WO2018038002A1 - 積層体の製造方法および電子デバイスの製造方法 - Google Patents
積層体の製造方法および電子デバイスの製造方法 Download PDFInfo
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- WO2018038002A1 WO2018038002A1 PCT/JP2017/029574 JP2017029574W WO2018038002A1 WO 2018038002 A1 WO2018038002 A1 WO 2018038002A1 JP 2017029574 W JP2017029574 W JP 2017029574W WO 2018038002 A1 WO2018038002 A1 WO 2018038002A1
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Images
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- 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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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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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
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/70858—Environment aspects, e.g. pressure of beam-path gas, temperature
- G03F7/70866—Environment aspects, e.g. pressure of beam-path gas, temperature of mask or workpiece
- G03F7/70875—Temperature, e.g. temperature control of masks or workpieces via control of stage temperature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
Definitions
- the present invention relates to a laminate manufacturing method and an electronic device manufacturing method.
- Resins such as polyimide and polybenzoxazole are excellent in heat resistance and insulation, and thus are used for insulating layers of electronic devices.
- polyimide and polybenzoxazole have low solubility in solvents, they are applied to a support in the state of a precursor (polyimide precursor or polybenzoxazole precursor) before the cyclization reaction, and then heated.
- a cured film is also formed by cyclizing a polyimide precursor or a polybenzoxazole precursor.
- Patent Documents 1 and 2 describe that a cured pattern film is produced using a photosensitive resin composition containing a polyimide precursor and a photopolymerization initiator.
- the present inventors As a result of studying a photosensitive resin composition including a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole, and a photopolymerization initiator, the present inventors It has been found that the film formed using the photosensitive resin composition that is included may have insufficient adhesion to a support or a metal layer.
- an object of the present invention is to provide a laminate manufacturing method and an electronic device manufacturing method excellent in adhesion.
- a photosensitive resin composition containing a polyimide precursor, a polyimide, a resin selected from a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator. It has been found that a film formed by using a film tends to require time until the film properties are stabilized after being applied on a support. And it discovered that the laminated body excellent in adhesiveness could be manufactured by providing a predetermined
- the present invention provides the following.
- a photosensitive resin composition obtained by applying a photosensitive resin composition containing a polyimide precursor, a polyimide, a resin selected from a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator on a support.
- a photosensitive resin composition layer forming step for forming a physical layer An exposure step of exposing the photosensitive resin composition layer in a pattern; and A development step of developing the photosensitive resin composition layer to form a pattern; A heating step for heating the pattern; Including a metal layer forming step of forming a metal layer on the pattern after heating, In at least one of the photosensitive resin composition layer formation step and the exposure step, between the exposure step and the development step, between the development step and the heating step, and between the heating step and the metal layer formation step.
- saves for 5 minutes or more in the state after surface temperature reaches fixed temperature.
- ⁇ 2> The method for producing a laminate according to ⁇ 1>, wherein a storage step is performed between the exposure step and the development step.
- ⁇ 3> The method for producing a laminate according to ⁇ 2>, wherein the storage step performed between the exposure step and the development step satisfies the following formula; 5 ⁇ t1 ⁇ (10 ⁇ 0.036 ⁇ T1 + 12.3 ) ⁇ 60 T1 is the average surface temperature in the storage process performed between the exposure process and the development process, and the unit is K; t1 is the time of the storage process performed between the exposure process and the development process, and the unit is minutes. is there.
- ⁇ 4> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 3>, wherein a storage step is performed between the photosensitive resin composition layer forming step and the exposure step.
- ⁇ 5> The method for producing a laminate according to ⁇ 4>, wherein the storage step performed between the photosensitive resin composition layer forming step and the exposure step satisfies the following formula: 5 ⁇ t2 ⁇ (10 ⁇ 0.031 ⁇ T2 + 10.7 ) ⁇ 60 T2 is an average surface temperature in the storage step performed between the photosensitive resin composition layer forming step and the exposure step, and the unit is K; t2 is between the photosensitive resin composition layer forming step and the exposure step.
- the time for the storage process to be performed in units of minutes.
- ⁇ 6> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 5>, wherein a storage step is performed between the development step and the heating step.
- ⁇ 7> The method for producing a laminate according to ⁇ 6>, wherein the storage step performed between the development step and the heating step satisfies the following formula; 5 ⁇ t3 ⁇ (10 ⁇ 0.02 ⁇ T3 + 8.0 ) ⁇ 60 T3 is the average surface temperature in the storage process performed between the development process and the heating process, and the unit is K; t3 is the time of the storage process performed between the development process and the heating process, and the unit is minutes. is there.
- ⁇ 8> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 7>, wherein a storage step is performed between the heating step and the metal layer forming step.
- the resin in the photosensitive resin composition is a polyimide precursor, and the polyimide precursor contains a radical polymerizable group, or the photosensitive resin composition contains a radical polymerizable compound other than the polyimide precursor, ⁇ The method for producing a laminate according to any one of 1> to ⁇ 8>.
- ⁇ 10> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 9>, wherein the polyimide precursor includes a repeating unit represented by the following formula (1); Formula (1) In formula (1), A 21 and A 22 each independently represent an oxygen atom or —NH—, R 21 represents a divalent organic group, R 22 represents a tetravalent organic group, R 23 and R 24 each independently represents a hydrogen atom or a monovalent organic group. ⁇ 11> The method for producing a laminate according to ⁇ 10>, wherein in formula (1), at least one of R 23 and R 24 contains a radical polymerizable group.
- R ⁇ 22 > in Formula (1) is a tetravalent group containing an aromatic ring
- a photosensitive resin composition layer forming step, an exposure step, a developing step, a heating step, and a metal layer forming step are performed in this order on the pattern after the metal layer forming step, and the photosensitive resin composition layer forming step and A series of cycles for performing the storage process in at least one of the exposure process, the exposure process and the development process, the development process and the heating process, and the heating process and the metal layer forming process.
- ⁇ 14> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 13>, which is a method for producing a laminate having a multilayer wiring structure.
- a photosensitive resin composition obtained by applying a photosensitive resin composition containing a polyimide precursor, a polyimide, a resin selected from a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator on a support.
- a photosensitive resin composition layer forming step for forming a physical layer An exposure step of exposing the photosensitive resin composition layer in a pattern; and A development step of developing the photosensitive resin composition layer to form a pattern; A heating step for heating the pattern; Including a metal layer forming step of forming a metal layer on the pattern after heating, In at least one of the photosensitive resin composition layer formation step and the exposure step, between the exposure step and the development step, between the development step and the heating step, and between the heating step and the metal layer formation step.
- the manufacturing method of an electronic device including the manufacturing method of a laminated body which performs the preservation
- the description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
- the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
- the light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
- an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
- EUV light extreme ultraviolet rays
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- (meth) acrylate represents both and / or “acrylate” and “methacrylate”
- (meth) allyl means both “allyl” and “methallyl”
- (Meth) acryl” represents either “acryl” and “methacryl” or any one
- “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
- the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC) measurement unless otherwise specified.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel.
- THF tetrahydrofuran
- detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
- the method for producing a laminate of the present invention comprises a photosensitive resin composition containing a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, and a photopolymerization initiator on a support.
- the storage step of storing for 5 minutes or more after the surface temperature reaches a certain temperature is performed.
- a laminate having excellent adhesion can be formed. It is assumed that the reason why such an effect is obtained is as follows. A film formed using a photosensitive resin composition containing the above-described resin and a photopolymerization initiator tends to require time until the film properties are stabilized. Sites where the reaction proceeds locally in the film when the next process is performed in a state where the film properties are not stable (for example, when an exposure process is subsequently performed after the photosensitive resin composition layer forming process) It is considered that stress may be locally applied to the film. On the other hand, according to the present invention, the storage process described above is provided between any of the above-described processes to stabilize the film properties and relax the residual stress of the film. It is considered that the process can be performed.
- the resin mentioned above in the photosensitive resin composition is a polyimide precursor
- This polyimide precursor contains a radically polymerizable group, or the photosensitive resin composition containing radically polymerizable compounds other than the polyimide precursor mentioned above In the case of using a product, the effect of the present invention is particularly remarkable.
- a photosensitive resin containing such a radical polymerizable component a polyimide precursor having a radical polymerizable group, a radical polymerizable compound other than the polyimide precursor
- an exposure step and During the development process a pattern is formed using a crosslinking reaction by radical polymerization of a radically polymerizable component, and the resulting pattern is heated to a high temperature to cause an imidization reaction, resulting in high heat resistance and high insulation.
- the film is formed.
- the reaction is complicated in multiple stages.
- the manufacturing method of the laminated body of this invention includes the photosensitive resin composition layer formation process which applies the photosensitive resin composition on a support body, and forms the photosensitive resin composition layer.
- the photosensitive resin composition will be described later.
- the type of support can be appropriately determined according to the application.
- an inorganic substrate, a resin substrate, a resin composite material substrate, or the like can be given.
- the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride (silicon nitride) substrate, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate.
- TFT thin film transistor
- the spin coating method is more preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.
- the thickness of the photosensitive resin composition layer is preferably applied such that the film thickness after exposure is 0.1 to 100 ⁇ m, and more preferably 1 to 50 ⁇ m.
- the thickness of the photosensitive resin composition layer formed does not necessarily need to be uniform. For example, when a photosensitive resin composition layer is formed on an uneven surface, the photosensitive resin composition layer may have a different thickness.
- the photosensitive resin composition layer formed on the support may be dried.
- the drying temperature is preferably 50 to 150 ° C., more preferably 70 to 130 ° C., and further preferably 90 to 110 ° C.
- the drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, still more preferably 3 to 7 minutes.
- a drying process is a process different from the preservation
- the manufacturing method of the laminated body of this invention includes the exposure process which exposes the said photosensitive resin composition layer in pattern shape.
- the exposure is not particularly defined as long as the photosensitive resin composition can be cured, but for example, it is preferably irradiated at 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and is preferably 200 to 8000 mJ / cm 2 . It is more preferable to irradiate.
- the exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and preferably 240 to 550 nm.
- the manufacturing method of the laminated body of this invention includes the image development process which develops the photosensitive resin composition layer with respect to the exposed photosensitive resin composition layer, and forms a pattern. Development is performed using a developer.
- the developer can be used without any particular limitation. Solvents are preferred. Examples of the solvent used in the developer include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides. About these details, the solvent demonstrated in the column of the resin composition mentioned later is mentioned.
- the development time is preferably 10 seconds to 5 minutes.
- the temperature at the time of development is not particularly defined, but it can be carried out at 20 to 40 ° C.
- rinsing may be further performed.
- the rinsing is preferably performed with a solvent different from the developer. For example, it can rinse using the solvent contained in the photosensitive resin composition.
- the rinse time is preferably 5 seconds to 1 minute.
- the manufacturing method of the laminated body of this invention includes the heating process which heats the pattern (resin layer) obtained by the image development process.
- a cyclization reaction of the polyimide precursor proceeds.
- curing of the unreacted radical polymerizable component also proceeds.
- the maximum heating temperature (maximum temperature during heating) is preferably from 100 to 500 ° C, more preferably from 140 to 400 ° C, and even more preferably from 160 to 350 ° C. Heating is preferably performed at a temperature rising rate of 1 to 12 ° C./min from a temperature of 20 to 150 ° C. to a maximum heating temperature, more preferably 2 to 10 ° C./min, and further preferably 3 to 10 ° C./min.
- the temperature at the start of heating is preferably 20 to 150 ° C., more preferably 20 to 130 ° C., and further preferably 25 to 120 ° C.
- the temperature at the start of heating refers to the heating temperature at the start of the step of heating to the maximum heating temperature.
- Heating is preferably performed for 10 to 360 minutes after reaching the maximum heating temperature, more preferably for 20 to 300 minutes, and particularly preferably for 30 to 240 minutes.
- Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, left at 180 ° C. for 60 minutes, from 180 ° C. to 200 ° C. raised at 2 ° C./min, and placed at 200 ° C. for 120 minutes. And the like. Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
- the heating step is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the polyimide precursor or the like.
- the oxygen concentration is preferably 50 ppm by volume or less, and more preferably 20 ppm by volume or less.
- the manufacturing method of the laminated body of this invention includes the metal layer formation process which forms a metal layer on the pattern (resin layer) after a heating.
- the metal layer is not particularly limited, and an existing metal species can be used.
- copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten can be mentioned, copper and aluminum are preferable, and copper is more preferable.
- the method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used.
- the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest portion.
- the manufacturing method of the laminated body of this invention may include the surface activation process process of carrying out the surface activation process of at least one part of the said metal layer and the photosensitive resin composition layer.
- the surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the photosensitive resin composition layer after the heating step, or may be performed on the metal layer and the photosensitive layer after the heating step.
- Each of the conductive resin composition layers may be performed at least partially.
- the surface activation treatment step is usually performed after the metal layer formation step. However, after the heating step, the surface activation treatment step may be performed on the photosensitive resin composition layer, and then the metal layer may be formed. .
- the surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is preferably performed on a part or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. .
- the surface activation treatment is preferably performed on the surface of the metal layer, the adhesion with the photosensitive resin composition layer layer provided on the surface can be improved.
- Surface activation treatment includes plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF 4 / O 2 , NF 3 / O 2 , SF 6 , NF 3 , etching treatment with NF 3 / O 2 , surface treatment by ultraviolet (UV) ozone method, compound having at least one amino group and thiol group after removing the oxide film by dipping in hydrochloric acid aqueous solution It is selected from an immersion treatment in an organic surface treatment agent contained and a mechanical surface roughening treatment using a brush, and a plasma treatment is preferred, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferred.
- the energy is preferably 500 ⁇ 200000J / m 2, more preferably 1000 ⁇ 100000J / m 2, and most preferably 10000 ⁇ 50000J / m 2.
- the method for producing a laminate of the present invention includes a photosensitive resin composition layer forming step and an exposure step, an exposure step and a development step, a development step and a heating step, and a heating step and a metal layer.
- a storage step is performed in which the surface temperature reaches a certain temperature and is stored for 5 minutes or longer.
- the storage step described above may be performed in all of the steps, and the storage step described above may be performed only in any one of the steps.
- the above-described storage step may be performed in at least one of the photosensitive resin composition layer forming step and the exposure step, between the exposure step and the development step, and between the development step and the heating step. It is preferable to perform a storage process between the exposure process and the development process. By performing a preservation
- the storage step means a step of storing for 5 minutes or longer after the surface temperature reaches a certain temperature.
- the surface temperature means the surface temperature of an object to be processed such as a photosensitive resin composition layer or a pattern (resin layer) formed by the photosensitive resin composition layer.
- the constant temperature in the storage process does not mean a specific temperature but may have a predetermined temperature range.
- the fluctuation range of the surface temperature of the object to be treated in the storage process is preferably 15 ° C. or less, more preferably 10 ° C. or less, and more preferably 5 ° C. or less. More preferably it is. If the fluctuation range of the surface temperature is in the above-described range, it is easy to stabilize the properties of the film, and it is easy to produce a laminate having excellent adhesion.
- the average surface temperature of the object to be treated in the storage step is preferably ⁇ 30 ° C. or higher, more preferably 4 ° C. or higher, still more preferably 10 ° C. or higher, and particularly preferably 20 ° C. or higher.
- the upper limit is preferably 100 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 45 ° C. or lower, and particularly preferably 30 ° C. or lower.
- the average surface temperature of a to-be-processed object means the average of the surface temperature of the to-be-processed object for every time.
- save process is performed for 5 minutes or more.
- the average surface temperature of the object to be treated in the PED process is preferably ⁇ 30 to 60 ° C., more preferably 4 to 45 ° C., and further preferably 20 to 30 ° C.
- the PED process is preferably performed for 5 to 720 minutes, more preferably 5 to 480 minutes, and further preferably 5 to 360 minutes.
- the fluctuation range of the surface temperature of the workpiece in the PED process is preferably 15 ° C. or less, more preferably 10 ° C. or less, and further preferably 5 ° C. or less.
- a PCD process should be performed on the conditions which satisfy
- the average surface temperature of the object to be treated in the PCD process is preferably ⁇ 30 to 60 ° C., more preferably 4 to 45 ° C., and further preferably 20 to 30 ° C.
- the PCD step is preferably performed for 5 to 360 minutes, more preferably 5 to 120 minutes, and further preferably 5 to 60 minutes.
- the fluctuation range of the surface temperature of the object to be processed in the PCD process is preferably 15 ° C. or less, more preferably 10 ° C. or less, and further preferably 5 ° C. or less.
- the average surface temperature of the object to be treated in the PDD process is preferably 4 to 80 ° C, more preferably 10 to 60 ° C, and further preferably 20 to 30 ° C.
- the PDD step is preferably performed for 5 to 1200 minutes, more preferably 5 to 720 minutes, further preferably 5 to 600 minutes, and particularly preferably 5 to 300 minutes.
