KR101780663B1

KR101780663B1 - Photosensitive resin composition, material for forming relief pattern, photosensitive film, polyimide film, cured relief pattern and method for producing same, and semiconductor device

Info

Publication number: KR101780663B1
Application number: KR1020147002626A
Authority: KR
Inventors: 켄지 와다; 쿄우헤이 아라야마; 타쿠마 아메미야
Original assignee: 후지필름 가부시키가이샤
Priority date: 2011-07-29
Filing date: 2012-07-12
Publication date: 2017-09-21
Also published as: WO2013018524A1; CN103718109A; CN103718109B; KR20140047105A; JP2013050696A; JP5887172B2

Abstract

A photosensitive resin composition capable of forming a cured relief pattern having a lithography performance excellent in resolution and sensitivity and capable of preventing warpage of a wafer by lowering stress in a so-called low-temperature cure, a relief pattern forming material using the photosensitive resin composition, , A polyimide film, a cured relief pattern, a method of manufacturing the same, and a semiconductor device including the cured relief pattern.
(a) a resin having a repeating unit represented by the following general formula (1), and (b) a compound which generates an acid upon irradiation with an actinic ray or radiation.

[In the general formula (1), R ¹ represents a tetravalent organic group. The plurality of R < ¹ ^> may be the same or different.
R ² represents a divalent organic group. The plurality of R ² may be the same or different.
Provided that at least one of the plurality of R < ² > is a divalent organic group having an alicyclic group.
Each R ³ independently represents a hydrogen atom or an organic group.
Provided that at least one of the plurality of -CO ₂ R ³ is a group that is decomposed by the action of an acid generating an alkali-soluble group;

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a relief pattern forming material, a photosensitive film, a polyimide film, a cured relief pattern, a method of manufacturing the same, PRODUCING SAME, AND SEMICONDUCTOR DEVICE}

The present invention relates to a positive type high heat-resistant photosensitive resin composition used as a surface protective film of a semiconductor device, an interlayer insulating film, an interlayer insulating film for a display device, a method of producing a cured relief pattern having heat resistance using the positive high heat- To a semiconductor device.

Negative polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics are used for the surface protective film and interlayer insulating film of semiconductor devices. This negative-type polyimide resin is presently provided in the form of a photosensitive polyimide precursor composition, and is applied to a surface protective film (not shown) on a semiconductor device by coating, patterning with an actinic ray, organic solvent development, , An interlayer insulating film, and the like can be easily formed, and the process can be significantly shortened in comparison with the conventional non-photosensitive polyimide precursor composition.

However, in a photosensitive negative-type polyimide precursor composition, it is necessary to use a large amount of organic solvent such as N-methyl-2-pyrrolidone as a developer in the development process, ) Measures against organic solvents have been demanded. In recent years, various proposals have been made for a heat-resistant photosensitive resin material that can be developed with an alkaline aqueous solution like photoresist.

Among them, a method of using a composition in which a polyamic acid (polyimide precursor) soluble in an alkaline aqueous solution or a hydroxypolyamide (polybenzoxazole) precursor is mixed with a photoactive component such as a photosensitive diazoquinone compound is used as a positive photosensitive resin composition Has recently attracted attention.

Since the photosensitive diazoquinone compound of the unexposed portion is insoluble in an alkaline aqueous solution, the photosensitive diazoquinone compound undergoes a chemical change to become an indenecarboxylic acid compound and is soluble in an alkaline aqueous solution . It is possible to form a relief pattern only for the unexposed portion using the difference in dissolution rate between the exposed portion and the unexposed portion with respect to the developing solution (see, for example, Patent Document 1).

On the other hand, in the field of semiconductor photoresist, as a technique for separating the photosensitive and insoluble functions of the unexposed portion, an acid of a catalytic amount is generated by exposure, and subsequently an alkali insoluble group in the composition is exposed to a catalyst A chemical amplification-type photosensitive composition which converts an alkali-soluble group into a chemical group by a chemical reaction is widely applied. Also in this technical field, a chemical amplification type photosensitive composition is disclosed (for example, see Patent Document 2). In particular, a chemically amplified photosensitive resin composition containing a polyimide precursor protected by a specific acid-decomposable protecting group from viewpoints of high resolution and high sensitivity is disclosed (see, for example, Patent Document 3 and Patent Document 4).

On the other hand, with the recent development of semiconductor technology, there is a demand for forming finer patterns and lowering the film thickness temperature (cure temperature) after pattern formation.

However, it is known that when the cure temperature is lowered, the imide cyclization becomes difficult to proceed. With respect to this problem, it has been reported that the problem is improved by adding, for example, a sulfonic acid, a sulfonic ester compound, or the like (Patent Document 5). However, it has been found that there are cases in which the strength and chemical resistance of the resultant film are insufficient, or the fine image-forming ability is impaired.

In addition, the problem of warpage of a silicon wafer having a polyimide film (hereinafter simply referred to as " wafer warpage ") has also become apparent due to the recent large-scale curing and lamination of silicon wafers. This is thought to be caused by the residual stress resulting from the difference in thermal expansion coefficient between the polyimide and the silicon wafer. Therefore, there is a strong demand for a polyimide having lower thermal expansion and lower stress (low stress) than conventional polyimide (for example, Non-Patent Document 1). Patent Document 2). In this structure, the i-line permeability, the solvent solubility, and the alkali solubility of the precursor are low and the sufficient thermal stability is not obtained even when the polyimide main chain is made straight and rigid. And the like. For example, Patent Document 6 discloses a positive photosensitive composition comprising a compound capable of generating an acid upon irradiation with radiation and a PBO precursor, wherein the polybenzoxazole film formed by the PBO precursor has a PBO precursor having a residual stress of 25 MPa or less , There are various problems in lithography performance such as sensitivity and profile.

Japanese Patent Application Laid-Open No. 56-27140 Japanese Patent Application Laid-Open No. 2002-526793 Japanese Patent Application Laid-Open No. 2009-244479 Japanese Patent Application Laid-Open No. 2009-192760 Japanese Patent Application Laid-Open No. 2006-010781 Japanese Patent Application Laid-Open No. 2001-214055

J. Photopolym. Sci. Technol., Vol. 15; NO.2; PAGE.167-172 (2002) The Latest Polyimide - Fundamentals and Applications - (Japan Polyimide Research Association)

The present invention has a lithography performance excellent in resolution and sensitivity, and has a low stress at 300 캜 or lower (preferably 250 캜 or lower) at a low temperature, a so-called low temperature cure to form a cured relief pattern preventing wafer warping A relief pattern forming material using the photosensitive resin composition, a photosensitive film, a polyimide film, a cured relief pattern, a method for producing the same, and a semiconductor device including the cured relief pattern .

The present invention has the following structure, and thus the above-described problems of the present invention are solved.

[One]

(a) a resin having a repeating unit represented by the following general formula (1), and

(b) a compound which generates an acid upon irradiation with an actinic ray or radiation.

[In the above general formula (1)

R ¹ represents a tetravalent organic group. The plurality of R < ¹ ^> may be the same or different.

R ² represents a divalent organic group. The plurality of R ² may be the same or different.

Provided that at least one of the plurality of R < ² > is a divalent organic group having an alicyclic group.

Each R ³ independently represents a hydrogen atom or an organic group.

Provided that at least one of the plurality of -CO ₂ R ³ is a group that is decomposed by the action of an acid generating an alkali-soluble group;

[2]

The resin (a) having a repeating unit represented by the general formula (1) is preferably a resin having a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3) The photosensitive resin composition described above.

[In the above general formula (2)

R ¹ 'is R ¹ and agreed in the general formula (1).

R ³ 'is R ³ and agreed in the general formula (1).

Provided that at least one of the plurality of -CO ₂ R ³ 'is a group which is decomposed by the action of an acid to generate an alkali-soluble group.

R ⁴ is a divalent organic group having an alicyclic group.

In the general formula (3)

R ¹ "is R ¹ and agreed in the general formula (1).

R ³ "is R ³ as agreed in the general formula (1).

Provided that at least one of -CO ₂ R ³ "is a group which is decomposed by the action of an acid to generate an alkali-soluble group.

R < ⁵ > is a divalent organic group different from R < ^{4 &}

[3]

The photosensitive resin composition according to [2], wherein R ⁵ in the general formula (3) is a divalent group having an aromatic group.

[4]

The photosensitive resin composition according to [3], wherein R ⁵ in the general formula (3) is a divalent group represented by any one of the following formulas.

[Wherein the hydrogen atoms of each aromatic ring are each independently substituted with at least one atom or group selected from the group consisting of fluorine atom, chlorine atom, bromine atom, methyl group, methoxy group, cyano group, phenyl group and trifluoromethyl group It may be.

[5]

The general formula (1) -CO ₂ R ^3, the general formula ₍₂₎ -CO 2 R ³ 'or the thermal decomposition temperature of -CO ₂ R ³ "in the general formula 3 in the in the The photosensitive resin composition according to any one of [1] to [4], wherein the photosensitive resin composition is 100 to 220 캜.

[6]

Of the acid to the -CO ₂ R ³ "in the general formula (1) -CO ₂ R ^3, the general formula ₍₂₎ -CO 2 R ³ 'or the general formula (3) according to the in The photosensitive resin composition according to any one of the above items [1] to [5], wherein the group which is decomposed by the action to generate an alkali-soluble group is an ester group in which the hydrogen atom of the carboxyl group is substituted with a group represented by the following general formula (III).

[Wherein, in the general formula,

Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

Rb represents a single bond or a divalent linking group.

Q represents an alkyl group, a heterocyclic group which may contain a hetero atom, or an aromatic group which may contain a hetero atom.

At least two of Ra, Rb and Q may be bonded to each other to form a ring]

[7]

The photosensitive resin composition according to [6], wherein Ra in the general formula (III) is a group represented by the following general formula (IV) or (V)

[Wherein, in the general formula,

Rc and Rd each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom; May form a ring by bonding to each other, and at least two of Re, Rf and Rg may be bonded to each other to form a ring)

[8]

[7], wherein at least one of Rc and Rd in the general formula (IV) is a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom Sensitive resin composition.

[9]

The photosensitive resin composition according to [8], wherein at least one of Rc and Rd in the general formula (IV) is an aryl group.

[10]

The photosensitive resin composition according to [6], wherein at least one of Ra, Rb and Q in the general formula (III) is a group having an electron-withdrawing group or an electron-withdrawing group.

[11]

The photosensitive resin composition according to [1], wherein R ¹ in the general formula (1) is a monocyclic or condensed polycyclic aliphatic group or a tetravalent linking group having an aromatic group.

[12]

The photosensitive resin composition according to [1] or [11], wherein R ² in the general formula (1) is a divalent group having an alicyclic group, a divalent group having an aromatic group, or a divalent group containing a silicon atom.

[13]

The photosensitive resin composition according to any one of [1] to [12], wherein the resin (a) has a mass average molecular weight of 200,000 or less.

[14]

The photosensitive resin composition according to any one of [1] to [13], further comprising (c) a basic compound.

[15]

The photosensitive resin composition according to any one of [1] to [14], wherein the compound (b) is an oxime compound.

[16]

The photosensitive resin composition according to any one of (1) to (15), further comprising (f) an adhesion promoter.

[17]

The photosensitive resin composition according to any one of the above [1] to [16], which is for positive type development.

[18]

A pattern forming material which is the photosensitive resin composition according to any one of [1] to [16].

[19]

A photosensitive film formed from the photosensitive resin composition according to any one of [1] to [16].

[20]

A polyimide film obtained by heat-treating the photosensitive resin composition according to any one of [1] to [16].

[21]

(A) a step of forming the photosensitive film described in [19] on a substrate,

(B) exposing the photosensitive film to an actinic ray or radiation,

(C) developing the exposed portion of the photosensitive film to remove with an aqueous alkali developer, and

(D) heat-treating the obtained relief pattern.

[22]

A cured relief pattern obtained by the production method described in [21].

[23]

A semiconductor device comprising the cured relief pattern described in [22].

[24]

A resin having a repeating unit represented by the following general formula (1).

[In the above general formula (1)

Each R ³ independently represents a hydrogen atom or an organic group.

(Effects of the Invention)

The photosensitive resin composition of the present invention has a lithography performance excellent in resolution and sensitivity and can form a cured relief pattern that prevents warpage of the wafer due to low stress in a so-called low temperature cure.

According to the present invention, it is possible to provide a relief pattern forming material having a lithography performance excellent in resolution and sensitivity, excellent in low stress characteristics in a so-called low-temperature cure and capable of forming a cured relief pattern preventing wafer warpage, , A cured relief pattern, a method of manufacturing the same, and a semiconductor device including the cured relief pattern.

In the present specification, the notation in which the substituent and the non-substituent are not described in the notation of the group (atomic group) includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term " active ray " or " radiation " in this specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray represented by an excimer laser, extreme ultraviolet ray (EUV light), X ray, electron beam (EB) In the present invention, light means an actinic ray or radiation.

The term " exposure " in the present specification refers to not only exposure by deep ultraviolet rays, X-rays, EUV light, and the like represented by mercury lamps and excimer lasers, but also imaging by particle beams such as electron beams and ion beams Are included in the exposure.

The photosensitive resin composition of the present invention comprises (a) a resin having a repeating unit represented by the following general formula (1), and

In the general formula (1)

Each R ³ independently represents a hydrogen atom or an organic group.

Provided that at least one of the plurality of -CO ₂ R ³ is a group that is decomposed by the action of an acid generating an alkali-soluble group.

The photosensitive resin composition of the present invention containing the resin (a) having a repeating unit represented by the general formula (1) has a lithography performance excellent in resolution and sensitivity, and has a low stress in a so-called low temperature cure to prevent wafer warping The reason why the cured relief pattern can be formed is not clear, but is estimated as follows.

The repeating unit represented by the general formula (1) can form a linear and rigid polyimide by thermosetting, and at least one of R ² present in a plurality of the resin (a) is a divalent organic group having an alicyclic group The linearity and the rigidity can be improved by setting. As a result, the thermal expansion can be made particularly low, low stress can be achieved, and wafer warpage can be prevented.

In addition, since at least one of R < ² > existing in a plurality of the resin (a) is a divalent organic group having an alicyclic group, it is possible to achieve lithography performance without deteriorating light transmittance such as i line at the time of exposure and excellent in resolution and sensitivity .

(a) a resin having a repeating unit represented by the general formula (1)

The resin (a) having a repeating unit represented by the general formula (1) is a resin whose solubility in an alkali developer is increased by the action of an acid. The resin having a repeating unit represented by the general formula (1) is preferably insoluble or sparingly soluble in an alkali developer.

The repeating unit represented by the general formula (1) is a compound having four carboxyl groups with R ¹ as a nucleus, a carboxylic acid anhydride thereof, or a hydrogen atom in at least one of the four carboxyl groups, , And a diamine component derived from a compound having two amino groups using R ² as a nucleus. In other words, an acid component which is a partial structure containing two carbonyl groups sandwiched between two carbonyl groups in the general formula (1) and a partial structure represented by -NH-R ² -NH- in the general formula (1) Diamine component.

The tetravalent organic group R ¹ preferably has 4 to 30 carbon atoms, more preferably a monocyclic or condensed polycyclic aliphatic group or a tetravalent linking group having an aromatic group. The plural R ^{1 s} present in the resin (a) may be the same or different.

Examples of the monocyclic aromatic group in the tetravalent organic group R ¹ include a benzene ring group and a pyridine ring group.

Examples of the condensed polycyclic aromatic group in the tetravalent organic group R ¹ include a naphthalene ring group and a perylene ring group.

Examples of the monocyclic aliphatic group in the tetravalent organic group R ¹ 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 ¹ include a bicyclo [2.2.1] heptane ring group, a bicyclo [2.2.2] octane ring group, a bicyclo [2.2.2] .

The monocyclic or condensed polycyclic aliphatic group or aromatic group per se of the tetravalent organic group R ¹ may be a monocyclic or condensed polycyclic aliphatic group or an aromatic group per se as the tetravalent linking group having an aromatic group or a monocyclic polycyclic aliphatic group or aromatic group, A polycyclic aliphatic group or an aromatic group may be connected through a single bond or a divalent linking group to form a quadrivalent linking group as R ¹ .

Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group and a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, Amide group and the like.

Specific examples of the acid component having R ¹ as a nucleus and having a group derived from at least four carboxyl groups include pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride, 2,3,3' Biphenyltetracarboxylic acid anhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid anhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid anhydride, 2,2 '',3,3'-benzophenonetetracarboxylic acid anhydride, 4,4' - (hexafluoroisopropylidene) 2 phthalic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 2,3 , 6,7-naphthalene tetracarboxylic acid anhydride, 2,3,5,6-pyridine tetracarboxylic acid anhydride, 3,4,9,10-perylene tetracarboxylic acid anhydride, (trifluoromethyl) pyro Di (trifluoromethyl) pyromellitic anhydride, di (heptafluoropropyl) pyromellitic anhydride, pentafluoroethyl pyromellitic anhydride, bis [3,5-di (trifluoromethyl) Pe 3,3 ', 4,4'-tetracarboxylic diphenyl ether dianhydride, 2,3', 3,4'-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4,4'- 4,4'-tetracarboxylic diphenylsulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2'-tetracarboxylic diphenylmethane dianhydride, Bis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxybiphenyl dianhydride, bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2 ', 5,5'-tetrakis (trifluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis (trifluoromethyl) ', 4,4'-tetracarboxylic diphenyl ether dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybenzophenone dianhydride, bis [ (Dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis Bis (4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4- Carboxyphenoxy) phenyl) hexafluoropropane dianhydride, and 5,5 '- [p-phenylenebis (oxycarbonyl)] dihydric phthalic acid, or a component derived from an aromatic tetracarboxylic acid 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] Tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride, (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid And a component derived from an aliphatic tetracarboxylic acid anhydride such as (2R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid dianhydride.

Preferably a component derived from pyromellitic anhydride, a component derived from 3,3 ', 4,4'-biphenyltetracarboxylic anhydride, a component derived from 2,3,3', 4'-biphenyltetracarboxylic acid A component derived from 2,2 ', 3,3'-biphenyltetracarboxylic acid anhydride, a component derived from 3,3', 4,4'-benzophenonetetracarboxylic acid anhydride, A component derived from 4,4 '- (hexafluoroisopropylidene) 2 phthalic anhydride, a component derived from 3,3', 4,4'-tetracarboxydiphenyl ether dianhydride, 1,2,5,6 - a component derived from naphthalene tetracarboxylic anhydride, a component derived from 5,5 '- [p-phenylenebis (oxycarbonyl)] diphthalic anhydride, a component derived from cyclobutane tetracarboxylic anhydride, A component derived from pentane tetracarboxylic acid anhydride, a component derived from bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid dianhydride and a component derived from (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride, &Lt; / RTI >

More preferably a component derived from pyromellitic anhydride, a component derived from 3,3 ', 4,4'-biphenyltetracarboxylic anhydride, a component derived from 4,4' - (hexafluoroisopropylidene) 2 phthalic acid A component derived from an anhydride, a component derived from a cyclobutane tetracarboxylic acid anhydride, a component derived from 3,3 ', 4,4'-tetracarboxydiphenyl ether dianhydride, a component derived from a cyclopentanetetracarboxylic acid anhydride, Component, a component derived from 5,5 '- [p-phenylenebis (oxycarbonyl)] dicarboxylic acid dianhydride, a component derived from (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic acid dianhydride, (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid 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 ¹ as nuclei in the resin (a) is preferably 20 to 70 mol% based on the total repeating units constituting the resin (a) , And more preferably from 30 to 60 mol%.

Examples of the divalent organic group R ² include a divalent group having an alicyclic group, a divalent group having an aromatic group, and a divalent group containing a silicon atom. The plurality of R ² present in the resin (a) may be the same or different.

Hereinafter, when R ² is a divalent group having an alicyclic group, a diamine component having R ² as a nucleus may be referred to as an alicyclic diamine component, and when R ² is a divalent group having an aromatic group, a diamine component having R ² as a nucleus a and sometimes called an aromatic diamine component, which may be referred to as R ² is a diamine component with the diamine component to the silicon of R ² when a divalent date containing silicon atoms as a core.

At least one of R < ² > in the diamine component present in a plurality of the resins (a) is a divalent group having an alicyclic group. When the resin (a) contains a diamine component having an alicyclic group, good solvent solubility, alkali dissolution rate, transparency and sensitivity can be realized.

