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

Abstract

The present invention addresses the problem of providing a composition from which it is possible to form a membrane having a small linear expansion coefficient and having excellent insulation reliability. A composition according to the present invention contains a resin and a liquid crystalline compound having a polymerizable group. The resin contains at least one selected from the group consisting of polyimides, silicone resins, polybenzoxazoles, phenol resins, epoxy resins, polyphenylene ether resins, benzocyclobutene resins, fluorene resins, liquid crystal polymers, polyethersulfones, polyarylates, polyether imides, polybenzimidazoles, polyphenylsulfones, polycarbonates, acrylonitrile-butadiene-styrene copolymer resins, polyphenylene sulfides, and precursors thereof.

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-described insulating film, for example, Patent Document 1 discloses a photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, (B) an epoxy resin, and (C) an active ester compound.

[0004] International Publication No. 2021 / 029021

[0005] In order to maintain device performance and prevent failure, the insulating film described above is required to have a small linear expansion coefficient and excellent insulating reliability. The present inventors have studied films obtained using the photosensitive resin composition described in Patent Document 1 and found that there is room for improvement in the linear expansion coefficient and insulating reliability of the obtained film. The insulating reliability refers to the wet heat resistance of the insulating properties of the film.

[0006] Therefore, an object of the present invention is to provide a composition that can form a film having a small linear expansion coefficient and excellent insulation reliability, as well as a transfer film, a method for manufacturing a laminate, a laminate, and a semiconductor package related 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 a liquid crystalline compound having a polymerizable group, wherein the resin comprises at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenolic resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin, polyphenylene sulfide, and precursors thereof. [2] The composition according to [1], wherein the liquid crystalline compound having a polymerizable group is a compound represented by formula (Z1) described below. [3] The composition according to [1] or [2], further comprising a photopolymerization initiator. [4] The composition according to any one of [1] to [3], wherein at least one of the resin and the liquid crystalline compound having a polymerizable group has an ethylenically unsaturated double bond. [5] The composition according to any one of [1] to [4], wherein the molecular weight of the liquid crystal compound having a polymerizable group is 2,000 or less. [6] The composition according to any one of [1] to [5], wherein the content of the liquid crystal compound having a polymerizable group is 1.0 to 50.0 mass% based on the total solid content of the composition. [7] The composition according to any one of [1] to [6], wherein the content of the liquid crystal compound having a polymerizable group is 1.0 to 30.0 mass% based on the total solid content of the composition. [8] The composition according to any one of [1] to [7], wherein the mass ratio of the content of the liquid crystal compound having a polymerizable group to the content of the resin is 0.01 to 3.00. [9] The composition according to any one of [1] to [8], wherein the resin comprises at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.

[10] The composition according to any one of [1] to [9], further comprising a filler.

[11] The composition according to

[10] , wherein the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

[12] The composition according to

[10] or

[11] , wherein the filler has an average particle size of 300 nm or less.

[13] The composition according to any one of

[10] to

[12] , wherein the average particle size of the filler is 150 nm or less.

[14] The composition according to any one of

[10] to

[13] , wherein the content of the filler is 30.0 mass % or more, based on the total solid content of the composition.

[15] The composition according to any one of

[10] to

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

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

[15] , which is used for forming an insulating film for a semiconductor package.

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

[16] .

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

[16] ; Step 2: forming a pattern including vias in the composition layer; and Step 3: subjecting the pattern to at least one of heating and exposure.

[19] A laminate manufactured by the method for manufacturing a laminate according to

[18] .

[20] A semiconductor package, comprising the laminate according to

[19] .

[0009] According to the present invention, there is provided a composition capable of forming a film having a small linear expansion coefficient and excellent insulation reliability. Also provided are a transfer film, a method for manufacturing 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, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, such as g-rays, h-rays, and i-rays, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). Furthermore, in the present invention, light refers to actinic rays or radiation. In this specification, "exposure" refers to not only exposure using far ultraviolet rays typified by mercury lamps and excimer lasers, extreme ultraviolet rays, and X-rays, but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.

[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 polymer 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 "composition") contains a resin and a liquid crystalline compound having a polymerizable group, and the resin contains at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenolic resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin, polyphenylene sulfide, and precursors thereof.

[0024] While the reason why the composition having the above-described 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. By including the specific resin described above in the composition of the present invention, the composition of the present invention can form a film with a low linear expansion coefficient. Furthermore, while components other than the resin contained in the composition (e.g., a polymerizable compound) tend to reduce the insulating reliability of the film, by including a liquid crystal compound having a polymerizable group, molecular motion is suppressed by the interaction between the components, thereby suppressing unintended reactions such as decomposition reactions in the film. As a result, it is speculated that the film formed by the composition of the present invention also has excellent insulating reliability. Hereinafter, the film formed by the composition of the present invention will also be referred to as a "specific film." Furthermore, as a characteristic of the composition, a small linear expansion coefficient of the specific film will simply be referred to as a "small linear expansion coefficient," excellent insulating reliability of the specific film will simply be referred to as "excellent insulating reliability," and achieving at least one of a smaller linear expansion coefficient and excellent insulating reliability will also be referred to as "excellent effects of the present invention."

[0025] The various components that may be contained in the composition of the present invention are described in detail below.

[0026] [Resin] The composition contains a resin, and the resin contains at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenolic resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin, polyphenylene sulfide, and precursors thereof. In terms of achieving superior effects of the present invention and achieving a smaller dielectric dissipation factor for the specific film, the resin preferably contains at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, polyphenylene ether resin, benzocyclobutene resin, liquid crystal polymer, and precursors thereof, and more preferably contains at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof. The precursor of the resin is a resin that can be converted into the resin by heat treatment, light treatment, or chemical treatment.

[0027] The resin may have a polymerizable group. Examples of the polymerizable group include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, with the radical polymerizable group being preferred. The radical polymerizable group is preferably a group having an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, and a vinyl ether group, with the (meth)acryloyl group being preferred. The resin also preferably has a polymerizable group that is polymerizable with the polymerizable group in the liquid crystal compound having a polymerizable group, which will be described later.

[0028] 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.

[0029] <Polyimide and Polyimide Precursor> Polyimide is a resin having an imide structure. As the polyimide, a resin having a cyclic imide structure is preferred, and 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 preferred. The polyimide precursor preferably has a repeating unit represented by formula (1).

[0030]

[0031] 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 １１４ R each independently represents a hydrogen atom or a monovalent organic group. １１５ represents a tetravalent organic group.

