WO2022158359A1 - 感光性樹脂組成物、並びにこれを用いたポリイミド硬化膜の製造方法及びポリイミド硬化膜 - Google Patents
感光性樹脂組成物、並びにこれを用いたポリイミド硬化膜の製造方法及びポリイミド硬化膜 Download PDFInfo
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- WO2022158359A1 WO2022158359A1 PCT/JP2022/000793 JP2022000793W WO2022158359A1 WO 2022158359 A1 WO2022158359 A1 WO 2022158359A1 JP 2022000793 W JP2022000793 W JP 2022000793W WO 2022158359 A1 WO2022158359 A1 WO 2022158359A1
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- WIPO (PCT)
- Prior art keywords
- photosensitive resin
- resin composition
- group
- polyimide
- carbon atoms
- Prior art date
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Images
Classifications
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
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- 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
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- 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
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- 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
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-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- 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
- G03F7/20—Exposure; Apparatus therefor
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Definitions
- the present disclosure relates to a photosensitive resin composition, a method for producing a cured polyimide film using the same, and a cured polyimide film.
- those provided in the form of a photosensitive resin composition can be heat-resistant by application, exposure, development, and ring-closure treatment (imidation, benzoxazolization) and thermal crosslinking by coating, exposure, development, and curing of the composition. can easily form a relief pattern film.
- Such a photosensitive resin composition has the feature of enabling a significant reduction in the process compared to conventional non-photosensitive materials, and is used in the production of semiconductor devices.
- semiconductor devices are mounted on printed circuit boards in various ways according to their purpose.
- a conventional element is generally manufactured by a wire bonding method in which a fine wire is used to connect an external terminal (pad) of the element to a lead frame.
- the difference in the wiring length of each terminal in mounting affects the operation of the device. Therefore, in mounting elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and it has become difficult to satisfy this requirement with wire bonding.
- flip-chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, the chip is flipped over, and the chip is directly mounted on a printed circuit board. . Since this flip-chip mounting can accurately control the wiring distance, it has been adopted for high-end devices that handle high-speed signals, and for mobile phones due to its small mounting size, and demand is growing rapidly. . More recently, a pre-processed wafer is diced to produce individual chips, the individual chips are reconstructed on a support, sealed with mold resin, and a rewiring layer is formed after removing the support.
- fan-out wafer level package (FOWLP) has been proposed (for example, Patent Document 1).
- FOWLP fan-out wafer level package
- the rewiring layer is formed with a thin film thickness, the height of the package can be reduced, and there are advantages such as high-speed transmission and cost reduction.
- the dielectric constant and dielectric loss tangent are high, the transmission loss increases due to the increase in dielectric loss.
- Polyimide resin has excellent insulation performance and thermo-mechanical properties, so it has high material reliability.
- High dielectric constant and dielectric loss tangent are regarded as problems.
- the dielectric loss tangent may be dependent on frequency, and it is considered preferable that the moisture permeability of the insulating layer is low.
- the present disclosure provides a photosensitive resin composition that has low dielectric properties and low moisture permeability and is capable of forming a cured relief pattern with high resolution, a method for producing a cured polyimide film using the same, and a cured polyimide film. With the goal.
- A 100 parts by mass of at least one resin selected from polyimides and polyimide precursors;
- B 0.5 to 10 parts by mass of a photosensitizer;
- C 100 to 300 parts by weight of a solvent;
- the imide group concentration U which is the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit, is 12 wt% to 26 wt%
- a photosensitive resin composition wherein the resin has a structure represented by the following general formula (14).
- R 15 is an organic group having 1 to 5 carbon atoms
- R 16 , R 17 and R 18 are each independently a single bond which may form a ring structure or a an alkyl group or an organic group containing an aromatic ring having 6 to 10 carbon atoms
- m 9 is an integer selected from 1 to 4
- m 10 , m 11 and m 12 are each independently from 0 to 4
- Z 2 is an integer selected
- Z 2 is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms
- * represents a connecting portion with the main chain of the resin.
- the polyimide precursor has a structure represented by the following general formula (4). ⁇ wherein X 1 is a tetravalent organic group having 6 to 40 carbon atoms, Y 1 is a divalent organic group having 6 to 40 carbon atoms, and n 1 is an integer of 2 to 150; and R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R 4 and R 5 is a group represented by the following general formula (5).
- R 6 , R 7 and R 8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10;
- ⁇ [6] (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors; (B) 0.5 to 10 parts by mass of a photosensitizer; (C) 100 to 300 parts by weight of a solvent;
- a photosensitive resin composition comprising When the resin contains a polyimide precursor, the polyimide precursor has the following general formula (4): ⁇ wherein X 1 is a tetravalent organic group having 6 to 40 carbon atoms, Y 1 is a divalent organic group having 6 to 40 carbon atoms, and n 1 is an integer of 2 to 150; and R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.
- R 4 and R 5 is a group represented by the following general formula (5).
- R 6 , R 7 and R 8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10;
- the resin has the following general formula (15): ⁇ Wherein, each Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and may form a cyclic structure, a represents an integer of 0 to 4, A is each independently an oxygen atom or a sulfur atom, and B is the following formula: It is one of them.
- ⁇ contains a structure represented by The resin has the following general formula (14):
- R 15 is an organic group having 1 to 5 carbon atoms
- R 16 , R 17 and R 18 are each independently a single bond which may form a ring structure or an alkyl group having 1 to 10 carbon atoms. or an organic group containing an aromatic ring having 6 to 10 carbon atoms
- m 9 is an integer selected from 1 to 4
- m 10 , m 11 and m 12 are each independently selected from 0 to 4
- Z 2 is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms
- * represents a connecting portion with the main chain of the resin.
- ⁇ including a structure represented by a photosensitive resin composition.
- the imide group concentration U When the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit is defined as the imide group concentration U, and the ratio of the total molecular weight of the aliphatic hydrocarbon groups is defined as the aliphatic hydrocarbon group concentration T, U is 12 wt%. ⁇ 26 wt%, and the following formula (1): -12.6 ⁇ UT ⁇ 16.0 (1) A photosensitive resin composition that satisfies ⁇ .
- a photosensitive resin composition comprising (A) In the IR spectrum of the polyimide obtained by heating and curing the polyimide precursor at 230 ° C., the maximum peak intensity of the absorption peaks in the range of 1450 cm -1 to 1550 cm -1 is Ph 1 , the second The peak intensity of the intensity of is Ph 2 , the peak intensity near 1380 cm ⁇ 1 is Im 1 , and when Ph 1 is normalized to 1, the following formula (2): 0.34 ⁇ Ph 2 ⁇ Im 1 ⁇ 1.2 (2)
- a photosensitive resin composition that satisfies [9] The photosensitive resin composition according to any one of items 1 to 8, wherein the resin is a reaction product of tetracarboxylic dianhydride and diamine.
- a cured resin film having excellent relief pattern resolution, low dielectric properties, low moisture permeability, and good chemical resistance can be produced.
- a polyimide precursor having a specific terminal cross-linking group and an aliphatic hydrocarbon group By using a polyimide precursor having a specific terminal cross-linking group and an aliphatic hydrocarbon group, the solubility of the pre-baked film in a developing solution is improved, thereby improving the resolution of the relief pattern.
- the hydrophobicity and crosslink density of the cured film the water vapor permeability is lowered and the chemical resistance is improved.
- the photosensitive resin composition of the present disclosure includes (A) 100 parts by mass of at least one resin selected from polyimides and polyimide precursors having a specific structure, and (B) 0.5 to 10 parts by mass of photopolymerization It contains an initiator and (C) 50 to 500 parts by mass of a solvent. Further, the photosensitive resin composition of the present disclosure optionally includes (D) a silane coupling agent, (E) an ethylenically unsaturated group-containing compound, (F) a thermal cross-linking agent, (G) in addition to the above components. It further contains fillers and other ingredients.
- At least one resin selected from polyimides and polyimide precursors preferably includes a structure represented by the following general formula (14) from the viewpoint of resolution, moisture permeability and low dielectric loss tangent.
- R 15 is an organic group having 1 to 5 carbon atoms
- R 16 , R 17 and R 18 are each independently a single bond which may form a ring structure or a an alkyl group or an organic group containing an aromatic ring having 6 to 10 carbon atoms
- m 9 is an integer selected from 1 to 4
- m 10 , m 11 and m 12 are each independently from 0 to 4
- Z 2 is an integer selected
- Z 2 is a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms
- * represents a connecting portion with the main chain of the resin.
- Z 2 is preferably a structure selected from a single bond, an organic group having a heteroatom, or an organic group having 1 to 13 carbon atoms, and the organic group having a heteroatom is represented by the following formula: Structures selected from are preferred.
- the organic group having a heteroatom is an organic group having at least one heteroatom selected from N, O, P, S, Cl, I and Br.
- Organic groups include unsaturated hydrocarbons and saturated hydrocarbons, more preferably saturated hydrocarbons.
- the organic group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
- a cured film with good relief pattern resolution and low moisture permeability can be obtained.
- the introduction of an organic group into the aromatic ring improves the solubility of the polyimide precursor in the developer, making it easier to ensure the contrast with the exposed area and improving the resolution of the relief pattern. be done.
- the introduction of an organic group into the aromatic ring increases the hydrophobicity of the film, making it difficult for moisture to permeate.
- Examples of the structure of general formula (14) include at least one structure selected from the group consisting of general formula (9) below.
- the structure of the above formula (14) is derived from the tetracarboxylic dianhydride when preparing the polyimide and the polyimide precursor, it contains at least one structure selected from the group consisting of the following general formula (10) is preferred.
- the structure of the above formula (14) is derived from the diamine compound in preparing the polyimide and the polyimide precursor, it preferably contains at least one structure selected from the group consisting of the following general formula (11).
- the structure of general formula (14) is not limited to the structures listed in (9) to (11) above.
- the above structures may be of one type or a combination of two or more types.
- At least one resin selected from polyimides and polyimide precursors also preferably includes a structure represented by the following general formula (15) from the viewpoint of resolution, moisture permeability and low dielectric loss tangent.
- each Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom and may form a cyclic structure
- a represents an integer of 0 to 4
- A is each independently an oxygen atom or a sulfur atom
- B is a single bond or It is one of them.
- the imide group concentration U in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition is 12 wt% to 26 wt%.
- the "imide group concentration U" refers to a structure derived from a tetracarboxylic dianhydride and a diamine compound in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ° C. refers to the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing
- the condition of heating and curing at 350° C. is to clarify the standard of the aliphatic hydrocarbon group concentration T by setting the state in which the polyimide precursor is almost 100% imidized as the standard. , the photosensitive resin composition is not intended to be heated and cured at 350° C. in actual use.
- the imide group concentration U is 12.0 wt% or more, the resolution of the relief pattern tends to be good.
- the imide group concentration U is preferably 12.5 wt% or more, more preferably 13.5 wt% or more.
- the imide group concentration U is 26 wt % or less, the resulting polyimide cured film tends to have a good dielectric loss tangent.
- the imide group concentration U is more preferably 23.0 wt % or less, and even more preferably 21.0 wt % or less.
- the imide group concentration U in the repeating unit of the cured polyimide film is expressed by the following formula (I) using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used when preparing the polyimide precursor: 70.02 ⁇ 2 / [Mw (A) + Mw (B) - 36] ⁇ 100 (I) ⁇ In formula (I), Mw (A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw (B) represents the molecular weight of the diamine. ⁇ .
- Mw (A1) represents the molecular weight of the first tetracarboxylic dianhydride
- Mw (A2) represents the molecular weight of the second tetracarboxylic dianhydride
- a1 represents the content of the first tetracarboxylic dianhydride
- a2 represents the content of the second tetracarboxylic dianhydride
- Mw (B1) represents the molecular weight of the first diamine compound
- Mw(B2) represents the molecular
- ⁇ When three or more kinds of tetracarboxylic dianhydrides and/or diamines are used, the same requirement is required.
- tetracarboxylic acid and/or tetracarboxylic acid dichloride is used as a raw material, the mass of the corresponding tetracarboxylic dianhydride is used for calculation.
- the polyimide and/or polyimide precursor resin may have at least one terminal structure selected from the group consisting of general formulas (1) to (3) below.
- W is a divalent to trivalent organic group
- R 1 to R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms
- m 1 is 1 to is an integer of 2
- m 2 is an integer of 2 to 10
- * means attached to the main chain of the resin.
- the structure of W is not particularly limited, but is preferably a divalent to trivalent organic group having a weight average molecular weight of less than 300, more preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, 2 ⁇ is a trivalent organic group.
- the polyimide precursor may have a polymerizable group at the end of the main chain.
- the (A) polyimide precursor having a polymerizable group preferably has a structure represented by the following general formula. ⁇ In formula (E1), a 1 contains at least one bond selected from an amide bond, an imide bond, a urea bond, and a urethane bond, b 1 is a reactive substituent that crosslinks with heat or light, and e 1 is a carbon a monovalent organic group having 1 to 30 numbers, R 19 and R 22 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and R 20 and R 21 are each independently or a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or a part of an aromatic ring or an aliphatic ring.
- both R 20 and R 21 are not hydrogen atoms.
- f 1 contains at least one bond selected from an amide bond, an imide bond, a urea bond, a urethane bond, and an ester bond
- g 1 is a reactive substituent that crosslinks with heat or light
- R 23 to R 27 each independently form a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or together form an aromatic ring or an aliphatic ring, provided that R 24 , R 25 and R 26 are hydrogen It does not become an atom.
- the polyimide precursor has low dielectric properties, low moisture permeability, good chemical resistance, and high-resolution negative photosensitive A resin composition can be obtained.
- f 1 preferably contains at least one group selected from an amide group, an imide bond, a urea group and a urethane group. If f 1 is an ester group, it is likely to be hydrolyzed and may not be crosslinked. These four groups (amide group, imide bond, urea group and urethane group) are resistant to hydrolysis and thus have high chemical resistance.
- the reactive substituent b1 that crosslinks with heat or light is, for example, an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, an ethynyl group, an imino group, It is preferably at least one selected from an isocyanato group, a cyanato group, a cycloalkyl group, an epoxy group, an oxetanyl group, a carbonate group, a hydroxyl group, a mercapto group, a methylol group, and an alkoxyalkyl group.
- b1 is at least one selected from an acryl group, a methacryl group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, and an ethynyl group. is preferred.
