Negative photosensitive resin composition, negative photosensitive resin composition coating, negative photosensitive resin composition film, cured film, and semiconductor device using these

Abstract

Provided is a resin composition which exhibits excellent pattern processability in the form of a thick film and does not cause organic deposits even if processed on a substrate having an aluminum pad electrode. This negative photosensitive resin composition contains: at least one polymer compound selected from the group consisting of a polyamide, a polyimide, a polyamideimide and a polybenzoxazole as a component (A); a cationic polymerizable compound as a component (B); and a cationic photopolymerization initiator as a component (C). The negative photosensitive resin composition is characterized in that the content of fluorine atoms in the component (A) is 1 mass% or less.

Description

Negative photosensitive resin composition, negative photosensitive resin composition coating, negative photosensitive resin composition film, cured film, and semiconductor device using these

[0001] The present invention relates to a negative photosensitive resin composition, a negative photosensitive resin composition coating, a negative photosensitive resin composition film, a cured film, and a semiconductor device using these. More specifically, the present invention relates to a resin composition suitable for use in surface protection films for semiconductor elements and electronic components, interlayer insulating films, and MEMS (microelectromechanical systems) structures.

[0002] Conventionally, polyimide-based materials and polybenzoxazole-based materials, which have excellent heat resistance, electrical insulation properties, and mechanical properties, have been widely used for surface protection films and interlayer insulating films of semiconductor elements. With the recent demand for higher density and performance of semiconductor elements, photosensitive materials are required for surface protection films and interlayer insulating films from the viewpoint of production efficiency.

[0003] Photosensitive materials such as polyimide-based materials and polybenzoxazole-based materials that have been rendered photosensitive have been used. The use of these materials can simplify the pattern formation process and shorten the cumbersome pattern manufacturing process. Positive-type photosensitive polyimide materials have been proposed as such photosensitive materials (e.g., Patent Document 1). Patent Document 1 states that the use of fluorine-free polyimide precursors or polybenzoxazole precursor resins prevents the formation of residues and corrosion on pad electrodes, enabling the manufacture of semiconductor devices with highly reliable organic insulating films. However, positive-type photosensitive materials generally have issues with their application to forming thick insulating films due to issues such as outgassing from the photosensitizer and significant film loss during development. Furthermore, the use of polyimide precursors or polybenzoxazole precursor resins results in significant shrinkage upon curing, making them difficult to apply to forming thick insulating films.

[0004] Meanwhile, as a photosensitive material, a cationic polymerization type negative photosensitive material containing a polymer compound such as polyimide, a cationic polymerizable compound such as an epoxy compound, and a cationic polymerization initiator has been disclosed (for example, Patent Document 2). By using a negative photosensitive material such as that in Patent Document 2, the effect of cure shrinkage is reduced compared to a positive photosensitive material such as that in Patent Document 1, and suitable patterning becomes possible even in applications requiring the formation of a thick insulating film.

[0005] JP 2009-283711 A JP 2021-055055 A

[0006] However, when a cationic polymerization type negative photosensitive material such as that described in Patent Document 2 is used to pattern a substrate having an aluminum pad electrode and then dry etching is performed, there is a problem in that organic deposits are generated on the aluminum pad electrode portion.

[0007] In view of this situation, the authors have conducted extensive research and have found that a negative-type photosensitive resin composition containing a polymer compound such as polyimide having a fluorine atom content of 1% by mass or less, a cationically polymerizable compound, and a photocationic polymerization initiator has excellent pattern processability in thick films and does not produce organic deposits even when processing is performed on a substrate having an aluminum pad electrode.

[0008] The present invention for solving the above problems is as follows.

[0009] <1> A negative-type photosensitive resin composition comprising, as a component (A), at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole; as a component (B), a cationically polymerizable compound; and as a component (C), a photocationic polymerization initiator, wherein the content of fluorine atoms in the component (A) is 1 mass% or less.

[0010] <2> The negative photosensitive resin composition according to <1>, wherein the component (A) contains a diamine residue derived from at least one diamine represented by the following general formulas (1) to (4):

[0011]

[0012] <3> The negative photosensitive resin composition according to <2>, wherein the total amount of diamine residues derived from diamines represented by general formulas (1) to (4) is 50 to 100 mol % relative to 100 mol % of all diamine residues in the component (A).

[0013] <4> The negative photosensitive resin composition according to <2>, wherein the total amount of diamine residues derived from the diamine represented by formula (3) or (4) is 50 to 100 mol % relative to 100 mol % of all diamine residues in the component (A).

[0014] <5> The negative photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) contains a diamine residue derived from a diamine represented by the following general formula (5):

[0015]

[0016] <6> The negative photosensitive resin composition according to any one of <1> to <4>, wherein the component (A) contains an alicyclic structure.

[0017] <7> The negative photosensitive resin composition according to any one of <1> to <5>, wherein the component (A) contains a carboxylic acid residue derived from an acid dianhydride represented by the following general formula (6):

[0018]

[0019] <8> The negative photosensitive resin composition according to <4>, wherein the component (A) contains a diamine residue derived from a diamine and a carboxylic acid residue, and wherein, when the total carboxylic acid residues contained in the component (A) are X mol and the total diamine residues are Y mol, a ratio Y / X of the total diamine residues to the total carboxylic acid residues is 0.55 to 0.85.

[0020] <9> The negative photosensitive resin composition according to any one of <1> to <7>, wherein the component (A) has an imidization rate of 70 to 100%.

[0021] <10> A negative photosensitive resin composition film comprising the negative photosensitive resin composition according to any one of <1> to <9>.

[0022] <11> A negative photosensitive resin composition film having the negative photosensitive resin composition coating according to <10> and a support.

[0023] <12> A cured film obtained by curing the negative photosensitive resin composition according to any one of <1> to <9> or the negative photosensitive resin composition film according to <10>.

[0024] <13> A semiconductor device having the cured film according to <12>.

[0025] <14> The semiconductor device according to <13>, having an aluminum pad electrode.

[0026] The present invention relates to a negative-type photosensitive resin composition, a negative-type photosensitive resin composition coating, a negative-type photosensitive resin composition film, a cured film, and a semiconductor device using these, which have excellent pattern processability in a thick film and do not produce organic deposits even when processed on a substrate having an aluminum pad electrode.

[0027] The negative-type photosensitive resin composition of the present invention is a negative-type photosensitive resin composition comprising, as component (A), at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, as component (B), a cationically polymerizable compound as component (B), and a photocationic polymerization initiator as component (C), wherein the content of fluorine atoms in component (A) is 1 mass% or less.

[0028] <Component (A)> The negative-type photosensitive resin composition of the present invention contains, as component (A), at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole (sometimes referred to as polymer compound (A)). By containing component (A), the negative-type photosensitive resin composition of the present invention has excellent film-forming properties when formed into a film.

[0029] The weight-average molecular weight of the component (A) is not particularly limited, but is preferably 1,000 or more and 200,000 or less. The polymer compound (A) may be used alone or in combination of two or more. The weight-average molecular weight of the polymer compound (A) in the present invention is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

[0030] Furthermore, it is important that the negative-type photosensitive resin composition of the present invention contains at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, and as long as it contains at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, it may also contain polymer compounds other than polyamide, polyimide, polyamideimide, and polybenzoxazole. Note that the polyimide precursor and polybenzoxazole precursor correspond to the above-mentioned polyamide, respectively.

[0031] In the present invention, the component (A) is preferably a compound having at least one structure selected from the structures represented by general formula (7) and general formula (8).

[0032]

[0033] (In the general formulas (7) and (8), X １ and X ２ each independently represents a divalent to decavalent organic group; Y １ and Y ２ each independently represents a divalent to tetravalent organic group, and R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. q is an integer of 0 to 2, and r, s, t, and u are each independently an integer of 0 to 4. X in general formulas (7) and (8) １ and X ２each independently represents a divalent to decavalent organic group and represents a carboxylic acid residue. Here, the carboxylic acid residue refers to a structure derived from a compound such as a dicarboxylic acid, a diacid chloride compound, a tetracarboxylic acid, or an acid dianhydride used in a direct polymerization reaction, which can constitute polyamide, polyimide, polyamideimide, and polybenzoxazole. For example, when acid dianhydride b is obtained from acid dianhydride a through a chemical reaction, and then acid dianhydride b is used in a polymerization reaction to obtain polyimide c, the carboxylic acid residue of polyimide c is acid dianhydride b, and acid dianhydride a does not correspond to the carboxylic acid residue of polyimide c. Y １ and Y ２ represents a divalent to tetravalent organic group and represents a diamine residue. Here, the diamine residue refers to a structure derived from the diamine used in the direct polymerization reaction, which can constitute polyamide, polyimide, polyamideimide, and polybenzoxazole. For example, when diamine b is obtained from diamine a through a chemical reaction, and then diamine b is used in a polymerization reaction to obtain polyimide d, the diamine residue of polyimide d is diamine b, and diamine a does not correspond to the diamine residue of polyimide d.

