JP2002308956A - Partially (meth)acryloylated novolak resin - Google Patents
Partially (meth)acryloylated novolak resinInfo
- Publication number
- JP2002308956A JP2002308956A JP2001118027A JP2001118027A JP2002308956A JP 2002308956 A JP2002308956 A JP 2002308956A JP 2001118027 A JP2001118027 A JP 2001118027A JP 2001118027 A JP2001118027 A JP 2001118027A JP 2002308956 A JP2002308956 A JP 2002308956A
- Authority
- JP
- Japan
- Prior art keywords
- novolak resin
- resin
- meth
- partially
- phenolic hydroxyl
- 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.)
- Granted
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は硬化性樹脂に関し、
詳しくは作業性、均一混合性等に優れる部分（メタ）ア
クリロイル化ノボラック樹脂に関するものである。The present invention relates to a curable resin,
More specifically, the present invention relates to a partially (meth) acryloylated novolak resin excellent in workability, uniform mixing property, and the like.
【０００２】[0002]
【従来の技術】従来より、接着剤、塗料、積層材、成形
材料など多くの分野で用いられてきた硬化性樹脂として
は、縮合硬化型のフェノール樹脂、或いはラジカル硬化
型の不飽和ポリエステル樹脂及びビニルエステル樹脂な
どが挙げられる。2. Description of the Related Art Curable resins which have been used in various fields such as adhesives, paints, laminates and molding materials include condensation-curable phenol resins and radical-curable unsaturated polyester resins. And vinyl ester resins.
【０００３】フェノール樹脂は、ヘキサミンで代表され
る架橋剤にて硬化させるノボラック型フェノール樹脂
と、メチロール基及び／又はジメチレンエーテル結合等
の架橋種によって自己硬化するレゾール樹脂が知られて
いる。しかしながら、これらの樹脂は以下に述べるよう
な縮合硬化に伴う幾つかの欠点を有するため、その用途
が余儀なく制約される。 （１）フェノール樹脂は、分子中にフェノール性水酸基
を有し、且つ硬化時には水、アンモニア、ホルムアルデ
ヒド等を発生するため、硬化物中に多数のガス孔が形成
され、故に、硬くて脆く、不透明である。 （２）樹脂の硬化が主にヘキサミンやメチロール基及び
／又はジメチレンエーテル結合等の活性化温度に依存す
るため、硬化条件の自由度が小さい。 （３）ヘキサミンを使用するノボラック樹脂において
は、未反応ヘキサミン、低級アミン等の不純物が硬化物
中に存在するため、電気絶縁性の低下や金属の腐食等、
電気・電子部品の材料として使用する際には不都合な問
題を生じやすい。 （４）レゾール樹脂においては、一般に硬化が遅く、そ
のため酸を使用することによる腐食問題がある。硬化の
速い物においては熱的に不安定であり、作業性や保存安
定性に問題がある。As the phenol resin, a novolak type phenol resin cured by a crosslinking agent represented by hexamine and a resol resin self-cured by a crosslinking species such as a methylol group and / or a dimethylene ether bond are known. However, these resins have some drawbacks associated with condensation curing, as described below, which limits their use. (1) A phenol resin has a phenolic hydroxyl group in a molecule and generates water, ammonia, formaldehyde, and the like at the time of curing, so that a large number of gas holes are formed in the cured product, and therefore, it is hard, brittle, and opaque. It is. (2) Since the curing of the resin mainly depends on the activation temperature of a hexamine or methylol group and / or a dimethylene ether bond, the degree of freedom of the curing conditions is small. (3) In the novolak resin using hexamine, impurities such as unreacted hexaamine and lower amine are present in the cured product, so that the electrical insulation is lowered and metal corrosion is caused.
When used as a material for electric / electronic parts, disadvantageous problems are likely to occur. (4) In the case of resole resins, curing is generally slow, and therefore, there is a corrosion problem due to the use of an acid. A fast-curing material is thermally unstable and has problems in workability and storage stability.
