JPWO2007000920A1 - Multifunctional (meth) acrylic acid ester composition and method for producing the same - Google Patents

Abstract

The polyfunctional (meth) acrylic acid ester composition is composed of a compound having two or more (meth) acryloyloxy groups as the main component (A) and the component (A) as a subcomponent (B). In which any one of (meth) acryloyloxy groups is substituted with a group represented by the following chemical formula (1). Content of the (B) component in a polyfunctional (meth) acrylic acid ester composition is 1000 ppm or less. [In chemical formula (1), R1 represents a hydrogen atom or a methyl group. ]

Description

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

  In recent years, for example, in the fields of paints, adhesives, and printing inks, use of UV curable or electron beam curable agents is increasing from the viewpoints of environmental protection, resource saving, energy saving, and the like. For example, (meth) acrylic acid ester having two or more (meth) acryloyl groups (referred to as polyfunctional (meth) acrylic acid ester in this application) is widely used as a reactive diluent for ultraviolet curable resins or electron beam curable resins. Has been. In particular, polyfunctional (meth) acrylic acid esters obtained by (meth) acryloylating trimethylolpropane, pentaerythritol, dipentaerythritol and their derivatives have characteristics such as fast curability and high hardness. The amount of use is increasing.

  Conventionally, a polyfunctional (meth) acrylic acid ester is produced by an esterification reaction of a polyhydric alcohol and (meth) acrylic acid in the presence of an acid catalyst such as sulfuric acid, methanesulfonic acid, and paratoluenesulfonic acid. In the reaction product thus obtained, a catalyst, unreacted substances, and side reaction products remain, and thus 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, an aqueous solution of sodium hydroxide (caustic soda) having a concentration of 1 to 25% and sodium carbonate are used. (Sodium carbonate) aqueous solution is used. Further, the reaction solution is purified using water.

  Specifically, when a hydroxyl group-containing (meth) acrylate ligomer is produced by addition polymerization of a hydroxyl group-containing (meth) acrylate ester in the presence of a catalyst, the reaction solution is adsorbent such as magnesium silicate. Or a method of purifying a reaction solution using an alkaline aqueous solution (for example, see Patent Document 1). Moreover, the manufacturing method of the following polyfunctional (meth) acrylic acid ester is disclosed (for example, refer 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.

  By the way, in the production of polyfunctional (meth) acrylic acid esters, in order to increase the density of (meth) acryloyl groups, the esterification reaction usually takes longer time than the production of monofunctional (meth) acrylic acid esters. Or at higher reaction temperatures. When the esterification reaction is performed under such conditions, a side reaction peculiar to (meth) acrylic acid ester occurs, and a side reaction product is generated.

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

In 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 the emulsifying compound cannot be sufficiently decomposed and removed. Therefore, when the polyfunctional (meth) acrylic acid ester from which the emulsifying compound has not been removed is used for applications that require emulsification resistance, such as ink, various ink bleeding, contamination of manufacturing equipment, etc. There was a problem that harmful effects occurred.
JP 61-134350 A JP-A-6-219991

  This invention is made in view of the above-mentioned subject, The polyfunctional (meth) acrylic acid ester composition which can suppress the bad effect by the emulsification from which the isolation | separation with the organic layer and water layer which generate | occur | produce in a post-processing process becomes inadequate, and It aims at providing the manufacturing method.

  In one embodiment of the present invention, a polyfunctional (meth) acrylic ester composition is provided. The polyfunctional (meth) acrylic acid ester composition comprises a compound having two or more (meth) acryloyloxy groups as the main component (A), and the component (B) as a subcomponent (B). Any one of the (meth) acryloyloxy groups in the component contains a compound substituted with a group represented by the following chemical formula (1). Content of the (B) component in a polyfunctional (meth) acrylic acid ester composition is 1000 ppm or less.

[In the chemical formula (1), R ¹ represents a hydrogen atom or a methyl group. ]
According to this configuration, the component (B) in which any one of the (meth) acryloyloxy groups in the component (A) is substituted with the group represented by the chemical formula (1) corresponds to a compound exhibiting emulsifiability, Since the content thereof is 1000 ppm or less, it is possible to reduce the emulsifying compound and to suppress the adverse effects caused by emulsification that causes insufficient separation of the organic layer and the aqueous layer in the post-treatment process.

