JP4778535B2 - Phenolic resin and method for producing the same - Google Patents

Description

  The present invention relates to a phenol resin (particularly a novolac type phenol resin) excellent in heat resistance and plasma resistance (or etching resistance), a production method thereof, a resin composition (such as a photosensitive resin composition) containing the phenol resin, and It is related with the pattern formed with the said 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- 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 phenol resin excellent in heat resistance, a method for producing the same, a resin composition (such as a photosensitive resin composition) containing the phenol resin, and a pattern formed from the photosensitive resin composition. Is to provide.

  Another object of the present invention is formed of a phenol resin excellent in plasma resistance or etching resistance, a production method thereof, a resin composition (such as a photosensitive resin composition) containing the phenol resin, and the photosensitive resin composition. Is to provide different patterns.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that the phenol component is obtained by reacting (condensation reaction) with a phenol component and a crosslinking agent component. When it is composed of specific fluorenes having a hydrocarbon skeleton, and the cross-linking agent component is composed of a specific cross-linking agent having an aromatic skeleton (aromatic cross-linking agent), the phenol component is a normal or conventional phenol (phenol, It was found that a phenol resin having significantly improved heat resistance and plasma resistance can be obtained as compared with the case of 9,9-bis (4-hydroxyphenylfluorene) and the like, and the present invention was completed.

  That is, the phenol resin of the present invention comprises at least one aromatic system selected from a phenol component (A) composed of a compound represented by the following formula (1), an aromatic polyol component, and an aromatic aldehyde component. It is a phenol resin obtained by reacting with a crosslinking agent (B) composed of a crosslinking agent.

(In the formula, ring Z ¹ and ring Z ² are condensed polycyclic 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 m1 and m2 are each 0 or an integer of 1 or more, and n1 and n2 are each 0 or an integer of 1 or more, provided that n1 + n2 ≧ 1.
In the formula (1), ring Z ¹ and ring Z ² are naphthalene rings, n 1 and n 2 are each 1 or 2, m 1 and m 2 are each 0 to 2, and R ^2a and R ^2b are hydrocarbons It may be a group. Typically, the compound represented by the formula (1) may be 9,9-bis (hydroxynaphthyl) fluorene.

  The said phenol component (A) may be comprised with the compound represented by Formula (1), and phenols (for example, cresol etc.). In such a case, the proportion of the phenols may be about 0.1 to 10 parts by weight with respect to 1 part by weight of the compound represented by the formula (1).

In the cross-linking agent (B), the aromatic polyol component is an arene dimethanol component (or di (hydroxymethyl) arene component, such as di (hydroxymethyl) C _6-20 arene component, particularly a xylylene glycol component, It may be a di (hydroxymethyl) naphthalene component and at least one selected from a di (hydroxymethyl) anthracene component. The aromatic polyol component (or arene dimethanol component) is, for example, at least one arene dimethane selected from arene dimethanols, di (halomethyl) arenes, and di (C _1-6 alkoxy-methyl) arenes. It may be a methanol component.

  The aromatic aldehyde component may be at least one selected from benzaldehydes and naphthaldehydes (particularly benzaldehyde).

  The crosslinking agent (B) may be composed of an aromatic crosslinking agent and a non-aromatic crosslinking agent (such as formaldehyde). In such a case, the ratio of the non-aromatic crosslinking agent may be about 0.1 to 5 parts by weight with respect to 1 part by weight of the aromatic crosslinking agent.

  In the phenol resin of the present invention, the proportion of the phenol component (A) and the crosslinking agent (B) is such that the phenolic hydroxyl group contained in the phenol component (A) is A mole, and the hydroxyl group contained in the entire crosslinking agent (B). When at least one functional group selected from aldehyde groups is defined as B mole, the ratio may be such that B / A is about 0.1 to 1.

  The phenolic resin of the present invention may usually be a novolac type phenolic resin (for example, naphthol novolac resin).

The present invention includes a method in which the phenol resin is produced by reacting the phenol component (A) with the crosslinking agent (B). Typically, such a method may be a method for producing a novolac type phenol resin in the presence of an acid catalyst.
Moreover, the hardened | cured material which the said phenol resin hardened | cured is also contained in this invention. Such a cured product may be a molded body or a molded product.

  The present invention also includes a resin composition containing at least the phenol resin. Such a resin composition may be a curable resin composition (thermosetting resin composition) containing the phenol resin and a curing agent or a curable resin [for example, an epoxy compound or the like]. And the hardened | cured material which such a curable resin composition hardened | cured is also contained in this invention.

  Further, the resin composition may be a photosensitive resin composition including the phenol resin and a photosensitive agent. Representative photosensitive resin compositions include negative photosensitive resin compositions composed of the phenol resin, 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.

