Sulfonic acid (METH)acrylate composition

Abstract

To provide a sulfonic acid (meth)acrylate composition having superior hydrophilicity and degradability while exhibiting reduced coloration during storage.SOLUTION: A sulfonic acid (meth)acrylate composition comprises a sulfonic acid (meth)acrylate (A) having a specific structure and a hydroxyalkane sulfonic acid (B). Assuming that the total of the sulfonic acid (meth)acrylate (A) and the hydroxyalkane sulfonic acid (B) is 100 mass%, the mass ratio (A):(B) of the sulfonic acid (meth)acrylate (A) to the hydroxyalkane sulfonic acid (B) is 99.95:0.05 to 85:15.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a sulfonic acid (meth)acrylate composition. [Background technology]

[0002] Ethylenically unsaturated monomers containing a sulfonic acid group are widely used as reactive emulsifiers in emulsion polymerization systems and for imparting antistatic properties to the resulting polymers, taking advantage of the excellent surface activity and hydrophilicity of the sulfonic acid group. Conventionally, a dehydration esterification reaction using an acid component such as p-toluenesulfonic acid or sulfuric acid as a catalyst has been widely used as a method for synthesizing monomers having an ethylenically unsaturated group. However, production methods using these acid components as raw materials have also been disclosed for ethylenically unsaturated monomers containing a sulfonic acid group (Patent Document 1, Patent Document 2).

[0003] On the other hand, in recent years, from the viewpoint of environmental consideration, efforts have been made to reduce organic solvent emissions and to develop materials that are easily degradable in the environment. Regarding the reduction of organic solvent emissions, there has been an active movement to switch from organic solvent-based to water-based systems in the development of various compositions such as printing inks, paints, and adhesives, and a wide range of materials with good water solubility have been developed (Patent Document 3). Furthermore, materials that are highly biodegradable in the environment have been disclosed that are characterized by being able to decompose quickly and prevent long-term retention in the environment even if discarded materials are released into the soil or ocean (Patent Document 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 63-284156 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-168937 [Patent Document 3] Japanese Patent Application Publication No. 2014-198766 [Patent Document 4] Japanese Patent Application Publication No. 2023-149391 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the sulfonic acid group-containing ethylenically unsaturated monomers obtained in Patent Documents 1 and 2 tend to yellow over time due to residual p-toluenesulfonic acid or sulfuric acid added as a catalyst, which has led to limitations on their use in applications where color change over time is a problem, such as inks and paints, or in applications where transparency is required, such as adhesives for electronic materials. Furthermore, the ethylenically unsaturated monomers containing sulfonic acid groups obtained in Patent Documents 1 and 2 use organic solvents such as xylene during the reaction, making it difficult to apply them to water-based paints or water-contact adhesives, which require organic solvent-free materials. Furthermore, although compounds containing sulfonic acid groups are known to exhibit a certain degree of biodegradability, when ethylenically unsaturated monomers containing sulfonic acid groups are used as components that impart hydrophilicity to aqueous materials as in Patent Document 3, if the hydrolysis property of the material is insufficient, disposal of the material becomes difficult, and there is a possibility that the energy required for disposal increases and the processing time may be extended. In light of this, there is a demand for a (meth)acrylate having a sulfonic acid group that can improve hydrolysis while maintaining hydrophilicity and is less likely to develop coloration during storage. There is also a demand for a (meth)acrylate having a sulfonic acid group that can be produced without using an organic solvent during the reaction. Therefore, an object of the present invention is to provide a (meth)acrylate composition having a sulfonic acid group, which can improve hydrolysis property while maintaining the hydrophilicity-imparting effect and is less likely to cause discoloration during storage. Another object of the present invention is to provide a method for producing a (meth)acrylate composition having a sulfonic acid group, which does not use an organic solvent during the reaction. [Means for solving the problem]

[0006] As a result of investigations aimed at solving the above problems, the present inventors have found that the above problems can be solved by a composition containing a sulfonic acid derivative having a specific structure and a sulfonic acid (meth)acrylate. That is, the present invention is as follows.