[0032] 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.

[0033] 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-. １１１As 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:

[0034]

[0035] 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 ２ A 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.

[0036] 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.

[0037] Ar ０The 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.

[0038] 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).

[0039]

[0040]

[0041] 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.

[0042] 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 polymerizable group, １１３ and R １１４ It is more preferable that both R and R represent a group having a polymerizable group. Examples of the polymerizable group include the groups exemplified as the polymerizable group that the resin may have. The monovalent organic group may be a monovalent organic group X, which will be described later. １１３ and R １１４ As the alkyl group, 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.

[0043]

[0044] 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.

[0045] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２００ As the alkyl group, a methyl group is preferred.

[0046] 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.

[0047] 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.

[0048] 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.

[0049]

[0050] 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.

[0051] In formula (5), R１１２ has the same meaning as A described above, and the preferred embodiments are also the same.

[0052] 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).

[0053]

[0054] 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.

[0055] 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.

[0056] Examples of the tetracarboxylic dianhydride include compounds represented by any one of formulas (DAA-1) to (DAA-5).

[0057]

[0058] (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.

[0059] 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.

[0060] 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).

[0061]

[0062] 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.

[0063] 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.

[0064] 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).

[0065] The polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] <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).

[0071]

[0072] 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.

[0073] 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:

[0074] 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:

[0075] 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.

[0076] 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.

[0077] 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.

[0078] Phenolic resins are resins having phenolic hydroxyl groups. Examples of phenolic resins include phenol novolac resins, cresol novolac resins, biphenyl aralkyl phenolic resins, naphthol aralkyl resins, and naphthol novolac resins. Examples of phenolic resins include AV Light series such as TR4020G, TR4050G, TR4080G, TR5020G, TR5050G, TR6020G, TR6050G, and TR6080G manufactured by Asahi Organic Chemicals Co., Ltd.; photoresist resin series manufactured by Sumitomo Bakelite Co., Ltd.; Resitop series manufactured by Gun-ei Chemical Industry Co., Ltd.; PR-30-40P, PR-100L, PR-100H, PR-50, PR-55, PR-56-1, PR-56-2, and WR. Phenolite series such as WR-101, WR-102, WR-103, and WR-104, manufactured by DIC Corporation; photoresist resins such as LF-100, LF-110, LF-120, LF-200, LF-400, and LF-500, manufactured by Lignite Corporation; MEHC-7851SS, MEHC-78004S, MEHC-7851-SS, MEHC-7851-S, MEHC-7851-M, MEHC-7851-H, MEHC-7800-4S, MEHC -7800-SS, MEHC-7800-S, MEHC-7800-M, and MEHC-7800-H, manufactured by Meiwa Kasei; GPH-65, GPH-103, and MEHC-7841-4S, manufactured by Nippon Kayaku; BisP-AP, BisP-MIBK, BisP-B, Bis-Z, BisP-CP, o,o'-BPF, BisP-IOTD, BisP-IBTD, BisP-DED, BisP-BA, Bis-C, Bis26X-A, BisOPP-A, Examples of the phenolic resin include BisOTBP-A, BisOCHP-A, BisOFP-A, BisOC-Z, BisOC-FL, BisOC-CP, BisOCHP-Z, MethylenebisP-CR, TM-BPF, BisOC-F, Bis3M6B-IBTD, BisOC-IST, BisP-IST, BisP-PRM, BisP-LV, BisE, and BisP-TMC manufactured by Honshu Chemical Co., Ltd.; and BisA, BisF, and BisP-M manufactured by Mitsui Chemicals Fine Co., Ltd. Examples of the phenolic resin include the resins described in JP 2021-157174 A.Further, examples of the phenolic resin include phenolic curing agents such as EPICLON series, EXB9451, EXB9460, EXB9460S, and HPC8000-65T (manufactured by DIC Corporation).

[0079] Epoxy resins are resins containing 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.

[0080] 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").

[0081] 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.

[0082] 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.

[0083] 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, with a branched structure being 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, ortho, and para positions, of at least one benzene ring constituting the polyphenylene ether resin.

[0084] 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 polymerizable group, or a mixture of a phenolic compound having hydrogen atoms at the ortho- and para-positions but no polymerizable group and a phenolic compound having no hydrogen atom at the ortho-position, a hydrogen atom at the para-position, and a polymerizable group.

[0085] 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.

[0086] It is also preferable that the polyphenylene ether resin has a polymerizable group. As the polymerizable 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 polymerizable 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.

[0087] 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.

[0088] The silicone resin is a resin having an organosiloxane structure. Examples of the silicone resin include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, and curable silicone resins are preferred. Examples of the curable silicone resin include addition reaction silicone resins, condensation reaction silicone resins, and ultraviolet or electron beam curable silicone resins.

[0089] Examples of addition reaction silicone resins include resins obtained by reacting and curing polydimethylsiloxane having vinyl groups introduced at the end or side chain with hydrogen siloxane using a platinum catalyst. Examples of condensation reaction silicone resins include resins with a three-dimensional crosslinked structure formed by condensing polydimethylsiloxane having hydroxyl groups at the end with polydimethylsiloxane having hydrogen atoms at the end using an organotin catalyst. Examples of ultraviolet curable silicone resins include those that utilize the same radical reaction as silicone rubber crosslinking, those that introduce unsaturated groups and photocure, those that decompose onium salts with ultraviolet or electron beams to generate strong acids and cleave epoxy groups to crosslink, and those that crosslink via the addition reaction of thiol to vinyl siloxane. Specific examples include acrylate-modified polydimethylsiloxane and glycidoxy-modified polydimethylsiloxane. Examples of silicone resins include a dimethylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, a dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer capped at both molecular chain terminals with trimethylsiloxy groups, and a dimethylsiloxane-diphenylsiloxane copolymer capped at both molecular chain terminals with dimethylvinylsiloxy groups.

[0090] The silicone resin preferably has an aromatic ring, preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and even more preferably a benzene ring.

[0091] As the silicone resin, a modified silicone resin obtained by reacting an organosilicon compound with a hydrosilylation agent is also preferred. The organosilicon compound preferably further has a polymerizable group. Examples of the polymerizable group include polymerizable groups contained in the resin. Examples of the organosilicon compound include compounds containing a silyl group, and 1,4-bis(dimethylsilyl)benzene or trivinylphenylsilane are preferred. The reaction temperature is preferably 100 to 200°C, and the reaction time is preferably 1 to 10 hours.

