JP6244871B2 - Polyimide precursor resin composition - Google Patents

Description

  The present invention relates to a resin composition having excellent storage stability, low stress of a cured film obtained, and excellent adhesion to a substrate even at low temperature curing, and a method for producing a pattern using the resin composition.

  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. The cured film is required to have properties such as thick film formability and high elastic modulus. 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.

  In order to reduce the stress while maintaining the high heat resistance and good mechanical properties of polyimide resin, it has been reported that it is effective to reduce the thermal expansion coefficient by making the polyimide skeleton a rigid and linear skeleton. Has been.

Further, when the resin film is thickened from the viewpoint of protecting the low-k layer, there is a problem that the i-line transmittance of the resin film is lowered and the pattern cannot be formed. On the other hand, in order to increase the i-line transmittance of the coating film, there is a method using a polyimide precursor containing fluorine.
However, a cured film obtained after heat-curing a fluorine-containing polyimide precursor has a drawback of low adhesion to a silicon substrate used as a substrate (for example, Patent Documents 1 and 2).

  In order to provide excellent adhesion to a silicon substrate, a resin composition using 3-isocyanatopropyltriethoxysilane has been reported (for example, Patent Document 3). However, since it has a highly reactive isocyanate group, there is a problem that the storage stability of the resin composition is deteriorated.

Japanese Patent Laid-Open No. 6-342211 JP 2003-313743 A JP 11-338157 A

According to the knowledge of the present inventors, a resin having excellent storage stability compared to the case of a conventional isocyanate group adhesion assistant by using an adhesion assistant in which a highly reactive isocyanate group is protected with ethanol. The cured film obtained as a composition has low stress and excellent adhesion to the substrate.
However, as a result of further studies, when the curing temperature was lowered, the protecting group was not easily removed, and a highly reactive isocyanate group did not contribute to adhesion, and the problem of poor adhesion was encountered.

  In order to solve such a problem, the present invention uses a resin composition that has excellent adhesion to a substrate even when the obtained cured film is cured at low temperature, and has excellent storage stability and photosensitive characteristics, and the resin composition. It aims at providing the manufacturing method of a cured film.

（式中、Ｒ^１は４価の有機基、Ｒ^２は２価の有機基、Ｒ^３及びＲ^４は各々独立に水素原子、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一価の有機基である。）

（式中、Ｒ^５は各々独立に炭素数１〜４のアルキル基、Ｒ^６は各々独立に水酸基又は炭素数１〜４のアルキル基、ａは０〜３の整数であり、ｎは１〜６の整数であり、Ｒ^７は下記一般式（３）の基である。）

（式中、Ｒ^８は２級、３級アルコール又はフェノール由来の１価の有機基である。）
２．前記一般式（１）中のＲ^２が、下記一般式（４）で表わされる２価の有機基である１記載の樹脂組成物。

（式中、Ｒ^９〜Ｒ^１６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^９〜Ｒ^１６の少なくとも一つはフッ素原子又はトリフルオロメチル基である。）
３．前記一般式（１）中のＲ^２が、一般式（５）で表わされる２価の有機基である１又は２記載の樹脂組成物。

（式中、Ｒ^１７及びＲ^１８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。）
４．さらに、（ｃ）成分として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）成分が、オキシムエステル化合物を含有する４記載の樹脂組成物。
６．前記（ｃ）成分が、下記式（６）で表される化合物、下記式（７）で表される化合物又は下記一般式（８）で表される化合物である４又は５記載の樹脂組成物。

（式（６）中、Ｒ及びＲ_１は、それぞれ炭素数１〜１２のアルキル基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基を示す。
Ｒ_２は、水素原子、−ＯＨ、−ＣＯＯＨ、−Ｏ（ＣＨ_２）ＯＨ、−Ｏ（ＣＨ_２）_２ＯＨ、−ＣＯＯ（ＣＨ_２）ＯＨ又は−ＣＯＯ（ＣＨ_２）_２ＯＨを示す。）

（式（７）中、Ｒ_３は、それぞれ炭素数１〜６のアルキル基を示し、Ｒ_４は、−ＮＯ_２又はＲ_２０ＣＯ−（ここで、Ｒ_２０はアリール基を示す。）を示す。
Ｒ_５及びＲ_６は、それぞれ炭素数１〜１２のアルキル基、フェニル基又はトリル基を示す。）

（式（８）中、Ｒ_７は、炭素数１〜６のアルキル基を示し、Ｒ_８はアセタール結合を有する有機基である。Ｒ_９及びＲ_１０は、それぞれ炭素数１〜１２のアルキル基、フェニル基又はトリル基を示す。）
７．前記（ｃ）成分の含有量が、前記（ａ）成分１００質量部に対して０．０１〜３０質量部である４〜６のいずれかに記載の樹脂組成物。
８．１〜７のいずれかに記載の樹脂組成物から形成される硬化膜。
９．１〜７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、塗膜を加熱処理する工程とを含む、硬化膜の製造方法。
１０．４〜７のいずれかに記載の樹脂組成物から形成されるパターン硬化膜。
１１．４〜７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後、現像してパターン樹脂膜を得る工程と、前記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, method for producing a cured film, and the like are provided.
1. The resin composition containing the following (a) component and (b) component.
(A) Polyimide precursor having a structural unit represented by the following general formula (1) (b) Compound represented by the following general formula (2)

(Wherein 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, a cycloalkyl group, or a carbon-carbon unsaturated double bond. A monovalent organic group.)