[0034] In the present invention, the fluorine atom content of the component (A) is 1% by mass or less. Having a fluorine atom content of 1% by mass or less in the component (A) makes it less likely that organic deposits will be formed as a result of a reaction between the fluorine-containing gas used in dry etching and the organic components in the negative-tone photosensitive resin composition of the present invention. From the viewpoint of suppressing the aforementioned organic deposits, the fluorine atom content of the component (A) is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. The component (A) having a fluorine atom content of 1% by mass or less, or a fluorine atom content within the aforementioned preferred range, can be obtained by reacting a fluorine-free dicarboxylic acid, diacid chloride compound, tetracarboxylic acid, or acid dianhydride with a fluorine-free diamine.

[0035] Furthermore, it is preferable that the component (A) contains a diamine residue derived from at least one diamine of the following general formulas (1) to (4):

[0036]

[0037] The component (A) containing a diamine residue derived from at least one diamine of the general formulas (1) to (4) is preferred in that it allows for the production of a negative-type photosensitive resin composition that exhibits excellent processability in pattern processing using an alkaline aqueous solution with low environmental impact as a developer.Furthermore, it is preferred in that the phenolic hydroxyl group contained in the diamine residue derived from the diamine of the general formulas (1) to (4) undergoes a crosslinking reaction with the cationically polymerizable compound (B) during curing at high temperatures, thereby allowing for the production of a negative-type photosensitive resin composition that exhibits excellent chemical resistance.

[0038] Furthermore, the total amount of diamine residues derived from diamines represented by general formulas (1) to (4) is preferably 50 to 100 mol %, and more preferably 70 to 100 mol %, relative to 100 mol % of all diamine residues in component (A). When the total amount of diamine residues derived from diamines represented by general formulas (1) to (4) is within the preferred range, the alkali solubility of the negative photosensitive resin composition is improved, which is advantageous in that it improves the resolution during pattern processing.

[0039] Furthermore, the total amount of diamine residues derived from diamines represented by general formula (3) or (4) is preferably 50 to 100 mol %, and more preferably 70 to 100 mol %, relative to 100 mol % of all diamine residues in component (A). Having the total amount of diamine residues derived from diamines represented by general formula (3) or (4) within this preferred range is advantageous in that it improves the resolution during pattern processing due to the improved solubility resulting from the cardo structure contained in the diamine of general formula (3) or the improved solubility resulting from the phenylene ether bond contained in the diamine of general formula (4).

[0040] Furthermore, when the total amount of diamine residues derived from diamines represented by general formula (3) or (4) is 50 to 100 mol % relative to 100 mol % of all diamine residues in component (A), where X mol is the total amount of carboxylic acid residues contained in component (A) and Y mol is the total amount of diamine residues, the ratio Y / X of all diamine residues to all carboxylic acid residues is preferably 0.55 to 0.85, and more preferably 0.58 to 0.75. When the ratio Y / X of all diamine residues to all carboxylic acid residues is at least the lower limit of the preferred range, the cured film of the negative-type photosensitive resin composition has sufficient heat resistance, and when it is at most the upper limit of the preferred range, the resolution is further improved without a decrease in sensitivity during pattern processing, which is preferable.

[0041] Furthermore, the component (A) preferably contains a diamine residue derived from a diamine of the following general formula (5):

[0042]

[0043] The component (A) preferably contains a diamine residue derived from the diamine of general formula (5), which allows for the production of a negative-type photosensitive resin composition with excellent processability in pattern processing using an alkaline aqueous solution with low environmental impact as a developer. Furthermore, the carboxyl group contained in the diamine residue derived from the diamine of general formula (5) undergoes a crosslinking reaction with the cationically polymerizable compound (B) during curing at high temperatures, allowing for the production of a negative-type photosensitive resin composition with excellent chemical resistance. Furthermore, the inclusion of a diamine residue derived from the diamine of general formula (5) is also preferred in that it allows for the production of a negative-type photosensitive resin composition with improved transparency and excellent processability, although the reason for this is unclear.

[0044] The diamine residue of component (A) may contain a diamine residue having an aromatic group other than those mentioned above. Copolymerization of these can improve heat resistance. Specific examples of diamine residues having an aromatic group include 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 sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, 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)biphenyl}. Examples of aromatic diamines include, but are not limited to, aromatic diamines such as {4-(phenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 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, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons have been substituted with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like.

[0045] The diamine residue of component (A) may include a silicone diamine residue. Copolymerization of these is expected to improve solubility and insulating properties. Specific examples of silicone diamine residues include, but are not limited to, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(p-aminophenyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(p-aminophenethyl)-1,1,3,3-tetramethyldisiloxane, and 1,7-bis(p-aminophenyl)-1,1,3,3,5,5,7,7-octamethyltetrasiloxane. The other diamines to be copolymerized can be used as they are, or as the corresponding diisocyanate compounds or trimethylsilylated diamines. Furthermore, two or more of these diamine components may be used in combination. When the component (A) contains diamine residues represented by any one of the general formulas (1) to (4) and silicone diamine residues, the total content of the silicone diamine residues is preferably 3 to 30 mol%, and more preferably 5 to 20 mol%, relative to 100 mol% of all diamine residues. Having the content of the silicone diamine residues at or above the lower limit of the preferred range is preferable in that the solubility of the component (A) is improved, resulting in improved resolution. Having the content of the silicone diamine residues at or below the upper limit of the preferred range is preferable in that the component (A) has sufficient alkali solubility, resulting in improved resolution.

[0046] When the component (A) contains a diamine residue represented by the general formula (5) and a silicone diamine residue, the total amount of the silicone diamine residues is preferably 10 to 80 mol%, more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, relative to 100 mol% of all diamine residues. Having the content of the silicone diamine residues at or above the lower limit of the preferred range is preferable in that the solubility of the component (A) is improved, resulting in improved resolution, and is also preferable in that insulating properties are improved. Having the content of the silicone diamine residues at or below the upper limit of the preferred range is preferable in that the component (A) has sufficient alkali solubility, resulting in improved resolution.

[0047] Furthermore, the component (A) preferably has an alicyclic structure. The component (A) having an alicyclic structure improves the transparency of the negative-tone photosensitive resin composition and improves pattern processability. Furthermore, the component (A) more preferably contains a carboxylic acid residue having an alicyclic structure, in order to improve the solubility of the negative-tone photosensitive resin composition. Specific examples of carboxylic acid dianhydrides having an alicyclic structure include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic acid-3,4:3',4'-dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, and 4-(2,5-dioxotetrahydrofuran-3-yl)-4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride. Preferred examples thereof include norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, and norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride.

[0048] Furthermore, the component (A) preferably contains a carboxylic acid residue derived from an acid dianhydride represented by the following general formula (6).

[0049]

[0050] The component (A) containing a carboxylic acid residue derived from the acid dianhydride represented by general formula (6) is preferable in that the solubility is increased and the resolution is improved, and in addition, the chemical resistance and ion migration resistance are improved when the negative-type photosensitive resin composition is cured.

[0051] The carboxylic acid residue may include a carboxylic acid residue other than a carboxylic acid residue having an alicyclic structure, specifically, 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, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and the like. 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 dianhydride, 9,9-bis(3,4-dicarboxyphenyl) Aromatic tetracarboxylic dianhydrides such as fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1 Examples of suitable dianhydrides include, but are not limited to, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, and 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0052] The imidization rate of the component (A) is preferably 70 to 100%, and more preferably 90 to 100%. The imidization rate of the component (A) within the preferred range is preferred in that the content of amide groups that may inhibit the reactivity of the cationically polymerizable compound (B) is reduced, thereby improving sensitivity during pattern processing. Furthermore, the change in the imide ring closure rate during thermal curing of the negative-type photosensitive resin composition is reduced, which is preferred in that curing shrinkage is reduced and stress can be reduced.

