JP2010077380A - Alkali-soluble resin, positive-type resist composition and negative-type resist composition each using the same - Google Patents

Abstract

[PROBLEMS] To produce a cured product having high heat resistance excellent in resolution and heat resistance, having high alkali solubility suitable for a resist composition, without generating low molecular components such as moisture in a heat treatment step. And a positive resist composition and a negative resist composition using the alkali-soluble resin.
An alkali-soluble resin having a ring-opening structure of a benzoxazine ring, wherein the resin includes a compound having a benzoxazine ring and an aromatic compound having at least one phenolic hydroxyl group on one benzene ring. It consists of a polymerized repeating unit, has the basic characteristics of benzoxazine resin such as insulation, mechanical strength, flame retardancy, and water resistance, and exhibits high alkali solubility derived from a phenolic hydroxyl group-containing compound.
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Description

The present invention has a high alkali solubility suitable for a resist composition, does not require high-temperature baking, and hardly generates low-molecular components such as moisture in the heat treatment step, and has excellent resolution and heat resistance. It is related with the alkali-soluble resin which can produce | generate. The present invention also relates to a positive resist composition and a negative resist composition using the alkali-soluble resin.

Since surface protection films and interlayer insulating films used for semiconductor elements are required to have characteristics such as insulating properties, heat resistance, and mechanical strength, polyimide resins and polybenzoxazole resins are widely used. In recent years, with the progress of miniaturization and high integration of semiconductor devices and simplification of processing steps, a method of forming a pattern using polyimide imparted with photosensitivity or polybenzoxazole imparted with photosensitivity attracted attention. (For example, Non-Patent Document 1). Further, there are an organic solvent type and an alkaline aqueous solution type as a developing solution used for pattern formation, but in recent years, an alkaline aqueous solution type has become mainstream from the viewpoint of environmental considerations.

In general, in the case of polyimide imparted with photosensitivity, a positive resist composition or a negative resist composition is prepared by using a polyamic acid or polyamic acid modified body, which is a photosensitive polyimide precursor, as an alkali-soluble resin, and a pattern is formed. After that, a polyimide film is formed by heat treatment.
In the case of polybenzoxazole to which photosensitivity is imparted, after forming a pattern by forming a positive resist composition or a negative resist composition using the precursor polyhydroxyamide or polyhydroxyamide modified product as an alkali-soluble resin, A polybenzoxazole film is formed by heat treatment.
However, these methods require not only a high-temperature heat treatment step (usually 300 ° C. or higher), but also low-molecular components such as water and organic substances are generated as outgass due to the condensation reaction in the heat treatment step. There has been a problem of causing a decrease in reliability such as generation of voids or contamination of semiconductor elements.

On the other hand, benzoxazine resin is known as a resin that is excellent in insulation and heat resistance and does not generate volatile components during thermosetting. However, since conventional benzoxazine resins have no solubility (or very low) in aqueous alkali solutions, they have hardly been used as alkali-soluble resins in resist compositions.

Polymer Papers, Vol. 63, no. 9, p561-576, 2006

The present invention has a high alkali solubility suitable for a resist composition, hardly generates low-molecular components such as moisture in the heat treatment step, does not require high-temperature baking, and is a cured product excellent in resolution and heat resistance. It is an object of the present invention to provide an alkali-soluble resin capable of producing the above. It is another object of the present invention to provide a positive resist composition and a negative resist composition using the alkali-soluble resin.

The present invention is an alkali-soluble resin comprising a repeating unit represented by the following general formula (1-1) or (1-2).

In formula (1-1), Ar ¹ represents a tetravalent aromatic group represented by the following general formula (2-1), (2-2) or (2-3), and R ¹ represents an aliphatic group. Represents an alicyclic group or an aromatic group, and R ^{2 to} R ⁴ may be the same or different and each represents a hydroxyl group, a hydrogen atom, an aliphatic group, an alicyclic group, or an aromatic group.
In formula (1-2), X represents a divalent organic group. R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic group, or a halogen group. R ^{5 to} R ⁷ may be the same or different and each represents a hydroxyl group, a hydrogen atom, an aliphatic group, an alicyclic group, or an aromatic group.

In formulas (2-1), (2-2), and (2-3), ** represents a bonding site to an oxygen atom, and the other represents a bonding site to a methylene group. Moreover, hydrogen of each aromatic ring may be substituted with a C1-C10 aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group. In Formula (2-1), X is at least 1 selected from the group consisting of a direct bond (no atom or atomic group), an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, and the following group A: Represents an aliphatic, alicyclic or aromatic hydrocarbon group which may contain a hetero element or a functional group.

