TW200909403A - Compounds and process for producing the same - Google Patents

Abstract

Disclosed is a compound as a material for a radiation-sensitive composition having excellent coatability which is capable of forming a resist film which enables to stably form a fine pattern with high precision. Specifically disclosed is a compound which is obtained by subjecting a compound represented by the general formula (1) below and a compound represented by the general formula (2) below to a condensation reaction, and then to hydrogenation.

Description

200909403 IX. Description of the Invention [Technical Field] The present invention relates to a novel compound and a method for producing the same, and more particularly to the formation of a far ultraviolet ray such as a KFF excimer laser or an ArF excimer laser. A novel compound contained in a sensitive radiation linear resin composition of a chemically amplified photoresist useful for fine processing of radiation, and a method for producing the same. [Prior Art] In the manufacture of semiconductors such as integrated circuit components, it is increasingly required to obtain a higher degree of integration. Recently, X-rays and electrons such as ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength i57 nm), synchrotron radiation, etc. have been developed in response to the demand for microlithography etching technology capable of fine processing of 100 nm or less. A lithography technique for beam and other radiation. Therefore, various sensitive radiation linear resin compositions suitable for radiation irradiation such as excimer lasers have been proposed, and the sensitive radiation linear resin composition is known to have, for example, an element having an acid dissociable functional group and being irradiated by radiation. An acid generator which generates an acid component, thereby utilizing a chemical amplification effect of a chemical amplification radiation linear resin composition or the like. Specifically, a photoresist composition having an organic low molecular weight having a film forming ability such as calixarene or fullerene has been proposed (for example, 'refer to Patent Document 丨~8), and contains a multivalent value. A photoresist composition of a phenol compound (for example, refer to Patent Documents 9 to 1 1). In addition, an organic low molecular (1,3,5-[4-(2-tert-butoxycarbonyloxy))benzene having a film forming energy of -5 to 200909403 other than calixarene and fullerene is also proposed. (1) Patent Document 1 (Japanese Patent Laid-Open Publication No. Hei 11-322656) (Patent Document 2) Japanese Patent Publication No. Hei No. Hei 1 - 7 2 9 1 6 Japanese Laid-Open Patent Publication No. Hei 9-211862 (Patent Document 5) Japanese Patent Publication No. Hei 9-211862 (Patent Document 6) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 1 1] Japanese Patent Publication No. 2 0 0 7 - 5 5 9 9 1 (Non-Patent Document 1) J. Photo Sci and Tech VOL12 No 2 375-376 (1999) [Draft] However, Patent Document 2 The photoresist composition described in 3, because of the extremely strong intermolecular interaction of its structure, for the imaging liquid Solvability bad, so there will not be a problem to get the satisfaction pattern. In addition, since the photoresist composition described in Patent Documents 4 to 8 and Patent Document 1 requires multi-stage synthesis in the production method, there is a problem that the mass production cannot be sufficiently performed, the production efficiency is poor, and stable quality cannot be provided. Further, the photoresist composition described in the above-mentioned Japanese Patent Publication No. 6-1-200909403 has a problem that the sensitivity is insufficient because of the lack of sensitivity. Therefore, in the resist compositions described in Patent Documents 2 to 11 and Non-Patent Document 1, in addition to the various problems described above, since the absorption of the length of 193 nm is large, the photoresist film is formed and exposed. If an ArF excimer laser is used, there is a case where the ArF excimer laser cannot be irradiated inside the photoresist film. Therefore, there is a problem that the line edge roughness (R) of the photoresist pattern on the photoresist film is large (the unevenness of the side surface of the photoresist when the line pattern of the photoresist is viewed from above). Further, there is a problem that the coating property (coating) of the substrate is insufficient. Further, although the photoresist composition described in Patent Document 1 can form a photoresist film excellent in resistance, since an ArF excimer is used after exposure to form a photoresist film at a wavelength of 1 93 nrn. Lei has the ArF excimer laser that cannot fully illuminate the interior of the photoresist film. Therefore, the line edge roughness of the photoresist pattern formed in the photoresist film is large. The present invention has been made in view of the above problems, and provides a chemical composition of a linear radiation resin composition using an ArF excimer laser as an exposure light source etching technique, The excellent permeability to the ArF excimer laser can reduce the line edge roughness of the photoresist pattern, and the coating property is excellent in addition to the photoresist film which can form a fine pattern with high precision. The inventors of the present invention actively explored the results of the above-mentioned problems, and the light of practical use is in the inter-wave, and the LER's line is fully etched into a large eclipse, and the ruthlessness of the rough material is so small that it is 7-200909403 A compound represented by the following formula (1) and a compound represented by the following formula (2) are subjected to a condensation reaction, and the benzene ring derived from the compound represented by the above formula (1) is unsaturated. The compound obtained by hydrogenation of a bond can achieve the above problems, and thus the present invention has been completed. That is, according to the present invention, a compound shown below and a method for producing the same are provided. [1] A compound ' is a condensation reaction of a compound represented by the following formula (1) and a compound represented by the following formula (2), and is derived from a benzene derived from the compound represented by the above formula (1) The ring unsaturated bond is hydrogenated to obtain:

