Resin composition, cured film, semiconductor device, and electronic component

Abstract

The purpose of the present invention is to provide a resin composition capable of forming an opening of an appropriate dimension during patterning of a thick film, and having good chemical resistance to a chemical solution used for photoresist stripping. The resin composition of the present invention comprises (a) a resin, (b) an amide group-containing tertiary amine, (c) an aromatic carboxylic acid compound, and (d) an organic solvent.

Description

Resin compositions, cured films, semiconductor devices, and electronic components

[0001] The present invention relates to a resin composition, a cured film, a semiconductor device, and an electronic component. More specifically, it relates to a resin composition suitably used as a surface protective film for semiconductor devices, an interlayer insulating film for electronic components, and an insulating layer for display devices such as organic light-emitting elements.

[0002] In recent years, power semiconductors have attracted attention as essential semiconductor devices for electric vehicles, where demand is expanding, and for power control in industrial applications. Power semiconductors are semiconductor devices that can handle high voltage and high current, and are mainly used for power conversion such as voltage and frequency conversion, and converting DC to AC and AC to DC.

[0003] These power semiconductors are used in power supply circuits for consumer electronics such as smartphones, personal computers, televisions, air conditioners, and refrigerators. In addition, they are widely used in high-power applications such as power control for electric vehicles, trains, and industrial equipment. Because they can flexibly convert power and voltage, they have low power loss and are an essential key device for achieving innovative energy savings.

[0004] Power semiconductors are used as power modules, which are formed by combining multiple power semiconductor elements into a single package module and encapsulating it with a sealing resin. However, it is necessary to form a surface protective film to improve the adhesion between the power semiconductor elements and the sealing resin, and to alleviate thermal stress caused by differences in the thermal expansion coefficients of the materials. Polyimide-based resin compositions and polybenzoxazole-based resin compositions, which have excellent heat resistance, electrical insulation, mechanical properties, and chemical resistance, are widely used as materials for this surface protective film.

[0005] Resin compositions for surface protective films of power semiconductors need to be able to pattern openings, such as through-holes, that expose the area where wire bonding is performed. Among resin compositions that can be patterned as surface protective films for semiconductors, there are photosensitive resin compositions that have been given photosensitivity and non-photosensitive resin compositions that can be patterned in combination with photoresists.

[0006] In the case of a positive-type photosensitive resin composition, the solubility of the light-irradiated area in the developer increases, so a positive-type pattern can be obtained in which the light-irradiated area dissolves during development. In the case of a negative-type photosensitive resin composition, the light-irradiated area becomes insoluble in the developer, so a negative-type pattern can be formed. On the other hand, in the case of a non-photosensitive resin composition that does not have photosensitivity, one method for forming openings is pattern processing using photoresist. This method involves coating the resin composition onto a substrate, coating it with photoresist, exposing it to light, developing it, peeling off the photoresist, and then performing a heat treatment.

[0007] While photosensitive resin compositions allow for a shorter pattern formation process compared to non-photosensitive resin compositions, the presence of additives such as photosensitive agents and dissolution modifiers in the cured film after heat curing, in addition to the main resin component, results in reduced film properties compared to non-photosensitive resin compositions. Consequently, they often fail to meet the high heat resistance, electrical insulation, mechanical properties, and chemical resistance requirements demanded for power semiconductor applications.

[0008] On the other hand, pattern processing of non-photosensitive resin compositions requires the application and removal of photoresist, but because they do not contain additives such as photosensitive agents other than the resin, the cured film after heat curing exhibits the inherent toughness of the resin. As a result, non-photosensitive resin compositions have been adopted by various power semiconductor manufacturers as surface protection film materials for power semiconductors and have a long track record.

[0009] Known resin compositions used as materials for surface protective films on semiconductors include a resin composition containing an alkali-soluble resin, an organic solvent, and an amine compound (Patent Document 1), and a resin composition containing a polyamic acid, two carboxylic acid compounds, and an organic solvent (Patent Document 2).

[0010] Japanese Patent Publication No. 2019-172975 Japanese Patent Publication No. 2010-106206

[0011] However, in recent years, the increasing performance of power semiconductors, such as higher voltage resistance and higher operating temperatures, has necessitated thicker films, presenting new challenges. While the thickness of surface protective films was conventionally around 5 μm, thicker films of 10 μm or more are now required. When patterning thick films using conventional resin compositions and photoresists, problems arise such as excessive enlargement of the opening dimensions on the film surface due to side etching during development, shape abnormalities due to discrepancies between the opening dimensions on the film surface and the film bottom surface, and cracks on the film surface caused by chemicals during photoresist removal (hereinafter referred to as cracks).

[0012] To solve the above problems, the resin composition of the present invention has the following configuration.

[0013] [1] A resin composition comprising (a) a resin, (b) an amide group-containing tertiary amine, (c) an aromatic carboxylic acid compound, and (d) an organic solvent.

[0014] [2] The resin composition according to [1], wherein the (b) amide group-containing tertiary amine has a structure represented by general formula (1) described later.

[0015] [3] The resin composition according to [1] or [2], wherein the content of the amide group-containing tertiary amine (b) in the organic solvent (d) is greater than 0 ppm by mass and 100 ppm by mass or less.

[0016] [4] The resin composition according to any one of [1] to [3], wherein the content of the aromatic carboxylic acid compound (c) in the organic solvent (d) is 10 ppm by mass or more and 500 ppm by mass or less.

[0017] [5] The resin composition according to any one of [1] to [4], wherein the (c) aromatic carboxylic acid compound contains at least one selected from the group consisting of compounds having a structure represented by general formulas (2) to (4) described later.

