JP2006137727A - Method for producing (meth)acrylic acid ester - Google Patents
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本発明は、多環性脂環式炭化水素基を有する（メタ）アクリル酸エステルの製造方法に関する。 The present invention relates to a method for producing a (meth) acrylic acid ester having a polycyclic alicyclic hydrocarbon group.
脂環式炭化水素基を有する（メタ）アクリル酸エステルは、塗料、接着剤、粘着剤、インキ用レジン、レジスト、成型材料、光学材料等に用いられる樹脂の原料として有用である。特に、集積回路の分野では、０．２０μｍ以下のレベルの微細加工が要求されるため、この製造工程で用いられる化学増幅型感放射線性レジスト用樹脂としては、ドライエッチング耐性の高いという理由から、脂環式炭化水素基を有する（メタ）アクリル酸エステルからなる樹脂が非常に有用である。 The (meth) acrylic acid ester having an alicyclic hydrocarbon group is useful as a raw material for resins used in paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials and the like. In particular, in the field of integrated circuits, fine processing of a level of 0.20 μm or less is required. Therefore, as a chemically amplified radiation-sensitive resist resin used in this manufacturing process, because of high dry etching resistance, A resin comprising a (meth) acrylic acid ester having an alicyclic hydrocarbon group is very useful.
脂環式炭化水素基を有する（メタ）アクリル酸エステルとして、特許文献１には、下記式（３−１）に示す化合物が提案されており、該化合物に由来する繰り返し単位を有する樹脂を含むレジストは、ドライエッチング耐性に優れ、基板密着性、アルカリ現像液に対し良好な溶解性を示し、高感度、高解像度であるとされている。 As (meth) acrylic acid ester having an alicyclic hydrocarbon group, Patent Document 1 proposes a compound represented by the following formula (3-1), and includes a resin having a repeating unit derived from the compound. The resist is excellent in dry etching resistance, exhibits good substrate adhesion and good solubility in an alkaline developer, and is said to have high sensitivity and high resolution.
また、脂環式炭化水素基を有する（メタ）アクリル酸エステルとして、特許文献１には、下記式（４−１）、（４−２）で表される化合物が開示され、該化合物に由来する繰り返し単位を有する樹脂を含むレジストは、透明性、感度、解像度、パターン形状、ドライエッチング耐性、露光後の加熱温度の変動に対する線幅安定性に優れるとされている。 Further, as (meth) acrylic acid ester having an alicyclic hydrocarbon group, Patent Document 1 discloses compounds represented by the following formulas (4-1) and (4-2), and is derived from the compound. A resist containing a resin having a repeating unit is said to be excellent in transparency, sensitivity, resolution, pattern shape, dry etching resistance, and line width stability against a change in heating temperature after exposure.
（式（４−１）および式（４−２）中、Ｒは水素原子またはメチル基を表す。）
式（４−１）、（４−２）で表される化合物は、例えば、式（３−１）に示す化合物における脂環式炭化水素基に結合するカルボキシル基をエステル化することで得ることができる。
このように、式（３−１）に示す化合物は、それ自体がレジスト用樹脂の原料として有用であり、かつ式（４−１）、（４−２）で表される化合物のような他の脂環式炭化水素基を有する（メタ）アクリル酸エステルの原料としても有用である。
(In the formulas (4-1) and (4-2), R represents a hydrogen atom or a methyl group.)
The compounds represented by formulas (4-1) and (4-2) can be obtained, for example, by esterifying a carboxyl group bonded to an alicyclic hydrocarbon group in the compound represented by formula (3-1). Can do.
As described above, the compound represented by the formula (3-1) is useful as a raw material for the resist resin itself, and other compounds such as the compounds represented by the formulas (4-1) and (4-2). It is also useful as a raw material for a (meth) acrylic acid ester having an alicyclic hydrocarbon group.
特許文献１において、式（３−１）に示す化合物は、下記式（３−２）で表されるノルボルネンカルボン酸ｔｅｒｔ−ブチルとメタクリル酸とを、硫酸および水の存在下で反応させることによって製造されている。 In Patent Document 1, the compound represented by the formula (3-1) is obtained by reacting tert-butyl norbornenecarboxylate represented by the following formula (3-2) with methacrylic acid in the presence of sulfuric acid and water. It is manufactured.
