JP2009126886A - Manufacturing method of modified novolac resin, and modified novolac resin - Google Patents
Manufacturing method of modified novolac resin, and modified novolac resin Download PDFInfo
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Abstract
Description
本発明は、変性ノボラック系樹脂の製造方法及び変性ノボラック系樹脂に関し、特に、耐熱性が高く、硬化時のガス発生がなくその硬化物の色合いが極めて淡色であり、液晶ディスプレイ部材のような高い透明性が求められる分野の材料として好適である変性ノボラック系樹脂の製造方法及び変性ノボラック系樹脂に関する。 The present invention relates to a method for producing a modified novolac resin and a modified novolac resin, and in particular, has high heat resistance, no gas generation during curing, and the color of the cured product is extremely light and high as in a liquid crystal display member. The present invention relates to a method for producing a modified novolac resin and a modified novolac resin that are suitable as materials in fields requiring transparency.
従来から、フェノール樹脂は、機械的強度、耐熱性、寸法安定性、電気絶縁性、耐酸性、難燃性などの特性に優れ様々な分野に使用されている。しかし、フェノール樹脂は容易に酸化され黄褐色〜赤褐色に着色する。さらに加熱硬化させた製品は、色調が濃化して濃黄褐色〜濃赤褐色となる。また、硬化物は経時により着色が濃くなる。フェノール樹脂が濃色に着色する原因は、フェノール性水酸基の水素原子が引抜かれ、フェノキシラジカルが生成し、キノン由来のトリフェニルメタン構造が主原因と考えられている。特許文献１には、これらを解決する目的で着色の少ないフェノールモノマーとして、ビスフェノールＡモノマーを使用することが記載されているが、硬化物の着色は少なくなるもののビスフェノールＡは、近年、環境保護のため、市場の要請もあり使用を控える傾向にある。 Conventionally, phenolic resins have excellent properties such as mechanical strength, heat resistance, dimensional stability, electrical insulation, acid resistance, and flame resistance, and are used in various fields. However, the phenolic resin is easily oxidized and colored yellowish brown to reddish brown. Further, the heat-cured product is darkened in color to dark yellowish brown to dark reddish brown. Further, the cured product becomes darker with time. The reason why the phenol resin is colored deeply is considered to be mainly due to the triphenylmethane structure derived from quinone, because the hydrogen atom of the phenolic hydroxyl group is extracted and a phenoxy radical is generated. Patent Document 1 describes the use of bisphenol A monomer as a less colored phenol monomer for the purpose of solving these problems, but bisphenol A, which is less colored in the cured product, has recently been used for environmental protection. For this reason, there is a tendency to refrain from use due to market demand.
また、フェノール樹脂の着色を抑える目的で、メラミン樹脂等のアミノ樹脂変性が特許文献２に開示されているが、アルデヒドに対する反応性はフェノール類とアミノ樹脂では異なるため共重合体はできず、経時によるフェノール類の着色がある。また、硬化の際に発生するアルデヒドは多くなり、環境面においても好ましくない。
特許文献３には、フェノール樹脂の硬化時に発生するガスをなくす目的で、ノボラック樹脂の水酸基にグリシジル（メタ）アクリレートと反応して得られる（メタ）アクリロイル化ノボラック樹脂が記載されているが、不飽和基を導入することにより、硬化時のガスは発生しないが、通常のノボラック樹脂をベースにしていることから、硬化物は濃く着色する。
Patent Document 3 describes a (meth) acryloylated novolak resin obtained by reacting a hydroxyl group of a novolak resin with glycidyl (meth) acrylate for the purpose of eliminating the gas generated when the phenol resin is cured. By introducing a saturated group, no gas is generated during curing, but the cured product is darkly colored because it is based on a normal novolac resin.