R ² is preferably a divalent alicyclic group having 3 to 20 carbon atoms, more preferably a monocyclic cycloalkylene group such as cyclopentylene group or cyclohexylene group, a bicyclo [2.2.1] heptylene group, a norbornylene group , Tetracyclodecanylene group, tetracyclododecanylene group, adamantylene group, and other polycyclic cycloalkylene groups.

The divalent group having an alicyclic group for R ² may be the aforementioned divalent group itself, but a plurality of alicyclic groups are preferably an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group and a propylene group) To form a bivalent group having an alicyclic group as R ^{2, or} an amino group and an alicyclic group in the diamine component may be connected by an alkylene group.

The above-mentioned vicinal group or alkylene group which may form a divalent group having an alicyclic group may have a substituent, and examples of such substituent include an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) and a halogen atom.

Particularly preferred examples of the diamine component having a pericyclic structure having R ² as a nucleus include a 5-amino-1,3,3-trimethylcyclohexane methylamine component, a cis-1,4-cyclohexane diamine component, a trans- Cyclohexane diamine component, 1,4-cyclohexane diamine component (cis, trans mixture), 4,4'-methylenebis (cyclohexylamine) component and its 3,3'-dimethyl substituent, bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-biadamantyl, 4,4'-hexafluoroisopropylidenebis Hexamylamine) component, among which 3,3'-diamino-1,1'-biadamantyl component and trans-1,4-cyclohexanediamine component are preferable from the viewpoint of lowering the stress.

The content of the alicyclic diamine component having two amino groups using R ² as a nucleus in the resin (a) is preferably 20 to 70 mol%, more preferably 30 to 60 mol%, based on the total repeating units constituting the resin (a) Is more preferable.

The aromatic group in the divalent group having an aromatic group for R ² is preferably an aromatic group having 5 to 16 carbon atoms, and examples thereof include a phenylene group and a naphthylene group. 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 and the like.

As the bivalent group having an aromatic group for R ² , the aromatic group itself may be used, but a plurality of aromatic groups may be connected through a single bond or a divalent linking group to form a bivalent group having an aromatic group as R ² . The amino group and the aromatic group may be connected through a divalent linking group.

The aromatic group and the alkylene group capable of forming a divalent group having an aromatic group may have a substituent. As such a substituent, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), a halogen atom, an alkoxy group such as a methoxy group, An aryl group such as an naphthyl group and a phenyl group, and the like.

As specific examples of the aromatic diamine component having R ² as a nucleus, there can be mentioned, 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'-diaminodiphenylsulfone component, 4,4'-diaminodiphenylsulfone component, 3 , 4'-diaminodiphenylsulfone component, 3,3'-diaminodiphenylmethane component, 4,4'-diaminodiphenylmethane component, 3,4'-diaminodiphenylmethane component, 4,4'-diaminodiphenylmethane component, Diaminodiphenyl ketone component, 3,4'-diaminodiphenylketone component, 2,2'-diaminodiphenylsulfone component, 3,3'-diaminodiphenylketone component, 4,4'-diaminodiphenylketone component, Bis (4-aminophenoxy) benzene component, 1,3-bis (4-aminophenyl) propane component, 2,2'- (4-aminophenoxy) benzene component, 4-methyl-2,4-bis (4- Aminophenyl) -1-pentene component, 1,4-bis (?,? -Dimethyl-4-aminobenzyl) benzene component, 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'-diamino azobenzene component, (4-aminophenoxy) biphenyl component, 2,2-bis [4- (4-aminophenoxy) phenyl] propane component, 2,2- Bis [4- (3-aminophenoxy) phenyl] benzophenone component, 4,4'-bis (4-aminophenoxy) phenyl] hexafluoropropane component, 2,2- (4-aminobenzyl) phenoxy] benzophenone component, 4,4'-bis [4- (α, Dimethyl-4-aminobenzyl) phenoxy] diphenyl sulfone 4,4'-diaminobiphenyl component, 3,4'-diaminobiphenyl component, 4,4'-diaminobipophenone component, phenylindanediamine component, 3,3'-dimethoxy- Dimethyl-4,4'-diaminobiphenyl component, 2,2'-dimethyl 4,4'-diaminobiphenyl component, 2,2'-bis (trifluoromethyl) benzidine component, o- (4-aminophenoxyphenyl) sulfone component, bis (4-aminophenoxyphenyl) sulfide component, 1,4- (4-aminophenoxyphenyl) benzene component, 1,3- (4-aminophenoxyphenyl) benzene component, 9,9- (4-aminophenyl) terephthalate component, 2- (4-aminophenyl) diphenylsulfone component, 4,4'-diaminobenzanilide component, Aminophenyl) benzoxazol-5-ylamine, 4,4 "-diamino-p-terphenyl component, etc., and aromatic nuclei of aromatic diamines There may be mentioned a structure substituted by a small atom chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, a group or an atom of at least one member selected from the group consisting of a phenyl group.

Particularly preferred aromatic diamine components are p-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 2 (4-aminophenoxy) benzene component, imino-di-p-phenylenediamine component, 4,4'-dia A 4,4'-diaminobenzophenone component, a 3,3'-dimethoxy-4,4'-diaminobiphenyl component, a 3,3'-dimethyl-4,4'-diaminobiphenyl component, (4-aminopropyl) phenyl, 2,2'-dimethyl 4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) benzidine, o-toluidine sulfone, (4-aminophenoxy) diphenyl sulfone component, 4,4'-diaminobenzanilide (4-aminophenoxy) diphenyl sulfone component, 4-aminophenyl benzoate component, bis (4-aminophenyl) terephthalate, 2- (4- Aminophenyl) benzoxazol-5-ylamine component and a 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 the bisaminophenol component include a 3,3'-dihydroxybenzidine component, a 3,3'-diamino-4,4'-dihydroxybiphenyl component, a 4,4'-diamino- , 3'-dihydroxybiphenyl component, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone component, 4,4'-diamino-3,3'-dihydroxydiphenyl (3-amino-4-hydroxyphenyl) methane component, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane component, bis- (4-amino-3-hydroxyphenyl) , 2,2-bis- (4-amino-3-hydroxyphenyl) propane component, 4,4'-diamino-3,3'-dihydroxybenzophenone component, 3,3'- , 4'-dihydroxybenzophenone component, 4,4'-diamino-3,3'-dihydroxydiphenyl ether component, 3,3'-diamino-4,4'-dihydroxydiphenyl Ether component, 1,4-di 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.

As a particularly preferable form of these bisaminophenol structures, R ² in the general formula (1) is a divalent group having an aromatic group selected from the following.

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, or -NHCO-. * Represents a bonding position with -NH- or -OH bonded to R ² in the general formula (1). Further, -NH- and -OH bonded to R < ² > in the above structure are bonded to each other at ortho positions (adjacent positions).

The content of the aromatic diamine component having two amino groups using R ² as a nucleus in the resin (a) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, based on the total repeating units constituting the resin (a) Is more preferable.

Further, in order to improve the adhesiveness with the substrate, a silicon diamine component may be used as a diamine component having R ² as a nucleus. Examples thereof include a bis (4-aminophenyl) dimethylsilane component, a bis (4-aminophenyl) tetramethyldisiloxane component, a bis , A bis (? -Aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis (? -Aminopropyl) tetraphenyldisiloxane component.

Examples of the silicon diamine component include the following structures.

In the above formula, R ₅ and R ₆ represent a divalent organic group, and R ₇ and R ₈ represent a monovalent organic group. The plurality of R < ₇ > may be the same or different. The plurality of R < ₈ > may be the same or different.

Examples of the divalent organic group represented by R ₅ and R ₆ include a linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group having 6 to 20 carbon atoms, a divalent cyclic group having 3 to 20 carbon atoms, Are combined with each other.

The monovalent organic group represented by R ₇ and R ₈ 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 using R ² as a nucleus in the resin (a) is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, based on all the repeating units constituting the resin (a) Is more preferable.

The resin (a) having a repeating unit represented by the above-mentioned general formula (1) has a viewpoint of preventing warpage of a wafer by achieving low stress by improving linearity and rigidity when thermally curing to form polyimide, Is preferably a resin having a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3) from the viewpoint of enhancing the alkali solubility after exposure and the like.

In the general formula (2)

R ¹ 'is R ¹ and agreed in the general formula (1).

R ³ 'is R ³ and agreed in the general formula (1).

R ⁴ is a divalent organic group having an alicyclic group.

In the general formula (3)

R ¹ "is R ¹ and agreed in the general formula (1).

R ³ "is R ³ as agreed in the general formula (1).

R ⁵ is a divalent organic group different from R ⁴ .

Preferable examples of the divalent organic group having an alicyclic group for R ⁴ include the same examples as the specific examples and preferable examples of the divalent group having an alicyclic group for R ² .

As the divalent organic group R ⁵ different from R ⁴ , a divalent group having an aromatic group and a divalent group containing a silicon atom described above for R ² can be given.

R ⁵ in the general formula (3) is preferably a divalent group having an aromatic group from the viewpoints of improving linearity and rigidity to achieve low stress to prevent warpage of wafers when heat-cured to polyimide, And preferred examples of the bivalent group having an aromatic group to R ⁵ include the same examples as the specific examples and preferred examples of the divalent group having an aromatic group to R ² . And more preferably a divalent group represented by any one of the following formulas.

Wherein the hydrogen atoms of each aromatic ring are each independently substituted with at least one atom or group selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, a phenyl group and a trifluoromethyl group There may be.

Examples of the organic group of R ³ , R ³ 'or R ³ "are those having 1 to 20 carbon atoms, specifically, a group capable of decomposing by the action of an acid to generate an alkali-soluble group, an alkyl group, a cycloalkyl group, kilgi, an alkenyl group, an alkynyl group, an alkoxy group, a group containing a silicon atom, -CORc (Rc is an alkyl group, an aryl group, a cycloalkyl group), -SO ₂ Rd (Rd represents an alkyl group, an aryl group, a cycloalkyl group, o- quinonediazide Group, or a combination thereof.

The alkyl group represented by R ³ , R ³ 'or R ³ "may have a substituent, is preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom and a nitrogen atom in the alkyl chain Specific examples thereof include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n- Branched alkyl groups such as a straight chain alkyl group such as isopropyl group, isobutyl group, t-butyl group, neopentyl group and 2-ethylhexyl group. Examples of the substituent include cyano group, halogen atom, hydroxyl group, An alkoxy group, a carboxyl group, and an alkoxycarbonyl group.

The cycloalkyl group represented by R ³ , R ³ 'or R ³ "may have a substituent, is preferably a cycloalkyl group having 3 to 20 carbon atoms, may be a polycyclic ring, or may contain an oxygen atom in the ring. A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The aryl group represented by R ³ , R ³ 'or R ³ "may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and an anthryl group .

The aralkyl group represented by R ³ , R ³ 'or R ³ "may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, And a naphthylethyl group.

The alkoxy group represented by R ³ , R ³ 'or R ³ "may have a substituent, and is preferably an alkoxy group having 1 to 20 carbon atoms. Examples of the alkoxy group include a methoxy group, ethoxy group, propoxy group, A pentyloxy group, a hexyloxy group, and a heptyloxy group.

The silicon atom-containing group represented by R ³ , R ³ 'or R ³ "is not particularly limited as long as it contains silicon, but a silyloxy group (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy) Do.

The alkenyl group represented by R ³ , R ³ 'or R ³ "includes a group having a double bond at an arbitrary position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group and silicon atom-containing group. Preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms, for example, a vinyl group and an allyl group are preferable.

The alkynyl group represented by R ³ , R ³ 'or R ³ "includes a group having a triple bond at any position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group and silicon atom-containing group. Preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms, for example, an ethynyl group and a propargyl group are preferable.

In the present invention, the resin (a) at least one of the plurality of -CO ₂ R ³ present in the dog is a group that is decomposed by the action of an acid generating an alkali-soluble group. The same is true for the -CO ₂ R ³ "of the -CO ₂ R ³ ', the formula (3) in the formula (2).

A group which is decomposed by the action of an acid to generate an alkali-soluble group means a group which is decomposed by the action of an acid and generates an alkali-soluble group such as a hydroxyl group or a carboxyl group on the resin side (hereinafter also referred to as an acid-decomposable group). In the present invention, the acid-decomposable group is preferably a group which is decomposed by the action of an acid and generates a carboxyl group as an alkali-soluble group on the resin side.

A preferable group as the acid decomposable group is a group in which the hydrogen atom of the alkali-soluble group is substituted with a group which is eliminated by an acid.

The group is eliminated by an acid, for example, _{-C (R 36) (R 37} ) (R 38), -C (R 36) (R 37) (OR 39), -C (R 01) (R 02 ) (OR ₃₉ ). In the formula, R ₃₆ to R ₃₉ each independently represent 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The acid decomposable group is preferably a tertiary alkyl ester group, an acetal ester group, a cumyl ester group or an en ester group. More preferably a tertiary alkyl ester group or an acetal ester group. By using this, a photosensitive film having high sensitivity and high resolution can be obtained.

As the tertiary alkyl ester group as the acid decomposable group, it is preferable that the hydrogen atom of the carboxyl group is an ester group substituted with a group represented by the following general formula (AI).

In the general formula (AI)

T represents a single bond or -Rt-COO- group. Rt represents an alkylene group or a cycloalkylene group.

Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight chain or branched chain) or a cycloalkyl group (monocyclic or polycyclic).

Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group, a - (CH ₂ ) ₂ - group or a - (CH ₂ ) ₃ - group.

As the alkyl group of Rx _{1 to} Rx ₃ , those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-

The cycloalkyl group represented by R x _{1 to} R x ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or a polycyclic cycloalkyl group such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group or adamantyl group.

Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a polycyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group Cycloalkyl groups are preferred. Particularly preferred is a monocyclic cycloalkyl group having 5 or 6 carbon atoms.

Rx ₁ is a methyl group or ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-mentioned cycloalkyl group.

Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) And the number of carbon atoms is preferably 8 or less.

Specific examples of the group represented by the general formula (AI) constituting the tertiary alkyl ester group as the acid decomposable group are shown below, but the present invention is not limited thereto.

In the specific examples, Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent which each of the above groups may have, and when there are a plurality of substituents, they are independent of each other. p represents 0 or a positive integer.

The tertiary alkyl ester group as the acid decomposable group is a group represented by the general formula (AI), and is a group having at least any one of a group represented by the following general formula (I) and a group represented by the following general formula (II) More preferably a tertiary alkyl ester group.

Among the formulas (I) and (II)

R ₂ , R ₄ , R ₅ and R ₆ each independently represent an alkyl group or a cycloalkyl group.

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.

The alkyl group for R ₂ may be linear or branched or may have a substituent.

The cycloalkyl group for R ₂ may be monocyclic or polycyclic, and may have a substituent.

R ₂ is preferably an alkyl group, more preferably from 1 to 10 carbon atoms, and still more preferably from 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and its carbon number is preferably 3 to 7, more preferably 5 or 6.

The alkyl group in R ₄ , R ₅ and R ₆ may be straight-chain, branched or may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic or may have a substituent. As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group are preferable.

Examples of the group represented by the general formula (I) include groups represented by the following general formulas (I-a) and (I-b).

In the formula, R ₂ is R ₂ as agreed in the formula (I).

It is preferable that the group represented by the general formula (II) is a group represented by the following general formula (II-a).

In the formula (II-a)

R ₄ and R ₅ are the same as those in formula (II).

Specifically, the acetal ester group as the acid decomposable group is preferably an ester group in which the hydrogen atom of the carboxyl group is substituted with a group represented by the following general formula (III).

Rb represents a single bond or a divalent linking group.

At least two of Ra, Rb and Q may be bonded to each other to form a ring. This ring is preferably a 5-membered ring or a 6-membered ring.

The alkyl group, cycloalkyl group, aryl group or aralkyl group as Ra may be the same as those described above as the alkyl group, cycloalkyl group, aryl group or aralkyl group for R ³ in the general formula (1).

Ra is particularly preferably a hydrogen atom, a methyl group, a phenyl group or a benzyl group, and a photosensitive film of good sensitivity can be obtained.

It is also preferable that Ra is a group represented by the following general formula (IV) or (V) from the viewpoint of inhibiting the decomposition of the acetal ester group as an acid decomposable group during storage by steric hindrance and preventing the lowering of the patterning property.

Rc, Rd, Re, Rf and Rg each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom , Rc and Rd may combine with each other to form a ring, or at least two of Re, Rf and Rg may be bonded to each other to form a ring.

When Ra is a group represented by the general formula (IV) or (V), the progress of the imidization reaction during storage can be suppressed in the resin having the repeating unit represented by the general formula (1) .

The alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group as Rc, Rd, Re, Rf and Rg is preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group for R ³ in the general formula (1) The same thing can be said.

The aryloxy group as Rc, Rd, Re, Rf and Rg is preferably an aryloxy group having 6 to 10 carbon atoms, and specific examples thereof include phenoxy, toluyloxy and 1-naphthoxy.

The alkoxycarbonyl group as Rc, Rd, Re, Rf and Rg is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof include methoxycarbonyl, ethoxycarbonyl, linear or branched propoxycarbonyl, cyclopentyloxycarbonyl , Cyclohexyloxycarbonyl, and the like.

Examples of the aryloxy moiety of the aryloxycarbonyl group as Rc, Rd, Re, Rf and Rg include the same aryloxy groups as mentioned above.

From the viewpoint of inhibiting decomposition of the acetal ester group as an acid decomposable group during storage and preventing the lowering of the patterning property, at least one of Rc and Rd in the formula (IV) is a cycloalkyl group, an aryl group, an aralkyl group, An aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and it is more preferable that at least one is an aryl group.

The divalent linking group as Rb 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) (preferably a cycloalkylene group, such as cyclopentyl group or a cyclohexylene group having a carbon number of 3~15), -S-, -O-, -CO- , -CS-, -SO 2 -, -N ( R ₀ ) -, or a combination of two or more thereof, and preferably has a total carbon number of 20 or less. Here, R ₀ represents a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically methyl, ethyl, propyl, n-butyl, sec- to be.

R b is preferably a divalent linking group consisting of a single bond, an alkylene group, or a combination of an alkylene group and at least one of -O-, -CO-, -CS- and -N (R ₀ ) -, And a divalent linking group composed of a combination of an alkylene group and -O- is more preferable. Here, R ₀ is synonymous with R ₀ described above.

The alkyl group as Q is, for example, the same as the above-mentioned alkyl group as Ra.

Examples of the perspiration and aromatic ring as Q include a cycloalkyl group and an aryl group as Ra described above. The carbon number thereof is preferably 3 to 18. In the present invention, a group in which a plurality of aromatic rings are linked through a single bond (e.g., a biphenyl group or a terphenyl group) is also included in the aromatic group as Q.

Examples of the aromatic ring containing a heteroatom and a heteroatom include aromatic rings such as thiiran, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, Benzoimidazole, triazole, thiadiazole, thiazole and pyrrolidone.

The ring and aromatic ring as Q may have a substituent, and examples thereof include an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group.

(-Rb-Q) is particularly preferably a methyl group, an aryloxyethyl group, a cyclohexylethyl group or an arylethyl group, and the solubility and thermal stability are improved.

Examples of the case where at least two of Ra, Rb and Q are bonded to each other to form a ring include, for example, a 5-membered ring or a 5-membered ring containing an oxygen atom, in which any one of Rb and Q is bonded to Ra to form a propylene group or a butylene group, 6-membered ring.

When indicated the total number of carbon atoms of Ra, Rb and Q by N _C, if the N _C is large, the before and after the elimination groups represented by formula (III), the alkali dissolution rate change of the resin (a) becomes large, melting The contrast is lightened and the resolution is improved. The range of N _C is preferably 2 to 20, particularly preferably 2 to 15. When N _C is 20 or less, the glass transition temperature of the polymer compound is inhibited from being lowered, and the generation of defects in which the desorption from the acid decomposable group adheres to the pattern is inhibited.

It is preferable that at least one of Ra, Rb and Q is a group having an electron-withdrawing group or an electron-withdrawing group. Accordingly, in the resin (a) having the repeating unit represented by the general formula (1), decomposition of the acid decomposable group during storage can be suppressed, and deterioration of the patterning property can be prevented.

Examples of the electron attractive group include an alkoxy group, an aryl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxyl group, a nitrile group (cyano group), an alkylsulfonyl group , An arylsulfonyl group, and a nitro group, and is preferably an alkoxy group, an aryl group or an acyl group.

Specific examples of the group represented by the general formula (III) constituting the acetal ester group as the acid decomposable group are shown below, but the present invention is not limited thereto.

