JP3238288B2 - Method for producing novolak type phenolic resin - Google Patents
Method for producing novolak type phenolic resinInfo
- Publication number
- JP3238288B2 JP3238288B2 JP20553294A JP20553294A JP3238288B2 JP 3238288 B2 JP3238288 B2 JP 3238288B2 JP 20553294 A JP20553294 A JP 20553294A JP 20553294 A JP20553294 A JP 20553294A JP 3238288 B2 JP3238288 B2 JP 3238288B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- novolak
- molecular weight
- reaction
- 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.)
- Expired - Lifetime
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Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、極めて狭い品質規格の
樹脂を得るために、反応途中に樹脂特性の誘導を行いな
がら反応する事を特徴とする、ノボラック型フェノール
樹脂の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novolak-type phenolic resin, which comprises reacting while inducing resin properties during the reaction in order to obtain a resin having a very narrow quality standard.
【０００２】[0002]
【従来の技術】ノボラック型フェノール樹脂は、耐熱
性、耐摩耗性、機械的強度、電気絶縁性、低発煙性、耐
酸性などにすぐれた特長を有するため、産業界のいろい
ろの分野で広く使用されている。これらのノボラック型
フェノール樹脂の生産方法は、フェノール類、アルデヒ
ド類、触媒等を一括または分割して仕込み、その後は加
熱温度、反応温度、反応時間、圧力等を一定に制御する
事により生産される。しかしながらノボラック型フェノ
ール樹脂は、分子量分布を持ったオリゴマーであり、汎
用プラントで上記の方法により生産を行った場合、生産
ロット間で特性値にバラツキを持ち、例えば５０％エタ
ノール溶液での溶液粘度を例にとると、その平均値に対
して５〜３０％のバラツキがでる。そのため、実用特性
上そのバラツキが許容できない用途では、樹脂特性の異
なる複数ロットを目標とする特性値を持つ様に配合して
使用している。2. Description of the Related Art Novolak-type phenolic resins are widely used in various fields in the industrial world because of their excellent properties such as heat resistance, abrasion resistance, mechanical strength, electrical insulation, low smoke generation and acid resistance. Have been. These novolak-type phenolic resins are produced by charging phenols, aldehydes, catalysts, and the like in a lump or dividedly, and thereafter controlling the heating temperature, the reaction temperature, the reaction time, the pressure, and the like to a constant value. . However, a novolak type phenol resin is an oligomer having a molecular weight distribution, and when produced by a general-purpose plant by the above method, there is a variation in characteristic values between production lots. For example, the solution viscosity in a 50% ethanol solution is reduced. For example, a variation of 5 to 30% with respect to the average value is obtained. Therefore, in applications where the variation cannot be tolerated due to practical characteristics, a plurality of lots having different resin characteristics are blended and used so as to have target characteristic values.
【０００３】ゆえに、ノボラック型フェノール樹脂を併
用することなく１つのロットだけで単独使用できる、生
産ロット間の特性値のバラツキの少ないノボラック型フ
ェノール樹脂が強く求められている。近年これらの要求
に対応するため、高精度の秤量機や定量ポンプの導入に
よる原料類の仕込み精度の向上や、シーケンサやコンピ
ュータの導入による反応条件の細かな制御によるノボラ
ック型フェノール樹脂の製造が行われているが、いまだ
品質が一定となる樹脂の製造方法は開発されていない。[0003] Therefore, there is a strong demand for a novolak-type phenolic resin that can be used alone in one lot without using a novolak-type phenolic resin and that has little variation in characteristic values between production lots. In order to respond to these demands in recent years, the introduction of high-precision weighing machines and metering pumps has led to the improvement of raw material charging accuracy, and the introduction of sequencers and computers has led to the production of novolak-type phenolic resins by finely controlling the reaction conditions. However, a method for producing a resin having a constant quality has not yet been developed.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、今ま
でノボラック型フェノール樹脂の樹脂特性の異なる複数
ロットを要求特性にあうように併用していた用途で、ノ
ボラック型フェノール樹脂の単独使用を可能としうる極
めて狭い品質規格（目標特性範囲）のノボラック型フェ
ノール樹脂の製造方法を提供する事にある。SUMMARY OF THE INVENTION An object of the present invention is to use a single novolak type phenolic resin in applications where a plurality of lots having different resin characteristics of the novolak type phenolic resin have been used together so as to meet required characteristics. An object of the present invention is to provide a method for producing a novolak-type phenol resin having a very narrow quality standard (target characteristic range) that can be realized.