しかしながら、この方法では、出発原料がノルボルネンカルボン酸ｔｅｒｔ−ブチルという一般に流通していない物質であり、また、入手できたとしても価格が高い等の問題がある。また、この方法では、式（３−１）に示す化合物の収率が低いという問題もある。
よって、本発明の目的は、入手しやすい原料を用い、安価に、かつ収率よく、多環性脂環式炭化水素基を有する（メタ）アクリル酸エステルを製造する方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a (meth) acrylic acid ester having a polycyclic alicyclic hydrocarbon group at a low cost and in a high yield, using easily available raw materials. .
本発明の（メタ）アクリル酸エステルの製造方法は、下記式（１−１）または式（１−２）で表される化合物に（メタ）アクリロイル基を導入して下記式（２−１）または式（２−２）で表される化合物を得ることを特徴とする。 In the method for producing a (meth) acrylic acid ester of the present invention, a (meth) acryloyl group is introduced into a compound represented by the following formula (1-1) or formula (1-2), and the following formula (2-1): Alternatively, a compound represented by the formula (2-2) is obtained.
（式（１−１）、式（１−２）、式（２−１）および式（２−２）中、Ｒ1 〜Ｒ9 、Ｒ11〜Ｒ19はそれぞれ独立に水素原子、または酸素原子を含んでもよい炭素数１〜４の１価の炭化水素基を表し、Ｒ20は水素原子またはメチル基を表す。） (In Formula (1-1), Formula (1-2), Formula (2-1), and Formula (2-2), R 1 to R 9 and R 11 to R 19 are each independently a hydrogen atom or oxygen. It contains atom represents a monovalent hydrocarbon group which may having 1 to 4 carbon atoms, R 20 represents a hydrogen atom or a methyl group.)
本発明の（メタ）アクリル酸エステルの製造方法によれば、入手しやすい原料を用い、安価に、かつ収率よく、上記式（２−１）または式（２−２）で表される化合物を製造することができる。 According to the method for producing a (meth) acrylic acid ester of the present invention, a compound represented by the above formula (2-1) or formula (2-2) at a low cost and in a high yield, using easily available raw materials. Can be manufactured.
本発明の（メタ）アクリル酸エステルの製造方法は、下記式（１−１）または式（１−２）で表される化合物に（メタ）アクリロイル基を導入して下記式（２−１）または式（２−２）で表される化合物を製造する方法である。本発明において「（メタ）アクリル酸」とはアクリル酸および／またはメタクリル酸を意味し、「（メタ）アクリロイル」とは、アクリロイルおよび／またはメタクリロイルを意味する。 In the method for producing a (meth) acrylic acid ester of the present invention, a (meth) acryloyl group is introduced into a compound represented by the following formula (1-1) or formula (1-2), and the following formula (2-1): Or it is the method of manufacturing the compound represented by Formula (2-2). In the present invention, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid, and “(meth) acryloyl” means acryloyl and / or methacryloyl.
式中、Ｒ1 〜Ｒ9 、Ｒ11〜Ｒ19は、水素原子；または酸素原子を含んでもよい炭素数１〜４の１価の直鎖、分岐、環状の炭化水素基を表す。酸素原子を含んでもよい炭素数１〜４の１価の直鎖、分岐、環状の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、メチルオキシ基、エチルオキシ基、ｎ−プロピルオキシ基、イソプロピルオキシ基、ｎ−ブチルオキシ基等が挙げられる。Ｒ1 〜Ｒ9 、Ｒ11〜Ｒ19は、式（１−１）または式（１−２）で表される化合物の入手しやすさの点で、水素原子またはメチル基が好ましく、水素原子が特に好ましい。
式中、Ｒ20は、水素原子またはメチル基を表す。
In the formula, R 1 to R 9 and R 11 to R 19 each represent a hydrogen atom; or a monovalent linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms that may contain an oxygen atom. Examples of the monovalent linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms that may contain an oxygen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. Group, tert-butyl group, methyloxy group, ethyloxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group and the like. R 1 to R 9 and R 11 to R 19 are each preferably a hydrogen atom or a methyl group from the viewpoint of availability of the compound represented by formula (1-1) or formula (1-2). Is particularly preferred.
