JPH06219991A - Production of polyfunctional @(3754/24)meth)acrylate - Google Patents
Production of polyfunctional @(3754/24)meth)acrylateInfo
- Publication number
- JPH06219991A JPH06219991A JP5029972A JP2997293A JPH06219991A JP H06219991 A JPH06219991 A JP H06219991A JP 5029972 A JP5029972 A JP 5029972A JP 2997293 A JP2997293 A JP 2997293A JP H06219991 A JPH06219991 A JP H06219991A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- parts
- reaction
- polyfunctional
- acid
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、多官能性（メタ）アク
リレートの製造方法に関する。詳しくは、特定の処理工
程を設けることにより、残留する酸触媒が効率よく除去
された多官能性（メタ）アクリレートの製造方法に関す
る。FIELD OF THE INVENTION The present invention relates to a method for producing a polyfunctional (meth) acrylate. Specifically, the present invention relates to a method for producing a polyfunctional (meth) acrylate in which a residual acid catalyst is efficiently removed by providing a specific treatment step.
【０００２】[0002]
【従来の技術】近年、塗料、接着、印刷インキなどの分
野においては、環境保全、省資源、省エネルギーなどの
観点から、紫外線硬化型または電子線硬化型のものが増
加しつつあり、多官能性（メタ）アクリレートは紫外線
硬化型樹脂または電子線硬化型樹脂の反応性希釈剤とし
て広く使用されている。特に、トリメチロールプロパ
ン、ペンタエリスリトール、ジペンタエリスリトールお
よびこれらの誘導体を（メタ）アクリル化して得られる
多官能性（メタ）アクリレートは、速硬化性、高硬度な
どの特徴がありその使用量は増大しつつある。2. Description of the Related Art In recent years, in the fields of paints, adhesives, printing inks, etc., ultraviolet curable type or electron beam curable type has been increasing from the viewpoint of environmental protection, resource saving, energy saving, etc. (Meth) acrylate is widely used as a reactive diluent for ultraviolet curable resins or electron beam curable resins. In particular, polyfunctional (meth) acrylates obtained by (meth) acrylate of trimethylolpropane, pentaerythritol, dipentaerythritol and their derivatives are characterized by fast curing, high hardness, etc. I am doing it.
【０００３】従来より、多官能性（メタ）アクリレート
は、多価アルコールと、（メタ）アクリル酸を、メタン
スルホン酸やパラトルエンスルホン酸などの酸触媒の存
在下に、エステル化反応させて製造されている。こうし
て得られる反応生成物中には、触媒や未反応物が残存す
るため、中和処理を施すことにより、精製が行われてい
る。Conventionally, polyfunctional (meth) acrylates have been produced by subjecting a polyhydric alcohol and (meth) acrylic acid to an esterification reaction in the presence of an acid catalyst such as methanesulfonic acid or paratoluenesulfonic acid. Has been done. Since the catalyst and unreacted substances remain in the reaction product thus obtained, purification is carried out by performing a neutralization treatment.
【０００４】また、多官能性（メタ）アクリレートを高
アクリル化物とするために前記エステル化反応は通常、
長時間行われるが、該反応時間が長くなるに従い、パラ
トルエンスルホン酸などの酸触媒がスルホン酸エステル
のような誘導体になる。しかし、反応生成物中から該酸
触媒誘導体を前記中和処理だけで取り除くことは困難で
ある。In order to make polyfunctional (meth) acrylate highly acrylated, the esterification reaction is usually performed.
Although the reaction is carried out for a long time, as the reaction time becomes longer, the acid catalyst such as paratoluenesulfonic acid becomes a derivative such as a sulfonic acid ester. However, it is difficult to remove the acid catalyst derivative from the reaction product only by the neutralization treatment.
【０００５】そのため、該触媒の誘導体が除去されてい
ない多官能性（メタ）アクリレートを、たとえばコーテ
ィング剤等の各種用途に供した場合には、コーティング
剤等が着色しやすい、貯蔵安定性が悪い、変異原性が陽
性になる、等のさまざまな問題があった。Therefore, when the polyfunctional (meth) acrylate from which the catalyst derivative is not removed is used for various purposes such as a coating agent, the coating agent is likely to be colored and the storage stability is poor. There were various problems such as positive mutagenicity.
【０００６】一方、エステル化反応時間を短くすれば、
酸触媒誘導体の残留量を減少させることができるが、エ
ステル化率が低くなるため、未反応の水酸基が多数残
り、速硬化性、高硬度など多官能性（メタ）アクリレー
トの特徴が損なわれてしまい好ましくない。On the other hand, if the esterification reaction time is shortened,
Although the residual amount of the acid catalyst derivative can be reduced, the esterification rate becomes low, so many unreacted hydroxyl groups remain, and the characteristics of the polyfunctional (meth) acrylate such as rapid curing and high hardness are impaired. It is not desirable.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、酸触媒誘導
体の残留量が少なく、かつ高エステル化率の多官能性
（メタ）アクリレートを製造する方法を提供することを
目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a polyfunctional (meth) acrylate having a low residual amount of an acid catalyst derivative and a high esterification rate.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、従来技術
の課題を解決すべく、鋭意検討を行った結果、通常の製
造方法により得られた多官能性（メタ）アクリレート
に、中和処理を行った後、さらにアミン類で処理を施し
た場合には、酸触媒誘導体の残留量を低減できるという
事実を見出だした。本発明は、かかる事実に基づいて完
成されたものである。Means for Solving the Problems As a result of intensive studies to solve the problems of the prior art, the present inventors have found that a polyfunctional (meth) acrylate obtained by an ordinary production method is neutralized. It was found that the residual amount of the acid catalyst derivative can be reduced when the treatment is further performed with amines after the treatment. The present invention has been completed based on this fact.
【０００９】すなわち、本発明は、多価アルコールと、
（メタ）アクリル酸および／または（メタ）アクリル酸
の誘導体を、酸触媒の存在下に有機溶媒中でエステル化
反応させて得られた反応生成物を、中和処理した後、さ
らにアミン類で処理することを特徴とする多官能性（メ
タ）アクリレートの製造方法に関する。That is, the present invention comprises a polyhydric alcohol and
The reaction product obtained by subjecting (meth) acrylic acid and / or a derivative of (meth) acrylic acid to an esterification reaction in an organic solvent in the presence of an acid catalyst is neutralized and then further treated with an amine. It relates to a method for producing a polyfunctional (meth) acrylate, which is characterized by treatment.
