JPWO2008081768A1 - Chloromethyl ethers containing alicyclic structure, polymerizable monomer for photoresist and method for producing the same - Google Patents

Abstract

Photoresist for photoresists with improved roughness in resists having an alkyladamantyl group or a lactone structure, comprising alicyclic structure-containing (meth) acrylic acid esters represented by the following general formula (II) It is the composition for photoresists containing the polymer which has. (Wherein R1 is a functional group having at least one ester group or keto group having an alicyclic structure having 4 to 9 carbon atoms, and R2 is a hydrogen atom, a methyl group or a trifluoromethyl group.)

Description

  The present invention relates to a photosensitive material for a photoresist, and more particularly, to an alicyclic structure-containing chloromethyl ether, a polymerizable monomer for a photoresist having improved roughness, and a method for producing the same.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, miniaturization has rapidly progressed due to advances in lithography technology. As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, conventionally, ultraviolet rays typified by g-line and i-line were used, but now KrF excimer laser (248 nm) is the center of mass production, and ArF excimer laser (193 nm) is mass-produced. It has begun to be introduced. Research is also being conducted on lithography technology using F ₂ excimer laser (157 nm), EUV (extreme ultraviolet light), EB (electron beam) or the like as a light source (radiation source).

It has been proposed to use a polymer obtained by polymerizing a polymerizable compound having an alicyclic skeleton such as 2-methyl-2-adamantyl methacrylate as a resist for manufacturing an ArF semiconductor (for example, see Patent Document 1).
In this case, in order to improve dry etching resistance, a compound having a highly hydrophobic functional group such as an adamantyl group is used, but this deteriorates the solubility in a developer.
In addition, as miniaturization progresses, development of a resist having high adhesion to a silicon substrate is desired.

Against the background as described above, a resist composition containing a monomer having a lactone structure as a constituent unit has also been developed, and a lactone-containing monomer has become an indispensable constituent unit of a resist (for example, Patent Document 2). 3).
However, with the miniaturization of semiconductor manufacturing technology, further improvement in roughness has been cited as a major issue. In Patent Document 1, an alkyladamantyl group is used as an acid leaving group. However, when such an alicyclic block is removed, roughness (unevenness generated during formation of a resist pattern) is poor.
On the other hand, in Patent Documents 2 and 3, a resist having a lactone structure is used. However, since the lactone structure is not a detached block, the effect of improving the roughness cannot be expected.

Japanese Patent Laid-Open No. 4-39665 JP 2006-219677 A JP 2006-317553 A

  An object of the present invention is to provide a photosensitive material for a photoresist having improved roughness in a resist having an alkyladamantyl group or a lactone structure.

  As a result of intensive studies to achieve the above object, the present inventors react alicyclic chloromethyl ethers having at least one selected from an ester group and a keto group with (meth) acrylic acids. It has been found that a photosensitive material for a photoresist having improved roughness can be obtained by using the alicyclic (meth) acrylic acid esters obtained in this way. The present invention has been completed based on such knowledge.

That is, the present invention provides the following alicyclic compounds, polymers, compositions and production methods.
1. An alicyclic structure-containing chloromethyl ether represented by the following general formula (I):

（式中、Ｒ¹は炭素数４〜９の脂環式基であってエステル基及びケト基から選ばれる少なくとも一つを有する基である。）

(In the formula, R ¹ is an alicyclic group having 4 to 9 carbon atoms and a group having at least one selected from an ester group and a keto group.)

  2. An alicyclic structure-containing (meth) acrylic acid ester represented by the following general formula (II):

（式中、Ｒ¹は炭素数４〜９の脂環式基あってエステル基及びケト基から選ばれる少なくとも一つを有する基、Ｒ²は水素原子，メチル基又はトリフルオロメチル基である。）

(In the formula, R ¹ is an alicyclic group having 4 to 9 carbon atoms and has at least one selected from an ester group and a keto group, and R ² is a hydrogen atom, a methyl group or a trifluoromethyl group. )

3. An alicyclic structure-containing (meth) acrylic acid ester polymer comprising the alicyclic structure-containing (meth) acrylic acid ester of 2 as a constituent component.
4). 3. A photoresist composition comprising the alicyclic structure-containing (meth) acrylic acid ester polymer described in 3 above.
5). The alicyclic structure-containing (meth) acrylic acid ester according to the above 2, characterized by reacting the alicyclic structure-containing chloromethyl ether according to the above 1 with a (meth) acrylic acid represented by the following general formula (III) Manufacturing method.