- the fluctuation range of the surface temperature of the object to be processed in the PDD process is preferably 30 ° C. or less, more preferably 20 ° C. or less, and further preferably 10 ° C. or less.
- the average surface temperature of the object to be processed in the PBD process is 4 to 100 ° C. Is preferable, 10 to 80 ° C. is more preferable, and 20 to 60 ° C. is still more preferable.
- the PBD step is preferably performed for 5 to 2400 minutes, more preferably 5 to 1200 minutes, further preferably 5 to 900 minutes, and particularly preferably 5 to 600 minutes.
- the fluctuation range of the surface temperature of the object to be processed in the PBD process is preferably 60 ° C. or less, more preferably 45 ° C. or less, and further preferably 30 ° C. or less.
- the photosensitive resin composition layer forming step, the exposure step, the developing step, the heating step and the metal layer forming step are further performed in this order on the pattern (resin layer) after the metal layer forming step. At least between the photosensitive resin composition layer forming step and the exposing step, between the exposing step and the developing step, between the developing step and the heating step, and between the heating step and the metal layer forming step. In one, it is also preferable to carry out a series of cycles for carrying out the storage step two or more times. The aforementioned cycle is preferably performed 2 to 7 times, more preferably 2 to 5 times.
- stacked alternately alternately can be manufactured.
- peeling tends to occur at the interface between the metal layer and the resin layer, the interface between the resin layers, and the interface between the resin layer and the support. For example, even when the number of stacked layers is increased, peeling between layers is unlikely to occur. For this reason, the effect of this invention is acquired more notably.
- FIG. 1 is a diagram showing an example of a multilayer body having a multilayer wiring structure.
- reference numeral 500 denotes a laminated body
- reference numerals 201 to 204 denote resin layers
- reference numerals 301 to 303 denote metal layers.
- a desired pattern is formed on the resin layer 201.
- this pattern can be formed by, for example, negative development.
- a metal layer 301 is formed on the surface of the resin layer 201.
- the metal layer 301 is formed so as to cover a part of the surface of the groove 401 formed in the resin layer 201.
- a resin layer 202 is formed on the metal layer 301.
- a desired pattern is formed on the resin layer 202, and a part of the metal layer 301 is exposed from the resin layer 202.
- a metal layer 302 is formed on the surface of the resin layer 202.
- the metal layer 302 is formed so as to cover a part of the surface of the groove 402 formed in the resin layer 202, and is electrically connected to the metal layer 301 exposed from the resin layer 202.
- a resin layer 203 is formed on the metal layer 302.
- a desired pattern is formed on the resin layer 203, and a part of the metal layer 302 is exposed from the resin layer 203.
- a metal layer 303 is formed on the surface of the resin layer 203.
- the metal layer 303 is formed so as to cover part of the surface of the groove 403 formed in the resin layer 203, and is electrically connected to the metal layer 302 exposed from the resin layer 203.
- a resin layer 204 is formed on the metal layer 303.
- a desired pattern is formed on the resin layer 204, and a part of the metal layer 303 is exposed from the resin layer 204. In FIG. 1, a part of the metal layer 302 is also exposed from the resin layer 204.
- the resin layers 201 to 204 function as insulating films, and the metal layers 301 to 303 function as wiring layers.
- Such a laminate can be preferably used as a rewiring layer in an electronic device.
- photosensitive resin composition (hereinafter also referred to as a resin composition) used in the method for producing a laminate of the present invention will be described.
- the resin composition in the present invention includes a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole.
- a resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole.
- a polyimide precursor or a polybenzoxazole precursor is used as the resin, the film properties tend to be difficult to stabilize.
- a polyimide precursor or a polybenzoxazole precursor is used as the resin, the effects of the present invention are particularly easily obtained.
- a polyimide precursor preferably, a polyimide precursor having a radical polymerizable group
- the effects of the present invention are particularly easily obtained.
- the resin content in the resin composition is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, still more preferably 60 to 99% by mass, and more preferably 70 to 99% by mass with respect to the total solid content of the resin composition. Is particularly preferred.
- the content of the polyimide precursor in the resin composition is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, and still more preferably 60 to 99% by mass with respect to the total solid content of the resin composition. 70 to 99% by mass is particularly preferable.
- the content of the polyimide precursor in the total mass of the resin contained in the resin composition is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.
- the resin contained in the resin composition is preferably substantially composed only of a polyimide precursor. When the resin contained in the resin composition is substantially composed only of the polyimide precursor, for example, the content of the resin other than the polyimide precursor contained in the resin composition is the content of the polyimide precursor. It is preferable that it is 3
- Polyimide precursor As a polyimide precursor, it is preferable that it is a polyimide precursor containing the repeating unit represented by Formula (1).
- a 21 and A 22 each independently represent an oxygen atom or —NH—
- R 21 represents a divalent organic group
- R 22 represents a tetravalent organic group
- R 23 and R 24 each independently represents a hydrogen atom or a monovalent organic group.
- a 21 and A 22 each independently represents an oxygen atom or —NH—, preferably an oxygen atom.
- R 21 represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aryl group, a linear or branched aliphatic group having 2 to 20 carbon atoms, and a carbon number of 6
- a group consisting of a cyclic aliphatic group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a combination thereof is preferable, and a group consisting of an aryl group having 6 to 20 carbon atoms is more preferable.
- the aryl group include the following.
- R 21 include diamine residues remaining after removal of the amino group of the following diamine.
- R 21 examples include diamine residues remaining after removal of the amino groups of diamines (DA-1) to (DA-18) shown below.
- R 21 is a diamine residue remaining after removal of the amino group of a diamine having two or more alkylene glycol units in the main chain.
- Preferred is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine residue containing no aromatic ring.
- Examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( Trade names, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propane Examples include, but are not limited to, -2-yl) oxy) propan-2-amine and the like.
- the structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.
- x, y, and z are average values.
- R 22 represents a tetravalent organic group, preferably a tetravalent group containing an aromatic ring, and a group represented by the following formula (1-1) or formula (1-2) Is more preferable.
- R 112 represents a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO.
- 2 - and -NHCO- is preferably a group selected from combinations thereof, a single bond, or an alkylene group which ⁇ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - More preferably, it is a divalent group selected from CO—, —S— and —SO 2 —, —CH 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, — More preferred is a divalent group selected from the group consisting of O—, —CO—, —S— and —SO 2 —.
- R 22 examples include a tetracarboxylic acid residue remaining after the acid anhydride group is removed from tetracarboxylic dianhydride. Specific examples include tetracarboxylic acid residues remaining after the acid anhydride group is removed from the following tetracarboxylic dianhydrides.
- R 22 also include tetracarboxylic acid residues remaining after the removal of anhydride groups from tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.
- R 22 preferably has an OH group. More specifically, examples of R 22 include tetracarboxylic acid residues remaining after removal of the acid anhydride groups from the above (DAA-1) to (DAA-5).
- R 23 and R 24 each independently represent a hydrogen atom or a monovalent organic group.
- the monovalent organic group represented by R 23 and R 24 include a linear or branched alkyl group, a cyclic alkyl group, a group containing an aromatic group, and a radical polymerizable group.
- at least one of R 23 and R 24 is preferably a group containing a radical polymerizable group. According to this aspect, the effects of the present invention tend to be obtained more remarkably.
- the photosensitive resin composition containing this polyimide precursor can be preferably used as a negative photosensitive resin composition.
- the radical polymerizable group include a group having an ethylenically unsaturated bond. Specific examples of the radical polymerizable group include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.
- R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
- R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a polyoxyalkylene group having 4 to 30 carbon atoms.
- suitable R 201 include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene.
- R 200 is a methyl group and R 201 is an ethylene group is particularly preferable.
- the linear or branched alkyl group preferably has 1 to 30 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, Examples include sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
- the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
- Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
- Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Can be mentioned.
- a cyclohexyl group is preferable from the viewpoint of achieving high sensitivity.
- the aromatic group a substituted or unsubstituted benzene ring group, naphthalene ring group, pentalene ring group, indene ring group, azulene ring group, heptalene ring group, indacene ring group, perylene ring group, pentacene ring group, acenaphthene ring group Phenanthrene ring group, anthracene ring group, naphthacene ring group, chrysene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, oxazole ring group, thiazole Ring group, pyridine ring group, pyrazine ring group,
- the polyimide precursor when A 22 is an oxygen atom and R 23 is a hydrogen atom, and / or when A 21 is an oxygen atom and R 24 is a hydrogen atom, the polyimide precursor is an ethylenic group. It may form a counter salt with a tertiary amine compound having a saturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
- the polyimide precursor preferably has a fluorine atom in the structural unit from the viewpoint of improving resolution.
- the fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking from the surface can be suppressed.
- the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.
- the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
- the main chain terminal of the polyimide precursor is sealed with a terminal sealing agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to do. Of these, it is more preferable to use a monoamine.
- a monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-aminonaphthalene.
- the polyimide precursor may consist of a repeating unit represented by the formula (1) and another repeating unit that is another polyimide precursor.
- the proportion of the other repeating units in the polyimide precursor is preferably 1 to 60 mol%, and more preferably 5 to 50 mol%.
- the polyimide precursor in the present invention may be configured to be substantially free of other polyimide precursors other than the polyimide precursor containing the repeating unit represented by the formula (1). “Substantially free” means, for example, that the content of the other polyimide precursor contained in the resin composition is 3% by mass or less of the content of the polyimide precursor.
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 20000 to 28000, more preferably 22000 to 27000, and further preferably 23000 to 25000.
- the degree of dispersion (Mw / Mn) of the polyimide precursor is not particularly defined, but is preferably 1.0 or more, more preferably 2.5 or more, and further preferably 2.8 or more. preferable.
- the upper limit of the degree of dispersion of the polyimide precursor is not particularly defined, but is preferably 4.5 or less, for example, or 3.4 or less.
- the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a compound represented by the following formula (4), and represented by the following formula (4). More preferably, the compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include the polymerizable groups described in the above polyimide precursor, and the preferred range is also the same.
- R 131 represents a divalent organic group
- R 132 represents a tetravalent organic group.
- a radical polymerizable group may be introduced into at least one of R 131 and R 132 , or as shown in the following formula (4-1) or formula (4-2) A radical polymerizable group may be introduced at the end of the polyimide.
- R 133 is a radical polymerizable group, and the other groups have the same meanings as those in formula (4).
- Formula (4-2) In the formula, at least one of R 134 and R 135 is a radical polymerizable group, the other is an organic group, and the other groups have the same meanings as those in formula (4).
- Examples of the divalent organic group represented by R 131 include the same groups as those described above for R 21 in Formula (1) of the polyimide precursor described above, and preferred ranges thereof are also the same.
- Examples of the tetravalent organic group represented by R 132 include the same groups as those described above for R 22 in Formula (1) of the polyimide precursor described above, and preferred ranges thereof are also the same.
- the polyimide preferably has an imidization ratio of 85% or more, more preferably 90% or more.
- the imidization ratio is 85% or more, film shrinkage due to ring closure that occurs when imidization is performed by heating is reduced, and generation of warpage can be suppressed.
- Polyimide In addition to all the repeating structural units of the formula based on one R 131 or R 132 (4), may include a repeating unit containing two or more different types of R 131 or R 132.
- the polyimide may also contain other types of repeating structural units in addition to the repeating unit of the above formula (4).
- polyimide can be prepared by reacting tetracarboxylic dianhydride with a diamine compound (partially replaced with a monoamine end-capping agent) at low temperature, or tetracarboxylic dianhydride (partially acid at low temperature).
- the polyimide precursor is obtained using a method such as a method of reacting with an end-capping agent which is A method of complete imidization using a dodation reaction method, a method of stopping imidation reaction in the middle and partially introducing an imide structure, and a blend of a completely imidized polymer and its polyimide precursor By doing so, it is possible to synthesize using a
- the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000.
- the weight average molecular weight is more preferably 20,000 or more.
- the weight average molecular weight of at least 1 type of polyimide is the said range.
- the polybenzoxazole precursor is not particularly limited in terms of its structure and the like, but is preferably a compound containing a repeating unit represented by the following formula (3).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group.
- R 123 and R 124 have the same meaning as R 23 in the formula (1), respectively, and the preferred ranges are also the same.
- the divalent organic group represented by R 121 is preferably a group containing at least one of an aliphatic group and an aromatic group.
- the aliphatic group a linear aliphatic group is preferable.
- R 121 is preferably a dicarboxylic acid residue.
- the dicarboxylic acid a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferred, and a dicarboxylic acid containing an aromatic group is more preferred.
- a dicarboxylic acid containing an aliphatic group a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a linear or branched (preferably linear) aliphatic group and two COOHs are used. More preferred is a dicarboxylic acid.
- the linear or branched (preferably linear) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms. It is particularly preferably 15 and more preferably 5 to 10.
- the linear aliphatic group is preferably an alkylene group.
- dicarboxylic acid containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid.
- Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
- the dicarboxylic acid containing an aromatic group is preferably a dicarboxylic acid having the following aromatic group, more preferably a dicarboxylic acid comprising only the following aromatic group and two COOH.
- A represents —CH 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, and —C (CH 3 ) 2 —.
- dicarboxylic acid containing an aromatic group are preferably 4,4'-carbonyldibenzoic acid and 4,4'-dicarboxydiphenyl ether terephthalic acid.
- R 122 represents a tetravalent organic group.
- examples of the tetravalent organic group include the groups described for R 22 in the above formula (1), and the preferred range is also the same.
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18000 to 30000, more preferably 20000 to 29000, and further preferably 22000 to 28000.
- the number average molecular weight (Mn) is preferably 7200 to 14000, more preferably 8000 to 12000, and further preferably 9200 to 11200.
- the degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more.
- the upper limit value of the degree of dispersion of the polybenzoxazole precursor is not particularly defined, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and more preferably 2.3 or less. Preferably, 2.2 or less is even more preferable.
- the polybenzoxazole is not particularly limited as long as it is a compound having a benzoxazole ring, but is preferably a compound having a repeating unit represented by the following formula (X), and represented by the following formula (X). More preferably, the compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include the radical polymerizable group described in the above polyimide precursor, and the preferred range is also the same.
- R 133 represents a divalent organic group
- R 134 represents a tetravalent organic group.
- a radical polymerizable group may be introduced into at least one of R 133 and R 134 , as shown in the following formula (X-1) or formula (X-2)
- a radical polymerizable group may be introduced at the terminal of polybenzoxazole.
- Examples of the divalent organic group represented by R 133 include aliphatic and aromatic groups. Specific examples include the group described for R 121 of the formula (3) of the polybenzoxazole precursor, and the preferred range is also the same.
- Examples of the tetravalent organic group represented by R 134 include the groups described for R 122 in the formula (3) of the polybenzoxazole precursor, and the preferred range is also the same.
- polybenzoxazole has the above formula (X containing two or more different types of R 133 or R 134. ) May be included.
- Polybenzoxazole may also contain other types of repeating structural units in addition to the repeating unit of the above formula (X).
- Polybenzoxazole is obtained, for example, by reacting a bisaminophenol derivative with a compound selected from dicarboxylic acid containing R 133 and dicarboxylic acid dichloride and dicarboxylic acid derivative of the above dicarboxylic acid to obtain a polybenzoxazole precursor.
- a compound selected from dicarboxylic acid containing R 133 and dicarboxylic acid dichloride and dicarboxylic acid derivative of the above dicarboxylic acid to obtain a polybenzoxazole precursor.
- dicarboxylic acid an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.
- the weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000.
- the weight average molecular weight is more preferably 20,000 or more.
- the weight average molecular weight of at least 1 type of polybenzoxazole is the said range.
- the resin composition in the present invention may further contain a radical polymerizable compound.
- a radical polymerizable compound By containing a radically polymerizable compound, it can be preferably used as a negative photosensitive resin composition. Furthermore, a cured film having excellent heat resistance can be formed.
- the radically polymerizable compound a compound having an ethylenically unsaturated bond is preferable, and a compound including two or more groups having an ethylenically unsaturated bond is more preferable.
- the radically polymerizable compound may be in any of chemical forms such as monomers, prepolymers, oligomers and mixtures thereof, and multimers thereof.
- the radically polymerizable compound in the present invention is a component different from the resin described above. That is, a polyimide precursor having a radical polymerizable group, a polyimide having a radical polymerizable group, a polybenzoxazole precursor having a radical polymerizable group, and a polybenzoxazole having a radical polymerizable group correspond to the resin.
- a monomer type radical polymerizable compound (hereinafter also referred to as a radical polymerizable monomer) is a compound different from a polymer compound.
- the radical polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably, it is a compound.
- the molecular weight of the radical polymerizable monomer is usually 100 or more.
- the oligomer type radical polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 radical polymerizable monomers are bonded.
