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
  • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
  • H10W20/41—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their conductive parts
  • H10W20/435—Cross-sectional shapes or dispositions of interconnections
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
• • 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
• • 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
  • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
• • 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
  • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
  • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
  • H10W20/48—Insulating materials thereof
• • 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
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/01—Manufacture or treatment
  • H10W70/05—Manufacture or treatment of insulating or insulated package substrates, or of interposers, or of redistribution layers

Definitions

• the present invention relates to a component, a method for manufacturing the component, a photosensitive resin composition, and a semiconductor component.
• 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.
• the damascene method is a method in which a groove in the shape of a wiring is formed in an interlayer insulating film and a metal such as copper is filled in.
• the damascene method has the advantage that even metals that are difficult to dry etch, such as copper, can be easily used as wiring materials.
• 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.
• Patent Document 1 describes a negative photosensitive resin composition that contains a polyimide or a polyimide precursor, a compound that generates an acid when irradiated with active light, and a crosslinking agent that acts by the acid, wherein the crosslinking agent contains at least one of a first compound having two or more functional groups of at least one type selected from the group consisting of a methylol group and an alkoxyalkyl group, and a second compound having two or more functional groups of at least one type selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, and a glycidyloxy group, and a method for producing a semiconductor device member using the composition.
• Non-Patent Document 1 describes the formation of a copper wiring layer by a dual damascene process using a negative thermosetting phenolic material.
• the object of the present invention is to provide a member in which peeling of a conductive pattern is suppressed, a method for manufacturing the member, a photosensitive resin composition used in the method for manufacturing the member, and a semiconductor member including the member.
• a substrate an insulating pattern disposed on the substrate;
• a component, wherein an angle formed between a bottom surface of the conductive pattern and a side surface of the conductive pattern is greater than 90° and is equal to or smaller than 110°.
• a member comprising: 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, a difference between a maximum value and a minimum value of a distance from the surface of the substrate to a surface of the conductive pattern on the opposite side to the substrate in a direction perpendicular to the substrate surface of the member is 500 nm or less; A component in which the angle formed between a bottom surface of the conductive pattern and a side surface of the conductive pattern in a region between the second insulating patterns is greater than 90° and is 110° or less.
• a method for producing a member having a conductive pattern present between the insulating patterns comprising the steps of: a conductive layer forming step of forming a conductive layer on the insulating pattern and in the regions between the insulating patterns of the base material on which the insulating patterns are formed, to obtain a member A; and a polishing step of polishing the member A to obtain a member having the conductive pattern and the insulating pattern exposed on a surface thereof;
• the angle between the bottom surface of the conductive pattern of the member and the side surface of the conductive pattern is greater than 90° and is not greater than 110°. Manufacturing method of components.
• a film forming step including applying a composition for forming an insulating pattern onto the substrate to form a film,
• the insulating pattern-forming composition is heated at 100° C. for 3 minutes to form a 3 ⁇ m-thick film, which has an i-line transmittance of 5% or more.
• the method includes, after the film-forming step, a drying step of drying the film, an exposure step of exposing the dried film to light, and a development step of developing the exposed film with a developer,
• a method for producing a member 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: The method includes steps A to C, a bottom surface of the conductive pattern of the component and a side surface of the conductive pattern form an angle greater than 90° and not greater than 110°.
• the photosensitive resin composition according to ⁇ 14> comprising a polyimide or a polyimide precursor.
• a semiconductor member comprising the member according to any one of ⁇ 1> to ⁇ 7>.
• the present invention provides a member in which peeling of a conductive pattern is suppressed, a method for manufacturing the member, a photosensitive resin composition used in the method for manufacturing the member, and a semiconductor member including the member.
• FIG. 1 is a schematic cross-sectional view showing an example of a first member of the present invention.
• 10 is a schematic cross-sectional view showing an example in which a conductive pattern is distorted.
• FIG. FIG. 2 is a schematic cross-sectional view showing an example of a second member of the present invention.
• 4A to 4C are process explanatory diagrams each showing, in cross section, a process of a method for producing a first member according to an embodiment of the present invention.
• 5A to 5C are process explanatory views each showing, in schematic cross-sectional views, a process (part) of a method for producing a second member according to an embodiment of the present invention.
• 5A to 5C are process explanatory diagrams each showing, in schematic cross-sectional views, a process (part) of the method for producing a second member according to one embodiment of the present invention (continuation of FIG. 5 ).
• a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower limit and upper limit, respectively.
• the term “step” includes not only an independent step, but also a step that cannot be clearly distinguished from another step, so long as the intended effect of the step can be achieved.
• groups (atomic groups) when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups).
• an "alkyl group” encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
• exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
• (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.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene equivalent values, unless otherwise specified.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns.
