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WO2017038598A1 - Procédé de fabrication de film durci, procédé de fabrication de film isolant intercouche pour couche de recâblage, et procédé de fabrication de dispositif semi-conducteur - Google Patents

Procédé de fabrication de film durci, procédé de fabrication de film isolant intercouche pour couche de recâblage, et procédé de fabrication de dispositif semi-conducteur Download PDF

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Publication number
WO2017038598A1
WO2017038598A1 PCT/JP2016/074742 JP2016074742W WO2017038598A1 WO 2017038598 A1 WO2017038598 A1 WO 2017038598A1 JP 2016074742 W JP2016074742 W JP 2016074742W WO 2017038598 A1 WO2017038598 A1 WO 2017038598A1
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Prior art keywords
group
cured film
ring
amine
compound
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English (en)
Japanese (ja)
Inventor
一郎 小山
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Fujifilm Corp
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Fujifilm Corp
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Priority to KR1020187005203A priority Critical patent/KR102028939B1/ko
Priority to JP2017537787A priority patent/JP6511146B2/ja
Publication of WO2017038598A1 publication Critical patent/WO2017038598A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

  • the present invention relates to a method for producing a cured film, a method for producing an interlayer insulating film for a rewiring layer, and a method for producing a semiconductor device.
  • the present invention relates to a method for producing a cured film using a heterocyclic-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor.
  • Thermosetting resins that are cured by cyclization are excellent in heat resistance and insulation, and are therefore used in insulating layers of semiconductor devices.
  • polyimides have low solubility in solvents, they are used in the state of a precursor (heterocycle-containing polymer precursor) before the cyclization reaction, applied to a substrate, etc., and then heated to form a heterocycle-containing polymer. It has been practiced to form a cured film by cyclizing the precursor.
  • Patent Document 1 discloses a polyimide precursor composition containing a polyimide precursor, a thermal base generator that generates a base by heat, and a solvent, and the polyimide precursor is represented by the following formula (1).
  • a polyimide precursor composition is disclosed, which is a polyamic acid having a repeating unit, and the thermal base generator is a neutral compound that undergoes thermal decomposition by heating at a temperature of 200 ° C. or lower to generate a secondary amine.
  • X represents a tetravalent organic group
  • Y represents a divalent organic group
  • the —COOH group is in an ortho position with the —CONH group, respectively.
  • Patent Document 2 discloses a polyamic acid composition comprising a polyamic acid, polyaniline, a dopant for making polyaniline conductive, a solvent, and a basic additive. Yes.
  • the corrosion resistance and chemical resistance of the cured film become a problem.
  • the cured films described in the examples of Patent Document 1 and Patent Document 2 are inferior in corrosion resistance and chemical resistance.
  • the present invention aims to solve the above-described problems, and provides a method for producing a cured film having excellent corrosion resistance and chemical resistance.
  • the manufacturing method of the interlayer insulation film for rewiring layers including the manufacturing method of the said cured film, and the manufacturing method of a semiconductor device.
  • An amine content of 50 comprising heating a layer comprising a composition containing at least one of a polyimide precursor and a polybenzoxazole precursor and an amine generator at a maximum heating temperature of 250 ° C. or less.
  • ⁇ 2> The method for producing a cured film according to ⁇ 1>, wherein the amine generator is at least one of a photoamine generator and a thermal amine generator.
  • ⁇ 3> The method for producing a cured film according to ⁇ 1> or ⁇ 2>, wherein the amine generator is a thermal amine generator.
  • ⁇ 4> The method for producing a cured film according to any one of ⁇ 1> to ⁇ 3>, wherein the composition does not contain an amine having a pKa of at least a conjugate acid.
  • ⁇ 7> The composition according to any one of ⁇ 1> to ⁇ 6>, wherein the composition contains the amine generator in a proportion of 0.01 to 45% by mass with respect to the total amount of the polyimide precursor and the polybenzoxazole precursor.
  • the polyimide precursor is represented by the following general formula (2)
  • the polybenzoxazole precursor is represented by the following general formula (3):
  • a method for producing a membrane General formula (2)
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group.
  • ⁇ 11> The method for producing a cured film according to any one of ⁇ 1> to ⁇ 10>, wherein the amine content of the cured film is 500 to 2,000 ppm.
  • ⁇ 12> The method for producing a cured film according to any one of ⁇ 1> to ⁇ 11>, wherein the composition further contains a crosslinking agent.
  • ⁇ 13> The method for producing a cured film according to ⁇ 12>, wherein the crosslinking agent has a molecular weight of 100 to 800.
  • the amine generator is at least one selected from an acidic compound that generates an amine when heated to 40 to 250 ° C., and an ammonium salt having an anion having an anion of pKa1 of 0 to 4 and an ammonium cation.
  • 1>- ⁇ 13> The method for producing a cured film according to any one of ⁇ 15>
  • the method for producing a cured film according to ⁇ 14>, wherein the acidic compound is a compound that generates an amine when heated to 40 to 250 ° C.
  • ⁇ 16> The method for producing a cured film according to ⁇ 14> or ⁇ 15>, wherein the acidic compound is a salt of an ammonium cation and a carboxylic acid anion.
  • a method for producing an interlayer insulating film for a rewiring layer comprising the method for producing a cured film according to any one of ⁇ 1> to ⁇ 16>.
  • a method for producing a semiconductor device comprising the method for producing a cured film according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 19> A cured film obtained by the method for producing a cured film according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 20> A semiconductor device obtained by the method for producing a cured film according to any one of ⁇ 1> to ⁇ 16>.
  • the present invention it is possible to provide a method for producing a cured film having excellent corrosion resistance and chemical resistance.
  • a method for manufacturing an interlayer insulating film for a rewiring layer and a method for manufacturing a semiconductor device including the method for manufacturing the cured film.
  • the description of the components in 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 description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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).
  • active light means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means actinic rays or radiation.
  • exposure means not only exposure using far ultraviolet rays, X-rays, EUV light typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in the exposure.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acrylate represents both and / or “acrylate” and “methacrylate”
  • (meth) allyl means both “allyl” and “methallyl”
  • (Meth) acryl” represents either “acryl” and “methacryl” or any one
  • “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
  • the term “process” not only means an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
  • solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group.
  • the production method of the present invention comprises a layer comprising a composition comprising at least one of a polyimide precursor and a polybenzoxazole precursor (hereinafter sometimes referred to as “heterocycle-containing polymer precursor”) and an amine generator. It includes heating at a maximum heating temperature of 250 ° C. or less, and producing a cured film having an amine content of 50 to 5,000 ppm. Thus, by adjusting the amine content, a cured film having excellent corrosion resistance and chemical resistance can be provided.
  • Patent Document 1 describes that the generated amine may remain in the cured film depending on the purpose, but the specific amount is not specified.
  • Patent Document 2 describes that the tertiary amine remaining in the cured film is preferably in the range of 1 to 5% by mass.
  • the cured film to be obtained preferably has an amine content of 100 ppm or more, more preferably 400 ppm or more, and further preferably 500 ppm or more.
  • an upper limit it is preferable that it is 2,000 ppm or less, and it is more preferable that it is 1,000 ppm. By setting it as such a range, it is excellent in corrosion resistance and chemical resistance. Furthermore, it tends to be excellent in outgassing property, which is preferable.
  • the manufacturing method of the cured film of this invention includes heating the layer which consists of said composition at the maximum heating temperature of 250 degrees C or less.
  • the layer made of the above composition is usually formed by applying, preferably applying, the composition on a substrate.
  • Application methods of the composition to the substrate include spinning, dipping, doctor blade coating, suspended casting, coating, spraying, electrostatic spraying, reverse roll coating, etc., spinning, electrostatic spraying and reverse.
  • Roll coating is preferred because it can be applied uniformly on the substrate. It is also possible to introduce a layer of the above composition onto a temporary, flexible carrier and then apply the final substrate, for example a copper-coated printed circuit board by layer movement by lamination. .
  • Examples of the substrate include inorganic substrates, resins, and resin composite materials.
  • Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate.
  • polystyrene polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Groups consisting of synthetic resins such as aromatic ethers, maleimide-olefins, cellulose, episulfide compounds And the like.
  • TFT thin film transistor
  • the amount of composition applied (layer thickness) and the type of substrate (layer carrier) depend on the field of application desired.
  • the range of the layer thickness is preferably 0.5 to 100 ⁇ m. It is preferable to dry after applying the composition to the substrate. The drying is preferably performed at 60 to 150 ° C. for 10 seconds to 2 minutes, for example.
  • Heating is performed so that the maximum heating temperature is 250 ° C. or lower.
  • the upper limit of the maximum heating temperature is preferably 240 ° C. or lower, more preferably 230 ° C. or lower, further preferably 220 ° C. or lower, further preferably 210 ° C. or lower, and even more preferably 200 ° C. or lower.
  • the lower limit of the maximum heating temperature is preferably 140 ° C or higher, more preferably 160 ° C or higher, further preferably 170 ° C or higher, and particularly preferably 180 ° C or higher.
  • the maximum heating temperature is a temperature range in which the sample experiences a total of 30 seconds or more among the temperatures experienced by the sample due to the heating performed for the cyclization reaction of the heterocyclic-containing polymer precursor. The highest temperature among them.
  • the maximum heating temperature is preferably 0 to 100 ° C., more preferably 30 to 60 ° C. higher than the temperature at which the amine generator generates amine.
  • Heating is preferably performed at a temperature rising rate of 1 to 10 ° C./min from a temperature of 20 to 150 ° C. to a maximum heating temperature, more preferably 2 to 10 ° C./min. Is more preferable, and 3 to 6 ° C./min is particularly preferable.
  • a temperature rising rate 1 to 10 ° C./min from a temperature of 20 to 150 ° C. to a maximum heating temperature, more preferably 2 to 10 ° C./min. Is more preferable, and 3 to 6 ° C./min is particularly preferable.
  • the temperature at the start of heating is preferably 20 to 150 ° C., more preferably 20 to 130 ° C., and further preferably 25 to 120 ° C.
  • the temperature at the start of heating refers to the temperature of the layer made of the composition when starting the step of heating to the maximum heating temperature.
  • the temperature is the temperature after the drying, for example, the temperature is gradually raised from the boiling point of the solvent contained in the composition— (30 to 200) ° C. preferable. Heating is preferably performed for 60 to 240 minutes after reaching the maximum heating temperature, more preferably for 100 to 230 minutes, and particularly preferably for 150 to 220 minutes. By setting it as such a range, it becomes easy to adjust the quantity of the amine in a cured film.
  • Heating may be performed in stages. For example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, placed at 180 ° C. for 60 minutes, heated from 180 ° C. to 200 ° C. at 2 ° C./minute, and placed at 200 ° C. for 120 minutes. Is mentioned. In this case, it is preferable to set the heating conditions so that all of the stepwise heating satisfies the above heating conditions. Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing the decomposition of the heterocyclic-containing polymer precursor such as polyimide.
  • the oxygen concentration is preferably 50 ppm by volume or less, and more preferably 20 ppm by volume or less.
  • the method for producing a cured film of the present invention preferably includes a step of applying (preferably applying) the composition to a substrate, and a layer (layered composition) comprising the composition applied to the substrate. And a step of curing.
  • a pattern forming step may be further performed between the step of applying the composition to the substrate and the step of curing.
  • the pattern forming step can be performed by, for example, a photolithography method. For example, the method of performing through the process of exposing and the process of developing is mentioned.
  • pattern formation by photolithography method uses a photosensitive resin composition containing a heterocyclic-containing polymer precursor, a compound having an ethylenically unsaturated bond as a crosslinking agent, and a radical photopolymerization initiator. It is preferable to carry out.
  • a photosensitive resin composition containing a heterocyclic ring-containing polymer precursor and a photoacid generator it is preferable to use a photosensitive resin composition containing a heterocyclic ring-containing polymer precursor and a photoacid generator.