  Since the cured product (or the curable resin composition or the photosensitive resin composition or pattern) is excellent in plasma resistance or etching resistance (for example, dry etching resistance), the cured product (or the curable property). The resin composition) may be a cured product (or curable 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.

  The novel phenol resin (especially novolak-type phenol resin) of the present invention comprises a phenol component composed of a specific fluorene having a phenolic hydroxyl group and a condensed polycyclic hydrocarbon skeleton, and a specific aromatic having an aromatic skeleton. The crosslinker component composed of a system crosslinker is used as a polymerizable component, and the resin has an aromatic skeleton at a high ratio, so it is excellent in heat resistance. In particular, since the phenol resin of the present invention is excellent in plasma resistance or etching resistance, it can be suitably applied to resist hard mask applications.

  The phenol resin of the present invention comprises a phenol component (A) composed of fluorenes having a phenolic hydroxyl group, and at least one aromatic cross-linking agent selected from an aromatic polyol component and an aromatic aldehyde component. It is a phenol resin obtained by reaction with the cross-linking agent (B).

[Phenol component (A)]
(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, ring Z ¹ and ring Z ² are condensed polycyclic 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 m1 and m2 are each 0 or an integer of 1 or more, and n1 and n2 are each 0 or an integer of 1 or more, provided that n1 + n2 ≧ 1.
In the above formula (1), a condensed polycyclic aromatic hydrocarbon ring represented by ring Z ¹ and ring Z ² (the condensed polycyclic aromatic hydrocarbon corresponding in detail is a condensed bicyclic aromatic carbon Hydrogen (for example, C _8-20 condensed bicyclic hydrocarbon such as indene and naphthalene, preferably C _10-16 condensed bicyclic hydrocarbon), condensed tricyclic aromatic hydrocarbon (for example, anthracene, phenanthrene, etc.) Examples of the condensed polycyclic aromatic hydrocarbon include naphthalene and anthracene, and naphthalene is particularly preferable, and rings Z ¹ and Z ² are preferable. May be the same or different rings, and may usually be the same 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 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.

  Typical fluorenes having a phenolic hydroxyl group include 9,9-bis (hydroxynaphthyl) fluorenes.

  Examples of the 9,9-bis (hydroxynaphthyl) fluorenes include 9,9-bis (hydroxynaphthyl) fluorenes {for example, 9,9-bis (hydroxynaphthyl) fluorene [for example, 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.], which may have a substituent such as 9,9-bis (monohydroxynaphthyl) fluorene}, and these 9,9-bis (monohydroxynaphthyl) fur 9,9-bis (polyhydroxynaphthyl) fluorenes (for example, 9,9-bis (di- or trihydroxynaphthyl) fluorenes) corresponding to fluorenes.

  In addition, 9,9-bis (hydroxynaphthyl) fluorenes are hydroxynaphthalenes (for example, naphthols such as naphthol) instead of phenols in the method for producing 9,9-bis (monohydroxyphenyl) fluorenes. , Polyhydroxynaphthalenes such as dihydroxynaphthalene).

  These fluorenes having a phenolic hydroxyl group may be used alone or in combination of two or more. Particularly preferred compounds represented by the formula (1) include 9,9-bis (hydroxynaphthyl) fluorene.

(Phenols)
The phenol component (A) may be at least composed of fluorenes having a phenolic hydroxyl group, may be composed of fluorenes having a phenolic hydroxyl group alone, or may be composed of fluorenes having a phenolic hydroxyl group (or the above formula ( The compound represented by 1) and phenols (specifically, phenols other than the compound represented by the formula (1)) may be used.

Examples of the phenols include phenols other than the fluorene having a phenolic hydroxyl group. Phenols are substituted groups [alkyl groups (C _1-8 alkyl groups such as methyl groups, preferably C _1-4 alkyl groups), cycloalkyl groups, aryl groups, alkoxy groups, carboxyl groups, alkoxycarbonyl groups, halogen atoms. (A fluorine atom, a chlorine atom, a bromine atom, 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.

  Examples of the phenols include a compound represented by the following formula (a1), a compound represented by the following formula (a2), and a plurality of these compounds having a linking group (for example, a methylene group, 1,1-dimethylmethylene). An alkylidene group such as a group, and an alkylene group such as an ethylene group).

