Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/065—Polyamides; Polyesteramides; Polyimides
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0387—Polyamides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
  • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• • 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
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • 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
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

• the present invention relates to a photosensitive polyimide resin composition, a resin film, and an electronic device.
• a resin film obtained by exposing a photosensitive polyimide resin composition having excellent heat resistance and insulating properties is widely used.
• Examples of the technique relating to such a photosensitive polyimide resin composition include those described in Patent Documents 1 and 2.
• Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin, a radically polymerizable compound, a photopolymerization initiator and a colorant, wherein the alkali-soluble resin is a polyimide, a polyimide precursor, or a polybenzoxazole precursor. And / or a bifunctional or higher functional (meth) acrylic compound containing a copolymer thereof and having a glass transition temperature of 150 ° C. or higher when the radically polymerizable compound is used as a homopolymer, and other tetrafunctional or higher functional compounds.
• a photosensitive resin composition containing the (meth) acrylic compound of the above is described.
• Patent Document 2 includes a precursor of a heterocyclic-containing polymer, a thermobase generator, and a radically polymerizable compound, and the precursor of the heterocyclic ring-containing polymer has a radically polymerizable group, and the above-mentioned radically polymerizable compound is described.
• a photosensitive resin composition comprising at least one radically polymerizable compound selected from the group consisting of a compound having four or more polymerizable functional groups and a compound having three polymerizable functional groups and having a molecular weight of 400 or less. Have been described.
• the photosensitive resin composition described in Patent Document 1 is inferior in thick film developability because the light transmittance is low and the light at the time of exposure does not easily reach the lower part of the film when the film is thick.
• the resin film tends to shrink when the polyimide precursor is dehydrated and closed to form polyimide, so that the pattern shape during thick film development deteriorates or the pattern cracks. Is likely to occur.
• the photosensitive resin composition when the photosensitive resin composition is a thick film, the amount of exposure required for curing is large, so that the pattern shape tends to be more tapered. That is, the composition containing the conventional photosensitive polyimide resin and the polyfunctional radically polymerizable compound has room for improvement in terms of thick film patterning property.
• the present invention has been made in view of the above circumstances, and provides a photosensitive polyimide resin composition having excellent thick film patterning property.
• the present inventors have made extensive studies to solve the above problems. As a result, by combining the closed ring polyimide resin (A) having a specific structure and molecular weight with the polyfunctional radically polymerizable compound (B) having 4 or more and 100 or less radically polymerizable functional groups, the photosensitive is photosensitive. We have found that the thick film patterning property of the polyimide resin composition can be improved, and completed the present invention.
• the photosensitive polyimide resin composition the resin film, and the electronic device shown below are provided.
• R is a tetravalent group having a cyclic structure, an acyclic structure, or a cyclic structure and a non-cyclic structure and having 4 or more and 10 or less carbon atoms.
• A has at least one group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an organosiloxane group, and has 2 or more and 39 or less carbon atoms. It is the basis of the price.
• the main chain of A is selected from the group consisting of -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2- , -C 2 H 4 O-, and -S-. At least one group may be intervened.
• n indicates the number of repeating units.
• the end of the above formula (1) is either the group represented by the following formula (2) or the formula (3), or a hydrogen atom, and at least one of the ends is the following formula (2) or the formula (3). It is the group shown.
• X and X 2 are independently groups having 2 or more and 15 or less carbon atoms, and at least one group selected from the group consisting of an ester bond and a double bond is used. You may have.
• Y and Y 2 are independently hydrogen atoms or methyl groups, respectively.
• the content of the closed ring polyimide resin (A) is 30% by mass or more when the total solid content of the photosensitive polyimide resin composition is 100% by mass, according to the above [1] or [2].
• Photosensitive polyimide resin composition [4]
• the content of the polyfunctional radically polymerizable compound (B) is 20 parts by mass or more and 100 parts by mass when the amount of the closed ring polyimide resin (A) contained in the photosensitive polyimide resin composition is 100 parts by mass.
• the photosensitive polyimide resin composition according to any one of the above [1] to [3] below.
• the content of the colorant is less than 10 parts by mass when the amount of the closed ring polyimide resin (A) contained in the photosensitive polyimide resin composition is 100 parts by mass.
• [1] to [4] The photosensitive polyimide resin composition according to any one of.
• [6] The photosensitive polyimide resin composition according to any one of [1] to [5] above, wherein the radically polymerizable functional group contains a (meth) acryloyl group.
• the closed ring polyimide resin (A) is 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 1- (4-aminophenyl) -2,3-dihydro-1,3,3. -Trimethyl-1H-inden-5-amine, 4,4'-oxybis [3- (trifluoromethyl) benzeneamine], or 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene
• the photosensitive polyimide resin composition according to any one of the above [1] to [9], which comprises at least one unit composed of.
• Polyimide resin composition [12] The photosensitive polyimide resin composition according to any one of the above [1] to [11], which is used for forming an insulating film. [13] A resin film comprising the photosensitive polyimide resin composition according to any one of the above [1] to [12] or a cured product of the photosensitive polyimide resin composition. [14] The resin film [15] according to the above [13], which has a film thickness of 20 ⁇ m or more. An electronic device provided with the resin film according to the above [14].
