WO2018159384A1 - Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur - Google Patents

Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur Download PDF

Info

Publication number
WO2018159384A1
WO2018159384A1 PCT/JP2018/005978 JP2018005978W WO2018159384A1 WO 2018159384 A1 WO2018159384 A1 WO 2018159384A1 JP 2018005978 W JP2018005978 W JP 2018005978W WO 2018159384 A1 WO2018159384 A1 WO 2018159384A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
resin composition
component
mass
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/005978
Other languages
English (en)
Japanese (ja)
Inventor
馬場修
奥田良治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP2018510541A priority Critical patent/JP7059927B2/ja
Publication of WO2018159384A1 publication Critical patent/WO2018159384A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a resin composition, a resin sheet, a cured pattern, and a semiconductor electronic component or semiconductor device. Specifically, the present invention relates to a resin composition suitably used for a protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the use thereof.
  • Positive-type and negative-type photosensitive resin compositions have advantages and disadvantages, respectively, and are selectively used according to the application so as to obtain desired characteristics.
  • the positive type is suitable for applications that require high resolution with an opening size of 10 ⁇ m or less
  • the negative type is suitable for applications that require a process with a chemical solution such as a resist stripping solution.
  • Patent Document 1 a resin composition containing a heat-resistant resin such as polyimide and a polyfunctional alkoxymethyl crosslinking agent has been proposed (for example, Patent Document 1).
  • Patent Document 2 a resin composition containing a resin having a flexible group such as alkylene glycol in the main chain has been proposed (for example, Patent Document 2).
  • Patent Document 1 loses the flexibility of the cured film due to cross-linking, and the cured film tends to be highly stressed and insufficiently stretched, causing a warp of the semiconductor chip, physical shock, or thermal shock. Tended to cause cracks.
  • these resin compositions are used in a subsequent solder reflow process (about 250 to 270 ° C.) when the maximum temperature of the heat treatment for curing (hereinafter sometimes referred to as firing) step is 220 ° C. or less.
  • An object of the present invention is to provide a resin composition having a small change in the shape of the cured pattern in the solder reflow process.
  • the present invention has the following configuration. (1) (a-1) an alkali-soluble polyimide resin having a glass transition temperature of 200 ° C. or higher and 300 ° C. or lower, and (a-2) an alkali-soluble polyimide or alkali-soluble polyimide having a glass transition temperature of 50 ° C. or higher and 150 ° C. or lower.
  • a resin composition comprising at least one resin selected from benzoxazole, alkali-soluble polyamideimide, precursors thereof and copolymers thereof, and (b) a photosensitizing agent, A resin composition containing 10 to 40 parts by mass of the component (a-2) with respect to 100 parts by mass of the component (a-1).
  • a resin sheet comprising the above resin composition.
  • a cured pattern made of a cured product of the above resin composition.
  • a method for producing a cured pattern using the resin composition wherein the maximum temperature in the step of heat-treating the developed resin pattern is lower than the glass transition temperature of the component (a-1), A method for producing a cured pattern, which is higher than the glass transition temperature of the component (a-2).
  • the obtained cured film is low stress and the shape change of the cured pattern in the subsequent solder reflow process Can be obtained.
  • the resin composition of the present invention is (A-1) an alkali-soluble polyimide resin having a glass transition temperature of 200 ° C. or more and 300 ° C. or less, (a-2) a glass transition temperature of 50 ° C. or more and 150 ° C. or less, an alkali-soluble polyimide, an alkali-soluble polybenzoxazole, A resin composition comprising an alkali-soluble polyamideimide, at least one resin selected from precursors thereof and copolymers thereof, and (b) a photosensitizer,
  • the component (a-2) is contained in an amount of 10 parts by weight to 40 parts by weight with respect to 100 parts by weight of the component (a-1).
  • the glass transition temperature can be determined using a differential scanning calorimeter (DSC). Details will be described later.
  • DSC differential scanning calorimeter
  • containing the resins of the component (a-1) and the component (a-2) having different glass transition temperatures improves the elongation of a cured film obtained by low-temperature baking at 150 ° C. or higher and 220 ° C. or lower, and This is important for reducing the stress and improving the resistance of the hardened pattern to the solder reflow process.
  • the inventors could not achieve the effects of the present invention by using a resin having a glass transition temperature of more than 150 ° C. and less than 200 ° C., which is an intermediate property between the two, instead of (a-1) It has been found that the effects of the present invention as described above can be achieved only when the component and the component (a-2) are used in combination. Specifically, instead of the component (a-1) and the component (a-2), when only a resin having a glass transition temperature of more than 150 ° C. and less than 200 ° C. is used, Similarly, the shape of the cured pattern cannot be maintained in the solder reflow process, and the shape tends to collapse. The estimation mechanism is described below.
  • the (a-1) component improves the resistance to the solder reflow process during low-temperature firing at 150 ° C. or higher and 220 ° C. or lower, and improves the elongation of the cured film from which the (a-2) component is obtained. I am letting.
  • the component (a-2) has a synergistic effect of relieving the stress of the obtained cured pattern and suppressing the deformation of the cured pattern in the solder reflow process when used in combination with the component (a-1). With these effects, it is possible to achieve high elongation of the cured film obtained by low-temperature baking at 150 ° C. or higher and 220 ° C. or lower, low stress, and resistance to the solder reflow process of the cured pattern.
  • the glass transition temperature of the component (a-1) is 200 ° C. or more and 300 ° C. or less, but is preferably 220 ° C. or more, more preferably 240 ° C. or more, from the viewpoint of resistance to the solder reflow process of the cured pattern. Further, from the viewpoint of storage stability of the resin composition, the glass transition temperature of the component (a-1) is more preferably 280 ° C. or less, further preferably 270 ° C. or less, particularly preferably 260 ° C. or less.
  • the glass transition temperature of the component (a-2) is 50 ° C. or higher and 150 ° C. or lower, but is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably, from the viewpoint of resistance to the solder reflow process of the cured pattern. It is 100 ° C or higher. Further, from the viewpoint of improving the elongation of the cured film and reducing the stress, the glass transition temperature of the component (a-2) is more preferably 140 ° C. or less, further preferably 130 ° C. or less, and particularly preferably 120 ° C. or less.
  • the stress of the cured film or cured pattern obtained by thermosetting the resin composition of the present invention at 210 ° C. is preferably 10 MPa or more and 30 MPa or less.
  • the stress of the cured film or the cured pattern can be measured with a stress measuring device. Details will be described later.
  • the stress of the cured film or the cured pattern is preferably 30 MPa or less, more preferably 25 MPa or less, further preferably 20 MPa or less, and particularly preferably 18 MPa or less, from the viewpoint of suppressing warpage of the semiconductor chip.
  • the stress of the cured film or the cured pattern is preferably 3 MPa or more, more preferably 5 MPa or more, and particularly preferably 10 MPa or more in order to maintain the pattern shape.
  • alkali-soluble resin in the present invention refers to a resin having an alkali dissolution rate measured by the following method of 60 nm / min or more and 1,000,000 nm / min or less.
  • ⁇ Dissolve the resin to be measured in ⁇ -butyrolactone so that the solid content is 35% by mass.
  • This solution is applied onto a 6-inch silicon wafer and pre-baked for 4 minutes on a hot plate at 120 ° C. to form a resin film having a thickness of 10 ⁇ m ⁇ 0.5 ⁇ m.
  • This was immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ⁇ 1 ° C. for 1 minute, and the thickness of the resin film dissolved per minute was determined from the change in the thickness of the resin film before and after immersion, The alkali dissolution rate is used. When the resin film is completely dissolved in less than 1 minute, the time taken for dissolution is measured, and the film thickness dissolved per minute is determined from this and the film thickness of the resin film before immersion. The alkali dissolution rate is used.
  • the content of the component (a-2) in the resin composition of the present invention is 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the component (a-1).
  • the content of the component (a-2) is preferably 12 parts by mass or more, more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more from the viewpoint of improving the elongation of the cured film and reducing the stress.
  • the content of the component (a-2) is more preferably 37 parts by mass or less, further preferably 34 parts by mass or less, and particularly preferably 30 parts by mass or less, from the viewpoint of improving the resistance to solder reflow process of the cured pattern. .
  • the difference between the glass transition temperature of the component (a-1) and the glass transition temperature of the component (a-2) is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, from the viewpoint of reducing the stress of the resulting cured film.
  • the difference in glass transition temperature is preferably 220 ° C. or less, and more preferably 190 ° C. or less, from the viewpoint of improving the elongation of the cured film.
  • the polyimide preferably used in the resin composition of the present invention is obtained, for example, by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride and the like with diamine, corresponding diisocyanate compound, and trimethylsilylated diamine.
  • the polyamic acid (polyimide precursor) can be obtained by dehydration and ring closure by heat treatment or chemical treatment such as acid or base.
  • the polybenzoxazole preferably used in the resin composition of the present invention is, for example, a polyhydroxyamide (polybenzoxazole precursor obtained by reacting bisaminophenol with dicarboxylic acid, corresponding dicarboxylic acid chloride, dicarboxylic acid active ester, etc. ) Can be obtained by dehydration and ring closure by heat treatment or chemical treatment of phosphoric anhydride, base, carbodiimide compound or the like.
  • the polyamideimide preferably used in the resin composition of the present invention is, for example, a heat treatment of a polyamideimide precursor obtained by reacting tricarboxylic acid, corresponding tricarboxylic anhydride, tricarboxylic anhydride halide, etc. with diamine or diisocyanate. Or it can obtain by carrying out dehydration ring closure by chemical treatments, such as an acid and a base.
  • the resin of the component (a-1) and the component (a-2) may be obtained by precipitating in a poor solvent for a polymer such as methanol or water after completion of the polymerization, and then washing and drying. More preferred. By this operation, since the low molecular weight component of the polymer can be removed, the mechanical properties of the resin composition after heat curing are improved.
  • the component (a-1) is preferably a resin having a structural unit represented by the general formula (1).
  • the number of structural units represented by the general formula (1) contained in one molecule of the resin is preferably 3 or more, more preferably 10 or more, and particularly preferably 15 or more. From the viewpoint of alkali solubility, the number of structural units is preferably 500 or less, more preferably 200 or less, still more preferably 100 or less, still more preferably 70 or less, and particularly preferably 50 or less.
  • R 1 represents a tetravalent organic group
  • R 2 represents a divalent to hexavalent organic group
  • p represents an integer of 0 to 4.
  • the component (a-1) has a structural unit represented by the general formula (4) from the viewpoint of improving adhesion to a metal wiring or metal electrode containing a copper element.
  • the number of structural units represented by the general formula (4) contained in one molecule of the resin is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 or more. From the viewpoint of alkali solubility, the number of structural units is preferably 100 or less, more preferably 50 or less, still more preferably 20 or less, and particularly preferably 10 or less.
  • R 9 represents a tetravalent organic group
  • Z represents one or more groups selected from the following group (Z-1).
  • R 10 represents a hydrogen atom, a hydroxyl group, a mercapto group, or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • any resin of polyimide, polybenzoxazole, polyamideimide, precursors thereof and copolymers thereof is preferably used.
