Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
• • 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
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating 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
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
• • 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

Definitions

• the present invention relates to a laminate, a device, a resin composition, a method for producing a cured product, a method for producing a laminate, and a method for producing a device.
• Cyclized resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulating properties.
• the use is not particularly limited, but in the case of a semiconductor device for mounting, use as a material for an insulating film or a sealing material, or as a protective film can be mentioned. It is also used as a base film or coverlay for flexible substrates.
• the cyclized resin such as polyimide is used in the form of a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.
• a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate. It can be a laminate.
• a precursor of the cyclized resin such as a polyimide precursor is cyclized, for example, by heating, and becomes a cyclized resin such as polyimide in the cured product.
• the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition to be applied. It can be said that it is excellent in sex.
• cyclized resins such as polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application and development of the above-mentioned resin compositions are increasingly expected.
• Patent Literature 1 describes a photosensitive resin composition containing component (A), which is a photosensitive polyimide precursor, and component (B) having a specific structure.
• Patent Document 2 describes a fluororesin containing micropowder of a fluororesin and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and having a water content of 5000 ppm or less according to the Karl Fischer method.
• a fluororesin-containing polyimide precursor solution composition is described which comprises at least a non-aqueous dispersion and a polyimide precursor solution.
• the present invention provides a laminate having excellent adhesion between a metal wiring and a cured product even after being exposed to high humidity conditions, a device comprising the laminate, and a metal even after being exposed to high humidity conditions.
• a resin composition that provides a cured product having excellent adhesion to the resin composition, a cured product comprising the resin composition, a method for producing the cured product, a method for producing a laminate containing the cured product, and the cured product or laminate. It is an object of the present invention to provide a method of manufacturing a device comprising:
• a base material provided with metal wiring A cured product obtained by curing a film containing a cyclized resin or its precursor, and a photosensitive agent, The cured product has a dielectric constant of 3.0 or less, The cured product is in contact with at least part of the metal wiring.
• ⁇ 5> The laminate according to ⁇ 4>, wherein the resin contains at least one resin selected from the group consisting of liquid crystal polymers and polyphenylene ethers.
• ⁇ 6> The laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the film further contains inorganic particles.
• the inorganic particles are hollow silica particles.
• the photosensitive agent is a radical photopolymerization initiator.
• ⁇ 9> The laminate according to any one of ⁇ 1> to ⁇ 8>, wherein the film contains a compound containing a polymerizable group and an aromatic polycyclic structure.
• a device comprising the laminate according to any one of ⁇ 1> to ⁇ 9>.
• ⁇ 11> a cyclized resin or a precursor thereof; a photosensitizer;
• the film made of the resin composition has a relative dielectric constant of 3.0 or less after curing.
• ⁇ 12> The resin composition according to ⁇ 11>, further comprising resin particles.
• ⁇ 13> The resin composition according to ⁇ 12>, wherein the resin particles are fluorine atom-containing resin particles.
• the film further contains a resin having a dielectric constant of 2.7 or less.
• ⁇ 15> The resin composition according to ⁇ 14>, wherein the resin contains at least one resin selected from the group consisting of liquid crystal polymers and polyphenylene ethers.
• the resin contains at least one resin selected from the group consisting of liquid crystal polymers and polyphenylene ethers.
• ⁇ 16> The resin composition according to any one of ⁇ 11> to ⁇ 15>, wherein the film further contains inorganic particles.
• ⁇ 17> The resin composition according to ⁇ 16>, wherein the inorganic particles are hollow silica particles.
• the photosensitizer is a photoradical polymerization initiator.
• ⁇ 19> A cured product obtained by curing the resin composition according to any one of ⁇ 11> to ⁇ 18>, wherein the cured product has a dielectric constant of 3.0 or less.
• an exposure step of selectively exposing the film, and a development step of developing the film exposed by the exposure step using a developer to form a pattern Between the film forming step and the curing step, an exposure step of selectively exposing the film, and a development step of developing the film exposed by the exposure step using a developer to form a pattern.
• the method for producing a cured product according to ⁇ 20> including the steps.
• ⁇ 22> The method for producing a cured product according to ⁇ 20> or ⁇ 21>, wherein the curing step is performed by heating.
• ⁇ 23> A method for producing a laminate, comprising as a step the method for producing a cured product according to any one of ⁇ 20> to ⁇ 22>.
• ⁇ 24> A method for producing a device, comprising as a step the method for producing a cured product according to any one of ⁇ 20> to ⁇ 22> or the method for producing a laminate according to ⁇ 23>.
• a laminate having excellent adhesion between a metal wiring and a cured product even after being exposed to high humidity conditions, a device comprising the above laminate, and after being exposed to high humidity conditions A resin composition that provides a cured product having excellent adhesion to metals, a cured product made of the resin composition, a method for producing the cured product, a method for producing a laminate containing the cured product, and the cured product or laminate
• a method of manufacturing a device including a body is provided.
• a numerical range represented by the symbol "to” means a range including the numerical values before and after "to” as lower and upper limits, respectively.
• the term "process” is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
• a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
• alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
• exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.
• Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
• (meth)acrylate means both or either of “acrylate” and “methacrylate”
• (meth)acrylic means both “acrylic” and “methacrylic”
• (meth)acryloyl means either or both of “acryloyl” and “methacryloyl”.
• Me in the structural formulas represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• total solid content refers to the total mass of all components of the composition excluding the solvent.
• the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
• UV ray ultraviolet
• a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
• the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as “upper”. and the opposite direction is called “down”.
• the composition may contain two or more compounds corresponding to each component contained in the composition.
• 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, unless otherwise stated. Combinations of preferred aspects are more preferred aspects herein.
• the laminate of the present invention comprises a base material having metal wiring, and a cured product obtained by curing a film containing a cyclized resin or its precursor and a photosensitive agent, and the cured product has a dielectric constant of 3.5. 0 or less, and the cured product is in contact with at least part of the metal wiring.
• the laminate of the present invention exhibits excellent adhesion between the metal wiring and the cured product even after being exposed to high humidity conditions.
• the dielectric constant of a substance is greatly related to the polarity of the material, and in general, the higher the polarity, the more likely it is to absorb water.
• the relative dielectric constant of the cured product of the present invention is 3.0 or less, it is considered that the cured product is suppressed in water absorption and has excellent adhesion even after being exposed to high humidity conditions.
• the cured product contained in the laminate of the present invention is a cured product obtained by curing a film containing a cyclized resin or its precursor and a photosensitive agent.
• the curing reaction proceeds step by step in the curing process by exposure and heating, so other components such as cross-linking units and particles (for example, resin particles, polymers with a low relative dielectric constant, inorganic particles, etc.) are likely to disperse evenly, making it difficult to form water permeation paths and areas with high water absorption.
• cross-linking units and particles for example, resin particles, polymers with a low relative dielectric constant, inorganic particles, etc.
• it has excellent adhesion to wiring.
• chemical resistance is improved because a crosslinked structure is formed between the specific resins, between the specific resin and the polymerizable compound, and between the polymerizable compounds by including the photosensitizer.
• the laminate tends to maintain its insulating properties even after being exposed to high humidity conditions due to the effect of being excellent in adhesion.
• the dielectric constant of the cured product obtained from the photosensitive resin composition described in Patent Document 1 is presumed to exceed 3.0.
• Such a cured product is considered to have high polarity and high water absorption. Therefore, it is considered that the adhesion between the cured product and the metal wiring is lowered after exposure to high humidity conditions in a laminate containing the metal wiring and such a cured product.
• the fluororesin-containing polyimide precursor solution composition described in Patent Document 2 does not contain a photosensitive agent. In such a composition, the curing reaction proceeds all at once, so it is presumed that the components in the cured product become unbalanced. As a result, it is believed that the adhesion of a laminate containing metal wiring and a cured product obtained from such a composition is reduced after exposure to high humidity conditions.
• the laminate of the present invention includes a substrate with metal wiring.
• the type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited.
• semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.
• a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate are more preferable.
• these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
• HMDS hexamethyldisilazane
• the shape of the substrate is not particularly limited, and may be circular or rectangular.
• the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm.
• the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
• a plate-like base material for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.
• a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the base material.
• Metals in metal wiring include tin (Sn), gold (Au), silver (Ag), copper (Cu), aluminum (Al), tungsten (W), vanadium (V), titanium (Ti), chromium (Cr ), palladium (Pd), platinum (Pt), cobalt (Co), nickel (Ni), zinc (Zn), ruthenium (Ru), iridium (Ir), rhodium (Rh), lead (Pb), bismuth (Bi ) and at least one metal selected from the group consisting of indium (In), more preferably at least one metal selected from the group consisting of copper, tin and nickel, More preferably, it contains copper.
• metal X inclusion of at least one of metal X or an alloy containing that metal is generically simply referred to as "comprising metal X.”
• the alloy may contain elements other than those exemplified above.
• a copper alloy may contain silicon atoms to form a Corson alloy.
• oxygen that is inevitably dissolved, organic residues of the raw material compound mixed during precipitation, and the like may be present.
• the metal wiring may be a wiring comprising a plurality of different members.
• the thickness of the metal wiring is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m, at the thickest portion. Also, the minimum value of the interval between adjacent metal wires is preferably 0.01 to 100 ⁇ m, more preferably 1 to 20 ⁇ m.
• the laminate of the present invention contains a cured product.
• the relative dielectric constant of the cured product is 3.0 or less, preferably 2.9 or less, more preferably 2.8 or less. Although the lower limit of the dielectric constant is not particularly limited, it is preferably 1.0 or more.
• the relative permittivity can be measured by the method described in Examples below.
• the dielectric loss tangent of the cured product is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less.
• the lower limit of the dielectric loss tangent is not particularly limited as long as it is 0 or more.
• the dielectric loss tangent can be measured by the method described in Examples below.
• the cured product may be electrically insulating, semiconducting, or electrically conductive, but is preferably electrically insulating.
• the degree of electrical insulation and conductivity is appropriately selected according to the design and purpose.
• the lower limit of the volume resistivity of the cured product is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more, and 1.0 ⁇ 10 12 ⁇ . ⁇ cm or more is particularly preferable.
• the upper limit of the volume resistivity is not particularly limited, it is preferably 1.0 ⁇ 10 19 ⁇ cm or less, for example.
• the shape of the cured product is not particularly limited and may be selected according to the application, but it is preferably in the form of a film.
• this cured product can be used according to the application, such as the formation of a protective film on the wall surface, the formation of via holes for conduction, the adjustment of impedance, capacitance or internal stress, and the provision of heat dissipation function. You can also choose the shape.
• the film used for forming the cured product contains a photosensitive agent, the patterning can be easily performed by the exposure process, the development process, and the like, which will be described later.
• the film thickness of the cured product is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
• the film is preferably cured by heating, and the heating temperature is more preferably in the range of 120 ° C. to 400 ° C., more preferably in the range of 140 ° C. to 380 ° C., and 170 ° C. to It is particularly preferred to be in the range of 350°C.
• the details of heating will be described in the method for producing a cured product.
• the shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
• the imidization rate is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher, from the viewpoint of mechanical properties of the cured product.
• the imidization rate is measured by the method described below.
• the elongation at break of the cured product is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
• the breaking elongation is measured by the method described in JIS (Japanese Industrial Standards)-K6251:2017 under an environment of 25° C. and 65% relative humidity.
• the glass transition temperature (Tg) of the cured product is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
• the glass transition temperature can be measured using Rheogel E4000 manufactured by UBM.
• the cured product contained in the laminate of the present invention is a cured product obtained by curing a film containing a cyclized resin or its precursor (also referred to as “specific resin”) and a photosensitive agent.
• the film is preferably obtained by removing the solvent from the resin composition of the present invention, which will be described later, by drying or the like.
• the drying method the same drying method as in the drying step in the method for producing a cured product described later can be mentioned, and preferred embodiments are also the same.
• the film does not have to be one from which the solvent has been completely removed, and may contain the solvent.
• the solvent content in the film can be, for example, 1% by mass or less with respect to the total mass of the film.
