JP2005170902A - New compound and radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound which has good solubility in a casting solvent for preparing a film, is stable in an alkali developer, and can be easily deprotected with acid under mild conditions, and to provide high-sensitivity and high-resolution patterning by using this compound. <P>SOLUTION: There is provided a new compound represented by formula (1). This new compound is blended with a radiation sensitive acid-generator to obtain a radiation-sensitive resin composition, wherein this new compound is used as an acid-dissociable group-containing resin which is originally alkali-insoluble or difficultly alkali-soluble and becomes easily alkali-soluble by the action of acid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a novel compound and a radiation-sensitive resin composition using the same, and in particular, far ultraviolet rays such as KrF excimer laser, ArF excimer laser (wavelength 193 nm) or F ₂ excimer laser (wavelength 157 nm), X such as synchrotron radiation. The present invention relates to a novel compound and a radiation-sensitive resin composition for forming a chemically amplified resist useful for microfabrication using various kinds of radiation such as charged particle beams such as beams and electron beams.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) or F ₂ excimer laser (wavelength 157 nm) are used. Lithography technology using a representative short wavelength radiation is widely used.
As a resist suitable for such excimer laser irradiation, an acid-dissociable group-containing resin that is insoluble in alkali or hardly soluble in alkali and easily soluble in alkali by the action of an acid, and a component that generates an acid upon irradiation with radiation. Resists utilizing the chemical amplification effect (hereinafter referred to as “chemically amplified resist”) have already been proposed.
In recent years, electron beam (EB) lithography is expected as a microfabrication technology that exceeds that limit. When a semiconductor device is directly manufactured by EB lithography, the EB resist to be used is particularly required to have dry etching resistance. To meet this demand, chemically stable aromatic compounds are used. However, since conventional resists are made of a high molecular weight and high molecular weight distribution, it has been difficult to further improve the resolution. This is because the main chain of the polymer itself is an obstacle to light, so that the light utilization efficiency is poor and the molecular mobility is poor. Therefore, development of a resist material having a rigid structure comparable to a polymer and heat resistance and a small molecular size is desired.
As one of chemically stable aromatic compound resist materials, an acid-dissociable group-containing resin using a calix resorcinarene derivative has been conventionally known (see Patent Document 1). Calix resorcinarene is a cyclic oligomer formed by the condensation of resorcin and paraformaldehyde. It is known that calixresorcinarenes and derivatives thereof have an inclusion function similar to crown ethers and cyclodextrins because of their unique structure in which a benzene ring is arranged along the frustoconical circumferential side.
However, when used as a chemically amplified resist material, it has excellent solubility in cast solvents during film production, and is stable under basic conditions and easily hydrolyzed under acidic conditions. There is a problem that there is no appropriate protecting group.
JP-A-11-322656

  The present invention has been made to cope with such problems, and is excellent in solubility in a casting solvent during film production, is stable to an alkaline developer, and is easily removed under mild conditions by an acid. It is an object of the present invention to provide a novel compound that can be protected and a radiation sensitive resin composition that can be expected to form a pattern with high sensitivity and high resolution by using this compound.

The novel compound of the present invention is represented by the following formula (1).

  The radiation-sensitive resin composition of the present invention contains an acid-dissociable group-containing resin that is insoluble or hardly soluble in alkali and easily soluble in alkali by the action of an acid, and a radiation-sensitive acid generator. The dissociable group-containing resin is a novel compound represented by the above formula (1).

In the present invention, a novel compound calixresorcinarene derivative having an acetal residue is obtained by chemical reaction under mild conditions. This novel compound exhibits high solubility in general organic solvents, undergoes thermal decomposition at around 300 ° C., and is excellent in heat resistance.
In addition, the radiation-sensitive resin composition using this novel compound as an acid-dissociable group-containing resin is stable in an alkali developer and can be easily deprotected under mild conditions by an acid generated by radiation irradiation. Become.

