Classifications

• • 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
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
  • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • 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
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins

Definitions

• the present invention relates to a composition, a transfer film, a method for manufacturing a laminate, a laminate, and a semiconductor package.
• conductive patterns such as an electrode pattern corresponding to the sensor of the visual recognition area
• wiring for the peripheral wiring and extraction wiring are provided inside the touch panel.
• Insulating films are used for the purposes of forming and protecting such electrode patterns and conductive patterns.
• insulating films are provided between each layer for the purposes of insulating and protecting the wiring between the wiring.
• Patent Document 1 discloses a photosensitive resin composition that contains (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, (B) an epoxy resin, and (C) an active ester compound.
• the insulating film as described above is required to have a small linear expansion coefficient and excellent insulating reliability.
• the present inventors have studied a film obtained using the photosensitive resin composition described in Patent Document 1 and found that there is room for improvement in the linear expansion coefficient and insulation reliability of the obtained film.
• the insulation reliability refers to the wet heat resistance of the insulation of the film.
• a liquid crystal display device comprising a resin and a liquid crystal compound having a polymerizable group,
• the composition wherein the resin comprises at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenol resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin, polyphenylene sulfide, and precursors thereof.
• the resin comprises at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenol resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, poly
• composition according to [1], wherein the liquid crystal compound having a polymerizable group is a compound represented by formula (Z1) described later.
• the liquid crystal compound having a polymerizable group has a molecular weight of 2,000 or less.
• content of the liquid crystal compound having a polymerizable group is 1.0 to 30.0% by mass based on the total solid content of the composition.
• a mass ratio of the content of the liquid crystal compound having a polymerizable group to the content of the resin is 0.01 to 3.00.
• the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.
• the filler has an average particle size of 300 nm or less.
• content of the filler is 90.0 mass% or less based on the total solid content of the composition.
• composition according to any one of [1] to [15] which is used for forming an insulating film for a semiconductor package.
• a semiconductor package comprising the laminate according to [19].
• the present invention it is possible to provide a composition capable of forming a film having a small linear expansion coefficient and excellent insulation reliability. Further, a transfer film, a method for producing a laminate, a laminate, and a semiconductor package relating to the composition can be provided.
• FIG. 2 is a schematic diagram showing an example of a layer structure of a transfer film.
• a numerical range expressed using “to” means a range that includes the numerical values before and after “to” as the lower and upper limits.
• the “content” of the component means the total content of those two or more components.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
• the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
• a combination of two or more preferred aspects is a more preferred aspect.
• process refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• the temperature condition may be 25°C.
• the temperature when performing each of the above steps may be 25°C unless otherwise specified.
• the term "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more.
• the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• actinic rays or “radiation” refers to, for example, the bright line spectrum of a mercury lamp such as g-line, h-line, and i-line, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB).
• light refers to actinic rays or radiation.
• exposure includes not only exposure to far ultraviolet light, extreme ultraviolet light, such as that typified by mercury lamps and excimer lasers, and X-rays, but also drawing with particle beams such as electron beams and ion beams.
• solids of a composition refers to the components that form the film formed using the composition.
• a solvent e.g., an organic solvent and water
• liquid components that form a film are also considered to be solids.
• the content ratio of each repeating unit in a polymer is a molar ratio.
• the molecular weight when there is a molecular weight distribution is the weight average molecular weight (Mw).
• Mw weight average molecular weight
• Mn number average molecular weight
• (meth)acrylic acid is a concept that includes both acrylic acid and methacrylic acid
• (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group
• (meth)acrylate is a concept that includes both acrylate and methacrylate
• (meth)acrylamide group is a concept that includes both acrylamide group and methacrylamide group.
• the bonding direction of a divalent group is not limited unless otherwise specified.
• a divalent group e.g., -CO-O-
• the compound when Y is -CO-O- in a compound represented by the formula "X-Y-Z", the compound may be either "X-O-CO-Z" or "X-CO-O-Z".
• the compounds described in this specification may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes. In addition, only one type of isomer or isotope may be contained, or multiple types of isomers and isotopes may be contained.
• the layer thickness is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 ⁇ m or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 ⁇ m.
• SEM scanning electron microscope
• TEM transmission electron microscope
• the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg).
• the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.
• composition contains a resin and a liquid crystalline compound having a polymerizable group, and the resin contains at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenol resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin, polyphenylene sulfide, and precursors thereof.
• the resin contains at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenol resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, poly
• composition having the above-mentioned configuration can solve the problems of the present invention.
• present inventors speculate as follows.
• the mechanism by which the effects are obtained is not limited by the following speculation. In other words, even if the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention.
• the composition of the present invention contains the above-mentioned specific resin, so that the composition of the present invention can form a film with a small linear expansion coefficient.
• the composition contains a liquid crystal compound having a polymerizable group, so that the molecular motion is suppressed by the interaction between the components, and unintended reactions such as decomposition reactions in the film are suppressed.
• the film formed by the composition of the present invention is also excellent in insulating reliability.
• the film formed by the composition of the present invention is also referred to as a "specific film.”
• the specific film having a small linear expansion coefficient is also referred to simply as a "small linear expansion coefficient”
• the specific film having excellent insulation reliability is also referred to simply as an “excellent insulation reliability”
• the achievement of at least one of a smaller linear expansion coefficient and excellent insulation reliability is also referred to as an "excellent effect of the present invention.”
• the composition includes a resin, and the resin includes at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenolic resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin, polyphenylene sulfide, and precursors thereof.
• the resin includes at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenolic resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butad
• the resin preferably contains at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, polyphenylene ether resin, benzocyclobutene resin, liquid crystal polymer, and precursors thereof, and more preferably contains at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
• the precursor of the resin is a resin that is converted into the resin by heat treatment, light treatment, or chemical treatment.
• the resin may have a polymerizable group.
• the polymerizable group include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, and the radical polymerizable group is preferred.
• the radical polymerizable group is preferably a group having an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, and a vinyl ether group, and a (meth)acryloyl group is preferred. It is also preferable that the resin has a polymerizable group capable of polymerizing with a polymerizable group in a liquid crystal compound having a polymerizable group, which will be described later.
• the resin may have an acid-decomposable group.
• the acid-decomposable group include the acid-decomposable groups described in paragraphs 0024 to 0031 of WO 2019/187881.
• Polyimide is a resin having an imide structure.
• the polyimide is preferably a resin having a cyclic imide structure, which may have a substituent.
• the polyimide is preferably a resin synthesized from a polyimide precursor having a repeating unit represented by formula (1) (e.g., a resin obtained by a ring-closing reaction).
• the polyimide precursor preferably has a repeating unit represented by formula (1).
• A1 and A2 each independently represent an oxygen atom or -NH-.
• R111 represents a divalent organic group.
• R113 and R114 each independently represent a hydrogen atom or a monovalent organic group.
• R115 represents a tetravalent organic group.
• a 1 and A 2 each independently represent an oxygen atom or -NH-.
• a 1 and A 2 are preferably an oxygen atom.
• R 111 represents a divalent organic group.
• the divalent organic group include a divalent aliphatic group, a divalent aromatic ring group, and a group combining these.
• the divalent organic group is preferably a divalent aliphatic group having 2 to 20 carbon atoms, a divalent aromatic ring group having 6 to 20 carbon atoms, or a group combining these, and more preferably a divalent aromatic ring group having 6 to 20 carbon atoms.
• the aliphatic group may be linear, branched, or cyclic.
• the aromatic ring group may be monocyclic or polycyclic.
• the aliphatic group and the aromatic ring group may have a heteroatom.
• the heteroatom may be included in the divalent organic group as, for example, -O-, -CO-, -S-, -SO 2 -, and -NHCO- groups.
• a divalent organic group derived from a diamine is also preferred as R 111.
• the diamine a diamine used in the production of a polyimide precursor is preferred, and an aliphatic diamine or an aromatic diamine is more preferred.
• the diamine is preferably a diamine having a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a combination thereof, and more preferably a diamine having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamine).
• aromatic ring group include groups having the following structure:
• A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO- or a combination of these, or a single bond.
• A is preferably an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -S- or -SO 2 -, more preferably -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 - or -C(CH 3 ) 2 -, and even more preferably -O-.
• Each Ar 0 independently represents a divalent aromatic hydrocarbon group.
• L 0 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO- or a combination of these, or a single bond.
• * represents a bonding position.
• Ar 0 may be the same or different.
• the number of carbon atoms in the divalent aromatic hydrocarbon group represented by Ar0 is preferably from 6 to 22, more preferably from 6 to 18, and even more preferably from 6 to 10.
• the aromatic hydrocarbon group is preferably a phenylene group.
• L 0 has the same meaning as A described above, and the preferred embodiments are also the same.
• diamines examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, or isophoronediamine; meta- or para-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether
• the diamine may also be one having two or more alkylene glycol units in the main chain, and the diamine having two or more alkylene glycol units in the main chain is preferably one having two or more ethylene glycol chains and/or propylene glycol chains in one molecule. Diamines not having an aromatic ring are also preferred.
• diamine examples include the Jeffamine (registered trademark) series (KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000 and D-4000, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.
• HUNTSMAN 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine
• 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine examples include the Jeffamine (registered trademark) series (KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000 and D-4000, manufactured by HUNTSMAN), 1-
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably represents a group having a polymerizable group, and more preferably both R 113 and R 114 represent a group having a polymerizable group. Examples of the polymerizable group include the groups exemplified as the polymerizable group that the above-mentioned resin may have.
• the monovalent organic group may be a monovalent organic group X, which will be described later.
• R 113 and R 114 are preferably a group having an ethylenically unsaturated double bond, and more preferably a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by formula (III).
• R 200 represents a hydrogen atom or a methyl group
• R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, or a (poly)oxyalkylene group having 4 to 30 carbon atoms
• * represents a bonding position
• R 200 represents a hydrogen atom or a methyl group.
• R 200 is preferably a methyl group.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, or a (poly)oxyalkylene group having 4 to 30 carbon atoms.
• the number of carbon atoms in the alkylene group constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
• the number of repeating oxyalkylene units constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
• the (poly)oxyalkylene group is a concept that encompasses both an oxyalkylene group and a polyoxyalkylene group.
• R 201 examples include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and —CH 2 CH(OH)CH 2 —.
• An ethylene group, a propylene group, a trimethylene group, or —CH 2 CH(OH)CH 2 — is preferable, and an ethylene group is more preferable.
• Examples of the monovalent organic group represented by R 113 or R 114 include an aliphatic group, an aromatic ring group, and an arylalkyl group having 1 to 3 acid groups. Examples include an aromatic ring group having 6 to 20 carbon atoms and having an acid group, and an arylalkyl group having 7 to 25 carbon atoms and having an acid group. More specific examples include a phenyl group having an acid group and a benzyl group having an acid group.
