WO2016035593A1 - 樹脂および感光性樹脂組成物 - Google Patents

樹脂および感光性樹脂組成物 Download PDF

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WO2016035593A1
WO2016035593A1 PCT/JP2015/073687 JP2015073687W WO2016035593A1 WO 2016035593 A1 WO2016035593 A1 WO 2016035593A1 JP 2015073687 W JP2015073687 W JP 2015073687W WO 2016035593 A1 WO2016035593 A1 WO 2016035593A1
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carbon atoms
mol
organic group
group
general formula
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PCT/JP2015/073687
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English (en)
French (fr)
Japanese (ja)
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増田有希
有本由香里
弓場智之
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東レ株式会社
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Priority to SG11201701691PA priority Critical patent/SG11201701691PA/en
Priority to KR1020177004290A priority patent/KR102384507B1/ko
Priority to JP2015543195A priority patent/JP6724363B2/ja
Priority to CN201580046940.7A priority patent/CN106795283B/zh
Publication of WO2016035593A1 publication Critical patent/WO2016035593A1/ja

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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
    • 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
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a resin containing a specific structure. More specifically, the present invention relates to a resin suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and a photosensitive resin composition using the same.
  • Polyimide resins have excellent heat resistance, electrical insulation, and mechanical properties, and are therefore widely used in surface protection films for semiconductor elements, interlayer insulation films, insulation layers for organic electroluminescent elements, and the like.
  • a composition containing a polyamic acid ester containing a phenolic hydroxyl group and an o-quinonediazide compound (Patent Document 1) or a solvent-capped polyimide that is soluble in a solvent And a composition containing a naphthoquinonediazide compound, and a composition containing a polybenzoxazole precursor and a naphthoquinonediazide compound (Patent Document 2).
  • Patent Document 1 a composition containing a polyamic acid ester containing a phenolic hydroxyl group and an o-quinonediazide compound
  • Patent Document 2 a solvent-capped polyimide that is soluble in a solvent
  • a composition containing a naphthoquinonediazide compound and a composition containing a polybenzoxazole precursor and a naphthoquinonediazide compound
  • Patent Documents 3 to 4 a photosensitive resin composition that achieves high sensitivity with a highly transparent polyimide using a tetracarboxylic acid anhydride having an alicyclic structure has been proposed (for example, Patent Documents 3 to 4).
  • JP-A-4-204945 JP-A-1-46862 International Publication No. 00/73853 JP 2010-196041 A JP 2007-183388 A
  • polyimide resins using tetracarboxylic anhydrides having an alicyclic structure so far have too high solubility in an alkali developer, and thus it is difficult to achieve the formation of a thick film structure.
  • the polyimide resin using a tetracarboxylic anhydride having a hexafluoropropyl group and an alicyclic structure has a very poor residual film rate, and it is difficult to achieve the formation of a highly sensitive thick film structure. .
  • an object of the present invention is to provide a resin having high sensitivity and a remaining film ratio when used in a photosensitive resin composition.
  • the present invention has the following configuration.
  • An acid having an alicyclic structure having 6 to 40 carbon atoms or a semi-alicyclic structure having both an alicyclic structure having 6 to 40 carbon atoms and an aromatic ring or an anhydride thereof has a total amount of the acid or the anhydride of 100.
  • each R 1 independently represents a monovalent or condensed polycyclic alicyclic structure having a tetravalent organic group having 6 to 40 carbon atoms, or an organic having a monocyclic alicyclic structure.
  • each R 2 is independently a divalent organic group having 2 to 40 carbon atoms.
  • R 3 represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, m and n each represent a range of 0 to 100,000, and m + n> 2.
  • R 4 to R 81 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms.
  • X 1 It represents an oxygen atom, a sulfur atom, a divalent crosslinked structure divalent organic group or they become linked two or more sulfonyl groups or 1 to 3 carbon atoms.
  • X 2 is a direct (It is a divalent crosslinked structure formed by linking two or more organic groups selected from a bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or an arylene group.)
  • (6) in the general formula (1), when the total amount of R 1 and R 2 is 100 mol%, the organic group containing a fluorine atom has 30 mol% or more (2) to ( The resin according to any one of 5).
  • each R 1 independently represents a monocyclic or condensed polycyclic alicyclic structure, a C 6-40 tetravalent organic group, or a monocyclic alicyclic structure.
  • a tetravalent organic group having 6 to 40 carbon atoms in which the organic groups having them are connected to each other directly or via a crosslinked structure, and a 6 to 40 carbon atom having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring The resin according to any one of (2) to (6), wherein one or more organic groups selected from tetravalent organic groups are contained in an amount of 25 to 80 mol% when the total amount of R 1 is 100 mol%.
  • each R 1 independently represents a monovalent or condensed polycyclic alicyclic structure, a tetravalent organic group having 6 to 40 carbon atoms and a monocyclic alicyclic structure.