• these molecular weights are measured using THF (tetrahydrofuran) as an eluent.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm.
• 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 content of each component in the composition means the total content of all compounds corresponding to that component.
• the temperature is 23° C.
• the pressure is 101,325 Pa (1 atm)
• the relative humidity is 50% RH.
• combinations of preferred aspects are more preferred aspects.
• a member according to a first aspect of the present invention (hereinafter also referred to as "first member") is a member having a substrate, an insulating pattern arranged on the substrate, and a conductive pattern existing between the insulating patterns, wherein the difference between the maximum and minimum distances from the substrate surface to the surface of the conductive pattern on the opposite side to the substrate in a direction perpendicular to the substrate surface is 500 nm or less, and the angle formed between a bottom surface of the conductive pattern and a side surface of the conductive pattern is greater than 90° and less than 110°.
• 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 conductive pattern may be in contact with the insulating pattern, or may further include a seed layer or the like between the conductive pattern and the insulating pattern.
• the first member of the present invention may further include a seed layer (a power supply layer for electrolytic copper plating).
• a seed layer is preferably present between the insulating pattern and the conductive pattern.
• the seed layer may be a layer made of a metal such as titanium, chromium, or nickel.
• FIG. 1 is a schematic cross-sectional view showing an example of a first member of the present invention.
• an insulating pattern 102 is formed on a substrate 100, and a seed layer 104 and a conductive pattern 106 are formed in the regions between the insulating patterns 102.
• the cyclization rate is measured by the method described below.
• the insulating pattern is preferably a cured product of a photosensitive resin composition described below.
• the first insulating pattern is preferably a cured product of a first insulating pattern forming composition described below.
• the first insulating pattern may have other layers formed between the pattern and the substrate, but it is preferable that the first insulating pattern is in contact with the substrate.
• the first insulating pattern is not particularly limited and may be a line and space pattern, a hole pattern, etc., but is preferably a hole pattern.
• the distance between the lines (space width) 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 second insulating pattern is not particularly limited and may be a line and space pattern, a hole pattern, etc., but is preferably a line and space pattern.
• the distance between the lines (space width) 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 thickness of the second 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 preferred aspects of the conductive pattern are the same as those of the conductive pattern of the first member described above.
• the conductive pattern may be in contact with the first insulating pattern, or may further include a seed layer or the like between the conductive pattern and the first insulating pattern.
• the conductive pattern may be in contact with the second insulating pattern, or may further include a seed layer or the like between the conductive pattern and the second insulating pattern.
• the second member of the present invention may further include a seed layer.
• the seed layer is preferably present at least one of between the first insulating pattern and the conductive pattern and between the second insulating pattern and the conductive pattern, and more preferably present in both.
• the preferred aspects of the seed layer are the same as those of the seed layer of the first member described above.
• the second member of the present invention may further include a barrier layer.
• the barrier layer is preferably present on the surface of the conductive pattern opposite the substrate.
• the preferred aspects of the barrier layer are the same as those of the barrier layer of the first member described above.
• FIG. 3 is a schematic cross-sectional view showing an example of the second member of the present invention.
• 3A shows a substrate 100 having an insulating pattern 114 and a conductive pattern 116 formed on a silicon wafer 112.
• all the second pattern angles are greater than 90° and equal to or less than 110°.
• the angle between the end point of the bottom surface of the conductive pattern and the end point of the exposed portion of the conductive pattern on the side opposite to the substrate is defined as the second pattern angle, which is the same as the first pattern angle.
• the second pattern angle can be adjusted by setting the composition of the second insulating pattern-forming composition (type of resin, physical properties of the polymerizable compound) described below, exposure conditions such as the exposure amount, exposure time, and focus position in the second exposure step, and the developer in the second development step.
• the semiconductor article of the present invention is a article including the first article or the second article of the present invention.
• the semiconductor member include the semiconductor members shown in FIG. 4(c) or FIG. 6(c) described below, and semiconductor members in which one or more other members are mounted on these members. That is, the semiconductor article of the present invention may be a member in which another member (such as a semiconductor chip) is further mounted on the first member or the second member.
• a method for producing a member according to a first aspect of the present invention is a method for producing a member having a base material, an insulating pattern arranged on the base material, and a conductive pattern present between the insulating patterns, the method comprising a conductive layer formation step of forming a conductive layer on the insulating pattern and in regions between the insulating patterns of the base material on which the insulating patterns are formed, to obtain member A, and a polishing step of polishing member A to obtain a member having the conductive pattern and the insulating pattern exposed on its surface, wherein an angle formed between a bottom surface of the conductive pattern of the member and a side surface of the conductive pattern is greater than 90° and is 110° or less.
