Method for producing polyimide precursor, method for producing photosensitive resin composition, method for producing cured product, polyimide precursor, polyimide precursor composition, photosensitive resin composition, and semiconductor device

Abstract

A method for producing a polyimide precursor, including a step for reacting a polyamide acid and a vinyl ether compound having a (meth)acryloyl group in the presence of a polymerization inhibitor.

Description

Method for producing polyimide precursor, method for producing photosensitive resin composition, method for producing cured product, polyimide precursor, polyimide precursor composition, photosensitive resin composition, and semiconductor device

[0001] The present disclosure relates to a method for producing a polyimide precursor, a method for producing a photosensitive resin composition, a method for producing a cured product, a polyimide precursor, a polyimide precursor composition, a photosensitive resin composition, and a semiconductor device.

[0002] In recent years, organic materials with high heat resistance, such as polyimide resins, have been widely used as protective film materials for semiconductor integrated circuits (LSIs) (see, for example, Patent Document 1). Protective films (cured films) using such polyimide resins are obtained by applying a polyimide precursor or a resin composition containing the polyimide precursor to a substrate, drying the applied resin film, and then heating the resin film to cure it.

[0003] Japanese Patent Application Laid-Open No. 2016-199662

[0004] Examples of methods for producing polyimide precursors include the isoimide method and the acid chloride method. In these methods, after synthesizing the polymer, it is necessary to remove impurities, including fluorine, sulfur, and chlorine, derived from additives such as trifluoroacetic anhydride used in the isoimide method and thionyl chloride used in the acid chloride method. Therefore, the polymer is reprecipitated and washed to remove the impurities, but the problem is that the impurities cannot be completely removed.

[0005] In light of the above issues, we are also investigating the synthesis of polyimide precursors by condensation methods that do not use additives containing fluorine, sulfur, chlorine, etc. In condensation methods, polyimide precursors are synthesized using, for example, carbodiimide compounds. However, condensation methods involve many reaction steps, and polyimide precursors obtained by condensation methods tend to have poor storage stability, presumably due to by-products. Furthermore, when polyimide precursors obtained by condensation methods are used in photosensitive resin compositions, the photosensitivity may be insufficient due to factors such as a reduced film retention rate upon curing or a reduced dissolution rate in solvents during development.

[0006] The present disclosure has been made in view of the above, and aims to provide a method for producing a polyimide precursor that can produce a photosensitive resin composition with excellent photosensitivity properties and can produce a polyimide precursor in a simple manner, as well as a method for producing a photosensitive resin composition and a method for producing a cured product using the production method. Furthermore, the present disclosure aims to provide a polyimide precursor that can produce a photosensitive resin composition with excellent photosensitivity properties, as well as a polyimide precursor composition, a photosensitive resin composition, and a semiconductor device that use the polyimide precursor.

[0007] Specific means for achieving the above object are as follows. <1> A method for producing a polyimide precursor, comprising the step of reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group in the presence of a polymerization inhibitor. <2> A method for producing a polyimide precursor according to <1>, further comprising the step of reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound to obtain the polyamic acid. <3> A method for producing a polyimide precursor according to <1> or <2>, wherein the polymerization inhibitor includes 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide. <4> A method for producing a polyimide precursor according to any one of <1> to <3>, wherein the molar ratio of the vinyl ether compound to the total of the tetracarboxylic dianhydride and the tetracarboxylic acid is 2 to 5. <5> A method for producing a polyimide precursor according to any one of <1> to <4>, wherein the vinyl ether compound includes 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. <6> The method for producing a polyimide precursor according to any one of <1> to <5>, wherein the step of obtaining a polyamic acid comprises reacting the tetracarboxylic dianhydride with the diamine compound in a solvent, the solvent containing a compound containing neither a nitrogen atom nor a sulfur atom in the molecule. <7> The method for producing a polyimide precursor according to <6>, the solvent containing at least one selected from the group consisting of γ-butyrolactone, cyclopentanone, a mixed solvent of 3-methoxy-3-methyl-1-butanol and propylene carbonate, and a mixed solvent of γ-butyrolactone and 3-methoxy-N,N-dimethylpropanamide. <8> A method for producing a photosensitive resin composition, the method comprising: producing a polyimide precursor by the method for producing a polyimide precursor according to any one of <1> to <7>; and producing a photosensitive resin composition using the polyimide precursor. <9> A method for producing a cured product, the method comprising producing a photosensitive resin composition by the method for producing a photosensitive resin composition according to <8>, and curing the produced photosensitive resin composition to produce a cured product. <10> A polymerizable compound including a structural unit represented by general formula (1) and a structural unit represented by general formula (2), wherein R of the structural unit represented by general formula (1) ６ and R ７a polyimide precursor in which, of the total of the above, a ratio of a structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group to a structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound is 40 mol % or more.

[0008]

[0009]

[0010] In general formula (1), X represents a tetravalent organic group, R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, and R ６ and R ７ At least one of the above is a monovalent organic group containing a (meth)acryloyl group, * represents a bonding position, and in general formula (2), Y represents a divalent organic group, and * represents a bonding position.

[0011] <11> R contained in polyimide precursor ６ and R ７ At least one of the structural units is a structural unit represented by the following general formula (3):

[0012]

[0013] In general formula (3), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group; R ８ represents a monovalent organic group containing a (meth)acryloyl group, and * represents a bonding position.

[0014] <12> A polyimide precursor composition comprising: a polyimide precursor including a structural unit represented by general formula (1) and a structural unit represented by general formula (2); and a polymerization inhibitor.

