to 10.
上記のフェノール性ノボラックの−OH基の一部を置換
するペルフルオロアルケニルオキシ基−ORf中のRfはC6F
11またはC9F17であり、このようなものとしてはヘキサ
フルオロプロペンの二量体もしくは三量体の残基、例え
ば次のような構造を有する残基が挙げられる： このようなペルフルオロアルケニルオキシ基−ORfに
よるフェノール性ノボラックの−OH基の置換率は１〜95
％、好ましくは10〜90％であり、小さすぎると本発明の
目的を達成することはできず、大きすぎるとグリシジル
エーテル基の割合が小さくなり、硬化特性が減少する。Rf perfluoroalkyl alkenyloxy group in -ORf for substituting a part of the -OH groups of the phenolic novolak is C 6 F
11 or C 9 F 17 , such as a dimeric or trimeric residue of hexafluoropropene, such as a residue having the structure: The substitution rate of the -OH group of the phenolic novolac by the perfluoroalkenyloxy group -ORf is 1 to 95.
%, Preferably 10 to 90%. If it is too small, the object of the present invention cannot be achieved, and if it is too large, the proportion of glycidyl ether groups becomes small and the curing characteristics are reduced.
本発明による含フッ素ノボラック型エポキシ樹脂にお
いては、−OH基のうち、−ORfによって置換された−OH
基以外の残余のものは実質的に全てがグリシジルエーテ
ル基 によって置換される。In the fluorine-containing novolac type epoxy resin according to the present invention, among the --OH groups, --OH substituted by --ORf is used.
Substantially all but the rest of the groups are glycidyl ether groups Is replaced by
従って、本発明による含フッ素ノボラック型エポキシ樹
脂の耐熱性や撥水耐水性等の諸特性はペルフルオロアル
ケニルオキシ基−ORfによる−OH基の置換率によって適
宜調整することができる。Therefore, various properties such as heat resistance and water repellency of the fluorine-containing novolac type epoxy resin according to the present invention can be appropriately adjusted by the substitution rate of the —OH group by the perfluoroalkenyloxy group —ORf.
本発明による上記の含フッ素ノボラック型エポキシ樹
脂の製造方法は特に限定的ではないが、好適な方法は、
前記のフェノール性ノボラックおよびヘキサフルオロプ
ロペンの二量体もしくは三量体を塩基性触媒の存在下で
反応させて得られるフッ素化ノボラックを、アルカリの
存在下でエピハロヒドリンと反応させることを特徴とす
る方法である。The method for producing the above fluorine-containing novolac type epoxy resin according to the present invention is not particularly limited, but a preferable method is
Fluorinated novolak obtained by reacting the dimer or trimer of the above-mentioned phenolic novolac and hexafluoropropene in the presence of a basic catalyst is reacted with epihalohydrin in the presence of an alkali. Is.
フェノール性ノボラックとヘキサフルオロプロペンの
二量体もしくは三量体の反応比は−ORf基による−OH基
の所望の置換率に応じて適宜選定すればよい。The reaction ratio of the dimer or trimer of phenolic novolac and hexafluoropropene may be appropriately selected depending on the desired substitution rate of the —OH group with the —ORf group.
塩基性触媒としてはトリメチルアミンやトリエチルア
ミン等の３級アミン、ピリジン、N,N−ジメチルアニリ
ン、および炭酸ナトリウムや炭酸カリウム等の無機塩類
が例示されるが、トリメチルアミンやトリエチルアミン
等の３級アミンが好ましい。Examples of the basic catalyst include tertiary amines such as trimethylamine and triethylamine, pyridine, N, N-dimethylaniline, and inorganic salts such as sodium carbonate and potassium carbonate, and tertiary amines such as trimethylamine and triethylamine are preferable.
このような塩基性触媒の使用量は通常、反応当量程度
であるが、これに限定されない。The amount of such a basic catalyst used is usually about the reaction equivalent amount, but is not limited thereto.