The general formula (1) -CO ₂ R ^3, the general formula ₍₂₎ -CO 2 R ³ 'or the thermal decomposition temperature of -CO ₂ R ³ "in the general formula 3 in the in the More preferably 120 to 210 deg. C, and particularly preferably 140 to 200 deg. C. The pyrolysis temperature can be obtained from, for example, differential thermal calorimetry.

If the thermal decomposition temperature is too low, the storage stability of the photosensitive resin composition of the present invention may be deteriorated. If the pyrolysis temperature is too high, the stress becomes large and the wafer warpage may increase. Further, decomposition products remain in the film, which may cause outgas and lowered reliability.

By setting the pyrolysis temperature to be 100 to 220 占 폚, the stress of the cured relief pattern according to the present invention is further lowered and the warpage of the wafer becomes smaller. The reason why the stress is further lowered is not clear, but when the thermal decomposition temperature is from 100 to 220 캜, -CO ₂ R ³ in the repeating unit represented by the general formula (1) becomes -CO ₂ H at low temperature curing, The in-plane orientation of the polyimide film is enhanced by cyclization, and it is presumed that the polyimide film becomes low in stress.

As the structure of R ³ , R ³ 'or R ³ "capable of achieving the thermal decomposition temperature as described above, specifically,

At least one of Rx ₁ to Rx ₃ in the general formula (AI) is a group represented by the following general formula (VI)

And a structure in which Ra in the general formula (III) is a group represented by the general formula (IV) or the following general formula (VII).

In the above general formula (VI)

R ₇ to R ₈ each independently represent a hydrogen atom, an alkyl group (straight chain or branched), or a cycloalkyl group (monocyclic or polycyclic), and at least one of R ₇ to R ₈ is a hydrogen atom.

In the general formula (VII)

Rh represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.

Specific examples of the alkyl group and cycloalkyl group for R ₇ to R ₈ include alkyl groups and cycloalkyl groups for R x _{1 to} R x _{3 which} are the same as the specific examples and preferred examples described above.

Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group as Rh include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkoxy group for R ³ in the general formula (1) .

The aryloxy group as Rh is preferably an aryloxy group having 6 to 10 carbon atoms, and specific examples thereof include phenoxy, toluyloxy, 1-naphthoxy and the like.

As the alkoxycarbonyl group as Rh, an alkoxycarbonyl group having 1 to 10 carbon atoms is preferable, and specifically, methoxycarbonyl, ethoxycarbonyl, straight-chain or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, etc. .

Examples of the aryloxy moiety of the aryloxycarbonyl group as Rh include the same aryloxy groups as mentioned above.

In the present invention, a hydrogen atom and an organic group may be mixed in R ³ . Is preferably 100 mol% to 20 mol%, more preferably 100 mol% to 40 mol%, based on all R ³ in the resin (a). By adjusting the hydrogen atom of R ³ and the amount of the organic group, the dissolution rate with respect to the aqueous alkaline solution is changed. Thus, a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

The proportion of the -CO ₂ R ³ in all the -CO ₂ R ³ groups in the resin (a), which is decomposed by the action of an acid to occupy the group capable of generating an alkali-soluble group, that is, the so-called protection ratio is preferably 40 to 100%, more preferably 45 to 100% Do.

Further, in the present invention, the terminal sealing agent may be reacted with the terminal of the polymer having the structural unit represented by the general formula (1) as a main component. The end sealant may be a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a mono-active ester compound. Is preferable in that the number of repeating structural units, that is, the molecular weight, can be controlled within a preferable range by reacting the terminal sealing agent. In addition, the end sealant can suppress acid deactivation due to neutralization of the terminal amine and the generated acid. Further, by reacting the end-capping 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.

The monoamine used in the end sealant is selected from the group consisting of 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, Aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-hydroxy- Amino-naphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy- Amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy- Amino naphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, Aminonaphthalene, 2-carboxy-3-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 2-carboxy- Aminonicotinic acid, 6-aminonicotinic acid, 4-aminonicotric acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-0-tolyloxanic acid, 2-aminobenzoic acid, 2-aminobenzoic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2 Aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8- aminonaphthalene, 1- Aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1- Aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-2-aminonaphthalene, 2-mercapto- 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine 2-aminothiophenol, 4-aminothiophenol, 2-ethynyl aniline, 3-ethynyl aniline, 4-ethynyl aniline, Diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1- Aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2- Ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene Aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 2- Aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,5-diethynyl- , 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene and 4,8-diethynyl-2-aminonaphthalene. However, it is not limited to these.

Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1- Aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, Aminophthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino Aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminosalicylic acid, -Aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynyl aniline, 4- A carbonyl such as aniline, 3,4-diethoxy-ethynyl aniline, 3,5-diethoxy-ethynyl aniline is preferred.

The acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and active ester compounds used as end-caps are selected from phthalic anhydride, maleic anhydride, anhydrous nadic acid, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride Carboxylic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy- Carboxy naphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy- Carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene 2-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2-carboxybenzenesulfonic acid, 4-diethynyl benzoic acid, 2,5-diethynyl benzoic acid, 2,6-diethynyl benzoic acid, 3,4-diethynyl benzoic acid, Naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl- Ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid and the like, monoacid chloride compounds in which these carboxyl groups are acid chloridated, and Terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2 -Dicarboxy naphthalene, 1,7-dicarboxy naphthalene, 1,8-di-naphthalene, 1,6-dicarboxy naphthalene, Monoacid chloride compounds in which only monocarboxylic groups of dicarboxylic acids such as carboxynaphthalene, 2,3-dicarboxy naphthalene, 2,6-dicarboxy naphthalene and 2,7-dicarboxy naphthalene are acid chloridated, And active ester compounds obtained by the reaction of chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide.

Of these, acid anhydrides such as phthalic anhydride, maleic anhydride, anhydrous nadic acid, cyclohexanedicarboxylic acid anhydride and 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, Carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3, 5-carboxybenzenesulfonic acid, -Diethynylbenzoic acid, and monocarboxylic acid compounds in which these carboxyl groups are acid chloridated, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxy naphthalene, 1 , 6-dicarboxy naphthalene, 1,7-dicarboxy naphthalene, 2,6-dicarb A monoacid chloride compound in which only a monocarboxylic group of a dicarboxylic acid such as naphthalene is acid chloridated, a monoacid chloride compound, and an N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3 - an active ester compound obtained by the reaction of dicarboxyimide and the like are preferable.

The introduction ratio of the monoamine used in the end sealant is preferably in the range of 0.1 to 60 mol%, particularly preferably in the range of 5 to 50 mol% based on the total amine component. The introduction ratio of the compound selected from acid anhydride, monocarboxylic acid, monoacid chloride compound and mono-active ester compound used as a terminal sealing agent is preferably in the range of 0.1 to 100 mol% based on the diamine component, 5 to 90 mol%. A plurality of other end groups may be introduced by reacting a plurality of end sealants.

The end encapsulant introduced into the polymer can be easily detected by the following method. For example, the polymer into which the end sealant is introduced is dissolved in an acidic solution to decompose into an amine component and an acid anhydride component, which are constituent units of the polymer. The end sealant can be easily detected by gas chromatography (GC) or NMR measurement. In addition, it is also easily detectable by directly pyrolysis gas chromatography (PGC), infrared spectroscopy and ^13C NMR spectroscopy of the polymer component into which the end sealant is introduced.

The resin (a) used in the photosensitive resin composition of the present invention preferably contains a structural unit represented by the general formula (1) as a main component. The main component herein means that the structural unit represented by the general formula (1) is contained in an amount of 70 mol% or more. , More preferably at least 80 mol%, and most preferably at least 90 mol%.

The resin used in the present invention may be a copolymer of a structural unit represented by the general formula (1) and another structural unit, or may be a mixture of a plurality of resins containing a structural unit represented by the general formula (1).

In addition, for the general formula (1) it indicated that the structure resin [for example, which does not contain a structural unit represented by the resin and general formula (1) containing units, only R ² is an aromatic ring in the general formula (1) Resin] may be used. In this case, the resin containing the structural unit represented by the general formula (1) is preferably contained in an amount of 50 mass% or more, more preferably 75 mass% or more.

The kind and amount of the structural unit used for copolymerization or mixing is preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.

The resin (a) containing the repeating unit represented by the above general formula (1) is preferably 200,000 or less in mass average molecular weight, more preferably 1,000 to 200,000, and more preferably 2,000 to 100,000 in terms of the alkali dissolution rate, More preferably from 3,000 to 100,000. By setting the molecular weight in this range, it is possible to obtain a photoresist film having low stress, excellent mechanical properties, and excellent resolution and low development defects. In the present invention, the molecular weight can be measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.

The dispersity (molecular weight distribution) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5.

As the method for producing the resin (a) in the present invention, any of conventionally known methods may be used (see, for example, the latest polyimide to base and application (Japanese Polyimide Research Association)).

For example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature in the case of a polyamic acid or a polyamic acid ester, a method of obtaining a diester by a tetracarboxylic acid dianhydride and an alcohol, A method in which a diester is obtained by a tetracarboxylic acid dianhydride and an alcohol and then the remaining dicarboxylic acid is acid chloridated and reacted with an amine; a method in which a part of the carboxyl groups in the side chain is subjected to heat treatment Or by alkyl esterification using an esterification reagent or the like.

Among them, a polyamic acid is obtained by reacting a diamine compound and a tetracarboxylic acid dianhydride in an organic solvent at -20 to 50 占 폚 for several minutes to several days, and then reacting with a basic lower halide, (Synthesis Method 1) of obtaining a polyamic acid ester of the general formula (1) by reaction of dimethylformamide with a dialkyl acetal, (Synthesis Method 2) synthesizing a dicarboxylic acid having an acid-decomposable group as described in Chem., 194, 511 to 521 (1993) and then polycondensation with a diamine is preferable in terms of cost, simplicity of operation, desirable.

(Synthesis method 1)

(Synthesis method 2)

In the scheme, R ¹ , R ² and R ³ are the same as those in the general formula (1).

Examples of the organic solvent that can be used for the synthesis reaction of the polyamic acid include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Amide solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile and pyridine; aromatic solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2- Halogen-based solvents such as tetrachloroethane, ether-based solvents such as tetrahydrofuran, dioxane and diglyme, and the like. Among them, an amide-based solvent is preferred, and a polyamide acid of high molecular weight can be obtained.

The boiling point of the organic solvent used in the polymerization reaction is preferably 50 占 폚 or higher, more preferably 100 占 폚 or higher, and particularly preferably 150 占 폚 or higher.

The concentration of the solute in the reaction liquid is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, and particularly preferably 10 to 20 mass%.

The polyamide acid ester obtained as described above is formed on a substrate such as a semiconductor substrate together with the component (b), and a relief pattern can be formed by a subsequent lithography process. By the heat treatment of this pattern, dehydration ring closure of polyamic acid ester or polyamic acid is generated to obtain a polyimide cured film.

In the present invention, the polyamic acid ester having the structural unit represented by the general formula (1) has an i-line transmittance of 1% or more, preferably 5% or more, per 20 m of film thickness, More preferably 10% or more, and particularly preferably 10 to 80%. If this value is less than 1%, it is difficult to obtain a photosensitive resin composition capable of forming a pattern having high resolution and good shape. The transmittance of the i-line (light having a wavelength of 365 nm) can be measured by a spectrophotometer (for example, Hitachi U3410, manufactured by Hitachi, Ltd.).

The residual stress of the polyimide cured film formed by imide cyclization from the polyamic acid ester having the structural unit represented by the general formula (1) is preferably 25 MPa or less, more preferably 20 MPa or less.

Here, if it exceeds 25 MPa, there is a drawback that the warpage of the silicon wafer and the residual deformation inside the silicon chip become large. The residual stress of the polyimide film can be measured at room temperature (25 캜) by a thin film stress measuring apparatus (for example, FLX-2320 manufactured by Tencor Corporation).

The polyamide acid ester having the structural unit represented by the general formula (1) satisfying these characteristics has a structure capable of forming a rigid and straight main chain by suppressing the directional ring-π conjugation length by selecting an appropriate monomer .

In the present invention, the resin (a) may be used singly or in combination. In addition, resins other than the resin (a) may be used in combination.

(b) a compound which generates an acid upon irradiation with an actinic ray or radiation

The composition of the present invention contains a compound (also referred to as a " photoacid generator " or " component (b) ") which generates an acid upon irradiation with an actinic ray or radiation. These may be used in combination of two or more. A sensitizer may also be used in combination for adjusting the sensitivity.

(b1)

Examples of the photoacid generator include photoinitiators for photo cationic polymerization, photoinitiators for photo-radical polymerization, photo-decoloring agents for colorants, photochromic agents, and known compounds that generate an acid upon irradiation with an actinic ray or radiation, And a mixture thereof can be suitably selected and used.

Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfone, disulfone and o-nitrobenzylsulfonate.

Further, a group capable of generating an acid upon irradiation with an actinic ray or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as those described in U.S. Patent No. 3,849,137, German Patent No. 3914407, Japanese Patent Application Laid-open Nos. 26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, Compounds described in JP 63-146029 A and the like can be used.

Compounds which generate an acid by the light described in U.S. Patent No. 3,779,778 and European Patent No. 126,712 can also be used.

Among the compounds capable of generating an acid upon irradiation with an actinic ray or radiation, compounds represented by the following general formulas (ZI), (ZII) and (ZIII) can be mentioned.

In the above general formula (ZI)

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

Among the general formulas (ZII) and (ZIII)

Each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group.

(Alkylsulfonyl) methide anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , and SbF ₆ ^{- is an} unsubstituted anion and X ^- is an unsubstituted anion, preferably a sulfonic acid anion, a carboxylic acid anion, , And preferably an organic anion having a carbon atom.

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

In the above general formula,

Rc ₁ represents an organic group.

As the organic group in Rc ₁ , an organic group having 1 to 30 carbon atoms can be exemplified, and an optionally substituted alkyl group, a cycloalkyl group, an aryl group, or a plurality of these groups may be bonded to form a single bond, -O-, -CO ₂ - , -S-, -SO ₃ -, -SO ₂ N (Rd ₁ ) -, and the like.

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 combined to form a ring.

The group formed by combining Rc ₃ and Rc ₄ includes an alkylene group, a cycloalkylene group, and an arylene group. Preferably a perfluoroalkylene group having 2 to 4 carbon atoms.

Rc ₁ and Rc _{3 to} Rc ₅ , preferably a phenyl group substituted by an alkyl group, fluorine atom or fluoroalkyl group whose 1-position is substituted by 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, since Rc ₃ and Rc ₄ are combined to form a ring, the acidity of the acid generated by the light irradiation is increased and the sensitivity is improved, which is preferable.

In the general formula (ZI)

The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20. As the organic group for R ~R ₂₀₁ ₂₀₃ may be mentioned an aryl group, an alkyl group, a cycloalkyl group and the like.

Also, R ₂₀₁ ~R by combining two of the dog ₂₀₃ may be bonded to form a ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group may be in the ring. R ₂₀₁ ~R ₂₀₃ The group formed by two of which in combination may be mentioned an alkylene group (e.g., a butylene group, a pentylene group).

In the general formulas (ZII) and (ZIII), the aryl group represented by R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, 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 and the like. The skeleton of the aryl group having a heterocyclic structure includes, for example, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene and the like.

The alkyl group and cycloalkyl group represented by 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 or pentyl group), a cycloalkyl group having from 3 to 10 carbon atoms Alkyl group (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent which the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms) (For example, having from 6 to 15 carbon atoms), an alkoxy group (for example, having from 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

The triarylsulfonium salt is particularly preferable in view of heat stability and sensitivity, and it is preferable to use a sensitizer in combination.

These compounds may be used in combination of two or more as necessary.

The triarylsulfonium salt preferably has at least one aryl group as an electron-withdrawing group as a substituent, and the total sum of the Hammett values of the substituents bonded to the aryl skeleton is preferably larger than 0.18.

Here, the electron-attracting group means a substituent having a Hammett value (Hammett substituent integer?) Of greater than zero. In the present invention, from the viewpoint of high sensitivity, the total sum of the Hammett values of the substituents bonded to the aryl skeleton in the specific photoacid generator is preferably 0.18 or more, more preferably 0.46, and even more preferably 0.60 .

The Hammett value indicates the degree of electron-withdrawing of the cation having a triarylsulfonium salt structure. From the viewpoint of high sensitivity, there is no upper limit value. From the viewpoint of reactivity and stability, however, the Hammet value is preferably more than 0.46 and less than 4.0 More preferably more than 0.50 and less than 3.5, particularly preferably more than 0.60 and less than 3.0.

The numerical values described in the present invention are described in Inamoto Naoki, Kagaku Seminar 10 Hemathematics - Structure and Reactivity - [1983, published by Maruzen Co., Ltd.].

Examples of the electron-attracting 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 [for example, -F (m: 0.34, p : 0.06), -Cl (m: 0.37, p: 0.23), - (For example, -COCH ₃ , o: 0.37, p: 0.45), a sulfoxide group (for example, _{g., -SOCH 3, m: 0.52,} p: 0.45), cyano groups (-CN, m: 0.56, p : 0.66), amide groups _{(e.g., -NHCOCH 3, m: 0.21,} p: 0.00), A carboxyl group (-COOH, m: 0.37, p: 0.45), a carbonyl group (-CHO, m: 0.36, p: 0.43) (M: 0.50) in the parentheses indicates the introduction position in the aryl skeleton of the substituent and its Hammett value, and (m: 0.50) means that the Hammett value when the substituent is introduced at the meta position is 0.50.

Among these substituents from the viewpoint of the hydrophobic nonionic substituent such as a halogen atom, a halogenated alkyl group, and preferably, -Cl is preferable from the viewpoint of reactivity, and among them, from the viewpoint of imparting a hydrophobic property is -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. Further, the number of the substituents introduced into each of the three aryl skeletons may be one or plural. In the present invention, the total sum of the Hammett values of the substituents introduced into these aryl skeletons preferably exceeds 0.18, and more preferably exceeds 0.46. The number of substituents introduced is arbitrary. For example, only one substituent group having a large Hammett value (for example, a Hammett value of more than 0.46) may be introduced into one of the aryl skeletons of the triarylsulfonium salt structure. It is also possible to introduce, for example, a compound in which a plurality of substituents are introduced and the total sum of the Hammett values exceeds 0.46.

As described above, since the Hammett value of the substituent varies depending on the position at which the substituent is introduced, the total sum of the Hammett values in the specific photoacid generator according to the present invention is determined by the kind of substituent, the introduction position, and the introduced number .

Also, the Hammett equation is usually expressed by the m-position and the p-position, but in the present invention, the substituent effect at the o-position as an index of the electron acceptability is calculated to be the same value as the p-position. The preferable substitution position is m position, p position is preferable from the viewpoint of synthesis, and p position is most preferable.

In the present invention, preferred is a sulfonium salt which is tri- or more substituted by a halogen atom, and most preferable is a sulfonium salt that is tri-substituted by a chloro group. Specifically, a halogen atom is added to each of three aryl skeletons, -Cl is preferably introduced, and it is more preferable that -Cl is substituted at the p-position.

As the sulfonic acid anion of the triarylsulfonium salt contained in the composition of the present invention, for example, an arylsulfonic acid anion, an alkanesulfonic acid anion and the like, and an anion substituted with an organic group having a fluorine atom or a fluorine atom are preferable.

Compounds having a triarylsulfonium salt structure are described, for example, in J. Am. Chem. Soc. 112 (16), 1990; pp.6004-6015, J. Org. Chem. 1988; pp.5571-5573, WO02 / 081439A1 pamphlet, European Patent (EP) No. 1113005, and the like.

Specific examples are given below, but the present invention is not limited thereto.

In addition, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfoniumtrifluoro Acetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium tri (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecarboxy) phenyl iodide Phenyl-4- (2'-hydroxy-1'-tetradecarboxy) phenyliodonium-p-toluenesulfonate, and the like; Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like;

As the imidosulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hepto-5-endocarboximide, succinimide trifluoromethylsulfonate, phthalimide p-toluenesulfonate, phthalate Hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide propanesulfonate, and the like.

Among the compounds which generate an acid upon irradiation with an actinic ray or radiation, oxime compounds and more preferably oxime sulfonate compounds are mentioned as the most preferable examples from the viewpoints of sensitivity, resolution, dielectric constant and dimensional stability.

As the compound having an oxime sulfonate compound, that is, an oxime sulfonate moiety, a compound containing an oxime sulfonate moiety represented by formula (b1) can be preferably exemplified.

[In the formula (b1), R ⁵ represents an alkyl group or an aryl group]

The alkyl group in R ⁵ may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ⁵ is preferably an aryl group having ⁶ to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a polycyclic alicyclic group such as a 7,7-dimethyl-2-oxononyl group, An alkyl group or the like).