The novel compound represented by the formula (1) can be synthesized through the following three steps.
As a first step, calix [4] resorcinarenes having an ethyl ester residue are synthesized from calix [4] resorcinarenes.
The raw material calix [4] resorcinarenes can be synthesized by known methods. For example, C-methyl-calix [4] resorcinarene can be synthesized by the reaction of resorcinol and paraaldehyde, and C-4-hydroxyphenylcalix [4] resorcinarene can be synthesized by the reaction of resorcinol and parahydroxybenzaldehyde, respectively.
In addition, introduction of an ethyl ester residue into calix [4] resorcinarenes can be carried out, for example, by reaction with ethyl bromoacetate.

As the second step, calix (4) resorcinarene derivatives having a carboxyl group are synthesized by hydrolyzing the ethyl ester residue. Hydrolysis can be performed using, for example, an aqueous potassium hydroxide solution.
As a third step, the reaction between the carboxyl group of the calix (4) resorcinarene derivatives having a carboxyl group and chloromethyl methyl ether is allowed to react under mild conditions using, for example, triethylamine as a base. It is possible to synthesize calix (4) resorcinarene derivatives having

The obtained calixresorcinarene derivative can be used as an acid-dissociable group-containing resin.
In the calix resorcinarene derivative, an acetal group is eliminated by an acid catalyst to generate a carboxyl group, whereby the solubility in a predetermined solvent is greatly changed. For this reason, a radiation sensitive resin composition is obtained by including this compound and a radiation sensitive acid generator.
As the radiation-sensitive acid generator, any component that generates an acid upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray can be used, and consists of a mother nucleus and a generated acid.
As the mother nucleus, iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), onium salt compounds such as phosphonium salts, diazonium salts, pyridinium salts, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, disulfonyldiazomethane compounds , Disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.
Examples of the acid generated include alkyl or fluorinated alkyl sulfonic acid, alkyl or fluorinated alkyl carboxylic acid, alkyl or fluorinated alkyl sulfonylimide acid, and the like.
The radiation-sensitive resin composition includes (1) an acid diffusion control agent having an action of controlling an undesired chemical reaction in a non-exposed region by controlling a diffusion phenomenon of an acid generated from an acid generator upon exposure in a resist film, (2) Dry etching resistance, pattern shape, alicyclic additive containing / not containing acid-dissociable organic group, which has the effect of further improving the adhesion to the substrate, (3) coating properties, developability, etc. Surfactant showing the action of improving, (4) Sensitizer showing the action of improving sensitivity, etc. (5) Addition of additives such as antihalation agent, adhesion aid, storage stabilizer, antifoaming agent, etc. can do.

  The radiation-sensitive resin composition according to the present invention is useful as a positive chemically amplified resist material sensitive to, for example, KrF, ArF, electron beam, X-ray and the like. Since the calix resorcinarene derivative has a certain degree of molecular weight, it has film-forming properties, so that this derivative alone can be used as a substrate for a chemically amplified resist material. Alternatively, it may be used as a base of a chemically amplified resist material in combination with other film-forming resins. Since the calix resorcinarene derivative has a smaller molecular size than a linear resin or the like, a resist material containing this compound can form a high-resolution pattern, and so-called edge roughness is reduced in the formed pattern. Moreover, the solubility with respect to a solvent improves by having R. Further, since this resist material is a positive type, there is an advantage that adverse effects due to swelling can be suppressed.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. Here, the part is based on weight unless otherwise specified.
Each measurement and evaluation in Examples and Reference Examples was performed by the following apparatuses and methods.
Infrared spectrometer (IR): JASCO Corporation FT / IR-420, BIORAD Co., Ltd. RT / IR-ExcaliberFTS 300MX
Nuclear magnetic resonance measuring apparatus ( ¹ H NMR): ECA-500 500 MHz-NMR, JEOL Ltd.
Mass Spectrometer (MALDI--TOFMS): Shimadzu SHIMAZU / KRATOS Matrix Assisted Laser Ionization Time-of-Flight Mass Spectrometer KOMPACTMALDIIVtDE
Thermogravimetry measuring device (TG / DTA): Seiko Instruments Inc. Seiko Instruments EXTAR 6000TG-DTA6200 (measuring conditions: heating rate 10 ° C./min under nitrogen stream, open aluminum pan)
Photoreactor Ultra high pressure mercury lamp: USHIOUIS-25102
Illuminance meter: USHIOUIT-150 UV integrated light meter Centrifuge: KUBOTA2010

