Patent Publication Number: US-6211328-B1

Title: Phenol resin

Description:
This application is based on Japanese Patent Application No. Hei 11-158797 and No. 2000-109779, the contents of which are incorporated herein by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a phenol resin, in particular to a phenol resin for resists suitable for use in forming resist patterns. 
     2. Background Art 
     With the recent high degree of integration of integrated circuits, pattern formation at quarter micron levels has been desired. As a means for achieving downsizing of patterns, mention may be made of a method for shortening the wavelength of the light used. As such, in particular, use of a KrF excimer laser has enabled production of 64M DRAMs and 256M DRAMs and hence has been paid much attention. 
     Under the circumstances, there has been an increasing demand for resist materials for high resolution lithography and a resist material that shows good pattern formation ability and has improved heat resistance, resolution and sensitivity has been keenly desired. 
     In accordance with the downsizing of patterns, there has been a shift in the etching process of wafers from wet etching to dry etching. As a result resists are required such that the heat upon dry etching does not deform their patterns, and hence improvement in the heat resistance of resists has been demanded. 
     Resists must be transparent to the above light source, so mainly polyvinylphenols have been used. However, they are insufficient in pattern shape, resolution, developability, and film retention properties and modification of polyvinylphenols has heretofore been performed. Modification of polyvinylphenols by hydrogenation and modification by various types of copolymerization with styrene monomers, acrylic monomers, etc. have been carried out to promote functionalization of polyvinylphenols. However, in pattern formation at sub-quarter-micron levels, there has been found no resist material that simultaneously satisfies the requirements for good pattern shape, resolution, sensitivity, developability, film retention properties, and heat resistance. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to provide a phenol resin that gives good pattern shape, heat resistance, resolution, and sensitivity simultaneously in resists for lithography, etc. 
     As a result of intensive research with a view to achieving the above object, the present inventors have found that condensation of a compound (A) represented by the following general formula (I) with a polymerizable phenol compound represented by the following general formula (II) or polyvinylphenol (B) that is a polymer of the polymerizable phenol compound can give rise to a phenol resin for resists that combines good pattern shape, resolution, sensitivity, developability, film retention properties, and heat resistance, thus accomplishing the present invention. 
     That is, the phenol resin of the present invention is a phenol resin obtained by reacting at least two components, i.e., a compound (A) represented by the following general formula (I) and a polymerizable phenol compound represented by the following general formula (II) or a polymer (B), which is a polymer of the polymerizable phenol compound, in a ratio of 1 to 50 moles of the compound (A) to 100 moles of the polymerizable phenol compound or 100 moles of structural unit of the polymerizable phenol compound contained in the polymer (B) in the presence of an acid and having a weight average molecular weight of 2,000 to 20,000                   
     (wherein R 1 , R 2 , R 3 , and R 4 , which are the same or different, independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a hydroxyl group or a halogen atom)                    
