Cyanate ester and its uses

Abstract

To provide a cyanate ester having an arene ring and a fluorene ring, and use thereof.SOLUTION: A cyanate ester is represented by the following formula (1). The cyanate ester is suitable as a resist material for forming a resist underlay coating and / or a resist antireflection coating. (In the formula, each of Z1 and Z2 indicates the same or a different arene ring, each of Ar1 and Ar2 indicates the same or a different arene ring, each of R1,R2,R3, and R4 indicates the same or a different substituent, each of m and n is 0 or an integer of 1 or more, and each of p and q indicates an integer of 0-4).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a cyanate ester having an arene ring such as a condensed polycyclic arene ring and its use, and particularly to a cyanate ester having high etching resistance and useful as a resist material for forming a resist underlayer film and the like, and its use.

Background Art

[0002] Cyanate esters form a triazine ring by trimerization and form a polymer with high heat resistance. Therefore, by utilizing such properties, cyanate esters are used in a wide range of fields such as prepregs, composite materials, molding materials, printed wiring boards, encapsulation of electronic components, and adhesives.

[0003] International Publication No. 2016 / 163456 (Patent Document 1) describes a material for forming an underlayer film for lithography containing a compound represented by the following formula (O).

[0004]

Chemical formula

[0005] (In formula (O), X represents an oxygen atom, a sulfur atom, or no crosslinking, R 1 is a 2n-valent group having 1 to 30 carbon atoms or a single bond, R 2 is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 10 carbon atoms, etc., and the alkyl group, the alkenyl group, and the aryl group may contain a cyano group or the like. m1 is an integer from 0 to 4, at least one m1 is an integer from 1 to 4, m2 is an integer from 0 to 3 independently of each other, and p is 0 or 1)

[0006] This Document 1 describes R 1As an example, a fluorene-9,9-diyl group is exemplified. In the examples of this document, dibenzoxanthene dicyanate, bis(4,4'-dicyanatobiphenyl-3-yl)biphenylmethane, etc. are used.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, this document does not specifically describe cyanates containing an arene ring and a fluorene ring, and it is not described that such cyanates are used as resist materials, particularly as lower layer film materials (materials for forming lower layer films for lithography) or anti-reflection film materials with high etching resistance.

[0009] Therefore, an object of the present invention is to provide a cyanate having an arene ring and a fluorene ring and its use (resist material).

[0010] Another object of the present invention is to provide a resist lower layer film or protective film material and a resist anti-reflection film material with high etching resistance.

Means for Solving the Problems

[0011] As a result of intensive studies to achieve the above problems, the inventors of the present invention have found that a cyanate in which an arene ring, particularly a condensed polycyclic arene ring, is introduced at the 9,9-positions of a fluorene ring exhibits high heat resistance and high etching resistance and is useful as a material for a lower layer film (protective film) and / or an anti-reflection film of a resist, and thus completed the present invention.

[0012] That is, the cyanate of the present invention is represented by the following formula (1).

[0013]

Chem.

[0014] (wherein Z 1 and Z 2 each represent the same or different arene ring, Ar 1 and Ar 2 each represent the same or different arene ring, R 1 , R 2 , R 3 and R 4 each represent the same or different substituents, m and n represent integers of 0 or 1 or more, and p and q represent integers of 0 to 4)

[0015] Z 1 and Z 2 may be a condensed polycyclic arene ring. The cyanate ester may be a compound represented by the following formula (1a).

[0016]

Chem.

[0017] (wherein m and n represent integers of 0 to 6, R 1 , R 2 , R 3 and R 4 , and p and q are the same as in the above formula (1))

[0018] The cyanate ester may be at least one selected from 9,9-bis(6-cyanato-2-naphthyl)fluorene and 9,9-bis(5-cyanato-1-naphthyl)fluorene. The cyanate ester may be in a crystalline form.

[0019] The present invention also includes a resist material containing the cyanate ester. This resist material may be a resist underlayer film material and / or a resist antireflection film material. In addition, the resist material may further contain an organic solvent.

[0020] The present invention also includes a resist underlayer film and / or a resist antireflection film formed of the resist material (at least one resistant film formed of a cured product of the resist material and selected from the resist underlayer film and the resist antireflection film). That is, the resist underlayer film and / or the resist antireflection film can be formed of the resist material. The present invention also includes a method for forming the underlayer film and / or the antireflection film. In this method, the resist material is applied directly or indirectly to a substrate and heated to form the underlayer film and / or the antireflection film.

[0021] The present invention also includes a semiconductor device including a substrate, an underlayer film and / or an antireflection film formed directly or indirectly on the substrate, and at least one photoresist layer formed on the underlayer film and / or the antireflection film, wherein at least the photoresist layer is formed in a predetermined pattern. In this semiconductor device, the underlayer film and / or the antireflection film are formed of the resist material.

[0022] Furthermore, the present invention includes a patterning method. In this method, an underlayer film and / or an antireflection film are formed on a substrate directly or indirectly with the resist material, and at least one photoresist layer is formed on the underlayer film and / or the antireflection film; the photoresist layer is irradiated (or exposed) with energy rays in a predetermined pattern and developed to form a pattern. Also in this method, the underlayer film and / or the antireflection film are formed of the resist material.

[0023] In the present specification and claims, the number of carbon atoms of a substituent may be indicated as C1, C6, C 10 and so on. For example, an alkyl group having 1 carbon atom is indicated as a "C1 alkyl group", and an aryl group having 6 to 10 carbon atoms is indicated as a "C 6-10 aryl group".

[0024] Also, in this specification and the claims, the "fluorene skeleton" (or "fluorene ring") is used to mean a skeleton containing a fluorene skeleton such as a benzofluorene skeleton (benzofluorene ring) and a dibenzofluorene skeleton (dibenzofluorene ring).