[0092] Examples of silicone resins include resins obtained from organosiloxanes and curable compositions described in JP-A-2020-026502.

[0093] Benzocyclobutene resins are resins having a benzocyclobutene ring, such as divinylsiloxane-bisbenzocyclobutene resins (e.g., CYCLOTENE resins, manufactured by The Dow Chemical Company).

[0094] Fluorene resins are resins having a fluorene ring. Examples of fluorene resins include resins obtained by reacting a fluorene compound having a hydroxyaryl structure with an aldehyde compound, and derivatives thereof. Examples of the fluorene compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(6-hydroxynaphthyl)fluorene.

[0095] A liquid crystal polymer is a resin that exhibits liquid crystallinity. A thermotropic liquid crystal polymer is preferred as the liquid crystal polymer. A thermotropic liquid crystal polymer refers to a polymer that exhibits liquid crystallinity within a predetermined temperature range. The thermotropic liquid crystal polymer may be any liquid crystal polymer that can be melt-molded, and examples thereof include thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides in which an amide bond is introduced into a thermoplastic liquid crystal polyester.

[0096] The liquid crystal polymer preferably has a repeating unit having an aromatic ring. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and even more preferably a benzene ring. The monomer from which the repeating unit having an aromatic ring is derived is preferably p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, or isophthalic acid. The liquid crystal polymer preferably contains two or more repeating units derived from compounds selected from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid, and more preferably contains four or five repeating units derived from the above compounds.

[0097] The liquid crystal polymer may contain repeating units derived from compounds other than the above compounds. Other compounds include, for example, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 3,3'-diphenyldicarboxylic acid, and 2,2'-diphenyldicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, chloro ... aromatic diols such as hydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, and 3,4'-dihydroxybiphenyl; aliphatic and alicyclic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanediol; aromatic hydroxycarboxylic acids such as 6-hydroxy-2-naphthoic acid and m-hydroxybenzoic acid; aromatic aminocarboxylic acids such as p-aminobenzoic acid and 6-amino-2-naphthoic acid; aromatic diamines such as 1,4-phenylenediamine, 4,4'-diaminobiphenyl, and 2,6-diaminonaphthalene; and aromatic hydroxyamines such as p-aminophenol. Examples of the liquid crystal polymer include the liquid crystal polymers described in JP 2006-299254 A and WO 2015 / 064437 A.

[0098] Examples of known resins include polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), and polyphenylene sulfide.

[0099] As mentioned above, the resin contained in the composition may be a precursor of each of the resins mentioned above.

[0100] 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.

[0101] The resin may be used alone or in combination of two or more. The resin content is preferably 1.0 to 99.0 mass% and more preferably 5.0 to 98.0 mass% based on the total solid content of the composition excluding the filler. The resin content is preferably 5.0 to 99.0 mass% based on the total solid content of the composition excluding the filler.

[0102] [Liquid Crystalline Compound Having a Polymerizable Group (Compound Z)] The composition contains Compound Z, which is a liquid crystal compound having a polymerizable group. Compound Z is a liquid crystal compound. Compound Z may be either a rod-shaped liquid crystal compound or a discotic liquid crystal compound, but a rod-shaped liquid crystal compound is preferred. Compound Z includes a compound having a polymerizable group and a mesogenic group exhibiting liquid crystallinity, and a compound in which the polymerizable group and the mesogenic group are linked via a spacer is preferred. Examples of the spacer include a chain aliphatic hydrocarbon group and a (poly)oxyalkylene group.

[0103] It is also preferable that compound Z is a low-molecular-weight liquid crystal compound. In terms of achieving better effects of the present invention, the molecular weight of compound Z is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. The molecular weight of compound Z is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more.

[0104] The polymerizable group possessed by compound Z may be any of a radically polymerizable group, a cationically polymerizable group, and an anionically polymerizable group, with a radically polymerizable group being preferred. As the radically polymerizable group, a group having an ethylenically unsaturated double bond is preferred. 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. The number of polymerizable groups possessed by compound Z is 1 or more, preferably 1 to 10, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 2.

[0105] The compound Z is preferably a compound represented by formula (Z1): Formula (Z1): P １ -L １ -ML ２ -P ２ In formula (Z1), 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.

[0106] In formula (Z1), P １ and P ２ each independently represents a polymerizable group. Examples of the polymerizable group include the polymerizable group contained in the compound Z described above, and preferred embodiments are also the same.

[0107] In formula (Z1), L １ and L ２ each independently represents a divalent linking group. Examples of the divalent linking group include —O—, —S—, —CO—, and —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 having 1 to 7 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, and even more preferably 2 to 8. The alkenylene group and alkynylene group preferably have 2 to 20 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 8. The divalent aliphatic hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom and a cyano group. Among the divalent aliphatic hydrocarbon groups, an alkylene group having 2 to 12 carbon atoms is particularly preferred.

[0108] 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 —O— or —CO—O—. ａ represents a divalent aliphatic hydrocarbon group. ａ The preferred embodiments of the divalent aliphatic hydrocarbon group represented by the formula: are as described above.

[0109] In formula (Z1), 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-*

[0110] In formula (M1), * represents a bonding position.

[0111] 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.

[0112] 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.

[0113] In formula (M1), m represents an integer of 1 to 3, preferably 2 or 3.

[0114] 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.

[0115]

[0116] Examples of compound Z are shown below, but the present invention is not limited to these. Compound Z can be synthesized by known methods, for example, by the method described in JP-A-11-513019.

[0117]

[0118]

[0119]

[0120] Compound Z may be used alone or in combination of two or more. In order to achieve more excellent effects of the present invention, the content of compound Z is preferably 1.0 to 85.0 mass%, more preferably 1.0 to 50.0 mass%, and even more preferably 1.0 to 30.0 mass%, relative to the total solid content of the composition. In order to achieve more excellent effects of the present invention, the mass ratio of the content of compound Z to the content of the resin is preferably 0.005 to 5.00, more preferably 0.01 to 3.00, and even more preferably 0.01 to 1.00.

[0121] In the composition, it is preferable that at least one of the resin and compound Z has an ethylenically unsaturated double bond, it is more preferable that compound Z has an ethylenically unsaturated double bond, and it is even more preferable that the resin and compound Z have an ethylenically unsaturated double bond. Note that an embodiment in which the resin and compound Z have an ethylenically unsaturated double bond includes an embodiment in which the resin and compound Z have a group having an ethylenically unsaturated double bond.

