TWI393702B - Method for producing (meth)acrylate and (meth)acrylate-based compound - Google Patents

Description

(甲基)丙烯酸酯之製法及(甲基)丙烯酸酯系組成物Method for preparing (meth) acrylate and (meth) acrylate composition

本發明係關於(甲基)丙烯酸酯之製法及(甲基)丙烯酸酯系組成物。The present invention relates to a process for producing a (meth) acrylate and a (meth) acrylate-based composition.

由於(甲基)丙烯酸酯係藉由紫外線照射或電子線照射以進行硬化的，所以用於光學透鏡或印刷油墨、塗布劑及接著劑等的各種工業用途，以作為光硬化性組成物的摻混成分。Since (meth)acrylate is cured by ultraviolet irradiation or electron beam irradiation, it is used in various industrial applications such as optical lenses or printing inks, coating agents, and adhesives, as a photocurable composition. Mixed ingredients.

然而，(甲基)丙烯酸酯的貯藏安定性或熱安定性為不良時會產生不合適的情形。However, when the storage stability or thermal stability of (meth) acrylate is poor, an inappropriate situation may occur.

例如，(甲基)丙烯酸酯的貯藏安定性為不良時，保管中會發生聚合反應而產生聚合物分，並使(甲基)丙烯酸酯分解且產生(甲基)丙烯酸等的酸成分。For example, when the storage stability of the (meth) acrylate is poor, a polymerization reaction occurs during storage to cause a polymer component, and the (meth) acrylate is decomposed to generate an acid component such as (meth)acrylic acid.

由於含有聚合物分之(甲基)丙烯酸酯的組成物會產生硬化斑或混濁，在重視均一性或光透過性之光學透鏡用途等無法合適地使用。Since a composition containing a polymer (meth) acrylate has a hard spot or turbidity, it cannot be suitably used in an optical lens application in which uniformity or light transmittance is emphasized.

又，產生酸成分之(甲基)丙烯酸酯係由於除了臭氣或裝置腐蝕的問題以外，還會使得耐水性悪化，所以在用於塗布劑或接著劑用途之情形中，硬化物吸收水分後會引起塗布面的剝離或接著強度的降低。Further, since the (meth) acrylate which generates an acid component is degraded in water resistance in addition to the problem of odor or device corrosion, in the case of use for a coating agent or an adhesive, the cured product absorbs moisture. This may cause peeling of the coated surface or a decrease in strength.

再者，(甲基)丙烯酸酯係在摻混時為了均一化而加以加熱攪拌，且在光硬化後使其曝露於耐熱試驗，但是熱安定性不良的(甲基)丙烯酸酯係由於除了如上述般的聚合物分或酸成分的發生外，還會產生著色，所以在透明性為必須之光學透鏡用途等中怎麼樣也不能使用。Further, the (meth) acrylate is heated and stirred for uniformity during blending, and is exposed to a heat resistance test after photocuring, but the (meth) acrylate having poor thermal stability is due to In addition to the occurrence of the above-mentioned polymer component or acid component, coloring occurs, so that it cannot be used in applications such as optical lenses where transparency is necessary.

還有，在本說明書中，總稱丙烯酸及甲基丙烯酸記載為「(甲基)丙烯酸」。Further, in the present specification, acrylic acid and methacrylic acid are collectively referred to as "(meth)acrylic acid".

(甲基)丙烯酸酯的貯藏安定性及熱安定性為不良的原因之一，可舉例如殘留於製品中之雜質的影響。The storage stability and thermal stability of (meth) acrylate are one of the causes of defects, and for example, the influence of impurities remaining in the product may be mentioned.

(甲基)丙烯酸酯係通常使(甲基)丙烯酸與醇類在酸觸媒存在下進行脫水酯化反應而製造的，但是酯化反應時會副生成各式各樣的雜質。為了除去此等之雜質，通常係對於脫水酯化後的反應液施加水或鹼性水溶液之洗淨操作，但是不一定能充分地去除雜質。The (meth) acrylate is usually produced by subjecting (meth)acrylic acid and an alcohol to a dehydration esterification reaction in the presence of an acid catalyst, but various impurities are formed in the esterification reaction. In order to remove such impurities, a washing operation of applying water or an alkaline aqueous solution to the reaction liquid after dehydration and esterification is usually carried out, but impurities are not necessarily sufficiently removed.

為此，強化(甲基)丙烯酸酯製造時的洗淨步驟之各種方法係受到檢討。For this reason, various methods for enhancing the washing step in the production of (meth) acrylate have been reviewed.

例如，專利文獻1係揭示在中和處理脫水酯化後的反應生成物後，再以胺類進行處理之方法。For example, Patent Document 1 discloses a method of neutralizing a reaction product after dehydration and esterification, followed by treatment with an amine.

然而，根據該方法的話，以胺類處理反應生成物後，為了將該胺類從反應生成物去除，繼續必須以酸性水溶液洗淨接著反應生成物，並將酸性成分混入反應生成物。因而，在該方法以酸性水溶液洗淨後，再一次以鹼性水溶液進行洗淨後，重複三次以軟水洗淨，因為步驟煩雜且需要長時間，所以生產性顯著地降低。又，該處理若進行工業上實施的話，係使用對於鹼性水溶液及酸性水溶液雙方不會腐蝕之特殊且高價材質的洗淨槽，且在鹼性水溶液的處理與酸性水溶液的處理係必須以其他的洗淨槽來實施，難謂適合於工業上的實施。However, according to this method, after the reaction product is treated with an amine, in order to remove the amine from the reaction product, it is necessary to wash the reaction product with an acidic aqueous solution and mix the acidic component into the reaction product. Therefore, after the method is washed with an acidic aqueous solution, it is washed again with an alkaline aqueous solution, and then washed three times with soft water. Since the procedure is complicated and takes a long time, the productivity is remarkably lowered. In addition, when this treatment is carried out industrially, a washing tank of a special and expensive material which does not corrode both the alkaline aqueous solution and the acidic aqueous solution is used, and the treatment of the alkaline aqueous solution and the treatment of the acidic aqueous solution must be carried out. The implementation of the cleaning tank is difficult to implement and is suitable for industrial implementation.

又，專利文獻2係揭示在中和或洗淨處理製造(甲基)丙烯酸酯後的反應液之際，添加陽離子系界面活性劑之方法，根據該方法的話，可防止在有機層與水層之界面附近的乳化，且可縮短有機層與水層的分離時間，其結果係可有效率地去除雜質。Further, Patent Document 2 discloses a method of adding a cationic surfactant when neutralizing or washing a reaction liquid after producing a (meth) acrylate, and according to the method, it is possible to prevent the organic layer and the water layer. Emulsification near the interface, and the separation time of the organic layer and the water layer can be shortened, and as a result, impurities can be efficiently removed.

然而，專利文獻2記載之方法雖然在有機層與水層的分離時間短縮化係為優異，但是所得(甲基)丙烯酸酯之貯藏安定性及熱安定性係為不充分者。However, the method described in Patent Document 2 is excellent in shortening the separation time between the organic layer and the aqueous layer, but the storage stability and thermal stability of the obtained (meth) acrylate are insufficient.

【專利文獻1】特開平6－219991號公報【專利文獻2】特開2001－048831號公報[Patent Document 1] JP-A-H06-219991 [Patent Document 2] JP-A-2001-048831

本發明之目的係提供一種藉由簡單的方法，可使所得之(甲基)丙烯酸酯之貯藏安定性及熱安定性係為提昇的(甲基)丙烯酸酯之製法。再者本發明之目的係提供一種貯藏安定性及熱安定性係為提昇的(甲基)丙烯酸酯系組成物。SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a (meth) acrylate which is improved in storage stability and thermal stability of the obtained (meth) acrylate by a simple method. Further, it is an object of the present invention to provide a (meth) acrylate-based composition which is improved in storage stability and thermal stability.

本發明的上述課題係藉由以下的<1>、<3>及<9>中記載之手段予以解決。較佳的實施態様<2>、<4>~<8>、<10>及<11>全部係記載如下。The above problems of the present invention are solved by the means described in the following <1>, <3> and <9>. The preferred embodiments 様<2>, <4>~<8>, <10>, and <11> are all described below.

<1>一種(甲基)丙烯酸酯之製法，其特徵係包含：在有機溶媒中藉由有機磺酸觸媒使(甲基)丙烯酸及、具有氧化烯基之醇進行脫水以形成(甲基)丙烯酸酯之酯化步驟，及將上述酯化步驟中所得(甲基)丙烯酸酯中的式(1)所示之化合物A控制在0ppm以上、100ppm以下之管理步驟，<1> A process for producing a (meth) acrylate, which comprises: dehydrating (meth)acrylic acid and an alcohol having an oxyalkylene group by an organic sulfonic acid catalyst in an organic solvent to form (methyl) The esterification step of the acrylate, and the management step of controlling the compound A represented by the formula (1) in the (meth) acrylate obtained in the esterification step to 0 ppm or more and 100 ppm or less.

〔在式(1)中，R¹ 表示烷基或芳基，R² 表示伸烷基，R³ 表示氫原子或甲基〕。 [In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkylene group, and R ³ represents a hydrogen atom or a methyl group].

<2>如<1>之(甲基)丙烯酸酯之製法，其中管理步驟係包含以下的1)~4)之至少1種手段，1)相對於在酯化步驟中醇之羥基1莫耳，使用(甲基)丙烯酸0.8莫耳以上、2.0莫耳以下。<2> The method for producing (meth) acrylate according to <1>, wherein the management step comprises at least one of the following 1) to 4), 1) relative to the hydroxyl group of the alcohol in the esterification step; Use (meth)acrylic acid at 0.8 mol or more and 2.0 mol or less.

2)在70℃以上、140℃以下進行酯化反應。2) The esterification reaction is carried out at 70 ° C or higher and 140 ° C or lower.

3)酯化反應係在大略完成的時點予以結束。3) The esterification reaction is terminated at the time of completion.

4)將藉由酯化步驟所得之反應液經由中和處理及水洗處理後所得之粗生成物中的化合物A於水分的存在下加熱，進行加水分解。4) The compound A obtained by the esterification step is heated in the presence of water by heating the compound A in the crude product obtained by the neutralization treatment and the water washing treatment to carry out hydrolysis.

<3>一種(甲基)丙烯酸酯之製法，其特徵係包含：在有機溶媒中藉由有機磺酸觸媒使(甲基)丙烯酸及、具有氧化烯基之醇進行脫水以形成(甲基)丙烯酸酯之酯化步驟(1)；將經由步驟(1)所得之反應液進行中和處理及水洗處理之步驟(2)；相對於步驟(2)所得之(甲基)丙烯酸酯，在含有1ppm以上的式(1)所示之化合物A的反應液中，添加選自於4級銨鹽、4級鏻鹽、脒、具有1級胺基及/或2級胺基之化合物、胺基脲以及吡啶所組成族群之至少1種特定處理劑之添加步驟， 〔在式(1)中，R¹ 表示烷基或芳基，R² 表示伸烷基，R³ 表示氫原子或甲基〕。<3> A method for producing a (meth) acrylate, which comprises: dehydrating (meth)acrylic acid and an alcohol having an oxyalkylene group by an organic sulfonic acid catalyst in an organic solvent to form a methyl group The esterification step (1) of the acrylate; the step (2) of subjecting the reaction liquid obtained in the step (1) to a neutralization treatment and a water washing treatment; and the (meth) acrylate obtained in the step (2), In the reaction liquid containing 1 ppm or more of the compound A represented by the formula (1), a compound selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, a hydrazine, a compound having a primary amine group and/or a secondary amine group, and an amine are added. a step of adding at least one specific treatment agent of a group consisting of a urea group and a pyridine, [In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkylene group, and R ³ represents a hydrogen atom or a methyl group].

<4>如<3>記載之(甲基)丙烯酸酯之製法，其係在添加上述特定處理劑的添加步驟之後，含有餾去有機溶媒之脫溶媒步驟。<4> The method for producing a (meth) acrylate according to <3>, which comprises the step of adding a solvent to the organic solvent after the step of adding the specific treating agent.

<5>如<3>記載之(甲基)丙烯酸酯之製法，其係在上述步驟(2)之後，含有：餾去有機溶媒之脫溶媒步驟、在脫溶媒步驟後的反應液中添加上述特定處理劑之添加步驟、及進行加熱之加熱步驟。<5> The method for producing a (meth) acrylate according to <3>, which after the step (2), comprises: a solvent removal step of distilling off the organic solvent; and adding the above to the reaction liquid after the solvent removal step a step of adding a specific treatment agent and a heating step of performing heating.

<6>如<5>記載之(甲基)丙烯酸酯之製法，其中上述加熱溫度為30~100℃。<6> The method for producing a (meth) acrylate according to <5>, wherein the heating temperature is 30 to 100 °C.

<7>如<1>~<6>項中任一項之(甲基)丙烯酸酯之製法，其中具有氧化烯基之醇係為多元醇之環氧烷加成物。<7> The method for producing a (meth) acrylate according to any one of <1> to <6> wherein the alcohol having an oxyalkylene group is an alkylene oxide adduct of a polyhydric alcohol.

<8>如<1>~<7>項中任一項之(甲基)丙烯酸酯之製法，其中具有氧化烯基之醇的氧化烯基為氧乙烯基或氧丙烯基，在式(1)中R² 的伸烷基為伸乙基或伸丙基。<8> The method for producing a (meth) acrylate according to any one of <1> to <7> wherein the oxyalkylene group of the alcohol having an oxyalkylene group is an oxyethylene group or an oxypropylene group, in the formula (1) The alkylene group of R ² is an exoethyl or a propyl group.

<9>一種(甲基)丙烯酸酯系組成物，其係含有具有使(甲基)丙烯酸與具有氧化烯基之醇在有機磺酸觸媒的存在下經脫水酯化反應所得氧化烯基的(甲基)丙烯酸酯之組成物，其係含有0ppm以上、100ppm以下的式(1)所示之化合物A， 〔在式(1)中，R¹ 表示烷基或芳基，R² 表示伸烷基，R³ 表示氫原子或甲基〕。<9> A (meth) acrylate-based composition comprising an oxyalkylene group obtained by dehydrating esterification of (meth)acrylic acid with an alcohol having an oxyalkylene group in the presence of an organic sulfonic acid catalyst a composition of (meth) acrylate, which contains 0 ppm or more and 100 ppm or less of the compound A represented by the formula (1), [In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkylene group, and R ³ represents a hydrogen atom or a methyl group].

<10>如<9>記載之(甲基)丙烯酸酯系組成物，其中具有氧化烯基之醇係為多元醇之環氧烷加成物。<10> The (meth) acrylate composition according to <9>, wherein the alcohol having an oxyalkylene group is an alkylene oxide adduct of a polyhydric alcohol.

<11>如<9>或<10>記載之(甲基)丙烯酸酯系組成物，其中具有氧化烯基之醇的氧化烯基為氧乙烯基或氧丙烯基，在式(1)中R² 的伸烷基為伸乙基或伸丙基。<11> The (meth) acrylate composition according to <9> or <10> wherein the oxyalkylene group of the alcohol having an oxyalkylene group is an oxyethylene group or an oxypropylene group, and R in the formula (1) The alkyl group of ² is an extended ethyl group or a stretched propyl group.

根據本發明係提供一種藉由簡單的方法，可提昇所得(甲基)丙烯酸酯之貯藏安定性及熱安定性，更具體而言，可提供一種能抑制酸價上昇之(甲基)丙烯酸酯之製法。再者，根據本發明可提供一種提昇貯藏安定性及熱安定性，更具體而言，能抑制酸價上昇之(甲基)丙烯酸酯系組成物。According to the present invention, it is possible to enhance the storage stability and thermal stability of the obtained (meth) acrylate by a simple method, and more particularly, to provide a (meth) acrylate capable of suppressing an increase in acid value. The method of production. Further, according to the present invention, it is possible to provide a (meth) acrylate-based composition which can improve storage stability and thermal stability, and more specifically, can suppress an increase in acid value.

實施發明之最佳形態Best form for implementing the invention

本發明人等係在(甲基)丙烯酸酯之製法中，對於(甲基)丙烯酸酯之貯藏安定性或熱安定性形成不良之原因物質進行各種的檢討。The present inventors have conducted various reviews on the cause of poor formation stability or thermal stability of (meth) acrylate in the production method of (meth) acrylate.

其結果發現在有特定的化合物以特定量存在於(甲基)丙烯酸酯中時，在經過長時間後酸成分係為上昇，且發現藉由使得該值為特定量以下，可提昇(甲基)丙烯酸酯之貯藏安定性或熱安定性，而完成本發明。As a result, it has been found that when a specific compound is present in the (meth) acrylate in a specific amount, the acid component rises after a long period of time, and it is found that the value is increased by a certain amount or less. The storage stability or thermal stability of the acrylate is completed by the present invention.

再者，發現當上述原因物質之特定化合物超過特定量之情形，藉由以特定的處理劑加以處理，能夠提昇(甲基)丙烯酸酯之貯藏安定性或熱安定性，而完成本發明。Further, it has been found that when the specific compound of the above-mentioned causative substance exceeds a certain amount, the storage stability or thermal stability of the (meth) acrylate can be improved by treating with a specific treating agent, and the present invention has been completed.

以下，詳細說明本發明。Hereinafter, the present invention will be described in detail.