[0007] [1] A sulfonic acid (meth)acrylate composition comprising a sulfonic acid (meth)acrylate (A) represented by the following formula (1) and a hydroxyalkanesulfonic acid (B) represented by the following formula (2), wherein the mass ratio (A):(B) of the sulfonic acid (meth)acrylate (A) to the hydroxyalkanesulfonic acid (B) is 99.95:0.05 to 85:15 when the total of the sulfonic acid (meth)acrylate (A) and the hydroxyalkanesulfonic acid (B) is 100 mass%. [ka] (In formula (1), R 1 represents a hydrogen atom or a methyl group. 2 represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. M represents a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, or NR 3 3, and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. [ka] (In formula (2), R 4 represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. [2] A method for producing a sulfonic acid (meth)acrylate composition containing a sulfonic acid (meth)acrylate (A) represented by the following formula (1) and a hydroxyalkanesulfonic acid (B) represented by the following formula (2), comprising a step of reacting acrylic acid or methacrylic acid with a hydroxyalkanesulfonic acid or a metal salt of a hydroxyalkanesulfonic acid, characterized in that no organic solvent is used during the reaction step: [ka] (In formula (1), R 1 represents a hydrogen atom or a methyl group. 2 represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. M represents a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, or NR 3 3, and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. [ka] (In formula (2), R 4 represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a sulfonic acid (meth)acrylate composition that can improve hydrolysis while maintaining the hydrophilicity-imparting effect and is less likely to cause coloration during storage. Also, it is possible to provide a method for producing a (meth)acrylate composition having a sulfonic acid group, which does not use an organic solvent during the reaction. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited to the embodiment described in this specification and can be modified in various ways without departing from the gist of the present invention. In this specification, numerical ranges defined using the symbol "to" are inclusive of the numerical values ​​at both ends (upper and lower limits) of the symbol "to." For example, "2 to 5" means 2 or more and 5 or less. In the present invention, "(meth)acrylic" is a general term that includes acrylic and methacrylic.

[0010] The composition of the present invention contains the sulfonic acid (meth)acrylate (A) represented by the above formula (1) and the hydroxyalkanesulfonic acid (B) represented by the above formula (2). Each component will be described below.

[0011] <Sulfonic acid (meth)acrylate (A)> The sulfonic acid (meth)acrylate (A) contained in the composition of the present invention is a compound represented by the following general formula (1). [ka] In formula (1), R 1 represents a hydrogen atom or a methyl group. R 2 R is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. 2 is more preferably an alkylene group having 1 to 6 carbon atoms or an oxyalkylene group having an average added mole number of 1 to 20. The alkylene group particularly preferably has 1 to 3 carbon atoms. From the viewpoint of availability, the alkylene group structure is more preferably a methylene group, an ethylene group, or a trimethylene group. R 2 The oxyalkylene group in the formula (I) is preferably an oxyalkylene group having 1 to 10 carbon atoms, and more preferably an oxyalkylene group having 2 to 3 carbon atoms. The structure of the oxyalkylene group is preferably oxyethylene or oxypropylene, and more preferably oxyethylene.

[0012] M is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, or a group of the general formula NR 33, and R 3 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. From the viewpoint of low coloration, M is more preferably selected from a lithium atom, a sodium atom, and a potassium atom, and is particularly preferably a sodium atom. 3 is more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.

[0013] Examples of the sulfonic acid (meth)acrylate (A) represented by formula (1) include 2-(acryloyloxy)ethanesulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, lithium 2-(methacryloyloxy)ethanesulfonate, sodium 2-(methacryloyloxy)ethanesulfonate, potassium 2-(methacryloyloxy)ethanesulfonate, ammonium 2-(methacryloyloxy)ethanesulfonate, sodium 3-(methacryloyloxy)propanesulfonate, sodium 5-(methacryloyloxy)pentanesulfonate, sodium 10-(methacryloyloxy)decanesulfonate, and sodium (methacryloyloxy)polyethylene glycol sulfonate. Among these, from the viewpoints of hydrophilicity and hydrolysis property, 2-(acryloyloxy)ethanesulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, lithium 2-(methacryloyloxy)ethanesulfonate, sodium 2-(methacryloyloxy)ethanesulfonate, potassium 2-(methacryloyloxy)ethanesulfonate, and ammonium 2-(methacryloyloxy)ethanesulfonate are preferred, and among these, sodium 2-(methacryloyloxy)ethanesulfonate is particularly preferred. The sulfonic acid (meth)acrylate (A) may be used alone or in combination of two or more kinds.