• the acid group is preferably a hydroxyl group or a carboxy group.
• R 113 and R 114 are also preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, or a 4-hydroxybenzyl group.
• the monovalent organic group represented by R 113 or R 114 also includes a leaving group which is eliminated by the action of an acid.
• R 115 represents a tetravalent organic group.
• a tetravalent organic group having an aromatic ring is preferable, and a group represented by formula (5) or a group represented by formula (6) is more preferable.
• R 112 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO- or a combination of these, or a single bond.
• * represents the bonding position.
• * represents a bonding position.
• R 112 has the same meaning as A described above, and the preferred embodiments are also the same.
• a tetravalent organic group is a tetracarboxylic acid residue remaining after removing the acid dianhydride group from a tetracarboxylic acid dianhydride.
• the tetracarboxylic acid dianhydride is preferably a compound represented by formula (7).
• R 115 represents a tetravalent organic group.
• R 115 in formula (7) has the same meaning as R 115 in formula (1), and the preferred embodiments are also the same.
• tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride.
• Tetracarboxylic dianhydrides include, for example, compounds represented by any of formulas (DAA-1) to (DAA-5).
• the monovalent organic group X is preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent, and more preferably an alkyl group which may have an aromatic ring group.
• the alkyl group may be linear, branched, or cyclic, and the cyclic group may be monocyclic or polycyclic.
• the linear or branched alkyl group preferably has 1 to 30 carbon atoms.
• the cyclic alkyl group (cycloalkyl group) preferably has 3 to 30 carbon atoms.
• alkyl group examples include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl groups; monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic cycloalkyl groups such as adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, t
• the aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and may be either a monocyclic or polycyclic group.
• the ring constituting the aromatic ring group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, and a triphenylene ring; a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring
• aromatic heterocyclic groups such as an imidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring.
• the substituent that the aromatic ring group may have is preferably the
• the repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or a repeating unit represented by formula (1-B).
• a 11 and A 12 represent an oxygen atom or -NH-.
• R 111 and R 112 each independently represent a divalent organic group.
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
• a 11 , A 12 , R 111 , R 113 and R 114 have the same meanings as A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), respectively, and the preferred embodiments are also the same.
• R 112 has the same meaning as R 112 in formula (5), and the preferred embodiments are also the same.
• the bonding positions of the carbonyl group to the benzene ring are preferably 4, 5, 3', and 4' in formula (1-A).
• the bonding positions of the carbonyl group to the benzene ring are preferably 1, 2, 4, and 5 in formula (1-B).
• the polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).
• the content of the repeating unit represented by formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, based on the total repeating units of the polyimide precursor.
• the upper limit is preferably 100 mol% or less.
• the polyimide precursor also preferably contains a fluorine atom.
• the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the polyimide precursor.
• the upper limit is preferably 50% by mass or less.
• the polyimide precursor may be obtained by copolymerizing the repeating unit represented by formula (1) with an aliphatic group having a siloxane structure, which can improve adhesion to the substrate.
• the aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.
• the weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000.
• the number average molecular weight (Mn) of the polyimide precursor is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and even more preferably from 4,000 to 25,000.
• the polydispersity (Mw/Mn) of the polyimide precursor is preferably from 1.5 to 3.5, and more preferably from 2.0 to 3.0.
• Polybenzoxazole is a resin having a benzoxazole ring.
• the polybenzoxazole is not particularly limited as long as it is a resin having a benzoxazole ring, and may have a substituent.
• the polybenzoxazole is preferably a resin synthesized from a polybenzoxazole precursor having a repeating unit represented by formula (2) (e.g., a resin obtained by a ring-closing reaction).
• the polybenzoxazole precursor preferably has a repeating unit represented by formula (2).
• R 121 represents a divalent organic group
• R 122 represents a tetravalent organic group
• R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
• R 121 represents a divalent organic group.
• the divalent organic group includes the divalent organic group represented by R 111 described above.
• R 122 represents a tetravalent organic group.
• examples of the tetravalent organic group include the tetravalent organic group represented by R 115 described above.
• R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
• R 123 and R 124 have the same meanings as R 113 and R 114 , and the preferred embodiments are also the same.
• the polybenzoxazole precursor may contain other repeating units in addition to the repeating unit represented by formula (2).
• Examples of the other repeating units include repeating units having a siloxane structure.
• Examples of the other repeating units include the repeating units described in paragraphs 0150 to 0154 of JP 2020-154205 A.
• the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000.
• the number average molecular weight (Mn) of the polybenzoxazole precursor is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and even more preferably from 4,000 to 25,000.
• the polydispersity (Mw/Mn) of the polybenzoxazole precursor is preferably from 1.5 to 3.5, more preferably from 2.0 to 3.0.
• the phenolic resin is a resin having a phenolic hydroxyl group.
• examples of the phenol resin include phenol novolac resin, cresol novolac resin, biphenyl aralkyl type phenol resin, naphthol aralkyl resin, and naphthol novolac resin.
• phenolic resins include AV Light series such as TR4020G, TR4050G, TR4080G, TR5020G, TR5050G, TR6020G, TR6050G, and TR6080G manufactured by Asahi Organic Chemicals Co., Ltd.; photoresist resin series manufactured by Sumitomo Bakelite Co., Ltd.; Resitop series manufactured by Gun-ei Chemical Industry Co., Ltd.; PR-30-40P, PR-100L, PR-100H, PR-50, PR-55, PR-56-1, PR-56-2, and WR.
• AV Light series such as TR4020G, TR4050G, TR4080G, TR5020G, TR5050G, TR6020G, TR6050G, and TR6080G manufactured by Asahi Organic Chemicals Co., Ltd.
• photoresist resin series manufactured by Sumitomo Bakelite Co., Ltd.
• Resitop series manufactured by Gun-ei Chemical Industry Co., Ltd. PR-30-40P, PR-100L,
• Phenolite series such as WR-101, WR-102, WR-103, and WR-104, manufactured by DIC Corporation; photoresist resins such as LF-100, LF-110, LF-120, LF-200, LF-400, and LF-500, manufactured by Lignite Corporation; MEHC-7851SS, MEHC-78004S, MEHC-7851-SS, MEHC-7851-S, MEHC-7851-M, MEHC-7851-H, MEHC-7800-4S, MEHC-7851-H ...
• phenol resins examples include those described in JP-A-2021-157174. Further, examples of the phenolic resin include phenolic curing agents such as EPICLON series, EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC Corporation).
• the epoxy resin is a resin having an epoxy group.
• epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins
• the epoxy resin contains an epoxy resin that is liquid at a temperature of 20°C (hereinafter also referred to as “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20°C (hereinafter also referred to as “solid epoxy resin”).
• liquid epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin is preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin is more preferred.
• liquid epoxy resins examples include HP4032, HP4032D, EXA4032SS, and HP4032SS (naphthalene type epoxy resins) manufactured by DIC Corporation; jER828EL (bisphenol A type epoxy resin), jER807 (bisphenol F type epoxy resin), and jER152 (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.
• HP4032SS or ZX1059 is preferred.
• solid epoxy resin tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, or naphthylene ether type epoxy resin is preferable, tetrafunctional naphthalene type epoxy resin, biphenyl type epoxy resin, or naphthylene ether type epoxy resin is more preferable, and biphenyl type epoxy resin is further preferable.
• solid epoxy resins examples include HP-4700, HP-4710 (tetrafunctional naphthalene type epoxy resin), N-690 (cresol novolac type epoxy resin), N-695 (cresol novolac type epoxy resin), HP7200, HP7200H, HP7200K-65I (dicyclopentadiene type epoxy resin), EXA7311, EXA7311-G3, and HP6000 (naphthylene ether type epoxy resin), and EPPN-502H (trisphenol epoxy resin) manufactured by DIC Corporation.
• epoxy resins examples include NC7000L (naphthol novolac type epoxy resin), NC3000H, NC3000, NC3000L, and NC3100 (biphenyl type epoxy resin), manufactured by Nippon Kayaku Co., Ltd.; ESN475 (naphthol novolac type epoxy resin) and ESN485 (naphthol novolac type epoxy resin), manufactured by Nippon Steel Chemical & Material Co., Ltd.; YX4000H, YL6121 (biphenyl type epoxy resin), and YX4000HK (bixylenol type epoxy resin), manufactured by Mitsubishi Chemical Corporation.
• the solid epoxy resin YX4000HK, NC3000L, or HP7200H is preferable.
• the polyphenylene ether resin is a resin having a phenylene ether group.
• the polyphenylene ether resin may have either a linear structure or a branched structure, and preferably has a branched structure.
• ether bonds are directly bonded to at least three positions, i.e., the ipso position, the ortho position, and the para position, of the benzene ring.
• the polyphenylene ether resin having a branched structure can be obtained, for example, by polymerizing two or more kinds of phenol compounds.
• the above-mentioned phenol compound is preferably a phenol compound having hydrogen atoms at the ortho and para positions and having a polymerizable group, or a mixture of a phenol compound having hydrogen atoms at the ortho and para positions and no polymerizable group and a phenol compound having no hydrogen atom at the ortho position, a hydrogen atom at the para position and having a polymerizable group.
• phenol compounds used in the synthesis of polyphenylene ether resins include o-vinylphenol, m-vinylphenol, o-allylphenol, m-allylphenol, 3-vinyl-6-methylphenol, 3-vinyl-6-ethylphenol, 3-vinyl-5-methylphenol, 3-vinyl-5-ethylphenol, 3-allyl-6-methylphenol, 3-allyl-6-ethylphenol, 3-allyl-5-methylphenol, 3-allyl-5-ethylphenol, phenol, o-cresol, m-cresol, o-ethylphenol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, o-tert-butylphenol, m-tert-butylphenol, o-phenylphenol, m-phenylphenol, and 2-dodecylphenol.
• the phenol compound is preferably 2,6-dimethylphenol or 2-allylphenol.
• the polyphenylene ether resin also preferably has a polymerizable group.
• the polymerizable group is preferably a group having an ethylenically unsaturated double bond, and more preferably a vinylphenyl group or a (meth)acryloyl group.
• the composition preferably contains a maleimide compound, which reacts with the polyphenylene ether resin to obtain a modified polyphenylene ether.
• modified polyphenylene ethers include resins obtained by curing the resin compositions described in WO 2022/102756.
• polyphenylene ether resins include poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether.
• polyphenylene ether resins include those described in JP-A-2022-157695.
• the silicone resin is a resin having an organosiloxane structure.
• the silicone resin include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, with curable silicone resins being preferred.
• the curable silicone resin include an addition reaction type silicone resin, a condensation reaction type silicone resin, and an ultraviolet or electron beam curable silicone resin.
• An example of an addition reaction type silicone resin is a resin obtained by reacting and curing polydimethylsiloxane having vinyl groups introduced at the terminals or side chains with hydrogen siloxane using a platinum catalyst.
