JP2006104171A - Novel di(meth)acrylate compounds - Google Patents
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Abstract
Description
本発明は、新規なジ（メタ）アクリレート類に関に関する。 The present invention relates to novel di (meth) acrylates.
従来、種々のビスフェノール化合物のジ（メタ）アクリレート類は、光学用材料、高分子改質剤、歯科用硬化材料、帯電防止剤、安定剤、フォトレジスト用モノマー、その他種々の機能性化学品やその原料として用いられているが、その機能性を一層向上させるために、更なる多様な構造を有するものが求められている。 Conventionally, di (meth) acrylates of various bisphenol compounds have been used in optical materials, polymer modifiers, dental curing materials, antistatic agents, stabilizers, photoresist monomers, and other various functional chemicals. Although it is used as the raw material, in order to further improve its functionality, those having further various structures are required.
そこで、分子中にシクロヘキシリデン構造を有するビスフェノール化合物のジ（メタ）アクリレート類が幾つか、例えば、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサンのジ（メタ）アクリレート（例えば、特許文献１参照）やビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサンのジ（メタ）アクリレート（例えば、特許文献２参照）が提案されている。しかしながら、光学用材料、高分子改質剤、フォトレジスト用モノマーの用途等においては、反応性、溶媒への溶解性、光透過性（透明性）、耐熱性等が更に改良されたジ（メタ）アクリレート類の開発が望まれている。
本発明は、ジ（メタ）アクリレート類に関する上述した事情に鑑みてなされたものであって、反応性、溶媒への溶解性、光透過性（透明性）、耐熱性等が更に改善された新規なジ（メタ）アクリレート類を提供することを目的とする。 The present invention has been made in view of the above-described circumstances regarding di (meth) acrylates, and has improved reactivity, solubility in a solvent, light transmittance (transparency), heat resistance, and the like. An object of the present invention is to provide di (meth) acrylates.
本発明によれば、一般式（Ｉ） According to the invention, the general formula (I)
（式中、Ｘは単結合又は一般式（II） Wherein X is a single bond or a general formula (II)
（式中、Ｒ3 とＲ4 はそれぞれ独立して水素原子又は炭素原子数１〜４のアルキル基を示す。）
で表されるアルキリデン基を示し、Ｒ1 は水素原子又はメチル基を示し、Ｒ2 は炭素原子数１〜４のアルキル基を示す。）
で表されるジ（メタ）アクリレート類が提供される。
(In the formula, R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 4 carbon atoms. )
The di (meth) acrylate represented by these is provided.
本発明による上記ジ（メタ）アクリレート類は、ジ（メタ）アクリレートのそれぞれのカルボキシル基にビスシクロヘキシル骨格又はビシクロヘキシル骨格に由来する第３級アルキル基を有するジ（メタ）アクリレート）類であって、反応性、溶媒への溶解性、光透過性（透明性）、耐熱性等にすぐれており、光学用材料、高分子改質剤、フォトレジスト用モノマーの用途等において有用である。 The di (meth) acrylates according to the present invention are di (meth) acrylates having a tertiary alkyl group derived from a biscyclohexyl skeleton or a bicyclohexyl skeleton at each carboxyl group of the di (meth) acrylate. It is excellent in reactivity, solubility in solvents, light transmission (transparency), heat resistance, etc., and is useful in applications such as optical materials, polymer modifiers, and photoresist monomers.
本発明によるジ（メタ）アクリレート）類は、一般式（Ｉ） The di (meth) acrylates) according to the invention have the general formula (I)
（式中、Ｘは単結合又は一般式（II） Wherein X is a single bond or a general formula (II)
（式中、Ｒ3 とＲ4 はそれぞれ独立して水素原子又は炭素原子数１〜４のアルキル基を示す。）
で表されるアルキリデン基を示し、Ｒ1 は水素原子又はメチル基を示し、Ｒ2 は炭素原子数１〜４のアルキル基を示す。）
で表される。本発明において、（メタ）アクリレートはアクリレート又はメタクリレートを意味するものとする。
(In the formula, R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 4 carbon atoms. )
It is represented by In the present invention, (meth) acrylate means acrylate or methacrylate.
