Negative-type photosensitive resin composition, dry film, cured matter, and electronic component

Abstract

To provide a novel negative-type photosensitive resin composition that has more excellent resolution and is capable of reducing development residue.SOLUTION: A negative-type photosensitive resin composition according to an embodiment includes (A) a polyhydroxyamide compound, (B) a photoacid generator, (C) a crosslinking agent, and (D) alcoholamines.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a negative photosensitive resin composition, a dry film, a cured product, and an electronic component. [Background technology]

[0002] Photosensitive resin compositions containing polybenzoxazole precursors exhibit excellent properties such as insulating properties, heat resistance, and mechanical strength, and are therefore widely used as insulating films in various fields such as semiconductors and electronic components.

[0003] In the past, there has been a demand for higher integration of semiconductor elements in response to the demand for higher performance and smaller size of electronic components and electrical equipment. In recent years, in order to meet these demands, technologies for higher performance and smaller size have been developed in the field of semiconductor element packaging, such as wafer-level packaging, and there has been an increasing demand for finer pattern formation (resolution) in insulating films used in rewiring layers.

[0004] Patent Document 1 discloses the use of a negative photosensitive resin composition containing a specific polyamide derivative, which is a photosensitive polybenzoxazole precursor, a compound that generates an acid upon irradiation with radiation, and a compound that can crosslink the specific polyamide derivative. According to the disclosure of Patent Document 1, a pattern with a good shape that is excellent in sensitivity, resolution, and heat resistance, and highly reliable electronic components are provided.

[0005] Patent Document 2 discloses that a pattern excellent in sensitivity and resolution can be formed by using a negative photosensitive resin composition that contains a polymer component consisting of two or more different types of heat-resistant polymers having reactive terminal groups, a compound that generates an acid when irradiated with actinic rays, and a compound that can be crosslinked or polymerized by the action of the acid. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2001-125267 A [Patent Document 2] JP 2008-033159 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0007] When the negative photosensitive resin composition of Patent Document 1 is used, a pattern with a resolution of 5 to 8 μm can be formed, and when the negative photosensitive resin composition of Patent Document 2 is used, a pattern with a resolution of 5 to 6 μm can be formed. However, there was a concern that the resolution level when using these negative photosensitive resin compositions was not sufficient to form a highly integrated circuit. Furthermore, when the pattern is finer, the pattern is more likely to remain undissolved (development residue) in the unexposed area that should be removed during development, and forming a circuit using such a pattern may cause poor conduction or the like.

[0008] Therefore, an object of the present disclosure is to provide a new negative type photosensitive resin composition that has superior resolution and can reduce development residues. Another object of the present disclosure is to provide a cured product using the negative type photosensitive resin composition, and electronic parts such as printed wiring boards and semiconductor elements using the same. [Means for solving the problem]

[0009] The present inventors have found that the above problems can be solved by combining a polyhydroxyamide compound, a photoacid generator, a crosslinking agent, and an alcohol amine, and have completed the present invention. That is, one aspect of the disclosed technology is The negative photosensitive resin composition includes (A) a polyhydroxyamide compound, (B) a photoacid generator, (C) a crosslinking agent, and (D) an alcohol amine. The (A) polyhydroxyamide compound preferably contains a structural unit represented by the following formula (1). [ka] (R in the formula 1 is a divalent organic group, R 2 is a tetravalent organic group. The (B) photoacid generator preferably contains an oxime sulfonate compound. The oxime sulfonate compound preferably has a structure represented by the following formula (2): [ka] (In the formula, X represents a hydrocarbon group or a halogen atom, m represents an integer of 0 to 3, and R 3 is a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom. The (C) crosslinking agent preferably has a heterocyclic skeleton. The (C) crosslinking agent is preferably a compound having at least one group selected from the group consisting of a methoxymethyl group and a methylol group. The alcohol amines are preferably alcohol amines having a plurality of alcohols bonded thereto. The negative photosensitive resin composition preferably contains (E) a compound containing a phenolic hydroxyl group. The (E) compound containing a phenolic hydroxyl group preferably contains a polyhydroxystyrene polymer or a polyhydroxystyrene copolymer. Another aspect of the disclosed technique is a dry film including a resin layer formed from the negative type photosensitive resin composition. Another aspect of the disclosed technique is a cured product formed from the negative photosensitive resin composition or the resin layer of the dry film. Another aspect of the present disclosure is an electronic component having the cured product. Effect of the Invention

[0010] According to the disclosed technique, it is possible to provide a new negative type photosensitive resin composition that has superior resolution and can reduce development residues. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the expression "a to b" in the description of a numerical range means a to b, unless otherwise specified.

[0012] 1. Negative-type photosensitive resin composition The negative photosensitive resin composition of this embodiment preferably contains (A) a polyhydroxyamide compound, (B) a photoacid generator, (C) a crosslinking agent, and (D) an alcohol amine. The negative photosensitive resin composition of this embodiment has high resolution, so that fine patterning can be formed. Specifically, the negative photosensitive resin composition of this embodiment can make the line / space (L / S) in the pattern of a semiconductor circuit or a circuit board 3.0 μm / 3.0 μm or less, and can also make it 2.0 μm / 2.0 μm or less, or even 1.0 μm / 1.0 μm or less. In addition, the aspect ratio (line height / line width) can be 1.0 or more, and can also be 2.0 or more, 2.5 or more, or even 3.0 or more. In addition, it is also possible to form a via with an opening diameter of 2.0 μm or less. The mechanism by which the disclosed technology can provide excellent resolution and reduce development residues is not clear, but is presumed to be as follows. When a resin layer made of a negative photosensitive resin composition is exposed to light, an acid is generated from the photoacid generator, and the reaction of the resin component and the crosslinking agent proceeds, making the exposed portion insoluble in the developer. At this time, since the acid generated by exposure diffuses in the resin layer, it is considered that the reaction proceeds sufficiently even at the bottom of the resin layer (for example, in the case of a resin layer formed on a substrate, this refers to the periphery of the interface between the resin layer and the substrate). On the other hand, the present inventors have found that when the acid generated by exposure diffuses to the unexposed portion, the unexposed portion also becomes insoluble in the developer, which may cause a decrease in resolution or development residue. In the disclosed technology, it is believed that the inclusion of alcohol amines, which are basic compounds, can adequately suppress the diffusion of acid generated by exposure, thereby making it possible to obtain excellent resolution and reduce development residues. In particular, it is presumed that the use of alcohol amines having an alcoholic hydroxyl group, which is an alkali-soluble group, makes it possible to reduce development residues due to their particularly excellent solubility in the developer.

