WO2020080216A1 - 硬化膜の製造方法、樹脂組成物、硬化膜、積層体の製造方法および半導体デバイスの製造方法 - Google Patents
硬化膜の製造方法、樹脂組成物、硬化膜、積層体の製造方法および半導体デバイスの製造方法 Download PDFInfo
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- WO2020080216A1 WO2020080216A1 PCT/JP2019/039778 JP2019039778W WO2020080216A1 WO 2020080216 A1 WO2020080216 A1 WO 2020080216A1 JP 2019039778 W JP2019039778 W JP 2019039778W WO 2020080216 A1 WO2020080216 A1 WO 2020080216A1
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- 0 CCCC(C)NC*NC(*)=O Chemical compound CCCC(C)NC*NC(*)=O 0.000 description 1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/145—Polyamides; Polyesteramides; Polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Definitions
- the present invention relates to a method for producing a cured film using a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer.
- the present invention also relates to a method for producing a resin composition, a cured film, a laminate, and a method for producing a semiconductor device.
- Resins that have been cyclized and cured such as polyimide resins and polybenzoxazole resins, have excellent heat resistance and insulation properties, and are therefore used in various applications. Although the use thereof is not particularly limited, when a semiconductor device for mounting is taken as an example, it may be used as a material for an insulating film or a sealing material or as a protective film. It is also used as a base film or coverlay for flexible substrates.
- polyimide resins have low solubility in solvents. Therefore, a method in which a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor is dissolved in a solvent is often used. Thereby, excellent handleability can be realized, and when each of the above-mentioned products is manufactured, it can be applied to a substrate or the like in various forms and processed.
- the polymer precursor can then be heated to cyclize to form a cured product.
- the heating is performed in an atmosphere such as a nitrogen atmosphere in which the oxygen concentration is reduced.
- Patent Document 1 describes forming a photosensitive polyimide resin layer by heating the photosensitive polyimide precursor layer at 200 ° C. or higher and 350 ° C. or lower in an environment where the oxygen concentration is 50 ppm or lower.
- Patent Document 2 describes that a resin film selected from a photosensitive polyimide precursor or a photosensitive polybenzoxazole precursor is heat-treated in a nitrogen atmosphere and then further heat-treated in an atmosphere containing oxygen. There is.
- an object of the present invention is to provide a method for producing a cured film having excellent mechanical properties, a resin composition, a cured film, a method for producing a laminate, and a method for producing a semiconductor device.
- a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radically polymerizable monomer is used as the resin composition. It was found that a cured film having excellent mechanical properties can be obtained by heat-curing a film obtained using this resin composition in an atmosphere with an oxygen partial pressure of 6 to 150 Pa, and to complete the present invention. I arrived.
- the present invention provides the following.
- a method for producing a cured film containing: ⁇ 2> The method for producing a cured film according to ⁇ 1>, wherein the atmospheric pressure in the heat curing step is 0.08 to 0.12 MPa.
- the step of ⁇ 3> heat curing the method for producing a cured film according to ⁇ 1> or ⁇ 2>, wherein the film is heated to 170 to 350 ° C.
- ⁇ 4> The method according to any one of ⁇ 1> to ⁇ 3>, which includes a step of exposing the film and a step of developing the exposed film between the step of forming the film and the step of heat curing.
- Method for producing cured film ⁇ 5>
- the method for producing a cured film according to any one of ⁇ 1> to ⁇ 4>, wherein the substrate to which the resin composition is applied is a metal substrate or a substrate including a metal layer.
- ⁇ 6> The method for producing a cured film according to any one of ⁇ 1> to ⁇ 5>, which is a method for producing a cured film for an insulating layer.
- a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a radical polymerizable monomer A resin composition used in the method for producing a cured film according to any one of ⁇ 1> to ⁇ 6>.
- a method for manufacturing a semiconductor device including the method for manufacturing a cured film according to any one of ⁇ 1> to ⁇ 6> or the method for manufacturing a laminated body according to ⁇ 9>.
- the present invention can provide a method for producing a cured film having excellent mechanical properties, a resin composition, a cured film, a method for producing a laminate, and a method for producing a semiconductor device.
- the components of the present invention described below may be described based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
- the notation of not having substitution and non-substitution includes not only those having no substituent but also those having 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).
- the term "exposure” includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified.
- the light used for the exposure generally includes a bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron rays, or radiation.
- EUV light extreme ultraviolet rays
- active rays such as electron rays, or radiation.
- (meth) acrylate” represents both “acrylate” and “methacrylate” or either
- (meth) acryl” means both “acrylic” and “methacryl”
- (Meth) acryloyl” means both "acryloyl” and "methacryloyl", or either.
- the term “process” is included in this term as long as the intended action of the process is achieved not only as an independent process but also when it cannot be clearly distinguished from other processes.
- the physical property values in the present invention are values under a temperature of 23 ° C. and an atmospheric pressure of 101325 Pa.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) unless otherwise specified, and are defined as polystyrene conversion values.
- 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, and TSKgel are used as columns. It can be determined by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). In this measurement, THF (tetrahydrofuran) is used as an eluent unless otherwise specified. Unless otherwise stated, the detection uses a detector having a wavelength of 254 nm of UV rays (ultraviolet rays). The temperature in the present invention is 23 ° C. unless otherwise specified.
- a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radically polymerizable monomer is applied to a substrate.
- the method is characterized by including a step of forming a film (film forming step) and a step of heating and curing the film in an atmosphere with an oxygen partial pressure of 6 to 150 Pa (heat curing step).
- a cured film having excellent mechanical properties such as elongation can be formed.
- the crosslinking density between the radically polymerizable monomer and the polymer precursor is originally increased by increasing the amount of oxygen present by performing heat curing of the film in the atmosphere of the predetermined oxygen partial pressure. It is presumed that this could be achieved by a slight decrease in the value, the interaction between the polymer precursors was relaxed, and the resistance in the stress direction was increased. It has been generally considered that the polymerization reaction of the radically polymerizable monomer is likely to be inhibited in the presence of oxygen.
- the oxygen partial pressure during heat curing is within the above range, it is possible to suppress substrate oxidation and the like. Therefore, it is particularly effective when a substrate including a metal layer or a metal substrate is used as the substrate.
- the method for producing a film of the present invention includes a step of exposing the film and a step of developing the exposed film between the step of forming the film (film forming step) and the step of heat curing (heat curing step). It is preferable. That is, the method for producing a film of the present invention preferably includes the following steps (a) to (d). According to this aspect, it is possible to form a pattern of a cured film having excellent mechanical properties such as elongation.
- the cured film thus formed can be preferably used as an insulating layer. In particular, it can be preferably used as an interlayer insulating film for a redistribution layer.
- A a step of applying a resin composition to a substrate to form a film
- B a step of exposing the film after the film forming step (exposure step)
- C a step of developing the exposed film (developing step)
- D A step of heating and curing the developed film in an atmosphere having an oxygen partial pressure of 6 to 150 Pa (heat curing step).
- a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a radical polymerizable monomer is applied to a substrate to form a film. Details of the resin composition will be described later.
- the type of board can be appropriately determined according to the application.
- an inorganic substrate, a resin substrate, a resin composite material substrate and the like can be mentioned.
- the inorganic substrate include a silicon substrate, a silicon nitride substrate, a polysilicon substrate, a silicon oxide substrate, an amorphous silicon substrate, a glass substrate, a quartz substrate, and a metal substrate.
- a metal layer such as molybdenum, titanium, aluminum or copper may be formed on the surface of the silicon substrate, the silicon nitride substrate, the polysilicon substrate, the silicon oxide substrate, the amorphous silicon substrate, the glass substrate or the quartz substrate.
- the resin substrate polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluororesin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, cross-linked fumaric acid diester, cyclic polyolefin, Group consisting of synthetic resin such as aromatic ether, maleimide, olefin, cellulose, episulfide compound And the like.
- a metal layer may be formed on the surface of the resin substrate.
- a cured film having excellent mechanical properties such as elongation can be formed while suppressing metal oxidation and the like, and thus such a substrate was used. It is particularly effective in some cases.
- Coating is the preferred means for applying the resin composition to the substrate.
- the applying means a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, And the inkjet method and the like.
- the spin coating method, the slit coating method, the spray coating method, and the inkjet method are more preferable.
- a film (resin composition layer) having a desired thickness can be obtained by adjusting appropriate solid content concentration and coating conditions according to the method.
- the coating method can be appropriately selected depending on the shape of the substrate.
- the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method, spray coating method, inkjet method, etc.
- the method is preferred.
- the coating can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.
- the resin composition may be applied to the substrate and then dried to remove the solvent.
- the drying temperature is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, further preferably 90 to 110 ° C.
- the drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, more preferably 3 to 7 minutes.
- the method for producing a film of the present invention may include a step of exposing the film (exposure step) after the film forming step.
- the film (resin composition layer) can be exposed in a pattern by using a stepper exposure device, a scanner exposure device, or the like through a mask having a predetermined mask pattern.
