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

Abstract

Provided is a method for producing a polyimide precursor composition, the method including a step in which a poly(amic acid) is reacted with a vinyl ether compound having a (meth)acryloyl group in a liquid comprising the poly(amic acid), the vinyl ether compound having a (meth)acryloyl group, and a polymerization inhibitor. A (meth)acryloyl-group-containing polyimide precursor which is a product of reaction between the poly(amic acid) and the vinyl ether compound having a (meth)acryloyl group comprises a structural unit represented by general formula (1) and a structural unit represented by general formula (2).

Description

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

[0001] This disclosure relates to a method for producing a polyimide precursor composition, a method for producing a photosensitive resin composition, a method for producing a cured product, 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). Such protective films (cured films) using polyimide resins are obtained by coating and drying a resin film formed by a polyimide precursor or a resin composition containing a polyimide precursor onto a substrate, and then heating and curing the resulting film.

[0003] Japanese Patent Publication No. 2016-199662

[0004] Methods for producing polyimide precursors include the isoimide method and the acid chromatography method. In these methods, after polymer synthesis, it is necessary to remove impurities containing fluorine, sulfur, chlorine, etc., derived from additives such as trifluoroacetic anhydride used in the isoimide method and thionyl chloride used in the acid chromatography method. Therefore, reprecipitation and washing of the polymer are performed to remove these impurities, but the inability to completely remove the impurities remains a challenge.

[0005] Based on the above challenges, we are also investigating the synthesis of polyimide precursors by a condensation method that does not use additives containing fluorine, sulfur, chlorine, etc. In the condensation method, polyimide precursors are synthesized using, for example, carbodiimide-based compounds. However, the condensation method involves many reaction steps, and polyimide precursors obtained by this method tend to exhibit poor storage stability, which is presumed to be due to by-products. Furthermore, when polyimide precursors obtained by the condensation method are applied to photosensitive resin compositions, the photosensitive properties may be insufficient due to factors such as a decrease in the residual film rate after curing or a decrease in the dissolution rate in the solvent during development.

[0006] The present inventors have intensively studied the above problems and considered reacting polyamic acid with a vinyl ether compound having a (meth)acryloyl group in the presence of a polymerization inhibitor. As a result, a polyimide precursor having a (meth)acryloyl group can be obtained by reacting the carboxy group contained in the polyamic acid with the vinyl group contained in a specific vinyl ether compound. By using a photosensitive resin composition containing such a polyimide precursor, a cured product having a high residual film ratio can be produced, and it has excellent photosensitive properties such as a high dissolution rate in a solvent during development.

[0007] On the other hand, the photosensitive resin composition containing the above-mentioned polyimide precursor is likely to gel or the viscosity is likely to increase during storage at room temperature, and there is room for improvement in terms of storage stability.

[0008] The present disclosure has been made in view of the above, and an object thereof is to provide a method for producing a polyimide precursor composition capable of producing a polyimide precursor composition excellent in storage stability, a method for producing a photosensitive resin composition using the production method, and a method for producing a cured product. Further, an object of the present disclosure is to provide a polyimide precursor composition excellent in storage stability, a photosensitive resin composition using the same, and a semiconductor device.

[0009] Specific means for achieving the above problems are as follows. <1> A step of reacting polyamic acid with a vinyl ether compound having a (meth)acryloyl group in a liquid containing polyamic acid, a vinyl ether compound having a (meth)acryloyl group, and a polymerization inhibitor, wherein the reaction product of the polyamic acid and the vinyl ether compound having a (meth)acryloyl group is a polyimide precursor having a (meth)acryloyl group, which is a polyimide precursor composition containing a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2).

[0010]

[0011]

[0012] In the general formula (1), X represents a tetravalent organic group not containing an aromatic ring, or when containing an aromatic ring, the aromatic ring is a tetravalent organic group not bonded to four carbonyl groups, and R６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, and is contained in the polyimide precursor. ６ and R ７At least one of the groups is a monovalent organic group containing a (meth)acryloyl group, where * represents the bond position, and in general formula (2), Y represents a divalent organic group, where * represents the bond position. <2> A method for producing a polyimide precursor composition according to <1>, further comprising the step of reacting a tetracarboxylic dianhydride or tetracarboxylic acid with a diamine compound to obtain the polyamic acid, wherein the tetracarboxylic dianhydride or tetracarboxylic acid is a compound that does not contain an aromatic ring, or a compound that contains an aromatic ring, the aromatic ring not bonded to four carbonyl groups. <4> A method for producing a polyimide precursor composition according to <2>, wherein the molar ratio of the vinyl ether compound to the total of the tetracarboxylic dianhydride and tetracarboxylic acid is 1 to 5. <4> A method for producing a polyimide precursor composition according to any one of <1> to <3>, wherein the polymerization inhibitor is 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide. <5> A method for producing a polyimide precursor composition according to any one of <1> to <4>, wherein the vinyl ether compound comprises 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. <6> A method for producing a polyimide precursor composition according to any one of <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 comprises a compound that does not contain nitrogen atoms or sulfur atoms in its molecule. <7> A method for producing a polyimide precursor composition according to <6>, wherein the solvent comprises 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 the steps of: producing a polyimide precursor composition by the method for producing a polyimide precursor composition according to any one of <1> to <7>; and producing a photosensitive resin composition using the polyimide precursor composition. <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 described in <8>, and curing the produced photosensitive resin composition to produce a cured product.<10> A polyimide precursor composition comprising a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and a polymerization inhibitor.

