WO2020066975A1 - 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス - Google Patents
樹脂組成物、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス Download PDFInfo
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- WO2020066975A1 WO2020066975A1 PCT/JP2019/037187 JP2019037187W WO2020066975A1 WO 2020066975 A1 WO2020066975 A1 WO 2020066975A1 JP 2019037187 W JP2019037187 W JP 2019037187W WO 2020066975 A1 WO2020066975 A1 WO 2020066975A1
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- resin composition
- mass
- cured film
- compound
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- XYXJKPCGSGVSBO-UHFFFAOYSA-N CC(C)(C)c1cc(C)c(CN(C(N(Cc2c(C)cc(C(C)(C)C)c(O)c2C)C(N2Cc3c(C)cc(C(C)(C)C)c(O)c3C)=O)=O)C2=O)c(C)c1O Chemical compound CC(C)(C)c1cc(C)c(CN(C(N(Cc2c(C)cc(C(C)(C)C)c(O)c2C)C(N2Cc3c(C)cc(C(C)(C)C)c(O)c3C)=O)=O)C2=O)c(C)c1O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N c1ccc2nn[nH]c2c1 Chemical compound c1ccc2nn[nH]c2c1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- JYBWAYHAOLQZJX-UHFFFAOYSA-N c1n[n](-c2ccccc2)nc1 Chemical compound c1n[n](-c2ccccc2)nc1 JYBWAYHAOLQZJX-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
Definitions
- the present invention relates to a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.
- the present invention also relates to a cured film, a laminate, a method for producing a cured film, and a semiconductor device using the resin composition containing the polymer precursor described above.
- Cyclic and cured resins such as polyimide resins and polybenzoxazole resins have been applied to various applications because of their excellent heat resistance and insulation properties.
- the application of the semiconductor device is not particularly limited.
- a semiconductor device for mounting may be used as a material for an insulating film or a sealing material, or as a protective film (see Non-Patent Documents 1 and 2). Further, it is also used as a base film or coverlay of a flexible substrate.
- Such a polyimide resin or the like generally has low solubility in a solvent. Therefore, a method of dissolving the polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor in a solvent is often used.
- Patent Document 1 describes an invention relating to a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor, and a thermal base generator. Patent Document 1 describes that by using a specific thermal base generator, storage stability is good and a cyclization reaction of a polyimide precursor or the like can be performed at a low temperature.
- a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor
- Patent Document 1 describes that by using a specific thermal base generator, storage stability is good and a cyclization reaction of a polyimide precursor or the like can be performed at a low temperature.
- Patent Document 1 the storage stability of a resin composition containing a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor could be improved.
- a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor
- further research and development are required to meet the recent diversified required characteristics of resin compositions containing these polymer precursors. For example, with respect to a cured film obtained from a resin composition containing a polymer precursor, further improvement in moisture resistance is desired.
- an object of the present invention is to provide a resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device, which can form a cured film having good storage stability and excellent moisture resistance.
- the present inventors have conducted intensive studies on a resin composition containing at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. Have been achieved, and the present invention has been completed.
- the present invention provides the following.
- a resin composition containing at least one polymer precursor selected from a polyimide precursor and a polybenzaoxazole precursor The total content of HNO 2 , NO 2 ⁇ , HNO 3 , NO 3 ⁇ , H 2 SO 4 , HSO 4 ⁇ , SO 4 2 ⁇ , H 2 SO 3 , HSO 3 ⁇ and SO 3 2 ⁇ is a resin composition.
- the resin composition is 1 mass ppb or more and 1000 mass ppm or less based on the total solid content of the resin composition.
- ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, which is used for forming a pattern by developing using a developer containing 90% by mass or more of an organic solvent.
- ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, which is used for forming a member that comes into contact with a metal.
- ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, which is used for forming an interlayer insulating film for a redistribution layer.
- ⁇ 9> A cured film obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 8>.
- ⁇ 10> The cured film according to ⁇ 9>, having a thickness of 1 to 30 ⁇ m.
- ⁇ 11> A laminate having two or more cured films according to ⁇ 9> or ⁇ 10> and having a metal layer between the two cured films.
- ⁇ 12> A method for producing a cured film, comprising a film forming step of forming a film by applying the resin composition according to any one of ⁇ 1> to ⁇ 8> to a substrate.
- the method for producing a cured film according to ⁇ 12> comprising an exposure step of exposing the film and a development step of developing the film.
- ⁇ 15> A semiconductor device having the cured film according to ⁇ 9> or ⁇ 10> or the laminate according to ⁇ 11>.
- a resin composition a cured film, a laminate, a method for producing a cured film, and a semiconductor device which can form a cured film having good storage stability and excellent moisture resistance.
- the description of the components of the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
- the notation of not indicating substituted or unsubstituted includes not only a group having no substituent but also a group 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).
- exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
- the light used for exposure generally includes an active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam.
- active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam.
- active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam.
- active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam.
- EUV light extreme ultraviolet
- X-ray extreme ultraviolet
- the physical property values in the present invention are values at a temperature of 23 ° C. and a pressure of 101325 Pa unless otherwise specified.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC measurement) and are defined as polystyrene equivalent values, unless otherwise specified.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, for example, using HLC-8220 (manufactured by Tosoh Corporation), and using guard columns HZ-L, TSKgel Super HZM-M, and TSKgel as columns.
- THF tetrahydrofuran
- detection is performed using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
- the resin composition of the present invention is a resin composition containing at least one polymer precursor selected from a polyimide precursor and a polybenzaoxazole precursor, and comprises HNO 2 , NO 2 ⁇ , HNO 3 , NO 3 ⁇ ,
- the total content of H 2 SO 4 , HSO 4 ⁇ , SO 4 2 ⁇ , H 2 SO 3 , HSO 3 ⁇ and SO 3 2 ⁇ is 1 mass ppb or more and 1000 mass ppm with respect to the total solid content of the resin composition. It is characterized by the following.
- HNO 2 , NO 2 ⁇ , HNO 3 , NO 3 ⁇ , H 2 SO 4 , HSO 4 ⁇ , SO 4 2 ⁇ , H 2 SO 3 , HSO 3 ⁇ and SO 3 2 ⁇ are collectively referred to as specific components. .
- the content of the specific component is 1 mass ppb or more based on the total solid content of the resin composition, the reaction of the polymer precursor during storage and the like can be suppressed, and as a result, excellent It is presumed that storage stability was obtained. Further, since the content of the specific component is 1000 mass ppm or less based on the total solid content of the resin composition, even when the cured film is exposed to a high-humidity environment, it is not easily hydrolyzed, and as a result, the moisture resistance is reduced. It is presumed that an excellent cured film could be formed.
- the resin composition of the present invention is suitable for use in forming a member that comes into contact with metal.
- the member to be brought into contact with the metal include an interlayer insulating film for a redistribution layer, an insulating tube, a sealing film, and a substrate material (such as a base film or a coverlay of a flexible printed circuit board).
- a substrate material such as a base film or a coverlay of a flexible printed circuit board.
- the total content of the specific components is less than 1000 ppm by mass with respect to the total solid content of the resin composition, from the viewpoint of moisture resistance of the obtained cured film and prevention of metal corrosion. It is preferably 900 ppm by mass or less, more preferably 800 ppm by mass or less, and particularly preferably 500 ppm by mass or less.
- the lower limit is the total solid content of the resin composition because it is easy to improve the storage stability of the resin composition, the moisture resistance of the obtained film, etc. due to the suppression reaction of components that promote deterioration, although the cause is not clear. It is preferably 1.0 mass ppb or more, more preferably 1.1 mass ppb or more, still more preferably 1.2 mass ppb or more, and preferably 1.5 mass ppb or more. Particularly preferred.
- each content is 1000 mass ppm or less with respect to the total solid content of the resin composition, more preferably 900 mass ppm or less, even more preferably 800 mass ppm or less, and 500 mass ppm. It is particularly preferred that: Further, the total content of HNO 2 and NO 2 ⁇ is preferably 1,000 mass ppm or less, more preferably 900 mass ppm or less, and 800 mass ppm or less based on the total solid content of the resin composition.
- the total content of HNO 3 and NO 3 ⁇ is preferably at most 1,000 ppm by mass, more preferably at most 900 ppm by mass, and at most 800 ppm by mass, based on the total solid content of the resin composition. Is more preferable, and particularly preferably 500 ppm by mass or less.
- the total content of H 2 SO 4 , HSO 4 ⁇ and SO 4 2 ⁇ is preferably 1000 ppm by mass or less, and preferably 900 ppm by mass or less based on the total solid content of the resin composition. It is more preferably at most 800 ppm by mass, particularly preferably at most 500 ppm by mass.
