JP4951967B2 - Production method of polyfunctional (meth) acrylate - Google Patents
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- JP4951967B2 JP4951967B2 JP2005379415A JP2005379415A JP4951967B2 JP 4951967 B2 JP4951967 B2 JP 4951967B2 JP 2005379415 A JP2005379415 A JP 2005379415A JP 2005379415 A JP2005379415 A JP 2005379415A JP 4951967 B2 JP4951967 B2 JP 4951967B2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 195
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 109
- 238000005886 esterification reaction Methods 0.000 claims description 78
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 56
- 239000003960 organic solvent Substances 0.000 claims description 45
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 19
- 230000001476 alcoholic effect Effects 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
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- 239000012295 chemical reaction liquid Substances 0.000 description 13
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
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- 239000007864 aqueous solution Substances 0.000 description 5
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 229960003280 cupric chloride Drugs 0.000 description 3
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- 229920002120 photoresistant polymer Polymers 0.000 description 3
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical group OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 description 1
- DOFIAZGYBIBEGI-UHFFFAOYSA-N 3-sulfanylphenol Chemical compound OC1=CC=CC(S)=C1 DOFIAZGYBIBEGI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 acrylate ester Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はジペンタエリスリトールからなる多価アルコールと（メタ）アクリル酸をエステル化反応させて多官能（メタ）アクリレートを製造する方法に関する。より詳細には、本発明は、ジペンタエリスリトールからなる多価アルコールと（メタ）アクリル酸を、反応液中の水分量を制御しながらエステル化反応させることによって、所望の種々の粘度を有する多官能（メタ）アクリレートを、高収率で、円滑に且つ効率よく製造する方法に関する。 The present invention relates to a method for producing a polyfunctional (meth) acrylate by esterifying a polyhydric alcohol composed of dipentaerythritol and (meth) acrylic acid. More specifically, in the present invention, polyhydric alcohols composed of dipentaerythritol and (meth) acrylic acid are esterified while controlling the amount of water in the reaction solution, thereby having various desired viscosities. The present invention relates to a method for producing a functional (meth) acrylate smoothly and efficiently in a high yield.
（メタ）アクリル酸と多価アルコールを反応させて得られる多官能（メタ）アクリレートは、従来からインキ、塗料などの種々の分野で用いられており、近年、その用途がますます拡大する傾向にある。特に、常圧で２２０℃以上の沸点を有する高沸点の多官能（メタ）アクリレートは、インキや塗料などの他に、電子材料分野（例えばフォトレジスト、レンズ用接着剤などとして）でも用いられるようになっており、用途の拡大に伴って、それぞれの用途や配合形態に適する所望の粘度を有する多官能（メタ）アクリレートを円滑に且つ効率よく製造することのできる方法の開発が求められている。 Polyfunctional (meth) acrylates obtained by reacting (meth) acrylic acid with polyhydric alcohols have been used in various fields such as inks and paints, and in recent years, their use has been increasing. is there. In particular, high-boiling polyfunctional (meth) acrylates having a boiling point of 220 ° C. or higher at normal pressure may be used in the field of electronic materials (for example, as photoresists and lens adhesives) in addition to inks and paints. With the expansion of applications, development of a method capable of smoothly and efficiently producing a polyfunctional (meth) acrylate having a desired viscosity suitable for each application and compounding form is required. .
多官能（メタ）アクリレートは、一般に、（メタ）アクリル酸と多価アルコールを、酸触媒の存在下に、水と共沸混合物を形成する有機溶媒中でエステル化反応させ、反応によって生成する水（縮合水）を有機溶媒との共沸混合物のかたちで系外に除去しながら、エステル化反応を完結させることによって製造されている。
しかしながら、従来は、目的とする所望の粘度を有する多官能（メタ）アクリレートを、高い収率で円滑に得ることはかなり困難であった。
In general, polyfunctional (meth) acrylate is obtained by subjecting (meth) acrylic acid and polyhydric alcohol to an esterification reaction in an organic solvent that forms an azeotrope with water in the presence of an acid catalyst, and water produced by the reaction. It is produced by completing the esterification reaction while removing (condensed water) out of the system in the form of an azeotrope with an organic solvent.
However, conventionally, it has been quite difficult to smoothly obtain a polyfunctional (meth) acrylate having a desired desired viscosity in a high yield.
一方、アルカンジオールと（メタ）アクリル酸を、炭化水素溶媒中で酸性イオン交換樹脂の存在下でエステル化反応させる方法が知られているが（特許文献１を参照）、この方法は、（メタ）アクリレート基を１個有する単官能のヒドロキシアルキルモノ（メタ）アクリレートの製造技術であることから、多官能（メタ）アクリレートの製造には適していない。
本発明の課題は、目的どおりの所定の粘度を有する多官能（メタ）アクリレートを高い収率で円滑に製造する方法を提供することである。
詳細には、本発明の課題は、目的どおりの、種々の粘度の多様な多官能（メタ）アクリレートを、それぞれ高収率でつくり分けることのできる、多官能（メタ）アクリレートの製造方法を提供することである。
An object of the present invention is to provide a method for smoothly producing a polyfunctional (meth) acrylate having a predetermined viscosity as intended in a high yield.
Specifically, the object of the present invention is to provide a method for producing a polyfunctional (meth) acrylate, which can produce various polyfunctional (meth) acrylates having various viscosities as desired, each with high yield. It is to be.
本発明者らは、前記した目的を達成するために鋭意検討を重ねてきた。その結果、（メタ）アクリル酸と５価以上の多価アルコール、特にジペンタエリスリトールをエステル化反応させて多官能（メタ）アクリレートを製造するに当り、反応率が８０％に到達する段階まで、反応液中に含まれる水分量を特定の値以下にすると、多官能（メタ）アクリレートが高い収率で円滑に得られることを見出した。
さらに、本発明者らは、反応液中に含まれる水分量を前記した特定の値以下に制御しながらエステル化反応を行う際に、反応液中に含まれる水分量を異ならせることにより、その水分量に応じて、最終的に得られる多官能（メタ）アクリレートの粘度が異なったものとなること、そのため当該方法において、反応液中の水分量を前記特定の値以下の範囲内で変えることによって、目的とするそれぞれの粘度を有する多官能（メタ）アクリレートを簡単に且つ円滑につくり分けられることを見出し、それらの知見に基づいて本発明を完成した。
The present inventors have intensively studied to achieve the above-described object. As a result, in producing a polyfunctional (meth) acrylate by esterifying (meth) acrylic acid and a polyhydric alcohol having a valence of 5 or more , particularly dipentaerythritol , until the reaction rate reaches 80%, It has been found that when the amount of water contained in the reaction solution is below a specific value, the polyfunctional (meth) acrylate can be obtained smoothly at a high yield.
Furthermore, the present inventors, when performing the esterification reaction while controlling the amount of water contained in the reaction solution below the specific value described above, by varying the amount of water contained in the reaction solution, Depending on the amount of water, the viscosity of the polyfunctional (meth) acrylate finally obtained will be different. Therefore, in this method, the amount of water in the reaction solution is changed within the range below the specified value. Thus, it was found that polyfunctional (meth) acrylates having respective target viscosities can be easily and smoothly produced, and the present invention was completed based on these findings.
すなわち、本発明は、
（１） （メタ）アクリル酸とジペンタエリスリトールをエステル化反応させて、ジペンタエリスリトール中の複数のアルコール性水酸基に（メタ）アクリル酸がエステル結合した多官能（メタ）アクリレートを製造する方法であって、反応率が８０％に到達する段階まで、反応液に含まれる水分量を、有機溶媒を除外した反応液成分の合計質量に対して５質量％以下に制御してエステル化反応を行うことを特徴とする多官能（メタ）アクリレートの製造方法である。
That is, the present invention
(1) (meth) by esterification reaction of acrylic acid with dipentaerythritol, a plurality of alcoholic hydroxyl groups in dipentaerythritol (meth) acrylic acid by the method of producing the polyfunctional (meth) acrylate ester-linked Until the reaction rate reaches 80%, the amount of water contained in the reaction solution is controlled to 5% by mass or less with respect to the total mass of the reaction solution components excluding the organic solvent, and the esterification reaction is performed. It is the manufacturing method of the polyfunctional (meth) acrylate characterized by the above-mentioned.
そして、本発明は、
（２） 反応率が８０％に達する段階まで、反応液に含まれる水分量を、有機溶媒を除外した反応液成分の合計質量に対して０．２〜５質量％の範囲に制御してエステル化反応を行う、前記（１）の多官能（メタ）アクリレートの製造方法；
（３） 粘度が３５００〜７５００ｍＰａ・ｓの多官能（メタ）アクリレートを製造する前記（１）または（２）の多官能（メタ）アクリレートの製造方法；
（４） （メタ）アクリル酸とジペンタエリスリトールのエステル化反応を、メタンスルホン酸、ｐ−トルエンスルホン酸、硫酸、次亜リン酸およびリン酸から選ばれる酸触媒の存在下に行う前記（１）〜（３）のいずれかの多官能（メタ）アクリレートの製造方法；および、
（５） （メタ）アクリル酸とジペンタエリスリトールのエステル化反応を、芳香族炭化水素溶媒、脂肪族炭化水素溶媒およびケトン類から選ばれる有機溶媒中で行う前記（１）〜（４）のいずれかの多官能（メタ）アクリレートの製造方法；
である。
And this invention,
(2) Until the reaction rate reaches 80%, the amount of water contained in the reaction solution is controlled within the range of 0.2 to 5% by mass with respect to the total mass of the reaction solution components excluding the organic solvent. A process for producing a polyfunctional (meth) acrylate according to the above (1), wherein the reaction is conducted
( 3 ) The method for producing a polyfunctional (meth) acrylate according to (1) or (2) , wherein a polyfunctional (meth) acrylate having a viscosity of 3500 to 7500 mPa · s is produced;
(4) The esterification reaction of (meth) acrylic acid and dipentaerythritol is carried out in the presence of an acid catalyst selected from methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hypophosphorous acid and phosphoric acid (1 )-(3) any one of the manufacturing method of polyfunctional (meth) acrylate; and
(5) Any of the above (1) to (4), wherein the esterification reaction of (meth) acrylic acid and dipentaerythritol is carried out in an organic solvent selected from an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent and ketones A method for producing such a polyfunctional (meth) acrylate;
It is.
