JP3814979B2 - Method for producing phenolic resin-based self-curing resin - Google Patents
Method for producing phenolic resin-based self-curing resin Download PDFInfo
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- JP3814979B2 JP3814979B2 JP26597697A JP26597697A JP3814979B2 JP 3814979 B2 JP3814979 B2 JP 3814979B2 JP 26597697 A JP26597697 A JP 26597697A JP 26597697 A JP26597697 A JP 26597697A JP 3814979 B2 JP3814979 B2 JP 3814979B2
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- Phenolic Resins Or Amino Resins (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、印刷回路板や多層印刷回路板等に用いられる積層板、半導体封止材などのエレクトロニクス用材料に最適な耐熱性を有する熱硬化性樹脂であるフェノール樹脂系自硬化性樹脂の改良された製造方法に関する。
【0002】
【従来の技術】
フェノール樹脂は、フェノール類とホルムアルデヒドとを塩基性あるいは酸性触媒の存在下に反応させて合成する樹脂であり、一般には、塩基性触媒下では、自硬化性のレゾール型フェノール樹脂、酸性触媒の存在下では、熱可塑性のノボラック型フェノール樹脂が得られる。ノボラック型フェノール樹脂は、それ自身だけでは硬化せず、ヘキサメチレンテトラミンなどの硬化剤が必要である。これらのフェノール樹脂は、硬化時に水やホルムアルデヒド、アンモニアなどの低分子量のガスを発生させる欠点がある。
【0003】
【発明が解決しようとする課題】
硬化時に低分子量のガスを発生させるフェノール樹脂に対し、重合可能で低分子量化合物を副生成しないフェノール樹脂として、特開昭49−47378号公報に開示されている、ホルムアルデヒドと第一ジアミンとフェノールから合成されるオキサジン環を有する樹脂がある。この樹脂は、前述した欠点がなく良好な性能を示すが、この特許で開示されている方法は、ホルムアルデヒド源にホルムアルデヒドの水溶液を用いているため、反応終了後、水相を分離するか、均一反応系で行うため高価なジオキサンなどの溶剤を使用しており樹脂を合成するプロセスが複雑であり、得られる樹脂のコストアップの要因となっていた。
そこで、従来のフェノール樹脂の欠点である低分子量物質の副生成がなく、また、特開昭49−47378号公報に記載されているようなオキサジン環を有する樹脂を記載されている方法とは異なる簡単な合成方法で製造することを目的に種々検討した。
【0004】
【課題を解決するための手段】
本発明は、フェノール類、アルデヒド類、第1級アミンを反応させて得られるオキサジン環を含むフェノール樹脂系自硬化性樹脂の製造方法において、アルコール系溶剤中でフェノール類、パラホルム及び芳香族ジアミンを反応させるフェノール樹脂系自硬化性樹脂の製造方法である。また、本発明は、前記アルコール系溶剤に、メタノール、エタノール、n−プロパノール、i−プロパノール、n−ブタノール、i−ブタノール、t−ブタノールの中から選ばれる少なくとも1種類以上の溶剤を使用し、92重量%以上のホルムアルデヒドの含有量であるパラホルムを用い、芳香族ジアミンが、4,4’−ジアミノジフェニルメタンであると好ましいフェノール樹脂系自硬化性樹脂の製造方法である。
【0005】
【発明の実施の形態】
本発明は、フェノール類とホルムアルデヒドと芳香族ジアミン類から脱水縮合して生成する水以外にはできるだけ水分が反応系内に少なくなるようにすることが、オキサジン環(オキサザテトラリン環)を有する樹脂の合成に都合が良いことが分かった。系内の水分を少なくするためには、前述した特許(特開昭49−47378号公報)に記載されているようなホルムアルデヒドの水溶液は使用すべきでなく、水分の少ないパラホルムをホルムアルデヒド源として使用する事によって、反応途中での反応物の粘度上昇がみられず、撹拌が容易にできる合成プロセスを確立するに至った。