  • the resin according to any one of (2) to (6), wherein one or more organic groups selected from tetravalent organic groups are contained in an amount of 40 to 70 mol% when the total amount of R 1 is 100 mol%.
  • (10) (a) a resin having a structure represented by the general formula (8) as a main component, (b) a photoacid generator, and (c) a solvent, and having positive photosensitivity.
  • a photosensitive resin composition (a) a resin having a structure represented by the general formula (8) as a main component, (b) a photoacid generator, and (c) a solvent, and having positive photosensitivity.
  • each R 1 independently represents a monovalent or condensed polycyclic alicyclic structure having a tetravalent organic group having 6 to 40 carbon atoms and a monocyclic alicyclic structure.
  • a tetravalent organic group having 6 to 40 carbon atoms in which the groups are connected to each other directly or via a crosslinked structure and a tetravalent group having 6 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring 1 to 1 organic group selected from the group consisting of 5 to 95 mol% when the total amount of R 1 is 100 mol%
  • each R 2 is independently a divalent organic group having 2 to 40 carbon atoms.
  • R 3 represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, m and n each represent a range of 0 to 100,000, and m + n> 2, provided that the general formula (8) The structure represented by the formula is required to have a fluorine component and a phenolic hydroxyl group.)
  • a step of obtaining a photosensitive resin film, a step of exposing the photosensitive resin film obtained by the step, a step of developing the photosensitive resin film after the exposure using an alkaline aqueous solution, and the photosensitive resin film after the development The manufacturing method of the heat resistant resin film including the process of heat-processing.
  • the present invention relates to an acid having an alicyclic structure having 6 to 40 carbon atoms or a semi-alicyclic structure having both an alicyclic structure having 6 to 40 carbon atoms and an aromatic ring, or an acid anhydride thereof.
  • the resin of the present invention has a structure represented by the following general formula (1).
  • the resin having the structure represented by the general formula (1) is a polyimide precursor that is closed by heating and becomes a polyimide having excellent heat resistance and solvent resistance, or a polyimide that is closed by heating, This is a polyimide precursor that is partially ring-closed by heating and imidized.
  • this invention is the photosensitive resin composition containing resin which has a structure represented by General formula (1).
  • each R 1 independently represents a monovalent or condensed polycyclic alicyclic structure having a tetravalent organic group having 6 to 40 carbon atoms, or an organic having a monocyclic alicyclic structure.
  • One or more organic groups selected from valent organic groups are contained in an amount of 5 to 95 mol% when the total amount of R 1 is 100 mol%, and R 2 is independently a divalent organic group having 2 to 40 carbon atoms.
  • R 3 represents hydrogen or an organic group having 1 to 20 carbon atoms, m and n each represent a range of 0 to 100,000, and m + n> 2.
  • the resin having the structure represented by the general formula (1) of the present invention includes a resin having a structure other than the structure represented by the general formula (1) and the structure represented by the general formula (1).
  • the copolymer may be used.
  • each R 1 is independently a monocyclic or condensed polycyclic alicyclic structure, a C 6-40 tetravalent organic group, or a monocyclic alicyclic structure. And a tetravalent organic group having 6 to 40 carbon atoms connected to each other directly or via a crosslinked structure, and a tetravalent 6 to 40 carbon atom having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring One or more organic groups selected from the above organic groups have 5 to 95 mol% when the total amount of R 1 is 100 mol%.
  • R 2 independently represents a divalent organic group having 2 to 40 carbon atoms.
  • R 3 represents hydrogen or an organic group having 1 to 20 carbon atoms.
  • n and n each represent a range of 0 to 100,000, where m + n> 2.
  • the resin has a low absorbance, so that a highly sensitive photosensitive resin composition can be obtained even with a thick film.
  • a polyimide resin in which all of R 1 has an alicyclic structure is too soluble in an alkali developer, so that the developed film is eluted and the remaining film rate is deteriorated, or the alkali developer is easily taken in. And residues are generated.
  • the polyimide resin containing an alicyclic structure having less than 6 carbon atoms or an alicyclic structure having 41 or more carbon atoms is insufficient in solubility in an alkaline developer, the sensitivity is insufficient and during development. There was a problem that residues were generated in the pattern.
  • a phenolic hydroxyl group when contained in the structure represented by the general formula (1), moderate solubility in an alkali developer is obtained and contributes to the interaction with the photosensitive agent. It is preferable because a resin film capable of increasing sensitivity can be obtained.
  • the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and thus is preferable in that high mechanical properties and chemical resistance can be obtained.
  • R 1 in the general formula (1) is preferably 1 or more selected from the following general formulas (2) to (7).
  • R 4 to R 81 each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms.
  • a hydrogen atom contained in the organic group may be substituted with a halogen atom.
  • X 1 is an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or a divalent crosslinked structure formed by linking two or more thereof.
