Composition, transfer film, method for producing laminate, laminate, and semiconductor package

Abstract

The present invention addresses the problem of providing a composition with which it is possible to form a film having exceptional dielectric characteristics and migration resistance. A composition according to the present invention contains a resin and an inorganic filler, wherein: the resin contains at least one selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, epoxy resins, polyphenylene ether resins, acrylic resins, and methacrylic resins; the inorganic filler is surface-modified using two or more surface modifiers; at least one of the two or more surface modifiers has a reactive group; and at least one of requirements 1 and 2 is satisfied. Requirement 1: The resin has a reactive group. Requirement 2: The composition contains a compound that has a reactive group, said compound being different from the resin.

Description

Composition, transfer film, laminate manufacturing method, laminate, semiconductor package

[0001] The present invention relates to a composition, a transfer film, a method for producing a laminate, a laminate, and a semiconductor package.

[0002] In display devices (e.g., organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance-type input device, conductive patterns such as an electrode pattern corresponding to a sensor in the viewing area, and wiring for peripheral wiring and lead-out wiring are provided inside the touch panel. An insulating film is used for the purpose of forming and protecting such electrode patterns and conductive patterns. Similarly, in multilayer printed wiring boards and build-up substrates for semiconductor packages, insulating films are provided between each layer for the purpose of insulating and protecting the wiring between the wiring.

[0003] As a composition capable of forming the above insulating film, Patent Document 1 discloses an epoxy resin composition containing an epoxy resin.

[0004] Japanese Patent Application Laid-Open No. 2007-254709

[0005] The present inventors have found that when a film is formed using a composition having a structure as described in Patent Document 1, it is difficult to obtain a film having both good dielectric properties and good migration resistance.

[0006] Therefore, an object of the present invention is to provide a composition capable of forming a film having excellent dielectric properties and excellent migration resistance, as well as a transfer film, a method for producing a laminate, a laminate, and a semiconductor package relating to the composition.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A composition comprising a resin and an inorganic filler, wherein the resin comprises at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, a polybenzoxazole, an epoxy resin, a polyphenylene ether resin, an acrylic resin, and a methacrylic resin, the inorganic filler is surface-modified with two or more surface modifiers, and at least one of the two or more surface modifiers has a reactive group, and the composition satisfies at least one of Requirement 1 and Requirement 2. Requirement 1: The resin has a reactive group. Requirement 2: The composition contains a compound different from the resin and having a reactive group. [2] The composition according to [1], wherein the two or more surface modifiers include a surface modifier A having a molecular weight of 220 or more and a surface modifier B having a molecular weight of less than 220. [3] The composition according to [1] or [2], wherein the reactive group is a group having an ethylenically unsaturated double bond. [4] The composition according to any one of [1] to [3], wherein the resin comprises at least one selected from the group consisting of a polyimide precursor and a polyimide. [5] The composition according to [4], wherein the surface modifier having a reactive group is a compound represented by formula (S) described below, the inorganic filler is silicon dioxide, and the two or more surface modifiers comprise at least one selected from the group consisting of a disilazane compound and a basic compound. [6] The composition according to [5], wherein the basic compound has a pKaH of 4.0 to 15.0. [7] The composition according to any one of [1] to [4], wherein the inorganic filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates. [8] The composition according to any one of [1] to [7], wherein the inorganic filler has an average particle size of 300 nm or less. [9] The composition according to any one of [1] to [8], wherein the inorganic filler has an average particle size of 150 nm or less.

[10] The composition according to any one of [1] to [9], wherein the content of the inorganic filler is 30.0 mass % or more based on the total solid content of the composition.

[11] The composition according to any one of [1] to

[10] , wherein the content of the inorganic filler is 90.0 mass % or less based on the total solid content of the composition.

[12] A transfer film having a temporary support and a composition layer formed using the composition according to any one of [1] to

[11] .

[13] A method for producing a laminate, comprising: Step 1: forming a composition layer on a substrate using the composition according to any one of [1] to

[11] ; Step 2: patternwise exposing the composition layer; Step 3: developing the patternwise exposed composition layer with a developer to form a pattern having vias; and Step 4: subjecting the obtained pattern to at least one of heating and exposure.

[14] A laminate produced by the method for producing a laminate according to

[13] .

[15] A semiconductor package comprising the laminate according to

[14] .

[0009] The present invention provides a composition capable of forming a film having excellent dielectric properties and excellent migration resistance. It also provides a transfer film, a method for producing a laminate, a laminate, and a semiconductor package relating to the composition.

[0010] FIG. 2 is a schematic diagram illustrating an example of a layer structure of a transfer film.

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] The term "step" in this specification includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

[0014] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, the temperature when performing each of the above steps may be 25° C. unless otherwise specified.

[0015] In this specification, "transparent" means that the average transmittance of visible light in the wavelength range 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.

[0016] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light, extreme ultraviolet light, X-rays, EUV light, etc., as typified by mercury lamps and excimer lasers, but also exposure using particle beams such as electron beams and ion beams.

[0017] In this specification, the "solid content" of a composition refers to the components that form a film formed using the composition. Typically, when the composition contains a solvent (e.g., an organic solvent and water), it refers to all components excluding the solvent. In addition, liquid components that form a film are also considered to be solid content.

[0018] In this specification, unless otherwise specified, the content ratio of each repeating unit of the resin is a molar ratio. In this specification, unless otherwise specified, the molecular weight when there is a molecular weight distribution is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​obtained by gel permeation chromatography (GPC) in terms of polystyrene.

[0019] In this specification, "(meth)acrylic acid" is a concept that encompasses both acrylic acid and methacrylic acid, "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate, and "(meth)acrylamide group" is a concept that encompasses both acrylamide group and methacrylamide group.

[0020] In this specification, the bonding direction of a divalent group (e.g., -CO-O-) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be "X-O-CO-Z" or "X-CO-O-Z." Unless otherwise specified, the compounds described in this specification may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, only one type of isomer or isotope may be contained, or multiple types may be contained.

[0021] In this specification, unless otherwise specified, the thickness (film thickness) of a layer is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0022] In this specification, unless otherwise specified, the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg). In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0023] [Composition] The composition of the present invention will be described in detail below. The composition of the present invention (hereinafter also simply referred to as the "composition") is a composition containing a resin and an inorganic filler, wherein the resin contains at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, a polybenzoxazole, an epoxy resin, a polyphenylene ether resin, an acrylic resin, and a methacrylic resin, the inorganic filler is surface-treated with two or more surface modifiers, and at least one of the two or more surface modifiers has a reactive group, and satisfies at least one of Requirement 1 and Requirement 2. Requirement 1: The resin has a reactive group. Requirement 2: The composition contains a compound that is different from the resin and has a reactive group. Hereinafter, an inorganic filler surface-treated with two or more surface modifiers will also be referred to as a "specific inorganic filler."

[0024] While the reason why the composition having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. It is speculated that a film formed using the composition has excellent dielectric properties due to the specific resin contained in the composition, and also has excellent migration resistance due to the specific inorganic filler contained in the composition. It is also speculated that the improvement in migration resistance is also contributed by at least one of the following: the surface modifier used to surface modify the specific inorganic filler contains a surface modifier having a reactive group, and the resin in the composition has a reactive group (Requirement 1); and the composition contains a compound that is different from the resin and has a reactive group (Requirement 2). Hereinafter, a film formed using the composition of the present invention will also be referred to as a "specific film." The achievement of at least one of the effects of excellent dielectric properties and excellent migration resistance of the specific film will also be referred to as the "effect of the present invention."

[0025] [Requirements 1 and 2] The composition satisfies at least one of requirements 1 and 2, and may satisfy both requirements 1 and 2. The reactive group possessed by the resin in requirement 1 and the compound having a reactive group in requirement 2 will be described later. It is more preferable that the reactive group possessed by the surface modifier and the reactive group possessed by the resin in requirement 1 are the same type of group.

[0026] The composition preferably has the following configuration: At least one of the two or more surface modifiers is a surface modifier having a first reactive group, and the composition satisfies at least one of Requirement 1A and Requirement 2A. Requirement 1A: The resin has a second reactive group that reacts with the first reactive group. Requirement 2A: The composition contains a compound that is different from the resin and has a second reactive group that reacts with the first reactive group. The first reactive group is preferably a reactive group that the resin described below can have. The second reactive group is not particularly limited as long as it is a group that reacts with the first reactive group. For example, when the first reactive group is a polymerizable group, the second reactive group may be the same type of polymerizable group as the first reactive group (for example, when both the first reactive group and the second reactive group are acryloyl groups).

[0027] The various components that may be contained in the composition of the present invention are described in detail below.

[0028] [Resin] The composition contains a resin. The resin contains at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, a polybenzoxazole, an epoxy resin, a polyphenylene ether resin, an acrylic resin, and a methacrylic resin. In terms of achieving better effects of the present invention, the resin preferably contains at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, a polybenzoxazole, an epoxy resin, and a polyphenylene ether resin, more preferably contains at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole, even more preferably contains at least one selected from the group consisting of a polyimide precursor and a polyimide, particularly preferably contains a polyimide precursor, and most preferably is a polyimide precursor. Precursors of various resins are resins that can be converted into various resins by heat treatment, light treatment, or chemical treatment.

[0029] The resin may have a reactive group. When the composition satisfies requirement 1, the resin has a reactive group. Examples of the reactive group include a polymerizable group and a functional group other than a polymerizable group. Examples of the polymerizable group include known polymerizable groups such as a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, with a radically polymerizable group being preferred. The radically 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, with a (meth)acryloyl group being preferred. Examples of functional groups other than the polymerizable group include an amino group, a hydroxyl group, and a thiol group, with an amino group being preferred, a secondary amino group (e.g., a phenylamino group, a methylamino group, an ethylamino group, etc.), or a primary amino group (-NH ２ ) is more preferred. Functional groups other than silanol groups (Si—OH) are also preferred.

[0030] The resin may have an acid-decomposable group. Examples of the acid-decomposable group include the acid-decomposable groups described in paragraphs 0024 to 0031 of WO 2019 / 187881.

[0031] <Polyimide and Polyimide Precursor> Polyimide is a resin having an imide structure. As the polyimide, a resin having a cyclic imide structure is preferable. Furthermore, the polyimide may have a substituent. As the polyimide, a resin synthesized from a polyimide precursor having a repeating unit represented by formula (1) (for example, a resin obtained by a ring-closing reaction) is preferable. The polyimide precursor preferably has a repeating unit represented by formula (1).

[0032]

[0033] In formula (1), A １ and A ２ R each independently represents an oxygen atom or —NH—. １１１ represents a divalent organic group. １１３ and R １１４R each independently represents a hydrogen atom or a monovalent organic group. １１５ represents a tetravalent organic group.

[0034] In formula (1), A １ and A ２ each independently represents an oxygen atom or —NH—. １ and A ２ is preferably an oxygen atom.

[0035] In formula (1), R １１１ represents a divalent organic group. Examples of the divalent organic group include a divalent aliphatic group, a divalent aromatic ring group, and a group formed by 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 formed by 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. Examples of the heteroatom include -O-, -CO-, -S-, and -SO. ２ It may be contained in the divalent organic group as a group such as - and -NHCO-. １１１ As the diamine, a divalent organic group derived from a diamine is also preferred. The diamine is preferably a diamine used in the production of a polyimide precursor, with aliphatic diamines or aromatic diamines being 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 group combining these, with diamines having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamines) being more preferred. Examples of the aromatic ring group include groups having the following structure:

[0036]

[0037] In AR-8 to AR-10, A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, —O—, —CO—, —S—, or —SO ２A represents an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, or -SO ２ - is preferred, and -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ - is more preferred, and -O- is even more preferred.

[0038] R １１１ As for *-Ar ０ -L ０ -Ar ０ -* is also preferred. ０ each independently represents a divalent aromatic hydrocarbon group. ０ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO ２ represents -, -NHCO-, a group formed by combining these, or a single bond. * represents the bonding position. ０ They may be the same or different from each other.

