Negative photosensitive resin composition, negative photosensitive resin composition coating film, negative photosensitive resin composition film, cured film, and electronic component comprising same

Abstract

The present invention provides a resin composition which has excellent pattern processability in a thick film and does not generate an organic deposit even when processing is performed on a substrate having an aluminum pad electrode. A negative photosensitive resin composition contains (B) a polymerizable compound and (C) a photopolymerization initiator. The content of fluorine atoms in the total solid content of the negative photosensitive resin composition is characterized to be 0.0% by mass to 1.0% by mass inclusive.

Description

Negative photosensitive resin composition, negative photosensitive resin composition coating, negative photosensitive resin composition film, cured film, and electronic components 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 electronic components 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, MEMS (microelectromechanical systems) structures, and the like.

[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 or 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 complicated 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 electronic components 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 polymerizable compound and a photopolymerization initiator, in which the fluorine atom content of the total solid content of the negative-type photosensitive resin composition is 0.0 mass % or more and 1.0 mass % or less, has excellent pattern processability in a thick film 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 containing (B) a polymerizable compound and (C) a photopolymerization initiator, wherein the fluorine atom content of the total solid content of the negative-type photosensitive resin composition is 0.0 mass% or more and 1.0 mass% or less.

[0010] <2> The negative photosensitive resin composition according to <1>, further comprising (A) a polymer compound, wherein the polymer compound (A) is at least one polymer compound selected from the group consisting of polyimide, polyamide, and polyamideimide.

[0011] <3> The negative photosensitive resin composition according to <2>, wherein the polymer compound (A) is soluble in an alkaline aqueous solution.

[0012] <4> The negative photosensitive resin composition according to <2> or <3>, wherein the component (A) (hereinafter, sometimes referred to as component (A)) contains at least one diamine residue derived from a diamine represented by any one of general formulas (8) to (12).

[0013]

[0014] (In the general formula (8), Z and Z ２ each independently represent a monovalent organic group having 1 to 20 carbon atoms and not containing a hydrogen atom or a fluorine atom. General formula (9) does not include the structure represented by general formula (8), and in general formula (9), Z3 represents a sulfonyl group, a carbonyl group, an oxygen atom, a divalent organic group having a linear aliphatic group having 2 to 20 carbon atoms and not containing a fluorine atom, or a single bond. In general formula (10), Z4 and Z5 each independently represent an amide group, a sulfonyl group, a carbonyl group, an oxygen atom, or a single bond. In general formula (11), Z6 and Z7 each independently represent a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom, or a phenylene group. In general formula (12), Z ８ and Z ９ each independently represents a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom or a phenylene group; Z １０ and Z １１ each independently represents an amide group, a sulfonyl group, a carbonyl group, an oxygen atom, or a single bond.

[0015] <5> The negative photosensitive resin composition according to <2> or <3>, wherein the component (A) contains at least one diamine residue derived from a diamine represented by any one of general formulas (3) to (6).

[0016]

[0017] <6> The negative photosensitive resin composition according to <5>, wherein the total amount of diamine residues derived from diamines represented by any one of general formulas (3) to (6) is 50 to 100 mol % relative to 100 mol % of all diamine residues in the component (A).

[0018] <7> The negative photosensitive resin composition according to <5>, wherein the total amount of diamine residues derived from the diamine represented by general formula (3) and the diamine residues derived from the diamine represented by general formula (4) is 20 to 80 mol %, relative to 100 mol % of all diamine residues in the component (A).

[0019] <8> The negative photosensitive resin composition according to <5>, in which the total of the diamine residues derived from the diamine represented by general formula (5) and the diamine residues derived from the diamine represented by general formula (6) is 20 to 80 mol % relative to 100 mol % of all diamine residues in the component (A).

[0020] <9> The negative photosensitive resin composition according to <5>, wherein the ratio of the total a mol % of diamine residues derived from diamines represented by general formula (3) and diamine residues derived from diamines represented by general formula (4) to the total b mol % of diamine residues derived from diamines represented by general formula (5) and diamine residues derived from diamines represented by general formula (6), relative to 100 mol % of all diamine residues of the component (A), is a:b=20:80 to 80:20.

[0021] <10> The negative photosensitive resin composition according to <5>, wherein the ratio of the mol % of diamine residues a(4) derived from diamine represented by general formula (4) to the mol % of diamine residues a(5) derived from diamine represented by general formula (5), relative to 100 mol % of all diamine residues in the component (A), is a(4):a(5)=20:80 to 80:20.

[0022] <11> The negative photosensitive resin composition according to <1>, wherein the (B) polymerizable compound is a radical polymerizable compound, and the (C) photopolymerization initiator is a photoradical polymerization initiator.

[0023] <12> The negative photosensitive resin composition according to any one of <1> to <3>, wherein the (B) polymerizable compound is a cationically polymerizable compound, and the (C) photopolymerization initiator is a photocationic polymerization initiator.

[0024] <13> The negative photosensitive resin composition according to <2> or <3>, containing 0.0001 to 0.05 parts by mass of at least one of 4-methyl-gamma-butyrolactone, methyl 4-methoxybutanoate, 1,4-dioxane, triethylene glycol dimethyl ether, and 2-butyltetrahydrofuran, per 100 parts by mass of the polymer compound (A).

[0025] <14> The negative photosensitive resin composition according to any one of <1> to <4>, which is used to form a negative pattern on an aluminum electrode.

[0026] <15> A negative photosensitive resin composition film formed from the negative photosensitive resin composition according to <1>.

[0027] <16> A negative photosensitive resin composition film having the negative photosensitive resin composition coating according to <15> and a support.

[0028] <17> A cured film obtained by curing the negative photosensitive resin composition according to <1> or the negative photosensitive resin composition film according to <15>.

[0029] <18> An electronic component comprising the cured film according to <17>.

[0030] 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 electronic components 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.

[0031] The negative-type photosensitive resin composition of the present invention is a negative-type photosensitive resin composition containing (B) a polymerizable compound and (C) a photopolymerization initiator, characterized in that the content of fluorine atoms in the total solid content of the negative-type photosensitive resin composition is 0.0 mass % or more and 1.0 mass % or less.

[0032] The fluorine atom content of the negative-type photosensitive resin composition of the present invention is 0.0 mass% or more and 1.0 mass% or less based on the total solid content. By having the fluorine atom content of the negative-type photosensitive resin composition of the present invention be 0.0 mass% or more and 1.0 mass% or less based on the total solid content, deposits are less likely to be formed during dry etching due to a reaction between aluminum and fluorine-containing organic components generated as decomposition gases in the negative-type photosensitive resin composition of the present invention. In other words, by using the negative-type photosensitive resin composition of the present invention, electronic components having aluminum electrodes can be made into highly reliable electronic components having organic insulating films.

