WO2009093646A1 - Process for production of (meth)acrylate composition - Google Patents

Abstract

Disclosed is a process for producing a (meth)acrylate composition which is characterized in that the (meth)acrylate composition can be produced by using inexpensive and readily available raw materials, that the (meth)acrylate composition produced by the process has excellent curing rate, that a cured product of the (meth)acrylate composition has excellent physical properties including hardness, and that the (meth)acrylate composition exhibits excellent emulsification resistance when used as an ink. Specifically disclosed is a (meth)acrylate composition comprising pentaerythritol tri(meth)acrylate (a tri-form), pentaerythritol tetra(meth)acrylate (a tetra-form) and a compound produced by the Michael addition of a hydroxy group in the tri-form to a (meth)acryloyl group in the tetra-form (compound M), wherein the tri-form, the tetra-form and the compound M are contained in the composition at a ratio of (0.1-2.0):100:(15.0-50.0) in terms of the peak areas as measured under predetermined measurement conditions for liquid chromatography. Also specifically disclosed is a process for producing the (meth)acrylate composition.

Description

Method for producing (meth) acrylate composition

The present invention relates to a method for producing a (meth) acrylate composition that can be cured by irradiation with active energy rays or by heating. The (meth) acrylate composition obtained by the method of the present invention can be used in the technical field using these as raw materials for paints, inks, adhesives, fillers, molding materials and the like.
In the present specification, an acryloyl group and / or a methacryloyl group are represented as a (meth) acryloyl group, an acrylate and / or methacrylate as a (meth) acrylate, and acrylic acid and / or methacrylic acid as (meth) acrylic acid. .

(Meth) acrylates having two or more (meth) acryloyl groups (hereinafter referred to as “polyfunctional (meth) acrylates”) have high curability by irradiation with active energy rays or by heating. A wide range of cured physical properties can be obtained by blending with (meth) acrylate. Therefore, this polyfunctional (meth) acrylate is conventionally used in a large amount as a crosslinking component of a blend of paints, inks, adhesives, fillers and molding materials, or as a reactive diluent component.

In particular, the polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups can be excellent in the hardness of the composition and can improve various physical properties, such as ink and hard coat. Are used in various applications.
Examples of the polyfunctional (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. (Meth) acrylate and the like are known.
These polyfunctional (meth) acrylates are produced by an esterification reaction (for example, Patent Documents 1 and 2) between a corresponding polyhydric alcohol and (meth) acrylic acid (for example, a patent) Literature 3 and 4).

Among these, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol tetra (meth) acrylate have no problem with the hardness of the resulting cured product, but the curing rate is insufficient. was there. Furthermore, when the polyfunctional (meth) acrylate is used for ink applications, the emulsion resistance may be insufficient.
On the other hand, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate have excellent performance without the above problems, but the raw alcohol may be expensive or difficult to obtain. Therefore, there is a demand for (meth) acrylates that are cheaper and easier to obtain and that have the above performance.

JP 2007-176881 A (Claims) JP 2007-176882 A (Claims) JP-A-8-319256 (Claims) JP-A-9-31018 (Claims)

By the way, as a method for producing polyfunctional (meth) acrylate other than the above, there is also known a method in which polyfunctional (meth) acrylate is heated in the presence of an acid catalyst, so-called Michael addition reaction (Patent Document 5). The invention described in the patent document is mainly intended for liquefaction of a polyfunctional (meth) acrylate that is solid at room temperature, and does not disclose technical means for solving the above-described problems.

The present inventors can manufacture with raw materials that are inexpensive and easily available, and the resulting (meth) acrylate composition has excellent curing speed, and the cured product has excellent physical properties such as hardness, and is used for ink applications. It is an object of the present invention to provide a method for producing a (meth) acrylate composition that is also excellent in emulsification resistance.

JP-A-7-101902 (Claims)

As a result of intensive studies to solve the above problems, the present inventors have determined that pentaerythritol tri (meth) acrylate (tri) and pentaerythritol tetra (meth) acrylate (tetra) are in the presence of an acid catalyst. It was found that a (meth) acrylate composition containing the tri-isomer, tetra-isomer and specific Michael adduct at a specific ratio can solve the above-mentioned problems by heating and allowing the Michael addition reaction of the tri-isomer and tetra-isomer to proceed. As a result of further research based on this finding, the present invention has been completed.

According to the production method of the present inventor, a desired (meth) acrylate composition is produced using inexpensive and easily available raw materials such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. Can do. The obtained (meth) acrylate composition is excellent in curing speed, the cured product is excellent in physical properties such as hardness, and is excellent in emulsification resistance when used in ink applications.

The present invention includes pentaerythritol tri (meth) acrylate (hereinafter referred to as “tri-form”), pentaerythritol tetra (meth) acrylate (hereinafter referred to as “tetra-form”), and formula (1):

(In the formula, R represents a hydrogen atom or a methyl group.)
A method for producing a (meth) acrylate composition comprising a compound represented by (hereinafter referred to as “compound M”),
A production method comprising adjusting a tri-form, a tetra-form and a compound M to be contained in the following proportion by reacting the tri-form and the tetra-form in the presence of an acid catalyst;
Tri-form: Tetra-form: Compound M = 0.1-2.0: 100: 15.0-50.0
The above ratio is the peak area ratio of each component of the composition measured by liquid chromatography under the following conditions, and represents the area ratio of the tri-isomer and the compound M when the area of the tetra-body is 100.
<Measurement conditions for liquid chromatography>
Equipment: High performance liquid chromatograph (HPLC)
Detector: Ultraviolet detector Column type: Column (inner diameter; 2.1 mm × length; 150 mm) made of silica gel modified with an alkyl group having 18 carbon atoms (particle diameter: 1.7 μm)
Column temperature: 40 ° C
Eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (indicating volume ratio, the same applies hereinafter) (initial) → 50/50 (10 minutes) → 30/70 (15 minutes) → 0/100 (18-20 minutes).