Advantages of the Invention

[0025] In the present invention, since the cyanate ester has an arene ring and a fluorene ring, it has high heat resistance and etching resistance and is suitable as a resist material. In particular, it has high etching resistance and is suitable as a material for forming a resist underlayer film (or protective film) and / or a resist antireflection film.

Brief Description of the Drawings

[0026]

Fig. 1

Embodiments for Carrying Out the Invention

[0027] [Cyanate Ester] In the above formula (1) representing the cyanate ester of the present invention, ring Z 1 and ring Z 2 Examples of the arene ring represented by include monocyclic arene rings such as benzene rings and polycyclic arene rings; examples of the polycyclic arene ring include condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings) and ring-assembled arene rings (ring-assembled polycyclic aromatic hydrocarbon rings). Examples of the condensed polycyclic arene ring include condensed bicyclic to tetracyclic arene rings; examples of the condensed bicyclic arene ring include condensed bicyclic C 10-16 arene rings such as naphthalene rings and indene rings, and examples of the condensed tricyclic arene ring include condensed tricyclic C 14-20 arene rings such as anthracene rings and phenanthrene rings. Examples of the ring-assembled arene ring include biarene rings such as biphenyl rings, phenylnaphthalene rings, and binaphthyl rings; and terarenene rings such as terphenyl rings. Preferred ring-assembled arene rings are C12-18 It is an arene ring.

[0028] Preferred arene rings are C 6-14 arene rings, preferably C arene rings such as benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 arene rings, more preferably C arene rings such as benzene ring, naphthalene ring, etc. 6-10 arene rings, especially naphthalene ring. Particularly preferred arene rings are fused polycyclic arene rings, preferably fused polycyclic C 10-14 arene rings, and more preferably naphthalene ring. Incidentally, ring Z 1 and ring Z 2 may be the same as or different from each other, and are preferably the same.

[0029] R 1 and R 2 Examples of the substituents represented by include halogen atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups; alkoxy groups; acyl groups; nitro groups; cyano groups; substituted amino groups, etc.

[0030] Examples of the halogen atoms include fluorine atom, chlorine atom, bromine atom, etc. Examples of the alkyl group include linear or branched C 1-6 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, etc. Examples of the cycloalkyl group include C 5-8 cycloalkyl groups such as cyclopentyl group, cyclohexyl group, etc. Examples of the aralkyl group include C 6-10 aryl-C 1-4 alkyl groups such as benzyl group, etc. Examples of the aryl group include C 6-10 aryl groups such as phenyl group, etc. Examples of the alkoxy group include linear or branched C 1-10 alkoxy groups such as methoxy group, etc. Examples of the acyl group include C 1-6 acyl groups such as acetyl group, etc. Examples of the substituted amino group include dialkylamino groups, diacylamino groups, and examples of the dialkylamino group include diC 1-4Examples of the alkylamino group include, and examples of the diacylamino group include a diC 1-4 such as a diacetylamino group. Examples of the acylamino group include. Note that R 1 and R 2 may be the same or different, and are preferably the same.

[0031] Preferred R 1 and R 2 are a linear or branched C 1-4 alkyl group, a C 5-8 such as a cyclohexyl group, a C 6-14 cycloalkyl group, a C 1-4 aryl group, a linear or branched C 1-3 such as a methoxy group; more preferably a linear or branched C 1-2 alkyl group such as a methyl group or an ethyl group; particularly a C 1 alkyl group such as a methyl group. R 2 and R 1 or R 2 When is an aryl group, it forms the ring assembly arenarene ring together with the bonding ring Z 1 and Z 2 .

[0032] R 1 and R 2 The substitution numbers m and n of may be 0 or an integer of 1 or more, for example, can be selected from integers of 0 to 8, and preferably, step by step, are 0 to 6, 0 to 4, 0 to 3, 0 to 2, 0 or 1, and particularly 0. Note that the substitution numbers m and n may be the same or different from each other. When the substitution number m or n is 2 or more, the types of two or more R 1 or R 2 may be the same or different from each other.

[0033] Examples of the arenarene ring (aromatic hydrocarbon ring) represented by Ar 1 and Ar 2 include a monocyclic arenarene ring such as a benzene ring, a condensed polycyclic arenarene ring, a ring assembly arenarene ring, and the like.

[0034] Examples of the condensed polycyclic arene ring include ring Z 1 and ring Z 2 and similar condensed polycyclic C 10-14 arene rings and the like. A preferred condensed polycyclic arene ring is a naphthalene ring.

[0035] Examples of the ring assembly arene ring include bi-C 6-12 arene rings such as a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring. A preferred ring assembly arene ring is a biphenyl ring.

[0036] In addition, the types of Ar 1 and Ar 2 may be the same as or different from each other, and are preferably the same. The preferred arene rings represented by Ar 1 and Ar 2 are a benzene ring, a biphenyl ring, or a naphthalene ring.

[0037] Ar 1 and Ar 2 When they are benzene rings, the bonding (or substitution) positions of ring Z 1 and ring Z 2 to the 9-position of the fluorene ring are not particularly limited. When ring Z 1 and ring Z 2 are biphenyl rings, they may be at the 3-position or 4-position of the biphenyl ring, preferably at the 3-position of the biphenyl ring; when ring Z 1 and ring Z 2 are naphthalene rings, they may be at the 1-position or 2-position of the naphthalene ring, preferably at the 2-position of the naphthalene ring (or in the relationship of 2-naphthyl).

[0038] R 3 and R 4 Examples of the substituents represented by include a halogen atom; an alkyl group, an aryl group, a cyano group, and the like.

[0039] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group include linear or branched C 1-6 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Examples of the aryl group include C 6-10 aryl groups such as a phenyl group. Note that the substituents represented by R 3 and R 4 may be the same or different.