The reagents and solvents used in Examples and Reference Examples are as follows.
Tetrabutylammonium bromide (hereinafter abbreviated as TBAB) was recrystallized from dehydrated ethyl acetate. N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), dimethylformamide (hereinafter abbreviated as DMF), pyridine, triethylamine (hereinafter abbreviated as TEA), 1,8-diazabicyclo [5.4.0] Undeca-7-ene (hereinafter abbreviated as DBU) was preliminarily dried using calcium hydroxide and then purified by distillation in the presence of calcium hydroxide. Tetrahydrofuran (hereinafter abbreviated as THF) was preliminarily dried using anhydrous magnesium sulfate and purified by distillation in the presence of sodium. Resorcinol, paraaldehyde, parahydroxybenzaldehyde, cesium carbonate, potassium carbonate, bromoacetic acid, ethyl bromoacetate, n-butyl vinyl ether, 2,3-dihydroxyfuran, triphenylphosphine, succinic anhydride, chloromethyl methyl ether, citric acid, Commercially available products were used as they were for pyridinium p-toluenesulfonate, potassium hydroxide, and sodium hydroxide. As the photoacid generator bis [4- (diphenylsulfonio) phenyl] sulfide-bis (hexafluorophosphate) (hereinafter abbreviated as DPSP), a commercially available product was used as it was.

Reference example 1
C-methyl-calix [4] resorcinarene (hereinafter abbreviated as CRA-a) was synthesized by the following method.
Resorcinol 33.00 g (0.3 mol) and paraaldehyde 2.30 g (0.1 mol) were dissolved in 200 ml of a mixed solution of methanol: distilled water = 1: 1. The solution was cooled to 5 ° C. with stirring, and 15 ml of hydrochloric acid was slowly added dropwise. After the addition, the solution was refluxed for 45 minutes. After completion of the reaction, the reaction mixture was cooled to room temperature, the precipitated yellow solid was filtered off, washed with distilled water three times and methanol twice, and then the solid was dried under reduced pressure at room temperature for 24 hours to obtain a powdery white solid. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 1.

Reference example 2
C-4-Hydroxyphenylcalix [4] resorcinarene (hereinafter abbreviated as CRA-b) was synthesized by the following method.
The reaction of resorcinol 5.50 g (5.0 mmol) and parahydroxybenzaldehyde 6.14 g (5.0 mmol) was refluxed in 20 ml of methanol for 45 minutes in the same manner as in Reference Example 1 using 2 ml of hydrochloric acid. Was done. After completion of the reaction, the reaction mixture was cooled to room temperature, and the deposited light red solid was filtered off and washed thoroughly in the order of distilled water, methanol, and acetone. This was dried under reduced pressure at room temperature for 24 hours to obtain a powdery light red solid. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 2.

１００ミリリットル容器にＣＲＡ−ａを５．５０ｇ（１０ミリモル水酸基当量８０ミリモル）と炭酸カリウムを１６．５８ｇ（１２０ミリモル）とＴＢＡＢを０．３２ｇ（０．２５ミリモル）を量り取り、ＮＭＰを２５ミリリットル加え、室温で１２時間攪拌した。これにブロモ酢酸エチルを２０．０２ｇ（１２０ミリモル）を加え、窒素雰囲気下、７５℃で４８時間攪拌した。反応後、塩をろ過により除去し、酢酸エチルで希釈し、次に反応混合物を蒸留水で５回洗浄を行なった。酢酸エチル層を硫酸マグネシウムで乾燥した後、乾燥剤をろ別、酢酸エチルを減圧留去し、ｎ−ヘキサンを用いて再沈精製を２回行なった。析出した沈殿物を室温で２４時間減圧乾燥を行ない淡褐色固体を得た。構造確認はＩＲ、¹Ｈ ＮＭＲスペクトルおよび質量分析により行なった。結果を表３に示す。