本発明の方法による場合は、原料として（メタ）アクリル酸とジペンタエリスリトールからなる多価アルコールを用いて、両者を本発明で規定する特定の条件下でエステル化反応させることにより、多官能（メタ）アクリレートを高い収率で円滑に製造することができる。
さらに、本発明の方法による場合は、反応率が８０％に到達する段階までの反応液の水分量を５質量％以下にするという条件を維持しながら、反応液の水分量を変えることで、低粘度品、中粘度品、高粘度品というように、所望の粘度を有する多官能（メタ）アクリレートを簡単に且つ円滑につくり分けることができる。
In the case of the method of the present invention, by using a polyhydric alcohol composed of (meth) acrylic acid and dipentaerythritol as a raw material, both are subjected to esterification reaction under specific conditions defined in the present invention. The (meth) acrylate can be produced smoothly with a high yield.
Furthermore, in the case of the method of the present invention, by maintaining the condition that the water content of the reaction liquid is 5% by mass or less until the reaction rate reaches 80%, the water content of the reaction liquid is changed, Polyfunctional (meth) acrylates having a desired viscosity can be easily and smoothly produced, such as low-viscosity products, medium-viscosity products, and high-viscosity products.
以下に本発明について詳細に説明する。
本発明では、（メタ）アクリル酸として、アクリル酸を単独で使用してもよいし、メタクリル酸を単独で使用してもよいし、またはアクリル酸とメタクリル酸を併用してもよい。そのうちでも、アクリル酸またはメタクリル酸を単独で使用することが、反応率の制御や所望の粘度の製品を得るという点から好ましい。
The present invention is described in detail below.
In the present invention, as (meth) acrylic acid, acrylic acid may be used alone, methacrylic acid may be used alone, or acrylic acid and methacrylic acid may be used in combination. Among them, it is preferable to use acrylic acid or methacrylic acid alone from the viewpoint of controlling the reaction rate and obtaining a product having a desired viscosity.
多官能（メタ）アクリレートの製造に用いる（メタ）アクリル酸としては、本発明の製造方法を円滑に進行させるために、水分含量を１．０質量％以下、特に０．１質量％以下にしたものを使用することが好ましい。 As (meth) acrylic acid used for the production of the polyfunctional (meth) acrylate, the water content is set to 1.0 mass% or less, particularly 0.1 mass% or less in order to smoothly proceed the production method of the present invention. It is preferable to use one.
本発明では、多価アルコールとして、ジペンタエリスリトールを用いる（以下、ジペンタエリスリトールを「多価アルコール」ということがある）。
ジペンタエリスリトールは、安価で汎用性を有する点から好ましい。
In the present invention, dipentaerythritol is used as the polyhydric alcohol (hereinafter, dipentaerythritol may be referred to as “polyhydric alcohol”) .
Dipentaerythritol is not preferable from the viewpoint of having versatility at a low cost.
（メタ）アクリル酸と多価アルコールの使用割合は、目的とする多官能（メタ）アクリレートの種類に応じて異なり得る。例えば、多価アルコールとしてジペンタエリスリトールのような６価の多価アルコールを用いる場合に、６個のアルコール性水酸基のすべてが（メタ）アクリル酸でエステル化されているヘキサ（メタ）アクリレートを製造する場合は、多価アルコール１モルに対して（メタ）アクリル酸を６モル以上の割合で用いるのがよく、６個のアルコール性水酸基のうちの５個が（メタ）アクリル酸でエステル化されているペンタ（メタ）アクリレートを製造する場合は、多価アルコール１モルに対して、（メタ）アクリル酸を５〜６モル程度の割合で用いるのがよく、また６個のアルコール性水酸基のうちの４個が（メタ）アクリル酸でエステル化されているテトラ（メタ）アクリレートを製造する場合は、多価アルコール１モルに対して（メタ）アクリル酸を４〜４．８モル程度の割合で用いるのがよく、また６個のアルコール性水酸基のうちの３個が（メタ）アクリル酸でエステル化されているトリ（メタ）アクリレートを製造する場合は、多価アルコール１モルに対して（メタ）アクリル酸を３〜３．６モル程度の割合で用いるのがよい。いずれにしても、（メタ）アクリル酸と多価アルコールの使用割合は、多価アルコール中の複数（２個以上）のアルコール性水酸基が（メタ）アクリル酸によってエステル化される割合とすることが必要である。
一般的には、多価アルコールのアルコール性水酸基１個（１当量）に対して、（メタ）アクリル酸を１当量（１モル）またはそれ以上の割合で用いて、多価アルコール中のアルコール性水酸基の全部または８０％以上が（メタ）アクリル酸によってエステル化されている多官能（メタ）アクリレートを製造するのが、エステル化反応によって得られる多官能（メタ）アクリレートの品質、生産性、経済性などの点から好ましい。
The use ratio of (meth) acrylic acid and polyhydric alcohol may vary depending on the type of the desired polyfunctional (meth) acrylate. For example, when a hexavalent polyhydric alcohol such as dipentaerythritol is used as the polyhydric alcohol, hexa (meth) acrylate in which all six alcoholic hydroxyl groups are esterified with (meth) acrylic acid is produced. In this case, (meth) acrylic acid is preferably used in a ratio of 6 mol or more per 1 mol of polyhydric alcohol, and 5 of 6 alcoholic hydroxyl groups are esterified with (meth) acrylic acid. In the case of producing penta (meth) acrylate, it is preferable to use (meth) acrylic acid at a ratio of about 5 to 6 moles with respect to 1 mole of polyhydric alcohol. Of the six alcoholic hydroxyl groups, In the case of producing tetra (meth) acrylate in which four of these are esterified with (meth) acrylic acid, (meth) per 1 mol of polyhydric alcohol It is better to use crylic acid at a ratio of about 4 to 4.8 moles, and to produce tri (meth) acrylate in which three of six alcoholic hydroxyl groups are esterified with (meth) acrylic acid. In this case, it is preferable to use (meth) acrylic acid at a ratio of about 3 to 3.6 mol with respect to 1 mol of polyhydric alcohol. In any case, the use ratio of (meth) acrylic acid and polyhydric alcohol may be such that a plurality (two or more) of alcoholic hydroxyl groups in the polyhydric alcohol are esterified by (meth) acrylic acid. is necessary.
In general, the alcoholic properties in polyhydric alcohol are obtained by using (meth) acrylic acid at a ratio of 1 equivalent (1 mole) or more to one alcoholic hydroxyl group (1 equivalent) of polyhydric alcohol. The production of polyfunctional (meth) acrylates in which all or at least 80% of the hydroxyl groups are esterified with (meth) acrylic acid is the quality, productivity and economy of the polyfunctional (meth) acrylate obtained by the esterification reaction. It is preferable from the viewpoint of sex.
（メタ）アクリル酸と多価アルコールのエステル化反応は、酸触媒の存在下に加熱、撹拌しながら行う。
酸触媒としては、（メタ）アクリル酸とアルコール類のエステル化反応に通常用いられているもののいずれもが使用でき、例えば、メタンスルホン酸、ｐ−トルエンスルホン酸、硫酸、次亜リン酸、リン酸などを挙げることができる。前記した酸触媒は単独で使用してもよいし、２種以上を併用してもよい。そのうちでも、メタンスルホン酸、ｐ−トルエンスルホン酸、硫酸が、安価で、得られる製品の着色が少ない点から好ましく用いられる。
酸触媒の使用量は、有機溶媒を含む反応液の質量に基づいて、０．３〜１０質量％、特に０．５〜５質量％であることが、エステル化反応の円滑な進行、色調などの製品品質などの点から好ましい。
The esterification reaction of (meth) acrylic acid and polyhydric alcohol is performed with heating and stirring in the presence of an acid catalyst.
As the acid catalyst, any of those commonly used in the esterification reaction of (meth) acrylic acid and alcohols can be used. For example, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hypophosphorous acid, phosphorus An acid etc. can be mentioned. The above acid catalysts may be used alone or in combination of two or more. Among these, methanesulfonic acid, p-toluenesulfonic acid, and sulfuric acid are preferably used because they are inexpensive and have little coloration in the resulting product.
The amount of the acid catalyst used is 0.3 to 10% by mass, particularly 0.5 to 5% by mass, based on the mass of the reaction solution containing the organic solvent. From the viewpoint of product quality and the like.