- the exposure amount is not particularly limited as long as the film (resin composition layer) can be cured, but for example, 100 to 10000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm is preferable, and 200 to 8000 mJ / cm 2 is preferable. Irradiation is more preferable.
- the exposure wavelength can be appropriately set within the range of 190 to 1000 nm, and is preferably 240 to 550 nm.
- the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h Line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h and i lines), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam and the like can be mentioned.
- exposure with a high pressure mercury lamp is particularly preferable, and exposure with i-line is particularly preferable. Thereby, a particularly high exposure sensitivity can be obtained.
- the method for producing a film of the present invention may include a step of developing the film (resin composition layer) after exposure (developing step). By developing, the unexposed portion (non-exposed portion) is removed.
- the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, dipping, ultrasonic wave, etc. can be adopted. Development is performed using a developer.
- the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
- the developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent.
- the developing solution preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably an organic solvent having a ClogP value of 0 to 3.
- the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
- the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl acetate, etc.)
- 3-alkyloxypropionic acid alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.
- the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and aromatic hydrocarbons such as toluene, xylene, anisole and limonene.
- Preferred examples of the sulfoxides include dimethyl sulfoxide.
- cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
- 50% by mass or more of the developer is preferably an organic solvent, more preferably 70% by mass or more of the organic solvent, and further preferably 90% by mass or more of the organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.
- the developing time is preferably 10 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly limited, but it is usually 20 to 40 ° C.
- rinsing may be further performed. Rinsing is preferably performed in a solvent different from the developing solution. For example, rinsing can be performed using the solvent contained in the resin composition.
- the rinse time is preferably 5 seconds to 1 minute.
- Heat curing step the film (the developed film when the exposure step and the development step are included) is heated. By heating, the cyclization reaction of the polymer precursor proceeds to obtain a cured film.
- the heat curing step can be performed, for example, by heating the film in a heating chamber.
- the above film is heated in an atmosphere having an oxygen partial pressure of 6 to 150 Pa.
- the upper limit of the oxygen partial pressure in the heating step is preferably 120 Pa or less, more preferably 100 Pa or less, and even more preferably 60 Pa or less for the purpose of suppressing corrosion of the substrate.
- the lower limit of the oxygen partial pressure is preferably 7 Pa or more, more preferably 10 Pa or more, and further preferably 30 Pa or more, because a cured film having more excellent mechanical properties such as elongation can be easily obtained.
- the oxygen partial pressure in the heating chamber corresponds to the oxygen partial pressure in the atmosphere of the heat curing step.
- a method of replacing the gas in the atmosphere in the heating chamber with an inert gas to adjust the oxygen partial pressure, and reducing the pressure in the heating chamber For example, a method of adjusting the oxygen partial pressure by replacing the gas in the atmosphere in the heating chamber with an inert gas is preferable for the reason of the stability of the film.
- the inert gas include nitrogen, helium, argon and the like.
- the atmospheric pressure in the heat curing step is preferably 0.08 to 0.12 MPa, and more preferably 0.09 to 0.11 MPa for the reason of film stability.
- the pressure in the heating chamber corresponds to the atmospheric pressure in the heat curing step.
- the oxygen concentration in the atmosphere of the heat curing step is preferably more than 60 volume ppm and 1500 volume ppm or less.
- the lower limit is preferably 65 volume ppm or more, more preferably 100 volume ppm or more, and further preferably 500 volume ppm or more.
- the upper limit is preferably 1400 volume ppm or less, more preferably 1200 volume ppm or less, and further preferably 1000 volume ppm or less.
- the heating temperature (maximum heating temperature) of the film in the heat curing step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. It is more preferable that the temperature is 160 ° C. or higher, still more preferably 160 ° C. or higher, and still more preferably 170 ° C. or higher.
- the upper limit is preferably 500 ° C or lower, more preferably 450 ° C or lower, further preferably 350 ° C or lower, further preferably 250 ° C or lower, and 220 ° C or lower. Even more preferable.
- the heating temperature (maximum heating temperature) of the film is preferably 170 to 350 ° C.
- the heating is preferably performed at a temperature rising rate of 1 to 12 ° C./min from the temperature at the start of heating to the 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 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C.
- the temperature at the start of heating refers to the temperature at which the step of heating to the maximum heating temperature is started.
- the temperature of the film (layer) after the drying is, for example, 30 to 200 ° C. lower than the boiling point of the solvent contained in the resin composition. It is preferable to gradually raise the temperature.
- the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
- the film is preferably heated at 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between cured films. The reason for this is not clear, but it is considered that at this temperature, the ethynyl groups of the interpolymer interlayer precursors are undergoing a crosslinking reaction.
- the heating may be performed in stages. As an example, the temperature is raised from 25 ° C to 180 ° C at 3 ° C / min, held at 180 ° C for 60 minutes, raised from 180 ° C to 200 ° C at 2 ° C / min, and held at 200 ° C for 120 minutes.
- a pretreatment step such as, may be performed.
- the heating temperature in the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C.
- the pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
- the pretreatment may be performed in two or more steps.
- the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
- the pretreatment step 2 may be performed in the range of 150 to 200 ° C. Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./minute.
- a cured film can be manufactured through the above steps.
- fields to which the cured film can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films.
- a sealing film, a substrate material (a base film or a coverlay of a flexible printed board, an interlayer insulating film), or an insulating film for mounting as described above may be patterned by etching.
- the cured film can also be used for the production of printing plates such as offset or screen printing plates, for use in etching molded parts, for the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.
- the method for producing a laminated body of the present invention comprises a step of forming a cured film by the above-described method of producing a cured film of the present invention (cured film forming step), and a step of forming a metal layer on the surface of the cured film (metal layer Forming step).
- the type of the metal layer formed on the surface of the cured film is not particularly limited, it is possible to use existing metal species, copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, Copper and aluminum are more preferred, and copper is even more preferred.
- 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-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501 and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered.
- the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m in the thickest part.
- the method for producing a laminate of the present invention it is also preferable that after the metal layer forming step, a cured film is formed again on the surface of the cured film (resin layer) or the metal layer by the above-described method for producing a cured film of the present invention. . Further, in the method for producing a laminate of the present invention, the cured film forming step and the metal layer forming step may be alternately performed a plurality of times (preferably 2 to 7 times, more preferably 2 to 5 times).
- a multilayer wiring structure such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer in which a plurality of cured films (resin layers) and metal layers are alternately laminated
- the body can be manufactured.
- the method of manufacturing a semiconductor device of the present invention includes the method of manufacturing a cured film of the present invention described above or the method of manufacturing a laminate of the present invention described above.
- the description in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. 1 can be referred to, and the contents thereof are incorporated in the present specification.
- the resin composition of the present invention contains a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor.
- the polymer precursor used in the present invention is preferably a polyimide precursor because the effects of the present invention can be more remarkably obtained.
- the polyimide precursor preferably contains a constitutional unit represented by the following formula (1).
- a 1 and A 2 each independently represent an oxygen atom or NH
- R 111 represents a divalent organic group
- R 115 represents a tetravalent organic group
- R 113 and R 114 each independently. Represents a hydrogen atom or a monovalent organic group.
- a 1 and A 2 are each independently an oxygen atom or NH, and an oxygen atom is preferable.
- R 111 represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group consisting of a combination thereof, which has 2 to 20 carbon atoms.
- An aromatic group having 6 to 20 carbon atoms is more preferable.
- R 111 is preferably derived from a diamine.
- Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one diamine may be used, or two or more diamines may be used. Specifically, the diamine is a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. And a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.
- A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—, —S A group selected from ( ⁇ O) 2 —, —NHCO—, and a combination thereof is preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, and —O— , —C ( ⁇ O) —, —S— and —SO 2 — are more preferred, and —CH 2 —, —O—, —S—, —SO 2 —, —C ( It is more preferably a divalent group selected from the group consisting of CF 3 ) 2 — and —C (CH 3 ) 2 —.
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether
- the diamines (DA-1) to (DA-18) shown below are also preferable.
- diamines having at least two or more alkylene glycol units in the main chain are also preferred examples.
- Diamines containing one or both of ethylene glycol chains and propylene glycol chains in one molecule in combination of two or more, and more preferably diamines containing no aromatic ring are preferred.
- x, y, z are average values.
- R 111 is preferably represented by —Ar 0 —L 0 —Ar 0 —.
- Ar 0 is independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and preferably a phenylene group.
- L 0 is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—, —S ( ⁇ O) It represents a group selected from 2-, -NHCO-, and combinations thereof. The preferred range is synonymous with A described above.
- R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
- the divalent organic group represented by the formula (61) is more preferable from the viewpoints of i-ray transmittance and availability.
- R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or It is a trifluoromethyl group.
- the monovalent organic group represented by R 50 to R 57 is an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl groups and the like.
- R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.
- Examples of the diamine compound giving the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. You may use these 1 type or may use it in combination of 2 or more type.
- R 115 in the formula (1) represents a tetravalent organic group.
