WO2013141376A1

WO2013141376A1 - Protectant, method for producing compound protected by protectant, resin protected by protectant, photosensitive resin composition containing resin protected by protectant, pattern-forming material, photosensitive film, cured relief pattern, method for producing same, and semiconductor device

Info

Publication number: WO2013141376A1
Application number: PCT/JP2013/058366
Authority: WO
Inventors: 恭平荒山; 雨宮　拓馬; 稲崎　毅
Original assignee: 富士フイルム株式会社
Priority date: 2012-03-23
Filing date: 2013-03-22
Publication date: 2013-09-26
Also published as: JPWO2013141376A1; JP5696254B2

Abstract

Provided are: a protectant of carboxyl groups or hydroxyl groups having excellent storage stability; a resin in which carboxyl groups or hydroxyl groups are protected by the protectant, the resin having excellent storage stability; a photosensitive resin composition containing the protected resin, the photosensitive resin composition having excellent resolution and sensitivity; a pattern-forming material, photosensitive film, and cured film in which the photosensitive resin composition is used; and a method for producing a cured relief pattern, the cured relief pattern obtained thereby, and a semiconductor device equipped with the cured relief pattern, in which the photosensitive resin composition is used. A protectant of hydroxl groups or carboxyl groups, which protectant is a compound represented by general formula (I). (In the general formula, R¹ and R² each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, R₁ and/or R² being an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom. R³ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. R¹ and R² may bond together to form a ring, or R¹ or R² may bond to R³ to form a ring. X represents a group that can be desorbed by the action of the hydroxyl groups or carboxyl groups.)

Description

Protective agent, method for producing compound protected by the protective agent, resin protected by the protective agent, photosensitive resin composition containing the resin protected by the protective agent, pattern forming material, photosensitive film, curing Relief pattern, manufacturing method thereof, and semiconductor device

The present invention relates to a protective agent for a carboxyl group or a hydroxyl group, a resin in which the carboxyl group or the hydroxyl group is protected by the protective agent, which is useful for use in the production of a chemically amplified resist composition, a pharmaceutical intermediate, and a paint. , A photosensitive resin composition containing the resin, a pattern forming material using the photosensitive resin composition, a photosensitive film, a cured film, and a method for producing a cured relief pattern using the photosensitive resin composition, The present invention relates to a cured relief pattern obtained thereby and a semiconductor device provided with the cured relief pattern.

The hemiacetal ester compound or acetal compound is a chemically amplified resist composition as a compound or resin in which a carboxyl group or a hydroxyl group is protected because a group derived from an alkyl vinyl ether is easily eliminated by heat, an acid catalyst or the like. It is useful for the production of pharmaceutical intermediates and paints.
A hemiacetal ester compound or an acetal compound is usually produced by reacting with alkyl vinyl ether or alkyl vinyl ether added with hydrogen halide as a protective agent and reacting with a compound having a carboxyl group or hydroxyl group. Is done.

However, alkyl vinyl ethers and halogenated alkyl ethers are extremely unstable and easily polymerized. For example, when 1-chloroethyl ethyl ether produced by the reaction of ethyl vinyl ether and hydrogen halide is reacted with a polymer having a carboxyl group or a hydroxyl group, a polymer derived from 1-chloroethyl ethyl ether is a subsidiary. There was a problem of being born.

In order to solve these problems, a method using an alkenyl ether represented by the following general formula or a halogenated alkyl ether as a protective agent for a carboxyl group or a hydroxyl group instead of the alkyl vinyl ether is known (for example, Patent Document 1, 2).

(Wherein R ^a , R ^b and R ^c are the same or different and each represents substituted or unsubstituted alkyl, substituted or unsubstituted aryl or substituted or unsubstituted aralkyl, or R ^a and R ^b are Together with adjacent carbon atoms form a cycloalkyl, X represents a halogen atom.)

However, the storage stability of the protective agent described above is insufficient, and the production methods described in Patent Documents 1 and 2 have problems that only a protective agent in which both R ^a and R ^b are alkyl groups can be synthesized.
Further, the storage stability of the compound or resin in which the carboxyl group or hydroxyl group is protected by the protective agent is insufficient, and the photosensitive resin composition containing the compound or resin in which the carboxyl group or hydroxyl group is protected is There are various problems in lithography performance such as sensitivity and profile, which are not satisfied in practice.

International Publication No. 2007/126050 Japanese Laid-Open Patent Publication No. 2008-26673

The object of the present invention is to protect the carboxyl group or hydroxyl group having excellent storage stability, the carboxyl group or hydroxyl group being protected by the protective agent, the resin having excellent storage stability, and the above-described protected product having excellent resolution and sensitivity. Photosensitive resin composition containing the resin, pattern forming material using the photosensitive resin composition, photosensitive film, and cured film, and method for producing a cured relief pattern using the photosensitive resin composition, Another object of the present invention is to provide a cured relief pattern obtained by the above and a semiconductor device having the cured relief pattern.

The present invention has the following configuration, which solves the above-described problems of the present invention.
[1]
A protective agent for a hydroxyl group or a carboxyl group, which is a compound represented by the following general formula (I).

(In the above general formula, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
R ³ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring. X represents a group capable of leaving by the action of the hydroxyl group or carboxyl group. )
[2]
The hydroxyl group or carboxyl group protecting agent according to [1], wherein at least one of R ¹ and R ^{2 in} the compound represented by the general formula (I) is an aryl group.
[3]
A method for producing a compound having a group represented by the following general formula (III) by reacting the protective agent according to [1] or [2] with a compound having a hydroxyl group or a carboxyl group.

(In the above general formula, R ¹ , R ² and R ³ are respectively synonymous with R ¹ , R ² and R ³ in the general formula (I), and at least one of R ¹ and R ² is an aryl group. , An alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
* Represents a binding site with a residue obtained by removing -OH from the group of the compound having a hydroxyl group or a carboxyl group. )
[4]
A resin selected from the group consisting of a polyhydroxystyrene resin, a novolac resin, a polyacrylic acid resin, a polymethacrylic acid resin, a polyamic acid as a polyimide precursor, and a polyhydroxyamide as a polybenzoxazole precursor, A resin in which all or a part of the hydroxyl group or carboxyl group is substituted with a group represented by the following general formula (III).

(In the above general formula, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring.
* Represents a binding site with a residue obtained by removing —OH from the hydroxyl group or carboxyl group of the resin. )
[5]
All or part of the hydroxyl groups of the polyhydroxystyrene resin having a repeating unit represented by the following general formula (V) and having a weight average molecular weight of 1,000 to 100,000 are groups represented by the following general formula (III) Polyhydroxystyrene resin substituted with

(In the above general formula, R ⁴ represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, and k represents an integer of 0 to 4)

(In the above general formula, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring.
* Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (V). )
[6]
All or part of the hydroxyl groups of the novolak resin having a repeating unit represented by the following general formula (VI) and having a weight average molecular weight of 1,000 to 100,000 is substituted with a group represented by the following general formula (III) Novolac resin.

(In the above general formula, R ⁵ represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, m represents an integer of 0 to 3, and R ⁶ and R ⁷ each independently represents Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.)

(In the above general formula, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring.
* Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (VI). )
[7]
All or part of the carboxyl groups of the polymer having a repeating unit represented by the following general formula (VII) and having a weight average molecular weight of 1,000 to 100,000 are substituted with a group represented by the following general formula (IV) Polyacrylic acid resin or polymethacrylic acid resin.

(In the above general formula, R ⁸ represents a hydrogen atom or an alkyl group.)

(In the above general formula, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring.
* Represents a binding site with a residue obtained by removing the carboxyl group from the repeating unit represented by the general formula (VII). )
[8]
The polyamic acid by which all or one part of the carboxyl group of the polyamic acid which has a repeating unit represented by the following general formula (VIII) was substituted by the group represented by the following general formula (IV).

(In the formula, R ⁹ represents a tetravalent organic group, and R ¹⁰ represents a divalent organic group.)

(In the above general formula, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring.
* Represents a binding site with a residue obtained by removing a carboxyl group from the repeating unit represented by the general formula (VIII). )
[9]
A polyhydroxyamide in which all or part of hydroxyl groups of a polyhydroxyamide having a repeating unit represented by the following general formula (IX) is substituted with a group represented by the following general formula (III).

(In the formula, R ¹¹ represents a tetravalent organic group, and R ¹² represents a divalent organic group.)

(In the above general formula, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring.
* Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (IX). )
[10]
(A) A photosensitive resin composition comprising the resin according to any one of [4] to [9], and (b) a compound that generates an acid upon irradiation with actinic rays or radiation.
[11]
The photosensitive resin composition according to [10], which is for positive development.
[12]
The pattern formation material which is the photosensitive resin composition as described in [10] or [11].
[13]
[10] A photosensitive film formed by the photosensitive resin composition according to [11].
[14]
A cured film obtained by heat-treating the photosensitive resin composition according to [10] or [11].
[15]
(A) forming the photosensitive film according to [13] on a substrate;
(A) a step of exposing the photosensitive film with actinic rays or radiation;
(C) A process for developing the photosensitive film so as to remove the exposed portion with an aqueous alkaline developer, and (d) a method for producing a cured relief pattern comprising a step of heat-treating the obtained relief pattern.
[16]
A cured relief pattern obtained by the production method according to [15].
[17]
[16] A semiconductor device comprising the cured relief pattern according to [16].

According to the present invention, a carboxyl group or hydroxyl group protecting agent having excellent storage stability, the carboxyl group or hydroxyl group being protected by the protecting agent, a resin having excellent storage stability, and the above-described protected product having excellent resolution and sensitivity. Photosensitive resin composition containing the resin, pattern forming material using the photosensitive resin composition, photosensitive film, and cured film, and method for producing a cured relief pattern using the photosensitive resin composition, The cured relief pattern obtained by the above and a semiconductor device comprising the cured relief pattern can be provided.

In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.

<Protecting agent for hydroxyl group or carboxyl group, which is a compound represented by formula (I)>
The hydroxyl group or carboxyl group protecting agent of the present invention (hereinafter also simply referred to as “protecting agent of the present invention”) is a compound represented by the following general formula (I).

In the above general formula, R ¹ and R ² are each independently an alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, acyl group (alkanoyl group), alkoxycarbonyl group, aryloxycarbonyl Represents a group, a cyano group or a halogen atom, and at least one of R ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an alkanoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom. .
R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R ¹ and R ² may be bonded to each other to form a ring, or R ¹ or R ² may be bonded to R ³ to form a ring. X represents a group capable of leaving by the action of the hydroxyl group or carboxyl group.
The compound represented by the general formula (I) reacts with a hydroxyl group of a compound having a hydroxyl group or a carboxyl group of a compound having a carboxyl group without requiring a complicated operation, and is represented by the following general formula (III). A compound having a group can be produced.

(In the formula, R ¹ , R ² and R ³ are respectively synonymous with R ¹ , R ² and R ³ in the general formula (I), and at least one of R ¹ and R ² is an aryl group, alkoxy A group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
* Represents a binding site with a residue obtained by removing —OH from the above group of a compound having a hydroxyl group or a carboxyl group. )
In addition, the partial structure derived from the compound represented by the general formula (I) can be eliminated from the compound having the group represented by the general formula (III) without requiring a complicated operation, and a hydroxyl group or a carboxyl group. The group can be regenerated.
Therefore, the compound represented by the general formula (I) functions as a hydroxyl group or carboxyl group protective agent.

In the present invention, the aryl group, alkoxy group, aryloxy group, alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group or halogen atom for R ¹ and R ² is an electron withdrawing group. ^At least one of ¹ and R ² is an aryl group, an alkoxy group, an aryloxy group, an alkanoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and is represented by the general formula (I) The decomposition reaction of the compound can be suppressed, and the storage stability of the compound represented by the general formula (I) can be improved.
Similarly, in the general formula (III), at least one of R ¹ and R ² is an aryl group, alkoxy group, aryloxy group, alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group or halogen atom. Thus, the compound having the group represented by the general formula (III), that is, a resin or compound in which a carboxyl group or a hydroxyl group is protected by the protective agent (hereinafter sometimes simply referred to as “protector”). Decomposition reaction can be suppressed and storage stability can be improved.

Hereinafter, each group in the general formula (I) or (III) will be described.
The alkyl group for R ¹ , R ² and R ³ may have a substituent and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom in the alkyl chain, You may have a sulfur atom and a nitrogen atom. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group And a branched alkyl group such as a linear alkyl group such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group.
The cycloalkyl group for R ¹ , R ² and R ³ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and has an oxygen atom in the ring. You may have. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
The aryl group for R ¹ , R ² and R ³ may have a substituent and is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a naphthyl group and an anthryl group. Can be mentioned.
The aralkyl group for R ¹ , R ² and R ³ may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group. And naphthylethyl group.
The alkoxy group for R ¹ and R ² may have a substituent and is preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group. , Pentyloxy group, hexyloxy group, heptyloxy group and the like.
The aryloxy group for R ¹ and R ² may have a substituent and is preferably an aryloxy group having 6 to 14 carbon atoms, such as a phenoxy group, a naphthoxy group, an anthryloxy group, etc. Is mentioned.
The acyl group (alkanoyl group) for R ¹ and R ² may have a substituent, and is preferably a linear or branched alkanoyl group having 2 to 7 carbon atoms, such as an acetyl group or propionyl group. Group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, heptanoyl group and the like.
As an alkoxycarbonyl group about R < ¹ > and R < ² >, you may have a substituent, For example, the thing similar to what was illustrated by the said alkoxy group as an alkoxy part is mentioned.
The aryloxycarbonyl group for R ¹ and R ² may have a substituent, and examples of the aryloxy moiety include those similar to those exemplified for the aryloxy group.
Examples of the halogen atom for R ¹ and R ² include fluorine, chlorine, bromine and iodine, preferably a chlorine atom.
The ring formed by combining R ¹ and R ² with each other may have a substituent, preferably has 3 to 8 carbon atoms, and may be saturated or unsaturated. Specific examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclopentene ring, a 1,3-cyclopentadiene ring, a cyclohexene ring, and a cyclohexadiene ring.
The ring formed by combining R ¹ or R ² with R ³ may have a substituent, preferably has 5 to 8 carbon atoms, and specifically includes an oxolane ring, an oxane ring, an oxepane. Ring, oxocan ring and the like.
Examples of the substituent that each of the above groups may have include a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkanoyl group, a carboxyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
The group capable of leaving by the action of the hydroxyl group or carboxyl group as X is, for example, a halogen atom such as chlorine atom, bromine atom, iodine atom, tosylate group, mesylate group, fluorosulfonate group, trifluoromethanesulfonate group, Examples thereof include a sulfonate group such as a nonafluorobutane sulfonate group, preferably a halogen atom, and more preferably a chlorine atom.
From the viewpoint of improvement in the resolution and sensitivity during pattern formation, it is preferable that at least one of R ¹ and R ² is an aryl group, and more preferably at least one of R ¹ and R ² is a phenyl group .
R ³ is preferably a group represented by the following general formula (X).

L ¹ represents an alkylene group or a cycloalkylene group, L ² represents a single bond or a divalent linking group, and R ¹³ represents an alkyl group, an alicyclic group which may contain a hetero atom, or a hetero atom. Represents an aromatic ring group which may contain
The alkylene group for L ¹ is preferably an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The cycloalkylene group for L ¹ is preferably a cycloalkylene group having 3 to 15 carbon atoms, and examples thereof include a cyclopentylene group and a cyclohexylene group.
The divalent linking group as L ² is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene A group (preferably a cycloalkylene group having 3 to 15 carbon atoms, such as a cyclopentylene group or a cyclohexylene group), —S—, —O—, —CO—, —CS—, —SO ₂ —, —N ( R ₀ ) —, or a combination of two or more thereof, and those having a total carbon number of 20 or less are preferred. Here, R ₀ is a hydrogen atom or an alkyl group (eg, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, Hexyl group and octyl group).
L ² is preferably a single bond, an alkylene group, or a divalent linking group comprising a combination of an alkylene group and at least one of —O—, —CO—, —CS— and —N (R ₀ ) —. A divalent linking group comprising a bond, an alkylene group, or a combination of an alkylene group and —O— is more preferable. Here, R ₀ has the same meaning as R ₀ described above.
The alkyl group as R ^{13 is the same} as the alkyl group described above, for example.
Examples of the alicyclic group and aromatic ring group as R ¹³ include the cycloalkyl group and aryl group described above. The number of carbon atoms is preferably 3-18. In the present invention, a group in which a plurality of aromatic rings are linked via a single bond (for example, a biphenyl group or a terphenyl group) is also included in the aromatic group as R ¹³ .
Examples of the alicyclic group containing a hetero atom and the aromatic ring group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole. And pyrrolidone.
The alicyclic group and aromatic ring group as R ¹³ may have a substituent, for example, an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkanoyl group, Examples thereof include a carboxyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

The compound represented by the general formula (I) can be obtained by a known method [for example, “New Experimental Chemistry Course (Vol. 14) Synthesis and Reaction of Organic Compounds (I)” edited by The Chemical Society of Japan, pages 590-591, Maruzen Co., Ltd. Company (January 20, 1985) etc.] can be synthesized and obtained. Thereby, the compound represented by the general formula (I), which is difficult to produce by the production methods described in Patent Documents 1 and 2 described above, can be produced.

