WO2007000920A1

WO2007000920A1 - Polyfunctional (meth)acrylic ester composition and process for producing the same

Info

Publication number: WO2007000920A1
Application number: PCT/JP2006/312377
Authority: WO
Inventors: Toshiyuki Wakayama; Shinji Kojima; Masayoshi Yoshikawa; Kouji Kimura
Original assignee: Toagosei Co., Ltd.
Priority date: 2005-06-27
Filing date: 2006-06-21
Publication date: 2007-01-04
Also published as: JPWO2007000920A1; JP4998263B2; TW200700380A

Abstract

A polyfunctional (meth)acrylic ester composition which comprises: an ingredient (A), as the main component, which is a compound having two or more (meth)acryloyloxy groups; and an ingredient (B), as a secondary component, which is a compound having a structure formed from the ingredient (A) by replacing any one of the (meth)acryloyloxy groups with a group represented by the following chemical formula (1). The content of the ingredient (B) in the polyfunctional (meth)acrylic ester composition is 1,000 ppm or lower. [In the chemical formula (1), R1 represents hydrogen or methyl.]

Description

Specification

Multifunctional (meth) acrylic acid ester composition and method for producing the same

Technical field

The present invention relates to a (meth) acrylic acid ester composition having two or more (meth) acryloyl groups, for example, used in the field of paints, adhesives, and printing inks, and a method for producing the same. In the present application, an acrylic acid ester or a methacrylic acid ester is referred to as a (meth) acrylic acid ester, and an allyloyloxy group or a methacryloyloxy group is referred to as a (meth) atarylloyoxy group.

Background art

[0002] In recent years, for example, in the fields of paints, adhesives, and printing inks, the use of UV curable or electron beam curable agents has increased from the viewpoints of environmental protection, resource saving, energy saving, and the like. I am doing. For example, a (meth) acrylic acid ester having two or more (meth) atalyloyl groups (referred to as polyfunctional (meth) acrylic acid ester in the present application) is a reactive diluent for ultraviolet curable resin or electron beam curable resin. Widely used. In particular, the polyfunctional (meth) acrylic acid ester obtained by (meth) atarily brewing trimethylolpropane, pentaerythritol, dipentaerythritol and their derivatives has features such as fast curability and high hardness. And its usage is increasing.

[0003] Conventionally, polyfunctional (meth) acrylic acid esters are produced by an esterification reaction of polyhydric alcohol and (meth) acrylic acid in the presence of an acid catalyst such as sulfuric acid, methanesulfonic acid, para-toluenesulfonic acid and the like. Is done. In the reaction product thus obtained, catalyst, unreacted substances, and side reactants remain, so that purification is performed by subjecting the reaction solution to various post-treatments. For example, neutralization treatment is performed for the purpose of removing unreacted (meth) acrylic acid and acid catalyst in the reaction solution. In this neutralization treatment, 1 to 25% concentration of sodium hydroxide (caustic soda) is used. ) Aqueous solutions and aqueous sodium carbonate (sodium carbonate) solutions are used. Further, the reaction solution is purified using water.

[0004] Specifically, a hydroxyl group-containing (meth) acrylate ligomer is produced by addition polymerization of a hydroxyl group-containing (meth) acrylate in the presence of a catalyst. In this case, a method is disclosed in which the reaction solution is brought into contact with an adsorbent such as magnesium silicate, or the reaction solution is purified using an alkaline aqueous solution (see, for example, Patent Document 1). In addition, a method for producing a polyfunctional (meth) acrylic acid ester as described below is disclosed (for example, see Patent Document 2). That is, in the presence of an acid catalyst, a polyhydric alcohol and (meth) acrylic acid undergo an esterification reaction in an organic solvent to obtain a reaction product. Next, the reaction product is subjected to a neutralization treatment and further subjected to a purification treatment using amines.

[0005] By the way, in the production of polyfunctional (meth) acrylic acid esters, in order to further increase the density of (meth) atallyloyl groups, the esterification reaction is usually performed with monofunctional (meth) acrylic acid esters. It takes longer time than production or at higher reaction temperature. When the esterification reaction is carried out under such conditions, a side reaction peculiar to (meth) acrylic acid ester occurs and a side reaction product is generated.

[0006] On the other hand, in the post-treatment after the esterification reaction, an emulsification phenomenon occurs in which the separation between the organic layer and the aqueous layer is insufficient in the neutralization step of the reaction solution and the washing step using water. There is. When such an emulsification phenomenon occurs, it takes a long time to separate the organic layer from the aqueous layer, resulting in a decrease in productivity, and further in a state where the separation between the organic layer and the aqueous layer is insufficient. When they are separated, there has been a problem that the purity is lowered due to impurities in the final product. The cause of such emulsification was suspected to be due to the side reaction product. In order to remove such side reaction products (hereinafter referred to as emulsifying compounds), physical adsorption is performed in the method using the adsorbent described in Patent Document 1. However, this method could not sufficiently remove the emulsifiable complex from the reaction product.

[0007] In addition, according to the method described in Patent Document 2, an acid catalyst derivative such as a sulfonic acid ester is decomposed in a treatment step using amines (see Patent Document 2). Therefore, this method does not pay attention to the decomposition of the emulsifying compound that causes emulsification, and has been unable to sufficiently decompose and remove the emulsifying compound. Therefore, the emulsifying compound is removed! In addition, when it is used in applications that require emulsification resistance such as ink, such as polyfunctional (meth) acrylic ester, When various harmful effects such as pollution There was a problem.