  • a resin having a structural unit represented by the general formula (1) is particularly preferable.
  • the structural unit of the general formula (1) is preferably 30% or more of the total number of all structural units of the component (a-2), more preferably 50% or more, further preferably 70% or more, and 90% It is particularly preferable to include the above.
  • R 1 represents a tetravalent organic group
  • R 2 represents a divalent to hexavalent organic group
  • p represents an integer of 0 to 4.
  • the component (a-2) is one or more structures selected from the structural units represented by the general formula (2) and the general formula (3) from the viewpoint of setting the glass transition temperature to 50 ° C. or higher and 150 ° C. or lower. It is preferable to have a unit.
  • the number of structural units represented by the general formula (2) or (3) contained in one molecule of the resin is preferably 3 or more, more preferably from the viewpoint of setting the glass transition temperature to 50 ° C. or more and 150 ° C. or less. It is 5 or more, more preferably 10 or more, and particularly preferably 15 or more. Further, the number of structural units is preferably 100 or less, more preferably 80 or less, still more preferably 50 or less, and particularly preferably 30 or less, from the viewpoint of maintaining high heat resistance of the cured pattern.
  • the structural units represented by the general formula (2) and the general formula (3) are in any form of a diamine compound residue, a dicarboxylic acid compound residue, a tricarboxylic acid compound residue, and a tetracarboxylic acid compound residue in the resin. However, it is preferable that it is contained as a diamine compound residue from the viewpoint of the elongation of the cured film.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and are the same But it can be different.
  • r represents an integer of 4 to 20, and s represents an integer of 2 to 20.
  • R 1 , R 2 (OH) p and R 9 in the general formula (1) and the general formula (4) can contain a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and the like in the skeleton.
  • a resin having an appropriate phenolic hydroxyl group, sulfonic acid group or thiol group a photosensitive resin composition excellent in alkali solubility and pattern forming property can be obtained.
  • R 1 and R 9 represent a tetracarboxylic acid compound residue.
  • the acid component containing R 1 and R 9 include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′.
  • R 2 (OH ) p represents an diamine compound residue.
  • diamine components containing R 2 (OH) p include 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 (3-amino- Hydroxyl group-containing diamines such as 4-hydroxyphenyl) fluorene; 3-sulfonic acid-containing diamines such as 4,4′-diaminodiphenyl ether; Thiol group-containing diamines such as dimercaptophenylenediamine; 3,4′-diaminodiphenyl ether 4,4'-Diaminodiphenyl ether
  • diamine containing a long-chain aliphatic group or a polyalkylene oxide group “Jephamine” (registered trademark) KH-511, Jeffamine ED-600, Jeffamine ED-900, which contains a polyethylene oxide group, Jeffermin ED-2003, Jeffermin EDR-148, Jeffermin EDR-176, Polyoxypropylenediamine Jeffermin D-200, Jeffermin D-400, Jeffermin D-2000, Jeffermin D-4000 Name, available from HUNTSMAN Co., Ltd.).
  • These 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.
  • the component (a-2) has a diamine residue containing a long-chain aliphatic group or a polyalkylene oxide group because the glass transition temperature of the resin can be lowered. Therefore, as the component (a-2), those having a diamine residue having a structural unit selected from the structural unit of the general formula (2) and the structural unit of the general formula (3) are particularly preferably used. On the other hand, the component (a-1) preferably does not contain these structural units from the viewpoint of maintaining a high glass transition temperature of the resin.
  • the structural unit of the component (a-1) and / or the component (a-2) has a fluorine atom.
  • the fluorine atom imparts water repellency to the surface of the resulting resin film, and soaking of the developer from the resin film surface during alkali development can be suppressed.
  • the fluorine atom content in the component (a-1) and the component (a-2) is preferably 10% by mass or more in order to obtain a sufficient penetration preventing effect, and 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution. Is preferred.
  • an aliphatic diamine having a siloxane structure may be copolymerized as R 2 (OH) p as long as the heat resistance is not lowered. Adhesiveness with the substrate can be improved. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane and the like are copolymerized as 1 to 10 mol% as the diamine component.
  • the component (a-1) and the component (a-2) are composed of a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactivity at the main chain end. It is preferable to seal with a terminal sealing agent such as an ester compound.
  • a terminal sealing agent such as an ester compound.
  • An ester compound or the like can also be used.
  • the introduction ratio is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, based on the total amine component. Further, it is preferably at most 60 mol%, particularly preferably at most 50 mol%, based on all amine components.
  • the introduction ratio is preferably 0.1 mol% or more, particularly preferably 5 with respect to the diamine component. More than mol%.
  • the introduction ratio of the end-capping agent is preferably 100 mol% or less, particularly preferably 90 mol% or less, with respect to the diamine component, in order to keep the resin molecular weight high.
  • a plurality of different end groups may be introduced by reacting a plurality of end-capping agents.
  • Monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1- Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-amino Benzoic acid, 3-aminobenzoic acid 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminos
  • Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, or monoactive ester compounds include acids such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc.
  • Anhydrides 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxy Monocarboxylic acids such as naphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid And monoacid chloride compounds in which these carboxyl groups are acid chlorides; terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene Monoacid chloride compounds in which only one carboxyl group of dicarboxy
  • the end capping agent introduced into the component (a-1) and the component (a-2) can be detected by the following method.
  • a resin into which a terminal blocking agent has been introduced is dissolved in an acidic solution, and decomposed into an amine component and an acid anhydride component, which are structural units, which are then subjected to gas chromatography (GC) or nuclear magnetic resonance (NMR).
  • GC gas chromatography
  • NMR nuclear magnetic resonance
  • the end-capping agent can be easily detected.
  • it is also possible to easily detect the resin component into which the end-capping agent has been introduced by directly measuring by pyrolysis gas chromatography (PGC), infrared spectrum and 13 C-NMR spectrum. It is.
  • PPC pyrolysis gas chromatography
  • imide ring cyclization rate when the molar ratio of imide ring-closing units to the total amount of all imide and imide precursor units is defined as imide ring cyclization rate (R IM (%)), R IM is 220 ° C. or less. From the viewpoint of mechanical properties and chemical resistance of the cured film during low-temperature firing, it is preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and particularly preferably 90% or more. Similarly, when polyimide is used as the component (a-2), the imide ring cyclization rate R IM is preferably 30% or more from the viewpoint of mechanical properties and chemical resistance of the cured film during low-temperature baking at 220 ° C. or lower. More preferably, it is 50% or more, further preferably 70% or more, and particularly preferably 90% or more.
  • Said imide ring closure rate (%) can be calculated
  • the polymer is heat-treated at 350 ° C. for 1 hour to completely close the imide ring, and then an infrared absorption spectrum is measured to obtain a peak intensity (Y) near 1377 cm ⁇ 1 .
  • the component (a-1) and the component (a-2) preferably have an alkali dissolution rate measured by the above-described method of 100 nm / min or more, more preferably 200 nm / min or more, Preferably it is 500 nm / min or more, Especially preferably, it is 1,000 nm / min or more.
  • the alkali dissolution rate is preferably 200,000 nm / min or less, more preferably 100,000 nm / min or less, further preferably 50,000 nm / min or less, Preferably it is 20,000 nm / min or less, Most preferably, it is 15,000 nm / min or less.
  • the weight average molecular weight of the component (a-1) and the component (a-2) is preferably 1,000 or more, more preferably 1,500 or more, and further preferably 5,000 or more, from the viewpoint of the mechanical properties of the cured film. Especially preferably, it is 10,000 or more.
  • the weight average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 40,000 or less, and particularly preferably 30,000 or less from the viewpoint of alkali solubility.
  • the weight average molecular weight in the present invention is a value determined in terms of polystyrene by gel permeation chromatography (GPC). Details will be described later.
  • the resin composition of the present invention may contain a phenol-containing resin as necessary.
  • the phenol-containing resin in the present invention is a resin having a phenol group as a structural unit, and examples thereof include, but are not limited to, polyhydroxystyrene resin, alkali-soluble novolak resin, resol resin, and benzyl ether type phenol resin. Not. Two or more of these may be used. Among these, from the viewpoint of the reliability of the cured film, it is particularly preferable to contain (a-3) a polyhydroxystyrene resin (hereinafter sometimes abbreviated as (a-3) component).
  • the polyhydroxystyrene resin can be obtained, for example, by addition polymerization of a phenol derivative having an unsaturated bond by a known method.
  • the phenol derivative having an unsaturated bond include hydroxystyrene, dihydroxystyrene, allylphenol, coumaric acid, 2′-hydroxychalcone, N-hydroxyphenyl-5-norbornene-2,3-dicarboxylic imide, resveratrol , 4-hydroxystilbene and the like, and two or more thereof may be used.
  • the copolymer with the monomer which does not contain phenolic hydroxyl groups, such as styrene may be sufficient. By doing so, the alkali dissolution rate can be easily adjusted.
  • the polyhydroxystyrene resin is preferably a copolymer having a hydroxystyrene residue and a styrene residue from the viewpoint of adjusting the alkali dissolution rate.
  • the content of the styrene residue is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 15 mol% or more with respect to 100 mol% of the hydroxystyrene residue.
  • the content of styrene residues is preferably 60 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, particularly preferably 25 mol% or less, based on 100 mol% of hydroxystyrene residues. It is.
  • the novolak resin, the resole resin, and the benzyl ether type phenol resin can be obtained by polycondensing phenols and aldehydes such as formalin by a known method.
  • phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3 , 4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene Bisphenol, methylenebis (p-cresol), resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p- Butoxy phenol, o- ethylphenol, m- ethylphenol, p- ethylphenol, 2,3-diethyl phenol, 2,5-diethyl phenol, o
  • aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. Two or more of these may be used.
  • the weight average molecular weight of the phenol-containing resin is preferably 500 or more, more preferably 700 or more, still more preferably 1,000 or more, and preferably 50,000 or less, more preferably 1,000 or less, from the viewpoint of alkali solubility, from the viewpoint of chemical resistance. Is 40,000 or less, more preferably 30,000 or less, and particularly preferably 20,000 or less.
  • the weight average molecular weight is a value determined in terms of polystyrene by gel permeation chromatography (GPC).
  • the glass transition temperature of the phenol-containing resin can be determined using a differential scanning calorimeter (DSC).
  • the glass transition temperature is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 100 ° C. or higher, from the viewpoint of resistance to the solder reflow process of the cured pattern.
  • the glass transition temperature is preferably 200 ° C. or less, more preferably 170 ° C. or less, and particularly preferably 150 ° C. or less, from the viewpoint of the elongation of the cured film.
  • the content of the phenol-containing resin is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the component (a-1), from the viewpoint of improving sensitivity when used as a photosensitive resin composition. More preferably, it is 15 parts by mass or more, and particularly preferably 18 parts by mass or more.
  • the content of the phenol-containing resin is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, still more preferably 200 parts by mass with respect to 100 parts by mass of the component (a-1), from the viewpoint of heat resistance of the cured film. Part or less, more preferably 100 parts by weight or less, and particularly preferably 50 parts by weight or less.
