JP5259117B2 - Thermosetting resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in heat resistance and etching property. <P>SOLUTION: This thermosetting resin composition is constituted by a phenol resin having phenol components consisting of fluorenes having a phenolic hydroxy group and phenols and having &ge;2,000 weight-average molecular weight, and an epoxy compound having a fluorene backbone. The phenol resin may be a condensate obtained by condensing the methylol form of the fluorenes having the phenolic hydroxy group with the phenols in the presence of an acid catalyst. In the epoxy compound having the fluorene backbone, 9,9-bis(glycidyloxyphenyl)fluorene, 9,9-bis(mono or di(a 1-4C alkyl)glycidyloxyphenyl)fluorene, 9,9-bis(glycidyloxynaphthyl)fluorene and their adducts with a 2-4C alkylene oxide are included. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a thermosetting resin composition excellent in heat resistance, plasma resistance or etching resistance and a cured product thereof (for example, a hard mask).

  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 phenolic resin, it is known to introduce a rigid skeleton such as a fluorene skeleton into the novolac phenolic 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 comprising a phenolic condensate condensed via an aldehyde (D), wherein the aromatics (B) is a compound represented by the following formula (1) Has been.

_{XCH 2 -R 1 -CH 2 X (} 1)
(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])

  Therefore, the objective of this invention is providing the thermosetting resin composition excellent in heat resistance, plasma resistance, or etching resistance, and its hardened | cured material.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that in the thermosetting resin composition composed of a phenol resin and an epoxy compound (or epoxy resin), both the phenol resin and the epoxy resin are fluorene. It has been found that a thermosetting resin composition excellent in heat resistance and plasma resistance can be obtained by comprising a specific compound having a skeleton, thereby completing the present invention.

  That is, the thermosetting resin composition of the present invention is a fluorene having a phenolic hydroxyl group and a phenol resin having phenol as a phenol component, the phenol resin having a weight average molecular weight of 2000 or more, and an epoxy having a fluorene skeleton. It is composed of compounds.

  In the thermosetting resin composition, the phenol resin may be a novolak type phenol resin having a weight average molecular weight of 3000 or more and a glass transition temperature of 100 ° C. or more.

  In the phenol resin, the fluorene having a phenolic hydroxyl group may be a compound represented by the following formula (1).

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a and R ^2b are the same or different and represent substituents. K1 and k2 are the same or different and represent 0-4. An integer, m1 and m2 are each 0 or an integer of 1 or more, and n1 and n2 are each an integer of 0 or 1. However, n1 + n2 ≧ 1.
In the formula (1), ring Z ¹ and ring Z ² are a benzene ring or a naphthalene ring, n1 and n2 are each 1 or 2, m1 and m2 are each 0 to 2, and R ^2a and R ^2b May be a hydrocarbon group (alkyl group, aryl group, etc.).

Further, in the formula (1), n1 and n2 are each 1, in each of the rings Z ¹ and the ring Z ^2, three of the carbon atoms located ortho and para to the hydroxyl group, unsubstituted And a carbon atom substituted by R ^2a and R ^2b . If such fluorenes are used, it is easy to prepare a high molecular weight phenol resin (novolac-type phenol resin) because the excessive polymethylol formation of the fluorenes can be suppressed.

Representative examples of the fluorene having a phenolic hydroxyl group include 9,9-bis (hydroxyphenyl) fluorenes [for example, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxy). Phenyl) fluorene, etc.], 9,9-bis (dihydroxyphenyl) fluorenes (eg, 9,9-bis (dihydroxyphenyl) fluorene), 9,9-bis (hydroxynaphthyl) fluorenes (eg, 9,9- Bis (hydroxynaphthyl) fluorene) and the like. The fluorenes having a phenolic hydroxyl group are, in particular, 9,9-bis (4-hydroxy-3-substituted phenyl) fluorene [or 9,9-bis (4-hydroxyphenyl) substituted at the 3-position of the phenyl group. Fluorenes such as 9,9-bis (4-hydroxy-3-alkylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cycloalkylphenyl) fluorene, and 9,9-bis (4-hydroxy-) At least one selected from 3-arylphenyl) fluorene], 9,9-bis (dihydroxyphenyl) fluorene or 9,9-bis (hydroxynaphthyl) fluorene, and in particular 9,9-bis ( 4-hydroxy _{-3-C 1-4} alkyl phenyl) fluorene or 9,9-bis (hydroxynaphthyl) fluorene May be used.

  The phenols may be, for example, cresol.

  In the phenol component, the proportion of phenols may be about 0.1 to 10 parts by weight with respect to 1 part by weight of fluorenes having a phenolic hydroxyl group.

  The phenol resin may be a condensate obtained by condensing a fluorene methylol body having a phenolic hydroxyl group and a phenol in the presence of an acid catalyst.

In a typical thermosetting resin composition, the phenol resin (novolac-type phenol resin) is a condensate obtained by condensing a fluorene methylol body having a phenolic hydroxyl group and a phenol in the presence of an acid catalyst. (I) a phenol having a phenolic hydroxyl group is 9,9-bis (4-hydroxy-3-C _1-4 alkylphenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene, or 9,9-bis (Hydroxynaphthyl) fluorene, (ii) the proportion of phenol is 0.2 to 3 parts by weight with respect to 1 part by weight of fluorene having a phenolic hydroxyl group, and (iii) the weight average molecular weight is 3000 or more. And (iv) a phenol resin having a glass transition temperature of 110 ° C. or higher.

  In the thermosetting resin composition of the present invention, the epoxy compound having the fluorene skeleton may be, for example, a compound 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 ring Z ¹ and the ring Z ² are a benzene ring or a naphthalene ring, R ^2a and R ^2b are an alkyl group or an aryl group, and m1 and m2 are 0 to 2, respectively. , R ^3a and R ^3b may be a C _2-4 alkylene group, n1 and n2 may each be 0 to 10, and p1 and p2 may each be 1 to 3.

Typically, the epoxy compound having a fluorene skeleton is 9,9-bis (glycidyloxyphenyl) fluorene, 9,9-bis (mono or diC _1-4 alkylglycidyloxyphenyl) fluorene, 9,9- It may be at least one selected from bis (mono- or di-C _6-10 arylglycidyloxyphenyl) fluorene 9,9-bis (glycidyloxynaphthyl) fluorene, and their C _2-4 alkylene oxide adducts. .

  In the thermosetting resin composition of the present invention, the proportion of the epoxy compound may be about 5 to 300 parts by weight with respect to 100 parts by weight of the phenol resin. The thermosetting resin composition may further contain a curing accelerator (such as phosphines).