[0018] [6] The resin composition according to any one of [1] to [5], wherein the (c) aromatic carboxylic acid compound contains at least one selected from the group consisting of compounds having a structure represented by general formulas (5) to (7) described later.

[0019] [7] The resin composition according to any one of [1] to [6], wherein the compound having the structure represented by general formula (5) is a compound having the structure represented by general formula (8) described later.

[0020] [8] The resin composition according to any one of [1] to [7], wherein the (c) aromatic carboxylic acid compound contains at least one selected from the group consisting of compounds having a structure represented by general formulas (9) to (11) described later.

[0021] [9] The resin composition according to any one of [1] to [8], wherein the resin (a) contains a polyimide precursor.

[0022]

[10] The resin composition according to any one of [1] to [9], wherein the (d) organic solvent contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and N,N-dimethylpropionamide.

[0023]

[11] A cured film obtained by curing any of the resin compositions described in [1] to

[10] above.

[0024]

[12] A semiconductor device comprising the cured film described in

[11] above.

[0025]

[13] An electronic component comprising the cured film described in

[11] above.

[0026] The present invention makes it possible to obtain a resin composition that can form openings of appropriate dimensions when patterning thick films and has good chemical resistance to chemicals when photoresist is removed.

[0027] This is a cross-sectional view of an enlarged aperture in a power semiconductor. This is a cross-sectional view of the coil portion of a thin-film inductor.

[0028] The resin composition of the present invention contains (a) a resin, (b) a tertiary amine containing an amide group, (c) an aromatic carboxylic acid compound, and (d) an organic solvent. Thereby, it is possible to form openings with appropriate dimensions during pattern processing of a thick film, and a resin composition with good chemical resistance to the chemical solution during photoresist stripping can be obtained. The reason for obtaining such an effect is presumed as follows.

[0029] First, in the resin composition, the tertiary amine containing an amide group and the aromatic carboxylic acid compound form a tertiary amine carboxylate and stably exist in the organic solvent. After the resin composition is applied to a substrate to form a film, when the solvent in the film volatilizes during pre-baking, the tertiary amine carboxylate is unevenly distributed from the bottom surface to the central to upper part of the film, and by promoting the curing of the film, it is considered that the excessive enlargement of the opening dimension of the film surface part due to side etching during development and the deviation of the opening dimension from the film bottom surface part are suppressed, and the chemical resistance to the chemical solution during photoresist stripping is improved.

[0030] <(a) Resin> The (a) resin of the present invention preferably contains one or more resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. Among them, it is more preferable to contain a polyimide precursor. These resins can become polymers having an imide ring, an oxazole ring, or other cyclic structures by heating or with a catalyst. By becoming a cyclic structure, the heat resistance and chemical resistance are dramatically improved.

[0031] In the present invention, the (a) resin preferably has (a-1) a diamine residue. Among them, it is more preferable to have an aromatic diamine residue. Here, the diamine residue refers to an organic group obtained by removing the amino group from diamines.

[0032] Also, in the present invention, the (a) resin preferably has (a-2) a carboxylic acid residue. Among them, it is more preferable to have an aromatic tetracarboxylic acid residue. Here, the carboxylic acid residue refers to an organic group obtained by removing the carboxy group from carboxylic acids.

[0033] Polyimides are obtained by dehydrating and cyclizing polyimide precursors, which have a (a-1) diamine residue and a (a-2) carboxylic acid residue, and are produced by reacting carboxylic acid derivatives such as tetracarboxylic dianhydrides or tetracarboxylic diester dichlorides with diamines, compounds obtained by diisocyanating diamines, or compounds obtained by trimethylsilyling diamines. For example, polyimides can be obtained by dehydrating and cyclizing polyamic acid, one of the polyimide precursors obtained by reacting diamines with tetracarboxylic dianhydrides, through heat treatment. During this heat treatment, a solvent that forms an azeotrope with water, such as m-xylene, can also be added. Alternatively, polyimides can be obtained by dehydrating and cyclizing through chemical heat treatment using a dehydration condensation agent such as a carboxylic acid anhydride or dicyclohexylcarbodiimide, or a base such as triethylamine, as a cyclization catalyst. Alternatively, polyimides can be obtained by adding a weakly acidic carboxylic acid compound and heat treatment at a low temperature of 100°C or lower to dehydrate and cyclize. Polyimide precursors will be described later.

[0034] Polybenzoxazoles have a (a-1) diamine residue with a phenolic hydroxyl group and a (a-2) carboxylic acid residue. They can be obtained by dehydrating and cyclizing a polybenzoxazole precursor obtained by reacting a bisaminophenol compound with a carboxylic acid derivative such as a dicarboxylic acid chloride or a dicarboxylic acid active ester. For example, polybenzoxazoles can be obtained by dehydrating and cyclizing a polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid chloride, through heat treatment. Alternatively, they can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc., and dehydrating and cyclizing through chemical heat treatment. Polybenzoxazole precursors will be described later.

[0035] Polyimide precursors and polybenzoxazole precursors are resins having amide bonds in their main chains, which undergo dehydration and cyclization by heat treatment or chemical treatment to become the aforementioned polyimide and polybenzoxazole. The number of repeating structural units is preferably 10 to 100,000. Examples of polyimide precursors include polyamic acid, polyamic acid esters, polyamic acid amides, and polyisoimides. Among these, polyamic acid is preferred. Examples of polybenzoxazole precursors include polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide. Among these, polyhydroxyamide is preferred.

[0036] In the present invention, the (a-1) diamine residue preferably has an aromatic diamine residue. Preferred structures of the aromatic diamine residue include the structures shown below, and structures in which some of the hydrogen atoms in these structures are replaced with 1 to 4 C1-C20 alkyl groups, fluoroalkyl groups, alkoxyl groups, ester groups, nitro groups, cyano groups, fluorine atoms, or chlorine atoms.

