JP6136486B2 - Resin composition and pattern forming method using the same - Google Patents

Description

    The present invention relates to a resin composition and a method for producing a cured pattern film.

  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). Also, in pattern formation on semiconductor integrated circuits, from the viewpoint of process simplification, there is a need for a method for forming a necessary pattern by exposing and developing a protective film material using a material imparted with photosensitivity. It has been.

As a method of 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 1).
Among these methods, the method of introducing a methacryloyl group into a polyimide precursor via an ester bond can freely select a monomer to be used when the polyimide precursor is synthesized. However, a method in which a tertiary amine having a methacryloyl group is added to a polyamic acid to form a carboxylic acid group in the polyamic acid and a quaternary ammonium salt, and the methacryloyl group is introduced via an ionic bond has a weak binding force. Therefore, when stored at room temperature, there has been a problem that the depolymerization of the polyamic acid easily occurs, the molecular weight is lowered, and the viscosity is lowered. Further, even if methacryloyl groups are cross-linked by photopolymerization by exposure, there is a problem that the photosensitive property is deteriorated because the effect of lowering the dissolution rate of the polyamic acid is weak (for example, see Patent Document 2).

  The method of introducing a methacryloyl group into a polyimide precursor via an ester bond is characterized by excellent stability over time because the methacryloyl group is introduced via a chemical bond. However, since the methacryloyl group crosslinking agent at the time of pattern formation is finally unnecessary, it is necessary to evaporate the polymer at the high temperature (375 ° C.). At 375 [deg.] C., there is a problem that a semiconductor element that is vulnerable to heat is damaged and the yield is deteriorated. Accordingly, development of an ester-type photosensitive polyimide resin composition that can be cured at a low temperature is desired.

Japanese Laid-Open Patent Publication No. 1995-242744 JP 2011-174020 A

  When a resin composition containing an ester-type photosensitive polyimide resin is finally cured through coating, exposure, and development, imidation is completed at, for example, about 300 ° C., but the temperature at which the additive evaporates is, for example, around 330 ° C. Therefore, it was necessary to raise the temperature to higher than 330 ° C.

An object of the present invention is to provide a resin composition having good photosensitive characteristics, capable of forming a cured film at a low final curing temperature, and having a high weight reduction temperature of the cured film.
An object of this invention is to provide the pattern cured film formation method using the said resin composition.

（一般式（１）中、Ａは、下記一般式（２ａ）〜（２ｅ）で表される４価の有機基のいずれかである。
Ｂは、下記一般式（３）で表される２価の有機基である。
Ｒ^１及びＲ^２は、各々独立に水素原子、又は１価の有機基である。
但し、式（１）中のＲ^１及びＲ^２の８０％以上は、炭素炭素不飽和二重結合を有する１価の有機基である。）

（一般式（２ｄ）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。
一般式（２ｅ）中、Ｚはエーテル結合（−Ｏ−）又はスルフィド結合（−Ｓ−）である。）

（一般式（３）中、Ｒ^３〜Ｒ^１０は、各々独立に水素原子又は１価の基である。
但し、Ｒ^３〜Ｒ^１０はハロゲン原子及びハロゲン原子を有する１価の有機基ではない。）

（一般式（４ａ）中、ｎは３以下の整数である。
一般式（４ｂ）中、Ｒ^１０１及びＲ^１０２は、各々独立に水素原子又は１価の基である。ｍは９以下の整数である。）
２．前記（ｂ）成分が、下記一般式（５）で表される化合物である１に記載の樹脂組成物。

（一般式（５）中、Ｒ^１１〜Ｒ^１７は、各々独立に水素原子又は１価の基を示す。）
３．前記（ｂ）成分が、下記式（６）で表される化合物である２に記載の樹脂組成物。

４．１〜３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、
前記工程で形成した塗膜に活性光線を照射してパターン状に露光する工程と、
前記露光部以外の未露光部を現像によって除去してパターン樹脂膜を得る工程と、
前記工程で得られたパターン樹脂膜を加熱処理してポリイミドパターンとする工程と、を含むパターン硬化膜の製造方法。
５．４に記載のパターン硬化膜の製造方法で得られるパターン硬化膜を有する半導体装置。 According to the present invention, the following resin composition and the like are provided.
1. A resin composition containing the following components (a) to (d).
(A) Polyimide precursor having a structural unit represented by the following general formula (1) (b) Compound that generates radicals upon irradiation with actinic rays (c) Compound represented by the following general formula (4a) or (4b) (D) Solvent

(In General Formula (1), A is any one of tetravalent organic groups represented by the following General Formulas (2a) to (2e).
B is a divalent organic group represented by the following general formula (3).
R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group.
However, 80% or more of R ¹ and R ^{2 in} the formula (1) is a monovalent organic group having a carbon-carbon unsaturated double bond. )

(In General Formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.
In general formula (2e), Z is an ether bond (—O—) or a sulfide bond (—S—). )

(In General Formula (3), R ^{3 to} R ¹⁰ are each independently a hydrogen atom or a monovalent group.
However, R < ³ > -R < ¹⁰ > is not a monovalent organic group having a halogen atom and a halogen atom. )

(In general formula (4a), n is an integer of 3 or less.
In general formula (4b), R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom or a monovalent group. m is an integer of 9 or less. )
2. 2. The resin composition according to 1, wherein the component (b) is a compound represented by the following general formula (5).