(In the formula, R ³ is a C _1-8 alkyl group or a C _1-8 alkoxy group, i is an integer of 1 to 3, j is an integer of 0 to 2, and the sum of i and j is 4 or less. is there)

(Wherein R ⁴ and R ⁵ are a C _1-8 alkyl group or a C _1-8 alkoxy group, h is an integer of 1 to 3, and g and f are each an integer of 0 to 2)
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 (A), the proportion of phenols can be selected from a range of 0.01 to 30 parts by weight (for example, 0.05 to 20 parts by weight) with respect to 1 part by weight of fluorenes having a phenolic hydroxyl group. 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, and more preferably 0.2 to 3 parts by weight (for example, 0.25 to 2). Part by weight), usually about 0.1 to 1.5 parts by weight (for example, 0.2 to 1 part by weight).

[Crosslinking agent (B)]
(Aromatic crosslinking agent)
The crosslinking agent (B) is composed of at least one aromatic crosslinking agent selected from an aromatic polyol component and an aromatic aldehyde component.

  Examples of the aromatic polyol component include an aromatic diol component such as a compound represented by the following formula (b1).

(In the formula, ring Z ³ is an aromatic hydrocarbon ring, R ⁶ and R ⁷ are the same or different and are divalent hydrocarbon groups, and X is a hydroxyl group, a halogen atom or a C _1-6 alkoxy group.)
In the above formula (b1), examples of the aromatic hydrocarbon ring represented by the ring Z ³ include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring (condensed 2 such as a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring). To 6-ring aromatic hydrocarbon ring, preferably a condensed 2- to 4-ring aromatic hydrocarbon ring). In addition, as long as the aromatic hydrocarbon ring has at least an aromatic hydrocarbon skeleton (benzene skeleton), a partially hydrogenated aromatic hydrocarbon ring [for example, dihydronaphthalene (1,4-dihydronaphthalene) Etc.), hydrogenated naphthalene rings such as 1,2,3,4-tetrahydronaphthalene, and the like]. The aromatic hydrocarbon ring has a substituent [an alkyl group (eg, a C _1-8 alkyl group such as a methyl group, preferably a C _1-4 alkyl group), a cycloalkyl group (eg, a C _5-10 such as a cyclohexyl group). A hydrocarbon group such as a cycloalkyl group) or an aryl group (for example, a C _6-10 aryl group such as a phenyl group); an alkoxy group (for example, a C _1-8 alkoxy group such as a methoxy group, preferably C _1-4 alkoxy) Group), a carboxyl group, an alkoxycarbonyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom and the like)]. In addition, when it has two or more substituents, the same or different substituent may be sufficient as a substituent. The number of substituents may be, for example, 0 to 4 (for example, 0 to 3), preferably about 0 to 2.

In the formula (b1), the divalent hydrocarbon groups R ⁶ and R ⁷ include an alkylidene group (C _1-4 alkylidene group such as methylene group or 1,1-dimethylmethylene group), an alkylene group (ethylene group). , C _2-6 alkylene group such as propylene group, preferably C _2-4 alkylene group). A preferred divalent hydrocarbon group is a methylene group. R ⁶ and R ⁷ may be the same or different groups. In X, examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and examples of the C _1-6 alkoxy group include a methoxy group, an ethoxy group, and a t-butoxy group. X may be the same or different groups.

Typical aromatic polyol components include arene dimethanol components [or di (hydroxymethyl) arene components] such as xylylene glycols (for example, 1,4-benzenedimethanol (p-xylylene glycol or terephthalyl). Alcohol), xylylene glycol such as 1,3-benzenedimethanol (m-xylylene glycol or isophthalyl alcohol), di (hydroxymethyl) naphthalene [for example, di (hydroxymethyl) naphthalene (for example, 1, 5-di (hydroxymethyl) naphthalene, 2,6-di (hydroxymethyl) naphthalene, etc.), di (hydroxymethyl) -dialkylnaphthalene [eg di (hydroxymethyl) dimethylnaphthalene [eg 2,6-di (hydroxy Methyl) -1,5- Di, such as methyl naphthalene, etc.] _{(hydroxymethyl) -C 1-4} alkyl-naphthalene], etc.], di (hydroxymethyl) anthracenes [e.g., di (hydroxymethyl) anthracene (e.g., 9,10-di (hydroxymethyl) Di (hydroxymethyl) arenes [eg di (hydroxymethyl) C _6-20 arenes, preferably di (hydroxymethyl) C _6-18 arenes, more preferably di (hydroxymethyl) ) C _6-16 arenes]; derivatives corresponding to these di (hydroxymethyl) arenes (for example, di (C _1-6 ) such as di (halomethyl) arenes, 1,4-di (methoxymethyl) benzene, etc. Alkoxy-methyl) arenes and the like] and the like.