[0040] Preferred R 3 and R 4 are a halogen atom, a linear or branched C 1-4 alkyl group, a cyano group, more preferably a linear or branched C 1-3 alkyl group such as a methyl group and an ethyl group, particularly a C 1-2 alkyl group such as a methyl group. The types of R 3 and R 4 may be the same as or different from each other, and are preferably the same.

[0041] The substitution numbers p and q of R 3 and R 4 are integers from 0 to 4, preferably, step by step, 0 to 3, 0 to 2, 0 or 1, and particularly 0. Note that the substitution numbers p and q may be the same as or different from each other. When the substitution numbers p and q are 2 or more, the types of two or more R 3 or R 4 may be the same as or different from each other. Note that the substitution positions of R 3 and R 4 are not particularly limited. When Ar 1 or Ar 2 is a benzene ring (when it is a fluorene ring), they are at the 2nd to 7th positions of the fluorene ring, preferably the 2nd, 3rd or 7th position.

[0042] In the formula (1), the substitution position of the cyanato group (-OCN) with respect to the ring Z 1 , the ring Z 2 is not particularly limited. For the ring Z 1 , the ring Z 2When it is a naphthalene ring, it is substituted at any position of the 5th to 8th positions of the naphthyl group bonded to the 9th position of the fluorene ring (Ar 1 and Ar 2 is a benzene ring), and the 1st or 2nd position of the naphthalene ring is substituted with respect to the 9th position of the fluorene ring (substituted in the relationship of 1-naphthyl or 2-naphthyl), and it is preferably substituted in the relationship of 1,5-position or 2,6-position with respect to this substitution position, and particularly preferably substituted at the 2,6-position.

[0043] Examples of the compound represented by the formula (1) include 9,9-bis(cyanatophenyl)fluorene such as 9,9-bis(4-cyanatophenyl)fluorene; 9,9-bis(cyanat-C 1-4 alkylphenyl)fluorene such as 9,9-bis(4-cyanato-3-methylphenyl)fluorene and 9,9-bis(4-cyanato-3,5-dimethylphenyl)fluorene; 9,9-bis(cyanato-biphenyl)fluorene such as 9,9-bis(4-cyanato-3-phenylphenyl)fluorene; 9,9-bis[cyanato-C 6-12 aryl]fluorene such as 9,9-bis(5-cyanato-1-naphthyl) and 9,9-bis(6-cyanato-2-naphthyl)fluorene can be exemplified.

[0044] Preferred compounds represented by the formula (1) are compounds having a fluorene ring represented by the following formula (1a) (Z 1 and Z 2 is a naphthalene ring and Ar 1 and Ar 2 is a benzene ring); compounds having a benzofluorene ring represented by the following formula (1b) (Z 1 and Z 2 is a naphthalene ring and one of Ar 1 and Ar 2 is a benzene ring and the other is a naphthalene ring); and dibenzofluorene rings represented by the following formulas (1c) and (1d) (Z 1 and Z 2 is a naphthalene ring and Ar 1 and Ar 2a compound having a compound in which the ring is a naphthalene ring).

[0045] [Chemical formula]

[0046] (In the formula, R 1 , R 2 , R 3 and R 4 , and m, n, p, and q are the same as those in the above formula (1)) In the above formulas (1a), (1b), (1c), and (1d), the fluorene ring and the ring corresponding to the fluorene ring are assigned position numbers.

[0047] Examples of such compounds include 9,9-bis(cyanatonaphthyl)fluorene represented by the above formula (1a), 11,11-bis(cyanatonaphthyl)-2,3-benzofluorene (11,11-bis(cyanatonaphthyl)-11H-benzo[b]fluorene) represented by the above formula (1b), 13,13-bis(cyanatonaphthyl)-2,3,6,7-dibenzofluorene (13,13-bis(cyanatonaphthyl)-13H-dibenzo[b,h]fluorene) represented by the above formula (1c), 13,13-bis(cyanatonaphthyl)-1,2,7,8-dibenzofluorene (13,13-bis(cyanatonaphthyl)-13H-dibenzo[a,i]fluorene) represented by the above formula (1d), and the like. The naphthalene ring is preferably bonded to the fluorene ring and the cyanato group in the relationship of the bonds of 1,5-diyl and 2,6-diyl.

[0048] More preferred compounds include a compound represented by the following formula (1a) (in the above formula (1), Z 1 and Z 2 are naphthalene rings, and Ar 1 and Ar 2 are benzene rings).

[0049] [Chemical formula]

[0050] (wherein, R 1 , R 2 , R 3 and R 4 , and m, n, p and q are the same as in the above formula (1))

[0051] In such compounds, preferred values of m, n, p and q are each 0. Therefore, preferred cyanate esters include 9,9-bis(cyanatonaftyl)fluorenes and the like. Examples of the 9,9-bis(cyanatonaftyl)fluorenes include 9,9-bis(6-cyanato-2-naphthyl)fluorene, 9,9-bis(5-cyanato-1-naphthyl)fluorene and the like. Among these compounds, 9,9-bis(6-cyanato-2-naphthyl)fluorene is particularly preferred.

[0052] Such cyanate esters may be in a liquid form at room temperature (20 °C), but are preferably in a crystalline form. Cyanate esters in a crystalline form have high handleability and are industrially advantageous. For example, in the above formula (1), the melting point of a cyanate ester in which the rings Ar 1 , Ar 2 , Z 1 , and Z 1 are benzene rings is 130 to 170 °C, preferably 140 to 160 °C, particularly 145 to 150 °C, and the melting point of a cyanate ester in which the rings Ar 1 , Ar 2 are benzene rings, the rings Z 1 , and Z 1 are naphthalene rings is 200 to 240 °C, preferably 210 to 235 °C, particularly 220 to 230 °C. Therefore, cyanate esters in which the rings Z 1 , and Z 1 are polycyclic arene rings, particularly condensed polycyclic arene rings, are suitable for forming a highly heat-resistant and highly etching-resistant resist film.

