JPH1192425A - Acrylate derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject derivative useful as a raw material for various kinds of coating materials, a monomer for crosslinking, a monomer or the like for resists by reacting specific oxyacrylic acid esters with a polybasic acid (anhydride). SOLUTION: (A) An oxyacrylic acid ester of formula I (R<1> is H or an organic residue; R<3> is an organic residue) (e.g. ethyl α-hydroxymethyl-acrylate) is reacted with (B) a polybasic acid (anhydride) (e.g. maleic anhydride) to provide the objective derivative of formula II (R<2> is an organic residue). A method or the like reacting, e.g. a component A with a component B in an amount of 0.01-5 mol based on 1 mol component A in the presence of a polymerization preventing agent (or polymerization inhibitor) (e.g. hydroquinonemonomethyl ether) and a molecular oxygen (e.g. air), preferably at 0-150 deg.C, more preferably at 30-120 deg.C is preferably adopted as the reaction method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to the following general formula (2):

[0002]

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(Wherein R ¹ represents a hydrogen atom or an organic residue, and R ² and R ³ each independently represent an organic residue) and a method for producing the same. It is.

The acrylate derivative is useful as a raw material for various paints, a crosslinking monomer, a resist monomer, and the like.

[0005]

2. Description of the Related Art Various methods have been studied for producing a carboxyl group-containing compound by reacting a compound having a hydroxyl group with a polybasic anhydride and / or a polybasic acid.

For example, Japanese Patent Application Laid-Open No. 4-294351 discloses that when 2-hydroxyethyl (meth) acrylate is reacted with succinic anhydride, the following formula (3) is obtained.

[0007]

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There is disclosed a synthesis example in which a carboxyl group-containing acrylate represented by the formula (wherein R ⁴ represents a hydrogen atom or a methyl group) is obtained.

However, the acrylate derivative represented by the general formula (2) and a method for producing the same have not been known so far.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an acrylate derivative represented by the general formula (2) and a method for producing the same, which can be used for various purposes.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies to provide an acrylate derivative represented by the general formula (2), and as a result, have found that oxyacrylate and polybasic anhydride and / or The inventors have found that an acrylate derivative represented by the general formula (2) can be obtained by reacting with a polybasic acid, thereby completing the present invention.

That is, the present invention provides a compound represented by the following general formula (1):

[0013]

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Wherein R ¹ represents a hydrogen atom or an organic residue, and R ³ represents an organic residue, and a polybasic anhydride and / or a polybasic acid. And reacting with the general formula (2):

[0015]

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(Wherein R ¹ represents a hydrogen atom or an organic residue, and R ² and R ³ each independently represent an organic residue).

Another aspect of the present invention provides a compound represented by the following general formula (2):

[0018]

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(Wherein, R ¹ represents a hydrogen atom or an organic residue, and R ² and R ³ each independently represent an organic residue).

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylate derivative according to the present invention is characterized in that, in the general formula (2), the substituent represented by R ¹ is a hydrogen atom or an organic residue, and the substituent represented by R ² Is a compound composed of a divalent organic residue and the substituent represented by R ³ is composed of an organic residue.

In the general formula (2), R ¹ is a hydrogen atom, and the group represented by R ² is

[0022]

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(Wherein, R ⁵ is a direct bond or a compound having 1 to 1 carbon atoms)
8 represents an alkyl group; R ⁶ and R ⁷ represent a direct bond or an alkyl group having 1 to 6 carbon atoms; R ⁸ and R ⁹ represent a direct bond or an alkyl group having 1 to 3 carbon atoms; May be substituted with an alkyl group, a hydroxyl group, a carboxyl group, or a halogen atom. ) And R ³
Is a linear or branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group,
Compounds which are 20 alkoxyalkyl groups and halogenated alkyl groups having 1 to 8 carbon atoms are preferred.

In the general formula (2), R ¹ is a hydrogen atom, and the group represented by R ² is

[0025]

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And the group represented by R ³ is an alkyl group having 1 to 8 carbon atoms.

In the general formula (2), R ¹ is a hydrogen atom, and the group represented by R ² is

[0028]

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And the group represented by R ³ is an alkyl group having 1 to 4 carbon atoms.

The method for producing the acrylate derivative of the present invention is not particularly limited. For example, by reacting an oxyacrylate with a polybasic anhydride and / or a polybasic acid. Easily manufactured. The manufacturing method will be described below.