[0039] Ar ０ The number of carbon atoms in the divalent aromatic hydrocarbon group represented by the formula (I) is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenylene group. ０ has the same meaning as A described above, and the preferred embodiments are also the same.

[0040] Examples of diamines 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, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethyl biphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4 -amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)anthracene ...3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraafluorobenzoate aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5- Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane , 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl. Further, examples of diamines include compounds represented by any one of formulas (DA-1) to (DA-18).

[0041]

[0042]

[0043] Further, the diamine also includes a diamine having two or more alkylene glycol units in the main chain, and as the diamine having two or more alkylene glycol units in the main chain, a diamine containing two or more ethylene glycol chains and / or two or more propylene glycol chains in one molecule is preferred. Diamines not containing aromatic rings are also preferred. Examples of the diamine 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.

[0044] In formula (1), R １１３ and R １１４R each independently represents a hydrogen atom or a monovalent organic group. １１３ and R １１４ Preferably, at least one of R represents a group having a reactive group, １１３ and R １１４ It is more preferable that both R and R represent a group having a reactive group. Examples of the reactive group include the groups exemplified as the reactive group that the resin may have. The monovalent organic group may be the monovalent organic group X described below. １１３ and R １１４ Examples of the reactive group include the reactive groups described above, and a group having an ethylenically unsaturated double bond is preferred, and a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by formula (III) is more preferred.

[0045]

[0046] In formula (III), R ２００ represents a hydrogen atom or a methyl group. 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. * indicates the bonding position.

[0047] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２００ As the alkyl group, a methyl group is preferred.

[0048] In formula (III), 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 ２０１Examples of the alkyl group 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 -, and examples thereof include an ethylene group, a propylene group, a trimethylene group, or -CH ２ CH(OH)CH ２ - is preferred, and an ethylene group is more preferred.

[0049] R １１３ or R １１４ Examples of the monovalent organic group represented by the formula (I) 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 specifically, 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 Also preferred as R is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, or a 4-hydroxybenzyl group. １１３ or R １１４ The monovalent organic group represented by the formula (I) also includes a leaving group which is eliminated by the action of an acid.

[0050] In formula (1), R １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group having an aromatic ring is preferred, and a group represented by formula (5) or a group represented by formula (6) is more preferred.

[0051]

[0052] In formula (5), 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 * represents a bonding position. In formula (6), * represents a bonding position.

[0053] In formula (5), R１１２ has the same meaning as A described above, and the preferred embodiments are also the same.

[0054] The tetravalent organic group may be, for example, 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).

[0055]

[0056] In formula (7), R １１５ represents a tetravalent organic group. １１５ is R in formula (1). １１５ The same definition and preferred embodiments are also the same.

[0057] Examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride. hydrate, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalene Examples thereof include tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

[0058] Examples of the tetracarboxylic dianhydride include compounds represented by any one of formulas (DAA-1) to (DAA-5).

[0059]

[0060] (Monovalent Organic Group X) 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. The cyclic group may be monocyclic or polycyclic. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 30. The number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 30. Examples of the alkyl group 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; monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic cycloalkyl groups such as adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, campholoyl, dicyclohexyl, and pinenyl. The substituent that the alkyl group may have is preferably an aromatic ring group, as described below.

[0061] The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic ring group may be either a monocyclic or polycyclic ring. Examples of rings 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, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyridine ... Examples of aromatic heterocyclic groups include 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.As the substituent that the aromatic ring group may have, the above-mentioned alkyl group is preferred.

[0062] 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).

[0063]

[0064] In formula (1-A) and formula (1-B), A １１ and A １２ represents an oxygen atom or —NH—. １１１ and R １１２ R each independently represents a divalent organic group. １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group.

[0065] In formula (1-A) and formula (1-B), A １１ , A １２ , R １１１ , R １１３ , and R １１４ are respectively represented by A in formula (1). １ , A２ , R １１１ , R １１３ , and R １１４ In formula (1-A), R １１２ In formula (5), R １１２ The same definition and preferred embodiments are also the same.

[0066] In formula (1-A), the bonding positions of the carbonyl group to the benzene ring are preferably 4, 5, 3', and 4' in formula (1-A).In formula (1-B), the bonding positions of the carbonyl group to the benzene ring are preferably 1, 2, 4, and 5 in formula (1-B).

[0067] The polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).

[0068] 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.

[0069] The polyimide precursor preferably contains fluorine atoms. 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.

[0070] 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 a substrate. Examples of the aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.

[0071] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyimide precursor has a polydispersity (Mw / Mn) of preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0072] <Polybenzoxazole and Polybenzoxazole Precursor> 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) (for example, a resin obtained by a ring-closing reaction). The polybenzoxazole precursor preferably has a repeating unit represented by formula (2).

[0073]

[0074] In formula (2), R １２１ represents a divalent organic group. １２２ represents a tetravalent organic group. １２３ and R １２４ each independently represents a hydrogen atom or a monovalent organic group.

[0075] In formula (2), R １２１ represents a divalent organic group. The divalent organic group may be any of the above-mentioned R １１１ Examples of the divalent organic group include a divalent organic group represented by the following formula:

[0076] In formula (2), R １２２ represents a tetravalent organic group. The tetravalent organic group may be any of the above-mentioned R １１５ Examples of the tetravalent organic group include a tetravalent organic group represented by the following formula:

[0077] In formula (2), R １２３ and R １２４ R each independently represents a hydrogen atom or a monovalent organic group. １２３and R １２４ is R １１３ and R １１４ The same definition and preferred embodiments are also the same.

[0078] 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.

[0079] The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polybenzoxazole precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polybenzoxazole precursor has a polydispersity (Mw / Mn) of preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0080] <Epoxy Resin> Epoxy resins are resins having epoxy groups. Examples of 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, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, and trimethylol type epoxy resins.

[0081] In terms of improving the flexibility and breaking strength of the specific film, it is also preferable that 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").

[0082] The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, or a naphthalene epoxy resin, and more preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a naphthalene epoxy resin. Examples of liquid epoxy resins include HP4032, HP4032D, EXA4032SS, and HP4032SS (naphthalene epoxy resins) manufactured by DIC Corporation; jER828EL (bisphenol A epoxy resin), jER807 (bisphenol F epoxy resin), and jER152 (phenol novolac epoxy resin) manufactured by Mitsubishi Chemical Corporation; and ZX1059 (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. The liquid epoxy resin is preferably HP4032SS or ZX1059.

[0083] As the 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 preferred, tetrafunctional naphthalene type epoxy resin, biphenyl type epoxy resin, or naphthylene ether type epoxy resin is more preferred, and biphenyl type epoxy resin is even more preferred. Examples of solid epoxy resins include HP-4700, HP-4710 (tetrafunctional naphthalene type epoxy resins), 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. Examples of suitable epoxy resins include NC7000L (naphthol novolac epoxy resin), NC3000H, NC3000, NC3000L, and NC3100 (biphenyl epoxy resin), manufactured by Nippon Kayaku Co., Ltd.; ESN475 (naphthol novolac epoxy resin) and ESN485 (naphthol novolac epoxy resin), manufactured by Nippon Steel Chemical & Materials; and YX4000H, YL6121 (biphenyl epoxy resin), and YX4000HK (bixylenol epoxy resin), manufactured by Mitsubishi Chemical Corporation. Preferred solid epoxy resins are YX4000HK, NC3000L, and HP7200H.

[0084] <Polyphenylene ether resin> 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 a branched structure is preferred. In the polyphenylene ether resin having a branched structure, it is preferred that ether bonds are directly bonded to at least three positions, i.e., the ipso position, the ortho position, and the para position, of at least one benzene ring constituting the polyphenylene ether resin.

[0085] The branched polyphenylene ether resin can be obtained, for example, by polymerizing two or more phenolic compounds. The phenolic compounds are preferably a phenolic compound having hydrogen atoms at the ortho- and para-positions and a reactive group, or a mixture of a phenolic compound having hydrogen atoms at the ortho- and para-positions but no reactive group and a phenolic compound having no hydrogen atoms at the ortho-position, a hydrogen atom at the para-position, and a reactive group.

[0086] Examples of 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. , 2-allyl-6-methylphenol, 2-allyl-6-ethylphenol, 2-allyl-6-phenylphenol, 2-allyl-6-styrylphenol, 2,6-divinylphenol, 2,6-diallylphenol, 2,6-diisopropenylphenol, 2,6-dibutenylphenol, 2,6-diisobutenylphenol, 2,6-diisopentenylphenol, 2-methyl-6-styrylphenol, 2-vinyl-6-methylphenol, 2-vinyl-6-ethylphenol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-n-butylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, and 2,6-ditolylphenol. Of these, 2,6-dimethylphenol or 2-allylphenol is preferred as the phenol compound.

[0087] It is also preferable that the polyphenylene ether resin has a reactive group. As the reactive group, a group having an ethylenically unsaturated double bond is preferable, and a vinylphenyl group or a (meth)acryloyl group is preferable. Furthermore, when the polyphenylene ether resin has a reactive group, the composition preferably contains a maleimide compound. The maleimide compound reacts with the polyphenylene ether resin to obtain a modified polyphenylene ether. As the modified polyphenylene ether, for example, a resin obtained by curing the resin composition described in WO 2022 / 102756 can be mentioned.

[0088] Examples of 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. Examples of polyphenylene ether resins include resins described in JP 2022-157695 A.

[0089] <(Meth)acrylic Resin> The (meth)acrylic resin is a resin having repeating units derived from a compound selected from (meth)acrylic acid and (meth)acrylic acid esters. Examples of repeating units derived from (meth)acrylic acid esters include repeating units derived from (meth)acrylic acid alkyl esters. The number of carbon atoms in the alkyl group (-COOR, the alkyl group in the R moiety) constituting the (meth)acrylic acid alkyl ester is preferably 1 to 50, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may be linear, branched, or cyclic. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate. The total content of repeating units derived from (meth)acrylic acid and (meth)acrylic acid esters is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total repeating units of the (meth)acrylic resin. The upper limit is preferably 100% by mass or less, more preferably 90% by mass or less.

[0090] The (meth)acrylic resin may have a repeating unit having an aromatic ring. The repeating unit having an aromatic ring may be a repeating unit derived from a (meth)acrylic acid ester. In other words, the repeating unit having an aromatic ring may be a repeating unit derived from a (meth)acrylic acid ester having an aromatic ring group. 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. Examples of repeating units having an aromatic ring include a repeating unit derived from a (meth)acrylate having an aromatic ring, a repeating unit derived from styrene, and a repeating unit derived from a polymerizable styrene derivative. Examples of (meth)acrylates having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Examples of styrene and polymerizable styrene derivatives include styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, and styrene trimer.

[0091] The (meth)acrylic resin may have a repeating unit having an alicyclic group. The repeating unit having an alicyclic group may be a repeating unit derived from a (meth)acrylic acid ester. In other words, the repeating unit having an alicyclic group may be a repeating unit derived from a (meth)acrylic acid ester having an alicyclic group. The alicyclic ring may be either a monocyclic ring or a polycyclic ring. Examples of the alicyclic ring include a dicyclopentanyl ring, a dicyclopentenyl ring, an isobornyl ring, an adamantane ring, and a cyclohexyl ring. Examples of monomers from which the repeating unit having an alicyclic ring is derived include dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0092] <Other Resins> The resin may contain other resins in addition to the various resins described above. Examples of other resins include phenol resin, silicone resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene resin, and polyphenylene sulfide.

[0093] As mentioned above, the resin contained in the composition may be a precursor of each of the resins mentioned above.

[0094] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the resin is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polydispersity (Mw / Mn) of the resin is preferably 1.0 to 3.5, and more preferably 2.0 to 3.0.

