JP4618037B2 - Phenolic resin compositions having excellent curability and cured products thereof - Google Patents
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本発明は、硬化時間をより短縮できるフェノール樹脂組成物及びこれらの硬化物に関するものである。 The present invention relates to a phenol resin composition capable of further shortening the curing time and these cured products.
フェノール樹脂には、熱可塑性であるノボラック型と熱硬化性であるレゾール型との２種類があり、ノボラック型フェノール樹脂は硬化剤を配合することによって熱硬化性を有するフェノール樹脂となるのに対し、レゾール型フェノール樹脂は硬化剤が不要であり、自己で熱硬化性を有する。硬化剤は殆どの場合、ホルムアルデヒド源としてヘキサメチレンテトラミンを使用する。これらはいずれも、耐熱性、耐久性、機械的強度、電気特性等が優れている為、成形材料、電子材料、積層板、接着剤、等に幅広く使用されている。 There are two types of phenolic resins, a novolak type that is thermoplastic and a resol type that is thermosetting, whereas a novolac type phenolic resin becomes a phenolic resin that has thermosetting properties by adding a curing agent. The resol type phenol resin does not require a curing agent and has thermosetting properties by itself. Hardeners most often use hexamethylenetetramine as the formaldehyde source. Since these are all excellent in heat resistance, durability, mechanical strength, electrical properties, etc., they are widely used in molding materials, electronic materials, laminates, adhesives, and the like.
しかしながら、従来のノボラック型フェノール樹脂とヘキサメチレンテトラミンとの硬化は、反応時にアンモニアが発生する為、環境面で悪影響を及ぼすという問題がある。その代替としてヘキサメトキシメチルメラミンが検討されているが、ヘキサメチレンテトラミンと同等の硬化速度を得るまでには至っていない。 However, the conventional curing of novolac type phenolic resin and hexamethylenetetramine has a problem of adversely affecting the environment because ammonia is generated during the reaction. As an alternative, hexamethoxymethylmelamine has been studied, but has not yet reached a curing rate equivalent to that of hexamethylenetetramine.
さらに、ノボラック型フェノール樹脂の硬化時間を短縮する様々な方法がとられてきた。例えば、高分子量体のノボラック型フェノール樹脂を使用する方法（特許文献１参照）、フェノール性水酸基に対してオルト−オルト位にメチレン鎖を有するハイオルソノボラック型フェノール樹脂を使用する方法（特許文献２参照）が挙げられる。これらの方法では、硬化時間の短縮にはある程度の効果があるものの、溶融時の粘度が高くなることによって流動性が低下したり、射出成形のような流動性を必要とする方式では作業性が悪化する等の新たな問題が発生し、生産時間が長くなってしまう。その為、更なる硬化時間の短縮が必要とされている。
そこでヘキサメチレンテトラミンを使用すること無く、硬化時間を短縮し、作業性の良いフェノール樹脂組成物が強く要望されている。
Furthermore, various methods for shortening the curing time of the novolac type phenolic resin have been taken. For example, a method using a high molecular weight novolak type phenol resin (see Patent Document 1), a method using a high ortho novolak type phenol resin having a methylene chain at the ortho-ortho position relative to a phenolic hydroxyl group (Patent Document 2). Reference). Although these methods have a certain effect on shortening the curing time, fluidity decreases due to an increase in viscosity at the time of melting, and workability is improved in a method that requires fluidity such as injection molding. New problems such as deterioration will occur and production time will become longer. Therefore, further shortening of the curing time is required.
Therefore, there is a strong demand for a phenol resin composition that shortens the curing time and has good workability without using hexamethylenetetramine.
そこで本発明の目的は、環境に優しく、硬化性に優れているフェノール樹脂組成物及びそれら硬化物を提供することにある。 Accordingly, an object of the present invention is to provide a phenol resin composition that is environmentally friendly and excellent in curability and a cured product thereof.
本発明者は、上記目的を達成するために鋭意検討した結果、ノボラック型フェノール樹脂（ａ）にレゾール型フェノール樹脂（ｂ）を配合することにより得られるフェノール樹脂組成物が硬化性に優れていることを見出し、本発明に至った。 As a result of intensive studies to achieve the above object, the present inventors have found that a phenol resin composition obtained by blending a resol type phenol resin (b) with a novolak type phenol resin (a) has excellent curability. As a result, they have reached the present invention.