[0033] The content of fluorine atoms in the total solid content contained in the negative photosensitive resin composition of the present invention can be analyzed by the following method, with the amount of the total solid content being taken as 100 mass %.

[0034] A negative photosensitive resin composition varnish or a negative photosensitive resin composition film with the protective film removed is precisely weighed as a sample. Using an automatic sample combustion device, it is burned in the combustion tube of an analyzer, and the generated gas is absorbed into a solution, after which a portion of the absorbed solution is analyzed by ion chromatography. The absorbed solution is H ２ O ２ 0.036% by weight can be used.

[0035] <Component (A)> The negative photosensitive resin composition of the present invention preferably further contains, as component (A), at least one polymer compound selected from the group consisting of polyimides, polyamides, and polyamideimides.

[0036] (The polymer compound (A) may be referred to as component (A).) By including the component (A), the negative photosensitive resin composition of the present invention has excellent film-forming properties when it is made into a film.

[0037] The (A) polymer compound is preferably soluble in an alkaline aqueous solution. When the (A) polymer compound is soluble in an alkaline aqueous solution, development with an alkaline aqueous solution can be performed during pattern processing without using organic solvents, which are a factor in environmental load. Here, "soluble in an alkaline aqueous solution" refers to a polymer compound in which 0.1 g or more of the (A) polymer compound dissolves in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C. To exhibit alkali solubility, the (A) polymer compound desirably has an alkali-soluble functional group. The alkali-soluble functional group is a functional group having acidity, and specific examples thereof include a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group. Among the above-mentioned alkali-soluble functional groups, the alkali-soluble functional group is preferably a phenolic hydroxyl group in view of issues such as the storage stability of the photosensitive resin composition and corrosion of copper wiring as a conductor.

[0038] 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 compounds in the component (A) may be used alone or in combination of two or more. The weight-average molecular weight of the polymer compounds in the component (A) in the present invention is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

[0039] The negative photosensitive resin composition of the present invention preferably contains at least one polymer compound selected from the group consisting of polyamide, polyimide, and polyamideimide, and may contain a polymer compound other than polyamide, polyimide, and polyamideimide as long as it contains at least one polymer compound selected from the group consisting of polyamide, polyimide, and polyamideimide. Note that the polyimide precursor does not correspond to the above-mentioned polyamide.

[0040] In the present invention, the component (A) is preferably a compound having at least one structure selected from the structures represented by general formula (1) and general formula (2).

[0041]

[0042] (In the general formulas (1) and (2), 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 (1) and (2) １ and X ２ each 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.

[0043] The component (A) preferably contains at least one diamine residue derived from a diamine represented by any one of the general formulas (8) to (12).

[0044] The component (A) containing at least one diamine residue derived from a diamine represented by any one of general formulas (8) to (12) 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 a diamine represented by any one of general formulas (8) to (12) undergoes a crosslinking reaction with the 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.

[0045] Furthermore, it is preferable that the component (A) contains at least one diamine residue derived from a diamine represented by any one of the general formulas (3) to (6).

[0046] The component (A) containing a diamine residue derived from at least one diamine of the general formulas (3) to (6) 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 (3) to (6) undergoes a crosslinking reaction with the 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.

[0047] Furthermore, the total amount of diamine residues derived from diamines represented by any one of general formulas (3) to (6) 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 (3) to (6) 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.

[0048] Furthermore, the total of the diamine residues derived from the diamine represented by general formula (3) and the diamine residues derived from the diamine represented by general formula (4) is preferably 20 to 80 mol %, and more preferably 30 to 60 mol %, relative to 100 mol % of all diamine residues in component (A). Having the total of the diamine residues derived from the diamine represented by general formula (3) or (4) within this preferred range is advantageous in that it improves the solubility of component (A) in solvents and the resolution during pattern processing.

[0049] Furthermore, the total of the diamine residues derived from the diamine represented by general formula (5) and the diamine residues derived from the diamine represented by general formula (6) is preferably 20 to 100 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 60 mol%, relative to 100 mol% of all diamine residues in component (A). When the total of the diamine residues derived from the diamine represented by general formula (5) or (6) is within the preferred range, the improved solubility resulting from the cardo structure contained in the diamine represented by general formula (5) or the improved solubility resulting from the phenylene ether bond contained in the diamine represented by general formula (6) is advantageous in that it improves the resolution during pattern processing.

[0050] Furthermore, the ratio of the total a mol % of diamine residues derived from diamines represented by general formula (3) and diamines represented by general formula (4) to the total b mol % of diamine residues derived from diamines represented by general formula (5) and diamines represented by general formula (6), relative to 100 mol % of all diamine residues in component (A), is preferably a:b=20:80 to 80:20. This range improves the long-term storage stability of component (A). This mechanism is presumed to be due to the fact that the diamine residues represented by general formula (3) or (4) and the diamine residues represented by general formula (5) or (6) being within the above ranges, resulting in an appropriate strength of interaction between components (A).

[0051] Furthermore, it is preferable that the component (A) contains a diamine residue derived from a diamine represented by general formula (4) and a diamine residue derived from a diamine represented by general formula (5), and the ratio of the diamine residues a(4) mol % derived from the diamine represented by general formula (4) to the diamine residues a(5) mol % derived from the diamine represented by general formula (5) relative to 100 mol % of all diamine residues is a(4):a(5) = 20:80 to 80:20. When the ratio of the diamine residues derived from the diamine represented by general formula (4) to the diamine residues derived from the diamine represented by general formula (5) is within this range, high processability and long-term storage stability can be obtained.

[0052] Furthermore, when the total carboxylic acid residues contained in the component (A) is X mol and the total diamine residues are Y mol, the ratio Y / X of all diamine residues to all carboxylic acid residues is preferably 0.55 to 0.95, and more preferably 0.60 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 photosensitive resin composition has sufficient heat resistance, and when it is at most the upper limit of the preferred range, the sensitivity during pattern processing is not reduced and resolution is further improved, which is preferable.

[0053] 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, as well as compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. The other diamine to be copolymerized can be used as is or as the corresponding diisocyanate compound or trimethylsilylated diamine. Two or more of these diamine components may also be used in combination.

[0054] 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.

[0055] Furthermore, the component (A) preferably contains a carboxylic acid residue derived from an acid dianhydride represented by the following general formula (7).

[0056]

[0057] When the component (A) contains a carboxylic acid residue derived from an acid dianhydride represented by the following general formula (7), the solubility is increased and the resolution is improved. In addition, when the negative-type photosensitive resin composition is formed into a cured film, the chemical resistance is improved and the ion migration resistance is improved, which is preferable.

[0058] 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.