[0095] The resins may be used alone or in combination of two or more. The resin content is preferably 1.0 to 99.0 mass%, more preferably 5.0 to 98.0 mass%, and even more preferably 5.0 to 50.0 mass%, based on the total solid content of the composition. The resin content is preferably 5.0 to 99.0 mass%, based on the total solid content of the composition excluding inorganic fillers. The total content of the polyimide precursor, polyimide, polybenzoxazole precursor, polybenzoxazole, epoxy resin, polyphenylene ether resin, acrylic resin, and methacrylic resin is preferably 10 to 100 mass%, more preferably 50 to 100 mass%, even more preferably 95 to 100 mass%, and particularly preferably 99 to 100 mass%, based on the total mass of the resins.

[0096] [Specific inorganic filler] The composition contains a specific inorganic filler. The specific inorganic filler is an inorganic filler that has been surface-treated with two or more surface modifiers. At least one of the two or more surface modifiers has a reactive group. In terms of achieving excellent effects of the present invention, the average particle size of the specific inorganic 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 specific inorganic filler is preferably more than 0 nm, more preferably 5 nm or more, even more preferably 10 nm or more, and particularly preferably 50 nm or more. The average particle size of the specific inorganic filler is also preferably 5 to 300 nm, more preferably 10 to 150 nm, and even more preferably 50 to 150 nm. The average particle size of the specific inorganic filler is a value calculated using the following particle size measurement method. Particle size measurement method: A rectangular area of ​​3 μm × 10 μm 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 long diameters of all the specific inorganic fillers observed within the area are measured at five different locations on the film. The average value of the long diameters of all the specific inorganic fillers measured in each step is taken as the average particle size of the specific inorganic filler.

[0097] The particle size measurement method is described in detail below. The composition is applied to a substrate (preferably a glass substrate) to form a composition layer. The thickness of the composition layer is preferably 3 μm or more. Furthermore, to form the composition layer, a drying treatment may be performed, if necessary, after the composition is applied. A cross section along the normal direction of the surface of the obtained composition layer (the surface opposite the substrate side) is cut out, and a rectangular region of 3 μm x 10 μm on the cross section is observed with a scanning electron microscope, and the major axes of all specific inorganic fillers observed within the region are measured. The scanning electron microscope used is a Hitachi High-Tech S-4800. The magnification used for observation is 50,000x. The above procedure is performed at five different locations on the composition layer, and the average (arithmetic mean) of the major axes of all specific inorganic fillers measured in each procedure is taken as the average particle size of the specific inorganic filler. The major axis refers to the length of the longest line segment connecting any two points on the outline of the specific inorganic filler's outer shape in the observed image. Furthermore, when the specific inorganic filler aggregates to form aggregates in the observed image, the major axis of each specific inorganic filler constituting the aggregate is measured.

[0098] In the case of a specific inorganic filler, the term "the inorganic filler constituting the specific inorganic filler has been surface-treated with a surface modifier" means that at least a portion of the surface of the inorganic filler constituting the specific inorganic filler is covered with a surface modifier or a component derived from the surface modifier. In other words, the specific inorganic filler means that at least a portion of the surface of the inorganic filler constituting the specific inorganic filler is covered with a surface modifier or a component derived from the surface modifier. Note that, when the surface modifier is a hydrolyzable compound, examples of the component derived from the surface modifier include a hydrolyzate of the surface modifier and a hydrolysis condensate thereof. It is preferable that at least a portion of the surface of the inorganic filler constituting the specific inorganic filler is covered with a surface modifier or a component derived from the surface modifier via a chemical bond, and it is more preferable that at least a portion of the surface of the inorganic filler constituting the specific inorganic filler is covered with a surface modifier via an "-Si-O-" bond.

[0099] <Inorganic Filler> The inorganic filler constituting the specific inorganic filler is preferably an inorganic filler. Examples of inorganic fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as chion-doped 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 inorganic filler preferably comprises at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably comprises silicon dioxide (silica).

[0100] The shape of the inorganic filler may be either spherical or non-spherical (for example, crushed or fibrous), with spherical being preferred.

[0101] The average particle size of the inorganic 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 inorganic filler is preferably more than 0 nm, more preferably 5 nm or more, even more preferably 10 nm or more, and particularly preferably 50 nm or more. The average particle size of the inorganic filler is also preferably 5 to 300 nm, more preferably 10 to 150 nm, and even more preferably 50 to 150 nm. The average particle size of the inorganic filler can be measured using the same measurement method as for the average particle size of the specific inorganic filler.

[0102] Examples of inorganic fillers include NSS-3N (manufactured by Tokuyama Corporation, silicon dioxide), NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), YA050C-MJE (manufactured by Admatechs Co., Ltd., silicon dioxide, solid content concentration 50% by mass MEK (methyl ethyl ketone) slurry), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide), and PMA-ST. (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., solids concentration 100% by mass), Y50SP-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass).

[0103] <Surface Modifier> The surface modifier used for surface modification of the inorganic filler is two or more types, and includes a surface modifier having a reactive group. Examples of surface modifiers include silane coupling agents, titanate coupling agents, disilazane compounds, and basic compounds. The surface modifier preferably contains at least two types selected from the group consisting of silane coupling agents, disilazane compounds, and basic compounds, more preferably contains a silane coupling agent and a disilazane compound or a basic compound, and even more preferably consists of only a silane coupling agent and a disilazane compound or a basic compound. Examples of surface modifiers having a reactive group include the surface modifiers exemplified above that have a reactive group, with silane coupling agents having a reactive group being preferred, and the compound represented by formula (S) described below being more preferred. As the reactive group, a reactive group that can be contained in the above-mentioned resin is preferred.

[0104] Examples of the reactive group include reactive groups that the resins described above may have. That is, examples of the reactive group include polymerizable groups and functional groups other than polymerizable groups. The polymerizable groups and functional groups other than polymerizable groups are as described above. The total content of the silane coupling agent which may have a reactive group, the disilazane compound which may have a reactive group, and the basic compound which may have a reactive group is preferably 90 to 100 mass%, more preferably 95 to 100 mass%, and even more preferably 99 to 100 mass%, based on the total mass of the two or more surface modifiers.

[0105] (Silane Coupling Agent) A silane coupling agent is a compound having a hydrolyzable group and / or a hydroxyl group bonded to a silicon atom directly or via a divalent linking group. Examples of the hydrolyzable group include an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms) and a halogen atom such as a chlorine atom. The number of hydrolyzable groups contained in the silane coupling agent is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit is preferably 10 or less. The number of hydrolyzable groups is also preferably 1 to 3. It is also preferable that the silane coupling agent has a functional group other than a hydrolyzable group and a hydroxyl group. Examples of functional groups include (meth)acryloyl groups, phenyl groups, epoxy groups, oxetanyl groups, vinyl groups, styryl groups, amino groups such as phenylamino groups, isocyanate groups, mercapto groups, and acid anhydride groups. The functional group may be the reactive group described above. The number of functional groups contained in the silane coupling agent may be 1 or 2 or more.

[0106] The silane coupling agent is preferably a compound represented by formula (S).

[0107] X-L Ｘ -Si(R Ｘ ) ３ (S)

[0108] In formula (S), X represents a reactive group. Ｘ represents a single bond or a divalent linking group. Ｘeach independently represents a hydrolyzable group or a hydroxyl group.

[0109] Examples of the reactive group represented by X include reactive groups that the above-mentioned resins can have, and a group having an ethylenically unsaturated double bond or an epoxy group is preferred, a (meth)acryloyl group, a styrene group or an epoxy group is more preferred, and a (meth)acryloyl group is even more preferred. Ｘ Examples of the divalent linking group represented by the formula (I) include -O-, -S-, -CO-, -NR Ｎ -, -CO-O-, -O-CO-O-, -CO-NR Ｎ -, and divalent aliphatic hydrocarbon groups, and groups formed by combining these groups. Ｎ represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms). Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, with an alkylene group being preferred. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, with a linear group being preferred. 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 divalent aliphatic hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom and a cyano group. The divalent aliphatic hydrocarbon group is preferably an alkylene group having 2 to 12 carbon atoms. As a group combining these, an alkylene group having -O- is preferred, with an -O-alkylene group- being more preferred. R Ｘ The hydrolyzable group represented by the formula (I) has the same meaning as the hydrolyzable group that the silane coupling agent can have, and the preferred embodiments are also the same.

[0110] Examples of silane coupling agents include 3-methacryloxytrimethoxypropylsilane (Mw=248.35), parastyryltrimethoxysilane (Mw=224.3), 3-glycidoxypropyltrimethoxysilane (Mw=236.3), N-phenyl-3-aminopropyltrimethoxysilane (Mw=255.4), vinyltrimethoxysilane (Mw=148.23), 3-acryloxytrimethoxypropylsilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-mercaptotriethoxysilane, and 3-ureidopropyltriethoxysilane. The silane coupling agent may also be a polyfunctional silane coupling agent. Examples include the silane coupling agents X-12 series (e.g., X-12-1048, X-12-1050, X-12-981S, and X-12-984S, manufactured by Shin-Etsu Chemical Co., Ltd.) Preferred silane coupling agents include 3-methacryloxytrimethoxypropylsilane, 3-acryloxytrimethoxypropylsilane, parastyryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and vinyltrimethoxysilane.

[0111] (Disilazane Compound) The disilazane compound is a compound having a —Si—N—Si— bond. The disilazane compound is preferably a compound represented by formula (Z).

[0112] (R Ｚ ) ３ -Si-N(R Ｎ )-Si-(R Ｚ ) ３ (Z)

[0113] In formula (Z), R Ｚ R each independently represents a hydrocarbon group which may have a hydrogen atom or a halogen atom. Ｎ represents a hydrogen atom or a hydrocarbon group.

[0114] R ＺExamples of hydrocarbon groups represented by the formula (I) include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aliphatic hydrocarbon group is preferably an alkyl group. The aromatic hydrocarbon group may be either a monocyclic or polycyclic ring. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 8. The aromatic hydrocarbon group is preferably a phenyl group. Examples of halogen atoms that the hydrocarbon group may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0115] Examples of the disilazane compound include 1,1,1,3,3,3-hexamethyldisilazane (Mw=161.14), 1,3-diphenyltetramethyldisilazane, 1,1,3,3-tetramethyldisilazane, heptamethyldisilazane, 1,3-bis(chloromethyl)tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane, with 1,1,1,3,3,3-hexamethyldisilazane being preferred.

[0116] (Basic Compound) The basic compound is a basic compound other than a silane coupling agent and a disilazane compound, which exhibits basicity when dissolved in a solvent (for example, water, an organic solvent, etc.). In addition, when the composition contains a specific inorganic filler whose surface has been modified with a basic compound, the specific inorganic filler can also function as a thermal base generator, which will be described later. The above function includes facilitating the synthesis of a corresponding resin from a resin precursor (for example, promoting the ring-closing reaction of a polyimide precursor). Examples of the basic compound include organic bases, ammonium hydroxide (NH ４Examples of basic compounds include inorganic bases such as methyl hydroxybenzoates (OH) and salts thereof. Examples of basic compounds also include bases generated by thermal base generators, which will be described later. Organic bases are basic compounds having at least one carbon atom.

[0117] Examples of the organic base include quaternary ammonium compounds, amine compounds, nitro compounds, nitroso compounds, oxime compounds, ketoxime compounds, aldoxime compounds, lactam compounds, and isocyanide compounds.

[0118] A quaternary ammonium compound is a salt consisting of a quaternary ammonium cation in which four hydrocarbon groups are substituted on a nitrogen atom, and an anion.

[0119] Examples of the quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, and tetra(hydroxyethyl)ammonium cation. Examples of the anion include hydroxide ion, fluoride ion, bromide ion, iodide ion, acetate ion, and carbonate ion.