本発明は、前記の課題を解決するためになされたもので、硬化時のガス発生がなくその硬化物の色合いが極めて淡色である変性ノボラック系樹脂の製造方法及び変性ノボラック系樹脂を提供することを目的とするものである。 The present invention has been made to solve the above-described problems, and provides a method for producing a modified novolac resin and a modified novolac resin in which the color of the cured product is extremely light without gas generation during curing. It is intended.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、少なくとも１つの水酸基を置換基として有する水酸基含有芳香族炭化水素とエチレン尿素又はプロピレン尿素とがメチレン結合を介して交互に繰り返した構造を有する窒素含有樹脂を原料として用いることにより、フェノール樹脂の着色原因と言われるトリフェニルメタン構造を生成し難くなり、不飽和基を含有することにより硬化時のガス発生がなく硬化後の色合いが極めて淡色である変性ノボラック系樹脂が得られることを見出し、本発明を完成するに至った。
すなわち、本発明は、少なくとも１つの水酸基を置換基として有する水酸基含有芳香族炭化水素と、エチレン尿素又はプロピレン尿素とがメチレン結合を介して交互に繰り返した構造を有する窒素含有樹脂に、グリシジルアクリレート及び／又はグリシジルメタクリレートを付加反応させる変性ノボラック系樹脂の製造方法、並びに、その製造方法により得られる変性ノボラック系樹脂を提供するものである。
As a result of intensive studies to achieve the above object, the present inventors have found that hydroxyl group-containing aromatic hydrocarbons having at least one hydroxyl group as a substituent and ethylene urea or propylene urea alternately through a methylene bond. By using a nitrogen-containing resin having a repeated structure as a raw material, it becomes difficult to produce a triphenylmethane structure, which is said to be a cause of coloring of the phenol resin, and by containing an unsaturated group, there is no gas generation during curing and after curing The present inventors have found that a modified novolac resin having a very light hue can be obtained.
That is, the present invention relates to a nitrogen-containing resin having a structure in which a hydroxyl group-containing aromatic hydrocarbon having at least one hydroxyl group as a substituent and ethylene urea or propylene urea are alternately repeated via a methylene bond, glycidyl acrylate and The present invention provides a method for producing a modified novolak resin in which glycidyl methacrylate is subjected to an addition reaction, and a modified novolak resin obtained by the production method.
本発明の製造方法により得られる変性ノボラック系樹脂は、耐熱性が高く、硬化時のガス発生がなくその硬化物の色合いが極めて淡色である。 The modified novolak resin obtained by the production method of the present invention has high heat resistance, no gas generation during curing, and the color of the cured product is extremely light.
本発明の変性ノボラック系樹脂の製造方法は、少なくとも１つの水酸基を置換基として有する水酸基含有芳香族炭化水素と、エチレン尿素又はプロピレン尿素とがメチレン結合を介して交互に繰り返した構造を有する窒素含有樹脂に、グリシジル（メタ）アクリレートを付加反応させる。
前記グリシジル（メタ）アクリレートは、グリシジルアクリレート及び／又はグリシジルメタクリレートを示す。
The method for producing a modified novolak resin of the present invention includes a nitrogen-containing structure in which a hydroxyl group-containing aromatic hydrocarbon having at least one hydroxyl group as a substituent and ethylene urea or propylene urea are alternately repeated via a methylene bond The resin is subjected to an addition reaction with glycidyl (meth) acrylate.
The glycidyl (meth) acrylate indicates glycidyl acrylate and / or glycidyl methacrylate.
水酸基含有芳香族炭化水素としては、環を構成する炭素数が６〜１８であると好ましく、６〜１２であるとさらに好ましい。水酸基以外の置換基を有していても良い。また、含有する水酸基は、１〜２個が好ましい。
このような水酸基含有芳香族炭化水素としては、例えば、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、ｏ−エチルフェノール、ｍ−エチルフェノール、ｐ−エチルフェノール、ｏ−イソプロピルフェノール、ｍ−プロピルフェノール、ｐ−プロピルフェノール、ｐ−ｓｅｃ−ブチルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−シクロヘキシルフェノール、ｐ−クロロフェノール、ｏ−ブロモフェノール、ｍ−ブロモフェノール、ｐ−ブロモフェノール等のフェノール類、α−ナフトール、β−ナフトール等のナフトール類、２，４−キシレノール、２，５−キシレノール、２，６−キシレノール等のキシレノール類等の一価フェノール類；レゾルシン、カテコール、ハイドロキノン、２，２−ビス（４'−ヒドロキシフェニル）プロパン、１，１'−ビス（ジヒドロキシフェニル）メタン、１，１'−ビス（ジヒドロキシナフチル）メタン、テトラメチルビフェノール、ビフェノール、ヘキサメチルビフェノール、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン等のナフタレンジオール類等の二価フェノール類；トリスヒドロキシフェニルメタン等の三価フェノール類を挙げることができる。
これらの中でも、特に、フェノール、ｏ−クレゾール、ｍ−クレゾール、ナフトール類、２，２−ビス（４'−ヒドロキシフェニル）プロパン、２，６−キシレノール、レゾルシン、ハイドロキノン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレンが好ましい。
これらは、単独でもしくは２種以上を併用して使用することができる。
The hydroxyl group-containing aromatic hydrocarbon preferably has 6 to 18 carbon atoms and more preferably 6 to 12 carbon atoms constituting the ring. You may have substituents other than a hydroxyl group. Moreover, 1-2 are preferable for the hydroxyl group to contain.