（式中、Ｒ²は水素原子，メチル基又はトリフルオロメチル基である。）

(In the formula, R ² is a hydrogen atom, a methyl group or a trifluoromethyl group.)

  In the alicyclic structure-containing (meth) acrylic acid ester polymer of the present invention, a polar block such as a lactone structure or a ketone group has an acid decomposability, so that it becomes a leaving block, and the roughness is improved. Therefore, it can be advantageously used as a photosensitive material for a photoresist that has been miniaturized.

  The alicyclic structure-containing (meth) acrylic acid esters (II) of the present invention are prepared by reacting alicyclic structure-containing chloromethyl ethers (I) with (meth) acrylic acids (III) according to the following reaction formula: Manufactured by.

In the above reaction formula, R ¹ is an alicyclic group having 4 to 9 carbon atoms and a group having at least one selected from an ester group and a keto group, R ² is a hydrogen atom, a methyl group or a trifluoromethyl group. is there.
Specific examples of alicyclic structure-containing chloromethyl ethers (I) include α-chloromethoxy-γ-butyrolactone, α-chloromethoxy-β-methyl-γ-butyrolactone, α-chloromethoxy-β, β-dimethyl. -γ-butyrolactone, β-chloromethoxy-γ-butyrolactone, 3-chloromethoxy-2,6-norbornanecarbolactone, 5-chloromethoxy-2,6- (7-oxanorbornane) carbolactone, 2-chloromethoxycyclo Pentan-1-one, 2-chloromethoxycyclohexane-1-one, 3-chloromethoxycyclopentan-1-one, 3-chloromethoxycyclohexane-1-one, 3,5,5-trimethyl-2-chloromethoxycyclohexane 4-oxa-8-chloromethoxy-tricyclo [5,2,1,0 ^2,6 ] -5-one and the like.

The alicyclic structure-containing chloromethyl ethers (I) are reacted with formaldehyde, paraformaldehyde, hydrogen chloride gas or hydrogen bromide gas on the alicyclic structure-containing alcohol represented by the following general formula (IV). Can be manufactured.
R ¹ OH (IV)
(R ¹ is an alicyclic group having 4 to 9 carbon atoms and a group having at least one selected from an ester group and a keto group.)

When the alicyclic structure-containing chloromethyl ethers (I) are produced by the above method, an organic solvent having a water solubility of 5% by mass or less in the organic solvent used at the reaction temperature is preferably used. Specific examples include hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether and dibutyl ether, and halogen solvents such as dichloromethane and carbon tetrachloride.
The reaction temperature is usually −200 to 200 ° C., preferably −50 to 100 ° C. The reaction pressure is an absolute pressure and is usually 0.01 to 10 MPa, preferably normal pressure to 1 MPa. By setting the pressure to 0.01 MPa or more, it is possible to avoid a decrease in the solubility of hydrogen chloride gas in the solvent and increase the reaction time. By setting the pressure to 10 MPa or less, a high-pressure apparatus can be used. This is economically advantageous because it is unnecessary.
After the reaction, the reaction product liquid can be separated into water produced by the reaction and an organic layer, whereby unreacted formaldehyde can be removed as an aqueous layer. By removing the solvent from the organic layer, preferably under reduced pressure, the alicyclic structure-containing chloromethyl ether represented by the general formula (I) can be obtained. It may be subjected to the next reaction for producing the class (II), or may be subjected to the next reaction after purification such as distillation or recrystallization, if necessary.