[0014] The hydroxyalkanesulfonic acid (B) of the present invention is a compound represented by the following general formula (2). [ka] In formula (2), R4 R is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. 4 R is more preferably an alkylene group having 1 to 6 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 20. 4 is particularly preferably an alkylene group having a carbon number of 1 to 3. From the viewpoint of availability, the structure of the alkylene group is more preferably a methylene group, an ethylene group, or a trimethylene group. R 4 The oxyalkylene group in the formula (I) is preferably an oxyalkylene group having 1 to 10 carbon atoms, and more preferably an oxyalkylene group having 2 to 3 carbon atoms. The structure of the oxyalkylene group is preferably oxyethylene or oxypropylene, and more preferably oxyethylene.

[0015] Examples of the hydroxyalkanesulfonic acid (B) represented by formula (2) include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 5-hydroxypentanesulfonic acid, 10-hydroxydecanesulfonic acid, and polyethylene glycol sulfonic acid. From the viewpoint of hydrophilicity, 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, and 5-hydroxypentanesulfonic acid are preferred, and among these, 2-hydroxyethanesulfonic acid is particularly preferred. The hydroxyalkanesulfonic acid (B) may be used alone or in combination of two or more kinds.

[0016] When the total amount of the sulfonic acid (meth)acrylate (A) and the hydroxyalkanesulfonic acid (B) is taken as 100.00% by mass, the content of the sulfonic acid (meth)acrylate (A) is 85.00 to 99.95% by mass, and the content of the hydroxyalkanesulfonic acid (B) is 0.05 to 15.00% by mass. By setting the content within these ranges, it is possible to obtain a sulfonic acid (meth)acrylate composition that is excellent in hydrophilicity and decomposability and is resistant to coloration during storage. From the viewpoint of decomposability, the content of the sulfonic acid (meth)acrylate (A) is preferably 99.00 mass% or less, more preferably 95.00 mass% or less, and from the viewpoint of decomposability, the content of the hydroxyalkanesulfonic acid (B) is preferably 1.00 mass% or more, more preferably 5.00 mass% or more. From the viewpoint of hydrophilicity, the content of the sulfonic acid (meth)acrylate (A) is preferably 88.00 mass% or more, more preferably 90.00 mass% or more, and even more preferably 92.00 mass% or more. From the viewpoint of hydrophilicity, the content of the hydroxyalkanesulfonic acid (B) is preferably 12.00 mass% or less, more preferably 10.00 mass% or less, and even more preferably 8 mass% or less.

[0017] Furthermore, the total amount of the sulfonic acid (meth)acrylate (A) and the hydroxyalkanesulfonic acid (B) relative to the total amount of the sulfonic acid (meth)acrylate composition is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0018] <Polymerization inhibitor> A polymerization inhibitor may be added to the composition of the present invention as needed. For example, 4-methoxyphenol, hydroquinone, dibutylhydroxytoluene, etc. can be used. The blending ratio of the polymerization inhibitor in the sulfonic acid (meth)acrylate composition is preferably 0.001 to 5.0 mass% and more preferably 0.001 to 1.0 mass% relative to 100 mass% of the sulfonic acid (meth)acrylate composition. By setting the amount of polymerization inhibitor added within the above range, the sulfonic acid (meth)acrylate composition is less likely to deteriorate during long-term storage or to become discolored during high-temperature storage.

[0019] <Water> The composition of the present invention may contain water as needed. The blending ratio of water in the sulfonic acid (meth)acrylate composition is preferably 3.0 mass% or less, more preferably 1.0 mass% or less, based on 100 mass% of the sulfonic acid (meth)acrylate composition. When the water content is 3.0 mass% or less, coloration that occurs during storage at high temperatures is less likely to progress.

[0020] <Method of producing the composition> The method for producing a sulfonic acid (meth)acrylate composition of the present invention includes a step of reacting (meth)acrylic acid with a hydroxyalkanesulfonic acid or a metal salt of a hydroxyalkanesulfonic acid, and is characterized in that no organic solvent is used during the reaction step. The (meth)acrylic acid used in the present invention is acrylic acid or methacrylic acid.