- a methacryl group is particularly preferred.
- Reactive substituent g 1 that crosslinks with heat or light is, for example, an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, an ethynyl group, an imino group, It is at least one selected from an isocyanato group, a cyanato group, a cycloalkyl group, an epoxy group, an oxetanyl group, a carbonate group, a hydroxyl group, a mercapto group, a methylol group, and an alkoxyalkyl group.
- g1 is at least one selected from an acryl group, a methacryl group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, and an ethynyl group. is preferred. g 1 is particularly preferably a methacryl group.
- the aliphatic hydrocarbon group concentration T of the polyimide cured film obtained by heating and curing the photosensitive resin composition is preferably 4 wt % to 35 wt %.
- the "aliphatic hydrocarbon group concentration T" refers to the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350 ° C., from a tetracarboxylic dianhydride and a diamine compound It refers to the ratio of the total molecular weight of the aliphatic hydrocarbon groups to the molecular weight of the repeating units. The reason why the heating and curing at 350° C.
- the "aliphatic hydrocarbon group” is selected from the group consisting of saturated aliphatic chains, unsaturated aliphatic chains, and alicyclic structures branched from the polyimide precursor main chain and containing no heteroatoms. It is a hydrocarbon group having at least one structure and may be straight or branched.
- the portion of the alkylene skeleton that constitutes part of the main chain, the quaternary carbon that constitutes part of the main chain (the carbon that is disubstituted and constitutes part of the main chain) is used in the calculation of the aliphatic hydrocarbon group concentration. not included in "aliphatic hydrocarbon group".
- the aliphatic hydrocarbon group that constitutes the side chain portion branched from the main chain may be saturated or unsaturated, chain-shaped or alicyclic, and "aliphatic included in "hydrocarbon group”.
- Structural examples of the "aliphatic hydrocarbon group” include structures represented by the following general formula (A1), the following general formula (A2), and the following general formula (A3).
- L may be a single bond, a linear or branched saturated hydrocarbon, or a linear or branched unsaturated hydrocarbon group.
- b is an integer of 1 to 6
- R a1 is an organic group having 1 to 8 carbon atoms which may have a ring structure or a hydrogen atom.
- * is a connecting group to the main chain structure.
- the aliphatic hydrocarbon group preferably has a monovalent aliphatic saturated hydrocarbon group having 1 to 3 carbon atoms, such as a methyl group. If the base concentration T is 4 wt % or more, the dielectric loss tangent of the polyimide cured film tends to be good.
- the aliphatic hydrocarbon group concentration T is preferably 5 wt % or more, more preferably 7 wt % or more, and even more preferably 8 wt % or more. When the aliphatic hydrocarbon group concentration T is 5 wt % or more, the moisture permeability tends to be good.
- the aliphatic hydrocarbon group concentration T is 35 wt % or less, the resulting polyimide cured film tends to have good resolution and moisture permeability.
- the aliphatic hydrocarbon group concentration T is more preferably 28 wt% or less, more preferably 17 wt% or less, and even more preferably 12% or less.
- the aliphatic hydrocarbon group concentration T is expressed by the following formula (I) using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used when preparing the polyamide and/or polyimide precursor: [Mw (P) + Mw (Q)] / [Mw (A) + Mw (B) - 36] ⁇ 100 (I) ⁇ In formula (I), Mw (P) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the tetracarboxylic dianhydride, and Mw (Q) represents the molecular weight of the aliphatic hydrocarbon groups in the diamine compound. , Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound. ⁇ .
- Mw (A1) represents the molecular weight of the first tetracarboxylic dianhydride
- Mw (A2) represents the molecular weight of the second tetracarboxylic dianhydride
- a1 represents the first tetracarboxylic acid represents the content ratio of the dianhydride
- a2 represents the content ratio of the second tetracarboxylic dianhydride
- Mw (B1) represents the molecular weight of the first diamine compound
- Mw (B2) represents the molecular weight of the second diamine compound
- b1 represents the content ratio of the first diamine compound
- b2 represents the content ratio of the second diamine compound.
- the same requirements apply when three or more tetracarboxylic dianhydrides and/or diamine compounds are used.
- tetracarboxylic acid and/or tetracarboxylic acid chloride is used as a raw material, the molecular weight of the corresponding tetracarboxylic dianhydride is used for calculation.
- At least one of the tetracarboxylic dianhydride and the diamine compound preferably has an aliphatic hydrocarbon group.
- the diamine compound has an aliphatic hydrocarbon group
- the moisture permeability tends to be low, which is preferable.
- both the diamine compound and the tetracarboxylic dianhydride have an aliphatic hydrocarbon group, the solubility in the developer is improved, which tends to improve the developing speed, which is preferable.
- the measurement conditions of the IR spectrum are performed by the method described in the examples below.
- the peak intensity on the low wavelength side and the high wavelength side of the peak top is a value lower than the peak intensity of the peak top, and either the peak intensity on the low wavelength side or the high wavelength side is the peak of the peak top A value higher than the intensity is not regarded as a peak.
- Ph 2 is set to 0.
- the peak intensity near 1380 cm ⁇ 1 is defined as the maximum peak value within the range of ⁇ 10 cm ⁇ 1 for each wavenumber.
- Ph 2 ⁇ Im 1 is preferably 0.34 or more, more preferably 0.36 or more, more preferably 0.40 or more, and when it is 0.45 or more, the resolution tends to be good. Although not bound by theory, it is believed that when Ph 2 ⁇ Im 1 is 0.34 or more, the solubility of the polyimide precursor is improved and the resolution is improved. On the other hand, Ph 2 ⁇ Im 1 is preferably 1.2 or less, and when it is 1.1 or less, the dielectric loss tangent tends to be good. Although not bound by theory, it is believed that when Ph 2 ⁇ Im 1 is 1.2 or less, the molecular motion in the high frequency region is reduced.
- the following formula (1) -12.6 ⁇ UT ⁇ 16.0 (1)
- U represents the imide group concentration of the polyimide
- T represents the aliphatic hydrocarbon group concentration of the polyimide.
- ⁇ is preferably satisfied.
- UT is preferably -12.6 or more, more preferably -11.0 or more, and -10 or more tends to be preferable for resolution.
- UT is preferably 16.0 or less, more preferably 12.5 or less, preferably 12.0 or less, and 11.0 or less tends to be excellent in moisture permeability. be. The reason why the heating and curing at 350° C.
- the photosensitive resin composition is not intended to be heated and cured at 350° C. in actual use.
- Polyimide precursors include polyamide precursors having a structural unit represented by the following general formula (4). ⁇ wherein X 1 is a tetravalent organic group having 6 to 40 carbon atoms, Y 1 is a divalent organic group having 6 to 40 carbon atoms, and n 1 is an integer of 2 to 150; and R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R 4 and R 5 is a group represented by the following general formula (5).
- R 6 , R 7 and R 8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10; ⁇
- R4 and R5 in the general formula ( 4 ) are also referred to as a side chain or a side chain structure of the polyimide precursor.
- R 6 in the general formula (5) is preferably a hydrogen atom or a methyl group, and R 7 and R 8 are preferably hydrogen atoms from the viewpoint of photosensitivity.
- m2 is an integer of 2 or more and 10 or less, preferably 2 or more and 4 or less, from the viewpoint of photosensitive characteristics.
- the ratio of photosensitive groups per repeating unit in (A) the polyimide precursor resin represented by the general formula (4) is preferably 15 wt% to 35 wt%.
- the number of photosensitive groups is preferably as small as possible, and from the viewpoint of resolution, the number of photosensitive groups is preferably large.
- the ratio of the photosensitive group means the ratio of the molecular weight of the photopolymerizable group-containing compound constituting the repeating unit based on the molecular weight of the entire repeating unit represented by the above general formula (4). means.
- Photopolymerizable groups include, for example, unsaturated double bonds.
- the proportion of photosensitive groups per repeating unit of the polyimide precursor resin is expressed by the following formula (I) using the molecular weights of the tetracarboxylic dianhydride and the diamine compound used during preparation of the polyimide precursor: [Mw (R)] / [Mw (A) + Mw (B) + Mw (R) - 36] ⁇ 100 (I) ⁇ In the formula (I), Mw (R) represents the sum of the molecular weights of the compound containing a photopolymerizable group (photopolymerizable group-containing compound), Mw (A) represents the molecular weight of the tetracarboxylic dianhydride, And Mw (B) represents the molecular weight of the diamine compound.
- c 1 represents the content of a compound containing a photopolymerizable group
- c 2 represents the content of a compound not containing a photopolymerizable group
- the molecular weight of the corresponding tetracarboxylic dianhydride is used for calculation.
- n1 in the general formula (4) is preferably an integer of 3 to 100 , more preferably an integer of 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.
- the tetravalent organic group represented by X 1 is preferably an organic group having 6 to 40 carbon atoms, more preferably, in terms of achieving both heat resistance and photosensitive properties.
- -COOR 1 group and -COOR 2 group and -CONH- group are aromatic groups or alicyclic aliphatic groups in the ortho position to each other.
- tetravalent organic group represented by X 1 include an aromatic ring-containing organic group having 6 to 40 carbon atoms, such as the following general formula (7): ⁇ In formula (7), R 11 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1 - C10 fluorine-containing hydrocarbon group; is an integer from 0-2, m 6 is an integer from 0-3, and m 7 is an integer from 0-4. ⁇ , but not limited thereto.
- the structure of X1 may be one or a combination of two or more. Group X 1 having the structure represented by the above formula (7) is particularly preferred in terms of achieving both heat resistance and photosensitive properties.
- the divalent organic group represented by Y 1 is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties.
- the structure of Y1 may be one type or a combination of two or more types.
- One Y group having the structure represented by the above formula (8) is particularly preferable in terms of achieving both heat resistance and photosensitive properties.
- At least one of X 1 which is a skeleton component derived from a tetracarboxylic acid compound, or Y 1 , which is a skeleton component derived from a diamine compound, has a structure in which two or more benzene rings are bonded. It is preferable to have The number of benzene rings may be 3 or more, 4 or more, 6 or less, 5 or less, or 4 or less, and more preferably 4.
- the polyimide precursor has such a structure, the resolution of the negative photosensitive resin composition is maintained, and the resulting cured relief pattern tends to have low dielectric properties.
- the divalent organic group represented by Y 1 preferably has the structure of general formula (14) above.
- the resolution tends to be excellent.
- An ester bond type polyimide precursor having at least one terminal structure selected from the group consisting of the general formulas (1) to (3) can be obtained by any of the following methods. For example, it can be obtained by first synthesizing an esterified tetracarboxylic dianhydride having a terminal structure, and then subjecting it to amide polycondensation with a diamine compound.
- Method 1 for introducing a terminal structure In order to form the terminal structure of the general formula (1) and the general formula (2), a tetracarboxylic dianhydride having a desired tetravalent organic group X and a compound having an isocyanate group are reacted. After that, alcohols having a photopolymerizable group (e.g., unsaturated double bond) are reacted to partially imidize or imide derivatize (structure derived from the general formula (2)) / esterified A tetracarboxylic acid (hereinafter also referred to as an acid/ester/imide form) is prepared.
- a photopolymerizable group e.g., unsaturated double bond
- a tetracarboxylic acid hereinafter also referred to as an acid/ester/imide form
- Pyridine, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc. can be used to promote the reaction between the tetracarboxylic dianhydride and the compound having an isocyanate group.
- Saturated aliphatic alcohols may optionally be used together with the alcohols having a photopolymerizable group.
- a tetracarboxylic dianhydride having a desired tetravalent organic group X and an alcohol having a photopolymerizable group (e.g., unsaturated double bond) is reacted with to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester form), and then reacted with a compound having an isocyanate group to obtain a partially esterified/amidated tetracarboxylic acid.
- a carboxylic acid hereinafter also referred to as an acid/ester/amide form is prepared.
- Pyridine, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, etc. can be used to promote the reaction between the tetracarboxylic dianhydride and the compound having an isocyanate group.
- Saturated aliphatic alcohols may optionally be used together with the alcohols having a photopolymerizable group.
- tetracarboxylic dianhydride having a tetravalent organic group X 1 having 6 to 40 carbon atoms which is preferably used for preparing an ester bond type polyimide precursor
- tetracarboxylic acid dianhydride derived from the above-mentioned structure for example, pyromellitic anhydride, diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, anhydride, biphenyl-3,3′,4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3′,4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3′,4 ,4′-tetracarboxylic dianhydride, 2,2-
- a terminal structure is formed using introduction method 1 or introduction method 2 described above.
- the order of reactions varies depending on the introduction method.
- alcohols having a photopolymerizable group examples include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2 -hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate , 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamide ethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy- 3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl meth
- saturated aliphatic alcohols that can optionally be used together with the alcohols having photopolymerizable groups
- saturated aliphatic alcohols having 1 to 4 carbon atoms are preferable. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.
- reaction solvent those which completely dissolve the tetracarboxylic acid dianhydride and alcohol as starting materials and the acid/ester body as the product are preferred. More preferably, the solvent completely dissolves the polyimide precursor, which is the amide polycondensation product of the acid/ester compound and the diamine.
- the polyimide precursor which is the amide polycondensation product of the acid/ester compound and the diamine.
- N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonization Hydrogens etc. can be mentioned.
- ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
- esters include methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate and the like.
- lactones include ⁇ -butyrolactone and the like.
- ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like.
- halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene and the like.
- hydrocarbons include hexane, heptane, benzene, toluene, and xylene. These may be used alone or in combination of two or more as needed.
- a suitable dehydration condensation agent is added to the acid/ester compound (typically in a solution state dissolved in the reaction solvent), preferably under ice cooling, and mixed to convert the acid/ester compound into a polyacid anhydride. and Then, to this, a diamine containing a divalent organic group Y 1 having 6 to 40 carbon atoms separately dissolved or dispersed in a solvent is added dropwise, and the two are subjected to amide polycondensation to obtain the desired polyimide precursor. can be obtained. Diaminosiloxanes may be used in combination with the diamines having the divalent organic group Y1.
- dehydration condensation agent examples include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N '-disuccinimidyl carbonate and the like. As described above, the intermediate polyacid anhydride is obtained.
- diamines having a divalent organic group Y 1 having 6 to 40 carbon atoms that are preferably used for the reaction with the polyacid anhydride obtained as described above, other than the diamines derived from the above-mentioned structures,
- 1, 3 -Diaminosiloxanes such as bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.
