WO2022059506A1 - 珪素含有モノマー混合物、ポリシロキサン、樹脂組成物、感光性樹脂組成物、硬化膜、硬化膜の製造方法、パターン硬化膜及びパターン硬化膜の製造方法 - Google Patents

珪素含有モノマー混合物、ポリシロキサン、樹脂組成物、感光性樹脂組成物、硬化膜、硬化膜の製造方法、パターン硬化膜及びパターン硬化膜の製造方法 Download PDF

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WO2022059506A1
WO2022059506A1 PCT/JP2021/032337 JP2021032337W WO2022059506A1 WO 2022059506 A1 WO2022059506 A1 WO 2022059506A1 JP 2021032337 W JP2021032337 W JP 2021032337W WO 2022059506 A1 WO2022059506 A1 WO 2022059506A1
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group
cured film
polysiloxane
carbon atoms
general formula
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French (fr)
Japanese (ja)
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毅 増渕
友大 片村
一広 山中
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Central Glass Co Ltd
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Central Glass Co Ltd
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Priority to JP2022550461A priority Critical patent/JPWO2022059506A1/ja
Priority to CN202180054622.0A priority patent/CN116034127B/zh
Priority to KR1020237011920A priority patent/KR20230062644A/ko
Publication of WO2022059506A1 publication Critical patent/WO2022059506A1/ja
Priority to US18/184,354 priority patent/US20230244145A1/en
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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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/247—Heating methods
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • C08G2150/00—Compositions for coatings
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the present disclosure discloses a silicon-containing monomer mixture, a resin composition containing a polymer compound containing a siloxane bond, a photosensitive resin composition, a cured film, and a pattern, which can be used as various optical devices, photosensitive materials, encapsulants, and the like.
  • the present invention relates to a cured film and a method for producing them.
  • Polymer compounds containing siloxane bonds utilize their high heat resistance and transparency, and are used as coating materials for liquid crystal displays and organic EL displays, coating materials for image sensors, and semiconductor fields. It is used as a sealing material in. Further, since polysiloxane has high oxygen plasma resistance, it is also used as a hard mask material for a multilayer resist. In order to use the polysiloxane as a patternable photosensitive material, it is required that the polysiloxane is soluble in an alkaline aqueous solution such as an alkaline developer.
  • a silanol group in the polysiloxane As a means for solubilizing the polysiloxane in the alkaline developer, there are examples of using a silanol group in the polysiloxane and introducing an acidic group into the polysiloxane.
  • an acidic group include a phenol group, a carboxyl group, a fluorocarbinol group and the like.
  • Patent Document 1 discloses a polysiloxane using a silanol group as a soluble group in an alkaline developer.
  • a polysiloxane having a phenol group is disclosed in Patent Document 2.
  • Patent Document 3 discloses a polysiloxane having a carboxyl group.
  • Patent Document 4 discloses a polysiloxane having a hexafluoroisopropanol group (2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [ ⁇ C (CF 3 ) 2 OH]].
  • these polysiloxanes are used as positive resist compositions.
  • the polysiloxane comprising the above has good transparency, heat resistance, and acid resistance. Therefore, a pattern structure based on the polysiloxane is promising as a permanent structure in various devices.
  • Japanese Unexamined Patent Publication No. 2012-242600 Japanese Unexamined Patent Publication No. 4-130324 Japanese Unexamined Patent Publication No. 2005-330488 JP-A-2015-129908 Japanese Unexamined Patent Publication No. 2014-156461
  • one object is to provide a polysiloxane having a high polymerization reaction rate and good storage stability.
  • Another object of the present invention is to provide a silicon-containing monomer mixture as a raw material of the polysiloxane, a resin composition containing the polysiloxane, a photosensitive resin composition, a cured film or a pattern cured film.
  • Another object of the present invention is to provide a resin composition containing the polysiloxane, a photosensitive resin composition, a cured film, or a method for producing a pattern cured film.
  • A is the content of the first silicon-containing monomer
  • B is the content of the second silicon-containing monomer
  • the molar ratio is B / (A + B)> 0.04
  • R 1s when there are a plurality of R 1s , each of them is independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, and a branched form having 3 to 10 carbon atoms.
  • R 2 is independently a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, and hydrogen in the alkyl group. All of the atoms may or may not be substituted with hydrogen atoms. Further, a part of the hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • R 1 , R 2 , R x , a and b are the same as those in the general formula (X).
  • each of the R 3s has a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, and a branched form having 3 to 10 carbon atoms.
  • R x is a hydrogen atom or an acid instability group.
  • m is a number of 0 or more and less than 3
  • n is a number of more than 0 and 3 or less
  • m + n 3.
  • R 3 , R x , m and n are the same as those in the general formula (1).
  • a film forming step of applying the photosensitive resin composition on the substrate to form a photosensitive resin film and The exposure process for exposing the photosensitive resin film and A developing process for developing a photosensitive resin film after exposure to form a patterned resin film, A curing process that turns the pattern resin film into a pattern curing film by heating the pattern resin film, A method for producing a pattern cured film containing the above is provided.
  • the photosensitive resin composition is (A) The above-mentioned polysiloxane as a component and (B) At least one photosensitive agent selected from the group consisting of a quinonediazide compound, a photoacid generator, a photobase generator, and a photoradical generator as a component. (C) A solvent may be contained as a component.
  • a polysiloxane having a high polymerization reaction rate and good storage stability is provided.
  • a silicon-containing monomer mixture which is a raw material of the polysiloxane, a resin composition containing the polysiloxane, a photosensitive resin composition, a cured film or a pattern cured film is provided.
  • a resin composition containing the polysiloxane, a photosensitive resin composition, a cured film or a method for producing a pattern cured film is provided.
  • a polysiloxane for an optical member a silicon-containing monomer mixture as a raw material of the polysiloxane (hereinafter, may be simply referred to as “mixture”), and a resin containing the polysiloxane.