As the aryl group for R ^5, an aryl group having ⁶ to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R < ⁵ > may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The oximesulfonate compound represented by the formula (b1) is particularly preferably an oximesulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5) Do.

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each of R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ 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, and m represents an integer of 0 to 6, Indicates]

In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ¹ may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ¹ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which 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 a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a s- , n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl groups.

The aryl group in R ¹ in formulas (OS-3) to (OS-5) is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the aryl group in R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, sulfonic acid groups, , And an alkoxysulfonyl group.

Examples of the aryl group for R ¹ include a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group.

The heteroaryl group in R ¹ in formulas (OS-3) to (OS-5) is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the heteroaryl group in R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, An alkoxy group, an alkoxy group, an alkoxy group,

Of the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group in R ¹ may be at least one of the rings is a heteroaromatic ring, and for example, a heterocyclic aromatic ring and a benzene ring may be coordinated.

Examples of the heteroaryl group for R ¹ include a ring selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring and a benzoimidazole ring which may have a substituent And a group excluding one hydrogen atom from the group represented by R < 1 >

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of the above formulas (OS-3) to (OS-5), one or two of R ² present in at least two of the compounds are preferably an alkyl group, an aryl group or a halogen atom, and one of them is an alkyl group, , It is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

In the above formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ² may have a substituent. Examples of the substituent which the alkyl group or aryl group in R ² may have include the same group as the substituent which the alkyl group or aryl group in R ¹ may have.

The alkyl group in R ² is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent and more preferably an alkyl group having 1 to 6 carbon atoms in total which may have a substituent.

Examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl 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- An ethyl group, an n-propyl group, an n-butyl group and an n-hexyl group are more preferable, and a methyl group is particularly preferable.

The aryl group in R ² is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Specific examples of the aryl group for R ² include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group.

Examples of the halogen atom in R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a chlorine atom and a bromine atom are preferable.

Of the above formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.

In the formulas (OS-3) to (OS-5), the ring containing X as reduction is a 5-membered ring or a 6-membered ring.

In the above formulas (OS-3) to (OS-5), n represents 1 or 2, and n is preferably 1 when X is O, and n is preferably 2 when X is S.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent which 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 a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- , n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl groups are preferred.

Of the above formulas (OS-3) to (OS-5), the alkyloxy group in R ⁶ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyloxy group of 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.

The alkyloxy group for R ⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group or an ethoxyethyloxy group.

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group and aminosulfonyl group have.

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group and 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, .

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).

Wherein 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, an alkyl group having 1 to 8 carbon atoms R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a methyl group, a halogen atom, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, Lt; / RTI &

Expression (OS-6) ~ R ¹ in (OS-11) is R ¹ and agreed in the formula (OS-3) ~ (OS -5), preferable form is also the same.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R ⁸ in formulas (OS-6) to (OS-11) represents 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, And is preferably 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, further preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group.

R ⁹ in formulas (OS-8) and (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, either of the three-dimensional structure (E, Z) of oxime may be used, or a mixture thereof may be used.

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.

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

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 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 a, R ⁵ ~R ⁷ represents an alkyl group or an aryl group .

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or 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 at least two of R ²¹ to R ²⁴ may be bonded to each other to form an aryl group. Among them, a form in which all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

All of the above-mentioned functional groups may further have a substituent.

The compound represented by the above 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 are respectively the same as those in the formula (OS-1), and preferred examples are also the same.

Among them, R ^{1 in the} formulas (OS-1) and (OS-2) is more preferably a cyano group or an aryl group, more preferably a form represented by the formula (OS-2) and R ¹ is a cyano group, Lt; / RTI > is most preferred.

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

Specific examples (Exemplary Compounds b-1 to b-34) of a compound represented by the formula (OS-1) which 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.

Of these compounds, b-9, b-16, b-31 and b-33 are preferred from the viewpoint of compatibility between sensitivity and stability.

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

Wherein (b2) of, R ⁵ represents an alkyl group or an aryl group, X is an alkyl group, an alkoxy group or a halogen atom, m is an integer of 0~3, m is 2 or 3, a plurality of X may be the same when the Or may be 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, X is a substituted position in the ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonobonylmethyl group, p-toluyl group is particularly preferable.

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

Wherein (b3) of, R ⁵ is R ⁵ as agreed in the formula (b1), X 'is an alkoxy group of the alkyl group, having 1 to 4 carbon atoms a halogen atom, a hydroxyl group, having 1 to 4 carbon atoms, a cyano group or a nitro group And L represents an integer of 0 to 5,

The R ⁵ in the formula (b3) is preferably a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- A n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.

X 'is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

L is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) [(Methylsulfonyloxyimino) -4-methoxyphenyl] acetophenone, which is used in the present invention, can be obtained by reacting an α- (n-butylsulfonyloxyimino) benzyl cyanide, Α - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, Butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and they may be used singly or in combination of two or more. The compounds (i) to (viii) are commercially available. It may 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 from 1 to 30 mass%, more preferably from 3 to 20 mass%, based on the total solid content of the photosensitive resin composition.

The acid generator may be used alone or in combination of two or more. When two or more compounds are used in combination, it is preferable to combine compounds that generate two kinds of organic acids different in total number of atoms except hydrogen atoms.

(b2)

A sensitizer may be added to the composition of the present invention in order to absorb the actinic ray or radiation to accelerate decomposition of the sulfonium salt. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the sulfonium to generate electron transfer, energy transfer, and heat generation. Accordingly, the polymerization initiator decomposes by causing a chemical change to generate radicals, acids or bases.

Examples of the preferable sensitizer include compounds having an absorption wavelength in the range of 350 nm to 450 nm belonging to the following compounds.

(E. G., Fluorene, eosine, erythrosine, rhodamine B, rose bengal), cyanines (e. G. , Thiocarbocyanine (e.g., thionine, methylene blue, toluidine blue), arsenic (such as thiocarbocyanine, oxacarbocyanine), merocyanines (Such as acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squaryliums (for example, squarylium), coumarins (for example, For example, 7-diethylamino-4-methylcoumarin).

Examples of the more preferable 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 represents a nonmetal atomic group which forms a basic nucleus of the pigment in association with the adjacent A ¹ and adjacent carbon atoms , R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetal atomic group, and R ⁵¹ and R ⁵² may combine with each other to form an acidic nucleus of the dye. 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 connected through a bond by -L ³ -. Here, L ³ represents -O- or -S-. W is synonymous with that shown in formula (IX).

In formula (XI), A ₂ represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetal atomic group which forms a basic nucleus of the dye together with the adjacent A ₂ and the carbon atom, and R ⁵³ , R ⁵⁴ and R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent group of a non-metallic 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 -, R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted an aryl group denotes, L ^5, L ⁶ is a ^3, a ⁴ and adjacent denotes a non-metallic atomic group forming a basic nucleus of a carbon atom in collaboration with the dye, R ^60, R ⁶¹ each independently represents a hydrogen atom which are adjacent to each other, each independently Or a monovalent nonmetal atomic group or may combine with each other to form an aliphatic or aromatic ring.

In the formula (XIII), R ⁶⁶ represents an aromatic ring or a heterocycle 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 nonmetal atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ may be bonded to each other to form an aliphatic or aromatic ring have.

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

As the sensitizer, an anthracene derivative is particularly preferable.

Preferable specific examples of the compounds represented by formulas (IX) to (XIV) include (C-1) to (C-26) shown below, but the present invention is not limited thereto.

The sensitizer as described above may be commercially available 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 from 1 to 30 mass%, more preferably from 3 to 20 mass%, based on the total solid content of the photosensitive resin composition.

(c) a basic compound

The composition according to the present invention preferably contains a basic compound in order to reduce the change in performance due to aging from exposure to heating.

The basic compound is preferably a compound having a structure represented by the following formulas (A) to (E).

Among the general formulas (A) and (E)

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having 6 to 20 carbon atoms) , Wherein R ²⁰¹ and R ²⁰² may be bonded to 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.

With regard to 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 amorphous.

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

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzoimidazole and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8- Cyclo [5,4,0] undeca-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 (T-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, . As the compound having an onium carboxylate structure, the anion portion of the compound having an onium hydroxide structure is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, perfluoroalkylcarboxylate and the like . Examples of the compound having a trialkylamine structure include tri (n-butyl) amine, tri (n-octyl) amine and the like. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutyl aniline and N, N-dihexyl aniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

Preferred examples of the basic compound 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.

The amine compound may be a primary, secondary or tertiary amine compound, and is preferably an amine compound in which at least one alkyl group is bonded to a nitrogen atom. More preferably, the amine compound is a tertiary amine compound. When the at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom, the amine compound may contain, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 12 carbon atoms) Or may be bonded to an atom. The amine compound preferably has an oxygen atom in the alkyl chain and is formed with an oxyalkylene group. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among 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, Oxyethylene group.

The ammonium salt compound may be a primary, secondary, tertiary or quaternary ammonium salt compound, and is preferably an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom. When the at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom, the ammonium salt compound may contain, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably 6 to 12 carbon atoms) Or may be bonded to an atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and is formed with an oxyalkylene group. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among 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, Oxyethylene group.

Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate. Among them, a halogen atom and a sulfonate are preferable. As the halogen atom, chloride, bromide and iodide are particularly preferable, and as the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkylsulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkylsulfonate include methanesulfonate, ethanesulfonate, butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutane Sulfonate and the like. The aryl group of the arylsulfonate includes 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 straight chain or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the straight chain or branched alkyl group and the cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group and an acyloxy group.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal on the opposite side to the nitrogen atom of the alkyl group of the amine compound or the 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 sulfonate ester group, an aryl group, an aralkyl group, . The substitution position of the substituent may be any of 2-6 positions. The number of substituents may be in the range of 1 to 5.

It is preferable that at least one oxyalkylene group is present between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among 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, Oxyethylene group.

The sulfonic acid ester group in the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group may be any of an alkylsulfonic acid ester, a cycloalkyl group sulfonic acid ester and an arylsulfonic acid ester. In the case of an alkylsulfonic acid ester, , The cycloalkyl group has 3 to 20 carbon atoms in the case of the cycloalkyl sulfonic acid ester and the aryl group has 6 to 12 carbon atoms in the case of the aryl sulfonic acid ester. The alkylsulfonic acid ester, the cycloalkylsulfonic acid ester and the arylsulfonic acid ester may have a substituent, and as the substituent, a halogen atom, cyano group, nitro group, carboxyl group, carboxylic acid ester group or sulfonic acid ester group is preferable.

And at least one oxyalkylene group is present between the sulfonate ester group and the nitrogen atom. The number of oxyalkylene groups in the molecule is at least 1, preferably from 3 to 9, more preferably from 4 to 6. Among 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, Oxyethylene group.

In addition, the following compounds are also preferable as basic compounds.

These basic compounds may be used singly or in combination of two or more kinds.

The content of the basic compound in the composition is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition, to be.

The ratio of the acid generator to the basic compound used 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 reduction of resolution in accordance with the thickness of the relief pattern with time after exposure to heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

(d) Thermal acid generator

The present invention may contain a thermal acid generator. A thermal acid generator is a compound which generates an acid by heat and usually has a thermal decomposition point in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. For example, a sulfonic acid, a carboxylic acid, a disulfonyl Amide and the like.

As the generated acid, an alkyl or aryl carboxylic acid substituted with a strong sulfonic acid or an electron-withdrawing group having a pKa of 2 or less, and a disulfonylimide substituted with an electron-withdrawing group are preferable. Examples of the electron-withdrawing group include a halogen atom such as F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

It is required that the thermal acid generator is not decomposed in the prebaking process during storage and aging, or after the composition is applied, and is decomposed quickly in the heat curing process after patterning. Therefore, the thermal decomposition point is preferably 100 占 폚 to 300 占 폚. More preferably 120 ° C to 250 ° C, and still more preferably 150 ° C to 200 ° C.

As the thermal acid generator, a photo acid generator that generates an acid by the above exposure can be applied. For example, an onium salt such as a sulfonium salt or an iodonium salt, an N-hydroxyimide sulfonate compound, oxime sulfonate, o-nitrobenzylsulfonate and the like.

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

In the 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 represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

R _T1 ~R _T5 of any two or more, R and R _T6 _T7 _T8 and R and R _T9 is coupled to each well to form a ring structure, the ring structure is an oxygen atom, a sulfur atom, a ketone bond, an ester bond, an amide Bond.

Examples of the group formed by combining 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 an unconjugated anion, and as described above, an alkyl or aryl carboxylic acid substituted with a strong sulfonic acid or an electron withdrawing group having a pKa of 2 or less, and a disulfonylimide substituted with an electron withdrawing group are preferred. Examples of the electron-withdrawing group include a halogen atom such as F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the 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 the 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 polycyclic aromatic ring such as a naphthalene ring or an anthracene ring It is also good.

X ^- represents an acetylenic anion.

In the general formula (TA-3)

R _T17 represents an alkyl group (straight chain or branched) or a cycloalkyl group, preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms, more preferably a straight chain or branched alkyl group having 1 to 12 carbon atoms (e.g., a methyl group, , A straight chain or branched butyl group, a straight chain or branched pentyl group). Examples of the cycloalkyl group include a monocyclic cyclic alkyl group such as cyclopentyl group and cyclohexyl group, as well as a cyclic alkyl group having a crosslinking site such as a norbornyl group, tricyclodecanyl group and adamantyl group.

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 represent 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 the 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 _T18 and R _T19 and R _T20 and R _T21 include a butylene group and a pentylene group.

X ^- represents an acetylenic anion.

The alkyl group as R _T1 to R _T17 may be any of straight chain and branched groups and includes, for example, straight chain and branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (for example, A propyl group, a straight chain or branched butyl group, a straight chain or branched pentyl group).

The cycloalkyl group as R _T1 to R _T17 is meant to include a cyclic alkyl group having a polycyclic or crosslinking site together with a monocyclic alkyl group. The cycloalkyl group as R _T12 to R _T16 is preferably a cycloalkyl group having 3 to 8 carbon atoms For example, a cyclopentyl group, a cyclohexyl group).

The cycloalkyl group as R _T17 is preferably a cyclic alkyl group having a crosslinking site such as a norbornyl group, a tricyclodecanyl group or an adamantyl group together with a cycloalkyl group having 3 to 8 carbon atoms (e.g., a cyclopentyl group or a cyclohexyl group) .

The alkoxy group as R _T1 to R _T5 and R _T12 to R _{T16 may} be any of linear, branched and cyclic, and includes, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a straight chain and branched alkoxy group having 1 to 5 carbon atoms (For example, a methoxy group, an ethoxy group, a straight chain or branched propoxy group, a straight chain or branched butoxy group, a straight chain or branched pentoxy group), a cyclic alkoxy group having from 3 to 8 carbon atoms (e.g., a cyclopentyloxy group, And the time of the birthday).

The thioalkoxy group as R _T12 to R _{T16 may} be any of linear, branched and cyclic, and includes, for example, a thioalkoxy group having 1 to 10 carbon atoms, preferably a straight chain and branched thioalkoxy group having 1 to 5 carbon atoms , A straight or branched thiopropoxy group, a straight chain or branched thiopentoxy group), a cyclic thioalkoxy group having 3 to 8 carbon atoms (e.g., a thioalkoxy group such as thio Cyclopentyloxy group, thiocyclohexyloxy group).

The non-nucleophilic anion represented by 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.

As the organic group in Rc ₁ , an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of _two or more thereof, which may have a substituent, , -S-, -SO ₃ -, -SO ₂ N (Rd ₁ ) -, and the like.

Rd ₁ represents a hydrogen atom or an alkyl group.

Rc ₂ is the first position represents an alkyl group substituted with an alkyl group with a fluorine atom or a fluoroalkyl group.

Rc ₃ and Rc ₄ each independently represent an alkyl group whose 1-position is substituted with a fluorine atom or a fluoroalkyl group. Preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

Rc ₃ and Rc ₄ may be bonded to each other may be to form a ring.

Preferable iodonium salts include compounds represented by the following general formula (TA-4).

In formula (TA-4), R ₄₁ and R ₄₂ each represent a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which 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, a nitro group, a halogen atom, a hydroxyl group or a carboxyl group.

a represents 1 to 5, and b represents 1 to 5.

Provided that at least one of R ₄₁ and R ₄₂ represents an alkyl group which may have a substituent having 5 or more carbon atoms, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, A good acyl group, or an acyloxy group which may have a substituent.

X represents R-SO ₃ , R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.

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

Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or t-butoxycarbonyl, pentyloxycarbonyl , t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecanoxycarbonyl group and the like. Examples of the acyl group include those having 1 to 25 carbon atoms such as a formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group and t-amylcarbonyl group which may have a substituent. Examples of the acyloxy group include acetoxy group, propionyloxy group, butyryloxy group, t-butyryloxy group, t-amyloxy group, n-hexanecarbonyloxy group, n-dodecanecarbonyloxy group, n-dodecanecarbonyloxy group, n-hexadecanecarbonyloxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituent for these groups is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, And the like. As described above, at least one of R ₁ and R ₂ is preferably an alkyl group which may have a substituent having 5 or more carbon atoms, a cycloalkyl group which 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, or 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 them, examples of the alkyl group which may have a substituent as R ₄₁ and R ₄₂ include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, An octyl group or a decanyl group is preferable, and the cycloalkyl group is preferably a cyclohexyl group, a cyclooctyl group or a cyclododecanyl group which may have a substituent, and as the alkoxy group, a methoxy group, an ethoxy group, N-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group and n-dodecaneoxy group are preferable, and alkoxy Examples of the carbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, a pentyloxycarbonyl group, Hexyloxycarbonyl , an n-octyloxycarbonyl group and an n-dodecanoxycarbonyl group are preferable. The acyl group is preferably a formyl group, an acetyl group, a butyryl group, a valeryl group, a hexanoyl group, an octanoyl group, Propyloxy group, butyryloxy group, t-butylyloxy group, t-amyloxy group, n-hexanecarbonyloxy group, n-hexylcarbonyloxy group, An octanecarbonyloxy group is preferred.

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

The iodonium compound represented by the general formula (TA-4) used in the present invention is a counter anion, X ^-, which is a sulfonic acid having a specific structure as described above. Examples of the aliphatic hydrocarbon group which may have a substituent for R in the counter anion include a linear or branched alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group. Also, R is an 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, And has 1 to 20 carbon atoms. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, an adamantyl group, a norbornyl group, a camphor group, a tricyclodecanyl group and a menthyl group which may have a substituent. Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent.

Among them, examples of the alkyl group which may have a substituent represented by R include methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, n-propyl, An n-pentyl group, an n-hexyl group, an n-octyl group, a heptadecafluorooctyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, . Examples of the aromatic group include a phenyl group, a naphthyl group, a pentafluorophenyl group, a p-toluyl group, a p-fluorophenyl group, a p-chlorophenyl group, a p- Mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group and 6-hydroxy-2-naphthyl group.

More specific examples of R ₄₁ and R ₄₂ among the above substituents are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n-octyloxy group, n-hexyloxy group, An acetyl group, a butyryl group, a hexanoyl group, an octanoyl group, an isopropenyl group, an iso-propyl group, an iso-propyl group, , a t-butylcarbonyl group, a t-amylcarbonyl group, an acetoxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amyloxy group, A hydroxyl group, a chlorine atom, a bromine atom, and a nitro group. Specific examples of the more preferred 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, amyloxycarbonyl group, n-octyloxycarbonyl group, dodecanoxycarbonyl group, valeryl group, hexanoyl group, octanoyl group, t-amylcarbonyl group, a t-amyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.

Specific examples of the more preferable sulfonic acid substituent R include methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, n-butyl, nonafluorobutyl, n- A phenyl group, a naphthyl group, a pentafluorophenyl group, a p-toluyl group, a p-fluorophenyl group, a p-chlorophenyl group, a p-methoxy group A phenyl group, a dodecylphenyl group, a mesityl group, a triisopropylphenyl group, a 4-hydroxy-1-naphthyl group and a 6-hydroxy-2-naphthyl group.

The total number of carbon atoms of the generated acid is preferably 1 to 30. More preferably 1 to 28, and still more preferably 1 to 25. If the total number of carbon atoms is less than 1, there may be a problem such as defective marine due to volatilization. If the total number of carbon atoms is more than 30, residue of development may occur.

Specific examples of the compound represented by the general formula (TA-4) are shown below, but the present invention is not limited thereto. These compounds may be used alone or in combination of two or more.

Examples of imidosulfonate compounds which are preferable as thermal acid generators include the following compounds.