(In the general formula (5), R ^{11 to} R ¹⁷ each independently represent a hydrogen atom or a monovalent group.)
3. 3. The resin composition according to 2, wherein the component (b) is a compound represented by the following formula (6).

4.1 The process of apply | coating the resin composition in any one of 1-3 to a board | substrate, and drying and forming a coating film,
Irradiating the coating film formed in the step with an actinic ray to expose it in a pattern; and
Removing a non-exposed portion other than the exposed portion by development to obtain a patterned resin film;
A process for producing a cured pattern film, comprising: heating the patterned resin film obtained in the process to a polyimide pattern.
The semiconductor device which has a pattern cured film obtained by the manufacturing method of the pattern cured film as described in 5.4.

According to the present invention, it is possible to provide a resin composition having good photosensitive characteristics, capable of forming a cured film at a low final curing temperature, and having a high weight reduction temperature of the cured film.
According to this invention, the pattern cured film formation method using the said resin composition can be provided.

[Resin composition]
The resin composition of the present invention contains the following components (a) to (d).
(A) a polyimide precursor having a structural unit represented by the following general formula (1),
(B) Compound that generates radicals upon irradiation with actinic rays (c) Compound represented by formula (4a) or (4b) described later (d) Solvent

In the resin composition of the present invention, the component (c) functions as a crosslinking agent, and the component (c) is a compound having a structure containing propylene, so that the decomposition temperature is low, and even when final curing is performed at a low temperature, A resin composition having a high decrease temperature can be obtained.
Hereinafter, each component of the resin composition will be described.

（一般式（１）中、Ａは、下記一般式（２ａ）〜（２ｅ）で表される４価の有機基のいずれかである。
Ｂは、下記一般式（３）で表される２価の有機基である。
Ｒ^１及びＲ^２は、各々独立に水素原子、又は１価の有機基である。
但し、式（１）中のＲ^１及びＲ^２の８０％以上は、炭素炭素不飽和二重結合を有する１価の有機基である。）

（一般式（２ｄ）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。
一般式（２ｅ）中、Ｚはエーテル結合（−Ｏ−）又はスルフィド結合（−Ｓ−）である。）

（一般式（３）中、Ｒ^３〜Ｒ^１０は、各々独立に水素原子又は１価の基である。
但し、Ｒ^３〜Ｒ^１０はハロゲン原子及びハロゲン原子を有する１価の有機基ではない。） [(A) component: polyimide precursor]
The polyimide precursor which is the component (a) of the resin composition of the present invention has a structural unit represented by the following general formula (1).

(In General Formula (1), A is any one of tetravalent organic groups represented by the following General Formulas (2a) to (2e).
B is a divalent organic group represented by the following general formula (3).
R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group.
However, 80% or more of R ¹ and R ^{2 in} the formula (1) is a monovalent organic group having a carbon-carbon unsaturated double bond. )

(In General Formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.
In general formula (2e), Z is an ether bond (—O—) or a sulfide bond (—S—). )

(In General Formula (3), R ^{3 to} R ¹⁰ are each independently a hydrogen atom or a monovalent group.
However, R < ³ > -R < ¹⁰ > is not a monovalent organic group having a halogen atom and a halogen atom. )

  A in the general formula (1) is a structure derived from a tetracarboxylic dianhydride used as a raw material for the polyimide precursor, and in order to reduce the stress of the cured film obtained from the resin composition, the general formula (2a ) To (2e).

（式中、Ｒ^１２は炭素原子又は珪素原子である。
Ｒ^１３は水素原子、又は、フッ素原子、塩素原子、臭素原子、ヨウ素原子から選択されるハロゲン原子である。
ｎ＝３である。） The “divalent group that is not conjugated with the benzene ring to be bonded” of X and Y in the general formula (2d) is —R ¹¹ — selected from —O—, —S—, or 2 represented by the following formula: Is a valent group.

(Wherein R ¹² represents a carbon atom or a silicon atom.
R ¹³ is a hydrogen atom or a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
n = 3. )

Examples of tetracarboxylic dianhydrides that give tetravalent organic groups represented by the formulas (2a) to (2e) having the structure of A include pyromellitic dianhydride and 2,3,6,7-naphthalenetetra. Carboxylic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, thioether diphthalic anhydride, represented by the following formulas (8) to (14) A tetracarboxylic dianhydride is mentioned.

  During polymerization of the polyimide precursor, these may be used alone or in combination of two or more tetracarboxylic dianhydrides. Among these, pyromellitic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, thioether diphthalic anhydride, Formula (8) and Formula (10 It is preferable to use tetracarboxylic dianhydride represented by the following formula: pyromellitic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, thioether di It is more preferable to use phthalic anhydride, tetracarboxylic dianhydride represented by the formula (8), pyromellitic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, 4,4 ′ -It is particularly preferable to use oxydiphthalic dianhydride or thioether diphthalic anhydride.

B in the general formula (1) is a structure derived from a diamine used as a raw material for the polyimide precursor, and is a divalent organic group represented by the general formula (3) from the viewpoint of low stress and i-line transmittance. is there.
In Formula (3), R ^{3 to} R ¹⁰ are not a monovalent organic group having a halogen atom and a halogen atom. When R ^{3 to} R ¹⁰ are a halogen atom or a monovalent organic group containing a halogen atom, when the cured film is subjected to plasma treatment, the bond between carbon-halogen atoms may be broken and the cured film may be deteriorated. There is.