  • the heterocyclic ring-containing polymer precursor preferably has an ethylenically unsaturated bond. Details of these will be described later.
  • a case where a pattern is formed by photolithography will be described.
  • the step of applying (preferably applying) the composition to the substrate and the step of curing the layered composition applied to the substrate are the same as described above, and the preferred range is also the same.
  • the photosensitive resin composition applied to the substrate is irradiated with a predetermined pattern of actinic rays or radiation.
  • the wavelength of the actinic ray or radiation varies depending on the composition of the photosensitive resin composition, but is preferably 200 to 600 nm, more preferably 300 to 450 nm.
  • a light source a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used.
  • Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • Exposure is preferably 1 ⁇ 1,000mJ / cm 2, more preferably 200 ⁇ 800mJ / cm 2.
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
  • (meth) acrylate and similar olefinically unsaturated compounds are used, their photopolymerization is prevented by oxygen in the air, as is well known, particularly in thin layers. This effect can be mitigated by known conventional methods such as temporary introduction of a coating layer of polyvinyl alcohol, pre-exposure or pre-conditioning in an inert gas.
  • an unexposed portion of the photosensitive resin composition is developed using a developer.
  • a developer an aqueous alkaline developer, an organic solvent, or the like can be used.
  • the alkali compound used in the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicic acid. Examples include potassium, ammonia, and amine.
  • amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide.
  • TMAH tetramethylammonium hydroxide
  • alkali compounds containing no metal are preferred.
  • Suitable aqueous alkaline developers are generally up to 0.5 N with respect to alkali, but may be diluted appropriately prior to use.
  • an aqueous alkaline developer having a concentration of about 0.15 to 0.4 N, preferably 0.20 to 0.35 N is also suitable. Only one alkali compound may be used, or two or more alkali compounds may be used. When there are two or more alkali compounds, the total is preferably in the above range.
  • an organic solvent the thing similar to the solvent which can be used for the composition mentioned later can be used.
  • preferable examples include n-butyl acetate, ⁇ -butyrolactone, cyclopentanone, and a mixture thereof.
  • composition used in the present invention contains at least one of a polyimide precursor and a polybenzoxazole precursor (hereinafter sometimes referred to as “heterocycle-containing polymer precursor”).
  • the polyimide precursor used in the present invention does not particularly define the structure or the like as long as it can be converted to a polyimide, and includes a polyamideimide precursor. It is preferable that the polyimide precursor used by this invention contains the repeating unit represented by following General formula (2).
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in the general formula (2) each independently represent an oxygen atom or NH, and preferably an oxygen atom.
  • at least one of A 1 and A 2 is an oxygen atom
  • R 113 and / or adjacent to oxygen atoms A 1 and A 2 and / or R 114 is preferably a monovalent organic group.
  • R 111 represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a group containing a cyclic aliphatic group and an aryl group, and a linear or branched aliphatic group having 2 to 20 carbon atoms.
  • R 111 is more specifically a diamine residue remaining after removal of the amino group of the diamine.
  • the diamine include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Specific examples include diamine residues remaining after removal of the amino groups of the following diamines.
  • 1,2-diaminoethane 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1, 2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (3-amino Cyclohexyl) methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4′- and 3,3′-diaminobiphenyl, 4, 4'- and 3,3'-diaminodiphenyl ether, 4,4
  • R 111 also include diamine residues remaining after removal of the amino groups of diamines (DA-1) to (DA-18) shown below.
  • R 111 also include a diamine residue remaining after removal of an amino group of a diamine having two or more alkylene glycol units in the main chain.
  • a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in one molecule Preferred is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine residue containing no aromatic ring.
  • Examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( Trade names, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propane Examples include, but are not limited to, -2-yl) oxy) propan-2-amine and the like.
  • the structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.
  • x, y, and z are average values.
  • R 115 represents a tetravalent organic group.
  • a tetravalent organic group the tetravalent organic group containing an aromatic ring is preferable, and the group represented by the following general formula (5) or general formula (6) is more preferable.
  • the divalent group includes a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO 2 — and —NHCO— and combinations thereof. A selected group is preferred.
  • R 112 is a single bond or a divalent group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— and —SO 2 —. More preferably a single bond or —CH 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, —O—, —CO—, —S— and —SO. 2 - divalent radical selected from the group consisting of is more preferable.
  • R 115 include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride.
  • Specific examples include tetracarboxylic acid residues remaining after the removal of anhydride groups from the following tetracarboxylic dianhydrides.
  • tetracarboxylic acid residue remaining tetracarboxylic dianhydride represented by the following from (DAA-1) ⁇ (DAA -5) after removal of the anhydride groups mentioned as examples of R 115.
  • R 111 and R 115 has an OH group. More specifically, as R 111 , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino) -3-Hydroxyphenyl) sulfone and the above (DA-1) to (DA-18) are mentioned as preferred examples, and as R 115 , the above (DAA-1) to (DAA-5) are mentioned as preferred examples. It is done.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • a substituent that improves the solubility in a developer is preferably used.
  • R 113 and R 114 are preferably a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include an aryl group and an aralkyl group having one, two or three, preferably one acidic group bonded to the carbon atom of the aryl group.
  • Specific examples include an aryl group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
  • the acidic group is preferably an OH group.
  • R 113 and R 114 are preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • R 113 and R 114 are preferably monovalent organic groups.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aryl group, and more preferably an alkyl group substituted with an aryl group.
  • the alkyl group preferably has 1 to 30 carbon atoms.
  • 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, Examples include octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group.
  • a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity.
  • the linear alkyl group substituted by the aryl group mentioned later is preferable.
  • aryl group examples include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring.
  • R113 and R114 has a polymerizable unsaturated group. According to this, a negative photosensitive resin with better sensitivity and resolution can be obtained.
  • a polymerizable unsaturated group particularly a radical polymerizable group
  • a polymerizable unsaturated group is not essential when a crosslinking agent (particularly a radically polymerizable compound) is blended.
  • Examples of the polymerizable unsaturated group include an epoxy group, an oxetanyl group, a group having an ethylenically unsaturated bond, a blocked isocyanate group, an alkoxymethyl group, a methylol group, and an amino group. Of these, a group having an ethylenically unsaturated bond is preferred because of its good sensitivity. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.
  • R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a polyoxyalkylene group having 4 to 30 carbon atoms.
  • R 201 examples include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, —CH 2 CH (OH) CH 2- , and ethylene, propylene, trimethylene, and —CH 2 CH (OH) CH 2 — are preferred.
  • R 200 is methyl and R 201 is ethylene.
  • the ratio of R 113 and R 114 being a polymerizable unsaturated group is preferably a molar ratio of polymerizable group: no polymerizable group, preferably 100: 0 to 5:95, more preferably 100: 0 to 20:80, and still more preferably 100: 0 to 50:50.
  • the polyimide precursor when R 113 is a hydrogen atom and / or when R 114 is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. It may be.
  • tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
  • the polyimide precursor preferably has a fluorine atom in the structural unit from the viewpoint of improving resolution.
  • the fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking in from the surface can be suppressed.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.
  • an aliphatic group having a siloxane structure may be copolymerized for the purpose of improving the adhesion to the substrate.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
  • the polyimide precursor is sealed at the end of the main chain with an end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. It is preferable. Of these, it is more preferable to use a monoamine.
  • Monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1- Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid, -Aminobenzoic acid, 4-aminosalicylic acid, 5-
  • the repeating unit represented by the general formula (2) is preferably a repeating unit represented by the general formula (1-1). That is, it is preferable that at least one of the heterocyclic ring-containing polymer precursors used in the present invention is a precursor having a repeating unit represented by the general formula (1-1). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.
  • a 1 and A 2 each represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently represent Represents a hydrogen atom or a monovalent organic group.
  • a 1, A 2, R 111 , R 113 and R 114 are each independently the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), the preferred range is also the same is there.
  • R 112 has the same meaning as R 112 in General Formula (5), and the preferred range is also the same.
  • the polyimide precursor may be one type of repeating structural unit represented by the general formula (2), but may be two or more types. Moreover, the structural isomer of the repeating unit represented by General formula (2) may be included. It goes without saying that the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the general formula (2).
  • polyimide precursor in the present invention a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all repeating units are repeating units represented by the general formula (2).
  • the body is illustrated.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 10,000 to 50,000, more preferably 14,000 to 30,000.
  • the number average molecular weight (Mn) is preferably 5,000 to 14,000.
  • the degree of dispersion of the polyimide precursor is preferably 2.0 or more, more preferably 2.1 or more.
  • the upper limit of the degree of dispersion of the polyimide precursor is not particularly defined, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, and still more preferably 3.2 or less, 3.1 or less is more preferable, 3.0 or less is even more preferable, 2.95 or less is particularly more preferable, and 2.6 or less is most preferable.
  • the polybenzoxazole precursor used in the present invention is not particularly limited as long as it is a compound that can be converted into polybenzoxazole, but is preferably a compound represented by the following general formula (3).
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group. Represents.
  • R 121 represents a divalent organic group.
  • the divalent organic group include an aliphatic group and an aryl group. The following are mentioned as an example of a bivalent aryl group.
  • A represents —CH 2 —, —O—, —S—, —SO 2 —, —CO—, —NHCO—, —C (CF 3 ) 2 —, and —C (CH 3 ) 2 —.
  • a linear aliphatic group is preferable from the viewpoint of promoting cyclization at a low temperature.
  • the linear aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms, and still more preferably 4 to 15 carbon atoms. Particularly preferred is 5-10.
  • the linear aliphatic group is preferably an alkylene group.
  • dicarboxylic acids containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid Acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid , Suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hex
  • Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the general formula (2), and preferred ranges are also the same.
  • R 122 is preferably a residue of a bisaminophenol derivative represented by the following general formula (A).
  • Ar (NH 2 ) 2 (OH) 2 (A)
  • Ar is an aryl group.
  • Examples of the bisaminophenol derivative represented by the general formula (A) include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, and 3,3 ′.
  • bisaminophenol derivatives represented by the general formula (A) bisaminophenol derivatives having the following aryl groups are preferable.
  • X 1 represents —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO—.
  • —OH and —NH 2 contained in the structure of the general formula (A) are bonded to each other at the ortho position (adjacent position).
  • the bisaminophenol derivative represented by the general formula (A) is represented by the following general formula (As) because a polybenzoxazole precursor that is highly transparent to i-line and can be cured at a low temperature can be obtained. Bisphenol is preferred.
  • R 1 is alkylene, substituted alkylene, —O—, —S—, —SO 2 —, —CO—, —NHCO—, a single bond, or an organic group selected from the group of the following formula (A-sc) It is.
  • R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
  • R 3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
  • R 2 is an alkyl group and R 3 is an alkyl group, which means that it has high transparency to i-line and a high cyclization rate when cured at low temperature.
  • R 3 is an alkyl group, which means that it has high transparency to i-line and a high cyclization rate when cured at low temperature.
  • a polybenzoxazole precursor having sufficient solubility and excellent balance can be obtained when an alkaline aqueous solution is used as a developer while maintaining the effect.
  • R 1 is preferably alkylene or substituted alkylene.
  • alkylene and substituted alkylene according to R 1 include —CH 2 —, —CH (CH 3 ) —, —C (CH 3 ) 2 —, —CH (CH 2 CH 3 ) —, —C (CH 3 ) (CH 2 CH 3 )-, -C (CH 2 CH 3 ) (CH 2 CH 3 )-, -CH (CH 2 CH 2 CH 3 )-, -C (CH 3 ) (CH 2 CH 2 CH 3 ) —, —CH (CH (CH 3 ) 2 ) —, —C (CH 3 ) (CH (CH 3 ) 2 ) —, —CH (CH 2 CH 2 CH 2 CH 3 ) —, —C (CH 3 ) (CH (CH 3 ) 2 ) —, —CH (CH 2 CH 2 CH 2 CH 3 ) —, —C (CH 3 ) (CH (CH 3 ) (CH (
  • R 123 and R 124 represent a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom or a polymerizable unsaturated group. It is preferable that at least one of R 123 and R 124 represents a polymerizable unsaturated group in that a negative photosensitive resin with better sensitivity and resolution can be obtained.