<Compound having a hydroxyl group that can be protected by reacting with the protective agent of the present invention, and a compound (resin) in which the hydroxyl group is protected by the protective agent of the present invention>
Examples of the compound having a hydroxyl group that can be protected by reacting with the protective agent of the present invention include alcohols and phenols.
Examples of the alcohol include methanol, ethanol, propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, benzyl alcohol and other monoalcohols, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol , Dodecanediol, O neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, and a polyhydric alcohol such as glycerin.
Phenols include phenol, resorcinol, hydroquinone, pyrocatechol, bisphenol A, dihydroxydiphenylmethane (bisphenol F), bisphenol S, tetrabromobisphenol A, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,4'- Dihydroxy-3,3′-dimethyldiphenylmethane, 4,4′-dihydroxybenzophenone, tris (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, novolac phenol, novolac cresol, bis (3,5-dimethyl- 4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, low molecular phenol compounds such as hydroxystyrene, novolac resin, polyhydroxystyrene resin, hydroxy It has a hydroxyl group such as a copolymer obtained by copolymerizing styrene with another monomer copolymerizable with styrene, a polyhydroxyamide used as a polybenzoxazole precursor, or a poly (meth) acrylate having a phenolic hydroxyl group. Examples thereof include resins and polymers.
The proportion of hydroxystyrene in the copolymer obtained by copolymerizing hydroxystyrene with another monomer copolymerizable therewith is not particularly limited, but is preferably 0.2 to 90 mol%, more preferably 0.8. 2 to 60 mol%.
Examples of the other monomer copolymerizable with hydroxystyrene include a polymerizable unsaturated monomer having a carboxyl group or another monomer copolymerizable therewith. Examples of the polymerizable unsaturated monomer having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, 2-hydroxymethyl-2-propenoic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride. An acid or its acid anhydride is mentioned.
Examples of other monomers copolymerizable with a polymerizable unsaturated monomer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Raw material is C1-C18 alcohol such as isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and (meth) acrylic acid Alkyl (meth) acrylates, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and other (meth) acrylates, 2-hydroxyethyl (meth) acrylate , Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and monoglycerol (meth) acrylate, glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and butanediol di (meth) acrylate , (Meth) acrylamide, (meth) acrylonitrile, diacetone (meth) acrylamide, nitrogen-containing monomers such as dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluoro Fluorine-containing vinyl monomers such as cyclohexyl (meth) acrylate, allyl glycidyl ether, monomers having an epoxy group such as glycidyl (meth) acrylate, styrene, α-methylstyrene, p -Styrene monomers such as methylstyrene, dimethylstyrene and divinylbenzene, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether, polybasic unsaturated carboxylic acids such as fumaric acid, maleic acid and maleic anhydride Examples include acids or esters of mono- or polyhydric alcohols thereof, allyl alcohol, allyl alcohol esters, vinyl chloride, vinylidene chloride, trimethylolpropane tri (meth) acrylate, vinyl acetate, vinyl propionate, and the like. These monomers may be used alone or in combination of two or more.
The polyhydroxystyrene resin or a copolymer obtained by copolymerizing hydroxystyrene with another monomer copolymerizable therewith may have a repeating unit represented by the following general formula (XI). preferable.

In the above general formula (XI), R ¹⁴ represents a hydrogen atom or a methyl group, and Ar represents an arylene group.
R ¹⁴ is more preferably a hydrogen atom.
The arylene group represented by Ar may have a substituent. These arylene groups are preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, more preferably a phenylene group or a naphthylene group which may have a substituent. Most preferred are phenylene groups which may have Moreover, as a substituent which these may have, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned, for example.
Although the specific example of the repeating unit represented by general formula (XI) is shown, this invention is not limited to this.

The polyhydroxystyrene resin is preferably a polyhydroxystyrene resin having a repeating unit represented by the following general formula (V) and having a weight average molecular weight of 1,000 to 100,000. The polyhydroxystyrene resin in which is protected is preferably a polyhydroxystyrene resin in which all or part of the hydroxyl groups of the polyhydroxystyrene resin are substituted with groups represented by the following general formula (III): .

(Wherein R ⁴ represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, and k represents an integer of 0 to 4)
Specific examples and preferred examples of the halogen atom for R ⁴ include those similar to the specific examples and preferred examples described above as the halogen atoms for R ¹ and R ² in formula (I).
Specific examples and preferred examples of an alkoxy group, an alkyl group, an aryl group, and an aralkyl group for R ⁴ include an alkoxy group, an alkyl group, an aryl group for R ¹ , R ^2, and R ³ in the general formula (I), Examples of the aralkyl group are the same as the specific examples and preferred examples described above.

(In the above general formula, R ¹ , R ² and R ³ are respectively synonymous with R ¹ , R ² and R ³ in the general formula (I), and at least one of R ¹ and R ² is an aryl group. , An alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom, wherein * is a residue obtained by removing a hydroxyl group from the repeating unit represented by the general formula (V) Represents the binding site.

Many of the novolak resins are available as commercial products. For example, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, Phenols such as 3,4-xylenol, 3,5-xylenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like, for example, formaldehyde, benzaldehyde, It can also be produced by polycondensation with aldehydes such as furfural and acetaldehyde in the presence of an acidic catalyst (for example, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, an organic acid such as p-toluenesulfonic acid). Good. The above phenols and aldehydes can be used alone or in combination of two or more.
The novolak resin is preferably a novolak resin having a repeating unit represented by the following general formula (VI) and having a weight average molecular weight of 1,000 to 100,000, and the hydroxyl group is protected by the protective agent of the present invention. The novolak resin is preferably a polyhydroxystyrene resin in which all or part of the hydroxyl groups of the novolak resin is substituted with a group represented by the following general formula (III).

(Wherein R ⁵ represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, m represents an integer of 0 to 3, and R ⁶ and R ⁷ each independently represents hydrogen Represents an atom, an alkyl group, an aryl group or an aralkyl group.)
Specific examples and preferred examples of the halogen atom for R ⁵ include those similar to the specific examples and preferred examples described above as the halogen atoms for R ¹ and R ² in formula (I).
Specific examples and preferred examples of the alkoxy group for R ⁵ include those similar to the specific examples and preferred examples described above as the alkoxy groups for R ¹ , R ² and R ³ in the general formula (I).
Specific examples and preferred examples of the alkyl group, aryl group and aralkyl group for R ⁵ , R ⁶ and R ⁷ include an alkoxy group, an alkyl group for R ¹ , R ² and R ³ in the general formula (I), Examples of the aryl group and aralkyl group are the same as the specific examples and preferred examples described above.

(In the above general formula, R ¹ , R ² and R ³ are respectively synonymous with R ¹ , R ² and R ³ in the general formula (I), and at least one of R ¹ and R ² is an aryl group. , An alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
* Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (VI). )

Polyhydroxyamide functions and can be used as a polybenzoxazole precursor. The polyhydroxyamide is preferably a polyhydroxyamide having a repeating unit represented by the following general formula (IX). Examples of the polyhydroxyamide whose hydroxyl group is protected by the protecting agent of the present invention include all or part of the hydroxyl groups of the polyhydroxyamide having a repeating unit represented by the following general formula (IX). The polyhydroxyamide substituted with a group represented by

(In the above general formula, R ¹¹ represents a tetravalent organic group, and R ¹² represents a divalent organic group.)

(In the above general formula, R ¹ , R ² and R ³ are respectively synonymous with R ¹ , R ² and R ³ in the general formula (I), and at least one of R ¹ and R ² is an aryl group. , An alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom, wherein * is a residue obtained by removing a hydroxyl group from the repeating unit represented by the general formula (IX) Represents the binding site.
In the general formula (IX), R ¹¹ is preferably a tetravalent organic group containing an aromatic ring, and the two amino groups and the two hydroxyl groups are bonded directly to the aromatic ring, respectively. Is more preferably a phenolic hydroxyl group, specifically, a residue obtained by removing two hydroxyl groups and two amino groups of hydroxydiamine. Furthermore, in order to provide heat resistance, R ¹¹ is preferably formed from bisaminophenol having one or more aromatic rings as a raw material.
Examples of the bisaminophenol include 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′- Dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, Bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 4,6-diaminoresorcinol, 4,5-diaminoresorcinol, etc., which may be used alone or It can be used in combination of more than seeds.
R ¹¹ is particularly preferably a tetravalent group selected from the following.

In the above formula, X ₁ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—. * Represents a bonding position with —NH— or —OH bonded to R ¹¹ in the general formula (IX). In the above structure, —NH— and —OH bonded to R ¹¹ are bonded to each other in the ortho position (adjacent position).
In the general formula (IX), R ¹² is not particularly limited as long as it is a divalent organic group, but preferably contains one or more aromatic ring groups in order to impart heat resistance to polyoxazole. Specific examples include those containing one or more aromatic rings such as a benzene ring and a naphthalene ring. Furthermore, in order to give the polyoxazole rigid, it is preferable that the two bonding sites of R ¹² are directly present on the aromatic ring. In this case, the two bonding sites may be present on the same aromatic ring, but may be present on different aromatic rings when having a plurality of aromatic rings. When R ¹² is a group containing a plurality of aromatic rings, the plurality of aromatic rings are a single bond, ether bond, methylene bond, ethylene bond, 2,2-propylene bond, 2,2-hexafluoropropylene. Bonding to each other through one or two bonds selected from a bond, a sulfone bond, a sulfoxide bond, a thioether bond and a carbonyl bond improves the heat resistance and mechanical properties of the polyoxazole resin formed after the heat treatment. To preferred.
The resin having the structural unit represented by the general formula (IX) is, for example, as shown in Polymer Science Society, New Polymer Experiments 3 Polymer Synthesis and Reaction (2) P177-P183 (1996). For example, it can be obtained by reacting dicarboxylic acid dihalide obtained by halogenating dicarboxylic acid and dihydroxydiamine.
Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) hexapropane, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxyphenyl ether, bis (4- Carboxyphenyl) sulfone, 2,2-bis (4-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-fluoroisophthalic acid, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 1,2 -Aliphatic dicarboxylic acids such as cyclobutanedicarboxylic acid, 1,4-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, etc., and these may be used alone or in combination of two or more Can be used in combination.

The poly (meth) acrylate having a phenolic hydroxyl group preferably has a repeating unit represented by the following general formula (XII).

In the general formula (XII), R ¹⁵ represents a hydrogen atom or a methyl group, L ² represents a single bond or an alkylene group, and Ar represents an arylene group.
R ¹⁵ is more preferably a methyl group.
The arylene group represented by Ar may have a substituent. These arylene groups are preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, more preferably a phenylene group or a naphthylene group which may have a substituent. Most preferred are phenylene groups which may have Moreover, as a substituent which these may have, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned, for example.
Specific examples of the repeating unit represented by the general formula (XII) are shown below, but the present invention is not limited thereto.

A commercially available resin can also be used as the hydroxyl group-containing resin or polymer.
The weight average molecular weight of the polymer having a hydroxyl group is preferably 1,000 to 200,000, more preferably 1,000 to 100,000, and 1,000 to 50,000. Further preferred.
The resin or polymer having a hydroxyl group can be purified and used as a solid. Moreover, when a solvent is used in the production, it can be used as a solution.

<Compound having a carboxyl group that can be protected by reacting with the protective agent of the present invention, and a compound (resin) in which the carboxyl group is protected by the protective agent of the present invention>
Examples of the compound having a carboxyl group that can be protected by reacting with the protective agent of the present invention include formic acid, acetic acid, propionic acid, propiolic acid, butyric acid, isobutyric acid, hexanoic acid, heptanoic acid, octylic acid, nonanoic acid, and isononanoic acid. Monocarboxylic acids such as decanoic acid, dodecanoic acid, stearic acid, benzoic acid, cinnamic acid, 2-naphthoic acid, nicotinic acid, isonicotinic acid, amin oil fatty acid, tall oil fatty acid, soybean oil fatty acid, dehydrated castor oil fatty acid, Succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanediic acid, compound having decamethylene dicarboxyl group, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Polyvalent carboxylic acids such as methyl hexahydrophthalic acid, lactic acid, citric acid, hydroxy Α, β-unsaturated monomers having a carboxyl group such as pivalic acid, hydroxycarboxylic acid such as 12-hydroxystearic acid, malic acid, acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, A homopolymer of a polymerizable unsaturated monomer having a carboxyl group such as a poly (meth) acrylic resin or a copolymer of a polymerizable unsaturated monomer having a carboxyl group and another monomer copolymerizable therewith. Polymers, polyesters having carboxyl groups, alkyd resins, urethane resins, epoxy resins, carboxyl group-modified epoxy resins, polymers containing carboxyl groups such as polyamic acids of polyimide precursors, etc., among others, containing carboxyl groups Polymerizable unsaturated monomer homopolymer, polymerizable unsaturated monomer containing carboxyl group, and Copolymers of copolymerizable other monomer, or polyamic acid used as a polyimide precursor preferable.
Examples of the polymerizable unsaturated monomer containing a carboxyl group and other monomers copolymerizable therewith include, for example, <a compound having a hydroxyl group that can be protected by reacting with the protective agent of the present invention, and the present invention. And the same as those described above in the section of compound (resin) in which the hydroxyl group is protected by the protecting agent. These monomers may be used alone or in combination of two or more.
Polymerization of a polymerizable unsaturated monomer containing a carboxyl group and copolymerization of a polymerizable unsaturated monomer containing a carboxyl group and another monomer copolymerizable therewith are carried out by known methods. be able to.

As a homopolymer of a polymerizable unsaturated monomer containing a carboxyl group, or a copolymer of a polymerizable unsaturated monomer containing a carboxyl group and another monomer copolymerizable therewith, A polyacrylic acid resin or polymethacrylic acid resin having a repeating unit represented by the following general formula (VII) is preferable. The polyacrylic acid resin or polymethacrylic acid resin in which the carboxyl group is protected by the protective agent of the present invention has a repeating unit represented by the following general formula (VII) and has a weight average molecular weight of 1,000 to 100,000. It is preferable that all or part of the carboxyl group of the coalescence is a polyacrylic acid resin or a polymethacrylic acid resin substituted with a group represented by the following general formula (IV).

(In the above general formula, R ¹ , R ² and R ³ are respectively synonymous with R ¹ , R ² and R ³ in the general formula (I), and at least one of R ¹ and R ² is an aryl group. , An alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, * represents a residue obtained by removing a carboxyl group from the repeating unit represented by the general formula (VII) Represents the binding site.)
The alkyl group for R ⁸ may have a substituent and is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group and an ethyl group. Examples of the substituent that can be included include a hydroxyl group, a halogen atom (such as a fluorine atom and a chlorine atom), a cyano group, and the like, and a hydroxyl group is preferable.

Polyamic acid can function and be used as a polyimide precursor. By using polyamic acid, it is possible to obtain a highly reliable cured relief pattern having excellent heat resistance and less outgassing after heat curing. As said polyamic acid, the polyamic acid containing the repeating unit represented by the following general formula (VIII) is preferable. As the polyamic acid in which the carboxyl group is protected by the protective agent of the present invention, all or part of the carboxyl group of the polyamic acid having a repeating unit represented by the following general formula (VIII) is represented by the following general formula (IV). A polyamic acid substituted with the group represented is preferable.

^(Wherein, R 1, ^{R 2} and ^{R 3} are respectively synonymous with ^R 1, ^{R 2} and ^{R 3} in Formula (I), at least one of ^{R 1} and ^{R 2,} an aryl group, an alkoxy A group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and * represents a residue obtained by removing the carboxyl group from the repeating unit represented by the general formula (VIII). Represents the binding site.)
The repeating unit represented by the general formula (VIII) includes a compound having four carboxyl groups with R ⁹ as a nucleus, a carboxylic acid anhydride thereof, or at least one of the four carboxyl groups represented by the general formula It composed of an acid component derived from a compound comprising substituted with a group represented by (IV), a diamine component derived from the R ¹⁰ in the compound having two amino groups as nucleus. In other words, an acid component which is a partial structure including the two carbonyl groups sandwiched between two carbonyl groups in the general formula (VIII), and —NH—R ² —NH— in the general formula (VIII) It is comprised from the diamine component which is the partial structure represented by these.
The tetravalent organic group R ⁹ preferably has 4 to 30 carbon atoms, and more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group. . A plurality of R ⁹ present in the resin may be the same or different.
Examples of the monocyclic aromatic group in the tetravalent organic group R ⁹ include a benzene ring group and a pyridine ring group.
Examples of the condensed polycyclic aromatic group in the tetravalent organic group R ⁹ include a naphthalene ring group and a perylene ring group.
Examples of the monocyclic aliphatic group in the tetravalent organic group R ⁹ include a cyclobutane ring group, a cyclopentane ring group, and a cyclohexane ring group.
Examples of the condensed polycyclic aliphatic group in the tetravalent organic group R ⁹ include a bicyclo [2.2.1] heptane ring group, a bicyclo [2.2.2] octane ring group, and a bicyclo [2.2. 2] Oct-7-ene ring group and the like.
As the tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group for the tetravalent organic group R ⁹ , the above-mentioned monocyclic or condensed polycyclic aliphatic group or The aromatic group itself may be used, but a plurality of monocyclic or condensed polycyclic aliphatic groups or aromatic groups are linked via a single bond or a divalent linking group, and 4 as R ⁹ A valent linking group may be formed.
The divalent linking group is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, or an ester bond. , Ketone group, amide group and the like.
Specific examples of the acid component having a group derived from at least four carboxyl groups with R ⁹ as a nucleus include pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2, 3,3 ′, 4′-biphenyltetracarboxylic anhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 2 , 2 ′, 3,3′-benzophenonetetracarboxylic acid anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic acid anhydride, 1,2,5,6-naphthalenetetracarboxylic acid anhydride, 2, 3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, (trifluoromethyl) pyromelli Acid anhydride, di (trifluoromethyl) pyromellitic acid anhydride, di (heptafluoropropyl) pyromellitic acid anhydride, pentafluoroethylpyromellitic acid anhydride, bis [3,5-di (trifluoromethyl) phenoxy Pyromellitic anhydride, 3,3 ′, 4,4′-tetracarboxydiphenyl ether dianhydride, 2,3 ′, 3,4′-tetracarboxydiphenyl ether dianhydride, 3,3 ′, 4,4 ′ -Tetracarboxydiphenylmethane dianhydride, 3,3 ', 4,4'-tetracarboxydiphenylsulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-Dicarboxyphenyl) hexafluoropropane dianhydride, 5,5′-bis (trifluoromethyl) -3,3 ′, 4,4′-tetracar Boxibiphenyl dianhydride, 2,2 ′, 5,5′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-tetracarboxybiphenyl dianhydride, 5,5′-bis (trifluoro Methyl) -3,3 ′, 4,4′-tetracarboxydiphenyl ether dianhydride, 5,5′-bis (trifluoromethyl) -3,3 ′, 4,4′-tetracarboxybenzophenone dianhydride, bis [(Trifluoromethyl) dicarboxyphenoxy] benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, 2 , 2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4- (3,4-dicarboxy) Components derived from aromatic tetracarboxylic anhydrides such as phenoxy) phenyl) hexafluoropropane dianhydride, 5,5 ′-[p-phenylenebis (oxycarbonyl)] diphthalic anhydride,

Cyclobutanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride, cyclohexanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3, 5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, or bicyclo [2.2.2] oct-7-ene-2,3,5 , 6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride, Examples include components derived from aliphatic tetracarboxylic anhydrides such as (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic dianhydride.
Preferably, a component derived from pyromellitic acid anhydride, a component derived from 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid anhydride A component derived from 2,2 ′, 3,3′-biphenyltetracarboxylic anhydride, a component derived from 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 4,4 Component derived from '-(hexafluoroisopropylidene) diphthalic anhydride, component derived from 3,3', 4,4'-tetracarboxydiphenyl ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic A component derived from an acid anhydride, a component derived from 5,5 ′-[p-phenylenebis (oxycarbonyl)] diphthalic anhydride, a component derived from cyclobutanetetracarboxylic anhydride, Component derived from tantetracarboxylic anhydride, component derived from bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, (1S, 2S, 4R, 5R)- A component derived from cyclohexanetetracarboxylic dianhydride, a component derived from (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic dianhydride,

More preferably a component derived from pyromellitic anhydride, a component derived from 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride A component derived from cyclobutanetetracarboxylic anhydride, a component derived from 3,3 ′, 4,4′-tetracarboxydiphenyl ether dianhydride, a component derived from cyclopentanetetracarboxylic anhydride, 5 , 5 ′-[p-phenylenebis (oxycarbonyl)] diphthalic anhydride component, (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride component, (1R, 2S, It is a component derived from 4S, 5R) -cyclohexanetetracarboxylic dianhydride. By using these, good solvent solubility, alkali dissolution rate, transparency, and stress characteristics can be realized.
The content of the acid component derived from the compound having four carboxyl groups with R ⁹ as the nucleus in the resin is preferably 20 to 70 mol% with respect to all repeating units constituting the resin. More preferably, it is ˜60 mol%.
Examples of the divalent organic group R ¹⁰ include a divalent group having an alicyclic group, a divalent group having an aromatic group, and a divalent group containing a silicon atom. A plurality of R ¹⁰ present in the resin may be the same as or different from each other.
Hereinafter, the diamine component of the R ¹⁰ to the core when the divalent group having a R ¹⁰ is an alicyclic group, sometimes called alicyclic diamine component, when R ¹⁰ is a divalent group having an aromatic group the diamine component of the R ¹⁰ and nuclei, sometimes called the aromatic diamine component, the diamine component of the R ¹⁰ to the core when the divalent group R ¹⁰ contains a silicon atom, that silicon diamine There is also.
It is preferable that at least one of R ^{10 in} the diamine component present in plural in the resin is a divalent group having an alicyclic group. When the resin contains a diamine component having an alicyclic group, good solvent solubility, alkali dissolution rate, transparency, and sensitivity can be realized.
The alicyclic group that R ¹⁰ may have is preferably a divalent alicyclic group having 3 to 20 carbon atoms, such as a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or bicyclo [2.2. 1] Polycyclic cycloalkylene groups such as a heptylene group, norbornylene group, tetracyclodecanylene group, tetracyclododecanylene group, adamantylene group, and the like can be given.
The divalent group having an alicyclic group for R ¹⁰ may be the alicyclic group itself, but a plurality of alicyclic groups is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, for example, Methylene group, ethylene group, propylene group, etc.) may be linked to form a divalent group having an alicyclic group as R ² , and the amino group and alicyclic group in the diamine component are alkylene groups. You may connect with.