[0037]

[0038] * indicates a joint.

[0039] In the present invention, the (a-2) carboxylic acid residue preferably has an aromatic tetracarboxylic acid residue. Furthermore, preferred structures of the aromatic tetracarboxylic acid residue include the structures shown below.

[0040]

[0041] Furthermore, (a-1) Aromatic diamines constituting the diamine residue include hydroxyl group-containing diamines such as 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, and bis(3-amino-4-hydroxyphenyl)fluorene. 3,5-diaminobenzoic acid, carboxyl group-containing diamines such as 3-carboxy-4,4'-diaminodiphenyl ether, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether, dithiohydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Nilsulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobi Examples include phenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, or compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms such as F, Cl, Br, and I.Furthermore, these diamines may have some of their hydrogen atoms substituted with C1-C10 alkyl groups such as methyl groups and ethyl groups, C1-C10 fluoroalkyl groups such as trifluoromethyl groups, or halogen atoms such as F, Cl, Br, and I.

[0042] Among the aromatic diamines constituting the (a-1) diamine residues mentioned above, m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether are preferred from the viewpoint of the mechanical properties of the cured film.

[0043] These diamines can be used as is, or as corresponding diisocyanate compounds or trimethylsilylated diamines. Alternatively, two or more of these may be used.

[0044] Furthermore, some of the (a-1) diamine residues may be replaced with silicon atom-containing diamines such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(4-anilino)tetramethyldisiloxane. Using these diamines can improve adhesion to the substrate and resistance to oxygen plasma and UV ozone treatments used for cleaning. It is preferable to use 1 to 10 mol% of these silicon atom-containing diamines in total diamine components. Using 1 mol% or more is preferable in terms of improving adhesion and resistance to plasma treatment. Using 10 mol% or less is preferable in terms of the mechanical properties of the resulting cured film.

[0045] (a-2) Aromatic tetracarboxylic dianhydride components constituting the carboxylic acid residue include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic acid dianhydride, 9,9-bis{4-(3,4- Dicarboxyphenoxy)phenyl fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Naphthalene succinate dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,Examples include, but are not limited to, 2-c]furan-1,3-dione and acidic dianhydrides with the structure shown in the following formula, as well as compounds in which some of the hydrogen atoms of the aromatic rings or hydrocarbons are substituted with C1-C10 alkyl groups, etc. These are used alone or in combination of two or more.

[0046] Among the aromatic tetracarboxylic dianhydride components listed above, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 2,2',3,3'-benzophenonetetracarboxylic dianhydride are preferred from the viewpoint of the mechanical properties of the cured film.

[0047] Furthermore, some of the (a-2) tetracarboxylic acid residues may be replaced with silicon atom-containing tetracarboxylic dianhydride. Using this can improve adhesion to the substrate and resistance to oxygen plasma and UV ozone treatment used for cleaning. It is preferable to use 1 to 10 mol% of the total acid component of this silicon atom-containing tetracarboxylic dianhydride, with 1 mol% or more being preferable in terms of substrate adhesion and the manifestation of effects against plasma treatment. Using 10 mol% or less is preferable in terms of the mechanical properties of the resulting cured film.

[0048] (a) By sealing the ends of the resin with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having an acidic group, a resin having an acidic group at the end of the main chain can be obtained. Known monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids having an acidic group may be used, or multiple such monoamines may be used.

[0049] The content of the end-capturing agent, such as the monoamine, acid anhydride, acid chloride, or monocarboxylic acid, is preferably in the range of 0.1 to 20 mol%, and more preferably 0.5 to 10 mol%, of the number of moles of monomers constituting the carboxylic acid residue or diamine residue. By setting the content within this range, it becomes easier to obtain a resin composition with excellent mechanical properties.

[0050] (a) The resin preferably has a weight-average molecular weight of 10,000 or more and 100,000 or less. If the weight-average molecular weight is 10,000 or more, the mechanical properties of the cured film after curing can be improved. More preferably, the weight-average molecular weight is 20,000 or more. On the other hand, if the weight-average molecular weight is 100,000 or less, the developability with various developing solutions can be improved, and if the weight-average molecular weight is 80,000 or less, the developability with alkaline solutions can be improved, which is therefore preferable.

[0051] The weight-average molecular weight (Mw) can be determined using a GPC (gel permeation chromatography) instrument (Waters 2690-996; manufactured by Waters Japan Ltd.). For example, it can be measured using N-methyl-2-pyrrolidone as the developing solvent and then calculated in terms of polystyrene equivalent.

[0052] <(b) Amide group-containing tertiary amine> The resin composition of the present invention contains (b) an amide group-containing tertiary amine. The (b) amide group-containing tertiary amine preferably has a structure represented by the following general formula (1).

[0053]

[0054] (In general formula (1), R １ and R ２ Each is independently a monovalent organic group having an alkyl group with 1 to 5 carbon atoms, R ３ and R ４ Each of these independently represents a hydrogen atom or a monovalent organic group having an alkyl group with 1 to 5 carbon atoms.) The content of the above (b) amide group-containing tertiary amine is preferably more than 0 ppm by mass and 100 ppm by mass or less relative to the (d) organic solvent described later, in terms of pattern processability. More preferably, it is 0.1 ppm by mass or more and 10 ppm by mass or less. Even more preferably, it is 0.5 ppm by mass or more and 2 ppm by mass or less. Pattern processability as used herein means that when an opening pattern is formed using a photoresist, the difference in the opening dimensions between the film surface and the film bottom surface can be made smaller.