- the molecular weight is preferably 2000 to 20000, more preferably 2000 to 15000, and still more preferably 2000 to 10000 in terms of polystyrene in gel permeation chromatography (GPC).
- the number of functional groups of the radical polymerizable compound in the present invention means the number of radical polymerizable groups in one molecule.
- the resin composition preferably contains at least one bifunctional or higher radical polymerizable compound containing two or more radical polymerizable groups, and preferably contains at least one bifunctional to tetrafunctional radical polymerizable compound. More preferably, seeds are included.
- radical polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof and amides, preferably unsaturated carboxylic acids. These are esters of acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional.
- unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
- esters thereof and amides preferably unsaturated carboxylic acids. These are esters of acids and polyhydric alcohol compounds, and amides
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
- radical polymerizable compound a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
- examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
- radical polymerizable compound examples include 2 groups having a fluorene ring and an ethylenically unsaturated bond described in JP 2010-160418 A, JP 2010-129825 A, Japanese Patent 4364216 A, and the like. It is also possible to use a compound having more than one, a cardo resin. Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
- n is an integer from 0 to 14, and m is an integer from 0 to 8.
- a plurality of R and T present in the molecule may be the same or different.
- at least one of the plurality of R is —OC ( ⁇ O) CH ⁇ CH 2 or —OC ( ⁇ O) represents a group represented by C (CH 3 ) ⁇ CH 2 .
- Specific examples of the compounds represented by the above formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-2699779.
- JP-A-10-62986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a radically polymerizable compound.
- the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as radically polymerizable compounds, the contents of which are incorporated herein.
- radical polymerizable compound examples include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku ( A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues.
- the structure is preferable. These oligomer types can also be used. Further, preferred examples include pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formulas (MO-1) and (MO-2). In addition, SR209 manufactured by Sartomer Co. can be used.
- the radical polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
- examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- a preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the said compound is the said range, it is excellent in manufacture and handleability, and also is excellent in developability. Moreover, radical polymerizability is favorable.
- a compound having a caprolactone structure can also be used.
- the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
- trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol Mention is made of ⁇ -caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying (meth) acrylic acid and ⁇ -caprolactone with polyhydric alcohols such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine Can do.
- compounds represented by the following formula (C) are preferred.
- R 1 represents a hydrogen atom or a methyl group
- m represents 1 or 2
- “*” represents a bond
- R 1 represents a hydrogen atom or a methyl group
- “*” represents a bond
- the number of the groups represented by 2 and the compound in which R 1 is all hydrogen atoms)
- the radical polymerizable compound is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).
- each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —
- Each y independently represents an integer of 0 to 10
- each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
- the total number of (meth) acryloyl groups is 3 or 4
- each m independently represents an integer of 0 to 10
- the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.
- the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.
- m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
- n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
- — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — is bonded to X at the end on the oxygen atom side.
- the form is preferred.
- a form in which all six Xs are acryloyl groups is preferable.
- Examples of commercially available compounds represented by formula (i) and formula (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pentylene manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
- radical polymerizable compound examples include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable monomers having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. You can also.
- urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (Shin Nakamura) Chemical Industry Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.) And Bremermer PME400 (manufactured by NOF Corporation).
- the radical polymerizable compound preferably has a partial structure represented by the following formula from the viewpoint of heat resistance. However, * in the formula is a connecting hand.
- the compound having the partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and the like. .
- the content of the radical polymerizable compound is preferably 1 to 50% by mass with respect to the total solid content of the resin composition from the viewpoint of good radical polymerizability and heat resistance.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 30% by mass or less.
- the mass ratio (resin / radical polymerizable compound) between the resin (preferably a polyimide precursor) and the radical polymerizable compound is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, 90/10 to 50/50 is more preferable.
- the radical polymerizable compound may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the resin composition in the present invention contains a photopolymerization initiator.
- the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferred.
- the resin composition in the present invention contains a photo radical polymerization initiator
- the resin composition is applied to a substrate such as a semiconductor wafer to form a resin composition layer, and then irradiated with light, resulting in radicals. Curing occurs and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubility can be easily produced according to the pattern of the electrode or the like. .
- the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators.
- a photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
- the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm).
- the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
- Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. Can be mentioned.
- ⁇ -hydroxyketone compounds ⁇ -aminoketone compounds, acylphosphine compounds and metallocene compounds can also be suitably used. More specifically, for example, a photopolymerization initiator described in JP-A-10-291969 and a photopolymerization initiator described in Japanese Patent No. 4225898 can also be used.
- ⁇ -hydroxyketone compound IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- ⁇ -aminoketone compound commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
- ⁇ -aminoketone compound compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
- the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- IRGACURE-819 and IRGACURE-TPO which are commercially available products can be used.
- the metallocene compound include IRGACURE-784 (manufactured by BASF).
- More preferred examples of the photopolymerization initiator include oxime compounds.
- the exposure latitude can be improved more effectively.
- Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a thermal base generator.
- Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
- Preferred oxime compounds include, for example, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.
- IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, light described in JP2012-14052A) A polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
- Adeka Arkles NCI-831 and Adeka Arkles NCI-930 made by ADEKA
- DFI-091 manufactured by Daitokemix Co., Ltd.
- an oxime compound having a fluorine atom examples include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013. And the compound (C-3) described in paragraph 0101 of JP-A No. 164471.
- oxime compounds having a specific substituent as disclosed in JP-A-2007-267979 there are oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.
- photopolymerization initiators from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls.
- At least selected from imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds 1 type is preferable, trihalomethyltriazine compound, ⁇ -hydroxyketone compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide More preferably, at least one selected from a compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound and an acetophenone compound, a trihalomethyltriazine compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, and an oxime compound , At least one selected from triarylimidazole dimers and benzophen
- Photopolymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), and the like.
- Aromatic ketones such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc.
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkylbenzoin
- benzyl derivatives such as benzyldimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- R 50 represents an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; a phenyl group; An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, and R 51 is the group represented by formula (II) or the same as R 50
- Each of R 52 to R 54 is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.
- R 55 is the alkyl
- the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition. %.
- the photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.
- the resin composition in the present invention preferably contains a polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis.
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the resin composition. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
- the resin composition in the present invention may contain a photobase generator.
- a photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure.
- the base (basic substance) ) Is not particularly limited as long as it generates. Since the base generated by the exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used in the negative photosensitive resin composition.
- the content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be a general content.
- the content of the photobase generator is preferably in the range of 0.01 parts by weight to less than 30 parts by weight with respect to 100 parts by weight of the resin composition, and in the range of 0.05 parts by weight to 25 parts by weight More preferably, it is more preferably in the range of 0.1 to 20 parts by mass.
- a known compound can be used as a photobase generator.
- M.M. Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al.
- An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound Can be mentioned. It is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).
- the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
- the generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the catalytic effect of the generated basic substance is large, the apparent sensitivity as the resin composition is improved. From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.
- the photobase generator is preferably a photobase generator that does not contain salt in the structure. It is preferred that there is no charge on the nitrogen atom of the base moiety generated in the photobase generator.
- the generated base is preferably latentized using a covalent bond, and the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated base moiety and the adjacent atom is cleaved. More preferably, the compound generates a base.
- the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is good and the pot life is improved.
- the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
- the photobase generator preferably has a latent base generated using a covalent bond as described above. More preferably, the generated base is latentized using an amide bond, carbamate bond, or oxime bond.
- photobase generators having a cinnamic acid amide structure described in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO2009 / 123122, Japanese Patent Application Laid-Open No. 2006-189591, and Japanese Patent Application Laid-Open No. 2008-247747. It is also possible to use a photobase generator having a carbamate structure described in the publication, a photobase generator having an oxime structure or a carbamoyloxime structure described in JP2007-249013A and JP2008-003581A. .
- examples of the photobase generator include compounds described in paragraph numbers 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraph numbers 0022 to 0069 of JP2013-194205A. And compounds described in paragraph numbers 0026 to 0074 of JP2013-204019A and compounds described in paragraph number 0052 of WO2010 / 064631.
- the resin composition in the present invention may contain a thermal base generator.
- the thermal base generator includes at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or more, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation.
- Thermal base generators are preferred.
- pKa1 represents a logarithmic representation ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can promote the cyclization reaction of the polyimide precursor and the like.
- the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, and more preferably 120 to 200 ° C.
- the upper limit of the base generation temperature is more preferably 190 ° C or lower, further preferably 180 ° C or lower, and further preferably 165 ° C or lower.
- the lower limit of the base generation temperature is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, and thus a resin composition having excellent stability can be prepared.
- the cyclization temperature of the polyimide precursor can be lowered.
- the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
- the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be made lower. Further, the boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.
- the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (A1) described later.
- the ammonium salt (A2) is preferably an acidic compound.
- the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound other than an acidic compound that generates a base when heated.
- the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or (102) and an anion.
- the anion may be bonded to any part of the ammonium cation via a covalent bond and may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation.
- numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
- the anion outside the molecule of the cation moiety is also referred to as a counter anion.
- R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group
- formula R 7 represents a hydrocarbon group.
- R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 may be bonded to form a ring.
- the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
- the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
- the lower limit is more preferably 0.5 or more, and further preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor and the like can be cyclized at a low temperature, and further, the stability of the resin composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the resin composition is good.
- the kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
- the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion.
- the stability, curability and developability of the resin composition can be further improved by using an anion of a divalent carboxylic acid.
- the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less.
- pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
- the stability of the resin composition can be further improved.
- pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and the determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Hafliger, O., Hafliger, O., Hafliger, O. Compilation: Braude, EA, Nachod, FC, Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RM C. ord; , Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
- the carboxylate anion is preferably represented by the following formula (X1).
- EWG represents an electron withdrawing group.
- the electron withdrawing group means a group having a positive Hammett's substituent constant ⁇ m.
- ⁇ m is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 631-642.
- the electron withdrawing group of this invention is not limited to the substituent described in the said literature.
- Me represents a methyl group
- Ac represents an acetyl group
- Ph represents a phenyl group.
- EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
- R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aryl group.
- the carboxylate anion is also preferably represented by the following formula (X).
- L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR X —, and a combination thereof, and R X represents a hydrogen atom, An alkyl group, an alkenyl group or an aryl group is represented.
- carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
- ammonium cation is preferably represented by any one of the following general formulas (Y1-1) to (Y1-6).
- R 101 represents an n-valent organic group
- R 102 to R 111 each independently represents a hydrogen atom or a hydrocarbon group
- R 150 and R 151 each independently represent a hydrocarbon group
- R 104 and R 105 , R 104 and R 150 , R 107 and R 108 , and R 109 and R 110 may be bonded to each other to form a ring
- Ar 101 and Ar 102 each independently represent an aryl group
- n represents an integer of 1 or more
- m represents an integer of 0 to 5.
- R 104 and R 105 , R 104 and R 150 , R 107 and R 108 , and R 109 and R 110 may be bonded to each other to form a ring.
- the ring include an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, a heterocyclic ring, and the like.
- the ring may be monocyclic or polycyclic.
- the linking group is selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group, and combinations thereof.
- the bivalent coupling group chosen is mentioned.
- the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole.
- the ammonium cation preferably has a structure represented by the formula (Y1-1) or (Y1-2), represented by the formula (Y1-1) or (Y1-2), and R 101 is aryl.
- a structure which is a group is more preferable, and a structure represented by the formula (Y1-1) and in which R 101 is an aryl group is particularly preferable. That is, in the present invention, the ammonium cation is more preferably represented by the following formula (Y).
- Ar 10 represents an aromatic group
- R 11 to R 15 each independently represent a hydrogen atom or a hydrocarbon group
- R 14 and R 15 are bonded to each other to form a ring.
- N may represent an integer of 1 or more.
- R 11 and R 12 each independently represents a hydrogen atom or a hydrocarbon group.
- the hydrocarbon group is not particularly limited, but is preferably an alkyl group, an alkenyl group or an aryl group.
- R 11 and R 12 are preferably a hydrogen atom.
- R 13 to R 15 each represents a hydrogen atom or a hydrocarbon group.
- the hydrocarbon group include the hydrocarbon groups described above for R 11 and R 12 .
- R 13 to R 15 are particularly preferably alkyl groups, and preferred embodiments are also the same as those described for R 11 and R 12 .
- R 14 and R 15 may be bonded to each other to form a ring.
- the ring include cycloaliphatic (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring and the like.
- the ring may be monocyclic or polycyclic.
- the linking group in the case where R 14 and R 15 are combined to form a ring includes —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
- Specific examples of the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole. Ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.
- R 13 to R 15 are a group in which R 14 and R 15 are bonded to each other to form a ring, or R 13 is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms).
- R 14 and R 15 are preferably each independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms).
- the total number of carbon atoms of R 13 , R 14 and R 15 is preferably 7 to 30, and more preferably 10 to 20.
- the amount of the chemical formula of “—NR 13 R 14 R 15 ” in the formula (Y) is preferably 80 to 2000, and more preferably 100 to 500, because an amine species having a high boiling point is likely to be generated.
- R 13 and R 14 are methyl groups or ethyl groups, and R 15 is a straight chain having 5 or more carbon atoms. Examples include a chain, branched or cyclic alkyl group, or an aryl group. R 13 and R 14 are methyl groups, and R 15 is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, a cyclic alkyl group having 6 to 10 carbon atoms, or a phenyl group.
- R 13 and R 14 are preferably methyl groups
- R 15 is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, a cyclic alkyl group having 6 to 8 carbon atoms, or a phenyl group. It is more preferable that By reducing the hydrophobicity of the amine species in this way, the affinity between the metal layer and polyimide or the like can be increased even when the amine adheres onto the metal layer such as copper.
- the acidic compound is also preferably a compound represented by the following formula (A1).
- This compound is acidic at room temperature, but by heating, the carboxyl group is lost by decarboxylation or dehydration cyclization, and the amine site that has been neutralized and inactivated becomes active. It becomes sex.
- the formula (A1) will be described.
- a 1 represents a p-valent organic group
- R 1 represents a monovalent organic group
- L 1 represents an (m + 1) -valent linking group
- m represents an integer of 1 or more
- p represents an integer of 1 or more.
- a 1 represents a p-valent organic group.
- the organic group include an aliphatic group and an aromatic group, and an aromatic group is preferable.
- the A 1 and aromatic group at lower temperatures, often invites a base having a boiling point higher. By increasing the boiling point of the generated base, volatilization or decomposition due to heating at the time of curing of the polyimide precursor can be suppressed, and cyclization of the polyimide precursor can proceed more effectively.
- the monovalent aliphatic group include an alkyl group and an alkenyl group.
- the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms.
- the alkyl group may be linear, branched or cyclic.
- the alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.
- the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
- the alkenyl group may be linear, branched or cyclic.
- the alkenyl group may have a substituent or may be unsubstituted.
- Examples of the alkenyl group include a vinyl group and a (meth) allyl group.
- Examples of the divalent or higher aliphatic group include groups obtained by removing one or more hydrogen atoms from the above monovalent aliphatic group.
- the aromatic group may be monocyclic or polycyclic.
- the aromatic group may be an aromatic heterocyclic group containing a hetero atom.
- the aromatic group may have a substituent or may be unsubstituted. Unsubstituted is preferred.
- aromatic group examples include benzene ring group, naphthalene ring group, pentalene ring group, indene ring group, azulene ring group, heptalene ring group, indacene ring group, perylene ring group, pentacene ring group, acenaphthene ring group, phenanthrene.
- a plurality of aromatic rings may be linked through a single bond or a linking group described later.
- the linking group for example, an alkylene group is preferable.
- the alkylene group is preferably linear or branched.
- Specific examples of the group in which a plurality of aromatic rings are linked through a single bond or a linking group include a biphenyl group, a diphenylmethane group, a diphenylpropane group, a diphenylisopropane group, a triphenylmethane group, and a tetraphenylmethane group.
- Examples of the substituent that the organic group represented by A 1 may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methoxy group, an ethoxy group and a tert-butoxy group.
- a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
- a methoxy group, an ethoxy group and a tert-butoxy group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- An acyloxy group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxalyl group; an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; And arylsulfanyl groups such as p-tolylsulfanyl group; alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; halogenated alkyl groups
- L 1 represents a (m + 1) -valent linking group.
- the linking group is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group (preferably a straight chain having 1 to 10 carbon atoms).
- the total carbon number of the linking group is preferably 3 or less.
- the linking group is preferably an alkylene group, a cycloalkylene group, or an alkenylene group, more preferably a linear or branched alkylene group, still more preferably a linear alkylene group, particularly preferably an ethylene group or a methylene group, and most preferably a methylene group.
- R 1 represents a monovalent organic group.
- the monovalent organic group include an aliphatic group and an aromatic group. Aliphatic group, for aromatic groups include those described in A 1 described above.