Specific examples of alicyclic structure-containing (meth) acrylic acid esters (II) include α-acryloyloxymethoxy-γ-butyrolactone, α-methacryloyloxymethoxy-γ-butyrolactone, α- (2-trifluoromethylacryloyl) ) Oxymethoxy-γ-butyrolactone, α-acryloyloxymethoxy-β-methyl-γ-butyrolactone, α-methacryloyloxymethoxy-β-methyl-γ-butyrolactone, α- (2-trifluoromethylacryloyl) oxymethoxy-β -Methyl-γ-butyrolactone, α-acryloyloxymethoxy-β, β-dimethyl-γ-butyrolactone, α-methacryloyloxymethoxy-β, β-dimethyl-γ-butyrolactone, α- (2-trifluoromethylacryloyl) oxy Methoxy-β, β-dimethyl-γ-butyrolactone, β-acryloyloxymethoxy-γ-butyrolactone β-methacryloyloxymethoxy-γ-butyrolactone, β- (2-trifluoromethylacryloyl) oxymethoxy-γ-butyrolactone, 5-acryloyloxymethoxy-2,6-norbornanecarbolactone, 5-methacryloyloxymethoxy-2,6 -Norbornanecarbolactone, 5- (2-trifluoromethylacryloyl) oxymethoxy-2,6-norbornanecarbolactone, 5-acryloyloxymethoxy-2,6- (7-oxanorbornane) carbolactone, 5-methacryloyloxymethoxy -2,6- (7-oxanorbornane) carbolactone, 5- (2-trifluoromethylacryloyl) oxymethoxy-2,6- (7-oxanorbornane) carbolactone, 2-acryloyloxymethoxycyclopentane-1- ON, 2-methacryloyloxymethoxycyclopentan-1-one, 2- (2-tri Fluoromethylacryloyl) oxymethoxycyclopentan-1-one, 2-acryloyloxymethoxycyclohexane-1-one, 2-methacryloyloxymethoxycyclohexane-1-one, 2- (2-trifluoromethylacryloyl) oxymethoxycyclohexane- 1-one, 3-acryloyloxymethoxycyclopentan-1-one, 3-methacryloyloxymethoxycyclopentan-1-one, 3- (2-trifluoromethylacryloyl) oxymethoxycyclopentan-1-one, 3-acryloyl Oxymethoxycyclohexane-1-one, 3-methacryloyloxymethoxycyclohexane-1-one, 3- (2-trifluoromethylacryloyl) oxymethoxycyclohexane-1-one, 3,5,5-trimethyl-2-acryloyloxymethoxy Cyclohexane, 3,5,5-trimethyl-2-methacryl Yl oxy methoxy cyclohexane, 3,5,5-trimethyl-2- (2-trifluoromethyl acryloyl) oxy methoxy cyclohexane, 4- oxa-8- (acryloyl) oxy methoxy - tricyclo [5,2,1,0 ^{2, 6} ] -5-one, 4-oxa-8- (methacryloyl) oxymethoxy-tricyclo [5,2,1,0 ^2,6 ] -5-one, 4-oxa-8- (2-trifluoromethylacryloyl) ) Oxymethoxy-tricyclo [5,2,1,0 ^2,6 ] -5-one.

As described above, the alicyclic structure-containing (meth) acrylic acid esters (II) are produced by reacting the alicyclic structure-containing chloromethyl ethers (I) with the (meth) acrylic acids (III). .
It is preferable to use a solvent for this reaction. Examples of the solvent include hydrocarbon solvents such as hexane, heptane and octane, aromatic solvents such as benzene, toluene and xylene, and ether solvents such as diethyl ether, diisopropyl ether and tetrahydrofuran. Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, γ-butyrolactone, acetone, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, etc. it can.
The reaction temperature is usually −200 to 200 ° C., preferably −50 to 100 ° C. The reaction pressure is 0.01 to 10 MPa in absolute pressure, preferably normal pressure. By setting the pressure to 10 MPa or less, a high-pressure device is unnecessary, which is economically advantageous. The (meth) acrylic acid (III) is usually used in an amount of 0.8 to 5 times mol, preferably 1.0 to 2.0 times mol for the alicyclic structure-containing chloromethyl ethers (I).