  The component (A) is preferably a compound having 3 or more (meth) acryloyloxy groups. Furthermore, the component (A) is more preferably dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate, and the component (B) is preferably represented by the following chemical formula (2). It is a compound. According to this structure, the above-mentioned effect can be exhibited about the polyfunctional (meth) acrylic acid ester of dipentaerythritol penta (meth) acrylic acid ester or dipentaerythritol hexa (meth) acrylic acid ester.

In [Formula (2), ^{R 1} represents a hydrogen atom or a methyl ^group, A 1 to A ⁵ represents a (meth) acryloyl group or a hydrogen atom. ]
In another aspect of the present invention, a method for producing the above-described polyfunctional (meth) acrylic acid ester composition is provided. This production method comprises a step of producing a polyfunctional (meth) acrylic acid ester composition by esterifying a 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) acrylic acid ester composition so that the content of the component (B) in the polyfunctional (meth) acrylic acid ester composition is 1000 ppm or less. According to this structure, the polyfunctional (meth) acrylic acid ester composition having the above-described effects can be easily produced by purifying the polyfunctional (meth) acrylic acid ester composition using the component (B) as an index. can do.

  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 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 treatment. A step of saponifying the subsequent treatment liquid. According to these structures, the polyfunctional (meth) acrylic acid ester composition which it has can be manufactured more easily.

  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. According to this configuration, the polyfunctional (meth) acrylic acid ester composition can be purified efficiently.

The chart which shows the NMR spectrum about the residue of the synthesis example 1. The chart which shows IR spectrum about the residue of the synthesis example 1. FIG. The chart which shows the MALDI-TOFMS spectrum about the residue of the synthesis example 1. The chart which shows the MALDI-TOFMS spectrum about the residue (methylesterified) of the synthesis example 1.

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

  The polyfunctional (meth) acrylic acid ester composition of this embodiment is a compound having two or more (meth) acryloyloxy groups as the main component (A), and the component (B) as a subcomponent. (A) The compound in which any one of the (meth) acryloyloxy group in a component was substituted by the group represented by following Chemical formula (1). Content of the (B) component in a polyfunctional (meth) acrylic acid ester composition is 1000 ppm or less. The content of the component (B) is measured by high performance liquid chromatography (hereinafter referred to as HPLC). Specifically, the content of the component (B) is measured under the following conditions.

Detector: UV detector Column type: ODS column Column temperature: 40 ° C
Eluent: acidic aqueous solution / methanol system (pH of acidic aqueous solution is preferably 2 to 3. As acidic aqueous solution, phosphoric acid aqueous solution is preferable.)

[In the chemical formula (1), R ¹ represents a hydrogen atom or a methyl group. ]
During the production of the polyfunctional (meth) acrylic acid ester, various side-reactions occur due to the esterification reaction at a high temperature and for a long time, and various emulsifying compounds are produced. The component (B) is also such an emulsifying compound. It is a compound that causes emulsification.

  The component (A) is preferably a compound having 3 or more (meth) acryloyloxy groups. Examples of the component (A) include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  When the component (A) is trimethylolpropane tri (meth) acrylate, the component (B) includes a compound represented by the following chemical formula (3).

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

  When the component (A) is pentaerythritol tri or tetra (meth) acrylic acid ester, examples of the component (B) include compounds represented by the following chemical formula (5).

  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).

In chemical formulas (2) to (5), R ¹ represents a hydrogen atom or a methyl group, and A ^{1 to} A ⁵ represent a (meth) acryloyl group or a hydrogen atom.

  Next, the manufacturing method of a polyfunctional (meth) acrylic acid ester composition is demonstrated.