Patent Document 1: Japanese Patent Laid-Open No. 61-134350

Patent Document 2: JP-A-6-219991

Disclosure of the invention

[0008] The present invention has been made in view of the above-described problems, and is a polyfunctional (meth) attalic acid capable of suppressing the adverse effects caused by emulsification that cause insufficient separation of the organic layer and the aqueous layer in the post-treatment step. It aims at providing an ester composition and its manufacturing method.

[0009] In one embodiment of the present invention, a polyfunctional (meth) acrylic acid ester composition is provided. The polyfunctional (meth) acrylic acid ester composition is composed of a compound having two or more (meth) ataryloxy groups as the main component (A), and the above component (B) as a subcomponent. The compound (A) may contain a compound in which one shift force of the (meth) ataryloxy group in the component is substituted with a group represented by the following chemical formula (1). The content of component (B) in the polyfunctional (meth) acrylic ester composition is lOOOppm or less.

[0010] [Chemical 1]

R ¹

I

― 0— CH ₂ CH-COOH ■ ■ ■ (1)

[In the chemical formula (1), R ¹ represents a hydrogen atom or a methyl group. ]

According to this configuration, any one of the (meth) ataryloxy groups in component (A) is substituted with the group represented by chemical formula (1), and component (B) corresponds to a compound exhibiting emulsifying properties. In addition, since its content is lOOOppm or less, it reduces emulsifying compounds and suppresses adverse effects caused by emulsification that causes insufficient separation of the organic layer and aqueous layer in the post-treatment process. It can be done.

[0012] The component (A) is preferably a compound having three or more (meth) ataryloxy groups. Furthermore, the component (A) is more preferably dipentaerythritol penta (meth) acrylic acid ester or dipentaerythritol hexa (meth) acrylic acid ester, and the component (B) is preferably represented by the following chemical formula (2). It is a compound represented. According to this configuration, dipenta The above-mentioned effects can be exerted on polyfunctional (meth) acrylates of erythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate.

[0013] [Chemical 2]

-COOH ■ ■. (2)

[In the chemical formula (2), R ¹ represents a hydrogen atom or a methyl group, and A to A ⁵ represent a (meth) atalyloyl group or a hydrogen atom. ]

In another aspect of the present invention, a method for producing the above-described polyfunctional (meth) acrylate composition is provided. This production method comprises a step of producing a polyfunctional (meth) acrylate composition by reacting a polyhydric alcohol and (meth) acrylic acid in an organic solvent in the presence of an acid catalyst. In the polyfunctional (meth) acrylic acid ester composition (

And B) purifying the polyfunctional (meth) acrylic acid ester composition so that the content of the component is 1OOOppm or less. According to this configuration, the multifunctional (meth) acrylate composition having the above-described effects can be easily obtained by purifying the polyfunctional (meth) acrylate composition using the component (B) as an index. Can be manufactured.

[0015] The step of purifying the polyfunctional (meth) acrylic acid ester composition preferably includes a step of neutralizing the reaction solution after the esterification reaction and a step of saponifying the treatment solution after the neutralization treatment. . The step of purifying the polyfunctional (meth) acrylic acid ester composition is preferably a step of washing the reaction solution after the esterification reaction, a step of neutralizing the treatment solution after the washing treatment, and a neutralization step. Including a step of saponifying the treated liquid after the treatment. According to these structures, the polyfunctional (meth) acrylic acid ester composition having it can be more easily produced.

[0016] In the step of purifying the polyfunctional (meth) acrylic acid ester composition, an alkaline aqueous solution is used. The polyfunctional (meth) acrylic acid ester composition is saponified. According to this configuration, the polyfunctional (meth) acrylic acid ester composition can be purified efficiently. Brief Description of Drawings

FIG. 1 is a chart showing an NMR spectrum of the residue of Synthesis Example 1.

FIG. 2 is a chart showing an IR spectrum for the residue of Synthesis Example 1.

FIG. 3 is a chart showing a MALDI-TOFMS spectrum of the residue of Synthesis Example 1.

FIG. 4 is a chart showing a MALDI-TOFMS spectrum for the residue (methyl esterified) in Synthesis Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Hereinafter, embodiments of the present invention will be described in detail.

[0019] The polyfunctional (meth) acrylic acid ester composition of the present embodiment is composed of a compound having two or more (meth) ataryloxy groups as the main component (A), and a subcomponent. As a certain (B) component, at least one of the (meth) ataryloxy groups in the component (A) contains a compound substituted with a group represented by the following chemical formula (1). The content of component (B) in the polyfunctional (meth) acrylic acid ester composition is lOOOOppm or less. The content of component (B) is measured by high performance liquid chromatography (hereinafter referred to as HPLC). Specifically, the content of component (B) is measured under the following conditions.

[0020] Detector: UV detector

Column type: ODS column

Column temperature: 40 ° C

Eluent: acidic aqueous solution Z methanol system (pH of acidic aqueous solution is preferably 2 to 3. As acidic aqueous solution, aqueous phosphoric acid solution is preferred.)

[0021] [Chemical 3]

R ¹

I

— 0— CH „CH-COOH ■ ■ ■ (1)

[In the chemical formula (1), R ¹ represents a hydrogen atom or a methyl group. ] During the production of polyfunctional (meth) acrylic acid esters, various side-reactions occur due to high-temperature and long-time esterification reactions, and various emulsifiable compounds are produced. It is one of the emulsifying compounds and a compound that causes emulsification.