The reaction for producing the alicyclic structure-containing (meth) acrylic acid esters (II) is preferably performed in the presence of a basic substance. Examples of basic substances include trimethylamine, triethylamine, tributylamine, trioctylamine, pyridine, lithium carbonate, potassium carbonate, sodium carbonate and the like. The usage-amount of a basic substance is 1-5 times mole normally with respect to (meth) acrylic acid (III), Preferably it is 1-2 times mole.
After completion of the reaction, washing is performed with a basic aqueous solution for the purpose of removing excess (meth) acrylic acid (III). Here, a general basic compound can be used as the basic compound, and among them, an inorganic basic substance is preferable. Specifically, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium phosphate, sodium hydroxide, water A potassium oxide etc. can be mentioned. Although organic bases such as trimethylamine, triethylamine, tributylamine, trioctylamine and pyridine can be used, they are more likely to remain in the product than inorganic bases.
The number of washings is performed until the (meth) acrylic acid (III) remaining in the product is 10000 ppm or less, preferably 2000 ppm or less. Then, after performing a general post-treatment operation, the alicyclic structure-containing (meth) acrylic acid esters (II) can be obtained by distilling off the solvent preferably under reduced pressure. This can be used as a product as it is, or purification such as distillation or crystallization may be performed depending on the properties of the substance and the type of impurities.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The physical property data of the alicyclic structure-containing chloromethyl ethers (I) and the alicyclic structure-containing (meth) acrylic acid esters (II) obtained in each Example were obtained using the following measuring apparatus.
(1) Gas chromatograph-mass spectrometry (GC-MS):
Measuring method: Electron ionization (EI) method Measuring device: GCMS-QP2010 manufactured by Shimadzu Corporation
(2) Nuclear magnetic resonance spectroscopy (NMR):
Measuring device: JNM-ECA500 manufactured by JEOL Ltd.
Solvent: chloroform-d

Example 1 [Synthesis of β-chloromethoxy-γ-butyrolactone (V)]
In a 300 mL three-necked flask equipped with a stirrer, a thermometer, and a nozzle for introducing hydrogen chloride gas, 10 g of β-hydroxy-γ-butyrolactone [molecular weight: 102.09, 98 mmol], 3.82 g of paraformaldehyde [molecular weight: 300.03, 127 mmol], 11.8 g of magnesium sulfate [molecular weight: 120.37, 98 mmol] and 200 mL of dichloromethane were added and stirred while maintaining the temperature at 0 ° C. Hydrogen chloride gas generated by mixing 250 g of sodium chloride and 150 mL of concentrated sulfuric acid was blown into the dichloromethane solution through a nozzle for 60 minutes.
After further stirring for 4 hours, the reaction mixture was subjected to gas chromatographic analysis (GC) and gas chromatograph-mass spectrometry (GC-MS). As a result, β-hydroxy-γ-butyrolactone was completely converted, and the selectivity was 96%. It was confirmed that β-chloromethoxy-γ-butyrolactone (V) was obtained. Magnesium sulfate was removed from the reaction solution by filtration, and the filtrate was directly used in the next reaction (Example 2).

(Physical property data)
Gas chromatograph-mass spectrometry (GC-MS): 152 (M ⁺ ( ³⁷ Cl), 0.27%), 150 (M ⁺ ( ³⁵ Cl), 0.74%), 122 (8.10%), 115 (3.27%), 92 (100%), 85 (26.35%), 57 (40.17%)