(in the above formula 1), X1 represents a carbon number of 1

Substituted or unsubstituted oxy, yl, or substituted or unsubstituted phenoxy 1 0

Substituted alkynyl, carbon number 7 to 1 oxime, substituted by carbon number 7 to 1 oxime or substituted or unsubstituted alkyl of 10, ethoxy group 'P represents 〇 or 1),

〇Hc - X2 - CHO 200909403 (In the above formula (2), X2 represents a carbon number of 1 to 8 substituted with a substituted alkyl group). [2] The compound according to the above [1], wherein the compound represented by the above 3⁄4^1 (1) and the condensation reaction product obtained by the condensation reaction represented by the above formula (2) It is a compound represented by the following formula (3) and a compound represented by the following formula (4) or a compound represented by the following @ ( >:

^ The formula (3) towel 'ΧΙ independently of each other means a substituted or unsubstituted alkyl group having a carbon number of 1 to 10, a substituted or unsubstituted alkenyl group having a carbon number of 2 to i, a carbon number of 2 to 1. () substituted or unsubstituted alkynyl group, carbon number 7 10 substituted aromatic group, carbon ... substituted or not == group, or substituted or unsubstituted phenoxy 'χ2 each other Independently stated. Or u, generation or unsubstituted extension of the base, suede this alone -9- 200909403

(In the above formula (4), X1 independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and a carbon number of 2~ a substituted or unsubstituted alkynyl group of 10, a substituted or unsubstituted aralkyl group having a carbon number of 10, a substituted or unsubstituted alkoxy group having a carbon number of 1 to 1 fluorene, or substituted Or an unsubstituted phenoxy group, X2 independently of each other represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and p independently of each other represents hydrazine or 1), -10-200909403 [Chemical 5]

(The above formula (1) towel 'X, this independently represents carbon number or unsubstituted:> Yanqi station machine U, the key replaces a certain, carbon _ 2~1 〇 substituted or unsubstituted stimulant fe number 2~1 取代 经 输 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± An oxy group, or a substituted or unsubstituted phenoxy group, P each independently exhibits 0 or 1, and n represents an integer of 0 or more. [3] The compound according to the above [2], wherein the compound represented by the above formula (3), the compound represented by the above formula (4) or the compound represented by the above formula (5) are each the following a compound represented by the formula (6), a compound represented by the formula (7) or a compound represented by the formula (8): -11 - 200909403 [Chemical 6]

[7]

〔化8〕

-12- 200909403 (in the above formula (8), η represents an integer of 0 or more). [4] The compound according to any one of the above [1] to [3] wherein the ratio of the unsaturated bond to be hydrogenated is 30 to 1 with respect to all the unsaturated bonds of all the benzene rings contained in the condensation reaction product. 〇〇%. [5] A method for producing a compound which is obtained by subjecting a compound represented by the following formula (1) and a compound represented by the following formula (2) to a condensation reaction and is derived from the above formula (〇 The benzene ring unsaturated bond in the compound is hydrogenated to obtain the compound: [Chemical 9]

Substituted or not taken

~W substituted or unsubstituted alkyl phenoxy group, p represents hydrazine or hydrazine), alkane (in the above formula (1), X1 represents a carbon number b alkyl group, carbon number 2 to 1 () 2 to 10 substituted or unsubstituted aralkyl, oxy, or substituted or unsubstituted phenoxylated 10

X2 - CHO (in the above formula (2), an alkyl group is substituted). X represents the carbon number 1

[6] The method for producing a compound according to the above [5], wherein the compound represented by the above formula (1) and the compound represented by the above formula (2) are subjected to a condensation reaction, and the source is obtained. Hydrogenation of a benzene ring unsaturated bond in the compound represented by the above formula (1) to obtain a compound represented by the following formula (9), a compound represented by the following formula (1 〇) or a formula (1) 1) Compound represented: [Chemical 1 1]

[Chemical 1 2]

(10) -14- 200909403 [Chem. 1 3]

(η in the above formula (11) represents an integer of 〇 or more). The compound of the present invention is a sensitive radiation linear resin composition material, and in the lithography lithography technique using an ArF excimer laser as an exposure light source, since the permeability to the ArF excimer laser is excellent, the photoresist pattern is lowered. The line edge roughness 'except for the photoresist film which can form a fine pattern with high precision and stability, and the coating property is also excellent and the effect is exhibited. The method for producing the compound of the present invention can attain a good effect of producing the compound of the present invention. The preferred embodiments of the present invention are described below, but the present invention is not limited to the following embodiments, and those skilled in the art can make the following embodiments based on the conventional knowledge without departing from the spirit of the invention. Appropriate changes, improvements, etc., are understood to be within the scope of the invention. [1] Compound: One embodiment of the compound of the present invention is such that the compound represented by the following general formula (1), Table -15 to 200909403, and the compound represented by the following formula (2) are subjected to a condensation reaction, and are derived from the above A compound obtained by hydrogenating a benzene ring unsaturated bond in the compound represented by the formula (1). By including the compound in the sensitive radiation linear resin composition, the sensitive radiation linear resin composition is excellent in permeability to ArF excimer laser in a lithography etching technique using an ArF excimer laser as an exposure light source. Therefore, it is possible to reduce the line edge roughness of the photoresist pattern. In addition to the photoresist film which can form a fine pattern with high precision and stability, it is also excellent in coatability. [Chem. 1 4]

