Vinylphenylpropionic Acid Derivatives, Processes for Production of the Derivatives, Polymers Thereof

专利摘要:
This invention relates to a vinylphenylpropionic acid derivative, its manufacturing method, its polymer, and a radiation sensitive resin composition containing this polymer. The polymer has a low absorption to radiation and is particularly useful as a resin component in a radiation sensitive resin composition suitable for chemically amplified resists. For example, 4-vinylphenylpropionic acid t-butyl ester reacts ① t-butylbromoacetate with tri n-butylphosphine, ② reacts the resulting quaternary phosphonium salt with a base, and ③ produces phosphorus. Ride can be prepared by reacting with 2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) methylstyrene and ④ hydrolyzing the resulting quaternary phosphonium salt. have.
公开号:KR20020050277A
申请号:KR1020027006176
申请日:2000-11-10
公开日:2002-06-26
发明作者:용 왕；야스아끼 무쯔가；시게오 시미즈；쯔또무 시모까와；아쯔시 구마노
申请人:마쯔모또 에이찌；제이에스알 가부시끼가이샤；
IPC主号:

专利说明:

Vinylphenylpropionic acid derivatives, preparation methods thereof, polymers thereof, and radiation-sensitive resin compositions {Vinylphenylpropionic Acid Derivatives, Processes for Production of the Derivatives, Polymers Thereof and Radiosensitive Resin Compositions}
[2] In the field of microfabrication represented by the manufacture of integrated circuit devices, in order to obtain higher integration, miniaturization of the processing size in lithography is progressing, and in recent years, development of a lithography process capable of stably performing microfabrication of 0.5 μm or less This is actively going on. Accordingly, lithographic processes have been developed that utilize shorter wavelengths (wavelengths of 300 nm or less) that can achieve a wider depth of focus and are effective for miniaturizing design rules.
[3] Examples of such short wavelength radiation include far ultraviolet rays such as KrF excimer laser (wavelength 248 nm) or ArF excimer laser (wavelength 193 nm), X-rays such as synchrotron radiation, and charged particle beams such as electron beams. In addition, as a high-resolution resist corresponding to these short-wavelength radiation, "chemical amplification resist" has been proposed by International Business Machine (IBM), and the improvement of this chemical amplification resist is currently being actively promoted.
[4] Chemically amplified resists are classified into positive and negative types. The positive chemically amplified resist is an alkali insoluble or alkali poorly soluble resin protected by an acid generating substance (hereinafter referred to as a "radiation sensitive acid generator") and an acid dissociable group, wherein the acid dissociable group dissociates. Is a resin that becomes alkali-soluble when used (hereinafter referred to as " acid dissociable group-containing resin "), and is formed from a radiation-sensitive acid generator by radiation to a resist film (hereinafter referred to as " exposure "). Is generated, the acid dissociable group is decomposed in the resist film by the catalysis of this acid, and a resist pattern is formed by using a phenomenon in which an exposed portion is dissolved in a developer.
[5] The acid dissociable group-containing resin is, by itself, alkali-insoluble or substituted with one or more acid dissociable groups capable of dissociating the acidic functional group of a resin containing at least one acidic functional group such as a phenolic hydroxyl group or a carboxyl group in the presence of an acid. Alkali poorly soluble resin. As the acid dissociable group-containing resin containing a carboxyl group, a copolymer of acrylic acid and methacrylic acid protected with a t-butyl group or tetrahydropyranyl group (THP) and other monomers is generally known. However, resins containing units of acrylic acid and methacrylic acid protected with t-butyl group or THP have poor dry etching resistance, and thus have to be used with units having strong dry etching resistance. Therefore, if there is an acid dissociable group-containing monomer having strong dry etching resistance, for example, an aliphatic carunic acid derivative substituted with a vinylphenyl group including an acid-decomposable substituent, it can be copolymerized with more monomers and useful for optimizing the resist resin structure. Was considered.
[6] Conventionally, it has been reported to synthesize vinylphenylpropionic acid using 4- (2'-chloroethyl) styrene as starting material (T. Ishizone, et. Al, Macromolecules, 1999, 32, 1453-1462, S. Watanabe, et. al, Macromol. Chem. 1992, 193, 2781-2792), since this synthesis process is a reaction with Greenian reagent and carbon dioxide, it is not suitable for inexpensive and safe industrial production. In addition, 4- (2'-chloroethyl) styrene, which is a synthetic raw material, is also not an inexpensive industrial raw material and could not be easily produced.
[7] In addition, as a conventional problem specific to such chemically amplified resists, the line width of the resist pattern changes or the T-shape changes depending on the variation in the delay time (hereinafter referred to as "PED") from exposure to heat treatment after exposure. Although a problem such as the like has been pointed out recently, a polymer comprising a repeating unit for reducing the solubility of the polymer in an alkali developing solution after exposure and a repeating unit containing a hydroxystyrene-based repeating unit, t-butyl (meth) acrylate. Various chemically amplified resists that can be applied to semiconductor devices have been proposed, including radiation-sensitive resin compositions (see Japanese Patent Application Laid-Open No. Hei 7-209868).
[8] However, with the recent progress of miniaturization of semiconductor devices, in the chemically amplified resist, in view of increasing the sensitivity while maintaining the rectangularity of the pattern, the absorption of the radiation, which is the main component of the radiation-sensitive resin composition, to the radiation component, can be ignored. It has become difficult and difficult to apply to the fabrication of finer pattern size semiconductor devices that would be required in the future with conventional chemically amplified resists.
[1] The present invention relates to a vinylphenylpropionic acid derivative, a production method thereof, a polymer thereof, and a radiation sensitive resin composition. More specifically, the vinylphenylpropionic acid derivative including an acid-decomposable substituent, a manufacturing method thereof, a polymer thereof, and a charge of far ultraviolet rays, electron beams, etc. containing the polymer and typified by KrF excimer laser or ArF excimer laser, etc. A radiation sensitive resin composition useful for microfabrication using various radiations such as X-rays such as particle beams and synchrotron radiation.
[49] 1 is a nuclear magnetic resonance spectrum of the compound obtained in Example 1.
[50] 2 is an infrared absorption spectrum of the compound obtained in Example 1. FIG.
[51] 3 is a nuclear magnetic resonance spectrum of the compound obtained in Example (1).
[52] 4 is an infrared absorption spectrum of the compound obtained in Example (1).
[53] 5 is a nuclear magnetic resonance spectrum of the compound obtained in Example 2 (2).
[54] 6 is an infrared absorption spectrum of the compound obtained in Example (2).
[55] 7 is a nuclear magnetic resonance spectrum of the compound obtained in Example 3. FIG.
[56] 8 is an infrared absorption spectrum of the compound obtained in Example 3.
[57] 9 is a nuclear magnetic resonance spectrum of a compound obtained in Example 4. FIG.
[58] 10 is an infrared absorption spectrum of the compound obtained in Example 4. FIG.
[59] Preferred Embodiments of the Invention
[60] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
[61] Vinylphenylpropionic acid derivative
[62] The vinylphenylpropionic acid derivative of the present invention is represented by the formula (1).
[63] In formula (1), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, or a phenyl group which may be substituted.
[64] The alkyl group of an alkyl group having 1 to 8 carbon atoms which may be substituted may be linear or branched or cyclic, and examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group and decyl group Can be mentioned. Moreover, as a substituent, For example, Alkoxyl, such as a methoxyl group and an ethoxyl group; And halogen atoms such as fluorine, chlorine, bromine and iodine.
[65] Moreover, as a substituent of the phenyl group which may be substituted, For example, Alkyl groups, such as a methyl group, an ethyl group, n-propyl group, i-propyl group; Alkoxyl groups, such as a methoxyl group and an ethoxyl group; And halogen atoms such as fluorine, chlorine, bromine and iodine.
[66] In Formula 1, Z ¹ is a group represented by Formula 2 or 3 above. R ⁴ , R ⁵ and R ⁶ in Formula 2 may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, or a phenyl group which may be substituted, or R ⁴ , R ⁵ and R ⁶ Any two of may bond with each other to form a cyclic aliphatic group together with the carbon atom to which they are bonded.
[67] Further, in the formula (1), bonding position of -CHR ² CHR ³ COOZ ¹ is not particularly limited, but is preferably the para-position from the performance, such as in the case where easily obtaining a raw material, used as a resist material.
[68] In addition, R ⁷ and R ⁸ in Chemical Formula 3 may be the same or different, respectively, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted, or a phenyl group which may be substituted, and R ⁹ may be substituted It may represent an alkyl group having 1 to 8 carbon atoms or a phenyl group which may be substituted, or any two of R ⁷ , R ⁸ and R ⁹ may be bonded to each other to form a cyclic aliphatic group together with the carbon atom to which they are bonded.
[69] In the general formulas (2) and (3), examples of the alkyl group having 1 to 8 carbon atoms which may be substituted and the phenyl group which may be substituted are the same as those exemplified in the general formula (1).
[70] In the formulas (2) and (3), the cyclic alicyclic group is preferably a 5- to 7-membered ring, particularly a 6-membered ring. For example, a cyclohexylidene group for the formula (2), and 2-oxacyclopentyl for the formula (3). A den, 2-oxacyclohexylidene group can be illustrated as a preferable thing.
[71] In Formula 1, The group represented by is preferably an acid dissociable group which generates a carboxyl group (-COOH) in the presence of an acid. As such an acid dissociable group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t- Butoxycarbonyl, n-pentyloxycarbonyl, t-pentyloxycarbonyl, n-hexyloxycarbonyl, 1-methyl-1-ethylpropoxycarbonyl, n-heptyloxycarbonyl, 1,1-dimethylpentyloxycarbonyl, 1, 1-dimethyl-3-methylbutoxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 1-methylcyclohexyloxycarbonyl group, 4-t Linear, branched or cyclic alkoxy such as -butylcyclohexyloxycarbonyl group, cycloheptyloxycarbonyl group, cyclooctyloxycarbonyl group and 1-methyl-1-cyclohexylpropoxycarbonyl group Group;
[72] Aryloxycarbonyl groups such as phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group and 1-naphthyloxycarbonyl group;
[73] Benzyloxycarbonyl group, 4-t-butylbenzyloxycarbonyl group, phenethyloxycarbonyl group, 4-t-butylphenethyloxycarbonyl group, 1-methyl-1-phenylethoxycarbonyl group, 1-phenyl-1- (4'-methylphenyl Aralkyloxycarbonyl groups such as) ethoxycarbonyl group;
[74] 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-i-propoxyethoxycarbonyl group, 1-n-butoxyethoxycarbonyl group, 1- (2 '-Methylpropoxy) ethoxycarbonyl group, 1- (1'-methylpropoxy) ethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1- (4'-t Linear, branched or cyclic 1-alkoxyethoxycarbonyl groups such as -butylcyclohexyloxy) ethoxycarbonyl group;
[75] 1-aryloxyethoxycarbonyl groups, such as a 1-phenoxy oxycarbonyl group, a 1- (4'-t-butylphenoxy) ethoxycarbonyl group, and a 1- (1'- naphthyloxy) ethoxycarbonyl group;
[76] 1-benzyloxyethoxycarbonyl group, 1- (4'-t-butylbenzyloxy) ethoxycarbonyl group, 1-phenethyloxyethoxycarbonyl group, 1- (4'-t-butylphenethyloxy) ethoxycarbonyl group, etc. 1-aralkyloxyethoxycarbonyl group of;
[77] Methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group, i-propoxycarbonylmethoxycarbonyl group, n-butoxycarbonylmethoxycarbonyl group, 2-methylpropoxy Foxoxycarbonylmethoxycarbonyl group, 1-methylpropoxycarbonylmethoxycarbonyl group, t-butoxycarbonylmethoxycarbonyl group, cyclohexyloxycarbonylmethoxycarbonyl group, 4-t-butylcyclohexyloxycarbonylmethoxycarbonyl group Linear, branched or cyclic alkoxycarbonylmethoxycarbonyl groups such as;
[78] Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, 2-methylpropoxycarbonylmethyl group, 1-methylpropoxy Linear, branched or cyclic alkoxycarbonylmethyl groups such as carbonylmethyl group, t-butoxycarbonylmethyl group, cyclohexyloxycarbonylmethyl group, and 4-t-butylcyclohexyloxycarbonylmethyl group;
[79] Aryloxycarbonylmethyl groups such as phenoxycarbonylmethyl group, 4-t-butylphenoxycarbonylmethyl group and 1-naphthyloxycarbonylmethyl group; Aralkyloxycarbonylmethyl groups such as benzyloxycarbonylmethyl group, 4-t-butylbenzyloxycarbonylmethyl group, phenethyloxycarbonylmethyl group, and 4-t-butylphenethyloxycarbonylmethyl group;
[80] 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propoxycarbonylethyl group, 2-i-propoxycarbonylethyl group, 2-n-butoxycarbonylethyl group, 2- (2 '-Methylpropoxy) carbonylethyl group, 2- (1'-methylpropoxy) carbonylethyl group, 2-t-butoxycarbonylethyl group, 2-cyclohexyloxycarbonylethyl group, 2- (4'- linear, branched or cyclic 2-alkoxycarbonylethyl groups such as t-butylcyclohexyloxycarbonyl) ethyl group;
[81] 2-aryloxycarbonylethyl groups such as 2-phenoxycarbonylethyl group, 2- (4'-t-butylphenoxycarbonyl) ethyl group, and 2- (1'-naphthyloxycarbonyl) ethyl group;
[82] 2-benzyloxycarbonylethyl group, 2- (4'-t-butylbenzyloxycarbonyl) ethyl group, 2-phenethyloxycarbonylethyl group, 2- (4'-t-butylphenethyloxycarbonyl) ethyl group 2-aralkyloxycarbonylethyl group, and
[83] 1-methyl-1-n-butoxypropoxycarbonyl group, 1-phenylcyclohexyloxycarbonyl group, (cyclohexyl) (phenoxy) methoxycarbonyl group, 1-phenyl-1-cyclohexyloxyethoxycarbonyl group, (cyclohexyl ) (Phenyl) (methoxy) methoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2- (2-methyltetrahydrofuranyl) oxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 2- (2,5 -Dimethyltetrahydropyranyl) oxycarbonyl group, 2- (2-phenyltetrahydropyranyl) oxycarbonyl group, etc. are mentioned.
[84] As the compound represented by Formula 1, for example, the compounds of Formulas 6-1 to 6-32 (Z ¹ in Formula ¹ is a group of Formula 2) and the compounds of Formulas 7-1 to 7-22 (Formula 1 In the above, Z ¹ is a group represented by the formula (3). Especially, it is preferable that a coupling position is a para position.
[85]
[86]
[87]
[88]
[89]
[90]
[91] Since these vinylphenylpropionic acid derivatives contain an acid-decomposable group in the side chain, a polymer obtained by polymerizing alone or with another monomer decomposes a hydrophobic alkoxycarbonyl group with an acid to form a high hydrophilic oxycarbonyl group, thereby realizing a polar change of the polymer. have. Moreover, since these vinylphenylpropionic acid derivatives contain a benzene ring with strong dry etching resistance, it can be combined with various monomers in the design of a resist resin, and is useful for the optimization of a resist resin structure.
[92] Preparation of Vinyl Phenylpropionate Derivatives
[93] The vinylphenylpropionic acid derivative of the present invention can be advantageously produced by the method of the present invention comprising the steps (i) to (iv) as described above.
[94] In step (i), the ethyl acetate represented by the general formula (4-1) and the trialkylphosphine represented by the general formula (4-2) can be reacted.
[95] In the formula (4-1), the definition of R ³ is the same as in formula (1), and specific examples thereof are also the same as those described above. In Chemical Formula 4-1, Z ² is a group represented by Chemical Formula 2 'or 3. The definitions of R ¹⁰ , R ¹¹ and R ¹² in the formula (2 ′) are the same as the definitions of R ⁴ , R ⁵ and R ⁶ in the formula (2). In Chemical Formula 4-1, X ₁ is a leaving group, and examples thereof include those commonly used in organic synthesis, for example, halogen atoms such as chlorine, bromine and iodine, methylsulfonyl groups, and p-methylphenylsulfonyl groups. Ponyyl group is mentioned.
[96] The trialkylphosphine used in the step (i) is not particularly limited, but preferred examples include triethylphosphine, tri n-butylphosphine, tricyclohexylphosphine, and the like.