• the present embodiment The embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail.
• the following embodiments are examples for explaining the present invention, and do not limit the contents of the present invention.
• the present invention can be appropriately modified and carried out within the scope of the gist thereof.
• the preferable provisions can be arbitrarily adopted, and it can be said that the combination of preferable ones is more preferable.
• the description of "XX to YY" means "XX or more and YY or less”.
• (meth) acrylate in the present embodiment means both “acrylate” and “methacrylate”. The same applies to other similar terms (“(meth) acrylic acid”, “(meth) acryloyl group”, etc.).
• Photosensitive polyimide resin composition The photosensitive polyimide resin composition according to the present embodiment has a structure represented by the following formula (1) and has a weight average molecular weight of 70,000 or less with the closed ring polyimide resin (A). 4. The polyfunctional radically polymerizable compound (B) having 4 or more and 100 or less radically polymerizable functional groups is contained.
• R is a tetravalent group having a cyclic structure, an acyclic structure, or a cyclic structure and an acyclic structure and having 4 or more and 10 or less carbon atoms.
• A has at least one group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an organosiloxane group, and has 2 or more and 39 or less carbon atoms. It is the basis of the price.
• the main chain of A is selected from the group consisting of -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2- , -C 2 H 4 O-, and -S-.
• n indicates the number of repeating units.
• the end of the above formula (1) is either the group represented by the following formula (2) or the formula (3), or a hydrogen atom, and at least one of the ends is the following formula (2) or the formula (3). It is the group shown.
• X and X 2 are independently groups having 2 or more and 15 or less carbon atoms, and have at least one group selected from the group consisting of an ester bond and a double bond. You may.
• Y and Y 2 are independently hydrogen atoms or methyl groups, respectively.
• the photosensitive polyimide resin composition according to the present embodiment has a structure represented by the above formula (1), and has a weight average molecular weight of 70,000 or less as a closed ring polyimide resin (A) and 4 or more and 100 or less. It is a composition containing a polyfunctional radically polymerizable compound (B) having a radically polymerizable functional group of the above and having excellent thick film patterning property.
• excellent in thick film patterning property means that when the film thickness of the resin film is, for example, a thick film of 20 ⁇ m or more, the pattern shape is good and the developability is excellent.
• a good pattern shape means a shape in which the lower width / upper width of the pattern is, for example, 0.80 or more and 1.20 or less, preferably 0.90 or more and 1.10 or less, and is excellent in developability. It means that there is little residue in the unexposed area after development.
• the photosensitive polyimide resin composition according to the present embodiment has a structure represented by the above formula (1), and has a weight average molecular weight of 70,000 or less as a closed ring polyimide resin (A) and 4 or more and 100 or less.
• the polyfunctional radically polymerizable compound (B) having the radically polymerizable functional group of the above the thick film patterning property is excellent.
• the reason is not clear, but it can be considered as follows. First, the developability is better as the difference in solubility in the developing solution between the exposed part and the unexposed part (hereinafter, also simply referred to as “developer solubility”) is larger. It is important to widen the difference in developer solubility in unexposed areas.
• the closed ring polyimide resin (A) having the structure represented by the above formula (1) and having a weight average molecular weight of 70,000 or less has high developer solubility, and therefore is not yet thickened even if the resin film is thickened. It is considered that the developer solubility of the exposed part is high. Further, since the closed ring polyimide resin (A) having the structure represented by the above formula (1) is excellent in transparency, even if the resin film is thickened, the light at the time of exposure easily reaches the lower part of the film, and the resin film is further formed.
• the cross-linking can be uniformly performed, and further, by combining with the polyfunctional radically polymerizable compound (B), the cross-linking density of the resin film can be improved and the solubility of the developing solution in the exposed portion can be lowered. Further, since the closed ring polyimide resin (A) is a resin for which imidization has already been completed, a dehydration ring closure step is not required. Therefore, it is considered possible to reduce the developer solubility of the exposed portion while suppressing deformation such as curing shrinkage of the resin film during exposure by combining with the polyfunctional radically polymerizable compound (B).
• the photosensitive polyimide resin composition according to the present embodiment by combining the closed ring polyimide resin (A) and the polyfunctional radically polymerizable compound (B), the developing liquid in the exposed portion and the unexposed portion is used. Since the difference in solubility can be increased, the thick film developability can be improved, and further, deformation such as curing shrinkage of the resin film during exposure can be suppressed, so that the thick film patterning property can be improved. It is thought that it was.
• the closed ring polyimide resin (A) has a structure represented by the following formula (1) and has a weight average molecular weight of 70,000 or less.
• R is a tetravalent group having a cyclic structure, an acyclic structure, or a cyclic structure and an acyclic structure and having 4 or more and 10 or less carbon atoms.
• A has at least one group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an organosiloxane group, and has 2 or more and 39 or less carbon atoms. It is the basis of the price.
• the main chain of A is selected from the group consisting of -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2- , -C 2 H 4 O-, and -S-.
• n indicates the number of repeating units.
• the end of the above formula (1) is either the group represented by the following formula (2) or the formula (3), or a hydrogen atom, and at least one of the ends is the following formula (2) or the formula (3). It is the group shown.