X represents a carbon number (alkyl group in the above formula (2)). Substituted or not taken - 16-200909403 [1-1] Condensation reaction: The compound of the present embodiment is a compound represented by the above formula (1) and a compound represented by the above formula (2) Obtained by condensation reaction. An advantage of the compound of the present embodiment as an object of the invention is that it can be easily synthesized by a condensation reaction of a compound represented by the above formula (1) and a compound represented by the above formula (2). Further, the compound represented by the formula (1) and the compound represented by the formula (2) may be used singly or in combination of plural kinds. The substituent of the substituted alkyl group having 1 to 10 carbon atoms in X1 in the compound represented by the formula (1) can be exemplified by, for example, a methyl group, an ethyl group, a propyl group, a butyl group or the like. Among these, the compound of the present embodiment is preferably a propyl group or a butyl group from the viewpoint of obtaining a high yield. Further, 'substituted alkenyl group having 2 to 10 carbon atoms, substituted alkynyl group having 2 to 10 carbon atoms, substituted aralkyl group having 7 to 10 carbon atoms, substituted alkoxy group having 1 to 1 carbon number The substituent in the substituted phenoxy group may be, for example, the same as the substituent of the above alkyl group having 1 to 1 carbon atom. The p in the compound represented by the formula (1) is preferably 0. In other words, the compound represented by the formula (1) can be obtained in a high yield. The compound of the present embodiment is preferably a compound represented by the following formula (1-1):

200909403 [Chem. 1 6] HO, (1-1) hct The number of carbon atoms in X2 in the compound represented by the formula (2), and the substituent of the substituted alkyl group can be exemplified by the above carbon number 1 to 10 The substituents of the alkyl group are the same. The compound represented by the formula (2) is any one of the alkylene groups having a carbon number of 1 to 8 (the structure of the obtained compound is different), and the obtained compound has no particular effect on the present invention, and can be produced in a high yield. In view of the above, X2 of the present embodiment is preferably an unsubstituted alkylene group having 2 to 6 carbon atoms and the most unsubstituted alkylene group having 3 carbon atoms. That is, the compound represented by the formula (2) is preferably a compound represented by the following formula (2-1) (glutaraldehyde) [I1] OHC-(CH2) 3 -CH0 (2-1) The structure of the main compound obtained by the condensation reaction is determined by the carbon number of X2 in the compound represented by (2). When X2 in the compound represented by the formula (2) is a propyl group, a compound represented by the formula (3) will be obtained, and in the compound of the formula (3, X2 is mainly a propyl group. Further, in the compound represented by the general formula (2), X2 which is a substituted -18-'8 substituted X3 may also be distinguished. In the case of the compound represented by the formula (4), the compound represented by the formula (4) will be mainly obtained, and in the compound represented by the formula (4), a compound in which X2 is a butyl group is mainly obtained. Further, when X2 in the compound represented by the formula (2) is an ethyl group, a compound represented by the formula (5) which will be described later is mainly obtained. The conditions (methods) of the condensation reaction are not particularly limited, and a conventionally known method can be employed, for example, a method in which dehydration condensation is carried out at 60 to 90 ° C for 12 to 48 hours in the presence of a catalyst such as an acid catalyst. Further, the mixing ratio (molar ratio) of the compound represented by the above formula (1) and the compound represented by the above formula (2) is not particularly limited, but from the viewpoint of improving the yield, The compound represented by the formula (2) represented by the formula (1) is preferably 1. 〇 8.0, more preferably 2.0 to 6.0, and most preferably 3. 〇 to 5. If it is outside the range of 1 〇 to 8 〇, the yield of the target compound is lowered. Further, the concentration of the substrate in the condensation reaction solution (the total concentration of the compound represented by the formula (1) and the compound represented by the formula (2)) is not particularly limited, but from the viewpoint of improving the yield, More preferably, it is more preferably 4 mol/liter or more, and 4 to 丨〇 mol/liter is most preferable. A concentration of the right substrate of less than 2 mol/liter lowers the yield of the target compound. The compound represented by the formula (1) and the compound represented by the formula (2) are preferably added to the reaction solvent. The reaction solvent is preferably an organic solvent, and the alcohol solvent is most preferred. The alcohol solvent may, for example, be, for example, methanol, ethanol, n-propanol, isopropanol or the like. Among these, methanol and ethanol are preferred from the viewpoint of increasing the yield of the compound of the present embodiment. -19- 200909403 After the condensation reaction, the resulting precipitate is preferably washed with an organic solvent, and examples of the organic solvent include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and 3- Ketones such as methylcyclopentanone and 2,6-dimethylcyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, cyclopentanol, cyclohexanol, 1 An alcohol such as 4-hexanediol or 1,4-hexanedimethanol; an ether such as diethyl ether, tetrahydrofuran or dioxane; an ester such as ethyl acetate, n-butyl acetate or isoamyl acetate; toluene; An aromatic hydrocarbon such as xylene or phenol, hydrazine or dimethylformamide. Among these, methanol, ethanol, diethyl ether and tetrahydrofuran are preferred. Further, the organic solvents may be used singly or in combination of plural kinds. The I® reaction product obtained by subjecting the compound represented by the formula (1) and the compound represented by the formula (2) to a condensation reaction is preferably represented by the following formula (3). a compound, a compound represented by the following formula (4) or a compound represented by the following formula (5): [Chem. 1 8] (X1)p