The ratio of tri-, tetra- and compound M in the composition is preferably 0.1 to 2.0: 100: 15.0 to 30.0.
Hereinafter, the present invention will be described in detail.

1. Raw material (meth) acrylate In the present invention, tri- and tetra-isomers are used as raw materials.
The ratio of the tri-body and tetra-body of the raw material is tri-body: tetra-body = 50.0 to 200.0: 100 in the area ratio (peak area ratio) measured under the measurement conditions of liquid chromatography described later. More preferably, it is more preferably 80.0 to 150.0: 100.
The tri- and tetra-forms of the raw material are an esterification reaction product of pentaerythritol and (meth) acrylic acid, or an ester exchange reaction product of pentaerythritol and alkyl (meth) acrylate (hereinafter referred to as “esterification product etc. It is easy to obtain and preferable.
In this case, the total of the tri- and tetra-isomers may usually be contained in the esterified product or the like in an amount of 50% by weight or more, preferably 50 to 80% by weight. In this case, compounds other than tri- and tetra-forms may be included. Specific examples include unreacted pentaerythritol, unreacted (meth) acrylic acid, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, and other (meth) acrylate oligomers. In the case of, alkyl (meth) acrylate is also mentioned. When the esterified product or the like is obtained by a transesterification reaction, the compound M is not included, but when it is obtained by an esterification reaction, the compound M may be included. In this case, it is preferable that the area ratio measured by the above-mentioned liquid chromatography measurement conditions includes 10 or less, and more preferably 8 or less of compound M with respect to tetra-body 100.
Furthermore, (meth) acrylates other than these may be included. Specific examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
As the raw tri- and tetra- (meth) acrylates and other (meth) acrylates, acrylates are preferred because of excellent reactivity.

2. The acid catalyst acid catalyst is used for the addition reaction of a tri-form hydroxyl group to a tetra-form (meth) acryloyl group. This reaction is usually referred to as a Michael addition reaction.
Various acid catalysts can be used. Specifically, for example, sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, boron trifluoride etherate and tetrachloride. Tin etc. are mentioned. Of these, sulfuric acid, methanesulfonic acid and paratoluenesulfonic acid are preferred because they have high catalytic activity and do not deactivate even in the presence of water, and methanesulfonic acid and paratoluenesulfonic acid are preferred because there are few side reactions. More preferred.

The usage ratio of the acid catalyst is preferably 0.1 to 15% by weight, more preferably 1.0 to 10% by weight, based on the total amount of (meth) acrylate containing tri- and tetra-forms in the raw material. Here, the total amount of the (meth) acrylate containing the tri- and tetra-forms means the total amount of the tri- and tetra-forms when the (meth) acrylate in the raw material is only the tri- and tetra-forms. And when (meth) acrylates other than a tri isomer and a tetra isomer are included in the raw material, it means the total amount of the tri isomer, tetra isomer and other (meth) acrylates. By making the use ratio of the acid catalyst 0.1% by weight or more, the addition reaction can proceed sufficiently, and by making it 15% by weight or less, the reaction system is prevented from becoming unstable due to excessive heat generation. Further, coloring of the product and further gelation can be prevented.

3. Other Components In the production method of the present invention, it is preferable to use a reaction solvent as necessary. The reaction solvent is used for diluting the above essential components, for example, aromatic hydrocarbons such as toluene, benzene and xylene; aliphatic hydrocarbons such as hexane, cyclohexane and heptane; and methyl ethyl ketone and cyclohexanone. Examples include ketones.
As the reaction solvent, considering the solubility of the substrate, one kind may be used alone, or two or more kinds may be used in arbitrary combination.
When a reaction solvent is used, the mixing ratio may be selected according to the purpose, but a ratio in which the nonvolatile content of the reaction solution is usually 10 to 80% by weight is preferable.

Moreover, in the manufacturing method of this invention, it is preferable to add the polymerization inhibitor for suppressing that a (meth) acryloyl group carries out radical polymerization to a reaction liquid, or introduce | transduces oxygen-containing gas into a reaction liquid.
Examples of the polymerization inhibitor include hydroquinone, tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, phenothiazine and the like. Organic polymerization inhibitors such as copper chloride and copper sulfate; and organic salt polymerization inhibitors such as copper dibutyldithiocarbamate. A polymerization inhibitor may be used individually by 1 type, or may be used in combination of 2 or more types arbitrarily.
The ratio of the polymerization inhibitor is preferably from 50 to 20,000 ppm, more preferably from 300 to 5,000 ppm, based on the total amount of the (meth) acrylate containing the tri- and tetra-forms of the raw material. By setting the proportion of the polymerization inhibitor to 50 ppm or more, the effect of preventing polymerization can be made sufficient, and by setting it to 20,000 ppm or less, the curability of the product is prevented from being lowered, and the product Can be prevented from coloring.
Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