     (wherein R 5  represents a hydrogen atom or a methyl group, R 6 , R 7 , R 8 , and R 9 , which are the same or different, independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a hydroxyl group or a halogen atom, provided that at least one of R 7  and R 9  is a hydrogen atom). 
     Such a phenol resin can provide good pattern shape, heat resistance, resolution, and sensitivity in resists for lithography, etc. and is useful as a light-sensitive resin such as a resist or as a resin precursor for obtaining the light-sensitive resin. Use of the phenol resin of the present invention enables improvement in the properties of resists. The light-sensitive resin composition comprising the phenol resin of the present invention is excellent in the balance of various properties of resists. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     In the general formula representing the compound (A), the alkyl groups in the substituents R 1  to R 4  are preferably linear, branched or cyclic and have one or more and 10 or less carbon atoms. As such alkyl groups, mention may be made of, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, a cyclohexyl group, etc. 
     The alkoxy groups in the substituents R 1  to R 4  preferably have 1 or more and 4 or less carbon groups. As such alkoxy groups, mention may be made of, for example, a methoxy group, a propoxy group, a t-butoxy group, etc. 
     The aryl groups in the substituents R 1  to R 4  include preferably a phenyl group, a naphthyl group, a tolyl group, a cumyl group, etc. 
     The aralkyl groups in the substituents R 1  to R 4  preferably have 6 or more and 10 or less carbon atoms. As such aralkyl groups, mention may be made of, for example, a benzyl group, a phenethyl group, a 1-methyl-1-phenylethyl group, etc. 
     Those preferred as the compound (A) include ones in which R 1  R 2 , R 3 , and R 4  are each a hydrogen atom or an alkyl group. As such compounds (A), mention may be made of, for example, 4-hydroxymethylphenol, 4-hydroxymethyl-2-methylphenol, 4-hydroxymethyl-3-methylphenol, 4-hydroxymethyl-2-ethylphenol, 4-hydroxymethyl-3-ethylphenol, 4-hydroxymethyl-2-n-propylphenol, 4-hydroxymethyl-3-n-propylphenol, 4-hydroxymethyl-2-isopropylphenol, 4-hydroxymethyl-3-isopropylphenol, 4-hydroxymethyl-2-n-butylphenol, 4-hydroxymethyl-3-n-butylphenol, 4-hydroxymethyl-2-s-butylphenol, 4-hydroxymethyl-3-s-butylphenol, 4-hydroxymethyl-2-t-butylphenol, 4-hydroxymethyl-3-t-butylphenol, 4-hydroxymethyl-2,3-diemthylphenol, 4-hydroxymethyl-2,5-diemthylphenol, 4-hydroxymethyl-2,6-dimethylphenol, 4-hydroxymethyl-3,5-dimethylphenol, 4-hydroxymethyl-2-isopropyl-6-methylphenol, 4-hydroxymethyl-2-t-butyl-6-methylphenol, 4-hydroxymethyl-2,6-diisopropylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 4-hydroxymethyl-2,3,5-trimethylphenol, 4-hydroxymethyl-2,3,6-trimethylphenol, etc. 
     Particularly preferred compounds (A) are those in which two or three out of R 1  to R 4  are alkyl groups and the remaining ones are hydrogen atoms. As such compounds (A), mention may be made of, for example, 4-hydroxymethyl-2-methylphenol, 4-hydroxymethyl-2,6-dimethylphenol, 4-hydroxymethyl-2,3,6-trimethylphenol, etc. 
     Other preferred compounds (A) include ones in which R 1 , R 2 , R 3 , and R 4  represent independently a hydrogen atom, an alkoxy group, a hydroxyl group or a halogen atom. As such compounds (A), mention may be made of, for example, 4-hydroxymethyl-2-methoxyphenol, 4-hydroxymethyl-3-methoxyphenol, 4-hydroxymethyl-2-hydroxyphenol, 4-hydroxymethyl-3-hydroxyphenol, 4-hydroxymethyl-2,6-difluorophenol, etc. 
     The polymerizable phenol compound to be condensed with the compound (A) and represented by the above general. formula (II) includes a vinylphenol compound and an isopropenylphenol compound. 
     The above vinylphenol compound is a compound that has a vinyl group (CH 2 ═CH—) at the para-position with respect to the phenolic hydroxyl group. 
