JP2008285470A - New fluorene compound having phenolic hydroxy group and methylol group and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorene compound excellent in heat resistance and etching resistance. <P>SOLUTION: This bishydroxyphenylindene compound (fluorene compound) is obtained by reacting a phenolic hydroxy group-having fluorene compound with a phenol compound and an aldehyde compound. In the formulas, a ring Z<SP>1</SP>, a ring Z<SP>2</SP>and a ring Z<SP>3</SP>are each an aromatic hydrocarbon ring; R<SP>1a</SP>, R<SP>1b</SP>, R<SP>2a</SP>, R<SP>2b</SP>and R<SP>2c</SP>are each identically or differently a substituent; k1, k2, m1, m2, m3, n1, n2, n3 are each an integer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel fluorene compound having a phenolic hydroxyl group and a methylol group, a method for producing the same, and a cured product obtained by curing the fluorene compound. The present invention also relates to a fluorene compound excellent in etching resistance, a resin composition thereof (for example, a photosensitive resin composition), and a pattern formed from the photosensitive resin composition.

  In general, novolac type phenolic resins are used for molded products, laminated products, shell molds, friction materials, grindstones, photosensitive agents, thermal papers, pressure sensitive papers, curing agents for epoxy resins for semiconductor sealing materials, and the like. With the rapid development of the IT field in recent years, a novolac type phenol resin having high heat resistance is craved.

  In order to improve the heat resistance of the novolac phenol resin, it is known to introduce a rigid skeleton such as a fluorene skeleton into the novolac phenol resin. For example, JP 2003-226727 A (Patent Document 1) discloses phenols (A) (phenols, naphthols, bisphenolfluorene type phenols, alkylphenols such as cresol, bisphenol A, bisphenol F, bisphenol S, resorcin, catechol. And polyaromatics obtained by reacting aromatics (B) excluding phenols and heterocyclic compounds (C) containing nitrogen as a hetero atom Discloses a flame retardant phenolic resin material containing a phenolic condensate condensed via an aldehyde (D), wherein the aromatics (B) is a compound represented by the following formula: .

XCH ₂ -R ₁ -CH ₂ X
(In the formula, R ₁ represents any _one of a biphenyl derivative, a phenylene derivative, a naphthalene derivative, a biphenylene derivative, a fluorene derivative, and a bisphenolfluorene derivative, and X represents any of a halogen atom, a hydroxyl group, and an alkoxyl group having 10 or less carbon atoms. .)
In this document, in a typical production method for obtaining the phenolic resin material, first, a condensation product is obtained by subjecting phenols (A) and aromatics (B) to a condensation reaction in the presence of an acid catalyst. In the condensation reaction, the amount of phenols (A) used is usually 0.3 to 20 mol, preferably 0.4 to 15 mol, per 1 mol of the compound represented by aromatics (B). It is described that.

In particular, as an example in which a fluorene skeleton is introduced, JP 2004-339499 A (Patent Document 2) discloses a composition containing a resin having a fluorene skeleton and an additive. This document describes a phenolic resin as a resin having a fluorene skeleton. In the production of a phenolic resin, a co-condensation component, for example, phenols (C _{1- 1} such as phenol and cresol) is used together with bisphenolfluorenes. _4- alkyl-phenol, dihydroxybenzene such as resorcin, etc.), urea, guanamines, melamines, etc. may be used in combination, and the ratio of bisphenolfluorenes and co-condensation component is the former / latter (molar ratio) = 100 It is described that it may be about / 0 to 5/95, preferably 100/0 to 10/90, and more preferably about 100/0 to 20/80.

In the phenol resins described in these documents, although a fluorene skeleton is introduced, characteristics such as heat resistance and plasma resistance are still insufficient, and further improvement of these characteristics is desired. Further, when the bisphenol having a fluorene skeleton as described above is condensed using a conventional method, the molecular weight of the resulting novolak type phenol resin cannot be sufficiently increased (for example, the weight average molecular weight is about 1000 at most). For this reason, even though a fluorene skeleton could be introduced, the molecular weight was small and it was not practical.
JP 2003-226727 A (Claims, paragraph number [0022], paragraph number [0045]) JP 2004-339499 A (claims, paragraph numbers [0068] to [0071])

  Accordingly, an object of the present invention is to provide a novel fluorene compound excellent in heat resistance, plasma resistance, or etching resistance, a cured product obtained by curing the compound, a resin composition (such as a photosensitive resin composition) containing the compound, and It is providing the pattern formed with the said photosensitive resin composition.

  As a result of intensive studies to achieve the above problems, the present inventors have reacted fluorenes having a phenolic hydroxyl group, phenols, and aldehydes (for example, formaldehydes such as formaldehyde and paraformaldehyde), It is found that a novel fluorene compound having a phenolic hydroxyl group and a methylol group can be obtained, and such a novel fluorene compound (or a cured product thereof) is excellent in heat resistance and etching resistance. completed.

  That is, the compound (fluorene compound) of the present invention is a compound represented by the following formula (1).

(In the formula, ring Z ¹ , ring Z ² and ring Z ³ are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a , R ^2b and R ^2c are the same or different and represent a substituent, and R ^3a , R ^{3 3b} , R ^3c and R ^3d are the same or different and each represents a hydrogen atom or a hydrocarbon group; k1 and k2 are the same or different and each represents 0 or an integer of 1 to 4; m1, m2 and m3 are each 0 or 1 or more N1, n2 and n3 each represent 0 or an integer of 1 or more, p1 represents an integer of 1 or more, and p2 and p3 represent 0 or an integer of 1 or more.)
In the formula (1), ring Z ¹ , ring Z ² and ring Z ³ are benzene rings or naphthalene rings, R ^2a , R ^2b and R ^2c are hydrocarbon groups, and m1, m2 and m3 are each 0. And n1, n2 and n3 may be 1 or 2, respectively. In the formula (1), p1 and p3 may be 1 or 2, respectively, and p2 may be 0 or 1.

  Typically, in the above formula (1), the following (i) or (ii) may be satisfied.

(I) In the above formula (1), ring Z ¹ , ring Z ² and ring Z ³ are benzene rings, R ^2a , R ^2b and R ^2c are alkyl groups or aryl groups, and R ^3a , R ^3b , R ^3c and R ^3d are hydrogen atoms, m1, m2 and m3 are each 0 to 2, n1, n2 and n3 are each 1, p1 is 1, p2 is 0 and p3 is 0 Or it is 1.

(Ii) In the formula (1), a ring ^{Z 1} and the ring ^{Z 2} is naphthalene ring, ring ^{Z 3} is a benzene ^{ring, R 3a, R 3b, R} 3c and ^{R 3d} is a hydrogen atom, m1, m2 and m3 are each 0 to 2, n1, n2 and n3 are each 1, p1 is 1, p2 is 0, and p3 is 0 or 1.

  The present invention also includes a method of producing the compound by reacting a compound represented by the following formula (A), a compound represented by the following formula (B), and a compound represented by the following formula (C). It is.

(In the formula, R ³ represents a hydrogen atom or a hydrocarbon group, and Z ¹ , Z ² , Z ³ , R ^1a , R ^1b , R ^2a , R ^2b , R ^2c , k1, k2, m1, m2, m3, n1, n2, and n3 are the same as above.)
In the said method, you may make it react in presence of an acid catalyst normally.

  The present invention also includes a cured product obtained by curing the compound.

  Furthermore, the present invention includes a resin composition containing at least the compound. Such a resin composition may be a photosensitive resin composition containing the compound and a photosensitizer. A typical photosensitive resin composition includes a negative photosensitive resin composition composed of the compound, a thermosetting resin curable by the action of an acid, and a photoacid generator. Furthermore, the present invention includes a pattern formed of the resin composition (photosensitive resin composition). Such a pattern may be formed by, for example, applying the photosensitive resin composition to a substrate to form a photosensitive layer, exposing the photosensitive layer, heat-treating, and developing the photosensitive layer.

  In the present specification, the “class” such as a compound name includes a case of “having no substituent” and a case of “having a substituent”, and “may have a substituent”. May mean. In the present specification, the “methylol group” means a methylol group (or hydroxymethyl group) substitution product (substitution having a methylol group as a substituent), and the “methylol group” means a methylol group ( Or a hydroxymethyl group) or a substituted methylol group substituted with an alkyl group (for example, an alkyl-substituted methylol group such as a 1-hydroxyethyl group).

  The novel fluorene compound of the present invention has a phenolic hydroxyl group and a methylol group, and is excellent in heat resistance, plasma resistance or etching resistance. Therefore, the fluorene compound and a resin composition thereof (for example, a photosensitive resin composition) can be suitably applied to a resist hard mask or the like.

[Fluorene compound]
The compound of the present invention (sometimes referred to as a fluorene compound) is represented by the following formula (1).

(In the formula, ring Z ¹ , ring Z ² and ring Z ³ are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a , R ^2b and R ^2c are the same or different and represent a substituent, and R ^3a , R ^{3 3b} , R ^3c and R ^3d are the same or different and each represents a hydrogen atom or a hydrocarbon group; k1 and k2 are the same or different and each represents 0 or an integer of 1 to 4; m1, m2 and m3 are each 0 or 1 or more N1, n2 and n3 each represent 0 or an integer of 1 or more, p1 represents an integer of 1 or more, and p2 and p3 represent 0 or an integer of 1 or more.)
In the above formula (1), examples of the aromatic hydrocarbon ring represented by ring Z ¹ , ring Z ² and ring Z ³ include a benzene ring and a condensed polycyclic hydrocarbon ring (specifically, at least a benzene ring is included). Condensed polycyclic hydrocarbon ring) and the like. The condensed polycyclic hydrocarbon corresponding to the condensed polycyclic hydrocarbon ring includes a condensed bicyclic hydrocarbon (for example, C _8-20 condensed bicyclic hydrocarbon such as indene and naphthalene, preferably C _10-16. Condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like. Preferable condensed polycyclic hydrocarbons include condensed polycyclic aromatic hydrocarbons (naphthalene, anthracene, etc.), and naphthalene is particularly preferable. Ring Z ¹ , ring Z ² and ring Z ³ may be the same or different from each other. Usually, ring Z ¹ and ring Z ² may be the same ring.