[0055] The content of the amide group-containing tertiary amine (b) can be obtained, for example, by a gas chromatograph or the like.

[0056] An example of the analysis is shown below. First, 0.2 g of the resin composition sample is dissolved in 1 mL of N,N-dimethylformamide. Then, chloroform is gradually added to bring the volume to 5 mL, and the solution is transferred to a screw vial (10 mL) and centrifuged. The supernatant is used as the sample solution. GC-MS analysis is performed using a GC-MS instrument (manufactured by Shimadzu Corporation) under the following conditions: column temperature: 40-250°C, carrier gas: helium, scan range: m / z 29-400. (b) The content of the amide-containing tertiary amine can be calculated by performing GC-MS analysis of the amide-containing tertiary amine under the same conditions as above and creating a calibration curve.

[0057] <(c) Aromatic carboxylic acid compound>The resin composition of the present invention contains (c) an aromatic carboxylic acid compound. Here, the (c) aromatic carboxylic acid compound is a compound in which a carboxyl group is bonded to an aromatic ring. Examples of the (c) aromatic carboxylic acid compound include benzoic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylbenzoic acid, 2,4,5-trimethylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 4-methylphthalic acid, 4,6-dimethylisophthalic acid, 2-methylterephthalic acid, 2,5-dimethylterephthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, mellitic acid, 3-phenylbenzoic acid, (1,1'-biphenyl)-3,4',5-tricarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, biphenyl-3,3',5,5'-tetracarboxylic acid, 1,3,5-tris(4-carboxyphenyl)benzene, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 3-benzoylbenzoic acid, 4-benzoylphthalic acid, benzophenone-2,4,5-tricarboxylic acid, 2-(4-carboxy-benzoyl)terephthalic acid, 4,4'-carbonyldiphthalic acid, 5,5'-carbonyldiisophthalic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalene-2,6-dicarboxylic acid, and the like, but are not limited thereto. These may be used alone or in combination of two or more. It is preferable that the (c) aromatic carboxylic acid compound contains at least one selected from the group consisting of compounds having a structure represented by the following general formulas (2) to (4).

[0058]

[0059] (In general formula (2), R ５ ~R １０ are each independently a monovalent organic group having a carboxyl group, a hydroxyl group, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and at least one of R ５ ~R １０ is a carboxyl group.)

[0060]

[0061] (In general formula (3), R １１ ~R ２０Each of these is independently a monovalent organic group having a carboxyl group, a hydroxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R １１ ~R ２０ At least one of them is a carboxyl group. X is -CO-, -SO ２ (This represents a divalent organic group having -, -NHCO-, -O-, -S-, an isopropylidene group, a hexafluoroisopropylidene group, or an alkyl group having 1 to 5 carbon atoms.)

[0062]

[0063] (In general formula (4), R ２１ ~R ３０ Each of these is independently a monovalent organic group having a carboxyl group, a hydroxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R ２１ ~R ３０ At least one of them is a carboxyl group.) In terms of pattern processability and resistance to stripping solutions, it is more preferable to include at least one selected from the group consisting of compounds having structures represented by general formulas (5) to (7) among the aromatic carboxylic acid compounds, and it is even more preferable that the compound having the structure represented by general formula (5) is a compound having the structure represented by general formula (8). Stripping solution resistance refers to resistance to chemicals when stripping photoresist.

[0064]

[0065] (In general formula (5), R ３１ ~R ３４ Each of these is independently a monovalent organic group having a carboxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R ３１ ~R ３４ (One to three of these are carboxyl groups.)

[0066]

[0067] (In general formula (6), R ３５ ~R ３８ Each of these is independently a monovalent organic group having a carboxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R ３５ ~R ３８(One to three of these are carboxyl groups.)

[0068]

[0069] (In general formula (7), R ３９ ~R ４２ Each of these is independently a monovalent organic group having a carboxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R ３９ ~R ４２ (One to three of these are carboxyl groups.)

[0070]

[0071] (In general formula (8), R ４３ (c) is a monovalent organic group having a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) In terms of pattern processability and resistance to stripping solution, it is even more preferable to include at least one selected from the group consisting of compounds having the structure represented by chemical formulas (9) to (11) among the aromatic carboxylic acid compounds.

[0072]

[0073]

[0074]

[0075] The content of the aromatic carboxylic acid compound (c) is preferably 10 ppm by mass or more and 500 ppm by mass or less relative to the organic solvent (d) described later, in terms of pattern processability. More preferably, it is 10 ppm by mass or more and 250 ppm by mass or less.

[0076] The content of the aromatic carboxylic acid compound (c) can be determined, for example, by high-performance liquid chromatography (HPLC).

[0077] An example of the analysis is shown below. First, acetonitrile is gradually added to 0.1 g of the resin composition sample to a final volume of 5 mL. This solution is transferred to a screw vial (10 mL) and centrifuged, and the supernatant is used as the sample solution. An LC-MS analysis is performed using an LC-MS instrument (manufactured by Shimadzu Corporation) under the following conditions: column temperature: 50°C, flow rate: 1.0 mL / min, scan range: m / z 50 to 750. (c) The content of aromatic carboxylic acid compounds can be calculated by performing an LC-MS analysis of aromatic carboxylic acid compounds under the same conditions as above and creating a calibration curve.

[0078] <(d) Organic Solvents> The resin composition of the present invention contains (d) organic solvents. Specific examples include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutylamide, N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide, as well as tetrahydrofuran and dioxa. Examples include ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate and 3-methyl-3-methoxybutyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol and 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be included. Among these, (a) an amide-based solvent with good resin solubility is preferred, and it is more preferable to include at least one selected from the group consisting of N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide and N,N-dimethylpropionamide.

