KR100676812B1 - Process for preparing norbornene lactone ester compound - Google Patents

Abstract

A method for preparing a norbornene lactone ester compound is provided to obtain the highly pure norbornene lactone ester compound having improved physical properties with high yield by controlling the ratio of exo isomers. The method comprises the steps of: (a) performing a Diels-Alder reaction on a cyclopentadiene compound represented by the formula(2) with an acrylic acid represented by the formula(3) so as to prepare a norbornene carboxylic acid compound represented by the formula(4); (b) performing an esterification of the compound of the formula(4) with a halogenating lactone represented by the formula(5) or a hydroxy lactone compound in the presence of a base such as tertiary amine, sodium carbonate, and sodium hydrogen carbonate so as to prepare a norbornene lactone ester compound represented by the formula(1); and (c) recrystallizing the compound of the formula(1) with a polar solvent such as ethyl acetate and methyl tertiary butyl ether, and a non-polar solvent such as hexane, heptane and pentane so as to lower exo-isomer ratio thereof. In the formulae, R1 is H or C1-19 linear, branched or cyclic alkyl, n is an integer from 2 to 4, and X is hydroxy or halogen.

Description

Process for preparing norbornene lactone ester compound {PROCESS FOR PREPARING NORBORNENE LACTONE ESTER COMPOUND}

The present invention relates to a method for producing a norbornene lactone ester compound which is a main raw material of a photoresist composition used in fabricating a microcircuit of a highly integrated semiconductor device.

In the drive for the high integration and high speed of large scale integration (LSI) devices, the refinement of pattern rules is very important. This is because transparent lenses with excellent numerical aperture (NA) and fine short wavelength exposure light are required. With development, the development of photoresist compositions with high resolution and high sensitivity is very important.

As the shortening of the exposure light continues, the initial pattern of about 0.8 μm was formed using G-line (wavelength 436 nm) such as high-pressure mercury, and about 0.5 μm using I-ray (365 nm wavelength). The pattern formation at the level is possible, and the development of KrF laser exposure technology that emits deep UV of 248 nm wavelength enables not only the pattern formation below 0.15 μm but also the pattern formation below 0.1 μm recently. .

In addition, very large scale integration (VLSI) processes beyond Giga Dynamic Random Access Memory (DRAM) use ArF excimer laser (193 nm) technology to form sub-70 nm micropatterns that could not be obtained with KrF exposure. According to 's technology roadmap, the micro pattern technology of 20 nm or less is expected to be commercialized in 2015.

It is essential to secure the dry etching resistance of the photoresist at 193 nm wavelength of the ArF excimer laser for the micro pattern processing of 65 nm or less.A positive type photoresist for chemical amplification using an acrylic polymer mainly used in ArF excimer laser as a main material 4,491,628 and 5,310,619) had a disadvantage of low dry plasma etching resistance due to a large amount of oxygen atoms.

In order to solve this problem, studies have been conducted on polymer resins containing a large number of alicyclic olefin groups as photoresists for ArF or F2 excimer lasers, for example, isobornyl or adamantanyl groups. ) Acrylate polymers, olefin polymers composed of pure norbornene derivatives, maleic anhydride-cycloolefins, and acrylic and cycloaliphatic (typically cycloolefin) resins (Japanese Patent Publications 1997-73173, 1998-10739 and 1997-230595, and International Patent Publication No. 97/33198). Of these, norbornene lactone ester compounds and derivatives thereof have been spotlighted as photoresist monomers for ArF excimer lasers due to their excellent etch resistance and adhesion to silicon wafers, and thus the development of high purity norbornene lactone ester compounds having better physical properties Attention is increasing (see Japanese Patent Application Laid-Open No. 2002-35531, US Patent Publication Nos. 6291131-B1 and 64662158-B1, and European Patent No. 1162506A1).