Example 2 [Synthesis of β-methacryloyloxymethoxy-γ-butyrolactone (VI)]
Into a 1 L four-necked flask equipped with a stirrer, thermometer and dropping funnel was placed 10.97 g [molecular weight: 86.09, 127.4 mmol], 250 mL of ethyl acetate and 15 mg of paramethoxyphenol as a polymerization inhibitor. Cooled to 0 ° C. in an ice bath. To this was added dropwise 19.83 g [molecular weight 101.19, 196 mmol] of triethylamine using a dropping funnel.
Subsequently, a dichloromethane solution of the compound (V) obtained in Example 1 was carefully added dropwise so that the internal temperature of the reaction solution did not exceed 5 ° C. Two hours after the completion of the dropwise addition, the reaction solution was sampled, and disappearance of the compound (V) was confirmed by GC analysis. After adding 100 mL of water to the reactor to stop the reaction, the reaction solution was transferred to a 1 L separatory funnel.
Thereafter, the organic layer was washed in the order of a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and then the organic layer was separated. After drying over anhydrous magnesium sulfate, the magnesium sulfate was filtered and the solvent was distilled off. The following β-methacryloyloxymethoxy-γ-butyrolactone (VI) [molecular weight: 200.19, yield 17.0 g, isolated yield 86. 8%, GC purity 96.7%].

(Physical property data)
Nuclear magnetic resonance spectroscopy (NMR):
¹ H-NMR: 1.97 (t, 3H), 2.61-2.81 (m, 3H), 4.34-4.47 (m, 2H), 4.60-4.65 (m, 1H), 5.37-5.45 (m, 2H), 5.69 (m, 1H), 6.18 (d, 1H)
¹³ C-NMR: 174.71, 166.54, 135.61, 127.06, 87.93, 74.94, 73.18, 35.29, 18.10
Gas chromatograph-mass spectrometry (GC-MS): 199 (M ⁺ -1,0.03%), 170 (1.12%), 115 (18.66%), 100 (9.06%), 85 ( 84.08%), 69 (100%), 57 (16.10%), 41 (45.51%)

Example 3 [Synthesis of 5-chloromethoxy-2,6-norbornanecarbolactone (VII)]
200 g of 5-hydroxy-2,6-norbornanecarbolactone [molecular weight: 154.16, 1.297 mol], paraformaldehyde 50 was added to a 2 L three-necked flask equipped with a stirrer, thermometer and nozzle for introducing hydrogen chloride gas. .64 g [molecular weight: 30.03, 1.687 mol], magnesium sulfate 156.1 g [molecular weight: 120.37, 1.297 mmol] and dichloromethane 1300 mL were added and stirred while maintaining the temperature at 0 ° C. Hydrogen chloride gas generated by mixing 1070 g of sodium chloride and 900 mL of concentrated sulfuric acid was blown into the dichloromethane solution through a nozzle for 5 hours.
After further stirring for 3 hours, the reaction solution was subjected to GC-MS analysis. As a result, 5-hydroxy-2,6-norbornanecarbolactone was completely converted and the selectivity was 96%, and the following 5-chloromethoxy-2,6 -It was confirmed that norbornanecarbolactone (VII) was obtained. After removing magnesium sulfate from the reaction solution by filtration, the filtrate was directly used in the next reaction (Example 4).

(Physical property data)
Gas chromatograph-mass spectrometry (GC-MS): 204 (M ⁺ ( ³⁷ Cl), 1.83%), 202 (M ⁺ ( ³⁵ Cl), 5.39%), 174 (9.29%), 167 (4.01%), 144 (15.11%), 138 (25.31%), 119 (13.04%), 105 (100%), 80 (60.96%), 66 (44.62) %), 55 (16.02%)

Example 4
[Synthesis of 5-methacryloyloxymethoxy-2,6-norbornanecarbolactone (VIII)]
In a 5 L four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 145.2 g [molecular weight: 86.09, 1.687 mol], ethyl acetate 1.3 L, and paramethoxyphenol 320 mg as a polymerization inhibitor And cooled to 0 ° C. with an ice bath. 262.6g [Molecular weight: 101.19, 2.595mol] of triethylamine was dripped here using the dropping funnel. Subsequently, a dichloromethane solution of compound (VII) obtained by the method of Example 3 was carefully added dropwise so that the internal temperature of the reaction solution did not exceed 5 ° C. Two hours after the completion of the dropwise addition, the reaction solution was sampled, and the disappearance of compound (VII) was confirmed by GC analysis. 500 mL of water was added to the reactor to stop the reaction, and the reaction solution was transferred to a separatory funnel. Thereafter, the organic layer was washed in the order of a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and then the organic layer was separated. After drying over anhydrous magnesium sulfate, the magnesium sulfate was filtered and the solvent was distilled off. The following crude 5-methacryloyloxymethoxy-2,6-norbornanecarbolactone (VIII) [molecular weight: 252.26, yield 317.0 g, Rate 96.9%] was obtained as a solid. This was recrystallized with a mixed solvent of ethyl acetate / hexane to give the product 5-methacryloyloxymethoxy-2,6-norbornanecarbolactone (VIII) [yield 180.3 g, isolated yield 55.1%, GC purity 99 .6%].