In the formula, R 20 represents a hydrogen atom or a methyl group.
本発明においては、上記式（１−１）で表される化合物として、下記式（１−３）で表されるエキソ体の比率が５０モル％以上であるものを用い、また、上記式（１−２）で表される化合物として、下記式（１−４）で表されるエキソ体の比率が５０モル％以上であるものを用いることが好ましい。 In the present invention, as the compound represented by the above formula (1-1), a compound having a ratio of exo isomer represented by the following formula (1-3) of 50 mol% or more is used. As the compound represented by 1-2), it is preferable to use a compound having a ratio of exo isomer represented by the following formula (1-4) of 50 mol% or more.
下記式（１−５）または式（１−６）で表されるエンド体にあっては、カルボキシル基が分子内の二重結合と反応し、下記式（１−７）または式（１−８）で表されるラクトン体を多く生成してしまう。式（１−３）または式（１−４）で表されるエキソ体からは、ほとんどラクトン体は生成しない。 In the endo isomer represented by the following formula (1-5) or formula (1-6), the carboxyl group reacts with a double bond in the molecule, and the following formula (1-7) or formula (1- A large amount of the lactone compound represented by 8) is produced. From the exo isomer represented by the formula (1-3) or the formula (1-4), almost no lactone form is generated.
式（１−３）で表されるエキソ体の比率が５０モル％以上であり、また、式（１−４）で表されるエキソ体の比率が５０モル％以上であれば、副生成物であるラクトン体の生成を少なく抑えることができ、収率が上がる。また、式（１−１）または式（１−２）で表される化合物の蒸留精製の際に副生成物がコンデンサー部分に析出しにくくなる。 If the ratio of the exo isomer represented by the formula (1-3) is 50 mol% or more and the ratio of the exo isomer represented by the formula (1-4) is 50 mol% or more, a by-product The production of the lactone body can be suppressed to a low level, and the yield increases. In addition, the by-product is less likely to be deposited on the condenser portion during the distillation purification of the compound represented by the formula (1-1) or the formula (1-2).
また、あらかじめ式（１−３）または式（１−４）で表されるエキソ体の比率を高めておくこと、および式（１−５）または式（１−６）で表されるエンド体がラクトン体となることの相乗効果によって、式（２−１）または式（２−２）で表される化合物のうち、下記式（２−３）または式（２−４）で表される化合物の比率が高くなる。式（２−３）または式（２−４）で表される化合物のカルボキシル基をエステル化したものは、下記式（２−５）または式（２−６）で表される化合物のカルボキシル基をエステル化したものに比べ、エステル基が酸により脱離しやすいことを本発明者らは見出しており、結果、式（２−３）または式（２−４）で表される化合物の比率が高い式（２−１）または式（２−２）で表される化合物のカルボキシル基をエステル化したものに由来する繰り返し単位を有する樹脂をレジスト用樹脂に用いた場合、高い感度が得られる。 Moreover, increasing the ratio of the exo-form represented by Formula (1-3) or Formula (1-4) in advance, and an endo-form represented by Formula (1-5) or Formula (1-6) Of the compounds represented by formula (2-1) or formula (2-2), the compound represented by formula (2-3) or formula (2-4) The compound ratio is increased. What esterified the carboxyl group of the compound represented by Formula (2-3) or Formula (2-4) is the carboxyl group of the compound represented by Formula (2-5) or Formula (2-6) below. The present inventors have found that the ester group is easily eliminated by an acid compared to the esterified product, and as a result, the ratio of the compound represented by formula (2-3) or formula (2-4) is When a resin having a repeating unit derived from the esterified carboxyl group of the compound represented by the high formula (2-1) or formula (2-2) is used as a resist resin, high sensitivity is obtained.