【０００４】一方、不飽和ポリエステル樹脂及びビニル
エステル樹脂は、ラジカル重合によって硬化するため、
ボイドの発生が無く、硬化方法及び硬化条件の自由度が
大きく、電気特性・光学特性などに優れる。しかしなが
ら、フェノール性水酸基を有しないため、フェノール性
水酸基に起因する特徴、即ち、エポキシ樹脂に代表され
る他樹脂との反応性、複合材料における基材、補強材等
との密着性、硬化した樹脂中のフェノール性水酸基の分
子間相互作用による強度等が、フェノール樹脂よりも低
下する。On the other hand, unsaturated polyester resins and vinyl ester resins are cured by radical polymerization,
No voids are generated, the degree of freedom of the curing method and curing conditions is large, and the electrical properties and optical properties are excellent. However, since it does not have a phenolic hydroxyl group, it is characterized by the phenolic hydroxyl group, that is, reactivity with other resins represented by an epoxy resin, adhesion to a substrate in a composite material, a reinforcing material, etc., and a cured resin. The strength and the like due to the intermolecular interaction of the phenolic hydroxyl groups therein are lower than those of the phenolic resin.
【０００５】ビニルエステル樹脂は一般的にエポキシ樹
脂と（メタ）アクリル酸とを反応させる方法で合成され
る。そのため、樹脂中にフェノール性水酸基を含有しな
い。また、ノボラック樹脂のフェノール性水酸基と、こ
れに対して当量以下のグリシジル（メタ）アクリレート
を反応させることにより、樹脂中にフェノール性水酸基
を含有するラジカル硬化型の樹脂が知られている（特開
平８−３１１１３７号公報）。[0005] Vinyl ester resins are generally synthesized by reacting an epoxy resin with (meth) acrylic acid. Therefore, the resin does not contain a phenolic hydroxyl group. Further, a radical-curable resin containing a phenolic hydroxyl group in a resin by reacting a phenolic hydroxyl group of a novolak resin with glycidyl (meth) acrylate in an equivalent amount or less with respect to the phenolic hydroxyl group has been known (Japanese Patent Application Laid-Open No. HEI 9-279421). 8-31137).
【０００６】[0006]
【発明が解決しようとする課題】特開平８−３１１１３
７号公報に記載された部分（メタ）アクリロイル化ノボ
ラック樹脂はフェノール性水酸基を含有するものであ
る。しかしながら、該樹脂はノボラック樹脂のフェノー
ル性水酸基とグリシジル（メタ）アクリレートを反応さ
せる際に粘度が高いため、ゲル化を起こし易い。また、
生成物が固形状であるめ有機過酸化物との混合時の危険
性があり、均一混合性が悪く、スポットゲル等により均
一に硬化を行うことが困難である。本発明の目的は、フ
ェノール樹脂、不飽和ポリエステル樹脂及びビニルエス
テル樹脂などのラジカル硬化型樹脂のそれぞれの特徴を
活かしつつ、作業性、均一混合性の優れる硬化性樹脂を
提供することにある。Problems to be Solved by the Invention
The partially (meth) acryloylated novolak resin described in JP-A No. 7-containing publication contains a phenolic hydroxyl group. However, the resin has a high viscosity when reacting the phenolic hydroxyl group of the novolak resin with glycidyl (meth) acrylate, and thus is liable to gel. Also,
Since the product is in a solid state, there is a danger at the time of mixing with an organic peroxide, the uniform mixing property is poor, and it is difficult to uniformly cure by a spot gel or the like. An object of the present invention is to provide a curable resin having excellent workability and uniform mixing properties while utilizing the characteristics of radical curable resins such as a phenol resin, an unsaturated polyester resin, and a vinyl ester resin.
【０００７】[0007]
【課題を解決するための手段】本発明者らは上記の如き
課題を有する硬化性樹脂について鋭意検討した結果、フ
ェノール類とアルデヒド類のモル比を特定範囲として製
造されたノボラック樹脂とグリシジル（メタ）アクリレ
ートとを反応させることにより常温で液状の部分（メ
タ）アクリロイル化ノボラック樹脂が得られ、該樹脂
は、作業性が良く、また有機過酸化物等との均一混合性
に優れる硬化性樹脂であることを見出し、本発明に到達
した。The present inventors have conducted intensive studies on curable resins having the above-mentioned problems, and as a result, have found that a novolak resin and a glycidyl (meth) resin prepared with a molar ratio of phenols to aldehydes in a specific range are used. ) By reacting with acrylate, a partially (meth) acryloylated novolak resin which is liquid at room temperature can be obtained. The resin is a curable resin having good workability and excellent in uniform mixing with organic peroxides and the like. The inventors have found that the present invention has reached the present invention.