【0006】
本発明のフェノール樹脂系自硬化性樹脂の製造方法を説明すると、フェノール類とパラホルム及び溶剤としてパラホルムと親和性のあるアルコール系溶剤を用い、系を加熱してパラホルムとフェノール類を溶剤に一部あるいは全部を溶解する。その後、反応系を70℃以下に冷却し、芳香族ジアミンを発熱反応による温度上昇を抑制しながら添加する。添加終了後、還流温度で反応を継続し、所定のゲル化時間になったところで、溶剤を留去し、減圧下脱水濃縮し、目的のゲル化時間で反応終点とする。
【0007】
本発明で使用するフェノール類は、フェノール、o−,m−,p−クレゾール、キシレノール、ノニルフェノール、p−,t−ブチルフェノール、オクチルフェノールなど一価のフェノール類が例示できる。
また、パラホルムは、80重量%以上のホルムアルデヒド含有量のもの、特に92重量%以上の含有量のものが好ましい。
芳香族ジアミンには、m−フェニレンジアミン、p−フェニレンジアミン、4、4’−ジアミノジフェニルメタン、4、4’−ジアミノジフェニルエーテル、4、4’−ジアミノジフェニルスルホン、2,2−ビス〔(4-アミノフェノキシ)フェニル〕プロパンなどが挙げられる。
また、本発明で使用するアルコール系溶剤には、メタノール、エタノール、n−プロパノール、i−プロパノール、n−ブタノール、i−ブタノール、t−ブタノールなどが挙げられる。特に、メタノールが価格、パラホルムとの親和性から好ましい。
【0008】
アルコール系溶剤中にパラホルムとフェノール類を添加し、一部あるいは全部を溶解する。その後、反応系を70℃以下に冷却し、芳香族ジアミンを発熱反応による温度上昇を抑制しながら添加する。芳香族ジアミンの添加は、反応系の温度を50℃〜70℃で行うのが好ましい。50℃未満では、芳香族ジアミンおよびパラホルムが溶解しないままに、反応が進み、未反応のパラホルム、芳香族ジアミンが反応系内に残り、樹脂として好ましくない。また、70℃を超えると、部分的に反応が進み、均一な樹脂が得られない。
使用するアルコール系溶剤の量は、パラホルムの量の0.5倍〜2.0倍、特に1.0〜1.5倍が好ましい。0.5倍未満では、パラホルムの未溶解部分が多くなり均一に反応しにくくなるため樹脂中に未反応の原料が残る。また、2.0倍を超えると、反応で副生成する水を除去するのに、多くの時間を要するようになる。
【0009】
本発明のフェノール樹脂系自硬化性樹脂は、化1に示す反応で得られるものと考えられる。反応は、十分解析されているわけではないが、芳香族ジアミンとしてジアミノジフェニルメタンを例にして説明すると、ジアミノジフェニルメタンにホルムアルデヒドが付加反応し、メチロール化合物を生じる。そして、このメチロール化合物とフェノールが縮合反応して、オキサジン環を形成する。そして、このオキサジン環含有化合物が、主として硬化時に開環し硬化する。そして、この硬化では副生物が生じない。この反応は、理想的には、芳香族ジアミン1モルに対し、ホルムアルデヒド4モル、フェノール類2モルの反応である。しかし、三者のモル比はこれに限定されるものではなく、フェノール類、ホルムアルデヒドを過剰にした場合でも芳香族ジアミンから生成したオキサジン環化合物とフェノール類、ホルムアルデヒド反応生成物を共重合させることもできる。
【0010】
【化1】
【0011】
本発明による樹脂は、従来のフェノール樹脂とは異なり、硬化時に水が副生成することがないので、耐熱性を必要とする種々の分野に応用することができる。たとえば、ガラス布や紙を基材とした金属張積層板や封止材などのエレクトロニクス分野、成型材料、摩擦材などの結合材分野に応用することができる。
以下に実施例を示し本発明をさらに具体的に説明する。
【0012】
【実施例】
(実施例1)
温度計、撹拌機、冷却器を備えた5リットルのフラスコに、フェノール940g(10モル)、メタノール900ml、92重量%含有パラホルム652g(20モル)をいれ、加熱還流して、パラホルムをフェノールに懸濁した。懸濁液が50℃になったら、4,4’−ジアミノジフェニルメタン990g(5モル)を分割して添加した。添加終了後、反応温度を上昇させ、還流する。反応液は乳化を示し乳化してから反応を2時間継続した。反応終了後、減圧下に、溶剤および副生成した水を留去した。反応の終点は、160℃の熱板上でのゲル化時間が15分になった時点とした。これに、さらにメチルエチルケトンを1000g添加してワニスを製造した。