(Physical property data)
Nuclear magnetic resonance spectroscopy (NMR):
¹ H-NMR: 1.56-1.69 (m, 2H), 1.96 (d, 3H), 1.98-2.10 (m, 2H), 2.50-2.58 (m, 2H), 3.16 (m, 1H), 3.66 (s, 1H), 4.54 (d, 1H), 5.39 (dd, 2H), 5.66 (t, 1H), 6. 18 (s, 1H)
¹³ C-NMR: 18.24, 31.69, 34.06, 38.27, 41.71, 44.91, 84.47, 85.28, 87.94, 126.83, 135.87, 166 51, 180.00
Gas chromatograph-mass spectrometry (GC-MS): 252 (M ⁺ , 0.01%), 222 (14.30%), 194 (7.37%), 167 (2.99%), 153 (14. 94%), 137 (6.29%), 93 (19.61%), 81 (37.88%), 69 (100%), 41 (39.07%)

Example 5
[Synthesis of 5-chloromethoxy-2,6- (7-oxanorbornane) carbolactone (IX)]
Instead of 200 g of 5-hydroxy-2,6-norbornanecarbolactone [molecular weight: 154.16, 1.297 mol], 202.5 g of 5-hydroxy-2,6- (7-oxanorbornane) carbolactone [molecular weight: 156 .14, 1.297 mol] was used in the same manner as in Example 3. After completion of the reaction, magnesium sulfate was removed from the reaction solution by filtration, and then used for the next reaction (Example 6).

（物性データ）
ガスクロマトグラフ−質量分析（ＧＣ−ＭＳ）：２０６(Ｍ⁺(³⁷Ｃｌ)，１．７１％)，２０４(Ｍ⁺(³⁵Ｃｌ)，５．１４％)，１７６(１．５２％)，１６９(６．７８％)，１６０(２．５５％)，１４７(３．０３％)，１３９(２６．２６％)，１３８(１２．７９％)，１３１(１４．４８％)，１２３(３３．５５％)，１２１(１００％)，１１０(２３．４９％)，１０８(２６．３１％)，８４(４０．５０％)，８１(６２．８１％)，６９(３８．２６％)，５５(８０．５２％)，４１(５１．０５％)

(Physical property data)
Gas chromatograph-mass spectrometry (GC-MS): 206 (M ⁺ ( ³⁷ Cl), 1.71%), 204 (M ⁺ ( ³⁵ Cl), 5.14%), 176 (1.52%), 169 (6.78%), 160 (2.55%), 147 (3.03%), 139 (26.26%), 138 (12.79%), 131 (14.48%), 123 (33 .55%), 121 (100%), 110 (23.49%), 108 (26.31%), 84 (40.50%), 81 (62.81%), 69 (38.26%) 55 (80.52%), 41 (51.05%)

Example 6
[Synthesis of 5-methacryloyloxymethoxy-2,6- (7-oxanorbornane) carbolactone (X)]
The reaction is carried out in the same manner as in Example 4 except that the dichloromethane solution of compound (IX) obtained by the method of Example 5 is used instead of the dichloromethane solution of compound (VII) obtained by the method of Example 3. 5-methacryloyloxymethoxy-2,6- (7-oxanorbornane) carbolactone (X) [molecular weight: 254.24, yield 201.2 g, isolated yield 61.0%, GC purity 98.5% ]