• An example of a condensation reaction type silicone resin is a resin having a three-dimensional crosslinked structure formed by condensing polydimethylsiloxane having a hydroxyl group at its terminal with polydimethylsiloxane having a hydrogen atom at its terminal using an organotin catalyst.
• ultraviolet-curable silicone resins include those that utilize the same radical reaction as silicone rubber crosslinking, those that introduce unsaturated groups to cause photocuring, those that use ultraviolet light or electron beams to decompose onium salts to generate strong acids and cleave epoxy groups to cause crosslinking, and those that crosslink by addition reaction of thiols to vinyl siloxanes.
• Specific examples include acrylate-modified polydimethylsiloxanes and glycidoxy-modified polydimethylsiloxanes.
• silicone resins include a dimethylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, a dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, and a dimethylsiloxane-diphenylsiloxane copolymer capped at both molecular chain terminals with dimethylvinylsiloxy groups.
• the silicone resin preferably has an aromatic ring.
• the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and even more preferably a benzene ring.
• the silicone resin a modified silicone resin obtained by reacting an organosilicon compound with a hydrosilylation agent is also preferred.
• the organosilicon compound preferably further has a polymerizable group, for example, a polymerizable group contained in the resin.
• the organosilicon compound may, for example, be a compound having a silyl group, and 1,4-bis(dimethylsilyl)benzene or trivinylphenylsilane is preferred.
• the reaction temperature is preferably 100 to 200° C., and the reaction time is preferably 1 to 10 hours.
• silicone resins examples include resins obtained from organosiloxanes and curable compositions described in JP 2020-026502 A.
• the benzocyclobutene resin is a resin having a benzocyclobutene ring.
• Benzocyclobutene resins include, for example, divinylsiloxane-bisbenzocyclobutene resins (eg, CYCLOTENE resins, manufactured by The Dow Chemical Company).
• the fluorene resin is a resin having a fluorene ring.
• the fluorene resin include a resin obtained by reacting a fluorene compound having a hydroxyaryl structure with an aldehyde compound, and a derivative thereof.
• the fluorene compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(6-hydroxynaphthyl)fluorene.
• a liquid crystal polymer is a resin that exhibits liquid crystallinity.
• the liquid crystal polymer is preferably a thermotropic liquid crystal polymer, which means a polymer that exhibits liquid crystallinity within a certain temperature range.
• the thermotropic liquid crystal polymer may be any liquid crystal polymer that can be melt-molded, and examples thereof include thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides in which amide bonds are introduced into thermoplastic liquid crystal polyesters.
• the liquid crystal polymer preferably has a repeating unit having an aromatic ring.
• the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and further preferably a benzene ring.
• the monomer from which the repeating unit having an aromatic ring is derived is preferably p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, or isophthalic acid.
• the liquid crystal polymer preferably contains two or more repeating units derived from a compound selected from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid, and more preferably contains four or five repeating units derived from the above compounds.
• the liquid crystal polymer may contain repeating units derived from compounds other than the above compounds.
• Other compounds include, for example, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 3,3'-diphenyldicarboxylic acid, and 2,2'-diphenyldicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl,
• Publications of known resins include polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), and polyphenylene sulfide.
• the resin contained in the composition may be a precursor of each of the resins mentioned above.
• the weight average molecular weight (Mw) of the resin is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 5,000 to 50,000.
• the number average molecular weight (Mn) of the resin is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and even more preferably from 4,000 to 25,000.
• the polydispersity (Mw/Mn) of the resin is preferably from 1.0 to 3.5, and more preferably from 2.0 to 3.0.
• the resins may be used alone or in combination of two or more.
• the content of the resin is preferably from 1.0 to 99.0 mass %, more preferably from 5.0 to 98.0 mass %, based on the total solid content of the composition.
• the content of the resin is preferably 5.0 to 99.0% by mass based on the total solid content of the composition excluding the filler.
• the composition contains a compound Z which is a liquid crystal compound having a polymerizable group.
• Compound Z is a liquid crystalline compound.
• Compound Z may be either a rod-shaped liquid crystalline compound or a discotic liquid crystalline compound, but is preferably a rod-shaped liquid crystalline compound.
• Examples of compound Z include compounds having a polymerizable group and a mesogenic group exhibiting liquid crystallinity, and compounds in which the polymerizable group and the mesogenic group are linked via a spacer are preferred.
• the spacer include a chain aliphatic hydrocarbon group and a (poly)oxyalkylene group.
• compound Z is a low molecular weight liquid crystal compound.
• the molecular weight of compound Z is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less.
• the molecular weight of compound Z is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more.
• the polymerizable group contained in the compound Z may be any one of a radically polymerizable group, a cationic polymerizable group, and an anionic polymerizable group, and is preferably a radically polymerizable group.
• the radical polymerizable group is preferably a group having an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, and a vinyl ether group, and a (meth)acryloyl group is preferred.
• the number of polymerizable groups possessed by compound Z is 1 or more, preferably 1 to 10, more preferably 2 to 6, still more preferably 2 or 3, and particularly preferably 2.
• the compound Z is preferably a compound represented by formula (Z1).
• Formula (Z1) P 1 -L 1 -ML 2 -P 2
• P1 and P2 each independently represent a polymerizable group
• L1 and L2 each independently represent a divalent linking group
• M represents a mesogenic group.
• P1 and P2 each independently represent a polymerizable group.
• the polymerizable group include the polymerizable group contained in the compound Z described above, and preferred embodiments thereof are also the same.
• L 1 and L 2 each independently represent a divalent linking group.
• the divalent linking group include -O-, -S-, -CO-, -NR N -, -CO-O-, -O-CO-O-, -CO-NR N -, divalent aliphatic hydrocarbon groups, and combinations of these.
• R N represents a hydrogen atom or an alkyl group (preferably having 1 to 7 carbon atoms).
• the divalent aliphatic hydrocarbon group includes an alkylene group, an alkenylene group, and an alkynylene group, and an alkylene group is preferable.
• the divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear.
• the alkylene group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms.
• the alkenylene group and alkynylene group preferably have 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms.
• the divalent aliphatic hydrocarbon group may have a substituent, for example, a halogen atom or a cyano group. Of the above divalent aliphatic hydrocarbon groups, alkylene groups having 2 to 12 carbon atoms are preferred.
• L1 and L2 are preferably a divalent linking group represented by * P -L a -A a -L b -* M .
• * P represents the bonding position with P1 or P2
• * M represents the bonding position with M.
• L a and L b each independently represent a single bond, —O—, —S—, —CO—, —NR N —, —CO—O—, —O—CO—O—, —CO—NR N —, or a group formed by combining these.
• L a is preferably a single bond, --O-- or --CO--O--.
• Lb is preferably --O--, --CO--, --CO--O-- or --O--CO--O--, and more preferably --O-- or --CO--O--.
• Aa represents a divalent aliphatic hydrocarbon group. The preferred embodiments of the divalent aliphatic hydrocarbon group represented by Aa are as described above.
• M represents a mesogenic group.
• the mesogenic group include known mesogenic groups, and a mesogenic group represented by formula (M1) is preferable.
• each Lm independently represents a single bond or a divalent linking group.
• the divalent linking group include the divalent linking groups represented by L 1 and L 2 described above.
• Lm is preferably a single bond, --O--, --CO--O--, --O--CO--O--, a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a group formed by combining these.
• the plurality of Lm 's may be the same or different.
• Wm and W each independently represent a divalent ring group.
• the divalent ring group include an arylene group, a heteroarylene group, a cyclic alkylene group, a cyclic alkenylene group, and a divalent aliphatic heterocyclic group, and an arylene group or a cyclic alkylene group is preferable.
• the divalent ring group may be either a monocyclic or polycyclic ring, and is preferably a monocyclic group.
• the divalent ring group preferably has 4 to 12 ring members, more preferably 5 to 8 ring members, and even more preferably 6 ring members.
• Examples of the divalent ring group include a 1,4-phenylene group, a 1,4-cyclohexanediyl group, a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group, a 1,3,4-thiadiazole-2,5-diyl group, a 1,3,4-oxadiazole-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,5-diyl group, a thiophene-2,5-diyl group, and a pyridazine-3,6-diyl group, and a 1,4-phenylene group or a 1,4-cyclohexanediyl group is preferable.
• the divalent ring group may be any isomer, and may be a mixture of any ratio in the composition.
• the divalent ring group may have a substituent.
• the substituent include a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a formyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, a nitro group, a trifluoromethyl group, and a difluoromethyl group.
• a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms is preferred.
• the plurality of Wm 's may be the same or different.
• m represents an integer of 1 to 3, preferably 2 or 3.
• mesogenic groups are examples of mesogenic groups, but the present invention is not limited to these.
• the mesogenic groups shown below may be substituted with the above-mentioned substituents.
• Compound Z can be synthesized by known methods, for example, by the method described in JP-A-11-513019.
• the compound Z may be used alone or in combination of two or more kinds.
• the content of compound Z is preferably 1.0 to 85.0 mass %, more preferably 1.0 to 50.0 mass %, and even more preferably 1.0 to 30.0 mass %, based on the total solid content of the composition.
• the mass ratio of the content of compound Z to the content of the resin is preferably from 0.005 to 5.00, more preferably from 0.01 to 3.00, and even more preferably from 0.01 to 1.00.
• the resin and compound Z has an ethylenically unsaturated double bond
• compound Z has an ethylenically unsaturated double bond
• both the resin and compound Z have an ethylenically unsaturated double bond.
• An example of an embodiment in which the resin and the compound Z have an ethylenically unsaturated double bond is an embodiment in which the resin and the compound Z have a group having an ethylenically unsaturated double bond.
• composition may contain are described in detail below.
• the composition preferably contains a photopolymerization initiator, in that the effect of the present invention is more excellent and the composition exhibits photolithographic properties.
• the term "exhibiting photolithographic properties" means a property that allows a pattern to be formed by a photolithography method.
• the composition is used in the production of a laminate and a semiconductor package, etc., as described below, it is preferable that the composition exhibits photolithographic properties in that a pattern can be formed with high precision.
• the photopolymerization initiator is a compound different from the various components described above.
• the photopolymerization initiator examples include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferable.
• the photopolymerization initiator preferably functions as a polymerization initiator for the polymerizable group of the compound Z described above.
• the photopolymerization initiator examples include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure).
• an oxime ester compound or an aminoacetophenone compound is preferable, and an oxime ester compound is more preferable.
• oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (product name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name: IRGACURE OXE-02, manufactured by BASF), [ 8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazoyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF Corporation), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl
• aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).
• photopolymerization initiators examples include 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO), H) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819).
• the photopolymerization initiator examples include the photopolymerization initi
• the photopolymerization initiator may be used alone or in combination of two or more kinds.