このワニスを離型剤処理したポリエチレンテレフタレート(PET)フィルムに塗布し、乾燥機で加熱し、溶剤を揮散させB−ステージ状態の樹脂を作製した。この樹脂をPETフィルムから剥離し、ステンレス鏡板に載せた50mm×50mmにくりぬいたテフロン製の型枠でつくったキャビティに所定量入れ、さらにステンレス鏡板を重ね、170℃、90分間、40Kg/cm2の条件で加熱加圧して厚さ1.5mmの樹脂板を作製した。樹脂板のガラス転移温度を粘弾性法で測定したところ215℃であった。
【0013】
(実施例2)
実施例1と同様にして、フラスコに、m、p−クレゾール1080g(10モル)、イソプロパノール500ml、95重量%含有パラホルム631.6g(20モル)を投入し、加熱還流して、パラホルムをm、p−クレゾールに懸濁した。懸濁液が50℃になったら、4,4’−ジアミノジフェニルメタン990g(5モル)を分割して添加した。添加終了後、反応温度を上昇させ、還流した。反応液は乳化を示し乳化してから反応を2時間継続した。反応終了後、減圧下に、溶剤および副生成した水を留去した。反応の終点は、160℃の熱板上でのゲル化時間が12分になった時点とした。これに、さらにメチルエチルケトンを1000g添加してワニスを製造した。
このワニスを離型剤処理したPETフィルムに塗布し、乾燥機で加熱し、溶剤を揮散させB−ステージ状態の樹脂を作製した。この樹脂をPETフィルムから剥離し、ステンレス鏡板に載せた50mm×50mmにくりぬいたテフロン製の型枠でつくったキャビティに所定量入れ、さらにステンレス鏡板を重ね、加熱加圧して厚さ1.5mmの樹脂板を作製した。樹脂板のガラス転移温度を粘弾性法で測定したところ209℃であった。
【0014】
(実施例3)
実施例1と同様にして、フラスコに、m、p−クレゾール1080g(10モル)、イソプロパノール500ml、95重量%含有パラホルム631.6g(20モル)を投入し、加熱還流して、パラホルムをm,p−クレゾールに懸濁した。懸濁液が50℃になったら、4,4’−ジアミノジフェニルエーテル1000g(5モル)を分割して添加した。添加終了後、反応温度を上昇させ、還流した。反応液は乳化を示し乳化してから反応を2時間継続した。反応終了後、減圧下に、溶剤および副生成した水を留去した。反応の終点は、160℃の熱板上でのゲル化時間が10分になった時点をとした。これに、さらにメチルエチルケトン1000g添加してワニスを製造した。
このワニスを離型剤処理したPETフィルムに塗布し、乾燥機で加熱し、溶剤を揮散させB−ステージ状態の樹脂を作製した。この樹脂をPETフィルムから剥離し、ステンレス鏡板に載せた50mm×50mmにくりぬいたテフロン製の型枠でつくったキャビティに所定量入れ、さらにステンレス鏡板を重ね、加熱加圧して厚さ1.5mmの樹脂板を作製した。樹脂板のガラス転移温度を粘弾性法で測定したところ215℃であった。
【0015】
(比較例)
実施例1と同様にして、フラスコに、フェノール940g(10モル)、ホルマリン(37重量%ホルムアルデヒド含有)1621g(20モル)を投入した。溶液は、均一透明になった。それに、4,4’−ジアミノジフェニルメタン990g(5モル)を約50℃で30分かけて反応系内に分割して投入しようとしたが、反応が進むにつれ溶液は白濁し、全部を添加する前に高分子量化してしまい撹拌が困難となり、反応を中断した。
【0016】
【発明の効果】
本発明のフェノール樹脂系自硬化性樹脂の製造方法は、系内の水分を少なくするためパラホルムと親和性の高いアルコール系溶剤を使用することにより、オキサジン環を有し、硬化時に水やホルムアルデヒドが発生しない耐熱性のフェノール樹脂系自硬化性樹脂を簡単な合成方法で製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is an improvement of a phenolic resin-based self-curing resin, which is a thermosetting resin having optimum heat resistance for electronic materials such as laminated boards used in printed circuit boards and multilayer printed circuit boards, and semiconductor encapsulants. Related to the manufacturing method.
