WO2018037997A1 - 感光性樹脂組成物及び硬化レリーフパターンの製造方法 - Google Patents
感光性樹脂組成物及び硬化レリーフパターンの製造方法 Download PDFInfo
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- WO2018037997A1 WO2018037997A1 PCT/JP2017/029554 JP2017029554W WO2018037997A1 WO 2018037997 A1 WO2018037997 A1 WO 2018037997A1 JP 2017029554 W JP2017029554 W JP 2017029554W WO 2018037997 A1 WO2018037997 A1 WO 2018037997A1
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- 0 C=CC1=CCC**1 Chemical compound C=CC1=CCC**1 0.000 description 5
- GLAHRQIBPKOGGL-UHFFFAOYSA-N C[Os](C(C1C=CC=CC1C1=O)=CC1=N)=O Chemical compound C[Os](C(C1C=CC=CC1C1=O)=CC1=N)=O GLAHRQIBPKOGGL-UHFFFAOYSA-N 0.000 description 1
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
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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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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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
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
Definitions
- the present invention relates to, for example, an insulating material for an electronic component, and a negative photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, and a cured relief pattern using the negative photosensitive resin composition. It relates to a manufacturing method.
- the present invention includes, for example, an insulating material for electronic components, and a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, a method for producing polyimide using the same, and
- the present invention relates to a semiconductor device.
- polyimide resin, polybenzoxazole resin, phenol resin, etc. which have excellent heat resistance, electrical characteristics and mechanical characteristics, are used for insulating materials for electronic parts and passivation films, surface protective films, interlayer insulating films for semiconductor devices, etc. It is used.
- these resins those provided in the form of a photosensitive resin composition easily form a heat-resistant relief pattern film by applying the composition, exposure, development, and thermal imidization treatment by curing. be able to.
- Such a photosensitive resin composition has a feature that enables a significant reduction in the process compared to conventional non-photosensitive materials.
- the mounting method of a semiconductor device on a printed wiring board has also changed from the viewpoint of improving the degree of integration and function and minimizing the chip size.
- the polyimide coating is directly applied to the solder bumps, such as BGA (ball gripped array) and CSP (chip size packaging), which can be mounted with higher density than conventional mounting methods using metal pins and lead-tin eutectic solder. Contacting structures are being used. When such a bump structure is formed, the film is required to have high heat resistance and chemical resistance.
- a method for improving the heat resistance and chemical resistance of a polyimide coating by adding a thermal crosslinking agent to a composition containing a polyimide precursor has been disclosed (see, for example, Patent Document 1).
- polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices.
- these polyimide resins those provided in the form of a photosensitive polyimide precursor composition can easily form a heat-resistant relief pattern film by applying the composition, exposure, development, and thermal imidization treatment by curing. It can be formed (for example, see Patent Document 2).
- Such a photosensitive polyimide precursor composition has a feature that the process can be significantly shortened as compared with a conventional non-photosensitive polyimide material.
- Photosensitive polyimides can be classified into negative and positive types according to the photosensitive mechanism.
- the resin In the negative type, the resin remains in the exposed area by exposure and development.
- the positive type In the positive type, the resin remains in the unexposed area by exposure and development.
- the positive type since the positive type is excellent in resolution, it is often used for applications in which fine patterns are generally required, and strict in-plane uniformity of film thickness is required.
- the negative type is inferior to the positive type in resolution, but because it is superior in reliability, it is often used for applications that require higher reliability than pattern accuracy. I didn't ask for it.
- JP 2003-287889 A Japanese Patent Laid-Open No. 06-342211
- ⁇ Problem to be solved by the first embodiment of the present invention> Usually, when a polyimide resin film is obtained by curing and dehydrating and ring-closing a polyimide precursor, a high temperature of 300 ° C. or higher is required. However, when cured under the conditions, there is a problem that the yield of the chip is lowered depending on the device. Therefore, recently, a process of curing at a low temperature of 200 ° C. or lower is desired. However, when the polyimide precursor is cured at a low temperature of 200 ° C. or lower, the imide cyclization reaction (imidization) is insufficient, and the polyimide precursor remains in the resin film.
- the present invention has been devised in view of such conventional circumstances, and is a negative type in which a resin layer having a good imidization rate and high chemical resistance can be obtained even under low-temperature curing conditions of 200 ° C. or less. It is an object of the present invention to provide a photosensitive resin composition and a method for producing a cured relief pattern using the photosensitive resin composition.
- the present invention has been devised in view of such conventional situations. That is, the objective of this invention is providing the negative photosensitive polyimide resin composition which improved the in-plane uniformity of the film thickness when it was set as the film
- ⁇ Means for solving the first problem> By using a photosensitive resin having a specific weight average molecular weight (Mw), the present inventors have successfully progressed polyimide imide cyclization (imidation) even under low temperature curing conditions of 200 ° C. or lower. The inventors have found that a resin layer having high chemical resistance can be obtained, and have completed the present invention. That is, the present invention is as follows.
- a negative photosensitive resin composition comprising
- the (A) polyimide precursor is represented by the following general formula (1): ⁇ 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 is an integer of 2 to 50 And R 1 and R 2 are each independently a hydrogen atom or the following general formula (2): (Wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10).
- Mw weight average molecular weight
- X 1 represents the following general formulas (4) to (6): At least one tetravalent organic group selected from:
- Y 1 represents the following general formula (7): Wherein R 9 to R 12 are a hydrogen atom or a monovalent aliphatic group having 1 to 4 carbon atoms, which may be different or the same, and General formula (8): Or the following general formula (9): [Wherein R 13 to R 14 each independently represents a fluorine atom, a trifluoromethyl group, or a methyl group] is at least one divalent organic group selected from [1] The negative photosensitive resin composition as described.
- X 1 is the comprises the general formula (6)
- Y 1 comprises the general formula (7), the negative photosensitive resin composition according to [2].
- Mw weight average molecular weight
- X 1 comprises the general formula (5)
- Y 1 comprises the general formula (8), negative-type photosensitive resin composition according to [2].
- X 1 comprises the general formula (4)
- Y 1 comprises the general formula (7), the negative photosensitive resin composition according to [2].
- Mw weight average molecular weight of the (A) polyimide precursor
- GPC gel permeation chromatography
- a positive photosensitive resin composition comprising:
- the (A) polybenzoxazole precursor is represented by the following general formula (12): ⁇ Wherein U and V are divalent organic groups ⁇ And The positive photosensitive resin composition, wherein the weight average molecular weight (Mw) of the (A2) polyimide precursor is 3,000 or more and less than 16,000 in terms of polystyrene by gel permeation chromatography (GPC).
- Mw weight average molecular weight
- GPC gel permeation chromatography
- U is a positive-type photosensitive resin according to [14], wherein U is a chain alkylene group having 1 to 8 carbon atoms and part or all of hydrogen atoms substituted with fluorine atoms Composition.
- V is a positive photosensitive resin composition according to any one of [14] to [16], wherein V is a divalent organic group containing an aromatic group.
- the positive photosensitive resin composition according to [17] wherein V includes at least one structure represented by the following general formulas (13) to (15).
- R 10 , R 11 , R 12 and R 13 are a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different.
- R 14 to R 21 are a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms, which may be the same or different.
- R 22 is a divalent group
- R 23 to R 30 are a hydrogen atom, a halogen atom, or a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different.
- V is a positive photosensitive resin composition as described in [18] containing the structure represented by the following general formula (16).
- [20] (1) forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [19] on the substrate; (2) exposing the photosensitive resin layer; (3) developing the photosensitive resin layer after the exposure to form a relief pattern; (4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern. [21] The method for producing a cured relief pattern according to [20], wherein the substrate is made of copper or a copper alloy.
- a negative photosensitive resin composition comprising a photosensitive polyimide precursor having a reactive substituent that reacts by heat or light at the end of a main chain, and having a viscosity of 80 poise or less.
- Said reactive substituents are in the following groups: Acrylic group, methacrylic group, vinyl group, alkenyl group, cycloalkenyl group, alkadienyl group, cycloalkadienyl group, styryl group, ethynyl group, imino group, isocyanato group, cyanato group, cycloalkyl group, epoxy group, oxetanyl group,
- the photosensitive resin composition according to [1] comprising at least one selected from the group consisting of a carbonate group, a hydroxyl group, a mercapto group, a methylol group, and an alkoxyalkyl group.
- the reactive substituent includes at least one selected from the group consisting of 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.
- the photosensitive polyimide precursor is represented by the following general formula (A1): ⁇ In general formula (A1), X is a tetravalent organic group, Y is a divalent organic group, R 5 and R 6 are each independently a hydrogen atom, the following general formula (R1): (In the general formula (R1), R 7 , R 8 , and R 9 are each independently a hydrogen atom or a C 1 -C 3 organic group, and p is an integer selected from 1 to 10. ) Or a C 1 -C 4 saturated aliphatic group. However, R 5 and R 6 are not simultaneously hydrogen atoms.
- E1 includes at least one group of an amide bond, an imide bond, a urea bond, and a urethane bond
- b1 is a reactive substituent that crosslinks with heat or light
- e1 is 1 having 1 to 30 carbon atoms.
- R 11 and R 14 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms
- R 12 and R 13 are each independently a hydrogen atom or 1 to 30 carbon atoms. 30 or any one of an aromatic ring or an aliphatic ring (provided that R 12 and R 13 are not hydrogen atoms at the same time).
- f1 contains at least one group of an amide bond, an imide bond, a urea bond, a urethane bond, and an ester bond
- g1 is a reactive substituent that crosslinks with heat or light
- R 15 to R 19 Each independently represents a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or a part of an aromatic ring or an aliphatic ring (provided that R 16 , R 17 , and R 18 are simultaneously hydrogen atoms). None become an atom.
- [6] The negative photosensitive resin composition according to [5], wherein b1 and g1 are reactive substituents having a double bond at a terminal.
- the f1 includes at least one group of an amide group, an imide group, a urea group, and a urethane group.
- B1 is an acryl group, a methacryl 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, an isocyanato group, a cyanato group, a cycloalkyl group, an epoxy group.
- the photosensitive resin composition according to [5] which contains at least one selected from the group consisting of oxetanyl group, carbonate group, hydroxyl group, mercapto group, methylol group, and alkoxyalkyl group.
- b1 includes at least one selected from the group consisting of 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.
- the photosensitive resin composition as described.
- the photosensitive resin composition according to [10], wherein the reactive substituent that crosslinks with b1 heat or light includes a methacryl group.
- the reactive substituent that crosslinks with g1 heat or light is an acryl group, a methacryl 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, an isocyanato group.
- the photosensitivity according to [5] comprising at least one selected from the group consisting of a 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.
- Resin composition comprising at least one selected from the group consisting of a 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.
- the reactive substituent that crosslinks with g1 heat or light is selected from the group consisting of 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.
- [14] The photosensitive resin composition according to [13], wherein the reactive substituent that crosslinks with g1 heat or light includes a methacryl group.
- X in the general formula (A1) is the following (B1) to (B3): Containing at least one tetravalent organic group selected from Y represents the following (C1) to (C3):
- R 10 to R 13 are a hydrogen atom or a C1 to C4 monovalent aliphatic group, which may be the same or different from each other.
- R 14 ⁇ R 21 is a hydrogen atom, a monovalent organic group halogen atoms, or C 1 ⁇ C 4, be different from each other, may be the same.
- the negative photosensitive resin composition according to [15] wherein in the general formula (A1), X includes the general formula (B3), and Y includes the general formula (C2).
- X includes the general formula (B2)
- Y includes at least one selected from the group consisting of the general formulas (C1) and (C3).
- the negative photosensitive resin composition as described.
- Mw weight average molecular weight of the (A) polyimide precursor
- GPC gel permeation chromatography
- a negative photosensitive resin composition comprising a photosensitive polyimide precursor having a reactive substituent that reacts with heat or light at the end of the main chain
- the photosensitive polyimide precursor is represented by the following general formula (A1): ⁇ In general formula (A1), X is a tetravalent organic group, Y is a divalent organic group, R 5 and R 6 are each independently a hydrogen atom, the following general formula (R1): (In the general formula (R1), R 7 , R 8 , and R 9 are each independently a hydrogen atom or a C 1 -C 3 organic group, and p is an integer selected from 1 to 10. ) Or a C 1 -C 4 saturated aliphatic group.
- E1 includes at least one bond of amide bond, imide bond, urea bond, and urethane bond
- b1 is a reactive substituent that crosslinks with heat or light
- e1 is 1 having 1 to 30 carbon atoms.
- R 11 and R 14 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms
- R 12 and R 13 are each independently a hydrogen atom or 1 to 30 carbon atoms.
- f1 contains at least one bond of amide bond, imide bond, urea bond, urethane bond, ester bond
- g1 is a reactive substituent that crosslinks with heat or light
- R 15 to R 19 Each independently represents a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or a part of an aromatic ring or an aliphatic ring (provided that R 16 , R 17 , and R 18 are simultaneously hydrogen atoms).
- the negative photosensitive resin composition according to [29] wherein b1 and g1 are reactive substituents having a double bond at a terminal.
- the f1 includes at least one group of an amide group, an imide group, a urea group, and a urethane group.
- a method for producing a cured relief pattern comprising: [34] [1]
- the photosensitive polyimide precursor has the following steps: A step of obtaining a polyimide by subjecting a diamine monomer and an acid dianhydride monomer to a polycondensation reaction in an excess state, and reacting with the amine or acid anhydride remaining at the end of the polyimide by heat or light Introducing the reactive substituent at the end of the main chain of the polyimide by reacting with a compound having a reactive substituent;
- ⁇ Effect of the first embodiment> by using a photosensitive resin having a specific weight average molecular weight (Mw), polyimide imide cyclization reaction (imidization) proceeds well even under low temperature curing conditions of 200 ° C. or less. . Accordingly, in the present invention, a photosensitive resin composition in which a polyimide layer is hardly left in the resin film and a resin layer having high chemical resistance is obtained, and production of a cured relief pattern using the photosensitive resin composition A method can be provided.
- Mw weight average molecular weight
- the first aspect in the present embodiment is as follows.
- ⁇ Negative photosensitive resin composition> The present invention comprises (A) 100 parts by weight of a polyimide precursor, and (B) 0.1-20 parts by weight of a photopolymerization initiator, and the weight average molecular weight (Mw) of the (A) polyimide precursor Is a negative photosensitive resin composition characterized by having a polystyrene conversion by gel permeation chromatography (GPC) of 3,000 or more and less than 16,000.
- GPC gel permeation chromatography
- the polyimide precursor used for this invention is demonstrated.
- the (A) polyimide precursor of the present invention contains at least one resin selected from the group consisting of a polyamic acid ester or a polyamic acid salt as a main component.
- the main component means that these resins are contained in an amount of 50% by mass or more of the total resin, and preferably 60% by mass or more. Moreover, other resin may be included as needed.
- the polyimide precursor is preferably a photosensitive resin in order to form a relief pattern.
- the photosensitive resin is a resin that becomes a negative photosensitive resin composition when used together with a photopolymerization initiator (B) described later, and causes a phenomenon of dissolution or undissolution in the subsequent development process.
- the polyimide precursor is mainly composed of at least one resin selected from the group consisting of a polyamic acid ester or a polyamic acid salt.
- one of the most preferred (A) polyimide precursors from the viewpoint of heat resistance and photosensitive characteristics is the following general formula (1): ⁇ 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 is an integer of 2 to 50 R 1 and R 2 are each independently a hydrogen atom, or the following general formula (2) or (3): (Wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10).
- R 6 , R 7 and R 8 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10). It is a group. However, R 1 and R 2 are not simultaneously hydrogen atoms. ⁇ It is a polyamic acid ester or polyamic acid salt represented by this.
- the tetravalent organic group represented by X 1 is preferably an organic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties. More preferably, it is an aromatic group or an alicyclic aliphatic group in which the —COOR 1 group, —COOR 2 group and —CONH— group are in the ortho positions to each other.
- the tetravalent organic group represented by X 1 is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring.
- R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms
- l is selected from 0 to 2
- M is an integer selected from 0 to 3
- n is an integer selected from 0 to 4.
- the following general formulas (4) to (6) are more preferable examples among the tetravalent organic groups represented by X 1 : And at least one organic group selected from the group consisting of: These organic groups are particularly preferred because they are excellent in chemical resistance, photosensitivity, and copper void suppression effects, but are not limited thereto. Further, it may be the structure of X 1 is one, may be two or more kinds.
- the divalent organic group represented by Y 1 is preferably an organic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance, photosensitivity, and copper void suppression effect.
- the following formula (31) ⁇ Wherein R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is selected from 0 to 4 Is an integer. ⁇ Is represented.
- the general formula (7) is a hydrogen atom or a monovalent aliphatic group having 1 to 4 carbon atoms, which may be different or the same
- General formula (8) Or the following general formula (9): (Wherein, R 13 to R 14 each independently represents a fluorine atom, a trifluoromethyl group, or a methyl group), and examples thereof include at least one divalent organic group.
- a structure in which X 1 includes the general formula (5) and Y 1 includes the general formula (7), (8), or (9) is preferable from the viewpoints of chemical resistance and copper void suppression effect. .
- a structure in which X 1 includes the general formula (4) and Y 1 includes the general formula (7) is preferable from the viewpoints of chemical resistance and copper void suppression effect.
- a structure in which X 1 includes the general formula (6) is preferable because it is excellent in chemical resistance and copper void suppression effect.
- a structure containing X 1 is the general formula (6), and, more preferably structures Y 1 comprises a general formula (8) or (7), X 1 Is a structure containing the general formula (6), and Y 1 is most preferably a structure containing the general formula (8).
- Examples of methods for imparting photosensitivity to the negative photosensitive resin composition according to this embodiment include an ester bond type and an ion bond type.
- the former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond, into the side chain of the polyimide precursor (A) by an ester bond.
- the latter is a method of imparting a photopolymerizable group by bonding a carboxyl group of a polyimide precursor and an amino group of a (meth) acrylic compound having an amino group via an ionic bond.
- R 1 and R 2 in the general formula (1) are each independently a hydrogen atom or the following general formula (2): (Wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10). . However, R 1 and R 2 are not simultaneously hydrogen atoms.
- R 3 in the general formula (2) is preferably a hydrogen atom or a methyl group, and R 4 and R 5 are preferably a hydrogen atom from the viewpoint of photosensitive properties.
- m is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive characteristics.
- R 1 and R 2 in the general formula (1) are each independently a hydrogen atom or the following general formula ( 3): (Wherein R 6 , R 7 and R 8 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10). However, R 1 and R 2 are not simultaneously hydrogen atoms.
