Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
  • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• • 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
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a soluble polymer compound, a method for producing a soluble polymer compound, a resin composition, a resin composition film, a cured film, and an electronic component. More specifically, the present invention relates to a soluble polymer compound that is suitable for use in surface protection films for semiconductor elements and electronic components, interlayer insulating films, and MEMS (microelectromechanical systems) structures.
• the object of the present invention is to provide a soluble polymer compound capable of exhibiting sufficient adhesion, storage stability, and fine pattern processability, a method for producing the soluble polymer compound, a resin composition containing the soluble polymer compound, a resin composition film made of the resin composition, a cured film obtained by curing the resin composition or the resin composition film, and an electronic component having the cured film.
• the present invention has the following configuration.
• ⁇ 1> Contains a structure having a repeating unit represented by chemical formula (1), A soluble polymer compound further comprising a structure derived from an acid anhydride silane residue,
• the soluble polymer compound (hereinafter referred to as “(a) soluble polymer compound”) contains a structure represented by chemical formula (2), A soluble polymer compound, characterized in that in said chemical formula (2), the acid anhydride silane residue is derived from a structure represented by chemical formula (4).
• A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms
• B represents a divalent diamine residue having two or more carbon atoms.
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms
• n represents an integer from 0 to 3.
• X represents a structure represented by chemical formula (3)
• an oxygen atom in chemical formula (3) is bonded to a Si atom in chemical formula (2).
• Y represents a hydrocarbon group having 1 to 10 carbon atoms
• Z represents a silane residue having 1 to 10 carbon atoms.
• a method for producing a soluble polymer compound according to ⁇ 1> A method for producing a soluble polymer compound, comprising copolymerizing raw materials used in a polymerization step under conditions that satisfy the following formula (1), where the total amount of tetracarboxylic dianhydrides is A mol, the total amount of diamines is B mol, and the total amount of acid anhydride silanes is C mol: 0.6 ⁇ B/(A+0.5C) ⁇ 0.98 Formula (1)
• a resin composition comprising the soluble polymer compound (a) according to ⁇ 1>.
• a negative photosensitive resin composition further comprising (b) a polymerizable compound and (c) a photopolymerization initiator in the resin composition according to ⁇ 4>.
• ⁇ 7> A resin composition film comprising the resin composition according to ⁇ 4>.
• ⁇ 8> A cured film obtained by curing the resin composition according to ⁇ 4> or the resin composition film according to ⁇ 7>.
• the present invention provides a soluble polymer compound capable of exhibiting sufficient adhesion, storage stability, and fine pattern processability, a method for producing the soluble polymer compound, a resin composition containing the soluble polymer compound, a resin composition film made of the resin composition, a cured film obtained by curing the resin composition or the resin composition film, and an electronic component having the cured film.
• the present invention relates to a polymerizable composition
• a polymerizable composition comprising a repeating unit represented by chemical formula (1), A soluble polymer compound further comprising a structure derived from an acid anhydride silane residue,
• the soluble polymer compound (hereinafter referred to as “(a) soluble polymer compound”) contains a structure represented by chemical formula (2),
• the soluble polymer compound is characterized in that in the above chemical formula (2), the acid anhydride silane residue is derived from a structure represented by chemical formula (4).
• A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms
• B represents a divalent diamine residue having two or more carbon atoms.
• A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
• B represents a divalent diamine residue having 2 or more carbon atoms
• n represents an integer from 0 to 3.
• X represents a structure represented by chemical formula (3), and the oxygen atom in chemical formula (3) is bonded to the Si atom in chemical formula (2).
• Y represents a hydrocarbon group having 1 to 10 carbon atoms
• Z represents a silane residue having 1 to 10 carbon atoms.
• the soluble polymer compound of the present invention contains a structure having a repeating unit represented by chemical formula (1).
• the composition has excellent storage stability when made into a composition, and the mechanical strength of the cured film is excellent.
• the weight average molecular weight of the soluble polymer compound of the present invention is not particularly limited, but it is preferable that the weight average molecular weight is 1,000 or more and 200,000 or less.
• the soluble polymer compound may be used alone or in combination of two or more kinds.
• the weight average molecular weight of the soluble polymer compound in the present invention is determined by measuring by gel permeation chromatography (GPC) and calculating in polystyrene equivalent.
• Soluble polymer compounds refer to polymer compounds that dissolve in an amount of 0.1 g or more in 100 g of gamma-butyrolactone solution at 25°C.
• the soluble polymer compound of the present invention is preferably alkali-soluble. If it is alkali-soluble, it is preferable because it can be developed with an alkaline aqueous solution without using organic solvents, which are a factor in environmental load, during development during pattern processing.
• Alkali-soluble here refers to a compound that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 25°C.
• the soluble polymer compound of the present invention In order to exhibit alkali solubility, it is desirable for the soluble polymer compound of the present invention to have an alkali soluble functional group.