  • the composition, the photosensitive resin composition, the cured film, the pattern cured film, and the method for producing them will be described.
  • the embodiments of the present invention are not construed as being limited to the contents described in the embodiments and examples shown below.
  • the notation "XY" in the description of the numerical range means X or more and Y or less unless otherwise specified.
  • the conventional polysiloxane After polymerizing the silicon-containing monomer as a raw material to obtain polysiloxane, the conventional polysiloxane is usually stored in a refrigerator. The faster the polymerization reaction rate, the higher the production efficiency. However, according to the study by the present inventors, if the polymerization reaction rate of the silicon-containing monomer is high, the obtained polysiloxane can be obtained even under refrigeration. It has become clear that the stability of the product during storage may be insufficient.
  • the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • cyclic alkyl group includes not only a monocyclic structure but also a polycyclic structure. The same applies to the "cycloalkyl group”.
  • (meth) acrylic in this specification represents a concept that includes both acrylic and methacrylic acid. The same applies to similar notations such as "(meth) acrylate”.
  • organic group in the present specification means an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
  • the “monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
  • hexafluoroisopropanol group represented by -C (CF 3 ) 2 OH may be referred to as "HFIP group”.
  • the mixture described below is one of the embodiments.
  • the mixture according to the present embodiment contains a silicon-containing monomer represented by the following general formula (X) and a silicon-containing monomer represented by the following general formula (Y).
  • A the content of the silicon-containing monomer represented by the general formula (X) contained in the mixture according to the present embodiment
  • B the content of the silicon-containing monomer represented by the general formula (Y)
  • B the content of the silicon-containing monomer represented by the general formula (Y)
  • the mixture according to the present embodiment can improve the reaction rate of the polymerization reaction.
  • the silicon-containing monomer (X) has a bulky HFIP group at the meta position
  • the silicon-containing monomer (Y) has a bulky HFIP group at the para position.
  • the silicon-containing monomer (Y) since the HFIP group is present at the para position farther from the silicon atom, the silicon atom is vulnerable to a nucleophilic attack by a nucleophile, and a hydrolysis reaction or a polycondensation reaction occurs. It is presumed that (formation of siloxane bond by dehydration) is likely to occur.
  • the value of B / (A + B) may be preferably 0.05 or more, more preferably 0.1 or more. Further, if it is a mixture, the upper limit value is not particularly limited, but may be, for example, 0.95 or less. Further, it is preferably 0.9 or less for the purpose of obtaining good storage stability of the polysiloxane described later.
  • each of the R 1s has a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, and a branched form having 3 to 10 carbon atoms.
  • all the hydrogen atoms in the alkyl group, the alkenyl group, or the phenyl group may or may not be substituted with the fluorine atom.
  • a part of the hydrogen atom in the alkyl group, the alkenyl group, or the phenyl group may be substituted with the fluorine atom.
  • each of them is an independent linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms.
  • all the hydrogen atoms in the alkyl group may or may not be substituted by the fluorine atom.
  • a part of the alkyl group may be substituted with a fluorine atom.
  • R x is a hydrogen atom or an acid instability group.
  • a is an integer of 0 to 2
  • b is an integer of 1 to 3
  • a + b 3 Satisfy the relationship.
  • Examples of the acid instability group include an alkyloxycarbonyl group, an acetal group, a silyl group, an acyl group and the like.
  • Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an i-propoxycarbonyl group.
  • acetal group examples include methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group and ethoxybutyl group. And ethoxyisobutyl group and the like. Further, an acetal group in which vinyl ether is added to a hydroxyl group can also be used.
  • silyl group examples include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, a tri-i-propylsilyl group and t-butyl.
  • Examples thereof include a dimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, a triphenylsilyl group and the like.
  • acyl group examples include an acetyl group, a propionyl group, a butyryl group, a heptanoyle group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a laurylloyl group, a myritoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group and a succinyl group.
  • Glutaryl group adipoil group, piperoyl group, suberoyl group, azella oil group, sebacyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoil group, fumaroyl group, mesaconoyl group, canhoroyl group, benzoyl group, phthaloyl group.
  • Examples thereof include a group, an isophthaloyl group, a terephthaloyl group, a naphthoyl group, a toluoil group, a hydroatropoil group, an atropoyl group, a cinnamoyl group, a floyl group, a tenoyl group, a nicotinoyle group, and an isonicotinoyl group.
  • these acid unstable groups in which some or all hydrogen atoms are replaced with fluorine atoms can also be used.
  • R 1 , R 2 , R x , a and b are the same as the definitions of R 1 , R 2 , R x , a and b in the general formula (X).
  • the method for producing the silicon-containing monomer (X) is not particularly limited. A typical manufacturing method will be described below.
  • the compound represented by the general formula (X) is known, and for example, the compound represented by the general formula (X) can be synthesized by referring to the method described in Patent Document 5.
  • the compound represented by the general formula (Y) is known, and for example, the compound represented by the general formula (Y) can be synthesized with reference to the method described in Patent Document 5.
  • the mixture may contain a solvent or the like.
  • the solvent is not particularly limited as long as it does not react with the compound represented by the general formula (X) and the compound represented by the general formula (Y), and hydrocarbons such as pentane, hexane, heptane, octane and toluene are not particularly limited.
  • Solvents such as tetrahydrofuran, diethyl ether, dibutyl ether, diisopropyl ether, methyl tertiary butyl ether, 1,2-dimethoxyethane, 1,4-dioxane, methanol, ethanol, 1-propanol, isopropanol, 1-butanol Alcohol-based solvents such as ethyl acetate, methyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and other ester-based solvents, acetone, methyl ethyl ketone, methyl tertiary butyl ketone, cyclohexanone and other ketone-based solvents, dichloromethane, A chlorine-based solvent such as chloroform, and a fluorine-based solvent such as Novec 7200, Novec 7000, Novec 7100, and Nove
  • the polysiloxane of this embodiment will be described below.