Such norbornene ester compounds are generally prepared by preparing acrylic esters and then reacting them with cyclopentadiene derivatives (Diels-Alder) (Korean Patent Publication No. 2001-81853), but polymers and oligomers when preparing acrylic esters Is easy to be formed, and it is cumbersome to separate the intermediate acrylate in order to obtain a high purity norbornene compound, which is the final target compound, and does not provide a separation process for isomers essential for improving physical properties or a complicated separation process for this purpose. There was a problem to be performed (M. Bednarski, Tetrahetron Letter , 26 (21), 2507-2508, 1985).

Accordingly, it is an object of the present invention to provide a method for easily producing a high purity norbornene lactone ester compound having improved physical properties by controlling the proportion of isomers in high yield.

According to the above object, in the present invention 1) preparing a norbornene carboxylic acid compound of the general formula (4) by following the Diels-Alder reaction of the cyclopentadiene compound of formula (2) and acrylic acid of the general formula (3); 2) preparing a norbornene lactone ester compound of the following Chemical Formula 1 by esterifying the norbornene carboxylic acid compound obtained in step 1) with a halogenated lactone or a hydroxy lactone compound of the following Chemical Formula 5 in the presence of a base; And 3) lowering the exo-isomer ratio by recrystallizing the norbornene lactone ester compound obtained in step 2) with a polar solvent and a nonpolar solvent. It provides a method of making:

<Formula 1>

Wherein R ₁ is hydrogen or C _1-18 straight, branched or cyclic alkyl, n is an integer from 2 to 4 and X is hydroxy or halogen.

Hereinafter, the present invention will be described in detail.

Unlike the conventional method in which polymers or oligomers are likely to be produced by including an acrylic ester synthesis process, the method of the present invention performs a Diels-Alder reaction using cyclopentadiene and acrylic acid, thereby causing a relatively slow polymerization rate than that of acrylic. It is characterized in that a polymer or oligomer is hardly formed by preparing the nene carboxylic acid compound and then esterifying it. In addition, through the recrystallization process it is possible to effectively reduce the ratio of the exo isomer of the norbornene lactone ester compound to improve the physical properties and to be produced in high purity and high yield.

In step 1) of the present invention, as shown in Scheme 1, the norbornene carboxylic acid compound (a compound by performing a conventional Diels-Alder reaction using a cyclopentadiene compound (Compound 2) and acrylic acid (Compound 3) Compound 4) is prepared.

Wherein R ₁ and n are as defined above.

In this case, in order to increase the yield of the norbornene carboxylic acid compound, the cyclopentadiene compound may be used in 1 to 4 equivalents to 1 equivalent of acrylic acid. In addition, the Diels-Alder reaction of step 1) was carried out according to a conventional method (A. Wasserman, Diels-Alder Reactions , Elsevier, London, 1965), in the absence of a catalyst, dichloromethane, chloroform, tetrahydrofuran, etc. Of the polar solvent may be carried out at 0 to 80 ℃, preferably 30 to 70 ℃, wherein the polar solvent may be used in 1 to 20 times by weight compared to the weight of acrylic acid. In addition, the Diels-Alder reaction in the case of using a catalyst such as Lewis acid is preferably performed at -40 to 0 ° C, wherein the catalyst may be used in an amount of 0.1 to 1 equivalents to 1 equivalent of acrylic acid.

The reaction can obtain an intermediate norbornene carboxylic acid compound in a high yield, and due to the norbornene structure difficult to form radicals, there is an advantage that little polymer and oligomer are formed during the manufacturing process.

In addition, in step 2) of the present invention, as shown in Scheme 2, norbornene is obtained by reacting norbornene carboxylic acid compound (compound 4) and lactone compound (compound 5) obtained in step 1) in the presence of a base. Lactone ester compound (Compound 1) is prepared.

In which R ₁ and n are as defined above; X is hydroxy or halogen.

