JP6146005B2 - Polyimide precursor composition and cured film using the composition - Google Patents

Description

  The present invention relates to a polyimide precursor composition and a cured film using the composition.

  In recent years, organic materials having high heat resistance such as polyimide resin have been widely applied as protective film materials for semiconductor integrated circuits (LSIs) (for example, Patent Documents 1 and 2). A protective film (cured film) using such a polyimide resin is obtained by heating and curing a resin film formed by applying and drying a polyimide precursor or a resin composition containing a polyimide precursor on a substrate. It is obtained with.

  With the miniaturization of semiconductor integrated circuits, an interlayer insulating film called a low-k layer for reducing the dielectric constant is required. Since the low-k layer has a pore structure, there is a problem that the mechanical strength is lowered. In order to protect such an interlayer insulating film having a low mechanical strength, a cured film formed of a polyimide resin is used. This cured film is required to have characteristics such as thick film formability (for example, 5 μm or more) and high elastic modulus (for example, 4 GPa or more). However, by increasing the film thickness and increasing the elastic modulus, the stress after curing increases, and the warpage of the semiconductor wafer increases, which may cause problems when transporting or fixing the wafer. Development is desired.

  As a method for reducing the stress of the polyimide resin, for example, a method of making a molecular chain a rigid skeleton in order to bring the thermal expansion coefficient of polyimide close to the thermal expansion coefficient of a silicon wafer (for example, Patent Document 3), and a flexible siloxane structure And a method of reducing the elastic modulus of polyimide by introducing a simple structure (for example, Patent Document 4).

On the other hand, if the polyimide resin composition used for forming the protective film is photosensitive, it is possible to easily form a patterned resin film (patterned resin film). By heating and curing such a patterned resin film, a pattern cured film (patterned cured film) can be easily formed.
As a method for making the polyimide resin composition photosensitive, there is a method for imparting photosensitivity to polyimide. As a method for imparting photosensitivity to polyimide, a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond, a method of using a soluble polyimide having a photopolymerizable olefin, a benzophenone skeleton, and nitrogen A method using a self-sensitized polyimide having an alkyl group at the ortho position of an aromatic ring to which atoms are bonded is known (for example, Patent Document 5). Among them, the method of introducing a methacryloyl group into a polyimide precursor through an ester bond can freely select a monomer to be used when synthesizing the polyimide precursor, and the methacryloyl group is bonded through a chemical bond. Since it is introduced, it is characterized by excellent stability over time.

  However, low-stress polyimide resins contain many conjugated aromatic ring units in the molecular chain, and even in the case of polyamic acid (polyimide precursor), which is a polyimide resin precursor, is absorbed in the ultraviolet region. Will have. Therefore, the transmittance of i-line (wavelength 365 nm), which is widely used in the exposure process for forming the pattern resin film, tends to decrease, and the sensitivity and resolution tend to decrease. That is, it has been difficult to achieve both improvement in i-line transmittance and reduction in stress of the cured film. Moreover, when the protective film obtained was thickened, there was a tendency that the i-line transmittance was further reduced and the pattern resin film could not be formed.

Japanese Patent No. 3526829 Japanese Patent No. 4524808 JP-A-5-295115 JP-A-7-304950 JP-A-7-242744

  An object of the present invention is to provide a resin composition capable of forming a cured film having a low stress regardless of a polymer skeleton, and a method for producing a cured film using the resin composition.

（式中、Ｒ^１は４価の有機基である。
Ｒ^２は２価の有機基である。
Ｒ^３及びＲ^４は、各々独立に水素原子、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、又は炭素炭素不飽和二重結合を有する１価の有機基である。）

（式中、Ｍ^１は、チタン及びジルコニウムから選択される金属原子である。
ｍは、０〜４までの整数であり、ｎは０〜４までの整数であり、ｍとｎの和は４である。
Ｒ^５は、各々独立に炭素数１〜１８のアルキル基である。
Ｒ^６は、各々独立に１価の有機基であり、前記１価の有機基は、水酸基、カルボニル基、及びアミノ基から選択されるＭ^１と配位結合可能な基を１以上を有する。）
２．前記式（２）で表される金属錯体化合物が下記式（３）で表わされる１に記載の樹脂組成物。

（式中、Ｍ^１は、チタン及びジルコニウムから選択される金属原子である。
ａは０〜４までの整数であり、ｂは０〜４までの整数であり、ｃは０〜４までの整数であり、ａとｂとｃの和は４である。
Ｒ^５は、各々独立に炭素数１〜１８のアルキル基である。
Ｒ^８及びＲ^９は、各々独立に水素原子、水酸基、炭素数１〜６の有機基、炭素数１〜６のアルキルアルコール基、又は炭素数１〜６のアミノアルキル基である。
Ｒ^１１〜Ｒ^１４は、各々独立に水素原子、水酸基、炭素数１〜６のアルキル基、又は炭素数１〜６のアルキルアルコール基である。
Ｒ^１１〜Ｒ^１４は、さらに水酸基、カルボニル基、及びアミノ基から選択されるＭ^１と配位結合可能な基を含んでもよい。）
３．前記金属錯体化合物が、前記ポリイミド前駆体１００質量部に対して０．００５〜１５質量部含まれる１又は２に記載の樹脂組成物。
４．さらに（ｃ）活性光線照射によりラジカルを発生する化合物を含有する１〜３のいずれかに記載の樹脂組成物。
５．前記（ｃ）活性光線照射によりラジカルを発生する化合物が、前記（ａ）ポリイミド前駆体１００質量部に対して０．１〜２０質量部含まれる４に記載の樹脂組成物。
６．１〜５のいずれかに記載の樹脂組成物から形成される硬化膜。
７．１〜５のいずれかに記載の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程と、得られた塗膜を加熱処理する工程とを含む、硬化膜の製造方法。
８．４又は５に記載の樹脂組成物から形成されるパターン硬化膜。
９．４又は５に記載の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程と、
前記工程で形成した塗膜に活性光線を照射後、現像してパターン樹脂膜を得る工程と、
パターン樹脂膜を加熱処理する工程とを含む、パターン硬化膜の製造方法。 According to the present invention, the following resin composition and the like are provided.
1. (A) A resin composition comprising a polyimide precursor having a structural unit represented by the following general formula (1), and (b) a metal complex compound represented by the following general formula (2).

(In the formula, R ¹ is a tetravalent organic group.
R ² is a divalent organic group.
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond. )

(Wherein M ¹ is a metal atom selected from titanium and zirconium.
m is an integer from 0 to 4, n is an integer from 0 to 4, and the sum of m and n is 4.
R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms.
R ⁶ each independently represents a monovalent organic group, and the monovalent organic group has one or more groups capable of coordinating with M ¹ selected from a hydroxyl group, a carbonyl group, and an amino group. )
2. 2. The resin composition according to 1, wherein the metal complex compound represented by the formula (2) is represented by the following formula (3).

(Wherein M ¹ is a metal atom selected from titanium and zirconium.
a is an integer from 0 to 4, b is an integer from 0 to 4, c is an integer from 0 to 4, and the sum of a, b, and c is 4.
R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms.
R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, an organic group having 1 to 6 carbon atoms, an alkyl alcohol group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms.
R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkyl alcohol group having 1 to 6 carbon atoms.
R ^{11 to} R ¹⁴ may further include a group capable of coordinating with M ¹ selected from a hydroxyl group, a carbonyl group, and an amino group. )
3. The resin composition according to 1 or 2, wherein the metal complex compound is contained in an amount of 0.005 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor.
4). Furthermore, (c) The resin composition in any one of 1-3 containing the compound which generate | occur | produces a radical by irradiation of actinic light.
5). 5. The resin composition according to 4, wherein the compound (c) that generates radicals upon irradiation with actinic rays is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the (a) polyimide precursor.
The cured film formed from the resin composition in any one of 6.1-5.
The manufacturing method of a cured film including the process of apply | coating the resin composition in any one of 7.1-5 on a board | substrate, drying and forming a coating film, and the process of heat-processing the obtained coating film .
A pattern cured film formed from the resin composition according to 8.4 or 5.
Applying the resin composition according to 9.4 or 5 on a substrate and drying to form a coating film;
Irradiating the coating film formed in the above step with actinic rays and developing to obtain a patterned resin film;
A method for producing a patterned cured film, comprising a step of heat-treating the pattern resin film.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the cured film using the resin composition which can form the cured film with low stress irrespective of polymer frame | skeleton, and the said resin composition can be provided.