【００１０】本発明の多官能性（メタ）アクリレートの
製造に用いられる多価アルコールとしては、２個以上の
水酸基を有していれば特に制限なく使用できるが、特に
ペンタエリスリトール、ジペンタエリスリトール、トリ
メチロールプロパン、グリセリン、ポリグリセリンおよ
びこれらの誘導体等の３個以上の水酸基を有する多価ア
ルコールを使用するのが、得られる多官能性（メタ）ア
クリレートを反応性希釈剤等として使用する場合に効果
的である。なお、前記多価アルコールの誘導体として
は、前記多価アルコールにエチレンオキサイドやプロピ
レンオキサイドなどを付加させた化合物などがあげられ
る。これら多価アルコールは１種を単独で使用してもよ
く、または２種以上を組み合わせて使用してもよい。The polyhydric alcohol used for producing the polyfunctional (meth) acrylate of the present invention can be used without particular limitation as long as it has two or more hydroxyl groups, but in particular pentaerythritol, dipentaerythritol, Use of a polyhydric alcohol having three or more hydroxyl groups such as trimethylolpropane, glycerin, polyglycerin and their derivatives is effective when the resulting polyfunctional (meth) acrylate is used as a reactive diluent or the like. It is effective. Examples of the polyhydric alcohol derivative include compounds obtained by adding ethylene oxide or propylene oxide to the polyhydric alcohol. These polyhydric alcohols may be used alone or in combination of two or more.
【００１１】また、多価アルコールとエステル化反応し
て多官能性（メタ）アクリレートを構成する酸成分とし
ては、（メタ）アクリル酸および（メタ）アクリル酸の
誘導体を使用できる。（メタ）アクリル酸の誘導体とし
ては、（メタ）アクリル酸低級アルキルエステル等の多
価アルコールとエステル交換反応が容易な（メタ）アク
リル酸エステル類や、（メタ）アクリル酸ダイマー、
（メタ）アクリル酸オリゴマーなどがあげられる。Further, (meth) acrylic acid and derivatives of (meth) acrylic acid can be used as the acid component constituting the polyfunctional (meth) acrylate by the esterification reaction with the polyhydric alcohol. Examples of the (meth) acrylic acid derivative include (meth) acrylic acid esters that are easily transesterified with polyhydric alcohols such as (meth) acrylic acid lower alkyl ester, and (meth) acrylic acid dimer,
Examples thereof include (meth) acrylic acid oligomer.
【００１２】多価アルコールおよび（メタ）アクリル酸
の使用量は、多価アルコールの水酸基１当量に対して
（メタ）アクリル酸を通常１〜２倍当量程度、好ましく
は１．１〜１．５倍当量とされる。１倍当量に満たない
場合は、エステル化反応時間が長くなり、また得られる
多官能性（メタ）アクリレート中の残留触媒量が増大す
る他、高分子量物等の副生成物も増大する傾向があり好
ましくない。また２倍当量を越える場合は、過剰のアク
リル酸を使用することとなり経済的に不利となるのみな
らず、反応生成物から未反応アクリル酸を除去する困難
性が増大するため好ましくない。The polyhydric alcohol and (meth) acrylic acid are used in an amount of usually 1 to 2 equivalents, preferably 1.1 to 1.5, of (meth) acrylic acid with respect to 1 equivalent of the hydroxyl group of the polyhydric alcohol. It is a double equivalent. If the amount is less than 1 equivalent, the esterification reaction time tends to be long, the amount of residual catalyst in the resulting polyfunctional (meth) acrylate increases, and by-products such as high molecular weight substances tend to increase. There is not preferable. On the other hand, if the amount exceeds 2 equivalents, excess acrylic acid is used, which is not economically disadvantageous, and it is difficult to remove unreacted acrylic acid from the reaction product, which is not preferable.
【００１３】本発明で使用するエステル化のための酸触
媒としては、従来公知の各種のものを使用できる。たと
えば硫酸、メタンスルホン酸、p-トルエンスルホン酸な
どをあげることができる。触媒の使用量は、エステル化
反応の時間および温度などを考慮して適宜決定される
が、通常は多価アルコールおよび（メタ）アクリル酸の
合計１００重量部に対して通常０．１〜１０重量部程
度、好ましくは３〜７重量部とされる。As the acid catalyst for esterification used in the present invention, various conventionally known ones can be used. Examples thereof include sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid. The amount of the catalyst used is appropriately determined in consideration of the time and temperature of the esterification reaction, but is usually 0.1 to 10 parts by weight based on 100 parts by weight of the total of the polyhydric alcohol and the (meth) acrylic acid. Parts, preferably 3 to 7 parts by weight.
【００１４】また、エステル化反応に際しては、有機溶
媒が使用される。有機溶媒としては特に制限はされず、
通常はヘキサン、シクロヘキサン、ベンゼン、トルエ
ン、キシレンなどの各種の不活性溶媒の中から１種を単
独でまたは２種以上を組み合わせて任意に選択して使用
できる。これら有機溶媒の使用により、エステル化反応
時に生成する水の系外への除去が容易になり反応時間を
短縮することができる。An organic solvent is used in the esterification reaction. The organic solvent is not particularly limited,
Usually, one kind alone or a combination of two or more kinds can be arbitrarily selected and used from among various inert solvents such as hexane, cyclohexane, benzene, toluene and xylene. By using these organic solvents, it is easy to remove the water generated during the esterification reaction from the system, and the reaction time can be shortened.
【００１５】エステル化反応の反応温度は通常５０〜１
３０℃程度、好ましくは６５〜９５℃とされる。また、
反応時間は特に制限はされないが得られる多官能性（メ
タ）アクリレートが高エステル化物となるように、通常
５〜１５時間程度とされる。エステル反応が不十分の場
合には未反応原料の存在により、後述する抽出工程での
操作が煩雑になり好ましくない。The reaction temperature for the esterification reaction is usually 50 to 1
The temperature is about 30 ° C, preferably 65 to 95 ° C. Also,
The reaction time is not particularly limited, but is usually about 5 to 15 hours so that the obtained polyfunctional (meth) acrylate becomes a highly esterified product. If the ester reaction is insufficient, the presence of unreacted raw materials complicates the operation in the extraction step described below, which is not preferable.