- R 6 in the general formula (3) is preferably a hydrogen atom or a methyl group, and R 7 and R 8 are preferably a hydrogen atom from the viewpoint of photosensitive properties.
- M 2 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive properties.
- the ester bond-type polyimide precursor is first composed of the tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X 1 , an alcohol having a photopolymerizable unsaturated double bond, and optionally 1 carbon atom.
- a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester form) is prepared by reacting with saturated aliphatic alcohols (1) to (4). Thereafter, it is obtained by amide polycondensation of this and a diamine containing the divalent organic group Y 1 described above.
- the tetracarboxylic dianhydride containing a tetravalent organic group X 1 that is suitably used for preparing an ester bond type polyimide precursor is a tetracarboxylic acid represented by the above general formula (30).
- acid dianhydrides for example, pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride Biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3 ′, 4 4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3 , 3-hexafluoropropane, etc.
- acid dianhydrides for example, pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride,
- Or pyromellitic anhydride diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 Examples thereof include, but are not limited to, ', 4,4'-tetracarboxylic dianhydride. These may be used alone or in combination of two or more.
- Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing an ester bond type polyimide precursor in the present invention include 2-acryloyloxyethyl alcohol and 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-phenoxy Propyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxye Alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl me
- methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. may be used as a mixture with the above alcohols as saturated aliphatic alcohols having 1 to 4 carbon atoms.
- the tetracarboxylic dianhydride suitable for the present invention and the alcohols are stirred and dissolved in a solvent as described later at a temperature of 20 to 50 ° C. for 4 to 10 hours in the presence of a basic catalyst such as pyridine. , By mixing, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.
- a suitable dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N′-disuccinimidyl carbonate, and the like are added and mixed to convert the acid / ester into a polyanhydride.
- the acid / ester polyanhydride obtained was added dropwise with a diamine containing a divalent organic group Y 1 suitably used in the present invention dissolved or dispersed in a solvent, and added dropwise.
- the target polyimide precursor can be obtained by polycondensation.
- the acid / ester can be reacted with a diamine compound in the presence of a base such as pyridine after the acid moiety has been acid chlorided using thionyl chloride or the like to obtain the target polyimide precursor. .
- diamines containing a divalent organic group Y 1 that are preferably used in the present invention include diamines having the structure represented by the general formula (31), for example, p-phenylenediamine, m-phenylenediamine, 4 , 4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3-
- 1,3-bis (3-aminophenoxy) benzene bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-amino) Phenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane,
- the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary. Thereafter, a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component. Furthermore, the polymer is purified by repeating redissolution, reprecipitation and the like, and vacuum drying is performed to isolate the target polyimide precursor. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.
- the ion-bonded polyimide precursor is typically obtained by reacting tetracarboxylic dianhydride with diamine.
- at least one of R 1 and R 2 in the general formula (1) is a hydrogen atom.
- the tetracarboxylic dianhydride is preferably a tetracarboxylic anhydride containing the structure of the above formula (30), and the diamine is preferably a diamine containing the structure of the above formula (31).
- a photopolymerizable group is imparted by an ionic bond between a carboxyl group and an amino group.
- Examples of (meth) acrylic compounds having amino groups include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylamino Dialkylaminoalkyl acrylates or methacrylates such as butyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate and diethylaminobutyl methacrylate are preferred. Of these, dialkylaminoalkyl acrylates or methacrylates having an alkyl group on the amino group of 1 to 10 carbon atoms and an alkyl chain of 1 to 10 carbon atoms are preferred from the viewpoint of photosensitive properties.
- the compounding amount of these (meth) acrylic compounds having an amino group is 1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and preferably 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics. It is excellent in photosensitivity by mix
- a known substituent that reacts with light irradiation or heat can be introduced into the polymer terminal of the polyimide precursor obtained by reacting the acid / ester with the diamine.
- substituents that react by light irradiation or heat include acrylate groups, allyl groups, alkoxymethyl groups, aldehyde groups, isocyanate groups, isothiocyanate groups, epoxy groups, oxazoline groups, oxetane groups, carbodiimide groups, glycidyl groups. , Triazine thiol group, bismaleimide group, benzoxazine group, methacrylate group, and methylol group, but are not limited thereto. Moreover, you may introduce
- 1, 3 -Diaminosiloxanes such as bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can also be copolymerized.
- the suitable range of the weight average molecular weight (Mw) of the (A) polyimide precursor which concerns on this embodiment is 3,000 or more and less than 16,000 in polystyrene conversion by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the weight average molecular weight (Mw) is larger than the above range, the molecular motion of the (A) polyimide precursor is insufficient under curing conditions, making it difficult for imidization to proceed, and the resulting resin layer has sufficient chemical resistance. No copper voids are likely to occur.
- the weight average molecular weight (Mw) is smaller than the above range, the molecular motion of the (A) polyimide precursor becomes active under curing conditions, and imidization easily proceeds.
- the weight average molecular weight (Mw) of the (A) polyimide precursor is small, the chemical resistance of the resin layer obtained after curing is not sufficient, and the generation of copper voids is easily suppressed.
- the imidation ratio is good even under a curing condition of 200 ° C. or less, and the chemical resistance of the obtained cured film is good, And resin which can suppress generation
- the more preferable range of the weight average molecular weight (Mw) of the said (A) polyimide precursor is 3,000 or more and 15,000 or less, More preferably, it is 3,000 or more and 13,000 or less, More preferably, 3, 000 or more and 11,000 or less, more preferably 3,000 or more and 10,000 or less, more preferably 3,000 or more and less than 10,000, more preferably 3,000 or more and 9,500 or less, particularly Preferably, it is 3,000 or more and 9,000 or less.
- the lower limit of the weight average molecular weight (Mw) of the (A) polyimide precursor may be 4,000 or more, 5,000 or more, 6,000 or more, It may be 000 or more.
- the upper limit of the weight average molecular weight (Mw) of the (A) polyimide precursor is 15,000 or less, 13,000 or less, 12,000 or less, 11,000 or less, or 10,000 or less, It may be less than 10,000.
- the preparation method which controls the weight average molecular weight (Mw) of a polyimide precursor is not specifically limited, The following techniques are known. For example, it can be achieved by appropriately controlling the addition molar ratio of the acid / ester containing the tetravalent organic group X 1 and the diamine containing the divalent organic group Y 1 during amino polycondensation.
- the weight average molecular weight (Mw) can be reduced by adding either one of the acid / ester containing the tetravalent organic group X 1 or the diamine containing the divalent organic group Y 1 in excess. is there.
- the measurement method of the weight average molecular weight (Mw) in this embodiment can be performed by gel permeation chromatography (GPC), and can be calculated by a calibration curve created using standard polystyrene. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography (GPC). As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
- the imidization rate can be easily calculated by the following method. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around -1, 1377 cm around -1) to confirm the presence of. Next, the polymer is heat-treated at 350 ° C. for 1 hour, and the infrared absorption spectrum after the heat treatment is measured. Then, the imidization rate in the polymer before heat treatment is calculated by comparing the peak intensity around 1377 cm ⁇ 1 with the intensity before heat treatment.
- the photopolymerization initiator used in the present invention will be described.
- the blending amount of the (B) photopolymerization initiator in the negative photosensitive resin composition is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- the said compounding quantity is 0.1 mass part or more from a viewpoint of photosensitivity or patterning property, and is 20 mass parts or less from a viewpoint of the film
- the photopolymerization initiator is preferably a photoradical polymerization initiator, and benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone.
- Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone
- Benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl- ⁇ -methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butyl 2-dione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxy) Carbonyl) oxime, 1-phenyl
- R 1 to R 3 are preferably used independently from a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, or a hydroxyalkyloxy group. And a group selected from a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms containing a hetero atom, an alkylaryl group, an arylalkyl group, and a hydroxyalkyloxy group.
- voids hereinafter also referred to as voids
- the adhesion between the copper layer and the polyimide layer can be increased, and the generation of voids can be suppressed.
- the following general formula (11) is preferably used as the (B) photopolymerization initiator: ⁇ Wherein Z is a sulfur or oxygen atom, and R 15 represents a methyl group, a phenyl group or a divalent organic group, and R 16 to R 18 each independently represents a hydrogen atom or a monovalent organic group. Represents. ⁇ It is an oxime ester compound represented by these.
- R 16 to R 18 are preferably each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, or a hydroxyalkyloxy group.
- (B) photopolymerization initiators suitably used include the following formula: At least one selected from is preferably used. Examples of such trade names include Irgacure OXE-01 manufactured by BASF, TR-PBG-305 manufactured by Changzhou Powerful New Electronic Materials Co., Ltd., TR-PBG-3057, NCI-930 manufactured by ADEKA, and the like.
- oxime ester photoinitiator By using such an oxime ester photoinitiator, a resin layer having a good imidization rate, high chemical resistance, and capable of suppressing the generation of copper voids can be obtained.
- the (A) polyimide precursor represented by the general formula (1) is an ion-bonded type
- (A) a photopolymerizable group is imparted to the side chain of the polyimide precursor via an ionic bond. Therefore, a (meth) acrylic compound having an amino group is used. In this case, a (meth) acrylic compound having an amino group is used as the (B) photopolymerization initiator.
- (meth) acrylic compound having an amino group for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, Dialkylaminoalkyl acrylates or methacrylates such as diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate and the like are preferred. Of these, dialkylaminoalkyl acrylates or methacrylates having an alkyl group on the amino group of 1 to 10 carbon atoms and an alkyl chain of 1 to 10 carbon atoms
- the compounding amount of these (meth) acrylic compounds having an amino group is 1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and preferably 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics.
- the (meth) acryl compound having an amino group is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of the (A) polyimide precursor, so that the photosensitivity is excellent, and 20 parts by mass or less is blended. Excellent thick film curability.
- the above-mentioned polyimide precursor resin composition and polyamide resin composition, which are negative resin compositions in the present embodiment, can contain a solvent for dissolving these resins.
- the photosensitive resin composition can also use the positive photosensitive resin composition containing (A2) polybenzoxazole precursor and (B2) photo-acid generator.
- A2) polybenzoxazole precursor and (B2) photo-acid generator As the photosensitive resin used in the polybenzoxazole precursor composition, poly (o-hydroxyamide) containing a repeating unit represented by the following general formula (12) can be used.
- U is preferably a divalent organic group having 1 to 30 carbon atoms, and a chain alkylene group having 1 to 15 carbon atoms (however, a hydrogen atom of the chain alkylene) May be substituted with a halogen atom), and a chain alkylene group having 1 to 8 carbon atoms and having some or all of the hydrogen atoms substituted with fluorine atoms is particularly preferred.
- V is preferably a divalent organic group containing an aromatic group, more preferably at least represented by the following general formulas (13) to (15).
- a divalent organic group containing one structure is preferable.
- R 10 , R 11 , R 12 and R 13 are a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different.
- R 14 to R 21 are a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms, which may be the same or different.
- R 22 is a divalent group
- R 23 to R 30 are a hydrogen atom, a halogen atom, or a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different. Good.
- R 22 in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.
- V is particularly preferably a divalent organic group including a structure represented by the following general formula (16).
- V is preferably a divalent organic group having 1 to 40 carbon atoms, more preferably a divalent chain aliphatic group having 1 to 40 carbon atoms, A divalent chain aliphatic group having 1 to 20 carbon atoms is particularly preferred.
- the polybenzoxazole precursor can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with a diamine. As the dihalide derivative, a dichloride derivative is preferable.
- the dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent.
- a halogenating agent thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid, can be used.
- the dichloride derivative As a method of synthesizing the dichloride derivative, it can be synthesized by a method of reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, a method of reacting in an excess halogenating agent, and then distilling off the excess.
- dicarboxylic acid used for the dicarboxylic acid derivative examples include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4 '-Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5- tert-Butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n -Butylmalonic acid, succinic acid, tetrafluorosuccinic
- hydroxy group-containing diamine examples include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, and bis (3-amino-4-hydroxyphenyl).
- Propane bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino) -4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3 -Hexafluoropropane and the like. You may mix and use these.
- the photoacid generator has a function of increasing the aqueous alkali solubility of the light irradiation part.
- the photoacid generator include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Of these, diazonaphthoquinone compounds are preferred because of their high sensitivity.
- the suitable range of the weight average molecular weight (Mw) of the (A) polybenzoxazole precursor according to this embodiment is 3,000 or more and less than 16,000 in terms of polystyrene by gel permeation chromatography (GPC). .
- the polybenzoxazole precursor (A) having a weight average molecular weight (Mw) within this range the cyclization reaction of polybenzoxazole proceeds well even under curing conditions of 200 ° C. or less, and chemical resistance is improved. A resin layer that is high and can suppress the generation of copper voids is obtained.
- the weight average molecular weight (Mw) is larger than the above range, the molecular motion of the (A2) polybenzoxazole precursor is insufficient under curing conditions and cyclization is difficult to proceed, and the resulting resin layer has chemical resistance. Insufficient copper voids are likely to occur.
- the weight average molecular weight (Mw) when the weight average molecular weight (Mw) is smaller than the above range, the molecular motion of the (A2) polybenzoxazole precursor becomes active under curing conditions, and imidization easily proceeds.
- the weight average molecular weight (Mw) of the (A2) polybenzoxazole precursor is small, the chemical resistance of the resin layer obtained after curing is not sufficient, and it becomes easy to suppress the generation of copper voids.
- the polybenzoxazole precursor (A2) having a weight average molecular weight (Mw) in this range the cyclization rate is good even under a curing condition of 200 ° C. or less, and the resulting cured film has good chemical resistance.
- the more preferable range of the weight average molecular weight (Mw) of the polybenzoxazole precursor (A2) is 3,000 or more and 15,000 or less, more preferably 3,000 or more and 13,000 or less, more preferably 3,000 or more and 11,000 or less, more preferably 3,000 or more and 10,000 or less, more preferably 3,000 or more and less than 10,000, more preferably 3,000 or more and 9,500 or less Particularly preferred is 3,000 or more and 9,000 or less.
- the lower limit of the weight average molecular weight (Mw) of the (A2) polybenzoxazole precursor may be 4,000 or more, 5,000 or more, or 6,000 or more, It may be 7,000 or more.
- the upper limit of the weight average molecular weight (Mw) of the (A2) polybenzoxazole precursor may be 15,000 or less, 13,000 or less, or 12,000 or less, It may be 11,000 or less, may be 10,000 or less, and may be less than 10,000.
- the preparation method which controls the weight average molecular weight (Mw) of a polybenzoxazole precursor is not specifically limited, The following techniques are known.
- the polycondensation can be achieved by appropriately controlling the addition molar ratio of the dicarboxylic acid containing the divalent organic group X 1 and the aminophenol containing the divalent organic group Y 1 . It is possible to reduce the weight average molecular weight (Mw) by adding either one of a dicarboxylic acid containing a divalent organic group X 1 or an aminophenol containing a divalent organic group Y 1 in excess. .
- the measurement method of the weight average molecular weight (Mw) in this embodiment can be performed by gel permeation chromatography (GPC), and can be calculated by a calibration curve created using standard polystyrene. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography (GPC). As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
- solvent examples include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols and the like.
- N-methyl-2-pyrrolidone N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate , Butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, ⁇ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfur
- N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene from the viewpoints of resin solubility, resin composition stability, and adhesion to a substrate.
- Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.
- N-methyl-2-pyrrolidone N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea And gamma-butyrolactone.
- the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. More preferably, it is in the range of 125 to 500 parts by mass.
- the photosensitive resin composition of the present invention may further contain components other than the components (A) and (B).
- a nitrogen-containing complex such as an azole compound or a purine derivative is used to suppress discoloration on copper.
- a ring compound can be arbitrarily blended.
- azole compound 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, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis ( ⁇ , ⁇ -Dimethylbe Benzyl) phenyl] -benzotriazole, 2- (3,5-di-tert-butyl
- tolyltriazole Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.
- purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Guanine, N- (3-ethylphenyl) guanine, 2-a Aden
- the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. From the viewpoint of characteristics, 0.5 to 5 parts by mass is more preferable.
- the compounding quantity with respect to 100 mass parts of (A) polyimide precursor of an azole compound is 0.1 mass part or more, when forming the negative photosensitive resin composition of this invention on copper or a copper alloy, copper Or discoloration of the copper alloy surface is suppressed.
- the compounding quantity of an azole compound is 20 mass parts or less, it is excellent in photosensitivity.
- a hindered phenol compound in the negative photosensitive resin composition of the present invention, can be arbitrarily blended in order to suppress discoloration on the copper surface.
- hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4.
- Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2,6-dimethyl) -4-Isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2 , 6-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2) , 6-Dimethylbenzyl)
- 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione and the like are particularly preferred.
- the blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. From the viewpoint of photosensitivity characteristics, it is more preferably 0.5 to 10 parts by mass.
- the compounding quantity with respect to 100 mass parts of (A) polyimide precursor of a hindered phenol compound is 0.1 mass part or more, For example, when forming the negative photosensitive resin composition of this invention on copper or a copper alloy Further, discoloration and corrosion of copper or copper alloy is prevented. On the other hand, when the amount of the hindered phenol compound is 20 parts by mass or less, the photosensitivity is excellent.
- the negative photosensitive resin composition of the present invention may contain an organic titanium compound.
- an organic titanium compound By containing an organic titanium compound, a photosensitive resin layer having excellent substrate adhesion can be formed even when cured at a low temperature of 200 ° C. or lower.
- Examples of usable organic titanium compounds include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.
- Titanium chelate compound a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition and a good pattern can be obtained.
- Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium di (n-butoxide) bis (2,4-pentanedionate, titanium diisopropoxide bis (2,4-pentanedionate).
- Tetraalkoxytitanium compounds for example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyloxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis [bis ⁇ 2,2- (allyloxymethyl) Butoxide ⁇ ] and the like.
- Titanocene compounds 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 and the like.
- Monoalkoxytitanium compound For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, and the like.
- Titanium oxide compound for example, titanium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
- Titanium tetraacetylacetonate compound For example, titanium tetraacetylacetonate.
- Titanate coupling agent For example, isopropyltridodecylbenzenesulfonyl titanate.
- the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint.
- titanium diisopropoxide bis (ethyl acetoacetate), 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 preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited.
- it is 10 parts by mass or less, the storage stability is excellent.