[0053] [Method for producing cyanate ester] The cyanate ester represented by the formula (1) can be prepared by using a conventional method, for example, reacting a compound represented by the following formula (2) with a cyanogen halide represented by the following formula (3) in a solvent in the presence of a basic compound (such as a tertiary amine like trialkylamine). The reaction may be carried out in the presence of a solvent that is immiscible with water. Also, as described in Patent Document 2, a compound represented by the following formula (2) and a cyanogen halide may be reacted under acidic conditions in a two-phase solvent system of water and an organic solvent in the presence of a tertiary amine.

[0054] [Chemical formula]

[0055] (In the formula, X represents a halogen atom, Z 1 , Z 2 , Ar 1 , Ar 2 , R 1 , R 2 , R 3 and R 4 , and m, n, p and q are the same as in the formula (1))

[0056] Examples of the cyanogen halide represented by the formula (3) include cyanogen chloride and cyanogen bromide. The amount of the cyanogen halide used is 0.7 to 5 moles, preferably 1 to 3.5 moles, more preferably 1.2 to 3 moles, per mole of the hydroxyl group of the compound represented by the formula (2).

[0057] The basic compound may be either an organic base or an inorganic base. Examples of the organic base include trialkylamines such as trimethylamine, triethylamine, and tri-n-butylamine; N,N-dialkylanilines such as N,N-dimethylaniline; aromatic heterocyclic amines such as pyridine; and aliphatic heterocyclic amines such as 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonene. Preferred organic bases are triC 1-4 alkylamines. The amount of the organic base used is 1 to 8 moles, preferably 1.2 to 3.5 moles, per mole of the hydroxy group of the compound represented by formula (2).

[0058] Examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; and alkali metal carbonates. Preferred inorganic base is sodium hydroxide. The amount of the inorganic base used is 1 to 5 moles, preferably 1.2 to 3.5 moles, per mole of the hydroxy group of the compound represented by formula (2).

[0059] Examples of the solvent include hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters, amides, sulfoxides, and nitriles. These solvents can also be used as a mixed solvent, and as the mixed solvent, a mixture of a solvent immiscible with water (a two-phase solvent of water and an organic solvent) can be used.

[0060] Examples of hydrocarbons include aliphatic hydrocarbons such as n-hexane and octane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Examples of halogenated hydrocarbons include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene, and bromobenzene. Examples of ethers include diethyl ether, dimethyl cellosolve, diglyme, dioxane, and tetrahydrofuran; examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; examples of esters include methyl acetate and ethyl acetate; examples of amides include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; examples of sulfoxides include dimethyl sulfoxide; and examples of nitriles include acetonitrile and benzonitrile.

[0061] The reaction can be carried out under normal pressure or under pressure, and the reaction temperature is -20°C to 50°C, preferably -15°C to 25°C, more preferably -10°C to 15°C. The reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

[0062] After completion of the reaction, the cyanate ester (1) can be separated and purified from the reaction mixture by conventional separation methods, such as separation means including filtration, washing, concentration, extraction, crystallization, recrystallization, column chromatography, or separation means combining these. For example, the reaction mixture may be concentrated if necessary, the precipitate may be filtered off, washed, and dried, or the precipitate may be crystallized.

[0063] [Uses of Cyanate Esters] The compound (cyanic acid ester) represented by formula (1) has film-forming properties on its own and has high solubility in organic solvents compared to, for example, novolak resins that are used as materials for resist underlayer films. In particular, it has a high glass transition temperature (heat resistance) and chemical resistance, excellent electrical insulation properties, and forms a cured film with a low dielectric constant and a small dielectric tangent. Therefore, the cyanic acid ester may form a resin composition in combination with a resin component. Examples of the resin component include thermoplastic resins such as polyolefin-based resins, polystyrene-based resins, polyester-based resins, polycarbonate-based resins, polyphenylene ether-based resins, and polyethersulfone resins, and thermosetting resins such as epoxy resins, vinyl ester-based resins, phenol resins, bismaleimide resins, oxetane resins, and benzoxazine compounds. These resin components can be used alone or in combination of two or more. Preferred resin components are polyphenylene ether-based resins, epoxy resins, phenol resins, and bismaleimide resins.

[0064] Examples of the epoxy resin include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and alicyclic epoxy resins in which a cyclohexene ring is epoxidized. Examples of the glycidyl ether type epoxy resin include bisphenol type epoxy resins, novolak type epoxy resins, and naphthalene type epoxy resins.

[0065] Examples of the bisphenol type epoxy resin include biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol E type epoxy resins, bisphenol Z type epoxy resins, and fluorene type epoxy resins (such as 9,9-bis(glycidyloxyC 6-10 aryl)fluorene, etc.), and the bisphenol type epoxy resin may be a phenoxy type epoxy resin with a large molecular weight. Examples of the novolak type epoxy resin include phenol novolak type epoxy resins and cresol novolak epoxy resins.

[0066] Examples of the phenolic resin include novolak-type phenolic resins and resol-type phenolic resins. A preferred phenolic resin is a novolak-type phenolic resin.

[0067] The content of the compound (cyanate ester) represented by the formula (1) is 10 to 120 parts by mass, preferably 20 to 100 parts by mass, and more preferably 25 to 75 parts by mass with respect to 100 parts by mass of the resin component.