[0120] An amine compound is a compound having an amino group in the molecule. Examples of the amine compound include a compound having a primary amino group (—NH ２ Examples of the amine compound salt include primary amines having a hydroxyl group (>NH) in the molecule, secondary amines having a secondary amino group (>NH) in the molecule, and tertiary amines having a tertiary amino group (>N-) in the molecule, as well as salts thereof. Examples of the salts of amine compounds include salts with inorganic acids in which at least one nonmetal selected from the group consisting of Cl, S, N, and P is bonded to hydrogen, and hydrochlorides, sulfates, or nitrates are preferred. Examples of the amine compound include alicyclic amine compounds and aliphatic amines.

[0121] Alicyclic amine compounds are amine compounds having a ring structure in the molecule. Examples of alicyclic amine compounds include N,N-dimethylcyclohexylamine, cis-2,6-dimethylpiperidine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), ε-caprolactam, 1,4-diazabicyclo[2.2.2]octane (DABCO), tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, and 1,5-diazabicyclo[4.3.0]-5-nonene. Preferred alicyclic amine compounds are N,N-dimethylcyclohexylamine or cis-2,6-dimethylpiperidine.

[0122] Examples of aliphatic amine compounds include alkylamines, dialkylamines, and trialkylamines. Trialkylamines are compounds having a tertiary amino group in which three alkyl groups are substituted on a nitrogen atom. Examples of trialkylamines include trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, diethylmethylamine, diethylpropylamine, diethylbutylamine, dipropylmethylamine, dipropylethylamine, dipropylbutylamine, dibutylmethylamine, dibutylethylamine, and dibutylpropylamine. Preferred trialkylamines are trimethylamine, diethylmethylamine, triethylamine, or tributylamine, and more preferred are trimethylamine or triethylamine.

[0123] The basic compound preferably includes an amine compound, more preferably includes at least one selected from the group consisting of an alicyclic amine compound and an aliphatic amine compound, and further preferably includes at least one selected from the group consisting of triethylamine, N,N-dimethylcyclohexylamine, and cis-2,6-dimethylpiperidine.

[0124] The pKaH of the basic compound (pKa of the conjugate salt of the basic compound) is preferably 4.0 to 15.0, more preferably 5.0 to 14.0, and even more preferably 6.0 to 12.0. The pKaH of the basic compound can be measured by acid titration.

[0125] Preferred embodiments of the two or more surface modifiers include the following embodiments 1 to 4. Embodiment 1: Contains 3-methacryloxytrimethoxypropylsilane and hexamethyldisilazane. Embodiment 2: Contains 3-methacryloxytrimethoxypropylsilane and triethylamine, dimethylcyclohexylamine, or cis-2,6-dimethylpiperidine. Embodiment 3: Contains vinyltrimethoxysilane and triethylamine, dimethylcyclohexylamine, or cis-2,6-dimethylpiperidine. Embodiment 4: Contains N-phenyl-3-aminopropyltrimethoxysilane and hexamethyldisilazane.

[0126] The two or more surface modifiers preferably include a surface modifier A having a molecular weight of 220 or more and a surface modifier B having a molecular weight of less than 220. The molecular weight of surface modifier A is preferably 1,000 or less, more preferably 500 or less, and even more preferably 300 or less. The molecular weight of surface modifier B is less than 220, preferably 200 or less, more preferably 180 or less, and even more preferably 170 or less. The lower limit is preferably 50 or more, more preferably 100 or more. Examples of surface modifier A and surface modifier B include surface modifiers that satisfy the respective molecular weights among the above-mentioned surface modifiers. Surface modifier A is preferably a silane coupling agent, and more preferably a compound represented by formula (S). Surface modifier B is preferably a silane coupling agent (preferably a compound represented by formula (S)), a disilazane compound, or a basic compound.

[0127] Examples of methods for producing the specific inorganic filler include a method of contacting an inorganic filler with a surface modifier. The method for producing the specific inorganic filler may be either a dry method in which the surface is modified in a gas phase or a wet method in which the surface is modified in a liquid phase. For example, a liquid mixture containing the specific inorganic filler may be prepared by mixing an unmodified inorganic filler with two or more surface modifiers in a liquid. The various surface modifiers contained in the two or more surface modifiers may be added all at once or in portions, either as the same type of surface modifier or as different types of surface modifiers. For example, an inorganic filler may be mixed with a surface modifier to prepare a liquid mixture containing an inorganic filler surface-modified with the surface modifier, and then a surface modifier different from the surface modifier may be added to the liquid mixture to prepare a liquid mixture containing the specific inorganic filler. If necessary, a heating treatment and a drying treatment may be performed, or the above procedure may be repeated.

[0128] A preferred method for producing the specific inorganic filler involves mixing an unsurface-modified inorganic filler with surface modifier A to prepare a first mixed liquid containing a first inorganic filler surface-modified with surface modifier A, and then adding surface modifier B to the first mixed liquid to prepare a second mixed liquid containing the specific inorganic filler. Another preferred method involves separating the first inorganic filler from the first mixed liquid, mixing the resulting first inorganic filler with a solvent to prepare a third mixed liquid, and adding surface modifier B to the third mixed liquid to prepare a fourth mixed liquid containing the specific inorganic filler. By surface-modifying the inorganic filler with surface modifier A, which has a relatively high molecular weight, and then surface modifier B, which has a relatively low molecular weight, as in the above-described method, the surface coverage of the inorganic filler can be improved, thereby achieving superior effects of the present invention.

[0129] The number of types of surface modifiers is two or more, preferably 2 to 4, and more preferably 2. In this specification, a single type of surface modifier, a hydrolysate derived from that surface modifier, and a hydrolysis-condensate derived from that surface modifier are counted as one type. Specifically, when a specific inorganic filler is obtained by surface-modifying an inorganic filler using 3-methacryloxytrimethoxypropylsilane and hexamethyldisilazane as surface modifiers, the inorganic filler can be surface-modified with at least one selected from the group consisting of 3-methacryloxytrimethoxypropylsilane, a hydrolyzate of 3-methacryloxytrimethoxypropylsilane, and a hydrolysis condensate of 3-methacryloxytrimethoxypropylsilane, and at least one selected from the group consisting of hexamethyldisilazane, a hydrolyzate of hexamethyldisilazane, and a hydrolysis condensate of hexamethyldisilazane, and in this case, the number of types of surface modifiers is two, namely, 3-methacryloxytrimethoxypropylsilane and hexamethyldisilazane.

[0130] The specific inorganic filler may be used alone or in combination of two or more.The content of the specific inorganic filler is preferably 20.0 mass% or more, more preferably 30.0 mass% or more, based on the total solid content of the composition.The content of the specific inorganic filler is preferably 90.0 mass% or less, more preferably 80.0 mass% or less, and even more preferably 75.0 mass% or less, based on the total solid content of the composition.

[0131] The various components that the composition may contain are described in detail below.

[0132] [Compound Having a Reactive Group] The composition may contain a compound having a reactive group. When the composition satisfies Requirement 2, the composition contains a compound having a reactive group. The compound having a reactive group is a compound different from the resin described above and has a reactive group. Furthermore, the compound having a reactive group is preferably a compound different from the surface modifier. Examples of the reactive group possessed by the compound having a reactive group include reactive groups that may be possessed by the resin described above, and a polymerizable group is preferred. In other words, the composition preferably contains a compound having a polymerizable group (hereinafter also referred to as a "polymerizable compound") as the compound having a reactive group. The compound having a reactive group may have one or more reactive groups, and may have two or more reactive groups. The number of reactive groups possessed by the compound having a reactive group is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6.

[0133] When the composition contains a polymerizable compound (preferably a compound having a group with an ethylenically unsaturated double bond), the composition preferably further contains a photopolymerization initiator, which will be described later.

[0134] The polymerizable compound is a compound having one or more polymerizable groups in one molecule. As the polymerizable compound, a compound having a group having an ethylenically unsaturated double bond is preferred, a compound having a (meth)acryloyl group, a vinyl group, or a styryl group is more preferred, and a compound having a (meth)acryloyl group is even more preferred.

[0135] The number of polymerizable groups in the polymerizable compound is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6. Examples of the polymerizable compound include a polymerizable compound having one polymerizable group in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound"), a polymerizable compound having two polymerizable groups in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound"), and a polymerizable compound having three or more polymerizable groups in one molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound"). The polymerizable compound is preferably a bifunctional polymerizable compound or a trifunctional or higher functional polymerizable compound.

[0136] Examples of bifunctional polymerizable compounds include polyethylene glycol (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Commercially available bifunctional polymerizable compounds include, for example, diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol #200 dimethacrylate (4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), SR205NS (manufactured by Sartomer Inc.), and SR209 (manufactured by Sartomer Inc.).

[0137] Examples of trifunctional or higher functional polymerizable compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton. "(Tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0138] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0139] Examples of the polymerizable compound include urethane (meth)acrylates (preferably tri- or higher functional urethane (meth)acrylates). The number of polymerizable groups in the urethane (meth)acrylate is preferably 6 or more, and more preferably 8 or more. The upper limit is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0140] The compound having a reactive group may have liquid crystallinity. When the compound having a reactive group has liquid crystallinity, it is preferably a polymerizable compound having liquid crystallinity (hereinafter also referred to as "compound M"). Compound M may be either a rod-shaped liquid crystal compound or a discotic liquid crystal compound, but a rod-shaped liquid crystal compound is preferred. Examples of compound M 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. Examples of the spacer include a chain aliphatic hydrocarbon group and a (poly)oxyalkylene group.

[0141] The compound M is preferably a compound represented by formula (M1).

[0142] Formula (M1): P １ -L１ -ML ２ -P ２

[0143] In formula (M1), P １ and P ２ each independently represents a polymerizable group. １ and L ２ each independently represents a divalent linking group, and M represents a mesogenic group.

[0144] In formula (M1), P １ and P ２ each independently represents a polymerizable group. Examples of the polymerizable group include the polymerizable groups that the resins described above can have, and preferred embodiments are also the same.

[0145] In formula (M1), L １ and L ２ each independently represents a divalent linking group. Examples of the divalent linking group include L Ｘ Examples of the divalent linking group include a divalent linking group represented by the following formula:

[0146] L １ and L ２ As for * Ｐ -L ａ -A ａ -L ｂ -* Ｍ A divalent linking group represented by the following formula is preferred. Ｐ Is P １ or P ２ represents the bonding position with Ｍ represents the bonding position with M. ａ and L ｂ each independently represents a single bond, —O—, —S—, —CO—, or —NR Ｎ -, -CO-O-, -O-CO-O-, and -CO-NR Ｎ -, and groups formed by combining these. ａ is preferably a single bond, —O—, or —CO—O—. ｂ is preferably —O—, —CO—, —CO—O—, or —O—CO—O—, and more preferably —CO—O—. ａ represents a divalent aliphatic hydrocarbon group. ａA preferred embodiment of the divalent aliphatic hydrocarbon group represented by the formula (S) is Ｘ Examples of the divalent aliphatic hydrocarbon group include a divalent aliphatic hydrocarbon group represented by the following formula:

[0147] In formula (M1), M represents a mesogenic group. Examples of the mesogenic group include known mesogenic groups, and a mesogenic group represented by formula (m1) is preferred. Formula (m1): *-(W ｍ -L ｍ ) ｍ -W-*

[0148] In formula (m1), * represents a bonding position.

[0149] In formula (m1), L ｍ each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include the above-mentioned L １ and L ２ Examples of the divalent linking group include a divalent linking group represented by the following formula: ｍ 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. ｍ If there are multiple L ｍ may be the same or different from each other.

[0150] In formula (m1), W ｍand W each independently represent a divalent cyclic group. Examples of the divalent cyclic group include an arylene group, a heteroarylene group, a cyclic alkylene group, a cyclic alkenylene group, and a divalent aliphatic heterocyclic group, with an arylene group or a cyclic alkylene group being preferred. The divalent cyclic group may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. The number of ring members in the divalent cyclic group is preferably 4 to 12, more preferably 5 to 8, and even more preferably 6. 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, with a 1,4-phenylene group or a 1,4-cyclohexanediyl group being preferred. When structural isomers (e.g., cis and trans isomers) exist, the divalent ring group may be either isomer or a mixture of these isomers in any proportion in the composition. The divalent ring group may have a substituent. Examples of 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, and 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. ｍ If there are multiple W ｍ may be the same or different from each other.