(Wherein R ⁵ is each independently an alkyl group having 1 to 4 carbon atoms, R ⁶ is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 3, and n is 1 to 1) 6 is an integer, and R ⁷ is a group of the following general formula (3).)

(In the formula, R ⁸ is a monovalent organic group derived from a secondary, tertiary alcohol or phenol.)
2. 2. The resin composition according to 1, wherein R ² in the general formula (1) is a divalent organic group represented by the following general formula (4).

(In the formula, R ^{9 to} R ¹⁶ each independently represents a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ^{9 to} R ¹⁶ is a fluorine atom or a trifluoromethyl group.)
3. 3. The resin composition according to 1 or 2, wherein R ² in the general formula (1) is a divalent organic group represented by the general formula (5).

(In the formula, R ¹⁷ and R ¹⁸ each independently represents a fluorine atom or a trifluoromethyl group.)
4). Furthermore, the resin composition in any one of 1-3 containing the compound which generate | occur | produces a radical by actinic ray irradiation as (c) component.
5). 5. The resin composition according to 4, wherein the component (c) contains an oxime ester compound.
6). The resin composition according to 4 or 5, wherein the component (c) is a compound represented by the following formula (6), a compound represented by the following formula (7), or a compound represented by the following general formula (8). .

(In the formula (6), R and _{R 1} are each an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group.
R ₂ represents a hydrogen atom, —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH. )

(In Formula (7), R ₃ represents an alkyl group having 1 to 6 carbon atoms, and R ₄ represents —NO ₂ or R ₂₀ CO— (wherein R ₂₀ represents an aryl group). .
R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. )

(In Formula (8), R ₇ represents an alkyl group having 1 to 6 carbon atoms, and R ₈ is an organic group having an acetal bond. R ₉ and R ₁₀ are each an alkyl group having 1 to 12 carbon atoms. Represents a phenyl group or a tolyl group.)
7). The resin composition according to any one of 4 to 6, wherein the content of the component (c) is 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (a).
The cured film formed from the resin composition in any one of 8.1-7.
The manufacturing method of a cured film including the process of apply | coating the resin composition in any one of 9.1-7 on a board | substrate, drying and forming a coating film, and the process of heat-processing a coating film.
The pattern cured film formed from the resin composition in any one of 10.4-7.
A step of applying the resin composition according to any one of 11.4 to 7 on a substrate and drying to form a coating film, and irradiating the coating film formed in the step with an actinic ray, followed by development to form a pattern resin The manufacturing method of a pattern cured film including the process of obtaining a film | membrane, and the process of heat-processing the said pattern resin film.

  ADVANTAGE OF THE INVENTION According to this invention, the cured film obtained provides the manufacturing method of the cured film using the resin composition which is excellent in adhesiveness with a base material even if it cures at low temperature, and is excellent in storage stability and a photosensitive characteristic, and the said resin composition. be able to.

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

  Below, the resin composition concerning this invention, the manufacturing method of a pattern cured film using the resin composition, a pattern cured film, and embodiment of an electronic component are demonstrated in detail. In addition, this invention is not limited by this embodiment.

（式中、Ｒ^１は４価の有機基、Ｒ^２は２価の有機基、Ｒ^３、Ｒ^４は各々独立に水素原子、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一価の有機基である。） <Resin composition>
The resin composition of the present invention contains the following components (a) and (b).
(A) Polyimide precursor having a structural unit represented by the following general formula (1) (b) Compound represented by the following general formula (2)

(Wherein 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, a cycloalkyl group, or a carbon-carbon unsaturated double bond. A monovalent organic group.)

（式中、Ｒ^５は炭素数１〜４のアルキル基を表し、Ｒ^６は各々独立に水酸基又は炭素数１〜４のアルキル基、ａは０〜３の整数であり、ｎは１〜６の整数であり、Ｒ^７は下記一般式（３）の基である。）

(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms, R ⁶ is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 3, and n is 1 to 6) And R ⁷ is a group of the following general formula (3).)

（式中、Ｒ^８は２級、３級アルコール、又はフェノール由来の１価の有機基である。）

(In the formula, R ⁸ is a monovalent organic group derived from secondary, tertiary alcohol, or phenol.)

  Component (b) is an adhesion aid. In the present invention, since a highly reactive isocyanate group is protected with a protecting group that is easily removed other than the primary alcohol, the temperature is lower than that of a conventional adhesion assistant protected with ethanol of a primary alcohol. However, the protecting group is easily removed. When the protecting group is removed, a highly reactive isocyanate group is formed, and it easily reacts with the polymer. Moreover, the cured film obtained is excellent in adhesion to the substrate even at low stress and low temperature curing. Hereinafter, each component will be described in detail.

（式中、Ｒ^１は４価の有機基、Ｒ^２は２価の有機基、Ｒ^３及びＲ^４は各々独立に水素原子、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一価の有機基である。） (A) Component: polyimide precursor having a structural unit represented by the general formula (1) The resin composition of the present invention comprises (a) a polyimide precursor having a structural unit represented by the following general formula (1). contains.

(Wherein 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, a cycloalkyl group, or a carbon-carbon unsaturated double bond. A monovalent organic group.)

  The residual stress of the cured film obtained by applying the polyimide precursor represented by the general formula (1) to the substrate and heat-curing is preferably 30 MPa or less when the thickness of the cured film is 10 μm. 27 MPa or less, more preferably 25 MPa or less. If the residual stress is 30 MPa or less, when the film is formed so that the film thickness after curing is 10 μm, the warpage of the wafer can be more sufficiently suppressed, and the problems that occur in the conveyance and suction fixation of the wafer are further reduced. Can be suppressed.