Examples of the monovalent group of R ^{3 to} R ¹⁰ include an alkyl group having 1 to 20 carbon atoms (such as a methyl group) and an alkoxy group having an alkyl group having 1 to 20 carbon atoms (such as a methoxy group).

Examples of the diamine that gives the structure of B include 2,2′-diaminobenzidine, 3,3′-diaminobenzidine, 2,2 ′, 3,3′-tetramethylbenzidine, 2,2′-dimethoxybenzidine, 3 3,3′-dimethoxybenzidine and the like can be used. Among these, 2,2′-diaminobenzidine and 3,3′-diaminobenzidine are preferably used, and 2,2′-diaminobenzidine is more preferably used.
In the polymerization of the polyimide precursor, these diamines may be used alone or in combination of two or more diamines.

R ¹ and R ² in the polyimide precursor represented by the general formula (1) are each independently a hydrogen atom or a monovalent organic group. However, 80% or more of R ¹ and R ² are monovalent organic groups having a carbon-carbon unsaturated double bond.
The polyimide precursor has a monovalent organic group having a carbon-carbon unsaturated double bond, so that it is combined with a compound that generates radicals upon irradiation with actinic rays (for example, i-line exposure), and intermolecular chains by radical polymerization. It becomes easy to make a negative resin composition.

Examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group, and an alkyl group. And methacryloxyalkyl groups having 1 to 10 carbon atoms.
Examples of the group having a carbon-carbon unsaturated double bond of R ¹ and R ² include an acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group, a methacryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group, and the like. Can be mentioned.

Specifically as a C1-C20 alkyl group, a methyl group, an ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group , N-dodecyl group and the like.
Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
Examples of the acryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include acryloxyethyl group, acryloxypropyl group, acryloxybutyl group and the like.
Examples of the methacryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxybutyl group.

As a method of imparting photosensitivity to a polyimide precursor, a method of adding a tertiary amine compound having a carbon-carbon unsaturated double bond to a corresponding polyamic acid is known. However, the carboxyl group in the polyamic acid and the tertiary amine form an ionic bond, and the state of the ionic bond may change due to the influence of pH and moisture of the varnish, which may reduce the storage stability.
Therefore, R ¹ and R ² are preferably not a hydrogen atom but a group introduced by an ester bond. Among these, from the viewpoint of good photosensitivity, R ¹ and R ² are each preferably an acryloxyethyl group, an acryloxybutyl group, a methacryloxyethyl group, or a methacryloxyethyl group introduced by an ester bond.

The polyimide precursor as component (a) may have a structural unit other than the structural unit represented by the general formula (1).
Examples of the tetracarboxylic dianhydride that gives a polyimide precursor having a structural unit other than the structural unit represented by the general formula (1) include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4 ′-[isopropylidenebis [(p-phenylene) oxy]] diphthalic acid 1,2: 1 ′, 2′-dianhydride, etc. Is mentioned.
Examples of the diamine that gives a polyimide precursor having a structural unit other than the structural unit represented by the general formula (1) include 4,4′-oxydianiline, 4,4′-diaminodiphenylmethane, 1,4-cyclohexanediamine, , 3′-bis (3-aminophenoxy) benzene and the like.

  From the viewpoint of reducing the stress, the total amount of the above-described tetracarboxylic dianhydride and diamine that gives a polyimide precursor having a structural unit other than the structural unit represented by the general formula (1) is represented by the general formula (1). The total amount of tetracarboxylic dianhydride and diamine used as a raw material to give the structural unit represented is preferably 20 mol% or less, more preferably 10 mol% or less, and the structure of the general formula (1) It is particularly preferred to use only tetracarboxylic dianhydrides and diamines which give

As for the molecular weight of the polyimide precursor as component (a), the weight average molecular weight in terms of polystyrene is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, and still more preferably 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, and if it is greater than 100,000, the solubility in a solvent may be reduced, or the viscosity of the solution may be increased and handleability may be increased. May decrease.
In addition, a weight average molecular weight can be measured by the gel permeation chromatography method, and is calculated | required by converting using a standard polystyrene calibration curve.

  The content of the polyimide precursor in the resin composition is preferably 20 to 60% by mass in the resin composition, more preferably 25 to 55% by mass, and further preferably 30 to 55% by mass. .

The polyimide precursor as component (a) can be synthesized by addition polymerization of tetracarboxylic dianhydride and diamine.
The molar ratio of tetracarboxylic dianhydride and diamine [tetracarboxylic dianhydride / diamine] used when synthesizing the polyimide precursor is preferably preferably 1.0, but the molecular weight and terminal residues are For the purpose of control, it may be carried out at a molar ratio in the range of 0.7 to 1.3. When the molar ratio is 0.7 to 1.3, the molecular weight of the obtained polyimide precursor becomes appropriate, and the stress after curing tends to be sufficiently lower.

（式（１５）中、Ｅは４価の有機基であって、式（１）のＡを含む４価の有機基である。
Ｒ^１及びＲ^２は、それぞれ式（１）中のＲ^１及びＲ^２と同じである。）

（式（１６）中、Ｅは４価の有機基であって、式（１）のＡ含む４価の有機基である。
Ｒ^１及びＲ^２は、それぞれ式（１）中のＲ^１及びＲ^２と同じである。） The polyimide precursor is derived from a tetracarboxylic dianhydride as a raw material into a diester derivative represented by the following general formula (15), and then converted to an acid chloride represented by the following general formula (16), And an acid chloride method in which condensation is performed in the presence of a basic compound.