• the above-mentioned first component of the present invention is produced. That is, the substrate, insulating pattern, conductive pattern, and the angle (first pattern angle) formed between the bottom surface of the conductive pattern of the component and the side surface of the conductive pattern in the manufactured component are as described above, and preferred aspects of these are also similar to the preferred aspects of these in the first component described above.
• the method for producing the first member of the present invention preferably has a film formation step including applying a composition for forming an insulating pattern (hereinafter also simply referred to as a "resin composition") onto the substrate to form a film prior to the conductive layer formation step.
• the i-line transmittance of a film having a thickness of 3 ⁇ m formed by heating the composition for forming an insulating pattern at 100° C. for 3 minutes is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more.
• the details of the composition for forming an insulating pattern will be described later.
• the resin composition is preferably applied to a substrate by coating.
• the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating, or inkjet methods are preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are more preferred.
• a film of a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the resin composition according to the means to be applied.
• 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 material 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 suitably 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 above-mentioned film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
• the method for producing the first member of the present invention may include a drying step of drying the film formed in the film forming step.
• the drying step is preferably carried out after the film-forming step and before the exposure step.
• the drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and even more 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 film may be subjected to an exposure step to selectively expose the film to light.
• Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film.
• the amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm 2 , and more preferably 200 to 8,000 mJ/cm 2 , calculated as exposure energy at a wavelength of 365 nm.
• 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, for example, (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, and 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,
• the exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.
• the film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step.
• the post-exposure baking step can be carried out after the exposure step and before the development step.
• the heating temperature in the post-exposure baking step is preferably from 50°C to 160°C, and more preferably from 60°C to 120°C.
• the heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes.
• the heating rate in the post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, and even more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
• the rate of temperature rise may be appropriately changed during heating.
• the heating means in the post-exposure baking step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used. It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
• the film may be subjected to a development step in which the film is developed with a developer to form a pattern.
• the first member manufacturing method of the present invention may include a development step of developing the film exposed in the exposure step with a developer to form a pattern. Development removes one of the exposed and unexposed areas of the film to form a pattern.
• development in which the non-exposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.
• the developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.
• examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
• TMAH tetramethylammonium hydroxide
• potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
• the compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent.
• the organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol
• examples of amides that are suitable include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
• 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.
• a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferable, a secondary amine, a tertiary amine, or an ammonium salt is more preferable, a secondary amine or a tertiary amine is even more preferable, and a tertiary amine is particularly preferable.
• the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
• the boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C.
• the basic compound used preferably has a boiling point of 80° C. or higher, and more preferably has a boiling point of 100° C. or higher.
• the developer may contain only one kind of basic compound, or may contain two or more kinds of basic compounds.
• basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples include pentane, N-methylhexy
• the preferred embodiment of the base generator is the same as the preferred embodiment of the base generator contained in the composition described above.
• the base generator is a thermal base generator.
• the developer may further comprise other components.
• other components include known surfactants and known defoamers.
• the method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film is formed in the developer, a paddle development method in which a developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
• a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
• a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
• Methods of supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like on the substrate, and a combination of these steps.
• the development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
• the temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
• the pattern may be washed (rinsed) with a rinse solution. Also, a method may be adopted in which a rinse solution is supplied before the developer in contact with the pattern has completely dried.
• the composition for forming an insulating pattern is applied to a silicon wafer, heated at 100° C. for 180 seconds, irradiated with i-rays at an exposure dose of 100 mJ/ cm2 , and heated at 110° C. for 3 minutes.
• the swelling rate of the film in the developer is preferably 15 vol. % or less, more preferably 12 vol. % or less, and even more preferably 10 vol. % or less.
• the rinse liquid may be, for example, water.
• the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).
• the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent.
• the organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably has a lower solubility for the pattern than the organic solvent contained in the developer.
• the organic solvent may be used alone or in combination of two or more.
• the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA, or PGME, and even more preferably cyclopentanone or PGMEA.
• the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinse solution. Furthermore, the organic solvent may account for 100% by mass, based on the total mass of the rinse solution.
• the rinse liquid may contain at least one of a basic compound and a base generator.
• a basic compound and a base generator when the developer contains an organic solvent, an embodiment in which the rinsing liquid contains an organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention.
• the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments thereof are also the same.
• the basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.
• the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinse solution.
• the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
• the content of the basic compound or base generator is also preferably 70 to 100 mass % based on the total solid content of the rinse liquid.
• the rinse solution may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds.
• the total amount thereof is preferably within the above range.
• the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
• the method of supplying the rinsing liquid in the rinsing step may be a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps.
• the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.