  • the polysiloxane according to the present embodiment includes a structural unit (1) represented by the following general formula (1) and a structural unit (2) represented by the following general formula (2).
  • the polysiloxane may be a copolymer polysiloxane containing both the structural unit (1) and the structural unit (2).
  • the above-mentioned silicon-containing monomer mixture is used to hydrolyze the "OR 2 " portion in the general formula (X) and the "OR 2 " portion in the general formula (Y) under an acidic catalyst or a basic catalyst. Then, a silanol group is generated, and two or more of the silanol groups are dehydrated and condensed to obtain the polysiloxane of the copolymer according to the present embodiment.
  • the polysiloxane of the copolymer according to the present embodiment can also be obtained by the condensation reaction between the generated silanol group and the "Si-OR 2 " moiety.
  • the polysiloxane of the copolymer according to the present embodiment can be obtained.
  • the polysiloxane of the copolymer according to the present embodiment can be obtained.
  • the silicon-containing monomer mixture When hydrolyzing and polycondensing the above-mentioned silicon-containing monomer mixture, the silicon-containing monomer mixture may be provided in a solution diluted with a solvent.
  • a solvent for example, Japanese Patent Application Laid-Open No. 2013-224279 describes that when a predetermined silicon-containing compound for forming a resist underlayer film is hydrolyzed and condensed, the monomer as a raw material thereof can be diluted with an organic solvent. ..
  • the solvent that can be used for dilution in the present invention is not particularly limited, but is preferably the same as the above-mentioned "solvent that may be contained in the mixture of the present invention".
  • the polysiloxane according to the present embodiment may contain the structural unit (1), and the content thereof is not particularly limited.
  • the abundance ratio of the structural unit (1) in the polysiloxane is (Aa) and the abundance ratio of the structural unit (2) in the polysiloxane is (Bb)
  • the polysiloxane according to the present embodiment is molar.
  • Bb / (Aa + Bb) may be 0.95 or less.
  • the storage stability is further improved, which is preferable.
  • the abundance ratio (Aa) of the constituent unit (1) and the abundance ratio (Bb) of the constituent unit (2) are in molar ratio.
  • Bb / (Aa + Bb)> 0.04 may be satisfied. It is preferable that Bb / (Aa + Bb) ⁇ 0.05.
  • each of the R 3s has a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, and a branched form having 3 to 10 carbon atoms.
  • All of the hydrogen atoms in the alkyl group, alkenyl group, phenyl group and alkoxy group may or may not be substituted by the fluorine atom.
  • a part of the alkyl group, alkenyl group, phenyl group and alkoxy group may be substituted with a fluorine atom.
  • R x is a hydrogen atom or an acid instability group.
  • m is a number greater than or equal to 0 and less than 3
  • n is a number greater than 0 and less than or equal to 3.
  • m + n 3 Satisfy the relationship.
  • the acid instability group the above-mentioned acid instability group can be used.
  • R 3 , R x , m and n are the same as the definitions of R 3 , R x , m and n described in the structural unit (1).
  • Equation (1-1) represents the case where n is 1.
  • Equation (1-2) represents the case where n is 2.
  • Equation (1-3) represents the case where n is 3.
  • n 1, the structural unit (1) and the structural unit (2) are located at the ends of the polysiloxane chain in the polysiloxane.
  • R z is the following formula (R z -1) or formula (R z -2).
  • R a and R b are independently synonymous with R 3 in the general formula (1).
  • the broken line represents the bond with the Si atom.
  • the wavy line portion represents the bond with the Si atom.
  • a silicon-containing monomer different from the silicon-containing monomer (X) or the silicon-containing monomer (Y) may be present in the reaction system. This makes it possible to obtain a copolymer containing three or more components. A copolymer containing three or more components will be further described.
  • the polysiloxane may further contain at least one of the structural unit (3) represented by the following general formula (3) and the structural unit (4) represented by the following general formula (4).
  • the structural unit (3) represented by the following general formula (3) and the structural unit (4) represented by the following general formula (4).
  • Ry is a monovalent organic group having 1 to 30 carbon atoms and containing any one of an epoxy group, an oxetane group, an acryloyl group, a methacryloyl group, or a lactone group.
  • R 4 is a hydrogen atom, a halogen element, an alkyl group having 1 or more and 3 or less carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 or more and 5 or less carbon atoms, or 1 or more and 3 or less carbon atoms. Fluoroalkyl group.
  • c is a number of 1 or more and 3 or less
  • p is a number of 0 or more and less than 3
  • q is a number of more than 0 and 3 or less.
  • c, p, and q are theoretical values of c being an integer of 1 to 3, p being an integer of 0 to 3, and q being 0. It is an integer of ⁇ 3.
  • c + p + q 4 means that the total theoretical value is 4.
  • c, p and q are obtained as average values, so c of the average value is rounded to a decimal number of 1 or more and 3 or less, and p is rounded off. It may be a decimal number of 0 or more and 3 or less (however, p ⁇ 3.0), and q may be a decimal number of 0 or more and 3 or less (where q ⁇ 0).
  • any of the above-mentioned substituents is independently selected as R y or R 4 .
  • R5 is a substituent selected from the group consisting of a halogen group, an alkoxy group and a hydroxy group.
  • d is a number greater than or equal to 0 and less than 4
  • r is a number greater than 0 and less than or equal to 4.
  • d is an integer of 0 to 4 and r is an integer of 0 to 4.
  • d and r are obtained as average values, so d of the average value is rounded to a decimal number of 0 or more and 4 or less (however, d ⁇ 4. 0) and r may be a decimal number (where r ⁇ 0) that is rounded to the nearest 0 or 4 (where r ⁇ 0).
  • the polysiloxane may be a group in which the monovalent organic group Ry is represented by the following general formula (2a), (2b), (2c), (3a) or (4a). ..
  • R g , R h , R i , R j and R k are independently linking groups or divalent organic groups, respectively. Represents. The broken line represents a bond.