[97] The reaction in step (i) is preferably carried out at -10 ° C to 80 ° C for 2 to 40 hours. More preferable reaction temperature and reaction time are 10-50 degreeC and 4-10 hours, respectively. In addition, it is preferable to perform this reaction in nitrogen atmosphere. As a solvent used for reaction of a process (i), a water miscible aprotic organic solvent is used preferably. As such a solvent, tetrahydrofuran, 1, 4- dioxane, N, N- dimethylformamide, dimethyl sulfoxide, acetonitrile, etc. are mentioned, for example. By the reaction of step (i), the first quaternary phosphonium salt represented by the general formula (4-3) is produced. Definitions of R ³ , Z and X ₁ in Formula 4-3 and the specific examples thereof are as described above.
[98] In step (ii), the base may be reacted with the first quaternary phosphonium salt produced in step (i).
[99] As the base, various bases from strong basic to super basic can be used. For example, 1,5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, potassium (or sodium, lithium) methoxide, potassium (or Sodium, lithium) ethoxide, potassium (or sodium, lithium) n-propoxide, potassium (or sodium, lithium) isopropoxide, potassium (or sodium, lithium) n-butoxide, potassium (or sodium, lithium ) sec-butoxide, potassium (or sodium, lithium) isobutoxide, potassium (or sodium, lithium) t-butoxide, lithium diisopropylamide, lithium (or sodium, potassium, calcium) hydride, methyllithium or n-butyl (or sec-butyl, t-butyl) lithium and the like. It is preferable that reaction of a process (ii) is performed at -80 degreeC-80 degreeC. In the case of a strong base, 20 to 50 degreeC is preferable, and in the case of a super base, the reaction temperature of -20 degreeC or less is preferable. 15 minutes-10 hours are preferable, and, as for reaction time, 30 minutes-2 hours are more preferable.
[100] By the reaction of step (ii), the phosphide represented by Chemical Formula 4-4 is produced. In the formula (4-4), the definitions and specific examples of R ³ and Z are as described above.
[101] In step (iii), the phosphide produced in step (ii) is reacted with a styrene derivative represented by the formula (4-5).
[102] In the general formula (4-5), definitions and embodiments of R ¹ and R ² are as described above. X ₂ is a leaving group, and specific examples thereof include the same as those exemplified for X ₁ in the general formula (4-1). 0 degreeC-80 degreeC and 1 to 96 hours are preferable, and, as for the temperature and reaction time of a process (iii), 20 degreeC-50 degreeC and 2 to 48 hours are more preferable.
[103] By reaction of step (iii), a second quaternary phosphonium salt represented by the formula (4-6) is produced. Definitions and embodiments of R ¹ , R ² , R ³ and Z in Formula 4-6 are as described above.
[104] Finally, in step (iv), the second quaternary phosphonium salt produced in step (iii) is hydrolyzed.
[105] 0 degreeC-80 degreeC and 1 to 48 hours are preferable, and, as for the reaction temperature and reaction time of reaction of a process (iv), 20 degreeC-50 degreeC and 2 to 24 hours are more preferable. As aqueous alkali solution used for this reaction, the normal aqueous solution of an inorganic or organic base can be used. As such a base, for example, sodium bicarbonate (or potassium), sodium (or potassium), sodium carbonate (or potassium), sodium hydroxide (or potassium), ammonia, tetramethylammonium carbonate (or hydroxide), tetrabutyl Ammonium carbonate (or hydroxide), triethylamine, 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7 and the like Can be.
[106] As a reaction solvent at the time of the hydrolysis reaction of a process (iv), the mixed solvent of water and water, and an organic solvent is used. When using a mixed solvent, especially organic solvents which are miscible with water, such as methanol, ethanol, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile and the like desirable.
[107] As for reaction temperature and reaction time of a process (iv), 0 degreeC-100 degreeC, 15 minutes-96 hours are preferable, respectively, 20 degreeC-80 degreeC, and 1 to 24 hours are more preferable.
[108] In addition, although the manufacturing method containing said process (i)-(iv) can be performed by one pot, the reaction solvent of process (ii) and process (iii) is the same organic solvent as the reaction solvent of process (i). It may be daily, and may also be a mixed solvent comprising the reaction solvent of step (i).
[109] Alternatively, the methylphenyl (or ethyl) vinylphenylpropionate represented by the following formula (5-1) is hydrolyzed to produce a vinylphenylpropionic acid represented by the following formula (5-2), and then the vinylphenylpropionic acid is a corresponding esterifying agent, for example For example, the vinylphenylpropionic acid derivative of the present invention can be produced by esterification with alcohol. This alternative is particularly useful when the chemical stability of the carboxylic acid derivative represented by the above formula (4-1) is poor.
[110] <Formula 5-1>
[111]
[112] In the formula, the definitions of R ¹ , R ^2, and R ³ are the same as those of Formula 1, and Y is a methyl group or an ethyl group.
[113] <Formula 5-2>
[114]
[115] In the formula, the definitions of R ¹ , R ² and R ³ are the same as in the above formula (1).
[116] The said hydrolysis reaction can be performed by the hydrolysis method of the carboxylic acid ester generally known. In addition, esterification reaction can be performed by the normalization of the esterification method of a normal carboxylic acid, and addition reaction of a carboxylic acid and an olefin, for example.
[117] It is preferable to use a polymerization inhibitor for the purpose of preventing a polymerization reaction in all the reaction of the manufacturing method of this invention, and an alternative method. As a polymerization inhibitor, for example, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tris (3 ', 5'-di- Commercially available polymerization inhibitors, such as t-butyl-4'-hydroxybenzyl) mesitylene), are mentioned. It is preferable that it is 0.001%-20 weight% of the total amount of raw materials other than the solvent used during reaction, and, as for the appropriate usage-amount of a polymerization inhibitor, it is more preferable that it is 1.1%-10%.
[118] (A) polymer
[119] The polymer in the present invention includes a polymer having a repeating unit represented by the general formula (1 ') (hereinafter referred to as "repeating unit (1')") as an essential unit (hereinafter referred to as "(A) polymer"). do.
[120] (A) It is preferable that content of the repeating unit (1 ') in a polymer is 5-80 weight%.
[121] The monomer which provides the repeating unit (1 ') is a vinylphenylpropionic acid derivative represented by the formula (1).
[122] (A) The polymer is a unit derived from a coherent monomer containing one polymerizable unsaturated bond in addition to the repeating unit (1 ') (hereinafter referred to as "the other repeating unit (α)") and / or two or more The unit derived from the polyfunctional monomer containing a polymerizable unsaturated bond (henceforth "other repeating unit ((beta))") can be included.
[123] As a monomer which provides another repeating unit ((alpha)), for example
[124] Styrene monomers which may be substituted by linear, branched or cyclic alkyl substitutions such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene and p-methylstyrene;
[125] styrene monomers substituted with hydroxyl groups such as o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, and p-hydroxy-α-methyl styrene;
[126] linear, branched, or o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, ot-butoxystyrene, mt-butoxystyrene, pt-butoxystyrene, p-cyclohexyloxystyrene, or the like Styrene monomers substituted with cyclic alkoxyl groups;
[127] p- (1-methoxyethoxy) styrene, p- (1-ethoxyethoxy) styrene, p- (1-n-propoxyethoxy) styrene, p- (1-i-propoxyethoxy) Styrene, p- (1-n-butoxyethoxy) styrene, p- (1-t-butoxyethoxy) styrene, p- (1-n-pentyloxyethoxy) styrene, p- (1-n -Hexyloxyethoxy) styrene, p- (1-cyclopentyloxyethoxy) styrene, p- (1-cyclohexyloxyethoxy) styrene, p- (1-benzyloxyethoxy) styrene, p- {1 Styrene-based monomers substituted with linear, branched or cyclic 1-alkoxyethoxy groups such as-(1'-naphthylmethoxy) ethoxy} styrene or styrene-based monomers substituted with 1-aralkyloxyethoxy groups Ryu;
[128] p- (1-methoxypropoxy) styrene, p- (1-ethoxypropoxy) styrene, p- (1-n-propoxypropoxy) styrene, p- (1-i-propoxypropoxy) Styrene, p- (1-n-butoxypropoxy) styrene, p- (1-t-butoxypropoxy) styrene, p- (1-n-pentyloxypropoxy) styrene, p- (1-n -Hexyloxypropoxy) styrene, p- (1-cyclopentyloxypropoxy) styrene, p- (1-cyclohexyloxypropoxy) styrene, p- (1-benzyloxypropoxy) styrene, p- {1 Styrene-based monomers substituted with linear, branched or cyclic 1-alkoxypropoxy groups or styrene-based monomers substituted with 1-aralkyloxypropoxy groups, such as-(1'-naphthylmethoxy) propoxy} styrene;
[129] p- (1-methoxy-1-methylethoxy) styrene, p- (1-ethoxy-1-methylethoxy) styrene, p- (1-n-propoxy-1-methylethoxy) styrene, p- (1-i-propoxy-1-methylethoxy) styrene, p- (1-n-butoxy-1-methylethoxy) styrene, p- (1-t-butoxy-1-methyl Methoxy) styrene, p- (1-n-pentyloxy-1-methylethoxy) styrene, p- (1-n-hexyloxy-1-methylethoxy) styrene, p- (1-cyclopentyloxy- 1-methylethoxy) styrene, p- (1-cyclohexyloxy-1-methylethoxy) styrene, p- (1-benzyloxy-1-methylethoxy) styrene, p- {1- (1 ' Styrene monomer or 1-aralkylalkyl-1-methyl substituted with a linear, branched or cyclic 1-alkoxy-1-methylethoxy group such as -naphthylmethoxy) -1-methylethoxy} styrene; Styrene monomers substituted with oxy groups;
[130] p- (1-methoxybutoxy) styrene, p- (1-ethoxybutoxy) styrene, p- (1-n-propoxybutoxy) styrene, p- (1-i-propoxybutoxy) Styrene, p- (1-n-butoxybutoxy) styrene, p- (1-t-butoxybutoxy) styrene, p- (1-n-pentyloxybutoxy) styrene, p- (1-n -Hexyloxybutoxy) styrene, p- (1-cyclopentyloxybutoxy) styrene, p- (1-cyclohexyloxybutoxy) styrene, p- (1-benzyloxybutoxy) styrene, p- {1 Styrene-based monomers substituted with linear, branched or cyclic 1-alkoxybutoxy groups such as-(1'-naphthylmethoxy) butoxy} styrene or styrene-based monomers substituted with 1-aralkylalkylbutoxy groups;
[131] p- (1-methoxy-2-methylpropoxy) styrene, p- (1-ethoxy-2-methylpropoxy) styrene, p- (1-n-propoxy-2-methylpropoxy) styrene, p- (1-i-propoxy-2-methylpropoxy) styrene, p- (1-n-butoxy-2-methylpropoxy) styrene, p- (1-t-butoxy-2-methylprop Foxy) styrene, p- (1-n-pentyloxy-2-methylpropoxy) styrene, p- (1-n-hexyloxy-2-methylpropoxy) styrene, p- (1-cyclopentyloxy- 2-methylpropoxy) styrene, p- (1-cyclohexyloxy-2-methylpropoxy) styrene, p- (1-benzyloxy-2-methylpropoxy) styrene, p- {1- (1 ' Styrene-based monomer or 1-aralkyloxy-2-methylpropoxy substituted with linear, branched or cyclic 1-alkoxy-2-methylpropoxy group, such as -naphthylmethoxy) -2-methylpropoxy} styrene; Styrene monomers substituted with groups;
[132] p- (1-methoxy-1-methylpropoxy) styrene, p- (1-ethoxy-1-methylpropoxy) styrene, p- (1-n-propoxy-1-methylpropoxy) styrene, p- (1-i-propoxy-1-methylpropoxy) styrene, p- (1-n-butoxy-1-methylpropoxy) styrene, p- (1-t-butoxy-1-methylprop Foxy) styrene, p- (1-n-pentyloxy-1-methylpropoxy) styrene, p- (1-n-hexyloxy-1-methylpropoxy) styrene, p- (1-cyclopentyloxy- 1-methylpropoxy) styrene, p- (1-cyclohexyloxy-1-methylpropoxy) styrene, p- (1-benzyloxy-1-methylpropoxy) styrene, p- {1- (1 ' Styrene-based monomers substituted with linear, branched or cyclic 1-alkoxy-1-methylpropoxy groups such as naphthylmethoxy) -1-methylpropoxy} styrene or 1-aralkyloxy-1-methylpropoxy Styrene monomers substituted with groups;
[133] p- (1-methoxypentyloxy) styrene, p- (1-ethoxypentyloxy) styrene, p- (1-n-propoxypentyloxy) styrene, p- (1-i-propoxypentyloxy) Styrene, p- (1-n-butoxypentyloxy) styrene, p- (1-t-butoxypentyloxy) styrene, p- (1-n-pentyloxypentyloxy) styrene, p- (1-n -Hexyloxypentyloxy) styrene, p- (1-cyclopentyloxypentyloxy) styrene, p- (1-cyclohexyloxypentyloxy) styrene, p- (1-benzyloxypentyloxy) styrene, p- {1 Styrene monomers substituted with linear, branched or cyclic 1-alkoxypentyloxy groups such as-(1'-naphthylmethoxy) pentyloxy} styrene or styrene monomers substituted with 1-aralkyloxypentyloxy group;
[134] p- (1-methoxy-1-methylbutoxy) styrene, p- (1-ethoxy-1-methylbutoxy) styrene, p- (1-n-propoxy-1-methylbutoxy) styrene, p- (1-i-propoxy-1-methylbutoxy) styrene, p- (1-n-butoxy-1-methylbutoxy) styrene, p- (1-t-butoxy-1-methyl moiety Methoxy) styrene, p- (1-n-pentyloxy-1-methylbutoxy) styrene, p- (1-n-hexyloxy-1-methylbutoxy) styrene, p- (1-cyclopentyloxy- 1-methylbutoxy) styrene, p- (1-cyclohexyloxy-1-methylbutoxy) styrene, p- (1-benzyloxy-1-methylbutoxy) styrene, p- {1- (1 ' Styrene-based monomers or 1-aralkylalkyl-1-methylbutoxy groups substituted with linear, branched or cyclic 1-alkoxy-1-methylbutoxy groups such as -naphthylmethoxy) -1-methylbutoxy} styrene; Styrene-based monomers substituted with;
[135] p- (1-methoxy-1,2-dimethylpropoxy) styrene, p- (1-ethoxy-1,2-dimethylpropoxy) styrene, p- (1-n-propoxy-1,2- Dimethylpropoxy) styrene, p- (1-i-propoxy-1,2-dimethylpropoxy) styrene, p- (1-n-butoxy-1,2-dimethylpropoxy) styrene, p- (1 -t-butoxy-1,2-dimethylpropoxy) styrene, p- (1-n-pentyloxy-1,2-dimethylpropoxy) styrene, p- (1-n-hexyloxy-1,2 -Dimethylpropoxy) styrene, p- (1-cyclopentyloxy-1,2-dimethylpropoxy) styrene, p- (1-cyclohexyloxy-1,2-dimethylpropoxy) styrene, p- (1 Linear, branched or cyclic 1-alkoxy such as benzyloxy-1,2-dimethylpropoxy) styrene and p- {1- (1'-naphthylmethoxy) -1,2-dimethylpropoxy} styrene Styrene monomers substituted with -1,2-dimethylpropoxy or styrene monomers substituted with 1-aralkyloxy-1,2-dimethylpropoxy;
[136] p- (1-methoxy-2,2-dimethylpropoxy) styrene, p- (1-ethoxy-2,2-dimethylpropoxy) styrene, p- (1-n-propoxy-2,2- Dimethylpropoxy) styrene, p- (1-i-propoxy-2,2-dimethylpropoxy) styrene, p- (1-n-butoxy-2,2-dimethylpropoxy) styrene, p- (1 -t-butoxy-2,2-dimethylpropoxy) styrene, p- (1-n-pentyloxy-2,2-dimethylpropoxy) styrene, p- (1-n-hexyloxy-2,2 -Dimethylpropoxy) styrene, p- (1-cyclopentyloxy-2,2-dimethylpropoxy) styrene, p- (1-cyclohexyloxy-2,2-dimethylpropoxy) styrene, p- (1 Linear, branched or cyclic 1-alkoxy such as benzyloxy-2,2-dimethylpropoxy) styrene, p- {1- (1'-naphthylmethoxy) -2,2-dimethylpropoxy} styrene Styrene monomers substituted with -2,2-dimethylpropoxy or styrene monomers substituted with 1-aralkyloxy-2,2-dimethylpropoxy;
[137] p- (1-methoxy-1-methylpentyloxy) styrene, p- (1-ethoxy-1-methylpentyloxy) styrene, p- (1-n-propoxy-1-methylpentyloxy) styrene, p- (1-i-propoxy-1-methylpentyloxy) styrene, p- (1-n-butoxy-1-methylpentyloxy) styrene, p- (1-t-butoxy-1-methylpentyl Oxy) styrene, p- (1-n-pentyloxy-1-methylpentyloxy) styrene, p- (1-n-hexyloxy-1-methylpentyloxy) styrene, p- (1-cyclopentyloxy- 1-methylpentyloxy) styrene, p- (1-cyclohexyloxy-1-methylpentyloxy) styrene, p- (1-benzyloxy-1-methylpentyloxy) styrene, p- {1- (1 ' Styrene-based monomers substituted with linear, branched or cyclic 1-alkoxy-1-methylpentyloxy groups such as naphthylmethoxy) -1-methylpentyloxy} styrene, or 1-aralkylalkyl-1-methylpentyloxy Styrene monomers substituted with groups;
[138] p- (1-methoxy-1,2,2-trimethylpropoxy) styrene, p- (1-ethoxy-1,2,2-trimethylpropoxy) styrene, p- (1-n-propoxy- 1,2,2-trimethylpropoxy) styrene, p- (1-i-propoxy-1,2,2-trimethylpropoxy) styrene, p- (1-n-butoxy-1,2,2- Trimethylpropoxy) styrene, p- (1-t-butoxy-1,2,2-trimethylpropoxy) styrene, p- (1-n-pentyloxy-1,2,2-trimethylpropoxy) styrene, p- (1-n-hexyloxy-1,2,2-trimethylpropoxy) styrene, p- (1-cyclopentyloxy-1,2,2-trimethylpropoxy) styrene, p- (1-cyclo Hexyloxy-1,2,2-trimethylpropoxy) styrene, p- (1-benzyloxy-1,2,2-trimethylpropoxy) styrene, p- {1- (1'-naphthylmethoxy)- Styrene-based monomer substituted with linear, branched or cyclic 1-alkoxy-1,2,2-trimethylpropoxy group such as 1,2,2-trimethylpropoxy} styrene or 1-aralkyloxy-1,2 Styrene monomers substituted with a 2-trimethylpropoxy group;
[139] p-methoxycarbonyloxystyrene, p-ethoxycarbonyloxystyrene, pn-propyloxycarbonyloxystyrene, pi-propyloxycarbonyloxystyrene, pn-butoxycarbonyloxystyrene, p-2-methyl Linear, branched or cyclic alkoxycarboxes such as propoxycarbonyloxystyrene, p-1-methylpropoxycarbonyloxystyrene, pt-butoxycarbonyloxystyrene and p-cyclohexyloxycarbonyloxystyrene Styrene monomers substituted with a carbonyloxy group;
[140] p-methoxycarbonylmethoxystyrene, p-ethoxycarbonylmethoxystyrene, pn-propyloxycarbonylmethoxystyrene, pi-propyloxycarbonylmethoxystyrene, pn-butoxycarbonylmethoxystyrene, linear such as p-2-methylpropoxycarbonylmethoxystyrene, p-1-methylpropoxycarbonylmethoxystyrene, pt-butoxycarbonylmethoxystyrene, p-cyclohexyloxycarbonylmethoxystyrene Styrene monomers substituted with a branched or cyclic alkoxycarbonylmethoxy group, and
[141] In addition to vinyl aromatic compounds, such as 4-vinylphenyl propionic acid and 3- (4'-vinylphenyl) -1-propanol,
[142] Unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride or acid anhydrides thereof;