• the content of the photopolymerization initiator is preferably from 0.01 to 10.0% by mass, more preferably from 0.1 to 5.0% by mass, and even more preferably from 0.1 to 3.0% by mass, based on the total solid content of the composition.
• the mass ratio of the content of compound Z to the content of the photopolymerization initiator is preferably from 0.01 to 100.0, more preferably from 0.1 to 75.0, still more preferably from 0.5 to 50.0, and particularly preferably from 0.7 to 40.0.
• the composition preferably contains a filler in that the dielectric loss tangent of the film formed is smaller.
• the average particle size of the filler is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 150 nm or less.
• the lower limit of the average particle size of the filler is more than 0 nm, preferably 5 nm or more, and more preferably 10 nm or more.
• the average particle size of the filler is also preferably 5 to 300 nm, and more preferably 10 to 150 nm.
• the average particle size of the filler is a value calculated by the following particle size measurement method.
• Particle size measurement method A rectangular region of 3 ⁇ m ⁇ 10 ⁇ m in a cross section along the normal direction of the surface of a composition layer formed using the composition is observed with a scanning electron microscope, and the operation of measuring the long diameters of all fillers observed within the above-mentioned region is performed at five different points on the above-mentioned film, and the average value of the long diameters of all fillers measured in each operation is regarded as the average particle size of the filler.
• the composition is applied onto a substrate (preferably a glass substrate) to form a composition layer.
• the thickness of the composition layer is preferably 3 ⁇ m or more.
• a drying treatment may be performed as necessary after the composition is applied.
• a cross section along the normal direction of the surface (surface opposite to the substrate side) of the obtained composition layer is cut out, and a rectangular area of 3 ⁇ m ⁇ 10 ⁇ m of the cross section is observed with a scanning electron microscope, and the major axis of all fillers observed within the area is measured.
• S-4800 manufactured by Hitachi High-Tech Corporation is used. The magnification during observation is 50,000 times.
• the above operation is carried out at five different locations in the composition layer, and the average value (arithmetic mean value) of all the major axis lengths of the filler particles measured in each operation is defined as the average particle size of the filler.
• the above-mentioned major axis refers to the length of the longest line segment among the line segments connecting any two points on the contour line of the outer shape of the filler in the observed image. Furthermore, when the filler particles are aggregated to form aggregates in the observed image, the major axis of each filler particle that constitutes the aggregate is measured.
• filler examples include organic fillers and inorganic fillers, with inorganic fillers being preferred.
• fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as chiandoped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride.
• the filler preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide (silica).
• the shape of the filler may be either spherical or non-spherical (eg, crushed or fibrous), with spherical being preferred.
• the filler may be surface-treated.
• the surface treatment include a treatment for introducing a functional group and a treatment using a known surface treatment agent.
• the functional group include a polymerizable group (e.g., a polymerizable group of the compound Z) and a hydrophobic group.
• the surface treatment agent include a silane coupling agent, a titanate coupling agent, and a silazane compound.
• methods for surface treatment of the filler include a dry method in which the surface treatment is performed in a gas phase, and a wet method in which the surface treatment is performed in a liquid phase.
• Fillers include, for example, NHM-5N (Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass), NHM-3N (Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass), Seahoster KE-S30 (Nippon Shokubai Co., Ltd., silicon dioxide, solids concentration 100% by mass), YA050C-MJE (Admatechs Co., Ltd., silicon dioxide, MEK slurry with solids concentration of 50% by mass), SFP-20M (Denka Co., Ltd., silicon dioxide), and PMA-ST (Nissan Chemical Co., Ltd., silicon dioxide).
• Examples include MEK-ST-L (Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (Nihon Solvay, solids concentration 100% by mass), Y50SP-AM1 (Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass).
• the refractive index of the filler is preferably 0.5 to 30.0, and more preferably 1.2 to 1.8.
• the refractive index can be measured by the method described above.
• the fillers may be used alone or in combination of two or more.
• the content of the filler is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, based on the total solid content of the composition.
• the content of the filler is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 70.0% by mass or less, based on the total solid content of the composition.
• the mass ratio of the filler content to the resin content is preferably from 0.5 to 30.0, and more preferably from 1.0 to 20.0.
• the composition also preferably includes a thermal base generator.
• a thermal base generator In the case where the composition contains a resin precursor, the reaction of the resin precursor is promoted by the composition containing a thermal base generator, and the linear expansion coefficient and insulation reliability are improved.
• the thermal base generator is preferably an acidic compound or an onium salt compound (a compound consisting of a cation and an anion) that generates a base upon heating.
• the onium salt compound is preferably an ammonium salt compound (a compound consisting of an ammonium cation and an anion), an iminium salt compound (a compound consisting of an iminium cation and an anion), a sulfonium salt compound (a compound consisting of a sulfonium cation and an anion), an iodonium salt compound (a compound consisting of an iodonium cation and an anion), or a phosphonium salt compound (a compound consisting of a phosphonium cation and an anion), and more preferably an ammonium salt compound or an iminium salt compound.
• the anion constituting the onium salt compound is preferably a carboxylate anion, a phenol anion, a phosphate anion or a sulfate anion, and more preferably a carboxylate anion. It is also preferable that the anion constituting the ammonium salt compound further has an aromatic ring. Examples of the aromatic ring include aromatic rings constituting the aromatic ring group represented by A a1 in formula (A1) described below.
• the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine.
• the base may be linear, branched, or cyclic, preferably cyclic.
• a a1 represents a p-valent organic group.
• R a1 represents a monovalent organic group.
• L a1 represents a (m+1)-valent linking group.
• m represents an integer of 1 or more.
• p represents an integer of 1 or more.
• a a1 represents a p-valent organic group.
• the organic group include an aliphatic hydrocarbon group and an aromatic ring group, with the aromatic ring group being preferred.
• Examples of the monovalent aliphatic hydrocarbon group include an alkyl group and an alkenyl group.
• the alkyl group may be linear, branched, or cyclic.
• the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 10 carbon atoms.
• alkyl group examples include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.
• the alkenyl group may be linear, branched, or cyclic.
• the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms.
• Examples of the alkenyl group include a vinyl group, an allyl group, and a methallyl group.
• Examples of the aliphatic hydrocarbon group having a valency of p include groups formed by removing (p-1) hydrogen atoms from the above-mentioned monovalent aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group may further have a substituent.
• the aromatic ring group may be either a monocyclic or polycyclic group.
• the aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
• Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group, a phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a fluorene ring group, a biphenyl ring group, a pyrrole ring group, a furan ring group, a
• the ring group examples include an isobenzofuran ring group, an indolizine ring group, an indole ring group, a benzofuran ring group, a benzothiophene ring group, an isobenzofuran ring group, a quinolizine ring group, a quinoline ring group, a phthalazine ring group, a naphthyridine ring group, a quinoxaline ring group, a quinoxazoline ring group, an isoquinoline ring group, a carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thianthrene ring group, a chromene ring group, a xanthene ring group, a phenoxathiin ring group, a phenothiazine ring group, and a phenazine ring group, with a
• R a1 represents a monovalent organic group.
• the monovalent organic group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group represented by A a1 .
• the monovalent organic group may further have a substituent, and the substituent is preferably a carboxy group.
• L a1 represents a linking group having a valence of (m+1).
• the (m+1)-valent linking group include divalent linking groups such as an ether group (-O-), a carbonyl group (-CO-), an ester group (-COO-), a thioether group (-S-), -SO 2 -, -NR N - (R N represents a hydrogen atom or a substituent), an alkylene group (preferably having 1 to 10 carbon atoms) and an alkenylene group (preferably having 2 to 10 carbon atoms); trivalent linking groups having a group represented by "-N ⁇ " and trivalent linking groups having a group represented by "-CR ⁇ " (R represents a hydrogen atom or a substituent); tetravalent linking groups having a group represented by ">C ⁇ "; k-valent linking groups having a cyclic group such as an aromatic ring group and an alicyclic group; and groups combining these.
• m represents an integer of 1 or more. As m, 1 or 2 is preferable, and 1 is more preferable.
• p represents an integer of 1 or more. As p, 1 or 2 is preferable, and 1 is more preferable.
• the ammonium cation constituting the ammonium salt compound is preferably a cation represented by the formula (101).
• the iminium cation constituting the iminium salt compound is preferably a cation represented by the formula (102).
• R 1 to R 4 each independently represent a hydrogen atom or an aliphatic group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
• R5 and R6 each independently represent a hydrogen atom or an aliphatic group.
• R7 represents an aliphatic group. At least two of R5 to R7 may be bonded to each other to form a ring.
• the aliphatic groups represented by R 1 to R 4 and R 5 to R 7 may be linear, branched, or cyclic.
• the aliphatic group preferably has 1 to 10 carbon atoms.
• the aliphatic group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
• the aliphatic group may have a substituent, such as an arylcarbonyl group.
• a methylene group (-CH 2 -) may be replaced with a heteroatom (for example, an oxygen atom, a sulfur atom, or -NR-, where R represents a hydrogen atom or a substituent).
• At least one of R 5 to R 7 is preferably an aliphatic group having —NR—, more preferably an alkyl group having —NR—. At least two of R 5 to R 7 may be bonded to each other to form a ring, and it is preferable that R 5 and R 7 , and R 6 and R 7 are bonded to each other to form a ring. In other words, the ring formed is preferably a polycyclic heterocycle, and more preferably a bicyclic heterocycle.
• thermal base generators examples include those described in WO 2018/038002.
• the temperature at which the thermal base generator generates a base is preferably the heating temperature in step 3 in the method for producing a laminate described below.
• the temperature at which the thermal base generator generates a base is, for example, preferably 50 to 400°C, and more preferably 100 to 250°C.
• the temperature at which the thermal base generator generates a base can be a measured value by a known measurement method or a literature value.
• the base generation temperature can be determined by the peak temperature of the lowest exothermic peak when the compound to be measured is heated to 250° C. at 5° C./min in a pressure-resistant capsule using differential scanning calorimetry.
• the thermal base generator may be used alone or in combination of two or more kinds.
• the content of the thermal base generator is preferably from 0.01 to 10.0 mass %, more preferably from 0.1 to 5.0 mass %, based on the total solid content of the composition.
• the mass ratio of the content of the thermal base generator to the content of the resin X is preferably from 0.0005 to 1.0, more preferably from 0.001 to 0.1, and even more preferably from 0.001 to 0.05.
• the composition may also include a plasticizer.
• the composition layer has excellent step conformability when laminated to an object to be pasted, and a specific film can be formed with high accuracy.
• the composition when the composition contains a filler, the composition preferably contains a plasticizer.
• the plasticizer is a compound different from the various components described above, and preferably does not have a polymerizable group.
• the molecular weight of the plasticizer is preferably 200-1,000, more preferably 250-800, and even more preferably 300-600.