Preferred aromatic polyol components include xylylene glycol components {for example, xylylene glycols (such as xylylene glycol), di (halomethyl) benzenes [such as di (halomethyl) benzene], di (C _1-6 alkoxy-methyl). ) benzenes [e.g., di (methoxymethyl) such as benzene di _{(C 1-6} alkoxy - methyl) benzene, preferably di _{(C 1-2} alkoxy - methyl) benzene], etc.}, di (hydroxymethyl) naphthalene component {For example, di (hydroxymethyl) naphthalenes [di (hydroxymethyl) naphthalene and the like], di (halomethyl) naphthalenes [for example, dihalomethylnaphthalene (for example, di ((1,5-di (chloromethyl) naphthalene, etc. Chloromethyl) naphthalene and the like], di (C _1-6 alkoxy) _Ci -methyl) naphthalene [eg, di (C _1-6 alkoxy-methyl) naphthalene such as di (methoxymethyl) naphthalene, preferably di (C _1-2 alkoxy-methyl) naphthalene], di (C _{1- 6} alkoxy - methyl) - dialkyl naphthalene [example, di _{(C 1-6} alkoxymethyl) dimethyl naphthalene [example, 2,6-di (methoxymethyl) -1,5-dimethyl-naphthalene, etc.] di, such as _{(C 1- 6} alkoxymethyl) - _{di-C 1-4} alkyl naphthalenes, preferably such as di _{(C 1-2 alkoxymethyl) -C 1-4} alkyl-naphthalene], etc.]}, di (hydroxymethyl) anthracene component {e.g., di (hydroxy Methyl) anthracenes [for example, di (hydroxymethyl) anthracene, etc.], di (halomethyl) Anthracenes [e.g., di-halomethyl anthracene (e.g., 9,10-di (such as chloromethyl) anthracene), etc.], di _{(C 1-6} alkoxy - methyl) anthracenes [e.g., di (such as methoxymethyl) anthracene Di (C _1-6 alkoxy-methyl) anthracene, preferably di (C _1-2 alkoxy-methyl) anthracene and the like] and the like}.

  The aromatic polyol components may be used alone or in combination of two or more.

  Examples of the aromatic aldehyde component include benzaldehydes (for example, benzaldehyde, salicylaldehyde, p-hydroxybenzaldehyde, terephthalaldehyde, etc.), naphthaldehydes (for example, naphthaldehyde, etc.), and the like.

  Preferred aromatic aldehyde components include benzaldehydes (particularly benzaldehyde).

  Aromatic aldehyde components may be used alone or in combination of two or more. Moreover, you may combine an aromatic polyol component and an aromatic aldehyde component.

  The crosslinking agent (B) may be composed of at least the aromatic crosslinking agent, may be composed of an aromatic crosslinking agent alone, or is composed of an aromatic crosslinking agent and a non-aromatic crosslinking agent. May be.

Non-aromatic crosslinking agents include non-aromatic polyol components {eg, aliphatic diol components [eg, alkane diols (ethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,4-butane diol, etc. , 1,2-butanediol, 1,3-butanediol, pentanediol, neopentylglycol and other C _1-10 alkane diols, preferably C _1-6 alkane diols)], alicyclic diol components [for example Di (hydroxyC _1-4 alkyl) C _5-8 cycloalkane etc. such as cyclopentanedimethanol, cyclohexanedimethanol, etc.], non-aromatic aldehyde components [eg formaldehydes such as formaldehyde, paraformaldehyde, trioxane, tetraoxane (or Formaldehyde source ), Aliphatic aldehyde components such as acetaldehyde] and the like. These non-aromatic crosslinking agents may be used alone or in combination of two or more.

  Of these non-aromatic crosslinking agents, formaldehydes are preferred.

  The ratio of the non-aromatic crosslinking agent is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 1 part by weight based on 1 part by weight of the aromatic crosslinking agent. It may be about parts by weight.

  The crosslinking agent (B) is typically (1) a crosslinking agent composed only of an aromatic polyol component, (2) a crosslinking agent composed of an aromatic polyol component and an aromatic aldehyde component, (3) A crosslinking agent composed of an aromatic crosslinking agent and a non-aromatic crosslinking agent is included.

  The ratio of the aromatic crosslinking agent to the entire crosslinking agent (B) is, for example, 30% by weight or more (for example, 40 to 100% by weight), preferably 50% by weight or more (for example, 60 to 100% by weight), It may be preferably 70% by weight or more (for example, 80 to 100% by weight).

  The ratio of the phenol component (A) to the crosslinking agent (B) is selected from A mole of the phenolic hydroxyl group contained in the phenol component (A), hydroxyl group and aldehyde group contained in the entire crosslinking agent (B). Furthermore, when at least one functional group is B mole, B / A = 0.05-2, preferably 0.08-1.5, more preferably about 0.1-1 Good.

  The phenolic resin of the present invention may be a resol type phenolic resin, but may usually be a novolac type phenolic resin (novolac phenolic resin). As will be described later, the novolac-type phenol resin is obtained by reacting (condensation reaction) the phenol component (A) and the crosslinking agent (B) in the presence of an acid catalyst.