[0013] 1-1.(A) Polyhydroxyamide compounds The polyhydroxyamide compound (A) is not particularly limited, but it is preferable that the compound contains a structural unit represented by the following formula (1) in order to enhance the resolution of a negative-type photosensitive resin composition, enable the formation of fine patterns, and provide a cured product having excellent insulation reliability. [ka] (In the formula, R 1 is a divalent organic group, R 2 is a tetravalent organic group.

[0014] R in formula (1) 1 is not particularly limited as long as it is a divalent organic group, and examples thereof include an alkylene group, a cycloalkylene group, an arylene group, an alkyl ether group, a ketone group, and an ester group. Among these, divalent aromatic hydrocarbon groups having a skeleton such as benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenyl propane, diphenyl hexafluoropropane, and benzophenone, or divalent aliphatic hydrocarbon groups having a skeleton such as butane and cyclobutane are preferred. From the viewpoint of the resolution of the negative photosensitive resin composition and the insulation reliability of the cured product, R 1 The carbon number of R is preferably 4 to 30, and phenyl, biphenyl, diphenyl ether, and diphenylhexafluoropropane are preferred. 1 It is also possible to contain two or more of the groups exemplified above as .

[0015] R in formula (1) 2is not particularly limited as long as it is a tetravalent organic group, but is preferably a tetravalent aromatic hydrocarbon group having a skeleton such as biphenyl, diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfoxide, diphenyl sulfone, or benzene, and more preferably an organic group having a structure represented by the following formula (3). [ka] (In the formula, a is an integer of 0 to 3, and * indicates a bond.)

[0016] The polyhydroxyamide compound (A) may have an alkali-soluble group at its terminal. The alkali-soluble group at the terminal is not particularly limited, but may be a functional group such as an alcoholic hydroxyl group, a phenolic hydroxyl group, an acid anhydride group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, or an active methylene group. From the viewpoint of solubility in a developer, it is preferable that the polyhydroxyamide compound has a carboxyl group or a phenolic hydroxyl group. Among these alkali-soluble groups, a phenolic hydroxyl group is particularly preferred. When the (A) polyhydroxyamide compound has a phenolic hydroxyl group at its terminal, the solubility of the (A) polyhydroxyamide compound in a developer can be improved. Furthermore, since the phenolic hydroxyl group has a lower reactivity than the carboxyl group, excessive reaction with the crosslinking agent is suppressed, and the solubility of the unexposed area in the developer can be maintained even when the PEB process is performed, and thus the resolution can be maintained. It is therefore presumed that a negative photosensitive resin composition capable of forming a finer L / S pattern with a high aspect ratio can be provided. The alkali-soluble groups located at the terminals of the polyhydroxyamide compound (A) may be those present as residues of monomers constituting the polyhydroxyamide compound (A) or may be those present as terminal structures introduced by a terminal-capping agent having an alkali-soluble group. The alkali-soluble groups located at the terminals of the polyhydroxyamide compound (A) are preferably those present as terminal structures introduced by a terminal-capping agent having an alkali-soluble group.

[0017] Examples of the end-capping agent include, but are not limited to, compounds having one amino group and a hydroxyl group, such as aminophenol compounds, hydroxybenzylamine compounds, aminobenzyl alcohol compounds, and alcoholamine compounds; compounds having one carboxyl group and a hydroxyl group, such as hydroxyacids; acid anhydride compounds having a hydroxyl group, such as hydroxyacid anhydrides; compounds having an amino group and a carboxyl group, such as aminobenzoic acid and amino acids; and acid anhydride compounds, such as phthalic anhydride and 5-norbornene-2,3-dicarboxylic anhydride.

[0018] The weight average molecular weight (Mw) of the (A) polyhydroxyamide compound is not particularly limited, but is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 15,000. By setting it within such a range, it becomes possible to form a finer L / S pattern with a higher aspect ratio. The number average molecular weight (Mn) of the (A) polyhydroxyamide compound is preferably from 1,000 to 10,000, more preferably from 1,500 to 7,000, and even more preferably from 3,000 to 5,000. The polydispersity index (PDI) of the (A) polyhydroxyamide compound is preferably from 1.5 to 4.0, more preferably from 1.5 to 3.5, and even more preferably from 2.0 to 3.0. When the weight-average molecular weight (Mw), number-average molecular weight (Mn) and molecular weight dispersity (PDI) of the (A) polyhydroxyamide compound are within the above ranges, the solubility in a developer in the unexposed area and the reaction with the (C) crosslinking agent upon exposure are well balanced, and a negative-type photosensitive resin composition having excellent resolution can be obtained. In this specification, the weight average molecular weight and the number average molecular weight are values ​​measured by gel permeation chromatography (GPC) (GL7700 manufactured by GL Science) and converted into standard polystyrene. Specific measurement conditions are as follows. Column: TSKgel αM (Tosoh Corporation) Column temperature: 40℃ Eluent composition: NMP solution containing 100mmol / L H3PO4 (H3PO4 85% aqueous solution used as raw material) and 10mmol / L LiBr Eluent flow rate: 0.5mL / min Calibration standard: Polystyrene Detector wavelength: 260nm and 300nm Detector temperature: Room temperature Baseline range at analysis: 15 to 40 minutes Molecular weight calculation range during analysis: 20 to 35 minutes In this specification, the polydispersity index (PDI) is calculated by the following formula (4). (Formula 4) PDI=Mw / Mn

[0019] When the (A) polyhydroxyamide compound contains a carboxyl group, the carboxyl group equivalent of the (A) polyhydroxyamide compound can be, for example, 1,500 g / eq or more. When the (A) polyhydroxyamide compound does not contain a carboxyl group or contains a carboxyl group, it is preferably 2,000 g / eq or more, and more preferably does not contain a carboxyl group. When the (A) polyhydroxyamide compound does not contain a carboxyl group or has a carboxyl group equivalent within the range, a negative photosensitive resin composition with better resolution can be obtained. Note that the carboxyl group has the function of improving the solubility of the polyhydroxyamide compound in a developer, but it is presumed that the reaction with the (C) crosslinking agent in the heat treatment (also called PEB (Post Exposure Bake)) performed before the development step proceeds excessively, reducing the solubility of the unexposed area in the developer, thereby worsening the resolution, but the details are unknown.

[0020] The hydroxyl equivalent of the (A) polyhydroxyamide compound is not particularly limited, but can be, for example, 100 to 400 g / eq, preferably 150 to 350 g / eq, and more preferably 200 to 300 g / eq.