• the alkali soluble functional group is a functional group having acidity, and specific examples include a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group.
• the soluble polymer compound of the present invention it is preferable for the soluble polymer compound of the present invention to be a compound having a phenolic hydroxyl group in the molecular chain.
• the soluble polymer compound of the present invention contains a structure derived from an acid anhydride silane residue.
• An acid anhydride silane refers to a silane compound having at least one acid anhydride group.
• the soluble polymer compound of the present invention is (a) a soluble polymer compound
• the (a) soluble polymer compound contains a structure represented by chemical formula (2).
• the (a) soluble polymer compound contains a structure represented by chemical formula (2), and thus exhibits good adhesion and storage stability.
• the soluble polymer compound is derived from the structure represented by chemical formula (4) in which the acid anhydride silane residue in the chemical formula (2) is represented by chemical formula (4).
• An example of an acid anhydride silane represented by chemical formula (4) is X-12-967C (product name, manufactured by Shin-Etsu Chemical Co., Ltd.).
• the soluble polymer compound of the present invention is preferably a polyimide or polyamideimide, but from the viewpoint of alkali solubility, it is more preferable that the compound has at least one structure selected from the structures represented by the following chemical formulas (5) and (6).
• X1 represents a divalent to decavalent organic group
• X2 represents a tetravalent to decavalent organic group
• Y1 and Y2 each independently represent a divalent to tetravalent organic group
• R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
• q represents an integer of 0 to 2
• r, s, t, and u each independently represent an integer of 0 to 4.
• Y1 and Y2 each independently represent a divalent to tetravalent organic group, and represent an organic group derived from a diamine.
• the resin B in the chemical formulas (1) and (2) and Y1 and Y2 in the chemical formulas (5) and (6) of the soluble polymer compound preferably contain a diamine residue having a phenolic hydroxyl group.
• the resin can be made moderately soluble in an alkaline developer, so that a high contrast between exposed and unexposed areas can be obtained, and a desired pattern can be formed.
• diamines having a phenolic hydroxyl group include, but are not limited to, aromatic diamines such as 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, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, as well as compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons are substituted with alkyl groups or fluoroalkyl groups
• B in the chemical formulas (1) and (2), and Y1 and Y2 in the chemical formulas (7) and (8) may contain a diamine residue having an aromatic group other than those mentioned above. By copolymerizing these, the heat resistance can be improved.
• the diamine residue having an aromatic group include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine,
• aromatic diamine examples include aromatic diamines such as 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and compounds in which a portion of the hydrogen atoms of these aromatic rings or hydrocarbons is substituted with an alkyl group or fluoroalkyl group having 1 to 10 carbon atoms, a halogen atom, or the like, but are not limited to these.
• X 1 and X 2 in the above chemical formulas (5) and (6) are preferably a carboxylic acid residue, X 1 is a divalent to decavalent organic group, and X 2 is a tetravalent to decavalent organic group.
• the carboxylic acid residue preferably has a structure derived from an alicyclic tetracarboxylic dianhydride.
• the soluble polymer compound is at least one compound selected from the group consisting of polyimide and polyamide-imide, and further has a structure derived from an alicyclic tetracarboxylic dianhydride.
• the carboxylic acid residue has a structure derived from an alicyclic tetracarboxylic dianhydride, which increases the light transmittance of the resin composition at the exposure wavelength, making it easier to process into a thick film of 20 ⁇ m or more.
• the soluble polymer compound has a structure derived from an alicyclic tetracarboxylic dianhydride, which is preferable in that it has higher cationic polymerization reactivity than aromatic acid dianhydrides, improving the chemical resistance of the film when the resin composition is made into a cured film.
• alicyclic tetracarboxylic dianhydrides having a polycyclic structure are preferred, as they improve the chemical resistance and ion migration resistance of the cured product.
• the soluble polymer compound in the present invention has a structure derived from an alicyclic tetracarboxylic dianhydride having a polycyclic structure
• the soluble polymer compound preferably has a structure derived from a compound represented by at least one of the following chemical formulas (7) or (8).
• R 1 , R 2 and R 3 each independently represent a hydrogen atom or a methyl group.
• the soluble polymer compound has a structure derived from the compound represented by chemical formula (7) or (8), and therefore the resin skeleton has flexibility, which makes the resin composition before curing highly soluble in organic solvents, less likely to cause resin precipitation in the resin composition, and is preferred in terms of excellent storage stability.
• the tetracarboxylic acid residue represented by A in the chemical formulas (1) and (2) is preferably an alicyclic tetracarboxylic acid dianhydride, more preferably an alicyclic tetracarboxylic acid dianhydride having a polycyclic structure, and even more preferably has a structure derived from a compound represented by at least one of chemical formulas (7) and (8).
