Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
  • H10W20/071—Manufacture or treatment of dielectric parts thereof
  • H10W20/081—Manufacture or treatment of dielectric parts thereof by forming openings in the dielectric parts
  • H10W20/084—Manufacture or treatment of dielectric parts thereof by forming openings in the dielectric parts for dual-damascene structures
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
  • H10W20/031—Manufacture or treatment of conductive parts of the interconnections
  • H10W20/032—Manufacture or treatment of conductive parts of the interconnections of conductive barrier, adhesion or liner layers
  • H10W20/033—Manufacture or treatment of conductive parts of the interconnections of conductive barrier, adhesion or liner layers in openings in dielectrics
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
  • H10W20/031—Manufacture or treatment of conductive parts of the interconnections
  • H10W20/032—Manufacture or treatment of conductive parts of the interconnections of conductive barrier, adhesion or liner layers
  • H10W20/042—Manufacture or treatment of conductive parts of the interconnections of conductive barrier, adhesion or liner layers the barrier, adhesion or liner layers being seed or nucleation layers
  • H10W20/043—Manufacture or treatment of conductive parts of the interconnections of conductive barrier, adhesion or liner layers the barrier, adhesion or liner layers being seed or nucleation layers for electroplating
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
  • H10W20/031—Manufacture or treatment of conductive parts of the interconnections
  • H10W20/056—Manufacture or treatment of conductive parts of the interconnections by filling conductive material into holes, grooves or trenches
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
  • H10W20/031—Manufacture or treatment of conductive parts of the interconnections
  • H10W20/062—Manufacture or treatment of conductive parts of the interconnections by smoothing of conductive parts, e.g. by planarisation
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
  • H10W20/071—Manufacture or treatment of dielectric parts thereof
  • H10W20/093—Manufacture or treatment of dielectric parts thereof by modifying materials of the dielectric parts
  • H10W20/097—Manufacture or treatment of dielectric parts thereof by modifying materials of the dielectric parts by thermally treating

Definitions

• SAP Semi Additive Process
• Damascene method a method in which a resist is formed in advance on non-circuit areas, the circuit areas are formed by plating, the resist is then removed to form wiring, and the spaces between the wiring are then filled with an insulating material.
• Single damascene is a method of forming a via pattern and a wiring pattern separately, for example by embedding copper wiring in an insulating film in which a via hole has been formed and polishing it, and then forming an insulating film with a wiring groove, embedding copper wiring in the wiring groove, and polishing it.
• dual damascene is a method in which an insulating film having wiring grooves and via holes is formed, then wiring metal is deposited to fill both the wiring grooves and the via holes at the same time, and then polishing is performed to form wiring.
• damascene method since the wiring metal is polished, a flat wiring structure can be obtained without flattening between layers, which is advantageous in that it is easy to form multiple layers of fine wiring.
• dual damascene is attracting attention as a technology that can reduce manufacturing costs because it can reduce the number of manufacturing steps.
• a method for producing a laminate including a substrate, a first insulating pattern present on the substrate, a second insulating pattern present on at least a portion of a surface of the first insulating pattern, and a conductive pattern providing electrical continuity between an area between the first insulating pattern and an area between the second insulating pattern, the method comprising the steps of: Step A, Step B1, Step C1 and Step D1, Step A, step B2, step C2 and step D2, or The method includes any one of step A, step B3, step C3, and step D3;
• a method for producing a laminate Step A: a preparation step of preparing a laminate A including a precursor pattern of a first insulating pattern and a precursor pattern of the second insulating pattern;
• Step B1 a conductive layer forming step of forming a conductive layer in the regions between the precursor patterns of the first insulating pattern of the laminate A, the regions between the precursor patterns of the second insulating pattern, and on
• Step D2 A heating step of heating the precursor pattern of the first insulating pattern and the precursor pattern of the second insulating pattern in the laminate B2 to form the first insulating pattern and the second insulating pattern to obtain the laminate D2.
• Step C2 A polishing step of polishing the laminate D2 to obtain a laminate having the conductive pattern and the precursor pattern of the second insulating pattern exposed on the surface.
• Step D3 A heating step of heating the precursor pattern of the first insulating pattern and the precursor pattern of the second insulating pattern in the laminate A to form the first insulating pattern and the second insulating pattern to obtain the laminate D3.
• Step B3 A conductive layer forming step of forming a conductive layer on the region between the first insulating patterns of the laminate D3, the region between the second insulating patterns, and the precursor pattern of the second insulating pattern to obtain the laminate B3.
• Step C3 A polishing step of polishing the laminate B3 to obtain a laminate having the conductive pattern and the precursor pattern of the second insulating pattern exposed on the surface.
• the method for producing a laminate described in ⁇ 1> further includes, between step A and steps B1, B2 and B3, a seed layer formation step of forming a seed layer present in a region between the precursor patterns of the first insulating pattern or in a region between the first insulating patterns, and in a region between the precursor patterns of the second insulating pattern or in a region between the second insulating patterns.
• a seed layer formation step of forming a seed layer present in a region between the precursor patterns of the first insulating pattern or in a region between the first insulating patterns, and in a region between the precursor patterns of the second insulating pattern or in a region between the second insulating patterns.
• the step A includes a second coating step of coating a second insulating pattern-forming composition on a precursor pattern of a first insulating pattern of a laminate X having a precursor pattern of a first insulating pattern on a base material,
• the second insulating pattern forming composition contains a solvent B,
• the method for producing a laminate according to any one of ⁇ 1> to ⁇ 3>, wherein a change in film thickness when the precursor pattern of the first insulating pattern is immersed in the solvent B at 25° C. for 5 minutes is 5% or less.
• ⁇ 6> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the second insulating pattern contains polyimide or polybenzoxazole.
• the solvent B includes a solvent containing a carbonyl group.
• the solvent B contains at least one solvent selected from the group consisting of ⁇ -butyrolactone, propylene glycol monomethyl ether acetate, and cyclopentanone.
• (meth)acrylate means both or either of “acrylate” and “methacrylate”
• (meth)acrylic means both or either of “acrylic” and “methacrylic”
• (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
• Me represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the total solid content refers to the total mass of all components of the composition excluding the solvent
• the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
• a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
• the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as “upper”, and the opposite direction is referred to as "lower”. Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper” direction in this specification may be different from the vertical upward direction.
• the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
• the method for producing a laminate of the present invention is a method for producing a laminate comprising a substrate, a first insulating pattern present on the substrate, a second insulating pattern present on at least a portion of the surface of the first insulating pattern, and a conductive pattern providing electrical conductivity between an area between the first insulating pattern and an area between the second insulating pattern, and includes any of steps A, B1, C1 and D1; steps A, B2, C2 and D2; or steps A, B3, C3 and D3.