【００１６】尚、上記反応に際しては（メタ）アクリル
酸の重合を防止するため重合防止剤を使用してもよく、
さらには微量の酸素または空気を反応液中にバブリング
してもよい。重合防止剤としては、例えばハイドロキノ
ン、パラメトキシフェノール、２，４−ジメチル−６−
ｔ−ブチルフェノール、パラベンゾキノン、フェノチア
ジン、Ｎ−ニトロジフェニルアミンなどを例示できる。In the above reaction, a polymerization inhibitor may be used to prevent the polymerization of (meth) acrylic acid,
Further, a slight amount of oxygen or air may be bubbled in the reaction solution. Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, 2,4-dimethyl-6-
Examples thereof include t-butylphenol, parabenzoquinone, phenothiazine and N-nitrodiphenylamine.
【００１７】上記エステル化反応により多官能性（メ
タ）アクリレートを主成分とする反応生成物が得られる
が、該エステル化反応生成物は不純物として未反応原
料、エステル化に用いた酸触媒およびその誘導体を含有
しているため、そのまま使用した場合には満足しうる性
能を発揮することができない。A reaction product containing a polyfunctional (meth) acrylate as a main component is obtained by the above esterification reaction. The esterification reaction product is an unreacted raw material as an impurity, an acid catalyst used for esterification, and its Since it contains a derivative, it cannot exhibit satisfactory performance when used as it is.
【００１８】しかして、本発明では上記の未反応原料お
よび残留触媒の除去工程、すなわち反応生成物の精製工
程が、本発明の製造方法の必須工程となる。以下に反応
生成物の精製工程につき詳述する。該工程は中和処理工
程およびアミン処理工程からなる。Therefore, in the present invention, the step of removing the unreacted raw material and the residual catalyst, that is, the step of purifying the reaction product, is an essential step of the production method of the present invention. The purification process of the reaction product will be described in detail below. The process consists of a neutralization process and an amine process.
【００１９】中和処理工程では、反応生成物に、アルカ
リ性物質を添加して、未反応原料たる残存アクリル酸モ
ノマーおよび酸触媒を中和する。使用されるアルカリ性
物質としては、アルカリ金属水酸化物、アルカリ土類金
属水酸化物、アルカリ金属炭酸塩、アルカリ金属炭酸水
素塩、アルカリ土類金属炭酸塩等があげられる。これら
の中でも副反応が少なく、取り扱いが容易なことから、
アルカリ金属水酸化物、たとえば水酸化ナトリウム等が
好適である。アルカリ性物質は通常は水溶液として添加
される。水溶液の濃度は通常は１〜３０重量％濃度程
度、好ましくは１０〜２０重量％濃度とされる。３０重
量％を越える高濃度の水溶液を用いると、得られた多官
能性（メタ）アクリレートが加水分解され、収率が低下
するため好ましくない。また、アルカリ性物質の使用量
は、前記でえられた反応生成物中のアクリル酸モノマー
および酸触媒を完全に中和できる量であればよく、これ
らアクリル酸モノマー等の残存量（酸価により決定）に
より適宜決定すればよいが、一般的には反応生成物の酸
価に対し、通常１０％程度過剰量までのアルカリ性物質
の水溶液を使用すればよい。In the neutralization treatment step, an alkaline substance is added to the reaction product to neutralize the residual acrylic acid monomer and the acid catalyst which are unreacted raw materials. Examples of the alkaline substance used include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates and alkaline earth metal carbonates. Among these, there are few side reactions and they are easy to handle,
Alkali metal hydroxides such as sodium hydroxide are preferred. The alkaline substance is usually added as an aqueous solution. The concentration of the aqueous solution is usually about 1 to 30% by weight, preferably 10 to 20% by weight. Use of a high-concentration aqueous solution exceeding 30% by weight is not preferable because the obtained polyfunctional (meth) acrylate is hydrolyzed and the yield is reduced. Further, the amount of the alkaline substance used may be an amount that can completely neutralize the acrylic acid monomer and the acid catalyst in the reaction product obtained above, and the residual amount of these acrylic acid monomers and the like (determined by the acid value) However, generally, an aqueous solution of an alkaline substance up to an excess of about 10% with respect to the acid value of the reaction product may be used.
【００２０】中和処理されたアクリル酸モノマー等のア
ルカリ金属塩は、多官能性（メタ）アクリレートを含む
有機層から効率よく水抽出される。ここで中和廃水は除
去しておく。なお、中和処理にあたり、エステル化反応
に使用しうる有機溶媒をさらに加えて行ってもよい。The neutralized alkali metal salt of acrylic acid monomer or the like is efficiently extracted with water from the organic layer containing the polyfunctional (meth) acrylate. Neutralization wastewater is removed here. The neutralization treatment may be carried out by further adding an organic solvent that can be used in the esterification reaction.
【００２１】次のアミン処理工程では、アミン類を前記
有機層に添加し、通常５０〜８０℃程度の温度で撹拌し
て、酸触媒誘導体（スルホン酸エステル）を分解する。
使用するアミンとしては３級アミンが好ましい。たとえ
ば、一般式（１）：Ｎ（Ｒ1）（Ｒ2 ）（Ｒ3 ）（Ｒ
1 、Ｒ2 、Ｒ3 はいずれもメチル基、エチル基、プロピ
ル基、ヒドロキシエチル基またはヒドロキシプロピル基
を表し、それぞれは同一でも、異なっていてもよい。）
で表される化合物およびトリエチレンジアミンなどの３
級アミンがあげられる。一般式（１）で表される化合物
の具体例としては、トリメチルアミン、トリエチルアミ
ン、Ｎ−メチルジエタノールアミン、トリエタノールア
ミンなどがあげられる。アミン類の使用量は多官能性
（メタ）アクリレートの種類や残留酸触媒誘導体（スル
ホン酸エステル）の量により異なるが、通常は反応生成
物（固形分）１００重量部に対して通常０．１〜５重量
部程度がよい。０．１重量部に満たない場合は残留酸触
媒誘導体を十分に分解することができず、５重量部を越
える場合には、得られた多官能性（メタ）アクリレート
の加水分解などの副反応の原因となり、さらには経済的
にも不利であり、いずれも好ましくない。In the next amine treatment step, amines are added to the organic layer and stirred at a temperature of usually 50 to 80 ° C. to decompose the acid catalyst derivative (sulfonic acid ester).