本發明的第1(甲基)丙烯酸酯製法之特徵係包含：在有機溶媒中藉由有機磺酸觸媒使(甲基)丙烯酸及、具有氧化烯基之醇進行脫水以形成(甲基)丙烯酸酯之酯化步驟；及將所得(甲基)丙烯酸酯中後述式(1)所示之化合物A控制在0ppm以上、100ppm以下(在本發明中，「0ppm以上、100ppm以下」亦可記載為「0~100ppm」或「0ppm~100ppm」。以下相同)之管理步驟。The first (meth) acrylate method of the present invention is characterized in that (meth)acrylic acid and an alcohol having an oxyalkylene group are dehydrated by an organic sulfonic acid catalyst to form a (meth) group in an organic solvent. The esterification step of the acrylate; and the compound A represented by the formula (1) to be described later in the obtained (meth) acrylate is controlled to be 0 ppm or more and 100 ppm or less (in the present invention, "0 ppm or more and 100 ppm or less" may be described. The management procedure is "0~100ppm" or "0ppm~100ppm". The same applies below.

又，本發明的第2(甲基)丙烯酸酯製法之特徵係包含：在有機溶媒中藉由有機磺酸觸媒使(甲基)丙烯酸及、具有氧化烯基之醇進行脫水以形成(甲基)丙烯酸酯之酯化步驟(1)；將經由步驟(1)所得之反應液進行中和處理及水洗處理之步驟(2)；相對於步驟(2)所得之(甲基)丙烯酸酯，在含有1ppm以上後述式(1)所示之化合物A的有機反應液中，添加選自於4級銨鹽、4級鏻鹽、脒、具有1級胺基及/或2級胺基之化合物、胺基脲以及吡啶所組成族群之至少1種特定處理劑之添加步驟。Further, the second (meth) acrylate method of the present invention is characterized in that: (meth)acrylic acid and an alcohol having an oxyalkylene group are dehydrated by an organic sulfonic acid catalyst in an organic solvent to form (A) The esterification step (1) of the acrylate; the step (2) of subjecting the reaction solution obtained in the step (1) to a neutralization treatment and a water washing treatment; and the (meth) acrylate obtained in the step (2), In the organic reaction solution containing 1 ppm or more of the compound A represented by the following formula (1), a compound selected from the group consisting of a grade 4 ammonium salt, a grade 4 onium salt, a phosphonium, a grade 1 amine group, and/or a grade 2 amine group is added. And a step of adding at least one specific treatment agent of the group consisting of aminourea and pyridine.

(化合物A)以下，說明式(1)所示之化合物A。(Compound A) Hereinafter, the compound A represented by the formula (1) will be described.

在式(1)中，R¹ 表示烷基或芳基，R² 表示伸烷基，R³ 表示氫原子或甲基。In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkylene group, and R ³ represents a hydrogen atom or a methyl group.

R¹ 表示烷基或芳基，該烷基及芳基可為無取代、亦可具有1以上的取代基。烷基係以碳數1~10為佳、芳基係以碳數6~12為佳。又，烷基係可為直鏈狀、分枝狀，且亦可具有環狀構造。R ¹ represents an alkyl group or an aryl group, and the alkyl group and the aryl group may be unsubstituted or may have one or more substituents. The alkyl group is preferably a carbon number of from 1 to 10, and the aryl group is preferably a carbon number of from 6 to 12. Further, the alkyl group may be linear or branched, and may have a cyclic structure.

可與烷基容許之取代基可例示如芳基、烷氧基、鹵素原子，較佳為芳基及鹵素原子、更佳係芳基、特佳為苯基。The substituent which may be bonded to the alkyl group may, for example, be an aryl group, an alkoxy group or a halogen atom, preferably an aryl group and a halogen atom, more preferably an aryl group, and particularly preferably a phenyl group.

又，可與芳基容許之取代基可例示如烷基、鹵素原子、烷氧基，較佳為烷基、碳數1~3的烷基為更佳。Further, the substituent which may be bonded to the aryl group may, for example, be an alkyl group, a halogen atom or an alkoxy group, more preferably an alkyl group or an alkyl group having 1 to 3 carbon atoms.

具體而言，R¹ 係可例示如甲基、苯基、甲苯醯基、乙基苯基及苄基為佳。Specifically, R ¹ is preferably a methyl group, a phenyl group, a tolyl group, an ethylphenyl group or a benzyl group.

在化合物A中，R¹ 係來自酯化反應中所使用之有機磺酸觸媒者。In the compound A, R ¹ is derived from an organic sulfonic acid catalyst used in the esterification reaction.

R¹ 為甲基的情形係為使用作為酸觸媒之甲磺酸之情形，以下相同地，苯基的情形為苯磺酸、甲苯醯基的情形為p－甲苯磺酸、乙基苯基的情形為乙基苯磺酸，又，苄基的情形為苄磺酸。In the case where R ¹ is a methyl group, the case of using methanesulfonic acid as an acid catalyst is as follows. In the same manner, in the case of a phenyl group, in the case of a benzenesulfonic acid or a tolylsulfonyl group, p-toluenesulfonic acid or ethylphenyl group is used. The case is ethylbenzenesulfonic acid, and the case of benzyl is benzylsulfonic acid.

R² 的伸烷基係以碳數4以下的伸烷基為佳、更佳係伸乙基及伸丙基。R² 係對應於酯化反應中所使用之醇的環氧烷基。The alkylene group of R ² is preferably an alkylene group having a carbon number of 4 or less, more preferably an ethyl group and a propyl group. R ² corresponds to an alkylene oxide of an alcohol used in the esterification reaction.

R³ 表示氫原子或甲基。R³ 係對應於酯化反應所使用之(甲基)丙烯酸。R ³ represents a hydrogen atom or a methyl group. R ³ corresponds to the (meth)acrylic acid used in the esterification reaction.

化合物A係推定為酯化反應中所使用之醇與有機磺酸觸媒的反應物。(甲基)丙烯酸酯中存在化合物A時，經過長時間的分解會產生酸，其係推論對於(甲基)丙烯酸酯的貯藏安定性或熱安定性是不良的。Compound A is presumed to be a reactant of an alcohol used in an esterification reaction with an organic sulfonic acid catalyst. When the compound A is present in the (meth) acrylate, an acid is generated after a long period of decomposition, which is inferior to the storage stability or thermal stability of the (meth) acrylate.

(甲基)丙烯酸酯中化合物A之含有比例的分析方法係舉例有液體層析法及氣體層析法等，以不使得化合物A分解且可安定地觀測之液體層析法為佳。The analysis method of the content ratio of the compound A in the (meth) acrylate is exemplified by liquid chromatography, gas chromatography, or the like, and liquid chromatography which does not decompose the compound A and can be stably observed.

此外，液體層析法係以因定量性．檢測感度優異之液體層析法/質量分析法(以下，稱為LC/MS)為佳。In addition, liquid chromatography is based on quantitative. A liquid chromatography/mass spectrometry (hereinafter referred to as LC/MS) excellent in detecting sensitivity is preferred.

藉由LC/MS之化合物A的定量條件係列舉如下。The series of quantitative conditions of Compound A by LC/MS are as follows.

○LC條件裝置：高速液體層析儀(HPLC)、管柱的種類：ODS管柱、管柱的溫度：40℃、溶離液：水/甲醇系○MS條件檢測器：ESI(＋)○ LC condition device: High-speed liquid chromatograph (HPLC), type of column: ODS column, column temperature: 40 ° C, eluent: water / methanol system ○ MS condition detector: ESI (+)

((甲基)丙烯酸酯之製法)本發明係首先在有機溶媒中藉由有機磺酸觸媒使(甲基)丙烯酸及、具有氧化烯基之醇進行脫水，以進行形成(甲基)丙烯酸酯之酯化步驟。以下，說明酯化步驟。(Production method of (meth) acrylate) The present invention first dehydrates (meth)acrylic acid and an alcohol having an oxyalkylene group by an organic sulfonic acid catalyst in an organic solvent to form a (meth)acrylic acid. The esterification step of the ester. Hereinafter, the esterification step will be described.

1.酯化步驟1. Esterification step

本發明中，首先使(甲基)丙烯酸與具有氧化烯基之醇(以下，亦有僅稱為「醇」)於有機溶媒中、在有機磺酸觸媒的存在下進行脫水酯化以形成(甲基)丙烯酸酯。脫水酯化反應係在加熱．攪拌下進行為佳。In the present invention, first, (meth)acrylic acid and an alcohol having an oxyalkylene group (hereinafter, simply referred to as "alcohol") are dehydrated and esterified in the presence of an organic sulfonic acid catalyst in an organic solvent to form an alcohol. (Meth) acrylate. The dehydration esterification reaction is heating. It is preferred to carry out under stirring.

在醇中的氧化烯基係以碳數4以下的氧化烯基為佳、更佳係氧乙烯基或氧丙烯基。The oxyalkylene group in the alcohol is preferably an oxyalkylene group having 4 or less carbon atoms, more preferably an oxyethylene group or an oxypropylene group.

在醇中的氧化烯基係亦可具有2以上重複單位之聚氧化烯基。The oxyalkylene group in the alcohol may have a polyoxyalkylene group having 2 or more repeating units.

醇係可使用各種的化合物，具體而言係列舉如以下所示之醇的環氧烷加成物等。Various compounds can be used for the alcohol system, and specifically, an alkylene oxide adduct of an alcohol shown below can be used.

[1]甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、正戊醇、環己醇、正庚醇、正辛醇、2－乙基己醇、異辛醇、正壬醇、異壬醇等的一價烷基醇及此等的環氧烷加成物。[1] methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, cyclohexanol, n-heptanol, n-octanol, 2-ethylhexanol, isooctanol, A monovalent alkyl alcohol such as n-nonanol or isodecyl alcohol and such an alkylene oxide adduct.

[2]酚、氯酚、溴酚、氟酚、萘酚、苯基酚、枯基酚、壬基酚、雙酚A、雙酚F、硫代雙酚及4,4’－磺醯二酚等的具有酚性羥基之化合物及此等的環氧烷加成物。[2] Phenol, chlorophenol, bromophenol, fluorophenol, naphthol, phenylphenol, cumylphenol, nonylphenol, bisphenol A, bisphenol F, thiobisphenol and 4,4'-sulfonate A compound having a phenolic hydroxyl group such as a phenol or the like, and an alkylene oxide adduct thereof.

[3]乙二醇、丙二醇、新戊二醇、二甘醇、三乙二醇、聚乙二醇、二丙二醇、三丙二醇、聚丙二醇等的醇類及此等的環氧烷加成物。[3] Alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and the like, and alkylene oxide adducts thereof .

[4]甘油、二甘油、三甘油、聚甘油等的甘油及此等的環氧烷加成物。[4] Glycerol such as glycerin, diglycerin, triglycerin or polyglycerin, and such an alkylene oxide adduct.

[5]丁二醇、戊二醇、己二醇、三羥甲基丙烷、二三羥甲基丙烷、季戊四醇、二季戊四醇等的多元醇及此等的環氧烷加成物。[5] Polyols such as butanediol, pentanediol, hexanediol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like, and alkylene oxide adducts thereof.

[6]參－2－羥基乙基三聚異氰酸酯。[6] Para-2-hydroxyethyl trimeric isocyanate.

還有，上述環氧烷係以碳數4以下的環氧烷為較佳、更佳為環氧乙烷及環氧丙烷。Further, the above alkylene oxide is preferably an alkylene oxide having 4 or less carbon atoms, more preferably ethylene oxide or propylene oxide.

每1莫耳化合物之環氧烷的平均加成莫耳數係以1~10莫耳為佳。The average addition mole number of alkylene oxide per 1 mole compound is preferably 1 to 10 moles.

本發明係更適合使用於在上述醇之中，對於所得之(甲基)丙烯酸酯中容易產生許多雜質，且多元醇的環氧烷加成物、或環氧烷加成數大的醇者。The present invention is more suitably used in the above-mentioned alcohols, and a large amount of impurities are easily generated in the obtained (meth) acrylate, and an alkylene oxide adduct of a polyhydric alcohol or an alcohol having a large alkylene oxide addition number is used.

多元醇之環氧烷加成物的較佳具體例係舉例如三羥甲基丙烷的環氧烷加成物、雙酚A的環氧烷加成物及二甘油的環氧烷加成物等，環氧烷加成物的具體例係舉例如環氧乙烷加成物及環氧丙烷加成物。Preferred specific examples of the alkylene oxide adduct of the polyhydric alcohol are, for example, an alkylene oxide adduct of trimethylolpropane, an alkylene oxide adduct of bisphenol A, and an alkylene oxide adduct of diglycerin. Specific examples of the alkylene oxide adduct include, for example, an ethylene oxide adduct and a propylene oxide adduct.

環氧烷加成數大之醇係舉例如每1莫耳的化合物具有平均加成莫耳數3莫耳以上的環氧烷基之醇，具體而言如壬基酚之環氧烷4莫耳加成物等，環氧烷加成物的具體例係舉例如環氧乙烷加成物及環氧丙烷加成物。The alcohol having a large number of alkylene oxide additions is, for example, an alkylene oxide having an average molar addition of 3 moles or more per 1 mole of the compound, specifically, an alkylene oxide 4 mole such as nonylphenol. Specific examples of the alkylene oxide adduct such as an adduct and the like are, for example, an ethylene oxide adduct and a propylene oxide adduct.

在脫水酯化反應中(甲基)丙烯酸與醇的使用比例係相對於醇之羥基1莫耳，(甲基)丙烯酸係以0.8~2.0莫耳為佳、更佳係1.0~1.5莫耳。丙烯酸的使用比例為0.8莫耳以上時，由於脫水酯化反應的時間小時短，且醇性羥基邁克耳加成至(甲基)丙烯酸酯之(甲基)丙烯醯基上等的副反應少，所以可得到良好的製品純度而為佳。又，丙烯酸的使用比例為2.0莫耳以下時，因為(甲基)丙烯酸邁克耳加成至(甲基)丙烯酸酯之(甲基)丙烯醯基上等的加成反應少，且得到良好的製品純度之外，於脫水酯化後去除未反應丙烯酸之必要變少而為佳。In the dehydration esterification reaction, the ratio of (meth)acrylic acid to alcohol is 1 mole relative to the hydroxyl group of the alcohol, and the (meth)acrylic acid is preferably 0.8 to 2.0 moles, more preferably 1.0 to 1.5 moles. When the use ratio of acrylic acid is 0.8 mol or more, the time of the dehydration esterification reaction is short, and the side reaction of the alcoholic hydroxymike addition to the (meth) acrylonitrile group of the (meth) acrylate is small. Therefore, it is preferred to obtain good product purity. Further, when the use ratio of acrylic acid is 2.0 mol or less, the addition reaction of the (meth)acrylic acid Michael addition to the (meth)acrylic acid group of (meth)acrylate is small, and good is obtained. In addition to the purity of the product, it is preferred to reduce the amount of unreacted acrylic acid after dehydration and esterification.

脫水酯化反應中所使用之有機磺酸觸媒可舉例如式(2)所示之有機磺酸觸媒。The organic sulfonic acid catalyst used in the dehydration esterification reaction may, for example, be an organic sulfonic acid catalyst represented by the formula (2).

在式(2)，R¹ 係與在式(1)中的R¹ 相同，又，較佳的範圍亦為相同。In the formula (2), R ¹ is the same as R ¹ in the formula (1), and the preferred range is also the same.

具體而言，有機磺酸觸媒係舉例如p－甲苯磺酸、甲磺酸、苯磺酸、乙基苯磺酸及苄磺酸等，其可單獨一種、或任意組合二種以上而使用。Specifically, the organic sulfonic acid catalyst may, for example, be p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid or benzylsulfonic acid, and may be used alone or in combination of two or more. .

有機磺酸觸媒的使用比例係相對於脫水酯化所供給之醇性羥基的莫耳數，以0.05mol%~10mol%為佳、更佳係0.5mol%~5mol%。有機磺酸觸媒的使用比例為0.5mol%以上時，由於可得到實用的反應速度而為佳。又，為10mol%以下時，因為副反應少且製品的細度高，又著色少，在精製步驟中觸媒的去除或製品的脫色操作中所需要的勞力少而為佳。The use ratio of the organic sulfonic acid catalyst is preferably 0.05 mol% to 10 mol%, more preferably 0.5 mol% to 5 mol%, based on the mole number of the alcoholic hydroxyl group supplied by the dehydration esterification. When the use ratio of the organic sulfonic acid catalyst is 0.5 mol% or more, a practical reaction rate can be obtained. In addition, when it is 10 mol% or less, since the side reaction is small, the fineness of the product is high, and the coloring is small, and the labor required for the removal of the catalyst or the decoloring operation of the product in the purification step is preferably small.

在本發明中，於酯化步驟所使用之有機溶媒係以使用與脫水酯化反應所生成之水的溶解度低之有機溶媒為佳。又，酯化步驟係一邊與水共沸餾去、一邊進行為佳。In the present invention, the organic solvent used in the esterification step is preferably an organic solvent having a low solubility in water produced by the dehydration esterification reaction. Further, the esterification step is preferably carried out while azeotropically distilling off with water.