Examples of such a hydroxyl group-containing aromatic hydrocarbon include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m- Phenols such as propylphenol, p-propylphenol, p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, α Monohydric phenols such as naphthols such as naphthol and β-naphthol, xylenols such as 2,4-xylenol, 2,5-xylenol and 2,6-xylenol; resorcin, catechol, hydroquinone, 2,2-bis (4'-hydro Cyphenyl) propane, 1,1′-bis (dihydroxyphenyl) methane, 1,1′-bis (dihydroxynaphthyl) methane, tetramethylbiphenol, biphenol, hexamethylbiphenol, 1,2-dihydroxynaphthalene, 1,3-dihydroxy Naphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene And dihydric phenols such as naphthalenediols such as 2,7-dihydroxynaphthalene; and trihydric phenols such as trishydroxyphenylmethane.
Among these, phenol, o-cresol, m-cresol, naphthols, 2,2-bis (4′-hydroxyphenyl) propane, 2,6-xylenol, resorcin, hydroquinone, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene are preferred.
These can be used alone or in combination of two or more.
本発明で用いる窒素含有樹脂は、前記水酸基含有芳香族炭化水素と、エチレン尿素又はプロピレン尿素ジメチロール体とを酸性触媒下で合成すると好ましい。
酸性触媒としては、特に限定されないが、蓚酸、塩酸、硫酸、パラトルエンスルホン酸、メタンスルホン酸等が挙げられる。
また、ジメチロール体を合成するためのアルデヒド類としては、例えば、ホルマリン、パラホルムアルデヒド、トリオキサン（メタホルムアルデヒド）等を挙げることができる。
これらは、単独でもしくは２種以上を併用して使用することができる。
The nitrogen-containing resin used in the present invention is preferably synthesized from the hydroxyl group-containing aromatic hydrocarbon and ethylene urea or propylene urea dimethylol body under an acidic catalyst.
Although it does not specifically limit as an acidic catalyst, Succinic acid, hydrochloric acid, a sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, etc. are mentioned.
Examples of aldehydes for synthesizing a dimethylol body include formalin, paraformaldehyde, and trioxane (metaformaldehyde).
These can be used alone or in combination of two or more.
本発明の製造方法において、窒素含有樹脂の水酸基当量１．０に対し、グリシジル（メタ）アクリレート０．２〜０．９当量を付加反応させると好ましく、０．３〜０．８当量を付加反応させるとさらに好ましい。グリシジル（メタ）アクリレートが０．２当量以上であれば、得られる変性ノボラック系樹脂の硬化性が良好であり、０．９当量以下であれば、得られる変性ノボラック系樹脂を硬化させてなる硬化物の基材に対する密着性が良好である。
また、本発明の製造方法においては、窒素含有樹脂とグリシジル（メタ)アクリレートを塩基性触媒存在下、５０〜１２０℃、好ましくは６０〜８５℃の温度範囲で反応することにより得られる。５０℃以上であれば、反応速度が十分で実用的であり、１２０℃以下であれば、合成中にゲル化する危険性が無い。なお、反応中にゲル化を防止する目的で重合禁止剤を加えても良い。また、反応中はエアーバブリングを行っても良い。
In the production method of the present invention, it is preferable to add 0.2 to 0.9 equivalents of glycidyl (meth) acrylate with respect to a hydroxyl group equivalent of 1.0 of the nitrogen-containing resin, and 0.3 to 0.8 equivalents of addition reaction. More preferably. If the glycidyl (meth) acrylate is 0.2 equivalent or more, the resulting modified novolak resin has good curability, and if it is 0.9 equivalent or less, the resulting modified novolak resin is cured. Good adhesion of the object to the substrate.