• the above molecular weight refers to the weight average molecular weight.
• the boiling point of the plasticizer is preferably from 230 to 500°C, more preferably from 280 to 480°C, further preferably from 300 to 450°C, and particularly preferably from 350 to 450°C.
• the above boiling point is the boiling point under normal pressure (760 mmHg).
• the boiling point of a compound is a value determined by the following measurement method. When a compound is distilled under normal pressure (760 mmHg), the gas temperature at the point when the evaporated gas starts to condense is defined as the boiling point (measured from 23° C. to 300° C., temperature rise rate 1° C./min).
• distillation of the compound is carried out using a Liebig condenser, and if distillation does not start at 300°C under normal pressure, distillation is carried out under reduced pressure.
• the same distillation (measurement from 23°C to 300°C, temperature increase rate 1°C/min, distillation at the next pressure if distillation does not start at 300°C) is carried out at pressures of 100 mmHg, 50 mmHg, and 5 mmHg in that order, and the boiling point at normal pressure calculated using the nomograph described in Science of Petroleum, Vol. II. p. 1281 (1938) from the temperature and pressure at which condensation of the evaporated gas begins is taken as the boiling point (calculated value).
• the boiling point at normal pressure is considered to be greater than 500°C.
• the method of using the nomograph is as known. Specifically, draw a straight line to connect the boiling point at reduced pressure on line A and the degree of reduced pressure on line C (step 1), read the numerical value at the intersection of the line drawn in step 1 with line B (step 2), and regard this as the boiling point at normal pressure.
• the viscosity of the plasticizer at 25° C. is preferably from 0.01 to 500 mPa ⁇ s, more preferably from 0.05 to 300 mPa ⁇ s, and even more preferably from 0.1 to 100 mPa ⁇ s.
• the viscosity can be measured by a Brookfield viscometer.
• Plasticizers include, for example, polycarboxylic acid esters, phosphoric acid esters, polyether esters, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and benzyl benzoate, with polycarboxylic acid esters being preferred.
• polycarboxylic acid esters examples include aliphatic dicarboxylic acid esters (e.g., adipic acid esters, azelaic acid esters, and sebacic acid esters); aromatic dicarboxylic acid esters (e.g., phthalic acid esters); trimellitic acid esters; and citrate esters (e.g., tributyl acetyl citrate).
• aliphatic dicarboxylic acid esters e.g., adipic acid esters, azelaic acid esters, and sebacic acid esters
• aromatic dicarboxylic acid esters e.g., phthalic acid esters
• trimellitic acid esters e.g., trimellitic acid esters
• citrate esters e.g., tributyl acetyl citrate
• polyvalent carboxylates examples include ethyl phthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetylcitrate, 2-ethylhexyl benzyl phthalate, bis(2-ethylhexyl) isophthalate, tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.
• phosphate esters examples include triamyl phosphate and tris(2-butoxyethyl) phosphate.
• the polyether esters are preferably organic acid esters of polyalkylene glycol.
• organic acids include monocarboxylic acids (e.g., butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexyl acid, and decanoic acid).
• polyether esters include triethylene glycol bis 2-ethylhexanoate.
• alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers include hexaethylene glycol monomethyl ether (mPEG6-OH), pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, and nonaethylene glycol dimethyl ether.
• mPEG6-OH hexaethylene glycol monomethyl ether
• pentaethylene glycol monomethyl ether tetraethylene glycol monomethyl ether
• heptaethylene glycol monomethyl ether octaethylene glycol monomethyl ether
• nonaethylene glycol monomethyl ether pentaethylene glycol dimethyl ether
• the plasticizers may be used alone or in combination of two or more.
• the content of the plasticizer is preferably from 5.0 to 50.0 mass %, more preferably from 10.0 to 30.0 mass %, based on the total solid content of the composition.
• the mass ratio of the plasticizer content to the resin content is preferably from 0.1 to 10.0, and more preferably from 0.5 to 7.0.
• the mass ratio of the plasticizer content to the filler content is preferably from 0.05 to 1.0, and more preferably from 0.2 to 0.7.
• composition also preferably comprises a surfactant.
• Surfactants include, for example, fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants.
• silicone-based surfactants are preferred. From the viewpoint of improving environmental compatibility, it is also preferred that the surfactant does not contain fluorine atoms.
• fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heat is applied, the functional group having the fluorine atom is cleaved and the fluorine atom is volatilized.
• fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), Megafac DS-21, etc.).
• the fluorosurfactant may be a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
• the fluorosurfactant may be a block polymer.
• the fluorine-based surfactant may be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).
• examples of the fluorine-based surfactant include fluorine-containing polymers having a group having an ethylenically unsaturated double bond in the side chain, specifically, Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).
• fluorosurfactants from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group with seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.
• PFOA perfluorooctanoic acid
• PFOS perfluorooctanesulfonic acid
• fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP.
• hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.
• glycerol trimethylolpropane
• trimethylolethane trimethylolethane
• propoxylates e.g., glycerol propoxylate and glycerol ethoxylate
• polyoxyethylene lauryl ether polyoxyethylene stearyl ether
• polyoxyethylene oleyl ether polyoxyethylene octylphenyl
• hydrocarbon surfactants include, for example, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Nippon Corporation); NCW-101, NCW-1001, and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Oil Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).
• silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and/or ends, and polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains.
• silicone surfactants polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains are preferred.
• the above polymers may be either random copolymers or block copolymers.
• the repeating unit having a group with a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).
• R each independently represents an alkyl group having 1 to 3 carbon atoms
• R1 represents a hydrogen atom or a methyl group
• L1 represents a single bond or a divalent organic group.
• the R's may be the same or different.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents an alkylene group having 1 to 10 carbon atoms.
• R 3 represents an alkyl group having 1 to 4 carbon atoms.
• n represents an integer of 5 to 50.
• the repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).
• R4 and R5 each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.
• silicone surfactants include, for example, EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2, and S-506 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Corporation); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-2 2-4515, KF-6004, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP
• the surfactant may also be a nonionic surfactant other than those mentioned above.
• examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
• the surfactant may be used alone or in combination of two or more kinds.
• the content of the surfactant is preferably from 0.01 to 3.0 mass %, more preferably from 0.05 to 1.0 mass %, and even more preferably from 0.1 to 0.8 mass %, based on the total solid content of the composition.
• the composition also preferably includes a rust inhibitor.
• the rust inhibitor may be, for example, a heterocyclic compound.
• the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, a pyrimidine compound, and a pyridine compound, and the triazole compound, the benzotriazole compound, or the tetrazole compound is preferable.
• the heterocyclic compound include compounds described in WO 2022/039027.
• the rust inhibitors may be used alone or in combination of two or more.
• the content of the rust inhibitor is preferably from 0.01 to 3.0 mass %, more preferably from 0.05 to 1.0 mass %, and even more preferably from 0.1 to 0.8 mass %, based on the total solid content of the composition.
• the composition may contain other additives in addition to those mentioned above.
• additives include photoacid generators, curing agents, aliphatic thiol compounds, thermal crosslinking compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, sensitizers, alkoxysilane compounds, maleimide compounds, and hydrosilylation agents.
• the composition may include a photoacid generator.
• the photoacid generator is a compound that generates an acid by light (for example, exposure light, etc.).
• the composition preferably contains a photoacid generator.
• photoacid generators include ionic photoacid generators and non-ionic photoacid generators.
• the ionic photoacid generator include a compound having a sulfonium structure, an onium salt compound having a diaryliodonium or triarylsulfonium structure, and an ammonium salt compound having a quaternary ammonium structure.
• Examples of the ionic photoacid generator include the ionic photoacid generators described in paragraphs 0114 to 0133 of JP2014-085643A.
• nonionic photoacid generators examples include trichloromethyl-s-triazine and its derivatives (trichloromethyl-s-triazine which may have a substituent), compounds having a diazomethane structure, compounds having an imide sulfonate structure, and compounds having an oxime sulfonate structure.
• examples of trichloromethyl-s-triazine and its derivatives, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs 0083 to 0088 of JP 2011-221494 A.
• Examples of oxime sulfonate compounds include the compounds described in paragraphs 0084 to 0088 of WO 2018/179640 A.
• the photoacid generators may be used alone or in combination of two or more.
• the content of the photoacid generator is preferably from 0.1 to 10.0% by mass, and more preferably from 0.5 to 5.0% by mass, based on the total solid content of the composition.
• the composition may also include a curing agent.
• the curing agent is not particularly limited as long as it is a compound that promotes the curing of various components contained in the composition.
• examples of the curing agent include cyanate ester curing agents and benzoxazine curing agents.
• Examples of the cyanate ester curing agent and the benzoxazine curing agent include those described in JP-A-2020-154325 and JP-A-2004-277460.
• the composition may include a solvent.
• the solvent is not particularly limited as long as it can dissolve or disperse various components other than the solvent that may be contained in the composition.
• the solvent include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these.
• the solvent may be used alone or in combination of two or more.
• the content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
• the composition may contain impurities.
• impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Since halide ions, sodium ions, and potassium ions are easily mixed in as impurities, it is preferable to set the contents to the following values.
• the content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, based on the total mass of the composition.
• the lower limit is often 0 ppb by mass or more, but may be 1 ppb by mass or more, or 0.1 ppm by mass or more, based on the total mass of the composition.
• the content of impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.
• Methods for adjusting the impurity content include, for example, using raw materials with low impurity contents as raw materials for the composition, purifying the raw materials for the composition before use, and preventing the inclusion of impurities when preparing the composition.
• the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably small.
• the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the composition.
• the lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the composition.
• the content of these compounds can be adjusted in the same manner as for the above-mentioned impurities, and the content of these compounds can be quantified by known measurement methods.
• Examples of the aliphatic thiol compound, the thermal crosslinking compound, the polymerization inhibitor, and the hydrogen donor compound include various components described in WO 2022/039027.
• Examples of the sensitizer and alkoxysilane compound include the components described in paragraphs 0097 to 0119 of WO 2018/179640.
• Examples of the maleimide compound (a compound having a maleimide ring) include known maleimide compounds and the maleimide compounds described in WO 2022/102756.
• hydrosilylation agents examples include platinum catalysts such as platinum metal-supported carbon powder, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum group metal catalysts such as platinum bisacetoacetate, palladium catalysts, and rhodium catalysts.
• platinum catalysts such as platinum metal-supported carbon powder, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins
• platinum group metal catalysts such as platinum bisacetoacetate, palladium catalysts, and rhodium catalysts.
• the hydrosilylation agent is preferably used as a curing agent when a silicone resin or a precursor thereof is used as the resin.
• the composition is used to form a specific film.
• the specific film is a film containing a component derived from the composition.