The alicyclic group and alkylene group that can form a divalent group having an alicyclic group may have a substituent, and an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) as such a substituent. ), Halogen atoms and the like.
Particularly preferred diamine components having an alicyclic group structure having R ¹⁰ as a nucleus include a 5-amino-1,3,3-trimethylcyclohexanemethylamine component, a cis-1,4-cyclohexanediamine component, and trans-1,4- Cyclohexanediamine component, 1,4-cyclohexanediamine component (cis, trans mixture), 4,4′-methylenebis (cyclohexylamine) component and its 3,3′-dimethyl-substituted product, bis (aminomethyl) bicyclo [2.2 .1] heptane component, 1,3-diaminoadamantane component, 3,3′-diamino-1,1′-biadamantyl component, 4,4′-hexafluoroisopropylidenebis (cyclohexylamine) component, Of which 3,3'-diamino-1,1'-biadamantyl component, trans-1,4-cycl From the viewpoint of hexane diamine component to lower the stress.

The content of the alicyclic diamine component having two amino groups with R ¹⁰ as a nucleus in the resin is preferably 20 to 70 mol%, and preferably 30 to 60 mol based on all repeating units constituting the resin. % Is more preferable.
The aromatic group in the divalent group having an aromatic group for R ¹⁰ is preferably an aromatic group having 5 to 16 carbon atoms, and examples thereof include a phenylene group and a naphthylene group. Further, the aromatic group may contain a hetero atom such as a nitrogen atom or an oxygen atom, and examples thereof include a divalent benzoxazole group.
The divalent group having an aromatic group for R ¹⁰ may be the aromatic group itself, but a plurality of aromatic groups may be linked via a single bond or a divalent linking group to form R ^2. The divalent group which has an aromatic group as may be formed, and the amino group in the diamine component and the aromatic group may be linked via a divalent linking group.
The divalent linking group is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, or an ester bond. , Ketone group, amide group and the like.
The aromatic group and alkylene group that can form a divalent group having an aromatic group may have a substituent, and an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) as such a substituent. ), An alkoxy group such as a halogen atom and a methoxy group, and an aryl group such as a cyano group and a phenyl group.

Specific examples of the aromatic diamine component having R ¹⁰ as a core include, for example, an m-phenylenediamine component, a p-phenylenediamine component, a 2,4-tolylenediamine component, a 3,3′-diaminodiphenyl ether component, 3, 4'-diaminodiphenyl ether component, 4,4'-diaminodiphenyl ether component, 3,3'-diaminodiphenyl sulfone component, 4,4'-diaminodiphenyl sulfone component, 3,4'-diaminodiphenyl sulfone component, 3,3 ' -Diaminodiphenylmethane component, 4,4'-diaminodiphenylmethane component, 3,4'-diaminodiphenylmethane component, 4,4'-diaminodiphenyl sulfide component, 3,3'-diaminodiphenyl ketone component, 4,4'-diaminodiphenyl Ketone component, 3,4'-diaminodiphenyl ketone component, , 2′-bis (4-aminophenyl) propane component, 2,2′-bis (4-aminophenyl) hexafluoropropane component, 1,3-bis (3-aminophenoxy) benzene component, 1,3-bis (4-aminophenoxy) benzene component, 1,4-bis (4-aminophenoxy) benzene component, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene component, 4-methyl-2, 4-bis (4-aminophenyl) -2-pentene component, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene component, imino-di-p-phenylenediamine component, 1,5-diamino Naphthalene component, 2,6-diaminonaphthalene component, 4-methyl-2,4-bis (4-aminophenyl) pentane component, 5 (or 6) -amino-1- (4-aminophenyl) ) -1,3,3-trimethylindane component, bis (p-aminophenyl) phosphine oxide component, 4,4′-diaminoazobenzene component, 4,4′-diaminodiphenylurea component, 4,4′-bis (4 -Aminophenoxy) biphenyl component, 2,2-bis [4- (4-aminophenoxy) phenyl] propane component, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane component, 2,2 -Bis [4- (3-aminophenoxy) phenyl] benzophenone component, 4,4'-bis (4-aminophenoxy) diphenylsulfone component, 4,4'-bis [4- (α, α-dimethyl-4- Aminobenzyl) phenoxy] benzophenone component, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfur Component, 4,4'-diaminobiphenyl component, 4,4'-diaminobenzophenone component, phenylindanediamine component, 3,3'-dimethoxy-4,4'-diaminobiphenyl component, 3,3'-dimethyl-4 , 4′-diaminobiphenyl component, 2,2′-dimethyl 4,4′-diaminobiphenyl component, 2,2′-bis (trifluoromethyl) benzidine component, o-toluidine sulfone component, 2,2-bis (4 -Aminophenoxyphenyl) propane component, bis (4-aminophenoxyphenyl) sulfone component, bis (4-aminophenoxyphenyl) sulfide component, 1,4- (4-aminophenoxyphenyl) benzene component, 1,3- (4 -Aminophenoxyphenyl) benzene component, 9,9-bis (4-aminophenyl) fluorene component, 4,4 ' Di- (3-aminophenoxy) diphenylsulfone component, 4,4′-diaminobenzanilide component, 4-aminophenyl-4′-aminophenylbenzoate component, bis (4-aminophenyl) terephthalate component, 2- (4- Aminophenyl) benzoxazol-5-ylamine, 4,4 ″ -diamino-p-terphenyl component, etc., and the hydrogen atom of the aromatic nucleus of these aromatic diamines is a chlorine atom, a fluorine atom, a bromine atom, a methyl group, Examples include a structure substituted with at least one group or atom selected from the group consisting of a methoxy group, a cyano group, and a phenyl group.

Particularly preferred aromatic diamine components include p-phenylenediamine component, 4,4′-diaminodiphenyl ether component, 3,3′-diaminodiphenylsulfone component, 4,4′-diaminodiphenylsulfone component, and 2,2′-bis. (4-aminophenyl) hexafluoropropane component, 1,4-bis (4-aminophenoxy) benzene component, imino-di-p-phenylenediamine component, 4,4'-diaminobiphenyl component, 4,4'-diamino Benzophenone component, 3,3′-dimethoxy-4,4′-diaminobiphenyl component, 3,3′-dimethyl-4,4′-diaminobiphenyl component, 2,2′-dimethyl 4,4′-diaminobiphenyl component, 2,2′-bis (trifluoromethyl) benzidine component, o-toluidine sulfone component, 2,2-bis (4-amino Nophenoxyphenyl) propane component, 9,9-bis (4-aminophenyl) fluorene component, 4,4′-di- (3-aminophenoxy) diphenylsulfone component, 4,4′-diaminobenzanilide component, 4- Aminophenyl-4′-aminophenylbenzoate component, bis (4-aminophenyl) terephthalate, 2- (4-aminophenyl) benzoxazol-5-ylamine component, 4,4 ″ -diamino-p-terphenyl component A film having good toughness and low stress can be obtained.
The diamine component may be substituted with a hydroxyl group. Examples of such bisaminophenol components include 3,3′-dihydroxybenzidine component, 3,3′-diamino-4,4′-dihydroxybiphenyl component, and 4,4′-diamino-3,3′-dihydroxy. Biphenyl component, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone component, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone component, bis- (3-amino-4-hydroxyphenyl) methane Component, 2,2-bis- (3-amino-4-hydroxyphenyl) propane component, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane component, 2,2-bis- (4 -Amino-3-hydroxyphenyl) hexafluoropropane component, bis- (4-amino-3-hydroxyphenyl) methane component, 2 2-bis- (4-amino-3-hydroxyphenyl) propane component, 4,4′-diamino-3,3′-dihydroxybenzophenone component, 3,3′-diamino-4,4′-dihydroxybenzophenone component, 4 , 4'-diamino-3,3'-dihydroxydiphenyl ether component, 3,3'-diamino-4,4'-dihydroxydiphenyl ether component, 1,4-diamino-2,5-dihydroxybenzene component, 1,3-diamino -2,4-dihydroxybenzene component, 1,3-diamino-4,6-dihydroxybenzene component and the like. These bisaminophenol components may be used alone or in combination.

Among these bisaminophenol structures, a particularly preferred embodiment includes a case where R ¹⁰ in the general formula (VIII) is a divalent group having an aromatic group selected from the following.

In the above formula, X ₁ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—. * Represents a bonding position with —NH— or —OH bonded to R ² in the general formula (1). In the above structure, —NH— and —OH bonded to R ² are bonded to each other in the ortho position (adjacent position).
The content of the aromatic diamine component having two amino groups with R ¹⁰ as a nucleus in the resin is preferably 5 to 40 mol% with respect to all repeating units constituting the resin, and preferably 10 to 30 mol. % Is more preferable.
Moreover, the R ¹⁰ to enhance the adhesion to the substrate can be a silicon diamine component as the diamine component to the nucleus. Examples include bis (4-aminophenyl) dimethylsilane component, bis (4-aminophenyl) tetramethylsiloxane component, bis (4-aminophenyl) tetramethyldisiloxane component, bis (γ-aminopropyl) tetramethyl. Examples thereof include a disiloxane component, a 1,4-bis (γ-aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis (γ-aminopropyl) tetraphenyldisiloxane component.
The following structure can also be mentioned as a silicon diamine component.

In the above formula, R ¹⁶ represents a divalent organic group, and R ¹⁷ represents a monovalent organic group. A plurality of R ¹⁶ may be the being the same or different. The plurality of R ¹⁷ may be the same as or different from each other.
Examples of the divalent organic group represented by R ¹⁶ include an optionally substituted linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group having 6 to 20 carbon atoms, and 3 to 3 carbon atoms. 20 represents a divalent alicyclic group or a group formed by combining these.
The monovalent organic group represented by R ¹⁷ represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent.
More specifically, the following can be mentioned.

The content of the silicon diamine component having at least two amino groups with R ¹⁰ as a nucleus in the resin is preferably 5 to 40 mol% with respect to all repeating units constituting the resin, and preferably 10 to 30 mol. % Is more preferable.
The polyamic acid containing the repeating unit represented by the general formula (VIII) is, for example, as shown in Polymer Science Society edited by New Polymer Experiments 3 Polymer Synthesis and Reaction (2) P155-P171 (1996). It can be obtained by reacting an acid component and a diamine in an organic solvent.
Examples of organic solvents include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, benzene, anisole, diphenyl ether, Aromatic solvents such as nitrobenzene, benzonitrile, pyridine, halogenated solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, ethers such as tetrahydrofuran, dioxane, diglyme Examples thereof include system solvents and dimethyl sulfoxide. Of these, amide solvents are preferred, and high molecular weight polyamic acid can be obtained.

You may make terminal blocker react with the terminal of the polyamic acid containing the repeating unit represented by general formula (VIII). As the terminal capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used. By making terminal blocker react, it is preferable at the point which can control the repeating number of a structural unit, ie, molecular weight, in a preferable range. Furthermore, acid deactivation due to neutralization of the terminal amine and the generated acid can be suppressed by the terminal blocking agent. In addition, by reacting a terminal blocking agent at the terminal, various organic groups such as a crosslinking reactive group having a carbon-carbon unsaturated bond can be introduced as a terminal group.
Monoamines used for end-capping agents are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy- 6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2 -Hydroxynaphthalene, 1-carboxy-8-amino Phthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy -2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5- Aminosalicylic acid, 6-aminosalicylic acid, 3-a No-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-aminobenzoic acid Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto- 2-aminonaphthalene, 1-amino-7-mercaptonaphthalene 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino -2-Mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3 -Aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3 , 5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1 -Aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethini 1-aminonaphthalene, 4,8-diethynyl-2-Amino-naphthalene, but it is not limited thereto.

Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline and the like are preferable.
Acid anhydrides, monocarboxylic acids, monoacid chloride compounds and active ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride Acid anhydrides such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1- Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxyl Naphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto -3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4- Ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1- Naphthoic acid, 3-ethynyl-1-na Toeic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2- Ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid Acids, monocarboxylic acids such as 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which these carboxyl groups are acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxyl Sinaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene , Monoacid chloride compounds in which only the monocarboxylic group of dicarboxylic acids such as 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3- Examples include active ester compounds obtained by reaction with dicarboximide.

Among these, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl benzoic acid Monocarboxylic acids, and monoacid chloride compounds in which these carboxyl groups are converted to an acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1 , 7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and the like monoacid chloride compounds in which only the monocarboxyl group of the dicarboxylic acid is converted to acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5- Active ester compounds obtained by reaction with norbornene-2,3-dicarboximide are preferred.
The introduction ratio of the monoamine used for the end-capping agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent is in the range of 0.1 to 100 mol% with respect to the diamine component. The amount is particularly preferably 5 to 90 mol%. A plurality of different end groups may be introduced by reacting a plurality of end capping agents.
The end-capping agent introduced into the polymer can be easily detected by the following method. For example, a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer. The end-capping agent can be easily detected by gas chromatography (GC) or NMR measurement. In addition, it can also be easily detected by directly measuring the polymer component into which the end capping agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ CNMR spectrum.

A commercially available resin can also be used as the resin or polymer containing a carboxyl group.
The ratio of the carboxyl group in the resin or polymer containing a carboxyl group is not particularly limited, but the acid value is preferably 20 to 200, more preferably 40 to 160. Here, the acid value is the number of mg of potassium hydroxide necessary to neutralize the carboxyl group contained in 1 g of the polymer.
The weight average molecular weight of the resin or polymer containing a carboxyl group is preferably 1,000 to 200,000, more preferably 3,000 to 10,000, and still more preferably 3,000 to 50,000. 000.
The polymer containing a carboxyl group can be purified and used as a solid. Moreover, when a solvent is used in the production, it can be used as a solution.

<Method for protecting hydroxyl group or carboxyl group using compound represented by formula (I)>
A method for protecting a hydroxyl group or a carboxyl group of a compound having a hydroxyl group or a carboxyl group using the compound represented by the general formula (I) is a method for producing a compound having a group represented by the general formula (III). It is also a method.
By reacting the compound represented by the general formula (I) with a compound having a hydroxyl group or a carboxyl group, the hydroxyl group or the carboxyl group can be protected and represented by the general formula (III). A compound having a group can be produced.
The use amount (molar ratio) of the compound represented by the general formula (I) with respect to the compound having a hydroxyl group or a carboxyl group is not particularly limited, but hydroxyl to be protected in a compound having a hydroxyl group or a carboxyl group The amount is preferably 0.1 to 10 mol, more preferably 0.2 to 5 mol, and still more preferably 0.3 to 3 mol with respect to 1 mol of the group or carboxyl group.
The reaction temperature is preferably 0 to 100 ° C, more preferably 0 to 50 ° C, still more preferably 0 to 20 ° C.
Moreover, it is preferable to contain a base in the reaction system. The base is not particularly limited, and examples thereof include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ethylamine, diethylamine, triethylamine, and diisopropylethylamine. Among them, triethylamine or diisopropylethylamine is preferable. . The content of the base is not particularly limited, but is preferably 1 to 10 mol, and more preferably 1 to 3 mol, per 1 mol of the compound represented by the general formula (I). Moreover, you may use an organic solvent as needed. Examples of the organic solvent include hydrocarbon solvents such as hexane, toluene and xylene, ether solvents such as dioxane and tetrahydrofuran, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, N, N-dimethylacetamide, N , N-dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like, and one or more of them are used.
After completion of the reaction, the compound having a group represented by the general formula (III) can be obtained by purification by a known method such as washing with water, distillation, crystallization, reprecipitation, etc., if necessary.
When the compound having a group represented by the general formula (III) is a compound having a polymerizable unsaturated double bond, if necessary, it may be used alone or in other polymerizable unsaturated units by a known method. It may be polymerized with a monomer.