In the formulas, 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 is any one of the following (1) to Lt; / RTI >

(1) each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group,

(2) form, together with C ₁ and C ₂ , a monocyclic or polycyclic ring which may contain one or more heteroatoms,

(3) form a condensed aromatic ring comprising C ₁ and C ₂ ,

(4) N-sulfonyloxyimide.

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.

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

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

When R ₅₁ and R ₅₂ correspond to the case of (4), the so-called at least two N-sulfonyloxyimide residues are present in the moieties of R ₅₁ and R ₅₂ having the partial structures of (1) to (3) Or a divalent organic group as shown below. However, the following connecting groups may be used singly or in combination of two or more.

[Bivalent organic group]: -O-, -S-, -SO-, -SO ₂ -, -NH-, -CO-, -CO ₂ -, -NHSO ₂ -, -NHCO-, -NHCO ₂ - ,

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

Examples of the alkyl group for R < ₅₃ > include a linear or branched alkyl group having 1 to 20 carbon atoms. Preferably a straight chain or branched alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms. In the case of an alkyl group having 21 or more carbon atoms, sensitivity and resolving power are lowered, which is not preferable. As the halogenated alkyl group, one or more hydrogen atoms of the alkyl group may be halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferably a fluorine atom, a chlorine atom, or a bromine atom, and particularly preferably a fluorine atom. The halogen atom to be substituted may be plural kinds 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, polycyclic groups such as norbornyl group, adamantyl group and tricyclodecanyl group. Examples of the alkenyl group include a straight chain or branched alkenyl group having 2 to 20 carbon atoms. Preferably a straight chain or branched alkenyl group having 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms. In the case of an alkenyl group having 21 or more carbon atoms, sensitivity and resolving power are lowered, which is not preferable.

Examples of the aryl group for R ₅₃ include a phenyl group and a naphthyl group, and the aralkyl group includes a benzyl group. Examples of the substituent of the aryl group and the aralkyl group include lower alkyl groups such as methyl, ethyl, propyl, isopropyl and tert-butyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, phenyl, A lower alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a sec-butoxy group or a tert-butoxy group, an alkenyl group such as a vinyl group, an allyl group, a propenyl group or a butenyl group , An acyl group such as a formyl group and an acetyl group, and a halogen atom such as a hydroxyl group, a carboxy group, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and tert-butyl group, a cyclohexyl group, phenyl group, toluyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec- And a halogen atom such as a lower alkoxy group such as a tert-butoxy group, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The substituents on the aryl group and the aralkyl group may be two or more.

Specific examples of these compounds are shown below, but the present invention is not limited thereto.

Examples of the oxime sulfonate compound which is preferable as a thermal acid generator include compounds represented by the following general formulas.

In the general formula (TA-6), R ₆₁ and R _{62 each} represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group which may have a substituent, an aryl group which may have a substituent, An aryl group, or a cyano group. R ₆₁ and R ₆₂ each independently represent an alkylene chain, an alkenylene chain, an alkynyl chain, or a substituted or unsubstituted phenylene, furylene, thienylene, -O-, -S May be bonded to R ₆₁ or R ₆₂ of the compound represented by the other general formula (TA-6) through a linking chain including -, -N- and -CO-. That is, the compound represented by the general formula (TA-6) includes two or three compounds having an oxime sulfonate structure through a connecting chain.

R ₆₃ represents an alkyl group, a cycloalkyl group, or an aryl group which may have a substituent, which may have 1 to 16 carbon atoms and may have a substituent.

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- an alkyl group such as an n-octyl group, an i-octyl group, an n-decyl group, an undecyl group, a dodecyl group and a hexadecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorobutyl group, -Butyl group, perfluorooctyl group, perfluorodecyl group, 1,1-bistrifluoromethyl group, and the like.

Examples of the alkenyl group in R ₆₁ and R ₆₂ include an allyl group, a methacryl group, a vinyl group, a methylallyl group, a 1-butenyl group, a 3-butenyl group, a 2-butenyl group, Hexenyl group, 2-oxo-3-pentenyl group, decapentenyl group, 7-octenyl group and the like.

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

Examples of the cycloalkyl group represented by 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, and a bicyclo [4.2.4] dodeca-3,7-dien-5-yl group .

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

Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom (fluorine atom, chlorine atom, iodine atom), cyano group, hydroxy group, carboxyl group, nitro group, aryloxy group, alkylthio group, ), And the like.

Here, the alkyl group and the cycloalkyl group are the same as those exemplified above. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a 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 formula, R ₆₁ and R ₆₂ is R ₆₁ and R ₆₂ with the consent of the general formula (TA-6).

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

As the oxime sulfonate-based acid generator which is preferable as the thermal acid generator, there can be mentioned a compound having at least one group represented by the following formula (TA-7).

[In the formula (TA-7), R ^70a and R ^70b each independently represent an organic group]

The organic group of R ^70a and R ^70b is a group containing a carbon atom and includes atoms other than carbon atoms such as a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, etc.) You can have it.

As the organic group of R ^70a , a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl group and aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom, a straight chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, and the like. Here, the term "having a substituent" means that a part or all of the hydrogen atoms of the alkyl group or the aryl group are substituted with a substituent.

The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, 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 preferable. Further, the partially halogenated alkyl group means an alkyl group in which a part of the hydrogen atoms are substituted with halogen atoms, and a completely halogenated alkyl group means an alkyl group in which all of the hydrogen atoms are substituted with halogen atoms. 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 fully halogenated aryl group is particularly preferable. Further, the partially halogenated aryl group means an aryl group in which a part of the hydrogen atoms are substituted with halogen atoms, and the completely halogenated aryl group means an aryl group in which all of the hydrogen atoms are substituted with halogen atoms.

As R ^70a , an alkyl group having 1 to 4 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms is particularly preferable.

The organic group of R ^70b is preferably a linear, branched or cyclic alkyl group, aryl group or cyano group. Examples of the alkyl group and aryl group of R ^70b include the same alkyl groups and aryl groups exemplified above for R ^70a .

As R ^70b , 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 is particularly preferable.

As the oxime sulfonate-based acid generator, a compound represented by the following general formula (TA-7a) or (TA-7b) is preferably used since it has high acid generation efficiency for irradiation with electron beams.

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

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

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

As the general formula of the preferable nitrobenzylsulfonate, there may be mentioned a compound represented by the general formula (TA-9).

Wherein Z is an alkyl group, an aryl group, an alkylaryl group, a halogen substituted alkyl group, a halogen substituted aryl group, a halogen substituted alkylaryl group, a nitro substituted aryl group, a nitro substituted alkylaryl group, An aryl group having a substituent, an alkylaryl group having a nitro substituent and a halogen substituent, and a group having the formula C ₆ H ₄ SO ₃ CHR'C ₆ H ₄ _- _m Q _m (NO) ₂ , and R is a hydrogen atom Or a methyl group, R 'is selected from a hydrogen atom, a methyl group, and a nitro substituted aryl group, each Q is independently selected from a hydrocarbon group, a hydrocarbyloxy group, NO ₂ , a halogen atom and an organic silicon group, m Is 0, 1 or 2, with the proviso that Q is not an acidic group.

Specific examples of the compound represented by the general formula (TA-9) include, for example, the following compounds.

Sulfonic acid esters can also be used.

Examples thereof include sulfonic acid esters represented by the following general formula (TA-1).

R'-SO ₂ -OR "(TA-1)

In the above formulas, R 'and R "each independently represent a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent or an aryl group having 6 to 20 carbon atoms which may have a substituent. A halogen atom, a cyano group, a vinyl group, an acetylene group, and a straight or cyclic alkyl group having 1 to 10 carbon atoms.

Specific preferred 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 in terms of heat resistance.

The molecular weight of the sulfonic acid ester is generally 230 to 1000, preferably 230 to 800.

A represents a linking group of h.

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 linking group of h as A is, for example, an alkylene group (e.g., methylene, ethylene, propylene), a cycloalkylene group (cyclohexylene, cyclopentylene, etc.), an arylene group A group excluding h-2 of any hydrogen atoms, which is a bivalent group formed by combining a group of the above-mentioned groups, such as a methylene group, an ethyl group, an isopropyl group, an isopropyl group, an isobutyl group, have.

The number of carbon atoms of the h-gethering group as A is generally 1 to 15, preferably 1 to 10, and more preferably 1 to 6.

The alkyl group of 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. Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl and the like.

The aralkyl group of 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. Specific examples thereof 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, and more preferably a cyclic alkyl group having 5 to 15 carbon atoms. Specific examples thereof include cyclopentyl, cyclohexyl, norbornyl, camphor group and the like.

The linking group as A may further have a substituent and examples of the substituent include an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl and the like, an aralkyl group having 7 to 15 carbon atoms (Specifically, phenyl, tolyl, xylyl, mesityl, naphthyl, etc.), an aryl group (an aryl group having 6 to 10 carbon atoms, specifically, benzyl, toluylmethyl, , An alkoxy group (the alkoxy group is an alkoxy group having 1 to 10 carbon atoms which may be any of linear, branched and cyclic, specifically methoxy, ethoxy, straight chain or branched propoxy, straight chain or branched butoxy, Cyclohexyloxy and the like), an aryloxy group (an aryloxy group having 6 to 10 carbon atoms, specifically, phenoxy, toluyloxy, 1-naphthoxy and the like), an alkylthio group (straight chain, Branched or cyclic alkyl group having 1 to 10 carbon atoms (Specifically methylthio, ethylthio, straight chain or branched propylthio, cyclopentylthio, cyclohexylthio), arylthio groups (arylthio groups having 6 to 10 carbon atoms, specifically, phenylthio, tolylthio (1-naphthylthio), an acyloxy group (acyloxy group having 2 to 10 carbon atoms, specifically, acetoxy, propanoyloxy, benzoyloxy), an alkoxycarbonyl group (having 1 to 10 carbon atoms, , Specifically, methoxycarbonyl, ethoxycarbonyl, straight chain or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, etc.).

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 and an ethyl group, and most preferably a hydrogen atom.

Specific examples of the sulfonic acid ester of the present invention include, but are not limited to, the following specific compounds.

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

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

(e) a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group

The composition of the present invention may contain a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group. In the low-temperature curing process, it is also possible to prevent the pattern from melting and shrinking 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 directly substituted on a nitrogen atom of an aromatic group or a urea structure by a triazine substitution .

The alkoxymethyl group or acyloxymethyl group of the compound is preferably 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.

The total number of alkoxymethyl groups and acyloxymethyl groups of 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 1,500 or less, more preferably 180 to 1,200.

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 the alkoxymethyl group or the acyloxymethyl group is directly substituted with an aromatic group include compounds represented by the following general formula.

Wherein, X represents an organic group with a valence bond or two, each R ₁₀₄ independently represent an alkyl group or an acyl group, R ₁₀₃ is by a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or the action of an acid A group represented by -C (R ⁴ ) ₂ COOR ⁵ (wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), a group which is decomposed and generates an alkali-soluble group (for example, And R < ⁵ > represents a group which is eliminated by the action of an acid.

R ₁₀₅ 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.

A group which is decomposed by the action of an acid and generates an alkali-soluble group, a group which is cleaved by the action of an acid, and a group represented by -C (R ⁴ ) ₂ COOR ⁵ are the same as those in the general formula (1).

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

The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or a compound synthesized by a known method.

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 amount of these compounds to be added is preferably from 1 to 20 parts by mass, more preferably from 3 to 15 parts by mass, per 100 parts by mass of the total amount of the resin of the present invention.

(e ') a compound containing a methacryloyl group or an acryloyl group

The composition of the present invention may contain a compound containing a methacryloyl group or an acryloyl group.

The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of an acrylate ester and a methacrylate ester. Since these compounds are insoluble in an alkali developing solution, they have a function of suppressing the alkali solubility of the composition and suppress the reduction of the film in the unexposed portion, which is helpful for good image formation. Further, although the specific reaction mechanism is not known, the acrylic or methacrylic group reacts with the compound in the composition at the stage of the cure reaction, thereby partially increasing the molecular weight of the component constituting the composition, thereby improving the film properties. 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, so that this compound can exert its function as a crosslinking compound.

Further, the skeleton containing an acryloyl group or a methacryloyl group preferably has a cyclic structure such as an aromatic ring or an alicyclic ring, more preferably an alicyclic structure, is more preferable for the transmittance of the exposure light and the rigidity of the curing film.

The length (n) of the ethylene oxide (EO) chain and the propylene oxide (PO) chain in the skeleton is preferably long in the range of n = 1 to 5 because the rigidity of the film disappears.

AMP-20GY, AM30G, AM90G, AM230G, ACB-3, A-BH, A-IB, A-SA, A- M-20G, M-90G, M230G, PHE-1G, SA, CB-1, CB-3, CB-23, TOPOLENE-M, A-BPE-10, A-BPE-10, A-BPE-10, S-1800M, IB, OC-18E, S, bifunctional A-200, A-400, A-600, A-1000, ABE-300, A-NOD-N, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A-B1206PE, , APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD-N, NOD, IND, BPE- AT-30E, A-TMPT-3EO, A-TMPT-3EO, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3PG, ATM-4E, AD-TMP, AD, TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM- -TMP-L, ATM-4P, A-TMMT, and A-DPH.

Particularly preferred examples include the following polyfunctional monomers.

The amount of the compound containing a methacryloyl group or acryloyl group in the molecule of the present invention is preferably 0.5 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the resin having a repeating unit represented by the general formula (1). More preferably 1 part by mass or more and 20 parts by mass or less, particularly preferably 2 parts by mass or more and 15 parts by mass or less. The effect of the present invention can be obtained by setting the addition amount to 0.5 parts by mass or more, and the decrease in the heat resistance of the curing film can be prevented by appropriately suppressing the addition amount.

(f) adhesion promoter

To the positive photosensitive resin composition of the present invention, an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent may be added as needed to impart adhesion. Examples of these include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxy Silane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Methacryloxypropyl Trimethoxysilane, urea propyl triethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. When the adhesion promoter is used, the amount is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass, per 100 parts by mass of the resin of the present invention.

(g) Solvent

The solvent is not particularly limited so long as it is capable of dissolving the composition of the present invention, but a solvent having a boiling point of 100 占 폚 or more is preferable in order to prevent the solvent from evaporating more than necessary upon application and to prevent the solid content of the composition from being deposited upon application. For example, there may be mentioned alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms) Preferably 4 to 10 carbon atoms), an organic solvent such as an alkylene carbonate, an alkyl alkoxyacetate, an alkyl pyruvate, or an amide solvent.

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 ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

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. .

As the lactic acid alkyl ester, for example, methyl lactate, ethyl lactate, propyl lactate, and butyl lactate are preferably used.

As the alkyl alkoxypropionate, for example, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate are preferably used.

Examples of the cyclic lactone include, for example,? -Propiolactone,? -Butyrolactone,? -Butyrolactone,? -Methyl-? -Butyrolactone,? -Methyl-? -Butyrolactone,? -Valerolactone ,? -caprolactone,? -octanoic lactone, and? -hydroxy-? -butyrolactone.

Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3- Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl- Heptanone, 2-methyl-3-heptanone, 5-methyl-3-hexanone, 3-decanone, 3-decanone, 3-decanone, 3-decanone, 3-heptanone, 2-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2-methylcyclopentanone, 2-methylcyclopentanone, 2-methylcyclopentanone, Cyclohexanone, 4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexane Trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 2,2,6-trimethylcyclohexanone, 3-methylcycloheptanone.

As the alkylene carbonate, for example, propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate are preferably used.

Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy- Acetic acid-1-methoxy-2-propyl.

As the alkyl pyruvate, for example, methyl pyruvate, ethyl pyruvate and propyl pyruvate are preferably used.

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 preferably used.

Among these, more preferred solvents include N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), N, N-dimethylacetamide (DMAc), 1,3- ), N, N-dimethylformamide (DMF), cyclopentanone, cyclohexanone, cycloheptanone and the like. More preferred are? -Butyrolactone and N-methylpyrrolidone, cyclopentanone, and cyclohexanone.

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

The total solid content concentration in the photosensitive resin composition of the present invention is generally from 10 to 40 mass%, more preferably from 10 to 30 mass%, and still more preferably from 15 to 30 mass%.

[Method for manufacturing relief pattern]

As a method for producing a relief pattern using the photosensitive resin composition of the present invention, there is a method of (a) coating the photosensitive resin composition of the present invention on a suitable substrate to form a photosensitive film, (b) baking the coated substrate Baking), (c) exposing to actinic radiation or radiation, (d) developing with an aqueous developer, and (e) curing to form a cured relief pattern. In the exposed portion of the coated photosensitive film, since -OH is decomposed by action of an acid on -CO ₂ R ³ in the general formula (1) to generate an alkali-soluble group and removed by an aqueous alkali developer, A cured relief pattern is obtained.

The coated and exposed substrate may be baked at a high temperature prior to development (postexposure baking). Further, the developed substrate may be rinsed before curing.

Thus, the photosensitive resin composition of the present invention is coated on a semiconductor element so that the thickness after heat curing becomes a predetermined thickness (for example, 0.1 to 30 mu m), and the semiconductor device is manufactured by prebaking, exposure, development, can do.

Hereinafter, a method for manufacturing a relief pattern will be described in more detail.

The photosensitive resin composition of the present invention is coated on a desired substrate. The substrate is, for example, a semiconductor material such as a silicon wafer or a ceramic substrate, glass, metal or plastic. Coating methods include, but are not limited to, spray coating, spin coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.

The coating film is baked at a temperature of about 70 to 150 DEG C for several minutes to a half hour to evaporate the residual solvent. Subsequently, the obtained film is exposed to an actinic ray or radiation through a mask. As the actinic ray or radiation, an X-ray, an electron beam, an ultraviolet ray, a visible ray or the like can be used. The most preferred radiation has a wavelength of 365 nm (i-line) or 436 nm (g-line).

Following exposure to actinic radiation or radiation, it is desirable to heat the exposed substrate to a temperature of about 70-150 占 폚. And is usually heated to a predetermined temperature for several seconds to several minutes. This method is referred to as post-exposure baking.

By this post-exposure baking, polyamic acid is produced from the polyamic acid ester in the general formula (1) as shown in the following scheme.

Subsequently, the coating film is developed with an aqueous developer to obtain a relief pattern. Examples of the aqueous developers include inorganic alkalis such as potassium hydroxide, sodium hydroxide and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di (for example, triethylamine), quaternary ammonium salts (for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetraethylammonium hydroxide, and the like) ), And mixtures of these. The most preferred developer is one containing tetramethylammonium hydroxide. In addition, a suitable amount of a surfactant may be added to the developer. The development can be carried out by dipping, spraying, paddling, or other similar developing methods.

In some cases, the relief pattern may be rinsed off with deionized water. Then, in order to obtain a final patterned film having a high heat resistance, a polyimide is produced from the polyamic acid ester by heating and curing the relief pattern as shown in the following scheme. The curing is preferably baking at a temperature higher than the glass transition temperature (Tg) of the polymer in order to obtain polyimide having high heat resistance. The heat curing temperature is preferably about 200 to 400 캜, and particularly preferably 250 to 400 캜.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

[Conditions for measuring GPC]

The GPC measurement thereafter was conducted by directly connecting three HPC-8220 GPC (Tosoh Corporation), a guard column: TSKguardcolumn SuperAW-H, and a column: TSKgel SuperAWM-H at a column temperature of 50 캜 and a sample concentration of 0.5% Pyrrolidone solution [containing LiBr (10 mM) and H ₃ PO ₄ (10 mM)] as an eluting solvent was flowed at a flow rate of 0.35 ml per minute And detecting a sample peak in the RI detecting apparatus. Mw and Mn were calculated using a calibration curve prepared using standard polystyrene.

&Lt; Synthesis Example of Resin >

[Synthesis of P-1]

Synthesis of polyamic acid

123.42 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigas Co., Ltd.) was placed in a 5000 ml flask equipped with a thermometer, a stirrer and a nitrogen introducing tube, and NMP (N-methyl-2-pyrrolidone) g, and then 300.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Kagaku K.K.) was added thereto. The mixture was stirred at 60 占 폚 for 4 hours, then allowed to stand at room temperature (25 占 폚) and cooled. Subsequently, 30.27 g of phthalic anhydride was added and stirred at room temperature for 10 hours to obtain a colorless transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.68 × 10 ⁴ , Mn = 0.62 × 10 ⁴ , and Mw / Mn = 2.71.