このフッ素化反応は通常は有機溶媒中において０〜10
0℃で行なう。This fluorination reaction is usually 0-10 in an organic solvent.
Perform at 0 ° C.
有機溶媒としてはアセトニトリル、N,N−ジメチルホ
ルムアミド、ジメチルスルホキサイド、Ｎ−メチルピロ
リドンおよびジグリム等の極性溶媒のほか、ベンゼン、
トルエン、キシレン、エーテル、テトラヒドロフラン等
が例示されるが、溶解性の点からはN,N−ジメチルホル
ムアミド、ジメチルスルホキサイドまたはＮ−メチルピ
ロリドン等が好ましい。Organic solvents include polar solvents such as acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and diglyme, benzene,
Toluene, xylene, ether, tetrahydrofuran and the like are exemplified, but N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like are preferable from the viewpoint of solubility.
このようにして得られるフッ素化ノボラックとエピハ
ロヒドリンの反応は通常アルカリ、例えば水酸化ナトリ
ウム、水酸化カリウム、水酸化リチウム、水酸化カルシ
ウムまたは水酸化マグネシウム等のアルカリ水酸化物の
存在下において約20〜120℃で生成水を適宜除去しなが
ら行なう。The reaction of the thus obtained fluorinated novolac with epihalohydrin is usually about 20 to about in the presence of an alkali, for example, an alkali hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide or magnesium hydroxide. At 120 ℃, remove the generated water as appropriate.
エピハロヒドリンとしては通常エピクロルヒドリンが
使用されるが、エピブロムヒドリンまたはメチルエピク
ロルヒドリン等を使用してもよい。Epichlorohydrin is usually used as epihalohydrin, but epibromhydrin, methylepichlorohydrin or the like may be used.
エピハロヒドリンの使用量は、通常フッ素化ノボラッ
クに残存する−OH基に対して２〜10モル倍であり、また
アルカリの使用量は通常フッ素化ノボラックに残存する
−OH基に対して当量であるが、これらに限定されない。The amount of epihalohydrin used is usually 2 to 10 times the molar amount of --OH groups remaining in the fluorinated novolac, and the amount of alkali is usually equivalent to the amount of --OH groups remaining in the fluorinated novolac. , But not limited to these.
フッ素化ノボラックとエピハロヒドリンの反応におい
てはエピハロヒドリン自体が反応溶媒となるが、所望に
より、アルコール類、エーテル類またはケトン類の有機
溶媒を適宜使用してもよい。In the reaction of fluorinated novolac with epihalohydrin, epihalohydrin itself serves as a reaction solvent, but if desired, organic solvents such as alcohols, ethers or ketones may be appropriately used.
以下、本発明を実施例によって説明する。 Hereinafter, the present invention will be described with reference to examples.
実施例１ 温度計、冷却管および滴下漏斗を備えた三つ口フラス
コ（300ml）内にフェノール性ノボラック（重合度２〜1
0）10.7g、トリエチルアミン9.1g（0.09モル）およびジ
メチルホルムアミド100mlを入れ、ヘキサフルオロプロ
ペンダイマー27.0g（0.09モル）を撹拌下で徐々に滴下
し、撹拌を約４時間続行した後、反応混合物を約2Nの塩
酸水溶液１中に加え、２層に分離した下層の油状生成
物をクロロホルム200mlに溶解させた。Example 1 A three-necked flask (300 ml) equipped with a thermometer, a condenser and a dropping funnel was charged with a phenolic novolak (polymerization degree: 2-1).
0) 10.7 g, triethylamine 9.1 g (0.09 mol) and dimethylformamide 100 ml were added, hexafluoropropene dimer 27.0 g (0.09 mol) was gradually added dropwise under stirring, and the stirring was continued for about 4 hours, then the reaction mixture was added to the reaction mixture. The mixture was added to about 2N hydrochloric acid aqueous solution 1 and the lower layer oily product separated into two layers was dissolved in 200 ml of chloroform.