In each formula included in group A, * represents a binding site to the aromatic ring in formula (2-1).
The present invention is described in detail below.

The alkali-soluble resin of the present invention has a ring-opening structure of a benzoxazine ring. Thereby, the outgas, such as water, does not generate | occur | produce at the time of thermosetting, high temperature baking is unnecessary, and the cured | curing material excellent in heat resistance can be formed. Furthermore, a cured product having the basic characteristics of the benzoxazine resin such as insulation, mechanical strength, flame retardancy, and water resistance can be obtained.
The alkali-soluble resin of the present invention has a phenolic hydroxyl group other than the phenolic hydroxyl group derived from the ring-opened structure of the benzoxazine ring. By having such a phenolic hydroxyl group, the alkali-soluble resin of the present invention exhibits high alkali solubility and can be suitably used for a resist composition, and a cured film having excellent resolution can be obtained.

In the alkali-soluble resin of the present invention, the preferable lower limit of the weight average molecular weight is 1000, and the preferable upper limit is 20,000. If the weight average molecular weight is less than 1000, the resist composition has weak holding power, and a pattern may not be formed. When the weight average molecular weight exceeds 20,000, it is difficult to synthesize the resin itself, and the alkali developability may be inferior.
In this specification, the weight average molecular weight is, for example, a value measured by a GPC (gel permeation chromatography) method using a column such as Shodex LF-804 manufactured by Showa Denko KK and tetrahydrofuran as a developing solvent. It means that converted to polystyrene.

The alkali-soluble resin of the present invention can be synthesized by alternately copolymerizing a compound having a benzoxazine ring and an aromatic compound having one or more phenolic hydroxyl groups on one benzene ring. Since the benzoxazine ring is deficient in electrons, the phenolic hydroxyl group-containing compound is electron-donating, and therefore can be easily made into an alternating copolymer by mixing and reacting them. Since the alkali-soluble resin of the present invention synthesized by such a method is a linear or branched polymer, it is soluble in a solvent or an alkaline aqueous solution. Moreover, since it has such a structure, the characteristic derived from benzoxazine and the high alkali solubility derived from a phenolic hydroxyl group containing compound are expressed.

The reaction of alternately copolymerizing a compound having a benzoxazine ring and an aromatic compound having one or more phenolic hydroxyl groups on one benzene ring can be represented by the following reaction formula (3) or (4).

In the above reaction formulas (3) and (4), n represents a positive integer.

In the reaction formula (3), a compound having a benzoxazine ring as a raw material includes a diol compound represented by HO—Ar ¹ —OH, a primary amine compound represented by NH ₂ —R ¹ , an aldehyde compound, Can be synthesized. The reaction when formaldehyde is used as the aldehyde compound is shown in the reaction formula (5).

Examples of the diol compound represented by the HO—Ar ¹ —OH include tetravalent aromatic groups represented by the general formulas (2-1), (2-2), and (2-3), Examples include compounds in which an OH group is bonded to a bond marked with * and H is bonded to another bond.

Of the diol compounds represented by HO—Ar ¹ —OH, an OH group is bonded to the bond of the tetravalent aromatic group represented by the above general formula (2-1), and the other bond. Examples of the compound in which H is bonded to the hand include 4,4′-biphenol, 2,2′-biphenol, 4,4′-dihydroxydiphenyl ether, 2,2′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylmethane, 2,2′-dihydroxydiphenylmethane, bisphenol A, bisphenol S, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis ( 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy) Ciphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene)] bisphenol (Mitsui Chemicals, Inc.) Bisphenol P, sold by Tokyo Chemical Industry under the compound name “α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene”, 4,4 ′-[1,3-phenylenebis (1-methyl) -Ethylidene)] bisphenol (Bisphenol M manufactured by Mitsui Chemicals), 9,9-bis (4-hydroxyphenyl) fluorene 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,3-bis (4-hydroxyphenoxy) benzene, 1,4-bis (3-hydroxyphenoxy) benzene, 2,6-bis ((2- As in hydroxyphenyl) methyl) phenol (a = 1 compound), etc., there are two benzene rings in the molecule except for the connecting part X, and one OH group is bonded to one benzene ring. And the like.