It is a schematic sectional drawing of one Embodiment of the semiconductor device using the resin composition of this invention.

（式中、Ｒ^１は４価の有機基である。
Ｒ^２は２価の有機基である。
Ｒ^３及びＲ^４は、各々独立に水素原子、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、又は炭素炭素不飽和二重結合を有する１価の有機基である。）

（式中、Ｍ^１は、チタン及びジルコニウムから選択されるいずれかの金属原子である。
ｍは、０〜４までの整数であり、ｎは０〜４までの整数であり、ｍとｎの和は４である。
Ｒ^５は、各々独立に炭素数１〜１８のアルキル基である。
Ｒ^６は、各々独立に炭素数１〜６の２価の有機基、又はアミノアルキレン基であり、前記炭素数１〜６の２価の有機基及びアミノアルキレン基は、各々独立に水酸基、カルボニル基又はアミノ基を置換基として含んでもよい。
Ｒ^７は、各々独立に水酸基、カルボニル基及びアミノ基から選択される基である。） [Resin composition]
The resin composition of the present invention includes (a) a polyimide precursor having a structural unit represented by the following general formula (1), and (b) a metal complex compound represented by the following general formula (2).

(In the formula, R ¹ is a tetravalent organic group.
R ² is a divalent organic group.
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond. )

(Wherein M ¹ is any metal atom selected from titanium and zirconium.
m is an integer from 0 to 4, n is an integer from 0 to 4, and the sum of m and n is 4.
R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms.
R ⁶ is each independently a divalent organic group having 1 to 6 carbon atoms or an aminoalkylene group, and the divalent organic group and aminoalkylene group having 1 to 6 carbon atoms are each independently a hydroxyl group, carbonyl A group or an amino group may be included as a substituent.
R ⁷ is a group independently selected from a hydroxyl group, a carbonyl group and an amino group. )

  The resin composition of this invention can make the stress of the cured film obtained low by setting it as the above structures. Hereinafter, each component will be described in detail.

（式中、Ｒ^１は４価の有機基である。
Ｒ^２は２価の有機基である。
Ｒ^３及びＲ^４は、各々独立に水素原子、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、又は炭素炭素不飽和二重結合を有する１価の有機基である。） [(A) Polyimide precursor]
The resin composition of this invention contains the polyimide precursor which has a structural unit represented by following General formula (1) as (a) component.

(In the formula, R ¹ is a tetravalent organic group.
R ² is a divalent organic group.
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond. )

The tetravalent organic group of R ¹ in formula (1) is a group having a structure derived from tetracarboxylic dianhydride used as a raw material for producing the polyimide precursor of formula (1). Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3 ′, 4,4′-tetra Carboxylic dianhydride, p-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2 , 3-Dicarboxyphenyl) propane dianhydride, 1, , 1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis {4 ′-(2,3-dicarboxyphenoxy) phenyl} propane dianhydride, 2,2-bis { 4 ′-(3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2′-bis {4 ′-(2,3-di Carboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2′-bis {4- (3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4 ' Sulfonyl di phthalic dianhydride. These are used alone or in combination of two or more.

In particular, from the viewpoint of the stress of the cured film, tetracarboxylic dianhydride having a tetravalent organic group of R ¹ is pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is preferred.

（式中、Ｘ及びＹは、各々独立に、各々が結合するベンゼン環と共役しない２価の基、又は単結合を示す。） From the viewpoint of reducing the thermal expansion coefficient of the cured film, the tetravalent organic group of R ^{1 in} the formula (1) is preferably any one of organic groups represented by the following formula.

(In the formula, X and Y each independently represent a divalent group that is not conjugated to the benzene ring to which each is bonded, or a single bond.)

The divalent organic group represented by R ^{2 in} the formula (1) is a group having a structure derived from a diamine used as a raw material for producing the polyimide precursor of the formula (1). Examples of the diamine include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 4,4′- Diaminooctafluorobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4 '-(or 3,4'-, 3 , 3'-, 2,4'-, 2,2 '-) diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'- ) Diaminodiphenyl sulfone, 4,4 ′-(or 3,4′-, 3,3′-, 2,4′-, 2,2 ′-) diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4 , 4'-methylene-bis- (2,6-diethi Aniline), 4,4′-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4′-benzophenonediamine, bis- {4- (4 '-Aminophenoxy) phenyl} sulfone, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5 Examples include 5′-tetramethyl-4,4′-diaminodiphenylmethane, bis {4- (3′-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl) propane, and diaminopolysiloxane. These are used alone or in combination of two or more.

In particular, from the viewpoint of low stress, good i-line transmittance, heat resistance, and the like, the divalent organic group diamine of R ² is 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl. 2,2′-bis (fluoro) -4,4′-diaminobiphenyl and 4,4′-diaminooctafluorobiphenyl are preferred.

（式中、Ｒ^１０〜Ｒ^１７は、各々独立に水素原子、フッ素原子又は１価の有機基を表し、Ｒ^１０〜Ｒ^１７の少なくとも１つはフッ素原子又はトリフルオロメチル基である）

（式中、Ｒ^１８及びＲ^１９は、各々独立にフッ素原子又はトリフルオロメチル基を表す） From the viewpoint of i-line transmittance, the divalent organic group represented by R ^{2 in} the formula (1) is preferably a divalent organic group represented by the following formula (5) or (6) and is easily available. From the viewpoint, the divalent organic group represented by the following formula (6) is more preferable.

(Wherein R ^{10 to} R ¹⁷ each independently represents a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ^{10 to} R ¹⁷ is a fluorine atom or a trifluoromethyl group)

(Wherein R ¹⁸ and R ¹⁹ each independently represents a fluorine atom or a trifluoromethyl group)

R ³ and R ^{4 in} Formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent having a carbon-carbon unsaturated double bond. Organic group.
The monovalent organic group having a carbon-carbon unsaturated double bond includes, for example, an acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group and a methacryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group, and n-dodecyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like.
Examples of the acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like, and a methacryloxyalkyl group in which the alkyl group has 1 to 10 carbon atoms. Examples thereof include a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxybutyl group.

When the resin composition of the present invention is a photosensitive resin, R ³ and / or R ⁴ is an acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group, or a methacrylic acid having 1 to 10 carbon atoms in the alkyl group. A monovalent organic group having a carbon-carbon unsaturated double bond such as a roxyalkyl group is desirable.
The composition in which the component (a) is as described above enables crosslinking between molecular chains by radical polymerization in combination with (c) a compound that generates radicals upon irradiation with actinic rays.

The residual stress of the cured film obtained by applying the polyimide precursor represented by the formula (1) to the substrate and heat-curing is preferably 35 MPa or less when the thickness of the cured film is 10 μm. Preferably it is 27 MPa or less, More preferably, it is 25 MPa or less.
If the residual stress of the cured film having a film thickness of 10 μm is 35 MPa or less, the wafer warpage of the cured film having a film thickness of 10 μm obtained from the composition of the present invention can be more sufficiently suppressed. The trouble which arises can be suppressed more.
The residual stress can be measured by a method of measuring the amount of warpage of the wafer using a thin film stress measuring device (FLX-2320 manufactured by KLA Tencor) and then converting it into stress.