[0002]
[Prior art]
A phenolic resin is a resin synthesized by reacting phenols with formaldehyde in the presence of a basic or acidic catalyst. Generally, in the presence of a basic catalyst, a self-curing resol phenolic resin or an acidic catalyst is present. Below, a thermoplastic novolac phenolic resin is obtained. The novolak type phenol resin is not cured by itself, and a curing agent such as hexamethylenetetramine is required. These phenolic resins have the drawback of generating low molecular weight gases such as water, formaldehyde and ammonia during curing.
[0003]
[Problems to be solved by the invention]
As a phenol resin that can be polymerized and does not by-produce a low molecular weight compound with respect to a phenol resin that generates a low molecular weight gas during curing, it is disclosed in JP-A-49-47378, from formaldehyde, a primary diamine, and phenol. There are resins with oxazine rings that are synthesized. This resin does not have the disadvantages described above and exhibits good performance. However, the method disclosed in this patent uses an aqueous solution of formaldehyde as the formaldehyde source. Since it is carried out in a reaction system, an expensive solvent such as dioxane is used, and the process for synthesizing the resin is complicated, resulting in an increase in the cost of the resulting resin.
Therefore, there is no by-product of low molecular weight substances, which is a drawback of conventional phenol resins, and it is different from the method described for resins having an oxazine ring as described in JP-A-49-47378. Various studies were conducted for the purpose of producing by a simple synthesis method.
[0004]
[Means for Solving the Problems]
The present invention relates to a method for producing a phenol resin-based self-curing resin containing an oxazine ring obtained by reacting phenols, aldehydes, and primary amines. In an alcohol solvent, phenols, paraform and aromatic diamine are mixed. It is a manufacturing method of the phenol resin self-curing resin to be reacted. Moreover, the present invention uses at least one solvent selected from methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and t-butanol as the alcohol solvent, This is a preferred method for producing a phenol resin-based self-curing resin, wherein paraform having a content of formaldehyde of 92% by weight or more is used and the aromatic diamine is 4,4′-diaminodiphenylmethane.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a resin having an oxazine ring (oxazatetralin ring) in which the amount of water other than water generated by dehydration condensation from phenols, formaldehyde and aromatic diamines is reduced in the reaction system as much as possible. It turned out to be convenient for the synthesis of In order to reduce the water content in the system, an aqueous solution of formaldehyde as described in the above-mentioned patent (Japanese Patent Laid-Open No. 49-47378) should not be used, and paraform with a low water content is used as the formaldehyde source. By doing this, the viscosity of the reaction product was not increased during the reaction, and a synthesis process that can be easily stirred was established.
[0006]
The process for producing the phenolic resin-based self-curing resin of the present invention will be described. Phenols, paraform, and an alcohol solvent having an affinity for paraform as a solvent are used. Alternatively, dissolve everything. Thereafter, the reaction system is cooled to 70 ° C. or lower, and the aromatic diamine is added while suppressing the temperature rise due to the exothermic reaction. After completion of the addition, the reaction is continued at the reflux temperature, and when the predetermined gelation time is reached, the solvent is distilled off, dehydrating and concentrating under reduced pressure, and the reaction is terminated at the target gelation time.
[0007]
Examples of the phenols used in the present invention include monohydric phenols such as phenol, o-, m-, p-cresol, xylenol, nonylphenol, p-, t-butylphenol, and octylphenol.