- Adhesion aids include ⁇ -aminopropyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3′-bis (
- the blending amount of the adhesion aid is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- silane coupling agent 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Silaace S810), 3-mercaptopropyltriethoxysilane (manufactured by Asmax Co., Ltd .: Trade name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name: LS1375, manufactured by Azumax Co., Ltd .: trade name: SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azumax Corporation: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane
- N- (3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) Urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea Urea, N- (3-methoxydi Propoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3- (3-
- silane coupling agent among the above-mentioned silane coupling agents, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxy Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent represented by the following structure are preferred.
- the amount of the silane coupling agent used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- the negative photosensitive resin composition of the present invention can optionally contain a sensitizer in order to improve photosensitivity.
- a sensitizer examples include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal).
- the blending amount of the sensitizer is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- the negative photosensitive resin composition of the present invention can optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern.
- a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate.
- the blending amount of the monomer having a photopolymerizable unsaturated bond is ( A) The amount is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor.
- thermal polymerization inhibitors include 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 salt, N-nitroso-N (1-n
- adhesion to dyes, surfactants, thermal acid generators, dissolution accelerators, and base materials conventionally used as additives for photosensitive resin compositions is enhanced.
- Adhesion aids for the purpose can be added as appropriate.
- the above additives include, for example, methyl violet, crystal violet, malachite green and the like as the dye.
- the surfactant include non-ionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, such as Fluorard (trade name, manufactured by Sumitomo 3M), Fluorosurfactants such as trade name, Dainippon Ink and Chemicals) or Lumiflon (trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical), DBE (trade name, manufactured by Chisso) ) And granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- adhesion assistant examples include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.
- the blending amount of the dye and the surfactant is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
- a thermal acid generator can be arbitrarily blended from the viewpoint of exhibiting good thermal and mechanical properties of the cured product.
- the thermal acid generator is preferably blended from the viewpoint of exhibiting good thermal and mechanical properties of the cured product even when the curing temperature is lowered.
- thermal acid generator examples include a salt formed from a strong acid such as an onium salt and a base having a function of generating an acid by heat, and an imide sulfonate.
- onium salts include diaryl iodonium salts such as aryl diazonium salts and diphenyl iodonium salts; Di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; Trialkylsulfonium salts such as trimethylsulfonium salts; dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salts; Examples include diarylmonoalkyliodonium salts such as diphenylmethylsulfonium salts; triarylsulfonium salts.
- di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid A dimethylphenylsulfonium salt, a diphenylmethylsulfonium salt of toluenesulfonic acid, and the like are prefer
- the salt formed from a strong acid and a base in addition to the onium salt described above, the following salt formed from a strong acid and a base, such as a pyridinium salt, can also be used.
- Strong acids include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, methanesulfonic acid, ethanesulfonic acid And alkylsulfonic acid such as butanesulfonic acid.
- the base include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines.
- imide sulfonate for example, naphthoyl imide sulfonate, phthalimide sulfonate, and the like can be used, but there is no limitation as long as the compound generates an acid by heat.
- the blending amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. More preferably, it is part by mass.
- the present invention also includes (1) a step of forming a resin layer on the substrate by applying the negative photosensitive resin composition of the present invention described above onto the substrate, and (2) exposing the resin layer.
- a cured relief pattern comprising: a step; (3) a step of developing the exposed resin layer to form a relief pattern; and (4) a step of forming a cured relief pattern by curing the relief pattern.
- a manufacturing method is provided. Hereinafter, typical aspects of each process will be described.
- the negative photosensitive resin composition of this invention is apply
- a coating method a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spray coating with a spray coater A method or the like can be used.
- the negative photosensitive resin composition is applied on a substrate to form a resin layer on the substrate,
- the resin layer may be formed by laminating a layer of a negative photosensitive resin composition on a substrate in the form of a negative photosensitive resin composition.
- a film of the negative photosensitive resin composition according to the present invention may be formed on a supporting substrate, and the supporting substrate may be removed after being laminated when the film is used. It may be removed.
- the coating film made of the negative photosensitive resin composition can be dried.
- a drying method methods such as air drying, heat drying using an oven or a hot plate, vacuum drying, and the like are used. Specifically, when air drying or heat drying is performed, the drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As described above, the resin layer can be formed on the substrate.
- Step of exposing the resin layer the resin layer formed above is exposed directly or directly through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, mirror projection, or stepper. Exposure is performed with an ultraviolet light source or the like.
- post-exposure baking PEB
- pre-development baking with any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity.
- the range of the baking conditions is that the temperature is 40 to 120 ° C. and the time is preferably 10 seconds to 240 seconds, but as long as the various characteristics of the negative photosensitive resin composition of the present invention are not impaired, It is not restricted to this range.
- the developer used for development is preferably a good solvent for the negative photosensitive resin composition or a combination of the good solvent and the poor solvent.
- a good solvent N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, and the like are preferable.
- Is preferably 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 depending on the solubility of the polymer in the photosensitive resin composition.
- two or more of each solvent for example, several types may be used in combination.
- Step of forming a cured relief pattern by curing the relief pattern the relief pattern obtained by the development is cured and converted to a cured relief pattern.
- a curing method various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected.
- the curing can be performed, for example, at 150 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmosphere gas for curing, and an inert gas such as nitrogen or argon may be used.
- the present invention also provides a semiconductor device including a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention.
- the present invention also provides a semiconductor device including a base material which is a semiconductor element, and a cured relief pattern of a resin formed on the base material by the above-described cured relief pattern manufacturing method.
- the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of the process.
- the semiconductor device of the present invention is a semiconductor device having a surface relief film, an interlayer insulation film, a rewiring insulation film, a flip chip device protection film, or a bump structure as a cured relief pattern formed by the above-described cured relief pattern production method. And can be manufactured by combining with a known method for manufacturing a semiconductor device.
- the negative photosensitive resin composition of the present invention is used for semiconductor devices as described above, as well as for interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, etc. Also useful.
- Embodiments of the present invention will be specifically described below. Throughout the present specification, when a plurality of structures represented by the same symbol in the general formula are present in a molecule, they may be the same as or different from each other.
- the second aspect according to the present embodiment is as follows.
- the photosensitive resin composition of the present invention is a negative photosensitive resin having a viscosity of 80 poise or less and containing a photosensitive polyimide precursor having a reactive substituent at the end of the main chain.
- photosensitive polyimide precursor The photosensitive polyimide precursor which has a reactive substituent at the terminal used for this invention is demonstrated. What is preferably used as the photosensitive polyimide precursor in the present invention has an i-ray absorbance of 0.1 to 2.0. The i-line absorbance is measured on a 10 ⁇ m thick film obtained after applying the photosensitive polyimide precursor as a single solution and pre-baking. In the cured relief pattern obtained from the photosensitive resin composition, the photosensitive resin composition of the present invention contains a photosensitive polyimide precursor that satisfies the above requirements in order to make the side surface of the opening into a forward tapered shape. Is preferred.
- the i-line absorbance of a 10 ⁇ m-thick film can be measured with a conventional spectrophotometer after prebaking a coating film in which a photosensitive polyimide precursor is formed on quartz glass alone.
- the absorbance obtained for the film is converted to a thickness of 10 ⁇ m according to Lambert-Beer's law, whereby an i-line absorbance of 10 ⁇ m thickness can be obtained.
- the i-ray absorbance is less than 0.1, the structure of the photosensitive polyimide precursor that satisfies this is limited, so that the mechanical properties, thermophysical properties, etc. are inferior.
- the i-line absorbance exceeds 2.0 the i-line absorption of the coating film is too large and light does not reach the bottom. Therefore, in the case of the negative type, there may be a problem that the bottom of the coating film is not cured.
- the photosensitive polyimide precursor of the present invention is preferably composed mainly of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide.
- the main component means that these resins are contained in an amount of 60% by mass or more, and preferably 80% by mass or more, based on the total resin.
- the photosensitive polyimide precursor may contain other resin as needed.
- the weight average molecular weight (Mw) of the photosensitive polyimide precursor is 1,000 or more in terms of polystyrene by gel permeation chromatography (GPC) from the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment. Is preferable, and more preferably 3,000 or more.
- the upper limit of the weight average molecular weight (Mw) is preferably 100,000 or less. From the viewpoint of solubility in a developer, the upper limit of the weight average molecular weight (Mw) is more preferably 50,000 or less.
- the reactive substituent at the end of the main chain of the photosensitive polyimide precursor of the present invention that reacts with heat or light is, for example, an acryl group, a methacryl group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, At least selected from cycloalkadienyl group, styryl group, ethynyl group, imino group, isocyanato group, cyanato group, cycloalkyl group, epoxy group, oxetanyl group, carbonate group, hydroxyl group, mercapto group, methylol group, alkoxyalkyl group It is a kind.
- 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 are preferably used.
- the photosensitive polyimide precursor used in the present invention is synthesized by a polycondensation reaction in which the amine portion of the diamine monomer and the acid anhydride portion of the acid dianhydride monomer form an amide bond. Since the polycondensation is carried out in an excess of either the diamine monomer or the acid dianhydride monomer, after the polycondensation, if the diamine is excessive, an amine is present at the end of the main chain, and if the acid dianhydride is excessive. An acid anhydride remains at the end of the main chain.
- a reactive substituent that reacts by heat or light can be introduced at the end of the main chain.
- the introduction of a reactive substituent into the diamine monomer or acid dianhydride monomer is not an introduction at the end of the main chain.
- the acid dianhydride monomer of the polyimide precursor is schematically represented as “A” and the diamine monomer as “B”. It is assumed that the acid dianhydride monomer A has a substituent X in the side chain, and the diamine monomer B has a substituent Y in the side chain. A reactive substituent M is introduced at the end of the main chain. That is, the polyimide precursor according to the present invention is expressed as follows. Here, a case where B is a terminal is taken as an example, but A may be a terminal.
- the polyimide precursor which concerns on this invention also includes the case where the terminal group M is the same as the substituent Y and X which the monomer has. Therefore, the present invention also includes a polyimide precursor schematically represented as follows.
- the reactive group M included in the polyimide precursor is “positively” introduced at the terminal of the “main chain” after polymerization, and the monomer originally has This is different from the substituent Y that had been used. Therefore, even if the end group M happens to be the same as the substituent Y originally possessed by the monomer, both should be distinguished.
- prior art documents describe polyamide precursors, but some of the ends of the main chain are not modified.
- the polyamide precursor described in this prior art document is schematically represented as follows.
- B is a terminal
- A may be a terminal.
- the reactivity referred to in the present invention is present even if there is a reactive substituent Y or X at the terminal of the main chain. It is not a group M having Further, introduction of the reactive substituents X and Y into the monomer A or the monomer B is not introduction at the end of the main chain.
- reacting with heat or light means that some chemical change occurs due to heat or light.
- it includes crosslinking with heat or light like a methacryloxy group, or removal of a protecting group with heat or light like a t-butyl carbonate group.
- the main chain end of the photosensitive polyimide precursor is usually an amino group or an acid anhydride group. Or a carboxyl group.
- a reactive substituent that reacts with heat or light is introduced into this terminal directly or via a divalent substituent having 1 to 20 carbon atoms such as an alkyl group or an aromatic group.
- the introduction of end groups may be at the monomer stage or after polymerization.
- the introduction ratio of the reactive substituent at the terminal is preferably 50% or more, and more preferably 80% or more. Moreover, you may introduce
- one of the most preferable photosensitive polyimide precursors is represented by the following general formula (A1): ⁇ In general formula (A1), X is a tetravalent organic group, Y is a divalent organic group, R 5 and R 6 are each independently a hydrogen atom, the following general formula (R1): (In the general formula (R1), R 7 , R 8 , and R 9 are each independently a hydrogen atom or a C 1 -C 3 organic group, and p is an integer selected from 1 to 10. ) Or a C 1 -C 4 saturated aliphatic group. However, R 5 and R 6 are not simultaneously hydrogen atoms.
- An ester-type photosensitive polyimide precursor including a structure represented by: p may be 2 to 10.
- the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties. More preferably, the —COOR group, the —COOR 2 group and the —CONH— group are an aromatic group or an alicyclic aliphatic group in the ortho position of each other.
- the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms and containing an aromatic ring.
- R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C 1 to C 10 hydrocarbon group, and a C 1 to C 10 fluorine-containing hydrocarbon group
- l is selected from 0 to 2
- M is an integer selected from 0 to 3
- n is an integer selected from 0 to 4.
- the structure represented by these is mentioned, it is not limited to these.
- the structure of X may be one type or a combination of two or more types.
- the X group having the structure represented by the above formula is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.
- tetravalent organic groups represented by X in the general formula (A1) the following (B1) to (B3): And at least one organic group selected from the group consisting of: These organic groups are particularly preferable from the viewpoint of improving the in-plane uniformity of the film thickness, but are not limited thereto. Further, the structure of X may be one type or a combination of two or more types.
- the divalent organic group represented by Y is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive characteristics.
- the following formula (31) ⁇ Wherein, R25 represents a hydrogen atom, a fluorine atom, a hydrocarbon group of C 1 ⁇ C 10, a monovalent group selected from a fluorine-containing hydrocarbon group of C 1 ⁇ C 10, and n is from 0 to 4 An integer chosen.
- R25 represents a hydrogen atom, a fluorine atom, a hydrocarbon group of C 1 ⁇ C 10, a monovalent group selected from a fluorine-containing hydrocarbon group of C 1 ⁇ C 10, and n is from 0 to 4 An integer chosen.
- the structure represented by these is mentioned, it is not limited to these.
- the structure of Y may be one type or a combination of two or more types.
- the Y group having the structure represented by the above formula (31) is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.
- R 7 in the general formula (R1) is preferably a hydrogen atom or a methyl group.
- R 8 and R 9 are preferably hydrogen atoms from the viewpoint of photosensitive properties.
- p is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive characteristics.
- divalent organic groups represented by Y in the general formula (A1) the following (C1) to (C3):
- R 10 to R 13 are a hydrogen atom or a C1 to C4 monovalent aliphatic group, which may be the same or different from each other.
- R 14 to R 21 are each a hydrogen atom, a halogen atom, or C 1 -C 4 1 Valent organic group, which may be different from each other or the same.
- These organic groups are particularly preferable from the viewpoint of improving the in-plane uniformity of the film thickness, but are not limited thereto.
- Y in the general formula (A1) contains the (C3).
- X in the general formula (A1) is the following (B3): And Y is the following (C2): It is particularly preferable to contain the film because the in-plane uniformity of the film thickness can be improved.
- X in general formula (A1) is following (B3):
- Y is the following (C3): It is particularly preferable to contain the film because the in-plane uniformity of the film thickness can be improved.
- X in general formula (A1) is following (B2):
- Y is the following (C2): It is particularly preferable to contain the film because the in-plane uniformity of the film thickness can be improved.
- X in general formula (A1) is following (B3):
- Y is the following (C1): It is preferable that the film contains an in-plane uniformity of the film thickness.
- a structure in which X includes the general formula (B3) and Y includes the general formula (C2) or (C1) is preferable.
- a structure in which X includes the general formula (B2) and Y includes the general formula (C1), (C2), or (C3) is preferable.
- a structure in which X includes the general formula (B1) and Y includes the general formula (C1) is preferable.
- These combinations are particularly preferred because they are excellent in chemical resistance and the effect of suppressing copper voids, but are not limited thereto.
- a structure in which X includes the general formula (B3) and Y includes the general formula (C2) is most preferable from the viewpoints of chemical resistance and copper void suppression effect.
- the preferred range of the weight average molecular weight (Mw) of the (A) polyimide precursor according to this embodiment is 3,000 or more and less than 16,000 in terms of polystyrene by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the weight average molecular weight (Mw) is larger than the above range, the molecular motion of the (A) polyimide precursor is insufficient under curing conditions, making it difficult for imidization to proceed, and the resulting resin layer has sufficient chemical resistance. No copper voids are likely to occur.
- the weight average molecular weight (Mw) is smaller than the above range, the molecular motion of the (A) polyimide precursor becomes active under curing conditions, and imidization easily proceeds.
- the weight average molecular weight (Mw) of the (A) polyimide precursor is small, the chemical resistance of the resin layer obtained after curing is not sufficient, and the generation of copper voids is easily suppressed.
- the imidation ratio is good even under a curing condition of 200 ° C. or less, and the chemical resistance of the obtained cured film is good, And resin which can suppress generation
- the more preferable range of the weight average molecular weight (Mw) of the said (A) polyimide precursor is 3,000 or more and 15,000 or less, More preferably, it is 3,000 or more and 13,000 or less, More preferably, 3, 000 or more and 11,000 or less, more preferably 3,000 or more and 10,000 or less, more preferably 3,000 or more and less than 10,000, more preferably 3,000 or more and 9,500 or less, particularly Preferably, it is 3,000 or more and 9,000 or less.
- the lower limit of the weight average molecular weight (Mw) of the (A) polyimide precursor may be 4,000 or more, 5,000 or more, 6,000 or more, It may be 000 or more.
- the upper limit of the weight average molecular weight (Mw) of the (A) polyimide precursor may be 15,000 or less, 13,000 or less, 12,000 or less, 000 or less, 10,000 or less, or less than 10,000.
- the preparation method which controls the weight average molecular weight (Mw) of a polyimide precursor is not specifically limited, The following techniques are known. For example, it can be achieved by appropriately controlling the addition molar ratio of the acid / ester containing the tetravalent organic group X 1 and the diamine containing the divalent organic group Y 1 during amino polycondensation.
- the weight average molecular weight (Mw) can be reduced by adding either one of the acid / ester containing the tetravalent organic group X 1 or the diamine containing the divalent organic group Y 1 in excess. is there.
- the measurement method of the weight average molecular weight (Mw) in this embodiment can be performed by gel permeation chromatography (GPC), and can be calculated by a calibration curve created using standard polystyrene. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography (GPC). As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
- examples of methods for imparting photosensitivity to the photosensitive resin composition include an ester bond type and an ion bond type.
- the former is a method in which a compound having a photopolymerizable group, that is, an olefinic double bond is introduced into the side chain of the polyimide precursor by an ester bond.
- the latter is a method for imparting a photopolymerizable group by bonding a carboxyl group of a polyimide precursor and an amino group of a (meth) acrylic compound having an amino group via an ionic bond.
- the ester bond type polyimide precursor is obtained as follows. That is, first, the tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X, an alcohol having a photopolymerizable unsaturated double bond, and optionally a saturated aliphatic alcohol having 1 to 4 carbon atoms. Is reacted to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester). Thereafter, this acid / ester is obtained by amide polycondensation of the diamine containing the divalent organic group Y described above.
- At least one terminal of the main chain of the photosensitive polyimide precursor has a structure represented by the following general formula (E1) or (F1).
