JPS6350361B2 - - Google Patents
Info
- Publication number
- JPS6350361B2 JPS6350361B2 JP59260322A JP26032284A JPS6350361B2 JP S6350361 B2 JPS6350361 B2 JP S6350361B2 JP 59260322 A JP59260322 A JP 59260322A JP 26032284 A JP26032284 A JP 26032284A JP S6350361 B2 JPS6350361 B2 JP S6350361B2
- Authority
- JP
- Japan
- Prior art keywords
- bisphenols
- phenol
- formalin
- reaction
- water
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 22
- 229930185605 Bisphenol Natural products 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- 229920003986 novolac Polymers 0.000 claims description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003822 epoxy resin Substances 0.000 description 16
- 229920000647 polyepoxide Polymers 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 239000012535 impurity Substances 0.000 description 11
- 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 10
- 150000002989 phenols Chemical class 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 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 class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
［技術分野］
本発明は、エポキシ樹脂の硬化剤として用いら
れるフエノールノボラツクの製造方法に関するも
のである。
［背景技術］
エポキシ樹脂は電子機器用途の積層板や成形
品、封止材料などとして極めて多様に用いられて
きている。そして電子機器の高信頼性、小型化、
軽量化および低コスト化が進むとともに、この用
途に用いられるエポキシ樹脂組成物の耐熱性や接
着性を向上させかつ低コストにすることが望まれ
るところである。
従来よりこのような用途のエポキシ樹脂組成物
において、硬化剤としてジシアンジアミド、ジハ
ロゲン化ジアミノジフエニルメタン、あるいはフ
エノールホルムアルデヒド樹脂などが工業的に使
用されている。ここで低コストという面ではフエ
ノールホルムアルデヒド樹脂が最も有利である。
しかしフエノールホルムアルデヒド樹脂には製造
の過程で低分子量の不純物が含有されることにな
り、この不純物によつてエポキシ樹脂の耐熱性や
接着性を低下させることになるという問題を有す
るものである。
［発明の目的］
本発明は、上記の点に鑑みて為されたものであ
り、エポキシ樹脂の硬化剤として用いてエポキシ
樹脂の耐熱性や接着性を向上させることができる
フエノールノボラツクの製造方法を提供すること
を目的とするものである。
［発明の開示］
しかして本発明は、反応の第一工程としてビス
フエノール類にホルマリンを反応させてビスフエ
ノール類の４メチロール化物を調製し、反応の第
二工程としてこの４メチロール化物にフエノール
類を反応させてフエノールノボラツクを調製する
にあたつて、第一工程の終了後生成物を有機溶剤
に溶解させて有機成分と水とに分離させ、さらに
有機成分を純水で洗浄したのちこれを第二工程の
反応に供するようにしたものである。すなわち、
低分子量の不純物は第一工程におけるホルマリン
の未反応分が第二工程におけるフエノール類と反
応することによつて生成されることになるもので
あるが、第一工程における生成物を有機成分と水
とに分離させて水に溶解するホルマリンを有機成
分から分離させ、さらに有機成分を純水で洗浄し
て有機成分からホルマリンを完全に除去させるよ
うにし、未反応の遊離のホルマリンが含有されな
い状態で第二工程の反応がなされるようにして、
低分子量の不純物が生成されないようにしたもの
である。
以下本発明を詳細に説明する。まず第一工程と
してビスフエノール類とホルマリンとを触媒の存
在下反応させる。ビスフエノール類としてはビス
フエノールＡやビスフエノールＦを用いることが
できる。また触媒としてはアルカリ金属の水酸化
物が一般に用いられるもので、たとえば水酸化ナ
トリウム、水酸化カルシウム、水酸化マグネシウ
ム等であり、これらは高濃度の水溶液として用い
られる。第一工程の反応操作としては、まずビス
フエノール類にアルカリ金属水酸化物の水溶液を
投入する。このときアルカリ金属水酸化物の量は
ビスフエノール類の−OHに対して0.5〜1.2モル
倍（好ましくは1.0〜1.1モル倍）に設定するのが
よく、アルカリ金属水酸化物は10〜30重量％の水
溶液として使用するのが好ましい。ビスフエノー
ル類がアルカリ金属水酸化物に溶解したのち、ホ
ルマリンを徐々に加える。用いるホルマリンの量
はビスフエノール類に対して４〜８モル倍（好ま
しくは4.0〜4.5モル倍）である。また反応に要す
る温度は30〜70℃（好ましくは40〜50℃）で、反
応に要する時間は１〜３時間である。ビスフエノ
ール類に対するホルマリンの反応によつて、ビス
フエノール類の４メチロール化物が生成される。
この第一工程の反応が終了したのち、りん酸や
塩酸等で中和して生成物を析出させ、この生成物
を有機溶剤に溶解させる。有機溶剤としては水は
溶解しないがビスフエノール類の４メチロール化
物は溶解させるものである必要があり、メチルイ
ソブチルケトン（MIBK）が用いられる。生成物
をMIBKに溶解させると、生成物はMIBKに溶解
するビスフエノール類の４メチロール化物を主成
分とする有機成分と、MIBKに溶解しない第一工
程の反応で縮合水として生成された水とに分離さ
れる。この水を除去したのち、有機成分を純水に
よつて３〜６回洗浄する。第一工程において反応
に寄与しなかつた未反応のホルマリンは上記分離
される水に溶解した状態で除去され、またこの純
水による洗浄でさらに溶解除去され、有機成分に
はほとんど未反応のホルマリンは含有されないこ
とになる。さらに不純物イオンも除去され含有さ
れないことになる。洗浄終了後、MIBKを減圧下
で除去し、ビスフエノール類の４メチロール化物
を主成分とする有機成分を純粋な形で得る。
第二工程はこのようにして得たビスフエノール
類の４メチロール化物とフエノール類とを触媒の
存在化反応させることによつておこなう。フエノ
ール類としてはフエノールの他にクレゾールなど
を用いることができる。また触媒としてはシユウ