[0013]

[0014]

[0015] <11> R contained in the polyimide precursor ６ and R ７ The polyimide precursor composition according to <10>, wherein at least one of them is a structural unit represented by the following general formula (3).

[0016]

[0017] In the general formula (3), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group, and R ８ represents a monovalent organic group containing a (meth)acryloyl group, and * represents the bonding position. <12> The polyimide precursor composition according to <10> or <11>, wherein the polymerization inhibitor contains 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide. <13> A photosensitive resin composition containing the polyimide precursor composition according to any one of <10> to <12>. <14> A semiconductor device including a cured product obtained by curing the photosensitive resin composition according to <13>.

[0018] According to the present disclosure, it is possible to provide a method for producing a polyimide precursor composition capable of producing a polyimide precursor composition having excellent storage stability, and a method for producing a photosensitive resin composition and a cured product using the production method. According to the present disclosure, it is possible to provide a polyimide precursor composition having excellent storage stability, and a photosensitive resin composition and a semiconductor device using the same.

[0019] It is a manufacturing process diagram of an electronic component according to an embodiment of the present disclosure. It is a graph showing the relationship between the exposure amount and the residual film ratio for Example 1, 2 and Comparative Example 1.

[0020] The forms for implementing this disclosure are described in detail below. However, this disclosure is not limited to the following embodiments. In this disclosure, the components (including elemental steps, etc.) are not essential unless otherwise explicitly stated. The same applies to numerical values ​​and their ranges, and they do not limit this disclosure. In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that are not clearly distinguishable from other processes, if their purpose is achieved. In this disclosure, numerical ranges indicated using "~" include the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this 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. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple substances corresponding to each component exist in a composition, the content or amount of each component refers to the total content or amount of those multiple substances present in the composition, unless otherwise specified. In this disclosure, the terms "layer" or "film" include cases where the layer or film is formed over the entire region when the region in which it exists is observed, as well as cases where it is formed only on a part of the region. 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 interferometry film thickness analyzer, a micrometer, etc. In this disclosure, if the thickness of a layer or film can be measured directly, it shall be measured using an optical interferometry film thickness analyzer 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 a cross-section of the object to be measured using an electron microscope.

[0021] In this disclosure, "(meth)acrylic" means "acrylic" and "methacrylic," "(meth)acrylate" means "acrylate" and "methacrylate," and "(meth)acryloyl group" means "acryloyl group" and "methacryloyl group." In this disclosure, "insulating film" is a concept that also includes insulating layers. In this disclosure, when a functional group has substituents, the number of carbon atoms in the functional group means the total number of carbon atoms, including the carbon atoms of the substituents. When embodiments are described in this disclosure with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Also, the size of the components in each figure is conceptual, and the relative relationship of the sizes between components is not limited thereto.

[0022] <Method for Producing Polyimide Precursor Composition> The method for producing the polyimide precursor composition of the present disclosure comprises the step of reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group in a liquid containing a polyamic acid, a vinyl ether compound having a (meth)acryloyl group, and a polymerization inhibitor, wherein the polyimide precursor having a (meth)acryloyl group, which is the reaction product of the polyamic acid and the vinyl ether compound having a (meth)acryloyl group, includes a structural unit represented by general formula (1) and a structural unit represented by general formula (2).

[0023]

[0024]

[0025] In general formula (1), X represents a tetravalent organic group that does not contain an aromatic ring, or, if it contains an aromatic ring, a tetravalent organic group in which the aromatic ring is not bonded to four carbonyl groups, and R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, and is contained in the polyimide precursor. ６ and R ７ At least one of the groups is a monovalent organic group containing a (meth)acryloyl group, where * represents the bond position. In general formula (2), Y represents a divalent organic group, where * represents the bond position.

[0026] In the method for producing the polyimide precursor composition of this disclosure, a polyamic acid is reacted with a vinyl ether compound having a (meth)acryloyl group (hereinafter also referred to as "specific vinyl ether compound") in the presence of a polymerization inhibitor. This reaction between the carboxyl group in the polyamic acid and the vinyl group in the specific vinyl ether compound yields a polyimide precursor having a (meth)acryloyl group. Such a polyimide precursor can be suitably used in the preparation of photosensitive resin compositions.

[0027] Furthermore, the polyimide precursor contains a structural unit represented by general formula (1), where X is a tetravalent organic group that does not contain an aromatic ring, or, if it contains an aromatic ring, a tetravalent organic group in which the aromatic ring is not bonded to any of the four carbonyl groups. By containing such a structure in the polyimide precursor that does not contain an aromatic ring or in which the aromatic ring is not bonded to any of the carbonyl groups, the increase in the imidation rate and the decrease in the esterification rate in the polyimide precursor can be more effectively suppressed, resulting in excellent storage stability. This is presumed to be because the structural unit represented by general formula (1) in the polyimide precursor produced by the manufacturing method of this disclosure has lower acidity than the structural unit represented by general formula (1) that contains a tetravalent organic group in which the aromatic ring is bonded to any of the four carbonyl groups. Note that a tetravalent organic group in which the aromatic ring is not bonded to any of the four carbonyl groups means that the aromatic ring is not bonded to any of the four carbonyl groups.