• the slurry also preferably contains an oxidizing agent, which acts on the surface of the insulating pattern, making the insulating pattern easier to remove, and is believed to increase the etching rate.
• an oxidizing agent include hydrogen peroxide, peroxides, nitrates, iodates, periodates, hypochlorites, chlorites, chlorates, perchlorates, persulfates, dichromates, permanganates, ozone water, silver (II) salts, and iron (III) salts.
• the content of the corrosion inhibitor in 1 L of the slurry is preferably 0.0001 to 1.0 mol, more preferably 0.0005 to 0.5 mol, and even more preferably 0.0005 to 0.05 mol. Two or more corrosion inhibitors may be used in combination. In this case, it is preferable that the total content of the corrosion inhibitors contained falls within the above numerical range.
• the amount of the surfactant added is preferably 0.0001 to 10 g, more preferably 0.0005 to 5 g, and particularly preferably 0.0005 to 3 g, per liter of slurry. Two or more surfactants may be used in combination. In this case, it is preferable that the total content of the surfactants contained falls within the above numerical range.
• the slurry may include a solvent.
• the solvent may be water, an organic solvent, or the like.
• the organic solvent include polar solvents such as alcohol and acetic acid.
• examples of the organic solvent include glycols, glycol monoethers, glycol diethers, alcohols, carbonates, lactones, ethers, ketones, phenols, dimethylformamide, n-methylpyrrolidone, ethyl acetate, ethyl lactate, sulfolane, and sulfoxides. Among them, at least one selected from dimethyl sulfoxide, glycol monoethers, alcohols, and carbonates is preferable.
• the solvent may be supplied during polishing or may be added to the slurry before polishing.
• the amount of the solvent used may be appropriately determined taking into consideration the state of the surface to be polished.
• the content of the organic solvent is preferably 0.01 to 90 parts by mass relative to 100 parts by mass of the slurry during polishing.
• the content is more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, in order to improve the wettability of the slurry to the substrate during polishing.
• the upper limit is more preferably 50 parts by mass or less, and even more preferably 10 parts by mass or less, in order to facilitate the manufacturing process.
• FIG. 4 is a process explanatory diagram showing, in schematic cross-sectional views, the process of the method for producing the first member according to one embodiment of the present invention.
• 4A shows a state in which insulating patterns 102 are formed on a substrate 100.
• the insulating patterns 102 have regions 103 between the insulating patterns.
• Step A a preparation step of preparing member A including the first insulating pattern and the second insulating pattern
• Step B a conductive layer formation step of forming a conductive layer in the areas between the first insulating patterns of member A, the areas between the second insulating patterns, and on the second insulating pattern to obtain member B
• Step C a polishing step of polishing member B to obtain a member in which the conductive patterns and the second insulating pattern are exposed.
• the method for producing the second member of the present invention includes a preparation step (step A) of preparing a member A including the first insulating pattern and the second insulating pattern.
• the member A may be manufactured by a known method, or may be obtained by means of purchase or the like. A manufacturing method for manufacturing the member A will be described below.
• the method for producing member A preferably includes a first film formation step of applying a photosensitive resin composition (a composition for forming a first insulating pattern) to a substrate to form a film, a first exposure step of selectively exposing the film formed by the first film formation step, a first development step of developing the film exposed by the first exposure step with a developer to form a first insulating pattern, a second film formation step of applying a photosensitive resin composition (a composition for forming a second insulating pattern) to the first insulating pattern to form a film, a second exposure step of selectively exposing the film formed by the second film formation step, and a second development step of developing the film exposed by the second exposure step with a developer to form a second insulating pattern.
• a photosensitive resin composition a composition for forming a first insulating pattern
• the manufacturing method of component A may include forming a first insulating pattern by etching or the like instead of the first exposure step and the first development step, and may include forming a second insulating pattern by etching or the like instead of the second exposure step and the second development step.
• first insulating pattern by etching or the like instead of the first exposure step and the first development step
• second insulating pattern by etching or the like instead of the second exposure step and the second development step.
• the method for producing a cured product of the present invention preferably includes a first film-forming step of applying a photosensitive resin composition to a substrate to form a film.
• the substrate in the first film-forming step is as described above.
• the film formed in the first film-forming step may be subjected to a first exposure step in which the film is selectively exposed to light.
• the first exposure step can be carried out in the same manner as the exposure step in the above-mentioned first member manufacturing method of the present invention, and the preferred embodiments are also the same.
• the film may be subjected to a post-exposure baking step (first post-exposure baking step).
• the first post-exposure baking step can be carried out in the same manner as the post-exposure baking step in the above-mentioned first member production method of the present invention, and the preferred embodiments are also the same.
• the film after exposure may be subjected to a first development step in which the film is developed with a developer to form a pattern.
