Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/12—Unsaturated polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
  • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
  • H10W20/48—Insulating materials thereof
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
  • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
  • H10W70/69—Insulating materials thereof
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers

Definitions

• This disclosure relates to a photosensitive resin composition, a cured product, and a semiconductor device.
• Photosensitive resin compositions containing alkali-soluble resins have been developed as materials for forming insulating films with all of these properties (see, for example, Patent Documents 1, 2, and 3). These photosensitive resin compositions are applied to a substrate and dried to form a resin film, which is then exposed to light and developed to obtain a patterned resin film (a resin film with a pattern formed thereon). The patterned resin film is then heated and cured to form a patterned cured film (a cured film with a pattern formed thereon), and the patterned cured film can be used as an insulating film.
• Photosensitive resin compositions for forming insulating films such as redistribution layers are required to have an excellent balance of micro-processability, mechanical properties, and dielectric properties (low dielectric constant and low dielectric tangent). Therefore, the present disclosure aims to provide a photosensitive resin composition capable of forming an insulating film having an excellent balance of micro-processability, mechanical properties, and dielectric properties.
• a photosensitive resin composition comprising a maleimide compound, a crosslinking agent, and a photopolymerization initiator, wherein the maleimide compound is a reaction product of a tetracarboxylic dianhydride (a1), a diamine (a2), a triamine (a3), and maleic anhydride (a4), and the diamine (a2) includes a dimer diamine.
• the diamine (a2) includes a second diamine other than dimer diamine.
• Tetracarboxylic dianhydride (a1) is 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dio
• the present disclosure provides a photosensitive resin composition capable of forming an insulating film having an excellent balance of micro-processability, mechanical properties, and dielectric properties, a cured product having an excellent balance of micro-processability, mechanical properties, and dielectric properties, and a semiconductor device having a redistribution layer including the cured product.
• a numerical range indicated using “ ⁇ ” indicates a range including the numerical values before and after " ⁇ " as the minimum and maximum values, respectively.
• the upper or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage.
• the upper or lower limit of the numerical range may be replaced with a value shown in the examples.
• “A or B” may include either A or B, or may include both.
• the materials exemplified in this specification may be used alone or in combination of two or more types. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.
• the terms “layer” and “film” include structures that are formed over the entire surface when observed in a plan view, as well as structures that are formed on only a portion of the surface.
• process includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• (meth)acryloyl means at least one of “acryloyl” and the corresponding “methacryloyl”, and the same applies to other similar expressions such as (meth)acrylic acid and (meth)acrylate.
• solid content refers to the non-volatile content excluding volatile substances (water, solvent, etc.) contained in the photosensitive resin composition, and includes components that are liquid, syrup-like, or wax-like at room temperature (around 25°C).
• the photosensitive resin composition according to the present embodiment contains, as essential components, a maleimide compound having a specific structure, a crosslinking agent, and a photopolymerization initiator. ), a reaction product of a diamine (a2), a triamine (a3), and maleic anhydride (a4), where the diamine (a2) comprises a dimer diamine.
• the photosensitive resin composition according to this embodiment may further contain a thermal polymerization initiator, a coupling agent, a rust inhibitor, a polymerization inhibitor, etc., as necessary.
• the photosensitive resin composition according to this embodiment is a negative-type photosensitive resin composition, and the cured product of the photosensitive resin composition can be suitably used as an insulating film for a redistribution layer.
• a thermal polymerization initiator e.g., a coupling agent, e.g., a rust inhibitor, a polymerization inhibitor, etc.
• the maleimide compound according to the present embodiment (hereinafter also referred to as “component (A)”) can be obtained by reacting tetracarboxylic dianhydride (a1) (hereinafter also referred to as “component (a1)”), diamine (a2) (hereinafter also referred to as “component (a2)”), triamine (a3) (hereinafter also referred to as “component (a3)”), and maleic anhydride (a4) (hereinafter also referred to as “component (a4)”). That is, the component (A) is a maleimide compound obtained by reacting the components (a1), (a2), (a3), and (a4).
• the component (a2) contains dimer diamine.
• the component (A) is a polyfunctional maleimide compound having two or more maleimide groups. The component (A) can be used alone or in combination of two or more.
• the tetracarboxylic dianhydride of component (a1) can be any known polyimide raw material.
• component (a1) include pyromellitic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.