(In the above formula (3), 'X1 independently of each other means a substituted carbon-20 to 200909403 or an unsubstituted alkyl group, a carbon number of 2 iu substituted or unsubstituted, and a carbon number of 2 to 1. Substituting a substituted or unsubstituted alkynyl group of φ, a substituted or unsubstituted aryl I*# substitution of a carbon-based 7~1〇1... a carbon number of 1 to 10 Substituted or unsubstituted, unsubstituted or unsubstituted phenoxy group, χ2 is substituted or unsubstituted with each other, and the skin is not 0 or 1). Furthermore, the above formula (3) may also be of the following formula (3_ 者..) 尸/τ不(化1 9)

(In the above formula (3-1), X1 independently represents a substituted or unsubstituted alkyl group having a carbon number, a substituted or unsubstituted alkenyl group having 2 to 2 carbon atoms, and a carbon number of 2 to 1; Substituted or unsubstituted alkynyl 'substituted or unsubstituted aralkyl group having a carbon number of 7 to ic, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or substituted Or an unsubstituted phenoxy group, χ2 independently of each other represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and ρ independently represents 0 or 1). Among the compounds represented by the formula (3), a compound of a propyl group of X2 is preferred. In the compound represented by the formula (3), X2 is a propyl group, and it is preferable because it can be produced in a high yield and at a low cost. Further, in the compound represented by the formula (3) wherein X2 is a propyl group, a compound represented by the following formula (6) is preferred. That is, in the formula (3), X2 is preferably a propyl group and p is 0. Such a compound represented by the following formula (6) (i.e., a compound in which the X2 is a propyl group and a p is 0 in the formula (3)) can be produced in a higher yield and at a lower cost. 〔化 2 0〕

The compound represented by the formula (6) can be obtained by a compound represented by the formula (丨-1) and a compound represented by the formula (2_1) (glutaraldehyde) in the presence of a catalyst such as an acid catalyst. Obtained by dehydration condensation at 60 to 90 ° C for 12 to 48 hours. -22- 200909403 (X1)p

(4) (In the above formula (4), X 1 independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms. a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 1 carbon number. A substituted or unsubstituted phenoxy group, X2 independently of each other represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and p independently of each other represents hydrazine or 1). Further, the above formula (4) may be as shown in the following formula (4-1) -23- 200909403 [Chem. 22]

(In the above formula (4_丨), the sputum team replaces or replaces the yard base, carbon number 2: stands for carbon number 1~1〇, the carbon number is 2, and the carbon number is substituted or a substituted or unsubstituted alkynyl group substituted with 1 ± a, a carbon number of 7 to 1 〇 = = a substituted aryl group, a carbon number substituted or not = a oxy group, or Substituted or unsubstituted phenoxy group, X, this alone::: substituted or unsubstituted extender base of carbon number, mutually exclusive or 1). Among the compounds represented by the formula (4), a quinone-based butyl group is preferred. Among the compounds represented by the formula (4), a compound wherein X2 is a butyl group is preferred because it can be produced in a high yield and at a low cost. Further, in the compound represented by the formula (4) wherein X2 is a butyl group, the compound represented by the following formula (7) is preferred. That is, in the formula (4), X2 is a butyl group, and ρ is preferably 0. The compound represented by the following formula (7) (i.e., the compound of the formula (4) wherein X2 is a butyl group and the hydrazine is a hydrazine) can be produced in a higher yield and at a lower cost. -24- 200909403 [Chem. 23]

The compound represented by the formula (7) can be used in the presence of a compound represented by the formula (1-1) and a compound represented by the formula (2-2) in the presence of a catalyst such as an acid catalyst, at 60~ Obtained by dehydration condensation at 90 ° C for 12 to 48 hours. 〔化 24〕 (2-2)

OHC— ( CH2 ) 4 —CHO 25

(3) -25- 200909403 (The above formula (5) towel's are independent of each other and represent a carbon number of μ. The substituted or unsubstituted garden base, the substituted or unsubstituted base of carbon 2~1〇, Substituted or unsubstituted alkynyl group having a carbon number of 2 to 1 Å, substituted or unsubstituted carbon number of 7 to 10, less than or less than the number of carbon atoms, carbon number 丨〇~丨〇 The substituted oxy group, or the substituted or unsubstituted phenoxy group, p each independently represents 1 or η represents an integer of 0 or more). Among the compounds represented by the formula (5), a compound represented by the following formula (8) is preferred. That is, the general formula (5) φ is preferably ρ. The compound represented by the following formula (8) (i.e., a compound in which ρ is ruthenium) can be produced in a high yield and at a low cost. If η in the aliquot represented by the following formula (8) is an integer greater than 丨, the advantage is that the coating property is better.