- the total content of H 2 SO 3 , HSO 3 ⁇ and SO 3 2 ⁇ is preferably 1,000 ppm by mass or less, and more preferably 900 ppm by mass or less based on the total solid content of the resin composition. It is more preferably at most 800 ppm by mass, particularly preferably at most 500 ppm by mass.
- the content of the specific component can be adjusted by adjusting the blending amount of the specific component or the raw material containing the specific component, or by adjusting the purification conditions of the resin composition and the raw material.
- the content of the specific component was analyzed by the ion chromatography method. Specifically, a measurement sample, a non-aqueous organic solvent, and water are mixed, and the amount of a specific component extracted into an aqueous solution by a liquid separation operation or centrifugation is measured by an ion chromatograph method. Of the specific component was calculated.
- NO 2 ⁇ , NO 3 ⁇ , HSO 4 ⁇ , SO 4 2 ⁇ , HSO 3 ⁇ and SO 3 2 ⁇ exist in a salt state. May be.
- HNO 2 , HNO 3 , H 2 SO 4 , and H 2 SO 3 may be ionized and exist in an ion state.
- the atoms or atomic groups constituting the salt are not particularly limited.
- alkali metals lithium, potassium, sodium, etc.
- alkaline earth metals calcium, beryllium, magnesium, strontium, barium
- the resin composition of the present invention is used to form a pattern by developing using a developer containing 90% by mass or more of an organic solvent.
- 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 effect of the present invention can be more remarkably obtained.
- the polyimide precursor preferably contains a structural 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 are 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 composed of a combination thereof.
- an aromatic group having 6 to 20 carbon atoms is more preferable.
- R 111 is derived from a diamine.
- diamine used in the production of the polyimide precursor examples include linear or branched aliphatic, cyclic aliphatic or aromatic diamines.
- Diamines may be used alone or in combination of two or more.
- the diamine may be a linear 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.
- the diamine is a diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 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 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-
- Diamines having two or more alkylene glycol units in the main chain are also preferred examples.
- it is a diamine containing one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably a diamine containing no aromatic ring.
- x, y, and z are average values.
- R 111 is preferably represented by -Ar 0 -L 0 -Ar 0- from the viewpoint of the flexibility of the obtained cured film.
- Ar 0 is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and is preferably a phenylene group.
- the preferred range is the same as that of A described above.
- R 111 is preferably a divalent organic group represented by the following formula (51) or (61) from the viewpoint of i-ray transmittance.
- a divalent organic group represented by the formula (61) is more preferable from the viewpoints of i-line 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.
- Examples of the monovalent organic group represented by R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 (preferably 1 to 6) carbon atoms and a fluorine atom having 1 to 10 (preferably 1 to 6) carbon atoms. Alkyl group and the like.
- R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
- Diamine compounds giving the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 '-Bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more may be used in combination.
- 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 (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 removing the acid dianhydride group from the tetracarboxylic dianhydride.
- the tetracarboxylic dianhydride may be used alone or in combination of two or more.
- the compound represented by the following formula (7) is preferable as the tetracarboxylic dianhydride.
- 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 4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride,
- DAA-1 tetracarboxylic dianhydrides
- DAA-5 tetracarboxylic dianhydrides
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
- at least one of R 113 and R 114 contains a radically polymerizable group, and more preferably both contain a radically polymerizable group.
- the radical polymerizable group is a group capable of undergoing a cross-linking reaction by the action of a radical, and a preferable example 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 (an alkylene group having 1 carbon atom To 12, preferably 1 to 6, more preferably 1 to 3, and the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.)
- a (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
- R201 examples include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene. , —CH 2 CH (OH) CH 2 —, and more preferably an ethylene group, a propylene group, a trimethylene group, and —CH 2 CH (OH) CH 2 —.
- R 200 is a methyl group and R 201 is an ethylene group.
- an aliphatic group, an aromatic group, and an aryl group having one, two or three, preferably one acid group And an alkyl group 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 specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified.
- 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 a developer is preferably used.
- R 113 or R 114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 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, and 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group.
- the cyclic alkyl group may be a monocyclic alkyl group or a polycyclic alkyl group.
- Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
- polycyclic alkyl group examples include, for example, 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.
- an alkyl group substituted with an aromatic group a linear alkyl group substituted with an aromatic group described below is preferable.
- 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, an azulene ring) Ring, heptarene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (group As the constituting cyclic structure, fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, a substituted or unsub
- the polyimide precursor has a fluorine atom in the structural unit.
- the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, 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). Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (paraaminophenyl) octamethylpentasiloxane, and the like can be given as the diamine component.
- the structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A) or (1-B).
- a 11 and A 12 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 It represents an organic group
- at least one of R 113 and R 114 is preferably a group containing a radical polymerizable group, and more preferably a radical polymerizable group.
- a preferred ranges of A 11 , A 12 , R 111 , R 113 and R 114 are each independently the same as the preferred ranges 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 formula (1-A). In the formula (1-B), 1,2,4,5 is preferable.
- the structural unit represented by the formula (1) may be one type, or may be two or more types. Further, it may contain a structural isomer of the structural unit represented by the formula (1). 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, more preferably 70 mol% or more, and particularly 90 mol% or more of all the structural units is a structural unit represented by the formula (1).
- the upper limit is practically 100 mol% or less.
- the weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and further preferably from 10,000 to 50,000.
- the number average molecular weight (Mn) is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and still more preferably from 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polyimide precursor is preferably from 1.5 to 3.5, more preferably from 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 the dicarboxylic acid or dicarboxylic acid derivative with a diamine.
- an organic solvent may be one type or two or more types.
- 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.
- the production of the polyimide precursor includes a step of depositing a solid.
- the polyimide precursor in the reaction solution can be precipitated in water and dissolved in a solvent in which the polyimide precursor is soluble, such as tetrahydrofuran, to perform solid deposition.
- 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 include an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6) and an aromatic group (preferably having 6 to 22 carbon atoms and 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable).
- the aromatic group constituting 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 range is also the same.
- the polybenzoxazole precursor may contain other types of structural units in addition to the structural unit of the above formula (2).
- the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
- R 1s is hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms is (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 having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms)
- at least one of R 3s , R 4s , R 5s and R 6s is aromatic Group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, particularly preferably having 6 to 10 carbon atoms), and the balance being a hydrogen atom or 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms).
- the a structure and the b structure may be block polymerization or random polymerization.
- the a structure is 5 to 95 mol%
- the b structure is 95 to 5 mol%
- 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 from 400 to 4,000, and more preferably from 500 to 3,000.
- the molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elasticity of the polybenzoxazole precursor after the dehydration and ring closure can be reduced, and both the effect of suppressing the warpage and the effect of improving the solubility can be achieved.
- the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit
- removal of an acid dianhydride group from tetracarboxylic dianhydride is further required in terms of improving alkali solubility.
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and further preferably from 10,000 to 50,000.
- the number average molecular weight (Mn) is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and still more preferably from 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polybenzoxazole precursor is 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 preferably 40% by mass or more based on the total solid content of the resin composition. Is more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably 70% by mass or more. Further, the content of the polymer precursor in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less based on the total solid content of the resin composition. , 98% by mass or less, more preferably 95% by mass or less.
- the resin composition of the present invention may contain only one kind of the polymer precursor, or may contain two or more kinds of the polymer precursor. When two or more kinds are included, the total amount is preferably in the above range.
- the resin composition of the present invention contains a thermal base generator.
- the type of the thermal base generator is not particularly limited, but is selected from an acidic compound which generates a base when heated to 40 ° C. or more, and an ammonium salt having an anion having an pKa of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of these.
- 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 pKa of 0 to 4 and an ammonium cation. Is preferred. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can promote the cyclization reaction of the polymer precursor, and the cyclization of the polymer precursor can be promoted. Can be performed at low temperatures.
- the solution obtained by stirring the solution is a compound having a value of less than 7 when 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, and further 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 is measured, for example, by differential scanning calorimetry, by heating the compound in a pressure-resistant capsule at 250C at 5C / min, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
- the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine.
- Tertiary amines are highly basic and can lower the cyclization temperature of the polymer precursor.
- 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 even more preferably 140 ° C. or higher.
- the molecular weight of the generated base is preferably from 80 to 2,000.
- the lower limit is more preferably 100 or more.
- the upper limit is more preferably 500 or less.
- the value of molecular weight is a theoretical value obtained from the structural formula.
- the acidic compound (A1) preferably contains at least one selected from an ammonium salt and a compound represented by the following formula (101) or (102).
- 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.)
- the compound may be a compound excluding an acidic compound which generates a base when heated to the step (1).
- the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or (102) and an anion.
