JP4955276B2 - Hydroxyphenyl (meth) acrylate composition, method for producing the same, and method for producing the polymer - Google Patents

Description

The present invention relates to a hydroxyphenyl (meth) acrylate composition, a method for producing the same, and a method for producing a polymer .

As a method for producing an ester, a method in which a carboxylic acid and an alcohol are reacted in the presence of a catalyst is generally used. However, it is known that an esterification reaction using a phenol as an alcohol hardly reacts. Therefore, a method is known in which phenols are reacted with (meth) acrylic anhydride to obtain (meth) acrylic acid phenyl ester (see, for example, Patent Document 1). In this patent document 1, the case where monohydric phenols are mainly used is mainly targeted, and there is no detailed description about the manufacturing method at the time of using dihydric phenols.
In addition, as a method for producing a hydroxyphenyl (meth) acrylate composition, a method of reacting a dihydric phenol with (meth) acrylic anhydride or (meth) acrylic acid chloride is known (for example, patent document). 2).

JP 2000-191590 A Japanese Patent Publication No.49-34667

However, when (meth) acrylic acid chloride is used in the method of Patent Document 2, there is a problem of corroding the reaction vessel, and not only is industrially advantageous because a large amount of waste liquid containing halide is generated. Since the halide is used, the obtained hydroxyphenyl (meth) acrylate composition is not suitable for use in electrical and electronic parts. On the other hand, when (meth) acrylic anhydride is used in the method of Patent Document 2, the above-mentioned problem does not occur, but the purity is relatively low including a relatively large amount of phenylene di (meth) acrylate as a by-product. Only hydroxyphenyl (meth) acrylate compositions can be obtained. Since this phenylene di (meth) acrylate becomes a cross-linking component at the time of polymerization, there is a problem that solvent solubility is lowered or gelation is caused at the time of polymerization.
Therefore, the present invention produces a high-purity hydroxyphenyl (meth) acrylate composition having good solvent solubility during polymerization and a high-purity hydroxyphenyl (meth) acrylate composition without using a halide. It aims to provide a method.

Therefore, as a result of diligent research and development, the present inventors have reacted dihydric phenols with (meth) acrylic anhydride to react hydroxyphenyl (meta). ) In the method for producing an acrylate composition, unreacted dihydric phenols are removed by washing with water to obtain crude crystals. The obtained crude crystals are dissolved in a solvent, and then contacted with a poor solvent to obtain phenylenediamine. The inventors have come up with the idea that removing (meth) acrylate is effective, and have completed the present invention.
That is, the present invention prepares a reaction solution containing hydroxyphenyl (meth) acrylate and by-product phenylene di (meth) acrylate by reacting dihydric phenols with (meth) acrylic anhydride. A step of removing unreacted dihydric phenols in the reaction solution by washing with water to prepare a crude crystal , and dissolving the crude crystal with a solvent that is toluene, xylene or a mixture thereof to obtain a solution. A method for producing a hydroxyphenyl (meth) acrylate composition, comprising a step of preparing, and a step of removing the phenylene di (meth) acrylate in the solution by bringing the solution into contact with a poor solvent. It is.
When the dihydric phenol and the (meth) acrylic anhydride are reacted, it is preferable to use an organic sulfonic acid or an inorganic acid as an acid catalyst.
For the total amount of 100 mol% of the unreacted dihydric phenols, the hydroxyphenyl (meth) acrylate and the phenylene di (meth) acrylate, the unreacted dihydric phenols are removed to 1.0 mol% or less, It is preferable to remove the phenylene di (meth) acrylate to 1.0 mol% or less.
Also, as the poor solvent, hexane, cyclohexane, it is desirable to use at least one selected from the group consisting of methyl cyclohexane, ethyl cyclohexane and heptane.
The present invention also relates to a hydroxyphenyl (meth) acrylate composition comprising only hydroxyphenyl (meth) acrylate, dihydric phenols and phenylene di (meth) acrylate, wherein the hydroxyphenyl (meth) acrylate, the divalent The content of the dihydric phenol is more than 0 mol% and not more than 0.2 mol% with respect to a total of 100 mol% of the phenols and the phenylene di (meth) acrylate, and the content of the phenylene di (meth) acrylate Is a hydroxyphenyl (meth) acrylate composition characterized by being more than 0 mol% and 1.0 mol% or less.

