JPH02188576A - Epoxidized (meth)acrylate composition - Google Patents

Abstract

PURPOSE:To obtain the title high-quality composition useful as an intermediate raw material for resin for coating compound without problems of admixture of polymers, white clouding, etc., by blending a (meth)acrylic ester with a combination of at least two specific polymerization inhibitors. CONSTITUTION:A cyclohexenylmethyl (meth)acrylate compound shown by formula I (R is H or methyl) is epoxidized with an oxidizing agent to give a compound shown by formula II, which is blended with (A) hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t- butylphenol, etc., and (B) phosphoric acid, potassium phosphate, sodium ammonium hydrogenphosphate, pyrophosphoric acid, pyrophosphoric acid 2-ethylhexyl ester, tripolyphosphate, etc., in the ratio of 0.001-0.1wt.% component A and 0.01-0.2wt.% component B.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to epoxidized (meth)acrylate compositions.

(Meth)acrylate compounds can be easily homopolymerized or copolymerized with other unsaturated group-containing compounds in the presence of heat, ultraviolet rays, ionizing radiation, and radical polymerization initiators, and can also be used as intermediate raw materials for paint resins. is also useful.

(Prior Art) Various acrylic acid ester monomers have been known.

For example, methyl acrylate, ethyl acrylate.

Monofunctional monomers such as 2-ethylhexyl acrylate and polyfunctional monomers such as trimethylolpropane triacrylate and pentaerythritol triacrylate are generally known.

However, when monofunctional monomers are used in printing inks and paints, the odor of unreacted monomers after curing becomes a serious problem.

Furthermore, when polyfunctional monomers are used as diluents for paints and printing inks, they have to be used in large amounts relative to resins, which has the disadvantage that the properties of the resins are lost.

In this respect, the cyclohexenyl (meth)acrylate compound represented by the formula (R represents a hydrogen atom or a methyl group) obtained by epoxidizing it with an oxidizing agent (in the formula, R represents a hydrogen atom or a methyl group) has a low It has high viscosity, low odor, and solubility in a wide range of resins, and is useful as a raw material or modifier for inks, paints, adhesives, coatings, and molding resins.

However, the epoxidized (meth)acrylic acid ester represented by this general formula (11) (hereinafter abbreviated as AETHB when R is a hydrogen atom, and METHB when R is a methyl group)
is extremely easy to polymerize during the manufacturing process.

It is known that during storage and transportation they often polymerize due to heat, light and other factors.

In order to prevent this, in Japanese Patent Application No. 10083/1983, it was proposed that the (meth)acrylic acid ester, that is, AETHB (ME
It is disclosed that amines, especially helysine, are preferred, although their ability to inhibit polymerization is insufficient for THB). In addition, although there is a description of a polymerization inhibitor in Japanese Patent Application No. 62-252217, there is no mention of its effect at all, so the application of Japanese Patent Application No. 1983-10083 is classified as AETHB (METHB).
This is essentially the only prior art related to a method for preventing polymerization.

(Problems to be Solved by the Invention) In response to this, the present inventors have
It was confirmed that the effect of inhibiting the polymerization of AETHB (M, ETHB) by using piperidine alone or in combination with so-called ordinary inhibitors such as heridine and hydroquinone as described in the No. 83 application was not yet sufficient.

One of the reasons for this is that at the time when Japanese Patent Application No. 10083/1983 was filed, AETHB (METHB) had not yet been produced on an industrial scale, so the quality that the product should have could not be fully predicted. be.

In other words, even if the product has a certain degree of J1 gold prevention effect, in order to produce it on an industrial scale, it is important whether the obtained product meets the desired quality.

Developments in this regard have progressed since then, and it has become clear that there is a problem if trace amounts of polymers are included in the product.

For example, when synthesizing an intermediate raw material for paint resin, if AETHB (METHB) containing a polymer is used, the polymer will precipitate as a sticky insoluble substance, causing some problems in the process and reducing the commercial value of the paint. This results in a significant decrease in

The trace amounts of polymers contained in the product AETHB (METHB) are thought to be mainly composed of low molecular weight polymers of AETHB (MBTHB) itself, but the content of these polymers is higher than that of n-hexane or n-hebutane in the product. This can be clearly confirmed by whether or not it becomes cloudy when a small amount of n-hebutane is dissolved.
).