• Step A a preparation step of preparing a laminate A including a precursor pattern of a first insulating pattern and a precursor pattern of the second insulating pattern;
• Step B1 a conductive layer forming step of forming a conductive layer in the regions between the precursor patterns of the first insulating pattern of the laminate A, the regions between the precursor patterns of the second insulating pattern, and on the precursor pattern of the second insulating pattern, to obtain a laminate B1;
• Step C1 a polishing step of polishing the laminate B1 to obtain a laminate C1 in which the conductive pattern and the precursor pattern of the second insulating pattern are exposed;
• Step D1 a heating step of heating the precursor pattern of the first insulating pattern and the precursor pattern of the second insulating pattern in the laminate C1 to form the first insulating pattern and the second insulating pattern, to obtain a laminate;
• Step B2 a conductive layer forming step of forming a conductive layer in the regions between the precursor patterns of the first insulating pattern of the
• Step D2 a heating step of heating the precursor pattern of the first insulating pattern and the precursor pattern of the second insulating pattern in the laminate B2 to form the first insulating pattern and the second insulating pattern, thereby obtaining a laminate D2;
• Step C2 a polishing step of polishing the laminate D2 to obtain a laminate having the conductive pattern and the precursor pattern of the second insulating pattern exposed on the surface;
• Step D3 a heating step of heating the precursor pattern of the first insulating pattern and the precursor pattern of the second insulating pattern in the laminate A to form the first insulating pattern and the second insulating pattern, thereby obtaining a laminate D3;
• Step B3 a conductive layer forming step of forming a conductive layer in the regions between the first insulating patterns, the regions between the second insulating patterns, and on the precursor pattern of the second insulating pattern of the laminate D3, thereby obtaining a laminate B3;
• Step C3 a polishing step of polishing the laminate B3 to obtain
• the precursor pattern of the first insulating pattern and the precursor pattern of the second insulating pattern are heated together, thereby hardening these precursor patterns at once to form the first insulating pattern and the second insulating pattern.
• the laminate manufacturing method of the present invention reduces the number of heating steps and is therefore considered to have superior manufacturing efficiency (time efficiency and energy efficiency) for the laminate.
• Patent Document 1 describes or suggests heating the precursor pattern of the first insulating pattern and the precursor pattern of the second insulating pattern all at once.
• the method for producing the laminate of the present invention will be described in detail below.
• the laminate obtained by the laminate manufacturing method of the present invention is a laminate comprising a substrate, a first insulating pattern present on the substrate, a second insulating pattern present on at least a portion of the surface of the first insulating pattern, and a conductive pattern providing electrical conductivity between the area between the first insulating pattern and the area between the second insulating pattern.
• the substrate is not particularly limited, and may be a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, or amorphous silicon, quartz, glass, an optical film, a ceramic material, a deposition film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, paper, SOG (Spin On Glass), a TFT (thin film transistor) array substrate, or an electrode plate for a plasma display panel (PDP).
• the substrate may have a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like provided on the surface.
• the substrate may be in the form of a wafer or a panel.
• a semiconductor substrate is particularly preferred, and a silicon substrate (silicon wafer) is more preferred.
• the substrate may have an electronic circuit region including an electronic circuit.
• the electronic circuit may have an element such as a semiconductor.
• the electronic circuit is preferably electrically connected to the conductive pattern.
• the first insulating pattern preferably comprises polyimide or polybenzoxazole, and more preferably comprises polyimide.
• the content of polyimide or polybenzoxazole (when two or more types are contained, the total content of these) is preferably 20 to 99.5 mass %, more preferably 30 to 99 mass %, even more preferably 40 to 98 mass %, and particularly preferably 50 to 97 mass %, relative to the total mass of the first insulating pattern.
• the ring closure rate of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
• the upper limit of the ring closure rate is not particularly limited, and it is sufficient if it is 100% or less.
• the first insulating pattern is not particularly limited and may be a line pattern, a hole pattern, or the like, but is preferably a hole pattern.
• the spacing between the lines is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and even more preferably 0.3 to 2 ⁇ m.
• the diameter of the bottom surface of the hole pattern is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and even more preferably 0.3 to 2 ⁇ m.
• the shape of the bottom surface of the hole pattern is not circular, the above diameter is calculated as a circle-equivalent diameter.
• the circle-equivalent diameter is the diameter of a circle having the same area as the area of the bottom surface of the hole pattern.
• the thickness of the first insulating pattern is not particularly limited, but is preferably 100 nm or more, more preferably 300 nm or more, even more preferably 500 nm or more, and even more preferably 1 ⁇ m or more. There is no particular upper limit, but it is preferably 1 mm or less, more preferably 500 ⁇ m or less, and even more preferably 200 ⁇ m or less.
• the thickness of the film can be measured using a known film thickness measuring device.
• the indentation elastic modulus of the first insulating pattern is not particularly limited, but is preferably 6.0 GPa or less, more preferably 4.0 to 6.0 GPa, and even more preferably 4.5 to 5.5 GPa.
• the indentation elastic modulus can be measured by a nanoindentation test.
• the ring closure rate is measured by the method described below.
• the insulating pattern is preferably a cured product of a photosensitive resin composition described below.
• the second insulating pattern is preferably a cured product of a second insulating pattern forming composition described below.
• the second insulating pattern is preferably in contact with the first insulating pattern, although other layers may be formed between this pattern and the first insulating pattern. It is preferable that the first insulating pattern and the second insulating pattern differ in at least a portion of the pattern in the surface direction of the base material.
• the second insulating pattern is not particularly limited and may be a line pattern, a hole pattern, or the like, but is preferably a line pattern.
• the spacing between the lines is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and even more preferably 0.3 to 3 ⁇ m.
• the diameter of the bottom of the hole pattern is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and even more preferably 0.3 to 2 ⁇ m.
• the shape of the bottom of the hole pattern is not circular, the diameter is calculated as the equivalent circle diameter.
• the equivalent circle diameter is the diameter of a circle having the same area as the area of the bottom of the hole pattern.
• the conductive pattern provides electrical continuity between the region between the first insulating patterns and the region between the second insulating patterns.
• the conductive pattern is preferably a conductive pattern that fills the area between the first insulating pattern and the area between the second insulating pattern, where filling means filling the area between the patterns so that no voids are formed in the area between the patterns, and another layer such as a seed layer may be present in the area between the patterns.
• the conductive pattern may be divided into two conductive patterns, one filling the area between the first insulating patterns and the other filling the area between the second insulating patterns, and these may be in electrical contact with each other.
• the alloy may contain elements other than those exemplified above.