[0053] In the present invention, the imidization rate can be easily determined, for example, by the following method. First, the infrared absorption spectrum of the polymer is measured, and the absorption peak of the imide structure due to polyimide (1780 cm －１ Near 1377 cm －１ Next, the polymer was heat-treated at 350°C for 1 hour, and the imidization rate was set to 100%. The infrared absorption spectrum was measured to confirm the presence of the peak at 1377cm of the resin before and after the heat treatment. －１ By comparing the peak intensities in the vicinity, the content of imide groups in the resin before heat treatment is calculated, and the imidization rate is determined.

[0054] Furthermore, the component (A) preferably has a structure at its molecular chain terminal derived from a carboxylic acid residue. By having the component (A) have a structure at its molecular chain terminal derived from a carboxylic acid residue, the molecular chain terminal can have a molecular structure that does not have an amine terminal structure that can serve as a functional group inhibiting cationic polymerization, and as a result, sufficient cationic polymerizability can be exhibited. Here, the structure at the molecular chain terminal derived from a carboxylic acid residue of the component (A) means that an organic group derived from a carboxylic acid residue that can constitute a polyamide, polyimide, or polyamideimide is located at the molecular chain terminal, and refers to a monocarboxylic acid, a dicarboxylic acid, a monoacid chloride compound, a diacid chloride compound, a tetracarboxylic acid, an acid anhydride, an acid dianhydride, etc.

[0055] Examples of the structure (organic group) at the molecular chain terminal of component (A) derived from a carboxylic acid residue include, but are not limited to, aromatic dicarboxylic acids, aromatic acid dianhydrides, alicyclic dicarboxylic acids, alicyclic acid dianhydrides, aliphatic dicarboxylic acids, aliphatic acid dianhydrides, etc. These may be used alone or in combination of two or more.

[0056] The molar ratio of the structures represented by general formulas (6) and (7) can be confirmed by a method of calculation from the molar ratio of the monomers used in polymerization, or by a method of detecting peaks of the polyamide structure, imide precursor structure, or imide structure in the obtained resin, resin composition, or cured film using a nuclear magnetic resonance (NMR) spectrometer.

[0057] The component (A) having a structure in which the molecular chain terminals are derived from carboxylic acid residues can be obtained, for example, in the case of a polyimide having a structure in which the molecular chain terminals are derived from carboxylic acid residues, by increasing the content of acid anhydride relative to the diamine used in polymerization. However, as another method for obtaining the component (A) having a structure in which the molecular chain terminals are derived from carboxylic acid residues, it can also be obtained by using a specific compound from among compounds generally used as an end-capping agent, specifically, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.

[0058] Furthermore, by capping the molecular chain ends of the component (A) with a terminal capping agent of a carboxylic acid or acid anhydride having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, the dissolution rate of the component (A) in an alkaline aqueous solution and the mechanical properties of the resulting cured film can be easily adjusted within preferred ranges. Furthermore, multiple terminal capping agents may be reacted to introduce multiple different terminal groups.

[0059] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds suitable as end-capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, and 3-carboxyphenol. Preferred are monocarboxylic acids such as cyclohexanedicarboxylic acid and 4-carboxybenzenesulfonic acid, monoacid chloride compounds in which the carboxyl group of these is converted to an acid chloride, monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene is converted to an acid chloride, and activated ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole, imidazole, or N-hydroxy-5-norbornene-2,3-dicarboximide. Two or more of these may be used.

[0060] Polymers incorporating these end-capping agents become the component (A) in which the molecular chain terminals are derived from carboxylic acid residues. The end-capping agents that can be used to obtain the component (A) in which the molecular chain terminals are derived from carboxylic acid residues can be easily detected by the following method. For example, the component (A) to which the end-capping agent has been incorporated is dissolved in an acidic solution and decomposed into the structural units, amine components and acid anhydride components, and the end-capping agents used in the present invention can be easily detected by gas chromatography (GC) or NMR. Alternatively, the resin component to which the end-capping agent has been incorporated can also be easily detected by directly measuring the resin component by pyrolysis gas chromatography (PGC), infrared spectroscopy, and C-NMR spectroscopy.

[0061] In the present invention, the component (A) is synthesized, for example, by the following method, but is not limited thereto. The polyimide structure is synthesized by a known method by replacing a portion of the diamine with a primary monoamine, which is an end-capping agent, or by replacing the tetracarboxylic dianhydride with a dicarboxylic anhydride, which is an end-capping agent. For example, a polyimide precursor is obtained by reacting a tetracarboxylic dianhydride with a diamine compound and a monoamine at low temperature, by reacting a tetracarboxylic dianhydride with a dicarboxylic anhydride and a diamine compound at low temperature, or by preparing a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine with a monoamine in the presence of a condensing agent. Then, a polyimide can be synthesized by a known imidization reaction method.

[0062] In the present invention, after the component (A) has been polymerized by the above method, it is preferably poured into a large amount of water or a mixture of methanol and water, precipitated, filtered, dried, and isolated. The drying temperature is preferably 40 to 100°C, more preferably 50 to 80°C. This operation removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties after thermal curing.

[0063] The total amount of the component (A) is preferably 15 to 70% by mass, and more preferably 25 to 60% by mass, based on 100% by mass of the entire resin composition of the present invention. Inclusion of the component (A) in an amount of 15% by mass or more relative to 100% by mass of the entire resin composition is preferred in terms of improving mechanical properties and thermal properties, while inclusion of the component (A) in an amount of 70% by mass or less is preferred in terms of reducing development residues.

[0064] <Component (B)> The negative photosensitive resin composition of the present invention contains a cationically polymerizable compound as component (B) (sometimes referred to as a (B) cationically polymerizable compound). By containing the (B) cationically polymerizable compound, the negative photosensitive resin composition of the present invention undergoes photocationic polymerization and exhibits excellent negative pattern processability.

[0065] Preferred examples of the cationically polymerizable compound (B) include cyclic ether compounds (such as epoxy compounds and oxetane compounds), ethylenically unsaturated compounds (such as vinyl ethers and styrenes), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters.

[0066] As the epoxy compound, known compounds can be used, and preferred examples include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

[0067] Preferred examples of the aromatic epoxy compound include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof).

[0068] Preferred examples of the alicyclic epoxy compound include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0069] Preferred examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxy compounds of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0070] As the oxetane compound, known compounds can be used, and preferred examples thereof include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.

[0071] As the ethylenically unsaturated compound, known cationically polymerizable monomers can be used, and preferred examples thereof include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationically polymerizable nitrogen-containing monomers.

[0072] Preferred examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0073] Preferred examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0074] Preferred examples of the polyfunctional vinyl ether include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0075] Preferred examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0076] Preferred examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

[0077] Preferred examples of bicyclo orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane.

[0078] Preferred examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0079] Preferred examples of the spiro orthoester include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0080] Of these cationically polymerizable compounds, epoxy compounds, oxetane compounds and vinyl ethers are preferred, and epoxy compounds and oxetane compounds are more preferred.

[0081] By including an epoxy compound having an isocyanurate skeleton as the cationically polymerizable compound (B), it is possible to reduce the dielectric constant and dielectric loss tangent of a cured film obtained by curing the resin composition while maintaining cationic polymerizability. Furthermore, when developing with an alkaline aqueous solution, although the reason is unclear, the epoxy compound itself does not dissolve in an alkaline aqueous solution, but by being made compatible with the alkali-soluble polymer compound (A), the alkali-solubility of the resin composition is not inhibited, thereby enabling pattern processing with an alkaline aqueous solution.

[0082] Preferred examples of epoxy compounds containing an isocyanurate skeleton include triglycidyl isocyanurates such as TEPIC-S, TEPIC-L, TEPIC-VL, TEPIC-PASB26L, TEPIC-PASB22, TEPIC-FL, and TEPIC-UC (trade names, all manufactured by Nissan Chemical Industries, Ltd.).