• Preferred aspects of the solvent are the same as the preferred aspects of the solvent in the resin composition to be described later.
• the details of the cyclized resin or its precursor, the photosensitive agent, and other components contained in the film are the same as the details of these components in the resin composition of the present invention described below, and the preferred embodiments are also the same.
• the preferred range of the content of each component contained in the film is the same as the preferred range of the content of each component contained in the resin composition, which will be described later, relative to the total solid content of the resin composition. For example, in the film, the content of a certain component relative to the total mass of the film (excluding the mass of the solvent if the film contains a solvent) minus the mass of the resin particles, the low dielectric resin and the inorganic particles is preferred.
• the range is the same as the preferable range of the content of a certain component with respect to the total solid content of the resin composition described later, excluding the content of the resin particles, the low dielectric resin and the inorganic particles.
• the resin composition described later when a preferred aspect of the content of a certain component is described as a ratio to the content of a specific resin, a preferred aspect of the content of that component in the film is the specific resin contained in the film is the same ratio for the content of Preferred aspects of the resin composition and preferred aspects of the film production method will be described later.
• the film is preferably a film formed by a film forming step to be described later.
• the dielectric constant of the film is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.8 or less.
• the lower limit of the dielectric constant is not particularly limited, it is preferably 1.0 or more.
• the dielectric loss tangent of the film is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less.
• the lower limit of the dielectric loss tangent is not particularly limited, and may be zero.
• the relative dielectric constant and dielectric loss tangent are values measured by the same measuring method and measuring conditions as those of the cured product described in the examples below.
• the film preferably contains at least one compound selected from the group consisting of resin particles, a resin having a dielectric constant of 2.7 or less, and inorganic particles.
• the film contains at least one compound selected from the group consisting of resin particles, a resin having a dielectric constant of 2.7 or less (hereinafter also referred to as "low dielectric resin"), and inorganic particles. is preferred.
• the film contains resin particles
• the polarity of the cured product is reduced, and the hygroscopicity and water absorption are reduced, so the deterioration of adhesion after reliability testing (that is, after exposure to high humidity conditions) is suppressed.
• the resin particles are easy to disperse in a specific resin, the particles themselves have good followability, and the followability with metal wiring under reliability tests (i.e., high humidity conditions) can be ensured, which is effective for adhesion. Conceivable.
• the film contains a low-dielectric resin
• the polarity of the cured product is reduced and the hygroscopicity and water absorption are reduced, so the deterioration of adhesion after reliability testing (that is, after exposure to high humidity conditions) is suppressed. It is possible.
• the film contains inorganic particles, it becomes easier to adjust the linear expansion coefficient and elastic modulus to values close to those of the base material and metal wiring by selecting the material, shape, and particle size of the inorganic particles. It is thought that the difference in stress between the base material and metal wiring and the cured product can be suppressed (that is, under high humidity conditions).
• the film preferably further contains resin particles.
• resin particles containing fluorine atoms polystyrene resin particles, hollow polymer resin particles, or polymerizable particles such as methyl methacrylate or styrene may be used. Particles having a reduced dielectric constant based on a monomer are preferred, and resin particles containing fluorine atoms are more preferred.
• the fluorine atom-containing resin in the fluorine atom-containing resin particles is not particularly limited, but is polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, and tetrafluoroethylene.
• ⁇ Propylene copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, ethylene/tetrafluoroethylene copolymer, ethylene/chlorotrifluoroethylene copolymer, tetrafluoroethylene/chlorotrifluoroethylene copolymer A coalescence etc. are mentioned.
• resin particles containing fluorine atoms coated with silica may be used.
• polystyrene resin particles include, but are not limited to, non-crosslinked polystyrene particles, crosslinked polystyrene particles, crosslinked methyl methacrylate-styrene copolymer particles, and crosslinked acrylic-styrene copolymer particles.
• hollow polymer resin particles include, but are not limited to, acrylic-styrene copolymer, polymethyl methacrylate, polyamide, polystyrene, polyvinyl chloride, etc., having a hollow polymer structure.
• particles having a reduced dielectric constant based on a polymerizable monomer such as methyl methacrylate or styrene include Techpolymer manufactured by Sekisui Chemical.
• the shape of the resin particles is not particularly limited, and fibrous, plate-like, scale-like, rod-like, spherical, tube-like, curved plate-like, needle-like and the like can be used without any particular limitation.
• the resin particles are preferably at least one resin particle selected from the group consisting of hollow particles and porous particles.
• the porosity is preferably 15 to 99.5%, more preferably 30 to 98%, and 40 to 92%. is more preferred.
• the dielectric constant of the resin particles is preferably 2.9 or less, more preferably 2.8 or less, and 2.7 or less. is more preferable.
• the lower limit of the dielectric constant is not particularly limited, it can be 1.0 or more.
• the dielectric loss tangent of the resin particles is preferably 0.01 or less, more preferably 0.005 or less, and 0.002 or less. It is even more preferable to have The lower limit of the dielectric loss tangent is not particularly limited, and may be zero.
• the dielectric constant and dielectric loss tangent are values obtained by measuring the dielectric constant and dielectric loss tangent of the compound itself forming the resin particles, respectively, using the same measurement method and measurement conditions as those described in Examples below.
• the particle diameter of the resin particles is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less. Moreover, the particle diameter of the resin particles is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 0.2 ⁇ m or more. The particle size is calculated by the method described in Examples below.
• the resin particles may contain a particulate mixture in which at least two types of particle groups with different particle sizes are mixed.
• the "particle diameter" of a certain particle group is also obtained by the same method as the "particle diameter” of the resin particles.
• small particles are buried between large particles, and the distance between resin particles is reduced and the number of contact points is increased compared to the case where only resin particles with a single diameter are included.
• Improves thermal conductivity For example, when two types of particle groups having different particle sizes are mixed, two peaks are observed in the particle size distribution of the resin particles containing these particle groups. Therefore, by confirming the number of peaks in the particle size distribution of the resin particles, it is possible to confirm how many types of particle groups with different particle diameters are included in the granular mixture of resin particles.
• the peak particle size ratio (ratio of particle sizes corresponding to peak apexes) between at least two peaks is 1.5 to 50. preferable.
• the lower limit is preferably 2 or more, more preferably 4 or more.
• the upper limit is preferably 40 or less, more preferably 20 or less.
• the peak ratio is within the above range, it becomes easy for the small resin particles to occupy the spaces between the large resin particles while preventing the large resin particles from becoming coarse particles.
• the peak intensity ratio of the large particle size peak to the small particle size peak is preferably 0.2 to 5.0.
• the lower limit is preferably 0.2 or more, more preferably 0.5 or more.
• the upper limit is preferably 5.0 or less, more preferably 3.0 or less.
• the resin particles may be electrically insulating, semiconducting, or conductive, but are preferably electrically insulating from the viewpoint of the insulating properties of the cured product.
• the degree of electrical insulation and conductivity is appropriately selected according to the design and purpose.
• the lower limit of the volume resistivity of the resin particles is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more, and 1.0 ⁇ 10 12 ⁇ . ⁇ cm or more is particularly preferable.
• the upper limit of the volume resistivity is not particularly limited, it is preferably 1.0 ⁇ 10 19 ⁇ cm or less, for example.
• the lower limit of the volume resistivity of the resin particles is not particularly limited, but is preferably 1.0 ⁇ 10 ⁇ 7 ⁇ cm or more.
• the upper limit of the volume resistivity is preferably less than 1.0 ⁇ 10 11 ⁇ cm.
• the density of the resin particles is, for example, preferably 20.0 g/cm 3 or less, more preferably 10.0 g/cm 3 or less, and 5.0 g/cm 3 . More preferably: Although the lower limit of the density of the resin particles is not particularly limited, it is preferably 0.5 g/cm 3 or more, for example. In the present specification, when the resin particles have voids or cavities such as porous or hollow particles, the density of the resin particles means the solid content of the components constituting the resin particles. means density.
• the thermal expansion coefficient of the resin particles is preferably 10 ⁇ 10 ⁇ 5 /K or less, more preferably 3 ⁇ 10 ⁇ 5 /K or less.
• the lower limit of the thermal expansion coefficient of the resin particles is not particularly limited, it is preferably 0/K or more, for example.
• the content of resin particles relative to the total solid content of the film is preferably 5% by mass or more, more preferably 10% by mass or more. It is more preferably 15% by mass or more.
• the upper limit of the content is not particularly limited, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
• the resin particles can be used singly or in combination of two or more. When two or more resin particles are used, the total amount thereof is preferably within the above range.
• the film preferably further contains a low dielectric resin.
• the dielectric constant of the low dielectric resin is 2.7 or less, preferably 2.6 or less, and more preferably 2.5 or less.
• the lower limit of the dielectric constant is not particularly limited, it can be 1.0 or more.
• the dielectric loss tangent of the low dielectric resin is preferably 0.01 or less, more preferably 0.005 or less, and 0.002 or less. is more preferable.
• the lower limit of the dielectric loss tangent is not particularly limited, and may be zero.
• the relative dielectric constant and dielectric loss tangent are values obtained by measuring the relative dielectric constant and dielectric loss tangent of the compound itself forming the low dielectric resin, respectively, by the method described in the examples below.
• At least one resin selected from the group consisting of liquid crystal polymers and polyphenylene ethers is preferable as the low dielectric resin from the viewpoint of adhesion after exposure to high humidity conditions.
• the liquid crystal polymer is not particularly limited as long as it exhibits liquid crystallinity, and examples thereof include liquid crystalline polyesters.
• Liquid crystalline polyesters include aromatic polyesters, polyester amides, polyester ethers, polyester carbonates, polyester imides, and the like.
• aromatic polyesters include aromatic polyesters obtained by polymerization of aromatic dicarboxylic acids and aromatic diols, aromatic hydroxycarboxylic acids, and the like.
• polyester synthesized from parahydroxybenzoic acid (PHB), terephthalic acid and 4,4-dihydroxybiphenyl polyester synthesized from PHB, terephthalic acid and ethylene glycol, PHB and 2,6-hydroxynaphthoic acid synthesized polyester and the like. Synthesis methods for these polyesters are not particularly limited as long as they have the same structure.
• the dielectric constant of the low dielectric resin is preferably 2.9 or less, more preferably 2.8 or less, and 2.7. More preferably: Although the lower limit of the dielectric constant is not particularly limited, it can be 1.0 or more. From the viewpoint of adhesion after exposure to high humidity conditions, the dielectric loss tangent of the low dielectric resin is preferably 0.01 or less, more preferably 0.005 or less, and 0.002 or less. is more preferable. The lower limit of the dielectric loss tangent is not particularly limited, and may be zero. The relative dielectric constant and dielectric loss tangent can be measured as the relative dielectric constant and dielectric loss tangent of the low dielectric resin itself, respectively, by the same measuring method and measuring conditions as those described in the examples below.
• the low dielectric resin may be electrically insulating, semiconducting, or conductive, but is preferably electrically insulating from the viewpoint of the insulating properties of the cured product.
• the degree of electrical insulation and conductivity is appropriately selected depending on the design and purpose.
• the lower limit of the volume resistivity of the low dielectric resin is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more, and 1.0 ⁇ 10 12 ⁇ cm or more is particularly preferable.
• the upper limit of the volume resistivity is not particularly limited, it is preferably 1.0 ⁇ 10 19 ⁇ cm or less, for example.
• the lower limit of the volume resistivity of the low-dielectric resin is not particularly limited, but is preferably 1.0 ⁇ 10 ⁇ 7 ⁇ cm or more.
• the upper limit of the volume resistivity is preferably less than 1.0 ⁇ 10 11 ⁇ cm.
• the density of the low dielectric resin is, for example, preferably 20.0 g/cm 3 or less, more preferably 10.0 g/cm 3 or less, and more preferably 5.0 g/cm 3 or less. It is more preferably 3 or less.
• the lower limit of the density of the low dielectric resin is not particularly limited, it is preferably 0.5 g/cm 3 or more, for example.
• the density of the low dielectric resin means means density of solids.
• the coefficient of thermal expansion of the low dielectric resin is preferably 10 ⁇ 10 ⁇ 5 /K or less, more preferably 3 ⁇ 10 ⁇ 5 /K or less.
