JPS62119220A - Production of polyhydroxyl compound - Google Patents
Production of polyhydroxyl compoundInfo
- Publication number
- JPS62119220A JPS62119220A JP25919885A JP25919885A JPS62119220A JP S62119220 A JPS62119220 A JP S62119220A JP 25919885 A JP25919885 A JP 25919885A JP 25919885 A JP25919885 A JP 25919885A JP S62119220 A JPS62119220 A JP S62119220A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- dihydroxymethyl
- component
- acid
- compound
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、新規なポリヒドロキシ化合物の製造法、詳し
くは狭い分子量分布幅を有する新規にして且つ有用なポ
リヒドロキシ化合物の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel method for producing polyhydroxy compounds, and more particularly to a method for producing novel and useful polyhydroxy compounds having a narrow molecular weight distribution width.
従 の 技 術
従来より、エポキシ樹脂の硬化剤としては、アミン類、
酸無水物、フェノールノボラック樹脂等が用いられてき
たが、近年、積層板、封止材等の用途においても、製品
の高性能化、低価格化の要請力ら、フェノールノボラッ
ク樹脂が見直され、該樹脂は殊に電気・電子材料関係に
好適に利用されている。しかして、該フェノールノボラ
ック樹脂は、一般にフェノール類とホルムアルデヒドと
を酸触媒の存在下で縮合反応させて得られ、主としてメ
チレン結合により結合されたフェノール核２〜２０個か
ら構成される直鎖状分子であると考えられている。上記
原料フェノール類としては、通常１個のフェノール性水
酸基を有する石炭酸、オルソクレゾール等が用いられ、
その結果得られる樹脂は未反応のフェノールモノマーと
２核体とからなる低分子量成分を含んでいる。之等のこ
とより、該樹脂はこれを硬化剤として用いた場合、架橋
密度の高い硬化物を提供し難く、従って得られる硬化物
は耐熱性、耐薬品性、機械特性等の点で満足しえないと
いう欠点がある。Conventional technology Traditionally, amines,
Acid anhydrides, phenol novolac resins, etc. have been used, but in recent years, phenol novolac resins have been reconsidered for applications such as laminates and sealants due to demands for higher performance and lower prices of products. This resin is particularly suitable for use in electrical and electronic materials. Therefore, the phenol novolak resin is generally obtained by a condensation reaction of phenols and formaldehyde in the presence of an acid catalyst, and is a linear molecule mainly composed of 2 to 20 phenol nuclei linked by methylene bonds. It is believed that As the above-mentioned raw material phenols, carbolic acid, orthocresol, etc., which usually have one phenolic hydroxyl group, are used.
The resulting resin contains a low molecular weight component consisting of unreacted phenol monomer and binuclear bodies. For these reasons, when this resin is used as a curing agent, it is difficult to provide a cured product with a high crosslinking density, and the resulting cured product is therefore unsatisfactory in terms of heat resistance, chemical resistance, mechanical properties, etc. There is a drawback that it is not possible.
また、従来（１）石炭酸、オルソクレゾール等の一価の
フェノール類、（２）バラ置換アルキルフェノール、バ
ラ置換アリールフェノール等のバラ置換フェノール類及
び（３）ホルムアルデヒドを同時に仕込んで縮合反応さ
せたフェノール−バラ置換フェノール系共縮合ノボラッ
ク樹脂も知られているが、これも上記一般的なフェノー
ルノボラック樹脂に見られると同様に、石炭酸の２核休
やパラ置換フェノール七ツマー等の、エポキシ基の反応
停止剤的な働きをすると考えられる低分子量成分を含み
、所望の硬化特性を発揮し得ない。In addition, conventionally, (1) monohydric phenols such as carbolic acid and orthocresol, (2) rose-substituted phenols such as rose-substituted alkylphenol and rose-substituted arylphenol, and (3) formaldehyde were simultaneously charged and subjected to a condensation reaction. Rose-substituted phenol-based cocondensation novolac resins are also known, but, like the general phenol novolak resins mentioned above, these resins also have the effect of stopping the reaction of epoxy groups such as dinuclear acid of carbolic acid and para-substituted phenol heptamers. It contains low molecular weight components that are thought to act as agents, and cannot exhibit the desired curing properties.