  Among the phenolic resins of the present invention, the weight average molecular weight of the novolak type phenolic 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 It may be 3000 or more (for example, about 3200 to 30000), more preferably about 3300 to 25000 (for example, 3500 to 20000).

  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).

  Moreover, the phenol resin of this invention has high heat resistance. For example, the glass transition temperature of the phenol resin of the present invention is, for example, 100 ° C. or higher (for example, about 105 to 300 ° C.), preferably 110 ° C. or higher (for example, about 115 to 250 ° C.), and more preferably 120 ° C. or higher ( For example, it may be about 125 to 230 ° C.), particularly 130 ° C. or more (for example, about 135 to 210 ° C.).

[Production method]
The phenol resin of this invention can be manufactured by making the said phenol component (A) and the said crosslinking agent (B) react. In the reaction, the ratio between the phenol component (A) and the crosslinking agent (B) is the same as described above.

  The reaction can usually be performed in the presence of a catalyst. A catalyst can be selected according to the kind of resol type phenol resin or novolak type phenol resin, and when obtaining a novolak type phenol resin, the reaction (condensation reaction) is usually in the presence of an acid catalyst (or under acidic conditions). Can be done. Hereinafter, the manufacturing method of a novolak type phenol resin is explained in full detail.

  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 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 1 part by weight of the phenol component (A). It may be a degree.

  The reaction (condensation 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 usage-amount of a solvent is not specifically limited, 0.1-100 weight part with respect to 1 weight part of total amounts of the said phenol component (A) and the said crosslinking agent (B), Preferably it is 0.5-50 weight part More preferably, it may be about 1 to 10 parts by weight.

  In the reaction (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 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 reaction may be performed under reflux.

  A phenol resin (novolak-type phenol resin) is obtained by the above condensation reaction.

  In addition, the reaction mixture after completion | finish of condensation reaction contains a solvent, a catalyst (acid catalyst etc.), an unreacted component, etc. other than a phenol resin. 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, reprecipitation, or a separation means combining these. . For use in resist hard mask applications, it is desirable that the molecular weight distribution be as narrow as possible (for example, the dispersity or the molecular weight distribution Mw / Mn is 2.0 or less).

[Use of phenolic resin]
The phenolic resin of the present invention can be used for various applications, and can be used as a thermoplastic resin or a thermosetting resin. That is, the phenolic resin of the present invention has self-crosslinking properties and can be cured alone. Such a cured product of phenol resin is excellent in heat resistance and plasma resistance (or etching resistance). Therefore, the cured product of the phenol resin (cured product obtained by curing the phenol resin) is also included in the present invention.

(Hardened phenolic resin)
The cured product of the phenol resin may be a cured product (crosslinked product, self-crosslinked product) obtained by curing (or crosslinking) the phenol resin alone as a resin component. Such a cured product can be obtained, for example, by heating the phenol resin. 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 phenol resin. ). The coating film may be formed, for example, by applying a coating liquid (coating liquid) containing the phenol resin 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, and more preferably 0.5 to 30 parts by weight with respect to 1 part by weight of the phenol resin. It may be a degree.

  In addition, the said coating liquid (or hardened | cured material) should just contain only the said phenol resin 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, and can be performed by heating the coating film (for example, a heating temperature of 40 to 120 ° C., preferably about 60 to 110 ° C.).

  In the heating of the phenol resin (or coating film), the heating temperature (or post-bake temperature) may be, for example, 120 to 300 ° C, preferably 140 to 250 ° C, 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 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 phenolic resin)
The phenol resin of this invention can also comprise a resin composition. Such a resin composition should just contain the said phenol resin at least, Even if it is a thermoplastic resin composition (For example, the resin composition containing the additive of the said illustration, resin other than the said phenol resin, etc.). It may be a curable resin composition. The curable resin composition may be a photosensitive resin composition as will be described later. In particular, a curable resin composition using the phenol resin of the present invention as a curable resin (thermosetting resin) or a curing agent is useful for obtaining a cured product (particularly a cured film) excellent in heat resistance and etching resistance. It is.

(Curable resin composition and cured product thereof)
The curable resin composition can be appropriately selected according to the case where the phenol resin is used as the curable resin component or the case where the phenol resin is used as the curing agent component. For example, (i) the curing composed of the phenol resin and the curing agent. And (ii) a curable resin composition composed of the phenol resin and a curable resin (or curable compound). Note that, as described above, the phenol resin can be cured alone (in the absence of a curing agent).