  • the alkali dissolution rate of the phenol-containing resin is preferably 100 nm / min or more, more preferably 200 nm / min or more, still more preferably 500 nm / min or more, particularly preferably 1,000 nm / min or more, from the viewpoint of appropriate development time. It is. Further, it is preferably 200,000 nm / min or less, more preferably 100,000 nm / min or less, further preferably 50,000 nm / min or less, further preferably 20,000 nm / min or less, particularly preferably 15,000 nm / min or less. It is.
  • the resin composition of the present invention contains (b) a photosensitizer. (B) Since the photosensitizer is contained, the solubility of the UV-exposed portion in the alkali developer or the organic developer changes, so that the resin pattern can be obtained by developing with a developer after UV exposure.
  • (b-1) a quinonediazide compound is used as (b) a photosensitive agent.
  • the resin composition contains the (b-1) quinonediazide compound, an acid is generated in the ultraviolet exposure area, and the solubility in the alkaline aqueous solution in the exposure area is increased. This resin pattern can be obtained.
  • Two or more quinonediazide compounds can also be used. Thereby, the ratio of the dissolution rate of an exposed part and an unexposed part can be enlarged more, and a highly sensitive photosensitive resin composition can be obtained.
  • Examples of the compound (b-1) include quinonediazide sulfonic acid bonded to a polyhydroxy compound, quinonediazide sulfonic acid bonded to a polyamino compound, and quinonediazide sulfonic acid ester to a polyhydroxypolyamino compound. Examples thereof include those bonded with one or more selected from a bond and a sulfonamide bond. 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), or g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.
  • both 5-naphthoquinonediazidesulfonyl group and 4-naphthoquinonediazidesulfonyl group are preferably used.
  • a compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.
  • the quinonediazide compound can be synthesized by a known method. For example, there is a method in which 5-naphthoquinonediazide sulfonyl chloride and a polyhydroxy compound are reacted in the presence of triethylamine.
  • the content of the compound (b-1) in the resin composition is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the component (a-1).
  • the content of the compound (b-1) is preferably 3 parts by mass or more.
  • the content of the compound (b-1) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
  • (b-2) a photopolymerization initiator is used as (b) a photosensitive agent.
  • the resin composition contains (b-2) a photopolymerization initiator and a compound (d) having a polymerizable unsaturated bond group, which will be described later, the exposed portion is exposed to an alkali developer or organic by ultraviolet exposure and subsequent heat treatment. Since it becomes insoluble in the developer, a negative pattern can be formed.
  • photopolymerization initiator examples include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.
  • Benzophenones such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone; 7-diethylamino-3- Tenonyl coumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl) ) Kumari such as -7-diethylaminocoumarin Anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone and 1,2-benzanthraquinone; benzoins such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl
  • the content of the (b-2) photopolymerization initiator in the resin composition is preferably 0.1 to 40 parts by mass per type with respect to 100 parts by mass of the resin (a-1). When two or more kinds are combined, the total amount is preferably 0.2 to 60 parts by mass.
  • the resin composition of the present invention preferably further contains (c) a thermal crosslinking agent.
  • a thermal crosslinking agent a compound having at least two groups selected from an alkoxymethyl group and a methylol group, or a compound having at least two groups selected from an epoxy group and an oxetanyl group Is preferably used, but is not limited thereto.
  • the resin composition contains (c) a thermal crosslinking agent, when the resin pattern formed using the resin composition is fired, the components (a-1), (a-2) and (c) The thermal crosslinking agent reacts to form a crosslinked structure, and the resistance of the obtained cured film to the solder reflow process is improved. Further, two or more kinds of thermal cross-linking agents may be used, which enables a wider range of designs.
  • Preferred examples of the compound having at least two groups selected from an alkoxymethyl group and 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, TMOM-BPAF,
  • Preferred examples of the compound having at least two groups selected from an epoxy group and an oxetanyl group include, for example, bisphenol A type epoxy resin, bisphenol A type oxetanyl resin, bisphenol F type epoxy resin, and bisphenol F.
  • Examples include, but are not limited to, type oxetanyl resins, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane.
  • EPICLON (registered trademark) 850-S, HP-4032, HP-7200, HP-820, HP-4700, EXA-4710, HP-4770, EXA-859CRP, EXA-1514, EXA- 4880, EXA-4850-150, EXA-4850-1000, EXA-4816, EXA-4822 (above, trade name, manufactured by DIC Corporation), “Lika Resin” (registered trademark) BEO-60E (trade name, Shin Nippon Rika) ), EP-4003S, EP-4000S (trade name, manufactured by ADEKA), "TECHMORE” (registered trademark) VG3101L, VG3101M80 (trade name, manufactured by Printec Co., Ltd.) Available from each company. Two or more of these may be contained.
  • the content of the thermal crosslinking agent (c) in the resin composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 10 parts by mass with respect to 100 parts by mass of the component (a-1). More than part by mass. Moreover, from the viewpoint of maintaining mechanical properties such as elongation, the content of (c) the thermal crosslinking agent is preferably 300 parts by mass or less, more preferably 200 parts by mass or less.
  • the resin composition preferably further contains (d) a compound having a polymerizable unsaturated bond group.
  • the exposed portion is insolubilized in an alkali or organic developer by ultraviolet exposure and subsequent heat treatment. Therefore, a negative pattern can be formed.
  • examples of the polymerizable unsaturated bond group include unsaturated double bond groups such as vinyl group, allyl group, acryloyl group, and methacryloyl group, and unsaturated triple bond groups such as propargyl group. . You may have 2 or more types of these. Among these, a group selected from a conjugated vinyl group, an acryloyl group, and a methacryloyl group is preferable in terms of polymerizability. From the viewpoint of stability, it is preferable to have 1 to 4 of these groups in one molecule.
  • component (d) examples include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylol Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, ⁇ -methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinyl naphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate , Isooctyl acrylate, isobornyl acrylate, cyclohe
  • the content of the component (d) in the resin composition is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the component (a-1), and more preferably 5 to 150 parts by mass from the viewpoint of compatibility. .
  • the resin composition preferably further contains (e) a polymerization inhibitor.
  • a polymerization inhibitor stops radical polymerization by capturing radicals generated during exposure or radicals at the polymer growth end of the polymer chain obtained by radical polymerization during exposure and holding them as stable radicals.
  • the resin composition contains an appropriate amount of (e) a polymerization inhibitor, thereby suppressing generation of residues after development, Resolution can be improved. This is presumed to be due to the excessive amount of radicals generated at the time of exposure or the radical at the growth terminal of the high molecular weight polymer chain being captured by the polymerization inhibitor, thereby suppressing the progress of excessive radical polymerization.
  • the polymerization inhibitor is preferably a phenol polymerization inhibitor.
  • the phenol polymerization inhibitor include 4-t-butylphenol, 4-methoxyphenol, 1,4-hydroquinone, 1,4-benzoquinone, 2-t-butyl-4-methoxyphenol, 3-t-butyl- 4-methoxyphenol, 4-t-butylcatechol, 2-t-butyl-1,4-hydroquinone, 2,6-di-t-butylphenol, 2,4,6-tri-t-butylphenol, 2,6- Di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butyl-1,4-hydroquinone, 2,5-di-t- Amyl-1,4-hydroquinone, 2-nitroso-1-naphthol, “IRGANOX” (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330,
  • the content of the (e) polymerization inhibitor in the resin composition is preferably 0.01 parts by mass or more, and 0.03 parts by mass or more with respect to 100 parts by mass of the compound (d) having a polymerizable unsaturated bond group. Is more preferably 0.05 parts by mass or more, and particularly preferably 0.1 parts by mass or more. When the content is within the above range, the resolution after development and the heat resistance of the cured film can be improved.
  • the content of (e) the polymerization inhibitor is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. The sensitivity at the time of exposure can be improved as content is in the said range.
  • the resin composition of the present invention may contain a solvent as necessary.
  • the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide; tetrahydrofuran, dioxane, propylene glycol Ethers such as monomethyl ether and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl Esters such as acetate; Alcohols such as ethyl lactate, methyl lactate, diacetone alcohol and 3-methyl-3-methoxybutanol; Fragrances such as
  • the content of the solvent in the resin composition is preferably 70 parts by mass or more, more preferably 100 parts by mass or more from the viewpoint of resin dissolution with respect to 100 parts by mass of the component (a-1). Further, from the viewpoint of obtaining an appropriate film thickness, the content of the solvent is preferably 1800 parts by mass or less, more preferably 1500 parts by mass or less.
  • the resin composition of the present invention preferably contains (f) a solvent having an ester structure (hereinafter sometimes abbreviated as (f) solvent) among the above-mentioned solvents.
  • a solvent having an ester structure hereinafter sometimes abbreviated as (f) solvent
  • the detailed reason is unknown by the fact that a small amount of the solvent (f) is contained in the cured pattern obtained by heat-treating the resin pattern formed using the resin composition, the elongation of the cured pattern is improved.
  • Preferred examples of the solvent having an ester structure include ⁇ -butyrolactone, ⁇ -valerolactone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate. , Ethyl lactate, methyl lactate and the like.
  • the content of the solvent (f) contained in the cured pattern is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass with respect to the cured pattern. % Or more, particularly preferably 0.015% by mass or more.
  • the content of the solvent (f) is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, particularly preferably. Is 0.03% by mass or less.
  • the resin composition of the present invention may further contain a thermal acid generator as necessary.
  • the thermal acid generator generates an acid by heating, (c) acceleration of the crosslinking reaction of the thermal crosslinking agent, and (a-1) and (a-2) imide ring structure and / or oxazole ring structure in which the components are not closed In the case where it has, the cyclization is promoted, and even when baked at 150 to 300 ° C. which is lower than usual, there is an effect of further improving the mechanical properties of the obtained cured film.
  • the thermal decomposition starting temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 220 ° C. or lower, and further preferably 180 ° C. or lower.
  • drying pre-baking: about 70 to 140 ° C.
  • final heating curing: about
  • the thermal acid generator As such, those having a thermal decomposition starting temperature not higher than the maximum temperature of the heat treatment step are preferably used.
  • the acid generated from the thermal acid generator is preferably a strong acid.
  • arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid
  • alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid
  • trifluoromethane ethanesulfonic acid
  • Haloalkyl sulfonic acids such as sulfonic acid are preferred. These are used as salts such as onium salts or as covalently bonded compounds such as imidosulfonates.
  • the content of the thermal acid generator in the resin composition is preferably 0.01 parts by mass with respect to 100 parts by mass of the component (a-1) in terms of crosslinking reaction and promotion of cyclization of the unclosed structure of the resin. As mentioned above, More preferably, it is 0.1 mass part or more. Further, from the viewpoint of electrical insulation of the cured film, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.
  • the resin composition of the present invention may further contain a low molecular compound having a phenolic hydroxyl group, if necessary.
  • a low molecular compound having a phenolic hydroxyl group By containing a low molecular weight compound having a phenolic hydroxyl group, it is easy to adjust alkali solubility during resin pattern formation.