In the method for producing an acrylate according to the present invention, the oxyacrylate used as a raw material is represented by the general formula (1), wherein R ^{1 is}
Is a compound in which the substituent represented by is composed of a hydrogen atom or an organic residue, and the substituent represented by R ³ is composed of an organic residue. Specific examples of the substituent represented by R ¹ include a hydrogen atom and an alkyl group having 1 to 8 carbon atoms. Specific examples of the substituent represented by R ³ include a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group, an alkoxyalkyl group having 2 to 20 carbon atoms, Halogenated alkyl groups of the formulas 1 to 8 and the like can be mentioned.

Specific examples of the oxyacrylate compound represented by the general formula (1) include, for example, methyl-α-hydroxymethyl acrylate, ethyl-α
-Hydroxymethyl acrylate, butyl-α-hydroxymethyl acrylate, 2-ethylhexyl-α-hydroxymethyl acrylate, methyl-α- (1-hydroxyethyl) acrylate, ethyl-α- (1-hydroxyethyl) acrylate, butyl-α -(1-hydroxyethyl) acrylate, 2-ethylhexyl-α
-(1-hydroxyethyl) acrylate and the like. One of these oxyacrylate compounds may be used alone, or two or more of them may be appropriately mixed. Of the compounds exemplified above, methyl-α-hydroxymethyl acrylate, ethyl-α-hydroxymethyl acrylate, butyl-α-hydroxymethyl acrylate, and 2-ethylhexyl-α-hydroxymethyl acrylate are preferable because of their excellent polymerizability.

The oxyacrylate compound is reacted with a conventionally known method, for example, by reacting the corresponding acrylate compound with an aldehyde compound in the presence of a catalyst for a basic ion exchange resin (JP-A-6-135896). And the like, can be easily obtained.

The polybasic acid and / or anhydride used as a raw material in the method for producing an acrylate ester according to the present invention include succinic acid, maleic acid, o-phthalic acid, isophthalic acid, terephthalic acid, o-hexahydroacid. Examples thereof include polybasic acids such as phthalic acid, m-hexahydrophthalic acid, p-hexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, diphenic acid, and anhydrides thereof, but are particularly limited. Not something.

The method of reacting the oxyacrylate compound with the polybasic anhydride and / or polybasic acid is not particularly limited, and various conventionally known methods can be used. For example, as a reaction method between the oxyacrylate compound and the polybasic anhydride, for example, a method in which the oxyacrylate compound and the polybasic anhydride are heated and reacted is preferable.

As a method of reacting the oxyacrylate compound with the polybasic acid, for example, a method of reacting the oxyacrylate compound with the polybasic acid by heating in the presence of a catalyst is preferable.

In the above method, the amount of the polybasic anhydride to be added to the oxyacrylate compound is in the range of 0.01 to 5 mol per mol of the oxyacrylate compound. I just need. When the added amount of the polybasic anhydride is less than 0.01 mol, unreacted oxyacrylate remaining after the reaction may increase. When the amount of the polybasic anhydride added is more than 5 mol, unreacted polybasic anhydride remaining after the reaction may increase.

The reaction conditions and the like for performing the above method are not particularly limited, but the oxyacrylate ester as a raw material and the acrylate ester as a product contain a vinyl group in the molecule. It has the property of being easily polymerized. Therefore, it is preferable to add a polymerization inhibitor (or polymerization inhibitor) or molecular oxygen to the reaction system in order to suppress the polymerization of the oxyacrylate or acrylate.

As the polymerization inhibitor, hydroquinone,
Hydroquinone monomethyl ether, p-benzoquinone,
Methylhydroquinone, t-butylhydrquinone, di-t-
Examples thereof include, but are not particularly limited to, butylhydroquinone, t-butylcatechol, and phenothiazine. These polymerization inhibitors may be used alone,
Further, two or more kinds may be appropriately mixed. The amount of the polymerization inhibitor to be added is not particularly limited.
The content may be in the range of 001% by weight to 5% by weight. As the molecular oxygen, for example, air can be used. In this case, air may be blown into the reaction system, that is, a mixture of oxyacrylic acid and polybasic anhydride (so-called bubbling). In order to sufficiently suppress the polymerization, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

In carrying out the above-mentioned method, it is not necessary to use a catalyst, but it is possible to use a catalyst. As the catalyst to be used, a known catalyst used for a reaction between a hydroxyl group and a polybasic anhydride can be used. Examples include tertiary amine compounds such as triethylamine, tributylamine and triphenylamine, and quaternary ammonium salts such as chloro salts and bromo salts thereof. When the catalyst is used, the amount of the catalyst used is 10% by weight or less, preferably 5% by weight, based on the oxyacrylate used.
The following is preferred. Large amounts are not economically advantageous.