  • the polymerizable unsaturated group is the same as described aspects R 113 and R 114 in formula (2), and preferred ranges are also the same.
  • the polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the general formula (3). It is preferable that the diamine residue represented with the following general formula (SL) is included as another type of repeating structural unit at the point which can suppress generation
  • SL general formula
  • Z has a structure and b structure
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
  • at least one of R 3s , R 4s , R 5s and R 6s is an aryl group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different.
  • the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
  • the mol% of the Z moiety is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and a + b is 100 mol%.
  • Z include those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by the general formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000.
  • the molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight within the above range, it is possible to reduce both the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor and to suppress the warp and to improve the solubility.
  • the diamine residue represented by the general formula (SL) is included as another type of repeating structural unit
  • the remaining tetra after the anhydride group is removed from the tetracarboxylic dianhydride is further improved in terms of alkali solubility.
  • an acid anhydride containing an aliphatic group or a cyclic group having at least one alkenyl group or alkynyl group as the terminal amino group of the polybenzoxazole precursor is used.
  • the amide is preferably capped.
  • the end-capping group As such a group derived from an acid anhydride containing an aliphatic group or cyclic group having at least one alkenyl group or alkynyl group after reacting with an amino group, that is, the end-capping group is, for example,
  • the following groups can be exemplified. These may be used alone or in combination of two or more.
  • the groups shown below are preferable because they can improve storage stability.
  • the polybenzoxazole precursor includes, for example, a bisaminophenol derivative represented by the general formula (A), a dicarboxylic acid containing R 121 and a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivative of the above dicarboxylic acid. It can be obtained by reaction.
  • dicarboxylic acid an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 8,000 to 30,000, more preferably 9,000 to 29,000 when used in the composition described below.
  • the preferred range is 10,000 to 28,000.
  • the number average molecular weight (Mn) is preferably 5,000 to 14,000, more preferably 6,000 to 12,000, and further preferably 6,500 to 11,200.
  • the degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more.
  • the upper limit value of the degree of dispersion of the polybenzoxazole precursor is not particularly defined, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and more preferably 2.3 or less. Preferably, 2.2 or less is even more preferable.
  • the content of the heterocyclic ring-containing polymer precursor in the composition used in the present invention is preferably 20 to 50% by mass, more preferably 25 to 40% by mass of the composition. Further, the content of the heterocyclic ring-containing polymer precursor in the composition used in the present invention is preferably 70% by mass or more, and more preferably 75% by mass or more, based on the solid content of the composition.
  • the upper limit is not particularly defined, but the total amount of the heterocyclic-containing polymer precursor and the amine generator may be 100% by mass of the solid content of the composition.
  • the composition used by this invention may contain only 1 type of heterocyclic containing polymer precursors, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
  • polyimide precursor and the polybenzoxazole precursor may be included, the aspect which consists only of 1 or more types of polyimide precursors, and the aspect which consists only of 2 or more types of polybenzoxazole precursors are more. preferable.
  • the amine generator is preferably a thermal amine generator or a photoamine generator, more preferably a thermal amine generator.
  • Examples of these amine generators generally include amines inactivated by a protecting group such as an alkoxycarbonyl group, nifedipines, salts formed with amines and acids, and quaternary ammonium salts.
  • a protecting group such as an alkoxycarbonyl group, nifedipines, salts formed with amines and acids, and quaternary ammonium salts.
  • thermal amine generator The type of the thermal amine generator is not particularly defined, but it has an acidic compound (A1) that generates an amine when heated to 40 to 250 ° C., and an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable to include at least one selected from ammonium salts (A2). By adopting such a compound, the outgassing property can be further improved.
  • pKa1 represents a logarithmic representation ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
  • the cyclization reaction of the heterocyclic ring-containing polymer precursor can be performed at a low temperature, and the composition can be made more stable.
  • the thermal amine generator does not generate amine unless it is heated, cyclization of the heterocyclic-containing polymer precursor during storage can be suppressed even in the presence of the heterocyclic-containing polymer precursor, and storage stability is improved. Are better.
  • Thermal amine generators generate amines when heated, so amines generated from these compounds can promote the cyclization reaction of the heterocyclic ring-containing polymer precursor, and cyclize the heterocyclic ring-containing polymer precursor at a low temperature. be able to.
  • these compounds are excellent in stability because even if they are present together with a heterocyclic-containing polymer precursor that is cured by cyclization with an amine, the cyclization of the heterocyclic-containing polymer precursor hardly proceeds unless heated.
  • a composition can be prepared.
  • the amine generation temperature of the thermal amine generator in the present invention is preferably 40 to 250 ° C, more preferably 120 to 250 ° C.
  • the upper limit of the temperature at which amine is generated is more preferably 240 ° C. or less, further preferably 230 ° C. or less, further preferably 220 ° C. or less, still more preferably 200 ° C. or less, still more preferably 190 ° C. or less, and 180 ° C. or less. Particularly preferred.
  • the lower limit of the temperature at which amine is generated is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher.
  • the amine generation temperature is measured using differential scanning calorimetry, the thermal amine generator is heated to 250 ° C.
  • the peak temperature of the lowest exothermic peak is read, and the peak temperature is the amine generation temperature.
  • the temperature at which the amine of the thermal amine generator is generated is 40 ° C. or higher, the amine is less likely to be generated during storage, so that a composition having more stability can be prepared. If the temperature for generating the amine of the thermal amine generator is 250 ° C. or lower, the cyclization temperature of the heterocyclic-containing polymer precursor can be lowered.
  • the amine generated by the thermal amine generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a heterocyclic containing polymer precursor can be lowered more.
  • the boiling point of the amine generated by the amine generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 140 ° C. or higher.
  • the molecular weight of the generated amine is preferably 60 to 300.
  • the lower limit is more preferably 100 or more, and further preferably 120 or more.
  • the upper limit is more preferably 250 or less, and even more preferably 200 or less.
  • the molecular weight value is a theoretical value obtained from the structural formula.
  • the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the general formula (1A) described later.
  • the ammonium salt (A2) is preferably an acidic compound.
  • the ammonium salt (A2) may be a compound containing an acidic compound that generates an amine when heated to 40 ° C. to 250 ° C. (preferably 120 to 200 ° C.), or 40 ° C. to 250 ° C. (preferably A compound that does not contain an acidic compound that generates an amine when heated to 120 to 200 ° C. may be used.
  • the ammonium salt means a salt of an ammonium cation represented by the general formula (11) or the general formula (12) and an anion.
  • the anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation.
  • numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
  • the anion outside the molecule of the cation moiety is also referred to as a counter anion.
  • R 1N to R 6N each independently represents a hydrogen atom or a hydrocarbon group
  • R 7N represents a hydrocarbon group
  • R 1N and R 2N , R 3N and R 4N , R 5N and R 6N , R 5N and R 7N may be combined to form a ring.
  • the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
  • the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the lower limit is more preferably 0.5 or more, and further preferably 1.0 or more.
  • the kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
  • a thermal amine generator that can further improve the stability, curability and developability of the composition can be obtained.
  • the stability, curability and developability of the composition can be further improved by using an anion of a divalent carboxylic acid.
  • the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved.
  • pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid. Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
  • the carboxylate anion is preferably represented by the formula (X1).
  • EWG represents an electron withdrawing group.
  • the electron withdrawing group means a group having a positive Hammett's substituent constant ⁇ m.
  • ⁇ m is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 631-642.
  • the electron withdrawing group of this invention is not limited to the substituent described in the said literature.
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group.
  • EWG preferably represents a group represented by the following general 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 hydroxy group, or a carboxy group
  • Ar represents an aryl group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted.
  • the substituent examples include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • a carboxy group is preferable.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkenyl group may have a substituent or may be unsubstituted.
  • Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • a carboxy group is preferable.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later. As the substituent, a carboxy group is preferable.
  • the carboxylate anion is also preferably represented by the following general formula (X).
  • L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR X —, and a combination thereof
  • R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
  • the alkylene group represented by L 10 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • the alkenylene group represented by L 10 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • the alkenylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkenylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • the number of carbon atoms of the arylene group represented by L 10 is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.
  • the arylene group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • the number of carbon atoms of the alkyl group represented by R X is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • the alkenyl group represented by R X preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • the number of carbon atoms of the aryl group represented by R X is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.
  • the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
  • the ammonium cation is preferably represented by any one of formulas (Y1-1) to (Y1-6).
  • R 101 represents an n-valent organic group
  • R 102 to R 111 each independently represents a hydrogen atom or a hydrocarbon group
  • R 150 and R 151 each independently represent a hydrocarbon group
  • R 104 and R 105 , R 104 and R 150 , R 107 and R 108 , and R 109 and R 110 may be bonded to each other to form a ring
  • Ar 101 and Ar 102 each independently represent an aryl group
  • n represents an integer of 1 or more
  • m represents an integer of 0 to 5.
  • R 101 represents an n-valent organic group.
  • the monovalent organic group include an alkyl group, an alkylene group, and an aryl group.
  • the divalent or higher organic group include those obtained by removing one or more hydrogen atoms from a monovalent organic group to form an n-valent group.
  • R 101 is preferably an aryl group. Specific examples of the aryl group include those described for Ar 10 described later.
  • R 102 to R 111 each independently represents a hydrogen atom or a hydrocarbon group
  • R 150 and R 151 each independently represent a hydrocarbon group.
  • the hydrocarbon group represented by R 102 to R 111 , R 150 and R 151 is preferably an alkyl group, an alkenyl group or an aryl group.
  • the alkyl group, alkenyl group and aryl group may further have a substituent. Examples of the substituent include those described for the organic group has optionally may substituent represented by A 1 to be described later.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent or may be unsubstituted.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkenyl group may have a substituent or may be unsubstituted.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent or
  • Ar 101 and Ar 102 each independently represents an aryl group.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aryl group may have a substituent or may be unsubstituted.
  • R 104 and R 105 , R 104 and R 150 , R 107 and R 108 , and R 109 and R 110 may be bonded to each other to form a ring.
  • the ring include cyclic aliphatic (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring and the like.
  • the ring may be monocyclic or polycyclic.
  • the linking group is selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group, and combinations thereof.
  • the bivalent coupling group chosen is mentioned.
  • the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole.
  • the ammonium cation preferably has a structure represented by the formula (Y1-1) or (Y1-2), represented by the formula (Y1-1) or (Y1-2), and R 101 is an aryl group.
  • a certain structure is more preferable, and a structure represented by the formula (Y1-1) in which R 101 is an aryl group is particularly preferable.
  • the ammonium cation is more preferably represented by the following general formula (Y).
  • Ar 10 represents an aryl group
  • R 11 to R 15 each independently represents a hydrogen atom or a hydrocarbon group
  • R 14 and R 15 are bonded to each other to form a ring.
  • n represents an integer of 1 or more.
  • Ar 10 represents an aryl group.
  • the aryl group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring.
  • a benzene ring, a naphthalene ring, an anthracene ring, a phenothiazine ring, or a carbazole ring is preferable, and a benzene ring or a naphthalene ring is most preferable.
  • aryl groups the substituents which may have include those described in the organic group has optionally may substituent represented by A 1 to be described later.
  • R 11 and R 12 each independently represents a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group is not particularly limited, but is preferably an alkyl group, an alkenyl group or an aryl group.