[0021] The chlorine atom concentration (or chlorine ion concentration) contained in the molecular structure of the (A) polyhydroxyamide compound is not particularly limited, but is preferably 5 mass ppm or less based on the total mass of the (A) polyhydroxyamide compound. The lower the chlorine atom concentration (or chlorine ion concentration) contained in the molecular structure of the negative photosensitive resin composition, the easier it is to improve the insulation reliability of the cured product.

[0022] 1-2.(B) Photoacid generator (B) The photoacid generator is not particularly limited as long as it is a compound that generates an acid by irradiation with light such as ultraviolet light or visible light, and examples thereof include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyamide sulfonates, aromatic N-oxyimide sulfonates, aromatic sulfamides, oxime sulfonate compounds, naphthalimides, and benzoquinone diazosulfonic acid esters. These may be used alone or in combination in any ratio. The photoacid generator is preferably an oxime sulfonate compound from the viewpoint of improving insulation reliability, and more preferably includes a structure represented by the following formula (2). [ka] (In the formula, X represents a hydrocarbon group or a halogen atom, m represents an integer of 0 to 3, and R 3 is a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom. X in formula (2) can be a hydrocarbon group (eg, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.) or a halogen atom. The hydrocarbon group may have a substituent and may have a linear, branched or cyclic structure. The hydrocarbon group is preferably a linear or branched group having 1 to 4 carbon atoms. As the halogen atom, a chlorine atom or a fluorine atom is preferably used.

[0023] In formula (2), m represents an integer of 0 to 3, and is preferably 0 or 1. When m is 2 or 3, multiple Xs may be the same or different.

[0024] R in Equation (2) 3 is preferably a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom. The hydrocarbon group (e.g., an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc.) may be unsubstituted or may be substituted with a halogen atom. The hydrocarbon group is preferably a straight-chain, branched-chain or cyclic group having 1 to 20 carbon atoms, and more preferably a straight-chain, branched-chain or cyclic group having 1 to 10 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom.

[0025] Commercially available oxime sulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203 manufactured by BASF.

[0026] 1-3.(C) Crosslinking agent The (C) crosslinking agent is not particularly limited and may be a known one, for example, a melamine compound, a guanamine compound, a triazine compound, an epoxy compound, an oxetane compound, an isocyanate compound, an oxazoline compound, etc. The crosslinking agent is preferably a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group. These crosslinking agents use the acid generated from the (B) photoacid generator as an active species to cause a crosslinking reaction with the phenolic hydroxyl group and the carboxyl group contained in the (A) polyhydroxyamide compound, etc., by heating, and thus negative photolithography (pattern formation) is realized by exposure, PEB, and development treatment. In addition, by further heating after pattern formation, the curing reaction of the negative photosensitive resin composition proceeds, and excellent properties are expressed as a cured product.

[0027] In addition, the (C) crosslinking agent preferably has a heterocyclic skeleton in order to improve the resolution of the negative photosensitive resin composition and the insulation reliability after curing. The heterocyclic ring is not particularly limited, and includes one or more heteroatoms such as boron, nitrogen, oxygen, phosphorus, sulfur, antimony, arsenic, bismuth, selenium, silicon, tellurium, and tin, and includes a 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, or 8-membered saturated or unsaturated ring. From the viewpoint of the resolution of the negative photosensitive resin composition and the insulation reliability of the cured product, the heterocyclic ring is preferably a nitrogen-containing heterocyclic ring, and more preferably a multiple nitrogen-containing heterocyclic ring. Specifically, compounds having a triazine structure such as hexamethylolmelamine and hexamethoxymethylmelamine, compounds having a guanamine structure such as tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanamine, compounds having a glycoluril structure such as tetramethylolglycoluril and tetramethoxyglycoluril, and compounds having an imidazolidinone structure such as 1,3-bis(methoxymethyl)-2-imidazolidinone are more preferred. Among these, compounds having a triazine structure containing a triazine ring and compounds having a guanamine structure are preferably used from the viewpoint of providing a negative photosensitive resin composition capable of forming an L / S pattern having a finer and higher aspect ratio.

[0028] 1-4.(D) Alcohol amines The negative photosensitive resin composition of the present embodiment preferably contains (D) alcohol amines. The (D) alcohol amines are not particularly limited, and may be a primary amine, a secondary amine, or a tertiary amine to which one or more primary alcohols, secondary alcohols, or tertiary alcohols are bonded. The alcohol bonded to the amine may be either a saturated alcohol or an unsaturated alcohol. Furthermore, when multiple alcohols are bonded to the amine, each alcohol may be the same or different alcohols. The number of carbon atoms contained in one alcohol bonded to the amine is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alcohol amines are preferably those in which an alcohol is bonded to a tertiary amine. These may be used alone or in combination in any desired ratio.

[0029] The alcohol amines are preferably those having a plurality of alcohols bonded thereto, and more preferably those having a plurality of diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, or N,N-dimethylethanolamine bonded thereto. Such alcohol amines can efficiently prevent the acid generated from the photoacid generator (B) by exposure from diffusing to the unexposed area, and can further reduce development residues generated in the unexposed area after development.

[0030] 1-5.(E) Compounds containing a phenolic hydroxyl group The negative photosensitive resin composition of this embodiment may contain (E) a compound containing a phenolic hydroxyl group. When the negative photosensitive resin composition contains (E) a compound containing a phenolic hydroxyl group, the resolution of the negative photosensitive resin composition becomes better. This is presumably due to the increase in the phenolic hydroxyl group in the negative photosensitive resin composition, which promotes the crosslinking reaction with the (C) crosslinking agent in the exposed area and the developability of the unexposed area, but the detailed mechanism is unclear because the resolution is improved significantly more than expected. It should be noted that (E) the compound containing a phenolic hydroxyl group is a compound different from (A) the polyhydroxyamide compound, (B) the photoacid generator, and (C) the crosslinking agent.

[0031] (E) The compound containing a phenolic hydroxyl group is not particularly limited as long as it contains one or more phenolic hydroxyl groups. (E) The compound containing a phenolic hydroxyl group may be, for example, a monomer such as phenol, o-cresol, m-cresol, p-cresol, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, hydroquinone, catechol, resorcinol, hydroxyquinol, phloroglucinol, pyrogallol, hexahydroxybenzene, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, 2,5-xylenol, m-ethylphenol, 3,5-xylenol, m-methoxyphenol, bisphenol A, or bisphenol F. Examples of polymers include phenolic resins such as resol-type phenolic resins and novolac-type phenolic resins; polyphenol polymers such as polyhydroxystyrene polymers obtained by polymerizing hydroxystyrene (which may be any of o-, m-, or p-); and polyphenol copolymers such as polyhydroxystyrene copolymers obtained by copolymerizing hydroxystyrene (which may be any of o-, m-, or p-) with other polymerizable compounds such as styrene. These can be used alone or in combination in any ratio. Among these, polyhydroxystyrene polymers obtained by polymerizing hydroxystyrene (which may be any of o-, m-, and p-) or polyhydroxystyrene copolymers obtained by copolymerizing hydroxystyrene (which may be any of o-, m-, and p-) with other polymerizable compounds are preferred, and polyhydroxystyrene copolymers obtained by copolymerizing hydroxystyrene (which may be any of o-, m-, and p-) with styrene are more preferred.