- the tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
- R 112 has the same meaning as A and the preferred range is also the same.
- tetravalent organic group represented by R 115 in the formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride.
- the tetracarboxylic dianhydride may be used alone or in combination of two or more.
- the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
- R 115 represents a tetravalent organic group.
- R 115 has the same meaning as R 115 in formula (1).
- tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4.
- DAA-1 to DAA-5 shown below are also preferred examples.
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R 113 and R 114 contains a radical polymerizable group, and it is more preferable that both contain a radical polymerizable group.
- the radically polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group and a group represented by the following formula (III).
- R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
- R 201 is an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atoms. The number of repetitions is preferably 1 to 12, more preferably 1 to 6, and most preferably 1 to 3).
- the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
- R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , —CH 2 CH (OH) CH 2 —, and an ethylene group, a propylene group, a trimethylene group, and —CH 2 CH (OH) CH 2 — are more preferable.
- R 200 is a methyl group and R 201 is an ethylene group.
- An alkyl group etc. are mentioned. Specific examples thereof include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specific examples include a phenyl group having an acid group and a benzyl group having an acid group.
- the acid group is preferably a hydroxyl group. That is, R 113 or R 114 is preferably a group having a hydroxyl group.
- R 113 or R 114 As the monovalent organic group represented by R 113 or R 114, a substituent that improves the solubility of the developer is preferably used. It is more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
- R 113 or R 114 is preferably a monovalent organic group.
- the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group or an aromatic group, more preferably an alkyl group substituted with an aromatic group.
- the alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group).
- the alkyl group may be linear, branched or cyclic.
- linear or branched alkyl group examples include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group. , Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
- the cyclic alkyl group may be either a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
- Examples of the monocyclic cyclic 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 cyclic 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.
- As the alkyl group substituted with an aromatic group a linear alkyl group substituted with an aromatic group described below is preferable.
- aromatic group examples include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, and azulene.
- the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, and azulene.
- the polyimide precursor preferably has a fluorine atom in the constituent unit.
- the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.
- an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by the formula (1) for the purpose of improving the adhesion to the substrate.
- the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
- the constitutional unit represented by the formula (1) is preferably a constitutional unit represented by the formula (1-A) or (1-B).
- a 11 and A 12 each represent an oxygen atom or NH
- R 111 and R 112 each independently represent a divalent organic group
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent group. It represents an organic group, and at least one of R 113 and R 114 is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.
- a 11 , A 12 , R 111 , R 113 and R 114 each independently have a preferable range which is the same as the preferable range of A 1 , A 2 , R 111 , R 113 and R 114 in the formula (1). ..
- a preferred range of R 112 has the same meaning as R 112 in formula (5), and more preferably among others oxygen atoms.
- the bonding position of the carbonyl group in the formula to the benzene ring is preferably 4,5,3 ′, 4 ′ in the formula (1-A). In the formula (1-B), 1,2,4,5 are preferable.
- the constitutional unit represented by the formula (1) may be one type or two or more types. Further, the structural unit represented by the formula (1) may contain a structural isomer. Further, the polyimide precursor may include other types of structural units in addition to the structural units of the above formula (1).
- a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of all the constituent units are constituent units represented by the formula (1) is exemplified.
- the upper limit is practically 100 mol% or less.
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and further preferably 4000 to 25000.
- the molecular weight dispersity of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
- the polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine.
- an organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
- a step of depositing a solid is included in the production of the polyimide precursor.
- solid precipitation can be performed by precipitating the polyimide precursor in the reaction solution in water and dissolving the polyimide precursor in a solvent in which the polyimide precursor is soluble.
- the polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
- R 121 represents a divalent organic group.
- the divalent organic group an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 and particularly preferably 1 to 6) and an aromatic group (preferably having 6 to 22 carbon atoms, 6 to 14 carbon atoms) Is more preferable, and 6 to 12 is particularly preferable).
- the aromatic group forming R 121 include the examples of R 111 in the above formula (1).
- the aliphatic group a linear aliphatic group is preferable.
- R 121 is preferably derived from 4,4′-oxydibenzoyl chloride.
- R 122 represents a tetravalent organic group.
- the tetravalent organic group has the same meaning as R 115 in the above formula (1), and the preferred range is also the same.
- R 122 is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
- R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group, have the same meaning as R 113 and R 114 in the above formula (1), and the preferred ranges are also the same.
- the polybenzoxazole precursor may contain other types of constitutional units in addition to the constitutional units of the above formula (2). It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit from the viewpoint of suppressing the occurrence of warpage of the cured film due to ring closure.
- SL diamine residue represented by the following formula
- Z has a structure and b structure
- R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)
- R 2s Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)
- at least one of R 3s , R 4s , R 5s , and R 6s is aromatic.
- a group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), the rest being hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, It is preferably an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, and they may be the same or different.
- the polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.
- preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
- the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
- the molecular weight can be determined by commonly used gel permeation chromatography. When the molecular weight is within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be made compatible.
- the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, it further improves alkali solubility, and further removes an acid dianhydride group from the tetracarboxylic dianhydride. It is preferable to include a tetracarboxylic acid residue remaining afterwards as a constituent unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and further preferably 4000 to 25000.
- the polybenzoxazole precursor has a molecular weight dispersity of preferably from 1.5 to 3.5, more preferably from 2 to 3.
- the content of the polymer precursor in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more based on the total solid content of the resin composition. Is more preferable, 50% by mass or more is more preferable, 60% by mass or more is still more preferable, and 70% by mass or more is still more preferable. Further, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less, and more preferably 99% by mass or less, based on the total solid content of the resin composition. Is more preferably 98% by mass or less, and further preferably 95% by mass or less.
- the resin composition of the present invention may include only one type of polymer precursor or may include two or more types of polymer precursors. When two or more kinds are contained, the total amount is preferably within the above range.
- the resin composition of the present invention contains a radically polymerizable monomer.
- a compound having radical-polymerizability can be used.
- the radically polymerizable group include groups having an ethylenically unsaturated bond such as vinyl group, allyl group, vinylphenyl group and (meth) acryloyl group.
- the radically polymerizable group is preferably a (meth) acryloyl group.
- the number of radically polymerizable groups contained in the radically polymerizable monomer may be 1 or 2 or more, but the radically polymerizable compound preferably has 2 or more radically polymerizable groups, and preferably 3 or more. More preferable.
- the upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.
- the molecular weight of the radically polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, even more preferably 900 or less.
- the lower limit of the molecular weight of the radically polymerizable monomer is preferably 100 or more.
- the resin composition of the present invention preferably contains at least one bifunctional or more radically polymerizable monomer containing two or more polymerizable groups, and at least one trifunctional or more radically polymerizable monomer. It is more preferable to include a seed. Further, it may be a mixture of a bifunctional radically polymerizable monomer and a trifunctional or higher functional radically polymerizable monomer.
- the number of functional groups of the radically polymerizable monomer means the number of radically polymerizable groups in one molecule.
- radical-polymerizable monomer examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters, and amides are preferable. They are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups.
- Substitution products of unsaturated carboxylic acid esters or amides having a leaving substituent such as or tosyloxy group with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable.
- the descriptions in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
- the radical polymerizable monomer is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure.
- examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
- polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-030490, epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
- the compounds described in paragraphs 0254 to 0257 of JP-A 2008-292970 are also suitable.
- a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be mentioned.
- a preferable radical polymerizable monomer other than the above an ethylenically unsaturated bond having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc. It is also possible to use a compound having two or more groups having a or a cardo resin.
- JP-B-46-043946, JP-B-01-040337, and JP-B-01-040336, and JP-A-02-025493 are described.
- the vinyl phosphonic acid-based compounds can also be used.
- the compounds containing a perfluoroalkyl group described in JP-A No. 61-022048 can also be used.
- the Japan Adhesive Association magazine, vol. 20, No. The compounds introduced as photopolymerizable monomers and oligomers on pages 7, 300 to 308 (1984) can also be used.
- dipentaerythritol triacrylate commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.
- dipentaerythritol tetraacrylate commercially available KAYARAD D-320; Nippon Kayaku (Nippon Kayaku) Ltd.
- A-TMMT Shin-Nakamura Chemical Co., Ltd.
- dipentaerythritol penta (meth) acrylate commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.
- dipentaerythritol hexa metal
- radically polymerizable monomers examples include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains, and urethane oligomer UAS-.
- radical-polymerizable monomer examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765.
- the urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
- compounds having an amino structure or a sulfide structure in the molecule which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-01-105238, are used as radically polymerizable monomers. It can also be used.
- the radically polymerizable monomer may be a compound having an acid group such as a carboxyl group or a phosphoric acid group.
- the radical polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to produce an acid.
- a compound having a group is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a compound.
- examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
- the acid value of the radically polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g.
- the acid value of the radical-polymerizable monomer is in the above range, the production and handling properties are excellent, and further the developability is excellent. Also, the polymerizability is good.
- a monofunctional radical-polymerizable monomer can be preferably used as the radical-polymerizable monomer from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film.