AETHB (ME, THB) that can be used as a product is HT
It is known that the liquid must be transparent or slightly cloudy.

AETHB (METHB>HTt!), which was obtained by re-testing the method of the old Japanese Patent Application No. 10083/1983, was found to be cloudy or cloudy so strong that a precipitate was deposited, so the quality was poor. judged not to be sufficient.

In other words, in order to industrially produce AETHB (METHB), it is necessary to establish a more effective method for inhibiting polymerization, and at the time the present inventors filed the application, there was still no technology that would make this possible. It didn't exist.

The present inventors have conducted intensive research to address these issues, and have combined specific polymerization inhibitors to create AETHB (ME
The present inventors have discovered that the above-mentioned object can be achieved by using the present invention as a THB) composition, and have completed the present invention.

(Structure of the Invention) That is, 1 the present invention is to epoxidize a cyclohexenyl (meth)acrylate compound represented by the general formula (I) (in which R represents a hydrogen atom or a methyl group) with an oxidizing agent to obtain a compound of the general formula ( II) A compound represented by (wherein R represents a hydrogen atom or a methyl group) and at least one compound each selected from the following [Group A] and [Group B] are coexisting. Epoxidized (meth)acrylate composition: [Group A] Hydroquinone, hydroquinone monomethyl ether,
P-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-
t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-
P-cresol, 2,5-dihydroxy-P-quinone,
Piperidine, ethanolamine, α-nitroso-β-naphthol, diphenylamine, phenothiazine, N-nitronphenylhydroxylamine, N,N-diethylhydroxylamine [group B] phosphoric acid, potassium phosphate, sodium phosphate, sulfuric acid Ammonium hydrogen, pyrophosphate, potassium pyrophosphate,
sodium pyrophosphate, birophosphate 2-ethylhexyl ester, potassium birophosphate 2-ethylhexyl ester, sodium birophosphate-2-ethylhexyl ester, tripolyphosphoric acid, potassium tripolyphosphate, and sodium tripolyphosphate.

The AETHB (METHB) composition of the present invention will be explained in detail below.

First, the reaction process for producing the epoxy compound which is the main component in the AETHB (MBTHB) composition will be explained.

That is, by epoxidizing the (meth)acrylate compound represented by general formula (I) with an oxidizing agent, AETHB<M ET' H represented by general formula (II) is obtained.
B) is obtained.

The oxidizing agent used for this removal may be any oxidizing agent that can epoxidize unsaturated bonds, such as performic acid, peracetic acid, perpropionic acid, m
-Various hydroperoxides such as chloroperbenzoic acid, trifluoroperacetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumylhydroperoxide, tetralyl hydroperoxide, diisopropylbenzene hydroperoxide, hydrogen peroxide For example,

The oxidizing agent may be used in combination with a catalyst. For example, when an organic peracid is used, an alkali such as soda carbonate or an acid such as [M] may be used in combination as a catalyst.

Similarly, when using the above-mentioned various hydroperoxas and ides, those having known catalytic ability such as molybdenum hexacarbonyl can be used, and when hydrogen peroxide is used, a mixture of tungstic acid and caustic soda can be used in combination.

When carrying out the reaction in batches, first a predetermined amount of cyclohexenyl (meth)acrylate is charged into one reaction vessel, a catalyst and a stabilizer are dissolved therein as required, and the oxidizing agent is dropped into this. Let's do it.

The reaction molar ratio between the oxidizing agent and cyclohexenyl (meth)acrylate is theoretically 1/1, but in the method of the present invention, it is in the range of 0.1 to 10, preferably in the range of 0.5 to 10. , more preferably in the range of 0°8 to 1.5°.