  According to the present invention, a high-purity hydroxyphenyl (meth) acrylate composition having good solvent solubility during polymerization and a high-purity hydroxyphenyl (meth) acrylate composition are produced without using a halide. A method can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The method for producing a hydroxyphenyl (meth) acrylate composition according to the present invention comprises:
(1) A step of reacting a dihydric phenol with (meth) acrylic anhydride to prepare a reaction solution containing hydroxyphenyl (meth) acrylate and a by-product phenylene di (meth) acrylate,
(2) a step of preparing crude crystals by removing unreacted dihydric phenols in the reaction solution by washing with water;
(3) a step of preparing a solution by dissolving the crude crystals with a solvent, and (4) a step of removing the phenylene di (meth) acrylate in the solution by bringing the solution into contact with a poor solvent. Is included.

  Specific examples of the dihydric phenols used in the present invention include catechol, resorcin, hydroquinone, methylhydroquinone and the like.

  The (meth) acrylic anhydride used in the present invention is acrylic anhydride and methacrylic anhydride. When used in the reaction, these commercially available products may be used as they are, but they can also be easily produced by known methods. Examples of the method for producing (meth) acrylic anhydride include a method of producing from acetic anhydride and (meth) acrylic acid, a method of producing from (meth) acrylic acid halide and (meth) acrylic acid by a condensation reaction, and the like. It is done. Moreover, unlike the (meth) acrylic acid chloride conventionally used, (meth) acrylic anhydride has low corrosiveness to general stainless steel as a material for the reaction vessel. Therefore, in this invention, even if it uses a general reaction container, a hydroxyphenyl (meth) acrylate composition can be manufactured on an industrial scale without the problem of corrosion.

  In this invention, the molar ratio at the time of making bihydric phenols and (meth) acrylic anhydride react is 0.5-1 of (meth) acrylic anhydride with respect to 1.0 mol of dihydric phenols. .2 mol, preferably 0.8 to 1.1 mol. If the amount of (meth) acrylic anhydride is less than 0.5 mol relative to 1.0 mol of the dihydric phenol, the yield is unfavorable. On the other hand, if the amount of (meth) acrylic anhydride exceeds 1.2 moles relative to 1.0 mole of dihydric phenols, a large amount of phenylene dimethacrylate as a by-product is generated, which is not preferable.

  In the reaction, it is preferable to use an organic solvent such as dioxane, tetrahydrofuran or acetone. The usage-amount of a solvent is 0-1000 mass parts with respect to 100 mass parts of total amounts of dihydric phenols and (meth) acrylic anhydride, Preferably it is 10-200 mass parts. The reaction is carried out at room temperature to 120 ° C. for 1 to 24 hours.

In the reaction, it is preferable to use an acid catalyst, and it is more preferable to use an organic sulfonic acid or an inorganic acid. Examples of the organic sulfonic acid include dimethyl sulfuric acid, diethyl sulfuric acid, p-toluene sulfonic acid, and methane sulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid. The amount of catalyst used can be arbitrarily determined depending on the amount of solvent used, reaction temperature, etc., but is preferably 0.001 with respect to 100 parts by mass of the total amount of dihydric phenols and (meth) acrylic anhydride. To 1 part by mass, more preferably 0.01 to 0.1 part by mass. If this reaction is carried out in the presence of a basic catalyst, a large amount of phenylene di (meth) acrylate is generated, which is not preferable. Completion of the reaction can be confirmed, for example, by disappearance of the acid anhydride group absorption (around 1783 cm ⁻¹ ) by IR measurement. After confirming completion of the reaction, neutralization may be carried out with triethylamine, sodium carbonate or the like, if necessary.

  In the reaction solution obtained by the reaction of dihydric phenols with (meth) acrylic anhydride, hydroxyphenyl (meth) acrylate, phenylene di (meth) acrylate as a by-product and unreacted dihydric phenols It is included. By washing this reaction solution with water, the content of unreacted dihydric phenols can be reduced. When the unreacted dihydric phenols are removed by sufficiently washing with water, crude crystals are precipitated in water. Here, with respect to 100 mol% in total of unreacted dihydric phenols, hydroxyphenyl (meth) acrylate and phenylene di (meth) acrylate, water washing until unreacted dihydric phenols became 1.0 mol% or less. Is preferably repeated. If the unreacted dihydric phenol exceeds 1.0 mol%, the yield of the hydroxyphenyl (meth) acrylate composition finally obtained may be deteriorated and the purity may be lowered.