[0079] Furthermore, the (d) organic solvent used in the resin composition of the present invention is preferably 100 parts by mass or more, particularly preferably 200 parts by mass or more, preferably 1500 parts by mass or less, and particularly preferably 1200 parts by mass or less, based on 100 parts by mass of the total amount of the (a) resin.

[0080] The resin composition of the present invention may contain a surfactant. The inclusion of a surfactant can improve wettability with the substrate.

[0081] Examples of surfactants include fluorine-based surfactants such as "FLUORAD" (registered trademark) (manufactured by 3M Japan Ltd.), "Megafac" (registered trademark) (manufactured by DIC Corporation), and "Surflon" (registered trademark) (manufactured by Asahi Glass Co., Ltd.); organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and "BYK" (registered trademark) (manufactured by Bic Chemie Co., Ltd.); acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.); and pluronic-type surfactants such as "Pronon" (registered trademark) (manufactured by NOF Corporation), all of which are available from the aforementioned companies.

[0082] The resin composition of the present invention may contain an adhesion improver. The inclusion of an adhesion improver can enhance adhesion to the substrate.

[0083] Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with alkoxy group-containing silicon compounds. Two or more of these may be included. By including these adhesion improvers, when developing the coated film, silicon wafers, ITO (indium tin oxide), SiO ２This improves the adhesion of the substrate to the development process, such as silicon nitride. Furthermore, it enhances resistance to oxygen plasma and UV ozone treatments used in cleaning.

[0084] Next, a method for producing the resin composition of the present invention will be described. For example, a resin composition can be obtained by dissolving (a) a resin, (b) an amide group-containing tertiary amine, (c) an aromatic carboxylic acid compound, and optionally other components such as a surfactant, in (d) an organic solvent. Dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually from room temperature to 95°C. Furthermore, the order in which each component is dissolved is not particularly limited; for example, one method is to dissolve the compounds with lower solubility first. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of other components due to bubble generation.

[0085] The obtained resin composition is preferably filtered using a filtration filter to remove dirt and particles. The pore size of the filter can be, but is not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.03 μm, 0.02 μm, 0.01 μm, or 0.005 μm. The material of the filtration filter can be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), but PE or PTFE are preferred.

[0086] <Cured Film> The cured film of the present invention is obtained by curing the resin composition of the present invention.

[0087] A method for producing a cured resin film using the resin composition of the present invention will be explained with examples.

[0088] First, the resin composition is applied to the substrate. While silicon wafers, ceramics, and gallium arsenide are used as substrates, they are not limited to these. The substrate may also be pre-treated with chemical solutions such as silane coupling agents and titanium chelating agents. For example, a solution prepared by dissolving the coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate at a concentration of 0.5 to 20% by mass is prepared, and the surface is treated by spin coating, immersion, spray coating, or steam treatment. In some cases, the reaction between the substrate and the coupling agent can then be advanced by applying a temperature of 50°C to 300°C.

[0089] Methods for applying resin compositions include rotary coating using a spinner, spray coating, and roll coating. The coating thickness varies depending on the coating method, the solid content concentration of the composition, viscosity, etc., but typically, the coating is applied so that the film thickness after drying is 1 to 50 μm.

[0090] Next, the substrate coated with the resin composition is dried to obtain a coating film. This process is sometimes called pre-baking. Drying is preferably carried out using an oven, hot plate, or infrared heater at a temperature of 70 to 140°C for 1 minute to several hours. When using a hot plate, the coating film is heated either directly on the plate or on a jig such as proximity pins placed on the plate. The proximity pins can be made of metal materials such as aluminum or stainless steel, or synthetic resins such as polyimide resin or "Teflon" (registered trademark). Any material with heat resistance can be used for the proximity pins. The height of the proximity pins varies depending on the size of the substrate, the type of coating film, and the purpose of heating, but 0.1 to 10 mm is preferred.

[0091] Next, a photoresist is formed on this coating film, and it is exposed by irradiating it with a chemical beam through a mask having the desired pattern. Chemical beams that can be used for exposure include ultraviolet light, visible light, electron beams, and X-rays, but in this invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. If the photoresist has positive-type photosensitivity, the exposed area dissolves in the developer. If it has negative-type photosensitivity, the exposed area hardens and becomes insoluble in the developer.

[0092] Next, a post-exposure bake treatment is performed as needed. The temperature for this is preferably in the range of 50 to 180°C, and more preferably in the range of 60 to 150°C. There are no particular restrictions on the time, but from the viewpoint of subsequent developability, 10 seconds to several hours is preferred.

[0093] To form a pattern on the coated film after exposure, if the photoresist is positive-type photosensitive, the exposed areas are removed using a developer. The developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. In some cases, one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, or dimethylacrylamide, alcohols such as methanol, ethanol, or isopropanol, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, or ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutyl ketone may be added to these alkaline aqueous solutions. After developing, it is common practice to rinse the film with water.

[0094] After development, the photoresist is removed using a stripping solution. Preferably, the stripping method involves immersion in the photoresist stripping solution at room temperature to 100°C for 5 seconds to 24 hours using methods such as showering, dipping, or paddle. Known photoresist stripping solutions can be used, including butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, methyl 3-methoxypropionate, and ethyl lactate.

[0095] After photoresist removal, the resulting coating pattern is heated in a temperature range of 150 to 500°C to convert the coating into a cured relief pattern. This heat treatment is preferably carried out by selecting a temperature and gradually increasing it, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. Examples include heat treatment at 130°C, 200°C, and 350°C for 30 minutes each, or by linearly increasing the temperature from room temperature to 320°C over 2 hours.