[0068] The resin composition may contain an elastomer and an additive. Examples of the elastomer include styrenic elastomers such as styrene-butadiene block copolymers, styrene-isoprene block copolymers, and styrene-hydrogenated butadiene block copolymers, olefinic elastomers such as ethylene-propylene-based elastomers, polyamide-based elastomers, and polyester-based elastomers. The content of the elastomer is 0 to 30 parts by mass, preferably 1 to 25 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the cyanate ester and the resin component.

[0069] Examples of the additive include fillers, silane coupling agents, stabilizers (such as antioxidants, ultraviolet absorbers, and storage stabilizers), curing agents according to thermosetting resins, antistatic agents, flame retardants, defoaming agents, leveling agents, and colorants.

[0070] Examples of the filler include inorganic fillers such as carbon black, silica, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, barium sulfate, clay, kaolin, and talc, and fibrous fillers such as glass fibers and carbon fibers. The amount of the filler used is 10 to 250 parts by mass, preferably 25 to 200 parts by mass, and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the total amount of the cyanate ester and the resin component.

[0071] Examples of the silane coupling agent include epoxy group-containing silane coupling agents such as 3-glycidyloxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl group-containing silane coupling agents such as 3-(meth)acryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyl-tri(2-methoxyethoxy)silane; and amino group-containing silane coupling agents such as 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

[0072] The amount of the silane coupling agent used is 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the cyanate ester and the resin component.

[0073] Such a resin composition can be effectively used as a prepreg, a laminate (including a metal foil-clad laminate), a printed wiring board (including a multilayer printed wiring board), a sealing agent, and the like.

[0074] [Resist material] Furthermore, the cyanate ester forms a cured film (resistant film) having high etching resistance (or radiation resistance, high energy ray resistance), and this cured film also has an antireflection ability. Therefore, the cyanate ester is suitable as a material for forming a protective film, for example, at least one resistant film selected from an underlayer resist film and / or an antireflection film (an underlayer resist film and an antireflection resist film) in pattern formation for forming a predetermined pattern (or circuit pattern) by lithography.

[0075] The resist material (composition) of the present invention only needs to contain at least the cyanate ester represented by the above formula (1) (the first cyanate ester), and may contain a second cyanate ester if necessary. Examples of the second cyanate ester include biphenyl type dicyanate esters, cyanate esters having a bisphenol fluorene skeleton, cyanate esters having a bisphenol alkane skeleton, cyanate esters having a triphenol alkane skeleton, novolak type cyanate esters, and the like.

[0076] Examples of the cyanate ester having a bisphenol fluorene skeleton include 9,9-bis(4-cyanatophenyl)-9H-fluorene, 9,9-bis(3-methyl-4-cyanatophenyl)-9H-fluorene, 9,9-bis(3,5-dimethyl-4-cyanatophenyl)-9H-fluorene, 9,9-bis[4-cyanato-3-phenylphenyl]fluorene, and the like. Examples of the cyanate ester having a bisphenol alkane skeleton include bisphenol A type dicyanate ester, bisphenol AP type dicyanate ester, bisphenol B type dicyanate ester, bisphenol C type dicyanate ester, bisphenol E type dicyanate ester, bisphenol F type dicyanate ester, bisphenol AD type dicyanate ester, bisphenol S type dicyanate ester, bisphenol Z type dicyanate ester, and the like. Examples of the cyanate ester having a triphenol alkane skeleton include tris(4-cyanatophenyl)methane, tris(4-cyanatophenyl)ethane, and the like. Examples of the novolak type cyanate ester include phenol novolak type cyanate ester, cresol novolak type cyanate ester, and the like.

[0077] The amount of the second cyanate ester used can be selected from the range of 0 to 100 parts by mass with respect to 100 parts by mass of the first cyanate ester, and is 2 to 75 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass.

[0078] The cyanate ester containing at least the first cyanate ester may be used as a resist material as it is. A preferred resist material (composition) contains an organic solvent in addition to the cyanate ester.

[0079] The organic solvent may be a hydrocarbon solvent, a ketone solvent, an ester solvent, a cellosolve solvent, etc. Examples of the hydrocarbon solvent include alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as toluene and xylene. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, and ethyl lactate. Examples of the cellosolve solvent include cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate, carbitols such as methyl carbitol and ethyl carbitol, and carbitol acetates such as methyl carbitol acetate, ethyl carbitol acetate, and butyl carbitol acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. The organic solvent can be used alone or in combination of two or more.

[0080] The compound (cyanate ester) represented by formula (1) can be cured by heating. Therefore, although not necessarily required, the resist material may contain an acid catalyst (acid generator), a crosslinking agent, etc.

[0081] The acid generator promotes the curing of the cyanate ester and may be either a photoacid generator or a thermal acid generator. Examples of the acid generator include onium salts, diazomethane derivatives, glyoxime derivatives, sulfonic acid esters, etc.

[0082] Examples of the onium salt include sulfonium trifluoromethanesulfonate, sulfonium p-toluenesulfonate, etc. Examples of sulfonium trifluoromethanesulfonate include triphenylsulfonium, (p-t-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-t-butoxyphenyl)sulfonium trifluoromethanesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, etc.; examples of sulfonium p-toluenesulfonate include triphenylsulfonium p-toluenesulfonate, (p-t-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, tris(p-t-butoxyphenyl)sulfonium p-toluenesulfonate, etc. Examples of the diazomethane derivative include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(naphthalenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(t-butylsulfonyl)diazomethane, etc.

[0083] Examples of the glyoxime derivative include bis-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-(n-butanesulfonyl)-α-dimethylglyoxime. Examples of the sulfonic acid ester include sulfonic acid ester derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, and N-hydroxyphthalimide benzenesulfonic acid ester; nitrobenzyl sulfonates such as 2,6-dinitrobenzyl p-toluenesulfonate; and tris-sulfonyloxybenzenes such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0084] The content of the acid generator is 0 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the cyanate ester.