4). Method for Producing (Meth) acrylate Composition Features of (Meth) acrylate Composition The (meth) acrylate composition of the present invention contains a tri-form, a tetra-form and a compound M in the following proportions. The body and the tetra-body are reacted in the presence of an acid catalyst, and the tri-body, the tetra-body and the compound M are adjusted to have the following composition ratio.
Tri isomer: tetra isomer: compound M = 0.1 to 2.0: 100: 15.0 to 50.0 (preferably tri isomer: tetra isomer: compound M = 0.1 to 2.0: 100: 15 0.0-30.0).
In addition, the said ratio is the peak area ratio of each component which measured this composition with the liquid chromatography of the following conditions, Comprising: The area of a tri body and the compound M when the area of a tetra body is set to 100 is represented.
<Measurement conditions for liquid chromatography>
Equipment: High performance liquid chromatograph (HPLC)
Detector: Ultraviolet detector Column type: Column (inner diameter; 2.1 mm × length; 150 mm) made of silica gel modified with an alkyl group having 18 carbon atoms (particle diameter: 1.7 μm)
Column temperature: 40 ° C
Eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (initial) → 50/50 (10 minutes) → 30/70 (15 minutes) → 0/100 (18-20 minutes)
The above-mentioned arrow “→” means that the composition ratio is changed stepwise so that the composition ratio (volume ratio) of the eluent shown over the time in parentheses is obtained.
That is, using 0.03% by weight aqueous trifluoroacetic acid solution (hereinafter referred to as “TFA”) and acetonitrile (hereinafter referred to as “AN”) as eluents, first, TFA / AN = 60/40 (volume ratio, the same applies hereinafter) Elution)
Then change to TFA / AN = 50/50 over 10 minutes, change to TFA / AN = 30/70 10 minutes to 15 minutes after starting (5 minutes), 18 minutes after 15 minutes from start After (3 minutes), it is changed to TFA / AN = 0/100, and TFA / AN = 0/100 is maintained for 18 minutes to 20 minutes (3 minutes) from the start.

Here, the compound M is a compound represented by the following formula (1), and is a compound in which a hydroxyl group of a tri isomer is Michael-added to a (meth) acryloyl group of the tetra isomer. In the formula (1), R represents a hydrogen atom or a methyl group. Compound M is a key compound of physical properties such as curability of the composition among various (meth) acrylates contained in the (meth) acrylate composition,
It is one of the features of the present invention that the ratio is controlled by paying attention to the compound M.
In formula (1), when acrylate is used as a raw material, R is a hydrogen atom, and when methacrylate is used as a raw material, R is a methyl group.

The measurement conditions for liquid chromatography in the present invention are as described above.
Silica gel modified with an alkyl group having 18 carbon atoms is commercially available, for example, Acquity BEH C18 manufactured by Japan Waters Co., Ltd.
Moreover, it is preferable to measure as the following conditions.
Flow rate: 0.3 mL / min, detection wavelength of ultraviolet detector: 210 nm, sample concentration: 0.1 wt% acetonitrile solution, injection volume: 1 μL.
In the present invention, the area value of the tetra-body peak is defined as 100, and the relative area value of the tri-body and the peak of the compound M is calculated.

In the present invention, in the (meth) acrylate composition obtained by the reaction, the area ratio of the tri isomer, the tetra isomer and the compound M is set to the tri isomer: tetra isomer: compound M = 0.1 to 2.0: 100: 15. 0 to 50.0. As a result, the curing rate is excellent, the cured product is excellent in physical properties such as hardness, and the emulsification resistance is excellent. Preferably, tri-isomer: tetra-isomer: compound M = 0.1 to 2.0: 100: 15.0 to 30.0.
In particular, by setting the ratio of the tribody to 0.1 or more, the curability can be excellent, and by setting the ratio to 2.0 or less, the emulsification resistance can be excellent. By making the ratio of the compound M 15.0 or more, the curability can be made excellent, and by making it 50.0 or less, the cured product can be made excellent in hardness.

First Embodiment In the production method of the present invention, raw tri- and tetra-forms are reacted in the presence of the acid catalyst in a reaction solvent as necessary, and in the presence of a polymerization inhibitor as necessary. Then, the above tri-form: tetra-form: compound M = 0.1-2.0: 100: 15.0-50.0. Specifically, heating and stirring may be performed under the following conditions.
The ratio of the tri- and tetra-isomers of the raw material is the area ratio (peak area ratio) measured under the liquid chromatography measurement conditions, and the tri-isomer: tetra-isomer = 50.0 to 200.0: 100 And more preferably 80.0 to 150.0: 100.
As the tri- and tetra-isomers, acrylate is preferred because of excellent reactivity.

In this case, the reaction temperature is preferably 60 to 130 ° C. By setting the reaction temperature to 60 ° C. or higher, the reaction can be accelerated. On the other hand, by setting the reaction temperature to 130 ° C. or lower, the reaction can be performed stably and gelation can be prevented.

The reaction time may be appropriately set according to the ratio of the tri- and tetra-isomers of the raw material, the reaction conditions, the ratio of the finally obtained tri- and tetra-isomers, and is usually preferably 2 to 20 hours.

Since the reaction may deteriorate in the presence of moisture, when the tri- and tetra-isomers obtained by the esterification reaction described below are used without drying, dehydration is performed under reduced pressure conditions. It is preferable to react while promoting. The degree of reduced pressure may be appropriately set according to the purpose, but is preferably 45 to 95 kPa, and more preferably 50 to 90 kPa.

An example of a preferred production method is that a reactor equipped with a stirrer and a thermometer is charged with a predetermined amount of tri- and tetra-isomers, and if necessary, a reaction solvent is used, and an appropriate amount of an acid catalyst and further a polymerization inhibitor are charged. A method of heating and stirring for a predetermined time under stirring can be mentioned.
After completion of the reaction, the reaction solution is neutralized and washed with water, and the aqueous layer is separated, and then the organic layer is heated under reduced pressure to distill off the solvent to obtain the desired (meth) acrylate composition.