• Carboxylic acid dianhydride 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride Water, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(ethyne-1,2-diy
• the (a1) component is selected from the group consisting of 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride
• the (a2) component contains dimer diamine (first diamine) as an essential component.
• dimer diamine is a compound derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid.
• dimer diamine is a compound derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid.
• the (a2) component preferably contains at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2).
• the bond shown by the dashed line is a carbon-carbon double bond
• formulas (1) and (2) have a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is reduced by one from the number shown in formulas (1) and (2).
• the dimer diamine may be a diamine represented by the above general formula (2), particularly a compound represented by the following formula (3), from the viewpoints of solubility in organic solvents, heat resistance, heat-resistant adhesion, low viscosity, and the like.
• dimer diamine products include, for example, PRIAMINE 1075 and PRIAMINE 1074 (both manufactured by Croda Japan Co., Ltd.).
• the (a2) component may further contain a diamine other than dimer diamine as the second diamine.
• a diamine other than dimer diamine By using an alicyclic diamine as the second diamine, the dielectric constant can be further reduced.
• an aromatic diamine as the second diamine By using an aromatic diamine as the second diamine, the elastic modulus and Tg of the cured product can be improved.
• the second diamine is a diamine that does not fall under the category of the above-mentioned dimer diamine.
• Examples of the second diamine include 1,3-diaminopropane, norbornane diamine, 4,4-methylenedianiline, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis[3-fluoro-4-aminophenyl]fluorene, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(a
• the molar ratio of the second diamine (moles of second diamine/(moles of dimer diamine+moles of second diamine)) may be 70 mol% or less, or may be 50 mol% or less. When this ratio is 70 mol% or less, a cured product with lower dielectric properties can be formed.
• the triamine of component (a3) may be any known compound.
• Examples of component (a3) include tris(2-aminomethyl)amine, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, 2-(aminomethyl)-2-methyl-1,3-propanediamine, trimer triamine, 3,4,4'-triaminodiphenyl ether, 1,2,4-triaminobenzene, 1,3,5-triaminobenzene, 1,2,3-triaminobenzene, 1,3,5-triazine-2,4,6-triamine, 2,4,6-triaminopyrimidine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,5-tris(4-aminophenoxy)benzene, and tris(4-aminophenyl)methane.
• aliphatic triamines are preferred from the viewpoint of the solubility of the synthesized maleimide compound in organic solvents, and tris(2-aminomethyl)amine and tris(2-aminoethyl)amine, which have a small number of carbon atoms, are more preferred from the viewpoint of achieving a high Tg.
• the content of the (a3) component may be 5 mol% or more, 8 mol% or more, or 10 mol% or more, or 50 mol% or less, 40 mol% or less, or 35 mol% or less, based on the total amount of the (a2) component and the (a3) component. If this ratio is 5 mol% or more, the elastic modulus and Tg of the cured product can be further improved, and if it is 50 mol% or less, it becomes easier to dissolve in a solvent and to synthesize. From the above viewpoint, the content of the (a3) component may be 5 to 50 mol% or 5 to 35 mol% based on the total amount of the (a2) component and the (a3) component.
• dimer diamine As the diamine, a cured product with lower dielectric properties can be formed.
• the elastic modulus and Tg of the cured product will decrease.
• the elastic modulus and Tg of the cured product can be improved while maintaining the dielectric properties of the cured product.
• the elastic modulus and Tg of the cured product can be further improved while maintaining the dielectric properties of the cured product.
• the maleimide compound may have a fluorene skeleton.
• at least one of the above-mentioned components (a1) and (a2) may contain a compound having a fluorene skeleton.
• the cured product obtained using the maleimide compound has a high elastic modulus and a high Tg while adequately maintaining a low dielectric constant and a low dielectric tangent.
• Component (A) can be produced by various known methods. For example, first, components (a1), (a2), and (a3) are polyaddition reacted at a temperature of about 60 to 120°C, preferably 70 to 90°C, for usually about 0.1 to 2 hours, preferably 0.1 to 1.0 hour. Next, the resulting polyaddition product is further subjected to an imidization reaction, i.e., a dehydration ring-closing reaction, at a temperature of about 80 to 250°C, preferably 100 to 200°C, for about 0.5 to 30 hours, preferably 0.5 to 10 hours.