[0059] The imidization rate of the component (A) is preferably 70 to 100%, and more preferably 90 to 100%. By setting the imidization rate of the component (A) within the preferred range, the content of amide groups that can inhibit the reactivity of the component (B) when it is a cationically polymerizable compound is reduced, which is preferable in that it improves sensitivity during pattern processing. Furthermore, it is preferable in that it reduces the change in the imide ring closure rate when the negative-type photosensitive resin composition is thermally cured, thereby reducing cure shrinkage and enabling stress reduction.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] The molar ratio of the structures represented by general formulas (1) and (2) 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] A monoamine can also be introduced into component (A) as an end-capping agent. When a monoamine is introduced as an end-capping agent, the ratio y / x (the total molar amount of diamine and (molar amount of monoamine / 2) y mol) to the amount x mol of acid anhydride used in polymerization is preferably 0.55 to 0.95. Introducing a monoamine in this range can exhibit sufficient cationic polymerizability and improve the storage stability of the negative-type photosensitive resin composition.

[0069] Examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, and 2-carboxy-7-aminonaphthalene. , 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-amino-4-tert-butylphenol, etc. can be used. Among these, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 2-amino-4-tert-butylphenol are preferred. Two or more of these may be used.

[0070] 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.

[0071] In the present invention, the component (A) can be polymerized by the above method, then poured into a large amount of water or a mixture of methanol and water, precipitated, filtered, dried, and isolated. In this case, the drying temperature is preferably 40 to 100°C, more preferably 50 to 80°C. This procedure removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties after thermal curing.

[0072] In the present invention, component (A) can be polymerized in solution and then stored and used as a polymerization solution without being filtered, dried, or isolated as described above. Specific examples of the solvent 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; 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; ketones such as acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone. alcohols such as ethanol, 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 others such as N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea, 2-pyrrolidone, o-nitroanisole, N-cyclohexyl-2-pyrrolidone, and N-(2-hydroxyethyl)-2-pyrrolidone.

[0073] By storing and using the component (A) in the form of a polymerization solution, the production process can be simplified and the environmental load can be reduced. In order to store and use the polymerization solution as is, it is preferable that component (A) contains diamine residues derived from at least one diamine of general formulas (3) to (6). The ratio of the total a mol % of diamine residues derived from diamines represented by general formula (3) and diamine residues derived from diamines represented by general formula (4) to the total b mol % of diamine residues derived from diamines represented by general formula (5) and diamine residues derived from diamines represented by general formula (6), relative to 100 mol % of all diamine residues in component (A), is preferably a:b=20:80 to 80:20. When the total carboxylic acid residues contained in component (A) are X mol and the total diamine residues are Y mol, the ratio Y / X of the total diamine residues to the total carboxylic acid residues is preferably 0.55 to 0.95. When a monoamine is introduced as an end-capping agent, the ratio y / x of the total y mol of the molar amount of diamine and (the molar amount of monoamine / 2) relative to the amount x mol of the acid anhydride used in the polymerization is preferably 0.55 to 0.95.

[0074] 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.

[0075] <Component (B)> The negative-tone photosensitive resin composition of the present invention contains a polymerizable compound as component (B) (the polymerizable compound (B) may be referred to as component (B)). By containing the polymerizable compound (B), the negative-tone photosensitive resin composition of the present invention undergoes a polymerization reaction, resulting in excellent negative-tone pattern processability. The polymerization method may be, but is not limited to, radical polymerization, cationic polymerization, anionic polymerization, addition polymerization, or other reaction methods.

[0076] The polymerizable compound (B) is preferably a radically polymerizable compound or a cationically polymerizable compound. More preferably, the polymerizable compound (B) is a cationically polymerizable compound. Since the cationic polymerization reaction is a ring-opening polymerization reaction, it has less cure shrinkage than a radically polymerizable compound and reduces internal stress after pattern processing, resulting in excellent thick-film formability.

[0077] The radical polymerizable compound may be any compound containing an unsaturated bond-containing group. Preferred examples of the unsaturated bond-containing group include unsaturated double bond-containing groups such as vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups, and unsaturated triple bond-containing groups such as propargyl groups. The radical polymerizable compound may contain two or more of these unsaturated bond-containing groups. Among these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred in terms of polymerizability. Furthermore, from the viewpoint of suppressing cracks in the pattern due to excessive crosslinking points caused by the polymerization reaction, the number of unsaturated bonds in the radical polymerizable compound is preferably 1 to 6.

[0078] Examples of the radical polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butane Diol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,Preferred examples include 6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, propylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, ethylene oxide isocyanurate-modified diacrylate, ethylene oxide isocyanurate-modified triacrylate, tricyclodecane dimethanol diacrylate, N-vinylpyrrolidone, N-vinylcaprolactam, divinyldimethoxysilane, trivinylmethoxysilane, and diallyldimethoxysilane. The radical polymerizable compound may contain two or more of these.

[0079] Among these, examples of the radical polymerizable compound include 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylene bisamide, N,N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, and N-methyl-2,2,6,6-tetramethyl Preferred are aryl piperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, propylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, ethylene oxide isocyanurate-modified diacrylate, ethylene oxide isocyanurate-modified triacrylate, tricyclodecane dimethanol diacrylate, N-vinylpyrrolidone, N-vinylcaprolactam, divinyldimethoxysilane, trivinylmethoxysilane, and diallyldimethoxysilane. Among these, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, propylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A methacrylate, ethylene oxide isocyanurate-modified triacrylate, tricyclodecane dimethanol diacrylate, divinyldimethoxysilane, trivinylmethoxysilane, and diallyldimethoxysilane are more preferred.

[0080] The radical polymerizable compound is preferably a compound having an octanol / water partition coefficient (log P value) of -2 or more and less than 6. Here, the log P value is an index of the lipophilicity or hydrophilicity of a substance, and is defined as the logarithm of the ratio of the concentration of the substance dissolved in the octanol phase to the concentration of the substance dissolved in the aqueous phase in an octanol / water two-phase system. A larger log P value indicates greater lipophilicity, while a smaller log P value indicates greater hydrophilicity. The log P value can be measured by the flask immersion method described in JIS-Z-7260-107:2000, but can also be calculated. In this specification, the log P value calculated using ChemDraw (registered trademark) manufactured by CambridgeSoft is used. A radical polymerizable compound having a log P value within the above range is preferred in terms of excellent compatibility with the (A) polymer compound and excellent pattern processability when developed with an alkaline aqueous solution.

[0081] Examples of radically polymerizable compounds having a log P value within the above range include, but are not limited to, BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd., ethylene oxide-modified bisphenol A dimethacrylate, log P value 5.54), DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., dimethylol-tricyclodecane diacrylate, log P value 3.05), dipentaerythritol hexaacrylate (log P value 2.72), dipentaerythritol pentaacrylate, log P value 1.81), and M-315 (manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified di- and triacrylate, log P value 0.75).