• the method for forming the specific film is not particularly limited, and examples thereof include a method of applying a composition onto a substrate, drying the composition, and subjecting the composition to at least one treatment selected from heating and exposure to light, and a method of transferring a composition layer onto a substrate using a transfer film described below, and subjecting the composition layer to at least one treatment selected from heating and exposure to light.
• the preferred aspects of the heating and exposure are the same as those in the below-described step 3.
• the specific film is preferably a film formed by at least heating.
• the specific film a part or all of the components contained in the composition may be reacted (e.g., polymerization of compound Z and conversion of the resin precursor to a resin), and a part of the components contained in the composition (e.g., plasticizer and solvent) may be removed.
• the specific film is preferably a cured film of the composition.
• the average thickness of the specific film is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, even more preferably 3.0 ⁇ m or more, and particularly preferably 5.0 ⁇ m or more, in terms of superior insulation reliability.
• the average thickness of the specific film is preferably 40 ⁇ m or less, more preferably 25 ⁇ m or less, even more preferably 20 ⁇ m or less, and particularly preferably 19 ⁇ m or less, in terms of superior pattern resolution.
• the transfer film of the present invention has a temporary support and a composition layer formed using the above-mentioned composition.
• FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a transfer film.
• the transfer film 100 shown in FIG. 1 has a configuration in which a temporary support 12, a composition layer 14, and a cover film 16 are laminated in this order. 1 has a cover film 16, the transfer film may have no cover film 16. As described later, the transfer film may further have an intermediate layer and/or a thermoplastic resin layer. Each component of the transfer film will be described in detail below.
• the transfer film has a temporary support.
• the temporary support is a member that supports the composition layer, and is ultimately removed by a peeling treatment.
• the temporary support may have either a single-layer structure or a multi-layer structure.
• the temporary support is preferably a film, more preferably a resin film.
• the temporary support is also preferably a film that has flexibility and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat.
• the film include polyethylene terephthalate (PET) film (e.g., biaxially stretched polyethylene terephthalate film, etc.), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, and polyethylene terephthalate film is preferred.
• PET polyethylene terephthalate
• the temporary support is preferably free of deformation such as wrinkles and scratches.
• the temporary support is preferably highly transparent, because it can be pattern-exposed through the temporary support.
• the transmittance at any wavelength of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more.
• the upper limit is preferably less than 100%.
• Preferred values of the transmittance at any wavelength are, for example, 87%, 92%, and 98%.
• the haze of the temporary support is preferably small.
• the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
• the lower limit is preferably 0% or more.
• the number of fine particles, foreign matter, and defects contained in the temporary support is small.
• the number of fine particles, foreign matter, and defects having a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces/10 mm2 or less , more preferably 10 pieces/10 mm2 or less , even more preferably 3 pieces/10 mm2 or less , and particularly preferably 0 pieces/10 mm2 .
• the thickness of the temporary support is preferably from 5 to 200 ⁇ m, and from the viewpoints of ease of handling and versatility, it is more preferably from 5 to 150 ⁇ m, further preferably from 5 to 50 ⁇ m, and particularly preferably from 5 to 35 ⁇ m.
• the thickness of the temporary support can be calculated as the average value of any five points measured by observing a cross section with a SEM (scanning electron microscope).
• the surface of the temporary support which comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.
• the exposure dose of UV irradiation is preferably 10 to 2000 mJ/ cm2 , more preferably 50 to 1000 mJ/ cm2 .
• Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. The lamp power and illuminance can be adjusted as appropriate.
• Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 ⁇ m, a biaxially oriented polyethylene terephthalate film having a thickness of 12 ⁇ m, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 ⁇ m.
• the temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and forming the resulting materials into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).
• the temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support for the purpose of imparting handleability.
• the diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 ⁇ m.
• the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
• temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).
• composition layer is a layer formed using the above composition.
• the various components that can be contained in the composition layer are the same as the various components that can be contained in the above composition, and the preferred embodiments are also the same.
• the preferred numerical range of the contents of the various components in the composition layer is the same as the preferred range obtained by replacing the above "content (% by mass) of the various components relative to the total solid content of the composition” with "content (% by mass) of the various components relative to the total mass of the composition layer.”
• the content of resin X is preferably 5.0% by mass or more relative to the total solid content of the composition” should be replaced with "The content of resin X is preferably 5.0% by mass or more relative to the total mass of the composition layer.”
• composition layer further contains a solvent.
• the solvent has the same meaning as the solvent that the above composition may contain, and the preferred embodiments are also the same.
• the average thickness of the composition layer is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, even more preferably 3.0 ⁇ m or more, and particularly preferably 5.0 ⁇ m or more, in terms of superior insulation reliability.
• the average thickness of the composition layer is preferably 40 ⁇ m or less, more preferably 25 ⁇ m or less, even more preferably 20 ⁇ m or less, and particularly preferably 19 ⁇ m or less, in terms of superior pattern resolution.
• the transfer film may have other layers in addition to those mentioned above.
• the transfer film may have an intermediate layer and/or a thermoplastic resin layer.
• Examples of the intermediate layer and the thermoplastic resin layer include those described in paragraphs 0164 to 0204 of WO 2021/166719, the contents of which are incorporated herein by reference.
• the transfer film may have a cover film.
• the number of fish eyes having a diameter of 80 ⁇ m or more contained in the cover film is preferably 5 or less per square meter.
• Fish eyes are foreign matter, unmelted matter, and/or oxidized deterioration products of the material that are introduced into the film when the material is thermally melted and the film is produced by a method such as kneading, extrusion and/or biaxial stretching and casting.
• the number of particles having a diameter of 3 ⁇ m or more contained in the cover film is preferably 30 pieces/mm2 or less , more preferably 10 pieces/mm2 or less , and even more preferably 5 pieces/mm2 or less . This makes it possible to suppress defects caused by unevenness due to the particles contained in the cover film being transferred to the composition layer.
• the arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably 0.03 ⁇ m or more. If Ra is within this range, for example, when the transfer film is long, the winding property of the transfer film is excellent. Furthermore, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
• cover film examples include a polyethylene terephthalate film, a polypropylene film, a polystyrene film, and a polycarbonate film.
• cover film examples include the cover films described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.
• cover films examples include Alphan (registered trademark) FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan (registered trademark) E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.).
• the cover film may be a recycled product.
• a recycled product may be a product obtained by cleaning and chipping a used film, and then forming the obtained material into a film.
• a commercially available recycled product may be the Ecouse series (manufactured by Toray Industries, Inc.).
• the transfer film may include other layers in addition to the layers described above.
• the other layers include, for example, a high refractive index layer.
• high refractive index layers include those described in paragraphs 0168 to 0188 of WO 2021/187549, the contents of which are incorporated herein by reference.
• the transfer film can be produced by a known production method.
• the method for producing the transfer film preferably involves applying a composition onto a temporary support to form a composition layer, and more preferably involves drying a coating of the composition to form a composition layer.
• Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
• a method for manufacturing the transfer film 100 shown in FIG. 1 includes a method including a step of applying a composition to the surface of the temporary support 12 to form a coating film, and then drying the coating film to form a composition layer 14. Furthermore, a cover film 16 is pressed onto the composition layer of the transfer film produced by the above-mentioned production method to produce the transfer film 100 shown in Fig. 1.
• the transfer film 100 shown in Fig. 1 may be wound up after production and stored as a roll of the transfer film 100.
• the transfer film 100 in the roll form can be provided in that form to the lamination step with a substrate in a roll-to-roll system described later.
• the transfer film may have an intermediate layer and/or a thermoplastic resin layer between the temporary support and the composition layer.
• the composition for forming an intermediate layer the method for forming an intermediate layer, the composition for forming a thermoplastic resin layer, and the method for forming a thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021/033451, the contents of which are incorporated herein by reference.
• the composition is used to form a specific film, and the specific film can be used for various purposes, such as an electrode protective film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plating member.
• the material include protective or insulating films for touch panel electrodes, protective or insulating films for printed wiring boards, protective or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, organic interposers, color filters, overcoat films for color filters, and etching resists for wiring formation.
• the composition and the transfer film can be suitably used for forming an insulating film, and the insulating film is preferably used as an insulating film for a semiconductor package. That is, the composition and the transfer film are preferably used for forming an insulating film for a semiconductor package.
• the composition and transfer film are also preferably used for producing a laminate having a composition layer having a pattern on a substrate.
• the method for producing the laminate of the present invention is not particularly limited as long as it is a method for forming a composition layer on a substrate using the above composition to obtain a laminate.
• the method for producing the laminate preferably includes the following steps 1 to 3. Step 1: forming a composition layer on a substrate using a composition; Step 2: forming a pattern including vias in the composition layer; Step 3: subjecting the pattern to at least one of heating and exposure.
• Step 1 is a step of forming a composition layer on a substrate using a composition.
• the composition layer may be formed by applying the composition.
• the composition may be applied by the composition application method in the above-mentioned method for producing a transfer film.
• the composition layer may be formed by drying a coating of the composition.
• the composition layer may be formed using the above-mentioned transfer film.
• Examples of a method for forming a composition layer using a transfer film include a method in which the surface of the composition layer in the transfer film opposite to the temporary support side is brought into contact with a substrate, and the transfer film and the substrate are laminated together.
• Examples of the lamination method include known transfer methods and lamination methods.
• a preferred method is to place a substrate on the surface of the composition layer and apply pressure and heat with a roll or the like.
• the lamination method may be carried out using a known laminator such as a vacuum laminator or an autocut laminator.
• the lamination temperature is not particularly limited, but is preferably from 70 to 130°C.
• a transfer film it is preferable that a roll-to-roll system be used in step 1.
• the substrate to which the transfer film is attached is preferably a resin film or a resin film having a conductive layer.
• the roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate before any step included in the manufacturing method for the laminate of the present invention, and a step of winding the substrate after any step, and at least any step (preferably all steps or all steps other than the heating step) is performed while transporting the substrate.
• a known method may be used in a manufacturing method that employs a roll-to-roll system.
• the substrate examples include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer.
• the refractive index of the substrate is preferably 1.50 to 1.52.
• the substrate may be a light-transmitting substrate such as a glass substrate, and may be, for example, a reinforced glass such as Gorilla Glass manufactured by Corning Inc.
• materials contained in the substrate include the materials described in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492.
• the resin substrate is preferably a resin film having small optical distortion and/or high transparency, such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.
• PET polyethylene terephthalate
• polyethylene naphthalate polyethylene naphthalate
• polycarbonate polycarbonate
• triacetyl cellulose polyimide
• a resin substrate having a conductive layer is preferred, and a resin film having a conductive layer is more preferred, in that it can be manufactured by a roll-to-roll method.
• the substrate having a conductive layer may be a laminate obtained by the above-mentioned method for manufacturing a laminate.
• the conductive layer may be, for example, any conductive layer used in general circuit wiring or touch panel wiring.