  • the content of the low molecular weight compound having a phenolic hydroxyl group is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the component (a-1). Moreover, from the viewpoint of maintaining mechanical properties such as elongation, the content is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.
  • the resin composition of the present invention comprises a surfactant for the purpose of improving the wettability with a support substrate as necessary; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; alcohols such as ethanol; cyclohexanone and methyl isobutyl. It may further contain ketones such as ketones; ethers such as tetrahydrofuran and dioxane.
  • the preferable content of the compound used for the purpose of improving the wettability with these supporting substrates is 0.001 part by mass or more with respect to 100 parts by mass of the component (a-1).
  • the content is preferably 1800 parts by mass or less, more preferably 1500 parts by mass or less.
  • the resin composition of the present invention may further contain inorganic particles.
  • Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like.
  • the primary particle size of these inorganic particles is preferably 100 nm or less, particularly preferably 60 nm or less, from the viewpoint of maintaining sensitivity.
  • a method for obtaining the primary particle diameter of the inorganic particles there is a calculation method obtained from the specific surface area as the number average particle diameter.
  • Specific surface area is defined as the sum of the surface areas contained in a unit mass of powder.
  • a specific method for measuring the specific surface area is the BET method, which can be measured using a specific surface area measuring device (such as HMmodel-1201 manufactured by Mounttech).
  • the resin composition may further contain a silane coupling agent such as trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane. Good.
  • the preferable content of the compound used for enhancing the adhesion to these silicon substrates is 0.01 parts by mass or more with respect to 100 parts by mass of the component (a-1). Further, from the viewpoint of maintaining mechanical properties such as elongation, the content is preferably 5 parts by mass or less.
  • the viscosity of the resin composition is preferably 2 to 5000 mPa ⁇ s.
  • the solid content concentration so that the viscosity becomes 2 mPa ⁇ s or more, it becomes easy to obtain a desired film thickness using the resin composition.
  • the viscosity is 5000 mPa ⁇ s or less, it becomes easy to obtain a highly uniform coating film.
  • a resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.
  • the cured pattern of the present invention is formed by curing a resin pattern formed in a predetermined shape using the resin composition of the present invention. That is, the cured pattern of the present invention comprises a cured product of the resin composition of the present invention.
  • the cured pattern includes a step of applying and drying the resin composition of the present invention on a support substrate to obtain a resin film, a step of exposing the resin film obtained by the step, and a step of exposing the resin film after the exposure to an alkaline aqueous solution. It can manufacture by the method of including the process of developing using A, and forming the resin pattern, and the process of heat-processing the resin pattern after the said image development.
  • the cured pattern is obtained by applying the resin composition of the present invention onto a substrate, then removing the organic solvent to obtain a resin sheet, and attaching the resin sheet obtained by the above process onto another support substrate.
  • a step of aligning, a step of exposing the resin sheet after bonding, a step of developing the resin sheet after exposure using an alkaline aqueous solution to form a resin pattern, and a step of heat-treating the resin pattern after development It can also manufacture by the method containing these.
  • the method for forming the cured pattern is as follows in more detail.
  • the resin composition of the present invention is applied to a support substrate.
  • a support substrate a wafer made of silicon, ceramics, gallium arsenide, or the like on which a metal is formed as an electrode and / or wiring is used, but is not limited thereto.
  • the resin composition of the present invention is also excellent in adhesion to the metal surface containing copper element
  • the support substrate is formed with at least one kind of metal wiring containing copper element and metal electrode containing copper element. It is preferable from the viewpoint of obtaining a highly durable semiconductor element.
  • Application methods include spin coating using a spinner, spray coating, slit coating, and roll coating.
  • the film thickness of the coating film obtained by applying the resin composition varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but usually the film thickness after drying is 0.1 to 150 ⁇ m. To be applied.
  • the support substrate can be pretreated with the above-described silane coupling agent.
  • a silane coupling agent was dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate at a concentration of 0.5 to 20% by mass.
  • a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate at a concentration of 0.5 to 20% by mass.
  • the support substrate is surface-treated by a technique such as spin coating, dipping, spray coating, or steam treatment. If necessary, a heat treatment is then performed at 50 to 300 ° C. to advance the reaction between the support substrate and the silane
  • the support substrate coated with the resin composition is dried to obtain a resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at 50 to 150 ° C. for 1 minute to several hours.
  • the resin film obtained by the above process is irradiated with actinic radiation through a mask having a desired pattern to expose the resin film.
  • actinic radiation used for exposure there are ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, mercury lamp i-line (365 nm), h-line (405 nm), g-line (436 nm), or these Actinic radiation having a mixed wavelength including is preferably used.
  • post exposure bake may be performed.
  • post-exposure baking effects such as improvement in resolution after development or increase in the allowable range of development conditions can be expected.
  • Post-exposure baking can be performed using an oven, a hot plate, infrared rays, a flash annealing apparatus, a laser annealing apparatus, or the like.
  • the post-exposure baking temperature is preferably 50 to 180 ° C., more preferably 60 to 150 ° C.
  • the post-exposure baking time is preferably 10 seconds to several hours. When the post-exposure bake time is within the above range, the reaction proceeds favorably and the development time may be shortened.
  • the desired resin pattern is formed by developing the exposed resin film using a developer.
  • a developer an alkaline aqueous solution is preferable.
  • alkaline aqueous solutions include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl
  • An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable.
  • polar solutions such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, and dimethylacrylamide; methanol, ethanol , Alcohols such as isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone are added singly or in combination. May be. After development, it is preferable to rinse with water.
  • alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
  • the resin pattern after development is heat-treated to cure the resin pattern and obtain a cured pattern.
  • the curing of the resin pattern is preferably performed by applying a temperature of 150 to 500 ° C. to the resin pattern to cause a thermal crosslinking reaction, an imide ring-closing reaction, an oxazole ring-closing reaction, and the like. Chemical resistance can be improved.
  • the resin composition of the present invention is excellent in that the shape change of the cured pattern in the solder reflow process is small even when the maximum temperature of the heat treatment process for curing is 150 ° C. or higher and 220 ° C. or lower.
  • the maximum temperature is preferably 150 ° C. or higher and 220 ° C. or lower.
  • the maximum temperature of the heat treatment step is lower than the glass transition temperature of the component (a-1) and higher than the glass transition temperature of the component (a-2), only the component (a-2) is cured.
  • the fluidity can be increased, which is preferable from the viewpoint of improving the elongation.
  • the 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 110 ° C., 160 ° C. and 200 ° C. for 30 minutes each is mentioned.
  • a method of linearly raising the temperature from room temperature to 200 ° C. over 1 hour can be mentioned. In such a heat treatment step, the temperature when the temperature becomes the highest is defined as the maximum temperature.
  • the resin sheet of the present invention is formed by molding the resin composition of the present invention into a sheet shape. However, when the resin composition contains a solvent, the resin sheet of the present invention is obtained by removing the solvent from the resin composition of the present invention.
  • a resin sheet can be produced by applying the above-described resin composition on a substrate. When a resin composition contains a solvent, after apply
  • a polyethylene terephthalate (PET) film or the like can be used as the substrate on which the resin composition is applied.
  • a PET film having a surface coated with a release agent such as a silicone resin is used.
  • Use as a substrate is preferable because the resin sheet and the substrate can be easily peeled off.
  • the thickness of the substrate is not particularly limited, but is preferably in the range of 30 to 80 ⁇ m from the viewpoint of workability.
  • Examples of the method for removing the organic solvent contained in the resin composition include heating with an oven or a hot plate, vacuum drying, heating with an electromagnetic wave such as infrared rays or microwaves. It is preferably carried out in the range of 50 to 140 ° C. for 1 minute to 1 hour using an oven.
  • the removal of the organic solvent is insufficient, the cured product obtained by the next curing treatment may be in an uncured state or may have poor thermomechanical characteristics.
  • a cover film may be bonded to the surface of the resin sheet.
  • two or more resin sheets may be bonded together to obtain a desired film thickness.
  • post-exposure baking, removal of exposed or unexposed areas using a developer to form a resin pattern, and curing of the resin pattern by applying a temperature of 150 ° C to 500 ° C A cured pattern can be obtained through the process of performing.
  • the resin composition of the present invention can be suitably used for applications such as semiconductor electronic parts and semiconductor devices.
  • the cured pattern formed using the resin composition of the present invention as described above is suitably used for applications such as an interlayer insulating film and a semiconductor protective film.
  • a cured pattern made of a cured product of the resin composition of the present invention is used as a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, an insulating layer for an organic electroluminescent element, etc.
  • the arranged semiconductor electronic component or semiconductor device is preferably used.
  • the film thickness of the resin film on the support substrate was measured using an optical interference type film thickness measuring device (Lambda Ace VM-1030 manufactured by SCREEN Holdings Co., Ltd.).
  • the refractive index of the resin film was measured as 1.629 for polyimide.
  • the glass transition temperature in this case is an intermediate glass transition temperature calculated from a change in calorie according to a method in accordance with JIS K 7121-2012 “Method for measuring plastic transition temperature”.
  • the alkali dissolution rate when the resin film is completely dissolved in a time of less than 1 minute, the time taken for the dissolution is measured, and from this and the film thickness of the resin film before immersion, the film thickness dissolved per minute is obtained, This was defined as the alkali dissolution rate.
  • the molecular weight of the resin was determined by using a gel permeation chromatography (GPC) apparatus (Waters 2690-996 manufactured by Nippon Waters Co., Ltd.), and the developing solvent was N-methyl-2-pyrrolidone (hereinafter referred to as NMP). And the polystyrene equivalent weight average molecular weight (Mw) was calculated.
  • GPC gel permeation chromatography
  • Imido ring closure rate (R IM (%)) A resin having an imide or imide precursor structure was dissolved in GBL to a concentration of 35% by mass. This solution was applied onto a 4-inch silicon wafer by spin coating using a spinner (1H-DX, manufactured by Mikasa Co., Ltd.), then baked for 3 minutes on a hot plate at 120 ° C., and a resin having a thickness of 4 to 5 ⁇ m. A membrane was prepared. This wafer with resin film was divided into two parts, and one of them was cleaned using a clean oven (CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.) under nitrogen flow (oxygen concentration of 20 ppm or less) at 140 ° C.
  • a clean oven CHC-21CD-S manufactured by Koyo Thermo System Co., Ltd.