[0083] When an epoxy compound having an isocyanurate skeleton is contained as the cationically polymerizable compound (B), the content thereof is preferably 40% by mass or more, more preferably 60% by mass or more, relative to 100% by mass of the total of the cationically polymerizable compounds (B). The upper limit of the content of the epoxy compound having an isocyanurate skeleton is 100% by mass.

[0084] Furthermore, using a polyfunctional epoxy compound that is liquid at room temperature as the (B) cationically polymerizable compound is preferable because it improves compatibility with the (A) polymer compound and allows for fine pattern processability. In this case, the polyfunctional epoxy compound preferably has an epoxy equivalent of 80 g / eq. or more and 160 g / eq. or less. By having an epoxy equivalent of 80 g / eq. or more and 160 g / eq. or less, the heat resistance and chemical resistance of the cured film can be improved when the polyfunctional epoxy compound is formed into a cured film. The epoxy equivalent of the polyfunctional epoxy compound is more preferably 80 g / eq. or more and 150 g / eq. or less, and even more preferably 85 g / eq. or more and 130 g / eq. or less.

[0085] Preferred examples of polyfunctional epoxy compounds that are liquid at room temperature and have an epoxy equivalent of 80 g / eq. or more and 160 g / eq. or less include TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.), bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, Showfree BATG, and Showfree PETG (trade names, all manufactured by Resonac Corporation), with TEPIC-VL, Showfree BATG, and Showfree PETG being more preferred from the viewpoint of resolution. Furthermore, the inclusion of a bifunctional or higher oxetane compound as the (B) cationically polymerizable compound is preferred in that it enhances the reactivity of cationic polymerization and improves sensitivity during pattern processing. Furthermore, it is preferred in that it reduces the hydroxyl group concentration of the cured film, lowering the water absorption rate and improving insulation reliability.

[0086] Preferred examples of bifunctional or higher functional oxetane compounds include OXT-121, OXT-221 (all trade names, manufactured by Toagosei Co., Ltd.), ETERNACOLL OXBP, and ETERNACOLL OXIPA (all trade names, manufactured by UBE Co., Ltd.), and from the viewpoint of resolution, OXT-121 and ETERNACOLL OXBP are more preferred. (B) The cationically polymerizable compounds may be used alone or in combination of two or more thereof.

[0087] The content of the (B) cationically polymerizable compound is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of the (A) polymer compound, from the viewpoint of exhibiting sufficient cationic curability and improving pattern processability. On the other hand, from the viewpoint of eliminating tack on the surface of the resin composition coating when formed into a film, i.e., a resin composition coating, making it easy to handle, and from the viewpoint of improving the strength and elongation of the cured film, the content of the (B) cationically polymerizable compound is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, per 100 parts by mass of the (A) polymer compound.

[0088] <Component (C)> The negative-type photosensitive resin composition of the present invention contains a cationic photopolymerization initiator as component (C) (sometimes referred to as cationic photopolymerization initiator (C)). The component (C) generates an acid when exposed to light, causing cationic polymerization.

[0089] Although known compounds can be used as component (C), it is preferred that component (C) contains a sulfonium salt and that the counter anion forming the sulfonium salt contains at least one selected from the group consisting of borate ions, phosphate ions, and gallate ions. This is preferred because cationic polymerization of component (B) proceeds sufficiently during pattern processing, resulting in the production of a good pattern.

[0090] Examples of the cations that form the sulfonium salt include triphenylsulfonium, tri-p-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio) phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenyl) 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolyls ...10-Dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoyl)phenylthio]phenyldiphenylsulfonium triarylsulfoniums such as 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, 5-tolylthiaanthrenenium, 5-(4-ethoxyphenyl)thiaanthrenenium, and 5-(2,4,6-trimethylphenyl)thiaanthrenenium; diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium, Preferred examples include diarylsulfonium such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium; and preferred examples include, but are not limited to, dimethylphenacylsulfonium, phenacylterahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

[0091] When the cationically polymerizable compound as component (C) contains a sulfonium salt, preferred counter anions that form the sulfonium salt include borate ions, phosphate ions, gallate ions, etc. Here, a borate ion is a complex ion having boron as the central atom, a phosphate ion is a complex ion having phosphorus as the central atom, and a gallate ion is a complex ion having gallium as the central atom.

[0092] Preferred examples of borate ions include pentafluorophenylborate, trifluorophenylborate, tetrafluorophenylborate, trifluoromethylphenylborate, bis(trifluoromethyl)phenylborate, pentafluoroethylphenylborate, bis(pentafluoroethyl)phenylborate, fluoro-bis(trifluoromethyl)phenylborate, fluoro-pentafluoroethylphenylborate, and fluoro-bis(pentafluoroethyl)phenylborate, but are not limited to these.

[0093] Preferred examples of the phosphate ion include, but are not limited to, hexafluorophosphate, tris(pentafluoroethyl)trifluorophosphate, and the like.

[0094] Preferred examples of the gallate ion include, but are not limited to, tetrakis(pentafluorophenyl)gallate and tetrakis(3,5-bis(trifluoromethyl)phenyl)gallate.

[0095] The content of the (C) component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the total resin composition. This allows the cationically polymerizable compound to exhibit sufficient curability and improve pattern processability. On the other hand, in order to improve the storage stability of the resin composition, the content of the (C) component is preferably 10% by mass or less, more preferably 8% by mass or less.

[0096] <Other Components> The negative photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer is a compound that absorbs light, donates the absorbed light energy to the component (C), and generates an acid to cause cationic polymerization. Furthermore, the sensitizer absorbs light at the wavelength of irradiation used during pattern processing, and can therefore reduce the transmittance of a negative photosensitive resin composition film formed from the negative photosensitive resin composition described below. Therefore, the transmittance of the negative photosensitive resin composition film can be controlled as desired by adjusting the content of the sensitizer in the negative photosensitive resin composition.

[0097] Although the sensitizer is not particularly limited, an anthracene compound is preferred, and for example, an anthracene compound having alkoxy groups at the 9th and 10th positions (9,10-dialkoxy-anthracene derivative) is more preferred. Preferred examples of the alkoxy group include C1 to C4 alkoxy groups such as methoxy, ethoxy, and propoxy. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Preferred examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine; C1 to C4 alkyl groups such as methyl, ethyl, and propyl; sulfonate alkyl ester groups; and carboxylate alkyl ester groups. Preferred examples of the alkyl in the sulfonate alkyl ester group or carboxylate alkyl ester group include C1 to C4 alkyls such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.

[0098] The content of the sensitizer is not particularly limited, but is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, when the mass of the entire negative-type photosensitive resin composition is taken as 100% by mass. This allows the transmittance of the negative-type photosensitive resin composition film to be reduced, and even on substrates with rough surfaces such as ceramics, reflected light from the substrate surface can be suppressed, making it easier to process fine patterns. On the other hand, from the viewpoint of suppressing deterioration in the mechanical properties and thermal properties of the cured film of the negative-type photosensitive resin composition film formed from the negative-type photosensitive resin composition, when the mass of the entire negative-type photosensitive resin composition is taken as 100% by mass, the content of the sensitizer is preferably 10% by mass or less, and more preferably 5% by mass or less.

[0099] The negative photosensitive resin composition of the present invention may contain a thermal crosslinking agent, and the thermal crosslinking agent is preferably a compound having an alkoxymethyl group or a methylol group.

[0100] Examples of compounds having an alkoxymethyl group or a methylol group include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM -MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC Preferred examples include MX-280, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0101] The negative-tone photosensitive resin composition of the present invention may further contain a silane compound. By containing a silane compound, the adhesion of the negative-tone photosensitive resin composition coating, which will be described later, is improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0102] Furthermore, the negative photosensitive resin composition of the present invention may contain, as necessary, a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate, an alcohol such as ethanol, a ketone such as cyclohexanone or methyl isobutyl ketone, or an ether such as tetrahydrofuran or dioxane, in order to improve wettability with the support. Furthermore, the composition may contain inorganic particles such as silicon dioxide or titanium dioxide, or polyimide powder, in order to suppress the thermal expansion coefficient or increase or decrease the dielectric constant.

[0103] <Negative Photosensitive Resin Composition Coating, Negative Photosensitive Resin Composition Film> The negative photosensitive resin composition of the present invention may be in any form before curing, and examples thereof include a varnish, a film, etc. The negative photosensitive resin composition coating of the present invention is made of the negative photosensitive resin composition of the present invention.