【０００５】[0005]
【課題を解決するための手段】本発明は、フェノール類
とアルデヒド類とを酸性触媒の存在下で反応させて得ら
れるノボラック型フェノール樹脂の製造方法において、
縮合反応途中に樹脂特性を測定して、その特性値があら
かじめ決めておいた目標値より大きければフェノール類
の添加を、小さければアルデヒド類の添加を行い、反応
を継続する事により、目標とする特性に誘導する事を特
徴とするノボラック型フェノール樹脂の製造方法に関す
るものである。本発明における分子量と相関する樹脂特
性としては、溶融粘度、平均分子量、融点、軟化点、溶
液粘度、屈折率などがあげられ、これらに限定されるも
のではないが、測定誤差が少なく短時間で測定できるも
のがよい。本発明において、溶液粘度とは、樹脂を良溶
媒に一定の濃度に溶解した溶液の粘度をいい、５０％の
エタノール溶液を測定することが多い。 The present invention relates to a method for producing a novolak type phenol resin obtained by reacting a phenol with an aldehyde in the presence of an acidic catalyst.
During the condensation reaction, the resin properties are measured, and if the property value is larger than a predetermined target value, phenols are added, and if the property value is smaller, aldehydes are added, and the reaction is continued. The present invention relates to a method for producing a novolak-type phenol resin, which is characterized by inducing properties. Resin properties correlated with molecular weight in the present invention
Properties include melt viscosity, average molecular weight, melting point, softening point,
Liquid viscosity, refractive index, etc., but are not limited thereto.
Although it is not possible to measure in a short time with little measurement error
Is good. In the present invention, the solution viscosity means that the resin
The viscosity of a solution dissolved at a certain concentration in a medium, 50%
Often, ethanol solutions are measured.
【０００６】本発明で使用するフェノール類としては、
フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−ク
レゾール、３，５−キシレノール、エチルフェノール、
アルキルフェノール類、ビスフェノール類などのフェノ
ール類から選ばれた１種または２種以上が使用できる。
また、アルデヒド類としては、ホルムアルデヒド、パ
ラホルムアルデヒド、アセトアルデヒド、ベンズアルデ
ヒド、サリチルアルデヒドなどのアルデヒド類から選ば
れた１種または２種以上が使用できる。使用する触媒と
しては、塩酸、硫酸、リン酸などの無機酸類、蓚酸、酢
酸などの有機酸類、および鉛、錫、亜鉛などの二価金属
の有機酸塩類などから選ばれる１種または２種以上の組
合わせで使用できる。The phenols used in the present invention include:
Phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, ethylphenol,
One or more selected from phenols such as alkylphenols and bisphenols can be used.
As the aldehyde, one or more aldehydes selected from formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde and the like can be used. As the catalyst to be used, one or more selected from inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as oxalic acid and acetic acid, and organic acid salts of divalent metals such as lead, tin and zinc. Can be used in combination.
【０００７】縮合反応途中の樹脂特性の目標値は、製品
特性と反応途中サンプルの特性値との相関関係により設
定される。縮合反応途中の樹脂特性の目標値を外れた場
合に製品の目標特性範囲へ誘導するためのフェノール類
またはアルデヒド類の添加量については、一定量または
外れ度合いに応じて添加する量を変えてもよく、好まし
くは、試作実験を行い樹脂特性の目標値に対する外れ度
合いに応じて適切な添加量を加えられる様に推算式を求
めておくとよい。縮合反応途中の樹脂特性の測定箇所は
特に限定はしないが、還流反応途中が適している。[0007] The target value of the resin properties during the condensation reaction is set by the correlation between the product properties and the property values of the sample during the reaction. Regarding the addition amount of phenols or aldehydes for deriving to the target characteristic range of the product when the target value of the resin properties during the condensation reaction deviates from the target value, even if the addition amount is changed depending on the fixed amount or the degree of departure. Preferably, it is preferable to perform a trial production experiment and obtain an estimation formula so that an appropriate addition amount can be added according to the degree of deviation of the resin characteristic from a target value. The location of measurement of the resin properties during the condensation reaction is not particularly limited, but is preferably during the reflux reaction.