  Moreover, the hardened | cured material which the said thermosetting resin composition hardened | cured is also contained in this invention.

  Since such a cured product (or the thermosetting resin composition) is excellent in plasma resistance or etching resistance (for example, dry etching resistance), the cured product (or the thermosetting resin composition). May be a cured product (or a thermosetting resin composition) used for a resist hard mask.

  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.

  Since the thermosetting resin composition of the present invention is composed of a specific compound in which both the phenol resin and the epoxy resin have a fluorene skeleton, the conventional thermosetting resin composition containing a phenol resin and an epoxy resin can be used. Compared with heat resistance, plasma resistance or etching resistance, it is superior. In particular, since the thermosetting resin composition of the present invention is excellent in plasma resistance, it can be suitably used for a resist hard mask.

<Thermosetting resin composition>
The thermosetting resin composition of the present invention comprises at least a specific phenol resin containing a fluorene skeleton and an epoxy compound (epoxy resin) having a fluorene skeleton.

[Phenolic resin]
The phenol resin is a phenol resin (fluorene skeleton-containing phenol resin) containing a fluorene having a phenolic hydroxyl group and a phenol (non-fluorene phenol) as a phenol component, and has a specific molecular weight. Such a phenol resin is usually a resin (or thermoplastic phenol resin) obtained by reacting a methylol body of a fluorene having a fluorene skeleton with a phenol in the presence of an acid catalyst, that is, a novolak. Type phenol resin (fluorene skeleton-containing novolac resin) may be used.

(Fluorenes having a phenolic hydroxyl group)
The fluorene having a phenolic hydroxyl group (sometimes simply referred to as fluorenes) is not particularly limited as long as it has a phenolic hydroxyl group and a fluorene skeleton, but is usually a compound represented by the following formula (1) It may be.

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a and R ^2b are the same or different and represent substituents. K1 and k2 are the same or different and represent 0-4. An integer, m1 and m2 are each 0 or an integer of 1 or more, and n1 and n2 are each an integer of 0 or 1. However, n1 + n2 ≧ 1.
In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z ¹ and the ring Z ² include a benzene ring and a condensed polycyclic hydrocarbon ring (specifically, a condensed polycyclic ring containing at least a benzene ring). Hydrocarbon ring). 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. Rings Z ¹ and Z ² may be the same or different rings, and may usually be the same ring.

Preferred rings Z ¹ and Z ² include a benzene ring and a naphthalene ring, and a naphthalene ring is particularly preferred.

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 and n2 of the hydroxyl group substituted on ring Z ¹ and ring Z ² is not particularly limited as long as n1 + n2 ≧ 1 is satisfied. Usually, n1 and n2 are each 1 or more, for example, 1 to 4, preferably May be 1 to 3, more preferably 1 to 2, especially 1. 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. In addition, the substitution numbers n1 and n2 of the hydroxyl group may be the same or different in each of the rings Z ¹ and Z ² and are usually the same in many cases.

Incidentally, the substitution position of the hydroxyl group is not particularly limited, as long as the replaced with appropriate substitution position of the ring Z ¹ and the ring Z ^2. 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.

As substituents R ^2a and R ^2b for substituting ring Z ¹ and ring Z ² (hereinafter, collectively referred to as ring Z), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group) C _1-20 alkyl group such as butyl group, s-butyl group, t-butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (cyclopentyl group, A C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 cycloalkyl group), an aryl group [eg, a phenyl group, an alkylphenyl group (methyl Phenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group, etc.), dimethylphenyl group (xylyl group, etc.), naphth _{C 6-10} aryl group such group, preferably a _{C 6-8} aryl group, especially a phenyl group, an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) Hydrocarbon groups such as; alkoxy groups (C _1-4 alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group and t-butoxy group); acyl groups (C ₁ such as acetyl group) _-6 an acyl group); an alkoxycarbonyl group (such as a C _1-4 alkoxycarbonyl group such as methoxycarbonyl group), a halogen atom (fluorine atom, such as chlorine atom); nitro group; cyano group; carboxyl group; amino group; substituted An amino group (dialkylamino group etc.) etc. are mentioned.
Preferred substituents R ^2a and R ^2b are an alkyl group (eg, a C _1-6 alkyl group), a cycloalkyl group (eg, a C _5-8 cycloalkyl group), an aryl group (eg, a C _6-10 aryl group). A hydrocarbon group such as an aralkyl group (for example, a C _6-8 aryl-C _1-2 alkyl group), in particular, a C _1-4 alkyl group (particularly a methyl group), a C _1-4 alkoxy group, a C _{6 A -8} aryl group is preferred. When m1 or m2 is 2 or more, the substituents R ^2a and R ^2b may be substituted alone or in combination of two or more in the same ring (ring Z ¹ or ring Z ² ). Further, the substituents R ^2a and R ^2b substituted on different rings Z ¹ and Z ² may be the same or different from each other, and may be usually the same.

The substitution numbers m1 and m2 of the substituents R ^2a and R ^2b can be appropriately selected according to the kind of the ring Z ¹ and the ring Z ² , and are not particularly limited. For example, 0 to 8, preferably 0 to 6 (For example, 1-5), More preferably, about 0-4 may be sufficient. In particular, when ring Z ¹ and ring Z ² are benzene rings, the number of substitutions m1 and m2 depends on the number of substitutions n1 and n2 of the hydroxyl group, but 0 to 3, preferably 1 to 2, respectively. 1 in particular. Incidentally, substituents which m1 and m2, in each ring Z ¹ and Z ^2, which may be identical or different, typically, is often the same.

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

In particular, three carbon atoms located in the ortho position and the para position are carbon atoms in which an unsubstituted carbon atom and an aldehyde (formaldehyde, etc.) cannot be substituted (for example, a substituent (R ^2a or R ^2b ), etc. And a carbon atom bonded to the 9-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.

  If the fluorenes having such a configuration are used, it may be possible to condense while suppressing cross-linking by methylol, so that it seems that it becomes easier to prepare a high molecular weight phenol resin (novolak type phenol resin).

  Typical fluorenes having a phenolic hydroxyl group include, for example, (1) 9,9-bis (hydroxyphenyl) fluorenes, (2) 9,9-bis (hydroxynaphthyl) fluorenes, and the like.