表３に示すように、ＩＲスペクトルではフェノール性水酸基が完全に消失し、代わってエチルエステル部位のカルボニル基に基づく吸収が１７５０ｃｍ^-1に認められた。また、¹Ｈ ＮＭＲの結果から、エチルエステル基に帰因するピークが確認されている。さらに、積分値が計算値と一致したことから、得られた生成物は目的とするＣＲＡ−１ａであることが明らかになった。 Reference example 3
A CRA-a derivative having an ethyl ester residue (hereinafter abbreviated as CRA-1a) was synthesized by the following method. The reaction formula is represented by Formula (2).

In a 100 ml container, weigh out 5.50 g of CRA-a (10 mmol hydroxyl equivalent 80 mmol), 16.58 g (120 mmol) of potassium carbonate and 0.32 g (0.25 mmol) of TBAB, and 25 ml of NMP. In addition, the mixture was stirred at room temperature for 12 hours. To this was added 20.02 g (120 mmol) of ethyl bromoacetate, and the mixture was stirred at 75 ° C. for 48 hours under a nitrogen atmosphere. After the reaction, the salt was removed by filtration, diluted with ethyl acetate, and then the reaction mixture was washed 5 times with distilled water. After drying the ethyl acetate layer with magnesium sulfate, the desiccant was filtered off, the ethyl acetate was distilled off under reduced pressure, and reprecipitation purification was performed twice using n-hexane. The deposited precipitate was dried under reduced pressure at room temperature for 24 hours to obtain a light brown solid. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 3.

As shown in Table 3, in the IR spectrum, the phenolic hydroxyl group completely disappeared, and absorption based on the carbonyl group at the ethyl ester site was observed at 1750 cm ⁻¹ instead. Moreover, the peak attributed to the ethyl ester group is confirmed from the result of ¹ H NMR. Furthermore, since the integrated value agreed with the calculated value, it was revealed that the obtained product was the target CRA-1a.

１００ミリリットル容器にＣＲＡ−ｂを８．８２ｇ（１０ミリモル水酸基当量１２０ミリモル）と炭酸カリウムを２４．９０ｇ（１８０ミリモル）とＴＢＡＢを０．５４ｇ（０．３８ミリモル）を量り取り、ＮＭＰを２５ミリリットル加え、室温で１２時間攪拌した。これにブロモ酢酸エチルを３０．１２ｇ（１８０ミリモル）を加え、 窒素雰囲気下、７５℃で４８時間攪拌した。反応後、塩をろ過により除去し、酢酸エチルで希釈し、次に反応混合物を蒸留水で５回洗浄を行った。酢酸エチル層を硫酸マグネシウムで乾燥した後、乾燥剤をろ別、酢酸エチルを減圧留去し、ｎ−ヘキサンを用いて再沈精製を２回行つた。析出した沈殿物を室温で２４時間減圧乾燥を行ない淡褐色固体を得た。構造確認はＩＲ、¹Ｈ ＮＭＲスペクトルおよび質量分析により行なった。結果を表４に示す。

表４に示すように、ＩＲスペクトルではフェノール性水酸基が完全に消失し、代わってエチルエステル部位のカルボニル基に基づく吸収が１７５９ｃｍ^-1、１７３３ｃｍ^-1に認められた。また、¹Ｈ ＮＭＲの結果から、エチルエステル基に帰因するピークが確認されている。さらに、積分値が計算値と一致したことから、得られた生成物は目的とするＣＲＡ−１ｂであることが明らかになった。 Reference example 4
A CRA-b derivative having an ethyl ester residue (hereinafter abbreviated as CRA-1b) was synthesized by the following method. The reaction formula is represented by Formula (3).

