JP2002145827A - Alicyclic tertiary (meth) acrylate compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern-forming material suitable in lithography using active rays such as ultraviolet rays, far-ultraviolet rays, electron beams, ion beams or X-rays regarding the photolithographic step in a semiconductor manufacturing process. SOLUTION: This pattern-forming material is a compound of the general formula 1. The other objective method for producing the compound of the general formula 1 comprises a reaction between an exo-8-alkyl-endo-8- hydroxytricyclo[5.2.1.02,6] decane or exo-8-alkyl-endo-8- hydroxytricyclo[5.2.1.02,6]dec-3(4)-ene of the general formula 2 and an acrylic halide derivative of the general formula 3 in the presence of a base (in the general formulas 1, 2 and 3, R1 is a 1-10C alkyl; R2 is H or a 1-4C alkyl; R3 and R4 are each H or a 1-10C alkyl; X is a halogen; and the broken line represents a signal or double bond).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound represented by the formula [1]:

[0002]

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(Wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ represent a hydrogen atom or Carbon number 1
10 represents an alkyl group, and a broken line represents a single bond or a double bond. Exo-8-alkyl-endo-8 represented by the formula:
-(Meth) acryloyloxytricyclo [5.2.
1.0 ^2,6 ] decane compound or exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,6 ] dec-3 (4) -ene compound And its manufacturing method.

The compound of the present invention relates to a photolithography step in a semiconductor manufacturing process, and relates to a monomer in the field of a pattern type material suitable for lithography using actinic rays such as ultraviolet rays, far ultraviolet rays, electron beams, ion beams and X-rays.

[0005]

2. Description of the Related Art As an alicyclic tertiary acryloyl ester compound, an exo-acryloyl norbornane compound (EP) is used.
There is a proposal of 10046868A2). The scheme is as follows.

[0006]

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(Where R ¹ is a hydrogen atom, methyl, CH ₂ C
Represents OR ^14, R ² is a hydrogen atom, methyl, CO ₂ COR ¹⁴
R ³ represents an alkyl group having 1 to 8 carbon atoms or 6 carbon atoms
Represents an allyl substituent having ２０20, and R ¹⁴ represents an alkyl group having 1 to 13 carbon atoms. That is, after an exo-methyl-endo-hydroxynorbornane compound is obtained by a Grignard reaction of an oxonorbornane compound, the compound is dehydrated with an acid catalyst to form a double bond, and then epoxidized with an organic peracid. Furthermore, this is hydrogenolyzed using a metal hydrogen complex compound to derive an endo-methyl-exo-hydroxynorbornane compound, and then reacted with an acrylic acid chloride compound to obtain an endo-alkyl-exo-acryloylnorbornane compound. I have. However, the acryloyl compound obtained by this production method requires five steps and many steps, and uses an expensive organic peracid or a metal hydride complex compound, and is a practically expensive compound.

[0008]

An object of the present invention relates to a photolithography step in a semiconductor manufacturing process, and relates to a pattern suitable for lithography using actinic rays such as ultraviolet rays, far ultraviolet rays, electron beams, ion beams and X-rays. Development of formal materials.

That is, in order to form a clear contrast and increase the resolution, a tertiary ester group, which is easy to hydrolyze an ester group of an acryloyl compound by an acid generated by exposure, is introduced. The challenge is to provide an acryloyl compound that can be synthesized in a short step in order to make the production process more efficient.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention.

That is, the compound of the present invention has the formula [1]

[0012]

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(Wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ represent a hydrogen atom or 1 carbon atom. Exo-8-alkyl-endo-8- which represents an alkyl group of 10 to 10 and a broken line represents a single bond or a double bond.
(Meth) acryloyloxytricyclo [5.2.1.
0 ^2,6 ] decane compound or exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,6 ] dec-3 (4) -ene compound. Equation [2]

[0014]

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(In the formula, R ¹ has the same meaning as described above.)
Exo-8-alkyl-endo-8-hydroxytricyclo [5.2.1.0 ^2,6 ] decane or exo-8-alkyl-endo-8-hydroxytricyclo [5. 2.1.0 ^2,6 ] dec-3 (4) -ene and formula [3]

[0016]

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(Wherein, R ² , R ³ and R ⁴ have the same meanings as described above, and X represents a halogen atom). The reaction is carried out in the presence of a base. Exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,6 ] decane represented by the formula [1], or exo-8-
The present invention relates to a method for producing an alkyl-endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,6 ] dec-3 (4) -ene compound.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,6 ] decane represented by the formula [1] of the present invention or exo-8-alkyl- A method for producing an endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,6 ] dec-3 (4) -ene compound is represented by the following reaction scheme.