  Next, the crude crystals precipitated in water are dissolved with a solvent. Examples of the solvent used for dissolution include toluene, xylene, or a mixture thereof. By using such a solvent, the yield of the finally obtained hydroxyphenyl (meth) acrylate composition is improved. When dissolving the crude crystal with a solvent, it is preferable to use 50 to 300 parts by mass, more preferably 100 to 200 parts by mass of the solvent with respect to 100 parts by mass of the crude crystal, and dissolve by heating if necessary. Good. At that time, the water contained in the crude crystals is preferably separated and removed from the solvent layer containing the crude crystals. Thus, the purity of the hydroxyphenyl (meth) acrylate composition finally obtained improves by dissolving a crude crystal with a solvent.

  Next, the phenylene di (meth) acrylate can be removed by bringing the solution in which the crude crystals are dissolved into contact with a poor solvent and washing. Examples of the method of washing with a poor solvent include a method in which a solution in which crude crystals are dissolved is poured into the poor solvent, or a method in which the poor solvent is added to a solution in which crude crystals are dissolved. Specific examples of the poor solvent include hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, and heptane, and at least one of these can be used. Here, with respect to a total of 100 mol% of unreacted dihydric phenols, hydroxyphenyl (meth) acrylate and phenylene di (meth) acrylate, phenylene di (meth) acrylate is used as a poor solvent until it becomes 1.0 mol% or less. It is preferable to repeat the washing. When phenylene di (meth) acrylate remains in excess of 1.0 mol%, the purity of the finally obtained hydroxyphenyl (meth) acrylate composition is reduced. When polymerization is performed using this as a raw material, phenylene di (( Since (meth) acrylate is a cross-linking component, the molecular weight of the polymer may be abnormally increased, gelation may occur in some cases, and solvent solubility may deteriorate.

  Finally, the poor solvent is removed and dried to obtain a high yield and high purity, specifically, 100 mol% of the total of dihydric phenols, hydroxyphenyl (meth) acrylate and phenylene dimethacrylate, A hydroxyphenyl (meth) acrylate composition having a dihydric phenol content of 1.0 mol% or less and a phenylene dimethacrylate content of 1.0 mol% or less can be obtained.

  The hydroxyphenyl (meth) acrylate obtained by the production method of the present invention is solid at room temperature and is relatively stable to heat and light, but the polymerization property is general (meth) acrylic acid. It has the feature of being equivalent to an ester.

  When a polymer is synthesized using the hydroxyphenyl (meth) acrylate composition obtained by the production method of the present invention, it is excellent in solvent solubility, alkali solubility, transparency, heat discoloration, etc., high Tg, and high thermal decomposition temperature. A polymer with a high refractive index is obtained. Therefore, it can be applied to alkali developing type photoresists used for semiconductor manufacturing, display members, printing plate making materials, and the like, and protective films requiring transparency and heat discoloration. It is also useful as a curing agent such as an epoxy resin.

  Moreover, the hydroxyphenyl (meth) acrylate composition obtained by the production method of the present invention has good copolymerizability with not only homopolymers but also other unsaturated group-containing polymerizable compounds. Specific examples of such unsaturated group-containing polymerizable compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, Citraconic anhydride, mesaconic anhydride, itaconic anhydride, vinyl benzoic acid, o-carboxyphenyl (meth) acrylate, m-carboxyphenyl (meth) acrylate, p-carboxyphenyl (meth) acrylate, o-carboxyphenyl (meth) Acrylamide, m-carboxyphenyl (meth) acrylamide, p-carboxyphenyl (meth) acrylamide, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono ( ) Acrylate, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [ 2.2.1] Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- 2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, tricyclo [5 .2.1.02,6] decan-8-yl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yloxyethyl (meth) acrylate,

Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3- Hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl glycoside,

Phenyl (meth) acrylate, benzyl (meth) acrylate, o-methoxyphenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate,

Diethyl maleate, diethyl fumarate, diethyl itaconate, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2. 2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2 -Ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl ) Bicyclo 2.2.1] Hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2 .1] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5- Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene,

Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl -1,3-butadiene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, o-hydroxyphenyl (meth) acrylamide, m-hydroxyphenyl (meth) acrylamide, p-hydroxyphenyl ( (Meth) acrylamide, 3,5-dimethyl-4-hydroxybenzyl (meth) acrylamide, phenylmaleimide, hydroxyphenylmaleimide, cyclohexylmaleimide, benzylmaleimide, trifluoromethyl (meth) acyl Rate, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxybutyl acrylate, Acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, vinyl glycidyl ether, allyl glycidyl ether, isopropenyl glycidyl ether, o-vinyl benzyl Glycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, vinylcyclohexene monooxide, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate And so on.

  Polymerization uses azo initiators typified by azobisisobutyronitrile, organic peroxides typified by benzoyl peroxide, etc., methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, ethylene glycol , Acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, acetic acid 3-methoxybutyl, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Conducted in an organic solvent such as acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybutanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethyl lactate be able to.