The amine used is preferably a tertiary amine. For example, the general formula (1): N (R 1 ) (R 2 ) (R 3 ) (R
1 , R 2 and R 3 each represent a methyl group, an ethyl group, a propyl group, a hydroxyethyl group or a hydroxypropyl group, and they may be the same or different. )
And compounds such as triethylenediamine
Examples include primary amines. Specific examples of the compound represented by the general formula (1) include trimethylamine, triethylamine, N-methyldiethanolamine and triethanolamine. The amount of amines used varies depending on the type of polyfunctional (meth) acrylate and the amount of residual acid catalyst derivative (sulfonic acid ester), but is usually 0.1 per 100 parts by weight of the reaction product (solid content). It is preferably about 5 parts by weight. When it is less than 0.1 part by weight, the residual acid catalyst derivative cannot be sufficiently decomposed, and when it exceeds 5 parts by weight, side reactions such as hydrolysis of the obtained polyfunctional (meth) acrylate are carried out. And is economically disadvantageous, neither of which is preferable.
【００２２】またアミン処理工程では、アミン類ととも
に通常３０重量％濃度以上の高濃度のアルカリ金属の水
酸化物の水溶液を共存させてもよい。高濃度のアルカリ
金属の水酸化物の水溶液を共存させた場合には酸触媒誘
導体（スルホン酸エステル）をより効率よく分解するこ
とができる。高濃度のアルカリ金属の水酸化物の水溶液
の使用量は反応生成物（固形分）１００重量部に対して
通常２０重量部以下程度がよい。２０重量部を越える場
合には得られた多官能性（メタ）アクリレートが加水分
解され、収率が低下するため好ましくない。In the amine treatment step, a high concentration aqueous solution of an alkali metal hydroxide having a concentration of 30% by weight or more may be allowed to coexist with the amines. When a high-concentration aqueous solution of an alkali metal hydroxide is allowed to coexist, the acid catalyst derivative (sulfonic acid ester) can be decomposed more efficiently. The amount of the high-concentration aqueous solution of alkali metal hydroxide used is usually about 20 parts by weight or less with respect to 100 parts by weight of the reaction product (solid content). If the amount exceeds 20 parts by weight, the obtained polyfunctional (meth) acrylate is hydrolyzed and the yield is reduced, which is not preferable.
【００２３】上記アミン処理工程により、酸触媒誘導体
（スルホン酸エステル）は容易に加水分解される（多官
能性（メタ）アクリレートはアミンでは加水分解されな
い）が、反応生成物からアミン類および酸触媒誘導体の
分解物等を完全に除去するため、引き続き洗浄に付され
る。洗浄は、まず、塩酸、硫酸、しゅう酸等の酸性水溶
液によりアミン成分等を完全に除去した後、次いでアル
カリ金属の水酸化物等を用い再度中和し液性を中性また
はアルカリ性とする。つづいて、多官能性（メタ）アク
リレートを含有する有機層を軟水で十分に洗浄する。軟
水の使用量は特に制限されないが通常は有機層に対して
１５〜４０重量％程度とするのがよい。その後、静置し
有機層と水層に分離する。かかる水洗いおよび静置を通
常２〜４回程度繰り返すことにより、酸触媒誘導体の分
解物をほぼ完全に水洗除去することができる。尚、水洗
い工程において濃厚食塩水や、硫酸ナトリウム水溶液を
用いて水洗を行ってもよい。By the above-mentioned amine treatment step, the acid catalyst derivative (sulfonic acid ester) is easily hydrolyzed (the polyfunctional (meth) acrylate is not hydrolyzed by the amine), but the reaction products produce amines and acid catalysts. In order to completely remove the decomposed product of the derivative and the like, the product is subsequently washed. The washing is performed by first completely removing the amine component and the like with an acidic aqueous solution of hydrochloric acid, sulfuric acid, oxalic acid and the like, and then neutralizing again with an alkali metal hydroxide or the like to make the liquid neutral or alkaline. Subsequently, the organic layer containing the polyfunctional (meth) acrylate is thoroughly washed with soft water. Although the amount of soft water used is not particularly limited, it is usually about 15 to 40% by weight based on the organic layer. Then, it is left to stand and separated into an organic layer and an aqueous layer. By repeating such washing with water and standing for about 2 to 4 times, the decomposed product of the acid catalyst derivative can be washed out with water almost completely. In the washing step, washing with concentrated saline or sodium sulfate aqueous solution may be performed.
【００２４】こうして水層と有機層を完全に分離したの
ち、有機層から有機溶媒を、減圧下に留去する。尚、溶
媒除去にあたっては、多官能性（メタ）アクリレートの
重合を防止するため重合防止剤を添加してもよい。該重
合防止剤としては、前記エステル化工程で例示したもの
と同様のものを使用できる。After the water layer and the organic layer are completely separated in this way, the organic solvent is distilled off from the organic layer under reduced pressure. When removing the solvent, a polymerization inhibitor may be added to prevent polymerization of the polyfunctional (meth) acrylate. As the polymerization inhibitor, the same ones as exemplified in the esterification step can be used.
【００２５】[0025]
【発明の効果】本発明の製造方法によれば、反応生成物
中の残留触媒を大幅に低減した多官能性（メタ）アクリ
レートを提供できる。こうして得られる多官能性（メ
タ）アクリレートは、従来公知の各種用途にそのまま使
用することができる。たとえば反応性希釈剤として使用
した場合に、速硬化性、高硬度に優れることは勿論のこ
と、着色性、貯蔵安定性、変異原性等の問題もなく、作
業環境の安全性も高いという諸効果を奏する。According to the production method of the present invention, it is possible to provide a polyfunctional (meth) acrylate in which the residual catalyst in the reaction product is significantly reduced. The polyfunctional (meth) acrylate thus obtained can be used as it is in various conventionally known applications. For example, when it is used as a reactive diluent, it is not only excellent in quick-curing property and high hardness, but also has no problems of colorability, storage stability, mutagenicity, etc. Produce an effect.
【００２６】[0026]
【実施例】以下に製造例、実施例及び比較例をあげて本
発明をさらに詳細に説明するが、本発明はこれら実施例
に限定されるものではない。尚、各例中の部および％は
重量基準である。EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. The parts and% in each example are based on weight.