Further, paraform having a formaldehyde content of 80% by weight or more, particularly 92% by weight or more is preferable.
Aromatic diamines include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 2,2-bis [(4- Aminophenoxy) phenyl] propane and the like.
Examples of the alcohol solvent used in the present invention include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and t-butanol. In particular, methanol is preferable from the viewpoint of price and affinity with paraform.
[0008]
Add paraform and phenols in an alcohol solvent and dissolve part or all. Thereafter, the reaction system is cooled to 70 ° C. or lower, and the aromatic diamine is added while suppressing the temperature rise due to the exothermic reaction. The aromatic diamine is preferably added at a reaction system temperature of 50 ° C to 70 ° C. If it is less than 50 ° C., the reaction proceeds without dissolving the aromatic diamine and paraform, and unreacted paraform and aromatic diamine remain in the reaction system, which is not preferable as a resin. Moreover, when it exceeds 70 degreeC, reaction will advance partially and uniform resin will not be obtained.
The amount of the alcohol solvent used is preferably 0.5 to 2.0 times, more preferably 1.0 to 1.5 times the amount of paraform. If it is less than 0.5 times, the undissolved part of paraform increases and it becomes difficult to react uniformly, so that unreacted raw materials remain in the resin. On the other hand, if it exceeds 2.0 times, it takes a lot of time to remove water by-produced by the reaction.
[0009]
The phenol resin self-curing resin of the present invention is considered to be obtained by the reaction shown in Chemical Formula 1. Although the reaction has not been sufficiently analyzed, when diaminodiphenylmethane is described as an example of an aromatic diamine, formaldehyde is added to diaminodiphenylmethane to produce a methylol compound. Then, this methylol compound and phenol undergo a condensation reaction to form an oxazine ring. The oxazine ring-containing compound is opened and cured mainly during curing. And by-product does not arise in this hardening. This reaction is ideally a reaction of 4 moles of formaldehyde and 2 moles of phenols per mole of aromatic diamine. However, the molar ratio of the three is not limited to this, and even when phenols and formaldehyde are excessive, an oxazine ring compound formed from an aromatic diamine, phenols, and formaldehyde reaction products can be copolymerized. it can.
[0010]
[Chemical 1]
[0011]
Unlike conventional phenolic resins, the resin according to the present invention does not by-produce water during curing, and therefore can be applied to various fields that require heat resistance. For example, it can be applied to the field of electronics such as metal-clad laminates and sealing materials based on glass cloth or paper, and the field of binders such as molding materials and friction materials.
The present invention will be described more specifically with reference to the following examples.
[0012]
【Example】
Example 1
In a 5 liter flask equipped with a thermometer, stirrer, and condenser, 940 g (10 mol) of phenol, 900 ml of methanol, and 652 g (20 mol) of paraform containing 92% by weight were heated and refluxed, and the paraform was suspended from phenol. It became cloudy. When the suspension reached 50 ° C., 990 g (5 mol) of 4,4′-diaminodiphenylmethane was added in portions. After the addition is complete, the reaction temperature is raised to reflux. The reaction solution showed emulsification, and after emulsification, the reaction was continued for 2 hours. After completion of the reaction, the solvent and by-product water were distilled off under reduced pressure. The end point of the reaction was the time when the gelation time on a hot plate at 160 ° C. became 15 minutes. To this, 1000 g of methyl ethyl ketone was further added to produce a varnish.
This varnish was applied to a polyethylene terephthalate (PET) film treated with a release agent, heated with a dryer, and the solvent was stripped to prepare a B-stage resin. This resin is peeled from the PET film and put in a predetermined amount in a cavity made of a Teflon mold frame hollowed to 50 mm × 50 mm placed on a stainless steel mirror plate, and further overlapped with a stainless steel mirror plate, 170 ° C., 90 minutes, 40 kg / cm 2 The resin plate having a thickness of 1.5 mm was prepared by heating and pressing under the conditions of It was 215 degreeC when the glass transition temperature of the resin plate was measured by the viscoelasticity method.