[143] Methyl ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, 2-methylpropyl ester, 1-methylpropyl ester, t-butyl ester, n-pentyl ester, n of the above unsaturated carboxylic acid -Hexyl ester, cyclohexyl ester, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 3-hydroxypropyl ester, 2,2-dimethyl-3-hydroxypropyl ester, benzyl ester, isoboroyl ester , Tricyclodecanyl ester, 1-adamantyl ester, 2-methyl-2-adamantyl ester, 2-ethyl-2-adamantyl ester, 2-n-propyladamantyl ester, 3-hydroxy -1-adamantyl ester, 2-methyl-3-hydroxy-1-adamantyl ester, 2-ethyl-3-hydroxy-1-adamantyl ester, 2-n-propyl-3-hydroxy -1-adamantyl ester, 2-i-propyl-1-adamantyl ester, 8-hydroxytetracyclododecane-3-methyl ester Esters such as 9-hydroxytetracyclododecane-3-methyl ester;
[144] Unsaturated nitriles such as (meth) acrylonitrile, malenitrile, fumaronitrile, mesaconitrile, citraconnitrile, and itaconitrile;
[145] (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, N- (meth) acryloylmorpholine, etc. Unsaturated amides; Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide;
[146] Unsaturated alcohols such as (meth) allyl alcohol, and
[147] N-vinyl aniline, vinyl pyridines, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole, etc. are mentioned.
[148] Among these monofunctional monomers, styrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, pt-butoxystyrene, p- (1-methoxyethoxy) styrene and p- (1-ethoxye Methoxy) styrene, p- (1-cyclohexyloxyethoxy) styrene, p- (1-benzyloxyethoxy) styrene, p- {1- (1'-naphthylmethoxy) ethoxy)} styrene, p- (1-methoxypropoxy) styrene, p- (1-ethoxypropoxy) styrene, p- (1-benzyloxypropoxy) styrene, p- {1- (1'-naphthylmethoxy) propoxy) } Styrene, p- (1-methoxy-1-methylethoxy) styrene, 4-vinylphenylpropionic acid, 3- (4'-vinylphenyl) -1-propanol, (meth) acrylic acid, (meth) acrylic acid t- Butyl, 2- (meth) acryloyloxy-2-methyladamantane, 2- (meth) acryloyloxy-2-ethyladamantane, 1- (meth) acryloyloxy-3-hydroxy Cydamantan, 3- (meth) acryloyloxymethyl-8-hydroxytetracyclododecane, 3- (meth) acryloyloxymethyl-9-hydroxytetracyclododecane, N, N- Dimethyl acrylamide, N-acryloyl morpholine, N-vinyl- epsilon caprolactam, N-vinylpyrrolidone, etc. are preferable.
[149] The monofunctional monomers may be used alone or in combination of two or more thereof.
[150] 80 weight% or less is preferable and, as for content of another repeating unit ((alpha)) in (A) polymer, 5-70 weight% is more preferable.
[151] Moreover, as a polyfunctional monomer which provides another repeating unit ((beta)), For example, the compound and the (meth) acrylic acid which contain two or more hydroxyl groups in molecules, such as a bivalent or more polyhydric alcohol, polyetherdiol, polyesterdiol, etc., Esters of; Adducts of a compound containing two or more epoxy groups and (meth) acrylic acid in a molecule represented by an epoxy resin; Condensation products of the compound containing two or more amino groups, and (meth) acrylic acid in a molecule | numerator are mentioned, Specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylol Propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,5-dimethyl-2,5-hexanediol Di (meth) acrylate of di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, ethylene glycol adduct of bisphenol A or propyl glycol adduct In addition, the (meth) acrylic acid chin of bisphenol A diglycidyl ether and the like epoxy (meth) acrylates, N, N'- methylene-bis (meth) acrylamides, such as water.
[152] Among these polyfunctional monomers, in particular, ethylene glycol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, bisphenol A di Preferred are (meth) acrylic acid adducts of glycidyl ether.
[153] The said polyfunctional monomer can be used individually or in combination of 2 or more types.
[154] When the polymer (A) contains other repeating units (β), an appropriate crosslinked structure is introduced to reduce the mobility of the polymer molecular chain, thereby suppressing thermal deformation and improving heat resistance and the like. Moreover, when the crosslinked structure introduced by the polyfunctional monomer has acid dissociation property, the molecular weight decrease by exposure becomes large compared with the case of linear resin and the case where a crosslinked structure does not have acid dissociation property, and an exposed part and an unexposed part As a result, the dissolution rate difference with respect to the developer increases, the resolution can be further improved.
[155] 10 weight% or less is preferable, as for content of another repeating unit ((beta)) in (A) polymer, 7 weight% or less is more preferable, 6 weight% or less is especially preferable.
[156] The polymer (A) is, for example, radically polymerized with a monomer corresponding to the repeating unit (1) together with a monomer corresponding to another repeating unit (α) and / or another repeating unit (β), as the case may be. The initiator can be appropriately selected and prepared by polymerization by appropriate methods such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, and bulk-suspension polymerization, preferably by solution polymerization.
[157] Azobisisobutyronitrile, dimethyl-2,2'- azobis (2-methylpropionate), etc. are mentioned as a preferable radical polymerization initiator used for superposition | polymerization which manufactures (A) polymer. In addition, although the reaction medium can be selected suitably, n-butyl acetate, tetrahydrofuran, propylene glycol monomethyl ether, etc. can be used, for example.
[158] It is preferable that reaction temperature is 50-90 degreeC, as for the polymerization conditions at the time of manufacturing a polymer (A), it is more preferable that it is 60-85 degreeC, and it is preferable that reaction time is 3-10 hours.
[159] (A) The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of the polymer is 1,000 to 500,000. However, the specific Mw of (A) polymer depends on the presence or absence of the crosslinked structure by a polyfunctional monomer.
[160] That is, the Mw of the polymer (A) not containing a crosslinked structure by the polyfunctional monomer is preferably from 1,000 to 100,000, more preferably from 3,000 to 40,000, still more preferably from 3,000 to 30,000. In this case, when the Mw of the polymer (A) is less than 1,000, the sensitivity and heat resistance as a resist decrease, while when it exceeds 100,000, the solubility in the developer decreases.
[161] Ratio (Mw / Mn) of Mw of (A) polymer which does not contain crosslinked structure by polyfunctional monomer and polystyrene conversion number average molecular weight (hereinafter referred to as "Mn") by gel permeation chromatography (GPC) Silver is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.
[162] Moreover, 3,000-500,000 are preferable, as for Mw of the polymer (A) containing the crosslinked structure by a polyfunctional monomer, 5,000-400,000 are more preferable, 8,000-300,000 are especially preferable. In this case, when the Mw of the polymer (A) is less than 3,000, the sensitivity and heat resistance as a resist decrease, while when exceeding 500,000, the developability as a resist decreases.
[163] 1.5-20.0 are preferable and, as for Mw / Mn of the polymer (A) containing the crosslinked structure by a polyfunctional monomer, 1.5-15.0 are more preferable.
[164] The polymer (A) has a very low absorption to radiation, and is particularly useful as a resin component in a radiation sensitive resin composition which is preferable for chemically amplified resists, and the radiation sensitive resin composition has an effective exposure dose between the upper and lower portions of the resist film. The difference can be reduced, the rectangularness of the pattern can be maintained even in the fine pattern size, and at the same time, it has an excellent characteristic of high sensitivity (low exposure energy amount).
[165] (B) radiation-sensitive acid generators
[166] The radiation sensitive resin composition of this invention contains the (B) radiation sensitive acid generator (henceforth "(B) acid generator") which generate | occur | produces an acid by the said (A) polymer and exposure. It features.
[167] (B) As an acid generator, (1) Onium salt, (2) sulfone compound, (3) sulfonic acid ester compound, (4) sulfonyloxyimide compound, (5) disulfonyl diazomethane compound, (6) disulfonyl methane derivative, etc. are mentioned, for example.
[168] Hereinafter, the example of such (B) acid generator is shown.
[169] ① Onium salt:
[170] Examples of the onium salts include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.
[171] As a specific example of an onium salt compound,
[172] Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) Iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium pyrenesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium benzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate , Bis (4-t-butylphenyl) iodonium n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) 4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium perfluorobenzenesulfonate,
[173] Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium pyrenesulfonate , Diphenyl iodonium n-dodecylbenzenesulfonate, diphenyl iodonium p-toluenesulfonate, diphenyl iodonium benzenesulfonate, diphenyl iodonium 10-camphorsulfonate, diphenyl iodonium n-octanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate,
[174] Di (p-toluyl) iodonium trifluoromethanesulfonate, di (p-toluyl) iodonium nonafluoro-n-butanesulfonate, di (p-toluyl) iodonium perfluoro -n-octanesulfonate, di (p-toluyl) iodonium pyrensulfonate, di (p-toluyl) iodonium n-dodecylbenzenesulfonate, di (p-toluyl) iodonium p -Toluenesulfonate, di (p-toluyl) iodonium benzenesulfonate, di (p-toluyl) iodonium 10-camposulfonate, di (p-toluyl) iodonium n-octanesulfonate , Di (p-toluyl) iodonium 2-trifluoromethylbenzenesulfonate, di (p-toluyl) iodonium 4-trifluoromethylbenzenesulfonate, di (p-toluyl) iodo Perfluorobenzenesulfonate,
[175] Di (3,4-dimethylphenyl) iodonium trifluoromethanesulfonate, di (3,4-dimethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (3,4-dimethylphenyl) Iodonium perfluoro-n-octanesulfonate, di (3,4-dimethylphenyl) iodonium pyrenesulfonate, di (3,4-dimethylphenyl) iodonium n-dodecylbenzenesulfonate, di (3,4-dimethylphenyl) iodonium p-toluenesulfonate, di (3,4-dimethylphenyl) iodonium benzenesulfonate, di (3,4-dimethylphenyl) iodonium 10-camphorsulfonate , Di (3,4-dimethylphenyl) iodonium n-octanesulfonate, di (3,4-dimethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (3,4-dimethylphenyl) Iodonium 4-trifluoromethylbenzenesulfonate, di (3,4-dimethylphenyl) iodonium perfluorobenzenesulfonate,
[176] p-nitrophenyl phenyl iodonium trifluoromethanesulfonate, p-nitrophenyl phenyl iodonium nonafluoro-n-butanesulfonate, p-nitrophenyl phenyl iodonium perfluoro-n- Octanesulfonate, p-nitrophenyl phenyl iodonium pyrenesulfonate, p-nitrophenyl phenyl iodonium n-dodecylbenzenesulfonate, p-nitrophenyl phenyl iodonium p-toluenesulfonate, p Nitrophenyl phenyl iodonium benzenesulfonate, p-nitrophenyl phenyl iodonium 10-camphorsulfonate, p-nitrophenyl phenyl iodonium n-octane sulfonate, p-nitrophenyl phenyl iodo 2-trifluoromethylbenzenesulfonate, p-nitrophenylphenyliodonium 4-trifluoromethylbenzenesulfonate, p-nitrophenylphenyliodonium perfluorobenzenesulfonate, di (3- Nitrophenyl) iodonium trifluoromethanesulfonate, di (3-nitrophenyl) iodonium Nonafluoro-n-butanesulfonate, di (3-nitrophenyl) iodonium perfluoro-n-octanesulfonate, di (3-nitrophenyl) iodonium pyrensulfonate, di (3-nitrophenyl Iodonium n-dodecylbenzenesulfonate, di (3-nitrophenyl) iodonium p-toluenesulfonate, di (3-nitrophenyl) iodonium benzenesulfonate, di (3-nitrophenyl) io Donium 10-camphorsulfonate, di (3-nitrophenyl) iodonium n-octanesulfonate, di (3-nitrophenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (3-nitrophenyl Iodonium 4-trifluoromethylbenzenesulfonate, di (3-nitrophenyl) iodonium perfluorobenzenesulfonate,
[177] 4-methoxyphenyl phenyl iodonium trifluoromethanesulfonate, 4-methoxyphenyl phenyl iodonium nonafluoro-n-butanesulfonate, 4-methoxyphenyl phenyl iodonium perfluoro -n-octanesulfonate, 4-methoxyphenylphenyl iodonium pyrenesulfonate, 4-methoxyphenylphenyl iodonium n-dodecylbenzenesulfonate, 4-methoxyphenylphenyl iodonium p Toluenesulfonate, 4-methoxyphenyl phenyl iodonium benzenesulfonate, 4-methoxyphenyl phenyl iodonium 10-camphorsulfonate, 4-methoxyphenyl phenyl iodonium n-octane sulfonate , 4-methoxyphenyl phenyl iodonium 2-trifluoromethylbenzenesulfonate, 4-methoxyphenyl phenyl iodonium 4-trifluoromethylbenzenesulfonate, 4-methoxyphenyl phenyl iodo Perfluorobenzenesulfonate,
[178] Di (4-chlorophenyl) iodonium trifluoromethanesulfonate, di (4-chlorophenyl) iodonium nonafluoro-n-butanesulfonate, di (4-chlorophenyl) iodonium perfluoro -n-octanesulfonate, di (4-chlorophenyl) iodonium pyrensulfonate, di (4-chlorophenyl) iodonium n-dodecylbenzenesulfonate, di (4-chlorophenyl) iodonium p Toluenesulfonate, di (4-chlorophenyl) iodonium benzenesulfonate, di (4-chlorophenyl) iodonium 10-camphorsulfonate, di (4-chlorophenyl) iodonium n-octanesulfonate , Di (4-chlorophenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (4-chlorophenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (4-chlorophenyl) iodo Perfluorobenzenesulfonate,
[179] Di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) Iodonium perfluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium pyrenesulfonate, di (4-trifluoromethylphenyl) iodonium n-dodecylbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodonium benzenesulfonate, di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate , Di (4-trifluoromethylphenyl) iodonium n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (4-trifluoromethylphenyl) Iodonium 4-trifluoromethylbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium perfluoro Xen-sulfonate,
[180] Di (1-naphthyl) iodonium trifluoromethanesulfonate, di (1-naphthyl) iodonium nonafluoro-n-butanesulfonate, di (1-naphthyl) iodonium perfluoro -n-octanesulfonate, di (1-naphthyl) iodonium pyrensulfonate, di (1-naphthyl) iodonium n-dodecylbenzenesulfonate, di (1-naphthyl) iodonium p Toluenesulfonate, di (1-naphthyl) iodonium benzenesulfonate, di (1-naphthyl) iodonium 10-camphorsulfonate, di (1-naphthyl) iodonium n-octanesulfonate , Di (1-naphthyl) iodonium 2-trifluoromethylbenzenesulfonate, di (1-naphthyl) iodonium 4-trifluoromethylbenzenesulfonate, di (1-naphthyl) iodo Perfluorobenzenesulfonate,
[181] Biphenylene iodonium trifluoromethanesulfonate, biphenylene iodonium nonafluoro-n-butanesulfonate, biphenylene iodonium perfluoro-n-octanesulfonate, biphenylene iodo Pyrenesulfonate, biphenylene iodonium n-dodecylbenzenesulfonate, biphenylene iodonium p-toluenesulfonate, biphenylene iodonium benzenesulfonate, biphenylene iodonium 10-camphor Sulfonate, biphenylene iodonium n-octane sulfonate, biphenylene iodonium 2-trifluoromethylbenzenesulfonate, biphenylene iodonium 4-trifluoromethylbenzenesulfonate, biphenylene Iodonium perfluorobenzenesulfonate,
[182] 2-chlorobiphenyleneiodonium trifluoromethanesulfonate, 2-chlorobiphenyleneiodonium nonafluoro-n-butanesulfonate, 2-chlorobiphenyleneiodonium perfluoro-n- Octanesulfonate, 2-chlorobiphenyleneiodonium pyrenesulfonate, 2-chlorobiphenyleneiodonium n-dodecylbenzenesulfonate, 2-chlorobiphenyleneiodonium p-toluenesulfonate, 2 -Chlorobiphenylene iodonium benzenesulfonate, 2-chlorobiphenylene iodonium 10-camphorsulfonate, 2-chlorobiphenylene iodonium n-octanesulfonate, 2-chlorobiphenylene iodo 2-trifluoromethylbenzenesulfonate, 2-chlorobiphenyleneiodonium 4-trifluoromethylbenzenesulfonate, 2-chlorobiphenyleneiodonium perfluorobenzenesulfonate,
[183] Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfon Phosphorium n-dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, triphenylsulfon Phosphorium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium 1-naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, triphenylsulfonium Hexafluoroantimonate,
[184] 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyl diphenylsulfonium Perfluoro-n-octanesulfonate, 4-t-butylphenyldiphenylsulfonium pyrenesulfonate, 4-t-butylphenyldiphenylsulfonium n-dodecylbenzenesulfonate, 4-t-butylphenyl Diphenylsulfonium p-toluenesulfonate, 4-t-butylphenyldiphenylsulfonium benzenesulfonate, 4-t-butylphenyldiphenylsulfonium 10-camphorsulfonate, 4-t-butylphenyl Diphenylsulfonium n-octanesulfonate, 4-t-butylphenyldiphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butylphenyldiphenylsulfonium 4-trifluoromethanebenzenesulfo Nate, 4-t-butylphenyl diphenylsulfonium perfluorobenzenesulfonate,
[185] 4-t-butoxyphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butoxyphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butoxyphenyldi Phenylsulfonium perfluoro-n-octanesulfonate, 4-t-butoxyphenyldiphenylsulfonium pyrenesulfonate, 4-t-butoxyphenyldiphenylsulfonium n-dodecylbenzenesulfonate, 4 -t-butoxyphenyl diphenylsulfonium p-toluenesulfonate, 4-t-butoxyphenyl diphenylsulfonium benzenesulfonate, 4-t-butoxyphenyl diphenylsulfonium 10-camphorsulfonate , 4-t-butoxyphenyl diphenylsulfonium n-octanesulfonate, 4-t-butoxyphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butoxyphenyldi Phenylsulfonium 4-trifluoromethylbenzenesulfonate, 4-t-butoxyphenyldiphenylsulfonium perfluorobenzenesulfonate,
