JP2011173952A - (meth)acrylate derivative composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multibranched (meth)acrylate composition that can be used without performing specific treatment, such as advanced filtration, after reaction, as well as a simple method for producing a multibranched (meth)acrylate. <P>SOLUTION: The method for producing a multibranched (meth)acrylate is provided, in which the multibranched (meth)acrylate is obtained by reaction of a multibranched polyether polyol with (meth)acrylic acid, wherein the multibranched polyether polyol is obtained by reaction of a hydroxyalkyloxetane with a monofunctional epoxy compound in the presence of a sulfonic acid-based esterification reaction catalyst. The method for producing a multibranched (meth)acrylate includes a process of treating the reaction liquid with a basic substance without performing a process of water washing and liquid separation operation for removing the sulfonic acid-based esterification reaction catalyst after the reaction. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for producing a multibranched (meth) acrylate in the presence of a sulfonic acid esterification reaction catalyst. Moreover, this invention relates to the multibranched (meth) acrylate composition obtained by this manufacturing method.

So far, the production of multi-branched polyether polyols, which are raw materials for branched resins, has been reported. For example, Patent Document 1 describes a polyol obtained by thermal cationic polymerization of an oxetane compound. Specifically, a method of charging a reactor with a mixture of an oxetane compound and a thermal cation initiator and heating to react, and a reactor with a mixture of an oxetane compound and a thermal cation initiator and heating to start the reaction Later, a method of dropping a mixture of an oxetane compound and a thermal cation initiator continuously or sequentially is mentioned.
Patent Document 2 discloses a multi-branched polyether polyol obtained by ring-opening reaction with a hydroxyalkyl oxetane and a monofunctional epoxidized compound, and a primary hydroxyl group and a secondary hydroxyl group are included in the structure. A possibly based polyether polyol is described.

Since the acrylate compound of the above-mentioned multi-branched polyether polyol has low viscosity, low shrinkage, high adhesion, and high curability in the field of UV curable resin, application development utilizing these characteristics is expected. Although the compound and its production method are frequently found in academic literature, patents, etc., their practical application has been delayed. The reason for this is that the production cost is remarkably high because it is difficult to produce the raw material multi-branched polyether polyol, and usually operations such as water washing, liquid separation and filtration are required for the treatment after the acrylic esterification reaction. It is mentioned that these problems are not solved.

For example, Patent Document 1 describes an esterification reaction product of a polyol and (meth) acrylic acid, and describes that the esterification reaction may be performed according to a conventional method. A method of reacting a polyol and (meth) acrylic acid in an organic solvent in the presence of an acid catalyst and a radical polymerization inhibitor is disclosed. Preferred examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid, organic acids such as benzenesulfonic acid, p-toluenesulfonic acid, trichloroacetic acid, oxalic acid and formic acid, or salts thereof. Examples thereof include solid acids such as cation exchange resins, Lewis acids such as zinc chloride, tin chloride, ferric chloride, cupric chloride and cupric sulfate, and activated clay. Among these, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, etc. are mentioned.

Further, as a method based on the transesterification method, Patent Document 3 describes a method using stannoxane as a catalyst. However, in this method, removal of tin from the product after completion of the reaction becomes a problem.

However, in the acrylic esterification reaction represented by the above document, it is necessary to carry out water washing and liquid separation operation after the completion of the reaction, so that a large amount of waste liquid is generated, and basic operation is performed without performing liquid separation operation. When the reaction solution is treated with a substance or the like, a precipitate derived from the acid catalyst is generated in the acrylate compound and cannot be transferred to the next process as it is, and there is a problem that a new process such as diatomaceous earth filtration is required. The situation has not been resolved.

JP 2003-335854 A JP 2006-282698 A JP 2004-190019 A

In view of the above-described background art, an object of the present invention is to provide a method for producing a simple multibranched (meth) acrylate, and to be used without any special treatment such as high filtration after the reaction is completed ( It is to provide a (meth) acrylate composition.

The inventors have
Multi-branch obtained by reacting multi-branched polyether polyol (A) obtained by reacting hydroxyalkyl oxetane with monofunctional epoxy compound in the presence of sulfonic acid esterification reaction catalyst and (meth) acrylic acid A method for producing (meth) acrylate,
A multi-branched (meth) acrylate comprising a step of treating the reaction solution with a basic substance without performing a water washing / separation operation step for removing the sulfonic acid esterification reaction catalyst after completion of the reaction. The above-described problems have been solved by providing a manufacturing method.

ADVANTAGE OF THE INVENTION According to this invention, while being able to provide the method of manufacturing a simple multibranched (meth) acrylate, the multibranched (meth) acrylate composition which can be used without performing the process of special high filtration after completion | finish of reaction, etc. You can offer things.

In order to solve the above-mentioned problems, the present inventor conducted a detailed study on the selection of the sulfonic acid esterification catalyst and the post-treatment method of the reaction,
1) Using a long-chain alkyl-substituted benzene sulfonic acid as a sulfonic acid esterification catalyst,
2) As a reaction treatment, these problems were solved at once by treating the reaction solution with a basic substance after completion of the reaction.

That is, the present invention
1. Multi-branch obtained by reacting multi-branched polyether polyol (A) obtained by reacting hydroxyalkyl oxetane with monofunctional epoxy compound in the presence of sulfonic acid esterification reaction catalyst and (meth) acrylic acid A method for producing (meth) acrylate,
After completion of the reaction, the method comprises a step of treating the reaction solution with a basic substance without performing a water washing / separation operation step for removing the sulfonic acid esterification reaction catalyst. Acrylate production method,
2. 1. The sulfonic acid esterification reaction catalyst is benzenesulfonic acid or vinylsulfonic acid having an alkyl group having 8 to 20 carbon atoms as a substituent. The manufacturing method of the hyperbranched (meth) acrylate as described in 2.
3. The method for producing a multibranched (meth) acrylate according to claim 2, wherein the benzenesulfonic acid having an alkyl group having 8 to 20 carbon atoms as a substituent is dodecylbenzenesulfonic acid.
4). 1. The basic substance is an alkaline solution ~ 3. A method for producing a multibranched (meth) acrylate according to any one of
5.1. ~ 4. A polymerizable unsaturated resin composition comprising a hyperbranched (meth) acrylate obtained by the production method according to any one of the above and a salt formed from a sulfonic acid catalyst and a basic substance,
6). Further, it contains a diluting solvent or a polymerizable monomer. A polymerizable unsaturated resin composition according to claim 1,
I will provide a.