  • the transmission infrared absorption spectrum of the resin film before and after curing was measured using an infrared spectrophotometer (FT-720, manufactured by Horiba, Ltd.), respectively, and an absorption peak (near 1780 cm ⁇ 1) of an imide structure attributed to polyimide. After confirming the presence of 1377 cm ⁇ 1 ), the peak intensity around 1377 cm ⁇ 1 (before curing: X, after curing: Y) was determined.
  • FT-720 infrared spectrophotometer
  • the i-line, h-line, and g-line of the mercury lamp are applied to the silicon wafer with a resin film after pre-baking using an exposure apparatus (Mask Aligner PEM-6M manufactured by Union Optical Co., Ltd.).
  • the actinic radiation of a wavelength including, such as the exposure amount of 5,000J / m 2 at the g-line, adding a step of irradiating the entire surface of the wafer.
  • This silicon wafer with a resin film was subjected to a heat treatment using a clean oven CLH-21CD-S at 120 ° C. for 30 minutes in a nitrogen stream (oxygen concentration of 20 ppm or less), then further heated to 180 ° C. for 1 hour. It was. Thereafter, when the temperature dropped to 50 ° C. or lower, the wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel the cured film from the wafer. This cured film was cut into strips having a width of 1 cm and a length of 9 cm, and was pulled at 23 ° C. and a tensile rate of 50 mm / min using a universal testing machine (Orientec Co., Ltd. Tensilon RTM-100).
  • the degree of measurement was taken. The measurement was performed on 10 strips per specimen, and the average value of the top 5 points was obtained. Very good when elongation at break is 15% or more (3), good when 5% or more and less than 15% (2), less than 5%, or failure when measurement is not possible due to insufficient film strength ( 1).
  • the i-line, h-line, and g-line of the mercury lamp are applied to the silicon wafer with a resin film after pre-baking using an exposure apparatus (Mask Aligner PEM-6M manufactured by Union Optical Co., Ltd.).
  • the actinic radiation of a wavelength including, such as the exposure amount of 5,000J / m 2 at the g-line, adding a step of irradiating the entire surface of the wafer.
  • This silicon wafer with a resin film was subjected to a heat treatment using a clean oven CLH-21CD-S at 120 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less), then further heated to 210 ° C. for 1 hour. It was.
  • the wafer with a cured film after the heat treatment was measured with a stress measuring device (FLX2908 manufactured by KLA Tencor). As a result, the stress value of 30 MPa or more was insufficient (1), the case of 20 MPa or more and less than 30 MPa was good (2), and the case of less than 20 MPa was very good (3).
  • a mask with a pattern cut is set on the exposure machine i-line stepper (NSR-2005i9C manufactured by Nikon Corporation), and the pre-baked silicon wafer with a resin film is applied. It was exposed while changing the exposure amount in 10 mJ / cm 2 steps in a range of 100 ⁇ 900mJ / cm 2.
  • a mask with a pattern cut is set in an exposure apparatus (Mask Aligner PEM-6M manufactured by Union Optics Co., Ltd.), and a mercury lamp is applied to the silicon wafer with a resin film after pre-baking.
  • Actinic radiation having a wavelength including i-line, h-line, and g-line is exposed to an exposure dose of 5,000 J / m 2 with g-line, and after exposure, 1 degree at 100 ° C. with an ACT-8 hot plate. Baked for a minute.
  • TMAH tetramethylammonium hydroxide
  • the developed silicon wafer with a resin pattern is cured using a clean oven CLH-21CD-S at 120 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less), then further heated to 180 ° C. for 1 hour.
  • the resin pattern was cured to obtain a cured pattern. Thereafter, the silicon wafer was taken out when the temperature dropped to 50 ° C. or lower, and the thickness of the cured pattern was measured.
  • the thickness of the resin film, the development paddle time, etc. were adjusted so that the thickness of the cured pattern after curing was 5 ⁇ m.
  • Two silicon wafers were processed for each level, and one of the wafers was baked on a hot plate at 250 ° C. for 5 minutes, and then removed from the hot plate and allowed to cool to room temperature three times. These silicon wafers with a cured pattern were cleaved with a diamond pen, and a cross section of a 20 ⁇ m wide trench pattern was observed using a scanning electron microscope (SEM, S-4800 manufactured by Hitachi High-Technologies Corporation).
  • a peak was assigned from the m / z of the obtained measurement spectrum and the molecular weight of the solvent, and the amount of gas generated corresponding to the solvent was determined.
  • a specimen different from that used for the measurement was immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel the cured film from the wafer, and the weight of the cured film was measured.
  • the solvent content in the cured film was calculated from the weight of the cured film 1 cm in length and 2 cm in width and the amount of generated gas.
  • a mask with a pattern cut is set on the exposure machine i-line stepper (NSR-2005i9C manufactured by Nikon Corporation), and the pre-baked silicon wafer with a resin film is applied. It was exposed while changing the exposure amount in 10 mJ / cm 2 steps in a range of 100 ⁇ 900mJ / cm 2.
  • a mask with a pattern cut is set in an exposure apparatus (Mask Aligner PEM-6M manufactured by Union Optics Co., Ltd.), and a mercury lamp is applied to the silicon wafer with a resin film after pre-baking.
  • Actinic rays having wavelengths including i-line, h-line, and g-line were exposed to an exposure dose of 5,000 J / m 2 with g-line, and after exposure, baked on a hot plate at 100 ° C. for 1 minute.
  • the film was developed by a dip method using a tetramethylammonium aqueous solution (manufactured by Tama Chemical Industry Co., Ltd.) diluted to 0.8% by weight with pure water, and then rinsed with pure water to give a film thickness of 5 A resin pattern of ⁇ 6 ⁇ m was obtained.
  • a tetramethylammonium aqueous solution manufactured by Tama Chemical Industry Co., Ltd.
  • the substrate with the resin pattern was cured at 120 ° C. for 30 minutes in a nitrogen stream (oxygen concentration of 20 ppm or less), then further heated to 180 ° C. for 1 hour to cure the resin pattern.
  • a cured pattern was obtained by curing.
  • a die shear tester (DAGE SERIES 4000, manufactured by Daisy Japan Co., Ltd.), a rectangular convex pattern with a length of 30 ⁇ m and a width of 120 ⁇ m is shared in the vertical direction at a test height of 1 ⁇ m and a range of 2.5 N, and then peeled off.
  • the operation for obtaining the maximum load at the time of peeling was performed for each of the five convex patterns of the same size, and the adhesion strength with the substrate was obtained from the average value and the pattern area.
  • the adhesion strength was 100 MPa or more as extremely good (3), 60 MPa or more and less than 100 MPa as good (2), and less than 60 MPa as bad (1).
  • HA diamine compound
  • Synthesis Example 3 Synthesis of Alkali-Soluble Polyimide Resin (A-2) 124.53 g (0.34 mol) of BAHF and 4.97 g (0.02) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane A polymerization reaction was carried out in the same manner as in Synthesis Example 2 except that the molar amount was changed to (mol) to obtain an alkali-soluble polyimide resin (A-2) powder.
  • Synthesis Example 8 Synthesis of Alkali-Soluble Polyimide-Benzoxazole Precursor Resin (A-7) 62.04 g (0.2 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added under a dry nitrogen stream. It was dissolved in 630 g of NMP. Here, 106.39 g (0.176 mol) of HA and 1.99 g (0.008 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added together with 20 g of NMP and reacted at 20 ° C. for 1 hour. Subsequently, it was made to react at 50 degreeC for 2 hours.
  • alkali-soluble polyamideimide precursor solution solid content concentration 20 mass%.
  • This solution was poured into 5 L of water to obtain a precipitate, and the precipitate was collected by filtration and washed with water three times to obtain an alkali-soluble polyamideimide precursor powder.
  • This powder was dried at 150 ° C. for 5 hours, then dried at 200 ° C. for 1 hour and 220 ° C. for 2 hours to obtain an alkali-soluble polyamideimide resin (A-8) powder.
  • the obtained polymer was dissolved in 1.6 L of acetone, 2 g of concentrated hydrochloric acid was added at 60 ° C. and stirred for 7 hours, and pt-butoxystyrene was deprotected and converted to hydroxystyrene. After completion of the reaction, the solution was poured into water to precipitate the polymer, and the resulting precipitate was washed three times with water and then dried in a vacuum dryer at 50 ° C. for 24 hours. A polyhydroxystyrene resin (A-10) having 25 mol% of styrene residues was obtained.
  • C Thermal crosslinking agent HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) (C-1), NIKACAL MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) (C-2), TECHMORE VG3101L (trade name, manufactured by Printec Co., Ltd.) (C-3) is shown below.
  • D Compound having a polymerizable unsaturated bond group, “Blemmer” (registered trademark) PDBE-200A (trade name, manufactured by NOF Corporation) (D-1), dipentaerythritol hexaacrylate (trade name DPHA, Nippon Kayaku Co., Ltd. (D-2) is shown below.
  • the alkali-soluble resins (A-1 to 11) obtained in Synthesis Examples 2 to 12 correspond to any of the components (a-1), (a-2), (a-3), and other resins.
  • the classification results and the glass transition temperature, alkali dissolution rate, weight average molecular weight, and imide ring closure rate (R IM (%)) determined by the above method are shown in Table 1.
  • Tables 6 and 7 show the results of evaluating the elongation at break, the stress measurement, and the solder reflow process resistance by the above method using the positive varnish produced as described above. In the table, it is also shown whether at least one of the component (a-2) and the other resin contains the structural unit of the general formula (2) or the general formula (3). In Table 7, “nd” indicates that the measurement was impossible due to insufficient film strength.
  • the elongation at break is 5% or more, the stress value is less than 30 MPa, and there is no change in the pattern shape in the solder reflow process resistance evaluation, The taper angle decrease was less than 20 °, and the result was good or very good.
  • the component (a-2) does not include the structural unit of the general formula (2) or the general formula (3).
  • the examples using W-19 and W-20 containing the structural units of general formula (2) and general formula (3) are more stressful The result was low.
  • Tg difference glass transition temperature
  • W-14 Tg difference: 184 ° C.
  • W-24 Tg difference
  • the elongation was higher than the example using the difference (205 ° C.).
  • W-2 Tg difference: 130 ° C.
  • W-20 Tg difference: 141 ° C.
  • W-21 Tg difference: 154 ° C.
  • W-23 Tg difference: 148 ° C.
  • the stress was lower.
  • Tables 8 and 9 show the results of evaluating the elongation at break, the stress measurement, and the solder reflow process resistance by the above method using the negative varnish produced as described above. In the table, it is also shown whether at least one of the component (a-2) and the other resin contains the structural unit of the general formula (2) or the general formula (3).
  • Examples 26 to 39 all have an elongation at break of 5% or more, a stress value of less than 30 MPa, and there is no change in the pattern shape in the solder reflow process resistance evaluation, The result was good or very good, with only a decrease in taper angle of less than 20 °.
  • the component (a-2) does not contain the structural unit of the general formula (2) or the general formula (3).
  • the examples using W-49 and W-50 containing structural units of the general formula (2) and the general formula (3) are more stressed. The result was low.
  • Tg difference difference in glass transition temperature (Tg difference) between the component (a-1) and the component (a-2)
  • W-49 Tg difference: 184 ° C.
  • W-54 Tg Compared to the example using the difference (205 ° C.), the elongation was higher and the stress was lower.
  • W-41 Tg difference: 130 ° C.
  • W-50 Tg difference: 141 ° C.
  • W-51 Tg difference: 154 ° C.
  • W-53 Tg difference: 148 ° C.
  • the stress was lower.
  • Table 10 shows the results of measuring the amount of solvent in the cured film by the above method using the varnish produced as described above.
  • GBL represents ⁇ -butyrolactone
  • EL represents ethyl lactate
  • PGME represents propylene glycol monomethyl ether
  • DAA diacetone alcohol
  • Tables 11 and 12 show the results of measuring the adhesion strength with copper by the above method using the varnish produced as described above. In the table, it is also shown whether the structural unit (a-1) contains the structural unit of the general formula (4).
  • Examples 48 to 52 and Comparative Example 31 using the resin containing the structural unit of the general formula (4) as the component (a-1) include the resin containing the structural unit of the general formula (4). Compared with Examples 53 to 57 and Comparative Examples 32 to 39, which had no adhesion, the adhesion strength with copper was better. Similarly, in Table 12, Examples 58 and 59 and Comparative Example 40 using the resin containing the structural unit of the general formula (4) as the component (a-1) include the structural unit of the general formula (4). Compared with Examples 60 to 64 and Comparative Examples 41 to 47 containing no resin, the adhesion strength with copper was better.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