• the copper alloy may contain silicon atoms to form a Corson alloy.
• oxygen that is inevitably dissolved, organic residues of raw material compounds mixed during precipitation, etc. may be present.
• the conductive pattern may be a wiring terminal including a plurality of different members. Of these, the conductive pattern is preferably a pattern made of copper.
• the manufacturing method of the laminate A may include forming a first precursor pattern by etching or the like instead of the first exposure step and the first development step, and may include forming a second precursor pattern by etching or the like instead of the second exposure step and the second development step.
• first precursor pattern by etching or the like instead of the first exposure step and the first development step
• second precursor pattern by etching or the like instead of the second exposure step and the second development step.
• the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred.
• the spin coating method for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
• a coating film formed by applying the coating to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
• the transfer method the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No.
• 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be used.
• a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinse (EBR) and back rinse.
• EBR edge bead rinse
• a pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
• the film may be subjected to drying in the first film formation step in order to remove the solvent.
• the drying temperature of the film is preferably 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. Drying may be performed under reduced pressure.
• the drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.
• the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.
• the exposure wavelength may be, in particular, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532 nm, third harmonic 355 nm, etc.
• semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 3
• the organic solvent may be used alone or in combination of two or more.
• a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
• the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the content may be 100% by mass.
• the developer may further contain at least one of a basic compound and a base generator.
• the performance of the pattern such as the breaking elongation, may be improved.
• an organic base is preferred.
• a basic compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, or the like is preferable.
• step A includes a second coating step of coating a second insulating pattern-forming composition onto a first precursor pattern of a laminate X having a first precursor pattern on a substrate, and it is preferable that the second insulating pattern-forming composition contains a solvent B, and that a change in film thickness when the precursor pattern of the first insulating pattern is immersed in the solvent B at 25° C. for 5 minutes is 5% or less.
• a second insulating pattern is formed on the laminate X, thereby obtaining a laminate A.
• solvent B is a mixed solvent containing the two or more kinds of solvents in the same ratio as the composition for forming a second insulating pattern.
• the conductive layer can be formed by plating, applying a conductive paste, or the like.
• the maximum thickness of the conductive layer formed in step B is not particularly limited, but is preferably 500 to 10,000 nm, and more preferably 1,000 to 5,000 nm.
• Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 230°C at 2°C/min, and held at 230°C for 180 minutes. It is also preferable to perform the process while irradiating ultraviolet rays as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
• step D is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the process under reduced pressure, etc.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
• the heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.
• FIG. 1( b ) shows a state in which a first photosensitive resin composition is applied onto a substrate 1 to form a film 10 .
• FIG. 1C shows a state in which the film in FIG. 1B has been exposed and developed to form a hole pattern 12 and a first precursor pattern 14 .
• FIG. 1( d ) shows a state in which a second photosensitive resin composition is applied onto the film 10 on which the hole pattern 12 has been formed, to form a film 20 .
• FIG. 1( e ) shows a state in which a line and space pattern (space portion) 22 is formed in the film 20 so that the space portion is positioned above the hole pattern in the film 10 , forming a second precursor pattern 24 .
• the laminate shown in FIG. 1( e ) corresponds to an example of the laminate A in the step A.
• a 1 and A 3 are preferably —O—.
• A2 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.
• a 1 and A 3 are —O— and A 2 is —C(CH 3 ) 2 — is also one of the preferred embodiments of the present invention.
• the number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.
• R 115 represents a tetravalent organic group.
• a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
• each * independently represents a bonding site to another structure.
• R 112 is a single bond or a divalent linking group and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, and a combination thereof, more preferably a single bond, or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO 2 -, and still more preferably a divalent group selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S-, and -SO 2 -.
• R 115 is also preferably a group represented by the following formula (7):
• R 115 is more preferably a group represented by the following formula (7-2).
• a 1 to A 3 each independently represent a single bond or a divalent linking group
• * represents a bonding site with the carbonyl group in formula (2)
• each of the four benzene rings described in formula (7) may have a substituent.
• a bond that crosses an edge of a ring structure is meant to replace any of the hydrogen atoms in that ring structure.
• * represents a bonding site with the carbonyl group in formula (2).
• R 115 is also preferably a group represented by the following formula (8): In the above embodiment, R 115 is more preferably a group represented by the following formula (8-2).
• L 1 is preferably a hydrocarbon group which may have a substituent, more preferably an aromatic hydrocarbon group, and further preferably a phenylene group. The hydrocarbon group in L1 may have a substituent.
• R each independently represents a substituent
• n is an integer of 0 to 4
• * represents a bonding site with the carbonyl group in formula (2).
• Each R is preferably a fluorine atom or a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted by a fluorine atom, and more preferably a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted by a fluorine atom.
• n is an integer of 0 to 2.
• an embodiment in which n is 2 is also one of the preferable embodiments of the present invention.
• R 115 include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride.
• the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R 115 .
• the tetracarboxylic dianhydride is preferably represented by the following formula (O).
• R 115 represents a tetravalent organic group.
• the preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.
• tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 2 ,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxy
• R 111 and R 115 may have an OH group. More specifically, R 111 may be a residue of a bisaminophenol derivative.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.
• R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
• * represents a bonding site with another structure.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
• R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
• alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-but
• the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
• the alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
• the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
• polyethyleneoxy group from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy group, polypropyleneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded is preferred, polyethyleneoxy group or polypropyleneoxy group is more preferred, and polyethyleneoxy group is even more preferred.
• the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiment of the number of repetitions of the ethyleneoxy group etc. in these groups is as described above.
• the acid-decomposable group examples include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
• the polyimide precursor has fluorine atoms in its structure.
• the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.
• the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
• a 1 and A 2 represent an oxygen atom
• R 111 and R 112 each independently represent a divalent organic group
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
• at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
• a 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred range is also the same.
• R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
• the polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2).
• the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).
• One embodiment of the polyimide precursor of the present invention is one in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units.
• the total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
• the number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
• the polyimide precursor has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.
• the polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable.
• the upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
• the polyimide contains fluorine atoms.
• the fluorine atom is preferably contained, for example, in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later.
• the amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.
• the polyimide contains a silicon atom.
• the silicon atom is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained in R 131 in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
• the silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more, and more preferably 20 mass % or less.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in the side chain.
• the ethylenically unsaturated bond is preferably radically polymerizable.
• the ethylenically unsaturated bond is preferably contained in R 132 or R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 132 or R 131 as a group having an ethylenically unsaturated bond.
• the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 131 as a group having an ethylenically unsaturated bond.
• the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).
• R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
• R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C( ⁇ O)O-, -O(C ⁇ O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
• the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
• the alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
• R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).