- E1 includes at least one bond of amide bond, imide bond, urea bond, and urethane bond
- b1 is a reactive substituent that crosslinks with heat or light
- e1 is 1 having 1 to 30 carbon atoms.
- R 11 and R 14 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms
- R 12 and R 13 are each independently a hydrogen atom or 1 to 30 carbon atoms.
- a monovalent organic group, an aromatic ring or a part of an aliphatic ring (however, R 12 and R 13 are not hydrogen atoms at the same time).
- f1 includes at least one bond of amide bond, imide bond, urea bond, urethane bond and ester bond
- g1 is a reactive substituent which crosslinks with heat or light
- R 15 to R 19 are Each is independently a hydrogen atom, a monovalent organic group having 1 to 30 carbon atoms, or an aromatic ring or a part of an aliphatic ring.
- R 16 , R 17 , and R 18 do not simultaneously become hydrogen atoms.
- f1 contains at least 1 group of an amide group, an imide bond, a urea group, and a urethane group. If f1 is an ester group, it is easily hydrolyzed and may not be crosslinked. Since these four groups (amide group, imide bond, urea group, urethane group) are hardly hydrolyzed, crosslinking by baking after development is efficiently performed. Therefore, chemical resistance is high.
- the reactive substituent b1 that crosslinks with heat or light is, for example, an acryl group, a methacryl 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 preferable.
- the reactive substituent g1 that crosslinks with heat or light is, for example, an acryl group, a methacryl 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 isocyanato group, cyanato group, cycloalkyl group, epoxy group, oxetanyl group, carbonate group, hydroxyl group, mercapto group, methylol group, and 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. A methacryl group is particularly preferable.
- examples of a method for introducing a reactive substituent that reacts with heat or light at the end of the main chain include the following methods. That is, first, for example, an excess of diamine is added during amide polycondensation. In this way, both ends of the main chain are made amino groups. And the compound which has a reactive substituent which reacts with a heat
- examples of the site that reacts with the amino group include an acid anhydride, an epoxy, and an isocyanate. Conversely, the following method can also be mentioned.
- a partially esterified tetracarboxylic acid is charged excessively so that both ends of the main chain become carboxyl groups. Then, a compound having a reactive group that reacts with heat or light and having a site that also reacts with the carboxyl group is reacted with the carboxyl group. At this time, examples of the site that reacts with the carboxyl group include amines and alcohols.
- the above is a method of introducing a reactive substituent that reacts with heat or light at the end of the main chain after amide polycondensation.
- a compound having a reactive substituent that reacts with heat or light and a site that reacts with an amino group may be added.
- a compound having a reactive substituent that reacts with heat or light and a site that reacts with a carboxyl group may be added.
- the tetracarboxylic dianhydride having a tetravalent organic group X preferably used for preparing an ester bond type polyimide precursor has a structure represented by the above general formula (30).
- acid dianhydrides for example, pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride Biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3 ′, 4 4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3 , 3-hexafluoropropane, etc.
- acid dianhydrides for example, pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride,
- Preferred examples include pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, and the like.
- Preferably pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 Examples include ', 4,4'-tetracarboxylic dianhydride.
- More preferable examples include pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, and the like. However, it is not limited to these. These may be used alone or in combination of two or more.
- alcohols having a photopolymerizable group that can be suitably used for preparing an ester bond type polyimide precursor in the present invention include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, and the like.
- 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 2-hydroxyethyl methacrylate), 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3- Mention may be made of phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cycl
- saturated aliphatic alcohol that can be optionally used together with the alcohol having the photopolymerizable group
- a saturated aliphatic alcohol having 1 to 4 carbon atoms is preferable. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.
- the above tetracarboxylic dianhydride suitable for the present invention and the above alcohols are preferably used in the presence of a basic catalyst such as pyridine, preferably in a suitable reaction solvent at a temperature of 20 to 50 ° C. for 4 to 10%. Mix by stirring for hours. Thereby, esterification reaction of an acid anhydride advances and a desired acid / ester body can be obtained (the above formula (D1)).
- a basic catalyst such as pyridine
- the reaction solvent is preferably a solvent that completely dissolves the raw materials, tetracarboxylic dianhydride and alcohols, and the product acid / ester. More preferably, it is a solvent that completely dissolves the photosensitive polyimide precursor that is an amide polycondensation product of the acid / ester and diamine.
- solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogens Hydrocarbons, hydrocarbons, etc. can be mentioned.
- ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
- 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, and tetrahydrofuran
- halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene and the like
- hydrocarbons include hexane, heptane, benzene, toluene, xylene, and the like. These may be used alone or in admixture of two or more as required.
- the acid / ester compound (typically in a solution state dissolved in the reaction solvent) is mixed with an appropriate dehydration condensing agent, preferably under ice-cooling, to thereby convert the acid / ester compound.
- a polyanhydride is obtained (the above formula (D2)).
- an appropriate chloride is added and mixed to convert the acid / ester into a polyacid oxide.
- a diamine having a divalent organic group Y that is preferably used in the present invention is added dropwise by dissolving or dispersing it in a solvent.
- the target photosensitive polyimide precursor can be obtained by carrying out amide polycondensation of both (the said Formula (D3)).
- Diaminosiloxanes may be used in combination with the diamine having the divalent organic group Y.
- the dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N
- Examples include '-disuccinimidyl carbonate.
- the chloride include thionyl chloride and phosphorus pentachloride. As described above, an intermediate polyacid anhydride or polyacid chloride is obtained.
- diamines having a divalent organic group Y that are preferably used for the reaction with the polyanhydride or polyacid chloride obtained as described above are represented by the general formula (31).
- substituents include 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, and 3,3′-dimethyl-4,4.
- '-Diaminodiphenylmethane 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl, etc .; And mixtures thereof.
- examples include 4,4′-diaminobiphenyl, 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl, and the like. More preferred examples include p-phenylenediamine, 4,4′-diaminodiphenyl ether, and mixtures thereof.
- the diamines are not limited to the above examples.
- diaminosiloxanes are used in the preparation of the photosensitive polyimide precursor.
- diamines containing Specific examples of such diaminosiloxanes include 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane. it can.
- a compound having a reactive substituent that reacts with heat or light and a site that reacts with an amino group which is used to introduce a reactive substituent that reacts with heat or light at the end of the main chain
- the compound having a reactive substituent that reacts with heat or light and has a site that also reacts with a carboxyl group include 4-aminostyrene, 4-ethynylaniline, and the like.
- the water absorption by-product of the dehydration condensing agent coexisting in the reaction solution is filtered off as necessary. Thereafter, an appropriate poor solvent such as water, an aliphatic lower alcohol, a mixed solution thereof, or the like is added to the solution containing the polymer component to precipitate the polymer component. Further, if necessary, the polymer is purified by repeating operations such as redissolution and reprecipitation. Then, the target photosensitive polyimide precursor is isolated by performing vacuum drying. In order to improve the degree of purification, ionic impurities may be removed by passing the polymer solution through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent. .
- the weight average molecular weight (Mw) of the ester bond type polyimide precursor is 1,000 or more in terms of polystyrene by gel permeation chromatography (GPC) from the viewpoint of heat resistance and mechanical properties of the film obtained after the heat treatment. It is preferable that it is 3,000 or more.
- the upper limit of the weight average molecular weight (Mw) is preferably 100,000 or less. From the viewpoint of solubility in a developer, the upper limit of the weight average molecular weight (Mw) is more preferably 50,000 or less. Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as a developing solvent for gel permeation chromatography.
- the molecular weight is determined from a calibration curve created using standard monodisperse polystyrene.
- standard monodisperse polystyrene it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
- the i-line absorbance of the pre-baked film formed independently takes various values depending on the molecular structure.
- the i-ray absorbance of the mixture is an arithmetic average of the i-ray absorbance of each component. Therefore, by combining two or more types of photosensitive polyimide precursors at an appropriate ratio, the i-line absorbance of the 10 ⁇ m-thick film after the pre-baking of the photosensitive polyimide precursor is 0 while maintaining the balance between mechanical properties and thermophysical properties. .1 to 2.0.
- the photosensitive resin composition of this invention may further contain components other than the said photosensitive polyimide precursor.
- a photopolymerization initiator is usually used as a photosensitive agent.
- the photopolymerization initiator is preferably a photoradical polymerization initiator, and is a benzophenone derivative such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, Acetophenone derivatives such as 2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl derivatives such as benzyl
- Benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione Oximes such as 2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, benzoyl perchloride, etc.
- the blending amount of these photosensitizers is 1 to 50 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor, and preferably 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics. It is excellent in photosensitivity by mix
- the photosensitive resin composition of the present invention is typically a liquid photosensitive resin composition in which the above-described components and optional components further used as necessary are dissolved in a solvent to form a varnish. used. Therefore, a solvent can be mentioned as another component.
- Other components include, for example, resins other than the above photosensitive polyimide precursors, sensitizers, monomers having a photopolymerizable unsaturated bond, adhesion assistants, thermal polymerization inhibitors, azole compounds, hindered phenol compounds. Etc.
- the solvent examples include polar organic solvents and alcohols.
- a polar organic solvent is preferably used from the viewpoint of solubility in the photosensitive polyimide precursor.
- N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, ⁇ -butyrolactone examples include ⁇ -acetyl- ⁇ -butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and the like. These can be used alone or in combination of two or more.
- the solvent containing alcohol is preferable from a viewpoint of improving the storage stability of the photosensitive resin composition.
- the alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and having no olefinic double bond.
- alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; Lactate esters such as ethyl lactate; Propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- ( propylene glycol monoalkyl ethers such as (n-propyl) ether; Monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether; 2-hydroxyisobutyric acid esters; Dialcohols such as ethylene glycol and propylene glycol; Etc.
- alkyl alcohols such as methyl
- lactic acid esters propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferred.
- ethyl lactate propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1- (n-propyl) ether are more preferable.
- the solvent is, for example, in the range of 30 to 1500 parts by weight, preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the photosensitive polyimide precursor, depending on the desired coating thickness and viscosity of the photosensitive resin composition. Can be used in a range.
- the solvent contains an alcohol having no olefinic double bond
- the content of the alcohol having no olefinic double bond in the entire solvent is preferably 5 to 50% by mass, More preferably, it is 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.
- content of the alcohol which does not have an olefin type double bond is 50 mass% or less, the solubility of the photosensitive polyimide precursor becomes favorable.
- the photosensitive resin composition of the present invention may further contain a resin component other than the above-described photosensitive polyimide precursor.
- the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin.
- the blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor.
- a sensitizer can be arbitrarily blended in order to improve photosensitivity.
- the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal).
- the blending amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor.
- a monomer having a photopolymerizable unsaturated bond can be arbitrarily blended in the photosensitive resin composition of the present invention.
- a monomer is preferably a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator.
- mono- or di (meth) acrylates of ethylene glycol or polyethylene glycol including diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate; Mono- or di (meth) acrylates of propylene glycol or polypropylene glycol; Mono, di or tri (meth) acrylates of glycerol; Cyclohexane di (meth) acrylate; 1,4-butanediol diacrylate and dimethacrylate, 1,6-hexanediol di (meth) acrylate; Di (meth) acrylate of neopentyl glycol; Mono or di (meth) acrylate of bisphenol A; Benzene trimethacrylate; Isobornyl (meth) acrylate; Acrylamide and its derivatives; Methacrylamide and derivatives thereof; Trimethylolpropane tri (meth) acrylate; Di- or tri (meth)
- the blending amount thereof is 100 mass of the photosensitive polyimide precursor.
- the amount is preferably 1 to 50 parts by mass with respect to parts.
- an adhesive aid can be arbitrarily blended in the photosensitive resin composition.
- the adhesion assistant include ⁇ -aminopropyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) ) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone
- adhesion assistants it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength.
- the blending amount thereof is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor.
- a thermal polymerization inhibitor is optionally added to the photosensitive resin composition in order to improve the stability during storage and the photosensitivity.
- the thermal polymerization inhibitor include 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-phenyl
- the blending amount of the thermal polymerization inhibitor when blended in the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor.
- a nitrogen-containing heterocyclic ring such as an azole compound purine derivative is used to suppress discoloration on copper.
- a compound can be arbitrarily blended.
- Examples of the azole compound include 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, hydroxy Phenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5 -Bis ( ⁇ , ⁇ -dimethyl) Rubenzyl) phenyl] -benzotriazole, 2- (3,5-di-tert-
- purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Guanine, N- (3-ethylphenyl) guanine, 2-a Aden
- the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor. From the viewpoint of photosensitivity characteristics, 0.5 to 5 parts by mass is more preferable.
- the compounding amount of the azole compound with respect to 100 parts by mass of the photosensitive polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition of the present invention is formed on copper or copper alloy, copper or copper alloy Surface discoloration is suppressed.
- the compounding amount of the azole compound is 20 parts by mass or less, the photosensitivity is excellent.
- a hindered phenol compound can be arbitrarily blended in place of the azole compound or together with the azole compound.
- the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl.
- 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione and the like are particularly preferred.
- the blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor, and 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. More preferred.
- the compounding quantity with respect to 100 mass parts of photosensitive polyimide precursors of a hindered phenol compound is 0.1 mass part or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, copper Or discoloration and corrosion of copper alloy is prevented.
- the blending amount of the hindered phenol compound is 20 parts by mass or less, the excellent photosensitivity of the photosensitive resin composition is maintained.
- the photosensitive resin composition of the present invention may contain a crosslinking agent.
- the cross-linking agent can cross-link the polyimide produced by heat curing, or the cross-linking agent itself can form a cross-linking network. It can be a cross-linking agent.
- the crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition.
- crosslinking agent examples include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, which are compounds containing a methylol group and / or an alkoxymethyl group.
- phenol novolac type epoxy resin cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol, which are oxirane compounds -Naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1 , 1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglyci Ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalen
- isocyanate group-containing compounds such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, takenate ( (Registered Trademark) 500, 600, Cosmonate (Registered Trademark) NBDI, ND (trade name, manufactured by Mitsui Chemicals), Duranate (Registered Trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402- B80T (trade name, manufactured by Asahi Kasei Chemicals Corporation) and the like.
- the bismaleimide compounds 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4 '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI- 3000, BMI-40 0, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-
- the blending amount is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the photosensitive polyimide precursor.
- the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited.
- the amount is 20 parts by mass or less, the storage stability is excellent.
- the viscosity of the photosensitive resin composition of the present invention is 80 poise or less, preferably 40 poise or less, and more preferably 20 poise or less.
- the viscosity said here is measured at 25 degreeC using the E-type viscosity meter (the Toki Sangyo make, RE80 type
- the viscosity is 80 poise or less, preferably 40 poise or less, more preferably 20 poise or less, the in-plane uniformity of the film thickness after coating is improved.
- the lower limit of the viscosity of the photosensitive resin composition is not particularly limited, but may be 1 poise or more, or 3 poise or more. Further, it may be 5 poise or more, or 8 poise or more.
- the present invention also provides a method for forming a cured relief pattern.
- the method for forming a cured relief pattern in the present invention includes, for example, the following steps: (1) A coating step of forming a photosensitive resin layer on the substrate by coating the photosensitive resin composition of the present invention described above on the substrate; (2) an exposure step of exposing the photosensitive resin layer; (3) a development step of forming a relief pattern by developing the exposed photosensitive resin layer; (4) a heating step of forming a cured relief pattern by heat-treating the relief pattern; In the order described above.
- typical aspects of each process will be described.
- the photosensitive resin composition of this invention is apply
- the substrate for example, a metal substrate made of silicon, aluminum, copper, copper alloy or the like; Resin substrates such as epoxy, polyimide, polybenzoxazole; A substrate on which a metal circuit is formed on the resin substrate; A substrate in which a plurality of metals or a metal and a resin are laminated in multiple layers; Etc. can be used.
- a coating method a method conventionally used for coating a photosensitive resin composition can be used. For example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine or the like, a spray coater or the like can be used.
- the photosensitive resin composition film can be dried.
- a drying method methods such as air drying, heat drying using an oven or a hot plate, vacuum drying, and the like are used.
- a photosensitive resin layer can be formed on the substrate.
- Exposure process In this process, the photosensitive resin layer formed above is exposed.
- the exposure apparatus for example, an exposure apparatus such as a contact aligner, a mirror projection, or a stepper is used. The exposure can be performed through a photomask or reticle having a pattern, or directly.
- the light beam used for exposure is, for example, an ultraviolet light source.
- post-exposure baking PEB
- pre-development baking by any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity.
- the range of baking conditions is preferably a temperature of 40 to 120 ° C. and a time of 10 seconds to 240 seconds. However, as long as the various characteristics of the photosensitive resin composition of the present invention are not impaired, the present invention is not limited to this range.
- the unexposed part of the exposed photosensitive resin layer is developed and removed.
- a developing method for developing the photosensitive resin layer after exposure (irradiation) a conventionally known photoresist developing method can be selected and used. For example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, or the like.
- post-development baking may be performed at any temperature and time combination as necessary.
- the post-development baking temperature can be, for example, 80 to 130 ° C.
- the post-development baking time can be, for example, 0.5 to 10 minutes.
- the developer used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent.
- the good solvent N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone and the like are preferable.
- the poor solvent toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable.
- 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 photosensitive resin composition.
- two or more of each solvent for example, several types may be used in combination.
- the relief pattern obtained by the development is heated to dilute the photosensitive component, and by imidizing the photosensitive polyimide precursor, it is converted into a cured relief pattern made of polyimide.
- various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising type oven capable of setting a temperature program can be selected.
- the heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.
- a cured relief pattern can be produced.
- the photosensitive resin composition of the present invention By using the photosensitive resin composition of the present invention, the flowability of the resin during spin coating is improved, and the state of interaction between the polymers during prebaking is changed. Thereby, the photosensitive resin layer which improved the in-plane uniformity of the coating film thickness can be formed. As a result, a cured relief pattern can be formed with high resolution.
- the photosensitive resin composition of the present invention is useful not only for application to semiconductor devices as described above, but also for applications such as interlayer insulation for multilayer circuits, cover coating for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. is there.
- Weight average molecular weight (Mw) The weight average molecular weight (Mw) of each (A) polyimide precursor was measured by the gel permeation chromatography method (standard polystyrene conversion). Three columns used in the measurement were trade names “Shodex KD-805”, “Shodex KD-804” and “Shodex KD-803” manufactured by Showa Denko KK in series in this order. As the standard monodisperse polystyrene, trade name “Shodex STANDARD SM-105” manufactured by Showa Denko Co., Ltd. was selected.
- N-methyl-2-pyrrolidone containing 0.01 mol / L lithium bromide was used, and the flow rate was measured at 1.0 mL / min.