Preferred ring Z ¹ , ring Z ² and ring Z ³ include a benzene ring and a naphthalene ring, and a naphthalene ring is particularly preferred. Ring ^{Z 1,} Exemplary combinations of the ring ^{Z 2} and Ring ^{Z 3,} (1) a combination ring ^{Z 1,} ring ^{Z 2} and Ring ^{Z 3} is a benzene ring, (2) Ring ^{Z 1} and the ring ^{Z 2} Includes a combination in which is a naphthalene ring and ring Z ³ is a benzene ring.

The substituents represented by the groups R ^1a and R ^1b are not particularly limited, and may be a cyano group, a hydrocarbon group (for example, an alkyl group or the like), and is usually an alkyl group in many cases. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . The groups R ^1a and R ^1b may be different from each other or the same. When k1 (or k2) is 2 or more, the groups R ^1a (or R ^1b ) may be different or the same in the same benzene ring. Note that the bonding position (substitution position) of the group R ^1a (or R ^1b ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers k1 and k2 are 0 or 1, in particular 0. The substitution numbers k1 and k2 may be different but are usually the same.

The number of substitutions n1, n2 and n3 of the hydroxyl group may be 1 or more, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1 respectively. In particular, when ring Z ¹ and ring Z ² are benzene rings, n 1 and n 2 may each be 1-2, especially 1. Incidentally, substituents which n1, n2 and n3 of the hydroxyl groups, each ring ^{Z 1,} in the ring ^{Z 2} and Ring ^{Z 3,} may be the same or different. Usually, ring Z ¹ and ring Z ² are often the same.

Incidentally, the substitution position of the hydroxyl group is not particularly limited, the ring Z ^1, it is sufficient to replace the appropriate substitution position of the ring Z ² and Ring Z ^3. In particular, when ring Z ¹ and ring Z ² are benzene rings, the hydroxyl group is 3-position (or meta-position) or 4-position (or para-position), particularly 4-position, relative to the position where the benzene ring is bonded to fluorene. Often substituted at least in the (para) position.

The substituents R ^2a , R ^2b, and R ^2c that are substituted on the ring Z ¹ , the ring Z ^2, and the ring Z ³ (hereinafter, collectively referred to as ring Z) include an alkyl group (for example, a methyl group, an ethyl group, and the like). A C _1-20 alkyl group such as a group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, preferably a C _1-8 alkyl group, more preferably a C _1-6 alkyl group). A cycloalkyl group (C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group, etc.), an aryl group [eg, phenyl Group, alkylphenyl group (methylphenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group etc.), dimethylphenyl group (xylyl group) Group), etc.), _{C 6-10} aryl group such as a naphthyl group, preferably a _{C 6-8} aryl group, especially a phenyl group, an aralkyl group (benzyl group, _{C 6-10} aryl _-C such phenethyl _1- Hydrocarbon group such as ₄ alkyl group); alkoxy group (such as C _1-4 alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group); acyl group (acetyl) A C _1-6 acyl group such as a group); an alkoxycarbonyl group (such as a C _1-4 alkoxycarbonyl group such as a methoxycarbonyl group); a halogen atom (fluorine atom, chlorine atom, etc.); a nitro group; a cyano group; Substituted amino groups (such as dialkylamino groups) and the like.

Preferred substituents R ^2a , R ^2b and R ^2c are alkyl groups (eg, C _1-6 alkyl groups), cycloalkyl groups (eg, C _5-8 cycloalkyl groups), aryl groups (eg, C _6-10). Aryl groups), aralkyl groups (for example, C _6-8 aryl-C _1-2 alkyl groups) and the like, in particular, C _1-4 alkyl groups (particularly methyl groups), C _1-4 alkoxy groups. , C _6-8 aryl groups are preferred. When m1 or m2 or m3 is 2 or more, the substituents R ^2a and R ^2b and R ^2c are substituted alone or in combination of two or more in the same ring (ring Z ¹ or ring Z ² or ring Z ³ ). You may do it. Further, the substituents R ^2a, R ^2b and R ^2c substituted on different ring Z ^1, ring Z ² and ring Z ³ may be the same or different from each other. Usually, the substituents R ^2a and R ^2b may be the same.

The number of substitutions m1, m2 and m3 can be appropriately selected depending on the kind of ring Z and the like, and is not particularly limited. For example, 0 to 8, preferably 0 to 6 (for example, 1 to 5), more preferably It may be about 0-4. In particular, when ring Z ¹ , ring Z ² and ring Z ³ are benzene rings, the number of substitutions m 1, m 2 and m 3 depends on the number of hydroxyl group substitutions n 1, n 2 and n 3, respectively. -3, preferably 1-2, especially 1. In addition, the number of substitutions m1, m2, and m3 may be the same or different in each of the ring Z ¹ , the ring Z ^2, and the ring Z ³ . Usually, m1 and m2 are often the same.

The substitution positions of the substituents R ^2a , R ^2b, and R ^2c are not particularly limited, and may be substituted at an appropriate substitution position depending on the substitution position of the hydroxyl group. , Phenolic hydroxyl group, phenolic hydroxyl group) at least one of the three carbon atoms positioned in the ortho-position and para-position (that is, the carbon atom that easily substitutes methylol) is unsubstituted (that is, the substituent is Hydrogen atom).

In particular, the three carbon atoms located at the ortho and para positions are carbon atoms that cannot be substituted with an unsubstituted carbon atom and an aldehyde (formaldehyde, etc.) (for example, a substituent (R ^2a or R ^2b or R ^2c ) or the like, or a carbon atom bonded to the 9th position of fluorene). Typically, in the formula (1), n1 and n2 are 1 or more, respectively (e.g., 1), in each ring Z ¹ and the ring Z ^2, positioned ortho and para positions to the hydroxyl group These three carbon atoms may be composed of an unsubstituted carbon atom and a carbon atom substituted by R ^2a and R ^2b . For example, among the 9,9-bis (hydroxyphenyl) fluorenes, when the hydroxyl group is at the 4-position, the fluorenes having a substituent at the 3-position and unsubstituted at the 5-position [for example, 9 , 9-bis (4-hydroxy-3-alkylphenyl) fluorene and the like] are preferable.

  When fluorenes having such a configuration are used, it seems that crosslinking with methylol can be efficiently suppressed.

The hydrocarbon groups represented by the groups R ^3a , R ^3b , R ^3c and R ^3d include the hydrocarbon groups exemplified in the above-mentioned groups R ^2a , R ^2b and R ^2c [for example, alkyl groups (for example, Methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group and other C _1-6 alkyl groups, preferably C _1-4 alkyl groups). The groups R ^3a , R ^3b , R ^3c and R ^3d may usually be a hydrogen atom or an alkyl group (such as a methyl group), preferably a hydrogen atom. In addition, the substitution number p1 of the methylol group substituted on the ring Z ¹ [that is, in the formula (1), the group — (CHR ^3a OH)] may be 1 or more, for example, 1 to 4, preferably 1 to 3, more preferably 1-2, especially 1. In particular, when ring Z ¹ is a benzene ring, p 1 may be 1 to 2, especially 1. Further, the substitution number p2 of the methylol group substituted on the ring Z ² [that is, the group — (CHR ^3b OH) in the formula (1)] may be 0 or more, for example, 0 to 3, preferably 0 to 3. 2, more preferably 0 to 1, in particular 0. In particular, when the ring ^{Z 2} is a benzene ring, p2 is 0-1, and may be especially 0. Furthermore, the substitution number p3 of the methylol group substituted on the ring Z ³ [that is, the group — (CHR ^3d OH) in the formula (1)] may be 0 or an integer of 1 or more. Preferably 0 to 3, more preferably 0 to 2 (for example, 0 to 1), especially 1. In particular, when Ring ^{Z 3} is a benzene ring, p3 is 0 to 2, may be especially 1.

The numbers of substitution p1, p2 and p3 may be the same or different in each ring Z ¹ , ring Z ² and ring Z ³ , and may usually be the same. In addition, the methylol group is similarly substituted according to the number of substitutions of the hydroxyl group or substituent R ^2a (or R ^2b or R ^2c ) and the substitution position thereof, for example, ring Z ¹ and ring Z ^2. Is a benzene ring and the hydroxyl group (phenolic hydroxyl group) is substituted at the 4-position of the phenyl group (specifically, the 4-position of the benzene ring substituted at the 9-position of fluorene), the 2-position (phenolic hydroxyl group) And / or the 3-position (meta position of the phenolic hydroxyl group), the 2-position and / or the 3-position and the 5-position and / or the 6-position may be substituted, preferably It may be substituted at least at the 3-position.

In the formula (1), typically, the ring Z ¹ , the ring Z ² and the ring Z ³ are benzene rings or naphthalene rings, and R ^2a , R ^2b and R ^2c are hydrocarbon groups (alkyl groups, aryl groups). M1, m2 and m3 may each be 0 to 2, and n1, n2 and n3 may each be 1 or 2. In the formula (1), typically, p1 and p3 may each be 1 or 2, and p2 may be 0 or 1.

  Preferred compounds represented by the formula (1) include the following compound (i) or compound (ii).

(I) In the formula (1), the ring Z ¹ and the ring Z ² are benzene rings, the ring Z ³ is a benzene ring or a naphthalene ring (particularly, the ring Z ¹ , the ring Z ² and the ring Z ³ are benzene rings). , R ^2a , R ^2b and R ^2c are hydrocarbon groups [eg, alkyl groups (particularly C _1-4 alkyl groups such as methyl groups) or aryl groups (particularly C _6-10 aryl groups such as phenyl groups)]. R ^3a , R ^3b , R ^3c and R ^3d are hydrogen atoms, m1, m2 and m3 are each 0 to 2 (especially 0 or 1), and n1, n2 and n3 are 1 or 2 ( Especially 1), p1 is 1, p2 is 0, and p3 is 0 or 1 (especially 1).

(Ii) In the formula (1), the ring Z ¹ and the ring Z ² are naphthalene rings, the ring Z ³ is a benzene ring or a naphthalene ring (particularly a benzene ring), and R ^3a , R ^3b , R ^3c and R ^3d is a hydrogen atom, an m1, m2 and m3 are each 0 to 2 (particularly 0) is n1, n2 and n3 are each 1 or 2 (especially 1), p1 is 1, p2 is A compound in which p is 0 and p3 is 0 or 1 (particularly 1).