(1) 9,9-bis (hydroxyphenyl) fluorenes (1a) 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 (trihydroxyphenyl) such as 9,9-bis (2,4,6-trihydroxyphenyl) fluorene In general, 9,9-bis (monohydroxyphenyl) fluorenes or 9,9-bis (dihydroxyphenyl) fluorenes, particularly 9,9-bis (monohydroxyphenyl) fluorenes are preferred. Can be 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) and the like], 9,9-bis (dihydroxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9, 9,9-bis (C _1-4 alkyl-dihydroxy) such as 9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluorene Phenyl) fluorene, 9,9-bis (2,4-dihydroxy-3,6-dimethyl) 9,9-bis (diC _1-4 alkyl-dihydroxyphenyl) fluorene, etc.] such as ruphenyl) fluorene, 9,9-bis (aryl-dihydroxyphenyl) fluorene [eg, 9,9-bis (3,4- 9,9-bis (C _6-8 aryl-dihydroxyphenyl) fluorene and the like] such as dihydroxy-5-phenylphenyl) fluorene] and the like.

  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. Further, fluorenes in which ring Z ¹ and ring Z ² such as 9,9-bis (hydroxynaphthyl) fluorene are condensed aromatic hydrocarbon rings such as naphthalene ring are not only improved in heat resistance and refractive index. Further, the thermal expansion can be reduced, which is advantageous in improving the dimensional accuracy.

(Phenols)
Examples of the phenols include phenols other than fluorene having a phenolic hydroxyl group (or phenols having no fluorene skeleton). The phenols may have a substituent (an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, etc.). The phenols may have the same or different substituents. In phenols, the number of substituents may be, for example, 0 to 6 (for example, 0 to 4), preferably 1 to 3, and more preferably about 1 to 2. In addition, a commercial item may be used for phenols, and it can also prepare it by the well-known method known in the said field | area.

Typical phenols include, for example, monophenols {eg, phenol, alkylphenol [cresol (o-cresol, m-cresol, p-cresol), ethylphenol (2-ethylphenol, etc.), butylphenol, octylphenol, nonylphenol]. mono _{C 1-20} alkylphenol (such as for example, mono _{C 1-10} alkylphenol); xylenol (2,3-dimethylphenol, 2,4-dimethylphenol, etc.) and di _{C 1-10} alkylphenols, etc.], cyclo alkyl phenols (Such as 2-cyclohexylphenol), arylphenol (such as o-phenylphenol), alkoxyphenol (such as anisole such as o-methoxyphenol), aminophenol, etc. Phenol having substituent; naphthol [e.g., naphthol (alpha-naphthol, beta-naphthol, etc.), alkyl naphthol (methyl naphthol, ethyl naphthol, dimethyl naphthol, etc. C _1-4 alkyl naphthol such as propyl naphthol), etc.], etc. }, Phenols having a plurality of phenolic hydroxyl groups [for example, dihydroxybenzene (catechol, resorcinol, hydroquinone), alkyl-dihydroxybenzene (mono- or di-C _1-6 alkyl-dihydroxybenzene such as dihydroxytoluene, dihydroxyxylene, etc.), aryl - dihydroxybenzene (2,3-dihydroxy-biphenyl, _{C 6-8} aryl, such as 3,4-dihydroxybiphenyl - such as dihydroxybenzene), alkoxy - dihydro Shibenzen (3-methoxy catechol such as mono- or di-C _1-6 alkoxy - such as dihydroxybenzene), trihydroxy benzenes (pyrogallol, hydroxyhydroquinone, phloroglucinol, etc.) polyhydric phenols such as 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 phenol component, the proportion of phenols can be selected from a range of 0.01 to 100 parts by weight (for example, 0.05 to 50 parts by weight) with respect to 1 part by weight of fluorenes having a phenolic hydroxyl group. 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 0.2 to 3 parts by weight (for example, 0.25 to 2 parts by weight) About 0.1 to 1.5 parts by weight (for example, 0.2 to 1 part by weight). In the present invention, a phenol resin having a high molecular weight (for example, a weight average molecular weight of 2000 or more) can be obtained even when fluorenes having a phenolic hydroxyl group in the above proportion are used.

  The weight average molecular weight of the phenol resin (usually a novolak type phenol resin) can usually be selected from the range of 2000 or more (for example, about 2200 to 50000), for example, 2500 or more (for example, about 2700 to 40000), preferably 3000. More than that (for example, about 3200 to 30000), more preferably 3300 to 25000 (for example, about 3500 to 20000), and usually about 3000 to 15000 (for example, about 3500 to 12000).

  Moreover, most of the phenol resins are composed of a relatively high molecular weight resin. For example, in the phenol resin, the proportion of a component having a weight average molecular weight of 1000 or less (phenol resin) is based on the whole phenol resin. 20% by weight or less (for example, about 0.1 to 17% by weight), preferably 15% by weight or less (for example, about 0.5 to 12% by weight), more preferably 10% by weight or less (for example, 1 to 8%). % By weight), particularly 7% by weight or less (for example, about 1.5 to 5% by weight), and usually about 2 to 15% by weight (for example, 3 to 10% by weight).

  The weight average molecular weight can usually be measured by GPC (gel permeation chromatography), and can be measured under predetermined conditions (for example, in terms of polystyrene).

  The molecular weight distribution (Mw / Mn) of the phenol resin is, for example, 1 to 7 (for example, 1.1 to 6), preferably 1.2 to 6.5 (for example, 1.5 to 6), Preferably, it may be about 1.5 to 5.5 (for example, 1.7 to 5), and 2.5 or less (for example, about 1.2 to 2.2, preferably about 1.5 to 2). You can also

  Moreover, since the phenol resin has a fluorene skeleton and a high molecular weight, it usually has high heat resistance. For example, the glass transition temperature of the phenol resin is, for example, 90 ° C. or higher (for example, about 95 to 250 ° C.), preferably 100 ° C. or higher (for example, about 105 to 230 ° C.), and more preferably 110 ° C. or higher (for example, 115-220 ° C.), particularly 120 ° C. or higher (eg, about 125-200 ° C.), and usually 110-210 ° C. (eg, 120-190 ° C.).

  Such a phenol resin is a phenol resin (usually a novolac-type phenol resin) having the phenol component as a condensation component, and is a reaction product of the phenol component and aldehydes. Such a phenol resin is usually a condensate obtained by condensation [usually condensation in the presence of an acid catalyst (or under acidic conditions)] with a methylol body of a fluorene having a phenolic hydroxyl group and a phenol. As will be described later, it can be efficiently obtained by a specific method in which a phenol component and aldehydes are reacted stepwise (in two steps). In addition, as long as the methylol body has a methylol group, at least in part, the methylol body of fluorenes having a phenolic hydroxyl group is condensed with each other (or a precondensate or a condensation unit such as a weight average). A condensate having a degree of polymerization of 2 to 5, preferably about 2 to 3, may be formed. Usually, the methylol body is often a monomer.