  • examples of the divalent organic group include alkylene groups having 1 to 20 carbon atoms, forming an ether bond. It may contain one or more sites. When the number of carbon atoms is 3 or more, the alkylene group may be branched, or distant carbons may be connected to form a ring. When there are two or more alkylene groups, oxygen may be inserted between carbons to form one or more ether bond sites, which are divalent organic groups. This is a preferred example.
  • R j and R k are divalent organic groups
  • R g , R h , R i , R j and R k are mentioned as preferable groups. I can list the ones again.
  • the R y group contains a lactone group
  • the R y group is represented by the structure of R y ⁇ Si
  • the R y group has the following formulas (5-1) to (5-20) and formula (6). It is preferably a group selected from -1) to (6-7), formulas (7-1) to (7-28), or formulas (8-1) to (8-12).
  • R y is synonymous with R y in the general formula (3)
  • R a and R b are independently synonymous with R y and R 4 in the general formula (3), respectively.
  • the broken line represents a bond with another Si atom.
  • the broken line represents a bond with a Si atom.
  • O 4/2 represented by the above general formula (3-1) is generally called a Q4 unit, and shows a structure in which all four bonds of Si atoms form a siloxane bond.
  • the general formula (4) may include a hydrolyzable / condensable group in the bond, such as the Q0, Q1, Q2, and Q3 units shown below. Further, the general formula (4) may have at least one selected from the group consisting of Q1 to Q4 units.
  • Q0 unit A structure in which all four bonds of the Si atom are groups capable of hydrolyzing and polycondensing (halogen groups, alkoxy groups, hydroxy groups, etc., or groups capable of forming a siloxane bond).
  • Q1 unit A structure in which one of the four bonds of the Si atom forms a siloxane bond and the remaining three are all hydrolyzable / polycondensable groups.
  • Q2 unit Of the four bonds of Si atoms, two form a siloxane bond and the remaining two are all hydrolyzable / polycondensable groups.
  • Q3 unit A structure in which three of the four bonds of the Si atom form a siloxane bond, and the remaining one is the above-mentioned hydrolyzable / polycondensable group.
  • the structural unit (4) represented by the general formula (4) has a structure close to SiO 2 in which organic components are eliminated as much as possible, the obtained pattern cured film has chemical resistance, heat resistance, transparency, or resistance. It can impart organic solvent properties.
  • the structural unit (4) represented by the general formula (4) is tetraalkoxysilane, tetrahalosilane (for example, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, etc.). Or, it can be obtained by using those oligomers as a raw material, hydrolyzing the oligomer, and then polymerizing (see “Polymerization Method" described later).
  • Oligomers include silicate 40 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.), ethyl silicate 40 (average pentamer, manufactured by Corcote Co., Ltd.), and silicate 45 (average heptameric, manufactured by Tama Chemical Industry Co., Ltd.).
  • M silicate 51 (average tetramer, manufactured by Tama Chemical Industry Co., Ltd.), methyl silicate 51 (average tetramer, manufactured by Corcote Co., Ltd.), methyl silicate 53A (average heptameric, manufactured by Corcote Co., Ltd.), ethyl silicate
  • examples thereof include silicate compounds such as 48 (average tetramer, manufactured by Corcote Co., Ltd.) and EMS-485 (mixture of ethyl silicate and methyl silicate, manufactured by Corcote Co., Ltd.). From the viewpoint of ease of handling, silicate compounds are preferably used.
  • the ratio of the constituent unit (1) and / or the constituent unit (2) with Si atoms is 1 to 100 mol% in total. It is preferable to have. Further, it may be more preferably 1 to 80 mol%, further preferably 2 to 60 mol%, and particularly preferably 5 to 50 mol%.
  • the ratio of each constituent unit in the Si atom is composed of each. It is preferable that the unit (3) is in the range of 0 to 80 mol% and the constituent unit (4) is in the range of 0 to 90 mol% (however, the constituent unit (3) and the constituent unit (4) are 1 to 90 mol% in total). Further, the structural unit (3) may be more preferably 2 to 70 mol%, still more preferably 5 to 40 mol%. Further, the structural unit (4) may be more preferably in the range of 5 to 70 mol%, still more preferably in the range of 5 to 40 mol%. Further, the total of the structural unit (3) and the structural unit (4) may be more preferably in the range of 2 to 70 mol%, still more preferably in the range of 5 to 60 mol%.
  • a total of 1 to 100 mol% of Si atoms of the constituent unit (1) and / or the constituent unit (2) and the constituent unit (3) and / or the constituent unit (4) may be contained. It may be preferably 2 to 80 mol%, more preferably 5 to 60 mol%.
  • the mol% of Si atoms can be determined, for example, from the peak area ratio in 29 Si-NMR.
  • chlorosilane examples include dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, diphenyldichlorosilane, bis (3,3,3-trifluoropropyl) dichlorosilane, and methyl (3,3,3-tri).
  • Fluoropropyl) dichlorosilane methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, isopropyltrichlorosilane, phenyltrichlorosilane, methylphenyltrichlorosilane, trifluoromethyltrichlorosilane, pentafluoroethyltrichlorosilane, and 3,3,3- Examples thereof include trifluoropropyltrichlorosilane.
  • alkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiphenoxysilane, and dipropyl.
  • phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane are preferable for the purpose of enhancing the heat resistance and transparency of the obtained pattern-cured film, and the obtained pattern-cured film is flexible.
  • Dimethyldimethoxysilane and dimethyldiethoxysilane are preferable for the purpose of enhancing the properties and preventing cracks and the like.
  • the ratio of Si atoms contained in the optional component when the total Si atom of the polysiloxane according to the present embodiment is 100 mol% is not particularly limited, but is, for example, 0 to 99 mol%, preferably 0 to 99 mol%. It may be 0 to 95% mol, more preferably 10 to 85 mol%.
  • the molecular weight of the polysiloxane according to the present embodiment may be 500 to 50,000 in weight average molecular weight, preferably 800 to 40,000, and more preferably 1,000 to 30,000.