[186] 4-hydroxyphenyl diphenylsulfonium trifluoromethanesulfonate, 4-hydroxyphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxyphenyl diphenylsulfonium perfluoro -n-octanesulfonate, 4-hydroxyphenyl diphenylsulfonium pyrenesulfonate, 4-hydroxyphenyl diphenylsulfonium n-dodecylbenzenesulfonate, 4-hydroxyphenyl diphenylsulfonium p Toluenesulfonate, 4-hydroxyphenyl diphenylsulfonium benzenesulfonate, 4-hydroxyphenyl diphenylsulfonium 10-camphorsulfonate, 4-hydroxyphenyl diphenylsulfonium n-octanesulfonate , 4-hydroxyphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-hydroxyphenyl diphenylsulfonium 4-trifluoromethylbenzenesulfonate, 4-hydroxyphenyldiphenylsul Phosphium perfluorobenzenesulfonate,
[187] Tri (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-methoxyphenyl) sulfonium perfluoro -n-octanesulfonate, tri (4-methoxyphenyl) sulfonium pyrenesulfonate, tri (4-methoxyphenyl) sulfonium n-dodecylbenzenesulfonate, tri (4-methoxyphenyl) sulfonium p Toluenesulfonate, tri (4-methoxyphenyl) sulfonium benzenesulfonate, tri (4-methoxyphenyl) sulfonium 10-camphorsulfonate, tri (4-methoxyphenyl) sulfonium n-octanesulfonate , Tri (4-methoxyphenyl) sulfonium 2-trifluoromethylbenzenesulfonate, tri (4-methoxyphenyl) sulfonium 4-trifluoromethylbenzenesulfonate, tri (4-methoxyphenyl) sul Phosphium perfluorobenzenesulfonate,
[188] Di (4-methoxyphenyl) p-toluylsulfonium trifluoromethanesulfonate, di (4-methoxyphenyl) p-toluylsulfonium nonafluoro-n-butanesulfonate, di (4-meth Methoxyphenyl) p-toluylsulfonium perfluoro-n-octanesulfonate, di (4-methoxyphenyl) p-toluylsulfonium pyrenesulfonate, di (4-methoxyphenyl) p-tolylsul Phenyl n-dodecylbenzenesulfonate, di (4-methoxyphenyl) p-toluylsulfonium p-toluenesulfonate, di (4-methoxyphenyl) p-toluylsulfonium benzenesulfonate, di (4 -Methoxyphenyl) p-toluylsulfonium 10-camphorsulfonate, di (4-methoxyphenyl) p-toluylsulfonium n-octanesulfonate, di (4-methoxyphenyl) p-tolylsul Phosphorus 2-trifluoromethylbenzenesulfonate, di (4-methoxyphenyl) p-tolylsulfonium 4-trifluoromethylbenzenesulfonate, di (4-methoxyphenyl) p-tolylsulfonium purple Fluorobenzenesulfonate,
[189] Phenyl tetramethylenesulfonium trifluoromethanesulfonate, phenyl tetramethylenesulfonium nonafluoro-n-butanesulfonate, phenyl tetramethylenesulfonium perfluoro-n-octanesulfonate, phenyl tetramethylenesulfonate Phenium pyrenesulfonate, phenyl tetramethylenesulfonium n-dodecylbenzenesulfonate, phenyl tetramethylenesulfonium p-toluenesulfonate, phenyl tetramethylenesulfonium benzenesulfonate, phenyl tetramethylenesulfonium 10-campo Sulfonate, phenyl tetramethylenesulfonium n-octanesulfonate, phenyl tetramethylenesulfonium 2-trifluoromethylbenzenesulfonate, phenyl tetramethylenesulfonium 4-trifluoromethylbenzenesulfonate, phenyl tetra Methylenesulfonium perfluorobenzenesulfonate,
[190] 4-hydroxyphenyl tetramethylenesulfonium trifluoromethanesulfonate, 4-hydroxyphenyl tetramethylenesulfonium nonafluoro-n-butanesulfonate, 4-hydroxyphenyl tetramethylenesulfonium perfluoro -n-octanesulfonate, 4-hydroxyphenyl tetramethylenesulfonium pyrenesulfonate, 4-hydroxyphenyl tetramethylenesulfonium n-dodecylbenzenesulfonate, 4-hydroxyphenyl tetramethylenesulfonium p Toluenesulfonate, 4-hydroxyphenyl tetramethylenesulfonium benzenesulfonate, 4-hydroxyphenyl tetramethylenesulfonium 10-camphorsulfonate, 4-hydroxyphenyl tetramethylenesulfonium n-octanesulfonate , 4-hydroxyphenyl tetramethylenesulfonium 2-trifluoromethylbenzenesulfonate, 4-hydroxyphenyl tetramethylenesulfonium 4-trifluoromethylbenzenesulfonate, 4-hydroxyphenyl tetramethylene sulfonate Phonium Fur By Luo benzenesulfonate,
[191] Phenyl biphenylenesulfonium trifluoromethanesulfonate, phenyl biphenylenesulfonium nonafluoro-n-butanesulfonate, phenyl biphenylenesulfonium perfluoro-n-octane sulfonate, phenyl biphenylene sulfonate Phenyl pyrenesulfonate, phenyl biphenylenesulfonium n-dodecylbenzenesulfonate, phenyl biphenylenesulfonium p-toluenesulfonate, phenyl biphenylenesulfonium benzenesulfonate, phenyl biphenylenesulfonium 10-camphor Sulfonate, phenyl biphenylenesulfonium n-octanesulfonate, phenyl biphenylenesulfonium 2-trifluoromethylbenzenesulfonate, phenyl biphenylenesulfonium 4-trifluoromethylbenzenesulfonate, phenyl bi Phenylenesulfonium perfluorobenzenesulfonate,
[192] (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-phenylthiophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-phenylthiophenyl) di Phenylsulfonium perfluoro-n-octanesulfonate, (4-phenylthiophenyl) diphenylsulfonium pyrenesulfonate, (4-phenylthiophenyl) diphenylsulfonium n-dodecylbenzenesulfonate, ( 4-phenylthiophenyl) diphenylsulfonium p-toluenesulfonate, (4-phenylthiophenyl) diphenylsulfonium benzenesulfonate, (4-phenylthiophenyl) diphenylsulfonium 10-camphorsulfonate , (4-phenylthiophenyl) diphenylsulfonium n-octanesulfonate, (4-phenylthiophenyl) diphenylsulfonium 2-trifluoromethylbenzenesulfonate, (4-phenylthiophenyl) di Phenylsulfonium 4-trifluoromethylbenzenesulfonate, (4-phenylthiophenyl) -diphenylsulfonium perfluorobenzenesulfonate,
[193] 4,4'-bis (diphenylsulfoniophenyl) sulfide di (trifluoromethanesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (nonafluoro-n- Butanesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (perfluoro-n-octanesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide Di (pyrenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (n-dodecylbenzenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide Di (p-toluenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (benzenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di ( 10-camphorsulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulphide di (n-octanesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulphide di ( 2-trifluoromethylbenzenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (4-trifluoromethylbenzenesulfonate), 4,4'-bis ( Diphenylsulfoniophenyl) sulphide di (perfluorobenzenesulfonate),
[194] 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-naph Tyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxy-1-naphthyltetrahydroti Ophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluor Romethanesulfonate, 4- (1'-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2'-methoxyethoxy) -1-naphthyltetra Hydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluor Methanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoro Methanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium tri Fluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2'-tetrahydrofuranyloxy) -1-naphthyltetra Hydrothiophenium trifluoromethanesulfonate, 4- (2'-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetra Hydrothiophenium trifluoromethanesulfonate, 1- (naphthylacetomethyl) tetrahydroti A penyum trifluoromethyl and the like can be mentioned methane sulfonate.
[195] ② sulfone compounds:
[196] As a sulfone compound, (beta) -keto sulfone, (beta) -sulfonyl sulfone, these (alpha)-diazo compounds, etc. are mentioned, for example.
[197] Specific examples of the sulfone compound include phenacylphenyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane, 4-trisfenacyl sulfone, and the like.
[198] ③ sulfonic acid ester compound:
[199] As a sulfonic acid ester compound, an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, an imino sulfonate, etc. are mentioned, for example.
[200] Specific examples of the sulfonic acid ester compound include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonnafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl -9,10- diethoxyanthracene-2-sulfonate, α-methylolbenzoin tosylate, α-methylolbenzoin n-octanesulfonate, α-methylolbenzoin trifluoromethanesulfonate, α- Methylol benzoin n-dodecanesulfonate etc. are mentioned.
[201] ④ sulfonyloxyimide compound:
[202] As a sulfonyloxyimide compound, the compound represented by following formula (8) is mentioned, for example.
[203]
[204] In formula, R <^3> represents bivalent groups, such as a linear, branched or cyclic alkylene group, arylene group, and an alkoxylene group, and R <^4> is a linear, branched or cyclic alkyl group, an aryl group, a straight chain, and a branch. Monovalent groups, such as a ground or cyclic halogen substituted alkyl group and a halogen substituted aryl group, are shown.
[205] As a specific example of a sulfonyloxyimide compound,
[206] N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (tri Fluoromethylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (Trifluoromethylsulfonyloxy) naphthylimide,
[207] N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsul Ponyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (10-camphorsulfonyl Oxy) naphthylimide,
[208] N- (n-octanesulfonyloxy) succinimide, N- (n-octanesulfonyloxy) phthalimide, N- (n-octanesulfonyloxy) diphenylmaleimide, N- (n-octanesul Ponyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (n-octanesulfonyl Oxy) naphthylimide,
[209] N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesul Ponyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (p-toluenesulfonyl Oxy) naphthylimide,
[210] N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) Diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylbenzene Sulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxyimide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide,
[211] N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) Diphenylmaleimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-trifluoromethylbenzene Sulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide,
[212] N- (perfluorobenzenesulfonyloxy) succinimide, N- (perfluorobenzenesulfonyloxy) phthalimide, N- (perfluorobenzenesulfonyloxy) diphenylmaleimide, N- (purple Fluorobenzenesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (perfluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (Perfluorobenzenesulfonyloxy) naphthylimide,
[213] N- (1-naphthalenesulfonyloxy) succinimide, N- (1-naphthalenesulfonyloxy) phthalimide, N- (1-naphthalenesulfonyloxy) diphenylmaleimide, N- (1-naphthalenesul Ponyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (1-naphthalenesulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (1-naphthalenesulfonyl Oxy) naphthylimide,
[214] N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n-butanesulfonyloxy) Diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (nonafluoro-n-butane Sulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxyimide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide,
[215] N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) phthalimide, N- (perfluoro-n-octanesulfonyloxy) Diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (perfluoro-n-octane Sulfonyloxy) -7-oxabicyclo [2,2.1] hepto-5-ene-2,3-dicarboxyimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxyimide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide,
[216] N- (benzenesulfonyloxy) succinimide, N- (benzenesulfonyloxy) phthalimide, N- (benzenesulfonyloxy) diphenylmaleimide, N- (benzenesulfonyloxy) bicyclo [2.2. 1] hepto-5-ene-2,3-dicarboxyimide, N- (benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N -(Benzenesulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (benzenesulfonyloxy) naphthylimide, etc. are mentioned.
[217] ⑤ disulfonyldiazomethane compounds:
[218] As a disulfonyl diazomethane compound, the compound represented by following formula (9) is mentioned, for example.
[219]
[220] In formula, R <^5> and R <^6> represents monovalent groups, such as a linear, branched or cyclic alkyl group, an aryl group, a linear, branched or cyclic halogen substituted alkyl group, and a halogen substituted aryl group independently of each other.
[221] Specific examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and bis (p-toluenesul Ponyl) diazomethane, bis (2, 4- dimethylphenylsulfonyl) diazomethane, methylsulfonyl p-toluenesulfonyl diazomethane, bis (4-t- butylphenylsulfonyl) diazomethane, bis ( 4-chlorophenylsulfonyl) diazomethane, cyclohexylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl 1- (1 ', 1'-dimethylethylsulfonyl) diazomethane, bis ( 1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sul Ponyyl) diazomethane, bis (1, 4- dioxaspiro [4.5] decan-7-sulfonyl) diazomethane, etc. are mentioned.
[222] ⑥ disulfonyl methane derivatives:
[223] As a disulfonyl methane derivative, the compound represented by following formula (10) is mentioned, for example.
[224]
[225] Wherein R ⁷ and R ⁸ independently of each other represent a monovalent linear or branched aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group or another monovalent organic group including a hetero atom, and V and W are mutually Independently an aryl group, a hydrogen atom, a monovalent linear or branched aliphatic hydrocarbon group or another monovalent organic group comprising a hetero atom, and at least one of V and W is an aryl group, or V and W are mutually Connected to form a monocyclic or polycyclic ring including one or more unsaturated bonds, or V and W are linked to each other to
[226]
[227] (V 'and W', independently of one another, represent a hydrogen atom, a halogen atom, a straight or branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, or V 'bonded to the same or different carbon atom.) W 'is connected to each other to form a carbon monocyclic structure, and a plurality of V' and W 'may be the same or different from each other, n is an integer of 2 to 10) to form a group represented by.
[228] Among these (B) acid generators, (1) onium salts, (4) sulfonyloxyimide compounds, (6) disulfonylmethane derivatives and the like are preferable, and bis (4-t-butylphenyl) iodonium nonafluoro-n-butane is particularly preferred. Sulfonates, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane, etc. are preferable.
[229] Said (B) acid generator can be used individually or in mixture of 2 or more types.
[230] In the present invention, the amount of the acid generator (B) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight per 100 parts by weight of the polymer (A).
[231] In the radiation-sensitive resin composition of the present invention, an acid having an action of controlling the diffusion phenomenon of the acid generated from the acid generator (B) into the resist film by exposure and suppressing an undesired chemical reaction in the non-exposed region. It is preferable to mix | blend a diffusion control agent.
[232] By using such an acid diffusion control agent, the storage stability of a composition is improved, the resolution is further improved as a resist, and the line width change of a resist pattern according to PED fluctuation can be further suppressed, and process stability is very excellent.
[233] As the acid diffusion control agent, a nitrogen-containing organic compound whose basicity does not change by exposure and heat treatment in the formation process of the resist pattern is preferable.
[234] As such a nitrogen-containing organic compound, for example, a compound represented by the following formula (11) (hereinafter referred to as "nitrogen-containing compound (I)"), a diamino compound containing two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen) Containing compounds (II) ", polyamino polymers containing three or more nitrogen atoms (hereinafter referred to as" nitrogen containing compounds (III) "), amide group containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like. Can be mentioned.
[235]
[236] In formula, R <^9> , R <^10> and R <^11> represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group independently of each other, and these groups may be substituted by functional groups, such as a hydroxyl group, for example. It may be.
[237] As nitrogen-containing compound (I), For example, Monoalkylamines, such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, methyl Dialkylamines such as cyclohexylamine and dicyclohexylamine; Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n- Trialkylamines such as nonylamine, tri-n-decylamine, dimethyl cyclohexylamine, methyl dicyclohexylamine, and tricyclohexylamine; Aromatics such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine Amines; and the like.
[238] As the nitrogen-containing compound (II), for example, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine , Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl Amine, 2,2-bis (4'-aminophenyl) propane, 2- (3'-aminophenyl) -2- (4'-aminophenyl) propane, 2- (4'-aminophenyl) -2- ( 3'-hydroxyphenyl) propane, 2- (4'-aminophenyl) -2- (4'-hydroxyphenyl) propane, 1,4-bis [1 '-(4 "-aminophenyl) -1' -Methylethyl] benzene, 1,3-bis [1 '-(4 "-aminophenyl) -1'-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) Ether and the like.
[239] Examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, and (co) polymers of N-2-dimethylaminoethylacrylamide.
[240] Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, Pyrrolidone, N-methylpyrrolidone, etc. are mentioned.
[241] Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n. -Butylthiourea etc. are mentioned.