  The residual stress can be measured by a method of measuring the amount of warpage of the wafer using a thin film stress measuring apparatus FLX-2320 manufactured by KLA Tencor and converting it to stress.

  In order to form the cured film obtained in the present invention so as to have a film thickness of 10 μm after curing, the resin composition is applied onto a substrate and dried to form a coating film, and then a thickness of about 20 μm. It is necessary to form with. For this reason, when a photosensitive resin composition is used in combination with a compound that generates radicals upon irradiation with actinic rays, it is important to exhibit high i-line transmittance.

  Specifically, when the film thickness is 20 μm, the i-line transmittance is preferably 5% or more, more preferably 8% or more, further preferably 15% or more, and 30% or more. Is particularly preferred. If it is lower than 5%, the i-line does not reach the deep part and sufficient radicals are not generated, so that there is a possibility that the photosensitive characteristics may be deteriorated, for example, the resin oozes out from the substrate side of the film during development.

  The i-line transmittance can be measured by measuring a transmitted UV spectrum using a U-3310 spcphotophotometer manufactured by HITACHI.

R ¹ in the general formula (1) is a structure derived from tetracarboxylic dianhydride used as a raw material. From the viewpoint of stress of the cured film, pyromellitic dianhydride, 2, 3, 6, 7 -Naphthalenetetracarboxylic dianhydride or 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is preferred. These are used alone or in combination of two or more.

  In addition, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, as long as the stress and i-line transmittance of the cured film are not lowered. 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m -Terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 1,1,1,3 , 3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (3 4-dicarboxyphenyl) propane dianhydride, 2,2-bi (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-dicarboxyphenoxy) 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'-sulfonyldiphthalic dianhydride and the like.

（式中、Ｒ^９〜Ｒ^１６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^９〜Ｒ^１６の少なくとも一つはフッ素原子又はトリフルオロメチル基である。Ｒ^１７及びＲ^１８は各々独立にフッ素原子又はトリフルオロメチル基である。） R ² in the general formula (1) is a structure derived from a diamine used as a raw material. From the viewpoint of i-line transmittance, R ² in the general formula (1) is preferably a divalent organic group represented by the following general formula (4) or (5).

(In the formula, R ^{9 to} R ¹⁶ each independently represents a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ^{9 to} R ¹⁶ is a fluorine atom or a trifluoromethyl group. R ¹⁷ And R ¹⁸ are each independently a fluorine atom or a trifluoromethyl group.)

In particular, from the viewpoint of i-line transmittance and availability, R ² in the general formula (1) is more preferably a divalent organic group represented by the general formula (5).

In the component (a), the structural unit in which R ² in the general formula (1) is represented by the general formula (5) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, More preferably, it is 30-90 mol%.

  The organic group that gives the structure of the general formula (4) or (5) is 2,2′-bis (trifluoromethyl) -4,4 from the viewpoints of low stress, good i-line transmittance and heat resistance. Examples include '-diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, or 4,4'-diaminooctafluorobiphenyl. These are used alone or in combination of two or more.

  Moreover, the diamine compound which gives structures other than General formula (4) and (5) can be used to such an extent that low stress property, favorable i line | wire transmittance, heat resistance, etc. are not reduced. Specifically, 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-diethylaniline), 4,4′-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4 , 4'-Benzophenonedia , Bis- {4- (4′-aminophenoxy) phenyl} sulfone, 2,2-bis {4- (4′-aminophenoxy) phenyl} propane, 3,3′-dimethyl-4,4′-diamino Diphenylmethane, 3,3 ′, 5,5′-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.

R ³ and R ⁴ in the general 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 an alkyl group having 1 to 10 carbon atoms. Examples include an acryloxyalkyl group and a methacryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group.

When imparting photosensitivity to the polyimide precursor, at least one of R ³ and R ⁴ is an acryloxyalkyl group having 1 to 10 carbon atoms or a methacryloxyalkyl group having 1 to 10 carbon atoms, It is preferable to combine with a compound having a carbon-carbon unsaturated double bond and generating a radical upon irradiation with actinic rays so that crosslinking between molecular chains by radical polymerization is possible.

（ここでＲ^１〜Ｒ^４は式（１）と同じである。） The component (a) of the present invention can be synthesized by addition polymerization of tetracarboxylic dianhydride and diamine. Moreover, after making the tetracarboxylic dianhydride represented by Formula (10) into a diester derivative, it converts into the acid chloride represented by Formula (11), and makes it react with the diamine represented by Formula (12). Can be synthesized.

(Here, R ^{1 to} R ⁴ are the same as in formula (1).)

（ここで式中のＲ^１９は、水素原子、アルキル基、炭素炭素不飽和二重結合を有する一価の有機基である。） The tetracarboxylic acid mono (di) ester dichloride represented by the general formula (11) includes a tetracarboxylic dianhydride represented by the general formula (10) and a compound represented by the following general formula (13). Can be obtained by reacting a tetracarboxylic acid mono (di) ester obtained by reacting with a chlorinating agent such as thionyl chloride or dichlorooxalic acid.

(Here, R ¹⁹ in the formula is a hydrogen atom, an alkyl group, or a monovalent organic group having a carbon-carbon unsaturated double bond.)