【０００８】[0008]
【実施例】以下に実施例を挙げて本発明を具体的に説明
するが、本発明はこれらの実施例によって何ら制約され
るものではない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by these examples.
【０００９】《実施例１〜７》 撹拌機、熱交換機、温度計のついた反応装置にフェノー
ル１０００部、３７％ホルマリン６４０部、蓚酸１０部
を仕込み、常圧下で３時間還流反応を行い、内容物の粘
度をＢ型粘度計で９５℃で測定した。ここで、内容物の
粘度測定値が目標値に対して低かったらホルマリンを添
加し、高かったらフェノールを添加し、目標値内ならば
そのままで、２時間還流反応を継続した。その後、液温
が１５０℃になるまで常圧で脱水反応を行い、さらに、
真空度が６０Torrで１８０℃まで脱水縮合反応を行って
ノボラック型フェノール樹脂を得た。上記の製造方法で
７ロットの生産を行った。反応途中サンプルの粘度目標
値および工程検査結果、目標を外れた場合のフェノール
またはホルマリンの添加量、および得られたノボラック
型フェノール樹脂の５０％エタノール溶液の溶液粘度測
定結果は表１に示す通りであった。表中、σは標準偏差
を示す。 Examples 1 to 7 A reactor equipped with a stirrer, a heat exchanger and a thermometer was charged with 1000 parts of phenol, 640 parts of 37% formalin and 10 parts of oxalic acid, and subjected to a reflux reaction under normal pressure for 3 hours. The viscosity of the contents was measured at 95 ° C. with a B-type viscometer. Here, if the measured viscosity value of the content was lower than the target value, formalin was added, if higher, phenol was added, and if it was within the target value, the reflux reaction was continued for 2 hours. Thereafter, a dehydration reaction is performed at normal pressure until the liquid temperature reaches 150 ° C., and further,
A novolak-type phenol resin was obtained by performing a dehydration-condensation reaction at 180 ° C. at a degree of vacuum of 60 Torr. Seven lots were produced by the above manufacturing method. Table 1 shows the viscosity target values and process inspection results of the sample during the reaction, the amount of phenol or formalin added when the target was not satisfied, and the solution viscosity measurement results of the obtained 50% ethanol solution of the novolak-type phenol resin. there were. In the table, σ is the standard deviation
Is shown.
【００１０】《比較例１〜７》実施例１と同型の反応装
置にフェノール１０００部、３７％ホルマリン６４０
部、蓚酸１０部を仕込み、常圧下で５時間還流反応を行
い、次いで、液温が１５０℃になるまで常圧で脱水反応
を行い、さらに、真空度が６０Torrで１８０℃まで脱水
縮合反応を行ってノボラック型フェノール樹脂を得た。
上記の製造方法で７ロットの生産を行った。得られたノ
ボラック型フェノール樹脂の５０％エタノール溶液の溶
液粘度測定結果は表１に示す通りであった。<< Comparative Examples 1 to 7 >> 1000 parts of phenol and 37% formalin 640 were added to a reactor of the same type as in Example 1.
And 10 parts of oxalic acid, refluxed under normal pressure for 5 hours, then dehydrated at normal pressure until the liquid temperature reached 150 ° C, and further dehydrated and condensed to 180 ° C at a vacuum of 60 Torr. Then, a novolak type phenol resin was obtained.
Seven lots were produced by the above manufacturing method. The results of measuring the solution viscosity of a 50% ethanol solution of the obtained novolak type phenol resin are as shown in Table 1.