(In Formula (15), E is a tetravalent organic group, Comprising: It is a tetravalent organic group containing A of Formula (1).
R ¹ and ^{R 2} are the same as ^{R 1} and ^{R 2,} respectively formula (1). )

(In Formula (16), E is a tetravalent organic group, Comprising: A of Formula (1) A containing tetravalent organic group.
R ¹ and ^{R 2} are the same as ^{R 1} and ^{R 2,} respectively formula (1). )

The diester derivative represented by the formula (15) can be synthesized by reacting at least 2 molar equivalents of alcohol in the presence of a basic catalyst with respect to 1 mol of tetracarboxylic dianhydride as a raw material. it can.
However, when the diester derivative represented by the formula (15) is converted into the acid chloride represented by the formula (16), if the unreacted alcohol remains, the chlorinating agent is converted to the unreacted alcohol. There is concern that the conversion to acid chloride will not proceed sufficiently. Therefore, the equivalent of alcohol is preferably 2.0 to 2.5 molar equivalent, more preferably 2.0 to 2.3 molar equivalent, relative to 1 mole of tetracarboxylic dianhydride. 2.0 to 2.2 molar equivalents are even more preferable.

Since 80% or more of R ¹ and R ² of the polyimide precursor represented by the formula (1) is a monovalent organic group having a carbon-carbon unsaturated double bond, 80% or more of the alcohols used are acrylic. An alcohol having a monovalent organic group having a carbon-carbon unsaturated double bond such as an alcohol having a roxyalkyl group or an alcohol having a methacryloxyalkyl group is used.

Examples of the alcohol include alcohols having an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, acryloxyalkyl groups having 1 to 10 carbon atoms in the alkyl group, or methacryloxy having 1 to 10 carbon atoms. Alcohol having an alkyl group can be used.
For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, n-hexanol, cyclohexanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2 -Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like. These may be used singly or in combination of two or more.

  Examples of the basic catalyst used in the reaction of tetracarboxylic dianhydride with alcohols include 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] nona. -5-ene or the like can be used.

  When two or more types of tetracarboxylic dianhydrides are used as raw materials, those obtained by separately introducing each tetracarboxylic dianhydride into an ester derivative may be used. Moreover, after mixing 2 or more types of tetracarboxylic dianhydride beforehand, you may guide | lead to an ester derivative simultaneously.

In order to convert the diester derivative represented by the formula (15) into the acid chloride represented by the formula (16), it is usually used by reacting 1 mol of the diester derivative with 2 mol equivalent of a chlorinating agent. However, in order to control the molecular weight of the synthesized polyimide precursor, the equivalent may be appropriately adjusted.
As the chlorinating agent, thionyl chloride or dichlorooxalic acid can be used, and the equivalent is preferably 1.5 to 2.5 molar equivalent, more preferably 1.6 to 2.4 molar equivalent, and 1.7. -2.3 molar equivalents are more preferred. If it is less than 1.5 molar equivalents, the molecular weight of the polyimide precursor may be too low and the stress after curing may not be sufficiently reduced. If it exceeds 2.5 molar equivalents, the unreacted chlorinating agent And the raw material diamine may react.

The polyimide precursor used by this invention is obtained by adding the diamine which is a raw material to acid chloride represented by Formula (16) in presence of a basic compound. The basic compound is used for the purpose of capturing hydrogen chloride generated when the acid chloride and diamine react.
As the basic compound, for example, pyridine, 4-dimethylaminopyridine, triethylamine and the like can be used. The amount used is preferably 1.5 to 2.5 molar equivalents, more preferably 1.7 to 2.4 molar equivalents relative to the amount of chlorinating agent, and 1.8 to 2.3. More preferably, the molar equivalent. If it is less than 1.5 molar equivalents, the molecular weight of the polyimide precursor may be low, and the stress after curing may not be sufficiently reduced. If it is more than 2.5 molar equivalents, the polyimide precursor may be colored.

The polyimide precursor described above can also be synthesized by an isoimide method or a DCC method other than the acid chloride method as described above.
In the isoimide method, polycarboxylic acid is synthesized by polycondensing tetracarboxylic dianhydride and diamine as raw materials, and trifluoromethylacetic anhydride is added to convert it to isoimide, and then an alcohol compound is added to form an ester bond. A polyimide precursor having s is synthesized.
In the DCC method, a polyimide precursor can be obtained by reacting a diester derivative represented by the formula (15) with 2 molar equivalents of DCC (dicyclohexylcarbodiimide) and then adding a diamine.

  The alcohol compound used in the isoimide method is preferably an alcohol having an acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group or a methacryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc. Is mentioned. These may be used singly or in combination of two or more.

（式（１７）中、Ｇは４価の有機基であって、式（１）のＡを含む４価の有機基である。
Ｒ^１８は、式（１）中のＲ^１又はＲ^２と同じである。） In the isoimide method, for the purpose of controlling the molecular weight, a part of tetracarboxylic dianhydride as a raw material is previously reacted with the alcohol compound to be converted into an ester compound represented by the formula (17), and then diamine. You may perform polycondensation with.