The (meth) acrylic acid ester composition is manufactured 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 of polyhydric alcohol and (meth) acrylic acid in an organic solvent in the presence of an acid catalyst. In the purification step, the polyfunctional (meth) acrylic acid ester composition is purified so that the ratio of the component (B) in the polyfunctional (meth) acrylic acid ester composition is 1000 ppm or less. Hereinafter, both steps will be described in order.
[Esterification reaction step]
The esterification reaction in this esterification reaction step is performed according to a conventional method in the production of polyfunctional (meth) acrylic acid esters. 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.

  Examples of the polyhydric alcohol include dihydric alcohols, branched or linear long-chain alkyl diols, polyalkylene glycols, bisphenols and alkylene oxide adducts of the bisphenols, polyols and alkylene oxide adducts of the polyols, and tris- 2-hydroxyethyl isocyanurate is mentioned. Examples of the dihydric 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 alcohol described above, since a polyfunctional (meth) acrylic acid ester having a high density of (meth) acryloyl groups is obtained, an alcohol having 3 to 6 hydroxyl groups or an alkylene oxide adduct thereof is obtained. preferable.

  (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 usage-amount of (meth) acrylic acid is adjusted with respect to 1 mol of all the hydroxyl groups of a polyhydric alcohol so that the polyfunctional (meth) acrylic ester obtained may have the target hydroxyl value.

  Examples of the acidic catalyst include sulfuric acid, paratoluenesulfonic acid, and methanesulfonic acid. The reaction temperature can be appropriately set according to the raw materials used and the purpose, but is preferably 65 to 140 ° C, more preferably 75 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization. When this reaction temperature is less than 65 ° C., the esterification reaction may be delayed or the yield may be reduced. When the reaction temperature exceeds 140 ° C., thermal polymerization of (meth) acrylic acid or the generated polyfunctional (meth) acrylic ester may occur.

  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 depressurization after the reaction or after the post-treatment, but when an organic solvent that does not have an odor problem is used, the organic solvent is used for adjusting the viscosity of the composition. It may remain in the composition without being left behind.

The esterification reaction is preferably carried out under normal pressure (0.1 MPa) or reduced pressure. In order to prevent thermal polymerization of (meth) acrylic acid or the generated polyfunctional (meth) acrylic acid ester, it is preferable that the esterification reaction is performed in the presence of oxygen. For the same purpose, a polymerization inhibitor is preferably added to the reaction solution. Examples of such polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxylthiophenol, α-nitroso-β-naphthol, p-benzoquinone, and copper salts. Can be mentioned. The addition amount of the polymerization inhibitor is preferably 0.001 to 5.0% by mass and more preferably 0.01 to 1.0% by mass with respect to the raw material (meth) acrylic acid. 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 is not further improved, so that an excessive polymerization inhibitor tends to be wasted. As a method for confirming the progress of the esterification reaction, for example, there is a method of monitoring the remaining amount of (meth) acrylic acid and polyhydric alcohol, and the amount of water produced by the esterification reaction, that is, the amount of dehydration is monitored. The method is preferred.
[Purification process]
Next, the purification process for removing the component (B) from the reaction product obtained in the esterification reaction process 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 catalyst acid content in the reaction solution after the esterification reaction in the esterification reaction step.

The neutralization treatment step is performed according to a conventional method. Examples of the conventional method include a method in which an aqueous alkali 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 time or more, preferably 1.1 to 1.6 times in terms of molar ratio to the acid content of the reaction solution. When this addition amount is less than 1 time in molar ratio with respect to the acid content of the reaction solution, neutralization of the acid content may be insufficient. The concentration of the alkaline aqueous solution is preferably 1 to 25% by mass, and more preferably 10 to 25% by mass. When the concentration of the alkaline aqueous solution is less than 1% by mass, the amount of drainage after neutralization may increase. When the concentration of the aqueous alkali 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, although the acid catalyst and unreacted (meth) acrylic acid are removed, the emulsifying compound such as the component (B) is not sufficiently removed.

  (B) As a removal method of emulsifying compounds, such as a component, removal methods by ion exchange resins, such as adsorption agents, such as calcium oxide, and a styrene divinylbenzene copolymer, are mentioned, for example. However, since the removal efficiency is high and industrially advantageous, a method of saponifying the treatment liquid by adding an alkaline aqueous solution to the treatment liquid after the neutralization treatment and stirring the treatment liquid is preferable. .