  In the curable resin composition (i), examples of the curing agent (including a curing accelerator or a curing assistant) include, for example, a methylol compound {or a methylol derivative, such as a melamine resin [or a melamine resin precursor (formaldehyde of melamine). Adducts or condensates) such as methylol melamine (mono to trimethylol melamine) or condensates thereof (partial condensates), methoxymethylol derivatives, etc.], epoxy compounds [or epoxy derivatives such as epichlorohydrin, diglycidyl, etc. Ether, polyol polyglycidyl ether (butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, etc.), diglycidyl aniline, cyclohexane Polyglycidyl ethers such as methanol diglycidyl ether, epoxy resins (epi-bis type epoxy resins, phenol type epoxy resins, brominated epoxy resins, glycol type epoxy resins, etc.), phosphines [eg, ethyl phosphine, propylene phosphine , Phenylphosphine, triphenylphosphine, organic phosphines such as trialkylphosphine (first, second, and third phosphines)], proton acids (for example, inorganic acids such as sulfuric acid and phosphoric acid, acetic acid, etc. Organic acids), acid anhydrides (phthalic anhydride, tetrahydromethyl phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, methyl nadic anhydride, etc.), amines and the like. These curing agents may be used alone or in combination of two or more.

  Preferred curing agents include methylol compounds and epoxy compounds.

  In the curable 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, based on 100 parts by weight of the phenol resin. Preferably, it may be about 0.5 to 30 parts by weight.

  In the curable resin composition (ii), the curable resin (specifically, the curable resin other than the phenol resin) is not particularly limited, and examples thereof include a phenol resin (such as a novolak phenol resin) and a furan resin. , Urea resins [or precursors of urea resins, such as mono- or dimethylol urea or condensates thereof (partial condensates), etc.], methylol compounds {or methylol derivatives, such as melamine resins [or precursors of melamine resins (of melamine Formaldehyde adduct or condensate), for example, methylol melamine (mono to trimethylol melamine) or its condensate (partial condensate, methoxymethylol derivative, etc.)}, unsaturated polyester resin, epoxy resin (epoxy compounds exemplified above, For example, epi-bis type epoxy resin, phenol type epoxy resin Resin, brominated epoxy resin, glycol type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, etc.), urethane resin (such as polyisocyanate multimer), silicone resin, polyimide, diallyl phthalate resin, vinyl ester resin And other thermosetting resins (or photocurable resins).

  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-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 (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 (or curable resins) can be used alone or in combination of two or more.

  In the curable resin composition (ii), the phenol resin may be non-reactive or reactive with the curable resin. For example, among the phenol resin 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.

  In the curable resin composition (ii), the ratio of the curable resin depends on the use, 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 phenol resin. More preferably, it may be about 5 to 300 parts by weight (for example, 10 to 200 parts by weight).

  The curable resin composition (ii) may further contain a curing agent (or a curing accelerator). Such a curing agent may be a curing agent for the phenol resin or the curable resin, or may be a curing agent for both the phenol resin and the curable 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 curable 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 curable resin composition (ii), the ratio of the curing 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 total amount of the phenol resin and the curable resin. More preferably, it may be about 0.5 to 30 parts by weight, and usually about 0.1 to 10 parts by weight.

  A preferable curable resin composition (ii) includes the phenol resin, a curable resin [in particular, a thermosetting resin that can act as a curing agent or a crosslinking agent for the phenol resin such as an epoxy resin], and the like. Further, a curable resin composition composed of a curing agent or a curing accelerator (such as phosphines) is included.

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

  Moreover, the curable resin composition (the curable resin composition (i) and the curable 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 curable 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 curable resin composition. Such a cured product may be, for example, in the form of a cured film (cured coating film) obtained by heating a coating film containing the curable resin composition. The coating film may be formed, for example, by applying a coating liquid (coating liquid) containing the curable 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 curable 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. 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 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 (or curable resin composition) may be a photosensitive resin composition. That is, the phenolic resin of the present invention can be suitably used as a resin (particularly a base resin) that constitutes the photosensitive resin composition. The photosensitive resin composition composed of the phenol resin is extremely useful for forming a pattern having high 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 phenol resin, may be composed of the phenol resin alone, the phenol resin 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 illustrative curing agents or curing resin (melamine resin Etc.), photopolymerizable oligomers or polymers (such as oligomers having a polymerizable group such as (meth) acryloyl group, allyl group, vinyl group, cinnamoyl group).

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 using other resin, the ratio of other resin is 1-200 weight part with respect to 100 weight part of said phenol resin, for example, Preferably it is 5-100 weight part, More preferably, it is about 10-50 weight part. It may be.