- the monovalent organic group represented by R 1 may have a substituent. Examples of the substituent include those described above.
- R 1 is preferably a group having a carboxyl group. That is, R 1 is preferably a group represented by the following formula. -L 2- (COOH) n
- L 2 represents an (n + 1) -valent linking group
- n represents an integer of 1 or more.
- Examples of the linking group represented by L 2 include the groups described above for L 1 , and the preferred ranges are also the same, an ethylene group or a methylene group is particularly preferred, and a methylene group is most preferred.
- n represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
- the upper limit of n is the maximum number of substituents that can take the linking group L 2 represents. If n is 1, a tertiary amine having a high boiling point is likely to be generated by heating at 200 ° C. or lower. Furthermore, the stability of the resin composition can be improved.
- m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
- the upper limit of m is the maximum number of substituents that the linking group represented by L 1 can take.
- m 1, a tertiary amine having a high boiling point is likely to be generated by heating at 200 ° C. or lower.
- p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
- the upper limit of p is the maximum number of substituents that can take the organic group A 1 represents. When p is 1, a tertiary amine having a high boiling point is likely to be generated by heating at 200 ° C. or lower.
- the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a).
- a 1 represents a p-valent organic group
- L 1 represents an (m + 1) -valent linking group
- L 2 represents an (n + 1) -valent linking group
- m represents an integer of 1 or more
- N represents an integer of 1 or more
- p represents an integer of 1 or more.
- a 1 , L 1 , L 2 , m, n, and p in the general formula (1a) have the same meanings as the ranges described in the general formula (A1), and preferred ranges are also the same.
- the compound represented by the formula (A1) is preferably N-aryliminodiacetic acid.
- a 1 in the general formula (A1) is an aromatic group
- L 1 and L 2 are methylene groups
- m is 1
- n is 1
- p is 1
- N-aryliminodiacetic acid tends to generate a tertiary amine having a high boiling point at 120 to 200 ° C.
- thermal base generator is not limited to these. These can be used alone or in admixture of two or more. Me in the following formulas represents a methyl group.
- (A-1) to (A-11), (A-18), and (A-19) are compounds represented by the above formula (A1). Of the compounds shown below, (A-1) to (A-11), (A-18) to (A-26) are more preferred, and (A-1) to (A-9), (A-18) ) To (A-21), (A-23), and (A-24) are more preferable.
- thermal base generator used in the present invention, compounds described in paragraph Nos. 0015 to 0055 of Japanese Patent Application No. 2015-034388 are also preferably used, the contents of which are incorporated herein.
- the content of the thermal base generator in the resin composition is preferably 0.1 to 50% by mass with respect to the total solid content of the resin composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
- 1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
- the resin composition in the present invention may contain a thermal radical polymerization initiator.
- a thermal radical polymerization initiator a known thermal radical polymerization initiator can be used.
- the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound.
- the thermal radical polymerization initiator By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor is advanced.
- a polyimide precursor contains a radically polymerizable group, since the polymerization reaction of a polyimide precursor can also be advanced with the cyclization of a polyimide precursor, higher heat resistance can be achieved.
- Thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable.
- the thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C. Specific examples include compounds described in paragraph numbers 0074 to 0118 of JP-A-2008-63554. In a commercial item, perbutyl Z and park mill D (made by NOF Corporation) can be used conveniently.
- the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, preferably 0.1 to 30% by mass with respect to the total solid content of the resin composition. Is more preferable, and 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.
- the resin composition in the present invention preferably contains a rust inhibitor.
- a resin composition contains a rust preventive agent, it can suppress effectively that the metal ion derived from a metal layer (metal wiring) moves into a resin composition layer.
- the rust inhibitor include a rust inhibitor described in paragraph 0094 of JP2013-15701A, a compound described in paragraphs 0073 to 0076 of JP2009-283711A, and paragraph 0052 of JP2011-59656A. And the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.
- a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine Ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, hydrazide Derivative compounds are mentioned.
- triazole compounds such as triazole and benzotriazole
- tetrazole compounds such as tetrazole and benzotetrazole are preferable.
- 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole 1H-tetrazole, 5-methyl-1H-tetrazole and 5-phenyl-1H-tetrazole are more preferred, and 1H-tetrazole is most preferred.
- KEMITEC BT-C Kemipro Kasei Co., Ltd., 1,2,3-benzotriazole
- 1HT Toyobo Co., Ltd., 1H-tetrazole
- P5T Toyobo Co., Ltd., 5- Phenyl-1H-tetrazole
- the content of the rust inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the resin. Only one type of rust inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
- the resin composition in the present invention preferably contains a silane coupling agent in order to improve adhesiveness with a metal material used for electrodes, wirings and the like.
- the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252A. Examples thereof include compounds described in paragraphs 0060 to 0061, compounds described in paragraphs 0045 to 0052 of JP 2014-41264 A, and compounds described in paragraph 0055 of international publication WO 2014/097594.
- silane coupling agent 2-((3- (triethoxysilyl) propyl) carbamoyl) benzoic acid, triethoxysilylpropyl maleamic acid, and the following compounds are also preferably used.
- Et represents an ethyl group.
- KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane
- KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane
- the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin.
- membrane obtained by making content of a silane coupling agent into 0.1 mass part or more becomes favorable, and it is obtained by making content of a silane coupling agent into 30 mass parts or less.
- the heat resistance and mechanical properties of the film are improved. Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
- Solvent when the resin composition is layered by coating, it is preferable to add a solvent to the resin composition.
- a known solvent can be arbitrarily used as the solvent. Examples thereof include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and the like.
- esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, and ⁇ -caprolactone , ⁇ -valerolactone, alkyl oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.
- alkyl oxyacetates for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl al
- 3-alkyloxypropionic acid alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropioate) Ethyl), methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
- 2-alkyloxypropionic acid alkyl esters for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2- Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
- 2-alkyloxy Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate for example
- ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
- ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
- aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
- Preferred examples of the sulfoxides include dimethyl sulfoxide.
- the solvent is preferably in the form of a mixture of two or more from the viewpoint of improving the properties of the coated surface.
- a mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- the content of the solvent is preferably such that the total solid concentration of the resin composition is 5 to 80% by mass from the viewpoint of applicability. More preferred is 10 to 60% by mass.
- the solvent content may be adjusted depending on the desired thickness and coating method. For example, if the coating method is spin coating or slit coating, the content of the solvent having a solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass. By adjusting the amount of solvent by the coating method, a resin composition layer having a desired thickness can be formed uniformly.
- One type of solvent may be sufficient and 2 or more types may be sufficient as it.
- the total is preferably in the above range.
- the contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are based on the total mass of the resin composition from the viewpoint of film strength. Less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.
- the resin composition in the present invention may contain a sensitizing dye.
- a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
- the sensitizing dye in an electronically excited state comes into contact with a thermal base generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
- the thermal base generator, the photobase generator, the thermal radical polymerization initiator, and the photopolymerization initiator are decomposed by a chemical change to generate radicals, acids, or bases.
- the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
- the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. More preferably, it is 0.5 to 10% by mass.
- a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
- the resin composition in the present invention may contain a chain transfer agent.
- the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
- As the chain transfer agent for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals.
- thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
- 2-mercaptobenzimidazoles for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
- the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition. Part, more preferably 1 to 5 parts by weight. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
- surfactant Various surfactants may be added to the resin composition in the present invention from the viewpoint of further improving applicability.
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
- the following surfactants are also preferable.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 2.0% by mass with respect to the total solid content of the resin composition. 1.0% by mass. Only one surfactant may be used, or two or more surfactants may be used. When two or more surfactants are contained, the total is preferably in the above range.
- a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the resin composition in the present invention, and it is applied to the surface of the composition in the process of drying after coating. It may be unevenly distributed.
- the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
- the resin composition in the present invention is within a range that does not impair the effects of the present invention, and various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, agglomerates, as necessary.
- An inhibitor or the like can be blended.
- blending these additives it is preferable that the total compounding quantity shall be 3 mass% or less of solid content of a resin composition.
- the water content of the resin composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of coating surface properties.
- the metal content of the resin composition is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and particularly preferably less than 0.5 ppm by weight.
- the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
- a raw material having a low metal content is selected as a raw material constituting the resin composition. Examples of the method include filtration and distillation under conditions where the inside of the apparatus is lined with polytetrafluoroethylene or the like and contamination is suppressed as much as possible.
- the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
- a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, Especially less than 0.5 mass ppm is preferable.
- the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.
- the resin composition can be prepared by mixing the above components.
- the mixing method is not particularly limited, and can be performed by a conventionally known method.
- the filter pore size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
- filters having different pore diameters and / or materials may be used in combination.
- Various materials may be filtered a plurality of times.
- circulation filtration may be used.
- you may pressurize and filter.
- the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
- impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- An electronic device 100 shown in FIG. 2 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
- the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described.
- the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.
- Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate.
- the uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
- the semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.
- the stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump.
- connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.
- An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.
- the stacked body 101 is stacked on the wiring substrate 120.
- the wiring substrate 120 for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used.
- the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).
- a surface electrode 120 a is provided on one surface of the wiring board 120.
- An insulating layer 115 in which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected.
- the insulating layer 115 is formed by using the laminate manufacturing method of the present invention.
- the insulating layer 115 may be a stacked body having a multilayer wiring structure as shown in FIG.
- One end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump.
- the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
- An underfill layer 110 a is formed between the insulating layer 115 and the stacked body 101.
- an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.
- the method for producing an electronic device of the present invention includes the above-described method for producing a laminate of the present invention.
- the electronic device manufacturing method of the present invention preferably manufactures a plurality of electronic devices under the same storage process conditions.
- reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added.
- the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C. During the addition of SOCl 2 the viscosity increased. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
- the mixture was further stirred at 75 ° C. for 2 hours under a nitrogen atmosphere.
- the polymer was precipitated by pouring into 5 liters of water and stirred for 15 minutes at a speed of 5000 rpm.
- the acrylic resin was collected by filtration, poured into 4 liters of water again, stirred for another 30 minutes, and collected again by filtration.
- the obtained acrylic resin was dried at 45 ° C. under reduced pressure for 3 days to obtain an acrylic polymer (P-6) represented by the following formula.
- composition ⁇ Preparation of photosensitive resin composition> The following components were mixed to prepare a photosensitive resin composition coating solution as a uniform solution.
- composition Resin: Mass part radical polymerizable compound described in the following table: Mass part photoradical polymerization initiator described in the following table: Mass part silane coupling agent described in the following table: Mass part rust preventive described in the following table: Mass parts polymerization inhibitor described in the following table: Mass parts base generator described in the following table: Mass parts solvent 1 (dimethyl sulfoxide) described in the following table: 100 parts by mass Solvent 2 ( ⁇ -butyrolactone): 25 parts by mass
- B-1 SR209 (manufactured by Sartomer, tetraethylene glycol diacrylate)
- B-2 NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate)
- B-3 A-TMMT (made by Shin-Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)
- B-4 A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)
- C-1 IRGACURE OXE 01 (manufactured by BASF, oxime compound)
- C-2 IRGACURE OXE 02 (manufactured by BASF, oxime compound)
- C-3 IRGACURE-784 (made by BASF, metallocene compound)
- C-4 Adeka Arcles NCI-831 (manufactured by ADEKA Corporation, oxime compound)
- (Silane coupling agent) D-1 KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., silane compound having an amino group)
- D-2 2-((3- (triethoxysilyl) propyl) carbamoyl) benzoic acid (manufactured by Aquila Pharmatech LLC, silane compound having a carboxyl group)
- D-3 Triethoxysilylpropyl maleamic acid (manufactured by Gelest, Inc., silane compound having a carboxyl group)
- E-1 KEMITEC BT-C (Chemipro Kasei Co., Ltd., 1,2,3-benzotriazole)
- E-2 1HT (Toyobo Co., Ltd., 1H-tetrazole)
- E-3 P5T (manufactured by Toyobo Co., Ltd., 5-phenyl-1H-tetrazole)
- Base generator A-1, A-21, A-40: Compounds having the following structure (thermal base generator) A-43: WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd., photobase generator. This compound is also a compound that decomposes upon heating to generate a base, that is, a thermal base generator.)
- a laminated body 1 was formed by forming a copper thin film of 5 ⁇ m.
- save process was left still in the clean constant temperature and humidity chamber (Espec Co., Ltd. product, PCR-3J) adjusted to the preset temperature as described in the following table
- a laminated body 2 was obtained by forming a copper thin film having a thickness of 5 ⁇ m on the layer.
- a laminated body 3 was obtained by forming a copper thin film having a thickness of 5 ⁇ m on the layer.
- the storage time in each condition described in the above table is the elapsed time after the surface temperature reaches the set temperature.
- the fluctuation range of the surface temperature in each storage process was 5 ° C. or less.
- save process was substantially the same as preset temperature.
- the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR2005 i9C). The exposure was performed using i-line, and the exposure was performed at a wavelength of 365 nm using a photomask of a fuse box in 1 ⁇ m increments from 5 ⁇ m to 25 ⁇ m at each exposure energy of 200 mJ / cm 2 .
- the exposed photosensitive resin composition layer was developed using cyclopentanone and propylene glycol methyl ether acetate as a developer. Specifically, cyclopentanone was sprayed on the exposed photosensitive resin composition layer, then propylene glycol methyl ether acetate was sprayed, and developed for 60 seconds.
- the line width at which the silicon wafer was exposed at the bottom of the fuse box was evaluated according to the following criteria.
- the measurement limit is 5 ⁇ m.
- the results are shown in the table. A: 5 to 8 ⁇ m B: Over 8 ⁇ m to 10 ⁇ m or less C: Over 10 ⁇ m to 15 ⁇ m or less D: Over 15 ⁇ m
- the example in which the storage step was performed was able to produce a laminate with good adhesion.
- the photosensitive resin compositions of Compositions 1 to 12 using a polyimide precursor as a resin have high limit resolution, and the laminates of Examples 1 to 33, 36, and 37 using this photosensitive resin composition are The metal wiring width can be made finer.