• X and X 2 are independently groups having 2 or more and 15 or less carbon atoms, and have at least one group selected from the group consisting of an ester bond and a double bond. You may.
• Y and Y 2 are independently hydrogen atoms or methyl groups, respectively.
• R in the above formula (1) has at least a cyclic structure
• the cyclic structure includes, for example, cyclohexane, cyclopentane, cyclobutane, bicyclopentane and steric isomers thereof except for four hydrogen atoms.
• examples thereof include tetravalent groups to be formed. More specifically, the tetravalent group includes a group represented by the following structural formula.
• a tetravalent group formed by removing four hydrogen atoms from cyclohexane is preferable.
• a in the above formula (1) has at least one group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an organosiloxane group, and has 2 carbon atoms. It is a divalent group of 39 or more and 39 or less.
• the main chain of A is selected from the group consisting of -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2- , -C 2 H 4 O-, and -S-. At least one group may be intervened.
• A is cyclohexane, dicyclohexylmethane, dimethylcyclohexane, isophorone, norbornan and alkyl-substituted products thereof, and halogen-substituted products thereof; benzene, naphthalene, biphenyl, diphenylmethane, diphenyl ether, diphenyl sulfone, benzophenone and these. Alkyl-substituted products of the above, as well as these halogen-substituted products; divalent groups formed by removing two hydrogen atoms from compounds such as organo (poly) siloxane.
• A preferably has a cyclic structure, and more preferably has at least one selected from an alicyclic hydrocarbon group and an aromatic ring. It is more preferable that A has an aromatic ring as an aromatic hydrocarbon group. More specifically, a divalent group having 6 or more and 27 or less carbon atoms represented by the following structural formula is preferably mentioned.
• the divalent group having 2 or more and 39 or less carbon atoms indicated by A contains at least one selected from the group consisting of the structures shown below.
• the divalent group having 2 or more and 39 or less carbon atoms indicated by A includes at least one group (IA) selected from the group consisting of the structures shown below.
• the divalent group having 2 or more and 39 or less carbon atoms indicated by A includes at least one group (Ib) selected from the group consisting of the structures shown below.
• the closed ring polyimide resin (A) according to the present embodiment has at least one configuration selected from the above (Ia), (Ib) and (Ic) as A in the above formula (1).
• the unit ratio is preferably 60 mol% or more from the viewpoint of developer solubility.
• the ratio of at least one structural unit selected from the above (Ia), (Ib) and (Ic) in A in the above formula (1) is more preferably 70 mol% or more, still more preferably 70 mol% or more. It is 80 mol% or more, more preferably 95 mol% or more, still more preferably 100 mol%. Above all, it is preferable to include the structural unit derived from the diamine represented by the formula (Ic) in the above ratio.
• N indicating the number of repeating units of the structural unit represented by the above formula (1) is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, from the viewpoint of further improving the mechanical properties of the obtained resin film. From the viewpoint of further improving the developer solubility of the obtained photosensitive polyimide resin composition, it is preferably 250 or less, more preferably 200 or less, still more preferably 150 or less.
• the closed ring polyimide resin (A) has either a group represented by the above formula (2) or the above formula (3) or a hydrogen atom at the end, and at least one of the ends is the above formula (2). ) Or the group represented by the formula (3).
• the closed ring polyimide resin (A) may have one end having a structure represented by the above formula (2) or the above formula (3), or both ends may be represented by the above formula (2) or the above formula (3). It may have a structure to be used.
• the group represented by X or X2 in the above formula ( 2 ) or formula (3) is a group having 2 or more carbon atoms and 15 or less carbon atoms, and is at least one selected from the group consisting of an ester bond and a double bond. It may have a group.
• the group represented by Y or Y 2 is a hydrogen atom or a methyl group.
• the structure represented by the above formula (2) or formula (3) more specifically corresponds to a structure obtained by reacting a terminal amine of a polyimide resin with a functional group-containing compound.
• the functional group-containing compound include compounds having an isocyanate group or an epoxy group and a (meth) acrylic group.
• the compound include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether.
• the structure represented by the above formula (2) or the formula (3) may have a structure in which the compound and the amine terminal of the polyimide resin are reacted.
• the weight average molecular weight of the closed ring polyimide resin (A) is 70,000 or less, preferably 60,000 or less, more preferably 50,000 or less, from the viewpoint of improving the developer solubility of the photosensitive polyimide resin composition. It is more preferably 45,000 or less, further preferably 40,000 or less, still more preferably 37,000 or less, and preferably 5,000 or more, more preferably 5,000 or more, from the viewpoint of further improving the mechanical properties of the obtained resin film. It is 10,000 or more, more preferably 13,000 or more, still more preferably 15,000 or more.
• the weight average molecular weight of the closed ring polyimide resin (A) is in the above range, the residual film ratio of the unexposed portion can be further lowered, and the developability of the photosensitive polyimide resin composition can be further improved.
• the weight average molecular weight is a polystyrene-equivalent weight average molecular weight.
• the closed ring polyimide resin (A) can be obtained by reacting the diamine component described in detail below with the tetracarboxylic acid component.
• diamine component examples include diamines, diisocyanates and diaminodisilanes, and diamines are preferable.