【００２７】実施例１（エステル化物の製造） 分水器付き冷却管、撹拌機、温度計および空気吹き込み
管を備えた反応装置に、ジペンタエリスリトール３１
１．５部、アクリル酸６８８．５部、ヒドロキノンモノ
メチルエーテル１．５部、パラトルエンスルホン酸５０
部、シクロヘキサン１５０部を仕込み、３０ｍｌ／分の
流量で空気を反応液中に吹き込みながら、反応系内の温
度を１時間かけて８５℃まで昇温し、シクロヘキサンを
還流した。次いで８５〜９２℃で還流下に約１３時間保
温し、生成水量が理論生成水量の９７％に達したのち、
反応を終了し、不揮発分濃度が８６％の反応生成物のシ
クロヘキサン溶液を得た。Example 1 (Production of esterified product) A dipentaerythritol 31 was placed in a reactor equipped with a condenser tube equipped with a water diverter, an agitator, a thermometer and an air blowing tube.
1.5 parts, acrylic acid 688.5 parts, hydroquinone monomethyl ether 1.5 parts, paratoluene sulfonic acid 50
And cyclohexane of 150 parts were charged, the temperature in the reaction system was raised to 85 ° C. over 1 hour while blowing air into the reaction solution at a flow rate of 30 ml / min, and cyclohexane was refluxed. Then, the mixture was kept under reflux at 85 to 92 ° C for about 13 hours, and after the amount of water produced reached 97% of the theoretical amount of water produced,
After completion of the reaction, a cyclohexane solution of a reaction product having a nonvolatile content of 86% was obtained.
【００２８】（中和処理工程）前記反応生成物溶液９８
３．７部、シクロヘキサン１９６．７部およびトルエン
７８６．９部をビーカーに入れ、次いで撹拌下に２０％
濃度の水酸化ナトリウム水溶液３９９．６部を徐々に加
え約３０分間撹拌し、未反応のアクリル酸および残留触
媒のパラトルエンスルホン酸を中和した。次いで、該中
和液を分液ロートに移し１時間放置し、水層部を除去
し、中和工程を終了した。なお、この時点での不揮発分
濃度は３９．６％である。(Neutralization step) The reaction product solution 98
3.7 parts, 196.7 parts of cyclohexane and 786.9 parts of toluene were placed in a beaker, then 20% with stirring.
399.6 parts of a sodium hydroxide aqueous solution having a concentration was gradually added and stirred for about 30 minutes to neutralize unreacted acrylic acid and residual catalyst para-toluenesulfonic acid. Then, the neutralized solution was transferred to a separating funnel and left for 1 hour to remove the aqueous layer portion, and the neutralization step was completed. The nonvolatile content concentration at this point is 39.6%.
【００２９】実施例２（エステル化物の製造） 実施例１のエステル化物製造工程において、ジペンタエ
リスリトール３１１．５部に代えてペンタエリスリトー
ル２６６．５部を用い、アクリル酸６８８．５部に代え
て７３３．５部を用いた他は、実施例１と同様にしてエ
ステル化物の製造を行った。Example 2 (Production of Esterified Product) In the process for producing an esterified product of Example 1, 266.5 parts of pentaerythritol were used instead of 311.5 parts of dipentaerythritol, and 688.5 parts of acrylic acid were used. An esterified product was produced in the same manner as in Example 1 except that 733.5 parts were used.
【００３０】（中和処理工程）実施例１の中和工程にお
いて、エステル化物として前記エステル化物を用い、中
和工程時に添加した有機溶媒（シクロヘキサン１９６．
７部およびトルエン７８６．９部）をｎ−ヘキサン２９
５．１部、ベンゼン６８８．６部に代えた他は、実施例
１と同様にして行った。なお、この時点での不揮発分濃
度は３８．７％である。(Neutralization Treatment Step) In the neutralization step of Example 1, the esterified product was used as the esterified product, and the organic solvent (cyclohexane 196.
7 parts and toluene 786.9 parts) with n-hexane 29
The same procedure as in Example 1 was repeated except that 5.1 parts and 688.6 parts of benzene were used. The nonvolatile concentration at this point is 38.7%.
【００３１】実施例３（エステル化物の製造） 実施例１のエステル化物製造工程において、ジペンタエ
リスリトール３１１．５部に代えてトリメチロールプロ
パン３２３．２部を用い、アクリル酸６８８．５部に代
えて６７６．８部を用いた他は、実施例１と同様にして
エステル化物の製造を行った。Example 3 (Production of esterified product) In the production process of esterified product of Example 1, 323.2 parts of trimethylolpropane were used instead of 311.5 parts of dipentaerythritol, and 688.5 parts of acrylic acid were used. Was used to prepare an esterified product in the same manner as in Example 1.
【００３２】（中和処理工程）実施例１の中和工程にお
いて、エステル化物として前記エステル化物を用いた他
は、実施例１と同様にして行った。なお、この時点での
不揮発分濃度は３９．２％である。(Neutralization Step) The same procedure as in Example 1 was carried out except that the esterified product was used as the esterified product in the neutralization process of Example 1. The nonvolatile content concentration at this point is 39.2%.
【００３３】実施例４（アミン処理工程） 温度計、撹拌機、冷却管を備えた反応容器に実施例１で
得られた反応液１００部、トリエチレンジアミン０．１
９部および重合禁止剤としてメトキシフェノール０．０
４部を仕込んだ後、８０℃に２時間保った。次いで、３
％濃度の硫酸水溶液２０部を加え室温で撹拌した後、静
置し水層（下層部）を除去した。続いて１０％濃度の水
酸化ナトリウム水溶液２０部を加え室温で撹拌した後、
静置し水層（下層部）を除去し、さらに軟水３０部を加
え室温で撹拌した後、静置し水層（下層部）を除去し
た。この操作を３回繰り返して得た残液（有機層）を２
０ｍｍＨｇの減圧下、８０℃で３０分間保った。次い
で、溶媒を除去し、淡黄色透明の反応生成物ジペンタエ
リスリトールポリアクリレート３５．８部を得た。生成
物中の硫黄分を測定した結果１３１．５ｐｐｍであっ
た。Example 4 (Amine treatment step) 100 parts of the reaction solution obtained in Example 1 and 0.1 parts of triethylenediamine were placed in a reaction vessel equipped with a thermometer, a stirrer and a cooling tube.