式（１−１）または式（１−２）で表される化合物は、シクロペンタジエン誘導体とアクリル酸誘導体とのディールス・アルダー反応によって得られる。例えば、シクロペンタジエンとアクリル酸とのディールス・アルダー反応によって下記式（５）で表されるノルボルネンカルボン酸が得られる。 The compound represented by the formula (1-1) or the formula (1-2) is obtained by a Diels-Alder reaction between a cyclopentadiene derivative and an acrylic acid derivative. For example, norbornene carboxylic acid represented by the following formula (5) is obtained by Diels-Alder reaction between cyclopentadiene and acrylic acid.
該反応で得られる式（１−１）または式（１−２）で表される化合物は、式（１−５）または式（１−６）で表されるエンド体の比率が高くなる。したがって、式（１−３）または式（１−４）で表されるエキソ体の比率を５０モル％以上にする操作を行うことが好ましい。
式（１−３）または式（１−４）で表されるエキソ体の比率を５０モル％以上にする方法としては、以下の方法が挙げられる。
In the compound represented by Formula (1-1) or Formula (1-2) obtained by the reaction, the ratio of the endo form represented by Formula (1-5) or Formula (1-6) is increased. Therefore, it is preferable to perform an operation of setting the ratio of the exo-form represented by the formula (1-3) or the formula (1-4) to 50 mol% or more.
Examples of the method for setting the ratio of the exo isomer represented by the formula (1-3) or the formula (1-4) to 50 mol% or more include the following methods.
下記式（６）で表されるノルボルネンカルボン酸エステルに、ナトリウムアルコキシド、アルキルリチウム、水素化ナトリウム、水酸化ナトリウム、水酸化カリウム等の塩基を作用させ、ノルボルネンカルボン酸エステルを異性化させた後、水を加えエステルを加水分解することでエキソ体の比率を５０モル％以上にする。 A base such as sodium alkoxide, alkyl lithium, sodium hydride, sodium hydroxide, potassium hydroxide or the like is allowed to act on the norbornene carboxylic acid ester represented by the following formula (6) to isomerize the norbornene carboxylic acid ester, By adding water to hydrolyze the ester, the ratio of exo form is increased to 50 mol% or more.
（式（６）中、Ｒ21は、炭化水素基を表す。）
さらに、エステルの加水分解を行う際に、ノルボルネンカルボン酸エステルのモル数と同モル数の水をゆっくり滴下して加水分解を行うことで、エキソ体の比率をさらに上げることができる。
なお、式（１−３）または式（１−４）で表されるエキソ体の比率を５１モル％以上にする方法は、この方法に限定されるものでない。
(In the formula (6), R 21 represents a hydrocarbon group.)
Further, when the ester is hydrolyzed, water of the same number of moles as that of the norbornene carboxylic acid ester is slowly dropped to perform the hydrolysis, whereby the ratio of the exo form can be further increased.
In addition, the method of making the ratio of the exo isomer represented by Formula (1-3) or Formula (1-4) 51 mol% or more is not limited to this method.