[0032] The weight average molecular weight (Mw) of the polyhydroxystyrene polymer or polyhydroxystyrene copolymer is preferably from 2,000 to 10,000, more preferably from 3,000 to 8,000, and even more preferably from 4,000 to 6,000. The number average molecular weight (Mn) of the polyhydroxystyrene polymer or polyhydroxystyrene copolymer is preferably from 1,000 to 5,000, more preferably from 1,500 to 4,000, and even more preferably from 2,000 to 3,000. The polyhydroxystyrene polymer or polyhydroxystyrene copolymer preferably has a polydispersity index (PDI) of 1.5 to 4.0, more preferably 1.5 to 3.0. When the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight dispersity (PDI) of the polyhydroxystyrene polymer or polyhydroxystyrene copolymer are within the above ranges, the resolution of the negative photosensitive resin composition can be made even better.

[0033] The hydroxyl group equivalent of the (E) compound containing a phenolic hydroxyl group is not particularly limited, but is, for example, preferably 100 to 300 g / eq, and more preferably 100 to 200 g / eq.

[0034] The chlorine atom concentration (or chlorine ion concentration) contained in the molecular structure of the (E) phenolic hydroxyl group-containing compound is not particularly limited, but is preferably 5 mass ppm or less based on the total mass of the (E) phenolic hydroxyl group-containing compound. The lower the chlorine atom concentration (or chlorine ion concentration) contained in the molecular structure of the negative photosensitive resin composition, the easier it is to improve the insulation reliability of the cured product.

[0035] 1-6.(F) Inorganic filler The negative photosensitive resin composition of the present embodiment may contain (F) an inorganic filler. The (F) inorganic filler is not particularly limited, and a conventionally known inorganic filler may be used, for example, silica, aluminum hydroxide, alumina, aluminum nitride, boron nitride, glass powder, magnesium carbonate, barium sulfate, barium titanate, hydrotalcite, etc. These may be used alone or in combination in any ratio. From the viewpoint of excellent insulation reliability and low thermal expansion coefficient of the negative photosensitive resin composition, it is preferable to use silica, and it is particularly preferable to use spherical silica.

[0036] The volume average particle diameter (D50) of the (F) inorganic filler can be 1.0 μm or less, preferably 500 nm or less, and particularly preferably 100 nm or less. The volume average particle diameter of the (F) inorganic filler can be measured by a laser diffraction method.

[0037] 1-7.Solvent The negative photosensitive resin composition of the present embodiment may contain a solvent. The solvent is not particularly limited, and examples thereof include ethers, esters, glycol esters, ketones, lactones, lactams, sulfoxides, tetramethylurea, dimethylsulfone, and pyridine.

[0038] Examples of ethers include 2-methoxy-1-methylethyl acetate (PGMEA), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0039] Examples of esters include ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, and ethyl 2-ethoxypropionate.

[0040] Ketones include methyl ethyl ketone, methyl isobutyl ketone (4-methyl-2-pentanone), 2-heptanone, Cycloalkanones, which are monoketones such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone; cycloalkanones such as diketones, 1,3-cyclopentanedione, 3-methyl-1,2-cyclopentanedione, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,4-cyclohexanedione, and 2-methyl-1,3-cyclopentanedione; Cycloalkenones such as 4-methyl-2-cyclopentenone, 2-cyclohexenone, 2-cyclopenten-1-one, and 2-cyclohexen-1-one; Examples include cyclic ketones having a heterocyclic skeleton, such as 2-azetidinone, 4,5-dihydro-3(2H)-thiophenone, 4-oxothiane, and dihydrolevogluconocene.

[0041] Examples of glycol esters include carbitol acetate, ethyl cellosolve acetate, and ethylene glycol monoethyl ether acetate.

[0042] Examples of lactones include γ-butyrolactone, etc. Examples of lactams include N-methylpyrrolidone, N-methylcaprolactam, etc. Examples of sulfoxides include dimethyl sulfoxide, hexamethyl sulfoxide, etc.

[0043] These solvents can be used alone or in combination of a plurality of solvents at any ratio. Among these solvents, lactones or cyclic ketones are preferred from the viewpoint of excellent affinity with each component in the negative photosensitive resin composition, and γ-butyrolactone or cyclopentanone are preferred. In addition, from the viewpoint of excellent solvent removability during drying of the negative photosensitive resin composition and compatibility with the edge rinse process in semiconductor manufacturing, cyclic ketones are preferred, and cycloalkanones, which are cyclic monoketones, are more preferred, and cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2-norbornanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 3-methylcyclohexanone, and 2,2-dimethylcyclopentanone are even more preferred, and cyclopentanone is particularly preferred.

[0044] 1-8.Other ingredients The negative photosensitive resin composition of the present embodiment may contain other components as long as the effects of the disclosed technology are not impaired. As the other components, known components that can be contained in negative photosensitive resin compositions can be used, and examples of such components include an adhesive, a surfactant, a plasticizer, a thermal acid generator, a sensitizer, a leveling agent, a colorant, fibers, and fine particles.

[0045] The surfactant is not particularly limited, and examples thereof include fluorosurfactants, silicon-based surfactants, etc. Commercially available fluorosurfactants include the "Megafac" series manufactured by DIC Corporation (e.g., Megafac F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-569, etc.). Examples of commercially available silicone surfactants include the BYK-Chemie Surface Conditioner Series (e.g., BYK-302, BYK-307, BYK-310, BYK-322, BYK-323, BYK-326, BYK-331, BYK-332, BYK-333, BYK-348, BYK-349, BYK-377, BYK-378, BYK-3455, BYK-3760, etc.). These may be used alone or in combination of two or more.

[0046] 2. Preparation of negative-type photosensitive resin composition The negative photosensitive resin composition of the present embodiment can be obtained by mixing the components (A) polyhydroxyamide compound, (B) photoacid generator, (C) crosslinker, (D) alcohol amines, and optional components including (E) compound containing a phenolic hydroxyl group and (F) inorganic filler. The components can be mixed under heating as necessary.