Among the diol compounds represented by HO—Ar ¹ —OH, an OH group is bonded to the bond of the tetravalent aromatic group represented by the general formula (2-2) with **, and other bonds. Examples of the compound in which H is bonded to the hand include 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6 Examples thereof include a compound having one naphthalene ring in the molecule and two OH groups bonded to the naphthalene ring, such as -dihydroxynaphthalene and 2,7-dihydroxynaphthalene.

Among the diol compounds represented by HO—Ar ¹ —OH, an OH group is bonded to the bond of the tetravalent aromatic group represented by the general formula (2-3) indicated by **, and other bonds. Examples of the compound in which H is bonded to the hand include one benzene in the molecule such as 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone). Examples thereof include a compound having a ring and two OH groups bonded to a benzene ring.

In the illustration of the diol compound represented by the above HO—Ar ¹ —OH, in the aromatic ring to which the OH group is bonded, except for the OH group and the connecting part X (in the case of the general formula (2-1)), there is no substitution. In any case, any one of the ortho positions of the OH group may be H which can be substituted, and the other part of the aromatic ring may be various substituents, for example, straight chain having 1 to 10 carbon atoms. Alternatively, it may be substituted with a branched aliphatic hydrocarbon group, alicyclic hydrocarbon group, or substituted or unsubstituted aromatic group. Even when the linking part X includes an aromatic ring, the aromatic ring may be various substituents such as a linear or branched aliphatic hydrocarbon group or alicyclic hydrocarbon group having 1 to 10 carbon atoms. May be substituted.

As a simple example of the substituted aromatic ring, in the case of the general formula (2-1), for example, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-Hydroxy-3-methylphenyl) methane is mentioned, and in the case of the general formula (2-3), for example, 2-methylresorcinol, 2,5-dimethylresorcinol and the like can be mentioned.

Examples of the primary amine compound represented by NH ₂ —R ¹ include aliphatic amines, alicyclic amines, and aromatic amines.
Examples of the aliphatic amine include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, and ralylamine.
Examples of the alicyclic amine include cyclohexylamine, adamantylamine, and norbornene monoamine.
Examples of the aromatic amine include aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, o-toluidine, m-toluidine, p-toluidine, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, and triphenyl. Examples include amine, α-naphthylamine, and β-naphthylamine.
Of these, methylamine, aniline, methylaniline and the like are preferable.

Examples of the aldehyde compound used in the reaction for synthesizing the compound having a benzoxazine ring in the reaction formula (3) include formaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde and the like. Of these, formaldehydes are preferable, and formalin, which is an aqueous solution of formaldehyde, and paraformaldehyde, which is a polymer of formaldehyde, are more preferable.

In the reaction for synthesizing the compound having a benzoxazine ring in the reaction formula (3), the phenolic hydroxyl group of the diol compound represented by the HO—Ar ¹ —OH and the primary amine represented by the NH ₂ —R ¹ It is preferable that the primary amine of the compound and the aldehyde compound are mixed and reacted so as to have a molar ratio of 1: 2: 4. In order to increase the reaction efficiency, the aldehyde compound may be added in a slight excess.

In the above reaction formula (4), a compound having a benzoxazine ring as a raw material is synthesized by reacting a diamine compound represented by H ₂ N—X—NH ₂ with a phenol compound and an aldehyde compound. Can do. The reaction when formaldehyde is used as the aldehyde compound is shown in the reaction formula (6).

In the diamine compound represented by the H ₂ N—X—NH ₂ , X represents a divalent organic group. Examples of such compounds include aliphatic diamine compounds, aromatic diamine compounds, alicyclic diamine compounds, silicon diamine compounds, and the like.
The said aliphatic diamine compound is not specifically limited, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine 1,18-octadecanediamine and the like.
The aromatic diamine compound is not particularly limited, and examples thereof include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 2, 2-bis [(4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) neopentane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [( 4-aminophenoxy) phenyl] biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] he Safluoropropane, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene and the like.
The alicyclic diamine compound is not particularly limited. For example, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0] decane, 2,5 (6) -bis ( Aminomethyl) bicyclo [2.2.1] heptane, 1,3-diaminoadamantane and the like.