[0082] The content of the radical polymerizable compound in the photosensitive resin composition of the present invention is preferably 40 parts by mass or more, and more preferably 50 parts by mass or more, per 100 parts by mass of the polymer compound (A), from the viewpoint of improving the residual film rate after development. On the other hand, the content of the radical polymerizable compound is preferably 150 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the polymer compound (A), from the viewpoint of improving the heat resistance of the cured film.

[0083] Preferred examples of the cationically polymerizable compound include cyclic ether compounds (such as epoxy compounds and oxetane compounds), ethylenically unsaturated compounds (such as vinyl ethers and styrenes), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters.

[0084] As the epoxy compound, known compounds can be used, and preferred examples include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

[0085] 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).

[0086] 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).

[0087] 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.).

[0088] 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.

[0089] 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.

[0090] Preferred examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0091] Preferred examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0092] Preferred examples of the polyfunctional vinyl ether include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0093] Preferred examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0094] Preferred examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] Of these cationically polymerizable compounds, epoxy compounds, oxetane compounds and vinyl ethers are preferred, and epoxy compounds and oxetane compounds are more preferred.

[0099] The cationically polymerizable compounds may be used alone or in combination of two or more kinds.

[0100] The content of the 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 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.

[0101] <Component (C)> The negative photosensitive resin composition of the present invention contains a photopolymerization initiator as component (C) (the (C) photopolymerization initiator is sometimes referred to as component (C)). The (C) photopolymerization initiator generates radicals or acids when exposed to light, thereby polymerizing the (B) polymerizable compound. More specifically, it is preferable that the (B) polymerizable compound is a radical polymerizable compound and the (C) photopolymerization initiator is a photoradical polymerization initiator, and it is also preferable that the (B) polymerizable compound is a cationically polymerizable compound and the (C) photopolymerization initiator is a photocationic polymerization initiator.

[0102] Preferred examples of the photoradical polymerization initiator for the component (C) include oximes, benzophenones, benzylidenes, coumarins, anthraquinones, benzoins, thioxanthones, mercaptos, glycine oximes, benzyl dimethyl ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, and 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole. Specifically, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl phenone), anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0103] Although known compounds can be used as the cationic photopolymerization initiator for the component (C), it is preferred that the cationic photopolymerization initiator 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. The cationic photopolymerization initiator 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, which is preferred in that the cationic polymerization of the cationically polymerizable compound proceeds sufficiently during pattern processing, resulting in a good pattern.

[0104] 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.

[0105] When the cationically polymerizable compound contains a sulfonium salt, preferred examples of the counter anion that forms the sulfonium salt include a borate ion, a phosphate ion, a gallate ion, 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.

[0106] 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.

[0107] Preferred examples of the phosphate ion include, but are not limited to, hexafluorophosphate, tris(pentafluoroethyl)trifluorophosphate, and the like.

[0108] Preferred examples of the gallate ion include, but are not limited to, tetrakis(pentafluorophenyl)gallate and tetrakis(3,5-bis(trifluoromethyl)phenyl)gallate.

[0109] 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.

[0110] <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.

[0111] 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.

[0112] 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 is suppressed, facilitating the processing of 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.

[0113] 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.

[0114] 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 of such a surfactant include MX-280, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0115] The negative-type photosensitive resin composition of the present invention may further contain a silane compound. By containing a silane compound, the adhesion of the negative-type 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.

[0116] 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.

[0117] The negative-type photosensitive resin composition of the present invention preferably contains 0.0001 to 0.05 parts by mass of at least one compound selected from the group consisting of 4-methyl-gamma-butyrolactone, methyl 4-methoxybutanoate, 1,4-dioxane, triethylene glycol dimethyl ether, and 2-butyltetrahydrofuran, per 100 parts by mass of the (A) polymer compound. The inclusion of these compounds can improve the resolution when the photosensitive resin composition is processed. More preferably, the content of each of these compounds is 0.001 to 0.02 parts by mass, per 100 parts by mass of the (A) polymer compound.

[0118] <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 formed from the negative photosensitive resin composition of the present invention.

[0119] The negative photosensitive resin composition film of the present invention is a film of the negative photosensitive resin composition of the present invention laminated 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 of the above-mentioned components (B) to (C) and any other optional components dissolved 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.

[0120] The thickness of the negative photosensitive resin composition coating of the present invention is preferably 1 μm or more, more preferably 5 μm or more, from the viewpoint of handleability. Furthermore, in order to easily form a thick film layer when producing an electronic component having the cured film of the present invention, which will be described later, the thickness is more preferably 20 μm or more, particularly preferably 30 μm or more. Furthermore, in order to suppress variation in film thickness, the thickness of the negative photosensitive resin composition coating is preferably 100 μm or less, more preferably 80 μm or less, particularly preferably 60 μm or less.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] <Cured Film, Electronic Components> 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] In either case, the substrates used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, piezoelectric substrates, and substrates on which circuit components are arranged. 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, silicon carbide substrates, lithium niobate substrates, and lithium tantalate substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of materials constituting the circuit include conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, low dielectrics containing glass-based materials and / or resins, high dielectrics containing resins and high-dielectric-constant inorganic particles, and insulators containing glass-based materials.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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 for electronic parts such as electronic components.

[0141] The electronic component of the present invention is an electronic component having the cured film of the present invention. Here, the term "electronic component" refers to any device that can function by utilizing the characteristics of a semiconductor element. Electronic components include electro-optical devices in which a semiconductor element is connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices that include these. Electronic components also include multilayer wiring boards for connecting semiconductor elements. Specifically, the cured film of the present invention 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 present invention is not limited to these applications and can be used for a variety of other purposes.

[0142] Furthermore, the negative-tone photosensitive resin composition of the present invention is characterized by the absence of organic deposits even when processed on a substrate having an aluminum electrode. Therefore, it is preferably used when forming a negative pattern on an aluminum electrode, and the electronic component of the present invention preferably has an aluminum electrode. As described above, the negative-tone photosensitive resin composition of the present invention has a fluorine atom content of 0.0 mass% or more and 1.0 mass% or less of the total solid content of the resin composition, which reduces the occurrence of deposits caused by the reaction of aluminum with fluorine-containing organic components generated as decomposition gases in the negative-tone photosensitive resin composition of the present invention during dry etching. In other words, by using the negative-tone photosensitive resin composition of the present invention, electronic components having highly reliable organic insulating films can be obtained, even in electronic components having aluminum electrodes.

[0143] Examples of electronic components having aluminum 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.

[0144] When the cured film of the present invention is measured by the ion elution amount measurement method described below, the ion elution amount is preferably 2000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 to 0 ppm.