Synthesis of polyamic acid ester

132.01 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 111.0 g of NMP was added and cooled. Then, 12.56 g of chloromethyl methyl ether and 12.56 g of N, N- 16.12 g of diisopropylethylamine was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 1175 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 24.6 g of the title compound (resin P-1) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.00 × 10 ⁴ and Mw / Mn = 1.91. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-2]

Polyamic acid was synthesized similarly to P-1. 132.01 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 111.0 g of NMP was added and cooled. 5.02 g of chloromethyl methyl ether and 5.02 g of N, N- 8.06 g of diisopropylethylamine was added. After 4 hours of reaction at 0 DEG C or lower, the reaction solution was added to 1175 g of methanol to obtain a precipitated solid which was filtered and dried to obtain 19.3 g of the title compound (resin P-2) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 1.88 × 10 ⁴ and Mw / Mn = 1.68. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result, the protection ratio was found to be 72% from the peak integral ratio of the carboxylic acid ester and the carboxylic acid.

[Synthesis of P-3]

Polyamic acid was synthesized similarly to P-1. 142.26 g of the polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 70.37 g of NMP was added thereto. The mixture was cooled, and 15.91 g of chloromethyl ethyl ether was added thereto, 17.39 g of diisopropylethylamine was added. After reacting at 0 ° C or lower for 4 hours, the reaction solution was added to 1267 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 23.6 g of the title compound (resin P-3) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.09 × 10 ⁴ and Mw / Mn = 1.73. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid to be 96%.

[Synthesis of P-7]

Polyamic acid was synthesized similarly to P-1. 132.01 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 111.0 g of NMP was added and cooled. 23.18 g of chloromethylcyclohexyl ether was added thereto at 0 캜 or lower, -Diisopropylethylamine < / RTI > was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 1175 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 24.8 g of the title compound (resin P-7) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.36 × 10 ⁴ and Mw / Mn = 1.72. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-8]

Polyamic acid was synthesized similarly to P-1. 132.01 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 111.0 g of NMP was added and cooled. 9.27 g of chloromethylcyclohexyl ether was added at 0 DEG C or lower, -Diisopropylethylamine were added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 1175 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 20.2 g of the title compound (resin P-8) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.13 x 10 ⁴ and Mw / Mn = 1.59. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. From the peak integral ratio of the carboxylic acid ester and the carboxylic acid, the protection ratio was calculated to be 64%.

[Synthesis of P-11]

Polyamic acid was synthesized similarly to P-1. 106.30 g of the polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 52.59 g of NMP was added thereto. The mixture was cooled, and 20.96 g of 2- (chloromethoxy) ethyl trimethylsilane, Subsequently, 13.00 g of N, N-diisopropylethylamine was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 947 g of methanol to obtain a precipitated solid which was filtered to obtain 13.5 g of the title compound (resin P-11) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 1.58 × 10 ⁴ and Mw / Mn = 1.55. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, which was 73%.

[Synthesis of P-16]

48.11 g of paraldehyde, 140.0 g of cyclohexane ethanol and 1.27 g of 10-camphorsulfonic acid were added to 150 g of hexane and refluxed in a Dean-Stark apparatus for 5 hours. The solution was washed twice with saturated sodium hydrogencarbonate solution and twice sequentially with water. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 157 g of a clear solution. Thereto was added 34.3 g of acetyl chloride, and the mixture was reacted at 50 DEG C for 5 hours, and then concentrated under reduced pressure to obtain 178 g of a transparent liquid. ¹ H-NMR spectrum was measured by dissolving in chloroform, and the content of cyclohexylethyl 1-chloroethyl ether was found to be 31% by mass.

105.61 g of the polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 52.23 g of NMP was added thereto. The mixture was cooled, 76.75 g of a 31 mass% solution, and then 26.87 g of N, N-diisopropylethylamine was added. After reaction at 0 DEG C or lower for 4 hours, the reaction solution was added to 940 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 16.5 g of the title compound (resin P-16) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.29 × 10 ⁴ and Mw / Mn = 1.75. The solid was dissolved in DMSO to measure the ¹ H-NMR spectrum and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid. As a result, it was 69%.

[Synthesis of P-19]

Polyamic acid was synthesized in the same manner as in P-1, and 106.30 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 52.59 g of NMP was added, 20.64 g of vinyl ether and 0.97 g of 10-camphorsulfonic acid were added sequentially. After reacting at 25 DEG C for 5 hours, the reaction solution was added to 947 g of acetonitrile to obtain a precipitated solid which was filtered to obtain 18.9 g of the title compound (resin P-19) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.50 × 10 ⁴ and Mw / Mn = 1.71. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-22]

105.29 g of the polyamic acid solution was added to a 300-ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 52.23 g of NMP was added thereto to obtain (1- (4-tert -Oxyl-phenoxy) -2-vinyloxy-ethane and 0.96 g of 10-camphorsulfonic acid were successively added to the reaction mixture at 25 DEG C. After the reaction was carried out at 25 DEG C for 5 hours, the reaction mixture was added to 940 g of acetonitrile, 22.1 g of a white solid (resin P-22) was obtained by analysis of the obtained resin by GPC, and Mw = 2.84 × 10 ⁴ and Mw / Mn = 1.71 The solid was dissolved in DMSO to obtain ¹ H -NMR spectrum was measured and the protection ratio was calculated from the peak atomic ratio of the carboxylic acid ester and the carboxylic acid to be 100%.

[Synthesis of P-26]

24.93 g of ethylene glycol monovinyl ether and 35.42 g of cyclohexylisocyanate were added to 150 ml of dehydrated ethyl acetate and the mixture was stirred at 70 캜 for 6 hours. The mixture was concentrated under reduced pressure and cooled to precipitate crystals. The crystals were filtered and rinsed with cold hexane to obtain 37.8 g of vinyl ether of the following structure as white needle crystals.

Polyamic acid was synthesized in the same manner as in P-1, and 79.19 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 39.18 g of NMP was added. - camphorsulfonic acid (0.72 g) were sequentially added. After reacting at 25 DEG C for 5 hours, the reaction solution was added to 705 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 15.1 g of the title compound (resin P-26) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.62 × 10 ⁴ and Mw / Mn = 1.76. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-27]

29.00 g of ethylene glycol monovinyl ether and 39.20 g of phenyl isocyanate were added to 150 ml of dehydrated ethyl acetate and the mixture was stirred at 70 캜 for 6 hours. (100 DEG C, 0.1 kPa) under reduced pressure to obtain 60.2 g of an oil-like vinyl ether of the following structure.

Polyamic acid was synthesized in the same manner as in P-1, and 79.19 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 39.18 g of NMP was added. - camphorsulfonic acid (0.72 g) were sequentially added. After reaction at 25 DEG C for 5 hours, the reaction solution was added to 705 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 17.6 g of the title compound (resin P-26) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.89 × 10 ⁴ and Mw / Mn = 1.95. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-29]

100 g of phenylacetaldehyde dimethylacetal and 54.3 g of acetyl chloride were added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and reacted at 50 DEG C for 5 hours, followed by concentration under reduced pressure to obtain a transparent liquid having the following structure.

Polyamic acid was synthesized in the same manner as in P-1, and 132.8 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 65.68 g of NMP was added and cooled. Solution, followed by the addition of 23.25 g of N, N-diisopropylethylamine. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 1182 g of methanol to obtain a precipitated solid which was filtered and dried to obtain 29.19 g of a white solid (resin P-29). Analysis of the obtained resin by GPC revealed that Mw = 2.49 × 10 ⁴ and Mw / Mn = 1.65. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 97%.

[Synthesis of P-31]

58.2 g of 1-ethylcyclopentanol and 250 ml of dry THF were added to a 2000 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 184 ml of n-butyllithium (2.6 M hexane) was added dropwise at -5 deg. And the mixture was stirred at -2 deg. C for 2 hours. 50.0 g of 3,3 ', 4,4'-biphenyltetracarboxylic anhydride was added to the mixture, and the mixture was stirred at room temperature for 1 hour, 200 ml of NMP was added, the mixture was further stirred at room temperature for 3 hours, Lt; / RTI > The mixture was neutralized with diluted hydrochloric acid and extracted with ethyl acetate (600 ml). The organic layer was washed twice with saturated brine and twice with water. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain a dicar To obtain 32.3 g of a carboxylic acid.

16.00 g of this dicarboxylic acid was added to a 100 ml flask equipped with a thermometer, a stirrer and a nitrogen-introducing tube, 58.28 g of NMP was added and cooled, and diphenyl (2,3-dihydro- (DBOP), 11.63 g of N, N-diisopropylethylamine and 3.43 g of trans-1,4-cyclohexanediamine were added in this order. After stirring at 0 DEG C or lower for 1 hour, the mixture was stirred at room temperature for one day. The reaction solution was added to 700 ml of methanol, and the precipitated solid was filtered to obtain a slurry with 1000 ml of acetonitrile. The solid was dissolved in 100 ml of NMP, 0.89 g of phthalic anhydride was added, and the mixture was stirred at 50 占 폚 for 1 hour. The reaction solution was added to methanol (800 ml) / water (200 ml) and dried to obtain 15.6 g of a white solid (resin P-31). Analysis of the obtained resin by GPC revealed that Mw = 0.90 × 10 ⁴ and Mw / Mn = 2.03. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-33]

In a 2000 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 94.4 g of 2-ethyl-2-adamantanol and 250 ml of dry THF were added, and n-butyllithium (2.6M hexane) And the mixture was stirred at 5 占 폚 for 1 hour. Thereto were added 70.0 g of 3,3 ', 4,4'-biphenyltetracarboxylic anhydride and 280 g of NMP, followed by stirring at room temperature for 2 hours and stirring at 40 ° C for 1 hour. The reaction mixture was allowed to stand, cooled, neutralized with 600 ml of 1 M hydrochloric acid, and then extracted with 1000 ml of ethyl acetate. The organic layer was washed with saturated brine twice and water twice in this order. 500 ml of 1M NaOH was added to extract the aqueous layer, and the mixture was washed with 300 ml of ethyl acetate. The aqueous layer was neutralized with 500 ml of 1M hydrochloric acid and extracted with 500 ml of ethyl acetate. The organic layer was washed twice with saturated brine and twice with water. Dried over sodium sulfate, and concentrated under reduced pressure to obtain 76.4 g of a dicarboxylic acid of the following structure.

15.00 g of this dicarboxylic acid was added to a 100 ml flask equipped with a thermometer, a stirrer and a nitrogen-introducing tube, and 52.69 g of NMP was added. The mixture was cooled, and diphenyl (2,3-dihydro- 20.66 g of N, N-diisopropylethylamine, and 2.56 g of trans-1,4-cyclohexanediamine were added in this order. After stirring at 0 ° C or lower for 1 hour, the mixture was stirred at room temperature for 4 hours. Subsequently, 0.67 g of phthalic anhydride was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to 1200 ml of methanol, and the precipitated solid was collected by filtration, followed by further slurry with 1000 ml of methanol. The solid was dried to obtain 14.7 g of the title compound as a white solid (Resin P-33). Analysis of the obtained resin by GPC revealed that Mw = 0.82 × 10 ⁴ and Mw / Mn = 1.64. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-34]

Polyamic acid was synthesized in the same manner as in P-1, 142.3 g of the polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 70.38 g of NMP was added, and bromoacetic acid 31.32 g of tert-butyl and 16.60 g of N, N-diisopropylethylamine were added. After reaction at room temperature for 7 hours, the reaction solution was added to 1267 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 34.07 g of the title compound (resin P-34) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.38 × 10 ⁴ and Mw / Mn = 2.68. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-36]

25 g of bromoacetyl bromide and 475 g of dehydrated NMP were added to a 1000 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 50 g of DBU was added while cooling. After cooling, 110.47 g of 1-ethylcyclopentanol was added at 10 DEG C or lower, and the reaction was allowed to proceed at room temperature for 4 hours. 600 ml of water was added and extracted twice with 500 ml of ethyl acetate. The organic layer was washed twice with saturated sodium hydrogencarbonate solution and twice with water, and the organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give Brown oil was obtained.

A polyamic acid was synthesized in the same manner as in P-1, 142.3 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 70.38 g of NMP was added, and the above halide 37.76 g, and N, N-diisopropylethylamine (16.60 g) were added. After reaction at room temperature for 7 hours, the reaction solution was added to 1267 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 36.97 g of the title compound (resin P-36) as a brown solid. Analysis of the obtained resin by GPC revealed that Mw = 3.64 × 10 ⁴ and Mw / Mn = 2.51. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-39]

111.9 g of bromoacetyl bromide and 360 g of dehydrated NMP were added to a 2000 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 50.7 g of DBU was added while cooling. 40.0 g of 2-ethyl-2-adamantanol was added at 10 DEG C or lower, and the reaction was allowed to proceed at room temperature for 4 hours. 600 ml of water was added and extracted twice with 500 ml of ethyl acetate. The organic layer was washed twice with saturated sodium hydrogencarbonate solution and twice with water, and the organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give Brown oil was obtained.

Polyamic acid was synthesized in the same manner as in P-1, and 133.10 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 65.87 g of NMP was added, and the above halide 36.46 g, and N, N-diisopropylethylamine (15.65 g) were added. After reaction at room temperature for 8 hours, the reaction solution was added to 1186 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 41.21 g of the title compound (resin P-39) as a brown solid. Analysis of the obtained resin by GPC revealed that Mw = 3.97 × 10 ⁴ and Mw / Mn = 2.59. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-41]

Synthesis of polyamic acid

64.04 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag) was placed in a 5000 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and NMP (N-methyl-2-pyrrolidone) 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 DEG C for 4 hours, allowed to cool to room temperature. Then, 89.29 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) was added and the mixture was stirred at 60 ° C for 2 hours. The mixture was left to cool to room temperature, cooled, 27.69 g of phthalic anhydride was added, and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.88 × 10 ⁴ , Mn = 0.74 × 10 ⁴ , and Mw / Mn = 2.55.

Synthesis of polyamic acid ester

132.20 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 65.47 g of NMP was added, followed by cooling. 11.39 g of chloromethyl methyl ether and 11.39 g of N, N- 14.62 g of diisopropylethylamine was added. After reacting at 0 ° C or lower for 4 hours, the reaction solution was added to 1178 g of methanol to obtain a precipitated solid which was filtered to obtain 25.9 g of the title compound (resin P-41) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.45 × 10 ⁴ and Mw / Mn = 1.68. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-42]

Polyamic acid was synthesized similarly to P-41. 132.20 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 65.47 g of NMP was added, cooled, and 3.80 g of chloromethyl methyl ether, 6.09 g of diisopropylethylamine was added. After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to 1178 g of methanol to obtain a precipitated solid which was filtered to obtain 18.8 g of the title compound (resin P-42) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.20 × 10 ⁴ and Mw / Mn = 1.58. The solid was dissolved in DMSO to measure the ¹ H-NMR spectrum and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid to be 52%.

[Synthesis of P-45]

Polyamic acid was synthesized similarly to P-41. 136.30 g of the polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 67.49 g of NMP was added thereto. The mixture was cooled, and 24.87 g of chloromethyl octyl ether was added thereto at 0 deg. 14.39 g of diisopropylethylamine was added. After 4 hours of reaction at 0 ° C or lower, the reaction solution was added to 1215 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 32.1 g of the title compound (resin P-45) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.83 × 10 ⁴ and Mw / Mn = 1.76. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

[Synthesis of P-47]

Polyamic acid was synthesized similarly to P-41. 146.80 g of the polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 72.69 g of NMP was added thereto. The mixture was cooled, and 22.28 g of chloromethylcyclohexyl ether and then N, N -Diisopropylethylamine < / RTI > was added. After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to 1308 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 31.8 g of the title compound (resin P-47) as a white solid. When the obtained resin was analyzed by GPC, Mw = 2.50 x 10 ⁴ and Mw / Mn = 1.85. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-49]

Polyamic acid was synthesized similarly to P-41. 157.30 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 77.88 g of NMP was added thereto. The mixture was cooled, and 9.55 g of chloromethylcyclohexyl ether was added thereto at 0 캜 or lower, -Diisopropylethylamine < / RTI > was added. After reacting at 0 ° C or lower for 4 hours, the reaction solution was added to 1402 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 26.19 g of the title compound (resin P-49) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.22 × 10 ⁴ and Mw / Mn = 1.94. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid to be 63%.

[Synthesis of P-50]

Polyamic acid was synthesized similarly to P-41. 132.20 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 65.47 g of NMP was added, and the mixture was cooled, and 22.15 g of chloromethylbenzyl ether and then N, N- 14.62 g of diisopropylethylamine was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 1178 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 26.1 g of the title compound (resin P-50) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.59 x 10 ⁴ and Mw / Mn = 1.83. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-52]

Polyamic acid was synthesized similarly to P-41. 117.51 g of this polyamic acid solution was added to a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 58.19 g of NMP was added thereto. The mixture was cooled, and 15.66 g of 2-methoxyethoxymethyl chloride and 15.66 g 13.00 g of N, N-diisopropylethylamine was added. After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to 1047 g of methanol, and the precipitated solid was collected by filtration and dried to obtain 20.5 g of the title compound (resin P-52) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 3.02 × 10 ⁴ and Mw / Mn = 1.59. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-55]

106.55 g of 2-chloroethyl vinyl ether was added to 385.86 g of a 28% methanol solution of sodium methoxide and refluxed for 12 hours. 200 ml of hexane was added, and the solution was washed with saturated brine three times and washed with water two times. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to give (2-methoxyethyl) vinyl ether .

Polyamic acid was synthesized in the same manner as in P-41, and 88.13 g of the polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 74.20 g of NMP was added, 9.63 g of the vinyl ether, - < / RTI > camphorsulfonic acid were sequentially added. After reacting at 25 DEG C for 5 hours, the reaction solution was added to 786 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 12.6 g of the title compound (resin P-55) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.96 × 10 ⁴ and Mw / Mn = 1.82. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-74]

5.61 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 0.45 g of trans-1,4-cyclohexanediamine (4.25 g) was dissolved in 132.24 g of N-methyl-2-pyrrolidone, and then 6.40 g of pyromellitic anhydride and 1.40 g of (1R, 2S, 4S, 5R) -Cyclohexanetetracarboxylic acid dianhydride (PMDA-HS, manufactured by Iwatani Gas Co., Ltd.) was added. After reacting at 4 占 폚 for 1 hour and then at 25 占 폚 for 24 hours, 1.77 g of phthalic anhydride was added and the mixture was stirred at room temperature for 2 hours. 77.79 g of NMP was added to the polyamic acid solution, and 20.469 g of (2-methoxyethyl) vinyl ether and 1.55 g of 10-camphorsulfonic acid were added sequentially. After reacting at 25 DEG C for 5 hours, the reaction solution was added to 1400 g of acetonitrile, and the precipitated solid was collected by filtration and dried to obtain 31.6 g of the title compound (resin P-74) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 3.26 × 10 ⁴ and Mw / Mn = 1.90. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-93]

In a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 6.85 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasagi KK) was added and dissolved in 182.71 g of N-methyl-2-pyrrolidone After that, 13.45 g of (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid dianhydride (PMDA-HS, manufactured by Iwatani Gas Co., Ltd.) was added at room temperature. Followed by reaction at room temperature for 1 hour and then at 60 ° C for 4 hours. Analysis of the obtained solution by GPC revealed that Mw = 5.53 × 10 ⁴ , Mn = 2.71 × 10 ⁴ , and Mw / Mn = 2.04. To this solution was added 0.89 g of phthalic anhydride and the mixture was stirred at room temperature for 2 hours and then cooled. Then, 15.22 g of chloromethyl methyl ether and 19.54 g of N, N-diisopropylethylamine were added at 0 ° C or lower. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 1218 g of methanol to obtain a precipitated solid which was filtered to obtain 26.1 g of the title compound (resin P-93) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 6.26 × 10 ⁴ and Mw / Mn = 2.11. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of R3]

Synthesis of polyamic acid (polyimide precursor)

8.49 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) was placed in a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, And 10.70 g of (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic acid dianhydride (PMDA-HS, manufactured by Iwatani Gas Co., Ltd.) was added thereto at 2 ° C under ice-cooling. After reacting at 4 DEG C for 1 hour and then at 25 DEG C for 12 hours, 1.62 g of phthalic anhydride was added and the mixture was stirred at room temperature for 2 hours. 109 g of NMP was added to the polyamic acid solution, and the mixture was cooled. 10.10 g of chloromethyl methyl ether and 12.97 g of N, N-diisopropylethylamine were added at 0 占 폚 or lower. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to methanol (1500 mL), and the precipitated solid was collected by filtration and dried to obtain 22.3 g of the title compound as a white solid (Resin R3). Analysis of the obtained resin by GPC revealed that Mw = 1.93 × 10 ⁴ and Mw / Mn = 1.82. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-110]

48.0 g of 1,1,2-trimethoxyethane, 29.8 g of acetyl chloride and 10 mg of zinc chloride were added to a 100 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and reacted at room temperature for 8 hours to obtain the following structure (b5-1 ) Was obtained as a transparent liquid in a yield of 76.3 g.