• an imidization reaction i.e., a dehydration ring-closing reaction
• the product that has undergone the dehydration ring-closing reaction and component (a4) are maleimidized, i.e., a dehydration ring-closing reaction, at a temperature of about 60 to 250°C, preferably 80 to 200°C, for about 0.5 to 30 hours, preferably 0.5 to 10 hours, to obtain the desired component (A).
• Reaction catalysts include, for example, aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as pyridine, picoline, isoquinoline, and organic acids such as methanesulfonic acid and paratoluenesulfonic acid monohydrate.
• Dehydrating agents include, for example, aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides such as benzoic anhydride.
• Organic solvents include, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and pseudocumene; alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ether solvents such as anisole; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclopentanone, cyclohexanone, isophorone, and acetophenone; cellosolves such as methyl cellosolve and ethyl cellosolve, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, and ⁇ -butyrolactone; Examples of the organic solvent include glycol ether solvent
• Component (A) can be purified by various known methods to increase its purity. For example, first, component (A) dissolved in an organic solvent and pure water are placed in a separatory funnel. The separatory funnel is then shaken and allowed to stand. After the aqueous layer and organic layer are separated, only the organic layer is collected, thereby purifying component (A).
• the (A) component produced by the above method may contain one or more of the structural units represented by the following general formulas (4) to (6).
• the range of the number of functional groups (number of maleimide groups) of the (A) component depends on the triamine content, but is expected to have 2 to 6 functional groups per molecule.
• the (A) component may be a mixture of multiple compounds having different structures or different numbers of functional groups.
• the (A) component may contain a compound having 3 or more functional groups per molecule, including one or more of the structural units represented by the following general formulas (5) to (6).
• X each independently represents a tetravalent organic group
• Y each independently represents a divalent organic group
• Z each independently represents a trivalent organic group.
• X, Y, and Z may be an aliphatic group, an organic group having an alicyclic structure or an aromatic ring, and may contain a heteroatom.
• Y may be an organic group derived from a dimer diamine
• Z may be an organic group derived from a triamine (a3).
• X, Y, and Z in formula (7) are the same as X, Y, and Z in general formulas (4) to (6).
• a represents an integer from 0 to 20
• b represents an integer from 0 to 30
• c represents an integer from 0 to 20
• d represents an integer from 1 to 30.
• the positions of the structural unit marked with the symbol a (structural unit represented by the above general formula (5)), the structural unit marked with the symbol b (structural unit represented by the above general formula (4)), and the structural unit marked with the symbol c (structural unit represented by the above general formula (6)) may be interchanged.
• Component (A) may contain a compound having three or more functional groups per molecule, in which at least one of a and c is an integer of 1 or more.
• the molecular weight of the (A) component can be controlled by the number of moles of the (a1), (a2), and (a3) components, and the smaller the number of moles of the (a1) component is compared to the combined number of moles of the (a2) and (a3) components, the smaller the molecular weight can be.
• [number of moles of the (a1) component]/[number of moles of the (a2) component + number of moles of the (a3) component] to be in the range of about 0.30 to 1.00, preferably 0.30 to 0.95, more preferably 0.30 to 0.90, and even more preferably 0.50 to 0.80.
• the molecular weight of component (A) may be 3000 or more, 5000 or more, 6000 or more, or 7000 or more in weight average molecular weight (Mw), or 40000 or less, 38000 or less, 35000 or less, 33000 or less, 30000 or less, 25000 or less, or 20000 or less. If the weight average molecular weight is 40000 or less, the solubility in organic solvents is good, and if it is 3000 or more, the effect of improving heat resistance tends to be sufficiently obtained. From the viewpoint of solubility in solvents and heat resistance, Mw may be 3000 to 40000, preferably 3000 to 30000, more preferably 5000 to 25000, even more preferably 6000 to 23000, and particularly preferably 7000 to 20000. Mw can be measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene.
• GPC gel permeation chromatography
• the crosslinking agent (hereinafter also referred to as "component (B)") may be a polymerizable crosslinking agent.
• the polymerizable group may be a photopolymerizable group or a thermally polymerizable group. Examples of the polymerizable group include a (meth)acryloyl group, an allyl group, and a vinyl group.
• the component (B) may be a polyfunctional compound having two or more polymerizable groups.
• the crosslinking agent can crosslink not only with itself but also with the component (A) during exposure of the photosensitive layer.