Second Embodiment As a production method of the present invention, an esterification reaction product of pentaerythritol and (meth) acrylic acid, that is, a mixture containing a tri-isomer and a tetra-isomer obtained by the esterification reaction is used as a raw material as it is. Thus, a (meth) acrylate composition can also be produced. That is, pentaerythritol and (meth) acrylic acid are reacted in the presence of an acid catalyst to obtain a mixture of a tri-form and a tetra-form, and then the presence of an acid catalyst using the mixture as a raw material in the first embodiment. You may make it react below and may manufacture a (meth) acrylate composition.

As a method for the dehydration esterification reaction of pentaerythritol and (meth) acrylic acid, various conventionally known methods may be used. For example, there is a method of dehydrating pentaerythritol and (meth) acrylic acid by heating and stirring in the presence of an acid catalyst.

The raw material pentaerythritol may contain other polyhydric alcohols as necessary. Specific examples include dipentaerythritol. Here, pentaerythritol alone and a mixture of pentaerythritol and another polyhydric alcohol are collectively referred to as “polyhydric alcohol containing pentaerythritol”. In this case, the content of the polyhydric alcohol other than pentaerythritol in the polyhydric alcohol containing pentaerythritol is usually 40% by weight or less, preferably 20% by weight or less, based on the total amount of the polyhydric alcohol. It is particularly preferably 10% by weight or less.

The proportion of polyhydric alcohol containing pentaerythritol and (meth) acrylic acid may be appropriately determined so that the tri- and tetra-isomers in the esterification reaction product are within the above preferred range. The molar ratio of (meth) acrylic acid to 1 mol of hydroxyl group in the polyhydric alcohol contained is preferably 0.6 to 1.8. In the case of a mixture of pentaerythritol and another polyhydric alcohol, the same ratio as described above is preferable.
By setting this ratio to 0.6 or more, a compound having a hydroxyl group other than a tri-form, for example, generation of unreacted pentaerythritol or (meth) acrylate having 2 or more hydroxyl groups, and addition reaction between these and a tetra-form can be achieved. Can be suppressed. Further, it is possible to prevent the product from becoming thicker and difficult to separate the two layers in the water washing after the reaction. On the other hand, by setting it as 1.8 or less, unreacted (meth) acrylic acid decreases, it is economical, and the alkali amount in neutralization can also be reduced.

The most suitable ratio between the polyhydric alcohol containing pentaerythritol and (meth) acrylic acid varies depending on the ratio of the desired tri- and tetra-isomers and reaction conditions, but can be easily set by an experimental method. . Moreover, in order to control the ratio of the tri isomer and the tetra isomer in the esterification reaction product to the target ratio, it is preferable to measure the amount of water distilled by the reaction.

As the acid catalyst, the same ones as described above can be used. The usage ratio of the acid catalyst is preferably 0.1 to 15% by weight, more preferably 1.0 to 10% by weight, based on the total amount of polyhydric alcohol containing pentaerythritol and (meth) acrylic acid.

The reaction temperature is preferably 80 to 130 ° C. By setting the reaction temperature to 80 ° C. or higher, the reaction rate can be increased. On the other hand, by setting the reaction temperature to 130 ° C. or lower, the reaction system becomes stable and gelation can be prevented.

The reaction time may be appropriately set according to the type, ratio and amount of raw materials to be used, the ratio of tri- and tetra-forms finally obtained, and is usually preferably 4 to 40 hours.

The reaction is preferably carried out under reduced pressure. Thereby, dehydration can be performed efficiently, the reaction can be completed in a short time, and coloring of the resulting composition can be prevented. The degree of reduced pressure may be appropriately set according to the purpose, but is preferably 45 to 95 kPa, and more preferably 50 to 90 kPa.

In the esterification reaction, it is preferable to use a reaction solvent because dehydration can be performed efficiently. As the reaction solvent, the same solvents as described above can be used.
Moreover, in the manufacturing method of this invention, it is preferable to add the polymerization inhibitor for suppressing that a (meth) acryloyl group carries out radical polymerization to a reaction liquid, or introduce | transduces oxygen-containing gas into a reaction liquid. Examples of the polymerization initiator and oxygen-containing gas include the same ones as described above.

A (meth) acrylate composition is produced by heating and stirring the mixture of tri- and tetra-isomers obtained by the esterification reaction in the presence of an acid catalyst. As the acid catalyst, the same ones as described above can be used.
In this case, without adding an acid catalyst to the resulting mixture of tri- and tetra-isomers, it may be heated as it is in the presence of the acid catalyst used in the esterification reaction, or a new acid catalyst is added. And may be heated.
There is also a method in which the obtained reaction mixture is neutralized and washed with water, the organic layer is separated, and an acid catalyst is newly added to the obtained organic layer and heated.
In this case, examples of the alkali for neutralization include an aqueous sodium hydroxide solution. According to the neutralization and water washing treatment, water-soluble components such as unreacted (meth) acrylic acid in the reaction mixture can be removed. Thereby, it is possible to preferably control the ratio of the tri-form and the tetra-form to be generated to the target ratio, and to prevent the separation of the water layer and the organic layer in the water washing step after the addition reaction. Can do.