When the molar ratio of the oxidizing agent and cyclohexenyl (meth)acrylate exceeds 10, it is preferable in terms of the conversion rate of cyclohexenyl (meth)acrylate, shortening the reaction time, and reducing loss due to polymerization of (meth)acrylate. However, a large amount of cost is required due to side reactions caused by excess oxidizing agent, selectivity of oxidizing agent, and recovery of unreacted oxidizing agent. There are drawbacks such as.

Conversely, if the molar ratio of the reaction between the oxidizing agent and cyclohexenyl (meth)acrylate is 0.1 or less, the selectivity of the oxidizing agent,
Although it is preferable in terms of conversion rate and suppressing side reactions caused by oxidizing agents, it requires loss due to polymerization of (meth)acrylate and a large amount of cost when recovering unreacted cyclohexenyl (meth)acrylate. There are drawbacks such as.

The reaction temperature is carried out below an upper limit such that the epoxidation reaction has priority over the decomposition reaction of the oxidizing agent, for example.

When peracetic acid is used, the temperature is preferably 70°C or lower, and when tert-butyl hydroperoxide is used, the temperature is preferably 150°C or lower.

If the reaction temperature is low, it will take a long time to complete the reaction, so it is preferable to carry out the reaction at a temperature higher than the lower limit of 0° C. if peracetic acid is used and 20° C. if tert-butyl hydroperoxide is used.

In addition, during the epoxidation reaction, a side reaction occurs in which the epoxy group is ring-opened with organic acids, alcohols, and water due to by-products from the oxidizing agent, so the temperature that reduces the amount of side reactions is set as described above. Select and implement from a temperature range.

The reaction pressure is generally operated at normal pressure, but it can also be carried out under elevated or low pressure.

One reaction can also be carried out in the presence of a solvent.

Reaction in the presence of a solvent is preferred because it has effects such as lowering the viscosity of the reaction crude liquid and stabilizing it by making the oxidizing agent more diluted.

Solvents used include aromatic compounds such as benzene, toluene, and xylene; halides such as chloroform, dimethyl chloride, carbon tetrachloride, and chlorobenzene;
Esterified products such as ethyl acetate and butyl acetate, ketone compounds such as acetone and methyl ethyl getone, 1.2-
Ether compounds such as dimethoxyethane can be used.

The amount of solvent used is preferably 0.5 to 5 times the amount of cyclohexenyl (meth)acrylate.

If the amount is less than 0.5 times, there will be little stabilizing effect by diluting the oxidizing agent, and conversely, if the amount is more than 5 times, the stabilizing effect will not improve much and it will take a lot of time to recover the solvent. It is wasteful because it costs money.

The key point of the present invention is that the composition contains a specific polymerization inhibitor.

By the way, if the inhibitor described in Japanese Patent Application No. 63-10083 is simply added during the epoxidation reaction, HT will result in cloudiness.

Polymerization occurs during the reaction, albeit to a small extent.

It is believed that this is for the purpose of

However, since such a phenomenon is so slight that it cannot be clearly detected even with analytical equipment such as liquid chromatography, it is overlooked.

While the reaction crude liquid, which becomes cloudy due to HT, undergoes a subsequent purification process and is turned into a product, polymerization proceeds further, and the HT of the product becomes cloudy to the extent that it is accompanied by a precipitate.

In response to such a phenomenon, the present inventors have developed the above-mentioned [A.

It has been found that the problem can be solved by using a composition in which at least one compound selected from Group B] is present in the manufacturing process, storage, and distribution process. At this time, the effect can be fully exerted by allowing molecular oxygen to coexist in the composition.

Specifically, air may be present in the tank during transportation or storage.

Normally, when a liquid is piped into a container at 5A, air exists in the space above the container without being particularly conscious of it, so a coexistence state is inevitably formed.

However, an operation for blowing air may be performed in advance.

The amount of blowing can be selected arbitrarily, but if it is too large, it is not preferable because it will result in solvent loss.

In addition, in order to avoid the formation of an explosive mixture in the system, it is normal to have nitrogen coexist with air in the system, but in that case, the oxygen concentration in the blown gas is 0°01% (volume) or more, Preferably it is 3% (capacity) or more. The higher the oxygen concentration, the more effective it is, but the upper limit is the lower explosive limit oxygen concentration in the system, and that value depends on the solvent used.