（メタ）アクリル酸と多価アルコールのエステル化反応は、溶媒を用いずに行うこともできるが、エステル化反応の進行に伴って反応液中に生成する水（縮合水）を反応液から円滑に除去して、反応率が８０％に到達する段階まで、反応液中の水分含量を５質量％以下に維持するためには、水と共沸混合物を形成する有機溶媒を用いることが望ましい。そのような有機溶媒としては、例えば、トルエン、ベンゼン、キシレンなどの芳香族炭化水素溶媒、ｎ−ヘキサン、ｎ−ヘプタン、シクロヘキサンなどの脂肪族炭化水素溶媒、メチルイソブチルケトンなどのケトン類を挙げることができる。
そのうちでも、トルエン、シクロヘキサンが、反応温度制御、共沸効果の点から好ましく用いられる。
有機溶媒の使用量は、（メタ）アクリル酸と多価アルコールの合計質量の０．１〜１０質量倍、特に０．３〜５質量倍であることが、エステル化反応の円滑な進行、反応液中の水の除去性、水洗などの洗浄操作性、有機溶媒の除去効率などの点から好ましい。
Although the esterification reaction of (meth) acrylic acid and polyhydric alcohol can be carried out without using a solvent, water (condensation water) generated in the reaction liquid as the esterification reaction proceeds is smoothly carried out from the reaction liquid. In order to maintain the water content in the reaction liquid at 5% by mass or less until the reaction rate reaches 80%, it is desirable to use an organic solvent that forms an azeotrope with water. Examples of such organic solvents include aromatic hydrocarbon solvents such as toluene, benzene and xylene, aliphatic hydrocarbon solvents such as n-hexane, n-heptane and cyclohexane, and ketones such as methyl isobutyl ketone. Can do.
Among these, toluene and cyclohexane are preferably used from the viewpoint of reaction temperature control and azeotropic effect.
The amount of the organic solvent used is 0.1 to 10 times by mass, particularly 0.3 to 5 times by mass of the total mass of (meth) acrylic acid and polyhydric alcohol. It is preferable from the viewpoints of water removability in the liquid, washing operability such as washing, and organic solvent removal efficiency.
また、（メタ）アクリル酸および生成した多官能（メタ）アクリレートの重合を防止するために、反応液に重合禁止剤を添加しておくことが好ましい。重合禁止剤としては、例えばハイドロキノン、ハイドロキノンモノメチルエ−テル、２，４−ジメチル−６−ｔ−ブチルフェノール、３−ヒドロキシチオフェノール、α−ニトロソ−β−ナフトール、ｐ−ベンゾキノン、２，５−ジヒドロキシ−ｐ−キノン、銅塩（例えば塩化第二銅など）などを挙げることができ、これらの１種または２種以上を用いることができる。
重合禁止剤の添加量は、原料である（メタ）アクリル酸の質量に基づいて、０．００１〜５．０質量％、特に０．０１〜１．０質量％であることが好ましい。重合禁止剤の添加量が０．００１質量％未満の場合は、重合禁止効果が不十分となることがあり、一方５．０質量％を超えても、重合禁止効果はそれ以上向上しないため不経済となる。
In order to prevent polymerization of (meth) acrylic acid and the generated polyfunctional (meth) acrylate, it is preferable to add a polymerization inhibitor to the reaction solution. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy -P-quinone, copper salt (for example, cupric chloride, etc.) etc. can be mentioned, These 1 type (s) or 2 or more types can be used.
The addition amount of the polymerization inhibitor is preferably 0.001 to 5.0% by mass, particularly 0.01 to 1.0% by mass, based on the mass of (meth) acrylic acid as a raw material. If the addition amount of the polymerization inhibitor is less than 0.001% by mass, the polymerization inhibition effect may be insufficient. On the other hand, if the addition amount exceeds 5.0% by mass, the polymerization inhibition effect will not be improved any further. It becomes economy.
（メタ）アクリル酸と多価アルコールのエステル化反応は、反応時間の短縮と重合防止の点から、６５〜１５０℃、特に７５〜１２０℃の温度で行うことが好ましい。エステル化反応時の温度が６５℃よりも低いと、反応速度の低下、多官能（メタ）アクリレートの収率の低下が生じ易くなり、一方１５０℃を超えると原料である（メタ）アクリル酸および／または生成した多官能（メタ）アクリレートの熱重合が起こり易くなる。
エステル化反応は、常圧かまたは若干減圧した状態、一般的には１００〜４０ｋＰａの圧力下で、エステル化反応によって生成した水を、有機溶媒との共沸混合物の形で反応系外に留去しながら行うことが、反応の円滑な進行、製品着色の抑制の点から好ましい。
更に、原料である（メタ）アクリル酸および／または生成した多官能（メタ）アクリレートの熱重合を防止する目的で、エステル化反応を酸素の存在下で行うことが望ましい。
The esterification reaction of (meth) acrylic acid and polyhydric alcohol is preferably performed at a temperature of 65 to 150 ° C., particularly 75 to 120 ° C. from the viewpoint of shortening the reaction time and preventing polymerization. If the temperature during the esterification reaction is lower than 65 ° C, the reaction rate tends to decrease and the yield of polyfunctional (meth) acrylate tends to decrease. On the other hand, if it exceeds 150 ° C, the raw material (meth) acrylic acid and // The thermal polymerization of the produced polyfunctional (meth) acrylate is likely to occur.
In the esterification reaction, water produced by the esterification reaction is kept outside the reaction system in the form of an azeotrope with an organic solvent under a normal pressure or a slightly reduced pressure, generally 100 to 40 kPa. It is preferable to perform while leaving from the viewpoint of smooth progress of reaction and suppression of product coloring.
Furthermore, for the purpose of preventing thermal polymerization of the raw material (meth) acrylic acid and / or the generated polyfunctional (meth) acrylate, it is desirable to carry out the esterification reaction in the presence of oxygen.
本発明では、（メタ）アクリル酸と多価アルコールのエステル化反応を、反応率が８０％に到達する段階までは、反応液に含まれる水分量を、有機溶媒を除外した反応液成分の合計質量に対して５質量％以下に制御しながら行うことが必要である。反応率が８０％に到達する段階までの間に、反応液中の水分量が継続して５質量％を超えると、目的とする多官能（メタ）アクリレートが円滑に得られなくなり、反応液からの多官能（メタ）アクリレートを精製する際に分離不良などの工程トラブルや、収率の低下、主成分濃度の低下などを生ずる。
本発明では、反応率が８０％に到達する段階まで、反応液に含まれる水分量を、０．２〜５質量％、特に０．２５〜４．５質量％に制御してエステル化反応を行うことが、目的とする多官能（メタ）アクリレートを高収率で円滑に得ることができ、しかも多官能（メタ）アクリレートを製造する際の熱効率を低く抑えることができ、更に製品純度を高めることができる点から好ましい。
In the present invention, the esterification reaction of (meth) acrylic acid and polyhydric alcohol is performed until the reaction rate reaches 80%, and the amount of water contained in the reaction solution is the total of the reaction solution components excluding the organic solvent. It is necessary to carry out while controlling to 5 mass% or less with respect to mass. If the water content in the reaction solution continuously exceeds 5% by mass until the reaction rate reaches 80%, the target polyfunctional (meth) acrylate cannot be obtained smoothly, and When the polyfunctional (meth) acrylate is purified, process troubles such as poor separation, a decrease in yield, a decrease in the main component concentration, and the like occur.
In the present invention, until the reaction rate reaches 80%, the amount of water contained in the reaction solution is controlled to 0.2 to 5% by mass, particularly 0.25 to 4.5% by mass, and the esterification reaction is performed. It is possible to obtain the desired polyfunctional (meth) acrylate smoothly in a high yield, and to reduce the thermal efficiency when producing the polyfunctional (meth) acrylate, and to further increase the product purity. It is preferable because it can be used.
ここで、本明細書でいうエステル化反応の「反応率」とは、（メタ）アクリル酸と多価アルコールの使用割合に応じて、以下の数式（１ａ）または数式（１ｂ）により求められる反応率（％）を意味し、反応率を求めるための具体的な手法は、以下の実施例の項に記載するとおりである。 Here, the “reaction rate” of the esterification reaction referred to in the present specification is a reaction obtained by the following formula (1a) or formula (1b) according to the use ratio of (meth) acrylic acid and polyhydric alcohol. The specific method for obtaining the reaction rate (%) is as described in the Examples section below.
（１）（メタ）アクリル酸の使用モル数が［多価アルコールのモル数］×［多価アルコールのアルコール性水酸基数］と同じか又はそれよりも多い場合：
反応率（％）＝｛（Ａ0−Ａ1）／Ｂ0｝×１００ （１ａ）
［式中、Ａ0＝エステル化反応に使用した（メタ）アクリル酸のモル数、Ａ1＝反応液中に含まれている（メタ）アクリル酸のモル数、Ｂ0＝（多価アルコールのモル数）×（多価アルコールのアルコール性水酸基数）を示す。］
(1) When the number of moles of (meth) acrylic acid used is equal to or greater than [number of moles of polyhydric alcohol] × [number of alcoholic hydroxyl groups of polyhydric alcohol]:
Reaction rate (%) = {(A 0 −A 1 ) / B 0 } × 100 (1a)
[Wherein, A 0 = number of moles of (meth) acrylic acid used in the esterification reaction, A 1 = number of moles of (meth) acrylic acid contained in the reaction solution, B 0 = (of polyhydric alcohol Number of moles) × (number of alcoholic hydroxyl groups of polyhydric alcohol). ]
（２）（メタ）アクリル酸の使用モル数が［多価アルコールのモル数］×［多価アルコールのアルコール性水酸基数］と同じか又はそれよりも少ない場合：
反応率（％）＝｛（Ａ0−Ａ1）／Ａ0｝×１００ （１ｂ）
［式中、Ａ0＝エステル化反応に使用した（メタ）アクリル酸のモル数、Ａ1＝反応液中に含まれている（メタ）アクリル酸のモル数を示す。］
(2) When the number of moles of (meth) acrylic acid used is equal to or less than [number of moles of polyhydric alcohol] × [number of alcoholic hydroxyl groups of polyhydric alcohol]:
Reaction rate (%) = {(A 0 −A 1 ) / A 0 } × 100 (1b)
[Wherein, A 0 = mole number of (meth) acrylic acid used in the esterification reaction, A 1 = mole number of (meth) acrylic acid contained in the reaction solution. ]
（メタ）アクリル酸の使用モル数が［多価アルコールのモル数］×［多価アルコールのアルコール性水酸基数］と同じである場合は、上記した数式（１ａ）または（１ｂ）のいずれで求めても、反応率は同じになる。 When the number of moles of (meth) acrylic acid used is the same as [number of moles of polyhydric alcohol] × [number of alcoholic hydroxyl groups of polyhydric alcohol], it is determined by either the above formula (1a) or (1b). However, the reaction rate is the same.