(In Formula (17), G is a tetravalent organic group, Comprising: It is a tetravalent organic group containing A of Formula (1).
R ¹⁸ is the same as R ¹ or R ^{2 in} formula (1). )

The addition polymerization, the condensation reaction, and the synthesis reaction of the diester derivative or acid chloride are preferably performed in an organic solvent.
The organic solvent to be used is preferably a polar solvent that completely dissolves the polyimide precursor to be synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetra Examples include methylurea, hexamethylphosphoric triamide, and γ-butyrolactone.

（一般式（５）中、Ｒ^１１〜Ｒ^１７は、各々独立に水素原子又は１価の基を示す。） [Component (b): Compound that generates radicals upon irradiation with actinic rays]
The compound (b) that generates radicals upon irradiation with actinic rays is used as a photoinitiator.
The compound that generates radicals upon irradiation with actinic rays (hereinafter sometimes referred to as a photoinitiator) is not particularly limited, but is preferably a compound represented by the following general formula (5).

(In the general formula (5), R ^{11 to} R ¹⁷ each independently represent a hydrogen atom or a monovalent group.)

Specifically, R ¹¹ represents, for example, a phenyl group (an alkyl group having 1 to 10 carbon atoms, a phenyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl mercapto group, or an alkyl group having 1 to 10 carbon atoms. An alkyl group having 1 to 20 carbon atoms (provided that the alkyl group has 2 to 20 carbon atoms, one or more oxygen atoms are inserted between the main chain carbon atoms). And / or may be substituted with one or more hydroxyl groups), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (however, having 1 to 6 carbon atoms) An alkyl group, a phenyl group, an alkoxyl group, a thioether group, or a dialkylamino group (which may be substituted), an alkoxycarbonyl group having 2 to 12 carbon atoms (however, the carbon of the alkoxyl group) When the number is 2 to 11, it may have one or more oxygen atoms between main chain carbon atoms and / or may be substituted with one or more hydroxyl groups), cyano group, nitro group, carbon number 1 A haloalkyl group having ˜4, an alkylsulfinyl group and alkylsulfonyl group having 1 to 6 carbon atoms, an arylsulfinyl group and an arylsulfonyl group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms, and having 1 to 12 carbon atoms) Which may be substituted with an alkyl group), an alkoxysulfonyl group having 1 to 6 carbon atoms, an aryloxysulfonyl group having 6 to 10 carbon atoms, or a diphenylphosphinoyl group.

R ¹² is, for example, an alkanoyl group having 2 to 12 carbon atoms (which may be substituted with one or more halogen atoms or a cyano group), α, β 4-6 carbon atoms having no unsaturated carbonyl structure. An alkenoyl group, a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, an alkoxyl group, a thioether group or a dialkylamino group), an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxy group One of carbonyl groups (however, it may be substituted with one or more alkyl groups having 1 to 6 carbon atoms or a halogen atom).

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently, for example, a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (however, a hydroxyl group, Mercapto group, alkoxy group having 1 to 12 carbon atoms and alkyl mercapto group (wherein at least one hydrogen atom in the alkyl chain is a hydroxyl group, mercapto group, cyano group, alkoxy group having 1 to 4 carbon atoms, carbon number 3-6 alkenyloxy group, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4-7 carbon atoms, alkylcarbonyloxy group having 2-5 carbon atoms, phenylcarbonyloxy group, carboxyl group, carbon number 2 to 5 alkoxylcarbonyl groups, 2 to 2 carbon atoms having one or more oxygen atoms between main chain carbon atoms Which may be substituted with any one of an alkoxyl group, an alkylcarbonyloxy group having 2 to 8 carbon atoms, and a phenyl group), a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, and a 2 to 12 carbon atoms An alkoxylcarbonyl group (provided that 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 is substituted with one or more hydroxyl groups) Phenoxycarbonyl group, phenoxy group and phenylthio group (wherein at least one hydrogen atom on the phenyl ring is a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, or an alkyl mercapto group having 1 to 6 carbon atoms). Group, alkyl group having 1 to 12 carbon atoms, carboxyl group, hydroxymethyloxycarbonyl group, hydroxyethyloxyca Optionally substituted with any of a sulfonyl group, a hydroxyethyloxy group, and a hydroxypropyloxy group), an alkylsulfinyl group and an alkylsulfonyl group having 1 to 6 carbon atoms, an arylsulfinyl group, and an arylsulfonyl group (however, an aryl group) Is an aryl group having 6 to 12 carbon atoms, which may be substituted with an alkyl group having 1 to 12 carbon atoms), an alkoxysulfonyl group having 1 to 6 carbon atoms, an aryloxysulfonyl group having 6 to 10 carbon atoms, One of dialkylamino groups having two alkyl groups having 1 to 10 carbon atoms, particularly from the viewpoint of sensitivity, an alkyl mercapto group having 1 to 12 carbon atoms (however, at least one hydrogen atom in the alkyl chain) Are a hydroxyl group, a mercapto group, a cyano group, an alkoxyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 6 carbon atoms. Ruoxy group, 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, alkoxyl having 2 to 5 carbon atoms A carbonyl group, an alkoxyl group having 2 to 6 carbon atoms having one or more oxygen atoms between main chain carbon atoms, an alkylcarbonyloxy group having 2 to 8 carbon atoms, or a phenyl group). A phenylthio group (wherein at least one hydrogen atom on the phenyl ring is a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, an alkyl mercapto group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, Carboxyl group, hydroxymethyloxycarbonyl group, hydroxyethyloxycarbonyl group, hydroxyethyloxy May be substituted by any of the hydroxypropyl group) it is preferable.