  • the molecular weight can be set within a desired range by adjusting the amount of the catalyst and the temperature of the polymerization reaction.
  • R 1 , a and b are the same as those in the general formula (X), and X x is a halogen atom.
  • a desired polysiloxane can be obtained by a hydrolysis polycondensation reaction using the alkoxysilane or the like exemplified above.
  • a desired polysiloxane can be obtained by a hydrolysis polycondensation reaction using the alkoxysilane or halosilane exemplified above.
  • the present hydrolysis polycondensation reaction can be carried out by a general method in the hydrolysis and condensation reaction of halosilanes (preferably chlorosilane) and alkoxysilane.
  • halosilanes and alkoxysilanes are placed in a reaction vessel at room temperature (particularly, the ambient temperature without heating or cooling, usually about 15 ° C. or higher and about 30 ° C. or lower; the same applies hereinafter).
  • room temperature particularly, the ambient temperature without heating or cooling, usually about 15 ° C. or higher and about 30 ° C. or lower; the same applies hereinafter.
  • water for hydrolyzing halosilanes and alkoxysilanes, a catalyst for advancing the polycondensation reaction, and if desired, a reaction solvent are added to the reaction vessel to prepare a reaction solution.
  • the order in which the reaction materials are added at this time is not limited to this, and the reaction solution can be prepared by adding them in any order.
  • other Si monomers may be added to the reaction vessel in the same manner as the halosilanes and alkoxysilanes.
  • the polysiloxane according to the present embodiment can be obtained by advancing the hydrolysis and condensation reaction at a predetermined temperature for a predetermined time while stirring the reaction solution.
  • the time required for hydrolysis condensation depends on the type of catalyst, but is usually 3 hours or more and 24 hours or less, and the reaction temperature is room temperature (for example, 25 ° C.) or more and 200 ° C. or less.
  • the reaction vessel should be closed or reflux such as a condenser to prevent unreacted raw materials, water, reaction solvent and / or catalyst in the reaction system from being distilled off from the reaction system. It is preferable to attach a device to reflux the reaction system.
  • the reaction from the viewpoint of handling the polysiloxane according to the present embodiment, it is preferable to remove the water remaining in the reaction system, the alcohol produced, and the catalyst.
  • Water, alcohol, and the catalyst may be removed by an extraction operation, or a solvent such as toluene that does not adversely affect the reaction may be added to the reaction system and azeotropically removed with a Dean-Stark tube.
  • the amount of water used in the hydrolysis and condensation reactions is not particularly limited. From the viewpoint of reaction efficiency, the amount of water used in the hydrolysis and condensation reactions is the total number of moles of hydrolyzable groups (alkoxy groups and halogen atomic groups) contained in the raw materials alkoxysilane and halosilanes. , 0.5 times or more and 5 times or less is preferable.
  • the catalyst for advancing the polycondensation reaction is not particularly limited, but an acid catalyst and a base catalyst are preferably used.
  • the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, arsenic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, tosilic acid, formic acid, Examples thereof include polyvalent carboxylic acids such as maleic acid, malonic acid, and succinic acid, or anhydrides thereof.
  • the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, and carbonic acid. Examples thereof include sodium and tetramethylammonium hydroxide.
  • the amount of the catalyst used is 1.0 ⁇ 10-5 times or more 1.0 with respect to the total number of moles of hydrolyzable groups (alkoxy groups and halogen atomic groups) contained in the raw materials alkoxysilane and halosilanes. It is preferably x10-1 times or less.
  • reaction solvent In the hydrolysis and condensation reaction, it is not always necessary to use a reaction solvent, and the raw material compound, water and the catalyst can be mixed and hydrolyzed and condensed.
  • the type thereof is not particularly limited. Among them, a polar solvent is preferable, and an alcohol solvent is more preferable, from the viewpoint of solubility in a raw material compound, water, and a catalyst. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, diacetone alcohol, propylene glycol monomethyl ether and the like.
  • the amount to be used when the reaction solvent is used any amount necessary for the hydrolysis condensation reaction to proceed in a uniform system can be used. Further, a solvent described later may be used as the reaction solvent.
  • Resin composition In one embodiment, a resin composition containing a polysiloxane and a solvent can be provided. Solvents contained in the resin composition include propylene grillecol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, ⁇ -butyrolactone, diacetone alcohol, diglyme, methylisobutylketone, 3-methoxybutyl acetate, 2-heptanone, etc.
  • At least one compound selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, glycols, and glycol ethers and glucol ether esters can be exemplified.
  • glycol, glycol ether, and glycol ether ester include Celtor (registered trademark) manufactured by Daicel Co., Ltd. and Highsolve (registered trademark) manufactured by Toho Chemical Industry Co., Ltd. Specifically, cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene.
  • the amount of the solvent contained in the resin composition is preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less.
  • the resin composition may contain the following components as additives as long as the excellent properties of the coating liquid are not significantly impaired.
  • an additive such as a surfactant may be contained for the purpose of improving coating property, leveling property, film forming property, storage stability, defoaming property and the like.
  • a commercially available surfactant product name Megafuck manufactured by DIC Co., Ltd., product number F142D, F172, F173 or F183, product name Florard manufactured by 3M Japan Co., Ltd., product number, FC-135, FC-170C, FC-430 or FC-431, trade name Surflon manufactured by AGC Seimi Chemical Co., Ltd., product numbers S-112, S-113, S-131, S-141 or S-145, or Toray Dow Corning Silicone. Examples thereof include product names manufactured by SH-28PA, SH-190, SH-193, SZ-6032 or SF-8428 manufactured by S.K.
  • the blending amount of the surfactant is preferably 0.001 part by mass or more and 10 parts by mass or less when the polysiloxane is 100 parts by mass.
  • Megafuck is the trade name of the fluorine-based additive (surfactant / surface modifier) of DIC Co., Ltd.