[0096] <Semiconductor Devices, Electronic Components> The semiconductor device or electronic component of the present invention comprises a cured film obtained from the resin composition of the present invention. The semiconductor device or electronic component of the present invention is preferable in terms of improving reliability by arranging the cured film of the present invention as a surface protective film or interlayer insulating film in contact with a conductor.

[0097] A semiconductor device on which the cured film of the present invention is arranged will be described with reference to the drawings. Figure 1 is an enlarged cross-sectional view of an opening in which the cured film of the present invention is formed as a surface protective film on a semiconductor substrate. As shown in Figure 1, a surface protective film 2 is formed on the semiconductor substrate 1.

[0098] A first preferred embodiment of the electronic component of the present invention has a coil structure in which the cured film of the present invention is repeatedly arranged in 2 to 10 layers as an interlayer insulating film. The coil structure of the present invention is preferable in terms of reducing signal transmission efficiency by reducing transmission loss, as dielectric loss at the interface between the stacked interlayer insulating films and the coil conductor is reduced.

[0099] The present invention will now describe an electronic component having a coil structure in which the cured film is repeatedly arranged in 2 to 10 layers as an interlayer insulating film, using drawings. Figure 2 is a cross-sectional view of the coil portion of a thin-film inductor in which the cured film of the present invention is arranged as an interlayer insulating film. As shown in Figure 2, an interlayer insulating film 12 is formed on a substrate 11, and an interlayer insulating film 13 is formed thereon. Ferrite or the like is used as the substrate 11. The cured film of the present invention is used for the interlayer insulating film 12 and the interlayer insulating film 13. A metal (Cr, Ti, etc.) film 14 is formed in the opening of the interlayer insulating film 13, and metal wiring (Ag, Cu, etc.) 15 is plated thereon. The metal wiring 15 (Ag, Cu, etc.) is formed in a spiral. The process from forming the interlayer insulating film 12 to forming the metal wiring 15 is repeated multiple times, and the layers are stacked to give it the function of a coil. Finally, the metal wiring 15 (Ag, Cu, etc.) is connected to an electrode 17 by metal wiring 16 (Ag, Cu, etc.) and sealed with a sealing resin 18. There is no upper limit to the number of insulating layers, but 2 to 10 layers are preferred. Using two or more interlayer insulating films can efficiently insulate the conductors formed between the interlayer insulating films, which can improve electrical properties. Using 10 or fewer interlayer insulating films can ensure flatness and improve processing accuracy.

[0100] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The resin compositions in the examples were evaluated by the following method.

[0101] <Preparation of cured relief pattern> A resin composition was spin-coated onto a 6-inch silicon wafer using MARK-7 (manufactured by Tokyo Electron Ltd.) to a film thickness of 16 μm after pre-baking. Then, the coated film was obtained by pre-baking at 120°C for 3 minutes using a hot plate.

[0102] Next, a positive-type photoresist, OFPR-800LB (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), was spin-coated onto this coating using MARK-7 (manufactured by Tokyo Electron Ltd.) to a photoresist film thickness of 2.5 μm. Then, a photoresist film was formed by pre-baking at 100°C for 2 minutes using a hot plate.

[0103] Subsequently, exposure was performed through a photomask patterned using a mask aligner PEM-6M (manufactured by Union Chemical Co., Ltd.). The exposure dose measured using the i-line was 200 mJ / cm². ２ The entire substrate was then exposed. After exposure, using a developing device AD-3000 (manufactured by Mikasa Corporation), the substrate with the photoresist film formed on the coated film was rotated at 50 rpm while NMD-3 (product name, 2.38% aqueous solution of tetramethylammonium hydroxide, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dispensed for 10 seconds, followed by standing at 0 rpm for 50 seconds. After that, the 10-second dispensing and 50-second standing process was repeated a total of three times, then the substrate was rinsed with pure water at 500 rpm and dried by spinning at 3000 rpm for 10 seconds, thereby developing the photoresist film and simultaneously developing the coated film to form a pattern.

[0104] After development, the photoresist was removed using methyl 3-methoxypropionate as a stripping solution to obtain a patterned coating film. This coating film was heated in an inert oven INH-21CD (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere (oxygen concentration of 20 ppm by mass or less) from 50°C to a curing temperature of 350°C over 60 minutes, and then heated at 350°C for 60 minutes. After that, it was slowly cooled until the temperature inside the oven was below 50°C to obtain a cured relief pattern.

[0105] <Evaluation of stripping solution resistance> The presence or absence of cracks around the openings of the cured relief pattern corresponding to the 50 μm square opening pattern of the photomask was confirmed by observing the area around the openings using a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). The observation area was divided into 10 sections, with each side of the substrate's outer perimeter being excluded by 10 mm.

[0106] The resistance to the stripping solution was evaluated as follows: 0-1 cracks were rated as good (3 points), 2-3 cracks as acceptable (2 points), and 4 or more cracks as insufficient (1 point).

[0107] <Evaluation of the Aperture Dimension Ratio of Film Surface / Film Bottom Surface> Next, for the apertures of the cured relief pattern corresponding to the 50 μm square aperture pattern of the photomask, the substrate was cut and the cross-section of the apertures was observed using a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) to measure the aperture dimensions of the film surface and the aperture dimensions of the film bottom surface. The measurement points were divided into 10 sections, with 10 mm removed from each side of the outer perimeter of the substrate. The average value of the aperture dimensions measured at these 10 locations was taken as the average aperture dimension. The aperture dimension ratio of the film surface / film bottom surface was calculated using the following formula.