[0021] Examples of hydroxyalkanesulfonic acids or metal salts of hydroxyalkanesulfonic acids used in the present invention include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 5-hydroxypentanesulfonic acid, 10-hydroxydecanesulfonic acid, polyethylene glycol sulfonic acid, lithium 2-hydroxyethanesulfonate, lithium 3-hydroxypropanesulfonate, lithium 5-hydroxypentanesulfonate, lithium 10-hydroxydecanesulfonate, lithium polyethylene glycol sulfonate, sodium 2-hydroxyethanesulfonate, sodium 3-hydroxypropanesulfonate, sodium 5-hydroxypentanesulfonate, sodium 10-hydroxydecanesulfonate, sodium polyethylene glycol sulfonate, potassium 2-hydroxyethanesulfonate, potassium 3-hydroxypropanesulfonate, potassium 5-hydroxypentanesulfonate, potassium 10-hydroxydecanesulfonate, and potassium polyethylene glycol sulfonate. The metal salts of hydroxyalkanesulfonic acids or hydroxyalkanesulfonic acids may be solid or in the form of an aqueous solution. Among these, from the viewpoint of hydrophilicity and hydrolysis property, 2-hydroxyethanesulfonic acid, lithium 2-hydroxyethanesulfonate, sodium 2-hydroxyethanesulfonate, and potassium 2-hydroxyethanesulfonate are preferred, and among these, sodium 2-hydroxyethanesulfonate is more preferred.

[0022] [Esterification Reaction] In the present invention, a sulfonic acid (meth)acrylate composition containing a sulfonic acid (meth)acrylate (A) represented by formula (1) and a hydroxyalkanesulfonic acid (B) represented by formula (2) can be produced by subjecting (meth)acrylic acid and a hydroxyalkanesulfonic acid or a metal salt of a hydroxyalkanesulfonic acid to an esterification reaction in the presence of a reaction catalyst.

[0023] The form of the hydroxyalkanesulfonic acid or metal salt of hydroxyalkanesulfonic acid used in the production method of the present invention is not particularly limited and may be a solid or an aqueous solution. In the case of an aqueous solution, however, dehydration is preferably carried out before the addition of the reaction catalyst. Dehydration may be carried out on the hydroxyalkanesulfonic acid or metal salt of hydroxyalkanesulfonic acid alone, or on the mixture with (meth)acrylic acid. The water content of the mixture of (meth)acrylic acid and hydroxyalkanesulfonic acid or metal salt of hydroxyalkanesulfonic acid before the addition of the reaction catalyst is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.

[0024] Examples of the reaction catalyst include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 5-hydroxypentanesulfonic acid, 10-hydroxydecanesulfonic acid, and polyethylene glycol sulfonic acid, and among these, 2-hydroxyethanesulfonic acid is preferred from the viewpoint of reactivity.

[0025] In the present invention, the molar ratio when reacting (meth)acrylic acid with a hydroxyalkanesulfonic acid or a metal salt of a hydroxyalkanesulfonic acid is preferably 4.0 to 30.0 mol, more preferably 6.0 to 25.0 mol, and even more preferably 8.0 to 20.0 mol of (meth)acrylic acid per 1.0 mol of a hydroxyalkanesulfonic acid or a metal salt of a hydroxyalkanesulfonic acid. When the ratio is 4.0 mol or more of (meth)acrylic acid per 1.0 mol of a hydroxyalkanesulfonic acid or a metal salt of a hydroxyalkanesulfonic acid, the dispersibility of the hydroxyalkanesulfonic acid or the metal salt of a hydroxyalkanesulfonic acid in the reaction solution is improved.

[0026] The dehydration esterification reaction is preferably carried out in the presence of a reaction catalyst at a temperature of preferably 100 to 150°C, more preferably 110 to 140°C, for about 1 to 24 hours. A reaction temperature of 100°C or higher facilitates the reaction. Furthermore, a reaction temperature of 150°C or lower can prevent the reaction solution from becoming discolored. The water generated in the dehydration esterification reaction may be removed by heating under reflux immediately after the start of the reaction, or by starting heating under reflux after a desired reaction rate has been reached. During the dehydration esterification reaction, it is preferable to blow in a gas having a polymerization-inhibiting effect. Known polymerization inhibitors can be used, and examples of the gas having a polymerization-inhibiting effect include air and oxygen / nitrogen mixed gas. Methods for blowing in a gas having a polymerization-inhibiting effect include blowing it into the gas phase of the reaction vessel or into the liquid phase. The flow rate of the gas blown in is not particularly limited as long as it is an amount that can prevent polymerization, but in the case of air, for example, a flow rate of 50 to 300 mL / min may be used for a 2 L reaction vessel.