• the crosslinking agent can also crosslink with itself during heating of the resin film after pattern formation.
• the component (B) can be used alone or in combination of two or more.
• the resin composition according to this embodiment may contain a polymerizable crosslinking agent having a (meth)acryloyl group as a crosslinking agent from the viewpoint of dielectric properties.
• the polymerizable crosslinking agent having a (meth)acryloyl group can crosslink not only with itself but also with component (A) when the photosensitive layer is exposed to light.
• the polymerizable crosslinking agent having a (meth)acryloyl group may be an acrylate compound or a methacrylate compound.
• Component (B) may contain a methacrylate compound from the viewpoint of dielectric properties.
• polymerizable crosslinking agents having a (meth)acryloyl group include, for example, tricyclodecane dimethanol di(meth)acrylate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, dioxane glycol di(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, 1,6-hexane
• diol di(meth)acrylates include diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decane
• the polymerizable crosslinking agent having a (meth)acryloyl group may contain at least one selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, and dioxane glycol di(meth)acrylate, from the viewpoints of heat resistance, dielectric properties, and fine processability, and may contain tris-(2-(meth)acryloyloxyethyl)isocyanurate from the viewpoints of heat resistance and dielectric properties.
• the resin composition according to this embodiment may contain a polymerizable crosslinking agent having an allyl group or a vinyl group as a crosslinking agent from the viewpoint of dielectric properties and heat resistance.
• the polymerizable crosslinking agent having an allyl group or a vinyl group can crosslink with itself when the resin film is heated after pattern formation.
• polymerizable crosslinking agents having an allyl group examples include 1,3,4,6-tetraallyl glycoluril, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl isocyanurate, triallyl trimellitate, and triallyl orthoformate.
• polymerizable crosslinking agents having vinyl groups examples include polyvinylbenzyl compounds and polyvinylbenzyl ether compounds.
• the polymerizable crosslinking agent having an allyl group or a vinyl group may contain at least one selected from the group consisting of 1,3,4,6-tetraallyl glycoluril, triallyl isocyanurate, diallyl isocyanurate, and polyvinyl benzyl ether compounds from the viewpoint of dielectric properties and fine processability, and may contain 1,3,4,6-tetraallyl glycoluril or triallyl isocyanurate from the viewpoint of dielectric properties.
• the content of component (B) is preferably less than 50 parts by mass when the total amount of components (A) and (B) is taken as 100 parts by mass, and may be 1 to 45 parts by mass, 5 to 40 parts by mass, 8 to 30 parts by mass, or 10 to 20 parts by mass.
• the photopolymerization initiator (hereinafter also referred to as “component (C)”) is not particularly limited as long as it is a compound that initiates polymerization upon irradiation with actinic rays (ultraviolet rays, etc.); examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, intramolecular hydrogen abstraction photopolymerization initiators, and oxime ester-based photopolymerization initiators.
• Alkylphenone-based photopolymerization initiators are available, for example, from IGM Resins B.V. as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 379EG, etc.
• Acylphosphine oxide-based photopolymerization initiators are available, for example, from IGM Resins B.V. as Omnirad 819, Omnirad TPO H, etc.
• Intramolecular hydrogen abstraction photopolymerization initiators are available, for example, from IGM Resins B.V. Omnirad MBF, Omnirad 754, etc. manufactured by BASF Japan Co., Ltd.
• Oxime ester photopolymerization initiators can be purchased, for example, as Irgacure OXE01, Irgacure OXE02, etc. manufactured by BASF Japan Co., Ltd.
• a titanocene photopolymerization initiator for example, Irgacure 784 manufactured by BASF Japan Co., Ltd.
• Irgacure 784 manufactured by BASF Japan Co., Ltd.
• the content of component (C) may be 0.1 to 10.0 parts by mass, 0.5 to 8.0 parts by mass, 0.8 to 6.0 parts by mass, or 1.0 to 5.0 parts by mass per 100 parts by mass of the total amount of components (A) and (B), since this makes it easier to obtain excellent micro-machining properties.
• the photosensitive resin composition according to the present embodiment may further contain a thermal polymerization initiator as component (D) from the viewpoint of promoting the polymerization reaction of the thermally polymerizable group.
• a thermal polymerization initiator as component (D) from the viewpoint of promoting the polymerization reaction of the thermally polymerizable group.