[0047] The content of the (A) polyhydroxyamide compound can be 50 to 80% by mass, assuming that the total mass of the solid content of the negative photosensitive resin composition is 100% by mass. Here, the solid content mass in this specification refers to the mass of the residue after the volatile components have been completely evaporated.

[0048] The content of the (B) photoacid generator can be 0.5 to 10 mass %, and preferably 1 to 5 mass %, when the total mass of the solid contents of the negative photosensitive resin composition is taken as 100 mass %.

[0049] The content of the (C) crosslinking agent can be 10 to 40% by mass, assuming that the total mass of the solid content of the negative photosensitive resin composition is 100% by mass. The content of the (C) crosslinking agent can be such that the ratio of the number of functional groups (reactive groups) contained in the (C) crosslinking agent (for example, the number of methoxymethyl groups and / or the number of methylol groups) to the number of phenolic hydroxyl groups contained in the negative photosensitive resin composition (methoxymethyl groups and / or methylol groups:phenolic hydroxyl groups) is 120:100 to 200:100. By setting the ratio in this way, the resolution of the negative photosensitive resin composition and the insulation reliability after curing can be improved.

[0050] The content of the (D) alcohol amines can be 0.01 to 0.50% by mass, and preferably 0.08 to 0.40% by mass, when the total mass of the solid content of the negative photosensitive resin composition is taken as 100% by mass. By setting the content within such a range, it becomes easier to suppress the occurrence of development residues in unexposed areas after the negative photosensitive resin composition is developed.

[0051] The content of the compound containing a phenolic hydroxyl group (E) when added can be 1 to 15 mass%, preferably 5 to 12 mass%, and more preferably 6 to 11 mass%, when the total mass of the solid content of the negative photosensitive resin composition is taken as 100 mass%. The content of the polyhydroxyamide compound (A): the content of the compound containing a phenolic hydroxyl group (E) (mass ratio) can be 80:20 to 99:1, preferably 80:20 to 95:5, and more preferably 85:15 to 90:10. The contents of the (A) polyhydroxyamide compound and (E) compound containing a phenolic hydroxyl group can be adjusted so that the ratio of the number of functional groups (reactive groups) (e.g., the number of methoxymethyl groups and / or the number of methylol groups) contained in the (C) crosslinking agent to the number of phenolic hydroxyl groups contained in the negative photosensitive resin composition (number of functional groups (reactive groups):phenolic hydroxyl groups) is 120: 100 to 200: 100. By setting such a ratio, the resolution of the negative photosensitive resin composition and the insulation reliability after curing can be improved.

[0052] The content of the (F) inorganic filler when added can be 1% by mass to 50% by mass, and preferably 10% by mass to 40% by mass, when the total mass of the solid content of the negative photosensitive resin composition is taken as 100% by mass. By setting the content in such a range, the cured product of the negative photosensitive resin composition can have a low thermal expansion coefficient while maintaining the developability of the negative photosensitive resin composition.

[0053] 3. Dry film The dry film of the present embodiment includes a substrate and a resin layer formed on the substrate using the negative type photosensitive resin composition of the present embodiment. In order to protect the resin layer, a protective film may be further laminated on the surface of the resin layer.

[0054] The substrate is not particularly limited, but examples thereof include metal foils such as copper foil; and films such as polyimide films, polyester films, and polyethylene naphthalate (PEN) films.

[0055] The protective film is not particularly limited, but polyethylene film, polytetrafluoroethylene film, polypropylene film, paper, etc. can be used. It is preferable to select a protective film in which the adhesive strength between the protective film and the resin layer is lower than that between the substrate and the resin layer. In order to make the adhesive strength between the protective film and the resin layer lower than that between the substrate and the resin layer, a protective film having a release treatment applied to its surface can be used.

[0056] The thickness of the resin layer is not particularly limited, but can be 1 to 150 μm depending on the application. The resin layer can be obtained, for example, by applying a negative photosensitive resin composition onto a substrate, adjusting the thickness of the resin layer using a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and drying the resin layer.

[0057] 4.Cured product The cured product of the present embodiment is obtained by curing the resin layer of the negative photosensitive resin composition or the dry film of the present embodiment. The cured product may be a patterned cured product. Examples of the method for producing the patterned cured product include the following method.

[0058] 4-1. Dry coating film formation process The dry coating film forming step is a step of applying the negative photosensitive resin composition of the present embodiment onto a substrate to form a coating film, and then drying the coating film. In the dry coating film forming step, a resin layer of a dry film can be transferred onto the substrate to form a dry coating film on the substrate.

[0059] The method of applying the negative photosensitive resin composition onto a substrate is not particularly limited, and examples thereof include a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., a spray application method using a spray coater, an inkjet method, etc. The thickness of the applied film is not particularly limited, and can be, for example, 10 μm or less, 5 μm or less, or 3 μm or less. By reducing the film thickness, finer L / S patterning is possible while maintaining the aspect ratio of the pattern.

[0060] The method for drying the coating film is not particularly limited, and examples thereof include air drying, heat drying in an oven or a hot plate, vacuum drying, etc. Conditions for heat drying are, for example, a heating temperature of 70 to 140° C. and a drying time of 1 to 30 minutes.

[0061] The transfer of the resin layer of the dry film onto the substrate is preferably carried out under pressure and heat using a vacuum laminator, etc. The heating temperature can be, for example, 60 to 100°C.

[0062] The substrate is not particularly limited, and may be, for example, a printed wiring board on which a circuit is formed, a flexible printed wiring board, or a wafer on which a semiconductor element is formed.

[0063] 4-2. Exposure process The exposure step is a step in which the dried coating film formed in the dry coating film forming step is irradiated with radiation through a photomask capable of forming a desired pattern, thereby sensitizing the photoacid generator (B) in the exposed area and generating active species. If patterning is not required, there is no need to use a photomask. Alternatively, a pattern may be directly drawn with a laser using a direct drawing device.

[0064] The wavelength of the radiation is such that the photoacid generator (B) can be activated, and in order to perform fine patterning, the maximum wavelength is preferably 410 nm or less. The irradiation energy can be adjusted depending on the thickness of the formed dry coating film, and is, for example, 10 to 1000 mJ / cm. 2 As the exposure light source, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, a KRF laser, or the like can be used.