• L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together;
• X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ⁇ represents a bonding site with the oxygen atom to which R21 in formula (IV) is bonded.
• formulas (R1) to (R3) preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R 21 in formula (IV).
• X is preferably an oxygen atom.
• * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
• the structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
• the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
• the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).
• the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.
• the polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
• the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
• the polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in, for example, R 131 in the repeating unit represented by formula (4) described below.
• the amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.
• the polyimide may have a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and preferred embodiments are also the same.
• the polarity conversion group is contained, for example, in R 131 and R 132 in the repeating unit represented by formula (4) described later, or at the terminal of the polyimide.
• the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
• the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
• the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
• the acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
• the acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
• pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa.
• pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified.
• ACD/ChemSketch registered trademark
• pKa the value listed in "Revised 5th Edition Chemistry Handbook: Basics” edited by the Chemical Society of Japan may be referred to.
• the acid group is a polyacid, such as phosphoric acid
• the pKa is the first dissociation constant.
• the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 132 or R 131 in the repeating unit represented by formula (4) described below.
• the amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide structure, but it is preferable that the polyimide contains a repeating unit represented by the following formula (4).
• R 131 represents a divalent organic group
• R 132 represents a tetravalent organic group.
• the polymerizable group may be located at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2).
• Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).
• R 131 represents a divalent organic group.
• the divalent organic group include the same as those of R 111 in formula (2), and the preferred range is also the same.
• R 131 may be a diamine residue remaining after removal of the amino group of the diamine.
• the diamine may be an aliphatic, cycloaliphatic or aromatic diamine. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
• R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.
• Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc.
• R 132 represents a tetravalent organic group.
• examples of the tetravalent organic group include the same as those of R 115 in formula (2), and the preferred range is also the same.
• the four bonds of the tetravalent organic group exemplified as R 115 bond to the four —C( ⁇ O)— portions in formula (4) to form a condensed ring.
• R 132 may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride.
• a specific example is R 115 in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 has an OH group. More specifically, preferred examples of R 131 include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and more preferred examples of R 132 include the above (DAA-1) to (DAA-5).
• the polyimide preferably contains a repeating unit represented by the following formula (4-3) as the repeating unit represented by formula (4).
• formula (4-3) X1 represents an organic group having 4 or more carbon atoms, Y1 represents an organic group having 4 or more carbon atoms, and each R1 independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more.
• R-1 L 1 represents a linking group having a valence of a2+1, A 1 represents a polymerizable group, a2 represents an integer of 1 or more, and * represents a bonding site with X 1 or Y 1 in formula (4-3).
• R 1 independently represents a structure represented by formula (R-1).
• L1 represents a2+1-valent linking group.
• L1 is preferably a group represented by the following formula (LR-1).
• Lx represents a2+1-valent linking group, a2 represents an integer of 1 or greater, * represents a bonding site with X1 or Y1 in formula (4-3), and # represents a bonding site with A1 in formula (R-1).
• Lx is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
• the preferred embodiments of a2 in formula (LR-1) are the same as the preferred embodiments of a2 in formula (R-1).
• a 1 represents a polymerizable group, and preferred embodiments of the polymerizable group are the same as those of the polymerizable group in the specific resin described above.
• at least one of A 1 in formula (R-1) included in formula (4-3) is preferably a group having an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group, or a (meth)acryloxy group, and more preferably a vinylphenyl group.
• a2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
• the number of ester bonds contained in formula (R-1) is preferably 1 or 0.
• X1 preferably includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulae (V-1) to (V-4).
• R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
• R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
• R X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or a trifluoromethyl group.
• the halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable.
• R 1 X2 and R 1 X3 each independently represent a hydrogen atom.
• R X2 and R X3 are bonded to form a ring structure
• the structure formed by bonding R X2 and R X3 is preferably a single bond, -O- or -CR 2 -, more preferably -O- or -CR 2 -, and even more preferably -O-.
• R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
• X 1 is a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by formula (V-1)
• X 1 is preferably a group represented by the following formula (V-1-1).
• * represents a bonding site with four carbonyl groups to which X 1 in formula (4-3) is bonded
• n1 represents an integer of 0 to 5, and is also preferably an integer of 1 to 5.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• m in the above formula (4-3) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in formula (4-3).
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), X 1 is preferably a group represented by the following formula (V-2-1) or formula (V-2-2), and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2).
• L X1 represents a single bond or -O-, and * represents a bonding site with the four carbonyl groups to which X 1 in formula (4-3) is bonded.
• R X1 are as described above.
• the hydrogen atoms in these structures may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• m in the above formula (4-3) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in formula (4-3).
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-3), X 1 is preferably a group represented by formula (V-3-1) or formula (V-3-2) below, and from the viewpoint of lowering the dielectric constant, it is preferably a group represented by formula (V-3-2).
• * represents a bonding site with four carbonyl groups to which X 1 in formula (4-3) is bonded.
• R X2 and R X3 are as described above.
• the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.
• m in the above formula (4-3) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in formula (4-3).
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), X 1 is preferably a group represented by the following formula (V-4-1).
• * represents a bonding site with four carbonyl groups to which X 1 in formula (4-3) is bonded
• n1 represents an integer of 0 to 5.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• m in the above formula (4-3) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in formula (4-3).
• X 1 may be a group in which m hydrogen atoms have been removed from the group represented by R 132 in the above formula (4).
• X1 does not contain an imide structure in the structure.
• X1 does not contain a urethane bond, a urea bond or an amide bond in the structure.
• R N is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
• Preferred aspects of R N are as described above.
• R N represents a hydrogen atom or a monovalent organic group
• * represents a bonding site with a carbon atom.
• X1 does not contain an ester bond in the structure.
• X 1 does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that X 1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.
• Y 1 is preferably a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) above.
• Y 1 is a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by formula (V-1)
• Y 1 is preferably a group in which n hydrogen atoms have been removed from a group represented by formula (V-1-2) below.
• * represents the bonding site with the two nitrogen atoms to which Y 1 in formula (4-3) is bonded
• n1 represents an integer of 1 to 5.
• R 1 in formula (4-3) n has the same meaning as n in formula (4-3).
• the hydrogen atoms in the structure below may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• Y 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), Y 1 is preferably a group represented by formula (V-2-3) or formula (V-2-4) below, and from the viewpoint of decreasing the dielectric constant, etc., it is preferably a group represented by formula (V-2-4).
• L X1 represents a single bond or -O-, and * represents a bonding site with the two nitrogen atoms to which Y 1 in formula (4-3) is bonded.
• R X1 is as described above.