[0151] In formula (m1), m represents an integer of 1 to 3, preferably 2 or 3.

[0152] Examples of mesogenic groups are shown below, but the present invention is not limited to these. The mesogenic groups shown below may be substituted with the above-mentioned substituents.

[0153]

[0154] Examples of Compound M are shown below, but the present invention is not limited to these. Compound M can be synthesized by known methods, for example, by the method described in JP-A-11-513019.

[0155]

[0156]

[0157]

[0158] The compound having a reactive group is preferably a low molecular weight compound. The molecular weight of the compound having a reactive group is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. The molecular weight of the compound having a reactive group is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more.

[0159] The compound having a reactive group may be used alone or in combination of two or more. The content of the compound having a reactive group is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, and even more preferably 20.0 mass% or less, based on the total solid content of the composition. The lower limit is preferably 1.0 mass% or more.

[0160] [Photopolymerization initiator] The composition preferably contains a photopolymerization initiator, since this provides a more excellent effect of the present invention and the composition exhibits photolithographic properties. The term "exhibiting photolithographic properties" means a property that allows a pattern to be formed by photolithography. When the composition is used in the manufacture of a laminate and a semiconductor package, as described below, the composition preferably exhibits photolithographic properties, since a pattern can be formed with high precision. The photopolymerization initiator is a compound different from the various components described above. Examples of photopolymerization initiators include photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators, with photoradical polymerization initiators being preferred.

[0161] Examples of the photopolymerization initiator include an oxime ester compound (a photopolymerization initiator having an oxime ester structure), an aminoacetophenone compound (a photopolymerization initiator having an aminoacetophenone structure), a hydroxyacetophenone compound (a photopolymerization initiator having a hydroxyacetophenone structure), an acylphosphine oxide compound (a photopolymerization initiator having an acylphosphine oxide structure), and a bistriphenylimidazole compound (a photopolymerization initiator having a bistriphenylimidazole structure). As the photopolymerization initiator, an oxime ester compound or an aminoacetophenone compound is preferred, and an oxime ester compound is more preferred.

[0162] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol-3-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), and OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF and trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou New Power Electronic Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou New Power Electronic Materials Co., Ltd.).

[0163] Examples of 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.).

[0164] Examples of the photopolymerization initiator 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-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO), and H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819). Examples of the photopolymerization initiator include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP 2011-095716 A and paragraphs 0064 to 0081 of JP 2015-014783 A.

[0165] The content of the photopolymerization initiator is preferably 0.01 to 10.0 mass %, more preferably 0.1 to 5.0 mass %, and still more preferably 0.1 to 3.0 mass %, based on the total solid content of the composition.

[0166] [Thermal Base Generator] The composition also preferably contains a thermal base generator. When the composition contains a resin precursor, the inclusion of a thermal base generator in the composition promotes the reaction of the resin precursor.

[0167] 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. The anion constituting the ammonium salt compound also preferably has an aromatic ring. The aromatic ring may be, for example, A in the formula (A1) described below. ａ１ Examples of aromatic rings that constitute aromatic ring groups represented by the following formula are given.

[0168] 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, and is preferably cyclic.

[0169] The acidic compound is preferably a compound represented by formula (A1).

[0170]

[0171] In formula (A1), A ａ１ represents a p-valent organic group. ａ１ represents a monovalent organic group. ａ１ represents an (m+1)-valent linking group, m represents an integer of 1 or more, and p represents an integer of 1 or more.

[0172] In formula (A1), Aａ１ represents a p-valent organic group. Examples of the organic group include an aliphatic hydrocarbon group and an aromatic ring group, with an 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. Examples of the alkyl group 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 p-valent aliphatic hydrocarbon groups (where p is an integer of 2 or greater) include groups formed by removing (p-1) hydrogen atoms from the above-mentioned monovalent aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may further have a substituent.

[0173] The aromatic ring group may be either a monocyclic or polycyclic ring. 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 thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyridine ring group, a pyrazine ring group, a pyrimidine ring group, a pyridazine ... 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 thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyr Examples of the aromatic ring group include a benzene 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, and a benzene ring group is preferred. The aromatic ring group may further have a substituent.

[0174] In formula (A1), R ａ１ represents a monovalent organic group. Examples of the monovalent organic group include A ａ１ Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group represented by the following formula: The monovalent organic group may further have a substituent. The substituent is preferably a carboxy group.

[0175] In formula (A1), L ａ１ represents an (m+1)-valent linking group. Examples of the (m+1)-valent linking group include an ether group (—O—), a carbonyl group (—CO—), an ester group (—COO—), a thioether group (—S—), and —SO ２ -, -NR Ｎ - (R Ｎrepresents a hydrogen atom or a substituent), divalent linking groups such as alkylene groups (preferably having 1 to 10 carbon atoms) and alkenylene groups (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 or an alicyclic group; and groups combining these.

[0176] In formula (A1), m represents an integer of 1 or greater. m is preferably 1 or 2, and more preferably 1.

[0177] In formula (A1), p represents an integer of 1 or greater. p is preferably 1 or 2, and more preferably 1.

[0178] Examples of the thermal base generator include the thermal base generators described in WO 2018 / 038002.

[0179] The temperature at which the thermal base generator generates a base is preferably the heating temperature in step 4 in the laminate manufacturing method described below. The temperature at which the thermal base generator generates a base is, for example, preferably 50 to 400°C, more preferably 100 to 250°C. The temperature at which the thermal base generator generates a base can be a measured value obtained by a known measurement method or a literature value. For example, the base generation temperature can be determined by differential scanning calorimetry, where a compound to be measured is heated to 250°C at 5°C / min in a pressure-resistant capsule, and the peak temperature of the lowest exothermic peak is the base generation temperature.

[0180] The thermal base generator may be used alone or in combination of two or more. The content of the thermal base generator is preferably 0.01 to 10.0 mass% and more preferably 0.1 to 5.0 mass% relative to the total solid content of the composition. The mass ratio of the content of the thermal base generator to the content of the resin is preferably 0.0005 to 1.0, more preferably 0.001 to 0.1, and even more preferably 0.001 to 0.05.

[0181] [Plasticizer] The composition may contain a plasticizer. When forming using a transfer film having a composition layer described later, it is preferable to contain a plasticizer in that the composition layer has excellent conformability to unevenness when laminated to an object to be laminated, and a specific film can be formed with high precision. The plasticizer is a compound different from the various components described above, and preferably does not have a reactive group.

[0182] The molecular weight of the plasticizer is preferably from 200 to 1000, more preferably from 250 to 800, and even more preferably from 300 to 600. When the plasticizer has a molecular weight distribution, the above molecular weight refers to the weight average molecular weight.

[0183] The boiling point of the plasticizer is preferably 230 to 500°C, more preferably 280 to 480°C, even more preferably 300 to 450°C, and particularly preferably 350 to 450°C. The above boiling point is the boiling point under normal pressure (760 mmHg). In this specification, 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 boiling point is the gas temperature at which condensation of the evaporated gas begins (measured from 23 to 300°C, temperature rise rate 1°C / min). The compound is distilled using a Liebig condenser, and if distillation does not begin at 300°C under normal pressure, the distillation is carried out under reduced pressure. Similar distillation was carried out sequentially at pressures of 100 mmHg, 50 mmHg, and 5 mmHg (measurement from 23 to 300°C, temperature increase rate 1°C / min, if distillation did not start at 300°C, distillation was carried out at the next pressure), and the boiling point at atmospheric pressure was 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 began. The boiling point at atmospheric pressure was taken as the calculated boiling point. If distillation did not start at 300°C under 5 mmHg, the boiling point at atmospheric pressure was deemed to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line was drawn between the boiling point at reduced pressure on line A and the degree of reduced pressure on line C (Procedure 1), and the value at the intersection of the line drawn in Procedure 1 and line B was read (Procedure 2), and this was deemed to be the boiling point at atmospheric pressure.

[0184] The viscosity of the plasticizer at 25° C. is preferably 0.01 to 500 mPa·s, more preferably 0.05 to 300 mPa·s, and even more preferably 0.1 to 100 mPa·s. The viscosity can be measured using a B-type viscometer.

[0185] Examples of the plasticizer include 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.

[0186] Examples of polycarboxylic acid esters include aliphatic dicarboxylic acid esters (e.g., adipic acid esters, azelaic acid esters, and sebacate esters); aromatic dicarboxylic acid esters (e.g., phthalic acid esters); trimellitic acid esters; and citrate esters (e.g., tributyl acetyl citrate). Examples of polycarboxylic acid esters include ethyl phthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetyl citrate, benzyl 2-ethylhexyl phthalate, bis(2-ethylhexyl) isophthalate, tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.

[0187] Examples of phosphate esters include triamyl phosphate and tris(2-butoxyethyl) phosphate.

[0188] The polyether esters are preferably organic acid esters of polyalkylene glycol. Examples of organic acids include monocarboxylic acids (e.g., butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexyl acid, and decanoic acid). Specific examples of polyether esters include triethylene glycol bis-2-ethylhexanoate.

[0189] Examples of 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.

[0190] The plasticizer may be used alone or in combination of two or more. The content of the plasticizer is preferably 5.0 to 50.0 mass% and more preferably 10.0 to 30.0 mass% relative to the total solid content of the composition. The mass ratio of the plasticizer content to the resin content is preferably 0.1 to 10.0 and more preferably 0.5 to 7.0. The mass ratio of the plasticizer content to the specific inorganic filler content is preferably 0.05 to 1.0 and more preferably 0.2 to 0.7.

[0191] [Surfactant] The composition also preferably contains a surfactant.

[0192] Examples of surfactants include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. Silicone-based surfactants are preferred as surfactants. From the viewpoint of improving environmental compatibility, it is also preferred that the surfactant does not contain fluorine atoms.

[0193] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21). Furthermore, the fluorosurfactant may be a polymer of a fluorine-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 fluorosurfactant may also 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). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group with an ethylenically unsaturated double bond in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0194] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0195] Commercially available 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 Corporation); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC); PolyFox Examples of such products include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by NEOS Corporation); and U-120E (manufactured by Unichem).

[0196] Examples of 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 ester. Commercially available 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 Japan 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 Yushi Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0197] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.Preferred silicone surfactants are polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.The polymers may be either random copolymers or block copolymers.

[0198] Commercially available 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 Co., Ltd.); X-22-4952, X-22-4272, and X-22-6266. , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, K F-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125 , KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Perform BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0199] Other examples of the surfactant include nonionic surfactants other than those mentioned above, such as those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0200] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.01 to 3.0 mass %, more preferably 0.05 to 1.0 mass %, and still more preferably 0.1 to 0.8 mass %, based on the total solid content of the composition.

[0201] [Rust inhibitor] The composition preferably contains a rust inhibitor. Examples of the rust inhibitor include heterocyclic compounds. Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, pyrimidine compounds, and pyridine compounds, and triazole compounds, benzotriazole compounds, or tetrazole compounds are preferred. Examples of heterocyclic compounds include compounds described in International Publication No. 2022 / 039027.

[0202] The content of the rust inhibitor is preferably 0.01 to 3.0 mass%, more preferably 0.05 to 1.0 mass%, and still more preferably 0.1 to 0.8 mass%, based on the total solid content of the composition.

[0203] [Other Additives] The composition may contain other additives in addition to those described above. Examples of the other additives include a photoacid generator, a curing agent, an aliphatic thiol compound, a thermally crosslinkable compound, a polymerization inhibitor, a hydrogen donor compound, a solvent, impurities, a sensitizer, an alkoxysilane compound, a maleimide compound, and a hydrosilylation agent.

[0204] <Solvent> The composition may contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse various components that may be contained in the composition other than the solvent. Examples of solvents 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 solvents may be used alone or in combination. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the composition.