即ち、本発明は、ノボラック型フェノール樹脂（ａ）にレゾール型フェノール樹脂（ｂ）を配合してなるフェノール樹脂組成物であり、加熱時に自己硬化性を特徴とするレゾール型フェノール樹脂を添加し、新たな架橋反応を導入しノボラック型フェノール樹脂の硬化性が優れていることを特徴とする。 That is, the present invention is a phenolic resin composition comprising a novolac type phenolic resin (a) and a resol type phenolic resin (b), and a resol type phenolic resin characterized by self-curing property when heated, A novel crosslinking reaction is introduced, and the curability of the novolac type phenol resin is excellent.
本発明のフェノール樹脂組成物は、ノボラック型フェノール樹脂（ａ）とレゾール型フェノール樹脂（ｂ）の各成分の配合が、ノボラック型フェノール樹脂（ａ）１００重量部に対して、レゾール型フェノール樹脂（ｂ）が０．１〜７０重量部である前記フェノール樹脂組成物である。 In the phenol resin composition of the present invention, the composition of each component of the novolac type phenol resin (a) and the resol type phenol resin (b) is 100 parts by weight of the novolac type phenol resin (a). It is the said phenol resin composition whose b) is 0.1-70 weight part.
本発明のフェノール樹脂組成物は、レゾール型フェノール樹脂を配合することにより、アンモニア等の環境に悪影響を与える反応副生物の生成がまったくなく、硬化時間をより短縮することができる。 In the phenol resin composition of the present invention, by adding a resol type phenol resin, there is no generation of reaction by-products that adversely affect the environment such as ammonia, and the curing time can be further shortened.
以下に本発明を詳細に説明する。本発明に使用するノボラック型フェノール樹脂（ａ）の一つ目の態様は、少なくともフェノール化合物と、ビスメトキシメチルビフェニル又は／及びビスクロロメチルビフェニルと、ホルムアルデヒドとを反応させて得られるノボラック型フェノール樹脂（ａ）である。本発明に使用するノボラック型フェノール樹脂（ａ）の二つ目の態様は、フェノール化合物と、ビスメトキシメチルビフェニル又は／及びビスクロロメチルビフェニルと、パラキシリレンジメチルエーテル又は／及びパラキシリレンジクロライドと、ホルムアルデヒドとを反応させて得られるノボラック型フェノール樹脂（ａ）である。 The present invention is described in detail below. The first embodiment of the phenolic novolak resin used in the present invention (a) has at least a phenol compound, a bis-methoxymethyl biphenyl or / and bis chloromethyl biphenyl novolak type phenolic resins obtained by reacting with formaldehyde (A). The second aspect of the novolak type phenol resin (a) used in the present invention is a phenol compound, bismethoxymethylbiphenyl or / and bischloromethylbiphenyl, paraxylylene dimethyl ether or / and paraxylylene dichloride, It is a novolak type phenol resin (a) obtained by reacting with formaldehyde.
本発明に使用するレゾール型フェノール樹脂（ｂ）は、特に制限はないが、好ましくは下記一般式（２）で表されるフェノール樹脂化合物縮合体である。レゾール型フェノール樹脂（ｂ）は、これらのフェノール樹脂化合物縮合体を単独または複数含んで使用することができる。 The resol type phenol resin (b) used in the present invention is not particularly limited, but is preferably a phenol resin compound condensate represented by the following general formula (2). The resol type phenol resin (b) can be used alone or in combination of these phenol resin compound condensates.
本発明に使用するレゾール型フェノール樹脂（ｂ）においては、前記一般式（１）のＡがキシリレン基またはビフェニレン基のフェノール樹脂化合物縮合体が特に好ましく、単独でも両方含まれていても何ら問題はない。 In the resol type phenol resin (b) used in the present invention, a phenol resin compound condensate in which A in the general formula (1) is a xylylene group or a biphenylene group is particularly preferable, and there is no problem even if both are included alone. Absent.