• n are substituted with R 1 in formula (4-3). n has the same meaning as n in formula (4-3).
• the hydrogen atoms in these structures may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• Y 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3), Y 1 is preferably a group represented by formula (V-3-3) or formula (V-3-4) below, and from the viewpoint of decreasing the dielectric constant, etc., it is preferably a group represented by formula (V-3-3).
• * represents a bonding site with the two nitrogen atoms to which Y 1 in formula (4-3) is bonded.
• R X2 and R X3 are as described above.
• n are substituted with R 1 in formula (4-3). n has the same meaning as n in formula (4-3).
• the hydrogen atoms in these structures may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• Y 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), Y 1 is preferably a group represented by formula (V-4-2) below.
• * represents a bonding site with the two nitrogen atoms to which Y 1 in formula (4-3) is bonded
• n1 represents an integer of 0 to 5.
• An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention.
• n are substituted with R 1 in formula (4-3).
• n has the same meaning as n in formula (4-3).
• the hydrogen atoms in the structure below may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• Y 1 may be a group in which n hydrogen atoms have been removed from the group represented by R 131 in the above formula (4).
• Y1 does not contain an imide structure in the structure. It is also preferred that Y1 does not contain a urethane bond, a urea bond or an amide bond in the structure. Furthermore, it is preferable that Y1 does not contain an ester bond in the structure.
• Y1 does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that Y1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.
• X 1 and Y 1 in formula (4-3) each include a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-4).
• n is preferably 1 or 2, and more preferably 2.
• the polyimide has fluorine atoms in its structure.
• the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.
• the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
• diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
• the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• monoamine compounds 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-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino
• the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
• the imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C.
• the polyimide may contain repeating units represented by the above formula (4) in which all of the repeating units have the same combination of R 131 and R 132 , or may contain repeating units represented by the above formula (4) containing two or more different combinations of R 131 and R 132.
• the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include the repeating units represented by the above formula (2).
• Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, monoacid chloride compound, or monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely
• the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
• the number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
• the polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the polyimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.
• the polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3).
• R 121 represents a divalent organic group
• R 122 represents a tetravalent organic group
• R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
• R 123 and R 124 have the same definition as R 113 in formula (2), and the preferred range is also the same. That is, it is preferable that at least one of them is a polymerizable group.
• R 121 represents a divalent organic group.
• the divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group.
• the aliphatic group is preferably a linear aliphatic group.
• R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
• dicarboxylic acid residue a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.
• the dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups.
• the number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10.
• the linear aliphatic group is preferably an alkylene group.
• Dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid.
• suberic acid dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentri
• Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.
• dicarboxylic acids containing an aromatic group the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of a group having an aromatic group and two -COOH groups are more preferred.
• A represents a divalent group selected from the group consisting of -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 -, and -C(CH 3 ) 2 -, and each * independently represents a bonding site to another structure.
• dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
• R 122 represents a tetravalent organic group.
• the tetravalent organic group has the same meaning as R 115 in formula (2) above, and the preferred range is also the same.
• R 122 is preferably a group derived from a bisaminophenol derivative.
• Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)me
• the following bisaminophenol derivatives having aromatic groups are preferred.
• X1 represents -O-, -S-, -C( CF3 ) 2- , -CH2- , -SO2- or -NHCO-, and * and # each represent a bonding site with another structure.
• R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. It is also preferable that R122 represents a structure represented by the above formula.
• R 122 is a structure represented by the above formula, of the total of four * and #, it is preferable that any two are bonding sites with the nitrogen atom to which R 122 in formula (3) is bonded, and the other two are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and the two * are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and the two # are bonding sites with the nitrogen atom to which R 122 in formula (3) is bonded, or it is more preferable that the two * are bonding sites with the nitrogen atom to which R 122 in formula (3) is bonded, and the two # are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and it is even more preferable that the two * are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and the two # are bonding sites with the nitrogen atom to which R 122 in formula (3) is bonded.
• the bisaminophenol derivative is also preferably a compound represented by formula (As).
• R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or an organic group selected from the group represented by the following formula (A-sc).
• R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
• R 3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
• R 2 is an alkyl group and R 3 is an alkyl group, since this can maintain the effects of high transparency to i-line and a high ring closure rate when cured at a low temperature.
• R 1 is an alkylene or a substituted alkylene.
• the alkylene and substituted alkylene for R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, and among these, -CH 2 -, -CH(CH 3 )-, and -C(CH 3 ) 2 - are more preferable in that they can provide a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and a high ring closure rate when cured at low temperature.
• the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of formula (3) above.
• the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that the occurrence of warping due to ring closure can be suppressed.
• Z has an a-structure and a b-structure
• R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• R 2s is a hydrocarbon group having 1 to 10 carbon atoms
• at least one of R 3s , R 4s , R 5s , and R 6s is an aromatic group
• the remaining are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different.
• Polymerization of the a-structure and the b-structure may be block polymerization or random polymerization.
• the mol % of the Z portion is 5 to 95 mol % for the a-structure, 95 to 5 mol % for the b-structure, and a+b is 100 mol %.
• preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
• the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
• the diamine residue represented by formula (SL) is contained as another type of repeating unit, it is also preferable to further contain a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit.
• a tetracarboxylic acid residue include the examples of R 115 in formula (2).
• the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000.
• the number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
• the polybenzoxazole precursor has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
• the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polybenzoxazole precursors as one resin are each within the above ranges.
• the polybenzoxazole is not particularly limited as long as it is a polymeric compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group.
• the polymerizable group is preferably a radically polymerizable group.
• it may be a compound represented by the following formula (X) having a polarity conversion group such as an acid-decomposable group.
• R 133 represents a divalent organic group
• R 134 represents a tetravalent organic group.
• the polarity conversion group such as a polymerizable group or an acid-decomposable group
• the polarity conversion group may be located at least one of R 133 and R 134 , or may be located at an end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).
• Formula (X-1) In formula (X-1), at least one of R 135 and R 136 is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups are as defined in formula (X).
• the polarity conversion group such as a polymerizable group or an acid-decomposable group, is the same as the polymerizable group described above for the polymerizable group possessed by the polyimide precursor.
• R 133 represents a divalent organic group.
• the divalent organic group may be an aliphatic group or an aromatic group. Specific examples include the examples of R 121 in the formula (3) of the polybenzoxazole precursor, and preferred examples are the same as R 121 .
• R 134 represents a tetravalent organic group.
• the tetravalent organic group include the examples of R 122 in the formula (3) of the polybenzoxazole precursor, and preferred examples are the same as those of R 122 .
• the four bonds of the tetravalent organic group exemplified as R 122 bond to the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring.
• R 134 is the following organic group, the following structure is formed.