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Abstract
Description
<1> ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される樹脂と、光重合開始剤と、を含む感光性樹脂組成物を支持体上に適用して感光性樹脂組成物層を形成する感光性樹脂組成物層形成工程と、
感光性樹脂組成物層をパターン状に露光する露光工程と、
感光性樹脂組成物層を現像してパターンを形成する現像工程と、
パターンを加熱する加熱工程と、
加熱後のパターン上に金属層を形成する金属層形成工程とを含み、
感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間、現像工程と加熱工程との間、および、加熱工程と金属層形成工程との間の少なくとも一つにおいて、表面温度が一定温度に達してから、その状態で5分以上保存する保存工程を行う、積層体の製造方法。
<2> 露光工程と現像工程との間に保存工程を行う、<1>に記載の積層体の製造方法。
<3> 露光工程と現像工程との間に行う保存工程が、下記式を満たす、<2>に記載の積層体の製造方法;
5≦t1<(10-0.036×T1+12.3)×60
T1は露光工程と現像工程との間に行う保存工程における平均表面温度であって単位はKである;t1は露光工程と現像工程との間に行う保存工程の時間であって単位は分である。
<4> 感光性樹脂組成物層形成工程と露光工程との間に保存工程を行う、<1>~<3>のいずれか1つに記載の積層体の製造方法。
<5> 感光性樹脂組成物層形成工程と露光工程との間に行う保存工程が、下記式を満たす、<4>に記載の積層体の製造方法;
5≦t2<(10-0.031×T2+10.7)×60
T2は感光性樹脂組成物層形成工程と露光工程との間に行う保存工程における平均表面温度であって単位はKである;t2は感光性樹脂組成物層形成工程と露光工程との間に行う保存工程の時間であって単位は分である。
<6> 現像工程と加熱工程との間に、保存工程を行う、<1>~<5>のいずれか1つに記載の積層体の製造方法。
<7> 現像工程と加熱工程との間に行う保存工程が、下記式を満たす、<6>に記載の積層体の製造方法;
5≦t3<(10-0.02×T3+8.0)×60
T3は現像工程と加熱工程との間に行う保存工程における平均表面温度であって単位はKである;t3は現像工程と加熱工程との間に行う保存工程の時間であって単位は分である。
<8> 加熱工程と金属層形成工程との間に保存工程を行う、<1>~<7>のいずれか1つに記載の積層体の製造方法。
<9> 感光性樹脂組成物における樹脂がポリイミド前駆体であり、ポリイミド前駆体がラジカル重合性基を含むか、あるいは、感光性樹脂組成物がポリイミド前駆体以外のラジカル重合性化合物を含む、<1>~<8>のいずれか1つに記載の積層体の製造方法。
<10> ポリイミド前駆体が下記式(1)で表される繰り返し単位を含む、<1>~<9>のいずれか1つに記載の積層体の製造方法;
式(1)
<11> 式(1)中、R23およびR24の少なくとも一方が、ラジカル重合性基を含む、<10>に記載の積層体の製造方法。
<12> 式(1)におけるR22は、芳香環を含む4価の基である、<10>または<11>に記載の積層体の製造方法。
<13> 金属層形成工程後のパターン上に、感光性樹脂組成物層形成工程、露光工程、現像工程、加熱工程および金属層形成工程をこの順で行い、感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間、現像工程と加熱工程との間、および、加熱工程と金属層形成工程との間の少なくとも一つにおいて、保存工程を行う一連のサイクルを2サイクル以上行う、<1>~<12>のいずれか1つに記載の積層体の製造方法。
<14> 多層配線構造の積層体の製造方法である、<1>~<13>のいずれか1つに記載の積層体の製造方法。
<15> ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される樹脂と、光重合開始剤と、を含む感光性樹脂組成物を支持体上に適用して感光性樹脂組成物層を形成する感光性樹脂組成物層形成工程と、
感光性樹脂組成物層をパターン状に露光する露光工程と、
感光性樹脂組成物層を現像してパターンを形成する現像工程と、
パターンを加熱する加熱工程と、
加熱後のパターン上に金属層を形成する金属層形成工程とを含み、
感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間、現像工程と加熱工程との間、および、加熱工程と金属層形成工程との間の少なくとも一つにおいて、表面温度が一定温度に達してから、その状態で5分以上保存する保存工程を行う、積層体の製造方法を含む、電子デバイスの製造方法。
<16> 同一の保存工程の条件にて複数の電子デバイスを製造する、<15>に記載の電子デバイスの製造方法。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基と共に置換基を有する基をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、「(メタ)アクリレート」は、「アクリレート」および「メタクリレート」の双方、または、いずれかを表し、「(メタ)アリル」は、「アリル」および「メタリル」の双方、または、いずれかを表し、「(メタ)アクリル」は、「アクリル」および「メタクリル」の双方、または、いずれかを表し、「(メタ)アクリロイル」は、「アクリロイル」および「メタクリロイル」の双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。また、固形分濃度は、特に述べない限り25℃における濃度をいう。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィー(GPC)測定に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、および、TSKgel Super HZ2000(東ソー(株)製)を用いることによって求めることができる。溶離液は特に述べない限り、THF(テトラヒドロフラン)を用いるものとする。また、検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
本発明の積層体の製造方法は、ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される樹脂と、光重合開始剤と、を含む感光性樹脂組成物を支持体上に適用して感光性樹脂組成物層を形成する感光性樹脂組成物層形成工程と、
感光性樹脂組成物層をパターン状に露光する露光工程と、
感光性樹脂組成物層を現像してパターンを形成する現像工程と、
パターンを加熱する加熱工程と、
加熱後のパターン上に金属層を形成する金属層形成工程とを含み、
感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間、現像工程と加熱工程との間、および、加熱工程と金属層形成工程との間の少なくとも一つにおいて、表面温度が一定温度に達してからその状態で5分以上保存する保存工程を行うことを特徴とする。
また、感光性樹脂組成物における上述した樹脂がポリイミド前駆体であり、このポリイミド前駆体がラジカル重合性基を含むか、あるいは、上述したポリイミド前駆体以外のラジカル重合性化合物を含む感光性樹脂組成物を用いた場合においては、特に本発明の効果が顕著である。詳細な理由は不明であるが、このようなラジカル重合性成分(ラジカル重合性基を有するポリイミド前駆体、ポリイミド前駆体以外のラジカル重合性化合物)を含む感光性樹脂を用いた場合、露光工程および現像工程時において、ラジカル重合性成分のラジカル重合による架橋反応を利用してパターンを形成し、得られたパターンを加熱工程において高温に加熱してイミド化反応を起こして、高耐熱、高絶縁性の膜を形成している。このように、上述のラジカル重合性成分を含む感光性組成物を用いた場合においては、反応が多段階で複雑であるが、上述の保存工程を設けることで、膜のミクロな状態を安定させることでき、形成した膜の性質を安定させて密着性に優れた積層体を製造することができたと推測する。
以下、本発明の積層体の製造方法における各工程について説明する。
本発明の積層体の製造方法は、感光性樹脂組成物を支持体上に適用して感光性樹脂組成物層を形成する感光性樹脂組成物層形成工程を含む。感光性樹脂組成物については後述する。
感光性樹脂組成物層の厚さは、露光後の膜厚が0.1~100μmとなるように塗布することが好ましく、1~50μmとなるように塗布することがより好ましい。また、形成される感光性樹脂組成物層の厚さは、必ずしも均一である必要はない。例えば、凹凸のある表面上に感光性樹脂組成物層を形成する場合、厚さの異なる感光性樹脂組成物層となることがある。
感光性樹脂組成物層形成工程では、支持体上に形成した感光性樹脂組成物層に対し、乾燥を行ってもよい。乾燥温度は50~150℃が好ましく、70~130℃がより好ましく、90~110℃がさらに好ましい。乾燥時間は、30秒~20分が好ましく、1~10分がより好ましく、3~7分が更に好ましい。なお、乾燥処理は、本発明における保存工程とは異なる工程である。
本発明の積層体の製造方法は、上記感光性樹脂組成物層をパターン状に露光する露光工程を含む。露光は、感光性樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で100~10000mJ/cm2にて照射することが好ましく、200~8000mJ/cm2にて照射することがより好ましい。露光波長は、190~1000nmの範囲で適宜定めることができ、240~550nmが好ましい。
本発明の積層体の製造方法は、露光された感光性樹脂組成物層に対して、感光性樹脂組成物層を現像してパターンを形成する現像工程を含む。現像は現像液を用いて行う。現像液は、特に制限なく使用できる。溶剤が好ましい。現像液に用いる溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類などの有機溶剤が挙げられる。これらの詳細については、後述する樹脂組成物の欄で説明する溶剤が挙げられる。
なかでも3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、シクロペンタノン、γ-ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートが好ましく、シクロペンタノン、γ-ブチロラクトンがより好ましい。
本発明の積層体の製造方法は、現像工程により得られたパターン(樹脂層)を加熱する加熱工程を含む。加熱工程では、ポリイミド前駆体などの環化反応が進行する。また、未反応のラジカル重合性成分の硬化なども進行する。最高加熱温度(加熱時の最高温度)としては、100~500℃が好ましく、140~400℃がより好ましく、160~350℃がさらに好ましい。
加熱は、20~150℃の温度から最高加熱温度まで1~12℃/分の昇温速度で行うことが好ましく、2~10℃/分がより好ましく、3~10℃/分がさらに好ましい。昇温速度を2℃/分以上とすることにより、高い生産性を確保しつつ、アミンの過剰な揮発を防止することができ、昇温速度を12℃/分以下とすることにより、得られる膜に残存する応力を緩和することができる。
加熱開始時の温度は、20~150℃が好ましく、20℃~130℃がより好ましく、25℃~120℃がさらに好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の加熱温度のことをいう。例えば、感光性樹脂組成物を基板の上に適用した後、乾燥させる場合、この乾燥後の温度であり、例えば、感光性樹脂組成物に含まれる溶剤の沸点よりも30~200℃低い温度から徐々に昇温させることが好ましい。
加熱は、最高加熱温度に到達した後、10~360分間加熱を行うことが好ましく、20~300分間加熱を行うことがさらに好ましく、30~240分間加熱を行うことが特に好ましい。
さらに、加熱後冷却してもよく、この場合の冷却速度としては、1~5℃/分であることが好ましい。
本発明の積層体の製造方法は、加熱後のパターン(樹脂層)上に金属層を形成する金属層形成工程を含む。金属層としては、特に限定なく、既存の金属種を使用することができる。例えば、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金およびタングステンが挙げられ、銅およびアルミニウムが好ましく、銅がより好ましい。金属層の形成方法は、特に限定なく、既存の方法を適用することができる。例えば、特開2007-157879号公報、特表2001-521288号公報、特開2004-214501号公報、特開2004-101850号公報に記載された方法を使用することができる。例えば、フォトリソグラフィ、リフトオフ、電解メッキ、無電解メッキ、エッチング、印刷、及びこれらを組み合わせた方法などが考えられる。より具体的には、スパッタリング、フォトリソグラフィおよびエッチングを組み合わせたパターニング方法、フォトリソグラフィと電解メッキとを組み合わせたパターニング方法が挙げられる。
金属層の厚さとしては、最も厚い部分で、0.1~50μmが好ましく、1~10μmがより好ましい。
本発明の積層体の製造方法は、上記金属層及び感光性樹脂組成物層の少なくとも一部を表面活性化処理する表面活性化処理工程を含んでいてもよい。表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、加熱工程後の感光性樹脂組成物層の少なくとも一部のみに行っても良いし、金属層および加熱工程後の感光性樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。
表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記加熱工程の後、感光性樹脂組成物層に、表面活性化処理工程を行ってから、金属層を形成してもよい。
表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に感光性樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる感光性樹脂組成物層層との密着性を向上させることができる。
また、表面活性化処理は、加熱工程後の感光性樹脂組成物層の一部または全部についても行うことが好ましい。このように、感光性樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や感光性樹脂組成物層との密着性を向上させることができる。
表面活性化処理としては、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF4/O2、NF3/O2、SF6、NF3、NF3/O2によるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200000J/m2が好ましく、1000~100000J/m2がより好ましく、10000~50000J/m2が最も好ましい。
本発明の積層体の製造方法は、感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間、現像工程と加熱工程との間、および、加熱工程と金属層形成工程との間の少なくとも一つにおいて、表面温度が一定温度に達してからその状態で5分以上保存する保存工程を行う。各工程間の全てにおいても上述の保存工程を行ってもよく、各工程間のいずれか一つのみにおいて、上述の保存工程を行ってもよい。本発明においては、感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間および現像工程と加熱工程との間の少なくとも一つにおいて上述の保存工程を行うことが好ましく、露光工程と現像工程との間に保存工程を行うことがより好ましい。露光工程と現像工程との間に保存工程を行うことで、感光性樹脂組成物層の密着性をより向上できる。
5≦t1<(10-0.036×T1+12.3)×60
T1はPED工程における平均表面温度であって単位はKである;t1はPED工程の時間であって単位は分である。
5≦t2<(10-0.031×T2+10.7)×60
T2はPCD工程における平均表面温度であって単位はKである;t2はPCD工程の時間であって単位は分である。
5≦t3<(10-0.02×T3+8.0)×60
T3はPDD工程における平均表面温度であって単位はKである;t3はPDD工程の時間であって単位は分である。
また、積層数を増やすに伴い、金属層と樹脂層との界面、樹脂層同士の界面、樹脂層と支持体との界面において剥がれが生じやすくなるが、本発明の積層体の製造方法によれば、積層数を増やしても各層間での剥がれが生じにくい。このため、本発明の効果がより顕著に得られる。
樹脂層201には所望のパターンが形成されている。例えば、このパターンは例えばネガ型現像によって形成することができる。樹脂層201の表面には金属層301が形成されている。この金属層301は樹脂層201に形成された溝401の表面の一部を覆うように形成されている。
金属層301上には、樹脂層202が形成されている。樹脂層202には所望のパターンが形成されて金属層301の一部が樹脂層202から露出している。樹脂層202の表面には金属層302が形成されている。この金属層302は樹脂層202に形成された溝402の表面の一部を覆うように形成され、樹脂層202から露出した金属層301と電気的に接続している。
金属層302上には、樹脂層203が形成されている。樹脂層203には所望のパターンが形成されて、金属層302の一部が樹脂層203から露出している。樹脂層203の表面には金属層303が形成されている。この金属層303は樹脂層203に形成された溝403の表面の一部を覆うように形成されており、樹脂層203から露出した金属層302と電気的に接続している。
金属層303上には、樹脂層204が形成されている。樹脂層204には所望のパターンが形成されて、金属層303の一部が樹脂層204から露出している。また、図1では金属層302の一部も樹脂層204から露出している。
この積層体は、樹脂層201~204が絶縁膜として働き、金属層301~303が配線層として機能する。このような積層体は、電子デバイスにおける再配線層として好ましく用いることができる。
次に、本発明の積層体の製造方法に用いる感光性樹脂組成物(以下、樹脂組成物ともいう)について説明する。
本発明における樹脂組成物は、ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される樹脂を含む。樹脂としてポリイミド前駆体やポリベンゾオキサゾール前駆体を用いた場合、膜の性状が安定しにくい傾向になる。このため、樹脂としてポリイミド前駆体やポリベンゾオキサゾール前駆体を用いた場合、特に本発明の効果が顕著に得られやすい。なかでも、樹脂としてポリイミド前駆体(好ましくは、ラジカル重合性基を有するポリイミド前駆体)を用いた場合、特に本発明の効果がより顕著に得られやすい。
また、樹脂組成物における、ポリイミド前駆体の含有量は、樹脂組成物の全固形分に対し20~99質量%が好ましく、50~99質量%がより好ましく、60~99質量%がさらに好ましく、70~99質量%が特に好ましい。
また、樹脂組成物に含まれる樹脂の全質量中におけるポリイミド前駆体の含有量は、80~100質量%であることが好ましく、90~100質量%であることがより好ましい。樹脂組成物に含まれる樹脂は、実質的にポリイミド前駆体のみで構成されていることが好ましい。樹脂組成物に含まれる樹脂が、実質的にポリイミド前駆体のみで構成されている場合とは、例えば、樹脂組成物に含まれるポリイミド前駆体以外の樹脂の含有量が、ポリイミド前駆体の含有量の3質量%以下であることが好ましい。
ポリイミド前駆体としては、式(1)で表される繰り返し単位を含むポリイミド前駆体であることが好ましい。
式(1)