[0028] The polyamic acid to be reacted with a specific vinyl ether compound is preferably a tetracarboxylic dianhydride or a compound obtained by reacting a tetracarboxylic acid with a diamine compound. The method for producing the polyimide precursor composition of this disclosure may further include a step of reacting a tetracarboxylic dianhydride or tetracarboxylic acid with a diamine compound to obtain the polyamic acid. In this case, the tetracarboxylic dianhydride or tetracarboxylic acid is preferably a compound that does not contain an aromatic ring, or a compound that contains an aromatic ring, the aromatic ring not being bonded to four carbonyl groups. The tetracarboxylic dianhydride, tetracarboxylic acid, and diamine compound may each be used independently, one alone or two or more in combination.

[0029] In the process of obtaining polyamic acid, it is preferable to use 50% to 100% by mass of a compound that does not contain an aromatic ring, or a compound that contains an aromatic ring but in which the aromatic ring is not bonded to four carbonyl groups, relative to the total amount of tetracarboxylic dianhydride or tetracarboxylic acid, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass.

[0030] Examples of tetracarboxylic dianhydrides (hereinafter also referred to as "specific tetracarboxylic dianhydrides") that do not contain an aromatic ring, or that contain an aromatic ring in which the aromatic ring is not bonded to four carbonyl groups, include the compounds represented by the following chemical formulas (A-1) to (A-6). Specific tetracarboxylic dianhydrides may be used individually or in combination of two or more. Examples of tetracarboxylic acids that do not contain an aromatic ring, or that contain an aromatic ring in which the aromatic ring is not bonded to four carbonyl groups, include the hydrolysates of the compounds represented by the following chemical formulas (A-1) to (A-6).

[0031]

[0032] The compounds represented by chemical formulas (A-1) and (A-5) are tetracarboxylic dianhydrides containing aromatic rings that are not bonded to the two acid anhydride groups. The compounds represented by chemical formulas (A-2) to (A-4) and the compound represented by chemical formula (A-6) are tetracarboxylic dianhydrides that do not contain aromatic rings.

[0033] The tetracarboxylic dianhydride preferably contains at least one of the compounds represented by chemical formula (A-2), chemical formula (A-4), and chemical formula (A-6). By synthesizing a polyamic acid using this compound and using it in the production of a photosensitive resin composition, it becomes easier to obtain a cured product with low stress.

[0034] In the process of obtaining polyamic acid, the tetracarboxylic dianhydride or tetracarboxylic acid may include a compound containing an aromatic ring, the aromatic ring of which is bonded to at least one carbonyl group.

[0035] Specific examples of tetracarboxylic dianhydrides, which are compounds containing an aromatic ring and in which the aromatic ring is bonded to at least one carbonyl group, 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, and 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, 1,1,4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane 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{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro Examples include -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 acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 2,2-bis{4-(4'-phenoxy)phenyl}propanetetracarboxylic acid 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 are preferred, and from the viewpoint of bonding at lower temperatures, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride is more preferred.

[0036] Specific examples of tetracarboxylic acids that contain an aromatic ring and whose aromatic ring is bonded to at least one carbonyl group include various compounds that are the same as the specific examples of tetracarboxylic dianhydrides mentioned above, but without 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 are preferred, and 3,3',4,4'-biphenyl ether tetracarboxylic acid is more preferred from the viewpoint of bonding at lower temperatures.

[0037] Specific examples of diamine compounds 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 ,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-A Minophenyl)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 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 adhesive properties. The diamine compounds may be used individually or in combination of two or more.

[0038] Polyamic acids may have non-volatile crosslinking groups at the ends of their main chains. These non-volatile crosslinking groups are functional groups located at the ends of the main chain of the polyamic acid that are capable of crosslinking reactions and do not volatilize due to heating, drying, etc. The non-volatile crosslinking groups may also include unsaturated double bonds.

[0039] When obtaining polyamic acid by reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound, a compound that forms a non-volatile crosslinking group at the main chain end of the polyamic acid (hereinafter also referred to as a non-volatile crosslinking group forming compound) may be further reacted. Examples of non-volatile crosslinking group forming compounds include maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, methacrylic anhydride, trimellitic anhydride, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-ethynyl phthalic anhydride, 4-vinyl phthalic anhydride, and di-t-butyl dicarbonate. These compounds react with amino groups derived from the diamine compound to obtain a compound having a non-volatile crosslinking group at the main chain end. One non-volatile crosslinking group forming compound may be used alone, or two or more may be used in combination.

[0040] When obtaining polyamic acid, the molar ratio of the total of tetracarboxylic dianhydride and tetracarboxylic acid (which may be read as "total of tetracarboxylic dianhydride, tetracarboxylic acid, and non-volatile crosslinking group forming compound") to the diamine compound (total of tetracarboxylic dianhydride and tetracarboxylic acid: diamine compound) may be 5:10 to 15:10, 7:10 to 10:10, or 8:10 to 9.5:10.

[0041] A solvent may be used when reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound. The solvent may be used alone or in combination of two or more solvents.

[0042] The aforementioned solvent preferably contains a compound that does not contain nitrogen or sulfur atoms in its molecule. This tends to facilitate the reaction between tetracarboxylic dianhydride or tetracarboxylic acid and diamine compounds. The solvent may consist of a compound that does not contain nitrogen or sulfur atoms in its molecule, or it may be a mixed solvent of a compound that does not contain nitrogen or sulfur atoms in its molecule and a compound that contains at least one of nitrogen or sulfur atoms in its molecule.

[0043] Examples of the aforementioned solvents 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.

[0044] The amount of solvent used may be 1 to 10 times, or 2 to 5 times, the total mass of the raw materials used in the production of polyamic acid.