The phenol compound is preferably a compound having one phenolic hydroxyl group and at least one of the ortho positions of the phenolic hydroxyl group being a hydrogen atom (unsubstituted). Examples of such compounds include phenol, cresols, xylenols, alkylphenols, allylphenols, aralkylphenols, aralkylphenols, alkenylphenols, alkoxyphenols, halogenated phenols, monofunctional phenols, etc. Is mentioned.
The said cresol is not specifically limited, For example, o-cresol, m-cresol, p-cresol, etc. are mentioned.
The xylenols are not particularly limited, and examples thereof include 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and the like.
The alkylphenols are not particularly limited. For example, o-ethylphenol, m-ethylphenol, p-ethylphenol, n-butylphenol, s-butylphenol, t-butylphenol, 2,3,4-trimethylphenol, 2,3 , 5-trimethylphenol, 2,4,5-trimethylphenol, 3,4,5-trimethylphenol and the like.
The allylphenols are not particularly limited, and examples thereof include o-phenylphenol, m-phenylphenol, and p-phenylphenol.
The aralkylphenols are not particularly limited, and examples thereof include o-benzylphenol, m-benzylphenol, and p-benzylphenol.
The alkenylphenols are not particularly limited, and examples thereof include o-vinylphenol, m-vinylphenol, p-vinylphenol, o-allylphenol, m-allylphenol, and p-allylphenol.
The alkoxyphenols are not particularly limited, and examples thereof include o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, and p-ethoxyphenol.
The halogenated phenols are not particularly limited, and examples thereof include o-chlorophenol, m-chlorophenol, and p-chlorophenol.
The monofunctional phenols are not particularly limited, and examples include α-naphthol and β-naphthol.

Examples of the aldehyde compound used in the reaction for synthesizing the compound having a benzoxazine ring in the above reaction formula (4) include formaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde and the like. Of these, formaldehydes are preferable, and formalin, which is an aqueous solution of formaldehyde, and paraformaldehyde, which is a polymer of formaldehyde, are more preferable.

In the reaction for synthesizing the compound having a benzoxazine ring in the reaction formula (4), the diamine compound represented by the H ₂ N—X—NH ₂ , the phenol compound, and the aldehyde compound are 1: 2: It is preferable to mix and react so that the molar ratio is 4. In order to increase the reaction efficiency, the aldehyde compound may be added in a slight excess.

In the reaction formula (3) or (4), examples of the aromatic compound having one or more phenolic hydroxyl groups on one benzene ring include phenol, 1,2-dihydroxybenzene (catechol), 1,3-dihydroxy. Benzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone), 1,2,3-trihydroxybenzene (pyrogallol), etc. are mentioned, and these are methyl group, ethyl group, propyl group, butyl on the aromatic ring. It may have an aliphatic group other than a hydroxyl group such as a group. However, at least two or more substituents on the aromatic ring are hydrogen atoms. Especially, since electron donating property is high and reactivity is high, 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone), 1,2, An aromatic compound having two or more phenolic hydroxyl groups on one benzene ring, such as 3-trihydroxybenzene (pyrogallol), is preferable.

In the reaction represented by the reaction formula (3) or (4), the compound having the benzoxazine ring and the aromatic compound having one or more phenolic hydroxyl groups on one benzene ring are alternately copolymerized. In the reaction for obtaining an alkali-soluble resin, the compound having the benzoxazine ring and the aromatic compound having one or more phenolic hydroxyl groups on one benzene ring are reacted at a molar ratio of 1: 2 to 2: 1. It is preferable. When the reaction is performed outside this range, a product having a predetermined molecular weight may not be obtained, or the solubility in an aqueous alkali solution may be too high or too low. Most preferably, the reaction is performed at a molar ratio of 1: 1.

The reactions (3) to (6) can be carried out without solvent or in a solvent.
When the reactions (3) to (6) are carried out in a solvent, the solvent to be used is not particularly limited. For example, aromatic solvents such as toluene and xylene, halogen solvents such as chloroform and dichloromethane, Alcohol solvents such as methanol, ethanol, propanol, butanol, ethyl lactate, tetrahydrofuran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethyl Examples include englycol diethyl ether and propylene glycol monomethyl ether acetate. Moreover, you may use the resist solvent mentioned later as it is, and mix | blend it as it is. Moreover, these may be used independently and may use 2 or more types together.
The reactions (3) to (6) are preferably performed by heating at about 50 to 200 ° C. for about several minutes to several hours.