  • a hydrogen atom contained in the organic group may be substituted with a halogen atom.
  • X 2 is a divalent bond formed by linking two or more selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms or an arylene group. Cross-linked structure.
  • a hydrogen atom contained in the organic group may be substituted with a halogen atom.
  • R 1 is a structure derived from an acid dianhydride.
  • a tetracyclic organic group having 6 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure and an organic group having a monocyclic alicyclic structure used in the present invention are directly or via a crosslinked structure.
  • a tetravalent organic group having 6 to 40 carbon atoms and a tetravalent organic group having 6 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring are directly or via a crosslinked structure.
  • anhydride examples include 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride , 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 Cyclohexene-1,2-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5 Alicyclic tetracarboxylic acids such as 6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride
  • the pattern obtained from the photosensitive resin composition in the present invention preferably has a high resolution.
  • the resolution means the minimum dimension obtained when forming a pattern using the photosensitive resin composition, and the resolution is so high that a fine pattern can be formed.
  • a photosensitive resin composition using a resin having a very low absorbance has an excessively high light collection rate and tends to have a pattern width equal to or larger than the target dimension. As a result, the resolution of the resulting pattern is reduced. For this reason, the content of the acid dianhydride when R 1 in the structure represented by the general formula (1) is 100 mol% is 25 mol% in that a pattern width having a target dimension can be obtained during pattern processing. More preferably, it is more preferably 40 mol% or more.
  • the content of the alicyclic structure is small, the light collection rate is low and a small pattern opening cannot be obtained, so that the resolution of the obtained pattern is lowered.
  • the content of the acid dianhydride when R 1 in the structure represented by the general formula (1) is 100 mol% is 80 in that the light collection rate is increased and a small pattern opening can be obtained. It is more preferable to set it as mol% or less, and it is still more preferable to set it as 70 mol% or less.
  • the resin having the structure represented by the general formula (1) preferably has a fluorine component.
  • R 1 and R 2 is an organic group having a fluorine atom.
  • an organic group having a fluorine atom is 100 mole% the total amount of R 1 and R 2, preferably at least 30 mol% .
  • Such a structure is introduced by using 30 mol% or more of a monomer containing a fluorine atom among the monomer components for introducing R 1 and R 2 . Further, in order to obtain adhesion to the substrate, the monomer containing fluorine atoms is preferably 90 mol% or less.
  • the compound having a fluorine atom specifically, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom
  • Aromatic dianhydrides such as acid dianhydrides having amide groups, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) -4,4 ′ -Aromatic diamines such as diaminobiphenyl, compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc.
  • the resin having the structure represented by the general formula (1) is preferably a resin including a structure derived from these compounds.
  • resin which has a structure represented by General formula (1) has a phenolic hydroxyl group component.
  • R 1 and R 2 is an organic group having a phenolic hydroxyl group.
  • the phenolic hydroxyl group can be appropriately dissolved in an alkali developer, and can interact with the photosensitizer to suppress the solubility of the unexposed area, thereby improving the remaining film ratio and increasing the sensitivity.
  • the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and thus is preferable in that high mechanical properties and chemical resistance can be obtained.
  • aromatic dianhydrides such as acid dianhydrides having an amide group, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis Hydroxyl group-containing diamines such as (3-amino-4-hydroxyphenyl) fluorene, Some of the hydrogen atoms of al the aromatic ring, an alkyl group or a fluoroalkyl
  • a photosensitive resin composition having a high residual film ratio and high sensitivity free from tack and development residue can be obtained.
  • R 1 in the general formula (1) may have a structure derived from other acid dianhydrides in addition to the above acid dianhydrides.
  • the acid dianhydride examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl
  • R 2 in the general formula (1) of the present invention may have a structure derived from other diamines in addition to the diamines described above.
  • Aliphatic diamine means a diamine that does not have an aromatic ring, and includes aliphatic alkyl diamines including polyalkyl groups, alkylene ether groups such as polyethylene ether groups, polyoxypropylene groups, tetramethylene ether groups, and alicyclic groups. Examples include diamines and aliphatic diamines having a siloxane structure. Specifically, examples of the aliphatic alkyl diamine include polyalkyl diamine tetramethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, and a diamine Jeffamine KH-511 containing a polyethylene ether group.
  • alicyclic diamines include cyclohexyldiamine and methylenebiscyclohexylamine.
  • Aliphatic diamines having a siloxane structure include bis (3-aminopropyl) tetramethyl.
  • the residue derived from the aliphatic alkyl diamine in all diamine residues is preferably 10 mol% or more, and from the viewpoint of heat resistance, it is preferably 50 mol% or less.
  • an aliphatic group having a siloxane structure is copolymerized within a range in which the heat resistance is not lowered, adhesion to the substrate can be improved.
  • a copolymer of 1 to 15 mol% is preferred.