【０００８】即ち本発明は、フェノール類（Ｐ）に対す
るアルデヒド類（Ｆ）のモル比（Ｆ／Ｐ）が０．１〜
０．３５で製造され、未反応フェノール類モノマー含有
率が０．５％以下であるノボラック樹脂と、該ノボラッ
ク樹脂のフェノール性水酸基に対して当量未満のグリシ
ジル（メタ）アクリレートとを反応させることにより得
られ、分子中にフェノール性水酸基を有し、常温で液状
であることを特徴とする部分（メタ）アクリロイル化ノ
ボラック樹脂である。That is, according to the present invention, the molar ratio (F / P) of the aldehyde (F) to the phenol (P) is 0.1 to 0.1.
By reacting a novolak resin produced at 0.35 with an unreacted phenolic monomer content of 0.5% or less, and glycidyl (meth) acrylate having an equivalent of less than the phenolic hydroxyl group of the novolak resin. A partially (meth) acryloylated novolak resin obtained, having a phenolic hydroxyl group in the molecule and being liquid at normal temperature.
【０００９】[0009]
【発明の実の施形態】本発明においてノボラック樹脂を
製造するために用いられるフェノール類モノマーは、水
酸基を芳香核に有する物であれば良く、例えば、フェノ
ールをはじめ、クレゾール、キシレノール、ブチルフェ
ノール、オクチルフェノール、ノニルフェノール等のア
ルキルフェノール類、更に、カテコール、レゾルシン、
ヒドロキノン等の多価フェノール類、ビスフェノール
Ａ、ビスフェノールＦ、ビスフェノールＳ等の多核フェ
ノール類等を挙げることができ、これらの１種若しくは
２種以上を組み合わせても良い。また、本発明において
ノボラック樹脂を製造するため用いられるアルデヒド類
は、例えば、ホルムアルデヒド、パラホルムアルデヒ
ド、フルフラール、ベンズアルデヒド等が挙げることが
でき、これらの１種若しくは２種以上を組み合わせても
良い。DETAILED DESCRIPTION OF THE INVENTION The phenolic monomer used for producing the novolak resin in the present invention may be any one having a hydroxyl group in an aromatic nucleus. For example, phenol, cresol, xylenol, butylphenol, octylphenol , Alkylphenols such as nonylphenol, further, catechol, resorcinol,
Examples thereof include polyhydric phenols such as hydroquinone, and polynuclear phenols such as bisphenol A, bisphenol F, and bisphenol S. These may be used alone or in combination of two or more. In addition, examples of the aldehyde used for producing the novolak resin in the present invention include formaldehyde, paraformaldehyde, furfural, and benzaldehyde, and one or more of these may be used in combination.
【００１０】本発明において、ノボラック樹脂の製造に
おけるフェノール類（Ｐ）に対するアルデヒド類（Ｆ）
のモル比（Ｆ／Ｐ）は０．１〜０．３５、好ましくは
０．２〜０．３３である。該モル比が０．３５を越える
と、グリシジル（メタ）アクリレートとの生成物である
部分（メタ）アクリロイル化ノボラック樹脂が常温で半
固形又は固形となり、粉体の部分（メタ）アクリロイル
化ノボラックを有機過酸化物と混合して硬化させる際、
混合時に爆発等の危険性があり、又混合物を硬化させる
際はスポットゲル等を発生させ、均一に硬化させること
が困難である。該モル比を０．３５以下とすることでグ
リシジル（メタ）アクリレートとの生成物が液状とな
り、均一に硬化をすることができる。また、該モル比が
０．１未満ではグリシジル（メタ）アクリレートとの生
成物である部分（メタ）アクリロイル化ノボラック樹脂
は常温で液状であるが、硬化物においては架橋密度が低
く、良好な物性が得られない。In the present invention, an aldehyde (F) relative to a phenol (P) in the production of a novolak resin is used.