[0045] A polyimide precursor is produced by reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group (a specific vinyl ether compound) in the presence of a polymerization inhibitor. The polyamic acid may be a liquid containing polyamic acid, for example, a liquid containing polyamic acid and a solvent.

[0046] Examples of polymerization inhibitors include 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, and nitrosamines. Among these, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide is preferred. Polymerization inhibitors may be used individually or in combination of two or more.

[0047] Examples of specific vinyl ether compounds include 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. Among these, 2-(2-vinyloxyethoxy)ethyl acrylate is preferred. A single specific vinyl ether compound may be used, or two or more may be used in combination.

[0048] When producing polyimide precursors, vinyl ether compounds other than 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. Specifically, these 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 linkage 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.

[0049] When producing a polyimide precursor, the amount of a specific vinyl ether compound used may be 50% to 100% by mass, 70% to 90% by mass, or 90% to 100% by mass, based on the total mass of the specific vinyl ether compound and other vinyl ether compounds.

[0050] When producing a polyimide precursor, the molar ratio of the vinyl ether compound (vinyl ether / tetracarboxylic acid + tetracarboxylic acid dianhydride) to the total of tetracarboxylic acid dianhydride and tetracarboxylic acid (which may be read as "total of tetracarboxylic acid dianhydride, tetracarboxylic acid, and non-volatile crosslinking group forming compound") may be 2 to 5, 2.5 to 4.5, or 3 to 4.

[0051] When producing a polyimide precursor, the amount of polymerization inhibitor used may be 0.1% to 1.0% by mass, 0.15% to 0.8% by mass, or 0.2% to 0.5% by mass, based on the total amount of raw materials for the polyimide precursor (for example, the sum of tetracarboxylic dianhydride and tetracarboxylic acid, diamine compounds, and specific vinyl ether compounds).

[0052] <Polyimide Precursor Composition> The polyimide precursor composition of the present disclosure comprises a polyimide precursor containing a structural unit represented by the above-mentioned general formula (1) and a structural unit represented by the above-mentioned general formula (2), and a polymerization inhibitor.

[0053] [Polyimide Precursor] The polyimide precursor of this disclosure comprises a structural unit represented by general formula (1) and a structural unit represented by general formula (2).

[0054]

[0055]

[0056] In general formula (1), X represents a tetravalent organic group that does not contain an aromatic ring, or, if it contains an aromatic ring, a tetravalent organic group in which the aromatic ring is not bonded to four carbonyl groups, and R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, and is contained in the polyimide precursor.６ and R ７ At least one of the groups is a monovalent organic group containing a (meth)acryloyl group, where * represents the bond position. In general formula (2), Y represents a divalent organic group, where * represents the bond position.

[0057] R of the structural unit represented by general formula (1) ６ and R ７ Of the total, the proportion of structures formed by the reaction of vinyl groups and carboxyl groups in vinyl ether compounds having (meth)acryloyl groups to structures formed by the reaction of vinyl groups and carboxyl groups in vinyl ether compounds is not particularly limited. From the viewpoint of producing a photosensitive resin composition with excellent photosensitivity, the above proportion may be 40 mol% or more, 50 mol% to 100 mol%, or 70 mol% to 100 mol%.

[0058] The reaction equation between a vinyl ether compound (compound (b) shown below) and a compound having a carboxyl group (compound (a) shown below) is as follows. This yields compound (c) having a structure formed by the reaction between the vinyl group and the carboxyl group in the vinyl ether compound. Note that the following reaction is just one example, and this disclosure is not limited thereto.

[0059]

[0060] The polyimide precursor may have multiple structural units represented by the above general formula (1) or the above general formula (2), and X, Y, R in the multiple structural units ６ and R ７ These may be the same or different. ６ and R ７ The combination of each is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups. For example, R ６ and R ７ At least one of them is a hydrogen atom, and the rest may be monovalent organic groups as described later, and they may all be the same or different monovalent organic groups. As mentioned above, when the polyimide precursor has multiple structural units represented by the general formula (1) above, the R of each structural unit ６and R ７ The combinations may be the same or different.

[0061] In general formula (6), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 4 to 13, and even more preferably 6 to 12 carbon atoms.

[0062] The tetravalent organic group represented by X may include an aromatic ring. If X includes an aromatic ring, that aromatic ring is not bonded to the four carbonyl groups.

[0063] In general formula (6), specific examples of X include the base shown below, but this disclosure is not limited to these specific examples.

[0064]

[0065] If X is a residue derived from a tetracarboxylic dianhydride, specific examples of the tetracarboxylic dianhydride from which the residue originates include the compounds represented by chemical formulas (A-1) to (A-6).

[0066] Furthermore, the polyimide precursor of this disclosure may also contain a structural unit (other structural unit) represented by general formula (1), in which X is a tetravalent organic group comprising an aromatic ring, and the aromatic ring is bonded to at least one carbonyl group. In the polyimide precursor, the proportion of other structural units may be 0 mol% to 10 mol%, or 0 mol% to 5 mol%, relative to the total amount of structural units represented by general formula (1).

[0067] In general formula (2), the divalent organic group represented by Y preferably has 6 to 25 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 12 to 14 carbon atoms. The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance and high elasticity, the divalent organic group represented by Y is preferably a divalent aromatic group.

[0068] Specific examples of divalent aromatic groups represented by Y include the groups represented by formulas (G) and (H) below.