- Methods for introducing a reactive substituent that reacts with heat or light to the end of the main chain include the following methods. First, at the time of amide polycondensation, for example, by charging an excessive amount of diamine, both ends of the main chain are made into amino groups. Then, a compound having a reactive substituent that reacts with heat or light and that has a site that also reacts with an amino group is reacted with the amino group. At this time, acid anhydrides, epoxies, isocyanates, and the like can be given as sites that react with amino groups. In addition, the following methods can also be mentioned.
- amide polycondensation an excessive amount of partially esterified tetracarboxylic acid is charged to convert both ends of the main chain to carboxyl groups. Then, a compound having a reactive substituent that reacts with heat or light and that has a site that also reacts with a carboxyl group is reacted with the carboxyl group. At this time, amine, alcohol, etc. can be mentioned as a site
- another synthesis method includes a method obtained by first synthesizing an esterified tetracarboxylic acid having a terminal structure, and then subjecting it to amide polycondensation with diamines.
- a tetracarboxylic dianhydride having a desired tetravalent organic group X 1 with a compound having an isocyanate group
- an alcohol having a photopolymerizable group e.g., an unsaturated double bond
- Saturated aliphatic alcohols may
- Examples of the compound having a reactive substituent that is used to introduce a reactive substituent that reacts with heat or light to the end of the main chain and that has a site that also reacts with an amino group include maleic anhydride , 5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, methacrylic anhydride, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-ethynyl phthalic anhydride, 4-vinyl phthalic anhydride, Di-t-butyl dicarbonate and the like can be mentioned.
- Examples of the compound having a reactive substituent that reacts with heat or light and having a site that reacts with a carboxyl group include 4-aminostyrene and 4-ethynylaniline.
- water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are optionally filtered off, and then a suitable poor solvent, such as water, is added to the solution containing the polymer component.
- a suitable poor solvent such as water
- Aliphatic lower alcohol, mixture thereof, etc. is added to precipitate the polymer component, and if necessary, the polymer is purified by repeating operations such as redissolution and reprecipitation, followed by vacuum drying.
- the desired polyimide precursor is isolated.
- the polymer solution may be passed through a column packed with anion and/or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.
- the weight average molecular weight of the polyimide precursor is 8,000 when measured by polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) from the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment. It is preferably from 150,000, more preferably from 9,000 to 50,000, and particularly preferably from 18,000 to 40,000. A weight-average molecular weight of 8,000 or more is preferable because mechanical properties are good, while a weight-average molecular weight of 150,000 or less is preferable because dispersibility in a developer and relief pattern resolution performance are good. . Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography.
- the molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene.
- standard monodisperse polystyrene it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.
- the photopolymerization initiator is a compound capable of generating radicals by actinic rays and polymerizing an ethylenically unsaturated group-containing compound or the like.
- examples of initiators that generate radicals with actinic rays include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime ester, acridine and phosphine oxide.
- Examples include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone , 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2 - aromatic ketones such as morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin, methylbenzoin, ethyl Benzoin compounds such as benzoin; 1,2-oc
- the (C) polymerization initiator explained above can be used alone or in combination of two or more.
- oxime ester compounds are more preferable from the viewpoint of resolution.
- the radical species is derived from a methyl group.
- the blending amount of the photopolymerization initiator is 0.5 parts by mass or more and 10 parts by mass or less, preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor.
- the above compounding amount is 0.5 parts by mass or more from the viewpoint of photosensitivity or patterning properties, and is preferably 10 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition. preferable.
- the solvent is not limited as long as it can uniformly dissolve or suspend (A) the polyimide precursor and (B) the photopolymerization initiator.
- solvents include ⁇ -butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetoacetamide, ⁇ -caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy- N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, etc. can be exemplified. These solvents may be used singly or in combination of two or more.
- the solvent is in the range of, for example, 30 to 1,500 parts by mass, preferably 100 to 1,000 parts per 100 parts by mass of the polyimide precursor (A). It can be used in the range of parts by mass.
- the solvent contains an alcohol having no olefinic double bond
- the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably It is preferably 10 to 30% by mass.
- the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when it is 50% by mass or less, (A) dissolution of the polyimide precursor becomes better.
- the photosensitive resin composition can optionally contain (D) a silane coupling agent.
- the silane coupling agent preferably has a structure represented by the following general formula (12). ⁇ Wherein , R 12 is at least one selected from the group consisting of substituents including an epoxy group, a phenylamino group, a urea group, an isocyanuric group, and a ureido group; 4, R 14 is a hydroxyl group or an alkyl group having 1-4 carbon atoms, d is an integer of 1-3, and m 8 is an integer of 1-6. ⁇
- d is not limited as long as it is an integer of 1 to 3, but is preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to the metal rewiring layer.
- m8 is not limited as long as it is an integer of 1 to 6 , it is preferably 1 or more and 4 or less from the viewpoint of adhesion to the metal rewiring layer. 2 or more and 5 or less are preferable from a developable viewpoint.
- R 12 is not limited as long as it is a substituent containing any structure of the group consisting of an epoxy group, a phenylamino group, a urea group, an isocyanuric group and a ureido group. Among these, at least one selected from the group consisting of a substituent containing a phenylamino group, a substituent containing a urea group, and a substituent containing a ureido group, from the viewpoint of developability and adhesiveness of the metal rewiring layer. A species is preferred, and a substituent containing a phenylamino group is more preferred.
- R 13 is not limited as long as it is an alkyl group having 1 to 4 carbon atoms.
- R 14 is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms the same alkyl groups as those for R 13 can be exemplified.
- Silane coupling agents containing epoxy groups include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Examples include sidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.
- Examples of phenylamino group-containing silane coupling agents include N-phenyl-3-aminopropyltrimethoxysilane.
- silane coupling agent containing a ureido group 3-ureidopropyltrialkoxysilane can be exemplified.
- a silane coupling agent containing an isocyanate group can be exemplified by 3-isocyanatopropyltriethoxysilane.
- the photosensitive resin composition can optionally contain (E) a radically polymerizable compound.
- a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and although it is not particularly limited to the following, ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate Or polyethylene glycol mono- or di-acrylate or methacrylate, propylene glycol or polypropylene glycol mono- or di-acrylate or methacrylate, glycerol mono-, di- or tri-acrylate or methacrylate, cyclohexane diacrylate or dimethacrylate, 1,4-butanediol di- acrylates or dimethacrylates, diacrylate or dimethacrylate of 1,6-hexanediol, diacrylate or dime
- the compounding amount of the compound having an ethylenically unsaturated double bond is 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- the photosensitive resin composition may optionally contain (F) a thermal cross-linking agent.
- a thermal cross-linking agent means a compound that causes an addition reaction or a condensation polymerization reaction by heat. These reactions occur in combinations of (A) resin and (F) thermal cross-linking agent, (F) thermal cross-linking agents themselves, and (F) thermal cross-linking agent and other components described later. °C or higher is preferred.
- the thermal cross-linking agent preferably contains a nitrogen atom. As a result, the interaction with the polyimide resin is increased, and higher chemical resistance can be expected.
- thermal crosslinking agents include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds.
- alkoxymethyl compounds include, but are not limited to, the following compounds.
- epoxy compounds include epoxy compounds containing bisphenol A type groups and hydrogenated bisphenol A diglycidyl ethers (eg Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.).
- the oxetane compounds include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3 -ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis(3-ethyl) -3-oxetanylmethyl) ether, bis(3-ethyl-3-oxetanylmethyl) diphenoate, trimethyl
- Bismaleimide compounds include 1,2-bis(maleimido)ethane, 1,3-bis(maleimido)propane, 1,4-bis(maleimido)butane, 1,5-bis(maleimido)pentane, 1,6- bis(maleimido)hexane, 2,2,4-trimethyl-1,6-bis(maleimido)hexane, N,N'-1,3-phenylenebis(maleimido), 4-methyl-N,N'-1, 3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide ) diphenylmethane, 3,3′-diethyl-5,5′-dimethyl-4,4′-bis(maleimido)diphenylmethane or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.
- Allyl compounds include allyl alcohol, allylanisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenylsulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and maleic acid.
- diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, triallyl citrate, etc. be done.
- hexamethylene diisocyanate-based blocked isocyanate for example, Asahi Kasei Co., Ltd. Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF -K60B and WM44-L70G, Mitsui Chemicals Takenate B-882N, Baxenden 7960, 7961, 7982, 7991, and 7992, etc.), tolylene diisocyanate-based blocked isocyanate (e.g., Mitsui Chemicals Co., Ltd.) Takenate B-830, etc.), 4,4′-diphenylmethane diisocyanate-based blocked isocyanate (for example, Takenate B-815N manufactured by Mitsui Chemicals, Bronate PMD-OA01 manufactured by Taiei Sangyo Co., Ltd., and
- the content of the (F) thermal cross-linking agent in the resin composition is 0.2% by mass to 40% by mass based on the total solid content of the resin composition, and from the viewpoint of low dielectric properties and chemical resistance , more preferably 1% by mass to 20% by mass, and even more preferably 2% by mass to 10% by mass.
- the photosensitive resin composition may optionally contain (G) a filler.
- the filler is not limited as long as it is an inert substance added to improve strength and various properties.
- the filler is preferably in the form of particles from the viewpoint of suppressing an increase in viscosity when made into a resin composition.
- the particle shape include acicular, plate, and spherical shapes. From the viewpoint of suppressing an increase in viscosity when the resin composition is formed, the filler is preferably spherical.
- acicular fillers examples include wollastonite, potassium titanate, xonotlite, aluminum borate, and acicular calcium carbonate.
- Plate-like fillers include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-like calcium carbonate.
- Spherical fillers include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, and barium titanate.
- silica, alumina, titanium oxide, and barium titanate are preferred, and silica and alumina are more preferred, from the viewpoint of electrical properties and storage stability when used as a resin composition.
- the size of the filler is defined as the primary particle diameter in the case of a spherical shape, and the length of the long side in the case of a plate-like or needle-like shape. If it is 10 nm or more, the resin composition tends to be sufficiently uniform, and if it is 1000 nm or less, photosensitivity can be imparted. From the viewpoint of imparting photosensitivity, it is preferably 800 nm or less, more preferably 600 nm or less, and particularly preferably 300 nm or less. From the viewpoint of adhesion and uniformity of the resin composition, the thickness is preferably 15 nm or more, more preferably 30 nm or more, and particularly preferably 50 nm or more.
- the content of the (G) filler in the resin composition is 1 vol% to 20 vol% based on the mass of the resin composition, and from the viewpoint of dielectric properties, it is preferably 5 vol% to 20 vol%. From the point of view, it is more preferably 5 vol % to 10 vol %.
- the photosensitive resin composition may further contain components other than the above components (A) to (G).
- other components include (A) resin components other than polyimide precursors; organic compounds containing metal elements, sensitizers, thermal polymerization inhibitors, azole compounds, and hindered phenol compounds.
- the photosensitive resin composition may further contain resin components other than (A) the polyimide precursor.
- resin components that can be contained in the photosensitive resin composition include polyimides, polyoxazoles, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, and acrylic resins.
- the blending amount of these resin components is preferably in the range of 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).
- the photosensitive resin composition may contain an organic compound containing a metal element.
- the organic compound containing a metal element preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule.
- the organic group preferably includes a hydrocarbon group and a hydrocarbon group containing a heteroatom.
- organotitanium or zirconium compounds are shown below in I) to VII):
- a compound having two or more alkoxy groups is more preferable because the storage stability of the photosensitive resin composition and a good pattern can be obtained.
- chelate compounds include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4- pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and compounds in which the titanium atom of these compounds is substituted with a zirconium atom. is not limited to
- tetraalkoxy compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, and titanium tetramethoxide.
- titanium tetramethoxypropoxide titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl )butoxide ⁇ ], and compounds in which the titanium atom of these compounds is substituted with a zirconium atom, but are not limited to these.
- Titanocene or zirconocene compounds include, for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis ( ⁇ 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, the titanium atom of these compounds replaced by a zirconium atom compounds include, but are not limited to.
- Monoalkoxy compounds include, for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and compounds in which the titanium atom of these compounds is substituted with a zirconium atom. is not limited to
- Titanium oxide or zirconium oxide compounds include, for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and compounds obtained by substituting the titanium atom of these compounds with a zirconium atom. include, but are not limited to.
- Titanium tetraacetylacetonate or zirconium tetraacetylacetonate compounds include, but are not limited to, titanium tetraacetylacetonate and compounds in which the titanium atom of these compounds is substituted with a zirconium atom. do not have.
- titanate coupling agents include, but are not limited to, isopropyl tridodecylbenzenesulfonyl titanate.
- the organotitanium compound is more preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. It is preferable from the viewpoint of exhibiting a good dielectric loss tangent.
- titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis( ⁇ 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-( 1H-pyrrol-1-yl)phenyl)titanium is preferred.
- the blending amount is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, per 100 parts by mass of the resin (A). .
- the amount is 0.01 part by mass or more, a good imidization ratio of the resin composition and the dielectric loss tangent of the cured film are exhibited, and when the amount is 10 parts by mass or less, the storage stability is excellent, which is preferable. .
- the photosensitizer resin composition contains an organic compound containing the above metal element to improve the imidization rate of the polyimide precursor contained in the resin composition, and the dielectric loss tangent of the cured film using the resin composition can be reduced.
- the reason for improving the imidization rate of the polyimide precursor is that the metal element contained in the organic compound containing the metal element is a carbonyl derived from the ester group and / or carboxyl group of the polyimide precursor. This is believed to be because the electron density of the carbon atom of the carbonyl group is reduced by coordinating to the group and the ring closure reaction is promoted.
- the photosensitive resin composition can optionally contain a sensitizer to improve photosensitivity.
- sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal).
- the photosensitive resin composition can optionally contain a thermal polymerization inhibitor, particularly in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage in a solvent-containing solution.
- Thermal polymerization inhibitors include, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2 , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl- N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium
- the photosensitive resin composition can optionally contain an azole compound in order to suppress discoloration of the substrate.
- Azole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis( ⁇
- the amount of the azole compound compounded is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of photosensitivity characteristics, it is 0.5 parts by mass to 5 parts by mass. It is more preferable to have If the blending amount of the azole compound relative to 100 parts by mass of the polyimide precursor (A) is 0.1 parts by mass or more, when the photosensitive resin composition is formed on copper or a copper alloy, the copper or copper alloy surface Discoloration is suppressed, and on the other hand, if it is 20 parts by mass or less, it is preferable because it is excellent in photosensitivity.