Moreover, in the manufacturing method of this invention, it obtains by reacting nitrogen-containing resin and glycidyl (meth) acrylate in the temperature range of 50-120 degreeC in the presence of a basic catalyst, Preferably it is 60-85 degreeC. If it is 50 ° C. or higher, the reaction rate is sufficient and practical, and if it is 120 ° C. or lower, there is no risk of gelation during synthesis. A polymerization inhibitor may be added for the purpose of preventing gelation during the reaction. Air bubbling may be performed during the reaction.
窒素含有樹脂とグリシジル（メタ）アクリレートの反応に用いる塩基性触媒は、反応を促進するものであれば特に限定されず、例えば、脂肪族アミン、芳香族アミン、イミダゾール類、リン系化合物等が使用できる。塩基性触媒の使用量は窒素含有樹脂１００質量部に対して、０．１〜１０質量部が好ましい。
また、重合禁止剤としては、特に限定されないが、例えば、キノン類、フェノール類、多価フェノール類、有機並びに無機の銅塩、アミン類、ニトロ化合物、オキシム類、硫黄類、Ｎ−ニトロソフェニルヒドロキシルアルミニウム塩等が挙げられる。
窒素含有樹脂とグリシジル（メタ）アクリレートとの反応は、メチルエチルケトン、メチルイソブチルケトン、アセトン等の反応溶媒中で行うと好ましい。
本発明の変性ノボラック系樹脂は、上述した製造方法によって得られるものであり、紫外線露光によって硬化する際、光重合開始剤が必要である。
The basic catalyst used in the reaction between the nitrogen-containing resin and glycidyl (meth) acrylate is not particularly limited as long as it accelerates the reaction. For example, aliphatic amines, aromatic amines, imidazoles, phosphorus compounds, etc. are used. it can. The amount of basic catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the nitrogen-containing resin.
The polymerization inhibitor is not particularly limited, but examples thereof include quinones, phenols, polyhydric phenols, organic and inorganic copper salts, amines, nitro compounds, oximes, sulfurs, N-nitrosophenylhydroxyl. An aluminum salt etc. are mentioned.
The reaction between the nitrogen-containing resin and glycidyl (meth) acrylate is preferably performed in a reaction solvent such as methyl ethyl ketone, methyl isobutyl ketone, and acetone.
The modified novolak resin of the present invention is obtained by the above-described production method, and requires a photopolymerization initiator when cured by ultraviolet exposure.
以下、実施例によって本発明をさらに記述するが、本発明は以下の実施例により限定されるものではない。以下、部及び％は質量基準である。
合成例１
冷却管、攪拌機を備えたフラスコに、エチレン尿素１００部、２５％水酸化ナトリウム８部を仕込み、内温５０℃にして、３７％ホルマリン１８８部を１時間かけて滴下した。その後、５０℃で２時間反応し、燐酸６部を添加し中和することでエチレン尿素のジメチロール体を得た。次に、フェノール３２８部、蓚酸１．５部を仕込み、還流温度で４時間反応後、２００℃、５０ｍｍＨｇの減圧下で未反応フェノールを除去した。ＧＰＣ（ゲルパーミエーションクロマトグラフィー）による重量平均分子量３７０、軟化点８０℃の窒素含有樹脂２８８部を得た。また、その水酸基当量は１４２であった。
得られた窒素含有樹脂は、1Ｈ−ＮＭＲスペクトルから、メチレン結合の化学シフトは４．２ｐｐｍ付近のことより、エチレン尿素とフェノールがメチレン結合を介して交互に繰り返した構造のオリゴマーである。
EXAMPLES Hereinafter, although this invention is further described according to an Example, this invention is not limited by a following example. Hereinafter, parts and% are based on mass.