  • R 11 and R 12 are preferably a hydrogen atom.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group 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, Examples include an ocdadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • R 13 to R 15 each represents a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group include the hydrocarbon groups described above for R 11 and R 12 .
  • R 13 to R 15 are particularly preferably alkyl groups, and preferred embodiments are also the same as those described for R 11 and R 12 .
  • R 14 and R 15 may be bonded to each other to form a ring.
  • the ring include cycloaliphatic (non-aromatic hydrocarbon ring), aromatic ring, heterocyclic ring and the like.
  • the ring may be monocyclic or polycyclic.
  • the linking group is composed of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group, and combinations thereof. And divalent linking groups selected from the group.
  • the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole.
  • R 13 to R 15 are a group in which R 14 and R 15 are bonded to each other to form a ring, or R 13 is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms).
  • R 14 and R 15 are preferably each independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, it is possible to easily generate amine species having a high boiling point.
  • R 13 to R 15 are preferably 7 to 30 in terms of the total number of carbon atoms of R 13 , R 14 and R 15 from the viewpoint of the basicity and boiling point of the generated amine species. It is more preferable.
  • the chemical formula amount of “—NR 13 R 14 R 15 ” in the general formula (Y) is preferably 80 to 2,000, and more preferably 100 to 500, because amine species having a high boiling point are likely to be generated.
  • R 13 and R 14 is a methyl group or an ethyl group, the number R 15 carbon 5 or more linear , A branched or cyclic alkyl group, or an aryl group.
  • R 13 and R 14 are methyl groups
  • R 15 is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, or a cyclic alkyl group having 6 to 10 carbon atoms.
  • R 13 and R 14 are methyl groups
  • R 15 is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, or 6 to 8 carbon atoms.
  • a cyclic alkyl group or a phenyl group is more preferable.
  • the acidic compound is also preferably a compound represented by the following general formula (1A).
  • This compound is acidic at room temperature. However, the carboxy group is lost by decarboxylation or dehydration cyclization by heating, and the neutralized and inactivated amine site becomes active. It becomes.
  • general formula (1A) is demonstrated.
  • a 1 represents a p-valent organic group
  • R 1 represents a monovalent organic group
  • L 1 represents a (m + 1) -valent organic group
  • m represents an integer of 1 or more
  • P represents an integer of 1 or more.
  • a 1 represents a p-valent organic group.
  • the organic group include an aliphatic group and an aryl group, and an aryl group is preferable.
  • the A 1 and aryl group at lower temperatures, often invites high boiling amines.
  • volatilization or decomposition due to heating at the time of curing of the heterocyclic ring-containing polymer precursor can be suppressed, and cyclization of the heterocyclic ring-containing polymer precursor can proceed more effectively.
  • the monovalent aliphatic group include an alkyl group and an alkenyl group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • the alkyl group may have a substituent or may be unsubstituted.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic.
  • the alkenyl group may have a substituent or may be unsubstituted.
  • Examples of the alkenyl group include a vinyl group and a (meth) allyl group.
  • Examples of the divalent or higher valent aliphatic group include groups obtained by removing one or more hydrogen atoms from the above monovalent aliphatic group.
  • the aryl group may be monocyclic or polycyclic.
  • the aryl group may be a heteroaryl group containing a heteroatom.
  • the aryl group may have a substituent or may be unsubstituted. Unsubstituted is preferred. Specific examples of the aryl group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, in
  • a plurality of aromatic rings may be linked through a single bond or a linking group described later.
  • the linking group for example, an alkylene group is preferable.
  • the alkylene group is preferably linear or branched.
  • Specific examples of the aryl group in which a plurality of aromatic rings are linked through a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, and tetraphenylmethane.
  • Examples of the substituent that the organic group represented by A 1 may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methoxy group, an ethoxy group and a tert-butoxy group.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • a methoxy group, an ethoxy group and a tert-butoxy group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group , Acyl groups such as benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; phenylsulfanyl group and p-tolylsulfani An arylsulfanyl group such as a methyl group; a linear or branched alkyl group such as a methyl group, an ethyl group, a tert-butyl group and a dodecyl group; a hal
  • L 1 represents a (m + 1) -valent linking group.
  • the linking group is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group (preferably a straight chain having 1 to 10 carbon atoms).
  • a chain or branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a linear or branched alkenylene group having 2 to 10 carbon atoms), and a plurality of these are linked Examples thereof include a linking group.
  • the total carbon number of the linking group is preferably 3 or less.
  • the linking group is preferably an alkylene group, a cycloalkylene group, or an alkenylene group, more preferably a linear or branched alkylene group, still more preferably a linear alkylene group, particularly preferably an ethylene group or a methylene group, and most preferably a methylene group.
  • R 1 represents a monovalent organic group.
  • the monovalent organic group include an aliphatic group and an aryl group. Aliphatic group, for the aryl group include those described in A 1 described above.
  • the monovalent organic group represented by R 1 may have a substituent.
  • R 1 is preferably a group having a carboxy group. That is, R 1 is preferably a group represented by the formula. -L 2- (COOH) n
  • L 2 represents an (n + 1) -valent linking group, and n represents an integer of 1 or more.
  • the linking group represented by L 2 include the groups described above for L 1 , and the preferred ranges are also the same, an ethylene group or a methylene group is particularly preferred, and a methylene group is most preferred.
  • n represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
  • the upper limit of n is the maximum number of substituents that can take the linking group L 2 represents.
  • n 1, a tertiary amine having a high boiling point is likely to be generated by heating below the maximum heating temperature. Furthermore, the stability of the composition can be improved.
  • m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
  • the upper limit of m is the maximum number of substituents that the linking group represented by L 1 can take.
  • p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
  • the upper limit of p is the maximum number of substituents that can take the organic group A 1 represents. When p is 1, a tertiary amine having a high boiling point is likely to be generated by heating below the maximum heating temperature.
  • the compound represented by the general formula (1A) is preferably a compound represented by the following general formula (1a).
  • a 1 , L 1 , L 2 , m, n and p in the general formula (1a) have the same meanings as the ranges described in the general formula (1A), and preferred ranges are also the same.
  • the compound represented by the general formula (1A) is preferably N-aryliminodiacetic acid.
  • a 1 in the general formula (1A) is an aryl group
  • L 1 and L 2 are methylene groups
  • m is 1
  • n is 1
  • p is 1.
  • N-aryliminodiacetic acid tends to generate a tertiary amine having a high boiling point at 120 to 200 ° C.
  • thermal amine generator in this invention is not limited to these. These can be used alone or in admixture of two or more. Me in the following formulas represents a methyl group.
  • (A-1) to (A-11), (A-18), and (A-19) are compounds represented by the above formula (1). Of the compounds shown below, (A-1) to (A-11), (A-18) to (A-26) are more preferred, and (A-1) to (A-9), (A-18) ) To (A-21), (A-23), and (A-24) are more preferable.
  • the photoamine generator can be suitably used in the negative type because the base generated by exposure works as a catalyst when the heterocyclic ring-containing polymer precursor is cured by heating.
  • photoamine generators can be used.
  • M.M. Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci.
  • amines form salts, such as those having a structure such as an ammonium salt, or those in which an amidine moiety is latentized by forming a salt with a carboxylic acid.
  • salts such as those having a structure such as an ammonium salt, or those in which an amidine moiety is latentized by forming a salt with a carboxylic acid.
  • examples thereof include ionic compounds that have been neutralized, and nonionic compounds in which the base component is made latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
  • Examples of amines generated from the photoamine generator include monoamines, polyamines such as diamines, and amidines.
  • the generated amine is preferably a diamine or an aliphatic amine.
  • Such amines have a strong catalytic effect on the dehydration condensation reaction in imidation or oxazolation of a heterocycle-containing polymer precursor, and the catalytic effect is exhibited in a dehydration condensation reaction at a lower temperature with a smaller amount of addition. This is because it becomes possible. That is, since the generated amine has a large catalytic effect, the apparent sensitivity of the composition is improved.
  • Examples of the amine according to the present invention include a base generator having a cinnamic amide structure as disclosed in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. 2009/123122, Japanese Patent Application Laid-Open No. 2006-189591, and A base generator having a carbamate structure as disclosed in JP-A-2008-247747, an oxime structure or a carbamoyloxime structure as disclosed in JP-A-2007-249013 and 2008-003581 Examples thereof include, but are not limited to, amines, and other known amine structures can be used.
  • the photoamine generator that can be used in the present invention will be described below with specific examples.
  • Examples of the ionic compound include those having the following structural formula.
  • acyl compound examples include compounds represented by the following formula.
  • examples of the photoamine generator include compounds represented by the following general formula (PB-1).
  • R 41 and R 42 each independently represent a hydrogen atom or an organic group, and may be the same or different, provided that at least one of R 41 and R 42 is present.
  • R 41 and R 42 may be bonded to each other to form a ring structure and may contain a heteroatom bond, and R 43 and R 44 are each independently an organic group.
  • R 45, R 46, R 47 and R 48 are each independently a hydrogen atom, a halogen atom, a hydroxyl , Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or an organic group, may be different even in the same .
  • R 45, R 46, R 47 and R 48 are each independently a hydrogen atom, a halogen atom, a hydroxyl , Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group
  • photoamine generator examples include compounds described in paragraph numbers 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraph numbers 0022 to 0069 of JP2013-194205A. Examples thereof include compounds described in JP-A-2013-204019, paragraphs 0026 to 0074, and compounds described in paragraph No. 0052 of international publication WO 2010/064631, the contents of which are incorporated herein. It is.
  • the content of the amine generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • the amine generator is preferably contained at a ratio of 0.01 to 45% by mass with respect to the total amount of the polyimide precursor and the polybenzoxazole precursor.
  • the lower limit of the amine generator relative to the total amount of the polyimide precursor and the polybenzoxazole precursor is more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. preferable.
  • the upper limit is more preferably 35.0% by mass or less, further preferably 28.0% by mass or less, still more preferably 12% by mass or less, and still more preferably 6.0% by mass or less.
  • the upper limit is more preferably 35.0% by mass or less, further preferably 28.0% by mass or less, still more preferably 12% by mass or less, and still more preferably 6.0% by mass or less.
  • composition used in the present invention may or may not use another thermal base generator in addition to the amine generator.
  • the composition in the present invention can be configured to be substantially free of other thermal base generators. “Substantially free” means, for example, 0.1% by mass or less of the amount of amine generator contained in the composition.
  • the composition used in the present invention does not contain an amine having a pKa of 8 or more as a conjugate acid.
  • the phrase “the composition does not contain an amine having a pKa of 8 or more of the conjugate acid” means that the composition does not contain an amine having a pKa of 8 or more of the conjugate acid in the composition at all, and also includes a case where the amine does not substantially contain.
  • “Substantially” means to include within a range not departing from the gist of the present invention, for example, when it is 0.001% by mass or less of the amine generator contained in the composition, or when it is below the detection limit. It can be said that it does not contain substantially.
  • the amine amount of a cured film can be adjusted more easily by not including the amine of pKa8 or more of a conjugate acid in the composition before starting the cyclization reaction of a heterocyclic-containing polymer precursor.
  • the composition in this invention does not contain an amine substantially before a heating. “Substantially” is intended to include the case where it is included within the scope of the present invention. For example, when it is 0.001% by mass or less of the amine generator contained in the composition, it is not substantially included. It can be said.
  • composition used in the present invention includes a heterocyclic ring-containing polymer precursor and an amine generator, other components are not particularly defined, but other components are appropriately blended depending on the use and the like. be able to.
  • the composition used in the present invention is preferably a photosensitive resin composition, but is not necessarily limited to applications having photosensitivity.
  • 1st embodiment of the photosensitive resin composition in this invention contains a heterocyclic containing polymer precursor and radical photopolymerization initiator.