しかも該共縮合ノボラック樹脂は、一般に分子量分布幅
が広く、蒸留等の操作により石炭酸モノマーの含有率を
１重量％以下に調整した場合でもＭｗ ／Ｍｎ （Ｍ
ｗは重層平均分子量値及びＭｎは数平均分子量値を示す
）が、１．５以上の高い値を示し、その溶融粘度の点か
ら取り扱い作業性の面でも硬化剤として不利がある。Moreover, the co-condensed novolak resin generally has a wide molecular weight distribution, and even when the content of the carbolic acid monomer is adjusted to 1% by weight or less by distillation or other operations, Mw /Mn (M
(w indicates the layer average molecular weight value and Mn indicates the number average molecular weight value) exhibits a high value of 1.5 or more, and is disadvantageous as a curing agent in terms of handling and workability due to its melt viscosity.
発明が解決しようとする問題点
本発明は、上記従来技術に鑑み、殊にエポキシ樹脂の硬
化剤として優れた特性を有する新しい多官能性フェノー
ル樹脂、より詳しくは低分子量縮合物の含有量を著しく
低減させ、しかも分子量分布幅の狭い多官能性フェノー
ル樹脂を製造する方法を提供することを目的とする。Problems to be Solved by the Invention In view of the above-mentioned prior art, the present invention is directed to a new polyfunctional phenolic resin having excellent properties as a curing agent for epoxy resins, and more specifically, to a new polyfunctional phenolic resin having a significantly reduced content of low molecular weight condensates. It is an object of the present invention to provide a method for producing a polyfunctional phenolic resin with a reduced molecular weight distribution and a narrow molecular weight distribution width.
同 点を解決するための手段
上記目的は、２，６−ジヒドロキシメチル−４−アルキ
ルフェノール及び２．６−ジヒドロキシメチル−４−ア
リールフェノールから選ばれるバラ置換フェノールのジ
メチロール誘導体とフェノール類とを酸触媒の存在下に
加熱反応させ、次いで脱水及び脱フェノールして、２核
体以下の成分の含有率が５重量％以下、好ましくは２．
５重量％以下であり且つ３核体成分の含有率が３０重量
％以上、好ましくは４０重量％以上であるポリヒドロキ
シ化合物を得ることを特徴とするポリヒドロキシ化合物
の製造法により達成される。Means for Solving the Same Point The above object is to process a dimethylol derivative of a substituted phenol selected from 2,6-dihydroxymethyl-4-alkylphenol and 2,6-dihydroxymethyl-4-arylphenol and phenols using an acid catalyst. The content of components of binuclear bodies or less is 5% by weight or less, preferably 2.
This is achieved by a method for producing a polyhydroxy compound characterized by obtaining a polyhydroxy compound in which the content of the trinuclear component is 5% by weight or less and 30% by weight or more, preferably 40% by weight or more.
本発明者らは、鋭意研究の結果、上記の通り２゜６−ジ
ヒドロキシメチル−４−アルキルフェノール及び２，６
−ジヒドロキシメチル−４−アリールフェノールから選
ばれるバラ置換フェノールのジメチロール誘導体を出発
原料として用い、これを酸触媒の存在下に過剰１１１の
フェノール類と反応させるときには、引続き通常の蒸留
操作等により脱水及び脱フェノールを行なうことにより
目的とする化合物が得られることを見出し、ここに本発
明を完成した。As a result of intensive research, the present inventors discovered that 2゜6-dihydroxymethyl-4-alkylphenol and 2,6
When using a dimethylol derivative of a rose-substituted phenol selected from -dihydroxymethyl-4-arylphenols as a starting material and reacting it with an excess of 111 phenols in the presence of an acid catalyst, it is then dehydrated and dehydrated by conventional distillation. It was discovered that the target compound could be obtained by removing phenol, and the present invention was thus completed.