能在酯化步驟中適當使用之有機溶媒，舉例如甲苯、苯及二甲苯等的芳香族烴、己烷、環己烷及庚烷等的脂肪族烴、以及甲基乙基酮及環己酮等的酮類。Examples of the organic solvent which can be suitably used in the esterification step include aromatic hydrocarbons such as toluene, benzene, and xylene, aliphatic hydrocarbons such as hexane, cyclohexane, and heptane, and methyl ethyl ketone and cyclohexane. Ketones such as ketones.

有機溶媒係考慮到基質的溶解性等，可單獨一種使用、或亦可任意組合二種以上使用為佳。The organic solvent is preferably used alone or in combination of two or more kinds in consideration of the solubility of the substrate.

有機溶媒的比例係以在反應液中為30~70重量%為佳。The ratio of the organic solvent is preferably from 30 to 70% by weight in the reaction liquid.

酯化反應溫度係以70~140℃為佳。反應溫度為70℃以上時，由於可快速進行反應而為佳。又，為140℃以下時，在酯化步驟中雜質的副生成少，而且不會產生膠化而為佳。The esterification reaction temperature is preferably 70 to 140 °C. When the reaction temperature is 70 ° C or more, it is preferred because the reaction can be carried out rapidly. Moreover, when it is 140 ° C or less, it is preferable that the amount of secondary generation of impurities is small in the esterification step, and gelation does not occur.

酯化反應其目的為了防止(甲基)丙烯醯基的聚合，以使用聚合抑制劑為佳，再者亦可將含氧氣體導入至反應液。The purpose of the esterification reaction is to prevent polymerization of a (meth) acrylonitrile group, and it is preferable to use a polymerization inhibitor, and an oxygen-containing gas may be introduced into the reaction liquid.

聚合抑制劑係舉例如氫醌、第三丁基氫醌、氫醌一甲基醚、2,6－二－第三丁基－4－甲基酚、2,4,6－三－第三丁基酚、苯醌、吩噻等的有機系聚合抑制劑、氯化銅及硫酸銅等的無機系聚合抑制劑，以及二丁基二硫代胺基甲酸銅等的有機鹽系聚合抑制劑等。聚合抑制劑係可單獨一種使用、或亦可任意組合二種以上使用為佳。聚合抑制劑的比例係以在反應液中為5~20,000wtppm為佳、更佳係25~3,000wtppm。The polymerization inhibitor is, for example, hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-third Butyl phenol, benzoquinone, phenothiazine An organic polymerization inhibitor such as an organic polymerization inhibitor, an organic polymerization inhibitor such as copper chloride or copper sulfate, or an organic salt polymerization inhibitor such as copper dibutyldithiocarbamate. The polymerization inhibitor may be used alone or in combination of two or more. The proportion of the polymerization inhibitor is preferably from 5 to 20,000 wtppm, more preferably from 25 to 3,000 wtppm, in the reaction liquid.

含氧氣體係舉例如空氣、氧與氮的混合氣體、氧與氦的混合氣體等。The oxygen-containing system includes, for example, air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

2.將(甲基)丙烯酸酯中的化合物A控制在0ppm以上、100ppm以下之管理步驟2. Management step of controlling compound A in (meth) acrylate to 0 ppm or more and 100 ppm or less

本發明的第1(甲基)丙烯酸酯之製法中，包含將所得之(甲基)丙烯酸酯中式(1)所示之化合物A控制在0ppm以上、100ppm以下之管理步驟。The method for producing the first (meth) acrylate of the present invention includes a management step of controlling the compound A represented by the formula (1) in the obtained (meth) acrylate to 0 ppm or more and 100 ppm or less.

(甲基)丙烯酸酯中化合物A的比例超過100ppm之情形，組成物的貯藏安定性或熱安定性係變得不良。When the ratio of the compound A in the (meth) acrylate exceeds 100 ppm, the storage stability or thermal stability of the composition becomes poor.

化合物A的比例係以0ppm以上、80ppm以下為佳，較佳係0~50ppm、0~30ppm為更佳，為無法檢測者(1ppm以下)為特佳。The ratio of the compound A is preferably 0 ppm or more and 80 ppm or less, more preferably 0 to 50 ppm and more preferably 0 to 30 ppm, and particularly preferably not detectable (1 ppm or less).

特別是，R¹ 含有芳香族基之情形中，化合物A係以0~80ppm為佳、0~50ppm為較佳、0~30ppm為較佳。又，R¹ 不含有芳香族基之情形，例如在無取代烷基之情形中，化合物A則是以0~30ppm為佳、0~10ppm為較佳、0~5ppm為較佳。In particular, in the case where R ¹ contains an aromatic group, the compound A is preferably 0 to 80 ppm, more preferably 0 to 50 ppm, and most preferably 0 to 30 ppm. Further, in the case where R ¹ does not contain an aromatic group, for example, in the case of an unsubstituted alkyl group, the compound A is preferably 0 to 30 ppm, more preferably 0 to 10 ppm, and most preferably 0 to 5 ppm.

使最終所得之(甲基)丙烯酸酯中化合物A的比例為100ppm以下之方法係可例示如(a)以溫和條件實施酯化反應之方法、(b)使其在(甲基)丙烯酸酯之製法中酯化反應後實施之實施精製步驟之方法等。The method of making the ratio of the compound A in the finally obtained (meth) acrylate to 100 ppm or less can be exemplified by (a) a method of performing an esterification reaction under mild conditions, and (b) making it in a (meth) acrylate. A method of performing a purification step, which is carried out after the esterification reaction in the production method, and the like.

(a)以溫和條件實施酯化反應之方法，具體而言可例示如以下的(a－1)~(a－3)。(a) A method of carrying out the esterification reaction under mild conditions, and specifically, the following (a-1) to (a-3) can be exemplified.

(a－1)對於醇不過剩使用(甲基)丙烯酸之方法對於醇之羥基1莫耳，(甲基)丙烯酸係以使用0.8~2.0莫耳為佳、使用1.0~1.5莫耳為較佳、使用1.0~1.2莫耳為更佳。(a-1) For the alcohol, the method of using (meth)acrylic acid is not preferred for the hydroxyl group of the alcohol, and the (meth)acrylic acid is preferably 0.8 to 2.0 moles, preferably 1.0 to 1.5 moles. It is better to use 1.0~1.2 moules.

(a－2)在過剩且高溫條件不進行酯化反應之方法酯化反應係在70~140℃下進行為佳、在80~130℃下進行為較佳、在90~120℃下進行為更佳。(a-2) Method of not performing esterification reaction in excess and high temperature conditions The esterification reaction is preferably carried out at 70 to 140 ° C, preferably at 80 to 130 ° C, and preferably at 90 to 120 ° C. Better.

(a－3)酯化反應係在大略完成的時點予以結束方法酯化反應係大致上結束這件事，可藉由定期測定反應液的酸價，從進料的(甲基)丙烯酸換算出反應液中所含未反應的(甲基)丙烯酸之方法，或是藉由酯化反應檢測餾出水的量來加以確認。(a-3) The esterification reaction is terminated at the point of completion of the process. The esterification reaction system is substantially completed, and the acid value of the reaction liquid can be periodically measured to be converted from the (meth)acrylic acid of the feed. The method of reacting unreacted (meth)acrylic acid in the reaction liquid or confirming the amount of the distilled water by the esterification reaction is confirmed.

酯化反應中，一般係在用於反應熟成之酯化反應後加熱數小時(後加熱)，但是在其加熱之後恐有產生化合物A之虞。因此，以酯化反應終了後不進行長時間加熱之方法為佳。在該情形的加熱時間係以在3小時以內者為佳、更佳係1小時以內。In the esterification reaction, it is generally heated for several hours (post-heating) after the esterification reaction for the reaction ripening, but it is feared that the compound A is produced after the heating. Therefore, it is preferred that the method of not heating for a long time after the end of the esterification reaction is preferred. The heating time in this case is preferably within 3 hours, more preferably within 1 hour.

又，在本發明中，亦可適當組合(a－1)~(a－3)。Further, in the present invention, (a-1) to (a-3) may be combined as appropriate.

又，(b)使其在(甲基)丙烯酸酯之製法中酯化反應後實施之實施精製步驟之方法中，精製步驟係舉例如中和處理及水洗處理等。Further, (b) in the method of performing the purification step which is carried out after the esterification reaction in the process for producing (meth) acrylate, the purification step is, for example, a neutralization treatment or a water washing treatment.

此外，實施上述方法而(甲基)丙烯酸酯中化合物A的比例超過100ppm時、或其目的係進一步減少化合物A的比例時，可例示如將藉由酯化步驟所得之反應液經由中和處理及水洗處理後所得之粗生成物中的化合物A於水分的存在下加熱，進行加水分解方法。Further, when the above method is carried out and the ratio of the compound A in the (meth) acrylate exceeds 100 ppm, or the purpose thereof further reduces the ratio of the compound A, the reaction solution obtained by the esterification step can be exemplified by neutralization treatment. The compound A in the crude product obtained after the water washing treatment is heated in the presence of water to carry out a hydrolysis method.

此情形之加熱溫度．時間可視其(甲基)丙烯酸酯中化合物A的比例而適當設定為佳，加熱溫度係以60~140℃為佳、60~120℃為較佳、60~100℃為更佳。又，加熱時間係以0.5小時~300小時為佳、5~200小時為較佳、20~150小時為更佳。The heating temperature in this case. The time is preferably set as appropriate in the ratio of the compound A in the (meth) acrylate, and the heating temperature is preferably 60 to 140 ° C, more preferably 60 to 120 ° C, and still more preferably 60 to 100 ° C. Further, the heating time is preferably from 0.5 to 300 hours, more preferably from 5 to 200 hours, even more preferably from 20 to 150 hours.

可以如採用上述(a)~(b)方法中任一者以上，且定期監視所得之(甲基)丙烯酸酯中化合物A的比例，來管理最終所得(甲基)丙烯酸酯中化合物A為100ppm以下。The compound A in the final (meth) acrylate can be managed to be 100 ppm by using any of the above methods (a) to (b) and periodically monitoring the ratio of the compound A in the obtained (meth) acrylate. the following.

上述的方法之中，選擇採用哪種手段、以怎樣的條件來實施係根據所使用之(甲基)丙烯酸、醇及磺酸觸媒的種類及量、所得之(甲基)丙烯酸酯中化合物A的比例、以及最終製品的用途等，來做適當的選擇為佳。Among the above methods, which method is used and under what conditions are used, depending on the type and amount of (meth)acrylic acid, alcohol, and sulfonic acid catalyst used, and the obtained compound in (meth) acrylate It is preferable to make an appropriate choice of the ratio of A and the use of the final product.

上述的方法之中，以溫和條件實施酯化反應之方法及中和．水洗後的(甲基)丙烯酸酯在水分的存在下加熱，使化合物A加水分解，然後再一次進行中和．水洗之方法為佳，從簡單且可以工業規模實施之點而言，以溫和條件實施酯化反應之方法為較佳。Among the above methods, the method and neutralization of the esterification reaction are carried out under mild conditions. The water-washed (meth) acrylate is heated in the presence of moisture to cause the compound A to be hydrolyzed and then neutralized again. The method of washing is preferably carried out, and a method of carrying out the esterification reaction under mild conditions is preferred from the viewpoint of being simple and can be carried out on an industrial scale.

3.中和處理及水洗處理3. Neutralization treatment and washing treatment

以下，就本發明的第1製法中採用的精製步驟之中和處理及水洗處理等，以及對於本發明的第2製法中酯化步驟後之反應液所實施的中和處理及水洗處理加以説明。Hereinafter, the neutralization treatment and the water washing treatment which are carried out in the purification step and the treatment, the water washing treatment, and the like used in the first production method of the present invention, and the reaction liquid after the esterification step in the second production method of the present invention will be described. .

3－1.中和處理 中和處理係以去除反應生成液中未反應(甲基)丙烯酸及有機磺酸觸媒等的酸性成分為目的而實施的，通常係使反應液與鹼性水溶液接觸而實施的。 3-1. Neutralization treatment The neutralization treatment is carried out for the purpose of removing acidic components such as unreacted (meth)acrylic acid and organic sulfonic acid catalyst in the reaction product liquid, usually by bringing the reaction solution into contact with an alkaline aqueous solution. And implemented.

中和處理係根據一般方法進行為佳，可舉例如於反應液中添加溶解鹼性成分之鹼性水溶液，並進行攪拌、混合之方法等。The neutralization treatment is preferably carried out according to a general method, and for example, a method in which an alkaline aqueous solution in which an alkaline component is dissolved is added to the reaction liquid, and the mixture is stirred and mixed is used.

上述鹼性成分係舉例如氫氧化鋰、氫氧化鈉及氫氧化鉀等的鹼性金屬鹽、以及氨等。鹼性成分係可單獨一種使用、或亦可任意組合二種以上使用為佳。此等之中，以氫氧化鈉因為效果優異、便宜且容易取得而為佳。The alkaline component is, for example, an alkali metal salt such as lithium hydroxide, sodium hydroxide or potassium hydroxide, or ammonia. The alkaline component may be used singly or in combination of two or more. Among these, sodium hydroxide is preferred because it is excellent in effect, inexpensive, and easy to obtain.

該情形、鹼性成分的量係相對於反應液的酸成分，以莫耳比1倍以上為佳、更佳係1.1~2.0倍。鹼性成分的添加量係相對於反應液的酸成分為莫耳比1倍以上時，因為酸成分的中和係能充分地進行而為佳。In this case, the amount of the alkaline component is preferably 1 time or more, more preferably 1.1 to 2.0 times the molar ratio of the acid component of the reaction liquid. When the amount of the alkaline component added is 1 or more times the molar ratio of the acid component of the reaction liquid, the neutralization system of the acid component can be sufficiently carried out.

又，鹼性水溶液的濃度係以1~25重量%為佳、更佳係10~25重量%。鹼性水溶液的濃度為1重量%以上時，由於能減少中和處理後的排水量而為佳。又，鹼性水溶液的濃度為25重量%以下時，因為沒有聚合(甲基)丙烯酸酯而為佳。Further, the concentration of the alkaline aqueous solution is preferably 1 to 25% by weight, more preferably 10 to 25% by weight. When the concentration of the alkaline aqueous solution is 1% by weight or more, it is preferred to reduce the amount of water discharged after the neutralization treatment. Further, when the concentration of the alkaline aqueous solution is 25% by weight or less, it is preferred that the (meth) acrylate is not polymerized.

鹼性水溶液添加時的攪拌、混合時間係根據反應液的量、其所含有酸成分的量及目的等而做適當設定為佳，以5分~120分左右為佳。The stirring and mixing time in the case where the alkaline aqueous solution is added is preferably set appropriately in accordance with the amount of the reaction liquid, the amount and the purpose of the acid component contained therein, and is preferably about 5 minutes to 120 minutes.

3－2.水洗處理 在本發明，對於上述酯化反應液(酯化步驟後的反應液)或中和處理液(酯化步驟後，進一步進行中和處理之反應液)進行水洗處理。水洗處理係在那個時點進行係可根據所使用之成分及目的而做適當選擇。 3-2. Water washing treatment In the present invention, the esterification reaction liquid (reaction liquid after the esterification step) or the neutralization treatment liquid (reaction liquid further subjected to neutralization treatment after the esterification step) is subjected to a water washing treatment. The washing treatment is carried out at that point in time and can be appropriately selected depending on the ingredients and purposes used.

水洗處理係根據一般方法進行為佳。具體而言，可舉例如對於上述酯化反應中所得之酯化反應液或上述中和處理液添加水或無機水溶液，並加以攪拌、混合之方法等。The washing treatment is preferably carried out according to a general method. Specifically, for example, a method in which water or an inorganic aqueous solution is added to the esterification reaction liquid or the neutralization treatment liquid obtained in the above esterification reaction, and the mixture is stirred and mixed.

在水洗步驟中通常係使用水。另一方面，在要求改善與有機層的分離、及高純度的製品之情形中，以使用含有無機鹽之水溶液為佳，具體而言可舉例如硫酸銨水溶液及氯化銨水溶液等的銨鹽水溶液、氯化鈉等的鈉鹽水溶液、以及鹽酸水溶液等的酸性水。Water is usually used in the water washing step. On the other hand, in the case where it is desired to improve the separation from the organic layer and the high-purity product, it is preferred to use an aqueous solution containing an inorganic salt, and specific examples thereof include an ammonium sulfate aqueous solution and an ammonium chloride aqueous solution. An acidic solution of an aqueous solution such as a sodium salt such as an aqueous solution or sodium chloride or an aqueous solution of hydrochloric acid.

3－3.其他 在上述中和處理及/或水洗處理中必要時可進行加熱。 3-3. Others Heating may be performed as necessary in the above neutralization treatment and/or water washing treatment.

加熱溫度係舉例如30~80℃，加熱時間則舉例如5分~5小時。The heating temperature is, for example, 30 to 80 ° C, and the heating time is, for example, 5 minutes to 5 hours.

在上述中和處理及/或水洗處理所使用的水係以使用蒸餾水為佳。It is preferred to use distilled water for the water used in the above neutralization treatment and/or water washing treatment.

在進行加熱之情形中，其目的為了防止(甲基)丙烯醯基之聚合的，以使用聚合抑制劑為佳、再者亦可將含氧氣體導入至反應液內。In the case of heating, in order to prevent polymerization of the (meth) acrylonitrile group, it is preferred to use a polymerization inhibitor, and an oxygen-containing gas may be introduced into the reaction liquid.