- the anion may be bonded to any part of the ammonium cation through a covalent bond and may be present outside the ammonium cation molecule, but may be present outside the ammonium cation molecule. preferable.
- numerator means the case where an ammonium cation and an anion are not couple
- an anion outside the cation moiety is also referred to as a counter anion.
- Equation (101) Equation (102) R 1 to R 6 each independently represent a hydrogen atom or a hydrocarbon group, and 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 the formulas (101) and (102) may be respectively bonded 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 pKa of 0 to 4 and an ammonium cation.
- the upper limit of the pKa1 of the anion is more preferably 3.5 or less, even more preferably 3.2 or less.
- the lower limit is preferably 0.5 or more, and more preferably 1.0 or more.
- the type of anion is preferably one selected from a carboxylate anion, a phenol anion and a phosphate anion, and is more preferably a carboxylate anion because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
- the carboxylate anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion.
- the thermal base generator that can further improve the stability, curability, and developability of the resin composition.
- the stability, curability and developability of the resin composition can be further improved.
- the carboxylate anion is preferably a carboxylate anion having a pKa of 4 or less.
- pKa1 is more preferably 3.5 or less, even more preferably 3.2 or less.
- the stability of the resin composition can be further improved.
- pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid and is determined by Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, Hafliger). Compiled by: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R., R.M. al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software will be used.
- the carboxylate anion is preferably represented by the following formula (X1).
- EWG represents an electron-withdrawing group.
- the electron withdrawing group means a group having a positive Hammett's substituent constant ⁇ m.
- ⁇ m is described by Yuno Tsuno, Synthetic Organic Chemistry Society, Vol. 631-642. Note that 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 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.
- the carboxylate anion is preferably represented by the following formula (XA).
- Formula (XA) In the 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 , 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.
- thermal base generator examples include the following compounds.
- 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, and still more preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less.
- One or more thermal base generators can be used. When two or more kinds are used, the total amount is preferably in the above range.
- the resin composition of the present invention preferably contains a radical polymerization initiator.
- the resin composition of the present invention preferably contains a radical polymerization initiator.
- the radical polymerization initiator include a photoradical polymerization initiator and a thermal radical polymerization initiator.
- the radical polymerization initiator used in the resin composition of the present invention is preferably a photoradical polymerization initiator.
- the photo-radical polymerization initiator is not particularly limited, and can be appropriately selected from known photo-radical polymerization initiators.
- a photo-radical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable.
- an activator that produces some action with the photoexcited sensitizer and generates an active radical may be used.
- the photo-radical 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.
- a known compound can be arbitrarily used as the photoradical polymerization initiator.
- halogenated hydrocarbon derivatives eg, 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.
- the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of WO 2015/199219 can be referred to, and the contents are incorporated herein.
- ketone compound examples include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
- Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also suitably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Patent No. 4225988 can also be used.
- a hydroxyacetophenone-based initiator IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, 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 a compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched to a light source having a wavelength of 365 nm or 405 nm can also be used.
- the acylphosphine 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 preferably used as the photoradical polymerization initiator.
- the exposure latitude can be more effectively improved.
- Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
- compounds described in JP-A-2001-233842 compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166 can be used.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
- an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
- Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (both manufactured by BASF) and Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, JP 2012-014052A).
- a radical polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
- Adeka Aquel's NCI-831 and Adeka Aquel's NCI-930 manufactured by ADEKA Corporation
- DFI-091 manufactured by Daito Mix
- Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013-2013.
- the most preferred oxime compounds include oxime compounds having a specific substituent described in JP-A-2007-269779, oxime compounds having a thioaryl group described in JP-A-2009-191061, and the like.
- the photoradical polymerization initiator may be 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 Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.
- More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds.
- At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferably used. Is even more preferred.
- the photo-radical polymerization initiators include N, N'-tetraalkyl-4,4'-diaminobenzophenone such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkylanthraquinone, etc.
- benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by at least one oxygen atom, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, An alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by at least one oxygen atom 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 And R I02 to R I04 are each independently alkyl having 1 to 12 carbons, alkoxy or halogen having 1 to 12 carbons.
- a photoradical polymerization initiator When a photoradical polymerization initiator is contained, its content is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. Yes, 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 one kind or two or more kinds. When two or more photoradical polymerization initiators are contained, the total 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 promotes a polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be advanced 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-A-2008-063554.
- thermal radical polymerization initiator When a thermal radical polymerization initiator is contained, its content is preferably from 0.1 to 30% by mass, more preferably from 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 kind or two or more kinds. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.
- the resin composition of the present invention preferably contains a polymerizable compound.
- a radical polymerizable compound can be used as the polymerizable compound.
- the radical polymerizable compound is a compound having a radical polymerizable group.
- examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
- the radical polymerizable group is preferably a (meth) acryloyl group.
- the number of radically polymerizable groups included in the radically polymerizable compound may be one, or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and more preferably three or more. More preferred.
- the upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.
- the molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less.
- the lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.
- the resin composition of the present invention preferably contains at least one kind of bifunctional or more radically polymerizable compound containing two or more polymerizable groups, and preferably contains at least one kind of trifunctional or more functional radically polymerizable compound. More preferably, it contains species. Further, a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound may be used.
- the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.
- radical polymerizable compound examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof.
- unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
- esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyamine compounds.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy compound is also preferably used.
- substitution products of unsaturated carboxylic esters or amides having a leaving substituent such as thiol or tosyloxy groups with monofunctional or polyfunctional alcohols, amines and thiols.
- the description of paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
- radical polymerizable compound a compound having a boiling point of 100 ° C. or more under normal pressure is also preferable.
- examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)
- JP-B-50-006034 urethane (meth) acrylates as described in JP-A-51-037193, JP-A-48-064183, JP-A-49-043191.
- polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-030490, epoxy acrylates which are reaction products of epoxy resins with (meth) acrylic acid, and mixtures thereof. Can be. Further, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
- a polyfunctional (meth) acrylate obtained by reacting a compound having an ethylenically unsaturated bond with a cyclic ether group such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid can also be mentioned.
- a polyfunctional (meth) acrylate obtained by reacting a compound having an ethylenically unsaturated bond with a cyclic ether group such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid can also be mentioned.
- preferred radical polymerizable compounds other than those described above JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216, which have a fluorene ring and have an ethylenically unsaturated bond It is also possible to use a compound having two or more groups having the formula or a cardo resin.
- radical polymerizable compound examples include dipentaerythritol triacrylate (a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (a commercially available product, KAYARAD @ D-320; Nippon Kayaku ( A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylates (commercially available products: KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and their (meth) acryloyl groups are linked via ethylene glycol residues or propylene glycol residues. Bonded structures are
- radical polymerizable compounds include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, and urethane oligomer UAS- manufactured by Nippon Kayaku Co., Ltd.
- radical polymerizable compound examples include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765.
- Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, 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 described in JP-A-63-277563, JP-A-63-260909, and JP-A-01-105238 may be used as radical polymerizable compounds. It can also be used.
- the radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group and a phosphoric acid group.
- the radical polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to form an acid. Radical polymerizable compounds having a group are more preferred.
- the aliphatic polyhydroxy compound is preferably pentaerythritol or dipentane.
- a compound that is erythritol examples include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g.
- a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage accompanying control of the elasticity of the cured film.
- the monofunctional radical polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
- N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam and the like, and allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc.
- Le compounds are preferably used.
- the monofunctional radically polymerizable compound a compound having a boiling point of 100 ° C. or more under normal pressure is also preferable in order to suppress volatilization before exposure.
- the resin composition of the present invention may further contain a polymerizable compound other than the above-mentioned radical polymerizable compound.
- a polymerizable compound other than the above-described radical polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
- 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 1 represents an organic group having 1 to 10 carbon atoms
- 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, 46DMOP (manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML- PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (Miwa Chemical Co., Ltd.) ), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-diacetomethylmethyl-p-cresol, and the like.
- 46DMOC manufactured by Asahi Organic Materials Co., Ltd.
- DML-MBPC DML-MBOC
- DML-OCHP DML-PCHP
- 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- 100LM (manufactured by Sanwa Chemical Co., Ltd.).
- 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 a temperature of 200 ° C. or lower and does not undergo a dehydration reaction due to the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing of the composition and suppression of warpage.
- the epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and the warpage can be suppressed.
- the polyethylene oxide group means that the number of constituent units of ethylene oxide is 2 or more, and it is preferable that the number of constituent units is 2 to 15.
- epoxy compounds 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 thereof include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane.
- Epicron (registered trademark) 850-S Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (manufactured by DIC Corporation), Rica Resin (registered trademark) BEO-60E (Shin Nippon Rika) Co., Ltd.), EP-4003S, EP-4 And the like 00S ((Ltd.) ADEKA).