[242] As said nitrogen-containing heterocyclic compound, For example, imidazole, such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl- 2-phenylimidazole, 2-phenyl benzimidazole; Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, 2,2 ', 6', 2 In addition to pyridines such as "-t-pyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, and acridine, pyrazine, pyrazole, pyridazine, quinozaline, purine, pyrrolidine, piperidine, mor Pauline, 4-methylmorpholine, piperazine, 1, 4- dimethyl piperazine, 1, 4- diazabicyclo [2.2.2] octane, etc. are mentioned.
[243] Among these nitrogen-containing organic compounds, nitrogen-containing compound (I), nitrogen-containing compound (II), nitrogen-containing heterocyclic compound, and the like are preferable.
[244] The acid diffusion control agents may be used alone or in combination of two or more thereof.
[245] As for the compounding quantity of an acid-diffusion control agent, 15 weight part or less is preferable per 100 weight part of (A) polymers, 0.001-10 weight part is more preferable, 0.005-5 weight part is especially preferable. In this case, when the compounding quantity of an acid diffusion control agent exceeds 15 weight part, there exists a tendency for the sensitivity as a resist and the developability of an exposure part to fall. Moreover, when the compounding quantity of an acid diffusion control agent is less than 0.001 weight part, there exists a possibility that the pattern shape and dimensional fidelity as a resist may fall depending on process conditions.
[246] In the radiation-sensitive resin composition of the present invention, a surfactant exhibiting an action of improving the coatability, striation of the composition, developability as a resist, and the like can be blended.
[247] As such surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenol ether, polyoxyethylene n-nonyl phenol ether, polyethylene glycol dilaurate, polyethylene Glycol distearate; and the like, and commercially available products include F-Top EF301, EF303, and EF352 (manufactured by Tochem Products, Inc.), Megafax F171, and F173 (manufactured by Dainippon Ink & Chemical Co., Ltd.); FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), KP341 (Shin-Etsu Chemical Co., Ltd.) KK Co., Ltd., Polyflow No. 75, No. 95 (Kyoeisha Chemical Co., Ltd. product), etc. are mentioned.
[248] The said surfactant can be used individually or in combination of 2 or more types. As for the compounding quantity of surfactant, 2 weight part or less is preferable per 100 weight part of (A) polymers.
[249] In addition, the radiation-sensitive resin composition of the present invention has the effect of absorbing radiation energy and transferring the energy to the acid generator (B), thereby increasing the amount of acid generated, thereby improving the apparent sensitivity of the resist. A sensitizer which has can be mix | blended.
[250] Examples of preferred sensitizers include benzophenones, rose bengals, anthracenes, and the like.
[251] As for the compounding quantity of a sensitizer, 50 weight part or less is preferable per 100 weight part of (A) polymers.
[252] Moreover, by mix | blending dye and / or a pigment, the latent image of an exposure part can be visualized and the influence of the halation at the time of exposure can be alleviated, and the adhesiveness with a board | substrate can be improved by mix | blending an adhesion | attachment adjuvant.
[253] In addition, as an additive other than the above, an antihalation agent such as 4-hydroxy-4'-methylchalcone, a shape improving agent, a storage stabilizer, an antifoaming agent, or the like may be added.
[254] In the radiation sensitive resin composition of this invention, after melt | dissolving uniformly in a solvent so that the total solid concentration may be 1-50 weight%, More preferably, 5-40 weight% at the time of the use, For example, the pore size 0.2 It is prepared as a composition solution by filtration with a filter of the order of μm.
[255] As a solvent used for manufacture of the said composition solution, for example
[256] Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate;
[257] Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether;
[258] Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether and propylene glycol di-n-butyl ether;
[259] Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate;
[260] Lactic acid esters such as methyl lactic acid, ethyl lactate, n-propyl lactic acid, and lactic acid i-propyl;
[261] N-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, propionic acid n Aliphatic carboxylic acid esters such as -butyl and i-butyl propionate;
[262] Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetic acid, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-ethoxy propionate methyl, 3-ethoxy propionate ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl- Other esters such as 3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate;
[263] Aromatic hydrocarbons such as toluene and xylene;
[264] Ketones such as methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone;
[265] Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; Lactones, such as (gamma) -butyrolactone, etc. are mentioned.
[266] These solvents may be used alone or in combination of two or more thereof.
[267] Formation of a resist pattern
[268] When forming a resist pattern from the radiation sensitive resin composition of this invention, the composition solution manufactured as mentioned above was made into silicon wafer, aluminum, for example, by appropriate application | coating means, such as rotational coating, casting | flow_spreading, and roll | coating. A resist film is formed by coating on a substrate such as a coated wafer, and optionally heat treatment (hereinafter referred to as "PB") at a temperature of about 70 to 160 degrees C in advance, and then exposed through a predetermined mask pattern. do.
[269] As radiation used for exposure, depending on the kind of (B) acid generator, charged particles, such as far ultraviolet rays and an electron beam, represented by ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), etc. X-rays, such as rays and synchrotron radiation, are appropriately selected and used. In addition, exposure conditions, such as an exposure amount, are suitably selected according to the compounding composition of a radiation sensitive resin composition, the kind of each additive, etc.
[270] In the present invention, in order to stably form a fine pattern with high precision, it is preferable to heat-process (for example, "PEB") for 30 second or more after exposure at the temperature of 70-160 degreeC, for example. In this case, when the temperature of PEB is less than 70 degreeC, there exists a possibility that the variation of a sensitivity may become large according to the kind of board | substrate.
[271] Then, using alkaline developing solution, Preferably it is 10 to 200 second at 10-50 degreeC, More preferably, it is 15 to 100 second at 15-30 degreeC, More preferably, on the conditions of 15 to 90 second at 20-25 degreeC By developing, a predetermined resist pattern is formed.
[272] Examples of the alkali developer include alkali metal hydroxides, ammonia water, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1 or more types of alkaline compounds, such as 1,8- diazabicyclo- [5.4.0] -7-undecene and 1,5- diazabicyclo- [4.3.0] -5-nonene, are preferably 1- Alkaline aqueous solution melt | dissolved so that it may become 10 weight%, More preferably, 1 to 5 weight%, More preferably, 1 to 3 weight% concentration is used.
[273] Moreover, you may add suitably water-soluble organic solvents, such as methanol and ethanol, and surfactant to the developing solution containing the said alkaline aqueous solution. Moreover, after image development with alkaline developing solution, it is preferable to wash with water and to dry.
[274] In forming the resist pattern, an organic or inorganic antireflection film may be formed on the substrate in advance in order to maximize the potential of the radiation-sensitive resin composition, and also in order to prevent the influence of basic impurities or the like contained in the environmental atmosphere. A protective film can be provided on a film, or these techniques can also be used together.
[9] It is an object of the present invention to provide a vinylphenylpropionic acid derivative which may include an acid-decomposable substituent in view of the above situation in the prior art.
[10] Another object of the present invention is to provide an industrially advantageous production method for producing the vinylphenylpropionic acid derivative of the present invention.
[11] It is still another object of the present invention to provide a polymer having a very low absorption to radiation and particularly useful as a resin component in a radiation sensitive resin composition which is preferable for chemically amplified resists.
[12] It is still another object of the present invention to contain a polymer, to reduce the difference in effective exposure between the upper and lower portions of the resist film, to ensure the rectangularity of the pattern even at the fine pattern size, and at the same time to excimer laser A radiation sensitive resin composition useful as a chemically amplified resist having high sensitivity (low exposure energy amount) to various radiations such as charged particle beams such as far ultraviolet rays, electron beams, and X-rays such as synchrotron radiation.
[13] Still another object of the present invention is to provide a radiation-sensitive resin composition which does not change the line width of a pattern or become a T-shape due to PED variation, and also has excellent resolution performance.
[14] Still other objects and advantages of the present invention will become apparent from the following description.
[15] According to the present invention, the above objects and advantages of the present invention are firstly achieved by a vinylphenylpropionic acid derivative represented by the following general formula (1).
[16]
[17] In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> and R <^3> may be same or different, respectively, and represents a hydrogen atom, the C1-C8 alkyl group which may be substituted, or a phenyl group which may be substituted, Z ¹ is a group represented by the following formula (2) or a group represented by the following formula (3).
[18]
[19] Wherein R ⁴ , R ⁵ and R ⁶ may be the same or different and may each be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted or a phenyl group which may be substituted, or R ⁴ , R ⁵ and R Any two of ⁶ may be bonded to each other to form a cyclic aliphatic group together with the carbon atom to which they are bonded.
[20]
[21] In formula, R <^7> , R <^8> and R <^9> may be same or different, respectively, and represent a hydrogen atom, a C1-C8 alkyl group which may be substituted, or a phenyl group which may be substituted, or R <^7> , R <^8> And any two of R ⁹ may be bonded to each other to form a cyclic aliphatic group together with the carbon atom to which they are bonded.
[22] In addition, the above object and advantage of the present invention, (i) reacting the acetic acid ester represented by the formula (4-1) and alkyl phosphine represented by the formula (4-2) represented by the formula (4-3) To produce a quaternary phosphonium salt of 1, (ii) reacting the resulting first quaternary phosphonium salt with a base to produce an inylide represented by the following formula (4-4), and (iii) a resulting inylide Reacting with a styrene derivative represented by the following formula (4-5) to produce a second quaternary phosphonium salt represented by the following formula (4-6), and then (iv) hydrolyzing the resulting quaternary phosphonium salt It is achieved by a method for producing a vinylphenylpropionic acid derivative represented by the formula (1) characterized in that.
[23] <Formula 4-1>
[24]
[25] In the formula, the definition of R ³ is the same as the formula (1), Z ² is a group represented by the following formula (2 ') or a group represented by the formula (3), X ₁ is a leaving group.
[26] <Formula 2 '>
[27]
[28] Wherein R ¹⁰ , R ¹¹ and R ¹² may be the same or different and may each be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted or a phenyl group which may be substituted, or R ¹⁰ , R ¹¹ and R ¹² Any two of them may be bonded to each other to form a cyclic aliphatic group together with the carbon atoms to which they are bonded.
[29] <Formula 4-2>
[30]
[31] In formula, R <^13> , R <^14> and R <^15> may be same or different, respectively, and is a C1-C8 alkyl group which may be substituted.
[32] <Formula 4-3>
[33]
[34] In the formula, the definition of R ³ is the same as in formula (1), the definitions of Z ² and X ₁ are the same as in formula (4-1), and the definitions of R ¹³ , R ¹⁴ and R ¹⁵ are the same as in formula (4-2).
[35] <Formula 4-4>
[36]
[37] In the formula, the definition of R ³ is the same as in formula 1, the definition of Z ² is the same as in formula 4-1, and the definition of R ¹³ , R ¹⁴ and R ¹⁵ is the same as in formula 4-2.
[38] <Formula 4-5>
[39]
[40] In the formula, the definition of R ¹ and R ² is the same as in the above formula (1), X ₂ is a leaving group.
[41] <Formula 4-6>
[42]
[43] Wherein, the definitions of R ¹ , R ^2, and R ³ are the same as in Formula 1, the definition of Z ² is the same as in Formula 4-1, and the definitions of R ¹³ , R ^14, and R ¹⁵ are the same as in Formula 4-2. same.
[44] According to the present invention, the above objects and advantages of the present invention comprise a third repeating unit represented by the following general formula (1 '), and at the same time the polystyrene reduced weight average molecular weight by gel permeation chromatography (GPC) is 1,000 to Achieved by a polymer of 500,000.
[45] <Formula 1 '>
[46]
[47] In formula, the definition of R <^1> , R <^2> , R <^3> and Z <^1> is the same as that of the said Formula (1).
[48] According to the present invention, the above objects and advantages of the present invention are finally achieved by a radiation-sensitive resin composition comprising (A) the polymer of the present invention and (B) a radiation-sensitive acid generator. .
[275] Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these.
[276] <Example 1>
[277] 47 g (0.23 mol) of tri n-butylphosphine and 90 ml of tetrahydrofuran (THF) were placed in a 1 L three-neck flask, and 44.8 g (0.23 mol) of t-butylbromoacetate was stirred at room temperature under a stream of nitrogen. Was added dropwise and stirred for 12 hours. Thereafter, the reaction vessel was ice-cooled, and 30 g (0.27 mol) of t-butoxy potassium dissolved in 100 ml of THF was added dropwise and stirred for 45 minutes, and then the reactor was returned to room temperature, and 2,4,6-tris ( 0.5 g of 3 ', 5'-di-t-butyl-4'-hydroxybenzyl) methylstyrene was added. Subsequently, 40 g (0.26 mol) of p-chloromesitylene was dripped, and it stirred at 40 degreeC for 12 hours, 140 g of 10% potassium carbonate aqueous solution was added, and it stirred at 40 degreeC for 8 hours, and hydrolyzed. THF in the reaction solution was distilled off under reduced pressure, the reaction product was extracted with n-hexane, washed with saturated brine, purified by silica gel column chromatography, and represented by the following chemical formula as a colorless transparent liquid. 38 g of 4-vinylphenylpropionate t-butyl, molecular formula: C ₁₅ H ₂₀ O ₂ ) was obtained. The yield was 71%. Elemental analysis (weight%) was C 77.32 (calculated value 77.55) and H 8.44 (calculated value 8.68). 1 shows the nuclear magnetic resonance spectrum of the compound, and FIG. 2 shows the infrared absorption spectrum.
[278]
[279] <Example 2>
[280] (1) Synthesis of 4-vinylphenylpropionic acid (Formula 5-1)
[281] Into a 1 L three-necked flask, 20 g (0.1 mol) of ethyl 4-vinylphenylpropionate was added, and 100 ml of THF was added to dissolve well, and 2,4,6-tris (3 ', 5'-di-t- 0.3 g of butyl-4'-hydroxybenzyl) mesitylene was added. 100 mL of 1.5N sodium hydroxide aqueous solution was dripped at room temperature, and it stirred at 50 degreeC for 1 hour and 30 minutes. Subsequently, THF was distilled off under reduced pressure, extracted twice with 100 ml of n-hexane, and 15 ml of 37% concentrated hydrochloric acid was added dropwise while stirring to form a white precipitate. The precipitate was separated by filtration and sufficiently washed with cold water, followed by vacuum drying at 50 ° C. for 12 hours to obtain 12 g of 4-vinylphenylpropionic acid (C ₁₁ H ₁₂ O ₂ ). The yield was 68%. Elemental analysis (wt%) was C 74.76 (calculated value 74.98) and H 6.91 (calculated value 6.86). FIG. 3 shows the nuclear magnetic resonance spectrum of the compound, and FIG. 4 shows the infrared absorption spectrum.
[282] (2) Synthesis of 4-vinylphenylpropionic acid-2'-tetrahydropyranyl