Is from 0.1 to 0.35, preferably from 0.2 to 0.33. When the molar ratio exceeds 0.35, the part (meth) acryloylated novolak resin, which is a product with glycidyl (meth) acrylate, becomes semi-solid or solid at room temperature, and the powdered part (meth) acryloylated novolak becomes When mixed with organic peroxide and cured,
There is a risk of explosion or the like during mixing, and when the mixture is cured, a spot gel or the like is generated, and it is difficult to uniformly cure the mixture. By setting the molar ratio to 0.35 or less, the product with glycidyl (meth) acrylate becomes liquid and can be uniformly cured. When the molar ratio is less than 0.1, the partially (meth) acryloylated novolak resin which is a product with glycidyl (meth) acrylate is liquid at room temperature, but the cured product has a low crosslink density and good physical properties. Can not be obtained.
【００１１】本発明において、製造されたノボラック樹
脂中の未反応フェノール類モノマーの含有率（以下、フ
リーフェノール含有率と云う）は０．５重量％以下であ
る。好ましくは０．２重量％以下である。０．５重量％
を越えると、部分（メタ）アクリロイル化ノボラック樹
脂の硬化時に、未反応フェノール類モノマーが重合禁止
剤又は遅延剤として働くため硬化性に悪影響を与える。
更に硬化物においては架橋密度を低下させ、耐熱性、機
械的特性等を低下させる原因となる。In the present invention, the content of unreacted phenolic monomers in the produced novolak resin (hereinafter referred to as free phenol content) is 0.5% by weight or less. It is preferably at most 0.2% by weight. 0.5% by weight
Is exceeded, the unreacted phenolic monomer acts as a polymerization inhibitor or a retarder when the partially (meth) acryloylated novolak resin is cured, which adversely affects the curability.
Further, in the cured product, the crosslinking density is reduced, which causes a reduction in heat resistance, mechanical properties, and the like.
【００１２】本発明による部分（メタ）アクリロイル化
ノボラック樹脂は、上記のノボラック樹脂とグリシジル
（メタ）アクリレートをアミン類等の塩基性触媒存在
下、公知の方法で５０〜１２０℃、好ましくは６０〜８
５℃の温度範囲で反応させることにより得られる。５０
℃未満では反応が遅く実用的ではない。又、１２０℃を
越えると合成中にゲル化を起こす危険性がある。樹脂を
合成する際は、反応中の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
をすることが望ましい。The partially (meth) acryloylated novolak resin according to the present invention can be prepared by subjecting the novolak resin and glycidyl (meth) acrylate to a known method at 50 to 120 ° C., preferably 60 to 120 ° C. in the presence of a basic catalyst such as an amine. 8
It is obtained by reacting in a temperature range of 5 ° C. 50
If the temperature is lower than ℃, the reaction is slow and not practical. On the other hand, when the temperature exceeds 120 ° C., there is a risk that gelation occurs during the synthesis. When synthesizing the resin, a polymerization inhibitor may be added for the purpose of preventing gelation during the reaction. It is desirable to perform air bubbling during the reaction.
【００１３】ノボラック樹脂とグリシジル（メタ）アク
リレートの反応に用いる塩基性触媒としては、反応を促
進する物であれば良く、例えば、脂肪族アミン、芳香族
アミン、イミダゾール等が使用できる。これらの触媒の
使用量は、処方条件に応じ適宜決められるが、一般的に
はノボラック樹脂１００重量部に対して０．１〜１０重
量部の範囲が適当である。The basic catalyst used in the reaction between the novolak resin and glycidyl (meth) acrylate may be any substance that promotes the reaction, and examples thereof include aliphatic amines, aromatic amines and imidazole. The amount of these catalysts used is appropriately determined according to the prescription conditions, but is generally in the range of 0.1 to 10 parts by weight per 100 parts by weight of the novolak resin.
【００１４】重合禁止剤としては、例えば、キノン類、
多価フェノール類、フェノール類、有機ならびに無機の
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ミンアルミニウム塩
等が挙げられる。また該反応は、反応溶媒として、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
の溶媒の存在下で行うことができる。As the polymerization inhibitor, for example, quinones,
Polyhydric phenols, phenols, organic and inorganic copper salts, amines, nitro compounds, oximes, sulfurs,
N-nitrosophenylhydroxylamine aluminum salt and the like. The reaction can be performed in the presence of a solvent such as methyl ethyl ketone, methyl isobutyl ketone, or acetone as a reaction solvent.