In the alkali-soluble resin of the present invention, at least one of R ^{2 to} R ⁴ in the above formula (1-1) or R ^{5 to} R ⁷ in the formula (1-2) is preferably a hydroxyl group. . In such a case, the reaction at the time of synthesis is easy to control, and the product has a high alkali solubility, and a resin having particularly desired characteristics can be obtained.
In order to obtain such a resin, 1,2-dihydroxybenzene as an aromatic compound having one or more phenolic hydroxyl groups on one benzene ring in the above reaction formula (3) or (4). (Catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone), 1,2,3-trihydroxybenzene (pyrogallol), etc. have two or more phenolic hydroxyl groups on one benzene ring An aromatic compound may be used. Among these, 1,2,3-trihydroxybenzene (pyrogallol) is particularly preferable from the viewpoint of high reactivity during synthesis and alkali solubility.

The alkali-soluble resin of the present invention has high alkali solubility, does not generate low-molecular components such as moisture in the heat treatment step, does not require high-temperature baking, and can produce a cured product having high heat resistance. Therefore, it can be used very suitably as an alkali-soluble resin of a resist composition. A positive resist composition and a negative resist composition using the alkali-soluble resin of the present invention are also one aspect of the present invention.

The positive resist composition of the present invention contains the alkali-soluble resin of the present invention and a photoacid generator.
It does not specifically limit as said photo-acid generator, The photo-acid generator used for a conventionally well-known positive type photosensitive resin composition can be used.
Examples of the photoacid generator include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and 2,3,6-trihydroxybenzophenone. 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3', 4 4 ′, 6-pentahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′, 4,4 ′, Polyhydroxybenzophenones such as 5 ′, 6-hexahydroxybenzophenone and 2,3,3 ′, 4,4 ′, 5′-hexahydroxybenzophenone It is done.

Examples of the photoacid generator include bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4′- Hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ', 4'-trihydroxyphenyl) propane, 4,4'-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, 3,3'-dimethyl- {1- [4- [2- (3-Methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol such as bis [(poly) hydroxyphenyl] a Cans and the like.

Examples of the photoacid generator include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, and bis (4-hydroxy-2,5-dimethyl). Phenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis Tris (hydroxyphenyl) methane such as (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane Or methyl-substituted products thereof.

Examples of the photoacid generator include bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, and bis (3- Cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis ( 5-cyclohexyl 4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3- Methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5- Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) such as cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, etc. Nyl) methanes or methyl-substituted products thereof, and sulfonic acids containing quinonediazide groups such as naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinonediazidesulfonic acid And complete ester compounds, partial ester compounds, amidated products, partially amidated products, and the like.

The blending amount of the photoacid generator is not particularly limited, but the preferable lower limit is 5% by weight and the preferable upper limit is 60% by weight with respect to the alkali-soluble resin of the present invention. If the blending amount of the photoacid generator is less than 5% by weight, a difference in solubility in alkali between the exposed part and the non-exposed part may not be obtained due to insufficient sensitivity, and if it exceeds 60% by weight, the dielectric constant and The physical properties of the coating such as mechanical properties may be deteriorated. A more preferable lower limit of the amount of the photoacid generator is 10% by weight, and a more preferable upper limit is 50% by weight.

The negative resist composition of the present invention contains the alkali-soluble resin of the present invention, a polymerizable unsaturated compound, and a photo radical initiator.
Although it does not specifically limit as said polymerizable unsaturated compound, For example, a polyfunctional (meth) acrylate compound is suitable. Moreover, a polyfunctional urethane (meth) acrylate compound can also be used suitably.

Examples of the bifunctional compound among the polyfunctional (meth) acrylate compounds include neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 2-butyl-2- Ethyl-1,3-propanediol di (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, diethylene glycol (meth) acrylate, triethylene Glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, nonaethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, trie Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate compounds include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

Although it does not specifically limit as a compounding quantity of the said polymeric unsaturated compound, A preferable minimum is 10 weight% with respect to the alkali-soluble resin of this invention, and a preferable upper limit is 200 weight%. When the blending amount of the polymerizable unsaturated compound is less than 10% by weight, the photocurability may be insufficient and a resist pattern may not be formed. When the blending amount exceeds 200% by weight, heat resistance, insulation, and mechanical properties may be formed. The physical properties of the coating film may be deteriorated.