上記一般式（Ｉ）で表されるジ（メタ）アクリレート類において、Ｒ1 は水素原子又はメチル基を示し、Ｒ2 は炭素原子数１〜４のアルキル基を示す。炭素原子数１〜４のアルキル基としては、メチル基、エチル基、プロピル基又はブチル基を挙げることができる。このうち、プロピル基とブチル基は直鎖状でもよく、分枝鎖状であってもよい。 In the di (meth) acrylates represented by the general formula (I), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, the propyl group and the butyl group may be linear or branched.
また、上記一般式（II）で表されるアルキリデン基において、Ｒ3 とＲ4 はそれぞれ独立して水素原子又は炭素原子数１〜４のアルキル基を示す。炭素原子数１〜４のアルキル基としては、メチル基、エチル基、プロピル基又はブチル基を挙げることができる。このうち、プロピル基とブチル基は直鎖状でもよく、分枝鎖状であってもよい。 In the alkylidene group represented by the general formula (II), R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, the propyl group and the butyl group may be linear or branched.
従って、本発明によるジ（メタ）アクリレート）類の具体例として、Ｘが単結合であるとき、例えば、
４，４’−ジ（メタ）アクリロイルオキシ−４，４’−ジメチルビシクロヘキシル、
４，４’−ジ（メタ）アクリロイルオキシ−４，４’−ジエチルビシクロヘキシル、
４，４’−ジ（メタ）アクリロイルオキシ−４，４’−ジ−ｎ−プロピルビシクロヘキシル、
４，４’−ジ（メタ）アクリロイルオキシ−４，４’−ジ−イソプロピルビシクロヘキシル、
４，４’−ジ（メタ）アクリロイルオキシ−４，４’−ジ−ｎ−ブチルビシクロヘキシル、
４，４’−ジ（メタ）アクリロイルオキシ−４，４’−ジ−イソブチルビシクロヘキシル等を挙げることができる。
Therefore, as a specific example of di (meth) acrylates) according to the present invention, when X is a single bond, for example,
4,4′-di (meth) acryloyloxy-4,4′-dimethylbicyclohexyl,
4,4′-di (meth) acryloyloxy-4,4′-diethylbicyclohexyl,
4,4′-di (meth) acryloyloxy-4,4′-di-n-propylbicyclohexyl,
4,4′-di (meth) acryloyloxy-4,4′-di-isopropylbicyclohexyl,
4,4′-di (meth) acryloyloxy-4,4′-di-n-butylbicyclohexyl,
4,4′-di (meth) acryloyloxy-4,4′-di-isobutylbicyclohexyl and the like can be mentioned.
また、Ｘがアルキリデン基であるとき、例えば、
ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）メタン、
ビス（４−（メタ）アクリロイルオキシ−４−エチルシクロヘキシル）メタン、
ビス（４−（メタ）アクリロイルオキシ−４−ｎ−プロピルシクロヘキシル）メタン、
ビス（４−（メタ）アクリロイルオキシ−４−イソプロピルシクロヘキシル）メタン、
ビス（４−（メタ）アクリロイルオキシ−４−ｎ−ブチルシクロヘキシル）メタン、
ビス（４−（メタ）アクリロイルオキシ−４−イソブチルシクロヘキシル）メタン、
１，１−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）エタン、１，１−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）プロパン、
１，１−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）ブタン、２−メチル−１，１−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）プロパン、
３−メチル−１，１−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）ブタン、
２，２−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）プロパン、
２，２−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）ブタン、４−メチル−２，２−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）ペンタン、
３，３−ビス（４−（メタ）アクリロイルオキシ−４−メチルシクロヘキシル）ペンタン等を挙げることができる。
When X is an alkylidene group, for example,
Bis (4- (meth) acryloyloxy-4-methylcyclohexyl) methane,
Bis (4- (meth) acryloyloxy-4-ethylcyclohexyl) methane,
Bis (4- (meth) acryloyloxy-4-n-propylcyclohexyl) methane,
Bis (4- (meth) acryloyloxy-4-isopropylcyclohexyl) methane,
Bis (4- (meth) acryloyloxy-4-n-butylcyclohexyl) methane,
Bis (4- (meth) acryloyloxy-4-isobutylcyclohexyl) methane,
1,1-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) ethane, 1,1-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) propane,
1,1-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) butane, 2-methyl-1,1-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) propane,
3-methyl-1,1-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) butane,
2,2-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) propane,
2,2-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) butane, 4-methyl-2,2-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) pentane,
3,3-bis (4- (meth) acryloyloxy-4-methylcyclohexyl) pentane and the like can be mentioned.