A A

[0023] The (A) component A is preferably a compound having 3 or more (meth) ataryloxy groups

2

It is. Examples of component (A) and OI include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) ) Acrylic acid ester, dipentaerythritol penta (meth) acrylic acid ester, and dipentaerythritol hexa (meth) acrylic acid ester.

[0024] The component (A) is trimethylolpropane tri (me o C cl

In the case of a single acrylate ester, the compound represented by the following chemical formula (3) can be used as the component (B).

H.

[0025] [Chemical 4]

CH ₃ — HC— C—CH- -0-CH ₂ -CH-COOH (3)

[0026] When component (A) is ditrimethylolpropane tri or tetra (meth) acrylic acid ester, examples of component (B) include compounds represented by the following chemical formula (4).

[0027] [Chemical 5]

^CH 3 ^_ 2 ^C C -CH O CH CH (4)

CH R

A— o O-CH ₂ -CH-COOH [0028] When the component (A) is pentaerythritol tri or tetra (meth) acrylic acid ester, the component (B) includes a compound represented by the following chemical formula (5).

[0029] [Chemical 6]

A ² -0

1 I I

A ~ 0 ~ H ₂ CC-CH ₂ -o-CH ₂ -CH ~ COOH ■ ■ ■ (5)

CH ₂

A ³ -0

[0030] When the component (A) is dipentaerythritol penta or hexa (meth) acrylic acid ester, examples of the component (B) include compounds represented by the following chemical formula (2).

[0031] [Chemical 7]

A ² —◦ 0-A ⁴

I I

^ ^H 2 CH _{2 R} 1

1 i I I

A -0-H ₂ CC-CH ₂ -0-CH ₂ -C-CH ₂ -0-CH ₂ -CH-COOH ■. ■ (2)

CH ₂ CH,

_Λ3 II,

A ³ -0 OA ⁵

In chemical formulas (2) to (5), R ¹ represents a hydrogen atom or a methyl group, and Ai to A ⁵ each represents a (meth) ataryloyl group or a hydrogen atom.

[0033] Next, a method for producing a polyfunctional (meth) acrylic acid ester composition will be described.

[0034] The (meth) acrylic acid ester composition is produced through an esterification reaction step and a subsequent purification step. In the esterification reaction step, a polyfunctional (meth) acrylic acid ester composition is produced by an esterification reaction between polyhydric alcohol and (meth) acrylic acid in an organic solvent in the presence of an acid catalyst. The In the purification step, the polyfunctional (meth) acrylic acid ester composition is purified so that the proportion of the component (B) in the polyfunctional (meth) acrylic acid ester composition is lOOOppm or less. Hereinafter, both steps will be described in order. [Estery soot reaction process]

The esterification reaction in this esterification reaction step is carried out according to a conventional method for producing a polyfunctional (meth) acrylic acid ester. That is, the esterification reaction is performed by dehydration condensation of a polyhydric alcohol and (meth) acrylic acid in an organic solvent in the presence of an acid catalyst.

[0035] Examples of the polyhydric alcohol include dihydric alcohols, branched or linear long-chain alkyl diols, polyalkylene glycols, bisphenols, and bisphenol-containing alkylene oxides, polyols, and polyols. Carotenes with alkylene oxide and tris-2-hydroxyethylisocyanurate are mentioned. Examples of the divalent alcohol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, and neopentyl glycol. Examples of the branched or linear long-chain alkyl diol include hydrogenated polybutadiene diol. Examples of the polyalkylene glycol include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol. Examples of bisphenol include bisphenol A and bisphenol F. Examples of the polyol include glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Among the specific examples of the polyhydric alcohols described above, since the (meth) atallyloyl group has a high density and a polyfunctional (meth) acrylic acid ester is obtained, the alcohol having 3 to 6 hydroxyl groups or an alkylene oxide thereof is attached. Addenda are preferred.

[0036] The (meth) acrylic acid is acrylic acid or methacrylic acid, and these are selected depending on whether the target ester is a polyfunctional acrylic ester or a polyfunctional methacrylate. The amount of (meth) acrylic acid used is adjusted with respect to 1 mol of all hydroxyl groups of the polyhydric alcohol so that the resulting polyfunctional (meth) acrylic acid ester has the desired hydroxyl value.

[0037] Examples of the acidic catalyst include sulfuric acid, p-toluenesulfonic acid, and methanesulfonic acid. Can be mentioned. The reaction temperature can be appropriately set according to the raw materials used and the purpose, but the viewpoint and power for shortening the reaction time and preventing polymerization are preferably 65 to 140 ° C, more preferably 75 to 120 ° C. If the reaction temperature is less than 65 ° C, the esterich reaction may be slowed or the yield may be lowered. If the reaction temperature exceeds 140 ° C, thermal polymerization of (meth) attalic acid or the resulting polyfunctional (meth) acrylate may occur.

[0038] In the esterification reaction, an organic solvent that forms an azeotrope with water produced by this reaction is used, and an organic solvent that promotes dehydration by azeotropically distilling water is preferably used. Preferred organic solvents include, for example, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones. Examples of aromatic hydrocarbons include toluene, benzene, and xylene. Examples of the aliphatic hydrocarbon include hexane and heptane. Examples of the ketone include methyl ethyl ketone and cyclohexanone. The amount of the organic solvent used is preferably 0.1 to 10 times (mass ratio), more preferably 2 to 5 times the total amount of the polyhydric alcohol and (meth) acrylic acid. This organic solvent may be distilled off by a decompression operation after the reaction or after the post-treatment, but when an organic solvent that does not have a problem of odor is used, it is necessary to adjust the viscosity of the composition. It may remain in the composition without being distilled off.