• the first developing step can be carried out in the same manner as the developing step in the above-mentioned first method for producing a member of the present invention, and the preferred embodiments are also the same.
• the film after development may be subjected to a first heating step to heat the film.
• the first heating step can be carried out in the same manner as the heating step in the above-mentioned first method for producing a member of the present invention, and the preferred aspects are also the same.
• heating may not be performed at this stage, and after a second insulating pattern, which will be described later, is formed, the first insulating pattern and the second insulating pattern may be heated together. This heating may be carried out before the polishing step after the conductive layer forming step, or after the polishing step.
• a first post-treatment step After the first development step, a first post-treatment step may be carried out in which post-treatment is carried out by at least one of heating and exposure.
• the heating temperature is preferably from 100 to 160°C, and more preferably from 120 to 160°C.
• the exposure may be performed by a method similar to that of the above-mentioned exposure step, in which the entire surface is exposed with an exposure dose of 1,000 to 50,000 mJ/cm 2 .
• the method for producing the member A preferably includes a second film-forming step of applying a photosensitive resin composition to the first insulating pattern to form a film.
• the second film-forming step can be carried out in the same manner as the first film-forming step described above, except that the photosensitive resin composition is applied to the first insulating pattern instead of the substrate, and the preferred aspects are also the same.
• the second exposure step and the second development step can be carried out in the same manner as the first exposure step and the first development step, and the preferred aspects are also the same. Furthermore, after the second exposure step, a second post-exposure baking step may be included which is carried out in the same manner as the above-mentioned first post-exposure baking step. Furthermore, after the second development step, a second post-treatment step may be included which is carried out in the same manner as the first post-treatment step described above.
• the film after development may be subjected to a second heating step to heat the film.
• the second heating step can be carried out in the same manner as the heating step in the above-mentioned first method for producing a member of the present invention, and the preferred embodiments are also the same.
• heating may not be performed at this stage, and after a second insulating pattern, which will be described later, is formed, the first insulating pattern and the second insulating pattern may be heated together. This heating may be carried out before the polishing step after the conductive layer forming step, or after the polishing step.
• the method for producing the second member of the present invention includes, as step B, a conductive layer formation step of forming a conductive layer in the regions between the first insulating patterns of member A, the regions between the second insulating patterns, and on the second insulating pattern to obtain member B.
• Step B can be carried out in the same manner as the conductive layer forming method in the above-mentioned first member producing method of the present invention, and the preferred embodiments are also the same.
• the method for manufacturing the second member of the present invention further includes, between step A and step B, a seed layer formation step of forming a seed layer present in the area between the first patterns and the area between the second patterns.
• the seed layer forming step is preferably a step of forming a seed layer along the inner walls (side and bottom surfaces) of the region between the first patterns and the region between the second patterns.
• a seed layer may also be formed on the second pattern. In such an embodiment, the seed layer can be removed by polishing in step C described below to finally expose the second insulating pattern.
• the seed layer formation process can be performed in the same manner as the seed layer formation process in the first component manufacturing method of the present invention described above, and the preferred embodiments are also the same.
• the method for producing the second member of the present invention includes, as step C, a polishing step of polishing the member B to obtain a member in which the conductive pattern and the second insulating pattern are exposed.
• the polishing step removes the surface of the conductive layer to provide a conductive pattern. If a seed layer is formed by the above-mentioned method, it is preferable to remove the seed layer as well.
• the polishing step can be carried out in the same manner as in the polishing step in the above-mentioned first method for producing a member of the present invention, and the preferred embodiments are also the same.
• the method for producing the second member of the present invention preferably further comprises, after step C, a barrier layer forming step of forming a barrier layer present on the conductive pattern.
• a barrier layer is formed on the exposed surface of the conductive pattern exposed by step C.
• the barrier layer forming step can be carried out in the same manner as the polishing step in the above-mentioned first method of producing a member of the present invention, and the preferred aspects are also the same.
• the second method of producing a member of the present invention may further include a barrier layer forming step of polishing the barrier layer.
• the barrier layer polishing step is not particularly limited and can be performed by a known method, for example, the same method as in the above-mentioned step C.
• the method for producing the second member of the present invention may further include other steps known in the art.
• FIG. 5 is a process explanatory diagram showing, in schematic cross-sectional views, a process (part) of a method for producing a second member according to an embodiment of the present invention.
• 5A shows a substrate 1 having an insulating pattern 4 and a conductive pattern 6 formed on a silicon wafer 2. Such a substrate can be manufactured by a conventional method or can be obtained by purchase or the like.
• FIG. 5A shows a substrate 1 having an insulating pattern 4 and a conductive pattern 6 formed on a silicon wafer 2.