[0122] The various components that the composition may contain are described in detail below.

[0123] [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 the ability to form a pattern by photolithography. When the composition is used to manufacture the laminate and semiconductor package described below, the composition preferably exhibits photolithographic properties, since this allows for accurate formation of a pattern. 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. The photopolymerization initiator preferably functions as a polymerization initiator for the polymerizable group of the compound Z described above.

[0124] 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.

[0125] 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.).

[0126] 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.).

[0127] 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.

[0128] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 0.01 to 10.0 mass%, more preferably 0.1 to 5.0 mass%, and even more preferably 0.1 to 3.0 mass%, relative to the total solid content of the composition. The mass ratio of the content of compound Z to the content of the photopolymerization initiator is preferably 0.01 to 100.0, more preferably 0.1 to 75.0, even more preferably 0.5 to 50.0, and particularly preferably 0.7 to 40.0.

[0129] [Filler] The composition preferably contains a filler, since this results in a smaller dielectric tangent of the film formed. In terms of more excellent insulation reliability, the average particle size of the filler is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 150 nm or less. The lower limit of the average particle size of the filler is greater than 0 nm, preferably 5 nm or more, and more preferably 10 nm or more. The average particle size of the filler is also preferably 5 to 300 nm, more preferably 10 to 150 nm. The average particle size of the filler is a value calculated by the following particle size measurement method. Particle size measurement method: A rectangular region of 3 μm × 10 μm in a cross section taken along the normal direction to the surface of a composition layer formed using the composition is observed with a scanning electron microscope, and the major axes of all fillers observed within the region are measured at five different locations on the film. The average value of the major axes of all fillers measured in each measurement is defined as the average particle size of the filler.

[0130] 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 of the resulting composition layer along the normal direction of its surface (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 using a scanning electron microscope, and the major axes of all fillers observed within the region are measured. The scanning electron microscope used is an S-4800 manufactured by Hitachi High-Tech Corporation. 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 fillers measured in each procedure is taken as the average particle size of the filler. The major axis refers to the length of the longest line segment connecting any two points on the outline of the filler's outer shape in the observed image. Furthermore, when fillers are aggregated to form aggregates in the observed image, the major axis of each filler constituting the aggregate is measured.

[0131] Examples of fillers include organic fillers and inorganic fillers, with inorganic fillers being preferred. Examples of 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 filler preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide (silica).

[0132] The shape of the filler may be either spherical or non-spherical (for example, crushed or fibrous), with spherical being preferred. The filler may be surface-treated. Examples of surface treatments include treatments to introduce functional groups and treatments using known surface treatment agents. Examples of the functional groups include polymerizable groups (for example, the polymerizable group possessed by compound Z) and hydrophobic groups. Examples of surface treatment agents include silane coupling agents, titanate coupling agents, and silazane compounds. Examples of methods for surface treatment of the filler include a dry method in which surface treatment is performed in a gas phase and a wet method in which surface treatment is performed in a liquid phase.

[0133] Examples of fillers include 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 slurry), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide), PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), and M Examples of such an emulsion include EK-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).

[0134] The refractive index of the filler is preferably 0.5 to 30.0, and more preferably 1.2 to 1.8. The refractive index can be measured by the method described above.

[0135] The filler may be used alone or in combination of two or more. The filler content is preferably 20.0 mass% or more, more preferably 30.0 mass% or more, based on the total solid content of the composition. The filler content is preferably 90.0 mass% or less, more preferably 80.0 mass% or less, and even more preferably 70.0 mass% or less, based on the total solid content of the composition. The mass ratio of the filler content to the resin content is preferably 0.5 to 30.0, more preferably 1.0 to 20.0.

[0136] [Thermal Base Generator] The composition preferably contains a thermal base generator. When the composition contains a resin precursor, the inclusion of the thermal base generator in the composition promotes the reaction of the resin precursor, resulting in better linear expansion coefficient and insulation reliability.

[0137] 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), with an ammonium salt compound or an iminium salt compound being more preferred. The anion constituting the onium salt compound is preferably a carboxylate anion, a phenol anion, a phosphate anion, or a sulfate anion, with a carboxylate anion being more preferred. 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.

[0138] 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.

[0139] The acidic compound is preferably a compound represented by formula (A1).

[0140]

[0141] 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.

[0142] In formula (A1), A ａ１ 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 groups may further have a substituent.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] In formula (A1), m represents an integer of 1 or greater. m is preferably 1 or 2, and more preferably 1.

[0147] In formula (A1), p represents an integer of 1 or greater. p is preferably 1 or 2, and more preferably 1.

[0148] The ammonium cation constituting the ammonium salt compound is preferably a cation represented by formula (101). The iminium cation constituting the iminium salt compound is preferably a cation represented by formula (102).

[0149]

[0150] In formula (101), R １ ~R ４ R each independently represents a hydrogen atom or an aliphatic group. １ ~R ４ At least two of R may be bonded to each other to form a ring. ５ and R ６ R each independently represents a hydrogen atom or an aliphatic group. ７ represents an aliphatic group. ５ ~R ７ At least two of these may be bonded to each other to form a ring.

[0151] R １ ~R ４ and R ５ ~R ７The aliphatic group represented by the formula (I) may be linear, branched, or cyclic. The number of carbon atoms in the aliphatic group is preferably 1 to 10. The aliphatic group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. The aliphatic group may have a substituent. Examples of the substituent include an arylcarbonyl group. The aliphatic group may have a substituent such that the methylene group (-CH ２ -) may be replaced with a heteroatom (for example, an oxygen atom, a sulfur atom, or -NR-, where R represents a hydrogen atom or a substituent). ５ ~R ７ At least one of the R is preferably an aliphatic group having —NR—, and more preferably an alkyl group having —NR—. ５ ~R ７ At least two of R may be bonded to each other to form a ring; ５ and R ７ , and R ６ and R ７ are preferably bonded to each other to form a ring. In other words, the ring formed is preferably a polycyclic heterocycle, more preferably a bicyclic heterocycle.

[0152] Examples of the thermal base generator include the thermal base generators described in WO 2018 / 038002.

[0153] The temperature at which the thermal base generator generates a base is preferably the heating temperature in step 3 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.

[0154] 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 resin X is preferably 0.0005 to 1.0, more preferably 0.001 to 0.1, and even more preferably 0.001 to 0.05.