酸を用いるのが一般的である。フエノール類の量
はビスフエノール類の４メチロール化物に対して
8.0〜12.0モル倍が好ましく、触媒としてのシユ
ウ酸の量はビスフエノール類の４メチロール化物
に対して0.1〜0.01モル倍が好ましい。反応に要
する温度は80〜120℃、反応に要する時間は10〜
12時間である。反応終了後、165℃程度まで昇温
してシユウ酸を分解し、その後80〜120℃で減圧
蒸留をおこない、水や未反応のフエノール類を除
去する。
このようにしてビスフエノール類の４メチロー
ル化物にフエノール類を反応させて、次の［１］
の構造式で示されるフエノールノボラツクを得る
ことができる。
（式中ＸはCH2またはＣ（CH3）2であり、ＹはＨ
またはCH3であつて４個のＹは総て同じであつて
も異なつてもよい。）
ここで第一工程における反応物の洗浄をおこな
わないときには、未反応のホルマリンが残つた状
態で第二工程の反応がなされて、ホルマリンがフ
エノール類と反応して次の［２］の構造式で示さ
れるフエノールノボラツクが副生成物として生成
されることになる。
そして低分子領域にこのような不純物が５重量
％以上存在すると、上記［１］のフエノールノボ
ラツクをエポキシ樹脂組成物の硬化剤として用い
た場合、エポキシ樹脂の耐熱性や接着性が低下す
ることになるものである。
次に本発明を実施例によつてさらに説明する。
実施例
ビスフエノールA27重量部に、水20重量部に水
酸化ナトリウム4.8重量部を溶解した水溶液を加
え、撹拌した。ビスフエノールＡがある程度溶解
したのち、37％ホルマリン39重量部を徐々に加え
た。そして反応温度40℃で２時間反応させた後、
冷却して希塩酸を用いて中和した。析出した生成
物を100重量部のMIBKに溶解させ、水層と有機
層とに分離した。さらに分離した有機層を100重
量部の純水で４回洗浄し、こののちMIBKを減圧
蒸留によつて除去した。このようにして得たもの
の構造をNMRで解析したところ、ビスフエノー
ルＡの４メチロール化物であることが判明した。
得られたビスフエノールＡの４メチロール化物
を20重量部採り、フエノール54重量部、シユウ酸
0.07重量部、水50重量部を用いて80℃で10時間反
応させた。反応終了後、165℃まで昇温してこの
温度を１時間保持した後、120℃で減圧蒸留をお
こない、水と未反応のフエノールを除去した。得
られた生成物の構造をGCP、NMRによつて解析
したところ、上記した［１］の構造を持つ化合物
が主生成物であり、低分子領域の不純物は５重量
％以下しか含まないことが判明した。またこの得
られた生成物の分子量分布を第１図に示す。
このようにして得たフエノールノボラツクを硬
化剤として用い、次の配合でエポキシ樹脂ワニス
を調製した。
（重量部）
●ブロム化ビスフエノールＡ型エポキシ樹脂（エ
ポキシ当量518） 85
●クレゾールノボラツク型エポキシ樹脂（エポキ
シ当量214） 15
●上記で得たフエノールノボラツク（OH当量
115） 27
●２−エチル−４−メチルイミダゾール 0.10
●メチルエチルケトン 100
このエポキシ樹脂ワニスをガラス布に含浸さ
せ、150℃で乾燥することによつてレジンコンテ
ント45％のプリプレグを得た。このプリプレグを
４枚重ね、さらにその上下に厚み0.035mmの銅箔
を重ね、これを180℃の熱板間に入れて40Kg／cm2、
90分間の条件で加熱加圧することにより銅張り積
層板を作成した。
比較例
実施例において、MIBKによつて有機層を水層
から分離したのち、純水で洗浄することなく
MIBKを除去して生成物を得るようにした他は、
実施例と同様にした。このようにして得た生成物
の構造をGPC、NMRによつて解析したところ、
上記した［１］の構造を持つ化合物が主生成物で
はあるが、低分子領域の不純物が５重量％以上含
むことが判明した。またこの得られた生成物の分
子量分布を第２図に示す。
またこのようにして得たフエノールノボラツク
を硬化剤として用い、実施例と同様にしてエポキ
シ樹脂ワニスを調製し、さらに実施例と同様にし
て銅張り積層板を作成した。
上記実施例及び比較例によつて作成した積層板
についてガラス転移温度、銅箔剥離強度、層間剥
離強度についての特性を試験した。結果を次表に
示す。ここでガラス転移温度（Tg）は、積層板
の銅箔をエツチングによつて除去した板を試験片
とし、岩本製作所製の固体粘弾性装置を用いて測
定した。銅箔剥離強度は積層板における銅箔の剥
離強度をJIS−Ｃ−6481に準拠して測定した。層
間剥離強度は積層板の層間の剥離強度を銅箔剥離
強度の場合と同様にして測定した。
[Technical Field] The present invention relates to a method for producing phenol novolak used as a curing agent for epoxy resins. [Background Art] Epoxy resins have been used in a wide variety of applications, such as laminates, molded products, and sealing materials for electronic devices. and high reliability and miniaturization of electronic equipment.
As weight and cost reductions progress, it is desired to improve the heat resistance and adhesive properties of epoxy resin compositions used for this purpose and to reduce costs. Hitherto, in epoxy resin compositions for such uses, dicyandiamide, dihalogenated diaminodiphenylmethane, or phenol formaldehyde resins have been industrially used as curing agents. Here, phenol formaldehyde resin is most advantageous in terms of low cost.