- the photosensitive resin composition can contain a hindered phenol compound in order to suppress discoloration of the substrate when using a substrate made of copper or a copper alloy.
- Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-
- 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.
- the amount of the hindered phenol compound is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 10 parts by mass. Part is more preferred. If the amount of the hindered phenol compound (A) per 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, copper or Discoloration and corrosion of the copper alloy are prevented, and on the other hand, if it is 20 parts by mass or less, it is preferable because it is excellent in photosensitivity.
- the present disclosure also provides a method for producing a cured polyimide film, which includes converting the photosensitive resin composition to polyimide.
- the method for producing a cured polyimide film of the present disclosure includes, for example, the following steps (1) to (5): (1) applying the photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of heating and drying the obtained photosensitive resin layer; (3) exposing the photosensitive resin layer after heating and drying; (4) a step of developing the photosensitive resin layer after exposure; and (5) a step of heat-treating the photosensitive resin layer after development to form a cured polyimide film; including.
- the photosensitive resin composition used in the method for producing a cured film preferably contains 100 parts by mass of a polyimide precursor, 0.5 to 10 parts by mass of a photosensitizer, and 100 to 300 parts by mass of a solvent. It is more preferable that a photoradical polymerization initiator is included as the agent, and it is even more preferable that the photosensitive resin composition is of a negative type.
- a step of applying a photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate the photosensitive resin composition of the present disclosure is applied onto a substrate, and if necessary Optionally, it is then dried to form a photosensitive resin layer.
- a method conventionally used for coating a photosensitive resin composition for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.
- the photosensitive resin composition film can be heated and dried.
- a drying method methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used.
- the drying of the coating film is carried out under such conditions that imidization of (A) the polyimide precursor (polyamic acid ester) in the photosensitive resin composition does not occur.
- air drying or heat drying drying can be performed at 20° C. to 140° C. for 1 minute to 1 hour.
- a photosensitive resin layer can be formed on the substrate.
- Step of exposing the photosensitive resin layer after heating and drying the photosensitive resin layer formed above is exposed.
- the exposure device for example, a contact aligner, a mirror projection, a stepper, or the like is used. Exposure can be through a patterned photomask or reticle or directly.
- the light used for exposure is, for example, an ultraviolet light source.
- post-exposure baking PEB
- pre-development baking may be performed at any combination of temperature and time, if necessary.
- the range of baking conditions is preferably a temperature of 40 to 120° C. and a time of 10 seconds to 240 seconds. .
- Step of developing the exposed photosensitive resin layer the exposed photosensitive resin layer is developed to form a relief pattern.
- the photosensitive resin composition is of a negative type
- the unexposed portion of the exposed photosensitive resin layer is removed by development.
- a developing method for developing the photosensitive resin layer after exposure any of conventionally known photoresist developing methods such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like can be used. method can be selected and used.
- post-development baking may be performed at any combination of temperature and time for the purpose of adjusting the shape of the relief pattern, etc., if necessary.
- a developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent.
- good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, and the like.
- Preferred examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water.
- the ratio of the poor solvent to the good solvent is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition.
- two or more kinds of each solvent can be used, for example, several kinds can be used in combination.
- the development time is preferably 30 seconds or less, more preferably 25 seconds or less, even more preferably 20 seconds or less.
- a step of heat-treating the photosensitive resin layer after development to form a polyimide cured film In this step, the relief pattern obtained by the development is heated to dilute the photosensitive component, and The polyimide precursor is imidized and converted into a cured relief pattern of polyimide.
- the heat curing method various methods such as a method using a hot plate, a method using an oven, and a method using a heating oven capable of setting a temperature program can be selected. Heating can be performed, for example, at 160° C. to 400° C. for 30 minutes to 5 hours.
- As the atmospheric gas for heat curing air may be used, or an inert gas such as nitrogen or argon may be used.
- a cured relief pattern (cured polyimide film) can be produced.
- the method for producing a cured polyimide film of the present disclosure includes, for example, coating the photosensitive resin composition of the present disclosure on a substrate, exposure treatment, development treatment, and then heat treatment, and is a method for producing a cured film.
- the cured film preferably has a dielectric loss tangent of 0.003 to 0.012 when measured at 40 GHz by a perturbation split cylinder resonator method.
- the dielectric loss tangent can be measured by the perturbation type split cylinder resonator method shown in the examples below.
- the present disclosure also provides a cured polyimide film obtained from the photosensitive resin composition described above.
- the cured film preferably has a moisture permeability of less than 800, more preferably less than 700. From the viewpoint of the dielectric loss tangent, the lower the moisture permeability, the less the frequency dependence of the dielectric loss tangent. It is more preferably 500 or more and less than 800 because the solubility becomes poor and the resolution becomes poor. By being less than 800, a highly reliable cured film can be obtained. See below for details on how to measure moisture permeability.
- the product of dielectric loss tangent and moisture permeability (tan ⁇ 40 ⁇ WVTR) is within a certain range, and a dielectric loss tangent value of 40 GHz was used.
- a dielectric loss tangent value of 40 GHz was used.
- 3.0 ⁇ tan ⁇ 40 ⁇ WVTR ⁇ 10.0 (3) is preferably satisfied.
- tan ⁇ 40 ⁇ WVTR is in the range of 3.0 to 10.0, a cured polyimide product with excellent resolution and dielectric properties and little frequency dependence can be obtained.
- the difference in dielectric loss tangent between 40 GHz and 10 GHz is preferably 0.0015 or less, more preferably 0.001 or less.
- the substrate on which the cured relief pattern produced according to the present disclosure is formed is formed on a substrate selected from the group consisting of resin, silicon (Si), copper (Cu), aluminum (Al) and combinations thereof. is preferred, and Cu is particularly preferred.
- a hardened relief pattern on Cu it may be formed on a Cu layer formed on a Si wafer.
- Another metal layer may be formed between the Si wafer and the Cu layer.
- the metal layer formed between the Si wafer and the Cu layer is preferably a Ti layer.
- the cured relief pattern has an aspect ratio of preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. By increasing the aspect ratio, finer wiring can be formed.
- a via of 20 ⁇ m or less is preferably opened, a via of 15 ⁇ m or less is more preferable, and a via of 10 ⁇ m or less is opened. is more preferred.
- the present disclosure can also provide a semiconductor device having a cured relief pattern obtained by the method for producing a cured relief pattern described above using the photosensitive resin composition of the present disclosure. Accordingly, there is provided a semiconductor device having a base material which is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-described cured relief pattern manufacturing method. The present disclosure can also be applied to a semiconductor device manufacturing method that uses a semiconductor element as a base material and includes the above-described cured relief pattern manufacturing method as part of the process.
- the cured relief pattern formed by the cured relief pattern manufacturing method may be used as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure. etc., and can be manufactured by combining with a known method for manufacturing a semiconductor device.
- the polyimide contained in the cured relief pattern (cured polyimide film) formed from the polyimide precursor composition has the following general formula (13): ⁇ In general formula (13), X 1 and Y 1 are the same as X 1 and Y 1 in general formula (4) above, and n 2 is an integer of 2-150. ⁇ is preferable.
- the present disclosure is a display device comprising a display element and a cured film provided on top of the display element using the photosensitive resin composition of the present disclosure, wherein the cured film is the above cured relief
- a display device that is a pattern can also be provided.
- the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween.
- the cured film include surface protective films, insulating films, and flattening films for TFT liquid crystal display elements and color filter elements, projections for MVA type liquid crystal display devices, and barrier ribs for cathodes of organic EL devices. .
- the photosensitive resin composition of the present disclosure in addition to application to the semiconductor device as described above, is also useful for applications such as interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. be.
- this photosensitive resin layer having a thickness of about 13.5 ⁇ m was formed.
- this photosensitive resin layer was irradiated with energy of 200 mJ/cm 2 from Prisma GHI (manufactured by Ultratech) fitted with an i-line filter.
- this photosensitive resin layer is spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to form a relief on Cu. Got a pattern.
- the spray development time at this time was defined as the development time.
- the wafer having the relief pattern formed on Cu is heated in a nitrogen atmosphere at 230 ° C. for 2 hours using a temperature-rising programmable curing furnace (VF-2000, manufactured by Koyo Lindbergh Co., Ltd.).
- VF-2000 temperature-rising programmable curing furnace
- a hardened relief pattern of resin having a thickness of about 10 ⁇ m was obtained.
- the formed relief pattern was observed under an optical microscope to determine the size of the minimum via opening pattern. At this time, if the area of the opening of the obtained pattern is 1/2 or more of the opening area of the corresponding pattern mask, it is regarded as resolved, and the opening having the minimum area among the resolved openings is determined. Based on the corresponding mask opening side length (opening pattern size), the resolution was determined according to the following evaluation criteria.
- the size of the minimum opening pattern is less than 10 ⁇ m
- B The size of the minimum opening pattern is 10 ⁇ m or more and less than 15 ⁇ m
- C The size of the minimum opening pattern is 15 ⁇ m or more and less than 20 ⁇ m
- D The size of the minimum opening pattern is 20 ⁇ m or more
- a photosensitive resin layer having a thickness of about 13.5 ⁇ m was formed. Then, using an aligner (PLA-501F, manufactured by Canon Inc.), the entire surface was exposed to ghi rays with an exposure amount of 600 mJ/cm 2 , and a vertical curing furnace (manufactured by Koyo Lindbergh, model name VF-2000B) was used in a nitrogen atmosphere. Then, heat curing treatment was performed at 230° C. for 2 hours to form a cured film of resin having a thickness of about 10 ⁇ m on the Al wafer.
- PPA-501F manufactured by Canon Inc.
- this cured film is cut into 80 mm long and 62 mm wide (for 10 GHz measurement) and 40 mm long and 30 mm wide (for 40 GHz measurement), and 10% It was immersed in an aqueous solution of hydrochloric acid and peeled off from the silicon wafer to obtain a film sample. After the film samples were dried in an oven at 50° C. for 24 hours, the dielectric constant (Dk) and dielectric loss tangent (Df) of the film samples at 10 GHz and 40 GHz were measured by the cavity perturbation method. The details of the measurement method are as follows.
- this cured film was cut into pieces of 80 mm long and 62 mm wide, immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer, forming a film sample. did.
- the moisture permeability was measured according to the cup method of JIS Z0208.
- the amount of calcium chloride used was 40 g, and the moisture permeation conditions were a temperature of 65° C. and a humidity of 90% RH. The test was carried out for 24 hours, after which the sample was taken out from the thermo-hygrostat, allowed to stand at room temperature for 30 minutes, and the weight was measured.
- WVTR Water permeability
- IR measurement For IR measurement, the film obtained in (3) above was measured by the ATR method using Nicolet 380 in a range of 700 cm -1 or more and 4000 cm -1 or less with 50 scans. . A silicon prism was used for the sample contact part. Of the absorption peaks in the range of 1450 cm -1 or more and 1550 cm -1 or less, the maximum peak intensity is Ph 1 , the second peak intensity is Ph 2 , the peak intensity near 1380 cm -1 is Im 1 , and Ph 1 was normalized to 1, Ph 2 and Im 1 were calculated. The peak intensity near 1380 cm ⁇ 1 was taken as the largest peak at 1380 cm ⁇ 1 ⁇ 10 cm ⁇ 1 .
- the concentrated residue was poured into 1.6 L of ion-exchanged water, and 2.5 L of ethyl acetate was further added for liquid separation and purification three times.
- the organic layer was collected and dried over MgSO4.
- impurities were removed by filtration, 800 mL of toluene was added to dissolve the residue, and the mixture was added to 4.0 L of methanol and stirred for 30 minutes.
- the filter cake was collected by filtration and dried at 80° C. for 12 hours.
- the reaction product obtained by drying was charged into a 5 L four-necked flask replaced with Ar, and 19.04 g of 5% Pd/C (EA) and 1.9 L of THF were added and stirred.
- the flask was heated to 40° C., H 2 bubbling (10 mL/min) was performed, and a reduction reaction was performed for 24 hours.
- the reaction mixture was filtered through celite, the target fraction was collected by silica gel chromatography, and concentrated under reduced pressure to obtain diamine X-1.
- polyimide precursor (polymer A-1): Put 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2-liter separable flask, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of ⁇ -butyrolactone, and stir at room temperature. While adding 79.1 g of pyridine, a reaction mixture was obtained. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and left still for 16 hours.
- ODPA 4,4′-oxydiphthalic dianhydride
- HEMA 2-hydroxyethyl methacrylate
- the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer.
- the resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
- the resulting crude polymer solution was purified using an anion exchange resin (“Amberlyst TM 15” manufactured by Organo Co., Ltd.) to obtain a polymer solution.
- the resulting polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum dried to obtain a powdery polymer A-1.
- Mw weight average molecular weight
- the polyimide obtained from polymer A-1 had an imide group concentration U of 19.6 wt % and an aliphatic hydrocarbon group concentration T of 8.4 wt % per repeating unit.
- the "imido group concentration U” and “aliphatic hydrocarbon group concentration T” are calculated by converting the cured polyimide film obtained by heating and curing at 350°C into polyimide (the same applies hereinafter).
- polyimide precursor (polymer A-2): In the synthesis of polymer A-1, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was used instead of 155.1 g of ODPA, and 2,2-bis[4-( Polymer A-1 except that 92.88 g of 2,2′-dimethylbiphenyl-4,4′-diamine (m-TB) was used in place of 191.87 g of 4-aminophenoxy)-3-methylphenyl]propane Polymer A-2 was obtained by carrying out the reaction in the same manner as described in the synthesis of . When the weight average molecular weight (Mw) of this polymer A-2 was measured, it was 23,000. The polyimide obtained from polymer A-2 had an imide group concentration U of 20.1 wt % and an aliphatic hydrocarbon group concentration T of 8.6 wt % per repeating unit.
- Mw weight average molecular weight
- Polymer A-3 In the synthesis of polymer A-1 above, 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane was replaced with 1,4-bis(4-aminophenoxy)-2 Polymer A-3 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-1, except that 146.3 g of .,3,5-trimethylbenzene was used. When the weight average molecular weight (Mw) of this polymer A-3 was measured, it was 20,000.
