JP7124541B2 - (Meth)acrylic acid ester and method for producing (meth)acrylic acid ester - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel (meth)acrylic acid ester having excellent hydrophilicity, a method for producing the novel (meth)acrylic acid ester, and a hydroxy compound used in the production method.

Generally, (meth)acrylic acid esters are useful in a wide variety of applications such as plastics, paints, adhesives, paper processing agents, textile oils, lubricating oil additives, building sealants, and inks. Also, as a resist polymer used in ArF excimer laser lithography, an acrylic polymer that is transparent to light with a wavelength of 193 nm has attracted attention. In recent years, as a resist composition suitable for shortening the wavelength of irradiation light and miniaturizing patterns, a polymer that becomes alkali-soluble due to elimination of an acid-labile group by the action of an acid and a photo-acid generator have been developed. A so-called chemically amplified resist composition has been proposed, and its development and improvement are proceeding.
As a monomer having an acid-leaving group, Patent Documents 1 and 2 disclose that the ester moiety is a hydrocarbon group containing a cycloalkyl group, and the bonding site between the oxygen atom constituting the ester bond and the cycloalkyl group is (Meth)acrylic acid esters with tertiary carbon atoms are described.

WO2011/062168 JP 2015-141353 A

In recent years, miniaturization of pattern formation by lithography has progressed rapidly, and development of a resist material capable of further improving various lithography properties such as pattern formability and line width roughness (LWR) is desired. By increasing the hydrophilicity of the resist material, the solubility in the developing solution can be improved, and as a result, performance such as LWR, MEEF (mask error factor), and DOF (depth of focus) can be improved. For that purpose, a more hydrophilic monomer is useful.
An object of the present invention is to provide a (meth)acrylic acid ester having excellent hydrophilicity, a method for producing the (meth)acrylic acid ester, and a hydroxy compound used in the production method.

The present invention has the following aspects.
[1] A (meth)acrylic acid ester represented by the following formula (1).

[wherein R ¹ is a hydrogen atom or a methyl group, one of R ²¹ , R ²² and R ²³ is an alkoxy group having 1 to 20 carbon atoms, and the other one is a an alkyl group, the remaining one is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Z ¹ is a substituted or unsubstituted divalent chain formula having 1 to 20 carbon atoms a hydrocarbon group, a substituted or unsubstituted divalent cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a heteroatom, or a single bond, Z ² is 2 having 1 to 12 carbon atoms A valent chain hydrocarbon group Z ³ is a cyclic hydrocarbon group optionally having a heteroatom having 3 to 10 carbon atoms together with the carbon atom to which (R ²¹ R ²² R ²³ )C— is bonded. and n is an integer of 0-3. ]
[2] A hydroxy compound represented by the following formula (4).

[In formula (4), one of R ²¹ , R ²² and R ²³ is an alkoxy group having 1 to 20 carbon atoms, the other one is an alkyl group having 1 to 20 carbon atoms, and the remaining one is hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Z ³ is a hetero atom having 3 to 10 carbon atoms together with the carbon atom to which (R ²¹ R ²² R ²³ )C— is bonded is an atomic group forming a cyclic hydrocarbon group which may have ]
[3] A (meth)acrylic acid ester obtained by reacting the hydroxy compound described in [2] above with a (meth)acrylic acid chloride to obtain a (meth)acrylic acid ester represented by the following formula (5): manufacturing method.

[wherein R ¹ is a hydrogen atom or a methyl group, one of R ²¹ , R ²² and R ²³ is an alkoxy group having 1 to 20 carbon atoms, and the other one is a an alkyl group, the remaining one is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, Z ³ is the carbon atom to which (R ²¹ R ²² R ²³ )C— is bonded It is an atomic group that forms a cyclic hydrocarbon group optionally having a heteroatom of 3 to 10 carbon atoms together with . ]

According to the present invention, a (meth)acrylic acid ester having excellent hydrophilicity can be obtained.
The hydroxy compound of the present invention is useful as an intermediate for (meth)acrylic acid esters.

The following term definitions apply throughout the specification and claims.
As used herein, "(meth)acrylic acid" means acrylic acid or methacrylic acid.
In this specification, the compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulas are similarly described.