In this case, when X is halogen, it is preferable that it is chlorine, bromine or iodine, and such a lactone compound may be used in an amount of 0.5 to 4 equivalents based on 1 equivalent of the norbornene carboxylic acid compound. As the base, tertiary amines such as triethylamine or pyridine, sodium carbonate, sodium hydrogen carbonate, and the like, preferably tertiary amines may be used in an amount of 1 to 5 equivalents to 1 equivalent of norbornene carboxylic acid. The reaction of step 2) may be performed at 20 to 100 ° C., preferably 40 to 80 ° C., in an aprotic polar solvent such as ethyl acetate, methyl isobutyl ketone, dichloromethane and methyl t-butyl ether, wherein the solvent May be used in an amount of 1 to 10 times the weight of the norbornene carboxylic acid compound.

After the reaction of step 2), a purification process can be performed using an aqueous alkaline solution to remove residual norbornene carboxylic acid compounds. In this case, as the base used in the aqueous alkali solution, it is preferable to use an inorganic base such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate in an amount of 0.1 to 50% by weight based on the weight of the norbornene carboxylic acid compound, and the aqueous alkali solution is 0.5 to 10 Weight percent concentration is preferred.

In the preparation method of the present invention, a separation process may be performed every time the steps 1) and 2) are completed, but after performing the two steps in situ in consideration of the simplicity and high yield of the process. It is preferable to carry out the separation process.

In the separation process, a general vacuum distillation may be performed. In this case, since a reverse-Dies-Alder reaction may proceed at a high temperature, decomposition may occur, so it is preferable to use a thin film distillator.

In addition, the norbornene lactone ester compound of the present invention may be present as stereoisomers as two isomers of endo and exo, and the viscosity increases as the ratio of the exo isomer is used as a photosensitive agent. May be unsuitable for Therefore, in the present invention, in order to improve the physical properties of the norbornene lactone ester compound, the step of step 3) to lower the exo ratio by sequentially adding and crystallizing the norbornene lactone ester compound separated in the separation step in a polar solvent and a non-polar solvent Essentially included.

In this case, as the polar solvent used in step 3), ethyl acetate or methyl tert-butyl ether may be used in an amount of 0.1 to 1.0 weight times, preferably 0.15 to 0.8 weight times, based on the weight of the norbornene lactone ester compound. Hexane, heptane or pentane and the like can be used, where the weight ratio of nonpolar solvent to polar solvent can range from 1: 0.01 to 0.2, preferably 1: 0.03 to 0.14. The temperature of the crystallization process may range from -50 to 30 ℃, preferably 0 to 10 ℃, the process of step 3) due to the process of the present invention is 10 to 10 to the exo-isomer ratio of the desired norbornene lactone ester compound 20%, preferably 10% or less.

On the other hand, before performing the recrystallization process of step 3), the norbornene lactone ester compound obtained in step 2) is dissolved in an aprotic polar solvent and a non-polar solvent, and further performing a decolorization process using activated carbon and silica as an adsorbent. In this case, the aprotic polar solvent is ethyl acetate, methyl isobutyl ketone, dichloromethane and methyl t-butyl ether, and the nonpolar solvent is hexane, heptane and pentane. 1: 2 to 4, preferably 1: 1 to 2 may be used. In addition, activated carbon and silica may be used in 1 to 10% by weight and 0.5 to 10% by weight relative to the weight of the norbornene lactone ester compound, respectively.

Therefore, the manufacturing method of the present invention can produce a high purity norbornene lactone ester compound in a high yield while effectively lowering the ratio of the exo isomers and improving the physical properties, so that giga DRAM (dynamic) using ArF excimer laser (193 nm) technology It can be usefully used for a very large scale integration (VLSI) process or more.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

Example 1 Preparation of Norbornene Gamma-Butyrolactone Ester

Step 1) Preparation of Norbornene Carboxylic Acid

395 g (5.48 mol) of acrylic acid and 1200 g of dichloromethane were added to a 5 L three-necked flask, and 398 g (6.03 mol) of cyclopentadiene was slowly added thereto for 4 hours while maintaining the internal temperature at 25 ° C. Stirred. After confirming the completion of the reaction by gas chromatography, the reaction product was reduced pressure to remove dichloromethane to prepare 631 g (98% yield) of the target compound with a purity of 98%.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 12.02 (s, 1H), 6.07 (d, 2H), 3.23 (s, 1H), 2.99 (m, 2H), 1.91 (s, 1H), 1.52 to 1.39 (m, 2 H), 1.29 (s, 1 H).