• the diamine content in the diamine component used as a raw material is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, still more preferably 95 mol% or more, and preferably 100 mol%. It is as follows.
• the diamine may be either an aliphatic diamine or an aromatic diamine, or a mixture thereof.
• the "aromatic diamine” represents a diamine in which an amino group is directly bonded to an aromatic ring, and a part of its structure contains an aliphatic group, an alicyclic group, and other substituents. May be good.
• the "aliphatic diamine” represents a diamine in which an amino group is directly bonded to an aliphatic group or an alicyclic group, and an aromatic group or other substituent may be contained as a part of the structure thereof.
• Examples of the aliphatic diamine include 4,4'-diaminodicyclohexylmethane, ethylenediamine, hexamethylenediamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, and 1,3-.
• Examples thereof include bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, m-xylylene diamine, p-xylylene diamine, isophorone diamine, norbornan diamine and siloxane diamines.
• aromatic diamine examples include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, diaminobenzophenone, 2,6.
• the diamine component is 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-. At least selected from inden-5-amine, 4,4'-oxybis [3- (trifluoromethyl) benzeneamine], and 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene. It is preferable to include one kind. By containing at least these diamines as the diamine component, the light transmittance and the developer solubility of the obtained photosensitive polyimide resin composition at a specific wavelength can be further improved.
• the closed ring polyimide resin (A) is 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 1- (4-aminophenyl) -2,3-dihydro-1. , 3,3-trimethyl-1H-inden-5-amine, 4,4'-oxybis [3- (trifluoromethyl) benzeneamine] or 1,3-bis [2- (4-aminophenyl) -2- It preferably contains at least one unit composed of [propyl] benzene.
• tetracarboxylic acid component examples include cyclohexanetetracarboxylic acid, cyclohexanetetracarboxylic acid esters, cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid, cyclobutanetetracarboxylic acid esters, cyclobutanetetracarboxylic acid dianhydride, and cyclo.
• the tetracarboxylic acid component preferably contains at least one selected from cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, and cyclopentanetetracarboxylic acid dianhydride, and cyclohexanetetracarboxylic acid. More preferably, it contains an acid dianhydride.
• the various tetracarboxylic acid components described above contain positional isomers.
• tetracarboxylic acid component is 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5- Cyclohexanetetracarboxylic acid methyl ester, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid methyl ester , 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid methyl ester, 1,2,4 , 5-Cyclopentanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride
• the tetracarboxylic acid component is 1,2,4,5-cyclohexanetetra because it is easy to increase the molecular weight when producing a polyimide resin and it is advantageous in that a flexible resin film can be easily obtained.
• the tetracarboxylic acid component may contain another tetracarboxylic acid or a derivative thereof, for example, as long as the flexibility and thermocompression bonding property of the resin film are not impaired.
• these other tetracarboxylic acids or derivatives thereof include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2, 2-Bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (3,4-dicarboxyphenyl) Phenyl) sulfone, bis (3,
• the light transmittance at a wavelength of 365 nm when the closed ring polyimide resin (A) according to the present embodiment has a solid content concentration of 3% by mass is a viewpoint of more uniformly cross-linking the resin film and further improving the thick film patterning property. Therefore, it is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more, still more preferably 90% or more.
• the closed ring polyimide resin (A) according to the present embodiment can be obtained, for example, by a production method including the following steps (1) and (2).
• Step (1) The tetracarboxylic acid component and the diamine component are reacted to obtain a polyimide resin having an amino group at the terminal.
• Step (2) The polyimide resin having an amino group at the terminal obtained in the above step (1) is reacted with the above functional group-containing compound (a compound having an isocyanate group or an epoxy group and a (meth) acrylic group). Let me.
• Step (1) the tetracarboxylic acid and the diamine component are reacted to obtain a polyimide resin having an amino group at the terminal.
• the organic solvent used for reacting the tetracarboxylic acid component and the diamine component is not particularly limited, but is an organic solvent containing at least one selected from the group consisting of, for example, cyclic ethers, cyclic ketones, cyclic esters, amides and ureas. Is preferable.
• the suitable solvent are not particularly limited, but ⁇ -butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, cyclo.
• aprotonic polar organic solvents such as pentanone, cyclohexanone, 1,3-dioxolane, 1,4-dioxane, tetramethylurea and tetrahydrofuran can be mentioned.
• ⁇ -butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide and N-methyl-2-pyrrolidone is more preferable.
• An imidization catalyst can be used when the tetracarboxylic acid component and the diamine component are reacted in the step (1).
• a tertiary amine compound is preferable, and specifically, trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine and triethylenediamine.
• the reaction temperature in the step (1) is, for example, 160 ° C. or higher and 230 ° C. or lower, preferably 170 ° C. or higher and 210 ° C. or lower, and more preferably 180 ° C. or higher and 200 ° C. or lower.
• the reaction temperature in the step (1) is equal to or higher than the above lower limit value, imidization and molecular weight increase can be promoted more effectively.
• the reaction temperature in the step (1) is not more than the above upper limit value, the solution viscosity can be maintained more appropriately, and problems such as the resin being burnt on the wall surface of the reaction vessel can be further avoided.
• an azeotropic dehydrating agent such as toluene or xylene may be used.