<(Meth) acrylic acid ester>
The (meth)acrylic acid ester of the present invention is a compound (1) represented by the following formula (1). Compound (1) is useful as a monomer having an acid-leaving group.

In formula (1), R ¹ is a hydrogen atom or a methyl group.
One of R ²¹ , R ²² and R ²³ is an alkoxy group having 1 to 20 carbon atoms, the other one is an alkyl group having 1 to 20 carbon atoms, the remaining one is a hydrogen atom, and the It is an alkoxy group or an alkyl group having 1 to 20 carbon atoms.

Among R ²¹ , R ²² , and R ²³ , it is preferable that the number of alkyl groups is 1 in that higher hydrophilicity can be easily obtained.
That is, it is preferable that one of R ²¹ , R ²² and R ²³ is an alkoxy group, the other one is an alkyl group, and the remaining one is a hydrogen atom or an alkoxy group.

The alkoxy group is preferably linear or branched. The number of carbon atoms in the alkoxy group is preferably 1-4, more preferably 1-3, and still more preferably 1 or 2.
The alkyl group may be linear, branched, or a cycloalkyl group. The number of carbon atoms in the linear or branched alkyl group is preferably 1-4, more preferably 1-3, and still more preferably 1 or 2.
The cycloalkyl group preferably has 3 to 8 carbon atoms, more preferably 5 or 6 carbon atoms.

Z ¹ is a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms and optionally having a hetero atom; or a single bond.
When Z ¹ is a divalent chain hydrocarbon group, it may be linear or branched. An alkylene group is preferred as the divalent chain hydrocarbon group. Substituents include -O-, -S-, -NH- and -PH-. The number of carbon atoms is preferably 1-10, more preferably 1-6.
When Z ¹ is a divalent cyclic hydrocarbon group, it may be monocyclic or polycyclic. A cyclic saturated hydrocarbon group is preferable as the cyclic hydrocarbon group. Heteroatoms include nitrogen, oxygen, sulfur and phosphorus atoms. A substituent may be bonded to a carbon atom constituting the ring. Examples of substituents include alkyl groups having 1 to 10 carbon atoms. Alkyl groups may be linear or branched.
Z1 is preferably a ^single bond from the viewpoint of increasing the solubility of the resist material in the developer.

Z ² is a divalent chain hydrocarbon group having 1 to 12 carbon atoms. It may be linear or branched. An alkylene group is preferred as the chain hydrocarbon group. The number of carbon atoms is preferably 1-6, more preferably 1-3.
n is an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1.

Z ³ is an atomic group forming a cyclic hydrocarbon group optionally having a heteroatom with 3 to 10 carbon atoms together with the carbon atom to which (R ²¹ R ²² R ²³ )C— is bonded; be. A cyclic hydrocarbon group may be monocyclic or polycyclic. The cyclic hydrocarbon group is preferably a hydrocarbon cyclic hydrocarbon group (having no heteroatoms).
The number of carbon atoms in the cyclic hydrocarbon group includes the carbon atom to which (R ²¹ R ²² R ²³ )C- is attached.
Cyclic hydrocarbon groups consisting of monocyclic hydrocarbons having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclopentenyl. group, cyclohexenyl group, cyclooctadienyl group, and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable from the viewpoint of availability.
Cyclic hydrocarbon groups consisting of polycyclic hydrocarbons having 3 to 10 carbon atoms include, for example, bicyclo[4.3.0]nonanyl, naphthalenyl, decahydronaphthalenyl, bornyl, isobornyl, norbornyl group, adamantyl group, noradamantyl group, and the like. Among these, a norbornyl group and an adamantyl group are preferred from the standpoint of availability.

Preferred embodiments of compound (1) include the following.
R ¹ is a hydrogen atom or a methyl group, and Z ³ is an atomic group forming a cyclopentyl group, a cyclohexyl group, a norbornyl group or an adamantyl group together with the carbon atom to which (R ²¹ R ²² R ²³ )C- is bonded. and R ²¹ , R ²² and R ²³ are any combination of a methoxy group, a methyl group and a hydrogen atom, any combination of two methoxy groups and a methyl group, or any combination of a methoxy group and two methyl groups and Z ¹ is a single bond and n=0.