• organic groups derived from alicyclic tetracarboxylic dianhydrides having a polycyclic structure include 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, lan-3-yl)-7-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-nor
• the carboxylic acid residue or tetracarboxylic acid dianhydride may include an acid dianhydride other than the alicyclic tetracarboxylic acid dianhydride having a polycyclic structure.
• an acid dianhydride other than the alicyclic tetracarboxylic acid dianhydride having a polycyclic structure.
• the molecular chain ends of the soluble polymer compound of the present invention may be blocked with a terminal blocking agent of a carboxylic acid or an acid anhydride having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group.
• a terminal blocking agent of a carboxylic acid or an acid anhydride having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group.
• the end-capping material it is preferable to use an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• an acid anhydride a monocarboxylic acid
• a monoacid chloride compound a monoactive ester compound.
• the molecular chain end of the soluble polymer compound becomes an acid anhydride residue, and when the soluble polymer compound is applied to a cationic polymerization type photosensitive resin composition, the cationic polymerization reaction proceeds more easily, which is preferable in that the chemical resistance of the cured film is improved.
• acid anhydrides monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds as end-capping agents
• acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride
• 3-carboxyphenol 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxyphenyl, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene ...5-
• the soluble polymer compound of the present invention is synthesized, for example, by a manufacturing method including the following steps 1 and 2, but is not limited thereto.
• Step 1 A step of reacting a tetracarboxylic dianhydride, a diamine, and at least one of an aminosilane and an acid anhydride silane in a solvent at low temperature to obtain a polyimide precursor.
• Step 2 A step of reacting the polyimide precursor at high temperature to form a polyimide.
• the tetracarboxylic dianhydride, diamine, and aminosilane or acid anhydride silane may be, for example, those described above.
• the synthesis may be performed by replacing part of the tetracarboxylic dianhydride and diamine with the end-capping agent.
• the solvent used in step 1 is preferably a polar solvent from the viewpoint of solubility, such as dimethylacetamide, N-methylpyrrolidone, and ⁇ -butyrolactone.
• the reaction temperature in step 1 is preferably a low temperature of 140°C or less in terms of improving reactivity, and is preferably 60°C or more in terms of the solubility of the tetracarboxylic dianhydride, diamine, and aminosilane or acid anhydride silane.
• the reaction temperature is preferably a high temperature of 160°C or higher in order to sufficiently imidize the polyimide precursor synthesized in step 1, and is preferably 220°C or lower, taking into account the boiling point of the solvent.
• known polyimide synthesis methods can be used for the manufacturing method of the soluble polymer compound of the present invention.
• methods for obtaining a polyimide precursor can include a method of reacting a tetracarboxylic dianhydride, a dicarboxylic anhydride, and a diamine compound at low temperature, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting the diamine and a monoamine in the presence of a condensing agent.
• Polyimide can then be synthesized using a known imidization reaction.
• At least one of aminosilane and acid anhydride silane can be added in any of the steps to obtain the soluble polymer compound of the present invention, but it is preferable to add it in the step of obtaining the polyimide precursor.
• the raw materials used in the polymerization step are copolymerized under conditions that satisfy the following formula (1), where the total amount of tetracarboxylic dianhydrides is A mol, the total amount of diamines is B mol, and the total amount of acid anhydride silanes is C mol.
• formula (1) where the total amount of tetracarboxylic dianhydrides is A mol, the total amount of diamines is B mol, and the total amount of acid anhydride silanes is C mol.
• the weight average molecular weight of the polymer compound is likely to be 1,000 or more, which is preferable in terms of excellent film formability and storage stability when the resin composition is made into a film.
• (A+0.5C) ⁇ 0.98 the proportion of polymer compounds having amine residues at the ends is reduced, which is preferable in terms of the ease with which the cationic polymerization reaction proceeds when the (a) soluble polymer compound is applied to a cationic polymerization type photosensitive resin composition, and thus the chemical resistance and pattern processability of the cured film are improved.
• the soluble polymer compound is preferably polymerized by the above method, then poured into a large amount of water or a mixture of methanol and water, precipitated, filtered, dried, and isolated.
• the drying temperature is preferably 40 to 100°C, and more preferably 50 to 80°C. This operation removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties after thermal curing.
• the imidization ratio in the present invention can be easily determined, for example, by the following method.
• the infrared absorption spectrum of the polymer is measured using a sample having an imidization ratio of 100% after heat treatment at 350°C for 1 hour, and the content of imide groups in the resin before heat treatment is calculated by comparing the peak intensities near 1377 cm -1 of the resin before and after heat treatment to determine the imidization ratio. Since this suppresses the change in the ring closure ratio during thermal curing and provides the effect of reducing stress, the imidization ratio is preferably 50% or more, and more preferably 80% or more.
• the resin composition of the present invention contains (a) a soluble polymer compound.