[0085] In addition, the resist material containing the acid generator may contain a basic compound in order to improve the storage stability. This basic compound serves as a quencher that captures a small amount of acid generated from the acid generator and is effective in improving the crosslinking reaction.

[0086] The basic compound may be either an organic base or an inorganic base, and the organic base may be any of amines (primary amine, secondary amine, tertiary amine). A preferred basic compound is an organic base, particularly a tertiary amine. Examples of the amines containing a tertiary amine include C 1-10 alkylamines such as trimethylamine and triethylamine; and tetra-C1-4 Alkylalkylene diamine; alkanolamines such as triethanolamine and dimethylaminoethanol; N,N-diC such as N,N-dimethylaniline 1-4 Alkyl C 6-10 Arene; diC such as benzyldimethylamine 1-4 Alkylamino C 1-4 Alkyl C 6-10 Examples of the heterocyclic amines include arenes, morpholine, N-methylmorpholine, N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylpyrrolidone, 1,4-diazabicyclo[2.2.2]octane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), and the like.

[0087] The content of the basic compound is 0 to 2 parts by mass, preferably 0 to 1 part by mass, based on 100 parts by mass of the resist material.

[0088] Examples of the crosslinking agent include melamines, guanamines (benzoguanamines), ureas, epoxies, vinyl ethers, azides, and the like.

[0089] Examples of the melamines include hexamethylol melamine and hexamethoxymethyl melamine; examples of the guanamines include tetramethylol guanamine and tetramethoxymethyl guanamine; and examples of the ureas include tetramethylol urea and tetramethoxymethyl urea. The epoxies include compounds having two or more, preferably 3 to 6 epoxy groups. Examples of such compounds include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin triglycidyl ether, trimethylol methane triglycidyl ether, trimethylol propane triglycidyl ether, and tris(2,3-epoxypropyl) isocyanurate. The vinyl ethers include compounds having two or more, preferably 3 to 6 vinyl ether groups in one molecule. Examples of such compounds include ethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, trimethylol propane trivinyl ether, 1,4-cyclohexanediol divinyl ether, and pentaerythritol tetravinyl ether.

[0090] The content of the crosslinking agent is 0 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the cyanate ester.

[0091] The resist material may contain additives if necessary. Examples of such additives include stabilizers (such as antioxidants and storage stabilizers), ultraviolet absorbers, surfactants, antistatic agents, flame retardants, and colorants.

[0092] The resist film can be formed by applying a resist material directly or indirectly to a substrate (or base plate) in a conventional manner and heating or baking the resulting coating film, and the coating film may be cured. More specifically, a resist pattern can be formed by applying the resist material onto a substrate to form a lower layer film (or coating film), forming at least one photoresist layer on this lower layer film, exposing or irradiating the photoresist layer with energy rays or radiation of a predetermined wavelength in a predetermined pattern, and developing to form a predetermined resist pattern (or circuit pattern).

[0093] Note that the resist film or the lower layer film has the property of absorbing the energy rays or radiation and also functions as an antireflection film. Therefore, the resist material is suitable for forming the lower layer film and / or the antireflection film.

[0094] As the substrate (or base material), a known substrate can be used, and examples include substrates formed of silicon, silicon nitride, titanium nitride, aluminum, etc. The substrate may be a laminate in which a film to be processed is laminated on a base material (support).

[0095] An adhesion layer for enhancing the adhesion to the resist film may be formed on the surface of the base material (or substrate). For applying the resist material to the base material (or substrate), coating methods such as spin coating and printing methods such as screen printing can be used.

[0096] After applying the resist material to the base material (or substrate), the lower layer film (or coating film) preferably has the solvent removed by drying, and then is heated or baked and cured. The heating or baking temperature can be selected from the range of 80 to 400 °C, preferably 100 to 300 °C, and more preferably 150 to 250 °C. The thickness of the lower layer film is 10 nm to 10 μm, preferably 20 to 1000 nm, and more preferably 50 to 800 nm.

[0097] The intermediate layer may be formed of a resist containing a polysilsesquioxane derivative in order to enhance the oxygen gas etching resistance, or may be formed using a PVD method (physical vapor deposition method) or a CVD method (chemical vapor deposition method). Further, when a silicon-containing film such as silicon oxide, silicon nitride, or SiON film is formed as the intermediate layer, the light absorptivity with respect to light rays having a predetermined wavelength can be enhanced, and an antireflection function can also be imparted.

[0098] Note that a conventional photoresist (positive or negative photoresist) can be used for the photoresist layer, and for forming a fine pattern, a positive photoresist, particularly a chemically amplified positive photoresist, can be used. As the photoresist, a material that is sensitive to high-energy rays having a wavelength of 300 nm or less can be used. Specifically, materials that are sensitive to excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, and X-rays can be used. A typical photoresist contains an organic solvent, an acid generator, particularly a photoacid generator, as described above.

[0099] The photoresist layer can be formed into a coating layer in the same manner as described above by applying a photoresist material to the lower layer film or the intermediate layer using a wet method such as spin coating or screen printing and then performing prebaking (PAB) at 80 to 180°C. The thickness of the coating layer is 20 to 500 nm, preferably 50 to 300 nm. By pattern exposing the coating layer, post-baking (post-exposure baking (PEB)), and developing, a resist pattern can be formed.

[0100] When etching using the resist pattern as a mask, an etching gas can be used. Examples of the etching gas include oxygen gas, inert gases such as helium and argon, hydrogen, nitrogen, carbon monoxide, carbon dioxide, ammonia, nitrogen dioxide, and sulfur dioxide. These etching gases can also be used as a mixed gas. A preferred etching gas is oxygen gas.

Example

[0101] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The evaluation methods in the examples and comparative examples are as follows.