Compound (1) is prepared by, for example, reacting hydroxy compound (4) represented by formula (4) below with (meth)acrylic acid chloride to obtain (meth)acrylic acid represented by formula (5) below. It can be produced by a method for obtaining ester (5).
The hydroxy compound (4) can be produced by reacting an ester compound (2) represented by the following formula (2) with a compound (3) represented by the following formula (3).

In formula (2), R ²¹ , R ²² and R ²³ are the same as R ²¹ , R ²² and R ²³ in formula (1) including preferred embodiments.
In formula (2), R ¹¹ is an alkyl group. The alkyl group may be linear, branched, or a cycloalkyl group. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable from the standpoint of availability.

In formula (3), Y ¹ is an alkylene group having 2 to 9 carbon atoms or a cycloalkylene group, and M ² and M ³ are each independently MgX (X is a halogen atom).
The alkylene group of Y ¹ may be linear or branched. Examples thereof include ethylene group, propylene group, isopropylene group, butylene group, pentylene group and hexylene group. A cyclohexylene group etc. are mentioned as a cycloalkylene group. Among these, a butylene group and a pentylene group are preferable from the viewpoint of availability.

In the reaction between compound (2) and compound (3), the amount of compound (3) to be used is not particularly limited, but from the viewpoint of obtaining compound (4) in good yield, 0 per mol of compound (2) .5 mol or more is preferable, and 5 mol or less is preferable from the viewpoint of suppressing side reactions and the load on the processing steps after the reaction.
Compound (3) is preferably 0.5 to 5 mol, more preferably 0.8 to 4 mol, even more preferably 1 to 3 mol, per 1 mol of compound (2).

A solvent may be used in the reaction between compound (2) and compound (3). The solvent is not particularly limited as long as it does not react with compound (3). Examples include aromatic solvents such as toluene and xylene; hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, diisopropyl ether, t-butylmethyl ether, tetrahydrofuran and dioxane. . These solvents may be used singly or in combination of two or more. The amount of solvent used can be set appropriately.

The reaction temperature between compound (2) and compound (3) may be the temperature for a normal cyclization reaction using compound (3). From the viewpoint of shortening the reaction time, the temperature is preferably −100° C. or higher, more preferably −80° C. or higher. In order to suppress problems such as side reactions, the temperature is preferably 100° C. or lower, more preferably 80° C. or lower.
Since the reaction time varies depending on the reaction temperature and the like, it may be determined appropriately. For example, about 0.5 to 30 hours is preferable.

Compound (4) obtained by the reaction of compound (2) and compound (3) may be purified.
Known purification methods such as alkaline water washing, water washing, distillation, crystallization, and filtration can be appropriately combined in consideration of the physical properties of the product, the type and amount of raw materials, the type of solvent, and the like.

Compound (5) is obtained by reacting compound (4) with (meth)acrylic acid chloride.
As the (meth)acrylic acid chloride, a commercially available product or a separately synthesized product may be used. The amount of (meth)acrylic acid chloride used is not particularly limited, but is preferably 0.5 mol or more per 1 mol of compound (4) from the viewpoint of obtaining compound (5) in good yield. From the viewpoint of preventing chloride-derived polymerization, the amount is preferably 4 mol or less.
The acrylic acid chloride is preferably 0.5 to 4 mol, more preferably 0.7 to 3 mol, even more preferably 0.9 to 2.5 mol, per 1 mol of compound (4).

In the reaction of compound (4) and (meth)acrylic acid chloride, a base may be added in order to obtain compound (5) in good yield. Examples of bases include n-butyllithium, s-butyllithium, t-butyllithium, methylmagnesium bromide, t-butylmagnesium chloride, triethylamine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0 ]-7-undecene and the like.
The amount of the base to be used is preferably 0.1 mol or more per 1 mol of compound (4) from the viewpoint of reaction yield, and is preferably 3 mol or less from the viewpoint of suppressing the load on the treatment process after the reaction.
The base is preferably 0.1 to 3 mol, more preferably 0.5 to 2 mol, per 1 mol of compound (4).

A solvent may be used in the reaction between compound (4) and (meth)acrylic acid chloride. The solvent is not particularly limited as long as it does not react with (meth)acrylic acid chloride. Examples include aromatic solvents such as toluene and xylene; hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, diisopropyl ether, t-butylmethyl ether, tetrahydrofuran and dioxane. . These solvents may be used singly or in combination of two or more. The amount of solvent used can be set appropriately.