- the differential refractive index detector is trade name “RI-2031 Plus” manufactured by JASCO Corporation
- the pump is trade name “PU-2080 Plus” manufactured by JASCO Corporation
- the column oven is JASCO Corporation.
- a negative photosensitive resin composition of the present invention was spin-coated on a 6-inch silicon wafer (Fujimi Electronics Industry Co., Ltd., thickness: 625 ⁇ 25 ⁇ m) and dried to obtain a thickness of about 11 ⁇ m.
- the coating film was formed as a photosensitive resin layer.
- This coating film was exposed using a reticle with a test pattern by irradiating energy of 500 mJ / cm 2 with a ghi stepper (Prisma-ghi, manufactured by Ultratech).
- the coating film formed on the wafer was spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone.
- a relief pattern of a polyimide precursor was obtained by rinsing with propylene glycol methyl ether acetate to develop and remove the unexposed portion.
- the wafer on which the relief pattern is formed is cured at 200 ° C. for 2 hours in a nitrogen atmosphere using a temperature rising programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan).
- VF-2000 type manufactured by Koyo Lindberg Co., Ltd., Japan
- the obtained polyimide pattern was immersed in a solution consisting of 1 wt% potassium hydroxide, 39 wt% 3-methoxy-3-methyl-1-butanol and 60 wt% dimethyl sulfoxide at 100 ° C. for 1 hour. After washing with water and air drying, the polyimide coating film was evaluated by film thickness measurement and observation under an optical microscope. Regarding the coating film after immersion, the film thickness fluctuation of the coating film before immersion is within ⁇ 1%, and the case where no crack is generated is “ ⁇ ”, and the film thickness fluctuation of the coating film is within ⁇ 3%. Yes, when the crack does not occur, “ ⁇ ”, when the film thickness variation is within ⁇ 5%, and when the crack does not occur, “ ⁇ ”, the film thickness variation is ⁇ 5 % Or a case where cracks occurred was evaluated as “x”.
- This coating film was irradiated with energy of 300 mJ / cm 2 by a parallel light mask aligner (PLA-501FA type, manufactured by Canon Inc.) using a mask with a test pattern. Subsequently, this coating film was spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO) using cyclopentanone as a developer. Then, a relief pattern on copper was obtained by rinsing with propylene glycol methyl ether acetate.
- the wafer on which the relief pattern was formed on copper was heat-treated at a temperature described in each example for 2 hours in a nitrogen atmosphere using a temperature-programmed cure furnace (VF-2000 type, manufactured by Koyo Lindberg). .
- VF-2000 type temperature-programmed cure furnace
- a cured relief pattern made of polyimide resin having a thickness of about 6 to 7 ⁇ m was obtained on copper.
- the copper surface from which the polyimide resin layer had been completely removed was observed 1000 times from directly above with an FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation). Then, a photograph was taken with the number of pixels of 1280 ⁇ 960 for an area of 126 ⁇ m ⁇ 87 ⁇ m. About the photograph image
- image analysis software A image kun, Asahi Kasei company make
- the area ratio of the void as viewed from above the copper surface was calculated.
- the void area ratio of copper voids is 0 to 3%, " ⁇ ”, when 3-4% is “ ⁇ +”, when 4-5% is “ ⁇ ”, when 5% to 10% “ ⁇ ” is greater than 10%, and “x” is assumed.
- the resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer.
- the produced crude polymer was separated by filtration and dissolved in 1.5 L of ⁇ -butyrolactone to obtain a crude polymer solution.
- the obtained crude polymer solution was dropped into 28 L of water to precipitate a polymer, and the resulting precipitate was filtered off and dried in vacuo to obtain a powdery polymer (polymer (A) -1).
- polymer (A) -1 was measured by gel permeation chromatography (standard polystyrene conversion)
- Mw weight average molecular weight
- N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) 28.57 g was added as bisaminophenol.
- bis (3-amino-4-hydroxyphenyl) hexafluoropropane 6FAP 28.57 g was added as bisaminophenol.
- pyridine was added, and the solution of dicarboxylic acid chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ° C., and stirring was continued for 30 minutes.
- the solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer (A3) -1)).
- the obtained powdery polymer (polymer (A3) -1)) had a weight average molecular weight (Mw) of 10,000.
- a negative photosensitive resin composition was prepared by the following method. 100 g of polymer (A) -2 (corresponding to (A) polyimide precursor), 4 g of B-1 component (corresponding to photopolymerization initiator), 4 g of tetraethylene glycol dimethacrylate (corresponding to (C) -1), It was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (corresponding to (D) -1) and 20 g of ethyl lactate ((E) -1). The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition.
- Examples 2 to 49> A negative photosensitive resin composition was prepared according to the blending amounts shown in Table 2. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance and evaluation of voids on the surface of the copper layer were as shown in Table 2-1.
- Examples 50 to 52> A positive photosensitive resin composition was prepared according to the blending amounts shown in Table 2. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance and evaluation of voids on the surface of the copper layer were as shown in Table 2-1.
- B-1 B-2: B-4: (D) -2 represents ⁇ -butyrolactone, and (E) -2 represents propylene glycol monomethyl ether acetate.
- Example 1 In the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -1 and (B) -1 was changed to (B) -4 in Example 1, a negative photosensitive resin composition was used. Was prepared. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "x" when the void evaluation which occupies for the surface of a copper layer was performed.
- Example 2 In the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -7 and (B) -1 was changed to (B) -4 in Example 1, a negative photosensitive resin composition was used. Was prepared. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "x" when the void evaluation which occupies for the surface of a copper layer was performed.
- Example 3 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -1 in Example 1. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "(triangle
- Example 4 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -7 in Example 1. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "(circle)" when the void evaluation which occupies for the surface of a copper layer was performed.
- Example 6 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -14 in Example 1. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "(circle)" when the void evaluation which occupies for the surface of a copper layer was performed.
- Example 7 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -15 in Example 1. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "(triangle
- Example 8 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -21 in Example 1. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "(circle)" when the void evaluation which occupies for the surface of a copper layer was performed.
- Example 10 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -28 in Example 1. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "(circle)" when the void evaluation which occupies for the surface of a copper layer was performed.
- Example 12 A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer (A) -2 was changed to (A) -35 in Example 1. When this composition was subjected to a chemical resistance test by the above method, the chemical resistance was "x". Moreover, it was "(circle)" when the void evaluation which occupies for the surface of a copper layer was performed.
- the results of Examples 1 to 52 are summarized in Table 2, and the results of Comparative Examples 1 to 12 are summarized in Table 3.
- the (A) polyimide precursor represented by the general formula (1) is a tetravalent organic group having 6 to 40 carbon atoms.
- the structure of X 1 by a particular group it can be assumed that occurrence of chemical resistance and copper voids were particularly excellent results to be suppressed.
- (B) the use of an oxime ester compound as a photopolymerization initiator suppresses chemical resistance and suppression of copper voids. The results can be made particularly excellent.
- the photosensitive resin composition by using a photosensitive resin having a specific weight average molecular weight (Mw), a photosensitive resin composition from which a resin layer having high chemical resistance can be obtained, the photosensitive resin composition It was confirmed that the manufacturing method of the cured relief pattern using a thing can be provided.
- a photosensitive resin having a specific weight average molecular weight (Mw) the polyimide imide cyclization reaction (imidization) proceeds well even under low temperature curing conditions of 200 ° C. or lower. For this reason, it is considered that the polyimide precursor does not remain in the resin film.
- Weight average molecular weight The weight average molecular weight (Mw) of each polyamic acid ester synthesize
- a negative photosensitive resin composition of the present invention was spin-coated on a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness: 625 ⁇ 25 ⁇ m), and dried to give a thickness of about 11 ⁇ m.
- the coating film was formed as a photosensitive resin layer.
- This coating film was exposed using a reticle with a test pattern by irradiating energy of 500 mJ / cm 2 with a ghi stepper (Prisma-ghi, manufactured by Ultratech).
- the coating film formed on the wafer was spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone.
- a relief pattern of a polyimide precursor was obtained by rinsing with propylene glycol methyl ether acetate to develop and remove the unexposed portion.
- the wafer on which the relief pattern is formed is cured at 200 ° C. for 2 hours in a nitrogen atmosphere using a temperature rising programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan).
- VF-2000 type manufactured by Koyo Lindberg Co., Ltd., Japan
- the obtained polyimide pattern was immersed in a solution consisting of 1 wt% potassium hydroxide, 39 wt% 3-methoxy-3-methyl-1-butanol and 60 wt% dimethyl sulfoxide at 100 ° C. for 1 hour. After washing with water and air drying, the polyimide coating film was evaluated by film thickness measurement and observation under an optical microscope. Regarding the coating film after immersion, the film thickness fluctuation of the coating film before immersion is within ⁇ 1%, and the case where no crack is generated is “ ⁇ ”, and the film thickness fluctuation of the coating film is within ⁇ 3%. Yes, when the crack does not occur, “ ⁇ ”, when the film thickness variation is within ⁇ 5%, and when the crack does not occur, “ ⁇ ”, the film thickness variation is ⁇ 5 % Or a case where cracks occurred was evaluated as “x”.
- Example 1 As an acid component, 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2 liter separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of ⁇ -butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.
- ODPA 4,4′-oxydiphthalic dianhydride
- HEMA 2-hydroxyethyl methacrylate
- ⁇ -butyrolactone 400 ml of ⁇ -butyrolactone
- the obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer.
- the produced crude polymer was collected by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then vacuum-dried to obtain a powdery polymer A-1.
- the weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20,000.
- Polymer A-1 100 g which is a polyimide precursor, 1 g-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime 4 g, tetraethylene glycol dimethacrylate 8 g, benzotriazole 0.5 g, N-
- NMP N-methyl-2-pyrrolidone
- ethyl lactate 20 g of ethyl lactate
- both ends of the main chain of the polymer (Wherein a1 includes at least one group of an amide bond, an imide bond, a urea bond, and a urethane bond, b1 is a reactive substituent that crosslinks with heat or light, and e1 is 1 having 1 to 30 carbon atoms.
- R 11 and R 14 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and R 12 and R 13 are each independently a hydrogen atom or 1 to 30 carbon atoms.
- Example 1 except that the type and amount of the acid component, the type and amount of the diamine component, the type and amount of the terminal modifier, and the viscosity (poise) of the negative photosensitive resin composition solution were changed as shown in Table 1.
- a negative photosensitive resin composition solution of Examples 2 to 29 was obtained by carrying out the same method as described in 1.
- Table 1 shows the weight average molecular weight (Mw), evaluation results of in-plane uniformity, and chemical resistance test results of the obtained polymer.
- Example 1 except that the type and amount of the acid component, the type and amount of the diamine component, the type and amount of the terminal modifier, and the viscosity (poise) of the negative photosensitive resin composition solution were changed as shown in Table 1.
- the negative photosensitive resin composition solutions of Reference Examples 1 to 4 were obtained by carrying out the same method as described in 1.
- the negative photosensitive resin composition solutions of Reference Examples 1 to 4 had a viscosity (poise) of 90 of the negative photosensitive resin composition solution.
- Table 1 shows the weight average molecular weight (Mw), evaluation results of in-plane uniformity, and chemical resistance test results of the obtained polymer.
- ⁇ Comparative Example 1> As an acid component, 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2 liter separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of ⁇ -butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.
- ODPA 4,4′-oxydiphthalic dianhydride
- HEMA 2-hydroxyethyl methacrylate
- ⁇ -butyrolactone 400 ml of ⁇ -butyrolactone
- the obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer.
- the produced crude polymer was collected by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer B-1.
- the weight average molecular weight (Mw) of this polymer B-1 was measured and found to be 20,000. This polymer B-1 does not have a reactive substituent that reacts by heat or light at the end of the main chain.
- polymer B-1 which is a polyimide precursor, 4 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime, 8 g of tetraethylene glycol dimethacrylate, 0.5 g of benzotriazole, N—
- NMP N-methyl-2-pyrrolidone
- ethyl lactate 20 g of ethyl lactate
- Comparative Example 2 Comparative Example 1 except that the type and amount of the acid component, the type and amount of the diamine component, the type and amount of the terminal modifier, and the viscosity (poise) of the negative photosensitive resin composition solution were changed as shown in Table 1.
- the negative photosensitive resin composition solution of Comparative Example 2 was obtained by performing the same method as described in 1.
- Table 4 shows the weight average molecular weight (Mw), evaluation results of in-plane uniformity, and chemical resistance test results of the obtained polymer.
- the type and amount of the acid component used in each Example and Comparative Example, the type and amount of the diamine component, the type and amount of the terminal modifier, the viscosity (poise) of the negative photosensitive resin composition solution, and the obtained polymer Table 4 shows the weight average molecular weight (Mw), the in-plane uniformity evaluation results, and the chemical resistance test results.
- a photosensitive polyimide precursor having a reactive substituent that reacts with heat or light at the end of the main chain at the end of the main chain and having a viscosity of 80 poise or less. It can be seen that the negative photosensitive resin composition is excellent in film thickness uniformity and chemical resistance.
- the negative photosensitive resin composition of the present invention can be cured at a low temperature and has excellent chemical resistance.
- it is a photosensitive material useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards. It can be suitably used in the field.