• the lower limit of the thermal expansion coefficient of the low dielectric resin is not particularly limited, but is preferably 0/K or more, for example.
• the content of the low dielectric resin relative to the total solid content of the film is preferably 1% by mass or more, more preferably 5% by mass or more. , more preferably 10% by mass or more.
• the upper limit of the content is not particularly limited, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
• the low dielectric resin can be used singly or in combination of two or more. When two or more low dielectric resins are used, the total amount thereof is preferably within the above range.
• the film preferably further contains inorganic particles.
• Inorganic particles include particles made of silica, quartz, glass, or ceramics. Examples of silica include fused silica, precipitated silica, fumed silica, colloidal silica, synthetic silica, and the like. Ceramics include alumina, zirconia, barium titanate, hydroxyapatite, silicon nitride, silicon carbide, fluorite, magnesite (magnesium carbonate), perovskite (calcium titanate), talc, mica, kaolin, bentonite, pyroferrite, etc. mentioned. Among these, the inorganic particles are preferably silica particles, more preferably hollow silica particles.
• the shape of the inorganic particles is not particularly limited, and fibrous, plate-like, scale-like, rod-like, spherical, tube-like, curved plate-like, needle-like and the like can be used without any particular limitation.
• the inorganic particles are preferably at least one inorganic particle selected from the group consisting of hollow particles and porous particles, more preferably hollow particles.
• the porosity is preferably 15 to 99.5%, more preferably 30 to 98%, and 40 to 92%. is more preferred.
• Preferred ranges of the relative dielectric constant, dielectric loss tangent and volume resistivity of the inorganic particles are the same as the preferred ranges of the dielectric constant, dielectric loss tangent and volume resistivity of the resin particles described above.
• the relative dielectric constant and dielectric loss tangent can be measured as the relative dielectric constant and dielectric loss tangent of the compound itself forming the inorganic particles, respectively, by the same measuring method and under the same measurement conditions as those described in the examples below.
• the particle diameter of the inorganic particles is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.3 ⁇ m or less.
• the particle diameter of the inorganic particles is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, and even more preferably 0.05 ⁇ m or more. The particle size is calculated by the method described in Examples below.
• the inorganic particles may contain a particulate mixture in which at least two types of particle groups with different particle sizes are mixed.
• the "particle diameter" of a certain particle group is also determined by the same method as the "particle diameter" of the inorganic particles. With such a configuration, small particles are buried between large particles, and the distance between inorganic particles decreases and the number of contact points increases compared to the case where only inorganic particles with a single diameter are included. Improves thermal conductivity. For example, when two types of particle groups having different particle sizes are mixed, two peaks are observed in the particle size distribution of the inorganic particles containing these particle groups. Therefore, by confirming the number of peaks in the particle size distribution of the inorganic particles, it is possible to confirm how many types of particle groups with different particle diameters are included in the particulate mixture of inorganic particles.
• the peak particle size ratio (ratio of particle sizes corresponding to peak apexes) between at least two peaks is 1.5 to 50. preferable.
• the lower limit is preferably 2 or more, more preferably 4 or more.
• the upper limit is preferably 40 or less, more preferably 20 or less.
• the peak ratio is within the above range, it becomes easy for the small-diameter inorganic particles to occupy the spaces between the large-diameter inorganic particles while suppressing the large-diameter inorganic particles from becoming coarse particles.
• the peak intensity ratio of the large particle size peak to the small particle size peak is preferably 0.2 to 5.0.
• the lower limit is preferably 0.2 or more, more preferably 0.5 or more.
• the upper limit is preferably 5.0 or less, more preferably 3.0 or less.
• the inorganic particles may be electrically insulating, semiconducting, or electrically conductive, but are preferably electrically insulating from the viewpoint of the insulating properties of the cured product.
• the degree of electrical insulation and conductivity is appropriately selected according to the design and purpose.
• the lower limit of the volume resistivity of the inorganic particles is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more, and 1.0 ⁇ 10 12 ⁇ . ⁇ cm or more is particularly preferable.
• the upper limit of the volume resistivity is not particularly limited, it is preferably 1.0 ⁇ 10 19 ⁇ cm or less, for example.
• the lower limit of the volume resistivity of the inorganic particles is not particularly limited, but is preferably 1.0 ⁇ 10 ⁇ 7 ⁇ cm or more.
• the upper limit of the volume resistivity is preferably less than 1.0 ⁇ 10 11 ⁇ cm.
• the density of the inorganic particles is, for example, preferably 20.0 g/cm 3 or less, more preferably 10.0 g/cm 3 or less, and 5.0 g/cm 3 . More preferably: Although the lower limit of the density of the inorganic particles is not particularly limited, it is preferably 0.5 g/cm 3 or more, for example. In the present specification, when the inorganic particles have voids or cavities such as porous or hollow particles, the density of the inorganic particles refers to the solid content of the components constituting the inorganic particles. means density.
• the thermal expansion coefficient of the inorganic particles is preferably 10 ⁇ 10 ⁇ 5 /K or less, more preferably 3 ⁇ 10 ⁇ 5 /K or less.
• the lower limit of the thermal expansion coefficient of the inorganic particles is not particularly limited, it is preferably 0/K or more, for example.
• the content of inorganic particles relative to the total solid content of the film is preferably 0.2% by mass or more, and is 2.0% by mass or more. is more preferable, and 10% by mass or more is even more preferable.
• the upper limit of the content is not particularly limited, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 55% by mass or less.
• the inorganic particles can be used singly or in combination of two or more. When two or more inorganic particles are included, the total amount thereof is preferably within the above range.
• the cured product and the metal wiring contained in the laminate are in contact with each other at least partially.
• the laminate may further have a cured product that is not in contact with the metal wiring, or may further have a metal wiring that is not in contact with the cured product. Also, all of the metal wiring may be in contact with the cured product.
• the aspect in which the metal wiring is covered with a cured product is also one of the preferred aspects of the present invention.
• the substrate has a plurality of metal wires
• the metal wires are insulated from each other by a cured product.
• the base material and the cured product are in contact with each other in a region in which the base material does not have the metal wiring.
• the laminate may have only one cured product and one metal wiring, but may have two or more.
• a laminate including at least a layer structure in which four layers, ie, a substrate, a first cured product, a metal layer, and a second cured product are laminated in this order, may be mentioned.
• the base material may be a base material having metal wiring
• the first cured product may be a cured product having a dielectric constant of 3.0 or less, or the first cured product and
• the metal layer may be a substrate having metal wiring
• the second cured product may be a cured product having a dielectric constant of 3.0 or less (in this case, the first cured product and the metal layer are , "a base material having a metal layer as a metal wiring"), or both.
• the metal layer is preferably used as a metal wiring such as a rewiring layer.
• the following configuration is also more preferable.
• Each of the above layers may have the same composition, shape, film thickness, etc., or may differ from each other.
• At least one of the above-mentioned cured products may be a cured product having a relative dielectric constant of 3.0 or less, or all of them may be cured products having a relative dielectric constant of 3.0 or less.
• the invention also discloses a device comprising the laminate of the invention. Moreover, this invention also discloses the manufacturing method of the semiconductor device containing the manufacturing method of the hardened
• the resin composition of the present invention contains a cyclized resin or a precursor thereof and a photosensitizer, and the cured film of the resin composition has a dielectric constant of 3.0 or less.
• the dielectric constant is preferably 2.9 or less, more preferably 2.8 or less.
• the lower limit of the dielectric constant is not particularly limited, it is preferably 1.0 or more.
• the dielectric loss tangent of the cured film made of the resin composition is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less.
• the lower limit of the dielectric loss tangent is not particularly limited, and may be zero.
• the dielectric constant and dielectric loss tangent of the cured film made of the resin composition are measured by the following methods.
• the resin composition is applied to a silicon wafer having an oxide film (SiO 2 ) formed on the surface with a thickness of 20 ⁇ m, dried at 100° C. for 5 minutes, and heated at 230° C. for 180 minutes to prepare a cured film,
• the dielectric constant and dielectric loss tangent of a single film of the composition obtained by immersing the composition in hydrogen fluoride and peeling off the cured film are measured.
• the dielectric constant and dielectric loss tangent of the single film can be measured according to the methods described in Examples below.
• the dielectric constant of the film made of the resin composition before curing is preferably 3.0 or less, more preferably 2.9 or less, and more preferably 2.8 or less.
• the lower limit of the dielectric constant is not particularly limited, it is preferably 1.0 or more.
• the dielectric loss tangent of the film made of the resin composition before curing is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less.
• the lower limit of the dielectric loss tangent is not particularly limited, and may be zero.
• the dielectric constant and dielectric loss tangent of the film made of the resin composition before curing are measured by the following methods.
• the resin composition is applied to a silicon wafer having an oxide film (SiO 2 ) formed thereon to a thickness of 20 ⁇ m and dried at 100° C. for 5 minutes to form a film.
• the dielectric constant and dielectric loss tangent of the film are measured.
• the relative dielectric constant and dielectric loss tangent are the values measured by the same measuring method and measuring conditions as the measuring method for the cured product described in the example described later for the relative dielectric constant and dielectric loss tangent of the film before curing, respectively. .
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of resin particles, a resin having a dielectric constant of 2.7 or less (low dielectric resin), and inorganic particles.
• a preferred embodiment of the resin particles, the resin having a dielectric constant of 2.7 or less, and the inorganic particles is a preferred embodiment of the resin particles, the resin having a dielectric constant of 2.7 or less, and the inorganic particles contained in the above-described film. is similar to
• the preferable contents of the resin particles, the resin having a dielectric constant of 2.7 or less, and the inorganic particles are the resin particles, the resin having a dielectric constant of 2.7 or less, and the inorganic particles contained in the above-described film.
• the description of "total solid content of the film" is read as "total solid content of the resin composition”.
• the resin composition of the present invention 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 its main chain structure.
• the main chain represents the relatively longest connecting chain in the resin molecule.
• cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
• a precursor of a cyclized resin is a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin.
• a resin that becomes a cyclized resin by forming a ring structure is more preferable.
• Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention contains, as a specific resin, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, and polyamideimide precursors. It preferably contains a resin (specific resin).
• the resin composition of the present invention preferably contains 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 described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred.
• a sensitizer described later can be included.
• a negative photosensitive film is formed from the resin composition of the present invention.
• the specific resin may have a polarity conversion group such as an acid-decomposable group.
• the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
• polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
• a 1 and A 2 each independently represent an oxygen atom or -NH-
• R 111 represents a divalent organic group
• R 115 represents a tetravalent organic group
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
• a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
• R 111 in formula (2) represents a divalent organic group.
• divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups 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 is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
• the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the ring member hydrocarbon group is a hetero atom.
• may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred.
• Ar is each independently an aromatic group
• L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally 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. Preferred ranges for these are as described above.
• R 111 is preferably derived from a diamine.
• Diamines used in the production of polyimide precursors 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. Specifically, 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 is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
• * represents a binding site with other structures.
• diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; ,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 or isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3, 3,3
• diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
• diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are preferably used.
• R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
• Ar is each 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.
• R 111 is preferably a divalent organic group represented by the following formula (51) or (61).
• a divalent organic group represented by Formula (61) is more preferable.
• Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
• the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
• R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a binding site to the nitrogen atom in formula (2) show.
• Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
• R 111 contains a polycyclic aromatic ring structure.
• Polycyclic aromatic ring structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, acenaphthylene ring structures, phenylene ether structures, and the like. are mentioned, but are not limited to these.
• R 111 preferably contains at least one of a polyphenyl structure and a fluorene ring structure.
• R 115 in formula (2) 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 (6) is more preferable.
• each * independently represents a binding site to another structure.
• R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from combinations thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, -C( It is more preferably a divalent group selected from the group consisting of CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
• R 115 contains a polycyclic aromatic ring structure.
• Polycyclic aromatic ring structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, acenaphthylene ring structures, phenylene ether structures, and the like. are mentioned, but are not limited to these.
• R 115 preferably contains at least one of a polyphenyl structure and a fluorene ring structure.