The chlorinating agent is usually used in an amount of 2 molar equivalents per 1 mol of tetracarboxylic acid mono (di) ester. Polymer synthesis is carried out by reacting with diamine in the presence of 2 molar equivalents of basic compound with respect to the chlorinating agent. In order to control the molecular weight of the synthesized polyimide precursor, You may adjust suitably. As an equivalent of a chlorinating agent, 1.5-2.5 molar equivalent is preferable, 1.6-2.4 molar equivalent is more preferable, 1.7-2.3 molar equivalent is further more preferable. If the amount is less than 1.5 molar equivalents, the molecular weight of the polyimide precursor is low, so that low stress after curing may not be sufficiently exhibited. May remain in the polyimide precursor in a large amount, and the electrical insulation of the cured polyimide may be reduced.
As the basic compound, pyridine, 4-dimethylaminopyridine, triethylamine or the like can be used, and it is preferably used in an amount of 1.5 to 2.5 times the chlorinating agent, and 1.7 to 2.4. A double amount is more preferable, and a 1.8 to 2.3-fold amount is even more preferable. 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.

  The tetracarboxylic dianhydride and the compound of the general formula (13) can also be synthesized by reacting in the presence of a basic catalyst. 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.

Among the compounds represented by the general formula (13), examples of the alcohol include alcohols in which R ¹⁹ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
Examples of the monovalent organic group having a carbon-carbon unsaturated double bond represented by R ¹⁹ include 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. Is mentioned.
Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, hexanol, cyclohexanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, Examples include 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.

  As for the molecular weight of the polyimide precursor of the present invention, 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 is less than 10,000, the stress after curing may not be sufficiently reduced, and if it is more than 100,000, the solubility in a solvent may be reduced, and the viscosity of the solution may be increased, resulting in a decrease in handleability. is there. 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.

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

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

  In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and the like can also be used. Specifically, 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-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These organic solvents may be used alone or in combination of two or more.

  In addition, as a heating temperature which heat-processes the polyimide precursor which is (a) component of this invention, advances imidization, and converts it into a polyimide, 80-450 degreeC is preferable, 100-300 degreeC is more preferable, 200 More preferably, it is -300 degreeC. If it is 80 ° C. or lower, imidization does not proceed sufficiently and heat resistance may be lowered. If it is performed at a temperature higher than 300 ° C., a substrate that is weak against heat may cause a defect.

（式中、Ｒ^５は各々独立に炭素数１〜４のアルキル基を表し、Ｒ^６は各々独立に水酸基又は炭素数１〜４のアルキル基、ａは０〜３の整数であり、ｎは１〜６の整数であり、Ｒ^７は下記一般式（３）の基である。） (B) Component: Compound Represented by General Formula (2) The resin composition of the present invention has the following general formula (b) as the component (b) from the viewpoint of improving the adhesion of the resulting cured film to the substrate. The compound represented by 2) is contained.

(In the formula, each R ⁵ independently represents an alkyl group having 1 to 4 carbon atoms, R ⁶ is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 3, and n is (It is an integer of 1 to 6, and R ⁷ is a group of the following general formula (3).)

（式中、Ｒ^８は２級、３級アルコール、又はフェノール由来の１価の有機基である。）

(In the formula, R ⁸ is a monovalent organic group derived from secondary, tertiary alcohol, or phenol.)

In said general formula (2), R < ⁵ > is respectively independently a C1-C4 alkyl group, Preferably they are a methyl group or an ethyl group.

In the general formula (2), each R ⁶ is independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Preferable examples of the alkyl group having 1 to 4 carbon atoms of R ⁶ are the same as those of the alkyl group having 1 to 4 carbon atoms of R ⁵ .

  In said general formula (2), a is 0-3, and 2 or 3 is preferable. In said general formula (2), n is an integer of 1-6, and the integer of 2-4 is preferable.

In the general formula (3), R ⁸ is a monovalent organic group derived from a secondary, tertiary alcohol, or phenol, and is a substituted or unsubstituted C3-C8 branched alkyl group or alkenyl group. Or a substituted or unsubstituted phenyl group is preferred, and a substituted or unsubstituted tertiary alkyl group having 3 to 8 carbon atoms or a substituted or unsubstituted phenyl group is more preferred. From the viewpoint of easy availability, a tertiary alkyl group having 3 to 8 carbon atoms is more preferable.

Examples of the substituent for the branched alkyl group or alkenyl group having 3 to 8 carbon atoms include isopropyl group, isobutyl group, isopentyl group, tertiary butyl group, and tertiary pentyl group.
Examples of the substituted or unsubstituted phenyl group include a phenyl group, a tolyl group, a xylyl group, and a group obtained by removing one hydrogen atom from benzene of benzoic acid.

  The resin composition of this invention can express the adhesiveness to the favorable board | substrate when it is set as a cured film by containing the compound represented by General formula (2) as (b) component. This is because, in the heat curing step of the resin film, the isocyanate protecting group of the compound represented by the general formula (2) is eliminated, the highly reactive isocyanate group is regenerated, and the carboxylic acid at the terminal of the polymer (polyimide precursor) This is thought to be due to the reaction with amines and chemical bonds. When the protective group is eliminated, it is considered that secondary alcohol, tertiary alcohol, and phenol are more easily eliminated than primary alcohol, and a highly reactive isocyanate group is likely to be regenerated. Therefore, it is considered that it can react with carboxylic acid and amine at a lower temperature to give strong adhesion.

  Moreover, the resin composition of this invention can express favorable storage stability by containing the compound represented by General formula (2) as (b) component. This is presumably because the protected isocyanate of the compound represented by the general formula (2) is in a low-reactive state in which the protective group is not eliminated before the heat curing step.

Examples of the component (b) include the following compounds, but 3-triethoxysilylpropyl-t-butylcarbamate is more preferable from the viewpoint of availability.

  As content of the said (b) component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, 1-10 mass parts is more preferable, and 1-6 mass parts is further more preferable. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.