La présente invention concerne une composition de résine contenant : (a-1) une résine de polyimide soluble dans les composés alcalins ayant une température de transition vitreuse de 200 à 300 °C ; (a-2) au moins une résine sélectionnée parmi les polyimides solubles dans les composés alcalins, les polybenzoxazoles solubles dans les composés alcalins, et les polyamideimides solubles dans les composés alcalins, et leurs précurseurs et copolymères, la résine ayant une température de transition vitreuse de 50 à 150 °C ; et (b) un agent de photosensibilisation, où, par rapport à 100 parties en masse du constituant (a-1), le constituant (a-2) est contenu en une quantité de 10 à 40 parties en masse. Selon la présente invention, même lorsque la température maximale d'un procédé de traitement thermique pour le durcissement est de 150 à 220 °C, il est possible d'obtenir une composition de résine pour laquelle un film durci résultant présente une faible contrainte et pour laquelle peu de changements apparaissent dans la forme d'un motif durci dans un procédé ultérieur de refusion de soudure.
PCT/JP2018/005978 2017-03-03 2018-02-20 Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur Ceased WO2018159384A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018510541A JP7059927B2 (ja) 2017-03-03 2018-02-20 樹脂組成物、樹脂シート、硬化パターンおよび半導体電子部品または半導体装置