  The photosensitive resin composition can be comprised with the said phenol resin (and other resin as needed), and is normally comprised with the said phenol resin (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 phenol resin, 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 phenol resin 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 phenol resin, 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 phenol resin 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. Product), (3) a photosensitive resin composition (positive photosensitive resin composition) composed of the above phenol resin [and other resins (for example, phenol resin, etc., if necessary)] and quinonediazides, etc. But Murrell.

  Among these photosensitive resin compositions, particularly, the phenol resin, 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 (eg, 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.

  The phenolic resin of the present invention (or curable resin composition, resin and curable resin composition may be simply referred to as “phenol resin”, “resin”, etc.) may have heat resistance, environmental resistance, mechanical properties. Excellent properties such as bending properties, toughness and thermal shock. And since such a phenol resin is excellent in molding processability, a molded object can be obtained simply and efficiently. Such a molded body can be obtained by a method of molding the phenol resin (novolak type phenol resin) into a predetermined shape, or forming a thin film on a substrate and curing it.

  Moreover, the curable resin composition of the present invention or the cured product (cured coating film) is excellent in plasma resistance and etching resistance.

  For this reason, the phenol resin of the present invention and its resin composition [or its (preliminary) cured product] are hardeners [for example, curing agents for epoxy resins (such as curing agents for epoxy resins for semiconductor encapsulation)], adhesion Agent, 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) Sticks, 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 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, relief images, etc.), resist (semiconductor manufacturing For Can be applied to various applications such as the lower film strike etc.) (hard mask). Moreover, the phenol resin and the resin composition [or (preliminary) cured product thereof] of the present invention are excellent in transparency, and are also useful as a thermosetting resin (or 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.

Example 1
450 parts by weight of 9,9-bis [6- (2-hydroxynaphthyl)] fluorene (Osaka Gas Chemical Co., Ltd.), 158 parts by weight of 1,4-dimethoxymethylbenzene, and methyl isobutyl ketone (MIBK) as a solvent 1350 parts by weight and 45 parts by weight of 35% hydrochloric acid as an acid catalyst were mixed and reacted for 20 hours under reflux with stirring.

  After 900 parts by weight of ion-exchanged water was added to the obtained reaction product, the mixture was stirred at 50 ° C. and then allowed to stand to remove the washing water separated at the bottom. This operation was performed until the chlorine concentration in the reaction product became 1 ppm or less. Thereafter, reflux dehydration was performed for 5 hours in order to remove moisture in the system. After refluxing dehydration, 900 parts by weight of n-heptane was added to extract unreacted monomers. 600 parts by weight of propylene glycol monomethyl ether acetate was added to the reaction solution from which unreacted monomers had been removed, and solvent substitution was performed under vacuum to remove MIBK, thereby obtaining 720 parts by weight of the intended naphthol resin.

  When the weight average molecular weight Mw of the obtained naphthol resin was measured, it was 10,500 and the molecular weight distribution (Mw / Mn) was 1.95. Moreover, the ratio of the component of the weight average molecular weight 1000 or less computed from the GPC chart was 1 weight% or less.

(Example 2)
In Example 1, instead of 158 parts by weight of 1,4-dimethoxymethylbenzene, 101 parts by weight of benzaldehyde and N-methylpyrrolidone was used instead of solvent-substituted propylene glycol monomethyl ether acetate. Similarly, a naphthol resin was obtained.

  When the weight average molecular weight Mw of the obtained naphthol resin was measured, it was 10,000 and the molecular weight distribution (Mw / Mn) was 1.90. Moreover, the ratio of the component of the weight average molecular weight 1000 or less computed from the GPC chart was 1 weight% or less.

(Example 3)
In Example 1, naphthol resin was used in the same manner as in Example 1 except that 151 parts by weight of bischloromethylanthracene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 158 parts by weight of 1,4-dimethoxymethylbenzene. Got.

  When the weight average molecular weight Mw of the obtained naphthol resin was measured, it was 3900, and molecular weight distribution (Mw / Mn) was 3.30.

(Comparative Example 1)
144 parts by weight of α-naphthol, 158 parts by weight of 1,4-dimethoxymethylbenzene, 324 parts by weight of MIBK as a solvent, and 11 parts by weight of 35% hydrochloric acid as an acid catalyst were mixed and reacted with stirring for 20 hours under reflux. I let you.

  After 900 parts by weight of ion-exchanged water was added to the obtained reaction product, the mixture was stirred at 50 ° C. and then allowed to stand to remove the washing water separated at the bottom. This operation was performed until the chlorine concentration in the reaction product became 1 ppm or less. After washing, 700 parts by weight of propylene glycol monomethyl ether acetate was added, and the solvent was replaced under vacuum to remove MIBK to obtain 820 parts by weight of the desired naphthol resin.