As the multi-branched polyether polyol obtained by reacting the hydroxyalkyl oxetane and the monofunctional epoxy compound used in the present invention, for example, a multi-branched polyether polyol described in JP-A-2006-282698 can be used.

The multibranched polyether polyol (A) of the present invention is a multibranched polyether polyol obtained by ring-opening reaction of a hydroxyalkyl oxetane and a monofunctional epoxy compound.

Here, examples of the hydroxyalkyl oxetane include those having a structure represented by the following general formula (1).

Here, in the general formula (1), R ₁ is a methylene group, ethylene group, or propylene group, while R ₂ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 1 to 1 carbon atoms. 5 represents an alkoxyalkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a 2-ethylhexyl group. As the alkoxyalkyl group having 1 to 5 carbon atoms, Includes a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a propoxyethyl group. Moreover, as a C1-C3 hydroxyalkyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group are mentioned.

Among the hydroxyalkyloxetanes represented by the general formula (1), compounds in which R ₁ is a methylene group and R ₂ is an alkyl group having 1 to 7 carbon atoms, particularly 3-hydroxymethyl-3- Ethyl oxetane and 3-hydroxymethyl-3-methyl oxetane are preferred.

Next, examples of the monofunctional epoxy compound that undergoes a ring-opening reaction with the hydroxyalkyl oxetane include olefin epoxide, alkyl glycidyl ether, and alkyl glycidyl ester.

Here, the olefin epoxide specifically includes propylene oxide, 1-butene oxide, 1-pentene oxide, 1-hexene oxide, 1,2-epoxyoctane, 1,2-epoxydodecane, cyclohexene oxide, cyclooctene oxide. , Cyclododecene oxide, styrene oxide, and fluoroalkyl epoxide having 1 to 18 fluorine atoms.

Alkyl glycidyl ether is methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, i-propyl glycidyl ether, n-butyl glycidyl ether, i-butyl glycidyl ether, n-pentyl glycidyl ether, 2-ethylhexyl-glycidyl ether, Undecyl glycidyl ether, hexadecyl glycidyl ether, aryl glycidyl ether, phenyl glycidyl ether, 2-methylphenyl glycidyl ether, 4-t-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, and Examples thereof include fluoroalkyl glycidyl ether having 1 to 18 fluorine atoms.

Alkyl glycidyl esters include glycidyl acetate, glycidyl propionate, glycidyl butyrate, glycidyl methacrylate, and glycidyl benzoate.

Here, specific examples of the method of ring-opening reaction of hydroxyalkyl oxetane and a monofunctional epoxy compound include the following (Method 1) to (Method 3).

(Method 1)
Method 1 comprises hydroxyalkyl oxetane and a monofunctional epoxy compound, on a molar basis, (hydroxyalkyl oxetane / monofunctional epoxy compound) = 1/1 to 1/10, preferably 1/1 to 1/3. These are mixed in a ratio such that they are peroxide-free organic solvents such as diethyl ether, di-i-propyl ether, di-n-butyl ether, di-i-butyl ether, di-t-butyl ether, t-amyl methyl It is dissolved in ether or dioxolane at a ratio of the raw material component / organic solvent mass ratio of 1/1 to 1/5, preferably 1 / 1.5-1 to 2.5.

The resulting solution is cooled while stirring to -10 ° C to -15 ° C, and then the polymerization initiator alone or in the solution state is 0.1 to 1 hour, preferably 0.3 to 0.5 hour. And dripping. Here, the polymerization initiator can be used at a ratio of 0.01 to 1% by mass, preferably 0.75 to 0.3% by mass, based on the total mass of the raw material monomers. Moreover, when using a polymerization initiator in a solution state, it is preferable that the density | concentration of the polymerization initiator in the said solution is 1-90 mass%, especially 25-50 mass%. Next, the polymerization solution is stirred until it reaches 25 ° C., then heated to a refluxing temperature, and the reaction is carried out until all the raw material components are reacted over 0.5 to 3 hours. The conversion rate of the raw material monomer can be controlled by confirming with GC, NMR, or IR spectrum.

After polymerization, the obtained multi-branched polyether polyol (A) is neutralized by stirring with an aqueous alkali hydroxide solution equivalent to the polymerization initiator, or by adding sodium alkoxide or potassium alkoxide equivalent to the polymerization initiator. To do. After neutralization, the mixture is filtered and the target product is extracted with a solvent, and then the solvent is distilled off under reduced pressure to obtain the target multi-branched polyether polyol (A).

(Method 2)
Method 2 comprises hydroxyalkyloxetane and monofunctional epoxy compound on a molar basis, (hydroxyalkyloxetane / monofunctional epoxy compound) = 1/1 to 1/10, preferably 1/1 to 1/3. It dissolves in a hydrocarbon solvent having a boiling point of 70 ° C. or higher. Here, examples of the hydrocarbon solvent include n-heptane, i-octane, and cyclohexane, and cyclohexane is particularly preferable from the viewpoint of solubility. The ratio of the raw material monomer to the hydrocarbon solvent is preferably 1: 1 to 1:10, particularly 1: 2.5 to 1: 3.5, the former: the latter.

The temperature of the mixture is maintained at 0 to 25 ° C., preferably 5 to 15 ° C., particularly preferably 10 to 15 ° C., and then 0.01 to 1 mol% with respect to the total amount of raw material monomers with stirring, in particular 0.05 to 0.15 mol% of polymerization initiator is added at once.
Immediately after the addition of the polymerization initiator, the system becomes heterogeneous and the system temperature rises to 25-40 ° C. Once cooled to 15-25 ° C., the reaction mixture is heated to 40-70 ° C., preferably 50-60 ° C., and all the raw material monomers are converted for 1-5 hours, preferably 2-3 hours. Perform the reaction until After completion of the reaction, the solution is neutralized and filtered in the same manner as in Method 1, and then the solvent is distilled off.