     AS the vinylphenol compound, the ones in which the substituents R 6  to R 9  in the above general formula (II) independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a hydroxyl group or a halogen atom, provided that at least one of R 7  and R 9  is a hydrogen atom are preferred. 
     The alkyl groups in the substituents R 6  to R 9  are preferably linear, branched or cyclic and have one or more and 10 or less carbon atoms. As such alkyl groups, mention may be made of, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, a cyclohexyl group, etc. 
     The alkoxy groups in the substituents R 6  to R 9  preferably have 1 or more and 4 or less carbon groups. As such alkoxy groups, mention may be made of, for example, a methoxy group, a propoxy group, a t-butoxy group, etc. 
     The aryl groups in the substituents R 6  to R 9  include preferably a phenyl group, a naphthyl group, a tolyl group, a cumyl group, etc. 
     The aralkyl groups in the substituents R 1  to R 4  preferably have 6 or more and 10 or less carbon atoms. As such aralkyl groups, mention may be made of, for example, a benzyl group, a phenethyl group, a 1-methyl-1-phenylethyl group, etc. 
     Those preferred as the vinylphenol compound include ones in which R 6  R 7 , R 8 , and R 9  are each a hydrogen atom or an alkyl group, provided that at least one of R 7  and R 9  is a hydrogen atom. As such vinylphenol compounds, mention may be made of, for example, 4-vinylphenol, 4-vinyl-2-methylphenol, 4-vinyl-3-methylphenol, 4-vinyl-2-ethylphenol, 4-vinyl-3-ethylphenol, 4-vinyl-2-n-propylphenol, 4-vinyl-3-n-propylphenol, 4-vinyl-2-isopropylphenol, 4-vinyl-3-isopropylphenol, 4-vinyl-2-n-butylphenol, 4-vinyl-3-n-butylphenol, 4-vinyl-2-s-butylphenol, 4-vinyl-3-s-butylphenol, 4-vinyl-2-t-butylphenol, 4-vinyl-3-t-butylphenol, 4-vinyl-2,3-diemthylphenol, 4-vinyl-2,5-diemthylphenol, 4-vinyl-3,5-dimethylphenol, 4-vinyl-2,3,5-trimethylphenol, etc. 
     Particularly preferred vinylphenol compounds are those in which two or three out of R 6  to R 9  are alkyl groups and the remaining ones are hydrogen atoms. As such vinylphenol compounds, mention may be made of, for example, 4-vinyl-2-methylphenol, 4-vinyl-2,6-dimethylphenol, 4-vinyl-2,3,6-trimethylphenol, etc. 
     Other preferred vinylphenol compounds include ones in which R 6 , R 7 , R 8 , and R 9  are each a hydrogen atom, an alkoxy group, a hydroxyl group or a halogen atom. As such vinylphenol compounds, mention may be made of, for example, 4-vinyl-2-methoxyphenol, 4-vinyl-3-methoxyphenol, 4-vinyl-2-hydroxyphenol, 4-vinyl-3-hydroxyphenol, 4-vinyl-2,6-difluorophenol, etc. 
     The above isopropenylphenol compound is a compound that has an isopropenyl group (CH 2 ═CCH 3 —) at the para-position with respect to the phenolic hydroxyl group and includes those compounds represented by the above general formula (II) in which R 6  to R 9  independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a hydroxyl group or a halogen atom, provided that at least one of R 7  and R 9  is a hydrogen atom. 
     The alkyl groups in the substituents R 6  to R 9  are preferably linear, branched or cyclic and have one or more and 10 or less carbon atoms. As such alkyl groups, mention may be made of, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, a cyclohexyl group, etc. 
     The alkoxy groups in the substituents R 6  to R 9  preferably have 1 or more and 4 or less carbon groups. As such alkoxy groups, mention may be made of, for example, a methoxy group, a propoxy group, a t-butoxy group, etc. 
     The aryl groups in the substituents R 6  to R 9  include preferably a phenyl group, a naphthyl group, a tolyl group, a cumyl group, etc. 
     The aralkyl groups in the substituents R 6  to R 9  preferably have 6 or more and 10 or less carbon atoms. As such aralkyl groups, mention may be made of, for example, a benzyl group, a phenethyl group, a 1-methyl-1-phenylethyl group, etc. 