<Method for removing group (protecting group) represented by formula (III)>
Examples of the method for removing the protecting group include a method of treating a compound having a group represented by the general formula (III) with heat or an acid.
When processing with heat, it is preferably performed at 150 to 250 ° C.
In the case of treatment with an acid, examples of the acid to be used include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, camphorsulfonic acid and the like, and among them, p-toluenesulfonic acid is preferable. The amount of the acid used is preferably 0.01 to 50 mol with respect to 1 mol of the structure derived from the compound represented by the general formula (I) to be eliminated. The temperature during the treatment with an acid is preferably 20 to 150 ° C. When treating with an acid, water may be added. The amount of water used is preferably 0.1 to 100% by mass relative to the compound having a group represented by the general formula (III). In addition, when water is added, the temperature during the treatment with an acid is preferably 20 to 80 ° C.
When desorbing the structure derived from the compound represented by the general formula (I), an organic solvent may be used. Examples of the organic solvent include those described above, and the amount used is preferably 10 to 300% by mass, and 20 to 100% by mass with respect to the compound represented by the general formula (I). Is more preferable.
In addition, a compound having a group represented by the general formula (III) and a photoacid generator are allowed to coexist, and the photoacid generator is irradiated with radiation or the like to generate an acid, thereby deprotecting the hydroxyl group. Alternatively, the carboxyl group can be regenerated.
As described above, the compound represented by the general formula (I) can be used for protecting and deprotecting a carboxyl group of a compound having a hydroxyl group or a compound having a carboxyl group. Therefore, the compound having a group represented by the general formula (III) can be used as a constituent component of a chemically amplified resist composition or the like.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention contains (a) a resin having a group represented by the general formula (III) or (IV), and (b) a compound that generates an acid upon irradiation with actinic rays or radiation. To do.
The resin having a group represented by the general formula (III) or (IV) (hereinafter sometimes simply referred to as “base polymer”) preferably has a repeating unit represented by the general formula (V). Polyhydroxystyrene resin in which all or part of hydroxyl groups of polyhydroxystyrene are substituted with groups represented by the above general formula (III), hydroxyl of novolak resin having a repeating unit represented by the above general formula (VI) A novolak resin in which all or part of the group is substituted with the group represented by the general formula (III), all or all of the carboxyl groups of the polyacrylate or polymethacrylate having the repeating unit represented by the general formula (VII) A polyacrylate resin or polymethacrylate resin partially substituted with a group represented by the general formula (IV), A polyamic acid in which all or part of the carboxyl groups of the polyamic acid having a repeating unit represented by the formula (VIII) are substituted with a group represented by the general formula (IV), represented by the general formula (IX) A polyhydroxyamide in which all or a part of hydroxyl groups of a polyhydroxyamide having a repeating unit is substituted with a group represented by the general formula (III).
The weight average molecular weight of the base polymer is preferably 1,000 to 200,000, more preferably 1,000 to 150,000, and still more preferably 1,000 to 100,000.
In the photosensitive resin composition of the present invention, the resin (a) having a group represented by the general formula (III) or (IV) may be used alone or in combination of two or more. Moreover, you may contain resin other than resin (a) which has group represented by the said general formula (III) or (IV).

(B) Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention is a compound that generates acid upon irradiation with actinic ray or radiation (also referred to as “photoacid generator” or “(b) component”). Containing. These may be used in combination of two or more. Moreover, a sensitizer etc. can also be used together for sensitivity adjustment.

(B1) Photoacid generator The photoacid generator is used as a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, or a microresist. Known compounds that generate an acid upon irradiation with active light or radiation and mixtures thereof can be appropriately selected and used.

Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

Further, a group that generates an acid upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. 3914407, JP 63-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP The compounds described in 63-146029 and the like can be used.

Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^— An organic anion having a carbon atom is preferable.
In the general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group. X ⁻ represents a non-nucleophilic anion.

Preferred organic anions include organic anions represented by the following general formula.

In the above general formula,
Rc ₁ represents an organic group.
Examples of the organic group in Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these which may be substituted is a single bond, —O—, — And groups linked by a linking group such as CO ₂ —, —S—, —SO ₃ —, —SO ₂ N (Rd ₁ ) —.
Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group.
Examples of the organic group for Rc ₃ , Rc ₄ and Rc ₅ include the same organic groups as those for Rc ₁ , preferably a perfluoroalkyl group having 1 to 4 carbon atoms.
Rc ₃ and Rc ₄ may be bonded to form a ring.
Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group, a cycloalkylene group, and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.
The organic group of Rc ₁ and Rc ₃ to Rc ₅ is preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. Further, Rc ₃ and Rc ₄ are combined to form a ring, so that the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.

In general formula (ZI),
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. _Examples of the organic group for R ₂₀₁ to R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.
Two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
In the general formulas (ZII) and (ZIII), the aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.
The alkyl group and cycloalkyl group in R ₂₀₄ to R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.

<Triarylsulfonium salt>
Triarylsulfonium salts are particularly preferable in terms of thermal stability and sensitivity, and it is preferable to use a sensitizer in combination.
Two or more kinds of such compounds can be used in combination as required.

In the triarylsulfonium salt, it is preferable that at least one aryl group has an electron withdrawing group as a substituent, and the total Hammett value of the substituents bonded to the aryl skeleton is preferably larger than 0.18. .

Here, the electron withdrawing group means a substituent having a Hammett value (Hammet substituent constant σ) larger than 0. In the present invention, from the viewpoint of high sensitivity, it is preferable that the sum total of the Hammett value is 0.18 or more substituents bonded to aryl skeletons in a particular photoacid generator, and more is greater than 0.46 Preferably, it is more preferably larger than 0.60.
The Hammett value represents the degree of electron withdrawing property of a cation having a triarylsulfonium salt structure, and there is no particular upper limit from the viewpoint of increasing sensitivity, but from the viewpoint of reactivity and stability. Is preferably more than 0.46 and less than 4.0, more preferably more than 0.50 and less than 3.5, and particularly preferably more than 0.60 and less than 3.0.

The Hammett value in the present invention uses the numerical values described in Naoki Inamoto, Chemistry Seminar 10 Hammett's Law-Structure and Reactivity (published by Maruzen Co., Ltd. in 1983).
Examples of the electron withdrawing group introduced into the aryl skeleton include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxyl group, and a carbonyl group. The Hammett values of these substituents are shown below. A trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), a halogen atom [eg, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), -Br (m: 0.39, p: 0.23), -I (m: 0.35, p: 0.18)], an ester group (for example, -COCH ₃ , O: 0.37, p: 0.45), sulfoxide group (for example, —SOCH ₃ , m: 0.52, p: 0.45), cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxy group (—COOH, m: 0.37, p: 0.45), a carbonyl group (— CHO, m: 0.36, p: (043)) and the like. The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is.

Among these substituents, nonionic substituents such as a halogen atom and a halogenated alkyl group are preferable from the viewpoint of hydrophobicity. Among them, —Cl is preferable from the viewpoint of reactivity, and imparts hydrophobicity. From the viewpoint, —F, —CF ₃ , —Cl, and —Br are preferable.

These substituents may be introduced into any one of the three aryl skeletons of the triarylsulfonium salt structure, or may be introduced into two or more aryl skeletons. Moreover, the substituent introduced into each of the three aryl skeletons may be one or plural. In the present invention, the sum of Hammett values of substituents introduced into these aryl skeletons is preferably more than 0.18, more preferably more than 0.46. The number of substituents to be introduced is arbitrary. For example, only one substituent having a particularly large Hammett value (for example, a Hammett value exceeding 0.46 alone) may be introduced into one position of an aryl skeleton having a triarylsulfonium salt structure. Moreover, for example, a plurality of substituents introduced and the sum of the Hammett values exceeding 0.46 may be introduced.

As described above, since the Hammett value of the substituent varies depending on the position where it is introduced, the sum of Hammett values in the specific photoacid generator according to the present invention is determined by the type of substituent, the position of introduction, and the number of introductions. become.
The Hammett's rule is usually expressed in the m-position and p-position, but in the present invention, the substituent effect at the o-position is calculated as the same value as the p-position as an index of electron withdrawing property. Preferred substitution positions are preferably m-position and p-position, and most preferably p-position from the viewpoint of synthesis.
Preferred in the present invention is a sulfonium salt that is tri- or more substituted with a halogen atom, and most preferred is a sulfonium salt that is tri-substituted with a chloro group, specifically, each of the three aryl skeletons. And preferably have a triarylsulfonium salt structure in which —Cl is introduced, and more preferably —Cl is substituted at the p-position.

Examples of the sulfonate anion possessed by the triarylsulfonium salt contained in the composition of the present invention include an aryl sulfonate anion, an alkane sulfonate anion, and the like, which are substituted with a fluorine atom or an organic group having a fluorine atom. An anion is preferred.

Examples of the compound having a triarylsulfonium salt structure are J.P. Am. Chem. Soc. 112 (16), 1990; 6004-6015, J.A. Org. Chem. 1988; It can be easily synthesized by the methods described in 5571-5573, WO02 / 081439A1, European Patent (EP) 1113005, and the like.

Specific examples are given below, but are not limited thereto.

Further, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate or 4-phenylthiophenyl diphenylsulfonium trifluoroacetate and the like.

Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2'-hydroxy- 1'-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetra Decaoxy) phenyliodonium-p-toluenesulfonate, etc .; diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butyl) Sulfonyl) diazomethane, bis (p- toluenesulfonyl) diazomethane;
Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide p-toluene sulfonate, phthalimide trifluoromethyl sulfonate, N-hydroxynaphthalimide methane. Examples thereof include sulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide propane sulfonate, and the like.

Among compounds that generate an acid upon irradiation with actinic rays or radiation, oxime compounds, more preferably oxime sulfonate compounds, are the most preferable examples from the viewpoint of sensitivity, resolution, dielectric constant, dimensional stability, and the like. Can be mentioned.

Preferred examples of the oxime sulfonate compound, that is, the compound having an oxime sulfonate residue include compounds containing an oxime sulfonate residue represented by the formula (b1).

(In formula (b1), R ⁵ represents an alkyl group or an aryl group.)
Any group may be substituted, and the alkyl group in R ⁵ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ⁵ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
The aryl group for R ⁵ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group for R ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The compound containing the oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5). Is particularly preferred.

(In the formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and each R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom. R ⁶ represents each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ¹ may have a substituent.
In the formula (OS-3) ~ (OS -5), the alkyl group in ^{R 1,} is preferably a alkyl group having 1 atoms in total may be carbon 30 have a substituent.
Examples of the substituent that the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group.

In the formulas (OS-3) to (OS-5), the aryl group for R ¹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the aryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. , A sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

The aryl group in R ^1, a phenyl group, p- methylphenyl group, p- chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o- methoxyphenyl groups include p- phenoxyphenyl group.

In the formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the heteroaryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl. Group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.

In the above formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ¹ may be a heteroaromatic ring. For example, a heteroaromatic ring and a benzene ring are condensed. May be.
The heteroaryl group for R ¹ is selected from the group consisting of optionally substituted thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring and benzimidazole ring. And a group obtained by removing one hydrogen atom from the ring.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the formulas (OS-3) to (OS-5), it is preferred that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
In the formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ² may have a substituent. Examples of the substituent that the alkyl group or aryl group in R ² may have include the same groups as the substituent that the alkyl group or aryl group in R ¹ may have.

The alkyl group for R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and is an alkyl group having 1 to 6 carbon atoms which may have a substituent. It is more preferable.
Examples of the alkyl group in R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, and chloromethyl group. , A bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group are preferable. A methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is preferable.

The aryl group for R ² is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Specifically, the aryl group in R ² is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
Examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these, a chlorine atom and a bromine atom are preferable.

In the formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.
In formulas (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferable.

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group for R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl are preferred.

In the formula (OS-3) ~ (OS -5), the alkyl group in ^{R 6,} is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.
Examples of the substituent that the alkyl group optionally has at R ^6, include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an amino group It is done.

As the alkyloxy group in R ⁶ , a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
In the above formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group. It is done.
In the above formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.

The compound containing an oxime sulfonate residue represented by the formula (b1) is particularly preferably an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11). .

(In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, Represents an alkyl group of 1 to 8, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group; ¹⁰ represents a hydrogen atom or a methyl group.)

R ¹ in the formulas (OS-6) to (OS-11) has the same meaning as R ¹ in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
R ⁷ in formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ⁸ in the formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl Represents an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable, and a methyl group is particularly preferable. R ⁹ in formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ¹⁰ in the formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

The compound containing an oxime sulfonate residue represented by the formula (b1) is also preferably a compound represented by the formula (OS-1).

In the general formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl. Represents a group. R ² represents an alkyl group or an aryl group.

X is -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H- or ^-CR 6 ^{R 7} - ^represents, ^R 5 ~ R ⁷ is an alkyl group or an aryl group Represents.
R ²¹ to R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or Represents an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.
As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom and an alkyl group are preferable, and an embodiment in which at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R ²¹ to R ²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

The compound represented by the formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

In the formula (OS-2), R ¹ , R ² and R ²¹ to R ²⁴ have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
Among these, an embodiment in which R ¹ in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), in which R ¹ is a cyano group, phenyl The embodiment which is a group or a naphthyl group is most preferred.

In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

Specific examples (exemplary compounds b-1 to b-34) of the compound represented by the formula (OS-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.

The above compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the following formula (b2).

(In the formula (b2), R ⁵ represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 0 to 3, and m is 2 or 3. In some cases, multiple Xs may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m is preferably 0 or 1.
In the formula (b2), m is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A compound that is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

The compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the formula (b3).

(In the formula (b3), ^{R 5} has the same meaning as ^{R 5} in the formula (b1), X 'is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and L represents an integer of 0 to 5.)

R ⁵ in the formula (b3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
X ′ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
L is preferably from 0 to 2, particularly preferably from 0 to 1.

Specific examples of the compound represented by the formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzyl. Cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- [(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl ] Acetonitrile, α-[(4-True Can be exemplified sulfonyl) -4-methoxyphenyl] acetonitrile.

Specific examples of preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (C) radiation-sensitive acid generators.

In the photosensitive resin composition of the present invention, the content of the photoacid generator is preferably 1 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the photosensitive resin composition.

The acid generator can be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.

(B2) Sensitizer A sensitizer may be added to the composition of the present invention in order to absorb actinic rays or radiation and promote the decomposition of the sulfonium salt. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with sulfonium, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin).

More preferred examples of the sensitizer include compounds represented by the following formulas (IX) to (XIV).

In formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with adjacent A ¹ and an adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

In the formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in Formula (IX).

In the formula (XI), A ₂ represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ₂ and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (XII), A ³ and A ⁴ each independently represent —S—, —NR ⁶² — or —NR ⁶³ —, and R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ^4, and adjacent carbon atoms, and R ⁶⁰ , R ⁶¹ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.

In formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or ═NR ⁶⁷ . R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

In formula (XIV), R ₆₈ and R ₆₉ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. R ₇₀ and R ₇₁ each independently represent a monovalent nonmetallic atomic group, and n represents an integer of 0 to 4. When n is 2 or more, R ₇₀ and R ₇₁ can be bonded to each other to form an aliphatic or aromatic ring.

As the sensitizer, an anthracene derivative is particularly preferable.

Specific preferred examples of the compounds represented by the formulas (IX) to (XIV) include (C-1) to (C-26) shown below, but are not limited thereto.

The sensitizer as described above may be a commercially available one or may be synthesized by a known synthesis method.

In the photosensitive resin composition of the present invention, the content of the sensitizer is preferably 1 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the photosensitive resin composition.

(C) Basic compound The composition according to the present invention preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like. As compounds having a diazabicyclo structure, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0 ] Undecar 7-ene and the like. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably 6 to 12 carbon atoms may be bonded to the nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. In addition to the alkyl group, the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. The halogen atom is particularly preferably chloride, bromide or iodide, and the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

In the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, the sulfonic acid ester group may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester. In the case of an alkyl sulfonate ester, the alkyl group has 1 to 20 carbon atoms, in the case of a cycloalkyl sulfonate ester, the cycloalkyl group has 3 to 20 carbon atoms, and in the case of an aryl sulfonate ester, the aryl group has 6 carbon atoms. ~ 12 are preferred. Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid. An ester group is preferred.

It is preferable to have at least one oxyalkylene group between the sulfonate group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.
The following compounds are also preferable as the basic compound.

These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.
The composition according to the present invention may or may not contain a basic compound. However, when it is contained, the content of the basic compound is usually 0.001 to on the basis of the total solid content of the composition. It is 10% by mass, preferably 0.01-5% by mass.

The use ratio of the acid generator and the basic compound is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the relief pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

(D) Thermal acid generator The present invention may contain a thermal acid generator. The thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C., for example, sulfonic acid, It is a compound that generates a low nucleophilic acid such as carboxylic acid or disulfonylimide.
As the generated acid, sulfonic acid, alkyl substituted with an electron withdrawing group or arylcarboxylic acid having a strong pKa of 2 or less, disulfonylimide substituted with an electron withdrawing group, and the like are preferable. Examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
The thermal acid generator is required not to be decomposed during storage time or in a pre-baking process after applying the composition, but to be quickly decomposed in a heat-curing process after patterning. Therefore, the thermal decomposition point is preferably 100 ° C to 300 ° C. More preferably, it is 120 ° C to 250 ° C, and further preferably 150 ° C to 200 ° C.
As the thermal acid generator, a photoacid generator that generates an acid by the above-described exposure can be applied. Examples thereof include onium salts such as sulfonium salts and iodonium salts, N-hydroxyimide sulfonate compounds, oxime sulfonates, o-nitrobenzyl sulfonates and the like.

Preferred examples of the sulfonium salt include compounds represented by the following general formulas (TA-1) to (TA-3).

In general formula (TA-1),
R _T1 to R _T5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _T6 and R _T7 each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.
R _T8 and R _T9 each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
Any two or more of R _T1 to R _T5 , R _T6 and R _T7, and R _T8 and R _T9 may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, a ketone A bond, an ester bond, or an amide bond may be included.
_Examples of the group formed by combining any two or more of R _T1 to R _T5 , R _T6 and R _T7, and R _T8 and R _T9 include a butylene group and a pentylene group.
X ⁻ represents a non-nucleophilic anion, and has a strong pKa of 2 or less as described above, a sulfonic acid or an alkyl or aryl carboxylic acid substituted with an electron withdrawing group, or a disulfonylimide substituted with an electron withdrawing group. Etc. are preferable. Examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In general formula (TA-2),
R _T10 and R _T11 each independently represent an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
R _T10 and R _T11 may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, a ketone bond, an ester bond, or an amide bond.
_{Examples of} the group formed by combining R _T10 and R _T11 include a butylene group and a pentylene group.
R _T12 to R _T16 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a thioalkoxy group, or a hydroxyl group, and two or more of them are bonded to each other to form a naphthalene ring, an anthracene ring, etc. A polycyclic aromatic ring may be formed.
X ⁻ represents a non-nucleophilic anion.

In general formula (TA-3),
R _T17 represents an alkyl group (straight chain or branched) or a cycloalkyl group, preferably a straight chain and branched alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms (for example, a methyl group, Ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group). Examples of the cycloalkyl group include not only a monocyclic cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group, but also a cyclic alkyl group having a bridging site such as a norbornyl group, a tricyclodecanyl group, and an adamantyl group. it can.
R _T18 and R _T19 each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.
R _T20 and R _T21 each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
R _T18 and R _T19 and R _T20 and R _T21 may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, a ketone bond, an ester bond, or an amide bond. Good. _{Examples of} the group formed by combining R _T18 and R _T19 and R _T20 and R _T21 include a butylene group and a pentylene group.
X ⁻ represents a non-nucleophilic anion.