  Typical methylol bodies include compounds represented by the following formula (2) (that is, compounds in which at least one methylol group is substituted on the fluorenes represented by the formula (1)).

(In the formula, R ^3a and R ^3b are the same or different and each represents a hydrogen atom or a hydrocarbon group, and p1 and p2 each represent 0 or an integer of 1 or more, provided that p1 + p2 ≧ 1. Ring Z ¹ , Ring Z ² , R ^1a , R ^1b , R ^2a , R ^2b , k1, k2, m1, m2, n1 and n2 are the same as above.)
In the above formula (2), the hydrocarbon group represented by the groups R ^3a and R ^3b is the hydrocarbon group exemplified in the section of the groups R ^2a and R ^2b [for example, an alkyl group (for example, a 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, etc.). The groups R ^3a and R ^3b may usually be a hydrogen atom or an alkyl group (such as a methyl group), preferably a hydrogen atom. Further, the substitution numbers p1 and p2 of the methylol group [that is, in the formula (2), the group — (CHR ^3a OH), the group — (CHR ^3b OH)] are not particularly limited as long as p1 + p2 ≧ 1 is satisfied. , P1 and p2 are each 1 or more, for example, 1 to 4, preferably 1 to 3, more preferably 1 according to the number of substitutions of the hydroxyl group or substituent R ^2a (or R ^2b ) and the substitution position thereof. It may be ˜2, especially 1. In particular, when ring Z ¹ and ring Z ² are benzene rings, p 1 and p 2 may each be 1-2, especially 1. Incidentally, substituents which p1 and p2, in each ring Z ¹ and Z ^2, which may be identical or different, may be generally the same. Similarly, the methylol group is substituted according to the number of hydroxyl groups and substituents R ^2a (or R ^2b ) and the substitution position thereof. For example, ring Z ¹ and ring Z ² are benzene rings. Yes, when 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 (ortho position of the 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 at least the 3-position May be substituted.

In the formula (2), Z ¹ , Z ² , R ^1a , R ^1b , R ^2a , R ^2b , k1, k2, m1, m2, n1 and n2 are the same as described above. That is, the compound represented by the formula (2) corresponds to the fluorenes represented by the formula (1), and at least one methylol is present in the ring Z ¹ and / or the ring Z ² of the fluorenes. A compound in which a group is substituted. Preferred rings, groups, substitution numbers and the like are the same as described above.

  Representative examples of the compound represented by the formula (2) include 9,9-bis (methylol-hydroxyphenyl) fluorenes and 9,9-bis (methylol-hydroxynaphthyl) fluorenes.

As 9,9-bis (methylol-hydroxyphenyl) fluorenes, 9,9-bis (monomethylol-hydroxyphenyl) fluorenes (in the above formula (2), ring Z ¹ and ring Z ² are benzene rings) , Compounds in which p1 and p2 are 1) {for example, 9,9-bis (methylol-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylolphenyl) fluorene and the like], 9 having a substituent , 9-bis (methylol-hydroxyphenyl) fluorene {e.g., 9,9-bis (methylol-alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-5-methyl-3-methylolphenyl) fluorene, 9,9-bis (4-hydroxy-5-ethyl-3-methylolphenyl) fluore , 9,9-bis (3-hydroxy-2-methyl-4-methylol-phenyl) fluorene such as 9,9-bis (methylol _{-C 1-4} alkyl - hydroxyphenyl) fluorene, 9,9-bis (4- hydroxy-2,6-dimethyl-3-methylol-phenyl) fluorene such as 9,9-bis (methylol - di _{C 1-4} alkyl - hydroxyphenyl) fluorene, etc.], 9,9-bis (methylol - cycloalkyl - hydroxy Phenyl) fluorene [9,9-bis (methylol-C _5-8 cycloalkyl-monohydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-5-cyclohexyl-3-methylol-phenyl) fluorene], 9,9-bis (methylol-aryl-hydroxyphenyl) fluorene [for example 9,9-bis (methylol-C _6-8 aryl-hydroxyphenyl) fluorene and the like such as 9,9-bis (4-hydroxy-5-phenyl-3-methylolphenyl) fluorene], 9,9-bis ( Methylol-aralkyl-hydroxyphenyl) fluorene [for example, 9,9-bis (methylol-C _6-8 arylC _1-, such as 9,9-bis (4-hydroxy-5-benzyl-3-methylol-phenyl) fluorene. ₂ alkyl - 9,9-bis such hydroxyphenyl) fluorene] (monomethylol - mono-hydroxyphenyl) fluorenes; these 9,9-bis (monomethylol - corresponding to mono-hydroxyphenyl) fluorenes 9,9 -Bis (monomethylol-polyhydroxyphenyl) fluorenes (eg 9 9-bis (3,4-dihydroxy-2-methylolphenyl) fluorene, 9,9-bis (3,4-dihydroxy-5-methylolphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6- 9,9-bis (monomethylol-dihydroxyphenyl) fluorenes such as methylolphenyl) fluorene (compounds wherein n1 and n2 are 1 in the formula (2)), etc., and these 9,9-bis (monomethylol) - corresponds to hydroxyphenyl) fluorenes 9,9-bis (polymethylolated - hydroxyphenyl) fluorenes (formula (2), the ring ^{Z 1} and the ring ^{Z 2} is a benzene ring, 2 p1 and p2, respectively And the like).

  Examples of 9,9-bis (methylol-hydroxynaphthyl) fluorenes include 9,9-bis (monomethylol-hydroxynaphthyl) fluorenes {eg, 9,9-bis [6- (2-hydroxy1-methylol). -Naphthyl)] fluorene, 9-bis [6- (2-hydroxy3-methylol-naphthyl)] fluorene, 9,9-bis [1- (5-hydroxy-6-methylolnaphthyl)] fluorene, 9,9- 9,9-bis (monomethylol-monohydroxynaphthyl) fluorene which may have a substituent such as bis [1- (5-hydroxy-8-methylolnaphthyl)] fluorene, these 9,9-bis ( 9,9-bis (monomethylol-polyhydroxynaphthyl) corresponding to monomethylol-monohydroxynaphthyl) fluorene ) Such fluorenes}, these 9,9-bis (monomethylol - hydroxynaphthyl) corresponding to fluorenes 9,9-bis (polymethylolated - hydroxynaphthyl) fluorene compounds and the like.