  The resin composition of the present invention may contain an organosilane compound other than the component (b) 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, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) Propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutyryl Emissions) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The blending amount is appropriately adjusted so as to obtain a desired effect.

(C) Component: Compound that generates radicals by actinic rays (a) At least a part of R ³ and / or R ⁴ in the polyimide precursor of component is a monovalent organic group having a carbon-carbon unsaturated double bond. In this case, a photosensitive resin composition can be obtained by dissolving it in a solvent in combination with a compound that generates radicals when irradiated with actinic rays.
In the present invention, when a photosensitive resin composition containing the component (c) is obtained, the resin composition is excellent in i-line transmittance, which is preferable.

The component (c) is not particularly limited as long as it is a compound capable of generating radicals upon irradiation with actinic rays.
As the component (c), N, N′-tetraalkyl-4,4′-diaminobenzophenone such as an oxime ester compound, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) described later , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, etc. Quinones fused with an aromatic ring such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal.

  Among these, in particular, the oxime ester compound is more sensitive and has a diamine residue represented by the above formula (4), particularly a polyimide precursor having a diamine residue represented by (5). In the photosensitive resin composition containing a body, a remarkably good pattern is given and it is more preferable.

  In particular, in the case of the component (a) having a diamine residue represented by the formula (5), the conventional resin composition often cannot obtain good photosensitive characteristics. From the viewpoint of obtaining good sensitivity and a remaining film ratio even with such a component (a), a compound represented by the following formula (6), a compound represented by the following formula (7), or the following general formula ( It is preferable that it is a compound represented by 8).

式（６）中、Ｒ及びＲ_１は、それぞれ炭素数１〜１２のアルキル基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基を示し、炭素数１〜８のアルキル基、炭素数４〜６のシクロアルキル基、フェニル基又はトリル基であることが好ましく、炭素数１〜４のアルキル基、炭素数４〜６のシクロアルキル基、フェニル基又はトリル基であることがより好ましく、メチル基、シクロペンチル基、フェニル基又はトリル基であることがさらに好ましい。
Ｒ_２は、水素原子、−ＯＨ、−ＣＯＯＨ、−Ｏ（ＣＨ_２）ＯＨ、−Ｏ（ＣＨ_２）_２ＯＨ、−ＣＯＯ（ＣＨ_２）ＯＨ又は−ＣＯＯ（ＣＨ_２）_２ＯＨを示し、水素原子、−Ｏ（ＣＨ_２）ＯＨ、−Ｏ（ＣＨ_２）_２ＯＨ、−ＣＯＯ（ＣＨ_２）ＯＨ又は−ＣＯＯ（ＣＨ_２）_２ＯＨであることが好ましく、水素原子、−Ｏ（ＣＨ_２）_２ＯＨ又は−ＣＯＯ（ＣＨ_２）_２ＯＨであることがより好ましい。

In formula (6), R and R ₁ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and an alkyl group having 1 to 8 carbon atoms, carbon A cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is more preferable. More preferably a methyl group, a cyclopentyl group, a phenyl group or a tolyl group.
R ₂ represents a hydrogen atom, —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH, hydrogen An atom, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH is preferred, and a hydrogen atom, —O (CH ₂ ) and more preferably ₂ OH or -COO _{(CH 2) 2} OH.

式（７）中、Ｒ_３は、それぞれ炭素数１〜６のアルキル基を示し、プロピル基であることが好ましい。
Ｒ_４は、−ＮＯ_２又はＲ_２０ＣＯ−（ここで、Ｒ_２０はアリール基を示す。）を示し、Ｒ_２０としては、トリル基が好ましい。
Ｒ_５及びＲ_６は、それぞれ炭素数１〜１２のアルキル基、フェニル基又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましい。

In Formula (7), R ₃ represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group.
R ₄ represents —NO ₂ or R ₂₀ CO— (wherein R ₂₀ represents an aryl group), and R ₂₀ is preferably a tolyl group.
R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, and preferably a methyl group, a phenyl group or a tolyl group.

式（８）中、Ｒ_７は、炭素数１〜６のアルキル基を示し、エチル基であることが好ましい。
Ｒ_８はアセタール結合を有する有機基であり、下記式（８−１）に示す化合物が有するＲ^８に対応する置換基であることが好ましい。
Ｒ_９及びＲ_１０は、それぞれ炭素数１〜１２のアルキル基、フェニル基又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましく、メチル基であることがより好ましい。

In formula (8), R ₇ represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group.
R ₈ is an organic group having an acetal bond, and is preferably a substituent corresponding to R ⁸ included in the compound represented by the following formula (8-1).
R ₉ and R ₁₀ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group, and more preferably a methyl group.

  As the compound represented by the above formula (6), a compound represented by the following formula (6-1) and a compound represented by the following formula (6-2) are preferable. The compound represented by the following formula (6-1) is available as IRGACURE OXE-01 (manufactured by BASF Corporation).

Examples of the compound represented by the above formula (7) include a compound represented by the following formula (7-1). This compound is available as DFI-091 (manufactured by Daito Chemix Co., Ltd.).

  Examples of the compound represented by the above formula (8) include a compound represented by the following formula (8-1). It is available as Adekaoptomer N-1919 (manufactured by ADEKA Corporation).

As other oxime ester compounds, the following compounds are preferably used.