• R 115 specifically includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
• the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types thereof, as the structure corresponding to R115 .
• the tetracarboxylic dianhydride is preferably represented by the following formula (O).
• R 115 represents a tetravalent organic group.
• the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
• tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride,
• tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
• R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
• R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
• At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
• the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
• the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done.
• a group having an ethylenically unsaturated bond is preferred.
• Groups 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., vinylphenyl group), and a (meth)acrylamide group.
• a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
• R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
• * represents a binding site with another structure.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
• R 201 examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
• alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2
• a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
• the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
• the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
• the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
• the said alkylene group may have a substituent.
• Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
• the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
• a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
• the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
• the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
• tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
• R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
• acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
• the polyimide precursor preferably has a fluorine atom in its structure.
• the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
• the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
• a 1 and A 2 represent an oxygen atom
• R 111 and R 112 each independently represent a divalent organic group
• R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group
• at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
• a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same.
• R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
• the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. Further, it may contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
• the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
• the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
• the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
• the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
• the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are within the ranges described above.
• the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyimide refers to a polyimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
• the term "main chain” refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term “side chain” refers to the other linking chain.
• the polyimide preferably has a fluorine atom.
• a fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
• the amount of fluorine atoms with respect to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
• the polyimide preferably has a silicon atom.
• a silicon atom for example, is preferably contained in R 131 in a repeating unit represented by formula (4) described later, and R 131 in a repeating unit represented by formula (4) described later is an organically modified (poly ) is more preferably contained as a siloxane structure.
• the silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 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 its main chain or in a side chain, preferably in a side chain.
• the ethylenically unsaturated bond preferably has radical polymerizability.
• the ethylenically unsaturated bond is preferably contained in R 132 in a repeating unit represented by the formula (4) described later, or R 131 in a repeating unit represented by the formula (4) described later.
• the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and ethylene It is more preferably included as a group having a polyunsaturated bond.
• the group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).
• R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
• R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C( ⁇ O)O—, —O(C ⁇ O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a group in which two or more of these are combined.
• the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
• an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
• R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
• L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are combined
• X represents an oxygen atom or a sulfur atom
• * represents a bonding site with another structure
• ⁇ represents a bonding site with the oxygen atom to which R 21 in formula (IV) bonds.
• a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
• X is preferably an oxygen atom.
• * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
• the structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
• the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
• the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.
• a polyimide having a hydroxy group such as a phenolic hydroxy group
• a compound having a glycidyl group and an ethylenically unsaturated bond e.g., glycidyl methacrylate, etc.
• * represents a binding site with another structure, preferably a binding site with the main chain of polyimide.
• the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.
• Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
• Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
• a polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
• the amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
• the polyimide may have a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
• Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.
• the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable. Also, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development” described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH.
• the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
• an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable from the viewpoint of both storage stability and developability.
• the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka.
• pKa is a value calculated by ACD/ChemSketch (registered trademark).
• the acid group is a polyvalent acid such as phosphoric acid
• the above pKa is the first dissociation constant.
• the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
• a phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
• the amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).
• R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
• the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in Formula (4-1)
• R 133 is a polymerizable group, and other groups are the same as in formula (4).
• Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
• R 131 represents a divalent organic group.
• the divalent organic group are the same as those of R 111 in formula (2), and the preferred range is also the same.
• R 131 also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R 111 in formula (2) of the polyimide precursor.
• R 131 is preferably a diamine residue having at least two alkylene glycol units in its main chain from the viewpoint of more effectively suppressing warping during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably the above diamine, which does not contain an aromatic ring. is.
• Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.
• R 132 represents a tetravalent organic group.
• examples of the tetravalent organic group are the same as those for R 115 in formula (2), and the preferred range is also the same.
• four bonds of a tetravalent organic group exemplified as R 115 combine with four —C( ⁇ O)— moieties in the above formula (4) to form a condensed ring.
• R 132 includes a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride.
• a specific example is the example of R 115 in formula (2) of the polyimide precursor. From the viewpoint of strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 has an OH group. More specifically, R 131 is 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are preferred examples. and more preferable examples of R 132 are the above (DAA-1) to (DAA-5).
• the polyimide preferably has a fluorine atom 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.
• the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
• the main chain end of the polyimide is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. preferably.
• a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound.
• monoamines it is more preferable to use monoamines, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7 -aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-
• the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulation properties, etc. of the resulting organic film. More preferably, it is 90% or more.
• the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
• the imidization rate is measured, for example, by the method described below. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C.
• the polyimide may contain repeating units represented by the above formula (4 ) that all contain one type of R 131 or R 132 , and the above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.
• polyimide for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor
• the weight average molecular weight (Mw) of polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties (e.g. elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
• the number average molecular weight (Mn) of polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
• the polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the polyimide molecular weight dispersity is not particularly defined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the resin composition contains a plurality of types of polyimide as the specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above-mentioned plural types of polyimides as one resin are within the ranges described above.
• polybenzoxazole precursor Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it 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. show.
• R 123 and R 124 each have the same meaning as R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
• R 121 represents a divalent organic group.
• the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferred.
• the aliphatic group a linear aliphatic group is preferred.
• 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.
• a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
• the dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred.
• 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, and 4 to 15 is more preferred, and 5-10 is particularly preferred.
• the linear aliphatic group is preferably an alkylene group.
• Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedi
• Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
• the dicarboxylic acid containing an aromatic group the following dicarboxylic acid having an aromatic group is preferable, and the following dicarboxylic acid consisting of only a group having an aromatic group and two -COOH is more preferable.
• A is -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 -, and -C(CH 3 ) 2 - represents a divalent group selected from the group consisting of * independently represents a binding site to another structure.
• dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
• R 122 represents a tetravalent organic group.
• the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same.
• R 122 is also preferably a group derived from a bisaminophenol derivative.
• bisaminophenol derivatives having the following aromatic groups are preferred.
• X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # respectively represent other structures and represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.
• R 122 is also preferably a structure represented by the above formula.
• any two of the total four * and # are binding sites with the nitrogen atom to which R 122 in formula (3) binds, and Another two are preferably bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and two * are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded. and two #s are binding sites to the nitrogen atom to which R 122 in formula (3) binds, or two * are binding sites to the nitrogen atom to which R 122 in formula (3) binds and two #s are more preferably binding sites to the oxygen atom to which R 122 in formula (3) binds, and two * are the oxygen to which R 122 in formula (3) binds. More preferably, it is a bonding site with an atom and two #s are bonding sites with a nitrogen atom to which R 122 in formula (3) is bonded.
• the bisaminophenol derivative is also preferably a compound represented by Formula (As).
• R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc).
• R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
• R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
• R 1 is alkylene or substituted alkylene.
• alkylene and substituted alkylene for R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which —CH 2 — and —CH(CH 3 ) -, -C(CH 3 ) 2 - have sufficient solubility in solvents while maintaining the effect of high i-line transparency and high cyclization rate when cured at low temperature. It is more preferable in that a polybenzoxazole precursor having excellent properties can be obtained.
• the polybenzoxazole precursor may also contain other types of repeating units in addition to the repeating units of formula (3) above.
• the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that warping due to ring closure can be suppressed.
• Z has an a structure and a b structure
• R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
• At least one of R 3s , R 4s , R 5s and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
• Polymerization of a structure and b structure may be block polymerization or random polymerization.
• the mol % of the Z moiety is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.
• preferred Z include 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.
• tetracarboxylic acid residues include those of R 115 in formula (2).
• the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, 000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
• the molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
• the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.
• the resin composition contains multiple types of polybenzoxazole precursors as specific resins
• the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polybenzoxazole precursor are within the above ranges. preferable. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the above plural kinds of polybenzoxazole precursors as one resin are within the ranges described above.
• Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group.
• a radically polymerizable group is preferred.
• it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.
• R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
• the polar conversion group such as a polymerizable group or an acid-decomposable group
• the polar conversion group may be located on at least one of R 133 and R 134 . It may be positioned at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2).
• R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups are the same as in formula (X).
• the polarity conversion group such as a polymerizable group or an acid-decomposable group is synonymous with the polymerizable group described above for the polymerizable group possessed by the polyimide precursor.
• R 133 represents a divalent organic group.
• Divalent organic groups include aliphatic groups and aromatic groups.
• a specific example is the example of R 121 in formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of R121 .
• R 134 represents a tetravalent organic group.
• Tetravalent organic groups include examples of R 122 in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of R122 .
• four bonds of a tetravalent organic group exemplified as R 122 combine with the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring.
• R 134 when R 134 is the following organic group, it forms the structure below. In the structures below, each * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X).
• Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more.
• the upper limit is not particularly limited, and may be 100%.
• the oxazolization rate is measured, for example, by the method described below.
• An infrared absorption spectrum of polybenzoxazole is measured to obtain a peak intensity Q1 near 1650 cm ⁇ 1 which is an absorption peak derived from the amide structure of the precursor.
• the polybenzoxazole may contain repeating units of the above formula (X) that all contain one type of R 131 or R 132 , or may contain repeating units of the above formula (X) that contain two or more different types of R 131 or R 132 ) repeating units.
• the polybenzoxazole may also contain other types of repeating units in addition to the repeating units of formula (X) above.
• Polybenzoxazole is obtained by, for example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor. , which is obtained by oxazolating it using a known oxazolating reaction method.
• a dicarboxylic acid an active ester type dicarboxylic acid derivative pre-reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield.
• the weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000.
• the weight average molecular weight is particularly preferably 20,000 or more.
• the weight average molecular weight of at least one kind of polybenzoxazole is within the above range.
• the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. be.
• the polybenzoxazole has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
• the upper limit of the polybenzoxazole molecular weight dispersity is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and even more preferably 2.3 or less.
• 2.2 or less is even more preferable.
• the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polybenzoxazole are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole as one resin are within the ranges described above.
• the polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
• R 117 represents a trivalent organic group
• R 111 represents a divalent organic group
• a 2 represents an oxygen atom or —NH—
• R 113 represents a hydrogen atom or a monovalent represents an organic group.
• R 117 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
• the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
• alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
• halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
• the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
• the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
• preferred halogenated alkylene groups include (ditrifluoromethyl)methylene groups and the like.
• the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
• R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
• a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be anhydrided.
• the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one of these tricarboxylic acid compounds may be used, or two or more thereof may be used.
• the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a Tricarboxylic acid compounds containing 6 to 20 aromatic groups, or groups in which two or more of these are combined via a single bond or a linking group are preferable, and aromatic groups having 6 to 20 carbon atoms, or carbon atoms via a single bond or a linking group are preferred. More preferred are tricarboxylic acid compounds containing groups in which two or more aromatic groups of numbers 6 to 20 are combined.
• tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
• (or phthalic anhydride) and benzoic acid are a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group
• Linked compounds and the like are included.
• These compounds may be compounds in which two carboxy groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride). There may be.
• R 111 , A 2 and R 113 have the same meanings as R 111 , A 2 and R 113 in formula (2) above, and preferred embodiments are also the same.
• Polyamideimide precursors may further comprise other repeating units.
• Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).
• R 116 represents a divalent organic group and R 111 represents a divalent organic group.
• R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
• the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
• alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
• halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
• the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
• the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
• preferred halogenated alkylene groups include (ditrifluoromethyl)methylene groups and the like.
• the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
• R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
• a compound having two carboxy groups is called a dicarboxylic acid compound
• a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
• the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
• linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids examples include acid dihalide compounds.
• One of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more thereof may be used.
• the dicarboxylic acid compound or dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms.
• a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms.
• dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9
• R 111 has the same definition as R 111 in formula (2) above, and preferred embodiments are also the same.
• the polyamideimide precursor preferably has a fluorine atom in its structure.
• the content of fluorine atoms in the polyamideimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used.
• An aspect in which the total content of units is 50 mol % or more of all repeating units is exemplified.
• the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
• the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are the repeating units represented by the formula (PAI-2), represented by the formula (PAI-1).
• the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is An embodiment in which it is 50 mol % or more of all repeating units is mentioned.
• the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
• the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), or represented by formula (PAI-1) may be any of the repeating units provided.