     Those preferred as the isopropenylphenol compound include ones in which R 6  R 7 , R 8 , and R 9  are independently a hydrogen atom or an alkyl group, provided that at least one of R 7  and R 9  is a hydrogen atom. As such isopropenylphenol compounds, mention may be made of, for example, 4-isopropenylphenol, 4-isopropenyl-2-methylphenol, 4-isopropenyl-3-methylphenol, 4-isopropenyl-2-ethylphenol, 4-isopropenyl-3-ethylphenol, 4-isopropenyl-2-n-propylphenol, 4-isopropenyl-3-n-propylphenol, 4-isopropenyl-2-isopropylphenol, 4-isopropenyl-3-isopropylphenol, 4-isopropenyl-2-n-butylphenol, 4-isopropenyl-3-n-butylphenol, 4-isopropenyl-2-s-butylphenol, 4-isopropenyl-3-s-butylphenol, 4-isopropenyl-2-t-butylphenol, 4-isopropenyl-3-t-butylphenol, 4-isopropenyl-2,3-diemthylphenol, 4-isopropenyl-2,5-diemthylphenol, 4-isopropenyl-3,5-dimethylphenol, 4-isopropenyl-2,3,5-trimethylphenol, etc. 
     Other preferred isopropenyl compounds include ones in which R 6 , R 7 , R 8 , and R 9  are each a hydrogen atom, an alkoxy group, a hydroxyl group or a halogen atom. As such isopropenylphenol compounds, mention may be made of, for example, 4-isopropenyl-2-methoxyphenol, 4-isopropenyl-3-methoxyphenol, 4-isopropenyl-2-hydroxyphenol, 4-isopropenyl-3-hydroxyphenol, 4-isopropenyl-2,6-difluorophenol, etc. 
     The compound (A) is reacted (condensed) with the polymerizable phenol compound, which is a vinylphenol compound or isopropenyl compound, or the polymer (B), which is a polymer of the polymerizable compound. The polymer (B) is preferably one that is obtained by preliminarily polymerizing at least one compound selected from the vinylphenol compounds and isopropenylphenol compounds described above by living anion polymerization or radical polymerization at the site of the double bond and has a weight average molecular weight of about 500 to 20,000, particularly 2,000 to 20,000. 
     As the polymer (B), mention may be made of, for example, a homopolymer (C) obtained by use of a compound selected from the above vinylphenol compounds and isopropenyl compounds, a copolymer (D) obtained by use of at least two compounds of the above vinylphenol compounds and isopropenyl compounds, and a copolymer (E) obtained by use of at least one compound selected from the above vinylphenol compounds and isopropenyl compounds and at least one other monomer. 
     As the homopolymer (C), mention may be made of, for example, polyparahydroxystyrene, polyparahydroxy-α-methylstyrene, etc. 
     As the copolymer (E), those obtained by copolymerizing the polymerizable phenol compound represented by the general formula (II) above (hereafter, sometimes referred to simply as polymerizable phenol compound) and other copolymerizable monomer by radical polymerization or the like using about 50 mol % or more, preferably 60 mol % or more of the polymerizable phenol based on the total moles of the polymerizable phenol and the copolymerizable monomer. 
     Novolak type phenol resin obtained by reacting the copolymer (E) and the compound (A) gives rise to resist patterns excellent in heat resistance, sensitivity, and resolution. 
     As the other copolymerizable monomer, mention may be made of, for example, styrenes, acrylic acid and ester derivatives thereof, α-substituted acrylic acid and ester derivatives thereof. As the styrenes, mention may be made of, for example, styrene, substituted styrenes, etc. As the acrylic acid and ester derivatives thereof, mention may be made of, for example, acrylic acid, methyl acrylate, etc. As the α-substituted acrylic acid and ester derivatives thereof, mention may be made of, for example, methacrylic acid, ethyl methacrylate, tertiary butyl methacrylate, etc. 
     As the copolymer (E), the copolymers of the above polymerizable phenol compound, styrenes and (meth)acrylic acid esters are preferred. As such copolymer (E), mention may be made of, for example, copolymers obtained by copolymerization of the above polymerizable phenol compound with tertiary butyl methacrylate, etc. 