- an epoxy resin containing a polyethylene oxide group is preferred in terms of suppressing warpage and having excellent heat resistance.
- Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licarezin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
- Oxetane compound (compound having oxetanyl group) >>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>> Examples of the oxetane compound include 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.
- Alon oxetane series eg, OXT-121, OXT-221, OXT-191, OXT-223 manufactured by Toagosei Co., Ltd. can be suitably used, and these can be used alone or You may mix two or more types.
- Benzoxazine Compound (Compound Having Benzoxazolyl Group) >>>> Benzoxazine compounds are preferred because they do not generate degassing during curing due to a cross-linking reaction derived from a ring-opening addition reaction, and further reduce heat shrinkage to suppress the occurrence of warpage.
- benzoxazine compound examples include Ba-type benzoxazine, Bm-type benzoxazine (manufactured by Shikoku Chemicals), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolak-type dihydrobenzoxazine compound. . These may be used alone or as a mixture of two or more.
- a polymerizable compound When a polymerizable compound is contained, its 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 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.
- One type of polymerizable compound may be used alone, or two or more types may be used in combination. 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 solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
- esters for example, 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 , ⁇ -valerolactone, alkyl alkyloxyacetates (eg, methyl alkyloxyacetate, ethylalkyloxyacetate, butylalkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, etc.) )), Alkyl 3-alkyloxypropionates (eg, methyl 3-alkyloxypropionate, ethyl 3-
- alkyl 2-alkyloxypropionates eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 Propyl alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvate Chill, propyl
- ethers for example, 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.
- Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
- Suitable aromatic hydrocarbons include, for example, toluene, xylene, anisole, limonene and the like.
- Suitable sulfoxides include, for example, dimethyl sulfoxide.
- Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
- a form in which two or more solvents are mixed is also preferable.
- solvents selected from butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more solvents is preferred. Particularly preferred is a combination of dimethyl sulfoxide and ⁇ -butyrolactone.
- the content of the solvent is preferably such that the total solid content of the resin composition of the present invention is 5 to 80% by mass, and more preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, even more preferably 40 to 70% by mass.
- the solvent content may be adjusted depending on the desired thickness and the coating method.
- the solvent may contain only one kind, or may contain two or more kinds. When two or more solvents are contained, the total is preferably within the above range.
- the resin composition of the present invention further contains a migration inhibitor.
- the migration inhibitor is not particularly limited, but may be 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
- an ion trapping agent for trapping anions such as halogen ions can be used.
- the migration inhibitor examples include rust preventives described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656.
- Compounds described in paragraph 0052, compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, 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 from 0.01 to 5.0% by mass, and more preferably from 0.05 to 2% by mass, based on the total solid content of the resin composition.
- the content is more preferably 0.0% by mass, and further preferably 0.1 to 1.0% by mass.
- the migration inhibitor may be only one kind or two or more kinds. When two or more types of migration inhibitors are used, the total is preferably 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, and 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, -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-ter
- polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO2015 / 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 from 0.01 to 5% by mass based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass.
- the polymerization inhibitor may be only one kind or two or more kinds. When there are two or more polymerization inhibitors, 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 a metal material used for an electrode or a wiring.
- a metal adhesion improver for improving the adhesion to a metal material used for an electrode or a wiring.
- the metal adhesion improver include a silane coupling agent.
- silane coupling agent examples include the compounds described in paragraph 0167 of WO 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, and the paragraphs of WO 2011/080992.
- the compounds described in paragraph 0055 are mentioned. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compound as the silane coupling agent.
- Et represents an ethyl group.
- the content of the metal adhesion improver is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, and still more preferably from 0 to 15 parts by mass, per 100 parts by mass of the polymer precursor. It is in the range of 5 to 5 parts by mass.
- the metal adhesion improver may be only one kind or two or more kinds. When two or more types are used, the total is preferably within the above range.
- the resin composition of the present invention may contain various additives, for example, 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 anti-agglomeration agent, and the like. When these additives are blended, 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 thermal acid generator is used for elimination of the protective group.
- the content of the thermal acid generator is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of the polymer precursor. Since the crosslinking reaction and the cyclization of the polymer precursor are promoted by containing 0.01 parts by mass or more of the thermal acid generator, the mechanical properties and chemical resistance of the cured film can be further improved. Further, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of the electrical 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 a specific actinic radiation and enters an electronically excited state.
- the sensitizing dye in the electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes effects such as electron transfer, energy transfer, and heat generation.
- the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.
- 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% by mass relative to the total solid content of the resin composition of the present invention.
- the content is more preferably 1 to 15% by mass, and 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 Society of Polymer Science, 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 generate a radical by donating hydrogen to a low activity radical, or can generate a radical by being oxidized and then deprotonated.
- a thiol compound can be preferably used.
- 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, preferably 1 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 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 there are two or more chain transfer agents, the total is preferably within the above range.
- Each type of surfactant may be added to the resin composition of the present invention from the viewpoint of further improving coatability.
- various types 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. Further, the following surfactants are also preferable.
- the content of the surfactant is preferably 0.001 to 2.0% by mass based on the total solid content of the resin composition of the present invention. , More preferably 0.005 to 1.0% by mass.
- the surfactant may be only one kind or two or more kinds. When two or more surfactants are used, the total is preferably 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, and is unevenly distributed on the surface of the composition in a drying process after application. May be. Further, as the higher fatty acid derivative, a compound described in paragraph 0155 of WO 2015/199219 can be used.
- the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention.
- the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total 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, 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 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
- the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably within the above range.
- a material having a low metal content is selected as a raw material constituting the resin composition of the present invention. Examples of the method include filtering the raw material constituting the product with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under the condition that contamination is suppressed as much as possible.
- the resin composition of the present invention has a halogen atom content of preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass, from the viewpoint of wiring corrosiveness, when considering the use as a semiconductor material. Is more preferred. Above all, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, even more preferably less than 0.5 ppm by mass.
- the halogen atom include a chlorine atom and a bromine atom. It is preferable that each of the chlorine atom and the bromine atom, or the total of the chlorine ion and the bromine ion is within the above range.
- the container for storing the resin composition of the present invention a conventionally known container can be used.
- the inner wall of the container is formed into a multi-layer bottle composed of six types and six layers of resin, or six types of resin is formed into a seven-layer structure. It is also preferred to use a bottle that has been used. Examples of such a container include a container described in JP-A-2015-123351.
- the resin composition of the present invention can be prepared by mixing the above components.
- the mixing method is not particularly limited, and can be performed by a conventionally known method.
- the filter pore size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
- the filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
- filters having different pore sizes or materials may be used in combination. Further, various materials may be filtered plural times. When filtration is performed a plurality of times, circulation filtration may be used. Also, filtration may be performed under pressure. In the case of performing filtration by applying pressure, the pressure to be applied 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.
- the adsorbent a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
- the cured film of the present invention is obtained by curing 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 can be set to 100 ⁇ m or less, and can be set to 30 ⁇ m or less.
- the thickness of the cured film of the present invention is preferably 1 to 30 ⁇ m.
- the cured film of the present invention may be formed into a laminate by laminating two or more, more preferably three to seven layers.
- 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.
- Fields to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- Other examples include patterning 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 by etching. These applications are described in, for example, Science & Technology Co., Ltd.
- the cured film according to the present invention can also be used for producing plate surfaces such as offset plate surfaces or screen plate surfaces, for use in etching molded parts, and for producing protective lacquers and dielectric layers in electronics, particularly microelectronics.
- the method for producing a cured film of the present invention includes using the resin composition of the present invention. Specifically, it is preferable to include the following steps (a) to (d). (A) a film forming step of forming a film by applying the resin composition to a substrate; (b) an exposing step of exposing the film after the film forming step; and (c) a developing treatment of the exposed resin composition layer. (D) heating step of heating the developed resin composition at 80 to 450 ° C. As in this embodiment, the exposed resin layer can be further cured by heating after development. .
- the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
- the step (a), the steps (a) to (c), or the step (a) is performed again.
- ) To (d) are performed.
- a metal layer on the portion where the cured film is provided, between the cured films, or both.
- the manufacturing method includes a film forming step (layer forming step) of applying a resin composition to a substrate to form a film (layered).
- the type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, an optical film, a ceramic material, a vapor-deposited film, and a magnetic film , A reflective film, a metal substrate of Ni, Cu, Cr, Fe, etc., paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, and an electrode plate of a plasma display panel (PDP).
- a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, an optical film, a ceramic material, a vapor-deposited film, and a magnetic film
- a semiconductor fabrication substrate is particularly preferable, and a silicon substrate is more preferable.
- the resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.