The present invention will be described more specifically with reference to the following examples, comparative examples and reference examples. However, the present invention is not limited to the following examples. Moreover, the measurement of the average molecular weight of the polymer in the reference example was performed by the following method. Example 3 is a reference example.
(Measurement of average molecular weight)
The value of the weight average molecular weight (Mw) of the obtained polymer was measured under the following conditions using gel permeation chromatography (GPC) and calculated in terms of polystyrene.
Column: sucrose c Dex KF-801 + KF-802 + KF-802 + KF-803
Column temperature: 40 ° C
Developing solvent: tetrahydrofuran Detector: differential refractometer (sucrose c index RI-101)
Flow rate: 1 mL / min

[Example 1]
Synthesis of 4-hydroxyphenyl methacrylate In a flask equipped with a stirrer, 100 parts by mass of hydroquinone, 140 parts by mass of methacrylic anhydride, 200 parts by mass of 1,4-dioxane and 1.0 part by mass of p-toluenesulfonic acid were added. The reaction was carried out at 4 ° C. for 4 hours. It was confirmed by IR measurement that carbonyl anhydride (1783 cm ⁻¹ ) of methacrylic anhydride had disappeared, and neutralized with 1.0 part by mass of triethylamine. ^{According to 1} H-NMR measurement, washing with ion-exchanged water was repeated until the unreacted hydroquinone was 0.1 mol% with respect to 100 mol% of the total of unreacted hydroquinone, p-hydroxyphenyl methacrylate and p-phenylene dimethacrylate. A slurry containing crude crystals was obtained. The chemical shift in ¹ H-NMR measurement was as follows: benzene ring of hydroquinone: 6.57 ppm, benzene ring of p-hydroxyphenyl methacrylate: 6.76 to 6.96 ppm, benzene ring of p-phenylene dimethacrylate: 1.49 ppm It is.
Next, 160 parts by mass of toluene was added, and the crude crystals were dissolved at 60 ° C. Water contained in the crude crystals was separated and removed at 60 ° C., and a toluene solution in which the crude crystals were dissolved was added to 110 parts by mass of hexane to precipitate crystals. Subsequently, washing with hexane was repeated until the by-product p-phenylene dimethacrylate was 0.3 mol%, and then hexane was dried to obtain 85 parts by mass of p-hydroxyphenyl methacrylate. The p-hydroxyphenyl methacrylate of this crystal was 99.6 mol%.

[Example 2]
Toluene used for dissolution of the crude crystals was changed to xylene, the dissolution temperature of the crude crystals was changed from 60 ° C. to 70 ° C., and the hexane as a poor solvent was changed to methylcyclohexane in the same manner as in Example 1, 84 parts by mass of p-hydroxyphenyl methacrylate was obtained. The purity of this crystal determined by ¹ H-NMR measurement was 99.5 mol%.

[Example 3]
Synthesis of 3-hydroxyphenyl methacrylate In a flask equipped with a stirrer, 100 parts by mass of resorcin, 140 parts by mass of methacrylic anhydride, 50 parts by mass of 1,4-dioxane and 0.1 part by mass of sulfuric acid were added, and the mixture was heated at 80 ° C. for 4 hours. Reacted. By IR measurement, it was confirmed that absorption of carbonyl of methacrylic anhydride (1783 cm ⁻¹ ) disappeared, and neutralized with 0.1 part by mass of triethylamine. ^{By 1} H-NMR measurement, washing with ion-exchanged water was repeated until the total amount of unreacted resorcin was 0.4 mol% with respect to the total of 100 mol% of unreacted resorcin, m-hydroxyphenyl methacrylate and m-phenylene dimethacrylate. A slurry containing crude crystals was obtained.
Next, 160 parts by mass of toluene was added, and the crude crystals were dissolved at 60 ° C. Water contained in the crude crystals was separated and removed at 60 ° C., and 110 parts by mass of cyclohexane was added to the toluene solution in which the crude crystals were dissolved to precipitate crystals. Subsequently, washing with hexane was repeated until the by-product m-phenylene dimethacrylate was 0.4 mol%, and then cyclohexane was dried to obtain 80 parts by mass of m-hydroxyphenyl methacrylate crystals. The purity of this crystal determined by ¹ H-NMR measurement was 99.2 mol%.