However, the phenol formaldehyde resin contains low molecular weight impurities during the manufacturing process, and this impurity has the problem of lowering the heat resistance and adhesiveness of the epoxy resin. [Object of the Invention] The present invention has been made in view of the above points, and provides a method for producing phenol novolak, which can be used as a curing agent for epoxy resins to improve the heat resistance and adhesive properties of epoxy resins. The purpose is to provide the following. [Disclosure of the Invention] Accordingly, in the present invention, in the first step of the reaction, bisphenols are reacted with formalin to prepare a tetramethylol compound of bisphenols, and in the second step of the reaction, a phenol is added to the tetramethylol compound. When preparing phenol novolak by reacting, after the first step, the product is dissolved in an organic solvent to separate the organic component and water, and the organic component is further washed with pure water. is subjected to the second step reaction. That is,
Low molecular weight impurities are produced when the unreacted portion of formalin in the first step reacts with phenols in the second step, but when the product in the first step is combined with organic components and water, The formalin that dissolves in water is separated from the organic component, and the organic component is further washed with pure water to completely remove formalin from the organic component, so that no unreacted free formalin is contained. Allowing the reaction of the second step to take place,
This prevents the production of low molecular weight impurities. The present invention will be explained in detail below. First, in the first step, bisphenols and formalin are reacted in the presence of a catalyst. As the bisphenols, bisphenol A and bisphenol F can be used. As the catalyst, alkali metal hydroxides are generally used, such as sodium hydroxide, calcium hydroxide, magnesium hydroxide, etc., and these are used as highly concentrated aqueous solutions. In the reaction operation of the first step, first, an aqueous solution of an alkali metal hydroxide is added to bisphenols. At this time, the amount of alkali metal hydroxide is preferably set to 0.5 to 1.2 times (preferably 1.0 to 1.1 times) by mole relative to -OH of the bisphenols, and the amount of alkali metal hydroxide is 10 to 30 times by mole. % aqueous solution. After the bisphenols are dissolved in the alkali metal hydroxide, formalin is gradually added. The amount of formalin used is 4 to 8 moles (preferably 4.0 to 4.5 times) relative to the bisphenols. Further, the temperature required for the reaction is 30 to 70°C (preferably 40 to 50°C), and the time required for the reaction is 1 to 3 hours. The reaction of formalin with bisphenols produces tetramethylolated bisphenols. After the reaction of this first step is completed, the product is precipitated by neutralization with phosphoric acid, hydrochloric acid, etc., and this product is dissolved in an organic solvent. The organic solvent must be one that does not dissolve water but can dissolve tetramethylol compounds of bisphenols, and methyl isobutyl ketone (MIBK) is used. When the product is dissolved in MIBK, the product consists of an organic component mainly consisting of 4-methylolated bisphenols that dissolves in MIBK, and water produced as condensation water in the first step reaction that does not dissolve in MIBK. separated into After removing this water, the organic components are washed 3 to 6 times with pure water. Unreacted formalin that did not contribute to the