     The phenol resin of the present invention can be produced advantageously by condensing at least two components, i.e., the above polymerizable phenol compound or polymer (B) and the compound (A), in a ratio of 1 to 50 moles, preferably 5 to 20 moles of the compound (A) per 100 moles of the above polymerizable phenol compound or 100 moles of polymerizable phenol compound as the structural unit contained in the polymer (B) in the presence of an acid. If the ratio of the compound (A) is less than 1 mole, the improvement that can be expected in the pattern shape of resists may not be large. If the ratio of the compound (A) exceeds 50 moles, the decrease in sensitivity is too great to be practical. 
     The above acid is used as an acid catalyst. As the acid catalyst, mention may be made of, for example, inorganic acids such as hydrochloric acid. Soluble, fusible resins obtained by condensation of phenols with acid catalysts are called novolak type resins. 
     The phenol resin of the present invention has a weight average molecular weight (hereafter, referred to as Mw) in the range of 2,000 to 20,000. If the Mw of the phenol resin is below 2,000, it is difficult to obtain resist patterns excellent in heat resistance, etc. If the Mw of the phenol resin is above 20,000, there arises the problem that it is difficult to dissolve in solvents such as ethyl lactate. Condensation time, etc., can adjust the Mw of the phenol resin. 
     As the method for producing the phenol resin, mention may be made of, for example, a method that comprises charging the compound (A) and the polymerizable phenol compound or the polymer (B) in a reactor in a ratio such that the amount of the compound (A) is 1 to 50 moles per 100 moles of the polymerizable phenol compound or 100 moles of the polymerizable phenol compound as the structural unit contained in the polymer (B) and condensing the compound (A) with the polymerizable phenol compound or the polymer (B) in a state dissolved in a solvent such as an alcohol-based solvent in the presence of an acid catalyst at a temperature of about 50 to 100° C. Precipitation of the produced phenol resin in water or the like followed by purification and drying the precipitate results in a phenol resin in the form of a powder. 
     Substituted phenol resins of which about 10 to 50 mol % of the hydroxyl groups of the phenol resin has been substituted by alkoxygroups are preferable as a resin for forming resist patterns. Substituted phenol resins have the property of becoming alkali soluble as a result of elimination of alkoxy groups due to acid generated by an photo-acid generator and then elimination of all the alkoxy groups by chemical amplification. 
     The substituted phenol resin can be obtained in the form of a powder by dissolving an unsubstituted phenol resin in a solvent (for example, an ester-based solvent such as ethyl acetate), adding to the resulting solution an alkoxylating agent (for example, di-tertiary butyl dicarbonate) and an alkoxylating catalyst (for example, a tertiary amine compound such as triethylamine) to substitute a portion of the phenolic hydroxyl groups into alkoxy groups, precipitating the resulting resin, and purifying and drying the precipitate. 
     The phenol resin of the present invention is useful as a resin for resists for use in the formation of resist patterns. A resist pattern can be formed, for example, by preparing a resist solution containing the phenol resin of the present invention, an photo-acid generator, and a solvent (for example, ethyl lactate), coating the resist solution on a substrate to form a resist film, exposing the resist film to light and developing it. Such a resist pattern is useful for the production of integrated circuits, etc. Here, as the photo-acid generator, mention may be made of diazo compounds such as bis(cyclohexylsulfonyl)diazomethane. 
    