聚合抑制劑係可舉例如與上述相同者、其比例係亦可舉例如與上述相同的比例。The polymerization inhibitor may, for example, be the same as the above, and the ratio thereof may be, for example, the same ratio as described above.

含氧氣體係可舉例如與上述相同者。The oxygen-containing system may, for example, be the same as described above.

在本發明的第1(甲基)丙烯酸酯之製法中，中和．水洗的處理液含有有機溶媒時係進行脫溶劑步驟。In the preparation method of the first (meth) acrylate of the present invention, neutralization. When the water-washing treatment liquid contains an organic solvent, a solvent removal step is performed.

說明脫溶劑步驟時，將中和處理液或水洗處理液移至脫溶劑槽內，利用中和處理或水洗處理以使得水層分離之後有機層中有機溶劑被去除。In the desolvation step, the neutralization treatment liquid or the water treatment treatment liquid is transferred to a desolvation tank, and the organic solvent in the organic layer is removed by a neutralization treatment or a water washing treatment to separate the aqueous layer.

脫溶劑處理係可根據一般方法，可舉例如於減壓下加熱脫溶劑槽以去除有機溶劑之方法等。The solvent removal treatment can be carried out, for example, according to a general method, for example, a method of heating a desolvation tank under reduced pressure to remove an organic solvent.

脫溶劑槽的減壓度係根據所使用之原料及目的而做適當設定為佳，較佳為0.5~50kPa，根據有機溶劑的去除程度而緩緩增加減壓度之方法為佳。The degree of pressure reduction of the desolvation tank is preferably set to be appropriately set depending on the raw materials and purpose to be used, and is preferably 0.5 to 50 kPa, and it is preferred to gradually increase the degree of pressure reduction depending on the degree of removal of the organic solvent.

加熱溫度係根據所得(甲基)丙烯酸酯、減壓度及目的而做適當設定為佳，惟以40~100℃為佳、更佳係60~80℃。為了抑制(甲基)丙烯酸酯的熱聚合，溫度係為持在80℃以下為佳。The heating temperature is preferably set in accordance with the obtained (meth) acrylate, the degree of pressure reduction, and the purpose, and is preferably 40 to 100 ° C, more preferably 60 to 80 ° C. In order to suppress thermal polymerization of (meth) acrylate, the temperature is preferably 80 ° C or lower.

在脫溶劑步驟中，為了抑制(甲基)丙烯酸酯的熱聚合，以提供氧、及添加聚合抑制劑為佳。聚合抑制劑係可舉例如與上述相同者、其比例係亦可舉例如與上述相同的比例。In the solvent removal step, in order to suppress thermal polymerization of (meth) acrylate, it is preferred to provide oxygen and to add a polymerization inhibitor. The polymerization inhibitor may, for example, be the same as the above, and the ratio thereof may be, for example, the same ratio as described above.

在進一步要求所構成製品的品質時，在脫溶劑步驟之後可更進行過濾。When the quality of the formed product is further required, filtration can be further performed after the solvent removal step.

該過濾步驟係可根據一般方法。This filtration step can be according to a general method.

4.處理劑添加步驟4. Treatment agent addition step

本發明的第2(甲基)丙烯酸酯之製法係包含：對於進行上述酯化步驟、中和處理、水洗處理所得之(甲基)丙烯酸酯，在含有1ppm以上的上述式(1)所示之化合物A的有機反應液中，添加選自於4級銨鹽、4級鎏鹽、脒、具有1級胺基及/或2級胺基之化合物、胺基脲以及吡啶所構成族群之至少1種特定處理劑(以下，亦有僅稱為處理劑)之添加步驟(處理劑添加步驟)。The method for producing a second (meth) acrylate according to the present invention is characterized in that the (meth) acrylate obtained by performing the esterification step, the neutralization treatment, and the water washing treatment is contained in the formula (1) containing 1 ppm or more. In the organic reaction solution of the compound A, at least a group selected from the group consisting of a grade 4 ammonium salt, a grade 4 onium salt, a phosphonium, a compound having a primary amine group and/or a secondary amine group, an amine urea, and a pyridine is added. The addition step (treatment agent addition step) of one specific treatment agent (hereinafter, also referred to as a treatment agent).

此等處理劑係可添加1種、亦可併用2種以上來使用。These treatment agents may be used alone or in combination of two or more.

以下，說明各個的處理劑。Hereinafter, each treatment agent will be described.

4－1. 4級銨鹽 4級銨鹽係可使用各種的化合物，較佳係舉例如下述式(3)所示之化合物(以下，稱為化合物3)。 4-1. The fourth-order ammonium salt 4-grade ammonium salt-based compound can be used, and a compound represented by the following formula (3) (hereinafter referred to as compound 3) is preferably used.

〔此外，在式(3)中，R¹ ~R³ 表示烷基，R⁴ 表示烷基或苄基，X^－ 表示無機陰離子〕 [ Further, in the formula (3), R ¹ to R ³ represent an alkyl group, R ⁴ represents an alkyl group or a benzyl group, and X ^- represents an inorganic anion]

在上述式(3)之R¹ ~R⁴ 中，烷基係可為直鏈狀者、亦可為分枝狀者為佳，惟以直鏈狀者為佳。又，碳數8以下的烷基為佳。In the case of R ¹ to R ⁴ in the above formula (3), the alkyl group may be a linear one or may be a branched form, and a linear one is preferred. Further, an alkyl group having 8 or less carbon atoms is preferred.

在上述式(3)之X^－ 中的無機陰離子係舉例如鹵素化物離子、氫氧化物離子及硫酸氫離子等。此等之中，尤以鹵素化物離子及氫氧化物離子為佳，鹵素化物離子係以氯離子及溴離子為較佳。The inorganic anion in X ^- in the above formula (3) is, for example, a halide ion, a hydroxide ion, a hydrogen sulfate ion or the like. Among these, a halide ion and a hydroxide ion are preferable, and a halide ion is preferably a chloride ion or a bromide ion.

化合物3的具體例係舉例如下述(1)及(2)之例。Specific examples of the compound 3 are, for example, the following examples (1) and (2).

(1)具有R¹ ~R⁴ 為烷基的化合物之例氯化四甲基銨、溴化四甲基銨、氫氧化四甲基銨、氯化四正丁基銨、溴化四正丁基銨、氫氧化四正丁基銨及硫酸氫四丁基銨等。(1) Examples of a compound having R ¹ to R ⁴ as an alkyl group, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, tetra-n-butylammonium chloride, tetra-n-butyl bromide Alkyl ammonium, tetra-n-butylammonium hydroxide, and tetrabutylammonium hydrogen sulfate.

(2)具有R¹ ~R³ 為烷基且R⁴ 為苄基的化合物之例氯化苄基三甲基銨、氯化苄基三乙基銨及氯化苄基三正丁基銨等。(2) Examples of a compound having R ¹ to R ³ as an alkyl group and R ⁴ being a benzyl group, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltri-n-butylammonium chloride, etc. .

4－2. 4級鏻鹽 4級鏻鹽係可使用各種的化合物，較佳係舉例如下述式(4)所示之化合物(以下，稱為化合物4)。 4-2. The fourth-stage sulfonium salt -grade sulfonium salt-based salt may be a compound of any kind, and a compound represented by the following formula (4) (hereinafter referred to as compound 4) is preferably used.

〔此外，在式(4)中，R¹ ~R³ 表示烷基，R⁴ 表示烷基或苄基，X^－ 表示無機陰離子〕 [ Further, in the formula (4), R ¹ to R ³ represent an alkyl group, R ⁴ represents an alkyl group or a benzyl group, and X ^- represents an inorganic anion]

在上述式(4)之R¹ ~R⁴ 中，烷基係可為直鏈狀者、亦可為分枝狀者，以直鏈狀者為佳。又，碳數8以下的烷基為佳。In the case of R ¹ to R ⁴ in the above formula (4), the alkyl group may be a linear one or a branched one, and a linear one is preferred. Further, an alkyl group having 8 or less carbon atoms is preferred.

在上述式(4)之X^－ 中的無機陰離子係舉例如鹵素化物離子、氫氧化物離子及硫酸氫離子等。此等之中，尤以鹵素化物離子及氫氧化物離子為佳，鹵素化物離子係以氯離子及溴離子為較佳。The inorganic anion in X ^- in the above formula (4) is, for example, a halide ion, a hydroxide ion, a hydrogen sulfate ion or the like. Among these, a halide ion and a hydroxide ion are preferable, and a halide ion is preferably a chloride ion or a bromide ion.

化合物4的具體例係舉例如氯化苄基-三正丁基鏻及溴化四正丁基鏻等。Specific examples of the compound 4 include, for example, benzyl-tri-n-butylphosphonium chloride and tetra-n-butylphosphonium bromide.

4-3.脒4-3.脒

脒只要為具有脒骨架之化合物，可使用各種的化合物。具體而言，舉例如1,8-二氮雜雙環(5.4.0)十一-7-烯(diazabicyclo[5.4.0]undec-7-ene；DBU)及1,5-二氮雜雙環(4.3.0)壬-5-烯(diazabicyclo[4.3.0]non-5-ene；DBN)等。As long as it is a compound having an anthracene skeleton, various compounds can be used. Specifically, for example, 1,8-diazabicyclo (5.4.0) undec-7-ene (diazabicyclo [5.4.0] undec-7-ene; DBU) and 1,5-diazabicyclo ( 4.3.0) 壬-5-ene (diazabicyclo [4.3.0] non-5-ene; DBN) and the like.

4-4.具有1級胺基及/或2級胺基之化合物4-4. Compounds having a grade 1 amine group and/or a grade 2 amine group

具有1級胺基及/或2級胺基之化合物(以下，稱為胺系化合物)係舉例如：具有1級胺基之化合物(以下，稱為1級胺)、具有2級胺基之化合物(以下，稱為2級胺)及具有1級胺基及2級胺基之化合物(以下，稱為1-2級胺)等。A compound having a primary amine group and/or a secondary amine group (hereinafter referred to as an amine compound) is, for example, a compound having a primary amine group (hereinafter referred to as a primary amine) and having a secondary amine group. A compound (hereinafter referred to as a secondary amine) and a compound having a primary amine group and a secondary amine group (hereinafter referred to as a 1-2 amine).

胺系化合物係可使用各種的化合物，可列舉如下述之例。As the amine compound, various compounds can be used, and examples thereof are as follows.

1級胺係舉例如：甲基胺、乙基胺、丙基胺、丁基胺、2-乙基己基胺及十六烷基胺等的烷基胺；1,6-己烷二胺等的烷基二胺；3-甲氧基丙基胺、3-乙氧基丙基胺及3-(2-乙基己基氧基)丙基胺等的烷氧基烷基胺；3-(二甲基胺)丙基胺、3-(二乙基胺)丙基胺及3-(二丁基胺)丙基胺等的(二烷基胺)烷基胺；羥基乙基胺及羥基丙基胺等的羥基烷基胺；N-甲基-3,3’-亞胺雙(丙基胺)等的N-烷基-亞胺雙(烷基胺)；以及烯丙基胺等。The amine of the first order is, for example, an alkylamine such as methylamine, ethylamine, propylamine, butylamine, 2-ethylhexylamine or hexadecylamine; 1,6-hexanediamine, etc. Alkyldiamine; alkoxyalkylamine such as 3-methoxypropylamine, 3-ethoxypropylamine and 3-(2-ethylhexyloxy)propylamine; 3-( (Dialkylamine)alkylamines such as dimethylamine) propylamine, 3-(diethylamine)propylamine and 3-(dibutylamine)propylamine; hydroxyethylamine and hydroxyl group a hydroxyalkylamine such as propylamine; an N-alkyl-imine bis(alkylamine) such as N-methyl-3,3'-imide bis(propylamine); and an allylamine .

此等之中，在具有烷基之化合物係以分枝狀的烷基為佳。Among these, a compound having an alkyl group is preferably a branched alkyl group.

還有，上述化合物之中，(二烷基胺)烷基胺及N－烷基－亞胺雙(烷基胺)係具有3級胺基者，因為具有1級胺基而能表現出本發明的效果。Further, among the above compounds, a (dialkylamine)alkylamine and an N-alkyl-iminebis(alkylamine) have a tertiary amino group, and since they have a primary amine group, they can exhibit The effect of the invention.

2級胺係可使用各種的化合物，舉例如二甲基胺、二乙基胺、二丙基胺、二丁基胺及二－2－乙基己基胺等的二烷基胺；二－2－乙氧基丙基胺及二－3－(2－乙基己基)丙基胺等的二烷氧基烷基胺等；以及二烯丙基胺等。As the secondary amine, various compounds can be used, for example, a dialkylamine such as dimethylamine, diethylamine, dipropylamine, dibutylamine or di-2-ethylhexylamine; a dialkoxyalkylamine such as ethoxypropylamine or di-3-(2-ethylhexyl)propylamine; and a diallylamine.

此等之中，在具有烷基之化合物中，以分枝狀的烷基為佳。Among these, among the compounds having an alkyl group, a branched alkyl group is preferred.

1－2級胺係舉例如3,3’－亞胺雙(丙基)胺及6,6’－亞胺雙(己基)胺等的亞胺雙(烷基)胺、以及3－(甲基胺)丙基胺等的(烷基胺)烷基胺等。The 1-2 amines are, for example, imine bis(alkyl)amines such as 3,3'-imine bis(propyl)amine and 6,6'-imide bis(hexyl)amine, and 3-(A) (Alkylamine) alkylamine or the like such as propylamine.

本發明的胺系化合物係必要時亦可以無機鹽的形態來使用。具體而言，舉例如上述化合物的鹽酸鹽及硫酸鹽等。The amine compound of the present invention can also be used in the form of an inorganic salt if necessary. Specific examples thereof include hydrochlorides and sulfates of the above compounds.

但是，胺系化合物係為非無機鹽形態之化合物者因為本發明的效果優異而為佳。However, the amine compound is preferably a compound having a non-inorganic salt form, and is excellent in the effect of the present invention.

胺系化合物係在此等之中，尤其是在脫溶劑步驟中，從處理劑難以蒸發時的理由，沸點為200℃以上的化合物為佳，在0.5kPa的沸點為60℃以上、300℃以下之化合物為佳。Among the above-mentioned amine-based compounds, in particular, in the solvent removal step, a compound having a boiling point of 200 ° C or higher is preferred because the treatment agent is difficult to evaporate, and a boiling point of 0.5 kPa is 60° C. or higher and 300° C. or lower. The compound is preferred.

具體而言，舉例如6,6’－亞胺雙(己基)胺、1,6－己烷二胺、十六烷基胺等。Specifically, for example, 6,6'-imine bis(hexyl)amine, 1,6-hexanediamine, hexadecylamine or the like can be mentioned.

4－5.胺基脲 胺基脲係至少具有1個胺基脲基之化合物。 4-5. Aminourea Aminourea is a compound having at least one aminoureido group.

可用於本發明之胺基脲係以下述式(5)所示之化合物為佳。The amine-based urea which can be used in the present invention is preferably a compound represented by the following formula (5).

式(5)中、R¹ 及R² 係表示1價的有機基，分別相同或不同均可。又，R¹ 及R² 係以取代或無取代的烷基或苯基為佳。具體而言，可例示如甲基、乙基、丙基、異丙基、硬脂醯基、苄基、及、羥基乙基等。此等之中，尤以碳數1~4的低級烷基為較佳。In the formula (5), R ¹ and R ^{2 each} represent a monovalent organic group, and may be the same or different. Further, R ¹ and R ² are preferably a substituted or unsubstituted alkyl group or a phenyl group. Specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a stearyl group, a benzyl group, a hydroxyethyl group or the like can be exemplified. Among these, a lower alkyl group having 1 to 4 carbon atoms is particularly preferred.

式(5)中、R³ 及R⁴ 係分別獨立地表示氫原子或1價的有機基，以氫原子為佳。In the formula (5), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group, and a hydrogen atom is preferred.

式(5)中、A表示氫原子或n價的有機基。A係n價的有機基為佳、2價或3價的有機基為較佳。In the formula (5), A represents a hydrogen atom or an n-valent organic group. The N-valent organic group of the A-based is preferably a divalent or trivalent organic group.

式(5)中、n為1以上的整數、1~3的整數為佳、2或3為較佳。In the formula (5), n is an integer of 1 or more, an integer of 1 to 3 is preferable, and 2 or 3 is preferable.

上述n價的有機基係沒有特別地限制，以由氫原子、碳原子、氮原子及/或氧原子所構成之基為佳，脂肪族基或脂環族基為較佳。The n-valent organic group is not particularly limited, and is preferably a group consisting of a hydrogen atom, a carbon atom, a nitrogen atom and/or an oxygen atom, and an aliphatic group or an alicyclic group is preferred.

胺基脲係可添加1種、亦可併用2種以上來使用。The amine-urea system may be used alone or in combination of two or more.

胺基脲係可使用各種的化合物，可舉例如藉由使異氰酸酯化合物與N,N－二取代肼進行反應所得之化合物。As the aminourea, various compounds can be used, and for example, a compound obtained by reacting an isocyanate compound with N,N-disubstituted anthracene can be mentioned.