According to the second embodiment, since a (meth) acrylate composition can be produced in one pot using polyhydric alcohol containing pentaerythritol and (meth) acrylic acid as raw materials, the process becomes simple and low cost. It is.
Also in this case, since the reactivity of a tri body and a tetra body is excellent, the acrylate manufactured using acrylic acid as a raw material is preferable.

5. Use of (meth) acrylate composition The (meth) acrylate composition obtained by the production method of the present invention is used as a raw material for a curable composition such as an active energy ray-curable composition or a thermosetting composition. It can be suitably used for various industrial applications such as inks, adhesives, fillers and molding materials.

As a curing means such as an irradiation method of active energy rays and a heating method, a general method known as a curing method of a radical polymerizable compound may be employed.

Various components described in detail below can be blended in the curable composition.

In addition, when using a (meth) acrylate (meth) acrylate composition as a curable composition, (meth) acrylate [other (meth) acrylate] other than the said (meth) acrylate can be mix | blended.

Other (meth) acrylates include a compound having one (meth) acryloyl group (hereinafter referred to as mono (meth) acrylate) and a compound having two or more (meth) acryloyl groups (hereinafter referred to as poly (meth) acrylate). Etc.

Examples of mono (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, Examples include hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 1,4-butanediol mono (meth) acrylate; alicyclic mono (meth) acrylates such as isobornyl acrylate. In addition to these, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, (meth) acryloylmorpholine, maleimide (meth) acrylate, glycidyl (meth) acrylate, and the like can be given.

Examples of poly (meth) acrylates include (meth) acrylates having two (meth) acryloyl groups such as pentaerythritol di (meth) acrylate monostearate, pentaerythritol tri (meth) acrylate, and trimethylolpropane tri Examples thereof include (meth) acrylate having three (meth) acryloyl groups such as (meth) acrylate. Besides these, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol propoxytetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and di A (meth) acrylate having 4 or more (meth) acryloyl groups such as (trimethylolpropane) tetra (meth) acrylate can also be used.

In addition, oligomers such as urethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate can also be used.

Among these, for the purpose of further imparting hardness to the cured product of the composition, it is more preferable to blend the poly (meth) acrylate described above.

When the polymerization initiator (meth) acrylate composition is used as an active energy ray curable composition, in particular, when a visible light or ultraviolet curable composition is used, a photopolymerization initiator is added to the composition. In addition, when setting it as an electron beam curable composition, it is not necessary to mix | blend a photoinitiator.

Specific examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 Acetophenones such as dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone; 2-methyl Anthraquinones such as anthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthate Such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide, etc. Benzophenone; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
A photosensitizer can be used in combination with the photopolymerization initiator as necessary. Examples of the photosensitizer include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethylamine, and triethanolamine.

When using a (meth) acrylate composition as a thermosetting composition, a thermal polymerization initiator is blended with the composition.
A well-known thing can be used as a thermal-polymerization initiator.

Other components In addition to the above components, an antifoaming agent, a leveling agent, an inorganic filler, an organic filler, a light stabilizer, an antioxidant, an ultraviolet absorber, a polymerization inhibitor, and the like can be blended as necessary.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following, “part” means part by weight.

Example 1
In a reactor equipped with a stirrer and a thermometer, an acrylate mixture containing a tri isomer, a tetra isomer, and a compound M, and a mixture containing 77 wt% of the tri isomer and the tetra isomer (with an area ratio measured under the following conditions, 80 parts of toluene as a reaction solvent, 2.1 parts of methanesulfonic acid as an acid catalyst, and 2 as a polymerization inhibitor , 6-di-tert-butyl-4-methylphenol and 0.01 part of hydroquinone monomethyl ether (hereinafter referred to as “MQ”) were added, heated to 80 ° C., and reacted for 8 hours.
After completion of the reaction, 30 parts of water was added to the reaction solution, stirred at 20 ° C. and allowed to stand, and the lower layer (aqueous layer) was removed. The upper layer (organic layer) was stirred at 80 ° C. for 4 hours under reduced pressure of 1 to 400 mmHg, and toluene was distilled off to obtain 79 parts of a liquid acrylate composition.
The obtained acrylate composition was analyzed by high performance liquid chromatography under the following conditions. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Compound M was separately analyzed by LC / MS [(UPLC) apparatus: Acquity UPLC system manufactured by Nippon Waters Co., Ltd., (MS) apparatus: Quattro premier API tandem quadrupole], and the above formula (1) In which R is a hydrogen atom.
Tri-form: Tetra-form: Compound M = 1.9: 100: 18.0
High-performance liquid chromatography measurement conditions:
High-performance liquid chromatograph: Acquity UPLC system manufactured by Japan Waters Co., Ltd. Column: Type: Silica gel modified with an alkyl group having 18 carbon atoms (Acquity BEH 1.7 μm C18) (Column: Inner diameter: 2.1 mm × Length 150 mm), column temperature; 40 ° C.
Eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (initial) → 50/50 (10 minutes) → 30/70 (15 minutes) → 0/100 (18-20 minutes), flow rate : 0.3 mL / min,
UV detector detection wavelength: 210 nm, sample concentration: 0.1 wt% acetonitrile solution, injection volume: 1 μL
-Tri-body peak retention time: 2.58 minutes, Tetra-body peak retention time: 6.17 minutes, Compound M peak retention time: 13.35 minutes * Tri-body peak area value as 100, The relative area value of the compound M peak was calculated.