この溶液を水200mlを用いて２回洗浄した後、クロロ
ホルム層を分取し、硫酸マグネシウムを用いて乾燥し、
濾過処理に付した後、クロロホルムをエバポレーターを
用いて留去させることによって黄褐色の含フッ素ノボラ
ック（１）30.7g得た。This solution was washed twice with 200 ml of water, then the chloroform layer was separated and dried with magnesium sulfate,
After filtration, chloroform was distilled off using an evaporator to obtain 30.7 g of a yellowish brown fluorinated novolak (1).
この生成物（１）の物性を表−１に示す。 The physical properties of this product (1) are shown in Table 1.
実施例２ 実施例１の手順に準拠し、次の配合処方によって含フ
ッ素ノボラック（２）を16.5g得た：成分 配合量(g) フェノール性ノボラック（重合度２〜10） 10.7 トリエチルアミン 5.5 ヘキサフルオロプロペンダイマー 15.0 この生成物（２）の物性を表−１に示す。Example 2 According to the procedure of Example 1, 16.5 g of a fluorinated novolak (2) was obtained by the following formulation: Component loading (g) Phenolic novolak (polymerization degree 2-10) 10.7 Triethylamine 5.5 Hexafluoro Propene dimer 15.0 The physical properties of this product (2) are shown in Table-1.
実施例３ 実施例１の手順に準拠し、次の配合処方によって含フ
ッ素ノボラック（３）を31.0g得た：成分 配合量(g) フェノール性ノボラック（重合度２〜10） 10.7 トリエチルアミン 5.5 ヘキサフルオロプロペントリマー 22.5 この生成物（３）の物性を表−１に示す。Example 3 According to the procedure of Example 1, 31.0 g of a fluorinated novolak (3) was obtained by the following formulation: Component loading (g) Phenolic novolak (degree of polymerization 2-10) 10.7 Triethylamine 5.5 Hexafluoro Propene trimer 22.5 The physical properties of this product (3) are shown in Table-1.
実施例４ 実施例１の手順に準拠し、次の配合処方によって含フ
ッ素ノボラック（４）を10.7g得た：成分 配合量(g) フェノール性ノボラック（重合度２〜10） 10.7 トリエチルアミン 2.0 ヘキサフルオロプロペントリマー 4.5 この生成物（４）の物性を表−１に示す。Example 4 According to the procedure of Example 1, 10.7 g of a fluorinated novolak (4) was obtained by the following formulation: Component loading (g) Phenolic novolak (degree of polymerization 2-10) 10.7 Triethylamine 2.0 Hexafluoro Propene trimer 4.5 The physical properties of this product (4) are shown in Table-1.
実施例５ 温度計、冷却管および滴下漏斗を備えた三つ口フラス
コ（200ml）内に実施例１において調製した生成物
（１）10.0gおよびエピクロルヒドリン30gを入れ、反応
温度を100〜110℃に保ちながら、水酸化ナトリウム25％
水溶液0.5gを撹拌下に約２時間かけて滴下した（反応
中、水を系外へ除去した）。Example 5 10.0 g of the product (1) prepared in Example 1 and 30 g of epichlorohydrin were placed in a three-necked flask (200 ml) equipped with a thermometer, a condenser and a dropping funnel, and the reaction temperature was adjusted to 100 to 110 ° C. Sodium hydroxide 25% while keeping
0.5 g of the aqueous solution was added dropwise with stirring over about 2 hours (water was removed from the system during the reaction).