  The neutralization treatment step and the saponification treatment step may be performed collectively or 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 step.

  Next, the case where a neutralization process process and a saponification process process are implemented separately is demonstrated.

  In the saponification treatment in the saponification treatment step, the organic layer obtained after the neutralization treatment step or after the water washing treatment step described later is treated with an alkali as a saponification treatment agent, whereby an emulsifying compound such as component (B) and the like A saponification reaction with an alkali is performed to decompose the emulsifying compound such as component (B). This saponification treatment step is performed separately from the neutralization treatment step, so that the saponification reaction can be effectively performed.

  Examples of the saponification 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 agent to be introduced can be selected widely. Therefore, the saponification treatment is carried out by converting the ester bond of the ester having a carboxyl group (B) into a corresponding (meth) acrylic acid [substantially (meth) acrylic alkali metal salt] and a polyhydric alcohol. Hydrolyzes. The decomposition products are removed by dissolving in water.

  As the alkali used as the saponification agent, an aqueous alkali solution is preferable. Examples of the alkali component in the alkaline aqueous 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. Examples of the alkaline earth metal hydroxide include calcium hydroxide. Among these, an alkali metal hydroxide is preferable because the effect of the saponification treatment is high. The concentration of the alkaline aqueous solution is preferably 1 to 25% by mass, and more preferably 10 to 25% by mass. The amount of alkali used is preferably 0.2 to 4 times the amount of alkali used during the neutralization treatment, and more preferably 0.5 to 2 times considering the size of the treatment tank and the amount of drainage. The saponification treatment is preferably performed under stirring, and the stirring time at that 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 emulsifying compound can be easily performed at ordinary temperature (20 ° C.) or with a little heating.

  Although the saponification process is completed by the process within the range of the preferable conditions described above, the progress of the saponification process can be managed as necessary. Examples of a method for managing the progress of the saponification treatment include a method of measuring the alkali number of the water layer, the conductivity (electric conductivity) of the organic layer, and the interfacial tension. The alkali number of the aqueous layer varies depending on, for example, the type of ester, the increase / decrease in side reactions, and the concentration of the aqueous alkali solution used, so 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 time point at which the fluctuation of the alkali number during the saponification process becomes small can be used as a measure for ending the saponification process.

  The conductivity of the organic layer becomes high when the ionic component contained in the organic layer is large. In such a state, the emulsifying compound is mainly present as an alkali metal salt. As the saponification reaction proceeds, the ionic component is decomposed and transferred from the organic layer to the alkaline aqueous solution layer. For this reason, as with the alkali value of the aqueous layer, the conductivity of the organic layer varies depending on the brand and formulation, but the time when the variation in the conductivity becomes small can be used as a measure of the end of the saponification treatment step.

The interfacial tension of the organic layer can also be considered similarly to the alkali number and conductivity described above. When the emulsifying compound is present in the organic layer, the interfacial tension becomes a small value, but the interfacial tension increases as the emulsifying compound is decomposed and removed. For this reason, the point in time when the fluctuation of the interfacial tension becomes small can be used as a measure for ending the saponification process.
(Washing process)
In the present invention, it is preferable that the reaction solution or the treatment solution is subjected to a water washing treatment. The water washing treatment can be performed on the reaction solution obtained by the esterification reaction, the organic layer after neutralization, and the organic layer after saponification treatment. The point at which the water washing treatment is performed is appropriately selected according to the components used and the purpose.

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

In this solvent removal treatment step, oxygen is supplied to the organic layer or a polymerization inhibitor is added to suppress the thermal polymerization of the polyfunctional (meth) acrylic acid ester, and the temperature is maintained at, for example, 80 ° C. or lower. Further processing is carried out under reduced pressure. The polyfunctional (meth) acrylic acid ester can be purified by rectification as necessary.
(Application examples for printing ink applications)
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 step And the subsequent processing is preferably performed as follows. That is, in the saponification treatment step, in order to promote the saponification reaction, the saponification treatment 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. Is done.