また、本明細書における「反応液に含まれる水分量」は、反応液に含まれる有機溶媒を除外した残りの成分の合計質量に対する水分量であり、その詳細な測定方法は以下の実施例の項に記載するとおりである。 Further, the “water content contained in the reaction liquid” in the present specification is the water content relative to the total mass of the remaining components excluding the organic solvent contained in the reaction liquid, and the detailed measurement method thereof is described in the following examples. As described in the section.
反応率が８０％に到達する段階までの反応液中の水分量と、最終的に得られる多官能（メタ）アクリレートの粘度には相関関係がある。水分量５質量％以下という条件を守りながら、前記段階までの反応液中の水分量が多いほど（水分量が５質量％に近いほど）、最終的に得られる多官能（メタ）アクリレートの粘度が高くなり、一方反応液中の水分量が少ないほど最終的に得られる多官能（メタ）アクリレートの粘度は低くなる。
かかる点から、反応率が８０％に到達する段階まで反応液中の水分量を５質量％以下に制御するという条件を満たしながら、例えば、当該水分量を０．３質量％、１．５質量％、２．５質量％または５．０質量％というように、所定の値に制御することによって、それぞれの用途や使用目的に適合した、低粘度の多官能（メタ）アクリレート、中粘度の多官能（メタ）アクリレートまたは高粘度の多官能（メタ）アクリレートという粘度の異なる多官能（メタ）アクリレートをそれぞれ製造することができる。
There is a correlation between the amount of water in the reaction solution until the reaction rate reaches 80% and the viscosity of the polyfunctional (meth) acrylate finally obtained. The viscosity of the polyfunctional (meth) acrylate finally obtained is increased as the amount of water in the reaction liquid up to the above stage is increased (the amount of water is closer to 5% by weight) while keeping the condition that the amount of water is 5% by weight or less. On the other hand, the lower the water content in the reaction solution, the lower the viscosity of the polyfunctional (meth) acrylate finally obtained.
From this point, while satisfying the condition that the water content in the reaction solution is controlled to 5% by mass or less until the reaction rate reaches 80%, for example, the water content is 0.3% by mass and 1.5% by mass. %, 2.5% by mass or 5.0% by mass, by controlling to a predetermined value, a low-viscosity polyfunctional (meth) acrylate suitable for each use and purpose of use, Polyfunctional (meth) acrylates having different viscosities such as functional (meth) acrylates or high-viscosity polyfunctional (meth) acrylates can be produced.
最終的に得られる多官能（メタ）アクリレートの粘度は（メタ）アクリル酸と反応させる多価アルコールの種類や量などに応じて異なり得るが、一般的には粘度が３５００〜７５００ｍＰａ・ｓの範囲になるように、反応を制御するのがよい。この場合に、例えば、低粘度の多官能（メタ）アクリレートの製造を目的として反応液の水分量を５質量％以下の所定の低い値に制御しながらエステル化反応を行っているときに、反応液中の水分量が一時的に当該所定の低い値を超えた場合であっても、反応液中の水分量５質量％以下という条件を満たしている場合は、できるだけ速やかに水分量を当該所定の低い値に戻すことによって、目的とする低粘度の多官能（メタ）アクリレートを製造することができる。
ここで、本明細書における「粘度」は、Ｅ型粘度計を使用して２５℃で測定した粘度値をいう。
The viscosity of the polyfunctional (meth) acrylate finally obtained may vary depending on the type and amount of the polyhydric alcohol to be reacted with (meth) acrylic acid, but generally the viscosity is in the range of 3500-7500 mPa · s. It is better to control the reaction so that In this case, for example, when the esterification reaction is performed while controlling the water content of the reaction solution to a predetermined low value of 5% by mass or less for the purpose of producing a low-viscosity polyfunctional (meth) acrylate. Even when the amount of water in the liquid temporarily exceeds the predetermined low value, if the condition that the amount of water in the reaction liquid is 5% by mass or less is satisfied, the amount of water is determined as soon as possible. By returning to a low value, a target low-viscosity polyfunctional (meth) acrylate can be produced.
Here, “viscosity” in the present specification refers to a viscosity value measured at 25 ° C. using an E-type viscometer.
反応液中の水分量は、「（メタ）アクリル酸と多価アルコールとのエステル化反応で反応液中に生成する水（縮合水）の量」と、「水と有機溶媒の共沸混合物の形で反応系から蒸発除去される（共沸により除かれる）水の量」との間のバランスを採ることによって、その増減を調整することができる。
具体的には、例えば、反応液が所定の温度（ＴA）（℃）になっているときに、外温（反応液を入れた容器の外周に設けた加熱ジャケットやオイルバスなどの温度）（ＴB）（℃）との温度差（ΔＴ）（ＴB−ＴA）を調整することによって、反応液中の水分量を制御することができる。温度差（ΔＴ）を小さくすると（外温をあまり高くしない場合は）反応液中の水分量が増し、温度差（ΔＴ）を大きくして反応液を外部からの加熱を強くすると反応液中の水分量は減少する。反応液と外温との適当な温度差（ΔＴ）は、それぞれの状況に応じて異なり得るが、一般的には、温度差（ΔＴ）を５〜５０℃、特に 〜４０℃にして、（メタ）アクリル酸と多価アルコールのエステル化反応を行うと、反応率８０％の段階までの反応液中の水分量を５質量％以下に円滑に制御することができ、しかもエステル化反応時の熱エネルギーの消費量を抑制しながら、目的とする多官能（メタ）アクリレートを高収率で得ることができる。
The amount of water in the reaction solution is “the amount of water (condensed water) produced in the reaction solution by the esterification reaction of (meth) acrylic acid and polyhydric alcohol” and “the azeotrope of water and organic solvent”. By adjusting the balance between the amount of water that is evaporated and removed from the reaction system in the form (removed by azeotropy), the increase or decrease can be adjusted.
Specifically, for example, when the reaction solution is at a predetermined temperature (T A ) (° C.), the external temperature (the temperature of the heating jacket or oil bath provided on the outer periphery of the container containing the reaction solution) By adjusting the temperature difference (ΔT) (T B −T A ) from (T B ) (° C.), the amount of water in the reaction solution can be controlled. When the temperature difference (ΔT) is reduced (when the external temperature is not increased too much), the amount of water in the reaction solution increases, and when the temperature difference (ΔT) is increased and the reaction solution is strongly heated from the outside, The amount of water decreases. The appropriate temperature difference (ΔT) between the reaction solution and the external temperature may vary depending on the situation, but in general, the temperature difference (ΔT) is set to 5 to 50 ° C., particularly to −40 ° C. When the esterification reaction of (meth) acrylic acid and a polyhydric alcohol is carried out, the water content in the reaction solution up to a stage with a reaction rate of 80% can be smoothly controlled to 5% by mass or less, and at the time of the esterification reaction The desired polyfunctional (meth) acrylate can be obtained in high yield while suppressing the consumption of heat energy.
エステル化反応の反応率が８０％に到達した後では、反応液中の水分量の多少は、目的とする多官能（メタ）アクリレートの収率、粘度、色調などに余り影響を及ぼさないので、反応液中の水分量を厳密に制御する必要はないが、一般的には水分量を０．０１〜１．０質量％の範囲にしておくことが、生産性の点から好ましい。
反応率が８０％に到達した後は、一般的には８０％到達時よりも水分量が多くならないようにしながら、反応液中の水分量が一定になるまでエステル化反応を継続して行い、水分量が一定になった時点でエステル化反応を終了するとよい。
After the reaction rate of the esterification reaction reaches 80%, the amount of water in the reaction solution does not significantly affect the yield, viscosity, color tone, etc. of the target polyfunctional (meth) acrylate. Although it is not necessary to strictly control the water content in the reaction solution, it is generally preferable from the viewpoint of productivity to keep the water content in the range of 0.01 to 1.0% by mass.
After the reaction rate has reached 80%, the esterification reaction is generally continued until the water content in the reaction solution becomes constant, while keeping the water content not higher than when reaching 80%. The esterification reaction may be terminated when the water content becomes constant.
上記によって得られた多官能（メタ）アクリレートを含有する反応液を後処理して多官能（メタ）アクリレートを回収する。
まず、上記で得られた多官能（メタ）アクリレートを含有する反応液中にアルカリ水溶液を添加して、反応液に含まれている酸触媒および未反応の（メタ）アクリル酸を中和する。アルカリ水溶液としては、水酸化ナトリウム、水酸化カリウムなどのアルカリの水溶液を用いるのが好ましく、水酸化ナトリウム水溶液を用いるのが中和の円滑性、経済性などの点からより好ましい。アルカリ水溶液の濃度は、一般に１〜２５質量％程度、特に５〜２０質量％程度が好ましい。
The reaction solution containing the polyfunctional (meth) acrylate obtained as described above is post-treated to recover the polyfunctional (meth) acrylate.