The photoinitiator is not particularly limited, and examples thereof include conventionally known photoinitiators such as benzoin, benzophenone, benzyl, thioxanthone, and derivatives thereof.
Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, Michler ketone, (4- (methylphenylthio) phenyl) failmethanone, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2 -Methyl-1-propan-1-one, 2-methyl-1 (4-methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphospho Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, 2-chloro Examples include thioxanthone. These photoinitiators may be used independently and 2 or more types may be used together.

The blending amount of the photoreaction initiator is not particularly limited, but a preferable lower limit is 0.5% by weight and a preferable upper limit is 20% by weight with respect to the polymerizable unsaturated compound. If the amount of the photoinitiator is less than 0.5% by weight, the photocurability may be insufficient and a resist pattern may not be formed. If the amount exceeds 20%, the resolution decreases, the dielectric constant, The physical properties of the coating such as mechanical properties may be deteriorated.

The positive resist composition and the negative resist composition of the present invention preferably contain a solvent for the purpose of adjusting viscosity and the like.
The solvent is not particularly limited, and examples thereof include aromatic hydrocarbon compounds, saturated or unsaturated hydrocarbon compounds, ethers, ketones, and esters.
The aromatic hydrocarbon compound is not particularly limited, and examples thereof include benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene.
The saturated or unsaturated hydrocarbon compound is not particularly limited. For example, cyclohexane, ethylcyclohexane, methylcyclohexane, cyclohexene, p-menthane, o-menthane, m-menthane dipentene, n-pentane, isopentane, n-hexane, isohexane. N-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane and the like.
The ethers are not particularly limited. For example, diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether , Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, 1, - dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, dipropyl ether, dibutyl ether and the like.
The ketones are not particularly limited, and examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.
The esters are not particularly limited, and for example, ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, stearin Examples include butyl acid.
These solvents may be used independently and 2 or more types may be used together.

Although it does not specifically limit as a compounding quantity of the said solvent, It mix | blends so that the solid content density | concentration of the positive resist composition of this invention and a negative resist composition may be 10 to 60 weight%, More preferably, it is 15 to 50 weight%. It is preferable from the viewpoints of coatability and coating film uniformity.

The positive type resist composition and the negative type resist composition of the present invention further include conventionally known additives such as surfactants, adhesion improvers, dissolution accelerators, inorganic fillers and the like within the range not impairing the object of the present invention. It may contain. Moreover, you may contain conventionally well-known resin components, such as an epoxy resin, an oxetane resin, a phenol resin, a melamine resin, a maleimide resin, a polyurethane resin, an acrylic resin, as needed. Moreover, you may contain a polyimide resin, polybenzoxazole resin, and those precursors. Moreover, you may contain the compound (it does not have a phenolic hydroxyl group) which has a benzoxazine ring to such an extent that developability is not impaired.

The method for producing the positive resist composition and the negative resist composition of the present invention is not particularly limited. The alkali-soluble resin of the present invention, essential components such as a photoacid generator, and the like are added as necessary. The method of mixing an additive using conventionally well-known various mixers is mentioned.

According to the present invention, it has high alkali solubility suitable for a resist composition, hardly generates low-molecular components such as moisture in the heat treatment step, does not require high-temperature baking, and has excellent resolution and heat resistance. An alkali-soluble resin capable of producing a cured product can be provided. Moreover, the positive resist composition and negative resist composition using this alkali-soluble resin can be provided.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

<Synthesis of alkali-soluble resin>
(Synthesis Example 1)
In a 500 mL beaker, 45.6 g (0.2 mol) of bisphenol A, 26.4 g (0.88 mol) of paraformaldehyde, and 37.2 g (0.4 mol) of aniline are added and stirred at room temperature for 30 minutes to form a slurry. Then, it was heated to 170 ° C. on a hot plate and allowed to react for 10 minutes. The reaction solution was cast on a fluororesin sheet and cooled to room temperature, and the solid material obtained was ground with a mortar to obtain a compound having two benzoxazine rings in one molecule.

In a 500 mL flask equipped with a reflux tube, 46.2 g (0.10 mol) of a compound having two benzoxazine rings in one molecule obtained, 12.6 g (0.10 mol) of pyrogallol, 137. 2 g was added and reacted at 120 ° C. for 30 minutes to obtain an alkali-soluble resin solution (solid content 30% by weight) of the present invention.