  • Such a photosensitive resin composition is preferably used as a negative photosensitive resin composition.
  • the heterocyclic ring-containing polymer precursor When used as a negative photosensitive resin composition, it is preferred that the heterocyclic ring-containing polymer precursor has a polymerizable unsaturated group or contains a crosslinking agent.
  • the crosslinking agent preferably includes a compound having an ethylenically unsaturated bond.
  • 2nd embodiment of the photosensitive resin composition in this invention contains a heterocyclic containing polymer precursor and a photo-acid generator.
  • Such a photosensitive resin composition is preferably used as a positive photosensitive resin composition.
  • the crosslinking agent is selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. At least one compound is preferred.
  • the negative photosensitive resin composition may contain a sensitizer, a polymerization inhibitor and the like. Moreover, it cannot be overemphasized that components other than these may also be included.
  • the positive photosensitive resin composition may contain a resin containing a phenolic OH group. Moreover, it cannot be overemphasized that components other than these may also be included. Details of these components will be described later.
  • the heterocyclic-containing polymer precursor contains a polybenzoxazole precursor.
  • the composition used in the present invention may also contain a ring-closed structure polyimide, polybenzoxazole, or the like.
  • the content of the heterocyclic ring-containing polymer precursor in the composition used in the present invention is preferably 20 to 100% by mass, more preferably 50 to 99% by mass, and 70 to 98% by mass with respect to the total solid content of the composition. More preferred is 80 to 95% by mass.
  • components that can be contained in the composition used in the present invention will be described. It goes without saying that the present invention may contain components other than these, and these components are not essential.
  • the composition used in the present invention contains a crosslinking agent.
  • a crosslinking agent By including a crosslinking agent, the cyclization reaction of the heterocyclic ring-containing polymer precursor at a low temperature can be more effectively advanced. Furthermore, the cured film which was more excellent in heat resistance can be formed by containing a crosslinking agent. Moreover, pattern formation by photolithography can also be performed.
  • the content of the crosslinking agent is preferably 1 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount of the heterocyclic polymer precursor in the composition. Only one type of crosslinking agent may be used, or two or more types may be used. When using 2 or more types of crosslinking agents, it is preferable that a total amount becomes the said range.
  • the crosslinking agent is a compound having a crosslinkable group, and a known compound that can undergo a crosslinking reaction with a radical, an acid, a base, or the like can be used.
  • the crosslinkable group is a group capable of undergoing a crosslinking reaction by the action of actinic rays, radiation, radicals, acids, or bases.
  • Preferred examples include a group having an ethylenically unsaturated bond, a hydroxymethyl group, Examples include an acyloxymethyl group, an alkoxymethyl group, an epoxy group, an oxetanyl group, and a benzoxazolyl group.
  • the compound having an ethylenically unsaturated bond used in the present invention is more preferably a compound containing two or more ethylenically unsaturated groups, and more preferably a compound containing 2 to 6 ethylenically unsaturated groups.
  • a compound containing 2 to 4 ethylenically unsaturated groups is particularly preferable.
  • the cross-linking agent may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer and a mixture thereof, and a multimer thereof.
  • the compound having an ethylenically unsaturated bond is preferably a monomer.
  • the monomer type cross-linking agent (hereinafter also referred to as cross-linkable monomer) is a compound different from the polymer compound.
  • the crosslinkable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2,000 or less, more preferably a low molecular compound having a molecular weight of 1,500 or less, and a molecular weight of 900 or less. More preferably, it is a low molecular weight compound.
  • the molecular weight of the crosslinkable monomer is usually 100 or more.
  • the oligomer type crosslinking agent is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 crosslinking monomers are bonded.
  • the weight average molecular weight is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000.
  • the number of functional groups of the crosslinking agent means the number of crosslinkable groups in one molecule.
  • the crosslinking agent preferably contains at least one bifunctional or higher functional crosslinking agent containing two or more crosslinkable groups, and more preferably contains at least one trifunctional or higher functional crosslinking agent.
  • the upper limit of the crosslinkable group is not particularly defined, but is, for example, 8 or less, and preferably 6 or less.
  • the crosslinkable group is preferably a radical polymerizable group. That is, examples of the crosslinking agent in the present invention include compounds having two or more radically polymerizable groups.
  • the heterocyclic ring-containing polymer precursor satisfies one of a radical polymerizable group and a crosslinking agent having a radical polymerizable group.
  • the crosslinking agent in this invention contains at least 1 sort (s) of trifunctional or more than trifunctional crosslinking agents from the point that a three-dimensional crosslinked structure can be formed and heat resistance can be improved. Further, it may be a mixture of a bifunctional or lower functional crosslinking agent and a trifunctional or higher functional crosslinking agent.
  • ⁇ Compound having an ethylenically unsaturated bond As a group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.
  • the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof, amides, and these Preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof esters thereof, amides
  • these Preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof.
  • an addition reaction product of an ester or amide of an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy is also preferably used.
  • a substitution reaction product of an ester or amide of an unsaturated carboxylic acid having a leaving substituent such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate.
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (me
  • Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
  • crotonic acid esters examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • isocrotonic acid esters examples include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
  • maleic acid esters examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
  • esters examples include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240.
  • the compounds having an aromatic skeleton described in JP-A No. 59-5241, JP-A-2-226149, compounds containing an amino group described in JP-A 1-165613, and the like are also preferably used. It is done.
  • amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic.
  • examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • Examples of other preferable amide monomers include monomers having a cyclohexylene structure described in JP-B No. 54-21726.
  • urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable.
  • Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • Examples thereof include vinylurethane compounds containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula to a polyisocyanate compound having two or more isocyanate groups. .
  • CH 2 C (R 4) COOCH 2 CH (R 5) OH (Wherein, R 4 and R 5 represents H or CH 3.)
  • urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable.
  • the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.
  • the compound which has an ethylenically unsaturated bond the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable.
  • monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (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
  • n is an integer of 0 to 14, and m is an integer of 1 to 8.
  • a plurality of R and T present in one molecule may be the same or different.
  • Specific examples of the compound having an ethylenically unsaturated bond represented by the general formulas (MO-1) to (MO-5) are described in paragraph numbers 0248 to 0251 of JP-A-2007-267979. The compound can be suitably used in the present invention.
  • JP-A-10-62986 compounds represented by general formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol are also included. Can be used as a polymerizable compound.
  • Examples of the compound having an ethylenically unsaturated bond include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320).
  • the compound having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group.
  • the polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group.
  • the ester is a polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
  • Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the polyfunctional monomer having an acid group one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed.
  • a preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Moreover, the crosslinkability is good.
  • a compound having a caprolactone structure can also be used.
  • the compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • the compounds having a caprolactone structure and an ethylenically unsaturated bond can be used alone or in admixture of two or more.
  • the compound having an ethylenically unsaturated bond is also preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —
  • Each y independently represents an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy group.
  • the total number of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40 It is. However, when the sum of each m is 0, any one of X is a carboxy group.
  • the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 It is. However, when the total of each n is 0, any one of X is a carboxy group.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • bonds with is preferable.
  • a form in which all six Xs are acryloyl groups is preferable.
  • the compound represented by the general formula (i) or (ii) is a conventionally known process in which a ring-opening skeleton is bonded by a ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol. And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).
  • pentaerythritol derivatives and dipentaerythritol derivatives are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • Examples of the compound having an ethylenically unsaturated bond include those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is.
  • polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds. Monomers can also be used.
  • urethane oligomer UAS-10 UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A -9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Manufactured by Kyoeisha Chemical Co., Ltd.), Bremer PME400 (manufactured by NOF Corporation) and the like.
  • the compound having an ethylenically unsaturated bond preferably has a partial structure represented by the following formula from the viewpoint of heat resistance. However, * in the formula is a connecting hand.
  • Specific examples of the compound having an ethylenically unsaturated bond having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, and isocyanuric acid ethylene oxide-modified tri (meth).
  • the content of the compound having an ethylenically unsaturated bond is preferably 1 to 50% by mass with respect to the total solid content of the composition from the viewpoint of good crosslinkability and heat resistance.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 25% by mass or less.
  • the compound having an ethylenically unsaturated bond one kind may be used alone, or two or more kinds may be mixed and used.
  • the mass ratio of the heterocyclic ring-containing polymer precursor to the compound having an ethylenically unsaturated bond is preferably 98/2 to 10/90, and 95/5 to 30. / 70 is more preferable, 90/10 to 50/50 is more preferable, and 90/10 to 70/30 is still more preferable. If the mass ratio of the heterocyclic ring-containing polymer precursor and the compound having an ethylenically unsaturated bond is in the above range, a cured film having excellent crosslinkability and heat resistance can be formed.
  • the compound having an ethylenically unsaturated bond may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • R 4 represents a t-valent organic group having 1 to 200 carbon atoms
  • R 5 represents the following general formula (AM2) or the following general formula (AM3)). Represents a group to be selected.
  • R 6 represents a hydroxyl group or an organic group having 1 to 10 carbon atoms.
  • the content of the compound represented by the general formula (AM1) is preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor. More preferably, it is 10 to 35 mass parts. Moreover, 10 mass% or more and 90 mass% or less of the compound represented by the following general formula (AM4) are contained in all the crosslinking agents, and the compound represented by the following general formula (AM5) is 10 mass% or more in all the crosslinking agents. It is also preferable to contain 90 mass% or less. These compounds may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • R 4 represents a divalent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by the following general formula (AM2) or the following general formula (AM3).
  • R 4 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by the following general formula (AM2) or the following general formula (AM3) Is shown.
  • R 6 represents a hydroxyl group or an organic group having 1 to 10 carbon atoms.
  • R a is an organic group having 2 to 20 carbon atoms
  • P 1 is a hydrogen atom or an alkyl group.
  • R a is preferably a hydrocarbon group.
  • P 1 is preferably a hydrogen atom. Details of these can be referred to the description of paragraphs 0010 to 0024 of International Publication WO2010 / 038742, and the contents thereof are incorporated in the present specification.
  • a 5% mass reduction temperature is preferably 350 ° C. or higher, more preferably 380 ° C. or higher.
  • Specific examples of the compound represented by the general formula (AM4) include 46DMOC, 46DMOEP (trade name, 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 (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl -P-cresol and the like.
  • Specific examples of the compound represented by the general formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, and HML-TPPHBA.
  • HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)
  • TM-BIP-A trade name, manufactured by Asahi Organic Materials Co., Ltd.
  • NIKALAC MX-280, NIKACALAC MX-270, NIKALAC MW-100LM trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • the following compounds are also preferable as a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group.
  • T2058 and B1525 are illustrated.
  • Epoxy compound (compound having an epoxy group)>
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy compound undergoes a cross-linking reaction at 200 ° C. or lower and does not cause a dehydration reaction in the cross-linking reaction, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and low warpage of the composition.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compound examples include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (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 (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron (registered trademark) EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rikaresin (registered trademark) BEO-60E , New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by
  • an epoxy resin containing a polyethylene oxide group is preferable in terms of excellent low warpage and heat resistance.
  • Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
  • the content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor. If the blending amount is 5 parts by mass or more, warpage of the cured film can be further suppressed, and if it is 50 parts by mass or less, pattern filling accompanying reflow during final heating (curing) can be further suppressed.
  • the epoxy compound may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • oxetane compound (compound having oxetanyl group)>
  • the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester.
  • Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. More than one species may be mixed.
  • the content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor.
  • One oxetane compound may be used, or two or more oxetane compounds may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • ⁇ Benzoxazine compound (compound having benzoxazolyl group)> Since a benzoxazine compound undergoes a crosslinking reaction by a ring-opening addition reaction, no degassing due to curing occurs and shrinkage due to heat is small. For this reason, generation
  • benzoxazine compound examples include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzoxazine. Compounds. These may be used alone or in combination of two or more.