本発明に使用するノボラック型フェノール樹脂（ａ）またはレゾール型フェノール樹脂（ｂ）のフェノール化合物とは、芳香環に少なくとも１個のフェノール性水酸基を有する化合物である。具体的に例示すると、フェノール、レゾルシノール、ヒドロキノンなどの無置換のフェノール類；クレゾール、エチルフェノール、ｎ−プロピルフェノール、オクチルフェノール、ノニルフェノール、フェニルフェノールなどの一置換フェノール類；キシレノール、メチルプロピルフェノール、ジプロピルフェノール、ジブチルフェノール、グアヤコール、グエトールなどの二置換フェノール類；トリメチルフェノールに代表される三置換フェノール類；ナフトール、メチルナフトールなどのナフトール類；ビスフェノール、ビスフェノールＡ、ビスフェノールＦなどのビスフェノール類などが挙げられる。このうち汎用的には、フェノール、クレゾールを用いることが好ましい。 The phenol compound of the novolak type phenol resin (a) or the resol type phenol resin (b) used in the present invention is a compound having at least one phenolic hydroxyl group in the aromatic ring. Specifically, unsubstituted phenols such as phenol, resorcinol and hydroquinone; monosubstituted phenols such as cresol, ethylphenol, n-propylphenol, octylphenol, nonylphenol and phenylphenol; xylenol, methylpropylphenol and dipropyl Disubstituted phenols such as phenol, dibutylphenol, guaiacol, guetol; trisubstituted phenols represented by trimethylphenol; naphthols such as naphthol and methylnaphthol; bisphenols such as bisphenol, bisphenol A, and bisphenol F . Of these, phenol and cresol are preferably used for general purposes.
ビスメトキシメチルビフェニルの各異性体としては、〔１，１’−ビフェニル〕−４，４’ジメチレン、〔１，１’−ビフェニル〕−２，２’ジメチレン、〔１，１’−ビフェニル〕−２，３’ジメチレン、〔１，１’−ビフェニル〕−２，４’ジメチレン、〔１，１’−ビフェニル〕−３，３’ジメチレン、〔１，１’−ビフェニル〕−３，４’ジメチレン、ビスグリコールビフェニル等が挙げられる。 The isomers of the bi scan methoxymethyl biphenyl, [1,1'-biphenyl] -4,4 'dimethylene, [1,1'-biphenyl] -2,2' dimethylene, [1,1'-biphenyl] -2,3 'dimethylene, [1,1'-biphenyl] -2,4' dimethylene, [1,1'-biphenyl] -3,3 'dimethylene, [1,1'-biphenyl] -3,4' Examples include dimethylene and bisglycol biphenyl.
ノボラック型フェノール樹脂（ａ）の合成に使用する触媒としては、有機酸である蓚酸、蟻酸、酢酸、および硫酸、ｐ−トルエンスルホン酸、硫酸ジエチルのようなフリーデルクラフト型触媒の存在において行うことができ、レゾール型フェノール樹脂（ｂ）の合成では水酸化ナトリウム、アンモニアのような無機触媒の存在において行うことができる。 The catalyst used for the synthesis of the novolak-type phenolic resin (a) is performed in the presence of Friedel-Craft type catalysts such as organic acids such as oxalic acid, formic acid, acetic acid, sulfuric acid, p-toluenesulfonic acid, and diethyl sulfate. The synthesis of the resol type phenol resin (b) can be carried out in the presence of an inorganic catalyst such as sodium hydroxide or ammonia.
硬化性に優れたフェノール樹脂組成物の合成方法としては、ノボラック型フェノール樹脂（ａ）とレゾール型フェノール樹脂（ｂ）を配合し、公知の混練機を用い、室温にて混練すればよい。 As a method for synthesizing a phenol resin composition having excellent curability, a novolac type phenol resin (a) and a resol type phenol resin (b) may be blended and kneaded at room temperature using a known kneader.
ノボラック型フェノール樹脂（ａ）とレゾール型フェノール樹脂（ｂ）の配合割合については、両者が混合されていれば特に問題はない。好ましくは、ノボラック型フェノール樹脂（ａ）１００重量部に対して、レゾール型フェノール樹脂（ｂ）が０．１〜７０重量部である。さらに好ましくは、ノボラック型フェノール樹脂（ａ）１００重量部に対して、レゾール型フェノール樹脂（ｂ）の下限値が１、５、１０および２０と増加させ、上限値も６０、５０と減少させた値から任意に選べる。最も好ましくは、ノボラック型フェノール樹脂（ａ）１００重量部に対して、レゾール型フェノール樹脂（ｂ）が２０〜５０重量部である。 About the compounding ratio of a novolak-type phenol resin (a) and a resol type phenol resin (b), if both are mixed, there will be no problem in particular. Preferably, the resol type phenol resin (b) is 0.1 to 70 parts by weight with respect to 100 parts by weight of the novolac type phenol resin (a). More preferably, the lower limit value of the resol type phenol resin (b) is increased to 1, 5, 10, and 20 and the upper limit value is decreased to 60, 50 with respect to 100 parts by weight of the novolak type phenol resin (a). You can choose any value. Most preferably, the resol type phenol resin (b) is 20 to 50 parts by weight with respect to 100 parts by weight of the novolac type phenol resin (a).