As for the molecular weight of a polyimide precursor, it is desirable that the weight average molecular weight in terms of polystyrene is 10,000 to 100,000, more desirably 15,000 to 100,000, and further desirably 20,000 to 85,000.
If the weight average molecular weight of the polyimide precursor is less than 10,000, the stress after curing may not be sufficiently reduced. If it is more than 100,000, the solubility in a solvent is reduced, the viscosity of the solution is increased, and the handleability is increased. May fall. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method, and can be calculated | required by converting using a standard polystyrene calibration curve.

（式中、Ｒ^１〜Ｒ^４は式（１）と同じである。） The (a) polyimide precursor of the present invention can be synthesized by addition polymerization of the above-described tetracarboxylic dianhydride and diamine. Moreover, after making the tetracarboxylic dianhydride represented by Formula (4) into a diester derivative, it converts into the acid chloride represented by Formula (5), and reacts with the diamine represented by Formula (6). Can also be synthesized.

^(Wherein, R 1 to R ⁴ is the same as equation (1).)

（式中、Ｒ^１５は、水素原子、アルキル基、シクロアルキル基、又は炭素炭素不飽和二重結合を有する１価の有機基である。） A tetracarboxylic acid mono (di) ester dichloride represented by the formula (5) is obtained by reacting a tetracarboxylic dianhydride represented by the formula (4) with a compound represented by the following general formula (7). The tetracarboxylic acid mono (di) ester is prepared, and the obtained tetracarboxylic acid mono (di) ester is reacted with a chlorinating agent such as thionyl chloride or dichlorooxalic acid.

(In the formula, R ¹⁵ is a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent organic group having a carbon-carbon unsaturated double bond.)

Examples of the alcohol represented by the formula (7) include alcohols having an alkyl group having 1 to 20 carbon atoms or cycloalkyl groups having 3 to 20 carbon atoms, and monovalent organic groups having a carbon-carbon unsaturated double bond ( For example, an alcohol having an acryloxyalkyl group having 1 to 10 carbon atoms in an alkyl group and a methacryloxyalkyl group having 1 to 10 carbon atoms in an alkyl group can be used.
Examples of alcohols represented by the formula (7) include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, hexanol, cyclohexanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl. Examples include methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. These may be used singly or in combination of two or more.

The chlorinating agent is usually used by reacting 2 mol equivalent of chlorinating agent with 1 mol of tetracarboxylic acid mono (di) ester in the presence of twice the amount of basic compound with respect to chlorinating agent. However, in order to control the molecular weight of the synthesized polyimide precursor, the equivalent may be appropriately adjusted.
The equivalent amount of the chlorinating agent is preferably 1.5 to 2.5 molar equivalents, more preferably 1.6 to 2.4 molar equivalents, and even more preferably 1.7 to 2.3 molar equivalents.
In the case of less than 1.5 molar equivalents, the low molecular weight of the polyimide precursor is low, so there is a possibility that the low stress property after curing is not sufficiently exhibited. On the other hand, when it exceeds 2.5 molar equivalents, a large amount of the hydrochloride of the basic compound remains in the polyimide precursor, and the electrical insulation properties of the cured polyimide may be reduced.

As the basic compound, for example, pyridine, 4-dimethylaminopyridine, triethylamine and the like can be used.
The basic compound is preferably used in an amount of 1.5 to 2.5 times the chlorinating agent, more preferably 1.7 to 2.4 times the amount, and 1.8 to 2.3 times the basic amount. More desirably, it is an amount. If the amount is less than 1.5 times, the molecular weight of the polyimide precursor is low, and the stress after curing may not be sufficiently reduced. If the amount is more than 2.5 times, the polyimide precursor may be colored.

In addition to the above, a tetracarboxylic acid mono (di) ester dichloride represented by the formula (5) can also be synthesized by reacting the tetracarboxylic dianhydride with the general formula (7) in the presence of a basic catalyst. it can.
Examples of the basic catalyst include 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and the like.

  The molar ratio of tetracarboxylic dianhydride and diamine when synthesizing the polyimide precursor is usually 1.0, but for the purpose of controlling the molecular weight and terminal residue, it is in the range of 0.7 to 1.3. You may carry out by molar ratio. When the molar ratio is less than 0.7 or more than 1.3, the molecular weight of the obtained polyimide precursor becomes small, and the low stress property after curing may not be sufficiently exhibited.

The above addition polymerization, condensation reaction, synthesis of diester derivatives, and synthesis of acid chlorides are desirably performed in an organic solvent.
The organic solvent to be used is preferably a polar solvent that completely dissolves the synthesized polyimide precursor, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetra Examples include methylurea, hexamethylphosphoric triamide, and γ-butyrolactone.
In addition to polar solvents, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and the like can also be used. For example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2- Examples include dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.
You may use said organic solvent individually or in combination of 2 or more types.

（式中、Ｍ^１は、チタン及びジルコニウムから選択される金属原子である。
ｍは、０〜４までの整数であり、ｎは０〜４までの整数であり、ｍとｎの和は４である。
Ｒ^５は、各々独立に炭素数１〜１８のアルキル基である。
Ｒ^６は、各々独立に１価の有機基であり、前記１価の有機基は、水酸基、カルボニル基、及びアミノ基から選択されるＭ^１と配位結合可能な基を１以上を有する。） [(B) Metal Complex Compound]
The resin composition of this invention contains the metal complex compound represented by following General formula (2) as (b) component.

(Wherein M ¹ is a metal atom selected from titanium and zirconium.
m is an integer from 0 to 4, n is an integer from 0 to 4, and the sum of m and n is 4.
R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms.
R ⁶ each independently represents a monovalent organic group, and the monovalent organic group has one or more groups capable of coordinating with M ¹ selected from a hydroxyl group, a carbonyl group, and an amino group. )

  When the resin composition of this invention contains the metal complex compound represented by (b) Formula (2), the thermal expansion coefficient of the obtained cured film can be made small and stress can be made low. This is considered because the component (b) improves the orientation of the polyimide cured film.

In Formula (2), M ¹ is any metal atom selected from titanium and zirconium, and is preferably titanium from the viewpoint of the mechanical strength of the cured film.
m is an integer from 0 to 4, n is an integer from 0 to 4, and the sum of m and n is 4.
From the viewpoint of storage stability, m is preferably 0 to 2, and n is preferably 1 to 4.

R ⁵ each independently represents an alkyl group having 1 to 18 carbon atoms.
Specifically, the alkyl group having 1 to 18 carbon atoms is methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group, An n-dodecyl group etc. are mentioned. From the viewpoint of storage stability, an isopropyl group is preferable.

R ⁶ is each independently a monovalent organic group, and the monovalent organic group has one or more groups capable of coordinating with M ¹ selected from a hydroxyl group, a carbonyl group, and an amino group.
Examples of the monovalent organic group for R ⁶ include an alkyl group having 1 to 6 carbon atoms. R ⁶ includes, for example, an aminoalkyl group composed of an alkyl group and an amino group; an alcohol amino group composed of an alkyl group, a hydroxyl group and an amino group; and a monovalent residue of a hydroxy acid composed of an alkyl group, a carbonyl group and a hydroxyl group.
Examples of the alkyl group having 1 to ⁶ carbon atoms of R ⁶ include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, and an n-hexyl group, preferably from the viewpoint of availability. An ethyl group.
Specific examples of R ⁶ include methanolamino group, ethanolamino group, diethanolamino group, triethanolamino group, propanolamino group, butanolamino group, pentanolamino group, hexanolamino group, acetylaceto group, and ethylacetylacetate group. And ethyl lactate group.
From the viewpoint of availability, R ⁶ is preferably an acetylaceto group.