- Monofunctional radically polymerizable monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl.
- the monofunctional radically polymerizable monomer a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
- the content of the radical-polymerizable monomer is preferably 1 to 60 mass% with respect to the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
- the radical polymerizable monomers may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
- the resin composition of the present invention may further contain a polymerizable compound other than the radically polymerizable monomer described above (hereinafter, also referred to as other polymerizable compound).
- a polymerizable compound other than the radically polymerizable monomer described above hereinafter, also referred to as other polymerizable compound.
- Other polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
- the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group is preferably a compound represented by the following formula (AM1), (AM4) or (AM5).
- t represents an integer of 1 to 20
- R 104 represents a t-valent organic group having 1 to 200 carbon atoms
- R 105 represents a group represented by —OR 106 or —OCO—R 107.
- R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 107 represents an organic group having 1 to 10 carbon atoms.
- R 404 represents a divalent organic group having 1 to 200 carbon atoms
- R 405 represents a group represented by —OR 406 or —OCO—R 407
- R 406 represents a hydrogen atom or a carbon atom
- R 407 represents an organic group having 1 to 10 carbon atoms.
- u represents an integer of 3 to 8
- R 504 represents a u-valent organic group having 1 to 200 carbon atoms
- R 505 represents a group represented by —OR 506 or —OCO—R 507.
- R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 507 represents an organic group having 1 to 10 carbon atoms.
- Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-.
- specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-. 100 LM (manufactured by Sanwa Chemical Co., Ltd.) may be mentioned.
- Epoxy Compound (Compound Having Epoxy Group)
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and a dehydration reaction due to the cross-linking does not occur, so that the film shrinkage hardly occurs. Therefore, the inclusion of the epoxy compound is effective for curing the composition at low temperature and suppressing warpage.
- the epoxy compound preferably contains a polyethylene oxide group.
- the polyethylene oxide group means that the number of constitutional units of ethylene oxide is 2 or more, and the number of constitutional units is preferably 2 to 15.
- epoxy compound examples include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane.
- Epiclon (registered trademark) 850-S Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, epicuron (registered trademark) HP-4770, epiclon (registered trademark) EXA-859CRP, epiclon (registered trademark) EXA-1514, epiclon (registered trademark) EXA-4880, epiclon (registered trademark) EXA-4850-150, Epiclon EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (manufactured by DIC Corporation), Licaresin (registered trademark) BEO-60E (Nippon Rika) Ltd.), EP-4003S, EP-4 And the like 00S ((Lt) 850
- an epoxy resin containing a polyethylene oxide group is preferable in terms of suppression of warpage and excellent heat resistance.
- Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and Lycaledin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
- Oxetane Compound (Compound Having Oxetanyl Group)
- oxetane compound a compound having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester.
- the Aron oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or You may mix 2 or more types.
- benzoxazine compound (compound having benzoxazolyl group)
- the benzoxazine compound is preferable because it does not generate degas during curing because it is a cross-linking reaction derived from a ring-opening addition reaction and further suppresses thermal contraction to suppress warpage.
- benzoxazine compound examples include Ba type benzoxazine, Bm type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenzoxazine compound. . These may be used alone or in combination of two or more.
- the content is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
- the other polymerizable compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
- the resin composition of the present invention preferably contains a thermal base generator.
- the type of the thermal base generator is not particularly limited, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of Here, pKa1 represents the logarithm ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the acid, which will be described in detail later.
- pKa1 represents the logarithm ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the acid, which will be described in detail later.
- the thermal base generator contains at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable.
- the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, and thus the base generated from these compounds can accelerate the cyclization reaction of the polymer precursor, thereby cyclizing the polymer precursor. It can be done at low temperatures.
- the solution obtained by stirring means a compound having a value of less than 7 measured at 20 ° C. using a pH (power of hydrogen) meter.
- the base generation temperature of the thermal base generator used in the present invention is preferably 40 ° C. or higher, more preferably 120 to 200 ° C.
- the upper limit of the base generation temperature is preferably 190 ° C or lower, more preferably 180 ° C or lower, still more preferably 165 ° C or lower.
- the lower limit of the base generation temperature is preferably 130 ° C or higher, more preferably 135 ° C or higher.
- the base generation temperature for example, using differential scanning calorimetry, the compound is heated in a pressure-resistant capsule at 5 ° C./min to 250 ° C., the peak temperature of the lowest exothermic peak is read, and the peak temperature is measured as the base generation temperature. can do.
- the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since the tertiary amine is highly basic, the cyclization temperature of the polymer precursor can be lowered.
- 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 further 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 value of the molecular weight is a theoretical value obtained from the structural formula.
- the acidic compound (A1) preferably contains one or more selected from ammonium salts and compounds represented by the formula (101) or (102) 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). ) It may be a compound excluding an acidic compound which generates a base when heated.
- the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion.
- the anion may be bound to any part of the ammonium cation through a covalent bond and may be present outside the ammonium cation molecule, but may be present outside the ammonium cation molecule. preferable.
- that the anion has outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond.
- the anion outside the molecule of the cation portion is also referred to as a counter anion.
- R 1 to R 6 each independently represent a hydrogen atom or a hydrocarbon group
- R 7 represents a hydrocarbon group.
- R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , and R 5 and R 7 in formulas (101) and (102) may be bonded to each other to form a ring.
- the ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).
- R 101 represents an n-valent organic group
- R 1 and R 7 have the same meaning as in formula (101) or formula (102).
- 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.
- the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation.
- the upper limit of pKa1 of the anion is more preferably 3.5 or less and even more preferably 3.2 or less.
- the lower limit is preferably 0.5 or more, more preferably 1.0 or more.
- the type 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 the stability of the salt and the thermal decomposability can be compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
- the carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid 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 the anion of divalent carboxylic acid.
- the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less.
- the pKa1 is more preferably 3.5 or less, still 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 dissociation constant of the first proton of the acid, and is the Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Haflig. , Nachod, F. C .; Compiled by: Braude, E. A., Nachod, F. C .; Academic Press, New York, 1955) and Data for Biochemical Research. al; Oxford, Clarendon Press, 1959) can be referred to.
- the value calculated from the structural formula using software of ACD / pKa manufactured by ACD / Labs
- the carboxylate anion is preferably represented by the following formula (X1).
- EWG represents an electron-withdrawing group.
- the electron-withdrawing group means that the Hammett's substituent constant ⁇ m exhibits a positive value.
- ⁇ m is as described in Yuho Tsuno, Review of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965) p. 631-642.
- the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.
- 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 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar is an aromatic group.
- the carboxylate anion is preferably represented by the following formula (XA).
- Formula (XA) L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR X — and a combination thereof, and R X represents a hydrogen atom. Represents an alkyl group, an alkenyl group or an aryl group.
- carboxylate anion examples include maleate anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion. These can be preferably used.
- the content of the thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, still more preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
- the thermal base generator can use 1 type (s) or 2 or more types. When two or more kinds are used, the total amount is preferably within the above range.
- the resin composition of the present invention preferably contains a radical polymerization initiator. Especially when a polymer precursor containing a radically polymerizable group is used or a radically polymerizable compound is used, the resin composition of the present invention preferably contains a radical polymerization initiator. Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator. The radical polymerization initiator used in the resin composition of the present invention is preferably a photo radical polymerization initiator.
- the photo radical polymerization initiator is not particularly limited and can be appropriately selected from known photo radical polymerization initiators.
- a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
- the photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm).
- the molar extinction coefficient of a 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.
- any known compound can be used.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
- ketone compound examples include the compounds described in paragraph 0087 of JP-A-2005-087611, the contents of which are incorporated herein.
- Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone type initiator described in JP-A-10-291969 and the acylphosphine oxide type initiator described in Japanese Patent No. 4225898 can be used.
- the hydroxyacetophenone-based initiator IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (manufactured by BASF) can be used.
- aminoacetophenone-based initiator the compound 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-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- commercially available products such as IRGACURE-819 and IRGACURE-TPO (manufactured by BASF) can be used.
- metallocene compound include IRGACURE-784 (manufactured by BASF).
- An oxime compound is more preferred as the photo-radical polymerization initiator.
- the exposure latitude can be more effectively improved.
- Oxime compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator.
- oxime compounds the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, and the compounds described in JP 2006-342166 A can be used.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy.
- an oxime compound oxime-based photopolymerization initiator
- the oxime-based photopolymerization initiator has a> C ⁇ N—O—C ( ⁇ O) — linking group in the molecule.
- IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA, Inc., JP 2012-14052 A).
- the radical polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changzhou Power Electronics New Materials Co., Ltd.
- ADEKA ARCRUZ NCI-831 and ADEKA ARCRUZ NCI-930 can also be used.
- DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.
- an oxime compound having a fluorine atom examples include the compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and JP 2013-2013 A.
- the compound (C-3) described in paragraph 0101 of JP-A-164471 can be mentioned.