• the reaction pressure is usually normal pressure, but if necessary, the reaction can be carried out under pressure.
• the holding time of the reaction temperature is preferably 1 hour or longer, more preferably 3 hours or longer. When the holding time of the reaction temperature is equal to or longer than the above lower limit value, imidization and molecular weight increase can be promoted more effectively. There is no particular upper limit to the reaction time, but the reaction time can be, for example, 10 hours or less.
• the step (1) it is preferable to react the tetracarboxylic acid component “A mol” and the diamine component “B mol” in the range of 0.80 ⁇ A / B ⁇ 0.99, preferably 0.85 ⁇ A. It is more preferable to react in the range of / B ⁇ 0.97.
• a / B ⁇ 0.99
• it is possible to make the end of the polyimide an excess of diamine a polyimide resin having an amino group at the end can be obtained, and the molecular weight has sufficient developer solubility.
• Polyimide resin can be obtained.
• 0.80 ⁇ A / B a polyimide resin having a molecular weight that exhibits sufficient flexibility can be obtained.
• a / B approaches 1.0, a polyimide resin having a high molecular weight can be obtained. Therefore, by appropriately adjusting the A / B, a polyimide resin having a desired molecular weight can be obtained.
• the step (2) is a step of modifying the end of the polyimide resin obtained in the above step (1). Specifically, as described above, the polyimide is reacted with the functional group-containing compound (a compound having an isocyanate group or an epoxy group and a (meth) acrylic group) to have a (meth) acrylic group at the terminal. Obtain a polyimide resin.
• the functional group-containing compound a compound having an isocyanate group or an epoxy group and a (meth) acrylic group
• the functional group-containing compound that modifies the terminal of the polyimide resin is a compound having an isocyanate group or an epoxy group and a (meth) acrylic group, and specifically, 2-isocyanatoethyl methacrylate and 2-isocyanatoethyl. Examples thereof include acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether. These functional group-containing compounds may be used alone or in combination of two or more.
• the functional group-containing compound is preferably used at a ratio of 0.1 to 30 mol times that of the polyimide resin having an amino group at the terminal.
• the reaction temperature in the step (2) is preferably in the range of 30 ° C. or higher and 100 ° C. or lower, and the reaction time is preferably 1 hour or longer and 10 hours or lower.
• the reaction may be carried out as it is, or may be reacted in the presence of a catalyst if necessary.
• the catalyst include amine compounds such as triethylamine and organophosphorus compounds such as triphenylphosphine, which may be used alone or in combination of two or more.
• a polymerization inhibitor may be used to suppress side reactions during the reaction. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone, and these may be used alone or in combination of two or more.
• the content of the closed ring polyimide resin (A) in the photosensitive polyimide resin composition according to the present embodiment further improves the thick film patterning property when the total solid content of the photosensitive polyimide resin composition is 100% by mass. From the viewpoint of the above, it is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, still more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass. % Or less, more preferably 70% by mass or less.
• the total solid content of the photosensitive polyimide resin composition is a component that remains as a solid content when the photosensitive polyimide resin composition is cured, and is volatilized by heating, for example, a solvent or the like. Ingredients are excluded.
• the components incorporated into the resin film when heat-cured are included in the total solid content.
• the polyfunctional radically polymerizable compound (B) has 4 or more and 100 or less radically polymerizable functional groups.
• the polyfunctional radically polymerizable compound (B) contains two or more kinds of polyfunctional radically polymerizable compounds having different numbers of radically polymerizable functional groups, the polyfunctional radically polymerizable compound (B) is used.
• the number of radically polymerizable functional groups a weighted average value of the number of radically polymerizable functional groups of each polyfunctional radically polymerizable compound can be adopted.
• the number of radically polymerizable functional groups of the polyfunctional radically polymerizable compound (B) according to the present embodiment is 4 or more and 100 or less, but is preferably 5 or more from the viewpoint of further improving the thick film patterning property.
• the number is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less.
• Examples of the radically polymerizable functional group include a (meth) acryloyl group, a vinyl group and the like, and a (meth) acryloyl group is preferable.
• Examples of the polyfunctional radically polymerizable compound constituting the polyfunctional radically polymerizable compound (B) include tricyclodecanedimethanol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
• polyglycerin-based (meth) acrylate refers to a compound having a polyglycerin skeleton and a (meth) acryloyl group.
• examples of the polyglycerin-based (meth) acrylate include SA-TE6, SA-TE60, and SA-ZE12 manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.
• ethoxylated trimethylolpropane tri (meth) acrylate examples include ethoxylated (3) trimethylolpropane triacrylate and ethoxylated (6) trimethylolpropane triacrylate and ethoxylated (15) trimethylolpropane manufactured by Arkema Co., Ltd. Triacrylate or the like can be used.
• the dendrimer (meth) acrylate refers to a polyfunctional (meth) acrylate having a dendrimer structure (including a hyperbranched structure).
• Examples of the dendrimer (meth) acrylate include Viscoat 1000, Viscoat 1020, and STAR-501 (SIRIUS-501, SUBARU-501) manufactured by Osaka Organic Chemical Industry Co., Ltd.
• the biscoat 1000 and the biscoat 1020 are mainly composed of a dendrimer type polyester acrylate having an acrylate group at the terminal.