式（１−１）または式（１−２）で表される化合物に（メタ）アクリロイル基を導入する方法は、特に限定されない。該方法としては、例えば、（Ａ）：式（１−１）または式（１−２）で表される化合物を、酸の存在下、メタクリル酸またはアクリル酸と反応させる方法、（Ｂ）：式（１−１）または式（１−２）で表される化合物に、酸の存在下、ギ酸、酢酸等を付加させた後、Ｔｉ系またはＳｎ系のエステル交換触媒存在下、メタクリル酸メチル等の（メタ）アクリル酸エステルとエステル交換反応させる方法が挙げられる。これらのうち、反応工程が短いことから、（Ａ）の方法が好ましい。（Ａ）の方法の場合、原料の投入順序は、式（１−１）または式（１−２）で表される化合物に酸を添加してからメタクリル酸またはアクリル酸を一括して投入または徐々に加えてもよいし、メタクリル酸またはアクリル酸に対し、酸と式（１−１）または式（１−２）で表される化合物の混合物を一括して投入または徐々に添加してもよい。なお、原料の投入順序はこれらに限定されるものではない。 The method for introducing the (meth) acryloyl group into the compound represented by formula (1-1) or formula (1-2) is not particularly limited. Examples of the method include (A): a method in which a compound represented by formula (1-1) or formula (1-2) is reacted with methacrylic acid or acrylic acid in the presence of an acid, and (B): After adding formic acid, acetic acid and the like to the compound represented by formula (1-1) or formula (1-2) in the presence of an acid, methyl methacrylate is added in the presence of a Ti-based or Sn-based transesterification catalyst. And a method of transesterification with a (meth) acrylic ester such as the above. Among these, since the reaction process is short, the method (A) is preferable. In the case of the method (A), the raw material is charged in the order of adding methacrylic acid or acrylic acid after adding an acid to the compound represented by formula (1-1) or formula (1-2). It may be gradually added, or a mixture of an acid and a compound represented by formula (1-1) or formula (1-2) may be added all at once or gradually added to methacrylic acid or acrylic acid. Good. Note that the order of starting materials is not limited to these.
酸としては、塩酸、硫酸、硝酸、メタンスルホン酸、トリフルオロメタンスルホン酸、トリフルオロ酢酸、ｐ−トルエンスルホン酸、強酸性のイオン交換樹脂、ＢＦ3 、りんタングステン酸等が挙げられる。
反応温度は、通常、１０℃〜２５０℃であり、３０℃〜１６０℃が好ましい。反応温度を１０℃以上にすることで、エステル化反応が進行しやすくなり、２５０℃以下とすることで、収率が低下しない。
Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, p-toluenesulfonic acid, strongly acidic ion exchange resin, BF 3 , and phosphotungstic acid.
The reaction temperature is usually 10 ° C to 250 ° C, preferably 30 ° C to 160 ° C. By making reaction temperature 10 degreeC or more, esterification reaction will advance easily, and a yield does not fall by setting it as 250 degrees C or less.
式（１−１）または式（１−２）で表される化合物の量は、（メタ）アクリル酸（１モル）に対し、通常、０．１〜３０モルであり、１〜１０モルが好ましい。式（１−１）または式（１−２）で表される化合物の量を０．１モル以上とすることで、反応収率が向上する。式（１−１）または式（１−２）で表される化合物の量を３０モル以下とすることで、未反応の（メタ）アクリル酸を減らすことができる。 The amount of the compound represented by formula (1-1) or formula (1-2) is usually 0.1 to 30 mol, and 1 to 10 mol is relative to (meth) acrylic acid (1 mol). preferable. By making the amount of the compound represented by formula (1-1) or formula (1-2) 0.1 mol or more, the reaction yield is improved. By making the amount of the compound represented by formula (1-1) or formula (1-2) 30 mol or less, unreacted (meth) acrylic acid can be reduced.
式（１−１）または式（１−２）で表される化合物に（メタ）アクリロイル基を導入する際には、必要に応じて、不活性溶媒等の、反応に影響を及ぼさない適当な溶媒、添加剤を用いてもよい。
また、（メタ）アクリル酸、または式（１−１）または式（１−２）で表される化合物の不都合な重合反応を制御すべく、適当な重合禁止剤を適量添加することが好ましい。重合禁止剤としては、公知の各種のものが充当可能であり、具体的には、ヒドロキノン、メトキノン、フェノチアジン、銅塩等が挙げられる。
When a (meth) acryloyl group is introduced into the compound represented by formula (1-1) or formula (1-2), an appropriate solvent such as an inert solvent that does not affect the reaction is used as necessary. Solvents and additives may be used.
Further, it is preferable to add an appropriate amount of an appropriate polymerization inhibitor in order to control an unfavorable polymerization reaction of (meth) acrylic acid or the compound represented by formula (1-1) or formula (1-2). Various known polymerization inhibitors can be used, and specific examples include hydroquinone, methoquinone, phenothiazine, and copper salts.