    
     EXAMPLES 
     Hereafter, the present invention will be described concretely by examples. In the following examples and comparative examples, all parts are by weight. 
     Example 1 
     Production of a Novolak Type Phenol Resin 
     In a separable flask, 150 g of polyparahydroxystyrene (Mw: 5,000) synthesized by a known method (0.0375 mole as polyparahydroxystyrene [containing 150/120 moles=1.25 moles as parahydroxystyrene unit (molecular weight: 120)]) and 300 g of methanol were charged and polyparahydroxystyrene was dissolved in methanol. After dissolving, 130 g of 35% HCl was added and the resulting mixture was stirred at room temperature. During the stirring, a methanol solution containing 20 g (0.132 mole) of 4-hydroxymethyl-2,6-dimethylphenol dissolved in methanol in advance was added dropwise over 1 hour at room temperature. After the addition, the temperature was elevated and a reaction was carried out for 8 hours under ref lux of methanol. After completion of the reaction, the reaction mixture was cooled down to room temperature and the reaction mixture was added dropwise into 3,000 g of deionized water to precipitate a resin, which was collected by filtration. The collected resin was washed with 1,000 g of deionized water and collected by filtration. This purification step was repeated 5 times. Then, the obtained resin was dried at 40° C. to obtain 160 g of novolak type phenol resin (Mw: 6,000). The Mw was measured by gel permeation chromatography (GPC). 
     In this example, the charged amount of 4-hydroxymethyl-2,6-dimethylphenol was in a ratio of 13.3 parts per 100 parts of polyparahydroxystyrene charged. The mole number (molar ratio) of 4-hydroxymethyl-2,6-dimethylphenol was in a ratio of 10.6 moles (=0.132×100/1.25 moles) per 100 moles of the structural unit of parahydroxystyrene in polyparahydroxystyrene. 
     The mole ratio of the charged compound (A) and the mole ratio of the charged polymerizable phenol compound are identical with the mole ratio of the structural unit of compound (A) in the phenol resin to be polymerized and the ratio of the mole number of the structural unit of polymerizable phenol compound, respectively. Therefore, the novolak type phenol resin obtained by condensation in this example contained the structural unit of 4-hydroxymethyl-2,6-dimethylphenol (compound A) in a ratio of 10.6 moles per 100 moles of the structural unit of parahydroxystyrene. 
     Production of Substituted Phenol Resin 
     The obtained novolak type phenol resin (100 g) was dissolved in 200 g of ethyl acetate, to which 55 g of di-tertiary butyl dicarbonate and 28 g of triethylamine were added and the mixture was reacted for 5 hours under reflux. After the reaction, 300 g of ethylene glycol monoethyl ether was added as a solvent and ethyl acetate was removed under reduced pressure. Then, the reaction mixture was added dropwise into 3,000 g of deionized water to precipitate a resin, which was collected by filtration. The collected resin was washed with 1,000 g of deionized water and collected by filtration. This purification step was repeated 5 times. Then, the obtained resin was dried at 40° C. to obtain 120 g of a substituted phenol resin, i.e., the above novolak type phenol resin of which 36 mole % of the phenolic hydroxyl groups was substituted by tertiary butoxy groups. 
     Formation of Resists Patterns 
     The obtained substituted phenol resin (100 g) and 5 g of photo-acid generator (bis(cyclohexylsulfonyl)diazomethane) were dissolved in 400 g of ethyl lactate to prepare a resist solution. The resist solution was filtered through a 0.2 μm membrane filter to obtain a resist solution. The resist solution was coated on a silicon wafer (substrate) using a spinner and the coated wafer was dried on a hot plate at 90° C. for 90 seconds to produce a resist film of 0.7 μm in thickness. This film was imagewise exposed to light using a reduced projection aligner and then heated at 110° C. for 90 seconds. Then, it was developed with an aqueous 2.38 wt % tetramethylammonium hydroxide solution for 30 seconds and rinsed with deionized water. The silicon wafer with a resist pattern after the development was left to stand in a clean oven set to various temperatures for 30 seconds and then the resist pattern was observed using a scanning electron microscope to evaluate the shape of the pattern and the like. The results of the observation are shown in Table 1. 
     Example 2 
     A novolak type phenol resin (Mw: 8,000) was obtained by repeating the same procedures as in Example 1 except that 150 g of polyparahydroxystyrene (Mw: 7,000) synthesized by a known method was used instead of 150 g of the polyparahydroxystyrene (Mw: 5,000) in Example 1. Then, a substituted phenol resin was obtained in the same manner as in Example 1 except that 100 g of this novolak type phenol resin was used instead of 100 g of the novolak type phenol resin in Example 1. A resist pattern was formed in the same manner as in Example 1 except that 100 g of the substituted phenol resin was used instead of 100 g of the substituted phenol resin in Example 1 and the shape of pattern and the like of the formed resist pattern were evaluated by observation using a scanning electron microscope. The results are shown in Table 1. 