reaction in the first step is removed while being dissolved in the separated water, and is further dissolved and removed by washing with this pure water, so that almost all unreacted formalin remains in the organic component. It will not be included. Further, impurity ions are also removed and no longer contained. After the washing is completed, MIBK is removed under reduced pressure to obtain an organic component mainly composed of tetramethylolated bisphenols in a pure form. The second step is carried out by reacting the thus obtained tetramethylolated bisphenols with phenols in the presence of a catalyst. As the phenols, cresol and the like can be used in addition to phenol. Further, oxalic acid is generally used as a catalyst. The amount of phenols is based on the 4-methylol compound of bisphenols.
The amount of oxalic acid as a catalyst is preferably 8.0 to 12.0 times by mole, and the amount of oxalic acid as a catalyst is preferably 0.1 to 0.01 times by mole relative to the tetramethylol compound of bisphenols. The temperature required for the reaction is 80-120℃, and the time required for the reaction is 10-120℃.
It is 12 hours. After the reaction is completed, the temperature is raised to about 165°C to decompose the oxalic acid, and then vacuum distillation is performed at 80 to 120°C to remove water and unreacted phenols. In this way, phenols are reacted with the tetramethylol compound of bisphenols to produce the following [1]
A phenol novolak having the structural formula can be obtained. (In the formula, X is CH 2 or C(CH 3 ) 2 , and Y is H
or CH 3 and all four Y's may be the same or different. ) If the reactants in the first step are not washed, the reaction in the second step is carried out with unreacted formalin remaining, and the formalin reacts with the phenols to form the following structural formula [2]. The phenol novolac shown in will be produced as a by-product. If 5% by weight or more of such impurities exist in the low molecular weight region, the heat resistance and adhesiveness of the epoxy resin will decrease when the phenol novolac described in [1] above is used as a curing agent for an epoxy resin composition. It is something that becomes. Next, the present invention will be further explained with reference to Examples. Example An aqueous solution prepared by dissolving 4.8 parts by weight of sodium hydroxide in 20 parts by weight of water was added to 27 parts by weight of Bisphenol A and stirred. After bisphenol A had dissolved to some extent, 39 parts by weight of 37% formalin was gradually added. After reacting for 2 hours at a reaction temperature of 40°C,
It was cooled and neutralized using dilute hydrochloric acid. The precipitated product was dissolved in 100 parts by weight of MIBK and separated into an aqueous layer and an organic layer. Furthermore, the separated organic layer was washed four times with 100 parts by weight of pure water, and then MIBK was removed by vacuum distillation. When the structure of the product thus obtained was analyzed by NMR, it was found to be a tetramethylol compound of bisphenol A. 20 parts by weight of the obtained tetramethylol of bisphenol A was taken, 54 parts by weight of phenol, and oxalic acid.