  (C) As content in the case of containing a component, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of (a) component, and it is more preferable that it is 0.01-20 mass parts. Preferably, it is 0.01-15 mass parts, More preferably, it is 0.05-10 mass parts. If the blending amount is 0.01 parts by mass or more, the exposed part is sufficiently cross-linked, and the photosensitivity becomes more favorable. If the blending amount is 30 parts by mass or less, the amount of light absorption becomes appropriate. The reaction proceeds sufficiently to improve the photosensitive characteristics.

(D) Component: Solvent A solvent can be used as the component (d) in the resin composition of the present invention as necessary.
As the component (d), a polar solvent that completely dissolves the polyimide precursor is preferable. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethyl Phosphoric acid triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, etc. It is done. These may be used alone or in combination of two or more.

(E) Component: Addition-polymerizable compound The resin composition of the present invention may contain an addition-polymerizable compound as the component (e) as necessary. Examples of addition polymerizable compounds include polypropylene glycol diacrylates such as propylene glycol diacrylate, tripropylene glycol diacrylate, and tetrapropylene glycol diacrylate; polypropylene glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; propylene Polypropylene glycol dimethyl ethers such as glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether and tetrapropylene glycol dimethyl ether; polyethylene glycol diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate and tetraethylene glycol diacrylate Rate; polyethylene glycol dimethacrylate such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate; trimethylolpropane diacrylate, 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, pentaerythritol trimethacrylate, penta Erythritol tetramethacrylate, styrene, dibi Benzene, 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 can be mentioned. These may be used alone or in combination of two or more.

  When the addition polymerizable compound is contained, the blending amount is preferably 1 to 100 parts by weight, more preferably 1 to 75 parts by weight, and more preferably 1 to 50 parts per 100 parts by weight of component (a). It is more preferable to set it as a mass part. If the blending amount 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.

  In addition, 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. As radical polymerization inhibitors or radical polymerization inhibitors, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N- Examples include phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These may be used alone or in combination of two or more.

  As a compounding quantity in the case of containing a radical polymerization inhibitor or a radical polymerization inhibitor, it is preferable that it is 0.01-30 mass parts with respect to 100 mass parts of polyimide precursors, and is 0.01-10 mass parts. More preferably, it is more preferably 0.05 to 5 parts by mass. If the blending amount is 0.01 parts by mass or more, the storage stability becomes better, and if it is 30 parts by mass or less, the radical polymerization reaction at the time of exposure is not hindered and good photosensitive characteristics can be maintained.

  The resin composition of the present invention is substantially composed of at least one of the components (a) and (b), and optionally the components (c) to (e), a radical polymerization inhibitor and a radical polymerization inhibitor. It may consist of only these components. “Substantially” means that the composition is composed mainly of the components (a) and (b), and optionally the components (c) to (e), a radical polymerization inhibitor and a radical polymerization inhibitor. It consists of one, for example, it means that these components are 95 weight% or more or 98 weight% or more with respect to the whole raw material.

<Method for producing cured film and patterned cured film>
The cured film of the present invention is a cured film formed from the above resin composition.
Moreover, the pattern cured film of this invention is a pattern cured film formed with the above-mentioned resin composition. The pattern cured film of this invention is formed when the above-mentioned resin composition contains (c) component.

  The method for producing a cured pattern film of the present invention includes a step of applying the above resin composition on a substrate and drying to form a coating film, and developing the coating film after irradiating the coating film formed in the above step with actinic rays. It is a manufacturing method of a pattern cured film including the process of obtaining a pattern resin film, and the process of heat-processing a pattern resin film.

Hereinafter, each process of the manufacturing method of a pattern cured film is demonstrated first.
The manufacturing method of the pattern cured film of this invention includes the process of apply | coating the above-mentioned resin composition on a board | substrate, and drying and forming a coating film. Examples of the method for applying the resin composition on the substrate include dipping, spraying, screen printing, and spin coating. 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.

  In the drying step, a solvent-free coating can be formed by removing the solvent by heating. In the drying step, an apparatus such as MARK-7 manufactured by TEL can be used. The drying temperature is preferably 90 to 130 ° C., and the drying time is preferably 100 to 400 seconds.

The manufacturing method of the pattern cured film of this invention includes the process of developing after irradiating the actinic ray to the coating film formed at the said process, and obtaining a pattern resin film. Thereby, a resin film on which a desired pattern is formed 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.

  There are no particular restrictions on the developer, but N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc. Solvents, mixed solvents of these good solvents and poor solvents such as lower alcohols, water and aromatic hydrocarbons are used. After development, rinsing with a poor solvent is performed as necessary.

The manufacturing method of the pattern cured film of this invention includes the process of heat-processing a pattern resin film.
An apparatus such as a vertical diffusion furnace manufactured by Koyo Thermo Systems Co., Ltd. can be used for this heat treatment, and it is preferably performed at a heating temperature of 80 to 300 ° C., and the heating time is preferably 5 to 300 minutes. 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.

  The manufacturing method of the cured film of this invention includes the process of apply | coating a resin composition on a board | substrate, and drying and forming a coating film, and the process of heat-processing a coating film. The process of forming a coating film and the process of heat-treating can be carried out in the same manner as in the method for producing a patterned cured film. The cured film of the present invention may be a cured film that is not patterned.

The cured film or patterned cured film of the present invention thus obtained 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.

  The cured film or pattern cured film of the present invention can be used for so-called package applications such as the cover coat material, the core material for rewiring, the color material for balls such as solder, the underfill material, and the like.

  The cured film or pattern cured film of the present invention has the cured film or pattern cured film of the present invention because it has excellent adhesion to a metal layer, a sealant, and the like, as well as excellent copper migration resistance and a high stress relaxation effect. The semiconductor element is extremely excellent in 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.