• * represents the bonding site with the nitrogen atom or oxygen atom in formula (X), respectively.
• the oxazolization rate of the polybenzoxazole is preferably 85% or more, more preferably 90% or more.
• the upper limit is not particularly limited, and may be 100%.
• the oxazolization rate of 85% or more the film shrinkage due to ring closure that occurs when the film is oxazolized by heating is reduced, and the occurrence of warpage can be more effectively suppressed.
• the oxazole ratio is measured, for example, by the following method.
• the infrared absorption spectrum of the polybenzoxazole is measured, and the peak intensity Q1 at about 1650 cm ⁇ 1 , which is an absorption peak derived from the amide structure of the precursor, is determined.
• the peak intensity Q1 is normalized by the absorption intensity of the aromatic ring observed at about 1490 cm ⁇ 1 .
• the infrared absorption spectrum is measured again, and the peak intensity Q2 at about 1650 cm ⁇ 1 is determined and normalized by the absorption intensity of the aromatic ring observed at about 1490 cm ⁇ 1 .
• the polybenzoxazole may contain repeating units of the above formula (X) having the same combination of R 133 and R 134 , or may contain repeating units of the above formula (X) having two or more different combinations of R 133 and R 134.
• the polybenzoxazole may contain other types of repeating units in addition to the repeating units of the above formula (X).
• Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, which is then oxazolized using a known oxazolization reaction method.
• dicarboxylic acids in order to increase the reaction yield, etc., it is also possible to use an active ester type dicarboxylic acid derivative which has been reacted in advance with 1-hydroxy-1,2,3-benzotriazole or the like.
• the weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more types of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is in the above range.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polybenzoxazoles as one resin are each within the above ranges.
• R 117 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group.
• a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
• the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
• the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
• examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
• the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms.
• preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
• the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.
• R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated.
• the halogenation is preferably chlorination.
• a compound having three carboxy groups is called a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be converted into acid anhydrides.
• the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor includes branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.
• tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2- , -C( CH3 ) 2- , -C( CF3 ) 2- , -SO2- , or a phenylene group.
• These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).
• R 111 , A 2 and R 113 have the same meanings as R 111 , A 2 and R 113 in formula (2) above, and preferred embodiments are also the same.
• the polyamideimide precursor may further include other repeat units.
• the other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1).
• R 116 represents a divalent organic group
• R 111 represents a divalent organic group
• R 116 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked by a single bond or a linking group.
• a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
• the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
• the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
• examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
• the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms.
• preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
• the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.
• R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
• a compound having two carboxy groups is called a dicarboxylic acid compound
• a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
• the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
• Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.
• the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound that contains a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound that contains an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group.
• dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, and hexadecafluorosuccinic
• fluorosebacic acid examples include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, dig
• R 111 has the same meaning as R 111 in formula (2) above, and preferred embodiments are also the same.
• the polyamideimide precursor has fluorine atoms in its structure.
• the fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more, and 20% by mass or less.
• the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine component.
• An embodiment of the polyamideimide precursor of the present invention includes a repeating unit represented by formula (PAI-2), a repeating unit represented by formula (PAI-1), and a repeating unit represented by formula (2).
• the total content of the repeating units is preferably 50 mol% or more of all repeating units, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• the upper limit of the total content is not particularly limited, and is 100 mol% or less. All repeating units in the polyamideimide precursor except for the terminals may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).
• Another embodiment of the polyamideimide precursor of the present invention includes a repeating unit represented by formula (PAI-2) and a repeating unit represented by formula (PAI-1).
• the total content of the repeating units is preferably 50 mol% or more of all repeating units, more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• the upper limit of the total content is not particularly limited, and is 100 mol% or less. All repeating units in the polyamideimide precursor except for the terminals may be either the repeating unit represented by formula (PAI-2) or the repeating unit represented by formula (PAI-1).
• the weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000.
• the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
• the molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polyamideimide precursor are in the above range. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyamideimide precursors as one resin are each in the above range.
• the polyamideimide used in the present invention may be an alkali-soluble polyamideimide, or may be a polyamideimide that is soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at least 0.1 g in 100 g of a 2.38 mass% aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, it is preferable that the polyamideimide dissolves at least 0.5 g, and more preferably at least 1.0 g.
• the upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
• the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.
• the polyamideimide contains a fluorine atom.
• the fluorine atom is preferably contained in, for example, R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later, and more preferably contained as a fluorinated alkyl group in R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later.
• the amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5% by mass or more and 20% by mass or less.
• the polyamideimide may have an ethylenically unsaturated bond.
• the polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable that the ethylenically unsaturated bond be in the side chain.
• the ethylenically unsaturated bond is preferably radically polymerizable.
• the ethylenically unsaturated bond is preferably contained in R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later, and more preferably contained as a group having an ethylenically unsaturated bond in R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later.
• Preferred embodiments of the group having an ethylenically unsaturated bond are the same as those of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.
• the amount of ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.
• the polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.
• examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable group other than the ethylenically unsaturated bond in the above-mentioned polyimide.
• a polymerizable group other than an ethylenically unsaturated bond is preferably contained in, for example, R 111 in the repeating unit represented by formula (PAI-3) described later.
• the amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.
• the polyamideimide may have a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group in the polyamideimide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and preferred embodiments are also the same.
• the acid value of the polyamideimide is preferably from 2 to 35 mgKOH/g, more preferably from 3 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
• the acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
• examples of the acid group contained in the polyamideimide include the same groups as the acid groups in the above-mentioned polyimides, and the preferred embodiments are also the same.
• the polyamideimide preferably has a phenolic hydroxy group.
• the polyamideimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later.
• the amount of phenolic hydroxy groups relative to the total mass of the polyamideimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.
• the polyamideimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3).
• R 111 and R 117 have the same meanings as R 111 and R 117 in formula (PAI-2), respectively, and preferred embodiments are also the same.
• the polyamide-imide has a polymerizable group
• the polymerizable group may be located at least one of R 111 and R 117 , or may be located at an end of the polyamide-imide.
• a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• the preferred aspects of the terminal capping agent are the same as the preferred aspects of the terminal capping agent for the polyimide described above.
• the polyamideimide may contain repeating units represented by the above formula (PAI-3) in which the combination of R 111 and R 117 is the same, or may contain repeating units represented by the above formula (PAI-3) containing two or more different combinations of R 111 and R 117. Furthermore, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).
• the upper limit of the molecular weight dispersity of the polyamideimide is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamideimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyamideimides as one resin are each within the above ranges.
• the polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, etc.
• the basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.
• -End-capping agent- In the method for producing a polyimide precursor or the like, in order to further improve storage stability, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like.
• examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability.
• Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
• Preferred monoamine compounds 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-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-car
• the method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain a polyimide precursor or the like. In order to improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.
• the resin composition of the present invention contains at least two types of resins.
• the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins.
• the resin composition of the present invention contains two or more specific resins, it preferably contains, for example, two or more polyimide precursors having different dianhydride-derived structures (R 115 in the above formula (2)).
• the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
• other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
• phenol resins polyamides
• epoxy resins polysiloxanes
• resins containing a siloxane structure resins containing a siloxane structure
• (meth)acrylic resins eth)acrylamide resins
• urethane resins urethane resins
• butyral resins ethyral resins
• styryl resins polyether resins
• polyester resins polyester resins.
• the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.
• the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
• the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
• the content of the other resin may be low.
• the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
• the lower limit of the content is not particularly limited, and may be 0% by mass or more.
• the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a polymerizable compound.
• the polymerizable compound may include a radical crosslinking agent or other crosslinking agents.
• the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
• the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
• a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
• the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.
• the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
• radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
• unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters and amides preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds
• amides of unsaturated carboxylic acids and polyvalent amine compounds amides of unsaturated carboxylic acids and polyvalent amine compounds.
• addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sul
• addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable.
• the radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in
• radical crosslinking agents urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable.
• radical crosslinking agents compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.
• the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group.
• the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride.
• a urethane bond is a bond represented by *--O--C(.dbd.O)-- NR.sub.N --*, where R.sub.N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.
• R.sub.N represents a hydrogen atom or a monovalent organic group
• * represents a bonding site with a carbon atom.
• the crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds.
• the total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group.
• a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
• n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1.
• m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and further preferably 1 or 2.
• the alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U.
• the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
• crosslinking agent U has an amide group
• R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
• the crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group. An embodiment having only one such structure in the molecule is also preferred.
• the hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U.
• the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U are linked via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
• the crosslinking agent U contains only one radically polymerizable group
• the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
• the crosslinking agent U contains an alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2
• the structure bonded to the side of the alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
• hydrocarbon group a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
• hydrocarbon group a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof can be mentioned.
• a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
• the structure bonded to the side of the amide group opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
• the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
• examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a bond between these groups.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure.
• the aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group.
• the crosslinking agent U is a compound having a structure that does not have an axis of symmetry.
• the fact that the crosslinking agent U does not have an axis of symmetry means that the compound is a bilaterally asymmetric compound that does not have an axis that would produce an identical molecule to the original molecule by rotating the entire compound.
• the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U within the composition film is suppressed.
• the method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxy group or an amino group.
• the content of the other crosslinking agent is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.
• halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
• acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles
• oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenones, ⁇ -hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc.
• ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference.
• Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
• Nippon Kayaku Co., Ltd. is also preferably used.
• ⁇ -Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).
• Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used.
• the contents of this specification are incorporated herein.
• an oxime compound is more preferably used as a photoradical polymerization initiator.
• an oxime compound By using an oxime compound, it becomes possible to more effectively improve the exposure latitude.
• Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.
• oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.
• Preferred oxime compounds include, for example, compounds having the following structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.
• an oxime compound as a photoradical polymerization initiator.
• oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (SARTOMER Also usable are oxime compounds having the following structure:
• an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189 an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
• oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.
• an oxime compound having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
• the electron-withdrawing group of the aromatic ring group Ar OX1 includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
• the benzoyl group may have a substituent.
• the substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and further preferably an alkoxy group, an alkyl
• the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2).
• R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group; R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl
• R X12 is an electron-withdrawing group
• R X10 , R X11 , R X13 and R X14 are each a hydrogen atom.
• oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.
• oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.
• the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.
• the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound.
• At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.
• a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
• two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity.
• crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time.
• bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in WO-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No.
• the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• the sensitizer absorbs specific active radiation and becomes electronically excited.
• the sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
• Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
• sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone.
• the content of the sensitizer is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %.
• the sensitizer may be used alone or in combination of two or more types.
• the resin composition of the present invention may contain a chain transfer agent.
• the chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
• Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization.
• RAFT Reversible Addition Fragmentation Chain Transfer
• chain transfer agent may be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solid content of the resin composition.
• the chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a photoacid generator.
• the photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm.
• the light to be irradiated is preferably light with a wavelength of 300 nm to 450 nm, more preferably light with a wavelength of 330 nm to 420 nm.
• the photoacid generator is preferably capable of generating an acid by being exposed to light, either alone or in combination with a sensitizer.
• photoacid generators examples include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, and onium salt compounds. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.
• Quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent amino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and/or sulfonamide-bonded to a polyhydroxy polyamino compound.
• a resin composition can be obtained that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays.
• hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisOC P-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P
• polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.
• the quinone diazide compound contains an ester of a phenol compound and a 4-naphthoquinone diazide sulfonyl group. This allows for higher sensitivity to i-line exposure and higher resolution.
• the content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of resin.
• a sensitizer or the like may be added as necessary.
• X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X3s are present, they may be the same or different.
• the alkyl group and alkoxy group in X3 may have a substituent.
• the alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
• the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
• the halogen atom is preferably a chlorine atom or a fluorine atom.
• m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, multiple X3s may be the same or different.
• R 34 represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W.
• W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.
• R s1 represents an alkyl group, an aryl group, or a heteroaryl group
• R s2 which may be present in plurality, each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom
• R s6 which may be present in plurality, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group
• Xs represents O or S
• ns represents 1 or 2
• ms represents an integer of 0 to 6.
• the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R s1 may have a substituent.
• R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
• R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.
• organic halogenated compounds include the compounds described in paragraphs 0042 to 0043 of JP 2015-087409 A, the contents of which are incorporated herein by reference.
• Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
• the cyclic structure may be either a monocyclic ring or a condensed ring, and it is preferable that a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
• the monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.
• the monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.
• Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in formula (B1), respectively.
• Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent.
• Rb 13 is preferably an arylalkyl group.
• Rb 33 and Rb 34 each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.
• an alkyl group preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and even more preferably having 1 to 3 carbon atoms
• an alkenyl group preferably having 2
• linear or branched chain alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
• the divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group containing a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom.
• the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
• the cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms.
• the group containing a combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
• the alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched.
• the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the base generator is preferably an amine in which the amino group is protected by a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.
• silane coupling agent examples include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
• Me represents a methyl group
• Et represents an ethyl group.
• R includes a structure derived from a blocking agent in a blocked isocyanate group.
• an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
• examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).
• R 1 S1 represents a monovalent organic group
• R 1 S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group
• n represents an integer of 0 to 2.