式（２−１）または式（２−２）で表される化合物は、有機溶媒および水を用いた抽出、水または有機溶媒による洗浄等によって、反応液から粗体として回収される。該粗体は、溶媒分別法、カラムクロマトグラフィ、蒸留等の公知の方法により精製することができる。
式（１−１）または式（１−２）で表される化合物として、ノルボルネンカルボン酸を用いた場合、式（２−１）または式（２−２）で表される化合物としては、下記式（２−ａ）〜（２−ｈ）で表される位置異性体および立体異性体、さらには、これらの光学異性体（構造式略）が存在しうる。
The compound represented by formula (2-1) or formula (2-2) is recovered as a crude product from the reaction solution by extraction with an organic solvent and water, washing with water or an organic solvent, and the like. The crude product can be purified by a known method such as solvent fractionation, column chromatography, or distillation.
When norbornene carboxylic acid is used as the compound represented by the formula (1-1) or the formula (1-2), the compound represented by the formula (2-1) or the formula (2-2) Positional isomers and stereoisomers represented by the formulas (2-a) to (2-h), and further optical isomers (structural formula is omitted) may exist.
以下、実施例を挙げて本発明をさらに詳細に説明する。なお、本発明はこれら実施例に限定されるものではない。
（評価方法）
ノルボルネンカルボン酸のエキソ体の比率は、ＦＩＤガスクロマトグラフィを用い、下記式により決定した。ここで、ＧＣ面積とは、ガスクロマトグラフィチャートのベースラインと各物質のピークで囲まれた面積のことである。
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.
(Evaluation methods)
The ratio of the exo form of norbornene carboxylic acid was determined by the following formula using FID gas chromatography. Here, the GC area is an area surrounded by the baseline of the gas chromatography chart and the peak of each substance.
反応液中の目的物および副生成物（ラクトン体）の比率は、ＦＩＤガスクロマトグラフィにより測定されたＧＣ面積比とした。
蒸留精製時のコンデンサー部への副生成物（ラクトン体）の付着の有無を目視で確認した。
The ratio of the target product and by-product (lactone form) in the reaction solution was the GC area ratio measured by FID gas chromatography.
The presence or absence of adhesion of by-products (lactone bodies) to the condenser during distillation purification was confirmed visually.
［実施例１］
攪拌機、温度計および還流冷却管を取り付けた１Ｌガラス製三口フラスコに、エキソ体比率７０モル％のノルボルネンカルボン酸６９．０ｇ（０．５０モル）、メタクリル酸１２９．０ｇ（１．５モル）、メタンスルホン酸４．８ｇ（０．０５モル）、を仕込み、攪拌しながら１３０℃まで温度を昇温した。その後、フラスコの温度を１３０℃に保ったまま、２時間反応させた。反応終了後の反応液のガスクロマトグラフィ分析より下記式（７）で表される化合物が生成していることを確認した。また、わずかにラクトン体も確認され、式（７）で表される化合物とラクトン体とのＧＣ面積比は９３：７であった。
[Example 1]
In a 1 L glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 69.0 g (0.50 mol) of norbornene carboxylic acid having an exo-form ratio of 70 mol%, 129.0 g (1.5 mol) of methacrylic acid, 4.8 g (0.05 mol) of methanesulfonic acid was charged, and the temperature was raised to 130 ° C. while stirring. Then, it was made to react for 2 hours, keeping the temperature of a flask at 130 degreeC. It was confirmed from the gas chromatographic analysis of the reaction liquid after completion of the reaction that the compound represented by the following formula (7) was produced. A slight amount of lactone was also confirmed, and the GC area ratio of the compound represented by formula (7) and the lactone was 93: 7.