(Method 3)
Method 3 is a hydrocarbon-based organic solvent having a boiling point of 70 ° C. or higher, with a polymerization initiator in an amount of 0.01 to 1 mol%, particularly 0.05 to 0.15 mol%, based on the total amount of raw material monomers. And is maintained at 0 to 25 ° C, preferably 5 to 15 ° C, particularly preferably 10 to 15 ° C. Here, examples of the hydrocarbon solvent include n-heptane, i-octane, and cyclohexane, and cyclohexane is particularly preferable from the viewpoint of solubility. The polymerization initiator concentration in the hydrocarbon solvent is preferably 0.01 to 1% by mass, particularly preferably 0.025 to 0.25% by mass.

With respect to this solution, hydroxyalkyl oxetane and monofunctional epoxy compound, on a molar basis, (hydroxyalkyl oxetane / 1 monofunctional epoxy compound) = 1/1 to 1/10, preferably 1/1 to 1 The mixed mixture is continuously dropped so that the temperature in the system becomes 20 to 35 ° C. at a ratio of / 3. Stirring is continued until the temperature in the system reaches 20 to 25 ° C. even after completion of the dropping.

Next, the reaction mixture is heated to 40 to 70 ° C., preferably 50 to 60 ° C., and the reaction is performed for 1 to 5 hours, preferably 2 to 3 hours until all the raw material monomers are converted. The conversion rate of the raw material monomer can be controlled by confirming with GC, NMR, or IR spectrum. After completion of the reaction, the solution is neutralized and filtered in the same manner as in Method 1, and then the solvent is distilled off.

The polymerization initiator used _{here, H 2 SO 4, HCl,} HBF 4, HPF 6, HSbF 6, HAsF 6, p- toluenesulfonic acid, Bronsted acids such as trifluoromethanesulfonic _acid, BF 3, AlCl _3, Lewis acids such as TiCl ₄ , SnCl ₄ , triarylsulfonium-hexafluorophosphate, triarylsulfonium-antimonate, diaryliodonium-hexafluorophosphate, diaryliodonium-antimonate, N-benzylpyridinium-hexa Onium salt compounds such as fluorophosphate, N-benzylpyridinium-antimonate, triphenylcarbonium-tetrafluoroborate, triphenylcarbonium-hexafluorophosphate, triphenylcarbonate Triphenylcarbonium salts such as nium-hexafluoroantimonate, p-toluenesulfonyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, p-toluenesulfonic acid anhydride, methanesulfonic acid anhydride, trifluoromethanesulfonic acid anhydride, Examples include alkylating agents such as p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, methanesulfonic acid methyl ester, trifluoromethanesulfonic acid methyl ester, and trifluoromethanesulfonic acid trimethylsilyl ester.

Among these, HPF ₆ , HSbF ₆ , HAsF ₆ , and triphenylcarbonium-hexafluorophosphate are particularly preferable from the viewpoint of excellent activity, and HPF ₆ and triphenylcarbonium-hexafluorophosphate are particularly preferable.

The multibranched polyether polyol (A) thus obtained has a primary hydroxyl group (H1) and a secondary hydroxyl group (H2) in its molecular structure, and the multibranched polyether polyol ( The number average molecular weight (Mn) of A) is 1,000 to 3,500, and the hydroxyl value is 150 to 350 mg · KOH / g.

That is, since the multi-branched polyether polyol (A) of the present invention has a multi-branched structure obtained by ring-opening reaction of a hydroxyalkyl oxetane and a monofunctional epoxy compound, the multi-branched polyether polyol (A) And the number average molecular weight (Mn) has a low value of 1,000 to 3,500, so that the fluidity is extremely good compared to the prior art, and workability as a urethane resin composition is improved. Dramatically improved. Moreover, since it has a hydroxyl value of 150 to 350 mg · KOH / g and a large number of hydroxyl groups for a small molecular weight, the crosslinking density at the time of curing is increased, and a hard coating film can be formed.

Specific structures of such a multi-branched polyether polyol (A) include various structures obtained by ring-opening reaction of a hydroxyalkyl oxetane and a monofunctional epoxy compound. Specifically, the following general formula (1)

(Here, in general formula (1), R ₁ and R ₂ are the same as described above.)
And a hydroxyalkyl oxetane represented by the following general formula (2)

(In the general formula (2), R ₃ represents another structure of the epoxy group of the monofunctional epoxy compound.) When the monofunctional epoxy compound represented by the following formula is subjected to a ring-opening reaction, The multi-branched polyether polyol (A) is composed of a repeating unit represented by a structure and a structural unit appropriately selected from terminal structural units.

Here, in each of the structural units, a solid line portion indicates a single bond in the structural unit, and a broken line portion indicates a single bond that forms an ether bond with another structural unit. In addition, OR _{1 to} OR ₃ , OE1 and OE2 are structural units derived from hydroxyalkyl oxetane, OR ₁ to OR ₃ represent repeating units, and OE1 and OE2 represent terminal structural units.
Further, ER1, EE1, and EE2 are structural units derived from the monofunctional epoxy compound, ER1 represents a repeating unit, and EE1 and EE2 represent terminal structural units.

In the multi-branched polyether polyol (A) of the present invention, a multi-branched structure is formed by the repeating unit selected from the OR _{1 to} OR ₃ and ER1, and the terminal is selected from the OE1, OE2, EE1, and EE2. It has a terminal structural unit. These repeating units and terminal structural units may be present at random, or OR ₁ to OR ₃ may constitute the central part of the molecular structure and have the terminal structural unit at the terminal. . In the present invention, since the secondary hydroxyl group (H2) is essential, the EE1 is present in the multi-branched polyether polyol (A) as an essential structural unit.