Step 2) Preparation of norbornene gamma-butyrolactone ester

To 631 g (4.57 mole) of norbornene carboxylic acid obtained in step 1, 2000 g of ethyl acetate and 504.14 g (4.98 mole) of triethylamine were added, and the mixture was added with alpha- while maintaining the temperature of 45 ° C. 685 g (4.15 mol) of bromo-gamma-butyrolactone were slowly added, and then the temperature was gradually raised to react at 52 ° C. for 17 hours. The reaction product was filtered to remove salt, and the filtrate was extracted with 1000 g of 10% aqueous potassium carbonate solution. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was distilled at 160 ° C. and 100 mtorr conditions to obtain 900 g of norbornene gamma-butyrolactone ester having a purity of 99% (yield: 88%).

Step 2 ′) Decolorization Process of Norbornene Gamma-Butyrolactone Ester

750 g of ethyl acetate and 1500 g of hexane were added to 750 g of norbornene gamma-butyrolactone ester obtained in step 2, followed by addition of 75 g of activated carbon. The resulting reaction mixture was passed through a column filled with 600 g of silica to obtain a colorless liquid, which was concentrated to give 650 g of the desired white solid (yield 80.8%).

Step 3) Exobiation of Norbornene Gamma-Butyrolactone Ester

To 110 g of norbornene gamma-butyrolactone ester obtained in step 2) or 2 ′), 20, 40, 60 or 80 g of ethyl acetate was added and cooled to 10 ° C., respectively. Slowly added and stirred at room temperature for 4 hours. Thereafter, the produced solid was filtered through a glass filter, washed with hexane, and dried in a vacuum oven to obtain 90.1 g (yield 81.9%) of the title compound. The obtained samples were named E2H55, E4H55, E6H55 and E8H55, respectively, and the ratio of endo and exo isomers of each sample was confirmed through an area ratio of 5.3 to 5.5 ppm of ¹ H-NMR. At this time, the position of specific hydrogen NMR was found in 5.3 to 5.4 ppm for endo and 5.45 ppm for exo.

E2H55 (endo 85%, exo 15%); ¹ H-NMR (CDCl ₃ , 500 MHz): δ 6.22 (m, H), 6.16 (q, H), 6.11 (q, H), 6.05 (m, H), 6.91 (m, H), 5.45 ( m, H), 5.39 (t, H), 5.34 (t, H), 4.47 (m, H), 4.30 (m, H), 3.26 (d, H), 3.08 (m, H), 2.93 (s , H), 2.66 (m, H), 2.27 (m, H), 1.94 (m, H), 1.44 (m, H), 1.30 (t, H).

E4H55 (endo 86%, exo 14%); ¹ H-NMR (CDCl ₃ , 500 MHz): δ 6.22 (m, H), 6.16 (q, H), 6.11 (q, H), 6.05 (m, H), 6.91 (m, H), 5.45 ( m, H), 5.39 (t, H), 5.34 (t, H), 4.47 (m, H), 4.30 (m, H), 3.26 (d, H), 3.08 (m, H), 2.93 (s , H), 2.66 (m, H), 2.27 (m, H), 1.94 (m, H), 1.44 (m, H), 1.30 (t, H).

E6H55 (endo 87%, exo 13%); ¹ H-NMR (CDCl ₃ , 500 MHz): δ 6.22 (m, H), 6.16 (q, H), 6.11 (q, H), 6.05 (m, H), 6.91 (m, H), 5.45 ( m, H), 5.39 (t, H), 5.34 (t, H), 4.47 (m, H), 4.30 (m, H), 3.26 (d, H), 3.08 (m, H), 2.93 (s , H), 2.66 (m, H), 2.27 (m, H), 1.94 (m, H), 1.44 (m, H), 1.30 (t, H).