(Synthesis Example 2)
In a 500 mL beaker, 40 g (0.2 mol) of 4,4′-dihydroxydiphenylmethane, 26.4 g (0.88 mol) of paraformaldehyde, and 37.2 g (0.4 mol) of aniline are added and stirred at room temperature for 30 minutes. After being made into a slurry, it was heated to 170 ° C. on a hot plate and allowed to react for 10 minutes. The reaction solution was cast on a fluororesin sheet and cooled to room temperature, and the solid material obtained was ground with a mortar to obtain a compound having two benzoxazine rings in one molecule.

In a 500 mL flask equipped with a reflux tube, 43.4 g (0.10 mol) of a compound having two benzoxazine rings in one molecule, 12.6 g of pyrogallol (0.10 mol), 130. 7 g was added and reacted at 120 ° C. for 30 minutes to obtain an alkali-soluble resin solution of the present invention (solid content: 30% by weight).

(Synthesis Example 3)
In a 500 mL flask equipped with a reflux tube and a Dean-Stark tube, 37.6 g (0.4 mol) of phenol, 39.6 g (0.2 mol) of 4,4′-diaminodiphenylmethane, 26.4 g (0.88 mol) of paraformaldehyde. ), 103.6 g of toluene was added, and the reaction was carried out at 120 ° C. for 3 hours while removing water generated during the reaction. The solution after the reaction was poured into a large amount of methanol, and the precipitate was collected and dried under reduced pressure to obtain a compound having two benzoxazine rings in one molecule.

In a 500 mL flask equipped with a reflux tube, 43.4 g (0.10 mol) of a compound having two benzoxazine rings in one molecule, 12.6 g of pyrogallol (0.10 mol), 130. 7 g was added and reacted at 120 ° C. for 30 minutes to obtain an alkali-soluble resin solution of the present invention (solid content: 30% by weight).

(Synthesis Example 4)
In a 500 mL flask equipped with a reflux tube and a Dean-Stark tube, 43.2 g (0.4 mol) of p-cresol, 39.6 g (0.2 mol) of 4,4′-diaminodiphenylmethane, 26.4 g of paraformaldehyde (0 .88 mol) and 109.2 g of toluene were added, and the mixture was reacted at 120 ° C. for 3 hours while removing water generated during the reaction. The solution after the reaction was poured into a large amount of methanol, and the precipitate was collected and dried under reduced pressure to obtain a compound having two benzoxazine rings in one molecule.

In a 500 mL flask equipped with a reflux tube, 46.2 g (0.10 mol) of a compound having two benzoxazine rings in one molecule obtained, 12.6 g (0.10 mol) of pyrogallol, 137. 2 g was added and reacted at 120 ° C. for 30 minutes to obtain an alkali-soluble resin solution (solid content 30% by weight) of the present invention.

(Synthesis Example 5)
Synthesis was performed in the same manner as in Synthesis Example 1 except that 11.0 g (0.10 mol) of catechol was used instead of pyrogallol and 133.4 g of ethyl lactate was used, and the solution of the alkali-soluble resin of the present invention (solid content 30) % By weight).

About resin obtained in the synthesis examples 1-5, GPC measurement was performed using Shodex LF-804 (made by Showa Denko KK) as a column and tetrahydrofuran as a developing solvent, and the weight average molecular weight (polystyrene conversion) was investigated.
The obtained resin was added to a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, and a solubility test was performed. The results are shown in Table 1.

<Preparation and evaluation of positive resist composition>
(Examples 1-5)
20.0 g of a resin solution having a solid content of 30% by weight obtained in Synthesis Examples 1 to 5 and three 5-naphthoquinonediazide sulfonyls on average in 2,3,4,4′-tetramethylbenzophenone as a photoacid generator 1.5 g of a group bonded (4NT-300, manufactured by Toyo Gosei Co., Ltd.), 0.015 g of a fluorosurfactant (PF-3320, manufactured by OMNOVA SOLUTIONS), 16.1 g of diethylene glycol methyl ethyl ether, A positive resist composition having a solid content of 20% by weight was obtained.

The obtained positive resist composition was applied on a silicon wafer to a thickness of 3 μm using a spin coater, then heated to 100 ° C. on a hot plate and dried for 2 minutes to obtain a coating film. .
The obtained coating film was irradiated with ultraviolet rays of 400 mJ / cm ² through a mask having a dot pattern of 4 to 20 μm and a line and space pattern. After irradiation with ultraviolet rays, a pattern was formed by developing for 30 seconds using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution and washing with water.