The multibranched (meth) acrylate of the present invention can be obtained by reacting the above multibranched polyether polyol (A) with (meth) acrylic acid.

In this specification, (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid, and the same applies to other similar expressions.
In the multi-branched polyether polyol (A) of the present invention, there is a hydroxymethyl group generated by an addition reaction between an oxetanyl group and an epoxy group of a polyfunctional oxetane compound. The multi-branched polyether polyol (A) is synthesized by a condensation reaction between a hydroxyl group of a hydroxymethyl group and (meth) acrylic acid.

The reaction between (meth) acrylic acid and the multi-branched polyether polyol (A) can be performed, for example, at a temperature range of about −50 to 150 ° C., preferably 0 to 100 ° C.

Although the usage-amount of (meth) acrylic acid is selected by the objective, 0.1-2.0 mol is suitable with respect to the hydroxy group chemical equivalent in the said multibranched polyether polyol (A). When the amount is less than 0.1 mol, the amount of (meth) acrylate groups to be introduced decreases, which is not preferable. On the other hand, if it is used in a large amount exceeding 2.0 mol, a large amount of unreacted (meth) acrylic acid remains in the reaction solution, which is not preferred because it may take a long time for the reduced pressure removal step. More preferably, it is 0.5-1.2 mol.

The reaction proceeds even in the presence of an organic solvent or in the absence of a solvent, but it is preferably performed in the presence of an organic solvent in order to improve the stirring efficiency during the reaction.
The organic solvent that can be used is not particularly limited as long as it does not affect the reaction with (meth) acrylate, and preferably includes a hydrocarbon organic solvent, an aromatic organic solvent, and an ether organic solvent. be able to. More specifically, examples of the hydrocarbon organic solvent include hexane, heptane, octane, cyclohexane, and methylcyclohexane. Examples of the aromatic organic solvent include benzene, toluene, xylene, and ethylbenzene. Examples of the ether organic solvent include diethyl ether, diisopropyl ether, cyclopentyl methyl ether and the like.

Although reaction temperature changes with the esterification reaction catalyst and organic solvent to be used, the temperature of -20 degreeC-150 degreeC can be mentioned normally, and reaction time can mention normally 1 to 48 hours.
A more preferable temperature is 50 to 100 ° C.

In this invention, it has the characteristics in the esterification reaction catalyst used by reaction with (meth) acrylate. In the production of the multibranched (meth) acrylate of the present invention, a normal esterification reaction catalyst can be used. Such as the esterification _{catalyst, H 2 SO 4, HCl,} HBF 4, HPF 6, HSbF 6, HAsF 6, p- toluenesulfonic acid, Bronsted acids such as trifluoromethanesulfonic _acid, BF 3, AlCl ₃ , Lewis acids such as TiCl ₄ and SnCl ₄ can be mentioned. In the present invention, a sulfonic acid esterification catalyst is particularly preferable. The amount of the sulfonic acid catalyst used is usually in the range of 0.01 to 20% by weight with respect to the total charged amount of (meth) acrylic acid and the multi-branched polyether polyol (A), more preferably 0.8. 1 to 5% by weight.

More preferable examples of the catalyst include benzenesulfonic acid having an alkyl group having 8 to 20 carbon atoms as a substituent. Examples of such benzenesulfonic acid include octylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, and the like. Particularly preferred is dodecylbenzenesulfonic acid available in
It has been confirmed that dodecylbenzenesulfonic acid does not produce precipitates in the composition after the reaction obtained through the step of treating the reaction solution after the esterification reaction with a basic substance.

Similarly, since a precipitate is not generated in the composition after the reaction, vinyl sulfonic acid can be mentioned as a suitable catalyst.
In the present invention, a polymerizable unsaturated resin composition containing a multibranched (meth) acrylate composition as a product is provided. However, various sulfonic acid esterification catalysts are studied and the above-mentioned problems can be solved. This was achieved after a number of studies were conducted, and it was found that the above problems could be solved particularly when long-chain alkylbenzene sulfonic acid or vinyl sulfonic acid was used.

In the reaction, air may be blown or a polymerization inhibitor may be added for the purpose of preventing gelation due to polymerization of the polymerizable double bond of (meth) acrylate.

Examples of polymerization inhibitors include commonly known compounds such as methoquinone, hydroquinone, toluhydroquinone, methoxyphenol, phenothiazine, triphenylantimony, copper chloride, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl. A polymerization inhibitor is mentioned.

The esterification reaction of the present invention includes a step of treating the reaction solution with a basic substance after completion of the reaction.
In the esterification reaction, as a method for removing the sulfonic acid esterification catalyst, it is common to remove the sulfonic acid esterification catalyst into the aqueous layer by adding water to the reaction solution, washing with water and performing a liquid separation operation. Is. However, in the production of the multibranched (meth) acrylate of the present invention,
Even if the separation operation is impossible, or even if the separation is difficult, strong turbidity occurs in the organic layer and the aqueous layer, and the separation and purification process of the product multi-branched (meth) acrylate is performed. There is a disadvantage that is required separately.
Therefore, the present invention includes a step of treating the reaction solution with a basic substance without performing washing and liquid separation operations.

The basic substance used in the present invention is not particularly limited as long as it neutralizes the sulfonic acid esterification catalyst used, but an alkaline solution (alcoholic or aqueous) is preferable. An aqueous alkali solution is particularly preferred.
Examples of the alkaline aqueous solution include a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and lithium hydroxide. The concentration of the aqueous solution is not limited, but less water is preferably used, for example, 20 to 50%. An aqueous solution having a concentration of The alkaline aqueous solution may be added to the reaction solution after completion of the esterification reaction. The addition amount of the alkaline aqueous solution is appropriately selected according to the purpose, but it is preferable to add at least an alkali compound necessary for neutralizing the sulfonic acid catalyst.