  • the content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor.
  • the benzoxazine compound may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the cross-linking agent used in the present invention preferably has a molecular weight of 100 to 1,500, more preferably 100 to 800, and even more preferably 100 to 600. By setting the molecular weight to 800 or less, further 600 or less, it is possible to more effectively improve the outgassing property.
  • composition in the present invention is an alkali-developable positive photosensitive resin composition
  • the inclusion of a resin containing a phenolic OH group adjusts the solubility in an alkali developer and provides good sensitivity. This is preferable.
  • Preferred examples of the resin containing a phenolic OH group include novolak resins and polyhydroxystyrene resins.
  • the novolak resin can be obtained by polycondensing phenols and aldehydes by a known method. Two or more novolac resins may be combined. Preferred examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol and the like.
  • the novolak resin preferably includes an m-cresol residue or a cresol novolak resin containing an m-cresol residue and a p-cresol residue.
  • the molar ratio of m-cresol residue to p-cresol residue (m-cresol residue / p-cresol residue, m / p) in the cresol novolak resin is preferably 1.8 or more. If it is this range, the moderate solubility to an alkali developing solution will be shown, and favorable sensitivity will be obtained. More preferably, it is 4 or more.
  • Preferred examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. Two or more of these aldehydes may be used.
  • R 1 represents an organic group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group
  • p is an integer of 1 to 3, preferably 2 to 3. It is an integer.
  • R 2 represents a group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group, and q is an integer of 0 to 3 inclusive.
  • a phenol compound having 1 to 3 and preferably 2 to 3 substituents is used, and the substituent has 1 or more carbon atoms. It is an organic group selected from 20 or less alkyl groups and alkoxy groups. Specific examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. Preferred examples of such a phenol compound include o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, and 3,4-dimethylphenol.
  • 3,5-dimethylphenol, 2-methyl-3-ethyl-phenol, 2-methyl-3-methoxyphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6 -Trimethylphenol or the like can be used.
  • 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,6-dimethylphenol Those selected from among them are preferred.
  • these phenols can be used alone or in combination of two or more.
  • the phenol resin has sufficient heat resistance necessary for the composition by suppressing intramolecular rotation. Can be obtained.
  • an aromatic aldehyde compound which is unsubstituted or has 3 or less substituents is used, and the substituent has 1 to 20 carbon atoms.
  • aromatic aldehyde compounds include benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehuman, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,3,4-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2,3,6-trimethylbenzaldehyde, 2, 4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-i Butylbenzaldehyde, 4-methoxybenzaldehyde, salicylaldehyde, 4-
  • an acidic catalyst is usually used.
  • the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like.
  • the amount of these acidic catalysts used is usually 1 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 1 mol per 1 mol of phenols.
  • water is usually used as a reaction medium. However, when a heterogeneous system is formed from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium.
  • hydrophilic solvent examples include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane.
  • lipophilic solvent examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.
  • the reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw material, but is usually 10 to 200 ° C.
  • phenols, aldehydes, acidic catalysts, etc. are charged all at once and reacted, or phenols, aldehydes, etc. are added as the reaction proceeds in the presence of acidic catalysts, etc. Can be adopted as appropriate.
  • the reaction temperature is generally increased to 130 to 230 ° C., and volatile components are reduced under reduced pressure. Remove and recover novolac resin.
  • the novolak resin has a polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of preferably 1,000 or more, and more preferably 2,000 or more. Moreover, 5,000 or less is preferable. Within this range, good sensitivity can be obtained.
  • Mw polystyrene equivalent weight average molecular weight
  • the content of the novolak resin is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the heterocyclic-containing polymer precursor. Within this range, a pattern that is highly sensitive and does not flow after heat treatment at a high temperature can be obtained. Only one type of novolac resin may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the hydroxystyrene resin is a polymer containing hydroxystyrene and / or a derivative thereof, and is not particularly limited, but may be a copolymer containing hydroxystyrene and / or a derivative thereof and a monomer other than these.
  • the monomer used here include ethylene, propylene, 1-butene, 2-methylpropene, styrene and derivatives thereof.
  • a copolymer composed of hydroxystyrene and / or a derivative thereof and styrene and / or a derivative thereof is preferable.
  • the above derivatives are those in which an alkyl group, an alkoxyl group, a hydroxy group or the like is substituted at the ortho, meta, and para positions of hydroxystyrene and the aromatic ring of styrene.
  • the hydroxystyrene of the hydroxystyrene resin may be any of orthohydroxystyrene, metahydroxystyrene, and parahydroxystyrene.
  • a plurality of the above hydroxystyrenes may be mixed.
  • the constituent ratio of the hydroxystyrene and its derivative in the hydroxystyrene resin is preferably 50% or more, and more preferably 60% or more.
  • the upper limit is preferably 90% or less, and more preferably 80% or less. By setting it as the said range, it has the effect excellent in coexistence of reduction of the post-exposure residue of an exposure part, and high sensitivity.
  • hydroxystyrene resins having a repeating structural unit represented by the following general formula (PHS-1) are preferred.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • a represents 1 to 4
  • b represents 1 to 3
  • a + b is within the range of 1 to 5.
  • R 2 represents an atom or one group selected from a hydrogen atom, a methyl group, an ethyl group, and a propyl group.
  • the structural unit represented by the general formula (PHS-1) is, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol.
  • aromatic vinyl compounds having a phenolic hydroxyl group such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, etc., alone or in combination, in a known manner. It is obtained by subjecting a part of the polymer or copolymer thus obtained to an addition reaction of an alkoxy group by a known method.
  • aromatic vinyl compound having a phenolic hydroxyl group p-hydroxystyrene and / or m-hydroxystyrene is preferably used, and styrene is preferably used as the aromatic vinyl compound.
  • the general formula (PHS ⁇ ) is used from the viewpoint of convenience that sensitivity can be further improved and solubility in an alkali developer can be adjusted.
  • a copolymer containing a structural unit represented by general formula (PHS-3) and general formula (PHS-4) is preferable.
  • the structural unit of the general formula (PHS-4) is preferably 50 mol% or less.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • c represents 1 to 4
  • d represents 1 to 3
  • c + d is in the range of 2 to 5 is there.
  • R 3 represents an atom or one group selected from a hydrogen atom, a methyl group, an ethyl group, and a propyl group.
  • R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e represents 1 to 5.
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the weight average molecular weight (Mw) of the hydroxystyrene resin is preferably 1,000 or more, more preferably 2,000 or more, particularly preferably 2,500 or more, and preferably 10,000 or less, more preferably 8, 000 or less, and particularly preferably 7,000 or less. By setting it as the said range, it has the effect which is excellent in coexistence of high-sensitivity and the normal temperature storage stability of a varnish.
  • the content of the hydroxystyrene resin is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor.
  • the composition in the present invention may contain a radical photopolymerization initiator.
  • the composition contains a photo-radical polymerization initiator
  • the composition is applied to a semiconductor wafer or the like to form a composition layer, and then irradiated with light to cause curing due to radicals and solubility in the light-irradiated part. Can be reduced.
  • region from which solubility differs can be easily produced according to the pattern of an electrode by exposing the said composition layer through the photomask with the pattern which masked only the electrode part, for example.
  • the radical photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known radical photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • an ultraviolet-visible spectrophotometer Cary-5 spect
  • radical photopolymerization initiator known compounds can be used without limitation.
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group
  • Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like.
  • halogenated hydrocarbon derivatives having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in GB 1388492, a compound described in JP-A-53-133428, a compound described in DE 3337024, F . C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, Examples include the compounds described in Japanese Patent No. 4221976.
  • Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) 1,3,4-oxadiazole, 2-trichloromethyl-5-
  • ketone compound examples include compounds described in paragraph No. 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kayacure DETX manufactured by Nippon Kayaku is also suitably used as a commercial product.
  • hydroxyacetophenone compounds As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator a compound described in JP-A-2009-191179 having an absorption maximum wavelength matched with a light source of 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • the metallocene compound include IRGACURE-784 (manufactured by BASF).
  • an oxime compound is more preferable.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Preferred oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.
  • Examples of the oxime compounds include JCSPerkin II (1979) p.1653-1660, JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP 2000 -66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • N-1919 manufactured by ADEKA
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arkles NCI-831 and Adeka Arkles NCI-930 made by ADEKA
  • WO2009 / 131189 US Patent containing triazine skeleton and oxime skeleton in the same molecule
  • the compound described in JP-A-7556910, the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used.
  • the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used.
  • the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorption and high sensitivity. It is preferable from the viewpoint.
  • a compound described in JP-A-2009-242469 which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used. It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph No. 0345 of JP-T-2014-500852, JP Examples thereof include compound (C-3) described in paragraph No. 0101 of 2013-164471. Specific examples include the following compounds. As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP 2007-26997A, and oxime compounds having a thioaryl group as disclosed in JP 2009-191061 A.
  • Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, tria from the viewpoint of exposure sensitivity.
  • Selected from the group consisting of a reel imidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and its derivative, a cyclopentadiene-benzene-iron complex and its salt, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound Are preferred.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds, and more preferred are trihalomethyltriazine compounds.
  • ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers and benzophenone compounds, and oxime compounds are most preferred.
  • the content of the radical photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the total solid content of the composition. More preferably, it is 0.1 to 10% by mass.
  • One type of radical photopolymerization initiator may be sufficient, and 2 or more types may be sufficient as it.
  • the total is preferably in the above range.
  • the composition in the present invention may contain a photoacid generator.
  • a photoacid generator By containing the photoacid generator, an acid is generated in the exposed area, and the solubility of the exposed area in the aqueous alkali solution is increased. Therefore, it can be used as a positive composition.
  • photoacid generators examples include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.
  • a quinonediazide compound is preferably used because it exhibits an excellent dissolution inhibiting effect and provides a composition with high sensitivity and small film loss.
  • quinonediazide sulfonic acid is ester-bonded to a polyhydroxy compound
  • quinonediazide sulfonic acid is sulfonamide-bonded to a polyamino compound
  • quinonediazide sulfonic acid is ester-bonded and / or sulfonamide to a polyhydroxypolyamino compound. Examples include those that are combined.
  • a positive composition sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which is a general ultraviolet ray can be obtained. .
  • all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferable that two or more functional groups per molecule are substituted with quinonediazide.
  • the following compounds are exemplified. In the above compound, 1 to 10% of the whole Q may be a hydrogen atom, and 4 to 6% may be a hydrogen atom.
  • Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TM -HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (
  • polyamino compounds examples include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diamino.
  • examples thereof include, but are not limited to, diphenyl sulfide.
  • examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but are not limited thereto.
  • both a compound having a 5-naphthoquinonediazidesulfonyl group and a compound having a 4-naphthoquinonediazidesulfonyl group are preferably used.
  • a compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.
  • Examples of the method for producing a quinonediazide compound include a method in which 5-naphthoquinonediazidesulfonyl chloride and a phenol compound are reacted in the presence of triethylamine.
  • Examples of the method for synthesizing a phenol compound include a method in which an ⁇ - (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acidic catalyst.
  • the content of the photoacid generator is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the heterocyclic ring-containing polymer precursor. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed. Only one type of photoacid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition in the present invention may contain a thermal acid generator.
  • a thermal acid generator is a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group in addition to generating an acid by heating and accelerating the cyclization of the heterocyclic-containing polymer precursor to further improve the mechanical properties of the cured film. And an effect of accelerating the crosslinking reaction of at least one compound selected from an epoxy compound, an oxetane compound and a benzoxazine compound.
  • the thermal decomposition starting temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 250 ° C. or less.
  • no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (curing: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select one that generates an acid, since a decrease in sensitivity during development can be suppressed.