反応終了後、反応液を氷浴で冷却し、攪拌しながら、トルエン２００ｍｌ、水１００ｍｌを加えた。これを分液ロートに移し、水層を除去した後、トルエン層を濃縮したところ、式（７）で表される化合物の粗体が１１０．０ｇ得られた。１１０．０ｇの粗体を減圧蒸留（４ｍＨｇ、１００〜１１０℃）したところ、コンデンサー部分への副生成物の付着は確認されなかった。７８．４ｇ（０．３５ｍｏｌ）の式（７）で表される化合物の精製物が得られた。 After completion of the reaction, the reaction solution was cooled in an ice bath, and 200 ml of toluene and 100 ml of water were added with stirring. This was transferred to a separatory funnel, the aqueous layer was removed, and then the toluene layer was concentrated. As a result, 110.0 g of a crude product of the compound represented by the formula (7) was obtained. When 110.0 g of the crude product was distilled under reduced pressure (4 mHg, 100 to 110 ° C.), no adhesion of by-products to the condenser part was confirmed. 78.4 g (0.35 mol) of a purified product of the compound represented by formula (7) was obtained.
［実施例２］
原料のノルボルネンカルボン酸として、エキソ体比率５０モル％のノルボルネンカルボン酸を用いた以外は、実施例１と同様に行った。
反応終了後の反応液のガスクロマトグラフィ分析より下記式（７）で表される化合物が生成していることを確認した。また、ラクトン体も確認され、式（７）で表される化合物とラクトン体とのＧＣ面積比は８５：１５であった。
[Example 2]
The same procedure as in Example 1 was performed except that norbornene carboxylic acid having an exo ratio of 50 mol% was used as the raw material norbornene carboxylic acid.
It was confirmed from the gas chromatographic analysis of the reaction liquid after completion of the reaction that the compound represented by the following formula (7) was produced. A lactone form was also confirmed, and the GC area ratio of the compound represented by formula (7) and the lactone form was 85:15.
反応終了後、反応液を氷浴で冷却し、攪拌しながら、トルエン２００ｍｌ、水１００ｍｌを加えた。これを分液ロートに移し、水層を除去した後、トルエン層を濃縮したところ、式（７）で表される化合物の粗体が１０３．５ｇ得られた。１０３．５ｇの粗体を減圧蒸留（４ｍＨｇ、１００〜１１０℃）したところ、コンデンサー部分への副生成物の付着は確認されなかった。６９．０ｇ（０．３１ｍｏｌ）の式（７）で表される化合物の精製物が得られた。 After completion of the reaction, the reaction solution was cooled in an ice bath, and 200 ml of toluene and 100 ml of water were added with stirring. This was transferred to a separatory funnel, the aqueous layer was removed, and then the toluene layer was concentrated. As a result, 103.5 g of a crude product of the compound represented by the formula (7) was obtained. When 103.5 g of the crude product was distilled under reduced pressure (4 mHg, 100 to 110 ° C.), adhesion of by-products to the condenser portion was not confirmed. A purified product of the compound represented by the formula (7) of 69.0 g (0.31 mol) was obtained.
［比較例１］
攪拌機、温度計および還流冷却管を取り付けた１Ｌガラス製三口フラスコに、エキソ体比率３０モル％のノルボルネンカルボン酸ｔｅｒｔ−ブチル９７．１ｇ（０．５０モル）、メタクリル酸１２９．０ｇ（１．５モル）、メタンスルホン酸４．８ｇ（０．０５モル）、を仕込み、攪拌しながら１３０℃まで温度を昇温した。その後、フラスコの温度を１３０℃に保ったまま、２時間反応させた。反応終了後の反応液のガスクロマトグラフィ分析より上記式（７）および下記式（８）で表される化合物が生成していることを確認した。また、ラクトン体も確認され、式（７）で表される化合物とラクトン体とのＧＣ面積比は６０：４０であった。
[Comparative Example 1]
To a 1 L glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 97.1 g (0.50 mol) of tert-butyl norbornenecarboxylate having an exo-form ratio of 30 mol% and 129.0 g of methacrylic acid (1.5 Mol) and 4.8 g (0.05 mol) of methanesulfonic acid were charged, and the temperature was raised to 130 ° C. while stirring. Then, it was made to react for 2 hours, keeping the temperature of a flask at 130 degreeC. It was confirmed from the gas chromatographic analysis of the reaction liquid after completion of the reaction that the compound represented by the above formula (7) and the following formula (8) was produced. A lactone form was also confirmed, and the GC area ratio of the compound represented by formula (7) and the lactone form was 60:40.