- coating is preferable. Specifically, as means to be applied, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, slit coating, And an inkjet method. From the viewpoint of the uniformity of the thickness of the resin composition layer, more preferred are a spin coating method, a slit coating method, a spray coating method and an ink jet method.
- a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and application conditions according to the method.
- the coating method can also be appropriately selected depending on the shape of the substrate.
- a spin coating method, a spray coating method, or an inkjet method is preferable.
- a slit coating method, a spray coating method, or an inkjet method is used. Method is preferred.
- a rotation speed of 500 to 2000 rpm can be applied for about 10 seconds to 1 minute.
- the production method of the present invention may include a step of drying after removing the solvent after forming the resin composition layer and after the film forming step (layer forming step).
- the preferred drying temperature is 50 to 150 ° C., more preferably 70 to 130 ° C., and even more preferably 90 to 110 ° C.
- the drying time is, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
- the production method of the present invention may include an exposure step of exposing the resin composition layer.
- the amount of exposure is not particularly limited as long as the resin composition can be cured.
- irradiation is preferably 100 to 10,000 mJ / cm 2 , and more preferably 200 to 8000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm. More preferred.
- the exposure wavelength can be appropriately determined within the range of 190 to 1000 nm, and preferably 240 to 550 nm.
- the exposure wavelength is, in terms of the light source, (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 (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength: 157 nm); (5) extreme ultraviolet; EUV (wavelength: 13.6 nm); (6) electron beam.
- exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, a particularly high exposure sensitivity can be obtained.
- the production method of the present invention may include a development processing step of performing development processing on the exposed resin composition layer. By performing the development, an unexposed portion (non-exposed portion) is removed.
- the developing method is not particularly limited as long as a desired pattern can be formed. For example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted. Development is performed using a developer.
- the developer can be used without particular limitation as long as the unexposed portions (non-exposed portions) are removed.
- the developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent.
- the developer preferably contains an organic solvent having a ClogP value of -1 to 5, 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, and ⁇ -butyrolactone.
- alkyl alkyl oxyacetates eg, methyl alkyl oxyacetate, ethyl oxyacetate, alkyl butyl oxyacetate (eg, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, Ethyl ethoxyacetate, etc.
- alkyl 3-alkyloxypropionates eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- alkyl 2-alkyloxypropionates eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 Propyl alkyloxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvate Tyl, propyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), alkyl 2-alkyloxypropionates (eg, methyl 2-alkyloxyprop
- dimethyl sulfoxide is preferably exemplified.
- cyclopentanone and ⁇ -butyrolactone are particularly preferred, and cyclopentanone is more preferred.
- the developer preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and even more preferably 90% by mass or more of an organic solvent. Further, 100% by mass of the developer may be an organic solvent.
- the development time is preferably from 10 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly limited, but it can be usually 20 to 40 ° C.
- rinsing may be further performed. Rinsing is preferably performed with a solvent different from the developer. For example, rinsing can be performed using a solvent contained in the resin composition.
- the rinsing time is preferably from 5 seconds to 1 minute.
- the manufacturing method of the present invention preferably includes a heating step after the film forming step (layer forming step), the drying step, or the developing step.
- a heating step a cyclization reaction of the polymer precursor proceeds.
- the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and more preferably 150 ° C. or higher. Is more preferably 160 ° C. or higher, and even more preferably 170 ° C. or higher.
- the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, even more preferably 350 ° C.
- Heating is preferably performed at a 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, even more preferably 3 to 10 ° C./min.
- the heating rate By setting the heating rate to 1 ° C./min or more, the amine can be prevented from being excessively volatilized while securing the productivity.
- the heating rate By setting the heating rate to 12 ° C./min or less, the cured film can be cured. The residual stress can be reduced.
- the temperature at the start of heating is preferably from 20 ° C to 150 ° C, more preferably from 20 ° C to 130 ° C, even more preferably from 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 heating time is preferably from 10 to 360 minutes, more preferably from 20 to 300 minutes, even more preferably from 30 to 240 minutes.
- the heating temperature is preferably from 180 ° C. to 320 ° C., and more preferably from 180 ° C. to 260 ° C., from the viewpoint of adhesion between the cured films.
- the reason is not clear, it is considered that the ethynyl groups of the polymer precursor between the layers are undergoing a crosslinking reaction at this temperature.
- the heating may be performed stepwise. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, maintained at 180 ° C. for 60 minutes, raised from 180 ° C. to 200 ° C. at 2 ° C./min, and maintained at 200 ° C. for 120 minutes. , Etc., may be performed.
- the heating temperature in the pretreatment step is preferably from 100 to 200 ° C, more preferably from 110 to 190 ° C, and even more preferably from 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547.
- 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 include two or more steps. For example, pretreatment step 1 may be performed at a temperature in the range of 100 to 150 ° C., and then pretreatment step 2 may be performed at a temperature in the range of 150 to 200 ° C. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
- the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polymer precursor.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
- the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the resin composition layer after the development processing.
- the metal layer is not particularly limited, and any existing metal species can be used.Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, and copper and aluminum are more preferable, and copper is preferable. 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-T-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
- the thickness of the metal layer at the thickest part is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m.
- the manufacturing method of the present invention further includes a lamination step.
- the laminating step means (a) a film forming step (layer forming step), (b) an exposing step, (c) a developing step, and (d) a heating step on the surface of the cured film (resin layer) or the metal layer. Are performed in this order. However, an embodiment in which only the film forming step (a) is repeated may be employed. Further, the heating step (d) may be performed at the end of or in the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated resin composition layers at once.
- a metal layer forming step may be included after the (c) developing step.
- the laminating step may further include the above-mentioned drying step, heating step and the like as appropriate.
- a surface activation treatment step may be further performed after the heating step, after the exposing step, or after the metal layer forming step.
- a plasma treatment is exemplified.
- the above lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
- a configuration of three to seven resin layers is preferable, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and more preferably three to five layers.
- a cured film (resin layer) of the resin composition is further formed so as to cover the metal layer.
- the present invention also discloses a semiconductor device having the cured film or the laminate of the present invention.
- the semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. 1 can be referred to. These contents are incorporated herein.
- Measurement method 20 g of a measurement sample, 50 g of tetrahydrofuran as a non-aqueous organic solvent, and 50 g of ultrapure water were mixed. If a solid precipitates due to the addition of water, remove the solid by centrifugation. If no solid precipitates, separate the organic layer and the aqueous layer (separation operation) and determine the content of the specific components extracted into the aqueous solution. It was measured by ion chromatography. As a measuring device, Shimadzu HIC-20A (manufactured by Shimadzu Corporation) was used.
- reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. The reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) SOCl 2 was added over 10 minutes keeping the temperature at ⁇ 10 ⁇ 4 ° C. The viscosity increased during the addition of SOCl 2 . After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
- the obtained wet solid was dissolved in 300 mL of tetrahydrofuran (THF), and then 300 mL of water was added, and the liquid separation operation was repeated three times.
- THF / polyimide precursor solution was reprecipitated using 5 L of water.
- the polyimide precursor was removed by filtration, stirred again in 4 L of water for 30 minutes, and filtered again.
- the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days.
- the weight average molecular weight of this polyimide precursor was 18,000.
- the weight average molecular weight of this polyimide precursor was 19,000. Further, specific components (HNO 2 , NO 2 ⁇ , HNO 3 , NO 3 ⁇ , H 2 SO 4 , HSO 4 ⁇ , SO 4 2 ⁇ , H 2 SO 3 , HSO 3 ⁇ and SO 3 ⁇ ) in this polyimide precursor are used. When the content of 2- ) was measured by ion chromatography, no specific component was detected.
- the polybenzoxazole precursor was then precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes.
- the polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes and filtered again.
- the obtained polybenzoxazole precursor was dried at 45 ° C. under reduced pressure for 3 days.
- the weight average molecular weight of this polybenzoxazole precursor was 15,000.
- Examples and Comparative Examples> The components shown in the following table were mixed to obtain each resin composition. Purification methods such as distillation and crystallization were repeated with respect to components other than the polymer precursor, with respect to the components described in the following table. When the content of the specific components in these components was confirmed by ion chromatography, it was confirmed that these components did not contain the specific components. The obtained resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m.
- Polymer precursor A-1 to A-5 The above-mentioned polymer precursors A-1 to A-5
- D-1 A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- D-2 SR-209 (manufactured by Sartomer, a compound having the following structure)
- D-3 A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- E-1 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
- E-2 Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
- E-3 paramethoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
- (Metal adhesion improver) G-1 to G-3 compounds having the following structures.
- Et represents an ethyl group.
- the resin compositions of Compositions 1 to 36 were applied on a silicon wafer by spin coating, and dried at 100 ° C. for 5 minutes using a hot plate to form a resin composition layer having a thickness of about 15 ⁇ m.