  In order to obtain a product having better dispersibility, the organic layer after the saponification treatment is preferably washed with acidic water. Examples of acidic water include an aqueous ammonium sulfate solution, an aqueous ammonium chloride solution, and an aqueous hydrochloric acid solution. As a result, sodium is eliminated from the compound containing sodium carboxylate (—COONa) produced by the side reaction and neutralization treatment. By this treatment, the emulsifiable 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 a treatment, an ink having excellent dispersibility of the ink pigment can be obtained.

  Now, the operation of the present embodiment will be described. In the production of the polyfunctional (meth) acrylic acid ester, the reaction product produced by the esterification reaction in the esterification reaction step is subjected to neutralization treatment, and further purified. Saponification treatment is performed in the saponification treatment step in the 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, (B) component is decomposed | disassembled into water-soluble compounds, such as (meth) acrylic acid and a polyhydric alcohol. Thereafter, these decomposition products are dissolved in water and removed by washing with water. As a result, the content of the component (B) in the (meth) acrylic acid ester composition is suppressed to 1000 ppm or less.

  This embodiment has the following advantages.

  The polyfunctional (meth) acrylic acid ester composition of this embodiment is a compound having two or more (meth) acryloyloxy groups as the main component (A), and the component (B) as a subcomponent. Any one of the (meth) acryloyloxy groups in the component (A) contains a compound substituted with the group represented by the chemical formula (1). Content of the (B) component in a polyfunctional (meth) acrylic acid ester composition is 1000 ppm or less. For this reason, the emulsifiable compound can be reduced, and the adverse effect of the polyfunctional (meth) acrylate composition being emulsifiable by the emulsifiable compound can be suppressed. As a result, when a polyfunctional (meth) acrylic acid ester is used in, for example, ink, it is possible to suppress ink bleeding and contamination of manufacturing equipment.

  The component (A) is preferably a compound having 3 or more (meth) acryloyloxy groups. Furthermore, (A) component is dipentaerythritol penta (meth) acrylic acid ester or dipentaerythritol hexa (meth) acrylic acid ester, and (B) component is a compound represented by said chemical formula (2) The above-described effects can be sufficiently exhibited with respect to those polyfunctional (meth) acrylic acid esters.

  In the method for producing a polyfunctional (meth) acrylic acid ester composition, a polyfunctional (meth) acrylic acid ester is obtained by esterification of a polyhydric alcohol and (meth) acrylic acid in an organic solvent in the presence of an acid catalyst. A 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 1000 ppm 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.

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

Hereinafter, 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 2 L reactor equipped with a stirrer and a thermometer, 315 g (1.24 mol) of dipentaerythritol, 643 g (8.9 mol) of acrylic acid, 526 g of toluene, 1.5 g of cupric chloride, 15 g of 78% sulfuric acid The esterification reaction was started by heating the reactor in an oil bath set at 100 ° C. under a pressure of 53 kPa. Condensed water azeotroped with toluene was removed with a Dean-Stark apparatus to proceed the esterification reaction, and the reaction was stopped after 8 hours. The reaction liquid weight at this time was 1380 g, and the acid value was 1.75 meq / g.

  After cooling the obtained reaction liquid, 740 g of toluene was added and diluted. The diluted reaction solution was transferred to a tank for neutralization treatment, 350 g of pure water was added and stirred for 5 minutes, and then allowed to stand for 30 minutes to separate the upper layer and the lower layer.

  To 700 g of the upper layer, 115 g of a 20% aqueous sodium hydroxide 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 and the lower layer. When the acid value of the upper layer was measured, the acid value was 0.82 meq / g.

  The weight of the separated upper layer was 650 g. Using this liquid (hereinafter referred to as this liquid), the component (B) was isolated and analyzed.