反応終了後、反応液を氷浴で冷却し、攪拌しながら、トルエン２００ｍｌ、水１００ｍｌを加えた。これを分液ロートに移し、水層を除去した後、トルエン層を濃縮したところ、式（７）で表される化合物の粗体が９８．６ｇ得られた。９８．６ｇの粗体を減圧蒸留（４ｍＨｇ、１００〜１１０℃）したところ、コンデンサー部分へ副生成物が多量に付着した。３０．１ｇ（０．１３ｍｏｌ）の式（７）で表される化合物の精製物が得られた。 After completion of the reaction, the reaction solution was cooled in an ice bath, and 200 ml of toluene and 100 ml of water were added with stirring. This was transferred to a separatory funnel, the aqueous layer was removed, and then the toluene layer was concentrated. As a result, 98.6 g of a crude product of the compound represented by the formula (7) was obtained. When 98.6 g of the crude product was distilled under reduced pressure (4 mHg, 100 to 110 ° C.), a large amount of by-products adhered to the condenser part. 30.1 g (0.13 mol) of a purified product of the compound represented by formula (7) was obtained.
［比較例２］
原料のノルボルネンカルボン酸ｔｅｒｔ−ブチルとして、エキソ体比率５０モル％のノルボルネンカルボン酸ｔｅｒｔ−ブチルを用いた以外は、比較例１と同様に行った。
反応終了後の反応液のガスクロマトグラフィ分析より式（７）および式（８）で表される化合物が生成していることを確認した。また、ラクトン体も確認され、式（７）で表される化合物とラクトン体とのＧＣ面積比は７５：２５であった。
[Comparative Example 2]
The same procedure as in Comparative Example 1 was conducted except that tert-butyl norbornenecarboxylate having a exo-form ratio of 50 mol% was used as the raw material tert-butyl norbornenecarboxylate.
From the gas chromatography analysis of the reaction solution after completion of the reaction, it was confirmed that the compounds represented by the formulas (7) and (8) were produced. A lactone form was also confirmed, and the GC area ratio of the compound represented by formula (7) and the lactone form was 75:25.
反応終了後、反応液を氷浴で冷却し、攪拌しながら、トルエン２００ｍｌ、水１００ｍｌを加えた。これを分液ロートに移し、水層を除去した後、トルエン層を濃縮したところ、式（７）で表される化合物の粗体が１０１．４ｇ得られた。１０１．４ｇの粗体を減圧蒸留（４ｍＨｇ、１００〜１１０℃）したところ、コンデンサー部分へ副生成物が多量に付着した。５５．０ｇ（０．２５ｍｏｌ）の式（７）で表される化合物の精製物が得られた。 After completion of the reaction, the reaction solution was cooled in an ice bath, and 200 ml of toluene and 100 ml of water were added with stirring. This was transferred to a separatory funnel, the aqueous layer was removed, and then the toluene layer was concentrated. As a result, 101.4 g of a crude product of the compound represented by the formula (7) was obtained. When 101.4 g of the crude product was distilled under reduced pressure (4 mHg, 100 to 110 ° C.), a large amount of by-products adhered to the condenser part. 55.0 g (0.25 mol) of a purified product of the compound represented by formula (7) was obtained.
本発明の（メタ）アクリル酸エステルの製造方法によれば、塗料、接着剤、粘着剤、インキ用レジン、レジスト、成型材料、光学材料等に用いられる樹脂の原料として有用である式（２−１）または式（２−２）で表される化合物を、入手しやすい原料を用い、安価に、かつ収率よく製造することができる。
According to the method for producing a (meth) acrylic acid ester of the present invention, the formula (2-) useful as a raw material for resins used in paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials and the like The compound represented by 1) or formula (2-2) can be produced at low cost and in high yield using easily available raw materials.
Claims (1)
A compound represented by the following formula (2-1) or formula (2-2) is obtained by introducing a (meth) acryloyl group into the compound represented by the following formula (1-1) or formula (1-2). A method for producing a (meth) acrylic acid ester.
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