[0205] Examples of the aliphatic thiol compound, thermal crosslinking compound, polymerization inhibitor, and hydrogen donor compound include the 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. Examples of the hydrosilylation agent 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 bisacetoacetate; and platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. The hydrosilylation agent is preferably used as a curing agent when a silicone resin or a precursor thereof is used as the resin.

[0206] [Specific Film] The composition is used to form a specific film. The specific film is a film containing components derived from the composition. The method for forming the specific film is not particularly limited, and examples include a method of applying the composition to a substrate, drying it, and then subjecting it to at least one treatment selected from heating and exposure, and a method of transferring a composition layer to a substrate using a transfer film described below, and then subjecting it to at least one treatment selected from heating and exposure. Preferred aspects of the heating and exposure are the same as the preferred aspects in step 3 described below. The specific film is preferably a film formed by at least heating. In the specific film, some or all of the components contained in the composition may have reacted (e.g., polymerization of compound Z and conversion of the resin precursor to a resin), or some of the components contained in the composition (e.g., plasticizer and solvent) may have been removed. The specific film is preferably a cured film of the composition.

[0207] The average thickness of the specific film is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, and particularly preferably 5.0 μm or more, from the viewpoint of more excellent insulation reliability. The average thickness of the specific film is preferably 40.0 μm or less, more preferably 25.0 μm or less, even more preferably 20.0 μm or less, and particularly preferably 19.0 μm or less, from the viewpoint of excellent pattern resolution.

[0208] [Transfer Film] The transfer film of the present invention has a temporary support and a composition layer formed using the above-described composition.

[0209] FIG. 1 is a cross-sectional schematic diagram 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. Although the transfer film 100 shown in FIG. 1 has the cover film 16, the transfer film may have no cover film 16. Furthermore, as described below, 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.

[0210] [Temporary Support] The transfer film has a temporary support, which is a member that supports the composition layer and is ultimately removed by a peeling treatment.

[0211] 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 is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate (PET) films (e.g., biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being preferred. Furthermore, the temporary support is preferably free of deformations such as wrinkles and scratches.

[0212] The temporary support preferably has high transparency in order to enable pattern exposure through the temporary support. Specifically, the transmittance at each of the wavelengths 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 each of the above wavelengths include, for example, 87%, 92%, and 98%. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, 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. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably small. The number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / 10 mm. ２ Preferably, 10 pieces / 10 mm or less ２ More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２is particularly preferred.

[0213] The thickness of the temporary support is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (scanning electron microscope).

[0214] In order to improve the adhesion between the temporary support and the composition layer, the surface of the temporary support that comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, etc. When the surface is modified by UV irradiation, the exposure dose of UV irradiation is 10 to 2000 mJ / cm. ２ is preferred, and 50 to 1000 mJ / cm ２ 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 output and illuminance can be adjusted as appropriate.

[0215] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. The temporary support may be a recycled product. Examples of the recycled product include a film obtained by cleaning and chipping used films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0216] Examples of temporary supports include those described in paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO 2012 / 081680, and paragraphs 0029 to 0040 of WO 2018 / 179370, the contents of which are incorporated herein by reference.

[0217] 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 μm. The film thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include 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.).

[0218] [Composition Layer] The composition layer is a layer formed using the above composition. The various components that can be contained in the composition layer are synonymous with the various components that can be contained in the above composition, and the preferred embodiments are also the same. However, the preferred numerical ranges for the contents of the various components in the composition layer are the same as the preferred ranges obtained by replacing the above "contents (% by mass) of the various components relative to the total solid content of the composition" with "contents (% by mass) of the various components relative to the total mass of the composition layer." Specifically, the statement "The resin content is preferably 5.0% by mass or more relative to the total solid content of the composition" should be replaced with "The resin content is preferably 5.0% by mass or more relative to the total mass of the composition layer."

[0219] The composition layer may further contain a solvent. The solvent has the same meaning as the solvent that may be contained in the composition, and the preferred embodiments are also the same.

[0220] The average thickness of the composition layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, and particularly preferably 5.0 μm or more, from the viewpoint of more excellent insulation reliability. The average thickness of the composition layer is preferably 40 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and particularly preferably 19 μm or less, from the viewpoint of excellent pattern resolution.

[0221] The transfer film may have other layers in addition to those described above, such as an intermediate layer, a thermoplastic resin layer, a cover film, and a high refractive index layer.

[0222] 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.

[0223] The transfer film may have a cover film. The number of fisheyes with a diameter of 80 μm or more contained in the cover film is 5 / m. ２ The following are preferred: Fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is introduced into the film when the material is thermally melted and then kneaded, extruded, and / or biaxially stretched, cast, or other methods are used to produce the film.

[0224] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 5 or less pieces / mm ２ The following is more preferable: This can suppress defects caused by the transfer of irregularities due to particles contained in the cover film to the composition layer.

[0225] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm 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.In addition, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0226] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film, and examples of the cover film include the cover films described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0227] Examples of cover films 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. Examples of recycled products include those obtained by cleaning and chipping used films and then forming the resulting material into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0228] The transfer film may have a high refractive index layer. Examples of 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.

[0229] [Method for manufacturing transfer film] A known manufacturing method can be applied to the manufacturing method of the transfer film. In the manufacturing method of the transfer film, it is preferable to coat a composition on a temporary support to form a composition layer, and it is more preferable to dry a coating film of the composition to form a composition layer. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0230] For example, a method for manufacturing the transfer film 100 shown in Fig. 1 includes a step of applying a composition to the surface of a temporary support 12 to form a coating film, and then drying this coating film to form a composition layer 14. Furthermore, the transfer film 100 shown in Fig. 1 is manufactured by pressing a cover film 16 onto the composition layer of the transfer film manufactured by the above manufacturing method. Furthermore, the transfer film 100 shown in Fig. 1 may be wound up after manufacturing and stored as a roll-form transfer film 100. The roll-form transfer film 100 can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0231] As described above, the transfer film may have an intermediate layer and / or a thermoplastic resin layer between the temporary support and the composition layer. Examples of the intermediate layer-forming composition, the method for forming the intermediate layer, the thermoplastic resin layer-forming composition, and the method for forming the 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.

[0232] [Uses] The composition is used to form a specific film, which can be used in a variety of applications. The specific film can be used, for example, 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. More specifically, examples of the specific film include a protective film or insulating film for a touch panel electrode, a protective film or insulating film for a printed wiring board, a protective film or insulating film for a TFT substrate, an interlayer insulating film in a build-up substrate for a semiconductor package, an organic interposer, a color filter, an overcoat film for a color filter, and an etching resist for wiring formation. In particular, the composition and transfer film can be suitably used to form an insulating film, and the insulating film is preferably used as an insulating film for a semiconductor package. That is, the composition and transfer film are preferably used to form an insulating film for a semiconductor package. The composition and transfer film are also preferably used to manufacture a laminate having a patterned composition layer on a substrate.

[0233] [Method for producing laminate] 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 composition to obtain a laminate. Specifically, the method for producing a laminate preferably includes the following steps 1 to 4. Step 1: A step of forming a composition layer on a substrate using the composition. Step 2: A step of pattern-exposing the composition layer. Step 3: A step of developing the pattern-exposed composition layer using a developer to form a pattern having vias. Step 4: A step of subjecting the obtained pattern to at least one of heating and exposure.

[0234] Each step of the method for producing the laminate will be described in detail below.

[0235] [Step 1] Step 1 is a step of forming a composition layer on a substrate using a composition. Examples of methods for forming the composition layer include a method of applying the composition. Examples of methods for applying the composition include 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 also be formed using the above-mentioned transfer film. Examples of methods 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 the temporary support side is brought into contact with the substrate and the transfer film and substrate are laminated together. Examples of lamination methods include known transfer methods and lamination methods. Preferred methods include a method in which the substrate is laminated on the surface of the composition layer and pressure and heat are applied using a roll or the like. Examples of lamination methods include known laminators such as a vacuum laminator and an auto-cut laminator. The lamination temperature is not particularly limited, but is preferably 70 to 130°C. When a transfer film is used, Step 1 is preferably performed using a roll-to-roll system. The substrate to which the transfer film is laminated 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 of the steps included in the method for producing a laminate of the present invention, and a step of winding the substrate after any of the steps, and at least any of the steps (preferably all of the steps or all of the steps other than the heating step) is performed while the substrate is being transported. As the unwinding method in the unwinding step and the winding method in the winding step, any method known in the art for production methods that apply the roll-to-roll method may be used.

[0236] <Substrate> Examples of the substrate 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 composed of a light-transmitting substrate such as a glass substrate, and tempered glass, such as Corning Gorilla Glass, can also be used. Materials contained in the substrate include, for example, materials used in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. When the substrate includes a resin substrate, a resin film with low optical distortion and / or high transparency is more preferred. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0237] The substrate having a conductive layer is preferably a resin substrate having a conductive layer, and more preferably a resin film having a conductive layer, because it can be produced by a roll-to-roll process. The substrate having a conductive layer may be a laminate obtained by the above-mentioned method for producing a laminate.

[0238] Examples of the conductive layer include any conductive layer used in general circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The conductive layer in the substrate having a conductive layer may be one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, it is preferable that each conductive layer is made of a different material. Examples of materials for the conductive layer include simple metals and conductive metal oxides. Examples of simple 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 ２The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10 ４ It is preferably less than Ωcm.

[0239] The conductive layer may be patterned. Examples of methods for producing a patterned conductive layer include subtractive methods such as etching and additive methods. Examples of etching methods include wet etching methods 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.

[0240] [Step 2] Step 2 is a step of patternwise exposing the composition layer. "Patternwise exposure" refers to a form of patternwise exposure, i.e., exposure in a form in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in the patternwise exposure is not particularly limited and may be adjusted as appropriate. The patternwise exposure may be performed from the side opposite the substrate of the composition layer, or from the substrate side of the composition layer.

[0241] The light source used for exposure may be any light source that irradiates light in a wavelength range (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm) to which various photosensitive components in the composition layer (e.g., photopolymerization initiator, photoacid generator, and Compound Z) are sensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 to 2000 mJ / cm. ２ is preferred, and 10 to 1000 mJ / cm ２ is more preferred.

[0242] When a composition layer is formed using a transfer film in step 1, in step 2, the temporary support may be peeled off from the composition layer before pattern exposure, or pattern exposure may be performed through the temporary support before peeling off the temporary support, and then the temporary support may be peeled off. To prevent mask contamination due to contact between the composition layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. The pattern exposure may be performed through a mask or by direct exposure using a laser or the like. Examples of masks include quartz masks, soda-lime glass masks, and film masks. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is exemplified. In particular, it is preferable to peel off the temporary support from the composition layer before step 3.

[0243] [Step 3] Step 3 is a step in which the composition layer that has been pattern-exposed after step 2 is developed with a developer to form a pattern having vias.

[0244] 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 having vias may be either a through hole or a via hole. Examples of the shape of the via include a square, trapezoid, and inverted trapezoid cross-sectional shape; and a circle and a square front shape (the shape when the via is observed from the direction in which the via bottom is visible). In order to improve the adhesion of plated copper to the via wall surface, an inverted trapezoid cross-sectional shape is preferred. The via size (diameter) is preferably 300 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more. The number of vias may be 1 or more, and preferably 2 or more.

[0245] Examples of the developer include an alkaline developer and an organic solvent developer.

[0246] The alkaline developer is preferably an alkaline aqueous solution. The alkaline aqueous solution preferably contains a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L. The water content in the alkaline 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 alkaline developer. The upper limit is preferably less than 100% by mass, based on the total mass of the alkaline developer. Examples of alkaline developers include aqueous sodium carbonate solutions, aqueous potassium carbonate solutions, aqueous sodium hydroxide solutions, aqueous potassium hydroxide solutions, and aqueous tetramethylammonium hydroxide (TMAH) solutions. Examples of the concentration of the alkaline component constituting the alkaline developer include aqueous solutions of 0.1% by mass, 1.0% by mass, and 2.38% by mass. The alkaline developer may also contain a water-soluble organic solvent, a surfactant, and the like. Examples of the alkaline developer include the developer described in paragraph 0194 of WO 2015 / 093271.