  • the acid generated from the thermal acid generator is preferably a strong acid.
  • arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid
  • alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid
  • trifluoromethane Haloalkyl sulfonic acids such as sulfonic acid are preferred.
  • Examples of such a thermal acid generator include those described in paragraph No. 0055 of JP2013-072935A.
  • those that generate an alkylsulfonic acid having 1 to 4 carbon atoms and a haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonate (4-((methoxy Carbonyl) oxy) phenyl) methylsulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy
  • JP2013-167742A is also preferable as the thermal acid generator.
  • thermal acid generator 0.01 mass part or more is preferable with respect to 100 mass parts of heterocyclic containing polymer precursors, and 0.1 mass part or more is more preferable.
  • 0.01 part by mass or more By containing 0.01 part by mass or more, the crosslinking reaction and the cyclization of the heterocyclic ring-containing polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
  • 20 mass parts or less are preferable, 15 mass parts or less are more preferable, and 10 mass parts or less are more preferable.
  • One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition in the present invention may contain a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator a known thermal radical polymerization initiator can be used.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the heterocyclic ring-containing polymer precursor is advanced.
  • the polymerization reaction of the heterocyclic ring-containing polymer precursor can be allowed to proceed together with the cyclization of the heterocyclic ring-containing polymer precursor.
  • Thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound.
  • the thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C. Specific examples include compounds described in paragraph numbers 0074 to 0118 of JP-A-2008-63554. In a commercial item, perbutyl Z and park mill D (made by NOF Corporation) can be used conveniently.
  • the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass with respect to the total solid content of the composition. Preferably, 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.
  • a corrosion inhibitor is added for the purpose of preventing the outflow of ions from the metal wiring.
  • the compound include a rust inhibitor described in paragraph No. 0094 of JP2013-15701A, and JP2009-283711A.
  • the compounds described in Paragraph Nos. 0073 to 0076, the compound described in Paragraph No. 0052 of JP 2011-59656 A, the compounds described in Paragraph Nos. 0114, 0116, and 0118 of JP 2012-194520 A are used. be able to.
  • a compound having a triazole ring or a compound having a tetrazole ring can be preferably used.
  • the content of the corrosion inhibitor is preferably in the range of 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor. Part range.
  • the corrosion inhibitor may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition in the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for electrodes, wirings and the like.
  • metal adhesion improvers include sulfide compounds described in paragraph numbers 0046 to 0049 of JP-A-2014-186186 and paragraph numbers 0032 to 0043 of JP-A-2013-072935.
  • the metal adhesion improver also include the following compounds.
  • the content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts per 100 parts by mass of the polyimide precursor. It is the range of mass parts.
  • membrane and metal after thermosetting becomes favorable, and the heat resistance of the film
  • Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
  • the composition in the present invention preferably contains a silane coupling agent in terms of improving the adhesion to the substrate.
  • the silane coupling agent include compounds described in paragraph numbers 0062 to 0073 of JP2014-191002, compounds described in paragraph numbers 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252.
  • the content of the silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor. Part range.
  • silane coupling agent Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • a dissolution accelerator a compound that promotes solubility
  • the solubility promoter include low molecular weight phenols (for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P (trade name, manufactured by Honshu Chemical Industry), BIR- PC, BIR-PTBP, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.), phenols described in paragraph numbers 0056 to 0062 of JP2013-152381A) and arylsulfonamide derivatives (for example, And compounds described in paragraph No.
  • the content of the dissolution accelerator is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor. It is a range. Only one type of dissolution promoter may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • composition in the present invention is a positive type using an alkali developer, it can contain a dissolution inhibitor (a compound that inhibits solubility) in order to adjust the solubility in an alkali developer.
  • a dissolution inhibitor a compound that inhibits solubility
  • onium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts, aryldiazonium salts, and the like.
  • diaryl compound examples include those in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are bonded via a linking group. Groups are preferred.
  • aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are bonded via a linking group. Groups are preferred.
  • tetraalkylammonium salt examples include tetraalkylammonium halides in which the alkyl group is a methyl group or an ethyl group.
  • those showing a good dissolution inhibiting effect include diaryl iodonium salts, diaryl ureas, diaryl sulfones, tetramethyl ammonium halides, etc.
  • diaryl ureas include diphenyl urea, dimethyl diphenyl urea, etc.
  • the methylammonium halide include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.
  • a diaryl iodonium salt represented by the general formula (Inh) is preferable.
  • X - represents a counteranion
  • R 7 and R 8 each independently represents a monovalent organic group
  • a and b are each independently an integer of 0 to 5
  • Examples of the counter anion X ⁇ include nitrate ion, boron tetrafluoride ion, perchlorate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, thiocyanate ion, chlorine ion, bromine ion, iodine ion and the like. It is done.
  • diaryliodonium salt examples include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, and diphenyliodonium.
  • diphenyliodonium chloride, diphenyliodonium iodide, diphenyliodonium-8-anilinonanaphthalene-1-sulfonate and the like can be used.
  • diphenyliodonium nitrate diphenyliodonium trifluoromethanesulfonate
  • diphenyliodonium-8-anilinonanaphthalene-1-sulfonate are preferable because of their high effects.
  • the content of the dissolution inhibitor is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the heterocyclic-containing polymer precursor from the viewpoints of sensitivity and an allowable range of development time. 0.1 to 15 parts by mass is more preferable, and 0.5 to 10 parts by mass is further preferable. Only one type of dissolution inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition in the present invention may contain a sensitizing dye.
  • a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizing dye in an electronically excited state is brought into contact with an amine generator, a thermal radical polymerization initiator, a photo radical polymerization initiator or the like, and causes actions such as electron transfer, energy transfer, and heat generation.
  • an amine generator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases.
  • preferable sensitizing dyes include those belonging to the following compounds and having a maximum absorption wavelength in the range of 300 nm to 450 nm.
  • polynuclear aromatics eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene
  • xanthenes eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • thioxanthones eg, 2,4-diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines eg, merocyanine, carbomerocyanine
  • thiazines eg, thionine, methylene blue, toluidine blue
  • acridines For example, acridine orange, chloroflavin, a
  • polynuclear aromatics for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, thioxanthones
  • distyrylbenzenes for example, thioxanthones
  • distyrylbenzenes for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, thioxanthones
  • distyrylbenzenes for example, thioxanthones
  • distyrylbenzenes for example, thioxanthones
  • the content of the sensitizing dye is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 15% by mass, based on the total solid content of the composition. More preferably, it is 5 to 10% by mass.
  • a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
  • the composition in the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in Polymer Dictionary 3rd 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, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • 2-mercaptobenzimidazoles for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the composition. More preferably, it is 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
  • the composition in the present invention preferably contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the heterocyclic-containing polymer precursor and the radical polymerizable compound during production or storage.
  • a polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert).
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • Various surfactants may be added to the composition of the present invention from the viewpoint of further improving coatability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • a fluorosurfactant liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved.
  • the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coated surface The coating property of is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • a block polymer can also be used as the fluorosurfactant, and specific examples include compounds described in JP2011-89090A.
  • the following compounds are also exemplified as the fluorosurfactant used in the present invention.
  • the weight average molecular weight of the above compound is, for example, 14,000.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 , Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.% by mass with respect to the total solid content of the composition. 0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more surfactants, the total is preferably in the above range.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the composition in the present invention, and it is unevenly distributed on the surface of the composition in the drying process after coating. May be.
  • the content of the higher fatty acid derivative or the like is preferably 0.1 to 10% by mass with respect to the total solid content of the composition. Only one type of higher fatty acid derivative or the like may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
  • ⁇ Solvent> When making the composition in this invention into a layer form by application
  • Any known solvent can be used without limitation as long as the composition can be formed into a layer.
  • the solvent used in the composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and lactic acid.
  • the solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface.
  • a mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is preferable.
  • the content of the solvent is preferably such that the total solid concentration of the composition is 5 to 80% by mass from the viewpoint of applicability, more preferably 5 to 70% by mass. Preferably, 10 to 60% by mass is more preferable.
  • One type of solvent may be sufficient and 2 or more types may be sufficient as it.
  • the total is preferably in the above range.
  • the contents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide are based on the total mass of the composition from the viewpoint of film strength. It is preferably less than 5% by mass, more preferably less than 1% by mass, further preferably less than 0.5% by mass, and still more preferably less than 0.1% by mass.
  • the composition in the present invention is within the range that does not impair the effects of the present invention, and various additives as necessary, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation.
  • An agent or the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the composition.
  • the water content of the composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of the coated surface.
  • the metal content of the composition in the present invention is preferably less than 5 ppm by weight, more preferably less than 1 ppm by weight, and even more preferably less than 0.5 ppm by weight from the viewpoint of insulation.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the composition, and filter filtration is performed on the raw material constituting the composition. Examples thereof include a method of performing distillation under a condition in which the inside of the apparatus is lined with polytetrafluoroethylene or the like and contamination is suppressed as much as possible.
  • the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosivity.
  • a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.
  • the composition in 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 pore size of the filter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • you may pressurize and filter and the pressure to pressurize is 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent.
  • filtration using a filter and removal of impurities using an adsorbent may be combined.
  • known adsorbents can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • the method for producing a cured film of the present invention can be preferably used in the fields of insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. That is, this invention also discloses the manufacturing method of a semiconductor device containing the manufacturing method of the cured film of this invention. In particular, since the resolution is good, it can be preferably used for manufacturing an interlayer insulating film for a rewiring layer in a three-dimensional mounting device. That is, this invention also discloses the manufacturing method of the interlayer insulation film for rewiring layers including the manufacturing method of the cured film of this invention.
  • the cured film obtained by the manufacturing method of the cured film of this invention and the semiconductor device obtained by the manufacturing method of the cured film of this invention are disclosed.
  • the cured film produced according to the present invention can also be used for a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist).
  • the cured film produced according to the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, the use for etching molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics, etc. .
  • a semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
  • the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described.
  • the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.
  • Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate.
  • the uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
  • the semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.
  • the stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump.
  • connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.
  • An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.
  • the stacked body 101 is stacked on the wiring board 120.
  • the wiring substrate 120 for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used.
  • the wiring substrate 120 to which the resin substrate is applied include a multilayer copper clad laminate (multilayer printed wiring board).
  • a surface electrode 120 a is provided on one surface of the wiring board 120.
  • An insulating layer 115 in which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected.
  • the insulating layer 115 is formed using the photosensitive resin composition in the present invention. That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump.
  • the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
  • An underfill layer 110 a is formed between the insulating layer 115 and the stacked body 101.
  • an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.
  • the cured film produced according to the present invention can be widely used in various applications using polyimide or polybenzoxazole.
  • polyimide and polybenzoxazole are resistant to heat
  • cured films and the like produced by the present invention are used for transparent plastic substrates for liquid crystal displays, display devices such as electronic paper, automotive parts, heat resistant paints, coating agents, and films. Can also be suitably used.
  • Mw and Mn are polystyrene conversion values measured by gel permeation chromatography (GPC), and were measured by the following method.
  • HLC-8220 manufactured by Tosoh Corp.
  • the eluent was measured using THF (tetrahydrofuran) at 40 ° C.
  • UV 254 nm detector was used for detection.
  • a sample in which a heterocyclic ring-containing polymer precursor was diluted and adjusted to 0.1% by mass with THF was used.
  • the polybenzoxazole precursor was collected by filtration, poured into 6 liters of water again, stirred for another 30 minutes, and filtered again. Next, the obtained polybenzoxazole precursor was dried at 45 ° C. under reduced pressure for 3 days. This polybenzoxazole precursor had a weight average molecular weight of 11,500, a number average molecular weight of 6,800, and a dispersity of 1.7.