1,2-ジアミノエタン、1,2-ジアミノプロパン、1,3-ジアミノプロパン、1,4-ジアミノブタンおよび1,6-ジアミノヘキサン;1,2-または1,3-ジアミノシクロペンタン、1,2-、1,3-または1,4-ジアミノシクロヘキサン、1,2-、1,3-または1,4-ビス(アミノメチル)シクロヘキサン、ビス-(4-アミノシクロヘキシル)メタン、ビス-(3-アミノシクロヘキシル)メタン、4,4’-ジアミノ-3,3’-ジメチルシクロヘキシルメタンおよびイソホロンジアミン;m-およびp-フェニレンジアミン、ジアミノトルエン、4,4’-および3,3’-ジアミノビフェニル、4,4’-および3,3’-ジアミノジフェニルエーテル、4,4’-および3,3’-ジアミノジフェニルメタン、4,4’-および3,3’-ジアミノジフェニルスルホン、4,4’-および3,3’-ジアミノジフェニルスルフィド、4,4’-および3,3’-ジアミノベンゾフェノン、3,3’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、2,2-ビス(4-アミノフェニル)プロパン、2,2-ビス(4-アミノフェニル)ヘキサフルオロプロパン、2,2-ビス(3-ヒドロキシ-4-アミノフェニル)プロパン、2,2-ビス(3-ヒドロキシ-4-アミノフェニル)ヘキサフルオロプロパン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-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、ビス(3-アミノ-4-ヒドロキシフェニル)スルホン、ビス(4-アミノ-3-ヒドロキシフェニル)スルホン、4,4’-ジアミノパラテルフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、ビス[4-(2-アミノフェノキシ)フェニル]スルホン、1,4-ビス(4-アミノフェノキシ)ベンゼン、9,10-ビス(4-アミノフェニル)アントラセン、3,3’-ジメチル-4,4’-ジアミノジフェニルスルホン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、3,3’-ジエチル-4,4’-ジアミノジフェニルメタン、3,3’-ジメチル-4,4’-ジアミノジフェニルメタン、4,4’-ジアミノオクタフルオロビフェニル、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、9,9-ビス(4-アミノフェニル)-10-ヒドロアントラセン、3,3’,4,4’-テトラアミノビフェニル、3,3’,4,4’-テトラアミノジフェニルエーテル、1,4-ジアミノアントラキノン、1,5-ジアミノアントラキノン、3,3-ジヒドロキシ-4,4’-ジアミノビフェニル、9,9’-ビス(4-アミノフェニル)フルオレン、4,4’-ジメチル-3,3’-ジアミノジフェニルスルホン、3,3’,5,5’-テトラメチル-4,4’-ジアミノジフェニルメタン、2,4-および2,5-ジアミノクメン、2,5-ジメチル-p-フェニレンジアミン、アセトグアナミン、2,3,5,6-テトラメチル-p-フェニレンジアミン、2,4,6-トリメチル-m-フェニレンジアミン、ビス(3-アミノプロピル)テトラメチルジシロキサン、2,7-ジアミノフルオレン、2,5-ジアミノピリジン、1,2-ビス(4-アミノフェニル)エタン、ジアミノベンズアニリド、ジアミノ安息香酸のエステル、1,5-ジアミノナフタレン、ジアミノベンゾトリフルオライド、1,3-ビス(4-アミノフェニル)ヘキサフルオロプロパン、1,4-ビス(4-アミノフェニル)オクタフルオロブタン、1,5-ビス(4-アミノフェニル)デカフルオロペンタン、1,7-ビス(4-アミノフェニル)テトラデカフルオロヘプタン、2,2-ビス[4-(3-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2-ビス[4-(2-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2-ビス[4-(4-アミノフェノキシ)-3,5-ジメチルフェニル]ヘキサフルオロプロパン、2,2-ビス[4-(4-アミノフェノキシ)-3,5-ビス(トリフルオロメチル)フェニル]ヘキサフルオロプロパン、p-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ベンゼン、4,4’-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ビフェニル、4,4’-ビス(4-アミノ-3-トリフルオロメチルフェノキシ)ビフェニル、4,4’-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ジフェニルスルホン、4,4’-ビス(3-アミノ-5-トリフルオロメチルフェノキシ)ジフェニルスルホン、2,2-ビス[4-(4-アミノ-3-トリフルオロメチルフェノキシ)フェニル]ヘキサフルオロプロパン、3,3’,5,5’-テトラメチル-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、4,4’-ジアミノ-2,2’-ビス(トリフルオロメチル)ビフェニル、2,2’,5,5’,6,6’-ヘキサフルオロトリジンおよび4,4’’’-ジアミノクアテルフェニルから選ばれる少なくとも1種のジアミン。
ピロメリット酸二無水物(PMDA)、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルスルフィドテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルメタンテトラカルボン酸二無水物、2,2’,3,3’-ジフェニルメタンテトラカルボン酸二無水物、2,3,3’,4’-ビフェニルテトラカルボン酸二無水物、2,3,3’,4’-ベンゾフェノンテトラカルボン酸二無水物、4,4’-オキシジフタル酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、1,4,5,7-ナフタレンテトラカルボン酸二無水物、2,2-ビス(3,4-ジカルボキシフェニル)プロパン二無水物、2,2-ビス(2,3-ジカルボキシフェニル)プロパン二無水物、2,2-ビス(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン二無水物、1,3-ジフェニルヘキサフルオロプロパン-3,3,4,4-テトラカルボン酸二無水物、1,4,5,6-ナフタレンテトラカルボン酸二無水物、2,2’,3,3’-ジフェニルテトラカルボン酸二無水物、3,4,9,10-ペリレンテトラカルボン酸二無水物、1,2,4,5-ナフタレンテトラカルボン酸二無水物、1,4,5,8-ナフタレンテトラカルボン酸二無水物、1,8,9,10-フェナントレンテトラカルボン酸二無水物、1,1-ビス(2,3-ジカルボキシフェニル)エタン二無水物、1,1-ビス(3,4-ジカルボキシフェニル)エタン二無水物、および1,2,3,4-ベンゼンテトラカルボン酸二無水物、並びに、これらの炭素数1~6のアルキル誘導体および炭素数1~6のアルコキシ誘導体から選ばれる少なくとも1種のテトラカルボン酸二無水物。
式(III)において、R201は、炭素数2~12のアルキレン基、-CH2CH(OH)CH2-または炭素数4~30のポリオキシアルキレン基を表す。好適なR201の例としては、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、-CH2CH(OH)CH2-が挙げられ、エチレン基、プロピレン基、トリメチレン基、-CH2CH(OH)CH2-がより好ましい。R200がメチル基で、R201がエチレン基である組み合わせが特に好ましい。
環状のアルキル基は、単環の環状アルキル基であってもよく、多環の環状アルキル基であってもよい。単環の環状アルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基およびシクロオクチル基が挙げられる。多環の環状アルキル基としては、例えば、アダマンチル基、ノルボルニル基、ボルニル基、カンフェニル基、デカヒドロナフチル基、トリシクロデカニル基、テトラシクロデカニル基、カンホロイル基、ジシクロヘキシル基およびピネニル基が挙げられる。中でも、高感度化との両立の観点から、シクロヘキシル基が好ましい。
芳香族基としては、置換または無置換のベンゼン環基、ナフタレン環基、ペンタレン環基、インデン環基、アズレン環基、ヘプタレン環基、インダセン環基、ペリレン環基、ペンタセン環基、アセナフテン環基、フェナントレン環基、アントラセン環基、ナフタセン環基、クリセン環基、トリフェニレン環基、フルオレン環基、ビフェニル環基、ピロール環基、フラン環基、チオフェン環基、イミダゾール環基、オキサゾール環基、チアゾール環基、ピリジン環基、ピラジン環基、ピリミジン環基、ピリダジン環基、インドリジン環基、インドール環基、ベンゾフラン環基、ベンゾチオフェン環基、イソベンゾフラン環基、キノリジン環基、キノリン環基、フタラジン環基、ナフチリジン環基、キノキサリン環基、キノキサゾリン環基、イソキノリン環基、カルバゾール環基、フェナントリジン環基、アクリジン環基、フェナントロリン環基、チアントレン環基、クロメン環基、キサンテン環基、フェノキサチイン環基、フェノチアジン環基またはフェナジン環基が挙げられる。ベンゼン環基が好ましい。
他の繰り返し単位を含む場合、ポリイミド前駆体における、他の繰り返し単位の割合は、1~60モル%であることが好ましく、5~50モル%であることがより好ましい。
本発明で用いるポリイミドとしては、イミド環を有する高分子化合物であればよく、特に限定されないが、下記式(4)で表される化合物であることが好ましく、下記式(4)で表される化合物であって、ラジカル重合性基を有する化合物であることがより好ましい。ラジカル重合性基としては、上記のポリイミド前駆体で説明した重合性基が挙げられ、好ましい範囲も同様である。
式(4)
式(4-1)
式(4-2)
ポリイミドの市販品としては、Durimide(登録商標)284(富士フイルム社製)、Matrimide5218(HUNTSMAN社製)が例示される。
本発明において、ポリベンゾオキサゾール前駆体としては、その構造等について特に限定するものではないが、好ましくは下記式(3)で表される繰り返し単位を含む化合物である。
式(3)
脂肪族基を含むジカルボン酸としては、直鎖または分岐(好ましくは直鎖)の脂肪族基を含むジカルボン酸が好ましく、直鎖または分岐(好ましくは直鎖)の脂肪族基と2つのCOOHからなるジカルボン酸がより好ましい。直鎖または分岐(好ましくは直鎖)の脂肪族基の炭素数は、2~30であることが好ましく、2~25であることがより好ましく、3~20であることがさらに好ましく、4~15であることが特に好ましく、5~10であることが一層好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。直鎖の脂肪族基を含むジカルボン酸の具体例としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ-n-ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、2,2-ジメチルスクシン酸、2,3-ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、2-メチルグルタル酸、3-メチルグルタル酸、2,2-ジメチルグルタル酸、3,3-ジメチルグルタル酸、3-エチル-3-メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、3-メチルアジピン酸、ピメリン酸、2,2,6,6-テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、1,9-ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、さらに下記式で表されるジカルボン酸等が挙げられる。
ポリベンゾオキサゾールとしては、ベンゾオキサゾール環を有する化合物であればよく、特に限定されないが、下記式(X)で表される繰り返し単位を有する化合物であることが好ましく、下記式(X)で表される化合物であって、ラジカル重合性基を有する化合物であることがより好ましい。ラジカル重合性基としては、上記のポリイミド前駆体で説明したラジカル重合性基が挙げられ、好ましい範囲も同様である。
式(X-1)
式(X-2)
本発明における樹脂組成物は、更に、ラジカル重合性化合物を含有していてもよい。ラジカル重合性化合物を含有させることにより、ネガ型感光性樹脂組成物として好ましく用いることができる。更には、耐熱性に優れた硬化膜を形成することができる。ラジカル重合性化合物としては、エチレン性不飽和結合を有する化合物が好ましく、エチレン性不飽和結合を有する基を2個以上含む化合物であることがより好ましい。ラジカル重合性化合物は、例えば、モノマー、プレポリマー、オリゴマーおよびそれらの混合物並びにそれらの多量体などの化学的形態のいずれであってもよい。エチレン性不飽和結合を有する基としては、スチリル基、ビニル基、(メタ)アクリロイル基および(メタ)アリル基が好ましく、(メタ)アクリロイル基がより好ましい。なお、本発明におけるラジカル重合性化合物は、上述した樹脂とは異なる成分である。すなわち、ラジカル重合性基を有するポリイミド前駆体、ラジカル重合性基を有するポリイミド、ラジカル重合性基を有するポリベンゾオキサゾール前駆体およびラジカル重合性基を有するポリベンゾオキサゾールは、樹脂に該当する。
また、オリゴマータイプのラジカル重合性化合物は、典型的には比較的低い分子量の重合体であり、10個から100個のラジカル重合性モノマーが結合した重合体であることが好ましい。分子量としては、ゲルパーミエーションクロマトグラフィー(GPC)法でのポリスチレン換算の重量平均分子量が、2000~20000であることが好ましく、2000~15000がより好ましく、2000~10000であることがさらに好ましい。
上記式(MO-1)~(MO-5)で表される化合物の各々において、複数のRの内の少なくとも1つは、-OC(=O)CH=CH2、または、-OC(=O)C(CH3)=CH2で表される基を表す。
上記式(MO-1)~(MO-5)で表される化合物の具体例としては、特開2007-269779号公報の段落0248~0251に記載されている化合物が挙げられる。
式(i)中、(メタ)アクリロイル基の合計は3個または4個であり、mは各々独立に0~10の整数を表し、各mの合計は0~40の整数である。但し、各mの合計が0の場合、Xのうちいずれか1つはカルボキシル基である。
式(ii)中、(メタ)アクリロイル基の合計は5個または6個であり、nは各々独立に0~10の整数を表し、各nの合計は0~60の整数である。但し、各nの合計が0の場合、Xのうちいずれか1つはカルボキシル基である。
式(ii)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が特に好ましい。
式(i)または式(ii)中の-((CH2)yCH2O)-または-((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。特に、式(ii)において、6個のX全てがアクリロイル基である形態が好ましい。
市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、NKエステルM-40G、NKエステル4G、NKエステルM-9300、NKエステルA-9300、UA-7200(新中村化学工業(株)製)、DPHA-40H(日本化薬(株)製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社化学(株)製)、ブレンマーPME400(日油(株)製)などが挙げられる。
また、樹脂(好ましくはポリイミド前駆体)とラジカル重合性化合物との質量割合(樹脂/ラジカル重合性化合物)は、98/2~10/90が好ましく、95/5~30/70がより好ましく、90/10~50/50がさらに好ましい。樹脂とラジカル重合性化合物との質量割合が上記範囲であれば、硬化性および耐熱性により優れた硬化膜を形成できる。ラジカル重合性化合物は、1種のみ用いても、2種以上用いてもよい。2種以上用いる場合は、合計量が上記範囲となることが好ましい。
本発明における樹脂組成物は、光重合開始剤を含む。光重合開始剤としては、光カチオン重合開始剤、光ラジカル重合開始剤などが挙げられ、光ラジカル重合開始剤が好ましい。本発明における樹脂組成物が光ラジカル重合開始剤を含むことにより、樹脂組成物を半導体ウエハなどの基板に適用して樹脂組成物層を形成した後、光を照射することで、ラジカルに起因する硬化が起こり、光照射部における溶解性を低下させることができる。このため、例えば、電極部のみをマスクするパターンを持つフォトマスクを介して樹脂組成物層を露光することで、電極などのパターンにしたがって、溶解性の異なる領域を簡便に作製できるという利点がある。
α-ヒドロキシケトン化合物としては、IRGACURE-184(IRGACUREは登録商標)、DAROCUR-1173、IRGACURE-500、IRGACURE-2959、IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。
α-アミノケトン化合物としては、市販品であるIRGACURE-907、IRGACURE-369、および、IRGACURE-379(商品名:いずれもBASF社製)を用いることができる。α-アミノケトン化合物としては、365nmまたは405nm等の波長光源に吸収極大波長がマッチングされた特開2009-191179号公報に記載の化合物も用いることができる。
アシルホスフィン化合物としては、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイドなどが挙げられる。また、市販品であるIRGACURE-819やIRGACURE-TPO(商品名:いずれもBASF社製)を用いることができる。
メタロセン化合物としては、IRGACURE-784(BASF社製)などが例示される。
オキシム化合物の具体例としては、特開2001-233842号公報に記載の化合物、特開2000-80068号公報に記載の化合物、特開2006-342166号公報に記載の化合物を用いることができる。好ましいオキシム化合物としては、例えば、3-ベンゾオキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイルオキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、および2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オンなどが挙げられる。
最も好ましいオキシム化合物としては、特開2007-269779号公報に示される特定置換基を有するオキシム化合物や、特開2009-191061号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。
本発明における樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としては、例えば、ヒドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-クレゾール、ピロガロール、p-tert-ブチルカテコール、p-ベンゾキノン、ジフェニル-p-ベンゾキノン、4,4′-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2′-メチレンビス(4-メチル-6-tert-ブチルフェノール)、N-ニトロソ-N-フェニルヒドロキシアミンアルミニウム塩、フェノチアジン、N-ニトロソジフェニルアミン、N-フェニルナフチルアミン、エチレンジアミン四酢酸、1,2-シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、2,6-ジ-tert-ブチル-4-メチルフェノール、5-ニトロソ-8-ヒドロキシキノリン、1-ニトロソ-2-ナフトール、2-ニトロソ-1-ナフトール、2-ニトロソ-5-(N-エチル-N-スルフォプロピルアミノ)フェノール、N-ニトロソ-N-(1-ナフチル)ヒドロキシアミンアンモニウム塩、ビス(4-ヒドロキシ-3,5-tert-ブチル)フェニルメタンなどが好適に用いられる。また、特開2015-127817号公報の段落0060に記載の重合禁止剤、および、国際公開WO2015/125469号の段落0031~0046に記載の化合物を用いることもできる。
本発明における樹脂組成物は、光塩基発生剤を含んでいてもよい。光塩基発生剤とは、露光により塩基を発生するものであり、常温常圧の通常の条件下では活性を示さないが、外部刺激として電磁波の照射と加熱が行なわれると、塩基(塩基性物質)を発生するものであれば特に限定されるものではない。露光により発生した塩基はポリイミド前駆体を加熱により硬化させる際の触媒として働くため、ネガ型感光性樹脂組成物において好適に用いることができる。
発生する塩基性物質は、より塩基性度の高いアミノ基を有する化合物が好ましい。ポリイミド前駆体のイミド化における脱水縮合反応等に対する触媒作用が強く、より少量の添加で、より低い温度での脱水縮合反応等における触媒効果の発現が可能となるからである。つまりは、発生した塩基性物質の触媒効果が大きい為、樹脂組成物としての見た目の感度が向上する。上記触媒効果の観点からアミジン、脂肪族アミンであることが好ましい。
本発明における樹脂組成物は、熱塩基発生剤を含んでいてもよい。熱塩基発生剤としては、40℃以上に加熱すると塩基を発生する酸性化合物(A1)、および、pKa1が0~4のアニオンとアンモニウムカチオンとを有するアンモニウム塩(A2)から選ばれる少なくとも一種を含む熱塩基発生剤が好ましい。ここで、pKa1とは、多価の酸の第一のプロトンの解離定数(Ka)の対数表示(-Log10Ka)を示す。
