JPS62212409A - Production of high-purity phenolic resin - Google Patents
Production of high-purity phenolic resinInfo
- Publication number
- JPS62212409A JPS62212409A JP5761786A JP5761786A JPS62212409A JP S62212409 A JPS62212409 A JP S62212409A JP 5761786 A JP5761786 A JP 5761786A JP 5761786 A JP5761786 A JP 5761786A JP S62212409 A JPS62212409 A JP S62212409A
- Authority
- JP
- Japan
- Prior art keywords
- condensate
- water
- phenol
- vacuum
- phenolic resin
- 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920001568 phenolic resin Polymers 0.000 title claims description 8
- 239000005011 phenolic resin Substances 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000012153 distilled water Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 2
- 235000006408 oxalic acid Nutrition 0.000 abstract 1
- -1 preferably Chemical compound 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 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 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 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 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［技術分野１
本発明は不純物や異物の少ないノボラック系フェノール
樹脂の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field 1] The present invention relates to a method for producing a novolak phenolic resin with few impurities and foreign substances.
［背景技術１
従来上り、／ボラック系７エ）−ル樹脂はへキサメチレ
ンチラミン等を混合して７エ／−ル樹脂成形材料等とし
て実用に供されており、これらの用途では不純物や異物
はあまり問題とはならなかった。[Background technology 1 Conventionally, borac-based 7-el resins have been mixed with hexamethylene lentilamine, etc. and used as 7-el resin molding materials, and in these applications, impurities and foreign substances was not much of a problem.
しかしながら半導体封止材料や積層板として用いるノボ
ラック系７１ノール型エポキシ樹脂とかエポキシ樹脂組
成物の硬化剤として採用される場合には、電気性能（絶
縁性）や耐湿性が要求される関係上、未反応原料（フエ
ノール類等）、残存する触媒等の不純物が問題とされる
。However, when used as a curing agent for novolak-based 71-nol epoxy resins and epoxy resin compositions used in semiconductor encapsulation materials and laminates, electrical performance (insulating properties) and moisture resistance are required. Impurities such as reaction raw materials (phenols, etc.) and residual catalysts are considered problems.
このため、従来では、例えば、特開昭６０−５３５１６
号公報に開示されているように、フェノール類とアルデ
ヒド類との縮合物を減圧下（２０Ｔｏｒｒ）、１０時間
かけて２６０℃まで加熱し、２時間かけて脱水させ、こ
の後１５０℃で蒸留水を入れ、水蒸気を吹き込んで水蒸
気蒸留を１時間行い、この後蒸留水を入れ、９０℃で分
離し、水を除去し、再度３時間かけて１５０℃まで加熱
脱水して取り出すことにより、高純度のフェノール樹脂
がｇ１造されているが、この方法は製造時間が長く、し
かも蒸気発生機も必要となって複雑な工程となってしま
っていた。For this reason, conventionally, for example, Japanese Patent Application Laid-Open No. 60-53516
As disclosed in the publication, a condensate of phenols and aldehydes is heated under reduced pressure (20 Torr) to 260°C over 10 hours, dehydrated over 2 hours, and then heated to 150°C with distilled water. and steam distillation for 1 hour by blowing in steam, then adding distilled water, separating at 90°C, removing water, heating to 150°C for 3 hours again, and taking out to obtain high purity. However, this method requires a long production time and requires a steam generator, resulting in a complicated process.
［発明の目的］
本発明は上記事情に鑑みて為されたものであり、その目
的とするところは、製造時間が短く、しかも比較的低温
で行うことができ、簡単な工程で高純度フェノール樹脂
を製造することにある。[Objective of the Invention] The present invention was made in view of the above circumstances, and its purpose is to produce a high-purity phenolic resin in a simple process that can be carried out in a short production time and at a relatively low temperature. The purpose is to manufacture.
［発明の開示１
本発明の高純度フェノール樹脂の製造方法は、フェノー
ル類とアルデヒド類との縮合物を減圧下１５０〜１８０
″Ｃまで加熱して脱水し、次いで常圧下１５ｏ−ｔｓｏ
℃で水洗し、この後減圧下ＺＯＯ−２４０℃虫で加熱し
て脱水することを特徴とするものであり、この構成によ
り上記目的を達成でさたものである。[Disclosure 1 of the Invention The method for producing a high-purity phenolic resin of the present invention is to prepare a condensate of phenols and aldehydes at 150 to 180% under reduced pressure.