The alkyl group as R _T1 to R _T17 may be linear or branched. For example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (for example, Methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
The cycloalkyl group as R _T1 to R _T17 is _{meant to} include a monocyclic alkyl group as well as a polycyclic and cyclic alkyl group having a bridging site, and the cycloalkyl group as R _T12 to R _T16 is preferably Is a cycloalkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group).
The cycloalkyl group as R _T17 has a cycloalkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group) and a cyclic group having a bridging site such as a norbornyl group, a tricyclodecanyl group, or an adamantyl group. Also preferred are alkyl groups.

The alkoxy group as R _T1 to R _{T5 and} R _T12 to R _T16 may be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 1 carbon atoms. 5 linear and branched alkoxy groups (for example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), cyclic alkoxy groups having 3 to 8 carbon atoms (for example, , Cyclopentyloxy group, cyclohexyloxy group).
The thioalkoxy group as R _T12 to R _T16 may be linear, branched or cyclic, for example, a thioalkoxy group having 1 to 10 carbon atoms, preferably a linear or branched group having 1 to 5 carbon atoms. A thioalkoxy group (for example, a thiomethoxy group, a thioethoxy group, a linear or branched thiopropoxy group, a linear or branched thiobutoxy group, a linear or branched thiopentoxy group), a cyclic thioalkoxy group having 3 to 8 carbon atoms (for example, thiocyclopentyl) Oxy group, thiocyclohexyloxy group).

The non-nucleophilic anion as X ⁻ is preferably an organic anion, and particularly preferably an organic anion represented by the following general formula.

In the above general formula,
Rc ₁ represents an organic group.
Examples of the organic group for Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these optionally having a substituent is a single bond, —O. _{-, - CO 2 -, -} S -, - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₂ represents 1-position an alkyl group substituted with a fluorine atom or a fluoroalkyl group.
Rc ₃ and Rc ₄ each independently represents an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group. Preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms.
Rc ₃ and Rc ₄ may be bonded to each other to form a ring.
Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group, a cycloalkylene group, and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.

Preferred examples of the iodonium salt include compounds represented by the following general formula (TA-4).

In formula (TA-4), R ₄₁ and R ₄₂ each have a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituent. An alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, a nitro group, a halogen atom, a hydroxyl group Represents a carboxyl group.
a represents 1 to 5, and b represents 1 to 5.
However, at least one of R ₄₁ and R ₄₂ has an alkyl group having 5 or more carbon atoms, which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. An alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, and an acyloxy group which may have a substituent.
X represents R—SO ₃ , and R represents an aliphatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group which may have a substituent.

As the alkyl group for R ₄₁ and R ₄₂ , an optionally substituted methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, Examples thereof include those having 1 to 25 carbon atoms such as hexyl group, heptyl group, octyl group, t-amyl group, decanyl group, dodecanyl group and hexadecanyl group. The cycloalkyl group has 3 to 25 carbon atoms which may have a substituent, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecanyl group, cyclohexadecanyl group and the like. Things. The alkoxy group may have a substituent, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a t-butoxy group, a pentyloxy group, t Examples thereof include those having 1 to 25 carbon atoms such as -amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecanoxy group and the like.

As the alkoxycarbonyl group, a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group or t which may have a substituent may be used. Those having 2 to 25 carbon atoms such as -butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecanoxycarbonyl group, etc. Can be mentioned. The acyl group may have a substituent and has 1 carbon atom such as formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group, t-amylcarbonyl group and the like. Up to 25 can be mentioned. As the acyloxy group, an acetoxy group, propionyloxy group, butyryloxy group, t-butyryloxy group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, which may have a substituent, Examples thereof include those having 2 to 25 carbon atoms such as n-dodecane carbonyloxy group, n-hexadecane carbonyloxy group, and the like. As the halogen atom, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

As a substituent for these groups, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, An alkoxycarbonyl group, a nitro group, etc. can be mentioned. As described above, at least one of R ₁ and R ₂ has 5 or more carbon atoms and may have a substituent, a cycloalkyl group that may have a substituent, An alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent . Examples of the substituent having 5 or more carbon atoms include those having 5 to 25 carbon atoms in the above specific examples.

Among these, as R ₄₁ and R ₄₂ , which may have a substituent, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and n-pentyl. Group, t-amyl group, n-hexyl group, n-octyl group and decanyl group are preferable, and the cycloalkyl group is preferably a cyclohexyl group, cyclooctyl group or cyclododecanyl group which may have a substituent. As the alkoxy group, which may have a substituent, a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, a pentyloxy group, a t-amyloxy group, n -Hexyloxy group, n-octyloxy group and n-dodecanoxy group are preferable, and the alkoxycarbonyl group may be a methoxy group which may have a substituent. Carbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n -Octyloxycarbonyl group and n-dodecanoxycarbonyl group are preferred, and the acyl group may have a substituent, formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butyl A carbonyl group and a t-amylcarbonyl group are preferable, and the acyloxy group may have an acetoxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, and an n-hexanecarbonyl group, which may have a substituent. Roxy group, n-octa N-carbonyloxy group is preferred.

The alkyl group having 5 or more carbon atoms and optionally having a substituent is preferably an n-pentyl group, a t-amyl group, an n-hexyl group, an n-octyl group or a decanyl group. The cycloalkyl group having 5 or more carbon atoms and optionally having a substituent is preferably a cyclohexyl group, a cyclooctyl group or a cyclododecanyl group. The alkoxy group having 5 or more carbon atoms and optionally having a substituent is preferably a pentyloxy group, a t-amyloxy group, a hexyloxy group, an n-octyloxy group, or a dodecanoxy group. Examples of the alkoxycarbonyl group having 5 or more carbon atoms which may have a substituent include a pentyloxycarbonyl group, a t-amyloxycarbonyl group, a hexyloxycarbonyl group, an n-octyloxycarbonyl group, and dodecaneoxycarbonyl. Groups are preferred. The acyl group having 5 or more carbon atoms and optionally having a substituent is preferably a valeryl group, a hexanoyl group, an octanoyl group or a t-amylcarbonyl group. As the acyloxy group having 5 or more carbon atoms, which may have a substituent, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group are preferable. Substituents for these groups include methoxy group, ethoxy group, t-butoxy group, chlorine atom, bromine atom, cyano group, hydroxyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group Groups are preferred.

The iodonium compound represented by formula (TA-4) used in the present invention uses sulfonic acid having a specific structure as described above as its counter anion, X ⁻ . Examples of the aliphatic hydrocarbon group which may have an R substituent in the counter anion include a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group. Moreover, R can mention the aromatic group which may have a substituent. Examples of the alkyl group for R include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and 2-ethylhexyl, which may have a substituent. And those having 1 to 20 carbon atoms such as a group, a decyl group and a dodecyl group. Examples of the cyclic alkyl group include an optionally substituted cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group, camphor group, tricyclodecanyl group, menthyl group and the like. Can do. Examples of the aromatic group include a phenyl group and a naphthyl group, which may have a substituent.

Among the above, as the alkyl group which may have a substituent of R, a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, n- Propyl group, n-butyl group, nonafluorobutyl group, n-pentyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, cyclic alkyl group A cyclopentyl group, a cyclohexyl group, and a camphor group can be mentioned. As the aromatic group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a p-toluyl group, a p-fluorophenyl group, a p-chlorophenyl group, a p-hydroxyphenyl group, p-, which may have a substituent. Examples thereof include a methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, and 6-hydroxy-2-naphthyl group.

Among the above substituents, more preferred specific examples of R ₄₁ and R ₄₂ are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, t- Amyl group, n-hexyl group, n-octyl group, cyclohexyl group, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n -Octyloxy group, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group, Butyryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group, t-amylca Bonyl group, acetoxy group, propionyloxy group, butyryloxy group, t-butyryloxy group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, hydroxyl group, chlorine atom, bromine atom, nitro group is there. Specific examples of more preferable groups having 5 or more carbon atoms include n-pentyl group, t-amyl group, n-hexyl group, n-octyl group, decanyl group, cyclohexyl group, pentyloxy group, t-amyloxy group, Hexyloxy group, n-octyloxy group, dodecaneoxy group, pentyloxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, dodecanoxyoxycarbonyl group, valeryl group, hexanoyl group, octanoyl group A t-amylcarbonyl group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octenecarbonyloxy group.

Specific examples of the more preferable sulfonic acid substituent R include methyl group, trifluoromethyl group, ethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-butyl group, nonafluorobutyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group P-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, 6-hydroxy-2-naphthyl group.

The total number of carbon atoms of the acid generated is preferably 1-30. More preferably, the number is 1 to 28, and still more preferably 1 to 25. If the total number of carbon atoms is less than 1, troubles such as poor resolution due to volatilization may occur, and if it exceeds 30, the development residue may be generated.
Specific examples of the compound represented by formula (TA-4) are shown below, but are not limited thereto. These compounds are used alone or in combination of two or more.

Examples of the imide sulfonate compound preferable as the thermal acid generator include compounds of the following general formula.

In the formula, C ₁ (carbon atom) and C ₂ (carbon atom) are bonded by a single bond or a double bond, and R ₅₁ or R ₅₂ may be the same or different, and the following (1) to (4) (1) each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or (2) a monocyclic or polycyclic ring that may contain one or more heteroatoms together with C ₁ and C ₂ (3) represents a residue containing N-sulfonyloxyimide that forms a condensed aromatic ring containing C ₁ and C ₂ .
R ₅₃ represents an alkyl group, a halogenated alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a camphor group.

In the general formula (TA-5), when R ₅₁ and R ₅₂ correspond to the case of (1), the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a tert-butyl group. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Examples of the aryl group include those having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group. When R ₅₁ and R ₅₂ correspond to the case (2), for example, the following partial structure can be given.

When R ₅₁ and R ₅₂ correspond to the case of (3), for example, the following partial structure can be given.

When R ₅₁ and R ₅₂ correspond to the case of (4), so-called at least two N-sulfonyloxyimide residues are a single bond at the R ₅₁ and R ₅₂ portions having the partial structures of (1) to (3) above. Or the thing couple | bonded with the following bivalent organic groups can be mention | raise | lifted. However, the following linking groups are used alone or in combination of two or more.
[Divalent organic _{group]: -O -, - S -,} - SO -, - SO 2 -, - NH -, - CO -, - CO 2 -, - NHSO 2 -, - NHCO -, - NHCO 2 -,

(R ₅₅ and R ₅₆ each represents a hydrogen atom or a methyl group. M represents an integer of 1 to 4.)

_Examples of the alkyl group for R ₅₃ include linear or branched alkyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable. Examples of the halogenated alkyl group include those in which one or two or more hydrogen atoms of the alkyl group are halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a fluorine atom. However, the halogen atom to be substituted may be plural types per molecule. Examples of the cyclic alkyl group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group, and polycyclic substituents such as norbornyl group, adamantyl group, and tricyclodecanyl group. I can give you. Examples of the alkenyl group include linear or branched alkenyl groups having 2 to 20 carbon atoms. A straight-chain or branched alkenyl group having 2 to 16 carbon atoms is preferable, and one having 2 to 12 carbon atoms is more preferable. In the case of an alkenyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.

_Examples of the aryl group of R ₅₃ include a phenyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group. Examples of the substituent of the aryl group and the aralkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group, a toluyl group, Aryl groups such as xylyl and mesityl groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, sec-butoxy groups, tert-butoxy groups and other lower alkoxy groups, vinyl groups, allyl groups, propenyl groups, butenyl groups, etc. And an acyl group such as alkenyl group, formyl group and acetyl group, and halogen atoms such as hydroxy group, carboxy group, cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Preferably, a lower alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, cyclohexyl group, phenyl group, toluyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy Group, lower alkoxy group such as tert-butoxy group, halogen atom such as cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Two or more kinds of substituents on the aryl group and the aralkyl group may be used.
Specific examples of these compounds are shown below, but are not limited thereto.

Preferred oxime sulfonate compounds as thermal acid generators include compounds of the following general formula.

In the above general formula (TA-6), R ₆₁ and R ₆₂ are an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, substituted group which may have a substituent having 1 to 16 carbon atoms. An aryl group, a heteroaryl group or a cyano group which may have a group. R ₆₁ and R ₆₂ are an alkylene chain, alkenylene chain, alkynylline chain, which may have a substituent having 2 to 8 carbon atoms, or phenylene, freelen, thienylene, which may have a substituent, It may be bonded to R ₆₁ or R _{62 of the} compound represented by another general formula (TA-6) through a linking chain containing —O—, —S—, —N—, and —CO—. . That is, the compound represented by the general formula (TA-6) includes those having two or three oxime sulfonate structures via a linking chain.
R ₆₃ represents an alkyl group, a cycloalkyl group, or an aryl group which may have a substituent, which may have a substituent having 1 to 16 carbon atoms.

Examples of the alkyl group having 1 to 16 carbon atoms in R ₆₁ to R ₆₃ include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, a t-amyl group, alkyl groups such as n-hexyl group, n-octyl group, i-octyl group, n-decyl group, undecyl group, dodecyl group, hexadecyl group, trifluoromethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro-t- Examples thereof include a butyl group, a perfluorooctyl group, a perfluoroundecyl group, and a 1,1-bistrifluoromethylethyl group.

Examples of the alkenyl group for R ₆₁ and R ₆₂ include allyl group, methallyl group, vinyl group, methylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, Examples include 2-oxo-3-pentenyl group, decapentaenyl group, 7-octenyl group and the like.

Examples of the alkynyl group in R ₆₁ and R ₆₂ include ethynyl group, propargyl group, 2-butynyl group, 4-hexynyl group, 2-octynyl group, phenylethynyl group, cyclohexylethynyl group and the like.

_Examples of the cycloalkyl group in R ₆₁ to R ₆₃ include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

Examples of the cycloalkenyl group for R ₆₁ and R ₆₂ include a cyclobutenyl group, a cyclohexenyl group, a cyclopentadienyl group, a bicyclo [4.2.4] dodeca-3,7-dien-5-yl group, and the like.

_Examples of the aryl group in R ₆₁ to R ₆₃ include those having 6 to 14 carbon atoms, such as phenyl group, tolyl group, methoxyphenyl group, and naphthyl group, which may have a substituent.

The above substituents include alkyl groups, cycloalkyl groups, alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms, iodine atoms), cyano groups, hydroxy groups, carboxy groups, nitro groups, aryloxy groups, alkylthio groups, aralkyls. And groups represented by the following general formula (1A).
Here, the alkyl group and the cycloalkyl group have the same meanings as described above. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group. Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, a furyl group, and a thienyl group.

In the above _{formula, R 61} and _{R 62} have the same meanings as _{R 61} and _{R 62} in formula (TA-6).

Specific examples of the compound represented by the general formula (TA-6) are shown below, but the present invention is not limited thereto.

Preferred examples of the oxime sulfonate-based acid generator as the thermal acid generator include compounds having at least one group represented by the following general formula (TA-7).

(In formula (TA-7), R ^70a and R ^70b each independently represents an organic group.)
The organic group of R ^70a and R ^{70b is} a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)) You may have.
As the organic group for R ^70a , a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable. The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. Means an aryl group substituted with.
R ^70a is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.

As the organic group for R ^70b , a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. As the alkyl group and aryl group for R ^70b, the same alkyl groups and aryl groups as those described above for R ^70a can be used.
R ^70b is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

As the oxime sulfonate-based acid generator, a compound represented by the following general formula (TA-7a) or (TA-7b) is preferably used because of its high acid generation efficiency against electron beam irradiation.

[In the formula (TA-7a), m ′ is 0 or 1; X is 1 or 2; R ₇₁ is a phenyl group, a heteroaryl group, or an alkyl group having 1 to 12 carbon atoms, or When m ′ is 0, an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenoxycarbonyl group, CN (cyano group); R ₇₂ is synonymous with R ₇₁ ; R ₇₃ ′ is 1 to 1 carbon atoms when X is 1; An alkyl group having 18 carbon atoms, an alkylene group having 2 to 12 carbon atoms when X is 2, a phenylene group; R ₇₄ and R ₇₅ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms; A is —S— , -O-, -N (R ₇₆ )-. _R76 represents an alkyl group, an aryl group or an aralkyl group. ]

[In the formula (TA-7b), R ₇₁ ′ is an alkylene group having 2 to 12 carbon atoms; R ₇₂ , R ₇₄ , R ₇₅ and A are as defined above; R ₇₃ is an alkyl group having 1 to 18 carbon atoms. . ]

As the above compound, the following thiolene-containing oxime sulfonate is particularly preferable.

Preferred examples of the general formula of nitrobenzyl sulfonate include compounds represented by the general formula (TA-9).

(Z in this formula is alkyl group, aryl group, alkylaryl group, halogen-substituted alkyl group, halogen-substituted aryl group, halogen-substituted alkylaryl group, nitro-substituted aryl group, nitro-substituted An alkylaryl group, an aryl group having a nitro substituent and a halogen substituent, an alkylaryl group having a nitro substituent and a halogen substituent, and the formula C ₆ H ₄ SO ₃ CHR′C ₆ H _4-m Q _m (NO ) is selected ₂ from the groups having, R represents a hydrogen atom or a methyl group, R 'are selected from hydrogen atoms and methyl groups, and nitro substituted aryl groups, each Q is a hydrocarbon radical, Hidorokarubono Independently selected from a xyl group, NO ₂ , a halogen atom and an organosilicon group, the value of m being 0, 1 or 2, provided that Q is not an acidic group)
Specific examples of the compound represented by the general formula (TA-9) include the following compounds.

Also sulfonic acid esters can be used.
For example, a sulfonic acid ester represented by the following general formula (TA-1) can be given.
R′—SO ₂ —O—R ″ (TA-1)
In the above formula, R ′ and R ″ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or an optionally substituted carbon group having 6 carbon atoms. Represents an aryl group of ˜20, and examples of the substituent include a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an acetylene group, and a linear or cyclic alkyl group having 1 to 10 carbon atoms.
Preferable specific examples of the sulfonic acid ester include the following.

As the sulfonic acid ester, a compound represented by the following general formula (TA-2) is more preferable from the viewpoint of heat resistance.
The molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.

A represents an h-valent linking group.
R ₀ represents an alkyl group, an aryl group, an aralkyl group, or a cyclic alkyl group.
R ₀ ′ represents a hydrogen atom, an alkyl group, or an aralkyl group.
h represents an integer of 2 to 8.

The h-valent linking group as A includes, for example, an alkylene group (eg, methylene, ethylene, propylene, etc.), a cycloalkylene group (eg, cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1,3). -Phenylene, 1,4-phenylene, naphthylene, etc.), an ether group, a carbonyl group, an ester group, an amide group, and a group obtained by removing h-2 arbitrary hydrogen atoms from a divalent group combining these groups. Can be mentioned.
The carbon number of the h-valent linking group as A is generally 1 to 15, preferably 1 to 10, and more preferably 1 to 6.