[0104] The negative photosensitive resin composition film of the present invention is a film formed by laminating the negative photosensitive resin composition of the present invention on a support, i.e., a negative photosensitive resin composition film having a support and a negative photosensitive resin composition coating formed from the negative photosensitive resin composition of the present invention. When used in varnish form, a solution prepared by dissolving the above-mentioned components (A) to (C) and any other optional components in an organic solvent can be used. The negative photosensitive resin composition film of the present invention can be obtained, for example, by applying the negative photosensitive resin composition of the present invention to a support and then drying it as necessary.

[0105] The negative photosensitive resin composition coating of the present invention is preferably 5 μm or more from the viewpoint of handleability. Furthermore, in order to easily form a thick film layer when producing a semiconductor device having the cured film of the present invention described below, the thickness is more preferably 20 μm or more, and particularly preferably 30 μm or more. Furthermore, in order to suppress variations in film thickness, the thickness of the negative photosensitive resin composition coating is preferably 100 μm or less, more preferably 80 μm or less, and particularly preferably 60 μm or less.

[0106] Next, a method for producing a negative-type photosensitive resin composition film using the negative-type photosensitive resin composition of the present invention will be described. The negative-type photosensitive resin composition film of the present invention can be obtained by applying a solution (varnish) of the negative-type photosensitive resin composition to a support and then drying it as necessary. The negative-type photosensitive resin composition varnish (negative-type photosensitive resin composition varnish means the negative-type photosensitive resin composition of the present invention in varnish form) can be obtained by adding an organic solvent to the negative-type photosensitive resin composition. The organic solvent used here may be any solvent that dissolves the negative-type photosensitive resin composition.

[0107] Specific examples of organic solvents include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, and acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Preferred examples of the solvent include ketones such as acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone; alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; and other solvents such as N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone.

[0108] The negative photosensitive resin composition varnish may be filtered using filter paper or a filter. Although the filtration method is not particularly limited, a method of filtering by pressure filtration using a filter with a retention particle size of 0.4 μm to 10 μm is preferred.

[0109] The negative-type photosensitive resin composition film of the present invention is formed on a support and used. The support is not particularly limited, and various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the negative-type photosensitive resin composition film may be subjected to a surface treatment with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like to improve adhesion and peelability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability.

[0110] Furthermore, the negative photosensitive resin composition film of the present invention may have a protective film on the film surface to protect the surface. This can protect the surface of the negative photosensitive resin composition film from pollutants such as dust and dirt in the atmosphere. Examples of the protective film include polyolefin films and polyester films. It is preferable that the protective film has low adhesive strength with the negative photosensitive resin composition film.

[0111] Examples of methods for applying the negative photosensitive resin composition varnish to a support include spin coating using a spinner, spray coating, roll coating, screen printing, and methods using a blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. The coating film thickness varies depending on the coating technique, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less.

[0112] For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and drying time may be within a range that allows the organic solvent to volatilize, and are preferably set appropriately within a range that leaves the negative photosensitive resin composition film in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 40°C to 120°C for 1 minute to several tens of minutes. Alternatively, the temperature may be increased stepwise using a combination of these temperatures; for example, heat treatment may be performed at 70°C, 80°C, and 90°C for 1 minute each.

[0113] <Cured Film, Semiconductor Device> Next, examples of a method for patterning a negative photosensitive resin composition varnish or a negative photosensitive resin composition film using the same, and a method for thermocompression bonding to other members will be described.

[0114] First, a method for forming a negative photosensitive resin composition film on a substrate using the negative photosensitive resin composition of the present invention or a negative photosensitive resin composition film using the same will be described.

[0115] When using a negative-type photosensitive resin composition varnish, the varnish is first applied to a substrate. Examples of application methods include spin coating using a spinner, spray coating, roll coating, and screen printing. The coating thickness varies depending on the application technique, the solids concentration, and viscosity of the negative-type photosensitive resin composition, but it is generally preferable to apply the varnish so that the film thickness after drying is 0.5 μm to 100 μm. Next, the substrate coated with the negative-type photosensitive resin composition varnish is dried to obtain a negative-type photosensitive resin composition film. Drying can be performed using an oven, a hot plate, infrared rays, or the like. The drying temperature and drying time should be within a range that allows the organic solvent to volatilize, and are preferably set appropriately so that the negative-type photosensitive resin composition film is in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature between 50 and 150°C for one minute to several hours.

[0116] When a negative photosensitive resin composition film is used, a protective film, if any, is peeled off, and the negative photosensitive resin composition film is placed opposite a substrate and bonded by thermocompression to obtain a negative photosensitive resin composition film. Thermocompression bonding can be performed by a heat press treatment, a heat lamination treatment, a thermal vacuum lamination treatment, or the like. The bonding temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, the bonding temperature is preferably 150°C or lower to prevent the negative photosensitive resin composition film from curing during bonding, which would deteriorate the resolution of pattern formation in the exposure and development steps.

[0117] In either case, the substrates used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and circuit components arranged on these substrates. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven cloth / epoxy copper-clad laminates, heat-resistant thermoplastic substrates such as polyetherimide resin substrates, polyetherketone resin substrates, and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit boards include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit components include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low-dielectric materials containing glass-based materials and / or resins; high-dielectric materials containing resins or high-dielectric-constant inorganic particles; and insulators containing glass-based materials.

[0118] Next, the negative photosensitive resin composition film formed by the above method is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. In the case of a negative photosensitive resin composition film, if the support is made of a material that is transparent to these rays, exposure may be performed without peeling the support from the negative photosensitive resin composition film.

[0119] To form a pattern, after exposure, the unexposed areas are removed with a developer. Examples of the developer include an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine, and other alkaline compounds. In some cases, these alkaline aqueous solutions may contain, alone or in combination, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone.

[0120] Development can be carried out by spraying the developer onto the coating surface, puddling the developer onto the coating surface, immersing the coating in the developer, or immersing the coating in the developer and applying ultrasonic waves, etc. The development conditions, such as the development time and the temperature of the developer in the development step, may be any conditions that allow the unexposed areas to be removed and a pattern to be formed.

[0121] After development, it is preferable to carry out a rinsing treatment with water. Here, too, the rinsing treatment may be carried out by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

[0122] If necessary, a baking treatment may be carried out before development. This may improve the resolution of the developed pattern and increase the tolerance for development conditions. The baking temperature is preferably in the range of 50 to 180°C, more preferably in the range of 60 to 120°C. The baking time is preferably from 5 seconds to several hours.

[0123] After pattern formation, unreacted cationically polymerizable compounds and photocationic polymerization initiators remain in the negative photosensitive resin composition film. Therefore, these may thermally decompose and generate gas during thermocompression bonding or curing. To avoid this, it is preferable to irradiate the entire surface of the negative photosensitive resin composition film after pattern formation with the above-described exposure light to generate acid from the photocationic polymerization initiator. By doing so, the reaction of the unreacted cationically polymerizable compounds proceeds during thermocompression bonding or curing, and the generation of gas due to thermal decomposition can be suppressed.

[0124] After development, a temperature of 150°C to 500°C is applied to promote a thermal crosslinking reaction. Crosslinking can improve heat resistance and chemical resistance. This heat treatment method can be selected by either selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. An example of the former is a method in which heat treatment is performed at 130°C and 200°C for 30 minutes each. An example of the latter is a method in which the temperature is linearly increased from room temperature to 400°C over 2 hours.

[0125] The cured film of the present invention is a cured film obtained by curing the negative photosensitive resin composition of the present invention or the negative photosensitive resin composition film of the present invention. The cured film of the present invention obtained by curing the negative photosensitive resin composition of the present invention or the negative photosensitive resin composition film in the negative photosensitive resin composition film can be used in electronic parts such as semiconductor devices.