より具体的な一例としては、ノボラック型フェノール樹脂（ａ）と配合するレゾール型フェノール樹脂（ｂ）は、下記一般式（１）で表されるポリスチレン換算重量平均分子量（Ｍｗ）が３００〜４０００である固形タイプのレゾールを用いる。配合量は、前記ノボラック型フェノール樹脂１００重量部に対して、０．１〜７０重量部であり、好ましくは１０〜５０重量部である。０．１重量部未満では、硬化性能が不充分であり、７０重量部を超えると、フェノール樹脂組成物としての流動性が損なわれる。 As a more specific example, resol type phenol resin blended with novolac-type phenol resin (a) (b) are polystyrene equivalent weight average molecular weight represented by the following general formula (1) (Mw) is 300 to 4000 A solid type resol is used. A compounding quantity is 0.1-70 weight part with respect to 100 weight part of said novolak-type phenol resins, Preferably it is 10-50 weight part. If it is less than 0.1 part by weight, the curing performance is insufficient, and if it exceeds 70 parts by weight, the fluidity as a phenol resin composition is impaired.
本発明のフェノール樹脂組成物は、さらにメチレン供与体である硬化剤を併用しても何ら問題は無い。該硬化剤としてはヘキサメトキシメチルメラミン等が挙げられる。ここで、硬化剤の配合量は、前述した一般式（１）ノボラック型フェノール樹脂（ａ）１００重量部に対して、０〜３０重量部が好適である。３０質量部を超えると、ヘキサメトキシメチルメラミンが分解して発生するメタノールが多くなり、作業性や環境に悪影響を及ぼす可能性生じることがある。 The phenol resin composition of the present invention has no problem even when a curing agent that is a methylene donor is used in combination. Examples of the curing agent include hexamethoxymethyl melamine. Here, 0-30 weight part is suitable for the compounding quantity of a hardening | curing agent with respect to 100 weight part of general formula (1) novolak-type phenol resin (a) mentioned above. If it exceeds 30 parts by mass, the amount of methanol generated by decomposition of hexamethoxymethylmelamine increases, which may adversely affect workability and the environment.
本発明で得られるフェノール樹脂組成物は、硬化時間を短縮することができ、また、反応副生物をまったく含まないことより、成形材料、電子材料、積層板、接着剤用途に使用することができる。 The phenol resin composition obtained in the present invention can shorten the curing time and can be used for molding materials, electronic materials, laminates, and adhesives because it does not contain any reaction by-products. .
以下、実施例及び比較例を挙げて本発明をより具体的に説明する。しかし、本発明はこれらの実施例に限定されるものではない。また、本文中「部」は重量部を示す。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the text, “parts” indicates parts by weight.
合成例１
温度計、仕込・留出口、冷却器および攪拌機を備えた容量２０００容量部のガラス製フラスコにｍ−クレゾール酸 ８４１部（７．７８７モル）、４，４’−ビスメトキシメチルビフェニル ６３．９部（０．２６４モル）、４２％ホルマリン ３３６．３部（４．７５モル）及び蓚酸 ２．８部を４つ口フラスコに入れ、内温９７℃にて１５ｈ反応させた。その後、２５％硫酸０．４部を添加し、１００℃にて脱水し、１７０℃まで４ｈかけて昇温することで脱メタノール反応をさせ、その後減圧４０ｔｏｒｒ−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は１３０℃、ＧＰＣによるポリスチレン換算数平均分子量（Ｍｎ）は１２３７で、重量平均分子量（Ｍｗ）は２０５７であった。
Synthesis example 1
841 parts (7.787 mol) of m-cresolic acid and 63.9 parts of 4,4′-bismethoxymethylbiphenyl were placed in a glass flask having a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer. (0.264 mol), 336.3 parts (4.75 mol) of 42% formalin and 2.8 parts of oxalic acid were placed in a four-necked flask and reacted at an internal temperature of 97 ° C. for 15 hours. Thereafter, 0.4 part of 25% sulfuric acid was added, dehydrated at 100 ° C., heated to 170 ° C. over 4 hours to cause demethanol reaction, and then unreacted components were removed by reduced pressure 40 torr-steaming treatment. did. The softening point of the obtained resin was 130 ° C., the number average molecular weight (Mn) in terms of polystyrene by GPC was 1237, and the weight average molecular weight (Mw) was 2057.