The alkyl group for R ₀ and R ₀ ′ is generally an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. is there. Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl and the like.
The aralkyl group for R ₀ and R ₀ ′ is generally an aralkyl group having 7 to 25 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 15 carbon atoms. is there. Specific examples include benzyl, toluylmethyl, mesitylmethyl, phenethyl and the like.
The cyclic alkyl group for R ₀ is generally a cyclic alkyl group having 3 to 20 carbon atoms, preferably a cyclic alkyl group having 4 to 20 carbon atoms, more preferably a cyclic alkyl group having 5 to 15 carbon atoms. is there. Specific examples include cyclopentyl, cyclohexyl, norbornyl, camphor group and the like.

The linking group as A may further have a substituent. The substituent is an alkyl group (an alkyl group having 1 to 10 carbon atoms, specifically, methyl, ethyl, propyl, butyl, hexyl). Octyl, etc.), aralkyl groups (aralkyl groups having 7 to 15 carbon atoms, specifically benzyl, toluylmethyl, mesitylmethyl, phenethyl, etc.), aryl groups (aryl groups having 6 to 10 carbon atoms, specifically Are phenyl, toluyl, xylyl, mesityl, naphthyl, etc.), an alkoxy group (the alkoxy group may be linear, branched or cyclic, and has 1 to 10 carbon atoms, specifically, Methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentoxy, cyclopentyloxy, cyclohexyloxy, etc.) A reeloxy group (an aryloxy group having 6 to 10 carbon atoms, specifically phenoxy, toluyloxy, 1-naphthoxy, etc.), an alkylthio group (which may be linear, branched or cyclic, the number of carbon atoms 1 to 10 alkylthio groups, specifically methylthio, ethylthio, linear or branched propylthio, cyclopentylthio, cyclohexylthio), arylthio groups (arylthio groups having 6 to 10 carbon atoms, specifically phenylthio , Toluylthio, 1-naphthylthio, etc.), acyloxy groups (acyloxy groups having 2 to 10 carbon atoms, specifically acetoxy, propanoyloxy, benzoyloxy, etc.), alkoxycarbonyl groups (alkoxycarbonyl having 1 to 10 carbon atoms) Groups such as methoxycarbonyl, ethoxycarbonyl, Or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, etc.), can be exemplified.

In the general formula (2), R ₀ is preferably an alkyl group or an aryl group. R ₀ ′ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.

Examples of the sulfonic acid ester in the present invention include the following specific compounds, but are not limited thereto.

As the sulfonic acid ester in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester of the present invention can be synthesized, for example, by reacting sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.

In the photosensitive resin composition of the present invention, the content of the thermal acid generator is preferably 1 to 20% by mass, more preferably 3 to 10% by mass based on the total solid content of the photosensitive resin composition.

(E) Compound containing at least one of alkoxymethyl group and acyloxymethyl group The composition of the present invention may contain a compound containing at least one of alkoxymethyl group and acyloxymethyl group. Even in the low-temperature curing process, it is possible to prevent melting and thermal shrinkage of the pattern during curing.

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, a compound in which an alkoxymethyl group or an acyloxymethyl group is substituted directly on an aromatic group or a nitrogen atom of the following urea structure on a triazine Can be cited as a representative structure.
The alkoxymethyl group or acyloxymethyl group of the compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups possessed by the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the compound is preferably 1500 or less, and preferably 180 to 1200.

R ₁₀₀ represents an alkyl group or an acyl group.
R ₁₀₁ and R ₁₀₂ independently represent a monovalent organic group, and may be bonded to each other to form a ring.

Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include compounds having the following general formula.

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, Or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by —C (R ⁴ ) ₂ COOR ⁵ (R ⁴ is a hydrogen atom or a carbon number) Represents an alkyl group of 1 to 4, and R ⁵ represents a group capable of leaving by the action of an acid))).
R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, and e is independently 0 to 3.
The group that decomposes by the action of an acid to generate an alkali-soluble group refers to a group that decomposes by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group (hereinafter also referred to as an acid-decomposable group).
A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
Examples of the group capable of leaving with an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R ₃₆ to R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.

As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product or a compound synthesized by a known method may be used.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
The addition amount of these compounds is preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the total amount of the resin of the present invention.

(E ′) Compound containing methacryloyl group or acryloyl group The composition of the present invention may contain a compound containing methacryloyl group or acryloyl group.
The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. Since these compounds are insoluble in an alkaline developer, they have a function of suppressing the alkali solubility of the composition, and are useful for good image formation in order to suppress film loss in unexposed areas. In addition, although the specific reaction mechanism is not grasped, the molecular weight of components constituting the composition partially increases due to the reaction of the acrylic group or methacrylic group with the compound in the composition at the stage of the cure reaction. As a result, film properties are improved. Therefore, it is preferable to use a compound having two or more acryloyl groups and methacryloyl groups in one molecule, more preferably four or more functional groups, because this compound can exhibit a function as a crosslinking compound.
Further, it is more preferable that the skeleton containing an acrylolyl group or a methacryloyl group is a ring structure such as an aromatic ring or an alicyclic ring, particularly a substance containing an alicyclic structure, because of the exposure light transmittance and the rigidity of the cured film.
Furthermore, if the length (n) of the ethylene oxide (EO) chain and propylene oxide (PO) chain in the skeleton is long, the rigidity of the film is lost, so that n = 1 to 5 is preferable.

Preferable specific examples include NK-10 series made by Shin-Nakamura Chemical Co., Ltd., monofunctional AMP-10G, AMP-20GY, AM30G, AM90G, AM230G, ACB-3, A-BH, A-IB, A-SA, A -OC-18E, 720A, S-1800A, ISA, AM-130G, LA, M-20G, M-90G, M230G, PHE-1G, SA, CB-1, CB-3, CB-23, TOPOLENE-M , S-1800M, IB, OC-18E, S, bifunctional A-200, A-400, A-600, A-1000, ABE-300, A-BPE-4, A-BPE-10, A- BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A-B1206PE, A-HD-N A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD-N, NOD, IND, BPE -100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3PG, 9PG, trifunctional A-9300, AT-30E, A-TMPT- 3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, TMPT, TMPT-9EO, 4 or more functional ATM-35E, ATM- Examples thereof include 4E, AD-TMP, AD-TMP-L, ATM-4P, A-TMMT, and A-DPH.
Particularly preferred examples include the following polyfunctional monomers.

The addition amount of the compound containing a methacryloyl group or an acryloyl group in the molecule of the present invention is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin having a repeating unit represented by the general formula (1). Is preferred. More preferably, they are 1 mass part or more and 20 mass parts or less, Most preferably, they are 2 mass parts or more and 15 mass parts or less. By making the addition amount 0.5 parts by mass or more, the effect of the present invention can be further obtained, and by suppressing the addition amount appropriately, it is possible to prevent a decrease in heat resistance of the cured film.

(F) Adhesion promoter In the positive photosensitive resin composition in the present invention, an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent for imparting adhesion may be added as necessary. Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl. Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris ( Acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like. When an adhesion promoter is used, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin of the present invention.

(G) Solvent The solvent is not particularly limited as long as it can dissolve the composition of the present invention. However, in order to prevent the solvent from evaporating more than necessary at the time of coating and precipitating the solid content of the composition at the time of coating, Solvents with the above boiling points are preferred.
For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound (preferably carbon And organic solvents such as alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, and amide solvents.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methyl Preferred is cycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
Preferred examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone and 1,3-dimethyl-2-imidazolidinone.
In addition, dimethyl sulfoxide and sulfolane are preferable.
Among the above, N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI) are more preferable solvents. , N, N-dimethylformamide (DMF), cyclopentanone, cyclohexanone, cycloheptanone and the like. More preferred are γ-butyrolactone, N-methylpyrrolidone, cyclopentanone, and cyclohexanone.
These solvents may be used alone or in combination of two or more.
The total solid concentration in the photosensitive resin composition of the present invention is generally 10 to 40% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 30% by mass.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition of the present invention, the base polymer, a photoacid generator, and if necessary, photosensitizers, organic solvent, basic compound, surfactant, dissolution modifiers, ultraviolet absorbers, storage stability It can be prepared as a solution by mixing additives such as an agent and an antifoaming agent. The order and method of mixing are not particularly limited.
Further, the photosensitive resin composition of the present invention may be a dry film. The dry film can be prepared, for example, by applying the above solution onto a support such as metal or polyethylene terephthalate, drying, and then peeling off the support. When the support is a film of polyethylene terephthalate or the like, it can be used as it is as the photosensitive resin composition of the present invention.
As a method for applying the photosensitive resin composition of the present invention on a support, for example, spin coating, roll coating, flow coating, dip coating, spray coating, and a known method such as doctor coating.
The thickness of the applied film can be set according to the use, but is preferably 0.05 to 200 μm, more preferably 0.1 to 100 μm.
Examples of the film used as the support include polyethylene terephthalate, polypropylene, polyethylene, polyester, and polyvinyl alcohol.
When the photosensitive resin composition of the present invention is a dry film, if necessary, the photosensitive resin composition is coated with a protective film for the purpose of protecting the photosensitive resin composition from scratches, dust, chemicals, and the like. May be. As a protective film, a polyethylene film, a polypropylene film, etc. are mentioned, for example, and the adhesive force with the photosensitive resin composition of this invention is smaller than a support body.
Moreover, you may provide the peeling layer between the protective film and the photosensitive resin composition of this invention.
The dry film may be wound up into a roll.

<Pattern forming material, photosensitive film, and cured film>
A step of forming a photosensitive film by coating the photosensitive resin composition of the present invention on a substrate, a step of heating the substrate, a step of exposing the photosensitive film on the substrate to actinic rays or radiation, after exposure A positive pattern can be formed using the photosensitive resin composition of the present invention by the step of heating the substrate and then the step of developing the substrate using an alkaline developer.
Therefore, the photosensitive resin composition of the present invention is a pattern forming material.
Although it does not specifically limit as a board | substrate, For example, metal plates, such as aluminum, zinc, gold | metal | money, silver, nickel, a copper foil laminated board, a glass plate, a silicon wafer etc. are mentioned.
As a method for coating the photosensitive resin composition of the present invention on a substrate, when the photosensitive resin composition of the present invention is a solution, for example, spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating Known methods such as The thickness of the applied photosensitive film can be set according to the use, but is preferably 0.05 to 200 μm, more preferably 0.1 to 100 μm.
When the photosensitive resin composition of the present invention is a dry film and there is a protective film, after the protective film is peeled off, the photosensitive resin composition layer is applied so as to directly touch the substrate, for example, a method of laminating Etc. By setting the temperature to 80 to 160 ° C. at the time of lamination, the heat treatment in the next step can be omitted.
After applying the photosensitive resin composition of the present invention to a substrate, the substrate may be heated. When the photosensitive resin composition of the present invention is a solution, examples of the heating method include known methods such as heating with a hot plate or an oven. By heating, it is possible to evaporate the organic solvent. The heating temperature is preferably 80 ~ 160 ° C..
When the photosensitive resin composition of the present invention is a dry film, this step can be omitted if heating is performed during lamination.
After heating, the photosensitive film can be irradiated with actinic rays or radiation using a photomask, a reduction projection exposure machine, a direct drawing machine or the like.
Examples of actinic rays or radiation include far-infrared rays, visible rays, g-rays, h-rays, i-rays and other near ultraviolet rays, KrF excimer lasers, ArF excimer lasers, DUV (far-ultraviolet rays), EUV (extreme ultraviolet rays), and electron beams. And X-rays. In a portion irradiated with radiation or the like, the photoacid generator is decomposed to generate an acid.

It is preferable to heat the substrate after irradiation. Examples of the heating method include those used for heating after coating. By heating, the structure derived from the compound represented by the general formula (I) is eliminated from the compound having the group represented by the general formula (III), and the hydroxyl group or the carboxyl group is regenerated. The heating temperature is preferably 80 to 160 ° C.
After heating, when the dry film is used, the support is removed, and when the dry film is not used, the development is performed with an alkaline developer to obtain a positive resist pattern. Examples of the developing method include known methods such as an immersion method, a paddle method, and a spray method. Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4. 3.0] -5-nonane and an alkaline aqueous solution obtained by dissolving a basic substance. You may use a basic substance individually or in mixture of 2 or more types. In addition, a suitable amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant can be added to the developer.

After development, the substrate may be washed with water or heat-dried as necessary.
The pattern formed on the substrate may be a known pattern such as dry etching of the substrate with a chlorine-based gas, a fluorine-based gas (CF ₄ / CH ₂ F ₂ mixed gas, etc.), an oxygen-based gas or the like using the pattern as a mask. It can be subjected to a process.
Furthermore, this invention relates to the cured film obtained by heat-processing the said photosensitive resin composition. Specifically, a resin having a group represented by formula (III), all or part of the carboxyl groups of the polyimide precursor containing a repeating unit represented by the general formula (VIII) is formula (IV) All or part of the hydroxyl group of the polyimide precursor substituted with the group represented by the formula (II) or the polybenzoxazole precursor containing the repeating unit represented by the formula (IX) is represented by the formula (III) In the case of a polybenzoxazole precursor substituted with a group, a polyimide film or a polybenzoxazole film having excellent film characteristics can be formed by heat-treating the obtained pattern to form an imidized or oxazolated film. The heating temperature is preferably 250 to 400 ° C.
The photosensitive resin composition of this invention is excellent in the stability in the heating process of the photosensitive film | membrane obtained, and long-term storage stability, and is excellent in a sensitivity and resolution.

<Hardened relief pattern and manufacturing method thereof>
The present invention also relates to a cured relief pattern and a method for producing the same.
Specifically, the cured relief pattern of the present invention is
(A) forming the photosensitive film on a substrate;
(A) a step of exposing the photosensitive film with actinic rays or radiation;
(C) It can be produced by a production method comprising a step of developing so as to remove an exposed portion of the photosensitive film with an aqueous alkaline developer, and (d) a step of heat-treating the obtained relief pattern. .
In addition, the photosensitive resin composition of the present invention is applied on a semiconductor element so that the thickness after heat curing becomes a predetermined thickness (for example, 0.1 to 30 μm), prebaked, exposed, developed, and heat cured. A semiconductor device can be manufactured.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[GPC measurement conditions]
In the GPC measurement thereafter, HPC-8220GPC (manufactured by Tosoh Corporation), guard column: TSK guard column Super AW-H, column: TSK gel Super AWM-H were directly connected, N-methyl having a column temperature of 50 ° C. and a sample concentration of 0.5 mass%. Inject 20 μl of -2-pyrrolidone solution, and flow N-methyl-2-pyrrolidone solution (containing LiBr (10 mM) and H ₃ PO ₄ (10 mM)) as an elution solvent at a flow rate of 0.35 ml / min. This was done by detecting the sample peak with a detector. Mw and Mn were calculated using a calibration curve prepared using standard polystyrene.
The acid value was determined by neutralization titration with a 0.1 mol / L KOH alcohol solution.

(Synthesis Example 1) Synthesis of 1-chloro-1-methoxy-2-phenylpropane In a 1 L flask equipped with a thermometer, a stirrer and a calcium chloride tube, 120.0 g of 2-phenylpropionaldehyde, 120.0 g of magnesium sulfate, 600 mL of methanol and 2.08 g of 10-camphorsulfonic acid were added and reacted at 50 ° C. for 11 hours. The reaction solution was cooled to 0 ° C., 4.53 g of triethylamine was added, and the mixture was stirred at 0 ° C. for 30 minutes. Magnesium sulfate was filtered, and the filtrate was extracted with ethyl acetate and saturated aqueous sodium hydrogen carbonate. The obtained organic phase was washed with distilled water and saturated brine, dried over sodium sulfate, and then concentrated under reduced pressure to obtain 144.2 g of a transparent liquid.
In a 1 L flask equipped with a thermometer, stirrer, and calcium chloride tube, 144.2 g of the above liquid and 84.2 g of acetyl chloride were added and reacted at room temperature (25 ° C.) for 2 hours, and then concentrated under reduced pressure to be transparent. 132.2 g of liquid was obtained. ^{From 1} H-NMR measurement (deuterated chloroform), it was confirmed that the liquid was 1-chloro-1-methoxy-2-phenylpropane (a-1).
¹ H-NMR δ 7.37-7.20 (5H, m), 5.58 (1H, m), 3.46 (3H, m), 3.28 (1H, m), 1.43 (3H , M)

Synthesis Example 2 Synthesis of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane In a 300 mL flask equipped with a thermometer, stirrer, and calcium chloride tube, 59.8 g of 2-phenylpropionaldehyde, sulfuric acid Magnesium 50.0 g, 2-methoxyethanol 101.8 g, and 10-camphorsulfonic acid 1.04 g were added and reacted at 50 ° C. for 12 hours. The reaction solution was cooled to 0 ° C., 2.26 g of triethylamine was added, and the mixture was stirred at 0 ° C. for 30 minutes. Magnesium sulfate was filtered, and the filtrate was extracted with ethyl acetate and saturated aqueous sodium hydrogen carbonate. The obtained organic phase was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain 91.6 g of a transparent liquid.
91.6 g of the above liquid and 42.0 g of acetyl chloride were added to a 300 mL flask equipped with a thermometer, a stirrer, and a calcium chloride tube, reacted at room temperature for 2 hours, concentrated under reduced pressure, and 97.1 g of a transparent liquid. Got. ^{From the 1} H-NMR measurement (deuterated chloroform), it was confirmed that the liquid was 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane (a-2).
¹ H-NMR δ 7.44-7.11 (5H, m), 5.75 (1H, m), 3.99 (1H, m), 3.78-3.25 (7H, m), 1 .48 (3H, m)

(Synthesis Example 3) Synthesis of 1-chloro-1,2-dimethoxypropane A reaction was conducted in the same manner as in Synthesis Example 1 except that 2-methoxypropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. 1-chloro-1,2-dimethoxy propane (a-3) was obtained as a clear liquid.
Synthesis Example 4 Synthesis of 1-chloro-1-methoxy-2-phenoxypropane The same reaction as in Synthesis Example 1 except that 2-phenoxypropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. 1-Chloro-1-methoxy-2-phenoxypropane (a-4) was obtained as a transparent liquid.
Synthesis Example 5 Synthesis of 2-acetyl-1-chloro-1-methoxypropane The same reaction as in Synthesis Example 1 except that 2-acetylpropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. And 2-acetyl-1-chloro-1-methoxypropane (a-5) was obtained as a transparent liquid.
Synthesis Example 6 Synthesis of 1-chloro-2- (ethoxycarbonyl) -1-methoxypropane Synthesis Example 1 except that 2- (ethoxycarbonyl) propionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. The reaction was carried out in the same manner as in 1 to obtain 1-chloro-2- (ethoxycarbonyl) -1-methoxypropane (a-6) as a transparent liquid.
Synthesis Example 7 Synthesis of 1-chloro-1-methoxy-2- (phenoxycarbonyl) propane Synthesis Example except that 2- (phenoxycarbonyl) propionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. The reaction was carried out in the same manner as in 1 to obtain 1-chloro-1-methoxy-2- (phenoxycarbonyl) propane (a-7) as a transparent liquid.