[0039] The esterification reaction is preferably carried out under normal pressure (0. IMPa) or reduced pressure. Further, for the purpose of preventing thermal polymerization of (meth) acrylic acid or the produced polyfunctional (meth) acrylic ester, it is preferable that the esterification reaction is carried out in the presence of oxygen. For the same purpose, a polymerization inhibitor is preferably added to the reaction solution. Such polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, 2,4 dimethyl 6-t-butylphenol, 3-hydroxythiophenol, ex-troso / 3 naphthol, p-benzozoquinone, and copper salts. It is done. The addition amount of the polymerization inhibitor is preferably 0.001 to 5.0% by mass with respect to the raw material (meth) acrylic acid, and more preferably 0.01 to L 0% by mass. When the addition amount of the polymerization inhibitor is less than 0.001% by mass, the polymerization inhibition effect tends to be insufficient. Even if the addition amount of the polymerization inhibitor exceeds 5.0% by mass, the polymerization inhibition effect does not improve any more, so excessive polymerization inhibitor tends to be wasted. . As a method for confirming the degree of progress of the esterification reaction, for example, there is a method of monitoring the remaining amount of (meth) acrylic acid and polyhydric alcohol. The amount of water produced by the esterification reaction, that is, the amount of dehydration is monitored. The method is preferred.

t Purification step)

Next, a purification process for removing the component (B) from the reaction product obtained in the esterification reaction step will be described. This purification process includes a neutralization treatment process, a saponification treatment process, a water washing treatment process, and a solvent removal treatment process.

(Neutralization process)

The neutralization treatment step is performed for the purpose of removing, for example, unreacted (meth) acrylic acid and the acid content of the acid catalyst in the reaction solution after the esterification reaction in the esterification reaction step.

[0040] The neutralization treatment step is performed according to a conventional method. Examples of the conventional method include a method in which an alkaline aqueous solution as an alkali component is added to the reaction solution and then stirred and mixed. Examples of the alkaline aqueous solution include a sodium hydroxide aqueous solution. In this case, the amount of the alkali component is usually 1 or more times in molar ratio with respect to the acid content of the reaction solution, and preferably 1.1 to 1.6 times. If this added amount is less than 1 time in molar ratio to the acid content of the reaction solution, neutralization of the acid content may be insufficient. The concentration of the aqueous alkaline solution is preferably 1 to 25% by mass, more preferably 10 to 25% by mass. If the concentration of the alkaline aqueous solution is less than 1% by mass, the amount of wastewater after neutralization may increase. When the concentration of the alkaline aqueous solution exceeds 25% by mass, the polyfunctional (meth) acrylic acid ester may be polymerized. The stirring and mixing time is preferably 5 to 60 minutes.

(Saponification process)

In the neutralization treatment step, the acid catalyst and unreacted (meth) acrylic acid are removed, but the emulsifying compound such as component (B) is not sufficiently removed.

[0041] Examples of the method for removing the emulsifying dig compound such as the component (B) include a method using an adsorbent such as calcium ichthy and an ion exchange resin such as a styrene-dibutylbenzene copolymer. . However, since the removal efficiency is high and industrially advantageous, the treatment solution is further stirred by adding an aqueous alkaline solution to the treatment solution after the neutralization treatment. A method of saponifying the liquid is preferred.

[0042] The neutralization treatment step and the saponification treatment step may be performed together! Or may be performed separately. When the neutralization treatment step and the saponification treatment step are performed together, the alkali component is added to the reaction product in excess of the amount necessary for neutralization. Specifically, it is preferable to use an alkali component at least 1.4 times the amount necessary for neutralization. The treatment time is preferably 10 minutes or more including the charging time. The treatment temperature is preferably 20 to 70 ° C. in consideration of heat of neutralization. When a high concentration alkaline aqueous solution is used, it is necessary to pay attention to polymerization and salting out because the concentration of sodium (meth) acrylate increases during the treatment process.

[0043] Next, the case where the neutralization treatment step and the saponification treatment step are performed separately will be described.

[0044] In the saponification treatment in the saponification treatment step, emulsification of the component (B) and the like by treatment with an alkali as an organic layer strength saponification treatment agent obtained after the neutralization treatment step or after the water washing treatment step described later. The saponification reaction between the chemical compound and the alkali is carried out, and the emulsifying compound such as component (B) is decomposed. This saponification treatment step is performed separately from the neutralization treatment step, so that the saponification reaction can be effectively performed.

[0045] Examples of the saponification treatment method include a method in which a saponification agent is added to the organic layer obtained after the neutralization treatment or after the water washing treatment described later and stirred and mixed.

In this saponification treatment step, the concentration, amount, stirring time, and treatment temperature of the alkaline aqueous solution as the saponification treatment agent to be charged can be selected widely. For this reason, the saponification treatment is carried out by converting the ester bond of the ester having a carboxyl group (B) with the corresponding (meth) acrylic acid (substantially (meth) acrylic alkali metal salt) and polyhydric alcohol. Hydrolyzes to The decomposition products are removed by dissolving in water.