[0145] <Method for measuring the amount of eluted ions> The cured film is placed in 10 times the mass of pure water and subjected to hot water extraction at 121°C for 20 hours, after which the supernatant of the extract is used as the test liquid. The test liquid and a standard solution of the target ions are introduced into an ion chromatograph, and the concentrations of formate ions, acetate ions, propionate ions, and sulfate ions in the test liquid are determined by the calibration curve method. The value converted into the mass of eluted ions relative to the mass of the organic film is used as the amount of eluted ions.

[0146] The specific method for measuring the amount of ion elution is as follows. The cured film prepared by the above method is placed in a PTFE pressurized sealed container with 10 times the mass of pure water, and hot water extraction is performed in a high-temperature oven at 121°C for 20 hours. The supernatant of the extract is filtered through a membrane filter to obtain the test solution. The mass of the cured film is preferably 0.1 to 5.0 g, with 0.3 to 3.0 g being preferred for workability and stable ion extraction. If necessary, the cured film may be freeze-pulverized using liquid nitrogen. The pure water used here is distilled and ion-exchanged, and is used for reagent preparation, microanalysis tests, etc., as specified in JIS K 0557 (1998). The hot water pressure extraction method procedure was based on Yoshimi Hashimoto, Analytical Chemistry (Bunseki Kagaku), 49, 8 (2000). The extraction temperature conditions were based on Ai Kitamura, Network Polymer, 33, 3 (2012). This test solution is analyzed in accordance with the ion chromatography method of Japanese Industrial Standards JIS K 0127 (2013) General Principles of Ion Chromatography. Standard solutions of formate ions, acetate ions, propionate ions, and sulfate ions are introduced into an ion chromatography analyzer to prepare a calibration curve. Next, 25 μL of the test solution is introduced, and the concentrations of formate ions, acetate ions, propionate ions, and sulfate ions are determined from the peak areas and the calibration curve. The values ​​converted into the eluted ion mass relative to the mass of the organic film are used as the eluted ion amount.

[0147] When the total amount of eluted formate ions, acetate ions, propionate ions, and sulfate ions of the cured film is measured by a method for measuring the amount of eluted ions, the amount being equal to or less than the above-mentioned value, corrosion of the metal wiring of the laminate under high temperature and high humidity conditions can be suppressed, and the cured film can be preferably used for applications such as electronic components.

[0148] In order to keep the amount of ion elution below the above value, the photoradical polymerization initiator in component (C) is preferably an oxime, and particularly preferably an o-benzoyloxime compound, and the photocationic polymerization initiator is preferably a sulfonium salt having tetrakis(pentafluorophenyl)gallate or tetrakis(3,5-bis(trifluoromethyl)phenyl)gallate as the counter anion.

[0149] When a compound having an alkoxymethyl group or a methylol group is used as the thermal crosslinking agent in order to keep the amount of ion elution at or below the above-mentioned value, the amount thereof is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of component (A).

[0150] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0151] <Fluorine Atom Content in Total Solids in Negative Photosensitive Resin Composition> A negative photosensitive resin composition varnish or a negative photosensitive resin composition film from which the protective film has been removed, prepared in each of the Examples and Comparative Examples described below, was precisely weighed as a sample. Using the automatic sample combustion apparatus described below, the sample was burned in the combustion tube of an analyzer, and the generated gas was absorbed into a solution. A portion of the absorbed solution was then analyzed by ion chromatography. In the case of a resin solution, the total fluorine atom content (% by mass) in the obtained sample was divided by the solids concentration (% by mass) to determine the fluorine atom content in the total solids in the negative photosensitive resin composition.

[0152] <Combustion and absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C Outlet 1000°C Gas: Ar / O ２200mL / min :O ２ / 400 mL / min Absorption liquid: H ２ O ２ 0.036 mass%, internal standard P 4 μg / mL Amount of absorption solution: 20 mL <Conditions for ion chromatography and anion analysis> System: ICS1600 (manufactured by DINONEX Co., Ltd.) Mobile phase: 2.7 mmol / L Na ２ CO ３ / 0.3 mmol / L NaHCO ３ Flow rate: 1.5 mL / min. Detector: electrical conductivity detector. Injection volume: 20 μL.

[0153] <Patterning on Silicon Substrate Having Aluminum Pad Electrode> Evaluations using the negative photosensitive resin composition films prepared in the examples and comparative examples described below are shown below.

[0154] 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.

[0155] 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 (hereinafter sometimes referred to as TMAH), and then 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.

[0156] The pattern thus obtained was observed under an optical microscope, and the minimum exposure dose necessary for pattern formation was taken as the sensitivity, and the minimum size when the pattern was free of abnormalities such as distortion or clogging was taken as the resolution. The exposure dose was calculated based on the illuminance measured with i-line.

[0157] 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.

[0158] 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.

[0159] The evaluation will be shown below using the negative photosensitive resin composition varnishes prepared in the examples and comparative examples described below.

[0160] Each of the negative photosensitive resin composition varnishes prepared in the examples and comparative examples described below was applied to a silicon substrate using a spinner and baked on a hot plate at 100°C for 3 minutes to form a resin composition coating film with a thickness of 15 µm.

[0161] Next, 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 the aluminum pad electrode portion and the silicon portion, respectively. A full wavelength exposure was performed using an ultra-high pressure mercury lamp under the condition of an exposure gap of 100 μm between the mask and the photosensitive resin composition film. After exposure, the film was post-exposure baked on a hot plate at 120 ° C for 1 minute. Thereafter, the unexposed portions were removed by dip development using a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH), 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.

[0162] The pattern thus obtained was observed under an optical microscope, and the minimum exposure dose necessary for pattern formation was taken as the sensitivity, and the minimum size when the pattern was free of abnormalities such as distortion or clogging was taken as the resolution. The exposure dose was calculated based on the illuminance measured with i-line.

[0163] 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.

[0164] 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.

[0165] <Storage Stability of Photosensitive Resin Composition> The negative photosensitive resin composition varnishes prepared in each of the Examples and Comparative Examples described below were stored in a sealed container at 25°C, and the rate of change in viscosity after 1 day to 20 days was measured.

[0166] <Amount of Ions Leached from Cured Film of Photosensitive Resin Composition> The negative photosensitive resin composition varnish prepared in each of the Examples and Comparative Examples described below was applied to a 6-inch silicon substrate, the weight of which had been measured in advance, using a spinner, and baked on a hot plate at 100°C for 3 minutes to form a resin composition film with a thickness of 15 µm. The resin composition film was heated to 1000 mJ / cm using an ultra-high pressure mercury lamp. ２ The exposure was calculated based on the illuminance measured with i-line. After exposure, the film was heated on a hot plate at 120°C for 1 minute. Then, the film was heated in an inert oven under N 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. The weight of the cured film alone was calculated from the weight of the silicon substrate measured in advance.