First, an aqueous alkali solution is added to the reaction solution containing the polyfunctional (meth) acrylate obtained above to neutralize the acid catalyst and unreacted (meth) acrylic acid contained in the reaction solution. As the aqueous alkali solution, an aqueous alkali solution such as sodium hydroxide or potassium hydroxide is preferably used, and an aqueous sodium hydroxide solution is more preferred from the standpoint of smoothness of neutralization and economy. The concentration of the alkaline aqueous solution is generally about 1 to 25% by mass, and particularly preferably about 5 to 20% by mass.
次に、中和後の反応液を、必要に応じて水洗処理する。水洗処理は、中和後に限定されず、場合によっては中和前に行なってもよいし、または中和前と中和後の両方で行なってもよい。水洗処理に使用する水としては、蒸留水、精製水などを用いるのが好ましく、場合によっては無機塩（例えば塩化ナトリウム、硫酸アンモニウムなど）を溶解させた前記水を使用してもよい。水洗処理は１回のみ行なってもよいし、または複数回行ってもよい。
水洗処理によって、反応液中に含まれている中和した酸触媒や未反応の（メタ）アクリル酸の塩、または塩になっていない触媒、未反応の（メタ）アクリル酸などが水相中に移行して有機溶媒相から除かれる。
Next, the neutralized reaction solution is washed with water as necessary. The water washing treatment is not limited after neutralization, and may be performed before neutralization or may be performed both before and after neutralization depending on circumstances. As water used for the water washing treatment, distilled water, purified water or the like is preferably used. In some cases, the water in which an inorganic salt (for example, sodium chloride, ammonium sulfate or the like) is dissolved may be used. The water washing process may be performed only once, or may be performed a plurality of times.
By washing with water, neutralized acid catalyst, unreacted (meth) acrylic acid salt, or non-salt catalyst, unreacted (meth) acrylic acid, etc. contained in the reaction solution are contained in the aqueous phase. To be removed from the organic solvent phase.
中和、水洗後の反応液を静置して、水相からなる下層と、有機溶媒溶液からなる上層に層分離させた後、上層の有機溶媒溶液を分取し、該有機溶媒溶液を蒸留処理して有機溶媒を留去して、目的とする多官能（メタ）アクリレートを取得する。蒸留処理は、一般に減圧下に、加熱して行なうのがよく、その際の圧力は０．１〜８０ｋＰａ、温度は４０〜１２０℃程度であることが、目的物である多官能（メタ）アクリレートを円滑に回収できる点から好ましい。 The reaction solution after neutralization and washing with water is allowed to stand, and after separating the layer into a lower layer composed of an aqueous phase and an upper layer composed of an organic solvent solution, the upper organic solvent solution is separated, and the organic solvent solution is distilled. The organic solvent is distilled off by treatment to obtain the desired polyfunctional (meth) acrylate. In general, the distillation treatment is preferably performed by heating under reduced pressure, and the pressure is 0.1 to 80 kPa and the temperature is about 40 to 120 ° C., which is the target polyfunctional (meth) acrylate. Is preferable because it can be recovered smoothly.
本発明の方法により得られる多官能（メタ）アクリレートは、インキ、塗料、刷板、フォトレジスト、光学フィルム用接着剤などの用途に有効に使用することができる。 The polyfunctional (meth) acrylate obtained by the method of the present invention can be effectively used for applications such as inks, paints, printing plates, photoresists and optical film adhesives.
以下に実施例などにより本発明について具体的に説明するが、本発明は以下の実施例に限定されるものではない。
以下の例において、反応率、反応液に含まれる水分量、最終的に得られた多官能アクリレートの粘度は、次のようにして測定または算出した。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
In the following examples, the reaction rate, the amount of water contained in the reaction solution, and the viscosity of the finally obtained polyfunctional acrylate were measured or calculated as follows.
（１）反応率：
反応開始時点での反応液の酸価（仕込み酸価）および各反応時点での反応液の酸価を滴定により測定して、下記の数式（Ｉａ’）から、反応率（％）を求めた。
反応率(％)＝[{仕込み酸価(mmol／ｇ)−反応液酸価(mmol／ｇ)}÷B0]×100 (１ａ')
［式中、
仕込み酸価(mmol/g)＝反応開始時のアクリル酸濃度(mmol/g)−酸触媒濃度(mmol/g)
反応液酸価(mmol/g) ＝各反応時点でのアクリル酸濃度(mmol/g)−酸触媒濃度(mmol/g)、
およびＢ0は使用した多価アルコール（ジペンタエリスリトール）のモル数(mmol/g)×多価アルコールのアルコール性水酸基の数（＝６）を示す。］
(1) Reaction rate:
The acid value (prepared acid value) of the reaction solution at the start of the reaction and the acid value of the reaction solution at each reaction time were measured by titration, and the reaction rate (%) was determined from the following formula (Ia ′). .
Reaction rate (%) = [{Feed acid value (mmol / g) −Reaction liquid acid value (mmol / g)} ÷ B 0 ] × 100 (1a ′)
[Where:
Charged acid value (mmol / g) = acrylic acid concentration (mmol / g) at the start of reaction−acid catalyst concentration (mmol / g)
Reaction solution acid value (mmol / g) = acrylic acid concentration (mmol / g) -acid catalyst concentration (mmol / g) at each reaction time point,
B 0 represents the number of moles of polyhydric alcohol (dipentaerythritol) used (mmol / g) × the number of alcoholic hydroxyl groups of the polyhydric alcohol (= 6). ]
但し、上記の数式(１ａ')において、酸触媒濃度は反応開始時と各反応時点で同じであるから、上記の数式(１ａ')における分子は、｛反応開始時のアクリル酸濃度(mmol/g)−各反応時点でのアクリル酸濃度(mmol/g)｝になり、したがって上記数式(１ａ')は、先に記載した数式（１ａ）と実質的に同じである。 However, in the above formula (1a ′), the acid catalyst concentration is the same at the start of the reaction and at each reaction time. Therefore, the numerator in the above formula (1a ′) is expressed as {acrylic acid concentration at start of reaction (mmol / g) —acrylic acid concentration at the time of each reaction (mmol / g)}, and therefore the above formula (1a ′) is substantially the same as the formula (1a) described above.
（２）反応液に含まれる水分量：
反応液に含まれる水分量（質量％）をカールフィッシャー水分計（三菱化学株式会社製「ＣＡ−１００」）を使用して測定し、また反応液に含まれる有機溶媒の量（質量％）を下記の条件下にガスクロマトグラフィーにて測定して、以下の数式（２）から反応液に含まれる水分量（質量％）を求めた。
［ガスクロマトグラフィー条件］
装置：株式会社島津製作所製「ＧＣ−１４Ｂ」
カラム：内径３ｍｍ×長さ１ｍ、充填剤：ポリマー系充填剤（Ｗａｔｅｒｓ社製「Ｐｏｒａｐａｋ Ｑ５０／８０」）
カラム温度：２３０℃
キャリアガス：窒素、０．７ｋｇ／ｃｍ2
注入口温度：２３０℃
検出方法：ＦＩＤ
検出器温度：２３０℃
水分量（質量％）＝｛Ｃ／（１００−Ｄ）｝×１００ （２）
［式中、Ｃは反応液の水分量（質量％）、Ｄは反応液に含まれ有機溶媒の量（質量％）を示す。］
(2) Water content in the reaction solution:
The amount of water (mass%) contained in the reaction solution was measured using a Karl Fischer moisture meter (“CA-100” manufactured by Mitsubishi Chemical Corporation), and the amount of organic solvent (mass%) contained in the reaction solution was determined. It was measured by gas chromatography under the following conditions, and the amount of water (mass%) contained in the reaction solution was determined from the following formula (2).
[Gas chromatography conditions]
Equipment: “GC-14B” manufactured by Shimadzu Corporation
Column: Inner diameter 3 mm × Length 1 m, Filler: Polymer filler (“Porapak Q50 / 80” manufactured by Waters)
Column temperature: 230 ° C
Carrier gas: nitrogen, 0.7 kg / cm 2
Inlet temperature: 230 ° C
Detection method: FID
Detector temperature: 230 ° C
Water content (mass%) = {C / (100−D)} × 100 (2)
[In the formula, C represents the water content (% by mass) of the reaction solution, and D represents the amount (% by mass) of the organic solvent contained in the reaction solution. ]
（３）多官能アクリレートの粘度：
Ｅ型粘度計（東機産業株式会社製「ＴＶ−２２形粘度計」、コーンプレートタイプ）を使用して、２５℃で測定した。
(3) Viscosity of polyfunctional acrylate:
Using an E type viscometer (“TV-22 viscometer” manufactured by Toki Sangyo Co., Ltd., cone plate type), the measurement was performed at 25 ° C.