本発明により得られるポリヒドロキシ化合物は、エポキ
シ基の反応停止剤的な働きをする低分子量成分を殆んど
含んでおらず、その分子量分布幅も狭く、従ってエポキ
シ樹脂の硬化剤として非常に浸れた硬化特性を発揮し、
架橋密度が高く、耐熱性、耐薬品性、機械特性等に優れ
た硬化物を与える特徴を有する。The polyhydroxy compound obtained by the present invention contains almost no low-molecular weight component that functions as a reaction terminator for epoxy groups, and has a narrow molecular weight distribution, so it is very difficult to use as a curing agent for epoxy resins. exhibits excellent hardening properties,
It has a high crosslinking density and is characterized by providing cured products with excellent heat resistance, chemical resistance, mechanical properties, etc.
本発明において、出発原料として用いられるバラ置換フ
ェノールのジメチロール誘導体としては、代表的には例
えば２．６−ジヒドロキシメチル−４−メチルフェノー
ル、２．６−ジヒドロキシメチル−４−エチルフェノー
ル、２．６−ジヒドロキシメチル−４−ｎ−プロピルフ
ェノール、２゜６−ジヒドロキシメチル−４−イソプロ
ピルフェノール、２，６−ジヒドロキシメチル−４−を
一ブチルフェノール、２．６−ジヒドロキシメチル−４
−アミルフェノール、２，６−ジヒドロキシメチル−４
−オクヂルフェノール、２．６−ジヒドロキシメチル−
４−フェニルフェノール等を例示できる。これらのバラ
置換フェノールジメチロール誘導体は、通常の方法に従
い製造できる。例えば２．６−ジヒドロキシメチル−４
−アルキルフェノールは、これに対応するバラ置換アル
キルフェノールとホルムアルデヒドとを水及び塩基性触
媒の存在下に反応させ、次いで酸析することにより高純
度の固形物として収得できる。また、本発明では上記２
，６−ジヒドロキシメチル−４−アルキルフェノールと
して、上記バラ置換アルキルフェノールとホルムアルデ
ヒドとの反応生成物を酸で中和して得られるレゾール型
オイル状物を、その後何らの精製をも行なうことなく使
用することもできる。２．６−ジヒドロキシメチル−４
−７リールフエノール類も、上記と同様にして製造でき
る。In the present invention, the dimethylol derivatives of rose-substituted phenol used as starting materials are typically, for example, 2.6-dihydroxymethyl-4-methylphenol, 2.6-dihydroxymethyl-4-ethylphenol, 2.6-dihydroxymethyl-4-ethylphenol, -dihydroxymethyl-4-n-propylphenol, 2゜6-dihydroxymethyl-4-isopropylphenol, 2,6-dihydroxymethyl-4-monobutylphenol, 2,6-dihydroxymethyl-4
-amylphenol, 2,6-dihydroxymethyl-4
-ocdylphenol, 2,6-dihydroxymethyl-
Examples include 4-phenylphenol. These rose-substituted phenol dimethylol derivatives can be produced according to conventional methods. For example 2,6-dihydroxymethyl-4
-Alkylphenol can be obtained as a highly pure solid by reacting the corresponding partially substituted alkylphenol with formaldehyde in the presence of water and a basic catalyst, followed by acid precipitation. In addition, in the present invention, the above 2
, 6-dihydroxymethyl-4-alkylphenol, a resol-type oil obtained by neutralizing the reaction product of the above-mentioned rose-substituted alkylphenol and formaldehyde with acid, without any subsequent purification. You can also do it. 2.6-dihydroxymethyl-4
-7 Reel phenols can also be produced in the same manner as above.
本発明におけるもう一方の原料であるフェノール類とし
ては、石炭酸の他、例えばクレゾール、キシレノール等
のバラ−又はオルソ−置換アルキルフェノール類、クロ
ロフェノール、ブロモフェノール等のハロゲン化フェノ
ール類等が挙げられる。これらのうちで反応性を考慮す
れば石炭酸及びクレゾールが好ましい。The other raw material phenols in the present invention include, in addition to carbolic acid, rose- or ortho-substituted alkylphenols such as cresol and xylenol, and halogenated phenols such as chlorophenol and bromophenol. Among these, carbolic acid and cresol are preferred in consideration of reactivity.