【００１５】ノボラック樹脂に反応せしめるグリシジル
（メタ）アクリレートの割合は、フェノール性水酸基に
対して当量未満であれば任意に決めることができるが、
好ましくは３０〜９０％、より好ましくは５０〜９０％
の変性率である。変性率が３０％未満であると生成物の
部分（メタ）アクリロイル化ノボラック樹脂の粘度が高
く取り扱いが困難であると共に、硬化物の架橋密度が低
下して良好な物性が得られない。また、変性率が９０％
を越えると粘度が低下して作業性が良好になるが、フェ
ノール性水酸基に起因する特長が得られない。The proportion of glycidyl (meth) acrylate to be reacted with the novolak resin can be arbitrarily determined as long as it is less than the equivalent to the phenolic hydroxyl group.
Preferably 30-90%, more preferably 50-90%
Is the denaturation rate. If the modification rate is less than 30%, the viscosity of the partially (meth) acryloylated novolak resin of the product is high and handling is difficult, and the crosslinked density of the cured product is lowered, so that good physical properties cannot be obtained. The denaturation rate is 90%
If it exceeds, the viscosity is reduced and the workability is improved, but the features derived from the phenolic hydroxyl group cannot be obtained.
【００１６】本発明による部分（メタ）アクリロイル化
ノボラック樹脂は、種々の目的で変性された物でも良
く、補助成分として、充填剤、離型剤、重合開始剤、重
合促進剤、シランカップリング剤、着色剤、難燃剤、可
塑剤、酸化防止剤、及び反応性希釈剤等の添加剤を加え
ても良い。The partially (meth) acryloylated novolak resin according to the present invention may be modified for various purposes, and may contain, as auxiliary components, a filler, a release agent, a polymerization initiator, a polymerization accelerator, a silane coupling agent. And additives such as a colorant, a flame retardant, a plasticizer, an antioxidant, and a reactive diluent.
【００１７】添加剤としては、例えばラジカル重合性モ
ノマーがあり、（メタ）アクリル酸類、（メタ）アクリ
ルアミド類、スチレン、ビニルピロリドン、ジアリルフ
タレート等が挙げられる。重合開始剤としては、有機系
過酸化物や無機系過酸化物、光開始剤のごとくラジカル
を発生する化合物等が挙げられる。また、前記重合開始
剤には必要に応じて重合促進剤、例えばナフテン酸コバ
ルト、ジメチルアニリン、トリエチルアミン等を適量併
用することができる。The additives include, for example, radically polymerizable monomers, and include (meth) acrylic acids, (meth) acrylamides, styrene, vinylpyrrolidone, diallyl phthalate and the like. Examples of the polymerization initiator include organic peroxides, inorganic peroxides, and compounds that generate radicals such as photoinitiators. If necessary, a suitable amount of a polymerization accelerator, for example, cobalt naphthenate, dimethylaniline, triethylamine or the like can be used as the polymerization initiator.
【００１８】また、本発明による部分（メタ）アクリロ
イル化ノボラック樹脂は、フェノール性水酸基を有する
ため、従来フェノール樹脂と同様に、エポキシ樹脂やイ
ソシアネート化合物等フェノール性水酸基と反応し得る
化合物を併用することが可能である。本発明の部分（メ
タ）アクリロイル化ノボラック樹脂は、通常の加熱手段
によって硬化を行うことができるが、必ずしもこれに限
定される物ではなく、使用目的に応じて紫外線、赤外
線、エックス線、電子線等を使用することもできる。Since the partially (meth) acryloylated novolak resin according to the present invention has a phenolic hydroxyl group, a compound capable of reacting with a phenolic hydroxyl group such as an epoxy resin or an isocyanate compound is used in the same manner as a conventional phenolic resin. Is possible. The partially (meth) acryloylated novolak resin of the present invention can be cured by ordinary heating means, but is not necessarily limited thereto, and may be ultraviolet, infrared, X-ray, electron beam, or the like depending on the purpose of use. Can also be used.