[0065] 4-3.PEB process The PEB process is a process in which the dried coating film exposed in the exposure process is heat-treated to impart development resistance to the exposed portion of the dried coating film (hereinafter, sometimes abbreviated as the exposed portion). In the PEB process, a crosslinking reaction between the (A) polyhydroxyamide compound or the (E) compound containing a phenolic hydroxyl group and the (C) crosslinking agent proceeds in the exposed portion using the acid generated by the (B) photoacid generator as an active species, and the exposed portion becomes insoluble in a developer. The heating temperature in the PEB process can be 90 to 150°C, and the heating time can be 0.5 to 10 minutes. Heating can be performed by a known method such as a hot plate or a heating furnace.

[0066] 4-4.Developing process The developing step is a step in which the dried coating film heated in the PEB step is treated with a developer to dissolve and remove the unexposed areas of the dried coating film in the developer, thereby obtaining a patterned coating film. As the developing method, a known method can be used, for example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, etc.

[0067] The developer may be a known one, and examples of the developer include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide, etc. If necessary, a water-soluble organic solvent such as methanol, ethanol, and isopropyl alcohol, or a surfactant may be added.

[0068] After the treatment with the developer, the coating film can be washed with a rinse liquid as necessary to obtain a patterned coating film. The rinse liquid is not particularly limited, and examples thereof include pure water, methanol, ethanol, isopropyl alcohol, etc. These can be used alone or in combination of two or more in any ratio.

[0069] 4-5. Post-development heating process The post-development heating step is a step of heating the patterned coating film formed in the development step to complete the curing of the patterned coating film and obtain a cured patterned coating film (cured product). The heating temperature can be 150 to 200°C, and the heating time can be 1 to 120 minutes. Heating can be performed by a known method such as a hot plate or an inert oven, and heating is preferably performed under a nitrogen atmosphere.

[0070] 5. Uses of negative-type photosensitive resin compositions The negative photosensitive resin composition of the present embodiment can be suitably used as a material for forming a display device, a semiconductor element, an electronic component, an optical component, a building material, and the like. Examples of materials for forming a semiconductor element include resist materials, buffer coat films, and insulating films for rewiring layers of wafer level packages (WLPs). The negative photosensitive resin composition of the present embodiment can form extremely fine wiring with an L / S of 3.0 μm / 3.0 μm or less and an aspect ratio of 1.0 or more, and therefore can be preferably used in a rewiring layer formation process using a damascene method. Examples of materials for forming electronic components include printed wiring boards, interlayer insulating films, and wiring coating films. EXAMPLES

[0071] The present disclosure will be described in more detail using examples, but the present disclosure is not limited to the examples.

[0072] The components used in the examples and comparative examples are as follows. <(A) Polyhydroxyamide compound> (Synthesis Example 1: Synthesis Example of Polyhydroxyamide Compound (A-1)) In a 500 mL flask equipped with a stirrer and a thermometer, 21.62 g (59.03 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was dissolved in 140 g of N-methylpyrrolidone (NMP) by stirring. The flask was then immersed in an ice bath, and 12.09 g (40.97 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over 10 minutes while keeping the temperature in the flask at 0-5°C, and the mixture was stirred in the ice bath for 30 minutes. After stirring at room temperature for 18 hours, 5.93 g (36.13 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added at room temperature, and stirring was continued for another 3 hours. The stirred solution was poured into a large amount of ion-exchanged water, and the precipitate was collected. The obtained solid was dissolved in 160 g of ethyl acetate. 20 g of anion exchange resin (Organo Corporation Amberlyst B-20) was added thereto and vigorously stirred for 1 hour. The stirred solution was concentrated and then added to a large amount of ion exchange water to recover the precipitate. The precipitated solid was recovered and then dried under reduced pressure to obtain a polyhydroxyamide compound (A-1) having carboxyl groups at both ends. The obtained polyhydroxyamide compound (A-1) had a weight average molecular weight (Mw) of 8,613, a number average molecular weight (Mn) of 4,557, a polydispersity index (PDI) of 1.9, a chloride ion concentration of 3.3 ppm, a phenolic hydroxyl group equivalent of 294 g / eq, and a carboxyl group equivalent of 2,279 g / eq.

[0073] (A-1) Polyhydroxyamide compound [ka]

[0074] (Synthesis Example 2: Synthesis Example of Polyhydroxyamide Compound (A-2)) In a 500 mL flask equipped with a stirrer and a thermometer, 14.93 g (44.39 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 4.90 g (44.84 mmol) of 3-aminophenol were stirred and dissolved in 79 g of N-methylpyrrolidone (NMP). The flask was then immersed in an ice bath, and while keeping the temperature in the flask at 0-5°C, 16.41 g (55.61 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over a period of 10 minutes, and the mixture was stirred in an ice bath for 30 minutes. After stirring at room temperature for 18 hours, the solution was poured into a large amount of ion-exchanged water, and the precipitate was collected. The obtained solid was dissolved in 135 g of ethyl acetate. 18 g of anion-exchange resin (Organo Corporation Amberlyst B-20) was added thereto, and the mixture was stirred vigorously for 1 hour. The stirred solution was concentrated, then poured into a large amount of ion-exchanged water, and the precipitate was collected. The precipitated solid was collected and dried under reduced pressure to obtain a polyhydroxyamide compound (A-2) having phenolic hydroxyl groups at both ends. The obtained polyhydroxyamide compound (A-2) had a weight average molecular weight (Mw) of 4,580, a number average molecular weight (Mn) of 1,696, a polydispersity index (PDI) of 2.7, a chloride ion concentration of 2.3 ppm, and a phenolic hydroxyl group equivalent of 218 g / eq.

[0075] (A-2) Polyhydroxyamide compound [ka]

[0076] (Synthesis Example 3: Synthesis Example of Polyhydroxyamide Compound (A-3)) In a 500 mL flask equipped with a stirrer and a thermometer, 14.93 g (44.39 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 2.45 g (22.42 mmol) of 3-aminophenol were stirred and dissolved in 79 g of N-methylpyrrolidone (NMP). The flask was then immersed in an ice bath, and while keeping the temperature in the flask at 0-5°C, 16.41 g (55.61 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over a period of 10 minutes, and the mixture was stirred in an ice bath for 30 minutes. After stirring at room temperature for 18 hours, the solution was poured into a large amount of ion-exchanged water, and the precipitate was collected. The obtained solid was dissolved in 79 g of ethyl acetate. 17 g of anion-exchange resin (Organo Corporation Amberlyst B-20) was added thereto, and the mixture was stirred vigorously for 1 hour. The stirred solution was concentrated, then poured into a large amount of ion-exchanged water, and the precipitate was collected. The precipitated solid was collected and dried under reduced pressure to obtain a polyhydroxyamide compound (A-3) having phenolic hydroxyl groups at both ends. The obtained polyhydroxyamide compound (A-3) had a weight average molecular weight (Mw) of 9,222, a number average molecular weight (Mn) of 3,561, a polydispersity index (PDI) of 2.6, a chloride ion concentration of 3.1 ppm, and a phenolic hydroxyl group equivalent of 252 g / eq.