  • diamines can be used as they are or as the corresponding diisocyanate compounds and trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components. In applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the total diamine.
  • the resin having a structure represented by the general formula (1) of the present invention can contain a sulfonic acid group, a thiol group, and the like.
  • a resin having moderately sulfonic acid groups and thiol groups By using a resin having moderately sulfonic acid groups and thiol groups, a positive photosensitive resin composition having moderate alkali solubility can be obtained.
  • m and n represent the number of repeating structural units of the resin and represent a range of 0 to 100,000, where m + n> 2. From the viewpoint of improving the elongation of the obtained resin, m + n is preferably 10 or more. On the other hand, m + n is 200,000 or less, preferably 1,000 or less, more preferably 100 or less, from the viewpoint of solubility of the resulting photosensitive resin composition containing a resin in an alkaline developer.
  • the weight average molecular weight of the resin having the structure represented by the general formula (1) is preferably 3,000 to 80,000, more preferably 8,000 to 50,000 in terms of polystyrene by gel permeation chromatography. is there. If it is this range, a thick film can be formed easily.
  • the terminal of the resin having the structure represented by the general formula (1) may be blocked with a terminal blocking agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid.
  • a terminal blocking agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid.
  • the resin having the structure represented by the general formula (1) can be produced according to a known method for producing a polyimide precursor.
  • a method of reacting a tetracarboxylic dianhydride having an R 1 group with a diamine compound having an R 2 group and a monoamino compound as a terminal blocking agent under low temperature conditions (II) an R 1 group A diester obtained by having a tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of a diamine compound having an R 2 group, a monoamino compound as a terminal blocking agent and a condensing agent, (III) R 1 group
  • examples include a method in which a diester is obtained from a tetracarboxylic dianhydride having an alcohol and an alcohol, and then the remaining two carboxyl groups are acid chlorideed and reacted with a diamine compound having an R 2 group and a monoamino compound as a terminal blocking agent.
  • the resin polymerized by the above method is preferably put into a large amount of water or a methanol / water mixture, precipitated, filtered, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved. Moreover, after imidating the polyimide precursor and ring-closing polyimide, after obtaining said polyimide precursor, it can synthesize
  • a diamine compound having an R 2 group is dissolved in a polymerization solvent.
  • a tetracarboxylic dianhydride having an R 1 group in a substantially equimolar amount with the diamine compound is gradually added.
  • the mixture is stirred at ⁇ 20 to 100 ° C., preferably 10 to 50 ° C. for 0.5 to 100 hours, more preferably 2 to 24 hours.
  • an end-capping agent after adding tetracarboxylic dianhydride, stirring at the required temperature and time, the end-capping agent may be added gradually or added all at once to react. You may let them.
  • the polymerization solvent is not particularly limited as long as it can dissolve the raw material monomers tetracarboxylic dianhydride and diamine.
  • the polymerization solvent is preferably used in an amount of 100 to 1900 parts by weight, more preferably 150 to 950 parts by
  • the photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the resin having the structure represented by the general formula (1).
  • examples thereof include resins introduced with a crosslinking group such as a group or an epoxy group, and copolymers thereof.
  • Such a resin is soluble in an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate.
  • an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate.
  • the resin containing the structure represented by the general formula (1) is preferably 30% by weight or more.
  • the photosensitive resin composition having positive photosensitivity of the present invention will be described, but the scope of the present invention is not limited to this.
  • a photosensitive resin composition having a negative photosensitivity in which the exposed part reacts by development when a low-transparency polyimide is used, the photoreaction efficiency of the photosensitive agent in the exposed part is deteriorated, resulting in a residual film. The rate becomes low and it becomes difficult to obtain a thick film structure. Therefore, it is necessary to develop a highly transparent polyimide for the highly sensitive photosensitive resin composition as in the positive type.
  • the photosensitive resin composition having positive photosensitivity of the present invention comprises (a) a resin mainly composed of a structure represented by the general formula (8), (b) a photoacid generator and (c) a solvent. contains.
  • the main component means that in the resin having the structure represented by the general formula (8), the structure represented by the general formula (8) is 50 mol% or more, preferably 70 mol% or more. More preferably, it is 90 mol% or more.
  • each R 1 independently represents a monovalent or condensed polycyclic alicyclic structure having a tetravalent organic group having 6 to 40 carbon atoms and a monocyclic alicyclic structure.
  • a tetravalent organic group having 6 to 40 carbon atoms in which the groups are connected to each other directly or via a crosslinked structure and a tetravalent group having 6 to 40 carbon atoms having a semi-alicyclic structure having both an alicyclic structure and an aromatic ring 1 to 1 organic group selected from the group consisting of 5 to 95 mol% when the total amount of R 1 is 100 mol%
  • each R 2 is independently a divalent organic group having 2 to 40 carbon atoms.