[0167] The cured film was divided into 16 sections, each consisting of 6-inch silicon, and placed in a sealed pressure-resistant decomposition vessel made of PTFE together with pure water in an amount 10 times the weight of the cured film alone. The section was then stored for 20 hours at 121°C, 100% humidity, and 2 atmospheres using a highly accelerated life tester (saturated pressure cooker tester). The supernatant of the extract was filtered through a membrane filter with a pore size of 0.45 μm to obtain the test solution.

[0168] Next, in accordance with the ion chromatography method of the Japanese Industrial Standards JIS K 0127 (2013) General Principles of Ion Chromatography, standard solutions of formate ions, acetate ions, propionate ions, and sulfate ions were introduced into an ion chromatography analyzer (ICS-3000 manufactured by Dionex Corporation) and a calibration curve was created. 25 μL of the test solution was introduced, and the concentrations of the formate ions, acetate ions, propionate ions, and sulfate ions in the test solution were determined from the resulting peaks and the calibration curve, and the total was taken as the amount of ion elution.

[0169] The compounds used in the examples and comparative examples were synthesized by the following methods.

[0170] 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 was added dropwise a solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone. After the addition was completed, the mixture was allowed to react at room temperature for 4 hours, and then the precipitated white solid was filtered and dried in vacuum at 50°C.

[0171] 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:

[0172]

[0173] 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.

[0174]

[0175] 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 78 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 10 g of GBL, and the mixture was stirred at 120° C. for 1 hour, then at 200° C. for 4 hours, and then cooled to obtain a solution of polyimide (A-1).

[0176] Synthesis Example 4 Synthesis of fluorine atom-free polyamideimide (A-2) A solution of fluorine atom-free polyamideimide (A-2) 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).

[0177] Synthesis Example 5 Synthesis of fluorine atom-free polyimide (A-3) A solution of fluorine atom-free polyimide (A-3) 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).

[0178] Synthesis Example 6 Synthesis of fluorine atom-free polyimide (A-4) A solution of fluorine atom-free polyimide (A-4) 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).

[0179] Synthesis Example 7 Synthesis of fluorine atom-free polyimide (A-5) A solution of fluorine atom-free polyimide (A-5) 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).

[0180] Synthesis Example 8 Synthesis of fluorine atom-free polyimide (A-6) A solution of fluorine atom-free polyimide (A-6) 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).

[0181] Synthesis Example 9 Synthesis of fluorine atom-free polyimide (A-7) A solution of fluorine atom-free polyimide (A-7) 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).

[0182] Synthesis Example 10 Synthesis of fluorine atom-free polyimide (A-8) A solution of fluorine atom-free polyimide (A-8) 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).

[0183] Synthesis Example 11 Synthesis of fluorine atom-free polyimide (A-9) A solution of fluorine atom-free polyimide (A-9) 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).

[0184] Synthesis Example 12 Synthesis of fluorine atom-free polyimide (A-10) A solution of fluorine atom-free polyimide (A-10) was obtained in the same manner as in Synthesis Example 3, except that APBS (8.41 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).

[0185] Synthesis Example 13 Synthesis of fluorine atom-free polyimide (A-11) A solution of fluorine atom-free polyimide (A-11) 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).

[0186] Synthesis Example 14 Synthesis of fluorine atom-free polyimide (A-12) A solution of fluorine atom-free polyimide (A-12) 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).

[0187] Synthesis Example 15 Synthesis of fluorine atom-free polyimide (A-13) A solution of fluorine atom-free polyimide (A-13) 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).

[0188] Synthesis Example 16 Synthesis of fluorine atom-free polyimide (A-14) A solution of fluorine atom-free polyimide (A-14) was obtained in the same manner as in Synthesis Example 3, except that AHPB (9.73 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).

[0189] Synthesis Example 17 Synthesis of fluorine atom-free polyimide (A-15) A solution of fluorine atom-free polyimide (A-15) 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).

[0190] Synthesis Example 18 Synthesis of fluorine atom-free polyimide (A-16) A solution of fluorine atom-free polyimide (A-16) 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).

[0191] Synthesis Example 19: Synthesis of fluorine atom-free polyimide (A-17) A solution of fluorine atom-free polyimide (A-17) 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).

[0192] Synthesis Example 20: Synthesis of fluorine atom-free polyimide (A-18) A solution of fluorine atom-free polyimide (A-18) 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).

[0193] Synthesis Example 21 Synthesis of fluorine atom-free polyimide (A-19) A solution of fluorine atom-free polyimide (A-19) 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).

[0194] Synthesis Example 22 Synthesis of fluorine atom-free polyimide (A-20) A solution of fluorine atom-free polyimide (A-20) 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).

[0195] Synthesis Example 23 Synthesis of fluorine atom-free polyimide (A-21) A solution of fluorine atom-free polyimide (A-21) 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).

[0196] Synthesis Example 24 Synthesis of fluorine atom-free polyimide (A-22) A solution of fluorine atom-free polyimide (A-22) 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).

[0197] Synthesis Example 25 Synthesis of fluorine atom-free polyimide (A-23) A solution of fluorine atom-free polyimide (A-23) 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).

[0198] Synthesis Example 26 Synthesis of fluorine atom-free polyimide (A-24) A solution of fluorine atom-free polyimide (A-24) 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).

[0199] Synthesis Example 27 Synthesis of Fluorine Atom-Free Polyimide Precursor (A-25) Under a dry nitrogen stream, BAP (23.25 g, 0.09 mol) was added to 80 g of GBL and stirred and dissolved 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 a solution of polyimide precursor (A-25).

[0200] Synthesis Example 28 Synthesis of fluorine atom-free polyimide precursor (A-26) A solution of fluorine atom-free polyimide (A-26) was obtained in the same manner as in Synthesis Example 27, except that ABPS (25.23 g, 0.09 mol) was used instead of BAP (23.25 g, 0.09 mol).

[0201] Synthesis Example 29 Synthesis of solution of fluorine atom-free polyimide precursor (A-27) A fluorine atom-free polyimide (A-27) was obtained in the same manner as in Synthesis Example 27, except that FDA (34.24 g, 0.09 mol) was used instead of BAP (23.25 g, 0.09 mol).

[0202] Synthesis Example 30 Synthesis of solution of fluorine atom-free polyimide precursor (A-28) A fluorine atom-free polyimide (A-28) was obtained in the same manner as in Synthesis Example 27, except that AHPB (29.19 g, 0.09 mol) was used instead of BAP (23.25 g, 0.09 mol).

[0203] Synthesis Example 31 Synthesis of fluorine atom-containing polyimide (A-29) A solution of fluorine atom-containing polyimide (A-29) 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).