(In the above formula (8), η represents an integer of 〇 or more). The compound represented by the formula (8) can be used in the presence of a compound represented by the formula (1-1) and a compound represented by the formula (2-3) in the presence of a catalyst such as an acid catalyst, in 60~ Dehydration condensation was carried out at 90 ° C for 12 to 48 hours and from -26 to 2009 09403. [Chem. 27] OHC—(CH2) 4 —CHO ( 2-2 ) Further, the compound represented by the above formula (2-3) can be, for example, a compound represented by the following formula (2-4) under an acid catalyst. , produced by reaction with water. According to this, the compound represented by the formula (1) and the compound represented by the following formula (2-4) can be subjected to dehydration condensation at 60 to 90 ° C in the presence of, for example, water and an acid catalyst. The compound represented by the formula (5) is obtained in ~48 hours.

[1-2] Hydrogenation: The compound of the present embodiment may be obtained by hydrogenating an unsaturated bond of a benzene ring derived from the compound represented by the formula (1) (hereinafter, simply referred to as "hydrogenation"). The condensation reaction product of the benzene ring before hydrogenation is a compound having a large absorption near a wavelength of 193 nm, but by hydrogenation, it becomes a compound which absorbs small at a wavelength of about 193 nm (the compound of this embodiment) Therefore, when the photoresist film is formed by the radiation sensitive linear resin composition containing the compound of the present embodiment as a material, the permeability of the formed photoresist film to the ArF excimer laser can be improved. Further, by hydrogenation, since the solubility in an organic solvent can be improved, the coating property when the linear composition containing the sensitive radiation of the compound of the embodiment of -27-200909403 is applied can be improved. The compound of the present embodiment is preferably a compound obtained by hydrogenating a compound represented by the formula (3), a compound represented by the formula (4) or a compound represented by the formula (5). (6) The compound represented by the formula (7) or the compound represented by the formula (8) is preferably hydrogenated, and the compound represented by the following formula (9) is represented by the following formula (1). In the compound represented by the following formula (11), n is preferably an integer of 1 or more. In the compound represented by the following formula (1 1 ), n is i or more. The integer is an advantage that the coating property is further improved. [Chem. 2 9]

Ho^^oh (qh2)3 ______ -28- 200909403 〔化3 0〕

〔化 3 1〕

(In the above formula (11), η represents an integer of 0 or more). In the compound of the present embodiment, the ratio of the hydrogenated unsaturated bond to the total unsaturated bond of all the benzene rings contained in the condensation reaction product is preferably 3 in terms of improving the permeability to the ArF excimer laser. 0 to 1 0 0 % 'In terms of improving the permeability of the ArF excimer laser, it is preferably 60 to 100%' and 1% by weight (all unsaturated bonds in the condensation reaction product are hydrogenated) Status) is optimal. As the method for hydrogenating (hydrogenation) the condensation reaction product, a conventionally used method for hydrogenating an unsaturated bond can be employed. That is, for example, -29 to 200909403, for example, a method of introducing hydrogen into a condensation reaction product in an organic solvent in the presence of a homogeneous or heterogeneous hydrogenation catalyst. The concentration of the condensation reaction product in the organic solvent is preferably from 1 to 70% by mass, more preferably from 1 to 40% by mass. Further, the organic solvent is not limited, and it can be used without particular limitation as long as it does not adversely affect the hydrogenation catalyst. Further, the organic solvent is preferably an alcohol solvent, and the alcohol solvent may, for example, be methanol, ethanol, n-butanol or isopropanol. Among these, methanol and ethanol are preferred. The hydrogenation catalyst can be used without particular limitation if it is a metal or non-metal catalyst having hydrogenation activity. Specific examples thereof include Fe, Co, Ni, Ru, Rh, Pd, Ir, Os, Pt, Cr, Te, Μη, Ti, V, Zr, Mo, and W-based hydrogenation catalysts. These catalysts may be used singly or in combination of plural kinds. The temperature of the hydrogenation reaction is preferably from 〇 to 300 ° C, more preferably from 2 0 to 1 5 . If the reaction temperature exceeds 300 ° C, side reactions are likely to occur. The hydrogen pressure at the time of the hydrogenation reaction is preferably 3939 Mpa, more preferably 0.5 to 20 MPa. After the hydrogenation reaction, the hydrogenation catalyst is preferably removed by a reprecipitation purification method, a precipitation method, a centrifugation method, a filtration method, or the like. [Examples] Hereinafter, the present invention will be specifically described based on examples of the present invention, but the present invention is not limited to the examples. In addition, in the examples and comparative examples, "parts" and "%" are subject to quality unless otherwise specified. (Example 1) -30- 200909403 2.20 g (20 mmol) of isophthalic acid was dissolved in 4.5 ml of ethanol' and 1.5 ml of hydrochloric acid was added. The solution was stirred and ice cooled to 5. (:, slowly add 1 · 0 0 g (5 mmol) of 50% aqueous solution of glutaraldehyde. Then, heat at 80 ° C for 48 hours. After the reaction, precipitate the solid and cool the reaction solution. After the mixture was stirred at room temperature, methanol was added and the solid was washed. After collecting the precipitate by filtration, the step of washing with methanol was repeated three times to filter. The obtained solid was dried under reduced pressure at room temperature for 24 hours. A pale yellow solid (yield: 1.18 g (yield: 83%), indicated by "A-1" in Table 1). The structure of the obtained pale yellow solid was confirmed by μALDI-TOF-MS (Model SHIMAZU) /KRATOS Matrix supports the laser ionization time-of-flight mass spectrometer "KOMPACT MALDI IV tDE", manufactured by Shimadzu Corporation, IR (model "FT-IR 420", manufactured by JASCO Corporation) and 1H-NMR (model " JNM-ECA- 5 00", manufactured by Nippon Denshi Co., Ltd.) The results are shown below. MALDI-TOF-MS: shows a compound having a molecular weight of 1704.63 〇IR (film method): (cm·1 ) 3406 ( v On) 2931 ( v cw) ; 1621 ' 1505 ' 1436 ( V c = c (aromatic)); h-NMROOOMHz' solvent DMSO-d6' internal standard TMS): δ (ppm) = 0.86~2.35 ( b, 12.OH) , 3.98 — 4.22 ( m, 4·0Η), 6.09~7·42 ( m, 8.0 H) , 8 · 6 5 to 9.5 6 (m, 8.0 H ) The obtained pale yellow solid is a compound represented by the following formula (6): -31 - 200909403 [32]