(Physical property data)
Nuclear magnetic resonance spectroscopy (NMR):
¹ H-NMR: 1.97 (3H), 1.98 (1H), 2.24 (1H), 2.72 (1H), 3.90 (1H), 4.69 (1H), 4.73 (1H), 5.34 (1H), 5.44 (2H), 5.68 (1H), 6.19 (1H)
¹³ C-NMR: 18.2, 33.6, 38.9, 80.6, 80.7, 83.6, 84.0, 87.9, 127.1, 135.7, 166.4, 176 .5
Gas chromatograph-mass spectrometry (GC-MS): 236 (M ⁺ -18, 0.04%), 224 (2.35%), 196 (3.12%), 178 (3.06%), 169 ( 2.56%), 155 (1.39%), 150 (12.56%), 140 (2.69%), 139 (5.68%), 99 (4.52%), 95 (6. 38%), 83 (6.02%), 69 (100%), 41 (34.84%)

Example 7
[Synthesis of β-acryloyloxymethoxy-γ-butyrolactone (XI)]
The reaction was performed in the same manner as in Example 2 except that 9.18 g of acrylic acid [molecular weight: 72.06, 127.4 mmol] was used instead of 10.97 g of methacrylic acid. The target β-acryloyloxymethoxy-γ-butyrolactone (XI) [molecular weight: 186.16, yield: 15.5 g, isolated yield: 85.0%, GC purity: 95.7%] was obtained.

(Physical property data)
Nuclear magnetic resonance spectroscopy (NMR):
¹ H-NMR: 2.58-2.80 (m, 2H), 4.34-4.47 (m, 2H), 4.60-4.65 (m, 1H), 5.36-5. 47 (m, 2H), 5.96 (d, 1H), 6.21 (dd, 1H), 6.59 (d, 1H)
¹³ C-NMR: 35.5, 73.3, 76.4, 87.5, 128.2, 131.3, 166.1, 174.8

Example 8
[Synthesis of 5-acryloyloxymethoxy-2,6-norbornanecarbolactone (XII)]
The reaction was performed in the same manner as in Example 4 except that 121.6 g [1.687 mol] of acrylic acid was used instead of 145.2 g of methacrylic acid. The desired 5-acryloyloxymethoxy-2,6-norbornanecarbolactone (XII) [molecular weight: 238.24, yield 174.9 g, isolated yield 56.6%, GC purity 99.0%] was obtained. .

(Physical property data)
Nuclear magnetic resonance spectroscopy (NMR):
¹ H-NMR: 1.56-1.69 (m, 2H), 2.00-2.10 (m, 2H), 2.52-2.60 (m, 2H), 3.16 (m, 1H), 3.69 (s, 1H), 4.55 (d, 1H), 5.37 (dd, 2H), 5.90 (d, 1H), 6.10 (dd, 1H), 6. 66 (dd, 1H)
¹³ C-NMR: 31.7, 34.0, 38.2, 41.8, 44.9, 84.3, 85.2, 87.4, 129.5, 130.9, 165.3, 180 .1

Example 9
[Synthesis of 5-acryloyloxymethoxy-2,6- (7-oxanorbornane) carbolactone (XIII)]
The reaction was performed in the same manner as in Example 6 except that 121.6 g [1.687 mol] of acrylic acid was used instead of 145.2 g of methacrylic acid. Objective 5-acryloyloxymethoxy-2,6- (7-oxanorbornane) carbolactone (XIII) [Molecular weight: 240.21, yield 178.2 g, isolated yield 57.2%, GC purity 98.0% ]was gotten.