''C to dehydrate, then boil under normal pressure at 15o-tso.
It is characterized in that it is washed with water at a temperature of .degree. C. and then dehydrated by heating at a ZOO-240.degree.
本発明ではフェノール類とアルデヒド類とｙ＞１ｇ合物
とは、通常の重合反応、即ちフェノール類とアルデヒド
類を触媒の存在下で重合させることにより得られるすべ
てのものをいう、ここで、フェノール類とは、フェノー
ル、クレゾール、キシレノール、レゾルシン等の７二）
−ル性水酸基を有するものすべてであり、アルデヒド類
とはホルムアルデヒド、ベンズアルデヒド、パラホルム
アルデヒド
る．又、触媒とは塩酸、し嗜う酸、硫酸等の７ボラツク
化反応触媒全般をいう．このようにして得たフェノール
類とアルデヒド類との縮合物を、まず減圧下（４００
− ６００Ｔｏｒｒ）、１５０−１８０℃、好適には１
６０℃まで加熱して３０〜６０分かけて脱水する。次い
で、常圧に戻して１５０〜１８０℃、好適には１６０℃
で約１時間かけて水洗する．水洗は縮合物と同量の蒸留
水で行う．この工程により水分と未反応のフェノール分
を共沸させて除去すると共に残存する触媒を除去する．
この場合、水と７ｘノールの共沸点は約９０℃であるの
で、その温度以上に加熱すればよいが、長時間要するこ
とから１５０〜１８０℃で水洗する．尚、１８０℃を超
えると突沸する恐れがある．この後減圧下で２００〜２
４０℃、好適には２１０℃まで加熱して約１時間かけて
脱水する．減圧度は３０〜６０Ｔｏｒｒ程度である．こ
の工程により不純物を略完全に除去する．この後取り出
して低フリーフェノール樹脂が得られる。In the present invention, the compound of phenol and aldehyde with y>1g refers to all compounds obtained by a normal polymerization reaction, that is, by polymerizing phenol and aldehyde in the presence of a catalyst. 72) Types include phenol, cresol, xylenol, resorcinol, etc.
Aldehydes include formaldehyde, benzaldehyde, and paraformaldehyde. In addition, the term "catalyst" refers to all catalysts for the 7-volatization reaction, such as hydrochloric acid, diluted acid, and sulfuric acid. The condensate of phenols and aldehydes thus obtained was first mixed under reduced pressure (400
- 600 Torr), 150-180°C, preferably 1
Heat to 60°C and dehydrate for 30 to 60 minutes. Then, the pressure is returned to normal pressure and the temperature is 150 to 180°C, preferably 160°C.
Wash with water for about 1 hour. Washing is done with the same amount of distilled water as the condensate. This step azeotropically removes water and unreacted phenol, as well as removing the remaining catalyst.
In this case, since the azeotropic point of water and 7xnol is about 90°C, it is sufficient to heat it above that temperature, but since it takes a long time, washing with water is carried out at 150-180°C. However, if the temperature exceeds 180°C, there is a risk of bumping. After this, under reduced pressure,
Heat to 40°C, preferably 210°C, and dehydrate for about 1 hour. The degree of pressure reduction is approximately 30 to 60 Torr. This process almost completely removes impurities. After this, it is taken out to obtain a low-free phenolic resin.
次に、本発明を実施例に基づいて具体的に説明する．以
下において％は重量％を示す。Next, the present invention will be specifically explained based on examples. In the following, % indicates weight %.
（実施例１乃至３）
種々の割合でフェノールとホルマリンとじ中う酸を反応
釜に仕込み、還流温度で６０分反応し、次に塩酸を加え
てさらに３５分間縮合させる．冷水を多量に添加して反
応を停止し、３０分間放置して分子量が５００〜６００
でそれぞれ７ Ｉ７ − フェノール含有量が９．４％
（実施例１）、１２．７％（実施例２）、１３．４％（
実施例３）の縮合物を調製した．この縮合物を減圧下（
６００Ｔｏｒｒ）、１６０℃まで加熱して４０分間かけ
て脱水し、次いで常圧下１６０℃で１時間かけて水洗し
、この後減圧下（４０〜５０Ｔｏｒｒ）、２１０℃まで
加熱して１時間かけて脱水してフェノール樹脂を得た．
水洗工程の前後及び最終的に得られたフェノール樹脂の
７リーフエノールの含有量を測定した（ＧＰＣ分析によ
る）、結果を第１表に示す．尚、電気伝導度は５μｓ／
ａｍ以下であった。(Examples 1 to 3) Phenol, formalin and ceric acid were charged into a reaction vessel in various ratios, reacted for 60 minutes at reflux temperature, then hydrochloric acid was added and condensed for an additional 35 minutes. Stop the reaction by adding a large amount of cold water, and leave it for 30 minutes until the molecular weight reaches 500-600.