[0047] As the alkali used as the saponification agent, an aqueous alkali solution is preferred. Examples of the alkali component in the aqueous alkali solution include alkali metal salts and alkaline earth metal salts, and examples thereof include alkali metal hydroxides, alkali metal carbonates, and alkaline earth metal hydroxides. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of the alkali metal carbonate include sodium carbonate. Can be mentioned. Examples of the alkaline earth metal hydroxide include hydroxide calcium. Among these, alkali metal hydroxides are preferable because the effect of the saponification treatment is high. The concentration of the alkaline aqueous solution is preferably 1 to 25% by mass, more preferably 10 to 25% by mass. The amount of alkali used is more preferably 0.5 to 2 times in consideration of the size of the treatment tank and the amount of drainage, which is preferably 0.2 to 4 times the amount of alkali used during the neutralization treatment. The saponification treatment is preferably performed under stirring, and the stirring time is preferably 10 minutes to 3 hours. In this case, both treatments can be performed efficiently by using the same treatment agent as the neutralization treatment agent as the saponification treatment agent. The treatment temperature of the saponification treatment is preferably 20 to 70 ° C. because the saponification treatment of the emulsifiable compound can be easily performed at room temperature (20 ° C.) or with a little heating.

[0048] The saponification step can be completed by the treatment within the above-mentioned preferable conditions. The progress of the saponification step can be managed as required. Methods for controlling the degree of progress of the saponification treatment include a method of measuring the alkali number of the aqueous layer, the conductivity (electrical conductivity) of the organic layer, and the interfacial tension. Since the alkali number of the aqueous layer varies depending on, for example, the type of ester, the increase or decrease in side reactions, and the concentration of the aqueous alkali solution used, it is necessary to examine the transition of the alkali number for each production brand and formulation. In general, in the management method based on the alkali number, the point at which the variation of the alkali number during the saponification process becomes small can be used as a measure of the end of the saponification process.

[0049] The conductivity of the organic layer increases when the ionic component contained in the organic layer is large. In such a state, the emulsifiable compound is mainly present as an alkali metal salt. As the saponification reaction proceeds, the ionic components are decomposed and transferred from the organic layer to the alkaline aqueous solution layer. Therefore, as with the alkali number of the aqueous layer, the conductivity of the organic layer varies depending on the brand and formulation, but the point at which the variation in conductivity becomes small can be used as a guideline for the end of the saponification process.

[0050] The interfacial tension of the organic layer can also be considered in the same manner as the above-described alkali number and conductivity. When the emulsifying compound is present in the organic layer, the interfacial tension becomes small, but the interfacial tension increases as the emulsifying compound is decomposed and removed. For this reason, the fluctuation force of the interfacial tension and the time point when it has become short can be used as a guideline for the end of the saponification process. (Washing process)

In the present invention, the reaction solution or the treatment solution is preferably subjected to a water washing treatment. The water washing treatment can be performed on the reaction solution obtained by the esterification reaction, the neutralized organic layer, and the saponification organic layer. The point at which the water washing treatment is performed is appropriately selected according to the components used and the purpose.

[0051] The water washing treatment is performed according to a conventional method. Examples of the conventional method include a method in which water is added to the reaction solution obtained by the esterification reaction, the neutralized organic layer, and the saponified organic layer and stirred and mixed.

(Solvent removal process)

After the neutralization treatment, saponification treatment or water washing treatment, an organic layer (upper layer) containing the produced polyfunctional (meth) acrylic acid esters is obtained, and then the organic solvent is removed from this organic layer by a known method. As a result, a polyfunctional (meth) acrylic acid ester can be obtained.

[0052] In this solvent removal treatment step, oxygen is supplied to the organic layer or a polymerization inhibitor is added to the organic layer in order to suppress thermal polymerization of the polyfunctional (meth) acrylic acid ester. C or lower, and further processing is performed under reduced pressure. The polyfunctional (meth) acrylic acid ester can be purified by rectification as necessary.

(Application example for printing ink)

Next, the polyfunctional (meth) acrylic acid ester of the present embodiment is particularly suitably used as a printing ink, but in order to obtain a polyfunctional (meth) acrylic acid ester having excellent ink properties, a saponification treatment is performed. It is preferable that the process and the subsequent processing are performed as follows! /. That is, in the saponification treatment step, in order to promote the saponification reaction, saponification is performed under the conditions of a treatment temperature of 30 to 60 ° C. and a concentration of an alkaline aqueous solution of preferably 1 to 25% by mass, more preferably 10 to 25% by mass. Processing is performed.

[0053] In order to obtain a product having better dispersibility, the organic layer after the saponification treatment is preferably washed with acidic water. Examples of the acidic water include an ammonium sulfate aqueous solution, a salt ammonium aqueous solution, and a hydrochloric acid aqueous solution. As a result, sodium is also eliminated from compound forces containing sodium carboxylate (one COONa) produced by side reactions and neutralization. It is. By this treatment, the emulsifying compound having the form of an alkali metal salt becomes a compound having an acid structure, and then removed by a solvent removal treatment. By performing such treatment, an ink having excellent dispersibility of the ink pigment can be obtained.

[0054] Now, the operation of the present embodiment will be described. When the polyfunctional (meth) acrylic acid ester is produced, the reaction product produced by the esterification reaction in the esterification reaction step is neutralized. In addition, saponification is performed in the saponification process in the purification process. In this saponification treatment, the ester bond of the ester compound having a carboxyl group as the component (B) is hydrolyzed by alkali. Thereby, the component (B) is decomposed into water-soluble compounds such as (meth) acrylic acid and polyhydric alcohol. Thereafter, these decomposition products are dissolved in water and removed by washing with water. As a result, the content of component (B) in the (meth) acrylic acid ester composition can be suppressed to lOOOppm or less.

This embodiment has the following advantages.