異氰酸酯化合物係以二異氰酸酯化合物為佳，可例示例如1,4－四亞甲基二異氰酸酯、1,5－五亞甲基二異氰酸酯、1,6－六亞甲基二異氰酸酯、2,2,4(或2,4,4)－三甲基－1,6－六亞甲基二異氰酸酯、賴胺酸二異氰酸酯、異佛酮二異氰酸酯、1,3－雙(異氰酸酯甲基)－環己烷、4,4’－二環己基甲烷二異氰酸酯、苯二甲基二異氰酸酯及四甲基甲苯二異氰酸酯等的脂肪族或脂環族二異氰酸酯；4,4’－二苯基甲烷二異氰酸酯、1,4－伸苯基二異氰酸酯、2,4－甲伸苯基二異氰酸酯及萘二異氰酸酯等的芳香族二異氰酸酯。又，可舉例如由此等二異氰酸酯所誘導之聚異氰酸酯；以及正丁基異氰酸酯、正己基異氰酸酯、正辛基異氰酸酯及苯基異氰酸酯等的單異氰酸酯等。The isocyanate compound is preferably a diisocyanate compound, and examples thereof include, for example, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2, 2, 4 (or 2,4,4)-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanate methyl)-cyclohexane An aliphatic or alicyclic diisocyanate such as alkane, 4,4'-dicyclohexylmethane diisocyanate, benzodimethyl diisocyanate or tetramethyltoluene diisocyanate; 4,4'-diphenylmethane diisocyanate, An aromatic diisocyanate such as 1,4-phenylene diisocyanate, 2,4-methylphenylene diisocyanate or naphthalene diisocyanate. Further, for example, a polyisocyanate induced by such a diisocyanate; a monoisocyanate such as n-butyl isocyanate, n-hexyl isocyanate, n-octyl isocyanate or phenyl isocyanate; and the like may be mentioned.

此等異氰酸酯化合物之中，以脂肪族或脂環族二異氰酸酯、及由其所誘導之聚異氰酸酯為佳。此等異氰酸酯化合物係亦可併用2種以上。Among these isocyanate compounds, an aliphatic or alicyclic diisocyanate and a polyisocyanate induced therefrom are preferred. These isocyanate compounds may be used in combination of two or more kinds.

N,N－二取代肼係舉例如N,N－二甲基肼、N,N－二乙基肼、N,N－二丙基肼、N,N－二異丙基肼、N,N－二硬脂醯肼、N－甲基－N－乙基肼、N－甲基－N－異丙基肼、N－甲基－N－苄基肼及N,N－二(β－羥基乙基)－肼等。N,N-disubstituted fluorene systems such as N,N-dimethylhydrazine, N,N-diethylanthracene, N,N-dipropylanthracene, N,N-diisopropylhydrazine, N,N - distearyl, N-methyl-N-ethyl hydrazine, N-methyl-N-isopropyl hydrazine, N-methyl-N-benzyl hydrazine and N,N-di(β-hydroxyl Ethyl)-肼 and the like.

異氰酸酯化合物與N,N－二取代肼的反應係無論溶劑的有無與否均可進行。在使用溶劑之情形中，對於異氰酸酯係必須使用惰性溶劑。The reaction between the isocyanate compound and the N,N-disubstituted fluorene can be carried out regardless of the presence or absence of the solvent. In the case of using a solvent, an inert solvent must be used for the isocyanate system.

反應係在－20~150℃下進行為佳、更佳係0~100℃。The reaction system is preferably carried out at -20 to 150 ° C, more preferably 0 to 100 ° C.

異氰酸酯與N,N－二取代肼係以大致當量使其反應為佳。The isocyanate and the N,N-disubstituted fluorene are preferably reacted in an approximate equivalent amount.

此等之中，尤以從酸價上昇抑制機能優異、容易取得之點，在上述式(5)中的R¹ 及R² 係以碳數1~4的低級烷基、R³ 及R⁴ 為具有氫原子之胺基脲基的胺基脲為佳。再者除了此等優點之外，在後述的脫溶劑步驟中，從處理劑難以蒸發時的理由而言，在上述式(5)中的R¹ 及R² 為碳數1~4的低級烷基，R³ 及R⁴ 為具有氫原子之胺基脲基，且分子量為200以上的化合物為較佳。Among these, R ¹ and R ² in the above formula (5) are preferably a lower alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ , in which the acid value increase suppression function is excellent and easy to obtain. Aminourea which is an aminoureido group having a hydrogen atom is preferred. In addition, in the solvent removal step which will be described later, in the case where the treatment agent is difficult to evaporate, R ¹ and R ² in the above formula (5) are lower alkylene having 1 to 4 carbon atoms. The compound wherein R ³ and R ⁴ are an aminoureido group having a hydrogen atom and has a molecular weight of 200 or more is preferred.

當該化合物係以1,4－四亞甲基雙－N,N－二甲基胺基脲、1,6－六亞甲基雙－N,N－二甲基胺基脲、1,1,1’,1’－四甲基－4,4’－(亞甲基二－p－伸苯基)二胺基脲及下述化合物等為佳。When the compound is 1,4-tetramethylene bis-N,N-dimethylamino urea, 1,6-hexamethylene bis-N,N-dimethylamino urea, 1,1 Further, 1',1'-tetramethyl-4,4'-(methylenebis-p-phenylene)diamine urea, and the like, and the like are preferred.

4－6.吡啶化合物 吡啶化合物只要是具有吡啶環之化合物，可使用各種的化合物。具體而言，以鹼性化合物為佳，可舉例如吡啶、甲基吡啶、乙基吡啶、丙基吡啶、丁基吡啶、4－(1－丁基戊基)吡啶、二甲基吡啶、三甲基吡啶、三乙基吡啶、苯基吡啶、胺吡啶、2－二甲基胺吡啶及4－二甲基胺吡啶等。 4-6. Pyridine compound The pyridine compound may be any compound as long as it is a compound having a pyridine ring. Specifically, a basic compound is preferred, and examples thereof include pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, lutidine, and the like. Methylpyridine, triethylpyridine, phenylpyridine, amine pyridine, 2-dimethylamine pyridine, 4-dimethylamine pyridine, and the like.

此等之中，尤以吡啶化合物為胺吡啶化合物為佳、2－二甲基胺吡啶或4－二甲基胺吡啶為較佳。Among these, a pyridine compound is preferred as the amine pyridine compound, and 2-dimethylaminopyridine or 4-dimethylamine pyridine is preferred.

4－7較佳的特定處理劑 在本發明的第2(甲基)丙烯酸酯之製法中，係使用選自於由4級銨鹽、4級鏻鹽、脒、具有1級胺基及/或2級胺基之化合物、胺基脲以及吡啶所構成族群之至少1種特定處理劑。此等之中，以4級銨鹽、4級鏻鹽、脒及胺基脲為佳、胺基脲為較佳。藉由使用胺基脲，因為對於所得(甲基)丙烯酸酯係除了酸價上昇抑制效果以外，還可賦予著色防止效果而為佳。 4-7 Preferred specific treatment agent is used in the preparation method of the second (meth) acrylate of the present invention, which is selected from the group consisting of a grade 4 ammonium salt, a grade 4 onium salt, a ruthenium, a grade 1 amine group and/or Or at least one specific treatment agent of a group consisting of a compound of a 2-stage amine group, an amine urea, and a pyridine. Among these, a 4-grade ammonium salt, a 4-grade phosphonium salt, an anthracene and an amine urea are preferred, and an amine urea is preferred. In addition to the effect of suppressing the increase in the acid value, the obtained (meth) acrylate is preferably used to impart a coloring preventing effect.

4－8.處理劑的添加方法 上述特定處理劑的添加時期只要為經歷中和處理及水洗處理後所得之反應液的話可為任意時期，具體而言，可舉例如在脫溶劑步驟的前．後進行過濾之情形中，係在過濾步驟的前．後，以及最終製品之時期。 4-8. Method of Adding Treatment Agent The addition period of the specific treatment agent may be any period as long as it is a reaction liquid obtained after the neutralization treatment and the water washing treatment, and specifically, for example, before the solvent removal step. In the case of post-filtration, it is before the filtration step. After, and the period of the final product.

此等之中，尤以在脫溶劑步驟之前添加特定處理劑之方法為佳。根據該方法，可合併脫溶劑步驟與特定處理劑的添加步驟且以1步驟來進行，由於可省略特定處理劑的添加步驟而為佳。Among these, a method of adding a specific treating agent before the solvent removal step is particularly preferred. According to this method, the addition step of the desolvation step and the specific treatment agent can be combined and carried out in one step, since the addition step of the specific treatment agent can be omitted.

上述處理劑的添加方法係舉例如以一邊攪拌．混合且一邊添加至(甲基)丙烯酸酯之方法等。The method of adding the above treatment agent is, for example, stirring at one side. A method of mixing and adding to a (meth) acrylate, etc.

上述特定處理劑的添加比例係相對於(甲基)丙烯酸酯，以2~10,000wtppm為佳、5~3,000wtppm為較佳、50~1,000wtppm為較佳。該值為2wtppm以上時，可有效地發揮特定處理劑的效果，另一方面，為10,000wtppm以下時，因為對於所得(甲基)丙烯酸酯之溶解性優異，且作為組成物使用時與其他成分的相溶性亦為優異之故而為佳。The specific treatment agent is preferably added in an amount of 2 to 10,000 wtppm, more preferably 5 to 3,000 wtppm, more preferably 50 to 1,000 wtppm, based on the (meth) acrylate. When the value is 2 wtppm or more, the effect of the specific treatment agent can be effectively exhibited. On the other hand, when it is 10,000 wtppm or less, the solubility in the obtained (meth) acrylate is excellent, and when it is used as a composition, it is combined with other components. The compatibility is also excellent for the sake of excellence.

在該處理劑的添加中，可在常溫下進行，必要時可進行加熱。In the addition of the treating agent, it can be carried out at normal temperature, and if necessary, heating can be carried out.

特別是，使用多元醇作為醇之情形中進行加熱為佳。其係因為在使用多元醇作為醇之情形中，所得之(甲基)丙烯酸酯係形成高黏度物，且藉由加熱可以短時間均勻地摻混處理劑。In particular, it is preferred to carry out heating in the case where a polyol is used as the alcohol. This is because in the case where a polyol is used as the alcohol, the obtained (meth) acrylate forms a high viscosity, and the treatment agent can be uniformly blended in a short time by heating.

加熱溫度及加熱時間可根據所得(甲基)丙烯酸酯及目的做適當設定為佳，加熱溫度係以30~100℃為佳、更佳係30~80℃，加熱時間係以5分~5小時為佳、更佳係30分~3小時。The heating temperature and heating time can be appropriately set according to the obtained (meth) acrylate and the purpose, and the heating temperature is preferably 30 to 100 ° C, more preferably 30 to 80 ° C, and the heating time is 5 minutes to 5 hours. Better, better, 30 minutes to 3 hours.

在進行加熱之情形中，其目的為了防止(甲基)丙烯醯基的聚合，以使用聚合抑制劑為佳，再者亦可將含氧氣體倒入至反應液內。In the case of heating, it is preferable to use a polymerization inhibitor in order to prevent polymerization of a (meth) acrylonitrile group, and it is also possible to pour an oxygen-containing gas into the reaction liquid.

聚合抑制劑係可舉例如與上述相同者，其比例係亦可舉例如與上述相同的比例。The polymerization inhibitor may, for example, be the same as the above, and the ratio thereof may be, for example, the same ratio as described above.

含氧氣體係可舉例如與上述相同者。The oxygen-containing system may, for example, be the same as described above.

5.脫溶媒步驟 中和．水洗的處理液含有有機溶媒時係進行脫溶媒步驟。此時，有機溶媒係可為酯化步驟中所使用之有機溶媒、亦可為在之後的中和處理及/或水洗處理中所添加者。 5. Desolvent step Neutralization . When the water-washed treatment liquid contains an organic solvent, the solvent removal step is carried out. In this case, the organic solvent may be an organic solvent used in the esterification step, or may be added in a subsequent neutralization treatment and/or water washing treatment.

說明脫溶媒步驟時，將中和處理液或水洗處理液移至脫溶媒槽內，利用中和處理或水洗處理以去除水層分離之後有機層中的有機溶媒。When the solvent removal step is described, the neutralization treatment liquid or the water treatment treatment liquid is transferred to the desolvation medium tank, and the organic solvent in the organic layer after the aqueous layer separation is removed by a neutralization treatment or a water washing treatment.

脫溶媒處理係可根據一般方法，可舉例如在減壓下加熱脫溶媒槽以去除有機溶媒之方法等。The solvent treatment can be carried out according to a general method, for example, a method in which a solvent solvent is heated under reduced pressure to remove an organic solvent.

脫溶媒槽的減壓度係根據所使用之原料及目的做適當設定為佳，較佳為0.5~50kPa，且根據有機溶媒的去除程度而緩緩增加減壓度之方法為佳。The degree of decompression of the desolvation tank is preferably set to be appropriately set depending on the raw materials and purpose to be used, and is preferably 0.5 to 50 kPa, and a method of gradually increasing the degree of pressure reduction depending on the degree of removal of the organic solvent is preferred.

加熱溫度可根據所得(甲基)丙烯酸酯、減壓度及目的做適當設定為佳，以40~100℃為佳、更佳係60~80℃。為了抑制(甲基)丙烯酸酯的熱聚合，將溫度維持在80℃以下為佳。The heating temperature can be appropriately set according to the obtained (meth) acrylate, the degree of pressure reduction, and the purpose, preferably 40 to 100 ° C, more preferably 60 to 80 ° C. In order to suppress thermal polymerization of (meth) acrylate, it is preferred to maintain the temperature at 80 ° C or lower.

在脫溶劑步驟中，為了抑制(甲基)丙烯酸酯的熱聚合，以供給氧、及添加聚合抑制劑為佳。聚合抑制劑係可舉例如與上述相同者、其比例係亦可舉例如與上述相同的比例。In the solvent removal step, in order to suppress thermal polymerization of (meth) acrylate, it is preferred to supply oxygen and to add a polymerization inhibitor. The polymerization inhibitor may, for example, be the same as the above, and the ratio thereof may be, for example, the same ratio as described above.

進一步要求所構成製品品質之情形中，可在脫溶劑步驟之後更進行過濾。In the case where the quality of the constituent product is further required, filtration may be further performed after the solvent removal step.

該過濾步驟係可根據一般方法，以進行加壓過濾為佳。The filtration step is preferably carried out according to a general method for performing pressure filtration.

加壓過濾的方法係舉例如在設置濾紙之過濾機中投入脫溶劑後的反應液，並一邊對過濾機內施加壓力、一邊進行過濾之方法。在該情形中，於脫溶劑後的反應液添加過濾助劑之方法、在過濾紙表面預塗布過濾助劑之方法、及併用此等之方法，從可提昇使過濾效率而言為佳。加壓中所使用之氣體係舉例如氮、含氧氣體(氧5容量%、氮95容量%)及空氣等。The method of the pressure filtration is, for example, a method in which a reaction liquid after desolvation is introduced into a filter provided with a filter paper, and while applying pressure to the inside of the filter. In this case, the method of adding a filter aid to the reaction liquid after the solvent removal, the method of precoating the filter aid on the surface of the filter paper, and the like are preferably used to improve the filtration efficiency. The gas system used for pressurization is, for example, nitrogen, an oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%), air, and the like.

6.組成物6. Composition

藉由本發明之製法所得的(甲基)丙烯酸酯係可使得得到的(甲基)丙烯酸酯之貯藏安定性及熱安定性向上提昇。為此，所得之(甲基)丙烯酸酯係適合作為活性能量線硬化型組成物的摻混成分，以使用於光學透鏡、印刷油墨、塗布劑及接著劑等的各種工業用途。The (meth) acrylate obtained by the process of the present invention can improve the storage stability and thermal stability of the obtained (meth) acrylate. Therefore, the obtained (meth) acrylate is suitable as a blending component of an active energy ray-curable composition, and is used in various industrial applications such as an optical lens, a printing ink, a coating agent, and an adhesive.

本發明的第3發明係關於一種(甲基)丙烯酸酯系組成物，其係含有具有使(甲基)丙烯酸與具有氧化烯基之醇在酸觸媒的存在下經脫水酯化反應所得氧化烯基的(甲基)丙烯酸酯之組成物，其係含有0ppm以上、100ppm以下之化合物A的(甲基)丙烯酸酯系組成物。According to a third aspect of the invention, there is provided a (meth) acrylate-based composition comprising an oxidation obtained by subjecting an alcohol having an oxyalkylene group to an alcohol having an oxyalkylene group by a dehydration esterification reaction in the presence of an acid catalyst. The (meth) acrylate composition of the alkenyl (meth) acrylate is a (meth) acrylate type composition containing 0 ppm or more and 100 ppm or less of the compound A.

組成物中化合物A的比例超過100ppm時，組成物的貯藏安定性或熱安定性係變得不良。When the ratio of the compound A in the composition exceeds 100 ppm, the storage stability or thermal stability of the composition becomes poor.

化合物A的比例係以0ppm以上、80ppm以下為佳、較佳係0~50ppm、0~30ppm為更佳，無法檢測為最佳。The ratio of the compound A is preferably 0 ppm or more and 80 ppm or less, more preferably 0 to 50 ppm, and more preferably 0 to 30 ppm, and it is not preferable to be detected.

(甲基)丙烯酸酯系組成物較佳係可使用為活性能量線硬化型組成物。The (meth) acrylate-based composition is preferably used as an active energy ray-curable composition.