[0019]

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(In the formula, R ¹ , R ² , R ³ , R ⁴ and X have the same meanings as described above.) First, as the OTCD as a raw material in the first step, tricyclo [5.2.1.0 ^2,6 ] decane-8-one (TCD
O) or tricyclo [5.2.1.0 ^2,6 ] dec-3
(4) -en-8-one (TCDE) can be used.

As TCDO, a commercially available product can be used as it is. TCDE can be synthesized by the following synthesis method.

[0022]

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That is, dicyclopentadiene (DCPD)
Is epoxidized with an oxidizing agent, and then TC
DE3 (tricyclo [5.2.1.0 ^2,6 ] dec-3-
En-8-one) and TCDE4 (tricyclo [5.
2.1.0 ^2,6 ] dec-4-en-8-one).

As the alkyl magnesium halide, a commercially available product can be used as it is. Further, it can be produced from metal magnesium and an alkyl halide. Examples of the type of alkyl halide include linear or branched carbon atoms having 1 carbon atom.
Compounds produced by combining an alkyl group of 10 to 10 with a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be applied.

Specifically, for example, methyl magnesium chloride, ethyl magnesium chloride, n-propyl magnesium chloride, i-propyl magnesium chloride, n-butyl magnesium chloride, i-
Butylmagnesium chloride, s-butylmagnesium chloride, n-pentylmagnesium chloride,
n-hexyl magnesium chloride, n-heptyl magnesium chloride, n-octyl magnesium chloride, n-nonyl magnesium chloride, n-decyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-propyl magnesium bromide, i-propyl magnesium bromide, Examples include n-butyl magnesium bromide, methyl magnesium iodide, ethyl magnesium iodide, n-propyl magnesium iodide, i-propyl magnesium iodide, and n-butyl magnesium iodide.

The reaction requires a solvent, examples of which include tetrahydrofuran (THF), ether derivatives such as diethyl ether and dioxane, and hydrocarbon derivatives such as hexane, heptane and toluene. The amount used is preferably 1 to 20 times by weight, particularly 2 to 10 times by weight, based on the starting ketone.

[0027] The reaction temperature is preferably from -20 to 120 ° C, and particularly from 0 to 80 ° C gives a high yield. The reaction time is completed in 1 to 10 hours.

The obtained reaction mixture is extracted with water and an organic solvent, and then the organic layer is concentrated to obtain the desired exo-8-.
Alkyl-endo-8-hydroxytricyclo [5.
2.1.0 ^2,6 ] decane (AHDA) or exo-8
-Alkyl-endo-8-hydroxytricyclo [5.2.1.0 ^2,6 ] dec-3 (4) -ene (AHD
E) is obtained.

Next, the second step will be described. The product of the first step, AHDA or AHDE, can be used as it is or after purification. On the other hand, the acrylic halide compound represented by the general formula [3] is obtained by converting the above acrylic acid compound into an acid halide with thionyl halide or the like.
Halogen includes F, Cl, Br and I, but the cheapest Cl is used. Specifically, acryloyl chloride, methacryloyl chloride, tiglyloyl chloride, 3,3-dimethylacryloyl chloride, 2-methyl-2-pentenoyl chloride,
2-ethyl-2-hexenoyl chloride and 2-octeroyl chloride. The amount used is A
1.0 to 3.0 equivalents are preferable to HDA or AHDE.

In this reaction, a base is indispensable, and the kind thereof is a chain alkylamine compound represented by trimethylamine, triethylamine and tripropylamine, and an aromatic represented by pyridine, aniline and N-methylaniline. Amine compounds, 1,5-diazabicyclo [4,3,0] no-5-ene (DBN), 1,4-diazabicyclo [2,2,2] octane (DBO) and 1,
Cyclic alkylamine compounds represented by 8-diazabicyclo [5,4,0] undec-7-ene (DBU) and the like;
Metal carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate are exemplified. Preferred among these bases are triethylamine and sodium carbonate. AHDA or A
1.0 to 3.0 equivalents (equivalent to acid chloride) based on HDE are preferred.