- the polyimide obtained from polymer A-3 had an imide group concentration U of 23.0 wt % and an aliphatic hydrocarbon group concentration T of 7.4 wt % per repeating unit.
- Polymer A-4 In the synthesis of polymer A-1, 155.1 g of ODPA was replaced with 147.1 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), except that Polymer A-4 was obtained by carrying out the reaction in the same manner as described in Synthesis. When the weight average molecular weight (Mw) of this polymer A-4 was measured, it was 21,000. The polyimide obtained from polymer A-4 had an imide group concentration U of 20.1 wt % and an aliphatic hydrocarbon group concentration T of 8.6 wt % per repeating unit.
- Mw weight average molecular weight
- Polymer A-5 In the synthesis of the polymer A-1, instead of 155.1 g of ODPA, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was used. A polymer A-5 was obtained by carrying out the reaction in the same manner as described in the synthesis. The weight average molecular weight (Mw) of this polymer A-5 was measured to be 24,000. The polyimide obtained from polymer A-5 had an imide group concentration U of 15.2 wt % and an aliphatic hydrocarbon group concentration T of 9.8 wt % per repeating unit.
- Polymer A-6 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-1. When the weight average molecular weight (Mw) of this polymer A-6 was measured, it was 22,000.
- the polyimide obtained from polymer A-6 had an imide group concentration U of 15.8 wt % and an aliphatic hydrocarbon group concentration T of 16.2 wt % per repeating unit.
- Polymer A-7 In the synthesis of polymer A-1, 260.2 g of 4,4'-(4,4'-isopropylidenediphenoxy) acid dianhydride was added in place of 155.1 g of ODPA, and 2,2-bis[4-( 4-Aminophenoxy)-3-methylphenyl]propane 191.87 g was replaced with 247.1 g of diamine X-1, but the reaction was carried out in the same manner as described in the synthesis of polymer A-1. to obtain polymer A-7. When the weight average molecular weight (Mw) of this polymer A-7 was measured, it was 20,000.
- the polyimide obtained from polymer A-7 had an imide group concentration U of 13.3 wt % and an aliphatic hydrocarbon group concentration T of 20.7 wt % per repeating unit.
- Polymer A-8 In the synthesis of polymer A-1, 109.06 g of pyromellitic dianhydride and 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane were used instead of 150.1 g of ODPA. Polymer A-8 was obtained by carrying out the reaction in the same manner as described in the synthesis of polymer A-1, except that 247.1 g of diamine X-1 was used instead. When the weight average molecular weight (Mw) of this polymer A-8 was measured, it was 14,000. The polyimide obtained from polymer A-8 had an imide group concentration U of 18.7 wt % and an aliphatic hydrocarbon group concentration T of 25.1 wt % per repeating unit.
- Polymer A-9 was obtained by carrying out the reaction. When the weight average molecular weight (Mw) of this polymer A-9 was measured, it was 21,000.
- the polyimide obtained from polymer A-9 had an imide group concentration U of 20.0 wt % and an aliphatic hydrocarbon group concentration T of 6.5 wt % per repeating unit.
- Polymer A-10 In the synthesis of polymer A-1, 247.1 g of diamine X-1 was used instead of 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. A polymer A-10 was obtained by carrying out the reaction in the same manner as in the synthesis of A-1. The weight average molecular weight (Mw) of this polymer A-10 was measured and found to be 16,000. The polyimide obtained from polymer A-10 had an imide group concentration U of 16.7 wt % and an aliphatic hydrocarbon group concentration T of 22.3 wt % per repeating unit.
- the resulting reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of crude polymer.
- the resulting crude polymer was collected by filtration and dissolved in 1000 g of ⁇ -butyrolactone to obtain a crude polymer solution.
- the resulting crude polymer solution was purified using an anion exchange resin (“Amberlyst TM 15” manufactured by Organo Co., Ltd.) to obtain a polymer solution.
- the resulting polymer solution was added dropwise to 8000 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdery polymer A-11.
- the weight average molecular weight (Mw) of this polymer A-11 was measured to be 22,000, the imide group concentration U per repeating unit was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%. there were.
- the resulting reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of crude polymer.
- the resulting crude polymer was collected by filtration and dissolved in 1000 g of ⁇ -butyrolactone to obtain a crude polymer solution.
- the resulting crude polymer solution was purified using an anion exchange resin (“Amberlyst TM 15” manufactured by Organo Co., Ltd.) to obtain a polymer solution.
- the resulting polymer solution was added dropwise to 8000 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain a powdery polymer A-12.
- the weight average molecular weight (Mw) of this polymer A-12 was measured to be 15,000, the imide group concentration U per repeating unit was 20.1 wt%, and the aliphatic hydrocarbon group concentration T was 8.6 wt%. there were.
- Polymer A-13 In the synthesis of polymer A-1, 147.1 g of BPDA was substituted for 155.1 g of ODPA, and 85 diaminodiphenyl ether was substituted for 191.87 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane. Polymer A-13 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-1, except that 0.8 g was used. The weight average molecular weight (Mw) of this polymer A-13 was measured to be 22,000. The polyimide obtained from polymer A-13 had an imide group concentration U of 30.5 wt % and an aliphatic hydrocarbon group concentration T of 0 wt % per repeating unit.
- Polymer A-14 In the synthesis of polymer A-1 above, polymer A- Polymer A-14 was obtained by carrying out the reaction in the same manner as in the synthesis of No. 1. When the weight average molecular weight (Mw) of this polymer A-14 was measured, it was 19,000. The polyimide obtained from polymer A-14 had an imide group concentration U of 28.8 wt % and an aliphatic hydrocarbon group concentration T of 6.2 wt % per repeating unit.
- Polyimide Precursor (Polymer A-15): In the synthesis of polymer A-1 above, 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane was replaced with 191.87 g of 2,2-bis ⁇ 4-(4-aminophenoxy) Polymer A-15 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-1, except that 179.59 g of phenyl ⁇ propane was used. The weight average molecular weight (Mw) of this polymer A-15 was measured and found to be 22,000. The polyimide obtained from Polymer A-15 had an imide group concentration U of 20.5 wt % and an aliphatic hydrocarbon group concentration T of 4.4 wt % per repeating unit.
- the polyimide obtained from polymer A-16 had an imide group concentration U of 14.1 wt % and an aliphatic hydrocarbon group concentration T of 12.1 wt % per repeating unit.
- Photopolymerization initiator B-1 TR-PBG-304 (manufactured by Changzhou Strong Electronics Co., Ltd.)
- Photopolymerization initiator B-2 TR-PBG-305 (manufactured by Changzhou Strong Electronics Co., Ltd.)
- Photopolymerization initiator B-3 TR-PBG-3057 (manufactured by Changzhou Strong Electronics Co., Ltd.)
- C-1 ⁇ -butyrolactone (GBL)
- C-2 dimethyl sulfoxide (DMSO)
- D-1 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
- D-2 N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
- Example 1 As shown in Table 1, using the polyimide precursor A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated.
- A-1 as a polyimide precursor: 100 g
- B-1 as a photopolymerization initiator: 5 g
- C GBL as a solvent: 180 g
- DMSO 20 g.
- the viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of GBL to prepare a negative photosensitive resin composition.
- the compositions were evaluated according to the methods described above. The results are shown in Table 2 below.
- Examples 2 to 26 Comparative Examples 1 to 3> A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that it was prepared at the compounding ratios shown in Tables 1, 3 and 5 below, and the same evaluation as in Example 1 was performed. The results are shown in Tables 2, 4 and 6 below.