【００１９】[0019]
【実施例】次に実施例により本発明を更に具体的に説明
する。但し本発明は以下の実施例により制限されるもの
では無い。なお、各実施例および比較例において得られ
た部分メタクリロイル化ノボラック樹脂の性能試験を次
のように行なった。すなわち、各実施例および比較例に
おいて得られた部分メタクリロイル化ノボラック樹脂１
００重量部に対してt-ブチルパーオキシベンゾエート
（日本油脂株式会社製、商品名「パーブチルＺ」）２重
量部を混合し、１２０℃で２時間、硬化反応をさせた。
熱膨張測定（TMA)からガラス転移温度（Tg）を求めた。Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples. In addition, the performance test of the partially methacryloylated novolak resin obtained in each of Examples and Comparative Examples was performed as follows. That is, the partially methacryloylated novolak resin 1 obtained in each of Examples and Comparative Examples
2 parts by weight of t-butyl peroxybenzoate (trade name "Perbutyl Z" manufactured by NOF Corporation) was mixed with 00 parts by weight, and a curing reaction was performed at 120 ° C. for 2 hours.
The glass transition temperature (Tg) was determined from the thermal expansion measurement (TMA).
【００２０】実施例１ 温度計、攪拌機及び還流冷却器を備えたセパラブルフラ
スコにフェノールノボラック樹脂（Ｆ／Ｐ＝０．３, フ
リーフェノール：０．１％）１００重量部、メチルエチ
ルケトン３０重量部、グリシジルメタクリレート１２５
重量部、N-ニトロソフェニルヒドロキシルアミンアルミ
ニウム塩０．０５重量部、トリエチルアミン４重量部を
仕込み、エアーバブリング中、８０℃で６時間反応し
た。真空脱溶媒を行い、２５℃で液状の部分メタクリロ
イル化ノボラック樹脂を得た。２５℃での粘度は２０Pa
・sであった。性能試験結果を第１表に示す。ガラス転
移温度（Tg）が１３２℃の良好な硬化物が得られた。Example 1 In a separable flask equipped with a thermometer, a stirrer and a reflux condenser, 100 parts by weight of phenol novolak resin (F / P = 0.3, free phenol: 0.1%), 30 parts by weight of methyl ethyl ketone, Glycidyl methacrylate 125
Parts by weight, N-nitrosophenylhydroxylamine aluminum salt 0.05 parts by weight, and triethylamine 4 parts by weight were charged and reacted at 80 ° C. for 6 hours in air bubbling. The solvent was removed under vacuum to obtain a liquid partially methacryloylated novolak resin at 25 ° C. The viscosity at 25 ° C is 20 Pa
・ It was s. Table 1 shows the performance test results. A good cured product having a glass transition temperature (Tg) of 132 ° C. was obtained.
【００２１】実施例２ 温度計、攪拌機及び還流冷却器を備えたセパラブルフラ
スコにフェノールノボラック樹脂（Ｆ／Ｐ＝０．３, フ
リーフェノール：０．１％）１００重量部、メチルエチ
ルケトン３０重量部、グリシジルメタクリレート９７．
５重量部、N-ニトロソフェニルヒドロキシルアミンアル
ミニウム塩０．０５重量部、トリエチルアミン２重量部
を仕込み、エアーバブリング中、８０℃で６時間反応し
た。真空脱溶媒を行い、２５℃で液状の部分メタクリロ
イル化ノボラック樹脂を得た。２５℃での粘度は２，０
００Pa・sであった。性能試験結果を第１表に示す。ガ
ラス転移温度（Tg）が７２℃の良好な硬化物が得られ
た。Example 2 100 parts by weight of a phenol novolak resin (F / P = 0.3, free phenol: 0.1%), 30 parts by weight of methyl ethyl ketone were placed in a separable flask equipped with a thermometer, a stirrer and a reflux condenser. Glycidyl methacrylate 97.
5 parts by weight, 0.05 parts by weight of N-nitrosophenylhydroxylamine aluminum salt and 2 parts by weight of triethylamine were charged and reacted at 80 ° C. for 6 hours in air bubbling. The solvent was removed under vacuum to obtain a liquid partially methacryloylated novolak resin at 25 ° C. The viscosity at 25 ° C is 2.0
It was 00 Pa · s. Table 1 shows the performance test results. A good cured product having a glass transition temperature (Tg) of 72 ° C. was obtained.