[283] In a 200-neck three-necked flask equipped with a cooling tube, 17.6 g (0.1 mol) of 4-vinylphenylpropionic acid obtained in (1), 2,4,6-tris (3 ', 5'-di-t-butyl-4 0.5 g of '-hydroxybenzyl) mesitylene and 20 ml of 3,4-dihydro-2H-pyran were added and stirred at 60 ° C for 10 hours. Thereafter, the reaction solution was returned to room temperature and purified by silica gel column chromatography to obtain a compound of the present invention represented by the following formula (4-vinylphenylpropionic acid-2'-tetrahydropyranyl, molecular formula: C ₁₆ H ₂₀ O ₃ ) 14 g. The yield was 54%. Elemental analysis (wt%) was C 73.73 (calculated value 73.82) and H 7.65 (calculated value 7.74). FIG. 5 shows the nuclear magnetic resonance spectrum of the compound, and FIG. 6 shows the infrared absorption spectrum.
[284]
[285] <Example 3>
[286] Ethyl bromoacetate 38 g (0.23 mol) of the one except that, in Example 1 in the same manner to the compound represented by the formula with (4-phenyl ethyl propionate, molecular _{formula: C 13 H 16 O 2)} 34 g to give the . The yield was 73%. Elemental analysis (weight%) was C 76.78 (calculated value 76.44) and H 7.84 (calculated value 7.90). FIG. 7 shows the nuclear magnetic resonance spectrum of the compound, and FIG. 8 shows the infrared absorption spectrum.
[287]
[288] <Example 4>
[289] A compound represented by the following formula (4-vinylphenylpropionic acid 1-hexadecanyl, Molecular Formula: C ₂₇ H) in the same manner as in Example 1 except that 84 g (0.23 mol) of 1-hexadecanylbromoacetate was used. ₄₄ 0 ₂ ) 53 g were obtained. The yield was 57% (In addition, 1-hexadecanylbromoacetate used for this synthesis | combination was synthesize | combined by the conventional ester synthesis | combination method using bromoacetyl bromide and 1-hexadecanol). Elemental analysis (weight%) was C 80.78 (calculated value 80.94) and H 11.12 (calculated value 11.07). 9 shows the nuclear magnetic resonance spectrum of the compound, and FIG. 10 shows the infrared absorption spectrum.
[290]
[291] Example 5
[292] 15 g of 4-vinylphenylpropionic acid t-butyl obtained in Example 1, 15 g of 1-acryloyloxy-3-hydroxyadamantane, p-acetoxystyrene 20 g, 0.34 g of t-dodecyl mercaptan, 1.68 g of azobisisobutyronitrile and 50 g of propylene glycol monomethyl ether were added, and the polymerization was carried out at 75 ° C. for 7 hours under a stream of nitrogen. After the completion of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, the precipitated polymer was separated by decantation, and then 15 g of triethylamine was added to react, and the acetoxy group in the p-acetoxystyrene unit was reacted. Hydrolysis.
[293] The composition of the obtained polymer is 4-vinylphenylpropionic acid t-butyl / 1-acryloyloxy-3-hydroxyadamantane / p-hydroxystyrene copolymer (copolymerization weight ratio = 30/30/40), and Mw is 14,000 and yield 70%. This polymer is called polymer (A-1).
[294] <Example 6>
[295] 15 g of 4-vinylphenylpropionic acid t-butyl obtained in Example 1, 15 g of 1-acryloyloxy-3-hydroxyadamantane, and Example 2 (1) in a 300 ml flask of nitrogen-substituted capacity 20 g of 4-vinylphenylpropionic acid obtained in the above, 0.32 g of t-dodecyl mercaptan, 1.61 g of azobisisobutyronitrile and 50 g of propylene glycol monomethyl ether were added, and polymerization was carried out at 75 ° C. for 7 hours under a stream of nitrogen. After the end of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, and the precipitated polymer was separated by decantation.
[296] The composition of the obtained polymer is 4-vinylphenylpropionic acid t-butyl / 1-acryloyloxy-3-hydroxyadamantane / 4-vinylphenylpropionic acid copolymer (copolymerization weight ratio = 30/30/40), and Mw is 14,000 and yield 78%. This polymer is called polymer (A-2).
[297] <Example 7>
[298] 20 g of 4-vinylphenylpropionic acid t-butyl obtained in Example 1, 10 g of 3-acryloyloxymethyl-8-hydroxytetracyclododecane, and p-acetoxy were carried out in a 300 ml flask of nitrogen-substituted capacity. 20 g of styrene, 0.32 g of t-dodecyl mercaptan, 1.62 g of azobisisobutyronitrile and 50 g of propylene glycol monomethyl ether were added and polymerized at 75 ° C. for 7 hours under a stream of nitrogen. After the completion of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, the precipitated polymer was separated by decantation, and then 15 g of triethylamine was added to react with the acetoxy group in the p-acetoxystyrene unit. Hydrolysis.
[299] The composition of the obtained polymer is 4-vinylphenylpropionate t-butyl / 3-acryloyloxymethyl-8-hydroxytetracyclododecane / p-hydroxystyrene copolymer (copolymer weight ratio = 40/20/40), Mw was 14,000 and the yield was 68%. This polymer is called polymer (A-3).
[300] <Example 8>
[301] 15 g of 4-vinylphenylpropionic acid 2'-tetrahydropyranyl obtained in Example 2 (2) and 15 g of 1-acryloyloxy-3-hydroxyadamantane were obtained in a nitrogen-substituted 300 ml eggplant flask. , 20 g of p-acetoxy styrene, 0.33 g of t-dodecyl mercaptan, 1.63 g of azobisisobutyronitrile and 50 g of propylene glycol monomethyl ether were added and polymerized at 75 ° C. for 7 hours under a stream of nitrogen. After the completion of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, the precipitated polymer was separated by decantation, and then 15 g of triethylamine was added to react with the acetoxy group in the p-acetoxystyrene unit. Hydrolysis.
[302] The composition of the obtained polymer was 4-vinylphenylpropionic acid 2'-tetrahydropyranyl / 1-acryloyloxy-3-hydroxyadamantane / p-hydroxystyrene copolymer (copolymerization weight ratio = 30/30/40) Mw was 14,000 and the yield was 72%. This polymer is called polymer (A-4).
[303] Example 9
[304] 15 g of 4-vinylphenylpropionic acid 2'-tetrahydropyranyl obtained in Example 2 (2) and 15 g of 1-acryloyloxy-3-hydroxyadamantane were obtained in a nitrogen-substituted 300 ml eggplant flask. , 20 g of 4-vinylphenylpropionic acid obtained in Example 2 (1), 0.31 g of t-dodecyl mercaptan, 1.57 g of azobisisobutyronitrile and 50 g of propylene glycol monomethyl ether were added, and 75 ° C under nitrogen stream. The polymerization was carried out at 7 hours. After the end of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, and the precipitated polymer was separated by decantation.
[305] The composition of the obtained polymer was 4-vinylphenylpropionic acid 2'-tetrahydropyranyl / 1-acryloyloxy-3-hydroxyadamantane / 4-vinylphenylpropionic acid copolymer (copolymerization weight ratio = 30/30/40) And Mw was 14,000 and the yield was 80%. This polymer is called polymer (A-5).
[306] <Example 10>
[307] 20 g of 4-vinylphenylpropionic acid 2'-tetrahydropyranyl obtained in Example 2 (2) and 3-acryloyloxymethyl-8-hydroxytetracyclododecane in 300 ml of nitrogen-substituted flasks 10 g, 20 g of p-acetoxystyrene, 0.31 g of t-dodecyl mercaptan, 1.56 g of azobisisobutyronitrile and 50 g of propylene glycol monomethyl ether were added, and the polymerization was carried out at 75 ° C. for 7 hours under a stream of nitrogen. After the completion of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, the precipitated polymer was separated by decantation, and then 15 g of triethylamine was added to react with the acetoxy group in the p-acetoxystyrene unit. Hydrolysis.
[308] The composition of the obtained polymer is 4-vinylphenylpropionic acid 2′-tetrahydropyranyl / 3-acryloyloxymethyl-8-hydroxytetracyclododecane / p-hydroxystyrene copolymer (copolymerization weight ratio = 40/20 / 40), Mw was 14,000, yield 67%. This polymer is called polymer (A-6).
[309] <Example 11>
[310] 12.5 g of 4-vinylphenylpropionic acid t-butyl obtained in Example 1, 12.5 g of 1-acryloyloxy-3-hydroxyadamantane, and Example 2 (1) were carried out in a 300 ml flask of nitrogen-substituted capacity. 22.5 g of 4-vinylphenylpropionic acid, 2.5 g of 2,5-dimethyl-2,5-hexanedioldiacrylate, 0.97 g of t-dodecylmercaptan, 1.62 g of azobisisobutyronitrile and propylene glycol monomethyl ether 60 g was added and superposed | polymerized at 75 degreeC under nitrogen stream for 7 hours. After the end of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, and the precipitated polymer was separated by decantation.
[311] The composition of the obtained polymer is 4-vinylphenyl propionic acid t-butyl / 1-acryloyloxy-3-hydroxyadamantane / 4-vinylphenylpropionic acid / 2,5-dimethyl-2,5-hexanediol diacrylate It was a copolymer (copolymer weight ratio = 25/25/45/5), Mw was 30,000 and the yield was 81%. This polymer is called polymer (A-7).
[312] <Example 12>
[313] 12.5 g of 4-vinylphenylpropionic acid t-butyl obtained in Example 1, 12.5 g of 1-acryloyloxy-3-hydroxyadamantane, and Example 2 (1) were carried out in a 300 ml flask of nitrogen-substituted capacity. 22.5 g of 4-vinylphenylpropionic acid, 2.5 g of tricyclodecane dimethanol diacrylate, 0.97 g of t-dodecyl mercaptan, 1.61 g of azobisisobutyronitrile and 60 g of propylene glycol monomethyl ether were added, followed by nitrogen. The polymerization was carried out at 75 ° C. for 7 hours under air flow. After the end of the polymerization, the reaction solution was cooled, poured into a large amount of methanol, and the precipitated polymer was separated by decantation.
[314] The composition of the obtained polymer is 4-vinylphenyl propionic acid t-butyl / 1-acryloyloxy-3-hydroxyadamantane / 4-vinylphenylpropionic acid / tricyclodecane dimethanol diacrylate 2.5 g copolymer (copolymerization weight ratio = 25/25/45/5), Mw was 30,000 and yield 78%. This polymer is called polymer (A-8).
[315] <Examples 13 to 22 and Comparative Example 1>
[316] Each component shown in Table 1 (where "part" is based on weight) was mixed to make a homogeneous solution, and then filtered with a Teflon membrane filter having a pore diameter of 0.2 µm to prepare a composition solution.
[317] Subsequently, each composition solution was spin-coated on a silicon wafer, and then PB was performed at the temperatures and times shown in Table 2 to form a resist film having a film thickness of 0.5 mu m. Then, the KrF excimer laser (wavelength 248 nm) manufactured by Nikon Corporation was used for this resist film, and the KrF excimer laser (wavelength 248 nm) was changed and exposed through the mask pattern. In addition, in some examples, a simple electron beam drawing device (acceleration voltage 50 KeV) was used instead of the KrF excimer laser, and the electron beam was exposed by changing the exposure amount through a mask pattern. After exposure, PEB was performed at the temperatures and times shown in Table 2.
[318] Thereafter, the solution was developed using an aqueous tetramethylammonium hydroxide solution, washed with water for 30 seconds, and dried to form a resist pattern.
[319] Table 3 shows the evaluation results of the examples and the comparative examples.
[320] Here, the measurement of Mw and the evaluation of each resist were performed by the following method.
[321] Mw
[322] Monodisperse polystyrene was used as a standard under analytical conditions of a flow rate of 1.0 ml / min, an eluting solvent tetrahydrofuran, and a column temperature of 40 ° C using a GPC column (two G2000HXL, one G3000HXL, and one G4000HXL) manufactured by Toso Corporation. It was measured by gel permeation chromatography (GPC).
[323] Sensitivity
[324] When the line-and-space pattern (1L1S) having a design line width of 0.22 µm was formed, an exposure amount formed with a line width of 1: 1 was regarded as an optimal exposure amount and evaluated at this optimum exposure amount.
[325] resolution
[326] When forming the line-and-space pattern 1L1S having a design line width of 0.22 µm, the minimum dimension of the resist pattern resolved when exposed at the optimum exposure dose was defined as the resolution.
[327] Radiation transmittance
[328] After spin-coating a composition solution on a circular quartz plate, the transmittance | permeability in wavelength 248nm of the resist film formed by PB was measured by the ultraviolet absorbance method. At this time, the film thickness of the resist film was measured by a stylus film thickness measuring apparatus, and the measured transmittance was normalized to a film thickness of 50 µm to obtain a radiation transmittance.
[329] PED stability
[330] When the PEB was developed immediately after the exposure and developed, the sample exposed at the optimum exposure dose was placed in a chamber in which the ammonia concentration in the atmosphere was controlled at 5 ppb for 2 hours, followed by the development of PEB, and the line and space pattern having a design line width of 0.22 μm. When (1LlS) was formed, the line width (Ltop) of the upper part of the pattern was measured with a scanning electron microscope, and the following reference | standard evaluated.
[331] 0.22 × 0.85 <Ltop <0.22 × 1.1: Good
[332] 0.22 × 0.85≥Ltop: thin and bad
[333] 0.22 × 1.1≤Ltop: Bad due to thick
[334] Each component other than the polymer (A-1)-(A-7) used by each Example and the comparative example is as follows.
[335] Other polymers
[336] a-1: p-hydroxy styrene / styrene / acrylic acid t-butyl copolymer
[337] (Copolymer weight ratio = 60/20/20, Mw = 14,000)
[338] (B) acid generator
[339] B-1: triphenylsulfonium trifluoromethanesulfonate
[340] B-2: N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide
[341] B-3: bis (4-t-butylphenyl) iodonium 10-camphorsulfonate
[342] B-4: bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate
[343] B-5: bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane
[344] Acid Diffusion Control
[345] C-1: N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine
[346] C-2: 2-phenylbenzimidazole
[347] C-3: tri-n-octylamine
[348] C-4: 2,2 ', 6', 2 "-t-pyridine
[349] C-5: 4-phenylpyridine
[350] menstruum
[351] D-1: ethyl lactate
[352] D-2: ethyl 3-ethoxypropionate
[353] D-3: Propylene Glycol Monomethyl Ether Acetate
[354] D-4: 2-heptanone
[355] Polymer (part)(B) acid generator (part)Acid Diffusion Control (part)Solvent (part) Example 13A-1 (100)B-3 (2.2) B-4 (2.4)C-1 (0.2)D-1 (400) D-2 (150) Example 14A-2 (100)B-3 (2.2) B-4 (2.4)C-1 (0.2)D-1 (400) D-3 (150) Example 15A-2 (100)B-2 (10.0)C-2 (0.1)D-1 (400) D-3 (150) Example 16A-3 (100)B-3 (2.2) B-4 (2.4)C-1 (0.2) C-5 (0.05)D-1 (400) D-2 (150) Example 17A-4 (100)B-5 (6.0)C-3 (0.1)D-1 (400) D-4 (150) Example 18A-5 (100)B-5 (6.0)C-1 (0.2)D-1 (400) D-2 (150) Example 19A-5 (100)B-1 (10.0)C-3 (0.1)D-1 (400) D-2 (150) Example 20A-6 (100)B-5 (6.0)C-2 (0.1)D-1 (400) D-3 (150) Example 21A-7 (100)B-3 (2.2) B-4 (2.4)C-1 (0.2)D-1 (400) D-4 (150) Example 22A-8 (100)B-2 (10.0) B-3 (2.0)C-4 (0.1)D-1 (400) D-3 (150) Comparative Example 1a-1 (100)B-3 (2.2) B-4 (2.4)C-1 (0.2)D-1 (400) D-2 (150)
[356] PBExposure light sourcePB Temperature (℃)Time in secondsTemperature (℃)Time in seconds Example 1314090KrF excimer laser14090 Example 1413060KrF excimer laser13090 Example 1513090KrF excimer laser11060 Example 1613090KrF excimer laser14090 Example 1711060KrF excimer laser10090 Example 1810060KrF excimer laser10090 Example 1911090Electron beam11590 Example 209090KrF excimer laser11090 Example 2114090KrF excimer laser14090 Example 2213090KrF excimer laser11090 Comparative Example 114090KrF excimer laser14090
[357] SensitivityResolution (μm)Radiation transmittance (%)PED stability Example 132.2 × 10 ² J / ㎡0.2080Good Example 142.8 × 10 ² J / ㎡0.1881Good Example 153.0 × 10 ² J / ㎡0.2085Good Example 163.2 × 10 ² J / ㎡0.1882Good Example 172.5 × 10 ² J / ㎡0.1886Good Example 183.3 × 10 ² J / ㎡0.1887Good Example 197 × 10 ^-2 C / ㎡0.1875Good Example 202.7 × 10 ² J / ㎡0.1888Good Example 213.0 × 10 ² J / ㎡0.1883Good Example 223.1 × 10 ² J / ㎡0.1881Good Comparative Example 13.6 × 10 ² J / ㎡0.2265Thick and bad
[358] According to the present invention as described above, a novel vinylphenylpropionic acid derivative can be obtained, and an appropriate substituent can be easily introduced. These vinylphenylpropionic acid derivatives have a polymerization activity and a polymer having physical properties according to the use can be obtained by using a vinylphenylpropionic acid derivative having an appropriate substituent introduced therein. There is also provided a method for easily synthesizing these novel vinylphenylpropionic acid derivatives.
[359] In particular, the polymer having the repeating unit represented by the above formula (1 ') as an essential unit has very low absorption to radiation, and is particularly useful as a resin component in a radiation sensitive resin composition which is preferable for chemically amplified resists. In addition, the radiation-sensitive resin composition of the present invention containing the polymer can reduce the difference in effective exposure amount between the upper and lower portions of the resist film, ensure the rectangularity of the pattern even in the fine pattern size, and at the same time KrF It has high sensitivity (low exposure energy amount) to various radiations such as X-rays such as far infrared rays, charged particle beams such as electron beams, synchrotron radiation, etc. represented by excimer lasers or ArF excimer lasers. It does not change or become a T-shape, and at the same time, the resolution performance is also excellent. Therefore, especially the radiation sensitive resin composition of this invention can be used very preferably as a chemical amplification type resist for manufacturing a semiconductor device which is expected to further refine further.