9 parts and methoxyphenol 0.0 as a polymerization inhibitor
After charging 4 parts, it was kept at 80 ° C. for 2 hours. Then 3
After adding 20 parts of a sulfuric acid solution having a concentration of 20% and stirring at room temperature, the mixture was allowed to stand and the aqueous layer (lower part) was removed. Then, after adding 20 parts of a 10% aqueous sodium hydroxide solution and stirring at room temperature,
The mixture was allowed to stand, the aqueous layer (lower layer portion) was removed, 30 parts of soft water was further added, and the mixture was stirred at room temperature, then allowed to stand and the aqueous layer (lower layer portion) was removed. This operation was repeated 3 times to obtain a residual liquid (organic layer) of 2
It was kept under a reduced pressure of 0 mmHg at 80 ° C. for 30 minutes. Then, the solvent was removed to obtain 35.8 parts of a light yellow transparent reaction product dipentaerythritol polyacrylate. As a result of measuring the sulfur content in the product, it was 131.5 ppm.
【００３４】実施例５（アミン処理工程） 実施例４と同じ反応容器に実施例１で得られた反応液１
００部、トリエチルアミン１．９部、および重合禁止剤
としてメトキシフェノール０．０４部を仕込んだ後、５
０℃に１．５時間保った。次いで、３％濃度の硫酸水溶
液２０部を加え室温で撹拌した後、静置し水層（下層
部）を除去した。続いて、１０％濃度の水酸化ナトリウ
ム水溶液２０部を加え室温で撹拌した後、静置し水層
（下層部）を除去し、さらに軟水３０部を加え室温で撹
拌した後静置し水層（下層部）を除去した。この操作を
３回繰り返して得た残液（有機層）を２０ｍｍＨｇの減
圧下、８０℃で３０分間保った。次いで、溶媒を除去
し、淡黄色透明の反応生成物ジペンタエリスリトールポ
リアクリレート３６．２部を得た。生成物中の硫黄分を
測定した結果１２６．４ｐｐｍであった。Example 5 (Amine treatment step) The reaction solution 1 obtained in Example 1 was placed in the same reaction vessel as in Example 4.
After charging 00 parts, 1.9 parts of triethylamine, and 0.04 parts of methoxyphenol as a polymerization inhibitor, 5
Hold at 0 ° C for 1.5 hours. Then, 20 parts of a 3% strength sulfuric acid aqueous solution was added, and the mixture was stirred at room temperature and then left standing to remove the aqueous layer (lower layer portion). Subsequently, 20 parts of a 10% strength aqueous sodium hydroxide solution was added and stirred at room temperature, and then allowed to stand to remove the water layer (lower layer part). Further, 30 parts of soft water was added and stirred at room temperature, and then allowed to stand, the water layer. (Lower layer part) was removed. The residual liquid (organic layer) obtained by repeating this operation three times was kept at 80 ° C. for 30 minutes under a reduced pressure of 20 mmHg. Then, the solvent was removed to obtain 36.2 parts of a light yellow transparent reaction product dipentaerythritol polyacrylate. As a result of measuring the sulfur content in the product, it was 126.4 ppm.
【００３５】実施例６（アミン処理工程） 実施例４と同じ反応容器に実施例１で得られた反応液１
００部、トリエチレンジアミン０．１９部、４８％濃度
の水酸化ナトリウム水溶液４部、および重合禁止剤とし
てメトキシフェノール０．０４部を仕込んだ後、８０℃
に２時間保った。次いで、３％濃度の硫酸水溶液２０部
を加え室温で撹拌した後、静置し水層（下層部）を除去
した。続いて、１０％濃度の水酸化ナトリウム水溶液２
０部を加え室温で撹拌した後、静置し水層（下層部）を
除去し、さらに軟水３０部を加え室温で撹拌した後静置
し水層（下層部）を除去した。この操作を３回繰り返し
て得た残液（有機層）を２０ｍｍＨｇの減圧下、８０℃
で３０分間保った。次いで、溶媒を除去し、淡黄色透明
の反応生成物ジペンタエリスリトールポリアクリレート
３５．０部を得た。生成物中の硫黄分を測定した結果１
０２．５ｐｐｍであった。Example 6 (Amine treatment step) The reaction solution 1 obtained in Example 1 was placed in the same reaction vessel as in Example 4.
After charging 00 parts, 0.19 part of triethylenediamine, 4 parts of 48% strength aqueous sodium hydroxide solution, and 0.04 part of methoxyphenol as a polymerization inhibitor, the mixture was heated to 80 ° C.
I kept it for 2 hours. Then, 20 parts of a 3% strength sulfuric acid aqueous solution was added, and the mixture was stirred at room temperature and then left standing to remove the aqueous layer (lower layer portion). Then, a 10% aqueous sodium hydroxide solution 2
After adding 0 part of the mixture and stirring at room temperature, the mixture was allowed to stand and the aqueous layer (lower layer part) was removed. Further, 30 parts of soft water was added and stirred at room temperature and then left still to remove the aqueous layer (lower layer part). This operation was repeated 3 times to obtain a residual liquid (organic layer) under reduced pressure of 20 mmHg at 80 ° C.
Kept for 30 minutes. Then, the solvent was removed to obtain 35.0 parts of a light yellow transparent reaction product dipentaerythritol polyacrylate. Result of measurement of sulfur content in product 1
It was 02.5 ppm.
【００３６】実施例７（アミン処理工程） 実施例４と同じ反応容器に実施例１で得られた反応液１
００部、トリエタノールアミン０．３部、４８％濃度の
水酸化ナトリウム水溶液３部、および重合禁止剤として
メトキシフェノール０．０３部を仕込んだ後、８０℃に
２時間保った。次いで、３％濃度の硫酸水溶液２０部を
加え室温で撹拌した後、静置し水層（下層部）を除去し
た。続いて、１０％濃度の水酸化ナトリウム水溶液２０
部を加え室温で撹拌した後、静置し水層（下層部）を除
去し、さらに軟水３０部を加え室温で撹拌した後静置し
水層（下層部）を除去した。この操作を３回繰り返して
得た残液（有機層）を２０ｍｍＨｇの減圧下、８０℃で
３０分間保った。次いで、溶媒を除去し、淡黄色透明の
反応生成物ジペンタエリスリトールポリアクリレート３
４．６部を得た。生成物中の硫黄分を測定した結果８
５．０ｐｐｍであった。Example 7 (Amine Treatment Step) The reaction solution 1 obtained in Example 1 was placed in the same reaction vessel as in Example 4.