[0204] Synthesis Example 32 Synthesis of fluorine atom-containing polyimide (A-30) A solution of fluorine atom-containing polyimide (A-30) 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).

[0205] Synthesis Example 33 Synthesis of fluorine atom-free polyimide (A-31) A solution of fluorine atom-free polyimide (A-31) was obtained in the same manner as in Synthesis Example 3, except that ABPS (22.42 g, 0.08 mol) and FDA (3.80 g, 0.01 mol) were 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).

[0206] Synthesis Example 34 Synthesis of fluorine atom-free polyimide (A-32) A solution of fluorine atom-free polyimide (A-32) was obtained in the same manner as in Synthesis Example 3, except that ABPS (19.60 g, 0.07 mol) and FDA (7.60 g, 0.02 mol) were 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).

[0207] Synthesis Example 35 Synthesis of fluorine atom-free polyimide (A-33) A solution of fluorine atom-free polyimide (A-33) was obtained in the same manner as in Synthesis Example 3, except that ABPS (14.00 g, 0.05 mol) and FDA (15.20 g, 0.04 mol) were 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).

[0208] Synthesis Example 36: Synthesis of fluorine atom-free polyimide (A-34) A solution of fluorine atom-free polyimide (A-34) was obtained in the same manner as in Synthesis Example 3, except that ABPS (5.60 g, 0.02 mol) and FDA (26.60 g, 0.07 mol) were 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).

[0209] Synthesis Example 37 Synthesis of fluorine atom-free polyimide (A-35) A solution of fluorine atom-free polyimide (A-35) was obtained in the same manner as in Synthesis Example 3, except that ABPS (2.80 g, 0.01 mol) and FDA (30.40 g, 0.08 mol) were 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).

[0210] Synthesis Example 38 Synthesis of Fluorine-Atom-Free Polyimide (A-36) Under a dry nitrogen stream, ODPA (31.02 g, 0.1 mol) was added to 68 g of GBL and dissolved with stirring at 120° C. Next, 3-aminophenol (3.10 g, 0.028 mol) was added together with 10 g of GBL, and the mixture was stirred at 120° C. for 15 minutes. Then, ABPS (11.20 g, 0.04 mol) and FDA (15.20 g, 0.04 mol) were added together with 10 g of GBL, and the mixture was stirred for 1 hour. Subsequently, the mixture was stirred at 200° C. for 4 hours and then cooled to obtain a solution of polyimide (A-36).

[0211] Synthesis Example 39 Synthesis of fluorine atom-free polyimide (A-37) A solution of fluorine atom-free polyimide (A-37) was obtained in the same manner as in Synthesis Example 38, except that BAP (10.33 g, 0.04 mol) was used instead of ABPS (11.20 g, 0.04 mol).

[0212] Synthesis Example 40 Synthesis of fluorine atom-free polyimide (A-38) A solution of fluorine atom-free polyimide (A-38) was obtained in the same manner as in Synthesis Example 38, except that AHPB (12.97 g, 0.04 mol) was used instead of FDA (15.20 g, 0.04 mol).

[0213] Synthesis Example 41 Synthesis of fluorine atom-free polyimide (A-39) A solution of fluorine atom-free polyimide (A-39) was obtained in the same manner as in Synthesis Example 38, except that BAP (10.33 g, 0.04 mol) and AHPB (12.97 g, 0.04 mol) were used instead of ABPS (11.20 g, 0.04 mol) and FDA (15.20 g, 0.04 mol).

[0214] Example 1 25.64 g of a solution of polyimide (A-1) as the component (A) (10 g as solids, assuming a solids concentration of the solution of 39%), 12.00 g of TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.) as the component (B), 0.60 g of CPI-310B (trade name, manufactured by San-Apro Co., Ltd.) as the component (C), and 0.40 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% by mass, with additives other than the solvent being considered as solids. 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.

[0215] 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.

[0216] Examples 2 to 36 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 having 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.

[0217] Example 37 256.41 g of a solution of polyimide (A-3) as the component (A) (100 g as solids when the solids concentration of the solution was 39%), 60.00 g of BP-6EM (trade name, manufactured by Kyoeisha Chemical Co., Ltd., ethylene oxide-modified bisphenol A dimethacrylate) as the component (B), 9.00 g of NCI-930 (trade name, manufactured by ADEKA Corporation, oximes) as the component (C), 20.00 g of NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) as a thermal crosslinking agent, 0.01 g of phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, and 2.00 g of KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent were dissolved in 25.00 g of ethyl lactate and 1.50 g of GBL as other components. Thereafter, the mixture was filtered under pressure using a filter with a retention particle size of 1 μm to obtain a negative photosensitive resin composition varnish.

[0218] The resulting negative-type photosensitive resin composition varnish was used to evaluate its pattern processability on a silicon substrate having an aluminum pad electrode, as described above. The results are shown in Table 2. The fluorine atom content of the total solid content in the negative-type photosensitive resin composition of Example 37 was 0.0 mass%.

[0219] Examples 38 to 62 Negative photosensitive resin composition varnishes were prepared in the same manner as in Example 37, 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, the storage stability of the photosensitive resin composition, and the amount of ion elution from a cured film of the photosensitive resin composition were evaluated. The results are shown in Table 2.

[0220] Comparative Examples 1 to 4 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 having 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.

[0221] Comparative Example 5 A negative photosensitive resin composition varnish was prepared in the same manner as in Example 37, 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, the storage stability of the photosensitive resin composition, and the amount of ion elution from a cured film of the photosensitive resin composition were evaluated. The results are shown in Table 2.

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229] As is clear from Tables 1 and 2, in Comparative Examples 1 to 5, the content of fluorine atoms in the total solid content of the negative photosensitive resin composition was more than 1.0 mass %, and therefore, when patterning was performed on a silicon substrate having an aluminum pad electrode, organic deposits were generated.

[0230] 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.

[0231] As a notable example, Examples 3, 33, 34, and Comparative Examples 3 and 4 differ only in the type and amount of component (C), and the fluorine atom contents relative to the total solid content of the negative-type photosensitive resin composition are 0.8 mass%, 1.0 mass%, 1.0 mass%, 1.1 mass%, and 1.2 mass%, respectively. As a result, it was shown that when the fluorine atom content relative to the total solid content of the negative-type photosensitive resin composition is 1.0 mass% or less, no organic deposits are formed when processing is performed on a silicon substrate having an aluminum pad electrode, but when the fluorine atom content exceeds 1.0 mass%, the organic deposits are formed.

[0232] The compounds used in each synthesis example, example and comparative example are shown below.

[0233] Compounds used in the synthesis of component (A) TDA-100: acid dianhydride represented by general formula (7) ODPA: acid dianhydride HBPDA: acid dianhydride having an alicyclic structure APB-N: diamine containing no fluorine atoms BAP: diamine represented by general formula (3) ABPS: diamine represented by general formula (4) FDA: diamine represented by general formula (5) AHPB: diamine represented by general formula (6) Fluorine atom-free diamine compound (a) Fluorine atom-containing diamine compound (b).