[0108] The ratio of the aperture dimensions of the membrane surface to the membrane bottom surface (%) = [average aperture dimension of the membrane surface] (μm) / [average aperture dimension of the membrane bottom surface] (μm) × 100 It is preferable that the ratio of the aperture dimensions of the membrane surface to the membrane bottom surface be close to 100%, with 100% or more and less than 115% being considered very good (5 points), 115% or more and less than 125% being considered very good (4 points), 125% or more and less than 135% being considered good (3 points), 135% or more and less than 145% being acceptable (2 points), and 145% or more being insufficient (1 point).

[0109] <Method for measuring film thickness> Using a Lambda Ace STM-602J (manufactured by Dainippon Screen Mfg. Co., Ltd.), film thickness was measured for polyimide, polybenzoxazole, or photoresist under conditions of a refractive index of 1.63.

[0110] <Abbreviations for raw materials> The names and abbreviations of the compounds shown in each example and comparative example are as follows. DAE: 4,4'-diaminodiphenyl ether BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride PMDA: pyromellitic anhydride BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane MAP: 3-aminophenol B1: 3-dimethylamino-N,N-dimethylpropanamide B2: tetramethyloxamide C1: trimellitic acid C2: 2-(4-carboxybenzoyl)terephthalic acid C3: (1,1'-biphenyl)-3,4',5-tricarboxylic acid C4: pyromellitic acid C5: 4,4'-carbonyl diphthalic acid C6: 3,3',4,4'-biphenyltetracarboxylic acid C7: benzenepentacarboxylic acid C8: naphthalene-2,6-dicarboxylic acid D1: N-methyl-2-pyrrolidone D2: 3-methoxy-N,N-dimethylpropionamide Here, D2 is obtained by continuously contacting 3-methoxy-N,N-dimethylpropionamide (trade name "KJCMPA" (registered trademark)-100), manufactured by KJ Chemicals, with 100 ml of ion exchange resin (trade name "Amberlist 16WET", manufactured by Organo (Rohm & Haas)) packed in an ion exchange resin column until the amide group-containing tertiary amine compound in solvent D2 is below the detection limit of GC-MS analysis. D3: N,N-dimethylisobutylamide D4: N,N-dimethylpropionamide [Example 1] Under a stream of dry nitrogen, 20.0 g (0.10 mol) of DAE (manufactured by Seika Co., Ltd.) was dissolved in 188.2 g of (d) organic solvent D1 (manufactured by Mitsubishi Chemical Corporation) heated to 40°C. To this, 16.1 g (0.05 mol) of BTDA (manufactured by Evonik Japan Co., Ltd.) and 10.9 g (0.05 mol) of PMDA (manufactured by Hi-Chem Co., Ltd.) were added, and the mixture was stirred at an internal temperature of 75 ± 10°C for 5 hours.The mixture was then cooled to room temperature, and (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) organic solvent at a concentration of 0.1 ppm by mass. (c) aromatic carboxylic acid compound C1 (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) organic solvent at a concentration of 100 ppm by mass. The mixture was stirred for a further 1 hour, and then filtered through a filtration filter with a pore size of 0.5 μm to obtain a polyimide precursor resin composition. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to stripping solution and the ratio of the opening dimensions of the film surface to the film bottom surface were evaluated.

[0111] [Example 2] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) the organic solvent at a concentration of 0.5 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0112] [Example 3] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) the organic solvent at a concentration of 1 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0113] [Example 4] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) the organic solvent at a concentration of 2 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0114] [Example 5] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) an organic solvent at a concentration of 5 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0115] [Example 6] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) the organic solvent at a concentration of 10 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0116] [Example 7] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) the organic solvent at a concentration of 50 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0117] [Example 8] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) the organic solvent at a concentration of 100 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0118] [Example 9] A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) the organic solvent at a concentration of 120 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0119] [Example 10] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C1 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 1 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0120] [Example 11] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C1 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 10 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0121] [Example 12] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C1 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 50 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0122] [Example 13] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C1 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 250 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0123] [Example 14] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C1 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 500 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0124] [Example 15] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C1 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 600 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0125] [Example 16] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C2 of an aromatic carboxylic acid compound (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to (d) an organic solvent at a concentration of 100 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0126] [Example 17] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C3 of an aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 100 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0127] [Example 18] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C4 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 100 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0128] [Example 19] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C5 of an aromatic carboxylic acid compound (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to (d) the organic solvent at a concentration of 100 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0129] [Example 20] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C6 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 100 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0130] [Example 21] A polyimide precursor resin composition was obtained in the same manner as in Example 4, except that (c) C7 of the aromatic carboxylic acid compound (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) the organic solvent at a concentration of 100 ppm by mass. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0131] [Example 22] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 1, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0132] [Example 23] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 2, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0133] [Example 24] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 3, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0134] [Example 25] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 4, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0135] [Example 26] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 5, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0136] [Example 27] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 6, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0137] [Example 28] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 7, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0138] [Example 29] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 8, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0139] [Example 30] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 9, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0140] [Example 31] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 10, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0141] [Example 32] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 11, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0142] [Example 33] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 12, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0143] [Example 34] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 13, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0144] [Example 35] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 14, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0145] [Example 36] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 15, except that the organic solvent was D2. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0146] [Example 37] Under a stream of dry nitrogen, 31.1 g (0.085 mol) of BAHF (manufactured by Central Glass Co., Ltd.) and 2.18 g (0.02 mol) of MAP (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 150 g of (d) organic solvent D1 and 52.8 g (0.6 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to -15°C. 29.5 g (0.10 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Soda Co., Ltd.) was dissolved in 50 g of (d) organic solvent D1, and this solution was added dropwise so that the internal temperature did not exceed 0°C. After the addition was complete, stirring was continued at -15°C for 6 hours. After the reaction was complete, the solution was added to 3 L of water containing 10% by weight methanol, and a white precipitate was collected. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain polyhydroxyamide, a polybenzoxazole precursor. 47.0 g of the obtained polyhydroxyamide was dissolved in 188.2 g of (d) organic solvent D1. Then, (b) amide group-containing tertiary amine B1 (manufactured by Pharmablock) was added to (d) organic solvent at a concentration of 2 ppm by mass, and (c) aromatic carboxylic acid compound C1 (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to (d) organic solvent at a concentration of 100 ppm by mass. The mixture was stirred for 1 hour, and then filtered through a filtration filter with a pore size of 0.5 μm to obtain a resin composition of polybenzoxazole precursor. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0147] [Example 38] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 4, except that the organic solvent was D3. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0148] [Example 39] (d) A resin composition of polyimide precursor was obtained in the same manner as in Example 4, except that the organic solvent was D4. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0149] [Example 40] (b) A resin composition of a polyimide precursor was obtained in the same manner as in Example 4, except that the amide group-containing tertiary amine was B2 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0150] [Example 41] (c) A resin composition of a polyimide precursor was obtained in the same manner as in Example 4, except that the aromatic carboxylic acid compound was C8 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0151] [Comparative Example 1] (b) A polyimide precursor resin composition was obtained in the same manner as in Example 1, except that B1 (manufactured by Pharmablock), an amide group-containing tertiary amine, was omitted. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0152] [Comparative Example 2] (c) A resin composition of polyimide precursor was obtained in the same manner as in Example 4, except that no aromatic carboxylic acid compound was added. Using the obtained resin composition, a cured relief pattern was prepared as described above, and the resistance to the stripping solution and the ratio of the opening dimensions of the film surface / film bottom surface were evaluated.