• the molecular weight of the biscoat 1000 is about 1000 to 2000, and the molecular weight of the viscoat 1020 is about 1000 to 3000.
• STAR-501 contains a core derived from dipentaerythritol and contains a dipentaerythritol hexaacrylate-linked multi-branched polyacrylate having an acrylate group at the terminal as a main component.
• the molecular weight of STAR501 is about 16000 to 24000.
• the content of the polyfunctional radically polymerizable compound (B) in the photosensitive polyimide resin composition according to the present embodiment is 100 parts by mass based on the amount of the closed ring polyimide resin (A) contained in the photosensitive polyimide resin composition.
• the shape of the obtained thick film pattern is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more.
• the viewpoint of further suppressing stickiness of the thick film pattern preferably 100 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, further. It is preferably 60 parts by mass or less.
• the photosensitive polyimide resin composition according to the present embodiment contains, for example, a photopolymerization initiator, a solvent, and an adhesion improver as other components other than the closed ring polyimide resin (A) and the polyfunctional radically polymerizable compound (B). It is preferable to further contain at least one selected from the group consisting of a surface conditioner and a sensitizer, and more preferably to further contain at least one selected from the group consisting of a photopolymerization initiator and a solvent.
• the photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
• photopolymerization initiators may be used alone or in combination of two or more.
• the content of the photopolymerization initiator in the photosensitive polyimide resin composition according to the present embodiment is, for example, 0 when the amount of the closed ring polyimide resin (A) contained in the photosensitive polyimide resin composition is 100 parts by mass. .1 part by mass or more and 10 parts by mass or less.
• solvent an aprotic polar solvent is desirable from the viewpoint of solubility.
• the solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphospho.
• examples thereof include rutriamide, N-acetyl- ⁇ -caprolactum, dimethylimidazolidonene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and ⁇ -butyrolactone. These solvents may be used alone or in combination of two or more.
• solvents such as toluene, xylene, diethyl ketone, methoxybenzene and cyclopentanone may be mixed as long as they do not adversely affect the solubility of the polymer.
• solvents such as toluene, xylene, diethyl ketone, methoxybenzene and cyclopentanone may be mixed as long as they do not adversely affect the solubility of the polymer.
• the photosensitive polyimide resin composition according to the present embodiment can be used in a solution (varnish) state, and the film forming property can be improved.
• the adhesion improver is not particularly limited, and known ones can be used, and an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a mercapto group-containing silane coupling agent, and a (meth) acrylic group-containing silane coupling agent can be used.
• Known coupling agents such as silane coupling agents such as agents, titanate coupling agents, and aluminate coupling agents can be used.
• the coupling agent include KP-390, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-.
• the content of the adhesion improver in the photosensitive polyimide resin composition according to the present embodiment is, for example, 0 when the amount of the closed ring polyimide resin (A) contained in the photosensitive polyimide resin composition is 100 parts by mass. It is 0005 parts by mass or more and 20 parts by mass or less.
• the surface conditioner is not particularly limited, and known ones can be used.
• a silicon-based surface conditioner an acrylic surface conditioner, a fluorine-based surface conditioner, a nonionic surface conditioner, a cationic surface conditioner, and an anionic surface conditioner can be used.
• Various surface conditioners such as surface conditioners can be used. These may be used alone or in combination of two or more.
• the content of the surface conditioner in the photosensitive polyimide resin composition according to the present embodiment is, for example, 0. It is 001 parts by mass or more and 20 parts by mass or less.
• the sensitizer is not particularly limited, and known ones can be used.
• an amino group-containing sensitizer can be mentioned, and a compound having an amino group and a phenyl group in the same molecule can be preferably exemplified.
• the content of the colorant in the photosensitive polyimide resin composition according to the present embodiment is the resin obtained when the amount of the closed ring polyimide resin (A) contained in the photosensitive polyimide resin composition is 100 parts by mass. From the viewpoint of further improving the transparency of the film and further improving the developability of the thick film, it is preferably less than 10 parts by mass, more preferably less than 5 parts by mass, still more preferably less than 1 part by mass, still more preferably 0.5 parts by mass. It is more preferably less than a portion, more preferably less than 0.1 part by mass, and the photosensitive polyimide resin composition according to the present embodiment does not contain a coloring agent.
• the colorant refers to an organic pigment, an inorganic pigment or a dye generally used in the field of photosensitive materials.
• the photosensitive polyimide resin composition according to the present embodiment is not particularly limited, and for example, the closed ring polyimide resin (A) and the polyfunctional radically polymerizable compound (B) are, if necessary, a photopolymerization initiator, a solvent, and the like. It can be obtained by mixing at least one selected from the group consisting of an adhesion improver, a surface conditioner, and a sensitizer.
• the photosensitive polyimide resin composition according to the present embodiment can be used, for example, to form a resin film such as a resist used in manufacturing an electronic device or a permanent film (cured film) constituting the electronic device.
• the resin film according to the present embodiment is made of a photosensitive polyimide resin composition or a cured product of the photosensitive polyimide resin composition.
• the resist is composed of, for example, a resin film obtained by applying the photosensitive polyimide resin composition according to the present embodiment on a substrate and removing a solvent as needed.