[0069]

[0070] In formulas (G) to (H), R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n independently represents an integer from 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)-), or a silylene bond (-Si(R) Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of the following independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more.) or a divalent group formed by combining at least two of these. Furthermore, specific examples of D in formula (H) represent a bond, or a structure represented by the following formula (C1), 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(RA)2-; RA each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n; RB each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more) or a divalent group formed by combining at least two of these. In formula (H), D is preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, or a group containing an ether bond, a phenylene group, and an alkylene group, each independently.

[0071] 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0072] 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 methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, and t-butoxy groups.

[0073] 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 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, fluoromethyl groups, difluoromethyl groups, and trifluoromethyl groups are preferred.

[0074] In formulas (G) to (H), n is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0075] Specific examples of divalent aliphatic groups represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups having a polyalkylene oxide structure.

[0076] 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 tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonameethylene, and 2-methyldecamethylene.

[0077] 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.

[0078] 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. Among these, polyethylene oxide structure or polypropylene oxide structure is preferred as the polyalkylene 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 one type or two or more types.

[0079] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of divalent groups 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, a C1-C20 alkyl group, or a C6-C18 aryl group. Specific examples of C1-C20 alkyl groups bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, and n-dodecyl group. Among these, the methyl group is preferred. The C6-C18 aryl group bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents when the aryl group has a substituent include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl groups, naphthyl groups, and benzyl groups. Among these, phenyl groups are 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 one type or two or more types. The silicon atoms constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via methylene groups, alkylene groups such as ethylene groups, or arylene groups such as phenylene groups.

[0080] The group represented by formula (G) is preferably the group represented by the following formula (G'), and the group represented by formula (H) is preferably the group represented by the following formula (H'), formula (H''), or formula (H''').

[0081]

[0082] In formula (H'''), R independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0083] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formulas (1) and (2) is not particularly limited.

[0084] R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, and is contained in the polyimide precursor. ６ and R ７ At least one of them is a monovalent organic group containing a (meth)acryloyl group.

[0085] R contained in polyimide precursors ６ and R ７ At least one of them is preferably a structural unit represented by the following general formula (3).

[0086]

[0087] In general formula (3), R １ , R ２ and R ３ Each of these independently represents a hydrogen atom, a halogen atom, or a monovalent organic group, R ８ R represents a monovalent organic group containing a (meth)acryloyl group, and * indicates the bond position. １ , R ２ and R ３ It is preferable that is a hydrogen atom.

[0088] R ８ The monovalent organic group containing the (meth)acryloyl group in this compound may have 1 to 10 or 2 to 5 carbon atoms excluding the (meth)acryloyl group.

[0089] R ８ The monovalent organic group containing the (meth)acryloyl group in this may be a group represented by the following general formula (4).

[0090]

[0091] In general formula (4), R ９ ~R １１ Each of these 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 bond position.

[0092] R in general formula (4) ９ ~R １１The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2. ９ ~R １１ Specific examples of the aliphatic hydrocarbon group represented by include methyl group, ethyl group, n-propyl group, isopropyl group, etc., with methyl group being preferred.

[0093] R in general formula (4) ９ ~R １１ As for combinations, R ９ and R １０ is a hydrogen atom, R １１ A combination of hydrogen atoms or methyl groups is preferred.

[0094] R in general formula (4) ｘ R is a divalent linking group, which may have 1 to 10 carbon atoms or 2 to 5 carbon atoms. ｘ It is preferable that it contains an ether bond.

[0095] In general formula (1), R ６ and R ７ Preferably, at least one of them is a group represented by the general formula (4), R ６ and R ７ It is more preferable that both are groups represented by the general formula (4).

[0096] If the polyimide precursor contains a compound having a structural unit represented by the general formula (1) above, the R of all structural units contained in the compound ６ and R ７ The group R is represented by the general formula (4) for the sum of 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. There is no particular upper limit, and it may be 100 mol%. The aforementioned proportion may be 0 mol% or more and less than 60 mol%.

[0097] Polymerization inhibitors included in the polyimide precursor composition of this disclosure include 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, nitrosamines, and the like. Among these, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide is preferred. Polymerization inhibitors may be used individually or in combination of two or more.

[0098] The polymerization inhibitor content may be 0.1% to 1.0% by mass, 0.2% to 0.8% by mass, or 0.2% to 0.5% by mass, based on the total amount of the polyimide precursor composition.

[0099] The polyimide precursor of this disclosure may contain a solvent. Preferred embodiments of the solvent are the same as those described in the section on the method for producing the polyimide precursor composition of this disclosure above.

[0100] <Method for producing a photosensitive resin composition> The method for producing a photosensitive resin composition according to the present disclosure includes the steps of: producing a polyimide precursor composition by the method for producing a polyimide precursor composition according to the present disclosure; and producing a photosensitive resin composition using the polyimide precursor composition. By using the polyimide precursor composition produced by the method for producing the present disclosure, the storage stability of the photosensitive resin composition is excellent.

[0101] A photosensitive resin composition can be produced by mixing a polyimide precursor composition produced by the method for producing the polyimide precursor composition of this disclosure with other components. The other components are not particularly limited and include 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 may contain at least one of these components. The polyimide precursor composition produced by the method for producing the polyimide precursor composition of this disclosure may be, for example, a polyimide precursor solution in which a polyimide precursor is dissolved in a solvent, or the aforementioned other components may be mixed with the polyimide precursor solution.

[0102] <Photosensitive Resin Composition> The photosensitive resin composition of this disclosure comprises the polyimide precursor composition of this disclosure described above. The photosensitive resin composition may also contain other components exemplified in the method for producing the polyimide precursor composition of this disclosure described above.