[0056] The polyfunctional (meth) acrylic acid ester composition of the present embodiment includes a compound having two or more (meth) attayloxy groups as the main component (A) and a subcomponent. As a certain component (B), the compound contains a compound in which at least one of the (meth) ataryloxy groups in the component (A) is substituted with the group represented by the chemical formula (1)! / The content of the component (B) in the polyfunctional (meth) acrylic acid ester composition is lOOOppm or less. For this reason, it is possible to reduce the emulsifying compound and suppress the adverse effect of the emulsifying compound on the polyfunctional (meth) acrylic acid ester composition. As a result, when a polyfunctional (meth) acrylate is used in an ink, for example, it is possible to suppress ink bleeding and contamination of manufacturing equipment.

[0057] The component (A) is preferably a compound having three or more (meth) ataryloxy groups. Further, (A) component is dipentaerythritol penta (meth) acrylic acid ester or dipentaerythritol hex (meth) acrylic acid ester, and (B) component is a compound represented by the chemical formula (2). Therefore, the above-described effects can be sufficiently exerted with respect to those polyfunctional (meth) acrylic acid esters.

[0058] In the method for producing a polyfunctional (meth) acrylic acid ester composition, a polyfunctional alcohol and (meth) acrylic acid react with each other in an organic solvent in the presence of an acid catalyst. A (meth) acrylic ester composition is produced. Next, the polyfunctional (meth) acrylic acid ester composition is purified so that the proportion of the component (B) in the polyfunctional (meth) acrylic acid ester composition is lOOOppm or less. In this production method, the polyfunctional (meth) acrylic acid ester composition having the above-described effects is easily produced by purifying the polyfunctional (meth) acrylic acid ester composition using the component (B) as an index. be able to.

[0059] Therefore, the polyfunctional (meth) acrylic acid ester composition obtained as described above should be suitably used in fields such as paints and adhesives that require emulsification resistance in addition to printing inks. Can do.

Example

[0060] The embodiment will be described more specifically with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples.

(Synthesis Example 1)

In a 2L reactor equipped with a stirrer and a thermometer, dipentaerythritol 315g (l. 24 monole), kuzinoleic acid 643g (8.9 monole), 卜 noren 526g, salt 匕 cupric 1.5g, Esterui reaction was started by charging 15 g of 78% sulfuric acid and heating the reactor in an oil bath set at 100 ° C under a pressure of 53 kPa. Condensed water azeotroped with toluene was removed using a Dean-Stark apparatus and the esterification reaction proceeded, and the reaction was stopped after 8 hours. The weight of the reaction solution at this time was 1380 g, and the acid value was 1.75 meq / g.

[0061] The obtained reaction solution was cooled, and diluted by adding 740 g of toluene. The diluted reaction solution was transferred to a neutralization tank, 350 g of pure water was added and stirred for 5 minutes, and then allowed to stand for 30 minutes to separate the upper and lower layers.

[0062] To 700 g of the upper layer, 115 g of a 20% sodium hydroxide aqueous solution (equal molar amount with respect to the acid content in the upper layer) was added, stirred for 5 minutes, and allowed to stand for 30 minutes to separate the upper layer from the lower layer. . When the acid value of the upper layer was measured, the acid value was 0.82 meq / g.

[0063] The weight of the separated upper layer was 650 g. Using this solution (hereinafter referred to as “this solution”), the component (B) was isolated and analyzed.

[0064] Isolation and analysis of component (B)

The liquid obtained in Synthesis Example 1 was reduced in pressure and concentrated to obtain a residue. 2.5 g of this residue After dissolving in 15 ml of chill, it was extracted twice with 10 ml of 0.5% aqueous sodium carbonate solution. After the lower layers obtained by these extractions were combined, 1M hydrochloric acid was added to obtain an acidic aqueous solution with a pH of 1.5. The aqueous solution was extracted with 15 ml of ethyl acetate, and the upper layer obtained by this extraction was washed with 5 ml of distilled water, and dehydrated by adding anhydrous sodium sulfate lg. The ethyl acetate solution obtained after filtration was immersed in a hot water bath and concentrated to obtain 15 mg of residue.

[0065] For the obtained residue, oc =, proton NMR (nuclear magnetic resonance spectrum) analysis method, IR (infrared absorption spectrum) analysis method and MALDI-TOFMS (matrix-assisted laser desorption ionization mass spectrum) The analysis was performed by the analytical method. The obtained spectra are shown in Figs. Further, the residue was treated with DMF (dimethylformamide) dimethyl acetal and methyl esterified to analyze the sample by MALDI-TOFMS. The obtained spectrum is shown in FIG.

From the above analysis results, it was possible to confirm the compound represented by the following chemical formula (6), the compound represented by the chemical formula (7), and the compound represented by the chemical formula (8).

[0067] [Chemical 8]

CH. CH

[0068] [Chemical 9]

= CH

CH ₂ = CH -C-0-H ₂ CC-CH ₂ -o-CH ₂ -C-CH ₂ -0-CH ₂ ~ CH ₂ COOH

CH,

I '(7)

= CH -C-O O-C-CH: CH

II

o O [0069] [Chemical 10]

[0070] In the compound represented by the chemical formula (6) and the compound represented by the chemical formula (7), in the chemical formula (2), R ¹ represents a hydrogen atom, and A to A ⁵ Four compounds represent an allyloyl group and the remaining one represents a hydrogen atom. The compound represented by the chemical formula (8) is a compound in which, in the chemical formula (2), R ¹ represents a hydrogen atom and ^ to A ⁵ represent an allyloyl group.