- the most preferable oxime compound includes oxime compounds having a specific substituent described in JP-A 2007-269779 and oxime compounds having a thioaryl group described in JP-A 2009-191061.
- the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl, from the viewpoint of exposure sensitivity.
- Photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, metallocene compounds or oxime compounds are even more preferable, and oxime compounds are preferable. Are even more preferred.
- the photo-radical polymerization initiators are benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) and other N, N'-tetraalkyl-4,4'-diaminobenzophenones, 2-benzyl.
- Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and alkylanthraquinones It is also possible to use quinones condensed with the aromatic ring, a benzoin ether compound such as benzoin alkyl ether, a benzoin compound such as benzoin and alkylbenzoin, and a benzyl derivative such as benzyldimethylketal. Moreover, the compound represented by the following formula (I) can also be used.
- R I00 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 alkoxyl group having 1 to 12 carbon atoms, a phenyl group, C1-C20 alkyl group, C1-C12 alkoxyl group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, C2-C interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenyl,
- R I01 is a group represented by formula (II), the same as R I00 R I02 to R I04 each independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or halogen.
- R I05 to R I07 are the same as R I02 to R I04 in the above formula
- the photoradical polymerization initiator When the photoradical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. %, More preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass.
- the photo-radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more photo-radical polymerization initiators are contained, the total amount is preferably within the above range.
- thermal radical polymerization initiator is a compound that generates a radical by the energy of heat and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be progressed together with the cyclization of the polymer precursor, so that higher heat resistance can be achieved.
- Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP 2008-63554 A.
- thermal radical polymerization initiator When the thermal radical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. %, And more preferably 5 to 15% by mass.
- the thermal radical polymerization initiator may contain only one type, or may contain two or more types. When two or more thermal radical polymerization initiators are contained, the total amount is preferably within the above range.
- the resin composition of the present invention preferably contains a solvent.
- Any known solvent can be used as the solvent.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides.
- the 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, ⁇ -caprolactone.
- alkyl alkyloxyacetate eg methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc. )
- 3-alkyloxypropionic acid alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- 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.
- Suitable 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 and the like.
- suitable aromatic hydrocarbons include toluene, xylene, anisole, and limonene.
- suitable sulfoxides include dimethyl sulfoxide.
- Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
- the solvent is preferably a mixture of two or more kinds.
- One solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or composed of two or more solvents Mixed solvents are preferred.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- the content of the solvent is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and preferably 5 to 75% by mass.
- the amount is more preferably 10 to 70% by mass, still more preferably 40 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness and coating method.
- the solvent may contain only 1 type, and may contain 2 or more types. When two or more kinds of solvents are contained, the total amount is preferably within the above range.
- the resin composition of the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the resin composition layer.
- the migration inhibitor is not particularly limited, but a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol compounds , Salicylic acid derivative compounds
- an ion trap agent that traps anions such as halogen ions can be used.
- Other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656A.
- the compounds described in Paragraph 0052, the compounds described in Paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, the compounds described in Paragraph 0166 of WO 2015/199219 and the like can be used.
- the migration inhibitor include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0 mass% with respect to the total solid content of the resin composition, and 0.05 to 2 It is more preferably 0.0% by mass, and further preferably 0.1 to 1.0% by mass. Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present invention preferably contains a polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4 ′.
- -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4 -Hydroxy-3,5-
- polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 can also be used. Further, the following compounds can be used (Me is a methyl group).
- the content of the polymerization inhibitor is preferably 0.01 to 5 mass% with respect to the total solid content of the resin composition of the present invention, and 0 The content is more preferably 0.02 to 3% by mass, further preferably 0.05 to 2.5% by mass. Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
- the resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to metal materials used for electrodes and wiring.
- a metal adhesion improver for improving the adhesion to metal materials used for electrodes and wiring.
- the metal adhesion improver include silane coupling agents.
- silane coupling agent examples include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP2014-191002A, paragraphs of WO2011 / 080992.
- the compound as described in paragraph 0055 is mentioned. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
- Et represents an ethyl group.
- the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0, relative to 100 parts by mass of the polymer precursor. It is in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit, the adhesion between the cured film and the metal layer after the curing step will be good, and when it is at most the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step will be good.
- the metal adhesion improver may be only one kind or two or more kinds. When two or more kinds are used, the total is preferably within the above range.
- the resin composition of the present invention is, if necessary, various additives such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, and a higher fatty acid derivative, as long as the effects of the present invention are not impaired.
- various additives such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, and a higher fatty acid derivative, as long as the effects of the present invention are not impaired.
- Inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an agglomeration inhibitor and the like can be added.
- the total blending amount is preferably 3% by mass or less of the solid content of the composition.
- the resin composition of the present invention may contain a thermal acid generator.
- the content of the thermal acid generator is preferably 0.01 parts by mass or more and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polymer precursor. By containing 0.01 part by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
- the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of electric insulation of the cured film. Only one thermal acid generator may be used, or two or more thermal acid generators may be used. When two or more kinds are used, the total amount is preferably within the above range.
- the resin composition of the present invention may contain a sensitizing dye.
- the sensitizing dye absorbs specific actinic radiation to be in an electronically excited state.
- the electron-excited sensitizing dye is brought into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
- the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base.
- the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
- the content of the sensitizing dye is preferably 0.01 to 20 mass% with respect to the total solid content of the resin composition of the present invention, The amount is more preferably 1 to 15% by mass, further preferably 0.5 to 10% by mass.
- the sensitizing dyes may be used alone or in combination of two or more.
- the resin composition of the present invention may contain a chain transfer agent.
- the chain transfer agent is defined, for example, in Polymer Dictionary, Third Edition (edited by The Polymer Society of Japan, 2005), pages 683-684.
- As the chain transfer agent for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can donate hydrogen to a low activity radical to generate a radical, or can generate a radical by being deprotonated after being oxidized. Particularly, a thiol compound can be preferably used.
- the chain transfer agent the compounds described in paragraphs 0152 to 0153 of WO 2015/199219 can also be used.
- the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition of the present invention, and 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, it is preferable that the total thereof is within the above range.
- surfactant From the viewpoint of further improving the coatability, various kinds of surfactants may be added to the resin composition of the present invention.
- various kinds of 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 compounds described in paragraphs 0159 to 0165 of WO 2015/199219 can also be used.
- the content of the surfactant is preferably 0.001 to 2.0 mass% with respect to the total solid content of the resin composition of the present invention. , And more preferably 0.005 to 1.0 mass%.
- the surfactant may be only one kind or two or more kinds. When two or more kinds of surfactants are used, it is preferable that the total amount is within the above range.
- the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen, and is unevenly distributed on the surface of the composition during the drying process after coating. You may let me. Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of WO 2015/199219 can also be used.
- the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% with respect to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more higher fatty acid derivatives are used, the total of them is preferably within the above range.
- the water content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of the properties of the coated surface.
- the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm from the viewpoint of insulating properties.
- the metal include sodium, potassium, magnesium, calcium, iron, chromium and nickel. When a plurality of metals are contained, the total of these metals is preferably within the above range.
- a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention
- the resin composition of the present invention examples thereof include a method in which a raw material constituting the product is filtered, and a distillation is performed under a condition in which the inside of the apparatus is lined with polytetrafluoroethylene or the like to suppress contamination as much as possible.
- the resin composition of the present invention has a halogen atom content of preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosivity. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
- the halogen atom include chlorine atom and bromine atom. It is preferable that the total of chlorine atom and bromine atom, or the total of chlorine ion and bromine ion be in the above ranges.
- a conventionally known container can be used as a container for the resin composition of the present invention.
- a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin, or 6 kinds of resin of 7 layers structure is used for the purpose of suppressing the mixing of impurities into raw materials and compositions. It is also preferable to use a bottle.
- a container for example, the container described in JP-A-2015-123351 can be mentioned.
- the resin composition of the present invention can be prepared by mixing the above components.
- the mixing method is not particularly limited, and a conventionally known method can be used. Further, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the composition.
- the pore size of the filter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
- the filter may be washed with an organic solvent in advance. In the filter filtration step, plural kinds of filters may be connected in series or in parallel and used.
- filters having different pore diameters or materials may be used in combination.
- various materials may be filtered multiple times.
- circulating filtration may be used.
- you may pressurize and may perform filtration.
- the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
- a treatment for removing impurities using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- a known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the cured film of the present invention is obtained from the resin composition of the present invention.
- the thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value may be 100 ⁇ m or less, and may be 30 ⁇ m or less.
- the thickness of the cured film of the present invention is preferably 1 to 30 ⁇ m.
- Two or more layers of the cured film of the present invention, or 3 to 7 layers may be laminated to form a laminate.
- the laminate having two or more cured films of the present invention preferably has a metal layer between the cured films.
- Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
- the fields to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like.
- a sealing film, a substrate material (a base film or a coverlay of a flexible printed board, an interlayer insulating film), or an insulating film for mounting as described above may be patterned by etching.
- the cured film according to the present invention can also be used for production of printing plates such as offset printing plates or screen printing plates, use for etching molded parts, and production of protective lacquers and dielectric layers in electronics, especially microelectronics.