Example 2
In a reactor equipped with a stirrer, a thermometer, and a water separator, 272 parts (2 mol) of pentaerythritol, 596 parts (8.27 mol) of acrylic acid, 460 parts of toluene as a reaction solvent, and paratoluenesulfonic acid (as an acid catalyst) (Hereinafter referred to as “PTS”) and 1.4 parts of MQ as a polymerization inhibitor were charged, and then heated under reflux at 80 kPa for 6 hours to distill 115 parts (6.4 mol) of water.
As a result of analyzing the reaction solution in the same manner as described above, the ratio of tri- and tetra-isomers was a mixture of 133.7: 100: 5.9 in area ratio.
To the reaction solution (1200 parts), 54 parts of PTS was added and stirred at 110 kPa at 80 kPa for 4 hours.
After completion of the reaction, 350 parts of toluene and 566 parts of a 10% aqueous sodium hydroxide solution were added to the reaction solution, stirred at 20 ° C. and allowed to stand, and the lower layer (aqueous layer) was separated to remove an excessive amount of acrylic acid. . Thereafter, 190 parts of water was added and stirred at 20 ° C., then allowed to stand, and the lower layer (aqueous layer) was removed. The upper layer (organic layer) was stirred at 80 ° C. for 5 hours under reduced pressure of 1 to 400 mmHg, and toluene was distilled off to obtain 650 parts of an acrylate composition.
The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 1.1: 100: 20.1

Example 3
In Example 2, the esterification reaction was carried out in the same manner as in Example 2 except that the amount of PTS was changed to 61 parts and the mixture was refluxed for 5 hours to distill 134 parts (7.4 mol) of water.
Furthermore, it was heated at 110 ° C. for 4 hours at 80 kPa, without adding an acid catalyst.
After completion of the reaction, neutralization and water washing were performed in the same manner as in Example 2 to obtain 635 parts of an acrylate composition.
The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 1.0: 100: 21.4

Comparative Example 1
In Example 2, the esterification reaction was carried out in the same manner as in Example 2 except that the amount of acrylic acid was changed to 760 parts (10.54 mol) and the amount of PTS was changed to 12 parts and refluxed for 6 hours. Part (7.4 mol) was distilled off.
Furthermore, it was heated at 110 ° C. for 4 hours at 80 kPa, without adding an acid catalyst.
After completion of the reaction, neutralization and water washing were performed in the same manner as in Example 2 to obtain 640 parts of an acrylate composition.
The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 3.9: 100: 13.5

Comparative Example 2
The mixture was refluxed for 6 hours under exactly the same conditions as in the esterification reaction of Example 2 to carry out the esterification reaction, and 115 parts (6.4 mol) of water was distilled off. In Comparative Example 2, only the esterification reaction was performed.
After completion of the reaction, neutralization and water washing were performed in the same manner as in Example 2 to obtain 610 parts of an acrylate composition.
The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri isomer: tetra isomer: compound M = 133.7: 100: 5.9

Comparative Example 3 (Additional test of Example 1 of Patent Document 5)
In a reactor equipped with a stirrer, a thermometer, and a water separator, 114 parts of pentaerythritol tetraacrylate [Aronix M-450 manufactured by Toagosei Co., Ltd.], pentaerythritol triacrylate [Aronix M-305 manufactured by Toagosei Co., Ltd.] 86 parts of toluene as a reaction solvent, 2 parts of sulfuric acid as an acidic catalyst, and 0.2 part of MQ as a polymerization inhibitor were charged, and then heated to reflux with stirring for 6 hours. After completion of the reaction, 100 parts of water was added to the reaction solution, stirred at 20 ° C. and allowed to stand to remove the lower layer (aqueous layer). The upper layer (organic layer) was stirred at 60 ° C. under reduced pressure of 1 to 400 mmHg to distill off toluene, thereby obtaining an acrylate composition.
The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 4.1: 100: 12.8

Comparative Example 4 (Additional test of Example 2 of Patent Document 5)
In a reactor equipped with a stirrer, a thermometer, and a water separator, 272 parts (2.0 mol) of pentaerythritol, 594 parts (8.25 mol) of acrylic acid, 370 parts of toluene as a reaction solvent, and 25 PTS as an acidic catalyst After charging 0.0 parts and 0.2 parts of MQ as a polymerization inhibitor, the mixture was refluxed with heating at 80 kPa for 6 hours with stirring to distill 130 parts (7.2 mol) of water. After completion of the reaction, 430 parts of a 10% aqueous sodium hydroxide solution was added to the reaction solution, and the mixture was stirred at 20 ° C. and allowed to stand, and the lower layer (aqueous layer) was separated to remove excess acrylic acid. As a result of analyzing the upper layer (organic layer) by gas chromatography under the following conditions, it was a mixture having a molar ratio of tri- and tetra-isomers of 67: 100.

Gas chromatography measurement conditions:
・ Gas chromatograph: GC-9A manufactured by Shimadzu Corporation
Column: TC-5 manufactured by GL Sciences Inc. (film thickness: 0.25 μm, inner diameter: 0.32 mm, length: 30 m)
・ Carrier gas; Helium ・ Detector; FID
Injection and detector temperature: 260 ° C
Sample concentration: 10% by weight acetone solution Injection volume: 1 μL
Column heating program: held at 100 ° C. for 3 minutes, then heated to 260 ° C. at a rate of 10 ° C./min and held at 260 ° C. for 10 minutes. Peak retention time of bird body; 11.5 minutes, Tetra-body peak retention time: 12.9 minutes * Calculating the content of di- and tri-isomers using meta-xylene as an internal standard substance