In carrying out the above method, it is not necessary to use a solvent, but a solvent may be used. The solvent used may be any solvent that does not inhibit the reaction,
Aromatic solvents and aliphatic solvents such as cyclohexane, benzene, toluene and xylene are preferably used.

The reaction temperature at the time of carrying out the above method is not particularly limited, but is preferably in the range of 0 ° C. to 150 ° C., and is preferably 30 to 12 ° C. in order to suppress the above-mentioned polymerization.
A temperature in the range of 0 ° C. is particularly preferred. If the reaction temperature is lower than 0 ° C., the reaction time may be too long, and the acrylate may not be efficiently produced. If the reaction temperature is higher than 150 ° C., the above-mentioned polymerization may not be able to be suppressed. Since the reaction between the oxyacrylic acid ester compound and the polybasic anhydride is an exothermic reaction, when reacting the two, excess heat is removed from the reaction system and an amount corresponding to the amount of heat removed from the reaction system. The reaction may be allowed to proceed while maintaining the reaction temperature substantially constant by adding the polybasic anhydride of the above to the reaction system in the form of powder or in a molten state or by dissolving it in a solvent. However, the above reaction does not necessarily have to proceed at a substantially constant reaction temperature. The reaction time may be appropriately set depending on the reaction temperature, the type and combination of the oxyacrylic acid ester compound and the polybasic anhydride, the amount used, and the like so that the above reaction is completed. The reaction pressure at this time is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

After completion of the reaction, the catalyst and the organic solvent are removed as required, and the desired acrylate derivative can be easily obtained. The method for removing the catalyst and the organic solvent is not particularly limited.

In the above-mentioned method, for example, α-hydroxyalkyl acrylate is used as the oxyacrylate compound, and the α-hydroxyalkyl acrylate and the polybasic acid are heated in the presence of a catalyst. Is preferred.

In carrying out the above method, the catalyst may be
A known catalyst used for an esterification reaction between a hydroxyl group and a carboxyl group can be used. For example, protonic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, benzenesulfonic acid, and acidic ion exchange resin are exemplified, and methanesulfonic acid and paratoluenesulfonic acid are preferably used. . One of these catalysts may be used alone, or two or more of them may be appropriately mixed.

The amount of the catalyst to be added to the oxyacrylate compound depends on the kind of the oxyacrylate to be used. For example, the ratio to the oxyacrylate is 0.001% by weight to 50% by weight.
, Preferably in the range of 0.01% by weight to 10% by weight. When the amount of catalyst added is 0.0
If the amount is less than 01% by weight, the reaction time may be too long, and the acrylate derivative may not be efficiently produced. Further, even if the addition amount of the catalyst is more than 50% by weight, further improvement of the effect such as reduction of the reaction time cannot be expected, and a part of the added catalyst may be wasted, which may be economically disadvantageous. is there.

When the above method is carried out, the amount of the polybasic acid added to the oxyacrylate compound is 0.0 mol per mol of the oxyacrylate ester.
The range may be 1 to 5 mol. If the amount of the polybasic acid is less than 0.01 mol, unreacted oxyacrylate remaining after the reaction may increase.
If the amount of the polybasic acid added is more than 5 mol, unreacted polybasic acid remaining after the reaction may increase.

The reaction conditions and the like for carrying out the above method are not particularly limited, but the oxyacrylate ester as a raw material and the acrylate ester as a product contain a vinyl group in the molecule. It has the property of being easily polymerized. Therefore, it is preferable to add a polymerization inhibitor (or polymerization inhibitor) or molecular oxygen to the reaction system in order to suppress the polymerization of the oxyacrylate or acrylate.

As the polymerization inhibitor, those mentioned in the reaction between oxyacrylic acid and polybasic anhydride can be used, but are not particularly limited. One of these polymerization inhibitors may be used alone, or two or more thereof may be appropriately mixed. Further, the amount of the polymerization inhibitor to be added is not particularly limited. For example, the ratio to the obtained acrylate is 0.001% by weight.
It may be within the range of 5% by weight. As the molecular oxygen, for example, air can be used. In this case, air may be blown into the reaction system, that is, a mixture of oxyacrylic acid and polybasic anhydride (so-called bubbling). In order to sufficiently suppress the polymerization, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

In the case of carrying out the above method, it is not necessary to use a solvent. However, since the reaction between oxyacrylic acid and polybasic acid is a dehydration reaction, it is used for the purpose of azeotropically removing the generated water used. Is more preferred. The solvent used may be any solvent that does not inhibit the reaction, but aromatic solvents such as cyclohexane, benzene, toluene and xylene and aliphatic solvents are preferably used.