[0103] <Method for Manufacturing a Cured Product> The method for manufacturing a cured product according to this disclosure includes the steps of manufacturing a photosensitive resin composition using the method for manufacturing a photosensitive resin composition according to this disclosure, and manufacturing a cured product by curing the manufactured photosensitive resin composition. The photosensitive resin composition used in manufacturing the cured product may be negative type or positive type.

[0104] The cured product may be a patterned cured product or a cured product without a pattern. The average thickness of the cured product is preferably 5 μm to 20 μm.

[0105] When the cured product is a patterned cured product, the method for manufacturing the patterned cured product preferably includes the steps of: applying a photosensitive resin composition onto a substrate and drying it to form a photosensitive resin film; pattern exposing the photosensitive resin film to light to obtain a resin film; developing the resin film after pattern exposure using a developer to obtain a patterned resin film; and heat-treating the patterned resin film.

[0106] If the cured product is a cured product without a pattern, the method for manufacturing the cured product without a pattern comprises the steps of forming a photosensitive resin film and heat treatment. Furthermore, it may also include an exposure step.

[0107] The substrates include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), and TiO2. ２ Substrate, SiO ２ Examples include metal oxide insulating substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

[0108] There are no particular restrictions on the method of applying the photosensitive resin composition of this disclosure, and it can be done using a spinner or the like.

[0109] Drying can be carried out using a hot plate, oven, or the like. The drying temperature is preferably 80°C to 150°C, and more preferably 80°C to 120°C from the viewpoint of ensuring dissolution contrast. 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 has been formed into a film.

[0110] 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.

[0111] Pattern exposure involves exposing a predetermined pattern, for example, through a photomask. The active light used for irradiation can be ultraviolet light such as i-rays, visible light, or radiation, but i-rays are preferred. Exposure devices such as parallel exposure machines, aligners, projection exposure machines, steppers, and scanner exposure machines can be used.

[0112] By developing the film, a patterned resin film (patterned resin film) can be obtained. The developer is not particularly limited, and for example, a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution may be used.

[0113] A surfactant may be added to the developer. The amount added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

[0114] The development time can be, for example, twice the time it takes for the photosensitive resin film to be immersed and completely dissolved. The development time also varies depending on the polyimide precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0115] After development, the film may be washed with a rinsing solution. The rinsing solution may be distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., either individually or in appropriate mixtures, or in a stepwise combination.

[0116] A patterned resin film can be heat-treated to obtain a patterned cured product. The polyimide precursor undergoes a dehydration and ring-closing reaction during the heat treatment process, becoming the corresponding polyimide resin.

[0117] The heat treatment temperature is preferably 250°C or lower, 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, enabling high-yield device production and energy savings in the process.

[0118] The heat treatment time is preferably 5 hours or less, and 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 proceed sufficiently. The heat treatment atmosphere may be air or an inert atmosphere such as nitrogen, but from the viewpoint of preventing oxidation of the pattern resin film, a nitrogen atmosphere is preferred.

[0119] Examples of equipment used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0120] The cured material can be used as an interlayer insulating film, a cover coat layer, or a surface protective film. Furthermore, the cured material can be used as a passivation film, a buffer coat film, etc. Using one or more selected from the group consisting of the above-mentioned passivation film, buffer coat film, interlayer insulating film, cover coat layer, and surface protective film, highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, stacked devices (multi-die fan-out wafer-level packages, etc.), and other electronic components can be manufactured.

[0121] <Semiconductor device> The semiconductor device of this disclosure includes a cured product obtained by curing the photosensitive resin composition of this disclosure described above.

[0122] An example of the manufacturing process of the semiconductor device of this disclosure will be described with reference to the drawings. Figure 1 is a manufacturing process diagram of a multilayer wiring structure semiconductor device according to one embodiment of this 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. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

[0123] Next, a photosensitive resin layer 5, such as a chlorinated rubber-based or phenol novolac-based resin, is formed on the interlayer insulating film 4, and a window 6A is provided so that a predetermined portion of the interlayer insulating film 4 is exposed by known photographic etching techniques.

[0124] The interlayer insulating film 4 with window 6A exposed is selectively etched to create 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 window 6B.

[0125] Furthermore, a second conductor layer 7 is formed using a known photoetching technique, and an electrical connection is made with the first conductor layer 3. When forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

[0126] Next, the window 6C is opened by pattern exposure using the photosensitive resin composition of this disclosure, and a surface protective film 8 is formed. The surface protective film 8 protects the second conductive 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 this disclosure.

[0127] The present disclosure will be described in more detail below based on examples and comparative examples. However, the present disclosure is not limited to the examples described below.

[0128] [Example 1] Tetracarboxylic acid dianhydride (compound represented by chemical formula (A-1)), trimellitic anhydride (TMA), and p-phenylenediamine (PPD) were prepared as raw materials. In a nitrogen-purged 0.1 liter 100 mL separable flask, 21.39 parts by mass of the compound represented by chemical formula (A-1), 1.44 parts by mass of TMA, and 7.3 parts by mass of PPD were added to 45 parts by mass of γ-butyrolactone, and the mixture was stirred at 60°C for 6 hours to obtain polyamic acid. The obtained polyamic acid contained constituent units derived from the compound represented by chemical formula (A-1) and constituent units derived from PPD, and had a non-volatile crosslinking group derived from TMA at the end of the main chain. To a reaction solution containing polyamic acid, 0.17 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide, a polymerization inhibitor, was added, and then 23.88 parts by mass of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark), a vinyl ether compound, was added. The mixture was stirred at 45°C for 6 hours to obtain a reaction solution containing polyimide precursor (A1). Based on the raw materials, the molar ratio of the compound represented by chemical formula (A-1), TMA, PPD, and VEEA was: compound represented by chemical formula (A-1):TMA:PPD:VEEA = 0.95:0.1:0.9:1.7.