Synthesis Example 8 Synthesis of 1-chloro-2-cyano-1-methoxypropane The same reaction as in Synthesis Example 1 except that 2-cyanopropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. 1-Chloro-2-cyano-1-methoxypropane (a-8) was obtained as a transparent liquid.
(Synthesis Example 9) Synthesis of 1,2-dichloro-1-methoxypropane A reaction was conducted in the same manner as in Synthesis Example 1 except that 2-chloropropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. 1,2-Dichloro-1-methoxypropane (a-9) was obtained as a transparent liquid.
Synthesis Example 10 Synthesis of 1-chloro-1- (cyclohexyloxy) -2-phenylpropane The same reaction as in Synthesis Example 2 was conducted except that cyclohexanol was used in place of 2-methoxyethanol in Synthesis Example 2. 1-chloro-1- (cyclohexyloxy) -2-phenylpropane (a-10) was obtained as a transparent liquid.
(Synthesis Example 11) Synthesis of 1-chloro-1-phenoxy-2-phenylpropane A reaction was conducted in the same manner as in Synthesis Example 2 except that phenol was used instead of 2-methoxyethanol in Synthesis Example 2. -1-Phenoxy-2-phenylpropane (a-11) was obtained as a transparent liquid.
(Synthesis Example 12) 1-chloro-1- (2-phenoxyethyl) -2-in Synthesis Example 2 of phenylpropane except for using 2-phenoxyethanol in place of 2-methoxyethanol in the same manner as in Synthesis Example 2 The reaction was performed to obtain 1-chloro-1- (2-phenoxyethoxy) -2-phenylpropane (a-12) as a transparent liquid.
(Synthesis Example 13) Synthesis of 1-bromo-1-methoxy-2-phenylpropane The reaction was conducted in the same manner as in Synthesis Example 1 except that acetyl bromide was used instead of acetyl chloride in Synthesis Example 1. -1-Methoxy-2-phenylpropane (a-13) was obtained as a yellow liquid.

(Comparative Synthesis Example 1) Synthesis of 1-chloro-1-ethoxyethane 8 g of ethyl vinyl ether was cooled to 5 ° C., and 3.3 g of hydrogen chloride gas was blown into the liquid over 1 hour, thereby allowing 10.1 g of a colorless transparent liquid. Got. ^{From 1} H-NMR measurement (deuterated chloroform), it was confirmed that the liquid was 1-chloro-1-ethoxyethane (a-14).
(Comparative Synthesis Example 2) Synthesis of 1-chloro-1-methoxy-2-methylpropane 0.19 g of p-toluenesulfonic acid monohydrate was dissolved in 128.2 g of methanol, and isobutyraldehyde was cooled to 20 ° C. or lower. 72.1 g was dripped. Washing with 200 g of 1% sodium carbonate aqueous solution, and distillation of the oil phase obtained by liquid separation at atmospheric pressure gave 35 g of isobutyraldehyde dimethyl acetal. To this, 0.06 g of p-toluenesulfonic acid monohydrate was dissolved and heated to 200 ° C. 12 g of the distilled liquid was collected, washed with 10 g of a 1% aqueous sodium carbonate solution, and the oily phase obtained by liquid separation was distilled under reduced pressure to obtain 8 g of a colorless transparent liquid. This was cooled to 5 ° C., and 3.7 g of hydrogen chloride gas was blown into the liquid over 1 hour to obtain 11.4 g of a colorless transparent liquid. ^{From 1} H-NMR measurement (deuterated chloroform), it was confirmed that the liquid was 1-chloro-1-methoxy-2-methylpropane (a-15).

(Examples 1 to 13 and Comparative Examples 1 and 2) Storage Stability Test of Protective Agents 5 g of the protective agents obtained in Synthesis Examples 1 to 13 and Comparative Synthesis Examples 1 and 2 were each filled into a 10 ml glass vial, After sealing, it was aged for 15 days in a constant temperature layer at 50 ° C. The remaining amount of the protective agent was quantified from ¹ H-NMR measurement (deuterated chloroform, internal standard: trimethoxybenzene) after the lapse of time, and the residual rate after aging was calculated based on the amount of the protective agent before the lapse of time. The results are shown in Table 1.

As is apparent from the results shown in Table 1, it can be seen that Comparative Examples 1 and 2 using a protective agent that does not satisfy the general formula (I) have a small residual rate after aging.
On the other hand, it can be seen that Examples 1 to 13 using the protective agent represented by the general formula (I) have a high residual ratio after aging and are extremely excellent in storage stability.

(Example 14) Protection of carboxyl group of methacrylic acid with 1-chloro-1-methoxy-2-phenylpropane (a-1) 10.0 g of methacrylic acid was dissolved in 30 ml of tetrahydrofuran and cooled to 0 ° C. 22.5 g of 1-chloro-1-methoxy-2-phenylpropane was added, and 14.1 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours. Distilled water (50 ml) was added to the reaction solution, extraction was performed with ethyl acetate, and the obtained organic phase was concentrated under reduced pressure to obtain 25.9 g of a tan liquid. ^{From the 1} H-NMR spectrum, it was confirmed that the liquid was 1-methoxy-2-phenylpropyl methacrylate (b-1).
¹ H-NMR δ 7.37-7.20 (5H, m), 6.32 (1H, s), 5.80 (1H, m), 5.59 (1H, m), 3.56 (3H , M), 3.39 (1H, m), 1.96 (3H, m), 1.43 (3H, m)

(Example 15) Protection of carboxyl group of methacrylic acid by 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane (a-2) 10.0 g of methacrylic acid was dissolved in 30 ml of tetrahydrofuran and dissolved at 0 ° C. After cooling, 27.9 g of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane was added, and 14.1 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours. Distilled water (50 ml) was added to the reaction solution, extracted with ethyl acetate, and the resulting organic phase was concentrated under reduced pressure to obtain 31.0 g of a tan liquid. ^{From the 1} H-NMR spectrum, it was confirmed that the liquid was 1- (2-methoxyethoxy) -2-phenylpropyl methacrylate (b-2) methacrylate.
¹ H-NMR δ 7.44-7.12 (5H, m), 6.34 (1H, s), 5.81 (1H, m), 5.60 (1H, m), 4.01 (1H , M), 3.78-3.25 (7H, m), 1.96 (3H, m), 1.45 (3H, m)

(Comparative Example 3) Protection of carboxyl group of methacrylic acid with 1-chloro-1-ethoxyethane (a-14) 10.0 g of methacrylic acid was dissolved in 30 ml of tetrahydrofuran, cooled to 0 ° C., and then 1-chloro- 13.2 g of 1-ethoxyethane was added, and 14.1 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of the addition, the mixture was stirred for about 2 hours. Distilled water (50 ml) was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic phase was concentrated under reduced pressure to obtain 15.1 g of 1-ethoxyethyl methacrylate (b-14).
(Comparative Example 4) Protection of carboxyl group of methacrylic acid with 1-chloro-1-methoxy-2-methylpropane (a-15) 10.0 g of methacrylic acid was dissolved in 30 ml of tetrahydrofuran and cooled to 0 ° C. 15.0 g of 1-chloro-1-methoxy-2-methylpropane was added, and 14.1 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours. Distilled water (50 ml) was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic phase was concentrated under reduced pressure to obtain 16.8 g of 1-methoxy-2-methylpropyl methacrylate (b-15).

(Example 16) Protection of hydroxyl group of m-cresol by 1-chloro-1-methoxy-2-phenylpropane (a-1) 10.0 g of m-cresol was dissolved in 30 ml of tetrahydrofuran and cooled to 0 ° C. Thereafter, 17.9 g of 1-chloro-1-methoxy-2-phenylpropane was added, and 11.2 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours. 50 ml of distilled water was added to the reaction solution, extracted with ethyl acetate, and the resulting organic phase was concentrated under reduced pressure to give (1-methoxy-2-phenylpropyl)-(3-methylphenyl) ether (c-1) 22.5 g was obtained.
Example 17 Protection of hydroxyl group of m-cresol by 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane (a-2) 10.0 g of m-cresol was dissolved in 30 ml of tetrahydrofuran, After cooling to 0 ° C., 22.2 g of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane was added, and 11.2 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours. 50 ml of distilled water was added to the reaction solution, extracted with ethyl acetate, and the resulting organic phase was concentrated under reduced pressure to give (1- (2-methoxyethoxy) -2-phenylpropyl)-(3-methylphenyl) ether. (C-2) 26.7 g was obtained.
(Comparative Example 5) Protection of hydroxyl group of m-cresol by 1-chloro-1-ethoxyethane (a-14) 10.0 g of m-cresol was dissolved in 30 ml of tetrahydrofuran and cooled to 0 ° C. 10.5 g of chloro-1-ethoxyethane was added, and 11.2 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours. 50 ml of distilled water was added to the reaction solution, extracted with ethyl acetate, and the obtained organic phase was concentrated under reduced pressure to obtain 13.7 g of (1-ethoxyethyl)-(3-methylphenyl) ether (c-14). Obtained.
(Comparative Example 6) Protection of hydroxyl group of m-cresol by 1-chloro-1-methoxy-2-methylpropane (a-15) 10.0 g of m-cresol was dissolved in 30 ml of tetrahydrofuran and cooled to 0 ° C. Thereafter, 11.9 g of 1-chloro-1-methoxy-2-methylpropane was added, and 11.2 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours. 50 ml of distilled water was added to the reaction solution, extracted with ethyl acetate, and the resulting organic phase was concentrated under reduced pressure to give (1-methoxy-2-methylpropyl)-(3-methylphenyl) ether (c-15) 15.1 g was obtained.

(Synthesis Example 14) Synthesis of polymethacrylic resin 100 g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a dropping device, a stirrer, a thermometer, a cooling tube and a nitrogen gas introduction tube, heated to 80 ° C., and under a nitrogen atmosphere 27.4 g of 1-methoxy-2-phenylpropyl methacrylate (b-1), 57.7 g of methyl methacrylate, 13.5 g of butyl methacrylate, and 10.0 g of azobisisobutyronitrile (AIBN) What was melt | dissolved uniformly was dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, a mixed solution of AIBN / propylene glycol monomethyl acetate = 0.15 g / 0.3 g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction. The obtained resin solution was purified by reprecipitation with hexane to obtain 79 g of a white solid (d-1). The weight average molecular weight of the solid was 7,500.
(Synthesis Example 15) Synthesis of polymethacrylic resin 100 g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a dropping device, a stirring device, a thermometer, a cooling tube and a nitrogen gas introduction tube, heated to 80 ° C., and under a nitrogen atmosphere 32.5 g of 1- (2-methoxyethoxy) -2-phenylpropyl (b-2) methacrylate, 57.7 g of methyl methacrylate, 13.5 g of butyl methacrylate and azobisisobutyronitrile (AIBN) ) A solution in which 10.0 g was uniformly dissolved was dropped from a dropping device over 4 hours. After completion of the dropwise addition, a mixed solution of AIBN / propylene glycol monomethyl acetate = 0.15 g / 0.3 g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction. The obtained resin solution was purified by reprecipitation with hexane to obtain 83 g of a white solid (d-2). The weight average molecular weight of the solid was 8,200.

(Comparative Synthesis Example 3) Synthesis of polymethacrylic resin 100 g of propylene glycol monomethyl ether acetate was charged in a flask equipped with a dropping device, a stirrer, a thermometer, a cooling tube and a nitrogen gas introduction tube, heated to 80 ° C., and a nitrogen atmosphere While stirring below, 27.4 g of 1-ethoxyethyl methacrylate (b-14), 57.7 g of methyl methacrylate, 13.5 g of butyl methacrylate and 10.0 g of azobisisobutyronitrile (AIBN) are uniformly dissolved. What was dripped was dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, a mixed solution of AIBN / propylene glycol monomethyl acetate = 0.15 g / 0.3 g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction. The obtained resin solution was purified by reprecipitation with hexane to obtain 72 g of a white solid (d-14). The weight average molecular weight of the solid was 7,100.
(Comparative Synthesis Example 4) Synthesis of polymethacrylic resin 100 g of propylene glycol monomethyl ether acetate was charged in a flask equipped with a dropping device, a stirrer, a thermometer, a cooling tube and a nitrogen gas introduction tube, heated to 80 ° C., and a nitrogen atmosphere While stirring at the bottom, 27.4 g of 1-methoxy-2-methylpropyl methacrylate (b-15), 57.7 g of methyl methacrylate, 13.5 g of butyl methacrylate and 10.0 g of azobisisobutyronitrile (AIBN) It was added dropwise over 4 hours from a dropping machine that uniformly dissolved. After completion of the dropwise addition, a mixed solution of AIBN / propylene glycol monomethyl acetate = 0.15 g / 0.3 g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction. The obtained resin solution was purified by reprecipitation with hexane to obtain 73 g of a white solid (d-15). The weight average molecular weight of the solid was 7,300.

(Example 18) Protection of hydroxyl group of phenol novolak resin with 1-chloro-1-methoxy-2-phenylpropane 2.7 g of phenol novolak resin [manufactured by Showa Polymer Co., Ltd.] having a weight average molecular weight of 3,220 was added to methyl ethyl ketone. was dissolved in 17.5 ml, this 1-chloro-1-methoxy-2-phenylpropane 2.30g in a solution was added and after complete dissolution by stirring, about 30 minutes triethylamine 2.53g stirring It was dripped over. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then added dropwise to 500 ml of pure water to cause reprecipitation to produce a pale yellow solid (e -1) 4.1 g was obtained. ^{From 1} H-NMR spectrum, it was found that 40 mol% of the hydroxyl group was substituted with 1-methoxy-2-phenylpropoxy group. The weight average molecular weight of the target product was 4,370.

(Example 19) Protection of hydroxyl group of phenol novolak resin with 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane Phenol novolak resin having a weight average molecular weight of 3,220 [manufactured by Showa Polymer Co., Ltd.] 2.7 g is dissolved in 17.5 ml of methyl ethyl ketone, and 2.85 g of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane is added to this solution, and the mixture is stirred to dissolve completely. Then, 2.53 g of triethylamine was added dropwise over about 30 minutes. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then added dropwise to 500 ml of pure water to cause reprecipitation to produce a pale yellow solid (e -2) 4.6 g was obtained. ^{From 1} H-NMR spectrum, it was found that 40 mol% of the hydroxyl group was substituted with 1- (2-methoxyethoxy) -2-phenylpropoxy group. The weight average molecular weight of the target product was 4,700.
(Comparative Example 7) Protection of hydroxyl group of phenol novolak resin with 1-chloro-1-ethoxyethane 2.7 g of phenol novolak resin having a weight average molecular weight of 3,220 [manufactured by Showa Polymer Co., Ltd.] was added to 17.5 ml of methyl ethyl ketone. After dissolution, 1.36 g of 1-chloro-1-ethoxyethane was added to this solution and stirred to dissolve completely, then 2.53 g of triethylamine was added dropwise over about 30 minutes with stirring. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then added dropwise to 500 ml of pure water to cause reprecipitation to produce a pale yellow solid (e -14) 3.2 g was obtained. ^{From 1} H-NMR spectrum, it was found that 30 mol% of the hydroxyl groups were substituted with 1-ethoxyethoxy group. The target product had a weight average molecular weight of 3,780.

(Comparative Example 8) Protection of hydroxyl group of phenol novolak resin by 1-chloro-1-methoxy-2-methylpropane 2.7 g of phenol novolak resin [manufactured by Showa Polymer Co., Ltd.] having a weight average molecular weight of 3,220 was added to methyl ethyl ketone. was dissolved in 17.5 ml, this 1-chloro-1-methoxy-2-methyl propane 1.53g in a solution was added and after complete dissolution by stirring, about 30 minutes triethylamine 2.53g stirring It was dripped over. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then added dropwise to 500 ml of pure water to cause reprecipitation to produce a pale yellow solid (e -15) 3.4 g was obtained. ^{From 1} H-NMR spectrum, it was found that 30 mol% of the hydroxyl group was substituted with 1-methoxy-2-methylpropoxy group. The target product had a weight average molecular weight of 3,890.

(Example 20) 1-chloro-1-methoxy-2-phenylpropane according polyhydroxystyrene polyhydroxystyrene protected weight average molecular weight of 20,000 of the hydroxyl groups (manufactured by Aldrich) 2.7 g of N, N-dimethyl Dissolve in 17.5 ml of acetamide, add 2.04 g of 1-chloro-1-methoxy-2-phenylpropane to this solution, stir to dissolve completely, then add 2.23 g of triethylamine to about 30 with stirring. Added dropwise over a period of minutes. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then dropped into 500 ml of pure water to cause reprecipitation, whereby a pale yellow solid (f -1) 3.6 g was obtained. ^{From 1} H-NMR spectrum, it was found that 35 mol% of the hydroxyl group was substituted with 1-methoxy-2-phenylpropoxy group. The weight average molecular weight of the target product was 25,200.
(Example 21) Protection of hydroxyl group of polyhydroxystyrene by 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane 2.7 g of polyhydroxystyrene (Aldrich) having a weight average molecular weight of 20,000 was used. After dissolving in 17.5 ml of N, N-dimethylacetamide and adding 2.52 g of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane to this solution and stirring to dissolve completely, While stirring, 2.23 g of triethylamine was added dropwise over about 30 minutes. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then dropped into 500 ml of pure water to cause reprecipitation, whereby a pale yellow solid (f -2) 4.0 g was obtained. ^{From 1} H-NMR spectrum, it was found that 35 mol% of the hydroxyl group was substituted with 1- (2-methoxyethoxy) -2-phenylpropoxy group. The weight average molecular weight of the target product was 26,800.