合成例２
温度計、仕込・留出口、冷却器および攪拌機を備えた容量２０００容量部のガラス製フラスコにｍ−クレゾール酸 ８４１部（７．７８７モル）、４，４’−ビスメトキシメチルビフェニル １９１．７部（０．７９２モル）、４２％ホルマリン ３３９．３部（４．７５モル）及び蓚酸 ２．８部を４つ口フラスコに入れ、内温９７℃にて１５ｈ反応させた。その後、２５％硫酸０．４部を添加し、１００℃にて脱水し、１７０℃まで４ｈかけて昇温することで脱メタノール反応をさせ、その後減圧４０ｔｏｒｒ−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は１３０℃、ＧＰＣによるポリスチレン換算数平均分子量（Ｍｎ）は１５１３で、重量平均分子量（Ｍｗ）は３９４１であった。
Synthesis example 2
In a glass flask having a capacity of 2000 parts by volume equipped with a thermometer, a charging / distilling outlet, a condenser and a stirrer, 841 parts (7.787 mol) of m-cresolic acid and 191.7 parts of 4,4′-bismethoxymethylbiphenyl (0.792 mol), 339.3 parts (4.75 mol) of 42% formalin and 2.8 parts of oxalic acid were placed in a four-necked flask and reacted at an internal temperature of 97 ° C. for 15 hours. Thereafter, 0.4 part of 25% sulfuric acid was added, dehydrated at 100 ° C., heated to 170 ° C. over 4 hours to cause demethanol reaction, and then unreacted components were removed by reduced pressure 40 torr-steaming treatment. did. The softening point of the obtained resin was 130 ° C., the number average molecular weight (Mn) in terms of polystyrene by GPC was 1513, and the weight average molecular weight (Mw) was 3941.
合成例３
温度計、仕込・留出口、冷却器および攪拌機を備えた容量２０００容量部のガラス製フラスコにｍ−クレゾール酸 ９６８部（８．９６３モル）、４，４’−ビスメトキシメチルビフェニル ２５５．６部（１．０５６モル）、４２％ホルマリン ３３９．３部（４．７５モル）及び蓚酸 ２．８部を４つ口フラスコに入れ、内温９７℃にて１５ｈ反応させた。その後、２５％硫酸０．４部を添加し、１００℃にて脱水し、１７０℃まで４ｈかけて昇温することで脱メタノール反応をさせ、その後減圧４０ｔｏｒｒ−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は１２８℃、ＧＰＣによるポリスチレン換算数平均分子量（Ｍｎ）は１４００で、重量平均分子量（Ｍｗ）は２８４８であった。
Synthesis example 3
In a glass flask having a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 968 parts (8.963 mol) of m-cresolic acid and 255.6 parts of 4,4′-bismethoxymethylbiphenyl (1.056 mol), 339.3 parts (4.75 mol) of 42% formalin and 2.8 parts of oxalic acid were placed in a four-necked flask and reacted at an internal temperature of 97 ° C. for 15 hours. Thereafter, 0.4 part of 25% sulfuric acid was added, dehydrated at 100 ° C., heated to 170 ° C. over 4 hours to cause demethanol reaction, and then unreacted components were removed by reduced pressure 40 torr-steaming treatment. did. The softening point of the obtained resin was 128 ° C., the number average molecular weight (Mn) in terms of polystyrene by GPC was 1400, and the weight average molecular weight (Mw) was 2848.