[0155] [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. In particular, when the composition contains a filler, it is preferable that the composition contains a plasticizer. The plasticizer is a compound different from the various components described above, and preferably does not have a polymerizable group.

[0156] 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.

[0157] 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°C to 300°C, with a temperature increase rate of 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°C 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] Examples of phosphate esters include triamyl phosphate and tris(2-butoxyethyl) phosphate.

[0162] 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.

[0163] 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.

[0164] 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 filler content is preferably 0.05 to 1.0 and more preferably 0.2 to 0.7.

[0165] [Surfactant] The composition also preferably contains a surfactant.

[0166] 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.

[0167] 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).

[0168] 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.

[0169] 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).

[0170] 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.).

[0171] 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.

[0172] The repeating unit having a group having a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).

[0173]

[0174] In formula (SX1), each R independently represents an alkyl group having 1 to 3 carbon atoms. １ represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. When a plurality of R's are present, the R's may be the same or different.

[0175]

[0176] In formula (SX2), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0177] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0178]

[0179] In formula (SX3), R ４ and R ５ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0180] 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).

[0181] 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.

[0182] 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.

[0183] [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.

[0184] 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.

[0185] [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.

[0186] <Photoacid Generator> The composition may contain a photoacid generator. The photoacid generator is a compound that generates an acid when exposed to light (e.g., exposure light). When the resin has an acid-decomposable group, the composition preferably contains a photoacid generator.

[0187] Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators. Examples of ionic photoacid generators include compounds having a sulfonium structure, onium salt compounds having a diaryliodonium or triarylsulfonium structure, and ammonium salt compounds having a quaternary ammonium structure. Examples of ionic photoacid generators include those described in paragraphs

[0114] to

[0133] of JP 2014-085643 A. Examples of nonionic photoacid generators include trichloromethyl-s-triazine and its derivatives (trichloromethyl-s-triazines which may have a substituent), compounds having a diazomethane structure, compounds having an imide sulfonate structure, and compounds having an oxime sulfonate structure. Examples of trichloromethyl-s-triazine and its derivatives, diazomethane compounds, and imide sulfonate compounds include those described in paragraphs

[0083] to

[0088] of JP 2011-221494 A. Furthermore, examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640.

[0188] The content of the photoacid generator is preferably 0.1 to 10.0 mass %, more preferably 0.5 to 5.0 mass %, based on the total solid content of the composition.

[0189] <Curing Agent> The composition may contain a curing agent. The curing agent is not particularly limited as long as it is, for example, a compound that promotes curing of the various components contained in the composition. Examples of the curing agent include cyanate ester curing agents and benzoxazine curing agents. Examples of cyanate ester curing agents and benzoxazine curing agents include those described in JP-A-2020-154325 and JP-A-2004-277460.

[0190] <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.

[0191] <Impurities> The composition may contain impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so the following contents are preferred.

[0192] The content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the composition. The lower limit is often 0 ppb by mass or more, and may be 1 ppb by mass or more, or 0.1 ppm by mass or more, relative to the total mass of the composition. The content of impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0193] Examples of methods for adjusting the content of impurities include using raw materials with low impurity contents as raw materials for the composition, purifying the raw materials for the composition before use, and preventing the inclusion of impurities during preparation of the composition.

[0194] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the composition is preferably low. Specifically, the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the composition. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the composition. The content of these compounds can be adjusted using the same method as for the impurities described above. Furthermore, these compounds can be quantified using known measurement methods.

[0195] 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.

[0196] [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.

[0197] 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 superior insulation reliability. The average thickness of the specific film 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 superior pattern resolution.

[0198] [Transfer Film] The transfer film of the present invention has a temporary support and a composition layer formed using the above-described composition.

[0199] 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.

[0200] [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.

[0201] 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.

[0202] 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.

[0203] 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).

[0204] 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.

[0205] 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.).

[0206] 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.

[0207] 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.).

[0208] [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 content of resin X is preferably 5.0% by mass or more relative to the total solid content of the composition" should be replaced with "The content of resin X is preferably 5.0% by mass or more relative to the total mass of the composition layer."

[0209] The composition layer preferably further contains 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.

[0210] 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.

[0211] The transfer film may have layers other than those described above.

[0212] [Intermediate layer and thermoplastic resin layer] 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.

[0213] [Cover Film] The transfer film may have a cover film. The number of fisheyes having 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.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] 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.).

[0218] The transfer film may include other layers in addition to the above-described layers. Examples of the other layers include a high refractive index layer. Examples of the high refractive index layer include those described in paragraphs 0168 to 0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0219] [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.

[0220] 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.

[0221] 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.

[0222] [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.

[0223] [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 above-mentioned composition to obtain a laminate. Specifically, the method for producing a laminate preferably includes the following steps 1 to 3: Step 1: Step of forming a composition layer on a substrate using the composition; Step 2: Step of forming a pattern including vias in the composition layer; Step 3: Step of subjecting the pattern to at least one of heating and exposure.

[0224] Each step of the method for producing the laminate will be described in detail below.

[0225] [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.

[0226] <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.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] [Step 2] Step 2 is a step of forming a pattern including vias in the composition layer. The pattern including vias may be formed only in the composition layer, or may be formed in both the composition layer and the substrate. The pattern including vias may be either 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 or square front shape (the shape when the via is observed from the direction in which the via bottom is visible). In view of improving 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.

[0231] Examples of methods for forming a pattern containing vias include methods using a drill, a laser, and plasma. When the composition has photolithographic properties, the step of forming a pattern containing vias preferably includes step 2-1 of patternwise exposing a composition layer and step 2-2 of developing the pattern-exposed composition layer using a developer to form a pattern. Note that "patternwise exposure" refers to a form of patternwise exposure, i.e., exposure in a form in which exposed areas and unexposed areas exist.

[0232] <Step 2-1> Step 2-1 is a step of patternwise exposing the composition layer. 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.

[0233] 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.

[0234] When a composition layer is formed using a transfer film in step 1, in step 2-1, patterned exposure may be performed after peeling the temporary support from the composition layer, or patterned exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. In order 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 patterned exposure without peeling off the temporary support. The patterned 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. It is preferable to peel the temporary support from the composition layer before step 2-2.

[0235] <Step 2-2> Step 2-2 is a step of forming a pattern by developing the composition layer exposed after step 2-1 using a developer. Examples of the developer include an alkaline developer and an organic solvent developer.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] [Step 3] Step 3 is a step of subjecting the pattern obtained in Step 2 to at least one of heating and exposure. Step 3 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 3 is preferably a step of at least heating.