[0247] Examples of organic solvent developers include developers containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Cyclopentanone or propylene glycol monomethyl ether acetate is preferred as the organic solvent developer, and cyclopentanone is more preferred. In the organic solvent developer, a mixture of multiple organic solvents may be used, or the organic solvent may be mixed with an organic solvent other than those mentioned above or with water. The water content of the organic solvent developer is preferably less than 10% by mass, based on the total mass of the organic solvent developer, and more preferably substantially free of water. The organic solvent content of 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.

[0248] Examples of development methods include puddle development, shower development, spin development, and dip development. In shower development, unnecessary portions can be removed by spraying a developer onto the composition layer after exposure. It is also preferable to spray a detergent 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.

[0249] [Step 4] Step 4 is a step of subjecting the pattern obtained in Step 3 to at least one of heating and exposure. Step 4 promotes the reaction of the resin precursors of the composition (for example, a ring-closing reaction of a polyimide precursor and a polybenzoxazole precursor), allowing the formation of a resin. Step 4 is preferably a step of at least heating.

[0250] The temperature and time of the heat treatment can be appropriately selected depending on the type of resin and its precursor. The heat treatment temperature is preferably 120 to 400°C, more preferably 150 to 400°C, and even more preferably 180 to 350°C. The heat treatment time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and even more preferably 1 to 9 hours. The heat treatment may be performed 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.

[0251] The light source and 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 5 to 2000 mJ / cm. ２ is preferred, and 10 to 2000 mJ / cm ２ is more preferred.

[0252] [Other Steps] The method for producing a laminate may include other steps in addition to those described above. Examples of other steps include the following steps.

[0253] <Cover Film Peeling Step> When the transfer film has a cover film in the laminate manufacturing method, it is preferable to include a step of peeling off the cover film of the transfer film. As the method for peeling off the cover film, a known method can be applied.

[0254] <Step of Reducing Visible Light Reflectance> When the substrate is a substrate having a conductive layer, the method for producing the laminate may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer. When the substrate is a substrate having a plurality of conductive layers, the treatment to reduce the visible light reflectance may be performed on some or all of the conductive layers. Examples of treatments to reduce the visible light reflectance include oxidation treatments. For example, copper can be oxidized to copper oxide, thereby blackening the conductive layer, thereby reducing the visible light reflectance of the conductive layer. Suitable embodiments of treatments to reduce 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.

[0255] <Etching Step> When the base material is a substrate having a conductive layer, the method for producing a 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. 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.

[0256] The method for producing the laminate also preferably uses a substrate having a plurality of conductive layers on both surfaces thereof, and sequentially or simultaneously forms patterns on the conductive layers formed on both surfaces. With this configuration, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface. Formation from both surfaces of the substrate by roll-to-roll is also preferred.

[0257] [Laminate] The laminate is a laminate obtained by the above-described laminate manufacturing method. The laminate has a substrate and a composition layer having a pattern including vias. The laminate is used, for example, in semiconductor devices. Examples of semiconductor devices include 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.).

[0258] [Method for manufacturing a semiconductor package] The method for manufacturing a laminate described above can be suitably applied as a method for manufacturing a semiconductor package. Examples of methods for manufacturing a semiconductor package include known manufacturing methods such as a method for manufacturing a build-up substrate. Specifically, examples include a manufacturing method having steps Z1 to Z5 in this order. Step Z1: A step of forming a composition layer on a substrate having a conductive layer. Step Z2: A step of pattern-exposing the composition layer. Step Z3: A step of developing the pattern-exposed composition layer with a developer to form a pattern having vias. Step Z4: A step of subjecting the obtained pattern to at least one of heating and exposure. Step Z5: A step of forming a circuit pattern on the pattern.

[0259] Steps Z1 to Z4 in the method for manufacturing a semiconductor package include the above-described steps 1 to 4, respectively.

[0260] [Step Z5] Step Z5 is a step of forming a circuit pattern on the pattern. A semi-additive process is preferred as a method for forming a circuit pattern because it allows for the formation of fine wiring. Examples of semi-additive processes include the following: First, after Step Z3, the via bottoms, via walls, 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 used to form a power supply layer for electrolytic copper plating, and the seed layer thickness is preferably 0.1 to 2.0 μm. A seed layer thickness of 0.1 μm or more tends to suppress a decrease in connection insulation reliability during electrolytic copper plating. A seed layer thickness of 2.0 μm or less tends to eliminate the need for a large etching amount when flash etching the seed layer between wirings, thereby tending to suppress damage to the wiring during etching. Electroless copper plating is performed by depositing metallic copper on the surface of a pattern having vias through a reaction between copper ions and a reducing agent. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst used in 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 used in 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 the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0261] After electroless copper plating, it is preferable to thermocompress the surface of the composition layer of the transfer film opposite the temporary support onto the electroless copper plating using a roll laminator. The thickness of the composition layer is preferably 5 to 30 μm, since it can be made thicker than the wiring height after electrolytic copper plating. After thermocompression bonding of the transfer film, the composition layer is exposed to light, for example, through a mask on which a desired wiring pattern is drawn. Examples of the exposure method include the exposure method in step 2. After 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 forming the pattern, development residues of the composition may be removed using plasma or the like. After development, electrolytic copper plating is performed to form a copper circuit layer and via filling. After electrolytic copper plating, the pattern is peeled off using an alkaline aqueous solution or an amine-based stripper. After peeling the pattern, the seed layer between the wiring is removed (flash etching). Flash etching is performed, for example, using an oxidizing solution containing sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of oxidizing solutions include "SAC" manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Co., Ltd. After flash etching, palladium and other materials 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.

[0262] After the pattern is removed or after the flash etching step, a post-baking treatment is preferably performed. The post-baking treatment sufficiently cures any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The preferred thermosetting conditions are a curing temperature of 150 to 240°C and a curing time of 15 to 500 minutes.

[0263] 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 step Z4 and before step Z5. By performing the roughening step, the surface of the pattern can be roughened to improve adhesion with the circuit wiring. Smears can also be removed at the same time. Examples of the roughening step include known desmearing treatments, and treatments involving contact with a roughening liquid are preferred. Examples of roughening liquids include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid, etc.), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.

[0264] The above-described steps are repeated depending on the number of layers required to manufacture a semiconductor package. It is preferable to form a solder resist on the outermost layer.

[0265] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes the specific film. The semiconductor package preferably includes the laminate described above, and more preferably is manufactured using the semiconductor package manufacturing method described above. In the 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.

[0266] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. In the following examples, "%" means "% by mass" unless otherwise specified.

[0267] [Preparation of Composition] Various components were mixed to prepare a mixture in the amounts (solid content ratio) shown in the table below. Next, the 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.

[0268] The various components contained in the composition are listed below.

[0269] [Resins] A-1: ​​Polyimide precursor, resin synthesized by the synthesis method for Resin A-1 described later A-2: Polyimide precursor, resin synthesized by the synthesis method for Resin A-2 described later A-3: Polyimide precursor, resin synthesized by the synthesis method for Resin A-3 described later A-4: Polybenzoxazole precursor, resin synthesized by the synthesis method for Resin A-4 described later A-5: Phenolic resin, TR4020G, manufactured by Asahi Organic Chemicals Co., Ltd. A-6: Epoxy resin, ZX1059 (mixture of bisphenol A epoxy resin and bisphenol F 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 for Resin A-7 described later A-11: Vinylbenzyl-modified polyphenylene ether resin, manufactured by Mitsubishi Gas Chemical Co., Inc., "OPE-2St 1200" toluene solution A-12: Acrylic resin, styrene / acrylic acid=71% by mass / 29% by mass, synthesized by the following method.

[0270]

[0271] <Method for Synthesizing Resin A-1> 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours, 20.0 g, 64.5 mmol), 2-hydroxyethyl methacrylate (16.8 g, 129 mmol), hydroquinone (0.05 g), pyridine (20.4 g, 258 mmol), and diethylene glycol dimethyl ether (100 g) were mixed and stirred at 60°C for 18 hours to obtain a reaction mixture (a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate). Next, the obtained diester was treated with thionyl chloride (SOCl ２) to obtain a reaction mixture. Next, a solution of 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) dissolved in N-methylpyrrolidone (100 mL) was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. After reacting the reaction mixture at 0°C for 1 hour, ethanol (70 g) was added and the mixture was stirred at room temperature for 1 day. The resulting reaction solution was added to water (5 L) and stirred at 5,000 rpm for 15 minutes to obtain a crude polymer precipitate. The precipitate collected by filtration from the mixture was stirred in water (3 L) for 30 minutes and collected by filtration again. The resulting precipitate was dried under reduced pressure at 45°C for 3 days to obtain Resin A-1, a polyimide precursor. The weight-average molecular weight (Mw) of Resin A-1 was 18,000.

[0272] <Method for Synthesizing Resin A-2> 4,4'-oxydiphthalic dianhydride (77.6 g) and diphenyl-3,3',4,4'-tetracarboxylic dianhydride (73.6 g) were placed in a 2 L separable flask, 2-hydroxyethyl methacrylate (134.0 g) and γ-butyrolactone (400 mL) were added, and pyridine (79.1 g) was added while stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, a solution of dicyclohexylcarbodiimide (DCC, 206.3 g) dissolved in γ-butyrolactone (180 mL) was added to the reaction mixture over 40 minutes while stirring under ice cooling. Next, a suspension of 4,4'-oxydianiline (ODA, Mw = 200.24, 93.0 g) in γ-butyrolactone (350 mL) was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, ethanol (30 mL) was added and stirred for 1 hour, after which γ-butyrolactone (400 mL) was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to ethyl alcohol (3 L) to obtain a crude polymer precipitate. The resulting crude polymer was collected by filtration and dissolved in tetrahydrofuran (1.5 L) to obtain a crude polymer solution. The resulting crude polymer solution was purified using an anion exchange resin (Amberlyst TM15, manufactured by Organo Corporation) to obtain a polymer solution. The resulting polymer solution was added dropwise to water (28 L) to precipitate the polymer, and the resulting precipitate was collected by filtration and dried under vacuum to obtain Resin A-2, a powdered polyimide precursor. 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.

[0273] <Method for synthesizing Resin A-3> Resin A-3, a polyimide precursor, was obtained using 4,4'-diaminodiphenyl ether as the diamine and 4,4'-oxydiphthalic anhydride as the dianhydride. The weight average molecular weight of Resin A-3 was 15,000.

[0274] <Method for synthesizing Resin A-4> Resin A-4, a polybenzoxazole precursor, was obtained using 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as a diamine and 4,4'-oxybis(benzoyl chloride) as an acid chloride. The weight-average molecular weight of Resin A-4 was 15,000.

[0275] <Method for synthesizing resin A-7> 1.3 g of di-μ-hydroxo-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu / TMEDA) and 1.59 mL of tetramethylethylenediamine (TMEDA) were added to a 1500 mL two-necked recovery flask and thoroughly dissolved. Oxygen was supplied at 10 mL / min. 52.5 g of 2,6-dimethylphenol and 6.5 g of 2-allylphenol were dissolved in 0.75 L of toluene to prepare a raw material solution. This raw material solution was added dropwise to the recovery flask and reacted at 45 °C for 5 hours while stirring at a rotation speed of 600 rpm. After completion of the reaction, the product was reprecipitated in a mixture of 10 L of methanol and 11 mL of concentrated hydrochloric acid, filtered, and dried at 70 °C for 24 hours to obtain resin A-7. Resin A-7 had a number average molecular weight of 25,000 and a weight average molecular weight of 66,000.