[0102] 1 1H-NMR: Using a nuclear magnetic resonance apparatus (BRUKER's "ADVANCE III HD"), with tetramethylsilane as the internal standard and CDCl3 as the solvent, 1 the 1H-NMR spectrum was measured.

[0103] Melting point: Measured using a differential scanning calorimeter (EXSTAR DSC6200 manufactured by SII NanoTechnology Inc.) under a nitrogen atmosphere at a measurement temperature of 30 to 300 °C and a heating rate of 10 °C / min. From the obtained DSC chart (DSC curve), the temperature at the peak top of the endothermic peak due to melting was determined as the melting point.

[0104] (Heat resistance (weight loss temperature)) Using a differential thermal gravimetric analyzer (TG / DTA6200 manufactured by Hitachi High-Technologies Corporation), the 5% weight loss temperature and 10% weight loss temperature were measured under the following conditions.

[0105] Measurement temperature range: 30 to 520 °C Heating rate: 10 °C / min Gas atmosphere: Under a nitrogen atmosphere.

[0106] (Heating residue) Heated to 180 °C, and the weight loss was measured when the weight change stopped and left for 1 minute.

[0107] (Purity) Using liquid chromatography (LC, LC-2010A manufactured by Shimadzu Corporation), measured with acetonitrile / water (volume ratio) = 70 / 30 → 95 / 5 → 70 / 30 as the eluent.

[0108] (Refractive index) Using a refractometer (manufactured by Atago Co., Ltd., "DR-M2"), the refractive index at a measurement temperature of 25°C and a wavelength of 589 nm was measured.

[0109] Synthesis Example 1 (Synthesis of 9,9-bis(6-cyanato-2-naphthyl)fluorene) Into a reactor equipped with a stirrer, a dropping funnel, a thermometer, and a three-way cock, 284 g (0.63 mol) of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF) (manufactured by Osaka Gas Chemical Co., Ltd.) was charged, and after purging with nitrogen gas, 2000 ml of tetrahydrofuran was added and dissolved, and the mixture was cooled to an internal temperature of 5°C or lower.

[0110] 276 g (2.52 mol) of bromocyan was added in portions over 5 minutes and dissolved, while cooling the internal temperature to 0°C or lower. While maintaining the internal temperature at 0 to 10°C, 350 ml (2.52 mol) of triethylamine was added over 150 minutes. Then, the temperature was raised to room temperature and the reaction was continued for 45 hours. The reaction solution was analyzed by high performance liquid chromatography (HPLC), and it was confirmed that the raw materials had disappeared.

[0111] The precipitate was separated by filtration, washed with tetrahydrofuran, and the filtrate and washing solution were collected and concentrated under heating and reduced pressure to obtain 273 g of a yellowish-brown mud-like substance (crude product yield: 86.6%).

[0112] Next, 273 g of the yellowish-brown mud-like substance was dissolved in 1000 ml of chloroform at 65°C, then 600 ml of ethyl acetate was added, and the mixture was cooled to room temperature over 60 minutes with stirring. Then, it was allowed to stand at 0°C for 30 minutes and then at -20°C overnight. The precipitate was separated by filtration, washed with a chloroform / ethyl acetate 0.6 L / 0.6 L (volume ratio 1:1) mixture cooled to -20°C, and then dried to dryness under heating and reduced pressure to obtain 9,9-bis(6-cyanato-2-naphthyl)fluorene (BNF cyanate ester) represented by the following formula as crystals.

[0113]

Chemical formula

[0114] NMR: 11H-NMR (CDCl3, 300 MHz) δ (ppm): 7.3 (m, 2H), 7.5 (d, 6H), 7.6 (d, 2H), 7.7 (s, 2H), 8.0 (m, 8H) Melting point: 224 °C.

[0115] Synthesis Example 2 (Synthesis of 9,9-bis(4-cyanatophenyl)fluorene) 9,9-Bis(6-hydroxynaphthalen-2-yl)fluorene (BNF) was replaced with 9,9-bis(4-hydroxyphenyl)fluorene (BPF, manufactured by Osaka Gas Chemical Co., Ltd.), and 9,9-bis(4-cyanatophenyl)fluorene (BPF cyanate ester) represented by the following formula was obtained as crystals in the same manner as in Synthesis Example 1 except for using BPF.

[0116] [Chemical formula]

[0117] NMR: 1 1H-NMR (CDCl3, 300 MHz) δ (ppm): 7.2 - 7.4 (m, 14H), 7.9 (d, 2H) Melting point: 147 °C.

[0118] [Examples 1 and 2 and Comparative Examples 1 and 2] Each resist composition having the following composition was applied to a silicon substrate using a spin coater, and heated (pre-baked; PAB) at a predetermined temperature and for a predetermined time as follows to form a cured film having a predetermined film thickness.

[0119] Example 1: A cyclohexanone solution containing 10% by mass of the BPF cyanate ester of Synthesis Example 1 (film thickness of cured film: 400 nm, PAB: 200 °C / 90 seconds) Example 2: A cyclohexanone solution containing 10% by mass of the BPF cyanate ester of Synthesis Example 2 (film thickness of cured film: 250 nm, PAB: 120 °C / 90 seconds) Comparative Example 1: BisA cyanate ester: 2,2-bis(4-cyanatophenyl)propane (manufactured by Kanto Chemical Co., Inc.) Comparative Example 2: ArF resist (TArF-P6111, a polymer having an acrylic lactone skeleton: Tokyo Ohka Kogyo Co., Ltd.) (film thickness of cured film: 260 nm, PAB: 130 °C / 60 seconds)

[0120] In Comparative Example 1, the curing of bisphenol A cyanate ester was attempted under various temperature conditions, but it did not cure. Instead, it melted, crystallized, and sublimated upon heating, making it difficult to form a cured film as a single substance. In contrast, cyanate esters having a fluorene skeleton (BNF cyanate ester and BPF cyanate ester) easily formed a cured film upon heating.