In particular, when two or more compounds prescribed in the present invention are used in combination, the effect is far superior to that obtained when each group of compounds is used alone or when only two compounds from each group are used in combination.
It is noteworthy that the synergistic effect is extremely large.

Next, the situation when producing the epoxidized (meth)acrylate composition of the present invention will be specifically explained.

Some of the [Group A] compounds used for the epoxidized (meth)acrylate composition of the present invention, such as hydroquinone, a combination of hydroquinone monomethyl ether and molecular oxygen, are so-called acrylic acid or acrylic ester. It is known that it is effective in preventing the polymerization of
The example of Japanese Patent Application No. 10083/1983 also compares the inhibition effect in an air atmosphere.

The reason why at least one compound of [Group B] is added as an essential component to the epoxidized (meth)acrylate composition of the present invention is that the oxidizing agent used decomposes, albeit in a small amount, and generates a radical source. This is because it is thought to be effective in suppressing people's behavior.

Next, the amount of polymerization inhibitor used can be arbitrarily changed depending on the type of target compound and manufacturing process conditions, but [Group A]
The compound is 0.005 to 5% by weight based on the reaction raw material cyclohexenylmethyl (meth)acrylate.
, more preferably 0°001 to O,1ffi amount%, [B
r1] is preferably added in an amount of o, ooi to 1% by weight, more preferably 0.01 to 0.2% by weight.

The addition method may be as a powder, or it may be added after being dissolved in a solvent.

The reaction is carried out continuously or batchwise, and in the case of continuous reaction, a piston flow type is preferred.

The polymerization inhibitors used at this time may be added individually, but if they are in powder form, they are preferably dissolved in a solvent before being added.

Alternatively, it may be dissolved in 2M ester and charged.

Further, although the same applies to the case of a batch method, a semi-batch method in which the oxidizing agent is added sequentially is preferable.

The key point of the present invention is to prevent polymerization by allowing at least one of each selected from [Group A] and [Group B] to coexist, but the present invention can also be effectively used for purification as is. be.

After the reaction is completed, the epoxidation reaction crude liquid contains a solvent, a low boiling point substance,
W can be produced by removing unreacted raw materials, catalysts, etc., neutralizing them, and treating them with adsorbents and ion exchange resins.

Particularly when an organic peracid is used as the oxidizing agent, it is preferable to neutralize and wash the reaction crude solution with water.

This is because if low-boiling components such as solvents are removed without neutralization, they are extremely likely to polymerize.

Examples of alkaline aqueous solutions used for neutralization include NaO
H%KOH, KCO, Na2CO3, NaHC
Aqueous solutions of alkaline substances such as O3, KHCO3, NH3, etc. can be used.

The concentration used can be freely selected from a wide range.

It is preferable to use an aqueous N a HCO3 solution.

Neutralization and water washing at 10-90°C, preferably 10-50°C
It is best to carry out in the temperature range of °C.

In order to remove low-boiling components from the reaction crude liquid that has been neutralized or washed with water, it is preferable to use a thin film evaporator or the like after adding a polymerization inhibitor.

In particular, there are cases where compounds selected from [groups A and B] contained in the crude reaction solution are extracted into the lower layer water and the content in the neutralized upper layer decreases. It is preferable to replenish an appropriate amount of the compound, and it is also desirable to blow molecular oxygen into the system during neutralization and washing with water.

In the neutralization water washing process, it is important to neutralize and remove residual organic peracids as well as remove residual organic peracids. Peracid content below 0.1%.

It is necessary to repeat neutralization and washing with water until the concentration is preferably 0.01% or less.

Therefore, in the case of continuous neutralization washing, a multi-stage method is required, but if the number of stages is usually 3 to 5, the organic peracid concentration can be lowered to below the specified value.

In the case of a multi-stage method, it is preferable to completely wash with water or use an alkaline aqueous solution of about 1% at most in the final stage.

This is because if the bottom liquid after removing low-boiling components is used as a product as it is, alkali metals will be mixed into the product and affect its quality.