A polymerization inhibitor may be present in the reaction system in order to suppress polymerization in the reaction between compound (4) and (meth)acrylic acid chloride. The polymerization inhibitor is not particularly limited, but includes hydroquinone monomethyl ether, hydroquinone, 4-hydroxy-2,2,6,6,-tetramethylpiperidine-N-oxyl, phenothiazine, copper salts and the like. These may be used alone or in combination of two or more.

The reaction temperature in the step of reacting compound (4) with (meth)acrylic acid chloride may be the temperature used in ordinary esterification. From the viewpoint of shortening the reaction time, the temperature is preferably −100° C. or higher, more preferably −80° C. or higher. Also, from the viewpoint of suppressing problems such as side reactions and polymerization, the temperature is preferably 65° C. or lower, more preferably 45° C. or lower.
Since the reaction time varies depending on the reaction temperature and the like, it may be determined appropriately. For example, about 0.5 to 20 hours is preferable.

It is preferable to purify the compound (5) obtained by the reaction of the compound (4) and (meth)acrylic acid chloride. The method for purifying compound (5) is a known purification method such as alkaline water washing, water washing, distillation, crystallization, filtration, etc., in consideration of the physical properties of the product, the raw material, the type and amount of the base, the type of solvent, etc. They can be combined as appropriate.

Preferred embodiments of the method for producing compound (5) include the following aspects (1) to (3). In the following, the methoxy group is sometimes referred to as "MeO-" and the ethoxy group as "EtO-".
Aspect (1): The following ester compound (2-1) is reacted with a compound (3-1) in which Y ¹ is a butylene group and M ² and M ³ are each MgBr in the formula (3), A method of obtaining the following hydroxy compound (4-1) and reacting the hydroxy compound (4-1) with (meth)acrylic acid chloride to obtain the following compound (5-1).
The compound (3-1) is a reaction product of 1,4-dibromobutane and metal Mg.

Embodiment (2): The compound (3-1) is reacted with the ester compound (2-2) below to obtain the hydroxy compound (4-2) below, and the hydroxy compound (4-2) and (meth) A method of obtaining the following compound (5-2) by reacting with acrylic acid chloride.

Aspect (3): The following ester compound (2-3) is reacted with the compound (3-1) to obtain the hydroxy compound (4-3), and the hydroxy compound (4-3) and (meth)acryl A method of obtaining the following compound (5-3) by reacting with an acid chloride.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Reaction tracking was performed by gas chromatography.
<Example 1>
A compound (5-1) was produced by the method of the aspect (1).
[Step 1]
2.54 g (63 mmol) of 60% by mass sodium hydride and 50 mL of tetrahydrofuran were added to a glass flask and cooled to 0°C. 5.00 g (42 mmol) of ethyl lactate dissolved in 28 mL of tetrahydrofuran was added and stirred at 0° C. for 20 minutes. 4.0 mL (63 mmol) of iodomethane was added, and the mixture was stirred at room temperature for 2.5 hours. 85 mL of a saturated ammonium chloride aqueous solution was added to separate the layers. The aqueous layer was extracted three times with 60 mL of diisopropyl ether, and the organic layer was washed with 20 mL of saturated brine. After drying with magnesium sulfate, the solvent was distilled off to obtain 2.97 g of compound (2-1).

[Step 2]
Next, 1.52 g (63 mmol) of magnesium shavings and 25 mL of tetrahydrofuran were added to a glass flask. dripped in time. Then, the mixture was stirred for 3 hours, cooled to −10° C., and 2.97 g (22 mmol) of compound (2-1) dissolved in 23 mL of tetrahydrofuran was added dropwise over 0.5 hour. After stirring at -10°C for 1 hour, the mixture was stirred at room temperature overnight. 50 mL of a 20% by mass ammonium chloride aqueous solution was added to separate the layers. The aqueous layer was extracted twice with 60 mL of ethyl acetate, and the organic layer was washed with 20 mL of a saturated sodium bicarbonate aqueous solution and then with 20 mL of saturated brine. After drying with magnesium sulfate, the solvent was distilled off to obtain 2.80 g of the desired compound.
¹ H-NMR analysis confirmed that the obtained compound was compound (4-1).
¹ H-NMR (270 MHz, CDCl ₃ ): δ 3.38 ppm (s, 3H), 3.23 ppm (q, 1H), 2.11 ppm (s, 1H), 1.84-1.51 ppm (m, 8H) , 1.15 ppm (d, 3H).