The obtained pattern was observed with an optical microscope, and the resolution was evaluated.
Further, the obtained pattern was further heat-treated at 220 ° C. for 60 minutes, then scraped off from the silicon wafer, and heat resistance was evaluated with a thermogravimetric measuring device (TG / DTA320, manufactured by Seiko Instruments Inc.). After the temperature was raised to 100 ° C. to remove the adsorbed moisture, this weight was taken as 100%, and the temperature was raised to 500 ° C. at a rate of temperature rise of 10 ° C./min, and the 5% weight loss temperature was measured.
The results are shown in Table 2.

<Preparation and evaluation of negative resist composition>
(Examples 6 to 10)
20.0 g of a resin solution having a solid content of 30% by weight obtained in Synthesis Examples 1 to 5, 6.0 g of pentaerythritol triacrylate as a polymerizable unsaturated compound, and 2-methyl-1 (4-methylthio) as a photopolymerization initiator Phenyl) -2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) 1.05 g, fluorosurfactant (PF-3320, manufactured by OMNOVA SOLUTIONS), 0.015 g, diethylene glycol methyl ethyl ether 38 0.1 g was mixed to obtain a negative resist composition having a solid content of 20% by weight.

The obtained negative resist composition was applied on a silicon wafer to a thickness of 3 μm using a spin coater, then heated to 100 ° C. on a hot plate and dried for 2 minutes to obtain a coating film. .
The obtained coating film was irradiated with ultraviolet rays of 400 mJ / cm ² through a mask having a dot pattern of 4 to 20 μm and a line and space pattern. After irradiation with ultraviolet rays, a pattern was formed by developing for 30 seconds using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution and washing with water.

The obtained pattern was observed with an optical microscope, and the resolution was evaluated.
Further, the obtained pattern was further heat-treated at 220 ° C. for 60 minutes, then scraped off from the silicon wafer, and heat resistance was evaluated with a thermogravimetric measuring device (TG / DTA320, manufactured by Seiko Instruments Inc.). After the temperature was raised to 100 ° C. to remove the adsorbed moisture, this weight was taken as 100%, and the temperature was raised to 500 ° C. at a rate of temperature rise of 10 ° C./min, and the 5% weight loss temperature was measured.
The results are shown in Table 3.

According to the present invention, a cured product having a high alkali solubility suitable for a resist composition and having high resolution and heat resistance without generating low molecular components such as moisture in the heat treatment step. It is possible to provide an alkali-soluble resin capable of producing Moreover, the positive resist composition and negative resist composition using this alkali-soluble resin can be provided.

Claims (5)

An alkali-soluble resin comprising a repeating unit represented by the following general formula (1-1) or (1-2).

In formula (1-1), Ar ¹ represents a tetravalent aromatic group represented by the following general formula (2-1), (2-2) or (2-3), and R ¹ represents an aliphatic group. Represents an alicyclic group or an aromatic group, and R ^{2 to} R ⁴ may be the same or different and each represents a hydroxyl group, a hydrogen atom, an aliphatic group, an alicyclic group, or an aromatic group.
In formula (1-2), X represents a divalent organic group. R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic group, or a halogen group. R ^{5 to} R ⁷ may be the same or different and each represents a hydroxyl group, a hydrogen atom, an aliphatic group, an alicyclic group, or an aromatic group.

In formulas (2-1), (2-2), and (2-3), ** represents a bonding site to an oxygen atom, and the other represents a bonding site to a methylene group. Moreover, hydrogen of each aromatic ring may be substituted with a C1-C10 aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a substituted or unsubstituted phenyl group. In Formula (2-1), X is at least 1 selected from the group consisting of a direct bond (no atom or atomic group), an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, and the following group A: Represents an aliphatic, alicyclic or aromatic hydrocarbon group which may contain a hetero element or a functional group.

In each formula included in group A, * represents a binding site to the aromatic ring in formula (2-1). The alkali-soluble resin according to claim 1, wherein the weight-average molecular weight is 1000 to 20,000. 3. The alkali-soluble composition according to claim 1, wherein at least one of R ^{2 to} R ⁴ in formula (1-1) or R ^{5 to} R ⁷ in formula (1-2) is a hydroxyl group. resin. A positive resist composition comprising the alkali-soluble resin according to claim 1, 2 or 3 and a photoacid generator. A negative resist composition comprising the alkali-soluble resin according to claim 1, 2 or 3, a polymerizable unsaturated compound, and a photo radical initiator.