After the addition of the aqueous alkali solution, a pressure reducing device is connected to the reaction system, and a step of removing the solvent, remaining (meth) acrylic acid, and a trace amount of water in the system may be performed while gradually increasing the degree of pressure reduction. As for the temperature in this step, a temperature of −20 ° C. to 150 ° C. can be mentioned normally, and preferably in the temperature range of 0 to 100 ° C.
In this way, the polymerizable unsaturated resin composition containing the multibranched (meth) acrylate aimed at in the present invention can be obtained. The multibranched (meth) acrylate is further diluted with a diluent solvent or a polymerizable unsaturated monomer. May be included.

Examples of the diluting solvent that can be used include organic solvents that are miscible with the polymerizable unsaturated resin composition, such as hydrocarbon-based organic solvents, aromatic-based organic solvents, ether-based organic solvents, and ketone-based organic solvents. A solvent and an ester organic solvent can be mentioned. More specifically, examples of the hydrocarbon-based organic solvent include hexane, heptane, octane, and cyclohexane. Examples of the aromatic-based organic solvent include toluene, xylene, and ethylbenzene. Examples of the solvent include tetrahydrofuran and diisopropyl ether. Examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester organic solvent include ethyl acetate and butyl acetate. And can be appropriately selected depending on the application.

Moreover, the polymerizable unsaturated resin composition of the present invention may contain a polymerizable unsaturated monomer, and examples of such polymerizable unsaturated monomer include usually known compounds. , Aromatic vinyl monomers, (meth) acrylates, allyl compounds, carboxylic acid vinyl esters, vinyl ethers, maleimide compounds, and the like. More specifically, examples of the aromatic vinyl monomer include styrene, vinyl toluene, t-butyl styrene, divinyl benzene, and the like. Examples of the (meth) acrylate include methyl (meth) acrylate, phenoxyethyl ( Examples thereof include monofunctional (meth) acrylates such as (meth) acrylate, polyfunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate, and trimethylolpropane ethylene oxide-modified (meth) acrylate. Examples of the allyl compound include diallyl phthalate and diethylene glycol bisallyl carbonate. Examples of the carboxylic acid vinyl ester include vinyl acetate and divinyl adipate. Examples of the vinyl ether include cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether, and triethylene. Examples of the maleimide compound include cyclohexyl maleimide and bisphenol A diphenyl ether bismaleimide. Other polymerizable unsaturated monomers include vinyl pyrrolidone, vinyl caprolactam, α-methylene-γ-butyrolactone, and the like, which are appropriately selected depending on the application.

In addition, since the multibranched (meth) acrylate of the present invention has a multibranched structure, compared with a linear polymer having the same molecular weight, there is no entanglement between molecules, so that it exhibits high solubility in various solvents, and a solution Viscosity can be reduced.

Furthermore, by mixing a photoradical polymerization initiator or a thermal radical polymerization initiator as a polymerization initiator into one or a mixture of two or more of the multi-branched (meth) acrylates of the present invention, photocurability or thermosetting. A polymerizable unsaturated resin composition is obtained.

As the radical photopolymerization initiator used as the polymerization initiator, known compounds that generate radicals upon irradiation with active energy rays can be used. Specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, and the like. Benzoin and alkyl ethers thereof; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 2-methylanthraquinone, 2-amylanthraquinone Anthraquinones such as 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; acetophenone di Ketals such as til ketal and benzyldimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, etc. Benzophenones; 2-methylthio-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- Aminoacetophenones such as ON; alkyl phosphines such as 2,4,6-trimethylbenzoylphosphine oxide; acridines such as 9-phenylacridine and the like. These radical photopolymerization initiators can be used alone or in combination of two or more.

The amount of these radical photopolymerization initiators is preferably 0.1 to 30 parts by mass per 100 parts by mass of the polymerizable unsaturated group-containing multibranched compound. When the amount of the radical photopolymerization initiator is less than the above range, it does not cure even when active energy rays are irradiated, or it is necessary to increase the irradiation time, making it difficult to obtain appropriate coating properties. On the other hand, even if a radical photopolymerization initiator is added in a larger amount than the above range, the curability does not change, which is not preferable in terms of physical properties and economically.

In the curable composition or photocurable / thermosetting composition of the present invention, a curing accelerator or a sensitizer is used in combination with the above-mentioned photo radical polymerization initiator in order to promote curing by active energy rays. May be.

Examples of the curing accelerator include triethylamine, triethanolamine, 2-dimethylaminoethanol, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl-4-dimethylaminobenzoate. Secondary amines; and thioethers such as β-thiodiglycol.
Examples of the sensitizer include sensitizing dyes such as (keto) coumarin and thioxanthene; and alkyl borates of dyes such as cyanine, rhodamine, safranine, malachite green, and methylene blue.

These curing accelerators or sensitizers can be used alone or in combination of two or more. The amount used is preferably 0.1 to 10 parts by mass per 100 parts by mass of the polymerizable unsaturated group-containing multibranched compound.

Examples of the thermal radical polymerization initiator used as the polymerization initiator include benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and t-butyl hydroperoxide. , Organic peroxides such as cumene hydroperoxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-di Valeronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), 1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis -4-Cyanobaric acid, 2-methyl-2,2'-azobispropaprop Azo initiators such as nitrile and the like, and more preferably non-cyan, halogen-free 1,1'-azobis (1-acetoxy-1-phenylethane) and the like.

The thermal radical polymerization initiator is preferably used in a proportion of 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass per 100 parts by mass of the polymerizable unsaturated group-containing multibranched compound.

In addition, when using an organic peroxide having a low curing rate as a thermal radical polymerization initiator, a tertiary amine such as tributylamine, triethylamine, dimethyl-p-toluidine, dimethylaniline, triethanolamine, diethanolamine, Alternatively, a metal soap such as cobalt naphthenate, cobalt octoate, or manganese naphthenate can be used as the accelerator.

The curable resin composition of the present invention can contain a thermosetting component. As the thermosetting component, a polyfunctional epoxy compound or oxetane compound having at least two oxirane groups or oxetanyl groups in one molecule can be suitably used.