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts of ethylene urea and 8 parts of 25% sodium hydroxide, the internal temperature was 50 ° C., and 188 parts of 37% formalin was added dropwise over 1 hour. Then, it reacted at 50 degreeC for 2 hours, and 6 parts of phosphoric acid was added and neutralized, and the dimethylol body of ethylene urea was obtained. Next, 328 parts of phenol and 1.5 parts of oxalic acid were charged, reacted at reflux temperature for 4 hours, and then unreacted phenol was removed under reduced pressure of 200 ° C. and 50 mmHg. 288 parts of a nitrogen-containing resin having a weight average molecular weight of 370 by GPC (gel permeation chromatography) and a softening point of 80 ° C. were obtained. The hydroxyl equivalent was 142.
From the 1 H-NMR spectrum, the obtained nitrogen-containing resin is an oligomer having a structure in which ethylene urea and phenol are alternately repeated via the methylene bond, since the chemical shift of the methylene bond is around 4.2 ppm.
実施例１
冷却管、攪拌機を備えたフラスコに、合成例１で得られた窒素含有樹脂１００部、メチルエチルケトン４０部、グリシジルメタクリレート７５部、ハイドロキノン０．０５部、トリエチルアミン２部を仕込み、内温８０℃で６時間反応し変性ノボラック系樹脂２１０部を得た。なお、エポキシ基／水酸基の当量比＝０．７５であった。
実施例２
実施例１において、グリシジルメタクリレートを５０部とした以外は同様に反応し、変性ノボラック系樹脂１８８部を得た。なお、エポキシ基／水酸基の当量比＝０．５であった。
Example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts of the nitrogen-containing resin obtained in Synthesis Example 1, 40 parts of methyl ethyl ketone, 75 parts of glycidyl methacrylate, 0.05 part of hydroquinone, and 2 parts of triethylamine. The reaction was conducted for 210 hours to obtain 210 parts of a modified novolac resin. The equivalent ratio of epoxy group / hydroxyl group was 0.75.
Example 2
In Example 1, the reaction was carried out in the same manner except that 50 parts of glycidyl methacrylate was used to obtain 188 parts of a modified novolac resin. The equivalent ratio of epoxy group / hydroxyl group was 0.5.
比較例１
冷却管、攪拌機を備えたフラスコに、ノボラック樹脂（重量平均分子量４４０）１００部、メチルエチルケトン４０部、グリシジルメタクリレート１０２部、ハイドロキノン０．０５部、トリエチルアミン２部を仕込み、内温８０℃で６時間反応し変性ノボラック系樹脂２３５部を得た。
比較例２
比較例１において、グリシジルメタクリレートを６８部とした以外は同様に反応し、変性ノボラック系樹脂２０２部を得た。
Comparative Example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts of a novolak resin (weight average molecular weight 440), 40 parts of methyl ethyl ketone, 102 parts of glycidyl methacrylate, 0.05 part of hydroquinone, and 2 parts of triethylamine, and reacted at an internal temperature of 80 ° C. for 6 hours. 235 parts of a modified novolac resin were obtained.
Comparative Example 2
In Comparative Example 1, the reaction was performed in the same manner except that 68 parts of glycidyl methacrylate was obtained, to obtain 202 parts of a modified novolac resin.
比較例３
冷却管、攪拌機を備えたフラスコに、ビスフェノールＡノボラック樹脂（重量平均分子量４６００）１００部、メチルエチルケトン４０部、グリシジルメタクリレート１８部、ハイドロキノン０．０５部、トリエチルアミン２部を仕込み、内温８０℃で６時間反応し変性ノボラック系樹脂１５０部を得た。
Comparative Example 3
A flask equipped with a condenser and a stirrer was charged with 100 parts of bisphenol A novolak resin (weight average molecular weight 4600), 40 parts of methyl ethyl ketone, 18 parts of glycidyl methacrylate, 0.05 part of hydroquinone, and 2 parts of triethylamine, and the internal temperature was 6 ° C. By reacting for a time, 150 parts of a modified novolac resin was obtained.