[0153] The composition and evaluation results of each example and comparative example are shown in Tables 1 and 2.

[0154]

[0155]

[0156] The present invention relates to a resin composition. More specifically, it can be suitably used as a surface protective film for semiconductor elements, an interlayer insulating film for electronic components, and an insulating layer for display devices such as organic light-emitting elements.

[0157] 1. Semiconductor substrate 2. Surface protective film 11. Substrate 12. Interlayer insulating film 13. Interlayer insulating film 14. Metal (Cr, Ti, etc.) film 15. Metal wiring (Ag, Cu, etc.) 16. Metal wiring (Ag, Cu, etc.) 17. Electrode 18. Sealing resin

Claims

1. A resin composition comprising (a) a resin, (b) an amide group-containing tertiary amine, (c) an aromatic carboxylic acid compound, and (d) an organic solvent.

2. The resin composition according to claim 1, wherein the (b) amide group-containing tertiary amine has a structure represented by general formula (1). (In general formula (1), R １ , R ２ Each is independently a monovalent organic group having an alkyl group with 1 to 5 carbon atoms, R ３ , R ４ Each of these independently represents a monovalent organic group having either a hydrogen atom or an alkyl group with 1 to 5 carbon atoms.

3. The resin composition according to claim 1 or 2, wherein the content of the amide group-containing tertiary amine (b) in the organic solvent (d) is greater than 0 ppm by mass and less than or equal to 100 ppm by mass.

4. The resin composition according to claim 1 or 2, wherein the content of the aromatic carboxylic acid compound (c) in the organic solvent (d) is 10 ppm by mass or more and 500 ppm by mass or less.

5. The resin composition according to claim 1 or 2, wherein the (c) aromatic carboxylic acid compound contains at least one selected from the group consisting of compounds having a structure represented by general formulas (2) to (4). (In general formula (2), R ５ ~R １０ are each independently a monovalent organic group having a carboxy group, a hydroxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and at least one of R ５ ~R １０ is a carboxy group.) (In general formula (3), R １１ ~R ２０ are each independently a monovalent organic group having a carboxy group, a hydroxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and at least one of R １１ ~R ２０ is a carboxy group. X represents -CO-, -SO ２ -, -NHCO-, -O-, -S-, an isopropylidene group, a hexafluoroisopropylidene group, or a divalent organic group having an alkyl group having 1 to 5 carbon atoms.) (In general formula (4), R ２１ ~R ３０ are each independently a monovalent organic group having a carboxy group, a hydroxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and at least one of R ２１ ~R ３０ is a carboxy group.) 6. The resin composition according to claim 1 or 2, wherein the (c) aromatic carboxylic acid compound contains at least one selected from the group consisting of compounds having a structure represented by general formulas (5) to (7). (In general formula (5), R ３１ ~R ３４ Each of these is independently a monovalent organic group having a carboxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R ３１ ~R ３４ (One to three of these are carboxyl groups.) (In general formula (6), R ３５ ~R ３８ Each of these is independently a monovalent organic group having a carboxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R ３５ ~R ３８ (One to three of these are carboxyl groups.) (In general formula (7), R ３９ ~R ４２ Each of these is independently a monovalent organic group having a carboxyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and R ３９ ~R ４２ (One to three of these are carboxyl groups.) 7. The resin composition according to claim 6, wherein the compound having the structure represented by general formula (5) is a compound having the structure represented by general formula (8). (In general formula (8), R ４３ (This refers to a monovalent organic group having a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) 8. The resin composition according to claim 1 or 2, wherein the (c) aromatic carboxylic acid compound contains at least one selected from the group consisting of compounds having a structure represented by general formulas (9) to (11).

9. The resin composition according to claim 1 or 2, wherein the resin (a) contains a polyimide precursor.

10. The resin composition according to claim 1 or 2, wherein the (d) organic solvent contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and N,N-dimethylpropionamide.

11. A cured film obtained by curing the resin composition according to claim 1 or 2.

12. A semiconductor device comprising the cured film described in claim 11.

13. An electronic component comprising the cured film described in claim 11.

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