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017040066 2017-03-03
JP2017-040066 2017-03-03
JP2017194282 2017-10-04
JP2017-194282 2017-10-04

Publications (1)

Publication Number Publication Date
WO2018159384A1 true WO2018159384A1 (fr) 2018-09-07

Family

ID=63370060

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/005978 Ceased WO2018159384A1 (fr) 2017-03-03 2018-02-20 Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur

Country Status (3)

Country Link
JP (1) JP7059927B2 (fr)
TW (1) TW201840643A (fr)
WO (1) WO2018159384A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018172533A (ja) * 2017-03-31 2018-11-08 太陽インキ製造株式会社 硬化性樹脂組成物、積層構造体、その硬化物、および電子部品
EP3734362A1 (fr) 2019-04-15 2020-11-04 Shin-Etsu Chemical Co., Ltd. Composition de résine photosensible positive, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film protecteur de surface et composant électronique
JP2021185232A (ja) * 2019-09-06 2021-12-09 昭和電工マテリアルズ株式会社 ポリアミドイミド樹脂、樹脂組成物、及び半導体装置
JP2021193411A (ja) * 2020-06-08 2021-12-23 住友ベークライト株式会社 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス
CN114524938A (zh) * 2021-10-28 2022-05-24 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件
JP2022147792A (ja) * 2021-03-23 2022-10-06 信越化学工業株式会社 ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、ポジ型感光性ドライフィルムの製造方法、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品
WO2022264934A1 (fr) * 2021-06-14 2022-12-22 東レ株式会社 Composition de résine photosensible, produit durci, procédé de production de produit durci, et dispositif d'affichage
CN116333303A (zh) * 2023-05-25 2023-06-27 明士(北京)新材料开发有限公司 一种抗模压的碱性水性显影的光敏胶膜及其应用
WO2023182327A1 (fr) * 2022-03-23 2023-09-28 東レ株式会社 Composition de résine photosensible positive, produit durci, dispositif d'affichage électroluminescent organique et procédé de production de produit durci
JP2024510332A (ja) * 2021-03-17 2024-03-06 ドンジン セミケム カンパニー リミテッド ポジ型感光性樹脂組成物、絶縁膜及びそれを含む表示装置