【００２２】比較例１ 温度計、攪拌機及び還流冷却器を備えたセパラブルフラ
スコにフェノールノボラック樹脂（Ｆ／Ｐ＝０．６, フ
リーフェノール：０．１％）１００重量部、メチルエチ
ルケトン３０重量部、グリシジルメタクリレート９６．
５重量部、N-ニトロソフェニルヒドロキシルアミンアル
ミニウム塩０．０５重量部、トリエチルアミン２重量部
を仕込み、エアーバブリング中、８０℃で６時間反応し
た。真空脱溶媒を行い、２５℃で固形の部分メタクリロ
イル化ノボラック樹脂を得た。この場合は固形樹脂のた
め作業性や混合性が悪く、上記の性能試験を行わなかっ
た。Comparative Example 1 100 parts by weight of a phenol novolak resin (F / P = 0.6, free phenol: 0.1%), 30 parts by weight of methyl ethyl ketone were placed in a separable flask equipped with a thermometer, a stirrer and a reflux condenser. Glycidyl methacrylate
5 parts by weight, 0.05 parts by weight of N-nitrosophenylhydroxylamine aluminum salt and 2 parts by weight of triethylamine were charged and reacted at 80 ° C. for 6 hours in air bubbling. The solvent was removed under vacuum to obtain a partially methacryloylated novolak resin solid at 25 ° C. In this case, workability and mixability were poor due to the solid resin, and the above-described performance test was not performed.
【００２３】比較例２ 温度計、攪拌機及び還流冷却器を備えたセパラブルフラ
スコにフェノールノボラック樹脂（Ｆ／Ｐ＝０．０５,
フリーフェノール：０．１％）１００重量部、メチルエ
チルケトン３０重量部、グリシジルメタクリレート９
８．４重量部、N-ニトロソフェニルヒドロキシルアミン
アルミニウム塩０．０５重量部、トリエチルアミン２重
量部を仕込み、エアーバブリング中、８０℃で６時間反
応した。真空脱溶媒を行い、２５℃で液状の部分メタク
リロイル化ノボラック樹脂を得た。２５℃での粘度は４
７０Pa・sであった。性能試験結果を第１表に示す。ガ
ラス転移温度（Tg）が室温以下であり、良好な硬化物は
得られなかった。Comparative Example 2 Phenol novolak resin (F / P = 0.05, phenol novolak resin) was placed in a separable flask equipped with a thermometer, a stirrer and a reflux condenser.
Free phenol: 0.1%) 100 parts by weight, methyl ethyl ketone 30 parts by weight, glycidyl methacrylate 9
8.4 parts by weight, 0.05 parts by weight of N-nitrosophenylhydroxylamine aluminum salt and 2 parts by weight of triethylamine were charged and reacted at 80 ° C. for 6 hours in air bubbling. The solvent was removed under vacuum to obtain a liquid partially methacryloylated novolak resin at 25 ° C. The viscosity at 25 ° C is 4
It was 70 Pa · s. Table 1 shows the performance test results. The glass transition temperature (Tg) was below room temperature, and no good cured product was obtained.
【００２４】比較例３ 実施例２において、フリーフェノール：１．０％のフェ
ノールノボラック樹脂を用いた以外は、実施例２と同様
に行った。得られた２５℃で液状の部分メタクリロイル
化ノボラック樹脂の２５℃での粘度は２０００Pa・sで
あった。性能試験結果を第１表に示す。ガラス転移温度
（Tg）が室温以下であり、良好な硬化物は得られなかっ
た。Comparative Example 3 The procedure of Example 2 was repeated, except that a phenol novolak resin containing 1.0% of free phenol was used. The viscosity at 25 ° C. of the obtained partially methacryloylated novolak resin liquid at 25 ° C. was 2000 Pa · s. Table 1 shows the performance test results. The glass transition temperature (Tg) was below room temperature, and no good cured product was obtained.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明による部分メタクリロイル化ノボ
ラック樹脂は、分子中にフェノール性水酸基を有する常
温で液状のラジカル硬化型の樹脂であり、作業性、均一
混合性等に優れていることから、塗料や接着剤などに有
利に用いることができる。The partially methacryloylated novolak resin according to the present invention is a radical-curable resin which has a phenolic hydroxyl group in the molecule and is liquid at room temperature and is excellent in workability and uniform mixing properties. And adhesives.