This also applies to repeated batch neutralizations. In addition, when the neutralization water washing is carried out in a continuous manner, there is no problem in using the lower layer water in a countercurrent manner for pre-neutralization, and it is more economical.

The amount of alkali used for neutralization washing with water is 0.5 to 3 times the equivalent amount of the total amount of organic peracid and organic acid in the crude reaction solution, preferably 1.1" and 1.5 ft!. It is often not economical to increase the amount more than necessary, and if the equivalence ratio is lowered more than necessary, it is not a good idea because a large amount of water is required to remove the organic peracid or organic acid. ,
Dissolution loss of solvent etc. into the lower water also increases.

Following the neutralization water wash step, the solvent is removed.

(Low-boiling removal process) A thin film evaporator is usually used for low-boiling removal, and the heating temperature is 50 to 180°C, preferably 60 to 180°C in order to prevent polymerization.
It is best to carry out the test at 00°C.

Although the pressure can be arbitrarily selected depending on the physical properties of the low boiling point component, it is common to operate under reduced pressure in relation to the heating temperature.

Molecular oxygen can be introduced into the evaporator at any location, but it is usually blown into the evaporator from the line where the bottom liquid is distilled.

The amount of injection can be selected arbitrarily, but the upper limit is determined by the capacity of the vacuum system, whether the bottom liquid flows down stably, and the recovery loss when collecting the distilled low-boiling components with a condenser. limited. Although the bottom liquid obtained in the low-boiling removal step has a purity of only 94 to 96%, as a result of the present invention, the quality is such that the HT is transparent or slightly cloudy.

Therefore, it can be used as a product for normal purposes.

In order to obtain a product with even higher purity, a productization step is performed next.The productization step completely removes the remaining low-boiling components and is carried out in the same way as the de-low-boiling step, but the degree of pressure reduction is further increased. It is generally carried out under high vacuum.

Examples will be described in more detail below.

Example-1 Inner capacity 200j with stirrer and cooling jacket
14.4 kg of cyclohexenyl methyl methacrylate, 52-18 kg of ethyl acetate, 12 gr of hydroquinone monomethyl ether, and 12 g of pyrophosphoric acid in a glass reactor.
and oxygen/nitrogen (10/nitrogen) from the insertion tube into the reactor.
A mixed gas of 90% by volume) was blown in at 100 Nj/Hr.

Next, the reaction temperature was kept at 50°C, and 30% peracetic acid solution 2
4.8 kg was charged over 4 hours using a metering pump. After completion of the charging, 1 g of the 0-reaction crude liquid was collected from which the reaction was completed after aging for an additional 4 hours, and dissolved in n-hebutane Log, which was transparent.

After cooling the reaction crude liquid to room temperature, 10% Na2CO350kg
was added and stirred for 30 minutes, then left to stand for 30 minutes to separate the liquids. After removing the lower layer water, 350 kg of 10% Na 2 C was added and the same operation was performed.

At this time, the residual peracetic acid concentration in the upper layer liquid was 0.02%, and acetic acid had completely disappeared.

Next, when 50 kg of 1% Na CO 3 was added and the same operation was performed, the peracetic acid concentration was 0.01% or less.

Next, 12 g of hydroquinone monomethyl ether and 12 g of birophosphoric acid were added to 70.5 kg of the neutralized upper layer liquid, and the mixture was subjected to low boiling treatment using a glass Smith type thin film evaporator. The operating conditions were a heating temperature of 80° C. and a pressure of 150 mmHg, and a mixed gas of oxygen/nitrogen (<10/90% by volume) was blown in from the bottom liquid distillation line at 100 Nj/Hr.

The amount of bottom liquid obtained was 14.2 kg.

In addition, the composition was investigated by gas chromatography analysis and found to be 894.7% METH, 1.8% ethyl acetate, 1.0% cyclohexenyl methyl methacrylate, and 2.5% others.
%Met.

When 1 g of the bottom liquid was dissolved in 10 g of n-hebutane, the solution was transparent.