[0013]
(Example 2)
In the same manner as in Example 1, 1080 g (10 mol) of m, p-cresol, 500 ml of isopropanol, and 631.6 g (20 mol) of paraform containing 95% by weight were put into a flask, heated to reflux, and the paraform was converted to m, Suspended in p-cresol. When the suspension reached 50 ° C., 990 g (5 mol) of 4,4′-diaminodiphenylmethane was added in portions. After completion of the addition, the reaction temperature was raised and refluxed. The reaction solution showed emulsification, and after emulsification, the reaction was continued for 2 hours. After completion of the reaction, the solvent and by-product water were distilled off under reduced pressure. The end point of the reaction was the time when the gelation time on a hot plate at 160 ° C. became 12 minutes. To this, 1000 g of methyl ethyl ketone was further added to produce a varnish.
This varnish was applied to a PET film treated with a release agent, heated with a dryer, and the solvent was stripped to prepare a B-stage resin. This resin is peeled from the PET film, put in a predetermined amount into a cavity made of a Teflon mold frame hollowed to 50 mm × 50 mm placed on a stainless steel mirror plate, and further laminated with a stainless steel mirror plate, heated and pressurized to a thickness of 1.5 mm A resin plate was prepared. It was 209 degreeC when the glass transition temperature of the resin plate was measured by the viscoelasticity method.
[0014]
Example 3
In the same manner as in Example 1, 1080 g (10 mol) of m, p-cresol, 500 ml of isopropanol, 631.6 g (20 mol) of paraform containing 95% by weight were charged into a flask, heated to reflux, and the paraform was converted to m, Suspended in p-cresol. When the suspension reached 50 ° C., 1000 g (5 mol) of 4,4′-diaminodiphenyl ether was added in portions. After completion of the addition, the reaction temperature was raised and refluxed. The reaction solution showed emulsification, and after emulsification, the reaction was continued for 2 hours. After completion of the reaction, the solvent and by-product water were distilled off under reduced pressure. The end point of the reaction was defined as the time when the gelation time on a hot plate at 160 ° C. reached 10 minutes. To this, 1000 g of methyl ethyl ketone was further added to produce a varnish.
This varnish was applied to a PET film treated with a release agent, heated with a dryer, and the solvent was stripped to prepare a B-stage resin. This resin is peeled from the PET film, put in a predetermined amount into a cavity made of a Teflon mold frame hollowed to 50 mm × 50 mm placed on a stainless steel mirror plate, and further laminated with a stainless steel mirror plate, heated and pressurized to a thickness of 1.5 mm A resin plate was prepared. It was 215 degreeC when the glass transition temperature of the resin plate was measured by the viscoelasticity method.
[0015]
(Comparative example)
In the same manner as in Example 1, 940 g (10 mol) of phenol and 1621 g (20 mol) of formalin (containing 37 wt% formaldehyde) were put into a flask. The solution became uniformly transparent. In addition, 990 g (5 mol) of 4,4′-diaminodiphenylmethane was divided and charged into the reaction system at about 50 ° C. over 30 minutes, but as the reaction progressed, the solution became cloudy and before all was added. The molecular weight was increased to make stirring difficult, and the reaction was interrupted.
[0016]
【The invention's effect】
The method for producing a phenol resin self-curing resin of the present invention has an oxazine ring by using an alcohol solvent having a high affinity with paraform in order to reduce moisture in the system. A heat-resistant phenol resin self-curing resin that does not occur can be produced by a simple synthesis method.
Claims (4)
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JP26597697A JP3814979B2 (en) | 1997-09-30 | 1997-09-30 | Method for producing phenolic resin-based self-curing resin |
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JP26597697A JP3814979B2 (en) | 1997-09-30 | 1997-09-30 | Method for producing phenolic resin-based self-curing resin |
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JP4956293B2 (en) * | 2007-06-25 | 2012-06-20 | 積水化学工業株式会社 | Thermosetting resin, thermosetting composition containing the same, and molded product obtained therefrom |
TW200914479A (en) * | 2007-08-02 | 2009-04-01 | Sekisui Chemical Co Ltd | Method for producing thermosetting resin having benzoxazine ring |
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