     Example 3 
     A novolak type phenol resin (Mw: 8,100) was obtained by repeating the same procedures as in Example 1 except that 21.8 g (0.131 mole) of 4-hydroxymethyl-2,3,6-trimethylphenol was used instead of 20 g of 4-hydroxymethyl-2,6-dimethylphenol in Example 1. In this example, the mole number of charged 4-hydroxylmethyl-2,3,6-trimethylphenol (compound (A)) was in a ratio of 10.5 moles per 100 moles of the structural unit of parahydroxystyrene. Then, a substituted phenol resin was obtained in the same manner as in Example 1 except that 100 g of this novolak type phenol resin was used instead of 100 g of the novolak type phenol resin. A resist pattern was formed in the same manner as in Example 1 except that 100 g of the substituted phenol resin was used instead of 100 g of the substituted phenol resin in Example 1 and the properties of the formed resist pattern were evaluated in the same manner as in Example 1. The results are shown in Table 1. 
     Example 4 
     A novolak type phenol resin (Mw: 8,000) was obtained by repeating the same procedures as in Example 1 except that 150 g (0.0214 mole as copolymer, or 1.26 moles as parahydroxystyrene unit) of parahydroxystyrene/styrene/tertiary butyl methacrylate copolymer (molar ratio of structural units of the copolymer components: 7/2/1, Mw: 7,000) synthesized by a known method was used instead of 150 g of the polyparahydroxystyrene (Mw: 5,000) of Example 1. In this example, the mole number of charged 4-hydroxylmethyl-2,6-dimethylphenol (compound (A)) was in a ratio of 1.04 moles per 100 moles of the structural unit of parahydroxystyrene in the parahydroxystyrene/styrene/tertiary butyl methacrylate copolymer [that is, structural units of polymerizable phenol compound contained in the polymer (B)] . Then, a substituted phenol resin was obtained in the same manner as in Example 1 except that 100 g of this novolak type phenol resin was used instead of 100 g of the novolak type phenol resin in Example 1 and that 40 g of di-tertiary butyl dicarbonate was used instead of 55 g of di-tertiary butyl dicarbonate in Example 1. A resist pattern was formed in the same manner as in Example 1 except that 100 g of the substituted phenol resin was used instead of 100 g of the substituted phenol resin in Example 1 and the properties of the formed resist pattern were evaluated in the same manner as in Example 1. The results are shown in Table 1. 
     Comparative Example 1 
     For comparison with Examples 1, 2 and 3, a polyparahydroxystyrene resin (Mw: 6,000) was synthesized by a known method. A substituted phenol resin was obtained in the same manner as in Example 1 except that 100 g of this polyparahydroxystyrene resin was used instead of 100 g of the novolak type phenol resin of Example 1. A resist pattern was formed in the same manner as in Example 1 except that 100 g of the substituted phenol resin was used instead of 100 g of the substituted phenol resin of Example 1. The resist pattern was observed using a scanning electron microscope to evaluate the pattern shape and the like of the formed resist. The results are shown in Table 1. 
     Comparative Example 2 
     For comparison with Example 4, a parahydroxystyrene/styrene/tertiary butyl methacrylate copolymer (molar ratio of structural units of the copolymer components: 7/2/1, Mw: 8,000) was synthesized by a known method. A substituted phenol resin was obtained in the same manner as in Example 4 except that 100 g of the parahydroxystyrene/styrene/tertiary butyl methacrylate copolymer was used instead of 100 g of the novolak type phenol resin of Example 4. A resist pattern was formed in the same manner as in Example 1 except that 100 g of the substituted phenol resin was used instead of 100 g of the substituted phenol resin of Example 4 and the properties thereof were evaluated in the same manner as in Example 4. The results are shown in Table 1. 
     The methods for determining the pattern shape and the like shown in Table 1 were as follows. 
     Pattern shape: The shape of the resist pattern after heating at 110° C. is shown in a magnified state in Table 1. 
     Heat resistance: When a resist pattern was heated, the temperature at which the resist pattern showed thermal deformation is shown in Table 1. 
     Sensitivity: Light exposure at which a 0.25 μm line and space were resolved at 1:1 is shown in Table 1 as the optimal exposure (Em). 
     Resolution: At the light exposure at which a 0.25 μm line and space were resolved at the 1:1, the minimum line width of a separated line and space was defined as the resolution of the evaluated resist. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                 Heat 
                   