Examples of the polyfunctional epoxy compound include novolak-type epoxy resins (for example, novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenol, alkylphenol and formaldehyde in the presence of an acid catalyst with epichlorohydrin or methyl epichlorohydrin. It is obtained by reaction, and commercially available products include EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN-S manufactured by Nippon Kayaku Co., Ltd .; manufactured by Dow Chemical DEN-431, DEN-438; DIC Corporation N-730, N-770, N-865, N-665, N-673, N-695, VH-4150, etc.), bisphenol A type epoxy resin (For example, bisphenol, bisphenol It is obtained by reacting bisphenols such as bisphenol and tetrabromobisphenol with epichlorohydrin or methyl epichlorohydrin, and commercially available products include Epicoat 1004 and Epicoat 1002 manufactured by Yuka Shell Epoxy Co., Ltd .; manufactured by Dow Chemical Co., Ltd. DER-330, DER-337, etc.), trisphenol methane type epoxy resin (for example, trisphenol methane, triskresol methane, etc., and epichlorohydrin or methyl epichlorohydrin are obtained. EPPN-501, EPPN-502, etc.), tris (2,3-epoxypropyl) isocyanurate, biphenol diglycidyl ether, other alicyclic epoxy resins, amino group-containing epoxy trees , Copolymerization type epoxy resin, cardo type epoxy resin, a calixarene type epoxy resins conventionally known epoxy resins may be used alone or in combination of two or more.

The polymerizable unsaturated group-containing hyperbranched compound of the present invention can be advantageously used as a resin additive in various fields. Examples thereof include molecular weight regulators such as polystyrene resins and acrylic resins, and crosslinking agents such as polyolefin resins and butadiene rubber. Moreover, it can be advantageously used as a photocurable component or a thermosetting component. The obtained cured product can be applied to various fields, such as woodwork, plastic, steel plate paint, UV curable ink, photosensitive resin letterpress, photocuring adhesive, anaerobic adhesive, concrete running agent, It can be used for various applications such as void repairing agents such as putty, FRP molded products, extruded resin molded products, films, and foamed resin molded products.

(Production Example 1) <Synthesis of multi-branched polyether polyol (A)>
In a 1000 mL three-necked flask equipped with nitrogen, an air reflux condenser, a magnetic stirring bar, and a thermometer, 1.24 g (8.7 mmol) of boron trifluoride diethyl ether complex was dried and free of peroxide. Diluted with 273 g of methyl-t-butyl ether.
In a separate container, 140 g (1.21 mol) of 3-hydroxymethyl-3-ethyloxetane and 70.0 g (1.21 mol) of propylene oxide were mixed, and the above three-necked flask was consumed with a metering pump for 5.5 hours. And dripped. At this time, the system was cooled by an ice bath as needed to keep the temperature in the system at 20 ° C. After completion of the dropwise addition, 63.0 g (1.08 mol) of propylene oxide was further added dropwise over 3 hours while keeping the temperature in the system at 20 ° C., and the mixture was further stirred for 4 hours. Here, 0.620 g (4.4 mmol) of boron trifluoride diethyl ether complex was added, and the mixture was further stirred at 20 ° C. for 6 hours.

The reaction mixture was adsorbed and removed by adding hydrotalcite 10 times the weight of boron trifluoride diethyl ether complex used in the reaction and refluxing for 1 hour. After the hydrotalcite was filtered off, methyl-t-butyl ether was removed to obtain 267 g of a transparent and highly viscous multi-branched polyether polyol (A).
This multi-branched polyether polyol (A) has Mn = 2,876 g / mol, Mw = 7,171 g / mol, hydroxyl value = 253 mg · KOH / g, and 3-hydroxymethyl- on a molar basis from proton NMR. It was found that 3-ethyloxetane: propylene oxide = 1: 1.9. The ratio of secondary hydroxyl groups to all hydroxyl groups was 40%. This is referred to as multi-branched polyether polyol (A) HB-1.

(Example 1) <Synthesis of polymerizable unsaturated group-containing hyperbranched polyether>
In a 500 mL four-necked flask equipped with a Dean-Stark tube, nitrogen and air inlet tube, stirring device, and thermometer, 155 g of the aforementioned multi-branched polyether polyol (A) HB-1, 51 g of acrylic acid, 200 g of cyclohexane Then, 0.21 g of hydroquinone monomethyl ether and 4 g (12.3 mmol) of dodecylbenzenesulfonic acid as a catalyst were charged, and the temperature was raised to 82 ° C. under a mixed gas flow of nitrogen and air 2: 1. Cyclohexane reflux began, and water flow began gradually. Thereafter, when the temperature was raised to 85 ° C. and reacted for 24 hours, it reached 70% of the theoretical dehydration amount, and cooling was started. After cooling to around 30 ° C., the Dean-Stark tube was replaced with a water-cooled condenser. Next, 0.98 g (12.3 mmol) of 50% sodium hydroxide was charged, and the temperature was raised to 80 ° C. and held. Next, it was connected to a decompression device, and a step of removing the solvent in the system, the remaining acrylic acid and a trace amount of water was performed while gradually increasing the degree of decompression. Since the acid value became 5 or less, it was taken out from the reaction vessel and filled into a glass bottle. The obtained polymerizable unsaturated group-containing multi-branched polyether had a hydroxyl value of 73.1 mg · KOH / g, and an acrylic ester value rate of all hydroxyl groups was 66%. The acrylic group concentration was calculated to be 2.54 mmol / g. Hereinafter, this is referred to as polymerizable unsaturated group-containing multi-branched polyether resin HBA-1. The appearance was visually confirmed one day after cooling at room temperature. It was light yellow and transparent, and there was no turbidity.