合成例４
温度計、仕込・留出口、冷却器および攪拌機を備えた容量２０００容量部のガラス製フラスコにｍ−クレゾール酸 ９６８部（８．９６３モル）、４，４’−ビスメトキシメチルビフェニル ６３．９部（０．２６４モル）、ｐ−キシレンジメチルエーテル ５０．８部（０．３０６モル）、４２％ホルマリン ３３９．３部（４．７５モル）及び蓚酸 ２．８部を４つ口フラスコに入れ、内温９７℃にて１５ｈ反応させた。その後、２５％硫酸０．４部を添加し、１００℃にて脱水し、１７０℃まで４ｈかけて昇温することで脱メタノール反応をさせ、その後減圧４０ｔｏｒｒ−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は１３０℃、ＧＰＣによるポリスチレン換算数平均分子量（Ｍｎ）は１２３４で、重量平均分子量（Ｍｗ）は２００５であった。
Synthesis example 4
In a glass flask having a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 968 parts (8.963 mol) of m-cresolic acid and 63.9 parts of 4,4′-bismethoxymethylbiphenyl (0.264 mol), 50.8 parts (0.306 mol) of p-xylene dimethyl ether, 339.3 parts (4.75 mol) of 42% formalin and 2.8 parts of oxalic acid were placed in a four-necked flask. The reaction was carried out at a temperature of 97 ° C. for 15 hours. Thereafter, 0.4 part of 25% sulfuric acid was added, dehydrated at 100 ° C., heated to 170 ° C. over 4 hours to cause demethanol reaction, and then unreacted components were removed by reduced pressure 40 torr-steaming treatment. did. The resulting resin had a softening point of 130 ° C., a polystyrene-reduced number average molecular weight (Mn) by GPC of 1234, and a weight average molecular weight (Mw) of 2005.
合成例５
温度計、仕込・留出口、冷却器および攪拌機を備えた容量２０００容量部のガラス製フラスコにフェノール１１０．１部（１．１７１モル）、パラキシリレンジメチルエーテル２９．５部（０．１７８モル）および硫酸０．０３５部を４つ口フラスコに入れ、内温１３５℃にて２ｈ脱メタノール反応させ、その後１６０℃にて２ｈ更に反応させた。内温１６０℃に保ったまま減圧４０ｔｏｒｒにて未反応成分を除去し、１００℃以下に冷却した後、水酸化ナトリウムを１８部添加した。４２％ホルマリンを２３．５部（０．３２９モル）添加後、６５℃まで昇温し、１ｈ反応させた。硫酸１３．０５部にて中和させた後、８５℃まで昇温し、減圧４０ｔｏｒｒにて縮合水を脱水除去した。得られた樹脂のＧＰＣによるポリスチレン換算数平均分子量（Ｍｎ）は１０５０、重量平均分子量（Ｍｗ）は４３００、１５０℃でのゲルタイムは２２０秒であった。
Synthesis example 5
In a glass flask having a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 110.1 parts (1.171 moles) of phenol and 29.5 parts (0.178 moles) of paraxylylene dimethyl ether Then, 0.035 part of sulfuric acid was placed in a four-necked flask and subjected to demethanol reaction at an internal temperature of 135 ° C. for 2 hours, and then further reacted at 160 ° C. for 2 hours. While maintaining the internal temperature at 160 ° C., unreacted components were removed at a reduced pressure of 40 torr, and after cooling to 100 ° C. or lower, 18 parts of sodium hydroxide was added. After adding 23.5 parts (0.329 mol) of 42% formalin, the temperature was raised to 65 ° C. and reacted for 1 hour. After neutralizing with 13.05 parts of sulfuric acid, the temperature was raised to 85 ° C., and the condensed water was dehydrated and removed at a reduced pressure of 40 torr. The number average molecular weight (Mn) in terms of polystyrene by GPC of the obtained resin was 1050, the weight average molecular weight (Mw) was 4300, and the gel time at 150 ° C. was 220 seconds.
実施例１〜９、実施例１０〜１８および実施例１９〜２４
表１、表２および表３に示す配合内容の原料を秤量し、公知の混錬機を用いて、粉砕混合し、下記に示す方法でゲルタイムの評価試験を行った。得られた結果を表１、表２および表３にそれぞれ併記して示した。
Examples 1-9, Examples 10-18 and Examples 19-24
The raw materials having the blending contents shown in Table 1, Table 2 and Table 3 were weighed, pulverized and mixed using a known kneader, and the gel time evaluation test was performed by the method shown below. The obtained results are shown in Table 1, Table 2 and Table 3, respectively.