The process preferably employs a solvent. Examples of the solvent include ether compounds such as tetrahydrofuran (THF), 1,2-dimethoxyethane, dioxane, and 2-methoxyethyl ether, N, N-dimethylformamide (DMF), and N, N-dimethylacetamide (DM
Ac), N-methylpyrrolidone and 1,3-dimethyl-
2-imidazolidinone (DMI) and the like are preferred. The amount used is preferably 1 to 10 times by weight, particularly preferably 2 to 5 times by weight, based on AHDA or AHDE.

The reaction temperature ranges from 0 to 150 ° C., preferably from 0 to 1
00 ° C is preferred. After the reaction, water is added to hydrolyze the residual acid chloride, the solvent is distilled off, and the residue is extracted with a poorly water-soluble solvent (aromatic hydrocarbon type, ether type or ester type), and then distilled or columnized. The desired product can be obtained by purification by chromatography. The above-described reaction and purification of the present invention can be performed in a batch system or a continuous system.

[0033]

EXAMPLES The present invention will be described in detail with reference to Reference Examples and Examples, but the present invention is not limited thereto. Reference Example 1

[0034]

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In a 50 ml four-necked reactor, 8.0 g (22 mmol) of a 3M-methylmagnesium chloride THF solution was added.
l) and tricyclo [5.2.1.0] at 5 ° C.
^2,6 ] decane-8-one (TCDO) 3.0 g (20 m
mol) was removed over 30 minutes. When the mixture was stirred at 25 ° C. for 1 hour, crystals were deposited, the degree of slurry was increased, and the stirring became worse. 15 g of THF was added, and the mixture was further stirred for 2 hours. After the reaction solution was cooled to 5 ° C., a solution of 1.32 g of ammonium sulfate dissolved in 10 g of water was added dropwise. The mixture was further concentrated, ethyl acetate and water were added to the residue, and the organic layer was washed with water and concentrated to dryness, whereby 3.32 g of crystals (20 mmol;
(100% yield).

The analysis results of this substance are shown below. MASS (FAB +, m / e (%)):. 166 (M +, 3), 149 (100) 1 H-NMR (CDCl 3, δppm): 0.819-0.923 (m, 2H), 1.03 (dd, J 1 =
_{3.05Hz, J 2 = 12.8Hz, 1H} ), 1.13-1.19 (m, 2H), 1.25 (d, J = 12.2
Hz, 3H), 1.32 (dd , J 1 = 1.83Hz, J 2 = 11.0Hz, 1H), 1.53-1.62
(m, 3H), 1.53-1.62 (m, 3H), 1.71 (s, 1H), 1.76-1.81 (m, 3H),
1.83 (s, 1H), 2.55 (dd, J 1 = 8.55Hz, J 2 = 17.1Hz, 1H) 13 C-NMR (CDCl 3, δppm):. 27.39,30.41,31.83,32.48,32.7
0,39.34,41.91,46.66,46.82,52.85,76.87,77.00,77.12. Mp. (° C): 66-67. From the above results, the compound was found to be exo-8-methyl-endo-8- (meth) acryloyl Oxytricyclo [5.
2.1.0 ^2,6 ] (HMTD).

Reference Example 2 76.0 g (150%) of a 33% methylmagnesium iodide / diethyl ether solution was placed in a 300 ml four-necked reactor.
mmol) and tricyclo [5.2.
1.0 ^2,6 ] decane-8-one (TCDO) 19.5 g
(130 mmol) was removed over 40 minutes. After stirring at 25 ° C., crystals started to precipitate, but the slurry was stirred for 5 hours. After cooling the reaction solution to 5 ° C., a solution of 1.32 g of ammonium sulfate dissolved in 20 g of water was added dropwise. Further concentrate, add ethyl acetate and water to the residue,
The organic layer was washed with water and concentrated to dryness, yielding 21.8 g of HMTD crystals
(Purity 96.8%: 127 mmol; yield 97.7%)
was gotten.