• Such a substrate can be manufactured by a conventional method or can be obtained by purchase or the like.
• FIG. 5( b ) shows a state in which a photosensitive resin composition used for forming a first insulating pattern is applied onto the substrate 1 to form a film 10 .
• FIG. 5C shows a state in which the film 10 in FIG. 5B has been exposed and developed to form a hole pattern 12, resulting in a first insulating pattern 14 before hardening.
• FIG. 5D 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. 5( e ) shows a state in which a line-and-space pattern (space portion) 22 is formed in film 20 so that the space portion is located over the hole pattern in film 10, forming a second insulating pattern before curing, and then heating changes the first insulating pattern before curing to first insulating pattern 16, and the second insulating pattern before curing to second insulating pattern 26.
• the member shown in FIG. 5( e ) corresponds to an example of member A in process A.
• the resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
• the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
• the term "main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
• the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
• the precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin.
• a resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred.
• the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. That is, the resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.
• the resin composition preferably contains a polyimide or a polyimide precursor as the specific resin.
• the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
• the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably contains a radical polymerization initiator and a radical crosslinking agent. If necessary, it can further contain a sensitizer. For example, a negative photosensitive film is formed from such a resin composition.
• the specific resin may also have a polarity conversion group such as an acid-decomposable group.
• the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or negative-type photosensitive film is formed.
• a 1 and A 2 each independently represent an oxygen atom or —NR z —, and preferably an oxygen atom.
• Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
• R 111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group.
• R 111 is preferably derived from a diamine.
• the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
• R 111 is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
• * represents a bonding site with other structures.
• diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphen
• diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.
• diamines having two or more alkylene glycol units in the main chain are also preferably used.
• diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of WO 2017/038598.
• R 111 is preferably represented by -Ar-L-Ar-.
• each Ar is independently an aromatic group
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above.
• Ar is preferably a phenylene group
• L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 -.
• the aliphatic hydrocarbon group here is preferably an alkylene group.
• Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.
• R 111 is also preferably a group represented by the following formula (71): In the above embodiment, R 111 is more preferably a group represented by the following formula (72).
• a 1 to A 3 each independently represent a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and each of the four benzene rings described in formula (71) may have a substituent.
• * represents a bonding site with the nitrogen atom in formula (2).
• a 1 to A 3 are preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, -S-, -S( ⁇ O) 2 -, -NHC( ⁇ O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, or a group consisting of a combination of two or more of these, and further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-.
• 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.
• aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH 2 -, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 -, with -C(CH 3 ) 2 - being preferred.
• substituents on the four benzene rings shown in formula (71) include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
• An embodiment in which all of the four benzene rings in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.
• R 111 is also preferably a group represented by the following formula (81): In the above embodiment, R 111 is more preferably a group represented by the following formula (82).
• A1 and A2 each independently represent a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and each of the three benzene rings described in formula (81) may have a substituent.
• * represents a bonding site with the nitrogen atom in formula (2).
• a 1 and A 2 are each preferably independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, -S-, -S( ⁇ O) 2 -, -NHC( ⁇ O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, or a group consisting of a combination of two or more of these, still more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-, and particularly preferably -C(CH 3 ) 2 -.
• 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.
• 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 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 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.
• 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 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.
• X 1 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 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 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 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 lowering 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.
• 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
• dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
• 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
• 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).
• 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 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 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.
• 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).
• Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of a 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.
• alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
• halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
• the organic solvent may be one type or two or more types.
• the resin composition of the present invention preferably contains a radical crosslinking agent.
• the radical crosslinking agent is a compound having a radical polymerizable group.
• the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
• Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
• a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
• 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.
• radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.
• 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 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.
• the radical polymerizable group in the crosslinking agent U 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. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
• the crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.
• R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
• R 3 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
• 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 a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
• R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
• the cross-linking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
• the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
• the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or propylene group, and particularly preferably an ethylene group.
• 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
• 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 carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.
• the crosslinking agent U has a hydroxy group.
• the crosslinking agent U preferably contains an aromatic group.
• the aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U.
• the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
• the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
• aromatic heterocyclic ring in such an aromatic heterocyclic group examples include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be further condensed with other rings, such as indole and benzimidazole.
• the heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
• the aromatic group is preferably contained in a linking group that links two or more radically polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.
• the number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.
• the crosslinking agent U contains two or more urea bonds or urethane bonds in total, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
• the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group” refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked that links these objects with the shortest length (minimum number of atoms).
• the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
• 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 molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.
• 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.
• crosslinking agent U Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited thereto.
• a difunctional methacrylate or acrylate for the resin composition.
• the compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl ...