(Physical property data)
Nuclear magnetic resonance spectroscopy (NMR):
¹ H-NMR: 1.98 (1H), 2.24 (1H), 2.72 (1H), 3.90 (1H), 4.69 (1H), 4.73 (1H), 5.34 (1H), 5.42 (2H), 5.91 (1H), 6.14 (1H), 6.65 (1H)
¹³ C-NMR: 33.6, 39.0, 80.4, 80.7, 83.6, 84.6, 87.6, 126.2, 134.9, 165.3, 178.3

(Synthesis of copolymer)
Copolymer P1
The following monomer A was charged as 39.13 g as a detachable monomer, and 14.29 g of the following monomer C as a non-detachable monomer, and 1 L of methyl isobutyl ketone was added to prepare a solution. 1.7 mol% of 2,2′-azobis (isobutyric acid) dimethyl was added thereto as a polymerization initiator, and heated at 82 ° C. for about 2 hours. Thereafter, the reaction solution was purified by pouring it into a mixed solvent of a large amount of methanol and water three times for precipitation. As a result, a copolymer P1 having a copolymer composition (molar ratio) of monomer A: monomer C = 42: 58, a weight average molecular weight (Mw) of about 5540, and a molecular weight distribution (Mw / Mn) of 1.41 was obtained. . The results are shown in Table 1.

Copolymers P2 to P5
Using the monomers shown in Table 1, copolymers P2 to P5 were synthesized in the same manner as copolymer P1. Further, Table 1 shows the copolymer composition ratio (molar ratio), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the copolymers P2 to P5.
The weight average molecular weight (Mw) was measured by a gel permeation chromatograph (GPC) method. For measurement of GPC, GPC columns TSKgel G4000HXL and TSKgel G2000HXL (both manufactured by Tosoh Corporation) were connected in series, and the temperature was 40 ° C., solvent tetrahydrofuran, flow rate 1.0 ml / min. The conditions were as follows. Molecular weight distribution was calculated | required from ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained from the measurement of GPC.
Monomers A to G are as follows.

Examples 11-13 and Comparative Examples 1-2
Examples 11 to 13 and Comparative Examples 1 and 2 were performed as follows using the copolymers P1 to P5 synthesized by the above method, respectively.
7 parts by weight of the copolymer shown in Table 2, 0.175 parts by weight of triphenylsulfonium nonafluorobutane sulfonate as a photoacid generator, 0.021 parts by weight of triethanolamine as a quencher, and a solvent As a mixture, 92.8 parts by mass of propylene glycol monomethyl ether acetate was prepared to prepare resist compositions R1 to R5 shown in Table 2, respectively.
An organic antireflection film DUV44-6 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a 65 nm antireflection film. The resist composition prepared as described above was applied thereon, and baked at 115 ° C. for 60 seconds to form a 150 nm resist film to obtain a wafer.
The wafer thus obtained was subjected to several points of open exposure with light having a wavelength of 248 nm at different exposure amounts. Immediately after the exposure, the wafer was heated at 115 ° C. for 90 seconds, and then developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 120 seconds. Among these, the half-exposed part was cut out and the surface roughness (Ra) was measured using an atomic force microscope (Auto Probe M5 manufactured by Thermo Micro Scope). At this time, the smaller the value of Ra, the smaller the roughness (unevenness). The measurement results are shown in Table 2.

  It is clear that the resist composition prepared using the copolymer containing the monomer of the present invention in the examples has a smaller surface roughness (Ra) after development than the comparative examples. This shows that the monomer of the present invention has a high effect of improving roughness.

Claims (5)

An alicyclic structure-containing chloromethyl ether represented by the following general formula (I):

(In the formula, R ¹ is an alicyclic group having 4 to 9 carbon atoms and a group having at least one selected from an ester group and a keto group.) An alicyclic structure-containing (meth) acrylic acid ester represented by the following general formula (II):

(In the formula, R ¹ is an alicyclic group having 4 to 9 carbon atoms and has at least one selected from an ester group and a keto group, and R ² is a hydrogen atom, a methyl group or a trifluoromethyl group. )   An alicyclic structure-containing (meth) acrylic acid ester polymer comprising the alicyclic structure-containing (meth) acrylic acid ester according to claim 2 as a constituent component.   A composition for a photoresist comprising the alicyclic structure-containing (meth) acrylic acid ester polymer according to claim 3. The alicyclic structure-containing chloromethyl ether according to claim 1 is reacted with (meth) acrylic acid represented by the following general formula (III): Method for producing (meth) acrylic acid esters.

(In the formula, R ² is a hydrogen atom, a methyl group or a trifluoromethyl group.)