权利要求:
Claims (4)
[1" claim-type="Currently amended] Vinylphenyl propionic acid derivative represented by the following formula (1).
<Formula 1>

In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> and R <^3> may be same or different, respectively, and represents a hydrogen atom, the C1-C8 alkyl group which may be substituted, or a phenyl group which may be substituted, Z ¹ is a group represented by the following formula (2) or a group represented by the following formula (3).
<Formula 2>

Wherein R ⁴ , R ⁵ and R ⁶ may be the same or different and may each be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted or a phenyl group which may be substituted, or R ⁴ , R ⁵ and R Any two of ⁶ may be bonded to each other to form a cyclic aliphatic group together with the carbon atom to which they are bonded.
<Formula 3>

In formula, R <^7> and R <^8> may be same or different, respectively, and represents a hydrogen atom, the C1-C8 alkyl group which may be substituted, or a phenyl group which may be substituted, and R <^9> may have a C1-C8 which may be substituted. Or an alkyl group of 8 or a phenyl group which may be substituted, or any two of R ⁷ , R ⁸ and R ⁹ may be bonded to each other to form a cyclic aliphatic group together with the carbon atom to which they are bonded.
[2" claim-type="Currently amended] (i) reacting the acetic acid ester represented by the following formula (4-1) with the trialkylphosphine represented by the following formula (4-2) to produce a first quaternary phosphonium salt represented by the following formula (4-3), ( ii) reacting the resulting first quaternary phosphonium salt with a base to produce an inylide represented by the following formula (4-4), and (iii) the resulting inylide with a styrene derivative represented by the following formula (4-5) Reacting to produce a second quaternary phosphonium salt represented by the following formula (4-6), and then (iv) hydrolyzing the generated quaternary phosphonium salt (vinylphenyl propionic acid) represented by the formula (1) Process for the preparation of derivatives.
<Formula 4-1>