[0027] By the above method, a reaction liquid containing a sulfonic acid (meth)acrylate composition containing a sulfonic acid (meth)acrylate (A) represented by formula (1) and a hydroxyalkanesulfonic acid (B) represented by formula (2) and the like is prepared.

[0028] [Filtration and drying] The reaction solution after the dehydration esterification reaction contains the sulfonic acid (meth)acrylate (A) represented by formula (1) present as a solid, the hydroxyalkanesulfonic acid (B) represented by formula (2) present as a solid, and unreacted raw materials such as (meth)acrylic acid, and exists in a slurry state. This slurry can be filtered by a known method to obtain a crude product. The filtered crude product can be washed with an organic solvent such as acetone, ethyl acetate, or methanol. As drying conditions, known methods can be used, but drying under reduced pressure is preferred from the viewpoint of production efficiency. The drying temperature is preferably 20 to 80°C, more preferably 30 to 60°C. As described above, the production method of the present invention makes it possible to obtain a highly pure hydroxyphenyl(meth)acrylate with little coloration. Therefore, the hydroxyphenyl(meth)acrylate obtained by the present invention can be suitably used as a raw material monomer for resist resins.

[0029] The sulfonic acid (meth)acrylate composition of the present invention can be used by being blended directly into paints, adhesives, etc., but can also be used after being polymerized by radical polymerization or the like. [Example]

[0030] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way. The sulfonic acid (meth)acrylate (A) and the hydroxyalkanesulfonic acid (B) in the sulfonic acid (meth)acrylate compositions shown in each of the Examples and Comparative Examples were quantified as follows: 1 The results were obtained by H-NMR (manufactured by JEOL Ltd., FT-NMR, resonance frequency: 400 MHz, deuterated solvent: DO). in particular, 1In H-NMR, the proton area of ​​the methylene moiety bonded to the sulfur atom of the sulfonic acid (meth)acrylate (A), detected at a chemical shift of approximately 3 ppm, and the proton area derived from the sulfonic acid group of the hydroxyalkanesulfonic acid (B), detected at a chemical shift of approximately 8 ppm, were used as the reference, and the ratio of each proton was converted into a percentage.

[0031] Example 1 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of 2-hydroxyethanesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A1) and (B1) were quantified by NMR analysis.

[0032] Example 2 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of 2-hydroxyethanesulfonic acid (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of 2-hydroxyethanesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing a predetermined amount of 2-(methacryloyloxy)ethanesulfonic acid (A2) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A2) and (B1) were quantified by NMR analysis.

[0033] Example 3 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of 2-hydroxyethanesulfonic acid (60% aqueous solution), 1044 g of acrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of 2-hydroxyethanesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C, it was stirred for 14 hours, cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing a predetermined amount of 2-(acryloyloxy)ethanesulfonic acid (A3) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A3) and (B1) were quantified by NMR analysis.

[0034] Example 4 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 3-hydroxypropanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 10 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 3-(methacryloyloxy)propanesulfonate (A4) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A4) and (B1) were quantified by NMR analysis.

[0035] Example 5 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 5-hydroxypentanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 10 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing sodium 5-(methacryloyloxy)pentanesulfonate (A5) and 2-hydroxyethanesulfonic acid (B1) in predetermined amounts. The amounts of (A5) and (B1) were quantified by NMR analysis.

[0036] Example 6 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 10-hydroxydecanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction mixture was then stirred while reducing the pressure inside the reaction vessel until the water content in the reaction mixture reached 1% or less. Next, 10 g of 2-hydroxyethanesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction mixture reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing sodium 10-(methacryloyloxy)decanesulfonate (A6) and 2-hydroxyethanesulfonic acid (B1) in predetermined amounts. The amounts of (A6) and (B1) were quantified by NMR analysis.