Example-2 Inner capacity 200J with stirrer and cooling jacket
14.4 kg of cyclohexenyl methyl methacrylate, 52.8 kg of ethyl acetate, 12 g of hydroquinone, and 2 g of sodium 2-ethylhexyl tripolyphosphate were added to a glass reactor, and oxygen/nitrogen (10/90 volume) was added to the reactor from an insertion tube. %) mixed gas at 100NJ/Hr
Then, the reaction temperature was kept at 40 °C and 30
% peracetic acid solution was charged over 4 hours using a metering pump.

After the completion of the preparation, 1 g of the 0-reaction crude liquid after the reaction was further aged for 6 hours was collected and dissolved in 10 g of n-hebutane, and the resultant mixture was transparent.

After cooling the reaction crude liquid to room temperature, 40 kg of 10% NaOH was added, stirred for 30 minutes, and then allowed to stand for 30 minutes to separate the liquid. After removing the lower layer water, 340 kg of 10% Na 2 C was added and the same operation was performed.

At this time, the residual peracetic acid concentration in the upper layer liquid was 0.03%, and acetic acid had completely disappeared.8 Next, 40 kg of 1% NaOH was added.
When the same operation was performed with the addition of
% or less.

Next, add 12% of hydroquinone to 69.6kg of the neutralized NJ solution.
g, 2-ethylhexyl sodium tripolyphosphate 12
g was added thereto, and low boiling temperature was removed using a glass Smith type thin film evaporator.

The operating conditions were a heating temperature of 100°C, a pressure of 150 mmHg, and a mixed gas of oxygen/nitrogen (10-/9090 volume) was blown in from the bottom liquid distillation line at 100 Nj/Hr. The amount of bottom liquid obtained was 13. 9 kg.The composition was also investigated by gas chromatography analysis and found to be METH895.5%.
, ethyl acetate 1°7%, cyclohexenylmethyl methacrylate 1°2%, the fl! ! It was 1.6%.

When 1g of the bottom liquid was dissolved in 10g of n-heptane, it became slightly cloudy, but no precipitate was observed. continue,
A high-purity product was obtained by further removing the low boiling point in the same apparatus under conditions of a heating temperature of 80° C. and a pressure of 2 to 3 mmHH.

At this time, a small amount of air was introduced into the system from the bottom of the tower.

The amount of bottom liquid obtained was 9.6 kg.

Gas chromatography analysis revealed M E 'I'
The HB purity was 98.1%. 1g of the bottom liquid was dissolved in 10g of n-hebutane.Although it became cloudy, it could be used as a product.

Contents: 200 with stirrer and cooling jacket
14.4 kg of cyclohexenyl methyl methacrylate and 52 kg of ethyl acetate were placed in a glass reactor. .

8 kg, 12 g of hydroquinone monomethyl ether, and 12 g of pyrophosphoric acid, and oxygen/oxygen was added to the reactor from the insertion tube.
Mixed gas of nitrogen (10/90% by volume) at 100Nj/
I injected it with HR.

Next, the reaction temperature was maintained at 50°C, and a 30% peracetic acid solution was added at 24°C.
．． 8 kg was charged over 4 hours using a metering pump.

After the preparation was completed, the reaction was terminated after further aging for 4 hours.9
When 1 g of the crude reaction solution was collected and dissolved in 10 g of n-hebutane, it was clear.

After cooling the reaction crude liquid to room temperature, 10% Na 2 C03
Add 50 kg, stir for 30 minutes, and leave to separate for 30 minutes.

After removing the lower layer water, 50 kg of 10% Na2CO3 was added and the same operation was performed.

At this time, the residual peracetic acid concentration in the upper layer liquid was 0.02%, and acetic acid had completely disappeared.

Next, when 350 kg of 1% Na CO was added and the same operation was performed, the peracetic acid concentration was 0.01% or less.

Next, 71.1 kg of the neutralized upper layer liquid was subjected to low boiling treatment using a glass Smith type thin film evaporator.