（式中、Ｍ^１、Ｒ^５、ｍ、及びｎは式（２）と同様である。
Ｒ^６’は、各々独立に炭素数１〜６の２価の有機基、又はアミノアルキレン基であり、当該炭素数１〜６の２価の有機基及びアミノアルキレン基は、各々独立に水酸基、カルボニル基又はアミノ基をさらに含んでもよい。
Ｒ^７は、各々独立に水酸基、カルボニル基及びアミノ基から選択される基である。） The metal complex compound represented by the formula (2) is preferably a metal complex compound represented by the following formula (2 ′).

(In the formula, M ¹ , R ⁵ , m, and n are the same as in formula (2).
R ^{6 ′} is each independently a divalent organic group having 1 to 6 carbon atoms or an aminoalkylene group, and the divalent organic group and aminoalkylene group having 1 to 6 carbon atoms are each independently a hydroxyl group, A carbonyl group or an amino group may further be included.
R ⁷ is a group independently selected from a hydroxyl group, a carbonyl group and an amino group. )

（式中、Ｍ^１は、チタン及びジルコニウムから選択される金属原子である。
ａは０〜４までの整数であり、ｂは０〜４までの整数であり、ｃは０〜４までの整数であり、ａとｂとｃの和は４である。
Ｒ^５は、各々独立に炭素数１〜１８のアルキル基である。
Ｒ^８及びＲ^９は、各々独立に水素原子、水酸基、炭素数１〜６の有機基、炭素数１〜６のアルキルアルコール基、又は炭素数１〜６のアミノアルキル基である。
Ｒ^１１〜Ｒ^１４は、各々独立に水素原子、水酸基、炭素数１〜６のアルキル基、又は炭素数１〜６のアルキルアルコール基である。
Ｒ^１１〜Ｒ^１４は、さらに水酸基、カルボニル基、及びアミノ基から選択されるＭ^１と配位結合可能な基を含んでもよい。） The metal complex compound represented by the formula (2) is preferably a metal complex compound represented by the following formula (3) from the viewpoint of availability.

(Wherein M ¹ is a metal atom selected from titanium and zirconium.
a is an integer from 0 to 4, b is an integer from 0 to 4, c is an integer from 0 to 4, and the sum of a, b, and c is 4.
R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms.
R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, an organic group having 1 to 6 carbon atoms, an alkyl alcohol group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms.
R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkyl alcohol group having 1 to 6 carbon atoms.
R ^{11 to} R ¹⁴ may further include a group capable of coordinating with M ¹ selected from a hydroxyl group, a carbonyl group, and an amino group. )

In Formula (3), M ¹ is a metal atom selected from titanium and zirconium, and is preferably titanium from the viewpoint of the mechanical strength of the cured film.
a is an integer from 0 to 4, b is an integer from 0 to 4, c is an integer from 0 to 4, and the sum of a, b, and c is 4. From the viewpoint of availability, a is preferably 0 to 2, b is preferably 1 to 4, and c is preferably 0 to 2. More preferably, the sum of a and c is 4 or b is 4.

R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms, and specific examples of the alkyl group having 1 to 18 carbon atoms are the same as R ^{5 in the} formula (2).

R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, an organic group having 1 to 6 carbon atoms, an alkyl alcohol group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms.
Specific examples of R ⁸ and R ⁹ include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, methanol amino group, ethanol amino group, diethanol amino group, tri Examples thereof include an ethanolamino group, a propanolamino group, a butanolamino group, a pentanolamino group, and a hexanolamino group, and a methyl group is preferable from the viewpoint of availability.

R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkyl alcohol group having 1 to 6 carbon atoms. R ^{11 to} R ¹⁴ are specifically methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group, n- Examples include dodecyl group, methanolamino group, ethanolamino group, diethanolamino group, triethanolamino group, propanolamino group, butanolamino group, pentanolamino group, and hexanolamino group.

In the metal complex compound of the formula (2) as the component (b), specific examples of the compound laughed by the formula (2) in which M ¹ is titanium include titanium diisopropoxybis (acetylacetonate), titanium tetraacetyl Acetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), titanium diisopropoxybis (triethanolaminate), titanium lactate Examples include ammonium salts and titanium lactate.
Specific examples of the compound in which M ¹ is zirconium in the metal complex compound of the formula (2) as the component (b) include monobutoxy trisacetylacetonatozirconium, dibutoxybisacetylacetonatozirconium, tributoxyacetylacetonato Zirconium, zirconium tetraacetylacetonate, butoxytrisethylacetylacetate zirconium, dibutoxybisethylacetoacetate zirconium, tributoxymonoethylacetylacetate zirconium, tetrakisethyl lactate zirconium, dibutoxybisethyl lactate zirconium, bisacetylacetonatobisethylacetyl Acetonatozirconium, monoacetylacetotrisethylacetylacetonatozirconium, monoacetylacetonato Examples thereof include bisethylacetylacetonatobutoxyzirconium and bisacetylacetonatobisethyllactonatozirconium.
These metal complex compounds may be used alone or in combination of two or more.

  In particular, from the viewpoint of low stress and storage stability, the metal complex compound as component (b) is preferably titanium tetraacetylacetonate, titanium diisopropoxybis (triethanolaminate), titanium diisopropoxybis (ethyl). Acetoacetate) or zirconium tetraacetylacetonate.

  (B) As a compounding quantity of the metal complex compound of a component, it is desirable that it is 0.005-15 weight part with respect to 100 weight part of (a) component, and it is more preferable that it is 0.01-10 weight part. Desirably, 0.01 to 5 parts by weight is more desirable. When the blending amount is less than 0.005 parts by weight, the crosslinking reaction with the component (a) and the orientation controllability of the component (a) are not exhibited at the time of curing, and when it exceeds 15 parts by weight, the elongation at break of the cured film is increased. May fall.

[Compounds that generate radicals by actinic rays]
In the composition of the present invention, when R ³ and / or R ^{4 of the} polyimide precursor represented by the formula (1) is a monovalent group having a carbon-carbon unsaturated double bond, the composition is (c) active. By further containing a compound that generates radicals when irradiated with light, a photosensitive resin composition can be obtained.
The resin composition of the present invention can further improve the i-line transmittance by including a compound that generates radicals when irradiated with actinic rays as component (c).

（式中、Ｒ^１０は、１価の芳香環基又はヘテロ環基であり、芳香環基及びヘテロ環基はそれぞれ置換基を有していてもよい。） The component (c) is not particularly limited as long as it is a compound that generates radicals upon irradiation with actinic rays. The component (c) is preferably a compound having a structure represented by the following formula (7) from the viewpoint of radical generation.

(In the formula, R ¹⁰ is a monovalent aromatic ring group or a heterocyclic group, and each of the aromatic ring group and the heterocyclic group may have a substituent.)

  Examples of the component (c) include compounds classified into oxime esters described later, N, N′-tetraalkyl-, such as benzophenone and N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone). 4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone -1 and other aromatic ketones, quinones fused with an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal.

（式（１７）中、Ｒ^３１は、炭素数１〜２０のアルキル基；１個以上の酸素原子によって中断された炭素数２〜２０のアルキル基；炭素数１〜１２のアルコキシ基；炭素数１〜４のアルキル基で置換されたフェニル基；フェニル基；炭素数１〜２０のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲン基、シクロペンチル基、シクロヘキシル基、炭素数１〜１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２〜１８のアルキル基及び／又は炭素数１〜４のアルキル基で置換されたフェニル基；又はビフェニリル基である。
Ｒ^３２は、下記式（１８）で表される基であるか、上記Ｒ^３１と同じの基である。
Ｒ^３３〜Ｒ^３５は、各々独立に炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、又はハロゲン原子である。）

（式（１８）中、Ｒ^３６〜Ｒ^３８は、各々独立に式（１７）のＲ^３３〜Ｒ^３５と同じ基である） In addition to the above, examples of the component (c) include compounds represented by the following formula (17).