(Example 2) <Synthesis of polymerizable unsaturated group-containing hyperbranched polyether>
In the same manner as in Example 1, in a 500 mL four-necked flask, 155 g of the above-mentioned multi-branched polyether polyol (A) HB-1, 51 g of acrylic acid, 200 g of cyclohexane, 0.21 g of hydroquinone monomethyl ether, vinylsulfone as a catalyst The acid 1.3g (12.3mmol) was prepared, and it heated up to 82 degreeC under the mixed gas circulation of nitrogen and air 2: 1. Cyclohexane reflux began, and water flow began gradually. Thereafter, the temperature was raised to 85 ° C. and the reaction was carried out for 20 hours. Since the amount reached 80% of the theoretical dehydration amount, cooling was started. After cooling to around 30 ° C., the Dean-Stark tube was replaced with a water-cooled condenser. Next, 0.98 g (12.3 mmol) of 50% sodium hydroxide was charged, and the temperature was raised to 80 ° C. and held. Next, it was connected to a decompression device, and a step of removing the solvent in the system, the remaining acrylic acid and a trace amount of water was performed while gradually increasing the degree of decompression. Since the acid value became 5 or less, it was taken out from the reaction vessel and filled into a glass bottle. The hydroxyl group value of the obtained polymerizable unsaturated group-containing multi-branched polyether was 50.5 mg · KOH / g, and the acrylic ester value rate of all hydroxyl groups was 76%. The acrylic group concentration was calculated to be 2.86 mmol / g. Hereinafter, this is referred to as polymerizable unsaturated group-containing multi-branched polyether resin HBA-2. As in Example 1, the appearance was visually confirmed. It was light yellow and transparent, and there was no turbidity.

(Comparative Example 1) <Synthesis of polymerizable unsaturated group-containing hyperbranched polyether>
In the same manner as in Example 1, in a 500 mL four-necked flask, 155 g of the above-mentioned multi-branched polyether polyol (A) HB-1, 51 g of acrylic acid, 200 g of cyclohexane, 0.21 g of hydroquinone monomethyl ether, and paratoluene as a catalyst. 2.1 g (12.3 mmol) of sulfonic acid was charged, and the temperature was raised to 82 ° C. under a mixed gas flow of nitrogen and air 2 to 1. Cyclohexane reflux began, and water flow began gradually. Then, when it heated up to 85 degreeC and made it react for 20 hours, since it reached 70% of theoretical dehydration amount, cooling was started. After cooling to around 30 ° C., the Dean-Stark tube was replaced with a water-cooled condenser. Next, 0.98 g (12.3 mmol) of 50% sodium hydroxide was charged, and the temperature was raised to 80 ° C. and held. Next, it was connected to a decompression device, and a step of removing the solvent in the system, the remaining acrylic acid, and a trace amount of water was carried out while gradually increasing the degree of decompression. Since the acid value became 5 or less, it was taken out from the reaction vessel and filled into a glass bottle. The hydroxyl group value of the obtained polymerizable unsaturated group-containing multi-branched polyether compound was 71.0 mg · KOH / g, and the acrylic acid ester value rate of all hydroxyl groups was 67%. The acrylic group concentration was calculated to be 2.57 mmol / g.
This is hereinafter referred to as polymerizable unsaturated group-containing multi-branched polyether HBA-3. As in Example 1, the appearance was visually confirmed. It was pale yellowish white and cloudy.

(Comparative Example 2) <Synthesis of polymerizable unsaturated group-containing hyperbranched polyether>
In the same manner as in Example 1, in a 500 mL four-necked flask, 155 g of the above-mentioned multi-branched polyether polyol (A) HB-1, 51 g of acrylic acid, 200 g of cyclohexane, 0.21 g of hydroquinone monomethyl ether, and paratoluene as a catalyst. 2.1 g (12.3 mmol) of sulfonic acid was charged, and the temperature was raised to 82 ° C. under a mixed gas flow of nitrogen and air 2 to 1. Cyclohexane reflux began, and water flow began gradually. Then, when it heated up to 85 degreeC and made it react for 20 hours, since it reached 70% of theoretical dehydration amount, cooling was started. Cooled to around 30 ° C. Next, 50 g (250 mmol) of 20% sodium hydroxide was added and stirred for 10 minutes while maintaining this temperature. Next, stirring was stopped, the whole amount was transferred to a separatory funnel, and allowed to stand to carry out a solvent / water separation step. Immediately after, it was milky white and emulsified. When confirmed after 24 hours, it was milky white and the solvent and water were not separated. Similarly, it was not separated after 3 days.
Therefore, in this production method, a polymerizable unsaturated group-containing multibranched polyether could not be obtained.

<Evaluation method>
<Verification of solubility in polymerizable unsaturated monomer (visual observation of appearance)>
60 g of the obtained polymerizable unsaturated group-containing multi-branched polyether resin and 40 g of styrene monomer were mixed and stirred while heating at 50 ° C. to prepare a solution. The appearance of the solution after one day of standing at room temperature was visually observed.
This result was evaluated in three stages.
○: Light yellow and transparent with no turbidity or precipitation.
Δ: Light yellow and transparent with turbidity observed.
X: Pale yellowish white, cloudy and precipitated.
The polymerizable unsaturated group-containing multi-branched polyether resin used for the evaluation is HBA-1 and HBA-2 obtained in Examples and HBA-3 obtained in Comparative Examples. The results are shown in Table-1.

<Confirmation of molecular weight increase by addition of small amount during synthesis of polystyrene resin>
9 g of styrene monomer, 1 g of toluene, 0.0018 g of a polymerization initiator (Perbutyl Z, manufactured by NOF Corporation) and 0.009 g of a polymerizable unsaturated group-containing multi-branched polyether resin were mixed and stirred at 30 ° C. to prepare a solution. This was charged into a glass ampule, purged with nitrogen, and sealed. This ampoule was immersed in an oil bath, and the oil in the bath was gradually heated from 130 ° C. to 160 ° C. over 5 hours. After allowing to cool at room temperature for about 5 hours, the ampoule was broken and the polymer was taken out. 1 g of this polymer is dissolved in 60 g of toluene and filtered through a 300-mesh SUS wire mesh to confirm the presence or absence of insoluble matter. Next, it was reprecipitated with 500 g of methanol, and the polymer was collected and dried at 60 ° C. for 12 hours by vacuum drying to obtain a polystyrene resin for evaluation. In addition, as a blank test, what did not use a polymerizable unsaturated group containing hyperbranched polyether resin was also compared simultaneously. The polymerizable unsaturated group-containing hyperbranched polyether used for evaluation is HBA-1 and HBA-2 obtained in Examples and HBA-3 obtained in Comparative Examples.