本発明によるこのようなジ（メタ）アクリレート類は、下記のスキームに示すように、例えば、ビスシクロヘキサノン（III) にメチルマグネシウムクロライド等のアルキルグリニヤール試薬（IV）を反応させ、次いで、得られた付加反応生成物（Ｖ）に塩化（メタ）アクリロイル（VI）等の（メタ）アクリル酸塩化物を反応させることによって得ることができる。 Such di (meth) acrylates according to the present invention were obtained by reacting, for example, biscyclohexanone (III) with an alkyl Grignard reagent (IV) such as methylmagnesium chloride as shown in the following scheme. It can be obtained by reacting the addition reaction product (V) with a (meth) acrylic acid chloride such as (meth) acryloyl chloride (VI).
上記スキームに示したように、本発明によれば、好ましくは、上記ビスシクロヘキサノンとアルキルグリニヤール試薬との付加反応生成物（Ｖ）に塩化（メタ）アクリロイルを反応させる。 As shown in the above scheme, according to the present invention, (meth) acryloyl chloride is preferably reacted with the addition reaction product (V) of the above biscyclohexanone and an alkyl Grignard reagent.
上記ビスシクロヘキサノン類としては、例えば、１，１’−ビシクロヘキシル−４，４’−ジオン、４，４’−メチレンビスシクロヘキサン−１−オン、４，４’−エチリデンビスシクロヘキサン−１−オン、４，４’−プロピリデンビスシクロヘキサン−１−オン、４，４’−ブチリデンビスシクロヘキサン−１−オン、４，４’−（２−メチルプロピリデン）ビスシクロヘキサン−１−オン、４，４’−（３−メチルブチリデン）ビスシクロヘキサン−１−オン、４，４’−（１−メチルエチリデン）ビスシクロヘキサン−１−オン、４，４’−（１−メチルプロピリデン）ビスシクロヘキサン−１−オン、４，４’−（１，３−ジメチルブチリデン）ビスシクロヘキサン−１−オン、４，４’−（１−エチルプロピリデン）ビスシクロヘキサン−１−オン等を挙げることができる。 Examples of the biscyclohexanones include 1,1′-bicyclohexyl-4,4′-dione, 4,4′-methylenebiscyclohexane-1-one, 4,4′-ethylidenebiscyclohexane-1-one, 4,4′-propylidenebiscyclohexane-1-one, 4,4′-butylidenebiscyclohexane-1-one, 4,4 ′-(2-methylpropylidene) biscyclohexane-1-one, 4,4 '-(3-Methylbutylidene) biscyclohexane-1-one, 4,4'-(1-methylethylidene) biscyclohexane-1-one, 4,4 '-(1-methylpropylidene) biscyclohexane-1 -One, 4,4 '-(1,3-dimethylbutylidene) biscyclohexane-1-one, 4,4'-(1-ethylpropylidene) biscyclo It may be mentioned hexane-1-one and the like.
本発明によれば、これらのなかでは、１，１’−ビシクロヘキシル−４，４’−ジオン、４，４’−メチレンビスシクロヘキサン−１−オン、４，４’−（１−メチルエチリデン）ビスシクロヘキサン−１−オンが好ましく用いられる。 According to the present invention, among these, 1,1′-bicyclohexyl-4,4′-dione, 4,4′-methylenebiscyclohexane-1-one, 4,4 ′-(1-methylethylidene) Biscyclohexane-1-one is preferably used.
他方、上記グリニヤール試薬としては、メチルマグネシウムクロライド、エチルマグネシウムクロライド、メチルマグネシウムブロマイド等が好ましく用いられる。上記ビスクロヘキサノン類とアルキルグリニヤール試薬との反応は溶媒中で行われる。溶媒としては、例えば、無水テトラヒドロフランが用いられる。 On the other hand, methylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide and the like are preferably used as the Grignard reagent. The reaction between the bisclohexanones and the alkyl Grignard reagent is carried out in a solvent. As the solvent, for example, anhydrous tetrahydrofuran is used.