• the weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. .
• the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
• the polyamidoimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly defined, it is 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 degree of dispersion of at least one type of polyamideimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.
• the polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution.
• a polyamideimide that dissolves 5 g or more is preferable, and a polyamideimide that dissolves 1.0 g or more is more preferable.
• the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
• the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
• the polyamideimide preferably has a fluorine atom.
• a fluorine atom is preferably contained in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later, and is preferably contained in a repeating unit represented by formula (PAI-3) described later It is more preferably contained in R 117 or R 111 as a fluorinated alkyl group.
• the amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of polyamideimide.
• the polyamideimide may have an ethylenically unsaturated bond.
• the polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, preferably in the side chain.
• the ethylenically unsaturated bond preferably has radical polymerizability.
• the ethylenically unsaturated bond is preferably contained in R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later, and the repeating unit represented by formula (PAI-3) described later.
• R 117 or R 111 It is more preferably contained as a group having an ethylenically unsaturated bond in R 117 or R 111 in .
• Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.
• the amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.
• Polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.
• the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the above polymerizable groups other than the ethylenically unsaturated bond in the polyimide.
• a polymerizable group other than an ethylenically unsaturated bond is preferably included in R 111 in a repeating unit represented by formula (PAI-3) described later, for example.
• the amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.
• -Polarity conversion group- Polyamideimide may have a polarity converting group such as an acid-decomposable group.
• the acid-decomposable group in polyamideimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
• the acid value of the polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g, from the viewpoint of improving developability. g or more is more preferable. Also, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
• the acid value of the polyamideimide is preferably 2 to 35 mgKOH/g, 3 ⁇ 30 mg KOH/g is more preferred, and 5 to 20 mg KOH/g is even more preferred.
• the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
• the acid group contained in the polyamideimide the same groups as the acid group in the polyimide described above can be mentioned, and the preferred embodiments are also the same.
• the polyamideimide preferably has a phenolic hydroxy group.
• Polyamideimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
• a phenolic hydroxy group is preferably included in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later.
• the amount of phenolic hydroxy groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.
• the polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it preferably contains a repeating unit represented by the following formula (PAI-3).
• R 111 and R 117 have the same definitions as R 111 and R 117 in formula (PAI-2), and preferred embodiments are also the same.
• the polymerizable group may be located at least one of R 111 and R 117 , or may be located at the end of the polyamideimide.
• the main chain end of the polyamideimide is blocked with a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• Preferred aspects of the terminal blocker are the same as the preferred aspects of the terminal blocker in the polyimide described above.
• the imidization rate (also referred to as "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. , more preferably 90% or more.
• the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
• the imidization rate is measured by the same method as the ring closure rate of the polyimide described above.
• Polyamideimide may contain repeating units represented by the above formula (PAI-3), all of which contain one type of R 111 or R 117 , and two or more different types of R 131 or R 132 . It may contain a repeating unit represented by the above formula (PAI-3). Moreover, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).
• Polyamideimide is, for example, a method of obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or stopping the imidization reaction in the middle and partially imidizing the imide structure and a method of partially introducing an imide structure by blending a completely imidized polymer with its polyamideimide precursor.
• the weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Further, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000. .
• the polyamidoimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the polyamidoimide molecular weight dispersity is not particularly defined, it is 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 degree of dispersion of at least one type of polyamideimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide as one resin are within the above ranges.
• Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, then a method of reacting in the presence of a diamine and a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
• the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferable.
• the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
• 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.
• organic solvent In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
• the organic solvent can be appropriately determined according to the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, and the like. is exemplified.
• a basic compound In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction.
• One type of basic compound may be used, or two or more types may be used.
• the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
• terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties.
• Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
• Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
• Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amin
• Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable.
• Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. is mentioned.
• Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
• the process for producing a polyimide precursor or the like may include a step of depositing a solid. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as re-dissolving, re-precipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
• the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more with respect to the total solid content of the resin composition excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles, It is more preferably 30% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more.
• the content of the resin in the resin composition of the present invention is 99.5% by mass or less with respect to the mass of the total solid content of the resin composition excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles.
• the resin composition of the present invention is preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less.
• the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains at least two resins.
• the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
• the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a precursor.
• the resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins").
• Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
• a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
• a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
• the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
• the content of the other resins is 0 with respect to the mass obtained by subtracting the mass of the resin particles, the low dielectric resin and the inorganic particles from the total solid content of the resin composition. It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 1% by mass or more, even more preferably 2% by mass or more, and 5% by mass or more. It is more preferable that the content is 10% by mass or more.
• the content of the other resin in the resin composition of the present invention is 80% by mass or less with respect to the mass of the total solid content of the resin composition excluding the mass of the resin particles, the low dielectric resin and the inorganic particles.
• the content of other resins may be low.
• the content of the other resin is preferably 20% by mass or less with respect to the mass of the total solid content of the resin composition excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles. It is more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less.
• the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
• the resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
• the resin composition of the present invention also preferably contains a dielectric constant adjusting compound.
• the dielectric constant of the cured product obtained from the resin composition of the present invention can be lowered.
• the dielectric constant adjusting compound include a compound containing an aromatic polycyclic structure, a compound containing a fluorine atom, a compound containing a siloxane group, and the like.
• Compounds containing an aromatic polycyclic structure include compounds containing an aromatic polycyclic structure such as a fluorene skeleton and a polyphenylene skeleton.
• Compounds having a fluorine atom include 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and the like.
• Compounds having a siloxane group include compounds containing a siloxane group derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and the like.
• the dielectric constant adjusting compound preferably has a dielectric constant lower than 3.0 when the film is formed by itself, more preferably 2.8 or less, and 2.6 or less. is more preferable.
• the lower limit of the dielectric constant is not particularly limited, and may be 0 or more.
• the dielectric loss tangent of the film formed from the compound is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.002 or less.
• the lower limit of the dielectric loss tangent is not particularly limited as long as it is 0 or more.
• the resin composition of the present invention preferably contains a compound containing a polymerizable group and an aromatic polycyclic structure, and more preferably contains a compound having a polymerizable group and a fluorene skeleton.
• the dielectric constant of the compound is preferably smaller than that of the specific resin contained in the resin composition.
• the difference between the relative dielectric constant when the film is formed from the resin and the relative dielectric constant when the film is formed from the compound is preferably 0.2 or more, and is 0.4 or more. is more preferred.
• the aromatic group in the compound having an aromatic group may be monocyclic or polycyclic, preferably polycyclic, more preferably condensed ring.
• aromatic polycyclic structures include polyphenyl structures such as biphenyl structures and terphenyl structures, naphthalene ring structures, phenanthrene ring structures, anthracene ring structures, pyrene ring structures, fluorene ring structures, and acenaphthylene ring structures. is not limited to
• the resin composition of the present invention preferably contains a polymerizable compound.
• Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
• the resin composition of the present invention preferably contains a radical cross-linking agent.
• a radical cross-linking agent is a compound having a radically polymerizable group.
• the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
• Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
• the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
• the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more.
• the radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
• the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6.
• the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
• the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
• radical cross-linking agent examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
• addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional is also preferably used.
• addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups
• substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols.
• paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
• the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
• Compounds having a boiling point of 100° C. or higher under normal pressure include compounds described in paragraph 0203 of International Publication No. 2021/112189. The contents of which are incorporated herein.
• Preferred radical cross-linking agents other than those described above include radically polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189. The contents of which are incorporated herein.
• dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku ( Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and their (meth)acryloyl groups are ethylene glycol,
• radical cross-linking agents examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd.
• DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation) etc.
• radical cross-linking agents examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, 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.
• compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also
• the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
• a radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable.
• the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound.
• Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
• the acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
• the resin composition preferably uses a bifunctional methacrylate or acrylate.
• Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate.
• PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
• a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product).
• Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
• N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam
• allyl glycidyl ether are preferably used.
• the monofunctional radical cross-linking agent a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
• Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
• a radical cross-linking agent When a radical cross-linking agent is contained, its content is more than 0% by mass and 60% by mass with respect to the total solid content of the resin composition of the present invention, with respect to the mass excluding the content mass of the resin particles, the low dielectric resin and the inorganic particles. % or less. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
• a single radical cross-linking agent may be used alone, or a mixture of two or more may be used. When two or more are used in combination, the total amount is preferably within the above range.
• the resin composition of the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
• the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them.
• the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds or reaction products thereof in the composition. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
• the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
• a photoacid generator or a photobase generator in the exposure step.
• cross-linking agents compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group and an alkoxymethyl group are preferred.
• a compound having a structure in which at least one group selected from the group consisting of groups is directly bonded to a nitrogen atom is more preferable.
• cross-linking agents include, for example, amino group-containing compounds such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which are reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atoms of the amino groups are converted into acyloxymethyl groups, methylol groups,
• a compound having a structure substituted with an ethylol group or an alkoxymethyl group can be mentioned.
• the method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
• a melamine-based crosslinking agent is a melamine-based crosslinking agent
• a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent
• an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent.
• a cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.
• an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or 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, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
• the total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
• the molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
• R 100 represents an alkyl group or an acyl group.
• R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
• Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
• X represents a single bond or a divalent organic group
• each R 104 independently represents an alkyl group or an acyl group
• R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
• R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
• R 5 in the group represented by —C(R 4 ) 2 COOR 5 a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
• R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
• R 36 and R 37 may combine with each other to form a ring.
• alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
• the alkyl group may be linear or branched.
• a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
• the cycloalkyl group may have 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, more preferably a phenyl group.
• an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
• the 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 the preferred embodiments of the alkyl and aryl groups described above.
• the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
• 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 is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.
• the compound having at least one group selected from the group consisting of acyloxymethyl group, methylol group, ethylol group and alkoxymethyl group includes at least one group selected from the group consisting of urea bond and urethane bond.
• compounds having A preferred embodiment of the above compound is the above-described crosslinking except that the polymerizable group is not a radically polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group and an alkoxymethyl group. It is the same as the preferred embodiment of agent U.
• 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.
• Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds 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 a commercially available one or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
• melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
• urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol.
• Uril 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, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril; urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated
• benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
• tetramethoxymethylated benzoguanamine monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.
• the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
• Compounds to which a seed group is directly attached are also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate.
• suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
• DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another cross-linking agent.
• Epoxy compound (compound having an epoxy group) -
• the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
• the epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warpage of the resin composition of the present invention.
• the epoxy compound preferably contains a polyethylene oxide group.
• the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.
• epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether.
• alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins
• polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether
• epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like.
• Epiclon (registered trademark) 850-S Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Jamaicaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark)
• n is an integer of 1-5 and m is an integer of 1-20.
• n 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.
• oxetane compound compound having an oxetanyl group
• the oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned.
• Aron oxetane series manufactured by Toagosei Co., Ltd. eg, OXT-121, OXT-221
• OXT-121, OXT-221 can be suitably used, and these can be used alone or in combination of two or more. good.
• a benzoxazine compound (compound having a benzoxazolyl group)-
• a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
• benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.
• the content of the other cross-linking agent is preferably 0.1 to 30% by mass based on the total solid content of the resin composition of the present invention, excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles. , more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
• Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.
• the resin composition of the present invention contains a photosensitizer.
• the photosensitive agent include photopolymerization initiators, photoacid generators, and the like, and preferably contain a photopolymerization initiator, and more preferably contain a radical photopolymerization initiator.
• the resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
• the radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred.
• the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
• any known compound can be used as the photoradical polymerization initiator.
• halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
• acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
• ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein.
• Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
• a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. 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. incorporated.
• ⁇ - ⁇ Omnirad 184 ⁇ Omnirad 1173 ⁇ Omnirad 2959 ⁇ Omnirad 127( ⁇ IGM Resins B.V. ⁇ ) ⁇ IRGACURE 184(IRGACURE ⁇ ) ⁇ DAROCUR 1173 ⁇ IRGACURE 500 ⁇ IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
• ⁇ -Aminoketone initiators include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
• acylphosphine oxide-based initiators for example, compounds described in paragraphs 0161 to 0163 of WO2021/112189 can also be preferably used. The contents of which are incorporated herein.