作為活性能量線硬化型組成物使用之情形中，可摻混光聚合開始劑、上述(甲基)丙烯酸酯以外之(甲基)丙烯酸酯〔其他(甲基)丙烯酸酯〕。以下，說明各成分的具體例。In the case of being used as an active energy ray-curable composition, a photopolymerization initiator or a (meth) acrylate (other (meth) acrylate) other than the above (meth) acrylate may be blended. Specific examples of the respective components will be described below.

其他(甲基)丙烯酸酯係舉例如具有1個(甲基)丙烯醯基之化合物〔以下稱為單(甲基)丙烯酸酯〕及具有2個以上(甲基)丙烯醯基之化合物〔以下稱為聚(甲基)丙烯酸酯〕等。The other (meth) acrylate is, for example, a compound having one (meth) acrylonitrile group (hereinafter referred to as mono(meth) acrylate) and a compound having two or more (meth) acryl oxime groups [below It is called poly(meth)acrylate].

單(甲基)丙烯酸酯係舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯及(甲基)丙烯酸丁酯等的(甲基)丙烯酸烷基酯；(甲基)丙烯酸2－羥基乙酯、(甲基)丙烯酸2－羥基丙酯及1,4－丁二醇單(甲基)丙烯酸酯等的(甲基)丙烯酸羥基烷酯；丙烯酸異冰片基酯等的脂環族單(甲基)丙烯酸酯等。此等以外，亦可舉例如(甲基)丙烯酸四氫糠基酯、卡必醇(甲基)丙烯酸酯、(甲基)丙烯醯基啉、順丁烯二醯亞胺(甲基)丙烯酸酯及縮水甘油(甲基)丙烯酸酯等。The mono(meth)acrylate is, for example, a (meth)acrylic acid alkyl ester such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate or butyl (meth)acrylate. a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 1,4-butanediol mono(meth)acrylate; An alicyclic mono(meth)acrylate such as isobornyl acrylate or the like. Other than this, for example, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, or (meth) acryl fluorenyl group Porphyrin, maleimide (meth) acrylate, glycidyl (meth) acrylate, and the like.

聚(甲基)丙烯酸酯係舉例如：季戊四醇二(甲基)丙烯酸酯一硬脂酸酯等的具有2個(甲基)丙烯醯基之(甲基)丙烯酸酯、以及季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯等的具有3個(甲基)丙烯醯基之(甲基)丙烯酸酯等。此等以外，亦可舉例如使用二季戊四醇六(甲基)丙烯酸酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯等的具有4個以上(甲基)丙烯醯基之(甲基)丙烯酸酯。The poly(meth)acrylate is, for example, a (meth) acrylate having two (meth) acrylonitrile groups such as pentaerythritol di(meth) acrylate monostearate, and pentaerythritol tris(methyl). A (meth) acrylate having three (meth) acrylonitrile groups such as acrylate or trimethylolpropane tri(meth)acrylate. In addition to these, for example, four or more (meth) acrylonitrile groups such as dipentaerythritol hexa(meth) acrylate or di(trimethylolpropane) tetra(meth) acrylate may be used. Base) acrylate.

又，亦可使用胺甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯及環氧(甲基)丙烯酸酯等的低聚合物。Further, a low polymer such as urethane (meth) acrylate, polyester (meth) acrylate or epoxy (meth) acrylate can also be used.

形成可見光線或紫外線硬化型組成物之情形係在組成物摻混光聚合開始劑。還有，形成電子線硬化型組成物之情形則不一定有摻混光聚合開始劑之必要。The case where a visible light ray or an ultraviolet curable composition is formed is a composition in which a photopolymerization initiator is blended. Further, in the case of forming an electron beam hardening type composition, it is not necessarily necessary to incorporate a photopolymerization initiator.

光聚合開始劑的具體例係舉例如苯偶因、苯偶因甲基醚及苯并異丙基醚等的苯偶因；乙醯苯、2,2－二甲氧基－2－苯基乙醯苯、2,2－二乙氧基－2－苯基乙醯苯、1,1－二氯乙醯苯、1－羥基環己基苯基酮、2－甲基－1－[4－(甲硫基)苯基]－2－啉代－丙－1－酮及N,N－二甲基胺乙醯苯等的乙醯苯；2－甲基蒽醌、1－氯蒽醌及2－戊基蒽醌等的蒽醌；2,4－二甲基噻噸酮、2,4－二乙基噻噸酮、2－氯噻噸酮及2,4－二異丙基噻噸酮等的噻噸酮；乙醯苯二甲基縮酮及苄基二甲基縮酮等的縮酮；二苯甲酮、甲基二苯甲酮、4,4’－二氯二苯甲酮、4,4’－雙二乙基胺二苯甲酮、米其勒酮及4－苯甲醯基－4’－甲基二苯基硫化物等的二苯甲酮；以及2,4,6－三甲基苯甲醯基二苯基氧化膦等。Specific examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, and benzoisopropyl ether; acetophenone, 2,2-dimethoxy-2-phenyl Acetylbenzene, 2,2-diethoxy-2-phenylethylbenzene, 1,1-dichloroethylbenzene, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4- (methylthio)phenyl]-2- Anthraquinone such as phenyl-propan-1-one and N,N-dimethylamine acetophenone; anthracene of 2-methylhydrazine, 1-chloroindole and 2-pentylhydrazine; Thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; a ketal such as methyl ketal and benzyl dimethyl ketal; benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethyl a benzophenone such as an amine benzophenone, a benzyl ketone or a 4-benzylidene-4'-methyldiphenyl sulfide; and a 2,4,6-trimethylbenzylidene group II Phenylphosphine oxide and the like.

光聚合開始劑中必要時可併用光增感劑。光增感劑係舉例如N,N－二甲基胺安息香酸乙基酯、N,N－二甲基胺安息香酸異戊基酯、三乙基胺及三乙醇胺等。A photo-sensitizer may be used in combination with the photopolymerization initiator. The photosensitizer is, for example, N,N-dimethylamine benzoic acid ethyl ester, N,N-dimethylamine benzoic acid isoamyl ester, triethylamine or triethanolamine.

上述成分以外，必要時亦可摻混消泡劑、勻染劑、無機填料、有機填料、光安定劑、抗氧化劑及紫外線吸收劑等。又，必要時亦可少量添加抗氧化劑、光安定劑、紫外線吸收劑及聚合抑制劑等為佳。In addition to the above components, an antifoaming agent, a leveling agent, an inorganic filler, an organic filler, a light stabilizer, an antioxidant, and an ultraviolet absorber may be blended as necessary. Further, if necessary, a small amount of an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, or the like may be added.

【實施例】[Examples]

以下係記載實施例及比較例，以進一步具體說明本發明。The examples and comparative examples are described below to further specifically describe the present invention.

[各種分析方法][various analysis methods] ○酸價○acid price

按照JIS K－0070－1992，將所得丙烯酸酯溶解於乙醇中，用酚酞作為指示藥之氫氧化鉀溶液進行滴定。試料的酸價係由下式算出。The obtained acrylate was dissolved in ethanol according to JIS K-0070-1992, and titrated with potassium hydroxide solution using phenolphthalein as an indicator. The acid value of the sample was calculated by the following formula.

酸價[mg－KOH/g]＝N×T×f×56.11/W N：醇性氫氧化鉀溶液的濃度[mol/L]T：醇性氫氧化鉀溶液的滴定量[ml]f：醇性氫氧化鉀溶液的力價W：試料重量[g]Acid value [mg-KOH/g]=N×T×f×56.11/WN: concentration of alcoholic potassium hydroxide solution [mol/L]T: titration of alcoholic potassium hydroxide solution [ml]f: alcohol Potency of potassium hydroxide solution W: sample weight [g]

○強制劣化試驗○ Forced deterioration test

於30ml玻璃容器中投入所得之5g丙烯酸酯，藉由在大氣陰涼之處靜置數日，將丙烯酸酯所含的水分濃度調整為1,000~3,000wtppm。The obtained 5 g of the acrylate was placed in a 30 ml glass vessel, and the water concentration in the acrylate was adjusted to 1,000 to 3,000 wtppm by allowing to stand for several days in a cool atmosphere.

之後，密封裝入丙烯酸酯之玻璃容器，並在保持於80℃之加熱裝置中加熱72小時。放冷後利用上述的方法來測定酸價。Thereafter, the acrylate glass container was sealed and heated in a heating device maintained at 80 ° C for 72 hours. After cooling, the acid value was measured by the above method.

○比較例1－1○Comparative Example 1-1

在設置回流管之附有1L側管的四口燒瓶中，投入雙酚A的環氧乙烷4莫耳加成物350g、丙烯酸180g、甲苯348g、對甲苯磺酸一水合物20.9g、氫醌0.52g及二氯化銅0.52g。一般吹入含氧氣體(氧5容量%、氮95容量%，以下相同)、一邊在反應液溫度100~119℃下進行加熱攪拌，一面使生成之水於迪安－斯達克管(Dean and Stark tube)去除至系外，且一面進行9小時的脫水酯化反應。In a four-necked flask equipped with a 1 L side tube with a reflux tube, 350 g of ethylene oxide 4 molar addition of bisphenol A, 180 g of acrylic acid, 348 g of toluene, 20.9 g of p-toluenesulfonic acid monohydrate, and hydrogen were introduced.醌 0.52g and 0.52g of copper dichloride. Generally, an oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume, the same applies hereinafter) is blown, and the resultant water is heated and stirred at a reaction liquid temperature of 100 to 119 ° C, and the generated water is applied to the Dean-Stark tube (Dean). And Stark tube) was removed to the outside of the system and subjected to a dehydration esterification reaction for 9 hours.

之後，使反應液冷卻至40℃以下，添加甲苯及水並進行抽出洗淨之後，添加20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the reaction liquid was cooled to 40° C. or lower, toluene and water were added thereto, and the mixture was washed and washed, and then a 20 wt% aqueous sodium hydroxide solution was added to carry out a neutralization treatment, and water was added thereto to carry out extraction washing.

在所得之得有機層中添加0.2g的氫醌一甲基醚(以下稱為MQ)，一邊吹入含氧氣體、一邊在減壓下〔665Pa；5mmHg〕加溫至60~80℃以餾去甲苯。To the obtained organic layer, 0.2 g of hydroquinone monomethyl ether (hereinafter referred to as MQ) was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure [665 Pa; 5 mmHg] to distill off. Remove toluene.

於加壓下進行過濾後，得到製品丙烯酸酯。After filtration under pressure, the product acrylate was obtained.

使用LC/MS且以下述的條件對於所得之丙烯酸酯進行化合物A分析的結果，確認含有382ppm之式(1)中的R¹ 為甲苯醯基、R² 為伸乙基、R³ 為氫原子之化合物(以下，稱為化合物A1)。Using the LC/MS and the result of the compound A analysis of the obtained acrylate under the following conditions, it was confirmed that R ¹ in the formula (1) containing 382 ppm was a tolyl group, R ² was an exoethyl group, and R ³ was a hydrogen atom. The compound (hereinafter referred to as compound A1).

還有，化合物A1的鑑定係根據化合物A1之標準物質的保持時間及碎片圖案而予以確認的。又，化合物A1的定量係就化合物A1之標準物質做成校正曲線，且基於該結果予以定量。Further, the identification of the compound A1 was confirmed based on the retention time of the standard substance of the compound A1 and the fragment pattern. Further, the quantitative amount of the compound A1 was made into a calibration curve for the standard substance of the compound A1, and was quantified based on the result.

(UPLC)裝置：日本WATERS(股)製Acquity UPLC系統管柱：ODS管柱；Acquity BEH 1.7μm C18(管柱：內徑；2.1mm×長度；50mm)管柱溫度：40℃溶離液：水/甲醇＝70/30(Initial)→65/35(10min)→50/50(20min)→0/100(21－23min)流速：0.4mL/min檢測器：光電二極管陣列(PDA)(200－400nm)試料濃度：1%甲醇溶液注入量：5 μ L(UPLC) device: Japan's WATERS (stock) Acquity UPLC system column: ODS column; Acquity BEH 1.7μm C18 (column: inner diameter; 2.1mm × length; 50mm) column temperature: 40 °C dissolving solution: water /methanol=70/30(Initial)→65/35(10min)→50/50(20min)→0/100(21-23min) Flow rate: 0.4mL/min Detector: Photodiode Array (PDA) (200- 400nm) sample concentration: 1% methanol solution injection amount: 5 μL

(MS)裝置：Quattro premier API串聯四極檢測：ESI正離子化檢測毛細電壓：3.5kV、MS：MRM(監控離子：m/z 271>99)、萃取器：4.0V、RF Lens：3.0V、脫溶媒氣體：800L/hr、錐形電壓：30V、錐形氣體流量：50L/hr源(source)溫度：120℃、脫溶媒溫度：400℃、碰撞能量：30V(MS) device: Quattro premier API series quadrupole detection: ESI positive ionization detection capillary voltage: 3.5kV, MS: MRM (monitoring ion: m/z 271> 99), extractor: 4.0V, RF Lens: 3.0V, Desolvent gas: 800L/hr, cone voltage: 30V, cone gas flow rate: 50L/hr source temperature: 120°C, solvent temperature: 400°C, collision energy: 30V

就所得之丙烯酸酯測定酸價。此外，為了評價貯藏安定性及加熱安定性，進行強制劣化試驗，之後測定酸價。彼等結果係如表1所示。The acid value was determined for the obtained acrylate. Further, in order to evaluate the storage stability and the heating stability, a forced deterioration test was performed, and then the acid value was measured. Their results are shown in Table 1.

○實施例1－1○Example 1-1

在比較例1－1中，除了分別將丙烯酸的進料量從180g改成150g、脫水酯化的反應溫度從100~119℃改成100~117℃、反應時間從9小時改成5小時30分以外，按照與比較例1－1同様的方法製造丙烯酸酯，且以同様的方法進行精製。In Comparative Example 1-1, the reaction temperature of the acrylic acid was changed from 180 g to 150 g, the reaction temperature of the dehydration esterification was changed from 100 to 119 ° C to 100 to 117 ° C, and the reaction time was changed from 9 hours to 5 hours. In the same manner as in Comparative Example 1-1, an acrylate was produced and purified by the same method.

關於所得之丙烯酸酯係使用與比較例1－1同様的方法，定量化合物A1，並測定酸價及強制劣化試驗後的酸價。彼等結果係如表1所示。The obtained acrylate was subjected to the same method as in Comparative Example 1-1, and the compound A1 was quantified, and the acid value and the acid value after the forced deterioration test were measured. Their results are shown in Table 1.

○實施例1－2○Example 1-2

將在實施例1－1中脫溶劑步驟後所得之粗生成物裝入500ml燒瓶內，於80℃下加熱攪拌後，添加水並調整水分濃度至4,000~5,000ppm。之後，密封燒瓶並繼續加熱攪拌72小時。The crude product obtained after the solvent removal step in Example 1-1 was placed in a 500 ml flask, and after heating and stirring at 80 ° C, water was added thereto, and the water concentration was adjusted to 4,000 to 5,000 ppm. Thereafter, the flask was sealed and heating and stirring was continued for 72 hours.

之後，將粗生成物冷卻至40℃以下，添加甲苯及20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the crude product was cooled to 40 ° C or lower, toluene and a 20 wt% aqueous sodium hydroxide solution were added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。Filtration is carried out under pressure to obtain an acrylate of the product.

關於所得之丙烯酸酯係使用與比較例1－1同様的方法，定量化合物A1，並測定酸價及強制劣化試驗後的酸價。彼等結果係如表1所示。The obtained acrylate was subjected to the same method as in Comparative Example 1-1, and the compound A1 was quantified, and the acid value and the acid value after the forced deterioration test were measured. Their results are shown in Table 1.

○比較例1－2○Comparative example 1-2

在與比較例1－1同様的燒瓶中，投入p－枯基酚的環氧乙烷1莫耳加成物350g、丙烯酸142g、甲苯321g、對甲苯磺酸一水合物16.5g、氫醌0.48g及二氯化銅0.48g。一邊吹入含氧氣體、一邊於反應液溫度100~119℃下進行加熱攪拌，且一面使生成的水於迪安－斯達克管去除至系外、一面進行9小時的脫水酯化反應。In a flask similar to Comparative Example 1-1, 350 g of an ethylene oxide 1 molar addition product of p-cumylphenol, 142 g of acrylic acid, 321 g of toluene, 16.5 g of p-toluenesulfonic acid monohydrate, and hydroquinone 0.48 were charged. g and copper dichloride 0.48 g. While the oxygen-containing gas was blown, the reaction mixture was heated and stirred at a temperature of 100 to 119 ° C, and the produced water was removed from the Dean-Stark tube to a dehydration esterification reaction for 9 hours.

之後，使反應液冷卻至40℃以下，添加甲苯及水且進行抽出洗淨之後，添加20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the reaction liquid was cooled to 40° C. or lower, toluene and water were added thereto, and the mixture was washed and washed, and then a 20 wt% aqueous sodium hydroxide solution was added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。Filtration is carried out under pressure to obtain an acrylate of the product.

關於所得之丙烯酸酯係使用與比較例1－1同様的方法，定量化合物A1，並測定酸價及強制劣化試驗後的酸價。彼等結果係如表1所示。The obtained acrylate was subjected to the same method as in Comparative Example 1-1, and the compound A1 was quantified, and the acid value and the acid value after the forced deterioration test were measured. Their results are shown in Table 1.