グリニヤール反応終了後、上述したように、生成した付加反応生成物に常法に従って塩化（メタ）アクリロイルを反応させることによって、目的とする新規なジ（メタ）アクリレート類を得ることができる。 After completion of the Grignard reaction, as described above, the objective addition novel di (meth) acrylate can be obtained by reacting the produced addition reaction product with (meth) acryloyl chloride according to a conventional method.
反応終了後、例えば、得られた反応混合物を飽和塩化アンモニウム水溶液等のアルカリ水溶液で中和した後、酢酸エチル、ジエチルエーテル等の溶媒を用いて目的物を抽出し、その後、洗浄、乾燥することによって、目的物の精製品を得ることができる。 After completion of the reaction, for example, the obtained reaction mixture is neutralized with an alkaline aqueous solution such as a saturated aqueous ammonium chloride solution, and then the target product is extracted using a solvent such as ethyl acetate or diethyl ether, and then washed and dried. Thus, a refined product of the target product can be obtained.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
（２，２−ビス（４−メタクリロイルオキシ−４−メチルシクロヘキシル）プロパンの合成）
アルゴン雰囲気下、反応容器に無水テトラヒドロフラン５０ｍＬを入れ、これにメチルマグネシウムクロライドの３．０モル／Ｌ濃度のテトラヒドロフラン溶液１４．８ｍＬを加え、攪拌した。アルゴン雰囲気下、このメチルマグネシウムクロライドのテトラヒドロフラン溶液を攪拌しながら、これに２，２−ビス（４−オキソシクロヘキシル）プロパン５．０ｇの無水テトラヒドロフラン１５０ｍＬの懸濁液を滴下漏斗から反応混合物の温度を５０℃以下に保ちながら滴下した後、無水テトラヒドロフラン１００ｍＬを加え、更に、１時間攪拌した。
Example 1
(Synthesis of 2,2-bis (4-methacryloyloxy-4-methylcyclohexyl) propane)
Under an argon atmosphere, 50 mL of anhydrous tetrahydrofuran was placed in the reaction vessel, and 14.8 mL of a 3.0 mol / L tetrahydrofuran solution of methylmagnesium chloride was added thereto and stirred. While stirring the tetrahydrofuran solution of methylmagnesium chloride under an argon atmosphere, a suspension of 150 mL of anhydrous tetrahydrofuran in 5.0 g of 2,2-bis (4-oxocyclohexyl) propane was added to the temperature of the reaction mixture through a dropping funnel. After dropwise addition while keeping the temperature at 50 ° C. or lower, 100 mL of anhydrous tetrahydrofuran was added, and the mixture was further stirred for 1 hour.
次いで、アルゴン雰囲気下、反応混合物を攪拌しながら、これに塩化メタクリロイル６．０８ｇを滴下し、１７時間室温で攪拌した。得られた反応混合物を飽和塩化アンモニウム水溶液中に注ぎ、酢酸エチルで抽出した。得られた有機層を飽和炭酸水素ナトリウム水溶液、水の順に洗浄した後、減圧濃縮した。得られた油状物をシリカゲルカラムクロマトグラフィ（溶出液５％酢酸エチル／ヘキサン）で精製し、無色油状の２，２−ビス（４−メタクリロイルオキシ−４−メチルシクロヘキシル）プロパン４．０ｇを得た。収率は４７％であった。 Next, while stirring the reaction mixture under an argon atmosphere, 6.08 g of methacryloyl chloride was added dropwise thereto and stirred at room temperature for 17 hours. The resulting reaction mixture was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The obtained organic layer was washed with a saturated aqueous sodium bicarbonate solution and water in this order, and then concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography (eluent 5% ethyl acetate / hexane) to obtain 4.0 g of colorless oily 2,2-bis (4-methacryloyloxy-4-methylcyclohexyl) propane. The yield was 47%.
赤外線吸収スペクトル：図１に示す。νＣ＝Ｏの吸収が１７１３ｃｍ-1にみられる。
プロトンＮＭＲスペクトル（溶媒ＣＤＣｌ3、４００ＭＨｚ）：
Infrared absorption spectrum: shown in FIG. Absorption of νC═O is seen at 1713 cm −1 .