                   
               
               
                   
                 Pattern 
                 resistance 
                 Sensitivity 
                 Resolution 
               
               
                   
                 shape 
                 (° C.) 
                 (mJ/cm 2 ) 
                 (μm) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Example 1 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 135 
                 34 
                 0.20 
               
               
                   
               
               
                 Example 2 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 135 
                 36 
                 0.20 
               
               
                   
               
               
                 Example 3 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 135 
                 40 
                 0.20 
               
               
                   
               
               
                 Example 4 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 130 
                 42 
                 0.20 
               
               
                   
               
               
                 Comparative Example 1 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 135 
                 50 
                 0.22 
               
               
                   
               
               
                 Comparative Example 2 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 130 
                 55 
                 0.22 
               
               
                   
               
            
           
         
       
     
     The mole number of charged compound (A), the mole number of the structural unit of polymerizable phenol compound in the polymer (B), the ratio of the mole number of charged compound (A) per 100 moles of the structural unit of the polymerizable phenol compound, and the Mw of the obtained novolak type phenol resin upon production of a novolak type phenol resin for Examples 1 to 4 are shown in Table 2. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                   
                 Mole number of 
                   
                   
               
               
                   
                 Mole number 
                 structural unit of 
                 Molar ratio of 
                   
               
               
                   
                 of compound (A) 
                 polymerizable phenol 
                 compound (A) 
                 Mw of phenol resin 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Example 1 
                 0.132 
                 1.25 
                 10.6 
                 6,000 
               
               
                 Example 2 
                 0.132 
                 1.25 
                 10.6 
                 8,000 
               
               
                 Example 3 
                 0.131 
                 1.25 
                 10.5 
                 8,100 
               
               
                 Example 4 
                 0.131 
                 1.26 
                 10.4 
                 8,000 
               
               
                   
               
            
           
         
       
     
     Table 1 indicates that the resist patterns of Examples 1 to 4 are superior to the resist patterns in Comparative Examples 1 and 2 in heat resistance, without showing rounded corners of the top portion of the resist pattern, and also in sensitivity and resolution. The resist patterns of Examples 1, etc. are summarized as follows. 
     Resist patterns of Examples 1 to 3: Resist pattern using the substituted phenol resin obtained by co-condensing the compound (A) and the homopolymer of polymerizable phenol compound and alkoxylating the co-condensation product. 
     Resist pattern of Example 4: Resist pattern using the substituted phenol resin obtained by co-condensing the compound (A) and the parahydroxystyrene/styrene/tertiary butyl methacrylate copolymer (copolymer of polymerizable phenol compound) and alkoxylating the co-condensation product. 
     Resist pattern of Comparative Example 1: Resist pattern using the substituted phenol resin obtained by alkoxylating the homopolymer of polymerizable phenol compound. 
     Resist Pattern of Comparative Example 2: Resist pattern using the substituted phenol resin obtained by alkoxylating the parahydroxystyrene/styrene/tertiary butyl methacrylate copolymer.