  In these compounds (i) and (ii), k1 and k2 are preferably 0 or 1, and particularly preferably 0.

Among these compounds, compound (i) in which m1 and m2 are 1 or 2 and compound (ii) (that is, a compound in which ring Z ¹ and ring Z ² in formula (1) are naphthalene rings) It is particularly excellent in etching property.

[Method for producing fluorene compound]
The compound represented by the formula (1) is not particularly limited, but is usually represented by a compound represented by the following formula (A), a compound represented by the following formula (B), and the following formula (C). It can manufacture by making the compound which reacts. In addition, the compound represented by said Formula (1) can be efficiently obtained by selecting suitably the usage rate of these compounds (A), (B), and (C), reaction conditions, etc.

(In the formula, R ³ represents a hydrogen atom or a hydrocarbon group, and Z ¹ , Z ² , Z ³ , R ^1a , R ^1b , R ^2a , R ^2b , R ^2c , k1, k2, m1, m2, m3, n1, n2, and n3 are the same as above.)
(Compound represented by Formula (A))
Representative compounds represented by the formula (A) (fluorenes having a phenolic hydroxyl group) include, for example, (1) 9,9-bis (hydroxyphenyl) fluorenes, (2) 9,9-bis. (Hydroxynaphthyl) fluorenes and the like are included.

(1) 9,9-bis (hydroxyphenyl) fluorenes 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (monohydroxyphenyl) fluorenes, 9,9-bis (dihydroxyphenyl) Fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes [for example, 9,9-bis (2,3,4-trihydroxyphenyl) fluorene, 9,9-bis (2,4,6-trihydroxy 9,9-bis (trihydroxyphenyl) such as phenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene ) Fluorene, etc.], usually 9,9-bis (monohydroxyphenyl) fluorenes or 9,9-bis (dihydroxy) Cyphenyl) fluorenes, particularly 9,9-bis (monohydroxyphenyl) fluorenes, can be preferably used.

As 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene) and the like], substituents 9,9-bis (hydroxyphenyl) fluorene {e.g., 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene (biscresol fluorene), 9 , 9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-butylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene, etc. 9,9-bis (C _1-4 alkyl-hydroxyphenyl) fluorene, 9,9-bis (diC _1-4 alkyl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene], 9,9-bis (cycloalkyl-hydroxy Phenyl) fluorene [9,9-bis (C _5-8 cycloalkyl-monohydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene], 9,9-bis (aryl -Hydroxyphenyl) fluorene [eg, 9,9-bis (C _6-8 aryl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene], 9,9-bis (Aralkyl-hydroxyphenyl) fluorene [e.g., 9,9-bis (4-hydroxy-3-benzene) Jirufeniru) 9,9-bis _{(C 6-8} aryl _{C 1-2} alkyl, such as fluorene - hydroxyphenyl) fluorene, etc.], etc.} and the like.

As 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9- Bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene), 9,9-bis (3,5-dihydroxyphenyl) fluorene, etc.], substituted 9,9-bis (dihydroxyphenyl) fluorene {e.g. 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluorene 9,9-bis (C _1-4 alkyl-dihydroxyphenyl) fluoro Ren, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene such as 9,9-bis _{(di-C 1-4} alkyl - dihydroxyphenyl) fluorene, etc.], 9,9-bis ( Aryl-dihydroxyphenyl) fluorene [for example, 9,9-bis (C _6-8 aryl-dihydroxyphenyl) fluorene such as 9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene, etc.] etc. Can be illustrated.

  Note that bis (monohydroxyphenyl) fluorenes can be prepared by various synthesis methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone in the presence of an acid catalyst (and alkyl mercaptan) A method of reacting alkylphenols (JP 2000-26349 A), (c) a method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP 2002-47227 A). (D), (d) in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), fluorenones and phenols are reacted to form hydrocarbons It can be produced by using a method of producing bisphenolfluorene by crystallization with a crystallization solvent composed of a kind and a polar solvent (Japanese Patent Laid-Open No. 2003-221352).

  In addition, 9,9-bis (di- or trihydroxyphenyl) fluorenes can be obtained by using the corresponding polyhydric alcohols (dihydroxy) instead of phenols in the above-mentioned 9,9-bis (monohydroxyphenyl) fluorenes production method. Phenols and trihydroxyphenols). Among these methods, in particular, when the method (c) using hydrochloric acid or the method (d) using a specific crystallization solvent is applied, the product may be obtained with higher yield and higher purity. Many.

(2) 9,9-bis (hydroxynaphthyl) fluorenes As 9,9-bis (hydroxynaphthyl) fluorenes, for example, 9,9-bis (hydroxynaphthyl) fluorenes {for example, 9,9-bis ( Hydroxynaphthyl) fluorene [e.g., 9,9-bis [6- (2-hydroxynaphthyl)] fluorene (or 6,6- (9-fluorenylidene) -di (2-naphthol)), 9,9-bis [1 -(6-hydroxynaphthyl)] fluorene (or 5,5- (9-fluorenylidene) -di (2-naphthol)), 9,9-bis [1- (5-hydroxynaphthyl)] fluorene (or 5,5 -(9-fluorenylidene) -di (1-naphthol)) etc.] may be substituted, and 9,9-bis (monohydroxynaphthyl) fluore }, 9,9-bis (polyhydroxynaphthyl) fluorenes corresponding to these 9,9-bis (monohydroxynaphthyl) fluorenes (for example, 9,9-bis (di- or trihydroxynaphthyl) fluorenes), etc. Is mentioned.

  In addition, 9,9-bis (hydroxynaphthyl) fluorenes are produced by using hydroxynaphthalenes (for example, naphthol (1-naphthol) instead of phenols in the method for producing 9,9-bis (monohydroxyphenyl) fluorenes. Naphthols such as 2-naphthol) and polyhydroxynaphthalenes such as dihydroxynaphthalene).

  These fluorenes having a phenolic hydroxyl group may be used alone or in combination of two or more.

Preferred fluorenes having a phenolic hydroxyl group include 9,9-bis (4-hydroxy-3-substituted phenyl) fluorene [for example, 9,9-bis (4-hydroxy-3-alkylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3-cycloalkylphenyl) fluorene, 9,9-bis (4-hydroxy-3-arylphenyl) fluorene, etc.], 9,9-bis (dihydroxyphenyl) fluorene, 9,9-bis (Hydroxynaphthyl) fluorene and the like, and in particular, 9,9-bis (4-hydroxy-3-alkylphenyl) fluorene [especially 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (biscresol). fluorene) such as 9,9-bis (4-hydroxy _{-3-C 1-4} alkyl phenyl) fluoride Ren], 9,9-bis (hydroxynaphthyl) fluorene.

In particular, the fluorene having a hydrocarbon group in the ring Z ¹ and the ring Z ² such as 9,9-bis (alkyl-hydroxyphenyl) fluorene and 9,9-bis (aryl-hydroxyphenyl) fluorene includes the ring Z ¹ and the ring Compared to the case of using fluorene having an unsubstituted fluorene skeleton in Z ² [for example, 9,9-bis (4-hydroxyphenyl) fluorene], it is advantageous in improving heat resistance and etching resistance. In addition, fluorenes in which the ring Z ¹ and the ring Z ² such as 9,9-bis (hydroxynaphthyl) fluorene are condensed aromatic hydrocarbon rings such as a naphthalene ring are more effective in improving heat resistance and etching resistance. In addition to being more advantageous, the thermal expansion can be further reduced, which is advantageous for improving the dimensional accuracy.

(Compound represented by Formula (B))
As a compound (namely, phenols) represented by the said Formula (B), it does not have phenols (or fluorene skeleton) other than the compound (namely, fluorene which has a phenolic hydroxyl group) represented by the said formula (A). Phenols). In addition, the compound (phenols) represented by Formula (B) may use a commercial item, and can also prepare it by the well-known method known in the said field | area.

Representative compounds (phenols) represented by the formula (B) include, for example, monophenols {for example, phenol, alkylphenol [cresol (o-cresol, m-cresol, p-cresol), ethylphenol (2 -Monophenols such as ethylphenol), mono- _C1-20 alkylphenols such as butylphenol, octylphenol, nonylphenol (eg mono- _C1-10 alkylphenols); xylenols (such as 2,3-dimethylphenol, 2,4-dimethylphenol), etc. di _{C 1-10} alkyl phenol, etc.], (such as 2-cyclohexyl phenol) cyclo alkyl phenols, (e.g., o- phenylphenol) arylphenols, it anisole such as alkoxy phenol (o- methoxyphenol ), Phenol having a substituent such as amino phenols; naphthol [e.g., naphthol (alpha-naphthol, beta-naphthol, etc.), alkyl naphthol (methyl naphthol, ethyl naphthol, dimethyl naphthol, C _1-4 alkyl, such as propyl naphthol Naphthol and the like], etc.], phenols having a plurality of phenolic hydroxyl groups [for example, dihydroxybenzene (catechol, resorcinol, hydroquinone), alkyl-dihydroxybenzene (mono- or di-C _1-6 alkyl such as dihydroxytoluene, dihydroxyxylene) - etc. dihydroxybenzene), aryl - dihydroxybenzene (2,3-dihydroxy-biphenyl, _{C 6-8} aryl, such as 3,4-dihydroxybiphenyl - dihydroxybenzene Etc.), alkoxy - mono- or di-C _1-6 alkoxy such as dihydroxybenzene (3-methoxy catechol - like dihydroxybenzene), polyhydric phenols such as trihydroxy benzenes (pyrogallol, hydroxyhydroquinone, phloroglucinol, etc.); Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.)] and the like.

  These phenols may be used alone or in combination of two or more.

  Among these phenols, monophenols such as phenol and alkylphenol are preferable, and substituted phenols such as cresol are particularly preferable.

  In the reaction, the ratio of the compound (phenols) represented by the formula (B) is 0.01 to 30 with respect to 1 part by weight of the compound (fluorenes having a phenolic hydroxyl group) represented by the formula (A). It can be selected from the range of parts by weight (for example, 0.05 to 20 parts by weight), for example, 0.05 to 15 parts by weight (for example, 0.1 to 10 parts by weight), preferably 0.15 to 5 parts by weight, More preferably, it is about 0.2 to 3 parts by weight (for example, 0.25 to 2 parts by weight), usually about 0.1 to 1.5 parts by weight (for example, 0.2 to 1 part by weight). Also good.