respectively 7 I7 - phenol content is 9.4%
(Example 1), 12.7% (Example 2), 13.4% (
The condensate of Example 3) was prepared. This condensate was mixed under reduced pressure (
600 Torr), heated to 160°C for 40 minutes, then washed with water at 160°C under normal pressure for 1 hour, then heated to 210°C under reduced pressure (40 to 50 Torr), and dehydrated for 1 hour. A phenolic resin was obtained.
The content of 7-leaf enol in the phenolic resin before and after the water washing process and finally obtained was measured (by GPC analysis), and the results are shown in Table 1. In addition, the electrical conductivity is 5μs/
It was below am.
第１表
実施例１ ９．４ ５，８ ０，４
０．０８実施例２ １２．７ ６．７ ０
．１４ 熊ｒ ３ １３．４ ８，２
０．２２ ０．０６【発明の効果１
本発明にあっては、フェノール類とアルデヒド類との縮
合物を減圧下１５０〜１８０”Ｃまで加熱して脱水し、
次いで常圧下１５０〜１８０’Ｃで水洗し、この後減圧
下２００〜２４０℃まで加熱して脱水するので、脱水工
程における水洗により水分の７工ノール分が共沸して、
低フリーフェノールの高純度７エ／−ル樹脂を得ること
ができるものであり、又製造時間が短く、しかも比較的
低温で行うことができ、従来と比べて簡単な工程となる
ものである。Table 1 Example 1 9.4 5,8 0,4
0.08 Example 2 12.7 6.7 0
．． 14 bear r 3 13.4 8,2
0.22 0.06 Effect of the invention 1 In the present invention, a condensate of phenols and aldehydes is dehydrated by heating to 150 to 180"C under reduced pressure,
Next, it is washed with water at 150 to 180'C under normal pressure, and then dehydrated by heating to 200 to 240°C under reduced pressure.
It is possible to obtain a high-purity 7 el resin with low free phenol content, and the production time is short and the process can be carried out at a relatively low temperature, making the process simpler than conventional methods.
代理人 弁理士 石 １）長 七 手続補正書（自発） 昭和６１年５月２日Agent Patent Attorney Ishi 1) Choshichi Procedural amendment (voluntary) May 2, 1986
Claims (1)
１５０〜１８０℃まで加熱して脱水し、次いで常圧下１
５０〜１８０℃で水洗し、この後減圧下２００〜２４０
℃まで加熱して脱水することを特徴とする高純度フエノ
ール樹脂の製造方法。(1) A condensate of phenols and aldehydes is heated to 150 to 180°C under reduced pressure to dehydrate it, and then 150°C under normal pressure.
Washed with water at 50-180°C, then heated at 200-240°C under reduced pressure.
A method for producing high-purity phenolic resin characterized by dehydration by heating to ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5761786A JPS62212409A (en) | 1986-03-14 | 1986-03-14 | Production of high-purity phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5761786A JPS62212409A (en) | 1986-03-14 | 1986-03-14 | Production of high-purity phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62212409A true JPS62212409A (en) | 1987-09-18 |
Family
ID=13060837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5761786A Pending JPS62212409A (en) | 1986-03-14 | 1986-03-14 | Production of high-purity phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62212409A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03149211A (en) * | 1989-11-06 | 1991-06-25 | Murata Mfg Co Ltd | Production of electronic part sealing material |
| JPH06287261A (en) * | 1993-04-06 | 1994-10-11 | Kanebo Nsc Ltd | Method for purifying novolak resin |
-
1986
- 1986-03-14 JP JP5761786A patent/JPS62212409A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03149211A (en) * | 1989-11-06 | 1991-06-25 | Murata Mfg Co Ltd | Production of electronic part sealing material |
| JPH06287261A (en) * | 1993-04-06 | 1994-10-11 | Kanebo Nsc Ltd | Method for purifying novolak resin |
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