After charging 00 parts, 0.3 part of triethanolamine, 3 parts of 48% concentration sodium hydroxide aqueous solution, and 0.03 part of methoxyphenol as a polymerization inhibitor, the mixture was kept at 80 ° C. for 2 hours. Then, 20 parts of a 3% strength sulfuric acid aqueous solution was added, and the mixture was stirred at room temperature and then left standing to remove the aqueous layer (lower layer portion). Then, a 20% aqueous solution of sodium hydroxide 20
After adding 30 parts of the mixture and stirring at room temperature, the mixture was allowed to stand and the aqueous layer (lower layer part) was removed. Further, 30 parts of soft water was added and stirred at room temperature and then allowed to stand still to remove the aqueous layer (lower layer part). The residual liquid (organic layer) obtained by repeating this operation three times was kept at 80 ° C. for 30 minutes under a reduced pressure of 20 mmHg. Then, the solvent was removed, and a light yellow transparent reaction product dipentaerythritol polyacrylate 3 was obtained.
4.6 parts were obtained. Result of measuring sulfur content in product 8
It was 5.0 ppm.
【００３７】実施例８（アミン処理工程） 実施例４と同じ反応容器に実施例２で得られた反応液１
００部、トリエチレンジアミン０．１５部および重合禁
止剤としてメトキシフェノール０．０３部を仕込んだ
後、８０℃に２時間保った。次いで、３％濃度の硫酸水
溶液２０部を加え室温で撹拌した後、静置し水層（下層
部）を除去した。続いて、１０％濃度の水酸化ナトリウ
ム水溶液２０部を加え室温で撹拌した後、静置し水層
（下層部）を除去し、さらに軟水３０部を加え室温で撹
拌した後静置し水層（下層部）を除去した。この操作を
３回繰り返して得た残液（有機層）を２０ｍｍＨｇの減
圧下、８０℃で３０分間保った。次いで、溶媒を除去
し、淡黄色透明の反応生成物ペンタエリスリトールポリ
アクリレート３４．８部を得た。生成物中の硫黄分を測
定した結果１０５．２ｐｐｍであった。Example 8 (Amine treatment step) The reaction solution 1 obtained in Example 2 was placed in the same reaction vessel as in Example 4.
After charging 00 parts, 0.15 part of triethylenediamine and 0.03 part of methoxyphenol as a polymerization inhibitor, the mixture was kept at 80 ° C. for 2 hours. Then, 20 parts of a 3% strength sulfuric acid aqueous solution was added, and the mixture was stirred at room temperature and then left standing to remove the aqueous layer (lower layer portion). Subsequently, 20 parts of a 10% strength aqueous sodium hydroxide solution was added and stirred at room temperature, and then allowed to stand to remove the water layer (lower layer part). Further, 30 parts of soft water was added and stirred at room temperature, and then allowed to stand, the water layer. (Lower layer part) was removed. The residual liquid (organic layer) obtained by repeating this operation three times was kept at 80 ° C. for 30 minutes under a reduced pressure of 20 mmHg. Then, the solvent was removed to obtain 34.8 parts of a light yellow transparent reaction product pentaerythritol polyacrylate. As a result of measuring the sulfur content in the product, it was 105.2 ppm.
【００３８】実施例９（アミン処理工程） 実施例４と同じ反応容器に実施例３で得られた反応液１
００部、トリエチレンジアミン０．１５部および重合禁
止剤としてメトキシフェノール０．０３部を仕込んだ
後、８０℃に２時間保った。次いで、３％濃度の硫酸水
溶液２０部を加え室温で撹拌した後、静置し水層（下層
部）を除去した。続いて、１０％濃度の水酸化ナトリウ
ム水溶液２０部を加え室温で撹拌した後、静置し水層
（下層部）を除去し、さらに軟水３０部を加え室温で撹
拌した後静置し水層（下層部）を除去した。この操作を
３回繰り返して得た残液（有機層）を２０ｍｍＨｇの減
圧下、８０℃で３０分間保った。次いで、溶媒を除去
し、淡黄色透明の反応生成物トリメチロールプロパント
リアクリレート３５．７部を得た。生成物中の硫黄分を
測定した結果７８．７ｐｐｍであった。Example 9 (Amine Treatment Step) The reaction solution 1 obtained in Example 3 was placed in the same reaction vessel as in Example 4.
After charging 00 parts, 0.15 part of triethylenediamine and 0.03 part of methoxyphenol as a polymerization inhibitor, the mixture was kept at 80 ° C. for 2 hours. Then, 20 parts of a 3% strength sulfuric acid aqueous solution was added, and the mixture was stirred at room temperature and then left standing to remove the aqueous layer (lower layer portion). Subsequently, 20 parts of a 10% strength aqueous sodium hydroxide solution was added and stirred at room temperature, and then allowed to stand to remove the water layer (lower layer part). Further, 30 parts of soft water was added and stirred at room temperature, and then allowed to stand, the water layer. (Lower layer part) was removed. The residual liquid (organic layer) obtained by repeating this operation three times was kept at 80 ° C. for 30 minutes under a reduced pressure of 20 mmHg. Then, the solvent was removed to obtain 35.7 parts of a pale yellow transparent reaction product trimethylolpropane triacrylate. As a result of measuring the sulfur content in the product, it was 78.7 ppm.
【００３９】比較例１ 実施例４と同じ反応容器に実施例１で得られた反応液１
００部、および軟水３０部を加え、室温で撹拌した後、
静置し水層（下層部）を除去した。この操作を３回繰り
返して得た残液（有機層）を２０ｍｍＨｇの減圧下、８
０℃で３０分間保った。次いで、溶媒を除去し、淡黄色
透明の反応生成物ジペンタエリスリトールポリアクリレ
ート３７．４部を得た。生成物中の硫黄分を測定した結
果１０３６ｐｐｍであった。Comparative Example 1 Reaction liquid 1 obtained in Example 1 in the same reaction vessel as in Example 4.
After adding 00 parts and 30 parts of soft water and stirring at room temperature,
The mixture was allowed to stand and the aqueous layer (lower layer portion) was removed. This operation was repeated 3 times to obtain a residual liquid (organic layer) under reduced pressure of 20 mmHg, and
Hold at 0 ° C. for 30 minutes. Then, the solvent was removed to obtain 37.4 parts of a pale yellow transparent reaction product dipentaerythritol polyacrylate. The sulfur content in the product was measured and found to be 1036 ppm.