(Compound represented by Formula (C))
The compound represented by the formula (C) (that is, aldehydes) is not particularly limited, and alkanals (for example, acetaldehyde), aromatic aldehydes and the like may be used. Formaldehydes such as formaldehyde (or formaldehyde source) can be preferably used. Aldehydes may be used alone or in combination of two or more. In addition, you may use aldehydes as a solution (for example, formaldehyde aqueous solution (formalin etc.)). Aldehydes can also be prepared by known methods known in the art.

  In the reaction, the ratio of the compound represented by the formula (C) is, for example, 0 with respect to 100 parts by weight of the total amount of the compound represented by the formula (A) and the compound represented by the formula (B). 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably about 1 to 20 parts by weight, and usually 1 to 50 parts by weight.

  In addition, reaction can be normally performed in presence of an acid catalyst (acidic conditions). The acid catalyst is not particularly limited, and inorganic acids [for example, proton acids (sulfuric acid, hydrogen chloride (or hydrochloric acid), phosphoric acid, etc.), Lewis acids (boron trifluoride, aluminum chloride, zinc chloride, etc.), etc.], Organic acids {for example, sulfonic acids (alkane sulfonic acids such as methane sulfonic acid, arene sulfonic acids such as p-toluene sulfonic acid), aliphatic carboxylic acids [for example, alkane acids (for example, alkane mono-acids such as acetic acid and oxalic acid) Or a carboxylic acid such as a dicarboxylic acid). These acid catalysts may be used alone or in combination of two or more.

  The amount of the acid catalyst used is, for example, 0.01 to 10 parts by weight, preferably 0 with respect to 1 part by weight of the total amount of the compound represented by the formula (A) and the compound represented by the formula (B). 0.05 to 8 parts by weight, more preferably about 0.1 to 5 parts by weight.

  The reaction may be performed in a solvent. Solvents are not particularly limited, and include water, alcohols (alkyl alcohols such as methanol, ethanol, isopropanol and butanol, cyclohexanol, etc.), ketones (alkyl ketones such as acetone and diisopropyl ketone, cyclohexanone, etc.), ethers ( Dialkyl ethers such as diisopropyl ether, cyclic ethers such as tetrahydrofuran), glycol ethers (such as ethylene glycol monomethyl ether), alkylene glycol monoalkyl ether acetates (such as methyl cellosolve acetate), esters (such as ethyl acetate), nitriles , Cellosolves, amides (dimethylformamide, etc.), sulfoxides, hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic charcoal Hydrogen (such as cyclohexane), and aromatic hydrocarbons (toluene, xylene, etc.) and the like. These solvents may be used alone or in combination of two or more.

  The amount of the solvent used is not particularly limited, and relative to 1 part by weight of the total amount of the compound represented by the formula (A), the compound represented by the formula (B) and the compound represented by the formula (C). 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably about 1 to 10 parts by weight.

  In the reaction, the reaction temperature may be, for example, about 0 to 250 ° C., preferably 40 to 200 ° C., more preferably about 70 to 180 ° C. (for example, 80 to 150 ° C.). The reaction time may be, for example, 30 minutes to 72 hours, preferably about 1 to 48 hours. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure.

  The compound represented by the formula (1) is obtained by the reaction as described above.

  In addition, the reaction mixture after completion | finish of reaction contains a solvent, a catalyst (acid catalyst etc.), an unreacted component, etc. besides the said compound. Therefore, the phenol resin may be separated and purified from the reaction product after the condensation reaction by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, and recrystallization, or a separation means that combines these. .

  Further, in the reaction mixture after the reaction, in addition to the compound represented by the formula (1), by-products (the compound represented by the formula (A) and the compound represented by the formula (B)) May be included in a compound in which the molar ratio is not 1/1. The ratio of such a by-product may be 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, with respect to the entire reaction mixture (or purified product).

[Uses of fluorene compounds]
The fluorene compound of the present invention (the compound represented by the formula (1)) can be used for various applications, and can usually be used as a thermosetting resin (or a thermosetting compound). That is, the fluorene compound of the present invention has self-crosslinking properties and can be cured alone. Such a cured product of a fluorene compound is excellent in heat resistance and plasma resistance (or dry etching resistance). Therefore, the cured product of the fluorene compound (cured product obtained by curing the fluorene compound) is also included in the present invention.

(Hardened fluorene compound)
The cured product of the fluorene compound may be a cured product (crosslinked product, self-crosslinked product) obtained by curing (or crosslinking) the fluorene compound alone as a resin component. Such a cured product can be obtained by heating the fluorene compound. Such a cured product can be molded using a conventional molding method (compression molding method, transfer molding method, etc.), for example, a cured film (cured coating film) obtained by heating a coating film containing the fluorene compound. ). The coating film may be formed, for example, by applying a coating liquid (coating liquid) containing the fluorene compound and a solvent to the substrate.

  Examples of the solvent include water, alcohols (methanol, ethanol, etc.), ethers (tetrahydrofuran, etc.), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl). Ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol monoalkyl ether acetates (methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, -Methoxybutyl-1-acetate, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.) Esters (ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate). These solvents may be used alone or in admixture of two or more.

  In the coating liquid, the ratio of the solvent is, for example, 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, more preferably 0.5 to 30 parts by weight with respect to 1 part by weight of the fluorene compound. It may be a degree.

  In addition, the said coating liquid (or hardened | cured material) should just contain only the said fluorene compound as a resin component, and may contain the additive etc. Examples of additives include stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), flame retardants, flame retardant aids, plasticizers, impact modifiers, depending on the application. , Fillers (or reinforcing agents), dispersants, antistatic agents, foaming agents, antibacterial agents, lubricants and the like. These additives may be used alone or in combination of two or more.

  The substrate is not particularly limited, and may be a substrate formed of metal, ceramic, glass, plastic, or the like, or a semiconductor substrate (such as a silicon wafer).

  In addition, you may give a drying process to the coating film after application | coating as needed. Drying may be natural drying or may be performed by heating the coating film (for example, a heating temperature of 40 to 120 ° C., preferably about 60 to 110 ° C.).

  In heating the fluorene compound (or coating film), the heating temperature (or post-baking temperature) may be, for example, 120 to 300 ° C, preferably 140 to 250 ° C, and more preferably about 160 to 220 ° C. . The heating time depends on the form or shape of the cured product, but may be, for example, 30 seconds to 10 hours, preferably 1 minute to 5 hours, and more preferably about 2 minutes to 3 hours.

  Such a cured product (or cured coating film) is excellent in heat resistance and dry etching resistance. In addition, the average thickness of a cured film can be suitably selected according to a use, for example, 0.01-1000 micrometers, Preferably it is 0.05-500 micrometers, More preferably, about 0.1-100 micrometers may be sufficient.

(Resin composition containing a fluorene compound)
The fluorene compound of the present invention can also constitute a resin composition (particularly a thermosetting resin composition). Such a resin composition should just contain the said fluorene compound at least, and may be a thermosetting resin composition normally. Moreover, the photosensitive resin composition may be sufficient so that it may mention later. In particular, a thermosetting resin composition using the fluorene compound of the present invention as a thermosetting resin or a curing agent is useful for obtaining a cured product (particularly a cured film) excellent in heat resistance and etching resistance.

(Thermosetting resin composition and its cured product)
When the fluorene compound is used as a thermosetting resin component, the thermosetting resin composition can be appropriately selected according to the case where the fluorene compound is used as a curing agent component. For example, (i) the fluorene compound and the curing agent (or curing acceleration) (Ii) a thermosetting resin composition composed of the fluorene compound and a curable resin (or curable compound), and the like. The fluorene compound can be cured alone (in the absence of a curing agent) as described above.

  In the thermosetting resin composition (i), examples of the curing agent (including a curing accelerator or a curing aid) include amines (for example, chain aliphatic amines (ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene). Chain aliphatic polyamines such as tetramine), cycloaliphatic amines [mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 3,9-bis (3-aminopropyl) -2, Monocyclic aliphatic polyamines such as 4,8,10-tetraoxaspiro (5.5) undecane, condensed cyclic or bridged cyclic polyamines such as norbornanediamine and hexamethylenetetramine], aromatic or araliphatic amines (Xylylenediamine metaphenylenediamine, diaminodiphenylmethane, etc.) etc. Phosphines [for example, organic phosphines (first, second, and third phosphines) such as ethylphosphine, propylenephosphine, phenylphosphine, triphenylphosphine, trialkylphosphine, etc.], amide compounds (dimer acid polyamide, etc.) ), Epoxy compounds [eg epichlorohydrin, diglycidyl ether, polyol polyglycidyl ether (butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, etc.), diglycidyl Polyglycidyl ethers such as aniline and cyclohexanedimethanol diglycidyl ether, epoxy resin (epi-bis type epoxy resin, phenol type epoxy resin) Resin, brominated epoxy resin, glycol type epoxy resin, etc.)], ptronic acid (for example, inorganic acid such as sulfuric acid and phosphoric acid, organic acid such as acetic acid), acid anhydride (phthalic anhydride, tetrahydromethyl phthalic anhydride) Acid, hexahydrophthalic anhydride, trimellitic anhydride, methyl nadic anhydride, etc.). These curing agents may be used alone or in combination of two or more.

  In the thermosetting resin composition (i), the ratio of the curing agent (or crosslinking agent) is 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, with respect to 100 parts by weight of the fluorene compound. More preferably, it may be about 0.5 to 30 parts by weight.

  In the thermosetting resin composition (ii), the curable resin (specifically, the curable resin other than the fluorene compound) is not particularly limited, and examples thereof include a phenol resin (such as a novolac phenol resin) and furan. Resin, urea resin [or a precursor of urea resin, such as mono- or dimethylol urea or its condensate (partial condensate)], methylol group-containing compound {for example, melamine resin [or melamine resin precursor (melamine formaldehyde Adducts or condensates), such as methylol melamine (mono to trimethylol melamine) or condensates thereof (partial condensates), etc.}, unsaturated polyester resins, epoxy resins (epi-bis type epoxy resins, phenol type epoxies) Resin, brominated epoxy resin, glycol type epoxy resin, glycidyl amide Type epoxy resins, glycidyl ester type epoxy resins, etc.), urethane resins (polyisocyanate multimers, etc.), silicone resins, polyimides, diallyl phthalate resins, vinyl ester resins, and other thermosetting resins (or photocurable resins). Can be mentioned.