- the dielectric loss tangent (Df) at 40 GHz of the photosensitive resin compositions of Examples 1 to 27 is as low as 0.0059 to 0.012 compared to Comparative Examples 1 to 3. showed that. Further, in the photosensitive resin compositions of Examples 1 to 27, the product of the moisture permeability and the dielectric loss tangent was 3.91 to 9.41, which was lower than that of the comparative examples. Comparative Examples 1 and 2 had longer development times, and Comparative Example 1 had a resolution of "D".
- the photosensitive resin composition according to the present invention By using the photosensitive resin composition according to the present invention, it is possible to obtain a cured film exhibiting high resolution in a thick film and a low dielectric loss tangent. Therefore, the photosensitive resin composition according to the present invention can be suitably used in the field of photosensitive materials useful for producing electric/electronic materials such as semiconductor devices and multilayer wiring boards.
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Abstract
Description
[1]
(A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、上記感光性樹脂組成物を350℃で加熱及び硬化して得られるポリイミド硬化膜のポリイミドにおいて、テトラカルボン酸二無水物とジアミンに由来する構造を含む繰り返し単位の分子量に対して、イミド基の分子量が占める割合であるイミド基濃度Uが、12wt%~26wt%であり、
上記樹脂が下記一般式(14)で示す構造を含む、感光性樹脂組成物。
[2]
上記感光性樹脂組成物を350℃で加熱及び硬化して得られるポリイミド硬化膜のポリイミドにおいて、テトラカルボン酸二無水物とジアミン化合物に由来する構造を含む繰り返し単位の分子量に対して、脂肪族炭化水素基の分子量の合計が占める割合である脂肪族炭化水素基濃度Tが4wt%~35wt%である、項目1に記載の感光性樹脂組成物。
[3]
一般式(14)で示される構造がジアミン由来である、項目1又は2に記載の感光性樹脂組成物。
[4]
上記樹脂がポリイミド前駆体である、項目1~3のいずれか一項に記載の感光性樹脂組成物。
[5]
上記ポリイミド前駆体が、以下の一般式(4)で表される構造を含む、項目4に記載の感光性樹脂組成物。
[6]
(A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、
上記樹脂がポリイミド前駆体を含む場合、上記ポリイミド前駆体が、以下の一般式(4):
上記樹脂が、下記一般式(15):
上記樹脂が、下記一般式(14):
[7]
(A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、上記感光性樹脂組成物を350℃で加熱及び硬化して得られるポリイミド硬化膜のポリイミドにおいて、テトラカルボン酸二無水物とジアミンに由来する構造を含む繰り返し単位の分子量に対して、イミド基の分子量が占める割合をイミド基濃度Uとし、脂肪族炭化水素基の分子量の合計が占める割合を脂肪族炭化水素基濃度Tとすると、Uが、12wt%~26wt%であり、かつ、下記式(1):
-12.6<U-T<16.0 (1)
{を満たす、感光性樹脂組成物。
[8]
(A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、
(A)ポリイミド前駆体を230℃で加熱及び硬化して得られるポリイミドのIRスペクトルで、1450cm-1以上1550cm-1以下の範囲にある吸収ピークの、一番大きなピーク強度をPh1、二番目の強度のピーク強度をPh2、1380cm-1付近のピーク強度をIm1とし、Ph1を1に規格化した時、下記式(2):
0.34≦Ph2×Im1≦1.2 (2)
を満たす、感光性樹脂組成物。
[9]
上記樹脂が、テトラカルボン酸二無水物とジアミンとの反応物である、項目1~8のいずれか一項に記載の感光性樹脂組成物。
[10]
上記樹脂を構成する上記テトラカルボン酸二無水物の少なくとも一種、及び上記ジアミンの少なくとも一種が、脂肪族炭化水素基を有する、項目9に記載の感光性樹脂組成物。
[11]
(D)シランカップリング剤を更に含む、項目1~10のいずれか一項に記載の感光性樹脂組成物。
[12]
(E)ラジカル重合性化合物を更に含む、項目1~11のいずれか一項に記載の感光性樹脂組成物。
[13]
(E)ラジカル重合性化合物がアルキル基を持つことを特徴とする、項目12に記載の感光性樹脂組成物。
[14]
(F)熱架橋剤を更に含む、項目1~13のいずれか一項に記載の感光性樹脂組成物。
[15]
(G)フィラーを更に含む、項目1~14のいずれか一項に記載の感光性樹脂組成物。
[16]
以下の工程:
項目1~15のいずれか一項に記載の感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程と;
得られた上記感光性樹脂層を加熱及び乾燥する工程と;
加熱及び乾燥後の上記感光性樹脂層を露光する工程と;
露光後の上記感光性樹脂層を現像する工程と;
現像後の上記感光性樹脂層を加熱処理して、ポリイミド硬化膜を形成する工程と;
を含む、ポリイミド硬化膜の製造方法。
[17]
上記塗布~上記現像工程は、上記現像工程において膜厚10μm~15μmの感光性樹脂層が得られるように行い、現像する際の現像時間が30秒以下である、項目16に記載のポリイミド硬化膜の製造方法。
[18]
ポリイミド硬化膜であって、摂動方式スプリットシリンダー共振器法による周波数40GHzの誘電正接が0.003~0.014であり、下記式(3):
3<tanδ40×WVTR<10 (3)
{式中、tanδ40は摂動方式スプリットシリンダー共振器法による周波数40GHzでの誘電正接を示し、WVTRは、膜厚10μmに換算したポリイミド硬化膜の透湿度を示す。}を満たす、ポリイミド硬化膜。
[19]
上記感光性樹脂組成物は、再配線層用途に使用される、項目1~15のいずれか一項に記載の感光性樹脂組成物。
本開示の感光性樹脂組成物は、(A)特定の構造を有するポリイミド及びポリイミド前駆体から選択される少なくとも一つの樹脂を100質量部と、(B)0.5~10質量部の光重合開始剤と、(C)50~500質量部の溶媒と、を含有する。また、本開示の感光性樹脂組成物は、所望により、上記の成分以外に、(D)シランカップリング剤、(E)エチレン性不飽和基含有化合物、(F)熱架橋剤、(G)フィラー、その他の成分をさらに含有する。
(A)ポリイミド及びポリイミド前駆体から選択される少なくとも一つの樹脂は、解像度、透湿度および低誘電正接の観点から、下記一般式(14)で表される構造を含むことが好ましい。
70.02×2/[Mw(A)+Mw(B)-36]×100 (I)
{式(I)中、Mw(A)はテトラカルボン酸二無水物の分子量を表し、そしてMw(B)はジアミンの分子量を表す。}で表される。尚、2種類以上のテトラカルボン酸二無水物及び/又はジアミン化合物を用いた場合、例えば、2種類のテトラカルボン酸二無水物及び/又はジアミン類を用いて調整する際は、下記式(II):
70.02×2/[Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2-36]×100 (II)
{式(II)中、Mw(A1)は、第一のテトラカルボン酸二無水物の分子量を表し、Mw(A2)は、第二のテトラカルボン酸二無水物の分子量を表し、a1は、第一のテトラカルボン酸二無水物の含有量を表し、a2は、第二のテトラカルボン酸二無水物の含有量を表し、Mw(B1)は、第一のジアミン化合物の分子量を表し、Mw(B2)は、第二のジアミン化合物の分子量を表し、b1は、第一のジアミン化合物の含有量を表し、そしてb2は、第二のジアミン化合物の含有量を表す。ただし、a1、a2、b1、b2は、それぞれ、a1+a2=1、b1+b2=1を満たす。}で表される。3種類以上のテトラカルボン酸二無水物及び/又はジアミン類を用いた場合も、同様に求められる。原料にテトラカルボン酸及び/又はテトラカルボン酸ジクロリドを使用した場合は、対応するテトラカルボン酸二無水物の質量を用いて計算する。
[Mw(P)+Mw(Q)]/[Mw(A)+Mw(B)-36]×100 (I)
{式(I)中、Mw(P)は、テトラカルボン酸二無水物中の脂肪族炭化水素基の分子量の和を表し、Mw(Q)は、ジアミン化合物中の脂肪族炭化水素基の分子量の和を表し、Mw(A)は、テトラカルボン酸二無水物の分子量を表し、そしてMw(B)は、ジアミン化合物の分子量を表す。}で表される。
[Mw(P1)×a1+Mw(P2)×a2+Mw(Q1)×b1+Mw(Q2)×b2]/[Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2-36] ×100 (II)
{式(II)中、Mw(P1)は第一のテトラカルボン酸二無水物中の脂肪族炭化水素基の分子量の和を表し、Mw(P2)は第二のテトラカルボン酸二無水物中の脂肪族炭化水素基の分子量の和を表し、Mw(Q1)は第一のジアミン化合物中の脂肪族炭化水素基の分子量の和を表し、Mw(Q2)は、第二のジアミン化合物中の脂肪族炭化水素基の分子量の和を表す。Mw(A1)は、第一のテトラカルボン酸二無水物の分子量を表し、Mw(A2)は、第二のテトラカルボン酸二無水物の分子量を表し、a1は、第一のテトラカルボン酸二無水物の含有比を表し、a2は、第二のテトラカルボン酸二無水物の含有比を表す。Mw(B1)は、第一のジアミン化合物の分子量を表し、Mw(B2)は、第二のジアミン化合物の分子量を表し、b1は、第一のジアミン化合物の含有比を表し、そしてb2は、第二のジアミン化合物の含有比を表す。また、a1、a2、b1、b2は、それぞれ、a1+a2=1、b1+b2=1を満たす。}で表される。3種類以上のテトラカルボン酸二無水物及び/又はジアミン化合物を用いた場合も、同様に求められる。原料にテトラカルボン酸及び/又はテトラカルボン酸クロリドを使用した場合は、対応するテトラカルボン酸二無水物の分子量を使用して計算する。
0.34≦Ph2×Im1≦1.2 (2)
を満たすことが好ましい。
-12.6<U-T<16.0 (1)
{式中、Uはポリイミドのイミド基濃度を示し、Tはポリイミドの脂肪族炭化水素基濃度を示す。}を満たすことが好ましい。U-Tは-12.6以上であることが好ましく、-11.0以上であることがより好ましく、-10以上であることで解像度が好ましい傾向にある。U-Tは16.0以下であることが好ましく、12.5以下であることがより好ましく、12.0以下であることが好ましく、11.0以下であることで、透湿度に優れる傾向にある。350℃で加熱及び硬化することを基準としているのは、ポリイミド前駆体をほぼ100%イミド化させた状態を基準とすることで、脂肪族炭化水素基濃度Tの調整を容易にするためであり、感光性樹脂組成物が実際の使用において350℃で加熱及び硬化されることを意図したものではない。
[Mw(R)]/[Mw(A)+Mw(B)+Mw(R)-36]×100 (I)
{式(I)中、Mw(R)は光重合性基を含む化合物(光重合性基含有化合物)の分子量の和を表し、Mw(A)はテトラカルボン酸二無水物の分子量を表し、そしてMw(B)はジアミン化合物の分子量を表す。}で表される。
尚、2種類以上のテトラカルボン酸二無水物及び/又はジアミン化合物を用いた場合は、上記脂肪族炭化水素基濃度Tの定義と同様に、原料の割合に応じて計算を行う。
また、光重合性基含有化合物と光重合性基を含まない化合物との共重合体の場合は、下記式(II):
[Mw(R)×c1]/[Mw(A)+Mw(B)+Mw(R)×c1+Mw(S)×c2-36]×100 (II)
{式(II)中、Mw(R)は光重合性基含有化合物の分子量の和を表し、Mw(S)は光重合性基を含まない化合物の分子量の和を表し、Mw(A)はテトラカルボン酸二無水物の分子量を表し、そしてMw(B)はジアミン化合物の分子量を表す。c1は光重合性基含有化合物の含有量を表し、c2は光重合性基を含まない化合物の含有量を表し、また、c1、c2は、それぞれ、c1+c2=1を満たす。}で表される。原料にテトラカルボン酸及び/又はテトラカルボン酸クロリドを使用した場合は、対応するテトラカルボン酸二無水物の分子量を用いて計算する。
上記一般式(1)~(3)からなる群から選択される少なくとも一つの末端構造を有するエステル結合型のポリイミド前駆体は、下記のいずれかの方法にて得ることができる。例えば、はじめに末端構造を形成したエステル化されたテトラカルボン酸二無水物を合成し、次いでジアミン化合物とアミド重縮合させることにより得ることができる。
上記一般式(1)、及び上記一般式(2)の末端構造を形成するには、所望の4価の有機基Xを有するテトラカルボン酸二無水物と、イソシアネート基を有する化合物とを反応させた後に、光重合性基(例えば、不飽和二重結合)を有するアルコール類を反応させて、部分的にイミド化、又はイミド誘導体化(上記一般式(2)由来の構造)/エステル化したテトラカルボン酸(以下、アシッド/エステル/イミド体ともいう)を調製する。テトラカルボン酸二無水物と、イソシアネート基を有する化合物の反応を促進させるために、ピリジン、トリエチルアミン、ジメチルアミノピリジン、1,4-ジアザビシクロ[2.2.2]オクタン等を用いることができる。上記光重合性基を有するアルコール類とともに、任意に飽和脂肪族アルコール類を併用してもよい。
上記一般式(3)の末端構造を形成するには、所望の4価の有機基Xを有するテトラカルボン酸二無水物と、光重合性基(例えば、不飽和二重結合)を有するアルコール類とを反応させて、部分的にエステル化したテトラカルボン酸(以下、アシッド/エステル体ともいう)を調製した後に、イソシアネート基を有する化合物を反応させて、部分的にエステル化/アミド化したテトラカルボン酸(以下、アシッド/エステル/アミド体ともいう)を調製する。テトラカルボン酸二無水物と、イソシアネート基を有する化合物の反応を促進させるために、ピリジン、トリエチルアミン、ジメチルアミノピリジン、1,4-ジアザビシクロ[2.2.2]オクタン等を用いることができる。上記光重合性基を有するアルコール類とともに、任意に飽和脂肪族アルコール類を併用してもよい。
エステル結合型のポリイミド前駆体を調製するために好適に用いられる、炭素数6~40の4価の有機基X1を有するテトラカルボン酸二無水物としては、上記で挙げられた構造由来のテトラカルボン酸二無水物以外に、例えば、無水ピロメリット酸、ジフェニルエーテル-3,3’,4,4’-テトラカルボン酸二無水物、ベンゾフェノン-3,3’,4,4’-テトラカルボン酸二無水物、ビフェニル-3,3’,4,4’-テトラカルボン酸二無水物、ジフェニルスルホン-3,3’,4,4’-テトラカルボン酸二無水物、ジフェニルメタン-3,3’,4,4’-テトラカルボン酸二無水物、2,2-ビス(3,4-無水フタル酸)プロパン、2,2-ビス(3,4-無水フタル酸)-1,1,1,3,3,3-ヘキサフルオロプロパン、4,4‘-(4,4’-イソプロピリデンジフェノキシ)二無水フタル酸、4,4‘-ビス(3,4-ジカルボキシフェノキシ)ベンゾフェノン二酸無水物等も挙げることができるが、これらに限定されるものではない。また、これらは単独で用いることができるのは勿論のこと、2種以上を混合して用いてもよい。
ケトン類として、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等が挙げられる。エステル類として、例えば、酢酸メチル、酢酸エチル、酢酸ブチル、シュウ酸ジエチル等が挙げられる。ラクトン類として、例えば、γ-ブチロラクトン等が挙げられる。エーテル類として、例えば、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、テトラヒドロフラン等が挙げられる。ハロゲン化炭化水素類として、例えば、ジクロロメタン、1,2-ジクロロエタン、1,4-ジクロロブタン、クロロベンゼン、o-ジクロロベンゼン等が挙げられる。炭化水素類として、例えば、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレン等が挙げられる。これらは必要に応じて、単独で用いても2種以上混合して用いてもよい。
上記アシッド/エステル体(典型的には上記反応溶媒中に溶解された溶液状態にある)に、好ましくは氷冷下、適当な脱水縮合剤を投入混合してアシッド/エステル体をポリ酸無水物とする。次いでこれに、炭素数6~40の2価の有機基Y1を含むジアミン類を別途溶媒に溶解又は分散させたものを滴下投入し、両者をアミド重縮合させることにより、目的のポリイミド前駆体を得ることができる。上記2価の有機基Y1を有するジアミン類とともに、ジアミノシロキサン類を併用してもよい。上記脱水縮合剤としては、例えば、ジシクロヘキシルカルボジイミド、1-エトキシカルボニル-2-エトキシ-1,2-ジヒドロキノリン、1,1-カルボニルジオキシ-ジ-1,2,3-ベンゾトリアゾール、N,N’-ジスクシンイミジルカーボネート等が挙げられる。以上のようにして、中間体であるポリ酸無水化物が得られる。