E8H55 (endo 88%, exo 12%); ¹ H-NMR (CDCl ₃ , 500 MHz): δ 6.22 (m, H), 6.16 (q, H), 6.11 (q, H), 6.05 (m, H), 6.91 (m, H), 5.45 ( m, H), 5.39 (t, H), 5.34 (t, H), 4.47 (m, H), 4.30 (m, H), 3.26 (d, H), 3.08 (m, H), 2.93 (s , H), 2.66 (m, H), 2.27 (m, H), 1.94 (m, H), 1.44 (m, H), 1.30 (t, H).

Comparative Example 1: Preparation of Norbornene Gamma-Butyrolactone Ester

Except for using 110 g of ethyl acetate and 220 g of hexane in step 3), the same process as in Example 1 was carried out to obtain 500 g of the target compound (yield 49.3%). The resulting solid was confirmed by NMR analysis has a ratio of 50% endo isomer and 50% exo isomer.

50% endo, 50% exo; ¹ H-NMR (CDCl ₃ , 500 MHz): δ 6.22 (m, H), 6.16 (q, H), 6.11 (q, H), 6.05 (m, H), 6.91 (m, H), 5.45 ( m, H), 5.39 (t, H), 5.34 (t, H), 4.47 (m, H), 4.30 (m, H), 3.26 (d, H), 3.08 (m, H), 2.93 (s , H), 2.66 (m, H), 2.27 (m, H), 1.94 (m, H), 1.44 (m, H), 1.30 (t, H).

As described above, the production method of the present invention has almost no polymer or oligomer formed during the manufacturing process due to the norbornene structure, which is difficult to form radicals, and improves physical properties by effectively reducing the ratio of the high purity norbornene lactone ester compound with exo isomers. Since it can be manufactured in high yield, Giga using ArF excimer laser (193 nm) technology can be usefully used for a very large scale integration (VLSI) process or the like beyond dynamic random access memory (DRAM).

Claims (11)

1) preparing a norbornene carboxylic acid compound represented by the following Chemical Formula 4 by diels-alder reacting the cyclopentadiene compound represented by Formula 2 with acrylic acid represented by Formula 3; 2) preparing a norbornene lactone ester compound of the following Chemical Formula 1 by esterifying the norbornene carboxylic acid compound obtained in step 1) with a halogenated lactone or a hydroxy lactone compound of the following Chemical Formula 5 in the presence of a base; And 3) preparing a norbornene lactone ester compound of Formula 1, comprising the step of recrystallizing the norbornene lactone ester compound obtained in step 2) with a polar solvent and a nonpolar solvent to lower the exo-isomer ratio Way: <Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

Wherein R ₁ is hydrogen or C _1-18 straight, branched or cyclic alkyl, n is an integer from 2 to 4 and X is hydroxy or halogen. The method of claim 1, Wherein the base in step 2) is selected from tertiary amines including triethylamine and pyridine, sodium carbonate, and sodium hydrogen carbonate. The method of claim 1, Performing steps 1) and 2) in an in situ reaction, followed by separation of the product before step 3). The method of claim 3, wherein And wherein the separation process is vacuum distillation using a thin film still. The method of claim 1, The polar solvent of step 3) is ethyl acetate or methyl tert-butyl ether. The method of claim 1, Characterized in that the nonpolar solvent of step 3) is hexane, heptane or pentane. The method of claim 1, Non-polar solvent: polar solvent in step 3), characterized in that the weight ratio ranges from 1: 0.01 to 0.2. The method of claim 1, The process of step 3) is carried out at -50 to 30 ℃. The method of claim 1, Before the process of step 3), further comprising the step of decolorizing the norbornene lactone ester compound using an adsorbent. The method of claim 9, Wherein the adsorbent is activated carbon and silica. The method of claim 10, Activated carbon and silica are used in an amount of 1 to 10% by weight and 0.5 to 10% by weight based on the weight of the norbornene lactone ester compound, respectively.