  The curable resin also includes a fluorene skeleton-containing compound having a plurality of functional groups (or crosslinkable groups). Examples of such a compound having a fluorene skeleton include an epoxy compound having a fluorene skeleton. Examples of the epoxy compound having a fluorene skeleton include compounds represented by the following formula (3).

(Wherein R ^4a and R ^4b are the same or different and are an alkylene group, q1 and q2 are the same or different and represent 0 or an integer of 1 or more, and Z ¹ , Z ² , R ^1a , R ^1b , R ^2a , R ^2b , k1, k2, m1, m2, n1, and n2 are the same as above.)
In the formula (3), the alkylene group represented by R ^4a and R ^4b is not limited, and examples thereof include a C _2-4 alkylene group (ethylene group, trimethylene group, propylene group, butane-1,2-diyl). Group etc.) etc. can be illustrated and a _C2-3 alkylene group (especially ethylene group, propylene group) is preferable. R ^4a and R ^4b may be the same or different alkylene groups, but are usually the same alkylene group. Moreover, although q1 and q2 are not specifically limited, they are the same or different and can be selected from the range of about 0-15, for example, 0-12 (for example, 1-12), preferably 0-8, more preferably 0. It may be about -6, especially about 0-4. When q1 (or q2) is 2 or more, the polyalkyleneoxy group may be composed of a mixture of the same or different alkoxy groups (for example, an ethoxy group and a propyleneoxy group).

As an epoxy compound (epoxy resin) having a typical fluorene skeleton, for example, 9,9-bis (glycidyloxyaryl) fluorene {for example, 9,9-bis (glycidyloxyphenyl) fluorene [for example, 9,9 -Bis (4-glycidyloxyphenyl) fluorene and the like], 9,9-bis (alkyl-glycidyloxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis 9,9-bis (mono or diC _1-4 alkyl-glycidyloxyphenyl) fluorene such as (4-glycidyloxy-3,5-dimethylphenyl) fluorene], 9,9-bis (arylglycidyloxyphenyl) Fluorene [9,9-bis (4-glycidyloxy-3-phenylphenol) 9,9-bis (glycidyloxyphenyl) fluorenes such as 9,9-bis (mono- or di-C _6-8 aryl-glycidyloxyphenyl) fluorene etc.] such as phenyl) fluorene; 9,9-bis (glycidyloxy) Naphthyl) fluorene [e.g., 9,9-bis [6- (2-glycidyloxynaphthyl)] fluorene, 9,9-bis [1- (6-glycidyloxynaphthyl)] fluorene, 9,9-bis [1- 9,9-bis (glycidyloxynaphthyl) fluorenes such as (5-glycidyloxynaphthyl)] fluorene], 9,9-bis (polyglycidyloxyaryl) fluorenes {for example, 9,9-bis [3 , 4-Di (glycidyloxy) phenyl] fluorene, 9,9-bis [3,4,5-tri (glycidyloxy) ) 9,9-bis (di or triglycidyloxyaryl) fluorene} such as phenyl] fluorene}, compounds corresponding to these compounds, wherein q1 and q2 are 1 or more in the above formula (3) {for example, 9,9 -Bis (glycidyloxyalkoxyphenyl) fluorene [for example, 9,9-bis (glycidyloxyC _2-4 alkoxyphenyl) fluorene such as 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene], 9,9 -Bis (alkyl-glycidyloxyalkoxyphenyl) fluorene [eg 9,9-bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxyethoxy-3,5-dimethyl) phenyl) fluorene such as 9,9-bis (mono or di _{C 1 4} alkyl glycidyloxy _{C 2-4} alkoxyphenyl) fluorene, etc.], 9,9-bis (9, such as aryl glycidyloxy alkoxyphenyl) fluorene [9,9-bis (4-glycidyloxy-ethoxy-3-phenylphenyl) fluorene , 9-bis (mono- or di-C _6-8 arylglycidyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis (glycidyloxyalkoxynaphthyl) fluorene [for example, 9,9-bis (glycidyloxy C) _2-4 alkoxynaphthyl) fluorene and the like], 9,9-bis [di or tri (glycidyloxyalkoxy) phenyl] fluorene [eg, 9,9-bis [3,4-di (2-glycidyloxyethoxy) phenyl] Fluorene, 9,9-bis [3,4,5-to (2-glycidyloxyethoxy) phenyl] 9,9-bis [di- or compounds q1 and q2 are 1 in birds the formula such as (glycidyloxy _{C 2-4} alkoxy) phenyl] fluorene] (3) of fluorene A compound corresponding to these compounds, wherein q1 and q2 are 2 or more in the formula (3) [for example, 9,9-bis {4- [2- (2-glycidyloxyethoxy) ethoxy] phenyl} fluorene, etc. 9,9-bis {[2- (2-glycidyloxy C _2-4 alkoxy) C _2-4 alkoxy] phenyl} fluorene etc.]} and the like. These epoxy compounds having a fluorene skeleton may be used alone or in combination of two or more.

Among these epoxy compounds having a fluorene skeleton, in particular, 9,9-bis (glycidyloxyaryl) fluorenes [for example, 9,9-bis (glycidyloxyphenyl) fluorene, 9,9-bis (alkyl-glycidyloxy) Phenyl) fluorene, 9,9-bis (glycidyloxynaphthyl) fluorene, etc.], C _2-4 alkylene oxide adducts of 9,9-bis (glycidyloxyaryl) fluorenes [for example, 9,9-bis (glycidyloxy) C _2-4 alkoxyphenyl) fluorene and the like] are preferable.

  These curable resins can be used alone or in combination of two or more.

  In the thermosetting resin composition (ii), the fluorene compound may be non-reactive or reactive with the curable resin. For example, among the fluorene compound and the curable resin, one component may act as a curing agent for the other component (or one component and the other component may be bonded by reaction) One component and the other component may be non-reactive with each other.

  Preferred curable resins include resins that act as curing agents for fluorene compounds, such as epoxy resins. In particular, an epoxy compound having a fluorene skeleton acts as a curing agent for the fluorene compound and is firmly bonded to each other so that a large amount of the fluorene skeleton can be introduced into a cured product. The constituted thermosetting resin composition is useful for obtaining a cured product having extremely excellent heat resistance and etching resistance.

  In the thermosetting resin composition (ii), the proportion of the curable resin depends on the application and the like, but is, for example, 1 to 1000 parts by weight, preferably 2 to 500 parts by weight with respect to 100 parts by weight of the fluorene compound. More preferably, it may be 5 to 300 parts by weight (for example, 10 to 200 parts by weight), particularly about 30 to 150 parts by weight.

  The thermosetting resin composition (ii) may further contain a curing agent (or a curing accelerator). Such a curing agent may be a curing agent for the fluorene compound or the thermosetting resin, or may be a curing agent for both the fluorene compound and the thermosetting resin. As a hardening | curing agent, the hardening agent (or hardening accelerator or hardening adjuvant, for example, phosphines etc.) illustrated by the term of the said thermosetting resin composition (i), etc. are mentioned. The curing agents may be used alone or in combination of two or more.

  Typical curing agents (or curing accelerators) include amines and phosphines.

  In the thermosetting resin composition (ii), the ratio of the curing agent is 0.1 to 100 parts by weight, preferably 0.3 to 50 parts per 100 parts by weight of the total amount of the fluorene compound and the thermosetting resin. It may be about 0.5 to 30 parts by weight, more preferably about 0.1 to 20 parts by weight (for example, 0.1 to 10 parts by weight).

  The preferred thermosetting resin composition (ii) includes a thermosetting resin that can act as a curing agent or a crosslinking agent for the fluorene compound, such as the fluorene compound and an epoxy resin (particularly, an epoxy compound having the fluorene skeleton). And a thermosetting resin composition containing a curing agent or a curing accelerator (such as phosphines) in addition to the thermosetting resin composition.

  The thermosetting resin composition (thermosetting resin composition (i) and thermosetting resin composition (ii)) may be a composition containing a solvent (coating composition) as described later. Good.

  Moreover, the thermosetting resin composition (thermosetting resin composition (i) and thermosetting resin composition (ii)) may contain an additive or the like. Examples of the additive include those exemplified above. The additives may be used alone or in combination of two or more.

  As described above, the thermosetting resin composition is useful for obtaining a cured product having excellent heat resistance and etching resistance. Such a cured product can be obtained by heating the thermosetting resin composition. Such a cured product can be molded using a conventional molding method (compression molding method, transfer molding method, etc.), for example, a cured film obtained by heating a coating film containing the thermosetting resin composition. It may be in the form of (cured coating). The coating film may be formed by, for example, applying a coating liquid (coating liquid) containing the thermosetting resin composition and a solvent to a substrate. The same solvent and substrate as described above can be used.

  In the coating liquid (or coating composition), the ratio of the solvent is, for example, 0.1 to 100 parts by weight, preferably 0.3 to 50 parts per 1 part by weight of the total amount of the phenol resin and the thermosetting resin. It may be about 0.5 to 30 parts by weight, more preferably about 0.5 to 30 parts by weight. In addition, you may give a drying process to the coating film after application | coating as needed. Drying may be natural drying or may be performed by heating the coating film (for example, a heating temperature of 40 to 120 ° C., preferably about 60 to 110 ° C.).

  In heating the thermosetting resin composition (or coating film), the heating temperature (or post-bake temperature) is, for example, 120 to 300 ° C, preferably 140 to 250 ° C, and more preferably about 160 to 220 ° C. There may be. The heating time depends on the form or shape of the cured product, but may be, for example, 30 seconds to 10 hours, preferably 1 minute to 5 hours, and more preferably about 2 minutes to 3 hours. Such a cured product (or cured coating film) is excellent in heat resistance and dry etching resistance. In addition, the average thickness of a cured film can be suitably selected according to a use, for example, 0.01-1000 micrometers, Preferably it is 0.05-500 micrometers, More preferably, about 0.1-100 micrometers may be sufficient.