[0234]

[0235] Component (B): Cationic polymerizable compound TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd., epoxy compound).

[0236] Radical polymerizable compounds BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd., ethylene oxide modified bisphenol A dimethacrylate) DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., dimethylol-tricyclodecane diacrylate) M-315 (manufactured by Toagosei Co., Ltd., isocyanuric acid EO modified di- and triacrylate) M-403 (manufactured by Toagosei Co., Ltd., dipentaerythritol penta- and hexaacrylate).

[0237] Component (C) Photocationic Polymerization Initiator CPI-310B (manufactured by San-Apro Ltd., sulfonium salt containing fluorine atoms and borate ions) CPI-310FG (manufactured by San-Apro Ltd., sulfonium salt containing fluorine atoms and gallate ions).

[0238] Photoradical polymerization initiators: NCI-930 (trade name, manufactured by ADEKA Corporation, o-methoxycarbonyl oximes); OXE-02 (manufactured by BASF Japan Ltd., o-methoxycarbonyl oximes); OXE-02 (manufactured by BASF Japan Ltd., o-methoxycarbonyl oximes); PBG-305 (trade name, manufactured by Changzhou Strong Electronic New Materials Co., Ltd., o-benzoyl oximes).

[0239] Other components: Silane coupling agent X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0240] Thermal crosslinking agent: NIKALAC MW-100LM (manufactured by Sanwa Chemical Co., Ltd.).

[0241] VG-3101L ("TECHMORE" (registered trademark) VG3101L product name, manufactured by Printec Co., Ltd.).

[0242] Polymerization inhibitor: Phenothiazine (Tokyo Chemical Industry Co., Ltd.).

[0243] Compound D1: 4-methyl gamma butyrolactone Compound D2: methyl 4-methoxybutanoate Compound D3: 1,4-dioxane Compound D4: triethylene glycol dimethyl ether Compound D5: 2-butyltetrahydrofuran

Claims

1. A negative-type photosensitive resin composition comprising (B) a polymerizable compound and (C) a photopolymerization initiator, wherein the content of fluorine atoms in the total solid content of the negative-type photosensitive resin composition is 0.0 mass% or more and 1.0 mass% or less.

2. The negative type photosensitive resin composition according to claim 1, further comprising (A) a polymer compound, said (A) being at least one polymer compound selected from the group consisting of polyimide, polyamide, and polyamideimide.

3. The negative photosensitive resin composition according to claim 2, wherein the polymer compound (A) is soluble in an alkaline aqueous solution.

4. The negative type photosensitive resin composition according to claim 2 or 3, wherein the (A) polymer compound (hereinafter, sometimes referred to as component (A)) contains at least one type of diamine residue derived from a diamine represented by any one of general formulas (8) to (12). (In the general formula (8), Z and Z ２ each independently represents a monovalent organic group having 1 to 20 carbon atoms and not containing a hydrogen atom or a fluorine atom. General formula (9) does not include the structure represented by general formula (8), and in general formula (9), Z3 represents a sulfonyl group, a carbonyl group, an oxygen atom, a divalent organic group having a linear aliphatic group having 2 to 20 carbon atoms and not containing a fluorine atom, or a single bond. In general formula (10), Z4 and Z5 each independently represent an amide group, a sulfonyl group, a carbonyl group, an oxygen atom, or a single bond. In general formula (11), Z6 and Z7 each independently represent a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom, or a phenylene group. In general formula (12), Z ８ and Z ９ each independently represents a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom or a phenylene group; Z １０ and Z １１ each independently represents an amide group, a sulfonyl group, a carbonyl group, an oxygen atom, or a single bond.

5. The negative photosensitive resin composition according to claim 2 or 3, wherein the component (A) contains at least one diamine residue derived from a diamine represented by any one of general formulas (3) to (6).

6. The negative type photosensitive resin composition according to claim 5, wherein the total amount of diamine residues derived from diamines represented by any one of general formulas (3) to (6) is 50 to 100 mol % relative to 100 mol % of all diamine residues in the component (A).

7. The negative type photosensitive resin composition according to claim 5, wherein the total of the diamine residues derived from the diamine represented by general formula (3) and the diamine residues derived from the diamine represented by general formula (4) is 20 to 80 mol % relative to 100 mol % of all diamine residues in the component (A).

8. The negative type photosensitive resin composition according to claim 5, wherein the total of the diamine residues derived from the diamine represented by general formula (5) and the diamine residues derived from the diamine represented by general formula (6) is 20 to 80 mol % relative to 100 mol % of all diamine residues in the component (A).

9. The negative photosensitive resin composition according to claim 5, wherein the ratio of the total a mol % of diamine residues derived from diamine represented by general formula (3) and diamine residues derived from diamine represented by general formula (4) to the total b mol % of diamine residues derived from diamine represented by general formula (5) and diamine residues derived from diamine represented by general formula (6) is a:b=20:80 to 80:20, relative to 100 mol % of all diamine residues of the component (A).

10. The negative photosensitive resin composition according to claim 5, wherein the ratio of mol % of diamine residues a(4) derived from diamine represented by general formula (4) to mol % of diamine residues a(5) derived from diamine represented by general formula (5) is a(4):a(5)=20:80 to 80:20, relative to 100 mol % of all diamine residues in the component (A).

11. The negative photosensitive resin composition according to claim 1, wherein the (B) polymerizable compound is a radically polymerizable compound, and the (C) photopolymerization initiator is a photoradical polymerization initiator.

12. The negative photosensitive resin composition according to claim 1, wherein the polymerizable compound (B) is a cationically polymerizable compound, and the photopolymerization initiator (C) is a photocationic polymerization initiator.

13. The negative type photosensitive resin composition according to claim 2 or 3, containing 0.0001 to 0.05 parts by mass of at least one selected from the group consisting of 4-methyl gamma butyrolactone, methyl 4-methoxybutanoate, 1,4-dioxane, triethylene glycol dimethyl ether, and 2-butyltetrahydrofuran, per 100 parts by mass of the (A) polymer compound.

14. The negative type photosensitive resin composition according to claim 1, which is used to form a negative type pattern on an aluminum electrode.

15. A negative-type photosensitive resin composition film formed from the negative-type photosensitive resin composition according to claim 1.

16. A negative photosensitive resin composition film comprising the negative photosensitive resin composition coating according to claim 15 and a support.

17. A cured film obtained by curing the negative type photosensitive resin composition according to claim 1 or the negative type photosensitive resin composition coating according to claim 15.

18. An electronic component comprising the cured film according to claim 17.

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