《実施例１》
（１）エステル化反応工程：
攪拌機、温度計、反応液の採取口およびディーンスターク装置を備えた２リットルの反応器に、ジペンタエリスリトール３１５ｇ（１．２４モル）、アクリル酸６４３ｇ（８．９モル）、トルエン５２６ｇ、７８％硫酸１５gおよび塩化第二銅１．５gを仕込み、５３ｋＰａの圧力下で、９４℃に設定したオイルバスで反応器を加熱して脱水エステル化反応を開始した。反応で生じる水は、トルエンと共沸させ、ディーンスターク装置で除去してエステル化反応を進めた。
このエステル化反応の間に、６０分毎に反応液を少量ずつ採取して、上記した方法で反応率および水分量を求めたところ、反応開始７２０分後に反応率が８０％に到達した。
反応開始から反応率が８０％に到達する時点までの反応液中の水分量は１．５〜３．７質量％の範囲に保たれていた（最大の水分量＝３．７質量％、反応率８０％の時点での水分量＝１．５質量％）。
このエステル化反応は、反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）が１３〜１４℃になるように、オイルバスの温度を微調整しながら反応を継続し、反応開始から１６時間後に反応液の酸価が一定になったので、エステル化反応を停止した。反応停止時の反応液の水分量は０．４質量％であり、反応器内の反応液の質量は１３８０ｇ、酸価は１．７５ｍｅｑ／ｇであった。また、反応停止時の反応率を上記した方法で求めたところ、８８％であった。
Example 1
(1) Esterification reaction step:
In a 2-liter reactor equipped with a stirrer, thermometer, reaction liquid sampling port and Dean-Stark apparatus, dipentaerythritol 315 g (1.24 mol), acrylic acid 643 g (8.9 mol), toluene 526 g, 78% 15 g of sulfuric acid and 1.5 g of cupric chloride were charged, and the dehydration esterification reaction was started by heating the reactor in an oil bath set at 94 ° C. under a pressure of 53 kPa. The water produced in the reaction was azeotroped with toluene and removed with a Dean-Stark apparatus to proceed with the esterification reaction.
During the esterification reaction, a small amount of the reaction solution was sampled every 60 minutes, and the reaction rate and water content were determined by the above-described method. The reaction rate reached 80% 720 minutes after the start of the reaction.
The water content in the reaction solution from the start of the reaction until the reaction rate reached 80% was kept in the range of 1.5 to 3.7% by mass (maximum water content = 3.7% by mass, reaction Water content at a rate of 80% = 1.5 mass%).
The esterification reaction is such that the temperature difference between the reaction temperature and (T A) and the oil bath temperature (T B) (ΔT) ( T B -T A) is 13 to 14 ° C., oil bath The reaction was continued while finely adjusting the temperature, and the esterification reaction was stopped because the acid value of the reaction solution became constant 16 hours after the start of the reaction. The water content of the reaction solution at the time of stopping the reaction was 0.4% by mass, the mass of the reaction solution in the reactor was 1380 g, and the acid value was 1.75 meq / g. Moreover, it was 88% when the reaction rate at the time of reaction stop was calculated | required by the above-mentioned method.
（２）後処理工程：
（ｉ） 上記（１）で得られた反応液１３８０ｇを３０℃に冷却した後、トルエン７４０ｇを加えて希釈し、それを中和処理用の槽に移し、純水３５０ｇを加えて５分間攪拌して水洗した後、３０分間静置して、水相（下層）と有機溶媒溶液相（上層）に層分離させ、下層の水相を除去した。
（ii） 次いで、有機溶媒溶液相に２０％水酸化ナトリウム水溶液３４５ｇを加えて５分間撹拌して有機溶媒溶液相に含まれる酸成分を中和した後、３０分間静置して、水相（下層）と有機溶媒溶液相（上層）に層分離させ、下層の水相を除去して有機溶媒溶液相を回収したところ１９００ｇであった。更に、２０％水酸化ナトリウム水溶液６９０ｇを加えて液温を３０℃に維持しながら１時間撹拌して不純物の除去を行った。次いで、３０分間静置して、水相（下層）と有機溶媒溶液相（上層）に層分離させ、下層を分取して除去した。これにより回収した有機溶媒溶液相に、洗浄のために蒸留水２１０ｇを加えて充分攪拌した後に静置し、分離した水相（下層）を除去し、上層の有機溶媒溶液相を回収した。
（iii） 上記（ii）で回収した有機溶媒溶液相に、ハイドロキノンモノメチルエーテル（ＭＱ）４００ｐｐｍを添加して、オイルバスの温度を８０℃に設定し、酸素を含む窒素ガスを吹き込みながら、減圧下（５ｋＰａ）に、トルエンの濃度が１質量％以下になるまで蒸留処理（脱溶媒処理）して、多官能アクリレート５７３ｇを得た。これにより得られた多官能アクリレートの粘度を、上記した方法で測定したところ、下記の表１に示すように６３７０ｍＰａ・ｓであった。
(2) Post-processing process:
(I) After cooling 1380 g of the reaction solution obtained in (1) above to 30 ° C., 740 g of toluene was added for dilution, transferred to a tank for neutralization treatment, 350 g of pure water was added, and the mixture was stirred for 5 minutes. After washing with water, the mixture was allowed to stand for 30 minutes, and separated into an aqueous phase (lower layer) and an organic solvent solution phase (upper layer), and the lower aqueous phase was removed.
(Ii) Next, 345 g of a 20% aqueous sodium hydroxide solution was added to the organic solvent solution phase, and the mixture was stirred for 5 minutes to neutralize the acid component contained in the organic solvent solution phase. The lower layer was separated into an organic solvent solution phase (upper layer), the lower aqueous phase was removed, and the organic solvent solution phase was recovered to find 1900 g. Further, 690 g of a 20% sodium hydroxide aqueous solution was added, and the impurities were removed by stirring for 1 hour while maintaining the liquid temperature at 30 ° C. Next, the mixture was allowed to stand for 30 minutes, and the aqueous phase (lower layer) and the organic solvent solution phase (upper layer) were separated, and the lower layer was separated and removed. The organic solvent solution phase thus recovered was added with 210 g of distilled water for washing and sufficiently stirred, and then allowed to stand. The separated aqueous phase (lower layer) was removed, and the upper organic solvent solution phase was recovered.
(Iii) To the organic solvent solution phase recovered in (ii) above, 400 ppm of hydroquinone monomethyl ether (MQ) was added, the temperature of the oil bath was set to 80 ° C., and nitrogen gas containing oxygen was blown in under reduced pressure. (5 kPa) was subjected to distillation treatment (desolvation treatment) until the toluene concentration became 1% by mass or less to obtain 573 g of a polyfunctional acrylate. When the viscosity of the polyfunctional acrylate thus obtained was measured by the method described above, it was 6370 mPa · s as shown in Table 1 below.
《実施例２》
（１） 実施例１の（１）のエステル化反応工程において、反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）が２２℃になるように、オイルバスの温度を調整しながら全体で７．５時間エステル化反応を行なった以外は実施例１の（１）と同様にしてエステル化反応を行なった。
この実施例２では、反応開始３３０分後にエステル化反応の反応率が８０％に到達し、反応開始から反応率が８０％に到達する時点までの反応液中の水分量は０．５〜１．５質量％の範囲に保たれていた（最大の水分量＝１．５質量％、反応率８０％の時点での水分量＝０．５質量％）。
エステル化反応を停止した反応開始７．５時間後の時点で、反応液の水分量は０．４質量％であり、反応器内の反応液の質量は１３８０ｇ、酸価は１．７３ｍｅｑ／ｇであり、上記した方法で求めた反応率は８９％であった。
（２） 続いて、上記（１）で生成した反応液を、実施例１の（２）と同様に後処理して、多官能アクリレートを製造した。これにより得られた多官能アクリレートの粘度を、上記した方法で測定したところ、下記の表１に示すように５３３０ｍＰａ・ｓであった。
Example 2
(1) in the esterification reaction step (1) of Example 1, the temperature difference between the reaction temperature and (T A) and the oil bath temperature (T B) (ΔT) ( T B -T A) is 22 The esterification reaction was carried out in the same manner as in (1) of Example 1 except that the esterification reaction was carried out for 7.5 hours in total while adjusting the temperature of the oil bath so that the temperature became 0 ° C.
In Example 2, the reaction rate of the esterification reaction reached 80% 330 minutes after the start of the reaction, and the amount of water in the reaction solution from the start of the reaction until the time when the reaction rate reached 80% was 0.5 to 1. It was kept in the range of 0.5% by mass (maximum water content = 1.5% by mass, water content at a reaction rate of 80% = 0.5% by mass).
At 7.5 hours after the start of the reaction when the esterification reaction was stopped, the water content of the reaction solution was 0.4% by mass, the mass of the reaction solution in the reactor was 1380 g, and the acid value was 1.73 meq / g. The reaction rate determined by the above method was 89%.
(2) Subsequently, the reaction solution produced in (1) above was post-treated in the same manner as in (2) of Example 1 to produce a polyfunctional acrylate. When the viscosity of the polyfunctional acrylate thus obtained was measured by the method described above, it was 5330 mPa · s as shown in Table 1 below.