(Photosensitive resin composition and pattern)
The resin composition may be a photosensitive resin composition. That is, the fluorene compound of the present invention can be suitably used as a resin (particularly a base resin) constituting the photosensitive resin composition. The photosensitive resin composition composed of the fluorene compound is extremely useful for forming a pattern having high etching resistance (particularly dry etching resistance). In addition, the photosensitive resin composition can be made into a negative type or a positive type photosensitive resin composition by selecting appropriately the photosensitive agent to combine and the other resin mentioned later.

  The resin component of the photosensitive resin composition may be composed of at least the fluorene compound, may be composed of the fluorene compound alone, the fluorene compound and other resins (hereinafter, “other resins”, etc.) May also be configured.).

Other resins include, for example, thermoplastic resins {for example, hydroxyl group-containing polymers [polyvinyl acetal, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, hydroxyl group-containing cellulose derivatives (such as hydroxyethyl cellulose), polyvinyl phenol resins, novolacs] Resin (novolak-type phenol resin, etc.), carboxyl group-containing polymer [polymerizable unsaturated carboxylic acid ((meth) acrylic acid, maleic anhydride, itaconic acid, etc.) alone or a copolymer, carboxyl group-containing cellulose derivative (carboxy Such as methyl cellulose or a salt thereof), ester group-containing polymer [a carboxylic acid vinyl ester (such as vinyl acetate), (meth) acrylic acid ester (such as methyl methacrylate) or the like alone or a copolymer Polyvinyl acetate, ethylene-vinyl acetate copolymers, (meth) acrylic resins, etc.), polyesters, etc.], polymers having ether groups (polyvinyl ether resins, etc.), polymers having amide groups or substituted amide groups (polyvinylpyrrolidone) , Polyurethane polymers, polyureas, polyamide polymers, poly (meth) acrylamide polymers, polyamino acids, proteins, etc.), polymers having nitrile groups (acrylonitrile polymers, etc.), polymers having glycidyl groups (glycidyl) (Meth) acrylate homopolymer or copolymer), polymer having non-aromatic cyclic group (for example, polymer of monomer having C _5-8 cycloalkyl group such as cyclohexyl (meth) acrylate); (meth) acrylic Acid norbornyl, (meth) acrylic Such as polymers of monomers) having a crosslinked cyclic C _7-20 aliphatic hydrocarbon ring groups such as adamantyl}, curable resin (thermal or photocurable resin) [the above-exemplified curable resins (such as melamine resin), Photopolymerizable oligomers or polymers (such as oligomers having a polymerizable group such as (meth) acryloyl group, allyl group, vinyl group, cinnamoyl group, etc.).

In addition, other resins have protective groups (especially the action of acids) from which hydrophilic groups (hydroxyl groups and / or carboxyl groups, etc.) of these resins (hydroxyl group-containing polymers, carboxyl group-containing polymers, etc.) can be removed. And a resin protected with a protecting group which can be removed by the above method. Removable protecting group [for example, a linear group optionally having a substituent such as an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, etc. Or a resin having a hydrophilic group protected with a branched C _1-6 alkyl group (for example, C _1-4 alkyl group, etc.)] and the like. Phenolic resins [vinylphenol monomers (such as vinylphenol) alone or copolymers (for example, polyvinylphenol), copolymers of vinylphenol monomers and copolymerizable monomers, etc.), Hydroxyl group and / or carboxyl group-containing (meth) acrylic resin [for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer, or hydroxyalkyl Le copolymer of (meth) acrylate and a copolymerizable monomer, etc.] and the like.

  These other resins may be used alone or in combination of two or more.

  In addition, when other resin is a thermoplastic resin, the weight average molecular weight of other resin may be 800-30000, for example, Preferably it is 1000-10000, More preferably, about 1500-7000 may be sufficient. Moreover, when other resin is curable resin, the weight average molecular weight of other resin may be 120-3000, for example, Preferably it is 130-2000, More preferably, about 150-1000 may be sufficient.

  When other resin is used, the ratio of the other resin is, for example, about 1 to 200 parts by weight, preferably about 5 to 100 parts by weight, and more preferably about 10 to 50 parts by weight with respect to 100 parts by weight of the fluorene compound. It may be.

  The photosensitive resin composition can be comprised with the said fluorene compound (and other resin as needed), and is normally comprised with the said fluorene compound (and other resin as needed) and a photosensitive agent.

  As the photosensitizer, depending on the type of positive type, negative type, etc., conventional photosensitizers or photosensitizers such as diazonium salts (diazonium salts, tetrazonium salts, polyazonium salts, etc.), quinonediazides (diazobenzoquinone derivatives, Diazonaphthoquinone derivatives, etc.), photoacid generators, dissolution inhibitors and the like can be selected.

As the photoacid generator, a sulfonium salt derivative [an arylalkanesulfonate such as sulfonate ester (1,2,3-tri (methylsulfonyloxy) benzene (especially C _6-10 aryl-C _1-2 alkanesulfonate)); 2 , 6-dinitrobenzyltoluenesulfonate, arylbenzenesulfonates such as benzoin tosylate (especially C _{6-10 aryltoluenesulfonate optionally} having benzoyl group); 2-benzoyl-2-hydroxy-2-phenylethyltoluenesulfonate aralkyl benzene sulphonates (especially optionally having benzoyl C _6-10 aryl -C _1-4 alkyl toluenesulfonate) and the like; Lewis acids salt (triphenylsulfonium; disulfonic such as diphenyl disulfone Xafluorophosphate, triphenylsulfonium hexafluoroantimonate, 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Triarylsulfonium salts such as phenylsulfonium nonafluorobutanesulfonate (especially triphenylsulfonium salts), etc.], phosphonium salt derivatives, diarylhalonium salt derivatives [diaryliodonium salts (diphenyliodonium hexafluorophosphate, 4,4′-di) (T-Butylphenyl) iodonium hexafluorophosphate 4,4′-di (t-butylphenyl) iodonium hexafluoroantimonate, 4,4′-di (t-butylphenyl) iodonium tetrafluoroborate, 4,4′-di (t-butylphenyl) Lewis acid salts such as iodonium trifluoromethanesulfonate, 4,4′-di (t-butylphenyl) iodonium camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenyl phenyliodonium trifluoromethanesulfonate, etc.], diazonium salt derivatives ( Lewis acid salts such as p-nitrophenyldiazonium hexafluorophosphate), diazomethane derivatives, triazine derivatives [1-methoxy-4- (3,5-di (trichloromethyl) triazinyl) benzene, Haloalkyltriazinyl arenes such as 1,2-methylenedioxy-4- (3,5-di (trichloromethyl) triazinyl) benzene, 1-methoxy-4- (3,5-di (trichloromethyl) triazinyl) naphthalene, 1-methoxy-4- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] benzene, 1,2-dimethoxy-4- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] Benzene, 1-methoxy-2- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] haloalkyltriazinylalkenyl arenes such as benzene], imidyl sulfonate derivatives [succinimidyl camphorsulfonate, succinimidyl phenyl sulfonate, Succinimidyl toluylsulfonate, sushi And the like, and the like.

  These photosensitizers may be used alone or in combination of two or more.

  The ratio of the photosensitive agent is, for example, 0.01 to 30 parts by weight, preferably 0, with respect to 100 parts by weight of the resin component of the photosensitive resin composition (the total amount of the phenol resin or the phenol resin and other resins). It may be about 1 to 10 parts by weight, more preferably about 0.5 to 8 parts by weight (for example, 1 to 5 parts by weight).

  The photosensitive resin composition may be a positive photosensitive resin composition or a negative photosensitive resin composition depending on the type of other resin or photosensitive agent to be combined. For example, as another resin, by using a resin capable of generating a hydrophilic group by the action of an acid (for example, a resin having a hydrophilic group protected by a protecting group that can be removed by the action of an acid), A positive photosensitive resin composition can be composed of a fluorene compound, a resin capable of generating a hydrophilic group by the action of an acid, and a photoacid generator. In addition, a photoacid generator is used as a photosensitizer (and, if necessary, a thermosetting resin that can be cured by an acid or a thermosetting resin that acts as a curing agent for the fluorene compound as another resin. The negative photosensitive resin composition can be constituted.

  Specific photosensitive resin compositions include, for example, (1) a photosensitive resin composed of the fluorene compound, a resin (such as a melamine resin) that can be crosslinked or cured by the action of an acid, and a photoacid generator. Composition (positive or negative photosensitive resin composition, especially negative photosensitive resin composition), (2) Resin capable of generating a hydrophilic group by the action of the fluorene compound and acid (for example, hydroxyl group Photosensitive resin composition (positive photosensitive resin composition) comprising a protective group (for example, an alkyl group) that can be removed by the action of an acid, and a photoacid generator. Etc.).

  Among these photosensitive resin compositions, in particular, the fluorene compound, a resin that can be crosslinked or cured by the action of an acid (for example, a thermosetting resin such as a melamine resin), and a photoacid generator are included. A photosensitive resin composition is preferred.

  The photosensitive resin composition may include a curing agent or a curing accelerator (for example, the curing agent exemplified above). Moreover, the photosensitive resin composition may contain the above-mentioned additive.

  Furthermore, the photosensitive resin composition may be a composition containing a solvent (coating composition) in order to improve workability such as coating properties. As the solvent, the solvents exemplified above can be used. The solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, and is, for example, 0.1 to 30 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 1 part by weight of the solid content of the photosensitive resin composition. May be about 0.5 to 5 parts by weight.

  The photosensitive resin composition has high sensitivity and high resolution, and is useful for obtaining a pattern having excellent heat resistance and etching resistance as described above. Therefore, the present invention includes a pattern formed from the photosensitive resin composition. Such a pattern formed of the photosensitive resin composition can be formed by applying a conventional lithography technique to the photosensitive layer formed of the photosensitive resin composition.

  The photosensitive layer can be formed by applying (coating or coating) the photosensitive resin composition to a substrate (or substrate). Depending on the characteristics and application of the pattern, substrates such as metals (aluminum, etc.), glass, ceramics (alumina, copper-doped alumina, tungsten silicate, etc.), plastics, semiconductor substrates such as silicon wafers, etc. Can be mentioned.