本発明方法では、まず上記バラ置換フェノールのジメチ
ロール誘導体とフェノール類とを、酸触媒の存在下に加
熱反応させる。ここで用いられる酸触媒としては、特に
制限されず通常のノボラック樹脂の製造に用いられる各
種のものをいずれも使用できる。そのうちで特にシュウ
酸は好適である。バラ置換フェノールジメチロール誘導
体に対するフェノール類の使用量は、該誘導体の有する
メチロール基に対して過剰量、通常約１．２〜１０倍モ
ル旦、好ましくは約１．５〜３．０倍モル量とするのが
よい。この量は上記誘導体そのものに対しては約２．４
〜２０倍モル量の範囲に相当する。上記フェノール類の
使用量がメチロール基に対して１．２倍モルをあまりに
下回る場合、得られる目的物の軟化点や溶融粘度が高く
なり好ましくない。In the method of the present invention, first, the dimethylol derivative of the above-described substituted phenol and a phenol are heated and reacted in the presence of an acid catalyst. The acid catalyst used here is not particularly limited, and any of the various types commonly used in the production of novolac resins can be used. Among these, oxalic acid is particularly suitable. The amount of phenol used for the rose-substituted phenol dimethylol derivative is an excess amount, usually about 1.2 to 10 times the molar amount, preferably about 1.5 to 3.0 times the molar amount, relative to the methylol group possessed by the derivative. It is better to This amount is approximately 2.4 for the above derivative itself.
This corresponds to a range of ~20 times the molar amount. If the amount of the phenol used is much less than 1.2 times the mole of the methylol group, the softening point and melt viscosity of the obtained target product will increase, which is undesirable.
上記反応条件は、該反応による未反応フェノール量、低
分子縮合生成物量、高分子縮合生成物量等を考慮して適
宜決定されるが、通常約５０〜１００℃、好ましくは約
６０〜８０℃の温度条件が採用でき、約３〜６時間上記
温度で加熱するのがよい。The above reaction conditions are appropriately determined taking into account the amount of unreacted phenol, the amount of low-molecular condensation products, the amount of high-molecular condensation products, etc. caused by the reaction, but are usually about 50 to 100°C, preferably about 60 to 80°C. Any temperature condition may be employed, preferably heating at the above temperature for about 3 to 6 hours.
本発明では、次いで脱水及び脱フェノールを行なう。こ
れは具体的には、通常の蒸留操作に従って実施できる。In the present invention, dehydration and dephenolization are then performed. This can be carried out in particular according to conventional distillation operations.
この蒸留方法は特に制限されず、公知の各種方法、例え
ば減圧蒸留、薄膜蒸留、水蒸気蒸留等のいずれによって
もよい。但しこの蒸゛ 留操作によっては２核体以
上の縮合物は殆んど除去できない。本発明では、上記の
ようにバラ置換フェノールのジメチロール誘導体に対し
て過剰のフェノール類を用いることにより、上記誘導体
のメチロール基相互の縮合反応を抑え、２核体以上の縮
合物の生成を最小限に抑制させるものである。This distillation method is not particularly limited, and any of various known methods such as vacuum distillation, thin film distillation, steam distillation, etc. may be used. However, this distillation operation hardly removes condensates of two or more nuclear bodies. In the present invention, as described above, by using an excess of phenols with respect to the dimethylol derivative of the rose-substituted phenol, the condensation reaction between the methylol groups of the derivative is suppressed, and the formation of condensates of two or more nuclei is minimized. This is to suppress it.
かくして本発明によれば２核体以下の成分の含有率が５
重量％以下であり且つ３核体成分の含有率が３０＠量％
以上（通常３０〜８０重Ｍ％の範囲にある）であり、分
子量分布幅の狭い所望のポリヒドロキシ化合物を得るこ
とができる。Thus, according to the present invention, the content of components of binuclear bodies or less is 5
% by weight or less, and the content of trinuclear components is 30% by weight
or more (usually in the range of 30 to 80% by weight), and a desired polyhydroxy compound with a narrow molecular weight distribution width can be obtained.