  • R 3 represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, m and n each represent a range of 0 to 100,000, and m + n> 2, provided that the general formula (8)
  • the structure represented by the formula is required to have a fluorine component and a phenolic hydroxyl group.
  • the photosensitive resin composition having positive photosensitivity of the present invention preferably contains a resin preferably used in the photosensitive resin composition of the present invention described above, and contains two or more of these. Also good.
  • the positive photosensitive resin composition of the present invention may contain other alkali-soluble resins in addition to the resin whose main component is the structure represented by the general formula (8).
  • examples thereof include resins introduced with a crosslinking group such as a group or an epoxy group, and copolymers thereof.
  • Such a resin is soluble in an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate.
  • an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate.
  • the photoacid generator as the component (b) of the present invention is a compound that generates acid when irradiated with light and gives the property of increasing the solubility in an alkaline aqueous solution of the light-irradiated portion.
  • the quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a sulfonic acid of quinonediazide is bonded to a polyamino compound in a sulfonamide, and a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound in an ester bond and / or sulfonamide. Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide.
  • a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.
  • Such compounds may be used alone or in combination of two or more. Further, by using two types of photoacid generators, the ratio of the dissolution rate between the exposed part and the unexposed part can be increased, and as a result, a highly sensitive photosensitive resin composition can be obtained.
  • 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-B P, TML- Q, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (
  • Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl Examples thereof include, but are not limited to, sulfhydrides.
  • 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.
  • quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group.
  • the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a naphthoquinone diazide sulfonyl ester compound can be obtained by using a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used as a mixture.
  • the molecular weight of the quinonediazide compound is 300 to 3000. More preferably, it is 350-1500.
  • the quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method in which 5-naphthoquinonediazide sulfonyl 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 acid catalyst.
  • the photoacid generator that appropriately stabilizes the acid component generated by exposure is preferably a sulfonium salt, a phosphonium salt, or a diazonium salt. Since the resin composition obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is environmentally undesirable for phosphorus or the like to remain, and it is necessary to consider the color tone of the film.
  • a sulfonium salt is preferably used. Particularly preferred is a triarylsulfonium salt.
  • the photosensitive resin composition of the present invention contains (b) a photoacid generator, an acid is generated in the light irradiation part, and the solubility of the light irradiation part in the alkaline aqueous solution is increased, so that the light irradiation part is dissolved. A positive pattern can be obtained.
  • the content of the photoacid generator used as the component (b) is preferably 0.00 with respect to 100 parts by weight of the resin whose main component is the structure represented by the general formula (8). 01 to 50 parts by weight.
  • the quinonediazide compound is preferably in the range of 3 to 40 parts by weight.
  • the total number of compounds selected from sulfonium salts, phosphonium salts, and diazonium salts is 0%.
  • the range of 05 to 40 parts by weight is preferable, and the range of 0.1 to 30 parts by weight is more preferable.
  • (B) By making content of a photo-acid generator into this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.
  • a compound having a phenolic hydroxyl group may be contained as long as the shrinkage after curing is not reduced.
  • the compound having a phenolic hydroxyl group is, for example, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP -PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis 6X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above,
  • preferred compounds having a phenolic hydroxyl group used in the present invention include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ. , BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F etc. are mentioned.
  • particularly preferred compounds having a phenolic hydroxyl group are, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC -F.
  • the obtained resin composition is hardly dissolved in an alkali developer before exposure, and is easily dissolved in an alkali developer upon exposure. Development is easy in a short time.
  • the content of such a compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight with respect to (a) 100 parts by weight of the resin whose main component is the structure represented by the general formula (8). A more preferred range is 3 to 40 parts by weight.
  • the positive photosensitive resin composition of the present invention contains (c) a solvent.
  • Solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, etc.
  • the content of the solvent is preferably 100 parts by weight or more and 1500 parts by weight or less with respect to 100 parts by weight of the resin whose main component is the structure represented by (a) the general formula (8).
  • the photosensitive resin composition having positive photosensitivity of the present invention may contain components other than the above (a) to (c), and contains a compound having an alkoxymethyl group, a methylol group, or an epoxy group. It is preferable to do. Since a methylol group and an alkoxymethyl group cause a crosslinking reaction in a temperature range of 100 ° C. or higher, they can be crosslinked by heat treatment to obtain a heat-resistant resin film having excellent mechanical properties.
  • Examples having an alkoxymethyl group or a methylol group include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TM M-BPAF, TMOM-BPAP, HML-TPPHBA,
  • the epoxy group thermally crosslinks with the polymer at 200 ° C. or less, and the dehydration reaction due to crosslinking does not occur, so that film shrinkage hardly occurs. Therefore, in addition to mechanical properties, it is effective for low temperature curing and low warpage.
  • the compound having an epoxy group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl) siloxane, and the like, silicone
  • the present invention is not limited to these.