The reaction temperature at the time of carrying out the above method is not particularly limited, but is preferably in the range of 0 ° C. to 150 ° C., and is preferably 30 to 12 to suppress the above-mentioned polymerization.
A temperature in the range of 0 ° C. is particularly preferred. If the reaction temperature is lower than 0 ° C., the reaction time may be too long, and the acrylate may not be efficiently produced. If the reaction temperature is higher than 150 ° C., the above-mentioned polymerization may not be able to be suppressed. Since the reaction between oxyacrylic acid and polybasic acid is a dehydration reaction, when reacting both, water generated from the reaction system is removed, and anhydrous polyhydric acid is added in an amount corresponding to the amount of heat removed from the reaction system. The reaction may be allowed to proceed while maintaining the reaction temperature substantially constant by adding the basic acid to the reaction system in a powdered or molten state or dissolved in a solvent. However, the above reaction does not necessarily have to proceed at a substantially constant reaction temperature. The reaction time may be appropriately set according to the reaction temperature, the type and combination of the oxyacrylic acid-based compound and the polybasic anhydride, the amount used, and the like so that the above reaction is completed. The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

After completion of the reaction, the desired acrylate derivative can be easily obtained by removing the catalyst and the solvent from the reaction system by a predetermined method. The method for removing the catalyst is not particularly limited. For example, a method of washing with an alkaline aqueous solution, or adding an acid adsorbent, adsorbing the catalyst in the reaction solution to the adsorbent to form an insoluble substance, and then filtering the reaction solution, etc. The catalyst can be removed. The method for removing the solvent is not particularly limited. For example, distillation by evaporation, removal by blowing air or an inert gas, and the like can be adopted.

[0053]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

The reaction product was identified by ¹ H-NMR
And ¹³ C-NMR.

Example 1 500 m equipped with a stirrer, thermometer and gas injection pipe
Into 1 reaction vessel, 130 g of ethyl α-hydroxymethyl acrylate, 98 g of maleic anhydride, and 0.046 g of hydroquinone monomethyl ether as a polymerization inhibitor were charged. While blowing air into the reaction solution, the temperature of the reaction solution was set to 80 to 90 ° C., and the reaction was performed while removing heat. After exotherm was no longer observed, the reaction solution was kept at 90 ° C. for 10 hours for aging. This liquid was subjected to suction filtration to obtain 58 g of a pale yellow transparent liquid. ¹ H-NM of the obtained reaction product
The R and ¹³ C-NMR spectra are shown in FIGS. As a result, it was specified that the obtained compound was α-((3-carboxy-1-oxopropenyl) oxymethyl) acrylic acid.

[0056]

The novel acrylate derivative represented by the general formula (2) is useful for a conventionally known monomer having a carboxyl group, for example, mono (2-acryloyloxyethyl) succinate. It can be used for similar applications. For example, an acrylate derivative or a polymer comprising the acrylate derivative can be used as a so-called paint adhesion improver. That is, by adding an acrylate derivative or a polymer composed of the acrylate derivative to a coating material, the adhesion of a coating film to an object to be coated can be improved.

The acrylic ester derivative or the polymer comprising the acrylic ester derivative is
A crosslinking monomer used for a crosslinking reaction such as an epoxy resin;
Since it is useful for ultraviolet curable resins and alkali-soluble resin monomers, it can be suitably used for resist materials such as etching resists and photoresists.

[Brief description of the drawings]

[1] ¹ H-NMR of the reaction product obtained in Example 1
It is a spectrum diagram.

FIG. 2 is a ¹³ C-NMR of the reaction product obtained in Example 1.
It is a spectrum diagram.

Claims (3)

[Claims] 1. General formula (1): (Wherein, R ¹ represents a hydrogen atom or an organic residue, and R ³ represents an organic residue), and a polybasic anhydride and / or a polybasic acid. General formula (2) characterized by the following: (Wherein, R ¹ represents a hydrogen atom or an organic residue, and R ² , R
³ each independently represents an organic residue). 2. General formula (2): (Wherein, R ¹ represents a hydrogen atom or an organic residue, and R ² and R ³ each independently represent an organic residue). 3. In the general formula (2), R ¹ is a hydrogen atom, and R ² is The acrylate derivative according to claim 2, wherein R ³ is an alkyl group having 1 to 4 carbon atoms.