- This resin composition layer was heated in a nitrogen atmosphere at a rate of 10 ° C./min, and after reaching 250 ° C., was heated for 3 hours to form a cured film.
- the silicon wafer on which the cured film is formed is put into a constant-temperature and constant-humidity layer at a temperature of 85 ° C.
- the resin compositions of Compositions 1 to 36 were applied on a copper wafer by spin coating, and dried at 100 ° C. for 5 minutes using a hot plate to form a resin composition layer having a thickness of about 15 ⁇ m.
- This resin composition layer was heated in a nitrogen atmosphere at a rate of 10 ° C./min, and after reaching 250 ° C., was heated for 3 hours to form a cured film.
- the copper wafer on which the cured film was formed was put into a constant-temperature and constant-humidity layer at a temperature of 85 ° C. and a humidity of 85% for 24 hours, and a portion where corrosion occurred on the copper wafer was observed with an optical microscope.
- the copper corrosivity was evaluated by observing what percentage of the area where the corrosion occurred relative to the area of the side of the copper wafer on which the cured film was provided.
- C The area of the corrosion occurrence portion is 10% or more and less than 20% with respect to the area of the surface on the side where the cured film of the copper wafer is provided
- Examples 1 to 9 and Comparative Examples 1 to 3 are test examples using a resin composition in which only the content of the specific component is different, but the content of the specific component is lower than the total solid content of the resin composition.
- Examples 1 to 9 using compositions 1 to 9 having a content of 1 mass ppb or more and 1000 mass ppm or less the resin compositions of compositions 22 to 24 in which the content of the specific component was outside the above range were used. It is shown that the evaluation of storage stability is superior to Comparative Examples 1 to 3 by one rank or more.
- Example 10 and Comparative Example 4 Example 11 and Comparative Example 5, Example 12 and Comparative Example 6, Example 13 and Comparative Example 7, Example 14 and Comparative Example 8, Example 15 and Comparative Example 9, From the results of Example 16 and Comparative Example 10, Example 17 and Comparative Example 11, Example 18 and Comparative Example 12, Example 19 and Comparative Example 13, Example 20 and Comparative Example 14, and Example 21 and Comparative Example 15. Also shows a similar tendency.
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Abstract
Description
このようなポリイミド樹脂等は、一般に、溶剤への溶解性が低い。そのため、環化反応前のポリマー前駆体、具体的には、ポリイミド前駆体やポリベンゾオキサゾール前駆体の状態で溶剤に溶解する方法がよく用いられる。これにより、優れた取り扱い性を実現することができ、上述のような各製品を製造する際に基板などに多様な形態で塗布して加工することができる。その後、加熱してポリマー前駆体を環化し、硬化した製品を形成することができる。ポリイミド樹脂等がもつ高い性能に加え、このような製造上の適応性に優れる観点から、その産業上の応用展開がますます期待されている。
一方、これらのポリマー前駆体を含む樹脂組成物に要求される近年の多様化した要求特性に応えるためには、さらなる研究開発が必要である。例えば、ポリマー前駆体を含む樹脂組成物から得られる硬化膜に関し、耐湿性についての更なる向上が望まれている。
HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-の合計の含有量が樹脂組成物の全固形分に対して1質量ppb以上1000質量ppm以下である、樹脂組成物。
<2> 更に、シランカップリング剤、熱塩基発生剤、ラジカル重合開始剤およびラジカル重合性化合物から選ばれる少なくとも1種を含む、<1>に記載の樹脂組成物。
<3> ポリマー前駆体がポリイミド前駆体を含む、<1>または<2>に記載の樹脂組成物。
<4> ポリイミド前駆体が下記式(1)で表される構成単位を有する、<3>に記載の樹脂組成物;
<5> 式(1)における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、<4>に記載の樹脂組成物。
<6> 有機溶剤を90質量%以上含む現像液を用いて現像してパターンを形成するために用いられる、<1>~<5>のいずれか1つに記載の樹脂組成物。
<7> 金属と接触させる部材の形成に用いられる、<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 再配線層用層間絶縁膜の形成に用いられる、<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> <1>~<8>のいずれか1つに記載の樹脂組成物を硬化して得られる硬化膜。
<10> 膜厚が1~30μmである、<9>に記載の硬化膜。
<11> <9>または<10>に記載の硬化膜を2層以上有し、2層の硬化膜の間に金属層を有する、積層体。
<12> <1>~<8>のいずれか1つに記載の樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
<13> 膜を露光する露光工程および膜を現像する現像工程を有する、<12>に記載の硬化膜の製造方法。
<14> 膜を80~450℃で加熱する工程を含む、<12>または<13>に記載の硬化膜の製造方法。
<15> <9>もしくは<10>に記載の硬化膜または<11>に記載の積層体を有する、半導体デバイス。
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。
本発明の樹脂組成物は、ポリイミド前駆体およびポリベンザオキサゾール前駆体から選ばれる少なくとも1種のポリマー前駆体を含む樹脂組成物であって、HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-の合計の含有量が樹脂組成物の全固形分に対して1質量ppb以上1000質量ppm以下であることを特徴とする。以下、HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-を合わせて特定成分ともいう。
また、HNO2とNO2 -との合計の含有量が樹脂組成物の全固形分に対して1000質量ppm以下であることが好ましく、900質量ppm以下であることがより好ましく、800質量ppm以下であることが更に好ましく、500質量ppm以下であることが特に好ましい。
また、HNO3とNO3 -との合計の含有量が樹脂組成物の全固形分に対して1000質量ppm以下であることが好ましく、900質量ppm以下であることがより好ましく、800質量ppm以下であることが更に好ましく、500質量ppm以下であることが特に好ましい。
また、H2SO4とHSO4 -とSO4 2-との合計の含有量が樹脂組成物の全固形分に対して1000質量ppm以下であることが好ましく、900質量ppm以下であることがより好ましく、800質量ppm以下であることが更に好ましく、500質量ppm以下であることが特に好ましい。
また、H2SO3とHSO3 -とSO3 2-の合計の含有量が樹脂組成物の全固形分に対して1000質量ppm以下であることが好ましく、900質量ppm以下であることがより好ましく、800質量ppm以下であることが更に好ましく、500質量ppm以下であることが特に好ましい。
また、本発明の樹脂組成物中において、上記特定成分のうちNO2 -、NO3 -、HSO4 -、SO4 2-、HSO3 -およびSO3 2-は、塩の状態で存在していることがある。また、上記特定成分のうちHNO2、HNO3、H2SO4、および、H2SO3は電離してイオンの状態で存在していることもある。塩を構成する原子または原子団としては特に限定はない。例えば、アルカリ金属(リチウム、カリウム、ナトリウムなど)、アルカリ土類金属(カルシウム、ベリリウム、マグネシウム、ストロンチウム、バリウム)などが挙げられる。
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、熱塩基発生剤を含む。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2008-063554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。
<<ラジカル重合性化合物>>