• PEG200 diacrylate refers to polyethylene glycol diacrylate having a formula weight of about 200 for the polyethylene glycol chain.
• a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent.
• the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
• the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
• the radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.
• the resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
• the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by a photoacid generator or a photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
• the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
• a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred.
• crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with an acyloxymethyl group, a methylol group, an ethylol group, or an alkoxymethyl group.
• the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used.
• the methylol groups of these compounds may be self-condensed to produce an oligomer.
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.
• Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine.
• the alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms.
• the total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
• the molecular weight of the compound is preferably 1,500 or less, and more preferably 180 to 1,200.
• Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:
• X represents a single bond or a divalent organic group
• each of R104 independently represents an alkyl group or an acyl group
• R103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by -C( R4 ) 2COOR5 (each of R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group that is eliminated by the action of an acid)).
• Each R 105 independently represents an alkyl group or an alkenyl group; each of a, b, and c independently represents 1 to 3; d represents 0 to 4; e represents 0 to 3; f represents 0 to 3; a+d is 5 or less; b+e is 4 or less; and c+f is 4 or less.
• the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
• the alkyl group may be either linear or branched.
• the above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
• the cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.
• the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
• the above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms.
• the above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the alkyl and aryl groups.
• the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have known substituents.
• R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
• the group that decomposes under the action of an acid to generate an alkali-soluble group, or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.
• Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures.
• Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds has been changed to an acyloxymethyl group.
• Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
• the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
• melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
• urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; Urea-based crosslinking agents such as
• benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.
• Such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis
• n is an integer from 1 to 5
• m is an integer from 1 to 20.
• hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.
• 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, as described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.
• 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.
• 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 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.
• Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.
• 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
• amino compounds include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.
• 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.
• the photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").
• the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably a compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105).
• 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.
• oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs [0064] to [0068] of JP2011-209692A and paragraphs [0158] to [0167] of JP2015-194674A, the contents of which are incorporated herein by reference.
• R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
• R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• the stereochemical structure of the oxime (E, Z) may be either one or a mixture.
• Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).
• Rb 3 is an alkyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), an alkenyl group (having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), an arylalkyl group (having 7 to 23 carbon atoms, preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), an arylalkenyl group (having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), an alkoxyl group (having 1 to 24 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryloxy group (having 6 to 22 carbon
• 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 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 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), and an aryl group is preferable.
• an alkyl group preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms
• an alkenyl group preferably having 2 to 12 carbon atoms, more preferably having 2
• L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the linking chain path is 3 or more.
• R and R each independently represent a monovalent organic group.
• linking chain refers to an atomic chain on a path connecting two atoms or atomic groups to be linked, which links these objects with the shortest distance (the smallest number of atoms).
• L is composed of a phenyleneethylene group, has an ethylene group as a saturated hydrocarbon group
• the linking chain is composed of four carbon atoms
• the number of atoms on the path of the linking chain i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain” is 4.
• L is a divalent linking group, and is preferably a divalent organic group.
• the linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more.
• the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
• the linking chain length is the number of atoms present in the atomic sequence that is the shortest path between the two carbonyl groups in the formula.
• R N1 and R N2 each independently represent a monovalent organic 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), and are preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms).
• the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, the aromatic ring, or the substituent.
• the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
• Examples of the aliphatic hydrocarbon group constituting R N1 and R N2 include a linear or branched chain alkyl group, a cyclic alkyl group, a group containing a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain.
• the linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms.
• 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.
• 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 42 , R 43 , R 44 , and R 45 each independently represent a hydrogen atom or a monovalent organic group
• R 46 and R 47 each independently represent a monovalent organic group
• n16 and n17 each independently represent an integer of 0 to 4
• m11 and m12 each independently represent an integer of 0 to 4
• at least one of m11 and m12 is an integer of 1 to 4.
• R11 , R12 , R13 , R14 , R15 , R16 , R17 , R18 , R19 and R20 are each preferably independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group.
• the liquid properties (particularly fluidity) when the coating liquid composition is prepared can be further improved, and the uniformity of the coating thickness and liquid saving can be further improved.
• the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and improving the coatability of the surface to be coated. This makes it possible to more suitably form a uniform film with minimal unevenness in thickness.
• the phenol-based compounds may be used alone or in combination of two or more.
• the content of the phenol-based compound is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.
• the other polymer compounds may be used either individually or in combination of two or more.
• the content of the other polymer compounds is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.
• the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
• the breaking elongation of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
• the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
• ⁇ resin ⁇ A-1 to A-10 Compounds having the following structure CA-1: Divinylbenzene/p-hydroxystyrene/styrene copolymer
• the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
• the reaction solution obtained was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude resin.