  When the weight average molecular weight Mw of the obtained naphthol resin was measured, it was 5,000 and the molecular weight distribution (Mw / Mn) was 4.10.

(Comparative Example 2)
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). 100 parts by weight of the obtained general-purpose novolak phenol resin, 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 a photoacid generator 3 parts by weight of a compound represented by the following formula (B) (triazine photoacid generator, manufactured by Midori Chemical Co., TAZ-107) is added to 1000 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Tokyo Chemical Industry). It was dissolved 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 4
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 naphthol resin obtained in Example 1 was used instead of 100 parts by weight of the general-purpose novolak type phenolic resin, and the etching rate was measured. As a result, the etching rate of the exposed part was 31.8 nm / min, and the etching rate of the unexposed part was 33.8 nm / min. When the etching rate (exposed portion or unexposed portion) of the film obtained in Comparative Example 2 is 100, the etching rate (hereinafter referred to as the etching rate) is 71 for the exposed portion and 73 for the unexposed portion. It was found that the etching resistance was excellent as compared with the novolac type phenolic resin.

(Example 5)
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 naphthol resin obtained in Example 2 was used instead of 100 parts by weight of the general-purpose novolak type phenolic resin, and the etching rate was measured. As a result, the etching rate of the exposed part was 31.4 nm / min, and the etching rate of the unexposed part was 32.8 nm / min. The etching rate was 70 in the exposed area and 71 in the unexposed area, which was found to be excellent in etching resistance as compared with the general-purpose novolac type phenol resin.

(Comparative Example 3)
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 naphthol resin obtained in Comparative Example 1 was used instead of 100 parts by weight of the general-purpose novolak-type phenol resin, and the etching rate was measured. As a result, the etching rate of the exposed part was 41.2 nm / min, and the etching rate of the unexposed part was 43.5 nm / min. The etching rate was 92 in the exposed area and 94 in the unexposed area.

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

Claims (16)

Phenol component (A) composed of a compound represented by the following formula (1), arene dimethanols, di (halomethyl) arenes, di (C _1-6 alkoxy-methyl) arenes and aromatic aldehyde components at least one aromatic-based crosslinking agent consists of a cross-linking agent (B) and phenolic resins are obtained found by reactions selected from.

(In the formula, ring Z ¹ and ring Z ² are condensed polycyclic 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 m1 and m2 are each 0 or an integer of 1 or more, and n1 and n2 are each 0 or an integer of 1 or more, provided that n1 + n2 ≧ 1. In formula (1), ring Z ¹ and ring Z ² are naphthalene rings, n 1 and n 2 are each 1 or 2, m 1 and m 2 are each 0 to 2, and R ^2a and R ^2b are hydrocarbon groups. The phenol resin according to claim 1.   The phenol resin according to claim 1, wherein the compound represented by the formula (1) is 9,9-bis (hydroxynaphthyl) fluorene.   The phenol resin according to claim 1, wherein the phenol component (A) comprises a compound represented by the formula (1) and phenols. Aromatic crosslinking agents include xylylene glycols, di (halomethyl) benzenes, di (C _1-6 alkoxy-methyl) benzenes, di (hydroxymethyl) naphthalenes, di (halomethyl) naphthalenes, di (C _{2. At} least one selected from _1-6 alkoxy-methyl) naphthalenes, di (hydroxymethyl) anthracenes, di (halomethyl) anthracenes, and di (C _1-6 alkoxy-methyl) anthracenes. The phenolic resin described.   The phenol resin according to claim 1, wherein the aromatic aldehyde component is at least one selected from benzaldehydes and naphthaldehydes.   The phenol resin according to claim 1, wherein the aromatic aldehyde component is benzaldehyde.   The phenol resin according to claim 1, wherein the crosslinking agent (B) comprises an aromatic crosslinking agent and a non-aromatic crosslinking agent.   The ratio of the phenol component (A) to the crosslinking agent (B) is at least selected from A mole of the phenolic hydroxyl group contained in the phenol component (A), hydroxyl group and aldehyde group contained in the entire crosslinking agent (B) The phenol resin according to claim 1, wherein the ratio of B / A is 0.1 to 1 when one kind of functional group is B mol.   The phenol resin according to claim 1, which is a novolac type phenol resin.   A method for producing the phenol resin according to claim 1 by reacting the phenol component (A) according to claim 1 with the crosslinking agent (B) according to claim 1.   The manufacturing method of Claim 11 which manufactures a novolak-type phenol resin in presence of an acid catalyst.   A resin composition comprising the phenol resin according to claim 1.   The resin composition according to claim 13, which is a photosensitive resin composition comprising the phenol resin according to claim 1 and a photosensitive agent.   The resin composition according to claim 14, which is a negative photosensitive resin composition comprising the phenol resin 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 14.