Reference Example 3 A 100 ml four-necked reactor was charged with 23.9 g (24 mmol) of a 12% methylmagnesium bromide THF solution and tricyclo [5.2.1.0 ^2,6 ] decane-8- at 5 ° C. 3.0 g (20 mmol) of ON (TCDO)
It was removed over 5 minutes. Stirred at 25 ° C. for 5 hours. The reaction was cooled to 5.degree.
g was dissolved in 10 g of water. Further concentrate,
Ethyl acetate and water were added to the residue, and the organic layer was washed with water and concentrated to dryness to obtain 3.23 g of HMTD crystals (purity: 82.8%:
16.1 mmol; yield 80.6%). still,
These crystals contained 11.1% of TCDO. Reference example 4

[0039]

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In a 50 ml four-necked reactor, 24.6 g (22 mmol) of a 13% ethyl magnesium bromide THF solution was added.
l) and tricyclo [5.2.1.0] at 5 ° C.
^2,6 ] decane-8-one (TCDO) 3.0 g (20 m
mol) was removed over 15 minutes. Stirred at 40 ° C. for a further 4 hours. After the reaction solution was cooled to 5 ° C., a solution of 1.32 g of ammonium sulfate dissolved in 10 g of water was added dropwise. After further concentration, ethyl acetate and water were added to the residue, and the organic layer was washed with water and concentrated to dryness to obtain 3.30 g of an oily substance. This was subjected to silica gel column chromatography (developing solution: heptane / ethyl acetate = 9/1). ). As a result, 2.54 g (14.1 mmol; yield: 7) of an oily substance was obtained.
0.6%). The oily substance solidified after standing at room temperature.

The analysis results of this substance are shown below. MASS (FAB +, m / e (%)):. 180 (M +, 4), 163 (100) 1 H-NMR (CDCl 3, δppm): 0.824-0.942 (m, 6H), 1.10-1.20 (m,
2H), 1.30 (dt, J 1 = 1.83Hz, J 2 = 10.0Hz, 1H), 1.38 (d, J = 6.11H
z, 1H), 1.49 (dd, J ₁ = 7.33Hz, J ₂ = 14.6Hz, 2H), 1.55 (dd, J ₁ =
_{4.58Hz, J 2 = 12.5Hz, 1H} ), 1.60 (dd, J 1 = 6.11Hz, J 2 = 12.2Hz, 1
H), 1.75-1.89 (m, 5H), 2.50 (dd, J ₁ = 8.55Hz, J ₂ = 17.1Hz, 1
^{. H) 13 C-NMR (} CDCl 3, δppm): 27.30,31.69,32.28,32.66,34.5
2,39.32,41.62,44.78,46.98,50.40,76.75,77.00,77.25,
79.33. Mp. (° C.): 36-37. From the above results, this compound was obtained using exo-8-ethyl-endo-8- (meth) acryloyloxytricyclo [5.
2.1.0 ^2,6 ] (HETD). Example 1

[0042]

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In a 50 ml four-necked reactor, exo-8-methyl-endo-8-hydroxytricyclo [5.2.
1.0 ^2,6 ] decane (HMTD) 1.66 g (10 mm
ol), 17 g of tetrahydrofuran (THF) and 3.03 g (30 mmol) of triethylamine.
And cooled to 3.12 g of methacryloyl chloride (3.
0 mmol) and 3.12 g of THF were added dropwise over 10 minutes. Thereafter, the temperature was raised to 40 ° C., and the mixture was stirred for 8 hours. After completion, 10 ml of water was added, and THF was distilled off. After adding 30 ml of toluene to the residue to extract the product, the residue was washed twice with 20 ml of water, and the organic layer was further concentrated. The obtained oil was purified by silica gel column chromatography (developing solution: heptane / ethyl acetate = 9/1). As a result, at room temperature, 2.14 g of an oily substance (9.12 mm
ol; yield: 91.2%). The analysis results of this substance are shown below. MASS (FAB +, m / e (%)): 234 (M +, 2), 219 (3), 191 (10), 176 (2
. 0), 149 (45) , 105 (52), 91 (82), 77 (100) 1 H-NMR (CDCl 3, δppm): 0.830-0.970 (m, 2H), 1.08-1.13 (m,
2H), 1.32 (d, J = 12.2Hz, 1H), 1.42 (dd, J 1 = 3.05Hz, J 2 = 13.4H
z, 1H), 1.45 (s, 3H), 1.53-1.59 (m, 1H), 1.64 (dd, J ₁ = 4.89H
z, J ₂ = 13.4Hz, 1H), 1.73-1.80 (m, 3H), 1.83 (d, J = 1.22Hz, 4
H), 2.13 (dd, J ₁ = 8.55Hz, J ₂ = 17.1Hz, 1H), 2.32 (s, 3H), 5.40
. (d, J = 1.22Hz, 1H), 5.94 (s, 1H) 13 C-NMR (CDCl 3, δppm): 17.35,24.57,26.22,30.23,30.7
1,31.51,38.91,39.71,44.04,45.73,50.46,85.64,123.3
2,136.54,165.76. Based on the above results, this compound was obtained as exo-8-methyl-endo-8- (meth) acryloyloxytricyclo [5.
2.1.0 ^2,6 ] decane (MMTD). Example 2