- B-1 IRGACURE OXE 01 (manufactured by BASF)
- B-2 IRGACURE OXE 02 (manufactured by BASF)
- B-3 IRGACURE 784 (manufactured by BASF)
- B-4 NCI-831 (manufactured by ADEKA Corporation)
- the obtained cured film was cut into a strip having a width of 3 mm using a dicing saw (DAD3350 type, manufactured by DISCO), and then stripped from the silicon wafer using 46% hydrofluoric acid.
- the elongation of the cured film peeled from the silicon wafer was measured and the mechanical properties were evaluated according to the following criteria.
- the elongation of the cured film was measured using a tensile tester (UTM-II-20 type, manufactured by Orientec Co., Ltd.) according to ASTM D882-09.
- C Elongation is 40 or more and less than 50%
- D Elongation is less than 40%
- a resin composition was spin-coated on a copper substrate so that the film thickness after curing was about 10 ⁇ m, dried, and then heated using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindbergh).
- the atmosphere in the furnace was adjusted to the conditions shown in the table below, and heating was performed under the conditions shown in the table below to obtain a cured film.
- the oxygen partial pressure and the oxygen concentration of the atmosphere in the furnace were adjusted by performing nitrogen substitution and using an oxygen concentration meter (manufactured by Yokogawa Electric).
- the obtained cured film was cut into a strip with a width of 3 mm using a dicing saw (DAD3350 type, manufactured by DISCO), and then peeled from the copper substrate using an aqueous solution of ferric chloride.
- the copper substrate after peeling off the cured film formed on the surface is referred to as a copper substrate 1.
- the copper substrate 1 is free from discoloration / corrosion, film thickness variation / irregularities, and has properties equivalent to those of the blank.
- the example was able to form a cured film having excellent mechanical properties.
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Abstract
Description
膜を酸素分圧が6~150Paの雰囲気下で加熱硬化する工程と、
を含む硬化膜の製造方法。
<2> 加熱硬化する工程の雰囲気圧力が0.08~0.12MPaである、<1>に記載の硬化膜の製造方法。
<3> 加熱硬化する工程は、膜を170~350℃に加熱する、<1>または<2>に記載の硬化膜の製造方法。
<4> 膜を形成する工程と加熱硬化する工程との間に、膜を露光する工程および露光後の膜を現像する工程を含む、<1>~<3>のいずれか1つに記載の硬化膜の製造方法。
<5> 樹脂組成物が適用される基板は、金属基板または金属層を含む基板である、<1>~<4>のいずれか1つに記載の硬化膜の製造方法。
<6> 絶縁層用の硬化膜の製造方法である、<1>~<5>のいずれか1つに記載の硬化膜の製造方法。
<7> ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群から選択される少なくとも1種のポリマー前駆体と、ラジカル重合性モノマーとを含む樹脂組成物であって、
<1>~<6>のいずれか1つに記載の硬化膜の製造方法に用いられる樹脂組成物。
<8> <7>に記載の樹脂組成物から得られる硬化膜。
<9> <1>~<6>のいずれか1つに記載の硬化膜の製造方法により硬化膜を形成する工程と、硬化膜の表面に金属層を形成する工程とを含む、積層体の製造方法。
<10> <1>~<6>のいずれか1つに記載の硬化膜の製造方法、または、<9>に記載の積層体の製造方法を含む、半導体デバイスの製造方法。
本明細書における基(原子団)の表記に於いて、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。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)をも包含するものである。
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、「(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。
本発明における物性値は特に述べない限り、温度23℃、気圧101325Paの下での値とする。
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、特に述べない限り、ゲル浸透クロマトグラフィ(GPC測定)によって測定されたものであり、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。この測定において、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。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。
本発明における温度は、特に述べない限り、23℃とする。
本発明の硬化膜の製造方法は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群から選択される少なくとも1種のポリマー前駆体と、ラジカル重合性モノマーとを含む樹脂組成物を基板に適用して膜を形成する工程(膜形成工程)と、上記膜を酸素分圧が6~150Paの雰囲気下で加熱硬化する工程(加熱硬化工程)と、を含むことを特徴とする。
(a)樹脂組成物を基板に適用して膜を形成する工程(膜形成工程)、
(b)膜形成工程の後、膜を露光する工程(露光工程)、
(c)露光後の膜を現像する工程(現像工程)、
(d)現像された膜を酸素分圧が6~150Paの雰囲気下で加熱硬化する工程(加熱硬化工程)。
膜形成工程では、ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群から選択される少なくとも1種のポリマー前駆体と、ラジカル重合性モノマーとを含む樹脂組成物を基板に適用して膜を形成する。樹脂組成物の詳細については後述する。
本発明の膜の製造方法は、膜形成工程の後、膜を露光する工程(露光工程)を含んでいてもよい。露光工程では、膜(樹脂組成物層)に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン状に露光することができる。
本発明の膜の製造方法は、露光後の膜(樹脂組成物層)を現像する工程(現像工程)を含んでもよい。現像を行うことにより、露光されていない部分(非露光部)が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えば、パドル、スプレー、浸漬、超音波等の現像方法が採用可能である。
現像は現像液を用いて行う。現像液は、露光されていない部分(非露光部)が除去されるのであれば、特に制限なく使用できる。現像液は、有機溶剤を含むことが好ましく、現像液が有機溶剤を90%以上含むことがより好ましい。本発明では、現像液は、ClogP値が-1~5の有機溶剤を含むことが好ましく、ClogP値が0~3の有機溶剤を含むことがより好ましい。ClogP値は、ChemBioDrawにて構造式を入力して計算値として求めることができる。
有機溶剤は、エステル類として、例えば、酢酸エチル、酢酸-n-ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、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: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: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: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、ならびに、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、ならびに、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、ならびに、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、スルホキシド類としてジメチルスルホキシドが好適に挙げられる。
本発明では、特にシクロペンタノン、γ-ブチロラクトンが好ましく、シクロペンタノンがより好ましい。
現像液は、50質量%以上が有機溶剤であることが好ましく、70質量%以上が有機溶剤であることがより好ましく、90質量%以上が有機溶剤であることがさらに好ましい。また、現像液は、100質量%が有機溶剤であってもよい。
現像液を用いた処理の後、さらに、リンスを行ってもよい。リンスは、現像液とは異なる溶剤で行うことが好ましい。例えば、樹脂組成物に含まれる溶剤を用いてリンスすることができる。リンス時間は、5秒~1分が好ましい。
加熱硬化工程では、膜(露光工程および現像工程を含む場合は、現像された膜)を加熱する。加熱によりポリマー前駆体の環化反応が進行して硬化膜が得られる。加熱硬化工程は、例えば、加熱チャンバー内で膜を加熱して行うことができる。
加熱は、加熱開始時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1℃/分以上とすることにより、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、硬化膜の残存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温度のことをいう。例えば、樹脂組成物を基板の上に適用した後、乾燥させる場合、この乾燥後の膜(層)の温度であり、例えば、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。
加熱時間(最高加熱温度での加熱時間)は、10~360分であることが好ましく、20~300分であることがより好ましく、30~240分であることがさらに好ましい。
特に多層の積層体を形成する場合、硬化膜の層間の密着性の観点から、膜を180℃~320℃で加熱することが好ましく、180℃~260℃で加熱することがより好ましい。その理由は定かではないが、この温度とすることで、層間のポリマー前駆体のエチニル基同士が架橋反応を進行しているためと考えられる。
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、上述した本発明の硬化膜の製造方法により硬化膜を形成する工程(硬化膜形成工程)と、この硬化膜の表面に金属層を形成する工程(金属層形成工程)とを含む。
また、本発明の積層体の製造方法は、硬化膜形成工程と、金属層形成工程とを交互に複数回(好ましくは2~7回、より好ましくは2~5回)行ってもよい。このようにすることで、硬化膜(樹脂層)と、金属層とが交互に複数積層した、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層のような多層配線構造の積層体を製造することができる。
本発明の半導体デバイスの製造方法は、上述した本発明の硬化膜の製造方法、または、上述した本発明の積層体の製造方法を含む。半導体デバイスの具体例としては、特開2016-027357号公報の段落0213~0218の記載および図1の記載を参酌でき、これらの内容は本明細書に組み込まれる。
次に、本発明の膜の製造方法に用いる樹脂組成物について説明する。
本発明の樹脂組成物は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体から選択されるポリマー前駆体を含む。本発明で用いられるポリマー前駆体は、より本発明の効果が顕著に得られやすいという理由からポリイミド前駆体であることが好ましい。
ポリイミド前駆体としては下記式(1)で表される構成単位を含むことが好ましい。このような構成とすることにより、より膜強度に優れた樹脂組成物が得られる。