• R S1 is preferably a structure containing a polymerizable group.
• Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group.
• R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
• n represents an integer of 0 to 2, and is preferably 1.
• n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and further preferably that n is 1 in at least two.
• oligomer type compounds commercially available products can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.
• the migration inhibitor examples include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
• a heterocycle pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole
• tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.
• an ion trapping agent that captures anions such as halogen ions can also be used.
• Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.
• migration inhibitors include the following compounds:
• the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the resin composition.
• the migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total is within the above range.
• the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.
• the resin composition contains a solvent
• that solvent is used as the solvent in the solution
• N-methyl-2-pyrrolidone is used.
• the solution of compound a is irradiated with exposure light, with the cumulative exposure dose being 500 mJ per mole of compound a.
• the molar absorption coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 , also referred to as “molar absorption coefficient 2”) of compound a at the wavelength of the exposure light is measured using the solution of compound a after exposure. From the above molar absorption coefficient 1 and molar absorption coefficient 2, the attenuation rate (%) is calculated based on the following formula.
• the photopolymerization initiator has sensitivity to a certain wavelength, meaning that the photopolymerization initiator generates a polymerization initiating species when exposed to light of a certain wavelength.
• the wavelength of the exposure light in terms of its light source, may include (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-lines), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron
• the wavelength of the exposure light may be selected from those to which the photopolymerization initiator has sensitivity, and preferably, h-line (wavelength 405 nm) or i-line (wavelength 365 nm), more preferably i-line (wavelength 365 nm).
• the light absorbent may be a compound that generates radical polymerization initiating species upon exposure to light, but from the viewpoints of resolution and chemical resistance, it is preferable that the light absorbent is a compound that does not generate radical polymerization initiating species upon exposure to light. Whether or not a light absorbent is a compound that generates a radical polymerization initiating species upon exposure to light can be judged by the following method.
• a solution containing a light absorber and a radical crosslinker at the same concentration as those contained in the resin composition is prepared.
• the radical crosslinker in the solution is the same compound as the radical crosslinker contained in the resin composition and at the same concentration.
• the naphthoquinone diazide compound includes a compound which generates indene carboxylic acid upon exposure and has a reduced absorbance at the exposure wavelength, and is preferably a compound having a 1,2-naphthoquinone diazide structure.
• the naphthoquinone diazide compound is preferably a naphthoquinone diazide sulfonic acid ester of a hydroxy compound.
• the hydroxy compound is preferably a compound represented by any one of the following formulas (H1) to (H6).
• Z represents a tetravalent organic group
• L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent organic group
• R 5 , R 6 , R 7 and R 8 each independently represent a monovalent organic group
• n3, n4, n5 and n6 each independently represent an integer from 0 to 3
• m3, m4, m5 and m6 each independently represent an integer from 0 to 2
• at least one of m3, m4, m5 and m6 is 1 or 2.
• R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group
• L 5 each independently represent a divalent organic group
• n7 represents an integer of 3 to 8.
• L6 represents a divalent organic group
• L7 and L8 each independently represent a divalent organic group containing an aliphatic tertiary or quaternary carbon.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom or a monovalent organic group
• L 9 , L 10 and L 11 each independently represent a single bond or a divalent organic group
• m7, m8, m9 and m10 each independently represent an integer of 0 to 2, and at least one of m7, m8, m9 and m10 is 1 or 2.
• R 24 represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
• n14, n15, and n16 each independently represent an integer of 0 to 2.
• R 30 represents a hydrogen atom or an alkyl group.
• R 25 , R 26 , R 27 and R 28 each independently represent a monovalent organic group, and are preferably a hydrogen atom, an alkyl group or a group represented by the above formula (R-1).
• n11, n12 and n13 each independently represent an integer of 0 to 2, and preferably 0 or 1.
• the compound represented by formula (H1-1) is preferably a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4).
• the compound represented by formula (H1-2) is preferably a compound represented by the following formula (H1-2-1) or (H1-2-2).
• the compound represented by formula (H1-3) is preferably a compound represented by the following formulas (H1-3-1) to (H1-3-3).
• R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• each L5 independently represents a group represented by the following formula (L-1).
• R 30 represents a monovalent organic group having 1 to 20 carbon atoms
• n14 represents an integer of 1 to 5
• * represents a bonding site to another structure.
• n7 is preferably an integer of 4 to 6. Examples of the compound represented by formula (H3) include the following compounds: In the following formula, each n independently represents an integer of 0 to 9.
• L 6 is preferably —C(CF 3 ) 2 —, —S( ⁇ O) 2 — or —C( ⁇ O)—.
• L 7 and L 8 are preferably each independently a divalent organic group having 2 to 20 carbon atoms. Examples of the compound represented by formula (H4) include the following compounds.
• L 9 , L 10 and L 11 each independently represent preferably a single bond, -O-, -S-, -S( ⁇ O) 2 -, -C( ⁇ O)-, -C( ⁇ O)O-, cyclopentylidene, cyclohexylidene, phenylene or a divalent organic group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulae (L-2) to (L-4).
• a hydroxy compound and a predetermined amount of naphthoquinone diazide sulfonyl chloride are reacted in a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to carry out esterification, and the resulting product is washed with water and dried to obtain the compound.
• a solvent such as dioxane, acetone, or tetrahydrofuran
• a basic catalyst such as triethylamine
• the weight average molecular weight of the above compound is preferably from 3,000 to 50,000, and more preferably from 5,000 to 30,000.
• a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorosurfactant.
• Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein by reference.
• examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.
• a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.
• the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably within the above range.
• thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.
• thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be included, or two or more types may be included. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.
• inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
• Organotitanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and provide a good curing pattern.
• titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.
• Tetraalkoxytitanium compounds for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl)butoxide ⁇ ], and the like.
• Titanocene compounds For example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
• Monoalkoxytitanium compounds For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
• the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function.
• the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
• the shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
• Step B Formation of Conductive Layer
• a seed layer was formed in the regions between the precursor patterns of the first insulating pattern of the laminate formed above, in the regions between the precursor patterns of the second insulating pattern, and on the precursor pattern of the second insulating pattern, and then a plated Cu layer was formed.
• a conductive layer is formed on the laminate formed above in process B, and heated in process D described below.
• the surface of the laminate is polished to expose the Ti layer formed as the first seed layer and the conductive pattern formed in the region between the second insulating patterns, and then polished so that the second insulating pattern and the conductive pattern formed in the region between the second insulating patterns are exposed on the surface and are flat.
• the laminate formed as described above was heated in Process D described below, and a conductive layer was formed in Process B.

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• 2023
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