  The compound represented by the formula (2) corresponds to these 9,9-bis (methylol-hydroxyphenyl) fluorenes and 9,9-bis (methylol-hydroxynaphthyl) fluorenes, and p1 = Also included are compounds that are not p2 (eg, p1 = 1 and p2 = 0, p1 = 1 and p2 = 2, etc.). The substitution number p1 or p2 of such a methylol group can be adjusted by appropriately adjusting the ratio of aldehydes to be reacted with the fluorenes.

Preferred compounds represented by the formula (2) include 9,9-bis (4-hydroxy-3-methylolphenyl) fluorenes [for example, 9,9-bis (4-hydroxy-3-methylol-5- Alkylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylol-5-cycloalkylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylol-5-arylphenyl) fluorene, etc.] 9,9-bis (monomethylol-hydroxyphenyl) fluorenes, especially 9,9-bis (4-hydroxy-3-methylol-5-alkylphenyl) fluorene [especially 9,9-bis ( 9,9-bis (4-hydroxy-3-methylol-) such as 4-hydroxy-3-methylol-5-methylphenyl) fluorene -C _1-4 alkylphenyl) fluorene] is preferred.

(Phenolic resin production method)
The phenol resin can be usually produced by reacting a fluorene methylol body having a phenolic hydroxyl group (sometimes simply referred to as a methylol body) with a phenol (usually reacting in the presence of an acid catalyst). By such a method, even if a fluorene having a phenolic hydroxyl group is used as a phenol component, a phenol resin having a relatively high molecular weight can be obtained efficiently.

  A fluorene methylol body having a phenolic hydroxyl group can be obtained by reacting a fluorene having a phenolic hydroxyl group with an aldehyde (methylolation reaction). Such a methylolation reaction can usually be performed in the presence of a base catalyst (under alkaline conditions). The “methylol group” means a substituted methylol group (or hydroxymethyl group), and the methylol group is a substituted methylol group substituted with an alkyl group (for example, an alkyl-substituted group such as a 1-hydroxyethyl group). A methylol group, etc.).

  The aldehydes are not particularly limited, and alkanals (for example, acetaldehyde and the like) may be used. Usually, a formaldehyde source such as formaldehyde and paraformaldehyde 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. The purity of the fluorenes used for the methylolation reaction is not particularly limited, but may be usually 95% by weight or more, preferably 99% by weight or more.

  The ratio of the aldehydes used in the preparation of the methylol body is, for example, 0.1 to 100 moles, preferably 0.1, in terms of formyl group (HCO-) or methylol group with respect to 1 mole of fluorenes having a phenolic hydroxyl group. It may be 5 to 50 mol, more preferably 1 to 30 mol, particularly about 1.5 to 20 mol. In particular, the ratio of aldehydes is, for example, 0.3 to 30 mol (for example, 0.5 to 20 mol) in terms of formyl group (HCO-) or methylol group with respect to 1 mol of phenolic hydroxyl group of the fluorenes. ), Preferably 0.7 to 15 mol (for example, 0.8 to 10 mol), more preferably 1 mol or more (for example, about 1.1 to 8 mol), and usually 1 to 7 mol ( For example, about 1.1-5 mol) may be sufficient.

  In addition, the preferable methylol body is comprised by the polymethylol body (namely, the compound which the average 2 or more methylol group substituted per 1 mole of fluorenes). Such a polymethylol body is prepared by adjusting the ratio of the aldehydes according to the type of fluorenes (for example, using 1 mol or more of aldehydes with respect to 1 mol of phenolic hydroxyl groups of fluorenes). Can do. Among such polymethylol bodies, in particular, from the viewpoint of obtaining a high molecular weight phenol resin by reaction with phenols, it is preferable that at least a dimethylol body is constituted. For example, the 9,9-bis (4-hydroxy-3-substituted phenyl) fluorene is a compound in which the ortho position with respect to two phenolic hydroxyl groups is substituted. A product can be efficiently obtained as a dimethylol body without polymethylolation (tetramethylolation or the like). In the methylol body (the total amount of the monomethylol body and the polymethylol body), the ratio of the polymethylol body (for example, dimethylol body) is, for example, 50 mol% or more (for example, about 55 to 100 mol%), preferably 60 mol%. It may be more than (for example, about 65 to 99 mol%), more preferably 70 mol% or more (for example, about 75 to 98 mol%), particularly 80 mol% or more (for example, about 85 to 95 mol%). .

  Further, as described above, the methylol body may be a condensate (oligomer) condensed at least in part.

  In the methylolation reaction, the basic catalyst (base catalyst) is not particularly limited, and metal hydroxide (alkali metal or alkaline earth metal water such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide) Oxides, etc.), metal carbonates (such as alkali carbonates or alkaline earth metal carbonates (hydrogen) salts such as sodium carbonate and sodium hydrogen carbonate), inorganic bases such as ammonia; amines [for example, primary to tertiary amines Monoamines such as (mono- to trialkylamines such as methylamine and triethylamine, aromatic primary to tertiary amines such as aniline and N, N-dimethylaniline), polyamines such as hexamethylenetetramine, etc.], carboxylate metal Salt (alkaline or alkaline earth metal acetate such as sodium acetate and calcium acetate) Etc. can be exemplified organic bases such as such). The base catalysts may be used alone or in combination of two or more.

  The use ratio of the base catalyst is, for example, 0.1 to 50 parts by weight (for example, 0.3 to 20 parts by weight), preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the fluorenes. May be about 1 to 5 parts by weight.

  The methylolation 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 is about 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 with respect to 1 part by weight of the fluorenes. May be.

  In the methylolation reaction, the reaction temperature may be, for example, about 0 to 250 ° C., preferably 20 to 150 ° C., more preferably about 30 to 100 ° C. (for example, 40 to 80 ° C.). The methylolation reaction time may be, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, more preferably about 1 to 10 hours. The methylolation reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), and may be performed under normal pressure or under pressure.

  A methylol body of fluorenes can be prepared as described above.

  In the reaction (condensation reaction) between the methylol body and the phenol, the proportion of the phenol can be selected from the same range as described above. The purity of the phenols used in the condensation reaction is not particularly limited, but is usually 95% by weight or more, for example, 97% by weight or more, preferably 99% by weight or more. The condensation reaction only needs to be performed using the methylol body produced by the methylolation reaction, and the reaction product after completion of the methylolation reaction (for example, a liquid reaction product containing a solvent) is directly used for the condensation reaction. Alternatively, a methylol body separated (separated and purified) from the reaction product after completion of the reaction may be subjected to a condensation reaction. In order to simplify the process, the reaction product after the methylolation reaction is often subjected to a condensation reaction as it is.