本発明方法により得られるポリヒドロキシ化合物は、下
記一般式（１）で表わされるフェノール核で換算して３
核体を主体とするフェノールノボラック樹脂であると推
定される。The polyhydroxy compound obtained by the method of the present invention has a phenolic nucleus represented by the following general formula (1).
It is presumed to be a phenolic novolac resin mainly consisting of nuclear bodies.
Ｈ
Ｒ１（１）
Ｃ式中、Ｒ１はアルキル基又はアリール基を、Ｒ２は水
素原子又はアルキル基を、Ｒ３は水素原子、アルキル基
又はハロゲン原子を各々示す。〕
本発明方法により得られる上記ポリヒドロキシ化合物は
、エポキシ樹脂の硬化剤として非常に有用である。該硬
化剤としての利用に当り、本発明ポリヒドロキシ化合物
は、各種エポキシ樹脂及び必要に応じて硬化促進剤、そ
の他の添加剤等と配合され、エポキシ樹脂組成物とされ
、例えば電子部品の封止材料、積層板、粉体塗料等の用
途に好適に使用することができる。更に該ポリヒドロキ
シ化合物は、ポリウレタン用のポリオール成分として或
いはエポキシ樹脂原料として用いることもできる。H R1 (1) In the formula, R1 represents an alkyl group or an aryl group, R2 represents a hydrogen atom or an alkyl group, and R3 represents a hydrogen atom, an alkyl group, or a halogen atom. ] The above polyhydroxy compound obtained by the method of the present invention is very useful as a curing agent for epoxy resins. When used as a curing agent, the polyhydroxy compound of the present invention is blended with various epoxy resins and, if necessary, a curing accelerator and other additives to form an epoxy resin composition, which can be used, for example, to seal electronic parts. It can be suitably used for materials, laminates, powder coatings, etc. Furthermore, the polyhydroxy compound can also be used as a polyol component for polyurethane or as a raw material for epoxy resin.
実 施 例
以下、本発明方法の実施例及び比較例を挙げ、本発明を
更に詳しく説明するが、本発明は之等各例に限定される
ものではない。尚、各例中、部及び％は特記しない限り
すべて重量基準である。EXAMPLES Hereinafter, the present invention will be explained in more detail by giving examples and comparative examples of the method of the present invention, but the present invention is not limited to these examples. In each example, all parts and percentages are based on weight unless otherwise specified.
実施例１
撹拌機、温度計及び冷却器を備えた１Ｑ容フラスコ内を
窒素ガスで置換した後、１，６−ジヒドロキシメチル−
４−ｔ−ブチルフェノール２１０部（１モル）、石炭酸
２８２部（３モル）及びシュウ酸１．４部を入れ、窒素
気流下に７０℃で４時間反応させ、その後減圧下に脱水
し、水蒸気蒸留により脱フェノールを行ない、フェノー
ルモノマー含量が１．０％以下になるように調整して、
本発明のポリヒドロキシ化合物を得た。これを「化合物
Ａ」という。Example 1 After purging the inside of a 1Q flask equipped with a stirrer, thermometer and condenser with nitrogen gas, 1,6-dihydroxymethyl-
210 parts (1 mol) of 4-t-butylphenol, 282 parts (3 mol) of carbolic acid, and 1.4 parts of oxalic acid were added and reacted at 70°C for 4 hours under a nitrogen stream, followed by dehydration under reduced pressure and steam distillation. to remove phenol and adjust the phenol monomer content to 1.0% or less,
A polyhydroxy compound of the present invention was obtained. This is called "compound A."
実施例２
実施例１において、石炭酸の使用量を４７０部（５モル
）に変化させた他は同様にして、フェノールモノマー含
量が１．０％以下のポリヒドロキシ化合物を得た。これ
を「化合物Ｂ」という。Example 2 A polyhydroxy compound having a phenol monomer content of 1.0% or less was obtained in the same manner as in Example 1, except that the amount of carbolic acid used was changed to 470 parts (5 moles). This is called "compound B."