  The substrate (substrate) may be surface-treated in advance in order to improve the adhesion with the photosensitive layer according to the application. For the surface treatment, for example, surface treatment with a silane coupling agent (hydrolyzable polymerizable silane coupling agent having a polymerizable group, etc.), anchor coating agent or base agent (polyvinyl acetal, acrylic resin, vinyl acetate resin) , Epoxy resin, urethane resin, etc.), or a coating treatment with a mixture of these base materials and inorganic fine particles.

  The photosensitive layer may be formed on at least the surface of the resist layer. The structure of the photosensitive layer can be selected according to a pattern formation process, a circuit structure, and the like, and may be a single layer structure or a multilayer structure (or a laminated structure or a composite structure).

  The thickness in particular of a photosensitive layer is not restrict | limited, For example, it can select from the range of 0.01-10 micrometers, Preferably it is 0.05-5 micrometers, More preferably, it is about 0.08-2 micrometers, Usually, 0.09-1 micrometers ( For example, it may be about 0.1 to 0.7 μm.

  The photosensitive layer can be formed by a conventional coating method such as a spin coating method, a dipping method, or a casting method. In addition, after apply | coating the photosensitive resin composition to a board | substrate, you may evaporate a solvent by drying. The removal of the solvent may be performed by, for example, soft baking (pre-baking) using a heating means such as a hot plate.

  The said pattern (especially fine pattern) can be performed using the conventional lithography technique which combined exposure, image development, etching, etc. For example, a pattern can be formed by applying the photosensitive resin composition to a substrate to form a photosensitive layer, exposing the photosensitive layer, subjecting it to heat treatment as necessary, and developing the photosensitive layer. In particular, in a photosensitive resin composition containing a photoacid generator, heat treatment (post-exposure baking (post-baking or post-exposure baking, PEB), etc.) is performed after exposure in order to efficiently diffuse the acid generated by exposure. Is preferred. In addition, after patterning by development, etching treatment may be performed by plasma treatment (oxygen plasma or the like).

The photosensitive layer can be exposed by a conventional method, for example, by irradiating a pattern with light or exposing it to light through a predetermined mask. As the light beam, various light beams (active light beams) depending on the photosensitive characteristics of the photosensitive resin composition, the fineness of the pattern, the type of the alkali-soluble resin, for example, light beams such as halogen lamps, high pressure mercury lamps, UV lamps; Line (436 nm), i line (365 nm), excimer laser (for example, XeCl (308 nm), KrF (248 nm), KrCl (222 nm), ArF (193 nm), ArCl (172 nm), F ₂ (157 nm), etc.), electron Radiation such as rays (EB), EUV (13 nm), X-rays and the like can be used, and may be a single wavelength or a composite wavelength. In particular, excimer lasers such as KrF (248 nm), ArF (193 nm), and F ₂ (157 nm) can be advantageously used.

  The exposure energy can be selected according to the photosensitive properties (solubility, etc.) of the photosensitive resin composition, and the exposure time is usually 0.005 seconds to 10 minutes, preferably 0.01 seconds to 5 minutes, Preferably, it can select from the range of about 0.1 second-3 minutes.

  The heating (pre-baking and PEB) temperature may be 50 to 150 ° C., preferably 60 to 150 ° C., more preferably about 70 to 130 ° C., and the heating time may be 30 seconds to 5 minutes, preferably 1 to 1. About 2 minutes.

  After pattern exposure, a pattern with high resolution can be formed by developing by a conventional method. Various developing solutions (water, alkaline aqueous solution, etc.) can be used for development according to the type of the photosensitive resin composition. A preferred developer is water or an alkali developer, and if necessary, a small amount of an organic solvent (for example, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves) , Hydrophilic or water-soluble solvents such as cellosolve acetate) and surfactants. The development method is not particularly limited, and for example, a paddle (meniscus) method, a dip method, a spray method, or the like can be adopted.

  The coating film (photosensitive layer) may be heated or cured at an appropriate temperature in an appropriate process from the application to the development of the photosensitive resin composition, not limited to the prebaking and PEB. For example, heat treatment may be performed as necessary after development.

In the present invention, a fluorene having a phenolic hydroxyl group (a compound represented by the above formula (A)) is substituted with a methylol group [specifically, an aryl group of 9,9-bis (hydroxyaryl) fluorene]. Compound is obtained. Since such a compound has high reactivity and also has a fluorene skeleton, when used as a resin raw material, a fluorene skeleton having excellent characteristics can be introduced efficiently. That is, since the novel fluorene compound has a phenolic hydroxyl group and a methylol group and is excellent in reactivity, it can be applied to various uses. For example, a conventional novolak-type phenol resin obtained by reacting a bisphenol having a fluorene skeleton (for example, a compound represented by the above formula (A)) and a conventional phenol in the presence of an acid catalyst, The fluorene compound and conventional phenols (mono C _1-20 alkylphenols such as phenol and cresol) are used as the phenol component, while having low molecular weight (for example, weight average molecular weight of about 1000) and low practicality. The phenol resin (novolak type phenol resin) obtained by polymerization (condensation) in the presence of an acid catalyst has a high molecular weight due to a high reaction of the fluorene compound. Therefore, many fluorene skeletons can be introduced into the phenol resin, and practicality is high.

  In addition, the fluorene compound of the present invention (or the compound represented by the formula (1)) is a resin resin (including various compounds having a phenolic hydroxyl group and / or a compound having a methylol group as a polymerization component in addition to a phenol resin ( For example, it can be suitably used for epoxy resin raw materials, acrylic resin raw materials (for example, photocurable acrylic resins such as polyfunctional (meth) acrylates), and resin raw materials such as polyester resin raw materials).

  Furthermore, the compound of the present invention has self-crosslinkability (or curability), and the cured product (cured coating film) is excellent in plasma resistance and etching resistance. Furthermore, the fluorene compound of the present invention is also useful as a resin component constituting the photosensitive resin composition. Such a photosensitive resin composition has high sensitivity and high resolution, and is excellent in etching resistance. ing.

  For this reason, the fluorene compound of the present invention and its resin composition [or its (preliminary) cured product] are a resin raw material (such as a phenol resin raw material) or a curing agent [for example, an epoxy resin curing agent (an epoxy resin for semiconductor encapsulation). Curing agent, etc.)], adhesive, paint (prime coating, etc.), rubber compounding agent, binder (binder for grindstone, abrasive paper, friction material, etc.), laminated material (or laminated product, for example, Copper-clad laminates, laminated tubes, laminated rods, etc.), heat-sensitive materials (heat-sensitive paper materials, etc.), carbon materials, insulating materials, foams, pressure-sensitive materials (pressure-sensitive paper materials, etc.), shell molds, various resin materials ( Raw materials for novolac type epoxy resins, resin binders, etc., molded bodies (molded bodies for electrical and electronic parts, thin films, etc.), circuit forming materials (resist for semiconductor manufacturing, printed wiring boards, etc.), image forming materials (printing plate materials, Reli Etc. off image), the lower film (hard mask of a resist (for semiconductor manufacturing resist, etc.)) can be applied to various applications such as.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In the examples, molecular weight and the like were measured as follows.

(Measurement of molecular weight)
A tetrahydrofuran solution (about 5% by weight solution) containing a sample (phenolic resin) was prepared, and weight averaged in terms of polystyrene under a measurement condition of 40 ° C. by gel permeation type chromatograph (manufactured by TOSOH, “HLC-8020”). Molecular weight (Mw) was measured.

(Dry etching resistance evaluation method)
Etching was performed under the following conditions using a reactive ion etching apparatus (Samco Co., Ltd., load lock type RIE apparatus).

Equipment: SAMCO load lock RIE equipment
Model RIE 200-L
Gas: O ₂ : SF ₆ = 5: 30 (sccm)
Pressure: 6Pa
Output: 150W / 24cmφ
Time: 3min
And the value which remove | divided the thickness (nm) of the film | membrane lose | disappeared by the etching by the etching time (minutes) was displayed as dry-etching resistance [or etching rate (nm / min)]. It shows that dry etching resistance is so high that this value is small.

(NMR)
^{The 1} H-NMR spectrum was measured using tetramethylsilane as a reference substance and CDCl ₃ as a solvent, and recorded with a JEOL GTX-400 spectrometer.

Example 1
378 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.), 63 parts by weight of a 37% formaldehyde aqueous solution, 270 parts by weight of orthocresol, and 10.8 oxalic acid The mixture was mixed with parts by weight and reacted at 100 ° C. with stirring for 24 hours. To the resulting reaction mixture, 1500 parts by weight of methyl isobutyl ketone was added, impurities were removed by neutralization and extraction, and filtration was performed to obtain 407 parts by weight of the intended reaction product (reaction product 1). . The obtained reaction product had a weight average molecular weight of 558.

Moreover, when the obtained reaction product was analyzed by ¹ H-NMR, it was confirmed that p1 and p3 were 1 and p2 was 0 in the formula (1). The ¹ H-NMR spectrum data of the obtained reaction product is shown below.

¹ H-NMR (CDCl ₃ , δ): 6.5 to 7.9 ppm (12H), 3.5 to 3.8 ppm (2.0H), 1.9 to 2.1 ppm (9.9H), 0.8. 8-0.9 ppm (2.8H).

(Example 2)
In Example 1, reaction product 2 was obtained in the same manner as Example 1 except that metacresol was used instead of orthocresol. The ¹ H-NMR spectrum data of the obtained reaction product is shown below.

¹ H-NMR (CDCl ₃ , δ): 7.8 ppm (2.0 H), 7.2 to 7.6 ppm (5.9 H), 6.7 to 6.9 ppm (3.8 H), 6.5 6.6 ppm (2.0 H), 2.1 ppm (2.7 H), 2.0 ppm (10.8 H), 0.8-0.9 ppm (8.3 H).

(Example 3)
In Example 1, reaction product 3 was obtained in the same manner as in Example 1 except that para-cresol was used instead of ortho-cresol.

Example 4
In Example 1, instead of 378 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 6,6 ′-(9-fluorenylidene) -di (2-naphthol) (or 6,6 The reaction product 4 was prepared in the same manner as in Example 1 except that 540 parts by weight of '-(9-fluorenylidene) -bis (2-naphthol), manufactured by Osaka Gas Chemical Co., Ltd., “Bisnaphtholfluorene”) was used. Obtained. The weight average molecular weight of the obtained reaction product was 643.