【００４０】比較例２ 実施例４と同じ反応容器に実施例２で得られた反応液１
００部、および軟水３０部を加え、室温で撹拌した後、
静置し水層（下層部）を除去した。この操作を３回繰り
返して得た残液（有機層）を２０ｍｍＨｇの減圧下、８
０℃で３０分間保った。次いで、溶媒を除去し、淡黄色
透明の反応生成物ペンタエリスリトールポリアクリレー
ト３７．０部を得た。生成物中の硫黄分を測定した結果
６３１ｐｐｍであった。Comparative Example 2 The reaction solution 1 obtained in Example 2 was placed in the same reaction vessel as in Example 4.
After adding 00 parts and 30 parts of soft water and stirring at room temperature,
The mixture was allowed to stand and the aqueous layer (lower layer portion) was removed. This operation was repeated 3 times to obtain a residual liquid (organic layer) under reduced pressure of 20 mmHg, and
Hold at 0 ° C. for 30 minutes. Then, the solvent was removed to obtain 37.0 parts of a pale yellow transparent reaction product pentaerythritol polyacrylate. As a result of measuring the sulfur content in the product, it was 631 ppm.
【００４１】比較例３ 実施例４と同じ反応容器に実施例３で得られた反応液１
００部、および軟水３０部を加え、室温で撹拌した後、
静置し水層（下層部）を除去した。この操作を３回繰り
返して得た残液（有機層）を２０ｍｍＨｇの減圧下、８
０℃で３０分間保った。次いで、溶媒を除去し、淡黄色
透明の反応生成物トリメチロールプロパントリアクリレ
ート３７．７部を得た。生成物中の硫黄分を測定した結
果４２７ｐｐｍであった。Comparative Example 3 The reaction solution 1 obtained in Example 3 was placed in the same reaction vessel as in Example 4.
After adding 00 parts and 30 parts of soft water and stirring at room temperature,
The mixture was allowed to stand and the aqueous layer (lower layer portion) was removed. This operation was repeated 3 times to obtain a residual liquid (organic layer) under reduced pressure of 20 mmHg, and
Hold at 0 ° C. for 30 minutes. Then, the solvent was removed to obtain 37.7 parts of a pale yellow transparent reaction product trimethylolpropane triacrylate. The sulfur content in the product was measured and found to be 427 ppm.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松本 圭三 大阪市鶴見区鶴見１丁目１番９号荒川化学 工業株式会社研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keizo Matsumoto 1-1-9 Tsurumi, Tsurumi-ku, Osaka Arakawa Chemical Industry Co., Ltd.
Claims (3)
および／または（メタ）アクリル酸の誘導体を、酸触媒
の存在下に有機溶媒中でエステル化反応させて得られた
反応生成物を、中和処理した後、さらにアミン類で処理
することを特徴とする多官能性（メタ）アクリレートの
製造方法。1. A reaction product obtained by subjecting a polyhydric alcohol and a (meth) acrylic acid and / or (meth) acrylic acid derivative to an esterification reaction in an organic solvent in the presence of an acid catalyst, A method for producing a polyfunctional (meth) acrylate, which comprises neutralizing and then further treating with an amine.
ル、ジペンタエリスリトール、トリメチロールプロパ
ン、グリセリン、ポリグリセリンおよびこれらの誘導体
から選ばれる少なくとも１種である請求項１記載の製造
方法。2. The production method according to claim 1, wherein the polyhydric alcohol is at least one selected from pentaerythritol, dipentaerythritol, trimethylolpropane, glycerin, polyglycerin and derivatives thereof.
記載の製造方法。3. The amine is a tertiary amine.
The manufacturing method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5029972A JP2546124B2 (en) | 1993-01-25 | 1993-01-25 | Method for producing polyfunctional (meth) acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5029972A JP2546124B2 (en) | 1993-01-25 | 1993-01-25 | Method for producing polyfunctional (meth) acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06219991A true JPH06219991A (en) | 1994-08-09 |
| JP2546124B2 JP2546124B2 (en) | 1996-10-23 |
Family
ID=12290883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5029972A Expired - Lifetime JP2546124B2 (en) | 1993-01-25 | 1993-01-25 | Method for producing polyfunctional (meth) acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2546124B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0775687A1 (en) * | 1995-11-22 | 1997-05-28 | Basf Aktiengesellschaft | Process for the preparation of esters of (meth)acrylic acid |
| JP2002037882A (en) * | 2000-07-25 | 2002-02-06 | Printing Bureau Ministry Of Finance | Polyglycerin acrylic acid ester, method of producing the same and resin composition cured by activated energy beam using the same |
| JP2002038065A (en) * | 2000-07-25 | 2002-02-06 | Printing Bureau Ministry Of Finance | Resin composition for intaglio printing ink, ink composition made by using it and printed matter obtained therefrom |
| JP2007001958A (en) * | 2005-06-27 | 2007-01-11 | Toagosei Co Ltd | Method for producing polyfunctional (meth)acrylate |
| WO2007058310A1 (en) * | 2005-11-21 | 2007-05-24 | Toagosei Co., Ltd. | Process for producing (meth)acrylic ester |
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| JP2007302596A (en) * | 2006-05-10 | 2007-11-22 | Toagosei Co Ltd | Method for producing (meth)acrylic ester |
| JP2008509136A (en) * | 2004-08-05 | 2008-03-27 | アーケマ・インコーポレイテッド | Removal of alkanesulfonic acid alkyl esters from alkanesulfonic acids and other organic media |
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1993
- 1993-01-25 JP JP5029972A patent/JP2546124B2/en not_active Expired - Lifetime
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0775687A1 (en) * | 1995-11-22 | 1997-05-28 | Basf Aktiengesellschaft | Process for the preparation of esters of (meth)acrylic acid |
| JP2002037882A (en) * | 2000-07-25 | 2002-02-06 | Printing Bureau Ministry Of Finance | Polyglycerin acrylic acid ester, method of producing the same and resin composition cured by activated energy beam using the same |
| JP2002038065A (en) * | 2000-07-25 | 2002-02-06 | Printing Bureau Ministry Of Finance | Resin composition for intaglio printing ink, ink composition made by using it and printed matter obtained therefrom |
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| JP2008509136A (en) * | 2004-08-05 | 2008-03-27 | アーケマ・インコーポレイテッド | Removal of alkanesulfonic acid alkyl esters from alkanesulfonic acids and other organic media |
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| JP5119926B2 (en) * | 2005-11-21 | 2013-01-16 | 東亞合成株式会社 | Method for producing (meth) acrylic acid ester |
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