(In formula (17), R ³¹ represents an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; Phenyl group substituted with 1 to 4 alkyl groups; phenyl group; alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen group, cyclopentyl group, cyclohexyl group, alkenyl with 1 to 12 carbon atoms A phenyl group substituted with a C2-C18 alkyl group and / or a C1-C4 alkyl group interrupted by one or more oxygen atoms; or a biphenylyl group.
R ³² is a group represented by the following formula (18) or the same group as R ³¹ described above.
R ^{33 to} R ³⁵ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. )

(In formula (18), R ^{36 to} R ³⁸ are each independently the same group as R ^{33 to} R ³⁵ in formula (17)).

  Among the components (c) described above, oxime esters, in particular, are more sensitive and have a diamine residue represented by the above (5) or (6), particularly the diamine residue represented by (6). In the photosensitive resin composition containing the polyimide precursor which has group, a remarkably favorable pattern is given and it is more preferable.

（式（８）中、Ｒ^２１〜Ｒ^２７は、各々独立に１価の基を表す。） In particular, in the case of the component (a) having a diamine residue represented by the formula (6), the conventional resin composition often cannot obtain good photosensitive characteristics. Particularly preferable oxime esters are compounds represented by the following formula (8) from the viewpoint of obtaining good sensitivity and remaining film ratio even with such component (a).

(In formula (8), R ^{21 to} R ²⁷ each independently represents a monovalent group.)

Preferable groups of the monovalent group of R ^{21 to} R ²⁷ are different from each other and are, for example, as follows.
R ²¹ is preferably a phenyl group (provided that an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR ^{39 ′} , —SR ^{40 ′} or —N (R ^{41 ′} ) (R ^{42 ′} )). R ^{39 ′ to} R ^{42 ′} are each an alkyl group having 1 to 20 carbon atoms; an alkyl group having 1 to 20 carbon atoms (provided that the alkyl group has 2 to 20 carbon atoms). In this case, it has one or more oxygen atoms between main chain carbon atoms and / or may be substituted with one or more hydroxyl groups.); A cycloalkyl group having 5 to 8 carbon atoms; 20 alkanoyl groups; substituted with one or more of a benzoyl group (wherein the alkyl group has 1 to 6 carbon atoms, a phenyl group, -OR ^{39 '} , -SR ^40' or -N (R ^{41 '} ) (R ^42' )) good ^{.R 39 '~R 42'} is be an alkyl group having 1 to 20 carbon atoms An alkoxycarbonyl group having 2 to 12 carbon atoms (provided that when the alkoxyl group has 2 to 11 carbon atoms, the alkoxyl group has one or more oxygen atoms between main chain carbon atoms, and / or) Phenoxycarbonyl group (however, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR ^{39 ′} or —N (R ^{41 ′} ) (R ⁴² ). ^′ ) May be substituted with one or more of R ^{39 ′} , R ^{41 ′} and R ^{42 ′} are alkyl groups having 1 to 20 carbon atoms); cyano group; nitro group; —CON (R ⁴¹ ) (R ⁴² ); a haloalkyl group having 1 to 4 carbon atoms; —S (O) _m —R ⁴³ (wherein R ⁴³ is substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 12 carbon atoms) An aryl group having 6 to 12 carbon atoms, Is 1 or 2);. Show or diphenylphosphino yl group; aryloxy sulfonyl group having 6 to 10 carbon atoms; alkoxysulfonyl group having 1 to 6 carbon atoms.

R ²² is preferably an alkanoyl group having 2 to 12 carbon atoms (provided that it may be substituted with one or more of a halogen atom or a cyano group); 6 alkenoyl groups; substituted with one or more of a benzoyl group (wherein the alkyl group has 1 to 6 carbon atoms, a halogen atom, a cyano group, -OR ³⁹ , -SR ⁴⁰ or -N (R ⁴¹ ) (R ⁴² )) An alkoxycarbonyl group having 2 to 6 carbon atoms; or a phenoxycarbonyl group (which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms or a halogen atom).

R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are preferably each independently a hydrogen atom; a halogen atom; an alkyl group having 1 to 12 carbon atoms; a cyclopentyl group; a cyclohexyl group; a phenyl group (provided that —OR ³⁹ , ^{-SR 40} or ^{-N (R 41) (R 42} ) may be substituted with 1 or more); benzyl group; a benzoyl group; an alkanoyl group having 2 to 12 carbon atoms; alkoxycarbonyl of 2 to 12 carbon atoms Group (provided that when the alkoxyl group has 2 to 11 carbon atoms, the alkoxyl group has one or more oxygen atoms between main chain carbon atoms and / or may be substituted with one or more hydroxyl groups) .); phenoxycarbonyl group; ^{-OR 39} (where, ^{-OR 39,} one of the 5-membered ring and a carbon atom in the substituent to the phenyl ring in or phenyl ring or 6 May form a ring); -. SR 40 ^(where, -SR ⁴⁰ may form a single bond to 5-membered or 6-membered ring with the carbon atom in the substituent to the phenyl ring in or phenyl ring -S (O) R ⁴⁰ (provided that -SR ⁴⁰ is bonded to one carbon atom in the phenyl ring or a substituent to the phenyl ring to form a 5-membered or 6-membered ring. -SO ₂ R ⁴⁰ (However, -SR ⁴⁰ is bonded to one carbon atom in the phenyl ring or a substituent to the phenyl ring to form a 5-membered or 6-membered ring. Or —N (R ⁴¹ ) (R ⁴² ) (wherein —NR ⁴¹ and / or —NR ⁴² is bonded to one carbon atom in the phenyl ring or in a substituent to the phenyl ring). And may form a 5-membered ring or a 6-membered ring).
However, at least one of R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ is —OR ³⁹ , —SR ⁴⁰ or —N (R ⁴¹ ) (R ⁴² ).

R ³⁹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a substituted alkyl group having 2 to 6 carbon atoms (provided that the substituent is a hydroxyl group, a mercapto group, a cyano group, or an alkoxyl group having 1 to 4 carbon atoms) , Alkenyloxy group having 3 to 6 carbon atoms, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, alkylcarbonyloxy group having 2 to 5 carbon atoms, phenylcarbonyloxy group, carboxyl group Or it consists of 1 or more of C2-C5 alkoxycarbonyl groups. }, An alkyl group having 2 to 6 carbon atoms having one or more oxygen atoms between main chain carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, — (CH ₂ CH ₂ O) _n H (where n is 1) , An alkenyl group having 3 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenyl group (however, a halogen atom, an alkyl group having 1 to 12 carbon atoms or a carbon number of 1). To 4 alkoxy groups), a phenylalkyl group having 7 to 9 carbon atoms, or —Si (R ⁴⁹ ) _r (R ⁵⁰ ) _3-r (wherein R ⁴⁹ is 1 to 1 carbon atoms) 8 represents an alkyl group, R ⁵⁰ represents a phenyl group, and r represents an integer of 1 to 3.

R ⁴⁰ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, a substituted alkyl group having 2 to 6 carbon atoms {provided that the substituent is a hydroxyl group or a mercapto group , Cyano group, alkoxy group having 1 to 4 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, and 2 to 5 carbon atoms It consists of one or more of an alkylcarbonyloxy group, a phenylcarbonyloxy group, a carboxyl group, or an alkoxycarbonyl group having 2 to 5 carbon atoms. }, An alkyl group having 2 to 12 carbon atoms having at least one oxygen atom or sulfur atom between main chain carbon atoms, a phenyl group (however, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or 1 to 4 carbon atoms) Or an alkyl group of 7 to 9 carbon atoms.