• the produced crude resin was filtered and dissolved in 1.5 L of tetrahydrofuran to obtain a crude resin solution.
• the crude resin solution obtained was dropped into 28 L of water to precipitate the resin, and the resulting precipitate was filtered and then dried in vacuum to obtain powdered resin A-1. It was confirmed by 1 H-NMR that the structure of resin A-1 was the structure represented by the above formula (A-5).
• the subscripts in parentheses represent the content ratio (mol %) of the repeating unit.
• the imidizable portion is imidized according to the above-mentioned imidization rate. These are the same in the following resins A-5 to A-9.
• the weight average molecular weight (Mw) and imidization rate (%) of Resin A-5 are shown in the above table.
• B-1 Compound having the following structure (Irgacure OXE01, manufactured by BASF)
• B-2 Compound having the following structure
• C-1 Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid
• C-2 and C-3 Compounds having the following structure
• G-1 Compound having the following structure
• G-2 4-hydroxy-TEMPO free radical (Tokyo Chemical Industry Co., Ltd.)
• G-3 Compound having the following structure
• H-1 Compound having the following structure
• H-2 8-azaadenine
• M-1 N-phenyldiethanolamine (Tokyo Chemical Industry Co., Ltd.)
• M-2 The following compound
• the resin composition layer on the silicon wafer was exposed using an i-line stepper (Canon: FPR-3000i5) at the exposure amount shown in the "i-line exposure amount (mJ/cm 2 )" column of the table, and at the focus position shown in the "Focus ( ⁇ m)" column of the table (the surface of the resin composition layer opposite the silicon wafer is set to 0 ⁇ m, the inward direction of the resin composition layer is set to +, and the outward direction of the resin composition is set to -) through a mask formed with a 1:1 line and space having a line width of 0.5 to 3.0 ⁇ m and spaced at 0.05 ⁇ m intervals.
• the layer was heated as a PEB (Post Exposure Bake) at the temperature and time shown in the "PEB (°C/min)” column of the table. Thereafter, the resist pattern was developed using the developer shown in the "Developer” column of the table for the time shown in the "Development Time (s)” column of the table, and then rinsed for 30 seconds with the rinse solution shown in the "Rinsing Solution” column of the table, to obtain a precursor pattern of an insulating pattern. Further, heating was performed at the temperature, for the time and by the heating method described in the "Heating conditions” column of "Step A” in the table, to obtain an insulating pattern having the thickness described in the "Insulating pattern thickness” column in the table.
• PEB Post Exposure Bake
• Step C Plating CMP
• the conductive layer formed in step B was polished using a CMP (Chemical Mechanical Polishing) machine manufactured by Fujikoshi Machinery Co., Ltd., using the slurry shown in the "Slurry used” column of "Step C” in the table, for the time and pressure shown in the "Polishing time (min.)” and “Polishing pressure (psi)” columns of “Step C” in the table, thereby exposing the insulating pattern on the surface, the Ti layer formed as a seed layer, and the conductive pattern formed in the region between the insulating patterns.
• 1 psi is 6.895 kPa.
• Step D Barrier Metal CMP
• a CMP (Chemical Mechanical Polishing) tool manufactured by Fujikoshi Machinery Co., Ltd. was used to polish the surface using the slurry shown in the "Slurry used” column for "Step D” in the table for the time shown in the "Polishing time (min.)” column for “Step D” in the table, until the second insulating pattern and the conductive pattern were exposed and flat on the surface.
• Step F Formation of Surface Barrier Metal
• a barrier metal layer having a thickness shown in the "Thickness” column of "Process F” in the table was formed on the surface of the conductive pattern using the material shown in the "Material type” column of "Process F” in the table.
• insulating wiring with L/S (line/space) 5 ⁇ m/5 ⁇ m was formed on a silicon wafer on which SiO 2 was vapor-deposited in various examples and comparative examples, and then the substrate on which metal wiring was embedded by process B was polished with Tribolab CMP (manufactured by Bruker) using the above-mentioned silica slurry (NP6220 (manufactured by Nitta DuPont)) at a polishing pressure of 3 psi until the insulating pattern was exposed. Thereafter, the presence or absence of scratches on the polished surface was evaluated using an SEM according to the following evaluation criteria. A: No scratches were observed. B: Scratches were observed.
• Sa arithmetic mean of the surface roughness was calculated using a color 3D laser microscope VK-9710 (manufactured by KEYENCE), and evaluated using the following evaluation criteria.
• the substrate was exposed to 121°C and 100% relative humidity for 50 hours, after which an 18 mm cross-cut test/checkerboard test compliant tape (manufactured by Nichiban Corp.) was affixed to the surface and peeled off at 90°, and the remaining squares were counted and evaluated according to the following criteria.

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