滴下終了後、過剰のエピクロルヒドリンを回収し、メ
チルエチルケトン50gおよび水50gを加え、樹脂および生
成塩を溶解させ、不溶物を濾別した後、有機層を分取し
た。この有機層を硫酸ナトリウムを用いて乾燥し、濾過
処理を付した後、メチルエチルケトンを留去させて黄褐
色の含フッ素ノボラック型エポキシ樹脂（Ｉ）を6.3g得
た。After completion of the dropping, excess epichlorohydrin was recovered, 50 g of methyl ethyl ketone and 50 g of water were added to dissolve the resin and the produced salt, and the insoluble matter was filtered off, and then the organic layer was separated. The organic layer was dried using sodium sulfate, filtered, and then methyl ethyl ketone was distilled off to obtain 6.3 g of a yellowish brown fluorinated novolac type epoxy resin (I).
この生成物（Ｉ）の物性を表−２に示す。 The physical properties of this product (I) are shown in Table 2.
実施例６ 実施例５の手順に準拠し、次の配合処方によって含フ
ッ素ノボラック型エポキシ樹脂（II）を1.5g得た：成分 配合量(g) 含フッ素ノボラック（２） 10.0 エピクロルヒドリン 50.0 水酸化ナトリウム25％水溶液 3.6 エポキシ樹脂（II）の物性を表−２に示す。Example 6 According to the procedure of Example 5, 1.5 g of a fluorinated novolac type epoxy resin (II) was obtained by the following formulation: Component blending amount (g) Fluorine-containing novolak (2) 10.0 epichlorohydrin 50.0 Sodium hydroxide 25% aqueous solution 3.6 Physical properties of epoxy resin (II) are shown in Table-2.
実施例７ 実施例５の手順に準拠し、次の配合処方によって含フ
ッ素ノボラック型エポキシ樹脂（III）を11.6g得た：成分 配合量(g) 含フッ素ノボラック（３） 10.0 エピクロルヒドリン 50.0 水酸化ナトリウム25％水溶液 2.7 エポキシ樹脂（III）の物性を表−２に示す。Example 7 According to the procedure of Example 5, 11.6 g of a fluorine-containing novolac type epoxy resin (III) was obtained by the following formulation: Component blending amount (g) Fluorine-containing novolac (3) 10.0 Epichlorohydrin 50.0 Sodium hydroxide 25% aqueous solution 2.7 Physical properties of epoxy resin (III) are shown in Table-2.
実施例８ 実施例５の手順に準拠し、次の配合処方によって含フ
ッ素ノボラック型エポキシ樹脂（IV）を9.0g得た：成分 配合量(g) 含フッ素ノボラック（４） 10.0 エピクロルヒドリン 40.0 水酸化ナトリウム25％水溶液 7.6 エポキシ樹脂（IV）の物性を表−２に示す。Example 8 According to the procedure of Example 5, 9.0 g of a fluorinated novolac type epoxy resin (IV) was obtained by the following formulation: Component blending amount (g) Fluorinated novolak (4) 10.0 Epichlorohydrin 40.0 Sodium hydroxide 25% aqueous solution 7.6 The physical properties of the epoxy resin (IV) are shown in Table-2.
比較例１ 実施例５の手順に準拠し、ノボラック（重合度２〜1
0）をそのままエポキシ化して調製したノボラック型エ
ポキシ樹脂について、水の接触角を測定したところ65.3
°となり、撥水性は認められなかった。Comparative Example 1 According to the procedure of Example 5, novolak (polymerization degree 2-1
The contact angle of water was measured for a novolac type epoxy resin prepared by epoxidizing
And the water repellency was not recognized.