• the resin composition of the present invention exhibits sufficient adhesion to the substrate and storage stability.
• the resin composition of the present invention is preferably a negative-type photosensitive resin composition characterized by containing (b) a polymerizable compound and (c) a photopolymerization initiator.
• a negative-type photosensitive resin composition is obtained that exhibits sufficient adhesion to a substrate, storage stability, and pattern processability.
• the (b) polymerizable compound preferably contains at least one of a radical polymerizable compound or a cationic polymerizable compound
• the (c) photopolymerization initiator preferably contains at least one of a photoradical polymerization initiator or a photocationic polymerization initiator.
• the (b) polymerizable compound contains a cationic polymerizable compound
• the (c) photopolymerization initiator contains a photocationic polymerization initiator.
• the radical polymerizable compound is a compound having a radical polymerizable group, and is a compound that reacts with radicals generated by irradiation with light such as ultraviolet light in the presence of a photoradical polymerization initiator.
• the radical polymerizable group that the radical polymerizable compound has include unsaturated double bond functional groups such as vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups, and/or unsaturated triple bond functional groups such as propargyl groups, and among these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred in terms of polymerizability.
• Radically polymerizable compounds include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, ⁇ -methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cycl
• a photoradical polymerization initiator is a compound that generates radicals when exposed to ultraviolet light, etc.
• the photoradical polymerization initiator include benzophenones such as benzophenone, Michler's ketone, 4,4-bis(diethylamino)benzophenone, and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; benzylidenes such as 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone and 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone; coumarins such as 7-diethylamino-3-nonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylmethylbenzimidazolyl)coumarin, and 3-(2-benzo
• anthraquinones benzoins such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether
• thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-isopropylthioxanthone
• mercapto compounds such as ethylene glycol di(3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole
• glycines such as N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-(p-chlorophenyl)glycine, and N-(4-cyanophenyl)glycine, 1-phenyl-1,2-butanedione-2-(o-meth
• Cationically polymerizable compounds are compounds that have a cationic polymerizable group and react with cations generated by irradiation with light such as ultraviolet light in the presence of a photocationic polymerization initiator.
• the cationic polymerizable compounds include cyclic ether compounds (epoxy compounds, oxetane compounds, etc.), ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters.
• epoxy compound known compounds can be used, including aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.
• Aromatic epoxy compounds include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts of these compounds).
• Alicyclic epoxy compounds include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).
• an oxidizing agent e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
• Aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxy compounds of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).
• Oxetane compounds that can be used include known compounds, such as 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.
• known compounds such as 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-e
• known cationic polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, and cationic polymerizable nitrogen-containing monomers.
• Aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.
• Aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.
• polyfunctional vinyl ethers examples include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.
• styrenes examples include styrene, ⁇ -methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.
• Cationically polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.
• Bicyclo orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane.
• spiro orthocarbonates examples include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.
• Spiro orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.
• epoxy compounds, oxetane compounds, and vinyl ethers are preferred, and epoxy compounds and oxetane compounds are more preferred.
• an epoxy compound having an isocyanurate skeleton as the cationically polymerizable compound, it is possible to keep the dielectric constant and dielectric tangent of the cured film obtained by curing the resin composition low while maintaining the cationic polymerizability. Furthermore, when developing with an alkaline aqueous solution, for reasons that are unclear, the compound itself does not dissolve in an alkaline aqueous solution, but by being made compatible with the (a) soluble polymer compound that is alkaline soluble, it is possible to perform pattern processing in an alkaline aqueous solution without inhibiting the alkaline solubility of the resin composition.
• epoxy compounds containing an isocyanurate skeleton include triglycidyl isocyanurate such as TEPIC-S, TEPIC-L, TEPIC-VL, TEPIC-PASB26L, TEPIC-PASB22, TEPIC-FL, and TEPIC-UC (product names, all manufactured by Nissan Chemical Industries, Ltd.).
• the content is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to 100% by mass of the total of the cationic polymerizable compounds.
• the upper limit of the content of the epoxy compound having an isocyanurate skeleton is 100% by mass.
• the polyfunctional epoxy compound preferably has an epoxy equivalent of 80 g/eq. or more and 160 g/eq. or less.
• the epoxy equivalent of the polyfunctional epoxy compound is more preferably 80 g/eq. or more and 150 g/eq. or less, and even more preferably 85 g/eq. or more and 130 g/eq. or less.
• polyfunctional epoxy compounds that are liquid at room temperature and have an epoxy equivalent of 80 g/eq. or more and 160 g/eq. or less include TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.), bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, Showfree BATG, Showfree PETG (trade names, all manufactured by Showa Denko K.K.), etc.
• the cationically polymerizable compounds may be used alone or in combination of two or more.