Abstract
Description
本発明は、例えば電子部品の絶縁材料、及び半導体装置におけるパッシベーション膜、バッファーコート膜、層間絶縁膜等のレリーフパターンの形成に用いられるネガ型感光性樹脂組成物、それを用いた硬化レリーフパターンの製造方法に関するものである。
本発明は、例えば電子部品の絶縁材料、及び半導体装置におけるパッシベーション膜、バッファーコート膜、層間絶縁膜等のレリーフパターンの形成に用いられる感光性樹脂組成物、それを用いたポリイミドの製造方法、及び半導体装置に関するものである。
従来、電子部品の絶縁材料、及び半導体装置のパッシベーション膜、表面保護膜、層間絶縁膜等には、優れた耐熱性、電気特性及び機械特性を併せ持つポリイミド樹脂、ポリベンゾオキサゾール樹脂、フェノール樹脂等が用いられている。これらの樹脂の中でも、感光性樹脂組成物の形態で提供されるものは、該組成物の塗布、露光、現像、及びキュアによる熱イミド化処理によって、耐熱性のレリーフパターン皮膜を容易に形成することができる。このような感光性樹脂組成物は、従来の非感光型材料に比べて、大幅な工程短縮を可能にするという特徴を有している。
従来、電子部品の絶縁材料、及び半導体装置のパッシベーション膜、表面保護膜、層間絶縁膜等には、優れた耐熱性、電気特性及び機械特性を併せ持つポリイミド樹脂が用いられている。このポリイミド樹脂の中でも、感光性ポリイミド前駆体組成物の形で提供されるものは、該組成物の塗布、露光、現像、及びキュアによる熱イミド化処理によって、耐熱性のレリーフパターン皮膜を容易に形成することができる(例えば特許文献2参照)。このような感光性ポリイミド前駆体組成物は、従来の非感光型ポリイミド材料に比べて、大幅な工程短縮を可能にするという特徴を有している。
通常、ポリイミド前駆体をキュアして脱水閉環させることにより、ポリイミド樹脂膜を得る場合、300℃以上の高温を必要とする。しかし、当該条件下でキュアすると、デバイスによってはチップの収率が低下するという問題がある。そこで、最近では200℃以下の低温でキュアさせるプロセスが望まれている。
しかしながら、ポリイミド前駆体を200℃以下の低温でキュアした場合、イミド環化反応(イミド化)が不十分であり、樹脂膜中にポリイミド前駆体が残存する。このため、ポリイミド樹脂膜の耐薬品性が十分ではないという問題点があった。
本発明は、このような従来の実情に鑑みて考案されたものであり、200℃以下の低温キュア条件下においても、イミド化率が良好で、耐薬品性が高い樹脂層が得られるネガ型感光性樹脂組成物、該感光性樹脂組成物を用いた硬化レリーフパターンの製造方法を提供することを目的とする。
電子機器の高性能化に伴い、昨今、感光性ポリイミドに対しても解像度と信頼性の両立が求められるようになって来た。そのため、従来、信頼性重視のため、比較的解像度に関しての要求が緩かったネガ型感光性ポリイミドに関しても、高解像度並びに厳しい膜厚の面内均一性が求められるようになってきた。
本発明者らは、特定の重量平均分子量(Mw)を有する感光性樹脂を用いることにより、200℃以下の低温キュア条件下においても、ポリイミドのイミド環化反応(イミド化)が良好に進行し、耐薬品性が高い樹脂層が得られることを見出し、本発明を完成するに至ったものである。すなわち、本発明は以下の通りである。
[1]
(A)ポリイミド前駆体:100質量部;及び
(B)光重合開始剤:0.1質量部~20質量部;
を含むネガ型感光性樹脂組成物であって、
前記(A)ポリイミド前駆体が、下記一般式(1):
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、16,000未満である、前記ネガ型感光性樹脂組成物。
[2]
前記一般式(1)において、X1が、下記一般式(4)~(6):
前記一般式(1)において、Y1が、下記一般式(7):
[3]
前記一般式(1)において、X1が、前記一般式(6)を含み、Y1が、前記一般式(8)を含む、[2]に記載のネガ型感光性樹脂組成物。
[4]
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、[3]に記載のネガ型感光性樹脂組成物。
[5]
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、10,000未満である、[4]に記載のネガ型感光性樹脂組成物。
[6]
前記一般式(1)において、X1が、前記一般式(6)を含み、Y1が、前記一般式(7)を含む、[2]に記載のネガ型感光性樹脂組成物。
[7]
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、[6]に記載のネガ型感光性樹脂組成物。
[8]
前記一般式(1)において、X1が、前記一般式(5)を含み、Y1が、前記一般式(8)を含む、[2]に記載のネガ型感光性樹脂組成物。
[9]
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、[8]に記載のネガ型感光性樹脂組成物。
[10]
前記一般式(1)において、X1が、前記一般式(5)を含み、Y1が、前記一般式(7)及び(9)からなる群から選択される少なくとも1つを含む、[2]に記載のネガ型感光性樹脂組成物。
[11]
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、[10]に記載のネガ型感光性樹脂組成物。
[12]
前記一般式(1)において、X1が、前記一般式(4)を含み、Y1が、前記一般式(7)を含む、[2]に記載のネガ型感光性樹脂組成物。
[13]
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、[12]に記載のネガ型感光性樹脂組成物。
[14]
(A2)ポリベンゾオキサゾール前駆体:100質量部;及び
(B2)光酸発生剤:0.1質量部~20質量部;
を含むポジ型感光性樹脂組成物であって、
前記(A)ポリベンゾオキサゾール前駆体が、下記一般式(12):
であり、
前記(A2)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、16,000未満である、前記ポジ型感光性樹脂組成物。
[15]
前記一般式(12)において、Uは、炭素数1~30の2価の有機基である、[14]に記載のポジ型感光性樹脂組成物。
[16]
前記一般式(12)において、Uは、炭素数1~8で且つ水素原子の一部または全部がフッ素原子で置換された鎖状アルキレン基である、[14]に記載のポジ型感光性樹脂組成物。
[17]
前記一般式(12)において、Vは、芳香族基を含む2価の有機基である、[14]から[16]のいずれかに記載のポジ型感光性樹脂組成物。
[18]
前記一般式(12)において、Vは、下記一般式(13)~(15)で表される少なくとも1つの構造を含む、[17]に記載のポジ型感光性樹脂組成物。
[19]
前記一般式(12)において、Vは、下記一般式(16)で表される構造を含む、[18]に記載のポジ型感光性樹脂組成物。
(1)[1]~[19]のいずれかに記載の感光性樹脂組成物を基板上に塗布することによって感光性樹脂層を前記基板上に形成する工程と、
(2)前記感光性樹脂層を露光する工程と、
(3)前記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工程と、
(4)前記レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する工程とを含む、硬化レリーフパターンの製造方法。
[21]
前記基板が、銅又は銅合金から構成されている、[20]に記載の硬化レリーフパターンの製造方法。
本発明者らは、末端に反応性の置換基を有するポリイミド前駆体を含む、特定の粘度のネガ型感光性樹脂組成物を用いることにより、上記の目的が達成されることを見出し、本発明を完成するに至った。すなわち、本発明は以下の通りである。
〔1〕
主鎖の末端に、熱又は光によって反応する反応性の置換基を有する感光性ポリイミド前駆体を含み、粘度が80ポイズ以下であることを特徴とする、ネガ型感光性樹脂組成物。
〔2〕
前記反応性の置換基が、以下の群:
アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基、イミノ基、イソシアナト基、シアナト基、シクロアルキル基、エポキシ基、オキセタニル基、カーボネート基、ヒドロキシル基、メルカプト基、メチロール基、およびアルコキシアルキル基からなる群から選ばれる少なくとも一つを含む、〔1〕に記載の感光性樹脂組成物。
〔3〕
前記反応性の置換基が、アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基からなる群から選ばれる少なくとも一つを含む、〔2〕に記載の感光性樹脂組成物。
〔4〕
前記反応性の置換基が、メタクリル基を含む、〔3〕に記載の感光性樹脂組成物。
〔5〕
前記感光性ポリイミド前駆体が下記一般式(A1):
前記感光性ポリイミド前駆体の主鎖の少なくとも一方の末端が下記一般式(E1)又は(F1)の構造を有する、〔1〕~〔4〕4のいずれかに記載の感光性樹脂組成物。
〔6〕
前記b1及びg1は末端に二重結合を有する反応性の置換基である〔5〕に記載のネガ型感光性樹脂組成物。
〔7〕
前記感光性ポリイミド前駆体の主鎖の少なくとも一方の末端が、前記一般式(F1)の構造を含む、〔5〕又は〔6〕に記載のネガ型感光性樹脂組成物。
〔8〕
前記f1がアミド基、イミド基、ウレア基、ウレタン基の少なくとも1つの基を含む、〔7〕に記載のネガ型感光性樹脂組成物。
〔9〕
前記b1が、アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基、イミノ基、イソシアナト基、シアナト基、シクロアルキル基、エポキシ基、オキセタニル基、カーボネート基、ヒドロキシル基、メルカプト基、メチロール基、およびアルコキシアルキル基からなる群から選ばれる少なくとも一つを含む、〔5〕に記載の感光性樹脂組成物。
〔10〕
前記b1が、アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基からなる群から選ばれる少なくとも一つを含む、〔9〕に記載の感光性樹脂組成物。
〔11〕
前記b1熱又は光で架橋する反応性の置換基が、メタクリル基を含む、〔10〕に記載の感光性樹脂組成物。
〔12〕
前記g1熱又は光で架橋する反応性の置換基が、アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基、イミノ基、イソシアナト基、シアナト基、シクロアルキル基、エポキシ基、オキセタニル基、カーボネート基、ヒドロキシル基、メルカプト基、メチロール基、およびアルコキシアルキル基からなる群から選ばれる少なくとも一つを含む〔5〕に記載の感光性樹脂組成物。
〔13〕
前記g1熱又は光で架橋する反応性の置換基が、アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基からなる群から選ばれる少なくとも一つを含む、〔12〕に記載の感光性樹脂組成物。
〔14〕
前記g1熱又は光で架橋する反応性の置換基が、メタクリル基を含む、〔13〕に記載の感光性樹脂組成物。
〔15〕
前記一般式(A1)中のXが、下記(B1)~(B3):
Yが、下記(C1)~(C3):
から選ばれる少なくとも1種以上の2価の有機基である、〔5〕に記載の感光性樹脂組成物。
〔16〕
前記一般式(A1)において、Xが、前記一般式(B3)を含み、Yが、前記一般式(C2)を含む、〔15〕に記載のネガ型感光性樹脂組成物。
〔17〕
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、〔16〕に記載のネガ型感光性樹脂組成物。
〔18〕
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、10,000未満である、〔17〕に記載のネガ型感光性樹脂組成物。
〔19〕
前記一般式(A1)において、Xが、前記一般式(B3)を含み、Yが、前記一般式(C1)を含む、〔15〕に記載のネガ型感光性樹脂組成物。
〔20〕
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、〔19〕に記載のネガ型感光性樹脂組成物。
〔21〕
前記一般式(A1)において、Xが、前記一般式(B2)を含み、Yが、前記一般式(C2)を含む、〔15〕に記載のネガ型感光性樹脂組成物。
〔22〕
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、〔21〕に記載のネガ型感光性樹脂組成物。
〔23〕
前記一般式(A1)において、Xが、前記一般式(B2)を含み、Yが、前記一般式(C1)及び(C3)からなる群から選択される少なくとも1つを含む、〔15〕に記載のネガ型感光性樹脂組成物。
〔24〕
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、〔23〕に記載のネガ型感光性樹脂組成物。
〔25〕
前記一般式(A1)において、Xが、前記一般式(B1)を含み、Yが、前記一般式(C1)、を含む、〔15〕に記載のネガ型感光性樹脂組成物。
〔26〕
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、〔25〕に記載のネガ型感光性樹脂組成物。
〔27〕
粘度が40ポイズ以下である、〔1〕~〔26〕のいずれかに記載の感光性樹脂組成物。
〔28〕
粘度が20ポイズ以下である、〔27〕に記載の感光性樹脂組成物。
〔29〕
主鎖の末端に、熱又は光によって反応する反応性の置換基を有する感光性ポリイミド前駆体を含むネガ型感光性樹脂組成物であって、
前記感光性ポリイミド前駆体が下記一般式(A1):
前記感光性ポリイミド前駆体の主鎖の少なくとも一方の末端が下記一般式(E1)又は(F1)で表される構造を有するネガ型感光性樹脂組成物。
〔30〕
前記b1及びg1は末端に二重結合を有する反応性の置換基である〔29〕に記載のネガ型感光性樹脂組成物。
〔31〕
前記感光性ポリイミド前駆体の主鎖の少なくとも一方の末端が、前記一般式(F1)の構造を含む、〔29〕又は〔30〕に記載のネガ型感光性樹脂組成物。
〔32〕
前記f1がアミド基、イミド基、ウレア基、ウレタン基の少なくとも1つの基を含む、〔31〕に記載のネガ型感光性樹脂組成物。
〔33〕
以下の工程:
(1)〔1〕~〔32〕のいずれかに記載の感光性樹脂組成物を基板上に塗布し、該基板上に感光性樹脂層を形成する塗布工程、
(2)該感光性樹脂層を露光する露光工程、
(3)該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現像工程、および、
(4)該レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する加熱工程、
を含むことを特徴とする、硬化レリーフパターンの製造方法。
〔34〕
〔1〕~〔32〕のいずれかに記載の感光性樹脂組成物の製造方法であって、
前記感光性ポリイミド前駆体は、以下の工程:
ジアミンモノマーと酸二無水物モノマーとを、一方が過剰の状態で重縮合反応させることにより、ポリイミドを得る工程、および
前記ポリイミドの末端に残存するアミンまたは酸無水物と、熱又は光によって反応する反応性置換基を有する化合物とを反応させることにより、前記ポリイミドの主鎖の末端に、該反応性置換基を導入する工程、
を含んで合成されることを特徴とする、感光性樹脂組成物の製造方法。
本発明によれば、特定の重量平均分子量(Mw)を有する感光性樹脂を用いることにより、200℃以下の低温キュア条件下においても、ポリイミドのイミド環化反応(イミド化)が良好に進行する。これにより本発明では、樹脂膜中にポリイミド前駆体が残存することが少なく、耐薬品性が高い樹脂層が得られる感光性樹脂組成物、該感光性樹脂組成物を用いた硬化レリーフパターンの製造方法を提供することができる。
本発明によれば、基板上に塗布して膜とした場合、膜厚の面内均一性に優れたネガ型感光性樹脂組成物を提供することができる。
以下、本発明を実施するための形態(以下、単に「本実施形態」という。)について詳細に説明する。なお、本実施形態は本発明を説明するための例示であり、本発明を限定することを意図するものではない。本発明は、その要旨の範囲内で適宜変形して実施することができる。
<ネガ型感光性樹脂組成物>
本発明は、(A)ポリイミド前駆体を100質量部、及び(B)光重合開始剤を0.1質量部~20質量部を含み、前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、16,000未満であることを特徴とするネガ型感光性樹脂組成物である。
本発明に用いられる(A)ポリイミド前駆体について説明する。本発明の(A)ポリイミド前駆体は、ポリアミド酸エステル又はポリアミド酸塩から成る群より選ばれる少なくとも一種の樹脂を主成分とする。ここで、主成分とは、これらの樹脂を全樹脂の50質量%以上含有することを意味し、60質量%以上含有することが好ましい。また、必要に応じて他の樹脂を含んでいてもよい。
この中で、X1が一般式(5)を含み、且つ、Y1が一般式(7)または(8)または(9)を含む構造が耐薬品性と銅ボイドの抑制効果の観点から好ましい。
この中で、X1が一般式(4)を含み、且つ、Y1が一般式(7)を含む構造が耐薬品性と銅ボイドの抑制効果の観点から好ましい。
この中で、X1が一般式(6)を含む構造が耐薬品性と銅ボイドの抑制効果に優れるため好ましい。特に耐薬品性と銅ボイドの抑制効果の観点から、X1が一般式(6)を含む構造で、且つ、Y1が一般式(8)または(7)を含む構造がより好ましく、X1が一般式(6)を含む構造で、且つ、Y1が一般式(8)を含む構造が最も好ましい。
これらの組み合わせは耐薬品性と銅ボイドの抑制効果に優れるため特に好ましいが、これらに限定されるものではない。
また、m2は、感光特性の観点から、2以上、10以下の整数、好ましくは2以上、4以下の整数である。
本発明で、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、4価の有機基X1を含むテトラカルボン酸二無水物としては、上記一般式(30)に示されるテトラカルボン酸二無水物をはじめ、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等を、好ましくは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を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。
上記アシッド/エステル体(典型的には後述する溶剤中の溶液)に、氷冷下、適当な脱水縮合剤、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を投入混合することにより、アシッド/エステル体をポリ酸無水物とする。その後、得られたアシッド/エステル体のポリ酸無水物に、本発明で好適に用いられる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、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。もしくは、上記アシッド/エステル体を、塩化チオニル等を用いてアシッド部分を酸クロライド化した後に、ピリジン等の塩基存在下に、ジアミン化合物と反応させることにより、目的のポリイミド前駆体を得ることができる。
上記(A)ポリイミド前駆体の重量平均分子量(Mw)の下限は、4,000以上であってもよく、5,000以上であってもよく、6,000以上であってもよく、7,000以上であってもよい。上記(A)ポリイミド前駆体の重量平均分子量(Mw)の上限は、
15,000以下であってもよく、13,000以下であってもよく、12,000以下であってもよく、11,000以下であってもよく、10,000以下であってもよく、10,000未満であってもよい。
本発明に用いられる(B)光重合開始剤について説明する。(B)光重合開始剤の、ネガ型感光性樹脂組成物中の配合量は、(A)ポリイミド前駆体100質量部に対して、0.1質量部~20質量部である。上記配合量は、光感度又はパターニング性の観点で0.1質量部以上であり、硬化性又は硬化後の感光性樹脂層の膜物性の観点から20質量部以下である。
オキシムエステル系光開始剤を使用、または、特定のポリイミドを使用することにより、銅層とポリイミド層との密着性を高めることができ、ボイドの発生を抑制することができる。
で表されるオキシムエステル化合物である。
このようなオキシムエステル系光開始剤を用いることにより、イミド化率が良好で、耐薬品性が高く、かつ、銅ボイドの発生を抑制できる樹脂層が得られる。
(B2)光酸発生剤、を含むポジ型感光性樹脂組成物を用いることもできる。
ポリベンゾオキサゾール前駆体組成物に用いる感光性樹脂としては、下記一般式(12)で表される繰り返し単位を含むポリ(o-ヒドロキシアミド)を用いることができる。
光酸発生剤は、光照射部のアルカリ水溶液可溶性を増大させる機能を有するものである。光酸発生剤としては、ジアゾナフトキノン化合物、アリールジアゾニウム塩、ジアリールヨードニウム塩、トリアリールスルホニウム塩等が挙げられる。このうち、ジアゾナフトキノン化合物は、感度が高く好ましい。
本実施形態に係る(A)ポリベンゾオキサゾール前駆体の重量平均分子量(Mw)の好適な範囲は、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、16,000未満である。当該範囲の重量平均分子量(Mw)の(A)ポリベンゾオキサゾール前駆体を用いることで、200℃以下のキュア条件下においても、ポリベンゾオキサゾールの環化反応が良好に進行し、耐薬品性が高く、かつ、銅ボイドの発生を抑制できる樹脂層が得られる。重量平均分子量(Mw)が当該範囲よりも大きいと、キュア条件中で(A2)ポリベンゾオキサゾール前駆体の分子運動が不十分で環化が進行し難くなり、得られる樹脂層の耐薬品性が十分でなく、銅ボイドが発生しやすくなる。一方で、重量平均分子量(Mw)が当該範囲よりも小さいと、キュア条件中で(A2)ポリベンゾオキサゾール前駆体の分子運動は活発になりイミド化は進行し易くなる。一方で(A2)ポリベンゾオキサゾール前駆体の重量平均分子量(Mw)が小さい為、キュア後に得られる樹脂層の耐薬品性が十分ではなく、銅ボイドの発生を抑制しやすくなる。重量平均分子量(Mw)が当該範囲の(A2)ポリベンゾオキサゾール前駆体を用いることで、200℃以下のキュア条件下でも環化率が良好で、かつ、得られる硬化膜の耐薬品性が良好で、かつ、銅ボイドの発生を抑制できる樹脂を得られる。
なお、上記(A2)ポリベンゾオキサゾール前駆体の重量平均分子量(Mw)のより好ましい範囲は、3,000以上、15,000以下、さらに好ましくは3,000以上、13,000以下、さらに好ましくは3,000以上、11,000以下、さらに好ましくは3,000以上、10,000以下、更に好ましくは、3,000以上、10,000未満、更に好ましくは、3,000以上、9,500以下、特に好ましくは、3,000以上、9,000以下、である。上記(A2)ポリベンゾオキサゾール前駆体の重量平均分子量(Mw)の下限は、4,000以上であってもよく、5,000以上であってもよく、6,000以上であってもよく、7,000以上であってもよい。上記(A2)ポリベンゾオキサゾール前駆体の重量平均分子量(Mw)の上限は、15,000以下であってもよく、13,000以下であってもよく、12,000以下であってもよく、11,000以下であってもよく、10,000以下であってもよく、10,000未満であってもよい。
溶剤としては、アミド類、スルホキシド類、ウレア類、ケトン類、エステル類、ラクトン類、エーテル類、ハロゲン化炭化水素類、炭化水素類、アルコール類等が挙げられる。
例えば、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ジメチルスルホキシド、テトラメチル尿素、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、酢酸メチル、酢酸エチル、酢酸ブチル、シュウ酸ジエチル、乳酸エチル、乳酸メチル、乳酸ブチル、γ-ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、ベンジルアルコール、フェニルグリコール、テトラヒドロフルフリルアルコール、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、モルフォリン、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、アニソール、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、メシチレン等を使用することができる。中でも、樹脂の溶解性、樹脂組成物の安定性、及び基板への接着性の観点から、N-メチル-2-ピロリドン、ジメチルスルホキシド、テトラメチル尿素、酢酸ブチル、乳酸エチル、γ-ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ベンジルアルコール、フェニルグリコール、及びテトラヒドロフルフリルアルコールが好ましい。
I)チタンキレート化合物:中でも、アルコキシ基を2個以上有するチタンキレートが、ネガ型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。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)等である。
熱酸発生剤は、硬化温度を下げた場合でも、良好な硬化物の熱物性及び機械的物性を発現させるという観点から、配合することが好ましい。
ジ(t-ブチルフェニル)ヨードニウム塩等のジ(アルキルアリール)ヨードニウム塩;
トリメチルスルホニウム塩のようなトリアルキルスルホニウム塩;ジメチルフェニルスルホニウム塩等のジアルキルモノアリールスルホニウム塩;
ジフェニルメチルスルホニウム塩等のジアリールモノアルキルヨードニウム塩;トリアリールスルホニウム塩等が挙げられる。
また、本発明は、(1)上述した本発明のネガ型感光性樹脂組成物を基板上に塗布することによって樹脂層を該基板上に形成する工程と、(2)該樹脂層を露光する工程と、(3)該露光後の樹脂層を現像してレリーフパターンを形成する工程と、(4)該レリーフパターンをキュアすることによって硬化レリーフパターンを形成する工程とを含む、硬化レリーフパターンの製造方法を提供する。以下、各工程の典型的な態様について説明する。
本工程では、本発明のネガ型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乾燥させて樹脂層を形成する。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。
本工程では、上記で形成した樹脂層を、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を用いて、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、紫外線光源等により露光する。
本工程においては、露光後の感光性樹脂層の未露光部を現像除去する。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。
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キュアすることによって、硬化レリーフパターンに変換する。キュアの方法としては、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。キュアは、例えば150℃~400℃で30分~5時間の条件で行うことができる。キュアの際の雰囲気気体としては空気を用いてもよく、窒素、アルゴン等の不活性ガスを用いることもできる。
本発明はまた、上述した本発明の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含む、半導体装置を提供する。本発明は、半導体素子である基材と、前記基材上に、上述した硬化レリーフパターン製造方法により形成された樹脂の硬化レリーフパターンとを含む半導体装置も提供する。また、本発明は、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。本発明の半導体装置は、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。
本発明の実施の形態について、以下に具体的に説明する。なお本明細書を通じ、一般式において同一符号で表されている構造は、分子中に複数存在する場合、互いに同一でも異なっていてもよい。
<感光性樹脂組成物>
本発明の感光性樹脂組成物は、主鎖の末端に、反応性の置換基を有する感光性ポリイミド前駆体を含む、粘度が80ポイズ以下のネガ型感光性樹脂であることを特徴とする。
本発明に用いられる、末端に反応性の置換基を有する感光性ポリイミド前駆体について説明する。