[0037] Example 7 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium polyethylene glycol sulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 10 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing sodium 2-(methacryloyloxy)polyethylene glycol sulfonate (A7) and 2-hydroxyethanesulfonic acid (B1) in predetermined amounts. The amounts of (A7) and (B1) were quantified by NMR analysis.

[0038] Example 8 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 0.2 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A1) and (B1) were quantified by NMR analysis.

[0039] Example 9 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 2 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A1) and (B1) were quantified by NMR analysis.

[0040] Example 10 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 20 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A1) and (B1) were quantified by NMR analysis.

[0041] Example 11 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of 3-hydroxypropanesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 3-hydroxypropanesulfonic acid (B2). The amounts of (A1) and (B2) were quantified by NMR analysis.

[0042] Example 12 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of 5-hydroxypentanesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 5-hydroxypentanesulfonic acid (B3) in predetermined amounts. The amounts of (A1) and (B3) were quantified by NMR analysis.

[0043] Example 13 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of 10-hydroxydecanesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 10-hydroxydecanesulfonic acid (B4) in predetermined amounts. The amounts of (A1) and (B4) were quantified by NMR analysis.

[0044] Example 14 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of polyethylene glycol sulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing sodium 2-(methacryloyloxy)ethanesulfonate (A1) and polyethylene glycol sulfonic acid (B5) in predetermined amounts. The amounts of (A1) and (B5) were quantified by NMR analysis.

[0045] Comparative Example 1 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. Next, 10 g of p-toluenesulfonic acid was added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing sodium 2-(methacryloyloxy)ethanesulfonate (A1) and p-toluenesulfonic acid (B'1) in predetermined amounts. The amounts of (A1) and (B'1) were quantified by NMR analysis.

[0046] Comparative Example 2 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 0.1 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A1) and (B1) were quantified by NMR analysis.

[0047] Comparative Example 3 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 1044 g of methacrylic acid, and 2 g of 4-methoxyphenol. Air was introduced at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 40 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature, and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate, stirred for 5 minutes, and then filtered again using a pressure filter. The resulting white solid was dried under reduced pressure at 20°C for 4 hours to obtain a sulfonic acid (meth)acrylate composition containing predetermined amounts of sodium 2-(methacryloyloxy)ethanesulfonate (A1) and 2-hydroxyethanesulfonic acid (B1). The amounts of (A1) and (B1) were quantified by NMR analysis.

[0048] Comparative Example 4 2-Acrylamide-2-methylpropanesulfonic acid (A'1) and 2-hydroxyethanesulfonic acid (B1) were mixed together to obtain a sulfonic acid monomer-containing composition.

[0049] Comparative Example 5 Sodium 2-acrylamido-2-methylpropanesulfonate (A'2) and 2-hydroxyethanesulfonic acid (B1) were mixed together to obtain a sulfone monomer-containing composition.

[0050] Comparative Example 6 A 2L four-neck flask equipped with a thermometer, air inlet tube, stirrer, Dimroth condenser, and oil-water separator was charged with 200 g of sodium 2-hydroxyethanesulfonate (60% aqueous solution), 200 g of methacrylic acid, 800 g of xylene, 2 g of 4-methoxyphenol, and 40 g of 2-hydroxyethanesulfonic acid. Air was blown in at a flow rate of 100 mL / min while the temperature was raised to 90 °C in an oil bath. The reaction vessel was then depressurized and stirred until the water content of the reaction solution reached 1% or less. 10 g of 2-hydroxyethanesulfonic acid was then added to the reaction vessel and heated to 115 °C in an oil bath. After the reaction solution reached 115 °C and was stirred for 14 hours, it was cooled to room temperature and the resulting precipitate was filtered using a pressure filter. 350 g of 2-propanol was added to the filtered precipitate and stirred for 5 minutes, after which it was filtered again using a pressure filter and dried under reduced pressure at 20°C for 4 hours to obtain a white solid. NMR analysis of the obtained white solid revealed that 90% of the sodium 2-hydroxyethanesulfonate used as a raw material remained relative to the charged amount, and the reaction had hardly progressed, so further evaluation was not carried out.

[0051] The structures of A1 to A7, A'1, A'2, B1 to B5, and B'1 used in each example and comparative example are represented by the formula (1) R 1 , R 2 , M, and R in Eq. (2) 4 The results are listed in Table 1. [Table 1] *In Table 1, EO means oxyethylene. Also, a and b represent the average number of moles of oxyethylene added.