R ⁴¹ and R ⁴² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms. , A cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a phenyl group (provided that it is substituted with one or more alkyl groups having 1 to 12 carbon atoms or alkoxyl groups having 1 to 4 carbon atoms) Or an alkanoyl group having 2 to 3 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, or a benzoyl group.
R ⁴¹ and R ⁴² are taken together to form an alkylene group having 2 to 6 carbon atoms (provided that one or more oxygen atoms or —NR ³⁹ — is present between main chain carbon atoms, and / or a hydroxyl group, carbon And may be substituted with one or more of an alkoxyl group having 1 to 4 carbon atoms, an alkanoyloxy group having 2 to 4 carbon atoms, or a benzoyloxy group.

Among these, in formula (8), a compound in which at least one of R ²³ , R ²⁴ , R ²⁵ , R ^26, and R ²⁷ is —SR ⁴⁰ is preferable because sensitivity and remaining film ratio are particularly excellent.

In the formula (8), R ²¹ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 4 to 7 carbon atoms, and particularly preferably a hexyl group. Preferably, 4 of R ^{23 to} R ²⁷ are hydrogen, more preferably R ²³ , R ²⁴ , R ²⁵ , R ²⁶ are hydrogen, and the rest is —SR ⁴⁰ . The —SR ⁴⁰ is preferably a cyclohexyl group, a phenyl group, or a phenylalkyl group having 7 to 10 carbon atoms, more preferably a phenyl group or a phenylalkyl group having 7 to 10 carbon atoms, and particularly preferably a phenyl group. It is.

(C) The compound which generates radicals by actinic rays is very preferably a compound represented by the following formula (3) from the viewpoint of providing a photosensitive resin composition having lower stress and higher sensitivity.

When the composition of this invention contains (c) component, as content of the compound which generate | occur | produces a radical by (c) actinic ray irradiation, it is 0.01-30 mass with respect to 100 mass parts of (a) component. Part is desirable, 0.01 to 15 parts by mass is more desirable, and 0.05 to 10 parts by mass is even more desirable.
When the content of the component (c) is 0.01 parts by mass or more, the exposed part is sufficiently crosslinked, and the photosensitive property is further improved. When the content of the component (c) is 30 parts by mass or less, the composition is more cured. There is a tendency for the heat resistance of the film to improve.

The resin composition of the present invention may contain other components such as a solvent shown below in addition to the components (a), (b), and (c).
[(D) Solvent]
The resin composition of this invention may contain a solvent as (d) component as needed.
The solvent is preferably a polar solvent that completely dissolves the polyimide precursor, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric acid. Examples include triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, and 1,3-dimethyl-2-imidazolidinone. These may be used alone or in combination of two or more.

[(E) Addition polymerizable compound]
The resin composition of the present invention may contain an addition polymerizable compound as the component (e) as necessary.
Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, Intererythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2 -Hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide and the like. These may be used alone or in combination of two or more.

When the addition polymerizable compound is contained, the content is preferably 1 to 100 parts by mass, more preferably 1 to 75 parts by mass with respect to 100 parts by mass of the (a) polyimide precursor. It is more desirable to set it to -50 mass parts.
If the content of the addition polymerizable compound is 1 part by mass or more, better photosensitive characteristics can be imparted, and if it is 100 parts by mass or less, the heat resistance of the cured film can be further improved.

[(F) Radical polymerization inhibitor or radical polymerization inhibitor]
The resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to ensure good storage stability.
Examples of radical polymerization inhibitors or radical polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like can be mentioned. These may be used alone or in combination of two or more.

  When the resin composition of the present invention contains a radical polymerization inhibitor or a radical polymerization inhibitor, the content is desirably 0.01 to 30 parts by mass with respect to 100 parts by mass of (a) polyimide precursor. , 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass. If the content is 0.01 parts by mass or more, the storage stability becomes better, and if it is 30 parts by mass or less, the heat resistance of the cured film can be further improved.

[(G) Organosilane compound]
The resin composition of the present invention may contain an organosilane compound in order to further improve the adhesion to a cured silicon substrate or the like.
Organic silane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropyltrimethoxy. Silane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) ) -3-Aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Can be mentioned.
The content of the organosilane compound is appropriately adjusted so as to obtain a desired effect.

（式中、Ｒ^４５〜Ｒ^５０は、各々独立に水素原子又は１価の有機基である。） [(H) Aluminum complex compound]
The resin composition of the present invention may further contain a metal complex compound (aluminum complex) represented by the following general formula (4) from the viewpoint of further reducing the thermal expansion coefficient (CTE) of the obtained cured film. Since the compound represented by Formula (4) has the effect | action which improves the orientation of a polyimide cured film, it is thought that a thermal expansion coefficient can be made small.

(In the formula, R ^{45 to} R ⁵⁰ are each independently a hydrogen atom or a monovalent organic group.)

Examples of the monovalent organic group represented by R ^{45 to} R ⁵⁰ include an alkyl group having 1 to 20 carbon atoms and an alkoxyl group having 1 to 20 carbon atoms. The three ligands may be the same or different.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group, and n-dodecyl group. Examples of the alkoxyl group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxyl group, an i-propoxy group, and a butoxy group.

Examples of the compound represented by the formula (4) include aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), alkyl acetoacetate aluminum diisopropylate, aluminum bisethylacetate. Acetate monoacetylacetonate, etc. are mentioned, Preferably aluminum tris (acetylacetonate) and aluminum bisethylacetoacetate monoacetylacetonate are mentioned.
These may be used alone or in combination of two or more.

  The content in the case where the resin composition of the present invention contains the aluminum complex represented by the formula (4) is 0.5 to 100 parts by weight with respect to 100 parts by weight of the polyimide precursor from the viewpoint of swelling suppression and film properties. 50 parts by weight is preferred, 0.5 to 20 parts by weight is more preferred, and 0.5 to 10 parts by weight is even more preferred.

The resin composition of the present invention may contain the components (a) and (b), and optionally the components (c) to (h), and may consist essentially of these components, or may consist only of these components. Good.
The above “substantially” means, for example, that the total amount of the component (a), the component (b), and the optional components (c) to (h) is 90% by weight or more, 95% by weight or more of the whole composition It means 97% by weight or more, 98% by weight or more, or 99% by weight or more.

[Pattern cured film and pattern cured film production method]
The pattern cured film of the present invention is a pattern cured film formed from the resin composition of the present invention, and can be formed when the resin composition is a photosensitive resin composition containing the component (c).

The method for producing a patterned cured film of the present invention includes a step of applying a resin composition on a substrate and drying to form a coating film, and irradiating the formed coating film with actinic rays and developing to obtain a patterned resin film. A process and a process of heat-treating the patterned resin film.
Hereinafter, each process of the manufacturing method of a pattern cured film is demonstrated first.

In the step of applying the upper resin composition on the substrate and drying to form a coating film, the method of applying the resin composition on the substrate may be, for example, a dipping method, a spray method, a screen printing method, a spin coating method. Is mentioned.
Examples of the base material include a silicon wafer, a metal substrate, and a ceramic substrate. Since the resin composition of the present invention can form a low-stress cured film, it is particularly suitable for application to a silicon wafer having a large diameter of 12 inches or more.

The solvent can be removed by heating after drying to form a non-adhesive coating film.
In the drying step, a device such as DATAPLATE (Digital Hotplate) manufactured by PMC can be used, the drying temperature is preferably 90 to 130 ° C., and the drying time is preferably 100 to 400 seconds.

By irradiating the formed coating film with actinic rays and then developing it to obtain a patterned resin film, a resin film having a desired pattern can be obtained.
Although the resin composition of the present invention is suitable for i-line exposure, ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays, and the like can be used as the active rays to be irradiated.
The developer is not particularly limited, but is a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous alkali solution such as an aqueous sodium carbonate solution and an aqueous tetramethylammonium hydroxide solution, N, N-dimethylformamide, dimethyl sulfoxide, Good solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc., and these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons A mixed solvent or the like is used. After development, rinsing with a poor solvent is performed as necessary.