(B) Isolation and analysis of component The liquid obtained in Synthesis Example 1 was decompressed and concentrated to obtain a residue. 2.5 g of this residue was dissolved in 15 ml of ethyl acetate and then extracted twice with 10 ml of 0.5% aqueous sodium carbonate solution. After combining the lower layers obtained by these extractions, 1M hydrochloric acid was added to obtain an acidic aqueous solution having 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 then dehydrated by adding 1 g of anhydrous sodium sulfate. The ethyl acetate solution obtained after filtration was immersed in a hot water bath and concentrated to obtain 15 mg of residue.

  The obtained residue was analyzed by proton-NMR (nuclear magnetic resonance spectrum) analysis, IR (infrared absorption spectrum) analysis, and MALDI-TOFMS (matrix-assisted laser desorption / ionization mass spectrum) analysis. The obtained spectrum is shown in FIGS. Further, a sample obtained by treating the residue with DMF (dimethylformamide) -dimethylacetal to be converted to methyl ester was analyzed by MALDI-TOFMS. The obtained spectrum is shown in FIG.

  From the above analysis results, 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) could be confirmed.

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 four of A ^{1 to} A ⁵ are acryloyl. A compound that represents a 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 A ^{1 to} A ⁵ represent an acryloyl group.

1) FIG. 1 (proton-NMR spectrum)
In FIG. 1, the signal of 2.5 to 2.6 ppm is derived from α-methylene of —O—CH ₂ —CH ₂ —COOH (carboxylic acid).

[Measurement equipment and conditions]
270 MHz, manufactured by JEOL Ltd., JNM-EX270 type Measurement conditions: Deuterated chloroform solution, number of integrations 32 times, normal temperature 2) Fig. 2 (IR spectrum)
In FIG. 2, 1721.7 cm ⁻¹ represents absorption of an ester bond.

[Measurement equipment and conditions]
Made by Nicorey, Impact-400D
Accessories: μ-ATR (manufactured by SensIR Technology), diamond crystal one-time reflection type Measurement conditions: resolution 4 cm ⁻¹ , number of integrations 32 times 3) FIG. 3 (MALDI-TOFMS spectrum)
In FIG. 3, m / z 564 shows the compound represented by the chemical formula (6) and the compound represented by the chemical formula (7) added with sodium derived from the ionization aid.

  m / z 586 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 ionization aid.

  m / z 618 indicates a compound represented by the chemical formula (8) in which sodium derived from an ionization aid is added.

  m / z640 shows what added the sodium derived from an ionization adjuvant to the sodium salt of the compound represented by Chemical formula (8).

[Measurement equipment and conditions]
Apparatus: PE biosystems, Voyager-DE RP type Laser: N ₂ laser (λ = 337 nm)
Accelerating voltage: 20 kV
Measurement mode: Linear mode Ion to be measured: Positive ion Sample preparation method a) 10 mg of each sample is dissolved in 1 ml of acetone.
b) Matrix: 10 mg of 2,5-dihydroxybenzoic acid (DHB) is dissolved in 1 ml of acetone.
c) Ionization aid: 5 mg of sodium iodide is dissolved in 1 ml of acetone.
d) 2 μl of each of the solutions a) to c) is collected and mixed, and 1 μl of the mixed solution is dropped on the sample plate for MALDI-TOFMS to produce crystals.

4) FIG. 4 (MALDI-TOFMS spectrum after methyl ester derivatization)
In FIG. 4, m / z 578 indicates a compound in which sodium derived from an ionization aid is added to a compound in which the carboxyl groups of chemical formulas (6) and (7) are methyl esterified.

  m / z 632 represents a compound obtained by adding sodium derived from an ionization aid to a compound in which the carboxyl group of the chemical formula (8) is methyl esterified.

(B) Quantification of component The liquid obtained in Synthesis Example 1 was analyzed by HPLC (high performance liquid chromatograph). As a result, component (B) [compounds of chemical formulas (6), (7) and (8)] contained 8000 ppm. It was. The HPLC conditions are shown below.
(HPLC analysis method and conditions)
Apparatus: LC-20AD type manufactured by Shimadzu Corporation Column: Inertsil ODS-2 (4.6 mm ID × 150 mm) manufactured by GL Sciences Inc.
Eluent: Flow rate 1.0ml / min
0.015% phosphoric acid water / methanol (mass ratio) = 55/45 (Initial)
= 50/50 (10 min)
= 30/70 (40 min)
= 20/80 (45 min)
= 0/100 (55 min)
Column temperature: 40 ° C
Detection wavelength: 210 nm
Sample: 100 mg / 10 ml (acetonitrile), injection volume 5 μl
(B) Component concentration calculation method: The concentration of component (B) was calculated by the following equation.