[0126] The semiconductor device of the present invention is a semiconductor device having the cured film of the present invention. Here, the term "semiconductor device" refers to any device that can function by utilizing the characteristics of a semiconductor element. Semiconductor devices include electro-optical devices in which semiconductor elements are connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices containing these. Semiconductor devices also include electronic components such as multilayer wiring boards for connecting semiconductor elements. Specifically, the cured film is suitable for applications such as interlayer insulating films for inductors, passivation films for semiconductors, surface protective films for semiconductor elements, interlayer insulating films between semiconductor elements and wiring, interlayer insulating films between multiple semiconductor elements, interlayer insulating films between wiring layers in multilayer wiring for high-density packaging, insulating layers for organic electroluminescent elements, interlayer insulating films for probe cards, interlayer insulating films for magnetic sensors, and structural components for wavelength-selective filters. However, the cured film can be used for a variety of applications, including but not limited to these.

[0127] Furthermore, since the negative-tone photosensitive resin composition of the present invention is characterized by the fact that organic deposits do not form even when processing is performed on a substrate having an aluminum pad electrode, the semiconductor device of the present invention preferably has an aluminum pad electrode. As mentioned above, the negative-tone photosensitive resin composition of the present invention has a fluorine atom content of 1 mass% or less in the component (A), which makes it less likely to produce organic deposits that would be produced by reaction between the fluorine-containing gas used in dry etching and the organic components in the negative-tone photosensitive resin composition of the present invention. In other words, by using the negative-tone photosensitive resin composition of the present invention, a semiconductor device having a highly reliable organic insulating film can be obtained, even in a semiconductor device having an aluminum pad electrode.

[0128] Examples of semiconductor devices having aluminum pad electrodes include, but are not limited to, semiconductor packages, multilayer wiring boards for high-density mounting, probe cards, magnetic sensors, inductors, and wavelength selection filters.

[0129] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0130] <Calculation of Fluorine Atom Content in Component (A)> For the component (A) produced in the synthesis examples described below, the fluorine atom content in the component (A) was calculated from the fluorine atom content of the raw materials used in the synthesis.

[0131] <Patterning on Silicon Substrate Having Aluminum Pad Electrode> The protective film was peeled off from the negative photosensitive resin composition film produced in each of the Examples and Comparative Examples described below, and the peeled surface was laminated onto a silicon substrate having a 5 cm square aluminum pad electrode using a vacuum diaphragm laminator (MVLP-500 / 600, manufactured by Meiki Seisakusho Co., Ltd.) under conditions of upper and lower heating platen temperatures of 80°C, vacuuming time of 20 seconds, vacuum pressing time of 30 seconds, and application pressure of 0.5 MPa, thereby forming a resin composition coating with a thickness of 40 μm on the silicon substrate.

[0132] Subsequently, after peeling off the support film, a mask having a pattern with via sizes of 100 μmφ, 80 μmφ, 60 μmφ, 50 μmφ, 40 μmφ, 30 μmφ, 20 μmφ, and 10 μmφ was set in the exposure device so that the via openings overlapped with the aluminum pad electrode portion and the silicon portion, respectively. Under the condition of an exposure gap of 100 μm between the mask and the photosensitive resin composition film, exposure was performed using an ultra-high pressure mercury lamp and an i-line bandpass filter. After exposure, the film was post-exposure baked on a hot plate at 120 ° C. for 10 minutes. Thereafter, the unexposed portions were removed by dip development using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and the film was rinsed with water. The development time was twice the time it took for the unexposed portions to completely dissolve. For the negative photosensitive resin composition film that was not dissolved in the alkaline developer, development was carried out in the same manner as above using propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) as the developer and isopropyl alcohol (hereinafter referred to as IPA) as the rinse solution. Then, using an inert oven (INL-60, manufactured by Koyo Thermo Systems Co., Ltd.), ２ The temperature was raised from room temperature to 200°C over 60 minutes in an atmosphere (oxygen concentration 20 ppm or less), and then heat-treated at 200°C for 60 minutes to obtain a cured film of the negative photosensitive resin composition patterned on a silicon substrate having an aluminum pad electrode.

[0133] The pattern thus obtained was observed under an optical microscope, and the minimum exposure amount necessary for pattern formation was taken as the sensitivity, and the minimum size when the pattern was free from abnormalities such as distortion and clogging was taken as the resolution.

[0134] Subsequently, the substrate having the patterned cured film was subjected to an etching treatment in an etching apparatus using a mixed gas consisting of oxygen:tetrafluoromethane = 20:80 volume % at a flow rate of 25 sccm, at an output of 100 W, and at a process pressure of 10 Pa for 7 minutes.

[0135] The pattern after etching was observed under an optical microscope to evaluate the presence or absence of organic deposits in the 100 μmφ opening of the aluminum pad electrode portion.

[0136] The compounds used in the examples and comparative examples were synthesized by the following methods.

[0137] Synthesis Example 1 Synthesis of Fluorine Atom-Free Diamine Compound (a) 19.0 g (0.05 mol) of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (hereinafter referred to as FDA) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide. To this solution, a solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was allowed to react at room temperature for 4 hours, and then the precipitated white solid was filtered and dried in vacuo at 50°C.

[0138] 30 g of the solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain fluorine-free diamine compound (a) represented by the following formula:

[0139]

[0140] Synthesis Example 2 Synthesis of fluorine atom-containing diamine compound (b) A fluorine atom- and amide group-containing diamine compound (b) represented by the following formula was obtained in the same manner as in Synthesis Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) (18.3 g, 0.05 mol) was used instead of FDA.

[0141]

[0142] Synthesis Example 3 Synthesis of Fluorine-Free Polyimide (A-1) Under a dry nitrogen stream, 26.31 g (0.09 mol) of 1,3-bis(3-aminophenoxy)benzene (hereinafter referred to as APB-N) was added to 80 g of γ-butyrolactone (hereinafter referred to as GBL) and dissolved with stirring at 120°C. Next, 30.03 g (0.1 mol) of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (hereinafter referred to as TDA-100) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, and then at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water, and the white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 5 hours to obtain polyimide (A-1).

[0143] Synthesis Example 4 Synthesis of polyimide (A-2) containing 0.60 mass% of fluorine atoms Polyimide (A-2) containing 0.60 mass% of fluorine atoms was obtained in the same manner as in Synthesis Example 2, except that fluorine atom-containing diamine compound (b) (1.81 g, 0.003 mol) and APB-N (25.43 g, 0.087 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0144] Synthesis Example 5 Synthesis of fluorine atom-free polyamideimide (A-3) A fluorine atom-free polyamideimide (A-3) was obtained in the same manner as in Synthesis Example 3, except that fluorine atom-free diamine compound (a) (55.68 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0145] Synthesis Example 6 Synthesis of fluorine atom-free polyimide (A-4) A fluorine atom-free polyimide (A-4) was obtained in the same manner as in Synthesis Example 3, except that 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter referred to as BAP) (23.25 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0146] Synthesis Example 7 Synthesis of fluorine atom-free polyimide (A-5) A fluorine atom-free polyimide (A-5) was obtained in the same manner as in Synthesis Example 3, except that bis(3-amino-4-hydroxyphenyl)sulfone (hereinafter referred to as ABPS) (25.23 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0147] Synthesis Example 8 Synthesis of fluorine atom-free polyimide (A-6) A fluorine atom-free polyimide (A-6) was obtained in the same manner as in Synthesis Example 3, except that FDA (34.24 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0148] Synthesis Example 9 Synthesis of fluorine atom-free polyimide (A-7) A fluorine atom-free polyimide (A-7) was obtained in the same manner as in Synthesis Example 3, except that 1,3-bis(4-amino-3-hydroxyphenoxy)benzene (hereinafter referred to as AHPB) (29.19 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0149] Synthesis Example 10 Synthesis of fluorine atom-free polyimide (A-8) A fluorine atom-free polyimide (A-8) was obtained in the same manner as in Synthesis Example 3, except that BAP (15.50 g, 0.06 mol) and APB-N (8.77 g, 0.03 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0150] Synthesis Example 11 Synthesis of fluorine atom-free polyimide (A-9) A fluorine atom-free polyimide (A-9) was obtained in the same manner as in Synthesis Example 3, except that BAP (7.75 g, 0.03 mol) and APB-N (17.54 g, 0.06 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0151] Synthesis Example 12 Synthesis of fluorine atom-free polyimide (A-10) A fluorine atom-free polyimide (A-10) was obtained in the same manner as in Synthesis Example 3, except that APB-N (26.31 g, 0.09 mol) was replaced by APBS (16.82 g, 0.06 mol) and APB-N (8.77 g, 0.03 mol).