[0015]

[0016]

[0017] In general formula (1), X represents a tetravalent organic group, R６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, and R ６ and R ７ At least one of the R in the polyimide precursor is a structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group, and is a monovalent organic group containing a (meth)acryloyl group, and * represents a bonding site, and in general formula (2), Y represents a divalent organic group, and * represents a bonding site. ６ and R ７ The polyimide precursor composition according to <12>, wherein at least one of the structural units is represented by the following general formula (3):

[0018]

[0019] In general formula (3), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group; R ８ represents a monovalent organic group containing a (meth)acryloyl group, and * represents a bonding position.

[0020] <14> The polyimide precursor composition according to <12> or <13>, wherein the polymerization inhibitor includes 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide. <15> A photosensitive resin composition comprising the polyimide precursor according to <10> or <11> or the polyimide precursor composition according to any one of <12> to <14>. <16> A semiconductor device comprising a cured product obtained by curing the photosensitive resin composition according to <15>.

[0021] According to the present disclosure, it is possible to provide a method for producing a polyimide precursor that can produce a photosensitive resin composition having excellent photosensitivity properties and can produce a polyimide precursor in a simple manner, as well as a method for producing a photosensitive resin composition and a method for producing a cured product using the production method. According to the present disclosure, it is possible to provide a polyimide precursor that can produce a photosensitive resin composition having excellent photosensitivity properties, as well as a polyimide precursor composition, a photosensitive resin composition, and a semiconductor device using the same.

[0022] 1 is a diagram illustrating a manufacturing process of an electronic component according to an embodiment of the present disclosure; 2 is a graph illustrating the relationship between the exposure dose and the remaining film ratio in each example and comparative example;

[0023] Modes for carrying out the present disclosure are described in detail below. However, the present disclosure is not limited to the following embodiments. In the present disclosure, components (including elementary steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure. In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple corresponding substances. When a composition contains multiple substances corresponding to each component, the content or amount of each component refers to the total content or amount of the multiple substances present in the composition, unless otherwise specified. In this disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire area when the layer or film is observed, as well as cases where the layer or film is formed only over a portion of the area. In this disclosure, the thickness of a layer or film refers to the maximum thickness of the layer or film in question. The thickness of a layer or film can be measured using an optical interference film thickness measuring device, a micrometer, or the like. In this disclosure, when the thickness of a layer or film can be measured directly, it is measured using an optical interference film thickness measuring device or a micrometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing the cross section of the object to be measured using an electron microscope.

[0024] In the present disclosure, "(meth)acrylic" means "acrylic" and "methacrylic", "(meth)acrylate" means "acrylate" and "methacrylate", and "(meth)acryloyl group" means "acryloyl group" and "methacryloyl group". In the present disclosure, the concept of "insulating film" also encompasses insulating layers. In the present disclosure, when a functional group has a substituent, the number of carbon atoms in the functional group refers to the total number of carbon atoms including the number of carbon atoms in the substituent. In the present disclosure, when embodiments are described with reference to drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of components in each drawing are conceptual, and the relative size relationships between components are not limited thereto.

[0025] <Method for Producing Polyimide Precursor> The method for producing a polyimide precursor according to the present disclosure includes a step of reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group in the presence of a polymerization inhibitor.

[0026] In the method for producing a polyimide precursor of the present disclosure, a polyamic acid is reacted with a vinyl ether compound having a (meth)acryloyl group (hereinafter also referred to as a "specific vinyl ether compound") in the presence of a polymerization inhibitor. This allows the carboxy group contained in the polyamic acid to react with the vinyl group contained in the specific vinyl ether compound, thereby producing a polyimide precursor having a (meth)acryloyl group. Such a polyimide precursor can be suitably used in the preparation of a photosensitive resin composition. A photosensitive resin composition containing a polyimide precursor produced by the method of the present disclosure has excellent photosensitive properties, such as the ability to produce a cured product with a high film retention rate and a high dissolution rate in solvents during development.

[0027] The polyamic acid to be reacted with the specific vinyl ether compound is preferably a compound obtained by reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound. The method for producing a polyimide precursor according to the present disclosure may further include a step of reacting the tetracarboxylic dianhydride or the tetracarboxylic acid with a diamine compound to obtain the polyamic acid.

[0028] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenonetetracarboxylic dianhydride, 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-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2- Examples of the dianhydride include 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, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone bisspironorbornane tetracarboxylic dianhydride, and 2,2-bis{4-(4'-phenoxy)phenyl}propane tetracarboxylic dianhydride.Among these, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, or 4,4'-oxydiphthalic acid dianhydride is preferred, and from the viewpoint of bonding at lower temperatures, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride is more preferred. The tetracarboxylic acid dianhydride may be used alone or in combination of two or more.

[0029] Specific examples of the tetracarboxylic acid include various compounds of the above-mentioned specific examples of the tetracarboxylic dianhydride, excluding the term "dianhydride." For example, 3,3',4,4'-biphenyl ether tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, or 4,4'-oxydiphthalic acid is preferred, and from the viewpoint of bonding at lower temperatures, 3,3',4,4'-biphenyl ether tetracarboxylic acid is more preferred.

[0030] Specific examples of the diamine compound include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, and 2,4'-diaminodiphenyl ether. , 2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6- diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-amino (aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,Examples of the diamine compound include 9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. Preferred diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. Among these, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane are more preferred from the viewpoint of having a flexible skeleton and excellent adhesiveness. The diamine compounds may be used alone or in combination of two or more.