1.0 g of the compound represented by the formula (6) and 45 g of the obtained product were placed in an autoclave and mixed. Subsequently, 0.6 g of 阮H Aldrich Co., Ltd. was added as a hydrogenation catalyst, and air was replaced with nitrogen. After replacement with nitrogen, the system was maintained at 2 (TC, maintained at a force of 50 kg/cm 2 for 30 minutes. Subsequently, the autoclave was immersed in a warm water bath for 3 hours to express the expression (6). After the reaction, the reaction solution is filtered, and the reacted monidene N i is separated. The filtrate is added to water to produce a precipitate, and then dried for 24 hours to obtain a compound represented by the following formula (9). The compound is represented by "A-2" in Table 1. Ethanol feed g Ni (the chlorine pressure in the system is 50%. The compound is introduced into the solution under reduced pressure) -32- 200909403 [Chem. 3 3]

In order to evaluate the obtained compound represented by the formula (9), the following composition was formulated. First, 100 parts of the compound represented by the formula (9), 600 parts of cyclohexanone as a solvent (indicated by "D -1" in Table 1), and 1500 parts of propylene glycol monomethyl ether acetate ( The mixture was mixed as "D-2j" in Table 1. Then, the mixture was filtered through a 200 nm membrane filter to prepare a homogeneous composition solution (sensitive radiation linear resin composition). The following evaluations were performed on the formulated composition solution. [Coating property] Using a "CLEAN TRACK ACT-8" manufactured by Tokyo Electronics Co., Ltd., the composition solution was spin-coated on a tantalum wafer, and then heat-treated at 7 ° C for 90 seconds (in Table 1) PB" shows), a photoresist film of 100 nm was obtained. The surface of the photoresist film was visually observed for applicability evaluation. The evaluation criteria indicated that the unseen stripes were indicated as "good", and when the stripes were observed, they were indicated as "bad". -33- 200909403 [Transmission rate] Using a "CLEAN TRACK ACT-8" manufactured by Tokyo Electronics Co., Ltd., the composition solution was spin-coated on a MgF 2 substrate and heat-treated at 70 ° C for 90 seconds (Table 1). In the middle of "PB", a photoresist film of 1 〇〇 nm is obtained. The transmittance at 193 nm was measured by a "VU-2 01 vacuum ultraviolet spectrophotometer" manufactured by Spectrophotometer. As a result of evaluation of the composition solution (sensitive radiation linear resin composition) prepared in the present example, the coating property was good and the transmittance was 90%. From the results of this evaluation, it was confirmed that the compound of the present example has a high transmittance due to the ArF excimer laser, and when it is contained in the linear radiation-sensitive resin composition, the photoresist film is formed by using the radiation-sensitive linear resin composition. Then, the inside of the photoresist film can be sufficiently irradiated with light (ArF excimer laser). Accordingly, when the compound of the present embodiment is used, it is considered that a photoresist film having a reduced line edge roughness of the photoresist pattern can be obtained. (Example 2) 100 parts of the compound represented by the formula (9) obtained in the examples and 2,100 parts of propylene glycol monomethyl ether acetate as a solvent were mixed. The mixture was filtered through a membrane filter having a pore size of 200 nm to prepare a homogenous composition solution (sensitive radiation linear resin composition), and evaluated. The evaluation results are shown in Table 1. -34- 200909403 [Table 1] Solvent solubility of compound PB1 丨 Conditional coating transmittance (%) Formulation amount (parts) Type of compounding amount (parts) Type of compounding amount (parts) Temperature (. 〇 time (seconds) Example 1 A-2 100 D-1 600 D-2 1500 Good 70 90 Good 90 Example 2 A-2 100 D-2 2100 Good 70 90 Good 90 Comparative Example 1 A-1 100 D-1 600 D-2 1500 Bad Comparative Example 2 A-1 100 _ - D-2 2100 Poor Comparative Example 3 A-3 100 D-1 600 D-2 1500 Good 70 90 Good 0 Comparative Example 4 A-4 100 D-1 600 D-2 1500 Good 70 90 Good 4 (Comparative Example 1) 1 part of the light yellow solid (the compound represented by the formula (6)) prepared in Example 1, 600 parts of cyclohexanone as a solvent, and 1 500 parts of propylene glycol Methyl ether acetate. However, the solubility was poor, and a uniform solution could not be obtained. Therefore, the applicability and the transmittance were not evaluated. (Comparative Example 2) 100 parts of the pale yellow solid prepared in Example 1 was mixed ( a compound represented by the formula (6)) and 2,100 parts of propylene glycol monomethyl ether acetate as a solvent. However, the solubility is poor and cannot be obtained. A homogeneous solution. Therefore, evaluation of coating properties and transmittance was not possible. (Comparative Example 3) 100 g of 4-third-butoxystyrene, 4.7 g of azobisisobutyronitrile, and 1.5 g of third-tenth were used. Dialkyl mercaptan and 100 g of propylene glycol monomethyl ether were put into a separatory funnel and stirred at room temperature to form a homogeneous solution. The temperature was raised to -35-200909403 80 ° C under nitrogen, and the polymerization was carried out under stirring. After the completion of the polymerization, a large amount of methanol was added to the reaction solution to reprecipitate and purify. 