比較例１
撹拌機、温度計及び冷却器を備えた１Ｑ容フラスコ内に
、窒素ガスで置換した後、石炭Ｍｌ ８８部（２モル）
、３７％ホルマリン１２２部（１，５モル）及びシュウ
酸０．７部を入れ、窒素気流下に還流温度下に３時間反
応させ、その接減圧下に脱水し、水蒸気蒸留により脱フ
ェノールを行ない、フェノールモノマー含量が１．０％
以下になるように調整して、ポリヒドロキシ化合物を得
た。これを「比較化合物Ｃ」という。Comparative Example 1 88 parts (2 mol) of coal Ml was placed in a 1Q flask equipped with a stirrer, thermometer, and cooler after purging with nitrogen gas.
, 122 parts (1.5 moles) of 37% formalin and 0.7 parts of oxalic acid were reacted under a nitrogen stream at reflux temperature for 3 hours, dehydrated under reduced pressure, and dephenolized by steam distillation. , phenol monomer content is 1.0%
A polyhydroxy compound was obtained by adjusting the following. This is called "comparative compound C."
上記実施例及び比較例で得られた各ポリヒドロキシ化合
物の性状を求めた結果を第１表及び第１図〜第３図に示
す。The results of determining the properties of each polyhydroxy compound obtained in the above Examples and Comparative Examples are shown in Table 1 and Figures 1 to 3.
第１表において、各成分含量及びＭｗ ／Ｍｎは、力５
ム（Ｇ−４０００Ｈ８及びＧ−２０００Ｈ８）゛
を用いて測定されたものであり、軟化点は環球法により
求められたものである。In Table 1, the content of each component and Mw /Mn are
(G-4000H8 and G-2000H8)
The softening point was determined using the ring and ball method.
第 １ 表
また第１図〜第３図は、化合物Ａ１化合物Ｂ及び比較化
合物Ｃの各々について高速液体クロマトグラフ測定装Ｍ
（東洋四速社製、ＨＬＣ−８０２Ａ、ｃｐ−８０００）
を用いて測定した分子量分布を示すグラフであり、図中
、横軸は溶出カウント数を、縦軸はピーク強度を示す。Table 1 and FIGS. 1 to 3 show the high performance liquid chromatograph measuring device M for each of Compound A, Compound B, and Comparative Compound C.
(Manufactured by Toyo Shisokusha, HLC-802A, cp-8000)
1 is a graph showing the molecular weight distribution measured using a method, in which the horizontal axis shows the elution count number and the vertical axis shows the peak intensity.
各図の対比より明ｄかな通り、本発明方法により得られ
るポリヒドロキシ化合物（第１図及び第２図）は、比較
例で得たそれ（第３図）に比し、分子量分布幅が狭く、
しかも３核体を主成分としていることが判る。As is clear from the comparison of each figure, the polyhydroxy compound obtained by the method of the present invention (Figures 1 and 2) has a narrower molecular weight distribution width than that obtained in the comparative example (Figure 3). ,
Furthermore, it can be seen that the main component is trinuclear bodies.
第１図〜第３図は、本発明実施例１及び２で得たポリヒ
ドロキシ化合物並びに比較例１で得たポリヒドロキシ化
合物の各々の分子量分布を求めたグラフである。
（以 上）1 to 3 are graphs showing the molecular weight distributions of the polyhydroxy compounds obtained in Examples 1 and 2 of the present invention and the polyhydroxy compound obtained in Comparative Example 1. (that's all)
Claims (2)
ノール及び２，６−ジヒドロキシメチル−４−アリール
フェノールから選ばれるパラ置換フェノールのジメチロ
ール誘導体とフェノール類とを酸触媒の存在下に加熱反
応させ、次いで脱水及び脱フェノールして、２核体以下
の成分の含有率が５重量％以下であり且つ３核体成分の
含有率が３０重量％以上であるポリヒドロキシ化合物を
得ることを特徴とするポリヒドロキシ化合物の製造法。(1) A dimethylol derivative of para-substituted phenol selected from 2,6-dihydroxymethyl-4-alkylphenol and 2,6-dihydroxymethyl-4-arylphenol is reacted with phenols by heating in the presence of an acid catalyst, and then A polyhydroxy compound obtained by dehydration and dephenolization to obtain a polyhydroxy compound in which the content of dinuclear components or less is 5% by weight or less and the content of ternary components is 30% by weight or more. Method of manufacturing the compound.