[0129] Dimethyl sulfoxide was added to a reaction solution containing polyimide precursor (A1) in a mass ratio of γ-butyrolactone:dimethyl sulfoxide = 8:2 to obtain polyimide precursor composition (A1). Next, to the polyimide precursor composition (A1), 2.5 parts by mass of 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) and 10 parts by mass of dipentaerythritol hexaacrylate (DPE-6A, corresponding to a polymerizable monomer) were added per 100 parts by mass of the total raw materials for the polyimide precursor (total of diamine compound, tetracarboxylic dianhydride, and vinyl ether compound) to obtain the photosensitive resin composition of Example 1.

[0130] [Example 2] As raw materials, tetracarboxylic dianhydride (compound represented by chemical formula (A-6)), 5-norbornene-2,3-dicarboxylic anhydride (NBDA), and m-phenylenediamine (MPD) were prepared. In a nitrogen-purged 0.1 liter 100 mL separable flask, 13.73 parts by mass of the compound represented by chemical formula (A-6), 2.30 parts by mass of NBDA, and 7.57 parts by mass of MPD were added to 35 parts by mass of γ-butyrolactone, and the mixture was stirred at 60°C for 6 hours to obtain polyamic acid. The obtained polyamic acid contains constituent units derived from the compound represented by chemical formula (A-6) and constituent units derived from MPD, and has a non-volatile crosslinking group derived from NBDA at the end of the main chain. To a reaction solution containing polyamic acid, 0.16 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide, a polymerization inhibitor, was added, and then 20.85 parts by mass of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark), a vinyl ether compound, was added. The mixture was stirred at 45°C for 6 hours to obtain a reaction solution containing polyimide precursor (A2). Based on the raw materials, the molar ratio of the compound represented by chemical formula (A-6), NBDA, MPD, and VEEA was: compound represented by chemical formula (A-6):NBDA:MPD:VEEA = 1.0:0.2:1.0:1.6.

[0131] Dimethyl sulfoxide was added to a reaction solution containing polyimide precursor (A2) in a mass ratio of γ-butyrolactone:dimethyl sulfoxide = 8:2 to obtain polyimide precursor composition (A2). The photosensitive resin composition of Example 2 was obtained in the same manner as in Example 1, except that polyimide precursor composition (A2) was used instead of polyimide precursor composition (A1).

[0132] [Comparative Example 1] As raw materials, 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), trimellitic anhydride (TMA), and m-phenylenediamine (MPD) were prepared by drying them in a 160°C oven for 24 hours. In a nitrogen-purged 0.1 liter 100 mL separable flask, 15.01 parts by mass of sBPDA, 2.31 parts by mass of TMA, and 6.49 parts by mass of MPD were added to 44.20 parts by mass of γ-butyrolactone, and the mixture was stirred at 60°C for 6 hours to obtain polyamic acid. The obtained polyamic acid contained constituent units derived from sBPDA and constituent units derived from MPD, and had a non-volatile crosslinking group derived from TMA at the end of the main chain. To a reaction solution containing polyamic acid, 0.18 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide, a polymerization inhibitor, was added, and then 17.09 parts by mass of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark), a vinyl ether compound, was added. The mixture was stirred at 45°C for 6 hours to obtain a reaction solution containing polyimide precursor (A3). Based on the raw materials, the molar ratios of sBPDA, TMA, MPD, and VEEA were sBPDA:TMA:MPD:VEEA = 0.85:0.2:1.0:1.5.

[0133] Dimethyl sulfoxide was added to a reaction solution containing polyimide precursor (A3) in a mass ratio of γ-butyrolactone:dimethyl sulfoxide = 8:2 to obtain polyimide precursor composition (A3). A photosensitive resin composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that polyimide precursor composition (A3) was used instead of polyimide precursor composition (A1).

[0134] [Evaluation of Hemiacetal Esterification Rate] For the polyimide precursors of Examples 1 and 2 and Comparative Example 1 before storage at room temperature. １ ¹H-NMR was measured, and the intensity ratio of the peak derived from protons of the hemiacetal ester structure (e.g., around 1.3 ppm to 1.5 ppm for the hemiacetal ester structure) and the peak derived from the aromatic ring (e.g., around 7.0 ppm to 8.5 ppm for the protons of the aromatic ring) was calculated. The hemiacetal esterification rate (before storage at room temperature) was then calculated from the ratio of the peak derived from protons of the hemiacetal ester structure to the theoretical value.

[0135] The hemiacetal esterification rate (after room temperature storage) was calculated for the polyimide precursors of Examples 1 and 2 and Comparative Example 1 after storage at room temperature (after one week of storage at room temperature), in the same manner as before storage at room temperature. A smaller hemiacetal esterification rate (after room temperature storage) indicates that the ester structure is decomposing more rapidly during room temperature storage. In terms of the storage stability of the composition, a larger hemiacetal esterification rate is desirable. Furthermore, in terms of the storage stability of the composition, it is desirable that the change in the hemiacetal esterification rate before and after room temperature storage (the absolute difference between the hemiacetal esterification rate (before room temperature storage) and the hemiacetal esterification rate (after room temperature storage)) be small. The results are shown in Table 1.