(Comparative Example 9) Protection of hydroxyl group of polyhydroxystyrene by 1-chloro-1-ethoxyethane 2.7 g of polyhydroxystyrene having a weight average molecular weight of 20,000 (Aldrich) was added to 17.5 ml of N, N-dimethylacetamide. 1-Chloro-1-ethoxyethane (1.20 g) was added to this solution, and the mixture was completely dissolved by stirring. Then, 2.23 g of triethylamine was added dropwise over about 30 minutes with stirring. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then dropped into 500 ml of pure water to cause reprecipitation, whereby a pale yellow solid (f -14) 2.9 g was obtained. ^{From 1} H-NMR spectrum, it was found that 30 mol% of the hydroxyl groups were substituted with 1-ethoxyethoxy group. The weight average molecular weight of the target product, was 22,500.
(Comparative Example 10) 1-chloro-1-methoxy-2-methylpropane by polyhydroxystyrene polyhydroxystyrene protected weight average molecular weight of 20,000 of the hydroxyl groups (manufactured by Aldrich) 2.7 g of N, N-dimethyl Dissolve in 17.5 ml of acetamide, add 1.35 g of 1-chloro-1-methoxy-2-methylpropane to this solution, stir to dissolve completely, then add 2.23 g of triethylamine to about 30 with stirring. Added dropwise over a period of minutes. After completion of dropping, the mixture was stirred for about 3 hours. Next, 20 times the amount of pure water was added to the resulting solution, extracted with methyl isobutyl ketone, the solvent was distilled off, and then dropped into 500 ml of pure water to cause reprecipitation, whereby a pale yellow solid (f -15) 3.0 g was obtained. ^{From 1} H-NMR spectrum, it was found that 30 mol% of the hydroxyl group was substituted with 1-methoxy-2-methylpropoxy group. The target product had a weight average molecular weight of 23,000.

(Synthesis Example 16) Synthesis of polyamic acid In a 5000 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 64.04 g of trans-1,4-cyclohexanediamine (manufactured by Iwatani Gas Co., Ltd.) was placed, and NMP (N -Methyl-2-pyrrolidone) was dissolved in 2427.2 g, and 275.00 g of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Corporation) was added. The mixture was stirred at 60 ° C. for 4 hours and allowed to cool to room temperature. Subsequently, 89.29 g of 2,2′-dimethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) was added and stirred at 60 ° C. for 2 hours. The mixture was allowed to cool to room temperature, 27.69 g of phthalic anhydride was added, and the mixture was stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. The obtained polyamic acid had a weight average molecular weight of 18,800.

(Example 22) Protection of carboxyl group of polyamic acid by 1-chloro-1-methoxy-2-phenylpropane 250.0 g of the polyamic acid solution obtained in Synthesis Example 16 was equipped with a thermometer, a stirrer, and a nitrogen introduction tube. Then, 124.0 g of NMP was added and cooled, and 28.51 g of N, N-diisopropylethylamine was added at 0 ° C. or lower, followed by 37.60 g of 1-chloro-1-methoxy-2-phenylpropane. After 0 ℃ 4 hours at below the reaction solution was added to isopropanol 2.7 L, and the precipitated solid collected by filtration and dried to give a white solid (g-1) 66.54g. The solid was dissolved in deuterated DMSO and ¹ H-NMR spectrum was measured. From the peak integral ratio of the carboxylic acid ester and carboxylic acid, 99% of the carboxyl groups were substituted with 1-methoxy-2-phenylpropyl groups. I understood. The weight average molecular weight of the obtained resin was 24,300.
(Example 23) Protection of carboxyl group of polyamic acid with 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane 125.0 g of the polyamic acid solution obtained in Synthesis Example 16 was added to a thermometer, stirrer, Add to a 300 mL flask equipped with a nitrogen inlet tube, add 62.0 g of NMP, cool, and at 0 ° C. or lower, 16.45 g of N, N-diisopropylethylamine, followed by 1-chloro-1- (2-methoxyethoxy) -2 -29.11 g of phenylpropane was added. After reacting at 0 ° C. or less for 4 hours, the reaction solution was added to 1.5 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 29.96 g of a white solid (g-2). The solid was dissolved in deuterated DMSO, and the ¹ H-NMR spectrum was measured. From the peak integration ratio of the carboxylic acid ester to the carboxylic acid, 96% of the carboxyl groups were converted to 1- (2-methoxyethoxy) -2-phenylpropoxy groups. It was found that it was replaced. The weight average molecular weight of the obtained resin was 24,400.
(Comparative Example 11) Protection of carboxyl group of polyamic acid with 1-chloro-1-ethoxyethane 125.0 g of the polyamic acid solution obtained in Synthesis Example 16 was placed in a 300 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube. In addition, 62.0 g of NMP was added and cooled, and at 0 ° C. or lower, 16.45 g of N, N-diisopropylethylamine was added, followed by 13.82 g of 1-chloro-1-ethoxyethane. After reacting at 0 ° C. or less for 4 hours, the reaction solution was added to 1.5 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 22.95 g of a white solid (g-14). The solid was dissolved in deuterated DMSO and ¹ H-NMR spectrum was measured. From the peak integration ratio of the carboxylic acid ester and carboxylic acid, it was found that 77% of the carboxyl groups were substituted with 1-ethoxyethyl groups. The weight average molecular weight of the obtained resin was 20,900.
(Comparative Example 12) Protection of carboxyl group of polyamic acid with 1-chloro-1-methoxy-2-methylpropane 125.0 g of the polyamic acid solution obtained in Synthesis Example 16 was equipped with a thermometer, stirrer and nitrogen introduction tube. Then, 62.0 g of NMP was added and cooled, and 16.45 g of N, N-diisopropylethylamine was added at 0 ° C. or lower, followed by 15.60 g of 1-chloro-1-methoxy-2-methylpropane. After reacting at 0 ° C. or lower for 4 hours, the reaction solution was added to 1.5 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 23.77 g of a white solid (g-15). The solid was dissolved in heavy DMSO and ¹ H-NMR spectrum was measured. From the peak integral ratio of carboxylic acid ester and carboxylic acid, 89% of the carboxyl groups were substituted with 1-methoxy-2-methylpropyl groups. I understood. The weight average molecular weight of the obtained resin was 21,300.

(Synthesis Example 17) Synthesis of polyhydroxyamide A flask equipped with a stirrer and a thermometer was charged with 129 g of 4,4′-dicarboxyphenyl ether and 700 mL of N-methylpyrrolidone. After the flask was cooled to 5 ° C., thionyl chloride was added. 59.4 g was added dropwise and reacted for 1 hour to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 600 mL of N-methylpyrrolidone was charged into a flask equipped with a stirrer, a thermometer, and a cooling tube, and 153.6 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and stirred. After dissolution, 158 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 1 hour, and stirring was continued for 1 hour. The solution was poured into 20 L of water, and the precipitate was collected and washed, and then dried under reduced pressure to obtain polyhydroxyamide. The resulting polyhydroxyamide had a weight average molecular weight of 18,000.
(Example 24) Protection of hydroxyl group of polyhydroxyamide by 1-chloro-1-methoxy-2-phenylpropane In a flask equipped with a stirrer and a thermometer, 20 g of polyhydroxyamide obtained above and 200 g of ethyl acetate After stirring and dissolving, 99.4 g of 1-chloro-1-methoxy-2-phenylpropane was added, and then 20.5 g of triethylamine was stirred at room temperature for 1 hour. Thereafter, the reaction solution was transferred to a separating funnel and separated into an organic phase and an aqueous phase. The organic phase is concentrated with an evaporator, diluted with acetone and poured into 1 liter of pure water. The precipitate is recovered, washed with n-hexane and pure water, dried under reduced pressure, and 23.8 g of a white solid (h-1). Got. ^{From 1} H-NMR spectrum, it was found that 38 mol% of the hydroxyl group was substituted with 1-methoxy-2-phenylpropoxy group. The weight average molecular weight of the target product, was 21,400.

(Example 25) Protection of hydroxyl group of polyhydroxyamide by 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane Into a flask equipped with a stirrer and a thermometer, the polyhydroxyamide obtained above was added. 20 g of ethyl acetate and 200 g of ethyl acetate were added and dissolved by stirring. Then, 123.1 g of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane was added, and then 20.5 g of triethylamine was stirred at room temperature for 1 hour. did. Thereafter, the reaction solution was transferred to a separating funnel and separated into an organic phase and an aqueous phase. The organic phase is concentrated with an evaporator, diluted with acetone and poured into 1 liter of pure water. The precipitate is recovered, washed with n-hexane and pure water, dried under reduced pressure, and 24.7 g of a white solid (h-2). Got. ^{From the 1} H-NMR spectrum, it was found that 36 mol% of the hydroxyl groups were substituted with 1- (2-methoxyethoxy) -2-phenylpropoxy group. The weight average molecular weight of the target product was 22,200.

(Comparative Example 13) Protection of hydroxyl group of polyhydroxyamide by 1-chloro-1-ethoxyethane A flask equipped with a stirrer and a thermometer was charged with 20 g of the polyhydroxyamide obtained above and 200 g of ethyl acetate and stirred. After dissolution, 58.5 g of 1-chloro-1-ethoxyethane was added, and then 20.5 g of triethylamine was stirred for 1 hour at room temperature. Thereafter, the reaction solution was transferred to a separating funnel and separated into an organic phase and an aqueous phase. The organic phase is concentrated with an evaporator, diluted with acetone and poured into 1 liter of pure water. The precipitate is collected, washed with n-hexane and pure water, dried under reduced pressure, and 21.5 g of a white solid (h-14). Got. ^{From the 1} H-NMR spectrum, it was found that 30 mol% of the hydroxyl groups were substituted with 1-ethoxyethyl groups. The weight average molecular weight of the target product was 19,300.

(Comparative Example 14) Protection of hydroxyl group of polyhydroxyamide with 1-chloro-1-methoxy-2-methylpropane In a flask equipped with a stirrer and a thermometer, 20 g of polyhydroxyamide obtained above and 200 g of ethyl acetate After stirring and dissolving, 66.0 g of 1-chloro-1-methoxy-2-methylpropane was added, and then 20.5 g of triethylamine was stirred at room temperature for 1 hour. Thereafter, the reaction solution was transferred to a separating funnel and separated into an organic phase and an aqueous phase. The organic phase is concentrated with an evaporator, diluted with acetone and poured into 1 liter of pure water. The precipitate is recovered, washed with n-hexane and pure water, dried under reduced pressure, and 22.0 g of a white solid (h-15). Got. ^{From the 1} H-NMR spectrum, it was found that 38 mol% of the hydroxyl groups were substituted with 1-methoxy-2-methylpropyl groups. The weight average molecular weight of the target product was 19,800.
Using the protective agent described in Table 2 below and a compound (or resin) that can be protected by reacting therewith, the protective body described in Table 2 below was produced by the same synthesis method as described above. The protection ratio (mol%) in the table is a value measured by ¹ H-NMR spectrum.

(Examples 26 to 109 and Comparative Examples 15 to 28) Storage Stability Test of Protective Body Protective bodies obtained in Examples 3 to 25, Synthesis Examples 14 and 15, Comparative Examples 3 to 14, and Comparative Synthesis Examples 3 and 4 A 2% by weight heavy dimethyl sulfoxide solution of each protector described in Table 2 above was prepared and aged for 15 days at 40 ° C. The protection rate was calculated from ¹ H-NMR measurement after the lapse of time, and the decomposition rate was determined from the following formula. The results are shown in Table 3.
Degradation rate (%) = (100−protection rate after aging (%)) / protection rate immediately after preparation (%)

As is apparent from the results shown in Table 3, Comparative Examples 15 to 28 using resins or compounds protected with a protective agent that does not satisfy the general formula (I) have a high decomposition rate and storage stability. It turns out that it is inferior to.
On the other hand, it can be seen that Examples 26 to 109 using resins or compounds protected with the protective agent represented by the above general formula (I) have a low decomposition rate and extremely excellent storage stability.

(Examples 110 to 169 and Comparative Examples 29 to 38) Formation of photosensitive resin composition and pattern The components shown in the following table were dissolved in the solvents shown in the same table to obtain a total solid concentration of 25% by mass, and a pore size of 0.1 μm. The mixture was filtered through a polytetrafluoroethylene cassette-type filter to prepare a photosensitive resin composition. In the table, the solid content of each component is expressed as mass%.

Abbreviations in the table are shown below.
PAI-101: α- (p-Tolylsulfonyloxyimino) -4-methoxyphenylacetonitrile (Midori Chemical Co., Ltd.)
NAI-105: N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (manufactured by Midori Chemical Co., Ltd.)
TESPEC: triethoxysilylpropyl ethyl carbamate EOA: amine of the following structure

PF6320: (made by OMNOVA, fluorine type)
PGMEA: Propylene glycol monomethyl ether acetate DMAc: N, N-dimethylacetamide

A pattern was formed by the following method, and the pattern shape was evaluated.
<Pattern formation method>
The prepared photosensitive resin composition was spin-coated on a 4 inch silicon wafer, subjected to pre-drying of 120 ° C. 3 minutes on a hot plate to give a film thickness of 5.0μm film (photosensitive film). Next, pattern exposure was performed using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon, Inc.) using a 1-30 μm via hole repeating pattern mask. Subsequently, it heated at 120 degreeC for 3 minute (s), carried out the paddle development with the 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, and the rinse process was performed with the pure water.
The patterns obtained in Examples 146 to 169 and Comparative Examples 35 to 38 were heated under nitrogen conditions at 350 ° C. for 60 minutes to obtain cured relief patterns.
<Resolution>
The obtained pattern film was observed with a length measurement SEM (Hitachi, Ltd. S-8840), and the resolved via hole had a minimum dimension of less than 2 μm, A, 2 μm or more and less than 5 μm, and C, and 5 μm or more. A and B were set to pass.
<Sensitivity>
The obtained pattern film was observed with a length measurement SEM (Hitachi, Ltd. S-8840), and the exposure amount obtained by resolving the via hole having the smallest dimension was defined as sensitivity. A less than 100 mJ / cm ² was A, 100 mJ / cm ² or more. 500 mJ / cm ² less than the B, and 500 mJ / cm ² or more was C. A and B were set to pass.

As is clear from the results shown in Table 4, it can be seen that Comparative Examples 29 to 38 are all inferior in resolution, and Comparative Examples 35 to 38 with respect to the cured relief pattern are also inferior in sensitivity.
On the other hand, it can be seen that the patterns obtained from the photosensitive resin compositions obtained in Examples 110 to 145 are excellent in both resolution and sensitivity.
Similarly, it can be seen that Examples 146 to 169 of the cured relief pattern are both excellent in resolution and sensitivity.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Mar. 23, 2012 (Japanese Patent Application No. 2012-068198), the contents of which are incorporated herein by reference.

Claims

A protective agent for a hydroxyl group or a carboxyl group, which is a compound represented by the following general formula (I).

(In the above general formula, R 1 and R 2 are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl. Represents a group, a cyano group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom. .
R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring. X represents a group capable of leaving by the action of the hydroxyl group or carboxyl group. )
The hydroxyl group or carboxyl group protective agent according to claim 1, wherein at least one of R 1 and R 2 in the compound represented by the general formula (I) is an aryl group.
A method for producing a compound having a group represented by the following general formula (III) by reacting the protective agent according to claim 1 or 2 with a compound having a hydroxyl group or a carboxyl group.

(In the above general formula, R 1 , R 2 and R 3 are respectively synonymous with R 1 , R 2 and R 3 in the general formula (I), and at least one of R 1 and R 2 is an aryl group. , An alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
* Represents a binding site with a residue obtained by removing —OH from the group of the compound having a hydroxyl group or a carboxyl group. )
A resin selected from the group consisting of a polyhydroxystyrene resin, a novolac resin, a polyacrylic acid resin, a polymethacrylic acid resin, a polyamic acid and a polyhydroxyamide, wherein all or part of the hydroxyl groups or carboxyl groups in the resin , resin substituted with a group represented by the following general formula (III).

(In the above general formula, R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
* Represents a binding site with a residue obtained by removing —OH from the hydroxyl group or carboxyl group of the resin. )
All or part of the hydroxyl groups of the polyhydroxystyrene resin having a repeating unit represented by the following general formula (V) and having a weight average molecular weight of 1,000 to 100,000 are groups represented by the following general formula (III) Polyhydroxystyrene resin substituted with

(In the above general formula, R 4 represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, and k represents an integer of 0 to 4)

(In the above general formula, R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, It represents a group or a halogen atom, at least one of R 1 and R 2, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
* Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (V). )
A repeating unit represented by the following general formula (VI), all or a portion of the hydroxyl groups of novolak resin having a weight average molecular weight of 1,000 to 100,000 is substituted with a group represented by the following general formula (III) Novolac resin.

(In the above general formula, R 5 represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, m represents an integer of 0 to 3, and R 6 and R 7 each independently represents Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.)

(In the above general formula, R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, It represents a group or a halogen atom, at least one of R 1 and R 2, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring. * Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (VI). )
All or part of the carboxyl groups of the polymer having a repeating unit represented by the following general formula (VII) and having a weight average molecular weight of 1,000 to 100,000 are substituted with a group represented by the following general formula (IV) Polyacrylic acid resin or polymethacrylic acid resin.

(In the above general formula, R 8 represents a hydrogen atom or an alkyl group.)

(In the above general formula, R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, It represents a group or a halogen atom, at least one of R 1 and R 2, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
* Represents a binding site with a residue obtained by removing a carboxyl group from the repeating unit represented by the general formula (VII). )
The polyamic acid by which all or one part of the carboxyl group of the polyamic acid which has a repeating unit represented by the following general formula (VIII) was substituted by the group represented by the following general formula (IV).

(In the above general formula, R 9 represents a tetravalent organic group, and R 10 represents a divalent organic group.)

(In the above general formula, R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, It represents a group or a halogen atom, at least one of R 1 and R 2, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
* Represents a binding site with a residue obtained by removing a carboxyl group from the repeating unit represented by the general formula (VIII). )
A polyhydroxyamide in which all or part of hydroxyl groups of a polyhydroxyamide having a repeating unit represented by the following general formula (IX) is substituted with a group represented by the following general formula (III).

(In the above general formula, R 11 represents a tetravalent organic group, and R 12 represents a divalent organic group.)

(In the above general formula, R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, It represents a group or a halogen atom, at least one of R 1 and R 2, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
* Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (IX). )
A photosensitive resin composition comprising (a) the resin according to any one of claims 4 to 9, and (b) a compound that generates an acid upon irradiation with actinic rays or radiation.
The photosensitive resin composition according to claim 10, which is for positive development.
The pattern formation material which is the photosensitive resin composition of Claim 10 or 11.
A photosensitive film formed from the photosensitive resin composition according to claim 10.
A cured film obtained by heat-treating the photosensitive resin composition according to claim 10 or 11.
(A) forming the photosensitive film according to claim 13 on a substrate;
(A) a step of exposing the photosensitive film with actinic rays or radiation;
(C) A process for developing the photosensitive film so as to remove the exposed portion with an aqueous alkaline developer, and (d) a method for producing a cured relief pattern comprising a step of heat-treating the obtained relief pattern.
A cured relief pattern obtained by the production method according to claim 15.
A semiconductor device comprising the cured relief pattern according to claim 16.