• component (D) a compound that decomposes by heating during curing to generate radicals and promote the polymerization reaction of the components (A) and (B) is preferable.
• an organic peroxide can be mentioned.
• organic peroxides include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-
• dropyroperoxide 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, ⁇ , ⁇ '-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxy
• the amount of the (D) component is not particularly limited, but may be 0.1 to 10.0 parts by mass, 0.3 to 8.0 parts by mass, 0.5 to 5.0 parts by mass, 0.7 to 3.0 parts by mass, or 0.7 to 2.0 parts by mass per 100 parts by mass of the total amount of the (A) and (B) components.
• the photosensitive resin composition according to the present embodiment may further contain a coupling agent from the viewpoint of improving the adhesion of the cured product of the photosensitive resin composition.
• the coupling agent may be a silane coupling agent.
• the silane coupling agent may have, for example, a vinyl group, an epoxy group, a styryl group, an acryloyl group, a methacryloyl group, an amino group, a ureido group, an isocyanate group, an isocyanurate group, a mercapto group, or the like.
• silane coupling agents having a vinyl group examples include KBM-1003 and KBE-1003 (product names manufactured by Shin-Etsu Chemical Co., Ltd.; the same applies below).
• Examples of silane coupling agents having an epoxy group include KBM-303, 402, 403, KBE-402, 403, X-12-981S, X-12-984S, etc.
• Examples of silane coupling agents having a styryl group include KBM-1403, etc.
• Examples of silane coupling agents having a methacryloyl group examples include KBM-502, 503, KBE-502, 503, etc.
• silane coupling agents having an acryloyl group examples include KBM-5103, X-12-1048, X-12-1050, etc.
• silane coupling agents having an amino group examples include KBM-602, 603, 903, 573, 575, KBE-903, 9103P, and X-12-972F.
• Examples of silane coupling agents having a ureido group include KBE-585.
• Examples of silane coupling agents having an isocyanate group include KBE-9007 and X-12-1159L.
• Examples of silane coupling agents having an isocyanurate group include KBM-9659.
• Examples of silane coupling agents having a mercapto group examples include KBM-802, 803, X-12-1154, and X-12-1156.
• the silane coupling agent may be a silane coupling agent having a methacryloyl group.
• the silane coupling agents may be used alone or in combination of two or more.
• the content of the silane coupling agent may be 0.01 to 10.0 parts by mass, 0.1 to 8.0 parts by mass, 0.3 to 6.0 parts by mass, 0.5 to 5.0 parts by mass, or 1.0 to 3.0 parts by mass, relative to 100 parts by mass of the total amount of the (A) component and the (B) component.
• the photosensitive resin composition according to the present embodiment may further contain a rust inhibitor from the viewpoint of suppressing corrosion or preventing discoloration of copper wiring.
• a rust inhibitor examples include triazole derivatives such as benzotriazole, and tetrazole derivatives.
• the rust inhibitor may be used alone or in combination of two or more.
• the content of the rust inhibitor may be 0.01 to 10.0 parts by mass, 0.1 to 5.0 parts by mass, 0.3 to 4.0 parts by mass, 0.5 to 3.0 parts by mass, or 1.0 to 3.0 parts by mass per 100 parts by mass of the total amount of components (A) and (B).
• the photosensitive resin composition according to this embodiment may further contain a polymerization inhibitor from the viewpoint of storage stability.
• polymerization inhibitors examples include 4-tert-butylcatechol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, and nitrosamines.
• Polymerization inhibitors may be used alone or in combination of two or more.
• the content of the polymerization inhibitor may be 0.01 to 10.0 parts by mass, 0.05 to 5.0 parts by mass, 0.10 to 2.0 parts by mass, or 0.10 to 1.0 parts by mass, per 100 parts by mass of the total amount of the (A) component and the (B) component.
• the photosensitive resin composition may further contain a sensitizer from the viewpoint of maintaining both the remaining film rate over a wide range of exposure doses and good resolution.
• Sensitizers include, for example, Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzyl, benzil dimethyl ketal ...
• sensitizer examples include diethyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutylate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, biscoumarin compounds, N-phenylglycine, N-phenyldiethanolamine, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone.
• One type of sensitizer may
• the content is preferably 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1.5 parts by mass, per 100 parts by mass of the total amount of components (A) and (B).