• the content of the cationic polymerizable compound is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more, per 100 parts by mass of the soluble polymer compound (a), in order to exhibit sufficient cationic curability and improve pattern processability.
• the content of the cationic polymerizable compound is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less, per 100 parts by mass of the soluble polymer compound (a), in order to exhibit sufficient cationic curability and improve pattern processability.
• the photocationic polymerization initiator generates an acid by the action of light, causing cationic polymerization.
• the photocationic polymerization initiator is preferably an onium salt.
• photocationic polymerization initiators include aromatic iodonium complex salts, aromatic sulfonium complex salts, aromatic borate complex salts, and aromatic gallate complex salts.
• aromatic iodonium complex salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate.
• photocationic polymerization initiators in addition to the above aromatic iodonium complex salts, include (4-hydroxyphenyl)dimethylsulfonium benzenesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium benzenesulfonate, benzyl (4-hydroxyphenyl)methylsulfonium benzenesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium benzenesulfonate, (4-hydroxyphenyl)methyl ((2-methylphenyl)methyl)sulfonium benzenesulfonate, (4-hydroxyphenyl)dimethylsulfonium camphorsulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium camphorsulfonate, benzyl (4-hydroxyphenyl)methylsulfonate
• initiators include (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium camphorsulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, benzyl (4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, "San-Aid” (registered trademark), SI-145, SI-200, SI-250, SI-B2A, SI-B3A, SI-B3, SI-B4, SI-B5 (manufactured by Sanshin Chemical Industry Co.
• an onium salt as a photocationic polymerization initiator, it is possible to proceed with sufficient initiation reaction of cationic polymerization when using a cyclic ether compound.
• the content of the cationic photopolymerization initiator is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.7 parts by mass or more, when the cationic polymerizable compound is taken as 100 parts by mass. This allows the cationic polymerizable compound to exhibit sufficient curability, and improves pattern processability.
• the content of the cationic photopolymerization initiator is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, when the cationic polymerizable compound is taken as 100 parts by mass.
• the resin composition of the present invention may contain a thermal crosslinking agent.
• the thermal crosslinking agent is preferably a compound having an alkoxymethyl group or a methylol group.
• Examples of compounds having an alkoxymethyl group or a methylol group include 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, T Examples include ML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA
• the resin composition of the present invention may further contain a silane compound.
• a silane compound By containing a silane compound, the adhesion of the resin composition coating described below is improved.
• Specific examples of silane compounds include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris( ⁇ -methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane,
• the resin composition of the present invention may contain, as necessary, a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane, in order to improve wettability with the support.
• the resin composition may contain inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder, in order to suppress the thermal expansion coefficient and increase or decrease the dielectric constant.
• the resin composition of the present invention may be in any shape before curing, and may be in the form of, for example, a varnish or a film.
• the resin composition of the present invention in the form of a film is also referred to as the negative-type photosensitive resin composition coating of the present invention (hereinafter, sometimes simply referred to as the "resin composition coating").
• the negative type photosensitive resin composition film of the present invention (hereinafter sometimes simply referred to as "resin composition film”) has a support and the resin composition of the present invention in the form of a film, that is, the resin composition film of the present invention is a resin composition film having a support and a resin composition coating formed from the resin composition of the present invention. Therefore, the resin composition film of the present invention is a resin composition film in the form of a film formed on a support, that is, a resin composition film having a resin composition coating formed from the resin composition of the present invention on a support.
• the components (a), (b), and (c) and any other components added as required can be dissolved in an organic solvent.
• a resin composition film can be obtained, for example, by applying the resin composition of the present invention onto a support and then drying it as required.
• the resin composition film of the present invention is a film made of the resin composition of the present invention, and can be obtained, for example, by applying a varnish of the resin composition of the present invention (hereinafter sometimes simply referred to as "resin composition varnish") onto a support and then drying it.
• the organic solvent used in the resin composition varnish may be any solvent that dissolves the resin composition.
• organic solvents include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate.
• ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethy
• ketones such as acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone; alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; and others such as N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and ⁇ -butyrolactone.
• alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butan
• the amount of organic solvent added is preferably adjusted so that the solids concentration is 20% by weight or more and 70% by weight or less, with additives other than the organic solvent being the solids content.
• the resin composition varnish may be filtered using filter paper or a filter.
• the filtration method is not particularly limited, but a method of filtering by pressure filtration using a filter with a retention particle size of 0.4 to 10 ⁇ m is preferred.
• the resin composition film of the present invention is a resin composition film made of the resin composition of the present invention, and therefore the resin composition film of the present invention is formed, for example, by forming a resin composition coating on a support.
• the support is not particularly limited, and various types of films that are usually commercially available can be used, such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film.
• PET polyethylene terephthalate
• the bonding surface between the support and the resin composition coating may be subjected to a surface treatment with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like in order to improve adhesion and peelability.