てフェノール類の仕込み比率が２．４〜２０モル倍であ
る特許請求の範囲第１項に記載の方法。(2) The method according to claim 1, wherein the molar ratio of the phenol to the dimethylol derivative of the para-substituted phenol is 2.4 to 20 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25919885A JPS62119220A (en) | 1985-11-18 | 1985-11-18 | Production of polyhydroxyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25919885A JPS62119220A (en) | 1985-11-18 | 1985-11-18 | Production of polyhydroxyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62119220A true JPS62119220A (en) | 1987-05-30 |
| JPH0569127B2 JPH0569127B2 (en) | 1993-09-30 |
Family
ID=17330741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25919885A Granted JPS62119220A (en) | 1985-11-18 | 1985-11-18 | Production of polyhydroxyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62119220A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62212410A (en) * | 1986-03-14 | 1987-09-18 | Asahi Chiba Kk | Production of novolak resin and its glycidyl ether |
| US5395915A (en) * | 1992-02-27 | 1995-03-07 | Mitsui Toatsu Chemicals, Inc. | Method for simultaneous preparation of bisphenol F and novolak phenol resins |
| WO2003042267A1 (en) * | 2001-11-16 | 2003-05-22 | Asahi Organic Chemicals Industry Co., Ltd. | Phenolic novolaks and process for production thereof |
| WO2013125620A1 (en) * | 2012-02-23 | 2013-08-29 | 新日鉄住金化学株式会社 | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof |
| WO2015175551A1 (en) * | 2014-05-12 | 2015-11-19 | Si Group, Inc. | Modified phenolic resins and methods of making and using the same as reinforcing resins |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5257153A (en) * | 1975-10-30 | 1977-05-11 | Sir Soc Italiana Resine Spa | Polyhydroxyphenol and process for preparing same |
-
1985
- 1985-11-18 JP JP25919885A patent/JPS62119220A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5257153A (en) * | 1975-10-30 | 1977-05-11 | Sir Soc Italiana Resine Spa | Polyhydroxyphenol and process for preparing same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62212410A (en) * | 1986-03-14 | 1987-09-18 | Asahi Chiba Kk | Production of novolak resin and its glycidyl ether |
| JPH0662731B2 (en) * | 1986-03-14 | 1994-08-17 | 旭チバ株式会社 | Production method of novolac resin |
| US5395915A (en) * | 1992-02-27 | 1995-03-07 | Mitsui Toatsu Chemicals, Inc. | Method for simultaneous preparation of bisphenol F and novolak phenol resins |
| WO2003042267A1 (en) * | 2001-11-16 | 2003-05-22 | Asahi Organic Chemicals Industry Co., Ltd. | Phenolic novolaks and process for production thereof |
| US7241833B2 (en) | 2001-11-16 | 2007-07-10 | Asahi Organic Chemicals Industry Co.., Ltp | Phenolic novolaks and process for production thereof |
| WO2013125620A1 (en) * | 2012-02-23 | 2013-08-29 | 新日鉄住金化学株式会社 | Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof |
| JPWO2013125620A1 (en) * | 2012-02-23 | 2015-07-30 | 新日鉄住金化学株式会社 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
| WO2015175551A1 (en) * | 2014-05-12 | 2015-11-19 | Si Group, Inc. | Modified phenolic resins and methods of making and using the same as reinforcing resins |
| US9765174B2 (en) | 2014-05-12 | 2017-09-19 | Si Group, Inc. | Modified phenolic resins and methods of making and using the same as reinforcing resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0569127B2 (en) | 1993-09-30 |
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