本発明における感光性ポリイミド前駆体として好ましく用いられるのは、i線吸光度が0.1~2.0のものである。i線吸光度は、感光性ポリイミド前駆体を単独の溶液として塗布し、プリベークした後に得られる、10μm厚フィルムについて測定される。
感光性樹脂組成物から得られる硬化レリーフパターンにおける、開口部の側面を順テーパー型にするために、本発明の感光性樹脂組成物は、上記の要件を満たす感光性ポリイミド前駆体を含有することが好ましい。
<i線吸光度の求め方>
10μm厚フィルムのi線吸光度は、感光性ポリイミド前駆体を単独で石英ガラス上に形成した塗膜について、プリベークした後、通常の分光光度計により測定することができる。形成されたフィルムの厚みが10μmでない場合には、該フィルムについて得られた吸光度を、ランベルト・ベールの法則に従って10μm厚に換算することにより、10μm厚のi線吸光度を求めることができる。
i線吸光度が0.1未満の場合には、これを満たす感光性ポリイミド前駆体の構造が限定されるため、機械物性、熱物性等が劣ることとなる。i線吸光度が2.0を超える場合には、塗膜のi線吸収が大きすぎて底部まで光が到達しない。そのため、ネガ型の場合、塗膜の底部が硬化しないという問題が出る場合がある。
で表される構造が挙げられるが、これらに限定されるものではない。また、Xの構造は1種でも2種以上の組み合わせでも構わない。上記式で表される構造を有するX基は、耐熱性と感光特性とを両立するという点で特に好ましい。
で表される構造が挙げられるが、これらに限定されるものではない。また、Yの構造は1種でも2種以上の組み合わせでも構わない。上記式(31)で表される構造を有するY基は、耐熱性及び感光特性を両立するという点で特に好ましい。
価の有機基であり、互いに異なっていても、同一であってもよい。)
から選ばれる少なくとも1種以上の2価の有機基が挙げられる。これらの有機基は、膜厚の面内均一性を向上させる観点から特に好ましいが、これらに限定されるものではない。その中でも特に、一般式(A1)中のYが、前記(C3)を含有することが好ましい。
この中で、Xが一般式(B2)を含み、Yが一般式(C1)または(C2)または(C3)を含む構造が好ましい。
この中で、Xが一般式(B1)を含み、Yが一般式(C1)を含む構造が好ましい。
これらの組み合わせは耐薬品性と銅ボイドの抑制効果に優れるため特に好ましいが、これらに限定されるものではない。これらの組み合わせの中で、耐薬品性と銅ボイドの抑制効果の観点から、Xが一般式(B3)を含み、Yが一般式(C2)を含む構造が最も好ましい。
上記(A)ポリイミド前駆体の重量平均分子量(Mw)の下限は、4,000以上であってもよく、5,000以上であってもよく、6,000以上であってもよく、7,000以上であってもよい。上記(A)ポリイミド前駆体の重量平均分子量(Mw)の上限は、15,000以下であってもよく、13,000以下であってもよく、12,000以下であってもよく、11,000以下であってもよく、10,000以下であってもよく、10,000未満であってもよい。
(ただしR16、R17、R18は同時に水素原子になることはない。)
上記一般式(E1)および(F1)において、b1及びg1は、末端に二重結合を有する反応性の置換基であることが、現像後ベークによる架橋の観点から好ましい。
またf1がアミド基、イミド結合、ウレア基、ウレタン基の少なくとも1つの基を含むことが好ましい。f1がエステル基であると加水分解しやすいので架橋されない可能性がある。これらの4つの基(アミド基、イミド結合、ウレア基、ウレタン基)は、加水分解されにくいので、現像後ベークによる架橋が効率よく行われる。そのため、耐薬品性が高い。
膜厚均一性の観点から、b1は、アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基から選ばれる少なくとも一つであることが好ましい。特にメタクリル基が好ましい。
膜厚均一性の観点から、g1は、アクリル基、メタクリル基、ビニル基、アルケニル基、シクロアルケニル基、アルカジエニル基、シクロアルカジエニル基、スチリル基、エチニル基から選ばれる少なくとも一つであることが好ましい。特にメタクリル基が好ましい。
本発明において、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、4価の有機基Xを有するテトラカルボン酸二無水物としては、上記一般式(30)に示される構造を有する酸二無水物をはじめ、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等を挙げることができる。好ましくは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、ビフェニル-3,3’,4,4’-テトラカルボン酸二無水物等を挙げることができる。好ましくは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等を挙げることができる。より好ましくは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、ビフェニル-3,3’,4,4’-テトラカルボン酸二無水物等を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、これらは単独でも、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を;
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
を;
ラクトン類として、例えば、γ-ブチロラクトン等を;
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を;
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を;
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、キシレン等を、それぞれ挙げることができる。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することにより、アシッド/エステル体をポリ酸無水物とする(上記式(D2))。もしくは適当な塩化物を投入混合することにより、アシッド/エステル体をポリ酸酸化物とする。次いでこれに、本発明で好適に用いられる2価の有機基Yを有するジアミン類を、別途溶媒に溶解又は分散させたものを滴下投入する。そして、両者をアミド重縮合させることにより、目的の感光性ポリイミド前駆体を得ることができる(上記式(D3))。上記2価の有機基Y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。上記塩化物としては、例えば、塩化チオニル、五塩化リン等が挙げられる。
以上のようにして、中間体であるポリ酸無水化物もしくはポリ酸塩化物が得られる。
及びこれらのベンゼン環上の水素原子の一部が、メチル基、エチル基、ヒドロキシメチル基、ヒドロキシエチル基、ハロゲン原子等で置換されたもの;
並びにこれらの混合物等が挙げられる。
及びこれらの混合物等が挙げられる。これらの中で好ましく用いられるものとして、p-フェニレンジアミン、4,4’-ジアミノジフェニルエーテル、2,2’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ビス(トリフルオロメチル)-4,4‘-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4‘-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等を挙げることができる。より好ましくはp-フェニレンジアミン、4,4’-ジアミノジフェニルエーテル等を、並びにこれらの混合物等を挙げることができる。ジアミン類は、上記の例示に限定されるものではない。
(1)無水マレイン酸:
本発明の感光性樹脂組成物は、上記感光性ポリイミド前駆体以外の成分を更に含有してもよい。
本発明の感光性樹脂組成物には、通常、感光剤としては光重合開始剤が用いられる。光重合開始剤としては、光ラジカル重合開始剤であることが好ましく、ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-ベンゾイル-4’-メチルジフェニルケトン、ジベンジルケトン、フルオレノン等のベンゾフェノン誘導体、2,2’-ジエトキシアセトフェノン、2-ヒドロキシ-2-メチルプロピオフェノン、1-ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン誘導体、チオキサントン、2-メチルチオキサントン、2-イソプロピルチオキサントン、ジエチルチオキサントン等のチオキサントン誘導体、ベンジル、ベンジルジメチルケタール、ベンジル-β-メトキシエチルアセタール等のベンジル誘導体、
溶剤としては、感光性ポリイミド前駆体に対する溶解性の点から、極性の有機溶剤を用いることが好ましい。具体的には、例えば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、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、シクロペンタノン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、テトラメチル尿素、1,3-ジメチル-2-イミダゾリノン、N-シクロヘキシル-2-ピロリドン等が挙げられる。これらは単独又は2種以上の組合せで用いることができる。
具体的な例としては、例えばメチルアルコール、エチルアルコール、n-プロピルアルコール、イソプロピルアルコール、n-ブチルアルコール、イソブチルアルコール、tert-ブチルアルコール等のアルキルアルコール類;
乳酸エチル等の乳酸エステル類;
プロピレングリコール-1-メチルエーテル、プロピレングリコール-2-メチルエーテル、プロピレングリコール-1-エチルエーテル、プロピレングリコール-2-エチルエーテル、プロピレングリコール-1-(n-プロピル)エーテル、プロピレングリコール-2-(n-プロピル)エーテル等のプロピレングリコールモノアルキルエーテル類;
エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコール-n-プロピルエーテル等のモノアルコール類;
2-ヒドロキシイソ酪酸エステル類;
エチレングリコール、プロピレングリコール等のジアルコール類;
等を挙げることができる。
これらの中では、乳酸エステル類、プロピレングリコールモノアルキルエーテル類、2-ヒドロキシイソ酪酸エステル類、及びエチルアルコールが好ましい。特に乳酸エチル、プロピレングリコール-1-メチルエーテル、プロピレングリコール-1-エチルエーテル、及びプロピレングリコール-1-(n-プロピル)エーテルがより好ましい。
以下に限定されるものではないが、特に、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又はジ(メタ)アクリレート;
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又はジ(メタ)アクリレート;
グリセロールのモノ、ジ又はトリ(メタ)アクリレート;
シクロヘキサンジ(メタ)アクリレート;
1,4-ブタンジオールのジアクリレート及びジメタクリレート、1,6-ヘキサンジオールのジ(メタ)アクリレート;
ネオペンチルグリコールのジ(メタ)アクリレート;
ビスフェノールAのモノ又はジ(メタ)アクリレート;
ベンゼントリメタクリレート;
イソボルニル(メタ)アクリレート;
アクリルアミド及びその誘導体;
メタクリルアミド及びその誘導体;
トリメチロールプロパントリ(メタ)アクリレート;
グリセロールのジ又はトリ(メタ)アクリレート;
ペンタエリスリトールのジ、トリ、又はテトラ(メタ)アクリレート;
並びに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。
感光性樹脂組成物の粘度の下限は特に限定はないが、1ポイズ以上であってもよく、3ポイズ以上であってもよい。また、5ポイズ以上であってもよく、8ポイズ以上であってもよい。
本発明はまた、硬化レリーフパターンの形成方法も提供する。
本発明における硬化レリーフパターンの形成方法は、例えば以下の工程:
(1)上述した本発明の感光性樹脂組成物を基板上に塗布することにより、該基板上に感光性樹脂層を形成する塗布工程と、
(2)感光性樹脂層を露光する露光工程と、
(3)露光後の感光性樹脂層を現像することによりレリーフパターンを形成する現像工程と、
(4)レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する加熱工程と、
を上記に記載の順に含むことを特徴とする。
以下、各工程の典型的な態様について説明する。
本工程では、本発明の感光性樹脂組成物を基板上に塗布し、必要に応じて、その後乾燥させることにより感光性樹脂層を形成する。
基板としては、例えばシリコン、アルミニウム、銅、銅合金等から成る金属基板;
エポキシ、ポリイミド、ポリベンゾオキサゾール等の樹脂基板;
前記樹脂基板に金属回路が形成された基板;
複数の金属、又は金属と樹脂とが多層に積層された基板;
等を使用することができる。
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を用いることができる。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。
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を選択して使用することができる。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である。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。現像後ベークの温度は、例えば80~130℃とすることができる。現像後ベーク時間は例えば0.5~10分とすることができる。
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、感光性ポリイミド前駆体をイミド化させることにより、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200℃~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を製造することができる。
本発明の感光性樹脂組成物を用いることにより、スピンコート時の樹脂のフロー性が向上し、かつプリベーク時のポリマー間の相互作用の状態が変わる。これにより、塗布膜厚の面内均一性を向上した感光性樹脂層を形成することができる。ひいては、硬化レリーフパターンを高解像度で形成することができる。
以下、実施例により本発明を具体的に説明するが、本発明はこれに限定されるものではない。実施例、比較例、及び製造例においては、ネガ型感光性樹脂組成物の物性を以下の方法に従って測定及び評価した。
各(A)ポリイミド前駆体の重量平均分子量(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)で測定した。測定に用いたカラムは昭和電工(株)製の商標名「Shodex KD-805」「Shodex KD-804」「Shodex KD-803」を、3本この順で直列に接続した。標準単分散ポリスチレンは、昭和電工(株)製の商標名「Shodex STANDARD SM-105」を選択した。展開溶媒は、0.01mol/Lの臭化リチウムを含有したN-メチル-2-ピロリドンを使用し、流速は1.0mL/分で測定した。示差屈折率検出器は、日本分光(株)製の商標名「RI-2031 Plus」、ポンプは、日本分光(株)製の商標名「PU-2080 Plus」、カラムオーブンは、日本分光(株)製の商標名「CO-2065 Plus」を使用して測定した。
6インチシリコンウェハー(フジミ電子工業株式会社製、厚み625±25μm)上に本発明のネガ型感光性樹脂組成物をスピン塗布し、乾燥することにより、約11μm厚の塗膜を感光性樹脂層として形成した。この塗膜にテストパターン付レチクルを用いてghiステッパー(Prisma-ghi、ウルトラテック社製)により、500mJ/cm2のエネルギーを照射して露光した。次いで、ウェハー上に形成した塗膜を、シクロペンタノンを用いて、現像機(D-SPIN636型、日本国、大日本スクリーン製造社製)でスプレー現像した。そして、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して未露光部を現像除去することにより、ポリイミド前駆体のレリーフパターンを得た。レリーフパターンを形成したウェハーを、昇温プログラム式キュア炉(VF-2000型、日本国、光洋リンドバーグ社製)を用いて、窒素雰囲気下、200℃で2時間キュアすることにより、約9μm厚のポリイミドの硬化レリーフパターンを得た。
浸漬後の塗膜について、浸漬前に対する塗膜の膜厚変動が±1%以内であり、かつ、クラックが発生していない場合を「◎」、塗膜の膜厚変動が±3%以内であり、かつ、クラックが発生していない場合を「○」、塗膜の膜厚変動が±5%以内であり、かつ、クラックが発生していない場合を「△」、膜厚変動が±5%を超えている、又はクラックが発生している場合を「×」と評価した。
6インチシリコンウェハー(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厚の銅をこの順にスパッタした。続いて、このウェハー上に、後述の方法により調製した感光性ポリアミド酸エステル組成物を、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、乾燥することにより10μm厚の塗膜を形成した。この塗膜に、テストパターン付マスクを用いて、平行光マスクアライナー(PLA-501FA型、キヤノン社製)により300mJ/cm2のエネルギーを照射した。次いで、この塗膜を、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)でスプレー現像した。そして、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、銅上のレリーフパターンを得た。
まず、銅上に該硬化レリーフパターンを形成したウェハーを、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、湿度5%の空気中で、150℃で168時間加熱した。続いて、プラズマ表面処理装置(EXAM型、神港精機社製)を用いて、銅上のポリイミド樹脂層をプラズマエッチングにより除去した。プラズマエッチング条件は下記の通りである。
出力:133W
ガス種・流量:O2:40ml/分 + CF4:1ml/分
ガス圧:50Pa
モード:ハードモード
エッチング時間:1800秒
なお、銅ボイドの発生面積比率が0~3%の場合を「◎」、3~4%の場合を「○+」、4~5%の場合を「○」、5%~10%の場合を「△」、10%よりも大きい場合を「×」とした。
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2L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)131.2gとγ―ブチロラクトン400mLを入れて室温下で攪拌し、攪拌しながらピリジン81.5gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間放置した。
ポリマー(A)-1の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は2,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから45.1gに変更した以外は、製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-2)の重量平均分子量(Mw)は3,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから57.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-3)の重量平均分子量(Mw)は11,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから60.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-4)の重量平均分子量(Mw)は12,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから67.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-5)の重量平均分子量(Mw)は15,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから70.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-6)の重量平均分子量(Mw)は16,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから75.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-7)の重量平均分子量(Mw)は17,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-8)の重量平均分子量(Mw)は2,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから45.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-9)の重量平均分子量(Mw)は3,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから57.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-10)の重量平均分子量(Mw)は11,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから60.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-11)の重量平均分子量(Mw)は12,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから67.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-12)の重量平均分子量(Mw)は15,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから70.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-13)の重量平均分子量(Mw)は16,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)の添加量を40.0gから75.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-14)の重量平均分子量(Mw)は17,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)21.6gに変更した以外は製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-15)の重量平均分子量(Mw)は2,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)24.3gに変更した以外は製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-16)の重量平均分子量(Mw)は3,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)30.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-17)の重量平均分子量(Mw)は11,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)32.4gに変更した以外は製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-18)の重量平均分子量(Mw)は12,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)36.2gに変更した以外は製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-19)の重量平均分子量(Mw)は15,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)37.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-20)の重量平均分子量(Mw)は16,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)40.6gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-21)の重量平均分子量(Mw)は17,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-2,2’-ジメチルベンジジン(m-TB)42.5gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-22)の重量平均分子量(Mw)は2,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-2,2’-ジメチルベンジジン(m-TB)47.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-23)の重量平均分子量(Mw)は3,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-2,2’-ジメチルベンジジン(m-TB)60.5gに変更した以外は、製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-24)の重量平均分子量(Mw)は11,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-2,2’-ジメチルベンジジン(m-TB)63.7gに変更した以外は製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-25)の重量平均分子量(Mw)は12,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-2,2’-ジメチルベンジジン(m-TB)71.1gに変更した以外は、製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-26)の重量平均分子量(Mw)は15,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-2,2’-ジメチルベンジジン(m-TB)74.3gに変更した以外は、製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-27)の重量平均分子量(Mw)は16,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-2,2’-ジメチルベンジジン(m-TB)79.6gに変更した以外は製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A)-28)の重量平均分子量(Mw)は17,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)64.0gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-29)の重量平均分子量(Mw)は2,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)72.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-30)の重量平均分子量(Mw)は3,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)91.3gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-31)の重量平均分子量(Mw)は11,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)96.1gに変更した以外は製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-32)の重量平均分子量(Mw)は12,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)107.3gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-33)の重量平均分子量(Mw)は15,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)112.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-34)の重量平均分子量(Mw)は16,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)120.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-35)の重量平均分子量(Mw)は17,000であった。