  • Epicron 850-S Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-1514, Epicron EXA-4880, Epicron EXA-4850-150, Epicron EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (named above, manufactured by Dainippon Ink & Chemicals, Inc.), Jamaica Resin BEO-60E Trade names, Shin Nippon Chemical Co., Ltd.), EP-4003S, EP-4000S (Adeka Co., Ltd.), and the like.
  • These compounds having an alkoxymethyl group, a methylol group, or an epoxy group may be contained in two or more kinds.
  • the content of the compound having an alkoxymethyl group, a methylol group, or an epoxy group is 10 to 50 parts by weight with respect to 100 parts by weight of the resin having the structure represented by the general formula (8) as a main component. It is preferably ⁇ 40 parts by weight.
  • the photosensitive resin composition of the present invention can further contain a silane compound.
  • a silane compound By containing the silane compound, the adhesion of the heat-resistant resin film is improved.
  • the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltri Methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Examples include methoxysilane, p-styryltrimethoxysilane,
  • the photosensitive resin composition having positive photosensitivity of the present invention is optionally provided with a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate for the purpose of improving the wettability with the substrate.
  • a surfactant such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.
  • inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder may be contained for the purpose of suppressing the thermal expansion coefficient, increasing the dielectric constant, and reducing the dielectric constant.
  • the viscosity of the positive photosensitive resin composition is preferably 1 to 10,000 mPa ⁇ s.
  • the photosensitive resin composition may be filtered through a filter having a pore size of 0.1 ⁇ m to 5 ⁇ m.
  • the photosensitive resin composition of the present invention can be formed into a polyimide pattern through a step of coating and drying on a support substrate, a step of exposing, a step of developing, and a step of heat treatment.
  • a photosensitive resin composition is applied on a substrate.
  • a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but not limited thereto.
  • the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating.
  • the coating film thickness varies depending on the coating method, the solid content concentration of the positive photosensitive resin composition, the viscosity, etc., but it is generally applied so that the film thickness after drying is 0.1 to 150 ⁇ m.
  • the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.
  • actinic radiation is irradiated on the photosensitive resin film through a mask having a desired pattern.
  • actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays.
  • i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are used. preferable.
  • the exposed portion may be removed using a developer after exposure.
  • Developer is tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate
  • An aqueous solution of a compound exhibiting alkalinity, such as cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred.
  • polar aqueous solutions such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol are used in these alkaline aqueous solutions.
  • One or more kinds of alcohols such as ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added. After development, it is common to rinse with water.
  • one or more alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, and 3-methoxymethylpropanoate may be added to water.
  • a temperature of 150 ° C. to 500 ° C. is applied to convert to a heat resistant resin film.
  • This heat treatment is preferably carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature.
  • a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, a method of linearly raising the temperature from room temperature to 320 ° C. over 2 hours, and the like can be mentioned.
  • the heat treatment is preferably performed at 250 ° C. or lower because there is a fear that the electrical characteristics of the element may change due to high-temperature heating or repetition thereof, and the warpage of the substrate may increase.
  • the heat-resistant resin film formed from the photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, it is suitably used for applications such as a semiconductor passivation film, a semiconductor element surface protective film, an interlayer insulating film, an interlayer insulating film of a multilayer wiring for high-density mounting, and an insulating layer of an organic electroluminescent element. It is not limited to this, and various structures can be taken.
  • FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention.
  • a passivation film 3 is formed on an input / output Al pad 2 in a silicon wafer 1, and a via hole is formed in the passivation film 3.
  • a pattern (insulating film) 4 made of the photosensitive resin composition of the present invention is formed thereon, and a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2.
  • the film 5 etches the periphery of the solder bump 10 to insulate between the pads.
  • Barrier metal 8 and solder bumps 10 are formed on the insulated pads.
  • the metal wiring 6 is formed by plating.
  • the photosensitive resin composition of the present invention is applied, and a pattern (insulating film 7) as shown in FIGS. 2 to 2d is formed through a photolithography process.
  • the photosensitive resin composition of the insulating film 7 is subjected to thick film processing in the scribe line 9.
  • each layer can be formed by repeating the above steps.
  • the total thickness of the interlayer insulating film is 10 ⁇ m or more, and is preferably 50 ⁇ m or less because of the influence on the warp of the chip and the like.
  • the photosensitive resin composition can obtain a heat-resistant resin coating film having a film thickness of 10 ⁇ m or more.
  • a high-resolution heat-resistant resin film is obtained.
  • the wafer is diced along the last scribe line 9 and cut into chips. If the insulating film 7 has no pattern formed on the scribe line 9 or if a residue remains, cracks or the like occur during dicing, which affects the reliability evaluation of the chip. For this reason, it is very preferable to provide pattern processing excellent in thick film processing as in the present invention in order to obtain high reliability of the semiconductor device.