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642682A (en) * 1968-12-13 1972-02-15 Desoto Inc Lacquers containing guanamine-based polyimide resins
JPH10120785A (ja) * 1996-10-21 1998-05-12 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物およびフィルム接着剤とその製造方法
JPH10231426A (ja) * 1997-02-18 1998-09-02 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物
JP2009132154A (ja) * 2003-04-07 2009-06-18 Mitsui Chemicals Inc ポリイミド金属積層板
JP2012255107A (ja) * 2011-06-09 2012-12-27 Mitsui Chemicals Inc 熱可塑性ポリイミド組成物、それを含む接着剤、積層体、及びデバイス
JP2014137434A (ja) * 2013-01-16 2014-07-28 Toray Ind Inc ポジ型感光性樹脂組成物
WO2015170432A1 (fr) * 2014-05-09 2015-11-12 日立化成株式会社 Composition d'agent adhésif photosensible de type positif, motif d'agent adhésif, tranche de semi-conducteur avec couche d'agent adhésif, dispositif à semi-conducteur et son procédé de production
JP2016009159A (ja) * 2014-06-26 2016-01-18 日立化成株式会社 ポジ型感光性接着剤組成物、接着剤パターン、接着剤層付半導体ウェハ及び半導体装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642682A (en) * 1968-12-13 1972-02-15 Desoto Inc Lacquers containing guanamine-based polyimide resins
JPH10120785A (ja) * 1996-10-21 1998-05-12 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物およびフィルム接着剤とその製造方法
JPH10231426A (ja) * 1997-02-18 1998-09-02 Sumitomo Bakelite Co Ltd ポリイミド樹脂組成物
JP2009132154A (ja) * 2003-04-07 2009-06-18 Mitsui Chemicals Inc ポリイミド金属積層板
JP2012255107A (ja) * 2011-06-09 2012-12-27 Mitsui Chemicals Inc 熱可塑性ポリイミド組成物、それを含む接着剤、積層体、及びデバイス
JP2014137434A (ja) * 2013-01-16 2014-07-28 Toray Ind Inc ポジ型感光性樹脂組成物
WO2015170432A1 (fr) * 2014-05-09 2015-11-12 日立化成株式会社 Composition d'agent adhésif photosensible de type positif, motif d'agent adhésif, tranche de semi-conducteur avec couche d'agent adhésif, dispositif à semi-conducteur et son procédé de production
JP2016009159A (ja) * 2014-06-26 2016-01-18 日立化成株式会社 ポジ型感光性接着剤組成物、接着剤パターン、接着剤層付半導体ウェハ及び半導体装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MURAYAMA, HIROSHI: "A recent trend of improvement on polyimides", CIRCUIT TECHNOLOGY, vol. 2, no. 2, 1987, pages 98 - 109 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018172533A (ja) * 2017-03-31 2018-11-08 太陽インキ製造株式会社 硬化性樹脂組成物、積層構造体、その硬化物、および電子部品
EP3734362A1 (fr) 2019-04-15 2020-11-04 Shin-Etsu Chemical Co., Ltd. Composition de résine photosensible positive, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film protecteur de surface et composant électronique
JP7310860B2 (ja) 2019-09-06 2023-07-19 株式会社レゾナック ポリアミドイミド樹脂、樹脂組成物、及び半導体装置
JP2021185232A (ja) * 2019-09-06 2021-12-09 昭和電工マテリアルズ株式会社 ポリアミドイミド樹脂、樹脂組成物、及び半導体装置
JP7392580B2 (ja) 2020-06-08 2023-12-06 住友ベークライト株式会社 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス
JP2023155261A (ja) * 2020-06-08 2023-10-20 住友ベークライト株式会社 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス
JP2021193411A (ja) * 2020-06-08 2021-12-23 住友ベークライト株式会社 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス
JP7647809B2 (ja) 2020-06-08 2025-03-18 住友ベークライト株式会社 感光性樹脂組成物、電子デバイスの製造方法および電子デバイス
JP2024510332A (ja) * 2021-03-17 2024-03-06 ドンジン セミケム カンパニー リミテッド ポジ型感光性樹脂組成物、絶縁膜及びそれを含む表示装置
JP2022147792A (ja) * 2021-03-23 2022-10-06 信越化学工業株式会社 ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、ポジ型感光性ドライフィルムの製造方法、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品
JP7495897B2 (ja) 2021-03-23 2024-06-05 信越化学工業株式会社 ポジ型感光性樹脂組成物、ポジ型感光性ドライフィルム、ポジ型感光性ドライフィルムの製造方法、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品
WO2022264934A1 (fr) * 2021-06-14 2022-12-22 東レ株式会社 Composition de résine photosensible, produit durci, procédé de production de produit durci, et dispositif d'affichage
CN114524938A (zh) * 2021-10-28 2022-05-24 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件
CN114524938B (zh) * 2021-10-28 2024-02-09 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件
WO2023182327A1 (fr) * 2022-03-23 2023-09-28 東レ株式会社 Composition de résine photosensible positive, produit durci, dispositif d'affichage électroluminescent organique et procédé de production de produit durci
CN116333303A (zh) * 2023-05-25 2023-06-27 明士(北京)新材料开发有限公司 一种抗模压的碱性水性显影的光敏胶膜及其应用
CN116333303B (zh) * 2023-05-25 2023-08-04 明士(北京)新材料开发有限公司 一种抗模压的碱性水性显影的光敏胶膜及其应用

Also Published As

Publication number Publication date
JP7059927B2 (ja) 2022-04-26
TW201840643A (zh) 2018-11-16
JPWO2018159384A1 (ja) 2019-12-26

Similar Documents

Publication Publication Date Title
JP7059927B2 (ja) 樹脂組成物、樹脂シート、硬化パターンおよび半導体電子部品または半導体装置
KR102456965B1 (ko) 감광성 수지 조성물, 수지 경화막의 제조 방법 및 반도체 장치
JP6048257B2 (ja) 耐熱性樹脂及びその前駆体組成物
JP6724363B2 (ja) 樹脂および感光性樹脂組成物
TWI724143B (zh) 感光性樹脂組成物、使用其之層間絕緣膜或表面保護膜的製造方法、以及層間絕緣膜及表面保護膜
JP6102736B2 (ja) ポジ型感光性樹脂組成物
JP6915533B2 (ja) 硬化膜およびその製造方法
KR102542822B1 (ko) 수지 조성물, 그의 경화 릴리프 패턴, 및 그것을 사용한 반도체 전자 부품 또는 반도체 장치의 제조 방법
WO2017217293A1 (fr) Composition de résine photosensible
JP6743692B2 (ja) 感光性樹脂組成物、感光性シート、半導体装置および半導体装置の製造方法
JP2009258634A (ja) ポジ型感光性樹脂組成物
JP6961342B2 (ja) ポリイミド樹脂およびポジ型感光性樹脂組成物
JP6939553B2 (ja) 樹脂組成物
JP2010229210A (ja) 樹脂組成物
JP2010210851A (ja) 感光性樹脂組成物
JP2017179364A (ja) ポリアミド樹脂の製造方法およびそれを用いた感光性樹脂組成物の製造方法
JP2018095721A (ja) 樹脂組成物、樹脂シートおよび硬化膜
TWI692490B (zh) 硬化膜及其製造方法
JP2010072143A (ja) ポジ型感光性樹脂組成物
WO2026088942A1 (fr) Composition de résine, produit durci et dispositif d'affichage électroluminescent organique
CN121443649A (zh) 树脂、感光性树脂组合物及这些的硬化物、以及使用所述硬化物的电子部件和显示装置
WO2021193091A1 (fr) Feuille de résine photosensible, composant électronique, filtre à ondes acoustiques et procédé de production de filtre à ondes acoustiques
TW201413387A (zh) 正型感光性樹脂組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018510541

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18761105

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18761105

Country of ref document: EP

Kind code of ref document: A1