• the photosensitive resin composition according to the present embodiment contains a solvent for dissolving and dispersing each component, which makes it easy to apply the composition to a substrate and forms a coating film of uniform thickness.
• the solvent may be used alone or in combination of two or more kinds.
• the solvent examples include ketone-based solvents such as methyl ethyl ketone, cyclohexanone, and cyclopentanone; aromatic hydrocarbon-based solvents such as toluene, xylene, tetramethylbenzene, mesitylene, and pseudocumene; glycol ether-based solvents such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ester-based solvents such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ⁇ -butyrolactone; and amide-based solvents such as N,N-dimethylformamide, N
• the amount of solvent used is not particularly limited, but may be an amount that results in a solid content of 5 to 60 mass %, 10 to 50 mass %, or 15 to 40 mass % in the photosensitive resin composition.
• the means and conditions for preparing the photosensitive resin composition are not particularly limited.
• the main components are thoroughly and uniformly stirred and mixed in the prescribed amounts using a mixer or the like, and then kneaded using a mixing roll, extruder, kneader, roll, extruder, or the like.
• the kneading method is not particularly limited.
• the dielectric constant at 10 GHz of the cured product of the photosensitive resin composition according to this embodiment may be 2.80 or less, 2.75 or less, or 2.70 or less.
• the dielectric tangent at 10 GHz of the cured product of the photosensitive resin composition may be 0.0060 or less, 0.0050 or less, 0.0045 or less, or 0.0040 or less.
• the dielectric constant and dielectric tangent can be measured by the method described in the examples using a cured film of the photosensitive resin composition.
• the photosensitive resin composition according to this embodiment is capable of forming a fine pattern.
• the photosensitive resin composition according to this embodiment is capable of forming an insulating film that exhibits low dielectric properties and has excellent insulating reliability.
• a semiconductor element having an interlayer insulating layer formed from the cured product of the above-mentioned photosensitive resin composition, and an electronic device including the semiconductor element can be produced.
• the semiconductor element can improve high-frequency characteristics by having a rewiring layer including the cured product of the photosensitive resin composition according to this embodiment.
• the semiconductor element may be, for example, a memory, a package, etc. having a multilayer wiring structure, a rewiring structure, etc. Examples of electronic devices include mobile phones, smartphones, tablet terminals, personal computers, and hard disk suspensions.
• dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was added dropwise.
• 1.44 parts by mass of tris(2-aminoethyl)amine manufactured by Tokyo Chemical Industry Co., Ltd.
• 4.57 parts by mass of norbornane diamine manufactured by Mitsui Fine Chemicals Co., Ltd.
• the obtained polyimide resin was cooled to 130°C, 11.61 parts by mass of maleic anhydride (manufactured by Fuso Chemical Co., Ltd.) was added, the temperature was raised to 160°C, and a dehydration ring-closing reaction was carried out at 160°C for 4 hours to remove water from the reaction liquid, thereby obtaining a maleimide compound.
• maleic anhydride manufactured by Fuso Chemical Co., Ltd.
• the obtained maleimide compound was placed in a separatory funnel, 500 parts by mass of pure water was added, and the separatory funnel was shaken and allowed to stand. After standing, the aqueous layer and the organic layer were separated, and only the organic layer was collected.
• the collected organic layer was placed in a 0.3 L glass vessel equipped with a cooler, nitrogen inlet tube, thermocouple, stirrer, and vacuum pump, heated to 88-93°C, and after removing the water, heated to 100°C and partially removing the solvent for 0.5 hours under a reduced pressure of 0.1 MPa from atmospheric pressure, to obtain a solution of maleimide compound (A-1), which is component (A).
• Non-volatile content 0.75 g ⁇ 0.25 g of the maleimide compound solution was weighed out using a precision balance into a metal petri dish, and then dried in a hot air dryer at 150° C. for 0.5 hours.
• the weight average molecular weight (Mw) of the maleimide compound was measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• a sample in which the maleimide compound was dissolved in tetrahydrofuran (THF) to a concentration of 3% by mass was injected in an amount of 50 ⁇ L into a column (GL-R420 ⁇ 1, GL-R430 ⁇ 1, GL-R440 ⁇ 1 (all manufactured by Hitachi High-Tech Fielding Corporation) heated to 30° C., and measurement was performed using THF as a developing solvent at a flow rate of 1.6 mL/min.