[0152] Synthesis Example 13 Synthesis of fluorine atom-free polyimide (A-11) A fluorine atom-free polyimide (A-11) was obtained in the same manner as in Synthesis Example 3, except that APB-N (26.31 g, 0.09 mol) was replaced by APBS (8.41 g, 0.03 mol) and APB-N (17.54 g, 0.06 mol).

[0153] Synthesis Example 14 Synthesis of fluorine atom-free polyimide (A-12) A fluorine atom-free polyimide (A-12) was obtained in the same manner as in Synthesis Example 3, except that FDA (30.44 g, 0.08 mol) and APB-N (2.92 g, 0.01 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0154] Synthesis Example 15 Synthesis of fluorine atom-free polyimide (A-13) A fluorine atom-free polyimide (A-13) was obtained in the same manner as in Synthesis Example 3, except that FDA (22.83 g, 0.06 mol) and APB-N (8.77 g, 0.03 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0155] Synthesis Example 16 Synthesis of fluorine atom-free polyimide (A-14) A fluorine atom-free polyimide (A-14) was obtained in the same manner as in Synthesis Example 3, except that FDA (11.41 g, 0.03 mol) and APB-N (17.54 g, 0.06 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0156] Synthesis Example 17 Synthesis of fluorine atom-free polyimide (A-15) A fluorine atom-free polyimide (A-15) was obtained in the same manner as in Synthesis Example 3, except that AHPB (25.95 g, 0.08 mol) and APB-N (2.92 g, 0.01 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0157] Synthesis Example 18 Synthesis of fluorine atom-free polyimide (A-16) A fluorine atom-free polyimide (A-16) was obtained in the same manner as in Synthesis Example 3, except that AHPB (19.46 g, 0.06 mol) and APB-N (8.77 g, 0.03 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0158] Synthesis Example 19 Synthesis of fluorine atom-free polyimide (A-17) A fluorine atom-free polyimide (A-17) was obtained in the same manner as in Synthesis Example 3, except that AHPB (9.73 g, 0.06 mol) and APB-N (8.77 g, 0.03 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0159] Synthesis Example 20 Synthesis of fluorine atom-free polyimide (A-18) A fluorine atom-free polyimide (A-18) was obtained in the same manner as in Synthesis Example 3, except that BAP (23.25 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and 4,4′-oxydiphthalic anhydride (hereinafter referred to as ODPA) (31.02 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0160] Synthesis Example 21 Synthesis of fluorine atom-free polyimide (A-19) A fluorine atom-free polyimide (A-19) was obtained in the same manner as in Synthesis Example 3, except that ABPS (25.23 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and ODPA (31.02 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0161] Synthesis Example 22 Synthesis of fluorine atom-free polyimide (A-20) A fluorine atom-free polyimide (A-20) was obtained in the same manner as in Synthesis Example 3, except that FDA (34.24 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and ODPA (31.02 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0162] Synthesis Example 23 Synthesis of fluorine atom-free polyimide (A-21) A fluorine atom-free polyimide (A-21) was obtained in the same manner as in Synthesis Example 3, except that AHPB (29.19 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and ODPA (31.02 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0163] Synthesis Example 24 Synthesis of fluorine atom-free polyimide (A-22) A fluorine atom-free polyimide (A-22) was obtained in the same manner as in Synthesis Example 3, except that BAP (23.25 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and dicyclohexyl-3,4,3′,4′-tetracarboxylic dianhydride (hereinafter referred to as HBPDA) (30.63 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0164] Synthesis Example 25 Synthesis of fluorine atom-free polyimide (A-23) A fluorine atom-free polyimide (A-23) was obtained in the same manner as in Synthesis Example 3, except that ABPS (25.23 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and HBPDA (30.63 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0165] Synthesis Example 26: Synthesis of fluorine atom-free polyimide (A-24) A fluorine atom-free polyimide (A-24) was obtained in the same manner as in Synthesis Example 3, except that FDA (34.24 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and HBPDA (30.63 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0166] Synthesis Example 27 Synthesis of fluorine atom-free polyimide (A-25) A fluorine atom-free polyimide (A-25) was obtained in the same manner as in Synthesis Example 3, except that AHPB (29.19 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and HBPDA (30.63 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0167] Synthesis Example 28 Synthesis of fluorine atom-free polyimide (A-26) A fluorine atom-free polyimide (A-26) was obtained in the same manner as in Synthesis Example 3, except that FDA (26.63 g, 0.07 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0168] Synthesis Example 29 Synthesis of fluorine atom-free polyimide (A-27) A fluorine atom-free polyimide (A-27) was obtained in the same manner as in Synthesis Example 3, except that AHPB (22.70 g, 0.07 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0169] Synthesis Example 30 Synthesis of Fluorine Atom-Free Polyimide Precursor (A-28) Under a dry nitrogen stream, BAP (23.25 g, 0.09 mol) was added to 80 g of GBL and dissolved by stirring at 120°C. Next, TDA-100 (30.03 g, 0.1 mol) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water, 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 5 hours to obtain polyimide precursor (A-28).

[0170] Synthesis Example 31 Synthesis of fluorine atom-free polyimide precursor (A-29) A fluorine atom-free polyimide (A-29) was obtained in the same manner as in Synthesis Example 30, except that ABPS (25.23 g, 0.09 mol) was used instead of BAP (23.25 g, 0.09 mol).

[0171] Synthesis Example 32 Synthesis of fluorine atom-free polyimide precursor (A-30) A fluorine atom-free polyimide (A-30) was obtained in the same manner as in Synthesis Example 30, except that FDA (34.24 g, 0.09 mol) was used instead of BAP (23.25 g, 0.09 mol).

[0172] Synthesis Example 33 Synthesis of fluorine atom-free polyimide precursor (A-31) A fluorine atom-free polyimide (A-31) was obtained in the same manner as in Synthesis Example 30, except that AHPB (29.19 g, 0.09 mol) was used instead of BAP (23.25 g, 0.09 mol).

[0173] Synthesis Example 34 Synthesis of fluorine atom-free polyimide (A-32) A fluorine atom-free polyimide (A-32) was obtained in the same manner as in Synthesis Example 3, except that 3,5-diaminobenzoic acid (hereinafter referred to as DABA) (13.69 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0174] Synthesis Example 35 Synthesis of fluorine atom-free polyimide (A-33) A fluorine atom-free polyimide (A-33) was obtained in the same manner as in Synthesis Example 3, except that DABA (10.65 g, 0.07 mol) and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (hereinafter referred to as SiDA) (4.97 g, 0.02 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0175] Synthesis Example 36 Synthesis of fluorine atom-free polyimide (A-34) A fluorine atom-free polyimide (A-34) was obtained in the same manner as in Synthesis Example 3, except that DABA (9.13 g, 0.06 mol) and SiDA (7.46 g, 0.03 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0176] Synthesis Example 37 Synthesis of fluorine atom-free polyimide (A-35) A fluorine atom-free polyimide (A-35) was obtained in the same manner as in Synthesis Example 3, except that DABA (7.61 g, 0.05 mol) and SiDA (9.94 g, 0.04 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0177] Synthesis Example 38 Synthesis of fluorine atom-free polyimide (A-36) A fluorine atom-free polyimide (A-36) was obtained in the same manner as in Synthesis Example 3, except that DABA (4.56 g, 0.03 mol) and SiDA (14.91 g, 0.06 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0178] Synthesis Example 39 Synthesis of fluorine atom-free polyimide (A-37) A fluorine atom-free polyimide (A-37) was obtained in the same manner as in Synthesis Example 3, except that DABA (3.04 g, 0.02 mol) and SiDA (17.40 g, 0.07 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0179] Synthesis Example 40 Synthesis of fluorine atom-free polyimide (A-38) A fluorine atom-free polyimide (A-38) was obtained in the same manner as in Synthesis Example 3, except that FDA (30.44 g, 0.08 mol) and SiDA (2.49 g, 0.01 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0180] Synthesis Example 41 Synthesis of polyimide (A-39) containing 12.15 mass% fluorine atoms A fluorine atom-containing polyimide (A-39) was obtained in the same manner as in Synthesis Example 3, except that fluorine atom-containing diamine compound (b) (54.41 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol).