比較例１〜５および比較例６〜９
表４および表５に示す配合内容の原料を秤量し、公知の混錬機を用いて、粉砕混合し、下記に示す方法でゲルタイムの評価試験を行った。得られた結果を表４、表５に併記して示した。
Comparative Examples 1-5 and Comparative Examples 6-9
The raw materials having the blending contents shown in Table 4 and Table 5 were weighed, pulverized and mixed using a known kneader, and the gel time evaluation test was performed by the method shown below. The obtained results are shown together in Tables 4 and 5.
上記の実施例および比較例の試料を１５０℃の熱板上に試料０．５ｇをのせ、あらかじめ熱板上で加熱したヘラを使用し、直径約３ｃｍの円状に広げ、１回／約１秒の速度で混錬した。試料とヘラの間に糸引きが無くなるまでの時間を計測した。即ちゲルタイムが短いほど硬化速度が速いことを意味する。 The sample of the above example and comparative example is placed on a hot plate at 150 ° C., 0.5 g of the sample is placed, and a spatula heated on the hot plate in advance is used to spread it into a circle having a diameter of about 3 cm. Kneaded at a speed of seconds. The time until stringing disappeared between the sample and the spatula was measured. That is, the shorter the gel time, the faster the curing speed.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5342239A (en) * | 1976-09-30 | 1978-04-17 | Matsushita Electric Works Ltd | Molding materials of phenolic resin |
| JPS6035047A (en) * | 1983-08-05 | 1985-02-22 | Sumitomo Bakelite Co Ltd | Phenolic resin composition |
| JPH06322240A (en) * | 1993-05-07 | 1994-11-22 | Toshiba Chem Corp | Phenol resin molding material and its molded article |
| JPH07196568A (en) * | 1994-01-06 | 1995-08-01 | Mitsui Toatsu Chem Inc | Bis(hydroxybenzyl)benzene compound, its epoxy resin and their production |
| JPH083346A (en) * | 1994-06-25 | 1996-01-09 | Toshiba Chem Corp | Production of heat-resistant phenolic resin molding |
| JPH08143648A (en) * | 1994-09-20 | 1996-06-04 | Meiwa Kasei Kk | New phenolic novolak condensate |
| JPH1171451A (en) * | 1997-08-29 | 1999-03-16 | Meiwa Kasei Kk | Phenol novolac condensate |
| JPH11140148A (en) * | 1997-11-07 | 1999-05-25 | Meiwa Kasei Kk | Biphenyl novolac condensate |
| JP2001123041A (en) * | 1999-10-26 | 2001-05-08 | Fudow Co Ltd | Phenolic resin molding material |
| JP2003286387A (en) * | 2002-03-28 | 2003-10-10 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and paper base phenolic resin laminate |
| JP2004284888A (en) * | 2003-03-24 | 2004-10-14 | Sumitomo Bakelite Co Ltd | Binder composition for refractory |
-
2005
- 2005-07-29 JP JP2005220256A patent/JP4618037B2/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5342239A (en) * | 1976-09-30 | 1978-04-17 | Matsushita Electric Works Ltd | Molding materials of phenolic resin |
| JPS6035047A (en) * | 1983-08-05 | 1985-02-22 | Sumitomo Bakelite Co Ltd | Phenolic resin composition |
| JPH06322240A (en) * | 1993-05-07 | 1994-11-22 | Toshiba Chem Corp | Phenol resin molding material and its molded article |
| JPH07196568A (en) * | 1994-01-06 | 1995-08-01 | Mitsui Toatsu Chem Inc | Bis(hydroxybenzyl)benzene compound, its epoxy resin and their production |
| JPH083346A (en) * | 1994-06-25 | 1996-01-09 | Toshiba Chem Corp | Production of heat-resistant phenolic resin molding |
| JPH08143648A (en) * | 1994-09-20 | 1996-06-04 | Meiwa Kasei Kk | New phenolic novolak condensate |
| JPH1171451A (en) * | 1997-08-29 | 1999-03-16 | Meiwa Kasei Kk | Phenol novolac condensate |
| JPH11140148A (en) * | 1997-11-07 | 1999-05-25 | Meiwa Kasei Kk | Biphenyl novolac condensate |
| JP2001123041A (en) * | 1999-10-26 | 2001-05-08 | Fudow Co Ltd | Phenolic resin molding material |
| JP2003286387A (en) * | 2002-03-28 | 2003-10-10 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and paper base phenolic resin laminate |
| JP2004284888A (en) * | 2003-03-24 | 2004-10-14 | Sumitomo Bakelite Co Ltd | Binder composition for refractory |
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