R ¹¹ is preferably an alkyl group having 1 to 10 carbon atoms.
Further, any one of R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is an alkyl mercapto group having 1 to 12 carbon atoms (provided that at least one hydrogen atom in the alkyl chain is a hydroxyl group, a mercapto group) Group, cyano group, C 1-4 alkoxyl group, C 3-6 alkenyloxy group, 2-cyanoethoxy group, C 4-7 2- (alkoxycarbonyl) ethoxy group, C 2-5 Alkylcarbonyloxy group, phenylcarbonyloxy group, carboxyl group, C2-C5 alkoxylcarbonyl group, C2-C6 alkoxyl group having one or more oxygen atoms between main chain carbon atoms, C2 -8 alkylcarbonyloxy group, which may be substituted with any of phenyl group) or phenylthio group (however, at least on the phenyl ring) In which one or more hydrogen atoms are a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, an alkyl mercapto group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a carboxyl group, a hydroxymethyloxycarbonyl group, a hydroxy group It is preferably substituted with an ethyloxycarbonyl group, a hydroxyethyloxy group, or a hydroxypropyloxy group.

Further, R ¹¹ is more preferably a hexyl group.
More preferably, R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ are hydrogen atoms, and R ¹⁵ is a phenylthio group. Among these, a compound represented by the formula (6) (1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime)) is more preferable.

  As content of (b) component, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of polyimide precursors which are (a) component, and it is 0.1-15 mass parts. More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-5 mass parts, It is very preferable that it is 1-5 mass parts. When the blending amount is 0.1 parts by mass or more, crosslinking of the exposed part proceeds more sufficiently and the photosensitive properties (sensitivity, resolution) tend to be better, and when it is 20 parts by mass or less, the cured film The heat resistance of can be made better.

  The resin composition of the present invention is excellent in photosensitive characteristics by combining the component (a) and the component (b), and the stress of the cured film to be formed becomes low. In particular, a polyimide precursor having a structural unit represented by general formula (1) as component (a) and a compound that generates radicals upon irradiation with actinic rays represented by general formula (5) as component (b) are used in combination. The compound that generates radicals upon irradiation with actinic rays represented by the general formula (5) exhibits high activity particularly when irradiated with an electron beam such as i-line, so that good photosensitive characteristics can be realized. it can. Furthermore, when it becomes a polyimide by heat treatment, it has a characteristic of exhibiting low stress due to its rigid skeleton.

（一般式（４ａ）中、ｎは３以下の整数である。
一般式（４ｂ）中、Ｒ^１０１及びＲ^１０２は、各々独立に水素原子又は１価の基である。
ｍは９以下の整数である。） [Component (c): Compound represented by Formula (4a) or (4b)]
The component (c) of the resin composition of the present invention is a compound represented by the following general formula (4a) or (4b).

(In general formula (4a), n is an integer of 3 or less.
In general formula (4b), R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom or a monovalent group.
m is an integer of 9 or less. )

  In formula (4a), by setting n to 3 or less, phase separation due to an increase in the molecular weight of component (c) can be prevented. Similarly, in the formula (4b), since no crosslinking group is contained, the phase separation due to the increase in the molecular weight of the component (c) can be prevented by setting m to 9 or less.

Examples of the monovalent group of R ¹⁰¹ and R ¹⁰² include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkenyl group having 1 to 5 carbon atoms.

Examples of the component (c) include propylene glycol diacrylate, dipropylene glycol, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, and propylene. Examples include glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, and polypropylene glycol dimethyl ether.
Among these, from the viewpoint of weight loss temperature, component (c) is preferably tripropylene glycol diacrylate, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, or polypropylene glycol dimethyl ether. More preferred is propylene glycol diacrylate.
These (c) components may be used independently and may be used in combination of 2 or more types.

  In the case of containing an addition polymerizable compound, the content of the component (c) is 1 to 100 masses with respect to 100 parts by mass of the polyimide precursor from the viewpoint of solubility in a developer and heat resistance of a cured film to be obtained. Part, preferably 1 to 75 parts by mass, and more preferably 1 to 50 parts by mass.

[(D) component: solvent]
The solvent that is component (d) is preferably a polar solvent that completely dissolves the polyimide precursor that is component (a).
Examples of the component (d) include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, δ- Examples include valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, and N, N′-dimethylpropylene urea.
These components (d) may be used alone or in combination of two or more.

  The solvent as component (d) is preferably contained in the resin composition in an amount of 40 to 80% by mass, more preferably 45 to 75% by mass, and even more preferably 45 to 70% by mass.

[Other ingredients]
The resin composition of the present invention comprises (a) a polyimide precursor having a structural unit represented by formula (1), (b) a compound that generates radicals upon irradiation with actinic rays, (c) formula (4a) or (4b) And (d) a solvent may be included, and the following other components may be further included.

The resin composition of the present invention may contain (e) an organosilane compound in order to improve 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.

  In the case of containing an organosilane compound, the content is preferably 0.1 to 20 parts by mass, and 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor, from the viewpoint of adhesion after curing. More preferably, the content is 0.5 to 10 parts by mass.