  The condensation reaction can usually be performed in the presence of an acid catalyst (or under 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 can be selected according to the type of the acid catalyst and the amount of the basic catalyst used for the methylolation reaction. For example, 0.1 to 10 parts by weight with respect to 1 part by weight of the fluorenes, Preferably, it may be about 0.2-8 parts by weight, more preferably about 0.3-7 parts by weight, and usually about 0.1-9 parts by weight. In the condensation reaction, the ratio of the acid catalyst present in the reaction system (the ratio of the acid catalyst excluding the acid catalyst used for neutralizing the basic catalyst) is, for example, 0 with respect to 1 part by weight of the fluorenes. 0.001 to 2 parts by weight, preferably 0.005 to 1 part by weight, and more preferably about 0.01 to 0.1 part by weight.

  The condensation reaction may be performed in a solvent. Examples of the solvent include the same solvents as those exemplified above, and the amount of solvent used can be selected from the same range as described above. In addition, when using the reaction product after completion | finish of the said methylolation reaction for a condensation reaction, the solvent of methylolation reaction may be used as a solvent as it is, and a solvent may be newly added.

  In the condensation reaction, the reaction temperature may be, for example, about 0 to 250 ° C., preferably 20 to 200 ° C., more preferably about 30 to 150 ° C. (for example, 50 to 100 ° C.). The condensation reaction time may be, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, more preferably about 1 to 10 hours. The condensation 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.

  A phenol resin is obtained by the above condensation reaction.

  The reaction mixture after completion of the condensation reaction contains, in addition to the phenol resin, a solvent, a catalyst (such as a base catalyst and an acid catalyst), an unreacted component (such as a phenol), and the like. 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. .

[Epoxy compound having fluorene skeleton]
Examples of the epoxy compound having a fluorene skeleton include a compound represented by the following formula (3) (an epoxy compound corresponding to the compound represented by the formula (1)).

(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-bis (4 -9,9-bis (mono- or di-C _1-4 alkyl-glycidyloxyphenyl) fluorene such as glycidyloxy-3,5-dimethylphenyl) fluorene], 9,9-bis (arylglycidyloxyphenyl) fluorene [ 9,9-bis (4-glycidyloxy-3-phenylpheny 9,9-bis (glycidyloxyphenyl) fluorenes such as 9,9-bis (mono- or di-C _6-8 aryl-glycidyloxyphenyl) fluorene, etc.] such as 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) fur 9,9-bis (di or triglycidyloxyaryl) fluorene} such as fluorene] fluorine}, 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 [eg, 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-dimethylphenyl) ) 9,9-bis fluorene (mono- or _{di-C 1-4} Ruki glycidyl oxy _{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 [eg, 9,9-bis (glycidyloxy C _{2 -4} alkoxy naphthyl) fluorene, 9,9-bis [di or tri (glycidyloxy alkoxyphenyl) phenyl] fluorene [e.g., 9,9-bis [3,4-di (2-glycidyloxyethoxy) phenyl] fluorene 9,9-bis [3,4,5-tri ( - Compound q1 and q2 are 1 in 9,9-bis glycidyl) phenyl] fluorene [di- or tri (the expression, such as glycidyloxy _{C 2-4} alkoxy) phenyl] fluorene] (3); these In the formula (3), q1 and q2 are 2 or more, such as 9 [9,9-bis {4- [2- (2-glycidyloxyethoxy) ethoxy] phenyl} fluorene, etc. , 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 (alkylglycidyloxyphenyl) ) Fluorene (eg, 9,9-bis (mono or di C _1-4 alkylglycidyloxyphenyl) fluorene), 9,9-bis (arylglycidyloxyphenyl) fluorene (eg, 9,9-bis (mono or di) C _6-10 arylglycidyloxyphenyl) fluorene), 9,9-bis (glycidyloxynaphthyl) fluorene, etc.}, C _2-4 alkylene oxide adducts of 9,9-bis (glycidyloxyaryl) fluorenes [eg, 9,9-bis (glycidyloxy C _2-4a Lucoxyphenyl) fluorene etc.] are preferred.

  These epoxy compounds having a fluorene skeleton can be used alone or in combination of two or more.

  In the thermosetting resin composition, the epoxy compound having the fluorene skeleton seems to be reactive with the phenol resin. Therefore, the epoxy compound having a fluorene skeleton acts as a curing agent for the phenol resin and is firmly bonded to each other, so that many fluorene skeletons can be introduced into the cured product. It is useful for obtaining a cured product having extremely excellent etching resistance.

  In the thermosetting resin composition of the present invention, the proportion of the epoxy compound having a fluorene skeleton depends on the use and the like, but is, for example, 1 to 1000 parts by weight, preferably 2 to 100 parts by weight with respect to 100 parts by weight of the phenol resin. It may be 500 parts by weight, more preferably 5 to 300 parts by weight (for example, 10 to 200 parts by weight), particularly about 30 to 150 parts by weight, and usually about 50 to 200 parts by weight.

  The thermosetting resin composition may further contain a curing accelerator (or a curing agent). Such a curing agent may be a curing agent for the phenol resin or the epoxy compound having the fluorene skeleton, or may be a curing agent for both the phenol resin and the epoxy compound having the fluorene skeleton.

  Curing accelerators (or curing aids) include amines (for example, chain aliphatic amines (chain aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine), cyclic aliphatic amines [mensen Such as diamine, isophorone diamine, bis (4-amino-3-methylcyclohexyl) methane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane Monocyclic aliphatic polyamines, norbornanediamines, condensed cyclic or bridged cyclic polyamines such as hexamethylenetetramine, etc.], aromatic or araliphatic amines (xylylenediamine metaphenylenediamine, diaminodiphenylmethane, etc.)}, phosphines [For example, ethylphosphine, propylene Organic phosphines (first, second and third phosphines) such as sphin, phenylphosphine, triphenylphosphine and trialkylphosphine], amide compounds (such as dimer acid polyamide), epoxy compounds [for example, epichloro Hydrin, diglycidyl ether, polyol polyglycidyl ether (butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, etc.), diglycidyl aniline, cyclohexane dimethanol diglycidyl ether, etc. Polyglycidyl ethers, epoxy resins (such as epi-bis type epoxy resins, phenol type epoxy resins, brominated epoxy resins, glycol type epoxy resins) )], Protonic acid (for example, inorganic acid such as sulfuric acid and phosphoric acid, organic acid such as acetic acid), acid anhydride (phthalic anhydride, tetrahydromethylphthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, Methyl nadic acid anhydride, etc.). These curing accelerators 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, the ratio of the curing agent (or cross-linking agent) depends on the type, but is 0.1 to 100 weights with respect to 100 parts by weight of the total amount of the epoxy resin and the epoxy compound having a fluorene skeleton. Parts, preferably 0.3 to 50 parts by weight, more preferably about 0.5 to 30 parts by weight, and usually about 0.1 to 20 parts by weight (for example, 0.1 to 10 parts by weight). There may be.