[0071] 1) Figure 1 (Proton NMR ^ vector)

In Fig. 1, 2.5 to 2.6 ppm of signole is O-CH-CH-COOH (force nore

twenty two

Boric acid) derived from OC-methylene.

[Measurement equipment and conditions]

270MHz, JEOL JNM—EX270 type

Measuring conditions: Heavy black mouth form solution, 32 times of integration, normal temperature

2) Figure 2 (IR ^ vector)

In FIG. 2, 1721.7 cm ^_1 indicates absorption of an ester bond.

[0073] [Measurement equipment and conditions]

Made by Nicole, Impact -400D

Accessories: μ-ATR (SensIR Technology), diamond crystal once-reflection type

Measurement conditions: Resolution 4cm ^{_ 1} , Accumulation count 32 times

3) Figure 3 (MALDI-TOFMS spectrum)

In FIG. 3, mZz564 is represented by the compound represented by the chemical formula (6) and the chemical formula (7). In which sodium derived from an ionization aid is added.

[0074] mZz586 represents a compound represented by the chemical formula (6) and a sodium salt of the compound represented by the chemical formula (7) added with sodium derived from an ionic assistant.

[0075] mZz618 represents a compound obtained by adding sodium derived from an ionization aid to the compound represented by the chemical formula (8).

[0076] mZz640 represents a compound obtained by adding sodium derived from an ionization aid to the sodium salt of the compound represented by the chemical formula (8).

[0077] [Measurement equipment and conditions]

Equipment: PE biosystems, Voyager—DE RP type

Laser: N laser (λ = 337nm)

2

Accelerating voltage: 20kV

Measurement mode: Linear one mode

Ion to be measured: Positive ion

Sample preparation method

a) Dissolve 10 mg of each sample in 1 ml of acetone.

b) Matrix: Dissolve 10 mg of 2,5-dihydroxybenzoic acid (DHB) in 1 ml of acetone.

c) Ionic aid: 5 mg of sodium iodide is dissolved in 1 ml of acetone.

d) Collect 2 μ 1 of each of the solutions a) to c) and mix them, and drop 1 μ 1 of the mixture onto the sample plate for MALDI-TO FMS to form crystals.

[0078] 4) Figure 4 (MALDI-TOFMS spectrum after methyl ester derivatization)

In FIG. 4, mZz578 is a compound obtained by adding sodium derived from an ionic assistant to the carboxylated methylesterified compounds of the chemical formulas (6) and (7).

[0079] mZz632 represents a compound obtained by adding sodium derived from a ionic assistant to the carboxyl group-methylated compound of formula (8).

[0080] Quantification of component (B)

When this liquid obtained in Synthesis Example 1 was analyzed by HPLC (high performance liquid chromatography), it contained 8000 ppm of (B) component [compounds of chemical formulas (6), (7) and (8)]! /, It was. HPLC conditions It is shown below.

(HPLC analysis method and conditions)

Equipment: LC-20AD made by Shimadzu Corporation

Column: Inertsil ODS-2 (4.6 mml. D. X 150 mm) manufactured by GL Sciences Inc. Eluent: Flow rate 1. Oml / min

0. 015% phosphoric acid water Z methanol (mass ratio) = 55Z45 (Initial)

= 50/50 (lOmin)

= 30/70 (40min)

= 20/80 (45min)

= 0/100 (55min)

Column temperature: 40 ° C

Detection wavelength: 210nm

Sample: lOOmgZlOml (acetonitrile), injection volume 5 μ 1

(Ii) Component concentration calculation method: The concentration of (iv) component was calculated by the following formula.

[0081] Concentration (ppm) = (Detection peak area of dig compound) Z (Total area of detection peak from 0 to 55 minutes) X 10 ⁶

Next, the following Examples 1 to 3 and Comparative Example 1 were carried out using the liquid. (Example 1)

To this liquid obtained in Synthesis Example 1, 20% aqueous solution of sodium hydroxide and sodium hydroxide was added (230g) twice the amount added during neutralization, and stirred for 1 hour while maintaining the liquid temperature at 30 ° C. Then, saponification was performed. And after leaving still for 30 minutes, the lower layer was removed. As a result of HPLC analysis of the upper layer, the component (B) was 10 ppm or less. 70 g of pure water was added to the upper layer, stirred for 5 minutes, allowed to stand for 1 hour, and then the upper layer was separated. Hydroquinone monomethyl ether was added to the upper layer at 400 ppm based on the solid content, and the solvent was removed under reduced pressure.

At this time, the oil bath temperature was set to 80 ° C. so that the liquid temperature did not exceed the temperature. Also, oxygen-containing nitrogen gas was blown as necessary to prevent polymerization. The component (B) in the obtained polyfunctional acrylic ester composition was lOOppm or less. The polyfunctional acrylic ester composition was subjected to an emulsification resistance test according to the following method. . The results are shown in Table 1.

(Emulsification resistance test method)

6.6 g of xylene was placed in a test tube, and 3.3 g of the resulting polyfunctional acrylate composition was added and dissolved, and 9.9 g of water was added to this solution. Then, after stirring the test tube at a speed of 10 reciprocations in 30 seconds, the test tube was allowed to stand and visually observed inside the test tube.

[0083] A: The upper layer and the lower layer are separated within 5 minutes, and the transparency of both layers is high.

[0084] ○: The upper layer and the lower layer are separated within 10 minutes, and the transparency of both layers is slightly lower than that of “◎”, but it is good.