上記酸性化合物(A1)および上記アンモニウム塩(A2)は、加熱すると塩基を発生するので、これらの化合物から発生した塩基により、ポリイミド前駆体などの環化反応を促進でき、ポリイミド前駆体などの環化を低温で行うことができる。また、これらの化合物は、塩基により環化して硬化するポリイミド前駆体などと共存させても、加熱しなければポリイミド前駆体などの環化が殆ど進行しないので、保存安定性に優れた樹脂組成物を調製することができる。
なお、本明細書において、酸性化合物とは、化合物を容器に1g採取し、イオン交換水とテトラヒドロフランとの混合液(質量比は水/テトラヒドロフラン=1/4)を50mL加えて、室温で1時間攪拌し、得られた溶液をpHメーターを用いて、20℃にて測定したpH値が7未満である化合物を意味する。
酸性化合物(A1)およびアンモニウム塩(A2)の塩基発生温度が120℃以上であれば、保存中に塩基が発生しにくいので、安定性に優れた樹脂組成物を調製することができる。酸性化合物(A1)およびアンモニウム塩(A2)の塩基発生温度が200℃以下であれば、ポリイミド前駆体の環化温度を低くすることができる。塩基発生温度は、例えば、示差走査熱量測定を用い、化合物を耐圧カプセル中5℃/分で250℃まで加熱し、最も温度が低い発熱ピークのピーク温度を読み取り、ピーク温度を塩基発生温度として測定することができる。
アニオンの種類は、カルボン酸アニオン、フェノールアニオン、リン酸アニオンおよび硫酸アニオンから選ばれる1種が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
カルボン酸アニオンは、2個以上のカルボキシル基を持つ2価以上のカルボン酸のアニオンが好ましく、2価のカルボン酸のアニオンがより好ましい。この態様によれば、樹脂組成物の安定性、硬化性および現像性をより向上できる熱塩基発生剤とすることができる。特に、2価のカルボン酸のアニオンを用いることで、樹脂組成物の安定性、硬化性および現像性をさらに向上できる。
本発明において、カルボン酸アニオンは、pKa1が4以下のカルボン酸のアニオンであることが好ましい。pKa1は、3.5以下がより好ましく、3.2以下がさらに好ましい。この態様によれば、樹脂組成物の安定性をより向上できる。
ここでpKa1とは、酸の第一解離定数の逆数の対数を表し、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値を用いることとする。
σmが正の値を示す置換基の例としては、例えば、CF3基(σm=0.43)、CF3CO基(σm=0.63)、HC≡C基(σm=0.21)、CH2=CH基(σm=0.06)、Ac基(σm=0.38)、MeOCO基(σm=0.37)、MeCOCH=CH基(σm=0.21)、PhCO基(σm=0.34)、H2NCOCH2基(σm=0.06)などが挙げられる。なお、Meはメチル基を表し、Acはアセチル基を表し、Phはフェニル基を表す。
R102~R111は、それぞれ独立に、水素原子、または、炭化水素基を表し、
R150およびR151は、それぞれ独立に、炭化水素基を表し、
R104とR105、R104とR150、R107とR108、および、R109とR110は、互いに結合して環を形成していてもよく、
Ar101およびAr102は、それぞれ独立に、アリール基を表し、
nは、1以上の整数を表し、
mは、0~5の整数を表す。
R11およびR12は、水素原子が好ましい。
炭化水素基としては、上述したR11、R12で説明した炭化水素基が挙げられる。R13~R15は、特にアルキル基が好ましく、好ましい態様もR11、R12で説明したものと同じである。
また、発生するアミン種の塩基性や沸点の観点から、R13とR14とR15の炭素原子の総数が7~30であることが好ましく、10~20であることがより好ましい。
また、沸点の高いアミン種を発生しやすいという理由から、式(Y)における「-NR13R14R15」の化学式量は、80~2000が好ましく、100~500がより好ましい。
1価の脂肪族基としては、例えば、アルキル基、アルケニル基等が挙げられる。
アルキル基の炭素数は、1~30が好ましく、1~20がより好ましく、1~10がさらに好ましい。アルキル基は直鎖、分岐、環状のいずれであってもよい。アルキル基は、置換基を有していてもよく、無置換であってもよい。アルキル基の具体例としては、メチル基、エチル基、tert-ブチル基、ドデシル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、アダマンチル基等が挙げられる。
アルケニル基の炭素数は、2~30が好ましく、2~20がより好ましく、2~10がさらに好ましい。アルケニル基は直鎖、分岐、環状のいずれであってもよい。アルケニル基は、置換基を有していてもよく、無置換であってもよい。アルケニル基としては、ビニル基、(メタ)アリル基等が挙げられる。
2価以上の脂肪族基としては、上記の1価の脂肪族基から水素原子を1個以上除いた基が挙げられる。
芳香族基は、単環であってもよく、多環であってもよい。芳香族基は、ヘテロ原子を含む芳香族複素環基であってもよい。芳香族基は、置換基を有していてもよく、無置換であってもよい。無置換が好ましい。芳香族基の具体例としては、ベンゼン環基、ナフタレン環基、ペンタレン環基、インデン環基、アズレン環基、ヘプタレン環基、インダセン環基、ペリレン環基、ペンタセン環基、アセナフテン環基、フェナントレン環基、アントラセン環基、ナフタセン環基、クリセン環基、トリフェニレン環基、フルオレン環基、ビフェニル環基、ピロール環基、フラン環基、チオフェン環基、イミダゾール環基、オキサゾール環基、チアゾール環基、ピリジン環基、ピラジン環基、ピリミジン環基、ピリダジン環基、インドリジン環基、インドール環基、ベンゾフラン環基、ベンゾチオフェン環基、イソベンゾフラン環基、キノリジン環基、キノリン環基、フタラジン環基、ナフチリジン環基、キノキサリン環基、キノキサゾリン環基、イソキノリン環基、カルバゾール環基、フェナントリジン環基、アクリジン環基、フェナントロリン環基、チアントレン環基、クロメン環基、キサンテン環基、フェノキサチイン環基、フェノチアジン環基、および、フェナジン環基が挙げられ、ベンゼン環基が最も好ましい。
芳香族基は、複数の芳香環が、単結合または後述する連結基を介して連結していてもよい。連結基としては、例えば、アルキレン基が好ましい。アルキレン基は、直鎖、分岐のいずれも好ましい。複数の芳香環が単結合または連結基を介して連結した基の具体例としては、ビフェニル基、ジフェニルメタン基、ジフェニルプロパン基、ジフェニルイソプロパン基、トリフェニルメタン基、テトラフェニルメタン基などが挙げられる。
R1は、カルボキシル基を有する基であることが好ましい。すなわち、R1は、下記式で表される基が好ましい。
-L2-(COOH)n
式中、L2は(n+1)価の連結基を表し、nは1以上の整数を表す。
L2が表す連結基は、上述したL1で説明した基が挙げられ、好ましい範囲も同様であり、エチレン基またはメチレン基が特に好ましく、メチレン基が最も好ましい。
nは1以上の整数を表し、1または2が好ましく、1がより好ましい。nの上限は、L2が表す連結基が取り得る置換基の最大数である。nが1であれば、200℃以下の加熱により、沸点の高い3級アミンを発生しやすい。更には、樹脂組成物の安定性を向上できる。
pは、1以上の整数を表し、1または2が好ましく、1がより好ましい。pの上限は、A1が表す有機基が取り得る置換基の最大数である。pが1であれば、200℃以下の加熱により、沸点の高い3級アミンを発生しやすい。
一般式(1a)のA1、L1、L2、m、nおよびpは、一般式(A1)で説明した範囲と同義であり、好ましい範囲も同様である。
熱塩基発生剤は、1種または2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。
本発明における樹脂組成物は、熱ラジカル重合開始剤を含んでいてもよい。熱ラジカル重合開始剤としては、公知の熱ラジカル重合開始剤を用いることができる。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性化合物の重合反応を開始または促進させる化合物である。熱ラジカル重合開始剤を添加することによって、ポリイミド前駆体の環化反応を進行させる際に、重合性化合物の重合反応を進行させることができる。また、ポリイミド前駆体がラジカル重合性基を含む場合は、ポリイミド前駆体の環化と共に、ポリイミド前駆体の重合反応を進行させることもできるので、より高耐熱化が達成できることとなる。
熱ラジカル重合開始剤としては、芳香族ケトン類、オニウム塩化合物、過酸化物、チオ化合物、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、アゾ系化合物等が挙げられる。中でも、過酸化物またはアゾ系化合物がより好ましく、過酸化物が特に好ましい。
本発明で用いる熱ラジカル重合開始剤は、10時間半減期温度が90~130℃であることが好ましく、100~120℃であることがより好ましい。
具体的には、特開2008-63554号公報の段落番号0074~0118に記載されている化合物が挙げられる。
市販品では、パーブチルZおよびパークミルD(日油(株)製)を好適に用いることができる。
本発明における樹脂組成物には、防錆剤を含有することが好ましい。樹脂組成物が防錆剤を含むことにより、金属層(金属配線)由来の金属イオンが樹脂組成物層内へ移動することを効果的に抑制できる。防錆剤としては、特開2013-15701号公報の段落0094に記載の防錆剤、特開2009-283711号公報の段落0073~0076に記載の化合物、特開2011-59656号公報の段落0052に記載の化合物、特開2012-194520号公報の段落0114、0116および0118に記載の化合物などを使用することができる。具体的には、複素環(ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、2H-ピラン環および6H-ピラン環、トリアジン環)を有する化合物、チオ尿素類およびメルカプト基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。なかでも、トリアゾール、ベンゾトリアゾール等のトリアゾール系化合物、テトラゾール、ベンゾテトラゾール等のテトラゾール系化合物が好ましく、1,2,4-トリアゾール、1,2,3-ベンゾトリアゾール、5-メチル-1H-ベンゾトリアゾール、1H-テトラゾール、5-メチル-1H-テトラゾール、5-フェニル-1H-テトラゾールがより好ましく、1H-テトラゾールが最も好ましい。市販品としては、KEMITEC BT-C(ケミプロ化成(株)製、1,2,3-ベンゾトリアゾール)、1HT(東洋紡(株)製、1H-テトラゾール)、P5T(東洋紡(株)製、5-フェニル-1H-テトラゾール)などが挙げられる。
本発明における樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるためシランカップリング剤を含んでいることが好ましい。シランカップリング剤の例としては、特開2014-191002号公報の段落0062~0073に記載の化合物、国際公開WO2011/080992A1号の段落0063~0071に記載の化合物、特開2014-191252号公報の段落0060~0061に記載の化合物、特開2014-41264号公報の段落0045~0052に記載の化合物、国際公開WO2014/097594号の段落0055に記載の化合物が挙げられる。また、特開2011-128358号公報の段落0050~0058に記載のように異なる2種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、2-((3-(トリエトキシシリル)プロピル)カルバモイル)安息香酸、トリエトキシシリルプロピルマレインアミド酸、下記化合物を用いることも好ましい。以下の式中、Etはエチル基を表す。市販品としては、KBM-602(信越化学工業(株)製、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン)などを用いることもできる。
本発明において、樹脂組成物を塗布によって層状にする場合、樹脂組成物に溶剤を配合することが好ましい。溶剤としては、公知の溶剤を任意に使用できる。例えば、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類などの化合物が挙げられる。
エステル類として、例えば、酢酸エチル、酢酸-n-ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ-ブチロラクトン、ε-カプロラクトン、δ-バレロラクトン、アルキルオキシ酢酸アルキル(例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル(例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等))、3-アルキルオキシプロピオン酸アルキルエステル類(例えば3-アルキルオキシプロピオン酸メチル、3-アルキルオキシプロピオン酸エチル等(例えば、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル等))、2-アルキルオキシプロピオン酸アルキルエステル類(例えば、2-アルキルオキシプロピオン酸メチル、2-アルキルオキシプロピオン酸エチル、2-アルキルオキシプロピオン酸プロピル等(例えば、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル))、2-アルキルオキシ-2-メチルプロピオン酸メチルおよび2-アルキルオキシ-2-メチルプロピオン酸エチル(例えば、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル等)、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル等が好適に挙げられる。
エーテル類として、例えば、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、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチ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モノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、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エチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が好適に挙げられる。
ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、2-ヘプタノン、3-ヘプタノン、N-メチル-2-ピロリドン等が好適に挙げられる。
芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等が好適に挙げられる。
スルホキシド類としてジメチルスルホキシド等が好適に挙げられる。
溶剤は1種のみでもよいし、2種以上であってもよい。溶剤が2種以上の場合は、その合計が上記範囲であることが好ましい。
また、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およびN,N-ジメチルホルムアミドの含有量は、膜強度の観点から、樹脂組成物の全質量に対して5質量%未満が好ましく、1質量%未満がより好ましく、0.5質量%未満がさらに好ましく、0.1質量%未満が一層好ましい。
本発明における樹脂組成物は、増感色素を含んでいてもよい。増感色素は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感色素は、熱塩基発生剤、光塩基発生剤、熱ラジカル重合開始剤、光重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱塩基発生剤、光塩基発生剤、熱ラジカル重合開始剤、光重合開始剤は化学変化を起こして分解し、ラジカル、酸或いは塩基を生成する。増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。樹脂組成物が増感色素を含む場合、増感色素の含有量は、樹脂組成物の全固形分に対し、0.01~20質量%が好ましく、0.1~15質量%がより好ましく、0.5~10質量%がさらに好ましい。増感色素は、1種単独で用いてもよいし、2種以上を併用してもよい。
本発明における樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内にSH、PH、SiH、GeHを有する化合物群が用いられる。これらは、低活性のラジカル種に水素供与して、ラジカルを生成するか、もしくは、酸化された後、脱プロトンすることによりラジカルを生成し得る。特に、チオール化合物(例えば、2-メルカプトベンズイミダゾール類、2-メルカプトベンズチアゾール類、2-メルカプトベンズオキサゾール類、3-メルカプトトリアゾール類、5-メルカプトテトラゾール類等)を好ましく用いることができる。樹脂組成物が連鎖移動剤を含有する場合、連鎖移動剤の含有量は、樹脂組成物の全固形分100質量部に対し、好ましくは0.01~20質量部、より好ましくは1~10質量部、さらに好ましくは1~5質量部である。連鎖移動剤は1種のみでもよいし、2種以上であってもよい。連鎖移動剤が2種以上の場合は、その合計が上記範囲であることが好ましい。
本発明における樹脂組成物には、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。また、下記界面活性剤も好ましい。
本発明における樹脂組成物には、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で組成物の表面に偏在させてもよい。樹脂組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、樹脂組成物の全固形分に対して、0.1~10質量%が好ましい。高級脂肪酸誘導体は1種のみでもよいし、2種以上であってもよい。高級脂肪酸誘導体が2種以上の場合は、その合計が上記範囲であることが好ましい。
本発明における樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種添加物、例えば、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は樹脂組成物の固形分の3質量%以下とすることが好ましい。
本発明における樹脂組成物の水分含有量は、塗布面性状の観点から、5質量%未満が好ましく、1質量%未満がさらに好ましく、0.6質量%未満が特に好ましい。
また、樹脂組成物に意図せずに含まれる金属不純物を低減する方法としては、樹脂組成物を構成する原料として金属含有量が少ない原料を選択する、樹脂組成物を構成する原料に対してフィルター濾過を行う、装置内をポリテトラフロロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。
樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
また、樹脂組成物中のゴミや微粒子等の異物を除去する目的で、フィルターを用いたろ過を行うことが好ましい。フィルター孔径は、1μm以下が好ましく、0.5μm以下がより好ましく、0.1μm以下がさらに好ましい。フィルターの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルターろ過工程では、複数種のフィルターを直列または並列に接続して用いてもよい。複数種のフィルターを使用する場合は、孔径および/または材質が異なるフィルターを組み合わせて使用しても良い。また、各種材料を複数回ろ過してもよい。複数回ろ過する場合は、循環ろ過であっても良い。また、加圧してろ過を行ってもよい。加圧してろ過を行う場合、加圧する圧力は0.05MPa以上0.3MPa以下が好ましい。
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行っても良い。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせても良い。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。
次に、本発明の積層体の製造方法を適用して得られる電子デバイスの一実施形態について説明する。図2に示す電子デバイス100は、いわゆる3次元実装デバイスであり、複数の半導体素子(半導体チップ)101a~101dが積層した積層体101が、配線基板120上に配置されている。なお、この実施形態では、半導体素子(半導体チップ)の積層数が4層である場合を中心に説明するが、半導体素子(半導体チップ)の積層数は特に限定されるものではなく、例えば、2層、8層、16層、32層等であってもよい。また、1層であってもよい。