0.07 parts by weight and 50 parts by weight of water were used to react at 80°C for 10 hours. After the reaction was completed, the temperature was raised to 165°C and maintained at this temperature for 1 hour, followed by vacuum distillation at 120°C to remove water and unreacted phenol. When the structure of the obtained product was analyzed by GCP and NMR, it was found that the compound having the structure [1] above was the main product, and that it contained less than 5% by weight of impurities in the low molecular region. found. Furthermore, the molecular weight distribution of the obtained product is shown in FIG. Using the phenol novolak thus obtained as a curing agent, an epoxy resin varnish was prepared according to the following formulation. (Parts by weight) ● Brominated bisphenol A type epoxy resin (epoxy equivalent: 518) 85 ● Cresol novolak type epoxy resin (epoxy equivalent: 214) 15 ● Phenol novolak obtained above (OH equivalent
115) 27 ●2-Ethyl-4-methylimidazole 0.10 ●Methyl ethyl ketone 100 Glass cloth was impregnated with this epoxy resin varnish and dried at 150°C to obtain a prepreg with a resin content of 45%. Layer 4 sheets of this prepreg, then layer copper foil with a thickness of 0.035 mm above and below it, and place this between hot plates at 180℃ to produce 40Kg/cm 2 .
A copper-clad laminate was produced by heating and pressing for 90 minutes. Comparative Example In the example, after separating the organic layer from the aqueous layer using MIBK, the organic layer was separated from the aqueous layer without washing with pure water.
Other than removing MIBK to obtain the product,
The same procedure as in the example was carried out. The structure of the product thus obtained was analyzed by GPC and NMR, and it was found that
Although the compound having the structure [1] described above was the main product, it was found that it contained 5% by weight or more of impurities in the low molecular region. Furthermore, the molecular weight distribution of the obtained product is shown in FIG. Using the phenol novolak thus obtained as a curing agent, an epoxy resin varnish was prepared in the same manner as in the Examples, and a copper-clad laminate was also prepared in the same manner as in the Examples. The properties of glass transition temperature, copper foil peel strength, and interlayer peel strength were tested for the laminates produced in the above Examples and Comparative Examples. The results are shown in the table below. The glass transition temperature (Tg) was measured using a solid viscoelastic device manufactured by Iwamoto Seisakusho, using a test piece prepared by removing the copper foil of the laminate by etching. The copper foil peel strength was measured by measuring the peel strength of the copper foil in the laminate in accordance with JIS-C-6481. The interlayer peel strength was measured by measuring the interlayer peel strength of the laminate in the same manner as the copper foil peel strength.
【表】
前表の結果、低分子量の不純物が５重量％以上
含まれる比較例のものを硬化剤として用いた場合
より、低分子量の不純物の含有を抑えた実施例の
ものを硬化剤として用いたものの方が、ガラス転
移温度が高くて耐熱性に優れ、接着力においても
優れることが確認される。
［発明の効果］
上述のように本発明にあつては、ビスフエノー
ル類とホルマリンとを反応させてビスフエノール
類の４メチロール化物を調製し、これを有機溶剤
に溶解させて有機成分と水とに分離し、有機成分
を純水によつて洗浄したのち、これにフエノール
類を反応させるようにしてフエノールノボラツク
を得るようにしたので、未反応のホルマリンを確
実に除去した状態でビスフエノール類の４メチロ
ール化物をフエノール類と反応させることがで
き、未反応のホルマリンがフエノール類と反応し
て生成される低分子量の不純物を低減することが
でき、フエノールノボラツクをエポキシ樹脂の硬
化剤として用いた場合のエポキシ樹脂の耐熱性や
接着性が低下することを防止できるものである。[Table] As a result of the table above, it was found that the example curing agent containing less low molecular weight impurities was used as a curing agent compared to the case where the comparative example containing 5% or more of low molecular weight impurities was used as a curing agent. It is confirmed that the glass transition temperature is higher, the heat resistance is higher, and the adhesive strength is also better. [Effects of the Invention] As described above, in the present invention, bisphenols and formalin are reacted to prepare a tetramethylol compound of bisphenols, and this is dissolved in an organic solvent to combine the organic component and water. After separating the organic components and washing the organic components with pure water, we reacted the organic components with phenols to obtain phenol novolak, so we made sure to remove the unreacted formalin before producing bisphenols. It is possible to react the tetramethylolated product of phenol with phenols, and it is possible to reduce the low molecular weight impurities produced when unreacted formalin reacts with phenols. This can prevent the heat resistance and adhesive properties of the epoxy resin from deteriorating even when the epoxy resin is exposed to heat.