本発明の樹脂組成物は重合性化合物を含むことが好ましい。重合性化合物としては、ラジカル重合性化合物を用いることができる。ラジカル重合性化合物は、ラジカル重合性基を有する化合物である。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化合物として、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化合物の好ましい酸価は、0.1~40mgKOH/gであり、特に好ましくは5~30mgKOH/gである。ラジカル重合性化合物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化合物以外の重合性化合物をさらに含むことができる。上述したラジカル重合性化合物以外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。
また、ラジカル重合性化合物を含有する場合、その含有量は、本発明の樹脂組成物の全固形分に対して、0質量%超60質量%以下であることが好ましい。下限は5質量%以上がより好ましい。上限は、50質量%以下であることがより好ましく、30質量%以下であることがさらに好ましい。
重合性化合物は1種を単独で用いてもよいが、2種以上を混合して用いてもよい。2種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。
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、特定熱塩基発生剤が保護基を有する場合、保護基の脱離に用いられる。
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、硬化膜、積層体、半導体デバイス、およびそれらの製造方法について説明する。
本発明の硬化膜は、本発明の樹脂組成物を硬化して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。
(a)樹脂組成物を基板に適用して膜を形成する膜形成工程
(b)膜形成工程の後、膜を露光する露光工程
(c)露光された樹脂組成物層に対して、現像処理を行う現像工程
(d)現像された樹脂組成物を80~450℃で加熱する加熱工程
この実施形態のように、現像の後、加熱することで露光された樹脂層をさらに硬化させることができる。
本発明の好ましい実施形態に係る製造方法は、樹脂組成物を基板に適用して膜(層状)にする、膜形成工程(層形成工程)を含む。
基板の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基板、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ni、Cu、Cr、Feなどの金属基板、紙、SOG(Spin On Glass)、TFT(薄膜トランジスタ)アレイ基板、プラズマディスプレイパネル(PDP)の電極板など特に制約されない。本発明では、特に、半導体作製基板が好ましく、シリコン基板がより好ましい。
また、樹脂層の表面や金属層の表面に樹脂組成物層を形成する場合は、樹脂層や金属層が基板となる。
樹脂組成物を基板に適用する手段としては、塗布が好ましい。
具体的には、適用する手段としては、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スプレーコート法、スピンコート法、スリットコート法、およびインクジェット法などが例示される。樹脂組成物層の厚さの均一性の観点から、より好ましくはスピンコート法、スリットコート法、スプレーコート法、インクジェット法である。方法に応じて適切な固形分濃度や塗布条件を調整することで、所望の厚さの樹脂層を得ることができる。また、基板の形状によっても塗布方法を適宜選択でき、ウェハ等の円形基板であればスピンコート法やスプレーコート法、インクジェット法等が好ましく、矩形基板であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、500~2000rpmの回転数で、10秒~1分程度適用することができる。
本発明の製造方法は、樹脂組成物層を形成後、膜形成工程(層形成工程)の後に、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は50~150℃で、70℃~130℃がより好ましく、90℃~110℃がさらに好ましい。乾燥時間としては、30秒~20分が例示され、1分~10分が好ましく、3分~7分がより好ましい。
本発明の製造方法は、上記樹脂組成物層を露光する露光工程を含んでもよい。露光量は、樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で100~10000mJ/cm2照射することが好ましく、200~8000mJ/cm2照射することがより好ましい。
露光波長は、190~1000nmの範囲で適宜定めることができ、240~550nmが好ましい。
露光波長は、光源との関係でいうと、(1)半導体レーザー(波長 830nm、532nm、488nm、405nm etc.)、(2)メタルハライドランプ、(3)高圧水銀灯、g線(波長 436nm)、h線(波長 405nm)、i線(波長 365nm)、ブロード(g,h,i線の3波長)、(4)エキシマレーザー、KrFエキシマレーザー(波長 248nm)、ArFエキシマレーザー(波長 193nm)、F2エキシマレーザー(波長 157nm)、(5)極端紫外線;EUV(波長 13.6nm)、(6)電子線等が挙げられる。本発明の樹脂組成物については、特に高圧水銀灯による露光が好ましく、なかでも、i線による露光が好ましい。これにより、特に高い露光感度が得られうる。
本発明の製造方法は、露光された樹脂組成物層に対して、現像処理を行う現像処理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。
本発明の製造方法は、膜形成工程(層形成工程)、乾燥工程、または現像工程の後に加熱する工程を含むことが好ましい。加熱工程では、ポリマー前駆体の環化反応が進行する。加熱工程における層の加熱温度(最高加熱温度)としては、50℃以上であることが好ましく、80℃以上であることがより好ましく、140℃以上であることがさらに好ましく、150℃以上であることが一層好ましく、160℃以上であることがより一層好ましく、170℃以上であることがさらに一層好ましい。上限としては、500℃以下であることが好ましく、450℃以下であることがより好ましく、350℃以下であることがさらに好ましく、250℃以下であることが一層好ましく、220℃以下であることがより一層好ましい。
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、加熱温度は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。
本発明の製造方法は、現像処理後の樹脂組成物層の表面に金属層を形成する金属層形成工程を含んでいることが好ましい。
金属層としては、特に限定なく、既存の金属種を使用することができ、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金およびタングステンが例示され、銅およびアルミニウムがより好ましく、銅がさらに好ましい。
金属層の形成方法は、特に限定なく、既存の方法を適用することができる。例えば、特開2007-157879号公報、特表2001-521288号公報、特開2004-214501号公報、特開2004-101850号公報に記載された方法を使用することができる。例えば、フォトリソグラフィ、リフトオフ、電解メッキ、無電解メッキ、エッチング、印刷、およびこれらを組み合わせた方法などが考えられる。より具体的には、スパッタリング、フォトリソグラフィおよびエッチングを組み合わせたパターニング方法、フォトリソグラフィと電解メッキを組み合わせたパターニング方法が挙げられる。
金属層の厚さとしては、最も厚肉部で、0.1~50μmが好ましく、1~10μmがより好ましい。
本発明の製造方法は、さらに、積層工程を含むことが好ましい。
積層工程とは、硬化膜(樹脂層)または金属層の表面に、再度、(a)膜形成工程(層形成工程)、(b)露光工程、(c)現像処理工程、(d)加熱工程を、この順に行うことを含む一連の工程である。ただし、(a)の膜形成工程のみを繰り返す態様であってもよい。また、(d)加熱工程は積層の最後または中間に一括して行う態様としてもよい。すなわち、(a)~(c)の工程を所定の回数繰り返し行い、その後に(d)の加熱をすることで、積層された樹脂組成物層を一括で硬化する態様としてもよい。また、(c)現像工程の後には(e)金属層形成工程を含んでもよく、このときにも都度(d)の加熱を行っても、所定回数積層させた後に一括して(d)の加熱を行ってもよい。積層工程には、さらに、上記乾燥工程や加熱工程等を適宜含んでいてもよいことは言うまでもない。
積層工程後、さらに積層工程を行う場合には、上記加熱工程後、上記露光工程後、または、上記金属層形成工程後に、さらに、表面活性化処理工程を行ってもよい。表面活性化処理としては、プラズマ処理が例示される。
上記積層工程は、2~5回行うことが好ましく、3~5回行うことがより好ましい。
例えば、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層のような、樹脂層が3層以上7層以下の構成が好ましく、3層以上5層以下がさらに好ましい。
本発明では特に、金属層を設けた後、さらに、上記金属層を覆うように、上記樹脂組成物の硬化膜(樹脂層)を形成する態様が好ましい。具体的には、(a)膜形成工程、(b)露光工程、(c)現像工程、(e)金属層形成工程、(d)加熱工程の順序で繰り返す態様、あるいは、(a)膜形成工程、(b)露光工程、(c)現像工程、(e)金属層形成工程の順序で繰り返し、最後または中間に一括して(d)加熱工程を設ける態様が挙げられる。樹脂組成物層(樹脂)を積層する積層工程と、金属層形成工程を交互に行うことにより、樹脂組成物層(樹脂層)と金属層を交互に積層することができる。
測定試料20gと、非水系の有機溶剤としてテトラヒドロフランを50gと、超純水を50gとを混合した。水添加により固体が析出した場合は遠心分離により固体を除去し、固体が析出しなかった場合は有機層と水層を分離し(分液操作)、水溶液へ抽出された特定成分の含有量をイオンクロマトグラフ法により測定した。測定装置としては、Shimadzu HIC-20A((株)島津製作所製)を用いた。
[ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテルおよびベンジルアルコールからのポリイミド前駆体(A-1:ラジカル重合性基を有さないポリイミド前駆体)の合成]
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥)と、14.22g(131.58ミリモル)のベンジルアルコールを、50mLのN-メチルピロリドンに懸濁させ、モレキュラーシーブで乾燥させた。懸濁液を100℃で3時間加熱した。反応混合物を室温に冷却し、21.43g(270.9ミリモル)のピリジンおよび90mLのN-メチルピロリドンを加えた。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。SOCl2を加えている間、粘度が増加した。50mLのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mLのN-メチルピロリドンに11.08g(58.7ミリモル)の4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、-5~0℃で20分かけて反応混合物に滴下した。次いで、反応混合物を0℃で1時間反応させたのち、エタノールを70g加えて、室温で1晩撹拌した。次いで、5Lの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5000rpmの速度で15分間撹拌した。
得られたウェット固体をテトラヒドロフラン(THF)300mLに溶解させ、次いで水300mLを加えて分液操作を3回繰り返した。得られたTHF/ポリイミド前駆体溶液を5Lの水を用いて再沈殿した。ポリイミド前駆体をろ過して除き、4Lの水の中で再度30分間撹拌し再びろ過した。次いで、得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥した。このポリイミド前駆体の重量平均分子量は、18,000であった。また、このポリイミド前駆体中の特定成分(HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-)の含有量をイオンクロマトグラフ法により測定したところ、特定成分は検出されなかった。
[ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-2:ラジカル重合性基を有するポリイミド前駆体)の合成]
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4gのピリジン(258ミリモル)と、100gのダイグライム(ジエチレングリコールジメチルエーテル)を混合し、60℃の温度で18時間撹拌して、ピロメリット酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、19,000であった。また、このポリイミド前駆体中の特定成分(HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-)の含有量をイオンクロマトグラフ法により測定したところ、特定成分は検出されなかった。
[4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-3:ラジカル重合性基を有するポリイミド前駆体)の合成]
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4gのピリジン(258ミリモル)と、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。また、このポリイミド前駆体中の特定成分(HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-)の含有量をイオンクロマトグラフ法により測定したところ、特定成分は検出されなかった。
[4,4’-オキシジフタル酸無水物、4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)および2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-4:ラジカル重合性基を有するポリイミド前駆体)の合成]
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥した)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4gのピリジン(258ミリモル)と、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノ-2,2’-ジメチルビフェニルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、19,000であった。また、このポリイミド前駆体中の特定成分(HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-)の含有量をイオンクロマトグラフ法により測定したところ、特定成分は検出されなかった。
[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、4,4’-オキシジベンゾイルクロリドからのポリベンゾオキサゾール前駆体(A-5)の合成]
N-メチル-2-ピロリドン100mLに、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13.92gを添加し、攪拌溶解した。続いて、温度を0~5℃に保ちながら、11.21gの4,4’-オキシジベンゾイルクロリドを10分間で滴下した後、60分間攪拌を続けた。次いで、6リットルの水の中でポリベンゾオキサゾール前駆体を沈殿させ、水-ポリベンゾオキサゾール前駆体混合物を5000rpmの速度で15分間撹拌した。ポリベンゾオキサゾール前駆体を濾過して除き、6リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリベンゾオキサゾール前駆体を減圧下で、45℃で3日間乾燥した。このポリベンゾオキサゾール前駆体の重量平均分子量は、15,000であった。また、このポリベンゾオキサゾール前駆体中には特定成分(HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-)は検出されなかった。
下記表に記載の成分を混合し、各樹脂組成物を得た。ポリマー前駆体以外の成分に関しても下記表中記載の成分に関しては蒸留、晶析などの精製方法を繰り返した。これらの成分中の特定成分の含有量をイオンクロマトグラフ法で確認したところ、これらの成分には特定成分が含まれていないことを確認した。得られた樹脂組成物を、細孔の幅が0.8μmのフィルターを通して加圧ろ過した。次に亜硝酸ナトリウム、硝酸、硝酸ナトリウム、硫酸、硫酸水素カリウム、硫酸ナトリウム、亜硫酸水、亜硫酸水素ナトリウムおよび亜硫酸ナトリウムを添加してHNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-の含有量を下記表に記載の含有量となるように調整して実施例および比較例の樹脂組成物を調製した。上記成分の含有量は、樹脂組成物に添加し、水抽出されるものをイオンクロマトグラフ法により測定した。
A-1~A-5:上述したポリマー前駆体A-1~A-5
C-1:IRGACURE OXE 01(BASF社製)
C-2:IRGACURE OXE 02(BASF社製)
C-3:IRGACURE 369(BASF社製)
E-1:2,6-ジ-tert-ブチル-4-メチルフェノール(東京化成工業社製)
E-2:パラベンゾキノン(東京化成工業社製)
E-3:パラメトキシフェノール(東京化成工業社製)
I-1:γ-ブチロラクトン(三和油化社製)
I-2:ジメチルスルホキシド(和光純薬工業社製)
I-3:N-メチル-2-ピロリドン(Ashland社製)
組成物1~36の樹脂組成物を、E型粘度計を用いて粘度(0日)を測定した。密閉容器中、25℃で14日間、樹脂組成物を静置した後、再度E型粘度計を用いて粘度(14日)を測定した。以下の式から、粘度変動率を算出した。粘度変動率が低ければ低い程、保存安定性が高いことを表す。
粘度変動率=|100×{1-(粘度(14日)/粘度(0日))}|
粘度の測定は25℃で行うこととし、その他はJIS Z 8803:2011に準拠することとした。
A:粘度変動率が5%以下
B:粘度変動率が5%を超えて10%以下
C:粘度変動率が10%を超えて15%以下
D:粘度変動率が15%を超えて20%以下
組成物1~36の樹脂組成物をスピンコート法でシリコンウェハ上に適用し、ホットプレートを用いて100℃で5分間乾燥して、約15μmの厚さの樹脂組成物層を形成した。この樹脂組成物層を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、250℃に達した後、3時間加熱して硬化膜を形成した。この硬化膜を形成したシリコンウェハを温度85℃湿度85%の恒温恒湿層24時間に投入し、硬化膜の面積に対する変性(白色化、ひび割れ)発生箇所の面積が何%であるかを観測して耐湿性を評価した。
A:変性発生箇所が硬化膜の面積の2%未満である
B:変性発生箇所が硬化膜の面積の2%以上5%未満である
C:変性発生箇所が硬化膜の面積の5%以上10%未満である
D:変性発生箇所が硬化膜の面積の10%以上である
組成物1~36の樹脂組成物をスピンコート法で銅ウェハ上に適用し、ホットプレートを用いて100℃で5分間乾燥して、約15μmの厚さの樹脂組成物層を形成した。この樹脂組成物層を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、250℃に達した後、3時間加熱して硬化膜を形成した。この硬化膜を形成した銅ウェハを温度85℃湿度85%の恒温恒湿層24時間に投入し、銅ウェハ上の腐食発生箇所を光学顕微鏡で観察した。銅ウェハの硬化膜が設けられている側の面の面積に対する腐食発生箇所の面積が何%であるかを観測して銅腐食性を評価した。
A:銅ウェハの硬化膜が設けられている側の面の面積に対する腐食発生箇所の面積が5%未満
B:銅ウェハの硬化膜が設けられている側の面の面積に対する腐食発生箇所の面積が5%以上10%未満
C:銅ウェハの硬化膜が設けられている側の面の面積に対する腐食発生箇所の面積が10%以上20%未満
D:銅ウェハの硬化膜が設けられている側の面の面積に対する腐食発生箇所の面積が20%以上
また、実施例1~9と比較例1~3は、特定成分の含有量のみが相違する樹脂組成物を用いた試験例であるが、特定成分の含有量が樹脂組成物の全固形分に対して1質量ppb以上1000質量ppm以下である組成物1~9を用いた実施例1~9は、特定成分の含有量が上記範囲外である組成物22~24の樹脂組成物を用いた比較例1~3よりもワンランク以上保存安定性の評価が優れていることが示されている。また、耐湿性および銅腐食性についても同等またはワンランク以上優れていることが示されている。
また、実施例10と比較例4、実施例11と比較例5、実施例12と比較例6、実施例13と比較例7、実施例14と比較例8、実施例15と比較例9、実施例16と比較例10、実施例17と比較例11、実施例18と比較例12、実施例19と比較例13、実施例20と比較例14、実施例21と比較例15の結果からも同様の傾向が示されている。
Claims (15)
- ポリイミド前駆体およびポリベンザオキサゾール前駆体から選ばれる少なくとも1種のポリマー前駆体を含む樹脂組成物であって、
HNO2、NO2 -、HNO3、NO3 -、H2SO4、HSO4 -、SO4 2-、H2SO3、HSO3 -およびSO3 2-の合計の含有量が前記樹脂組成物の全固形分に対して1質量ppb以上1000質量ppm以下である、樹脂組成物。 - 更に、シランカップリング剤、熱塩基発生剤、ラジカル重合開始剤およびラジカル重合性化合物から選ばれる少なくとも1種を含む、請求項1に記載の樹脂組成物。
- 前記ポリマー前駆体がポリイミド前駆体を含む、請求項1または2に記載の樹脂組成物。
- 前記式(1)における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、請求項4に記載の樹脂組成物。
- 有機溶剤を90質量%以上含む現像液を用いて現像してパターンを形成するために用いられる、請求項1~5のいずれか1項に記載の樹脂組成物。
- 金属と接触させる部材の形成に用いられる、請求項1~6のいずれか1項に記載の樹脂組成物。
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~7のいずれか1項に記載の樹脂組成物。
- 請求項1~8のいずれか1項に記載の樹脂組成物を硬化して得られる硬化膜。
- 膜厚が1~30μmである、請求項9に記載の硬化膜。
- 請求項9または10に記載の硬化膜を2層以上有し、前記2層の硬化膜の間に金属層を有する、積層体。
- 請求項1~8のいずれか1項に記載の樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
- 前記膜を露光する露光工程および前記膜を現像する現像工程を有する、請求項12に記載の硬化膜の製造方法。
- 前記膜を80~450℃で加熱する工程を含む、請求項12または13に記載の硬化膜の製造方法。
- 請求項9もしくは10に記載の硬化膜または請求項11に記載の積層体を有する、半導体デバイス。
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CN115702213A (zh) * | 2020-07-22 | 2023-02-14 | 富士胶片株式会社 | 树脂组合物、膜、滤光器、固体摄像元件、图像显示装置及树脂 |
WO2023190064A1 (ja) * | 2022-03-29 | 2023-10-05 | 富士フイルム株式会社 | 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス |
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