  In addition, the composition (coating composition) containing a solvent may be sufficient as a thermosetting resin composition so that it may mention later.

  The thermosetting resin composition of the present invention may contain additives and the like. 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. In addition, the thermosetting resin composition of the present invention has other resin components [for example, a phenol resin (a phenol resin not belonging to the category of the phenol resin), an epoxy resin ( A thermosetting resin such as an epoxy resin not belonging to the category of the epoxy compound having a fluorene skeleton].

  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.

  In the coating liquid, 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 acetate Ether ether, 3-methoxybutyl-1-acetate), 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, 2-hydroxy-2 -Methyl butanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc.) That. These solvents may be used alone or in admixture of two or more.

  In the coating liquid, the proportion of the solvent is, for example, 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, more preferably 1 part by weight of the epoxy compound having the phenol resin and the fluorene skeleton. May be about 0.5 to 30 parts by weight.

  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 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.

  The thermosetting resin composition of the present invention is excellent in various properties such as heat resistance, environmental resistance, and mechanical properties (such as bending properties, toughness, and thermal shock properties). And since such a thermosetting resin composition is excellent in molding processability, a molded object can be obtained simply and efficiently. Such a molded body can be obtained by a method such as molding the thermosetting resin composition into a predetermined shape, or forming a thin film on a substrate and curing it. In particular, the thermosetting resin composition or the cured product (cured coating film) of the present invention is excellent in plasma resistance and etching resistance.

  For this reason, the thermosetting resin composition [or its (preliminary) cured product] of the present invention is a curing agent [for example, a curing agent for epoxy resin (such as a curing agent for epoxy resin for semiconductor encapsulation)], an adhesive. , Paint (undercoat paint, etc.), rubber compounding agent, binder (binder for grindstone, abrasive paper, friction material, etc.), laminated material (or laminated product, for example, copper-clad laminate, laminated tube, laminated rod) Etc.), thermal materials (thermal 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 epoxy resins, resin binders, etc.) ), Molded bodies (molded bodies for electric and electronic parts, thin films, etc.), circuit forming materials (resist for semiconductor manufacturing, printed wiring boards, etc.), image forming materials (printing plate materials, relief images, etc.), resist (for semiconductor manufacturing) Under the resist) Film (hard mask) can be applied to various applications such as. Further, the thermosetting resin composition [or its (preliminary) cured product] of the present invention is excellent in transparency and is also useful as a thermosetting resin composition for optical devices.

  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 glass transition temperature were measured as follows.

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

(Measurement of glass transition temperature)
The glass transition temperature (Tg) was measured with a differential scanning calorimeter (DSC, manufactured by SII, “DSC6220”).

(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.

(Synthesis Example 1)
454 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (Osaka Gas Chemical Co., Ltd.), 86 parts by weight of p-formaldehyde, 840 parts by weight of water as a solvent, and 120 parts by weight of methanol Then, 104 parts by weight of sodium hydroxide (caustic soda) as an alkali was mixed and reacted at 50 ° C. with stirring for 6 hours.

When the obtained reaction product was analyzed by ¹ H-NMR, it was confirmed to be 9,9-bis (4-hydroxy-3-methylol-5-methylphenyl) fluorene.

The ¹ H-NMR spectrum data of the obtained reaction product is shown below.

¹ H-NMR (CDCl ₃ , d): 2.0 ppm [6H (CH ₃ )], 4.55 ppm [4H (hydrogen of methylene group of methylol group)], 4.95 ppm [2H (of hydroxyl group of methylol group) Hydrogen)], 6.6 to 6.7 ppm [2H (hydrogen at the 2-position of the benzene ring substituted at the 9-position of fluorene)], 6.8 to 6.9 ppm [2H (benzene ring substituted at the 9-position of fluorene) 6-position hydrogen)], 7.1-7.4 ppm [6H (hydrogens 2-4 and 5-7 of fluorene)], 7.7 ppm [2H (hydrogens 1-position and 8-position of fluorene) ], 8.2 ppm [2H (hydrogen of phenolic hydroxyl group)].

  After adding 840 parts by weight of methyl isobutyl ketone and 100 parts by weight of 35% hydrochloric acid to the obtained reaction product, 130 parts by weight of orthocresol and 2 parts by weight of oxalic acid were further added and stirred at 90 ° C. while stirring. Reacted for hours. Subsequently, impurities were removed by neutralization and extraction, and the reaction product obtained by filtration was dried to obtain 400 parts by weight of the target phenol resin (novolak type phenol resin). When the weight average molecular weight Mw of the obtained phenol resin was measured, it was 4,328 and molecular weight distribution (Mw / Mn) was 2.1. Moreover, the ratio of the component of the weight average molecular weight 1000 or less computed from the GPC chart was 10 weight% or less. Furthermore, as a result of measuring the glass transition temperature (Tg) of the obtained phenol resin, it was found to be 126 ° C. and excellent in heat resistance.

(Synthesis Example 2)
In Synthesis Example 1, a phenol resin was obtained in the same manner as in Synthesis Example 1 except that 130 parts by weight of metacresol was used instead of 130 parts by weight of ortho-cresol. When the weight average molecular weight Mw of the obtained phenol resin was measured, it was 7,533 and molecular weight distribution (Mw / Mn) was 2.8. Moreover, the ratio of the component of the weight average molecular weight 1000 or less computed from the GPC chart was 10 weight% or less. Furthermore, as a result of measuring the glass transition temperature (Tg) of the obtained phenolic resin, it was found to be 166 ° C. and excellent in heat resistance.

(Synthesis Example 3)
In Synthesis Example 1, a phenol resin was obtained in the same manner as in Synthesis Example 1 except that 130 parts by weight of para-cresol was used instead of 130 parts by weight of ortho-cresol. When the weight average molecular weight Mw of the obtained phenol resin was measured, it was 6,079 and the molecular weight distribution (Mw / Mn) was 6.4. Moreover, the ratio of the component of the weight average molecular weight 1000 or less computed from the GPC chart was 10 weight% or less. Furthermore, as a result of measuring the glass transition temperature (Tg) of the obtained phenolic resin, it was found to be 155 ° C. and excellent in heat resistance.