In a 100 ml container, weigh 8.82 g of CRA-b (10 mmol hydroxyl group equivalent 120 mmol), 24.90 g (180 mmol) of potassium carbonate, 0.54 g (0.38 mmol) of TBAB, and 25 ml of NMP. In addition, the mixture was stirred at room temperature for 12 hours. To this was added 30.12 g (180 mmol) of ethyl bromoacetate, and the mixture was stirred at 75 ° C. for 48 hours under a nitrogen atmosphere. After the reaction, the salt was removed by filtration, diluted with ethyl acetate, and then the reaction mixture was washed 5 times with distilled water. After drying the ethyl acetate layer with magnesium sulfate, the desiccant was filtered off, the ethyl acetate was distilled off under reduced pressure, and reprecipitation purification was performed twice using n-hexane. The deposited precipitate was dried under reduced pressure at room temperature for 24 hours to obtain a light brown solid. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 4.

As shown in Table 4, in the IR spectrum, the phenolic hydroxyl group completely disappeared, and absorption based on the carbonyl group at the ethyl ester site was observed at 1759 cm ⁻¹ and 1733 cm ⁻¹ instead. Moreover, the peak attributed to the ethyl ester group is confirmed from the result of ¹ H NMR. Furthermore, since the integrated value agreed with the calculated value, it was revealed that the obtained product was the target CRA-1b.

１００ミリリットルナスフラスコにエチルエステル残基を有するＣＲＡ−１ａを１．２３ｇ（１．０ミリモル水酸基当量８．０ミリモル）、ＴＢＡＢを０．３２ｇ（０．３２モル)、ＫＯＨを０．７３ｇ（１２．０ミリモル）、さらに１０ミリリットルの蒸留水加え７０℃で６時間攪拌させた。反応終了後、溶液をクエン酸水溶液に滴下し、 室温で１時聞攪袢した。この混合物を遠心分離機により固層と液層に分け、得られた固体を５０ミリリットルの蒸留水でよく洗浄し、遠心分離機を用いて固体を回収した。得られた固体にＴＨＦ２５０ミリリットル加え、３時間攪拌し、沈殿物を桐山ロートで回収した。得られた個体を室温で２４時間減圧乾燥を行ない粉末白色固体を得た。構造確認はＩＲ、¹Ｈ ＮＭＲスペクトルおよび質量分析により行なった。結果を表５に示す。

ＩＲスペクトルではエチルエステル部位のカルボニル基に基づくＣ＝Ｏの吸収１７５０ｃｍ^-1が１６９０ｃｍ^-1にシフトしているためカルボキシル基が確認できる。また、ＭＡＬＤＩ−ＴＯＦＭＳの結果から、ピークが確認されていることから、得られた生成物は目的とするＣＲＡ−２ａであると認められる。 Reference Example 5
A CRA-a derivative having a carboxyl group (hereinafter abbreviated as CRA-2a) was synthesized by the following method. The reaction formula is represented by Formula (4).

In a 100 ml eggplant flask, CRA-1a having an ethyl ester residue 1.23 g (1.0 mmol hydroxyl equivalent 8.0 mmol), TBAB 0.32 g (0.32 mol), KOH 0.73 g (12 0.0 mmol) and further 10 ml of distilled water were added and stirred at 70 ° C. for 6 hours. After completion of the reaction, the solution was added dropwise to an aqueous citric acid solution and stirred at room temperature for 1 hour. This mixture was separated into a solid layer and a liquid layer by a centrifuge, and the obtained solid was thoroughly washed with 50 ml of distilled water, and the solid was recovered using a centrifuge. To the obtained solid, 250 ml of THF was added and stirred for 3 hours, and the precipitate was collected with a Kiriyama funnel. The obtained solid was dried under reduced pressure at room temperature for 24 hours to obtain a powder white solid. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 5.

In the IR spectrum, the carboxyl group can be confirmed because the absorption 1750 cm ^{−1 of} C═O based on the carbonyl group at the ethyl ester site is shifted to 1690 cm ⁻¹ . Moreover, since the peak is confirmed from the result of MALDI-TOFMS, it is recognized that the obtained product is the target CRA-2a.