[0077] (A-3) Polyhydroxyamide compound [ka]

[0078] (Synthesis Examples 4 to 8: Synthesis Examples of Polyhydroxyamide Compounds (A-4 to A-8)) Polyhydroxyamide compounds were synthesized in the same manner as in Synthesis Example 3, except that the amounts of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 3-aminophenol, and 4,4'-oxybis(benzoyl chloride) (DEDC) were set to the ratios shown in Table 1. The polyhydroxyamide compounds (A-4 to A-8) had phenolic hydroxyl groups at both ends. The weight average molecular weight, number average molecular weight, and molecular weight dispersity of the obtained polyhydroxyamide compounds are also shown in Table 1.

[0079] [Table 1]

[0080] (Synthesis Example 9: Synthesis Example of Polyhydroxyamide Compound (A-9)) In a 500 mL flask equipped with a stirrer and a thermometer, 18.90 g (51.60 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was dissolved in 80 g of N-methylpyrrolidone (NMP) by stirring. The flask was then immersed in an ice bath, and 14.28 g (48.40 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over 10 minutes while keeping the temperature in the flask at 0-5°C, and the mixture was stirred in the ice bath for 30 minutes. After stirring at room temperature for 18 hours, 1.05 g (6.40 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added at room temperature, and stirring was continued for another 3 hours. The stirred solution was poured into a large amount of ion-exchanged water, and the precipitate was collected. The obtained solid was dissolved in 140 g of ethyl acetate. 8 g of anion exchange resin (Organo Corporation Amberlyst B-20) was added thereto and vigorously stirred for 1 hour. After concentrating the stirred solution, it was added to a large amount of ion exchange water and the precipitate was collected. After collecting the precipitated solid, it was dried under reduced pressure to obtain a polyhydroxyamide compound having carboxyl groups at both ends. The obtained polyhydroxyamide compound had a weight average molecular weight (Mw) of 32,992, a number average molecular weight (Mn) of 12,310, a polydispersity index (PDI) of 2.7, a chloride ion concentration of 2.8 ppm, a phenolic hydroxyl group equivalent of 294 g / eq, and a carboxyl group equivalent of 6,155 g / eq.

[0081] Polyhydroxyamide compounds [ka]

[0082] (Synthesis Example 10: Synthesis Example of Polyamic Acid Compound (A-10)) In a 500 mL flask equipped with a stirrer and a thermometer, 96 g of 2-methoxy-1-methylethyl acetate (PGMEA) and 14.87 g (46.45 mmol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB) were charged and stirred to dissolve. After confirming that the monomers were completely dissolved, 23.79 g (53.55 mmol) of 6FDA was added as a solid over a period of 5 minutes, and stirring was continued at room temperature for 1 hour. Then, 2.33 g (14.20 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a solid to the stirred solution, and stirring was continued at room temperature for 16 hours. The stirred solution was poured into a large amount of ion-exchanged water, and the precipitate was collected. The mixture was dried under reduced pressure to obtain a polyamic acid compound with carboxyl groups at both ends. The resulting polyamic acid compound had a weight average molecular weight (Mw) of 10,324, a number average molecular weight (Mn) of 4,382, a polydispersity index (PDI) of 2.4, a chloride ion concentration of 2.1 ppm, and a carboxyl group equivalent of 382 g / eq.

[0083] Polyamic acid compounds [ka]

[0084] <(B) Photoacid generator> (B-1) PAG-103 (oxime sulfonate compound manufactured by BASF) [ka]

[0085] (B-2) SP606 (ADEKA naphthalimide compound) [ka]

[0086] <(C) Crosslinking agent> (C-1) MW-390 (Hexamethoxymethylmelamine compound manufactured by Nippon Carbide Industries Co., Ltd.) [ka]

[0087] <(D) Alcohol amines> (D-1) Triethanolamine (TEA)

[0088] <(E) Compounds containing a phenolic hydroxyl group> (E-1) VPS-2515 (polyhydroxystyrene-styrene copolymer manufactured by Nippon Soda Co., Ltd., weight average molecular weight (Mw): 4,667, number average molecular weight (Mn): 2,593, molecular weight dispersity (PDI): 1.8, chloride ion concentration: 2.8 ppm, phenolic hydroxyl group equivalent: 140 g / eq) <(F) Inorganic filler> (F-1) Y50SV-AH2 (spherical silica manufactured by Admatechs, volume average particle diameter D50 = 50 nm) <Surfactant> BYK-310 (BYK-Chemie, silicone surfactant) <Solvent> γ-Butyrolactone (manufactured by Taishin Chemical Co., Ltd.) Cyclopentanone (Tokyo Chemical Industry Co., Ltd.)

[0089] <Preparation of negative type photosensitive resin composition> Each component was mixed in the amount shown in Tables 2 to 4, and dissolved and adjusted in a solvent so that the concentration of non-volatile components in the varnish was 30%, to obtain a varnish of a negative photosensitive resin composition of each Example and Comparative Example. Note that, among the amounts of each component in Tables 2 to 4, the amounts of the components other than the amount of the solvent are shown as solid content masses. Tables 2 to 4 also show the equivalent ratios (NCHOCH:OH) of the functional groups of the crosslinking agent and the phenolic hydroxyl groups calculated from the amounts of the raw materials of the negative photosensitive resin composition.

[0090] <Evaluation> The varnishes obtained in each of the Examples and Comparative Examples were subjected to the following evaluations. The evaluation results are shown in Tables 2 to 4.

[0091] (Edge rinse property evaluation) The varnish of each Example and Comparative Example was spin-coated onto a Si substrate, and then, while each substrate was rotated at 600 rpm, OK73 thinner (Tokyo Ohka Kogyo Co., Ltd.) was ejected from a nozzle for 45 seconds onto the edge portion of each substrate (where the varnish of each Example and Comparative Example had been applied during spin-coating). Then, each substrate was rotated at 1000 rpm for 5 seconds. The resulting substrates were evaluated for residual film on the substrate edge portion. Those without any residual film were evaluated as "A" (good), and those with residual film were evaluated as "B" (bad).