  • Polybenzoxazole was collected by filtration, poured into 6 liters of water again, stirred for another 30 minutes, and filtered again. Subsequently, the obtained polybenzoxazole was dried at 45 ° C. under reduced pressure for 3 days. This polybenzoxazole had a weight average molecular weight of 17,500, a number average molecular weight of 10,000, and a dispersity of 1.8.
  • Synthesis Example 6 PIp-C>
  • the same procedure was performed except that 21.2 g of 4,4′-oxydiphthalic dianhydride was changed to 20.1 g of diphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride.
  • a polyimide precursor was obtained.
  • 20.1 g of diphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (dried at 140 ° C.
  • composition of composition >> Heterocycle-containing polymer precursor:% by mass shown in Table 6 or 7 Amine generator: mass% as described in Table 6 or 7 Polymerization initiator: mass% described in Table 6 or 7 Crosslinking agent:% by mass described in Table 6 or 7 Solvent: mass% listed in Table 6 or 7
  • PIp-A of the heterocyclic ring-containing polymer precursor indicates the kind of the precursor, and the value “33” indicates the blending amount (unit: mass%) in the composition.
  • PIp-A indicates the kind of the precursor
  • value “33” indicates the blending amount (unit: mass%) in the composition.
  • TBG4 has an amine generation temperature of 145 ° C.
  • TBG5 has an amine generation temperature of 150 ° C.
  • TBG6 has an amine generation temperature of 180 ° C.
  • INI1 is IRGACURE-OXE01 manufactured by BASF.
  • INI2 is IRGACURE-OXE02 manufactured by BASF.
  • INI3 was synthesized by the method described in Synthesis Example 4 in the pamphlet of International Publication WO05 / 069075.
  • INI4 is IRGACURE784 manufactured by BASF.
  • SLV1 ⁇ -butyrolactone
  • SLV2 dimethyl sulfoxide
  • SLV3 N-methyl-2-pyrrolidone
  • the link 1 has a molecular weight of 330 and is 4G manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the link 2 has a molecular weight of 536 and is 9G manufactured by Shin-Nakamura Chemical Co., Ltd.
  • link3 has a molecular weight of 1136 and is 23G manufactured by Shin-Nakamura Chemical Co., Ltd.
  • link4 has a molecular weight of 318 and is T2058 manufactured by Tokyo Chemical Industry.
  • the link 5 has a molecular weight of 168 and is B1525 manufactured by Tokyo Chemical Industry.
  • link6 has a molecular weight of 951.
  • ⁇ Amine amount> The amount of amine in the cured film was quantified under the following conditions using gas chromatography (manufactured by Agilent) connected with a headspace sampler.
  • a 4-inch silicon wafer (1 inch is 2.54 cm) was spin-coated with the composition described in Table 6 or 7 at 1,000 rpm, and heated on a hot plate at 100 ° C. for 2 minutes to form a film.
  • the obtained wafer was heat-cured on the hot plate under a nitrogen stream under the conditions shown in Table 6 or 7.
  • the heating temperature in Tables 6 and 7 means the maximum heating temperature at the time of heat curing, and the heating time means the heating time after reaching the maximum heating temperature.
  • the temperature at the start of temperature rise is 25 degreeC.
  • the obtained wafer was divided, filled into 20 mL vials, and the components in the cured film were volatilized with a headspace sampler at 230 ° C. for 7 minutes.
  • the volatilized component was introduced into gas chromatography (manufactured by Agilent) and heated at 150 ° C. for 5 minutes using a capillary column HP-1MS (manufactured by Agilent), and then heated at a temperature rising rate of 5 ° C./min. It isolate
  • the amine content in the cured film was calculated from the peak area of the obtained amine and the separately prepared amine calibration curve.
  • the corresponding amine was weighed into various amounts of vials, measured under the same conditions as the sample, and a calibration curve was created from the obtained peak area and the weighed value.
  • a 4-inch silicon wafer was spin-coated with the composition described in Table 6 or 7 at 1,000 rpm, and heated on a hot plate at 100 ° C. for 2 minutes to form a film.
  • the obtained wafer was heat-cured on the hot plate under a nitrogen stream under the conditions shown in Table 6 or 7. After curing, the resulting wafer was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropyl alcohol, and then air-dried. The presence or absence of cracks in the cured film of the obtained wafer was visually observed.
  • the chemical resistance was evaluated from the following viewpoints. A: No cracks were found on the entire wafer surface B: Cracks were found on part of the wafer C: Cracks were found on the entire wafer surface
  • a cured film having excellent corrosion resistance and chemical resistance was obtained by the production method of the present invention.
  • a cured film having more excellent various performances was obtained.
  • Example 100 The photosensitive resin composition of Example 11 was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m, and then applied to a resin substrate on which a copper thin layer was formed by spinning (3,500 rpm, 30 seconds). did.
  • the photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes, and then exposed using an aligner (Karl-Suss MA150). Exposure was performed with a high-pressure mercury lamp, and exposure energy at a wavelength of 365 nm was measured. After exposure, the image was developed with cyclopentanone for 75 seconds. Subsequently, it heated at 180 degreeC for 20 minutes.

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Abstract

L'invention concerne un procédé de fabrication d'un film durci doté d'excellentes résistance à la corrosion et résistance chimique. L'invention concerne également un procédé de fabrication d'un film isolant intercouche pour une couche de recâblage, ainsi qu'un procédé de fabrication d'un dispositif semi-conducteur, mettant en oeuvre le procédé de fabrication de film durci. La présente invention concerne en particulier un procédé de fabrication d'un film durci présentant une teneur en amines de 50 à 5 000 ppm, ledit procédé consistant à chauffer, à une température ne dépassant pas une température de chauffage maximale de 250 °C, une couche contenant une composition comprenant un agent générant une amine et un précurseur de polyimide et/ou un précurseur de polybenzoxazole.
PCT/JP2016/074742 2015-08-28 2016-08-25 Procédé de fabrication de film durci, procédé de fabrication de film isolant intercouche pour couche de recâblage, et procédé de fabrication de dispositif semi-conducteur Ceased WO2017038598A1 (fr)

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JP2017537787A JP6511146B2 (ja) 2015-08-28 2016-08-25 硬化膜の製造方法、再配線層用層間絶縁膜の製造方法、および、半導体デバイスの製造方法

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WO2018181182A1 (fr) * 2017-03-29 2018-10-04 富士フイルム株式会社 Composition de résine photosensible, film durci, stratifié, procédé de production de film durci, et dispositif à semi-conducteur
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TWI669569B (zh) * 2017-07-14 2019-08-21 南韓商Ｌｇ化學股份有限公司 製造絕緣膜和半導體封裝的方法
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007056196A (ja) * 2005-08-26 2007-03-08 Tokyo Institute Of Technology ポリイミド前駆体組成物、ポリイミド膜の製造方法及び半導体装置
JP2007056182A (ja) * 2005-08-26 2007-03-08 Fuji Xerox Co Ltd ポリアミック酸組成物、ポリイミド無端ベルト、及び画像形成装置
WO2015199219A1 (fr) * 2014-06-27 2015-12-30 富士フイルム株式会社 Générateur de base thermique, composition de résine thermodurcissable, film durci, procédé de fabrication de film durci, et dispositif semi-conducteur

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102076774B (zh) * 2008-04-28 2014-07-09 日本瑞翁株式会社 辐射敏感树脂组合物、叠层体及其制造方法、以及半导体器件
TWI486335B (zh) * 2011-12-29 2015-06-01 Eternal Materials Co Ltd 鹼產生劑

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007056196A (ja) * 2005-08-26 2007-03-08 Tokyo Institute Of Technology ポリイミド前駆体組成物、ポリイミド膜の製造方法及び半導体装置
JP2007056182A (ja) * 2005-08-26 2007-03-08 Fuji Xerox Co Ltd ポリアミック酸組成物、ポリイミド無端ベルト、及び画像形成装置
WO2015199219A1 (fr) * 2014-06-27 2015-12-30 富士フイルム株式会社 Générateur de base thermique, composition de résine thermodurcissable, film durci, procédé de fabrication de film durci, et dispositif semi-conducteur

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2018181182A1 (ja) * 2017-03-29 2020-05-14 富士フイルム株式会社 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法および半導体デバイス
US11480876B2 (en) 2017-03-29 2022-10-25 Fujifilm Corporation Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device
WO2018181182A1 (fr) * 2017-03-29 2018-10-04 富士フイルム株式会社 Composition de résine photosensible, film durci, stratifié, procédé de production de film durci, et dispositif à semi-conducteur
KR20190120320A (ko) * 2017-03-29 2019-10-23 후지필름 가부시키가이샤 감광성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법 및 반도체 디바이스
KR102266086B1 (ko) * 2017-03-29 2021-06-17 후지필름 가부시키가이샤 감광성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법 및 반도체 디바이스
US11361878B2 (en) 2017-07-14 2022-06-14 Lg Chem, Ltd. Method for manufacturing insulating film and semiconductor package
TWI669569B (zh) * 2017-07-14 2019-08-21 南韓商Ｌｇ化學股份有限公司 製造絕緣膜和半導體封裝的方法
KR20190082602A (ko) * 2018-01-02 2019-07-10 삼성전자주식회사 포토레지스트 현상액 조성물 및 이를 이용한 반도체 패키지 제조방법
US10908505B2 (en) 2018-01-02 2021-02-02 Samsung Electronics Co., Ltd. Photoresist developer composition and manufacturing method of semiconductor package using the same
KR102089286B1 (ko) * 2018-01-02 2020-03-16 삼성전자주식회사 포토레지스트 현상액 조성물 및 이를 이용한 반도체 패키지 제조방법
WO2021020463A1 (fr) 2019-07-29 2021-02-04 旭化成株式会社 Composition de résine photosensible négative, procédé de production de polyimide, procédé de production de motif en relief durci, et dispositif à semi-conducteur
WO2021100768A1 (fr) 2019-11-21 2021-05-27 富士フイルム株式会社 Procédé de formation de motif, composition de résine photodurcissable, procédé de fabrication de corps stratifié et procédé de fabrication de dispositif électronique
WO2022172962A1 (fr) * 2021-02-12 2022-08-18 富士フイルム株式会社 Composition de résine, produit durci, corps stratifié, procédé de fabrication d'un produit durci, dispositif à semi-conducteur et précurseur de résine de cyclisation
JPWO2022172962A1 (fr) * 2021-02-12 2022-08-18
WO2022202647A1 (fr) 2021-03-22 2022-09-29 富士フイルム株式会社 Composition de résine photosensible négative, produit durci, stratifié, procédé de production d'un produit durci et dispositif à semi-conducteur
WO2023032545A1 (fr) 2021-08-31 2023-03-09 富士フイルム株式会社 Procédé de production de produit durci, procédé de production de stratifié, procédé de fabrication de dispositif à semi-conducteur et liquide de traitement
WO2023120037A1 (fr) 2021-12-23 2023-06-29 富士フイルム株式会社 Procédé de production de corps assemblé, corps assemblé, procédé de production de stratifié, stratifié, procédé de production de dispositif, dispositif et composition pour former une partie précurseur contenant du polyimide
WO2023162687A1 (fr) 2022-02-24 2023-08-31 富士フイルム株式会社 Composition de résine, article durci, stratifié, procédé de production d'article durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2023190064A1 (fr) 2022-03-29 2023-10-05 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2024010026A1 (fr) * 2022-07-08 2024-01-11 富士フイルム株式会社 Composition de résine, produit durci, corps multicouche, procédé de production d'un produit durci, procédé de production d'un corps multicouche, procédé de production d'un dispositif semiconducteur et dispositif semiconducteur
WO2024070963A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Procédé de production de film, composition de résine photosensible, procédé de production de produit durci, produit durci et stratifié
WO2024071237A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2024071380A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci

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TW201714934A (zh) 2017-05-01
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