【００１１】[0011]
【表１】 [Table 1]
【００１２】《実施例８〜１４》 実施例１と同型の反応装置ににクレゾール１０００部、
３７％ホルマリン５７０部、３０％塩酸２．５部を仕込
み、常圧下で５時間還流反応を行い、内容物の重量平均
分子量（Ｍｗ）をゲルパーミエーションクロマト法で測
定した。ここで、内容物の重量平均分子量が目標値に対
して低かったらホルマリンを添加し、高かったらクレゾ
ールを添加し、目標値内ならばそのままで、２時間還流
反応を継続した。その後、液温が１４０℃になるまで常
圧で脱水反応を行い、さらに、真空度が８０Torrで１６
０℃まで脱水縮合反応を行ってノボラック型クレゾール
樹脂を得た。上記の製造方法で７ロットの生産を行っ
た。反応途中サンプルの重量平均分子量の目標値、およ
び工程検査結果、目標を外れた場合のクレゾールまたは
ホルマリンの添加量、およびノボラック型クレゾール樹
脂の重量平均分子量測定結果は表２に示す通りであっ
た。表中、σは標準偏差を示す。 << Examples 8 to 14 >> In a reactor of the same type as in Example 1, 1000 parts of cresol was added.
570 parts of 37% formalin and 2.5 parts of 30% hydrochloric acid were charged and refluxed at normal pressure for 5 hours, and the weight average molecular weight (Mw) of the content was measured by a gel permeation chromatography method. Here, if the weight average molecular weight of the content was lower than the target value, formalin was added, and if it was higher, cresol was added. If the weight average molecular weight was within the target value, the reflux reaction was continued for 2 hours. Thereafter, a dehydration reaction is carried out at normal pressure until the liquid temperature reaches 140 ° C.
A novolak-type cresol resin was obtained by performing a dehydration condensation reaction to 0 ° C. Seven lots were produced by the above manufacturing method. The target value of the weight average molecular weight of the sample during the reaction, the result of the process inspection, the addition amount of cresol or formalin when the target was not satisfied, and the measurement result of the weight average molecular weight of the novolak cresol resin were as shown in Table 2. In the table, σ indicates a standard deviation.
【００１３】《比較例８〜１４》実施例１と同型の反応
装置にクレゾール１０００部、３７％ホルマリン５７０
部、３０％塩酸２．５部を仕込み、常圧下で７時間還流
反応を行い、次いで、液温が１４０℃になるまで常圧で
脱水反応を行い、さらに、真空度が８０Torrで１６０℃
まで脱水縮合反応を行ってノボラック型クレゾール樹脂
を得た。上記の製造方法で７ロットの生産を行った。得
られたノボラック型クレゾール樹脂の重量平均分子量測
定結果は表２に示す通りであった。Comparative Examples 8 to 14 In a reactor of the same type as in Example 1, 1000 parts of cresol and 570 of 37% formalin were added.
And 2.5 parts of 30% hydrochloric acid, refluxed under normal pressure for 7 hours, then dehydrated at normal pressure until the liquid temperature reaches 140 ° C., and further heated to 160 ° C. at a vacuum of 80 Torr.
A novolak-type cresol resin was obtained by performing a dehydration condensation reaction until this. Seven lots were produced by the above manufacturing method. The measurement results of the weight average molecular weight of the obtained novolak cresol resin are as shown in Table 2.
【００１４】[0014]
【表２】 [Table 2]
【００１５】実施例１〜７および８〜１４によるノボラ
ック型フェノール樹脂は、比較例１〜７および８〜１４
によるノボラック型フェノール樹脂に比べ、ロット間バ
ラツキが極めて小さい。The novolak type phenolic resins according to Examples 1 to 7 and 8 to 14 are comparative examples 1 to 7 and 8 to 14
The variation between lots is extremely small as compared with the novolak-type phenol resin.
【００１６】[0016]
【発明の効果】本発明の製造方法によれば、製造ロット
間バラツキが極めて小さいノボラック型フェノール樹脂
を得ることができる。従って、本発明によるノボラック
型フェノール樹脂の製造方法を用いれば極めて狭い品質
規格の樹脂を安定して生産する事ができる。According to the production method of the present invention, it is possible to obtain a novolak-type phenol resin having a very small variation between production lots. Therefore, if the method for producing a novolak phenolic resin according to the present invention is used, a resin having an extremely narrow quality standard can be stably produced.