Polyamic acid was synthesized in the same manner as in P-41, and 125.8 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 62.3 g of NMP was added, , 17.71 g of N-diisopropylethylamine, and 27.69 g of the above-described transparent liquid to the compound represented by the above structure (b5-1). After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to 1.2 L of methanol, and the precipitated solid was collected by filtration and dried to obtain 22.71 g of the title compound (resin P-110) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.52 × 10 ⁴ and Mw / Mn = 1.91. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

As a result of analyzing the differential thermal balance of Resin P-110, the endothermic peak temperature was 206 占 폚 and the weight loss rate was 34%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the pyrolysis temperature of R ³ is 206 ° C.

[Synthesis of P-111]

60.0 g of 1,1,2-trimethoxyethane, 190.0 g of 2-methoxyethanol, 1.74 g of 10-camphorsulfonic acid and 200 ml of hexane were added to a 500 ml flask equipped with a thermometer, a stirrer, a Dean Stark and a reflux tube And refluxed for 48 hours. The reaction solution was cooled to 0 캜, and 3.79 g of triethylamine was added thereto. The mixture was stirred at 0 캜 for 30 minutes, and then extracted with ethyl acetate and saturated aqueous sodium hydrogencarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain 97.2 g of a transparent liquid.

97.2 g of the above solution, 43.0 g of acetyl chloride and 10 mg of zinc chloride were added to a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was reacted at room temperature for 8 hours. 93.8 g of a compound represented as a transparent liquid was obtained.

Polyamic acid was synthesized in the same manner as in P-41, and 125.8 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 62.3 g of NMP was added, 16.60 g of N-diisopropylethylamine and 33.07 g of the above-mentioned transparent liquid to the compound represented by the above structure (b5-2) were added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to methanol (1.5 L), and the precipitated solid was collected by filtration and dried to obtain 23.86 g of the title compound (resin P-111) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.62 × 10 ⁴ and Mw / Mn = 1.62. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

As a result of analyzing the differential thermal balance of Resin P-111, the endothermic peak temperature was 210 ° C and the weight loss rate was 42%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the pyrolysis temperature of R ³ is 210 ° C.

[Synthesis of P-112]

150.0 g of 1,1,2-trimethoxyethane, 379.5 g of 2-phenoxyethanol, 4.35 g of 10-camphorsulfonic acid and 200 ml of hexane were added to a 1 L flask equipped with a thermometer, a stirrer, a Dean Stark and a reflux tube, And refluxed for 48 hours. The reaction solution was cooled to 0 캜, and 9.47 g of triethylamine was added thereto. The mixture was stirred at 0 캜 for 30 minutes, and then extracted with ethyl acetate and saturated aqueous sodium hydrogencarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and then concentrated under reduced pressure to obtain 532.4 g of a clear liquid.

532.4 g of the above solution, 117.6 g of acetyl chloride and 10 mg of zinc chloride were added to a 1 L flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was reacted at room temperature for 4 hours and then concentrated under reduced pressure to give the following structure (b5-3) 518.2 g of a losing compound was obtained as a transparent liquid.

Polyamic acid was synthesized in the same manner as in P-41, and 260.4 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 129.2 g of NMP was added, 36.55 g of N-diisopropylethylamine, and 216.87 g of the above-described transparent liquid for the compound represented by the above structure (b5-3) were added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 3 liters of methanol, and the precipitated solid was collected by filtration and dried to obtain 68.68 g of the title compound (resin P-112) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.56 x 10 ⁴ and Mw / Mn = 1.85. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 97%.

As a result of analyzing the differential thermal balance of Resin P-112, the endothermic peak temperature was 211 ° C and the weight reduction rate was 51%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the pyrolysis temperature of R ³ is 211 ° C.

[Synthesis of P-113]

50.0 g of 1,1,2-trimethoxyethane, 91.7 g of cyclohexanol, 1.45 g of 10-camphorsulfonic acid and 200 ml of hexane were added to a 500 ml flask equipped with a thermometer, a stirrer, a Dean Stark and a reflux tube, Lt; / RTI > The reaction solution was cooled to 0 占 폚, and 3.16 g of triethylamine was added thereto. The mixture was stirred at 0 占 폚 for 30 minutes and then extracted with ethyl acetate and saturated aqueous sodium hydrogencarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and then concentrated under reduced pressure to obtain 84.4 g of a clear liquid.

84.4 g of the above solution, 31.0 g of acetyl chloride and 10 mg of zinc chloride were added to a 200-ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was reacted at room temperature for 4 hours and then concentrated under reduced pressure to give 91.2 g of a compound represented as a transparent liquid was obtained.

Polyamic acid was synthesized in the same manner as in P-41, and 125.8 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 62.3 g of NMP was added, , 16.60 g of N-diisopropylethylamine, and 43.66 g of the above-described transparent liquid to the compound represented by the above structure (b5-4) were added. After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to methanol (1.5 L), and the precipitated solid was collected by filtration and dried to obtain 26.40 g of a white solid (resin P-113). Analysis of the obtained resin by GPC revealed that Mw = 2.52 × 10 ⁴ and Mw / Mn = 1.64. The solid was dissolved in DMSO to measure the ¹ H-NMR spectrum and the protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 88%.

As a result of analyzing the differential thermal balance of Resin P-113, the endothermic peak temperature was 177 DEG C and the weight reduction rate was 46%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the pyrolysis temperature of R ³ is 177 ° C.

[Synthesis of P-114]

50.0 g of isobutylaldehyde, 50.0 g of magnesium sulfate, 200 ml of methanol and 1.61 g of 10-camphorsulfonic acid were added to a 500 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and reacted at 50 ° C for 8 hours. The reaction solution was cooled to 0 ° C, and 3.51 g of triethylamine was added thereto, followed by stirring at 0 ° C for 30 minutes. Magnesium sulfate was filtered out, and the filtrate was extracted with hexane and saturated aqueous sodium bicarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and then concentrated under atmospheric pressure to obtain 58.3 g of a transparent liquid.

58.3 g of the above solution, 42.0 g of acetyl chloride and 10 mg of zinc chloride were added to a 500-ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and reacted at 50 ° C for 24 hours to obtain the compound represented by the following structure (b5-5) 81.0 g was obtained as a liquid.

Polyamic acid was synthesized in the same manner as in P-41, and 125.8 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 62.3 g of NMP was added, , 22.14 g of N-diisopropylethylamine, and 33.16 g of the above-described transparent liquid to the compound represented by the above structure (b5-5) were added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to methanol (1.5 L), and the precipitated solid was collected by filtration and dried to obtain 20.12 g of the title compound (resin P-114) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.28 × 10 ⁴ and Mw / Mn = 1.74. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result, the protection ratio was found to be 91% from the peak integral ratio of the carboxylic acid ester and the carboxylic acid.

As a result of analyzing the differential thermal balance of Resin P-114, the endothermic peak temperature was 163 DEG C and the weight reduction rate was 32%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating units represented by the general formula (1), and the pyrolysis temperature of R ³ is 163 ° C.

[Synthesis of P-115]

50.0 g of isobutylaldehyde, 77.8 g of magnesium sulfate, 158.3 g of 2-methoxyethanol and 1.61 g of 10-camphorsulfonic acid were added to a 500-ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and reacted at 50 ° C for 10 hours. The reaction solution was cooled to 0 ° C, and 3.51 g of triethylamine was added thereto, followed by stirring at 0 ° C for 30 minutes. Magnesium sulfate was filtered off, and the filtrate was extracted with ethyl acetate and saturated aqueous sodium hydrogencarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and then concentrated under reduced pressure to obtain 105.9 g of a transparent liquid.

105.9 g of the above solution and 48.3 g of acetyl chloride were added to a 500 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was reacted at room temperature for 4 hours and then concentrated under reduced pressure to obtain the compound represented by the following structure (b5-6) 111.1 g was obtained as a liquid.

Polyamic acid was synthesized in the same manner as in P-41, and 125.8 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 62.3 g of NMP was added, , 22.14 g of N-diisopropylethylamine and subsequently 35.80 g of the above-described transparent liquid for the compound represented by the above structure (b5-6) were added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to methanol (1.5 L), and the precipitated solid was collected by filtration and dried to obtain 19.76 g of the title compound as a white solid (Resin P-115). Analysis of the obtained resin by GPC revealed that Mw = 2.64 × 10 ⁴ and Mw / Mn = 1.62. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

As a result of analyzing the differential thermal balance of Resin P-115, the endothermic peak temperature was 164 캜 and the weight loss rate was 42%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the pyrolysis temperature of R ³ is 164 ° C.

[Synthesis of P-118]

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 to a 1 L flask equipped with a thermometer, a stirrer and a calcium chloride tube, and reacted at 50 DEG C for 11 hours. The reaction solution was cooled to 0 캜, 4.53 g of triethylamine was added, and the mixture was stirred at 0 캜 for 30 minutes. Magnesium sulfate was filtered off, and the filtrate was extracted with ethyl acetate and saturated aqueous sodium hydrogencarbonate. The obtained organic layer 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.

144.2 g of the above solution and 84.2 g of acetyl chloride were added to a 1 L flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was reacted at room temperature for 2 hours and then concentrated under reduced pressure to obtain the compound represented by the following structure (b5-9) Was obtained.

Polyamic acid was synthesized in the same manner as in P-41, and 250.0 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 124.0 g of NMP was added, 28.51 g of N-diisopropylethylamine and then 40.82 g of the above-described transparent liquid to the compound represented by the above structure (b5-9) were added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 2.7 L of isopropanol to obtain a precipitated solid which was filtered to obtain 66.54 g of the title compound (resin P-118) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.43 × 10 ⁴ and Mw / Mn = 2.13. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

As a result of analyzing the differential thermal balance of Resin P-118, the endothermic peak temperature was 165 ° C and the weight reduction rate was 44%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the pyrolysis temperature of R ³ is 165 ° C.

[Synthesis of P-120]

59.8 g of 2-phenylpropionaldehyde, 50.0 g of magnesium sulfate, 101.8 g of 2-methoxyethanol and 1.04 g of 10-camphorsulfonic acid were added to a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube and reacted at 50 DEG C for 12 hours . The reaction solution was cooled to 0 deg. C, 2.26 g of triethylamine was added, and the mixture was stirred at 0 deg. C for 30 minutes. Magnesium sulfate was filtered off, and the filtrate was extracted with ethyl acetate and saturated aqueous sodium hydrogencarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain 91.6 g of a clear liquid.

91.6 g of the above solution 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, and the mixture was reacted at room temperature for 2 hours and then concentrated under reduced pressure to obtain the compound represented by the following formula (b5-10) Was obtained.

Polyamic acid was synthesized in the same manner as in P-41, and 125.0 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 62.0 g of NMP was added and cooled. , 16.45 g of N-diisopropylethylamine, and 68.97 g of the above-mentioned transparent liquid to the compound represented by the above structure (b5-10). After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to methanol (1.5 L), and the precipitated solid was collected by filtration and dried to obtain 29.96 g of a white solid (resin P-120). Analysis of the obtained resin by GPC revealed that Mw = 2.44 × 10 ⁴ and Mw / Mn = 1.67. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid to be 96%.

As a result of analyzing the differential thermal balance of the resin P-120, the endothermic peak temperature was 162 占 폚 and the weight loss rate was 50%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the thermal decomposition temperature of R ³ is 162 ° C. Also, an endothermic peak, which is seen as imide ring closure, was observed at 198 ° C.

[Synthesis of P-122]

120.0 g of 2-phenylpropionaldehyde, 100.0 g of magnesium sulfate, 204.9 g of 2-propoxyethanol and 2.08 g of 10-camphorsulfonic acid were added to a 500 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was reacted at 50 DEG C for 12 hours . The reaction solution was cooled to 0 캜, 4.53 g of triethylamine was added, and the mixture was stirred at 0 캜 for 30 minutes. Magnesium sulfate was filtered off, and the filtrate was extracted with ethyl acetate and saturated aqueous sodium hydrogencarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain a clear liquid.

The whole amount of the above solution and 84.2 g of acetyl chloride were added to a 1 L flask equipped with a thermometer, a stirrer, and a calcium chloride tube, and the mixture was reacted at room temperature for 2 hours and then concentrated under reduced pressure to obtain a compound represented by the following formula (b5-11) 211.7 g.

Polyamic acid was synthesized in the same manner as in P-41, and 260.4 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 129.2 g of NMP was added, 36.55 g of N-diisopropylethylamine and 173.21 g of the above-described transparent liquid to the compound represented by the above structure (b5-11) were added. After reacting at 0 DEG C or lower for 4 hours, the reaction mixture was added to 3 liters of methanol, and the precipitated solid was collected by filtration and dried to obtain 64.02 g of the title compound (resin P-122) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.71 × 10 ⁴ and Mw / Mn = 1.82. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

As a result of analyzing the differential thermal balance of Resin P-122, the endothermic peak temperature was 163 DEG C and the weight reduction rate was 54%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating units represented by the general formula (1), and the pyrolysis temperature of R ³ is 163 ° C. In addition, an endothermic peak, which is seen as imide ring closure at 206 ° C, was also observed.

[Synthesis of P-127]

39.2 g of pivalic aldehyde, 40.0 g of magnesium sulfate, 50 ml of methanol, 200 ml of hexane and 1.06 g of 10-camphorsulfonic acid were added to a 500 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and reacted at 50 ° C for 12 hours. The reaction solution was cooled to 0 캜, 2.30 g of triethylamine was added, and the mixture was stirred at 0 캜 for 30 minutes. Magnesium sulfate was filtered out, and the filtrate was extracted with hexane and saturated aqueous sodium bicarbonate. The obtained organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and then concentrated under atmospheric pressure to obtain 82.1 g of a clear liquid.

76.6 g of the above solution, 17.0 g of acetyl chloride and 10 mg of zinc chloride were added to a 200 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, and the mixture was allowed to react at 50 ° C for 12 hours to obtain the compound represented by the following structure (b5-14) 112.0 g was obtained as a liquid.

Polyamic acid was synthesized in the same manner as in P-41, and 125.8 g of this polyamic acid solution was added to a 300 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 62.3 g of NMP was added, , 17.71 g of N-diisopropylethylamine, and 51.47 g of the transparent liquid for the compound represented by the above structure (b5-14) were added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to methanol (1.5 L), and the precipitated solid was collected by filtration and dried to obtain 15.27 g of the title compound as a white solid (Resin P-127). Analysis of the obtained resin by GPC revealed that Mw = 2.57 x 10 ⁴ and Mw / Mn = 1.57. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

As a result of analyzing the differential thermal balance of Resin P-127, the endothermic peak temperature was 230 deg. C and the weight loss rate was 37%. This weight reduction ratio corresponds to the weight of R ^{3 in} the repeating unit represented by the general formula (1), and the thermal decomposition temperature of R ³ is 230 ° C.

[Synthesis of P-130]

Synthesis of polyamic acid

20.96 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag) was placed in a 1 L flask equipped with a thermometer, a stirrer and a nitrogen introducing tube, and 628.8 g of NMP (N-methyl-2-pyrrolidone) , 90.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) was added. The mixture was stirred at 60 DEG C for 4 hours, allowed to cool to room temperature. Then, 27.27 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 154.6 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was allowed to cool to room temperature, cooled, and added with 3.63 g of phthalic anhydride and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 2.44 × 10 ⁴ , Mn = 0.95 × 10 ⁴ , and Mw / Mn = 2.58.

Synthesis of polyamic acid ester

246.71 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 122.87 g of NMP was added thereto. The mixture was cooled, and 27.96 g of N, N-diisopropylethylamine 40.04 g of the (b5-9) liquid synthesized in P-118 was added. After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to 2.6 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 62.92 g of the title compound (resin P-130) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 3.33 × 10 ⁴ and Mw / Mn = 2.02. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

[Synthesis of P-131]

246.71 g of the polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 122.87 g of NMP was added thereto. The mixture was cooled, and N, N- 27.96 g of N-diisopropylethylamine and 112.94 g of the liquid of (b5-11) synthesized in P-122 were subsequently added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 70.16 g of the title compound (resin P-131) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 3.85 × 10 ⁴ and Mw / Mn = 1.90. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

[Synthesis of P-132]

Synthesis of polyamic acid

20.96 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag) was placed in a 1 L flask equipped with a thermometer, a stirrer and a nitrogen introducing tube, and 628.8 g of NMP (N-methyl-2-pyrrolidone) , 90.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) was added. The mixture was stirred at 60 DEG C for 4 hours, allowed to cool to room temperature. Then, 25.98 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 147.2 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. After cooling to room temperature, the mixture was cooled, 1.81 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. Analysis of the obtained solution by GPC revealed that Mw = 3.04 × 10 ⁴ , Mn = 1.19 × 10 ⁴ , and Mw / Mn = 2.55.

Synthesis of polyamic acid ester

243.92 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 121.72 g of NMP was added and cooled. Then, 27.41 g of N, N-diisopropylethylamine 39.25 g of the (b5-9) liquid synthesized in P-118 was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 2.6 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 61.84 g of the title compound (resin P-132) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 4.12 × 10 ⁴ and Mw / Mn = 2.35. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-133]

243.92 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 121.72 g of NMP was added and cooled, and N, N- 27.41 g of N-diisopropylethylamine and 110.72 g of the liquid (b5-11) synthesized in P-122 were added. After reacting at 0 DEG C or lower for 4 hours, the reaction mixture was added to 3 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 71.19 g of the title compound (resin P-133) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 4.79 × 10 ⁴ and Mw / Mn = 1.98. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

[Synthesis of P-134]

Synthesis of polyamic acid

A 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube was charged with 10.48 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag), 2,2'-dimethyl-4,4'- Phenyl] (manufactured by Wakayama Seika Co., Ltd.) was added and dissolved in 397.2 g of NMP (N-methyl-2-pyrrolidone), and then 3,3 ', 4,4'- biphenyltetracarboxylic anhydride [ (Manufactured by Mitsubishi Kagaku K.K.) were added. The mixture was stirred at 60 DEG C for 6 hours, allowed to cool to room temperature. 4.53 g of phthalic anhydride was added and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 2.10 x 10 ⁴ , Mn = 0.76 x 10 ⁴ , and Mw / Mn = 2.77.

240.0 g of 2-phenylpropionaldehyde, 240.0 g of magnesium sulfate, 558.9 g of 2-propoxyethanol and 17.01 g of p-toluenesulfonic acid monohydrate were added to a 1 L flask equipped with a thermometer, a stirrer and a calcium chloride tube and reacted at room temperature for 12 hours . The reaction solution was cooled to 0 deg. C, 45.25 g of triethylamine was added, and the mixture was stirred at 0 deg. C for 30 minutes. 500 mL of ethyl acetate was added, and 1 L of distilled water was added to completely dissolve the magnesium sulfate. After separating, the organic layer was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain 657.8 g of a clear liquid.

652.8 g of the above liquid and 168.5 g of acetyl chloride were added to a 1 L flask equipped with a thermometer, a stirrer, and a calcium chloride tube, and reacted at room temperature for 4 hours, followed by concentration under reduced pressure to obtain 716.6 g of a transparent liquid (b5-11).

Synthesis of polyamic acid ester

251.63 g of the polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 124.6 g of NMP was added, and the mixture was cooled. 28.78 g of N, N-diisopropylethylamine, (b5-11) was added. After reacting at 0 ° C or lower for 4 hours, the reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 73.69 g of the title compound (resin P-134) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 3.21 x 10 ⁴ and Mw / Mn = 1.86. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

[Synthesis of P-135]

Synthesis of polyamic acid

A 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube was charged with 10.48 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag), 2,2'-dimethyl-4,4'- Phenyl] (manufactured by Wakayama Seika Co., Ltd.) were placed and dissolved in 391.7 g of NMP (N-methyl-2-pyrrolidone), and then 3,3 ', 4,4'- biphenyltetracarboxylic anhydride [ (Manufactured by Mitsubishi Kagaku K.K.) were added. The mixture was stirred at 60 DEG C for 6 hours, allowed to cool to room temperature. And 1.81 g of phthalic anhydride was added thereto, followed by stirring at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 3.46 x 10 ⁴ , Mn = 1.25 x 10 ⁴ , and Mw / Mn = 2.76.