[0240] 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.

[0241] 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.

[0242] [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.

[0243] <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.

[0244] <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.

[0245] <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.

[0246] 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.

[0247] [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.).

[0248] [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 including steps Z1 to Z4 in this order. Step Z1: A step of forming a composition layer on a substrate having a conductive layer. Step Z2: A step of forming a pattern having vias in the composition layer. Step Z3: A step of heat-treating the pattern. Step Z4: A step of forming a circuit pattern on the pattern.

[0249] Steps Z1 to Z3 in the method for manufacturing a semiconductor package include the above-mentioned steps 1 to 3, respectively.

[0250] [Step Z4] Step Z4 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 serves 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 suppressing 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.

[0251] 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, for example, through a mask on which the desired wiring pattern is drawn. Examples of the exposure method include the exposure method in step 2-1. 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.

[0252] 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.

[0253] 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 Z3 and before step Z4. By performing the roughening step, the surface of the pattern can be roughened to improve adhesion to 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.

[0254] 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.

[0255] [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.

[0256] 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.

[0257] [Preparation of Composition] Various components were mixed to prepare a mixture in the amounts (solid content ratio) shown in the table below. Next, the upper mixture was diluted with a mixed solvent containing 25% by mass of MEK (methyl ethyl ketone) and 75% by mass of NMP (N-methylpyrrolidone) to a solid content of 30% by mass.

[0258] The various components contained in the composition are listed below.

[0259] [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-8: Silicone resin, average unit formula M ２ D ３ M: (CH ２ =CH)(CH ３ ) (C ６ H ５ ) SiO １／２ D: (C ６ H ５ ) ２ SiO ２／２ A-9: Benzocyclobutene resin, Cyclotene resin XUR-JW-1148-200201415-47, manufactured by The Dow Chemical Company. A-10: Liquid crystal polyester, a resin synthesized by the synthesis method for resin A-10 described below. A-11: Vinylbenzyl-modified polyphenylene ether resin, manufactured by Mitsubishi Gas Chemical Company, Inc., "OPE-2St 1200" toluene solution. A-12: Acrylic resin, ARUFON UC-3000, manufactured by Toagosei Co., Ltd.

[0260]

[0261] <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 precipitate, which was a crude polymer. 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.

[0262] <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.

[0263] <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.

[0264] <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.

[0265] <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.

[0266] <Method for synthesizing resin A-10> A 2.5 L reaction vessel equipped with a stirring blade and a distillation tube was charged with 435 g of p-hydroxybenzoic acid, 164 g of 4,4'-dihydroxybiphenyl, 44 g of hydroquinone, 146 g of terephthalic acid, 78 g of isophthalic acid, and 684 g of acetic anhydride, and the mixture was stirred under a nitrogen atmosphere while reacting at 150 ° C. for 2.5 hours, and then heated to 300 ° C. over 3.5 hours. Thereafter, the polymerization temperature was maintained at 300 ° C., the pressure was reduced to 1.0 mmHg over 1.0 hour, and the reaction was continued for another 2 hours. Next, the inside of the reaction vessel was pressurized to 0.12 MPa, and resin A-10 was discharged into a strand-like substance to obtain resin A-10.

[0267] 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 solids concentration of 65% by mass, manufactured by DIC Corporation. J-3: Organosilicon compound (silyl compound): Compound synthesized by the following method. 700.0 g of 1,4-bis(dimethylsilyl)benzene (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.36 g of 5% by mass platinum carbon powder (manufactured by N.E. Chemcat Corporation) were added to a 2 L four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, and the mixture was heated to 90 ° C. using an oil bath. 149 g of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise to the mixture. After the dropwise addition was completed, the mixture was stirred at 95 ° C. for 4 hours. After stirring, the mixture was returned to 25°C, 8.4 g of activated carbon was added, and the mixture was stirred for 2 hours. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 500 g of a silyl compound. The silyl compound was a mixture of compounds having a structure represented by any one of formulas (a) to (e), with the ratio of each compound being (a):(b):(c):(d):(e) = 29:21:16:9:25 (mol%). Components (a) to (e) are shown below.

[0268]

[0269]

[0270]

[0271]

[0272] [Compound Z]

[0273]

[0274] [Other components] Oxe-01: photopolymerization initiator, Irgacure OXE-01, manufactured by BASF NHM-5N: filler, silicon dioxide (spherical silica), average particle size 100 nm, manufactured by Tokuyama Corporation NHM-3N: filler, silicon dioxide (spherical silica), average particle size 150 nm, manufactured by Tokuyama Corporation YA050C-MJE: filler, silicon dioxide (spherical silica slurry), average particle size 50 nm, manufactured by Admatec Co., Ltd. NP-5N: filler, silicon dioxide (spherical silica), average particle size 100 nm, manufactured by Tokuyama Corporation E-1: thermal base generator, compound having the following structure

[0275]

[0276] ・EPEG: plasticizer, ethylphthalylethyl glycolate, manufactured by Tokyo Chemical Industry Co., Ltd. ・S-506: silicone surfactant, manufactured by DIC Corporation ・F-551A: Megafac (registered trademark) F551A, fluorine-based surfactant, manufactured by DIC Corporation ・HAT: rust inhibitor, 5-amino-1H-tetrazole ・J-4: platinum catalyst: hydrosilylation agent, polysiloxane diluted product of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 1% by mass), component (C) of JP2020-026502A ・J-5: isopropylidene group-containing maleimide compound, MIR-500-60T, toluene solution ・TEGDA: polymerizable compound without liquid crystallinity, tetraethylene glycol diacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0277] [Evaluation] The obtained compositions of each of the Examples and Comparative Examples were evaluated for photolithographic properties of the composition, and the linear expansion coefficient, insulating reliability, and dielectric properties of the specific film.

[0278] [Photolithography] The prepared composition was applied to a copper substrate and dried at 100°C to obtain a laminate having a 5 µm thick composition layer on the copper substrate. The obtained laminate was exposed to light (ultra-high pressure mercury lamp, wavelength 365 nm, cumulative illuminance measured with an illuminometer: 1000 mJ / cm2) from the side opposite to the substrate side of the composition layer. ２) After exposure, development was carried out at room temperature using the developer shown in the table below until the composition layer in the unexposed areas disappeared. Thereafter, the boundary between the exposed and unexposed areas was observed using an optical microscope, and the presence or absence of photolithographic properties was evaluated according to the following evaluation criteria. If a residual film was observed in the exposed area, the composition layer had photolithographic properties. The details of the developers in the table are as follows: CPO: cyclopentanone, organic solvent developer 5% TMAH aqueous solution: 5% by mass tetramethylammonium hydroxide aqueous solution, alkaline developer 1% Na ２ CO ３ Aqueous solution: 1% by mass sodium carbonate aqueous solution, alkaline developer

[0279] <Evaluation Criteria> A: A residual film was observed in the exposed area. B: No residual film was observed in the exposed area.