90 g of the polymer thus obtained was dissolved in 500 g of propylene glycol monomethyl ether, and concentrated under reduced pressure. About 250 g of the concentrated polymer solution under reduced pressure and 40 g of a 1% aqueous solution of sulfuric acid were fed into the separatory funnel, and the hydrolysis reaction was carried out under stirring and reflux. Subsequently, a large amount of ion-exchanged water was added and purified by reprecipitation. And drying under vacuum at 50 ° C, thereby obtaining 60 g of a 4-hydroxystyrene polymer. Further, the polymer is represented by "A-3" in Table 1. The Mw of the 4-hydroxystyrene polymer was measured. Μη, and calculate Mw/Mn. The measurement of Mw and Μη is in TOS GPC pipe made by TOSOH Co., Ltd. (product name "G2000HXL": 2 pieces, "G3000HXL": 1 piece, "G4 000HXL": 1 piece) is used for the high-speed GPC device (type "HLC-8120") manufactured by OH Corporation. The flow rate was 1. 〇ml/min, and tetrahydrofuran was used as the eluent. The gel was subjected to gel permeation chromatography (GPC) under the conditions of column temperature 4 (TC analysis using monodisperse polystyrene as a standard). The 4-hydroxystyrene polymer obtained in the synthesis example had a Mw of 1,800 and a Mw/Mn of 1.58. 1 〇 of the obtained 4-hydroxystyrene polymer, 600 parts of cyclohexanone as a solvent, and 1500 parts of propylene glycol monomethyl ether acetate were mixed. The mixture was filtered through a membrane filter having a pore size of 2 0 0 nm to prepare a homogeneous composition solution, and evaluated. The evaluation results are shown in Table 1. (Comparative Example 4) -36-200909403 3.5 g of the pale yellow solid (the compound represented by the formula (6)) prepared in Example 1 was added to 40 g of 1-methyl-2-pyrrolidone, and further added with hydrazine. 8 g of tetrabutylammonium bromide was dissolved by stirring at 70 ° C for 4 hours. After the dissolution, 3.3 g of potassium carbonate was added, and the mixture was stirred at 70 t for 1 hour. Subsequently, 6.9 g of 2-methyl-2-adamantyl bromoacetate previously dissolved in 20 g of 1-methyl-2-pyrrolidone was slowly added, and stirred at 70 ° C for 6 hours. After stirring, it was cooled to room temperature and extracted with water/dichloromethane. Subsequently, it was washed three times with 100 ml of a 3 % aqueous solution of oxalic acid, and then washed twice with water. After the aqueous layer was discarded, the organic layer was dried over magnesium sulfate. Subsequently, it was purified by hydrazine column chromatography using hexane:ethyl acetate = 1:4 as an eluate to obtain 3.2 g of a compound represented by the following formula (A-4) (indicated by "A-4" in Table 1 "). Further, iH-NMR analysis was carried out to confirm the protection ratio of the compound represented by the following formula (A-4) (the hydrogen atom of the phenolic hydroxyl group in the compound represented by the following formula (A-4) was 2-methyl-2 The ratio of the adamantyloxycarbonylmethyl group (the group represented by the following formula (R-1)) is 40%. [Chem. 3 4]

-37-200909403 (wherein R in the above formula (A-4) is independently a hydrogen atom or a formula represented by the following formula). [Chem. 3 5]

Ο-CH2-C—0 100 parts of the obtained compound represented by the formula (A-4), 6 parts of cyclohexanone as a solvent, and 1 500 parts of propylene glycol monomethyl ether acetate vinegar were mixed. The mixture was filtered through a membrane filter having a pore size of 2 0 0 n m to prepare a homogeneous composition solution and evaluated. The evaluation results are shown in Table 1. As is clear from Table 1, the sensitive radiation linear resin composition containing the compound of Examples 1 and 2 (the compound represented by the formula (9)) can be confirmed as compared with the sensitive radiation linear resin composition of Comparative Examples 3 and 4. Excellent in permeability and coating properties to ArF excimer lasers. Therefore, in the lithography etching technique using the ArF excimer laser as the exposure light source, the line edge roughness of the photoresist pattern can be reduced, and a highly precise and stable fine pattern photoresist film can be formed. [Possibility of Industrial Applicability] The compound of the present invention can be suitably used as a linear composition of a radiation sensitive film, which can reduce the line edge roughness of the photoresist pattern, and form a high precision and stable fine pattern photoresist. The film of the film is extremely useful as a material for predicting a photoresist film for manufacturing a semiconductor device which is further miniaturized in the future. -38-