[0031] The polyamic acid may have a nonvolatile crosslinking group at the end of the main chain. The nonvolatile crosslinking group is a functional group capable of crosslinking, which is located at the end of the main chain of the polyamic acid and does not volatilize upon heating, drying, etc. The nonvolatile crosslinking group may be a functional group containing an unsaturated double bond.

[0032] When a tetracarboxylic dianhydride or tetracarboxylic acid is reacted with a diamine compound to obtain a polyamic acid, a compound that forms a nonvolatile crosslinking group at the main chain end of the polyamic acid (hereinafter also referred to as a nonvolatile crosslinking group-forming compound) may be further reacted. Examples of nonvolatile crosslinking group-forming compounds include maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, methacrylic anhydride, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-ethynylphthalic anhydride, 4-vinylphthalic anhydride, and di-t-butyl dicarbonate. These compounds react with amino groups derived from the diamine compound to obtain a compound having a nonvolatile crosslinking group at the main chain end. One type of nonvolatile crosslinking group-forming compound may be used alone, or two or more types may be used in combination.

[0033] When obtaining a polyamic acid, the molar ratio of the total of the tetracarboxylic dianhydride and the tetracarboxylic acid (which may be read as "the total of the tetracarboxylic dianhydride, the tetracarboxylic acid, and the non-volatile cross-linking group-forming compound") to the diamine compound (total of the tetracarboxylic dianhydride and the tetracarboxylic acid:diamine compound) may be 5:10 to 15:10, 7:10 to 10:10, or 8:10 to 9.5:10.

[0034] When the tetracarboxylic dianhydride or tetracarboxylic acid is reacted with the diamine compound, an organic solvent may be used. The organic solvent may be used alone or in combination of two or more kinds.

[0035] The organic solvent preferably contains a compound that does not contain a nitrogen atom or a sulfur atom in its molecule. This tends to facilitate the reaction between the tetracarboxylic dianhydride or tetracarboxylic acid and the diamine compound. The organic solvent may be a compound that does not contain a nitrogen atom or a sulfur atom in its molecule, or a mixed solvent of a compound that does not contain a nitrogen atom or a sulfur atom in its molecule and a compound that contains at least one of a nitrogen atom and a sulfur atom in its molecule.

[0036] Examples of the organic solvent include γ-butyrolactone, cyclopentanone, a mixed solvent of 3-methoxy-3-methyl-1-butanol and propylene carbonate, and a mixed solvent of γ-butyrolactone and 3-methoxy-N,N-dimethylpropanamide.

[0037] The amount of the organic solvent used may be 1 to 10 times, or may be 2 to 5 times, the total mass of the raw materials used in the production of the polyamic acid.

[0038] A polyimide precursor is produced by reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group (specific vinyl ether compound) in the presence of a polymerization inhibitor. The polyamic acid may be a liquid containing the polyamic acid, or may be a liquid containing the polyamic acid and an organic solvent, for example.

[0039] Examples of the polymerization inhibitor include 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, and nitrosamines. Among these, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide is preferred. One type of polymerization inhibitor may be used alone, or two or more types may be used in combination.

[0040] The specific vinyl ether compound may be 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. Of these, 2-(2-vinyloxyethoxy)ethyl acrylate is preferred. The specific vinyl ether compound may be used alone or in combination of two or more.

[0041] When producing a polyimide precursor, vinyl ether compounds other than the specific vinyl ether compounds (also referred to as "other vinyl ether compounds") may be used. Examples of other vinyl ether compounds include vinyl ether compounds that do not have a (meth)acryloyl group. Specific examples include vinyl ether compounds having a linear or branched, saturated or unsaturated hydrocarbon skeleton, such as isopropyl vinyl ether, sec-butyl vinyl ether, and sec-pentyl vinyl ether; vinyl ether compounds containing an alicyclic saturated hydrocarbon skeleton, such as cyclohexyl vinyl ether, tricyclodecanyl vinyl ether, and pentacyclopentadecanyl vinyl ether; and vinyl ethers containing an ether bond in a linear or branched, saturated or unsaturated hydrocarbon skeleton, such as 1-methoxyethyl vinyl ether, 1-ethoxyethyl vinyl ether, 1-methyl-2-methoxyethyl vinyl ether, and 1-methyl-2-ethoxyethyl vinyl ether.

[0042] When producing a polyimide precursor, the amount of the specific vinyl ether compound used may be 50% by mass to 100% by mass, 70% by mass to 90% by mass, or 90% by mass to 100% by mass, based on the total mass of the specific vinyl ether compound and the other vinyl ether compounds.

[0043] When producing a polyimide precursor, the molar ratio of the vinyl ether compound (vinyl ether / tetracarboxylic acid+tetracarboxylic acid dianhydride) to the total of the tetracarboxylic acid and the tetracarboxylic acid (which may be read as "the total of the tetracarboxylic acid dianhydride, the tetracarboxylic acid, and the non-volatile cross-linking group-forming compound") may be 2 to 5, 2.5 to 4.5, or 3 to 4.

[0044] When producing a polyimide precursor, the amount of the polymerization inhibitor used may be 0.1% by mass to 1.0% by mass, 0.2% by mass to 0.8% by mass, or 0.2% by mass to 0.5% by mass, based on the total amount of raw materials for the polyimide precursor (for example, the total amount of tetracarboxylic dianhydride and tetracarboxylic acid, the diamine compound, and the specific vinyl ether compound).