  • Florard is the trade name of the fluorine-based surfactant manufactured by 3M Japan Co., Ltd.
  • Surflon is AGC Seimi Chemical Co., Ltd. It is a trade name of the company's fluorine-based surfactant, and each is registered as a trademark.
  • a curing agent can be added for the purpose of improving the chemical resistance of the obtained cured film or pattern cured film.
  • the curing agent include a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, an isocyanate curing agent, and an epoxy curing agent. It is considered that the curing agent mainly reacts with the "-OH" of the structural unit (3) and / or the structural unit (4) to form a crosslinked structure.
  • isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or diphenylmethane diisocyanate, and melamine resins or ureas such as isocyanurate, blocked isocyanate or buret compound, alkylated melamine, methylol melamine, imino melamine and the like.
  • An example thereof is an epoxy curing agent having two or more epoxy groups obtained by reacting an amino compound such as a resin or a polyvalent phenol such as bisphenol A with epichlorohydrin.
  • a curing agent having a structure represented by the formula (11) is more preferable, and specifically, a melamine derivative or a urea derivative represented by the formulas (11a) to (11d) (manufactured by Sanwa Chemical Co., Ltd.). (Note that in equation (11), the broken line means the bond).
  • the amount of the curing agent is preferably 0.001 part by mass or more and 10 parts by mass or less when the polysiloxane is 100 parts by mass.
  • a cured film formed by curing polysiloxane is provided. Further, in one embodiment, a cured film formed by curing a resin composition is provided.
  • the cured film according to these embodiments can be used as a coating material for liquid crystal displays and organic EL displays, a coating material for image sensors, a sealing material in the semiconductor field, and a hard mask material for multilayer resists.
  • a cured film formed by curing a polysiloxane or a resin composition is provided.
  • a cured film can be formed by applying the polysiloxane according to the present embodiment on a substrate and then heating it at a temperature of 100 ° C to 350 ° C.
  • a cured film can be formed by applying the resin composition according to the present embodiment on a substrate and then heating it at a temperature of 100 to 350 ° C.
  • Photosensitive resin composition In one embodiment, the polysiloxane according to the above-mentioned embodiment as the component (A) and the quinonediazide compound, the photoacid generator, the photobase generator, and the photoradical generator as the component (B).
  • a photosensitive resin composition containing at least one photosensitive agent selected from the group consisting of (C) and a solvent as a component (C) is provided.
  • Photosensitizer for example, at least one selected from the group consisting of naphthoquinone diazide, a photoacid generator, a photobase generator and a photoradical generator can be used, but is limited thereto. It's not a thing.
  • the naphthoquinone diazide compound releases nitrogen molecules and decomposes to generate carboxylic acid groups in the molecules, thus improving the solubility of the photosensitive resin film in an alkaline developer. Further, in the unexposed portion, the naphthoquinone diazide compound suppresses the alkali solubility of the photosensitive resin film. Therefore, by using the photosensitive resin composition containing the naphthoquinone diazide compound, a soluble contrast in the alkaline developer is generated in the unexposed portion and the exposed portion, and a positive pattern can be formed.
  • the naphthoquinone diazide compound is a compound having a quinone diazide group, for example, a 1,2-quinone diazide group.
  • the 1,2-quinone diazide compound include 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, and 1,2-naphthoquinone-2-diazide.
  • Examples thereof include -4-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.
  • the quinone diazide compound By using the quinone diazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (436 nm) of a mercury lamp which is a general ultraviolet ray. ..
  • naphthoquinone diazide compounds examples include NT series, 4NT series, PC-5 manufactured by Toyo Gosei Co., Ltd., and TKF series, PQ-C manufactured by Sanbo Chemical Industrial Co., Ltd.
  • the blending amount of naphthoquinone diazide as a photosensitive agent in the present photosensitive resin composition is not necessarily limited, but when the polysiloxane according to the present embodiment is 100 parts by mass, the blending of naphthoquinone diazide as a photosensitive agent is performed.
  • the amount is, for example, preferably 2 parts by mass or more and 40 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less.
  • the photoacid generator is a compound that generates an acid by irradiation with light.
  • the acid generated at the exposed portion promotes the silanol condensation reaction, that is, the solgel polymerization reaction, and can realize a significant decrease in the dissolution rate by the alkaline developer, that is, resistance to the alkaline developer.
  • the polysiloxane according to the present embodiment has an epoxy group or an oxetane group, it is preferable because it is possible to accelerate each curing reaction. On the other hand, this action does not occur in the unexposed portion, and the unexposed portion is dissolved by the alkaline developer to form a negative pattern according to the shape of the exposed portion.
  • the photoacid generator examples include a sulfonium salt, an iodonium salt, a sulfonyldiazomethane, an N-sulfonyloxyimide or an oxime-O-sulfonate. These photoacid generators may be used alone or in combination of two or more. Specific examples of commercially available products include product names: Irgacure 290, Irgacure PAG121, Irgacure PAG103, Irgacure CGI1380, Irgacure CGI725 (all manufactured by BASF in the United States), and product names: PAI-101, PAI-106, NAI-105.
  • the amount of the photoacid generator as the photosensitive agent in the photosensitive resin composition is not necessarily limited, but when the polysiloxane according to the present embodiment is 100 parts by mass, the photoacid as the photosensitive agent is used.
  • the blending amount of the generator is, for example, preferably 0.01 part by mass or more and 10 parts by mass or less, and more preferably 0.05 part by mass or more and 5 parts by mass or less.
  • a photobase generator is a compound that generates a base (anion) by irradiation with light.
  • the base generated at the exposed portion promotes the sol-gel reaction, and the dissolution rate of the alkaline developer can be significantly reduced, that is, the resistance to the alkaline developer can be realized.
  • this action does not occur in the unexposed portion, and the unexposed portion is dissolved by the alkaline developer to form a negative pattern according to the shape of the exposed portion.
  • photobase generators include amides and amine salts.