  • Varnish was spin-coated on an 8-inch silicon wafer, and then baked for 3 minutes on a 120 ° C. hot plate (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) to prepare a pre-baked film having a thickness of 10 ⁇ m. .
  • This film was exposed using an i-line stepper (NIKON NSR i9) at an exposure dose of 0 to 1000 mJ / cm 2 in 10 mJ / cm 2 steps.
  • the exposure amount (hereinafter referred to as the minimum exposure amount Eth) at which the exposed portion was not completely eluted after exposure and development was defined as sensitivity. If Eth is 400 mJ / cm 2 or less, it can be determined that the sensitivity is high. 300 mJ / cm 2 or less is more preferable.
  • the developing film was heated to 250 ° C. at an oxygen concentration of 20 ppm or less at 5 ° C./min, and heat-treated at 250 ° C. for 1 hour. .
  • the temperature reached 50 ° C. or lower, the silicon wafer was taken out and the thickness of the heat resistant resin film on the silicon wafer was measured.
  • thermal crosslinkable compounds used in each example and comparative example are shown below.
  • Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (a) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was reacted at ⁇ 15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.
  • Synthesis Example 2 Synthesis of quinonediazide compound (b) Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86 g of 5-naphthoquinonediazidesulfonyl acid chloride (0.10 mol) and 13.43 g (0.05 mol) of 4-naphthoquinonediazide sulfonyl chloride were dissolved in 50 g of 1,4-dioxane and brought to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not exceed 35 ° C.
  • TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
  • Synthesis Example 3 Synthesis of quinonediazide compound (c) Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40.28 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (c) represented by the following formula was obtained in the same manner as in Synthesis Example 2.
  • Synthesis Example 4 Synthesis of quinonediazide compound (d) Under a dry nitrogen stream, TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 28.83 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 13.43 g (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Using 20.24 g of triethylamine mixed with 50 g of 1,4-dioxane, a quinonediazide compound (d) represented by the following formula was obtained in the same manner as in Synthesis Example 2.
  • Synthesis Example 5 Synthesis of Acrylic Resin (e) In a 500 ml flask, 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) 150 g was charged. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred at 5 ° C. for 5 hours.
  • PGMEA propylene glycol monomethyl ether acetate
  • a novolac resin (f) polymer solid was obtained. From GPC, Mw was 3,500. ⁇ -Butyrolactone (GBL) was added to the obtained novolak resin (f) to obtain a novolak resin (f) solution having a solid content concentration of 43% by weight.
  • Synthesis Example 7 Synthesis of polybenzoxazole precursor (g) In a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was adjusted. Cooled to -15 ° C. A solution prepared by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C.
  • the solution was poured into 3 L of water containing 10% by weight of methanol to precipitate a white precipitate.
  • This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble polybenzoxazole precursor (g).
  • GBL was added to the obtained polybenzoxazole precursor (g) to obtain a polybenzoxazole precursor (g) solution having a solid content concentration of 43% by weight.
  • Synthesis Example 8 Synthesis of polyhydroxystyrene (h) 500 ml of tetrahydrofuran and 0.01 mol of sec-butyllithium as an initiator were added to a mixed solution of pt-butoxystyrene and styrene in a molar ratio of 3: 1. 20 g was added and polymerized with stirring for 3 hours. The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the precipitated polymer was dried to obtain a white polymer. Further, dissolve in 400 ml of acetone, add a small amount of concentrated hydrochloric acid at 60 ° C.
  • Example 1 Under a dry nitrogen stream, 15.57 g (0.04 mol) of BAHF and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. PMDA-HH (1.12 g, 0.005 mol) and 6FDA (19.99 g, 0.045 mol) were added together with NMP (10 g) and reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (A).
  • PMDA-HH 1.12 g, 0.005 mol
  • 6FDA (19.99 g, 0.045 mol) were added together with NMP (10 g) and reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C
  • Example 2 Under a dry nitrogen stream, 11.90 g (0.03 mol) of BAHF, 2.0 g (0.01 mol) of DAE, and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. PMDA-HH (0.009 g, 0.045 mol) and 6FDA (2.22 g, 0.005 mol) were added together with NMP (10 g), and the mixture was reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (B).
  • PMDA-HH 0.009 g, 0.045 mol
  • 6FDA 2.22 g, 0.005 mol
  • Example 3 Under a dry nitrogen stream, 25.68 g (0.04 mol) of the compound (a) obtained in Synthesis Example 1 and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. To this, 4.48 g (0.02 mol) of PMDA-HH and 9.31 g (0.03 mol) of ODPA were added together with 10 g of NMP, and reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 13.10 g (0.11 mol) of N, N-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the solution was poured into 2 L of water, and a solid precipitate was collected by filtration. The resin solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor resin (C).