製造例1において、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、2,3,6,7-ナフタレンテトラカルボン酸二無水物(NTCDA)134.0gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを4,4’-チオジアニリン(TDA)59.5gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A)-36)の重量平均分子量(Mw)は10,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)24.3gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-1)の重量平均分子量(Mw)は3,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)30.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-2)の重量平均分子量(Mw)は11,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)32.4gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-3)の重量平均分子量(Mw)は12,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)36.2gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-4)の重量平均分子量(Mw)は15,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)37.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-5)の重量平均分子量(Mw)は16,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ジメチルベンジジン(m-TB)47.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-6)の重量平均分子量(Mw)は3,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ジメチルベンジジン(m-TB)60.5gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-7)の重量平均分子量(Mw)は11,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ジメチルベンジジン(m-TB)63.7gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-8)の重量平均分子量(Mw)は12,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ジメチルベンジジン(m-TB)71.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-9)の重量平均分子量(Mw)は15,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ジメチルベンジジン(m-TB)74.3gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-10)の重量平均分子量(Mw)は16,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)72.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-11)の重量平均分子量(Mw)は3,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)91.3gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-12)の重量平均分子量(Mw)は11,000であった。
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)96.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-13)の重量平均分子量(Mw)は12,000であった。
<製造例50>(ポリマー(A2)-14の合成)
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)107.3gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-14)の重量平均分子量(Mw)は15,000であった。
<製造例51>(ポリマー(A2)-15の合成)
製造例1において、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを2,2’-ビス(トリフルオロメチル)ベンジジン(TFMB)112.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-15)の重量平均分子量(Mw)は16,000であった。
<製造例52>(ポリマー(A2)-16の合成)
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを48.1gに変更した以外は、製造例1と同様にして合成した。得られた粉末状のポリマー(ポリマー(A2)-16)の重量平均分子量(Mw)は5,000であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを52.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-17)の重量平均分子量(Mw)は9,500であった。
製造例1において、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、4,4’-オキシジフタル酸二無水物(ODPA)155.1gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを62.1gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-18)の重量平均分子量(Mw)は13,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)24.3gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-19)の重量平均分子量(Mw)は3,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)30.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-20)の重量平均分子量(Mw)は11,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)32.4gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-21)の重量平均分子量(Mw)は12,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)36.2gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-22)の重量平均分子量(Mw)は15,000であった。
製造例1において、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、ピロメリット酸無水物(PMDA)109.6gに変更し、4,4’-ジアミノジフェニルエーテル(DADPE)40.0gを1,4-フェニレンジアミン(PPD)37.8gに変更した以外は、製造例1と同様にして合成した。
得られた粉末状のポリマー(ポリマー(A2)-23)の重量平均分子量(Mw)は16,000であった。
攪拌機、温度計を備えた0.5リットルのフラスコ中に、ジカルボン酸として4,4’-ジフェニルエーテルジカルボン酸15.48g、N-メチルピロリドンを仕込み、フラスコを5℃に冷却した後、塩化チオニルを滴下し、30分間反応させて、ジカルボン酸クロリドの溶液を得た。次いで、攪拌機、温度計を備えた0.5リットルのフラスコ中に、N-メチルピロリドンを仕込み、ビスアミノフェノールとしてビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン(6FAP)28.57gとm-アミノフェノール2.18gを攪拌溶解した後、ピリジンを添加し、温度を0~5℃に保ちながら、ジカルボン酸クロリドの溶液を30分間で滴下した後、30分間攪拌を続けた。溶液を3リットルの水に投入し、析出物を回収、純水で3回洗浄した後、減圧乾燥してポリマー(ポリベンゾオキサゾール前駆体(ポリマー(A3)-1))を得た。
得られた粉末状のポリマー(ポリマー(A3)-1))の重量平均分子量(Mw)は10,000であった。
ジカルボン酸をセバシン酸(12.13g)に変更した以外は前述のポリマー(A3)-1に記載の方法と同様にして反応を行い、ポリベンゾオキサゾール前駆体(A3)-2を得た。
得られた粉末状のポリマー(ポリマー(A3)-2)の重量平均分子量(Mw)は11,000であった。
ジカルボン酸をジシクロペンタジエンジカルボン酸(DCPD)(11.3g)に変更した以外は前述のポリマー(A3)-1に記載の方法と同様にして反応を行い、ポリベンゾオキサゾール前駆体(A3)-3を得た。
得られた粉末状のポリマー(ポリマー(A3)-3)の重量平均分子量(Mw)は9,000であった。
ポリマー(A)-2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た。
ポリマー(A)-2((A)ポリイミド前駆体に該当)100gを、B-1成分(光重合開始剤に該当)4g、テトラエチレングリコールジメタクリレート((C)-1に該当)4gと共に、N-メチル-2-ピロリドン((D)-1に該当)80gと乳酸エチル((E)-1)20gからなる混合溶媒に溶解した。得られた溶液の粘度を、少量の前記混合溶媒を更に加えることによって約35ポイズ(poise)に調整し、ネガ型感光性樹脂組成物とした。
この組成物について、上述の方法により200℃でキュアして耐薬品性試験を実施したところ、「○」であった。また、上述の方法により銅層上に硬化レリーフパターンを作製した。高温保存試験を行った後、銅層の表面に占めるボイド評価を行ったところ、「〇+」であった。
表2に示す配合量によりネガ型感光性樹脂組成物を調整した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性および銅層の表面に占めるボイド評価は表2-1に示す通りとなった。
表2に示す配合量によりポジ型感光性樹脂組成物を調整した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性および銅層の表面に占めるボイド評価は表2-1に示す通りとなった。
実施例1において、ポリマー(A)-2を(A)-1に、(B)-1を(B)-4に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「×」であった。
実施例1において、ポリマー(A)-2を(A)-7に、(B)-1を(B)-4に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「×」であった。
実施例1において、ポリマー(A)-2を(A)-1に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「△」であった。
実施例1において、ポリマー(A)-2を(A)-7に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「○」であった。
実施例1において、ポリマー(A)-2を(A)-8に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「△」であった。
実施例1において、ポリマー(A)-2を(A)-14に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「○」であった。
実施例1において、ポリマー(A)-2を(A)-15に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「△」であった。
実施例1において、ポリマー(A)-2を(A)-21に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「○」であった。
実施例1において、ポリマー(A)-2を(A)-22に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「△」であった。
実施例1において、ポリマー(A)-2を(A)-28に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「○」であった。
実施例1において、ポリマー(A)-2を(A)-29に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「△」であった。
実施例1において、ポリマー(A)-2を(A)-35に変更した以外は、実施例1と同様にしてネガ型感光性樹脂組成物を調製した。
この組成物について、上記の方法により耐薬品性試験を実施したところ、耐薬品性は「×」であった。また、銅層の表面に占めるボイド評価を行ったところ、「○」であった。
これら実施例1~52の結果を表2に、比較例1~12の結果を表3にまとめて示す。
これに対し、重量平均分子量(Mw)が、3,000未満、あるいは16,000以上であるポリマーを用いた比較例では、耐薬品性および銅ボイドの発生が抑制される結果が劣っていることがわかる。
また、実施例26と、その他の実施例とを比較してわかるように、一般式(1)で表される(A)ポリイミド前駆体において、炭素数6~40の4価の有機基であるX1の構造を特定の基にすることにより、耐薬品性および銅ボイドの発生が抑制される結果を特に優れたものとすることができる。
また、実施例50~実施例52とその他の実施例とを比較して分かるように、(B)光重合開始剤にオキシムエステル化合物を用いることにより、耐薬品性および銅ボイドの抑制が抑制される結果を特に優れたものとすることができる。
これは、特定の重量平均分子量(Mw)を有する感光性樹脂を用いることにより、200℃以下の低温キュア条件下においても、ポリイミドのイミド環化反応(イミド化)が良好に進行する。このため樹脂膜中にポリイミド前駆体が残存しないためと考察される。
以下、実施例により本発明を具体的に説明するが、本発明はこれに限定されるものではない。実施例、比較例、及び製造例における感光性樹脂組成物の物性は、以下の方法に従って測定及び評価した。
後述の方法により合成した各ポリアミド酸エステルの重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー法(GPC)を用いて、標準ポリスチレン換算により測定した。GPCの分析条件を以下に記す。
カラム:昭和電工社製 商標名 Shodex 805M/806M直列
標準単分散ポリスチレン:昭和電工(株)製Shodex STANDARD SM-105
溶離液:N-メチル-2-ピロリドン 40℃
流速:1.0ml/分
検出器:昭和電工製 商標名 Shodex RI-930
6インチシリコンウェハー(フジミ電子工業株式会社製、厚み625±25μm)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、乾燥することにより10μm厚の塗布膜を形成した。この塗布膜について、非接触型膜厚測定器(ナノメトリクス製、ナノスペック/AFT 5100型)を用いて、面内の39点の膜厚を測定し、その平均値と最大及び最小の膜厚の差を求めた。このときの膜厚の最大と最小の差を面内均一性の指標とした。
6インチシリコンウェハー(フジミ電子工業株式会社製、厚み625±25μm)上に本発明のネガ型感光性樹脂組成物をスピン塗布し、乾燥することにより、約11μm厚の塗膜を感光性樹脂層として形成した。この塗膜にテストパターン付レチクルを用いてghiステッパー(Prisma-ghi、ウルトラテック社製)により、500mJ/cm2のエネルギーを照射して露光した。次いで、ウェハー上に形成した塗膜を、シクロペンタノンを用いて、現像機(D-SPIN636型、日本国、大日本スクリーン製造社製)でスプレー現像した。そして、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して未露光部を現像除去することにより、ポリイミド前駆体のレリーフパターンを得た。レリーフパターンを形成したウェハーを、昇温プログラム式キュア炉(VF-2000型、日本国、光洋リンドバーグ社製)を用いて、窒素雰囲気下、200℃で2時間キュアすることにより、約9μm厚のポリイミドの硬化レリーフパターンを得た。
浸漬後の塗膜について、浸漬前に対する塗膜の膜厚変動が±1%以内であり、かつ、クラックが発生していない場合を「◎」、塗膜の膜厚変動が±3%以内であり、かつ、クラックが発生していない場合を「○」、塗膜の膜厚変動が±5%以内であり、かつ、クラックが発生していない場合を「△」、膜厚変動が±5%を超えている、又はクラックが発生している場合を「×」と評価した。
酸成分として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を加えた。室温下で攪拌しながら、ピリジン79.1gを加えることにより、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。
このポリマーA-1の重量平均分子量(Mw)を測定したところ、20,000であった。
実施例1で用いた酸成分の種類と量、ジアミン成分の種類と量、末端変性剤の種類と量を、ネガ型感光性樹脂組成物溶液の粘度(ポイズ)、得られたポリマーの重量平均分子量(Mw)、面内均一性の評価結果、および耐薬品性試験の結果と併せて表1に示す。
酸末端であると、ポリマーの主鎖の両末端が
熱又は光で架橋する反応性の置換基であり、e1は炭素数1~30の1価の有機基であり、R11、R14はそれぞれ独立に水素原子又は炭素数1~30の1価の有機基であり、R12、R13はそれぞれ独立に水素原子、炭素数1~30の1価の有機基、芳香族環または脂肪族環の一部のいずれかである。(ただしR12とR13は同時に水素原子であることはない。)
の構造となっていることを示し、
酸末端/ジアミン末端の項目がアミン末端であると、ポリマーの主鎖の両末端が
の構造となっていることを示す。
また、表1の結合の種類の項目は、
ポリマーの主鎖の両末端が(E1)の場合には、a1の結合の種類を表し、ポリマーの主鎖の両末端が(F1)の場合には、f1の結合の種類を表している。
酸成分の種類と量、ジアミン成分の種類と量、末端変性剤の種類と量、ネガ型感光性樹脂組成物溶液の粘度(ポイズ)を表1に記載の通り変更した以外は、実施例1に記載の方法と同様の方法を行うことで、実施例2~29のネガ型感光性樹脂組成物溶液を得た。
得られたポリマーの重量平均分子量(Mw)、面内均一性の評価結果、耐薬品性試験の結果は表1に記載の通りである。
酸成分の種類と量、ジアミン成分の種類と量、末端変性剤の種類と量、ネガ型感光性樹脂組成物溶液の粘度(ポイズ)を表1に記載の通り変更した以外は、実施例1に記載の方法と同様の方法を行うことで、参考例1~4のネガ型感光性樹脂組成物溶液を得た。
参考例1~4のネガ型感光性樹脂組成物溶液はネガ型感光性樹脂組成物溶液の粘度(ポイズ)が90であった。得られたポリマーの重量平均分子量(Mw)、面内均一性の評価結果、耐薬品性試験の結果は表1に記載の通りである。
酸成分として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を加えた。室温下で攪拌しながら、ピリジン79.1gを加えることにより、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。
このポリマーB-1の重量平均分子量(Mw)を測定したところ、20,000であった。このポリマーB-1は主鎖の末端に、熱又は光によって反応する反応性の置換基を有していない。
ポリイミド前駆体であるポリマーB-1 100gを、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)-オキシム4g、テトラエチレングリコールジメタクリレート8g、ベンゾトリアゾール 0.5g、N-[3-(トリエトキシシリル)プロピル]フタルアミド酸1.5gと共に、N-メチル-2-ピロリドン(以下ではNMPという)80gと乳酸エチル20gからなる混合溶媒に溶解した。得られた溶液の粘度を、前記混合溶媒を更に加えることによって15ポイズに調整し、ネガ型感光性樹脂組成物溶液とした。
この溶液を前述の方法によりシリコンウェハ上に塗布し、膜厚の面内均一性と耐薬品性を求めた。
膜厚の面内均一性と耐薬品性の評価結果は表1の通りである。
酸成分の種類と量、ジアミン成分の種類と量、末端変性剤の種類と量、ネガ型感光性樹脂組成物溶液の粘度(ポイズ)を表1に記載の通り変更した以外は、比較例1に記載の方法と同様の方法を行うことで、比較例2のネガ型感光性樹脂組成物溶液を得た。得られたポリマーの重量平均分子量(Mw)、面内均一性の評価結果、耐薬品性試験の結果は表4に記載の通りである。
本発明のネガ型感光性樹脂組成物は、低温でキュアすることができ、耐薬品性に優れたものとなり、例えば半導体装置、多層配線基板等の電気・電子材料の製造に有用な感光性材料の分野で好適に利用できる。
本発明の膜厚の面内均一性が向上したネガ型感光性ポリイミド前駆体を用いることで、高度な電子機器を製造するに当たって材料に求められる、解像度と信頼性を両立させることができる。
Claims (21)
- (A)ポリイミド前駆体:100質量部;及び
(B)光重合開始剤:0.1質量部~20質量部;
を含むネガ型感光性樹脂組成物であって、
前記(A)ポリイミド前駆体が、下記一般式(1):
前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、16,000未満である、前記ネガ型感光性樹脂組成物。 - 前記一般式(1)において、X1が、前記一般式(6)を含み、Y1が、前記一般式(8)を含む、請求項2に記載のネガ型感光性樹脂組成物。
- 前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、請求項3に記載のネガ型感光性樹脂組成物。
- 前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、10,000未満である、請求項4に記載のネガ型感光性樹脂組成物。
- 前記一般式(1)において、X1が、前記一般式(6)を含み、Y1が、前記一般式(7)を含む、請求項2に記載のネガ型感光性樹脂組成物。
- 前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、請求項6に記載のネガ型感光性樹脂組成物。
- 前記一般式(1)において、X1が、前記一般式(5)を含み、Y1が、前記一般式(8)を含む、請求項2に記載のネガ型感光性樹脂組成物。
- 前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、請求項8に記載のネガ型感光性樹脂組成物。
- 前記一般式(1)において、X1が、前記一般式(5)を含み、Y1が、前記一般式(7)及び(9)からなる群から選択される少なくとも1つを含む、請求項2に記載のネガ型感光性樹脂組成物。
- 前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、請求項10に記載のネガ型感光性樹脂組成物。
- 前記一般式(1)において、X1が、前記一般式(4)を含み、Y1が、前記一般式(7)を含む、請求項2に記載のネガ型感光性樹脂組成物。
- 前記(A)ポリイミド前駆体の重量平均分子量(Mw)が、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算において、3,000以上、13,000以下である、請求項12に記載のネガ型感光性樹脂組成物。
- 前記一般式(12)において、Uは、炭素数1~30の2価の有機基である、請求項14に記載のポジ型感光性樹脂組成物。
- 前記一般式(12)において、Uは、炭素数1~8で且つ水素原子の一部または全部がフッ素原子で置換された鎖状アルキレン基である、請求項14に記載のポジ型感光性樹脂組成物。
- 前記一般式(12)において、Vは、芳香族基を含む2価の有機基である、請求項14から請求項16のいずれか1項に記載のポジ型感光性樹脂組成物。
- (1)請求項1~19のいずれか1項に記載の感光性樹脂組成物を基板上に塗布することによって感光性樹脂層を前記基板上に形成する工程と、
(2)前記感光性樹脂層を露光する工程と、
(3)前記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工程と、
(4)前記レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する工程とを含む、硬化レリーフパターンの製造方法。 - 前記基板が、銅又は銅合金から構成されている、請求項20に記載の硬化レリーフパターンの製造方法。
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KR102268692B1 (ko) | 2021-06-23 |
JP2018169627A (ja) | 2018-11-01 |
KR20220013011A (ko) | 2022-02-04 |
TW202136376A (zh) | 2021-10-01 |
JP6368066B2 (ja) | 2018-08-01 |
CN115755526A (zh) | 2023-03-07 |
US20230221639A1 (en) | 2023-07-13 |
JP6644113B2 (ja) | 2020-02-12 |
TWI644943B (zh) | 2018-12-21 |
US20180373147A1 (en) | 2018-12-27 |
KR20180055875A (ko) | 2018-05-25 |
US11163234B2 (en) | 2021-11-02 |
CN108475020A (zh) | 2018-08-31 |
TW201835159A (zh) | 2018-10-01 |
JP2018200470A (ja) | 2018-12-20 |
TW201815889A (zh) | 2018-05-01 |
US20220011669A1 (en) | 2022-01-13 |
JPWO2018037997A1 (ja) | 2018-09-13 |
TWI716709B (zh) | 2021-01-21 |
KR20210018522A (ko) | 2021-02-17 |
US11640112B2 (en) | 2023-05-02 |
JP6797866B2 (ja) | 2020-12-09 |
KR20210076219A (ko) | 2021-06-23 |
KR102354532B1 (ko) | 2022-02-08 |
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