  • Specific examples of commercially available products include trade names: WPBG-165, WPBG-018, WPBG-140, WPBG-027, WPBG-266, WPBG-300, WPBG-345 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
  • photoacid generators and photobase generators may be used alone or in combination of two or more, or in combination with other compounds.
  • combination with other compounds include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, and ethyl.
  • Combinations with amines such as -4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate, further combined with iodonium salts such as diphenyliodonium chloride, dyes such as methylene blue and amines, etc. Can be mentioned.
  • the amount of the photobase generator as the photosensitive agent in the photosensitive resin composition is not necessarily limited, but when the polysiloxane according to the present embodiment is 100 parts by mass, the photobase as the photosensitive agent is used.
  • the blending amount of the generator is, for example, preferably 0.01 part by mass or more and 10 parts by mass or less, and more preferably 0.05 part by mass or more and 5 parts by mass or less.
  • the photosensitive resin composition may further contain a sensitizer.
  • a sensitizer By containing the sensitizer, the reaction of the photosensitive agent is promoted in the exposure treatment, and the sensitivity and the pattern resolution are improved.
  • the sensitizer is not particularly limited, but preferably a sensitizer that vaporizes by heat treatment or a sensitizer that fades by light irradiation is used.
  • This sensitizer needs to have light absorption for the exposure wavelength in the exposure process (for example, 365 nm (i line), 405 nm (h line), 436 nm (g line)), but the pattern cured film as it is. If it remains in the visible light region, the transparency will decrease due to the presence of absorption in the visible light region. Therefore, in order to prevent the decrease in transparency due to the sensitizer, the sensitizer used is preferably a compound that vaporizes by heat treatment such as heat curing or a compound that fades by light irradiation such as bleaching exposure described later.
  • the blending amount thereof is preferably 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polysiloxane according to the present embodiment.
  • Pattern cured film In one embodiment, a pattern cured film having a pattern structure obtained by curing a photosensitive resin composition is provided. Further, the pattern structure may include a concavo-convex structure having a pattern dimension of 500 ⁇ m or less.
  • the "pattern cured film” in the present specification is a cured film obtained by developing to form a pattern after the exposure step and curing the obtained pattern.
  • FIG. 1 is a schematic diagram illustrating a method for manufacturing a negative type pattern cured film 111 according to an embodiment of the present invention.
  • the method for producing the pattern cured film 111 according to the present embodiment can include the following first to fourth steps.
  • First step A film forming step of applying a photosensitive resin composition on a substrate 101 to form a photosensitive resin film 103.
  • Second step An exposure step for exposing the photosensitive resin film 103.
  • Third step A developing step of developing the photosensitive resin film after exposure to form the pattern resin film 107.
  • Fourth step A curing step of heating the pattern resin film to make the pattern resin film into a pattern curing film 111.
  • the base material 101 is prepared (step S1-1).
  • the base material 101 to which the photosensitive resin composition according to the present embodiment is applied is selected from a silicon wafer, a metal, a glass, a ceramic, and a plastic base material, depending on the use of the pattern cured film to be formed.
  • silicon, silicon nitride, glass, polyimide (Kapton), polyethylene terephthalate, polycarbonate, polyethylene naphthalate and the like can be mentioned.
  • the base material 101 may have an arbitrary layer such as silicon, metal, glass, ceramic, or resin on the surface thereof, and "on the base material" means that the layer is also on the surface of the base material. It may be through.
  • the method for applying the photosensitive resin composition according to the present embodiment onto the substrate 101 is not particularly limited to known coating methods such as spin coating, dip coating, spray coating, bar coating, applicator, inkjet or roll coater. Can be used.
  • the photosensitive resin film 103 can be obtained by drying the base material 101 coated with the photosensitive resin composition (step S1-2).
  • the drying treatment may be performed as long as the solvent can be removed to the extent that the obtained photosensitive resin film 103 does not easily flow or deform, and may be heated at, for example, 80 to 120 ° C. for 30 seconds or more and 5 minutes or less.
  • the photosensitive resin film 103 obtained in the first step is shielded from light by a light-shielding plate (photomask) 105 having a desired shape for forming a desired pattern, and the photosensitive resin film 103 is irradiated with light.
  • the photosensitive resin film 103 after exposure can be obtained by performing the exposure treatment (step S2).
  • the photosensitive resin film 103 after exposure includes an exposed portion 103a, which is an exposed portion, and an unexposed portion.
  • a known method can be used for the exposure process.
  • the light source a light ray having a light source wavelength in the range of 10 nm to 600 nm can be used.
  • a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an EUV light (wavelength 13.5 nm) and the like can be used.
  • the exposure amount can be adjusted according to the type and amount of the photosensitive agent to be used, the manufacturing process, and the like, and is not particularly limited, but is about 1 to 10000 mJ / cm 2 , preferably 10 to 5000 mJ / cm 2 . Degree.
  • post-exposure heating can be performed before the development process.
  • the temperature of post-exposure heating is preferably 60 to 180 ° C., and the post-exposure heating time is preferably 30 seconds to 10 minutes.
  • step S3 by developing the photosensitive resin film 103 after exposure obtained in the second step, the film other than the exposed portion 103a is removed, and a film having a pattern of a desired shape (hereinafter referred to as "pattern resin film"). 107 (which may be called) can be formed (step S3).
  • pattern resin film a film having a pattern of a desired shape
  • the negative type pattern curing film 111 is obtained in FIG. 1, in the case of the positive type pattern curing film, the exposed portion 103a is removed by developing, and the photosensitive resin film 103 shaded by the light shielding plate 105. Becomes a pattern resin film.
  • Development is to form a pattern by dissolving, washing and removing an unexposed part or an exposed part using an alkaline solution as a developing solution. As described above, the unexposed portion is melted and washed and removed when a negative pattern resin film is obtained, and the exposed portion is melted and removed when a positive pattern resin film is obtained.