[0044]

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In a 50 ml four-necked reactor, exo-8-ethyl-endo-8-hydroxytricyclo [5.2.
1.0 ^2,6 ] decane (EHTD) 4.32 g (24 mm
ol), 15 g of tetrahydrofuran (THF) and 7.30 g (72 mmol) of triethylamine.
C. and cooled to 7.50 g of methacryloyl chloride (7.
A mixture of 2 mmol) and 7.50 g of THF was added dropwise in 20 minutes. Thereafter, the temperature was raised to 40 ° C., and the mixture was stirred for 6 hours. After completion, 20 ml of water was added, and THF was distilled off. After adding 30 ml of toluene to the residue to extract the product, the residue was washed twice with 20 ml of water, and the organic layer was further concentrated. The obtained oil was purified by silica gel column chromatography (developing solution: heptane / ethyl acetate = 9/1).

As a result, 4.63 g of an oily substance (1
8.6 mmol; yield 77.8%). The analysis results of this substance are shown below. MASS (FAB +, m / e (%)):. 248 (M +, 8), 163 (100), 74 (23) 1 H-NMR (CDCl 3, δppm): 0.728 (t, J = 7.63Hz, 3H ), 0.844-0.9
28 (m, 2H), 1.09-1.14 (m, 2H), 1.31-1.35 (m, 2H), 1.57 (dd, J
₁ = 6.11Hz, J ₂ = 12.22Hz, 1H), 1.65 (dd, J ₁ = 4.89Hz, J ₂ = 13.44
Hz, 1H), 1.71-1.81 (m, 4H), 1.84 (s, 4H), 2.05-2.15 (m, 2H),
2.40 (s, 1H), 5.41 (d, J = 1.83Hz, 1H), 5.96 (s, 1H) 13 C-NMR (CDCl 3, δppm):. 7.71,18.40,27.27,29.59,31.45,
31.70,32.62,40.16,40.68,43.10,46.91,49.74,89.94,12
4.36,137.32,166.63. From the above results, this compound was obtained using exo-8-ethyl-endo-8- (meth) acryloyloxytricyclo [5.
2.1.0 ^2,6 ] decane (EMTD).

[0047]

The alicyclic tertiary (meth) acrylate compound of the present invention is used in a photolithography step in a semiconductor manufacturing process, and the acid generated by exposure causes hydrolysis of the ester group of the acryloyl compound. It is a compound into which an easy tertiary ester is introduced. This makes it possible to form a clear contrast. In addition, the compound of the present invention can be produced from commercially available raw materials in a short process and in a high yield.

Claims (3)

[Claims] [Claim 1] Formula [1] (Wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms,
R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a broken line represents a single bond or a double bond. Exo-8-alkyl-endo-8- (meth) represented by
Acryloyloxytricyclo [5.2.1.0 ^2,6 ]
Decane compound or exo-8-alkyl-endo-8
-(Meth) acryloyloxytricyclo [5.2.
1.0 ^2,6 ] dec-3 (4) -ene compound. 2. Formula [2] (Wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms,
Dashed lines represent single or double bonds. Exo-8-alkyl-endo-8-hydroxytricyclo [5.2.1.0 ^2,6 ] decane or exo-8-alkyl-endo-8-hydroxytricyclo [5 .2.
1.0 ^2,6 ] dec-3 (4) -ene and formula [3] (Wherein, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁴ represent a hydrogen atom or 1 to 10 carbon atoms.
And X represents a halogen atom. (1) wherein the acrylic halide derivative represented by the formula (1) is reacted in the presence of a base. (Wherein, R ¹ , R ² , R ³ , R ⁴ and the dashed line have the same meanings as described above.) Exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5 .
2.1.0 ^2,6 ] decane compound or exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,6 ] dec-3 (4)- A method for producing an ene compound. 3. The exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5.] according to claim 2, wherein the base is an alkylamine, an aromatic amine or a metal carbonate. 2.1.0 ^2,6 ] decane compound or exo-8-alkyl-endo-8- (meth) acryloyloxytricyclo [5.2.1.0 ^2,
6 ] A method for producing a dec-3 (4) -ene compound.