Production Example 1 (Synthesis of polyamic acid ester a1)
In a 0.5 liter plastic bottle, 17.45 g (80 mmol) of pyromellitic dianhydride, 21.97 g (169 mmol) of 2-hydroxyethyl methacrylate and 0. 088 g was dissolved in 158 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 A methacrylate diester (PMDA (HEMA)) solution was obtained.

6.20 g (20 mmol) of 4,4′-oxydiphthalic dianhydride and 5.62 g (43 mmol) of 2-hydroxyethyl methacrylate, which were dried in a 0.5 liter plastic bottle with a dryer at 160 ° C. for 24 hours. 0.022 g of hydroquinone was dissolved in 47.31 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 to perform esterification. , 4′-oxydiphthalic acid-hydroxyethyl methacrylate diester (ODPA (HEMA)) solution was obtained.

  In a 0.5 liter flask equipped with a stirrer and a thermometer, 195.56 g of PMDA (HEMA) solution and 58.65 g of ODPA (HEMA) solution were placed, and then 25.91 g (220 mmol) of thionyl chloride was added under ice cooling. The reaction solution was added dropwise using a dropping funnel so as to keep the temperature of the reaction solution at 10 ° C. or lower. After the dropwise addition of thionyl chloride was completed, the mixture was stirred for 1 hour under ice cooling to obtain a solution of PMDA (HEMA) and ODPA (HEMA) chloride. Then, 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 added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to give polyamic acid ester a1 (pyromellitic acid-hydroxyethyl methacrylate diester / 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester / 2 , 2′-bis (trifluoromethyl) benzidine condensation polymer (PMDA / ODPA / TFMB)) was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion was 32,000.

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 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: UV 270 nm

Production Example 2 (Synthesis of polyamic acid ester a2)
11.77 g (40 mmol) of 3,3′-4,4′-biphenyltetracarboxylic dianhydride and 2-hydroxy methacrylate were dried for 24 hours in a dryer at 160 ° C. in a 0.5 liter plastic bottle. 10.98 g (80.2 mmol) of ethyl and 0.066 g of hydroquinone were dissolved in 136.5 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, 24 hours at room temperature (25 ° C.). Stirring was performed for esterification for 3,5′-4,4′-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester (s-BPDA (HEMA)) solution.

18.61 g (60 mmol) of 4,4′-oxydiphthalic dianhydride and 16.48 g (120.3 mmol) of 2-hydroxyethyl methacrylate dried in a 0.5-liter plastic bottle with a dryer at 160 ° C. for 24 hours. ) And 0.044 g of hydroquinone are dissolved in 93.57 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture is stirred at room temperature (25 ° C.) for 24 hours for esterification. 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester (ODPA (HEMA)) solution was obtained.

  In a 0.5 liter flask equipped with a stirrer and a thermometer, 169.28 g of s-BPDA (HEMA) solution and 116.02 g of ODPA (HEMA) solution were placed, and then 25.91 g (220 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 PMDA (HEMA) and s-BPDA (HEMA) chloride. Then, using a dropping funnel, 21.02 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 added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to give polyamic acid ester a2 (3,3′-4,4′-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester / 4,4. '-Oxydiphthalic acid-hydroxyethyl methacrylate diester / 2,2'-dimethylbenzidine condensation polymer (BPDA / ODPA / DMB)) was obtained. Similarly to the above, the weight average molecular weight determined by standard polystyrene conversion was 45,000.

Examples 1-4, Comparative Examples 1-2
Components (a) to (c) were dissolved in N-methylpyrrolidone with the formulation shown in Table 1 to prepare a photosensitive resin composition.
In Table 1, the numbers in parentheses in each column of the components (b) and (c) indicate the addition amount (parts by mass) relative to 100 parts by mass of the component (a). Further, N-methylpyrrolidone was used as a solvent, and the amount used was 1.5 times (150 parts by mass) with respect to 100 parts by mass of component (a).
In addition, 20 mass parts of tetraethylene glycol dimethacrylate was mix | blended with the said photosensitive resin composition with respect to (a) component.
Table 1 shows the results of measuring the adhesiveness of the cured film, the storage stability of the composition, and the residue of the pattern opening at the time of evaluating the photosensitive properties of the photosensitive resin compositions prepared in Examples and Comparative Examples. The evaluation method is as follows.

(Measurement of residual stress)
The obtained photosensitive resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 3 minutes to volatilize the solvent, and a coating film having a thickness of 10 μm after curing was formed. Obtained. This 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 (cured film). The residual stress of the cured polyimide film was measured at room temperature using a thin film stress measuring apparatus FLX-2320 manufactured by KLA Tencor.

(Evaluation of adhesion)
The obtained photosensitive resin composition is applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 200 seconds to evaporate the solvent, and a coating film having a film thickness of 10 μm after curing is obtained. Obtained. This was heat-cured at 270 ° C. for 4 hours in a nitrogen atmosphere using a vertical diffusion furnace manufactured by Koyo Thermo Systems Co., to obtain a polyimide film (cured film). In order to confirm the adhesion between the polyimide film and the silicon wafer used as the substrate, before and after exposing the polyimide film at 121 ° C., 2 atm, 100% RH for 100 hours (PCT0hr and PCT100hr) The adhesion was examined according to JIS K5400-8.5 (JIS D0202).
The case where the polyimide film remained 80 squares or more on the substrate was A, the case where 50 to 79 squares remained was B, the case of 50 squares or less was C, and A or more was evaluated as having good adhesion.