R111は2価の有機基を表す。2価の有機基としては、直鎖または分岐の脂肪族基、環状の脂肪族基、および芳香族基、複素芳香族基、またはこれらの組み合わせからなる基が例示され、炭素数2~20の直鎖の脂肪族基、炭素数3~20の分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数6~20の芳香族基、または、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基がより好ましい。
R111は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖または分岐の脂肪族、環状の脂肪族または芳香族ジアミンなどが挙げられる。ジアミンは、1種のみ用いてもよいし、2種以上用いてもよい。
具体的には、ジアミンは、炭素数2~20の直鎖脂肪族基、炭素数3~20の分岐または環状の脂肪族基、炭素数6~20の芳香族基、または、これらの組み合わせからなる基を含むものであることが好ましく、炭素数6~20の芳香族基を含むジアミンであることがより好ましい。芳香族基の例としては、下記が挙げられる。
ジェファーミン(登録商標)KH-511、ジェファーミン(登録商標)ED-600、ジェファーミン(登録商標)ED-900、ジェファーミン(登録商標)ED-2003、ジェファーミン(登録商標)EDR-148、ジェファーミン(登録商標)EDR-176の構造を以下に示す。
R50~R57の1価の有機基として、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(1)におけるR115は、4価の有機基を表す。4価の有機基としては、芳香環を含む基であることが好ましく、下記式(5)または式(6)で表される基がより好ましい。
式(1)におけるR113およびR114は、それぞれ独立に、水素原子または1価の有機基を表す。R113およびR114の少なくとも一方がラジカル重合性基を含むことが好ましく、両方がラジカル重合性基を含むことがより好ましい。ラジカル重合性基としては、ラジカルの作用により、架橋反応することが可能な基であって、好ましい例として、エチレン性不飽和結合を有する基が挙げられる。エチレン性不飽和結合を有する基としては、ビニル基、アリル基、(メタ)アクリロイル基、下記式(III)で表される基などが挙げられる。
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(アルキレン基としては炭素数1~12が好ましく、1~6がより好ましく、1~3が特に好ましい;繰り返し数は1~12が好ましく、1~6がより好ましく、1~3が特に好ましい)を表す。なお、(ポリ)オキシアルキレン基とは、オキシアルキレン基またはポリオキシアルキレン基を意味する。
好適なR201の例は、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。
特に好ましくは、R200がメチル基で、R201がエチレン基である。
R113またはR114が表す1価の有機基としては、現像液の溶解度を向上させる置換基が好ましく用いられる。
R113またはR114が、水素原子、2-ヒドロキシベンジル、3-ヒドロキシベンジルおよび4-ヒドロキシベンジルであることが、水性現像液に対する溶解性の点からは、より好ましい。
アルキル基の炭素数は1~30が好ましい(環状の場合は3以上)。アルキル基は直鎖、分岐、環状のいずれであってもよい。直鎖または分岐のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イソプロピル基、イソブチル基、sec-ブチル基、t-ブチル基、1-エチルペンチル基、および2-エチルヘキシル基が挙げられる。環状のアルキル基は、単環の環状のアルキル基であってもよく、多環の環状のアルキル基であってもよい。単環の環状の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。多環の環状の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。また、芳香族基で置換されたアルキル基としては、次に述べる芳香族基で置換された直鎖アルキル基が好ましい。
R112の好ましい範囲は、式(5)におけるR112と同義であり、中でも酸素原子であることがより好ましい。
式中のカルボニル基のベンゼン環への結合位置は、式(1-A)において、4,5,3’,4’であることが好ましい。式(1-B)においては、1,2,4,5であることが好ましい。
ポリイミド前駆体の分子量の分散度は、1.5~3.5が好ましく、2~3がより好ましい。
ポリイミド前駆体の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は1種でもよいし、2種以上でもよい。
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドンおよびN-エチルピロリドンが例示される。
ポリベンゾオキサゾール前駆体は、下記式(2)で表される構成単位を含むことが好ましい。
式(2)において、R122は、4価の有機基を表す。4価の有機基としては、上記式(1)におけるR115と同義であり、好ましい範囲も同様である。R122は、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に由来することが好ましい。
R123およびR124は、それぞれ独立に、水素原子または1価の有機基を表し、上記式(1)におけるR113およびR114と同義であり、好ましい範囲も同様である。
閉環に伴う硬化膜の反りの発生を抑制できる点で、ポリベンゾオキサゾール前駆体は、下記式(SL)で表されるジアミン残基を他の種類の構成単位として含むことが好ましい。
ポリベンゾオキサゾール前駆体の分子量の分散度は、1.5~3.5が好ましく、2~3がより好ましい。
本発明の樹脂組成物は、ポリマー前駆体を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本発明の樹脂組成物はラジカル重合性モノマーを含む。ラジカル重合性モノマーとしては、ラジカル重合性を有する化合物を用いることができる。ラジカル重合性基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基などのエチレン性不飽和結合を有する基が挙げられる。ラジカル重合性基は、(メタ)アクリロイル基が好ましい。
また、上述以外の好ましいラジカル重合性モノマーとして、特開2010-160418号公報、特開2010-129825号公報、特許第4364216号公報等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を2個以上有する化合物や、カルド樹脂も使用することが可能である。
さらに、その他の例としては、特公昭46-043946号公報、特公平01-040337号公報、特公平01-040336号公報に記載の特定の不飽和化合物や、特開平02-025493号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭61-022048号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。さらに日本接着協会誌 vol.20、No.7、300~308ページ(1984年)に光重合性モノマーおよびオリゴマーとして紹介されているものも使用することができる。
酸基を有するラジカル重合性モノマーの好ましい酸価は、0.1~40mgKOH/gであり、特に好ましくは5~30mgKOH/gである。ラジカル重合性モノマーの酸価が上記範囲であれば、製造や取扱性に優れ、さらには、現像性に優れる。また、重合性が良好である。
本発明の樹脂組成物は、上述したラジカル重合性モノマー以外の重合性化合物(以下、他の重合性化合物ともいう)をさらに含むことができる。他の重合性化合物としては、ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物;エポキシ化合物;オキセタン化合物;ベンゾオキサジン化合物が挙げられる。
ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物としては、下記式(AM1)、(AM4)または(AM5)で示される化合物が好ましい。
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、組成物の低温硬化および反りの抑制に効果的である。
オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成株式会社製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221、OXT-191、OXT-223)が好適に使用することができ、これらは単独で、あるいは2種以上混合してもよい。
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、さらに熱収縮を小さくして反りの発生が抑えられることから好ましい。
本発明の樹脂組成物は、熱塩基発生剤を含むことが好ましい。熱塩基発生剤としては、その種類等は特に定めるものではないが、40℃以上に加熱すると塩基を発生する酸性化合物、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から選ばれる少なくとも1種を含む熱塩基発生剤を含むことが好ましい。ここで、pKa1とは、酸の第一のプロトンの解離定数(Ka)の対数(-Log10Ka)を表し、詳細は後述する。
このような化合物を配合することにより、ポリマー前駆体などの環化反応を低温で行うことができる。また、熱塩基発生剤は、加熱しなければ塩基を発生しないので、ポリマー前駆体と共存させても、保存中におけるポリマー前駆体の環化を抑制でき、保存安定性に優れている。
式(101) 式(102)
式(Y1-1)~(Y1-5)において、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。
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。
本実施形態において、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以下が一層好ましい。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、酸の第一のプロトンの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、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。
式(XA)
本発明の樹脂組成物はラジカル重合開始剤を含有することが好ましい。特にポリマー前駆体としてラジカル重合性基を含むものを用いた場合や、ラジカル重合性化合物を用いた場合においては、本発明の樹脂組成物はラジカル重合開始剤を含有することが好ましい。ラジカル重合開始剤としては、光ラジカル重合開始剤、熱ラジカル重合開始剤が挙げられる。本発明の樹脂組成物で用いられるラジカル重合開始剤は光ラジカル重合開始剤であることが好ましい。
光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。
光ラジカル重合開始剤は、約300~800nm(好ましくは330~500nm)の範囲内で少なくとも約50のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計(Varian社製Cary-5 spectrophotometer)にて、酢酸エチル溶剤を用い、0.01g/Lの濃度で測定することが好ましい。
ヒドロキシアセトフェノン系開始剤としては、IRGACURE 184(IRGACUREは登録商標)、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127(BASF社製)を用いることができる。
アミノアセトフェノン系開始剤としては、市販品であるIRGACURE 907、IRGACURE 369、および、IRGACURE 379(BASF社製)を用いることができる。
アミノアセトフェノン系開始剤として、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。
アシルホスフィン系開始剤としては、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(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2000-080068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、下記の構造の化合物や、3-ベンゾイル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。本発明の樹脂組成物においては、特に光ラジカル重合開始剤としてオキシム化合物(オキシム系の光重合開始剤)を用いることが好ましい。オキシム系の光重合開始剤は、分子内に >C=N-O-C(=O)- の連結基を有する。
さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開2010-262028号公報に記載されている化合物、特表2014-500852号公報の段落0345に記載されている化合物24、36~40、特開2013-164471号公報の段落0101に記載されている化合物(C-3)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。
さらに好ましい光ラジカル重合開始剤は、トリハロメチルトリアジン化合物、α-アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α-アミノケトン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物からなる群より選ばれる少なくとも1種の化合物が一層好ましく、メタロセン化合物またはオキシム化合物を用いるのがより一層好ましく、オキシム化合物がさらに一層好ましい。