[0045] <Polyimide Precursor> The polyimide precursor of the present disclosure includes a structural unit represented by general formula (1) and a structural unit represented by general formula (2), and R of the structural unit represented by general formula (1) ６ and R ７ Of the total, the ratio of the structure formed by the reaction of a vinyl group with a carboxy group in the vinyl ether compound having a (meth)acryloyl group to the structure formed by the reaction of a vinyl group with a carboxy group in the vinyl ether compound (hereinafter also referred to as the specific ratio) is 40 mol % or more. The polyimide precursor of the present disclosure makes it possible to produce a photosensitive resin composition with excellent photosensitivity properties. The specific ratio may be 50 mol % to 100 mol %, or may be 70 mol % to 100 mol %.

[0046]

[0047]

[0048] In general formula (1), X represents a tetravalent organic group, R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, and R ６ and R ７ At least one of the above is a monovalent organic group containing a (meth)acryloyl group, * represents a bonding position, and in general formula (2), Y represents a divalent organic group, and * represents a bonding position.

[0049] The reaction formula between a vinyl ether compound (compound (b) shown below) and a compound having a carboxy group (compound (a) shown below) is as follows. This results in a compound (c) having a structure formed by the reaction of the vinyl group and the carboxy group in the vinyl ether compound. Note that the following reaction is an example, and the present disclosure is not limited thereto.

[0050]

[0051] The polyimide precursor may have a plurality of structural units represented by the general formula (1) or a plurality of structural units represented by the general formula (2), and X, Y, R in the plurality of structural units ６ and R ７ may be the same or different. ６ and R ７ are each independently a hydrogen atom or a monovalent organic group, the combination of which is not particularly limited. For example, R ６ and R ７ At least one of R may be a hydrogen atom and the rest may be a monovalent organic group described later, or they may be the same or different monovalent organic groups. ６ and R ７ The combinations may be the same or different.

[0052] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may contain an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (e.g., aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., heterocyclic rings having 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent on the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group. When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be connected by a single bond, or may be connected by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or greater.) or a composite linking group comprising at least two of these linking groups. Furthermore, two benzene rings may be linked at two positions by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

[0053] In the general formula (1), -COOR ６The —COOR group and the —CO— group are preferably in the ortho position relative to each other, ７ The group and the —CO— group are preferably in the ortho position relative to each other.

[0054] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulae (A) to (F). Among them, from the viewpoint of excellent flexibility, a group represented by the following formula (E) is preferred, and in the formula (E) below, C is more preferably a group containing an ether bond, and even more preferably an ether bond. The following formula (F) is a structure in which C in the following formula (E) is a single bond. It should be noted that the present disclosure is not limited to the following specific examples.

[0055]

[0056] In formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups that are not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represent a hydrogen atom, an alkyl group, or a phenyl group. Among these, A and B each independently preferably represent a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.

[0057] In formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R'sＢ each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group combining at least two of these. C preferably contains an ether bond, and is preferably an ether bond. C may also contain a structure represented by the following formula (C1):

[0058]

[0059] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethylethylene group, a branched-chain alkylene groups such as 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene; and the like. Among these, a methylene group is preferred.

[0060] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in formula (E) above has been substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.

[0061] R contained in the silylene bond or siloxane bond Ａ or R Ｂ The alkyl group represented by R is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Ａ or R Ｂ Specific examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0062] Specific examples of the tetravalent organic group represented by X may be groups represented by the following formulae (J) to (O).

[0063]

[0064] In general formula (2), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bonding positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of the divalent aromatic group include a divalent aromatic hydrocarbon group (for example, an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (for example, a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.

[0065] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formulae (G) and (H).

[0066]

[0067] In formulas (G) to (H), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents an integer of 0 to 4. In formula (H), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂeach independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group combining at least two of them. D may also be a structure represented by the above formula (C1). Specific examples of D in formula (H) are the same as the specific examples of C in formula (E). As D in formula (H), each independently is preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, or the like.

[0068] The alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in formulas (G) to (H) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0069] The alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (H) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0070] The halogenated alkyl group represented by R in formulas (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0071] In formulae (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0072] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, and a divalent group having a polyalkylene oxide structure.

[0073] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.

[0074] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.

[0075] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Of these, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be of one type or two or more types.

[0076] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a 2-ethylhexyl group, and an n-dodecyl group. Among these, a methyl group is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of the substituent in the aryl group include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Of these, a phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or of two or more types. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0077] The group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H'), formula (H'') or formula (H''').

[0078]

[0079] In formula (H'''), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0080] In the general formulas (1) and (2), the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited.

[0081] R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, and R ６ and R ７ At least one of the groups is a monovalent organic group containing a (meth)acryloyl group.

[0082] R contained in the polyimide precursor ６ and R ７ At least one of the above is preferably a structural unit represented by the following general formula (3).

[0083]

[0084] In general formula (3), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group; R ８ represents a monovalent organic group containing a (meth)acryloyl group, and * represents a bonding position. １ , R ２ and R ３ is preferably a hydrogen atom.

[0085] R ８ The monovalent organic group containing a (meth)acryloyl group in the formula (I) may have 1 to 10 carbon atoms, or 2 to 5 carbon atoms, excluding the (meth)acryloyl group.

[0086] R ８ The monovalent organic group containing a (meth)acryloyl group in the formula (1) may be a group represented by the following general formula (4).

[0087]

[0088] In general formula (4), R ９ ~R １１ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘ represents a divalent linking group, and * represents the bonding position.

[0089] R in general formula (4) ９ ~R １１ The aliphatic hydrocarbon group represented by R has 1 to 3 carbon atoms, preferably 1 or 2. ９ ~R １１ Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0090] R in general formula (4) ９ ~R １１ As a combination of ９ and R １０ is a hydrogen atom, and R １１ is preferably a hydrogen atom or a methyl group.