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

  As a content in the case of containing a radical polymerization inhibitor and / or a radical polymerization inhibitor, from the viewpoint of storage stability of the resin composition and heat resistance of the resulting cured film, 100 parts by mass of the polyimide precursor, It is preferable that it is 0.01-30 mass parts, It is more preferable that it is 0.01-10 mass parts, It is further more preferable that it is 0.05-5 mass parts.

The resin composition of the present invention may contain components (a) to (d) and optionally components (e) and / or (f), and may consist essentially of these components, only these components. It may consist of
The “substantially” means, for example, that the total amount of components (a) to (d) and components (e) to (f) in the resin composition is 95% by weight or more of the total composition, or 98% by weight. It means that it is more than%.

[Pattern cured film and pattern cured film manufacturing method]
The cured pattern film of the present invention can be obtained by exposing and heating the resin composition of the present invention. The pattern cured film of the present invention is preferably used as a protective layer of a low-k material which is an interlayer insulating film. Examples of the low-k material include porous silica, benzocyclobutene, hydrogen silsesquioxane, polyallyl ether, and the like.

  The method for producing a patterned cured film of the present invention includes a step of applying the resin composition of the present invention on a substrate and drying to form a coating film, a step of irradiating the formed coating film with an actinic ray and exposing to a pattern And a step of removing an unexposed portion other than the exposed portion by development to obtain a patterned resin film, and a step of heat-treating the obtained patterned resin film to form a polyimide pattern.

In the step of applying the resin composition onto the substrate and drying to form a coating film, examples of the method of applying the resin composition onto the substrate include dipping, spraying, screen printing, and spin coating. It is done.
Examples of the substrate 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.

After the resin composition is applied on the substrate, the solvent is removed (dried) by heating to form a coating film (resin film) with less adhesiveness.
In addition, it is preferable that the heating temperature at the time of drying is 80-130 degreeC, and it is preferable that drying time is 30-300 second. Drying is preferably performed using an apparatus such as a hot plate.

In the step of irradiating the coating film with an actinic ray and exposing it to a pattern and the step of removing the unexposed portion other than the exposed portion by development to obtain a pattern resin film, the pattern exposure is performed on the obtained coating film, This is performed by irradiating actinic rays through a mask on which a desired pattern is drawn.
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.

A desired pattern resin film can be obtained by dissolving and removing the unexposed portion with an appropriate developer after exposure.
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 (for example, water, ethanol, 2-propanol) or the like is performed as necessary.

In the step of heat-treating the pattern resin film, the resulting pattern is heated, for example, at 80 to 325 ° C. for 5 to 300 minutes, so that the imidation of the polyimide precursor contained in the resin composition is advanced to form a pattern cured film. Can be obtained.
In order to suppress the oxidative deterioration of the polyimide during heating, it is preferable to use a curing furnace that can be cured at a low oxygen concentration of 100 ppm or less, for example, an inert gas oven or a vertical diffusion furnace. Can do.

[Semiconductor device]
The semiconductor device of the present invention has a cured pattern film obtained by the production method of the present invention. Examples of the semiconductor device include a logic semiconductor device such as an MPU, and a memory semiconductor device such as a DRAM and a NAND flash.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to these Examples.

Example 1-4 and Comparative Example 1-7
[Synthesis of polyamic acid ester (polyimide precursor)]
2 equivalents of 2-hydroxyethyl methacrylate and a catalytic amount of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) to 4,4′-oxydiphthalic dianhydride 1 The resultant was dissolved in N-methyl-2-pyrrolidone 4 times as much as 4,4′-oxydiphthalic dianhydride, and stirred at room temperature for 48 hours to obtain an ester solution 1.
While the ester solution 1 was cooled in an ice bath, 2.2 equivalents of thionyl chloride was added dropwise to the total amount of the ester solution 1, and then stirred for 1 hour to prepare an acid chloride solution.
Prepare a solution prepared by dissolving pyridine equivalent to twice the thionyl chloride in N-methyl-2-pyrrolidone four times as much as 2,2′-dimethylbenzidine by mass ratio. The solution was added dropwise while cooling in an ice bath. After completion of the dropping, the reaction solution was dropped into distilled water, and the resulting precipitate was collected by filtration, washed several times with distilled water, and then vacuum dried to obtain a polyamic acid ester.

[Preparation of photosensitive resin composition]
100 parts by mass of the polyamic acid ester obtained above, 20 parts by mass of the compound represented by the general formula (4a) or (4b) shown in Table 1, IRGACURE OXE-01, 1- [4- (phenylthio) manufactured by BASF Stir until phenyl] -1,2-octanedione 2- (O-benzoyloxime) [component (b)] is uniformly dissolved in 150 parts by mass of N-methyl-2-pyrrolidone [component (d)]. After that, the resin composition was obtained by carrying out pressure filtration using a 1 micrometer filter.
The following evaluation was performed about the obtained resin composition. The evaluation results are shown in Table 1.