• THF tetrahydrofuran
• the detector used was an L-3350 RI detector (manufactured by Hitachi, Ltd.), and Mw was calculated from the elution time using a molecular weight/elution time curve prepared using standard polystyrene (manufactured by Tosoh Corporation).
• component (B) As component (B), the following compounds were prepared.
• A-9300 Tris-(2-acryloyloxyethyl)isocyanurate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
• TA-G 1,3,4,6-tetraarylglycoluril (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.)
• TAIC Triallyl isocyanurate (product name, manufactured by Shinryo Corporation)
• Component (C) Oxime ester photopolymerization initiator (manufactured by BASF Japan Ltd., product names "Irgacure OXE01” and “Irgacure OXE02")
• Component (D) ⁇ , ⁇ '-bis(t-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation, trade name "Perbutyl P")
• Coupling agent 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
• Polymerization inhibitor 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyradical (TEMPOL) (manufactured by Tokyo Chemical Industry Co., Ltd.) Rust inhibitor: 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) Rust inhibitor: 1,2,3-benzotriazole (manufacture
• Photosensitive resin composition Each component in the amount (parts by weight, solid content) shown in Table 2 or Table 3 was mixed with 210 parts by weight of the solvent, stirred at 25° C. for 30 minutes or more, and then filtered through a filter with an opening of 0.5 ⁇ m. Photosensitive resin compositions of the examples were prepared.
• the photosensitive resin composition was applied onto copper foil using a knife coater, then air-dried for 15 minutes, and dried in a dryer at 90°C for 15 minutes to form a coating film.
• the coating film was exposed to light using a high-pressure mercury lamp (exposure amount: 1000 mJ/cm 2 ) and post-exposure baked on a hot plate (100°C, 1 minute) to form a resin film having a thickness of 100 ⁇ m.
• the resin film was then cured in a nitrogen atmosphere at 200°C for 2 hours using a clean oven.
• the copper foil was then dissolved and removed with ammonium persulfate to obtain a cured film.
• the cured film was cut into a length of 80 mm and a width of 80 mm to prepare an evaluation sample.
• the dielectric constant (Dk) and dielectric loss tangent (Df) of the evaluation sample at 10 GHz were measured at room temperature using a SPDR dielectric resonator (manufactured by QWED) and an analyzer (manufactured by Agilent Technologies, product name "PNA Network Analyzer N5227A").
• the cured film was cut into a length of 40 mm and a width of 2 mm to prepare an evaluation sample.
• the evaluation sample was measured using a thermomechanical analyzer (manufactured by TA Instruments Japan, Inc., product name "Q-400") under conditions of a nitrogen atmosphere, tension mode, load of 5 mN, measurement temperature range of -50 to 220°C, heating rate of 10°C/min, and chuck distance of 10 mm, and the coefficient of linear expansion (CTE) was calculated from the amount of displacement from 0 to 40°C.
• 5% weight loss temperature 6.0 to 10.0 mg of the cured film was weighed out and placed in an open-type sample container (manufactured by Hitachi High-Tech Science Corporation, product name "GCA-0055"), and the nitrogen flow rate was 300 mL/min, the starting temperature was 40°C, and the heating rate was 10°C.
• the 5% weight loss temperature (T d5 ) was measured under the condition of 0.05 g/min using a NEXTA STA200RV (manufactured by Hitachi High-Tech Science Corporation).
• a photosensitive resin composition was spin-coated on a silicon wafer, and dried by heating at 90°C for 5 minutes using a hot plate to form a resin film with a thickness of 7 ⁇ m.
• the resin film was pattern-exposed using an i-line stepper exposure machine (manufactured by Therma Precision Co., Ltd., product name "Sc6k”) at an exposure dose of 300 mJ/ cm2 , and then heated using a hot plate at 100°C for 1 minute.
• the film was developed using a developer (a mixture of cyclopentanone and propylene glycol monomethyl ether acetate) at 25°C for 30 seconds (15 seconds twice), and washed with propylene glycol monomethyl ether acetate.
• a developer a mixture of cyclopentanone and propylene glycol monomethyl ether acetate
• the case where the minimum via diameter was 20 ⁇ m or less where these defects could not be confirmed was evaluated as "A”
• the case where the minimum via diameter was more than 20 ⁇ m was evaluated as "B".

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