[0091] R in general formula (4) ｘ is a divalent linking group, and may have 1 to 10 carbon atoms or 2 to 5 carbon atoms. ｘ Preferably, contains an ether bond.

[0092] In general formula (1), R ６ and R ７ At least one of R is preferably a group represented by the general formula (4), ６ and R ７ It is more preferable that both of the above are groups represented by the general formula (4).

[0093] When the polyimide precursor contains a compound having a structural unit represented by the general formula (1), the R６ and R ７ R which is a group represented by general formula (4) ６ and R ７ The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. The upper limit is not particularly limited and may be 100 mol%. The proportion may be 0 mol% or more and less than 60 mol%.

[0094] <Polyimide precursor composition> The polyimide precursor composition of the present disclosure comprises a polyimide precursor comprising a structural unit represented by the aforementioned general formula (1) and a structural unit represented by the aforementioned general formula (2), and a polymerization inhibitor. The polyimide precursor composition of the present disclosure makes it possible to produce a photosensitive resin composition with excellent photosensitivity properties. The polyimide precursor contained in the polyimide precursor composition of the present disclosure differs from the polyimide precursor of the present disclosure in that the ratio of the structure formed by the reaction of a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group to the structure formed by the reaction of a vinyl group and a carboxy group in a vinyl ether compound is not particularly limited. Preferred forms of the polyimide precursor contained in the polyimide precursor composition of the present disclosure are the same as the preferred forms of the polyimide precursor of the present disclosure.

[0095] Examples of polymerization inhibitors contained in the polyimide precursor composition of the present disclosure include 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, and nitrosamines. Among these, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide is preferred. One type of polymerization inhibitor may be used alone, or two or more types may be used in combination.

[0096] The content of the polymerization inhibitor may be 0.1% by mass to 1.0% by mass, 0.2% by mass to 0.8% by mass, or 0.2% by mass to 0.5% by mass, relative to the total amount of the polyimide precursor composition.

[0097] <Method for producing photosensitive resin composition> The method for producing a photosensitive resin composition of the present disclosure includes a step of producing a polyimide precursor by the method for producing a polyimide precursor of the present disclosure, and a step of producing a photosensitive resin composition using the polyimide precursor. By using the polyimide precursor produced by the production method of the present disclosure, it is possible to produce a cured product with a high film retention rate, and a photosensitive resin composition with excellent photosensitivity properties such as a high dissolution rate in a solvent during development can be produced.

[0098] A photosensitive resin composition can be produced by mixing the polyimide precursor produced by the method for producing a polyimide precursor of the present disclosure with other components. The other components are not particularly limited and include, but are not limited to, solvents, polymerizable monomers, photopolymerization initiators, sensitizers, coupling agents, thermal polymerization initiators, polymerization inhibitors, antioxidants, surfactants, leveling agents, rust inhibitors, nitrogen-containing compounds, dicarboxylic acids, fillers, etc., and the composition may contain at least one component selected from these. The polyimide precursor produced by the method for producing a polyimide precursor of the present disclosure may be, for example, a polyimide precursor solution in which a polyimide precursor is dissolved in an organic solvent, or the polyimide precursor solution may be mixed with the other components described above.

[0099] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure includes the polyimide precursor of the present disclosure or the polyimide precursor composition of the present disclosure. The photosensitive resin composition may include other components exemplified in the method for producing a polyimide precursor of the present disclosure.

[0100] <Method for producing a cured product> The method for producing a cured product of the present disclosure includes the steps of producing a photosensitive resin composition using the method for producing a photosensitive resin composition of the present disclosure and curing the produced photosensitive resin composition to produce a cured product. The photosensitive resin composition used to produce the cured product may be either negative or positive.

[0101] The cured product may be a patterned cured product or a non-patterned cured product. The average thickness of the cured product is preferably 5 μm to 20 μm.

[0102] When the cured product is a patterned cured product, the method for producing the patterned cured product preferably includes the steps of applying a photosensitive resin composition onto a substrate and drying to form a photosensitive resin film, exposing the photosensitive resin film to a pattern to obtain a resin film, developing the resin film after the patterned exposure using a developer to obtain a patterned resin film, and heat-treating the patterned resin film.

[0103] When the cured product has no pattern, the method for producing the pattern-free cured product includes a step of forming a photosensitive resin film and a step of performing a heat treatment. It may further include a step of exposing the film to light.

[0104] The substrate may be a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), or a TiO ２ Substrate, SiO ２ Examples of the substrate include a metal oxide insulator substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

[0105] The method for applying the photosensitive resin composition of the present disclosure is not particularly limited, and can be carried out using a spinner or the like.

[0106] Drying can be carried out using a hot plate, oven, or the like. The drying temperature is preferably 80°C to 150°C, and from the viewpoint of ensuring dissolution contrast, more preferably 80°C to 120°C. The drying time is preferably 30 seconds to 5 minutes. Drying may be carried out two or more times. This makes it possible to obtain a photosensitive resin film in which the photosensitive resin composition is formed into a film.

[0107] The average thickness of the photosensitive resin film is preferably 5 μm to 100 μm, more preferably 6 μm to 50 μm, and even more preferably 7 μm to 30 μm.

[0108] The pattern exposure is performed by exposing the film to a predetermined pattern through a photomask, for example. The actinic ray to be irradiated may be ultraviolet light such as i-ray, visible light, or radiation, but i-ray is preferred. The exposure device may be a parallel exposure device, an aligner, a projection exposure device, a stepper, a scanner exposure device, or the like.