１００ミリリットルナスフラスコにエチルエステル残基を有するＣＲＡ−１ｂを１．９２ｇ（１．０ミリモル水酸基当量１．２ミリモル）、ＴＢＡＢを０．５４ｇ（０．４８モル）、ＫＯＨを１．１１ｇ（１８ミリモル）、さらに１０ミリリットルの蒸留水加え７０℃で６時間撹拌させた。反応終了後、溶液をクエン酸水溶液に滴下し、室温で１時間攪拌した。この混合物を遠心分離機により固層と液層に分け、得られた固体を５０ミリリットルの蒸留水でよく洗浄し、遠心分離機を用いて固体を回収した。得られた固体にＴＨＥ２５０ミリリットル加え、３時間攪拌し、沈殿物を桐山ロートで回収した。得られた個体を室温で２４時間減圧乾燥を行ない粉末黄色固体を得た。構造確認はＩＲ、¹Ｈ ＮＭＲスペクトルおよび質量分析により行なった。結果を表６に示す。

ＩＲスペクトルではエチルエステル部位のカルボニル基に基づくＣ＝Ｏの吸収１７５９ｃｍ^-1、１７３３ｃｍ^-1が１７３０ｃｍ−１にシフトしているためカルボキシル基が確認できる。また、ＭＡＬＤＩ−ＴＯＦＭＳの結果から、ピークが確認されていることから、得られた生成物は目的とするＣＲＡ−２ａ，２ｂであることが認められる。 Reference Example 6
A CRA-b derivative having a carboxyl group (hereinafter abbreviated as CRA-2b) was synthesized by the following method. The reaction formula is represented by Formula (5).

In a 100 ml eggplant flask, 1.92 g (1.0 mmol hydroxyl equivalent 1.2 mmol) of CRA-1b having an ethyl ester residue, 0.54 g (0.48 mol) of TBAB, 1.11 g of KOH (18 Mmol) and 10 ml of distilled water were further added and stirred at 70 ° C. for 6 hours. After completion of the reaction, the solution was added dropwise to an aqueous citric acid solution and stirred at room temperature for 1 hour. This mixture was separated into a solid layer and a liquid layer by a centrifuge, and the obtained solid was thoroughly washed with 50 ml of distilled water, and the solid was recovered using a centrifuge. 250 ml of THE was added to the obtained solid and stirred for 3 hours, and the precipitate was collected with a Kiriyama funnel. The obtained solid was dried under reduced pressure at room temperature for 24 hours to obtain a powdery yellow solid. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 6.

Carboxyl group can be confirmed because the C = absorption of O 1759cm ^-1 based on the carbonyl group of an ethyl ester moiety in the IR spectrum, is 1733 cm ^-1 shifted to 1730 cm-1. Moreover, since the peak is confirmed from the result of MALDI-TOFMS, it is recognized that the obtained product is the target CRA-2a and 2b.

２５ミリリットル容器にＣＲＡ−２ａを２．５２ｇ（２５ミリモル水酸基当量２００ミリモル）とトリエチルアミンを４．０１ｇ（４００ミリモル）を量り取り、ＤＭＦを２０ミリリットル加え、回転子を入れ、室温で１時間攪拌した。これにクロロメチルメチルエーテルを２．３９ｇ（３００ミリモル）を加え、窒素雰囲気下、室温で２時間攪袢した。反応後、塩をろ過により除去し、酢酸エチルで希釈し、反応混合物を蒸留水で５回洗浄した。次に、酢酸エチル層を硫酸マグネシウムで乾燥した。乾燥剤をろ過後、減圧留去し、析出した固体を室温で２４時間減圧乾燥した。その結果、生成物として粉末状の白色固体を得た。構造確認はＩＲ、¹Ｈ ＮＭＲスペクトルおよび質量分析により行なった。結果を表７および図１に示す。

ＩＲスペクトルでは、カルボキシル基のＯＨのピークが完全に消失し、Ｃ＝Ｏのピークが１６９０ｃｍ^-1から１７６３ｃｍ^-1にシフトし、さらに、アセタール基に起因するピークが９２９ｃｍ^-1に確認された。また、¹Ｈ ＮＭＲの結果から、アセタール基に帰因するピークが現れ、さらに、積分値が計算値と一致した。これらの結果から、得られた生成物は目的とするＣＲＡ−３ａであることが確認された。 Example 1
A CRA-a derivative (hereinafter abbreviated as CRA-3a) having an acetal residue of a novel compound was synthesized by the following method. The reaction formula is represented by Formula (6).