○實施例1－3○Examples 1-3

在比較例1－2中，將脫溶劑步驟後所得之粗生成物裝入500ml燒瓶內，且於80℃下進行加熱攪拌後，添加水以調整水分濃度至4,000~5,000ppm。之後，密封燒瓶並繼續加熱攪拌72小時。In Comparative Example 1-2, the crude product obtained after the solvent removal step was placed in a 500 ml flask, and after heating and stirring at 80 ° C, water was added to adjust the water concentration to 4,000 to 5,000 ppm. Thereafter, the flask was sealed and heating and stirring was continued for 72 hours.

之後，使粗生成物冷卻至40℃以下，添加甲苯及20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the crude product was cooled to 40 ° C or lower, toluene and a 20 wt% aqueous sodium hydroxide solution were added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。關於所得之丙烯酸酯係使用與比較例1－1同様的方法，定量化合物A1，並測定酸價及強制劣化試驗後的酸價。彼等結果係如表1所示。Filtration is carried out under pressure to obtain an acrylate of the product. The obtained acrylate was subjected to the same method as in Comparative Example 1-1, and the compound A1 was quantified, and the acid value and the acid value after the forced deterioration test were measured. Their results are shown in Table 1.

○比較例1－3○Comparative Example 1-3

在與比較例1－1同様的燒瓶中，投入壬基酚的環氧丙烷2.5莫耳加成物350g、丙烯酸106g、甲苯295g、對甲苯磺酸一水合物12.3g、氫醌0.44g及二氯化銅0.44g。一邊吹入含氧氣體、一邊於反應液溫度100~119℃下進行加熱攪拌，且一面使生成的水於迪安－斯達克管去除至系外、一面進行9小時的脫水酯化反應。In the flask of the same manner as in Comparative Example 1-1, 350 g of a propylene oxide 2.5 mol addition product of nonylphenol, 106 g of acrylic acid, 295 g of toluene, 12.3 g of p-toluenesulfonic acid monohydrate, and 0.44 g of hydroquinone and two were charged. Copper chloride 0.44 g. While the oxygen-containing gas was blown, the reaction mixture was heated and stirred at a temperature of 100 to 119 ° C, and the produced water was removed from the Dean-Stark tube to a dehydration esterification reaction for 9 hours.

之後，使反應液冷卻至40℃以下，添加甲苯及水且進行抽出洗淨之後，添加20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the reaction liquid was cooled to 40° C. or lower, toluene and water were added thereto, and the mixture was washed and washed, and then a 20 wt% aqueous sodium hydroxide solution was added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。Filtration is carried out under pressure to obtain an acrylate of the product.

關於所得之丙烯酸酯，使用LC/MS且在以下的條件下進行化合物A的分析。其結果，確認含有288ppm之式(1)中的R¹ 為甲苯醯基、R² 為伸丙基、R³ 為氫原子之化合物(以下，稱為化合物A2)。With respect to the obtained acrylate, analysis of Compound A was carried out using LC/MS under the following conditions. As a result, it was confirmed that 288 ppm of the compound of the formula (1) wherein R ¹ is a tolyl group, R ² is a propyl group, and R ³ is a hydrogen atom (hereinafter referred to as a compound A2).

還有，化合物A2的鑑定係藉由化合物A2標準物質的保持時間及碎片圖案而予以確認。又，化合物A2的定量係就化合物A2的標準物質做成校正曲線，且基於該結果予以定量。Further, the identification of the compound A2 was confirmed by the retention time of the compound A2 standard material and the fragment pattern. Further, the quantitative amount of the compound A2 was made into a calibration curve for the standard substance of the compound A2, and was quantified based on the result.

(UPLC)與比較例1－1相同。(UPLC) is the same as Comparative Example 1-1.

(MS)除了下述以外，與比較例1－1相同。MS：MRM(監控離子：m/z 285>113)、萃取器：3.0V、RF Lens：2.0V、脫溶媒氣體：800L/hr、錐形電壓：30V、錐形氣體流量：50L/hr、源(source)溫度：120℃、脫溶媒溫度：400℃、碰撞能量：10V)(MS) was the same as Comparative Example 1-1 except for the following. MS: MRM (monitoring ion: m/z 285> 113), extractor: 3.0 V, RF Lens: 2.0 V, desolvent gas: 800 L/hr, cone voltage: 30 V, cone gas flow: 50 L/hr, Source temperature: 120 ° C, solvent temperature: 400 ° C, collision energy: 10 V)

○實施例1－4○Example 1-4

在比較例1－3中，將脫溶劑步驟後所得之粗生成物裝入500ml燒瓶內，且於80℃下進行加熱攪拌後，添加水以調整水分濃度至4,000~5,000ppm。之後，密封燒瓶並繼續加熱攪拌72小時。In Comparative Example 1-3, the crude product obtained after the solvent removal step was placed in a 500 ml flask, and after heating and stirring at 80 ° C, water was added to adjust the water concentration to 4,000 to 5,000 ppm. Thereafter, the flask was sealed and heating and stirring was continued for 72 hours.

之後，使粗生成物冷卻至40℃以下，添加甲苯及20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the crude product was cooled to 40 ° C or lower, toluene and a 20 wt% aqueous sodium hydroxide solution were added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.3g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.3 g of MQ was added, and an oxygen-containing gas was blown thereto, and the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。關於所得之丙烯酸酯，利用與比較例1－3同樣的方法，定量化合物A2，且測定酸價及強制劣化試驗後的酸價。彼等結果係如表1所示。Filtration is carried out under pressure to obtain an acrylate of the product. With respect to the obtained acrylate, Compound A2 was quantified by the same method as Comparative Example 1-3, and the acid value and the acid value after the forced deterioration test were measured. Their results are shown in Table 1.

○實施例1－5○Example 1-5

在與比較例1－1同様的燒瓶中，投入雙酚A的環氧乙烷4莫耳加成物350g、丙烯酸180g、甲苯341g、甲磺酸10.6g、氫醌0.51g及二氯化銅0.51g。一邊吹入含氧氣體、一邊於反應液溫度100~119℃下進行加熱攪拌，且一面使生成的水於迪安－斯達克管去除至系外、一面進行9小時的脫水酯化反應。In a flask similar to Comparative Example 1-1, 350 g of an ethylene oxide 4 molar addition product of bisphenol A, 180 g of acrylic acid, 341 g of toluene, 10.6 g of methanesulfonic acid, 0.51 g of hydroquinone, and copper dichloride were charged. 0.51g. While the oxygen-containing gas was blown, the reaction mixture was heated and stirred at a temperature of 100 to 119 ° C, and the produced water was removed from the Dean-Stark tube to a dehydration esterification reaction for 9 hours.

之後，使反應液冷卻至40℃以下，添加甲苯及水且進行抽出洗淨之後，添加20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the reaction liquid was cooled to 40° C. or lower, toluene and water were added thereto, and the mixture was washed and washed, and then a 20 wt% aqueous sodium hydroxide solution was added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

將所得之粗生成物投入500ml燒瓶內，且於80℃下進行加熱攪拌後，添加水以調整水分濃度至4,000~5,000ppm。之後，密封燒瓶並繼續加熱攪拌72小時。The obtained crude product was placed in a 500 ml flask, and after heating and stirring at 80 ° C, water was added to adjust the water concentration to 4,000 to 5,000 ppm. Thereafter, the flask was sealed and heating and stirring was continued for 72 hours.

之後，使粗生成物冷卻至40℃以下，添加甲苯及20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the crude product was cooled to 40 ° C or lower, toluene and a 20 wt% aqueous sodium hydroxide solution were added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。Filtration is carried out under pressure to obtain an acrylate of the product.

關於所得之丙烯酸酯，使用LC/MS且在以下的條件下進行化合物A的分析。其結果，確認含有23ppm之式(1)中的R¹ 為甲基、R² 為伸乙基、R³ 為氫原子之化合物(以下，稱為化合物A3)。With respect to the obtained acrylate, analysis of Compound A was carried out using LC/MS under the following conditions. As a result, it was confirmed that 23 ppm of the compound of the formula (1) wherein R ¹ is a methyl group, R ² is an exoethyl group, and R ³ is a hydrogen atom (hereinafter referred to as a compound A3).

還有，化合物A1－3的鑑定係根據化合物A3標準物質的保持時間及碎片圖案而予以確認。又，化合物A3的定量係就化合物A3的標準物質做成校正曲線，且基於該結果予以定量。Further, the identification of the compound A1-3 was confirmed based on the retention time of the compound A3 standard substance and the fragment pattern. Further, the quantitative amount of the compound A3 was made into a calibration curve for the standard substance of the compound A3, and was quantified based on the result.

(UPLC)除下述以外，其餘與比較例1－1相同。溶離液：水/甲醇＝10/90(Initial一5min)→0/100(10－11min)試料濃度：2%甲醇溶液(UPLC) The same as Comparative Example 1-1 except the following. Dissolution: water/methanol = 10/90 (Initial - 5 min) → 0/100 (10-11 min) Sample concentration: 2% methanol solution

(MS)除下述以外，其餘與比較例1－1相同。毛細電壓：4.5kVMS：MRM(監控離子：m/z 195>99)、萃取器：2.0V、RF Lens：3.0V、脫溶媒氣體：800L/hr、錐形電壓：20V、錐形氣體流量：50L/hr、源(source)溫度：120℃、脫溶媒溫度：400℃、碰撞能量：10V(MS) The same as Comparative Example 1-1 except the following. Capillary voltage: 4.5kVMS: MRM (monitoring ion: m/z 195>99), extractor: 2.0V, RF Lens: 3.0V, desolvent gas: 800L/hr, cone voltage: 20V, cone gas flow: 50L / hr, source temperature: 120 ° C, solvent temperature: 400 ° C, collision energy: 10V

○實施例1－6○Example 1-6

在與比較例1－1同様的燒瓶中，投入三羥甲基丙烷的環氧丙烷6莫耳加成物350g、丙烯酸227g、甲苯372g、甲磺酸13.3g、氫醌0.56g及二氯化銅0.56g。一邊吹入含氧氣體、一邊於反應液溫度100~120℃下進行加熱攪拌，且一面使生成的水於迪安－斯達克管去除至系外、一面進行9小時的脫水酯化反應。In a flask similar to Comparative Example 1-1, 350 g of a propylene oxide 6-mol addition product of trimethylolpropane, 227 g of acrylic acid, 372 g of toluene, 13.3 g of methanesulfonic acid, 0.56 g of hydroquinone, and dichlorination were charged. Copper 0.56g. While the oxygen-containing gas was blown, the reaction mixture was heated and stirred at a temperature of 100 to 120 ° C, and the produced water was removed from the Dean-Stark tube to the outside of the system for 9 hours to carry out a dehydration esterification reaction.

之後，使反應液冷卻至40℃以下，添加甲苯及水且進行抽出洗淨之後，添加20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the reaction liquid was cooled to 40° C. or lower, toluene and water were added thereto, and the mixture was washed and washed, and then a 20 wt% aqueous sodium hydroxide solution was added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

將所得之粗生成物投入500ml燒瓶內，且於80℃下進行加熱攪拌後，添加水以調整水分濃度至4,000~5,000ppm。之後，密封燒瓶並繼續加熱攪拌72小時。The obtained crude product was placed in a 500 ml flask, and after heating and stirring at 80 ° C, water was added to adjust the water concentration to 4,000 to 5,000 ppm. Thereafter, the flask was sealed and heating and stirring was continued for 72 hours.

之後，使粗生成物冷卻至40℃以下，添加甲苯及20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the crude product was cooled to 40 ° C or lower, toluene and a 20 wt% aqueous sodium hydroxide solution were added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中添加0.2g的MQ，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of MQ was added, and while blowing an oxygen-containing gas, the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。Filtration is carried out under pressure to obtain an acrylate of the product.

關於所得之丙烯酸酯，使用LC/MS且在以下的條件下進行化合物A的分析結果，確認含有7ppm之式(1)中的R¹ 為甲基、R² 為伸丙基、R³ 為氫原子之化合物(以下，稱為化合物A4)。With respect to the obtained acrylate, the result of analysis of the compound A was carried out under the following conditions using LC/MS, and it was confirmed that R ¹ in the formula (1) containing 7 ppm was a methyl group, R ² was a propyl group, and R ³ was hydrogen. A compound of an atom (hereinafter referred to as a compound A4).

還有，化合物A4的鑑定係根據化合物A4標準物質的保持時間及碎片圖案而予以確認。又，化合物A4的定量係就化合物A4的標準物質做成校正曲線，且基於該結果予以定量。Further, the identification of the compound A4 was confirmed based on the retention time of the compound A4 standard substance and the fragment pattern. Further, the quantitative amount of the compound A4 was made into a calibration curve for the standard substance of the compound A4, and was quantified based on the result.

(UPLC)除下述以外，其餘與比較例1－1相同。溶離液：水/甲醇＝10/90(Initial－5min)→0/100(10－11min)試料濃度：2%甲醇溶液(UPLC) The same as Comparative Example 1-1 except the following. Dissolution: water/methanol = 10/90 (Initial-5min) → 0/100 (10-11min) Sample concentration: 2% methanol solution

(MS)除下述以外，其餘與比較例1－1相同。毛細電壓：4.5kV MS：MRM(監控離子：m/z 209>113)、萃取器：2.0V、RF Lens：3.0V、脫溶媒氣體：800L/hr、錐形電壓：20V、錐形氣體流量：50L/hr、源(source)溫度：120℃、脫溶媒溫度：400℃、碰撞能量：10V(MS) The same as Comparative Example 1-1 except the following. Capillary voltage: 4.5kV MS: MRM (monitoring ion: m/z 209> 113), extractor: 2.0V, RF Lens: 3.0V, desolvation gas: 800L/hr, cone voltage: 20V, cone gas flow : 50L / hr, source temperature: 120 ° C, solvent temperature: 400 ° C, collision energy: 10V

○比較例2－1○Comparative example 2-1

在設置回流管之附有1L側管的四口燒瓶中，投入雙酚A的環氧乙烷4莫耳加成物350g、丙烯酸150g、甲苯348g、對甲苯磺酸一水合物(以下稱為PTS)20.9g、氫醌(以下稱為HQ)0.52g及二氯化銅0.52g。一邊吹入含氧氣體(氧5容量%、氮95容量%、以下相同)、一邊於反應液溫度100~118℃下進行加熱攪拌，使生成的水一面自迪安－斯達克管去除至系外、且一面進行7小時的脫水酯化反應。In a four-necked flask equipped with a 1 L side tube with a reflux tube, 350 g of an ethylene oxide 4 molar addition product of bisphenol A, 150 g of acrylic acid, 348 g of toluene, and p-toluenesulfonic acid monohydrate (hereinafter referred to as PTS) 20.9 g, hydroquinone (hereinafter referred to as HQ) 0.52 g, and copper dichloride 0.52 g. While blowing an oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%, or less), the mixture was heated and stirred at a temperature of 100 to 118 ° C to remove the generated water from the Dean-Stark tube. The dehydration esterification reaction was carried out for 7 hours while being externally.

之後，使反應液冷卻至40℃以下，添加甲苯及水且進行抽出洗淨之後，添加20wt%氫氧化鈉水溶液以進行中和處理，並且添加水以進行抽出洗淨。Thereafter, the reaction liquid was cooled to 40° C. or lower, toluene and water were added thereto, and the mixture was washed and washed, and then a 20 wt% aqueous sodium hydroxide solution was added to carry out a neutralization treatment, and water was added to carry out extraction washing.

在所得之有機層中，添加0.2g的氫醌一甲基醚(以下稱為MQ)，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。To the obtained organic layer, 0.2 g of hydroquinone monomethyl ether (hereinafter referred to as MQ) was added, and an oxygen-containing gas was blown thereto, and the mixture was heated to 60 to 80 ° C under reduced pressure to distill off toluene.

於加壓下進行過濾後，以得到製品丙烯酸酯。Filtration is carried out under pressure to obtain an acrylate of the product.

關於所得之丙烯酸酯係使用與比較例1－1同様的方法，定量化合物A1，並測定酸價及強制劣化試驗後酸價。彼等結果係如表2所示。The obtained acrylate was subjected to the same method as in Comparative Example 1-1, and the compound A1 was quantified, and the acid value and the acid value after the forced deterioration test were measured. Their results are shown in Table 2.

○實施例2－1○Example 2-1

以與比較例2－1同樣的方法及條件，進行酯化、中和處理及抽出洗淨。Esterification, neutralization treatment, and extraction washing were carried out in the same manner and under the same conditions as in Comparative Example 2-1.

在所得之有機層中，相對於丙烯酸酯添加348wtppm之0.2g的MQ與處理劑的溴化四丁基銨並加以攪拌，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。In the obtained organic layer, 348 wtppm of 348 wtppm of MQ and a treatment agent of tetrabutylammonium bromide were added to the acrylate and stirred, and an oxygen-containing gas was blown while heating to 60 ° under reduced pressure. At 80 ° C, toluene was distilled off.

使脫溶劑後的反應液在加壓下進行過濾，以得到丙烯酸酯。The reaction liquid after desolvation was filtered under pressure to obtain an acrylate.

測定所得丙烯酸酯在製造之後不久及強制劣化試驗後的酸價。彼等結果係如表3所示。The acid value of the obtained acrylate immediately after the production and after the forced deterioration test was measured. Their results are shown in Table 3.