The obtained polystyrene resin was dissolved in THF, and the molecular weight distribution was measured. Two detectors were used to measure the molecular weight: a refractive index formula and multi-angle laser scattering detection. Let the weight average molecular weight obtained from the refractive index formula be RI-Mw. Let the weight average molecular weight obtained from multi-angle laser scattering detection be MALS-Mw. The results are shown in Table-2. In addition, as a blank test, the result which did not use polymerizable unsaturated group containing multibranched polyether resin is also shown in Table-2 (evaluation example 1).

<Confirmation of UV curable coating film performance (evaluation of UV curable resin suitability)>
Polymeric unsaturated group-containing multi-branched polyether resin 50 g, methyl ethyl ketone 50 g, photoinitiator 1 g hydroxy-cyclohexyl-phenyl-ketone) was stirred at 50 ° C. in the dark to prepare a solution. The appearance of the solution after one day of standing at room temperature was visually observed.
This result was evaluated in three stages.
○: Light yellow and transparent with no turbidity or precipitation.
(Triangle | delta): It is light yellow transparent and a thin turbidity is recognized.
X: Pale yellowish white, cloudy and precipitated.
The polymerizable unsaturated group-containing multi-branched polyether resin used for the evaluation is HBA-1 and HBA-2 obtained in Examples and HBA-3 obtained in Comparative Examples. The results are shown in Table-1.

Next, an ultraviolet curable coating film was prepared using this solution. After coating on a 100 micron PET film using a bar coater, it was dried for 5 minutes in a dryer at 80 ° C. and cooled to room temperature. The coated material obtained with a thickness of about 100 μm was irradiated twice with a metal halide lamp having a conveyor speed of 5 m / min and an output of 160 W / cm under the condition of 0.8 J / cm ² . The obtained cured product was evaluated according to the following method.
Hardness evaluation: Pencil hardness A pencil scratch test according to JIS K-5400 was performed, and evaluation was performed by tearing the cured product.
Bending test: A PET film having a coating film was bent at 180 ° C., and cracking and peeling of the coating film were visually observed.
This result was evaluated in three stages.
○: No cracking or peeling of the coating film is observed.
(Triangle | delta): The crack of a coating film is recognized.
X: The crack of a coating film and peeling are recognized.
Transparency of coating film: A test piece was placed on black drawing paper, and the presence or absence of turbidity was visually confirmed.
The polymerizable unsaturated group-containing hyperbranched polyether used for evaluation is HBA-1 and HBA-2 obtained in Examples and HBA-3 obtained in Comparative Examples. The results are shown in Table 3 (Evaluation Example 2).

<Explanation of abbreviations in the table>
DBSA: Dodecylbenzenesulfonic acid VSA: Vinylsulfonic acid PTSA: p-toluenesulfonic acid SM: Styrene monomer

As can be seen from Table 1, according to the production method of the present invention, the polymerizable unsaturated group-containing multi-branched polyether resin can be easily recovered and produced because it is not washed with water. Only a small amount of water (condensed water) is discarded, and the recovered reaction solvent and unreacted (meth) acrylic acid can be reused. The obtained polymerizable unsaturated resin of the present invention has no turbidity and is not turbid even when used as a solution, and can be used as a resin raw material for many applications.

Further, as can be seen from Table-2, the polymerizable unsaturated resin of the present invention is also useful as a molecular weight regulator of polystyrene resin, and increases the molecular weight but hardly generates insoluble matter and is easy to control. Further, as can be seen from Table-3, the coating film obtained by UV curing the polymerizable unsaturated resin of the present invention is transparent, excellent in substrate followability, and exhibits appropriate hardness. It is also useful.

On the other hand, in the conventional method of performing alkaline water washing after the acid catalyst reaction, the polymerizable unsaturated group-containing multi-branched polyether resin is easily emulsified with water and difficult to separate, and cannot be recovered, resulting in poor mass productivity.
Although it is possible to react in the same manner using conventional short-chain alkylbenzenesulfonic acid such as p-toluenesulfonic acid, turbidity of the resin due to precipitation of sulfonate and the like occurs, and filtration is difficult. Therefore, when used as it is, there are quality problems such as turbidity and generation of insoluble matter. Therefore, it is difficult to use as a resin raw material for many applications.

The multi-branched (meth) acrylate of the present invention can be used as a polymerizable unsaturated resin composition.

Claims (6)

Multi-branch obtained by reacting multi-branched polyether polyol (A) obtained by reacting hydroxyalkyl oxetane with monofunctional epoxy compound in the presence of sulfonic acid esterification reaction catalyst and (meth) acrylic acid A method for producing (meth) acrylate,
After completion of the reaction, the method comprises a step of treating the reaction solution with a basic substance without performing water washing and a liquid separation operation step for removing the sulfonic acid esterification reaction catalyst. Method for producing acrylate. The method for producing a multibranched (meth) acrylate according to claim 1, wherein the sulfonic acid esterification reaction catalyst is benzenesulfonic acid having a C8-20 alkyl group as a substituent or vinylsulfonic acid. The method for producing a multibranched (meth) acrylate according to claim 2, wherein the benzenesulfonic acid having an alkyl group having 8 to 20 carbon atoms as a substituent is dodecylbenzenesulfonic acid. The method for producing a multibranched (meth) acrylate according to any one of claims 1 to 3, wherein the basic substance is an alkaline solution. A polymerizable unsaturated resin composition comprising a hyperbranched (meth) acrylate obtained by the production method according to claim 1, and a salt formed from a sulfonic acid esterification reaction catalyst and a basic substance. . Furthermore, the polymerizable unsaturated resin composition of Claim 5 containing a dilution solvent or a polymerizable unsaturated monomer.