＜変性ノボラック系樹脂の評価＞
実施例１〜２及び比較例1〜３で得られた変性ノボラック系樹脂のそれぞれに、不揮発分が５０％になるようメチルエチルケトンを加えた１００部に対して、光重合開始剤（ダロキュア１１７３（商品名）：チバガイギー社製）を２．５部添加して光硬化性樹脂組成物を得た。
これをアルミニウム金属板（１１５０Ｐ ２０ｍｍ×３０ｍｍ×０．３ｍｍ）に♯２４ バーコーターで塗布し、ＵＶ照射量５００ｍＪ／ｃｍ2で照射して硬化させて樹脂硬化物塗膜を形成し、これを試験片とした。
<Evaluation of modified novolac resin>
To 100 parts of each of the modified novolak resins obtained in Examples 1 and 2 and Comparative Examples 1 to 3 with methyl ethyl ketone added so that the nonvolatile content is 50%, a photopolymerization initiator (Darocur 1173 (product) Name): 2.5 parts of Ciba Geigy Co.) was added to obtain a photocurable resin composition.
This was applied to an aluminum metal plate (1150P 20 mm x 30 mm x 0.3 mm) with a # 24 bar coater, and cured by irradiating with a UV irradiation amount of 500 mJ / cm 2 to form a cured resin coating film. A piece.
（１）加熱減量
樹脂硬化物の加熱減量について、セイコー電子工業製ＴＧＡ測定装置ＳＳＣ／５２００Ｈ（商品名）を用いて測定した。昇温速度：１０℃／分。
（２）硬化物の色合い
樹脂硬化物の色合いについて、ＭＩＮＯＬＴＡ製色彩色差計ＣＴ−２１０（商品名）で測定した。
（３）密着性の評価
樹脂硬化物塗膜にカッターを用いて、碁盤目を作成し、セロハンテープにより剥離試験を行い、残った碁盤目の数を記載した。値が大きい程、密着性に優れる。
（４）硬化性
樹脂硬化物塗膜に、ガーゼ１６枚を重ねメチルエチルケトンに浸した２ポンドのハンマーを往復させ、基材が表面に現れた回数を終点とする。また、最大往復数は１００回とする。
(1) Heat loss The heat loss of the cured resin was measured using a TGA measuring device SSC / 5200H (trade name) manufactured by Seiko Denshi Kogyo. Temperature increase rate: 10 ° C./min.
(2) Color of cured product The color of the cured resin was measured with a color difference meter CT-210 (trade name) manufactured by MINOLTA.
(3) Evaluation of adhesiveness A grid was created using a cutter on the cured resin coating film, a peel test was performed using a cellophane tape, and the number of grids remaining was described. The larger the value, the better the adhesion.
(4) Curability A 16-gauze layered two-pound hammer is reciprocated on the cured resin coating film and dipped in methyl ethyl ketone, and the number of times the base material appears on the surface is defined as the end point. The maximum number of round trips is 100.
本発明の製造方法により得られる変性ノボラック系樹脂は、耐熱性が高く、硬化時のガス発生がなくその硬化物は極めて淡色である。このため、液晶ディスプレイ部材のような透明性の高いことが求められる分野の材料として好適である。 The modified novolac resin obtained by the production method of the present invention has high heat resistance, does not generate gas during curing, and its cured product is extremely light in color. For this reason, it is suitable as a material in a field where high transparency such as a liquid crystal display member is required.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311137A (en) * | 1995-05-18 | 1996-11-26 | Sumitomo Bakelite Co Ltd | Curable resin composition |
| JP2005232389A (en) * | 2004-02-23 | 2005-09-02 | Sumitomo Bakelite Co Ltd | Curable resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08311137A (en) * | 1995-05-18 | 1996-11-26 | Sumitomo Bakelite Co Ltd | Curable resin composition |
| JP2005232389A (en) * | 2004-02-23 | 2005-09-02 | Sumitomo Bakelite Co Ltd | Curable resin composition |
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| JP2016183309A (en) * | 2015-03-27 | 2016-10-20 | アイカＳｄｋフェノール株式会社 | Epoxy resin and thermosetting resin composition |
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