Claims (1)

200909403 X. Patent Application No. 1 A compound, which captures Ν γ, + is a compound represented by the following formula (1) and is expressed in the following formula (2). a condensation reaction, and a compound obtained by hydrogenating a benzene ring unsaturated bond in a ruthenium of the above formula (1) into rfn » P ^ ^ ^ /, wherein: (Chemical 1) (1) (In the above formula (1), a substituted or unsubstituted alkyl group having a carbon number of 1 to 10, a carbon number of 2 to 1 (), an I substituted or unsubstituted alkene Substituted or unsubstituted or unsubstituted aralkyl, 2 - 1 芳 aralkyl, disc, Λ - substituted or unsubstituted alkoxy having 1 to 10 carbon atoms Base, or substituted or not, Ke Take ^ 十々! > Gan people not replaced by the base, ρ means 〇 or 丨), [Chemical 2] OHC —X2__ch〇( 2 ) (The above formula (2 In the formula, X2 represents a substituted or unsubstituted alkylene group of the carbon number. 2. The compound of claim 1, wherein the condensation reaction product obtained by subjecting the compound represented by the above formula (1) and the compound represented by the above formula (2) to a condensation reaction is the following formula (3) -39- 200909403 A compound represented by the following formula or a compound represented by the following formula (5): [Chemical 3] (3) (In the above formula (3), X1 is heterozygous with each other; this alone represents a carbon number of 1 to fluorene or unsubstituted alkyl group, a carbon number of 2 " a substituent, and a carbon number of 2 to 10. Substituted or substituted alkynyl, ^I substituted alkynyl, carbon number Q > \substituted or unsubstituted aromatic 1 U θ - 棊, carbon number 1~1 〇 substituted or $ #驭代的克氧, or X taken unsubstituted 千千胎 unsubstituted phenoxy group, χ2 吒2 吒 袠 袠 碳 碳 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠 袠Unsubstituted alkylene, Ρ each other alone -200909403 (In the above formula (4), X1 independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and a carbon number of 2~ a substituted or unsubstituted alkynyl group of 10, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 1 carbon number, or The substituted or unsubstituted phenoxy group, X2 independently of each other represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and p independently of each other represents hydrazine or 1), -41 - 200909403 [Chemical 5] In the above formula (5), the alkyl group which is unsubstituted or unsubstituted, the carbon number independently represents a substituted group having 1 to 10 carbon atoms, and the substituted carbon number is 2 to 10: substituted or unsubstituted 1〇 Substituted dilute substituted or unsubstituted aromatic: substituted alkynyl, carbon 357, substituted alkoxy, or substituted h(tetra) 1~1〇 substituted or unsubstituted or unsubstituted Phenoxy group, P is unique to each other, and η represents an integer above 〇).武. The compound of claim 2, wherein the compound represented by the above formula (3), the compound represented by the above formula (4), and the compound of the formula (5) τρ: The compound represented by the following formula (6), the compound represented by the formula (7) or the compound represented by the formula (8): -42- 200909403 6 (6) [Chemistry 7] (7) (8) -43 - 200909403 (In the above formula (8), 'η represents an integer of 〇 or more). 4. The compound according to any one of claims 1 to 3, wherein the ratio of the unsaturated bond to the hydrogenation is 30 to 100% relative to the total unsaturated bond of all the benzene rings contained in the condensation reaction product. . A method for producing a compound obtained by subjecting a compound represented by the following formula (丨) and a compound represented by the following formula (2) to a condensation reaction, and a compound derived from the above formula (1) Hydrogenation of a benzene ring unsaturated bond to obtain a compound: [Chemical 9] (in the above formula), X1 represents a carbon number of 1 to 1 (), substituted by an alkyl group, a carbon number of 7 k, or a substituted 2 to 10 substituted or unsubstituted 2 to 10 or Unsubstituted alkynyl, _, dilute, unsubstituted aralkyl X number 7 to 10 substituted or substituted, carbon number 1~1 0 substituted by oxy, or substituted hydrazine Or an unsubstituted alkane sub-substituted phenoxy group, p represents 0 or 10 CHO 〇 HC, X2. (the above formula (2) - substituted for the base). I represents a substituted or unsubstituted carbon number of 1 to 8 -44 - 200909403. 6. A process for producing a compound represented by the above formula (1), wherein the compound represented by the above formula (1) (2) The compound is subjected to a condensation reaction, and a benzene ring unsaturated bond derived from the compound represented by the above formula (1) is hydrogenated to obtain a compound represented by the following formula (9), which has the following formula ( a compound represented by 1 0 ) or a compound represented by the following formula (1 1 ): [Chemical Formula 1] [Chemical 1 2] (10) -45 - 200909403 OH (11) OH (in the above formula (11), n represents an integer of 0 or more) -46 - 200909403 is a map of the map element table: the representative map of the table ' ' generation /-S One or two fingers CC 'seven unclear single -4-