• the permanent film is composed of a cured film obtained by exposing and developing the resin film, patterning it into a desired shape, and then curing it by heat treatment or the like.
• the permanent film can be suitably used as an insulating film such as a surface protective film and an interlayer insulating film.
• the surface protective film is formed on the surface of an electronic component or electronic device or the surface of wiring of a wiring board, and refers to an insulating film for protecting the surface, and the type thereof is not particularly limited.
• Examples of such a surface protective film include a passivation film or buffer coat layer provided on a semiconductor element, or a cover coat provided on a flexible substrate.
• the interlayer insulating film refers to an insulating film provided in a multilayer structure, and the type thereof is not particularly limited.
• the interlayer film include those used in semiconductor device applications such as an interlayer insulating film constituting a multilayer wiring structure of a semiconductor element, a build-up layer or a core layer constituting a wiring substrate, and the like.
• the interlayer film for example, a flattening film covering a thin film transistor in a display device, a liquid crystal alignment film, a protrusion provided on a color filter substrate of the liquid crystal display device, a partition wall for forming a cathode of an organic EL element, or the like. Some are used in display device applications.
• the method for applying the photosensitive polyimide resin composition according to the present embodiment to the substrate is not particularly limited, and for example, an inkjet method, a spin coating method, a casting method, a micro gravure method, a gravure coating method, a bar coating method, and the like. Examples thereof include a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, and a die coating method.
• the solid content concentration of the photosensitive polyimide resin composition according to the present embodiment When applied onto a substrate, it is preferable to adjust the solid content concentration of the photosensitive polyimide resin composition according to the present embodiment so as to be in the range of 5 to 50% by mass.
• an aprotic polar solvent is preferable from the viewpoint of solubility. Specifically, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortri.
• Suitable examples include amide, N-acetyl- ⁇ -caprolactam, dimethylimidazolidonene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ⁇ -butyrolactone and the like. These solvents may be used alone or in combination of two or more. In order to further improve the coatability, solvents such as toluene, xylene, diethyl ketone, methoxybenzene and cyclopentanone may be mixed as long as they do not adversely affect the solubility of the polymer.
• Examples of the base material include glass, silicon wafers, metal foils, plastic films and the like. Among the above base materials, silicon wafers and copper foils are preferable.
• the exposure of the film may be performed, for example, by irradiating a film made of a photosensitive polyimide resin composition formed on a substrate with light (usually using ultraviolet rays) through a photomask having a predetermined pattern. can.
• the exposed film has a portion where light is blocked by a photomask and a portion irradiated with light, that is, an exposed portion and an unexposed portion.
• the polyimide resin in the photosensitive polyimide resin composition is crosslinked to form a crosslinked polyimide film, and a pattern is formed by the next developing step.
• the polyimide resin since the polyimide resin is not crosslinked in the unexposed portion, it becomes an uncrosslinked polyimide film that is dissolved and removed by development.
• the ultraviolet irradiation amount is preferably 100 to 8,000 mJ / cm 2 and more preferably 200 to 6,000 mJ / cm 2 as the integrated irradiation amount.
• an organic solvent as the developing solution.
• the developer is not particularly limited as long as it can dissolve the photosensitive polyimide resin composition according to the present embodiment. Specifically, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortri.
• Preferable examples include amide, N-acetyl- ⁇ -caprolactam, dimethylimidazolidonene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ⁇ -butyrolactone and the like. These developers may be used alone or in combination of two or more.
• the relief pattern formed by development is washed with a rinsing solution to remove the developer.
• a rinsing solution include methanol, ethanol, isopropyl alcohol, and water, which are miscible with the developing solution.
• the relief pattern obtained by the above-mentioned treatment is heat-treated at a temperature selected from the range of 80 to 250 ° C., the solvent is dried, and the photosensitive polyimide resin composition according to the present embodiment is cured. Pattern) can be obtained.
• a photosensitive polyimide resin composition having excellent developability that is, a photosensitive polyimide resin composition in which the exposed portion is sufficiently cured and the unexposed portion is sufficiently removed, the obtained relief pattern can be obtained with high resolution. Can be done.
• the line represents the pattern width and the space represents the spacing between adjacent patterns.
• the fact that the line / space 30 ⁇ m / 30 ⁇ m patterning is possible means that “a pattern having no residue in the space portion (unexposed portion) can be obtained”.
• the film thickness of the resin film according to the present embodiment is preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more, further preferably 30 ⁇ m or more, and preferably 85 ⁇ m or less, more preferably 60 ⁇ m or less.
• the film thickness is in the above range, it can be used as an excellent insulating film.
• the thicker the film that is, the more photosensitive polyimide resin composition to be applied to the substrate), the more often problems occur in the developer solubility of the polyimide resin.
• the closed ring polyimide resin (A) having a specific structure and a specific terminal structure and having a specific molecular weight range, and a plurality of radically polymerizable functional groups having 4 or more and 100 or less.
• the resin film according to the present embodiment can be suitably used, for example, in an insulating film application where a high voltage is expected to be applied.
• the resin film obtained from the photosensitive polyimide resin composition according to the present embodiment containing the closed ring polyimide resin (A) and the polyfunctional radically polymerizable compound (B) can effectively suppress the generation of cracks and the like. It can be made and has excellent physical properties.