5.0 parts of PTS was added to the upper layer (organic layer), and the mixture was heated and stirred at 110 ° C. for 8 hours. After completion of the reaction, 120 parts of water was added to the reaction solution, stirred at 20 ° C. and allowed to stand to remove the lower layer (aqueous layer). The upper layer (organic layer) was stirred at 60 ° C. at a reduced pressure of 400 mmHg and reduced to 1 mmHg over 1 hour to distill off toluene, and further stirred at 60 ° C. for 1 hour under reduced pressure of 1 mmHg. An acrylate composition was obtained.
The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 8.9: 100: 20.9

Comparative Example 5
[Step 1]
In a cylindrical separable flask equipped with a stirrer, a thermometer, and a condenser, 225 parts of the acrylate composition obtained in Comparative Example 1, 342 parts of n-heptane, 2,6-di-tert-butyl-4-methylphenol 0 0.034 part was added, and stirring was performed while heating the liquid temperature to 60 ° C. (extraction tank). In addition, the stirring is carried out by separating the layer containing the acrylate composition as the main component (extraction tank lower layer) and the layer containing n-heptane as the main component and a part of the acrylate composition dissolved (upper extraction tank layer). Slowly went to maintain.
[Step 2]
On the other hand, 820 parts of n-heptane was charged into a cylindrical separable flask equipped with a stirrer, a thermometer, a cooler, and a coiled heat exchanger, and cooled so that the liquid temperature became −10 ° C. (separation tank). ).
The upper liquid of the extraction tank was pumped up using a Hycera pump (manufactured by Iwaki Co., Ltd.) and supplied to the lower part of the separation tank (supply rate; 6.8 parts / min). The liquid pumped from the upper layer of the extraction tank contained 97% by weight of n-heptane and 3% by weight of components derived from the acrylate composition.
[Step 3]
Simultaneously with step 2, the internal solution was pumped from the upper part of the separation tank using a Hycera pump and supplied to the lower layer of the extraction tank (feed rate: 6.8 parts / min). The liquid pumped from the upper part of the precipitation tank contained 99.7% by weight of n-heptane and 0.15% by weight of components derived from the polyfunctional acrylate composition.
By continuing the operations of Steps 1 to 3 for 26 hours, the tetrabodies were led to the separation tank. Tetra-white crystals were deposited in the separation tank.

After the upper part of the extraction tank was pumped up and extracted, the lower part of the extraction tank was stirred while blowing air at 70 ° C. under a reduced pressure of 1 to 500 mmHg to distill off n-heptane to obtain 47 parts of an acrylate composition. It was. The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri isomer: tetra isomer: compound M = 31.8: 100: 205.6

Comparative Example 6
A slurry was prepared by mixing 380 g of silica gel for column chromatography and n-hexane, and then packed in a column for flash chromatography. After dropping 12 g of the acrylate composition obtained in Example 3 into the packed slurry from the top of the column, supplying 8000 ml of a solvent in which n-hexane and ethyl acetate were mixed at a volume ratio of 3: 1 from the top of the column, The solvent was extracted and collected using 40 Erlenmeyer flasks of 200 ml each (fractions 1 to 40). Thereafter, while supplying 3000 ml of ethyl acetate from the upper part of the column, the solvent was extracted from the lower part of the column, and 3000 ml was collected in a round bottom flask (fraction 41).
About 41 obtained fraction meters, it analyzed by the high performance liquid chromatography on the same conditions as the above, and the ratio of the tri isomer, the tetra isomer, and the compound M was specified. As a result, the avian body was contained only in the 26th to 30th fractions.

After mixing all the fractions (1 to 25 and 31 to 41) except fractions 26 to 30, the solvent was distilled off using an evaporator while blowing air at 60 ° C. under reduced pressure of 1 to 500 mmHg to obtain 11 g of acrylate. A composition was obtained. The obtained acrylate composition was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of the tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 0: 100: 20.0

Test example 1
The following evaluation was performed using the obtained acrylate composition.

1) Curability To 100 parts of the acrylate composition, 2 parts of a photopolymerization initiator [1-hydroxycyclohexyl-phenylketone, trade name “Ilgar Cure 184” manufactured by Ciba Japan Co., Ltd.] was added and mixed to form an ultraviolet curable composition. A product was prepared.
The UV curable composition was applied to a bonderite steel plate to a thickness of 10 μm, and this was passed under a 80 W / cm condensing type high-pressure mercury lamp (focal length 30 cm) at a speed of 8 m / min using a conveyor, The number of passes required to eliminate the tack was measured, and the curability was evaluated.

2) Hardness A cured film that was completely cured in the curability test was used and evaluated by pencil hardness according to JIS K5600-5-4.

3) Emulsification resistance 3.3 g of each of the acrylate compositions obtained in the above examples and comparative examples, 6.6 g of paraxylene, and 9.9 g of pure water were put in a test tube.
The upper part of the test tube was closed with a rubber stopper, turned upside down over 30 seconds and allowed to stand after 10 reciprocations. The determination of the emulsification resistance was carried out by visually evaluating the time required for the organic layer and the aqueous layer to separate after standing and the transparency of the organic layer and the aqueous layer at the time when the two layers were separated. Judgment was made by ◎, ○, Δ and ×.
◎: Transparent ○: Slightly cloudy △: Cloudy, but the other side can be seen through the test tube ×: Cloudy and the other side of the test tube cannot be seen at all