[0092] (Resolution evaluation) Line / space (L / S) measurement, aspect ratio measurement The varnish of each Example and Comparative Example was applied onto a silicon wafer using a spin coater so that the film thickness after curing would be 3.0 μm or 3.5 μm, and then dried at 110° C. for 3 minutes using a hot plate to obtain a dried coating film of the negative type photosensitive resin composition of each Example and Comparative Example. This dried coating was exposed to a test pattern with L / S of 0.5 / 0.5 μm, 0.6 / 0.6 μm, 0.7 / 0.7 μm, 0.8 / 0.8 μm, 1 / 1 μm, 1.2 / 1.2 μm, 1.5 / 1.5 μm, 1.7 / 1.7 μm, 2 / 2 μm, 3 / 3 μm, 4 / 4 μm, and 5 / 5 μm using a line stepper (reduced projection exposure device: NSR-2005i9C (Nikon Corporation; NA (numerical aperture) = 0.5, σ = 0.68, light source: high pressure mercury lamp)), and post-exposure baking (PEB) was performed on a hot plate at 140 ° C. for 60 minutes. Thereafter, development was performed using a 2.38% TMAH aqueous solution for 60 seconds, followed by rinsing with ultrapure water for 30 seconds, and spin drying for 30 seconds. A sample having a pattern of the negative photosensitive resin composition of each Example and Comparative Example was obtained. The exposure conditions (exposure amount and focus) for the negative photosensitive resin composition of each Example and Comparative Example were selected to obtain the best resolution for each negative photosensitive resin composition of each Example and Comparative Example. The exposure conditions for each Example and Comparative Example are shown in Tables 2 to 4. The obtained samples of each Example and Comparative Example were cut so that a cross section perpendicular to the longitudinal direction of the pattern could be observed. The cut surface of the pattern was observed using a scanning electron microscope (observation magnification: 10,000 times) to determine the minimum L / S where the pattern was normally patterned. Note that a sample where each pattern was vertically patterned without falling over was judged to be normally patterned. In addition, the aspect ratio (=film thickness÷minimum L / S line width) was determined for the minimum L / S pattern formed with the negative photosensitive resin composition of each Example and Comparative Example. In addition, when the cross-sections of the minimum L / S that were normally patterned were observed as described above, the presence or absence of development residues in the unexposed areas was also observed. Samples in which slight development residues were observed throughout the entire unexposed area were recorded in the minimum L / S column in Tables 2 to 4 as (Residues ×), and samples in which development residues were observed in part of the unexposed area were recorded as (Residues ◯). No record was made for samples in which no development residues were observed.

[0093] - Measurement of via opening diameter Using a contact exposure device (light source: high-pressure mercury lamp), test patterns with opening diameters of 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 15.0, and 20.0 μm were exposed. The minimum via opening diameter that could be patterned was determined using the same method as the above L / S measurement, except for the exposure process. For samples in which slight development residues were observed throughout the entire unexposed area, it was noted in the column for minimum via opening diameter in Tables 2 to 4 as (Residue ×), and for samples in which development residues were observed in part of the unexposed area, it was noted as (Residue ◯). Note that no description was given for samples in which development residues were observed.

[0094] (Insulation reliability evaluation) The varnish of each Example and Comparative Example was applied to a Kyocera Corporation comb-shaped wiring substrate with L / S=12 / 13 μm using a spin coater to a thickness of 20 μm. The coating was dried at 110° C. for 5 minutes using a hot plate to obtain a negative photosensitive resin composition coating film of each Example and Comparative Example formed on the comb-shaped wiring substrate. The coating film was exposed to light (1000 mJ / cm 2 ) using a high-pressure mercury lamp over the entire surface. 2) and heat curing was performed in an inert oven under a nitrogen atmosphere at 200°C for 1 hour. Thereafter, the cured material on the electrode portion of the comb-field wiring board was removed with a cutter knife, and a power plug was soldered to obtain an insulation reliability evaluation board. A voltage of 20V (1.7V / μm for a wiring of 12 μm) was applied to this evaluation board in an environment of 130°C and 85 RH%, and the time until the resistance between the comb-field wirings (cured material made of the negative photosensitive resin composition) became 10 MΩ or less was measured. Note that when the resistance between the comb-field wirings (negative photosensitive resin composition film) became 10 MΩ or less, the circuit was deemed to have failed. If the measurement result states ">300h," it means that the resistance between the comb-field wirings (negative photosensitive resin composition film) did not become 10MΩ or less even after 300 hours. If the measurement result states "<20h," it means that the resistance between the comb-field wirings (negative photosensitive resin composition film) became 10MΩ or less in less than 20 hours.

[0095] [Table 2]

[0096] [Table 3]

[0097] [Table 4]

Claims

1. (A) a polyhydroxyamide compound; (B) a photoacid generator; and (C) a crosslinking agent; and (D) an alcohol amine.

2. 2. The negative type photosensitive resin composition according to claim 1, wherein the polyhydroxyamide compound (A) contains a structural unit represented by the following formula (1): 【Chemistry 1】 (In the formula R １ is a divalent organic group, R ２ is a tetravalent organic group.

3. The negative type photosensitive resin composition according to claim 1 or 2, wherein the photoacid generator (B) comprises an oxime sulfonate compound.

4. The negative type photosensitive resin composition according to claim 3 , wherein the oxime sulfonate compound has a structure represented by the following formula (2): 【Chemistry 2】 (wherein X is a hydrocarbon group or a halogen atom, m is an integer of 0 to 3, R ３ is a hydrogen atom, a hydrocarbon group, an organic group including a ketone group, or a halogen atom.

5. The negative type photosensitive resin composition according to claim 1 or 2, wherein the (C) crosslinking agent has a heterocyclic skeleton.

6. 3. The negative type photosensitive resin composition according to claim 1, wherein the (C) crosslinking agent is a compound having at least one selected from the group consisting of a methoxymethyl group and a methylol group.

7. 3. The negative photosensitive resin composition according to claim 1, wherein the alcohol amine (D) is an alcohol amine having a plurality of alcohols bonded thereto.

8. The negative type photosensitive resin composition according to claim 1 or 2, further comprising (E) a compound containing a phenolic hydroxyl group.

9. 9. The negative photosensitive resin composition according to claim 8, wherein the compound (E) containing a phenolic hydroxyl group comprises a polyhydroxystyrene polymer or a polyhydroxystyrene copolymer.

10. A dry film comprising a resin layer formed from the negative photosensitive resin composition according to claim 1 or 2.

11. A cured product formed from the negative photosensitive resin composition according to claim 1 or 2 or the resin layer of the dry film according to claim 10.

12. An electronic component comprising the cured product according to claim 11.

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