[Step 3]
2.80 g (19 mmol) of the compound (4-1) obtained above and 46 mL of tetrahydrofuran were added to a glass flask and cooled to -40°C under nitrogen flow. 20 mL of n-butyllithium (15% by mass hexane solution, 32 mmol) was added dropwise, and the mixture was stirred at 0° C. for 1 hour. After cooling to −40° C. again, 4.0 mL (42 mmol) of methacrylic acid chloride was added dropwise, followed by stirring at 0° C. for 1.5 hours. After adding 19.45 g of a 10% by mass lithium hydroxide aqueous solution and stirring at 50° C. for 2 hours, the liquids were separated. The aqueous layer was extracted with 20 mL of ethyl acetate three times, and the organic layer was washed with 30 mL of saturated aqueous sodium hydrogencarbonate solution and then with 15 mL of saturated brine. After drying with magnesium sulfate, the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 3.34 g of the desired compound.
¹ H-NMR analysis confirmed that the obtained compound was compound (5-1).
¹ H-NMR (270 MHz, CDCl ₃ ): δ 6.03 ppm (m, 1H), 5.50 ppm (m, 1H), 4.17 ppm (q, 1H), 3.36 ppm (s, 3H), 1.90 ppm (s, 1H), 2.14-1.56 ppm (m, 8H), 1.09 ppm (d, 3H).

<Example 2>
Example 2 is a reference example.
A compound (5-2) was produced by the method of the aspect (2).
Compound (2-2) was obtained in the same manner as in Step 1 of Example 1, except that ethyl lactate was changed to methyl 2-hydroxyisobutyrate.
Compound (4-2) was obtained in the same manner as in Step 2 of Example 1, except that compound (2-2) obtained above was used instead of compound (2-1). ¹ H-NMR analysis confirmed that the obtained compound was compound (4-2).
¹ H-NMR (270 MHz, CDCl ₃ ): δ 3.24 ppm (s, 3H), 2.36 ppm (s, 1H), 1.90-1.54 ppm (m, 8H), 1.17 ppm (s, 6H) .

The target compound was obtained in the same manner as in Example 1, Step 3, except that the compound (4-2) obtained above was used instead of the compound (4-1).
¹ H-NMR analysis confirmed that the obtained compound was compound (5-2).
¹ H-NMR (270 MHz, CDCl ₃ ): δ 6.00 ppm (m, 1H), 5.48 ppm (m, 1H), 3.25 ppm (s, 3H), 1.91 ppm (s, 1H), 2.06 -1.56 ppm (m, 8H), 1.24 ppm (d, 3H).

<Comparative Example 1>
Isopropylcyclopentyl methacrylate (compound described in paragraph 0245 of International Publication No. 2011/062168, structural formula is shown in Table 1) was used as a comparative compound.
Cyclopentanone (8.4 g) and tetrahydrofuran (200 mL) were added to a three-necked flask and cooled to 0°C. 166 mL of lanthanum trichloride bislithium chloride complex (0.6 mol/L tetrahydrofuran solution) was added dropwise at 0° C. and stirred for 30 minutes. Then, 100 mL of isopropylmagnesium bromide (1.0 mol/L tetrahydrofuran solution) was added dropwise at 0° C. and stirred for 2 hours. Subsequently, 100 mL of saturated aqueous ammonium chloride solution was added, the aqueous phase was extracted twice with 200 mL of ethyl acetate, the organic phases were combined, washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine, and the solvent was distilled off. The obtained crude product was purified by silica gel chromatography to obtain 11.4 g of 1-isopropylcyclopentanol (88% yield).
1-Isopropylcyclopentanol (11.4 g) was added to 200 mL of tetrahydrofuran and cooled to -40°C. 55 mL of normal butyllithium (1.6 mol/L hexane solution) was added dropwise at -40°C and stirred at 0°C for 1 hour. After cooling the reaction solution to −40° C. again, 8.4 g of methacryloyl chloride was added dropwise and the temperature was raised to room temperature. After stirring for 1 hour, the mixture was cooled to 0° C. and 100 mL of water was added. The aqueous phase was extracted twice with 200 mL of ethyl acetate, the organic phases were combined, washed with water and saturated brine, and the solvent was distilled off. The resulting crude product was purified by silica gel chromatography to give isopropylcyclopentyl methacrylate (12.3 g) (yield 86%).