• the photoradical polymerization initiator is more preferably an oxime compound.
• an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
• Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
• oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
• Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
• an oxime compound an oxime-based radical photopolymerization initiator
• DFI-091 manufactured by Daito Chemix Co., Ltd.
• SpeedCure PDO manufactured by SARTOMER ARKEMA
• an oxime compound having the following structure can be used.
• photoradical polymerization initiators examples include oxime compounds having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, and oximes having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring.
• Compounds, oxime compounds having fluorine atoms can also be used. The contents of which are incorporated herein.
• an oxime compound having a nitro group an oxime compound having a benzofuran skeleton, and a substituent having a hydroxy group on the carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021/020359 are used. Bound oxime compounds can also be used. The contents of which are incorporated herein.
• an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
• the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
• a benzoyl group may have a substituent.
• substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
• a sulfanyl group or an amino group is more preferred.
• the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
• R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
• R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
• R X12 is an electron-withdrawing group
• R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
• oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
• oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
• photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
• More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds.
• At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
• radical photopolymerization initiator compounds described in paragraphs 0175 to 0179 of International Publication No. 2021/020359 can be used. The contents of which are incorporated herein.
• radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
• a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
• the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
• Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
• the content thereof is 0.1 to 30% by mass based on the total solid content of the resin composition of the present invention, excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles. preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
• the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
• Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.
• Sensitizers include, for example, 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-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole,
• the content of the sensitizer is 0.01 to 0.01 with respect to the mass of the total solid content of the resin composition excluding the mass of the resin particles, the low dielectric resin and the inorganic particles. It is preferably 20% by mass, more preferably 0.1 to 15% by mass, even more preferably 0.5 to 10% by mass.
• the sensitizers may be used singly or in combination of two or more.
• the resin composition of the present invention may contain a chain transfer agent.
• the chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684.
• Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer )
• Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
• thiol compounds can be preferably used.
• chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
• the content of the chain transfer agent is the total solid content of the resin composition of the present invention minus the content of the resin particles, the low dielectric resin and the inorganic particles. It 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.
• One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a photoacid generator.
• a photoacid generator is 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 a photoacid generator capable of generating an acid upon exposure.
• generated acids include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric monoesters, phosphoric diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, Sulfonamide and the like are preferred.
• Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salt compounds.
• Organic halogen compounds, oxime sulfonate compounds and onium salt compounds are preferred from the viewpoint of sensitivity and storage stability, and oxime esters are preferred from the viewpoint of the mechanical properties of the film to be formed.
• quinonediazide compounds include monovalent or polyvalent hydroxy compounds in which quinonediazide sulfonic acids are ester-bonded, monovalent or polyvalent amino compounds in which quinonediazide sulfonic acids are bonded via sulfonamides, and polyhydroxypolyamino compounds. Examples thereof include quinonediazide sulfonic acids bound by ester bonds and/or sulfonamides. Although not all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may be substituted with quinonediazide, it is preferred that 40 mol % or more of all functional groups on average be substituted with quinonediazide. .
• 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, BisOCP-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
• amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.
• polyhydroxypolyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto. .
• the quinonediazide compound preferably contains a phenol compound and an ester with a 4-naphthoquinonediazide sulfonyl group. This makes it possible to obtain higher sensitivity to i-line exposure and higher resolution.
• the content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin.
• a sensitizer or the like may be added as necessary.
• the photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound").
• the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. 105) is preferably an oxime sulfonate compound.
• X3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple X3 's, they may be the same or different.
• the alkyl group and alkoxy group in X3 above may have a substituent.
• the alkyl group for X 3 is preferably a C 1-4 linear or branched alkyl group.
• the alkoxy group for X 3 above is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
• halogen atom for X3 a chlorine atom or a fluorine atom is preferable.
• m3 represents an integer of 0 to 3, preferably 0 or 1.
• R 34 represents an alkyl group or an aryl 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, a carbon It is preferably a halogenated alkoxy group of number 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
• W is 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; group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
• m3 is 3
• X 3 is a methyl group
• the substitution position of X 3 is the ortho position
• R 34 is a linear alkyl group having 1 to 10 carbon atoms
• Compounds with a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group are particularly preferred.
• oxime sulfonate compound represented by formula (OS-1) are described in paragraph numbers 0064 to 0068 of JP-A-2011-209692 and paragraph numbers 0158-0167 of JP-A-2015-194674.
• the following compounds are exemplified, the contents of which are incorporated herein.
• R s1 represents an alkyl group, an aryl group or a heteroaryl group
• each R s2 which may be present in plurality, is independently a hydrogen atom, an alkyl group, or an aryl represents a group or a halogen atom
• each R s6 which may be present in plurality independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
• Xs represents O or S.
• ns represents 1 or 2
• ms represents an integer of 0-6.
• an alkyl group preferably having 1 to 30 carbon atoms
• an aryl group preferably having 6 to 30 carbon atoms
• a heteroaryl group preferably having 6 to 30 carbon atoms represented by R s1 Numbers 4 to 30 are preferable
• R s1 Numbers 4 to 30 may have a known substituent as long as the effects of the present invention can be obtained.
• R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , a hydrogen atom or an alkyl group.
• One or two of Rs2 which may be present in the compound at least two, are preferably an alkyl group, an aryl group, or a halogen atom, and more preferably one is an alkyl group, an aryl group, or a halogen atom.
• one is an alkyl group and the rest are hydrogen atoms.
• the alkyl group or aryl group represented by R s2 may have a known substituent as long as the effects of the present invention can be obtained.
• Xs represents O or S, preferably O.
• the ring containing Xs as a ring member is a 5- or 6-membered ring.
• ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 is preferred.
• the alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R s6 are substituents. may have.
• ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0 is particularly preferred.
• the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
• the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS -108) or a compound represented by the formula (OS-109).
• R t1 represents an alkyl group, an aryl group or a heteroaryl group
• R t7 represents a hydrogen atom or a bromine atom
• R t8 represents a hydrogen atom, the number of carbon atoms 1 to 8 alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group
• R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
• t2 represents a hydrogen atom or a methyl group.
• R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
• R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group. or represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.
• R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.
• R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
• the oximes may have either one of the three-dimensional structures (E, Z) or may be a mixture.
• Specific examples of the oxime sulfonate compounds represented by the formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs of JP-A-2015-194674. Compounds described in numbers 0168-0194 are exemplified, the contents of which are incorporated herein.
• oximesulfonate compound containing at least one oximesulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
• R u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, It represents an aryl group or a heteroaryl group.
• An aspect in which Ru9 is a cyano group or an aryl group is more preferred, and an aspect in which Ru9 is a cyano group, a phenyl group or a naphthyl group is even more preferred.
• R u2a represents an alkyl group or an aryl group.
• Xu is -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 —, and R u5 to R u7 each independently represent an alkyl group or an aryl group.
• R u1 to R u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group. , an arylcarbonyl group, an amido group, a sulfo group, a cyano group or an aryl group.
• Two of R u1 to R u4 may each combine to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
• R u1 to R u4 are preferably hydrogen atoms, halogen atoms or alkyl groups, and an aspect in which at least two of R u1 to R u4 are bonded to each other to form an aryl group is also preferable. Among them, an aspect in which all of R u1 to R u4 are hydrogen atoms is preferable. Any of the substituents described above may further have a substituent.
• the compound represented by formula (OS-101) is more preferably a compound represented by formula (OS-102).
• the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
• Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195-0207 of JP-A-2015-194674. and the contents of which are incorporated herein.
• the following b-9, b-16, b-31 and b-33 are preferred.
• 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.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. can be done.
• organic halogenated compounds examples include compounds described in paragraphs 0042 to 0043 of JP-A-2015-087409. The contents of which are incorporated herein.
• the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, based on the total solid content of the resin composition, excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles, and 0.5 to 20% by mass. It is more preferable to use 18% by mass, more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and 0.5 to 1.2% by mass. is even more preferred.
• a photo-acid generator may be used individually by 1 type, or may be used in combination of multiple types. In the case of a combination of multiple types, the total amount thereof is preferably within the above range.
• the resin composition of the present invention may contain a base generator.
• the base generator is a compound capable of generating a base by physical or chemical action.
• Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
• the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
• the base generator may be an ionic base generator or a non-ionic base generator.
• bases generated from base generators include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
• Nonionic base generator examples include compounds represented by Formula (B1), Formula (B2), or Formula (B3).
• Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 are not hydrogen atoms at the same time. Also, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
• the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.
• Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure.
• the cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed.
• the monocyclic ring is preferably a 5- or 6-membered ring, more preferably a 6-membered ring.
• the monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.
• Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have a substituent as long as the effects of the present invention are exhibited.
• Rb 1 and Rb 2 may combine with each other to form a ring.
• the ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring.
• Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent.
• Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms).
• an aryl group preferably
• Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
• the compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.
• Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
• Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited.
• Rb 13 is preferably an arylalkyl group.
• Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
• an alkyl group preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms
• an alkenyl group preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3
• an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10
• Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, still more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
• an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms
• an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred
• an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, still more preferably 6 to 12
• the compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).
• Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
• Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
• Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
• an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms
• an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred
• an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12
• L is a divalent hydrocarbon group having a saturated hydrocarbon group on a connecting chain route connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the connecting chain route is represents a hydrocarbon group of 3 or more.
• R N1 and R N2 each independently represent a monovalent organic group.
• the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected.
• L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group
• the linking chain is composed of four carbon atoms, and on the route of the linking chain
• the number of atoms of (that is, the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or “linking chain length”) is 4.
• the number of carbon atoms in L (including carbon atoms other than carbon atoms in the connecting chain) in formula (B3) is preferably 3-24.
• the upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more.
• the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred.
• the linking chain length of L is preferably 4 or 5, most preferably 4.
• Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO2020/066416, and the compounds described in paragraphs 0143 to 0177 of WO2018/038002. mentioned.
• the base generator preferably contains a compound represented by the following formula (N1).
• R N1 and R N2 each independently represent a monovalent organic group
• RC1 represents a hydrogen atom or a protecting group
• L represents a divalent linking group
• L is a divalent linking group, preferably a divalent organic group.
• the linking chain length of the linking group is preferably 1 or more, 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 arrangement that provides the shortest path between two carbonyl groups in the formula.
• R N1 and R N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred.
• a monovalent organic group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms
• a hydrocarbon group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms
• an aliphatic hydrocarbon group preferably 1 to
• an aliphatic hydrocarbon group as R N1 and R N2 because the generated base is highly basic.
• the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent.
• an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
• Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains.
• Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms.
• Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
• the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
• Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
• Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
• Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
• the alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
• An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
• R 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms.
• a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
• RN1 and RN2 may be linked to each other to form a ring structure.
• the chain may have an oxygen atom or the like.
• the cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
• the cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.
• N1 nitrogen atom in formula (N1)
• R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
• the protective group is preferably a protective group that is decomposed by the action of an acid or a base, and preferably includes a protective group that is decomposed by an acid.
• protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain.
• Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like.
• the chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned.
• Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.
• the divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group.
• the hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred.
• the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
• the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
• the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
• a group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
• linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
• a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group and an arylene alkylene group are preferred.
• the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
• the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
• the group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
• An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
• the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
• the linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms.
• the linear or branched chain alkenylene group preferably has 1 to 10 C ⁇ C bonds, more preferably 1 to 6, even more preferably 1 to 3.
• the cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
• the number of C ⁇ C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
• the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
• a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.
• base generators include the following, but the present invention should not be construed as being limited thereto.
• the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
• the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
• Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
• ammonium salts include the following compounds, but the present invention is not limited thereto.
• iminium salts include the following compounds, but the present invention is not limited thereto.
• the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
• the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
• the upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
• One or two or more base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
• the solvent is preferably an organic solvent.
• Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
• Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
• 3-alkyloxypropionic acid alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
• 2-alkyloxypropionate alkyl esters e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
• 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
• ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate
• Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.
• Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
• Suitable sulfoxides include, for example, dimethyl sulfoxide.
• Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
• Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
• a combination of dimethyl sulfoxide and ⁇ -butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly
• the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass.
• the solvent content may be adjusted according to the desired thickness of the coating and the method of application.
• the resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
• metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
• silane coupling agent examples include compounds described in paragraph 0316 of International Publication No. 2021/112189 and compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are herein described. incorporated. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Me represents a methyl group and Et represents an ethyl group.
• silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
• xypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimeth
• Aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
• the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
• One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
• Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
• heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
• an ion trapping agent that traps anions such as halogen ions can be used.
• migration inhibitors include the following compounds.
• the content of the migration inhibitor is the total solid content of the resin composition of the present invention, minus the content of the resin particles, the low dielectric resin and the inorganic particles. On the other hand, it is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, even more preferably 0.1 to 1.0% by mass.
• migration inhibitor Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a polymerization inhibitor.
• Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
• Specific compounds of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, phenoxazine, and the like. The contents of which are incorporated herein.
• the content of the polymerization inhibitor is the total solid content of the resin composition of the present invention, minus the content of the resin particles, the low dielectric resin and the inorganic particles. On the other hand, it is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
• polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
• the resin composition of the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating.
• the acid scavenger refers to a compound that can scavenge the generated acid when present in the system, and is preferably a compound with low acidity and high pKa.
• the acid scavenger is preferably a compound having an amino group, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. Primary amine, secondary amine, tertiary amine, ammonium salt are preferred, and secondary amines, tertiary amines and ammonium salts are more preferred.
• acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl groups and/or ether bonds, and anilines having hydroxyl groups and/or ether bonds. Derivatives and the like can be mentioned preferably.
• the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. is preferred.
• acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
• Acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4 ,0]undecar-7-ene and the like.
• Acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris ( t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like.
• acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine.
• Acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline and N,N-dihexylaniline.
• acid scavengers having a pyridine structure include pyridine and 4-methylpyridine.
• alkylamine derivatives having hydroxyl groups and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine and the like.
• aniline derivatives having hydroxyl groups and/or ether bonds include N,N-bis(hydroxyethyl)aniline.
• preferred acid scavengers 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, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexyl
• the composition according to the present invention may or may not contain an acid scavenger, but when it does contain an acid scavenger, the content of the acid scavenger is the total solid content of the composition, the resin particles, the low dielectric resin and the inorganic particles. It is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the mass excluding the content of.
• the acid generator/acid scavenger (molar ratio) is more preferably 5.0-200, still more preferably 7.0-150.
• the resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
• additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
• Organic titanium compounds, antioxidants, anti-agglomerating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (eg, antifoaming agents, flame retardants, etc.), etc. can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No.
• the total blending amount is preferably 3% by mass or less of the mass of the solid content of the resin composition of the present invention excluding the mass of the resin particles, the low dielectric resin and the inorganic particles. .
• surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
• the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
• the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved. can do. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
• Fluorinated surfactants include compounds described in paragraph 0328 of WO2021/112189. The contents of which are incorporated herein.
• the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
• a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
• the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
• a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
• Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
• the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
• a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
• Silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants are described in paragraphs 0329 to 0334 of WO 2021/112189, respectively. compound. The contents of which are incorporated herein.
• the content of the surfactant is preferably 0.001 to 2.0% by mass, preferably 0.005%, based on the total solid content of the composition, excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles. ⁇ 1.0% by mass is more preferred.
• the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after coating. may be unevenly distributed on the surface of the
• the content of the higher fatty acid derivative is the total solid content of the resin composition of the present invention minus the content of the resin particles, the low dielectric resin and the inorganic particles. On the other hand, it is preferably 0.1 to 10% by mass. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
• the resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator.
• a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved.
• the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
• thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
• the content thereof is 0.1 to 30% by mass based on the total solid content of the resin composition of the present invention, excluding the mass content of the resin particles, the low dielectric resin and the inorganic particles. It is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass.
• One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
• the resin composition of the present invention may contain inorganic particles.
• inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
• the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferred.
• the average particle size of the inorganic particles is the primary particle size and the volume average particle size.
• the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
• the composition of the present invention may contain an ultraviolet absorber.
• an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. Specific examples of UV absorbers include compounds described in paragraphs 0341 to 0342 of WO2021/112189. The contents of which are incorporated herein.
• the above various ultraviolet absorbers may be used singly or in combination of two or more.
• the composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain the ultraviolet absorber, the content of the ultraviolet absorber is determined based on the total solid mass of the composition of the present invention, the resin particles, the low dielectric resin and It is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less, relative to the mass excluding the content of the inorganic particles.
• the resin composition of this embodiment may contain an organic titanium compound. By including the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
• Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained.
• titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
• Tetraalkoxytitanium compounds for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide.
• titanium tetramethoxypropoxide titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl) butoxide ⁇ ] and the like.
• Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
• Monoalkoxy titanium compounds for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.
• Titanium oxide compounds for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
• the organotitanium compound at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance.
• titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
• the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
• the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
• compositions of the present invention may contain antioxidants.
• an antioxidant as an additive, it is possible to improve the elongation properties of the film after curing and the adhesion to the metal material.
• Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Specific examples of antioxidants include compounds described in paragraphs 0348 to 0357 of WO2021/112189. The contents of which are incorporated herein.
• the amount of antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
• the addition amount 0.1 parts by mass or more By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment.
• the interaction with the agent improves the sensitivity of the resin composition.
• Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
• Anti-aggregating agents include sodium polyacrylate and the like.
• the aggregation inhibitor may be used alone or in combination of two or more.
• the composition of the present invention may or may not contain an anti-aggregation agent, but when it is included, the content of the anti-aggregation agent is determined based on the total solid mass of the composition of the present invention, the resin particles, the low dielectric resin and the It is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, relative to the mass excluding the content of the inorganic particles.
• the resin composition of the present embodiment may contain a phenolic compound as necessary.
• phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
• one type of phenolic compound may be used alone, or two or more types may be used in combination.
• the composition of the present invention may or may not contain a phenolic compound, but when it does, the content of the phenolic compound is calculated from the total solid mass of the composition of the present invention, the resin particles, the low dielectric resin and the It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, based on the mass excluding the content of the inorganic particles.
• Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof.
• Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
• composition of the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is calculated from the total solid mass of the composition of the present invention, the resin particles, It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less based on the mass excluding the mass of the low dielectric resin and the inorganic particles.
• the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 3,000 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is less than 1,000 mm 2 /s, it is difficult to apply the film to a film thickness required for , for example, a rewiring insulating film. .
• the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is 2.0% or more, the storage stability of the resin composition may be impaired.
• Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
• the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
• a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention.
• Examples include a method of performing filter filtration on the raw material constituting the product, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.
• the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred.
• those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
• Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
• ion exchange treatment and the like are preferably mentioned.
• a conventionally known container can be used as the container for the resin composition of the present invention.
• the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
• the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention and has a dielectric constant of 3.0 or less.
• the shape of the cured product of the resin composition of the present invention is cured in the laminate of the present invention described above. It is the same as the preferred embodiment of the physical properties of the object.
• the resin composition of the present invention can be prepared by mixing the components described above.
• the mixing method is not particularly limited, and conventionally known methods can be used. Mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like.
• the temperature during mixing is preferably 10-30°C, more preferably 15-25°C.
• the filter pore size is, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. HDPE (high density polyethylene) is more preferable when the material of the filter is polyethylene.
• a filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use.
• filters with different pore sizes or materials may be used in combination.
• a connection mode for example, a mode in which an HDPE filter with a pore size of 1 ⁇ m is connected in series as a first stage and an HDPE filter with a pore size of 0.2 ⁇ m as a second stage are connected in series.
• various materials may be filtered multiple times.
• circulation filtration may be used.
• you may filter by pressurizing.
• the pressure to be applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less.
• impurities may be removed using an adsorbent.
• You may combine filter filtration and the impurity removal process using an adsorbent.
• a known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• the resin composition filled in the bottle may be subjected to a degassing step under reduced pressure.
• the method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate having metal wiring to form a film, and a curing step of curing the film.
• the dielectric constant of the cured product obtained by the production method of the cured product of the present invention is 3.0 or less, preferably 2.9 or less, and more preferably 2.8 or less.
• the lower limit of the dielectric constant is not particularly limited, it can be 1.0 or more. From the viewpoint of adhesion after exposure to high humidity conditions, etc., the dielectric loss tangent of the resin particles is preferably 0.01 or less, more preferably 0.005 or less, and 0.002 or less.
• the method for producing a cured product of the present invention includes, between the film forming step and the curing step, an exposure step of selectively exposing the film formed by the film forming step, and an exposure step. It is more preferable to include a developing step of developing the coated film with a developer to form a pattern.
• the method for producing a cured product of the present invention includes the film forming step, the exposing step, the developing step, and a heating step of heating the pattern obtained by the developing step, and after development of exposing the pattern obtained by the developing step. It is particularly preferred to include at least one of the exposure steps. Moreover, it is also preferable that the curing step is performed by heating. Details of each step will be described below.
• the resin composition of the present invention can be used in a film-forming step in which a film is formed by applying it onto a substrate.
• the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a substrate to form a film.
• the base material include the base material having the metal wiring described in the laminate of the present invention.
• Specific 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, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred.
• a film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method.
• the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, ink jet method, etc.
• slit coating and spray coating are preferable for rectangular substrates.
• method, inkjet method, and the like are preferred.
• spin coating for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
• a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
• the transfer method the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.
• a step of removing excess film at the edge of the substrate may be performed.
• processes include edge bead rinsing (EBR), back rinsing, and the like.
• EBR edge bead rinsing
• a pre-wetting process may also be employed in which the base material is coated with various solvents before the resin composition is applied to the base material to improve the wettability of the base material, and then the resin composition is applied.
• the film may be subjected to a step of drying the formed film (layer) to remove the solvent (drying step) after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Moreover, the drying step is preferably performed after the film formation 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, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction.
• the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
• the film may be subjected to an exposure step that selectively exposes the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film forming step. Selectively exposing means exposing a portion of the film. Also, by selectively exposing, the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions). The amount of exposure is not particularly defined as long as the resin composition of the present invention can be cured . is more preferred.
• the exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
• the exposure wavelength is as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
• the resin composition of the present invention exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
• the method of exposure is not particularly limited as long as at least a part of the film made of the resin composition of the present invention is exposed. mentioned.
• the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the exposed film in the exposure step.
• the post-exposure heating step can be performed after the exposure step and before the development step.
• the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
• the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
• the heating rate in the post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature. Also, the rate of temperature increase may be appropriately changed during heating.
• the heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used. Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.
• the film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
• the method for producing a cured product of the present invention may include a development step of developing a film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
• development in which the unexposed portion of the film is removed by the development process is called negative development
• development in which the exposed portion of the film is removed by the development process is called positive development.
• Examples of the developer used in the development process include an aqueous alkaline solution and a developer containing an organic solvent.
• 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)am
• the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
• the compound described in paragraph 0387 of International Publication No. 2021/112189 can be used as the organic solvent.
• Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, Dimethylformamide and the like are also suitable.
• the organic solvent can be used singly 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, and cyclopentanone and ⁇ -butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
• the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.
• the developer may further contain other components.
• Other components include, for example, known surfactants and known antifoaming agents.
• the method of supplying the developer is not particularly limited as long as the desired pattern can be formed.
• the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned. From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable.
• the method of supplying with a spray nozzle is more preferable.
• the substrate is spun to remove the developer from the substrate.
• a step of removing from above may be employed, and this step may be repeated multiple times.
• the method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material.
• a process of vibrating with sound waves or the like and a process of combining them can be adopted.
• the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
• the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
• the pattern may be washed (rinsed) with a rinse.
• a method of supplying the rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
• Rinse liquid When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse.
• the developer is a developer containing an organic solvent, 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) is used as the rinse liquid. be able to.
• the organic solvent when the rinse liquid contains an organic solvent examples 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 an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower pattern solubility than the organic solvent contained in the developer.
• the organic solvent can be used singly or in combination of two or more.