[0136] [Measurement of Residual Film Percentage] The photosensitive resin composition obtained before and after storage at room temperature was spin-coated onto a silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electron Limited), dried at 100°C for 2 minutes, and a photosensitive resin film with a dry thickness of approximately 8 μm was formed. The development time was set to twice the time it took for the exposed areas to completely dissolve when the obtained photosensitive resin film was immersed in cyclopentanone. A photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was exposed using a mask aligner MA-8 (manufactured by Suss Microtec). The i-line equivalent was 100-1100 mJ / cm². ２The film was irradiated. After exposure, the resin film was paddle-developed in a 2.38% TMAH aqueous solution using Act8 for the development time described above to obtain a resin film. The film thickness after heating on a 100°C hot plate for 2 minutes and the film thickness after development were measured by exposing a silicon wafer by scratching a portion of the film, and measuring the height from the exposed silicon wafer surface to the film surface using a Dektak 150 (Bruker) needle-type profiler (film thickness measurement was the same below). The film thickness after development was divided by the film thickness after heating on a 100°C hot plate for 2 minutes, and the percentage was expressed to determine the residual film percentage after development. Specifically, it was calculated based on the following formula. The results are shown in Figure 2. Residual film percentage (%) = 100 × (film thickness after development / film thickness after heating)

[0137]

[0138] As shown in Table 1, the change in hemiacetal esterification rate before and after storage at room temperature was smaller in Examples 1 and 2 than in Comparative Example 1. From these points, the photosensitive resin compositions of Examples 1 and 2 exhibited excellent storage stability at room temperature. Furthermore, as shown in Figure 2, there was almost no change in the residual film percentage before and after storage at room temperature in Examples 1 and 2, but in Comparative Example 1, the residual film percentage decreased sharply after storage at room temperature, reaching almost 0%. From these results, it was also found that the photosensitive resin compositions of Examples 1 and 2 exhibited excellent storage stability at room temperature.

[0139] All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

[0140] 1. Semiconductor substrate 2. Protective film 3. First conductive layer 4. Interlayer insulating film 5. Photosensitive resin layer 6A, 6B, 6C windows 7. Second conductive layer 8. Surface protective film

Claims

1. A method for producing a polyimide precursor composition comprising the step of reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group in a liquid containing a polyamic acid, a vinyl ether compound having a (meth)acryloyl group, and a polymerization inhibitor, wherein the polyimide precursor having a (meth)acryloyl group, which is the reaction product of the polyamic acid and the vinyl ether compound having a (meth)acryloyl group, comprises a structural unit represented by general formula (1) and a structural unit represented by general formula (2). In general formula (1), X represents a tetravalent organic group that does not contain an aromatic ring, or, if it contains an aromatic ring, a tetravalent organic group in which the aromatic ring is not bonded to four carbonyl groups, and R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, and is contained in the polyimide precursor. ６ and R ７ At least one of the groups is a monovalent organic group containing a (meth)acryloyl group, where * represents the bond position. In general formula (2), Y represents a divalent organic group, where * represents the bond position.

2. A method for producing a polyimide precursor composition according to claim 1, further comprising the step of reacting a tetracarboxylic dianhydride or tetracarboxylic acid with a diamine compound to obtain the polyamic acid, wherein the tetracarboxylic dianhydride or tetracarboxylic acid is a compound that does not contain an aromatic ring, or a compound that contains an aromatic ring, the aromatic ring not bonded to four carbonyl groups.

3. The method for producing a polyimide precursor composition according to claim 2, wherein the molar ratio of the vinyl ether compound to the total of the tetracarboxylic dianhydride and the tetracarboxylic acid is 1 to 5.

4. A method for producing a polyimide precursor composition according to any one of claims 1 to 3, wherein the polymerization inhibitor comprises 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide.

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

6. A method for producing a polyimide precursor composition 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 comprises a compound that does not contain nitrogen atoms and sulfur atoms in its molecule.

7. A method for producing a polyimide precursor composition according to claim 6, wherein the solvent comprises 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 the steps of: producing a polyimide precursor composition by the method for producing a polyimide precursor composition described in any one of claims 1 to 7; and producing a photosensitive resin composition using the polyimide precursor composition.

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 described in claim 8, and curing the produced photosensitive resin composition to produce a cured product.

10. 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 general formula (1), X represents a tetravalent organic group that does not contain an aromatic ring, or, if it contains an aromatic ring, a tetravalent organic group in which the aromatic ring is not bonded to four carbonyl groups, and R ６ and R ７ Each of these independently represents a hydrogen atom or a monovalent organic group, and is contained in the polyimide precursor. ６ and R ７ At least one of the structures is formed by the reaction of a vinyl group and a carboxyl group in a vinyl ether compound having a (meth)acryloyl group, and is a monovalent organic group containing a (meth)acryloyl group, where * represents the bond position, and in general formula (2), Y represents a divalent organic group, where * represents the bond position.

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

12. The polyimide precursor composition according to claim 10 or claim 11, wherein the polymerization inhibitor comprises 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-2,3-dioxide.

13. A photosensitive resin composition comprising the polyimide precursor composition according to any one of claims 10 to 12.

14. A semiconductor device comprising a cured product obtained by curing the photosensitive resin composition described in claim 13.

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