• the thickness of the support is not particularly limited, but from the viewpoint of workability, it is preferably in the range of 10 to 100 ⁇ m.
• the resin composition film of the present invention may have a protective film on the resin composition coating in order to protect the surface. This makes it possible to protect the surface of the resin composition film from pollutants such as dust and dirt in the air.
• protective films include polyolefin films and polyester films. It is preferable that the protective film has low adhesive strength with the resin composition film.
• Methods for applying the resin composition varnish to a support include spin coating using a spinner, spray coating, roll coating, screen printing, and methods using a blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, and slit die coater.
• the coating thickness varies depending on the coating method, the solids concentration of the resin composition, and the viscosity, but it is usually preferable for the coating thickness after drying to be 0.5 ⁇ m or more and 100 ⁇ m or less.
• drying an oven, a hot plate, infrared rays, etc. can be used.
• the drying temperature and drying time may be within a range that allows the organic solvent to volatilize, and it is preferable to set the drying temperature and time appropriately within a range that allows the resin composition film to be in an uncured or semi-cured state.
• drying is preferably performed in the range of 40°C to 120°C for one minute to several tens of minutes.
• the temperature may be increased stepwise by combining these temperatures, for example, heat treatment may be performed at 70°C, 80°C, and 90°C for one minute each.
• the resin composition varnish When using a resin composition varnish to form a resin composition coating on a substrate, the resin composition varnish is first applied onto the substrate. Coating methods include spin coating using a spinner, spray coating, roll coating, screen printing, and the like. The coating thickness varies depending on the coating technique, the solids concentration and viscosity of the resin composition, and the like, but it is generally preferable to apply the coating so that the film thickness after drying is 0.5 ⁇ m or more and 100 ⁇ m or less. Next, the substrate coated with the resin composition varnish is dried to form a resin composition coating.
• Drying can be performed using an oven, a hot plate, infrared rays, etc.
• the drying temperature and drying time may be within a range that allows the organic solvent to volatilize, and it is preferable to set the drying temperature and time appropriately so that the resin composition coating is in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 50 to 150°C for one minute to several hours.
• the resin composition film when used, if there is a protective film, this is peeled off, and the resin composition film is placed opposite the substrate and bonded by thermocompression to form a resin composition coating on the substrate.
• Thermocompression can be performed by heat pressing, heat lamination, heat vacuum lamination, or the like.
• the lamination temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability.
• the lamination temperature is preferably 150°C or lower to prevent the resin composition film from hardening during lamination, which could result in poor resolution in the pattern formation in the exposure and development process.
• the substrates used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and these substrates on which circuit components are disposed.
• organic circuit boards include glass-based copper-clad laminates such as glass cloth/epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven cloth/epoxy copper-clad laminates, heat-resistant/thermoplastic substrates such as polyetherimide resin substrates, polyetherketone resin substrates, and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates.
• inorganic circuit boards include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates.
• circuit components include conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, low dielectrics containing glass-based materials and/or resins, high dielectrics containing resins and high-dielectric-constant inorganic particles, and insulators containing glass-based materials.
• the resin composition film formed by the above method is exposed to actinic radiation through a mask having a desired pattern.
• Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp.
• i-rays 365 nm
• h-rays (405 nm
• g-rays 436 nm
• developer solutions are aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine.
• alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylened
• these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, either alone or in combination.
• polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide
• alcohols such as methanol, ethanol, and isopropanol
• esters such as ethyl
• Development can be carried out by spraying the developer on the coating surface, piling the developer on the coating surface, immersing the coating in the developer, or immersing the coating in the developer and applying ultrasonic waves.
• the development conditions such as the development time, development steps, and developer temperature, may be any conditions that allow the unexposed areas to be removed and a pattern to be formed.
• alcohols such as ethanol or isopropyl alcohol, or esters such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to the water for rinsing.
• a baking process may be performed before development. This may improve the resolution of the pattern after development and increase the tolerance of the development conditions.
• the baking temperature is preferably in the range of 50 to 180°C, more preferably in the range of 60 to 120°C.
• the time is preferably from 5 seconds to several hours.
• a temperature of 150 to 500°C is applied to allow the thermal crosslinking reaction to proceed.
• Crosslinking can improve heat resistance and chemical resistance.
• This heat treatment can be performed by selecting a temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours.
• An example of the former is a method in which heat treatment is performed at 130°C and 200°C for 30 minutes each.
• An example of the latter is a method in which the temperature is increased linearly from room temperature to 400°C over a period of 2 hours.
• the cured film of the present invention is a cured film obtained by curing the resin composition of the present invention or the resin composition film of the present invention.
• the cured film of the present invention can be used in electronic components such as semiconductor devices.
• the electronic components of the present invention include the cured film of the present invention.