Proton NMR spectrum (solvent CDCl 3 , 400 MHz):
実施例２
（４，４’−ジメタクリロイルオキシ−４，４’−ジメチルビシクロヘキシルの合成）
アルゴン雰囲気下、反応容器に４，４’−ジオキソビシクロヘキシル５．０ｇの無水テトラヒドロフラン１５０ｍＬの懸濁液を入れ、これに攪拌しながら、メチルマグネシウムクロライドの３．０モル／Ｌ濃度のテトラヒドロフラン溶液１８．０ｍＬを滴下漏斗から反応混合物の温度を４０℃以下に保ちながら滴下した後、滴下漏斗を無水テトラヒドロフラン２５ｍＬで洗浄し、この洗浄液も滴下漏斗から滴下した。この後、無水テトラヒドロフラン１００ｍＬを加え、更に、１時間攪拌した。
Example 2
(Synthesis of 4,4′-dimethacryloyloxy-4,4′-dimethylbicyclohexyl)
Under argon atmosphere, a suspension of 150 mL of anhydrous tetrahydrofuran in 5.0 g of 4,4′-dioxobicyclohexyl was placed in a reaction vessel, and while stirring, a 3.0 mol / L concentration tetrahydrofuran solution of methylmagnesium chloride. After dropping 18.0 mL from the dropping funnel while keeping the temperature of the reaction mixture at 40 ° C. or lower, the dropping funnel was washed with 25 mL of anhydrous tetrahydrofuran, and this washing solution was also dropped from the dropping funnel. Thereafter, 100 mL of anhydrous tetrahydrofuran was added, and the mixture was further stirred for 1 hour.
次いで、アルゴン雰囲気下、反応混合物を攪拌しながら、これに塩化メタクリロイル７．４０ｇを滴下し、１７時間室温で攪拌した。得られた反応混合物を飽和塩化アンモニウム水溶液中に注ぎ、酢酸エチルで抽出した。得られた有機層を飽和炭酸水素ナトリウム水溶液、水の順に洗浄した後、減圧濃縮した。得られた油状物をシリカゲルカラムクロマトグラフィー（溶出液１０％酢酸エチル／ヘキサン）で精製し、白色固体状の４，４’−ジメタクリロイルオキシ−４，４’−ジメチルビシクロヘキシル１．６ｇを得た。収率は１８％であった。 Next, while stirring the reaction mixture under an argon atmosphere, 7.40 g of methacryloyl chloride was added dropwise thereto and stirred at room temperature for 17 hours. The resulting reaction mixture was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The obtained organic layer was washed with a saturated aqueous sodium bicarbonate solution and water in this order, and then concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography (eluent: 10% ethyl acetate / hexane) to obtain 1.6 g of 4,4′-dimethacryloyloxy-4,4′-dimethylbicyclohexyl as a white solid. It was. The yield was 18%.
赤外線吸収スペクトル：図２に示す。νＣ＝Ｏの吸収が１７１２ｃｍ-1にみられる。
プロトンＮＭＲスペクトル（溶媒ＣＤＣｌ3、４００ＭＨｚ）：
Infrared absorption spectrum: shown in FIG. Absorption of νC═O is seen at 1712 cm −1 .
Proton NMR spectrum (solvent CDCl 3 , 400 MHz):
Claims (3)
で表されるアルキリデン基を示し、Ｒ1 は水素原子又はメチル基を示し、Ｒ2 は炭素原子数１〜４のアルキル基を示す。）
で表されるジ（メタ）アクリレート類。 Formula (I)
In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 4 carbon atoms. )
Di (meth) acrylates represented by
2,2-bis (4-methacryloyloxy-4-methylcyclohexyl) propane.
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| EP1736828A1 (en) * | 2005-06-24 | 2006-12-27 | Dongjin Semichem Co., Ltd | Photoresist monomer, polymer thereof and photoresist composition including the same |
| KR101190527B1 (en) | 2005-08-12 | 2012-10-16 | 주식회사 동진쎄미켐 | Polymer for photoresist and photoresist composition including the same |
| CN105392770A (en) * | 2013-06-21 | 2016-03-09 | 株式会社大赛璐 | Polyfunctional (meth)acrylate, and method for producing same |
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