(1) Photosensitive property evaluation The obtained photosensitive resin composition was applied on a 6-inch silicon wafer by using a Mark-7 manufactured by Tokyo Electron Co., Ltd. by spin coating, and dried on a hot plate at 100 ° C. for 200 seconds. A coating film having a thickness of 10 μm was formed. At this time, the coating film was checked for the presence or absence of phase separation. The results are shown in Table 1.
If phase separation is not, through the photomask obtained coating film, by using an i-line stepper FPA-3000iW manufactured by Canon Inc., the predetermined i-line of 30~330mJ / cm ² at 30 mJ / cm ² increments The pattern was irradiated and exposed. In addition, the development time is set to twice the time until an unexposed coating film having the same thickness is completely dissolved by being immersed in cyclopentanone, and the wafer after exposure is immersed in cyclopentanone for paddle development. Thereafter, rinsing with PGMEA was performed. A case where a 300 mJ / cm ² pattern was obtained was marked as ◯, and a case where a pattern was not obtained was marked as x.

(2) Measurement of thermal weight loss The obtained photosensitive resin composition was applied to a 6-inch silicon wafer having a thickness of 625 μm, and spin-coated so that the film thickness after curing was about 5 μm. The obtained coating film was heated and cured at 300 ° C., 325 ° C., 350 ° C. and 375 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace manufactured by Koyo Thermo Systems, and a polyimide film (cured film) was obtained. Obtained.
The cured polyimide film was immersed in a 4.9% hydrofluoric acid solution, the polyimide film was peeled off from a 6-inch silicon wafer, and the peeled film was measured. The measurement results are shown in Table 1.

In Table 1, the numerical value of n represents the number of ethylene chain or propylene chain repeats. Also,
Td 1%, Td 3%, and Td 5% represent temperatures when weight is reduced by 1, 3 and 5%, respectively, Tg represents a glass transition temperature, and CTE represents an average linear thermal expansion between 100 ° C. and 200 ° C.

  In Examples 1 to 4 using an additive having a propylene chain, the thermogravimetric decrease temperature is 15 ° C. or more higher than that of the comparative example at 300 ° C. to 325 ° C., whereas it has an ethylene chain. Comparative Examples 1 to 3 showed results lower by 15 ° C. or more than the Examples. When a methacrylate group was present at the end of Comparative Examples 4 and 5, or when n was 11 or more as in Comparative Examples 6 and 7, phase separation occurred after PB, and evaluation was not possible. The photosensitivity results were good in all systems that did not phase separate.

  The resin composition of the present invention can be used as a protective film material or a pattern film forming material for electronic parts such as semiconductor devices.

Claims (7)

A resin composition containing the following components (a) to (d).
(A) Polyimide precursor having a structural unit represented by the following general formula (1) (b) Compound that generates radicals upon irradiation with actinic rays (c) Compound represented by the following general formula (4b) (d) Solvent

(In General Formula (1), A is any one of tetravalent organic groups represented by the following General Formulas (2a) to (2e).
B is a divalent organic group represented by the following general formula (3).
R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group.
However, 80% or more of R ¹ and R ^{2 in} the formula (1) is a monovalent organic group having a carbon-carbon unsaturated double bond. )

(In General Formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.
In general formula (2e), Z is an ether bond (—O—) or a sulfide bond (—S—). )

(In General Formula (3), R ^{3 to} R ¹⁰ are each independently a hydrogen atom or a monovalent group.
However, R < ³ > -R < ¹⁰ > is not a monovalent organic group having a halogen atom and a halogen atom. )

(In General Formula (4b), R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom , an alkyl group having 1 to 5 carbon atoms , or an alkenyl group having 1 to 5 carbon atoms . M is an integer of 9 or less. .) The resin composition according to claim 1, wherein the component (b) is a compound represented by the following general formula (5).

(In the general formula (5), R ^{11 to} R ¹⁷ each independently represent a hydrogen atom or a monovalent group.) The resin composition according to claim 2, wherein the component (b) is a compound represented by the following formula (6).

  A resin composition containing the following components (a) to (d).
  (A) A polyimide precursor having a structural unit represented by the following general formula (1)
  (B) A compound that generates radicals upon irradiation with actinic rays and is represented by the following general formula (5) or (6)
  (C) one or more compounds selected from the group consisting of propylene glycol diacrylate, tripropylene glycol diacrylate, and tetrapropylene glycol diacrylate
  (D) Solvent

(In General Formula (1), A is any one of tetravalent organic groups represented by the following General Formulas (2a) to (2e).
  B is a divalent organic group represented by the following general formula (3).
  R ¹ And R ² Are each independently a hydrogen atom or a monovalent organic group.
  However, R in formula (1) ¹ And R ² 80% or more of is a monovalent organic group having a carbon-carbon unsaturated double bond. )

(In General Formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.
  In general formula (2e), Z is an ether bond (—O—) or a sulfide bond (—S—). )

(In the general formula (3), R ³ ~ R ¹⁰ Are each independently a hydrogen atom or a monovalent group.
  However, R ³ ~ R ¹⁰ Is not a halogen atom or a monovalent organic group having a halogen atom. )

(In the general formula (5), R ¹¹ ~ R ¹⁷ Each independently represents a hydrogen atom or a monovalent group. )

Applying the resin composition according to any one of claims 1 to 4 on a substrate and drying to form a coating film;
Irradiating the coating film formed in the step with an actinic ray to expose it in a pattern; and
Removing a non-exposed portion other than the exposed portion by development to obtain a patterned resin film;
A process for producing a cured pattern film, comprising: heating the patterned resin film obtained in the process to a polyimide pattern.   The pattern cured film produced using the resin composition in any one of Claims 1-4. A semiconductor device comprising the patterned cured film according to claim 6 .