In the process of heat-treating the pattern resin film, the heat treatment can be performed using an apparatus such as a vertical diffusion furnace (manufactured by Koyo Lindberg), preferably at a heating temperature of 80 to 400 ° C., and a heating time of 5 to 300. Preferably it is minutes.
As for the said heating temperature which advances the imidation of a polyimide precursor and converts into a polyimide, 100-400 degreeC is more preferable, and it is more preferable that it is 200-400 degreeC. If it is 80 ° C. or lower, imidization does not proceed sufficiently and the heat resistance may be lowered. If it is performed at a temperature higher than 400 ° C., the polyimide obtained by curing may be deteriorated.
By this step, imidation of the polyimide precursor in the resin composition can be advanced to obtain a patterned cured film containing a polyimide resin.

[Curing film and method for producing cured film]
The cured film of this invention is a cured film formed from the resin composition of this invention, and includes the cured film in which the pattern is not formed.
The method for producing a cured film according to the present invention includes a step of applying a resin composition on a substrate and drying to form a coating film, and a step of heat-treating the coating film. The process to do is the same as the manufacturing method of the said pattern cured film.

The cured film or pattern cured film of the present invention can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer, or the like of a semiconductor device.
FIG. 1 is a schematic cross-sectional view of a semiconductor device having a rewiring structure according to an embodiment of the present invention. The semiconductor device of this embodiment has a multilayer wiring structure. An Al wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, and an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the Al wiring layer 2. A (surface protective film) 4 is formed. A rewiring layer 6 is formed from the pad portion 5 of the wiring layer 2 and extends to an upper portion of the core 8 which is a connection portion with a conductive ball 7 formed of solder, gold or the like as an external connection terminal. Further, a cover coat layer 9 is formed on the surface protective layer 4. The rewiring layer 6 is connected to the conductive ball 7 through the barrier metal 10, and a collar 11 is provided to hold the conductive ball 7. When a package having such a structure is mounted, an underfill 12 may be interposed in order to further relieve stress.

As shown in FIG. 1, the cured film of the present invention or the patterned cured film of the present invention is a so-called package application such as a cover coat material for semiconductor devices, a core material for rewiring, a color material for balls such as solder, an underfill material, etc. Can be used for
In addition, the cured film or pattern cured film of the present invention is excellent in adhesion to a metal layer, a sealant, etc., and has excellent copper migration resistance and a high stress relaxation effect. A semiconductor element having a very excellent reliability.

  The electronic component of the present invention is particularly limited except that it has a cover coat using the cured film or pattern cured film of the present invention, a core for rewiring, a ball collar such as solder, an underfill used in flip chips, etc. Instead, it can take various structures.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited by these.

Synthesis Example 1 (Synthesis of pyromellitic acid-hydroxyethyl methacrylate diester)
In a 0.5 liter plastic bottle, pyromellitic dianhydride 43.624 g (200 mmol), 2-hydroxyethyl methacrylate 54.919 g (401 mmol) and hydroquinone 0.220 g dried for 24 hours with a dryer at 160 ° C. Was dissolved in 394 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25 ° C.) for 24 hours, esterified, and pyromellitic acid-hydroxyethyl methacrylate diester. A solution was obtained. Let the obtained solution be a PMDA (HEMA) solution.

Synthesis Example 2 (Synthesis of 3,3′-4,4′-biphenyltetracarboxylic acid diester)
30.893 g (105 mmol) of 3,3′-4,4′-biphenyltetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, dried in a dryer at 160 ° C. for 24 hours in a 0.5 liter plastic bottle 28.833 g (210 mmol) and 0.110 g of hydroquinone were dissolved in 239 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25 ° C.) for 24 hours. The pyromellitic acid-hydroxyethyl methacrylate diester solution was obtained. Let the obtained solution be s-BPDA (HEMA) solution.

Synthesis Example 3 (Synthesis of 4,4′-oxydiphthalic acid diester)
49.634 g (160 mmol) of 4,4′-oxydiphthalic acid, 44.976 g (328 mmol) of 2-hydroxyethyl methacrylate and hydroquinone 0 which were dried in a dryer of 160 ° C. for 24 hours in a 0.5 liter plastic bottle. 176 g was dissolved in 378 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25 ° C.) for 48 hours to perform esterification, and 4,4′- An oxydiphthalic acid-hydroxyethyl methacrylate diester solution was obtained. Let the obtained solution be an ODPA (HEMA) solution.

Synthesis Example 4 (Synthesis of Polymer I) s-BPDAHEMA // TFDB
282.125 g of the s-BPDA (HEMA) solution obtained in Synthesis Example 2 was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and then 25.9 g (217.8 mmol) of thionyl chloride under ice-cooling. ) Was dropped using a dropping funnel so that the reaction solution temperature was kept at 10 ° C. or lower. After completion of the dropwise addition of thionyl chloride, the mixture was stirred for 1 hour under ice cooling to obtain a solution of s-BPDA (HEMA) chloride. Next, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2′-bis (trifluoromethyl) benzidine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone -A solution of 90.211 g of methylpyrrolidone was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester.
The weight average molecular weight calculated | required by standard polystyrene conversion of the obtained polyamic acid ester was 85,000. This is polymer I.

The measurement conditions of the weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer I are as follows. The measurement was performed using a solution of 1 mL of a solvent [THF / DMF = 1/1 (volume ratio)] per 0.5 mg of the polymer. In the following synthesis examples, the weight average molecular weight was measured in the same manner.
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min
Detector: UV270nm

1 g of polymer I is dissolved in 1.5 g of N-methylpyrrolidone, applied onto a glass substrate by spin coating, heated on a hot plate at 100 ° C. for 180 seconds to evaporate the solvent, and a coating film having a thickness of 20 μm is formed. did. At this time, the i-line transmittance of the obtained coating film was 60%.
The i-line transmittance was measured using a spectrophotometer (U-3310 manufactured by HITACHI). The i-line transmittance was similarly evaluated in the following synthesis examples.

Synthesis Example 5 (Synthesis of Polymer II) PMDAHEMA / ODPAHEMA // TFDB
In a 0.5 liter flask equipped with a stirrer and a thermometer, 195.564 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 and 58.652 g of the ODPA (HEMA) solution obtained in Synthesis Example 3 were placed. Under ice cooling, 25.9 g (217.8 mmol) of thionyl chloride was added dropwise using a dropping funnel so that the temperature of the reaction solution was kept at 10 ° C. or lower. After the addition of thionyl chloride was completed, the reaction was carried out for 2 hours under ice cooling to obtain a solution of PMDA (HEMA) and ODPA (HEMA) acid chloride. Next, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2′-bis (trifluoromethyl) benzidine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone -A solution of 90.211 g of methylpyrrolidone was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester.
The weight average molecular weight calculated | required by standard polystyrene conversion of the obtained polyamic acid ester was 34,000. This is polymer II.

  1 g of Polymer II is dissolved in 1.5 g of N-methylpyrrolidone, applied onto a glass substrate by spin coating, heated on a hot plate at 100 ° C. for 180 seconds to evaporate the solvent and form a 20 μm thick coating film. did. At this time, the i-line transmittance of the obtained coating film was 30%.