Synthesis of polyamic acid ester

251.85 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 125.4 g of NMP was added, and the mixture was cooled. 28.54 g of N, N-diisopropylethylamine 110.43 g of the liquid (b5-11) synthesized in P-134 was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 74.57 g of the title compound (resin P-135) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 5.49 × 10 ⁴ and Mw / Mn = 2.02. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

[Synthesis of P-136]

Synthesis of polyamic acid

A 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube was charged with 10.48 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag), 2,2'-dimethyl-4,4'- Phenyl] (manufactured by Wakayama Seika Co., Ltd.) was added and dissolved in 389.8 g of NMP (N-methyl-2-pyrrolidone), and then 3,3 ', 4,4'-biphenyltetracarboxylic anhydride [ (Manufactured by Mitsubishi Kagaku K.K.) were added. The mixture was stirred at 60 DEG C for 6 hours, allowed to cool to room temperature. 0.91 g of phthalic anhydride was added and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 5.71 x 10 ⁴ , Mn = 2.07 x 10 ⁴ , and Mw / Mn = 2.76.

Synthesis of polyamic acid ester

255.29 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 127.4 g of NMP was added and cooled. 28.84 g of N, N-diisopropylethylamine 111.57 g of the liquid (b5-11) synthesized in P-134 was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 78.88 g of the title compound (resin P-136) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 8.58 × 10 ⁴ and Mw / Mn = 2.09. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-138]

Synthesis of polyamic acid

6.99 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag) was placed in a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and NMP (N-methyl-2-pyrrolidone) g, and 45.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) was added thereto. The mixture was stirred at 60 DEG C for 4 hours, allowed to cool to room temperature. Subsequently, 20.78 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 117.8 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was allowed to cool to room temperature, cooled, and added with 3.63 g of phthalic anhydride and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.82 × 10 ⁴ , Mn = 0.71 × 10 ⁴ , and Mw / Mn = 2.55.

Synthesis of polyamic acid ester

260.66 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 129.4 g of NMP was added, and the mixture was cooled, and 28.51 g of N, N-diisopropylethylamine 110.22 g of the liquid (b5-11) synthesized in P-134 was added. After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to 3.2 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 72.98 g of the title compound (resin P-138) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.76 × 10 ⁴ and Mw / Mn = 1.79. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 99%.

[Synthesis of P-139]

Synthesis of polyamic acid

8.73 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigas Co., Ltd.) was placed in a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and NMP (N-methyl-2-pyrrolidone) g, and 45.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) was added thereto. The mixture was stirred at 60 DEG C for 4 hours, allowed to cool to room temperature. Then, 17.53 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 99.4 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was allowed to cool to room temperature, cooled, and added with 3.63 g of phthalic anhydride and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.68 × 10 ⁴ , Mn = 0.65 × 10 ⁴ , and Mw / Mn = 2.58.

Synthesis of polyamic acid ester

255.32 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and 126.7 g of NMP was added and cooled. 28.51 g of N, N-diisopropylethylamine 110.22 g of the liquid (b5-11) synthesized in P-134 was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 3.2 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 71.56 g of the title compound (resin P-139) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.67 × 10 ⁴ and Mw / Mn = 1.78. The solid was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The protection ratio was calculated from the peak integral ratio of the carboxylic acid ester and the carboxylic acid, and as a result, it was 98%.

[Synthesis of P-141]

Synthesis of polyamic acid

13.04 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasagi) was placed in a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and NMP (N-methyl-2-pyrrolidone) g, and 48.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Corporation) was added thereto. The mixture was stirred at 60 DEG C for 4 hours, allowed to cool to room temperature. Then, 11.78 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 66.7 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was allowed to cool to room temperature, cooled, added with 3.87 g of phthalic anhydride, and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.54 × 10 ⁴ , Mn = 0.53 × 10 ⁴ , and Mw / Mn = 2.89.

Synthesis of polyamic acid ester

254.85 g of the polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and 126.4 g of NMP was added thereto. The mixture was cooled, and 29.69 g of N, N-diisopropylethylamine 114.82 g of the (b5-11) liquid synthesized in P-134 was added. After reacting at 0 DEG C or less for 4 hours, the reaction solution was added to 3.2 L of isopropanol to obtain a precipitated solid which was filtered and dried to obtain 73.07 g of the title compound (resin P-141) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.52 × 10 ⁴ and Mw / Mn = 1.76. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-142]

Synthesis of polyamic acid

15.21 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag) was placed in a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and NMP (N-methyl-2-pyrrolidone) g, and 49.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) was added. The mixture was stirred at 60 DEG C for 4 hours, allowed to cool to room temperature. Then, 8.49 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 48.1 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was allowed to cool to room temperature, cooled, added with 3.95 g of phthalic anhydride, and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.56 x 10 ⁴ , Mn = 0.52 x 10 ⁴ , and Mw / Mn = 2.99.

Synthesis of polyamic acid ester

249.29 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 123.6 g of NMP was added and cooled, and 29.69 g of N, N-diisopropylethylamine 114.82 g of the (b5-11) liquid synthesized in P-134 was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 3.2 L of isopropanol to obtain a precipitated solid which was filtered to obtain 73.21 g of the title compound (resin P-142) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.65 × 10 ⁴ and Mw / Mn = 1.78. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-143]

Synthesis of polyamic acid

17.47 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag) was placed in a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and NMP (N-methyl-2-pyrrolidone) g, and then 50.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Kagaku K.K.) was added thereto. The mixture was stirred at 60 DEG C for 4 hours, allowed to cool to room temperature. Then, 5.05 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 28.6 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was left to cool to room temperature, cooled, and 4.03 g of phthalic anhydride was added thereto. The mixture was stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.54 × 10 ⁴ , Mn = 0.41 × 10 ⁴ , and Mw / Mn = 3.73.

Synthesis of polyamic acid ester

243.73 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 120.9 g of NMP was added, and the mixture was cooled, and 29.69 g of N, N-diisopropylethylamine 114.57 g of the liquid of (b5-11) synthesized in P-134 was added. After the reaction was conducted at 0 DEG C or lower for 4 hours, the reaction solution was added to 3.2 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 72.50 g of the title compound (resin P-143) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.68 × 10 ⁴ and Mw / Mn = 1.80. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-144]

Synthesis of polyamic acid

10.48 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasag) was placed in a 500 ml flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, and NMP (N-methyl-2-pyrrolidone) 314.4 g. The mixture was heated to 70 占 폚, and 15.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) was added and stirred at 70 占 폚 for 15 minutes. Further, 15.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic anhydride was added and the mixture was stirred at 70 ° C for 15 minutes. Further, 15.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic anhydride was added, and the mixture was stirred at 60 ° C for 4 hours, allowed to cool to room temperature. Then, 14.29 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 81.0 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was allowed to cool to room temperature, cooled, and added with 3.63 g of phthalic anhydride and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.50 × 10 ⁴ , Mn = 0.60 × 10 ⁴ , and Mw / Mn = 2.50.

Synthesis of polyamic acid ester

249.99 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 124.0 g of NMP was added and cooled, and 28.51 g of N, N-diisopropylethylamine 107.22 g of the (b5-11) liquid synthesized in P-134 was added. After the reaction was carried out at 0 ° C or lower for 4 hours, the reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 72.20 g of the title compound (resin P-144) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 2.39 × 10 ⁴ and Mw / Mn = 1.76. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-145]

Synthesis of polyamic acid

45.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) and 50 g of NMP (N-methyl-2-thiophene) were placed in a 500 ml flask equipped with a thermometer, -Pyrrolidone), and the mixture was heated to 70 DEG C with stirring. A solution obtained by dissolving 10.48 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigas Co., Ltd.) in 80 g of NMP was added dropwise to the flask over 30 minutes, stirred at 60 ° C for 4 hours, cooled to room temperature . Then, 14.29 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 81.0 g of NMP were added and the mixture was stirred at 60 ° C for 2 hours. The mixture was allowed to cool to room temperature, cooled, and added with 3.63 g of phthalic anhydride and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 1.21 × 10 ⁴ , Mn = 0.47 × 10 ⁴ , and Mw / Mn = 2.58.

Synthesis of polyamic acid ester

249.99 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 124.0 g of NMP was added and cooled, and 28.51 g of N, N-diisopropylethylamine 107.22 g of the (b5-11) liquid synthesized in P-134 was added. After reacting at 0 ° C or lower for 4 hours, the reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 67.95 g of the title compound (resin P-145) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 1.94 × 10 ⁴ and Mw / Mn = 1.69. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

[Synthesis of P-146]

Synthesis of polyamic acid

45.00 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride (manufactured by Mitsubishi Chemical Corporation) and 50 g of NMP (N-methyl-2-thiophene) were placed in a 500 ml flask equipped with a thermometer, -Pyrrolidone), and the mixture was heated to 70 DEG C while stirring. 10.48 g of trans-1,4-cyclohexanediamine (manufactured by Iwatanigasagi) and 14.29 g of 2,2'-dimethyl-4,4'-diaminobiphenyl [manufactured by Wakayama Seika Co., Was added dropwise to the flask over a period of 30 minutes, followed by stirring at 60 DEG C for 6 hours. The solution was allowed to cool to room temperature. Then, 3.63 g of phthalic anhydride was added and stirred at room temperature for 10 hours to obtain a slightly brown transparent polyamic acid solution. Analysis of the obtained solution by GPC revealed that Mw = 2.26 x 10 ⁴ , Mn = 0.85 x 10 ⁴ , and Mw / Mn = 2.65.

Synthesis of polyamic acid ester

249.99 g of this polyamic acid solution was added to a 1 L flask equipped with a thermometer, a stirrer and a nitrogen inlet tube, 124.0 g of NMP was added and cooled, and 28.51 g of N, N-diisopropylethylamine 107.22 g of the (b5-11) liquid synthesized in P-134 was added. After reacting at 0 DEG C or lower for 4 hours, the reaction solution was added to 3.1 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 72.30 g of the title compound (resin P-146) as a white solid. Analysis of the obtained resin by GPC revealed that Mw = 3.75 × 10 ⁴ and Mw / Mn = 1.93. The solids were dissolved in DMSO and the ¹ H-NMR spectrum was measured. As a result of calculating the protection ratio from the peak integral ratio of carboxylic acid ester and carboxylic acid, it was 100%.

Other resins were synthesized in the same manner. These are of a synthetic resin, derived from a tetravalent organic group R ¹ around the structure a monomer structure, the divalent organic group R ² around the diamine monomer, R ¹ and the monomer that forms the peripheral structure, the input molar ratio of the R ² around the diamine monomer , A group which is decomposed by the action of an acid on R ³ to generate an alkali-soluble group (in the case of combination, the respective molar ratios), the protection rate of the carboxyl group by that group, the end encapsulant, the synthesis method, the mass average molecular weight, Mw / Mn) were as shown in Tables 1 to 4 below.

The abbreviations in the table are shown below.

[Preparation of Photosensitive Resin Composition]

The components shown in the following table were dissolved in a solvent shown in the table to obtain a total solid content concentration of 25 mass% and filtration was performed with a cassette filter made of polytetrafluoroethylene having a pore diameter of 0.1 占 퐉 to prepare a photosensitive resin composition. In the table, the solid content of each component is expressed as mass%.

After the photosensitive resin composition of Example 110 was left at room temperature for 4 weeks, the solution of the composition was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The imidization rate was calculated from the peak integral value of amide NH 3, %. After the photosensitive resin composition of Example 122 was left at room temperature for 4 weeks, the solution of the composition was dissolved in DMSO and the ¹ H-NMR spectrum was measured. The imidation rate was calculated from the peak integral value of amide NH 3 The rate of drought was less than 1%.

When the photosensitive resin composition of Example 114 was aged at room temperature for 4 weeks, the viscosity was lowered. Further, the acid value of the photosensitive resin composition was measured. As a result, the acid value was lowered, and the acid decomposable group including the structure represented by (a5-5) of the resin P-114 was partially decomposed. When the photosensitive resin composition of Example 122 was aged at room temperature for 4 weeks, no decrease in viscosity or acid value was observed.

[Image performance evaluation]

The prepared photosensitive resin composition was spin-coated on a 4-inch silicon wafer, and pre-dried at 120 ° C for 3 minutes on a hot plate to obtain a film having a film thickness of 5.0 μm. Subsequently, pattern exposure was performed using a via hole repetition pattern mask of 1 to 30 mu m in an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). Subsequently, it was heated at 120 DEG C for 3 minutes, padded with 2.38 mass% of TMAH aqueous solution, and rinsed with pure water. Thereafter, heating was performed on a hot plate at 100 DEG C for 2 minutes.

The obtained pattern film was observed with a measuring SEM (Hitachi Seisakusho S-8840, manufactured by Hitachi Seisakusho S-8840), and the minimum dimension of the resolved via hole was A to less than 3 탆, B to not less than 3 탆 and less than 5 탆, C ", and " D "

The obtained pattern film was observed with a line-of-sight SEM (Hitachi SEISAKUSHO S-8840, manufactured by Hitachi Seisakusho S-8840) to obtain a sensitivity of less than 250 mJ / cm 2 and a sensitivity of 250 mJ / cm 2 to less than 500 mJ / B, 500mJ / cm2 or more, 750mJ / cm2 or less, and 750mJ / cm2 or more.

[Evaluation of film properties]

The prepared photosensitive resin composition was spin-coated on a 4-inch silicon wafer, and pre-dried at 120 ° C for 3 minutes on a hot plate to obtain a film having a film thickness of 5.0 μm. Subsequently, the film was heated and cured at 250 DEG C for 60 minutes under a nitrogen atmosphere to obtain a polyimide film.

The film after curing was subjected to a stress measurement at 25 캜 by a thin film stress measuring apparatus (FLX-2320 made by Tencor Corporation). The smaller the value of the stress, the smaller the deflection of the wafer.

In the following table, numerical values in parentheses when solvents are used together represent mass ratios.

The abbreviations in the table are shown below.

[Acid generator]

[Increase / decrease]

[Thermal acid generator]

[Basic compound]

DIA: 2,6-diisopropylaniline

PEA: N-phenyldiethanolamine

DBU: 1,8-diazabicyclo [5.4.0] undeca-7-ene

EOA: Amine of structure

[Surfactants]

F176: Megapack F176 [manufactured by Dainippon Ink Kagaku Kogyo Co., Ltd.]

F475: Megapack F-475 (manufactured by Dainippon Ink and Chemicals, Incorporated)

PF6320: (manufactured by OMNOVA, fluorine)

BYK307: (manufactured by Big Chemical)

[Adhesion promoter]

GPTMS: 3-glycidyloxypropyltrimethoxysilane

MAPTMS: 3-methacryloxypropyltrimethoxysilane

TESPEC: triethoxysilylpropyl ethyl carbamate

[solvent]

GBL:? -Butyrolactone

NMP: N-methylpyrrolidone

CX: Cyclohexanone

CP: cycloheptanone

DMI: 1,3-dimethyl-2-imidazolidinone

[Polymerizable compound]

DPHA: dipentaerythritol hexaacrylate

As clearly shown from the results shown in Tables 5 to 8, Comparative Example 1 having an acid-decomposable group as R ³ in the general formula (1) but not having an alicyclic group as R ² has a low solubility in an alkali developing solution, It can be understood that sufficient results can not be obtained with respect to image performance such as sensitivity and sensitivity. Further, it can be seen that stress curves can be caused by wafer warpage.

Comparative Example 2, which has an alicyclic group as R ² but does not have an acid-decomposable group as R ³ , can not be judged even with a latent image, and sufficient results can not be obtained with respect to image performance such as resolution and sensitivity. Further, it can be seen that stress curves can be caused by wafer warpage.

Comparative Example 3 having an acid-decomposable group as R ³ in the general formula (1) but not having an alicyclic group as R ² is relatively good in image performance such as resolution and sensitivity, but is capable of causing wafer warping due to a large stress Able to know.

On the other hand, Examples 1 to 146 using the resin (a) which satisfies the requirements of the general formula (1) are excellent in image performance such as resolution and sensitivity, and have a small stress and can suppress the occurrence of wafer warpage .

(Industrial availability)

The present invention can be suitably used as a surface protective film, an interlayer insulating film, and an interlayer insulating film for a display device of a semiconductor device, and has lithography performance excellent in resolution and sensitivity, excellent in low stress characteristics in low temperature curing, There can be provided a relief pattern forming material, a photosensitive film, a polyimide film, a cured relief pattern, a method for producing the same, and a semiconductor device including the cured relief pattern capable of forming a cured relief pattern that prevents warpage.

Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

This application is based on Japanese Patent Application (Japanese Patent Application No. 2011-167622) filed on July 29, 2011 and Japanese Patent Application (Japanese Patent Application No. 2012-068197) filed on March 23, 2012, Which is incorporated herein by reference.

Claims

(a) a resin having a repeating unit represented by the following general formula (1), and
(b) a compound which generates an acid upon irradiation with an actinic ray or radiation.

[In the above general formula (1)
R ¹ represents a tetravalent organic group. The plurality of R < ¹ ^> may be the same or different.
R ² represents a divalent organic group. The plurality of R ² may be the same or different.
Provided that at least one of the plurality of R < ² > is a divalent organic group having an alicyclic group.
Each R ³ independently represents a hydrogen atom or an organic group.
Provided that at least one of the plurality of R < ³ > is a group represented by the following general formula (III)

[Wherein, in the general formula,
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
Rb represents a single bond or a divalent linking group.
Q represents an unsubstituted heterocyclic group or an alicyclic group substituted with an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group or an alkoxycarbonyl group;

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The method according to claim 1,
The resin (a) having a repeating unit represented by the general formula (1) is a resin having a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3) Sensitive resin composition.

[In the above general formula (2)
R ¹ 'is R ¹ and agreed in the general formula (1).
R ³ 'is R ³ and agreed in the general formula (1).
Provided that at least one of the plurality of R < ³ >'is a group represented by the above general formula (III).
R ⁴ is a divalent organic group having an alicyclic group.
In the general formula (3)
R ¹ "is R ¹ and agreed in the general formula (1).
R ³ "is R ³ as agreed in the general formula (1).
Provided that at least one of the plural R < ³ > s is a group represented by the above general formula (III).
R < ⁵ > is a divalent organic group different from R < ^{4 &}

The method of claim 3,
Wherein R ⁵ in the general formula (3) is a divalent group having an aromatic group.

5. The method of claim 4,
Wherein R ⁵ in the general formula (3) is a divalent group represented by any one of the following formulas.

The method according to claim 1,
Wherein the thermal decomposition temperature of -CO ₂ R ³ in the general formula (1) is 100 to 220 ° C.

delete

The method according to claim 1,
Wherein Ra in the general formula (III) is a group represented by the following general formula (IV) or (V).

[Wherein, in the general formula,
Rc and Rd each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom; May form a ring by bonding to each other, and at least two of Re, Rf and Rg may be bonded to each other to form a ring)

9. The method of claim 8,
Wherein at least one of Rc and Rd in formula (IV) is a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom Resin composition.

10. The method of claim 9,
Wherein at least one of Rc and Rd in the general formula (IV) is an aryl group.

The method according to claim 1,
Wherein at least one of Ra, Rb and Q in the general formula (III) is a group having an electron-withdrawing group or an electron-withdrawing group.

The method according to claim 1,
R ¹ in the general formula (1) is a monocyclic or condensed polycyclic aliphatic group or a tetravalent linking group having an aromatic group.

The method according to claim 1,
R ² in the general formula (1) is a divalent group having an alicyclic group, a divalent group having an aromatic group, or a divalent group containing a silicon atom.

The method according to claim 1,
Wherein the resin (a) has a mass average molecular weight of 200,000 or less.

The method according to claim 1,
(c) a basic compound.

The method according to claim 1,
Wherein the compound (b) is an oxime compound.

The method according to claim 1,
(f) an adhesion promoting agent.

The method according to claim 1,
Wherein the photosensitive resin composition is for positive type development.

A pattern forming material characterized by being the photosensitive resin composition according to claim 1.

A photosensitive film formed by the photosensitive resin composition according to claim 1.

A polyimide film obtained by subjecting the photosensitive resin composition according to claim 1 to heat treatment.

(A) a step of forming the photosensitive film described in (20) on a substrate,
(B) exposing the photosensitive film to an actinic ray or radiation,
(C) developing the exposed portion of the photosensitive film to remove with an aqueous alkali developer, and
(D) heat-treating the obtained relief pattern.

A cured relief pattern characterized by being obtained by the manufacturing method according to claim 22.

A semiconductor device comprising the cured relief pattern according to claim 23.

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