[0109] By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed areas are removed with a developer. As the developer, a good solvent for the photosensitive resin film can be used alone, or an appropriate mixture of a good solvent and a poor solvent can be used. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, and cyclohexanone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0110] A surfactant may be added to the developer in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.

[0111] The development time can be, for example, twice the time required for the photosensitive resin film to be immersed and completely dissolved. The development time varies depending on the polyimide precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from the viewpoint of productivity, even more preferably 20 seconds to 5 minutes.

[0112] After development, the resist may be washed with a rinse solution, such as distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, or propylene glycol monomethyl ether, which may be used alone or in appropriate mixtures, or in stepwise combinations.

[0113] A patterned cured product can be obtained by heat-treating the patterned resin film, in which the polyimide precursor undergoes a dehydration ring-closing reaction to form the corresponding polyimide resin.

[0114] The temperature of the heat treatment is preferably 250° C. or less, more preferably 120° C. to 250° C., and even more preferably 160° C. to 200° C. By keeping the heat treatment temperature within the above range, damage to the substrate or device can be minimized, devices can be produced with a high yield, and energy savings can be achieved in the process.

[0115] The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. By keeping the heat treatment time within the above range, the crosslinking reaction or the dehydration ring-closing reaction can be sufficiently progressed. The heat treatment atmosphere may be air or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the patterned resin film.

[0116] Examples of equipment used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealer, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0117] The cured product can be used as an interlayer insulating film, a cover coat layer, or a surface protective film. Furthermore, the cured product can be used as a passivation film, a buffer coat film, etc. Highly reliable electronic components such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (such as multi-die fan-out wafer-level packages) can be manufactured using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, and surface protective film.

[0118] <Semiconductor Device> The semiconductor device of the present disclosure includes a cured product obtained by curing the photosensitive resin composition of the present disclosure described above.

[0119] An example of a manufacturing process for a semiconductor device according to the present disclosure will be described with reference to the drawings. Figure 1 is a diagram illustrating a manufacturing process for a semiconductor device having a multilayer wiring structure according to an embodiment of the present disclosure. In Figure 1, a semiconductor substrate 1, such as a Si substrate, having circuit elements is covered with a protective film 2, such as a silicon oxide film, except for predetermined portions of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. An interlayer insulating film 4 is then formed on the semiconductor substrate 1.

[0120] Next, a photosensitive resin layer 5 such as a chlorinated rubber or phenol novolac resin is formed on the interlayer insulating film 4, and windows 6A are formed by known photoetching techniques so that predetermined portions of the interlayer insulating film 4 are exposed.

[0121] The interlayer insulating film 4 where the window 6A is exposed is selectively etched to provide a window 6B. Next, the photosensitive resin layer 5 is removed using an etching solution that corrodes the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed through the window 6B.

[0122] Furthermore, a second conductor layer 7 is formed using a known photolithography technique, and electrically connected to the first conductor layer 3. When forming a multilayer wiring structure having three or more layers, the above steps can be repeated to form each layer.

[0123] Next, the photosensitive resin composition of the present disclosure is used to open windows 6C by pattern exposure, and a surface protective film 8 is formed. The surface protective film 8 protects the second conductor layer 7 from external stress, alpha rays, etc., and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film 4 can also be formed using the photosensitive resin composition of the present disclosure.

[0124] The present disclosure will be described in more detail below based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0125] Example 1 Synthesis Example 1 (Synthesis of A1) 48.38 parts by mass of γ-butyrolactone as a solvent was added to a 100 mL separable flask, followed by the addition of 1.75 parts by mass (0.0162 mol) of paraphenylenediamine (PPD) and 3.44 parts by mass (0.0162 mol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP), which were diamine compounds, and the mixture was stirred to dissolve the diamine compounds in the solvent. 6.70 parts by mass (0.0216 mol) of 4,4'-oxydiphthalic anhydride (ODPA) and 4.24 parts by mass (0.0144 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), which were tetracarboxylic dianhydrides, were added to the resulting mixture, and the mixture was stirred at 60°C for 6 hours to obtain a polyamic acid. To the reaction liquid containing polyamic acid, 0.129 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and then 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was added, and the mixture was stirred at 60°C for 6 hours to obtain a reaction liquid containing a polyimide precursor (A1).

[0126] 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) was added to the reaction liquid containing the polyimide precursor (A1) so that the amount was 2% by mass relative to the polyimide precursor (A1), thereby obtaining a photosensitive resin composition of Example 1.

[0127] Example 2 A reaction solution containing a polyimide precursor (A2) was obtained in the same manner as in Example 1, except that the amount of the polymerization inhibitor was changed to 0.119 parts by mass and the amount of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) was changed to 23.46 parts by mass (0.1260 mol).

[0128] 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) was added to the reaction liquid containing the polyimide precursor (A2) so that the amount was 2% by mass relative to the polyimide precursor (A2), thereby obtaining a photosensitive resin composition of Example 1.

[0129] Example 3 A reaction solution containing a polyimide precursor (A3) was obtained in the same manner as in Example 1, except that the amount of the polymerization inhibitor was changed to 0.109 parts by mass and the amount of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) was changed to 20.11 parts by mass (0.1080 mol).

[0130] 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) was added to the reaction liquid containing the polyimide precursor (A3) so that the amount was 2% by mass relative to the polyimide precursor (A3), thereby obtaining the photosensitive resin composition of Example 1.