[0181] Synthesis Example 42 Synthesis of polyimide (A-40) containing 12.01 mass% of fluorine atoms

[0143] A fluorine atom-containing polyimide (A-40) was obtained in the same manner as in Synthesis Example 3, except that fluorine atom-containing diamine compound (b) (54.41 g, 0.09 mol) was used instead of APB-N (26.31 g, 0.09 mol) and ODPA (31.02 g, 0.1 mol) was used instead of TDA-100 (30.03 g, 0.1 mol).

[0182] Synthesis Example 43 Synthesis of polyimide (A-41) containing 1.92 mass% of fluorine atoms A polyimide (A-41) containing 1.92 mass% of fluorine atoms was obtained in the same manner as in Synthesis Example 3, except that fluorine atom-containing diamine compound (b) (6.05 g, 0.01 mol) and APB-N (23.39 g, 0.08 mol) were used instead of APB-N (26.31 g, 0.09 mol).

[0183] Example 1 10 g of polyimide (A-1) as the component (A), 12 g of TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.) as the component (B), 0.6 g of CPI-310B (trade name, manufactured by San-Apro Co., Ltd.) as the component (C), and 0.4 g of X-12-967C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent were dissolved in GBL. The amount of solvent added was adjusted so that the solids concentration was 60 mass%, with additives other than the solvent considered to be the solids content. Thereafter, the mixture was pressure-filtered using a filter with a retention particle size of 1 μm, to obtain a negative photosensitive resin composition varnish.

[0184] The resulting negative-type photosensitive resin composition varnish was applied to a 50 μm-thick PET film using a comma roll coater and dried at 120°C for 8 minutes. A 30 μm-thick polypropylene (PP) film was then laminated onto the film as a protective film to obtain a negative-type photosensitive resin composition film. The film thickness of the negative-type photosensitive resin composition film was adjusted to 40 μm. The resulting negative-type photosensitive resin composition film was used to evaluate its patternability on a silicon substrate with an aluminum pad electrode, as described above. The results are shown in Table 2.

[0185] Examples 2 to 50 Negative-type photosensitive resin composition films were prepared in the same manner as in Example 1, except that components (A) to (C) and other components were changed to compounds with structures shown in Table 1. As described above, the pattern processability on a silicon substrate having an aluminum pad electrode was evaluated. The results are shown in Table 2.

[0186] Comparative Examples 1 to 3 Resin composition films were prepared in the same manner as in Example 1, except that components (A) to (C) and other components were changed to compounds with structures shown in Table 1. As described above, the pattern processability on a silicon substrate having an aluminum pad electrode was evaluated. The results are shown in Table 2.

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] The "Diamine residue mol % (A)" column in Table 1 lists the total of diamine residues derived from diamines represented by general formulas (1) to (4) relative to 100 mol % of all diamine residues in component (A). The "Diamine residue mol % (B)" column in Table 1 lists the total of diamine residues derived from diamines represented by general formula (3) or (4) relative to 100 mol % of all diamine residues in component (A). The "Fluorine atom content" column in Table 1 lists the fluorine atom content in component (A).

[0194] As is clear from Tables 1 and 2, in Comparative Examples 1, 2, and 3, organic deposits were generated when patterning was performed on a silicon substrate having an aluminum pad electrode.

[0195] In contrast, the negative photosensitive resin composition of this example was shown to have excellent pattern processability in a thick film, and to produce no organic deposits even when processed on a substrate having an aluminum pad electrode.

[0196] Furthermore, a comparison of Examples 1 and 2 with Examples 4 to 17 shows that, by containing a diamine residue derived from at least one diamine represented by general formulas (1) to (4), excellent alkaline developability can be obtained in addition to the characteristics of the present examples described above.

[0197] Furthermore, by comparing Example 3 with Examples 4 to 17, it was shown that by containing a diamine residue derived from at least one diamine of general formulas (1) to (4), in addition to the characteristics of this example described above, pattern processability excellent in sensitivity or resolution can be obtained.

[0198] Furthermore, a comparison of Examples 1 and 2 with Examples 36 to 41 shows that, in addition to the characteristics of the present examples described above, excellent alkali developability can be obtained by containing a diamine residue derived from a diamine of general formula (5).

[0199] Furthermore, a comparison of Example 3 with Examples 36 to 41 shows that, in addition to the characteristics of this example described above, pattern processability with excellent sensitivity or resolution can be obtained by including diamine residues derived from diamines of general formula (5). Furthermore, a comparison of Examples 4 and 5 with Examples 6 and 7 shows that, in addition to the characteristics of this example described above, pattern processability with extremely excellent resolution can be obtained by including diamine residues derived from diamines of general formula (3) or (4) in a total amount of 50 to 100 mol % relative to 100 mol % of all diamine residues in component (A).

[0200] The compounds used in each synthesis example, example and comparative example are shown below.

[0201] Compounds used in the synthesis of component (A) TDA-100: acid dianhydride represented by general formula (5) ODPA: acid dianhydride HBPDA: acid dianhydride having an alicyclic structure APB-N: diamine containing no fluorine atoms BAP: diamine represented by general formula (1) ABPS: diamine represented by general formula (2) FDA: diamine represented by general formula (3) AHPB: diamine represented by general formula (4) DABA: diamine represented by general formula (5) SiDA: silicone diamine Fluorine atom-free diamine compound (a) Fluorine atom-containing diamine compound (b).

[0202]

[0203]

[0204] (B) Cationic polymerizable compounds TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd., epoxy compound), PETG (manufactured by Resonac Corporation, epoxy compound), BATG (manufactured by Resonac Corporation, epoxy compound), YL980 (manufactured by Mitsubishi Chemical Corporation, epoxy compound), OXT-121 (manufactured by Toagosei Co., Ltd., oxetane compound), OXBP (manufactured by UBE Corporation, oxetane compound), OXT-221 (manufactured by Toagosei Co., Ltd., oxetane compound).

[0205] (C) Photocationic Polymerization Initiator CPI-310B (manufactured by San-Apro Ltd., sulfonium salt containing borate ions) CPI-310FG (manufactured by San-Apro Ltd., sulfonium salt containing gallate ions).

[0206] Silane coupling agent X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.).

Claims

1. A negative-type photosensitive resin composition comprising as component (A) at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, as component (B) a cationic polymerizable compound, and as component (C) a photocationic polymerization initiator, wherein the fluorine atom content of component (A) is 1 mass% or less.

2. The negative type photosensitive resin composition according to claim 1, wherein the component (A) contains a diamine residue derived from at least one diamine represented by the following general formulas (1) to (4):

3. The negative type photosensitive resin composition according to claim 2, wherein the total of the diamine residues derived from the diamines represented by the general formulas (1) to (4) is 50 to 100 mol % relative to 100 mol % of all diamine residues in the component (A).

4. The negative type photosensitive resin composition according to claim 2, wherein the total amount of diamine residues derived from the diamine represented by general formula (3) or (4) is 50 to 100 mol % relative to 100 mol % of all diamine residues in the component (A).

5. The negative type photosensitive resin composition according to claim 1, wherein the component (A) contains a diamine residue derived from a diamine represented by the following general formula (5):

6. The negative type photosensitive resin composition according to claim 1, wherein the component (A) contains an alicyclic structure.

7. The negative photosensitive resin composition according to claim 1, wherein the component (A) contains a carboxylic acid residue derived from an acid dianhydride represented by the following general formula (6):

8. The negative type photosensitive resin composition according to claim 4, wherein the component (A) contains diamine residues derived from diamine, and also contains carboxylic acid residues, and wherein, when the total carboxylic acid residues and the total diamine residues contained in the component (A) are X mol and Y mol, respectively, the ratio Y / X of the total diamine residues to the total carboxylic acid residues is 0.55 to 0.

85.

9. The negative type photosensitive resin composition according to claim 1, wherein the imidization rate of the component (A) is 70 to 100%.

10. A negative type photosensitive resin composition coating comprising the negative type photosensitive resin composition according to claim 1.

11. A negative photosensitive resin composition film comprising the negative photosensitive resin composition coating according to claim 10 and a support.

12. A cured film obtained by curing the negative type photosensitive resin composition according to claim 1 or the negative type photosensitive resin composition film according to claim 10.

13. A semiconductor device having the cured film according to claim 12.

14. The semiconductor device according to claim 13, further comprising an aluminum pad electrode.