In a 25 ml vessel, 2.52 g of CRA-2a (25 mmol hydroxyl group equivalent: 200 mmol) and 4.01 g (400 mmol) of triethylamine were weighed, 20 ml of DMF was added, a rotor was added, and the mixture was stirred at room temperature for 1 hour. . To this was added 2.39 g (300 mmol) of chloromethyl methyl ether, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. After the reaction, the salt was removed by filtration, diluted with ethyl acetate, and the reaction mixture was washed 5 times with distilled water. Next, the ethyl acetate layer was dried over magnesium sulfate. The desiccant was filtered and then distilled off under reduced pressure, and the precipitated solid was dried under reduced pressure at room temperature for 24 hours. As a result, a powdery white solid was obtained as a product. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 7 and FIG.

The IR spectra were peak completely disappeared in OH of the carboxyl group, the peak of C = O is shifted from 1690 cm ^-1 to 1763cm ^-1, further, a peak attributed to the acetal group was observed at 929 cm ^-1. Further, from the result of ¹ H NMR, a peak attributed to the acetal group appeared, and the integrated value coincided with the calculated value. From these results, it was confirmed that the obtained product was the target CRA-3a.

２５ミリリットル容器にＣＲＡ−２ｂを１．６ｇ（１０ミリモル水酸基当量１２０ミリモル）とトリエチルアミンを２．４２ｇ（２４０ミリモル）を量り取り、ＤＭＦを２０ミリリットル加え、回転子を入れ、室温で１時間攪拌した。これにクロロメチルメチルエーテルを１．４１ｇ（１８０ミリモル）を加え、窒素雰囲気下、室温で２時間攪拌した。反応後、塩をろ過により除去し、酢酸エチルで希釈し、反応混合物を蒸留水で５回洗浄した。次に、酢酸エチル層を硫酸マグネシウムで乾燥した。乾燥剤をろ過後、減圧留去し、析出した固体を室温で２４時間減圧乾燥した。その結果、生成物として粉末状の淡黄色固体を得た。構造確認はＩＲ、¹Ｈ ＮＭＲスペクトルおよび質量分析により行なった。結果を表８および図２に示す。

ＩＲスペクトルでは、カルボキシル基のＯＨのピークが完全に消失し、Ｃ＝Ｏのピークが１７３０ｃｍ^-1から１７６９ｃｍ^-1にシフトし、さらに、アセタール基に起因するピークが９２８ｃｍ^-1に確認された。また、¹Ｈ ＮＭＲスペクトルの結果から、アセタール基に帰因するピークが現れ、さらに、積分値が計算値と一致した。これらの結果から、得られた生成物は目的とするＣＲＡ−３ｂであることが確認された。 Example 2
A novel compound CRA-b derivative having an acetal residue (hereinafter abbreviated as CRA-3b) was synthesized by the following method. The reaction formula is represented by Formula (7).

In a 25 ml container, 1.6 g of CRA-2b (10 mmol hydroxyl group equivalent 120 mmol) and 2.42 g (240 mmol) of triethylamine were weighed, 20 ml of DMF was added, a rotor was added, and the mixture was stirred at room temperature for 1 hour. . To this was added 1.41 g (180 mmol) of chloromethyl methyl ether, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. After the reaction, the salt was removed by filtration, diluted with ethyl acetate, and the reaction mixture was washed 5 times with distilled water. Next, the ethyl acetate layer was dried over magnesium sulfate. The desiccant was filtered and then distilled off under reduced pressure, and the precipitated solid was dried under reduced pressure at room temperature for 24 hours. As a result, a powdery pale yellow solid was obtained as a product. The structure was confirmed by IR, ¹ H NMR spectrum and mass spectrometry. The results are shown in Table 8 and FIG.