[0131] Example 4 Synthesis Example 4 (Synthesis of A4) 45.4 parts by mass of γ-butyrolactone as a solvent was added to a 100 mL separable flask, and then 1.75 parts by mass (0.0162 mol) of paraphenylenediamine (PPD) and 3.44 parts by mass (0.0162 mol) of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) as diamine compounds were added, followed by stirring to dissolve the diamine compounds in the solvent. To the resulting mixture were added 5.58 parts by mass (0.0180 mol) of 4,4'-oxydiphthalic anhydride (ODPA) and 3.18 parts by mass (0.0108 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), which were tetracarboxylic dianhydrides, and 1.18 parts by mass (0.0072 mol) of 5-norbornene-2,3-dicarboxylic anhydride, which was a dicarboxylic anhydride, and the mixture was stirred at 60°C for 6 hours to obtain a polyamic acid. To the reaction liquid containing polyamic acid, 0.126 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and then 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was added, and the mixture was stirred at 60°C for 6 hours to obtain a reaction liquid containing a polyimide precursor (A4).

[0132] 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) was added to the reaction liquid containing the polyimide precursor (A4) so ​​that the amount was 2% by mass relative to the polyimide precursor (A4), thereby obtaining a photosensitive resin composition of Example 4.

[0133] Example 5 Synthesis Example 5 (Synthesis of A5) 44.54 parts by mass of γ-butyrolactone as a solvent was added to a 100 mL separable flask, followed by the addition of 1.75 parts by mass (0.0162 mol) of paraphenylenediamine (PPD) and 3.44 parts by mass (0.0162 mol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP), which were diamine compounds, and the mixture was stirred to dissolve the diamine compounds in the solvent. 8.47 parts by mass (0.0288 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), which was a tetracarboxylic dianhydride, and 1.18 parts by mass (0.0072 mol) of 5-norbornene-2,3-dicarboxylic anhydride were added to the resulting mixture, which was then stirred at 60°C for 6 hours to obtain a polyamic acid. To the reaction liquid containing polyamic acid, 0.125 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and then 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was added, and the mixture was stirred at 60°C for 6 hours to obtain a reaction liquid containing a polyimide precursor (A5).

[0134] 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) was added to the reaction liquid containing the polyimide precursor (A5) so as to be 2% by mass relative to the polyimide precursor (A5), thereby obtaining a photosensitive resin composition of Example 5.

[0135] [Example 6] (Synthesis Example 6 (Synthesis of A6)) 54.14 parts by mass of γ-butyrolactone as a solvent was added to a 100 mL separable flask, followed by the addition of 6.88 parts by mass (0.0324 mol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) as a diamine compound, and stirring to dissolve the diamine compound in the solvent. 11.17 parts by mass (0.0360 mol) of 4,4'-oxydiphthalic anhydride (ODPA) as a tetracarboxylic dianhydride was added to the resulting mixture, and stirring was continued at 60°C for 6 hours to obtain a polyamic acid. To the reaction liquid containing polyamic acid, 0.135 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and then 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was added, and the mixture was stirred at 60°C for 6 hours to obtain a reaction liquid containing a polyimide precursor (A6).

[0136] 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) was added to the reaction liquid containing the polyimide precursor (A6) so that the amount was 2% by mass relative to the polyimide precursor (A6), thereby obtaining a photosensitive resin composition of Example 6.

[0137] Comparative Example 1 Synthesis Example 7 (Synthesis of A7) 258.5 parts by mass of γ-butyrolactone, 258.5 parts by mass of dimethyl sulfoxide, and 67.0 parts by mass (0.216 mol) of 4,4′-oxydiphthalic anhydride (ODPA) as a tetracarboxylic dianhydride were added to a 1000 mL plastic bottle, and then 59.3 parts by mass (0.456 mol) of hydroxyethyl methacrylate (HEMA), and catalytic amounts of 1,8-diazabicycloundecene (DBU) and 0.23 parts by mass (0.00216 mol) of benzoquinone (BQ) were further added. In another 1000 mL plastic bottle, 159.5 parts by mass of γ-butyrolactone, 159.5 parts by mass of dimethyl sulfoxide, and 42.4 parts by mass (0.144 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) were added, and 39.4 parts by mass (0.302 mol) of hydroxyethyl methacrylate (HEMA), and catalytic amounts of 1,8-diazabicycloundecene (DBU) and 0.156 parts by mass (0.00144 mol) of benzoquinone (BQ) were further added. After stirring for 48 hours, each mixture was added to a 3000 mL separable flask and 1-hydroxybenzotriazole monohydrate (HOBt.H ２ 113.0 parts by mass (0.738 mol) of diisopropylcarbodiimide (DIC) was added to the mixture and stirred for 60 minutes. Next, 93.1 parts by mass (0.738 mol) of diisopropylcarbodiimide (DIC) was added to the mixture and stirred for 120 minutes. Thereafter, a solution prepared by dissolving 17.5 parts by mass (0.0162 mol) of diamine compounds paraphenylenediamine (PPD) and 34.4 parts by mass (0.162 mol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) in 102.0 parts by mass of γ-butyrolactone and 102.0 parts by mass of dimethyl sulfoxide was added, and the mixture was stirred overnight. By-products were filtered off to obtain a reaction solution containing polyimide precursor (A7). This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration, washed several times, and then dried under reduced pressure to obtain polyimide precursor (A7).

[0138] To 100 parts by mass of the dried polyimide precursor (A7), 0.44 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide, 45 parts by mass of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark), 164 parts by mass of γ-butyrolactone, and 2 parts by mass of 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) were added to obtain a photosensitive resin composition of Comparative Example 1.