(B)光重合開始剤は、活性光線によりラジカルを発生し、エチレン性不飽和基含有化合物等を重合することができる化合物である。活性光線でラジカルを発生する開始剤としては、例えば、ベンゾフェノン、N-アルキルアミノアセトフェノン、オキシムエステル、アクリジン及びホスフィンオキサイド等の構造を含む化合物が挙げられる。その例としては、ベンゾフェノン、N,N,N’,N’-テトラメチル-4,4’-ジアミノベンゾフェノン(ミヒラーケトン)、N,N,N’,N’-テトラエチル-4,4’-ジアミノベンゾフェノン、4-メトキシ-4’-ジメチルアミノベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-プロパノン-1、アクリル化ベンゾフェノン、4-ベンゾイル-4’-メチルジフェニルサルファイド等の芳香族ケトン;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル化合物;ベンゾイン、メチルベンゾイン、エチルベンゾイン等のベンゾイン化合物;1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)(BASFジャパン(株)製、Irgacure Oxe02)、1-[4-(フェニルチオ)フェニル]-3-シクロペンチルプロパン-1,2-ジオン-2-(o-ベンゾイルオキシム)(上州強力電子材料(株)製、PBG305)、1,2-プロパンジオン,3-シクロヘキシル-1-[9-エチル-6-(2-フラニルカルボニル)-9H-カルバゾール-3-イル]-,2-(O-アセチルオキシム)(日興ケムテック(株)製TR-PBG-326、製品名)等のオキシムエステル化合物;ベンジルジメチルケタール等のベンジル誘導体;9-フェニルアクリジン、1,7-ビス(9,9’-アクリジニル)ヘプタン等のアクリジン誘導体;N-フェニルグリシン等のN-フェニルグリシン誘導体;クマリン化合物;オキサゾール化合物;2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド等のホスフィンオキサイド化合物が挙げられるが、これらに限定されるものではない。上記で説明された(C)重合開始剤は、単独、又は2種以上混合して用いることもできる。上記の光重合開始剤の中では、特に解像性の観点から、オキシムエステル化合物がより好ましい。これらの中でも、ラジカル種がメチル基由来であることが特に好ましい。
(C)溶媒は、(A)ポリイミド前駆体、(B)光重合開始剤、を均一に溶解または懸濁させうる溶媒であれば限定されない。そのような溶媒として、γ―ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール、アセト酢酸エチル、N,N-ジメチルアセトアセトアミド、ε―カプロラクトン、1,3-ジメチル―2-イミダゾリジノン、3-メトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、N,N-ジメチルホルムアミド、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N,N-ジメチルアセトアミド、などを例示することができる。これらの溶媒は一種単独で用いてもよいし、2種以上を混合して用いてもよい。
レリーフパターンの密着性を向上させるために、感光性樹脂組成物は、(D)シランカップリング剤を任意に含むことができる。(D)シランカップリング剤は、下記一般式(12)で表される構造を有することが好ましい。
レリーフパターンの解像度を向上させるために、感光性樹脂組成物は、(E)ラジカル重合性化合物を任意に含むことができる。このような化合物としては、光重合開始剤によりラジカル重合反応する(メタ)アクリル化合物が好ましく、特に以下に限定するものではないが、ジエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレートをはじめとする、エチレングリコール又はポリエチレングリコールのモノ若しくはジアクリレート又はメタクリレート、プロピレングリコール又はポリプロピレングリコールのモノ若しくはジアクリレート又はメタクリレート、グリセロールのモノ、ジ若しくはトリアクリレート又はメタクリレート、シクロヘキサンジアクリレート又はジメタクリレート、1,4-ブタンジオールのジアクリレート又はジメタクリレート、1,6-ヘキサンジオールのジアクリレート又はジメタクリレート、ネオペンチルグリコールのジアクリレート又はジメタクリレート、ビスフェノールAのモノ若しくはジアクリレート又はメタクリレート、ベンゼントリメタクリレート、イソボルニルアクリレート又はメタクリレート、アクリルアミド、その誘導体、メタクリルアミド、その誘導体、トリメチロールプロパントリアクリレート又はメタクリレート、グリセロールのジ若しくはトリアクリレート又はメタクリレート、ペンタエリスリトールのジ、トリ若しくはテトラアクリレート又はメタクリレート、これら化合物のエチレンオキサイド又はプロピレンオキサイド付加物等の化合物を挙げることができる。また、これらのモノマーは、1種で用いても2種以上の混合物で用いてもよい。
硬化後膜の耐薬品性を向上させるために、感光性樹脂組成物は、(F)熱架橋剤を任意に含むことができる。
硬化後膜の耐薬品性を向上させるために、感光性樹脂組成物は、(G)フィラーを任意に含むことができる。フィラーとは、強度や各種性質を改良するために、添加される不活性な物質であれば限定されない。
感光性樹脂組成物は、上記(A)~(G)成分以外の成分をさらに含有してもよい。その他の成分としては、例えば、(A)ポリイミド前駆体以外の樹脂成分;金属元素を含む有機化合物、増感剤、熱重合禁止剤、アゾール化合物、及びヒンダードフェノール化合物などが挙げられる。
I)キレート化合物としては、アルコキシ基を2個以上有する化合物が、感光性樹脂組成物の保存安定性及び良好なパターンが得られることからより好ましい。キレート化合物として具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)、これらの化合物のチタン原子をジルコニウム原子で置換した化合物が挙げられるが、これらに限定されるものではない。
本開示は、感光性樹脂組成物をポリイミドに変換する工程を含む、ポリイミド硬化膜の製造方法もまた提供する。本開示のポリイミド硬化膜の製造方法は、例えば、以下の工程(1)~(5):
(1)本開示の感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程;
(2)得られた感光性樹脂層を加熱及び乾燥する工程;
(3)加熱及び乾燥後の感光性樹脂層を露光する工程;
(4)露光後の感光性樹脂層を現像する工程;及び
(5)現像後の感光性樹脂層を加熱処理して、ポリイミド硬化膜を形成する工程;
を含む。
本工程では、本開示の感光性樹脂組成物を基材上に塗布し、必要に応じて、その後に乾燥させて、感光性樹脂層を形成する。塗布方法としては、従来から感光性樹脂組成物の塗布に用いられていた方法、例えば、スピンコーター、バーコーター、ブレードコーター、カーテンコーター、スクリーン印刷機等で塗布する方法、スプレーコーターで噴霧塗布する方法等を用いることができる。
必要に応じて、感光性樹脂組成物膜を加熱し、乾燥させることができる。乾燥方法としては、風乾、オーブン又はホットプレートによる加熱乾燥、真空乾燥等の方法が用いられる。また、塗膜の乾燥は、感光性樹脂組成物中の(A)ポリイミド前駆体(ポリアミド酸エステル)のイミド化が起こらないような条件で行うことが望ましい。具体的には、風乾又は加熱乾燥を行う場合、20℃~140℃で1分~1時間の条件で乾燥を行うことができる。以上により基板上に感光性樹脂層を形成できる。
本工程では、上記で形成した感光性樹脂層を露光する。露光装置としては、例えばコンタクトアライナー、ミラープロジェクション、ステッパー等の露光装置が用いられる。露光は、パターンを有するフォトマスク又はレチクルを介して、又は直接に行うことができる。露光に使用する光線は、例えば、紫外線光源等である。
本工程では、露光後の感光性樹脂層を現像して、レリーフパターンを形成する。感光性樹脂組成物がネガ型である場合、露光後の感光性樹脂層のうち未露光部を現像除去する。露光(照射)後の感光性樹脂層を現像する現像方法としては、従来知られているフォトレジストの現像方法、例えば、回転スプレー法、パドル法、超音波処理を伴う浸漬法等の中から任意の方法を選択して使用することができる。また、現像の後、レリーフパターンの形状を調整する等の目的で、必要に応じて、任意の温度及び時間の組合せによる現像後ベークを施してもよい。現像に使用される現像液としては、例えば、ネガ型感光性樹脂組成物に対する良溶媒、又は該良溶媒と貧溶媒との組合せが好ましい。良溶媒としては、例えば、N-メチル-2-ピロリドン、N-シクロヘキシル-2-ピロリドン、N,N-ジメチルアセトアミド、シクロペンタノン、シクロヘキサノン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン等が好ましい。貧溶媒としては、例えば、トルエン、キシレン、メタノール、エタノール、イソプロピルアルコール、乳酸エチル、プロピレングリコールメチルエーテルアセテート及び水等が好ましい。良溶媒と貧溶媒とを混合して用いる場合には、ネガ型感光性樹脂組成物中のポリマーの溶解性によって良溶媒に対する貧溶媒の割合を調整することが好ましい。また、各溶媒を2種以上、例えば数種類組合せて用いることもできる。露光後の感光性樹脂層を現像する工程において、膜厚10μm~15μmの感光性樹脂層が得られるように、上記塗布~現像工程を行うことが好ましい。現像時間は30秒以下であることが好ましく、25秒以下がより好ましく、20秒以下がさらに好ましい。理論には拘束されないが、現像時間が30秒以下であることで、露光部との溶解性に差が出ることでコントラストが付き、パターンの解像性が向上する。
本工程では、上記現像により得られたレリーフパターンを加熱して感光成分を希散させるとともに、(A)ポリイミド前駆体をイミド化させて、ポリイミドからなる硬化レリーフパターンに変換する。加熱硬化の方法としては、ホットプレートによるもの、オーブンを用いるもの、温度プログラムを設定できる昇温式オーブンを用いるもの等種々の方法を選ぶことができる。加熱は、例えば160℃~400℃で30分~5時間の条件で行うことができる。加熱硬化の際の雰囲気気体としては空気を用いてもよいし、窒素、アルゴン等の不活性ガスを用いてもよい。以上のようにして、硬化レリーフパターン(ポリイミド硬化膜)を製造することができる。
3.0<tanδ40×WVTR<10.0 (3)
を満たすことが好ましい。tanδ40×WVTRが3.0~10.0の範囲にあることで、解像性と誘電特性に優れ、周波数依存性の少ないポリイミド硬化物が得られる。40GHzと10GHzにおける誘電正接の差異は0.0015以下が好ましく、0.001以下であることが好ましい。
本開示は、本開示の感光性樹脂組成物を用いて、上述した硬化レリーフパターンの製造方法により得られる硬化レリーフパターンを有する、半導体装置も提供することができる。したがって、半導体素子である基材と、上述した硬化レリーフパターン製造方法により該基材上に形成されたポリイミドの硬化レリーフパターンとを有する半導体装置が提供される。また、本開示は、基材として半導体素子を用い、上述した硬化レリーフパターンの製造方法を工程の一部として含む半導体装置の製造方法にも適用できる。半導体装置は、上記硬化レリーフパターン製造方法で形成される硬化レリーフパターンを、表面保護膜、層間絶縁膜、再配線用絶縁膜、フリップチップ装置用保護膜、又はバンプ構造を有する半導体装置の保護膜等として形成し、既知の半導体装置の製造方法と組合せることで製造することができる。
本開示は、本開示の感光性樹脂組成物を用いて、表示体素子と該表示体素子の上部に設けられた硬化膜とを備える表示体装置であって、該硬化膜は上述の硬化レリーフパターンである表示体装置も提供することができる。ここで、当該硬化レリーフパターンは、当該表示体素子に直接接して積層されていてもよく、別の層を間に挟んで積層されていてもよい。例えば、該硬化膜として、TFT液晶表示素子及びカラーフィルター素子の表面保護膜、絶縁膜、及び平坦化膜、MVA型液晶表示装置用の突起、並びに有機EL素子陰極用の隔壁を挙げることができる。
(1)重量平均分子量
各感光性樹脂の重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー法(標準ポリスチレン換算)により測定した。測定に用いたカラムは昭和電工社製 商標名 Shodex 805M/806M直列であり、標準単分散ポリスチレンは、昭和電工(株)製Shodex STANDARD SM-105を選び、展開溶媒はN-メチル-2-ピロリドンであり、検出器は昭和電工製 商標名 Shodex RI-930を使用した。
6インチ・シリコンウェハ(フジミ電子工業株式会社製、厚み625±25μm)上に、スパッタ装置(L-440S-FHL型、キヤノンアネルバ社製)を用いて200nm厚のTi、400nm厚のCuをこの順にスパッタした。続いて、このウェハ上に、後述の方法により調製した感光性樹脂組成物をコーターデベロッパー(D-Spin60A型、SOKUDO社製)を用いて回転塗布し、ホットプレート上で110℃3分間、加熱乾燥することにより約13.5μm厚の感光性樹脂層を形成した。この感光性樹脂層に、テストパターン付マスクを用いて、i線フィルターを装着したプリズマGHI(ウルトラテック社製)により200mJ/cm2のエネルギーを照射した。次いで、この感光性樹脂層を、現像液としてシクロペンタノンを用いてコーターデベロッパー(D-Spin60A型、SOKUDO社製)でスプレー現像し、プロピレングリコールメチルエーテルアセテートでリンスすることにより、Cu上のレリーフパターンを得た。この時の、スプレー現像の時間を現像時間とした。Cu上に該レリーフパターンを形成したウェハを、昇温プログラム式キュア炉(VF-2000型、光洋リンドバーグ社製)を用いて、窒素雰囲気下、230℃で2時間加熱処理することにより、Cu上に約10μm厚の樹脂からなる硬化レリーフパターンを得た。作製したレリーフパターンを、光学顕微鏡下で観察し、ビアの最少開口パターンのサイズを求めた。このとき、得られたパターンの開口部の面積が、対応するパターンマスク開口面積の1/2以上であれば解像されたものとみなし、解像された開口部のうち最小面積を有するものに対応するマスク開口辺の長さ(開口パターンのサイズ)に基づき、以下の評価基準で解像度を判定した。
(評価基準)
A:最小開口パターンのサイズが10μm未満
B:最小開口パターンのサイズが10μm以上15μm未満
C:最小開口パターンのサイズが15μm以上20μm未満
D:最小開口パターンのサイズが20μm以上
6インチ・シリコンウェハ(フジミ電子工業株式会社製、厚み625±25μm)上に、スパッタ装置(L-440S-FHL型、キヤノンアネルバ社製)を用いて100nm厚のアルミニウム(Al)をスパッタし、スパッタAlウェハ基板を準備した。後述の方法により調製した感光性樹脂組成物を、スピンコート装置(D-spin60A型、SOKUDO社製)を使用して上記スパッタAlウェハ基板にスピンコートし、110℃で180秒間加熱乾燥して、約13.5μm厚の感光性樹脂層を形成した。その後、アライナ(PLA-501F、キャノン社製)を用いて露光量600mJ/cm2のghi線で全面露光し、縦型キュア炉(光洋リンドバーグ製、形式名VF-2000B)を用いて、窒素雰囲気下、230℃で2時間の加熱硬化処理を施し、Alウェハ―上に約10μm厚の樹脂からなる硬化膜を作製した。この硬化膜を、ダイシングソー(ディスコ製、型式名DAD-2H/6T)を用いて、縦80mm、横62mm(10GHz測定用)と縦40mm、横30mm(40GHz測定用)にカットし、10%塩酸水溶液に浸漬してシリコンウェハ上から剥離し、フィルムサンプルとした。フィルムサンプルを50℃のオーブンで24時間乾燥させた後、フィルムサンプルを共振器摂動法にて10GHzと40GHzにおける比誘電率(Dk)と誘電正接(Df)を、それぞれ、測定した。測定方法の詳細は以下の通りである。
(測定方法)
摂動方式スプリットシリンダー共振器法
(装置構成)
ネットワークアナライザ:
PNA Network analyzer N5224B
(KEYSIGHT社製)
スプリットシリンダー共振器:
CR-710(関東電子応用開発社製、測定周波数:約10GHz)
CR-740(関東電子応用開発社製、測定周波数:約40GHz)
6インチ・シリコンウェハ(フジミ電子工業株式会社製、厚み625±25μm)上に、スパッタ装置(L-440S-FHL型、キヤノンアネルバ社製)を用いて100nm厚のアルミニウム(Al)をスパッタし、スパッタAlウェハ基板を準備した。後述の方法により調製した感光性樹脂組成物を、スピンコート装置(D-spin60A型、SOKUDO社製)を使用して上記スパッタAlウェハ基板にスピンコートし、110℃で180秒間加熱乾燥して、約13.5μm厚の感光性樹脂層を形成した。その後、アライナ(PLA-501F、キャノン社製)を用いて露光量600mJ/cm2のghi線で全面露光し、縦型キュア炉(光洋リンドバーグ製、形式名VF-2000B)を用いて、窒素雰囲気下、230℃で2時間の加熱硬化処理を施し、Alウェハ―上に約10μm厚の樹脂からなる硬化膜を作製した。この硬化膜を、ダイシングソー(ディスコ製、型式名DAD-2H/6T)を用いて、縦80mm、横62mmにカットし、10%塩酸水溶液に浸漬してシリコンウェハ上から剥離し、フィルムサンプルとした。透湿度の測定は、JIS Z0208のカップ法に準じて行った。なお、使用する塩化カルシウムの使用量は40gで、透湿条件は温度65℃/湿度90%RHで実施した。試験は24時間行い、その後恒温恒湿機から取り出し、室温で30分間放置し、重量測定を行った。透水性(WVTR)は下記の計算式より求めた。
WVTR={(試験後の重量)-(試験前の重量)}/(0.032×π) (式X)
{式X中、0.03はカップの半径(m)を示す}
ここでいう、WVTRは10umの硬化膜に対する値であり、膜厚に依存する値である。例えば、膜厚が20umの場合は、10umで得られたWVTR値の1/2となる。WVTRは数値が低いほど、フィルムの水蒸気透過率が低いことを意味する。また、フィルムが疎水性であることや、フィルムの密度が高いほどWVTRは低くなる傾向にある。
IR測定は、上記(3)で得らえたフィルムを、Nicolet 380を用いて、ATR法にて700cm-1以上4000cm-1以下の範囲をスキャン数50回で測定を行った。サンプル接触部にはシリコンプリズムを使用した。1450cm-1以上1550cm-1以下の範囲にある吸収ピークの、一番大きなピーク強度をPh1、二番目の強度のピーク強度をPh2、1380cm-1付近のピーク強度をIm1とし、Ph1を1に規格化することで、Ph2とIm1を算出した。なお、1380cm-1付近のピーク強度は、1380cm-1±10cm-1の中で最も大きいピークとした。