The acrylate compositions obtained in Examples 1 to 3 were excellent in curability and emulsification resistance, and the resulting cured films had high hardness.
On the other hand, in the present invention, the acrylate composition obtained in Comparative Example 1 exceeds the upper limit of the ratio of the tri-isomer and is less than the lower limit of 15.0 of the ratio of the compound M, and the curability is insufficient. Thus, the emulsion resistance required a little time for separation, and the transparency was lowered.
In the present invention, the acrylate composition obtained in Comparative Example 2 greatly exceeds the upper limit of 2.0 to the tri-isomer ratio, and is less than the lower limit of 15.0 of the ratio of compound M. Separation took time, and the organic layer became cloudy.
Further, in Comparative Example 3 corresponding to the supplementary test of Example 1 of Patent Document 5, in the present invention, the upper limit of the proportion of tri-isomer exceeds 2.0 and the lower limit of the proportion of compound M is less than 15.0. In terms of emulsification resistance, a large amount of high-boiling components were produced in the production, and the separation required about 5 times as much as in Examples, the transparency of the organic layer was lowered, and the aqueous layer became cloudy.
In Comparative Example 4 corresponding to the supplementary test of Example 2 of Patent Document 5, in the present invention, the ratio of the compound M is satisfied, but greatly exceeds the upper limit of the ratio of the tri-isomer, and in emulsification resistance, Separation took time, and both the organic layer and the aqueous layer became cloudy.
In the present invention, the acrylate composition obtained in Comparative Example 5 greatly exceeds the upper limit 2.0 of the tri-isomer ratio, and greatly exceeds the upper limit 50.0 of the compound M ratio of the compound M. Then, because of the production of a large amount of high-boiling components in the production, the separation required about 4 times as much as in the examples, the organic layer became cloudy, and the transparency of the aqueous layer was lowered.
In the present invention, the acrylate composition obtained in Comparative Example 6 is 0, which is less than the lower limit 0.1 of the tri-isomer ratio, and the curability becomes insufficient, and the transparency is lowered in the emulsion resistance. I got stuck.

The (meth) acrylate composition obtained by the present invention can be usefully used in various industrial fields in which these are used as raw materials for paints, inks, adhesives, fillers and molding materials.

Claims (7)

Pentaerythritol tri (meth) acrylate (hereinafter referred to as “tri-form”), pentaerythritol tetra (meth) acrylate (hereinafter referred to as “tetra-form”), and formula (1):

(In the formula, R represents a hydrogen atom or a methyl group.)
A method for producing a (meth) acrylate composition comprising a compound represented by (hereinafter referred to as “compound M”),
A method for producing a (meth) acrylate composition in which a tri-form and a tetra-form of a raw material are reacted in the presence of an acid catalyst so that the tri-form, tetra-form and compound M are contained in the following proportions;
Tri-form: Tetra-form: Compound M = 0.1-2.0: 100: 15.0-50.0
The above ratio is the peak area ratio of each component of the composition measured by liquid chromatography under the following conditions, and represents the area ratio of the tri-isomer and the compound M when the area of the tetra-body is 100.
<Measurement conditions for liquid chromatography>
Equipment: High performance liquid chromatograph (HPLC)
Detector: Ultraviolet detector Column type: Column (inner diameter; 2.1 mm × length; 150 mm) made of silica gel modified with an alkyl group having 18 carbon atoms (particle diameter: 1.7 μm)
Column temperature: 40 ° C
Eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (indicating volume ratio, the same applies hereinafter) (initial) → 50/50 (10 minutes) → 30/70 (15 minutes) → 0/100 (18-20 minutes). The process for producing a (meth) acrylate composition according to claim 1, wherein the reaction is carried out at a reaction temperature of 60 to 130 ° C and stirred. The acid catalyst is used for the total amount of tri- and tetra-forms, or for the total amount of tri-, tetra- and other (meth) acrylates when (meth) acrylate other than tri- and tetra-forms is included The method for producing a (meth) acrylate composition according to claim 1 or 2, wherein 0.1 to 15% by weight is used. The ratio of the tri-form and tetra-form of the raw material is tri-form: tetra-form = 50.0 to 200.0: 100 in the area ratio measured by the measurement conditions of the liquid chromatography described above. 4. The method for producing a (meth) acrylate composition according to any one of 3 above. The polyhydric alcohol containing pentaerythritol and (meth) acrylic acid are reacted in the presence of an acid catalyst to obtain a mixture of a tri-form and a tetra-form, and then the mixture is any one of claims 1 to 4. A method for producing a (meth) acrylate composition that is used as a raw material in the production method. Pentaerythritol tri (meth) acrylate (hereinafter referred to as “tri-form”), pentaerythritol tetra (meth) acrylate (hereinafter referred to as “tetra-form”), and formula (1):

(In the formula, R represents a hydrogen atom or a methyl group.)
A (meth) acrylate composition comprising a compound represented by formula (hereinafter referred to as “compound M”), wherein the tri-form, tetra-form and compound M are contained in the following proportions:
Tri-form: Tetra-form: Compound M = 0.1-2.0: 100: 15.0-50.0
The above ratio is the peak area ratio of each component of the composition measured by liquid chromatography under the following conditions, and represents the area ratio of the tri-isomer and the compound M when the area of the tetra-body is 100.
<Measurement conditions for liquid chromatography>
Equipment: High performance liquid chromatograph (HPLC)
Detector: Ultraviolet detector Column type: Column (inner diameter; 2.1 mm × length; 150 mm) made of silica gel modified with an alkyl group having 18 carbon atoms (particle diameter: 1.7 μm)
Column temperature: 40 ° C
Eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (indicating volume ratio, the same applies hereinafter) (initial) → 50/50 (10 minutes) → 30/70 (15 minutes) → 0/100 (18-20 minutes). A curable composition comprising the (meth) acrylate composition according to claim 6.