  • the developer to be used is not particularly limited as long as it can remove a desired photosensitive resin film by a predetermined developing method.
  • Specific examples thereof include an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a quaternary ammonium salt, and an alkaline aqueous solution using a mixture thereof.
  • alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (abbreviation: TMAH) can be mentioned.
  • TMAH tetramethylammonium hydroxide
  • it is preferable to use a TMAH aqueous solution and in particular, it is preferable to use a TMAH aqueous solution of 0.1% by mass or more and 5% by mass or less, more preferably 2% by mass or more and 3% by mass or less.
  • the developing method known methods such as a dipping method, a paddle method, and a spraying method can be used.
  • the development time may be 0.1 minutes or more and 3 minutes or less, preferably 0.5 minutes or more and 2 minutes or less. After that, washing, rinsing, drying, etc. are performed as necessary to form the desired pattern resin film 107 on the base material 101.
  • the pattern resin film 107 it is preferable to further perform bleaching exposure on the pattern resin film 107 after forming the pattern resin film 107.
  • the purpose is to improve the transparency of the finally obtained pattern cured film 111 by photodecomposing the photosensitive agent remaining in the pattern resin film 107.
  • the same exposure processing as in the second step can be performed.
  • the pattern resin film (including the bleached exposed pattern resin film) 107 obtained in the third step is heat-treated to obtain the final pattern cured film 111 (step S4).
  • the heat treatment makes it possible to condense the alkoxy group or silanol group that remains as an unreactive group in the polysiloxane. Further, if the photosensitive agent remains, it can be removed by thermal decomposition.
  • the heating temperature at this time is preferably 80 ° C. or higher and 400 ° C. or lower, and more preferably 100 ° C. or higher and 350 ° C. or lower.
  • the heat treatment time may be 1 minute or more and 90 minutes or less, preferably 5 minutes or more and 60 minutes or less.
  • the cured film or pattern cured film described above can be used as an antireflection film, a lens, an optical waveguide, a light-shielding film, or a flattening film. Further, the antireflection film, the lens, the optical waveguide, the light shielding film or the flattening film can be used for a solid-state image pickup device or a display device.
  • Examples of the electronic device having the solid-state image sensor include a video camera, a digital camera, a mobile phone with a camera function, a copying machine, a game device, an automatic door, and the like.
  • Examples of the image pickup device having the solid-state image pickup device include an endoscope camera, a microscope, a medical camera using light receiving infrared light, an in-vehicle camera, a surveillance camera, a person authentication camera, and an industrial camera.
  • Examples of the display device include a liquid crystal display, an organic EL display, a quantum dot display, a micro LED display, and the like.
  • HFA-Si (m form) A compound represented by the following chemical formula
  • HFA-Si (p-form) A compound represented by the following chemical formula
  • GPC Global Permeation Chromatography
  • the weight average molecular weight (Mw) was 1850.
  • the peak of the raw material total of HFA-Si (m body) and HFA-Si (p body) was not confirmed, and the conversion rate was 100%.
  • the weight average molecular weight (Mw) was 1850.
  • the peak of the raw material total of HFA-Si (m body) and HFA-Si (p body) was not confirmed, and the conversion rate was 100%.
  • the weight average molecular weight (Mw) was 2500.
  • the peak of the raw material total of HFA-Si (m body) and HFA-Si (p body) was not confirmed, and the conversion rate was 100%.
  • the obtained cyclohexanone in the organic layer was distilled off by an evaporator to obtain 3 g of a polysiloxane solution 7 having a solid content concentration of 33 wt%.
  • the weight average molecular weight (Mw) was 1500.
  • the conversion rate calculated from the area% of the peak of the raw material total of HFA-Si (m body) and HFA-Si (p body)) and the polymer peak was 25%.
  • Table 1 shows the measurement results of the conversion rate from the raw material to the polysiloxane and the weight average molecular weight 3 hours after the start of the reaction for the polysiloxanes of each Example and Comparative Example.
  • Example 7 1 g of the polysiloxane solution of Example 5 was put into a vial and stored in a refrigerator.
  • the weight average molecular weight (Mw) was measured by GPC 1 day and 4 days after the start of storage. The result was Mw2230 after 1 day and Mw2250 after 4 days.
  • Example 8 1 g of the polysiloxane solution of Example 6 was put into a vial and stored in a refrigerator.
  • the weight average molecular weight (Mw) was measured by GPC 1 day and 4 days after the start of storage. The result was Mw2450 after 1 day and Mw2500 after 4 days.
  • the obtained cyclohexanone in the organic layer was distilled off by an evaporator to obtain 10 g of a polysiloxane solution 8 having a solid content concentration of 33 wt%.
  • the weight average molecular weight (Mw) was 2480.
  • FIG. 2 shows the relationship between the storage time and the weight average molecular weight of the polysiloxanes of Examples 7 and 8 and Comparative Example 2.
  • the polysiloxane of the present invention has a high weight average molecular weight (Mw) and good storage stability.
  • the mixture of the silicon-containing monomer (X) and the silicon-containing monomer (Y) obtained by the present invention contains a polymer resin synthetic raw material, a polymer modifier, an inorganic compound surface treatment agent, various coupling agents, and organic synthesis. It is useful as an intermediate raw material. Further, the polysiloxane containing the structural unit (1) and the structural unit (2) and the film obtained from the polysiloxane are soluble in an alkaline developing solution, have patterning performance, and are excellent in heat resistance and transparency, and thus are semiconductors.
  • fine particles such as polytetrafluoroethylene, silica, titanium oxide, zirconium oxide, or magnesium fluoride can be used for the purpose of adjusting the refractive index. It can be mixed and used in proportion.

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PCT/JP2021/032337 2020-09-16 2021-09-02 珪素含有モノマー混合物、ポリシロキサン、樹脂組成物、感光性樹脂組成物、硬化膜、硬化膜の製造方法、パターン硬化膜及びパターン硬化膜の製造方法 Ceased WO2022059506A1 (ja)

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