最上段の半導体素子101aは、貫通電極を有さず、その一方の面に電極パッド(図示せず)が形成されている。
半導体素子101b~101dは、貫通電極102b~102dを有し、各半導体素子の両面には、貫通電極に一体に設けられた接続パッド(図示せず)が設けられている。
すなわち、貫通電極を有さない半導体素子101aの電極パッドと、これに隣接する貫通電極102bを有する半導体素子101bの半導体素子101a側の接続パッドが、半田バンプ等の金属バンプ103aで接続され、貫通電極102bを有する半導体素子101bの他側の接続パッドが、それに隣接する貫通電極102cを有する半導体素子101cの半導体素子101b側の接続パッドと、半田バンプ等の金属バンプ103bで接続されている。同様に、貫通電極102cを有する半導体素子101cの他側の接続パッドが、それに隣接する貫通電極102dを有する半導体素子101dの半導体素子101c側の接続パッドと、半田バンプ等の金属バンプ103cで接続されている。
配線基板120としては、例えば樹脂基板、セラミックス基板、ガラス基板等の絶縁基板を基材として用いた多層配線基板が使用される。樹脂基板を適用した配線基板120としては、多層銅張積層板(多層プリント配線板)等が挙げられる。
配線基板120と積層体101との間には、再配線層105が形成された絶縁層115が配置されており、配線基板120と積層体101とは、再配線層105を介して電気的に接続されている。絶縁層115は、本発明の積層体の製造方法を用いて形成してなるものである。絶縁層115は、図1に示すような多層配線構造の積層体であってもよい。
再配線層105の一端は、半田バンプ等の金属バンプ103dを介して、半導体素子101dの再配線層105側の面に形成された電極パッドに接続されている。また、再配線層105の他端は、配線基板の表面電極120aと、半田バンプ等の金属バンプ103eを介して接続している。
そして、絶縁層115と積層体101との間には、アンダーフィル層110aが形成されている。また、絶縁層115と配線基板120との間には、アンダーフィル層110bが形成されている。
次に、本発明の電子デバイスの製造方法を説明する。本発明の電子デバイスの製造方法は、上述した本発明の積層体の製造方法を含む。本発明の電子デバイスの製造方法は、同一の保存工程の条件にて複数の電子デバイスを製造することが好ましい。
[ピロメリット酸二無水物、4,4’-オキシジアニリンおよびベンジルアルコールからのポリイミド前駆体(P-1:ラジカル重合性基を有さないポリイミド前駆体)の合成]
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥)と、14.22g(131.58ミリモル)のベンジルアルコールとを、50mlのN-メチルピロリドンに懸濁させ、モレキュラーシーブで乾燥させた。懸濁液を100℃で3時間加熱した。加熱を開始してから数分後に透明な溶液が得られた。反応混合物を室温に冷却し、21.43g(270.9ミリモル)のピリジンおよび90mlのN-メチルピロリドンを加えた。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。SOCl2を加えている間、粘度が増加した。50mlのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mlのN-メチルピロリドンに11.08g(58.7ミリモル)の4,4’-オキシジアニリンを溶解させた溶液を、20~23℃で20分かけて反応混合物に滴下した。次いで、反応混合物を室温で1晩撹拌した。次いで、5リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5000rpmの速度で15分間撹拌した。ポリイミド前駆体を濾取し、再度4リットルの水に投入してさらに30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥し、下記式で表される繰り返し単位を含むポリイミド前駆体(P-1)を得た。
[ピロメリット酸二無水物、4,4’-オキシジアニリンおよび2-ヒドロキシエチルメタクリレートとからのポリイミド前駆体(P-2:ラジカル重合性基を有するポリイミド前駆体)の合成]
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥した)と、18.6g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、10.7gのピリジンと、140gのダイグライム(ジエチレングリコールジメチルエーテル)とを混合し、60℃の温度で18時間撹拌して、ピロメリット酸と2-ヒドロキシエチルメタクリレートとのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-オキシジアニリンでポリイミド前駆体に変換し、合成例1と同様の方法で、下記式で表される繰り返し単位を含むポリイミド前駆体(P-2)を得た。
[4,4’-オキシジフタル酸無水物、4,4’-オキシジアニリンおよび2-ヒドロキシエチルメタクリレートとからのポリイミド前駆体(P-3:ラジカル重合性基を有するポリイミド前駆体)の合成]
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、18.6g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、10.7gのピリジンと、140gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートとのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-オキシジアニリンでポリイミド前駆体に変換し、合成例1と同様の方法で、下記式で表される繰り返し単位を含むポリイミド前駆体(P-3)を得た。
27.0g(153.2ミリモル)のベンジルメタクリレート、20g(157.3ミリモル)のN-イソプロピルメタクリルアミド、39g(309.2ミリモル)のメタクリル酸アリル、13g(151.0ミリモル)のメタクリル酸、重合開始剤(V-601、和光純薬工業製)3.55g(15.4ミリモル)、および3-メトキシ-2-プロパノール300gを混合した。混合液を、窒素雰囲気下、75℃に加熱した3-メトキシ-2-プロパノール300gの中に、2時間かけて滴下した。滴下終了後、さらに窒素雰囲気下、75℃で2時間撹拌した。反応終了後、5リットルの水に投入してポリマーを沈殿させて、5000rpmの速度で15分間撹拌した。アクリル樹脂を濾取し、再度4リットルの水に投入してさらに30分間撹拌し、再び濾取した。次いで、得られたアクリル樹脂を減圧下、45℃で3日間乾燥して、下記式で表されるアクリル系ポリマー(P-6)を得た。
下記記載の成分を混合し、均一な溶液として、感光性樹脂組成物の塗布液を調製した。
(組成)
樹脂:下記表に記載の質量部
ラジカル重合性化合物:下記表に記載の質量部
光ラジカル重合開始剤:下記表に記載の質量部
シランカップリング剤:下記表に記載の質量部
防錆剤:下記表に記載の質量部
重合禁止剤:下記表に記載の質量部
塩基発生剤:下記表に記載の質量部
溶剤1(ジメチルスルホキシド):100質量部
溶剤2(γ-ブチロラクトン):25質量部
(樹脂)
P-1~P-3:合成例1~3で合成したポリイミド前駆体(P-1)~(P-3)
P-5:Matrimid5218(Huntsman Corporation製、閉環型ポリイミド)
P-6:合成例5で合成したアクリル系ポリマー(P-6)(アクリル樹脂)
P-7:ポリメタクリル酸メチル(Mw=15000、シグマアルドリッチジャパン合同会社製)
B-1:SR209(サートマー社製、テトラエチレングリコールジアクリレート)
B-2:NKエステルA-9300(新中村化学工業(株)製、エトキシ化イソシアヌル酸トリアクリレート)
B-3:A-TMMT(新中村化学工業(株)製、ペンタエリスリトールテトラアクリレート)
B-4:A-DPH(新中村化学工業(株)製、ジペンタエリスリトールヘキサアクリレート)
C-1:IRGACURE OXE 01(BASF社製、オキシム化合物)
C-2:IRGACURE OXE 02(BASF社製、オキシム化合物)
C-3:IRGACURE-784(BASF製、メタロセン化合物)
C-4:アデカアークルズNCI-831((株)ADEKA製、オキシム化合物)
D-1:KBM-602(信越化学工業(株)製、アミノ基を有するシラン化合物)
D-2:2-((3-(トリエトキシシリル)プロピル)カルバモイル)安息香酸(Aquila Pharmatech LLC製、カルボキシル基を有するシラン化合物)
D-3:トリエトキシシリルプロピルマレインアミド酸(Gelest,Inc製、カルボキシル基を有するシラン化合物)
E-1:KEMITEC BT-C(ケミプロ化成(株)製、1,2,3-ベンゾトリアゾール)
E-2:1HT(東洋紡(株)製、1H-テトラゾール)
E-3:P5T(東洋紡(株)製、5-フェニル-1H-テトラゾール)
F-1:4-メトキシフェノール
F-2:pーベンゾキノン
F-3:1-ニトロソ-2-ナフトール
A-1、A-21、A-40:下記構造の化合物(熱塩基発生剤)
A-43:WPBG-266(和光純薬工業(株)製、光塩基発生剤。なおこの化合物は加熱によっても分解して塩基を発生する化合物でもある。すなわち熱塩基発生剤でもある。)
各感光性樹脂組成物を、細孔の幅が0.8μmのフィルターを通して加圧濾過した後、シリコンウエハ上にスピンコート法により層状に適用し、ホットプレートを用いて100℃で5分間乾燥して感光性樹脂組成物層を形成した。次に、下記表に記載の時間と温度にて保存工程(PCD工程)を行った後、感光性樹脂組成物層に対し、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで露光した。次に、露光後の感光性樹脂組成物層を下記表に記載の時間と温度にて保存工程(PED工程)を行った後、シクロペンタノンを用いて60秒間現像して、直径10μmのホールを形成した。次に、下記表に記載の時間と温度にて保存工程(PDD工程)を行った後、窒素雰囲気下で230℃で3時間加熱して樹脂層(パターン)を形成した。次に、加熱後の樹脂層(パターン)を室温まで冷却し、下記表に記載の時間と温度にて保存工程(PBD工程)を行った後、銅メッキ処理を行い、樹脂層上に厚さ5μmの銅薄膜を形成して、積層体1を形成した。
なお、各保存工程は、下記表に記載の設定温度に調整されたクリーン恒温恒湿器(エスペック(株)製、PCR-3J)に静置して行った。
次に、積層体1の銅薄膜に対し、酸素プラズマを照射した後、再度、感光性樹脂組成物の適用、露光、現像、加熱および各保存工程を行った後、銅メッキ処理を行い、樹脂層上に厚さ5μmの銅薄膜を形成して積層体2を得た。
次に、積層体2の銅薄膜に対し、酸素プラズマを照射した後、再度、感光性樹脂組成物の適用、露光、現像、加熱および各保存工程を行った後、銅メッキ処理を行い、樹脂層上に厚さ5μmの銅薄膜を形成して積層体3を得た。
[剥離欠陥(評価1)]
積層体2を、垂直方向に切断して幅5mmの断面を観察して、樹脂層/樹脂層間、及び、銅/樹脂層間での剥がれの有無を確認した。剥がれの発生がなければ、優れた密着性を有していることを表し、好ましい結果となる。
A:剥がれの発生なし
B:剥がれの発生が1~2個
C:剥がれの発生が3~5個
D:剥がれの発生が6個以上
積層体3を、垂直方向に切断して幅5mmの断面を観察して、樹脂層/樹脂層間、及び、銅/樹脂層間での剥がれの有無を確認した。剥がれの発生がなければ、優れた密着性を有していることを表し、好ましい結果となる。
A:剥がれの発生なし
B:剥がれの発生が1~2個
C:剥がれの発生が3~5個
D:剥がれの発生が6個以上
シリコンウエハ上の感光性樹脂組成物層を、ステッパー(Nikon NSR2005 i9C)を用いて露光した。露光はi線で行い、波長365nmにおいて、200mJ/cm2の各露光エネルギーで、5μm~25μmまで1μm刻みのヒューズボックスのフォトマスクを使用して露光を行った。露光した感光性樹脂組成物層について、現像液としてシクロペンタノンとプロピレングリコールメチルエーテルアセテートとを用いて現像を行った。具体的には露光した感光性樹脂組成物層にシクロペンタノンを噴霧し、次いで、プロピレングリコールメチルエーテルアセテートを噴霧して、60秒間現像した。ヒューズボックスの底部においてシリコンウエハが露出している線幅を以下の基準で評価した。線幅が小さければ小さいほどその後のメッキ工程で形成される金属配線幅を微細化できることを表し、好ましい結果となる。測定限界は5μmである。結果を表に示す。
A:5μm以上8μm以下
B:8μmを超えて10μm以下
C:10μmを超えて15μm以下
D:15μmを超えた
101a~101d:半導体素子
101:積層体
102b~102d:貫通電極
103a~103e:金属バンプ
105:再配線層
110、110a、110b:アンダーフィル層
115:絶縁層
120:配線基板
120a:表面電極
201~204:樹脂層
301~303:金属層
401~403:溝
500:積層体
Claims (16)
- ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される樹脂と、光重合開始剤と、を含む感光性樹脂組成物を支持体上に適用して感光性樹脂組成物層を形成する感光性樹脂組成物層形成工程と、
前記感光性樹脂組成物層をパターン状に露光する露光工程と、
前記感光性樹脂組成物層を現像してパターンを形成する現像工程と、
前記パターンを加熱する加熱工程と、
加熱後のパターン上に金属層を形成する金属層形成工程とを含み、
感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間、現像工程と加熱工程との間、および、加熱工程と金属層形成工程との間の少なくとも一つにおいて、表面温度が一定温度に達してから、その状態で5分以上保存する保存工程を行う、積層体の製造方法。 - 露光工程と現像工程との間に前記保存工程を行う、請求項1に記載の積層体の製造方法。
- 露光工程と現像工程との間に行う前記保存工程が、下記式を満たす、請求項2に記載の積層体の製造方法;
5≦t1<(10-0.036×T1+12.3)×60
T1は露光工程と現像工程との間に行う保存工程における平均表面温度であって単位はKである;t1は露光工程と現像工程との間に行う保存工程の時間であって単位は分である。 - 感光性樹脂組成物層形成工程と露光工程との間に前記保存工程を行う、請求項1~3のいずれか1項に記載の積層体の製造方法。
- 感光性樹脂組成物層形成工程と露光工程との間に行う前記保存工程が、下記式を満たす、請求項4に記載の積層体の製造方法;
5≦t2<(10-0.031×T2+10.7)×60
T2は感光性樹脂組成物層形成工程と露光工程との間に行う保存工程における平均表面温度であって単位はKである;t2は感光性樹脂組成物層形成工程と露光工程との間に行う保存工程の時間であって単位は分である。 - 現像工程と加熱工程との間に前記保存工程を行う、請求項1~5のいずれか1項に記載の積層体の製造方法。
- 現像工程と加熱工程との間に行う前記保存工程が、下記式を満たす、請求項6に記載の積層体の製造方法;
5≦t3<(10-0.02×T3+8.0)×60
T3は現像工程と加熱工程との間に行う保存工程における平均表面温度であって単位はKである;t3は現像工程と加熱工程との間に行う保存工程の時間であって単位は分である。 - 加熱工程と金属層形成工程との間に前記保存工程を行う、請求項1~7のいずれか1項に記載の積層体の製造方法。
- 前記感光性樹脂組成物における前記樹脂がポリイミド前駆体であり、
前記ポリイミド前駆体がラジカル重合性基を含むか、あるいは、前記感光性樹脂組成物が前記ポリイミド前駆体以外のラジカル重合性化合物を含む、請求項1~8のいずれか1項に記載の積層体の製造方法。 - 前記式(1)中、R23およびR24の少なくとも一方が、ラジカル重合性基を含む、請求項10に記載の積層体の製造方法。
- 前記式(1)におけるR22は、芳香環を含む4価の基である、請求項10または11に記載の積層体の製造方法。
- 前記金属層形成工程後のパターン上に、前記感光性樹脂組成物層形成工程、前記露光工程、前記現像工程、前記加熱工程および前記金属層形成工程をこの順で行い、前記感光性樹脂組成物層形成工程と前記露光工程との間、前記露光工程と前記現像工程との間、前記現像工程と前記加熱工程との間、および、前記加熱工程と前記金属層形成工程との間の少なくとも一つにおいて、前記保存工程を行う一連のサイクルを2サイクル以上行う、請求項1~12のいずれか1項に記載の積層体の製造方法。
- 多層配線構造の積層体の製造方法である、請求項1~13のいずれか1項に記載の積層体の製造方法。
- ポリイミド前駆体、ポリイミド、ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾールから選択される樹脂と、光重合開始剤と、を含む感光性樹脂組成物を支持体上に適用して感光性樹脂組成物層を形成する感光性樹脂組成物層形成工程と、
前記感光性樹脂組成物層をパターン状に露光する露光工程と、
前記感光性樹脂組成物層を現像してパターンを形成する現像工程と、
前記パターンを加熱する加熱工程と、
加熱後のパターン上に金属層を形成する金属層形成工程とを含み、
感光性樹脂組成物層形成工程と露光工程との間、露光工程と現像工程との間、現像工程と加熱工程との間、および、加熱工程と金属層形成工程との間の少なくとも一つにおいて、表面温度が一定温度に達してから、その状態で5分以上保存する保存工程を行う、積層体の製造方法を含む、電子デバイスの製造方法。 - 同一の保存工程の条件にて複数の電子デバイスを製造する、請求項15に記載の電子デバイスの製造方法。
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WO2019189110A1 (ja) * | 2018-03-29 | 2019-10-03 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス |
WO2019189112A1 (ja) * | 2018-03-29 | 2019-10-03 | 富士フイルム株式会社 | 積層体の製造方法および熱硬化性有機膜形成用組成物 |
JP2019215452A (ja) * | 2018-06-13 | 2019-12-19 | 日立化成株式会社 | 感光性樹脂組成物、配線層及び半導体装置 |
WO2022202647A1 (ja) | 2021-03-22 | 2022-09-29 | 富士フイルム株式会社 | ネガ型感光性樹脂組成物、硬化物、積層体、硬化物の製造方法、及び、半導体デバイス |
WO2023032545A1 (ja) | 2021-08-31 | 2023-03-09 | 富士フイルム株式会社 | 硬化物の製造方法、積層体の製造方法、及び、半導体デバイスの製造方法、並びに、処理液 |
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JPWO2019189112A1 (ja) * | 2018-03-29 | 2021-02-25 | 富士フイルム株式会社 | 積層体の製造方法および熱硬化性有機膜形成用組成物 |
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JP7153064B2 (ja) | 2018-03-29 | 2022-10-13 | 富士フイルム株式会社 | 積層体の製造方法および熱硬化性有機膜形成用組成物 |
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WO2023032545A1 (ja) | 2021-08-31 | 2023-03-09 | 富士フイルム株式会社 | 硬化物の製造方法、積層体の製造方法、及び、半導体デバイスの製造方法、並びに、処理液 |
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TW201826392A (zh) | 2018-07-16 |
JPWO2018038002A1 (ja) | 2019-04-11 |
TWI733882B (zh) | 2021-07-21 |
KR20190027881A (ko) | 2019-03-15 |
JP6633767B2 (ja) | 2020-01-22 |
KR102212731B1 (ko) | 2021-02-08 |
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