《実施例３》
（１）エステル化反応工程：
実施例１の（１）で使用したのと同じ反応器に、ジペンタエリスリトール２６６ｇ（１．０５モル）、アクリル酸６７８．５ｇ（９．４モル）、トルエン５３９ｇ、７８％硫酸９．９g、ｐ−トルエンスルホン酸４５ｇおよび塩化第二銅１．５gを仕込み、５３ｋＰａの圧力下で、９４℃に設定したオイルバスで反応器を加熱して脱水エステル化反応を開始した。反応で生じる水は、トルエンと共沸させ、ディーンスターク装置で除去してエステル化反応を進めた。
このエステル化反応の間に、６０分毎に反応液を少量ずつ採取して、上記した方法で反応率および水分量を求めたところ、反応開始６００分後に反応率が８０％に到達した。
反応開始から反応率が８０％に到達する時点までの反応液中の水分量は２．５〜４．３質量％の範囲に保たれていた（最大の水分量＝４．３質量％、反応率８０％の時点での水分量＝３．５質量％）。
このエステル化反応は、反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）が１３〜１５℃になるように、オイルバスの温度を微調整しながら反応を継続し、反応開始から１５時間後に反応液の酸価が一定になったので、エステル化反応を停止した。反応停止時の反応液の水分量は０．１質量％であり、反応器内の反応液の質量は１４２０ｇ、酸価は２．３５ｍｅｑ／ｇであった。また、反応停止時の反応率を上記した方法で求めたところ、９９％であった。
Example 3
(1) Esterification reaction step:
In the same reactor used in (1) of Example 1, 266 g (1.05 mol) of dipentaerythritol, 678.5 g (9.4 mol) of acrylic acid, 539 g of toluene, 9.9 g of 78% sulfuric acid, 45 g of p-toluenesulfonic acid and 1.5 g of cupric chloride were charged, and the dehydration esterification reaction was started by heating the reactor in an oil bath set at 94 ° C. under a pressure of 53 kPa. The water produced in the reaction was azeotroped with toluene and removed with a Dean-Stark apparatus to proceed with the esterification reaction.
During the esterification reaction, a small amount of the reaction solution was sampled every 60 minutes, and the reaction rate and water content were determined by the method described above. The reaction rate reached 80% 600 minutes after the start of the reaction.
The amount of water in the reaction solution from the start of the reaction until the reaction rate reached 80% was kept in the range of 2.5 to 4.3% by mass (maximum amount of water = 4.3% by mass, reaction Water content at a rate of 80% = 3.5% by mass).
This esterification reaction is carried out so that the temperature difference (ΔT) (T B −T A ) between the reaction liquid temperature (T A ) and the oil bath temperature (T B ) is 13 to 15 ° C. The reaction was continued while finely adjusting the temperature, and since the acid value of the reaction solution became constant 15 hours after the start of the reaction, the esterification reaction was stopped. The water content of the reaction solution at the time of stopping the reaction was 0.1% by mass, the mass of the reaction solution in the reactor was 1420 g, and the acid value was 2.35 meq / g. Moreover, when the reaction rate at the time of reaction stop was calculated | required by the above-mentioned method, it was 99%.
（２）後処理工程：
（ｉ） 上記（１）で得られた反応液１４２０ｇを３０℃に冷却した後、トルエン７７０ｇを加えて希釈し、それを中和処理用の槽に移し、４％硫酸アンモニウム水溶液７３０ｇを加えて５分間攪拌して水洗した後、３０分間静置して、水相（下層）と有機溶媒溶液相（上層）に層分離させ、下層の水相を除去した。有機溶媒溶液相の酸価を測定したところ、０．８０ｍｅｑ／ｇであった。
（ii） 次いで、有機溶媒溶液相に２０％水酸化ナトリウム水溶液５２０ｇを加えて液温を３０℃に保ちながら１０分間撹拌して有機溶媒溶液相に含まれる酸成分を中和した後、３０分間静置して、水相（下層）と有機溶媒溶液相（上層）に層分離させ、下層の水相を除去して有機溶媒溶液相を回収したところ１９００ｇであった。回収した有機溶媒溶液相に、４％硫酸アンモニウム水溶液２７０ｇを加えて液温を３０℃に保ちながら５分間各般した後に１時間静置して、水相（下層）と有機溶媒溶液相（上層）に層分離させ、下層を分取して除去した。
（iii） 上記（ii）で回収した有機溶媒溶液相に、ハイドロキノンモノメチルエーテル（ＭＱ）４２０ｐｐｍを添加して、オイルバスの温度を８０℃に設定し、酸素を含む窒素ガスを吹き込みながら、減圧下（５ｋＰａ）に、トルエンの濃度が１質量％以下になるまで蒸留処理（脱溶媒処理）して、多官能アクリレート５１５ｇを得た。これにより得られた多官能アクリレートの粘度を、上記した方法で測定したところ、下記の表１に示すように５７８０ｍＰａ・ｓであった。
(2) Post-processing process:
(I) After cooling 1420 g of the reaction solution obtained in the above (1) to 30 ° C., 770 g of toluene was added for dilution, transferred to a tank for neutralization treatment, and 730 g of 4% aqueous ammonium sulfate solution was added to add 5 After stirring for 30 minutes and washing with water, the mixture was allowed to stand for 30 minutes to separate the aqueous phase (lower layer) and the organic solvent solution phase (upper layer), and the lower aqueous phase was removed. The acid value of the organic solvent solution phase was measured and found to be 0.80 meq / g.
(Ii) Next, 520 g of a 20% sodium hydroxide aqueous solution was added to the organic solvent solution phase, and the mixture was stirred for 10 minutes while maintaining the liquid temperature at 30 ° C. to neutralize the acid component contained in the organic solvent solution phase, and then for 30 minutes. The mixture was allowed to stand and separated into an aqueous phase (lower layer) and an organic solvent solution phase (upper layer). The lower aqueous phase was removed and the organic solvent solution phase was recovered to find 1900 g. 270 g of 4% ammonium sulfate aqueous solution was added to the recovered organic solvent solution phase, and the solution temperature was kept at 30 ° C. for 5 minutes, and then allowed to stand for 1 hour, to the aqueous phase (lower layer) and the organic solvent solution phase (upper layer). The layers were separated and the lower layer was separated and removed.
(Iii) To the organic solvent solution phase recovered in (ii) above, 420 ppm of hydroquinone monomethyl ether (MQ) was added, the temperature of the oil bath was set to 80 ° C., and nitrogen gas containing oxygen was blown under reduced pressure. (5 kPa) was distilled (desolvent treatment) until the concentration of toluene was 1% by mass or less to obtain 515 g of a polyfunctional acrylate. When the viscosity of the polyfunctional acrylate thus obtained was measured by the method described above, it was 5780 mPa · s as shown in Table 1 below.
《実施例４》
（１） 実施例３の（１）のエステル化反応工程において、反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）が２０℃になるように、オイルバスの温度を微調整しながら全体で６．５時間エステル化反応を行なった以外は、実施例３の（１）と同様にしてエステル化反応を行なった。
この実施例４では、反応開始２４０分後にエステル化反応の反応率が８０％に到達し、反応開始から反応率が８０％に到達する時点までの反応液中の水分量は０．５〜２．３質量％の範囲に保たれていた（最大の水分量＝２．３質量％、反応率８０％の時点での水分量＝０．５質量％）。
エステル化反応を停止した反応開始６．５時間後の時点で、反応液の水分量は０．１質量％であり、反応器内の反応液の質量は１４２０ｇ、酸価は２．３５ｍｅｑ／ｇであり、上記した方法で求めた反応率は９９％であった。
（２） 続いて、上記（１）で生成した反応液を、実施例３の（２）と同様に後処理して、多官能アクリレートを製造した。これにより得られた多官能アクリレートの粘度を、上記した方法で測定したところ、下記の表１に示すように４０００ｍＰａ・ｓであった。
Example 4
(1) in the esterification reaction step (1) of Example 3, the temperature difference between the reaction temperature and (T A) and the oil bath temperature (T B) (ΔT) ( T B -T A) is 20 The esterification reaction was carried out in the same manner as (1) of Example 3 except that the esterification reaction was conducted for a total of 6.5 hours while finely adjusting the temperature of the oil bath so that the temperature was 0 ° C.
In Example 4, the reaction rate of the esterification reaction reached 80% 240 minutes after the start of the reaction, and the amount of water in the reaction solution from the start of the reaction until the reaction rate reached 80% was 0.5-2. It was kept in the range of 3% by mass (maximum water content = 2.3% by mass, water content at a reaction rate of 80% = 0.5% by mass).
At 6.5 hours after the start of the reaction when the esterification reaction was stopped, the water content of the reaction solution was 0.1% by mass, the mass of the reaction solution in the reactor was 1420 g, and the acid value was 2.35 meq / g. The reaction rate determined by the above method was 99%.
(2) Subsequently, the reaction solution produced in (1) above was post-treated in the same manner as (2) in Example 3 to produce a polyfunctional acrylate. When the viscosity of the polyfunctional acrylate thus obtained was measured by the method described above, it was 4000 mPa · s as shown in Table 1 below.
《実施例５》
（１） 実施例１の（１）のエステル化反応工程において、反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）が４０℃になるように、オイルバスの温度を微調整しながら全体で４時間エステル化反応を行なった以外は、実施例１の（１）と同様にしてエステル化反応を行なった。
この実施例５では、反応開始１８０分後にエステル化反応の反応率が８０％に到達し、応開始から反応率が８０％に到達する時点までの反応液中の水分量は０．２〜０．３質量％の範囲に保たれていた（最大の水分量＝０．３質量％、反応率８０％の時点での水分量＝０．２質量％）。
エステル化反応を停止した反応開始４時間後の時点で、反応液の水分量は０．１質量％であり、反応器内の反応液の質量は１４２０ｇ、酸価は２．３５ｍｅｑ／ｇであり、上記した方法で求めた反応率は９９％であった。
（２） 続いて、上記（１）で生成した反応液を、実施例１の（２）と同様に後処理して、多官能アクリレートを製造した。これにより得られた多官能アクリレートの粘度を、上記した方法で測定したところ、下記の表１に示すように３８００Ｐａ・ｓであった。
Example 5
(1) in the esterification reaction step (1) of Example 1, the temperature difference between the reaction temperature and (T A) and the oil bath temperature (T B) (ΔT) ( T B -T A) is 40 The esterification reaction was carried out in the same manner as in Example 1 (1) except that the esterification reaction was carried out for 4 hours in total while finely adjusting the temperature of the oil bath so that the temperature became 0 ° C.