[0121] Reactive Ion Etching (RIE) Test Then, a reactive ion etching (RIE) test was conducted under the following conditions. Taking the etching rate of Comparative Example 2 (ArF resist) as "1", the etching rates of the cyanate esters of Example 1 and Example 2 were evaluated. That is, as described above, three silicon wafers on which cured films of each resist composition were formed were prepared. Masking tape was attached across the center of each silicon wafer to prepare test pieces. All the test pieces were placed in the chamber of a reactive ion etching (RIE) apparatus, and reactive ion etching was performed under the following conditions. In Example 1 and Comparative Example 2, one test piece of each resist composition was sequentially taken out after 30 seconds, 60 seconds, and 120 seconds from the start of etching. In Example 2, one test piece of each resist composition was sequentially taken out after 60 seconds, 90 seconds, and 120 seconds from the start of etching. The test was terminated by visually confirming whether the bottom of the chamber was colored or the cured film disappeared and the silicon substrate was exposed. Also, such an operation was repeated 4 times.

[0122] [RIE Dry Etching Conditions] Gas species: CF4 = 100 ml / min, O2 = 2 ml / min RF output: 150 W Pressure: 10 Pa Time: 30 seconds → 60 seconds → 120 seconds

[0123] Film thickness T (nm) and etching time ET (Seconds), the etching rate equation was obtained. The relationship between the etching time (processing time) and the film thickness is shown in Fig. 1.

[0124] The etching rate equation and the etching rate were as follows. Example 1 (BNF cyanate ester): T = -0.848×E T +400 Etching rate: 0.848 nm / second Example 2 (BPF cyanate ester): T = -1.08×E T +254 Etching rate: 1.08 nm / second Comparative Example 2 (ArF resist): T = -1.50×E T +269 Etching rate: 1.50 nm / second

[0125] When the etching rate of Comparative Example 2 (ArF resist) was set to "1.0", the etching rate ratios of Example 1 (BNF cyanate ester) and Example 2 (BPF cyanate ester) were as follows.

[0126] Comparative Example 2 (ArF resist) / Example 2 (BPF cyanate ester) / Example 1 (BNF cyanate ester) = 1.0 / 0.72 / 0.56

[0127] As is clear from this etching rate ratio and the slope of the graph in Fig. 1, Example 2 (BPF cyanate ester) showed higher etching resistance than Comparative Example 2 (ArF resist), and in particular, it was confirmed that Example 1 (BNF cyanate ester) had high etching resistance.

Industrial Applicability

[0128] The cyanate ester of the present invention forms a cured film with high heat resistance and chemical resistance. Therefore, the cyanate ester can be used as a modifier for various thermosetting resins. Further, in combination with epoxy resins, phenol resins, bismaleimide resins, etc., it can be used as paints, inks, adhesives, etc., and is also suitable for forming resin compositions (including flame-retardant resin compositions) suitable for structural materials. In particular, due to its high electrical insulation and small dielectric constant and dielectric loss tangent, the said cyanate ester and resin composition are suitable as electrical and electronic materials, and the composition containing cyanate ester can be used for prepregs, composite materials, molding materials, printed wiring boards, encapsulants for electronic components, etc. Furthermore, a cured film with high etching resistance can be formed. Therefore, the cyanate ester can be used as a component of a resist material (composition), and in the manufacture of semiconductor devices that form fine processing or a predetermined pattern (circuit pattern) by lithography using a photoresist material, it is advantageous for forming resistant films such as an underlying film (protective film) and an antireflection film.

Claims

1. A resist material containing a cyanate ester represented by the following formula (1). 【Chemical Formula 1】 (wherein Z １ and Z ２ each represent the same or different fused polycyclic arene rings, Ar １ and Ar ２ each represent the same or different arene rings, R １ , R ２ , R ３ and R ４ each represent the same or different substituents, m and n represent integers of 0 or 1 or more, and p and q represent integers of 0 to 4)

2. The resist material according to Claim 1, wherein the cyanate ester is represented by the following formula (1a). 【Chemical 2】 (wherein, m and n represent integers of 0 to 6, and R １ , R ２ , R ３ and R ４ , and p and q are the same as those in the formula (1) of claim 1)

3. The resist material according to Claim 1 or 2, wherein the cyanate ester is at least one selected from 9,9-bis(6-cyanato-2-naphthyl)fluorene and 9,9-bis(5-cyanato-1-naphthyl)fluorene.

4. The resist material according to any one of Claims 1 to 3, wherein the cyanate ester is in a crystalline form.

5. The resist material according to any one of Claims 1 to 4, which is at least one selected from a resist underlayer film material and a resist antireflection film material.

6. The resist material according to any one of Claims 1 to 5, further containing an organic solvent.

7. A resistive film of at least one selected from a resist underlayer film and a resist antireflection film, formed of the resist material according to any one of Claims 1 to 6.

8. A method of forming an underlayer film and / or an antireflection film by applying the resist material according to any one of Claims 1 to 6 directly or indirectly onto a substrate and heating it.

9. A semiconductor device including a substrate, an underlayer film and / or an antireflection film formed directly or indirectly on the substrate, and at least one photoresist layer formed on the underlayer film and / or the antireflection film, wherein at least the photoresist layer is formed in a predetermined pattern, and the underlayer film and / or the antireflection film is formed of the resist material according to any one of Claims 1 to 6.

10. A patterning method of forming an underlayer film and / or an antireflection film directly or indirectly on a substrate, forming at least one photoresist layer on the underlayer film and / or the antireflection film, and irradiating and developing the photoresist layer with energy rays in a predetermined pattern, wherein the underlayer film and / or the antireflection film is formed of the resist material according to any one of Claims 1 to 6.

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