[Comparative Example 1]
In a flask equipped with a stirrer, 100 parts by mass of hydroquinone, 131 parts by mass of methacrylic anhydride, 900 parts by mass of tetrahydrofuran and 6.0 parts by mass of sulfuric acid were added and reacted at room temperature in a nitrogen atmosphere for 21 hours. It was confirmed by IR measurement that absorption of carbonyl of methacrylic anhydride (1783 cm ⁻¹ ) disappeared, and the resulting reaction solution was poured into 5000 parts by mass of water and neutralized with sodium hydroxide. Furthermore, after stirring for 1 hour in a nitrogen atmosphere and removing the supernatant, washing with a large amount of hexane was repeated, but p-phenylene dimethacrylate was only removed up to 1.5 mol%. Hexane was dried to obtain 62 parts by mass of p-hydroxyphenyl methacrylate crystals. The p-hydroxyphenyl methacrylate content in the crystals was 98.4 mol%.

[Reference Example 1]
In a flask equipped with a reflux condenser and a stirrer, 100 parts by mass of p-hydroxyphenyl methacrylate crystals (composition) obtained in Example 1, 300 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and azobis as a polymerization initiator. 4.0 parts by mass of isobutyronitrile was charged and reacted at 80 ° C. for 6 hours. The weight average molecular weight (Mw) of the obtained polymer was 19,900.

[Reference Examples 2-3 and Comparative Reference Example 1]
Using the hydroxyphenyl methacrylate crystals (composition) obtained in Examples 2 to 3 and Comparative Example 1, a polymer was obtained in the same manner as in Reference Example 1. Table 1 shows the weight average molecular weight (Mw) of the obtained polymer.

  In Reference Examples 1 to 3, polymers were obtained, but in Comparative Reference Example 1, the viscosity increased abnormally during the polymerization and lost fluidity. This is considered to be because a large amount of p-phenylene dimethacrylate is contained in the hydroxyphenyl methacrylate crystal obtained in Comparative Example 1.

Claims (8)

A hydroxyphenyl (meth) acrylate composition consisting only of hydroxyphenyl (meth) acrylate, dihydric phenols and phenylene di (meth) acrylate,
The content of the dihydric phenols is more than 0 mol% and 0.2 mol% or less with respect to 100 mol% in total of the hydroxyphenyl (meth) acrylate, the dihydric phenols and the phenylene di (meth) acrylate. And the content of the said phenylene di (meth) acrylate is more than 0 mol% and 1.0 mol% or less, The hydroxyphenyl (meth) acrylate composition characterized by the above-mentioned. A step of preparing a reaction solution containing hydroxyphenyl (meth) acrylate and by-product phenylene di (meth) acrylate by reacting dihydric phenols with (meth) acrylic anhydride,
Removing unreacted dihydric phenols in the reaction solution by washing with water to prepare crude crystals;
A step of preparing a solution by dissolving the crude crystals with a solvent that is toluene, xylene or a mixture thereof ; and the phenylene di (meth) acrylate in the solution by contacting the solution with a poor solvent. The manufacturing method of the hydroxyphenyl (meth) acrylate composition characterized by including the process of removing.   The hydroxyphenyl (meth) acrylate composition according to claim 2, wherein an organic sulfonic acid or an inorganic acid is used as an acid catalyst when the dihydric phenol and the (meth) acrylic anhydride are reacted. Manufacturing method.   For the total amount of 100 mol% of the unreacted dihydric phenols, the hydroxyphenyl (meth) acrylate and the phenylene di (meth) acrylate, the unreacted dihydric phenols are removed to 1.0 mol% or less, The said phenylene di (meth) acrylate is removed to 1.0 mol% or less, The manufacturing method of the hydroxyphenyl (meth) acrylate composition of Claim 2 or 3 characterized by the above-mentioned. The poor solvent is hexane, cyclohexane, hydroxyphenyl (meth) acrylate composition according to any one of claims 2-4, characterized in that at least one selected from methylcyclohexane, ethylcyclohexane and heptane Manufacturing method. The hydroxyphenyl (meth) acrylate composition according to any one of claims 2 to 5, further comprising a step of removing and drying the poor solvent after the removal of the phenylene di (meth) acrylate. Manufacturing method. A method for producing a polymer, wherein the hydroxyphenyl (meth) acrylate composition according to claim 1 is used as a polymerization raw material. Hydroxyphenyl (meth) acrylate containing dihydric phenols and phenylene di (meth) acrylate as impurities,
The content of the dihydric phenol is more than 0 mol% and not more than 0.2 mol% and the content of the phenylene di (meth) acrylate is more than 0 mol% with respect to 100 mol% of the hydroxyphenyl (meth) acrylate. Hydroxyphenyl (meth) acrylate characterized by being 1.0 mol% or less.