Δ: Although the upper layer and the lower layer are separated, the transparency of both layers is not good.

[0086] X: The upper layer and the lower layer are not separated, or an intermediate layer is generated between the upper layer and the lower layer.

(Example 2)

Example 1 except that 115 g of a 20% sodium hydroxide aqueous solution (the same amount as 20% sodium hydroxide used in the neutralization treatment) was used for the main solution obtained in Synthesis Example 1. A saponification treatment was carried out in the same manner as above to obtain a polyfunctional acrylic ester composition. The obtained polyfunctional acrylic ester composition was evaluated in the same manner as in Example 1. The results are shown in Table 1. (Example 3)

In Example 2, a polyfunctional acrylate composition was obtained in the same manner as in Example 2, except that the stirring time was 3 hours. The obtained polyfunctional acrylic ester composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)

To this liquid obtained in Synthesis Example 1, 70 g of pure water was added, stirred for 5 minutes, allowed to stand for 5 hours, and then the lower layer was removed. In other words, the power to perform saponification was not enough. Then, the upper layer was subjected to a solvent removal treatment under reduced pressure in the same manner as in Example 1 to obtain a polyfunctional acrylic ester composition. The obtained polyfunctional acrylate composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0087] [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Input amount during neutralization in saponification

Double amount

Amount of aqueous sodium hydroxide solution to 1 time 1 time-Stirring time 1 hour 1 hour 1 hour-Multifunctional (meth) acrylic acid ester

1 00 or less 1 00 or less 1 00 or less 8000 Concentration of component (B) in composition (ppm) Emulsification resistance test ◎ ○ ◎ X

[0088] As shown in Table 1, in Example 13 the content of component (B) in the polyfunctional acrylate composition is all lOOppm or less, so the results of the emulsification resistance test Was also good. On the other hand, in Comparative Example 1, since the content of the component (B) in the polyfunctional acrylic ester composition was 8000 ppm, the result of the emulsification resistance test was poor.

[0089] The embodiment may be embodied with the following modifications.

[0090] As the emulsifiable compound, the polyfunctional (meta)

) Purification of the acrylic ester composition may be performed.

[0091] In order to further reduce the content of the emulsifying compound in the polyfunctional (meth) acrylic acid ester composition, the saponification treatment may be performed a plurality of times. In that case, it is preferable that the concentration of the alkaline aqueous solution used as the saponification agent is changed or the treatment temperature is changed.

[0092] As the saponification agent, an aqueous solution of an alkali metal salt such as sodium carbonate and an alkaline earth metal such as calcium hydroxide may be used.

[0093] The saponification treatment may be performed at a treatment temperature of less than 20 ° C, and the treatment time of the saponification treatment may be long.

Claims

Claims [1] A compound having two or more (meth) attayloxy groups as the main component (A), and (meth) in the component (A) as a subcomponent (B) A multi-functional (meth) acrylic acid occollll H et H one-ster composition containing a compound in which any one of the allyloyloxy groups is substituted with a group represented by the following chemical formula (1): A polyfunctional (meth) acrylic acid ester composition, wherein the content of the component (B) in the polyfunctional (meth) acrylic acid ester composition is lOOOOppm or less.

[Chemical 1]

2

R ¹

I

― 0— CH ₂ CH-COOH ■ ■ ■ (1)

[2] The polyfunctional (meth) acrylic acid ester composition according to claim 1, wherein the component (A) is a compound having three or more (meth) ataryloxy groups.

[3] The component (A) is dipentaerythritol penta (meth) acrylic acid ester or dipentaerythritol hexa (meth) acrylic acid ester, and the component (B) is a compound represented by the following chemical formula (2). The polyfunctional (meth) acrylic acid ester composition according to claim 2, wherein

[Chemical 2]

AO -A ⁴

⁰ⁿ 2 R ¹

A -OH ₂ C CH ₂ -0-CH ₂ -C-CH -0-CH,-CH-COOH (2

A

[In the chemical formula (2), R ¹ represents a hydrogen atom or a methyl group, and ^ to A ⁵ represent a (meth) atalyloyl group or a hydrogen atom. ]

[4] A method for producing a polyfunctional (meth) acrylic acid ester composition according to claim 1, A step of producing a polyfunctional (meth) acrylic acid ester composition by esterification reaction of polyhydric alcohol and (meth) acrylic acid in an organic solvent in the presence of an acid catalyst;

And a step of purifying the polyfunctional (meth) acrylate composition so that the content of the component (B) in the polyfunctional (meth) acrylate composition is lOOOppm or less. A method for producing a (meth) acrylic ester composition.

[5] The step of purifying the polyfunctional (meth) acrylic acid ester composition includes a step of neutralizing the reaction solution after the esterification reaction, and a step of saponifying the treatment solution after the neutralization treatment. Item 5. A method for producing a polyfunctional (meth) acrylic acid ester composition according to Item 4.

[6] The step of purifying the polyfunctional (meth) acrylic acid ester composition includes a step of washing the reaction solution after the esterification reaction, a step of neutralizing the treatment solution after the washing treatment, and a neutralization treatment. 5. The method for producing a polyfunctional (meth) acrylic acid ester composition according to claim 4, comprising a step of saponifying the subsequent treatment liquid.

[7] In the step of purifying the polyfunctional (meth) acrylic acid ester composition, the polyfunctional (meth) acrylic acid ester composition is saponified using an alkaline aqueous solution. A method for producing a polyfunctional (meth) acrylic acid ester composition according to any one of the preceding items.