[0139] (Measurement of Dissolution Rate) The obtained photosensitive resin composition was spin-coated onto a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited) and dried at 100°C for 200 seconds to form a photosensitive resin film with a dry film thickness as shown in Table 1. The obtained photosensitive resin film was immersed in cyclopentanone for 7 seconds, and the dissolved film thickness was measured. Furthermore, the dissolution rate (μm / s) was measured from the remaining film thickness. The results are shown in Table 1.

[0140] (Measurement of film remaining rate) The obtained photosensitive resin composition was spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), and dried at 100°C for 200 seconds to form a photosensitive resin film. The dry film thickness of the obtained photosensitive resin film was measured. The rotation speed during spin coating was 1000 rpm (revolutions / min) in each example, and 2700 rpm in Comparative Example 1. In addition, a photosensitive resin film was formed in the same manner as above, and the obtained photosensitive resin film was exposed to light at an exposure dose of 100 mJ / cm using an i-line stepper NES2WA06 (manufactured by Nikon Corporation). ２ ~1100mJ / cm ２ The resin film after exposure and heating was subjected to puddle development in cyclopentanone using Act8 for a development time of 20 seconds (each Example) or 66 seconds (Comparative Example 1), and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film. Exposure dose: 100 mJ / cm ２ ~1100mJ / cm ２ The remaining film ratio of the patterned resin film under the above conditions was calculated based on the following formula. The results are shown in Table 2 and FIG. 2. Remaining film ratio (%) = 100 x (film thickness after development (μm) / dry film thickness (μm))

[0141]

[0142]

[0143] In Examples 1 to 6, as shown in Table 1, the dissolution rate was higher than that of Comparative Example 1, and as shown in Table 2 and Figure 2, the residual film rate was higher than that of Comparative Example 1. From the above points, photosensitive resin compositions having excellent photosensitivity properties were obtained in Examples 1 to 6.

[0144] All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

[0145] REFERENCE SIGNS LIST 1 semiconductor substrate 2 protective film 3 first conductor layer 4 interlayer insulating film 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductor layer 8 surface protective film

Claims

1. A method for producing a polyimide precursor, comprising the step of reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group in the presence of a polymerization inhibitor.

2. A method for producing a polyimide precursor according to claim 1, further comprising the step of reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound to obtain the polyamic acid.

3. The method for producing a polyimide precursor according to claim 1 or 2, wherein the polymerization inhibitor includes 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.

4. A method for producing a polyimide precursor according to any one of claims 1 to 3, wherein the molar ratio of the vinyl ether compound to the total of the tetracarboxylic dianhydride and tetracarboxylic acid is 2 to 5.

5. The method for producing a polyimide precursor according to any one of claims 1 to 4, wherein the vinyl ether compound includes 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

6. A method for producing a polyimide precursor according to any one of claims 1 to 5, wherein in the step of obtaining the polyamic acid, the tetracarboxylic dianhydride and the diamine compound are reacted in a solvent, and the solvent contains a compound that does not contain a nitrogen atom or a sulfur atom in the molecule.

7. The method for producing a polyimide precursor according to claim 6, wherein the solvent includes at least one selected from the group consisting of γ-butyrolactone, cyclopentanone, a mixed solvent of 3-methoxy-3-methyl-1-butanol and propylene carbonate, and a mixed solvent of γ-butyrolactone and 3-methoxy-N,N-dimethylpropanamide.

8. A method for producing a photosensitive resin composition, comprising: producing a polyimide precursor by the method for producing a polyimide precursor according to any one of claims 1 to 7; and producing a photosensitive resin composition using the polyimide precursor.

9. A method for producing a cured product, comprising the steps of producing a photosensitive resin composition using the method for producing a photosensitive resin composition according to claim 8, and curing the produced photosensitive resin composition to produce a cured product.

10. A compound comprising a structural unit represented by general formula (1) and a structural unit represented by general formula (2), wherein R of the structural unit represented by general formula (1) ６ and R ７ and wherein, of the total of the above, a ratio of a structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group to a structure formed by a reaction between a vinyl group and a carboxy group in the vinyl ether compound is 40 mol % or more. In the general formula (1), X represents a tetravalent organic group; ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, and R ６ and R ７ At least one of the above is a monovalent organic group containing a (meth)acryloyl group, * represents a bonding site, and in general formula (2), Y represents a divalent organic group, * represents a bonding site.

11. R contained in polyimide precursor ６ and R ７ The polyimide precursor according to claim 10 , wherein at least one of the structural units is represented by the following general formula (3): In general formula (3), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group; R ８ represents a monovalent organic group containing a (meth)acryloyl group, and * represents the bonding position.

12. A polyimide precursor composition comprising: a polyimide precursor containing a structural unit represented by general formula (1) and a structural unit represented by general formula (2); and a polymerization inhibitor. In the general formula (1), X represents a tetravalent organic group; ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group, and R ６ and R ７ at least one of the following is a structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group, and is a monovalent organic group containing a (meth)acryloyl group, * represents a bonding site, and in general formula (2), Y represents a divalent organic group, and * represents a bonding site.

13. R contained in polyimide precursor ６ and R ７ The polyimide precursor composition according to claim 12 , wherein at least one of the structural units is represented by the following general formula (3): In general formula (3), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group; R ８ represents a monovalent organic group containing a (meth)acryloyl group, and * represents the bonding position.

14. The polyimide precursor composition according to claim 12 or 13, wherein the polymerization inhibitor comprises 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.

15. A photosensitive resin composition comprising the polyimide precursor according to claim 10 or 11 or the polyimide precursor composition according to any one of claims 12 to 14.

16. A semiconductor device comprising a cured product obtained by curing the photosensitive resin composition according to claim 15.

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