5L4つ口フラスコをArで置換し、4,4’-ブチルインデンビス(6-tert-ブチル-m-クレゾール)を172.02g、4-クロロニトロベンゼン155.84g、DMF1.5Lを投入し、撹拌した。そこにK2CO3を186.42g加えて150℃で5時間加熱し、TLCで原料と中間体の消失を確認した。室温まで冷却した後、反応液をろ過し、ろ液を80℃で減圧濃縮した。濃縮残渣はイオン交換水1.6Lに注ぎ、さらに酢酸エチル2.5Lを加えて3回分液精製した。有機層は回収し、MgSO4を加えて乾燥させた。乾燥後、ろ過して不純物を除き、トルエン800mLを加えて溶解させたものを、メタノール4.0Lに加えて30分間撹拌した。撹拌後、ろ過してろ物を回収し、80℃で12時間乾燥させた。乾燥して得られた反応物を、Arで置換した5L4つ口フラスコに投入し、さらに5%Pd/C(EA)19.04g、THF1.9Lを投入し、撹拌した。フラスコは40℃に加熱し、H2バブリング(10mL/min)を行って、24時間還元反応を行った。反応液をセライトろ過し、シリカゲルクロマトグラフィーで目的物のフラクションを回収し、減圧濃縮してジアミンX-1を得た。
ポリイミド前駆体(ポリマーA-1)の合成:
4,4’-オキシジフタル酸二無水物(ODPA)155.1gを2リットル容量のセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)134.0g及びγ-ブチロラクトン400mlを加えて室温下で攪拌しながらピリジン79.1gを加えて、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に16時間静置した。
上記ポリマーA-1の合成において、ODPA155.1gに代えて4,4’-(4,4’-イソプロピリデンジフェノキシ)酸二無水物260.2gを用い、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えて2,2’-ジメチルビフェニル-4,4’-ジアミン(m-TB)92.88gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-2を得た。このポリマーA-2の重量平均分子量(Mw)を測定したところ、23,000であった。ポリマーA-2から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは20.1wt%、脂肪族炭化水素基濃度Tは8.6wt%であった。
上記ポリマーA-1の合成において、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えて、1,4-ビス(4-アミノフェノキシ)-2,3,5-トリメチルベンゼン146.3gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-3を得た。このポリマーA-3の重量平均分子量(Mw)を測定したところ、20,000であった。ポリマーA-3から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは23.0wt%、脂肪族炭化水素基濃度Tは7.4wt%であった。
上記ポリマーA-1の合成において、ODPA155.1gに代えて、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(BPDA)147.1gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-4を得た。このポリマーA-4の重量平均分子量(Mw)を測定したところ、21,000であった。ポリマーA-4から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは20.1wt%、脂肪族炭化水素基濃度Tは8.6wt%であった。
上記ポリマーA-1の合成において、ODPA155.1gに代えて、4,4’-(4,4’-イソプロピリデンジフェノキシ)酸二無水物260.2gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-5を得た。このポリマーA-5の重量平均分子量(Mw)を測定したところ、24,000であった。ポリマーA-5から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは15.2wt%、脂肪族炭化水素基濃度Tは9.8wt%であった。
上記ポリマーA-1の合成において、ODPA155.1gに代えて、4,4’-(4,4’-イソプロピリデンジフェノキシ)酸二無水物260.2gを、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えて、1,4-ビス(4-アミノフェノキシ)-2,5-ジ―t-ブチルベンゼン176.98gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-6を得た。このポリマーA-6の重量平均分子量(Mw)を測定したところ、22,000であった。ポリマーA-6から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは15.8wt%、脂肪族炭化水素基濃度Tは16.2wt%であった。
上記ポリマーA-1の合成において、ODPA155.1gに代えて、4,4’-(4,4’-イソプロピリデンジフェノキシ)酸二無水物260.2gを、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えて、ジアミンX-1を247.1g用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-7を得た。このポリマーA-7の重量平均分子量(Mw)を測定したところ、20,000であった。ポリマーA-7から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは13.3wt%、脂肪族炭化水素基濃度Tは20.7wt%であった。
上記ポリマーA-1の合成において、ODPA150.1gに代えてピロメリット酸二無水物109.06gを、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えてジアミンX-1を247.1g用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-8を得た。このポリマーA-8の重量平均分子量(Mw)を測定したところ、14,000であった。ポリマーA-8から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは18.7wt%、脂肪族炭化水素基濃度Tは25.1wt%であった。
上記ポリマーA-1の合成において、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えて2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン95.93g、2,2-ビス{4-(4-アミノフェノキシ)フェニル}プロパン89.8gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-9を得た。このポリマーA-9の重量平均分子量(Mw)を測定したところ、21,000であった。ポリマーA-9から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは20.0wt%、脂肪族炭化水素基濃度Tは6.5wt%であった。
上記ポリマーA-1の合成において、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えてジアミンX-1を247.1g用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-10を得た。このポリマーA-10の重量平均分子量(Mw)を測定したところ、16,000であった。ポリマーA-10から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは16.7wt%、脂肪族炭化水素基濃度Tは22.3wt%であった。
酸成分として、4,4’-(4,4’-イソプロピリデンジフェノキシ)ジフタル酸無水物93.7gを1リットル容量のセパラブルフラスコに入れ、γ―ブチロラクトン175gを加えて室温下で攪拌しながら、別途用意した2-イソシアナトエチルメタクリレート4.7g、ピリジン28.9gをγ-ブチロラクトン20gに溶解させたγ-ブチロラクトン溶液を5分かけて加えて、50℃で1時間加熱し、次いで2-ヒドロキシエチルメタクリレート(HEMA)48.7gを加え、さらに50℃で4時間加熱し、反応による発熱の終了後、室温まで放冷した。更に16時間静置し、反応混合物を得た。
酸成分として、4,4’-(4,4’-イソプロピリデンジフェノキシ)ジフタル酸無水物93.7gを1リットル容量のセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)48.7g及びγ―ブチロラクトン175gを加えて室温下で攪拌しながらピリジン28.5gを加えて、50℃で4時間加熱し、反応による発熱の終了後、室温まで放冷した。更に16時間静置し、反応混合物を得た。
上記ポリマーA-1の合成において、ODPA155.1gに代えてBPDA147.1gを、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えてジアミノジフェニルエーテル85.8gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-13を得た。このポリマーA-13の重量平均分子量(Mw)を測定したところ、22,000であった。ポリマーA-13から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは30.5wt%、脂肪族炭化水素基濃度Tは0wt%であった。
上記ポリマーA-1の合成において、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えてm-TB92.88gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-14を得た。このポリマーA-14の重量平均分子量(Mw)を測定したところ、19,000であった。ポリマーA-14から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは28.8wt%、脂肪族炭化水素基濃度Tは6.2wt%であった。
上記ポリマーA-1の合成において、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えて2,2-ビス{4-(4-アミノフェノキシ)フェニル}プロパン179.59gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-15を得た。このポリマーA-15の重量平均分子量(Mw)を測定したところ、22,000であった。ポリマーA-15から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは20.5wt%、脂肪族炭化水素基濃度Tは4.4wt%であった。
上記ポリマーA-1の合成において、ODPA155.1gに代えて2,2’,3,3’,5,5’-ヘキサメチル[1,1’-ビフェニル]-4,4’-ジイル=ビス(1,3-ジオキソ-1,3-ジヒドロ-2-ベンゾフラン-5-カルボキシラート)309.29g、2,2-ビス[4-(4-アミノフェノキシ)-3-メチルフェニル]プロパン191.87gに代えて2,2-ビス{4-(4-アミノフェノキシ)フェニル}プロパン179.59gを用いた以外は、ポリマーA-1の合成に記載の方法と同様にして反応を行うことにより、ポリマーA-16を得た。このポリマーA-16の重量平均分子量(Mw)を測定したところ、29,000であった。ポリマーA-16から得られるポリイミドの、繰り返し単位当たりのイミド基濃度Uは14.1wt%、脂肪族炭化水素基濃度Tは12.1wt%であった。
実施例、比較例には下記化合物を用いた。
光重合開始剤B-1:TR-PBG-304(常州強力電子社製)
光重合開始剤B-2:TR-PBG-305(常州強力電子社製)
光重合開始剤B-3:TR-PBG-3057(常州強力電子社製)
C-1:γ―ブチロラクトン(GBL)
C-2:ジメチルスルホキシド(DMSO)
D-1:3-グリシドキシプロピルトリメトキシシラン(信越化学社製)
D-2:N-フェニル-3-アミノプロピルトリメトキシシラン(信越化学社製)
D-3:(3-トリエトキシシリルプロピル)-tert-ブチルカルバメート
D-4:ウレイドプロピルトリエトキシシラン(信越化学社製)
E-1:1,9-ノナンジオールジメタクリレート(新中村化学株式会社製)
E-2:1,6-ヘキサンジオールジメタクリレート(新中村化学株式会社製)
E-3:ポリオキシプロピレン化ビスフェノールAのジアクリレート(共栄社化学株式会社製)
F-1:BMI-5100(大和化成工業株式会社製)
F-2:SBB70P(旭化成製)
G-1:K180SP-CY1(アドマテックス社製)
表1に示すように、ポリイミド前駆体A-1を用いて以下の方法でネガ型感光性樹脂組成物を調製し、調製した組成物の評価を行った。(A)ポリイミド前駆体としてA-1:100g、(B)光重合開始剤としてB-1:5g、(C)溶媒としてGBL:180g、DMSO:20gに溶解した。得られた溶液の粘度を、少量のGBLをさらに加えることによって、約40ポイズに調整し、ネガ型感光性樹脂組成物とした。該組成物を、前述の方法に従って評価した。結果を以下の表2に示す。
以下の表1、3及び5に示すとおりの配合比で調製した以外は、実施例1と同様のネガ型感光性樹脂組成物を調製し、実施例1と同様の評価を行った。結果を以下の表2、4及び6に示す。
Claims (19)
- (A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、前記感光性樹脂組成物を350℃で加熱及び硬化して得られるポリイミド硬化膜のポリイミドにおいて、テトラカルボン酸二無水物とジアミンに由来する構造を含む繰り返し単位の分子量に対して、イミド基の分子量が占める割合であるイミド基濃度Uが、12wt%~26wt%であり、
前記樹脂が下記一般式(14)で示す構造を含む、感光性樹脂組成物。
- 前記感光性樹脂組成物を350℃で加熱及び硬化して得られるポリイミド硬化膜のポリイミドにおいて、テトラカルボン酸二無水物とジアミン化合物に由来する構造を含む繰り返し単位の分子量に対して、脂肪族炭化水素基の分子量の合計が占める割合である脂肪族炭化水素基濃度が4wt%~35wt%である、請求項1に記載の感光性樹脂組成物。
- 一般式(14)で示される構造がジアミン由来である、請求項1又は2に記載の感光性樹脂組成物。
- 前記樹脂がポリイミド前駆体である、請求項1~3のいずれか一項に記載の感光性樹脂組成物。
- (A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、
前記樹脂がポリイミド前駆体を含む場合、前記ポリイミド前駆体が、以下の一般式(4):
前記樹脂が、下記一般式(15):
前記樹脂が、下記一般式(14):
- (A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、前記感光性樹脂組成物を350℃で加熱及び硬化して得られるポリイミド硬化膜のポリイミドにおいて、テトラカルボン酸二無水物とジアミンに由来する構造を含む繰り返し単位の分子量に対して、イミド基の分子量が占める割合をイミド基濃度Uとし、脂肪族炭化水素基の分子量の合計が占める割合を脂肪族炭化水素基濃度Tとすると、Xが、12wt%~26wt%であり、かつ、下記式(1):
-12.6<U-T<16.0 (1)
{を満たす、感光性樹脂組成物。 - (A)100質量部のポリイミド及びポリイミド前駆体から選ばれる少なくとも一つの樹脂と;
(B)0.5~10質量部の感光剤と;
(C)100~300質量部の溶媒と;
を含む、感光性樹脂組成物であって、
(A)ポリイミド前駆体を230℃で加熱及び硬化して得られるポリイミドのIRスペクトルで、1450cm-1以上1550cm-1以下の範囲にある吸収ピークの、一番大きなピーク強度をPh1、二番目の強度のピーク強度をPh2、1380cm-1付近のピーク強度をIm1とし、Ph1を1に規格化した時、下記式(2):
0.34≦Ph2×Im1≦1.2 (2)
を満たす、感光性樹脂組成物。 - 前記樹脂が、テトラカルボン酸二無水物とジアミンとの反応物である、請求項1~8のいずれか一項に記載の感光性樹脂組成物。
- 前記樹脂を構成する前記テトラカルボン酸二無水物の少なくとも一種、及び前記ジアミンの少なくとも一種が、脂肪族炭化水素基を有する、請求項9に記載の感光性樹脂組成物。
- (D)シランカップリング剤を更に含む、請求項1~10のいずれか一項に記載の感光性樹脂組成物。
- (E)ラジカル重合性化合物を更に含む、請求項1~11のいずれか一項に記載の感光性樹脂組成物。
- (E)ラジカル重合性化合物がアルキル基を持つことを特徴とする、請求項12に記載の感光性樹脂組成物。
- (F)熱架橋剤を更に含む、請求項1~13のいずれか一項に記載の感光性樹脂組成物。
- (G)フィラーを更に含む、請求項1~14のいずれか一項に記載の感光性樹脂組成物。
- 以下の工程:
請求項1~15のいずれか一項に記載の感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程と;
得られた前記感光性樹脂層を加熱及び乾燥する工程と;
加熱及び乾燥後の前記感光性樹脂層を露光する工程と;
露光後の前記感光性樹脂層を現像する工程と;
現像後の前記感光性樹脂層を加熱処理して、ポリイミド硬化膜を形成する工程と;
を含む、ポリイミド硬化膜の製造方法。 - 前記塗布~前記現像工程は、前記現像工程において膜厚10μm~15μmの感光性樹脂層が得られるように行い、現像する際の現像時間が30秒以下である、請求項16に記載のポリイミド硬化膜の製造方法。
- ポリイミド硬化膜であって、摂動方式スプリットシリンダー共振器法による周波数40GHzの誘電正接が0.003~0.014であり、下記式(3):
3<tanδ40×WVTR<10 (3)
{式中、tanδ40は摂動方式スプリットシリンダー共振器法による周波数40GHzでの誘電正接を示し、WVTRは、膜厚10μmに換算したポリイミド硬化膜の透湿度を示す。}を満たす、ポリイミド硬化膜。 - 前記感光性樹脂組成物は、再配線層用途に使用される、請求項1~15のいずれか一項に記載の感光性樹脂組成物。
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