Synthesis Example 6 (Synthesis of Polymer III) PMDAHAMA / ODPAHEMA // TFDB / DMAP
In a 0.5 liter flask equipped with a stirrer and a thermometer, 150.152 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 and 118.335 g of the ODPA (HEMA) solution obtained in Synthesis Example 3 were placed. Under ice cooling, 25.9 g (217.8 mmol) of thionyl chloride was added dropwise using a dropping funnel so that the temperature of the reaction solution was kept at 10 ° C. or lower. After the addition of thionyl chloride was completed, the reaction was carried out for 2 hours under ice cooling to obtain a solution of PMDA (HEMA) and ODPA (HEMA) acid chloride. Next, using a dropping funnel, 6.305 g (29.7 mmol) of 2,2′-dimethylbenzidine, 22.187 g (69.3 mmol) of 2,2′-bis (trifluoromethyl) benzidine, and 34.457 g of pyridine ( 435.6 mmol) and N-methylpyrrolidone 113.968 g solution of hydroquinone 0.076 g (0.693 mmol) was added dropwise with ice cooling so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester.
The weight average molecular weight determined by standard polystyrene conversion was 34,000. This is polymer III.

  1 g of Polymer III is dissolved in 1.5 g of N-methylpyrrolidone, applied onto a glass substrate by spin coating, heated on a hot plate at 100 ° C. for 180 seconds to evaporate the solvent, and a coating film having a thickness of 20 μm is formed. did. At this time, the i-line transmittance of the obtained coating film was 15%.

Synthesis Example 7 (Synthesis of Polymer IV) ODPAHEMA // DMAP
In a 0.5 liter flask equipped with a stirrer and a thermometer, 181.944 g of the ODPA (HEMA) solution obtained in Synthesis Example 3 was placed, and then 25.9 g (217.8 mmol) of thionyl chloride was added under ice cooling. The reaction solution was dropped using a dropping funnel so that the temperature of the reaction solution was kept at 10 ° C. or lower. After completion of the dropwise addition of thionyl chloride, the mixture was stirred for 1 hour under ice cooling to obtain a solution of ODPA (HEMA) chloride. Then, using a dropping funnel, 21.017 g (99.0 mmol) of 2,2′-dimethylbenzidine, 34.457 g (435.6 mmol) of pyridine, and 0.076 g (0.693 mmol) of hydroquinone 59. The 817 g solution was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. The weight average molecular weight calculated | required by standard polystyrene conversion of the obtained polyamic acid ester was 35,000. This is polymer IV.

  1 g of polymer IV is dissolved in 1.5 g of N-methylpyrrolidone, applied onto a glass substrate by spin coating, heated on a hot plate at 100 ° C. for 180 seconds to evaporate the solvent, and a coating film having a thickness of 20 μm is formed. did. At this time, the i-line transmittance of the obtained coating film was 40%.

Example 1-17 and Comparative Example 1-8
Resin composition solutions were prepared with the components and blending amounts shown in Table 1.
In Table 1, the numbers in parentheses are the blended parts by mass of component (b) and component (c) with respect to 100 parts by mass of polymer (a). Further, N-methylpyrrolidone was used as a solvent, and the amount used was 1.5 times that of 100 parts by weight of component (a).
In Example 1-17 and Comparative Example 1-8, when the photosensitive resin composition includes the component (c), tetraethylene glycol dimethacrylate is further added to the component (a) for the composition. 20 parts by weight was blended.

The various components used for the preparation of the composition are as follows.
[Component (b)]
b1: Titanium tetraacetylacetonate (Matsumoto Fine Chemical, TC-401)
b2: Titanium diisopropoxybis (triethanolaminate) (Matsumoto Fine Chemical, TC-400)
b3: Titanium diisopropoxybis (ethyl acetoacetate) (Matsumoto Fine Chemical, TC-750)
b4: Zirconium tetraacetylacetonate (Matsumoto Fine Chemical, ZC-150)
b5: Aluminum trisacetylacetonate (Kawaken Fine Chemicals, Aluminum Chelate A (w))
b6: Aluminum bisethylacetoacetate monoacetylacetonate (Kawaken Fine Chemicals: Aluminum Chelate D)

[Component (c)]
c1: 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime c2: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (Ciba Specialty Chemicals, IRGACURE OXE-01, the following structural compounds)

Each of the resin compositions prepared in Example 1-17 and Comparative Example 1-8 was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 3 minutes, and the solvent was volatilized and cured. Each coating film having a post film thickness of about 10 μm was obtained.
The obtained coating film was heat-cured at 375 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace manufactured by Koyo Lindberg to obtain a polyimide film. The residual stress of the obtained cured polyimide film was measured at room temperature using a thin film stress measuring device (FLX-2320 manufactured by KLA Tencor). The results are shown in Table 1.

In the cured film obtained from the composition of Example 1-17, it can be confirmed that the stress is further reduced by adding the titanium complex compound or the zirconium complex compound to the rigid polyimide having low stress. It was also confirmed that the stress was reduced to 35 MPa by adding a titanium complex compound or a zirconium complex compound to polymer IV having a stress value of 40 or more.
On the other hand, for example, as shown in Comparative Example 1-8, the effect of stress reduction cannot be confirmed with no metal complex compound or with an aluminum complex compound. For example, in Comparative Examples 7 and 8, the stress exceeds 40 MPa.

  The resin composition of the present invention can be used for so-called package applications such as cover coat materials, rewiring core materials, ball color materials such as solder, and underfill materials, which form electronic components such as semiconductor devices. .

DESCRIPTION OF SYMBOLS 1 Interlayer insulating layer 2 Al wiring layer 3 Insulating layer 4 Surface protection layer 5 Pad part of wiring layer 6 Rewiring layer 7 Conductive ball 8 Core 9 Cover coat layer 10 Barrier metal 11 Color 12 Underfill

Claims (8)

(A) a polyimide precursor having a structural unit represented by the following general formula (1) , ( b) a metal complex compound represented by the following general formula (2) , and (c) generating radicals upon irradiation with actinic rays. A resin composition containing a compound .

(In the formula, R ¹ is a tetravalent organic group.
R ² is a divalent organic group represented by the following formula (6).

(Wherein R ¹⁸ and R ¹⁹ each independently represents a fluorine atom or a trifluoromethyl group)
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond. )

(Wherein M ¹ is a metal atom selected from titanium and zirconium.
m is an integer from 0 to 4, n is an integer from 0 to 4, and the sum of m and n is 4.
R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms.
R ⁶ each independently represents a monovalent organic group, and the monovalent organic group has one or more groups capable of coordinating with M ¹ selected from a hydroxyl group, a carbonyl group, and an amino group. ) The resin composition according to claim 1, wherein the metal complex compound represented by the formula (2) is represented by the following formula (3).

(Wherein M ¹ is a metal atom selected from titanium and zirconium.
a is an integer from 0 to 4, b is an integer from 0 to 4, c is an integer from 0 to 4, and the sum of a, b, and c is 4.
R ⁵ is each independently an alkyl group having 1 to 18 carbon atoms.
R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, an organic group having 1 to 6 carbon atoms, an alkyl alcohol group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms.
R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkyl alcohol group having 1 to 6 carbon atoms.
R ^{11 to} R ¹⁴ may further include a group capable of coordinating with M ¹ selected from a hydroxyl group, a carbonyl group, and an amino group. )   The resin composition according to claim 1 or 2, wherein the metal complex compound is contained in an amount of 0.005 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor. The resin composition according to any one of claims 1 to 3 , wherein the compound (c) that generates radicals upon irradiation with actinic rays is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the (a) polyimide precursor. object. The cured film formed from the resin composition in any one of Claims 1-4 . A method for producing a cured film, comprising a step of applying the resin composition according to any one of claims 1 to 4 on a substrate and drying to form a coating film, and a step of heat-treating the obtained coating film. . The pattern cured film formed from the resin composition in any one of Claims 1-4 . Forming a coating film by applying and drying the resin composition defined above onto a substrate to any one of claims 1 to 4,
Irradiating the coating film formed in the above step with actinic rays and developing to obtain a patterned resin film;
A method for producing a patterned cured film, comprising a step of heat-treating the pattern resin film.

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