(Evaluation of storage stability)
The obtained photosensitive resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 200 seconds to evaporate the solvent, and a coating film having a thickness of 15 μm was obtained. The film thickness at this time was defined as the initial film thickness. After storing the photosensitive resin composition at 25 ° C. for 7 days, it was coated on a 6-inch silicon wafer under the same conditions as the measurement of the initial film thickness, and heated on a hot plate at 100 ° C. for 200 seconds. The solvent was volatilized to obtain a coating film. This film thickness was taken as the film thickness after storage for 7 days.
A when the difference between the initial film thickness and the film thickness after storage for 7 days is within ± 0.5 μm, A when the absolute value of the film thickness difference exceeds 0.5 μm and within 1.0 μm, B A value larger than 0.0 μm was defined as C, and A or higher was evaluated as having good storage stability.

(Evaluation of photosensitive characteristics (pattern opening) (residue evaluation))
The photosensitive resin composition was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100 ° C. for 200 seconds to evaporate the solvent, and a coating film having a thickness of 15 μm was obtained. The development time was set to twice the time required for this coating film to be completely dissolved by being immersed in cyclopentanone. A wafer subjected to 300 mJ / cm ² exposure in terms of i-line was immersed in cyclopentanone through a photomask using an i-line stepper FPA-3000iW manufactured by Canon Inc. through a photomask. After paddle development, the substrate was rinsed with PGMEA (propylene glycol monomethyl ether acetate). The case where there was no residue in the pattern opening was evaluated as ◯, and the case where there was a residue was evaluated as x.

In Table 1, the component (a) is the following compound.
a1: Polyamic acid ester a1 synthesized in Production Example 1 (PMDA / ODPA / TFMB)
a2: Polyamic acid ester a1 synthesized in Production Example 1 (BPDA / ODPA / DMB)

In Table 1, the component (b) is a compound represented by the following structural formula.

b1: 3-triethoxysilylpropyl-t-butyl carbamate (manufactured by gelest, SIT-8186.5)
b2: triethoxysilylpropyl ethyl carbonate (manufactured by gelest, SIT-8188.0)
b3: γ ureido triethoxysilane (manufactured by United chemical, UCT-801)

ｃ２：上記式（６−２）で表される化合物
ｃ３：上記式（１４）で表される化合物（株式会社ＡＤＥＫＡ製、商品名「アデカクルーズＮＣＩ−８３１）） In Table 1, the following compounds were used as the component (c).
c1: 1,2-octanedione, 1- [4- (phenylthio) -phenyl, 2- (O-benzoyloxime)] (trade name “IRGACURE OXE-01” manufactured by BASF Corporation)

c2: Compound represented by the above formula (6-2) c3: Compound represented by the above formula (14) (trade name “Adeka Cruz NCI-831” manufactured by ADEKA Corporation)

  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, underfill materials, etc., 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)

The following (a) component and (b) component , and
The resin composition containing the following (c) component .
(A) Polyimide precursor having a structural unit represented by the following general formula (1) (b) Compound represented by the following general formula (2)
(C) A compound represented by the following general formula (6), a compound represented by the following general formula (7), or a compound represented by the following general formula (8)

(In formula (1) , 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, a cycloalkyl group, or a carbon-carbon unsaturated divalent group. (It is a monovalent organic group having a heavy bond.)

(In Formula (2) , R ⁵ is each independently an alkyl group having 1 to 4 carbon atoms, R ⁶ is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, a is an integer of 0 to 3, and n Is an integer of 1 to 6, and R ⁷ is a group of the following general formula (3).)

(In Formula (3) , R ⁸ is a monovalent organic group derived from a secondary, tertiary alcohol or phenol.)

(In the formula (6), R and _{R 1} are each an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group.
R ₂ represents a hydrogen atom, —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH. )

(In Formula (7), R ₃ represents an alkyl group having 1 to 6 carbon atoms, and R ₄ represents —NO ₂ or R ₂₀ CO— (wherein R ₂₀ represents an aryl group). .
R ₅ and R ₆ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. )

(In Formula (8), R ₇ represents an alkyl group having 1 to 6 carbon atoms, and R ₈ is an organic group having an acetal bond. R ₉ and R ₁₀ are each an alkyl group having 1 to 12 carbon atoms. Represents a phenyl group or a tolyl group.) The resin composition according to claim 1, wherein R ² in the general formula (1) is a divalent organic group represented by the following general formula (4).

(In Formula (4) , R < ⁹ > -R < ¹⁶ > represents a hydrogen atom, a fluorine atom, or a monovalent organic group each independently, and at least 1 of R < ⁹ > -R < ¹⁶ > is a fluorine atom or a trifluoromethyl group. ) The resin composition according to claim 1 or 2, wherein R ² in the general formula (1) is a divalent organic group represented by the general formula (5).

(In Formula (5) , R ¹⁷ and R ¹⁸ each independently represents a fluorine atom or a trifluoromethyl group.) Content of the said (c) component is 0.01-30 mass parts with respect to 100 mass parts of said (a) component, The resin composition in any one of Claims 1-3 . The cured film formed from the resin composition in any one of Claims 1-4 . The manufacturing method of a cured film including the process of apply | coating the resin composition in any one of Claims 1-4 on a board | substrate, drying and forming a coating film, and the process of heat-processing a coating film. The pattern cured film formed from the resin composition in any one of Claims 1-4 . 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 irradiating the coating film formed in the step with an actinic ray, followed by development to form a pattern resin The manufacturing method of a pattern cured film including the process of obtaining a film | membrane, and the process of heat-processing the said pattern resin film.

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