第１図及び第２図は実施例及び比較例における
生成物の分子量分布を示すグラフである。
FIGS. 1 and 2 are graphs showing the molecular weight distribution of products in Examples and Comparative Examples.
Claims (1)
てビスフエノール類の４メチロール化物を調製
し、これを有機溶剤に溶解させて有機成分と水と
に分離し、有機成分を純水によつて洗浄したの
ち、これにフエノール類を反応させることを特徴
とするフエノールノボラツクの製造方法。 ２ 有機溶剤がメチルイソブチルケトンであるこ
とを特徴とする特許請求の範囲第１項記載のフエ
ノールノボラツクの製造方法。[Claims] 1. A tetramethylol compound of bisphenols is prepared by reacting bisphenols with formalin, and this is dissolved in an organic solvent to separate an organic component and water, and the organic component is dissolved in pure water. 1. A method for producing a phenol novolak, which comprises washing the phenol novolak with a phenol and then reacting the phenol with a phenol. 2. The method for producing phenol novolak according to claim 1, wherein the organic solvent is methyl isobutyl ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26032284A JPS61138614A (en) | 1984-12-10 | 1984-12-10 | Production of phenolic novolac |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26032284A JPS61138614A (en) | 1984-12-10 | 1984-12-10 | Production of phenolic novolac |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61138614A JPS61138614A (en) | 1986-06-26 |
| JPS6350361B2 true JPS6350361B2 (en) | 1988-10-07 |
Family
ID=17346402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26032284A Granted JPS61138614A (en) | 1984-12-10 | 1984-12-10 | Production of phenolic novolac |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61138614A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0674308B2 (en) * | 1985-07-12 | 1994-09-21 | 日立化成工業株式会社 | Bisphenol A Novolac Resin |
| JPH05156120A (en) * | 1991-12-04 | 1993-06-22 | Sumitomo Bakelite Co Ltd | Thermosetting molding material |
| US6746896B1 (en) * | 1999-08-28 | 2004-06-08 | Georgia Tech Research Corp. | Process and material for low-cost flip-chip solder interconnect structures |
| TWI324164B (en) * | 2006-06-21 | 2010-05-01 | Chang Chun Plastics Co Ltd | Novel phenolic resin, its preparation and its use |
| JP2009185187A (en) * | 2008-02-07 | 2009-08-20 | Taoka Chem Co Ltd | Manufacturing method for alkylphenol-formaldehyde co-condensed resin |
| JP5238777B2 (en) * | 2010-09-14 | 2013-07-17 | 太陽ホールディングス株式会社 | Photosensitive resin, curable resin composition containing the same, dry film thereof, and printed wiring board using them |
| KR20180099681A (en) * | 2015-12-25 | 2018-09-05 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | COMPOUND, RESIN, COMPOSITION, METHOD FOR FORMING RESIST PATTERN, |
| TWI784484B (en) * | 2020-04-24 | 2022-11-21 | 南韓商Ｌｇ化學股份有限公司 | Curing agent, adhesive composition for semiconductor containing the same, adhesive film for semiconductor, and semiconductor package including the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52112696A (en) * | 1976-03-18 | 1977-09-21 | Mitsubishi Chem Ind Ltd | Preparation of fibers of films of phenolic resins |
| JPS5730716A (en) * | 1980-07-31 | 1982-02-19 | Dainippon Ink & Chem Inc | Treating method of phenolic resin |
-
1984
- 1984-12-10 JP JP26032284A patent/JPS61138614A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52112696A (en) * | 1976-03-18 | 1977-09-21 | Mitsubishi Chem Ind Ltd | Preparation of fibers of films of phenolic resins |
| JPS5730716A (en) * | 1980-07-31 | 1982-02-19 | Dainippon Ink & Chem Inc | Treating method of phenolic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61138614A (en) | 1986-06-26 |
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