○實施例2－2~同2－8○Example 2-2~ Same 2-8

在實施例2－1中，除了於脫溶劑步驟中添加既定量的下述表3記載之處理劑以外，藉由與實施例2－1同樣的方法來製造丙烯酸酯。In Example 2-1, an acrylate was produced in the same manner as in Example 2-1, except that a treatment agent described in Table 3 below was added in a predetermined amount in the solvent removal step.

使脫溶劑後的反應液在加壓下進行過濾，以得到丙烯酸酯。The reaction liquid after desolvation was filtered under pressure to obtain an acrylate.

測定所得丙烯酸酯在製造之後不久及強制劣化試驗後的酸價。彼等結果係如表3所示。The acid value of the obtained acrylate immediately after the production and after the forced deterioration test was measured. Their results are shown in Table 3.

表3的略號係意味如下。The abbreviations of Table 3 are as follows.

．TBAB：溴化四丁基銨．TBAOH：氫氧化四丁基銨．TMAOH：氫氧化四甲基銨．TBPB：溴化四丁基鏻．IBHA：6,6’－亞胺雙(己基)胺．DMAP：4－二甲基胺吡啶．HMSC：1,6－六亞甲基雙－N,N－二甲基胺基脲. TBAB: tetrabutylammonium bromide. TBAOH: tetrabutylammonium hydroxide. TMAOH: tetramethylammonium hydroxide. TBPB: tetrabutylphosphonium bromide. IBHA: 6,6'-imine bis(hexyl)amine. DMAP: 4-dimethylamine pyridine. HMSC: 1,6-hexamethylenebis-N,N-dimethylaminourea

○實施例2－9~同2－11○Example 2-9~同2-11

在上述實施例2－1中，不添加處理劑來進行脫溶劑處理。In the above Example 2-1, the treatment agent was not added to carry out the solvent removal treatment.

於流去甲苯後所得之粗製品中添加既定量的下述表4中記載之處理劑，在70℃中攪拌1小時以使其均勻混合。之後，於加壓下進行過濾後，得到丙烯酸酯。To the crude product obtained by removing toluene, a predetermined amount of the treating agent described in the following Table 4 was added, and the mixture was stirred at 70 ° C for 1 hour to uniformly mix. Thereafter, filtration was carried out under pressure to obtain an acrylate.

測定所得丙烯酸酯在製造之後不久及強制劣化試驗後的酸價。彼等結果係如表4所示。The acid value of the obtained acrylate immediately after the production and after the forced deterioration test was measured. Their results are shown in Table 4.

表4的略號係意味如下。The abbreviations of Table 4 are as follows.

．DBA：二丁基胺．BA：丁基胺．DEA．HCl：二乙基胺鹽酸鹽. DBA: Dibutylamine. BA: Butylamine. DEA. HCl: diethylamine hydrochloride

○實施例2－12○ Example 2-12

在上述實施例2－1~2－8中，不添加處理劑來進行脫溶劑處理。In the above Examples 2-1 to 2-8, the solvent removal treatment was carried out without adding a treatment agent.

於餾去甲苯餾去後所得之粗製品中，以與實施例2－1~2－8同様的比例添加處理劑，在70℃中攪拌1小時以使其均勻混合。之後，於加壓下進行過濾後，得到丙烯酸酯。The crude product obtained by distilling off the toluene was added in the same manner as in Examples 2-1 to 2-8, and the mixture was stirred at 70 ° C for 1 hour to uniformly mix. Thereafter, filtration was carried out under pressure to obtain an acrylate.

所得之丙烯酸酯係與上述實施例2－1~2－8同様的，強制劣化試驗後的酸價低。The obtained acrylate was the same as those of the above Examples 2-1 to 2-8, and the acid value after the forced deterioration test was low.

○比較例2－2○Comparative Example 2-2

在與比較例2－1同樣的燒瓶中，投入三羥甲基丙烷的環氧丙烷6莫耳加成物372g、丙烯酸200g、甲苯294g、PTS19.0g、HQ0.89g及二氯化銅0.89g，一邊吹入含氧氣體，一邊使其在反應液溫度80~110℃、反應系壓力400~650mmHg的範圍內予以加熱攪拌。使生成的水一面在迪安－斯達克管去除至系外，且一面進行7小時的脫水酯化反應。In the same flask as in Comparative Example 2-1, 372 g of propylene oxide 6-mol addition product of trimethylolpropane, 200 g of acrylic acid, 294 g of toluene, 19.0 g of PTS, 0.89 g of HQ, and 0.89 g of copper dichloride were charged. While blowing an oxygen-containing gas, the mixture was heated and stirred at a reaction solution temperature of 80 to 110 ° C and a reaction system pressure of 400 to 650 mmHg. The generated water was removed to the outside of the Dean-Stark tube, and a dehydration esterification reaction was carried out for 7 hours.

反應終了後，反應液係藉由與比較例2－1同樣的方法進行中和處理，然後添加水後抽出洗淨，並進行脫溶劑處理。After the completion of the reaction, the reaction liquid was subjected to a neutralization treatment in the same manner as in Comparative Example 2-1, and then water was added thereto, and the mixture was washed and subjected to a solvent removal treatment.

關於所得之丙烯酸酯，利用與比較例1－3同樣的方法，定量化合物A2，且並測定酸價及強制劣化試驗後酸價。彼等結果係如表5所示。With respect to the obtained acrylate, Compound A2 was quantified by the same method as Comparative Example 1-3, and the acid value and the acid value after the forced deterioration test were measured. Their results are shown in Table 5.

○實施例2－13○Example 2-13

以與比較例2－2同樣的方法及條件，進行酯化、中和處理及抽出洗淨。Esterification, neutralization treatment, and extraction washing were carried out in the same manner and under the same conditions as in Comparative Example 2-2.

在所得之有機層中，相對於丙烯酸酯添加570wtppm之0.2g的MQ與處理劑的氫氧化四丁基銨，一邊吹入含氧氣體、且一邊在減壓下加溫至60~80℃，以餾去甲苯。In the obtained organic layer, 570 wtppm of 570 wtppm of MQ and 1,4-butylammonium hydroxide as a treating agent were added to the acrylate, and an oxygen-containing gas was blown and heated to 60 to 80 ° C under reduced pressure. Toluene was distilled off.

使脫溶劑後的反應液在加壓下進行過濾，以得到丙烯酸酯。The reaction liquid after desolvation was filtered under pressure to obtain an acrylate.

對所得之丙烯酸酯測定酸價，並在強制劣化試驗後測定酸價。彼等結果係如表6所示。The acid value of the obtained acrylate was measured, and the acid value was measured after the forced deterioration test. Their results are shown in Table 6.

○實施例2－14~同2－18○Example 2-14~同2-18

除了在實施例2－13之脫溶劑步驟中添加既定量的下述表6記載之處理劑以外，藉由與實施例2－13同樣的方法來製造丙烯酸酯。An acrylate was produced in the same manner as in Example 2-13 except that the treating agent described in the following Table 6 was added in the desolvation step of Example 2-13.

使脫溶劑後的反應液在加壓下進行過濾，以得到丙烯酸酯。The reaction liquid after desolvation was filtered under pressure to obtain an acrylate.

測定所得丙烯酸酯在製造之後不久及強制劣化試驗後的酸價。彼等結果係如表6所示。The acid value of the obtained acrylate immediately after the production and after the forced deterioration test was measured. Their results are shown in Table 6.

○實施例2－19○ Example 2-19

在上述實施例2－13中，不添加處理劑來進行脫溶劑處理。In the above Examples 2 to 13, the treatment agent was not added to carry out the solvent removal treatment.

於甲苯餾去後所得之粗製品中既定量添加下述表7記載之處理劑，在70℃中攪拌1小時以使其均勻混合。之後，於加壓下進行過濾後，得到丙烯酸酯。The crude product obtained by distilling off toluene was quantitatively added to the treatment agent shown in the following Table 7, and stirred at 70 ° C for 1 hour to uniformly mix. Thereafter, filtration was carried out under pressure to obtain an acrylate.

測定所得丙烯酸酯在製造之後不久及強制劣化試驗後的酸價。彼等結果係如表7所示。The acid value of the obtained acrylate immediately after the production and after the forced deterioration test was measured. Their results are shown in Table 7.

○實施例2－20○ Example 2-20

在上述實施例2－13~2－18係不添加處理劑來進行脫溶劑處理。In the above Examples 2-13 to 2-18, no solvent was added to carry out the solvent removal treatment.

在餾去甲苯後所得之粗製品中，以與實施例2－13~2－18同様的比例來添加處理劑，將其在70℃攪拌1小時以使其均勻混合。之後，於加壓下進行過濾後，得到丙烯酸酯。In the crude product obtained after distilling off toluene, a treating agent was added in a ratio of the same as that of Examples 2-13 to 2-18, and the mixture was stirred at 70 ° C for 1 hour to uniformly mix. Thereafter, filtration was carried out under pressure to obtain an acrylate.

所得之丙烯酸酯係與上述實施例2－13~2－18同様地，為強制劣化試驗後的酸價較低者。The obtained acrylate was the same as the above Examples 2-13 to 2-18, and was the lower in acid value after the forced deterioration test.

【產業上的利用可能性】[Industrial use possibilities]

本發明之製法係可利用於(甲基)丙烯酸酯之製法。The process of the present invention can be utilized in the production of (meth) acrylate.

此外所得之(甲基)丙烯酸酯係適合使用於光學透鏡、印刷油墨、塗布劑及接著劑等的各種工業用途，作為光硬化性組成物的摻混成分。Further, the obtained (meth) acrylate is suitably used in various industrial applications such as an optical lens, a printing ink, a coating agent, and an adhesive, and is a blending component of a photocurable composition.

Claims (11)

一種(甲基)丙烯酸酯之製法，其特徵係包含：在有機溶媒中藉由有機磺酸觸媒使(甲基)丙烯酸、及具有氧化烯基之醇進行脫水以形成(甲基)丙烯酸酯之酯化步驟，及將該酯化步驟中所得(甲基)丙烯酸酯中的式(1)所示之化合物A控制在0ppm以上100ppm以下之管理步驟；該管理步驟包含：(a)以溫和條件實施酯化反應之方法，(b)實施在(甲基)丙烯酸酯之製法中酯化反應後所實施的精製步驟之方法，且採用該(a)~(b)方法中任1種以上，並定期監視所得之(甲基)丙烯酸酯中化合物A的比例，來管理最終所得(甲基)丙烯酸酯中化合物A為100ppm以下； 〔在式(1)中，R¹ 表示烷基或芳基，R² 表示伸烷基，R³ 表示氫原子或甲基〕。A method for producing a (meth) acrylate, which comprises: dehydrating (meth)acrylic acid and an alcohol having an oxyalkylene group by an organic sulfonic acid catalyst in an organic solvent to form a (meth) acrylate The esterification step, and the management step of controlling the compound A represented by the formula (1) in the (meth) acrylate obtained in the esterification step to be 0 ppm or more and 100 ppm or less; the management step comprises: (a) mild A method of performing an esterification reaction under conditions, (b) a method of performing a purification step performed after an esterification reaction in a method for producing a (meth) acrylate, and using any one of the methods (a) to (b) And regularly monitoring the ratio of the compound A in the obtained (meth) acrylate to manage the compound A in the finally obtained (meth) acrylate to be 100 ppm or less; [In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkylene group, and R ³ represents a hydrogen atom or a methyl group]. 如申請專利範圍第1項之(甲基)丙烯酸酯之製法，其中管理步驟包含以下的1)~4)之至少1種手段， 1)相對於在酯化步驟中醇之羥基1莫耳，使用(甲基)丙烯酸0.8莫耳以上2.0莫耳以下，2)在70℃以上140℃以下進行酯化反應，3)酯化反應係在大略完成的時點予以結束，4)將藉由酯化步驟所得之反應液經由中和處理及水洗處理後所得之粗生成物中的化合物A，於水分的存在下加熱，進行加水分解。 The method for preparing a (meth) acrylate according to the first aspect of the patent application, wherein the management step comprises at least one of the following 1) to 4), 1) relative to the hydroxyl group of the alcohol in the esterification step, using (meth)acrylic acid 0.8 mol or more and 2.0 mol or less, 2) esterification reaction at 70 ° C or more and 140 ° C or less, 3) esterification reaction When the reaction liquid obtained by the esterification step is subjected to the neutralization treatment and the water-washing treatment, the compound A in the crude product obtained by the esterification step is heated in the presence of water to be hydrolyzed. 一種(甲基)丙烯酸酯之製法，其特徵係包含：在有機溶媒中藉由有機磺酸觸媒使(甲基)丙烯酸、及具有氧化烯基之醇進行脫水以形成(甲基)丙烯酸酯之酯化步驟(1)；將經由步驟(1)所得之反應液進行中和處理及水洗處理之步驟(2)；相對於步驟(2)所得之(甲基)丙烯酸酯，在含有1ppm以上的式(1)所示之化合物A的反應液中，添加選自於4級銨鹽、4級鏻鹽、脒以及胺基脲所組成族群之至少1種特定處理劑之添加步驟， 〔在式(1)中，R¹ 表示烷基或芳基，R² 表示伸烷基，R³ 表示氫原子或甲基〕。A method for producing a (meth) acrylate, which comprises: dehydrating (meth)acrylic acid and an alcohol having an oxyalkylene group by an organic sulfonic acid catalyst in an organic solvent to form a (meth) acrylate The esterification step (1); the step (2) of subjecting the reaction solution obtained in the step (1) to a neutralization treatment and a water washing treatment; and the (meth) acrylate obtained in the step (2), containing 1 ppm or more In the reaction liquid of the compound A represented by the formula (1), a step of adding at least one specific treatment agent selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, hydrazine, and an amino urea is added. [In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkylene group, and R ³ represents a hydrogen atom or a methyl group]. 如申請專利範圍第3項之(甲基)丙烯酸酯之製法，其係在添加該特定處理劑的添加步驟之後，包含餾去有機溶媒之脫溶媒步驟。 The method for producing a (meth) acrylate according to claim 3, which comprises the step of desolvating the organic solvent after the step of adding the specific treating agent. 如申請專利範圍第3項之(甲基)丙烯酸酯之製法，其係在該步驟(2)之後，包含：餾去有機溶媒之脫溶媒步驟；在脫溶媒步驟後的反應液中添加該特定處理劑之添加步驟；及進行加熱之加熱步驟。 The method for producing a (meth) acrylate according to claim 3, after the step (2), comprising: a solvent removal step of distilling off the organic solvent; and adding the specific component to the reaction liquid after the solvent removal step a step of adding a treating agent; and a heating step of performing heating. 如申請專利範圍第5項之(甲基)丙烯酸酯之製法，其中該加熱溫度為30~100℃。 The method for producing a (meth) acrylate according to claim 5, wherein the heating temperature is 30 to 100 °C. 如申請專利範圍第1至6項中任一項之(甲基)丙烯酸酯之製法，其中具有氧化烯基之醇係為多元醇之環氧烷加成物。 The process for producing a (meth) acrylate according to any one of claims 1 to 6, wherein the alcohol having an oxyalkylene group is an alkylene oxide adduct of a polyhydric alcohol. 如申請專利範圍第1至6項中任一項之(甲基)丙烯酸酯之製法，其中具有氧化烯基之醇的氧化烯基為氧乙烯基或氧丙烯基，且在式(1)中R² 的伸烷基為伸乙基或伸丙基。The method for producing a (meth) acrylate according to any one of claims 1 to 6, wherein the oxyalkylene group of the alcohol having an oxyalkylene group is an oxyethylene group or an oxypropylene group, and in the formula (1) The alkylene group of R ² is an exoethyl or a propyl group. 一種(甲基)丙烯酸酯系組成物，其係包含具有使(甲基)丙烯酸與具有氧化烯基之醇在有機磺酸觸媒的存在下經脫水酯化反應所得氧化烯基的(甲基)丙烯酸酯之組成物，其中含有0ppm以上100ppm以下的式(1)所示之化合物A。 〔在式(1)中，R¹ 表示烷基或芳基，R² 表示伸烷基，R³ 表示氫原子或甲基〕。A (meth) acrylate-based composition comprising an oxyalkylene group obtained by dehydrating esterification of (meth)acrylic acid with an alcohol having an oxyalkylene group in the presence of an organic sulfonic acid catalyst (methyl group) A composition of an acrylate containing 0 ppm or more and 100 ppm or less of the compound A represented by the formula (1). [In the formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkylene group, and R ³ represents a hydrogen atom or a methyl group]. 如申請專利範圍第9項之(甲基)丙烯酸酯系組成物，其中具有氧化烯基之醇係為多元醇之環氧烷加成物。 The (meth) acrylate composition according to claim 9 wherein the alcohol having an oxyalkylene group is an alkylene oxide adduct of a polyhydric alcohol. 如申請專利範圍第9或10項之(甲基)丙烯酸酯系組成物，其中具有氧化烯基之醇的氧化烯基為氧乙烯基或氧丙烯基，且在式(1)中R² 的伸烷基為伸乙基或伸丙基。A (meth) acrylate-based composition according to claim 9 or 10, wherein the oxyalkylene group of the alcohol having an oxyalkylene group is an oxyethylene group or an oxypropylene group, and R ² in the formula (1) The alkyl group is an ethyl or propyl group.