フロントページの続き (56)参考文献 特開 平６−322054（ＪＰ，Ａ) 特開 平３−152460（ＪＰ，Ａ) 特開 昭55−104322（ＪＰ，Ａ) 特開 平４−76023（ＪＰ，Ａ) 特開 平４−88001（ＪＰ，Ａ) 特開 昭60−92315（ＪＰ，Ａ) 実開 昭57−202121（ＪＰ，Ｕ) 東独国経済特許第219870号明細書 (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 8/00 - 8/38 C08G 85/00 G01N 1/00 - 1/34 G01N 25/00 - 25/72 G01N 30/00 - 30/96 G01N 33/44 G05D 21/00 - 21/02 G05D 24/00 - 24/02 ＷＰＩ／Ｌ（ＱＵＥＳＴＥＬ) ＪＩＣＳＴファイル（ＪＯＩＳ)Continuation of front page (56) References JP-A-6-322054 (JP, A) JP-A-3-152460 (JP, A) JP-A-55-104322 (JP, A) JP-A-4-76023 (JP) JP-A-4-88001 (JP, A) JP-A-60-92315 (JP, A) JP-A-57-202121 (JP, U) East German Economic Patent No. 219870 (58) Field (Int.Cl. 7 , DB name) C08G 8/00-8/38 C08G 85/00 G01N 1/00-1/34 G01N 25/00-25/72 G01N 30/00-30/96 G01N 33 / 44 G05D 21/00-21/02 G05D 24/00-24/02 WPI / L (QUESTEL) JICST file (JOIS)
Claims (2)
媒の存在下で反応させて得られるノボラック型フェノー
ル樹脂の製造方法において、縮合反応途中に分子量と相
関する樹脂特性を測定して、その特性値が予め決めてお
いた目標値より大きければフェノール類の添加を、小さ
ければアルデヒド類の添加を行い、反応を継続する事に
より、目標とする特性に誘導する事を特徴とするノボラ
ック型フェノール樹脂の製造方法。In a method for producing a novolak-type phenol resin obtained by reacting a phenol and an aldehyde in the presence of an acidic catalyst, a resin property correlated with a molecular weight is measured during the condensation reaction, and the characteristic value is measured. Novolak type phenolic resin is characterized by adding phenols if it is larger than the predetermined target value, and adding aldehydes if it is smaller than the predetermined value and continuing the reaction to induce the target properties. Production method.
る樹脂特性が、溶融粘度、ゲルパーミエーションクロマ
トグラフィーによる平均分子量、融点、軟化点、溶液粘
度、屈折率である請求項１記載のノボラック型フェノー
ル樹脂の製造方法。2. The novolak type according to claim 1, wherein the resin properties correlated with the molecular weight measured during the condensation reaction are melt viscosity , average molecular weight determined by gel permeation chromatography, melting point, softening point, solution viscosity, and refractive index. Method for producing phenolic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20553294A JP3238288B2 (en) | 1994-08-30 | 1994-08-30 | Method for producing novolak type phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20553294A JP3238288B2 (en) | 1994-08-30 | 1994-08-30 | Method for producing novolak type phenolic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0867728A JPH0867728A (en) | 1996-03-12 |
| JP3238288B2 true JP3238288B2 (en) | 2001-12-10 |
Family
ID=16508452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20553294A Expired - Lifetime JP3238288B2 (en) | 1994-08-30 | 1994-08-30 | Method for producing novolak type phenolic resin |
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| Country | Link |
|---|---|
| JP (1) | JP3238288B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60045704D1 (en) * | 1999-12-16 | 2011-04-21 | Sumitomo Bakelite Co | Process for the preparation of phenolic resin |
| US7005181B2 (en) | 2000-04-06 | 2006-02-28 | American Aerogel Corporation | Organic, open cell foam materials, their carbonized derivatives, and methods for producing same |
-
1994
- 1994-08-30 JP JP20553294A patent/JP3238288B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 東独国経済特許第２１９８７０号明細書 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0867728A (en) | 1996-03-12 |
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