[0276] <Method for synthesizing resin A-12> 1-methoxy-2-acetoxypropane (PGMEA, 60 parts) and propylene glycol monomethyl ether (PGME, 240 parts by mass) were placed in a 2000 mL flask to prepare a mixed solution. The resulting mixed solution was heated to 90°C while stirring at a stirring speed of 250 rpm. Dropping solution (1) was obtained by mixing styrene (71 parts by mass) and acrylic acid (29 parts by mass) and diluting with PGMEA (60 parts by mass). Dropping solution (2) was obtained by dissolving V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 9.637 parts by mass) in PGMEA (136.56 parts by mass). Next, Dropping Solution (1) and Dropping Solution (2) were simultaneously added dropwise over 3 hours to a 2000 mL flask containing the mixed solution heated to 90°C. After completion of the dropwise addition, V-601 (2.401 parts by mass) was added to the flask three times every hour. The mixture was then stirred at 90°C for an additional 3 hours. The reaction solution obtained in the flask was then diluted with PGMEA to obtain a solution containing Resin A-6 (solid concentration 36.3% by mass).

[0277] 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 a solid content concentration of 65% by mass, manufactured by DIC Corporation.

[0278] [Specific inorganic fillers and comparative inorganic fillers] Specific inorganic fillers B-1 to B-10 and comparative inorganic fillers b-1 to b-2, which will be described later, were used as the specific inorganic fillers or comparative inorganic fillers.

[0279] <Method for preparing specific inorganic filler B-1> 100 g of silica (VP RM 30, manufactured by Nippon Aerosil Co., Ltd.) surface-modified with 3-methacryloxytrimethoxypropylsilane was added to 1,000 g of a 1% by mass MEK solution of hexamethyldisilazane and stirred for 30 minutes to obtain a mixed solution. The resulting mixed solution was then filtered using a 50 nm diameter PTFE membrane filter (manufactured by Advantec Toyo Co., Ltd., TCF-005), and the resulting residue was added to 500 g of MEK and stirred for 30 minutes to wash. Thereafter, the mixture was again filtered using a 50 nm diameter PTFE membrane filter (manufactured by Advantec Toyo Co., Ltd., TCF-005), and the residue was surface-modified with 3-methacryloxytrimethoxypropylsilane and hexamethyldisilazane to obtain specific inorganic filler B-1.

[0280] <Method for preparing specific inorganic fillers B-2 to B-10 and comparative inorganic fillers b-1 to b-2> Specific inorganic fillers B-2 to B-10 and comparative inorganic fillers b-1 to b-2 were obtained using the same procedure as in the preparation method for specific inorganic filler B-1 described above, except that the raw materials were changed to those shown in the table below. Note that for specific inorganic fillers B-6 to B-10, the inorganic fillers shown in the table were surface-modified with surface modifier A, and then the obtained inorganic fillers surface-modified with surface modifier A were further surface-modified with surface modifier B to obtain specific inorganic fillers B-6 to B-10.

[0281] In the table, Mw indicates the molecular weight of each surface modifier. The pKaH of the basic compound is a value measured by the method described above.

[0282]

[0283] [Thermal base generator] C-1: Compound having the following structure

[0284]

[0285] C-2: U-CAT SA841 (manufactured by San-Apro Co., Ltd.)

[0286] [Compounds having a reactive group (polymerizable compounds)] D-1: Compound having the following structure

[0287]

[0288] SR205NS: Bifunctional polymerizable compound, manufactured by Sartomer Corporation SR209: Bifunctional polymerizable compound, manufactured by Sartomer Corporation

[0289] [Other components] HAT: additive, 5-amino-1H-tetrazole S-506: silicone surfactant, manufactured by DIC Corporation F-551A: Megafac (registered trademark) F551A, fluorine-based surfactant, manufactured by DIC Corporation Oxe-01: photopolymerization initiator, Irgacure OXE-01, manufactured by BASF Corporation Oxe-02: photopolymerization initiator, Irgacure OXE-02, manufactured by BASF Corporation EPEG: plasticizer, ethyl phthalyl ethyl glycolate, manufactured by Tokyo Chemical Industry Co., Ltd. J-5: isopropylidene group-containing maleimide compound, toluene solution, MIR-500-60T, manufactured by Nippon Kayaku Co., Ltd.

[0290] [Evaluation] The dielectric properties and migration resistance of the specific film were evaluated using the compositions of each example and each comparative example. The average particle size was also measured for each example and each comparative example. The average particle size of the specific inorganic filler or the comparative inorganic filler is shown in the table below. The average particle size was measured using the particle size measurement method described above.

[0291] [Dielectric Properties] A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and the compositions shown in the table were applied to the substrate and dried to obtain a laminate having a composition layer of 30.0 μm thickness on the substrate. The obtained laminate was exposed to light (high-pressure mercury lamp, wavelength 365 nm, cumulative illuminance measured with an illuminometer: 1000 mJ / cm2). ２ ), and then heated in an oven (200°C, 1.5 hours). After that, the film 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 derived from the composition layer. If the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week to be peeled off. The obtained free-standing film was cut into a size of 2 cm x 3 cm to prepare a measurement sample. The average dielectric loss tangent was measured using a 28 GHz split cylinder resonator (manufactured by Kanto Electronics Application Development Co., Ltd.). Three samples were measured, and the average value was used. The obtained results were evaluated according to the following criteria.

[0292] <Evaluation criteria> "A": Dielectric loss tangent is 0.010 or less "B": Dielectric loss tangent is more than 0.010 and less than 0.015 "C": Dielectric loss tangent is more than 0.015

[0293] [Migration Resistance] A comb-shaped copper pattern having a thickness of 2.0 μm and a line / space ratio of 20 μm / 40 μm was formed on a silicon wafer substrate to prepare a substrate. The prepared composition was applied to the 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 μm. Next, the obtained composition layer was exposed to light using an ultra-high pressure mercury lamp. At this time, the cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 1000 mJ / cm. ２ After the exposure, a heat treatment was carried out in a nitrogen atmosphere at 200°C for 90 minutes to prepare samples for evaluation. Ten evaluation samples were prepared, and each evaluation sample was placed in a chamber at 130°C and 85% RH (relative humidity) using a HAST tester (highly accelerated life tester) for 168 hours. Thereafter, a voltage of 5.0 V was applied, and the time and number of samples for which migration occurred were evaluated according to the following criteria. The fewer the number of samples for which migration occurred, the better the migration resistance. Note that the initial resistance value when first measured at room temperature was 1 x 10 １４ Ω or more in samples, 1 × 10 ３ If migration occurs when the resistance drops below Ω, it is counted.

[0294] <Evaluation criteria> A: Migration occurred in 2 or fewer samples. B: Migration occurred in 3 to 5 samples. C: Migration occurred in 6 to 7 samples. D: Migration occurred in 8 to 10 samples.

[0295] [Results] The contents of various components and the evaluation results are shown below. In the table, "amount" indicates the content (% by mass) relative to the total solid content of the composition. Table 3 is a continuation of Table 2.

[0296]

[0297]

[0298] From the results shown in the above table, it was confirmed that the composition of the present invention can form a film having excellent dielectric properties and excellent migration resistance.

[0299] It was confirmed that when the resin contained at least one selected from the group consisting of polyimide precursor, polyimide, polybenzoxazole precursor, polybenzoxazole, epoxy resin, and polyphenylene ether resin, the dielectric properties were better (e.g., comparison of Examples 3 to 5, 8 to 16, and 23 to 28 with Examples 29 to 31). From a comparison of Examples 32 to 36 with Example 37, it was confirmed that when the average particle size of the specific inorganic filler was 300 nm or less, the migration resistance was better.

[0300] Instead of a laminate having a composition layer formed using the composition, a laminate having a composition layer formed using a transfer film produced by the following procedure was evaluated in the same manner as the above-mentioned [Dielectric properties] and [Migration resistance]. As a result, evaluation results equivalent to the evaluation results of [Dielectric properties] and [Migration resistance] for the specific film formed using the composition were obtained.

[0301] The composition of each example was applied to a temporary support (QS62, manufactured by Toray Industries, Inc., 31 μm thick PET film) and dried at 100°C to form a composition layer. The film thickness of the composition layer was adjusted to 15 μm after drying. Next, a cover film (Oji F-Tex Co., Ltd., polypropylene film, FG-201, 30 μm thick) was attached to the side of the composition layer opposite the temporary support to obtain a transfer film. After peeling the cover film from the transfer film, each transfer film was laminated so that the composition layer of each transfer film contacted both sides of a glass epoxy substrate (CCL-EL190T, 1.0 mm thick, manufactured by Mitsubishi Gas Chemical Co., Inc.) on which a circuit pattern had been formed, thereby forming a composition layer on both sides of the glass epoxy substrate. A vacuum laminator was used for this. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 50°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. The composition layer was subjected to pattern exposure, and the pattern-exposed composition layer was further developed using a developer to form a pattern with vias having a diameter of 80 μm at predetermined positions. The pattern was then subjected to a heat treatment, and the residue was removed using a sodium permanganate aqueous solution as a roughening solution, followed by electroless plating. Next, a resist pattern was formed at a predetermined position using a known dry film resist, followed by electrolytic plating. The resist pattern was then stripped using a stripping solution. Finally, a seed layer etching process was performed, followed by a heat treatment (180°C, 1 hour) to form copper wiring on the cured film. The above steps from lamination to heat treatment were performed a total of three times. Finally, a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted at a predetermined position on a printed wiring board to obtain a semiconductor package substrate. It was confirmed that the resulting semiconductor package substrate operated normally.

[0302] 12: Temporary support 14: Composition layer 16: Cover film 100: Transfer film

Claims

1. A composition comprising a resin and an inorganic filler, wherein the resin comprises at least one selected from the group consisting of a polyimide precursor, a polyimide, a polybenzoxazole precursor, a polybenzoxazole, an epoxy resin, a polyphenylene ether resin, an acrylic resin, and a methacrylic resin, the inorganic filler is surface-modified with two or more surface modifiers, and at least one of the two or more surface modifiers has a reactive group, and the composition satisfies at least one of Requirement 1 and Requirement 2. Requirement 1: The resin has a reactive group. Requirement 2: The composition comprises a compound that is different from the resin and has a reactive group.

2. The composition according to claim 1, wherein the two or more types of surface modifiers include a surface modifier A having a molecular weight of 220 or more and a surface modifier B having a molecular weight of less than 220.

3. The composition according to claim 1, wherein the reactive group is a group having an ethylenically unsaturated double bond.

4. The composition according to claim 1, wherein the resin comprises at least one selected from the group consisting of polyimide precursors and polyimides.

5. The composition according to claim 4, wherein the surface modifier having a reactive group is a compound represented by formula (S), the inorganic filler is silicon dioxide, and the two or more types of surface modifiers include at least one selected from the group consisting of disilazane compounds and basic compounds. X-L Ｘ -Si(R Ｘ ) ３ (S) In formula (S), X represents a reactive group. Ｘ represents a single bond or a divalent linking group. Ｘ each independently represents a hydrolyzable group or a hydroxyl group.

6. The composition according to claim 5, wherein the basic compound has a pKaH of 4.0 to 15.

0.

7. The composition of claim 1, wherein said inorganic filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

8. The composition according to claim 1, wherein the average particle size of the inorganic filler is 300 nm or less.

9. The composition according to claim 1, wherein the average particle size of said inorganic filler is 150 nm or less.

10. The composition according to claim 1, wherein the content of the inorganic filler is 30.0 mass% or more based on the total solid content of the composition.

11. The composition according to claim 1, wherein the content of the inorganic filler is 90.0 mass % or less based on the total solid content of the composition.

12. A transfer film having a temporary support and a composition layer formed by using the composition according to any one of claims 1 to 11.

13. A method for producing a laminate, comprising: step 1 of forming a composition layer on a substrate using the composition according to any one of claims 1 to 11; step 2 of pattern-exposing the composition layer; step 3 of developing the pattern-exposed composition layer using a developer to form a pattern having vias; and step 4 of subjecting the obtained pattern to at least one of heating and exposure.

14. A laminate produced by the method for producing a laminate according to claim 13.

15. A semiconductor package comprising the laminate of claim 14.

Images