[0052] <Evaluation of hydrophilicity> 0.5 g of each composition of Examples 1 to 14 and Comparative Examples 1 to 5 was dissolved in 99.5 g of water to prepare a 0.5% aqueous solution. The contact angle of this aqueous solution with glass was measured using an automatic contact angle meter, DropMaster R501Hi (manufactured by Kyowa Interface Science Co., Ltd.). In this evaluation, a smaller contact angle value indicates better hydrophilicity. The evaluation criteria are as follows: A: The contact angle is less than 31°. ○: The contact angle is 31° or more and less than 40°. ×: The contact angle is 40° or more.

[0053] <Evaluation of hydrolysis> 6.0 g of each composition of Examples 1 to 14 and Comparative Examples 1 to 5 and 24.0 g of water were placed in a sample bottle and heated in a constant temperature oven at 60°C for 3 hours. The acid values ​​of the samples before and after heating were measured, and the hydrolysis rate was calculated using the following mathematical formula 1.

number

[0054] <Evaluation of coloring> 10.0 g of each of the compositions of Examples 1 to 14 and Comparative Examples 1 to 5 was placed in an aluminum tray and heated in a thermostatic oven at 60° C. for 24 hours. The color after heating was visually confirmed. In this evaluation, the closer the hue after the storage test is to the original white, the lower the coloring. The evaluation criteria are as follows: ◎: The color is white. ○: The hue is yellow. ×: The color is brown.

[0055] [Table 2]

[0056] [Table 3]

[0057] [Table 4]

[0058] As shown in Tables 2, 3 and 4, sulfonic acid (meth)acrylate (A) and hydroxyalkanesulfonic acid (B) were selected, blended according to the blending ratio, and mixed to obtain each composition. From the results shown in Tables 2, 3 and 4, it can be seen that in Examples 1 to 14 according to the present invention, sulfonic acid (meth)acrylate compositions excellent in all physical properties were obtained. Comparative Example 1 contained an acid different from the hydroxyalkanesulfonic acid (B), and the hydrophilicity, hydrolysis resistance at 60°C, and coloration during storage at 60°C were deteriorated. In Comparative Example 2, the content of hydroxyalkanesulfonic acid (B) in the sulfonic acid (meth)acrylate composition was low, and hydrolysis resistance at 60°C was poor. In Comparative Example 3, the content of hydroxyalkanesulfonic acid (B) in the sulfonic acid (meth)acrylate composition was high, and discoloration during storage at 60°C was poor. In Comparative Example 4, a sulfonic acid monomer different from the sulfonic acid (meth)acrylate (A) was contained, and hydrophilicity was poor. In Comparative Example 5, a sulfonic acid monomer different from the sulfonic acid (meth)acrylate (A) was contained, and hydrophilicity and hydrolysis resistance at 60°C were insufficient.

Claims

1. A sulfonic acid (meth)acrylate composition comprising a sulfonic acid (meth)acrylate (A) represented by the following formula (1) and a hydroxyalkanesulfonic acid (B) represented by the following formula (2), wherein the mass ratio (A):(B) of the sulfonic acid (meth)acrylate (A) to the hydroxyalkanesulfonic acid (B) is 99.95:0.05 to 85:15 when the total of the sulfonic acid (meth)acrylate (A) and the hydroxyalkanesulfonic acid (B) is 100 mass%. 【Chemical 1】 (In formula (1), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. M represents a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, or NR ３ ３ and R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 【Chemistry 2】 (In formula (2), R ４ represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100.

2. A method for producing a sulfonic acid (meth)acrylate composition containing a sulfonic acid (meth)acrylate (A) represented by formula (1) and a hydroxyalkanesulfonic acid (B) represented by formula (2), the method comprising the step of reacting (meth)acrylic acid with a hydroxyalkanesulfonic acid or a metal salt of a hydroxyalkanesulfonic acid, wherein no organic solvent is used during the reaction step. 【Chemistry 3】 (In formula (1), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100. M represents a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, or NR ３ ３ and R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 【Chemistry 4】 (In formula (2), R ４ represents an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having an average number of added moles of 1 to 100.

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