[0280] [Linear expansion coefficient] The prepared composition was applied to a copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) substrate and dried to obtain a laminate having a 30 μm-thick composition layer on the copper substrate. When the composition exhibited photolithographic properties in the evaluation of [Photolithographic properties] above (i.e., was rated A), a free-standing film of the composition was obtained by the following procedure. The obtained laminate was exposed to light (ultra-high pressure mercury lamp, integrated illuminance of 100 mJ / cm2 measured with an illuminometer at a wavelength of 365 nm) from the side opposite to the substrate side of the composition layer. ２), and then heat-treated in an oven (200°C, 8 hours) to form a specific film. The laminate was immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, rinsed (in pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film (specific film) derived from the composition layer. If the composition did not exhibit photolithographic properties in the above-mentioned [Photolithographic Properties] evaluation (i.e., it was rated B), a free-standing film of the composition was obtained by the following procedure. The obtained laminate was heat-treated in an oven (200°C, 8 hours) to form a specific film, then immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, rinsed (in pure water at room temperature for 1 hour), and then peeled off from the substrate to obtain a free-standing film (specific film) derived from the composition layer. If the free-standing film could not be peeled off by the above-mentioned peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week and peeled off. The produced free-standing film was cut into a strip (19 mm x 5 mm), and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a temperature rise rate of 10°C / min, a chuck distance of 10 mm, and a load of 40 mN. The linear expansion coefficient was measured as a value (ppm / K) in the temperature range of 50 to 150°C during heating, and was calculated as the average value of three measurements. The obtained linear expansion coefficient was evaluated according to the following evaluation criteria.

[0281] <Evaluation criteria> A: 36 ppm / K or less B: More than 36 ppm / K, 145 ppm / K or less C: More than 145 ppm / K

[0282] [Insulation Reliability] A copper pattern having a thickness of 5 μm and L / S=30 μm / 30 μm formed in a comb shape on a silicon wafer substrate was prepared as 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. When the composition exhibited photolithographic properties in the evaluation of [Photolithographic Properties] above (i.e., was rated A), an evaluation sample was prepared according to the following procedure. The obtained laminate was exposed to light (ultra-high pressure mercury lamp, cumulative illuminance of 100 mJ / cm2 measured with an illuminometer at a wavelength of 365 nm) from the side opposite the substrate side of the composition layer. ２) was prepared. After exposure, the laminate was heat-treated at 200°C for 480 minutes in a nitrogen atmosphere to prepare an evaluation sample. When the composition did not exhibit photolithographic properties in the evaluation of [Photolithographic Properties] above (i.e., it was rated B), an evaluation sample was prepared by the following procedure. The laminate was heat-treated at 200°C for 480 minutes in a nitrogen atmosphere to prepare an evaluation sample. Ten evaluation samples were prepared, and each evaluation sample was placed in the chamber of a HAST tester at 130°C and 85% RH (relative humidity). After 200 hours, a voltage of 3.3 V was applied, and the number of samples in which migration occurred was counted. The initial resistance value when initially measured at room temperature (23°C) was 1 x 10 １４ Ω or more, the resistance value is 1 × 10 ３ It was determined that migration had occurred when the resistance dropped to Ω or less. Based on the occurrence of migration, insulation reliability was evaluated according to the following evaluation criteria. The fewer samples in which migration occurred, the better the insulation reliability.

[0283] <Evaluation criteria> A: Migration occurred in one or less samples. B: Migration occurred in two or three samples. C: Migration occurred in four or five samples. D: Migration occurred in six or seven samples. E: Migration occurred in eight or more samples.

[0284] [Dielectric Properties] The freestanding films obtained by the same method as in the above [Linear Expansion Coefficient] were measured for their average dielectric loss tangent using a 28 GHz split cylinder resonator (manufactured by Kanto Electronics Application Development Co., Ltd.) The measurement was performed on three samples, and the average value was taken as the average dielectric loss tangent Df, and the dielectric properties were evaluated according to the following evaluation criteria.

[0285] <Evaluation criteria> A: Df<0.01 B: 0.01≦Df<0.02 C: 0.02≦Df<0.03 D: 0.03≦Df

[0286] [Results] The contents of various components, the developers used for development, and the evaluation results are shown below. In the tables, "amount" indicates the content (mass%) relative to the total solid content of the composition. In the tables, the "B / A" column indicates the mass ratio of the content of (B) compound Z to the content of (A) resin (content of (B) compound Z / content of (A) resin). Table 2 is a continuation of Table 1, Table 4 is a continuation of Table 3, and Table 6 is a continuation of Table 5.

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293] From the results shown in the above table, it was confirmed that the composition of the present invention can form a film having a small linear expansion coefficient and excellent insulating reliability.

[0294] Comparison of Examples 22 to 24 with other Examples confirmed that when the composition contained a photopolymerization initiator, it exhibited photolithographic properties. Comparison of Examples 6 to 9, 19 to 21, 43, 54, 65, 76, 87, 98, 109, 120, 131, and 142 with other Examples confirmed that when the content of Compound Z was 85.0 mass% or less, relative to the total solids content of the composition, the insulating reliability was better, when it was 50.0 mass% or less, the insulating reliability was even better, and when it was 30.0 mass% or less, the insulating reliability was particularly excellent. Comparison of Examples 6 to 9 and 19 to 21 with other Examples confirmed that when the mass ratio of the content of Compound Z to the content of the resin was 3.00 or less, the insulating reliability was better, and when it was 1.00 or less, the insulating reliability was even better. A comparison of Examples 1 to 4, 38 to 41, 49 to 52, 60 to 63, 71 to 74, 82 to 85, 93 to 96, 104 to 107, 115 to 118, 126 to 129, and 137 to 140 confirmed that when the resin contained at least one selected from the group consisting of polyimide, polybenzoxazole, polyphenylene ether resin, silicone resin, benzocyclobutene resin, liquid crystal polymer, and precursors thereof, the dielectric properties were superior, and when the resin contained at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof, the dielectric properties were even superior. A comparison of Examples 31 to 37 with Examples 26 to 29 confirmed that when the composition contained a filler, the dielectric properties were superior.