• the organic solvent can be used singly or in combination of two or more.
• cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.
• the rinse liquid contains an organic solvent
• the rinse liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and 90% by mass or more of the organic solvent. is more preferred. Further, 100% by mass of the rinse liquid may be an organic solvent.
• the rinse liquid may contain at least one of a basic compound and a base generator.
• a basic compound and a base generator.
• the embodiment in which the rinse contains an organic solvent and a base is also one of the preferred embodiments of the present invention.
• 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-diaminopentane, N-methylhexy
• the base generator is the same as the preferred embodiments of the base generator contained in the composition described above.
• the base generator is preferably a thermal base generator.
• 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 compound corresponding to at least one of the basic compound and the base generator is 10% by mass or less with respect to the total mass of the rinse solution. is preferable, and it is more preferably 5% by mass or less. Although the lower limit of the content is not particularly limited, it is preferably 0.1% by mass or more, for example.
• the content of the compound corresponding to at least one of the basic compound and the base generator is equal to the total solid content of the rinse liquid. It is also preferable that it is 70 to 100% by mass.
• 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 is preferably within the above range.
• the rinse solution may further contain other components.
• Other components include, for example, known surfactants and known antifoaming agents.
• the method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the base material in the rinse solution, a method of supplying the rinse solution to the base material by piling up the base material, and a method of supplying the rinse solution to the base material by showering. and a method of continuously supplying the rinsing liquid onto the substrate by means of a straight nozzle or the like.
• the permeability of the rinse liquid From the viewpoint of the permeability of the rinse liquid, the removability of the non-image areas, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of the permeability of the rinsing liquid to the image area, the method of supplying the rinsing liquid with a spray nozzle is more preferable.
• the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
• the rinsing step is preferably a step of supplying the rinse liquid to the film after exposure through a straight nozzle or a step of continuously supplying the same, and more preferably a step of supplying the rinse liquid through a spray nozzle.
• the method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state.
• a process of vibrating with sound waves or the like and a process of combining them can be employed.
• the rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
• the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.
• the development step may include a step of bringing the pattern into contact with the processing solution after processing with the developer or after washing the pattern with the rinse solution.
• a method of supplying the processing liquid before the developing liquid or rinsing liquid in contact with the pattern is completely dried may be adopted.
• the treatment liquid examples include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
• Preferred embodiments of the organic solvent and at least one of the basic compound and the base generator are the same as the preferred embodiments of the organic solvent and at least one of the basic compound and the base generator used in the rinse solution described above. .
• the method of supplying the treatment liquid to the pattern the same method as the above-described method of supplying the rinsing liquid can be used, and the preferred embodiments are also the same.
• the content of the compound corresponding to at least one of the basic compound and the base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. preferable. Although the lower limit of the content is not particularly limited, it is preferably 0.1% by mass or more, for example. Further, when at least one of the basic compound and the base generator is solid in the environment where the treatment liquid is used, the content of the compound corresponding to at least one of the basic compound and the base generator is the total solid content of the treatment liquid. It is also preferable that it is 70 to 100% by mass.
• the treatment liquid may contain only one of at least one of the basic compound and the base generator, or may contain two or more of them. .
• the total is preferably within the above range.
• the pattern obtained by the development step may be subjected to a heating step of heating the pattern obtained by the development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. Moreover, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step or a film obtained by the film forming step. In the heating step, a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
• the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable.
• the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base generated from the base generator by heating.
• Heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
• the rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min.
• By setting the temperature increase rate to 1°C/min or more it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity.
• the residual stress of the object can be relaxed.
• the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
• the temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started.
• the temperature of the film (layer) after drying is, for example, the boiling point of the solvent contained in the resin composition of the present invention.
• the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.
• the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
• the upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.
• Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
• the pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
• the pretreatment may be performed in two or more steps.
• the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.
• the heating step is preferably carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or under reduced pressure, in order to prevent decomposition of the specific resin.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
• a heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
• the pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) is subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
• the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step.
• the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
• the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator is promoted. can do.
• the post-development exposure step at least part of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern be exposed.
• the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. preferable.
• the post-development exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.
• the pattern obtained by the development step may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of the heating step and the post-development exposure step). is preferred.
• the metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.
• the method of forming the metal layer is not particularly limited, and existing methods can be applied.
• use the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, US Patent No. 9177926B2 can do.
• photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered.
• a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.
• a preferred embodiment of plating is electroplating using a copper sulfate or copper cyanide plating solution.
• the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m, at the thickest part.
• Fields to which the cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress buffer films.
• pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above can be used.
• the method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of plates such as offset plates or screen plates, for etching molded parts, for protective lacquers and dielectrics in electronics, especially microelectronics. It can also be used for the production of layers and the like.
• the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention as a step, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.
• the laminate of the present invention includes two or more layers made of the cured material and a metal layer between any of the layers made of the cured material.
• the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product between the methods for producing the cured product performed multiple times. Preferred aspects of the metal layer forming step are as described above.
• the method for manufacturing the laminate of the present invention includes a lamination step.
• the lamination step means that the surface of the pattern (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and development It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of (a) the film forming step and (d) the heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, (e) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.
• a surface activation treatment process may be further performed.
• a plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
• the lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
• Each of the layers described above may have the same composition, shape, film thickness, etc., or may differ from each other.
• a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer.
• the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order.
• the film forming step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order.
• the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least part of the metal layer and the resin composition layer to surface activation treatment.
• the surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to surface activation treatment.
• the metal layer forming step may be performed.
• the surface activation treatment may be performed only on at least part of the metal layer, may be performed only on at least part of the resin composition layer after exposure, or may be performed on the metal layer and the resin composition layer after exposure. Both may be done at least partially, respectively.
• the surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which the resin composition layer is formed.
• the surface of the metal layer By subjecting the surface of the metal layer to the surface activation treatment in this manner, the adhesiveness to the resin composition layer (film) provided on the surface can be improved.
• the resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of crude polymer.
• the resulting crude polymer was separated by filtration and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution.
• the resulting crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered and dried in vacuum to obtain a powdery polymer (polyimide precursor) A1.
• polyimide precursor polyimide precursor
• reaction mixture was then cooled to -5°C and 16.12 g (135.5 mmol) of SOCl 2 was added over 2 hours while maintaining the temperature at -5 ⁇ 2°C. Then, a solution of 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added over 2 hours while adjusting the temperature to -5 to 0°C. It was added dropwise to the reaction mixture. After reacting the reaction mixture at 0° C. for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 hour.
• the polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes.
• the polyimide precursor was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the resulting polyimide precursor was dried under reduced pressure at 45° C. for 2 days to obtain polymer A3.
• Mw weight average molecular weight
• the resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of crude polymer.
• the resulting crude polymer was separated by filtration and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution.
• the resulting crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered and dried in vacuum to obtain a powdery polymer (polyamideimide precursor) A4. .
• Mw weight average molecular weight
• reaction solution was cooled to ⁇ 5° C. or lower using an ice/methanol bath, and while maintaining the reaction temperature at ⁇ 0° C. or lower, 9.59 g (0.090 mol) of butyryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. ) and 34.5 g of NMP was added dropwise. After the addition was complete, it was stirred for an additional 16 hours.
• the reaction was diluted with 550 g of NMP and poured into 4 L of vigorously stirred deionized water/methanol (80/20 volume ratio) mixture, the precipitated white powder was collected by filtration and washed with deionized water. bottom. The polymer was dried under vacuum at 50° C. for 2 days to give resin A5.
• each resin composition was obtained by mixing the components described in the "Composition” column of the table below.
• the components described in the "Composition” column of the table below were mixed to obtain each comparative composition.
• the content of each component other than the solvent described in the table was the amount (parts by mass) described in each column of the table.
• the amount of each component other than the solvent described in the table indicates the amount of solid content of that component.
• the content of the solvent was adjusted so that the solid content concentration was the value shown in the table, with the value shown in the table as the mass ratio.
• the resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.5 ⁇ m.
• the description of "-" indicates that the composition does not contain the corresponding component.
• the particle size was measured as the volume average particle size using a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.).
• ⁇ C1 Microdispers-200 (particles containing fluorine atoms manufactured by Techno Chemical Co., Ltd.) particle size 200 to 300 nm
• ⁇ C2 PTFE MPT-N8 (particles containing fluorine atoms, manufactured by Mitsubishi Pencil Co., Ltd.) particle size 200 nm
• C3 Fluon+ (registered trademark) EA-2000 PW10 (manufactured by AGC Co., Ltd.) Particle size 2 to 3 ⁇ m
• ⁇ Additive ⁇ ⁇ J1 A compound having the following structure ⁇ J2: N-phenyldiethanolamine
• the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) of the cured product produced in the method for producing the cured product were measured using a PNA-L network analyzer N5230A (manufactured by KEYSIGHT TECHNOLOGIES) and split cylinder resonance.
• a device CR-728 manufactured by Kanto Denshi Applied Development Co., Ltd.
• measurement was performed by the resonator method under conditions of 24° C. and a frequency of 28 GHz. The measurement results are shown in the column of "relative permittivity (28 GHz)" in the table.
• the resin composition was applied to a silicon wafer having an oxide film (SiO 2 ) formed on the surface with a thickness of 20 ⁇ m, dried at 100° C. for 5 minutes, and heated at 230° C. for 180 minutes. Then, a cured film was produced. The relative dielectric constant and dielectric loss tangent of the single film of the composition obtained by immersing the cured film in hydrogen fluoride and peeling it off were measured. .
• the cured product prepared in the method for preparing a cured product was immersed in a resist stripping solution (MS6310) heated to 75° C. for 15 minutes, washed with running water for 1 minute, and air-dried. After that, the chemical resistance was evaluated based on the residual ratio (%) of the film thickness before and after being immersed in the resist stripping solution.
• the residual rate (%) is a value represented by the following formula.
• Residual rate (%) film thickness of cured product after immersion in resist stripper ( ⁇ m) / film thickness of cured product before immersion in resist stripper ( ⁇ m) ⁇ 100
• the evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Chemical resistance" column of the table. It can be said that the higher the residual rate, the better the chemical resistance of the cured product.
• B The residual rate was more than 60% and 70% or less.
• C The residual rate was 60% or less.
• the film was developed using cyclopentanone and rinsed with PGMEA, then using a clean oven CLH-2 manufactured by Koyo Thermo Systems Co., Ltd., heated at a heating rate of 5° C./min under an N atmosphere, The temperature described in the "curing temperature” column of the table was maintained for the time described in the "curing time” column to prepare a reliability evaluation substrate.
• Adhesion reduction rate (%) ⁇ (adhesion before test) - (adhesion after dew condensation cycle) ⁇ / (adhesion before test) x 100 -Evaluation criteria-
• the laminate of the present invention maintains adhesion between the cured product and the metal wiring even after being exposed to high humidity conditions. It is also found that the resin composition of the present invention can provide a cured product that maintains adhesion to metals even after being exposed to high humidity conditions.
• the comparative composition in Comparative Example 1 has a dielectric constant exceeding 3.0. In such a mode, it can be seen that the adhesion between the cured product and the metal wiring in the laminate is greatly reduced after exposure to high humidity conditions. Further, it can be seen that the cured product obtained from the comparative composition in Comparative Example 1 has significantly reduced adhesion to metal after being exposed to high humidity conditions.
• the comparative composition in Comparative Example 2 does not contain a photosensitizer.
• Example 101 The resin composition used in Example 1 was applied in a layer by spin coating to the surface of the thin copper layer of the resin base material on which the thin copper layer was formed, and dried at 100° C. for 4 minutes to obtain a film thickness. After forming a resin composition layer of 20 ⁇ m, it was exposed using a stepper (NSR1505 i6 manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After exposure, it was heated at 100° C. for 4 minutes.
• NSR1505 i6 manufactured by Nikon Corporation
• the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
• the temperature was raised at a rate of 10° C./min, reaching 230° C., and then maintained at 230° C. for 3 hours to form an interlayer insulating film for rewiring layers.
• This interlayer insulating film for rewiring layer was excellent in insulating properties.
• a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

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