発明の効果 本発明による含フッ素ノボラック型エポキシ樹脂は耐
熱性のほかに、撥水性や耐湿耐水性および防汚性や非透
湿性にも優れているので、例えばコンデンサー、抵抗、
IC、LSI等の電気電子部品等の封止剤として従来品より
も優れた特性を発揮する。 EFFECTS OF THE INVENTION The fluorine-containing novolac type epoxy resin according to the present invention is excellent not only in heat resistance but also in water repellency, moisture resistance, water resistance, stain resistance and moisture impermeable property, and therefore, for example, a capacitor, a resistance
As a sealant for electric and electronic parts such as ICs and LSIs, it exhibits superior properties to conventional products.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊藤 孝治郎 兵庫県神戸市中央区加納町６丁目２番１号 株式会社ネオス内 (56)参考文献 特開 昭63−22822（ＪＰ，Ａ) 特開 昭62−240316（ＪＰ，Ａ) 特開 昭60−221418（ＪＰ，Ａ) 特開 昭59−199710（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Kojiro Ito, 6-2-1, Kano-cho, Chuo-ku, Kobe-shi, Hyogo Neos Co., Ltd. (56) Reference JP-A-63-22822 (JP, A) Kai 62-240316 (JP, A) JP 60-221418 (JP, A) JP 59-199710 (JP, A)
Claims (2)
がペルフルオロアルケニルオキシ基−ORf（式中、RfはC
6F11またはC9F17を示す）によって置換され、残余の該
−OH基の実質的に全てがグリシジルエーテル基 によって置換されたことを特徴とする含フッ素ノボラッ
ク型エポキシ樹脂。1. The following formula: (In the formula, n represents a number of 0 to 18) 1 to 95% of the -OH group of the phenolic novolac represented by
Is a perfluoroalkenyloxy group —ORf (wherein Rf is C
6 F 11 or C 9 F 17 ) and substantially all of the remaining --OH groups are glycidyl ether groups. Fluorine-containing novolac type epoxy resin characterized by being replaced by.
ロプロペンの二量体もしくは三量体を塩基性触媒の存在
下で反応させて得られるフッ素化ノボラックをアルカリ
の存在下でエピハロドリンと反応させることを特徴とす
る、該フェノール性ノボラックの−OH基の１〜95％がペ
ルフルオロアルケニルオキシ基−ORf（式中、RfはC6F11
またはC9F17を示す）によって置換され、残余の該−OH
基の実質的に全てがグリシジルエーテル基 によって置換された含フッ素ノボラック型エポキシ樹脂
の製造方法。2. The following formula: (In the formula, n represents a number of 0 to 18) A fluorinated novolak obtained by reacting a dimer or trimer of a phenolic novolak and hexafluoropropene represented by and wherein the reaction with Epiharodorin in the presence of an alkali 1 to 95 percent in perfluoroalkenyl group-ORF (formula -OH groups of the phenolic novolak, Rf is C 6 F 11
Or C 9 F 17 ), and the rest of the --OH
Substantially all of the groups are glycidyl ether groups Of producing a fluorine-containing novolac type epoxy resin substituted by fluorene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20331087A JPH0813870B2 (en) | 1987-08-13 | 1987-08-13 | Fluorine-containing novolac type epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20331087A JPH0813870B2 (en) | 1987-08-13 | 1987-08-13 | Fluorine-containing novolac type epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6445423A JPS6445423A (en) | 1989-02-17 |
| JPH0813870B2 true JPH0813870B2 (en) | 1996-02-14 |
Family
ID=16471913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20331087A Expired - Fee Related JPH0813870B2 (en) | 1987-08-13 | 1987-08-13 | Fluorine-containing novolac type epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813870B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6474215A (en) * | 1987-09-11 | 1989-03-20 | Daikin Ind Ltd | Epoxy resin composition |
| JP4496441B2 (en) * | 1999-07-28 | 2010-07-07 | Ｄｉｃ株式会社 | Manufacturing method of high purity epoxy resin |
| KR20220158809A (en) * | 2020-03-27 | 2022-12-01 | 샌트랄 글래스 컴퍼니 리미티드 | Novolac resin, epoxy resin, photosensitive resin composition, curable resin composition, cured product, electronic device, method for producing novolak resin, and method for producing epoxy resin |
-
1987
- 1987-08-13 JP JP20331087A patent/JPH0813870B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6445423A (en) | 1989-02-17 |
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| R250 | Receipt of annual fees |
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