[0295] Instead of a laminate having a composition layer formed using the composition, a laminate having a composition layer formed using a transfer film prepared according to the following procedure was evaluated using the same procedure as the above-mentioned [Linear Expansion Coefficient]. Evaluation results equivalent to the [Linear Expansion Coefficient] evaluation results for the specific film formed using the composition were obtained. The composition of each example was applied to a temporary support (16QS, manufactured by Toray Industries, Inc., 16 μm thick PET film) and dried at 100°C to form a composition layer. The film thickness of the composition layer was adjusted to 10 μm after drying. Next, a cover film (manufactured by Oji F-Tex Co., Ltd., polypropylene film, FG-201, thickness 30 μm) was laminated to the side of the composition layer opposite the temporary support to obtain a transfer film having a composition layer. The cover film was peeled off from the resulting transfer film, and the exposed composition layer was laminated onto a copper-clad polyimide film (Metaloyal, manufactured by Toray Industries, Inc.) substrate to transfer the composition layer, and then the temporary support was peeled off. Lamination was performed using a vacuum laminator (manufactured by MCK Corporation) at a rubber roller temperature of 100° C. and a conveying speed of 1 m / min. Further, the operation of transferring a composition layer onto the obtained composition layer on the substrate in the same manner was repeated twice to obtain a laminate having a composition layer with a thickness of 30 μm on the substrate.

[0296] The cover film was peeled off from the transfer film obtained by the above method, and the exposed composition layer was laminated onto a copper substrate to transfer the composition layer. Lamination was performed using a vacuum laminator (manufactured by MCK Corporation) at a rubber roller temperature of 100°C and a conveying speed of 1 m / min. The obtained laminate was exposed to light (ultra-high pressure mercury lamp, cumulative illuminance of 1000 mJ / cm measured with an illuminometer at a wavelength of 365 nm) from the side opposite to the substrate side of the composition layer. ２ After exposure, development was carried out at room temperature using the developer shown in the table until the composition layer in the unexposed areas disappeared. Thereafter, the boundary between the exposed and unexposed areas was observed with an optical microscope and evaluated according to the same evaluation criteria as in the above-mentioned [Photolithographic properties]. The evaluation results were the same as those for a composition layer formed by applying and drying the composition.

[0297] The transfer film of each example obtained by the above-described method was applied to a glass epoxy substrate (CCL-EL190T, thickness 1.0 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern had been formed, and a composition layer was formed on both sides of the glass epoxy substrate. Lamination was performed using a vacuum laminator (manufactured by MCK Corporation) under conditions of a substrate temperature of 40°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. A pattern having vias with a diameter of 60 μm was formed at predetermined positions on the composition layer and subjected to a heat treatment. After that, residues were removed using a sodium permanganate aqueous solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed at predetermined positions using a known dry film resist, and electrolytic plating was performed. The resist pattern was then peeled off using a stripping solution. Finally, a seed layer etching treatment was performed, followed by a heat treatment (200°C, 1.5 hours) to form copper wiring on the cured film. The above process from lamination to heat treatment was repeated 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 in a predetermined position on a printed wiring board to obtain a semiconductor package substrate. The resulting semiconductor package substrate was confirmed to operate normally.

[0298] 12: Temporary support 14: Composition layer 16: Cover film 100: Transfer film

Claims

1. a resin and a liquid crystal compound having a polymerizable group, The composition, wherein the resin comprises at least one selected from the group consisting of polyimide, silicone resin, polybenzoxazole, phenolic resin, epoxy resin, polyphenylene ether resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polybenzimidazole, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene copolymer resin, polyphenylene sulfide, and precursors thereof.

2. The composition according to claim 1 , wherein the liquid crystal compound having a polymerizable group is a compound represented by formula (Z1): Formula (Z1): P １ -L １ -M-L ２ -P ２ In formula (Z1), P １ and P ２ each independently represents a polymerizable group. L １ and L ２ each independently represents a divalent linking group. M represents a mesogenic group.

3. The composition of claim 1 further comprising a photoinitiator.

4. The composition according to claim 1 , wherein at least one of the resin and the liquid crystal compound having a polymerizable group has an ethylenically unsaturated double bond.

5. 2. The composition according to claim 1, wherein the liquid crystal compound having a polymerizable group has a molecular weight of 2,000 or less.

6. 2. The composition according to claim 1, wherein the content of the liquid crystal compound having a polymerizable group is 1.0 to 50.0% by mass based on the total solid content of the composition.

7. 2. The composition according to claim 1, wherein the content of the liquid crystal compound having a polymerizable group is 1.0 to 30.0% by mass based on the total solid content of the composition.

8. 2. The composition according to claim 1, wherein the mass ratio of the content of the liquid crystal compound having a polymerizable group to the content of the resin is 0.01 to 3.

00.

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

10. The composition of claim 1 further comprising a filler.

11. 11. The composition of claim 10, wherein the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

12. The composition according to claim 10, wherein the average particle size of the filler is 300 nm or less.

13. The composition according to claim 10, wherein the filler has an average particle size of 150 nm or less.

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

15. The composition according to claim 10, wherein the content of the filler is 90.0 mass% or less based on the total solid content of the composition.

16. Further comprising a photopolymerization initiator, the resin contains at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof; The composition of claim 1 further comprising a filler.

17. At least one of the resin and the liquid crystal compound having a polymerizable group has an ethylenically unsaturated double bond, the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates; 17. The composition of claim 16, wherein the filler has an average particle size of 150 nm or less.

18. The composition according to any one of claims 1 to 17, which is used for forming an insulating film for a semiconductor package.

19. The composition described in claim 3, used to form an insulating film for a semiconductor package.

20. A transfer film having a temporary support and a composition layer formed using the composition according to any one of claims 1 to 17.

21. A transfer film having a temporary support and a composition layer formed using the composition of claim 1, the composition further comprises a photopolymerization initiator; The transfer film, wherein the resin contains at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.

22. Step 1: forming a composition layer on a substrate using the composition according to any one of claims 1 to 17; Step 2: forming a pattern including vias in the composition layer; and step 3 of subjecting the pattern to at least one of heating and exposure to light.

23. A laminate produced by the method for producing a laminate according to claim 22.

24. A semiconductor package comprising the laminate of claim 23.