  • C polyimide precursor resin
  • Example 4 Under a dry nitrogen stream, 11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. To this, 4.48 g (0.02 mol) of PMDA-HH and 13.33 g (0.03 mol) of 6FDA were added together with 10 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (D).
  • D closed ring polyimide resin
  • Example 5 Under a dry nitrogen stream, 11.91 g (0.04 mol) of APBS and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. To this, 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added together with 10 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed ring polyimide resin (E).
  • E closed ring polyimide resin
  • a varnish E of positive photosensitive resin composition was obtained by adding 1.0 g of KBM-403 to 50 g of GBL. Using the obtained varnish E, sensitivity evaluation, residual film ratio evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.
  • Example 6 BAHF 9.16g (0.03mol), DAE2.0 (0.01mol), ED600 4.5g (0.008mol), SiDA 0.62g (0.003mol) were dissolved in NMP 100g under dry nitrogen stream. I let you. To this, 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added together with 10 g of NMP, and reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 13.10 g (0.11 mol) of N, N-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the solution was poured into 2 L of water, and a solid precipitate was collected by filtration. The resin solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor resin (F).
  • F polyimide precursor resin
  • Example 7 BAHF 9.16g (0.03mol), DAE2.0 (0.01mol), ED600 4.5g (0.008mol), SiDA 0.62g (0.003mol) were dissolved in NMP 100g under dry nitrogen stream. I let you. To this, 6.01 g (0.02 mol) of TDA-100 and 9.31 g (0.03 mol) of ODPA were added together with 10 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (G).
  • G closed ring polyimide resin
  • Varnish G of a positive photosensitive resin composition was obtained by adding 1.0 g of KBM-403 to 50 g of GBL. Using the obtained varnish G, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.
  • Example 8 Under a dry nitrogen stream, 15.57 g (0.04 mol) of BAHF and 0.62 g (0.003 mol) of SiDA were dissolved in 100 g of NMP. To this, 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added together with 10 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed ring polyimide resin (M).
  • M closed ring polyimide resin
  • Example 9 Under a dry nitrogen stream, BAHF 9.16 g (0.03 mol), ED6002.0 (0.01 mol), ED600 9.0 g (0.015 mol), SiDA 0.62 g (0.003 mol) were dissolved in NMP 100 g. I let you. To this, 6.01 g (0.02 mol) of TDA-100 and 13.33 g (0.03 mol) of 6FDA were added together with 10 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (N).
  • Example 10 Under a dry nitrogen stream, BAHF 9.16 g (0.03 mol), ED600 9.0 g (0.015 mol), SiDA 0.62 g (0.003 mol) were dissolved in NMP 100 g. To this, 8.97 g (0.05 mol) of PMDA-HH and 4.44 g (0.01 mol) of 6FDA were added together with 10 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (O).
  • NMP 100 g 8.97 g (0.05 mol) of PMDA-HH and 4.44 g (0.01 mol) of 6FDA were added together with 10 g of NMP, reacted at 60 ° C
  • Varnish O of a positive photosensitive resin composition was obtained by adding 1.0 g of KBM403 to 50 g of GBL. Using the obtained varnish O, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.
  • Example 11 Under a dry nitrogen stream, BAHF 9.16 g (0.03 mol), ED6009.0 (0.015 mol), and SiDA 0.62 g (0.003 mol) were dissolved in 100 g of NMP. To this, 2.80 g (0.013 mol) of PMDA-HH and 16.66 g (0.037 mol) of 6FDA were added together with 10 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (P).
  • P closed ring polyimide resin
  • Varnish H of a positive photosensitive resin composition was obtained by adding 1.0 g of KBM-403 to 50 g of GBL. Using the obtained varnish H, sensitivity evaluation, residual film ratio evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.
  • Varnish I of positive photosensitive resin composition was obtained by adding 1.0 g of KBM-403 to 50 g of GBL. Using the obtained varnish I, sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.
  • the resin solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor resin (J) 17.5 g of the obtained resin (J), the quinonediazide compound (b) obtained in Synthesis Example 2.
  • 3 g, 16 g of the acrylic resin (e) obtained in Synthesis Example 5, 3.0 g of the crosslinking agent MX-270, and 1.0 g of KBM-403 were added to 50 g of GBL to obtain a varnish J of a positive photosensitive resin composition. .
  • sensitivity evaluation, residual film rate evaluation, development film pattern evaluation, thick film formation evaluation, and resolution evaluation were performed as described above. The evaluation results are shown in Table 2.

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WO2017221776A1 (ja) * 2016-06-24 2017-12-28 東レ株式会社 ポリイミド樹脂、ポリイミド樹脂組成物、それを用いたタッチパネルおよびその製造方法、カラーフィルタおよびその製造方法、液晶素子およびその製造方法、有機ｅｌ素子およびその製造方法
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US11347146B2 (en) 2016-09-09 2022-05-31 Toray Industries, Inc. Resin composition
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