(Comparative Example 1)
70 parts by weight of metacresol (MCR), 30 parts by weight of paracresol (PCR), 77 parts by weight of p-formaldehyde, 300 parts by weight of water and 60 parts by weight of methanol, and 51 parts by weight of sodium hydroxide (caustic soda) as an alkali The mixture was mixed and reacted for 6 hours with stirring at 50 ° C. to prepare a general-purpose novolac type phenol resin (Mw = 4899). Then, 100 parts by weight of the obtained general-purpose novolac-type phenol resin was dissolved in 1000 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Tokyo Chemical Industry) to obtain a coating composition. After the cleaned silicon wafer is treated with hexamethyldisilazane, the coating composition prepared using a spin coater is applied so that the film thickness after drying is 0.4 μm, and is heated on a hot plate at 100 ° C. for 5 minutes. Heated. Subsequently, it heated at 180 degreeC for 20 minute (s), and the film | membrane was obtained. As a result of measuring the etching rate of the film thus obtained, it was 36.3 nm / min.

(Example 5)
A film was prepared in the same manner as in Comparative Example 3 except that 100 parts by weight of the reaction product 1 obtained in Example 1 was used instead of 100 parts by weight of the general-purpose novolak-type phenol resin, and the etching resistance was measured. The speed was 30.2 nm / min. The etching rate (hereinafter referred to as the etching rate) when the etching rate of the film obtained in Comparative Example 1 is 100 is 83 (30.2 ÷ 36.3 × 100), which is compared with the general-purpose novolac type phenol resin. It was found that the etching resistance was excellent.

(Example 6)
A film was prepared in the same manner as in Comparative Example 1 except that 100 parts by weight of the reaction product 2 obtained in Example 2 was used instead of 100 parts by weight of the general-purpose novolak-type phenol resin, and the etching resistance was measured. The speed was 30.9 nm / min. The etching rate was 85, and it was found that the etching resistance was excellent as compared with the general-purpose novolac type phenol resin.

(Example 7)
A film was prepared in the same manner as in Comparative Example 1 except that 100 parts by weight of the reaction product 3 obtained in Example 3 was used instead of 100 parts by weight of the general-purpose novolak-type phenol resin, and the etching resistance was measured. The speed was 31.9 nm / min. The etching rate was 88, and it was found that the etching resistance was excellent as compared with the general-purpose novolac type phenol resin.

(Example 8)
A film was prepared in the same manner as in Comparative Example 1 except that 100 parts by weight of the reaction product 4 obtained in Example 4 was used instead of 100 parts by weight of the general-purpose novolak-type phenol resin, and the etching resistance was measured. The speed was 27.9 nm / min. The etching rate was 77, which was found to be extremely excellent in etching resistance as compared with general-purpose novolac type phenol resins.

  Table 1 below summarizes the results of etching rate and etching rate.

(Comparative Example 2)
100 parts by weight of a general-purpose novolak type phenolic resin obtained in Comparative Example 1, 25 parts by weight of a compound represented by the following formula (a) as a crosslinking agent (melamine / formaldehyde resin, manufactured by American Cyanamide Co., Ltd., trade name cymel303), And 3 parts by weight of a compound represented by the following formula (b) as a photoacid generator (triazine photoacid generator, manufactured by Midori Chemical Co., TAZ-107), propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Tokyo Chemical Industry Co., Ltd.) ) It was dissolved in 1000 parts by weight to obtain a photosensitive resin composition.

  After the cleaned silicon wafer is treated with hexamethyldisilazane, the photosensitive resin composition prepared using a spin coater is applied so that the film thickness after drying is 0.4 μm, and is heated on a hot plate at 100 ° C. Heated for 1 minute. Next, a test mask having line and space patterns with different line widths using a reduction projection exposure machine (Canon, FPA-3000EX5, NA = 0.63) having an exposure wavelength of 248 nm (KrF excimer laser) Then, the exposure amount was changed in stages. The wafer was heated on a hot plate at 120 ° C. for 2 minutes and then paddle developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 1 minute to obtain a negative pattern. As a result of measuring the etching rate of the film thus obtained, the etching rate of the exposed portion was 44.8 nm / min, and the etching rate of the unexposed portion was 46.3 nm / min.

Example 9
In Comparative Example 2, a film was prepared in the same manner as in Comparative Example 2 except that 100 parts by weight of the reaction product 1 obtained in Example 1 was used instead of 100 parts by weight of the general-purpose novolak type phenolic resin. As a result of the measurement, the etching rate of the exposed part was 36.1 nm / min, and the etching rate of the unexposed part was 37.1 nm / min. The etching rate (hereinafter referred to as the etching rate) when the etching rate (exposed portion or unexposed portion) of the film obtained in Comparative Example 2 is 100 is 81 for the exposed portion and 80 for the unexposed portion. It was found that the etching resistance was excellent as compared with the novolac type phenolic resin.

(Example 10)
In Comparative Example 2, a film was prepared in the same manner as in Comparative Example 2 except that 100 parts by weight of the reaction product 2 obtained in Example 2 was used instead of 100 parts by weight of the general-purpose novolak-type phenol resin, and the etching rate was increased. As a result of the measurement, the etching rate of the exposed portion was 40.6 nm / min, and the etching rate of the unexposed portion was 41.7 nm / min. The etching rate was 91 in the exposed area and 90 in the unexposed area, and it was found that the etching rate was superior to that of a general-purpose novolac type phenol resin.

(Example 11)
In Comparative Example 2, a film was prepared in the same manner as in Comparative Example 2 except that 100 parts by weight of the reaction product 3 obtained in Example 3 was used instead of 100 parts by weight of the general-purpose novolak type phenolic resin, and the etching rate was adjusted. As a result of the measurement, the etching rate of the exposed portion was 39.5 nm / min, and the etching rate of the unexposed portion was 42.0 nm / min. The etching rate was 88 in the exposed area and 91 in the unexposed area, and it was found that the etching rate was superior to that of a general-purpose novolac type phenol resin.

(Example 12)
In Comparative Example 2, a film was prepared in the same manner as in Comparative Example 2 except that 100 parts by weight of the reaction product 4 obtained in Example 4 was used instead of 100 parts by weight of the general-purpose novolak-type phenol resin, and the etching rate was adjusted. As a result of the measurement, the etching rate of the exposed part was 32.8 nm / min, and the etching rate of the unexposed part was 34.2 nm / min. The etching rate was 73 in the exposed area and 74 in the unexposed area, and it was found that the etching rate was extremely excellent as compared with the general-purpose novolac type phenol resin.

  Table 2 below summarizes the results of etching rate and etching rate.

(Resist performance (dissolution rate) evaluation)
The resist performance of the films obtained in the examples and comparative examples was evaluated. The dissolution rate was measured using a resist development analyzer RDA-805 manufactured by Risotech Japan. The light source was a monochromatic light of LED 950 nm.

(Comparative Example 3)
The film obtained in the same manner as in Comparative Example 2 was measured for the dissolution rate of the unexposed area. As a result, it was 70 nm / second, and the exposed area was not dissolved.

(Example 13)
The film obtained in the same manner as in Example 10 was measured for the dissolution rate of the unexposed area. As a result, it was 653 nm / second, and the exposed area was not dissolved. Therefore, it was found that the resist performance is superior to that of a general-purpose novolac type phenol resin.

Claims (12)

A compound represented by the following formula (1).

(In the formula, ring Z ¹ , ring Z ² and ring Z ³ are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a , R ^2b and R ^2c are the same or different and represent a substituent, and R ^3a , R ^{3 3b} , R ^3c and R ^3d are the same or different and each represents a hydrogen atom or a hydrocarbon group; k1 and k2 are the same or different and each represents 0 or an integer of 1 to 4; m1, m2 and m3 are each 0 or 1 or more N1, n2 and n3 each represent 0 or an integer of 1 or more, p1 represents an integer of 1 or more, and p2 and p3 represent 0 or an integer of 1 or more.) In the formula (1), the ring ^{Z 1,} ring ^{Z 2} and Ring ^{Z 3} is a benzene ring or a naphthalene ^ring, R ^{2a, R 2b} and ^{R 2c} is a hydrocarbon group, m1, m @ 2 and m3 is 0, respectively 2. The compound according to claim 1, wherein n1, n2 and n3 are each 1 or 2.   The compound according to claim 1, wherein in formula (1), p1 and p3 are each 1 or 2, and p2 is 0 or 1. In formula (1), ring Z ¹ , ring Z ² and ring Z ³ are benzene rings, R ^2a , R ^2b and R ^2c are alkyl groups or aryl groups, and R ^3a , R ^3b , R ^3c and R ^3d is a hydrogen atom, m1, m2 and m3 are each 0 to 2, n1, n2 and n3 are each 1, p1 is 1, p2 is 0 and p3 is 0 or 1 The compound of claim 1. In the formula (1), ring Z ¹ and ring Z ² are naphthalene rings, ring Z ³ is a benzene ring, R ^3a , R ^3b , R ^3c and R ^3d are hydrogen atoms, m1, m2 and m3 The compound according to claim 1, wherein n is 0 to 2, n1, n2 and n3 are each 1, p1 is 1, p2 is 0, and p3 is 0 or 1. The method of manufacturing the compound of Claim 1 by making the compound represented by the compound represented by the following formula (A), the compound represented by the following formula (B), and the following formula (C) react.

(In the formula, R ³ represents a hydrogen atom or a hydrocarbon group, and Z ¹ , Z ² , Z ³ , R ^1a , R ^1b , R ^2a , R ^2b , R ^2c , k1, k2, m1, m2, m3, n1, n2, and n3 are the same as above.)   The production method according to claim 6, wherein the reaction is carried out in the presence of an acid catalyst.   A cured product obtained by curing the compound according to claim 1.   A resin composition comprising at least the compound according to claim 1.   The resin composition according to claim 9, which is a photosensitive resin composition comprising the compound according to claim 1 and a photosensitive agent.   The resin composition according to claim 10, which is a negative photosensitive resin composition comprising the compound according to claim 1, a thermosetting resin curable by the action of an acid, and a photoacid generator.   The pattern formed with the resin composition of Claim 11.