フロントページの続き Ｆターム(参考） 4J027 AA08 AH03 AJ04 4J033 CA02 CA03 CA04 CA05 CA11 CA12 CA13 CA14 CA18 CA19 CB03 CD03 HA12 HA28 HB01 HB08 HB09 Continued on the front page F-term (reference) 4J027 AA08 AH03 AJ04 4J033 CA02 CA03 CA04 CA05 CA11 CA12 CA13 CA14 CA18 CA19 CB03 CD03 HA12 HA28 HB01 HB08 HB09
Claims (2)
類（Ｆ）のモル比（Ｆ／Ｐ）が０．１〜０．３５で製造
され、未反応フェノール類モノマー含有率が０．５％以
下であるノボラック樹脂と、該ノボラック樹脂のフェノ
ール性水酸基に対して当量未満のグリシジル（メタ）ア
クリレートとを反応させることにより得られ、分子中に
フェノール性水酸基を有し、常温で液状であることを特
徴とする部分（メタ）アクリロイル化ノボラック樹脂。1. The method according to claim 1, wherein the molar ratio (F / P) of the aldehyde (F) to the phenol (P) is 0.1 to 0.35, and the unreacted phenol monomer content is 0.5% or less. It is obtained by reacting a certain novolak resin with glycidyl (meth) acrylate in an amount equivalent to less than the phenolic hydroxyl group of the novolak resin, has a phenolic hydroxyl group in the molecule, and is liquid at normal temperature. (Meth) acryloylated novolak resin.
ノール性水酸基の当量比が０．５〜０．９である請求項
１に記載の部分（メタ）アクリロイル化ノボラック樹
脂。2. The partially (meth) acryloylated novolak resin according to claim 1, wherein the equivalent ratio of glycidyl (meth) acrylate / phenolic hydroxyl group is 0.5 to 0.9.
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|---|---|---|---|
| JP2001118027A JP5038557B2 (en) | 2001-04-17 | 2001-04-17 | Partially (meth) acryloylated novolak resin |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001118027A JP5038557B2 (en) | 2001-04-17 | 2001-04-17 | Partially (meth) acryloylated novolak resin |
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| JP5038557B2 JP5038557B2 (en) | 2012-10-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263412A (en) * | 2008-04-22 | 2009-11-12 | Showa Highpolymer Co Ltd | Wet friction material and method for producing the same |
| WO2022140641A1 (en) * | 2020-12-23 | 2022-06-30 | Si Group, Inc. | Self-polymerizable phenolic resins |
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| JPH10180403A (en) * | 1996-12-26 | 1998-07-07 | Sumitomo Bakelite Co Ltd | Resin composition, permanent resist resin composition, and hardened resin thereof |
| JPH11100422A (en) * | 1997-09-29 | 1999-04-13 | Sumitomo Bakelite Co Ltd | Curable resin composition |
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| JP2002299510A (en) * | 2001-03-30 | 2002-10-11 | Sumitomo Bakelite Co Ltd | Semiconductor device |
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2001
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|---|---|---|---|---|
| JPS6296513A (en) * | 1985-10-23 | 1987-05-06 | Showa Highpolymer Co Ltd | Ultraviolet-curable resin composition |
| JPH0551507A (en) * | 1991-08-26 | 1993-03-02 | Soken Kagaku Kk | Thermosetting acrylate composition |
| JPH08120038A (en) * | 1994-10-24 | 1996-05-14 | Honshu Chem Ind Co Ltd | Liquid phenol novolak resin and its production |
| JPH08311137A (en) * | 1995-05-18 | 1996-11-26 | Sumitomo Bakelite Co Ltd | Curable resin composition |
| JPH10180403A (en) * | 1996-12-26 | 1998-07-07 | Sumitomo Bakelite Co Ltd | Resin composition, permanent resist resin composition, and hardened resin thereof |
| JPH11100422A (en) * | 1997-09-29 | 1999-04-13 | Sumitomo Bakelite Co Ltd | Curable resin composition |
| JP2000248042A (en) * | 1999-02-25 | 2000-09-12 | Sumitomo Bakelite Co Ltd | Curable resin composition and its thickening |
| JP2002299510A (en) * | 2001-03-30 | 2002-10-11 | Sumitomo Bakelite Co Ltd | Semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009263412A (en) * | 2008-04-22 | 2009-11-12 | Showa Highpolymer Co Ltd | Wet friction material and method for producing the same |
| WO2022140641A1 (en) * | 2020-12-23 | 2022-06-30 | Si Group, Inc. | Self-polymerizable phenolic resins |
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| Publication number | Publication date |
|---|---|
| JP5038557B2 (en) | 2012-10-03 |
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