(Synthesis Example 4)
In Synthesis Example 1, 454 parts by weight of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was changed to 6,6 ′-(9-fluorenylidene) -di (2-naphthol) (manufactured by Osaka Gas Chemical Co., Ltd., A “phenol resin” was obtained in the same manner as in Synthesis Example 1 except that “bisnaphtholfluorene”) was changed to 540 parts by weight. When the weight average molecular weight Mw of the obtained phenol resin was measured, it was 5,215 and the molecular weight distribution (Mw / Mn) was 2.6. Moreover, the ratio of the component of the weight average molecular weight 1000 or less computed from the GPC chart was 10 weight% or less. Furthermore, as a result of measuring the glass transition temperature (Tg) of the obtained phenol resin, it was found to be 184 ° C. and a resin excellent in heat resistance.

(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 1
100 parts by weight of the phenol resin obtained in Synthesis Example 1, 100 parts by weight of 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (or bisphenoxyethanol fluorenediglycidyl ether, BPEFG, manufactured by Osaka Gas Chemical Co., Ltd.) And 1 part by weight of triphenylphosphine (TPP, manufactured by Nacalai) as a curing catalyst was dissolved in 200 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 hexamethylsilazane, the coating composition prepared using a spin coater is applied so that the film thickness after drying is 0.4 μm, and heated at 100 ° C. for 5 minutes on a hot plate. did. Subsequently, it heated at 180 degreeC for 20 minute (s), and the film | membrane was obtained. The etching rate of the film thus obtained was measured and found to be 33.1 nm / min. When the etching rate of the film obtained in Comparative Example 1 is set to 100, the etching rate (hereinafter referred to as an etching rate) is 91, which is excellent in etching resistance as compared with the film obtained in Comparative Example 1. all right.

(Example 2)
In Example 1, a membrane was prepared in the same manner as in Example 1 except that 100 parts by weight of the phenol resin obtained in Synthesis Example 2 was used instead of 100 parts by weight of the phenol resin obtained in Synthesis Example 1. As a result of measuring the etching performance, the etching rate was 27.3 nm / min. The etching rate was 75, which was found to be excellent in etching resistance as compared with the film obtained in Comparative Example 1.

(Example 3)
In Example 1, a membrane was prepared in the same manner as in Example 1 except that 100 parts by weight of the phenol resin obtained in Synthesis Example 3 was used instead of 100 parts by weight of the phenol resin obtained in Synthesis Example 1. As a result of measuring the etching performance, the etching rate was 31.6 nm / min. The etching rate was 87, which was found to be excellent in etching resistance as compared with the film obtained in Comparative Example 1.

Example 4
In Example 1, a membrane was prepared in the same manner as in Example 1 except that 100 parts by weight of the phenol resin obtained in Synthesis Example 4 was used instead of 100 parts by weight of the phenol resin obtained in Synthesis Example 1. As a result of measuring the etching performance, the etching rate was 25.8 nm / min. The etching rate was 71, which was found to be excellent in etching resistance as compared with the film obtained in Comparative Example 1.

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

Claims (15)

A phenolic resin fluorenes and the phenols having a phenolic hydroxyl group and phenolic component, a phenolic resin having a higher weight average molecular weight of 2000, a thermosetting resin composition composed of an epoxy compound having a fluorene skeleton A cured product that is used as a resist hard mask . The cured product according to claim 1, wherein the phenol resin is a novolak type phenol resin having a weight average molecular weight of 3000 or more and a glass transition temperature of 100 ° C or more. The cured product according to claim 1, wherein the fluorene having a phenolic hydroxyl group is a compound represented by the following formula (1).

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a , R ^1b , R ^2a and R ^2b are the same or different and represent substituents. K1 and k2 are the same or different and represent 0-4. An integer, m1 and m2 are each 0 or an integer of 1 or more, and n1 and n2 are each an integer of 0 or 1. However, n1 + n2 ≧ 1. In the formula (1), the ring Z ¹ and the ring Z ² are a benzene ring or a naphthalene ring, n1 and n2 are each 1 or 2, m1 and m2 are each 0-2, and R ^2a and R ^2b are The cured product according to claim 3, which is a hydrocarbon group. The phenol having a phenolic hydroxyl group is 9,9-bis (4-hydroxy-3-substituted phenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene or 9,9-bis (hydroxynaphthyl) fluorene Item 1. A cured product according to item 1. Fluorenes having a phenolic hydroxyl group, 9,9-bis (4-hydroxy _{-3-C 1-4} alkyl phenyl) fluorene or 9,9-bis (hydroxy naphthyl) according to claim 1 cured product according fluorene. The cured product according to claim 1, wherein the phenol is cresol. The hardened | cured material of Claim 1 whose ratio of phenols is 0.1-10 weight part with respect to 1 weight part of fluorenes which have a phenolic hydroxyl group. The cured product according to claim 1, wherein the phenol resin is a condensate obtained by condensing a methylol body of fluorene having a phenolic hydroxyl group and a phenol in the presence of an acid catalyst. A phenol resin is a condensate obtained by condensing a methylol body of a fluorene having a phenolic hydroxyl group and a phenol in the presence of an acid catalyst, and (i) the phenol having a phenolic hydroxyl group is 9,9-bis. (4-hydroxy-3- _C1-4 alkylphenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene or 9,9-bis (hydroxynaphthyl) fluorene, and (ii) the proportion of phenols is phenol 2. The fluorene having a functional hydroxyl group is 0.2 to 3 parts by weight based on 1 part by weight, (iii) a weight average molecular weight of 3000 or more, and (iv) a glass transition temperature of 110 ° C. or more. Cured product . The cured product according to claim 1, wherein the epoxy compound having a fluorene skeleton is a compound 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 those defined in claim 3.) In Formula (3), Ring Z ¹ and Ring Z ² are a benzene ring or a naphthalene ring, R ^2a and R ^2b are an alkyl group or an aryl group, m1 and m2 are each 0 to 2, and R ^3a The cured product according to claim 11, wherein R ^3b is a C _2-4 alkylene group, n 1 and n 2 are each 1 to 3, and q 1 and q 2 are each 0 to 8. Epoxy compounds having a fluorene skeleton include 9,9-bis (glycidyloxyphenyl) fluorene, 9,9-bis (mono or diC _1-4 alkylglycidyloxyphenyl) fluorene, 9,9-bis (mono or diC) _2. The cured product according to claim 1, which is at least one selected from _6-10 arylglycidyloxyphenyl) fluorene, 9,9-bis (glycidyloxynaphthyl) fluorene, and a C _2-4 alkylene oxide adduct thereof . The hardened | cured material of Claim 1 whose ratio of an epoxy compound is 5-300 weight part with respect to 100 weight part of phenol resins. Further, according to claim 1 cured product further comprising a curing accelerator.