Concentration (ppm) = (Detection peak area of compound) / (Total area of detection peak from 0 to 55 minutes) × 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 sodium hydroxide solution was added in an amount twice as much as that added during neutralization (230 g), and the mixture was stirred for 1 hour while maintaining the liquid temperature at 30 ° C. Processed. And after leaving still for 30 minutes, the lower layer was removed. When the upper layer was analyzed by HPLC, the component (B) was 100 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. To the upper layer, 400 ppm of hydroquinone monomethyl ether was added to 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. In addition, oxygen-containing nitrogen gas was blown in as necessary to prevent polymerization. The component (B) in the obtained polyfunctional acrylic ester composition was 100 ppm 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)
Into a test tube, 6.6 g of xylene was added, and 3.3 g of the obtained polyfunctional acrylate composition was added and dissolved, and 9.9 g of water was added to this solution. Then, the test tube was stirred at a speed of 10 reciprocations in 30 seconds, and then left still, and the inside of the test tube was visually observed and judged according to the following criteria.

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

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

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

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)
Saponification was carried out in the same manner as in Example 1 except that 115 g of 20% aqueous sodium hydroxide solution (the same amount as 20% sodium hydroxide used in the neutralization treatment) was used for the main solution obtained in Synthesis Example 1. Processing was performed 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. That is, the saponification process was not performed. 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 acrylic ester composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 3, since the content of the component (B) in the polyfunctional acrylic ester composition is 100 ppm or less, the results of the emulsification resistance test are also good. Met. 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.

  The embodiment can be embodied with the following modifications.

  As the emulsifying compound, the polyfunctional (meth) acrylic acid ester composition may be purified using the component (B) and other compounds as indicators.

  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.

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

  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 increased.

Claims (7)

Any one of a compound having two or more (meth) acryloyloxy groups as the main component (A) and a (meth) acryloyloxy group in the component (A) as the subcomponent (B) Is a polyfunctional (meth) acrylic acid ester composition containing a compound substituted with a group represented by the following chemical formula (1),
The polyfunctional (meth) acrylic acid ester composition, wherein the content of the component (B) in the polyfunctional (meth) acrylic acid ester composition is 1000 ppm or less.

[In the chemical formula (1), R ¹ represents a hydrogen atom or a methyl group. ]   The polyfunctional (meth) acrylic acid ester composition according to claim 1, wherein the component (A) is a compound having three or more (meth) acryloyloxy groups. The component (A) is dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate, 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.

In [Formula (2), ^{R 1} represents a hydrogen atom or a methyl ^group, A 1 to A ⁵ represents a (meth) acryloyl group or a hydrogen atom. ] It is a manufacturing method of the polyfunctional (meth) acrylic acid ester composition according to claim 1,
A step of producing a polyfunctional (meth) acrylic acid ester composition by esterifying a 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 1000 ppm or less. A method for producing a (meth) acrylic acid ester composition.   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. The manufacturing method of the polyfunctional (meth) acrylic acid ester composition of description.   The step of purifying the polyfunctional (meth) acrylic acid ester composition includes a step of washing the reaction liquid after the esterification reaction, a step of neutralizing the treatment liquid after the water washing treatment, and a treatment after the neutralization treatment. The manufacturing method of the polyfunctional (meth) acrylic acid ester composition of Claim 4 including the process of saponifying a liquid.   7. The saponification treatment of the polyfunctional (meth) acrylic acid ester composition is performed using an alkaline aqueous solution in the step of purifying the polyfunctional (meth) acrylic acid ester composition. The manufacturing method of the polyfunctional (meth) acrylic acid ester composition as described in 1 above.

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