In the formula, the definition of R ³ is the same as the formula (1), Z ² is a group represented by the following formula (2 ') or a group represented by the formula (3), X ₁ is a leaving group.
<Formula 2 '>

Wherein R ¹⁰ , R ¹¹ and R ¹² may be the same or different and may each be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted or a phenyl group which may be substituted, or R ¹⁰ , R ¹¹ and R ¹² Any two of them may be bonded to each other to form a cyclic aliphatic group together with the carbon atoms to which they are bonded.
<Formula 4-2>

In formula, R <^13> , R <^14> and R <^15> may be same or different, respectively, and is a C1-C8 alkyl group which may be substituted.
<Formula 4-3>

In the formula, the definition of R ³ is the same as in formula (1), the definitions of Z ² and X ₁ are the same as in formula (4-1), and the definitions of R ¹³ , R ¹⁴ and R ¹⁵ are the same as in formula (4-2).
<Formula 4-4>

In the formula, the definition of R ³ is the same as in formula 1, the definition of Z ² is the same as in formula 4-1, and the definition of R ¹³ , R ¹⁴ and R ¹⁵ is the same as in formula 4-2.
<Formula 4-5>

In the formula, the definition of R ¹ and R ² is the same as in the above formula (1), X ₂ is a leaving group.
<Formula 4-6>

Wherein, the definitions of R ¹ , R ^2, and R ³ are the same as in Formula 1, the definition of Z ² is the same as in Formula 4-1, and the definitions of R ¹³ , R ^14, and R ¹⁵ are the same as in Formula 4-2. same.
[3" claim-type="Currently amended] A polymer comprising a repeating unit represented by the following Chemical Formula 1 ', and having a polystyrene reduced weight average molecular weight of 1,000 to 500,000 by gel permeation chromatography (GPC).
<Formula 1 '>

In formula, the definition of R <^1> , R <^2> , R <^3> and Z <^1> is the same as that of the said Formula (1).
[4" claim-type="Currently amended] The radiation sensitive resin composition containing (A) the polymer of Claim 3, and (B) a radiation sensitive acid generator.

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同族专利:

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公开号 | 公开日

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WO2001036370A1|2001-05-25|

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EP1231205A1|2002-08-14|

---

TWI258465B|2006-07-21|

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US6770780B1|2004-08-03|

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EP1231205A4|2004-05-26|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-11-15|Priority to JPJP-P-1999-00324413

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1999-11-15|Priority to JP32441399A

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2000-05-02|Priority to JP2000133334A

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2000-05-02|Priority to JPJP-P-2000-00133334

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2000-11-10|Application filed by 마쯔모또 에이찌, 제이에스알 가부시끼가이샤

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2000-11-10|Priority to PCT/JP2000/007950

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2002-06-26|Publication of KR20020050277A

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-1999-00324413|1999-11-15|

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JP32441399A|JP2001139632A|1999-11-15|1999-11-15|Styrene compound having carboxy group on side chain and its production method|

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JP2000133334A|JP2001316333A|2000-05-02|2000-05-02|Vinylphenylpropionic acid derivative and method for producing the same|

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JPJP-P-2000-00133334|2000-05-02|

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PCT/JP2000/007950|WO2001036370A1|1999-11-15|2000-11-10|Vinylphenylpropionic acid derivatives, processes for production of the derivatives, polymers thereof and radiosensitive resin compositions|