• the electronic device according to the present embodiment includes the resin film according to the present embodiment.
• the electronic device according to the present embodiment is not particularly limited as long as it includes a resin film formed by the photosensitive polyimide resin composition according to the present embodiment.
• the resin film according to the present embodiment is flattened.
• Semiconductor device Examples thereof include a semiconductor device using the resin film according to the present embodiment as a build-up layer or a core layer constituting a wiring substrate.
• the semiconductor device is preferable as the electronic device according to the present embodiment.
• the electronic device according to the present embodiment can be manufactured based on known information except that the resin film according to the present embodiment is used. Since the electronic device according to the present embodiment includes a resin film having a good patterning shape, dielectric breakdown and the like are unlikely to occur, and the electronic device is excellent in reliability.
• Weight average molecular weight (Mw) Mw was determined by GPC analysis.
• the equipment and analysis conditions used for the analysis are as follows.
• a photosensitive polyimide resin composition varnish was prepared in Examples and Comparative Examples described below.
• the varnishes obtained in each Example and Comparative Example were applied on a silicon wafer with a spin coater so that the film thickness after removing the solvent was 30 ⁇ m, and then heated at 100 ° C. for 5 minutes to remove the solvent.
• the unexposed part is removed by spraying ⁇ -butyrolactone as a developer for 30 seconds, washed with methanol as a rinsing solution, and placed under air flow. The solvent was removed.
• Example 1 10.0 g of the closed ring polyimide resin (A1) obtained in Synthesis Example 1 was dissolved in 12.2 g of GBL, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DIPE-A, Shin-Nakamura Chemical Industry Co., Ltd.) , Number of radically polymerizable functional groups: 5.5) 5.0 g, 1-hydroxycyclohexylphenylketone (manufactured by BASF, Omnirad 184) 0.15 g, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF) , Omnirad819) 0.35g, LE-304 (Kyoeisha Chemical Co., Ltd., silicon-based surface conditioner) 0.01g as a surface conditioner, KP-390 (Shinetsu Chemical Industry Co., Ltd., paint additive) as an adhe
• DIPE-A dipentaery
• This photosensitive polyimide resin composition varnish was applied onto a silicon wafer so that the film thickness after drying was 30 ⁇ m, and dried at 100 ° C. for 5 minutes.
• a mask aligner (MA-10B) manufactured by Mikasa Co., Ltd. was used to irradiate and expose the light of a high-pressure mercury lamp whose wavelength was less than 365 nm with an integrated irradiation amount of 4000 mJ / cm 2 (calculated from the illuminance of 365 nm).
• a pattern with a space of 30 ⁇ m / 30 ⁇ m was prepared.
• Examples 2 to 4 and Comparative Examples 1 to 3 A photosensitive resin composition was prepared in the same manner as in Example 1 above, and its characteristics were evaluated, except that the formulations and integrated irradiation doses shown in Table 1 below were used. The results are shown in Table 1. However, in Examples 1 to 4 and Comparative Examples 1 and 2, the integrated irradiation amount (exposure amount), which was the most excellent in developability when exposed with a plurality of different integrated irradiation amounts, was adopted. Comparative Example 3 is an example in which the integrated irradiation amount is changed in Comparative Example 2. The unit of the blending amount shown in Table 1 is "g".
• the polyfunctional radically polymerizable compounds used in Examples and Comparative Examples are as follows.
• TMP-A Trimethylolpropane triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., number of radically polymerizable functional groups: 3
• DIPE-A Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., number of radically polymerizable functional groups: 5.5
• Viscoat 802 Mixture of tripentaerythritol acrylate and mono and dipentaerythritol acrylate and polypentaerythritol acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., number of radically polymerizable functional groups: 7.8 Viscoat 1000LT: (Dendrimer (meth) acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., radically polymerizable functional group number: 14)
• the photosensitive polyimide resin composition of the example when used, a pattern without a residue was obtained in the space portion, and the photosensitive polyimide resin composition of the example was excellent in thick film developability. Further, when the photosensitive polyimide resin composition of the example was used, a good pattern shape could be obtained with a BTM width / TOP width close to 1.0. That is, the photosensitive polyimide resin composition of the example was excellent in thick film patterning property. On the other hand, the photosensitive polyimide resin compositions of Comparative Examples 1 to 3 were inferior in at least one of the thick film developability and the pattern shape (BTM width / TOP width), and were inferior in the thick film patterning property.

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• 2021
  • 2021-11-10 EP EP21900374.6A patent/EP4257622A4/en active Pending
  • 2021-11-10 JP JP2022566807A patent/JPWO2022118619A1/ja active Pending
  • 2021-11-10 CN CN202180080165.2A patent/CN116547327A/zh active Pending
  • 2021-11-10 WO PCT/JP2021/041279 patent/WO2022118619A1/ja not_active Ceased
  • 2021-11-10 US US18/038,574 patent/US20240085789A1/en active Pending
  • 2021-11-10 KR KR1020237018092A patent/KR20230113556A/ko active Pending
  • 2021-11-15 TW TW110142325A patent/TWI900691B/zh active

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