• the conductive layer from the viewpoints of electrical conductivity and fine line formability, one or more layers selected from the group consisting of a metal layer (e.g., a metal foil), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer are preferable, a metal layer is more preferable, and a copper layer or a silver layer is even more preferable.
• the conductive layer in the substrate having the conductive layer may be either one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, the conductive layers are preferably made of different materials.
• Examples of materials for the conductive layer include elemental metals and conductive metal oxides.
• Examples of elemental metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.
• Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and SiO 2. Conductive means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm, and preferably the volume resistivity is less than 1 ⁇ 10 4 ⁇ cm.
• the conductive layer may be in a pattern.
• methods for producing a patterned conductive layer include subtractive methods and additive methods such as etching.
• Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching.
• the etching method may also be a method using an etching resist.
• Step 2 is a step of forming a pattern including vias in the composition layer.
• the pattern having vias may be formed only in the composition layer, or may be formed in both the composition layer and the substrate.
• the pattern including vias may be either through holes or via holes.
• the shape of the via may be, for example, a rectangle, a trapezoid, or an inverted trapezoid in cross-sectional shape; and a circle or a rectangle in front shape (the shape of the via when observed from a direction in which the via bottom is visible).
• An inverted trapezoid is preferred as the cross-sectional shape because it increases the adhesion of plated copper to the via wall surface.
• the via size is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, further preferably 50 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
• the lower limit is preferably 1 ⁇ m or more.
• the number of the vias may be one or more, and is preferably two or more.
• Methods for forming a pattern including vias include, for example, methods using a drill, a laser, and plasma.
• the step of forming a pattern including a via preferably includes a step 2-1 of pattern-exposing the composition layer, and a step 2-2 of developing the pattern-exposed composition layer with a developer to form a pattern.
• pattern exposure refers to a form of pattern-wise exposure, that is, exposure in a form in which exposed areas and unexposed areas exist.
• Step 2-1 is a step of pattern-exposing the composition layer.
• the positional relationship between the exposed and unexposed areas in the pattern exposure is not particularly limited and may be appropriately adjusted.
• the pattern exposure may be performed from the side opposite the substrate to the composition layer, or from the substrate side of the composition layer.
• the light source used for exposure may be any light source that irradiates light in a wavelength range (e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.) to which various photosensitive components in the composition layer (e.g., photopolymerization initiator, photoacid generator, compound Z, etc.) are sensitive.
• a wavelength range e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.
• various photosensitive components in the composition layer e.g., photopolymerization initiator, photoacid generator, compound Z, etc.
• Specific examples of the light source include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
• the exposure dose is preferably from 5 to 2000 mJ/ cm2 , and more preferably from 10 to 1000 mJ/ cm2
• the temporary support may be peeled off from the composition layer and then pattern exposure may be performed, or the temporary support may be peeled off before the temporary support is peeled off.
• the pattern exposure may be exposure through a mask or direct exposure using a laser or the like. Examples of the mask include a quartz mask, a soda lime glass mask, and a film mask. The quartz mask is preferred because of its excellent dimensional accuracy, and the film mask is preferred because it can be easily made large in size.
• the material of the film mask is preferably a polyester film, more preferably a polyethylene terephthalate film, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.). It is preferable to peel off the temporary support from the composition layer before step 2-2.
• Step 2-2 is a step of developing the exposed composition layer using a developer to form a pattern after the above step 2-1.
• the developer may be, for example, an alkaline developer or an organic solvent developer.
• the alkaline developer is preferably an alkaline aqueous solution.
• the alkaline aqueous solution is preferably a solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol/L.
• the content of water in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the alkaline developer.
• the upper limit is preferably less than 100% by mass based on the total mass of the alkaline developer.
• Examples of the alkaline developer include an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, and an aqueous solution of tetramethylammonium hydroxide (TMAH).
• concentration of the alkaline component constituting the alkaline developer is, for example, a 0.1% by mass aqueous solution, a 1.0% by mass aqueous solution, and a 2.38% by mass aqueous solution.
• the alkaline developer may contain a water-soluble organic solvent, a surfactant, etc. Examples of the alkaline developer include the developer described in paragraph [0194] of WO2015/093271.
• organic solvent developers include developers containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• organic solvent developer cyclopentanone or propylene glycol monomethyl ether acetate is preferred, and cyclopentanone is more preferred.
• a plurality of organic solvents may be mixed, or may be mixed with an organic solvent other than the above or water.
• the content of water in the organic solvent developer is preferably less than 10% by mass, more preferably substantially free of water, based on the total mass of the organic solvent developer.
• the content of organic solvent in the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent developer.
• the upper limit is preferably 100% by mass or less, based on the total mass of the organic solvent developer.
• Examples of development methods include paddle development, shower development, spin development, and dip development.
• shower development unnecessary parts can be removed by spraying a developer onto the composition layer after exposure. It is also preferable to spray a cleaning agent or the like onto the layer after development and remove development residues by rubbing with a brush or the like.
• the temperature of the developer is preferably 20 to 40°C.
• Step 3 is a step of subjecting the pattern obtained in step 2 to at least one of heating and exposure to light. Step 3 may facilitate reaction of the resin precursors of the composition (eg, ring-closing reaction of the polyimide precursor and the polybenzoxazole precursor) to form a resin. Step 3 is preferably a step of at least heating.
• the temperature and time of the heat treatment can be appropriately selected depending on the type of the resin and its precursor.
• the temperature of the heat treatment is preferably from 120 to 400°C, more preferably from 150 to 400°C, and even more preferably from 180 to 350°C.
• the heat treatment time is preferably from 1 to 24 hours, more preferably from 1 to 12 hours, and even more preferably from 1 to 9 hours.
• the heat treatment may be carried out in either an air environment or a nitrogen-substituted environment.
• the atmospheric pressure in the heat treatment environment is preferably 8.1 kPa or more, more preferably 50.66 kPa or more.
• the upper limit is preferably 121.6 kPa or less, more preferably 111.46 kPa or less, and even more preferably 101.3 kPa or less.
• the light source and the exposure dose for the exposure treatment can be appropriately selected depending on the type of photosensitive component in the composition.
• Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
• the exposure dose is preferably from 5 to 2000 mJ/ cm2 , and more preferably from 10 to 2000 mJ/ cm2 .
• the method for producing the laminate may include other steps in addition to those described above. Examples of other steps include the following steps:
• ⁇ Cover film peeling process> when the transfer film has a cover film, it is preferable to include a step of peeling off the cover film of the transfer film.
• the cover film can be peeled off by a known method.
• the method for producing a laminate may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer.
• the treatment for reducing the visible light reflectance may be performed on some or all of the conductive layers.
• the visible light reflectance can be reduced by oxidation treatment. For example, copper can be oxidized to form copper oxide, which is blackened, thereby reducing the visible light reflectance of the conductive layer.
• Suitable embodiments of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of JP 2014-150118 A, and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, the contents of which are incorporated herein by reference.
• the method for producing the laminate may include a step (etching step) of etching the conductive layer in an area where the etching resist film is not disposed, using the pattern (film) formed in step 2 or step 3 as an etching resist film.
• the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP-A-2010-152155 and the like, and known dry etching methods such as plasma etching.
• a substrate having a plurality of conductive layers on each of its two surfaces is preferably used, and patterns are formed on the conductive layers formed on both surfaces successively or simultaneously.
• the first conductive pattern can be formed on one surface of the substrate, and the second conductive pattern can be formed on the other surface of the substrate. It is also preferable to form the conductive patterns from both sides of the substrate by roll-to-roll.
• the laminate is a laminate obtained by the above-mentioned method for producing a laminate, and has a substrate and a composition layer having a pattern including vias.
• the laminate is used, for example, in semiconductor devices, including various semiconductor devices such as semiconductor packages used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).
• Step Z1 A step of forming a composition layer on a substrate having a conductive layer
• Step Z2 A step of forming a pattern having a via in the composition layer
• Step Z3 A step of heat-treating the pattern
• Step Z4 A step of forming a circuit pattern on the pattern.
• Steps Z1 to Z3 in the semiconductor package manufacturing method include steps 1 to 3 described above, respectively.
• Step Z4 is a step of forming a circuit pattern on the pattern.
• a semi-additive process is preferable because it is capable of forming fine wiring.
• Examples of the semi-additive process include the following methods. First, after the above-mentioned step Z3, the via bottom, the via wall surface and the entire surface of the pattern are subjected to electroless copper plating using a palladium catalyst or the like to form a seed layer.
• the seed layer is for forming a power supply layer for electrolytic copper plating, and the thickness of the seed layer is preferably 0.1 to 2.0 ⁇ m.
• the electroless copper plating process is carried out by reacting copper ions with a reducing agent to deposit metallic copper on the surface of a pattern having vias.
• the catalyst for the electroless plating process is preferably a palladium-tin mixed catalyst.
• the average primary particle size of the mixed catalyst is preferably 10 nm or less.
• the plating composition for the electroless plating process preferably contains hypophosphorous acid as a reducing agent.
• Commercially available electroless copper plating solutions include, for example, “MSK-DK” manufactured by Atotech Japan, and “ThruCup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.
• the composition layer of the transfer film opposite to the temporary support onto the electroless copper plating is heat-press the surface of the composition layer of the transfer film opposite to the temporary support onto the electroless copper plating using a roll laminator.
• the thickness of the composition layer is preferably 5 to 30 ⁇ m, since this allows the thickness to be greater than the height of the wiring after electrolytic copper plating.
• the composition layer is exposed to light through a mask having a desired wiring pattern drawn thereon, for example. Examples of the exposure method include the exposure method in step 2-1. After the exposure, the temporary support of the transfer film is peeled off, and the exposed composition layer is developed using an alkaline developer to form a pattern. After the pattern is formed, the development residue of the composition may be removed using plasma or the like.
• electrolytic copper plating is carried out to form a copper circuit layer and fill vias.
• the pattern is stripped using an alkaline aqueous solution or an amine-based stripper.
• the seed layer between the wirings is removed (flash etching). Flash etching is performed using an oxidizing solution containing, for example, sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of the oxidizing solution include "SAC” manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Co., Ltd.
• Palladium and the like adhering to the portions between the wirings are removed as necessary. Palladium can be removed using an acidic solution such as nitric acid and hydrochloric acid.
• a post-baking treatment is preferably performed to sufficiently thermally cure any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper.
• a curing temperature of 150 to 240° C. and a curing time of 15 to 500 minutes are preferable.
• the method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias.
• the roughening step is preferably performed after the step Z3 and before the step Z4.
• the surface of the pattern is roughened to improve adhesion with the circuit wiring.
• smears can also be removed.
• the roughening step may be, for example, a known desmear treatment, and is preferably a treatment in which a roughening liquid is brought into contact with the surface.