In the IR spectrum, the OH peak of the carboxyl group disappeared completely, the C═O peak shifted from 1730 cm ⁻¹ to 1769 cm ⁻¹ , and a peak attributed to the acetal group was confirmed at 928 cm ⁻¹ . In addition, from the result of ¹ H NMR spectrum, a peak attributed to the acetal group appeared, and the integrated value coincided with the calculated value. From these results, it was confirmed that the obtained product was the target CRA-3b.

Example 3
DPSP, which is a Bronsted acid-generating photoacid generator, is added to the calix resorcinarene derivative obtained in Example 1 in an amount of 5 mol% based on the acetal residue, and dissolved in chloroform until uniform. A radiation sensitive resin composition was obtained by stirring.

Example 4
DPSP, which is a Bronsted acid-generating photoacid generator, is added to the calix resorcinarene derivative obtained in Example 2 in an amount of 5 mol% based on the acetal residue, and dissolved in chloroform until uniform. A radiation sensitive resin composition was obtained by stirring.

Radiation-sensitive resin compositions obtained in Example 3 and Example 4 by TG measurement of the thermal properties of the novel compound calixresorcinarene derivative, which is the acid-dissociable group-containing resin obtained in Example 1 and Example 2. The photodepolymerization property of the product was measured by light irradiation of an ultra-high pressure mercury lamp. Moreover, the solubility with respect to various solvents and the film formation ability were investigated.
(1) Thermal properties About 5 mg of a sample of calixresorcinarene derivative TG obtained in Example 1 and Example 2 was placed in an open aluminum pan using a thermogravimetry apparatus, and the mixture was raised in a nitrogen stream. Measurement was performed at a temperature rate of 10 ° C./min. The results are shown in FIG. In each sample, thermal decomposition started at about 300 ° C., and no change was observed at a lower temperature.
(2) Photodepolymerization The radiation-sensitive resin composition obtained in Example 3 and Example 4 was applied to a KBr plate to produce a film. Thereafter, a 250 W ultra-high pressure mercury lamp (15.0 mW / cm ^{2 at} 365 nm) was used as a light source, and light irradiation was performed for 5 minutes. The conversion rate of the depolymerization reaction was measured by a decrease in the absorption peak of the acetal residue using an FT-IR measuring apparatus with reference to the absorption peak of the phenyl group. The results are shown in FIG.
As shown in FIG. 4, after 2 minutes of irradiation, the conversion rates of Example 3 and Example 4 reached 80% and 77%, respectively, and no further change was observed. From the above results, it has been clarified that the photodeprotection reaction proceeds in a chain manner at room temperature when the acid generated by light irradiation acts as a catalyst.
(3) Solubility 1 ml of various solvents were added to 3 mg of calixresorcinarene derivative obtained in Example 1 and Example 2 to conduct a solubility test. As a result, calixresorcinarene derivatives are shown against methanol, 2-propanol, dimethylsulfoxide, dimethylacetamide, NMP, dimethylformamide, acetone, THF, ethyl acetate, 2-heptanone, ethyl lactate, chloroform, propylene glycol monomethyl ether acetate. Dissolved at room temperature. Moreover, it had film forming ability.

  Since the novel compound according to the present invention is represented by the formula (1), photodepolymerization easily occurs in a chain manner. Moreover, the solubility with respect to the casting solvent at the time of film preparation is excellent, and it is excellent in heat resistance. As a result, it can be used extremely favorably in the manufacture of integrated circuit elements that are expected to become increasingly finer in the future.

2 is a ¹ H NMR analysis result of Example 1. 2 is a ¹ H NMR analysis result of Example 2. 2 is a TG of Example 1 and Example 2. It is a figure which shows the conversion rate in the depolymerization reaction of Example 1 and Example 2.

Claims (2)

A novel compound represented by the following formula (1).

A radiation-sensitive resin composition comprising an acid-dissociable group-containing resin that is insoluble or hardly soluble in alkali and easily soluble in alkali by the action of an acid, and a radiation-sensitive acid generator,
The radiation-sensitive resin composition, wherein the acid-dissociable group-containing resin is the novel compound according to claim 1.

Images