In Example 5, the reaction rate of the esterification reaction reached 80% 180 minutes after the start of the reaction, and the water content in the reaction solution from the start of the reaction until the time when the reaction rate reached 80% was 0.2-0. It was kept in the range of 3% by mass (maximum water content = 0.3% by mass, water content at a reaction rate of 80% = 0.2% by mass).
At 4 hours after the start of the esterification reaction, the water content of the reaction solution is 0.1% by mass, the mass of the reaction solution in the reactor is 1420 g, and the acid value is 2.35 meq / g. The reaction rate determined by the above method was 99%.
(2) Subsequently, the reaction solution produced in (1) above was post-treated in the same manner as in (2) of Example 1 to produce a polyfunctional acrylate. When the viscosity of the polyfunctional acrylate thus obtained was measured by the method described above, it was 3800 Pa · s as shown in Table 1 below.
《実施例６》
（１） 実施例３の（１）のエステル化反応工程において、反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）が５０℃になるように、オイルバスの温度を制御しながら全体で４時間エステル化反応を行なった以外は、実施例３の（１）と同様にしてエステル化反応を行なった。
この実施例６では、反応開始１８０分後にエステル化反応の反応率が８０％に到達し、反応開始から反応率が８０％に到達する時点までの反応液中の水分量は０．１〜０．２質量％の範囲に保たれていた（最大の水分量＝０．２質量％、反応率８０％の時点での水分量＝０．１質量％）。
エステル化反応を停止した反応開始４時間後の時点で、反応液の水分量は０．２質量％で、反応器内の反応液の質量は１４２０ｇ、酸価は２．３５ｍｅｑ／ｇであり、上記した方法で求めた反応率は９９％であった。
（２） 続いて、上記（１）で生成した反応液を、実施例３の（２）と同様に後処理して、多官能アクリレートを製造した。これにより得られた多官能アクリレートの粘度を、上記した方法で測定したところ、下記の表１に示すように３８００ｍＰａ・ｓであった。
この実施例６では、エステル化反応を停止した段階での反応率は実施例５と同じように９９％であり、また得られた多官能アクリレートの粘度が３８００ｍＰａ・ｓであって、実施例５と同じであったが、エステル化反応時の反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）を５０℃と大きくしたことにより、エステル化反応に要した熱量が、実施例５の１．２５倍であった。
Example 6
(1) in the esterification reaction step (1) of Example 3, the temperature difference between the reaction temperature and (T A) and the oil bath temperature (T B) (ΔT) ( T B -T A) is 50 The esterification reaction was performed in the same manner as in (1) of Example 3 except that the esterification reaction was performed for 4 hours in total while controlling the temperature of the oil bath so that the temperature became 0 ° C.
In Example 6, the reaction rate of the esterification reaction reached 80% 180 minutes after the start of the reaction, and the amount of water in the reaction solution from the start of the reaction until the time when the reaction rate reached 80% was 0.1-0. .2% by mass (maximum water content = 0.2% by mass, water content at a reaction rate of 80% = 0.1% by mass).
At 4 hours after the start of the reaction when the esterification reaction was stopped, the water content of the reaction solution was 0.2% by mass, the mass of the reaction solution in the reactor was 1420 g, and the acid value was 2.35 meq / g. The reaction rate determined by the above method was 99%.
(2) Subsequently, the reaction solution produced in (1) above was post-treated in the same manner as (2) in Example 3 to produce a polyfunctional acrylate. When the viscosity of the polyfunctional acrylate thus obtained was measured by the method described above, it was 3800 mPa · s as shown in Table 1 below.
In Example 6, the reaction rate at the stage where the esterification reaction was stopped was 99% as in Example 5, and the viscosity of the obtained polyfunctional acrylate was 3800 mPa · s. The temperature difference (ΔT) (T B −T A ) between the reaction liquid temperature (T A ) and the oil bath temperature (T B ) during the esterification reaction was increased to 50 ° C. The amount of heat required for the esterification reaction was 1.25 times that of Example 5.
《比較例１》
（１） 実施例３の（１）のエステル化反応工程において、反応液の温度（ＴA）とオイルバスの温度（ＴB）との温度差（ΔＴ）（ＴB−ＴA）が４℃になるように、オイルバスの温度を微調整しながら酸価の変化がなるまで全体で３０時間エステル化反応を行なった以外は、実施例３の（１）と同様にしてエステル化反応を行なった。
この比較例１では、反応開始１２００分後にエステル化反応の反応率が８０％に到達し、反応開始から反応率が８０％に到達する時点までの反応液中の水分量は５〜６質量％の範囲であった（最大の水分量＝６質量％、反応率８０％の時点での水分量＝５質量％）。
エステル化反応を停止した反応開始３０時間後の時点で、反応液の水分量は０．５質量％であり、反応器内の反応液の質量は１５００ｇ、酸価は２．５５ｍｅｑ／ｇであり、上記した方法で求めた反応率は９３％であった。
（２） 上記（１）で生成した反応液を、実施例３の（２）と同様に後処理しようとしたところ、中和後、４％硫酸アンモニウム水溶液で洗浄した時点で、水相と有機溶媒溶液相が乳化してしまい、下層（水相）と上層（有機溶媒溶液相）に層分離しなかったため、有機溶媒溶液相を回収できず、多官能アクリレートを得ることができなかった。
<< Comparative Example 1 >>
(1) in the esterification reaction step (1) of Example 3, the temperature difference between the reaction temperature and (T A) and the oil bath temperature (T B) (ΔT) ( T B -T A) is 4 The esterification reaction was carried out in the same manner as (1) of Example 3 except that the esterification reaction was performed for 30 hours in total until the acid value changed while finely adjusting the temperature of the oil bath so that the oil bath temperature was I did it.
In Comparative Example 1, the reaction rate of the esterification reaction reached 80% 1200 minutes after the start of the reaction, and the water content in the reaction solution from the start of the reaction until the time when the reaction rate reached 80% was 5 to 6% by mass. (Maximum water content = 6% by mass, water content at a reaction rate of 80% = 5% by mass).
At 30 hours after the start of the reaction when the esterification reaction was stopped, the water content of the reaction solution was 0.5% by mass, the mass of the reaction solution in the reactor was 1500 g, and the acid value was 2.55 meq / g. The reaction rate determined by the above method was 93%.
(2) When the reaction solution produced in (1) was to be post-treated in the same manner as in (2) of Example 3, the aqueous phase and the organic solvent were washed after washing with 4% ammonium sulfate aqueous solution after neutralization. Since the solution phase was emulsified and the layers were not separated into a lower layer (aqueous phase) and an upper layer (organic solvent solution phase), the organic solvent solution phase could not be recovered and a polyfunctional acrylate could not be obtained.
表１の実施例１〜６の結果にみるように、エステル化反応時に反応率が８０％に到達する段階まで反応液の水分量を５質量％以下にすることにより、多官能アクリレートを円滑に得ることができる。また、その際に、反応液の水分量を５質量％以下という要件を満たしながら変えることで、低粘度、中粘度、高粘度というように、それぞれ所望の粘度の多官能アクリレートを製造することができる。特に、エステル化反応時に反応率が８０％に到達する段階まで反応液の水分量を０．２〜５質量％の範囲に制御した実施例１〜５では、エステル化反応時の熱効率を良好に保ちながら、目的とする多官能アクリレートを円滑に得ることができた。
一方、比較例１では、エステル化反応の反応率が８０％に到達する段階まで反応液の水分量が５質量％を超えていることにより、多官能アクリレートを円滑に得ることができない。
As can be seen from the results of Examples 1 to 6 in Table 1, the polyfunctional acrylate is made smooth by reducing the water content of the reaction solution to 5% by mass or less until the reaction rate reaches 80% during the esterification reaction. Obtainable. At that time, by changing the water content of the reaction solution while satisfying the requirement of 5% by mass or less, a polyfunctional acrylate having a desired viscosity such as low viscosity, medium viscosity, and high viscosity can be produced. it can. In particular, in Examples 1 to 5 in which the water content of the reaction solution was controlled in the range of 0.2 to 5% by mass until the reaction rate reached 80% during the esterification reaction, the thermal efficiency during the esterification reaction was improved. The desired polyfunctional acrylate could be obtained smoothly while maintaining.
On the other hand, in Comparative Example 1, the polyfunctional acrylate cannot be obtained smoothly because the water content of the reaction solution exceeds 5% by mass until the reaction rate of the esterification reaction reaches 80%.
本発明の方法により、（メタ）アクリル酸および５価以上の多価アルコールを原料として用いて、低粘度品、中粘度品、高粘度品というように、所望の粘度を有する多官能（メタ）アクリレートを高い収率で円滑に製造することができるので、本発明は多官能（メタ）アクリレートの製造方法として有用である。
本発明の方法により得られる多官能（メタ）アクリレートは、インキ、塗料、刷板、フォトレジスト、光学フィルム用接着剤などの用途に有効に用いることができる。
Using the method of the present invention, a polyfunctional (meth) having a desired viscosity such as a low-viscosity product, a medium-viscosity product, or a high-viscosity product using (meth) acrylic acid and a polyhydric alcohol having a valence of 5 or higher Since the acrylate can be produced smoothly at a high yield, the present invention is useful as a method for producing a polyfunctional (meth) acrylate.
The polyfunctional (meth) acrylate obtained by the method of the present invention can be effectively used for applications such as inks, paints, printing plates, photoresists and optical film adhesives.
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