• the roughening solution examples include a roughening solution containing chromium and sulfuric acid, a roughening solution containing an alkaline permanganate (such as a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.
• a roughening solution containing chromium and sulfuric acid examples include a roughening solution containing chromium and sulfuric acid, a roughening solution containing an alkaline permanganate (such as a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.
• the above-mentioned steps can be repeated depending on the number of layers required to manufacture a semiconductor package. It is also preferable to form a solder resist on the outermost layer.
• the semiconductor package is not particularly limited as long as it contains the specific film.
• the semiconductor package preferably includes the above-mentioned laminate, and is more preferably manufactured using the above-mentioned method for manufacturing a semiconductor package.
• the specific film may be used as an insulating film, or may be used as an organic interposer or insulating film in a so-called build-up substrate.
• a mixture was prepared by mixing various components in the amounts (solid content ratio) shown in the table below. Next, the upper mixture was diluted with a mixed solvent containing 25% by mass of MEK (methyl ethyl ketone) and 75% by mass of NMP (N-methylpyrrolidone) to a solid content of 30% by mass.
• MEK methyl ethyl ketone
• NMP N-methylpyrrolidone
• A-1 Polyimide precursor, resin synthesized by the synthesis method of resin A-1 described later
• A-2 Polyimide precursor, resin synthesized by the synthesis method of resin A-2 described later
• A-3 Polyimide precursor, resin synthesized by the synthesis method of resin A-3 described later
• A-4 Polybenzoxazole precursor, resin synthesized by the synthesis method of resin A-4 described later
• A-5 Phenol resin, TR4020G, manufactured by Asahi Organic Chemicals Co., Ltd.
• A-6 Epoxy resin, ZX1059 (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (1:1)), manufactured by Nippon Steel Chemical & Material Co., Ltd.
• A-7 Polyphenylene ether resin having a branched structure, resin synthesized by the synthesis method of resin A-7 described later
• A-9 Benzocyclobutene resin, cyclotene resin XUR-JW-1148-200201415-47, manufactured by Dow Chemical Company
• A-10 Liquid crystal polyester, resin synthesized by the synthesis method of resin A-10 described later
• A-11 Vinylbenzyl-modified polyphenylene ether resin, manufactured by Mitsubishi Gas Chemical Company, "OPE-2St 1200" toluene solution
• A-12 Acrylic resin, ARUFON UC-3000, manufactured by Toa
• SOCl 2 thionyl chloride
• the reaction solution obtained was added to ethyl alcohol (3 L) to obtain a precipitate, which is a crude polymer.
• the crude polymer obtained was filtered and dissolved in tetrahydrofuran (1.5 L) to obtain a crude polymer solution.
• the crude polymer obtained was purified using an anion exchange resin (Amberlyst TM15, manufactured by Organo Corporation) to obtain a polymer solution.
• the polymer solution obtained was dropped into water (28 L) to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polyimide precursor resin A-2.
• the weight average molecular weight (Mw) of Resin A-2 was 22,000.
• the imide group content of the polyimide obtained from Resin A-2 was 27.4% by mass per repeating unit.
• Resin A-7 The number average molecular weight of Resin A-7 was 25,000, and the weight average molecular weight was 66,000.
• J-1 Jer828: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation J-2: HPC8000-65T: Dicyclopentadiene type diphenol compound (polycyclopentadiene type diphenol compound) type active ester curing agent, toluene solution with solid content concentration of 65% by mass, manufactured by DIC Corporation J-3: Organosilicon compound (silyl compound): Compound synthesized by the following method 700.0 g of 1,4-bis(dimethylsilyl)benzene (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.36 g of 5% by mass platinum carbon powder (manufactured by N.E.
• the components (a) to (e) are shown below.
• Oxe-01 Photopolymerization initiator, Irgacure OXE-01, manufactured by BASF NHM-5N: Filler, silicon dioxide (spherical silica), average particle size 100 nm, manufactured by Tokuyama NHM-3N: Filler, silicon dioxide (spherical silica), average particle size 150 nm, manufactured by Tokuyama YA050C-MJE: Filler, silicon dioxide (spherical silica slurry), average particle size 50 nm, manufactured by Admatec NP-5N: Filler, silicon dioxide (spherical silica), average particle size 100 nm, manufactured by Tokuyama E-1: Thermal base generator, compound having the following structure
• EPEG plasticizer, ethyl phthalyl ethyl glycolate, manufactured by Tokyo Chemical Industry Co., Ltd.
• S-506 silicone surfactant, manufactured by DIC Corporation F-551A: Megafac (registered trademark) F551A, fluorine-based surfactant, manufactured by DIC Corporation HAT: rust inhibitor, 5-amino-1H tetrazole J-4: platinum catalyst: hydrosilylation agent, dilution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex into polysiloxane (platinum content: 1% by mass), component (C) of JP2020-026502A J-5: isopropylidene group-containing maleimide compound, MIR-500-60T, toluene solution TEGDA: polymerizable compound without liquid crystallinity, tetraethylene glycol diacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.
• the prepared composition was applied onto a copper substrate and dried at 100°C to obtain a laminate having a composition layer of 5 ⁇ m thickness on the copper substrate.
• the obtained laminate was exposed to light from the side opposite to the substrate side of the composition layer (ultra-high pressure mercury lamp, cumulative illuminance measured with a 365 nm wavelength illuminometer: 1000 mJ/cm 2 ).
• development was performed at room temperature using the developer shown in the table below until the composition layer in the unexposed area disappeared. Thereafter, the boundary between the exposed and non-exposed areas was observed with an optical microscope, and the presence or absence of photolithographic properties was evaluated according to the following evaluation criteria. If a residual film was confirmed in the exposed area, the composition layer has photolithographic properties.
• the prepared composition was applied onto a copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) substrate and dried to obtain a laminate having a 30 ⁇ m-thick composition layer on the copper substrate.
• a free-standing film of the composition was obtained by the following procedure.
• the obtained laminate was exposed to light (accumulated illuminance of 100 mJ/ cm2 measured with an ultra-high pressure mercury lamp and a 365 nm wavelength illuminometer) from the side opposite to the substrate side of the composition layer, and then heated in an oven (200°C, 8 hours) to form a specific film.
• the laminate was immersed in 2M hydrochloric acid for 8 hours for peeling treatment, rinsed (pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film (specific film) derived from the composition layer.
• a free-standing film of the composition was obtained by the following procedure.
• the obtained laminate was subjected to a heat treatment in an oven (200°C, 8 hours) to form a specific film, and then the laminate was immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, rinsed (in pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film (specific film) derived from the composition layer.
• the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about one week until it was peeled off.
• the produced free-standing film was cut into a rectangular shape (19 mm x 5 mm), and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM” manufactured by TA Instruments). The measurement conditions were a heating rate of 10°C/min, a chuck distance of 10 mm, and a load of 40 mN.
• the linear expansion coefficient was measured as a value (ppm/K) in the range of 50 to 150°C during heating, and was calculated as the average value of three measurements. The obtained linear expansion coefficient was evaluated according to the following evaluation criteria.
• the prepared composition was applied onto a substrate and dried at 100° C. to form a composition layer, thereby obtaining a laminate.
• the thickness of the composition layer was adjusted so that the thickness of the composition layer on the copper pattern after drying was 10 ⁇ m.
• an evaluation sample was prepared by the following procedure.
• the obtained laminate was exposed to light from the side opposite to the substrate side of the composition layer (ultra-high pressure mercury lamp, cumulative illuminance measured with a 365 nm wavelength illuminometer: 100 mJ/cm 2 ). After exposure, the laminate was heat-treated at 200° C. for 480 minutes in a nitrogen atmosphere to prepare an evaluation sample.
• an evaluation sample was prepared by the following procedure. The laminate was subjected to a heat treatment at 200° C. for 480 minutes in a nitrogen atmosphere to prepare a sample for evaluation.
• a laminate having a composition layer formed using a transfer film prepared by the following procedure was evaluated in the same manner as the above-mentioned [Linear expansion coefficient], and the evaluation results obtained were equivalent to the evaluation results of the [Linear expansion coefficient] for the specific film formed using the composition.
• the composition of each example was applied onto a temporary support (16QS, manufactured by Toray Industries, Inc., PET film having a thickness of 16 ⁇ m) and dried at 100° C. to form a composition layer. The film thickness of the composition layer was adjusted to 10 ⁇ m after drying.
• a cover film (manufactured by Oji F-Tex Co., Ltd., polypropylene film, FG-201, thickness 30 ⁇ m) was attached to the side of the composition layer opposite the temporary support to obtain a transfer film having a composition layer.
• the cover film was peeled off from the obtained transfer film, and the exposed composition layer was laminated on a copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) substrate to transfer the composition layer, and then the temporary support was peeled off.
• the lamination was performed using a vacuum laminator (manufactured by MCK Corporation) at a rubber roller temperature of 100°C and a conveying speed of 1 m/min. Furthermore, the operation of transferring the composition layer onto the obtained composition layer on the substrate in the same manner was repeated twice, and a laminate having a composition layer of 30 ⁇ m thickness on the substrate was obtained.
• the cover film was peeled off from the transfer film obtained by the above method, and the exposed composition layer was laminated on a copper substrate to transfer the composition layer.
• the lamination was performed using a vacuum laminator (manufactured by MCK Corporation) at a rubber roller temperature of 100° C. and a conveying speed of 1 m/min.
• the obtained laminate was exposed to light (ultra-high pressure mercury lamp, cumulative illuminance measured with a 365 nm wavelength illuminometer of 1000 mJ/cm 2 ) from the side opposite to the substrate side of the composition layer. After exposure, development was performed at room temperature using the developer shown in the table until the composition layer in the unexposed area disappeared. Thereafter, the boundary between the exposed and unexposed areas was observed with an optical microscope and evaluated according to the same evaluation criteria as in the above-mentioned [Photolithographic properties], and the same evaluation results as those of the composition layer formed by applying and drying the composition were obtained.
• the transfer film of each Example obtained by the above-mentioned method was applied to a glass epoxy substrate (CCL-EL190T, thickness 1.0 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern was formed, and composition layers were formed on both sides of the glass epoxy substrate.
• Lamination was performed using a vacuum laminator (manufactured by MCK Corporation) under the conditions of a substrate temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N/cm, and a conveying speed of 2 m/min.
• a pattern having a via with a diameter of ⁇ 60 ⁇ m was formed at a predetermined position on the composition layer, and then heat treatment was performed, and the residue was removed with a sodium permanganate aqueous solution as a roughening solution, and electroless plating treatment was performed.
• a resist pattern was formed at a predetermined position using a known dry film resist, and electrolytic plating treatment was performed.
• the resist pattern was peeled off with a peeling solution.
• a seed layer etching treatment was performed, and then a heat treatment (200° C., 1.5 hours) was performed to form copper wiring on the cured film.

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