• a semiconductor device which is one type of electronic component, generally refers to any device that can function by utilizing the characteristics of a semiconductor element. Electro-optical devices in which a semiconductor element is connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices that include these are all included in semiconductor devices. Electronic components such as multilayer wiring boards for connecting semiconductor elements are also included in semiconductor devices.
• the electronic components of the present invention are suitable for use as passivation films for semiconductors, surface protective films for semiconductor elements, interlayer insulating films between semiconductor elements and wiring, interlayer insulating films between multiple semiconductor elements, interlayer insulating films between wiring layers in multilayer wiring for high-density mounting, and insulating layers for organic electroluminescent devices, but are not limited to these and can be used for a variety of purposes.
• a support film was present, it was peeled off, and exposure was performed using an ultra-high pressure mercury lamp at an exposure dose of 500 mJ/cm 2 (i-line equivalent, full wavelength exposure). After exposure, post-exposure heating was performed on a hot plate at 80°C for 10 minutes. Then, using an inert oven (INL-60, manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised from room temperature to 200°C over 60 minutes in a N2 atmosphere (oxygen concentration 20 ppm or less), and then heat-treated at 200°C for 60 minutes to obtain a cured film of the resin composition film formed on the silicon wafer.
• an inert oven INL-60, manufactured by Koyo Thermo Systems Co., Ltd.
• the obtained cured film was treated in an unsaturated pressure cooker test (130°C, humidity 85%) for 96 hours. After the test, a cross-cut test was carried out on the sample, and it was evaluated on a four-point scale as follows. A+: A case not corresponding to A, B, or C, and no peeling was observed in any of the lattices. A: Not corresponding to B or C, slight peeling was observed near the intersections of the grid. B: Not corresponding to C, partial peeling was observed along the lattice lines. C: Peeled off completely.
• melt viscosity was measured using a rheometer (MCR-302, manufactured by Anton Paar Co., Ltd.) under conditions of a frequency of 0.2 Hz and a strain of 1%.
• the melt viscosity at 80°C at this time was designated as ⁇ 0 .
• the resin composition film was then stored at 25°C for one week, and the melt viscosity was measured in the same manner as above.
• the melt viscosity at 80°C at this time was designated as ⁇ 1 .
• the rate of change in melt viscosity was calculated according to the following formula (2).
• ⁇ Evaluation of pattern processability> In the same manner as in the evaluation method of adhesion, a resin composition film was formed on a silicon wafer. Then, after peeling off the support film, a mask having a pattern with via sizes of 30 ⁇ m ⁇ , 20 ⁇ m ⁇ , and 10 ⁇ m ⁇ was set in an exposure device, and exposure was performed at an exposure dose of 1000 mJ/cm 2 (i-line equivalent, full wavelength exposure) using an ultra-high pressure mercury lamp under the condition of an exposure gap of 100 ⁇ m between the mask and the photosensitive resin composition film. After exposure, post-exposure heating was performed on a hot plate at 120° C. for 10 minutes. Thereafter, the unexposed portion was removed by dip development using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, and rinsed with water. The development time was twice the time when the unexposed portion was completely dissolved.
• Residual film rate is 90% or more, and the minimum opening size is 10 ⁇ m ⁇ A: The remaining film rate is 90% or more, and the minimum opening size is 20 ⁇ m ⁇ B: Residual film rate is 90% or more, and the minimum opening size is 30 ⁇ m ⁇ C: Residual film rate is less than 90% or the minimum opening size is 0
• Synthesis Example 1 Synthesis of Soluble Polymer Compound (a-1) Under a dry nitrogen stream, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) (29.30 g, 0.08 mol) was added to 80 g of ⁇ -butyrolactone (hereinafter referred to as GBL) and dissolved by stirring at 120°C.
• BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
• TDA-100 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (hereinafter referred to as TDA-100) (27.02 g, 0.09 mol) and X-12-967C (5.24 g, 0.02 mol) were added together with 20 g of GBL and stirred at 120°C for 1 hour. Then, the mixture was stirred at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 5 hours.
• TDA-100 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride
• Synthesis Example 2 Synthesis of soluble polymer compound (a-2) A soluble polymer compound (a-2) was obtained in the same manner as in Synthesis Example 1, except that the amount of BAHF added was changed to 34.79 g, or 0.095 mol.
• Synthesis Example 3 Synthesis of soluble polymer compound (a-3) A soluble polymer compound (a-3) was obtained in the same manner as in Synthesis Example 1, except that the amount of BAHF added was changed to 36.08 g, or 0.0985 mol.
• Synthesis Example 4 Synthesis of soluble polymer compound (a-4) A soluble polymer compound (a-4) was obtained in the same manner as in Synthesis Example 1, except that the amount of BAHF added was changed to 23.81 g, or 0.065 mol.