The operating conditions were a heating temperature of 100°C, a pressure of 150 mmHg, a mixed gas of oxygen/nitrogen (10/90% by volume) blown from the bottom liquid line at 100 Nj/Hr, and a bottom liquid of 3.3 k.
However, the operation was interrupted due to abnormal vibration noise of the evaporator.

When the evaporator was disassembled, resin-like polymers were found adhering to the walls and stirring blades. When 1 g of the obtained tower bottom liquid was dissolved in 10 g of n-hebutane, a large amount of white precipitate was deposited.

Patent applicant: Daicel Chemical Industries, Ltd. 1゜ 2゜ Procedural amendment (voluntary) Display of incidents 1999 Patent Application No. 581, name of invention epoxidized (meth)acrylate composition Name (290) Daicel Chemical Industries, Ltd. 5. Contents of correction (1) Amend the claims as per the attached appendix.

(2) Line 13 of page 4 of the specification, line 2 from the bottom of page 8, line 2 from the bottom of page 11, line 2 of page 12, line 7 of page 12, line 8 of page 12 Line 9, page 12, line 15, page 12, lines 19-20, "--hexenyl (meth)..." is corrected to r-kai...hexenylmethyl (meth)-@-J.

(3) On page 10, line 4 of the specification, "...ammonium hydrogen..." is amended to "φ...ammonium sodium hydrogen...". (White space below) Claims column and Detailed description of the invention column (4) On page 10, line 9 of the specification, "phosphoric acid, potassium tripolyphosphate tripolyphosphoric acid" was replaced with "phosphoric acid, potassium tripolyphosphate". Potassium ethylhexyl tripolyphosphate,
2-Ethylhexyltripolyphosphate". (Space below) Attachment 2, Claims A cyclohexenyl methyl (meth)acrylate compound represented by the general formula (I) (wherein R represents a hydrogen atom or a methyl group) is epoxidized with an oxidizing agent and the general formula ( 11) A compound represented by (wherein R represents a hydrogen atom or a methyl group) and at least one compound each selected from the following [Group A] and [Group B] are coexisting. Epoxidized (meth)acrylate composition: [Group A] Hydroquinone, hydroquinone monomethyl ether,
P-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-
t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-
P-cresol, 2,5-dihydroxy-P-quinone,
Piperidine, ethanolamine, α-nitroso-β-naphthol, diphenylamine, phenothiazine, N-nitrosophenylhydroxylamine, N,N-diethylhydroxylamine [group B] phosphoric acid, potassium phosphate, sodium phosphate, ammonium hydrogen phosphate Sodium, pyrophosphoric acid, potassium pyrophosphate, sodium pyrophosphate, birophosphate 2-ethylhexyl ester, potassium birophosphate 2-ethylhexyl ester, sodium pyrophosphate-2-ethylhexyl ester, tripo IJ phosphoric acid, 2-ethylhexyl potassium tripolyphosphate, 2 - Sodium ethylhexyl tripolyphosphate, sodium 2-ethylhexyltetrapolyphosphate, potassium 2-ethylhexyltetrapolyphosphate. (Margin below)

Claims (1)

[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a hydrogen atom or a methyl group) A cyclohexenyl (meth)acrylate compound represented by an oxidizing agent Epoxidized with the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R represents a hydrogen atom or a methyl group) and the following [Group A] and [Group B] ] An epoxidized (meth)acrylate composition characterized by the coexistence of at least one compound selected from the following: [Group A] Hydroquinone, hydroquinone monomethyl ether,
P-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-
t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-
P-cresol, 2,5-dihydroxy-P-quinone,
Piperidine, ethanolamine, α-nitroso-β-naphthol, diphenylamine, phenothiazine, N-nitrosophenylhydroxylamine, N,N-diethylhydroxylamine [group B] phosphoric acid, potassium phosphate, sodium phosphate, ammonium hydrogen phosphate , pyrophosphoric acid, potassium pyrophosphate, sodium pyrophosphate, 2-ethylhexyl pyrophosphate, potassium 2-ethylhexyl pyrophosphate, sodium 2-ethylhexyl pyrophosphate, tripolyphosphoric acid, potassium tripolyphosphate, sodium tripolyphosphate.