<Comparative Example 2>
As a comparative compound, t-butylcyclopentyl methacrylate (the compound described in paragraph 0408 of JP-A-2015-141353, whose structural formula is shown in Table 1) was used.
In Comparative Example 1, t-butylcyclopentyl methacrylate was obtained in the same manner as in Comparative Example 1, except that t-butylmagnesium bromide was used instead of isopropylmagnesium bromide.

<Test Example 1: Evaluation of hydrophilicity>
Using the methacrylic acid esters obtained in the above Examples and Comparative Examples as samples, silica gel surface-treated with a hydrocarbon group having 18 carbon atoms was used as a column packing material, and reversed-phase liquid chromatography measurements were performed under the following conditions. .
[Measurement condition]
Apparatus: Liquid chromatography system ACQUITY UPLC H-Class (product name) manufactured by Waters.
Column: ACQUITY UPLC BEH C18 (product name) manufactured by Waters, 1.7 μm (particle size).
Mobile phase: acetonitrile/water = 3/1.
Flow rate: 0.5 mL/min.
UV detection wavelength: 220 nm.

According to the OECD Guidelines for the Testing of Chemicals, Section 1 (Test No. 117), in reversed-phase liquid chromatography using silica gel surface-treated with long-chain hydrocarbon groups (e.g., C8, C18) as a packing material, the sample does not migrate. The solvent of the phase migrates over the hydrocarbon silica gel (stationary phase). The sample is retained on the stationary phase by the partition coefficient between the stationary phase (hydrocarbon groups) and the mobile phase (water). Therefore, hydrophilic compounds are eluted earlier, and hydrophobic compounds are eluted later. That is, it can be determined that a sample with a shorter retention time is superior in hydrophilicity.
Table 1 shows the measurement results of the retention time.

As shown in the hydrophilicity evaluation results in Table 1, liquid chromatography using the compound obtained in Example 1 as a sample has a shorter retention time than the compound obtained in Comparative Example 1, and the hydrophilicity is improved. It was recognized that Similarly, liquid chromatography using the compound obtained in Example 2 as a sample showed that the retention time was shorter than that of the compound obtained in Comparative Example 2, and the hydrophilicity was improved.

The (meth)acrylic acid ester provided by the present invention has excellent hydrophilicity and is useful as a raw material for semiconductor resists to improve lithography properties. It is also useful for applications such as plastics and paints.

Claims (2)

A (meth)acrylic acid ester represented by the following formula (1).

[wherein R ¹ is a hydrogen atom or a methyl group, one of R ²¹ , R ²² and R ²³ is an alkoxy group having 1 to 20 carbon atoms, and the other one is a an alkyl group, the remaining one is a hydrogen atom, Z ¹ is a single bond , Z ³ is an atomic group forming a cyclopentyl group together with the carbon atom to which (R ²¹ R ²² R ²³ )C- is bonded, n is is 0 . ] A (meth)acrylic acid ester represented by the following formula (5) by reacting a hydroxy compound represented by the following formula (4) with a (meth)acrylic acid chloride to obtain a (meth)acrylic acid ester represented by the following formula (5) Production method.

[In formula (4), one of R ²¹ , R ²² and R ²³ is an alkoxy group having 1 to 20 carbon atoms, the other one is an alkyl group having 1 to 20 carbon atoms, and the remaining one is hydrogen The atom, Z ³ , is a group of atoms that, together with the carbon atom to which (R ²¹ R ²² R ²³ )C— is attached, forms a cyclopentyl group . ]

[wherein R ¹ is a hydrogen atom or a methyl group, one of R ²¹ , R ²² and R ²³ is an alkoxy group having 1 to 20 carbon atoms, and the other one is a an alkyl group, the remaining one is a hydrogen atom, and Z ³ is an atomic group forming a cyclopentyl group together with the carbon atom to which (R ²¹ R ²² R ²³ )C- is bonded. ]