• Synthesis Example 5 Synthesis of soluble polymer compound (a-5) A soluble polymer compound (a-5) was obtained in the same manner as in Synthesis Example 1, except that the amount of BAHF added was changed to 20.14 g, or 0.055 mol.
• Synthesis Example 6 Synthesis of soluble polymer compound (a-6) A soluble polymer compound (a-6) was obtained in the same manner as in Synthesis Example 1, except that the amount of X-12-967C added was changed to 1.31 g, or 0.005 mol.
• Synthesis Example 7 Synthesis of soluble polymer compound (a-7) A soluble polymer compound (a-7) was obtained in the same manner as in Synthesis Example 1, except that the amount of X-12-967C added was changed to 0.52 g, 0.002 mol.
• Synthesis Example 8 Synthesis of soluble polymer compound (a-8) A soluble polymer compound (a-8) was obtained in the same manner as in Synthesis Example 1, except that the amount of X-12-967C added was changed to 10.49 g, or 0.04 mol.
• Synthesis Example 9 Synthesis of soluble polymer compound (a-9) A soluble polymer compound (a-9) was obtained in the same manner as in Synthesis Example 1, except that the amount of X-12-967C added was changed to 15.74 g, or 0.06 mol.
• Synthesis Example 10 Synthesis of soluble polymer compound (a-10) A soluble polymer compound (a-10) was obtained in the same manner as in Synthesis Example 1, except that BAHF was changed to 30.44 g, 0.08 mol of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (hereinafter, referred to as FDA).
• FDA 9,9-bis(3-amino-4-hydroxyphenyl)fluorene
• Synthesis Example 11 Synthesis of soluble polymer compound (a-11) Under a dry nitrogen stream, BAHF (29.30 g, 0.08 mol) was added to 80 g of GBL and stirred and dissolved at 120°C. Next, TDA-100 (30.02 g, 0.10 mol) was added together with 20 g of GBL and stirred at 120°C for 1 hour. Then, the mixture was stirred at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 5 hours.
• Synthesis Example 12 Synthesis of soluble polymer compound (a-12) Under a dry nitrogen stream, BAHF (29.30 g, 0.08 mol) was added to 80 g of GBL and stirred and dissolved at 120° C. Next, TDA-100 (27.02 g, 0.09 mol) and X-12-967C (5.25 g, 0.02 mol) were added together with 20 g of GBL and stirred at 120° C. for 1 hour to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 5 hours. The polymer compounds synthesized in Synthesis Examples 1 to 12 were dissolved in an amount of 0.1 g or more in 100 g of ⁇ -butyrolactone solution at 25° C., and thus demonstrated solubility.
• Example 1 (a) 1 g of the soluble polymer compound (a-1) obtained in Synthesis Example 1 as the component, (b) 1.2 g of TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.) as the polymerizable compound, and (c) 0.06 g of CPI-310FG (trade name, manufactured by San-Apro Co., Ltd.) as the photopolymerization initiator were dissolved in GBL. The amount of solvent added was adjusted so that the solids concentration was 50% by weight, with additives other than the solvent being the solids. Thereafter, the mixture was pressure-filtered using a filter with a retention particle size of 1 ⁇ m to obtain a resin composition varnish.
• TEPIC-VL trade name, manufactured by Nissan Chemical Industries, Ltd.
• CPI-310FG trade name, manufactured by San-Apro Co., Ltd.
• the obtained resin composition varnish was applied to a silicon wafer using a spinner at 1500 rpm for 30 seconds, and then dried on a hot plate at 80°C for 3 minutes to form a resin composition film on the silicon wafer.
• the obtained resin composition film was used to evaluate adhesion, storage stability, and pattern processability as described above. The results are shown in Table 1.
• Comparative Examples 1 to 3 Resin composition varnishes were prepared in the same manner as in Example 1, except that the components (a) to (c) and other components were changed to the compounds shown below and their mixing ratios were changed as shown in the table. The adhesion, storage stability, and pattern processability were evaluated as described above. The results are shown in Table 2.
• Soluble polymer compound a-1 to a-10: Soluble polymer compounds containing a structure having a repeating unit represented by chemical formula (1), containing a structure derived from an acid anhydride silane residue, and containing a structure represented by chemical formula (2), wherein in said chemical formula (2), the acid anhydride silane residue is derived from a structure represented by chemical formula (4).
• a-11 A soluble polymeric compound having a structure having a repeating unit represented by chemical formula (1).
• a-12 A soluble polymer compound that does not contain a structure having a repeating unit represented by chemical formula (1) and has a structure derived from an acid anhydride silane residue represented by chemical formula (4).
• Photopolymerization initiator CPI-310FG (onium salt-based photocationic polymerization initiator, manufactured by San-Apro Co., Ltd.).
• Silane compound X-12-967C (Shin-Etsu Chemical Co., Ltd.), acid anhydride silane.

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