また、光ラジカル重合開始剤は、ベンゾフェノン、N,N’-テトラメチル-4,4’-ジアミノベンゾフェノン(ミヒラーケトン)等のN,N’-テトラアルキル-4,4’-ジアミノベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1,2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-プロパノン-1等の芳香族ケトン、アルキルアントラキノン等の芳香環と縮環したキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体などを用いることもできる。また、下記式(I)で表される化合物を用いることもできる。
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、重合性を有する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、ポリマー前駆体の環化と共に、ポリマー前駆体の重合反応を進行させることもできるので、より高度な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、具体的には、特開2008-63554号公報の段落0074~0118に記載されている化合物が挙げられる。
本発明の樹脂組成物は、溶剤を含有することが好ましい。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、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、アミ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なものとして挙げられる。
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なものとして挙げられる。
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-ヘプタノン等が好適なものとして挙げられる。
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、リモネン等が好適なものとして挙げられる。
スルホキシド類として、例えば、ジメチルスルホキシドが好適なものとして挙げられる。
アミド類として、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、N,N-ジメチルホルムアミド等が好適なものとして挙げられる。
本発明では、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、N-メチル-2-ピロリドン、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から選択される1種の溶剤、または、2種以上で構成される混合溶剤が好ましい。ジメチルスルホキシドとγ-ブチロラクトンとの併用が特に好ましい。
溶剤は1種のみ含有していてもよいし、2種以上含有していてもよい。溶剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。
本発明の樹脂組成物は、さらにマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制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可能となる。
マイグレーション抑制剤としては、特に制限はないが、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、チオ尿素類およびスルファニル基を有する化合物、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。特に、1,2,4-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、1H-テトラゾール、5-フェニルテトラゾール等のテトラゾール系化合物が好ましく使用できる。
本発明の樹脂組成物は、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、1,4-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-スルホプロピルアミノ)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、国際公開第2015/125469号の段落0031~0046に記載の化合物を用いることもできる。また、下記化合物を用いることができる(Meはメチル基である)。
本発明の樹脂組成物は、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の金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、シランカップリング剤などが挙げられる。
本発明の樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種の添加物、例えば、熱酸発生剤、増感色素、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、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。
本発明の樹脂組成物は、熱酸発生剤を含んでいてもよい。
熱酸発生剤は、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。
本発明の樹脂組成物は、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、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル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、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸ある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。
本発明の樹脂組成物は、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、およびGeHを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、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うる。特に、チオール化合物を好ましく用いることができる。
また、連鎖移動剤は、国際公開第2015/199219号の段落0152~0153に記載の化合物を用いることもできる。
本発明の樹脂組成物には、塗布性をより向上させる観点から、各種類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類の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。
本発明の樹脂組成物は、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。
また、高級脂肪酸誘導体は、国際公開第2015/199219号の段落0155に記載の化合物を用いることもできる。
本発明の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、本発明の樹脂組成物の全固形分に対して、0.1~10質量%であることが好ましい。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。
本発明の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%未満がより好ましく、0.6質量%未満がさらに好ましい。
また、本発明の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、本発明の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、本発明の樹脂組成物を構成する原料に対してフィルターろ過を行う、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。
本発明の樹脂組成物は、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、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よい。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よい。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よい。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よい。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、本発明の硬化膜について説明する。
本発明の硬化膜は、本発明の樹脂組成物から得られるものである。本発明の硬化膜の膜厚は、例えば、0.5μm以上とすることができ、1μm以上とすることができる。また、上限値としては、100μm以下とすることができ、30μm以下とすることもできる。本発明の硬化膜の膜厚は1~30μmであることが好ましい。
下記表に記載の成分を混合して樹脂組成物を得た。
B-1:IRGACURE OXE 01(BASF社製)
B-2:IRGACURE OXE 02(BASF社製)
B-3:IRGACURE 784(BASF社製)
B-4:NCI-831((株)ADEKA製)
C-1:SR-209(Arkema社製)
C-2:M-306(東亞合成(株)製)
C-3:A-TMMT(新中村化学工業(株)製)
C-4:KAYARAD DPHA(日本化薬(株)製)
D-1:N-メチルピロリドン
D-2:乳酸エチル
D-3:γ-ブチロラクトン
D-4:ジメチルスルホキシド
G-1:1,4-ベンゾキノン
G-2:4-メトキシフェノール
H-1:1,2,4-トリアゾール
H-2:1H-テトラゾール
<<機械特性の評価>>
銅金属層が表面に形成されたシリコンウエハーに、硬化後の膜厚が約10μmとなるように樹脂組成物をスピン塗布し、乾燥した後、昇温プログラム式キュア炉(VF-2000型、光洋リンドバーグ社製)を用いて、炉内の雰囲気を下記表に記載の条件に調整し、下記表に記載の条件で加熱を行い、硬化膜を得た。なお、炉内の雰囲気の酸素分圧および酸素濃度は、窒素置換を行い、酸素濃度計(横河電機製)にて調整した。
得られた硬化膜をダイシングソー(DAD3350型、DISCO社製)を用いて3mm幅の短冊状にカットした後、46%フッ化水素酸を用いてシリコンウエハーから剥がした。シリコンウエハーから剥離した硬化膜の伸度を測定して以下の基準で機械特性を評価した。硬化膜の伸度は、引張試験機(UTM-II-20型、オリエンテック社製)を用いて、ASTM D882-09に従って測定した。
A:伸度が60%以上
B:伸度が50%以上60%未満
C:伸度が40以上50%未満
D:伸度が40%未満
銅基板上に、硬化後の膜厚が約10μmとなるように樹脂組成物をスピン塗布し、乾燥した後、昇温プログラム式キュア炉(VF-2000型、光洋リンドバーグ社製)を用いて、炉内の雰囲気を下記表に記載の条件に調整し、下記表に記載の条件で加熱を行い、硬化膜を得た。なお、炉内の雰囲気の酸素分圧および酸素濃度は、窒素置換を行い、酸素濃度計(横河電機製)にて調整した。
得られた硬化膜をダイシングソー(DAD3350型、DISCO社製)を用いて3mm幅の短冊状にカットした後、塩化第二鉄水溶液を用いて銅基板から剥がした。表面に形成された硬化膜を剥離した後の銅基板を銅基板1とする。
硬化膜を形成する前の銅基板(ブランク)と、表面に形成された硬化膜を剥離した後の銅基板(銅基板1)について、光学顕微鏡(Nikon製)による表面観察(変色・腐食の確認)と、走査電子顕微鏡(日立製)による断面観察(膜厚変動・凹凸の確認)を行い、以下の基準で銅腐食性を評価した。
A:銅基板1は変色・腐食、膜厚変動・凹凸がなく、ブランクと同等の性状である。
B:銅基板1はブランクに比べて、少し紫色が濃くなっているが、膜厚変動や凹凸がない。
C:銅基板1はブランクに比べて、少し紫色が濃くなっており、銅がやや壊れて少し凹凸になっている。
D:銅基板1はブランクに比べて、濃紫色になっており、更に、銅が壊れて激しい凹凸がある。
Claims (10)
- ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群から選択される少なくとも1種のポリマー前駆体と、ラジカル重合性モノマーとを含む樹脂組成物を基板に適用して膜を形成する工程と、
前記膜を酸素分圧が6~150Paの雰囲気下で加熱硬化する工程と、
を含む硬化膜の製造方法。 - 前記加熱硬化する工程の雰囲気圧力が0.08~0.12MPaである、請求項1に記載の硬化膜の製造方法。
- 前記加熱硬化する工程は、前記膜を170~350℃に加熱する、請求項1または2に記載の硬化膜の製造方法。
- 前記膜を形成する工程と前記加熱硬化する工程との間に、前記膜を露光する工程および露光後の膜を現像する工程を含む、請求項1~3のいずれか1項に記載の硬化膜の製造方法。
- 前記樹脂組成物が適用される基板は、金属基板または金属層を含む基板である、請求項1~4のいずれか1項に記載の硬化膜の製造方法。
- 絶縁層用の硬化膜の製造方法である、請求項1~5のいずれか1項に記載の硬化膜の製造方法。
- ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群から選択される少なくとも1種のポリマー前駆体と、ラジカル重合性モノマーとを含む樹脂組成物であって、
請求項1~6のいずれか1項に記載の硬化膜の製造方法に用いられる樹脂組成物。 - 請求項7に記載の樹脂組成物から得られる硬化膜。
- 請求項1~6のいずれか1項に記載の硬化膜の製造方法により硬化膜を形成する工程と、前記硬化膜の表面に金属層を形成する工程とを含む、積層体の製造方法。
- 請求項1~6のいずれか1項に記載の硬化膜の製造方法、または、請求項9に記載の積層体の製造方法を含む、半導体デバイスの製造方法。
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